Na2CaV12O32 crystallizes in the monoclinic Cm space group. Na(1) is bonded to one O(1), one O(2), one O(21), and one O(6) atom to form distorted corner-sharing NaO4 trigonal pyramids. Ca(1) is bonded in a rectangular see-saw-like geometry to one O(20), one O(5), and two equivalent O(3) atoms. There are nine inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(10), one O(13), one O(23), and two equivalent O(18) atoms. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(11), one O(14), one O(22), and two equivalent O(18) atoms. In the third V site, V(3) is bonded in a 5-coordinate geometry to one O(12), one O(15), one O(16), one O(17), and one O(24) atom. In the fourth V site, V(4) is bonded in a 5-coordinate geometry to one O(1), one O(19), one O(8), and two equivalent O(9) atoms. In the fifth V site, V(5) is bonded in a 5-coordinate geometry to one O(2), one O(20), one O(7), and two equivalent O(9) atoms. In the sixth V site, V(6) is bonded in a 5-coordinate geometry to one O(21), one O(3), one O(7), one O(8), and one O(9) atom. In the seventh V site, V(7) is bonded in a 5-coordinate geometry to one O(14), one O(17), one O(4), and two equivalent O(24) atoms. In the eighth V site, V(8) is bonded in a 5-coordinate geometry to one O(13), one O(16), one O(5), and two equivalent O(24) atoms. In the ninth V site, V(9) is bonded in a 5-coordinate geometry to one O(15), one O(18), one O(22), one O(23), and one O(6) atom. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to two equivalent Na(1) and one V(4) atom. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to two equivalent Na(1) and one V(5) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Ca(1) and one V(6) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one V(7) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to one Ca(1) and one V(8) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one V(9) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one V(5) and two equivalent V(6) atoms. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(4) and two equivalent V(6) atoms. In the ninth O site, O(9) is bonded in a distorted trigonal non-coplanar geometry to one V(4), one V(5), and one V(6) atom. In the tenth O site, O(10) is bonded in a single-bond geometry to one V(1) atom. In the eleventh O site, O(11) is bonded in a single-bond geometry to one V(2) atom. In the twelfth O site, O(12) is bonded in a single-bond geometry to one V(3) atom. In the thirteenth O site, O(13) is bonded in a bent 120 degrees geometry to one V(1) and one V(8) atom. In the fourteenth O site, O(14) is bonded in a bent 120 degrees geometry to one V(2) and one V(7) atom. In the fifteenth O site, O(15) is bonded in a bent 120 degrees geometry to one V(3) and one V(9) atom. In the sixteenth O site, O(16) is bonded in a trigonal non-coplanar geometry to one V(8) and two equivalent V(3) atoms. In the seventeenth O site, O(17) is bonded in a trigonal non-coplanar geometry to one V(7) and two equivalent V(3) atoms. In the eighteenth O site, O(18) is bonded in a trigonal non-coplanar geometry to one V(1), one V(2), and one V(9) atom. In the nineteenth O site, O(19) is bonded in a single-bond geometry to one V(4) atom. In the twentieth O site, O(20) is bonded in a distorted linear geometry to one Ca(1) and one V(5) atom. In the twenty-first O site, O(21) is bonded in a linear geometry to one Na(1) and one V(6) atom. In the twenty-second O site, O(22) is bonded in a 3-coordinate geometry to one V(2) and two equivalent V(9) atoms. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one V(1) and two equivalent V(9) atoms. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one V(3), one V(7), and one V(8) atom.
