Crystal structures of [bis(triisobutylphosphonium)trisulfane]-di[nonachlorooxodiniobiate(V)], [(((CH3)2CHCH2)3P)2S3][Nb2OCl9]2 and [octachloro(triisobutylphosphinesulfide)-oxodiniobium(V)], [Nb2OCl8{((CH3)2CHCH2)3PS}]

Abstract

Abstract Red crystals of [(((CH3)2CHCH2)3P)2S3] [Nb2OCl9]2 1 and [Nb2OCl8{((CH3)2CHCH2)3PS}] 2 were obtained from equimolar solutions of niobium pentachloride and triisobutylphosphinesulfide in dichloromethane. The oxygen in the compounds originates from a reaction of the educts with traces of water. The complexes were characterized by single crystal structure determination. 1, triclinic, S.G.: P[unk] (Nr. 2), a = 10.986(1) Å, b = 11.069(1) Å, c = 26.473(2) Å, α = 95.16(l)°, β = 92.97(1)°, γ = 116.61(1)°, V = 2851.2(4) Å3, Z = 2. 2, triclinic, S.G.: P[unk] (Nr. 2), a = 10.818(1) Å, b = 16.705(2) Å, c = 16.782(2) Å, α = 65.69(1)°, β = 82.23(1)°, γ = 88.63(1)°, V = 2736.8(5) Å3, Z = 4. The asymmetric unit of 1 consists of a [(((CH3)2CHCH2)3P)2S3] cation with a PSSSP-chain and two [Nb2OCl9)]−-anions. The anions have nearly linear Nb–O–Nb bridges (bond angles 169.3(3)° and 172.1(3)°) and Nb–O bond lengths of 1.746(5) Å for the short and 2.121(5) Å for the long bonds. Two anions are linked by symmetric chlorine bridges with bond lengths of 2.76 Å and 2.77 Å to form a dimer. 2 is built of neutral [Nb2OCl8{((CH3)2CHCH2)3PS}] complexes. The Nb–O–Nb angles and Nb–O bond distances correspond to those found in 1. The neutral complexes in 2 are linked by symmetric chlorine bridges, analog 1, to dimers.