CaV(GeO3)2 crystallizes in the monoclinic P2_1/c space group. Ca(1) is bonded in a 7-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one O(6), and two equivalent O(1) atoms. V(1) is bonded to one O(3), one O(4), two equivalent O(5), and two equivalent O(6) atoms to form VO6 octahedra that share corners with three equivalent Ge(1)O4 tetrahedra, corners with three equivalent Ge(2)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(4), one O(5), and two equivalent O(2) atoms to form GeO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra and corners with two equivalent Ge(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-61°. In the second Ge site, Ge(2) is bonded to one O(3), one O(6), and two equivalent O(1) atoms to form GeO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra and corners with two equivalent Ge(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-70°. There are six inequivalent O sites. In the first O site, O(5) is bonded to one Ca(1), two equivalent V(1), and one Ge(1) atom to form a mixture of distorted corner and edge-sharing OCaV2Ge trigonal pyramids. In the second O site, O(6) is bonded to one Ca(1), two equivalent V(1), and one Ge(2) atom to form a mixture of distorted corner and edge-sharing OCaV2Ge tetrahedra. In the third O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Ca(1) and two equivalent Ge(2) atoms. In the fourth O site, O(2) is bonded in a trigonal planar geometry to one Ca(1) and two equivalent Ge(1) atoms. In the fifth O site, O(3) is bonded in a distorted T-shaped geometry to one Ca(1), one V(1), and one Ge(2) atom. In the sixth O site, O(4) is bonded in a distorted trigonal planar geometry to one Ca(1), one V(1), and one Ge(1) atom.
CaV(GeO3)2 crystallizes in the monoclinic P2_1/c space group. Ca(1) is bonded in a 7-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one O(6), and two equivalent O(1) atoms. The Ca(1)-O(2) bond length is 2.48 Å. The Ca(1)-O(3) bond length is 2.52 Å. The Ca(1)-O(4) bond length is 2.33 Å. The Ca(1)-O(5) bond length is 2.42 Å. The Ca(1)-O(6) bond length is 2.39 Å. There is one shorter (2.63 Å) and one longer (2.67 Å) Ca(1)-O(1) bond length. V(1) is bonded to one O(3), one O(4), two equivalent O(5), and two equivalent O(6) atoms to form VO6 octahedra that share corners with three equivalent Ge(1)O4 tetrahedra, corners with three equivalent Ge(2)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. The V(1)-O(3) bond length is 2.17 Å. The V(1)-O(4) bond length is 2.14 Å. There is one shorter (2.18 Å) and one longer (2.22 Å) V(1)-O(5) bond length. There is one shorter (2.13 Å) and one longer (2.20 Å) V(1)-O(6) bond length. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(4), one O(5), and two equivalent O(2) atoms to form GeO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra and corners with two equivalent Ge(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-61°. The Ge(1)-O(4) bond length is 1.73 Å. The Ge(1)-O(5) bond length is 1.76 Å. Both Ge(1)-O(2) bond lengths are 1.83 Å. In the second Ge site, Ge(2) is bonded to one O(3), one O(6), and two equivalent O(1) atoms to form GeO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra and corners with two equivalent Ge(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-70°. The Ge(2)-O(3) bond length is 1.75 Å. The Ge(2)-O(6) bond length is 1.76 Å. There is one shorter (1.80 Å) and one longer (1.86 Å) Ge(2)-O(1) bond length. There are six inequivalent O sites. In the first O site, O(5) is bonded to one Ca(1), two equivalent V(1), and one Ge(1) atom to form a mixture of distorted corner and edge-sharing OCaV2Ge trigonal pyramids. In the second O site, O(6) is bonded to one Ca(1), two equivalent V(1), and one Ge(2) atom to form a mixture of distorted corner and edge-sharing OCaV2Ge tetrahedra. In the third O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Ca(1) and two equivalent Ge(2) atoms. In the fourth O site, O(2) is bonded in a trigonal planar geometry to one Ca(1) and two equivalent Ge(1) atoms. In the fifth O site, O(3) is bonded in a distorted T-shaped geometry to one Ca(1), one V(1), and one Ge(2) atom. In the sixth O site, O(4) is bonded in a distorted trigonal planar geometry to one Ca(1), one V(1), and one Ge(1) atom.