Crystal structure of homodinuclear platinum complex containing a metal-metal bond bridged by hydride and phosphide ligands.

In the title compound, µ-di-phenyl-phosphido-µ-hydrido-bis-[bromido-(tri-phenyl-phosphane-κP)platinum(II)] diethyl ether monosolvate, [Pt2Br2(C12H10P)H(C18H15P)2]·C4H10O or [Pt2(µ-H)(µ-PPh2)Br2(PPh3)2]·(C2H5)2O, the PtII atoms are coordinated in a distorted square-planar arrangement, with one hydrido and one phosphido ligand bridging in a trans position. In the lattice, C-H⋯·O and C-H⋯π interactions are present. This complex has a total number of 32 electrons, 16 electrons for each PtII atom. One of the Br atoms is disordered over two positions in a 0.92:0.08 ratio.

Synthesis, structure characterization, photoluminescence properties and TD-DFT calculations for two new borates.

Due to their rich structural chemistry and wide variety of applications, borate materials have provided a rich area of research. In a continuation of this research, diethylammonium bis(2-oxidobenzoato-κ2O1,O2)borate, C4H12N+·BO4(C7H4O)2-, (1), and propylammonium bis(2-oxidobenzoato-κ2O1,O2)borate, C3H10N+·BO4(C7H4O)2-, (2), have been synthesized by the reaction of boric acid with salicylic acid under ambient conditions. In both structures, the B atom exhibits a slightly distorted tetrahedral environment formed by the bidentate coordination of two salicylate anions via the O atoms of the central carboxylate and oxide groups. In the crystals of salts (1) and (2), mixed cation-anion layers lying parallel to the (101) plane are formed through N-H...O, C-H...O and C-H...π/N-H...O hydrogen-bonding interactions, resulting, in each case, in a two-dimensional supramolecular architecture in the solid state. The photoluminescence properties of the salts were studied using the as-synthesized samples and reveal that salts (1) and (2) both display a strong blue-light emission, with maxima at 489 and 491 nm, respectively. In DFT/TD-DFT (time-dependent density functional theory) studies, the blue emission appears to be derived from an intramolecular charge transfer (ICT) excited state. In addition, IR and UV-Vis spectroscopies were used to investigate the title salts.

Crystal structure, thermal and fluorescence properties of 2,2':6',2''-terpyridine-1,1',1''-triium tetra-chlorido-nickelate(II) chloride.

The title compound, (C15H14N3)[NiCl4]Cl, comprises an NiII cation tetra-hedrally coordinated by four chloride anions, a non-coordinating chloride anion and an essentially planar terpyridinium trication (tpyH33+), in which the central pyridinium ring forms dihedral angles of 5.7 (2) and 6.0 (2)° with the peripheral pyridinium rings. Three inter-species N-H⋯Cl hydrogen bonds are formed with the Cl- anion, which also forms a link between the (tpyH33+) cations through an aromatic C-H⋯Cl inter-action, forming a zigzag chain extending along the 21 (b) screw axis. Two of the anionic Cl atoms of the [NiCl4]2- anions form Ni-Cl⋯π inter-actions with separate pyridinium rings [Ni⋯Cg = 3.669 (3) and 3.916 (4) Å]. In the crystal, successive undulating inorganic and organic layers are formed, extending across the (100) plane. Thermogravimetric and differential thermal analysis (TGA/DTA) indicate that the compound starts to decompose at 313 K and may be a candidate for use as a blue-light luminescent material.

Crystal structure of bis[bis(4-azaniumylphenyl) sulfone] tetranitrate monohydrate.

In the title compound, the hydrated tetra-(nitrate) salt of dapsone (4,4'-di-amino-diphenyl-sulfone), 2C12H14N2O2S2+·4NO3-·H2O {alternative name: bis[bis-(4,4'-di-aza-niumylphen-yl) sulfone] tetra-nitrate monohydrate}, the cations are conformationally similar, with comparable dihedral angles between the two benzene rings in each of 70.03 (18) and 69.69 (19)°. In the crystal, mixed cation-anion-water mol-ecule layers lying parallel to the (001) plane are formed through N-H⋯O, O-H⋯O and C-H⋯O hydrogen-bonding inter-actions and these layers are further extended into an overall three-dimensional supra-molecular network structure. Inter-ring π-π inter-actions are also present [minimum ring centroid separation = 3.693 (3) Å].

Bis(tetra-phenyl-phospho-nium) tetra-chlorido-cobaltate(II).

The title compound, (C24H20P)2[CoCl4], was prepared under hydro-thermal conditions. In the crystal, the tetra-phenyl-phospho-nium cations are linked by pairs of weak C-H⋯π inter-actions into supra-molecular dimers; the Co(II) cations lie on twofold rotation axes and the tetra-hedral [CoCl4](2-) anions are linked with the tetra-phenyl-phospho-nium cations via weak C-H⋯Cl hydrogen bonds.

Di-aqua-bis-[2-(2-hy-droxy-eth-yl)pyridine-κ(2) N,O]cobalt(II) dichloride.

