The crystal structure of 1 is similar to that of the bromide salt (2), possessing anion···C5F5N···C6H5 motifs, whilst that of 3 contains columns of alternating iodide anions and parallel tetrafluoropyridyl rings. All three crystal structures possess C(1)–H∙∙∙X− and C(2)–H∙∙∙X− hydrogen bonding. DFT calculations reveal that the strengths of the hydrogen bonding interactions lie in the order C(1)–H···X− > C(3)–H···X− > C(2)–H···X− for the same halide (X−) and Cl− > Br− > I− for each position. It is suggested that salt 3 adopts a different structure to salts 1 and 2 because of the larger size of iodide.The crystal structures of 1--3-benzylimidazolium chloride ( However, we hypothesize that simple monoatomic anions, which differ in size and consequent properties, such as polarizability, can also exert a strong influence on the crystal structures adopted by 1-polyfluoroaryl-3-benzylimidazolium salts. In order to test this hypothesis we chose to investigate the crystal structures of the halide salts of 1--3-benzylimidazolium  and polively + and [(NC5F4NC3H3NCH2Ph).2X]− peaks in the positive and negative ion mass spectra, respectively of 1 (X = Cl) and 3 (X = I), and the absence of [(NC5F4NC3H3NCH2Ph)2.Br]+ and [(NC5F4NC3H3NCH2Ph).2Br]−. Attempts to prepare the fluoride analogue by the same method were unsuccessful. Salt 1 crystallized from chloroform in the polar orthorhombic space group Pna21, the same as that of 2. Salt 3 crystallized from dichloromethane in the centrosymmetric monoclinic space group P21/c. Crystal data are given in 1 and 3, together with the positions of the closest halide anions, are shown in 1--3-benzylimidazolium chloride –C(9) for 1 and 2, but parallel for 3 –H···X− hydrogen bonding, with that of salt 3 possessing two C(1)–H···X− interactions. As expected, the C···X− distances  − 378.0516. C30H20F8N635Cl3 requires 723.0784; found [2M + Cl]− 723.1200.MS (positive ion): C3.  15H10F4N3 requires 308.0811; found [M − I]+ 308.1033. C30H20F8N6I requires 743.0666; found [2M − I]+ 743.1140. MS (negative ion): I requires 126.9045; found [M − C15H10F4N3]− 126.9181. C15H10F4N3I2 requires 561.8900; found [M + I]− 561.9393.MS (positive ion): C1 and 3 were obtained by slow evaporation of solvent from solutions in chloroform and dichloromethane, respectively. Crystal data are listed in α radiation. The structures of 1 and 3 were solved using Olex2 [3)) was used for subsequent refinements. The function minimized was [w(|Fo|2 − |Fc|2)] with reflection weights w−1 = [σ2 |Fo|2 + (g1P)2 + (g2P)] where p = [max |Fo|2 + 2|Fc|2]/3. Crystals of ng Olex2  and refing Olex2  refineme1) and 2063364 (3) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.CCDC 2063365 -3-benzylimidazolium bromide are 1.083 Å within experimental error [ 1.322 Å .−···C5F4N···C6H5 motifs, whilst the iodide salt, because of the larger size of the anion, adopts a different crystal structure containing columns of alternating tetrafluoropyridyl rings and iodide anions. The strength of charge-assisted hydrogen bonding interactions lie in the order C(1)–H···X− > C(3)–H···X− > C(2)–H···X− for the same anion and Cl− > Br− > I− for each position. The strengths of the X−···C5F4N interactions also decreases in the order Cl− > Br− > I−.1--3-benzylimidazolium chloride and bromide adopt similar crystal structures with X


Correction to: BMC Biotechnol (2022) 22:33 10.1186/s12896-022-00765-3Following publication of the original article , the autIncorrect 22ama121022j0001 → Correct JP22ama121022j0001Incorrect 17H06305 → Correct JP17H06305Incorrect 20H03243 → Correct JP20H03243The original article has been corrected.


II ion has an N4 square-planar coordination geometry defined by the four N atoms of two bidentate 2,3-di-2-pyridylpyrazine ligands.In the title complex, the central Pd 14H10N4)2](NO3)2·CH3CN, consists of a cationic PdII complex, two anions and one lattice solvent molecule, all in general positions. In the complex, the PdII cation is four-coordinated in a slightly distorted square-planar geometry defined by the four N atoms of two bidentate 2,3-di-2-pyridylpyrazine ligands. The complex, anions and solvent molecule are linked by weak C—H⋯O intermolecular hydrogen bonds. In the crystal, the complex molecules are stacked in columns along the a axis.The title compound, [Pd(C The Pd—N bond lengths are almost equal [2.0170 (18) to 2.0286 (19) Å]. In the crystal, the pyridine rings are considerably inclined to the least-squares plane of the [PdN4] unit [maximum deviation = 0.0204 (7) Å], with dihedral angles of 70.56 (7) (ring N3⋯C9), 67.63 (6) (ring N4⋯C14), 71.32 (6) (ring N7⋯C23) and 71.64 (7)° (ring N8⋯C28). The nearly planar pyrazine rings [maximum deviation = 0.027 (2) Å] are fairly perpendicular to the [PdN4] unit plane, with dihedral angles of 82.07 (7) (ring N1⋯C4) and 84.20 (7)° (ring N5⋯C18).The title compound consists of a cationic Pdle Fig. 1. In the a axis. In the columns, numerous intra- and intermolecular π–π interactions between adjacent six-membered rings are present. For Cg1 (the centroid of ring N4⋯C14) and Cg1i [symmetry code: (i) −x + 2, −y + 2, −z + 1), the centroid-to-centroid separation is 3.688 (2) Å and the planes are parallel and shifted by 1.683 Å.In the crystal structure Fig. 2, the com3)2·2H2O  and stirred for 1 h at room temperature. The formed precipitate was recrystallized from MeOH/ether, washed with ether, and dried under vacuum, to give a white powder (0.378 g). Crystals suitable for X-ray analysis were obtained by slow evaporation of a MeOH/CH3CN solution, at room temperature.To a solution of 2,3-di-2-pyridylpyrazine  in acetone (30 ml) was added Pd(NO−3) and the deepest hole (−0.49 e Å−3) in the last difference-Fourier map are located 1.02 and 0.97 Å, respectively, from atom O3.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S241431462100153X/bh4059sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S241431462100153X/bh4059Isup2.hklStructure factors: contains datablock(s) I. DOI: 2062092CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal structure of a biologically important pharmacophore containing chalcone is reported. 18H17FO5, the conformation about the C=C bond of the central enone group is trans. The dihedral angle between the benzene rings is 13.08 (3)°. The hydroxy group attached to the benzene ring is involved in an intramolecular O—H⋯O hydrogen bond. In the crystal, weak C—H⋯O hydrogen bonds link the molecules into chains along [001].In the title molecule, C Especially when they have a hydroxyl group at the ortho position of an aromatic ring adjacent to the carbonyl group, they play important roles as precursors to form other flavonoids such as flavones, flavanones, flavonols and isoflavones °. An intramolecular O5—H5⋯O1 hydrogen bond °] and the para methoxy group is almost coplanar with the ring [C6—C7—O4—C12 = 177.1 (2)°]. The methoxy group at the ortho position is rotated significantly from the ring plane [C4—C5—O2—C10 = −123.9 (2)°]. In the crystal, weak C—H⋯O hydrogen bonds link the molecules into chains propagating along [001] ethanone  in 40 ml of anhydrous ethanol was added 2,3,4-trimethoxybenzaldehyde  and the temperature was adjusted to around 275–277 K in an ice bath. To the cooled reaction mixture was added 3 ml of 40% aqueous KOH solution and the reaction mixture was stirred at room temperature for 20 h. After completion of the reaction (monitored by thin-layer chromatography), this mixture was poured into ice water (100 ml) and the resulting solution acidified with 6 Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2414314620000711/lh4051sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314620000711/lh4051Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314620000711/lh4051Isup3.cmlSupporting information file. DOI: 1979111CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II complexes bearing a tridentate polypyridine ligand and N-coordinating thiocyanato ligands at the axial or equatorial position are compared.The crystal structures of two Ru viz. cis-aqua(thiocyanato-κN)(triphenylphosphine-κP)ruthenium(II) hexafluoridophosphate–acetone–water (1/0.5/1), [Ru(NCS)(C21H13N5)(C18H15P)(H2O)]PF6·0.5C3H6O·H2O (I) and trans-bis(pyridine-κN)(thiocyanato-κN)ruthenium(II) thiocyanate, [Ru(NCS)(C21H13N5)(C5H5N)2]NCS (II), with an N-coordinating thiocyanato group and a tridentate polypyridyl supporting ligand, are reported. The RuII atom in each of the cationic complexes adopts a distorted octahedral coordination sphere, defined by an N atom of the thiocyanato ligand, three N atoms from the tridentate polypyridyl ligand, and an O and P atom in (I) or two pyridine-N atoms in (II) derived from monodentate ligands. The thiocyanato ligand in (I) coordinates in an axial manner to the {Ru-dnp} unit , whereas it coordinates in an equatorial manner in (II). In the crystal structure of compound (I), intramolecular C—H⋯O, C—H⋯N and O—H⋯N hydrogen bonds as well as π–π contacts are present, in addition to intermolecular C—H⋯F, C—H⋯O and O—H⋯O hydrogen bonds. In the crystal structure of compound (II), intramolecular C—H⋯N hydrogen bonds are observed along with intermolecular C—H⋯N and C—H⋯S hydrogen bonds as well as a π–π interaction.The molecular and crystal structures of two ruthenium(II) complexes,  Their crystal structures are reported and compared in this communication.During the current study, the reaction of precursors with different axially bound ligands with the NCS2.II atoms in (I)et al., 20133 or pyridine and the non-coordinating N atoms in dnp or the monodentate ligands [OH2 in (I)NCS in (II)]. In (I)Cg1⋯Cg2 = 3.640 (4) Å and Cg3⋯Cg4 = 3.749 (3) Å where Cg1, Cg2, Cg3, and Cg4 are the centroids of the N1/C1–C5, C29–C34, N3/C9–C13, and C35–C40 rings, respectively] are present, with a slippage of 1.2 Å for Cg1⋯Cg2. It is inferred from these results that both π–π interactions are not exactly cofacial. The slippage angle β is 19.2° for Cg1⋯Cg2 and 16.2° for Cg3⋯Cg4.Figs. 1II complexes containing polypyridines have been determined structurally, but the N-atom coordination is overwhelmingly dominant. These complexes can be distinguished crystallographically by the Ru—X—C bond angle (X = N or S) through the coordinating atom. For example, the Ru—S—C bond angles (for S-ligating examples) are 104–106° II atoms in both compounds exhibit an N-coordination.As mentioned above, it is important to distinguish the coordination atom of the thiocyanato ligand because of its ambidentate coordination mode. Both S- and N-coordinated RuII atom and the nitrogen atom in (I)II–NCS}+ moieties  per formula unit. Apart from Coulombic forces, there are weak C—H⋯F hydrogen bonds between the complex cation and the PF6− anion n Table 1 and the n Table 1.X (X = N or S) hydrogen-bonding interactions exist between the complex cation and the NCS− anion (Table 2Cg5⋯Cg5i = 4.0093 (15) Å; Cg5 is the centroid of the N5/C17–C21 ring; symmetry code: (i) 1 − x, 1 − y, 1 − z] with a centroid slippage of 1.263 Å for Cg5⋯Cg5i are present. The slippage angle β is 18.4° for Cg5⋯Cg5i. These interactions lead to the formation of a three-dimensional network structure n Table 2 along wire Fig. 4.4.II complexes with both N-coordinating thiocyanato and tridentate terpyridine derivative ligands (tpyR) of the form [Ru(tpyR)(NCS)L2]n  have been reported, as revealed by a search of the Cambridge Crystal Structure Database 2(H2O)](PF6)2  . Crystals suitable for use in X-ray diffraction (XRD) studies were grown by vapor diffusion of diethyl ether into an acetone solution of (I)CN at 2130 cm−1.A methanolic solution (40 ml) containing [Ru(dnp)(PPh2(H2O)](PF6)2  . The yield was 9 mg (40%). Single crystals suitable for XRD studies were obtained by recrystallization from acetone. FTIR using a KBr pellet showed νCN at 2121 (ligand) and 2055 cm−1 (counter-ion).For the synthesis of compound (II)6.Uiso(H) = 1.2Ueq(C). The acetone solvent molecule in (I)Table 310.1107/S2056989022004443/wm5641sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989022004443/wm5641Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989022004443/wm5641IIsup3.hklStructure factors: contains datablock(s) II. DOI: 2168839, 2168838CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The molecule is planar (r.m.s. deviation = 0.0164 Å) and in the crystal, inversion-symmetric dimers are formed as a result of pairs of strong O—H⋯O and weak C—H⋯O hydrogen bonds. A brief comparison is made with structurally related compounds deposited in the CSD. In addition, the synthesis and some spectroscopic details are presented.The structure of 2-chloro-1-(3-hydroxyphenyl)ethanone, C All bond lengths and angles fall within the expected ranges for organic structures.The molecule of I Fig. 1 is plana3.O⋯O2i and O1i—H1Oi⋯O2 , giving an i and C2i—H2i⋯O2 (Table 1i = 2.22 (3) Å]. These interactions are all illustrated in Fig. 2ii [symmetry code: (ii) −x + y − z + 1 screw-related molecules, which loosely connect the dimers into layers parallel to . QAJNAS  was added dropwise to a stirred mixture of 3-hydroxyacetophenone  in 5 ml of methanol and 10 ml of ethyl acetate/dichloromethane at 293–303 K. After completion of the addition, it was allowed to return to RT with stirring for 1 h. The reaction was monitored by TLC. Then the solvent was removed under reduced pressure by rotary evaporation to give the desired product in 95% yield. An overall reaction scheme is depicted in Fig. 4Spectroscopic data: Infrared and NMR spectroscopic details are as follows.−1): 3400 , 2987 (C—H stretching), 1694 (C=C stretching), 1789 , 832 .FTIR : 4.7 , 5.671 , 7.14 , 7.36–7.4 , 7.493–7.51 .6.sp2—H) and 0.99 Å (R2CH2). The hydroxyl hydrogen atom coordinates were refined freely. In all cases, Uiso(H) values were set to 1.2Ueq of the attached atom.Crystal data, data collection, and structure refinement details are given in Table 210.1107/S2056989022009835/vm2272sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989022009835/vm2272Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022009835/vm2272Isup3.cmlSupporting information file. DOI: 2211527CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


N-[1-(2-pyrazinyl)ethylidene]propanehydrazide, is a ligand able to form polynuclear metal complexes. The molecule is not planar due to a twist between the oxime and amide groups. In the crystal, molecules are linked by O—H⋯O hydrogen bonds into supramolecular chains.The title compound, 2-hydroxyimino- 9H11N5O2, the oxime and hydrazide groups are situated in a cis-position in relation to the C—C bond linking the two functional groups. The CH3C(=NOH)C(O)NH fragment deviates from planarity because of a twist between the oxime and amide groups. In the crystal, molecules are linked by O—H⋯O hydrogen bonds, forming zigzag chains in the [013] and [0In the molecule of the title compound, C In recent decades, a number of ligands based on 2-hydroxyiminopropanehydrazide have been obtained. It was shown that such a type of ligand reveals a strong tendency for the formation of polynuclear complexes (Anwar N-[1-(pyrazin-2-yl)ethylidene]propanohydrazide (1), was first described in the work of Feng and co-workers propanehydrazide derivatives. Such a conformation is stabilized additionally by an H4⋯N5 attractive interaction (2.33 Å). Despite the distance being shorter than the sum of the van der Waals radii C(O)NH fragment deviates from planarity (r.m.s. deviation of 0.362 Å) because of a twist between the oxime and the amide groups about the C7—C8 bond. The maximum deviations are 0.8763 (9) and 0.3355 (18) Å, respectively, for hydrogen (H9C) and non-hydrogen (O1) atoms. The O1—C7—C8—N5 torsion angle is 165.1 (3)°, significantly less than the average value in 2-(hydroxyimino)propanehydrazide derivatives published previously [172.1 (4)°]. Thus, such a twist distortion of the molecule seems to be a result of the crystal packing.The CH3.i and C2—H2A⋯O2ii intermolecular hydrogen bonds [symmetry codes: (i) −x + y + 1, z + x + y − 1, z − A⋯N2iii intermolecular hydrogen bonds [symmetry code: (iii) −x + 1, −y − 1, z + In the crystal, molecules are linked by O2—H2⋯O1ns Fig. 2. These c4.et al., 2007CrystalExplorer17  from red  through white to blue . The Hirshfeld surface of the title compound mapped over dnorm, in the colour range −0.6441 to 1.3084 a.u. is shown in Fig. 3A⋯N2 are the most noticeable intermolecular interactions. In addition, a C2—H2A⋯O2 weak intermolecular interaction is observed.The Hirshfeld surface analysis  pair with the full fingerprint plot outlined in grey. Fig. 4d) reveals two sharp spikes along 1.9 Å < id + ed < 2.4 Å, which are associated with the O2—H2⋯O1 hydrogen bond.A fingerprint plot delineated into specific interatomic contacts contains information related to specific intermolecular interactions. The blue colour refers to the frequency of occurrence of the  level .The calculated geometric parameters are in good agreement with experimental values. It is important to note that the accuracy of the semi-empirical GFN2-xTB method is close to that of the DFT calculations, even though GFN2-xTB calculations are significantly computationally ‘cheaper’  and C7—N4 is shorter  than calculated. Such calculation errors are probably typical for hydrazide derivatives at this level of theory . The maximum number of metal centres per molecule for the discrete complexes of this type is 12 propanehydrazide derivatives. Most of them are polynuclear 37.et al., 20181H NMR, 400.13 MHz, (DMSO-d6): 11.97 , 10.21 , 9.31 , 8.56 , 8.55 , 2.37 , 2.02 . IR : 1658 (CO amid I), 1034 (NO oxime). Analysis calculated for C9H11N5O2: C 48.86, H 5.01, N 31.66%; found: C 48.49, H 5.22, N 31.42%.The title compound was prepared according to a slightly modified procedure (Feng 8.Uiso = nUeq of the carrier atom (n = 1.5 for methyl groups and n = 1.2 for other hydrogen atoms).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989022007927/vm2270sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022007927/vm2270Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022007927/vm2270Isup3.cdxSupporting information file. DOI: 2195126CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal structure of the title compound was redetermined at 100 K in order to achieve improved structural data, especially with respect to the C—C distances and the hydrogen bonding. 2(C4H9)4Cl2(OH)2], was redetermined at 100 K by use of an area detector to provide new data to improve the structural parameters for detailed analysis. Noteworthy is the folding of the central, non-symmetric, four-membered [SnO]2 ring [dihedral angle about the O⋯O axis = 1.09 (3)°], as well as the elongation of the Sn—Cl bonds [mean value = 2.5096 (4) Å], as a result of intermolecular O—H⋯Cl hydrogen bonds; the latter lead to a chain-like arrangement of dimeric molecules along [101].The structure of the dimeric title compound, [Sn The structure of the title compound has been determined previously at room temperature using point detector data as part of a paper describing the series of dimeric di-tert-butyltin(IV) hydroxide halides, [tBu2Sn(OH)X]2 with X = F, Cl and Br I]2 I]2 compounds [pure state: d(Sn—C)mean = 2.190 (3) Å mean = 2.193 (10) Å  to 1.532 (2) Å [mean value: 1.527 (4) Å], Cmethyl—C—Cmethyl angles in the range 107.1 (1) to 111.1 (1)° [mean value: 109.5 (11)°] and Sn—C—C angles of 107.1 (1) to 111.1 (1)° [mean value: 108.9 (12)°]. These new data are of the same precision and absolute values as those found in the iodide compound both in the pure state , which are considerably longer in comparison with other Brønstedt-Base (BB) stabilized diorganotin(IV)-hydroxide-chlorides 2 molecules along [101], Fig. 3These unusually long Sn—Cl bonds in the title compound arise from the fact that the chloride atoms are involved in intermolecular O—H⋯Cl hydrogen bonds Table 1, resultiet al.  I. DOI: 10.1107/S2414314623000561/tk4087Isup2.hklStructure factors: contains datablock(s) I. DOI: 2237568CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


