In the title mol-ecular salt, 2C6H10N3O+·C8H4O42-, the N atom of each of the two 2-amino-4-meth-oxy-6-methyl-pyrimidine mol-ecules lying between the amine and methyl groups has been protonated. The dihedral angles between the pyrimidine rings of the cations and the benzene ring of the succinate dianion are 5.04 (8) and 7.95 (8)°. Each of the cations is linked to the anion through a pair of N-H⋯O(carboxyl-ate) hydrogen bonds, forming cyclic R22(8) ring motifs which are then linked through inversion-related N-H⋯O hydrogen bonds, giving a central R24(8) motif. Peripheral amine N-H⋯O hydrogen-bonding inter-actions on either side of the succinate anion, also through centrosymmetric R22(8) extensions, form one-dimensional ribbons extending along [211]. The crystal structure also features π-π stacking inter-actions between the aromatic rings of the pyrimidine cations [minimum ring centroid separation = 3.6337 (9) Å]. The inter-molecular inter-actions were also investigated using Hirshfeld surface studies and two-dimensional fingerprint images.
In the title mol-ecular salt, C6H10N3O(+)·C7H5O3(-), the cation is protonated at the N atom lying between the amine and methyl substituents and the dihedral angle between the carboxyl group and its attached ring in the anion is 4.0 (2)°. The anion features an intra-molecular O-H⋯O hydrogen bond, which closes an S(6) ring. The cation and anion are linked by two N-H⋯O hydrogen bonds [R2(2)(8) motif] to generate an ion pair in which the dihedral angle between the aromatic rings is 8.34 (9)°. Crystal symmetry relates two ion pairs bridged by further N-H⋯O hydrogen bonds into a tetra-meric DDAA array. The tetra-mers are linked by pairs of C-H⋯O hydrogen bonds to generate [100] chains. Hirshfeld surface and fingerprint plot analyses are presented.
2-(Benzo-furan-2-yl)-2-oxoethyl 2-chloro-benzoate, C17H11ClO4 (I), and 2-(benzo-furan-2-yl)-2-oxoethyl 2-meth-oxy-benzoate, C18H14O5 (II), were synthesized under mild conditions. Their chemical and mol-ecular structures were analyzed by spectroscopic and single-crystal X-ray diffraction studies, respectively. These compounds possess different ortho-substituted functional groups on their phenyl rings, thus experiencing extra steric repulsion force within their mol-ecules as the substituent changes from 2-chloro (I) to 2-meth-oxy (II). The crystal packing of compound (I) depends on weak inter-molecular hydrogen bonds and π-π inter-actions. Mol-ecules are related by inversion into centrosymmetric dimers via C-H⋯O hydrogen bonds, and further strengthened by π-π inter-actions between furan rings. Conversely, mol-ecules in compound (II) are linked into alternating dimeric chains propagating along the [101] direction, which develop into a two-dimensional plate through extensive inter-molecular hydrogen bonds. These plates are further stabilized by π-π and C-H⋯π inter-actions.
The asymmetric unit of the title compound, C15H15N3O3·0.5H2O, comprises two 2-{[(4-iminiumyl-3-methyl-1,4-di-hydro-pyridin-1-yl)meth-yl]carbamo-yl}benzoate zwitterions (A and B) and a water mol-ecule. The dihedral angles between the pyridine and phenyl rings in the zwitterions are 53.69 (10) and 73.56 (11)° in A and B, respectively. In the crystal, mol-ecules are linked by N-H⋯O, O-H⋯O, C-H⋯O and C-H⋯π(ring) hydrogen bonds into a three-dimensional network. The crystal structure also features π-π inter-actions involving the centroids of the pyridine and phenyl rings [centroid-centroid distances = 3.5618 (12) Å in A and 3.8182 (14) Å in B].
The full mol-ecule of the binuclear title compound, [Cd2Cl2(C6H8O4)(C6H8N2)2(H2O)2], is generated by the application of a centre of inversion located at the middle of the central CH2-CH2 bond of the adipate dianion; the latter chelates a CdII atom at each end. Along with two carboxyl-ate-O atoms, the CdII ion is coordinated by the two N atoms of the chelating benzene-1,2-di-amine ligand, a Cl- anion and an aqua ligand to define a distorted octa-hedral CdClN2O3 coordination geometry with the monodentate ligands being mutually cis. The disparity in the Cd-N bond lengths is related to the relative trans effect exerted by the Cd-O bonds formed by the carboxyl-ate-O and aqua-O atoms. The packing features water-O-H⋯O(carboxyl-ate) and benzene-1,2-di-amine-N-H⋯Cl hydrogen bonds, leading to layers that stack along the a-axis direction. The lack of directional inter-actions between the layers is confirmed by a Hirshfeld surface analysis.
