CaTi3V5O16 crystallizes in the triclinic P1 space group. Ca(1) is bonded to one O(11), one O(12), one O(15), and one O(3) atom to form distorted CaO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(5)O6 octahedra, and corners with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-69°. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(14), one O(2), one O(3), one O(4), one O(7), and one O(9) atom to form distorted TiO6 octahedra that share corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Ca(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-54°. In the second Ti site, Ti(2) is bonded to one O(16), one O(2), one O(3), one O(4), one O(8), and one O(9) atom to form distorted TiO6 octahedra that share corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Ca(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-47°. In the third Ti site, Ti(3) is bonded to one O(1), one O(11), one O(12), one O(13), one O(5), and one O(6) atom to form distorted TiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Ca(1)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles are 55°. There are five inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(10), one O(2), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share corners with two equivalent Ti(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(5)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. In the second V site, V(2) is bonded to one O(14), one O(16), one O(3), one O(4), one O(7), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Ca(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-55°. In the third V site, V(3) is bonded to one O(11), one O(12), one O(14), one O(15), one O(16), and one O(9) atom to form VO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent Ca(1)O4 tetrahedra,  an edgeedge with one Ti(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, and  an edgeedge with one V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. In the fourth V site, V(4) is bonded to one O(10), one O(12), one O(13), one O(15), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Ca(1)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-51°. In the fifth V site, V(5) is bonded to one O(1), one O(10), one O(11), one O(13), one O(15), and one O(5) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Ca(1)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles are 48°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Ti(3), one V(1), and one V(5) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1), one Ti(2), and one V(1) atom. In the third O site, O(3) is bonded to one Ca(1), one Ti(1), one Ti(2), and one V(2) atom to form distorted OCaTi2V tetrahedra that share  a cornercorner with one O(11)CaTiV2 tetrahedra,  a cornercorner with one O(12)CaTiV2 tetrahedra, and  a cornercorner with one O(15)CaV3 tetrahedra. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1), one Ti(2), and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Ti(3), one V(4), and one V(5) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Ti(3), one V(1), and one V(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Ti(1), one V(1), and one V(2) atom. In the eighth O site, O(8) is bonded in a trigonal non-coplanar geometry to one Ti(2), one V(1), and one V(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Ti(1), one Ti(2), and one V(3) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one V(1), one V(4), and one V(5) atom. In the eleventh O site, O(11) is bonded to one Ca(1), one Ti(3), one V(3), and one V(5) atom to form OCaTiV2 tetrahedra that share  a cornercorner with one O(3)CaTi2V tetrahedra,  a cornercorner with one O(12)CaTiV2 tetrahedra,  a cornercorner with one O(15)CaV3 tetrahedra,  an edgeedge with one O(12)CaTiV2 tetrahedra, and  an edgeedge with one O(15)CaV3 tetrahedra. In the twelfth O site, O(12) is bonded to one Ca(1), one Ti(3), one V(3), and one V(4) atom to form OCaTiV2 tetrahedra that share  a cornercorner with one O(3)CaTi2V tetrahedra,  a cornercorner with one O(11)CaTiV2 tetrahedra,  a cornercorner with one O(15)CaV3 tetrahedra,  an edgeedge with one O(11)CaTiV2 tetrahedra, and  an edgeedge with one O(15)CaV3 tetrahedra. In the thirteenth O site, O(13) is bonded in a distorted trigonal non-coplanar geometry to one Ti(3), one V(4), and one V(5) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Ti(1), one V(2), and one V(3) atom. In the fifteenth O site, O(15) is bonded to one Ca(1), one V(3), one V(4), and one V(5) atom to form OCaV3 tetrahedra that share  a cornercorner with one O(3)CaTi2V tetrahedra,  a cornercorner with one O(11)CaTiV2 tetrahedra,  a cornercorner with one O(12)CaTiV2 tetrahedra,  an edgeedge with one O(11)CaTiV2 tetrahedra, and  an edgeedge with one O(12)CaTiV2 tetrahedra. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one Ti(2), one V(2), and one V(3) atom.
