Depending on the chalcogen employed and the crystallization conditions, different binding motifs were found. With sulfur centres as Lewis acidic interaction sites, only weak chalcogen bonding was observed. For selenium-based compounds, however, different bidentate coordination motifs were found between the chalcogen-bonding donor and the respective counter-ions. i.e. the activation of quinolines, sulfur- and selenium-based chalcogen-bonding catalysts showed comparable properties, which is unexpected, as the selenium-containing catalysts should show superior catalytic properties due to the increased polarizability of selenium compared to sulfur. Herein, we present four crystal structures of the respective 1,3-bis(benzimidazoliumyl)benzene-based chalcogen-bonding catalyst containing sulfur (S3) and selenium  as Lewis acidic centres. The sulfur-containing catalyst shows weaker chalcogen bonding compared to its selenium analogue, as well as anion–π interactions. The selenium-based analogues, on the other hand, show stronger chalcogen-bonding motifs compared to the sulfur equivalent, depending on the crystallization conditions, but in every case, the intermolecular interactions are comparable in strength. Other interactions, such as hydrogen bonding and anion–π, were also observed, but in the latter case, the interaction distances are longer compared to those of the sulfur-based equivalent. The solid-state structures could not further explain the high catalytic activity of the sulfur-containing catalysts. Therefore, a comparison of their σ-hole depths from density functional theory (DFT) gas-phase calculations was performed, which are again in line with the previously found properties in the solid-state structures.1,3-Bis(benzimidazoliumyl)benzene-based chalcogen-bonding catalysts were previously successfully applied in different benchmark reactions. In one of those examples,  Furthermore, the interaction site is not limited to a single atom and can vary between tellurium, selenium and sulfur, which consequently allows the fine tuning of the interaction strength. Less electronegativity and easier polarization of the chalcogen leads to an increased anisotropic electron distribution and thus an enlarged electropositive region (σ-hole), as well as to a lower-lying σ*-orbital of the R—Ch bond. Hence, the strength of the chalcogen bonding increases with the atomic number of chalcogen (S < Se < Te). Another difference to hydrogen and halogen bonding is the second substituent located at the interacting atom. This interaction was observed in several solid-state systems, such as Ebselen, a synthetic organoselenium drug   using mirror monochromators and a HyPix-6000HE Hybrid photon counting X-ray detector. The crystals were mounted in Hampton CryoLoops using GE/Bayer silicone grease. Data were recorded and reduced using Crysalis PRO software  aluminium sheets  were used for TLC analysis. Substances were detected by fluorescence under UV light (wavelength λ = 254 nm). Column chromatography was performed with silica gel  and distilled solvents. The solvents used as eluents with the corresponding H-1,3-benzodiazol-3-ium) bis(trifluoromethanesulfonate), 1 benzene  was added and dissolved in 30 ml dry methanol (52.3 mM). To the solution were added 1.00 g sulfur  and 1.28 g Cs2CO3 . The resulting suspension was stirred for 24 h under reflux. The mixture was filtered over a pad of silica, which was rinsed twice with dichloromethane (DCM). The solvents were removed under reduced pressure and the crude solid was purified by column chromatography with pentane–EtOAc (2:1 v/v) (RF = 0.33). The solvents were removed under reduced pressure and product S2 was obtained as a white solid (m.p. 240 °C). Yield: 0.547 g . 1H NMR : δ (ppm) = 7.82–7.75 , 7.48 , 7.36 , 7.29–7.23 , 3.92 . 13C NMR : δ (ppm) = 170.30, 136.84, 132.73, 132.64, 130.36, 128.19, 127.74, 123.83 , 110.59, 109.05, 31.48. ATR-IR: −1) = 3030 (w), 2924 (m), 2345 (w), 1736 (m), 1728 (m), 1601 (s), 1589 (m), 1476 (s), 1454 (m), 1427 (s), 1377 (vs), 1337 (vs), 1302 (s), 1265 (s), 1211 (vs), 1161 (m), 1144 (m), 1119 (s), 1015 (m), 993 (m), 924 (m), 887 (w), 849 (w), 806 (s), 743 (vs), 714 (vs), 692 (vs), 615 (s), 559 (vs), 540 (m), 471 (s), 432 (m), 420 (vs). EI–MS (70 eV): m/z(+) = 402.2 [M]+, 369.2 [M − S]+.A reported procedure was slightly modified for the synthesis of compound Se2  was added and dissolved in 15 ml dry methanol (52.3 mM). To this solution were added 0.155 g selenium  and 0.638 g Cs2CO3 . The resulting suspension was stirred for 24 h under reflux. The mixture was filtered over a pad of silica, which was rinsed twice with DCM. The solvents were removed under reduced pressure and the crude solid was purified by column chromatography with pentane–EtOAc (1:1 v/v) (RF = 0.59). The solvents were removed under reduced pressure and product Se2 was obtained as a white solid (m.p. = 266 °C). Yield: 0.234 g . 1H NMR : δ (ppm) = 7.86–7.75 , 7.48 , 7.36 , 7.31–7.24 , 3.92 . 13C NMR : δ (ppm) = 167.36, 137.58, 133.97, 133.67, 130.52, 128.97, 128.97, 124.29 , 111.31, 109.58, 33.58. ATR-IR: −1) = 3053 (w), 2922 (m), 2853 (w), 1726 (w), 1601 (m), 1589 (m), 1493 (m), 1474 (s), 1456 (m), 1425 (m), 1375 (s), 1333 (vs), 1306 (s), 1298 (s), 1263.37 (s), 1211 (s), 1161 (m), 1144 (m), 1121 (s), 1084 (s), 1015 (m), 991 (m), 874 (m), 853 (m), 808 (s), 802 (s), 745 (vs), 709 (s), 691 (s), 675 (m), 646 (m), 617 (m), 592 (m), 557 (s), 534 (m), 469 (m), 430 (m). EI–MS (70 ev): m/z = 417.10 [M − Se]+.A reported procedure was slightly modified for the synthesis of compound S3  dissolved in 15 ml dry DCM (66.3 mM). Afterwards, 0.281 ml methyl trifluoromethanesulfonate  was added dropwise. The mixture was stirred for 24 h at room temperature. The solvent was removed under reduced pressure. The crude solid was washed three times with diethyl ether and three times with pentane, and then dried under high vacuum. Product S3 was obtained as a pale-yellow solid (m.p. = 222 °C). Yield: 0.630 g . 1H NMR : δ (ppm) = 8.14 , 8.07–8.01 , 7.99–7.94 , 7.75 , 7.58 , 4.22 , 2.51 . 13C NMR : δ (ppm) = 151.97, 135.33, 134.21, 133.95, 131.59, 129.21, 128.85, 127.87, 114.35, 113.82, 34.55, 18.20. 19F NMR : δ (ppm) = −79.31 . ATR-IR: −1) = 3066 (w), 3045 (w), 1604 (w), 1508 (m), 1498 (m), 1483 (m), 1463 (m), 1398 (w), 1319 (w), 1254 (vs), 1223 (vs), 1148 (vs), 1088 (m), 1028 (vs), 982 (m), 925 (w), 849 (w), 818 (m), 799 (w), 767 (s), 754 (s), 746 (s), 698 (s), 633 (vs), 573 (s), 559 (s), 515 (vs), 444 (m), 417 (m). ESI–MS: m/z(+) = calc. 581.10 [M + OTf]+; found 581.10 [M + OTf]+. m/z(−) = calc. 148.95 [OTf]−; found 149.29 [OTf]−.A reported procedure was slightly modified for the synthesis of compound Se3  dissolved in 20 ml dry DCM (15.1 mM). Afterwards, 85.5 µl methyl trifluoromethanesulfonate  was added dropwise. The mixture was stirred for 24 h at room temperature. The solvent was removed under reduced pressure. The crude solid was washed three times with diethyl ether and three times with pentane, and then dried under high vacuum. The crude solid was dissolved in the minimum amount of acetonitrile and precipitated by the addition of diethyl ether. The solid was filtered off and dried under high vacuum. Product Se3 was obtained as a pale-yellow solid (m.p. = 239 °C) after washing with diethyl ether and pentane. Yield: 0.230 g . 1H NMR : δ (ppm) = 8.14 , 8.07–8.01 , 7.99–7.94 , 7.82–7.68 , 7.58 , 4.22 , 2.50 . 13C NMR : δ (ppm) = 148.30, 136.11, 134.90, 134.21, 133.71, 128.93, 128.59, 128.28, 114.33, 113.87, 35.73, 11.10. 19F NMR : δ (ppm) = −79.34 . ATR-IR: −1) = 3082 (w), 2951 (w), 2360 (w), 1740 (w), 1605 (w), 1506 (m), 1476 (m), 1458 (m), 1404 (w), 1360 (w), 1308 (w), 1254 (vs), 1221 (s), 1138 (s), 1092 (w), 1078 (w), 1026 (vs), 935 (w), 908 (w), 829 (w), 773 (w), 758 (s), 739 (m), 710 (w), 692 (m), 667.37 (w), 633 (vs), 571 (m), 557 (m), 515 (s), 469 (w), 449 (w), 430 (w). ESI–MS: m/z(+) = calc. 676.99 [M − OTf]+, 264.02 [M − 2OTf]2+; found 676.64 [M − OTf]+, 263.00 [M − 2OTf]2+. m/z(−) = calc. 148.95 [OTf]−; found 148.64 [OTf]−.A reported procedure was slightly modified for the synthesis of compound Uiso(H) = 1.5Ueq(C) for methyl H atoms, and C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 1Introduction, selenium-based chalcogen-bonding catalysts deriving from a 1,3-bis(benzimidazoliumyl)benzene frame were applied in several reactions. Whereas the first report describes the application in a stoichiometric activation of a carbon–bromine bond  were synthesized. The preparation of these compounds followed an already reported route  under basic conditions. The final step, methylation of the urea compound, yielded the all-methylated compounds S3 and Se3.To further investigate this issue, the non-preorganized sulfur- and selenium-based catalysts were subjected to crystallization studies to investigate the chalcogen-bonding properties. Crystallization of these compounds proved difficult despite various efforts made while varying parameters that affect the crystallization process, such as temperature, concentration and crystallization techniques. The octyl chains, which are responsible for the good solubility of the catalysts in organic solvents, are most likely the reason for this. To avoid this challenge, the respective all-methylated catalysts , b = 22.5823 (6) and c = 18.2338 (5) Å, with a volume of 3160.16 (15) Å3 and a density of 1.536 Mg m−3. The unit cell is built up of four ion pairs. Within this structure, an intermolecular interaction between atoms S1 and F1 of a trifluoromethanesulfonate anion is observed. The S1⋯F1 distance is 3.154 (3) Å, 96% of the van der Waals radii (Σrω), and the directionality is rather poor (C1—S1⋯F1 = 146.9°). The supposedly more Lewis basic O atoms of the trifluoromethanesulfonate anion are involved in two anion–π interactions with the imidazole unit of benzimidazole. These interactions have distances O6⋯cent = 2.894 (4) Å and O3⋯cent = 3.068 (3) Å from the calculated centroid (cent) of the imidazole unit to the trifluoromethanesulfonate O atoms. From this O atom to the closest C atom, the distances in both cases are 11% shorter than the Σrω . In addition, hydrogen bonding between atoms O4 and H15 in the 2-position of the central arene core  is observed.Next, crystallization studies were carried out. The vapour diffusion method was applied successfully to crystallize compound ne Fig. 2. This corω. Additional weak hydrogen bonding found in this structure between the backbone H atoms of the arene core and the benzimidazolium unit will not be further discussed in this article.Overall, merely a chalcogen-bonding interaction between sulfur and fluorine was observed with a distance that corresponds to 96% of the ΣSe3 crystallizes also in the monoclinic space group P21/c , b = 13.12863 (8) and c = 31.27496 (18) Å, with a volume of 3181.02 (3) Å3 and a density of 1.722 Mg m−3. The unit cell contains four ion pairs and bidentate chalcogen bonding from the Se1 and Se2 centres of Se3 to trifluoromethanesulfonate atom O4 is observed. Some of the anions involved in these interactions are disordered over two positions. The interaction distances are Se1⋯O4 = 3.031 (2) Å and Se2⋯O4 = 3.080 (2) Å, with angles of C3—Se1⋯O4 = 165.31° and C11—Se2⋯O4 = 159.89°. The sum of the van der Waals radii is 3.42 Å and therefore the observed distances amount to 89 and 90% of this measure, thus classifying this interaction as stronger chalcogen bonding compared to the interaction found in the structure of S3. Atom Se2, which already features chalcogen bonding in the elongation of the benzimidazole C11—Se bond, faces also a second chalcogen-bonding interaction to atom O3A of the second trifluoromethanesulfonate anion in the elongation of the CH3—Se bond, with an Se2⋯O3A distance of 3.035 (3) Å and a C2—Se2⋯O3A angle of 158.07° (89% of Σrω). This additional interaction vividly demonstrates the property of chalcogens to form two noncovalent interactions based on their Lewis acidity. Although only one electron-withdrawing substituent is used, both axes simultaneously seem to be available for chalcogen bonding.Under the same crystallization conditions, the selenium-containing equivalent /c Fig. 3. The unirω with 99 and 100%. Atom O5 faces additional hydrogen bonding, formed with atom H20 sitting in the 4-position of the central arene core . Moreover, atom O1A of the trifluoromethanesulfonate anion is employed in a second hydrogen-bonding interaction to H24, sitting in the 2-position of the central arene core . These two hydrogen-bonding interactions indicate a Lewis acidic character of the benzene H atoms. The overall picture of the unit cell is therefore described by two chalcogen-bonding donors which are bridged with two trifluoromethanesulfonate anions via chalcogen bonding, hydrogen bonding and anion–π interactions. This structure features comparable binding distances within the chalcogen-bonding donor, e.g. the distances of the carbon–selenium bonds and also similar distances of the observed intermolecular chalcogen bonding to a related compound  of this trifluoromethanesulfonate anion are involved in two anion–π interactions to an imidazole group of benzimidazole [O5⋯cent = 3.269 (3) Å and O6⋯cent = 3.307 (3) Å]. These interactions can be considered very weak, as the distances are close to the actual ΣSe3 was obtained from crystallization at lower temperatures (4–5 °C) , b = 7.7558 (2) and c = 29.3267 (7) Å, with a volume of 3144.59 (14) Å3 and a density of 1.742 Mg m−3. The unit cell once more consists of four ion pairs. Different to the previously described solid-state structure (A of Se3), each selenium centre features its own chalcogen-bonding interaction to an O atom of a trifluoromethanesulfonate anion. The distances of these interactions are Se1⋯O3 = 3.074 (4) Å (90% of Σrω) and Se2⋯O1 = 3.052 (4) Å (89% of Σrω), with C3—Se1⋯O3 = 167.87° and C5—Se2⋯O1 = 171.26°. Besides these interactions and differences, yet another short contact is observed. Atom Se1, already featuring chalcogen bonding in the elongation of the benzimidazole C3—Se1 bond, faces also a second chalcogen-bonding interaction to atom O5 of the second trifluoromethanesulfonate anion in the elongation of the CH3—Se bond. This interaction  gives Se1 again a biaxial character. However, only one of the two Se atoms features this biaxial system, as also seen in structure A of Se3  and similar angles below 160°, which are less directional than the interactions in the elongation of the benzimidazole C—Se bond. Similar to the previously described structures, the 2-position hydrogen (H19) of the central arene core shows its Lewis acidic potential in a hydrogen-bonding interaction to one of the trifluoromethanesulfonate anions (O6) .Besides this structure, a second crystal structure (B) of C) Fig. 4. The crye Fig. 3. BetweenSe3) , b = 13.3265 (2) and c = 13.6445 (1) Å, with a volume of 1647.49 (3) Å3 and a density of 1.762 Mg m−3 was obtained. The unit cell is built up of two ion pairs along with four crystallized 1,2-dichloromethane molecules. The binding distances and angles within the donor are comparable to the previously described structure of Se3. The crystal structure features two independent intermolecular interactions. The first one includes the Se1 centre and atom Cl1 of 1,2-dichloroethane, with an Se1⋯Cl1 distance of 3.535 (24) Å, which corresponds to 97% of the Σrω, and a C3A—Se1A⋯Cl1A angle of 176°. The second short contact can be found between the Se2 centre and trifluoromethanesulfonate atom O3, with an Se2⋯O3 distance of 3.133 (4) Å (92% of Σrω) and a C11—Se2⋯O3 angle of 168°. This Se⋯O interaction is again comparable to the other observed chalcogen-bonding interactions for Se3. The distance of Se1A to the Cl1A atom of 1,2-dichloroethane is very close to the Σrω, which indicates a weaker interaction compared to the interaction of selenium with a trifluoromethanesulfonate O atom. However, since the solvent is not charged and thus a neutral chalcogen-bonding acceptor is involved in the Se⋯Cl interaction, a weaker interaction is expected. The slightly longer distance to the trifluoromethanesulfonate O atom compared to the distance in structures A and B of Se3 can be explained by the fact that two independent Se⋯O/Cl chalcogen-bonding interactions, yet no co-operative effect, are present.Changing the solvent in the crystallization experiments from dichloromethane to 1,2-dichloroethane ended up yielding yet another structural variation (structure C of ) Fig. 5. In thisB⋯cent = 3.063 (4) Å]. Atom O2 sitting on the same trifluoromethanesulfonate anion as O1 also forms an anion–π interaction [O2⋯cent = 2.920 (3) Å], becoming therefore a bridging moiety between two chalcogen-bonding donors. The imidazole system of this interaction does not feature a second anion–π interaction. The distances of these interactions are 5–13% shorter than the Σrω of the O atom to the closest C atom. These anion–π interactions are up to 10% shorter compared to those found in structure A of Se3  calculations to further evaluate and elucidate chalcogen-bonding properties of the herein considered catalyst system. For the a), 8(c) and 8(e)]. According to the expected tendency, the surface map values for these σ-holes (at Ch1 and Ch2) are decreasing with the decreasing atomic number of the implemented chalcogen . The comparison of Se3 and S3 is of special interest, as these data can be compared with the previously reported catalysis data , 8(d) and 8(f)] could provide hints on the origins of the comparable catalytic properties. Te3 shows defined σ-holes [Fig. 8b)] in this region with decreased absolute values of potentials [with respect to those of the C(benzim)—Ch bond] of 147.8 and 147.2 kcal mol−1. Besides this electron-poor area, the H atom in the 2-position of the central arene core also features an electropositive potential of 145.2 kcal mol−1.Shining light on the remaining σ-holes of these systems, that in the elongation of the CHSe3, these σ-holes are less defined and less separated from the electron-poor region at the central arene core [Fig. 8d)]. In contrast to Te3, the four chalcogen-based electron-deficient areas for Se3 show comparable energies  is spotted and a connected electron-deficient system covering these σ-holes and the 2-position H atom of the central core is observed. The surface map values —S bond σ-holes are those that are the least Lewis acidic. Matching this with the crystal structure of S3, these data are confirmed, as no chalcogen bonding in the elongation of the C(benzim)—S bond is found, but one intermolecular action is observed in the elongation of the CH3—S bond which is theoretically favoured. Like Se3, the most electron-deficient area of S3 is again observed between the central arene core and the chalcogen. However, in the case of S3, the difference to the second most Lewis acidic centre  is larger than the difference in Se3 . Since sulfur is more electron withdrawing, the larger electron deficient area might be explained by the more electron-withdrawing sulfur, which impacts the whole structure. This might also explain the reason for the catalytic activity in the reduction of quinolones. Nevertheless, it is necessary to mention that various reference experiments were carried out in that reaction which indicate an activation based on chalcogen bonding, for instance, by using the respective hydrogen-bonding equivalents.Continuing these investigations with s Table 2, entry 3in silico-calculated respective structures to shine some light on the fairly surprising results of their application in the activation of quinolines. The structure of S3 features one chalcogen-bonding interaction from sulfur to fluorine of the trifluoromethanesulfonate counter-anion, which has an interaction distance close to the sum of the van der Waals radii, whilst also anion–π interactions and hydrogen bonding are observed. These results are in line with the theoretically predicted data. In three crystal structures of the selenium-based analogue Se3, different mono- and bidentate, as well as biaxial binding motifs to neutral and negatively charged molecules based on chalcogen bonding, are present. Nevertheless, these structures also contained anion–π interactions along with hydrogen bonding. The results could also be related to calculational data. We further extended the DFT calculations to the appropriate tellurium-based compound, which could not be synthesized, and observed the most suitable theoretical properties for chalcogen bonding. However, the unusual activities of the previous report on the reduction of quinolines could not be satisfactorily explained.In summary, we presented four solid-state structures of sulfur- and selenium-containing chalcogen-bonding catalysts. The structures and their interactions are matched with 10.1107/S2053229622011536/qw3003sup1.cifCrystal structure: contains datablock(s) ts-049_3S, TS-056_3Se-C, TS-056_twin_twin1_hklf4_3Se-B, TS-058_3Se_A, global. DOI: 10.1107/S2053229622011536/qw3003ts-049_3Ssup2.hklStructure factors: contains datablock(s) ts-049_3S. DOI: 10.1107/S2053229622011536/qw3003TS-056_3Se-Csup3.hklStructure factors: contains datablock(s) TS-056_3Se-C. DOI: 10.1107/S2053229622011536/qw3003TS-056_twin_twin1_hklf4_3Se-Bsup4.hklStructure factors: contains datablock(s) TS-056_twin_twin1_hklf4_3Se-B. DOI: 10.1107/S2053229622011536/qw3003TS-058_3Se-Asup5.hklStructure factors: contains datablock(s) TS-058_3Se-A. DOI: 10.1107/S2053229622011536/qw3003sup6.txtEnergies of computed structures. DOI: 10.1107/S2053229622011536/qw3003sup7.txtCoordinates of computed structures. DOI: 10.1107/S2053229622011536/qw3003sup8.pdfAdditional tables, figures and spectra. DOI: 2201758, 2201759, 2201760, 2201761CCDC references:


