CaV4(GeO4)4 crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(13), one O(15), one O(2), and one O(5) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(13), one O(15), one O(16), one O(2), and one O(7) atom. In the second V site, V(2) is bonded to one O(11), one O(14), one O(3), one O(5), one O(8), and one O(9) atom to form VO6 octahedra that share corners with three equivalent Ge(4)O4 tetrahedra, corners with two equivalent Ge(1)O5 trigonal bipyramids, edges with two equivalent V(3)O6 octahedra, and  an edgeedge with one Ge(3)O5 trigonal bipyramid. In the third V site, V(3) is bonded to one O(12), one O(14), one O(3), one O(6), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent Ge(4)O4 tetrahedra, corners with three equivalent Ge(1)O5 trigonal bipyramids, edges with two equivalent V(2)O6 octahedra, and  an edgeedge with one Ge(2)O5 trigonal bipyramid. In the fourth V site, V(4) is bonded in a 5-coordinate geometry to one O(1), one O(10), one O(13), one O(2), and one O(4) atom. There are four inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(14), one O(16), one O(6), one O(7), and one O(8) atom to form distorted GeO5 trigonal bipyramids that share corners with two equivalent V(2)O6 octahedra, corners with three equivalent V(3)O6 octahedra, and corners with two equivalent Ge(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 45-56°. In the second Ge site, Ge(2) is bonded to one O(12), one O(15), one O(4), one O(6), and one O(7) atom to form distorted GeO5 trigonal bipyramids that share corners with two equivalent Ge(1)O5 trigonal bipyramids and  an edgeedge with one V(3)O6 octahedra. In the third Ge site, Ge(3) is bonded to one O(1), one O(10), one O(11), one O(13), and one O(5) atom to form distorted GeO5 trigonal bipyramids that share  an edgeedge with one V(2)O6 octahedra and  an edgeedge with one Ge(4)O4 tetrahedra. In the fourth Ge site, Ge(4) is bonded to one O(10), one O(11), one O(3), and one O(9) atom to form GeO4 tetrahedra that share corners with two equivalent V(3)O6 octahedra, corners with three equivalent V(2)O6 octahedra, and  an edgeedge with one Ge(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 41-62°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one V(4), and one Ge(3) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), and one V(4) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(2), one V(3), and one Ge(4) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one V(4) and one Ge(2) atom. In the fifth O site, O(5) is bonded in a T-shaped geometry to one Ca(1), one V(2), and one Ge(3) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one V(3), one Ge(1), and one Ge(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1), one Ge(1), and one Ge(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Ge(1) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Ge(4) atom. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Ca(1), one V(4), one Ge(3), and one Ge(4) atom. In the eleventh O site, O(11) is bonded in a distorted T-shaped geometry to one V(2), one Ge(3), and one Ge(4) atom. In the twelfth O site, O(12) is bonded in a water-like geometry to one V(3) and one Ge(2) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Ca(1), one V(1), one V(4), and one Ge(3) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Ge(1) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), and one Ge(2) atom. In the sixteenth O site, O(16) is bonded in a water-like geometry to one V(1) and one Ge(1) atom.
CaV4(GeO4)4 crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(13), one O(15), one O(2), and one O(5) atom. The Ca(1)-O(1) bond length is 2.25 Å. The Ca(1)-O(10) bond length is 2.37 Å. The Ca(1)-O(13) bond length is 2.68 Å. The Ca(1)-O(15) bond length is 2.35 Å. The Ca(1)-O(2) bond length is 2.24 Å. The Ca(1)-O(5) bond length is 2.22 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(13), one O(15), one O(16), one O(2), and one O(7) atom. The V(1)-O(13) bond length is 2.50 Å. The V(1)-O(15) bond length is 1.90 Å. The V(1)-O(16) bond length is 1.76 Å. The V(1)-O(2) bond length is 1.79 Å. The V(1)-O(7) bond length is 1.99 Å. In the second V site, V(2) is bonded to one O(11), one O(14), one O(3), one O(5), one O(8), and one O(9) atom to form VO6 octahedra that share corners with three equivalent Ge(4)O4 tetrahedra, corners with two equivalent Ge(1)O5 trigonal bipyramids, edges