NaMgV4O10 crystallizes in the monoclinic C2/m space group. Na(1) is bonded in a distorted linear geometry to two equivalent Mg(1), four equivalent O(2), and four equivalent O(3) atoms. Mg(1) is bonded to two equivalent Na(1), two equivalent O(2), and two equivalent O(3) atoms to form MgNa2O4 octahedra that share corners with two equivalent Mg(1)Na2O4 octahedra and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-29°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(4) atoms to form distorted VO6 octahedra that share  a cornercorner with one Mg(1)Na2O4 octahedra, corners with two equivalent V(1)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-29°. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), and three equivalent O(5) atoms. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one V(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a bent 150 degrees geometry to two equivalent Na(1), one Mg(1), and one V(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to two equivalent Na(1), one Mg(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the fifth O site, O(5) is bonded to one V(1) and three equivalent V(2) atoms to form a mixture of distorted edge and corner-sharing OV4 trigonal pyramids.
NaMgV4O10 crystallizes in the monoclinic C2/m space group. Na(1) is bonded in a distorted linear geometry to two equivalent Mg(1), four equivalent O(2), and four equivalent O(3) atoms. Both Na(1)-Mg(1) bond lengths are 2.03 Å. All Na(1)-O(2) bond lengths are 2.78 Å. All Na(1)-O(3) bond lengths are 2.81 Å. Mg(1) is bonded to two equivalent Na(1), two equivalent O(2), and two equivalent O(3) atoms to form MgNa2O4 octahedra that share corners with two equivalent Mg(1)Na2O4 octahedra and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-29°. Both Mg(1)-O(2) bond lengths are 1.90 Å. Both Mg(1)-O(3) bond lengths are 1.94 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(4) atoms to form distorted VO6 octahedra that share  a cornercorner with one Mg(1)Na2O4 octahedra, corners with two equivalent V(1)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-29°. The V(1)-O(2) bond length is 1.75 Å. The V(1)-O(5) bond length is 2.00 Å. There is one shorter (1.90 Å) and one longer (1.99 Å) V(1)-O(1) bond length. Both V(1)-O(4) bond lengths are 2.07 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), and three equivalent O(5) atoms. The V(2)-O(1) bond length is 1.96 Å. The V(2)-O(3) bond length is 1.72 Å. The V(2)-O(4) bond length is 1.90 Å. There are two shorter (2.09 Å) and one longer (2.29 Å) V(2)-O(5) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one V(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a bent 150 degrees geometry to two equivalent Na(1), one Mg(1), and one V(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to two equivalent Na(1), one Mg(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the fifth O site, O(5) is bonded to one V(1) and three equivalent V(2) atoms to form a mixture of distorted edge and corner-sharing OV4 trigonal pyramids.