NaV6O13 crystallizes in the triclinic P1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to one O(13), one O(9), two equivalent O(11), two equivalent O(5), and two equivalent O(8) atoms. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one O(14), one O(18), two equivalent O(16), two equivalent O(19), and two equivalent O(22) atoms. There are twelve inequivalent V sites. In the first V site, V(1) is bonded to one O(12), one O(2), one O(20), one O(7), and two equivalent O(1) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 23°. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(21), one O(3), one O(5), and two equivalent O(2) atoms. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(24), one O(3), one O(6), one O(8), and two equivalent O(4) atoms. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to one O(10), one O(25), one O(4), one O(7), and two equivalent O(6) atoms. In the fifth V site, V(5) is bonded in a 5-coordinate geometry to one O(11), one O(15), one O(18), and two equivalent O(9) atoms. In the sixth V site, V(6) is bonded to one O(11), one O(14), one O(17), one O(8), and two equivalent O(13) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 24°. In the seventh V site, V(7) is bonded to one O(10), one O(13), one O(16), one O(19), and two equivalent O(14) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 24°. In the eighth V site, V(8) is bonded in a 5-coordinate geometry to one O(12), one O(16), one O(9), and two equivalent O(18) atoms. In the ninth V site, V(9) is bonded in a 6-coordinate geometry to one O(17), one O(2), one O(20), one O(23), and two equivalent O(21) atoms. In the tenth V site, V(10) is bonded in a 6-coordinate geometry to one O(19), one O(21), one O(24), one O(3), and two equivalent O(23) atoms. In the eleventh V site, V(11) is bonded in a 6-coordinate geometry to one O(22), one O(24), one O(26), one O(6), and two equivalent O(25) atoms. In the twelfth V site, V(12) is bonded to one O(15), one O(20), one O(25), one O(7), and two equivalent O(26) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 24°. There are twenty-six inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded to one V(1), one V(9), and two equivalent V(2) atoms to form distorted corner-sharing OV4 trigonal pyramids. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(10), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(4) and two equivalent V(3) atoms. In the fifth O site, O(5) is bonded in a 1-coordinate geometry to two equivalent Na(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one V(11), one V(3), and two equivalent V(4) atoms. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one V(1), one V(12), and one V(4) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one V(3), and one V(6) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(1), one V(8), and two equivalent V(5) atoms. In the tenth O site, O(10) is bonded in a linear geometry to one V(4) and one V(7) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one V(5), and one V(6) atom. In the twelfth O site, O(12) is bonded in a linear geometry to one V(1) and one V(8) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Na(1), one V(7), and two equivalent V(6) atoms. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Na(2), one V(6), and two equivalent V(7) atoms. In the fifteenth O site, O(15) is bonded in a linear geometry to one V(12) and one V(5) atom. In the sixteenth O site, O(16) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(2), one V(7), and one V(8) atom. In the seventeenth O site, O(17) is bonded in a linear geometry to one V(6) and one V(9) atom. In the eighteenth O site, O(18) is bonded in a 4-coordinate geometry to one Na(2), one V(5), and two equivalent V(8) atoms. In the nineteenth O site, O(19) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(2), one V(10), and one V(7) atom. In the twentieth O site, O(20) is bonded in a distorted T-shaped geometry to one V(1), one V(12), and one V(9) atom. In the twenty-first O site, O(21) is bonded in a 4-coordinate geometry to one V(10), one V(2), and two equivalent V(9) atoms. In the