H-indole ring system is nearly planar, while the conformation of the 4H-pyran ring is close to a flattened boat. The mean planes of these fragments are approximately perpendicular to each other. In the crystal, the molecules are connected into layers by N—H⋯N and N—H⋯O hydrogen bonds.In the title structure, the 2,3-dihydro-1 17H14BrN3O4, an admixture [0.0324 (11)] of its 7-bromo isomer. The 2,3-dihydro-1H-indole ring system is nearly planar, while the conformation of the 4H-pyran ring is close to a flattened boat. The mean planes of these fragments form a dihedral angle of 86.67 (9)°. The carboxylate group lies near the plane of 4H-pyran, its orientation is stabilized by an intramolecular C—H⋯O contact. In the crystal, the molecules are connected into layers by N—H⋯N and N—H⋯O hydrogen bonds. The most important contributions to the crystal packing are from H⋯H (33.1%), O⋯H/H⋯O (16.3%), N⋯H/H⋯N (12.1%), Br⋯H/H⋯Br (11.5%) and C⋯H/H⋯C (10.6%) interactions.The crystal used for structure determination contained, along with the title compound, C The mean planes of the 2,3-dihydro-1H-indole system and the 4H-pyran ring are approximately perpendicular to each other, forming a dihedral angle of 86.67 (9)°. The carboxylate group lies near the plane of 4H-pyran, with O3—C13—C10—C11 and O4—C13—C10—C3 torsion angles of −13.4 (3) and −8.8 (2)°, respectively. An intramolecular C16—H16A⋯O3 contact stabilizes the conformation of the molecule  ring motif :0.0324 (11) ratio, whereas the positions of other atoms of these isomers coincide with each other Fig. 2. The 2,3le Fig. 2, generat3.H-pyran and benzene rings link adjacent molecules within these layers  Table 1 ▸ ▸. ICrystalExplorer17  ring motif. The molecules are linked by pairs of N—H⋯O hydrogen bonds into ribbons extending along the b-axis direction and consisting of In the crystal of II, the six-membered pyran ring adopts a conformation close to a flattened boat, as in the title structure. The molecules are joined by pairs of N—H⋯N hydrogen bonds into dimers, those are linked by N—H⋯O contacts to form ribbons along the a-axis direction.In the crystal of III, the pyran ring is nearly planar. The molecules are joined by pairs of N—H⋯N hydrogen bonds into centrosymmetric dimers, which are linked by N—H⋯O contacts into ribbons along the c-axis direction.In the crystal of 5.The title compound was synthesized using the reported procedure , N8—H8A = 0.88 (3) and N8—H8B = 0.86 (3) Å], but their isotropic displacement parameters were constrained to take a value of 1.2Ueq(N). All H atoms bound to C atoms were positioned geometrically and refined as riding with C—H = 0.95 (aromatic), 0.99 (methylene) and 0.98 Å (methyl), withUiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for all others.Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989022008271/yk2174sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022008271/yk2174Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022008271/yk2174Isup3.cmlSupporting information file. DOI: 2202347CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The compound crystallizes with one molecule in the asymmetric unit in the monoclinic space group P21/n with a rather long b axis [33.8752 (2) Å]. Weak C—H⋯O and C—H⋯N interactions consolidate the crystal packing. The nitrite-O atoms each occupy a single position in the coordination geometry.The molecular structure of the title compound, [Ag(NO The nitrito ligand coordinates in a near symmetric fashion with similar bond lengths . The pseudo-tetrahedral coordination environment exhibited around the AgI atom stems from the three coordinating ligands, with corresponding bond angles of P1—Ag1—P2 [124.597 (16)°], P1—Ag1—O1 [116.26 (6)°], P1—Ag1—O2 [125.62 (4)°], P2—Ag1—O1 [107.68 (7)°], and P2—Ag1—O2 [107.83 (4)°]. The bidentate coordination of the nitrito ligand is underpinned by the O1—Ag1—O2 bite angle of 50.80 (7)°. The ipso-aryl carbon atoms of each of the phosphine ligands overlap in a near-staggered fashion when viewed down the P1—Ag1—P2 axis, presumably due to the steric effect of the bulky phosphine ligands. Corresponding torsion angles are P2—Ag1—P1—C1 = 9.90 (7)°, P2—Ag1—P1—C8 = −108.02 (8)°, P2—Ag1—P1—C15 = 128.73 (9)°, P1—Ag1—P2—C22 = −172.57 (7)°, P1—Ag1—P2—C36 = 70.75 (8)°, and P1—Ag1—P2—C29 = −47.35 (7)°. All of the aforementioned bond lengths and angles closely correspond to those of related AgI phosphine complexes  and silver nitrite (1 mmol) were dissolved separately in acetonitrile (10 ml). The two solutions were carefully mixed together and heated to 353 K for approximately 2 h. The solution was left to crystallize, and small clear colourless crystals were obtained.Tris-Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2414314622011488/wm4174sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622011488/wm4174Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314622011488/wm4174Isup3.cdxSupporting information file. DOI: 2223249CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal structure, the cations and anions are interconnected via several N—H⋯O and C—H⋯O hydrogen bonds.The title compound, C 6H2N3O7−·C10H13Cl2N2+, crystallizes with one 1-piperazine (DP) cation and one picrate (PA) anion in the asymmetric unit. In the crystal structure, the DP cation and PA anion are interconnected via several N—H⋯O and C—H⋯O hydrogen bonds. The DP cation and PA anion are further connected through C—Cl⋯π  and N—O⋯π [3.7814 (4) Å] interactions. The DP cations are further interconnected via a weak intermolecular Cl⋯Cl [3.2613 (4) Å] halogen–halogen interaction. The combination of these supramolecular interactions leads to a herringbone like supramolecular architecture.The title compound, C Inversion-related cation–anion pairs are also linked through N1—H1A⋯O4, N1—H1B⋯O2 and C17—H17⋯O1 hydrogen bonds, forming an Cg1, C—Cl⋯Cg3v and N—O⋯Cg3; symmetry codes: (v) 1 − x, 2 − y, 1 − z] with C⋯π distances of 3.8201 (4) and 3.7785 (4) Å, and N⋯π = 3.782 (2) Å, with C—Cl⋯π angles of 74.15 (7) and 76.91 (7)° and an N—O⋯π angle of 68.80 (12)°. The combination of N—H⋯O and C—H⋯O hydrogen bonds and C—Cl⋯π and N—O⋯π interactions leads to the formation of a three-dimensional supramolecular herringbone architecture, which propagates along the a- and c-axis directions  interactions [3.2613 (4) Å] piperazine (DP)  and picric acid (PA)  were dissolved independently in water and ethanol. The reactants were then mixed together in a 100 ml beaker and heated over a water bath at 90°C for 1 h Fig. 5. The cleCrystal data, data collection and structure refinement details are summarized in Table 210.1107/S2414314621003795/bv4037sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314621003795/bv4037Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314621003795/bv4037Isup3.cmlSupporting information file. DOI: 2076126CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the title compound, the pentofuranose ring has a twisted conformation while the other five-membered ring has an envelope conformation; the two hydroxy groups C are involved in an infinite network of O—H⋯ O bonds, forming a layer parallel to the (001) plane. 8H14O5, the pentofuranose five-membered ring has a twisted conformation on two carbon atoms while the five-membered ring of the isopropylidene group has an envelope conformation on an oxygen atom. Hydroxy groups are involved an infinite network of O—H⋯O hydrogen bonds that leads to the formation of a layer parallel to the (001) plane. Only weak C—H⋯O contacts exist between neighboring layers.In the title compound C Our interest in 1 stems from the possibility of conducting deoxygenation at its C3 position to obtain 3-deoxy-1,2-O-isopropylidene-β-d-threo-pentofuranose as a chiral synthon for further synthetic work  side to furnish 1,2-O-isopropylidene-5-O–t-butyldiphenylsilyl-β-d-lyxo-furanose, whose desilylation gave the target 1. It should be pointed out that under these isopropylidenation conditions, d-lyxose furnished only its α,β-2,3-O-isopropylidenefuranose  Å, φ = 117.6 (2)°]. The five-membered ring of the isopropylidene group has an envelope conformation on atom O1 . Puckering parameters  distance is 3.389 (2) Å. Similar hydrogen bonds have been observed in various carbohydrates  plane Table 1. Only wep Table 1 may addiet al.  and a probability of the absolute configuration being correct of 1.000.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2414314620016302/zq4044sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314620016302/zq4044Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314620016302/zq4044Isup3.cdxSupporting information file. DOI: 10.1107/S2414314620016302/zq4044sup4.txtCuK CIF file for chirality confirmation. DOI: 2050681CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, C—H⋯O and C—H⋯N hydrogen bonds connect the molecules into [001] chains. 12H9ClN2O, the dihedral angle between the aromatic rings is 1.78 (4)° and an intramolecular O—H⋯N hydrogen bond closes an S(6) ring. In the crystal, C—H⋯O and C—H⋯N hydrogen bonds connect the molecules into [001] chains.In the title compound, C S(6) ring. The disposition of the aromatic rings is trans as indicated by the C2—N2—C13—C7 torsion angle of −179.7 (2)° ° and an intramolecular O—H⋯N hydrogen bond closes an )° Fig. 1. In the )° Fig. 1 generateps Fig. 2. These aps Fig. 2.et al.  and 2-hydroxy benzaldehyde (1.2 mmol) were mixed in 20 ml of absolute ethanol with the addition of few drops of piperidine as catalyst. The mixture was refluxed for 5 h at 60–70°C. Colourless blocks of the title compound were obtained from the mother solution on cooling.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2414314620000115/hb4333sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2414314620000115/hb4333Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314620000115/hb4333Isup3.cmlSupporting information file. DOI: 1975774CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Scientific Reports 10.1038/s41598-021-00096-x, published online 19 October 2021Correction to: The original version of this Article contained an error in the legend of Figure 1.A) Effect on IFN-γ (a) and IL-10 expression (b) and IFN-γ to IL-10 expression ratio (c) in LPS-stimulated macrophage cells. (B) Effect on IFN-γ (a) and IL-10 expression (b) and IFN-γ to IL-10 expression ratio (c) in resident macrophage cells. Macrophage cells (1 × 106/mL) isolated from peritoneal cavity were incubated with Lactobacillus rhamnosus NK210  or Bifidobacterium longum NK219  in the absence or presence of LPS. Normal control group (CON) was treated with saline instead of LPS. Data values were described as mean ± SD (n = 4). Data values indicate mean ± SD. #p < 0.05 versus NC group. *p < 0.05 versus LP group.”“Effect of NK210 and NK219 on the expression of interferon (IFN)-γ and IL-10 in macrophages stimulated with or without LPS. (now reads:A) Effect on IFN-γ (a) and IL-10 expression (b) and IFN-γ to IL-10 expression ratio (c) in resident macrophage cells. (B) Effect on IFN-γ (a) and IL-10 expression (b) and IFN-γ to IL-10 expression ratio (c) in LPS-stimulated macrophage cells. Macrophage cells (1 × 106/mL) isolated from peritoneal cavity were incubated with Lactobacillus rhamnosus NK210  or Bifidobacterium longum NK219  in the absence or presence of LPS. Normal control group (CON) was treated with saline instead of LPS. Data values were described as mean ± SD (n = 4). Data values indicate mean ± SD. #p < 0.05 versus NC group. *p < 0.05 versus LP group.”“Effect of NK210 and NK219 on the expression of interferon (IFN)-γ and IL-10 in macrophages stimulated with or without LPS. (The original Article has been corrected.


