NaV2(PO7)2 crystallizes in the triclinic P1 space group. Na(1) is bonded to one O(1), one O(10), one O(11), one O(12), one O(13), one O(14), and one O(4) atom to form distorted NaO7 pentagonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(4), one O(5), and one O(6) atom. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(10), one O(12), one O(2), one O(7), one O(8), and one O(9) atom. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(4), one O(6), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Na(1)O7 pentagonal bipyramids. In the second P site, P(2) is bonded in a tetrahedral geometry to one O(3), one O(5), one O(7), and one O(8) atom. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one Na(1) and one V(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one V(2) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Na(1), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one V(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one V(2) and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one V(2) and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one V(2) and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Na(1), one V(2), and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one O(13) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Na(1), one V(2), and one O(14) atom. In the thirteenth O site, O(13) is bonded in a bent 120 degrees geometry to one Na(1) and one O(11) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one Na(1) and one O(12) atom.
NaV2(PO7)2 crystallizes in the triclinic P1 space group. Na(1) is bonded to one O(1), one O(10), one O(11), one O(12), one O(13), one O(14), and one O(4) atom to form distorted NaO7 pentagonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra. The Na(1)-O(1) bond length is 2.86 Å. The Na(1)-O(10) bond length is 2.70 Å. The Na(1)-O(11) bond length is 2.65 Å. The Na(1)-O(12) bond length is 2.61 Å. The Na(1)-O(13) bond length is 2.87 Å. The Na(1)-O(14) bond length is 2.88 Å. The Na(1)-O(4) bond length is 2.71 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(4), one O(5), and one O(6) atom. The V(1)-O(1) bond length is 1.63 Å. The V(1)-O(3) bond length is 1.98 Å. The V(1)-O(4) bond length is 2.01 Å. The V(1)-O(5) bond length is 1.99 Å. The V(1)-O(6) bond length is 1.98 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(10), one O(12), one O(2), one O(7), one O(8), and one O(9) atom. The V(2)-O(10) bond length is 2.00 Å. The V(2)-O(12) bond length is 2.76 Å. The V(2)-O(2) bond length is 1.59 Å. The V(2)-O(7) bond length is 1.92 Å. The V(2)-O(8) bond length is 1.93 Å. The V(2)-O(9) bond length is 1.92 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(4), one O(6), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Na(1)O7 pentagonal bipyramids. The P(1)-O(10) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.53 Å. The P(1)-O(9) bond length is 1.58 Å. In the second P site, P(2) is bonded in a tetrahedral geometry to one O(3), one O(5), one O(7), and one O(8) atom. The P(2)-O(3) bond length is 1.53 Å. The P(2)-O(5) bond length is 1.53 Å. The P(2)-O(7) bond length is 1.58 Å. The P(2)-O(8) bond length is 1.57 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one Na(1) and one V(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one V(2) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Na(1), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one V(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one V(2) and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one V(2) and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one V(2) and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Na(1), one V(2), and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one O(13) atom. The O(11)-O(13) bond length is 1.23 Å. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Na(1), one V(2), and one O(14) atom. The O(12)-O(14) bond length is 1.24 Å. In the thirteenth O site, O(13) is bonded in a bent 120 degrees geometry to one Na(1) and one O(11) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one Na(1) and one O(12) atom.