High-quality single crystals of the title compound, 2C13H11NO2·H2O, were grown and a structural analysis was performed. The asymmetric unit comprises one mol-ecule of 3-(3-hy-droxy-phen-yl)-1-(1H-pyrrol-2-yl)prop-2-en-1-one (3HPPP), which was recently discovered to be a promising anti-MRSA candidate, and a half-mol-ecule of water. The compound crystallizes in the monoclinic space group P2/c. The crystal structure features inter-molecular pyrrole-N-H⋯O (water), carbon-yl/keto-C-O⋯H-O-phenol and phenol-C-O⋯H (water) hydrogen bonds, which help to consolidate the crystal packing. A Hirshfeld surface analysis for the components in the asymmetric unit showed that H⋯H (40.9%) and H⋯C/C⋯H (32.4%) contacts make the largest contributions to the inter-molecular inter-actions of 3HPPP. Considering the presence of water, in its vicinity H⋯O/O⋯H and H⋯C/C⋯H are the most significant contacts, contributing 48.7 and 29.8%, respectively.
The title CuII macrocyclic complex salt tetra-hydrate, [Cu(C22H46N6O2)](C2H3O2)2·4H2O, sees the metal atom located on a centre of inversion and coordinated within a 4 + 2 (N4O2) tetra-gonally distorted coordination geometry; the N atoms are derived from the macrocycle and the O atoms from weakly associated [3.2048 (15) Å] acetate anions. Further stability to the three-ion aggregate is provided by intra-molecular amine-N-H⋯O(carboxyl-ate) hydrogen bonds. Hydrogen bonding is also prominent in the mol-ecular packing with amide-N-H⋯O(amide) inter-actions, leading to eight-membered {⋯HNCO}2 synthons, amide-N-H⋯O(water), water-O-H⋯O(carboxyl-ate) and water-O-H⋯O(water) hydrogen bonds featuring within the three-dimensional architecture. The calculated Hirshfeld surfaces for the individual components of the asymmetric unit differentiate the water mol-ecules owing to their distinctive supra-molecular association. For each of the anion and cation, H⋯H contacts predominate (50.7 and 65.2%, respectively) followed by H⋯O/O⋯H contacts (44.5 and 29.9%, respectively).
The title thio-urea derivative, C17H19N3OS, adopts a U-shaped conformation with the dihedral angle between the terminal aromatic rings being 73.64 (5)°. The major twist in the mol-ecule occurs about the ethane bond with the Ci-Ce-Ce-Cb torsion angle being -78.12 (18)°; i = imine, e = ethane and b = benzene. The configuration about the imine bond is E, the N-bound H atoms lie on opposite sides of the mol-ecule and an intra-molecular amine-N-H⋯N(imine) hydrogen bond is evident. In the mol-ecular packing, hydroxyl-O-H⋯S(thione) and amine-N-H⋯O hydrogen bonding feature within a linear, supra-molecular chain. The chains are connected into a layer in the ab plane by a combination of methyl-ene-C-H⋯S(thione), methyl-ene-C-H⋯O(hydrox-yl), methyl-C-H⋯π(phen-yl) and phenyl-C-H⋯π(hy-droxy-benzene) inter-actions. The layers stack without directional inter-actions between them. The analysis of the calculated Hirshfeld surface highlights the presence of weak methyl-C-H⋯O(hydrox-yl) and H⋯H inter-actions in the inter-layer region. Computational chemistry indicates that dispersion energy is the major contributor to the overall stabilization of the mol-ecular packing.
The title zinc bis-(thio-semicarbazone) complex, [Zn(C22H17N4O2S)2], comprises two N,S-donor anions, leading to a distorted tetra-hedral N2S2 donor set. The resultant five-membered chelate rings are nearly planar and form a dihedral angle of 73.28 (3)°. The configurations about the endocyclic- and exocyclic-imine bonds are Z and E, respectively, and that about the ethyl-ene bond is E. The major differences in the conformations of the ligands are seen in the dihedral angles between the chelate ring and nitro-benzene rings [40.48 (6) cf. 13.18 (4)°] and the N-bound phenyl and nitro-benzene ring [43.23 (8) and 22.64 (4)°]. In the crystal, a linear supra-molecular chain along the b-axis direction features amine-N-H⋯O(nitro) hydrogen bonding. The chains assemble along the 21-screw axis through a combination of phenyl-C-H⋯O(nitro) and π(chelate ring)-π(phen-yl) contacts. The double chains are linked into a three-dimensional architecture through phenyl-C-H⋯O(nitro) and nitro-O⋯π(phen-yl) inter-actions.
