Bis[tris(phenanthroline-κ2 N,N′)cobalt(II)] undecatungsto(VI)vanado(V)phosphate dihydrate

In the title hydrated salt, [Co(C12H8N2)3]2[PVW11O40]·2H2O, the complete Kegggin ion is generated by crystallographic inversion symmetry, which imposes statistical disorder on the O atoms of its central PO4 group. The V atom is statistically disordered over all the metal sites of the anion. In the cation, the Co2+ ion is coordinated by three bidentate 1,10-phenanthroline (phen) ligands, generating a distorted CoN6 octahedron. Possible very weak intramolecular C—H⋯π interactions occur in the cation. In the crystal, the components are linked by O—H⋯O and C—H⋯O interactions, building a three-dimensional network featuring one-dimensional voids along the c-axis direction.

In the title hydrated salt, [Co(C 12 H 8 N 2 ) 3 ] 2 [PVW 11 O 40 ]Á2H 2 O, the complete Kegggin ion is generated by crystallographic inversion symmetry, which imposes statistical disorder on the O atoms of its central PO 4 group. The V atom is statistically disordered over all the metal sites of the anion. In the cation, the Co 2+ ion is coordinated by three bidentate 1,10phenanthroline (phen) ligands, generating a distorted CoN 6 octahedron. Possible very weak intramolecular C-HÁ Á Á interactions occur in the cation. In the crystal, the components are linked by O-HÁ Á ÁO and C-HÁ Á ÁO interactions, building a three-dimensional network featuring one-dimensional voids along the c-axis direction.

Experimental
A reaction mixture of Na 2 WO 4 ·2H 2 O (2 g, 6.064 mmol), NaH 2 PO 4 ·2H 2 O (0.1034 g, 0.6628 mmol), CoCl 2 ·6H 2 O (0.1951 g, 0.8196 mmol), V 2 O 5 (0,0455 g; 0.25 mmol) and phen·H 2 O (0.3196 g, 1.7758 mmol) were added to water (10 ml). The mixture was adjusted to pH = 5.5 by the addition of 4M HCl aqueous solution then stirred for 30 min in air. The mixture solution was transferred into a 23 ml Teflon-lined autoclave and crystallized at 180°C for 4 days. Then the autoclave was cooled at 10°C.h -1 to room temperature. The resulting dark yellow block crystals of I were filtered off, washed with water, and dried at ambient temperature to give yields of 68% based on W.

Refinement
All H atoms attached to C atoms were fixed geometrically and treated as riding, with C-H = 0.93 Å and U iso (H) =

1.2Ueq(C). Water H atoms were refined using restraints
Many trials of crystal growing are unsuccessful and despite the good quality of selected crystal for experimental X-Ray,the largest isolated one has a relatively small size (crystal size: 0.04 × 0.08 × 0.013 mm), which lead to the poor diffraction at higher angles.      View of intramolecular C-H···π interaction in (I). The H-atoms not included in H-bond scheme are omitted.

Bis[tris(phenanthroline-κ 2 N,N′)cobalt(II)] undecatungsto(VI)vanado(V)phosphate dihydrate
Crystal data [Co(C 12  Special details Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > σ(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.