In the title salt, [Co(C7H9NO)2(H2O)2]Cl2, the Co(II) cation, located on an inversion center, is N,O-chelated by two hy-droxy-ethyl-pyridine ligands and coordinated by two water mol-ecules in a distorted O4N2 octa-hedral geometry. In the crystal, the Cl(-) anions link with the complex cations via O-H⋯Cl hydrogen bonds, forming a three-dimensional supra-molecular architecture. π-π stacking is observed between the pyridine rings of adjacent mol-ecules [centroid-centroid distance = 3.5810 (11) Å].

4-(Di-methyl-amino)-pyridinium trichlorido[4-(di-methyl-amino)-pyridine-κN]cobaltate(II).

In the anion of the title compound, (C7H11N2)[CoCl3(C7H10N2)], the Co(II) ion is coordinated by one N atom from a 4-(di-methyl-amino)-pyridine (DMAP) ligand and three Cl atoms, forming a CoNCl3 polyhedron with a distorted tetra-hedral geometry. In the crystal, cations and anions are linked via weak N-H⋯Cl and C-H⋯Cl hydrogen bonds. Double layers of complex anions stack along the b- axis direction, which alternate with double layers of 4-(di-methyl-amino)-pyridinium cations.

Bis(azido-κN)bis-[4-(dimethyl-amino)-pyridine-κN]zinc.

In the title complex, [Zn(N3)2(C7H10N2)2], the Zn(II) atom is coordinated by two N atoms from two 4-(dimethyl-amino)-pyridine (DMAP) ligands and by two N atoms from two azide anions in a distorted tetra-hedral coordination geometry. In the crystal, weak C-H⋯N hydrogen bonds between the DMAP and azide ligands link these discrete complex mol-ecules into a three-dimensional supra-molecular network.

catena-Poly[[bis-[4-(dimethyl-amino)-pyridine-κN (1)]cobalt(II)]-di-µ-azido-κ(4) N (1):N (3)].

The title layered polymer, [Co(N3)2(C7H10N2)2] n , contains Co(II), azide and 4-(dimethyl-amino)-pyridine (4-DMAP) species with site symmetries m2m, 2 and m, respectively. The Co(2+) ion adopts an octa-hedral coordination geometry in which four N atoms from azide ligands lie in the equatorial plane and two 4-DMAP N atoms occupy the axial positions. The Co(II) atoms are connected by two bridging azide ligands, resulting in a chain parallel to the c axis.

l-Leucinium fluoride monohydrate.

The asymmetric unit of the title hydrated salt, C(6)H(14)NO(2) (+)·F(-)·H(2)O, contains a discrete cation with a protonated amino group, a halide anion and one water mol-ecule. The crystal structure is composed of double layers parallel to (010) held together by N-H⋯O, N-H⋯F, O-H⋯F and C-H⋯F hydrogen bonds, forming a two-dimensional network, and stacked along the c axis, viz. hydro-philic layers at z = 0 and 1/2 and hydro-phobic layers at z = 1/3 and 2/3.

Bis(adeninium) bis-(hydrogensulfate) sulfate.

The title compound, 2C5H7N5(2+)·2HSO4(-)·SO4(2-), was synthesized from adenine and sulfuric acid. The asymmetric unit contains two diprotonated adeninium cations, two bis-ulfate anions and one sulfate anion. The crystal structure is stabilized by classical N-H⋯O and O-H⋯O hydrogen bonds, and weak C-H⋯O and C-H⋯N hydrogen bonds, generating a three-dimensional network.

dl-Tyrosinium chloride dihydrate.

In the title compound, C(9)H(12)NO(3) (+)·Cl(-)·2H(2)O, the cation has a protonated amino group resulting from proton transfer from chloridric acid. The structure displays double layers parallel to the [010] direction held together by N-H⋯O, N-H⋯Cl, O-H⋯O and O-H⋯Cl hydrogen bonds. These layers are stacked along the c axis at b = 1/2; within each layer, the tyrosinium cations are arranged in an alternating head-to-tail sequence, forming inversion dimers [R(2) (2)(10) motif]. The water mol-ecules allow for the construction of a three-dimensional hydrogen-bonded network formed by centrosymmetric R(6) (6)(28) and R(8) (8)(34) motifs.

Influence of anion substitution on hydrogen-bonding patterns of salt compounds: cytosinium hydrogen sulfate and cytosinium perchlorate.

In the two title compounds, cytosinium hydrogen sulfate, C(4)H(6)N(3)O(+).HSO(4)(-), (I), and cytosinium perchlorate, C(4)H(6)N(3)O(+).ClO(4)(-), (II), the asymmetric units comprise a cytosinium cation with hydrogen sulfate and perchlorate anions, respectively. The crystal structures of (I) and (II) are similar; that of (I) is characterized by a three-dimensional N-H...O, O-H...O and C-H...O hydrogen-bonded network. In (I) and (II), two-dimensional layers are formed by N-H...O and C-H...O hydrogen bonds and, in the case of (I), they are linked by O-H...O hydrogen bonds where the anion acts as a donor and the cation as an acceptor. The hydrogen-bonded sheets in (II) form an angle of 87.1 degrees.

