CaV4(CoO4)3 crystallizes in the triclinic P1 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(1), one O(12), one O(14), one O(15), one O(17), one O(20), one O(22), one O(23), one O(4), one O(6), one O(7), and one O(9) atom to form CaO12 cuboctahedra that share  a faceface with one V(1)O6 octahedra,  a faceface with one V(2)O6 octahedra,  a faceface with one V(3)O6 octahedra,  a faceface with one V(4)O6 octahedra,  a faceface with one V(5)O6 octahedra,  a faceface with one V(6)O6 octahedra,  a faceface with one V(7)O6 octahedra, and  a faceface with one V(8)O6 octahedra. In the second Ca site, Ca(2) is bonded to one O(10), one O(11), one O(13), one O(16), one O(18), one O(19), one O(2), one O(21), one O(24), one O(3), one O(5), and one O(8) atom to form CaO12 cuboctahedra that share  a faceface with one V(1)O6 octahedra,  a faceface with one V(2)O6 octahedra,  a faceface with one V(3)O6 octahedra,  a faceface with one V(4)O6 octahedra,  a faceface with one V(5)O6 octahedra,  a faceface with one V(6)O6 octahedra,  a faceface with one V(7)O6 octahedra, and  a faceface with one V(8)O6 octahedra. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(13), one O(15), one O(17), one O(19), one O(6), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(6)O6 octahedra, corners with two equivalent V(7)O6 octahedra,  a faceface with one Ca(1)O12 cuboctahedra, and  a faceface with one Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 35-38°. In the second V site, V(2) is bonded to one O(14), one O(16), one O(18), one O(20), one O(5), and one O(7) atom to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(5)O6 octahedra, corners with two equivalent V(8)O6 octahedra,  a faceface with one Ca(1)O12 cuboctahedra, and  a faceface with one Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 35-37°. In the third V site, V(3) is bonded to one O(11), one O(22), one O(24), one O(5), one O(7), and one O(9) atom to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(6)O6 octahedra, corners with two equivalent V(7)O6 octahedra,  a faceface with one Ca(1)O12 cuboctahedra, and  a faceface with one Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 35-37°. In the fourth V site, V(4) is bonded to one O(10), one O(12), one O(21), one O(23), one O(6), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(5)O6 octahedra, corners with two equivalent V(8)O6 octahedra,  a faceface with one Ca(1)O12 cuboctahedra, and  a faceface with one Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 35-38°. In the fifth V site, V(5) is bonded to one O(1), one O(14), one O(16), one O(21), one O(23), and one O(3) atom to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(7)O6 octahedra,  a faceface with one Ca(1)O12 cuboctahedra, and  a faceface with one Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 36-38°. In the sixth V site, V(6) is bonded to one O(13), one O(15), one O(2), one O(22), one O(24), and one O(4) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(8)O6 octahedra,  a faceface with one Ca(1)O12 cuboctahedra, and  a faceface with one Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 36-38°. In the seventh V site, V(7) is bonded to one O(1), one O(11), one O(17), one O(19), one O(3), and one O(9) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(5)O6 octahedra,  a faceface with one Ca(1)O12 cuboctahedra, and  a faceface with one Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 35-38°. In the eighth V site, V(8) is bonded to one O(10), one O(12), one O(18), one O(2), one O(20), and one O(4) atom to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(6)O6 octahedra,  a faceface with one Ca(1)O12 cuboctahedra, and  a faceface with one Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 35-38°. There are six inequivalent Co sites. In the first Co site, Co(1) is bonded in a square co-planar geometry to one O(18), one O(19), one O(21), and one O(24) atom. In the second Co site, Co(2) is bonded in a square co-planar geometry to one O(2), one O(3), one O(5), and one O(8) atom. In the third Co site, Co(3) is bonded in a square co-planar geometry to one O(10), one O(11), one O(13), and one O(16) atom. In the fourth Co site, Co(4) is bonded in a square co-planar geometry to one O(17), one O(20), one O(22), and one O(23) atom. In the fifth Co site, Co(5) is bonded in a square co-planar geometry to one O(1), one O(4), one O(6), and one O(7) atom. In the sixth Co site, Co(6) is bonded in a square co-planar geometry to one O(12), one O(14), one O(15), and one O(9) atom. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Ca(1), one V(5), one V(7), and one Co(5) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ca(2), one V(6), one V(8), and one Co(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ca(2), one V(5), one V(7), and one Co(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ca(1), one V(6), one V(8), and one Co(5) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Ca(2), one V(2), one V(3), and one Co(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), one V(4), and one Co(5) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Ca(1), one V(2), one V(3), and one Co(5) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Ca(2), one V(1), one V(4), and one Co(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Ca(1), one V(3), one V(7), and one Co(6) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Ca(2), one V(4), one V(8), and one Co(3) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Ca(2), one V(3), one V(7), and one Co(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Ca(1), one V(4), one V(8), and one Co(6) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Ca(2), one V(1), one V(6), and one Co(3) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Ca(1), one V(2), one V(5), and one Co(6) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), one V(6), and one Co(6) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Ca(2), one V(2), one V(5), and one Co(3) atom. In the seventeenth O site, O(17) is bonded in a 4-coordinate geometry to one Ca(1), one V(1), one V(7), and one Co(4) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one Ca(2), one V(2), one V(8), and one Co(1) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Ca(2), one V(1), one V(7), and one Co(1) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Ca(1), one V(2), one V(8), and one Co(4) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Ca(2), one V(4), one V(5), and one Co(1) atom. In the twenty-second O site, O(22) is bonded in a 3-coordinate geometry to one Ca(1), one V(3), one V(6), and one Co(4) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Ca(1), one V(4), one V(5), and one Co(4) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Ca(2), one V(3), one V(6), and one Co(1) atom.
CaV4(CoO4)3 crystallizes in the triclinic P1 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(1), one O(12), one O(14), one O(15), one O(17), one O(20), one O(22), one O(23), one O(4), one O(6), one O(7), and one O(9) atom to form CaO12 cuboctahedra that share  a faceface with one V(1)O6 octahedra,  a faceface with one V(2)O6 octahedra,  a faceface with one V(3)O6 octahedra,  a faceface with one V(4)O6 octahedra,  a faceface with one V(5)O6 octahedra,  a faceface with one V(6)O6 octahedra,  a faceface with one V(7)O6 octahedra, and  a faceface with one V(8)O6 octahedra. The Ca(1)-O(1) bond length is 2.62 Å. The Ca(1)-O(12) bond length is 2.63 Å. The Ca(1)-O(14) bond length is 2.63 Å. The Ca(1)-O(15) bond length is 2.61 Å. The Ca(1)-O(17) bond length is 2.59 Å. The Ca(1)-O(20) bond length is 2.63 Å. The Ca(1)-O(22) bond length is 2.63 Å. The Ca(1)-O(23) bond length is 2.64 Å. The Ca(1)-O(4) bond length is 2.65 Å. The Ca(1)-O(6) bond length is 2.60 Å. The Ca(1)-O(7) bond length is 2.63 Å. The Ca(1)-O(9) bond length is 2.60 Å. In the second Ca site, Ca(2) is bonded to one O(10), one O(11), one O(13), one O(16), one O(18), one O(19), one O(2), one O(21), one O(24), one O(3), one O(5), and one O(8) atom to form CaO12 cuboctahedra that share  a faceface with one V(1)O6 octahedra,  a faceface with one V(2)O6 octahedra,  a faceface with one V(3)O6 octahedra,  a faceface with one V(4)O6 octahedra,  a faceface with one V(5)O6 octahedra,  a faceface with one V(6)O6 octahedra,  a faceface with one V(7)O6 octahedra, and  a faceface with one V(8)O6 octahedra. The Ca(2)-O(10) bond length is 2.62 Å. The Ca(2)-O(11) bond length is 2.60 Å. The Ca(2)-O(13) bond length is 2.64 Å. The Ca(2)-O(16) bond length is 2.63 Å. The Ca(2)-O(18) bond length is 2.64 Å. The Ca(2)-O(19) bond length is 2.60 Å. The Ca(2)-O(2) bond length is 2.66 Å. The Ca(2)-O(21) bond length is 2.64 Å. The Ca(2)-O(24) bond length is 2.63 Å. The Ca(2)-O(3) bond length is 2.64 Å. The Ca(2)-O(5) bond length is 2.62 Å. The Ca(2)-O(8) bond length is 2.59 Å. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(13), one O(15), one O(17), one O(19), one O(6), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(6)O6 octahedra, corners with two equivalent V(7)O6 octahedra,  a faceface with one Ca(1)O12 cuboctahedra, and  a faceface with one Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 35-38°. The V(1)-O(13) bond length is 1.96 Å. The V(1)-O(15) bond length is 1.97 Å. The V(1)-O(17) bond length is 1.90 Å. The V(1)-O(19) bond length is 1.93 Å. The V(1)-O(6) bond length is 2.02 Å. The V(1)-O(8) bond length is 1.99 Å. In the second V site, V(2) is bonded to one O(14), one O(16), one O(18), one O(20), one O(5), and one O(7) atom to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(5)O6 octahedra, corners with two equivalent V(8)O6 octahedra,  a faceface with one Ca(1)O12 cuboctahedra, and  a faceface with one Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 35-37°. The V(2)-O(14) bond length is 2.00 Å. The V(2)-O(16) bond length is 1.99 Å. The V(2)-O(18) bond length is 1.91 Å. The V(2)-O(20) bond length is 1.88 Å. The V(2)-O(5) bond length is 2.00 Å. The V(2)-O(7) bond length is 2.03 Å. In the third V site, V(3) is bonded to one O(11), one O(22), one O(24), one O(5), one O(7), and one O(9) atom to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(6)O6 octahedra, corners with two equivalent V(7)O6 octahedra,  a faceface with one Ca(1)O12 cuboctahedra, and  a faceface with one Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 35-37°. The V(3)-O(11) bond length is 1.99 Å. The V(3)-O(22) bond length is 1.99 Å. The V(3)-O(24) bond length is 1.99 Å. The V(3)-O(5) bond length is 1.92 Å. The V(3)-O(7) bond length is 1.90 Å. The V(3)-O(9) bond length is 2.01 Å. In the fourth V site, V(4) is bonded to one O(10), one O(12), one O(21), one O(23), one O(6), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(5)O6 octahedra, corners with two equivalent V(8)O6 octahedra,  a faceface with one Ca(1)O12 cuboctahedra, and  a faceface with one Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 35-38°. The V(4)-O(10) bond length is 2.00 Å. The V(4)-O(12) bond length is 2.02 Å. The V(4)-O(21) bond length is 1.97 Å. The V(4)-O(23) bond length is 1.97 Å. The V(4)-O(6) bond length is 1.90 Å. The V(4)-O(8) bond length is 1.93 Å. In the fifth V site, V(5) is bonded to one O(1), one O(14), one O(16), one O(21), one O(23), and one O(3) atom to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(7)O6 octahedra,  a faceface with one Ca(1)O12 cuboctahedra, and  a faceface with one Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 36-38°. The V(5)-O(1) bond length is 1.98 Å. The V(5)-O(14) bond length is 1.93 Å. The V(5)-O(16) bond length is 1.93 Å. The V(5)-O(21) bond length is 1.96 Å. The V(5)-O(23) bond length is 1.97 Å. The V(5)-O(3) bond length is 1.98 Å. In the sixth V site, V(6) is bonded to one O(13), one O(15), one O(2), one O(22), one O(24), and one O(4) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(8)O6 octahedra,  a faceface with one Ca(1)O12 cuboctahedra, and  a faceface with one Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 36-38°. The V(6)-O(13) bond length is 1.97 Å. The V(6)-O(15) bond length is 1.97 Å. The V(6)-O(2) bond length is 1.96 Å. The V(6)-O(22) bond length is 1.94 Å. The V(6)-O(24) bond length is 1.93 Å. The V(6)-O(4) bond length is 1.98 Å. In the seventh V site, V(7) is bonded to one O(1), one O(11), one O(17), one O(19), one O(3), and one O(9) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(5)O6 octahedra,  a faceface with one Ca(1)O12 cuboctahedra, and  a faceface with one Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 35-38°. The V(7)-O(1) bond length is 1.97 Å. The V(7)-O(11) bond length is 1.93 Å. The V(7)-O(17) bond length is 2.01 Å. The V(7)-O(19) bond length is 1.99 Å. The V(7)-O(3) bond length is 1.96 Å. The V(7)-O(9) bond length is 1.91 Å. In the eighth V site, V(8) is bonded to one O(10), one O(12), one O(18), one O(2), one O(20), and one O(4) atom to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(6)O6 octahedra,  a faceface with