CaTi3V5O16 crystallizes in the triclinic P1 space group. Ca(1) is bonded to one O(11), one O(12), one O(15), and one O(3) atom to form distorted CaO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(5)O6 octahedra, and corners with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-69°. The Ca(1)-O(11) bond length is 2.14 Å. The Ca(1)-O(12) bond length is 2.13 Å. The Ca(1)-O(15) bond length is 2.12 Å. The Ca(1)-O(3) bond length is 2.21 Å. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(14), one O(2), one O(3), one O(4), one O(7), and one O(9) atom to form distorted TiO6 octahedra that share corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Ca(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-54°. The Ti(1)-O(14) bond length is 1.88 Å. The Ti(1)-O(2) bond length is 1.88 Å. The Ti(1)-O(3) bond length is 1.98 Å. The Ti(1)-O(4) bond length is 1.95 Å. The Ti(1)-O(7) bond length is 2.22 Å. The Ti(1)-O(9) bond length is 2.17 Å. In the second Ti site, Ti(2) is bonded to one O(16), one O(2), one O(3), one O(4), one O(8), and one O(9) atom to form distorted TiO6 octahedra that share corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Ca(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-47°. The Ti(2)-O(16) bond length is 2.02 Å. The Ti(2)-O(2) bond length is 2.18 Å. The Ti(2)-O(3) bond length is 2.12 Å. The Ti(2)-O(4) bond length is 1.88 Å. The Ti(2)-O(8) bond length is 1.95 Å. The Ti(2)-O(9) bond length is 1.90 Å. In the third Ti site, Ti(3) is bonded to one O(1), one O(11), one O(12), one O(13), one O(5), and one O(6) atom to form distorted TiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Ca(1)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles are 55°. The Ti(3)-O(1) bond length is 1.96 Å. The Ti(3)-O(11) bond length is 2.03 Å. The Ti(3)-O(12) bond length is 2.09 Å. The Ti(3)-O(13) bond length is 1.89 Å. The Ti(3)-O(5) bond length is 2.08 Å. The Ti(3)-O(6) bond length is 1.96 Å. There are five inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(10), one O(2), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share corners with two equivalent Ti(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(5)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. The V(1)-O(1) bond length is 2.11 Å. The V(1)-O(10) bond length is 2.07 Å. The V(1)-O(2) bond length is 1.95 Å. The V(1)-O(6) bond length is 2.15 Å. The V(1)-O(7) bond length is 1.77 Å. The V(1)-O(8) bond length is 1.92 Å. In the second V site, V(2) is bonded to one O(14), one O(16), one O(3), one O(4), one O(7), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Ca(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-55°. The V(2)-O(14) bond length is 2.03 Å. The V(2)-O(16) bond length is 1.99 Å. The V(2)-O(3) bond length is 2.08 Å. The V(2)-O(4) bond length is 2.08 Å. The V(2)-O(7) bond length is 2.07 Å. The V(2)-O(8) bond length is 2.07 Å. In the third V site, V(3) is bonded to one O(11), one O(12), one O(14), one O(15), one O(16), and one O(9) atom to form VO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent Ca(1)O4 tetrahedra,  an edgeedge with one Ti(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, and  an edgeedge with one V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. The V(3)-O(11) bond length is 2.10 Å. The V(3)-O(12) bond length is 2.12 Å. The V(3)-O(14) bond length is 2.06 Å. The V(3)-O(15) bond length is 2.08 Å. The V(3)-O(16) bond length is 1.99 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(13), one O(15), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Ca(1)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-51°. The V(4)-O(10) bond length is 1.97 Å. The V(4)-O(12) bond length is 1.94 Å. The V(4)-O(13) bond length is 2.04 Å. The V(4)-O(15) bond length is 2.01 Å. The V(4)-O(5) bond length is 1.96 Å. The V(4)-O(6) bond length is 1.97 Å. In the fifth V site, V(5) is bonded to one O(1), one O(10), one O(11), one O(13), one O(15), and one O(5) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Ca(1)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles are 48°. The V(5)-O(1) bond length is 1.95 Å. The V(5)-O(10) bond length is 1.97 Å. The V(5)-O(11) bond length is 1.97 Å. The V(5)-O(13) bond length is 2.04 Å. The V(5)-O(15) bond length is 1.99 Å. The V(5)-O(5) bond length is 1.96 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Ti(3), one V(1), and one V(5) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1), one Ti(2), and one V(1) atom. In the third O site, O(3) is bonded to one Ca(1), one Ti(1), one Ti(2), and one V(2) atom to form distorted OCaTi2V tetrahedra that share  a cornercorner with one O(11)CaTiV2 tetrahedra,  a cornercorner with one O(12)CaTiV2 tetrahedra, and  a cornercorner with one O(15)CaV3 tetrahedra. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1), one Ti(2), and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Ti(3), one V(4), and one V(5) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Ti(3), one V(1), and one V(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Ti(1), one V(1), and one V(2) atom. In the eighth O site, O(8) is bonded in a trigonal non-coplanar geometry to one Ti(2), one V(1), and one V(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Ti(1), one Ti(2), and one V(3) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one V(1), one V(4), and one V(5) atom. In the eleventh O site, O(11) is bonded to one Ca(1), one Ti(3), one V(3), and one V(5) atom to form OCaTiV2 tetrahedra that share  a cornercorner with one O(3)CaTi2V tetrahedra,  a cornercorner with one O(12)CaTiV2 tetrahedra,  a cornercorner with one O(15)CaV3 tetrahedra,  an edgeedge with one O(12)CaTiV2 tetrahedra, and  an edgeedge with one O(15)CaV3 tetrahedra. In the twelfth O site, O(12) is bonded to one Ca(1), one Ti(3), one V(3), and one V(4) atom to form OCaTiV2 tetrahedra that share  a cornercorner with one O(3)CaTi2V tetrahedra,  a cornercorner with one O(11)CaTiV2 tetrahedra,  a cornercorner with one O(15)CaV3 tetrahedra,  an edgeedge with one O(11)CaTiV2 tetrahedra, and  an edgeedge with one O(15)CaV3 tetrahedra. In the thirteenth O site, O(13) is bonded in a distorted trigonal non-coplanar geometry to one Ti(3), one V(4), and one V(5) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Ti(1), one V(2), and one V(3) atom. In the fifteenth O site, O(15) is bonded to one Ca(1), one V(3), one V(4), and one V(5) atom to form OCaV3 tetrahedra that share  a cornercorner with one O(3)CaTi2V tetrahedra,  a cornercorner with one O(11)CaTiV2 tetrahedra,  a cornercorner with one O(12)CaTiV2 tetrahedra,  an edgeedge with one O(11)CaTiV2 tetrahedra, and  an edgeedge with one O(12)CaTiV2 tetrahedra. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one Ti(2), one V(2), and one V(3) atom.