Li4V3Mn(P2O7)4 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a see-saw-like geometry to one O(1), one O(14), one O(2), and one O(28) atom. In the second Li site, Li(2) is bonded in a see-saw-like geometry to one O(11), one O(17), one O(22), and one O(27) atom. In the third Li site, Li(3) is bonded in a see-saw-like geometry to one O(10), one O(16), one O(21), and one O(8) atom. In the fourth Li site, Li(4) is bonded in a see-saw-like geometry to one O(15), one O(20), one O(23), and one O(9) atom. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(12), one O(15), one O(22), one O(23), and one O(4) 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,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, and  a cornercorner with one P(8)O4 tetrahedra. In the second V site, V(2) is bonded to one O(10), one O(13), one O(14), one O(2), one O(21), and one O(3) atom to form VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(7)O4 tetrahedra, and  a cornercorner with one P(8)O4 tetrahedra. In the third V site, V(3) is bonded to one O(1), one O(17), one O(18), one O(26), one O(27), and one O(28) 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(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra,  a cornercorner with one P(7)O4 tetrahedra, and  a cornercorner with one P(8)O4 tetrahedra. Mn(1) is bonded to one O(16), one O(19), one O(20), one O(7), one O(8), and one O(9) atom to form MnO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, and  a cornercorner with one P(7)O4 tetrahedra. There are eight inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(22), one O(5), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-49°. In the second P site, P(2) is bonded to one O(12), one O(17), one O(24), and one O(3) 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 P(5)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-49°. In the third P site, P(3) is bonded to one O(13), one O(16), one O(4), and one O(5) 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 Mn(1)O6 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-49°. In the fourth P site, P(4) is bonded to one O(11), one O(2), one O(6), and one O(9) 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 Mn(1)O6 octahedra, and  a cornercorner with one P(7)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-53°. In the fifth P site, P(5) is bonded to one O(20), one O(21), one O(24), and one O(27) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-49°. In the sixth P site, P(6) is bonded to one O(15), one O(19), one O(25), and one O(26) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one P(8)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 32-49°. In the seventh P site, P(7) is bonded to one O(14), one O(18), one O(6), 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,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-50°. In the eighth P site, P(8) is bonded to one O(10), one O(23), one O(25), 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 P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-49°. There are twenty-eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(3), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(4) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one V(2) and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one V(1) and one P(3) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one P(4) and one P(7) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Mn(1) and one P(7) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(3), one Mn(1), and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(4), one Mn(1), and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(3), one V(2), and one P(8) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(2), one V(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(2) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one V(2) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one P(7) atom. In the fifteenth O site, O(15) is bonded in a distorted T-shaped geometry to one Li(4), one V(1), and one P(6) atom. In the sixteenth O site, O(16) is bonded in a distorted T-shaped geometry to one Li(3), one Mn(1), and one P(3) atom. In the seventeenth O site, O(17) is bonded in a distorted T-shaped geometry to one Li(2), one V(3), and one P(2) atom. In the eighteenth O site, O(18) is bonded in a bent 150 degrees geometry to one V(3) and one P(7) atom. In the nineteenth O site, O(19) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(6) atom. In the twentieth O site, O(20) is bonded in a distorted trigonal planar geometry to one Li(4), one Mn(1), and one P(5) atom. In the