Na3MgVH6O7 crystallizes in the triclinic P1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(5), and one O(7) atom. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one H(3), one O(1), one O(3), one O(4), one O(5), and one O(6) atom. In the third Na site, Na(3) is bonded in a 3-coordinate geometry to one O(1), one O(6), and one O(7) atom. Mg(1) is bonded to one O(1), one O(2), one O(4), and one O(7) atom to form MgO4 tetrahedra that share  a cornercorner with one V(1)O4 tetrahedra and  an edgeedge with one V(1)O4 tetrahedra. V(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form VO4 tetrahedra that share  a cornercorner with one Mg(1)O4 tetrahedra and  an edgeedge with one Mg(1)O4 tetrahedra. There are six inequivalent H sites. In the first H site, H(1) is bonded in a distorted single-bond geometry to one O(2) and one O(5) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(6) atom. In the third H site, H(3) is bonded in a single-bond geometry to one Na(2) and one O(7) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(4) and one O(5) atom. In the fifth H site, H(5) is bonded in a distorted single-bond geometry to one O(2) and one O(6) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one O(3) atom. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Mg(1), and one V(1) atom. In the second O site, O(2) is bonded in a distorted trigonal bipyramidal geometry to one Na(1), one Mg(1), one V(1), one H(1), and one H(5) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Na(1), one Na(2), one V(1), and one H(6) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Mg(1), one V(1), and one H(4) atom. In the fifth O site, O(5) is bonded in a water-like geometry to one Na(1), one Na(2), one H(1), and one H(4) atom. In the sixth O site, O(6) is bonded in a distorted water-like geometry to one Na(2), one Na(3), one H(2), and one H(5) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Na(1), one Na(3), one Mg(1), and one H(3) atom.
Na3MgVH6O7 crystallizes in the triclinic P1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(5), and one O(7) atom. The Na(1)-O(1) bond length is 2.78 Å. The Na(1)-O(2) bond length is 2.43 Å. The Na(1)-O(3) bond length is 2.59 Å. The Na(1)-O(5) bond length is 2.83 Å. The Na(1)-O(7) bond length is 2.46 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one H(3), one O(1), one O(3), one O(4), one O(5), and one O(6) atom. The Na(2)-H(3) bond length is 2.51 Å. The Na(2)-O(1) bond length is 2.46 Å. The Na(2)-O(3) bond length is 2.35 Å. The Na(2)-O(4) bond length is 2.50 Å. The Na(2)-O(5) bond length is 2.50 Å. The Na(2)-O(6) bond length is 2.33 Å. In the third Na site, Na(3) is bonded in a 3-coordinate geometry to one O(1), one O(6), and one O(7) atom. The Na(3)-O(1) bond length is 2.23 Å. The Na(3)-O(6) bond length is 2.32 Å. The Na(3)-O(7) bond length is 2.39 Å. Mg(1) is bonded to one O(1), one O(2), one O(4), and one O(7) atom to form MgO4 tetrahedra that share  a cornercorner with one V(1)O4 tetrahedra and  an edgeedge with one V(1)O4 tetrahedra. The Mg(1)-O(1) bond length is 1.96 Å. The Mg(1)-O(2) bond length is 2.02 Å. The Mg(1)-O(4) bond length is 1.96 Å. The Mg(1)-O(7) bond length is 1.99 Å. V(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form VO4 tetrahedra that share  a cornercorner with one Mg(1)O4 tetrahedra and  an edgeedge with one Mg(1)O4 tetrahedra. The V(1)-O(1) bond length is 1.91 Å. The V(1)-O(2) bond length is 2.00 Å. The V(1)-O(3) bond length is 1.98 Å. The V(1)-O(4) bond length is 1.91 Å. There are six inequivalent H sites. In the first H site, H(1) is bonded in a distorted single-bond geometry to one O(2) and one O(5) atom. The H(1)-O(2) bond length is 1.66 Å. The H(1)-O(5) bond length is 1.03 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(6) atom. The H(2)-O(6) bond length is 0.99 Å. In the third H site, H(3) is bonded in a single-bond geometry to one Na(2) and one O(7) atom. The H(3)-O(7) bond length is 0.97 Å. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(4) and one O(5) atom. The H(4)-O(4) bond length is 1.74 Å. The H(4)-O(5) bond length is 1.02 Å. In the fifth H site, H(5) is bonded in a distorted single-bond geometry to one O(2) and one O(6) atom. The H(5)-O(2) bond length is 1.68 Å. The H(5)-O(6) bond length is 1.02 Å. In the sixth H site, H(6) is bonded in a single-bond geometry to one O(3) atom. The H(6)-O(3) bond length is 0.99 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Mg(1), and one V(1) atom. In the second O site, O(2) is bonded in a distorted trigonal bipyramidal geometry to one Na(1), one Mg(1), one V(1), one H(1), and one H(5) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Na(1), one Na(2), one V(1), and one H(6) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Mg(1), one V(1), and one H(4) atom. In the fifth O site, O(5) is bonded in a water-like geometry to one Na(1), one Na(2), one H(1), and one H(4) atom. In the sixth O site, O(6) is bonded in a distorted water-like geometry to one Na(2), one Na(3), one H(2), and one H(5) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Na(1), one Na(3), one Mg(1), and one H(3) atom.