CaTi3V5O16 crystallizes in the triclinic P1 space group. Ca(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 distorted CaO6 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, and  a faceface with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a 5-coordinate geometry to one O(14), one O(2), one O(3), one O(4), and one O(9) atom. In the second Ti site, Ti(2) is bonded in a 5-coordinate geometry to one O(14), one O(3), one O(4), one O(8), and one O(9) atom. 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 TiO6 octahedra that share corners with two equivalent Ca(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(1)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 52°. There are five inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(10), one O(11), one O(12), one O(15), and one O(6) atom to form VO6 octahedra that share corners with three equivalent V(3)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and  a faceface with one Ca(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-24°. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(16), one O(3), one O(4), one O(7), and one O(9) atom. 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 distorted VO6 octahedra that share corners with three equivalent V(1)O6 octahedra,  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 20-24°. 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 Ca(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. 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 Ca(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-47°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), one Ti(3), one V(1), and one V(5) atom to form distorted OCaTiV2 trigonal pyramids that share  a cornercorner with one O(6)CaTiV2 trigonal pyramid,  a cornercorner with one O(10)CaV3 trigonal pyramid,  an edgeedge with one O(6)CaTiV2 trigonal pyramid,  an edgeedge with one O(10)CaV3 trigonal pyramid, and  an edgeedge with one O(15)V4 trigonal pyramid. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Ca(1) and one Ti(1) atom. In the third O site, O(3) is bonded in a trigonal non-coplanar geometry to one Ti(1), one Ti(2), and one V(2) atom. In the fourth O site, O(4) is bonded in a trigonal planar 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 T-shaped geometry to one Ti(3), one V(4), and one V(5) atom. In the sixth O site, O(6) is bonded to one Ca(1), one Ti(3), one V(1), and one V(4) atom to form distorted OCaTiV2 trigonal pyramids that share  a cornercorner with one O(1)CaTiV2 trigonal pyramid,  a cornercorner with one O(10)CaV3 trigonal pyramid,  an edgeedge with one O(1)CaTiV2 trigonal pyramid,  an edgeedge with one O(10)CaV3 trigonal pyramid, and  an edgeedge with one O(15)V4 trigonal pyramid. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Ca(1) and one V(2) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one Ca(1) and one Ti(2) atom. In the ninth O site, O(9) is bonded in a distorted see-saw-like geometry to one Ti(1), one Ti(2), one V(2), and one V(3) atom. In the tenth O site, O(10) is bonded to one Ca(1), one V(1), one V(4), and one V(5) atom to form OCaV3 trigonal pyramids that share  a cornercorner with one O(1)CaTiV2 trigonal pyramid,  a cornercorner with one O(6)CaTiV2 trigonal pyramid, corners with three equivalent O(15)V4 trigonal pyramids,  an edgeedge with one O(1)CaTiV2 trigonal pyramid, and  an edgeedge with one O(6)CaTiV2 trigonal pyramid. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Ti(3), one V(1), one V(3), and one V(5) atom. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to one Ti(3), one V(1), one V(3), and one V(4) atom. 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 Ti(2), and one V(3) atom. In the fifteenth O site, O(15) is bonded to one V(1), one V(3), one V(4), and one V(5) atom to form distorted OV4 trigonal pyramids that share corners with three equivalent O(10)CaV3 trigonal pyramids,  an edgeedge with one O(1)CaTiV2 trigonal pyramid, and  an edgeedge with one O(6)CaTiV2 trigonal pyramid. In the sixteenth O site, O(16) is bonded in a distorted water-like geometry to one V(2) and one V(3) atom.
