SYNTHESIS AND CHARACTERIZATION OF (PH(4)P)(2)[NI2AS4S8], (ME(4)N)(2)[MO2O2AS2S7], AND (ET(4)N)(2)[MO2O2AS2SE7], NEW ONE-DIMENSIONAL POLYMERIC COMPOUNDS CONTAINING THIOARSENATE AND SELENOARSENATE LIGANDS

The compounds (Ph(1)P)(2)[Ni2As4S8] (I), (Me(4)N)(2)[Mo2O2As2S7] (II), and (Et(4)N)(2)[Mo2O2As2Se7] (III) were synthesized by the hydrotherm al reactions of NiCl2/K3AsS3/Ph(4)PBr, MoO3/K3AsS3/Me(4)NCl, and MoO3/ K3AsSe3/Et4NBr in a 1:3:4, 1:2:4, and 1:4:6 molar ration, respectively . The (Ph(4)P)(2)[Ni2As4S8] (I) crystallizes in the triclinic space gr oup <P(1)over bar> (No. 2) with a = 10.613(3) Angstrom, b = 13.230(2) Angstrom, c = 9.617(2) Angstrom, alpha = 93.53(2)degrees, beta = 96.69 (2)degrees, gamma = 71.59(2)degrees, V = 1272(1) Angstrom(3), and Z = 2. The one-dimensional [Ni2As4S8](2n-)(n) consists of alternating squa re planar Ni2+ ions and [As4S8](4-) ligands. The (Me(4)N)(2)[Mo2O2As2S 7] (II) crystallizes in the orthorhombic space group Pbca (No. 61) wit h a = 18.176(4) Angstrom, b = 17.010(2) Angstrom, c = 16.556(7) Angstr om, V = 5118(4) Angstrom(3), and Z = 4. The [Mo2O2As2S7](2n-)(n) macro anion possesses a one-dimensional chain-like structure consisting of [ Mo2O2S2](2+) cores linked by [As2S5](4-) ligands. The (Et(4)N)(2)[Mo2O 2As2Se7] (III) crystallizes in the orthorhombic space group Cmca No. 6 4) with a = 15.480(2) Angstrom, b = 18.506(2) Angstrom, c = 22.793(2) Angstrom, V = 6350(1) Angstrom(3), and Z = 4. The [Mo2O2As2Se7](2n-)(n ) is isostructural to the anion in II. The solid state optical spectra of these compounds are reported.