The title compound, {[Zn(C9H11N2S2)2]·0.5C6H7N} n , comprises two independent, but chemically similar, Zn[S2CN(Et)CH2py]2 residues and a 4-methyl-pyridine solvent mol-ecule in the asymmetric unit. The Zn-containing units are connected into a one-dimensional coordination polymer (zigzag topology) propagating in the [010] direction, with one di-thio-carbamate ligand bridging in a μ2-κ(3) mode, employing one pyridyl N and both di-thio-carbamate S atoms, while the other is κ(2)-chelating. In each case, the resultant ZnNS4 coordination geometry approximates a square pyramid, with the pyridyl N atom in the apical position. In the crystal, the chains are linked into a three-dimensional architecture by methyl- and pyridyl-C-H⋯S, methyl-ene-C-H⋯N(pyrid-yl) and pyridyl-C-H⋯π(ZnS2C) inter-actions. The connection between the chain and the 4-methyl-pyridine solvent mol-ecule is of the type pyridyl-C-H⋯N(4-methyl-pyridine).
In the title cluster complex hexane solvate, [Ru6(C30H32P2)(CO)22]·C6H14, two Ru3(CO)11 fragments are linked by a Ph2P(CH2)6PPh2 bridge with the P atoms equatorially disposed with respect to the Ru3 triangle in each case; the hexane solvent mol-ecule is statistically disordered. The Ru⋯Ru distances span a relatively narrow range, i.e. 2.8378 (4) to 2.8644 (4) Å. The hexyl chain within the bridge has an all-trans conformation. In the mol-ecular packing, C-H⋯O inter-actions between cluster mol-ecules, and between cluster and hexane solvent mol-ecules lead to a three-dimensional architecture. In addition, there are a large number of C≡O⋯π(arene) inter-actions in the crystal. The importance of the carbonyl groups in establishing the packing is emphasized by the contribution of 53.4% to the Hirshfeld surface by O⋯H/H⋯O contacts.
The title CuII complex, [Cu(C13H11N2OS2)2], features a trans-N2S2 donor set as a result of the CuII atom being located on a crystallographic centre of inversion and being coordinated by thiol-ate-S and imine-N atoms derived from two di-thio-carbazate anions. The resulting geometry is distorted square-planar. In the crystal, π(chelate ring)-π(fur-yl) [inter-centroid separation = 3.6950 (14) Å and angle of inclination = 5.33 (13)°] and phenyl-C-H⋯π(phen-yl) inter-actions sustain supra-molecular layers lying parallel to (02). The most prominent inter-actions between layers, as confirmed by an analysis of the calculated Hirshfeld surface, are phenyl-H⋯H(phen-yl) contacts. Indications for Cu⋯Cg(fur-yl) contacts (Cu⋯Cg = 3.74 Å) were also found. Inter-action energy calculations suggest the contacts between mol-ecules are largely dispersive in nature.
In the title tri-substituted thio-urea derivative, C13H18N2O3S, the thione-S and carbonyl-O atoms lie, to a first approximation, to the same side of the mol-ecule [the S-C-N-C torsion angle is -49.3 (2)°]. The CN2S plane is almost planar (r.m.s. deviation = 0.018 Å) with the hy-droxy-ethyl groups lying to either side of this plane. One hy-droxy-ethyl group is orientated towards the thio-amide functionality enabling the formation of an intra-molecular N-H⋯O hydrogen bond leading to an S(7) loop. The dihedral angle [72.12 (9)°] between the planes through the CN2S atoms and the 4-tolyl ring indicates the mol-ecule is twisted. The experimental mol-ecular structure is close to the gas-phase, geometry-optimized structure calculated by DFT methods. In the mol-ecular packing, hydroxyl-O-H⋯O(hydrox-yl) and hydroxyl-O-H⋯S(thione) hydrogen bonds lead to the formation of a supra-molecular layer in the ab plane; no directional inter-actions are found between layers. The influence of the specified supra-molecular inter-actions is apparent in the calculated Hirshfeld surfaces and these are shown to be attractive in non-covalent inter-action plots; the inter-action energies point to the important stabilization provided by directional O-H⋯O hydrogen bonds.
