CaV4(CoO4)3 crystallizes in the triclinic P-1 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent O(1), two equivalent O(11), two equivalent O(3), two equivalent O(5), two equivalent O(8), and two equivalent O(9) atoms to form CaO12 cuboctahedra that share faces with two equivalent V(1)O6 octahedra, faces with two equivalent V(2)O6 octahedra, faces with two equivalent V(4)O6 octahedra, and faces with two equivalent V(6)O6 octahedra. In the second Ca site, Ca(2) is bonded to two equivalent O(10), two equivalent O(12), two equivalent O(2), two equivalent O(4), two equivalent O(6), and two equivalent O(7) atoms to form CaO12 cuboctahedra that share faces with two equivalent V(1)O6 octahedra, faces with two equivalent V(3)O6 octahedra, faces with two equivalent V(5)O6 octahedra, and faces with two equivalent V(6)O6 octahedra. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(3), one O(4), one O(7), 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,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(5)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°. In the second V site, V(2) is bonded to two equivalent O(11), two equivalent O(3), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(6)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 36-38°. In the third V site, V(3) is bonded to two equivalent O(12), two equivalent O(4), and two equivalent O(6) atoms 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(6)O6 octahedra, and faces with two equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 35-38°. In the fourth V site, V(4) is bonded to two equivalent O(1), two equivalent O(11), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(6)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 36°. In the fifth V site, V(5) is bonded to two equivalent O(12), two equivalent O(2), and two equivalent O(7) atoms 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(6)O6 octahedra, and faces with two equivalent 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(1), one O(10), one O(2), one O(5), one O(6), 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,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(5)O6 octahedra, corners with two equivalent V(1)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 four inequivalent Co sites. In the first Co site, Co(1) is bonded in a square co-planar geometry to one O(1), one O(2), one O(3), and one O(4) atom. In the second Co site, Co(2) is bonded in a square co-planar geometry to two equivalent O(6) and two equivalent O(7) atoms. In the third Co site, Co(3) is bonded in a square co-planar geometry to one O(10), one O(11), one O(12), and one O(9) atom. In the fourth Co site, Co(4) is bonded in a square co-planar geometry to two equivalent O(5) and two equivalent O(8) atoms. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Ca(1), one V(4), one V(6), and one Co(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ca(2), one V(5), one V(6), and one Co(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), one V(2), and one Co(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ca(2), one V(1), one V(3), and one Co(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Ca(1), one V(2), one V(6), and one Co(4) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Ca(2), one V(3), one V(6), and one Co(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Ca(2), one V(1), one V(5), and one Co(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), one V(4), and one Co(4) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Ca(1), one V(1), one V(6), and one Co(3) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Ca(2), one V(1), one V(6), and one Co(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Ca(1), one V(2), one V(4), and one Co(3) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Ca(2), one V(3), one V(5), and one Co(3) atom.
CaV4(CoO4)3 crystallizes in the triclinic P-1 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent O(1), two equivalent O(11), two equivalent O(3), two equivalent O(5), two equivalent O(8), and two equivalent O(9) atoms to form CaO12 cuboctahedra that share faces with two equivalent V(1)O6 octahedra, faces with two equivalent V(2)O6 octahedra, faces with two equivalent V(4)O6 octahedra, and faces with two equivalent V(6)O6 octahedra. Both Ca(1)-O(1) bond lengths are 2.64 Å. Both Ca(1)-O(11) bond lengths are 2.62 Å. Both Ca(1)-O(3) bond lengths are 2.66 Å. Both Ca(1)-O(5) bond lengths are 2.61 Å. Both Ca(1)-O(8) bond lengths are 2.62 Å. Both Ca(1)-O(9) bond lengths are 2.61 Å. In the second Ca site, Ca(2) is bonded to two equivalent O(10), two equivalent O(12), two equivalent O(2), two equivalent O(4), two equivalent O(6), and two equivalent O(7) atoms to form CaO12 cuboctahedra that share faces with two