Showing papers in "Acta Crystallographica Section E: Crystallographic Communications in 2019"
TL;DR: This contribution highlights tools for this analysis such as Crystal Explorer and NCIPLOT, which are used to evaluate the nature, i.e. attractive/weakly attractive/repulsive, of specific contacts.
Abstract: The analysis of atom-to-atom and/or residue-to-residue contacts remains a favoured mode of analysing the molecular 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). CrystEngComm 11, 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 molecules assemble in molecular crystals.
323 citations
TL;DR: In the title compound, the dihydrobenzothiazine moiety is folded about the S1⋯N1 axis and inversion dimers are linked into stepped ribbons extending parallel to [110] by C—HPrpnit ⋯OThz (Thz = thiazine) hydrogen bonds.
Abstract: The title compound, C18H12Cl2N2OS, consists of a dihydrobenzothiazine unit linked by a –CH group to a 2,4-dichlorophenyl substituent, and to a propanenitrile unit is folded along the S⋯N axis and adopts a flattened-boat conformation. The propanenitrile moiety is nearly perpendicular to the mean plane of the dihydrobenzothiazine unit. In the crystal, C—HBnz⋯NPrpnit and C—HPrpnit⋯OThz (Bnz = benzene, Prpnit = propanenitrile and Thz = thiazine) hydrogen bonds link the molecules into inversion dimers, enclosing R22(16) and R22(12) ring motifs, which are linked into stepped ribbons extending along [110]. The ribbons are linked in pairs by complementary C=O⋯Cl interactions. π–π contacts between the benzene and phenyl rings, [centroid–centroid distance = 3.974 (1) A] may further stabilize the structure. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (23.4%), H⋯Cl/Cl⋯H (19.5%), H⋯C/C⋯H (13.5%), H⋯N/N⋯H (13.3%), C⋯C (10.4%) and H⋯O/O⋯H (5.1%) interactions. Hydrogen bonding and van der Waals interactions are the dominant interactions in the crystal packing. Computational chemistry calculations indicate that the two independent C—HBnz⋯NPrpnit and C—HPrpnit⋯OThz hydrogen bonds in the crystal impart about the same energy (ca 43 kJ mol−1). Density functional theory (DFT) optimized structures at the B3LYP/6–311 G(d,p) level are compared with the experimentally determined molecular structure in the solid state. The HOMO–LUMO behaviour was elucidated to determine the energy gap.
16 citations
TL;DR: The title compound has a single protonated psilacetin cation and one half of a fumarate dianion in the asymmetric unit and is applicable to high-performance liquid chromatography.
Abstract: The title compound (systematic name: bis{2-[4-(acetyloxy)-1H-indol-3-yl]ethan-1-aminium} but-2-enedioate), 2C14H19N2O2+·C4H2O42−, has a single protonated psilacetin cation and one half of a fumarate dianion in the asymmetric unit. There are N—H⋯O hydrogen bonds between the ammonium H atoms and the fumarate O atoms, as well as N—H⋯O hydrogen bonds between the indole H atoms and the fumarate O atoms. The hydrogen bonds hold the ions together in infinite one-dimensional chains along [111].
15 citations
TL;DR: X-ray powder diffraction was used to determine the structures of six different rare-earth oxyapatites that were shown to be isostructural.
Abstract: Six different rare-earth oxyapatites, including Ca2RE8(SiO4)6O2 (RE = La, Nd, Sm, Eu, or Yb) and NaLa9(SiO4)6O2, were synthesized using solution-based processes followed by cold pressing and sintering. The crystal structures of the synthesized oxyapatites were determined from powder X-ray diffraction (P-XRD) and their chemistries verified with electron probe microanalysis (EPMA). All the oxyapatites were isostructural within the hexagonal space group P63/m and showed similar unit-cell parameters. The isolated [SiO4]4− tetrahedra in each crystal are linked by the cations at the 4f and 6h sites occupied by RE3+ and Ca2+ in Ca2RE8(SiO4)6O2 or La3+ and Na+ in NaLa9(SiO4)6O2. The lattice parameters, cell volumes, and densities of the synthesized oxyapatites fit well to the trendlines calculated from literature values.
14 citations
TL;DR: The asymmetric unit of the title 1:2 co-crystal has a half molecule of twofold symmetric dithiodibenzoic acid and a full molecule of benzoic acids connected into three-molecule aggregates via hydroxy-O—H⋯O(hydroxy) hydrogen bonds.
