MgV4(CuO4)3 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a 8-coordinate geometry to one Cu(2), one O(1), one O(2), one O(3), one O(5), one O(7), one O(8), and one O(9) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), one O(2), one O(3), one O(5), and one O(6) atom to form corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 34-40°. In the second V site, V(2) is bonded to one O(1), one O(12), one O(3), one O(4), one O(5), and one O(9) atom to form corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 34-41°. In the third V site, V(3) is bonded to one O(1), one O(12), one O(2), one O(6), one O(7), and one O(8) atom to form corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 34-43°. In the fourth V site, V(4) is bonded to one O(10), one O(11), one O(4), one O(7), one O(8), and one O(9) atom to form corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 34-43°. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a rectangular see-saw-like geometry to one O(2), one O(4), one O(6), and one O(9) atom. In the second Cu site, Cu(2) is bonded in a 6-coordinate geometry to one Mg(1), one O(12), one O(3), one O(4), one O(6), and one O(8) atom. In the third Cu site, Cu(3) is bonded in a rectangular see-saw-like geometry to one O(1), one O(10), one O(11), and one O(12) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Mg(1), one V(2), one V(3), and one Cu(3) atom. In the second O site, O(2) is bonded to one Mg(1), one V(1), one V(3), and one Cu(1) atom to form OMgV2Cu trigonal pyramids that share  a cornercorner with one O(4)V2Cu2 trigonal pyramid, corners with three equivalent O(6)V2Cu2 trigonal pyramids, and  an edgeedge with one O(9)MgV2Cu trigonal pyramid. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), one V(2), and one Cu(2) atom. In the fourth O site, O(4) is bonded to one V(2), one V(4), one Cu(1), and one Cu(2) atom to form distorted OV2Cu2 trigonal pyramids that share  a cornercorner with one O(2)MgV2Cu trigonal pyramid, corners with three equivalent O(9)MgV2Cu trigonal pyramids, and  an edgeedge with one O(6)V2Cu2 trigonal pyramid. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one V(2) atom. In the sixth O site, O(6) is bonded to one V(1), one V(3), one Cu(1), and one Cu(2) atom to form distorted OV2Cu2 trigonal pyramids that share  a cornercorner with one O(9)MgV2Cu trigonal pyramid, corners with three equivalent O(2)MgV2Cu trigonal pyramids, and  an edgeedge with one O(4)V2Cu2 trigonal pyramid. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Mg(1), one V(3), and one V(4) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(3), one V(4), and one Cu(2) atom. In the ninth O site, O(9) is bonded to one Mg(1), one V(2), one V(4), and one Cu(1) atom to form OMgV2Cu trigonal pyramids that share  a cornercorner with one O(6)V2Cu2 trigonal pyramid, corners with three equivalent O(4)V2Cu2 trigonal pyramids, and  an edgeedge with one O(2)MgV2Cu trigonal pyramid. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one Cu(3) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one Cu(3) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one V(2), one V(3), one Cu(2), and one Cu(3) atom.
MgV4(CuO4)3 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a 8-coordinate geometry to one Cu(2), one O(1), one O(2), one O(3), one O(5), one O(7), one O(8), and one O(9) atom. The Mg(1)-Cu(2) bond length is 2.26 Å. The Mg(1)-O(1) bond length is 2.54 Å. The Mg(1)-O(2) bond length is 1.97 Å. The Mg(1)-O(3) bond length is 2.48 Å. The Mg(1)-O(5) bond length is 2.07 Å. The Mg(1)-O(7) bond length is 2.07 Å. The Mg(1)-O(8) bond length is 2.36 Å. The Mg(1)-O(9) bond length is 1.99 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), one O(2), one O(3), one O(5), and one O(6) atom to form corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 34-40°. The V(1)-O(10) bond length is 1.93 Å. The V(1)-O(11) bond length is 1.88 Å. The V(1)-O(2) bond length is 2.02 Å. The V(1)-O(3) bond length is 2.05 Å. The V(1)-O(5) bond length is 2.01 Å. The