A novel tetranuclear copper(I) sulfanide complex with bis(diphenylphosphino)amine

The title novel mixed μ₂‐SH‐ and μ₃‐SH‐bridged tetranuclear copper(I) complex, cyclo‐bisμ₂‐bis(diphenylphosphino)amine]di‐μ₃‐sulfanido‐di‐μ₂‐sulfanido‐tetracopper(I) methanol disolvate, Cu₄(SH)₄(C₂₄H₂₁NP₂)₂]·2CH₃OH, has crystallographically imposed centrosymmetry and affords a neutral Cu₄S₄ core with a distorted step‐like structure. The distances of 2.8458 (16) and 2.8179 (16) Å between copper(I) centres indicate the presence of ligand‐supported Cu...Cu interactions. Strong N—H...O and O—H...S hydrogen bonds between the tetranuclear cluster and methanol solvent molecules result in a two‐dimensional hydrogen‐bonded supramolecular network. This complex is the first example of a coinage tetranuclear metal complex with mixed μ₂‐SH‐ and μ₃‐SH‐bridged chromophores.