Abstract: The asymmetric unit of the title 1:2 co-crystal, C14H10O4S2·2C7H6O2, comprises half a molecule of dithiodibenzoic acid [systematic name: 2-[(2-carboxyphenyl)disulfanyl]benzoic acid, DTBA], as the molecule is located about a twofold axis of symmetry, and a molecule of benzoic acid (BA). The DTBA molecule is twisted about the disulfide 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 carboxylic 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 molecule [dihedral angle = 3.65 (15)°]. Three-molecule aggregates are formed in the crystal whereby two BA molecules are connected to a DTBA molecule via hydroxy-O—H⋯O(hydroxy) hydrogen bonds and eight-membered {⋯HOC=O}2 synthons. These are connected into a supramolecular layer in the ab plane through C—H⋯O interactions. The interactions between layers to consolidate the three-dimensional architecture are π–π stacking interactions between DTBA and BA rings [inter-centroid separation = 3.8093 (10) A] and parallel DTBA-hydroxy-O⋯π(BA) contacts [O⋯ring centroid separation = 3.9049 (14) A]. The importance of the specified interactions 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 interaction energies.
13 citations
TL;DR: The molecular system displays a planar conformation between the phenyl and imidazo[1,2-a] pyridine rings and weak C—H⋯π and π–π interactions consolidate the three-dimensional network structure.
Abstract: The title imidazo[1,2-a] pyridine derivative, C13H8Br2N2, was synthesized via a single-step reaction method. The title molecule is planar, showing a dihedral angle of 0.62 (17)° between the phenyl and the imidazo[1,2-a] pyridine rings. An intramolecular C—H⋯N hydrogen bond with an S(5) ring motif is present. In the crystal, a short H⋯H contact links adjacent molecules into inversion-related dimers. The dimers are linked in turn by weak C—H⋯π and slipped π–π stacking interactions, forming layers parallel to (110). The layers are connected into a three-dimensional network by short Br⋯H contacts. Two-dimensional fingerprint plots and three-dimensional Hirshfeld surface analysis of the intermolecular contacts reveal that the most important contributions for the crystal packing are from H⋯Br/Br⋯H (26.1%), H⋯H (21.7%), H⋯C/C⋯H (21.3%) and C⋯C (6.5%) interactions. Energy framework calculations suggest that the contacts formed between molecules are largely dispersive in nature. Analysis of HOMO–LUMO energies from a DFT calculation reveals the pure π character of the aromatic rings with the highest electron density on the phenyl ring, and σ character of the electron density on the Br atoms. The HOMO–LUMO gap was found to be 4.343 eV.
13 citations
TL;DR: The centrosymmetric binuclear complex cation of the title compound, [Cu2(C12H10N2O6)(C 12H8N2)4]-NO3]2·C12h12N2E6·8H2O, is composed of a CuII atom with a distorted trigonal-bipyramidal coordination environment defined by four N atoms from two bidentate 1,10-phenanthroline ligands and one oxygen atom from one-half of the monodentate N,N'-(1
Abstract: The centrosymmetric binuclear complex cation of the title compound, [Cu2(C12H10N2O6)(C12H8N2)4](NO3)2·C12H12N2O6·8H2O, is composed of a CuII atom with a distorted trigonal-bipyramidal coordination environment defined by four N atoms from two bidentate 1,10-phenanthroline ligands and one oxygen atom from one-half of the monodentate N,N'-(1,4-phenyl-enedicarbon-yl)diglycinate anion. The asymmetric unit is completed by one-half of the N,N'-(1,4-phenyl-enedicarbon-yl)diglycine solvent mol-ecule, which is located on a centre of inversion, by one nitrate counter-anion and four water mol-ecules. In the crystal, the cationic complexes are linked via inter-molecular π-π stacking and through lone-pair⋯π inter-actions involving the N,N'-(1,4-phenyl-enedicarbon-yl)diglycinate anion and the phenanthroline ligands. The N,N'-(1,4-phenyl-enedicarbon-yl)diglycine solvent mol-ecule is involved in classical and non-classical hydrogen-bonding inter-actions, as well as π-π stacking inter-actions. The centroid-to-centroid distances between aromatic entities are in the range 3.5402 (5)-4.3673 (4) A. The crystal structure is stabilized by further C-H⋯O contacts as well as by O-H⋯O and N-H⋯O hydrogen bonds between water mol-ecules, the nitrate anions, the N,N'-(1,4-phenyl-enedicarbon-yl)diglycinate ligands, N,N'-(1,4-phenyl-enedicarbon-yl)diglycine solvent mol-ecules and phenanthroline ligands, giving rise to a supra-molecular framework. A Hirshfeld surface analysis was carried out to qu-antify these inter-actions.
12 citations
TL;DR: Three specific examples of structure determinations are discussed, for which an understanding of these aspects of symmetry avoids mistakes that can readily be made by reliance on automatic procedures.
