Low-Dimensional Sulfoantimonates with Metal Complexes as Counterions. Hydrothermal Synthesis and Properties of [M(en)(3)]Sb(2)S(4) (M = Co, Ni) and [M(en)(3)]Sb(4)S(7) (M = Fe, Ni).
[M(en)(3)]Sb(2)S(4) (M = Co, Ni) and [M(en)(3)]Sb(4)S(7) (M = Fe, Ni) were prepared from the MX(2)/Na(3)SbS(3)/en system (X = Cl, Br; en = ethylenediamine) under hydrothermal conditions. Orange-yellow [Ni(en)(3)]Sb(2)S(4) (1) crystallizes in the monoclinic space group P2(1)/c (No. 14) with a = 10.538(2) Å, b = 14.460(4) Å, c = 12.434(5) Å, beta = 99.93(2) degrees, and Z = 4. Green-yellow [Co(en)(3)]Sb(2)S(4) (2) crystallizes as a superstructure of 1 with a = 21.131(4) Å, b = 14.619(2) Å, c = 12.540(2) Å, beta = 100.50(1) degrees, and Z = 8. The antimony sulfide frameworks in 1 and 2 consist of SbS(3) pyramids sharing two corners to form 1/infinity[SbS(2)](-) chains. Orange-yellow [Ni(en)(3)]Sb(4)S(7) (3) crystallizes in the monoclinic space group P2(1)/c (No. 14) with a = 9.930(1) Å, b = 14.212(2) Å, c = 17.242(2) Å, beta = 102.55(1) degrees, and Z = 4. The 1/infinity[Sb(4)S(7)](2)(-) chains are formed by corner-sharing SbS(3) units. Three of these pyramids are arranged to cyclic Sb(3)S(6) trimers which share two of the three exocyclic S-atoms with the fourth SbS(3) units to form infinite chains. [Fe(en)(3)]Sb(4)S(7) (4) is isostructural to 3. In all four compounds the tris(ethylenediamine)metal(II) complexes act as counterions. The thermal, magnetic and optical properties of compounds 1-4 are reported.
Stephan
Hans-Oscar
HO
Department of Chemistry and Center for Fundamental Materials Research, Michigan State University, East Lansing, Michigan 48824.
Kanatzidis
Mercouri G.
MG