Li3V12O29 crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(14), and two equivalent O(17) atoms. In the second Li site, Li(2) is bonded to one O(22), one O(24), and two equivalent O(6) atoms to form LiO4 trigonal pyramids that share  a cornercorner with one V(9)O6 octahedra and corners with two equivalent Li(2)O4 trigonal pyramids. The corner-sharing octahedral tilt angles are 24°. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(28), two equivalent O(13), and two equivalent O(15) atoms. There are twelve inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(16), one O(2), one O(4), and two equivalent O(18) atoms to form distorted corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 1-30°. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(6), and two equivalent O(21) atoms. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(1), one O(4), one O(5), one O(7), and two equivalent O(20) atoms. In the fourth V site, V(4) is bonded to one O(10), one O(11), one O(7), one O(8), and two equivalent O(25) atoms to form distorted corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 30°. In the fifth V site, V(5) is bonded in a 5-coordinate geometry to one O(11), one O(13), one O(9), and two equivalent O(27) atoms. In the sixth V site, V(6) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(12), one O(14), and two equivalent O(29) atoms. In the seventh V site, V(7) is bonded in a 6-coordinate geometry to one O(15), one O(18), one O(19), one O(20), and two equivalent O(1) atoms. In the eighth V site, V(8) is bonded in a 5-coordinate geometry to one O(17), one O(19), one O(21), and two equivalent O(3) atoms. In the ninth V site, V(9) is bonded to one O(19), one O(20), one O(22), one O(23), and two equivalent O(5) atoms to form distorted VO6 octahedra that share corners with two equivalent V(9)O6 octahedra and  a cornercorner with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles are 34°. In the tenth V site, V(10) is bonded in a 6-coordinate geometry to one O(23), one O(25), one O(26), one O(29), and two equivalent O(10) atoms. In the eleventh V site, V(11) is bonded in a 6-coordinate geometry to one O(24), one O(26), one O(27), one O(28), and two equivalent O(9) atoms. In the twelfth V site, V(12) is bonded to one O(16), one O(26), one O(28), one O(29), and two equivalent O(12) atoms to form distorted corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 1-30°. There are twenty-nine inequivalent O sites. In the first O site, O(1) is bonded to one V(1), one V(3), and two equivalent V(7) atoms to form a mixture of distorted edge and corner-sharing OV4 tetrahedra. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one V(2) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one V(2) and two equivalent V(8) atoms. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one V(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one V(3) and two equivalent V(9) atoms. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Li(2) and one V(2) atom. In the seventh O site, O(7) is bonded in a linear geometry to one V(3) and one V(4) atom. In the eighth O site, O(8) is bonded in a single-bond geometry to one V(4) atom. In the ninth O site, O(9) is bonded in a distorted trigonal non-coplanar geometry to one V(5) and two equivalent V(11) atoms. In the tenth O site, O(10) is bonded to one V(4), one V(6), and two equivalent V(10) atoms to form a mixture of distorted edge and corner-sharing OV4 trigonal pyramids. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one V(4), 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(6) and two equivalent V(12) atoms. In the thirteenth O site, O(13) is bonded in a distorted single-bond geometry to two equivalent Li(3) and one V(5) atom. In the fourteenth O site, O(14) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(6) atom. In the fifteenth O site, O(15) is bonded in a trigonal planar geometry to two equivalent Li(3) and one V(7) atom. In the sixteenth O site, O(16) is bonded in a linear geometry to one V(1) and one V(12) atom. In the seventeenth O site, O(17) is bonded in a distorted single-bond geometry to two equivalent Li(1) and one V(8) atom. In the eighteenth O site, O(18) is bonded in a distorted trigonal non-coplanar geometry to one V(7) and two equivalent V(1) atoms. In the nineteenth O site, O(19) is bonded in a distorted trigonal planar geometry to one V(7), one V(8), and one V(9) atom. In the twentieth O site, O(20) is bonded to one V(7), one V(9), and two equivalent V(3) atoms to form a mixture of distorted edge and corner-sharing OV4 trigonal pyramids. In the twenty-first O site, O(21) is bonded in a distorted trigonal non-coplanar geometry