The structure of the title compound (systematic name: N-{[(2-hydroxyphenyl)methylidene]amino}morpholine-4-carbothioamide), C12H15N3O2S, was previously determined (Koo et al., 1977) using multiple-film equi-inclination Weissenberg data, but has been redetermined with higher precision to explore its conformation and the hydrogen-bonding patterns and supramolecular interactions. The molecular structure shows intramolecular O—H...N and C—H...S interactions. The configuration of the C=N bond is E. The molecule is slightly twisted about the central N—N bond. The best planes through the phenyl ring and the morpholino ring make an angle of 43.44 (17)°. In the crystal, the molecules are connected into chains by N—H...O and C—H...O hydrogen bonds, which combine to generate sheets lying parallel to (002). The most prominent contribution to the surface contacts are H...H contacts (51.6%), as concluded from a Hirshfeld surface analysis.
In the title compound, C17H21NO4S, the 1,4-dihydropyridine ring has an envelope conformation with the Csp3 atom at the flap. The thiophene ring is nearly perpendicular to the best plane through the 1,4-dihydropyridine ring, the dihedral angle being 82.19 (13)°. In the crystal, chains running along the b-axis direction are formed through N—H...O interactions between the 1,4-dihydropyridine N atom and one of the O atoms of the ester groups. Neighbouring chains are linked by C—H...O and C—H...π interactions. A Hirshfeld surface analysis shows that the most prominent contributuion to the surface contacts are H...H contacts (55.1%).
The title hydrated molecular salt (systematic name: tetra-n-butylammonium 2,6-dioxo-1,2,3,6-tetrahydropyrimidine-4-carboxylate monohydrate), C16H36N+·C5H3N2O4−·H2O, crystallizes with N—H...O and O—H...O hydrogen-bonded double-stranded antiparallel ribbons consisting of the hydrophilic orotate monoanions and water molecules, separated by the bulky hydrophobic cations. The hydrophobic and hydrophilic regions of the structure are joined by weaker non-classical C—H...O hydrogen bonds. An accurate structure analysis conducted at T = 100 K is compared to a lower-resolution less accurate determination using data measured at T = 295 K. The results of both analyses are evaluated using a knowledge-based approach, and it is found that the less accurate room-temperature structure analysis provides geometric data that are similar to those derived from the accurate low-temperature analysis, with both sets of results consistent with previously analyzed structures. A minor disorder of one methyl group in the cation at low temperature was found to be slightly more complex at room temperature; while still involving a minor fraction of the structure, the disorder at room temperature was found to require a non-routine treatment, which is described in detail.
The non-porous three-dimensional structure of poly[(μ 5 -2-aminobenzene-1,4-dicarboxylato)(μ 6 -oxalato)(oxomium)europium(III)], [Eu(C 8 H 5 NO 4 )(C 2 O 4 )(H 3 O)] n or [Eu III (NH 2 –BDC)(ox)(H 3 O)] n (NH 2 –BDC 2− = 2-aminoterephthalate and ox 2− = oxalate) is constructed from two-dimensional layers of Eu III –carboxylate–oxalate, which are connected by NH 2 –BDC 2− pillars. The basic structural unit of the layer is an edge-sharing dimer of TPRS -{Eu III O 9 }, which is assembled through the ox 2− moiety. The intralayer void is partially occupied by TPR -{Eu III O 6 } motifs. Weak C—H...O and strong, classical intramolecular N—H...O and intermolecular O—H...O hydrogen-bonding interactions, as well as weak π–π stacking interactions, affix the organic pillars within the framework. The two-dimensional layer can be simplified to a uninodal 4-connected sql/Shubnikov tetragonal plane net with point symbol {4 4 .6 2 }.
