Structure of thiocarbamide-containing cobalt(III) dioximates with [BeF4]2− and [BF4]− anions

Abstract

The crystal structure of the complexes [Co(DH)2(Tu)2]2[BeF4]·C2H5OH (I) and [Co(DfH)2(Tu)2][BF4] 0.5H2 (II) (where DH− is the dimethylglyoxime monoanion, DfH− is the α-benzyldioxime monoanion, and Tu is thiourea) has been determined by X-ray diffraction analysis. The coordination polyhedron of the Co3+ atom is an N4S2 octahedron formed by four nitrogen atoms of the dioxime molecule and two sulfur atoms of the fragments of thiourea (Tu); the latter have parallel and perpendicular orientations relative to the dioxime residue. The deviation of the cobalt atom from the four-angle plane (formed by the nitrogen atoms of the dimethylglyoxime residues) does not exceed 0.019 A. The Co-N and Co-S distances vary from 1.877(3) A to 1.901(3) A and from 2.280(1) A to 2.307(1) A, respectively. The statistically disordered cations [BeF4]2− and [BF4]− play an important role in crystal formation — they form a complex system of hydrogen bonds.