Synthesis and Characterization of (Ph₄P)₂[Ni₂As₄S₈], (Me₄N)₂[Mo₂O₂As₂S₇], and (Et₄N)₂[Mo₂O₂As₂Se₇]. New One-Dimensional Polymeric Compounds Containing Thio- and Selenoarsenate Ligands

Abstract

The compounds (Ph 4 P) 2 [Ni 2 As 4 S 8 ] ( I ), (Me 4 N) 2 [Mo 2 O 2 As 2 S 7 ] ( II ), and (Et 4 N) 2 [Mo 2 O 2 As 2 Se 7 ] ( III ) were synthesized by the hydrothermal reactions of NiCl 2 /K 3 AsS 3 /Ph 4 PBr, MoO 3 /K 3 AsS 3 /Me 4 NCl, and MoO 3 /K 3 AsSe 3 /Et 4 NBr in a 1:3:4, 1:2:4, and 1:4:6 molar ratio, respectively. The (Ph 4 P) 2 [Ni 2 As 4 S 8 ] ( I ) crystallizes in the triclinic space group P 1̄ (No. 2) with a = 10.613(3) Å, b = 13.230(2) Å, c = 9.617(2) Å, α = 93.53(2)°, β = 96.69(2)°, γ = 71.59(2)°, V = 1272(1) Å 3, and Z = 2. The one-dimensional [Ni 2 As 4 S 8 ] n 2 n - consists of alternating square planar Ni 2+ ions and [As 4 S 8 ] 4 - ligands. The (Me 4 N) 2 [Mo 2 O 2 As 2 S 7 ] ( II ) crystallizes in the orthorhombic space group Pbca (No. 61) with a = 18.176(4) Å, b = 17.010(2) Å, c = 16.556(7) Å, V = 5118(4) Å 3, and Z = 4. The [Mo 2 O 2 As 2 S 7 ] n 2 n - macroanion possesses a one-dimensional chain-like structure consisting of [Mo 2 O 2 S 2 ] 2+ cores linked by [As 2 S 5 ] 4 - ligands. The (Et 4 N) 2 [Mo 2 O 2 As 2 Se 7 ] ( III ) crystallizes in the orthorhombic space group Cmca No. 64) with a = 15.480(2) Å, b = 18.506(2) Å, c = 22.793(2) Å, V = 6350(1) Å 3, and Z = 4. The [Mo 2 O 2 As 2 Se 7 ] n 2 n - is isostructural to the anion in II . The solid state optical spectra of these compounds are reported.