The synthesis, spectroscopic data, crystal and molecular structures of two N ′-(1-phenylbenzylidene)-2-(thiophen-3-yl)acetohydrazides, namely N ′-[1-(4-hydroxyphenyl)benzylidene]-2-(thiophen-3-yl)acetohydrazide, C 13 H 10 N 2 O 2 S, (3a), and N ′-[1-(4-methoxyphenyl)benzylidene]-2-(thiophen-3-yl)acetohydrazide, C 14 H 14 N 2 O 2 S, (3b), are described. Both compounds differ in the substituent at the para position of the phenyl ring: –OH for (3a) and –OCH 3 for (3b). In (3a), the thiophene ring is disordered over two orientations with occupancies of 0.762 (3) and 0.238 (3). The configuration about the C=N bond is E . The thiophene and phenyl rings are inclined by 84.0 (3) and 87.0 (9)° for the major- and minor-occupancy disorder components in (3a), and by 85.89 (12)° in (3b). Although these dihedral angles are similar, the conformation of the linker between the two rings is different [the C—C—C—N torsion angle is − ac for (3a) and − sc for (3b), while the C6—C7—N9—N10 torsion angle is + ap for (3a) and − sp for (3b)]. A common feature in the crystal packing of (3a) and (3b) is the presence of N—H...O hydrogen bonds, resulting in the formation of chains of molecules running along the b -axis direction in the case of (3a), or inversion dimers for (3b). The most prominent contributions to the surface contacts are those in which H atoms are involved, as confirmed by an analysis of the Hirshfeld surface.
The reaction of benzoyl chloride and ethyl-endi-amine in the presence of potassium thio-cyanate yielded a white solid, C18H18N4O2S2, which consists of two benzoyl-thio-ureido moieties connected by an ethyl-ene chain. The asymmetric unit consists of one half of the mol-ecule, the complete mol-ecule being generated by crystallographic inversion symmetry. Both thio-urea moieties are in a trans conformation. An intra-molecular N-H⋯O hydrogen bond occurs. In the crystal, C-H⋯S and C-H⋯O hydrogen bonds link the molecules, forming layers parallel to the ac plane.
The title compound, C11H9F3N4S, was synthesized from 2-(trifluoromethyl)aniline by a multi-step reaction. It crystallizes in the non-centrosymmetric space group Pna21, with one molecule in the asymmetric unit, and is constructed from a pair of aromatic rings [2-(trifluoromethyl)phenyl and tetrazole], which are twisted by 76.8 (1)° relative to each other because of significant steric hindrance of the trifluoromethyl group at the ortho position of the benzene ring. In the crystal, very weak C—H...N and C—H...F hydrogen bonds and aromatic π–π stacking interactions link the molecules into a three-dimensional network. To further analyse the intermolecular interactions, a Hirshfeld surface analysis, as well as interaction energy calculations, were performed.
The molecular structure of the title compound, C13H7Cl3OS, consists of a 2,5- dichlorothiophene ring and a 2-chlorophenyl ring linked via a prop-2-en-1-one spacer. The dihedral angle between the 2,5-dichlorothiophene and 2-chlorophenyl rings is 9.69 (12)°. The molecule has an E configuration about the C=C bond and the carbonyl group is syn with respect to the C=C bond. The molecular conformation is stabilized by two intramolecular C—H...Cl contacts and one intramolecular C—H...O contact, forming S(5)S(5)S(6) ring motifs. In the crystal, the molecules are linked along the a-axis direction through van der Waals forces and along the b axis by face-to-face π-stacking between the thiophene rings and between the benzene rings of neighbouring molecules, forming corrugated sheets lying parallel to the bc plane. The intermolecular interactions in the crystal packing were further analysed using Hirshfield surface analysis, which indicates that the most significant contacts are Cl...H/ H...Cl (28.6%), followed by C...H/H...C (11.9%), C...C (11.1%), H...H (11.0%), Cl...Cl (8.1%), O...H/H...O (8.0%) and S...H/H...S (6.6%).