In the title Schiff base, the dihedral angle between the phenyl rings of the benzil unit is 74.14 (5)°. 20H14ClNO, obtained from the reaction of 4-chloro aniline with benzil, has an approximate T shape. The dihedral angle between the phenyl rings of the benzil unit is 74.14 (15)°. The extended structure features C—H⋯O hydrogen bonds.The title Schiff base, C The C1–C6 phenyl ring makes dihedral angles of 20.56 (6) and 74.03 (6)°with the C9–C10 and C15–C16 phenyl ring, respectively, of the benzil unit. The dihedral angle between the phenyl rings of the benzil unit is 74.14 (5)°. The C—N iminium bond length [1.268 (3) Å] is comparable to that observed in (E)-1-[4-({4-[(4-methoxybenzylidene)amino]phenyl}sulfanyl)phenyl]ethan-1-one . Together, these hydrogen bonds lead to the formation of a three-dimensional network. Aromatic π–π stacking generates inversion dimers featuring the C15–C20 phenyl rings with a centroid–centroid distance of 3.744 (3) Å [Fig. 3b)]. Along the c-axis direction, weak C—H⋯π(ring) interactions occur.In the crystal, the molecules are aligned head-to-foot along the g Table 1. The C18Crystal Explorer 3.1  and shape-index. The red spots in Fig. 4a) reflect the formation of C—H⋯O, C—H⋯π and π–π stacking interactions. In the shape-index map [Fig. 4b)], the adjacent red and blue triangle-like patches represent concave regions that indicate C—H⋯π(ring) and π–π stacking interactions. The two-dimensional FP plots indicate that the most important contributions to the packing, in descending percentage contribution, are from H⋯C (37.7%), H⋯H (34.6%), H⋯Cl (14.0%), H⋯O (6.1%), H⋯N (4.0%) and C⋯C (1.9%) contacts.A Hirshfeld surface (HS) analysis was performed and the associated two-dimensional fingerprint (FP) plots , 1660 (C=O), 3064 (aromatic C—H), 1212 (C—N) and 718 (C—Cl).To a solution of benzil  and 1 ml of acetic acid in ethanol (20 ml) was added 4-chloro aniline (0.01 mmol) dissolved in ethanol (15 ml). The mixture was stirred for 3 h under reflux. The product was isolated, recrystallized from ethanol solution and then dried in a vacuum to give the title compound . Yellow single crystals suitable for X-ray analysis were obtained by slow evaporation of a ethanol solution. IR ν, cmCrystal data, data collection and structure refinement details are summarized in Table 210.1107/S2414314623000652/hb4414sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314623000652/hb4414Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314623000652/hb4414Isup3.cmlSupporting information file. DOI: 2237868CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Compounds 1–3 are obtained by reacting Me‐cAAC=PK (amino)carbene) and dihaloaryl borane in toluene. All three compounds were characterized by X‐ray crystallography. Quantum mechanical studies indicated that these compounds have two lone pairs on the P center viz., an σ‐type lone pair and a “hidden” π‐type lone pair. Hence, these compounds can act as double Lewis bases, and the basicity of the π‐type lone pair is higher than the σ‐type lone pair.Herein, the synthesis and characterization of the carbene‐stabilized boryl phosphinidenes  What hides within: Three different singlet boryl phosphinidenes were synthesized by using cAAC carbene, and their inversely polarized phosphaalkene characteristics were investigated. Quantum mechanical studies suggest that the P center of these boryl phosphinidenes contains two lone pairs viz., an σ‐type lone pair and a “hidden” π‐type lone pair. FoiPr2NP̈:), which was formed as a transient intermediate while thermolysis of dibenzo‐7‐phosphanorbornadiene (Scheme h).i). The reactivities of phosphino‐phosphinidene were studied using several nucleophiles such as CO, isocyanides, carbenes, and phosphines, etc. –1–3) which are also characterized as inversely polarized phosphaalkenes. DFT calculations are employed to obtain further insight into the bonding and structure–property relationship of the newly developed carbene‐stabilized boryl phosphinidenes.In 2012, Cummins et al. reported a mono‐coordinated phosphinidene  in a 1 : 1 molecular ratio.Compounds 1, 2, and 3 were obtained in good yield at 0 °C from the concentrated toluene solution. Compounds 1–3 were fully characterized by NMR  and mass spectrometry (LIFDI). All these compounds are highly stable in the solid‐state and in solutions at room temperature under an inert atmosphere for months. However, they are unstable under ambient conditions and slowly change their intense yellow color to a colorless form. Single‐crystal X‐ray diffraction and elemental analysis confirmed the compositions of 1, 2, and 3.The block‐shaped yellow crystals of 13C, 31P, and 11B NMR spectroscopy provided a wealth of structural information on the inversely polarized phosphaalkene. The 13C{1H} signal of C=P unit of inversely polarized phosphaalkenes appeared at 220.9 , 220.8 , and 220.7  ppm for compounds 1, 2, and 3 respectively. The observed 13C{1H} NMR signals and JC‐P coupling constants for the C=P units are similar to the reported phosphaalkenes.31P NMR shifts for the compounds are strongly affected by the electronic nature of the substituents and the hybridization of the phosphorus atom. The introduction of an electropositive boryl group provides a deshielding effect on the phosphorus chemical shift. Also, the halogen atoms such as Cl, Br, and I on the boron center typically move the chemical shift significantly downfield. The 31P{1H} NMR signal appeared at 35.5, 47.1, and 66.9 ppm for compounds 1, 2, and 3, respectively. This observation is in accordance with the increasing order of Lewis acidity of the boron center, which increases when the halogen changes from Cl to I.31P{1H} NMR spectroscopy supports the formation of delocalized C−P−B π‐system and the extent of delocalization increases from compound 1 to 3. Note that the 31P chemical shift values move downfield compared to inversely polarized phosphaalkenes.31P chemical shifts for phosphatriafulvenes show inverse polarity around −23.2 to −74.1 ppm.11B{1H} nucleus and the asymmetric local fields in compounds usually result in broad 11B{1H} NMR resonances. The 11B{1H} NMR resonances appear at 72.83, 71.81, and 69.80 ppm for the compounds 1, 2, and 3, respectively. The 31P and 11B NMR data indicate that the B−P bond has considerable double‐bond character and 31P and 11B resonances are similar to those reported phosphinidene boranes (R−B=P−R).1, 2, and 3 consist of a C−P−B backbone with an almost coplanar halogen  atom ° (1), 179.02 (6)° (2), and 177.70 (6)° (3). The C=P=B skeleton is significantly bent with a bond angle of 114.68°, 111.94°, 110.78° and the dihedral angles between C17−C16−N1 and X1−B1−C1 planes are 25.06°, 21.43° and 31.50° for compounds 1, 2, and 3, respectively.The solid‐state structures of complexes cis to the C−P bond (C16−P1 1.7709 (15) Å) in complex 1, whereas the B−X bonds in complexes 2 (B1−Br1 2.0085(15) Å), and 3 (B1−I1 2.2504 (15) Å) are in trans position to the C−P bonds, respectively. Furthermore, the nearly anti‐periplanar alignment represented by torsion angles N−C−P−B (1 172.74(12)°, 2 164.82(9)°, 3 157.78(10)°) decrease from species 1 to 3. The P1−C16 (1 1.7709 (15) Å, 2 1.7850 (14) Å, 3 1.7944(14) Å) bond lengths are longer than reported double bond lengths in phosphaalkenes (1.61–1.71 Å)The molecular structures reveal that in the solid state, the B1−Cl1 (1.8046(18) Å) bond is 1 1.8607(18) Å, 2 1.8607(15) Å, 3 1.8456(15) Å) bond lengths are elongated compared to phosphaborenes (1.8211(16)–1.8309(16) Å)tert‐butyl‐1‐phosphaethene)(diethylhydroborato)titanocene] (2.054(3) Å)3 complex (1.931(4)–1.943(4) Å)1–3), the most elongated P−C bond length (1.7944(14) Å) and the shortest B−P bond length (1.8456(15) Å) were found in 3 (X=I). This is due to the high Lewis acidity of the boron center of compound 3 compared to 1–2 (X=Cl and Br), and the phosphinidene lone pair being relatively more engaged in donating to the boron center and compared to back‐bonding to the carbene center of cAAC. Additionally, Ccarbene−N bond lengths in 1–3 (1 1.3352(19) Å, 2 1.3379(16) Å, 3 1.3306(16) Å) are elongated (1.9–2.5 %) compared to that in free cAAC (1.3053(13) Å),Similarly, P1−B1  to I . The isomer 1′, where the B−Cl bond is oriented similar to B−X bonds in complexes 2 and 3, is less stable by 1.82 kcal mol−1. It can be attributed to the shorter P−Cl distance (2.97 Å), resulting in strong repulsions between the lone pairs on P and Cl centers .Quantum mechanical calculations were carried out at the M06‐2X/def2‐TZVPP//BP86/def2‐TZVP level of theory by incorporating Grimme empirical dispersion correction with Becke–Johnson damping (GD3BJ) to explore the bonding and reactivity of the molecules 1 reveals that HOMO‐2 is a σ‐type lone pair orbital with a larger contribution from the P atom , P−B (1.31–1.41) and Ccarbene−N (1.29–1.32) bonds. Note that these Wiberg bond indices are lower than the Ccarbene−N Wiberg bond index of free cAAC . The difference in electronegativity also induces polarity in the Ccarbene−P, P−B and Ccarbene−N bonds, reducing the bond index values. These bond index values support the partial double bond character observed in these bonds. The overall high positive group charge on cAAC (0.14–0.18) implies that σ‐donation from cAAC is higher than the π‐back donation from the P center. The NBO analysis shows considerable polarization of the P−CcAAC σ‐MO and π‐MO in opposite directions (Table S8), thus indicating the inversely polarized phosphaalkene nature. However, the net polarization is minimal, as seen from the natural charges on CcAAC (0.10–0.13 e) and P (0.06–0.08 e).The molecular orbital (MO) analysis of −1 when halogen atom is Cl (1), 2.6 kcal mol−1 for Br (2), and 2.7 kcal mol−1 for I (3). On the other hand, the energetics corresponding to the donation from halogen to B center is significantly high and decreases as 40.7 kcal mol−1 for 1, 35.3 kcal mol−1 for 2, and 30.31 kcal mol−1 for 3. The strength of the donation from the halogen atom is a deciding factor for the P−B and B−X bond lengths. The P−B bond length is shortest for 3 (1.860 Å); this is in agreement with the weaker donation of I lone pairs to the formally empty p‐orbital on B. Note that the strength of the donation from P−C π‐NBO to the B center is also significant viz., 38.4 kcal mol−1 for 1, 49.6 kcal mol−1 for 2, and 56.0 kcal mol−1 for 3. The balance between these second‐order interactions results in the intermediate dihedral angles between the planes defined by terminal B and C atoms with their corresponding substituents (23.5–33.7°).Three major interactions are responsible for the geometry of the compounds viz., the donation of σ‐lone pair on P to B center, the donation of lone pair of electrons from halogen atom to B center, and the donation from P−C π‐NBO to the B center. The strength of interaction corresponding to the donation of σ‐lone pair on P to B center is 5.4 kcal mol1–3 is monovalent, forming an electron sharing bond with B center while accepting a lone pair of electrons from cAAC. The bonding is schematically represented in Figure −1 . Hence, the P atom can act as a coordinating center for accepting electrons from cAAC. The calculated dissociation energy of compounds 1–3 to respective singlet boryl phosphinidene and cAAC was found to be moderately high, indicative of the strong binding between P−C centers . P−C bond dissociation energy values for carbene stabilized phosphinidenes have been calculated to fall in the range 43–75 kcal mol−1 at BP86/TZ2P level of theory.Based on the geometrical, MO and NBO analyses, the P center in −1) and close to that of NHCs  and C(PH3)2  but less than that in carbodicarbenes, C(NHCMe)2 .1–3. This suggests that the delocalized π‐MO in 1–3 is more basic than the σ‐lone pair having a very high s‐character (53.8–54.4 %). Hence, the delocalized π‐MO can be considered as a hidden lone pair. Frenking and co‐workers have used the term hidden lone pair for a delocalized π‐MO in carbodicarbenes and related C(0) compounds, which show very high proton affinity.A bent geometry with an active σ‐lone pair and a delocalized π‐MO is the prominent feature of carbones and related species.carbene−P (0.7–1.3 %) and P−B (2.5–2.7 %) bonds and a shortening of the Ccarbene−N bond . This corroborated well with increased cAAC group charge (0.49–0.52) and decreased negative natural charge on N (−0.35) atom. The MO analysis indicates an active lone pair (35.0–38.2 % s character) with a major coefficient on the P atom . The presence of an active lone pair with relatively low s‐character induces the addition of the second proton at the P center. The calculated second proton affinity is also quite high , indicating that P (I) center in molecules 1–3 can act as a double Lewis base.The first protonation induces an elongation in C1–3 feature a P(I) center with two lone pairs, viz. a highly reactive “hidden” π‐lone pair and a σ‐lone pair.In conclusion, we have designed, synthesized, and characterized three cAAC‐stabilized boryl‐phosphinidenes, which also show inversely polarized phosphaalkene characteristics. Quantum mechanical calculations reveal that compounds Essential experimental: Crystal data for 1 at 100(2) K: C35H54Cl2BClNP, Mr=566.02 g/mol, 0.401×0.303×0.139 mm, monoclinic, P21/n, a=9.810(2) Å, b=17.822(3) Å, c=19.840(3) Å, β=92.64(2)°, V=3465.0(11) Å3, Z=4, μ(MoKα)=0.179 mm−1, θmax=25.510°, 78252 reflections measured, 6411 independent (Rint=0.0530), R1=0.0364 [I>2σ(I)], wR2=0.0943 , res. density peaks: 0.383 to −0.237 e A−3, CCDC: 2058117.2 at 100(2) K: C35H54BBrNP, Mr=610.48 g/mol, 0.584×0.317×0.309 mm, triclinic, P1‾, a=9.805(2) Å, b=11.181(2) Å, c=16.560(3) Å, α=73.82(2)°, β=82.35(2)°, γ=88.07(3)°, V=1728.0(6) Å3, Z=2, μ(MoKα)=1.258 mm−1, θmax=27.934°, 53463 reflections measured, 8274 independent (Rint=0.0469), R1=0.0265 [I>2σ(I)], wR2=0.0674 , res. density peaks: 0.368 to −0.357 e A−3.Crystal data for 3 at 100(2) K: C42H62BINP, Mr=749.60 g/mol, 0.341×0.253×0.235 mm, triclinic, P1‾, a=10.676(2) Å, b=12.167(2) Å, c=16.836(3) Å, α=107.24(2)°, β=94.60(2)°, γ=101.62(3)°, V=2022.8(7) Å3, Z=2, μ(Mo Kα)=0.859 mm−1, θmax=27.200°, 82576 reflections measured, 9022 independent (Rint=0.0303), R1=0.0213 [I>2σ(I)], wR2=0.0531 , res. density peaks: 0.452 to −0.462 e A−3.Crystal data for λ correction1 was applied using SADABS.F2 using SHELXLAll crystals were selected under cooling by using an X‐Temp2 device.1), 2058118 (2), and 2058119 (3)2058117  should be addressed to the authors.Supporting InformationClick here for additional data file.


