MgV2(RhO4)2 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom to form MgO6 octahedra that share corners with two equivalent Rh(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Rh(1)O6 octahedra, and  a faceface with one Rh(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form VO6 octahedra that share corners with four equivalent Rh(2)O6 octahedra, edges with two equivalent Mg(1)O6 octahedra, and edges with two equivalent Rh(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-58°. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(7), and one O(8) atom. There are two inequivalent Rh sites. In the first Rh site, Rh(1) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form RhO6 octahedra that share corners with four equivalent Rh(2)O6 octahedra, edges with two equivalent Mg(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-57°. In the second Rh site, Rh(2) is bonded to one O(1), one O(2), one O(4), one O(6), one O(7), and one O(8) atom to form distorted RhO6 octahedra that share corners with two equivalent Mg(1)O6 octahedra, corners with four equivalent V(1)O6 octahedra, corners with four equivalent Rh(1)O6 octahedra, and  a faceface with one Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-58°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Mg(1), one V(1), one V(2), and one Rh(2) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(2), one Rh(1), and one Rh(2) atom. In the third O site, O(3) is bonded to one Mg(1), one V(1), one V(2), and one Rh(1) atom to form distorted OMgV2Rh trigonal pyramids that share  a cornercorner with one O(7)MgV2Rh trigonal pyramid,  a cornercorner with one O(8)MgVRh2 trigonal pyramid,  an edgeedge with one O(7)MgV2Rh trigonal pyramid, and  an edgeedge with one O(8)MgVRh2 trigonal pyramid. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(1), one Rh(1), and one Rh(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Rh(1) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one Rh(1), and one Rh(2) atom. In the seventh O site, O(7) is bonded to one Mg(1), one V(1), one V(2), and one Rh(2) atom to form distorted OMgV2Rh trigonal pyramids that share  a cornercorner with one O(3)MgV2Rh trigonal pyramid,  a cornercorner with one O(8)MgVRh2 trigonal pyramid,  an edgeedge with one O(3)MgV2Rh trigonal pyramid, and  an edgeedge with one O(8)MgVRh2 trigonal pyramid. In the eighth O site, O(8) is bonded to one Mg(1), one V(2), one Rh(1), and one Rh(2) atom to form a mixture of distorted corner and edge-sharing OMgVRh2 trigonal pyramids.
MgV2(RhO4)2 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom to form MgO6 octahedra that share corners with two equivalent Rh(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Rh(1)O6 octahedra, and  a faceface with one Rh(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. The Mg(1)-O(1) bond length is 2.10 Å. The Mg(1)-O(2) bond length is 2.14 Å. The Mg(1)-O(3) bond length is 1.94 Å. The Mg(1)-O(6) bond length is 1.96 Å. The Mg(1)-O(7) bond length is 2.07 Å. The Mg(1)-O(8) bond length is 2.07 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form VO6 octahedra that share corners with four equivalent Rh(2)O6 octahedra, edges with two equivalent Mg(1)O6 octahedra, and edges with two equivalent Rh(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-58°. The V(1)-O(1) bond length is 2.09 Å. The V(1)-O(3) bond length is 1.95 Å. The V(1)-O(4) bond length is 1.88 Å. The V(1)-O(5) bond length is 2.04 Å. The V(1)-O(6) bond length is 2.00 Å. The V(1)-O(7) bond length is 1.98 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(7), and one O(8) atom. The V(2)-O(1) bond length is 1.96 Å. The V(2)-O(2) bond length is 1.93 Å. The V(2)-O(3) bond length is 2.36 Å. The V(2)-O(5) bond length is 1.79 Å. The V(2)-O(7) bond length is 2.10 Å. The V(2)-O(8) bond length is 2.04 Å. There are two inequivalent Rh sites. In the first Rh site, Rh(1) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form RhO6 octahedra that share corners with four equivalent Rh(2)O6 octahedra, edges with two equivalent Mg(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-57°. The Rh(1)-O(2) bond length is 2.08 Å. The Rh(1)-O(3) bond length is 2.08 Å. The Rh(1)-O(4) bond length is 2.01 Å. The Rh(1)-O(5) bond length is 2.04 Å. The Rh(1)-O(6) bond length is 2.08 Å. The Rh(1)-O(8) bond length is 2.07 Å. In the second Rh site, Rh(2) is bonded to one O(1), one O(2), one O(4), one O(6), one O(7), and one O(8) atom to form distorted RhO6 octahedra that share corners with two equivalent Mg(1)O6 octahedra, corners with four equivalent V(1)O6 octahedra, corners with four equivalent Rh(1)O6 octahedra, and  a faceface with one Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-58°. The Rh(2)-O(1) bond length is 2.12 Å. The Rh(2)-O(2) bond length is 2.08 Å. The Rh(2)-O(4) bond length is 1.99 Å. The Rh(2)-O(6) bond length is 2.19 Å. The Rh(2)-O(7) bond length is 2.06 Å. The Rh(2)-O(8) bond length is 2.04 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Mg(1), one V(1), one V(2), and one Rh(2) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(2), one Rh(1), and one Rh(2) atom. In the third O site, O(3) is bonded to one Mg(1), one V(1), one V(2), and one Rh(1) atom to form distorted OMgV2Rh trigonal pyramids that share  a cornercorner with one O(7)MgV2Rh trigonal pyramid,  a cornercorner with one O(8)MgVRh2 trigonal pyramid,  an edgeedge with one O(7)MgV2Rh trigonal pyramid, and  an edgeedge with one O(8)MgVRh2 trigonal pyramid. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(1), one Rh(1), and one Rh(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Rh(1) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one Rh(1), and one Rh(2) atom. In the seventh O site, O(7) is bonded to one Mg(1), one V(1), one V(2), and one Rh(2) atom to form distorted OMgV2Rh trigonal pyramids that share  a cornercorner with one O(3)MgV2Rh trigonal pyramid,  a cornercorner with one O(8)MgVRh2 trigonal pyramid,  an edgeedge with one O(3)MgV2Rh trigonal pyramid, and  an edgeedge with one O(8)MgVRh2 trigonal pyramid. In the eighth O site, O(8) is bonded to one Mg(1), one V(2), one Rh(1), and one Rh(2) atom to form a mixture of distorted corner and edge-sharing OMgVRh2 trigonal pyramids.