The asymmetric unit of the centrosymmetric title salt solvate, 2C17H17F6N2O+· C4H4O42−·CH3CH2OH, (systematic name: 2-{[2,8-bis(trifluoromethyl)quinolin-4-yl](hydroxy)methyl}piperidin-1-ium butanedioate ethanol monosolvate) comprises two independent cations, with almost superimposable conformations and each approximating the shape of the letter L, a butanedioate dianion with an all-trans conformation and an ethanol solvent molecule. In the crystal, supramolecular chains along the a-axis direction are sustained by charge-assisted hydroxy-O—H...O(carboxylate) and ammonium-N—H...O(carboxylate) hydrogen bonds. These are connected into a layer via C—F...π(pyridyl) contacts and π–π stacking interactions between quinolinyl-C6 and –NC5 rings of the independent cations of the asymmetric unit [inter-centroid separations = 3.6784 (17) and 3.6866 (17) Å]. Layers stack along the c-axis direction with no directional interactions between them. The analysis of the calculated Hirshfeld surface reveals the significance of the fluorine atoms in surface contacts. Thus, by far the greatest contribution to the surface contacts, i.e. 41.2%, are of the type F...H/H...F and many of these occur in the inter-layer region. However, these contacts occur at separations beyond the sum of the van der Waals radii for these atoms. It is noted that H...H contacts contribute 29.8% to the overall surface, with smaller contributions from O...H/H...O (14.0%) and F...F (5.7%) contacts.
The molecular structure of the title compound, C17H14ClFO3, consists of a 4-chloro-3-fluorophenyl ring and a 3,4-dimethoxyphenyl ring linked via a prop-2-en-1-one spacer. The molecule has an E configuration about the C=C bond and the carbonyl group is syn with respect to the C=C bond. The F and H atoms at the meta positions of the 4-chloro-3-fluorophenyl ring are disordered over two orientations, with an occupancy ratio of 0.785 (3):0.215 (3). In the crystal, molecules are linked via pairs of C—H...O interactions with an R22(14) ring motif, forming inversion dimers. The dimers are linked into a tape structure running along [10\overline{1}] by a C—H...π interaction. The intermolecular contacts in the crystal were further analysed using Hirshfield surface analysis, which indicates that the most significant contacts are H...H (25.0%), followed by C...H/H...C (20.6%), O...H/H...O (15.6%), Cl...H/H...Cl (10.7%), F...H/H...F (10.4%), F...C/C...F (7.2%) and C...C (3.0%).
The asymmetric unit of the title compound, trans -diaqua(3,10-dimethyl-1,3,5,8,10,12-hexaazacyclotetradecane-κ 4 N 1 , N 5 , N 8 , N 12 )copper(II) 4,4′-methylenebis(3-hydroxynaphthalene-2-carboxylate), [Cu(C 10 H 26 N 6 )(H 2 O) 2 ](C 23 H 14 O 6 ) {[Cu( L )(H 2 O) 2 ](pam), where L = 3,10-dimethyl-1,3,5,8,10,12-hexaazacyclotetradecane and pam = dianion of pamoic acid} consists of two independent halves of the [Cu( L )(H 2 O) 2 ] 2+ cation and one dicarboxylate anion. The Cu II atoms, lying on inversion centres, are coordinated by the four secondary N atoms of the macrocyclic ligands and the mutually trans O atoms of the water molecules in a tetragonally elongated octahedral geometry. The average equatorial Cu—N bond length is significantly shorter than the average axial Cu—O bond length [2.007 (10) and 2.486 (18) Å, respectively]. The macrocyclic ligand in the complex cations adopts the most energetically stable trans -III conformation. The complex cations and anions are connected via hydrogen-bonding interactions between the N—H groups of the macrocycles and the O—H groups of coordinated water molecules as the proton donors and the O atoms of the carboxylate as the proton acceptors into layers lying parallel to the (1\overline{1}1) plane.
The asymmetric unit of the title compound, C21H17Cl2N3, contains two crystallographically independent molecules (A and B). Both molecules have E configurations for both imine double bonds with regard to the aryl and pyridine groups. The conformations of the two molecules differ with the 4-chlorophenyl rings being inclined to the central pyridine ring by 77.64 (6) and 86.18 (6)° in molecule A, and 80.02 (5) and 43.41 (6)° in molecule B. In the crystal, molecules are linked by a number of C—H...π interactions, forming layers parallel to the bc plane.
