V3(PO4)2 crystallizes in the triclinic P-1 space group. There are six inequivalent V sites. In the first V site, V(1) is bonded in a 3-coordinate geometry to one O(1), one O(3), and two equivalent O(10) atoms. In the second V site, V(2) is bonded in a 5-coordinate geometry to one P(1), one O(12), one O(7), and two equivalent O(4) atoms. In the third V site, V(3) is bonded in a 1-coordinate geometry to one O(11) and one O(8) atom. In the fourth V site, V(4) is bonded in a distorted single-bond geometry to one O(11), one O(13), and one O(16) atom. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one V(6), one P(4), one O(11), one O(12), one O(15), and one O(4) atom. In the sixth V site, V(6) is bonded in a 5-coordinate geometry to one V(5), one O(11), one O(3), one O(5), and one O(6) atom. There are four inequivalent P sites. In the first P site, P(1) is bonded in a 2-coordinate geometry to one V(2), one O(2), and one O(6) atom. In the second P site, P(2) is bonded in a 3-coordinate geometry to one O(15), one O(3), and one O(7) atom. In the third P site, P(3) is bonded in a distorted single-bond geometry to one O(1), one O(10), and one O(9) atom. In the fourth P site, P(4) is bonded in a 1-coordinate geometry to one V(5), one O(12), one O(14), one O(4), and one O(8) atom. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted water-like geometry to one V(1) and one P(3) atom. In the second O site, O(2) is bonded in a single-bond geometry to one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one V(1), one V(6), one P(2), and one O(7) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one V(5), two equivalent V(2), one P(4), and one O(15) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one V(6) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one V(6), one P(1), and one O(16) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one V(2), one P(2), and one O(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(3) and one P(4) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one P(3), one O(10), and one O(14) atom. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to two equivalent V(1), one P(3), one O(13), and one O(9) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one V(3), one V(4), one V(5), and one V(6) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one V(2), one V(5), one P(4), and one O(14) atom. In the thirteenth O site, O(13) is bonded in a single-bond geometry to one V(4) and one O(10) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one P(4), one O(12), and one O(9) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one V(5), one P(2), and one O(4) atom. In the sixteenth O site, O(16) is bonded in a bent 120 degrees geometry to one V(4) and one O(6) atom.
V3(PO4)2 crystallizes in the triclinic P-1 space group. There are six inequivalent V sites. In the first V site, V(1) is bonded in a 3-coordinate geometry to one O(1), one O(3), and two equivalent O(10) atoms. The V(1)-O(1) bond length is 1.93 Å. The V(1)-O(3) bond length is 2.04 Å. There is one shorter (2.15 Å) and one longer (2.80 Å) V(1)-O(10) bond length. In the second V site, V(2) is bonded in a 5-coordinate geometry to one P(1), one O(12), one O(7), and two equivalent O(4) atoms. The V(2)-P(1) bond length is 2.11 Å. The V(2)-O(12) bond length is 2.07 Å. The V(2)-O(7) bond length is 2.56 Å. There is one shorter (2.19 Å) and one longer (2.43 Å) V(2)-O(4) bond length. In the third V site, V(3) is bonded in a 1-coordinate geometry to one O(11) and one O(8) atom. The V(3)-O(11) bond length is 2.41 Å. The V(3)-O(8) bond length is 1.91 Å. In the fourth V site, V(4) is bonded in a distorted single-bond geometry to one O(11), one O(13), and one O(16) atom. The V(4)-O(11) bond length is 2.16 Å. The V(4)-O(13) bond length is 1.26 Å. The V(4)-O(16) bond length is 2.20 Å. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one V(6), one P(4), one O(11), one O(12), one O(15), and one O(4) atom. The V(5)-V(6) bond length is 1.79 Å. The V(5)-P(4) bond length is 2.45 Å. The V(5)-O(11) bond length is 2.06 Å. The V(5)-O(12) bond length is 2.59 Å. The V(5)-O(15) bond length is 2.41 Å. The V(5)-O(4) bond length is 2.48 Å. In the sixth V site, V(6) is bonded in a 5-coordinate geometry to one V(5), one O(11), one O(3), one O(5), and one O(6) atom. The V(6)-O(11) bond length is 2.06 Å. The V(6)-O(3) bond length is 2.45 Å. The V(6)-O(5) bond length is 2.06 Å. The V(6)-O(6) bond length is 2.37 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded in a 2-coordinate geometry to one V(2), one O(2), and one O(6) atom. The P(1)-O(2) bond length is 1.71 Å. The P(1)-O(6) bond length is 1.33 Å. In the second P site, P(2) is bonded in a 3-coordinate geometry to one O(15), one O(3), and one O(7) atom. The P(2)-O(15) bond length is 1.72 Å. The P(2)-O(3) bond length is 1.42 Å. The P(2)-O(7) bond length is 1.29 Å. In the third P site, P(3) is bonded in a distorted single-bond geometry to one O(1), one O(10), and one O(9) atom. The P(3)-O(1) bond length is 1.28 Å. The P(3)-O(10) bond length is 2.04 Å. The P(3)-O(9) bond length is 1.94 Å. In the fourth P site, P(4) is bonded in a 1-coordinate geometry to one V(5), one O(12), one O(14), one O(4), and one O(8) atom. The P(4)-O(12) bond length is 2.09 Å. The P(4)-O(14) bond length is 2.06 Å. The P(4)-O(4) bond length is 2.25 Å. The P(4)-O(8) bond length is 1.53 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted water-like geometry to one V(1) and one P(3) atom. In the second O site, O(2) is bonded in a single-bond geometry to one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one V(1), one V(6), one P(2), and one O(7) atom. The O(3)-O(7) bond length is 1.52 Å. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one V(5), two equivalent V(2), one P(4), and one O(15) atom. The O(4)-O(15) bond length is 1.41 Å. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one V(6) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one V(6), one P(1), and one O(16) atom. The O(6)-O(16) bond length is 1.27 Å. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one V(2), one P(2), and one O(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(3) and one P(4) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one P(3), one O(10), and one O(14) atom. The O(9)-O(10) bond length is 1.93 Å. The O(9)-O(14) bond length is 1.48 Å. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to two equivalent V(1), one P(3), one O(13), and one O(9) atom. The O(10)-O(13) bond length is 1.79 Å. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one V(3), one V(4), one V(5), and one V(6) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one V(2), one V(5), one P(4), and one O(14) atom. The O(12)-O(14) bond length is 1.36 Å. In the thirteenth O site, O(13) is bonded in a single-bond geometry to one V(4) and one O(10) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one P(4), one O(12), and one O(9) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one V(5), one P(2), and one O(4) atom. In the sixteenth O site, O(16) is bonded in a bent 120 degrees geometry to one V(4) and one O(6) atom.