CaVFe(P2O7)2 crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(13), one O(2), one O(4), one O(6), and one O(8) atom. V(1) is bonded to one O(1), one O(12), one O(2), one O(4), one O(5), 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, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. Fe(1) is bonded to one O(10), one O(11), one O(13), one O(14), one O(3), and one O(9) atom to form FeO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(3), one O(4), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-48°. In the second P site, P(2) is bonded to one O(14), one O(2), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 23-48°. In the third P site, P(3) is bonded to one O(1), one O(13), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 27-47°. In the fourth P site, P(4) is bonded to one O(11), one O(12), one O(5), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-47°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Ca(1), one V(1), and one P(3) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Ca(1), one V(1), and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one P(4) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Ca(1), one V(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Ca(1), one P(2), and one P(4) atom. In the ninth O site, O(9) is bonded in a distorted bent 120 degrees geometry to one Fe(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 Fe(1), and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted bent 120 degrees geometry to one Fe(1) and one P(4) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one V(1) and one P(4) atom. In the thirteenth O site, O(13) is bonded in a 2-coordinate geometry to one Ca(1), one Fe(1), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(2) atom.
CaVFe(P2O7)2 crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(13), one O(2), one O(4), one O(6), and one O(8) atom. The Ca(1)-O(1) bond length is 2.42 Å. The Ca(1)-O(10) bond length is 2.37 Å. The Ca(1)-O(13) bond length is 2.84 Å. The Ca(1)-O(2) bond length is 2.66 Å. The Ca(1)-O(4) bond length is 2.46 Å. The Ca(1)-O(6) bond length is 2.35 Å. The Ca(1)-O(8) bond length is 2.36 Å. V(1) is bonded to one O(1), one O(12), one O(2), one O(4), one O(5), 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, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The V(1)-O(1) bond length is 2.12 Å. The V(1)-O(12) bond length is 1.97 Å. The V(1)-O(2) bond length is 2.07 Å. The V(1)-O(4) bond length is 2.10 Å. The V(1)-O(5) bond length is 1.95 Å. The V(1)-O(6) bond length is 2.08 Å. Fe(1) is bonded to one O(10), one O(11), one O(13), one O(14), one O(3), and one O(9) atom to form FeO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The Fe(1)-O(10) bond length is 2.10 Å. The Fe(1)-O(11) bond length is 2.00 Å. The Fe(1)-O(13) bond length is 2.11 Å. The Fe(1)-O(14) bond length is 1.97 Å. The Fe(1)-O(3) bond length is 2.01 Å. The Fe(1)-O(9) bond length is 2.02 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(3), one O(4), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-48°. The P(1)-O(10) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.50 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(7) bond length is 1.62 Å. In the second P site, P(2) is bonded to one O(14), one O(2), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 23-48°. The P(2)-O(14) bond length is 1.52 Å. The P(2)-O(2) bond length is 1.53 Å. The P(2)-O(8) bond length is 1.68 Å. The P(2)-O(9) bond length is 1.52 Å. In the third P site, P(3) is bonded to one O(1), one O(13), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 27-47°. The P(3)-O(1) bond length is 1.53 Å. The P(3)-O(13) bond length is 1.53 Å. The P(3)-O(6) bond length is 1.55 Å. The P(3)-O(7) bond length is 1.60 Å. In the fourth P site, P(4) is bonded to one O(11), one O(12), one O(5), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-47°. The P(4)-O(11) bond length is 1.51 Å. The P(4)-O(12) bond length is 1.54 Å. The P(4)-O(5) bond length is 1.53 Å. The P(4)-O(8) bond length is 1.64 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Ca(1), one V(1), and one P(3) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Ca(1), one V(1), and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one P(4) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Ca(1), one V(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Ca(1), one P(2), and one P(4) atom. In the ninth O site, O(9) is bonded in a distorted bent 120 degrees geometry to one Fe(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 Fe(1), and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted bent 120 degrees geometry to one Fe(1) and one P(4) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one V(1) and one P(4) atom. In the thirteenth O site, O(13) is bonded in a 2-coordinate geometry to one Ca(1), one Fe(1), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(2) atom.