Ga5(PS)3 crystallizes in the orthorhombic Pmm2 space group. There are three inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to one P(1), one S(2), and two equivalent S(1) atoms to form GaPS3 tetrahedra that share  a cornercorner with one Ga(2)P4 tetrahedra, corners with three equivalent Ga(1)PS3 tetrahedra, and corners with four equivalent Ga(3)P3S tetrahedra. In the second Ga site, Ga(2) is bonded to two equivalent P(1) and two equivalent P(2) atoms to form GaP4 tetrahedra that share corners with two equivalent Ga(2)P4 tetrahedra, corners with two equivalent Ga(1)PS3 tetrahedra, and corners with eight equivalent Ga(3)P3S tetrahedra. In the third Ga site, Ga(3) is bonded to one P(2), two equivalent P(1), and one S(1) atom to form GaP3S tetrahedra that share corners with three equivalent Ga(3)P3S tetrahedra, corners with four equivalent Ga(2)P4 tetrahedra, and corners with four equivalent Ga(1)PS3 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one Ga(1), one Ga(2), and two equivalent Ga(3) atoms to form corner-sharing PGa4 tetrahedra. In the second P site, P(2) is bonded to two equivalent Ga(2) and two equivalent Ga(3) atoms to form corner-sharing PGa4 tetrahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded in a trigonal non-coplanar geometry to one Ga(3) and two equivalent Ga(1) atoms. In the second S site, S(2) is bonded in a water-like geometry to two equivalent Ga(1) atoms.
Ga5(PS)3 crystallizes in the orthorhombic Pmm2 space group. There are three inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to one P(1), one S(2), and two equivalent S(1) atoms to form GaPS3 tetrahedra that share  a cornercorner with one Ga(2)P4 tetrahedra, corners with three equivalent Ga(1)PS3 tetrahedra, and corners with four equivalent Ga(3)P3S tetrahedra. The Ga(1)-P(1) bond length is 2.36 Å. The Ga(1)-S(2) bond length is 2.21 Å. Both Ga(1)-S(1) bond lengths are 2.36 Å. In the second Ga site, Ga(2) is bonded to two equivalent P(1) and two equivalent P(2) atoms to form GaP4 tetrahedra that share corners with two equivalent Ga(2)P4 tetrahedra, corners with two equivalent Ga(1)PS3 tetrahedra, and corners with eight equivalent Ga(3)P3S tetrahedra. Both Ga(2)-P(1) bond lengths are 2.36 Å. Both Ga(2)-P(2) bond lengths are 2.34 Å. In the third Ga site, Ga(3) is bonded to one P(2), two equivalent P(1), and one S(1) atom to form GaP3S tetrahedra that share corners with three equivalent Ga(3)P3S tetrahedra, corners with four equivalent Ga(2)P4 tetrahedra, and corners with four equivalent Ga(1)PS3 tetrahedra. The Ga(3)-P(2) bond length is 2.35 Å. Both Ga(3)-P(1) bond lengths are 2.34 Å. The Ga(3)-S(1) bond length is 2.31 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one Ga(1), one Ga(2), and two equivalent Ga(3) atoms to form corner-sharing PGa4 tetrahedra. In the second P site, P(2) is bonded to two equivalent Ga(2) and two equivalent Ga(3) atoms to form corner-sharing PGa4 tetrahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded in a trigonal non-coplanar geometry to one Ga(3) and two equivalent Ga(1) atoms. In the second S site, S(2) is bonded in a water-like geometry to two equivalent Ga(1) atoms.