MgV4(PbO6)2 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a 5-coordinate geometry to one O(11), one O(2), one O(7), and two equivalent O(10) atoms. There are four inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(1), one O(5), one O(9), and two equivalent O(4) atoms. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(12), one O(2), one O(6), and two equivalent O(3) atoms. In the third V site, V(3) is bonded to one O(10), one O(3), one O(8), and two equivalent O(2) atoms to form distorted VO5 trigonal bipyramids that share  a cornercorner with one Pb(1)O5 square pyramid and corners with two equivalent V(3)O5 trigonal bipyramids. In the fourth V site, V(4) is bonded to one O(11), one O(4), one O(7), and two equivalent O(1) atoms to form distorted VO5 trigonal bipyramids that share corners with two equivalent Pb(1)O5 square pyramids and corners with two equivalent V(4)O5 trigonal bipyramids. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded to one O(8), two equivalent O(11), and two equivalent O(9) atoms to form distorted PbO5 square pyramids that share  a cornercorner with one V(3)O5 trigonal bipyramid, corners with two equivalent V(4)O5 trigonal bipyramids, and edges with two equivalent Pb(1)O5 square pyramids. In the second Pb site, Pb(2) is bonded in a 4-coordinate geometry to two equivalent O(12) and two equivalent O(5) atoms. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one V(1) and two equivalent V(4) atoms. In the second O site, O(2) is bonded in a distorted square co-planar geometry to one Mg(1), one V(2), and two equivalent V(3) atoms. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(3) and two equivalent V(2) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one V(4) and two equivalent V(1) atoms. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one V(1) and two equivalent Pb(2) atoms. In the sixth O site, O(6) is bonded in a single-bond geometry to one V(2) atom. In the seventh O site, O(7) is bonded in an L-shaped geometry to one Mg(1) and one V(4) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one V(3) and one Pb(1) atom. In the ninth O site, O(9) is bonded in a single-bond geometry to one V(1) and two equivalent Pb(1) atoms. In the tenth O site, O(10) is bonded in a T-shaped geometry to two equivalent Mg(1) and one V(3) atom. In the eleventh O site, O(11) is bonded to one Mg(1), one V(4), and two equivalent Pb(1) atoms to form distorted corner-sharing OMgVPb2 tetrahedra. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one V(2) and two equivalent Pb(2) atoms.
MgV4(PbO6)2 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a 5-coordinate geometry to one O(11), one O(2), one O(7), and two equivalent O(10) atoms. The Mg(1)-O(11) bond length is 2.01 Å. The Mg(1)-O(2) bond length is 2.48 Å. The Mg(1)-O(7) bond length is 2.07 Å. Both Mg(1)-O(10) bond lengths are 2.01 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(1), one O(5), one O(9), and two equivalent O(4) atoms. The V(1)-O(1) bond length is 2.00 Å. The V(1)-O(5) bond length is 1.72 Å. The V(1)-O(9) bond length is 1.69 Å. Both V(1)-O(4) bond lengths are 1.93 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(12), one O(2), one O(6), and two equivalent O(3) atoms. The V(2)-O(12) bond length is 1.77 Å. The V(2)-O(2) bond length is 1.98 Å. The V(2)-O(6) bond length is 1.65 Å. Both V(2)-O(3) bond lengths are 1.93 Å. In the third V site, V(3) is bonded to one O(10), one O(3), one O(8), and two equivalent O(2) atoms to form distorted VO5 trigonal bipyramids that share  a cornercorner with one Pb(1)O5 square pyramid and corners with two equivalent V(3)O5 trigonal bipyramids. The V(3)-O(10) bond length is 1.90 Å. The V(3)-O(3) bond length is 1.99 Å. The V(3)-O(8) bond length is 1.69 Å. Both V(3)-O(2) bond lengths are 1.96 Å. In the fourth V site, V(4) is bonded to one O(11), one O(4), one O(7), and two equivalent O(1) atoms to form distorted VO5 trigonal bipyramids that share corners with two equivalent Pb(1)O5 square pyramids and corners with two equivalent V(4)O5 trigonal bipyramids. The V(4)-O(11) bond length is 1.94 Å. The V(4)-O(4) bond length is 1.99 Å. The V(4)-O(7) bond length is 1.71 Å. Both V(4)-O(1) bond lengths are 1.97 Å. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded to one O(8), two equivalent O(11), and two equivalent O(9) atoms to form distorted PbO5 square pyramids that share  a cornercorner with one V(3)O5 trigonal bipyramid, corners with two equivalent V(4)O5 trigonal bipyramids, and edges with two equivalent Pb(1)O5 square pyramids. The Pb(1)-O(8) bond length is 2.41 Å. There is one shorter (2.45 Å) and one longer (2.46 Å) Pb(1)-O(11) bond length. There is one shorter (2.73 Å) and one longer (2.74 Å) Pb(1)-O(9) bond length. In the second Pb site, Pb(2) is bonded in a 4-coordinate geometry to two equivalent O(12) and two equivalent O(5) atoms. Both Pb(2)-O(12) bond lengths are 2.41 Å. Both Pb(2)-O(5) bond lengths are 2.59 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one V(1) and two equivalent V(4) atoms. In the second O site, O(2) is bonded in a distorted square co-planar geometry to one Mg(1), one V(2), and two equivalent V(3) atoms. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(3) and two equivalent V(2) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one V(4) and two equivalent V(1) atoms. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one V(1) and two equivalent Pb(2) atoms. In the sixth O site, O(6) is bonded in a single-bond geometry to one V(2) atom. In the seventh O site, O(7) is bonded in an L-shaped geometry to one Mg(1) and one V(4) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one V(3) and one Pb(1) atom. In the ninth O site, O(9) is bonded in a single-bond geometry to one V(1) and two equivalent Pb(1) atoms. In the tenth O site, O(10) is bonded in a T-shaped geometry to two equivalent Mg(1) and one V(3) atom. In the eleventh O site, O(11) is bonded to one Mg(1), one V(4), and two equivalent Pb(1) atoms to form distorted corner-sharing OMgVPb2 tetrahedra. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one V(2) and two equivalent Pb(2) atoms.