Abstract: In the context of increasing hardware and software automation in the process of crystal structure determination by X-ray diffraction, and based on conference sessions presenting some of the experience of senior crystallographers for the benefit of younger colleagues, an outline is given here of some basic concepts and applications of symmetry in crystallography. Three specific examples of structure determinations are discussed, for which an understanding of these aspects of symmetry avoids mistakes that can readily be made by reliance on automatic procedures. Topics addressed include pseudo-symmetry, twinning, real and apparent disorder, chirality, and structure validation.
11 citations
TL;DR: The asymmetric unit of the title compound contains two independent organic molecules which differ primarily in the dihedral angle between the aromatic rings, viz. 7.79 (7) and 29.89 (7)°.
Abstract: The asymmetric unit of the title compound, C20H20N4O·0.5H2O, contains two independent organic molecules (1 and 2) and a water molecule of crystallization. The two molecules differ primarily in the dihedral angles between the aromatic rings, which are 7.79 (7) and 29.89 (7)° in molecules 1 and 2, respectively. In each molecule there is intramolecular C—H⋯O hydrogen bond forming an S(6) ring motif. In molecule 1 there is an intramolecular N—H⋯π(pyrazole) interaction and an intramolecular C—H⋯π(pyrazole) interaction present. Molecule 1 is linked to molecule 2 by a C—H⋯π(benzene ring) interaction. An intramolecular N—H⋯N hydrogen bond and an intramolecular C—H⋯N hydrogen bond are also present in molecule 2. In the crystal, the three components are linked by Owater—H⋯N, N—H⋯Owater and N—H⋯N hydrogen bonds, forming chains along the [100] direction. The chains are linked by C—H⋯O and C—H⋯N hydrogen bonds, forming layers parallel to the ab plane. Finally, the layers are linked by C—H⋯π interactions, forming a three-dimensional structure.
10 citations
TL;DR: In the title compound, the seven-membered diazepine ring adopts a boat-shaped conformation and molecules are linked by pairs of N—H⋯O hydrogen bonds, forming inversion dimers with an (8) ring motif.
Abstract: In the title compound, C10H8Cl2N2O, the seven-membered diazepine ring adopts a boat-shaped conformation. The mean planes of the two rings of the benzodiazepine unit are inclined to each other by 22.05 (6)°. In the crystal, molecules are linked by pairs of N—H⋯O hydrogen bonds, forming inversion dimers with an R22(8) ring motif. The dimers are linked by C—H⋯π interactions, forming layers lying parallel to (10\overline{1}). The roles of the intermolecular interactions in the crystal packing were clarified using Hirshfeld surface analysis; the most important contributions are from Cl⋯H/H⋯Cl (30.5%) and H⋯H (22.5%) interactions.
10 citations
TL;DR: The title pyridazin-3(2H)-one derivative, C25H19FN2O2, crystallizes with two independent mol-ecules (A and B) in the asymmetric unit.
Abstract: The title pyridazin-3(2H)-one derivative, C25H19FN2O2, crystallizes with two independent molecules (A and B) in the asymmetric unit. In molecule A, the 4-fluorophenyl ring, the benzyl ring and the phenyl ring are inclined to the central pyridazine ring by 86.54 (11), 3.70 (9) and 84.857 (13)°, respectively. In molecule B, the corresponding dihedral angles are 86.80 (9), 10.47 (8) and 82.01 (10)°, respectively. In the crystal, the A molecules are linked by pairs of C—H⋯F hydrogen bonds, forming inversion dimers with an R22(28) ring motif. The dimers are linked by C—H⋯O hydrogen bonds and a C—H⋯π interaction, forming columns stacking along the a-axis direction. The B molecules are linked to each other in a similar manner and form columns separating the columns of A molecules.
TL;DR: In the crystal, the molecules are linked by N—H⋯O and C—H—O interactions, forming a three-dimensional network, and the theoretical geometrical parameters are in good agreement with XRD results.
Abstract: In the title compound, C10H10N2OS, the five atoms of the thiophene ring are essentially coplanar (r.m.s. deviation = 0.0037 A) and the pyridazine ring is non-planar. In the crystal, pairs of N—H⋯O hydrogen bonds link the molecules into dimers with an R22(8) ring motif. The dimers are linked by C—H⋯O interactions, forming layers parallel to the bc plane. The theoretical geometric parameters are in good agreement with XRD results. The intermolecular interactions were investigated using a Hirshfeld surface analysis and two-dimensional fingerprint plots. The Hirshfeld surface analysis of the title compound suggests that the most significant contributions to the crystal packing are by H⋯H (39.7%), C⋯H/H⋯C (17.3%) and O⋯H/H⋯O (16.8%) contacts.
