Two polymorphs of tetraethylammonium [hydrogen tris(3,5‐dimethylpyrazolyl)borato]di‐μ2‐sulfido‐disulfido(η2‐tetrasulfido)ditungsten(V) with Z′ = 1 and 2

Two polymorphs of the title compound, (C₈H₂₀N)W₂S₄(S₄)(C₁₅H₂₂BN₆)], have been obtained unexpectedly by attempted recrystallization of a mixed‐metal–sulfur cluster complex from different solvents. The dinuclear complex anion contains W^V in two different coordination environments, one of them distorted octahedral with a tris(pyrazolyl)borate anion, a terminal sulfide and two bridging sulfide ligands, the other distorted square‐pyramidal with a terminal sulfide, two bridging sulfide and a chelating tetrasulfide ligand. The three independent anions in the two polymorphs have essentially the same geometry. The central W₂S₂ ring is a slightly folded rhombus with acute angles at the S atoms, and the WS₄ chelate ring is an envelope with one noncoordinating S atom as the flap. The second polymorph, with Z′ = 2 and pseudo‐inversion symmetry relating the anions of the asymmetric unit, also displays pseudo‐translation features in its layer structure, and all examined crystals were found to be twinned, possibly as a consequence of this structural feature.