A stair-like two-dimensional silver(I) coordination polymer of N'-(3-cyanobenzylidene)nicotinohydrazide.

The structure of the title compound, poly[[[mu3-N'-(3-cyanobenzylidene)nicotinohydrazide]silver(I)] hexafluoroarsenate], {[Ag(C14H10N4O)](AsF6)}n, at 173 K exhibits a novel stair-like two-dimensional layer and a three-dimensional supramolecular framework through C-H...Ag hydrogen bonds. The Ag(I) cation is coordinated by three N atoms and one O atom from N'-(3-cyanobenzylidene)nicotinohydrazide (L) ligands, resulting in a distorted tetrahedral coordination geometry. The organic ligand acts as a mu3-bridging ligand through the pyridyl and carbonitrile N atoms and deviates from planarity in order to adapt to the coordination geometry. Two ligands bridge two Ag(I) cations to construct a small 2+2 Ag2L2 ring. Four ligands bridge one Ag(I) cation from each of four of these small rings to form a large grid. An interesting stair-like two-dimensional (3,6)-net is formed through Ag(I) metal centres acting as three-connection nodes and through L molecules as tri-linkage spacers.

Bis[N'-(3-cyano-benzyl-idene)isonicotino-hydrazide]silver(I) trifluoro-acetate.

In the title compound, [Ag(C(14)H(10)N(4)O)(2)]CF(3)CO(2), the Ag(I) ion is coordinated by two N atoms of the pyridine rings of two N'-(3-cyano-benzyl-idene)isonicotinohydrazide ligands in a nearly linear geometry. In the crystal structure, a combination of close contacts formed via Ag⋯N inter-actions [Ag⋯N = 3.098 (2) and 3.261 (2) Å] from symmetry-related mol-ecules and inter-molecular N-H⋯O hydrogen bonds between CF(3)CO(2) (-) anions and the hydrazone groups of two ligands give rise to chains. Furthermore, there are Ag⋯O inter-actions with a separation of 2.765 (2) Šbetween chains. The F atoms of the CF(3)CO(2) (-) anion are disordered over two sites with refined occupancies of 0.593 (5) and 0.407 (5).

Dichlorido(2,9-diprop-oxy-1,10-phenanthroline-κN,N')cadmium(II).

In the title complex, [CdCl(2)(C(18)H(20)N(2)O(2))], the Cd(II) ion is coordinated by two N atoms from a bis-chelating 2,9-diprop-oxy-1,10-phenanthroline ligand and two Cl atoms in a distorted tetra-hedral environment. The two Cd-Cl bond distances are significantly different from each other and the N-Cd-N bond angle is acute. In the crystal structure, there are π-π stacking inter-actions between symmetry-related phenanthroline ring systems, with a centroid-centroid distance of 3.585 (3) Å.

Bis[N'-(3-cyano-benzyl-idene)isonicotino-hydrazide-κN]silver(I) trifluoro-methane-sulfonate.

In the title compound, [Ag(C(14)H(10)N(4)O)(2)]CF(3)SO(3), two N atoms from two independent pyridyl rings of two N'-3-cyano-benzyl-ideneisonicotinohydrazide ligands coordinate to the unique Ag(I) ion, forming a nearly linear coordination geometry. Adjacent silver complexes are primarily linked together by Ag⋯N inter-actions, with Ag⋯N separations of 2.877 (2) and 3.314 (2) Å. On the other hand, one CF(3)SO(3) (-) anion inter-acts with hydrazone groups of two neighbouring ligands via N-H⋯O hydrogen bonds. These weak inter-molecular inter-actions contribute to the formation of supra-molecular chains. In addition, there are Ag⋯O inter-actions [2.787 (2) Å] between Ag and O atoms from adjacent chains.

Cinnamyl 2-oxo-2H-chromene-3-carboxyl-ate.

The title compound, C(19)H(14)O(4), was prepared by the reaction of 2-oxo-2H-chromene-3-acyl chloride with cinnamic alcohol. The whole mol-ecule is not planar, the dihedral angle between the planes of coumarin and benzene rings being 13.94 (4)°, but the plane of the coumarin ring and that of the ester group are almost coplanar, making a dihedral angle of 2.9 (1)°. In the crystal structure, weak inter-molecular C-H⋯O hydrogen bonds link two mol-ecules into dimers, and π-π stacking inter-actions between inversion-related rings of the coumarin groups [centroid-centroid distance 3.8380 (15) Šwith a slippage of 1.535 Å], which connect the dimers into columns extending along [010].