TL;DR: Six new 1-aroyl-4-(4-methoxyphenyl)piperazines have similar molecular structures, but their supramolecular assembly ranges from simple chains, via a chain of rings, to complex sheets.
Abstract: Six new 1-aroyl-4-(4-methoxyphenyl)piperazines have been prepared, using coupling reactions between benzoic acids and N-(4-methoxyphenyl)piperazine. There are no significant hydrogen bonds in the structure of 1-benzoyl-4-(4-methoxyphenyl)piperazine, C18H20N2O2, (I). The molecules of 1-(2-fluorobenzoyl)-4-(4-methoxyphenyl)piperazine, C18H19FN2O2, (II), are linked by two C—H⋯O hydrogen bonds to form chains of rings, which are linked into sheets by an aromatic π–π stacking interaction. 1-(2-Chlorobenzoyl)-4-(4-methoxyphenyl)piperazine, C18H19ClN2O2, (III), 1-(2-bromobenzoyl)-4-(4-methoxyphenyl)piperazine, C18H19BrN2O2, (IV), and 1-(2-iodobenzoyl)-4-(4-methoxyphenyl)piperazine, C18H19IN2O2, (V), are isomorphous, but in (III) the aroyl ring is disordered over two sets of atomic sites having occupancies of 0.942 (2) and 0.058 (2). In each of (III)–(V), a combination of two C—H⋯π(arene) hydrogen bonds links the molecules into sheets. A single O—H⋯O hydrogen bond links the molecules of 1-(2-hydroxybenzoyl)-4-(4-methoxyphenyl)piperazine, C18H20N2O3, (VI), into simple chains. Comparisons are made with the structures of some related compounds.
TL;DR: The title compound, the potassium salt of a benzothiazol(methylsulfanyl)pyriminidine, was obtained in a reaction designed to deliver a neutral 2-pyrimidylbenzothiazole.
Abstract: The title compound, K+·C18H14N5O2S3−·C3H7NO·0.5H2O, was obtained in a reaction designed to deliver a neutral 2-pyrimidylbenzothiazole. The anion is deprotonated at the sulfonamide nitrogen. The asymmetric unit of the title compound contains two potassium cations, two anions, two molecules of DMF and one of water. The anions display some conformational differences but each contains an intramolecular N—H⋯Nbenzothiazole hydrogen bond. The potassium ions both display a highly irregular six-coordination, different for each potassium ion. The anions, together with the DMF and water molecules, are linked by four classical hydrogen bonds to form chains parallel to the b-axis direction.
TL;DR: In the crystal, molecules are linked by C—H⋯Cl hydrogen bonds stacking in a column along the a axis by face-to-faceπ–π stacking interactions between the centres of the similar aromatic rings of the adjacent molecules.
Abstract: In the title compound, C14H8Cl3FN2, the planes of the 4-fluorophenyl ring and the 4-chlorophenyl ring make a dihedral angle of 56.13 (13)°. In the crystal, molecules are stacked in a column along the a axis via a weak C—H⋯Cl hydrogen bond and face-to-face π–π stacking interactions [centroid–centroid distances = 3.8615 (18) and 3.8619 (18) A]. The crystal packing is further stabilized by short Cl⋯Cl contacts. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from Cl⋯H/H⋯Cl (31.2%), H⋯H (14.8%), C⋯H/H⋯C (14.0%), F⋯H/H⋯F (12.8%), C⋯C (9.0%) and Cl⋯Cl (6.7%) interactions.
TL;DR: The molecular structure of the title compound, C23H34N2O4, has C2 symmetry and in the crystal, interlocked dimers are formed through quadruple N-H⋯O hydrogen bonds between pyrrole N—H groups and carbonyl O atoms.
Abstract: The molecular structure of the title compound, C23H34N2O4, has C2 symmetry. In the crystal, interlocked dimers are formed through quadruple N—H⋯O hydrogen bonds between pyrrole N—H groups and carbonyl O atoms.
TL;DR: In this article, the synthesis, spectroscopic data and crystal and mol-ecular structures of four 3-phenyl-prop-1-ene-3-one-1yl)thio-phene derivatives are described.
