IONIC CLUSTER DITHIOPHOSPHINATES [MO3S4(R2PS2)3PY3]- (M=ZN.PY, CD.PY,HG)([MI3])

Reactions of clusters Mo3S4L4 (2) (L = R2P(S)S-; R = Et (a), Pr (b)) w ith MI2 (M = Zn, Cd, Hg) in the presence of pyridine yielded ionic clu sters [Mo3S4L3py3]+[MI3py]- (M = Zn (9), Cd (10); R = Et (a), Pr (b)) and [Mo3S4L3py3]+[HgI3]- (11) (L = Pr2P(S)S-), respectively. The clust er cations consist of a triangular array of Mo atoms which are bridged by three S atoms and capped by the fourth S atom. Each of the Mo atom s is chelated by one L and coordinated by one pyridine. 9a crystallize s in the monoclinic space group P2(1) with Z = 2 formula units in the unit cell of dimensions a = 1120.9(2), b = 1756.3(3), c = 1447.3(2) pm , beta = 105.31(l)-degrees, D(c) = 1.98 mg/mm3. The crystal structure was refined to R = 0.04 using 5599 observed reflections and consists o f [Mo3S4(Et2PS)3py3]+[ZnI3py]-. The coordination number of the Mo atom s is 8. The average distance Mo-Mo is 276.6(2) pm. The Zn atom is coor dinated tetrahedrally with average distance Zn-I of 259.0(2) and Zn-N of 208.8(11) pm.