Volatile heteroligand compounds of Zn(i-Bu2PS2)(2) with Phen, 2,2'-Bipy, and 4,4'-Bipy were synthesized. The structure of Zn(4,4'-Bipy)(i-Bu2PS2)(2) was determined from the single-crystal X-ray data (CAD-4 diffractometer, MoKalpha radiation, 2539 reflections. R = 0.0320). The crystals are triclinic: a = 9.090(2); b = 9.465(2), c = 10.179(2) Angstrom; alpha = 93.13(3)degrees, beta = 107.33(3)degrees, gamma = 103.89(3)degrees, V= 804.0(3) Angstrom(3), Z= 1, rho(calcd) = 1.322 g/cm(3), space group P (1) over bar. The structure is formed from linear polymeric chains oriented along the [110] direction. The coordination polyhedron of the Zn atom is a distorted octahedron (4S + 2N); and the polyhedron of the P atoms is a (2S + 2C) tetrahedron. The study of the thermal properties in air and in vacuo showed that these compounds are of interest as precursors for chemical vapor deposition of ZnS films.