Abstract: The synthesis, spectroscopic data and crystal and molecular structures of four 3-(3-phenylprop-1-ene-3-one-1-yl)thiophene derivatives, namely 1-(4-hydroxyphenyl)-3-(thiophen-3-yl)prop-1-en-3-one, C13H10O2S, (1), 1-(4-methoxyphenyl)-3-(thiophen-3-yl)prop-1-en-3-one, C14H12O2S, (2), 1-(4-ethoxyphenyl)-3-(thiophen-3-yl)prop-1-en-3-one, C15H14O2S, (3), and 1-(4-bromophenyl)-3-(thiophen-3-yl)prop-1-en-3-one, C13H9BrOS, (4), are described. The four chalcones have been synthesized by reaction of thiophene-3-carbaldehyde with an acetophenone derivative in an absolute ethanol solution containing potassium hydroxide, and differ in the substituent at the para position of the phenyl ring: –OH for 1, –OCH3 for 2, –OCH2CH3 for 3 and –Br for 4. The thiophene ring in 4 was found to be disordered over two orientations with occupancies 0.702 (4) and 0.298 (4). The configuration about the C=C bond is E. The thiophene and phenyl rings are inclined by 4.73 (12) for 1, 12.36 (11) for 2, 17.44 (11) for 3 and 46.1 (6) and 48.6 (6)° for 4, indicating that the –OH derivative is almost planar and the –Br derivative deviates the most from planarity. However, the substituent has no real influence on the bond distances in the α,β-unsaturated carbonyl moiety. The molecular packing of 1 features chain formation in the a-axis direction by O—H⋯O contacts. In the case of 2 and 3, the packing is characterized by dimer formation through C—H⋯O interactions. In addition, C—H⋯π(thiophene) interactions in 2 and C—H⋯S(thiophene) interactions in 3 contribute to the three-dimensional architecture. The presence of C—H⋯π(thiophene) contacts in the crystal of 4 results in chain formation in the c-axis direction. The Hirshfeld surface analysis shows that for all four derivatives, the highest contribution to surface contacts arises from contacts in which H atoms are involved.
TL;DR: The crystal structures of the fumarate salts of the psychomimetics MiPT and 4-HO-MiPT are reported, and the extended structure of both compounds feature two-dimensional networks of ions connected through N—H⋯O and O—H–O hydrogen bonds.
Abstract: The solid-state structures of the salts of two substituted tryptamines, namely N-isopropyl-N-methyltryptaminium (MiPT) fumarate {systematic name: [2-(1H-indol-3-yl)ethyl](methyl)propan-2-ylazanium 3-carboxyprop-2-enoate}, C14H21N2+·C4H3O4−, and 4-hydroxy-N-isopropyl-N-methyltryptaminium (4-HO-MiPT) fumarate monohydrate {systematic name: [2-(4-hydroxy-1H-indol-3-yl)ethyl](methyl)propan-2-ylazanium 3-carboxyprop-2-enoate monohydrate}, C14H21N2O+·C4H3O4−·H2O, are reported. Both salts possess a protonated tryptammonium cation and a 3-carboxyacrylate (hydrogen fumarate) anion in the asymmetric unit; the 4-HO-MiPT structure also contains a water molecule of crystallization. Both cations feature disorder of the side chain over two orientations, in a 0.630 (3):0.370 (3) ratio for MiPT and a 0.775 (5):0.225 (5) ratio for 4-HO-MiPT. In both extended structures, N—H⋯O and O—H⋯O hydrogen bonds generate infinite two-dimensional networks.
TL;DR: In the title pyridazinone derivative, the unsubstituted phenyl ring and the pyridine ring are inclined to each other, making a dihedral angle of 17.41 (13)°, whereas the Cl-substituting phenylRing is nearly orthogonal to the pyrsidazine ring, which contains one independent molecule.
Abstract: The title pyridazinone derivative, C21H19ClN2O3, is not planar. The unsubstituted phenyl ring and the pyridazine ring are inclined to each other, making a dihedral angle of 17.41 (13)° whereas the Cl-substituted phenyl ring is nearly orthogonal to the pyridazine ring [88.19 (13)°]. In the crystal, C—H⋯O hydrogen bonds generate dimers with R22(10) and R22(24) ring motifs which are linked by C—H⋯O interactions, forming chains extending parallel to the c-axis direction. The intermolecular interactions were investigated using Hirshfeld surface analysis and two-dimensional fingerprint plots, revealing that the most significant contributions to the crystal packing are from H⋯H (44.5%), C⋯H/H⋯C (18.5%), H⋯O/H⋯O (15.6%), Cl⋯H/H⋯Cl (10.6%) and C⋯C (2.8%) contacts.
TL;DR: In the case of quinoline derivatives, C14H14ClNO3, there is an intra-molecular C-H⋯O hydrogen bond forming an S(6) graph-set motif as discussed by the authors.
Abstract: In the title quinoline derivative, C14H14ClNO3, there is an intramolecular C—H⋯O hydrogen bond forming an S(6) graph-set motif. The molecule is essentially planar with the mean plane of the ethyl acetate group making a dihedral angle of 5.02 (3)° with the ethyl 6-chloro-2-ethoxyquinoline mean plane. In the crystal, offset π–π interactions with a centroid-to-centroid distance of 3.4731 (14) A link inversion-related molecules into columns along the c-axis direction. Hirshfeld surface analysis indicates that H⋯H contacts make the largest contribution (50.8%) to the Hirshfeld surface.
