π-π stacking force in the solid structure of mixed-metal complexes:: Zn(phen)2MS4 (M=W, Mo)

The inter-diffusion of NN-dimethylformamide solution of Zn(phen)(2)Cl-2 and (NH4)(2)MS4 (M = W, Mo) in an H-shape tube produced crystals of Zn(phen)(2)WS4 1 and Zn(phen)(2)MoS4 2 (phen = 1,10-phenanthroline). The structures of isomorphous complexes 1 and 2 have been determined by X-ray single-crystal structure analyses. Four nitrogen atoms from the phenanthroline ligands and two sulfur atoms from the MS42- anion forming a distorted octahedron coordinate each zinc atom. Through pi-pi interactions of adjacent aromatic rings of the phenanthroline ligands, a quasi one-dimensional zigzag-stacking column is formed in each complex. Complex 1 crystallizes, in monoclinic space group C2/c, with a = 10.447(8), b = 22.016(9), c = 12.824(8) Angstrom, beta = 103.56(6)degrees, V = 2867.7(8)Angstrom (3), Z = 4, C24H16N4S4WZn, M-r = 737.90, D-c = 1.71 g/cm(3), F(000) = 1424, mu = 5.25 mm(-1), the final R = 0.054 and Rw = 0.075 for 2315 observations with I>3 sigma (I). Complex 2 crystallizes in monoclinic space group C2/c, with a = 10.410(6), b = 22.095(7), c = 12.830(6)Angstrom, beta = 103.19(8)degrees, V = 2873.1(5) Angstrom (3), Z = 4, C24H16MoN4S4Zn, M-r = 649.99, D-c = 1.50 g/cm(3), F(000) = 1296, mu = 1.58 mm(-1), the final R = 0.072 and Rw = 0.100 for 1631 observations with I>3 sigma (I).