The title diorganotin Schiff base derivative, [Sn(C4H9)2(C15H13N3O2S)], features a penta-coordinated tin centre defined by the N,O,S-donor atoms of the di-anionic Schiff base ligand and two methyl-ene-C atoms of the n-butyl substituents. The resultant C2NOS donor set defines a geometry inter-mediate between trigonal-bipyramidal and square-pyramidal. In the crystal, amine-N-H⋯O(meth-oxy) hydrogen bonding is found in a helical, supra-molecular chain propagating along the b-axis direction. The chains are assembled into a layer parallel to (01) with methyl-ene-C-H⋯π(phen-yl) inter-actions prominent; layers stack without directional inter-actions between them. The analysis of the calculated Hirshfeld surface showed the presence of weak methyl-ene-C-H⋯π(phen-yl) inter-actions and short H⋯H contacts in the inter-layer region. Consistent with the nature of the identified contacts, the stabilization of the crystal is dominated by the dispersion energy term.
The title phosphanegold(I) thiol-ate, C26H22AuFNOPS or [Au(C8H7FNOS)(C18H15P)], has the AuI centre coordinated by phosphane-P [2.2494 (8) Å] and thiol-ate-S [2.3007 (8) Å] atoms to define a close to linear geometry [P-Au-S = 176.10 (3)°]. The thiol-ate ligand is orientated so that the meth-oxy-O atom is directed towards the Au atom, forming an Au⋯O close contact of 2.986 (2) Å. In the crystal, a variety of inter-molecular contacts are discerned with fluoro-benzene-C-H⋯O(meth-oxy) and phenyl-C-H⋯F inter-actions leading to dimeric aggregates. These are assembled into a three-dimensional architecture by phenyl-C-H⋯S(thiol-ate) and phenyl-C-H⋯π(fluorobenzene, phen-yl) inter-actions. Accordingly, the analysis of the calculated Hirshfeld surface shows 30.8% of all contacts are of the type C⋯H/H⋯C but this is less than the H⋯H contacts, at 44.9%. Other significant contributions to the surface come from H⋯F/F⋯H [8.1%], H⋯S/S⋯H [6.9%] and H⋯O/O⋯H [3.2%] contacts. Two major stabilization energies have contributions from the phenyl-C-H⋯π(fluoro-benzene) and fluoro-benzene-C-H⋯C(imine) inter-actions (-37.2 kcal mol-1), and from the fluoro-benzene-C-H⋯F and phenyl-C-H⋯O inter-actions (-34.9 kcal mol-1), the latter leading to the dimeric aggregate.
The complete mol-ecule of the title hydrazine carbodi-thio-ate derivative, C32H30N4O2S4, is generated by a crystallographic twofold axis that bis-ects the di-sulfide bond. The mol-ecule is twisted about this bond with the C-S-S-C torsion angle of 90.70 (8)° indicating an orthogonal relationship between the symmetry-related halves of the mol-ecule. The conformation about the imine bond [1.282 (2) Å] is E and there is limited delocalization of π-electron density over the CN2C residue as there is a twist about the N-N bond [C-N-N-C torsion angle = -166.57 (15)°]. An intra-molecular hydroxyl-O-H⋯N(imine) hydrogen bond closes an S(6) loop. In the crystal, methyl-ene-C-H⋯π(tol-yl) contacts assemble mol-ecules into a supra-molecular layer propagating in the ab plane: the layers stack without directional inter-actions between them. The analysis of the calculated Hirshfeld surfaces confirm the importance of H⋯H contacts, which contribute 46.7% of all contacts followed by H⋯C/C⋯H contacts [25.5%] reflecting, in part, the C-H⋯π(tol-yl) contacts. The calculation of the inter-action energies confirm the importance of the dispersion term and the influence of the stabilizing H⋯H contacts in the inter-layer region.