It was confirmed that ethyl l-sorboside formed α-pyranose with a 2C5 conformation. In the crystal, molecules are linked by O—H⋯O hydrogen bonds, forming a three-dimensional network. The unit-cell volume of the title ethyl α-l-sorboside is 940.63 Å3 (Z = 4), which is about 194.69 Å3 (26.1%) bigger than that of l-sorbose [745.94 Å3 (Z = 4)]. Ethyl  The crystal structure of ethyl l-sorboside features a three-dimensional hydrogen-bonded network  global, I. DOI: 10.1107/S2414314620016259/bv4033Isup2.hklStructure factors: contains datablock(s) I. DOI: 2046786CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Current models for oxazaborolidine-catalyzed transition-statestructuresare determined by C–H···O–B and C–H···O=Sformyl hydrogen bonding between the electrophile and catalyst. However,selectivity in the oxazaborolidine-catalyzed Mukaiyama aldol cannotbe fully rationalized using these models. Combined density functionaltheory and noncovalent interaction analyses reveal a new reactionmodel relying on C–H···O, C–H···π,and π–π interactions between the nucleophile, electrophile,and catalyst to induce selectivity. These analyses reveal a new reaction model, distinct from the Coreyand Wong models, which involves a series of noncovalent C–H···O,C–H···π, and π–π interactions(defined in the Supporting Information).Selectivity through this model is validated on several sets of experimentalconditions.Herein, we report the resultsof a thorough computational analysisof the full TS complex for an NTOB-catalyzed Mukaiyama aldol usinga trimethylsilyl enol ether derived from acetophenone 3.16 ConfSupporting Information). TS-1, the lowest-energymajor TS, is found to be 2.5 kcal mol–1 lower inenergy than TS-2, the lowest-energy minor TS .A total of 328 unique TSs wereobtained for the NTOB-catalyzedMukaiyama aldol, of which 47 selected low-energy conformers were reoptimizedat a higher level of theory . Thus, severalimportant noncovalent C–H···O, C–H···π,and π–π interactions between the nucleophile, electrophile,and catalyst contribute to the overall stability of TS-1 and TS-2, lowering their free energy compared to theCorey and Wong models. Accordingly, TS-3 and TS-4, the lowest-energy major TSs located representing Corey and Wong-likebinding, respectively, are found to be 2.7 and 6.5 kcal mol–1 higher in energy than TS-1 .47 Indeed, theformation of attractive π–π interactions betweenthe aromatic aldehyde and the electron-rich indole was an importantelement of Corey’s original model.25 However, in TS-1 and TS-2, the aldehydeis positioned perpendicular to the indole, removing the possibilityof such interactions between these components. Nonetheless, both TS-1 and TS-2 possess face-centered π–πinteractions between the N-sulfonyl aromatic andthe electron-deficient boron substituent of the catalyst. Additionally,in TS-1, there is a significant interaction of approximately2 kcal mol–1  betweenthe electron-deficient aromatic boron substituent and the electron-richphenyl of the silyl enol ether. This interaction is geometricallyimpossible in TS-2 due to the positioning of the silylenol ether. This arrangement of overlapping aromatics results in significantstabilization of TS-1, lowering its free energy withrespect to TS-2 and inducing selectivity in the reaction.These findings are in line with previous quantum chemical analyseson the oxazaborolidinium-catalyzed cycloadditions of maleimides, whichfound that NCIs between the substrate and aromatic catalyst were vitalto inducing selectivity and that the importance of nonclassical C–H···Ohydrogen bonding had been overstated by the previous models.48As evidenced from and TS-2 4 reveal TS-1 and TS-2 were reoptimized with the boron substituentreplaced by a nonsubstituted phenyl group , while the same interaction remains impossible in TS-2-Ph. As a result, TS-1-Ph increases in freeenergy relative to TS-2-Ph, and selectivity becomes poorer.To further assess the impact of thesenucleophile–catalystπ–π interactions on selectivity, additional calculationswere performed with alternative boron substituents. First, yl group 6. Conseqn-butyl used inthe experimental work, and a new conformational analysis was performed.A total of 74 unique TSs were obtained, of which 25 selected low-energyconformers were reoptimized at a higher level of theory (full detailsin the Supporting Information). In contrastto previous systems, no π–π interactions couldform between the nonaromatic boron substituent and either the silylenol ether or N-sulfonyl group. Nevertheless, selectivityis preserved in both experiment and DFT; TS-1-Me .16 In lieu of π–π interactions betweenthe silyl enol ether and boron substituent, the N-sulfonyl group in TS-1-Me is able to direct itselftoward the top face of the oxazaborolidinone ring, allowing a π–πinteraction with the phenyl of the aldehyde of approximately 2.3 kcalmol–1 . This kind ofinteraction is not geometrically possible in TS-2-Me,where the alternative binding of the silyl enol ether sterically screensthe N-sulfonyl group from occupying any positionon the top face of the ring, resulting in its higher free energy.With the exclusion of π–π interactions, TS-2-Me otherwise shares the reaction model as TS-2. Thus,selectivity is preserved, despite the lack of an aromatic boron substituent.The aromatic boron substituent was then replacedwith a methylgroup, as an approximation for the  TS-1-Me 7, the loIn conclusion, our computational analysesreveal a new reactionmodel for the NTOB-catalyzed Mukaiyama aldol, which matches experimentalselectivity and is validated on systems with less polarized and nonaromaticboron substituents. While previous models focused on interactionsbetween the catalyst and electrophile, nucleophile–catalystinteractions are found to be vital in stabilizing the TS complex andinducing selectivity. A variety of nonclassical C–H···O,C–H··· π, and π–π interactionsare important in the model, while traditional formyl C–H···Ointeractions, such as those in the Corey and Wong models, are absent.Selectivity is rationalized by the presence of π–πinteractions in the major TSs that are not geometrically possiblein the minor TS due to the direction of nucleophilic binding.


N-benzylcinchonidinium bromide and the sesquihydrate are reported. O—H hydrogen-bond donor interactions and numerous C—H⋯Br contacts dominate the intermolecular features.The crystal structures of anhydrous  N-benzylcinchonidinium bromide, C26H29N2O+·Br−, with the systematic name (R)-[-1-benzyl-5-ethenyl-1-azoniabicyclo[2.2.2]octan-2-yl](quinolin-4-yl)methanol bromide, is a quaternary ammonium salt of the cinchona alkaloid cinchonidine. This salt is widely used as a chiral phase-transfer catalyst and chiral resolution agent. Both classical and non-classical hydrogen-bonding interactions, as well as anion effects have been shown to play key mechanistic roles in the catalysis of cinchona alkaloids. In an effort to understand the effects of water on these intermolecular interactions, the structures of anhydrous N-benzylcinchonidinium bromide, (I), and the sesquihydrate, C26H29N2O+·Br−·1.5H2O, (II), were determined. We report here the structures of 2.P21. The asymmetric unit of (I)P41212. The asymmetric unit of (II)z = 0.5. For (I)S, R, S, S, and R, respectively, by anomalous dispersion and are consistent with previous structures of cinchonidine.The anhydrous compound (I)N-benzylcinchonidinium cation atom coordinates of (I)A⋯O1 are found in both (I)B⋯O1 contact  Tables 3 and 5 ▸.3.The extended structure of (I)The sesquihydrate (II)4.ConQuest version 2022.1.0; Groom et al., 2016N-benzylcinchonidinium salts as well as the pseudo-enantiomer N-benzylcinchoninium. The 2-fluorobenzyl bromide sesquihydrate analog XUNQIG . Crystals of the anhydrous form (I)N-benzylcinchonidinium bromide. Crystals of the sesquihydrate (II)N-benzylcinchonidinium bromide.6.2, vinyl C9—H9, methylene C—H, and methine C—H, respectively, and with Uiso(H) = k·Ueq(C), k = 1.2 for all C—H and 1.5 for the hydroxyl H1.Crystal data, data collection and structure refinement details are summarized in Table 510.1107/S2056989022005096/pk2664sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989022005096/pk2664Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989022005096/pk2664IIsup3.hklStructure factors: contains datablock(s) II. DOI: 2172120, 2172119CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


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It is a salt containing a tetracationic dimercury species with six cobaltoceniumselenolate ligands, four hexafluoridophosphate counter-ions and two acetonitrile solvent molecules. The cation (point group 2Se6} core with two bridging Se atoms and four terminal Se atoms.The title compound, [Co The four Cipso—Se—Hg1 angles are slightly compressed, ranging from 98.79 (7) to 106.04 (7)°, as was also observed for cobaltocenium selenolate gold complexes 4][Hg2(C6H5Se)6] .The sole comparable compound found in the literature is [YbAu]PF6  were suspended in 5 ml of dry ortho-dichlorobenzene. Approximately 0.1 ml of liquid mercury was added and the mixture stirred for 48 h. This reaction was originally carried out with the aim of removing selenium from the desired compound. The bright-orange precipitate was filtered off, washed with two portions of 10 ml of diethyl ether and dissolved in 5 ml of acetonitrile. This orange solution was concentrated to about 1 ml. Bright-orange needle-shaped crystals were obtained by diffusion-crystallization with diethyl ether at 253 K. 1H NMR : δ 5.70 , 5.51 , 5.46 .In a 50 ml Schlenk flask, 11.1 mg of [(CcSe)(PPh6 anions (P2) shows disorder of four fluorine atoms over two sets of sites in a 2:1 ratio for F7, F8, F9, F10 and F7A, F8A, F9A, F10A. Another positional disorder occurs for the complete acetonitrile solvent molecule in a 1:1 ratio. All disordered atoms were refined with anisotropic displacement parameters without further restraints, but with fixed occupation factors.Crystal data, data collection and structure refinement details are summarized in Table 110.1107/S241431462101083X/wm4154sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S241431462101083X/wm4154Isup2.hklStructure factors: contains datablock(s) I. DOI: 2116450CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the article “Random number generation and the ability of mentally reconstructingcontext in patients with organic amnesia”, with DOI code number10.1590/1980-5764-DN-2021-0021, published in the Dement Neuropsychol 2022March;16(1):19-27, on page 19:Where it was written:4Centro Paulista de Neuropsicologia, São Paulo SP, Brazil.Should read:4Centro Universitário São Camilo, São Paulo SP, Brazil.


