Na2VBPO7 crystallizes in the monoclinic P2_1/c space group. There are two 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(4), and one O(7) atom. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one O(6) atom. V(1) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form VO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra. B(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. P(1) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-43°. There are seven inequivalent O sites. In the first O site, O(4) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one V(1), and one P(1) atom. In the second O site, O(5) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(1) atom. In the third O site, O(6) is bonded in a 3-coordinate geometry to one Na(2), one V(1), and one P(1) atom. In the fourth O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one V(1), and one P(1) atom. In the fifth O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one B(1) atom. In the sixth O site, O(2) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(2), one V(1), and one B(1) atom. In the seventh O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one V(1), and one B(1) atom.
Na2VBPO7 crystallizes in the monoclinic P2_1/c space group. There are two 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(4), and one O(7) atom. The Na(1)-O(1) bond length is 2.19 Å. The Na(1)-O(2) bond length is 2.32 Å. The Na(1)-O(3) bond length is 2.30 Å. The Na(1)-O(4) bond length is 2.55 Å. The Na(1)-O(7) bond length is 2.68 Å. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one O(6) atom. The Na(2)-O(1) bond length is 2.19 Å. The Na(2)-O(2) bond length is 2.32 Å. The Na(2)-O(3) bond length is 2.30 Å. The Na(2)-O(4) bond length is 2.55 Å. The Na(2)-O(6) bond length is 2.68 Å. V(1) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form VO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra. The V(1)-O(2) bond length is 1.90 Å. The V(1)-O(3) bond length is 1.89 Å. The V(1)-O(4) bond length is 2.11 Å. The V(1)-O(5) bond length is 2.05 Å. The V(1)-O(6) bond length is 1.95 Å. The V(1)-O(7) bond length is 1.96 Å. B(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. The B(1)-O(1) bond length is 1.30 Å. The B(1)-O(2) bond length is 1.43 Å. The B(1)-O(3) bond length is 1.45 Å. P(1) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-43°. The P(1)-O(4) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.56 Å. The P(1)-O(7) bond length is 1.56 Å. There are seven inequivalent O sites. In the first O site, O(4) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one V(1), and one P(1) atom. In the second O site, O(5) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(1) atom. In the third O site, O(6) is bonded in a 3-coordinate geometry to one Na(2), one V(1), and one P(1) atom. In the fourth O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one V(1), and one P(1) atom. In the fifth O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one B(1) atom. In the sixth O site, O(2) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(2), one V(1), and one B(1) atom. In the seventh O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one V(1), and one B(1) atom.