The title compound, C23H24N2O9, is a tetra-substituted pyrrolidine derivative with a twisted conformation, with the twist evident in the C-C bond bearing the adjacent acet-yloxy substituents. These are flanked on one side by a C-bound 4-meth-oxy-phen-yl group and on the other by a methyl-ene group. The almost sp2-N atom [sum of angles = 357°] bears a 4-nitro-benzyl-oxycarbonyl substituent. In the crystal, ring-methyl-ene-C-H⋯O(acet-yloxy-carbon-yl) and methyl-ene-C-H⋯O(carbon-yl) inter-actions lead to supra-molecular layers lying parallel to (01); the layers stack without directional inter-actions between them. The analysis of the calculated Hirshfeld surfaces indicates the combined importance of H⋯H (42.3%), H⋯O/O⋯H (37.3%) and H⋯C/C⋯H (14.9%) surface contacts. Further, the inter-action energies, largely dominated by the dispersive term, point to the stabilizing influence of H⋯H and O⋯O contacts in the inter-layer region.
The title compound, C20H20N4O3, is constructed about a tri-substituted 1,2,3-triazole ring, with the substituent at one C atom flanked by the C and N atoms being a substituted amide group, and with the adjacent C and N atoms bearing phenyl and benzyl groups, respectively; the dihedral angle between the pendant phenyl rings is 81.17 (12)°, indicative of an almost orthogonal disposition. In the crystal, pairwise amide-N-H⋯O(carbon-yl) hydrogen bonds lead to a centrosymmetric dimer incorporating methyl-ene-C-H⋯π(benzene) inter-actions. The dimers are linked into a supra-molecular layer in the ab plane via methyl-ene-C-H⋯N(azo) and benzene-C-H⋯O(amide) inter-actions; the layers stack along the c-axis direction without directional inter-actions between them. The above-mentioned inter-molecular contacts are apparent in the analysis of the calculated Hirshfeld surface, which also provides evidence for short inter-layer H⋯C contacts with a significant dispersion energy contribution.
The title hydrazine carbodi-thio-ate chloro-form hemisolvate, 2C15H14N2O2S2·CHCl3, comprises two independent hydrazine carbodi-thio-ate mol-ecules, A and B, and a chloro-form mol-ecule; the latter is statistically disordered about its mol-ecular threefold axis. The common features of the organic mol-ecules include an almost planar, central CN2S2 chromophore [r.m.s. deviation = 0.0203 Å (A) and 0.0080 Å (B)], an E configuration about the imine bond and an intra-molecular hydroxyl-O-H⋯N(imine) hydrogen bond. The major conformational difference between the mol-ecules is seen in the relative dispositions of the phenyl rings as indicated by the values of the dihedral angles between the central plane and phenyl ring of 71.21 (6)° (A) and 54.73 (7)° (B). Finally, a difference is seen in the disposition of the outer hydroxyl-H atoms, having opposite relative orientations. In the calculated gas-phase structure, the entire mol-ecule is planar with the exception of the perpendicular phenyl ring. In the mol-ecular packing, the A and B mol-ecules assemble into a two-mol-ecule aggregate via N-H⋯S hydrogen bonds and eight-membered {⋯HNCS}2 synthons. The dimeric assemblies are connected into supra-molecular chains via hydroxyl-O-H⋯O(hydrox-yl) hydrogen bonds and these are linked into a double-chain through hy-droxy-O-H⋯π(phen-yl) inter-actions. The double-chains are connected into a three-dimensional architecture through phenyl-C-H⋯O(hydrox-yl) and phenyl-C-H⋯π(phen-yl) inter-actions. The overall assembly defines columns along the a-axis direction in which reside the chloro-form mol-ecules, which are stabilized by chloro-form-methine-C-H⋯S(thione) and phenyl-C-H⋯Cl contacts. The analysis of the calculated Hirshfeld surfaces, non-covalent inter-action plots and inter-action energies confirm the importance of the above-mentioned inter-actions, but also of cooperative, non-standard inter-actions such as π(benzene)⋯π(hydrogen-bond-mediated-ring) contacts.