with two equivalent V(3)O6 octahedra, and  an edgeedge with one Ge(3)O5 trigonal bipyramid. The V(2)-O(11) bond length is 2.14 Å. The V(2)-O(14) bond length is 2.02 Å. The V(2)-O(3) bond length is 2.26 Å. The V(2)-O(5) bond length is 1.99 Å. The V(2)-O(8) bond length is 1.96 Å. The V(2)-O(9) bond length is 2.12 Å. In the third V site, V(3) is bonded to one O(12), one O(14), one O(3), one O(6), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent Ge(4)O4 tetrahedra, corners with three equivalent Ge(1)O5 trigonal bipyramids, edges with two equivalent V(2)O6 octahedra, and  an edgeedge with one Ge(2)O5 trigonal bipyramid. The V(3)-O(12) bond length is 1.74 Å. The V(3)-O(14) bond length is 2.05 Å. The V(3)-O(3) bond length is 1.99 Å. The V(3)-O(6) bond length is 2.08 Å. The V(3)-O(8) bond length is 2.24 Å. The V(3)-O(9) bond length is 1.97 Å. In the fourth V site, V(4) is bonded in a 5-coordinate geometry to one O(1), one O(10), one O(13), one O(2), and one O(4) atom. The V(4)-O(1) bond length is 1.93 Å. The V(4)-O(10) bond length is 2.23 Å. The V(4)-O(13) bond length is 2.01 Å. The V(4)-O(2) bond length is 1.96 Å. The V(4)-O(4) bond length is 1.95 Å. There are four inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(14), one O(16), one O(6), one O(7), and one O(8) atom to form distorted GeO5 trigonal bipyramids that share corners with two equivalent V(2)O6 octahedra, corners with three equivalent V(3)O6 octahedra, and corners with two equivalent Ge(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 45-56°. The Ge(1)-O(14) bond length is 1.88 Å. The Ge(1)-O(16) bond length is 1.97 Å. The Ge(1)-O(6) bond length is 1.82 Å. The Ge(1)-O(7) bond length is 1.96 Å. The Ge(1)-O(8) bond length is 1.92 Å. In the second Ge site, Ge(2) is bonded to one O(12), one O(15), one O(4), one O(6), and one O(7) atom to form distorted GeO5 trigonal bipyramids that share corners with two equivalent Ge(1)O5 trigonal bipyramids and  an edgeedge with one V(3)O6 octahedra. The Ge(2)-O(12) bond length is 1.85 Å. The Ge(2)-O(15) bond length is 1.91 Å. The Ge(2)-O(4) bond length is 1.78 Å. The Ge(2)-O(6) bond length is 2.06 Å. The Ge(2)-O(7) bond length is 1.87 Å. In the third Ge site, Ge(3) is bonded to one O(1), one O(10), one O(11), one O(13), and one O(5) atom to form distorted GeO5 trigonal bipyramids that share  an edgeedge with one V(2)O6 octahedra and  an edgeedge with one Ge(4)O4 tetrahedra. The Ge(3)-O(1) bond length is 1.77 Å. The Ge(3)-O(10) bond length is 2.04 Å. The Ge(3)-O(11) bond length is 1.85 Å. The Ge(3)-O(13) bond length is 1.81 Å. The Ge(3)-O(5) bond length is 1.83 Å. In the fourth Ge site, Ge(4) is bonded to one O(10), one O(11), one O(3), and one O(9) atom to form GeO4 tetrahedra that share corners with two equivalent V(3)O6 octahedra, corners with three equivalent V(2)O6 octahedra, and  an edgeedge with one Ge(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 41-62°. The Ge(4)-O(10) bond length is 1.84 Å. The Ge(4)-O(11) bond length is 1.80 Å. The Ge(4)-O(3) bond length is 1.78 Å. The Ge(4)-O(9) bond length is 1.80 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one V(4), and one Ge(3) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), and one V(4) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(2), one V(3), and one Ge(4) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one V(4) and one Ge(2) atom. In the fifth O site, O(5) is bonded in a T-shaped geometry to one Ca(1), one V(2), and one Ge(3) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one V(3), one Ge(1), and one Ge(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1), one Ge(1), and one Ge(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Ge(1) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Ge(4) atom. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Ca(1), one V(4), one Ge(3), and one Ge(4) atom. In the eleventh O site, O(11) is bonded in a distorted T-shaped geometry to one V(2), one Ge(3), and one Ge(4) atom. In the twelfth O site, O(12) is bonded in a water-like geometry to one V(3) and one Ge(2) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Ca(1), one V(1), one V(4), and one Ge(3) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Ge(1) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), and one Ge(2) atom. In the sixteenth O site, O(16) is bonded in a water-like geometry to one V(1) and one Ge(1) atom.