Dichlorido(2,9-dieth-oxy-1,10-phenanthroline-κN,N')zinc(II).

All non-H atoms except for the Cl atoms lie on a mirror plane in the title complex, [ZnCl(2)(C(16)H(16)N(2)O(2))]. The Zn(II) ion is coordinated by two N atoms from a bis-chelating 2,9-dieth-oxy-1,10-phenanthroline ligand and two symmetry-related Cl atoms in a distorted tetra-hedral environment. The two Zn-N bond lengths are significantly different from each other and the N-Zn-N angle is acute. In the crystal structure, there are weak but significant π-π stacking inter-actions between phenanthroline rings, with a centroid-centroid distance of 3.764 (1) Å.

Dichlorido(2,9-dimeth-oxy-1,10-phenanthroline-κN,N')zinc(II).

In the crystal structure of the title compound, [ZnCl(2)(C(14)H(12)N(2)O(2))], the Zn(II) center is four-coordinated by two N atoms from one 2,9-dimeth-oxy-1,10-phenanthroline ligand and two Cl atoms. The coordination geometry is distorted tetra-hedral, as the Zn-N bond distances are shorter than the Zn-Cl distances, and the Cl-Zn-N and Cl-Zn-Cl bond angles are much larger than the N-Zn-N angle. For the ligand, the O and C atoms of the meth-oxy groups are almost in the plane defined by the phenanthroline ring. The two O atoms deviate from the phenanthroline mean plane by 0.076 (2) and 0.084 (2) Å, and the two methyl C atoms deviate from the phenanthroline mean plane by 0.035 (3) and 0.361 (3) Å. There are medium π-π stacking interactions between two parallel phenanthroline rings with a centroid-centroid distance of 3.7860 (2) Šand a dihedral angle between the plane defined by the two parallel phenanthroline rings of 1.13 (5)°.

catena-Poly[[[[N'-(4-cyano-benzyl-idene)nicotinohydrazide]silver(I)]-µ-[N'-4-cyano-benzyl-idene)nicotinohydrazide]] hexa-fluoridoarsenate].

In the title compound, {[Ag(C(14)H(10)N(4)O)(2)]AsF(6)}(n), the Ag(I) ion is coordinated by two N atoms from two different pyridyl rings and one N atom from one carbonitrile group of three different N'-(4-cyano-benzyl-idene)nicotinohydrazide ligands in a distorted T-shaped geometry. The Ag-N(carbonitrile) bond distance is significant longer than those of Ag-N(pyrid-yl). The bond angles around the Ag(I) atom are also not in line with those in an ideal T-shaped geometry. One type of ligand acts as the bridge that connects Ag(I) atoms into chains along [01]. These chains are linked to each other via N-H⋯O hydrogen bonds and Ag⋯O inter-actions with an Ag⋯O separation of 2.869 (2) Å. In addition, the [AsF(6)](-) counter-anions are linked to the hydrazone groups through N-H⋯F hydrogen bonds. Four of the F atoms of the [AsF(6)](-) anion are disordered over two sets of sites with occupancies of 0.732 (9) and 0.268 (9).

A grid-like two-dimensional Ag(I)coordination polymer: poly[[[mu3-N'-(4-cyanobenzylidene)isonicotinohydrazide]silver(I)] perchlorate].

This study presents new coordinating modes of a Schiff base with three coordinating groups and an interesting two-dimensional framework based on two types of constructing units. In the title compound, {[Ag(C(14)H(10)N(4)O)]ClO(4)}(n), the Ag(I) ion is coordinated by three N atoms and one O atom from three different N'-(4-cyanobenzylidene)isonicotinohydrazide (L) ligands, forming a primary distorted square-planar coordination geometry. Two ligands each bridge two metal centres through one carbonitrile N atom in a monodentate mode and the hydrazide N and O atoms in a bidentate mode to form a small centrosymmetric (2+2)-Ag(2)L(2) ring as a principal constructing unit. The pyridyl N atoms from four ligands in four of these small rings coordinate to Ag atoms in adjacent rings to form a large hexanuclear silver grid. A two-dimensional framework of rectangular grids is constructed from these small rings and large grids. Two perchlorate anions are located in each large grid and are bound to the grid by N-H...O hydrogen bonding. Crosslinking between the layers is achieved through long Ag...O interactions between the perchlorate anions and Ag atoms in adjacent layers.