twenty-first O site, O(21) is bonded in a distorted trigonal planar geometry to one Li(3), one V(2), and one P(5) atom. In the twenty-second O site, O(22) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one P(1) atom. In the twenty-third O site, O(23) is bonded in a distorted trigonal planar geometry to one Li(4), one V(1), and one P(8) atom. In the twenty-fourth O site, O(24) is bonded in a bent 120 degrees geometry to one P(2) and one P(5) atom. In the twenty-fifth O site, O(25) is bonded in a bent 120 degrees geometry to one P(6) and one P(8) atom. In the twenty-sixth O site, O(26) is bonded in a distorted bent 120 degrees geometry to one V(3) and one P(6) atom. In the twenty-seventh O site, O(27) is bonded in a distorted trigonal planar geometry to one Li(2), one V(3), and one P(5) atom. In the twenty-eighth O site, O(28) is bonded in a distorted trigonal planar geometry to one Li(1), one V(3), and one P(8) atom.
Li4V3Mn(P2O7)4 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a see-saw-like geometry to one O(1), one O(14), one O(2), and one O(28) atom. The Li(1)-O(1) bond length is 2.02 Å. The Li(1)-O(14) bond length is 2.11 Å. The Li(1)-O(2) bond length is 2.00 Å. The Li(1)-O(28) bond length is 2.06 Å. In the second Li site, Li(2) is bonded in a see-saw-like geometry to one O(11), one O(17), one O(22), and one O(27) atom. The Li(2)-O(11) bond length is 2.00 Å. The Li(2)-O(17) bond length is 2.07 Å. The Li(2)-O(22) bond length is 2.06 Å. The Li(2)-O(27) bond length is 2.01 Å. In the third Li site, Li(3) is bonded in a see-saw-like geometry to one O(10), one O(16), one O(21), and one O(8) atom. The Li(3)-O(10) bond length is 1.99 Å. The Li(3)-O(16) bond length is 2.03 Å. The Li(3)-O(21) bond length is 2.05 Å. The Li(3)-O(8) bond length is 2.02 Å. In the fourth Li site, Li(4) is bonded in a see-saw-like geometry to one O(15), one O(20), one O(23), and one O(9) atom. The Li(4)-O(15) bond length is 2.10 Å. The Li(4)-O(20) bond length is 2.01 Å. The Li(4)-O(23) bond length is 2.01 Å. The Li(4)-O(9) bond length is 2.01 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(12), one O(15), one O(22), one O(23), and one O(4) 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,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, and  a cornercorner with one P(8)O4 tetrahedra. The V(1)-O(11) bond length is 2.06 Å. The V(1)-O(12) bond length is 2.00 Å. The V(1)-O(15) bond length is 2.07 Å. The V(1)-O(22) bond length is 2.07 Å. The V(1)-O(23) bond length is 2.07 Å. The V(1)-O(4) bond length is 1.98 Å. In the second V site, V(2) is bonded to one O(10), one O(13), one O(14), one O(2), one O(21), and one O(3) atom to form VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(7)O4 tetrahedra, and  a cornercorner with one P(8)O4 tetrahedra. The V(2)-O(10) bond length is 2.08 Å. The V(2)-O(13) bond length is 1.97 Å. The V(2)-O(14) bond length is 2.08 Å. The V(2)-O(2) bond length is 2.04 Å. The V(2)-O(21) bond length is 2.07 Å. The V(2)-O(3) bond length is 2.00 Å. In the third V site, V(3) is bonded to one O(1), one O(17), one O(18), one O(26), one O(27), and one O(28) 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(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra,  a cornercorner with one P(7)O4 tetrahedra, and  a cornercorner with one P(8)O4 tetrahedra. The V(3)-O(1) bond length is 2.07 Å. The V(3)-O(17) bond length is 2.10 Å. The V(3)-O(18) bond length is 1.98 Å. The V(3)-O(26) bond length is 1.99 Å. The V(3)-O(27) bond length is 2.04 Å. The V(3)-O(28) bond length is 2.09 Å. Mn(1) is bonded to one O(16), one O(19), one O(20), one O(7), one O(8), and one O(9) atom to form MnO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, and  a cornercorner with one P(7)O4 tetrahedra. The Mn(1)-O(16) bond length is 2.16 Å. The Mn(1)-O(19) bond length is 1.96 Å. The Mn(1)-O(20) bond length is 2.07 Å. The Mn(1)-O(7) bond length is 1.97 Å. The Mn(1)-O(8) bond length is 2.05 Å. The Mn(1)-O(9) bond length is 2.17 Å. There are eight inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(22), one O(5), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-49°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(22) bond length is 1.53 Å. The P(1)-O(5) bond length is 1.61 Å. The P(1)-O(8) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(12), one O(17), one O(24), and one O(3) 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 P(5)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-49°. The P(2)-O(12) bond length is 1.52 Å. The P(2)-O(17) bond length is 1.52 Å. The P(2)-O(24) bond length is 1.63 Å. The P(2)-O(3) bond length is 1.53 