The prepared supramolecular assemblies were characterized by single crystal X-ray diffraction, an elemental analysis, FT-IR spectroscopy and a thermal analysis based on thermogravimetry (TG) combined with differential scanning calorimetry (DSC). Additionally, their melting points through TG/DSC measurements were established. All fabricated adducts demonstrated the same stoichiometry, displayed as 1:1. The integration of HBTA with selected N-containing co-formers yielded different forms of multi-component crystalline phases: zwitterionic co-crystals (1–3), true co-crystal (4) or true salt (5). In the asymmetric units of 1–4, the acidic ingredient is protonated, whereas the corresponding N-containing entities take either the zwitterionic form (1–3) or remain in the original neutral figure (4). The molecular structure of complex 5 is occupied by the real ionic forms of both components, namely the (benzylthio)acetate anion (BTA−) and the tryptaminium cation (TPA+). In crystals 1–5, the respective molecular residues are permanently bound to each other via strong H-bonds provided by the following pairs of donor···acceptor: Ocarboxylic···Ocarboxylate and Npyrrolidinium···Ocarboxylate in 1–3, Ocarboxylic···Npyridine and Namine···Ocarboxylic in 4 as well as Nindole···Ocarboxylate and Naminium···Ocarboxylate in 5. The crystal structures of conglomerates 1–5 are also stabilized by numerous weaker intermolecular contacts, including C–H···O , C–H···S , C–H···N (5), C–H···C (5), C–H···π (1–5) as well as π···π (4) interactions. The different courses of registered FT-IR spectral traces and thermal profiles for materials 1–5 in relation to their counterparts, gained for the pure molecular ingredients, also clearly confirm the formation of new crystalline phases.The co-crystallization of (benzylthio)acetic acid (HBTA) with L-proline (L-PRO), D-proline (D-PRO), DL-proline (DL-PRO), isonicotinamide (INA) and tryptamine (TPA) led to the formation of five novel crystalline compounds: L-PRO The rational design and synthesis of new supramolecular crystalline systems, with specific crystal networks and physiochemical properties based on the skilful use of noncovalent interactions present between molecules, is broadly understood as the paramount objective of crystal engineering ,2. The c2, OH, SO2, NO2, halogens, N, O, S, and CH/CH2/CH3, act as excellent and versatile functional components in the creation of supramolecular architectures, as they provide various kinds of hydrogen bond acceptors and/or donors and the π-conjugated system for extending their networks [2 entities, an organic sulphide –S– species and an aryl unit.The carboxylic derivatives containing additionally aromatic/cyclic rings composed of mono- or heteroatoms and other potential binding sites, such as NHnetworks . Accordi− anions forming primarily coordination bonds with the metal centres only through the carboxylate oxygens (Cu (II) and Zn (II) complexes) or with the simultaneous partnership of sulphur (Co (III) and Cd (II) compounds).As arises from the crystalline structure of single-component HBTA crystals , all typConQuest2022.1.0 program [1/cP2 [12121P2 [P-1 [54 different carboxylic:PRO crystal structures [1/cP2 [Pc [Pbca [1Pca2 [186 crystal structures [12121P2 phase [35 reported organic crystal structures [The eponymous N-containing species , such asm [P21/c ,24 varia[P212121 ,26,27 ans [P21/c ,29,30 syPc [Pbca  and Pca2a [Pca21 . Due to a [Pca21  in an ac21 phase . Among 3This work presents an exploration of the ability of the HBTA component to supramolecular complexation via the participation of co-formers in the form of enantiomeric and racemic proline compounds, isonicotinamide and tryptamine . The dis1–5, were prepared by using the co-crystallization process that entailed mixing the corresponding N-containing ingredients with (benzylthio)acetic acid (HBTA) at a 1:1 ratio. Well-shaped crystals were then isolated under ambient conditions utilizing the natural solvent-evaporating technique with the addition of short-chained alcohols, due to the similar and high levels of solubility of the title building units in given alcohols. The synthetic pathway for the production of the adducts 1–5 is depicted in 1–5 were subjected to the SC X-ray diffraction measurements. All complexes crystallized without solvent molecules. The revealed structures showed that the co-crystallization products are identified as zwitterionic co-crystals (1–3), true co-crystals (4) and true salts (5). The obtained multicomponent crystalline phases were also analysed with FT-IR spectroscopy as well as the thermal analysis.All of the noncovalent-bonded supramolecular architectures, 1), D-proline (2), DL-proline (3), isonicotinamide (4) and tryptamine (5), is described below. The analysed structures are designated as follows: L-PRO±·HBTA (1), D-PRO±·HBTA (2), DL-PRO±·HBTA (3), INA·HBTA (4) and TPA+·BTA− (5). The summary of crystal data, experimental details and refinement results of structures in question as well as the geometry of intermolecular interactions in the crystals 1–5 are shown in The X-ray crystallographic study of the five new structures of S-containing carboxylic acid, namely (benzylthio)acetic acid (HBTA) with L-proline  and 1.333 (4) Å (in 2); C1‒O2:1.205 (5) Å (in 1) and 1.207 (4) Å (in 2)) as well as carboxylate groups within both L-PRO± (C14‒O3: 1.249 (4) Å; C14‒O4: 1.252 (3) Å) and D-PRO± (C14‒O3: 1.251 (5) Å; C14‒O4: 1.260 (3) Å) zwitterion ions indicating the formation of L-PRO±·HBTA (1) and D-PRO±·HBTA (2) zwitterionic co-crystals, not salts.The enantiomeric adducts imension . The atohiometry . The deshiometry  support 1 and 2 °/−58.8 (1)° for D-PRO±·HBTA. The absolute values of the torsion angles are the same, within the experimental error, and the difference in the sign does not affect the crystal structure of either of the compounds, which are analogous.The bond lengths and angles of the prolinium ions and acid molecules of 1 and 2  are withnent see . The tor± itself is further associated with two other prolinium zwitterion ions by three intermolecular N‒H···O bonds  and the dihedral angle is equal to 15.7 (5)°. The use of a racemic proline for the synthesis of co-crystals resulted in significant changes in the conformation of the acid molecule acetic acid takes place through O1‒H1O1···O4 contact  and synthon III (N1‒H···O3), as presented in DL-proline and (benzylthio)acetic acid also form a 1:1 co-crystal 3 . It crysistances  of the Hd angles  are simi 1 and 2 . Further3 differs from that observed for the co-crystal of (benzylthio)acetic acid with L-proline and D-proline. The described supramolecular synthons in DL-PRO±·HBTA form a 2D network, as shown in 1. Moreover, the weak C–H···π interaction between acid molecules and the C‒H···O contact between DL-PRO± and HBTA were determined  Å and 1.208 (2) Å (2 (the torsion angles: C1–C2–S1–C3/C2–S1–C3–C4 are −75.5 (1)°/−56.5 (1)°), and the dihedral angle between the plane of the phenyl ring and the pyridine moiety is 15.3 (2)°.The crystal structure analysis of 08 (2) Å , indicat2 part of the carboxamide group of INA to the carbonyl moiety (a) of other INA molecules (N2–H1···O3) and of (b) carboxylic acid forms (a) a homomeric R22 (8) dimer (Synthon II) and (b) a linear N2–H2···O2 interaction (synthon III), respectively. In crystals, these supramolecular hydrogen bonds generate an infinite ribbon  and 1.250 (3) Å in the BTA− molecule acetate anion  spectroscopy is a valuable technique for analysing the structure of solid materials based on the identification of the various functional groups present in the tested samples; therefore, this analytical method is also an excellent approach to the characterization and study of the solid crystalline phases of co-crystallization products. The FT-IR spectral signatures of the starting components and the supramolecular aggregates in question were performed in order to ascertain the crystalline form of received solid phases 1–5 is reflected by the presence of vibrational bands corresponding to the functional groups derived from both co-formers. Additionally, the generation of new crystalline phases 1–5 is also demonstrated by the occurrence of the appropriate shifts of characteristic stretching vibrations in the FT-IR spectra of adducts 1–5 in comparison to their positions shown in the spectra of the starting species. The crystal structures of adducts 1–5 are established via various energetic H-bonds, among which the privileged ones are those formed by the strong functional groups, such as COO−/COOH, NH3+/amide as well as the pyrrolidinium/pyridine/indole nitrogen atom, respectively; hence, the strongest shifts of stretching vibrations are related to these beneficial functional groups.The formation of new products ν (C=O) of the COOH group. The absorption band associated with this vibrational mode for free HBTA agents is located at 1697 cm−1 (KBr pellet) [−1 (ATR mode) [1–4, the most intense peaks, situated at 1712 cm−1 (1 and 2), 1716 cm−1 (3) and 1699 cm−1 (4), respectively, are connected with the carbonyl stretches originating from the acidic unit. These results point to the fact that the HBTA molecular ingredient after co-crystallization remains in its neutral and protonated form. The observed shifts in the free acid absorption band towards higher wave numbers (higher energies) confirm that the complexes 1–4 crystallize in the form of co-crystals, which is consistent with X-ray crystal structures. In the spectra of complexes 1–3, the two absorption bands, corresponding to the stretching asν (COO−) and sν (COO−) vibrations derived from the negatively charged carboxylate group of the zwitterionic form of proline compounds, are also observed. The peaks connected with the stretching asν (COO−) and sν (COO−) vibrations of the deprotonated carboxylate group of L-PRO±, D-PRO± and DL-PRO± zwitter ions are located at 1596 cm−1 and 1415 cm−1 for complexes 1 and 2, as well as 1586 cm−1 and 1391 cm−1 for aggregate 3, respectively, which is in line with the spectral data obtained for zwitterionic co-crystals with phenylboronic and 4-iodophenylboronic acids [2+ moiety resulting from the proton transfer from the acidic part to the pyrrolidine nitrogen atom within the molecule, so the two high-energy stretching ν (NH) vibrations of the protonated NH2+ group appeared as a relatively broad and uniquely strong band [1–3, the absorption bands related to the stretching ν (NH) vibrations came from the NH2+ group and are situated at 3414 cm−1 and 3255 cm−1 for enantiomers 1 and 2 as well as 3418 cm−1 and 3143 cm−1 for racemate 3.The key H-bonding functional group in the HBTA agent is the acidic moiety. The most specific vibrational mode of the organic acid function is attributed to the carbonyl stretching TR mode) , and is ic acids . The zwiong band . In the ν (C=O) vibrational mode at 1681 cm−1 (ν (C=O): 1667 cm−1 [4, only one distinct band is observed near 1700 cm−1. This most intensive absorption peak located at 1699 cm−1 is probably