The asymmetric unit of the three-component title compound, 2,2'-di-thiodi-benzoic acid-2-chloro-benzoic acid-N,N-di-methyl-formamide (1/1/1), C14H10O4S2·C7H5ClO2·C3H7NO, contains a mol-ecule each of 2,2'-di-thiodi-benzoic acid (DTBA), 2-chloro-benzoic acid (2CBA) and di-methyl-formamide (DMF). The DTBA mol-ecule is twisted [the C-S-S-C torsion angle is 88.37 (17)°] and each carb-oxy-lic group is slightly twisted from the benzene ring to which it is connected [CO2/C6 dihedral angles = 7.6 (3) and 12.5 (3)°]. A small twist is evident in the mol-ecule of 2CBA [CO2/C6 dihedral angle = 4.4 (4)°]. In the crystal, the three mol-ecules are connected by hydrogen bonds with the two carb-oxy-lic acid residues derived from DTBA and 2CBA forming a non-symmetric eight-membered {⋯HOCO}2 synthon, and the second carb-oxy-lic acid of DTBA linked to the DMF mol-ecule via a seven-membered {⋯HOCO⋯HCO} heterosynthon. The three-mol-ecule aggregates are connected into a supra-molecular chain along the a axis via DTBA-C-H⋯O(hydroxyl-2CBA), 2CBA-C-H⋯O(hydroxyl-DTBA) and DTBA-C-H⋯S(DTBA) inter-actions. Supra-molecular layers in the ab plane are formed as the chains are linked via DMF-C-H⋯S(DTBA) contacts, and these inter-digitate along the c-axis direction without specific points of contact between them. A Hirshfeld surface analysis points to additional but, weak contacts to stabilize the three-dimensional architecture: DTBA-C=O⋯H(phenyl-DTBA), 2CBA-Cl⋯H(phenyl-DTBA), as well as a π-π contact between the delocalized eight-membered {⋯HOC=O}2 carb-oxy-lic dimer and the phenyl ring of 2CBA. The latter was confirmed by electrostatic potential (ESP) mapping.
In the redetermination of the title compound, C3H5N2OS+·CI-, the asymmetric unit consists of one independent 2-oxo-1,3-thia-zolidin-4-iminium cation and one independent chloride anion. The cation inter-acts with a chloride anion via N-H⋯Cl hydrogen bonds forming a supra-molecular chain along [010]. These supra-molecular chains are further extended by weak C-H⋯Cl and C-H⋯O inter-actions, forming a two-dimensional network parallel to (001). The crystal structure is further stabilized by weak C-O⋯π inter-actions, supporting a three-dimensional architecture. The structure was previously determined by Ananthamurthy & Murthy [Z. Kristallogr. (1975). 8, 356-367] but has been redetermined with higher precision to allow the hydrogen-bonding patterns and supra-molecular inter-actions to be investigated.
A new polymorphic form of the title compound, C8H8O3, is described in the centrosymmetric monoclinic space group P21/c with Z' = 1 as compared to the first polymorph, which crystallizes with two conformers (Z' = 2) in the asymmetric unit in the same space group. In the crystal of the second polymorph, inversion dimers linked by O-H⋯O hydrogen bonds occur and these are linked into zigzag chains, propagating along the b-axis direction by C-H⋯O links. The crystal structure also features a weak π-π inter-action, with a centroid-to-centroid distance of 3.8018 (6) Å. The second polymorph of the title compound is less stable than the reported first polymorph, as indicated by its smaller calculated lattice energy.