Å. In the third P site, P(3) is bonded to one O(13), one O(16), one O(4), and one O(5) 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 Mn(1)O6 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-49°. The P(3)-O(13) bond length is 1.52 Å. The P(3)-O(16) bond length is 1.52 Å. The P(3)-O(4) bond length is 1.54 Å. The P(3)-O(5) bond length is 1.63 Å. In the fourth P site, P(4) is bonded to one O(11), one O(2), one O(6), and one O(9) 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 Mn(1)O6 octahedra, and  a cornercorner with one P(7)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-53°. The P(4)-O(11) bond length is 1.54 Å. The P(4)-O(2) bond length is 1.54 Å. The P(4)-O(6) bond length is 1.62 Å. The P(4)-O(9) bond length is 1.52 Å. In the fifth P site, P(5) is bonded to one O(20), one O(21), one O(24), and one O(27) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-49°. The P(5)-O(20) bond length is 1.54 Å. The P(5)-O(21) bond length is 1.53 Å. The P(5)-O(24) bond length is 1.61 Å. The P(5)-O(27) bond length is 1.54 Å. In the sixth P site, P(6) is bonded to one O(15), one O(19), one O(25), and one O(26) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one P(8)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 32-49°. The P(6)-O(15) bond length is 1.52 Å. The P(6)-O(19) bond length is 1.53 Å. The P(6)-O(25) bond length is 1.63 Å. The P(6)-O(26) bond length is 1.53 Å. In the seventh P site, P(7) is bonded to one O(14), one O(18), one O(6), 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,  a cornercorner with one Mn(1)O6 octahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-50°. The P(7)-O(14) bond length is 1.52 Å. The P(7)-O(18) bond length is 1.52 Å. The P(7)-O(6) bond length is 1.62 Å. The P(7)-O(7) bond length is 1.54 Å. In the eighth P site, P(8) is bonded to one O(10), one O(23), one O(25), 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 P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-49°. The P(8)-O(10) bond length is 1.53 Å. The P(8)-O(23) bond length is 1.54 Å. The P(8)-O(25) bond length is 1.62 Å. The P(8)-O(28) bond length is 1.53 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 Li(1), one V(3), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(4) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one V(2) and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one V(1) and one P(3) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one P(4) and one P(7) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Mn(1) and one P(7) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(3), one Mn(1), and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(4), one Mn(1), and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(3), one V(2), and one P(8) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(2), one V(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(2) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one V(2) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one P(7) atom. In the fifteenth O site, O(15) is bonded in a distorted T-shaped geometry to one Li(4), one V(1), and one P(6) atom. In the sixteenth O site, O(16) is bonded in a distorted T-shaped geometry to one Li(3), one Mn(1), and one P(3) atom. In the seventeenth O site, O(17) is bonded in a distorted T-shaped geometry to one Li(2), one V(3), and one P(2) atom. In the eighteenth O site, O(18) is bonded in a bent 150 degrees geometry to one V(3) and one P(7) atom. In the nineteenth O site, O(19) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(6) atom. In the twentieth O site, O(20) is bonded in a distorted trigonal planar geometry to one Li(4), one Mn(1), and one P(5) atom. In the twenty-first O site, O(21) is bonded in a distorted trigonal planar geometry to one Li(3), one V(2), and one P(5) atom. In the twenty-second O site, O(22) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one P(1) atom. In the twenty-third O site, O(23) is bonded in a distorted trigonal planar geometry to one Li(4), one V(1), and one P(8) atom. In the twenty-fourth O site, O(24) is bonded in a bent 120 degrees geometry to one P(2) and one P(5) atom. In the twenty-fifth O site, O(25) is bonded in a bent 120 degrees geometry to one P(6) and one P(8) atom. In the twenty-sixth O site, O(26) is bonded in a distorted bent 120 degrees geometry to one V(3) and one P(6) atom. In the twenty-seventh O site, O(27) is bonded in a distorted trigonal planar geometry to one Li(2), one V(3), and one P(5) atom. In the twenty-eighth O site, O(28) is bonded in a distorted trigonal planar geometry to one Li(1), one V(3), and one P(8) atom.