[(B3O3H3)(n)M]+ (n = 1, 2;M = Cu, Ag, Au): a new class of metal-cation complexes.

A density functional theory (DFT) investigation into the structures and bonding characteristics of [(B3O3H3)nM](+)(n = 1, 2;M = Cu, Ag, Au) complexes was performed. DFT calculations and natural bond orbital (NBO) analyses indicate that the ΙB metal complexes of boroxine exhibit intriguing bonding characteristics, different from the typical cation-π interactions between ΙB metal-cations and benzene. The complexes of [B3O3H3M](+) and [(B3O3H3)2 M](+) (M = Cu, Ag, and Au) favor the conformation of perfectly planar structures with the C2v and D2h symmetry along one of the threefold molecular axes of boroxine, respectively. Detailed natural resonance theory (NRT) and canonical molecular orbitals (CMOs) analyses show that interaction between the metal cation and the boroxine in [B3O3H3M](+) (M = Cu, Ag, and Au) is mainly ionic, while the ΙB metal-cations←π donation effect is responsible for the binding site. In these complexes, boroxine serves as terminals η(1)-B3O3H3 with one O atom of the B3O3 ring. The infra-red (IR) spectra of [B3O3H3M](+) were simulated to facilitate their future experimental characterization. The complexes all give two IR active modes at about 1,300 and 2,700 cm(-1), which are inactive in pure boroxine. Simultaneously, the B-H stretching modes of the complexes are red-shifted due to the interaction between the metal-cation and boroxine. To explore the possibility of the structural pattern developed in this work forming mesoporous materials, complexes [(B3O3H3M)6](6+) (M = Cu, Ag, and Au) were also studied, which appear to be unique and particular interesting: they are all true minima with D6h symmetries and pore sizes ranging from 12.04 Å to 13.65 Å.

catena-Poly[[(1,10-phenanthroline-κN,N')copper(I)]-µ-thio-cyanato-κN:S].

In the title complex, [Cu(NCS)(C(12)H(8)N(2))](n), the Cu(I) ion is in a distorted tetra-hedral CuN(3)S coordination geometry. The thio-cyanate ligand acts as bridging ligand, forming chains along [100]. A crystallographic mirror plane runs through the Cu(I) ion, the thio-cyanate ligand and the middle of the phenanthroline ligand.

Diaqua-(nitrato-κO,O')[2-(1H-1,2,4-triazol-1-yl-κN)-1,10-phenanthroline-κN,N']cadmium(II) nitrate.

In the title complex, [Cd(C(14)H(9)N(5))(NO(3))(H(2)O)(2)]NO(3), the Cd(II) ion is coordinated in a distorted penta-gonal-bipyramidal geometry. The equatorial sites are occupied by a 2-(1H-1,2,4-triazol-1-yl)-1,10-phenanthroline ligand in a tridentate coordination mode and a bis-chelating nitrate ligand. Two aqua ligands are coordinated at the axial sites. All non-H atoms in the equatorial plane are co-planar within 0.0673 Å. In the crystal, inter-molecular O-H⋯O and O-H⋯N hydrogen bonds connect the components into a two-dimensional network parallel to (001). In addition, there is a π-π stacking inter-action between symmetry-related benzene rings, with a centroid-centroid distance of 3.598 (3) Å.

Dichlorido[2,2'-(1,10-phenanthrolin-2-ylimino)diethanol]cadmium(II).

In the title complex, [CdCl(2)(C(16)H(17)N(3)O(2))], the metal atom exhibits a distorted trigonal-bipyramidal coordination geometry. O-H⋯O and O-H⋯Cl hydrogen bonds involving hydr-oxy groups and one of coordinated Cl atoms link complexes in the crystal packing. There is a π-π stacking inter-action between adjacent 1,10-phenanthroline rings, with a distance of 3.675 (2) Šbetween the centroids of the pyridine and benzene rings.

2,9-Bis(4-pyridylmeth-oxy)-1,10-phenanthroline.

In the title mol-ecule, C(24)H(18)N(4)O(2), the dihedral angles between the mean plane of the phenanthroline ring system and the pyridine rings are 82.52 (5) and 71.58 (4)°. The dihedral angle between the two pyridine ring planes is 53.54 (6)°. In the crystal structure, there are π-π stacking inter-actions between 1,10-phenanthroline rings, with centroid-centroid distances of 3.6101 (11) and 3.5864 (11) Å.

Chlorido[2,2'-(oxydimethyl-ene)-dipyridine]copper(II) perchlorate-aqua-chlorido[2,2'-(oxydimethyl-ene)-dipyridine]copper(II) perchlorate (1/1).