twenty-second O site, O(22) is bonded in a distorted single-bond geometry to two equivalent Na(2) and one V(11) atom. In the twenty-third O site, O(23) is bonded in a distorted T-shaped geometry to one V(9) and two equivalent V(10) atoms. In the twenty-fourth O site, O(24) is bonded in a distorted bent 150 degrees geometry to one V(10), one V(11), and one V(3) atom. In the twenty-fifth O site, O(25) is bonded to one V(12), one V(4), and two equivalent V(11) atoms to form distorted corner-sharing OV4 trigonal pyramids. In the twenty-sixth O site, O(26) is bonded in a distorted T-shaped geometry to one V(11) and two equivalent V(12) atoms.
NaV6O13 crystallizes in the triclinic P1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to one O(13), one O(9), two equivalent O(11), two equivalent O(5), and two equivalent O(8) atoms. The Na(1)-O(13) bond length is 2.87 Å. The Na(1)-O(9) bond length is 2.53 Å. There is one shorter (2.50 Å) and one longer (2.51 Å) Na(1)-O(11) bond length. There is one shorter (2.43 Å) and one longer (2.44 Å) Na(1)-O(5) bond length. There is one shorter (2.61 Å) and one longer (2.62 Å) Na(1)-O(8) bond length. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one O(14), one O(18), two equivalent O(16), two equivalent O(19), and two equivalent O(22) atoms. The Na(2)-O(14) bond length is 2.84 Å. The Na(2)-O(18) bond length is 2.53 Å. There is one shorter (2.50 Å) and one longer (2.51 Å) Na(2)-O(16) bond length. There is one shorter (2.59 Å) and one longer (2.61 Å) Na(2)-O(19) bond length. There is one shorter (2.43 Å) and one longer (2.44 Å) Na(2)-O(22) bond length. There are twelve inequivalent V sites. In the first V site, V(1) is bonded to one O(12), one O(2), one O(20), one O(7), and two equivalent O(1) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 23°. The V(1)-O(12) bond length is 1.89 Å. The V(1)-O(2) bond length is 2.09 Å. The V(1)-O(20) bond length is 2.06 Å. The V(1)-O(7) bond length is 1.83 Å. Both V(1)-O(1) bond lengths are 1.90 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(21), one O(3), one O(5), and two equivalent O(2) atoms. The V(2)-O(1) bond length is 2.00 Å. The V(2)-O(21) bond length is 2.41 Å. The V(2)-O(3) bond length is 1.86 Å. The V(2)-O(5) bond length is 1.65 Å. There is one shorter (1.93 Å) and one longer (1.94 Å) V(2)-O(2) bond length. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(24), one O(3), one O(6), one O(8), and two equivalent O(4) atoms. The V(3)-O(24) bond length is 2.37 Å. The V(3)-O(3) bond length is 1.81 Å. The V(3)-O(6) bond length is 2.04 Å. The V(3)-O(8) bond length is 1.71 Å. Both V(3)-O(4) bond lengths are 1.92 Å. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to one O(10), one O(25), one O(4), one O(7), and two equivalent O(6) atoms. The V(4)-O(10) bond length is 1.69 Å. The V(4)-O(25) bond length is 2.37 Å. The V(4)-O(4) bond length is 1.99 Å. The V(4)-O(7) bond length is 1.91 Å. Both V(4)-O(6) bond lengths are 1.94 Å. In the fifth V site, V(5) is bonded in a 5-coordinate geometry to one O(11), one O(15), one O(18), and two equivalent O(9) atoms. The V(5)-O(11) bond length is 1.80 Å. The V(5)-O(15) bond length is 1.69 Å. The V(5)-O(18) bond length is 2.01 Å. There is one shorter (1.94 Å) and one longer (1.95 Å) V(5)-O(9) bond length. In the sixth V site, V(6) is bonded to one O(11), one O(14), one O(17), one O(8), and two equivalent O(13) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 24°. The V(6)-O(11) bond length is 1.84 Å. The V(6)-O(14) bond length is 2.07 Å. The V(6)-O(17) bond length is 1.93 Å. The V(6)-O(8) bond length is 2.11 Å. Both V(6)-O(13) bond lengths are 1.91 Å. In the seventh V site, V(7) is bonded to one O(10), one O(13), one O(16), one O(19), and two equivalent O(14) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 24°. The V(7)-O(10) bond length is 1.93 Å. The V(7)-O(13) bond length is 2.07 Å. The V(7)-O(16) bond length is 1.84 Å. The V(7)-O(19) bond length is 2.12 Å. There is one shorter (1.90 Å) and one longer (1.91 Å) V(7)-O(14) bond length. In the eighth V site, V(8) is bonded in a 5-coordinate geometry to one