The crystal and mol-ecular structures of two di-phenyl-tin bis-(di-thio-carbamate)s, [Sn(C6H5)2(C5H10NOS2)2], (I), and [Sn(C6H5)2(C7H14NO2S2)2], (II), are described. In (I), in which the metal atom lies on a twofold rotation axis, the di-thio-carbamate ligand coordinates with approximately equal Sn-S bond lengths and the ipso-C atoms of the Sn-bound phenyl groups occupy cis-positions in the resulting octa-hedral C2S4 donor set. A quite distinct coordination geometry is noted in (II), arising as a result of quite disparate Sn-S bond lengths. Here, the four S-donors define a trapezoidal plane with the ipso-C atoms lying over the weaker of the Sn-S bonds so that the C2S4 donor set defines a skewed trapezoidal bipyramid. The packing of (I) features supra-molecular layers in the ab plane sustained by methyl-ene-C-H⋯π(Sn-ar-yl) inter-actions; these stack along the c-axis direction with no specific inter-actions between them. In (II), supra-molecular chains along the b-axis direction are formed by methyl-ene-C-O(ether) inter-actions; these pack with no directional inter-actions between them. A Hirshfeld surface analysis was conducted on both (I) and (II) and revealed the dominance of H⋯H inter-actions contributing to the respective surfaces, i.e. >60% in each case, and other features consistent with the description of the mol-ecular packing above.
The complete binuclear molecule of the title compound, [Cd2I4(C14H12N2O2)2], is generated by the application of a centre of inversion. The Cd-I bond lengths of the central core are close and uniformly longer than the exocyclic Cd-I bond. The coordination sphere of the Cd(II) atom is completed by two N atoms of a chelating methyl 4-[(pyridin-2-yl-methyl-idene)amino]-benzoate ligand, and is based on a square pyramid with the terminal I atom in the apical position. The three-dimensional crystal packing is stabilized by C-H⋯O and C-H⋯π inter-actions, each involving the pyridine ring.
The complete mol-ecule of the title compound, [Sn(C4H9)2(C5H10NOS2)2], is generated by a crystallographic mirror plane, with the SnIV atom and the two inner methyl-ene C atoms of the butyl ligands lying on the mirror plane; statistical disorder is noted in the two terminal ethyl groups, which deviate from mirror symmetry. The di-thio-carbamate ligand coordinates to the metal atom in an asymmetric mode with the resulting C2S4 donor set defining a skew trapezoidal bipyramidal geometry; the n-butyl groups are disposed to lie over the longer Sn-S bonds. Supra-molecular chains aligned along the a-axis direction and sustained by methyl-ene-C-H⋯S(weakly coordinating) inter-actions feature in the mol-ecular packing. A Hirshfeld surface analysis reveals the dominance of H⋯H contacts in the crystal.
The crystal and mol-ecular structures of the title salt, C8H8N3S2 (+)·Cl(-), (I), and salt hydrate, C8H7ClN3S2 (+)·Cl(-)·H2O, (II), are described. The heterocyclic ring in (I) is statistically planar and forms a dihedral angle of 9.05 (12)° with the pendant phenyl ring. The comparable angle in (II) is 15.60 (12)°, indicating a greater twist in this cation. An evaluation of the bond lengths in the H2N-C-N-C-N sequence of each cation indicates significant delocalization of π-electron density over these atoms. The common feature of the crystal packing in (I) and (II) is the formation of charge-assisted amino-N-H⋯Cl(-) hydrogen bonds, leading to helical chains in (I) and zigzag chains in (II). In (I), these are linked by chains mediated by charge-assisted iminium-N(+)-H⋯Cl(-) hydrogen bonds into a three-dimensional architecture. In (II), the chains are linked into a layer by charge-assisted water-O-H⋯Cl(-) and water-O-H⋯O(water) hydrogen bonds with charge-assisted iminium-N(+)-H⋯O(water) hydrogen bonds providing the connections between the layers to generate the three-dimensional packing. In (II), the chloride anion and water mol-ecules are resolved into two proximate sites with the major component being present with a site occupancy factor of 0.9327 (18).