Bis(3-carboxy-anilinum) bis-(perchlorate) monohydrate.

In the structure of the title compound, 2C(7)H(8)NO(2) (+)·2ClO(4) (-)·H(2)O, the ions are connected via N-H⋯O, N-H⋯(O,O), O-H⋯O, O-H⋯(O,O) and C-H⋯O hydrogen bonds into a three-dimensional network.

3-Carboxy-anilinium hemioxalate.

In the title compound, C(7)H(8)NO(2) (+)·0.5C(2)O(4) (2-), the asymmetric unit consists of an 3-carboxy-anilinium cation, and one-half of an oxalate anion, which lies on a twofold rotation axis. The crystal packing is consolidated by inter-molecular N-H⋯O and O-H⋯O hydrogen bonds. The structure is built from infinite chains of cations and oxalate anions extending parallel to the b and c axes. The crystal studied was a non-merohedral twin. The ratio of the twin components refined to 0.335 (3):0.665 (3).

trans-Di-µ-iodido-bis-[(3H-1,2-benzodithiole-3-thione)iodidomercury(II)].

The complete molecule of the dinuclear title compound, [Hg(2)I(4)(C(7)H(4)S(3))(2)], is generated by crystallographic inversion symmetry. The complex has a dimeric structure in which each Hg(II) ion adopts a tetra-hedral geometry and is coordinated by two bridging I atoms, one terminal iodide ion and one thio-carbonyl S atom (C=S) of the ligand. The square plane formed by the Hg and I atoms and their symmetry counterparts makes a dihedral angle of 89.66 (3)° with the DDT plane. There is no classical hydrogen bonding, but weak S⋯S inter-actions of 3.4452 (7) and 3.6859 (7) Šmaintain the cohesion of the crystal structure.

dl-Asparaginium nitrate.

In the title compound, C(4)H(9)N(2)O(3) (+)·NO(3) (-), alternatively called (1RS)-2-carbamoyl-1-carboxy-ethanaminium nitrate, the asymmetric unit comprises one asparaginium cation and one nitrate anion. The strongest cation-cation O-H⋯O hydrogen bond in the structure, together with other strong cation-cation N-H⋯O hydrogen bonds, generates a succession of infinite chains of R(2) (2)(8) rings along the b axis. Additional cation-cation C-H⋯O hydrogen bonds link these chains into two-dimensional layers formed by alternating R(4) (4)(24) and R(4) (2)(12) rings. Connections between these layers are provided by the strong cation-anion N-H⋯O hydrogen bonds, as well as by one weak C-H⋯O inter-action, thus forming a three-dimensional network. Some of the cation-anion N-H⋯O hydrogen bonds are bifurcated of the type D-H⋯(A(1),A(2)).

dl-Asparaginium perchlorate.

Two enantiomeric counterparts (l- and d-asparginium cations related by glide planes) are present in the structure of the title compound, C(4)H(9)N(2)O(3) (+)·ClO(4) (-), with a 1:1 cation-anion ratio. The structure is built up from asparginium cations and perchlorate anions. In the crystal, mol-ecules assemble in double layers parallel to (100) through N-H⋯O, O-H⋯O and C-H⋯O hydrogen bonds. In the asparginium layers, hydrogen bonds generate alternating R(2) (2)(8) and R(4) (3)(18) graph-set motifs. Further hydrogen bonds involving the anions and cations result in the formation of a three-dimensional network.

Adeninium cytosinium sulfate.

In the title compound, C(5)H(6)N(5) (+)·C(4)H(6)N(3)O(+)·SO(4) (2-), the adeninium (AdH(+)) and cytosinium (CytH(+)) cations and sulfate dianion are involved in a three-dimensional hydrogen-bonding network with four different modes, viz. AdH(+)⋯AdH(+), AdH(+)⋯CytH(+), AdH(+)⋯SO(4) (2-) and CytH(+)⋯SO(4) (2-). The adeninium cations form N-H⋯N dimers through the Hoogsteen faces, generating a characteristic R(2) (2)(10) motif. This AdH(+)⋯AdH(+) hydrogen bond in combination with AdH(+)⋯CytH(+ )H-bonds leads to two-dimensional cationic ribbons parallel to the a axis. The sulfate anions inter-link the ribbons into a three-dimensional hydrogen-bonding network and thus reinforce the crystal structure.

Adeninium 3-carboxy-anilinium bis-(perchlorate) trihydrate.

In the title salt, C(5)H(6)N(5) (+)·C(7)H(8)NO(2) (+)·2ClO(4) (-)·3H(2)O, the 3-carboxy-anilinium and adeninium cations are monoprotonated at the amino group and at a pyrimidine N atom respectively. In the crystal, the components are involved in extensive three-dimensional hydrogen-bonding networks composed of O-H⋯O, N-H⋯O, O-H⋯N, N-H⋯N and C-H⋯O inter-actions. Bifurcated hydrogen bonds are observed between perchlorate O atoms and adeninium cations.