attributed to both the stretching ν (C=O) vibrational mode of the protonated HBTA unit as well as the ν (C=O) vibrational fundamental of the amide part of INA, due to their participation in the formation of the hydrogen bonds. The absorption bands of stretching asν (NH2) and sν (NH2) vibrations of the primary amine from INA are found in the FT-IR profile of complex 4 at 3361 cm−1 and 3160 cm−1, respectively, which is in agreement with the spectral data obtained for free INA (asν (NH2): 3370 cm−1 and sν (NH2): 3186 cm−1 [asν (NH2): 3383 cm−1 and sν (NH2): 3159 cm−1 [The free INA ingredient shows the carbonyl stretching 667 cm−1 ). As res5, the carbonyl stretching ν (C=O) absorption band of the acid disappeared completely and was replaced by new characteristic absorption bands of stretching asν (COO−) and sν (COO−) vibrations found at 1562 cm−1 and 1384 cm−1, respectively, which confirms the occurrence of the carboxylate group belonging to the deprotonated anionic form of the HBTA component. The neutral molecule of the tryptamine agent consists of the aliphatic ethylamino chain attached to the indole core. From the viewpoint of supramolecular complexation, the most important absorption bands in the infrared trace of TPA are connected with the stretching vibrations asν (NH2) and sν (NH2) of the amine moiety as well as the stretching vibrational mode ν (NH) of the indole unit. The asν (NH2) and sν (NH2) fundamental modes are active in the TPA spectral profile at 3344 cm−1 and 3283 cm−1, respectively, which are in accordance with the vibrational data obtained for 5-hydroxytryptamine (asν (NH2): 3318 cm−1 and sν (NH2): 3272 cm−1) [ν(NH) stretching mode at 3418 cm−1, which is in line with the wavenumber (ν (NH): 3419 cm−1) found for the basic indole system [asν (NH2) and sν (NH2) in the spectral signature of complex 5 with the simultaneous presence of an absorption peak attributed to the stretching fundamental ν (NH) of the indole at the same position indicates that, during the co-crystallization process, the acidic proton was directed into the amine, not the indole, nitrogen atom of tryptamine, resulting in the formation of the aminium NH3+ group. The intense absorption band seen at 3285 cm−1 corresponds to the stretching vibrations of the H-bonded NH3+ moiety. What is more, the extended absorption, involving numerous combination bands and overtones, to about 2000 cm−1 with a clearly noticeable peak located at 2106 cm−1 as well as the strong band of the symmetric deformation vibrations observed at 1531 cm−1, also confirm the existence of NH3+ species in the structure of adduct 5 [+) and (benzylthio)acetate anion (BTA−) is corroborated with the crystal structure of complex 5, defining this solid phase as a true salt.In the infrared spectrum of adduct e system . The absadduct 5 . The facA thermal analysis as an important tool for determining the thermal stability of various classes of materials because it provides information about the possible presence of solvent molecules in their structures as well as the mass loss and peak values related to the exothermic and/or endothermic effects occurring at different temperature ranges .1), 77 °C (2), 89 °C (3), 108 °C (4) and 154 °C (5) correspond to the melting points of the obtained aggregates. The DSC results revealed that the melting points of all the adducts are distinct from HBTA (64 °C) [±·HBTA (1), D-PRO±·HBTA (2) and DL-PRO±·HBTA (3) exhibit melting points in between the two components , also found in between the two ingredients (4) displays a decrease in the thermal stability of isonicotinamide and an improvement in the thermal stability of HBTA. The true salt TPA+·BTA− (5) shows a noticeably higher thermal stability than that of the tryptamine and HBTA  and differential scanning calorimetry (DSC). The TG and DSC traces registered for all adducts are illustrated in mponents , thus thredients , impliesand HBTA , which iAll co-formers and solvents were sourced from commercial products with analytical grades and used without further purification. (Benzylthio)acetic acid (HBTA) and L-proline were provided by Sigma-Aldrich. D-proline was obtained from Reanal Laboratory Chemicals Ltd. whereas the DL-proline was sourced from Tokio Chemical Industry Co., Ltd. (TCI). Isonicotinamide was received from Alfa Aesar-Thermo Fisher Scientific while tryptamine was purchased from Acros Organics B.V.B.A. Solvents in the form of methanol and ethanol were received from Avantor Performance Materials Poland S.A. (formerly POCH S.A.).1–5 were harvested as a result of engagement of slow solvent evaporation technique from methanolic or ethanolic solution, containing equimolar amounts of HBTA and respective N-containing entities at room temperature.Co-crystallization process was applied in order to produce good crystals quality of synthesized supramolecular associations. Well-shaped single crystals of adducts 1–5 are presented below:The details of synthesis, the colours and shapes of collected crystals, yield of co-crystallization experiments, and the results of elemental analysis performed for complexes ±·HBTAL-PRO (1): HBTA  and L-PRO  were dissolved separately in 5 mL of MeOH each. Both solutions were then combined and stirred for 5 min. The resulting solution was allowed to evaporate naturally at ambient temperature and after a few days, light-brown, plate-like crystals were obtained.1: 0.545 g (91.75%); Elemental analysis results for 1 (C5H9NO2±·C9H10O2S) Calcd (%): C, 56.55; H, 6.44; N, 4.71; S, 10.78. Found (%): C, 56.28; H, 6.31; N, 4.85; S, 10.93.Yield for ±·HBTAD-PRO (2): HBTA  was dissolved in 5 mL MeOH. D-PRO , also dissolved in 5 mL of MeOH, was added to this solution. After several days, by slow evaporation of the solvent at room temperature, light-brown, cube-shaped crystals were obtained.2: 0.567 g (95.45%); Elemental analysis results for 2 (C5H9NO2±·C9H10O2S) Calcd (%): C, 56.55; H, 6.44; N, 4.71; S, 10.78. Found (%): C, 56.37; H, 6.29; N, 4.89; S, 10.97.Yield for ±·HBTADL-PRO (3): HBTA  and DL-PRO  was dissolved separately in 5 mL of MeOH each. Next, the solutions were mixed together and stirred for a few minutes. Light-brown, block-shaped crystals were harvested after allowing the final mixture to evaporate at ambient temperature for a few days.3: 0.269 g (90.57%); Elemental analysis results for 3 (C5H9NO2±·C9H10O2S) Calcd (%): C, 56.55; H, 6.44; N, 4.71; S, 10.78. Found (%): C, 56.71; H, 6.37; N, 4.63; S, 10.69.Yield for INA·HBTA (4): An ethanolic solution (5 mL) of INA  was added to an ethanolic solution (5 mL) of HBTA . Next, the combined solution was stirred for a while and left to evaporate at room temperature, producing light-brown, plate-like crystals after several days.4: 0.285 g (93.75%); Elemental analysis results for 4 (C6H6N2O·C9H10O2S) Calcd (%): C, 59.19; H, 5.30; N, 9.20; S, 10.53. Found (%): C, 58.84; H, 5.18; N, 9.03; S, 10.79.Yield for +·BTA−TPA (5): The methanolic solution (5 mL) of HBTA  was mixed with the methanolic solution (5 mL) of TPA . The obtained solution was stirred for 5 min and left to evaporate for a few days at ambient temperature, resulting in a growth of needle-like crystals of brown colour.5: 0.301 g (88.01%); Elemental analysis results for 5 (C10H13N2+·C9H9O2S−) Calcd (%): C, 66.64; H, 6.48; N, 8.18; S, 9.36. Found (%): C, 66.80; H, 6.65; N, 8.07; S, 9.54.Yield for 1–5 was performed by means of a Perkin Elmer 2400 Series II CHNS/O elemental analyser , utilizing the CHNS mode of operation.The determination of the weight percentages of carbon, hydrogen, nitrogen and sulphur content in the supramolecular assemblies 1–5 and free components were recorded on FT/IR-4600  FT-IR spectrometer utilizing the KBr pellet technique in the spectral range between 4000 and 400 cm−1.The infrared spectra of supramolecular complexes 3 h−1. Weights of 8.149 to 8.770 mg of tested samples placed in the alumina crucibles were heated over the temperature range of 30–800 °C at a constant heating rate of 10 °C min−1.The thermal behaviour of multicomponent crystalline products and free co–formers were investigated on the basis of the thermogravimetry (TG) coupled with differential scanning calorimetry (DSC). The TG/DSC measurements were conducted on a SETSYS 16/18  thermal apparatus with the dynamic purge of air 0.75 dm1–5 were performed on an Oxford Diffraction Xcalibur CCD diffractometer  with graphite-monochromated MoKα radiation (λ = 0.71073 Å). The diffraction data for adducts 1, 2 and 4 were collected at 293 (2) K while the data sets for complexes 3 and 5 were gathered at 100 (2) K and 120 (2) K, respectively, using the ω scan technique with an angular scan width of 1.0°. The CrysAlis PRO v. 1.171.37.35g  and CrysAlis PRO v. 1.171.39.46  software packages [SHELXS-86 [F2 using SHELXL-2018/3 [WinGX 2021.1 software [Mercury 2022.1.0 program [The crystallographic measurements of multi-component crystals packages ,43 were HELXS-86  and by fL-2018/3  within t program  was expl±·HBTA, D-PRO±·HBTA, DL-PRO±·HBTA; 1–3), true co-crystals  and true salts . The individual building units present in crystal structures 1–5 are dominantly bound with each other with the COOH···O (1–3), COOH···N and NH2···COOH (4) or NH3+···COO− and NindoleH···COO− (5) synthons, which show the importance of these interactions in the formation of the co-crystals or salts under investigation, respectively. The analysed structures show some similarities. The ribbon patterns, with the N-containing component inside and the acid molecules outside, were observed. The distinct geometries of the N-containing species as well as the different sets of weaker intermolecular contacts, such as C–H···O, C–H···S, C–H···N, C–H···C, C–H···π, and π···π, have resulted in the construction of varied 3D supramolecular architectures, in which the crystallographically unique molecules form AABB or ABAB motifs.(Benzylthio)acetic acid (HBTA) was successfully applied as a co-former in the preparation of the first five noncovalent-bonded supramolecular associations with proline (PRO) compounds, isonicotinamide (INA) as well as tryptamine (TPA). The co-crystallization experiments, depending on the type of incorporated N-containing species, contributed to the generation of diverse crystalline phases of the supramolecular materials in question as zwitterionic co-crystals . In this case, each of the two carboxylate oxygens act as a double acceptor, ultimately giving as many as four strong Naminium/indole−H··· COO− hydrogen bonds with a similar strength sustained the TPA+ and BTA− residues. The carboxylic oxygen atoms of neutral HBTA in co-crystals 1–4 also take part in hydrogen bonding but their involvement in the creation of strong H-bonds is weaker than that in the salt, due to the fact that they act only as a single donor  or a single donor and a single acceptor   .The results show that (benzylthio)acetic acid is a good building unit to be embodied into co-crystals or salts to make diversely formed, hydrogen-bonded structures with different stabilities.