one Ca(1)O12 cuboctahedra, and  a faceface with one Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 35-38°. The V(8)-O(10) bond length is 1.92 Å. The V(8)-O(12) bond length is 1.90 Å. The V(8)-O(18) bond length is 2.00 Å. The V(8)-O(2) bond length is 1.98 Å. The V(8)-O(20) bond length is 2.03 Å. The V(8)-O(4) bond length is 1.97 Å. There are six inequivalent Co sites. In the first Co site, Co(1) is bonded in a square co-planar geometry to one O(18), one O(19), one O(21), and one O(24) atom. The Co(1)-O(18) bond length is 2.06 Å. The Co(1)-O(19) bond length is 2.05 Å. The Co(1)-O(21) bond length is 2.01 Å. The Co(1)-O(24) bond length is 2.03 Å. In the second Co site, Co(2) is bonded in a square co-planar geometry to one O(2), one O(3), one O(5), and one O(8) atom. The Co(2)-O(2) bond length is 2.00 Å. The Co(2)-O(3) bond length is 2.00 Å. The Co(2)-O(5) bond length is 2.07 Å. The Co(2)-O(8) bond length is 2.05 Å. In the third Co site, Co(3) is bonded in a square co-planar geometry to one O(10), one O(11), one O(13), and one O(16) atom. The Co(3)-O(10) bond length is 2.05 Å. The Co(3)-O(11) bond length is 2.05 Å. The Co(3)-O(13) bond length is 2.01 Å. The Co(3)-O(16) bond length is 2.03 Å. In the fourth Co site, Co(4) is bonded in a square co-planar geometry to one O(17), one O(20), one O(22), and one O(23) atom. The Co(4)-O(17) bond length is 2.05 Å. The Co(4)-O(20) bond length is 2.07 Å. The Co(4)-O(22) bond length is 2.02 Å. The Co(4)-O(23) bond length is 2.00 Å. In the fifth Co site, Co(5) is bonded in a square co-planar geometry to one O(1), one O(4), one O(6), and one O(7) atom. The Co(5)-O(1) bond length is 2.00 Å. The Co(5)-O(4) bond length is 2.00 Å. The Co(5)-O(6) bond length is 2.05 Å. The Co(5)-O(7) bond length is 2.06 Å. In the sixth Co site, Co(6) is bonded in a square co-planar geometry to one O(12), one O(14), one O(15), and one O(9) atom. The Co(6)-O(12) bond length is 2.05 Å. The Co(6)-O(14) bond length is 2.03 Å. The Co(6)-O(15) bond length is 2.01 Å. The Co(6)-O(9) bond length is 2.05 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Ca(1), one V(5), one V(7), and one Co(5) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ca(2), one V(6), one V(8), and one Co(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ca(2), one V(5), one V(7), and one Co(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ca(1), one V(6), one V(8), and one Co(5) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Ca(2), one V(2), one V(3), and one Co(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), one V(4), and one Co(5) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Ca(1), one V(2), one V(3), and one Co(5) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Ca(2), one V(1), one V(4), and one Co(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Ca(1), one V(3), one V(7), and one Co(6) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Ca(2), one V(4), one V(8), and one Co(3) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Ca(2), one V(3), one V(7), and one Co(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Ca(1), one V(4), one V(8), and one Co(6) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Ca(2), one V(1), one V(6), and one Co(3) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Ca(1), one V(2), one V(5), and one Co(6) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), one V(6), and one Co(6) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Ca(2), one V(2), one V(5), and one Co(3) atom. In the seventeenth O site, O(17) is bonded in a 4-coordinate geometry to one Ca(1), one V(1), one V(7), and one Co(4) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one Ca(2), one V(2), one V(8), and one Co(1) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Ca(2), one V(1), one V(7), and one Co(1) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Ca(1), one V(2), one V(8), and one Co(4) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Ca(2), one V(4), one V(5), and one Co(1) atom. In the twenty-second O site, O(22) is bonded in a 3-coordinate geometry to one Ca(1), one V(3), one V(6), and one Co(4) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one Ca(1), one V(4), one V(5), and one Co(4) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Ca(2), one V(3), one V(6), and one Co(1) atom.