TL;DR: The title hydrated salt, tris[hexaamminecobalt(III)] tetroxidorhenate(VII) tetrakis[hexafluoridorenate(IV)] hexahydrate, arose unexpectedly due to possible contamination of the K2ReF6 starting material with KReO4.
Abstract: The title hydrated salt, tris[hexaamminecobalt(III)] tetraoxidorhenate(VII) tetrakis[hexafluoridorhenate(IV)] hexahydrate, arose unexpectedly due to possible contamination of the K2ReF6 starting material with KReO4. It consists of octahedral [Co(NH3)6]3+ cation (Co1 site symmetry 1), tetrahedral [ReVIIO4]− anions (Re site symmetry 1) and octahedral [ReIVF6]2− anions (Re site symmetries 1and \overline{3}). The [ReF6]2− octahedral anions (mean Re—F = 1.834 A), [Co(NH3)6]3+ octahedral cations (mean Co—N = 1.962 A), and the [ReO4]− tetrahedral anion (mean Re—O = 1.719 A) are slightly distorted. A network of N—H⋯F hydrogen bonds consolidates the structure. The crystal studied was refined as a two-component twin.
TL;DR: In the title compound, intermolecular C—H⋯O, O—H–O and N–O hydrogen bonds link the molecules into a three-dimensional supramolecular network.
Abstract: In the title compound, C13H14N2O3, the dihydropyridazine ring (r.m.s. deviation = 0.166 A) has a screw-boat conformation. The dihedral angle between its mean plane and the benzene ring is 0.77 (12)°. In the crystal, intermolecular O—H⋯O hydrogen bonds generate C(5) chains and N—H⋯O hydrogen bonds produce R22(8) motifs. These types of interactions lead to the formation of layers parallel to (12\overline{1}). The three-dimensional network is achieved by C—H⋯O interactions, including R24(8) motifs. Intermolecular interactions were additionally investigated using Hirshfeld surface analysis and two-dimensional fingerprint plots. The most significant contributions to the crystal packing are by H⋯H (43.3%), H⋯C/C⋯H (19.3%), H⋯O/H⋯O (22.6%), C⋯N/N⋯C (3.0%) and H⋯N/N⋯H (5.8%) contacts. C—H⋯π interactions and aromatic π–π stacking interactions are not observed.
TL;DR: A theoretical study was performed using the density functional theory at B3LYP with the 6–311 G++(d,p) basis set level to compare with the experimental results of the X-ray analysis and UV–vis absorption analysis in term of the geometrical parameters, HOMO-LUMO energy gap and charge distributions.
Abstract: The asymmetric unit of the title halogenated chalcone derivative, C15H10BrFO, contains two independent molecules, both adopting an s-cis configuration with respect to the C=O and C=C bonds. In the crystal, centrosymmetrically related molecules are linked into dimers via intermolecular hydrogen bonds, forming rings with R12(6), R22(10) and R22(14) graph-set motifs. The dimers are further connected by C—H⋯O interactions into chains parallel to [001]. A Hirshfeld surface analysis suggests that the most significant contribution to the crystal packing is by H⋯H contacts (26.3%). Calculations performed on the optimized structure obtained using density functional theory (DFT) at B3LYP with the 6–311 G++(d,p) basis set reveal that the HOMO–LUMO energy gap is 4.12 eV, indicating the suitability of this crystal for optoelectronic and biological applications. The nucleophilic and electrophilic binding site regions are elucidated using the molecular electrostatic potential (MEP).
TL;DR: In the crystals of the two isotypic compounds, molecules are linked by weak halogen–halogen contacts and C—Cl⋯π interactions into sheets lying parallel to the ab plane.
Abstract: In the two isotypic title compounds, C14H8BrCl2N3O2, (I), and C14H8Cl3N3O2, (II), the substitution of one of the phenyl rings is different [Br for (I) and Cl for (II)]. Aromatic rings form dihedral angles of 60.9 (2) and 64.1 (2)°, respectively. Molecules are linked through weak X⋯Cl contacts [X = Br for (I) and Cl for (II)], C—H⋯Cl and C—Cl⋯π interactions into sheets parallel to the ab plane. Additional van der Waals interactions consolidate the three-dimensional packing. Hirshfeld surface analysis of the crystal structures indicates that the most important contributions for the crystal packing for (I) are from C⋯H/H⋯C (16.1%), O⋯H/H⋯O (13.1%), Cl⋯H/H⋯Cl (12.7%), H⋯H (11.4%), Br⋯H/H⋯Br (8.9%), N⋯H/H⋯N (6.9%) and Cl⋯C/C⋯Cl (6.6%) interactions, and for (II), from Cl⋯H / H⋯Cl (21.9%), C⋯H/H⋯C (15.3%), O⋯H/H⋯O (13.4%), H⋯H (11.5%), Cl⋯C/C⋯Cl (8.3%), N⋯H/H⋯N (7.0%) and Cl⋯Cl (5.9%) interactions. The crystal of (I) studied was refined as an inversion twin, the ratio of components being 0.9917 (12):0.0083 (12).