The asymmetric unit of the title 1:2 co-crystal, C14H10O4S2·2C7H6O2, comprises half a mol-ecule of di-thiodi-benzoic acid [systematic name: 2-[(2-carb-oxy-phen-yl)disulfan-yl]benzoic acid, DTBA], as the mol-ecule is located about a twofold axis of symmetry, and a mol-ecule of benzoic acid (BA). The DTBA mol-ecule is twisted about the di-sulfide bond [the C-S-S-C torsion angle is -83.19 (8)°] resulting in a near perpendicular relationship between the benzene rings [dihedral angle = 71.19 (4)°]. The carb-oxy-lic acid group is almost co-planar with the benzene ring to which it is bonded [dihedral angle = 4.82 (12)°]. A similar near co-planar relationship pertains for the BA mol-ecule [dihedral angle = 3.65 (15)°]. Three-mol-ecule aggregates are formed in the crystal whereby two BA mol-ecules are connected to a DTBA mol-ecule via hy-droxy-O-H⋯O(hydroxy) hydrogen bonds and eight-membered {⋯HOC=O}2 synthons. These are connected into a supra-molecular layer in the ab plane through C-H⋯O inter-actions. The inter-actions between layers to consolidate the three-dimensional architecture are π-π stacking inter-actions between DTBA and BA rings [inter-centroid separation = 3.8093 (10) Å] and parallel DTBA-hy-droxy-O⋯π(BA) contacts [O⋯ring centroid separation = 3.9049 (14) Å]. The importance of the specified inter-actions as well as other weaker contacts, e.g. π-π and C-H⋯S, are indicated in the analysis of the calculated Hirshfeld surface and inter-action energies.
In the title chalcone derivative, C15H9BrCl2O, the aryl rings are inclined to each by 14.49 (17)°, and the configuration about the C=C bond is E. There is a short intra-molecular C-H⋯Cl contact present resulting in the formation of an S(6) ring motif. In the crystal, the shortest inter-molecular contacts are Cl⋯O contacts [3.173 (3) Å] that link the mol-ecules to form a 21 helix propagating along the b-axis direction. The helices stack up the short crystallographic a axis, and are linked by offset π-π inter-actions [inter-centroid distance = 3.983 (1) Å], forming layers lying parallel to the ab plane. A qu-anti-fication of the inter-molecular contacts in the crystal were estimated using Hirshfeld surface analysis and two-dimensional fingerprint plots.
The title compound, C16H18N2O3, is constructed about a central oxopyridazinyl ring (r.m.s. deviation = 0.0047 Å), which is connected to an ethyl-acetate group at the N atom closest to the carbonyl group, and benzyl and methyl groups second furthest and furthest from the carbonyl group, respectively. An approximately orthogonal relationship exists between the oxopyridazinyl ring and the best plane through the ethyl-acetate group [dihedral angle = 77.48 (3)°]; the latter lies to one side of the central plane [the Nr-Nr-Cm-Cc (r = ring, m = methyl-ene, c = carbon-yl) torsion angle being 104.34 (9)°]. In the crystal, both H atoms of the N-bound methyl-ene group form methyl-ene-C-H⋯O(ring carbon-yl) or N(pyridazin-yl) inter-actions, resulting in the formation of a supra-molecular tape along the a-axis direction. The tapes are assembled into a three-dimensional architecture by methyl- and phenyl-C-H⋯O(ring carbon-yl) and phenyl-C-H⋯O(ester carbon-yl) inter-actions. The analysis of the calculated Hirshfeld surface indicates the dominance of H⋯H contacts to the overall surface (i.e. 52.2%). Reflecting other identified points of contact between mol-ecules noted above, O⋯H/H⋯O (23.3%), C⋯H/H⋯C (14.7%) and N⋯H/H⋯N (6.6%) contacts also make significant contributions to the surface.
The mol-ecular structure of the title chalcone derivative, C15H10FNO3, is nearly planar and the mol-ecule adopts a trans configuration with respect to the C=C double bond. The nitro group is nearly coplanar with the attached benzene ring, which is nearly parallel to the second benzene ring. In the crystal, mol-ecules are connected by pairs of weak inter-molecular C-H⋯O hydrogen bonds into inversion dimers. The dimers are further linked by another C-H⋯O hydrogen bond and a C-H⋯F hydrogen bond into sheets parallel to (104). π-π inter-actions occur between the sheets, with a centroid-centroid distance of 3.8860 (11) Å. Hirshfeld surface analysis was used to investigate and qu-antify the inter-molecular inter-actions.
