RbHo2Cu3S5 crystallizes in the orthorhombic Cmcm space group. Rb(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), and four equivalent S(3) atoms. Ho(1) is bonded to one S(2), two equivalent S(3), and three equivalent S(1) atoms to form HoS6 octahedra that share  a cornercorner with one Ho(1)S6 octahedra, corners with four equivalent Cu(1)S4 tetrahedra, edges with four equivalent Ho(1)S6 octahedra, edges with two equivalent Cu(2)S4 tetrahedra, and edges with three equivalent Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 28°. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent S(1) and two equivalent S(3) atoms to form distorted CuS4 tetrahedra that share corners with four equivalent Ho(1)S6 octahedra, corners with two equivalent Cu(1)S4 tetrahedra, corners with two equivalent Cu(2)S4 tetrahedra, edges with three equivalent Ho(1)S6 octahedra, and  an edgeedge with one Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-60°. In the second Cu site, Cu(2) is bonded to two equivalent S(2) and two equivalent S(3) atoms to form distorted CuS4 tetrahedra that share corners with two equivalent Cu(2)S4 tetrahedra, corners with four equivalent Cu(1)S4 tetrahedra, and edges with four equivalent Ho(1)S6 octahedra. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Rb(1), three equivalent Ho(1), and two equivalent Cu(1) atoms to form a mixture of distorted edge and corner-sharing SRbHo3Cu2 octahedra. The corner-sharing octahedral tilt angles are 51°. In the second S site, S(2) is bonded in a 6-coordinate geometry to two equivalent Rb(1), two equivalent Ho(1), and two equivalent Cu(2) atoms. In the third S site, S(3) is bonded in a 7-coordinate geometry to two equivalent Rb(1), two equivalent Ho(1), one Cu(2), and two equivalent Cu(1) atoms.
RbHo2Cu3S5 crystallizes in the orthorhombic Cmcm space group. Rb(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), and four equivalent S(3) atoms. Both Rb(1)-S(1) bond lengths are 3.30 Å. Both Rb(1)-S(2) bond lengths are 3.37 Å. All Rb(1)-S(3) bond lengths are 3.48 Å. Ho(1) is bonded to one S(2), two equivalent S(3), and three equivalent S(1) atoms to form HoS6 octahedra that share  a cornercorner with one Ho(1)S6 octahedra, corners with four equivalent Cu(1)S4 tetrahedra, edges with four equivalent Ho(1)S6 octahedra, edges with two equivalent Cu(2)S4 tetrahedra, and edges with three equivalent Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 28°. The Ho(1)-S(2) bond length is 2.67 Å. Both Ho(1)-S(3) bond lengths are 2.70 Å. There is one shorter (2.70 Å) and two longer (2.80 Å) Ho(1)-S(1) bond lengths. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent S(1) and two equivalent S(3) atoms to form distorted CuS4 tetrahedra that share corners with four equivalent Ho(1)S6 octahedra, corners with two equivalent Cu(1)S4 tetrahedra, corners with two equivalent Cu(2)S4 tetrahedra, edges with three equivalent Ho(1)S6 octahedra, and  an edgeedge with one Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-60°. Both Cu(1)-S(1) bond lengths are 2.35 Å. There is one shorter (2.39 Å) and one longer (2.49 Å) Cu(1)-S(3) bond length. In the second Cu site, Cu(2) is bonded to two equivalent S(2) and two equivalent S(3) atoms to form distorted CuS4 tetrahedra that share corners with two equivalent Cu(2)S4 tetrahedra, corners with four equivalent Cu(1)S4 tetrahedra, and edges with four equivalent Ho(1)S6 octahedra. Both Cu(2)-S(2) bond lengths are 2.28 Å. Both Cu(2)-S(3) bond lengths are 2.61 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Rb(1), three equivalent Ho(1), and two equivalent Cu(1) atoms to form a mixture of distorted edge and corner-sharing SRbHo3Cu2 octahedra. The corner-sharing octahedral tilt angles are 51°. In the second S site, S(2) is bonded in a 6-coordinate geometry to two equivalent Rb(1), two equivalent Ho(1), and two equivalent Cu(2) atoms. In the third S site, S(3) is bonded in a 7-coordinate geometry to two equivalent Rb(1), two equivalent Ho(1), one Cu(2), and two equivalent Cu(1) atoms.