In the title 1:2 co-crystal, C—I⋯N halogen bonds between one of the 1,2,3,5-tetrafluoro-4,6-diiodobenzene molecules and the 5-{[4-(dimethylamino)phenyl]ethynyl}pyrimidine molecule form [110] chains while the second 1,2,3,5-tetrafluoro-4,6-diiodobenzene molecule resides in [100] channels. 14H13N3·2CF4I2. In the extended structure, two unique C—I⋯N halogen bonds from one of the 1,2,3,5-tetrafluoro-4,6-diiodobenzene molecules to the pyrimidine N atoms of the 5-{[4-(dimethylamino)phenyl]ethynyl}pyrimidine molecule generate [110] chains and layers of these chains are π-stacked along the a-axis direction. The second 1,2,3,5-tetrafluoro-4,6-diiodobenzene molecule resides in channels formed parallel to the a-axis direction between stacks of 5-{[4-(dimethylamino)phenyl]ethynyl}pyrimidine molecules and interacts with them via C—I⋯π contacts.The treatment of 5-{[4-(dimethylamino)phenyl]ethynyl}pyrimidine with a threefold excess of 1,2,3,5-tetrafluoro-4,6-diiodobenzene in dichloromethane solution led to the formation of the unexpected 1:2 title co-crystal, C The APEP and the halogen-bonded 13DIFP molecule are essentially coplanar: the interplanar angle between the pyrimidine ring and the aminophenyl ring is 4.24 (15)° and the interplanar angle between the pyrimidine ring and the halogen-bonded 13DIFP molecule is 6.63 (15)°. The two unique C—I⋯N halogen bonds that combine to form a zigzag alternating halogen-bonded chain, shown in Fig. 2i = 2.853 (2) and 2.901 (2) Å and angles C15—I1⋯N1 and C17—I2⋯N2i = 174.8 (9) and 173.8 (8)°, respectively . These distances and angles are similar to those previously reported in the 1:1 co-crystal formed between these two molecules of 2.920 (2) Å and 178.27 (6)°  1 − x, 2 − y, 1 − z] separations of 3.276 (3) and 3.316 (3) Å, respectively. These are significantly less than the sum of the van der Waals radii of 3.68 Å at 89 and 90%, respectively. The second I atom has close I⋯F contacts to two neighboring 13DIFB molecules with I3⋯F6iii and I3⋯F3iv separations of 3.2142 (17) and 3.30129 (15) Å as compared to the sum of the van der Waals radii of 3.38 Å .The pair of loosely π-stacked 13DIFB molecules interact with the surrounding molecules as shown in the Hirshfeld surface plot in Fig. 5The pyrimidine APEP (8.3 mg) was dissolved in 2 ml of dichloromethane in a screw-cap vial. Three equivalents of 13DIFB were added and the solvent was allowed to slowly evaporate until crystals formed when the vial was sealed to prevent further loss of solvent.Crystal data, data collection and structure refinement details are summarized in Table 110.1107/S2414314622003807/hb4404sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622003807/hb4404Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314622003807/hb4404Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2414314622003807/hb4404Isup4.cmlSupporting information file. DOI: 2164881CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Two of the copper(I) atoms are additionally linked to PMe3 ligands, giving a distorted trigonal coordination.The molecular structure of the title complex consists of an eight-membered Cu 4(C9H11)4(C3H9P)2] or [Cu4(Mes)4(PMe3)2] , was synthesized from copper(I) mesityl and trimethylphosphane in THF as solvent. The molecular structure of the complex has C2 symmetry and consists of four copper(I) atoms bridged by four μ-mesityl groups, giving an eight-membered puckered {Cu4C4} ring. Additionally, two copper(I) atoms at opposite corners of the Cu4 rhomb are each linked to a terminal PMe3 ligand. The PMe3-bearing copper(I) atoms exhibit a distorted trigonal–planar coordination mode whereas the remaining Cu atoms linked to two mesityl groups are nearly linearly coordinated.The title compound, [Cu I organyls, mesitylcopper is one of the most extensively studied compounds. Since its first synthesis in 1981 , the reaction proceeds under retention of the tetranuclear cluster structure to form [Cu4(Mes)4(THT)2] 2]·C7H8 with a yet unknown crystal structure 2Cu][CuMes2] 4(PMe3)2] (1).In order to get some insight into the reactivity of mesitylcopper towards sterically less demanding phosphanes, trimethylphosphane was chosen as a ligand. Treatment of a solution of mesitylcopper in THF with PMe1) comprises four copper(I) atoms that are linked by four μ-mesityl groups to give an eight-membered {Cu4C4} ring –2.4625 (5) Å] suggest cuprophilic interactions. The Cu⋯Cu separations between the copper atoms at opposite corners of the rhomb are 4.2013 (5) Å for Cu2⋯Cu2i , [Cu4(o-Tol)4(SMe2)2] 2]  exhibits two types of differently coordinated Cu atoms °] is clearly more pronounced than in [Cu4Mes4] (164.05–165.70°). Apart from two mesityl groups, Cu2 bears a PMe3 unit as a third ligand. The increased coordination number leads to a further enlargement of the Cu—C distances with values of 2.093 (3) and 2.095 (3) Å. The coordination around Cu2 is planar with a C—Cu—C angle of 163.0 (1)° and C—Cu—P angles of 97.9 (1)° and 99.0 (1)° (sum of the angles around Cu2: 359.9°). Comparison of the bond lengths of compound (1) and related [Cu4Mes4L2] complexes reveals that the ligand PMe3 leads to a larger increase of the Cu—C distances for the tricoordinate copper atoms than other ligands investigated so far. In [Cu4Mes4L2] complexes with L = piperidine, allyl methyl sulfide, 2,5-dithiahexane, tetrahydrothiophene and bis{2-[1-(dimethylamino)ethyl]phenylthiolato}magnesium, the mean Cu—C distances for the tricoordinated copper atoms are in the range 2.054–2.064 Å. In the case of the dicoordinated Cu there is no particular effect. Furthermore, there is a slight influence on the C—Cu—C angles for the dicoordinated [138.3 (1)°] and the tricoordinate copper atoms [163.0 (1)°], which are smaller than in the [Cu4Mes4L2] complexes mentioned above .The molecular structure of  = 2.87 Å, C17—H17A⋯Cg2 = 167° .The molecular packing reveals no special supramolecular features Fig. 2. Most ofI aryl compounds with auxiliary phosphane ligands are relatively rare. According to the CSD database ] -type compounds are 1.922 Å for the PPh3 derivative 4(PMe3)2] may be attributed to the lower coordination number of the copper atoms. The same effect is also visible for the Cu—P distances of 2.189 Å 2] (R′= Et) with two phosphane units attached to copper. In this case, the copper atom exhibits a distorted trigonal–planar coordination with markedly enlarged Cu—C (1.979 Å) and Cu—P (2.250 and 2.256 Å) distances magnesium units as ligands 4(PMe3)2] (1) was precipitated by the addition of 30 ml of n-hexane. After filtration, the colorless product was washed with diethyl ether (2 × 5 ml) and dried under vacuum. Single crystals suitable for X-ray analysis were obtained by slow diffusion of n-hexane into a THF solution of the product. Yield: 0.33 g (60%). C42H62Cu4P2 (883.01 g mol−1). Analysis: Cu 29.0%  IR (cm−1) 2997(w), 2963(m), 2901(m), 2855(w), 2842(w), 2802(w), 2705(w), 1589(w), 1637(w), 1376(w), 1448(w), 1418(m), 1362(w), 1302(w), 1286(m), 1257(w), 1215(w), 1164(w), 1024(w), 939(s), 873(w), 844(s), 730(s), 710(w), 670(m), 576(w), 538(m), 484(w), 357(m), 328(m), 301(m), 275(w). 1H NMR (C6D6): δ 0.60 , 2.08 , 2.73 , 6.68 . 13C{1H} NMR (C6D6): δ 15.4 , 21.4 , 28.7 , 125.6 , 127.4 , 134.4 , 150.0 . 31P{1H} NMR (C6D6): δ −44.6 (s br).A solution of 0.46 g (2.5 mmol) mesitylcopper  I. DOI: 10.1107/S2414314621005940/wm4146Isup2.hklStructure factors: contains datablock(s) I. DOI: 2088681CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


It exhibits a defect disk-shaped architecture. DC magnetic property studies in the 2.0–300 K range revealed antiferromagnetic interactions between the CoII ions.A mixed-valence Co 2L) bearing O2N donors for the preparation of a novel Co6 cluster is reported. The hexanuclear cobalt complex, namely, di-μ2-acetatotetrakis{μ2-2-[(4-chloro-2-oxidobenzylideneamino)methyl]phenolato}tetra-μ3-methanolato-tetracobalt(II)dicobalt(III), [CoII4CoIII2(C14H10ClNO2)4(CH3COO)2(CH3O)4], was obtained using Co(CH3COO)2·4H2O and H2L as starting materials in MeOH under solvothermal conditions. The six metal ions are linked together by the μ3-O atoms of four deprotonated MeOH molecules, two CH3COO− units and six phenolate O atoms of four L2− ligands to form a defect disk-shaped topology. DC magnetic susceptibility investigations revealed the existence of antiferromagnetic interactions in the Co6 cluster.The employment of the new Schiff base ligand 2-[(4-chloro-2-hydroxybenzylideneamino)methyl]phenol (H The tube was sealed and heated at 80 °C for 48 h under autogenous pressure. It was then cooled to room temperature and dark-red needle-like crystals were obtained. The crystals were collected, washed with MeOH (2 ml) and dried in air . Analysis calculated (%) for C64H58Cl4Co6N4O16: C 47.03, H 3.58, N 3.43; found (%): C 46.18, H 4.048, N 3.280. Selected IR data for 1 (cm−1): 1637 (s), 1590 (s), 1523 (s), 1450 (m), 1419 (m), 1286 (w), 1248 (s), 1185 (s), 1089 (m), 1021 (m), 933 (s), 874 (m), 852 (w), 755 (s).To a Pyrex tube (10 ml) was added a mixture of HPLATON  = 1.2Ueq(C). The H atoms of CH3 groups were refined as rotating groups, with Uiso(H) = 1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 12L and Co(CH3COO)2·4H2O in MeOH in the presence of NEt3 under solvothermal conditions led to the isolation of 1 in moderate yield. Co(CH3COO)2·4H2O is a good starting material because it not only serves as a convenient metal source, but also provides CH3COO− bridging ligands. In the solid state, complex 1 is stable in air and its elemental analysis is consistent with the given molecular formula.The reaction of H1 . The signals of the carboxyl νas(CO2) and νs(CO2) vibrations were found in the 1637–1419 cm−1 range. The vibrations of the C=N bond appear at 1450 cm−1. Several bands in the 1286–1185 cm−1 range were assigned to the vibrations of the aromatic rings. The sharp signals in the 979–766 cm−1 range were ascribed to the vibrations of C—H bonds.The vibrational bands in the IR spectrum agree well with the formulation of complex 1 were obtained from MeOH under solvothermal conditions. Complex 1 crystallized in the orthorhombic space group P212121. The structure is shown in Fig. 11 is composed of six cobalt ions, four 2-[(4-chloro-2-oxidobenzylideneamino)methyl]phenolate (L2−) ligands, two acetate ligands and four