The title 1:1 solvate, C14H10O4S2·C3H7NO, features a twisted mol-ecule of 2,2'-di-thiodi-benzoic acid (DTBA), with the central C-S-S-C torsion angle being -88.57 (6)°, and a mol-ecule of di-methyl-formamide (DMF). The carb-oxy-lic acid groups are, respectively, close to co-planar and twisted with respect to the benzene rings to which they are connected as seen in the CO2/C6 torsion angles of 1.03 (19) and 7.4 (2)°. Intra-molecular, hypervalent S←O inter-actions are noted [S⋯O = 2.6140 (9) and 2.6827 (9) Å]. In the crystal, four-mol-ecule aggregates are formed via DTBA-O-H⋯O(DMF) and DTBA-O-H⋯O(DTBA) hydrogen bonding, the latter via an eight-membered {⋯OHCO}2 homosynthon. These are linked into supra-molecular layers parallel to (011) via benzene-C-H⋯O(DTBA) and DTBA-C=O⋯π(benzene) inter-actions, with the connections between these, giving rise to a three-dimensional architecture, being of the type benzene-C-H⋯π(benzene). An analysis of the calculated Hirshfeld surfaces indicates, in addition to the aforementioned inter-molecular contacts, the presence of stabilizing inter-actions between a benzene ring and a quasi-π-system defined by O-H⋯O hydrogen bonds between a DTBA dimer, i.e. the eight-membered {⋯OCOH}2 ring system, and between a benzene ring and a quasi-π(OCOH⋯OCH) system arising from the DTBA-O-H⋯O(DMF) hydrogen bond. The inter-centroid separations are 3.65 and 3.49 Å, respectively.
The CoII atom in the title complex, [Co(SO4)(C12H8N2)(H2O)3] (or C12H14CoN2O7S), is octa-hedrally coordinated within a cis-N2O4 donor set defined by the chelating N-donors of the 1,10-phenanthroline ligand, sulfate-O and three aqua-O atoms, the latter occupying an octa-hedral face. In the crystal, supra-molecular layers lying parallel to (110) are sustained by aqua-O-H⋯O(sulfate) hydrogen bonding. The layers stack along the c-axis direction with the closest directional inter-action between them being a weak phenanthroline-C-H⋯O(sulfate) contact. There are four significant types of contact contributing to the calculated Hirshfeld surface: at 44.5%, the major contribution comes from O-H⋯O contacts followed by H⋯H (28.6%), H⋯C/C⋯H (19.5%) and C⋯C (5.7%) contacts. The dominance of the electrostatic potential force in the mol-ecular packing is also evident in the calculated energy frameworks. The title complex is isostructural with its manganese, zinc and cadmium containing analogues and isomeric with its mer-tri-aqua analogue.
The title di-substituted thio-urea, C12H16N2O3S, has the hy-droxy-lethyl and ethyl benzoate substituents bound to the same amine-N atom, and is twisted, having a (+)syn-clinal conformation with the Namine-C-C-O(hydroxyl, carbon-yl) torsion angles of 49.39 (13) and 59.09 (12)°, respectively; the dihedral angle between the almost planar CN2S core and the pendent benzene ring is 69.26 (4)°. In the crystal, supra-molecular layers propagating in the ac plane are formed via a combination of hydroxyl-O-H⋯S(thione), amine-N-H⋯O(hydroxyl, carbon-yl) hydrogen-bonds. The layers stack along the b axis with inter-digitation of the benzene rings allowing the formation of π-π stacking [inter-centroid separation = 3.8722 (7) Å] and parallel C=O⋯π inter-actions. A computational chemistry study shows the conventional hydrogen bonding in the crystal leads to significant electrostatic stabilization but dispersion terms are also apparent, notably through the inter-actions involving the benzene residue.
