KV6O14 crystallizes in the triclinic P-1 space group. K(1) is bonded to one O(3), one O(4), one O(9), two equivalent O(11), and two equivalent O(12) atoms to form distorted KO7 pentagonal bipyramids that share corners with two equivalent V(5)O5 trigonal bipyramids, corners with two equivalent V(6)O5 trigonal bipyramids, and edges with two equivalent K(1)O7 pentagonal bipyramids. There are six inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), one O(5), and one O(7) atom. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(6), and one O(8) atom. In the third V site, V(3) is bonded to one O(1), one O(10), one O(5), one O(6), and one O(7) atom to form distorted corner-sharing VO5 square pyramids. In the fourth V site, V(4) is bonded in a 5-coordinate geometry to one O(2), one O(5), one O(6), one O(8), and one O(9) atom. In the fifth V site, V(5) is bonded to one O(11), one O(13), one O(8), and two equivalent O(14) atoms to form distorted VO5 trigonal bipyramids that share corners with two equivalent K(1)O7 pentagonal bipyramids, corners with two equivalent V(6)O5 trigonal bipyramids,  an edgeedge with one V(5)O5 trigonal bipyramid, and  an edgeedge with one V(6)O5 trigonal bipyramid. In the sixth V site, V(6) is bonded to one O(12), one O(14), one O(7), and two equivalent O(13) atoms to form distorted VO5 trigonal bipyramids that share corners with two equivalent K(1)O7 pentagonal bipyramids,  a cornercorner with one V(3)O5 square pyramid, corners with two equivalent V(5)O5 trigonal bipyramids,  an edgeedge with one V(5)O5 trigonal bipyramid, and  an edgeedge with one V(6)O5 trigonal bipyramid. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one V(4) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one K(1) and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one K(1) and one V(1) atom. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one V(1), one V(3), and one V(4) atom. In the sixth O site, O(6) is bonded in a trigonal non-coplanar geometry to one V(2), one V(3), and one V(4) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one V(1), one V(3), and one V(6) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one V(2), one V(4), and one V(5) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one K(1) and one V(4) atom. In the tenth O site, O(10) is bonded in a single-bond geometry to one V(3) atom. In the eleventh O site, O(11) is bonded in a distorted single-bond geometry to two equivalent K(1) and one V(5) atom. In the twelfth O site, O(12) is bonded in a distorted single-bond geometry to two equivalent K(1) and one V(6) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal non-coplanar geometry to one V(5) and two equivalent V(6) atoms. In the fourteenth O site, O(14) is bonded in a distorted trigonal non-coplanar geometry to one V(6) and two equivalent V(5) atoms.
KV6O14 crystallizes in the triclinic P-1 space group. K(1) is bonded to one O(3), one O(4), one O(9), two equivalent O(11), and two equivalent O(12) atoms to form distorted KO7 pentagonal bipyramids that share corners with two equivalent V(5)O5 trigonal bipyramids, corners with two equivalent V(6)O5 trigonal bipyramids, and edges with two equivalent K(1)O7 pentagonal bipyramids. The K(1)-O(3) bond length is 2.79 Å. The K(1)-O(4) bond length is 2.86 Å. The K(1)-O(9) bond length is 2.75 Å. There is one shorter (2.74 Å) and one longer (2.78 Å) K(1)-O(11) bond length. There is one shorter (2.83 Å) and one longer (2.86 Å) K(1)-O(12) bond length. There are six inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), one O(5), and one O(7) atom. The V(1)-O(1) bond length is 1.87 Å. The V(1)-O(2) bond length is 1.85 Å. The V(1)-O(4) bond length is 1.62 Å. The V(1)-O(5) bond length is 2.01 Å. The V(1)-O(7) bond length is 2.00 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(6), and one O(8) atom. The V(2)-O(1) bond length is 1.98 Å. The V(2)-O(2) bond length is 1.97 Å. The V(2)-O(3) bond length is 1.62 Å. The V(2)-O(6) bond length is 2.00 Å. The V(2)-O(8) bond length is 2.07 Å. In the third V site, V(3) is bonded to one O(1), one O(10), one O(5), one O(6), and one O(7) atom to form distorted corner-sharing VO5 square pyramids. The V(3)-O(1) bond length is 2.17 Å. The V(3)-O(10) bond length is 1.63 Å. The V(3)-O(5) bond length is 2.02 Å. The V(3)-O(6) bond length is 2.01 Å. The V(3)-O(7) bond length is 1.99 Å. In the fourth V site, V(4) is bonded in a 5-coordinate geometry to one O(2), one O(5), one O(6), one O(8), and one O(9) atom. The V(4)-O(2) bond length is 2.22 Å. The V(4)-O(5) bond length is 1.88 Å. The V(4)-O(6) bond length is 1.88 Å. The V(4)-O(8) bond length is 1.80 Å. The V(4)-O(9) bond length is 1.64 Å. In the fifth V site, V(5) is bonded to one O(11), one O(13), one O(8), and two equivalent O(14) atoms to form distorted VO5 trigonal bipyramids that share corners with two equivalent K(1)O7 pentagonal bipyramids, corners with two equivalent V(6)O5 trigonal bipyramids,  an edgeedge with one V(5)O5 trigonal bipyramid, and  an edgeedge with one V(6)O5 trigonal bipyramid. The V(5)-O(11) bond length is 1.64 Å. The V(5)-O(13) bond length is 1.97 Å. The V(5)-O(8) bond length is 2.02 Å. There is one shorter (1.98 Å) and one longer (1.99 Å) V(5)-O(14) bond length. In the sixth V site, V(6) is bonded to one O(12), one O(14), one O(7), and two equivalent O(13) atoms to form distorted VO5 trigonal bipyramids that share corners with two equivalent K(1)O7 pentagonal bipyramids,  a cornercorner with one V(3)O5 square pyramid, corners with two equivalent V(5)O5 trigonal bipyramids,  an edgeedge with one V(5)O5 trigonal bipyramid, and  an edgeedge with one V(6)O5 trigonal bipyramid. The V(6)-O(12) bond length is 1.63 Å. The V(6)-O(14) bond length is 1.87 Å. The V(6)-O(7) bond length is 1.90 Å. There is one shorter (1.88 Å) and one longer (2.01 Å) V(6)-O(13) bond length. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one V(4) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one K(1) and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one K(1) and one V(1) atom. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one V(1), one V(3), and one V(4) atom. In the sixth O site, O(6) is bonded in a trigonal non-coplanar geometry to one V(2), one V(3), and one V(4) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one V(1), one V(3), and one V(6) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one V(2), one V(4), and one V(5) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one K(1) and one V(4) atom. In the tenth O site, O(10) is bonded in a single-bond geometry to one V(3) atom. In the eleventh O site, O(11) is bonded in a distorted single-bond geometry to two equivalent K(1) and one V(5) atom. In the twelfth O site, O(12) is bonded in a distorted single-bond geometry to two equivalent K(1) and one V(6) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal non-coplanar geometry to one V(5) and two equivalent V(6) atoms. In the fourteenth O site, O(14) is bonded in a distorted trigonal non-coplanar geometry to one V(6) and two equivalent V(5) atoms.