methanol-solvent-derived MeO− ligands. There exists an approximate C2 symmetry in the molecule. The imine N atom and both phenolate O-atom donors of each L2− ligand coordinate each cobalt centre. Bond valence calculations ]. Of the six cobalt centres, the Co1, Co3, Co4 and Co5 ions are six-coordinated, and the Co2 and Co6 ions are five-coordinated. The coordination environments of the Co2 and Co6 ions, and the Co3 and Co5 ions are individually identical. The Co1 centre is present in a distorted octahedral O6 coordination environment, among which two O atoms are from two μ2-κ4O:O,O′,N L2− ligands and four O atoms are from four μ3-O− MeO− ligands. The Co2 centre is enclosed by the N and O atoms of one μ2-κ4O:O,O′,N L2− ligand, one O atom of a μ3-κ5O:O,N,O′:O′ L2− ligand and one O atom of one μ3-O− MeO− ligand. The six-coordinate NO5 environment around the Co3 ion is accomplished by two μ3-O− MeO− groups, one O atom from one acetate bridge and the N and O atoms of one μ3-κ5O:O,N,O′:O′ L2− ligand. The six O-donor atoms around the Co6 centre originate from bridging acetate ligands, two μ3-O− MeO− groups and two μ3-κ5O:O,N,O′:O′ L2− ligands. The H2L ligand exhibits two types of coordination mode.Single crystals of SHAPE  geometry for both atoms, with a minimum CShM (contunuous shape measure) value of 1.065 for Co2 and 1.172 for Co6.The geometries of the five-coordinated Co2 and Co6 atoms were analyzed with the program 1 joins a small family of Co6 clusters. Hexanuclear cobalt complexes mainly exhibit wheel, cage and ring topologies /C. The Curie constant C = 12.09 cm3 mol−1 K and the Weiss constant θ = −37.24 K were obtained. The negative θ value proves the antiferromagnetic interactions.Magnetic susceptibility data as a function of temperature for complex 1 was also explored. The ac magnetic susceptibilities for 1 at 1000 Hz under a zero-dc field in the temperature range 2–25 K were shown in Fig. S2 (see supporting information). The χ′′ susceptibilities at 1000 Hz did not increase upon lowering the temperature and no peaks were determined. These phenomena revealed that complex 1 is not a single-molecule magnet.The magnetic dynamic behaviour of 2IIICo4II(L)4(CH3COO)2(MeO)4] (1), based on the hydroxy-containing Schiff base ligand 2-[(4-chloro-2-hydroxybenzylideneamino)methyl]phenol (H2L) was prepared and characterized. Complex 1 exhibits a defect disk-shaped topology. Four cobalt ions are six-coordinated and two cobalt ions are five-coordinated. An investigation of the magnetic properties revealed that there exist antiferromagnetic interactions between the CoII ions.A hexanuclear cobalt complex of composition [Co10.1107/S2053229622005885/wv3009sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2053229622005885/wv3009Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2053229622005885/wv3009sup3.pdfIR spectrum, magnetic susceptibility figure, geometry details and table of CShM values. DOI: 1991979CCDC reference:


I atom exhibits a distorted tetrahedral coordination environment, defined by three P atoms of three benzyl-diphenylphosphane ligands and one O atom of a nitrato ligand.The central Ag 3)(C19H17P)3], exhibits a severely distorted tetrahedral coordination environment around the central AgI atom, comprising one O and three P atoms. Apart from a primary Ag—O coordination of the nitrato ligand of 2.667 (3) Å, a second (weaker) secondary interaction of the nitrato ligand via the other O atom of 3.118 (4) Å is observed. The compound crystallizes with a complete molecule in the asymmetric unit. Weak C—H⋯O interactions consolidate the packing.The molecular structure of the title complex, [Ag(NO The nitrato coordinates to the AgI atom via O2 (Ag1—O2 = 2.667 (5) Å). A secondary weak interaction between O1 and Ag1 is also observed, with an interaction distance of 3.118 (4) Å, which is thought to help stabilize the coordination around Ag1. The three N—O bond lengths of the nitrato ligand are nearly identical with a range between 1.221 (3) and 1.233 (3) Å. The NO3 ligand and the Ag1—P3 bond all lie  within the same plane, with P1 and P2 on either side of the plane. Corresponding torsion angles are N1—O2—Ag1—P1 = 110.78 (18)°, N1—O2—Ag1—P2 = −127.26 (19)°, and N1—O2—Ag1—P3 = −5.9 (2)°. The concentration of bulky arene groups from the three phosphine ligands also does not appear to notably affect the tetrahedral environment of each of the P atoms, with typical C′—P—C′′ bond angles between 99.02 (10)–105.80 (11)°, and an average of 103.40°.The molecular structure of the title compound is shown in Fig. 13 rich layer and an alternating arene-rich layer  was added to a solution of silver nitrate (1 mmol) in 20 ml acetonitrile. The reaction mixture was heated under reflux for a few hours. It was filtered and left to form crystals. Small colourless crystals were obtained overnight.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2414314622011476/wm4175sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622011476/wm4175Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314622011476/wm4175Isup3.cdxSupporting information file. DOI: 2223250CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title molecule is essentially flat. In the crystal the molecules are linked by a system of N—H⋯N hydrogen bonds formed by the hydrazinyl group, a Br⋯Br halogen bond, and π-stacking between the pyridine rings. 5H6BrN3, crystallizes in the orthorhombic space group P212121 with two molecules with different conformations in the asymmetric unit. In the crystal, N—H⋯N and bifurcated N—H⋯ hydrogen bonds link the molecules into [100] chains; a short Br⋯Br halogen bond and π–π stacking interactions are also observed.The title compound, C The asymmetric unit contains two conformationally non-equivalent molecules of 6-bromopyridin-2-ylhydrazine, (I1) and (I2), as shown in Fig. 1I1) and (I2), respectively. The spatial arrangements of the hydrazino groups, as defined by the torsion angles H2A—N2—N3—H3A = 137 (3)° and H5—N5—N6—H6A = 121 (3)°, correspond to the low-energy conformation that has been calculated for acyl hydrazides  and (I2), however. While in (I1) the hydrazine nitrogen atom N3 is in the syn-disposition with respect to the pyridine nitrogen atom N1, with N1—C5—N2—N3 = 5.4 (3)°, in (I2) the hydrazine group is in the anti-conformation, with the corresponding torsion angle N4—C10—N5—N6 = 171.0 (2)°. For comparison, in 3-chloropyrid-2-ylhydrazine  for which X-ray diffraction data are available is 2-hydrazinopyridine; however, no crystal structure of this molecule as a free base is known. In crystalline palladium(II)  is extensive and involves all nitrogen atoms of both hydrazine groups and pyridine rings (Table 1I1) and (I2), as shown in Fig. 1A and H3B, and N6 acts as a double acceptor  Å, symmetry code: (i) −1 + x, y, z] is about 0.18 Å shorter than the sum of the van der Waals radii. The aromatic rings of both (I1) and (I2) are involved in a well-defined system of staggered π–π stacking interactions  Å], which satisfies the distance and directionality conditions Table 2 for a has Table 3. These vs Table 3.et al., 2004The title compound was prepared following an established synthetic route  I. DOI: 10.1107/S2414314623001694/hb4424Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314623001694/hb4424Isup3.cmlSupporting information file. DOI: 2243041CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal and molecular structure of 2-amino-4-ferrocenylthiazole has been determined. The crystal packing features intermolecular N—H⋯N and C—H⋯π interactions. 5H5)(C8H7N2S)], was synthesized by the direct reaction of acetylferrocene, thiourea and resublimed iodine. The structure shows one molecule in the asymmetric unit. The aminothiazole ring makes an angle of 14.53 (13)° with the ferrocenyl ring to which it is attached. In the crystal, pairs of complex molecules interact via intermolecular N—H⋯N hydrogen bonds, forming a cyclic dimer which then interacts with other dimers through C—H⋯π interactions.The title compound, [Fe(C The steric effect is also evident in the dihedral angle of 14.77 (17)° subtended by the planes of the heterocycle (C14/C15/S11/C12/N13) and the Cp plane (C1–C5).3.Cg(C1–C5) the H-to-ring distance is 2.89 Å, as shown in Table 1bc plane  and C—H⋯π interactions. For C10—H10⋯ne Fig. 2. The str4.et al., 2016et al., 2005et al., 2007et al., 2006bet al., 2006aet al., 2005et al., 2006aet al., 2020et al., 20052sp hybridization for all C and N atoms.A search of the Cambridge Structural Database  ν 3099 (ArCH), 2921 (CH3), 1658 (C=N); 1H NMR : 4.62 ; 4.25 ; 4.10 ; 5.00 , 6.35 .The title compound was synthesized according to the reported method (Chopra 6.Uiso(H) = 1.2Ueq(N). C-bound H atoms were positioned geometrically (C—H = 0.93–0.98 Å) and refined with isotropically Uiso(H) = 1.2Ueq(C) using a riding model.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989022007228/dj2046sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022007228/dj2046Isup3.hklStructure factors: contains datablock(s) I. DOI: 1841501CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the title compound, the salicylaldehyde alcohol group is engaged in an intramolecular O—H⋯N hydrogen bond with the imine nitrogen atom, while the tertiary alcohol is engaged in a weak intermolecular O—H⋯F hydrogen bond with an adjacent molecule. 