NaMg2V3O10 crystallizes in the triclinic P-1 space group. Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(5), one O(8), and two equivalent O(2) atoms. There are two inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to one O(10), one O(2), one O(4), one O(7), one O(8), and one O(9) atom to form MgO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, and  an edgeedge with one Mg(2)O6 octahedra. In the second Mg site, Mg(2) is bonded to one O(3), one O(4), one O(5), one O(9), and two equivalent O(6) atoms to form MgO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with four equivalent V(3)O4 tetrahedra,  an edgeedge with one Mg(1)O6 octahedra, and  an edgeedge with one Mg(2)O6 octahedra. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form VO4 tetrahedra that share corners with two equivalent Mg(1)O6 octahedra, corners with two equivalent Mg(2)O6 octahedra, and  a cornercorner with one V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-60°. In the second V site, V(2) is bonded to one O(1), one O(10), one O(7), and one O(8) atom to form VO4 tetrahedra that share corners with three equivalent Mg(1)O6 octahedra,  a cornercorner with one V(1)O4 tetrahedra, and  a cornercorner with one V(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 35-61°. In the third V site, V(3) is bonded to one O(3), one O(6), one O(7), and one O(9) atom to form VO4 tetrahedra that share corners with two equivalent Mg(1)O6 octahedra, corners with four equivalent Mg(2)O6 octahedra, and  a cornercorner with one V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-64°. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Na(1), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a 4-coordinate 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 linear geometry to one Mg(2) and one V(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Mg(1), one Mg(2), and one V(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Na(1), one Mg(2), and one V(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to two equivalent Mg(2) and one V(3) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Mg(1), one V(2), and one V(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Na(1), one Mg(1), and one V(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Mg(1), one Mg(2), and one V(3) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(1), one Mg(1), and one V(2) atom.
NaMg2V3O10 crystallizes in the triclinic P-1 space group. Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(5), one O(8), and two equivalent O(2) atoms. The Na(1)-O(1) bond length is 2.75 Å. The Na(1)-O(10) bond length is 2.44 Å. The Na(1)-O(5) bond length is 2.42 Å. The Na(1)-O(8) bond length is 2.40 Å. There is one shorter (2.41 Å) and one longer (2.60 Å) Na(1)-O(2) bond length. There are two inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to one O(10), one O(2), one O(4), one O(7), one O(8), and one O(9) atom to form MgO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, and  an edgeedge with one Mg(2)O6 octahedra. The Mg(1)-O(10) bond length is 2.02 Å. The Mg(1)-O(2) bond length is 2.08 Å. The Mg(1)-O(4) bond length is 2.10 Å. The Mg(1)-O(7) bond length is 2.16 Å. The Mg(1)-O(8) bond length is 2.11 Å. The Mg(1)-O(9) bond length is 2.08 Å. In the second Mg site, Mg(2) is bonded to one O(3), one O(4), one O(5), one O(9), and two equivalent O(6) atoms to form MgO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with four equivalent V(3)O4 tetrahedra,  an edgeedge with one Mg(1)O6 octahedra, and  an edgeedge with one Mg(2)O6 octahedra. The Mg(2)-O(3) bond length is 2.02 Å. The Mg(2)-O(4) bond length is 2.08 Å. The Mg(2)-O(5) bond length is 2.04 Å. The Mg(2)-O(9) bond length is 2.08 Å. There is one shorter (2.07 Å) and one longer (2.18 Å) Mg(2)-O(6) bond length. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form VO4 tetrahedra that share corners with two equivalent Mg(1)O6 octahedra, corners with two equivalent Mg(2)O6 octahedra, and  a cornercorner with one V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-60°. The V(1)-O(1) bond length is 1.81 Å. The V(1)-O(2) bond length is 1.71 Å. The V(1)-O(4) bond length is 1.71 Å. The V(1)-O(5) bond length is 1.68 Å. In the second V site, V(2) is bonded to one O(1), one O(10), one O(7), and one O(8) atom to form VO4 tetrahedra that share corners with three equivalent Mg(1)O6 octahedra,  a cornercorner with one V(1)O4 tetrahedra, and  a cornercorner with one V(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 35-61°. The V(2)-O(1) bond length is 1.76 Å. The V(2)-O(10) bond length is 1.66 Å. The V(2)-O(7) bond length is 1.81 Å. The V(2)-O(8) bond length is 1.67 Å. In the third V site, V(3) is bonded to one O(3), one O(6), one O(7), and one O(9) atom to form VO4 tetrahedra that share corners with two equivalent Mg(1)O6 octahedra, corners with four equivalent Mg(2)O6 octahedra, and  a cornercorner with one V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-64°. The V(3)-O(3) bond length is 1.66 Å. The V(3)-O(6) bond length is 1.70 Å. The V(3)-O(7) bond length is 1.86 Å. The V(3)-O(9) bond length is 1.72 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Na(1), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a 4-coordinate 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 linear geometry to one Mg(2) and one V(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Mg(1), one Mg(2), and one V(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Na(1), one Mg(2), and one V(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to two equivalent Mg(2) and one V(3) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Mg(1), one V(2), and one V(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Na(1), one Mg(1), and one V(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Mg(1), one Mg(2), and one V(3) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(1), one Mg(1), and one V(2) atom.