The 1:1 co-crystallization of 1,4-di-aza-bicyclo-[2.2.2]octane (DABCO) with 4-nitro-benzoic acid in ethanol-water (3/1) gave the salt dihydrate C6H13N2 (+)·C7H4NO4 (-)·2H2O, (1), whereas from methanol, the salt C6H14N2 (2+)·2C7H4NO4 (-), (2), was isolated. In (1), the cation and anion are linked by a strong N-H⋯O hydrogen bond, and the carboxyl-ate anion is close to planar [dihedral angle between terminal residues = 6.83 (9)°]. In (2), a three-ion aggregate is assembled by two N-H⋯O hydrogen bonds, and the carboxyl-ate anions are again close to planar [dihedral angles between terminal residues = 1.7 (3) and 5.9 (3)°]. Through the inter-vention of solvent water mol-ecules, which self-assemble into helical supra-molecular chains along the b axis, the three-dimensional architecture in (1) is stabilized by water-DABCO O-H⋯N and water-carboxyl-ate O-H⋯O hydrogen bonds, with additional stability afforded by C-H⋯O inter-actions. The global crystal structure comprises alternating layers of water mol-ecules and ion pairs stacked along the c axis. In the crystal of (2), the three-ion aggregates are assembled into a three-dimensional architecture by a large number of methyl-ene-carboxyl-ate/nitro C-H⋯O inter-actions as well as π-π contacts between inversion-related benzene rings [inter-centroid distances = 3.5644 (16) and 3.6527 (16) Å]. The cations and anions assemble into alternating layers along the c axis.
The common feature of the title compounds, [Zn(C5H10NO2S2)2(C10H8N2)]·2H2O, (I), and [Zn(C6H12NOS2)2(C10H8N2)], (II), is the location of the Zn(II) atoms on a twofold rotation axis. Further, each Zn(II) atom is chelated by two symmetry-equivalent and symmetrically coordinating di-thio-carbamate ligands and a 2,2'-bi-pyridine ligand. The resulting N2S4 coordination geometry is based on a highly distorted octa-hedron in each case. In the mol-ecular packing of (I), supra-molecular ladders mediated by O-H⋯O hydrogen bonding are found whereby the uprights are defined by {⋯HO(water)⋯HO(hy-droxy)⋯} n chains parallel to the a axis and with the rungs defined by 'Zn[S2CN(CH2CH2)2]2'. The water mol-ecules connect the ladders into a supra-molecular layer parallel to the ab plane via water-O-H⋯S and pyridyl-C-H⋯O(water) inter-actions, with the connections between layers being of the type pyridyl-C-H⋯S. In (II), supra-molecular layers parallel to the ab plane are sustained by hy-droxy-O-H⋯S hydrogen bonds with connections between layers being of the type pyridyl-C-H⋯S.
In the title compound, C15H20BrNO2, there are two independent mol-ecules (A and B) comprising the asymmetric unit and these adopt very similar conformations. In A, the dihedral angle between the CO2 and MeC=CMe2 groups is 80.7 (3)°, and these make dihedral angles of 3.5 (3) and 84.09 (16)°, respectively, with the bromo-benzene ring. The equivalent dihedral angles for mol-ecule B are 78.4 (3), 2.1 (3) and 78.37 (12)°, respectively. The most prominent inter-actions in the crystal packing are amine-N-H⋯O(carbon-yl) hydrogen bonds between the two independent mol-ecules, resulting in non-centrosymmetric ten-membered {⋯OC2NH}2 synthons. Statistical disorder is noted for each of the terminal methyl groups of the ethyl residues.
In the title complex salt, [Au2{(C6H5)2PCH2P(C6H5)2}]Cl2·(CH3)2C=O·H2O, the dication forms an eight-membered {-PCPAu}2 ring with a transannular aurophilic inter-action [Au⋯Au = 2.9743 (2) Å]. The ring approximates a flattened boat conformation, with the two methyl-ene C atoms lying ca 0.58-0.59 Å above the least-squares plane defined by the Au2P4 atoms (r.m.s. deviation = 0.0849 Å). One Cl(-) anion functions as a weak bridge between the Au(I) atoms [Au⋯Cl = 2.9492 (13) and 2.9776 (12) Å]. The second Cl(-) anion forms two (water)O-H⋯Cl hydrogen bonds about a centre of inversion, forming a centrosymmetric eight-membered {⋯HOH⋯Cl}2 supra-molecular square. Globally, the dications and loosely associated Cl(-) anions assemble into layers lying parallel to the ac plane, being connected by C-H⋯Cl,π(phen-yl) inter-actions. The supra-molecular squares and solvent acetone mol-ecules are sandwiched in the inter-layer region, being connected to the layers on either side by C-H⋯Cl,O(acetone) inter-actions.
The asymmetric unit of the title compound, 2[Zn(C32H16N8)(C7H9N)]·3C7H9N, comprises two independent complex mol-ecules and three benzyl-amine solvent mol-ecules. Each complex mol-ecule features a penta-coordinated Zn(2+) ion within a square-pyramidal geometry, whereby the N5 donor set is defined by four atoms of the phthalocyaninate dianion (PC) and an N-bound benzyl-amine mol-ecule; it is the relative orientations of the latter that differentiate between the independent complex mol-ecules. The uncoordinated benzyl-amine mol-ecules display different conformations in the structure, with syn-Car-Car-Cm-N (ar = aromatic, m = methyl-ene) torsion angles spanning the range -28.7 (10) to 35.1 (14)°. In the crystal, N-H⋯N and N-H⋯π inter-actions lead to supra-molecular layers in the ab plane. The layers have a zigzag topology, have the coordinating and non-coordinating benzyl-amine mol-ecules directed to the inside, and present the essentially flat PC resides to the outside. This arrangement enables adjacent layers to associate via π-π inter-actions [inter-centroid distance between pyrrolyl and fused-benzene rings = 3.593 (2) Å] so that a three-dimensional architecture is formed.