28H24FNO2, crystallizes in the orthorhombic space group P212121. A hydrogen-bonding network between the tertiary alcohol group and the fluoro substituent results in [010] chains in the solid state.The title compound, C S)- or (R)-2-amino-1,1,3-triphenylpropanol  imine, C28H24FNO2, crystallizes in the orthorhombic space group P212121 as shown in Fig. 1l-enantiomer structure was collected at 100 K while the d-enantiomer was collected at 293 K. The unit-cell parameters in the current room-temperature structure are slightly larger (average 1.3%), presumably due to the higher temperature of the data collection. The absolute structure parameter of −0.1 (3) has a large uncertainty but the absolute configuration was verified by synthesis and polarimetry.2-Hydroxy-5-fluoro-benzaldehyde 2The compound has the expected imine–phenol structure as opposed to the iminium–phenoxide tautomer seen in derivatives with less steric bulk. The C23–C28 phenol aromatic ring is close to co-planar with atoms O2 [deviation from the ring plane = 0.040 (2) Å], C22 [–0.061 (2) Å], N1 [–0.034 (2) Å] and C2 [–0.039 (2) Å]. These four atoms exhibit less deviation from the plane than the enantiomer. The C22—N1—C2—C1 torsion angle is 110.2 (2)°, which places atom O1 1.555 (2) Å above the plane of the ring. This deviation is 0.166 Å larger than that for the enantiomer at 100 K, although the torsion angle is almost identical.et al., 2019The bonds between C27—C28, C23—C28 and C23—C24 are long at 1.39–1.41 Å while those between C24—C25, C25—C26 and C26—C27 are shorter at 1.36–1.37 Å. In contrast, the aromatic rings on the benzyl and phenyl substituents have typical C—C bond distances ranging from 1.37–1.39 Å. The aromatic C28—O2 bond at 1.349 (3) Å is substantially shorter than the aliphatic C1—O1 bond [1.439 (3) Å]. This bonding motif has been seen in related structures (Sha S(6) ring and a long-range intermolecular hydrogen bond between the tertiary alcohol O1—H1 and the F1 atom of an adjacent molecule as shown in Fig. 2There is an intramolecular O2—H2⋯N1 hydrogen bond Table 1 between et al., 2019Preparative details of the material have been reported previously  global, I. DOI: 10.1107/S2414314620015801/hb4369Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314620015801/hb4369Isup3.cmlSupporting information file. DOI: 1970566CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Zr‐bptc  shows a high SO2 uptake of 6.2 mmol g−1 at 0.1 bar and 298 K, reflecting excellent capture capability and removal of SO2 at low concentration (2500 ppm). Dynamic breakthrough experiments confirm that the introduction of amine, atomically‐dispersed CuII or heteroatomic sulphur sites into the pores enhance the capture of SO2 at low concentrations. The captured SO2 can be converted quantitatively to a pharmaceutical intermediate, aryl N‐aminosulfonamide, thus converting waste to chemical values. In situ X‐ray diffraction, infrared micro‐spectroscopy and inelastic neutron scattering enable the visualisation of the binding domains of adsorbed SO2 molecules and host–guest binding dynamics in these materials at the atomic level. Refinement of the pore environment plays a critical role in designing efficient sorbent materials.We report reversible high capacity adsorption of SO 2 uptake. The incorporation of atomically‐dispersed CuII, amine or heteroatomic sulphur sites enhances the uptake of SO2 at low concentrations. This work confirms that control of pore environments is an important approach for optimising the adsorption of SO2 at low concentrations.A series of Zr‐based metal–organic framework materials have been investigated for reversible SO MOFs constructed from {Zr6} clusters are renowned for their high stability. and Zr‐DMTDC6(μ3‐O)4(μ3‐OH)4(OOCR)12} clusters bridged by dicarboxylates to give cubic structures of fcu topology 4(μ3‐OH)4(OOCR)12} clusters and tetracarboxylate ligands in an open framework of ftw topology.2 g−1. MFM‐1336(OH)8(OH)8(OOCR)8} clusters and thcb4− ligands ‐2,2′,4,4′,6,6′‐hexamethyl‐1,1′‐biphenyl) to form a flu topology. MFM‐133 shows an axially elongated octahedral cage (10.4×10.4×25.9 Å) and a BET surface area of 2156 m2 g−1 8(OH)8(OOCR)8} clusters with the tetratopic ligand 3,3′′,5,5′′‐tetrakis(4‐carboxyphenyl)‐p‐terphenyl (H4tcpt) to give a neutral framework of sqc topology. MFM‐422 is comprised of a trigonal cage  and a hexagonal cage .Zr‐bptc is built from 12‐connected {Zr2 have been recorded for these MOFs at 273–298 K and from 0–1 bar  (36.7 mmol g−1) under the same conditions.2, UiO‐66‐CuII, Zr‐DMTDC, Zr‐bptc, MFM‐133 and MFM‐422, show fully reversible uptakes of SO2 of 8.6, 8.8, 8.2, 9.6, 7.8, 8.9 and 13.6 mmol g−1, respectively . The comparable adsorption uptakes of UiO‐66, UiO‐66‐NH2 and UiO‐66‐CuII at 1 bar (8.2–8.8 mmol g−1) suggest that decoration of the pore environment with functional groups or open CuII sites has little impact on the total uptake capacity, which is determined primarily by the surface area. The slightly higher uptake of Zr‐DMTDC (9.6 mmol g−1) is consistent with its higher surface area (1345 m2 g−1), compared with the other three UiO‐66 materials. In contrast, enhancements in the uptake at 0.1 bar were observed for UiO‐66‐NH2, UiO‐66‐CuII and Zr‐DMTDC, compared with UiO‐66  for SO2 uptake show decreasing values of 45–50, 44–32, 38–34, 32–29, 37–27, 31–27 and 26–19 kJ mol−1 for Zr‐bptc, UiO‐66‐NH2, UiO‐66‐CuII, Zr‐DMTDC, UiO‐66, MFM‐422 and MFM‐133, respectively. Compared with UiO‐66, the materials UiO‐66‐NH2, UiO‐66‐CuII and Zr‐DMTDC show higher values for Qst, consistent with the enhanced adsorption at low pressure. The relatively low values of Qst for MFM‐133 and MFM‐422 are consistent with their large pores, reducing the strength of host–guest interactions.Gravimetric adsorption isotherms of SO2 and N2 have also been recorded for Zr‐bptc, UiO‐66‐NH2, UiO‐66‐CuII, Zr‐DMTDC and UiO‐66 to assess the adsorption selectivity 2/CO2 (1/99) and SO2/N2 (1/99)  at 298 K and 1.0 bar. UiO‐66, UiO‐66‐NH2, Zr‐DMTDC and UiO‐66‐CuII exhibit retention times for SO2 in the expected order of 33, 53, 58 and 100 min g−1, respectively  with retention times of 80, 175, 157 and 175 min g−1 for UiO‐66, UiO‐66‐NH2, Zr‐DMTDC and UiO‐66‐CuII, respectively  and SO2/N2 (2500 ppm SO2/75 % CO2 in He), respectively 4(bdc)6 ⋅ (SO2)7.7] reveal two binding sites I and II located in cage T (SO2/{Zr6}=5.1) and cage O (SO2/{Zr6}=2.6), respectively  Å] and dipole–dipole interaction [O2S⋅⋅⋅phenyl ring=3.69(2) Å] stabilise SO2 (I)  is stabilised by two hydrogen bonds  4(bdc−NH2)6 ⋅ (SO2)8.1], two binding sites I′ and II′ are observed in cage T (SO2/{Zr6}=4.7) and cage O (SO2/{Zr6}=3.4), respectively  Å] was identified and works together with an interaction [O2S⋅⋅⋅phenyl ring=3.58(1) Å] and hydrogen bonding [OSO⋅⋅⋅μ3‐HO=2.94(5) Å] that stabilise SO2 binding at site I′  Å, SO2⋅⋅⋅NH2=1.73(3), 2.43(6), 2.87(7), 3.21(1), 3.30(3) and 3.63(8) Å], which work together with two further dipole–dipole interactions [O2S⋅⋅⋅NH2=2.40(4) and 3.10(7) Å] to stabilise SO2 at site II′ 4(DMTDC)2 ⋅ (SO2)13.1], four binding sites were revealed (I′′‐IV′′). Sites I′′, II′′ and III′′ are localised in cage T   and 3.52(7) Å; O2S⋅⋅⋅thiophene ring=3.65(3) Å]  and 2.70(4) Å; O2S⋅⋅⋅thiophene ring=3.72(3) and 3.72(3) Å] and supramolecular interaction [O2S⋅⋅⋅μ3‐O=3.63(9) Å]. In addition, dipole–dipole interaction between SO2 at sites I′′ and II′′ [OSO(I′′)⋅⋅⋅SO2(II′′)=2.81(7) Å] was identified  Å] and [OSO⋅⋅⋅S‐ring=3.97(6) Å] were identified between SO2(III′′) and the framework  and 3.77(8) Å] and a hydrogen bond [OSO⋅⋅⋅H3C=2.42(2) Å] 4(bptc)3 ⋅ (SO2)5.8], six binding sites were revealed (I–VI)  Å] and by two hydrogen bonds [OSO⋅⋅⋅H−C=2.79(8) Å and OSO⋅⋅⋅μ3‐OH=2.36(5) Å] ⋅⋅⋅SO2(I)=2.06(8) and 3.07(2) Å, OSO(I)⋅⋅⋅SO2(II)=3.28(1) Å] with SO2 at site I ⋅⋅⋅OSO(V)=2.99(7) Å, OSO(III)⋅⋅⋅SO2(V)=3.13(5) Å] with SO2 at site V immobilised by dipole–dipole interactions [O2S⋅⋅⋅phenyl ring=3.72(5) Å] and two‐fold electrostatic interactions [OSO⋅⋅⋅H−C=2.78(1) and 2.93(9) Å]  Å] and dipole–dipole interaction [OSO(IV)⋅⋅⋅SO2(VI)=3.83(5) Å] with SO2 at site VI , 1.88(6), 2.23(5), 2.23(5) and 2.69(7) Å] and two dipole–dipole interactions [O2S⋅⋅⋅OOC=3.07(2) and 3.07(2) Å]  and carboxylic groups and multiple strong hydrogen bonding at site VI jointly facilitate the exceptional SO2 uptake at low pressure.In SO2 (0–1 bar) in the UiO‐66 type systems have been analysed by in situ synchrotron infrared micro‐spectroscopy. For all the MOFs, clear binding of SO2 to the hydroxyl group is observed with a red shift of the −OH stretching vibration at ≈3671 cm−1 by 86, 95, 83 and 82 cm−1 in UiO‐66, UiO‐66‐NH2, UiO‐66‐CuII and Zr‐DMTDC, respectively  mode was monitored to examine the displacement of bound CO2 by SO2  stretch corresponding to the bare and CO2‐loaded materials are approximately equal. Due to weak interaction between CO2 and the μ3‐OH group, the bare μ3‐OH band is not fully depleted but a new peak at 3643 cm−1 appears and is assigned to the [OH⋅⋅⋅OCO] band , there is a steady change in the ν(μ3‐OH) region that includes new bands appearing in a similar manner to the pure SO2 experiment, indicating that bound CO2 does not impede SO2 adsorption . Upon 30 % SO2‐loading, the characteristic [OH⋅⋅⋅OCO] band has fully disappeared showing that SO2 readily displaces bound CO2 in the pore as a result of stronger binding. Hence, selective capture of SO2 from a mixture of SO2/CO2 can be achieved as demonstrated in separation experiments. Furthermore, 40 %, 45 % and 50 % SO2‐loadings fully displace CO2 in UiO‐66‐NH2, Zr‐DMTDC and UiO‐66, respectively . The competitive binding studies of SO2/CO2 further confirm enhanced SO2 binding in the decorated MOFs. The decreasing partial pressure of SO2 on full displacement of CO2 in UiO‐66‐CuII, UiO‐66‐NH2 and Zr‐DMTDC is consistent with that observed in static and dynamic adsorption studies.Upon stepwise dosing of the COIn situ INS, coupled with DFT calculations, enables the visualization of binding dynamics for SO2‐loaded Zr‐bptc. Seven major changes in the INS spectra were observed on the adsorption of SO2 in Zr‐bptc  was observed at 0.1 bar and 298 K. Furthermore, the captured SO2 in Zr‐bptc can be converted readily into fine chemicals, paving new pathways to “waste‐to‐chemicals” technologies. In situ SXPD, microFTIR and INS studies, coupled with DFT calculations, unravel the molecular details of host–guest binding that result in the enhancement of SO2 adsorption at low pressure in these materials. These studies confirm that control of pore environments is an important approach for improving the adsorption of SO2.Powerful drivers exist for the development of new regenerable sorbents for SO6(OH)8(OH)8(tcpt)2], [Zr6O4(OH)4(bptc)3 ⋅ (SO2)5.8], [Zr6O4(OH)4(DMTDC)6 ⋅ (SO2)13.1], [Zr6O4(OH)4(bdc)6 ⋅ (SO2)7.7] and [Zr6O4(OH)4(bdc−NH2)6 ⋅ (SO2)8.1] are available free of charge from the Cambridge Crystallographic Data Centre .Additional crystallographic information, gas adsorption data, thermogravimetric analysis, density function theory (DFT) calculations and breakthrough data are available in the Supporting Information. The crystal structures of [ZrThe 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.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.