to one V(8) and two equivalent V(2) atoms. In the twenty-second O site, O(22) is bonded in a distorted bent 150 degrees geometry to one Li(2) and one V(9) atom. In the twenty-third O site, O(23) is bonded in a linear geometry to one V(10) and one V(9) atom. In the twenty-fourth O site, O(24) is bonded in a bent 150 degrees geometry to one Li(2) and one V(11) atom. In the twenty-fifth O site, O(25) is bonded in a distorted trigonal non-coplanar geometry to one V(10) and two equivalent V(4) atoms. In the twenty-sixth O site, O(26) is bonded in a distorted trigonal planar geometry to one V(10), one V(11), and one V(12) atom. In the twenty-seventh O site, O(27) is bonded in a distorted T-shaped geometry to one V(11) and two equivalent V(5) atoms. In the twenty-eighth O site, O(28) is bonded in a 2-coordinate geometry to one Li(3), one V(11), and one V(12) atom. In the twenty-ninth O site, O(29) is bonded to one V(10), one V(12), and two equivalent V(6) atoms to form a mixture of distorted edge and corner-sharing OV4 tetrahedra.
Li3V12O29 crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(14), and two equivalent O(17) atoms. The Li(1)-O(2) bond length is 1.98 Å. Both Li(1)-O(14) bond lengths are 2.18 Å. Both Li(1)-O(17) bond lengths are 2.58 Å. In the second Li site, Li(2) is bonded to one O(22), one O(24), and two equivalent O(6) atoms to form LiO4 trigonal pyramids that share  a cornercorner with one V(9)O6 octahedra and corners with two equivalent Li(2)O4 trigonal pyramids. The corner-sharing octahedral tilt angles are 24°. The Li(2)-O(22) bond length is 2.01 Å. The Li(2)-O(24) bond length is 1.91 Å. Both Li(2)-O(6) bond lengths are 2.10 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(28), two equivalent O(13), and two equivalent O(15) atoms. The Li(3)-O(28) bond length is 1.98 Å. Both Li(3)-O(13) bond lengths are 2.59 Å. Both Li(3)-O(15) bond lengths are 2.17 Å. There are twelve inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(16), one O(2), one O(4), and two equivalent O(18) atoms to form distorted corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 1-30°. The V(1)-O(1) bond length is 2.18 Å. The V(1)-O(16) bond length is 1.78 Å. The V(1)-O(2) bond length is 1.68 Å. The V(1)-O(4) bond length is 2.17 Å. Both V(1)-O(18) bond lengths are 1.92 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(6), and two equivalent O(21) atoms. The V(2)-O(2) bond length is 2.36 Å. The V(2)-O(3) bond length is 2.03 Å. The V(2)-O(4) bond length is 1.79 Å. The V(2)-O(6) bond length is 1.66 Å. Both V(2)-O(21) bond lengths are 1.92 Å. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(1), one O(4), one O(5), one O(7), and two equivalent O(20) atoms. The V(3)-O(1) bond length is 2.22 Å. The V(3)-O(4) bond length is 2.03 Å. The V(3)-O(5) bond length is 1.97 Å. The V(3)-O(7) bond length is 1.76 Å. Both V(3)-O(20) bond lengths are 1.93 Å. In the fourth V site, V(4) is bonded to one O(10), one O(11), one O(7), one O(8), and two equivalent O(25) atoms to form distorted corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 30°. The V(4)-O(10) bond length is 2.18 Å. The V(4)-O(11) bond length is 2.10 Å. The V(4)-O(7) bond length is 1.89 Å. The V(4)-O(8) bond length is 1.64 Å. Both V(4)-O(25) bond lengths are 1.91 Å. In the fifth V site, V(5) is bonded in a 5-coordinate geometry to one O(11), one O(13), one O(9), and two equivalent O(27) atoms. The V(5)-O(11) bond length is 1.82 Å. The V(5)-O(13) bond length is 1.64 Å. The V(5)-O(9) bond length is 2.00 Å. Both V(5)-O(27) bond lengths are 1.92 Å. In the sixth V site, V(6) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(12), one O(14), and two equivalent O(29) atoms. The V(6)-O(10) bond length is 2.28 Å. The V(6)-O(11) bond length is 2.03 Å. The V(6)-O(12) bond length is 2.04 Å. The V(6)-O(14) bond length is 1.68 Å. Both V(6)-O(29) bond lengths are 1.95 Å. In the seventh V site, V(7) is bonded in a 6-coordinate geometry to one O(15), one O(18), one O(19), one O(20), and two equivalent O(1) atoms. The V(7)-O(15) bond length is 1.68 Å. The V(7)-O(18) bond length is 2.03 Å. The V(7)-O(19) bond length is 2.01 Å. The V(7)-O(20) bond length is 2.29 Å. Both V(7)-O(1) bond lengths are 1.96 Å. In the eighth V site, V(8) is bonded in a 5-coordinate geometry to one O(17), one O(19), one O(21), and two equivalent O(3) atoms. The V(8)-O(17) bond length is 1.64 Å. The V(8)-O(19) bond length is 1.80 Å. The V(8)-O(21) bond length is 2.04 Å. Both V(8)-O(3) bond lengths are 1.92 Å. In the ninth V site, V(9) is bonded to one O(19), one O(20), one O(22), one O(23), and two equivalent O(5) atoms to form distorted VO6 octahedra that share corners with two equivalent