LiV6O15 crystallizes in the monoclinic Cm space group. Li(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(10) and two equivalent O(6) atoms. There are six inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(5), one O(9), and two equivalent O(12) atoms. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(15), one O(9), and two equivalent O(4) atoms. In the third V site, V(3) is bonded in a 5-coordinate geometry to one O(3), one O(5), one O(6), and two equivalent O(13) atoms. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to one O(1), one O(4), one O(5), one O(7), and two equivalent O(15) atoms. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(15), one O(8), and two equivalent O(1) atoms. In the sixth V site, V(6) is bonded in a 5-coordinate geometry to one O(10), one O(11), one O(13), and two equivalent O(3) atoms. There are fifteen inequivalent O sites. In the first O site, O(1) is bonded to one V(1), one V(4), and two equivalent V(5) atoms to form a mixture of distorted edge and corner-sharing OV4 trigonal pyramids. In the second O site, O(2) is bonded in a single-bond geometry to one V(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(3) and two equivalent V(6) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one V(4) and two equivalent V(2) atoms. In the fifth O site, O(5) is bonded in a trigonal planar 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 planar geometry to two equivalent Li(1) and one V(3) atom. In the seventh O site, O(7) is bonded in a single-bond geometry to one V(4) atom. In the eighth O site, O(8) is bonded in a single-bond geometry to one V(5) atom. In the ninth O site, O(9) is bonded in a linear geometry to one V(1) and one V(2) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to two equivalent Li(1) and one V(6) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one V(2), one V(5), and one V(6) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal non-coplanar geometry to one V(5) and two equivalent V(1) atoms. In the thirteenth O site, O(13) is bonded in a trigonal non-coplanar geometry to one V(6) and two equivalent V(3) atoms. In the fourteenth O site, O(14) is bonded in a single-bond geometry to one V(2) atom. In the fifteenth O site, O(15) is bonded to one V(2), one V(5), and two equivalent V(4) atoms to form a mixture of distorted edge and corner-sharing OV4 trigonal pyramids.
LiV6O15 crystallizes in the monoclinic Cm space group. Li(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(10) and two equivalent O(6) atoms. Both Li(1)-O(10) bond lengths are 2.46 Å. Both Li(1)-O(6) bond lengths are 2.17 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(5), one O(9), and two equivalent O(12) atoms. The V(1)-O(1) bond length is 2.32 Å. The V(1)-O(2) bond length is 1.62 Å. The V(1)-O(5) bond length is 2.10 Å. The V(1)-O(9) bond length is 1.83 Å. Both V(1)-O(12) bond lengths are 1.92 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(15), one O(9), and two equivalent O(4) atoms. The V(2)-O(11) bond length is 2.21 Å. The V(2)-O(14) bond length is 1.63 Å. The V(2)-O(15) bond length is 2.26 Å. The V(2)-O(9) bond length is 1.79 Å. Both V(2)-O(4) bond lengths are 1.91 Å. In the third V site, V(3) is bonded in a 5-coordinate geometry to one O(3), one O(5), one O(6), and two equivalent O(13) atoms. The V(3)-O(3) bond length is 2.04 Å. The V(3)-O(5) bond length is 2.00 Å. The V(3)-O(6) bond length is 1.67 Å. Both V(3)-O(13) bond lengths are 1.94 Å. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to one O(1), one O(4), one O(5), one O(7), and two equivalent O(15) atoms. The V(4)-O(1) bond length is 2.40 Å. The V(4)-O(4) bond length is 2.06 Å. The V(4)-O(5) bond length is 1.85 Å. The V(4)-O(7) bond length is 1.61 Å. Both V(4)-O(15) bond lengths are 1.91 Å. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(15), one O(8), and two equivalent O(1) atoms. The V(5)-O(11) bond length is 1.89 Å. The V(5)-O(12) bond length is 2.04 Å. The V(5)-O(15) bond length is 2.39 Å. The V(5)-O(8) bond length is 1.61 Å. Both V(5)-O(1) bond lengths are 1.90 Å. In the sixth V site, V(6) is bonded in a 5-coordinate geometry to one O(10), one O(11), one O(13), and two equivalent O(3) atoms. The V(6)-O(10) bond length is 1.64 Å. The V(6)-O(11) bond length is 1.87 Å. The V(6)-O(13) bond length is 1.95 Å. Both V(6)-O(3) bond lengths are 1.90 Å. There are fifteen inequivalent O sites. In the first O site, O(1) is bonded to one V(1), one V(4), and two equivalent V(5) atoms to form a mixture of distorted edge and corner-sharing OV4 trigonal pyramids. In the second O site, O(2) is bonded in a single-bond geometry to one V(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(3) and two equivalent V(6) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one V(4) and two equivalent V(2) atoms. In the fifth O site, O(5) is bonded in a trigonal planar 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 planar geometry to two equivalent Li(1) and one V(3) atom. In the seventh O site, O(7) is bonded in a single-bond geometry to one V(4) atom. In the eighth O site, O(8) is bonded in a single-bond geometry to one V(5) atom. In the ninth O site, O(9) is bonded in a linear geometry to one V(1) and one V(2) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to two equivalent Li(1) and one V(6) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one V(2), one V(5), and one V(6) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal non-coplanar geometry to one V(5) and two equivalent V(1) atoms. In the thirteenth O site, O(13) is bonded in a trigonal non-coplanar geometry to one V(6) and two equivalent V(3) atoms. In the fourteenth O site, O(14) is bonded in a single-bond geometry to one V(2) atom. In the fifteenth O site, O(15) is bonded to one V(2), one V(5), and two equivalent V(4) atoms to form a mixture of distorted edge and corner-sharing OV4 trigonal pyramids.