CaTi3V5O16 crystallizes in the triclinic P1 space group. Ca(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 distorted CaO6 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, and  a faceface with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. The Ca(1)-O(1) bond length is 2.58 Å. The Ca(1)-O(10) bond length is 2.54 Å. The Ca(1)-O(2) bond length is 2.26 Å. The Ca(1)-O(6) bond length is 2.51 Å. The Ca(1)-O(7) bond length is 2.32 Å. The Ca(1)-O(8) bond length is 2.27 Å. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a 5-coordinate geometry to one O(14), one O(2), one O(3), one O(4), and one O(9) atom. The Ti(1)-O(14) bond length is 1.92 Å. The Ti(1)-O(2) bond length is 1.70 Å. The Ti(1)-O(3) bond length is 2.11 Å. The Ti(1)-O(4) bond length is 1.94 Å. The Ti(1)-O(9) bond length is 2.18 Å. In the second Ti site, Ti(2) is bonded in a 5-coordinate geometry to one O(14), one O(3), one O(4), one O(8), and one O(9) atom. The Ti(2)-O(14) bond length is 2.24 Å. The Ti(2)-O(3) bond length is 1.94 Å. The Ti(2)-O(4) bond length is 2.01 Å. The Ti(2)-O(8) bond length is 1.68 Å. The Ti(2)-O(9) bond length is 2.05 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 TiO6 octahedra that share corners with two equivalent Ca(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(1)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 52°. The Ti(3)-O(1) bond length is 1.91 Å. The Ti(3)-O(11) bond length is 2.08 Å. The Ti(3)-O(12) bond length is 2.13 Å. The Ti(3)-O(13) bond length is 1.85 Å. The Ti(3)-O(5) bond length is 2.11 Å. The Ti(3)-O(6) bond length is 1.92 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(11), one O(12), one O(15), and one O(6) atom to form VO6 octahedra that share corners with three equivalent V(3)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and  a faceface with one Ca(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-24°. The V(1)-O(1) bond length is 2.14 Å. The V(1)-O(10) bond length is 2.01 Å. The V(1)-O(11) bond length is 2.17 Å. The V(1)-O(12) bond length is 2.02 Å. The V(1)-O(15) bond length is 2.00 Å. The V(1)-O(6) bond length is 2.10 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(16), one O(3), one O(4), one O(7), and one O(9) atom. The V(2)-O(16) bond length is 2.02 Å. The V(2)-O(3) bond length is 1.95 Å. The V(2)-O(4) bond length is 1.98 Å. The V(2)-O(7) bond length is 1.67 Å. The V(2)-O(9) bond length is 2.15 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 distorted VO6 octahedra that share corners with three equivalent V(1)O6 octahedra,  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 20-24°. The V(3)-O(11) bond length is 2.16 Å. The V(3)-O(12) bond length is 2.07 Å. The V(3)-O(14) bond length is 1.92 Å. The V(3)-O(15) bond length is 2.19 Å. The V(3)-O(16) bond length is 1.73 Å. The V(3)-O(9) bond length is 1.95 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 Ca(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. The V(4)-O(10) bond length is 2.00 Å. The V(4)-O(12) bond length is 2.05 Å. The V(4)-O(13) bond length is 2.06 Å. The V(4)-O(15) bond length is 2.10 Å. The V(4)-O(5) bond length is 2.09 Å. The V(4)-O(6) bond length is 2.01 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 Ca(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-47°. The V(5)-O(1) bond length is 2.03 Å. The V(5)-O(10) bond length is 2.00 Å. The V(5)-O(11) bond length is 2.00 Å. The V(5)-O(13) bond length is 2.07 Å. The V(5)-O(15) bond length is 1.99 Å. The V(5)-O(5) bond length is 1.81 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), one Ti(3), one V(1), and one V(5) atom to form distorted OCaTiV2 trigonal pyramids that share  a cornercorner with one O(6)CaTiV2 trigonal pyramid,  a cornercorner with one O(10)CaV3 trigonal pyramid,  an edgeedge with one O(6)CaTiV2 trigonal pyramid,  an edgeedge with one O(10)CaV3 trigonal pyramid, and  an edgeedge with one O(15)V4 trigonal pyramid. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Ca(1) and one Ti(1) atom. In the third O site, O(3) is bonded in a trigonal non-coplanar geometry to one Ti(1), one Ti(2), and one V(2) atom. In the fourth O site, O(4) is bonded in a trigonal planar 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 T-shaped geometry to one Ti(3), one V(4), and one V(5) atom. In the sixth O site, O(6) is bonded to one Ca(1), one Ti(3), one V(1), and one V(4) atom to form distorted OCaTiV2 trigonal pyramids that share  a cornercorner with one O(1)CaTiV2 trigonal pyramid,  a cornercorner with one O(10)CaV3 trigonal pyramid,  an edgeedge with one O(1)CaTiV2 trigonal pyramid,  an edgeedge with one O(10)CaV3 trigonal pyramid, and  an edgeedge with one O(15)V4 trigonal pyramid. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Ca(1) and one V(2) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one Ca(1) and one Ti(2) atom. In the ninth O site, O(9) is bonded in a distorted see-saw-like geometry to one Ti(1), one Ti(2), one V(2), and one V(3) atom. In the tenth O site, O(10) is bonded to one Ca(1), one V(1), one V(4), and one V(5) atom to form OCaV3 trigonal pyramids that share  a cornercorner with one O(1)CaTiV2 trigonal pyramid,  a cornercorner with one O(6)CaTiV2 trigonal pyramid, corners with three equivalent O(15)V4 trigonal pyramids,  an edgeedge with one O(1)CaTiV2 trigonal pyramid, and  an edgeedge with one O(6)CaTiV2 trigonal pyramid. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Ti(3), one V(1), one V(3), and one V(5) atom. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to one Ti(3), one V(1), one V(3), and one V(4) atom. 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 Ti(2), and one V(3) atom. In the fifteenth O site, O(15) is bonded to one V(1), one V(3), one V(4), and one V(5) atom to form distorted OV4 trigonal pyramids that share corners with three equivalent O(10)CaV3 trigonal pyramids,  an edgeedge with one O(1)CaTiV2 trigonal pyramid, and  an edgeedge with one O(6)CaTiV2 trigonal pyramid. In the sixteenth O site, O(16) is bonded in a distorted water-like geometry to one V(2) and one V(3) atom.