Na2CaV12O36 crystallizes in the monoclinic Cm space group. Na(1) is bonded to one O(10), one O(11), one O(15), one O(25), one O(26), and one O(6) atom to form NaO6 octahedra that share  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(7)O6 trigonal bipyramid, and edges with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 49°. Ca(1) is bonded in an octahedral geometry to one O(14), one O(5), two equivalent O(12), and two equivalent O(27) atoms. There are nine inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(2), one O(22), one O(4), one O(8), and two equivalent O(24) atoms. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(23), one O(5), one O(7), and two equivalent O(24) atoms. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(22), one O(23), one O(24), one O(3), one O(6), and one O(9) atom. In the fourth V site, V(4) is bonded to one O(13), one O(17), one O(20), one O(25), and two equivalent O(18) atoms to form distorted VO6 octahedra that share corners with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 49°. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(14), one O(16), one O(19), one O(26), and two equivalent O(18) atoms. In the sixth V site, V(6) is bonded in a 6-coordinate geometry to one O(15), one O(16), one O(17), one O(18), one O(21), and one O(27) atom. In the seventh V site, V(7) is bonded to one O(10), one O(19), one O(23), one O(7), and two equivalent O(3) atoms to form distorted VO6 trigonal bipyramids that share corners with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 47°. In the eighth V site, V(8) is bonded in a 6-coordinate geometry to one O(11), one O(20), one O(22), one O(8), and two equivalent O(3) atoms. In the ninth V site, V(9) is bonded in a 6-coordinate geometry to one O(1), one O(12), one O(2), one O(21), one O(24), and one O(9) atom. There are twenty-seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(2) and two equivalent V(9) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(9) atoms. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(3), one V(7), and one V(8) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one V(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to one Ca(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a linear geometry to one Na(1) and one V(3) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one V(2) and one V(7) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(8) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one V(3) and one V(9) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to two equivalent Na(1) and one V(7) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one V(8) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Ca(1) and one V(9) atom. In the thirteenth O site, O(13) is bonded in a single-bond geometry to one V(4) atom. In the fourteenth O site, O(14) is bonded in a linear geometry to one Ca(1) and one V(5) atom. In the fifteenth O site, O(15) is bonded in a linear geometry to one Na(1) and one V(6) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal non-coplanar geometry to one V(5) and two equivalent V(6) atoms. In the seventeenth O site, O(17) is bonded in a distorted trigonal non-coplanar geometry to one V(4) and two equivalent V(6) atoms. In the eighteenth O site, O(18) is bonded in a distorted trigonal non-coplanar geometry to one V(4), one V(5), and one V(6) atom. In the nineteenth O site, O(19) is bonded in a linear geometry to one V(5) and one V(7) atom. In the twentieth O site, O(20) is bonded in a linear geometry to one V(4) and one V(8) atom. In the twenty-first O site, O(21) is bonded in a linear geometry to one V(6) and one V(9) atom. In the twenty-second O site, O(22) is bonded in a 4-coordinate geometry to one V(1), one V(8), and two equivalent V(3) atoms. In the twenty-third O site, O(23) is bonded in a 4-coordinate geometry to one V(2), one V(7), and two equivalent V(3) atoms. In the twenty-fourth O site, O(24) is bonded in a 4-coordinate geometry to one V(1), one V(2), one V(3), and one V(9) atom. In the twenty-fifth O site, O(25) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one V(4) atom. In the twenty-sixth O site, O(26) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one V(5) atom. In the twenty-seventh O site, O(27) is bonded in a distorted bent 120 degrees geometry to one Ca(1) and one V(6) atom.
Na2CaV12O36 crystallizes in the monoclinic Cm space group. Na(1) is bonded to one O(10), one O(11), one O(15), one O(25), one O(26), and one O(6) atom to form NaO6 octahedra that share  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(7)O6 trigonal bipyramid, and edges with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 49°. The Na(1)-O(10) bond length is 2.50 Å. The Na(1)-O(11) bond length is 2.51 Å. The Na(1)-O(15) bond length is 2.35 Å. The Na(1)-O(25) bond length is 2.46 Å. The Na(1)-O(26) bond length is 2.50 Å. The Na(1)-O(6) bond length is 2.29 Å. Ca(1) is bonded in an octahedral geometry to one O(14), one O(5), two equivalent O(12), and two equivalent O(27) atoms. The Ca(1)-O(14) bond length is 2.31 Å. The Ca(1)-O(5) bond length is 2.26 Å. Both Ca(1)-O(12) bond lengths are 2.39 Å. Both Ca(1)-O(27) bond lengths are 2.40 Å. There are nine inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(2), one O(22), one O(4), one O(8), and two equivalent O(24) atoms. The V(1)-O(2) bond length is 2.07 Å. The V(1)-O(22) bond length is 2.38 Å. The V(1)-O(4) bond length is 1.61 Å. The V(1)-O(8) bond length is 1.80 Å. Both V(1)-O(24) bond lengths are 1.93 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(23), one O(5), one O(7), and two equivalent O(24) atoms. The V(2)-O(1) bond length is 2.50 Å. The V(2)-O(23) bond length is 2.28 Å. The V(2)-O(5) bond length is 1.64 Å. The V(2)-O(7) bond length is 1.74 Å. Both V(2)-O(24) bond lengths are 1.89 Å. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(22), one O(23), one O(24), one O(3), one O(6), and one O(9) atom. The V(3)-O(22) bond length is 1.94 Å. The V(3)-O(23) bond length is 1.89 Å. The V(3)-O(24) bond length is 2.33 Å. The V(3)-O(3) bond length is 2.28 Å. The V(3)-O(6) bond length is 1.62 Å. The V(3)-O(9) bond length is 1.76 Å. In the fourth V site, V(4) is bonded to one O(13), one O(17), one O(20), one O(25), and two equivalent O(18) atoms to form distorted VO6 octahedra that share corners with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 49°. The V(4)-O(13) bond length is 1.66 Å. The V(4)-O(17) bond length is 2.05 Å. The V(4)-O(20) bond length is 2.21 Å. The V(4)-O(25) bond length is 1.76 Å. Both V(4)-O(18) bond lengths are 1.92 Å. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(14), one O(16), one O(19), one O(26), and two equivalent O(18) atoms. The V(5)-O(14) bond length is 1.67 Å. The V(5)-O(16) bond length is 2.14 Å. The V(5)-O(19) bond length is 2.24 Å. The V(5)-O(26) bond length is 1.74 Å. Both V(5)-O(18) bond lengths are 1.89 Å. In the sixth V site, V(6) is bonded in a 6-coordinate geometry to one O(15), one O(16), one O(17), one O(18), one O(21), and one O(27) atom. The V(6)-O(15) bond length is 1.65 Å. The V(6)-O(16) bond length is 1.90 Å. The V(6)-O(17) bond length is 1.92 Å. The V(6)-O(18) bond length is 2.10 Å. The V(6)-O(21) bond length is 2.29 Å. The V(6)-O(27) bond length is 1.75 Å. In the seventh V site, V(7) is bonded to one O(10), one O(19), one O(23), one O(7), and two equivalent O(3) atoms to form distorted VO6 trigonal bipyramids that share corners with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 47°. The V(7)-O(10) bond length is 1.64 Å. The V(7)-O(19) bond length is 1.89 Å. The V(7)-O(23) bond length is 2.52 Å. The V(7)-O(7) bond length is 1.96 Å. Both V(7)-O(3) bond lengths are 1.88 Å. In the eighth V site, V(8) is bonded in a 6-coordinate geometry to one O(11), one O(20), one O(22), one O(8), and two equivalent O(3) atoms. The V(8)-O(11) bond length is 1.65 Å. The V(8)-O(20) bond length is 1.71 Å. The V(8)-O(22) bond length is 2.40 Å. The V(8)-O(8) bond length is 2.11 Å. Both V(8)-O(3) bond lengths are 1.95 Å. In the ninth V site, V(9) is bonded in a 6-coordinate geometry to one O(1), one O(12), one O(2), one O(21), one O(24), and one O(9) atom. The V(9)-O(1) bond length is 1.88 Å. The V(9)-O(12) bond length is 1.64 Å. The V(9)-O(2) bond length is 1.94 Å. The V(9)-O(21) bond length is 1.87 Å. The V(9)-O(24) bond length is 2.39 Å. The V(9)-O(9) bond length is 1.94 Å. There are twenty-seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(2) and two equivalent V(9) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(9) atoms. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(3), one V(7), and one V(8) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one V(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to one Ca(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a linear geometry to one Na(1) and one V(3) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one V(2) and one V(7) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(8) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one V(3) and one V(9) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to two equivalent Na(1) and one V(7) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one V(8) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Ca(1) and one V(9) atom. In the thirteenth O site, O(13) is bonded in a single-bond geometry to one V(4) atom. In the fourteenth O site, O(14) is bonded in a linear geometry to one Ca(1) and one V(5) atom. In the fifteenth O site, O(15) is bonded in a linear geometry to one Na(1) and one V(6) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal non-coplanar geometry to one V(5) and two equivalent V(6) atoms. In the seventeenth O site, O(17) is bonded in a distorted trigonal non-coplanar geometry to one V(4) and two equivalent V(6) atoms. In the eighteenth O site, O(18) is bonded in a distorted trigonal non-coplanar geometry to one V(4), one V(5), and one V(6) atom. In the nineteenth O site, O(19) is bonded in a linear geometry to one V(5) and one V(7) atom. In the twentieth O site, O(20) is bonded in a linear geometry to one V(4) and one V(8) atom. In the twenty-first O site, O(21) is bonded in a linear geometry to one V(6) and one V(9) atom. In the twenty-second O site, O(22) is bonded in a 4-coordinate geometry to one V(1), one V(8), and two equivalent V(3) atoms. In the twenty-third O site, O(23) is bonded in a 4-coordinate geometry to one V(2), one V(7), and two equivalent V(3) atoms. In the twenty-fourth O site, O(24) is bonded in a 4-coordinate geometry to one V(1), one V(2), one V(3), and one V(9) atom. In the twenty-fifth O site, O(25) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one V(4) atom. In the twenty-sixth O site, O(26) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one V(5) atom. In the twenty-seventh O site, O(27) is bonded in a distorted bent 120 degrees geometry to one Ca(1) and one V(6) atom.