Bis[µ-3-(1H-pyrazol-1-yl)benzonitrile-κN:N']bis-[perchloratosilver(I)].

In the title centrosymmetric complex, [Ag(2)(ClO(4))(2)(C(10)H(7)N(3))(2)], the unique Ag(I) ion is coordinated by an N atom from a carbonitrile group, an N atom from a symmetry-related pyrazole group and an O atom of a perchlorate ligand to form a distorted T-shaped environment. Two 3-(1H-pyrazol-1-yl)benzonitrile ligands each bridge two Ag(I) ions to form a dinuclear complex. In the crystal structure, there are weak Ag⋯O inter-actions within the range 2.70-3.01 Šlinking dimeric units into layers approximately parallel to (100). The O atoms of the perchlorate ligand are disordered over two sites with occupancies of 0.570 (11) and 0.430 (11), respectively.

catena-Poly[[(2,9-dieth-oxy-1,10-phen-anthroline-κN,N')cadmium(II)]-di-µ-dicyan-amido-κN:N].

In the title polymer, [Cd(C(2)N(3))(2)(C(16)H(16)N(2)O(2))](n), the Cd(II) ion is coordinated by two N atoms from one 2,9-dieth-oxy-1,10-phenanthroline mol-ecule and four N atoms from four symmetry-related dicyanamide ions in a distorted octa-hedral geometry. In the 2,9-dieth-oxy-1,10-phenanthroline ligand, the O and C atoms of the eth-oxy groups are located almost in the plane defined by the phenanthroline ring system. Two dicyanamide ions bridge two Cd(II) ions, which are located on a twofold axis, forming a one-dimensional zigzag chain along the [001] direction. The 2,9-dieth-oxy-1,10-phenanthroline mol-ecules act as bidentate terminal ligands. There are π-π inter-actions between polymeric chains, characterized by a centroid-centroid distance of 3.7624 (2) Šbetween the phenanthroline rings of two neighbouring chains.

A one-dimensional Ag coordination polymer: catena-poly[[[[N'-(4-cyano-benzyl-idene)nicotinohydrazide]silver(I)]-µ-N'-(4-cyano-benzyl-idene)nicotino-hydrazide] trifluoro-methane-sulfonate].

In the title compound, {[Ag(C(14)H(10)N(4)O)(2)]CF(3)SO(3)}(n), the unique Ag(I) ion is coordinated by two N atoms from two pyridine rings of two independent N'-(4-cyano-benzyl-idene)nicotinohydrazide ligands and one N atom of a carbonitrile group of a symmetry-related N'-(4-cyano-benzyl-idene)nicotino-hydrazide ligand, forming a distorted T-shaped coordination environment. One of the independent ligands acts as a bridge connecting Ag(I) ions, forming chains along the a axis. In the crystal structure, two neighbouring anti-parallel chains are connected through N-H⋯O hydrogen bonds. In addition, there are relatively short Ag⋯O contacts of 2.723 (3) Å, which connect the chains into a three-dimensional structure.

(2,9-Dieth-oxy-1,10-phenanthroline-κN,N')bis-(thio-cyanato-κN)cobalt(II).

In the title complex, [Co(NCS)(2)(C(16)H(16)N(2)O(2))], the Co(II) ion is coordinated by two N atoms from one 2,9-dieth-oxy-1,10-phenanthroline ligand and two N atoms from two different thio-cyanate ligands in a distorted tetra-hedral environment. The Co-N bonds involving the thio-cyanate ligands are significantly shorter than the other two Co-N bonds. The atoms of one of the eth-oxy groups are essentially coplanar with the phenanthroline ring [N=C-O-C = 178.8 (4)°], while the other eth-oxy group is slightly twisted from the phenanthroline ring plane [N=C-O-C = 167.2 (4)°]. In the crystal structure, there is a weak π-π stacking inter-action between two symmetry-related phenanthroline rings with a centroid-centroid distance of 3.706 (4) Å.

catena-Poly[[[diaqua-bis(2-methyl-6-oxo-1,6-dihydro-3,4'-bipyridine-5-carbo-nitrile)copper(II)]-µ-sulfato] tetra-hydrate].

