The title compound, [Cu(C5H5NO2S2)(C18H15P)2]·CHCl3, features a tetrahedrally coordinated CuI atom within a P2S2 donor set defined by two phosphane P atoms and by two S atoms derived from a symmetrically coordinating dithiocarbamate ligand. Both intra- and intermolecular hydroxy-O-H...O(hydroxy) hydrogen bonding is observed: the former closes an eight-membered {...HOC2NC2O} ring, whereas the latter connects centrosymmetrically related molecules into dimeric aggregates via eight-membered {...H-O...H-O}2 synthons. The complex molecules are arranged to form channels along the c axis in which reside the chloroform molecules, being connected by Cl...[pi](arene) and short S...Cl [3.3488 (9) Å] interactions. The intermolecular interactions have been investigated further by Hirshfeld surface analysis, which shows the conventional hydrogen bonding to be very localized with the main contributors to the surface, at nearly 60%, being H...H contacts. Solution NMR studies indicate that whilst the same basic molecular structure is retained in solution, the triphenylphosphane ligands are highly labile, exchanging rapidly with free Ph3P at room temperature.
