Bis(2-chloro-1,10-phenanthroline-κ2 N,N′)(thiocyanato-κN)zinc (2-chloro-1,10-phenanthroline-κ2 N,N′)tris(thiocyanato-κN)zincate

The asymmetric unit of the title compound, [Zn(NCS)(C12H7ClN2)2][Zn(NCS)3(C12H7ClN2)], contains two cations and two anions. In the cations, the ZnII ions have distorted trigonal–bipyramidal environments formed by four N atoms from two 2-chloro-1,10-phenanthroline (cphen) ligands and one N atom from a thiocyanate ligand. The ZnII atoms in the complex anions also have distorted trigonal–bipyramidal environments, formed by two N atoms from a cphen ligand and three N atoms from three thiocyanato ligands. The crystal packing exhibits π–π interactions between the rings of the cphen ligands [shortest centroid–centroid distance = 3.586 (5) Å] and short intermolecular S⋯Cl [3.395 (5) Å] and S⋯S [3.440 (4) Å] contacts.

The asymmetric unit of the title compound, [Zn(NCS)-(C 12 H 7 ClN 2 ) 2 ][Zn(NCS) 3 (C 12 H 7 ClN 2 )], contains two cations and two anions. In the cations, the Zn II ions have distorted trigonal-bipyramidal environments formed by four N atoms from two 2-chloro-1,10-phenanthroline (cphen) ligands and one N atom from a thiocyanate ligand. The Zn II atoms in the complex anions also have distorted trigonal-bipyramidal environments, formed by two N atoms from a cphen ligand and three N atoms from three thiocyanato ligands. The crystal packing exhibitsinteractions between the rings of the cphen ligands [shortest centroid-centroid distance = 3.586 (5) Å ] and short intermolecular SÁ Á ÁCl [3.395 (5) Å ] and SÁ Á ÁS [3.440 (4) Å ] contacts. The asymmetric unit of (I) (Fig. 1) contains two cationic and two anionic complexes, respectively. The cationic complex involves two cphen neutral ligands and one thiocyanate anionic ligand, whereas the anionic complex involves one cphen neutral ligands and three thiocyanate anionic ligands. In both complexes, the zinc(II) ions assume distorted trigonal bipyramidal coordinated geometry.

Experimental
A 5 mL H 2 O solution of NaNCS (0.0232 g, 0.286 mmol) was added into 15 mL methanol solution containing Zn(ClO 4 ).6H 2 O (0.0678 g, 0.182 mmol) and 2-chloro-1,10-phenanthroline (0.0436 g, 0.203 mmol), and the mixed solution was stirred for a few minutes. The yellow single crystals were obtained after the filtrate had been allowed to stand at room temperature for about one week.

Refinement
All H atoms were placed in calculated positions, and refined as riding, with C-H = 0.93 Å, U iso = 1.2U eq (C).
supplementary materials sup-2 Figures Fig. 1. The content of asymmetric unit of (I) showing the atomic numbering and 30% probability displacement ellipsoids.

Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.