In the title polymer, {[Cu(SO(4))(C(12)H(9)N(3)O)(2)(H(2)O)(2)]·4H(2)O}(n), both the metal center and the sulfate anion are located on a twofold axis. The Cu(II) ion is coordinated by two pyridyl N atoms from two symmetry-related organic ligands, two O atoms from two symmetry-related water mol-ecules, and two O atoms from two symmetry-related sulfate anions, resulting in a distorted octa-hedral geometry. The sulfate anions act as µ(2)-bridges and connect metal ions, forming a one-dimensional chain along the b axis. The three-dimensional crystal structure is established through inter-molecular N-H⋯O and O-H⋯O hydrogen bonds involving the organic ligands, sulfate anions, coordinated and uncoordinated water mol-ecules, and through π-π inter-acting 2-pyridone rings, with centroid-centroid separations of ca 3.96 Šand tilt angles of ca 2.62°.

catena-Poly[[[N'-(4-cyano-benzyl-idene)nicotinohydrazide)silver(I)]-µ-N'-(4-cyano-benzyl-idene)nicotinohydrazide] hexa-fluorido-phosphate].

In the title polymer, {[Ag(C(14)H(10)N(4)O)(2)]PF(6)}(n), each Ag(I) ion is coordinated by two N atoms from two pyridyl rings of independent N'-(4-cyano-benzyl-idene)nicotinohydrazide ligands, and one N atom from one carbonitrile group of a symmetry-related ligand in a distorted T-shaped geometry. The ligands exhibit two modes of coordination. One acts as a bridge connecting Ag atoms to form one-dimensional chains along [01]. The other acts as a terminal monodentate ligand, coordinating to Ag through its pyridyl N atom. Two neighbouring anti-parallel chains in the crystal are connected through N-H⋯O hydrogen bonds. Other adjacent chains are packed via Ag⋯O inter-actions, with Ag⋯O separations of 2.876 (2) Å. In addition, PF(6) (-) counter-anions inter-act with the hydrazone groups through N-H⋯F hydrogen bonds. The PF(6) (-) anion is disordered over two sites, with occupancies of 0.773 (8) and 0.227 (8).

Chloridobis(2,9-dieth-oxy-1,10-phenanthroline-κN,N')copper(II) perchlorate.

In the title complex, [CuCl(C(16)H(16)N(2)O(2))(2)]ClO(4), the Cu(II) ion is coordinated by four N atoms from two chelating 2,9-dieth-oxy-1,10-phenanthroline ligands and one chloride ion in a slightly disorted trigonal-bipyramidal environment. Two N atoms and the Cl atom are in equatorial positions while the remaining two N atoms occupy apical sites, the equatorial Cu-N bonds being significantly longer than the two apical Cu-N bonds. The N=C-O-C torsion angles involving the four eth-oxy groups are in the range 161.5 (8) to 177.0 (5)°. In the crystal structure, there are significant π-π stacking inter-actions between inversion-related rings of phenanthroline groups with centroid-centroid distances in the range 3.649 (4)-3.790 (4) Å.

The first 1D twofold interpenetrating metal-organic network generated by 1D triple helical chains with nanosized cages.

Reaction of AgPF(6) with the asymmetric ligand 1,6-dihydro-2-methyl-6-oxo-(3,4'-bipyridine)-5-carbonitrile (1), afforded a significant silver coordination polymer {[Ag(2)(1)(3)](2).(CH(3)OH)(3).(PF(6))(4)}(n) (2) with unique 1D twofold interpenetrating metal-organic frameworks constructed by 1D triple helical chains with nanosized cages hosting counterions as guests. This compound exhibits high thermal stability and blue-shift emission with large intensity enhancement compared with that of the free ligand.