N-naphthylpent-3-en-2-one molecules by O—H⋯O-type hydrogen bonds.In the title compound, the dihedral angle between the naphthalene ring system and the aminopentenone fragment mean plane (C=C—N—C=O) is 76.91 (19)°. In the crystal, a water molecules are connected with the  15H15NO·0.5H2O, was prepared from α-naphthylamine and 2,4-pentanedione in a 1:1 ratio. An intramolecular N—H⋯O hydrogen bond in the N-naphthylpent-3-en-2-one molecule involving the amine and carbonyl groups strengthens the structure. The water molecule interacts with two symmetry-related N-naphthylpent-3-en-2-one molecules viaby O—H⋯O hydrogen bonds.The title compound, C Slow evaporation of the solution at room temperature was carried out, leading to grey crystals suitable for a single-crystal X-ray diffraction study (yield 63%).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2414314621009895/xu4045sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314621009895/xu4045Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314621009895/xu4045Isup3.cmlSupporting information file. DOI: 2111316CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Myelodysplastic syndromes/myeloproliferative neoplasm with ring sideroblasts and thrombocytosis (MDS/MPN-RS-T) is a myeloid disorder with myelodysplastic and myeloproliferative features , 2. MDS/Luspatercept is a first-in-class erythroid maturation agent that binds several transforming growth factor-β superfamily ligands, enhancing late-stage erythropoiesis . The res9/dL) and serum ferritin (1062 vs 1460 µg/dL), and higher serum erythropoietin (sEPO) (71.9 vs 54.0 U/L)  had MDS/MPN-RS-T; 14 were randomized to luspatercept and 9 to placebo. Baseline characteristics that differed between the two arms included lower median leukocyte count (4.8 vs 7.5 × 10/L) Fig. . Median P values are descriptive and not adjusted for multiplicity.The primary endpoint in the MEDALIST study was RBC transfusion independence (RBC-TI) ≥8 weeks during weeks 1–24. Secondary endpoints included: modified hematologic response–erythroid  ; ≥1.0 g/P = 0.028); mHI-E ; and clinical benefit , vs placebo  during weeks 1–24, and a significantly greater proportion achieved mHI-E   and mHI-E  . RBC-TI ≥48 weeks at any time during treatment was achieved by 28.6% of patients randomized to luspatercept vs no placebo patients; among those patients in the luspatercept group who had reached RBC-TI ≥8 weeks at any time during treatment, 40.0% achieved RBC-TI ≥48 weeks, vs no placebo patients  Fig. . A numer63) Fig. . RBC-TI nts Fig. .Fig. 2TrDespite limited numbers, the value of luspatercept for patients with MDS/MPN-RS-T is supported by comparisons with data from the entire MEDALIST study population. The achievement of RBC-TI ≥8 weeks during weeks 1–24 among patients with MDS/MPN-RS-T randomized to luspatercept vs placebo (64.3 vs 22.2%) was higher than in the overall MEDALIST population (37.9 vs 13.2%) . Similar9/dL), and neutrophils (3.4 [2.4]–5.1 [3.4] × 109/dL), while platelet levels remained stable (515 [156] and 539 [274] × 109/dL)  as expected, had lower median sEPO (59.9 vs 153.2 U/L), were less likely to have received iron chelation therapy (26.1 vs 48.5%), and had lower median transfusion burden (4.0 vs 5.0 units/8 weeks), consistent with their higher RBC-TI and mHI-E response rates  hemoglobin (7.7 [0.5]–9.5 [1.1] g/dL), leukocytes (5.3 [2.6]–7.8 [4.1] × 10dL) Fig. . AlthougP = 0.202) vs none randomized to luspatercept.The most common TEAEs of any grade in the luspatercept arm were dizziness, nausea, diarrhea, and asthenia Fig. . TEAEs lRecommendations for the treatment of patients with MDS/MPN-RS-T include ESAs and transfusions for anemia, and lenalidomide for anemia and platelet-level reduction , 8. RecoIn conclusion, this subgroup analysis provides the first clinical trial data to support the efficacy of luspatercept in patients with MDS/MPN-RS-T, a population who currently have no proven effective treatment options. Overall, luspatercept was found to be effective—significantly reducing transfusion burden and improving mHI-E and leukocyte levels—with a generally well-tolerated safety profile.


This signaling would contribute to the elimination of this nerve terminal. Here, we investigate the involvement of the P/Q-, N-, and L-subtype channels in transgenic B6.Cg-Tg (Thy1-YFP)16-Jrs/J mice during synapse elimination. Then, the axon number and postsynaptic receptor cluster morphologic maturation were evaluated. The results show that both L- and P/Q-type VGCC (but not the N-type) are equally involved in synapse elimination. Their normal function favors supernumerary axonal loss by jointly enhancing intracellular calcium [Ca2+]i. The block of these VGCCs or [Ca2+]i  i sequestration results in the same delay of axonal loss as the cPKCβI and nPKCε isoform block or PKA activation. The specific block of the muscle cell’s contraction with μ-conotoxin GIIIB also delays synapse maturation, and thus, a retrograde influence from the postsynaptic site regulating the presynaptic CaV1.3 may contribute to the synapse elimination.During the nervous system development, synapses are initially overproduced. In the neuromuscular junction (NMJ) however, competition between several motor nerve terminals and the synapses they made ends with the maturation of only one axon. The competitive signaling between axons is mediated by the differential activity-dependent release of the neurotransmitter ACh, co-transmitters, and neurotrophic factors. A multiple metabotropic receptor-driven downstream balance between PKA and PKC isoforms modulates the phosphorylation of targets involved in transmitter release and nerve terminal stability. Previously, we observed in the weakest endings on the polyinnervated NMJ that MThe online version contains supplementary material available at 10.1007/s12035-022-02818-2. BAPTA is a Caignaling –42.5–3 , 10 mM; and peptide εV1–2, , 1 mM. The working solutions used were Che (1 µM); CaC (200 nM); βIV5–3 (10 µM); and εV1–2 (10 µM).The stock solutions were chelerythrine , 10 mM; calphostin C , 2.5 mM; peptide βIVBryostatin-1 , 10 µM; phorbol 12-myristate 13-acetate , 10 mM; 12-deoxyphorbol-13-phenylacetate-20-acetate , 1 mg/mL; 2-((2-pentylcyclopropyl)methyl) cyclopropaneoctanoic acid , 100 mM. The working solutions used were BRY (1 nM); PMA (10 nM); dPPA (0.2 µg/mL); and FR236924 (100 nM).The stock solutions were dihydrochloride , 5 mM; 8-bromoadenosine-3′,5′-cyclic monophosphorothioate, Rp-isomer sodium salt , 5 mM; and adenosine-3′,5′-cyclic monophosphorothioate, Rp-isomer sodium salt , 5 mM. The working solutions used were H89 (5 µM); Rp-8-Br-cAMPS (100 µM); and Rp-cAMPs (100 µM).The stock solution was adenosine 3′,5′-cyclic monophosphorothioate,8-bromo-, Sp-isomer, sodium salt , 5 mM. The working solution was 10 µM.Stock solutions were prepared using PBS or DMSO in accordance with the commercial product information. All these solutions are referenced as specific, but possible nonspecific effects of inhibitors and stimulators cannot be discarded.V1.3 (CACNA1D) antibody voltage-dependent L-type calcium channel subunit α1D ; anti-CaV2.1 (CACNA1A) antibody voltage-dependent P/Q-type calcium channel subunit α1A ; anti-CaV2.2 (CACNA1B) antibody voltage-dependent N-type calcium channel subunit α1B ; Munc18-1 antibody ; PKCε (22B10) antibody .Anti-Camiddle of the axonal loss process. The nerve terminal elimination coincides with the morphological maturation of the postsynaptic component on the NMJ. From the beginning, a uniform nAChR distributed oval plaque (S1) modifies into an increasingly structured pattern of independent primary gutters (S4)  or 500 μM magnesium ions in the bath, MC or Che , 70–72. C or Che , 72. The-channel , 72–74. It’s known that PQ-type channels are the primary channels responsible for neurotransmission at the NMJ. Our results showed similar levels of innervation when NT and W-Aga were used. Even if both channels contributed equally to presynaptic calcium signals at this stage of development, blocking either channel would be unlikely to produce equal effects on total calcium signal blocking with BAPTA. However, we favor the hypothesis that only a part of the calcium inflow is devoted to contribute to the axonal retraction and this aliquot, probably acting through a saturable mechanism, can be indistinctly carried by the operative VGCC present in the endings in process of elimination. Because of this consideration, we think that the effects of L- and PQ-type channel block (or activation) may not be additive.2+ channel in skeletal muscle, functions primarily as a voltage sensor that couples depolarization of the transverse tubules to ryanodine receptor opening and release of Ca2+ from the sarcoplasmic reticulum promoting contraction. Dihydropyridine actions on the muscle CaV1.1 could contribute to synapse elimination by affecting both directly a change in the postsynaptic activity and postsynaptic specializations and the nerve terminals via retrograde signals. This possibility can be not disconsidered and merits further analysis because, in fact, modulation of the BDNF-TrkB retrograde signaling affects axonal elimination i? It is plausible that a calcium-activated neutral protease (CANP) present in nerve endings could contribute o increased from 0.5 to 1 mM, but decreased significantly at 2 mM i elevation in some nerve terminals through L- and P/Q-type VGCC Below is the link to the electronic supplementary material.


