Na2VBPO7 crystallizes in the triclinic P1 space group. There are eight inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(13), one O(2), one O(21), one O(6), and one O(9) atom. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(1), one O(10), one O(14), one O(22), and one O(5) atom. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one O(1), one O(13), one O(24), one O(6), and one O(9) atom. In the fourth Na site, Na(4) is bonded in a 5-coordinate geometry to one O(10), one O(14), one O(2), one O(23), and one O(5) atom. In the fifth Na site, Na(5) is bonded in a 5-coordinate geometry to one O(11), one O(15), one O(26), one O(3), and one O(8) atom. In the sixth Na site, Na(6) is bonded in a 5-coordinate geometry to one O(12), one O(16), one O(25), one O(4), and one O(7) atom. In the seventh Na site, Na(7) is bonded in a 5-coordinate geometry to one O(11), one O(15), one O(27), one O(4), and one O(8) atom. In the eighth Na site, Na(8) is bonded in a 5-coordinate geometry to one O(12), one O(16), one O(28), one O(3), and one O(7) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(13), one O(20), one O(21), one O(24), and one O(6) atom to form VO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. In the second V site, V(2) is bonded to one O(12), one O(15), one O(18), one O(26), one O(27), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. In the third V site, V(3) is bonded to one O(14), one O(19), one O(22), one O(23), one O(5), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. In the fourth V site, V(4) is bonded to one O(11), one O(16), one O(17), one O(25), one O(28), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. There are four inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(4), one O(5), and one O(9) atom. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(10), one O(3), and one O(6) atom. In the third B site, B(3) is bonded in a trigonal planar geometry to one O(11), one O(2), and one O(7) atom. In the fourth B site, B(4) is bonded in a trigonal planar geometry to one O(1), one O(12), and one O(8) atom. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(15), one O(17), one O(21), and one O(23) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-39°. In the second P site, P(2) is bonded to one O(16), one O(18), one O(22), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-41°. In the third P site, P(3) is bonded to one O(13), one O(19), one O(25), and one O(27) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 33-39°. In the fourth P site, P(4) is bonded to one O(14), one O(20), one O(26), and one O(28) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-40°. There are twenty-eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(2), one Na(3), and one B(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(4), and one B(3) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Na(5), one Na(8), and one B(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Na(6), one Na(7), and one B(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(4), one V(3), and one B(1) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(3), one V(1), and one B(2) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Na(6), one Na(8), one V(4), and one B(3) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Na(5), one Na(7), one V(2), and one B(4) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one V(3), and one B(1) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one V(1), and one B(2) atom. In the eleventh O site, O(11) is bonded in a distorted tetrahedral geometry to one Na(5), one Na(7), one V(4), and one B(3) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(6), one Na(8), one V(2), and one B(4) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one V(1), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one V(3), and one P(4) atom. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one Na(5), one Na(7), one V(2), and one P(1) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 150 degrees geometry to one Na(6), one Na(8), one V(4), and one P(2) atom. In the seventeenth O site, O(17) is bonded in a bent 150 degrees geometry to one V(4) and one P(1) atom. In the eighteenth O site, O(18) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the nineteenth O site, O(19) is bonded in a bent 150 degrees geometry to one V(3) and one P(3) atom. In the twentieth O site, O(20) is bonded in a bent 150 degrees geometry to one V(1) and one P(4) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Na(1), one V(1), and one P(1) atom. In the twenty-second O site, O(22) is bonded in a 3-coordinate geometry to one Na(2), one V(3), and one P(2) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Na(4), one V(3), and one P(1) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Na(3), one V(1), and one P(2) atom. In the twenty-fifth O site, O(25) is bonded in a 3-coordinate geometry to one Na(6), one V(4), and one P(3) atom. In the twenty-sixth O site, O(26) is bonded in a distorted bent 150 degrees geometry to one Na(5), one V(2), and one P(4) atom. In the twenty-seventh O site, O(27) is bonded in a 3-coordinate geometry to one Na(7), one V(2), and one P(3) atom. In the twenty-eighth O site, O(28) is bonded in a 3-coordinate geometry to one Na(8), one V(4), and one P(4) atom.