In the title compound, C15H16N2S2, the central CN2S2 residue is almost planar (r.m.s. deviation = 0.0354 Å) and forms dihedral angles of 56.02 (4) and 75.52 (4)° with the phenyl and tolyl rings, respectively; the dihedral angle between the aromatic rings is 81.72 (5)°. The conformation about the N-N bond is gauche [C-N-N-C = -117.48 (15)°]. Overall, the mol-ecule has the shape of the letter L. In the crystal packing, supra-molecular chains along the a axis are formed by N-H⋯S(thione) hydrogen bonds whereby the thione S atom accepts two such bonds. The hydrogen bonding leads to alternating edge-shared eight-membered {⋯HNCS}2 and 10-membered {⋯HNNH⋯S}2 synthons. The chains are connected into layers by phen-yl-tolyl C-H⋯π inter-actions; the layers stack along the c axis with no specific inter-actions between them.
The title compound, C12H11N3O2, is a second monoclinic polymorph (P21, with Z' = 4) of the previously reported monoclinic (P21/c, with Z' = 2) form [Akhmad Aznan et al. (2010 ▶). Acta Cryst. E66, o2400]. Four independent mol-ecules comprise the asymmetric unit, which have the common features of a syn disposition of the pyridine N atom and the toluene ring, and an intra-molecular amine-nitro N-H⋯O hydrogen bond. The differences between mol-ecules relate to the dihedral angles between the rings which range from 2.92 (19) to 26.24 (19)°. The geometry-optimized structure [B3LYP level of theory and 6-311 g+(d,p) basis set] has the same features except that the entire mol-ecule is planar. In the crystal, the three-dimensional architecture is consolidated by a combination of C-H⋯O, C-H⋯π, nitro-N-O⋯π and π-π inter-actions [inter-centroid distances = 3.649 (2)-3.916 (2) Å].
The title compound, C9H11N3O2S, is a second monoclinic (P21/c) polymorph of the previously reported Cc form [Tan et al. (2008b ▶). Acta Cryst. E64, o2224]. The mol-ecule is non-planar, with the dihedral angle between the N3CS residue (r.m.s. deviation = 0.0816 Å) and the benzene ring being 21.36 (4)°. The conformation about the C=N bond [1.292 (2) Å] is E, the two N-bound H atoms are anti, and the inner hy-droxy O-bound and outer amide N-bound H atoms form intra-molecular hydrogen bonds to the imine N atom. Crucially, the H atom of the outer hy-droxy group is approximately syn to the H atom of the benzene C atom connecting the two C atoms bearing the hy-droxy substituents. This arrangement enables the formation of supra-molecular tubes aligned along [010] and sustained by N-H⋯O, O-H⋯S and N-H⋯S hydrogen bonds; the tubes pack with no specific inter-actions between them. While the mol-ecular structure in the Cc form is comparable, the H atom of the outer hy-droxy group is approximately anti, rather than syn. This different orientation leads to the formation a three-dimensional architecture based on N-H⋯O and O-H⋯S hydrogen bonds.
The asymmetric unit of the title compound, {(C34H28FeP2)[Au(C5H8NS2)]2}, comprises half a mol-ecule, with the full mol-ecule being generated by the application of a centre of inversion. The independent Au(I) atom is coordinated by thiol-ate S and phosphane P atoms that define an approximate linear geometry [S-Au-P = 169.35 (3)°]. The deviation from the ideal linear is traced to the close approach of the (intra-molecular) non-coordinating thione S atom [Au⋯S = 3.1538 (8) Å]. Supra-molecular layers parallel to (100) feature in the crystal packing, being sustained by phen-yl-thione C-H⋯S inter-actions, with the non-coordinating thione S atom in the role of a dual acceptor. Layers stack with no specific inter-actions between them.
In the title compound, C12H15IO7, the 3,4-di-hydro-2H-pyran ring is in a distorted half-boat conformation with the atom bearing the acet-yloxy group adjacent to the C atom bearing the methyl-acetate group lying 0.633 (6) Å above the plane of the remaining ring atoms (r.m.s. deviation = 0.0907 Å). In the crystal, mol-ecules are linked into a supra-molecular chain along the a axis through two C-H⋯O inter-actions to the same acceptor carbonyl O atom; these chains pack with no specific inter-molecular inter-actions between them.