V(9)O6 octahedra and  a cornercorner with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles are 34°. The V(9)-O(19) bond length is 2.10 Å. The V(9)-O(20) bond length is 2.21 Å. The V(9)-O(22) bond length is 1.67 Å. The V(9)-O(23) bond length is 1.98 Å. Both V(9)-O(5) bond lengths are 1.93 Å. In the tenth V site, V(10) is bonded in a 6-coordinate geometry to one O(23), one O(25), one O(26), one O(29), and two equivalent O(10) atoms. The V(10)-O(23) bond length is 1.71 Å. The V(10)-O(25) bond length is 2.06 Å. The V(10)-O(26) bond length is 2.01 Å. The V(10)-O(29) bond length is 2.24 Å. Both V(10)-O(10) bond lengths are 1.95 Å. In the eleventh V site, V(11) is bonded in a 6-coordinate geometry to one O(24), one O(26), one O(27), one O(28), and two equivalent O(9) atoms. The V(11)-O(24) bond length is 1.63 Å. The V(11)-O(26) bond length is 1.81 Å. The V(11)-O(27) bond length is 2.03 Å. The V(11)-O(28) bond length is 2.41 Å. Both V(11)-O(9) bond lengths are 1.93 Å. In the twelfth V site, V(12) is bonded to one O(16), one O(26), one O(28), one O(29), and two equivalent O(12) atoms to form distorted corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 1-30°. The V(12)-O(16) bond length is 1.83 Å. The V(12)-O(26) bond length is 2.11 Å. The V(12)-O(28) bond length is 1.68 Å. The V(12)-O(29) bond length is 2.17 Å. Both V(12)-O(12) bond lengths are 1.91 Å. There are twenty-nine inequivalent O sites. In the first O site, O(1) is bonded to one V(1), one V(3), and two equivalent V(7) atoms to form a mixture of distorted edge and corner-sharing OV4 tetrahedra. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one V(2) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one V(2) and two equivalent V(8) atoms. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one V(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one V(3) and two equivalent V(9) atoms. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Li(2) and one V(2) atom. In the seventh O site, O(7) is bonded in a linear geometry to one V(3) and one V(4) atom. In the eighth O site, O(8) is bonded in a single-bond geometry to one V(4) atom. In the ninth O site, O(9) is bonded in a distorted trigonal non-coplanar geometry to one V(5) and two equivalent V(11) atoms. In the tenth O site, O(10) is bonded to one V(4), one V(6), and two equivalent V(10) atoms to form a mixture of distorted edge and corner-sharing OV4 trigonal pyramids. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one V(4), 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(6) and two equivalent V(12) atoms. In the thirteenth O site, O(13) is bonded in a distorted single-bond geometry to two equivalent Li(3) and one V(5) atom. In the fourteenth O site, O(14) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(6) atom. In the fifteenth O site, O(15) is bonded in a trigonal planar geometry to two equivalent Li(3) and one V(7) atom. In the sixteenth O site, O(16) is bonded in a linear geometry to one V(1) and one V(12) atom. In the seventeenth O site, O(17) is bonded in a distorted single-bond geometry to two equivalent Li(1) and one V(8) atom. In the eighteenth O site, O(18) is bonded in a distorted trigonal non-coplanar geometry to one V(7) and two equivalent V(1) atoms. In the nineteenth O site, O(19) is bonded in a distorted trigonal planar geometry to one V(7), one V(8), and one V(9) atom. In the twentieth O site, O(20) is bonded to one V(7), one V(9), and two equivalent V(3) atoms to form a mixture of distorted edge and corner-sharing OV4 trigonal pyramids. In the twenty-first O site, O(21) is bonded in a distorted trigonal non-coplanar geometry to one V(8) and two equivalent V(2) atoms. In the twenty-second O site, O(22) is bonded in a distorted bent 150 degrees geometry to one Li(2) and one V(9) atom. In the twenty-third O site, O(23) is bonded in a linear geometry to one V(10) and one V(9) atom. In the twenty-fourth O site, O(24) is bonded in a bent 150 degrees geometry to one Li(2) and one V(11) atom. In the twenty-fifth O site, O(25) is bonded in a distorted trigonal non-coplanar geometry to one V(10) and two equivalent V(4) atoms. In the twenty-sixth O site, O(26) is bonded in a distorted trigonal planar geometry to one V(10), one V(11), and one V(12) atom. In the twenty-seventh O site, O(27) is bonded in a distorted T-shaped geometry to one V(11) and two equivalent V(5) atoms. In the twenty-eighth O site, O(28) is bonded in a 2-coordinate geometry to one Li(3), one V(11), and one V(12) atom. In the twenty-ninth O site, O(29) is bonded to one V(10), one V(12), and two equivalent V(6) atoms to form a mixture of distorted edge and corner-sharing OV4 tetrahedra.