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) Å] and parallel DTBA-hydroxy-O...π(BA) contacts [O...ring centroid separation = 3.9049 (14) Å]. 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.
The reaction of 2-methylthio-5-amino-1,3,4-thiadiazole (Me-SNTD; C3H5N3S2) with copper(II) acetate monohydrate [Cu(OAc)2·H2O; C4H8CuO5] resulted in the formation of the title binuclear compound, [Cu2(C2H3O2)4(C3H5N3S2)2] or [Cu2(OAc)4(Me-SNTD)2]. The structure has triclinic (P \overline{1}) symmetry with a crystallographic inversion centre located at the midpoint of the line connecting the Cu atoms in the dimer. These two Cu atoms of the dimer [Cu...Cu = 2.6727 (6) Å] are held together by four carboxylate groups. Each Cu atom is further coordinated to the N atom of an Me-SNTD molecule and exhibits a Jahn–Teller-distorted octahedral geometry. The dimers are connected into infinite chains by hydrogen bonds between the NH (Me-SNTD) and the carboxylate groups of neighbouring molecules, generating an R22(12) ring motif. The molecules are further linked by C—H...π interactions between the thiadiazole rings and the methyl groups of the acetate units.
Structural characterization of the ionic title complex, [MgBr(THF)(5)]-[Co(dpbz)(2)]center dot 2THF [THF is tetrahydrofuran, C4H8O; dpbz is 1,2-bis(diphenylphosphanyl)benzene, C30H24P2], revealed a well-separated cation and anion co-crystallized with two THF solvent molecules that interact with the cation via weak C -H center dot center dot center dot O contacts. The geometry about the cobalt center is pseudotetrahedral, as is expected for a d(10) metal center, only deviating from an ideal tetrahedral geometry because of the restrictive bite angles of the bidentate phosphane ligands. Three THF ligands of the cation and one co-crystallized THF solvent molecule are each disordered over two orientations. In the extended structure, the cations and THF solvent molecules are arranged in (100) sheets that alternate with layers of anions, the latter of which show various pi-interactions, which may explain the particular packing arrangement.
In the title pyrazoline derivative, C 16 H 16 N 2 O 3 ·H 2 O, the pyrazoline ring has an envelope conformation with the substituted sp 2 C atom on the flap. The pyrazoline ring makes angles of 86.73 (12) and 13.44 (12)° with the trisubstituted and disubstituted benzene rings, respectively. In the crystal structure, the molecules are connected into chains running in the b -axis direction by O—H...N hydrogen bonding. Parallel chains interact through N—H...O hydrogen bonds and π–π stacking of the trisubstituted phenyl rings. The major contribution to the surface contacts are H...H contacts (44.3%) as concluded from a Hirshfeld surface analysis.
The crystal and molecular structures of the title CuII complex, isolated as a dihydrate, [Cu(C21H14N3O3)2]·2H2O, reveals a highly distorted coordination geometry intermediate between square-planar and tetrahedral defined by an N2O2 donor set derived from two mono-anionic bidentate ligands. Furthermore, each six-membered chelate ring adopts an envelope conformation with the Cu atom being the flap. In the crystal, imidazolyl-amine-N—H...O(water), water-O—H...O(coordinated, nitro and water), phenyl-C—H...O(nitro) and π(imidazolyl)–π(nitrobenzene) [inter-centroid distances = 3.7452 (14) and 3.6647 (13) Å] contacts link the components into a supramolecular layer lying parallel to (101). The connections between layers forming a three-dimensional architecture are of the types nitrobenzene-C—H...O(nitro) and phenyl-C—H...π(phenyl). The distorted coordination geometry for the CuII atom is highlighted in an analysis of the Hirshfeld surface calculated for the metal centre alone. The significance of the intermolecular contacts is also revealed in a study of the calculated Hirshfeld surfaces; the dominant contacts in the crystal are H...H (41.0%), O...H/H...O (27.1%) and C...H/H...C (19.6%).