In the crystal, molecules of the title compound are connected through C—H⋯N and C—H⋯O hydrogen bonds, I⋯O halogen bonds, π–π stacking interactions between the benzene and pyrimidine rings, and edge-to-edge electrostatic interactions, as shown by the analysis of the Hirshfeld surface and two-dimensional fingerprint plots, as well as intermolecular interaction energies. 10H8FIN2O3S, are connected through C—H⋯N and C—H⋯O hydrogen bonds, I⋯O halogen bonds, π–π stacking interactions between the benzene and pyrimidine rings, and edge-to-edge electrostatic interactions, as shown by the analysis of the Hirshfeld surface and two-dimensional fingerprint plots, as well as intermolecular interaction energies calculated using the electron-density model at the HF/3–21 G level of theory.In the crystal, molecules of the title compound, C Its derivatives are well known for their biological activities such as anti-analgesic, anti-inflammatory, anti-hypertensive, sedative, hypnotic, anti-histaminic, anti-tumor, anti-microbial, anti-convulsant, anti-bacterial, anti-fungal, enzyme inhibition, and anti-HIV activities (Kumar 2.2)2SO2F side chain, the C9/C10/S1 fragment forming a dihedral angle of 76.1 (5)° with the quinazoline (N1/N2/C1–C8) system mean plane, whereas the I1 and O1 substituents do not deviate appreciably from the latter plane. The molecule is stabilized by a weak intramolecular C10—H10B⋯O1 hydrogen bond, forming an S(6) ring motif. The S1 atom has a slightly distorted tetrahedral geometry. In the heterocycle, the N1=C1 bond [1.271 (8) Å] is essentially double, while those at the three-coordinate N2 atom are nominally single .The molecular structure of (I)et al., 2014et al., 2012et al., 2013et al., 2011et al., 2009et al., 2018abThe bond lengths and angles are in agreement with those in related structures , with a mean interplanar separation of 3.503 (4) Å  contact of 3.152 (6) Å is considerably shorter than the sum of the van der Waals radii of 3.61 Å -ethyl-2-cyano-2-(3H-quinazoline-4-ylidene)acetate -quinazolinedione -4-[(quinazolin-4-yl) level of theoryamino]benzene-1-sulfonamide and N--4-[(quinazolin-4-yl)amino]benzene-1-sulfonamide  is shown in Fig. 4The Hirshfeld surfaces and two-dimensional fingerprint plots were calculated using 6.CrystalExplorer17.5 software. Eleven molecules surrounding the original one with shortest intermolecular atom–atom distances of 3.8 Å or less were included in the calculations. The total interaction energy (Etot) between each pair of molecules comprises coloumbic (Eele), dispersion (Edis), polarization (Epol) and exchange-repulsion interaction energies (Erep) −1), but is remarkable given that only one pair of atoms is actually in contact.Quantification of intermolecular interactions energies is important for molecular recognition, protein modelling and drug design -one  in DMF (2 mL), a solution of 2-bromoethanesulfonyl fluoride  in DMF (1 mL) was added, under an N2 atmosphere. The reaction was heated at 353 K for 4 h under an N2 atmosphere (monitored by TLC). After the complete conversion of the reactants as confirmed from TLC analysis, the reaction mixture was quenched with saturated NH4Cl solution (25 mL), extracted with EtOAc (25 mL) and the collected organic layer was further washed with water (25 mL) and brine (25 mL), then dried over anhydrous Na2SO4 and concentrated under vacuum. Compound (I)To an ice-cooled stirred suspension of NaH  and 6-iodoquinazolin-4 = 1.2Ueq(C) for both.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698902201221X/zv2021sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698902201221X/zv2021Isup3.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698902201221X/zv2021Isup3.cmlSupporting information file. DOI: 1987361CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


These new complexes and some previously reported partially protonated rare earth biphenolate complexes [Ln(mbmp)(mbmpH)(thf)n] react with lithium, aluminium, potassium and zinc organometallic reagents to form lanthanoid‐main group heterobimetallic species. When reaction mixtures containing the Ln biphenolate complexes were treated with n‐butyllithium, both molecular ([Li(thf)2Ln(mbmp)2(thf)n]  and Er 8, Yb 9, and Lu 10 (n=1)) and charge separated ([Li(thf)4][Ln(mbmp)2(thf)2]  complexes were isolated. Treatment with trimethylaluminium also led to isolation of molecular ([AlMe2Ln(mbmp)2(thf)2] ) and ionic [La(mbmp)(thf)5][AlMe2(mbmp)] (18) complexes. One gadolinium‐potassium ([K(thf)3Gd(mbmp)2(thf)2] (19)), and one ytterbium‐zinc species ([ZnEtYb(mbmp)2(thf)] (20)) were isolated from treatment of reaction mixtures with potassium bis(trimethylsilyl)amide and diethylzinc respectively.Several new trivalent dinuclear rare earth 2,2’‐methylenebis (mbmp2‐) complexes with the general form [Ln2(mbmp)3(thf)n] react with lithium, aluminium, potassium and zinc organometallic reagents to form lanthanoid‐main group heterobimetallic species. The selectivity is not due to lanthanoid ion size, and perhaps solubility is a key factor.We have previously described a similar synthetic approach to yield mononuclear, partially deprotonated rare earth biphenolate complexes with the general form .1–4 are consistent with complete deprotonation of mbmpH2 as the v(OH) bands of the biphenol (ca. 3600 cm−1 and 3390 cm−1) are absent.Satisfactory microanalyses and complexometric Ln analyses were obtained for 1–5 and selected bond lengths of these complexes have been summarised below with the appropriate structural figures.X‐ray crystal structures were determined for 1 and 2 are isostructural with a previously reported dinuclear dysprosium complex.2− ligands , and two cis thf molecules (O(7)‐Ln(1)‐O(8) 94.22(17)° (1) and 92.08(9)° (2)). The Ln(2) atom is five‐coordinate, with a distorted square pyramidal donor array. It is equatorially ligated by a single oxygen  of two bridging mbmp2− ligands, one equatorial chelating mbmp2−  and one axial thf molecule.Complexes 3 and 4 are isostructural, and the composition varies from complexes 1 and 2 by one less coordinated thf molecule. Both metal atoms have a distorted square pyramidal stereochemistry  and O(3) terminal, and O(2) and O(4) bridging to Ln(2), and a thf donor. The other metal atom, Ln(2), is coordinated by the bridging oxygens, a terminal, chelating mbmp2− ((O(5) and O(6)), and a thf molecule.Complexes 5 is comprised of a six‐coordinate cerium centre, with a distorted octahedral donor array 3] with mbmpH2 and was treated with azobenzene to give a dimethylaluminum derivative.2 with the corresponding rare earth chloride.Lanthanoid biphenolate heterobimetallic chemistry is still limited and few complexes have been reported. We previously reported the synthesis of an yttrium‐aluminium bimetallic complex from treating the partially protonated yttrium biphenolate complex   or (c) for the formation of putative La and Pr analogues which so far have not been crystallised, were treated with n‐butyllithium (Ln : Li=1 : 1), heterobimetallic complexes 6–14 were successfully obtained (Scheme 6–10), or a discrete cation‐anion pair (complexes 11–14). Elemental analyses of the complexes were determined after drying under reduced pressure, and therefore some exhibited loss of lattice solvent and in some cases coordinated solvent from the crystal composition as determined by X‐ray crystallography. Thus, microanalyses of 6 and 7, which have no lattice solvent, corresponded to the crystal composition. Complex 8 exhibited loss of two lattice C6D6 and two coordinated thf, 10 loss of three C6D6 lattice solvent, 11 loss of one lattice thf and two coordinated thf, 12 and 13 exhibited loss of 0.5 lattice thf, and 14 exhibited loss of one lattice thf and four coordinated thf molecules. These results were supported by complexometric titration to determine the % rare earth metal. Crystals of complex 9 were isolated, but only in low yields, hence only an X‐ray crystal structure could be obtained.When RTP reaction mixtures (a) for the formation of 6–14 are consistent with complete deprotonation of the mbmpH2 starting material (no v(OH) absorption). Of these complexes only the 1H NMR spectra of 6 and 10 were able to be recorded and interpreted, and both confirm biphenolate:thf ratios observed in the X‐ray crystal structures. The molecular Li/Ln complexes show the bridging CH2 resonance split into an apparent AB doublet (slightly broadened in the case of 10).IR spectra of complexes 6 and 7 are isomorphous (Table S1) molecular compounds and are comprised of a six‐coordinate, distorted octahedral Ln atom, bridged by phenolate oxygen atoms to a four‐coordinate, distorted tetrahedral Li atom , with one oxygen of each bound solely to the Ln atom in the axial positions, and the other oxygen of each bridging between the Ln and the Li atoms, and two cis thf molecules in the equatorial sites. The Li atom is bound by two bridging mbmp2− oxygens, and two thf molecules. The bridging oxygens of the two mbmp2− ligands have considerably longer Ln−O bond lengths than their non‐bridging counterparts.Complexes m Figure . The Ln 8–10 are isostructural molecular compounds and are comprised of a five‐coordinate, distorted square pyramidal Ln atom, linked to a four‐coordinate, distorted tetrahedral Li atom , each with one terminal oxygen, and one oxygen bridging the Ln and Li atoms, and one thf. The two bridging mbmp2− oxygens, and two molecules of thf ligate the Li atom. Again, the bridging Ln−O bond lengths are considerably longer than their non‐bridging counterparts. A previously prepared Yb−Li analogueComplexes m Figure . Similar11–14 are isostructural ionic compounds, with a six‐coordinate, octahedral Ln atom in the anion, and a four‐coordinate, tetrahedral Li atom in the cation ‐Sm(1)‐O(6)=82.46(7)°) in the equatorial positions. The Ln−O bonds of the mbmp2− ligands are considerably longer in the axial positions. The [Li(thf)4]+ cation is widely reported in the literature, with 595 structural studies.4][Ln(mbmp)(N(SiCH3)3)2] (Ln=Nd and Yb) have previously been synthesised by treatment of chloride bridged rare earth biphenolate complexes with lithium bis(trimethylsilyl)amide,4]+ cation shows slightly longer Li‐O(thf) bond lengths (average Li‐O(thf)=1.908 Å) than complexes 11–14 (average Li‐O(thf)=1.845 Å). The difference in bond length could be attributed to elevated temperatures during data collection for the [Li(thf)4][Ln(mbmp)(N(SiCH3)3)2] compounds (193 K vs 100 K for 11–14).Complexes n Figure . The Ln n] and which give [Ln2(mbmp)3(thf)n] complexes in RTP reactions, the factors deciding which Ln metals give molecular Li/Ln bimetallics  and which give charge separated species  are not clear. Whilst the latter appear associated with mid‐sized Ln3+, a break between Ho and Y/Er is surprising. The division cannot be correlated with the two different classes of reagent, as some from each class fall into each class of heterobimetallics. Moreover, the molecular/ charge separated division for Li/Ln bimetallics does not relate to the division within Al/Ln bimetallics (below) where La and Pr fall into different classes and Sm now gives a molecular Al/Sm species. It may be that solubilities and crystallization conditions decide the outcome.Just as there was no obvious correlation between which Ln elements form [Ln(mbmp)(mbmpH)(thf)2(mbmp)3(thf)n] 2) with trimethylaluminium 2(thf)] (Ln=Pr (15), Sm (16), and Tb (17)), or a discrete cation‐anion pair in [AlMe2(mbmp)][La(mbmp)(thf)4] (18)  absorptions were observed signifying total deprotonation of the mbmpH2 ligand. The 1H NMR spectrum of paramagnetic 17 was able to be collected and interpreted, confirming biphenolate:thf:Me(Al) ratios. Complex 17 also shows the splitting of the bridging CH2 resonance observed for the Li/Ln heterobimetallics, but this feature is shifted to lower energies, whereby one of the signals is slightly masked by the thf resonance.Elemental analyses were collected after drying under reduced pressure. Complex 15–17 are isostructural molecular compounds, comprised of a six‐coordinate, distorted trigonal prismatic Ln atom, linked to a