The analysis of atom-to-atom and/or residue-to-residue contacts remains a favoured mode of analysing the mol-ecular packing in crystals. In this contribution, additional tools are highlighted as methods for analysis in order to complement the 'crystallographer's tool', PLATON [Spek (2009). Acta Cryst. D65, 148-155]. Thus, a brief outline of the procedures and what can be learned by using Crystal Explorer [Spackman & Jayatilaka (2009). CrystEngComm11, 19-23] is presented. Attention is then directed towards evaluating the nature, i.e. attractive/weakly attractive/repulsive, of specific contacts employing NCIPLOT [Johnson et al. (2010). J. Am. Chem. Soc. 132, 6498-6506]. This is complemented by a discussion of the calculation of energy frameworks utilizing the latest version of Crystal Explorer. All the mentioned programs are free of charge and straightforward to use. More importantly, they complement each other to give a more complete picture of how mol-ecules assemble in mol-ecular crystals.
The crystal and mol-ecular structures of C14H12Cl2, (I), and C14H12Br2, (II), are described. The asymmetric unit of (I) comprises two independent mol-ecules, A and B, each disposed about a centre of inversion. Each mol-ecule approximates mirror symmetry [the Cb-Cb-Ce-Ce torsion angles = -83.46 (19) and 95.17 (17)° for A, and -83.7 (2) and 94.75 (19)° for B; b = benzene and e = ethyl-ene]. By contrast, the mol-ecule in (II) is twisted, as seen in the dihedral angle of 59.29 (11)° between the benzene rings cf. 0° in (I). The mol-ecular packing of (I) features benzene-C-H⋯π(benzene) and Cl⋯Cl contacts that lead to an open three-dimensional (3D) architecture that enables twofold 3D-3D inter-penetration. The presence of benzene-C-H⋯π(benzene) and Br⋯Br contacts in the crystal of (II) consolidate the 3D architecture. The analysis of the calculated Hirshfeld surfaces confirm the influence of the benzene-C-H⋯π(benzene) and X⋯X contacts on the mol-ecular packing and show that, to a first approximation, H⋯H, C⋯H/H⋯C and C⋯X/X⋯C contacts dominate the packing, each contributing about 30% to the overall surface in each of (I) and (II). The analysis also clearly differentiates between the A and B mol-ecules of (I).
The title compound, 2C14H14N4O·H2O, comprises a neutral mol-ecule containing a central pyrazol-3-one ring flanked by an N-bound phenyl group and a C-bound 5-methyl-1H-pyrazol-3-yl group (at positions adjacent to the carbonyl substituent), its zwitterionic tautomer, whereby the N-bound proton of the central ring is now resident on the pendant ring, and a water mol-ecule of crystallization. Besides systematic variations in geometric parameters, the two independent organic mol-ecules have broadly similar conformations, as seen in the dihedral angle between the five-membered rings [9.72 (9)° for the neutral mol-ecule and 3.32 (9)° for the zwitterionic tautomer] and in the dihedral angles between the central and pendant five-membered rings [28.19 (8) and 20.96 (8)° (neutral mol-ecule); 11.33 (9) and 11.81 (9)°]. In the crystal, pyrazolyl-N-H⋯O(carbon-yl) and pyrazolium-N-H⋯N(pyrazol-yl) hydrogen bonds between the independent organic mol-ecules give rise to non-symmetric nine-membered {⋯HNNH⋯NC3O} and {⋯HNN⋯HNC3O} synthons, which differ in the positions of the N-bound H atoms. These aggregates are connected into a supra-molecular layer in the bc plane by water-O-H⋯N(pyrazolide), water-O-H⋯O(carbon-yl) and pyrazolyl-N-H⋯O(water) hydrogen bonding. The layers are linked into a three-dimensional architecture by methyl-C-H⋯π(phen-yl) inter-actions. The different inter-actions, in particular the weaker contacts, formed by the organic mol-ecules are clearly evident in the calculated Hirshfeld surfaces, and the calculated electrostatic potentials differentiate the tautomers.
In the mol-ecule of the title compound, C21H17N3O2, the 5,6-di-hydro-benzimidazo[1,2-c]quinazoline moiety is disordered over two orientations about a pseudo-mirror plane, with a refined occupancy ratio of 0.863 (2):0.137 (2). The dihedral angles formed by the benzimidazole ring system and the benzene ring of the quinazoline group are 14.28 (5) and 4.7 (3)° for the major and minor disorder components, respectively. An intra-molecular O-H⋯O hydrogen bond is present. In the crystal, mol-ecules are linked by O-H⋯N hydrogen bonds, forming chains running parallel to [10-1].