Na2VBPO7 crystallizes in the triclinic P1 space group. There are eight inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(13), one O(2), one O(21), one O(6), and one O(9) atom. The Na(1)-O(13) bond length is 2.63 Å. The Na(1)-O(2) bond length is 2.20 Å. The Na(1)-O(21) bond length is 2.61 Å. The Na(1)-O(6) bond length is 2.29 Å. The Na(1)-O(9) bond length is 2.34 Å. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(1), one O(10), one O(14), one O(22), and one O(5) atom. The Na(2)-O(1) bond length is 2.19 Å. The Na(2)-O(10) bond length is 2.35 Å. The Na(2)-O(14) bond length is 2.63 Å. The Na(2)-O(22) bond length is 2.59 Å. The Na(2)-O(5) bond length is 2.29 Å. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one O(1), one O(13), one O(24), one O(6), and one O(9) atom. The Na(3)-O(1) bond length is 2.19 Å. The Na(3)-O(13) bond length is 2.63 Å. The Na(3)-O(24) bond length is 2.60 Å. The Na(3)-O(6) bond length is 2.29 Å. The Na(3)-O(9) bond length is 2.35 Å. In the fourth Na site, Na(4) is bonded in a 5-coordinate geometry to one O(10), one O(14), one O(2), one O(23), and one O(5) atom. The Na(4)-O(10) bond length is 2.34 Å. The Na(4)-O(14) bond length is 2.62 Å. The Na(4)-O(2) bond length is 2.20 Å. The Na(4)-O(23) bond length is 2.63 Å. The Na(4)-O(5) bond length is 2.30 Å. In the fifth Na site, Na(5) is bonded in a 5-coordinate geometry to one O(11), one O(15), one O(26), one O(3), and one O(8) atom. The Na(5)-O(11) bond length is 2.32 Å. The Na(5)-O(15) bond length is 2.58 Å. The Na(5)-O(26) bond length is 2.69 Å. The Na(5)-O(3) bond length is 2.19 Å. The Na(5)-O(8) bond length is 2.31 Å. In the sixth Na site, Na(6) is bonded in a 5-coordinate geometry to one O(12), one O(16), one O(25), one O(4), and one O(7) atom. The Na(6)-O(12) bond length is 2.30 Å. The Na(6)-O(16) bond length is 2.64 Å. The Na(6)-O(25) bond length is 2.60 Å. The Na(6)-O(4) bond length is 2.20 Å. The Na(6)-O(7) bond length is 2.27 Å. In the seventh Na site, Na(7) is bonded in a 5-coordinate geometry to one O(11), one O(15), one O(27), one O(4), and one O(8) atom. The Na(7)-O(11) bond length is 2.32 Å. The Na(7)-O(15) bond length is 2.58 Å. The Na(7)-O(27) bond length is 2.66 Å. The Na(7)-O(4) bond length is 2.19 Å. The Na(7)-O(8) bond length is 2.32 Å. In the eighth Na site, Na(8) is bonded in a 5-coordinate geometry to one O(12), one O(16), one O(28), one O(3), and one O(7) atom. The Na(8)-O(12) bond length is 2.31 Å. The Na(8)-O(16) bond length is 2.65 Å. The Na(8)-O(28) bond length is 2.59 Å. The Na(8)-O(3) bond length is 2.20 Å. The Na(8)-O(7) bond length is 2.27 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(13), one O(20), one O(21), one O(24), and one O(6) atom to form VO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The V(1)-O(10) bond length is 1.84 Å. The V(1)-O(13) bond length is 2.00 Å. The V(1)-O(20) bond length is 1.99 Å. The V(1)-O(21) bond length is 2.01 Å. The V(1)-O(24) bond length is 2.01 Å. The V(1)-O(6) bond length is 1.98 Å. In the second V site, V(2) is bonded to one O(12), one O(15), one O(18), one O(26), one O(27), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The V(2)-O(12) bond length is 1.89 Å. The V(2)-O(15) bond length is 2.08 Å. The V(2)-O(18) bond length is 2.04 Å. The V(2)-O(26) bond length is 1.96 Å. The V(2)-O(27) bond length is 1.97 Å. The V(2)-O(8) bond length is 1.91 Å. In the third V site, V(3) is bonded to one O(14), one O(19), one O(22), one O(23), one O(5), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The V(3)-O(14) bond length is 2.01 Å. The V(3)-O(19) bond length is 2.00 Å. The V(3)-O(22) bond length is 2.02 Å. The V(3)-O(23) bond length is 1.98 Å. The V(3)-O(5) bond length is 1.98 Å. The V(3)-O(9) bond length is 1.85 Å. In the fourth V site, V(4) is bonded to one O(11), one O(16), one O(17), one O(25), one O(28), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The V(4)-O(11) bond length is 1.85 Å. The V(4)-O(16) bond length is 1.97 Å. The V(4)-O(17) bond length is 1.99 Å. The V(4)-O(25) bond length is 2.03 Å. The V(4)-O(28) bond length is 2.03 Å. The