four‐coordinate, distorted tetrahedral Al atom ‐Ln(1)‐O(6)=149.45(13)° (15), 148.71(10)° (16), 150.1(2)° (17)). One oxygen of each mbmp2− ligand is coordinated solely to the Ln, whilst the other is bridging between the Ln and Al atoms. The aluminium atom is coordinated by the two bridging mbmp2− oxygens, and two methyl groups. Again, the Ln−O bond lengths of the bridging oxygens are significantly longer than their non‐bridging counterparts. Analogous rare earth‐aluminium biphenolate bimetallics with the general form [AlMe2Ln(mbmp)2(thf)2]  i18 is an ionic compound, comprised of a seven‐coordinate, distorted pentagonal bipyramidal lanthanum cation and a four‐coordinate, distorted tetrahedral aluminium anion ‐La(1)‐O(2)=92.93(7)°) and five thf molecules, one in an axial, and four in equatorial positions. The aluminium atom is ligated by two methyl groups, and one chelating mbmp2− ligand.Complex n Figure . The lan3]3)2, yielding [K(thf)3Gd(mbmp)2(thf)2] (19) (Scheme 19 shows complete deprotonation of the mbmpH2 ligand by the absence of a v(OH) band. An interpretable 1H NMR spectrum could not be collected due to the paramagnetic nature of Gd3+. The elemental analysis of 19 after drying under vacuum showed loss of one half of a lattice thf molecule, and this was supported by complexometric titration to determine % Gd.One rare earth‐potassium heterobimetallic complex was isolated, which was from the reaction of  ) with diethylzinc resulted in redistribution, yielding a zinc biphenolate complex, [Zn(mbmp)2(thf)]2 instead of the targeted heterobimetallic.4 was treated with two equivalents of diethylzinc in the presence of one equivalent of mbmpH2, [ZnEtYb(mbmp)2(thf)] (20) was isolated (Scheme 20 displayed no v(OH) absorption, confirming complete deprotonation of mbmpH2. Yb3+ is paramagnetic in nature and no interpretable 1H NMR spectrum of 20 could be collected. The elemental analysis after drying under vacuum showed loss of one and a half lattice C6D6 molecules .Previous attempts of synthesising rare earth‐zinc biphenolate heterobimetallic complexes, by treatment of partially protonated rare earth biphenolates (2.Complex y Figure . The ytt2(mbmp)3(thf)n]  and Ho 3, Yb 4 n=3), alongside one previously reported cerium(IV) complex [Ce(mbmp)2(thf)2] (5), have been synthesised by RTP reactions between free Ln metals, Hg(C6F5)2, and mbmpH2. These dinuclear complexes, as well as some known partially protonated [Ln(mbmp)(mbmpH)(thf)n] complexes, generated in situ, were treated with various organometallic bases  to yield a range of heterobimetallic complexes. Use of in situ generated complexes greatly simplifies the bimetallic synthesis. Two types of rare earth–lithium bimetallic complexes were obtained, namely molecular compounds with the general form [Li(thf)2Ln(mbmp)2(thf)n]  and Er 8, Yb 9, and Lu 10 (n=1)) or ionic species with the general form [Li(thf)4][Ln(mbmp)2(thf)2] . Similarly, treatment with trimethylaluminium led to both molecular compounds with the general form [AlMe2Ln(mbmp)2(thf)2] , and an ionic species in the case of lanthanum, [La(mbmp)(thf)5][AlMe2(mbmp)] 18. One each of potassium and zinc heterobimetallic species, namely [K(thf)3Gd(mbmp)2(thf)2] 19 and [ZnEtYb(mbmp)2(thf)] 20 were also isolated from reactions with potassium bis(trimethylsilyl)amide and diethylzinc respectively. The structures of the molecular heterobimetallics feature mbmp2− ligands bridging through one of the phenolate oxygens with the other bound solely to the lanthanoid metal.A variety of dinuclear rare earth biphenolate complexes of the general form  or [La2(mbmp)3(thf)x]. Excess lanthanum metal and mercury were allowed to settle before isolating the supernatant liquid by a filtration cannula. nButylltihium  was added to the resulting solution and stirred overnight. The solution was concentrated to ∼5 mL and crystals grew upon standing overnight . M. p. 228–230 °C; Anal. Calc. for C62H92O8LaLi (1111.24 g.mol−1): 67.01, H 8.34, La 12.50. Found: C 66.71, H 8.02, La 12.30%. 1H‐NMR : δ=7.50 , 7.19 , 5.03 , 3.68 , 3.32 , 2.33 , 1.60 3), 1.12  ppm. IR : 2667 w, 2390 w, 2110 w, 1744 m, 1605 m, 11462 s, 1372 s, 1258 s, 1200 w, 1025 s, 914 m, 861 m, 808 s, 784 m, 730 s.A Schlenk flask equipped with a magnetic stirrer bar was charged with mbmpH6 but with praseodymium filings  in place of lanthanum to form either [Pr(mbmp)(mbmpH)(thf)n] or [Pr2(mbmp)3(thf)x] before treatment with nBuLi. Crystals grew overnight from the mother liquor . M. p. 168–170 °C; Anal. Calc. for C62H92O8PrLi (1113.24 g.mol−1): C 66.89, H 8.33, Pr 12.66. Found: C 66.17, H 7.69, Pr 12.27%. IR : 2377 w, 2271 w, 2050 m, 1891 m, 1744 s, 1568 s, 1225 s, 918 s, 861 s, 812 m, 722 m, 669 s.Synthesised as per 6 but with erbium filings  in place of lanthanum to form [Er(mbmp)(mbmpH)(thf)3] before treatment with n‐BuLi. Crystals grew overnight from C6D6 . M. p. 170–172 °C; Anal. Calc. for C50H68O5ErLi (923.27 g.mol−1 after loss of two coordinated thf and two lattice C6D6): C 65.04, H 7.42, Er 18.12. Found: C 64.72, H 7.06, Er 17.84%. IR : 2724 s, 2536 w, 2479 w, 2373 w, 2279 w, 2066 m, 1890 m, 1735 s, 1600 s, 1563 m, 1204 w, 1016 m, 922 w, 856 m, 677 m.Synthesised as per 6 but with ytterbium filings  in place of lanthanum to form 4 before treatment with nBuLi. A small amount of crystals were grown from a layering of the mother liquor with n‐hexane. No further characterisation could be completed.Synthesised as per 6 but with lutetium filings  in place of lanthanum to form [Lu(mbmp)(mbmpH)(thf)3] before treatment with n‐BuLi. Crystals grew overnight from C6D6 . M. p. 230–232 °C; Anal. Calc. for C58H84O7LuLi (1075.19 g.mol−1 after loss of three lattice C6D6): C 64.79, H 7.87, Lu 16.27. Found: C 64.28, H 7.35, Lu 15.89%. 1H‐NMR : δ=7.34 , 7.11 , 4.69 , 3.80 , 3.15 , 2.27 , 1.60 3), 1.05  ppm. IR : 2725 w, 2385 w, 2271 m, 1895 w, 1748 s, 1605 s, 1462 s, 1376 s, 1258 m, 1025 m, 861 w, 800 m, 722 m, 673 m.Synthesised as per 6 but with yttrium filings  in place of lanthanum to form [Y(mbmp)(mbmpH)(thf)3] before treatment with n‐BuLi. Crystals grew overnight from the mother liquor . M. p. 132–134 °C; Anal. Calc. for C62H92O8YLi (1061.24 g.mol−1 after loss of two lattice thf and one coordinated thf): C 70.17, H 8.74, Y 8.38. Found: C 69.83, H 8.11, Y 8.05%. IR : 2370 w, 2275 w, 2049 w, 1883 w, 1741 s, 1605 s, 1381 s, 1254 s, 1204 m, 1172 m, 1139 m, 1025 s, 955 w, 865 s, 788 s, 722 m, 677 m.Synthesised as per 6 but with samarium filings  in place of lanthanum to form 1 before treatment with nBuLi. Crystals grew overnight from the mother liquor . M. p. 175–177 °C; Anal. Calc. for C70H108O10SmLi : C 66.36, H 8.59, Sm 11.87. Found: C 66.12, H 7.95, Sm 11.43%. IR : 2721 m, 2475 w, 2373 m, 2271 m, 2059 m, 1891 s, 1740 s, 1601 s, 1556 s, 1258 w, 1070 w, 874 w, 722 m, 673 s, 583 s.Synthesised as per 6 but with dysprosium powder  in place of lanthanum to form [Dy(mbmp)(mbmpH)(thf)3] before treatment with n‐BuLi. Crystals grew overnight from the mother liquor . M. p. 200–202 °C; Anal. Calc. for C70H108O10DyLi : C 65.73, H 8.51, Dy 12.70. Found: C 65.08, H 7.95, Dy 12.19. IR : 2484 w, 2373 w, 2279 w, 2063 m, 1891 m, 1728 s, 1601 s, 1376 s, 1262 s, 1204 w, 1139 m, 1025 s, 914 m, 861 s, 788 m, 677 m.Synthesised as per 6 but with holmium filings  in place of lanthanum to form 3 before treatment with nBuLi. Crystals grew overnight from the mother liquor . M. p. 182–184 °C; Anal. Calc. for C54H76O6HoLi : C 65.31, H 7.71, Ho 16.61. Found: C 64.87, H 7.44, Ho 16.15%. IR : 2725 m, 2586 w, 2365 w, 2275 m, 1907 m, 1732 s, 1601 s, 1556 m, 1204 w, 1143 w, 1074 m, 1029 s, 861 m, 792 m, 722 m, 673 s, 587 s.Synthesised as per 7 to form either [Pr(mbmp)(mbmpH)(thf)n] or [Pr2(mbmp)3(thf)x] then treated with AlMe3  in place of n‐BuLi. Crystals were grown overnight from C6D6 . M. p. 130–132 °C; Anal. Calc. for C56H82O6PrAl (1019.14 g.mol−1 after loss of two lattice C6D6): C 66.00, H 8.11, Pr 13.83. Found: C 59.48, H 7.82, Pr 13.51%. IR : 2381 s, 2271 s, 2083 w, 2034 m, 1895 m, 1752 s, 1703 s, 1609 s, 1376 w, 1250 m, 1102 m, 1021 s, 967 w, 865 m, 788 s, 718 m, 692 s.Synthesised as per 15 but with samarium filings  in place of praseodymium to form 1 before treatment with AlMe3. Crystals grew overnight from C6D6 . Anal. Calc. for C59H82D3O6SmAl : 66.19, H 8.28, Sm 14.04. Found: C 66.04, H 8.13, Sm 13.82%. IR : 2381 s, 2271 s, 2083 w, 2034 m, 1895 m, 1752 s, 1703 s, 1609 s, 1376 w, 1250 m, 1102 m, 1021 s, 967 w, 865 m, 788 s, 718 m, 692 s.Synthesised as per 15 but with terbium filings  in place of praseodymium to form 2 before treatment with AlMe3. Crystals grew overnight from C6D6 . M. p. 175–177 °C; Anal. Calc. for C56H82O6TbAl (1037.15 g.mol−1 after loss of two lattice C6D6): C 64.85, H 7.97, Tb 15.32. Found: C 64.57, H 7.63, Tb 15.08%. 1H‐NMR : δ=7.28 , 7.18 , 4.23 , 3.59 , 3.56 , 2.29 , 1.61 3), 0.97 , −0.27  ppm. IR : 2385 w, 2297 s, 1744 s, 1454 s, 1372 s, 1278 s, 1196 s, 1029 m, 996 s, 914 m, 895 s, 800 m.Synthesised as per 15 but with lanthanum filings  in place of praseodymium to form either [La(mbmp)(mbmpH)(thf)n] or [La2(mbmp)3(thf)x] before treatment with AlMe3. Crystals grew overnight from the mother liquor . M. p. 180–182 °C; Anal. Calc. for C60H90O7LaAl (1089.24 g.mol−1 after loss of one lattice and two coordinated thf): C 66.16, H 8.33, La 12.75. Found: C 66.04, H 8.21, La 12.34%. IR : 2373 w, 2283 w, 2030 w, 1891 m, 1744 s, 1605 s, 1239 w, 1021 m, 865 m, 665 m.Synthesised as per 6 but with gadolinium filings  in place of lanthanum to form [Gd(mbmp)(mbmpH)(thf)3], and KN(SiMe3)2  in place of n‐BuLi. Crystals grew overnight from the mother liquor . M. p. 268–270 °C; Anal. Calc. for C66H100O9GdK : C 64.25, H 8.17, Gd 12.74. Found: C 63.79, H 7.82, Gd 12.36. IR : 2549 m, 2410 w, 2369 w, 2283 w, 2079 m, 1891 m, 1744 s, 1609 s, 1560 m, 1233 m, 959 w, 681 s, 583 m.Synthesised as per 6 but with ytterbium filings  in place of lanthanum to form 4, and ZnEt2  was used in place of n‐BuLi. Crystals grew overnight from C6D6 . M. p. 138–140 °C; Anal. Calc. for C55H73D3O5YbZn : C 62.40, H 7.52. Found: C 62.18, H 7.37%. IR : 2553 w, 2434 w, 2377 m, 2267 s, 2132 m, 2034 m, 1748 s, 1605 s, 1376 w, 1208 m, 628 m.Synthesised as per Single crystals covered with viscous hydrocarbon oil were mounted on a glass fibre. Data were obtained at −173 °C (100 K) on the MX1: Macromolecular Crystallography beamline at the Australian Synchrotron, Victoria, Australia. Data collection and integration on the MX1: Macromolecular Crystallography beamline was accomplished using Blu‐Ice.The authors declare no conflict of interest.1As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re‐organized for online delivery, but are not copy‐edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.Supporting InformationClick here for additional data file.