In the crystal, the molecules are linked by O—H⋯O and N—H⋯O hydrogen bonds into a three-dimensional network. 6H8NO+·C2H3O2−, the cations and anions are linked by O—H⋯O and N—H⋯O hydrogen bonds, generating a three-dimensional network.In the title molecular salt, C The C—OH bond length (C2—O1) of 1.3520 (9) Å is similar to that observed for structures containing 2-hydroxybenzenaminium as a cation [1.350 (3) Å; Jin & Wang, 2013C⋯O3 cation–anion hydrogen bonds generate a succession of infinite chains [graph set c-axis direction  and acetic acid. This mixture was obtained by dissolution and agitation under reflux for 3 h of 0.5 g of the 2-aminophenol and 0.27 g of acetic acid in a 1:1 stoichiometric ratio in a hot ethanolic solution (20 ml). After warming for a few minutes using a water bath, the solution was cooled and kept at room temperature. Within a few days, yellow needle-like crystals suitable for the X-ray analysis were obtained (yield 60%) by evaporation of the solution.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2414314622001122/vm4050sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622001122/vm4050Isup3.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314622001122/vm4050Isup3.cmlSupporting information file. DOI: 2149479CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The plane resulting from the NO2 coordination to Ag is nearly perpendicular to the plane from the coordination of the phosphine-P atoms to Ag [dihedral angle = 86.43 (9)°].The title Ag P21/c with Z = 4. The asymmetric unit contains one complete silver complex molecule, featuring an AgI atom, two diphenyl-p-tolylphosphine ligands, and one NO2 coordinating in a bidentate fashion. Near-identical Ag—P bond lengths are observed [Ag1—P1 = 2.4209 (7) Å and Ag1—P2 = 2.4251 (8) Å]. The nitrito ligand is similarly coordinating in a near symmetric fashion (Ag1—O1 = 2.422 (2), Ag1—O2 = 2.415 (2), N1—O1 = 1.253 (4) and N1–O2 = 1.255 (4) Å). As seen in Fig. 1ipso-carbon atoms of each of the phosphine ligands overlap in a near-eclipsed fashion when viewed down the P1—Ag1—P2 plane Pl2. Corresponding torsion angles are Ag1—P1—C1—C2 = −23.4 (3)°, Ag1—P1—C7—C8 = −51.9 (3)°, Ag1—P1—C13—C14 = 147.8 (3)°, Ag1—P2—C20—C21 = −29.0 (3)°, Ag1—P2—C26—C27 = 133.3 (3) and Ag1—P2—C32—C33 = 132.3 (3)°. The complex packs in three dimensions as layers of molecules, leaving thin corrugated channels in between the inorganic layers when viewed along the a axis  was dissolved in acetonitrile (10 ml). Silver nitrite (1 mmol) was dissolved in acetonitrile (5 ml). The diphenyl-p-tolylphosphine solution (10 ml) was added to the silver nitrite solution (5 ml), to give a 2:1 molar ratio reaction. The mixture was heated under reflux for 2 h after which the solution was left to crystallize.Diphenyl-For full experimental details including crystal data, data collection and structure refinement details, refer to Table 110.1107/S2414314622007714/tk4082sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622007714/tk4082Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314622007714/tk4082Isup3.cdxSupporting information file. DOI: 2193913CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, weak C—H⋯Cl/O/π interactions are observed.The title compound, [RuCl 2(C10H14)(C21H21O3P)], crystallizes with two complex molecules in the asymmetric unit. The RuII atom has a classical three-legged piano-stool environment being coordinated by a cymene ligand [Ru—centroid = 1.707 (2)/1.704 (2) Å], a tris(4-methoxyphenyl)phosphane ligand [Ru—P = 2.3629 (15)/2.3665 (15) Å] and two chloride atoms with the Ru—Cl bonds adopting two distinct values of 2.4068 (16)/2.4167 (16) and 2.4016 (15)/2.4244 (16) Å. The effective cone and solid angles for the phosphane ligands were calculated to be 149.5/150.2° and 25.3/25.6°, respectively. In the crystal, weak C—H⋯Cl/O/π interactions are observed. The crystal was refined as a two-component twin.The title compound, [RuCl II–arene complexes is well known in the catalytic transfer hydrogenation of carbonyl compounds 3, as part of ongoing structural investigations into these type of complexes.The activity of the half-sandwich RuPZ = 4), with its two unique molecules adopting a distorted pseudo-octahedral arrangement, revealing the typical three-legged piano-stool geometry. The coordination sphere of the ruthenium is occupied by a cymene, a tris(4-methoxyphenyl)phosphane and two chloride atoms  and 1.704 (2) Å for the two independent molecules; the mean Ru—C bond lengths are 2.217 (6) and 2.214 (6) Å. The coordination of the remaining ligands to the Ru atom shows a slight deviation from the typical octahedral geometry with Cl—Ru—Cl = 88.47 (6) and 88.77 (6)°, respectively; Cl—Ru—P = 86.50 (5)/88.03 (5) and 86.05 (5)/88.21 (6)°. The Ru—P bond lengths are 2.3629 (15) and 2.3665 (15) Å, while the Ru—Cl bonds adopt two distinct values of 2.4068 (16)/2.4167 (16) and 2.4016 (15)/2.4244 (16) Å for Ru1 and Ru2, respectively. The above bond lengths are within normal ranges as data extracted from the Cambridge Structural Database RuCl2(PR3) systems from 429 hits, containing 535 usable Ru—Cl observations, show a mean value of 2.412 (12) Å in a range from 2.378 to 2.459 Å. The same group of structures show for the Ru—P distance a mean value of 2.34 (3) Å in a range from 2.235 to 2.434 Å. The geometries of the two independent molecules are virtually identical, as seen from a superimposed fit with an r.m.s. deviation of 0.0525 Å 3  in CH2Cl2 (10 ml) was added to a stirred orange solution of [Ru(p-cymene)Cl2]2  under Ar in the same solvent (15 ml) and stirred at r.t. for 24 h. The resulting red reaction mixture was filtered, the filtrate concentrated under reduced pressure to ca 5 ml. Cold diethyl ether (10 ml) was carefully added and the solvent left to slowly evaporate whereby a sample of [RuCl2(C10H14)(C21H21O3P)] suitable for single-crystal X-ray diffraction was obtained as orange crystals.A solution of P: δ (p.p.m.) 21.39 (s). 1H NMR : δ (p.p.m.) 1.11 ; 1.84 ; 2.87 ; 3.78 ; 4.93 ; 5.20 ; 6.85 ; 7.69 .Analytical data: −3) is located at 0.59 Å from Ru1 and the highest peak (3.95 e Å−3) 0.90 Å from Ru1. Initial refinement of data indicated a two-component twin with a 180° rotation about the [100] reciprocal direction. Refinement with the appropriate twin law yields a batch scaling factor of 0.18.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2414314621012591/tk4072sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2414314621012591/tk4072Isup2.hklStructure factors: contains datablock(s) I. DOI: 2124507CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal features 4 16H13ClN2O3)(C3H4N2)], the NiII ion is coordinated by two O atoms and one N atom derived from the dianionic N′-[(1E)-1-(5-chloro-2-hydroxyphenyl)ethylidene]-4-methoxybenzohydrazide ligand and one N atom from the imidazole molecule. The N2O2 donor set defines an approximate square-planar geometry. The dihedral angles between the imidazole ring and the fused six-membered and methoxybenzene rings are 17.78 (14) and 13.23 (16)°, respectively; the dihedral angle between the C6 rings is 6.63 (12)°. The most prominent feature of the molecular packing is the formation of 41-helical chains  mediated by imidazole-N—H⋯O(phenoxide) hydrogen bonding; these are linked by methyl-C—H⋯Cl interactions.In the title complex, [Ni(C In this complex, the Ni atom is located in a slightly distorted square-planar environment  and C10–C15 (B), and the imidazole ring (C) make dihedral angles of 6.63 (12)° (A/B), 17.78 (14)° (A/C) and 13.23 (16)° (B/C).The Nint Fig. 1. The Ni—c axis, which leads to a 41 helical chain. The chains are connected by C—H⋯Cl interactions (Table 2The molecular packing is consolidated by imidazole-N—H⋯O(phenoxide) hydrogen bonding Table 2 along ths Table 2 into a tN′-[(1E)-1-(5-chloro-2-hydroxyphenyl)ethylidene]-4-methoxybenzohydrazide , 1H-imidazole , Ni(NO3)2·6H2O , methanol (10 ml) and distilled water (5 ml) were mixed in a 50 ml flask. The mixture was stirred at room temperature for 1 h, the pH was adjusted with saturated sodium carbonate solution to about 8 followed by filtration. Red rectangular block-shaped crystals were obtained after about one month by evaporating the filtrate in air (yield 31%).The Schiff base ligand, Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2414314622002954/tk4076sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622002954/tk4076Isup2.hklStructure factors: contains datablock(s) I. DOI: 2159183CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: