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(CuBr)2P8Se3 crystallizes in the orthorhombic Pbcm space group. The structure is zero-dimensional and consists of four bromocopper molecules, eight phosphine molecules, and twelve PPSe clusters. In each PPSe cluster, P+0.75+ is bonded in a distorted single-bond geometry to one Se2- atom. The P–Se bond length is 2.29 Å. Se2- is bonded in an L-shaped geometry to two equivalent P+0.75+ atoms.
(CuBr)3(P4Se3)2 crystallizes in the orthorhombic Pnma space group. The structure is one-dimensional and consists of eight tetraphosphorous triselenide molecules and six CuBr ribbons oriented in the (1, 0, 0) direction. In each CuBr ribbon, Cu+1.67+ is bonded in a water-like geometry to two equivalent Br1- atoms. There are one shorter (2.47 Å) and one longer (2.50 Å) Cu–Br bond lengths. Br1- is bonded in a bent 120 degrees geometry to two equivalent Cu+1.67+ atoms.