The asymmetric unit of the title 1:2 co-crystal, C14H14N4O2·2C7H5ClO2, comprises a half-mol-ecule of oxalamide (4LH2), being located about a centre of inversion, and a mol-ecule of3-chloro-benzoic acid (3-ClBA) in a general position. From symmetry, the 4LH2 mol-ecule has a (+)anti-periplanar conformation with the 4-pyridyl residues lying to either side of the central, planar C2N2O2 chromophore with the dihedral angle between the core and pyridyl ring being 74.69 (11)°; intra-molecular amide-N-H⋯O(amide) hydrogen bonds are noted. The 3-ClBA mol-ecule exhibits a small twist as seen in the C6/CO2 dihedral angle of 8.731 (12)°. In the mol-ecular packing, three-mol-ecule aggregates are formed via carb-oxy-lic acid-O-H⋯N(pyrid-yl) hydrogen bonding. These are connected into a supra-molecular tape along [111] through amide-N-H⋯O(carbon-yl) hydrogen bonding. Additional points of contact between mol-ecules include pyridyl and benzoic acid-C-H⋯O(amide), methyl-ene-C-H⋯O(carbon-yl) and C-Cl⋯π(pyrid-yl) inter-actions so a three-dimensional architecture results. The contributions to the calculated Hirshfeld surface are dominated by H⋯H (28.5%), H⋯O/O⋯H (23.2%), H⋯C/C⋯H (23.3%), H⋯Cl/Cl⋯H (10.0%) and C⋯Cl/C⋯Cl (6.2%) contacts. Computational chemistry confirms the C-Cl⋯π inter-action is weak, and the importance of both electrostatic and dispersion terms in sustaining the mol-ecular packing despite the strong electrostatic term provided by the carb-oxy-lic acid-O-H⋯N(pyrid-yl) hydrogen bonds.
The title compound, C13H19NO8, is based on a tetra-substituted pyrrolidine ring, which has a twisted conformation about the central C-C bond; the Cm-Ca-Ca-Cme torsion angle is 38.26 (15)° [m = methyl-carboxyl-ate, a = acet-yloxy and me = methyl-ene]. While the N-bound ethyl-carboxyl-ate group occupies an equatorial position, the remaining substituents occupy axial positions. In the crystal, supra-molecular double-layers are formed by weak methyl- and methyl-ene-C-H⋯O(carbon-yl) inter-actions involving all four carbonyl-O atoms. The two-dimensional arrays stack along the c axis without directional inter-actions between them. The Hirshfeld surface is dominated by H⋯H (55.7%) and H⋯C/C⋯H (37.0%) contacts; H⋯H contacts are noted in the inter-double-layer region. The inter-action energy calculations point to the importance of the dispersion energy term in the stabilization of the crystal.
Each of the title dis-symmetric di-Schiff base compounds, C15H12Cl2N2O2 (I) and C14H9BrCl2N2O (II), features a central azo-N-N bond connecting two imine groups, each with an E-configuration. One imine bond in each mol-ecule connects to a 2,6-di-chloro-benzene substituent while the other links a 2-hydroxyl-3-meth-oxy-substituted benzene ring in (I) or a 2-hydroxyl-4-bromo benzene ring in (II). Each mol-ecule features an intra-molecular hydroxyl-O-H⋯N(imine) hydrogen bond. The C-N-N-C torsion angles of -151.0 (3)° for (I) and 177.8 (6)° (II) indicates a significant twist in the former. The common feature of the mol-ecular packing is the formation of supra-molecular chains. In (I), the linear chains are aligned along the a-axis direction and the mol-ecules are linked by meth-oxy-C-H⋯O(meth-oxy) and chloro-benzene-C-Cl⋯π(chlorobenzene) inter-actions. The chain in (II) is also aligned along the a axis but, has a zigzag topology and is sustained by Br⋯O [3.132 (4) Å] secondary bonding inter-actions. In each crystal, the chains pack without directional inter-actions between them. The non-covalent inter-actions are delineated in the study of the calculated Hirshfeld surfaces. Dispersion forces make the most significant contributions to the identified inter-molecular inter-actions in each of (I) and (II).
The X-ray crystal structure of the title phthalazin-1-one derivative, C17H16N2O3S {systematic name: 2-[(2,4,6-tri-methyl-benzene)-sulfon-yl]-1,2-di-hydro-phthalazin-1-one}, features a tetra-hedral sulfoxide-S atom, connected to phthalazin-1-one and mesityl residues. The dihedral angle [83.26 (4)°] between the organic substituents is consistent with the mol-ecule having the shape of the letter V. In the crystal, phthalazinone-C6-C-H⋯O(sulfoxide) and π(phthalazinone-N2C4)-π(phthalazinone-C6) stacking [inter-centroid distance = 3.5474 (9) Å] contacts lead to a linear supra-molecular tape along the a-axis direction; tapes assemble without directional inter-actions between them. The analysis of the calculated Hirshfeld surfaces confirm the importance of the C-H⋯O and π-stacking inter-actions but, also H⋯H and C-H⋯C contacts. The calculation of the inter-action energies indicate the importance of dispersion terms with the greatest energies calculated for the C-H⋯O and π-stacking inter-actions.