equivalent V(1)O6 octahedra, faces with two equivalent V(3)O6 octahedra, faces with two equivalent V(5)O6 octahedra, and faces with two equivalent V(6)O6 octahedra. Both Ca(2)-O(10) bond lengths are 2.63 Å. Both Ca(2)-O(12) bond lengths are 2.61 Å. Both Ca(2)-O(2) bond lengths are 2.63 Å. Both Ca(2)-O(4) bond lengths are 2.65 Å. Both Ca(2)-O(6) bond lengths are 2.63 Å. Both Ca(2)-O(7) bond lengths are 2.60 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(3), one O(4), one O(7), 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,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(5)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(1)-O(10) bond length is 1.99 Å. The V(1)-O(3) bond length is 1.97 Å. The V(1)-O(4) bond length is 2.04 Å. The V(1)-O(7) bond length is 1.89 Å. The V(1)-O(8) bond length is 1.91 Å. The V(1)-O(9) bond length is 2.00 Å. In the second V site, V(2) is bonded to two equivalent O(11), two equivalent O(3), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(6)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 36-38°. Both V(2)-O(11) bond lengths are 2.01 Å. Both V(2)-O(3) bond lengths are 1.98 Å. Both V(2)-O(5) bond lengths are 1.90 Å. In the third V site, V(3) is bonded to two equivalent O(12), two equivalent O(4), and two equivalent O(6) atoms 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(6)O6 octahedra, and faces with two equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 35-38°. Both V(3)-O(12) bond lengths are 2.01 Å. Both V(3)-O(4) bond lengths are 1.90 Å. Both V(3)-O(6) bond lengths are 1.97 Å. In the fourth V site, V(4) is bonded to two equivalent O(1), two equivalent O(11), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(6)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 36°. Both V(4)-O(1) bond lengths are 1.99 Å. Both V(4)-O(11) bond lengths are 1.90 Å. Both V(4)-O(8) bond lengths are 2.01 Å. In the fifth V site, V(5) is bonded to two equivalent O(12), two equivalent O(2), and two equivalent O(7) atoms 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(6)O6 octahedra, and faces with two equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 36-38°. Both V(5)-O(12) bond lengths are 1.90 Å. Both V(5)-O(2) bond lengths are 1.98 Å. Both V(5)-O(7) bond lengths are 2.02 Å. In the sixth V site, V(6) is bonded to one O(1), one O(10), one O(2), one O(5), one O(6), 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,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(5)O6 octahedra, corners with two equivalent V(1)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(6)-O(1) bond length is 1.98 Å. The V(6)-O(10) bond length is 1.92 Å. The V(6)-O(2) bond length is 1.98 Å. The V(6)-O(5) bond length is 2.04 Å. The V(6)-O(6) bond length is 1.95 Å. The V(6)-O(9) bond length is 1.91 Å. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded in a square co-planar geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Co(1)-O(1) bond length is 2.01 Å. The Co(1)-O(2) bond length is 2.01 Å. The Co(1)-O(3) bond length is 2.00 Å. The Co(1)-O(4) bond length is 2.04 Å. In the second Co site, Co(2) is bonded in a square co-planar geometry to two equivalent O(6) and two equivalent O(7) atoms. Both Co(2)-O(6) bond lengths are 2.00 Å. Both Co(2)-O(7) bond lengths are 2.04 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(12), and one O(9) atom. The Co(3)-O(10) bond length is 2.04 Å. The Co(3)-O(11) bond length is 2.04 Å. The Co(3)-O(12) bond length is 2.04 Å. The Co(3)-O(9) bond length is 2.05 Å. In the fourth Co site, Co(4) is bonded in a square co-planar geometry to two equivalent O(5) and two equivalent O(8) atoms. Both Co(4)-O(5) bond lengths are 2.02 Å. Both Co(4)-O(8) bond lengths are 2.04 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Ca(1), one V(4), one V(6), and one Co(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ca(2), one V(5), one V(6), and one Co(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), one V(2), and one Co(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ca(2), one V(1), one V(3), and one Co(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Ca(1), one V(2), one V(6), and one Co(4) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Ca(2), one V(3), one V(6), and one Co(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Ca(2), one V(1), one V(5), and one Co(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), one V(4), and one Co(4) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Ca(1), one V(1), one V(6), and one Co(3) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Ca(2), one V(1), one V(6), and one Co(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Ca(1), one V(2), one V(4), and one Co(3) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Ca(2), one V(3), one V(5), and one Co(3) atom.