In the title hydrazinecarbodithioate derivative, C27H26N2O2S2, the asymmetric unit is comprised of four molecules (Z = 8 and Z′ = 4). The 4-methoxyphenyl rings are slightly twisted away from their attached olefinic double bonds [torsion angles = 5.9 (4)–19.6 (4)°]. The azomethine double bond has an s-trans configuration relative to one of the C=C bonds and an s-cis configuration relative to the other [C=C—C= N = 147.4 (6)–175.7 (2) and 15.3 (3)–37.4 (7)°, respectively]. The torsion angles between the azomethine C=N double bond and hydrazine-1-carbodithioate moiety indicate only small deviations from planarity, with torsion angles ranging from 0.9 (3) to 6.9 (3)° and from 174.9 (3) to 179.7 (2)°, respectively. The benzyl ring and the methylenesulfanyl moiety are almost perpendicular to each other, as indicated by their torsion angles [range 93.7 (3)–114.6 (2)°]. In the crystal, molecules are linked by C—H...O, N—H...S and C—H...π(ring) hydrogen-bonding interactions into a three-dimensional network. Structural details of related benzyl hydrazine-1-carbodithioate are surveyed and compared with those of the title compound.
The crystal structures of an intermediate, C10H9ClN4O, 3-[(6-chloro-7H-purin-7-yl)methyl]cyclobutan-1-one (I), and two N-7 and N-9 regioisomeric oxetanocin nucleoside analogs, C10H13ClN4O, 3-[(6-chloro-8,9-dihydro-7H-purin-7-yl)methyl]cyclobutan-1-ol (II) and C10H11ClN4O, 3-[(6-chloro-9H-purin-9-yl)methyl]cyclobutan-1-ol (IV), are reported. The crystal structures of the nucleoside analogs confirmed the reduction of the N-7- and N-9-substituted cyclobutanones with LiAl(OtBu)3 to occur with facial selectivity, yielding cis-nucleosides analogs similar to those found in nature. Reduction of the purine ring of the N-7 cyclobutanone to a dihydropurine was observed for compound (II) but not for the purine ring of the N-9 cyclobutanone on formation of compound (IV). In the crystal of (I), molecules are linked by a weak Cl...O interaction, forming a 21 helix along [010]. The helices are linked by offset π–π interactions [intercentroid distance = 3.498 (1) Å], forming layers parallel to (101). In the crystal of (II), molecules are linked by pairs of O—H...N hydrogen bonds, forming inversion dimers with an R22(8) ring motif. The dimers are linked by O—H...N hydrogen bonds, forming chains along [001], which in turn are linked by C—H...π and offset π–π interactions [intercentroid distance = 3.509 (1) Å], forming slabs parallel to the ac plane. In the crystal of (IV), molecules are linked by O—H...N hydrogen bonds, forming chains along [101]. The chains are linked by C—H...N and C—H...O hydrogen bonds and C—H...π and offset π–π interactions [intercentroid distance = 3.364 (1) Å], forming a supramolecular framework.
The title complex, [(CH3)2NH2][Cr(C6H10NO4)2Cl]·H2O, was synthesized sonochemically. The complex anion consists of a chromium(II) ion ligated by two 3-carb-oxy-2-(di-methyl-amino)-propano-ate anions. They coordinate in a bidentate manner, with a carboxyl-ate oxygen atom and the nitro-gen atom cis to each other in the equatorial plane, while the apical position is occupied by a Cl- ion. Hence, the chromium(II) ion is five-coordinate with a quasi-ideal square-pyramidal geometry; τ5 parameter = 0.01. The complex crystallizes as a monohydrate and in the crystal, the water mol-ecule and the di-methyl-ammonium counter-ion link the complex cations via N-H⋯O, N-H⋯Cl, Owater-H⋯O, O-H⋯Owater and O-H⋯O hydrogen bonds, forming a supra-molecular framework. There are also a number of C-H⋯O hydrogen bonds present that reinforce the framework structure. The crystal studied was refined as a racemic twin.