TL;DR: In the title compound, intermolecular N—H⋯O hydrogen bonds link the molecules into a three-dimensional supramolecular network.
Abstract: In this paper, we describe the synthesis of a new dihydro-2H-pyridazin-3-one derivative. The molecule, C18H16N2O, is not planar; the benzene and pyridazine rings are twisted with respect to each other, making a dihedral angle of 11.47 (2)°, and the toluene ring is nearly perpendicular to the pyridazine ring, with a dihedral angle of 89.624 (1)°. The molecular conformation is stabilized by weak intramolecular C—H⋯N contacts. In the crystal, pairs of N—H⋯O hydrogen bonds link the molecules into inversion dimers with an R22(8) ring motif. The intermolecular interactions were investigated using Hirshfeld surface analysis and two-dimensional (2D) fingerprint plots, revealing that the most important contributions for the crystal packing are from H⋯H (56.6%), H⋯C/C⋯H (22.6%), O⋯H/H⋯O (10.0%) and N⋯C/C⋯N (3.5%) interactions.
TL;DR: In the title dithioglycoluril derivative, there is a difference in the torsion angles between the thioimidazole moiety and the methoxyphenyl groups on either side of the molecule.
Abstract: In the title dithioglycoluril derivative, C19H20N4O3S2, there is a difference in the torsion angles between the thioimidazole moiety and the methoxyphenyl groups on either side of the molecule [C—N—Car—Car = 116.9 (2) and −86.1 (3)°, respectively]. The N—C—N bond angle on one side of the dithioglycoluril moiety is slightly smaller compared to that on the opposite side, [110.9 (2)° cf. 112.0 (2)°], probably as a result of the steric effect of the methyl group. In the crystal, N—H⋯S hydrogen bonds link adjacent molecules to form chains propagating along the c-axis direction. The chains are linked by C—H⋯S hydrogen bonds, forming layers parallel to the bc plane. The layers are then linked by C—H⋯π interactions, leading to the formation of a three-dimensional supramolecular network. Hirshfeld surface analysis and two-dimensional fingerprint plots were used to investigate the molecular interactions in the crystal.
TL;DR: The title tri-substituted thiourea derivative is twisted with a dihedral angle of 72.12 (9)° between the planes through the CN2S atoms and the 4-tolyl ring; an intramolecular N–H⋯O hydrogen bond leads to an S(7) loop.
Abstract: In the title tri-substituted thiourea derivative, C13H18N2O3S, the thione-S and carbonyl-O atoms lie, to a first approximation, to the same side of the molecule [the S—C—N—C torsion angle is −49.3 (2)°]. The CN2S plane is almost planar (r.m.s. deviation = 0.018 A) with the hydroxyethyl groups lying to either side of this plane. One hydroxyethyl group is orientated towards the thioamide functionality enabling the formation of an intramolecular 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 molecule is twisted. The experimental molecular structure is close to the gas-phase, geometry-optimized structure calculated by DFT methods. In the molecular packing, hydroxyl-O—H⋯O(hydroxyl) and hydroxyl-O—H⋯S(thione) hydrogen bonds lead to the formation of a supramolecular layer in the ab plane; no directional interactions are found between layers. The influence of the specified supramolecular interactions is apparent in the calculated Hirshfeld surfaces and these are shown to be attractive in non-covalent interaction plots; the interaction energies point to the important stabilization provided by directional O—H⋯O hydrogen bonds.
TL;DR: Two compounds and their respective crystal structures, obtained via fragmentation of the triazene moiety in a PCN pincer iridium complex, are discussed and one showcases a novel (dppm)C(N2dppM) PCP pincers.