V(4)-O(7) bond length is 1.99 Å. There are four inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(4), one O(5), and one O(9) atom. The B(1)-O(4) bond length is 1.31 Å. The B(1)-O(5) bond length is 1.40 Å. The B(1)-O(9) bond length is 1.48 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(10), one O(3), and one O(6) atom. The B(2)-O(10) bond length is 1.48 Å. The B(2)-O(3) bond length is 1.31 Å. The B(2)-O(6) bond length is 1.40 Å. In the third B site, B(3) is bonded in a trigonal planar geometry to one O(11), one O(2), and one O(7) atom. The B(3)-O(11) bond length is 1.48 Å. The B(3)-O(2) bond length is 1.31 Å. The B(3)-O(7) bond length is 1.39 Å. In the fourth B site, B(4) is bonded in a trigonal planar geometry to one O(1), one O(12), and one O(8) atom. The B(4)-O(1) bond length is 1.30 Å. The B(4)-O(12) bond length is 1.45 Å. The B(4)-O(8) bond length is 1.43 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(15), one O(17), one O(21), and one O(23) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-39°. The P(1)-O(15) bond length is 1.54 Å. The P(1)-O(17) bond length is 1.56 Å. The P(1)-O(21) bond length is 1.55 Å. The P(1)-O(23) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(16), one O(18), one O(22), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-41°. The P(2)-O(16) bond length is 1.57 Å. The P(2)-O(18) bond length is 1.55 Å. The P(2)-O(22) bond length is 1.55 Å. The P(2)-O(24) bond length is 1.55 Å. In the third P site, P(3) is bonded to one O(13), one O(19), one O(25), and one O(27) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 33-39°. The P(3)-O(13) bond length is 1.55 Å. The P(3)-O(19) bond length is 1.55 Å. The P(3)-O(25) bond length is 1.54 Å. The P(3)-O(27) bond length is 1.56 Å. In the fourth P site, P(4) is bonded to one O(14), one O(20), one O(26), and one O(28) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-40°. The P(4)-O(14) bond length is 1.55 Å. The P(4)-O(20) bond length is 1.55 Å. The P(4)-O(26) bond length is 1.56 Å. The P(4)-O(28) bond length is 1.54 Å. There are twenty-eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(2), one Na(3), and one B(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(4), and one B(3) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Na(5), one Na(8), and one B(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Na(6), one Na(7), and one B(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(4), one V(3), and one B(1) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(3), one V(1), and one B(2) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Na(6), one Na(8), one V(4), and one B(3) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Na(5), one Na(7), one V(2), and one B(4) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one V(3), and one B(1) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one V(1), and one B(2) atom. In the eleventh O site, O(11) is bonded in a distorted tetrahedral geometry to one Na(5), one Na(7), one V(4), and one B(3) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(6), one Na(8), one V(2), and one B(4) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one V(1), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one V(3), and one P(4) atom. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one Na(5), one Na(7), one V(2), and one P(1) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 150 degrees geometry to one Na(6), one Na(8), one V(4), and one P(2) atom. In the seventeenth O site, O(17) is bonded in a bent 150 degrees geometry to one V(4) and one P(1) atom. In the eighteenth O site, O(18) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the nineteenth O site, O(19) is bonded in a bent 150 degrees geometry to one V(3) and one P(3) atom. In the twentieth O site, O(20) is bonded in a bent 150 degrees geometry to one V(1) and one P(4) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Na(1), one V(1), and one P(1) atom. In the twenty-second O site, O(22) is bonded in a 3-coordinate geometry to one Na(2), one V(3), and one P(2) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Na(4), one V(3), and one P(1) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Na(3), one V(1), and one P(2) atom. In the twenty-fifth O site, O(25) is bonded in a 3-coordinate geometry to one Na(6), one V(4), and one P(3) atom. In the twenty-sixth O site, O(26) is bonded in a distorted bent 150 degrees geometry to one Na(5), one V(2), and one P(4) atom. In the twenty-seventh O site, O(27) is bonded in a 3-coordinate geometry to one Na(7), one V(2), and one P(3) atom. In the twenty-eighth O site, O(28) is bonded in a 3-coordinate geometry to one Na(8), one V(4), and one P(4) atom.