V(1)-O(6) bond length is 2.03 Å. In the second V site, V(2) is bonded to one O(1), one O(12), one O(3), one O(4), one O(5), and one O(9) atom to form corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 34-41°. The V(2)-O(1) bond length is 2.04 Å. The V(2)-O(12) bond length is 2.12 Å. The V(2)-O(3) bond length is 1.95 Å. The V(2)-O(4) bond length is 2.08 Å. The V(2)-O(5) bond length is 1.82 Å. The V(2)-O(9) bond length is 1.97 Å. In the third V site, V(3) is bonded to one O(1), one O(12), one O(2), one O(6), one O(7), and one O(8) atom to form corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 34-43°. The V(3)-O(1) bond length is 1.87 Å. The V(3)-O(12) bond length is 1.95 Å. The V(3)-O(2) bond length is 2.00 Å. The V(3)-O(6) bond length is 2.04 Å. The V(3)-O(7) bond length is 1.99 Å. The V(3)-O(8) bond length is 2.13 Å. In the fourth V site, V(4) is bonded to one O(10), one O(11), one O(4), one O(7), one O(8), and one O(9) atom to form corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 34-43°. The V(4)-O(10) bond length is 2.01 Å. The V(4)-O(11) bond length is 2.16 Å. The V(4)-O(4) bond length is 2.01 Å. The V(4)-O(7) bond length is 1.84 Å. The V(4)-O(8) bond length is 1.92 Å. The V(4)-O(9) bond length is 2.05 Å. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a rectangular see-saw-like geometry to one O(2), one O(4), one O(6), and one O(9) atom. The Cu(1)-O(2) bond length is 1.95 Å. The Cu(1)-O(4) bond length is 2.00 Å. The Cu(1)-O(6) bond length is 1.97 Å. The Cu(1)-O(9) bond length is 1.98 Å. In the second Cu site, Cu(2) is bonded in a 6-coordinate geometry to one Mg(1), one O(12), one O(3), one O(4), one O(6), and one O(8) atom. The Cu(2)-O(12) bond length is 2.21 Å. The Cu(2)-O(3) bond length is 1.96 Å. The Cu(2)-O(4) bond length is 1.93 Å. The Cu(2)-O(6) bond length is 1.91 Å. The Cu(2)-O(8) bond length is 1.96 Å. In the third Cu site, Cu(3) is bonded in a rectangular see-saw-like geometry to one O(1), one O(10), one O(11), and one O(12) atom. The Cu(3)-O(1) bond length is 2.16 Å. The Cu(3)-O(10) bond length is 1.93 Å. The Cu(3)-O(11) bond length is 1.94 Å. The Cu(3)-O(12) bond length is 2.04 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Mg(1), one V(2), one V(3), and one Cu(3) atom. In the second O site, O(2) is bonded to one Mg(1), one V(1), one V(3), and one Cu(1) atom to form OMgV2Cu trigonal pyramids that share  a cornercorner with one O(4)V2Cu2 trigonal pyramid, corners with three equivalent O(6)V2Cu2 trigonal pyramids, and  an edgeedge with one O(9)MgV2Cu trigonal pyramid. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), one V(2), and one Cu(2) atom. In the fourth O site, O(4) is bonded to one V(2), one V(4), one Cu(1), and one Cu(2) atom to form distorted OV2Cu2 trigonal pyramids that share  a cornercorner with one O(2)MgV2Cu trigonal pyramid, corners with three equivalent O(9)MgV2Cu trigonal pyramids, and  an edgeedge with one O(6)V2Cu2 trigonal pyramid. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one V(2) atom. In the sixth O site, O(6) is bonded to one V(1), one V(3), one Cu(1), and one Cu(2) atom to form distorted OV2Cu2 trigonal pyramids that share  a cornercorner with one O(9)MgV2Cu trigonal pyramid, corners with three equivalent O(2)MgV2Cu trigonal pyramids, and  an edgeedge with one O(4)V2Cu2 trigonal pyramid. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Mg(1), one V(3), and one V(4) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(3), one V(4), and one Cu(2) atom. In the ninth O site, O(9) is bonded to one Mg(1), one V(2), one V(4), and one Cu(1) atom to form OMgV2Cu trigonal pyramids that share  a cornercorner with one O(6)V2Cu2 trigonal pyramid, corners with three equivalent O(4)V2Cu2 trigonal pyramids, and  an edgeedge with one O(2)MgV2Cu trigonal pyramid. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one Cu(3) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one Cu(3) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one V(2), one V(3), one Cu(2), and one Cu(3) atom.