Na2CaV12O32 crystallizes in the monoclinic Cm space group. Na(1) is bonded to one O(1), one O(2), one O(21), and one O(6) atom to form distorted corner-sharing NaO4 trigonal pyramids. The Na(1)-O(1) bond length is 2.28 Å. The Na(1)-O(2) bond length is 2.32 Å. The Na(1)-O(21) bond length is 2.21 Å. The Na(1)-O(6) bond length is 2.42 Å. Ca(1) is bonded in a rectangular see-saw-like geometry to one O(20), one O(5), and two equivalent O(3) atoms. The Ca(1)-O(20) bond length is 2.21 Å. The Ca(1)-O(5) bond length is 2.41 Å. Both Ca(1)-O(3) bond lengths are 2.25 Å. There are nine inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(10), one O(13), one O(23), and two equivalent O(18) atoms. The V(1)-O(10) bond length is 1.60 Å. The V(1)-O(13) bond length is 1.78 Å. The V(1)-O(23) bond length is 2.19 Å. Both V(1)-O(18) bond lengths are 1.93 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(11), one O(14), one O(22), and two equivalent O(18) atoms. The V(2)-O(11) bond length is 1.60 Å. The V(2)-O(14) bond length is 1.77 Å. The V(2)-O(22) bond length is 2.19 Å. Both V(2)-O(18) bond lengths are 1.94 Å. In the third V site, V(3) is bonded in a 5-coordinate geometry to one O(12), one O(15), one O(16), one O(17), and one O(24) atom. The V(3)-O(12) bond length is 1.60 Å. The V(3)-O(15) bond length is 1.78 Å. The V(3)-O(16) bond length is 1.94 Å. The V(3)-O(17) bond length is 1.93 Å. The V(3)-O(24) bond length is 2.20 Å. In the fourth V site, V(4) is bonded in a 5-coordinate geometry to one O(1), one O(19), one O(8), and two equivalent O(9) atoms. The V(4)-O(1) bond length is 1.72 Å. The V(4)-O(19) bond length is 1.64 Å. The V(4)-O(8) bond length is 2.01 Å. Both V(4)-O(9) bond lengths are 1.93 Å. In the fifth V site, V(5) is bonded in a 5-coordinate geometry to one O(2), one O(20), one O(7), and two equivalent O(9) atoms. The V(5)-O(2) bond length is 1.70 Å. The V(5)-O(20) bond length is 1.68 Å. The V(5)-O(7) bond length is 2.07 Å. Both V(5)-O(9) bond lengths are 1.87 Å. In the sixth V site, V(6) is bonded in a 5-coordinate geometry to one O(21), one O(3), one O(7), one O(8), and one O(9) atom. The V(6)-O(21) bond length is 1.66 Å. The V(6)-O(3) bond length is 1.72 Å. The V(6)-O(7) bond length is 1.89 Å. The V(6)-O(8) bond length is 1.91 Å. The V(6)-O(9) bond length is 2.04 Å. In the seventh V site, V(7) is bonded in a 5-coordinate geometry to one O(14), one O(17), one O(4), and two equivalent O(24) atoms. The V(7)-O(14) bond length is 1.87 Å. The V(7)-O(17) bond length is 2.04 Å. The V(7)-O(4) bond length is 1.59 Å. Both V(7)-O(24) bond lengths are 1.90 Å. In the eighth V site, V(8) is bonded in a 5-coordinate geometry to one O(13), one O(16), one O(5), and two equivalent O(24) atoms. The V(8)-O(13) bond length is 1.85 Å. The V(8)-O(16) bond length is 2.05 Å. The V(8)-O(5) bond length is 1.62 Å. Both V(8)-O(24) bond lengths are 1.88 Å. In the ninth V site, V(9) is bonded in a 5-coordinate geometry to one O(15), one O(18), one O(22), one O(23), and one O(6) atom. The V(9)-O(15) bond length is 1.85 Å. The V(9)-O(18) bond length is 2.04 Å. The V(9)-O(22) bond length is 1.89 Å. The V(9)-O(23) bond length is 1.89 Å. The V(9)-O(6) bond length is 1.61 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to two equivalent Na(1) and one V(4) atom. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to two equivalent Na(1) and one V(5) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Ca(1) and one V(6) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one V(7) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to one Ca(1) and one V(8) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one V(9) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one V(5) and two equivalent V(6) atoms. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(4) and two equivalent V(6) atoms. In the ninth O site, O(9) is bonded in a distorted trigonal non-coplanar geometry to one V(4), one V(5), and one V(6) atom. In the tenth O site, O(10) is bonded in a single-bond geometry to one V(1) atom. In the eleventh O site, O(11) is bonded in a single-bond geometry to one V(2) atom. In the twelfth O site, O(12) is bonded in a single-bond geometry to one V(3) atom. In the thirteenth O site, O(13) is bonded in a bent 120 degrees geometry to one V(1) and one V(8) atom. In the fourteenth O site, O(14) is bonded in a bent 120 degrees geometry to one V(2) and one V(7) atom. In the fifteenth O site, O(15) is bonded in a bent 120 degrees geometry to one V(3) and one V(9) atom. In the sixteenth O site, O(16) is bonded in a trigonal non-coplanar geometry to one V(8) and two equivalent V(3) atoms. In the seventeenth O site, O(17) is bonded in a trigonal non-coplanar geometry to one V(7) and two equivalent V(3) atoms. In the eighteenth O site, O(18) is bonded in a trigonal non-coplanar geometry to one V(1), one V(2), and one V(9) atom. In the nineteenth O site, O(19) is bonded in a single-bond geometry to one V(4) atom. In the twentieth O site, O(20) is bonded in a distorted linear geometry to one Ca(1) and one V(5) atom. In the twenty-first O site, O(21) is bonded in a linear geometry to one Na(1) and one V(6) atom. In the twenty-second O site, O(22) is bonded in a 3-coordinate geometry to one V(2) and two equivalent V(9) atoms. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one V(1) and two equivalent V(9) atoms. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one V(3), one V(7), and one V(8) atom.