A new conjugated carbazole chalcone compound, (E)-3-[4-(9,9a-di-hydro-8aH-carbazol-9-yl)phen-yl]-1-(4-nitro-phen-yl)prop-2-en-1-one (CPNC), C27H18N2O3, was synthesized using a Claisen-Schmidt condensation reaction. CPNC crystallizes in the monoclinic non-centrosymmetric space group Cc and adopts an s-cis conformation with respect to the ethyl-enic double bonds (C=O and C=C). The crystal packing features C-H⋯O and C-H⋯π inter-actions whose percentage contribution was qu-anti-fied by Hirshfeld surface analysis. Quantum chemistry calculations including geometrical optimization and mol-ecular electrostatic potential (MEP) were analysed by density functional theory (DFT) with a B3LYP/6-311 G++(d,p) basis set.
The asymmetric unit of the title 1:2 co-crystal, C14H14N4O2·2C7H5ClO2, comprises two half mol-ecules of oxalamide (4LH2), as each is disposed about a centre of inversion, and two mol-ecules of 4-chloro-benzoic acid (CBA), each in general positions. Each 4LH2 mol-ecule has a (+)anti-periplanar conformation with the pyridin-4-yl residues lying to either side of the central, planar C2N2O2 chromophore with the dihedral angles between the respective central core and the pyridyl rings being 68.65 (3) and 86.25 (3)°, respectively, representing the major difference between the independent 4LH2 mol-ecules. The anti conformation of the carbonyl groups enables the formation of intra-molecular amide-N-H⋯O(amide) hydrogen bonds, each completing an S(5) loop. The two independent CBA mol-ecules are similar and exhibit C6/CO2 dihedral angles of 8.06 (10) and 17.24 (8)°, indicating twisted conformations. In the crystal, two independent, three-mol-ecule aggregates are formed via carb-oxy-lic acid-O-H⋯N(pyrid-yl) hydrogen bonding. These are connected into a supra-molecular tape propagating parallel to [100] through amide-N-H⋯O(amide) hydrogen bonding between the independent aggregates and ten-membered {⋯HNC2O}2 synthons. The tapes assemble into a three-dimensional architecture through pyridyl- and methyl-ene-C-H⋯O(carbon-yl) and CBA-C-H⋯O(amide) inter-actions. As revealed by a more detailed analysis of the mol-ecular packing by calculating the Hirshfeld surfaces and computational chemistry, are the presence of attractive and dispersive Cl⋯C=O inter-actions which provide inter-action energies approximately one-quarter of those provided by the amide-N-H⋯O(amide) hydrogen bonding sustaining the supra-molecular tape.
The title hydrazine carbodi-thio-ate, C13H18N2OS2, is constructed about a central and almost planar C2N2S2 chromophore (r.m.s. deviation = 0.0263 Å); the terminal meth-oxy-benzene group is close to coplanar with this plane [dihedral angle = 3.92 (11)°]. The n-butyl group has an extended all-trans conformation [torsion angles S-Cm-Cm-Cm = -173.2 (3)° and Cm-Cm-Cm-Cme = 180.0 (4)°; m = methyl-ene and me = meth-yl]. The most prominent feature of the mol-ecular packing is the formation of centrosymmetric eight-membered {⋯HNCS}2 synthons, as a result of thio-amide-N-H⋯S(thio-amide) hydrogen bonds; these are linked via meth-oxy-C-H⋯π(meth-oxy-benzene) inter-actions to form a linear supra-molecular chain propagating along the a-axis direction. An analysis of the calculated Hirshfeld surfaces and two-dimensional fingerprint plots point to the significance of H⋯H (58.4%), S⋯H/H⋯S (17.1%), C⋯H/H⋯C (8.2%) and O⋯H/H⋯O (4.9%) contacts in the packing. The energies of the most significant inter-actions, i.e. the N-H⋯S and C-H⋯π inter-actions have their most significant contributions from electrostatic and dispersive components, respectively. The energies of two other identified close contacts at close to van der Waals distances, i.e. a thione-sulfur and meth-oxy-benzene-hydrogen contact (occurring within the chains along the a axis) and between methyl-ene-H atoms (occurring between chains to consolidate the three-dimensional architecture), are largely dispersive in nature.