CaV4(PO5)4 crystallizes in the triclinic P-1 space group. Ca(1) is bonded in a distorted hexagonal planar geometry to two equivalent O(10), two equivalent O(3), and two equivalent O(9) atoms. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(10), one O(2), one O(3), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-35°. In the second V site, V(2) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 35°. In the third V site, V(3) is bonded to two equivalent O(6), two equivalent O(7), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 30°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-43°. In the second P site, P(2) is bonded to one O(10), one O(4), one O(6), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-46°. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one V(3) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(3) and one P(1) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), and one P(2) atom.
CaV4(PO5)4 crystallizes in the triclinic P-1 space group. Ca(1) is bonded in a distorted hexagonal planar geometry to two equivalent O(10), two equivalent O(3), and two equivalent O(9) atoms. Both Ca(1)-O(10) bond lengths are 2.32 Å. Both Ca(1)-O(3) bond lengths are 2.40 Å. Both Ca(1)-O(9) bond lengths are 2.27 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(10), one O(2), one O(3), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-35°. The V(1)-O(1) bond length is 1.88 Å. The V(1)-O(10) bond length is 2.11 Å. The V(1)-O(2) bond length is 1.93 Å. The V(1)-O(3) bond length is 2.01 Å. The V(1)-O(8) bond length is 1.79 Å. The V(1)-O(9) bond length is 2.08 Å. In the second V site, V(2) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 35°. Both V(2)-O(3) bond lengths are 1.82 Å. Both V(2)-O(4) bond lengths are 2.01 Å. Both V(2)-O(5) bond lengths are 1.94 Å. In the third V site, V(3) is bonded to two equivalent O(6), two equivalent O(7), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 30°. Both V(3)-O(6) bond lengths are 1.92 Å. Both V(3)-O(7) bond lengths are 1.92 Å. Both V(3)-O(8) bond lengths are 1.83 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-43°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(5) bond length is 1.56 Å. The P(1)-O(7) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(10), one O(4), one O(6), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-46°. The P(2)-O(10) bond length is 1.55 Å. The P(2)-O(4) bond length is 1.54 Å. The P(2)-O(6) bond length is 1.55 Å. The P(2)-O(9) bond length is 1.55 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one V(3) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(3) and one P(1) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), and one P(2) atom.