Li2VCr(P2O7)2 crystallizes in the monoclinic P2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a see-saw-like geometry to one O(3), one O(4), one O(5), and one O(7) atom. In the second Li site, Li(2) is bonded in a see-saw-like geometry to one O(10), one O(11), one O(12), and one O(14) 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  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. Cr(1) is bonded to one O(10), one O(11), one O(12), one O(13), one O(14), and one O(9) atom to form CrO6 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. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(13), one O(2), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(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 34-50°. In the second P site, P(2) is bonded to one O(1), one O(10), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(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 46-50°. In the third P site, P(3) is bonded to one O(14), one O(6), 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 Cr(1)O6 octahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-50°. In the fourth P site, P(4) is bonded to one O(11), one O(12), one O(3), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-49°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(2) is bonded in a distorted bent 120 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 Li(1), one V(1), and one P(4) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(1) and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one P(3) and one P(4) atom. In the ninth O site, O(9) is bonded in a distorted bent 120 degrees geometry to one Cr(1) and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(2), one Cr(1), and one P(2) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(2), one Cr(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(2), one Cr(1), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the fourteenth O site, O(14) is bonded in a distorted T-shaped geometry to one Li(2), one Cr(1), and one P(3) atom.
Li2VCr(P2O7)2 crystallizes in the monoclinic P2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a see-saw-like geometry to one O(3), one O(4), one O(5), and one O(7) atom. The Li(1)-O(3) bond length is 2.01 Å. The Li(1)-O(4) bond length is 2.05 Å. The Li(1)-O(5) bond length is 2.00 Å. The Li(1)-O(7) bond length is 2.07 Å. In the second Li site, Li(2) is bonded in a see-saw-like geometry to one O(10), one O(11), one O(12), and one O(14) atom. The Li(2)-O(10) bond length is 2.00 Å. The Li(2)-O(11) bond length is 2.07 Å. The Li(2)-O(12) bond length is 2.00 Å. The Li(2)-O(14) bond length is 2.08 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  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 V(1)-O(2) bond length is 1.99 Å. The V(1)-O(3) bond length is 2.06 Å. The V(1)-O(4) bond length is 2.07 Å. The V(1)-O(5) bond length is 2.06 Å. The V(1)-O(6) bond length is 2.00 Å. The V(1)-O(7) bond length is 2.08 Å. Cr(1) is bonded to one O(10), one O(11), one O(12), one O(13), one O(14), and one O(9) atom to form CrO6 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 Cr(1)-O(10) bond length is 2.04 Å. The Cr(1)-O(11) bond length is 2.03 Å. The Cr(1)-O(12) bond length is 2.05 Å. The Cr(1)-O(13) bond length is 1.98 Å. The Cr(1)-O(14) bond length is 2.04 Å. The Cr(1)-O(9) bond length is 2.00 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(13), one O(2), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(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 34-50°. The P(1)-O(1) bond length is 1.63 Å. The P(1)-O(13) bond length is 1.52 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(7) bond length is 1.52 Å. In the second P site, P(2) is bonded to one O(1), one O(10), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Cr(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 46-50°. The P(2)-O(1) bond length is 1.61 Å. The P(2)-O(10) bond length is 1.53 Å. The P(2)-O(4) bond length is 1.53 Å. The P(2)-O(5) bond length is 1.54 Å. In the third P site, P(3) is bonded to one O(14), one O(6), 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 Cr(1)O6 octahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-50°. The P(3)-O(14) bond length is 1.53 Å. The P(3)-O(6) bond length is 1.52 Å. The P(3)-O(8) bond length is 1.63 Å. The P(3)-O(9) bond length is 1.53 Å. In the fourth P site, P(4) is bonded to one O(11), one O(12), one O(3), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-49°. The P(4)-O(11) bond length is 1.54 Å. The P(4)-O(12) bond length is 1.53 Å. The P(4)-O(3) bond length is 1.53 Å. The P(4)-O(8) bond length is 1.61 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(2) is bonded in a distorted bent 120 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 Li(1), one V(1), and one P(4) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(1) and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one P(3) and one P(4) atom. In the ninth O site, O(9) is bonded in a distorted bent 120 degrees geometry to one Cr(1) and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(2), one Cr(1), and one P(2) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(2), one Cr(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(2), one Cr(1), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the fourteenth O site, O(14) is bonded in a distorted T-shaped geometry to one Li(2), one Cr(1), and one P(3) atom.