Two independent mol-ecules (A and B) comprise the asymmetric unit of the title compound, C21H18O4. There are significant conformational differences between the mol-ecules relating in particular to the relative orientation of the 3-oxo-2-(phenyl-methyl-idene)but-oxy substituent with respect to the superimposable chromen-2-one residues. To a first approximation, the substituents are mirror images; both are approximately perpendicular to the chromen-2-one fused ring system with dihedral angles of 88.50 (7) (A) and 81.96 (7)° (B). Another difference between the independent mol-ecules is noted in the dihedral angles between the adjacent phenyl and but-3-en-2-one groups of 8.72 (12) (A) and 27.70 (10)° (B). The conformation about the ethene bond in both mol-ecules is E. The crystal packing features C-H⋯O, C-H⋯π(ar-yl) and π-π [Cg⋯Cg = 3.6657 (8) and 3.7778 (8) Å] stacking inter-actions, which generate a three-dimensional network.
In the title compound, C11H12O2S2, two independent but virtually superimposable mol-ecules, A and B, comprise the asymmetric unit. In each mol-ecule, the 1,3-di-thiane ring has a chair conformation with the 1,4-disposed C atoms being above and below the plane through the remaining four atoms. The substituted benzene ring occupies an equatorial position in each case and forms dihedral angles of 85.62 (9) (mol-ecule A) and 85.69 (8)° (mol-ecule B) with the least-squares plane through the 1,3-di-thiane ring. The difference between the mol-ecules rests in the conformation of the five-membered 1,3-dioxole ring which is an envelope in mol-ecule A (the methyl-ene C atom is the flap) and almost planar in mol-ecule B (r.m.s. deviation = 0.046 Å). In the crystal, mol-ecules of A self-associate into supra-molecular zigzag chains (generated by glide symmetry along the c axis) via methyl-ene C-H⋯π inter-actions. Mol-ecules of B form similar chains. The chains pack with no specific directional inter-molecular inter-actions between them.
In the title compound, C23H21N3Se, the C-bound phenyl ring is almost coplanar with the central five-membered ring [dihedral angle = 2.84 (10)°], but the N-bound benzene ring is inclined [dihedral angle = 47.52 (10)°]. The dihedral angle between the Se-bound rings is 69.24 (9)°. An intra-molecular Se⋯N inter-action of 3.0248 (15) Å is noted. In the crystal, C-H⋯π inter-actions connect mol-ecules into double layers that stack along the a axis with no directional inter-actions between them.
In the title compound, C15H16N2S3 {systematic name: [({[(4-methyl-phen-yl)meth-yl]sulfan-yl}methane-thio-yl)amino][1-(thio-phen-2-yl)ethyl-idene]amine}, the central CN2S2 residue is almost planar (r.m.s. deviation = 0.0061 Å) and forms dihedral angles of 7.39 (10) and 64.91 (5)° with the thienyl and p-tolyl rings, respectively; the dihedral angle between these rings is 57.52 (6)°. The non-thione S atoms are syn, and with respect to the thione S atom, the benzyl group is anti. In the crystal, centrosymmetrically related mol-ecules self-associate via eight-membered {⋯HNCS}2 synthons. The dimeric aggregates stack along the a axis and are are consolidated into a three-dimensional architecture via methyl-C-H⋯π(benzene) and benzene-C-H⋯π(thien-yl) inter-actions.
In the title hydrate, C9H12N4S·H2O (systematic name: 3-methyl-1-{(E)-[(3-methyl-pyridin-2-yl)methyl-idene]amino}-thio-urea monohydrate), a small twist is noted between the pyridine ring and the rest of the organic mol-ecule [dihedral angle = 6.96 (5)°]. The imine and pyridine N atoms are syn, and the amine H atoms are anti. The latter arrangement allows for the formation of an intra-molecular N-H⋯N(imine) hydrogen bond. Both the N-bonded H atoms form hydrogen bonds to symmetry-related water mol-ecules, and the latter forms O-H hydrogen bonds with the pyridine N and thione S atoms. These inter-actions lead to supra-molecular layers that stack along the a-axis direction with no specific inter-actions between them.
In the title compound, C10H11NO2, two independent but virtually superimposable mol-ecules, A and B, comprise the asymmetric unit. The heterocyclic ring in each mol-ecule has a screw-boat conformation, and the methyl-hydroxyl group occupies a position to one side of this ring with N-C-C-O torsion angles of -55.30 (15) (mol-ecule A) and -55.94 (16)° (mol-ecule B). In the crystal, O-H⋯O and N-H⋯O hydrogen bonding leads to 11-membered {⋯HNCO⋯HO⋯HNC2O} heterosynthons, involving three different mol-ecules, which are edge-shared to generate a supra-molecular chain along the a axis. Inter-actions of the type C-H⋯O provide additional stability to the chains, and link these into a three-dimensional architecture.