The asymmetric unit of the title compound, [CuCl(C(12)H(12)N(2)O)][CuCl(C(12)H(12)N(2)O)(H(2)O)](ClO(4))(2), contains two different discrete cations. In one cation, the Cu(II) ion is coordinated in a slightly distorted square-planar geometry, while in the other the Cu(II) ion is in a slightly distorted square-pyramidal environment. In the crystal structure, there are O-H⋯O hydrogen bonds between coordinated water mol-ecules and perchlorate anions. Both types of cations are linked into one-dimensional chains along the b axis by weak electrostatic Cu⋯Cl inter-actions, with Cu⋯Cl distances of 2.8088 (16) and 3.2074 (17) Å.

Aqua-bis(3'-hydr-oxy-2,2'-bipyridine-3-olato-κN,N')zinc(II).

In the title complex, [Zn(C(10)H(7)N(2)O(2))(2)(H(2)O)], the Zn(II) ion and water O atom are located on a crystallographic twofold rotation axis and the metal atom assumes a distorted trigonal-bipyramidal ZnN(4)O coordination geometry. An intra-molecular O-H⋯O hydrogen bond occurs within the ligand and inter-molecular O-H⋯O hydrogen bonds involving the water mol-ecule result in a sheet structure in the crystal structure. In addition, a short C-O⋯π contact between the O atom of the deprotonated hydroxyl group and a nearby pyridine ring [O⋯Cg = 3.977 (2) Å, where Cg is the centroid of the pyridine ring] is observed.

(Dicyanamido)[tris-(2-pyridylmeth-yl)amine]zinc(II) perchlorate.

In the title complex, [Zn(C(2)N(3))(C(18)H(18)N(4))]ClO(4), the Zn(II) ion has a slightly distorted trigonal-bipyramidal ZnN(5) coordination geometry. The crystal structure is stabilized by weak inter-molecular C-H⋯O and C-H⋯N hydrogen bonds. In addition, there are relatively close contacts between the O atoms of the perchlorate anion and symmetry-related pyridine rings [O⋯Cg = 3.179 (3) and 3.236 (3) Å, where Cg is the centroid of a pyridine ring], and between the terminal N atom of the dicyanamide ligand and pyridine rings [N⋯Cg = 3.381 (4)-3.761 (3) Å]. The central N atom of the dicyanamide ligand is disordered over two sites in an approximately 0.6:0.4 ratio.

Bis(2-dimethylamino-1,10-phenanthroline-κN,N')bis-(thio-cyanato-κN)nickel(II) methanol disolvate.

In the title complex, [Ni(NCS)(2)(C(14)H(13)N(3))(2)]·2CH(3)OH, the Ni(II) atom lies on a crystallographic twofold rotation axis and is in a slightly distorted octa-hedral NiN(6) coordination environment. The crystal structure is stabilized by a combination of weak π-π stacking inter-actions between symmetry-related 1,10-phenanthroline ligands [centroi-centroid distance between benzene rings = 3.5936 (18) Å] and weak O-H⋯S, C-H⋯O and C-H⋯S hydrogen bonds between methanol and complex mol-ecules.

(2-Meth-oxy-1,10-phenanthroline-κN,N')bis-(thio-cyanato-κN)zinc(II).

In the title complex, [Zn(NCS)(2)(C(13)H(10)N(2)O)], the Zn(II) ion is in a distorted tetra-hdral ZnN(2)Cl(2) coordination environment. In the crystal structure, there is a weak π-π stacking inter-action between adjacent 1,10-phenanthroline rings, with a pyridine centroid-centroid distance of 3.6620 (15) Å.

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

There are two molecules of the title complex, [ZnCl(2)(C(13)H(10)N(2)O)], in the asymmetric unit. Each Zn atom assumes a distorted tetra-hedral ZnN(2)Cl(2) coordination geometry. There are weak π-π stacking inter-actions between adjacent 1,10-phenanthroline rings [centroid-centroid distances = 3.6356 (18) and 3.6353 (18) Å].

9-(2-Pyridylmeth-oxy)-1,10-phenanthrolin-1-ium perchlorate methanol solvate.

In the title organic salt, C(18)H(14)N(3)O(+)·ClO(4) (-)·CH(4)O, there is a π-π stacking inter-action between neighbouring 1,10-phenanthroline rings and the relevant distances are 3.5453 (18) Šfor the centroid-centroid distance and 3.354 Šfor the perpendicular distance. There is also a relatively close contact between a C-H bond and a symmetry-related pyridine ring. There are classical N-H⋯O and O-H⋯N hydrogen bonds and non-classical C-H⋯O hydrogen bonds involving the cation, methanol solvent mol-ecule and perchlorate anion.