Ca5V3O13 crystallizes in the hexagonal P6_3 space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 9-coordinate geometry to three equivalent O(1), three equivalent O(3), and three equivalent O(4) atoms. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to three equivalent O(3) and three equivalent O(4) atoms. In the third Ca site, Ca(3) is bonded to one O(4), one O(5), two equivalent O(1), and two equivalent O(2) atoms to form distorted CaO6 pentagonal pyramids that share corners with six equivalent Ca(3)O6 pentagonal pyramids, corners with three equivalent V(1)O4 tetrahedra, and  an edgeedge with one V(1)O4 tetrahedra. V(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form VO4 tetrahedra that share corners with three equivalent Ca(3)O6 pentagonal pyramids and  an edgeedge with one Ca(3)O6 pentagonal pyramid. There are five inequivalent O sites. In the first O site, O(4) is bonded to one Ca(1), one Ca(2), one Ca(3), and one V(1) atom to form distorted edge-sharing OCa3V tetrahedra. In the second O site, O(5) is bonded in a trigonal planar geometry to three equivalent Ca(3) atoms. In the third O site, O(1) is bonded in a 4-coordinate geometry to one Ca(1), two equivalent Ca(3), and one V(1) atom. In the fourth O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Ca(3) and one V(1) atom. In the fifth O site, O(3) is bonded in a 3-coordinate geometry to one Ca(1), one Ca(2), and one V(1) atom.
Ca5V3O13 crystallizes in the hexagonal P6_3 space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 9-coordinate geometry to three equivalent O(1), three equivalent O(3), and three equivalent O(4) atoms. All Ca(1)-O(1) bond lengths are 2.94 Å. All Ca(1)-O(3) bond lengths are 2.41 Å. All Ca(1)-O(4) bond lengths are 2.50 Å. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to three equivalent O(3) and three equivalent O(4) atoms. All Ca(2)-O(3) bond lengths are 2.38 Å. All Ca(2)-O(4) bond lengths are 2.46 Å. In the third Ca site, Ca(3) is bonded to one O(4), one O(5), two equivalent O(1), and two equivalent O(2) atoms to form distorted CaO6 pentagonal pyramids that share corners with six equivalent Ca(3)O6 pentagonal pyramids, corners with three equivalent V(1)O4 tetrahedra, and  an edgeedge with one V(1)O4 tetrahedra. The Ca(3)-O(4) bond length is 2.43 Å. The Ca(3)-O(5) bond length is 2.45 Å. There is one shorter (2.34 Å) and one longer (2.50 Å) Ca(3)-O(1) bond length. There is one shorter (2.34 Å) and one longer (2.45 Å) Ca(3)-O(2) bond length. V(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form VO4 tetrahedra that share corners with three equivalent Ca(3)O6 pentagonal pyramids and  an edgeedge with one Ca(3)O6 pentagonal pyramid. The V(1)-O(1) bond length is 1.73 Å. The V(1)-O(2) bond length is 1.74 Å. The V(1)-O(3) bond length is 1.73 Å. The V(1)-O(4) bond length is 1.76 Å. There are five inequivalent O sites. In the first O site, O(4) is bonded to one Ca(1), one Ca(2), one Ca(3), and one V(1) atom to form distorted edge-sharing OCa3V tetrahedra. In the second O site, O(5) is bonded in a trigonal planar geometry to three equivalent Ca(3) atoms. In the third O site, O(1) is bonded in a 4-coordinate geometry to one Ca(1), two equivalent Ca(3), and one V(1) atom. In the fourth O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Ca(3) and one V(1) atom. In the fifth O site, O(3) is bonded in a 3-coordinate geometry to one Ca(1), one Ca(2), and one V(1) atom.