Abstract: The structure of [IrCl2(C58H51N3P4)]Cl·5.5CH3CN or [IrCl2(NHCHPh)(((dppm)C(N2dppm))-κ3P,C,P)]Cl·5.5CH3CN [3, dppm = bis(diphenylphosphino)methane; systematic name: dichlorido(1,1,3,3,7,7,9,9-octaphenyl-4,5-diaza-1,3λ5,7λ4,9-tetraphosphanona-3,5-dien-6-yl-κ2P1,P9)(phenylmethanimine-κN)iridium(III) chloride acetonitrile hemihendecasolvate], resulting from an oxygen-mediated cleavage of a triazeneylidenephosphorane ligand producing a diazomethylenephosphorane and a nitrene moiety, which in turn rearrange via a Staudinger reaction and a 1,2-hydride shift to the first title complex, involves a six-coordinate IrIII complex cation coordinated by a facial PCP pincer ligand, a benzaldimine and two chlorido ligands. The pincer system features a five- and a seven-membered ring, with the central divalent carbon of the PCP pincer ligand being connected to a phosphine and a diazophosphorane. The chlorido ligands are positioned trans to the central carbon atom and to the phosphorus donor of the seven-membered ring of the pincer system, respectively. A chloride ion serves as counter-ion for the monocationic complex. The structure of [IrI(C26H22N2P2)(C26H22P2)(C6H7N)]I(I3)·0.5I2·CH3OH·0.5CH2Cl2 or [IrI(NHCHPh)((dppm)C(N2)-κ2P,C)(dppm-κ2P,P′)]I(I3)·0.5I2·CH3OH·0.5CH2Cl2 {4, systematic name: (4-diazo-1,1,3,3,-tetraphenyl-1,3λ4-diphosphabutan-4-yl-κP1)iodido[methylenebis(diphenylphosphine)-κ2P,P′](phenylmethanimine-κN)iridium(III) iodide–triiodide–dichloromethane–iodine–methanol (2/2/1/1/2)}, accessed via treatment of the triazeneylidenephosphorane complex [Ir((BnN3)C(dppm)-κ3P,C,N)(dppm-κ2P,P′)]Cl with hydroiodic acid, consists of a dicationic six-coordinate IrIII complex, coordinated by a bidentate diazomethylenephosphorane, a benzaldimine, a chelating dppm moiety and an iodido ligand. The phosphorus atoms of the chelating dppm are trans to the central carbon atom of the diazomethylenephosphorane and the iodide ligand, respectively. Both an iodide and a triiodide moiety function as counter-ions. The acetonitrile solvent molecules in 3 are severely disordered in position and occupation. In 4, the I3− anion is positionally disordered (ratio roughly 1:1), as is the I− anion with a ratio of 9:1. The dichloromethane solvent molecule lies near a twofold rotation axis (disorder) and was refined with an occupancy of 0.5. Another disorder occurs for the solvent methanol with a 1:1 ratio.
TL;DR: In the title compound, the phenyl and pyridazine rings are inclined to each other by 10.55 (12)°, whereas the 4-methylbenzyl ring is nearly orthogonal to the pyridine ring with a dihedral angle of 72.97”(10)°.
Abstract: The title pyridazinone derivative, C20H18N2O3, is not planar. The phenyl ring and the pyridazine ring are inclined to each other by 10.55 (12)°, whereas the 4-methylbenzyl ring is nearly orthogonal to the pyridazine ring, with a dihedral angle of 72.97 (10)°. In the crystal, molecules are linked by pairs of O—H⋯O hydrogen bonds, forming inversion dimers with an R22(14) ring motif. The dimers are linked by C—H⋯O hydrogen bonds, generating ribbons propagating along the c-axis direction. The intermolecular interactions were additionally investigated using Hirshfeld surface analysis and two-dimensional fingerprint plots. They revealed that the most significant contributions to the crystal packing are from H⋯H (48.4%), H⋯O/O⋯H (21.8%) and H⋯C/C⋯H (20.4%) contacts. Molecular orbital calculations providing electron-density plots of HOMO and LUMO molecular orbitals and molecular electrostatic potentials (MEP) were also computed, both with the DFT/B3LYP/6–311 G++(d,p) basis set.
TL;DR: The tin coordination geometry in (C6H5)3Sn[S2CN(i-Pr)2] is based on a tetrahedron but the geometry of the C3S donor set is distorted by the close proximity of the second thione-S atom.
Abstract: The crystal and molecular structures of the title triorganotin dithiocarbamate, [Sn(C6H5)3(C7H14NS2)], are described. The molecular geometry about the metal atom is highly distorted being based on a C3S tetrahedron as the dithiocarbamate ligand is asymmetrically chelating to the tin centre. The close approach of the second thione-S atom [Sn⋯S = 2.9264 (4) A] is largely responsible for the distortion. The molecular packing is almost devoid of directional interactions with only weak phenyl-C—H⋯C(phenyl) interactions, leading to centrosymmetric dimeric aggregates, being noted. An analysis of the calculated Hirshfeld surface points to the significance of H⋯H contacts, which contribute 66.6% of all contacts to the surface, with C⋯H/H⋯C [26.8%] and S⋯H/H⋯H [6.6%] contacts making up the balance.