O(12), one O(16), one O(9), and two equivalent O(18) atoms. The V(8)-O(12) bond length is 1.69 Å. The V(8)-O(16) bond length is 1.80 Å. The V(8)-O(9) bond length is 2.01 Å. There is one shorter (1.94 Å) and one longer (1.95 Å) V(8)-O(18) bond length. In the ninth V site, V(9) is bonded in a 6-coordinate geometry to one O(17), one O(2), one O(20), one O(23), and two equivalent O(21) atoms. The V(9)-O(17) bond length is 1.69 Å. The V(9)-O(2) bond length is 2.38 Å. The V(9)-O(20) bond length is 1.91 Å. The V(9)-O(23) bond length is 1.99 Å. Both V(9)-O(21) bond lengths are 1.94 Å. In the tenth V site, V(10) is bonded in a 6-coordinate geometry to one O(19), one O(21), one O(24), one O(3), and two equivalent O(23) atoms. The V(10)-O(19) bond length is 1.70 Å. The V(10)-O(21) bond length is 2.04 Å. The V(10)-O(24) bond length is 1.81 Å. The V(10)-O(3) bond length is 2.39 Å. Both V(10)-O(23) bond lengths are 1.92 Å. In the eleventh V site, V(11) is bonded in a 6-coordinate geometry to one O(22), one O(24), one O(26), one O(6), and two equivalent O(25) atoms. The V(11)-O(22) bond length is 1.65 Å. The V(11)-O(24) bond length is 1.86 Å. The V(11)-O(26) bond length is 1.99 Å. The V(11)-O(6) bond length is 2.40 Å. Both V(11)-O(25) bond lengths are 1.94 Å. In the twelfth V site, V(12) is bonded to one O(15), one O(20), one O(25), one O(7), and two equivalent O(26) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 24°. The V(12)-O(15) bond length is 1.89 Å. The V(12)-O(20) bond length is 1.83 Å. The V(12)-O(25) bond length is 2.08 Å. The V(12)-O(7) bond length is 2.06 Å. There is one shorter (1.90 Å) and one longer (1.91 Å) V(12)-O(26) bond length. There are twenty-six inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded to one V(1), one V(9), and two equivalent V(2) atoms to form distorted corner-sharing OV4 trigonal pyramids. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(10), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(4) and two equivalent V(3) atoms. In the fifth O site, O(5) is bonded in a 1-coordinate geometry to two equivalent Na(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one V(11), one V(3), and two equivalent V(4) atoms. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one V(1), one V(12), and one V(4) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one V(3), and one V(6) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(1), one V(8), and two equivalent V(5) atoms. In the tenth O site, O(10) is bonded in a linear geometry to one V(4) and one V(7) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one V(5), and one V(6) atom. In the twelfth O site, O(12) is bonded in a linear geometry to one V(1) and one V(8) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Na(1), one V(7), and two equivalent V(6) atoms. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Na(2), one V(6), and two equivalent V(7) atoms. In the fifteenth O site, O(15) is bonded in a linear geometry to one V(12) and one V(5) atom. In the sixteenth O site, O(16) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(2), one V(7), and one V(8) atom. In the seventeenth O site, O(17) is bonded in a linear geometry to one V(6) and one V(9) atom. In the eighteenth O site, O(18) is bonded in a 4-coordinate geometry to one Na(2), one V(5), and two equivalent V(8) atoms. In the nineteenth O site, O(19) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(2), one V(10), and one V(7) atom. In the twentieth O site, O(20) is bonded in a distorted T-shaped geometry to one V(1), one V(12), and one V(9) atom. In the twenty-first O site, O(21) is bonded in a 4-coordinate geometry to one V(10), one V(2), and two equivalent V(9) atoms. In the twenty-second O site, O(22) is bonded in a distorted single-bond geometry to two equivalent Na(2) and one V(11) atom. In the twenty-third O site, O(23) is bonded in a distorted T-shaped geometry to one V(9) and two equivalent V(10) atoms. In the twenty-fourth O site, O(24) is bonded in a distorted bent 150 degrees geometry to one V(10), one V(11), and one V(3) atom. In the twenty-fifth O site, O(25) is bonded to one V(12), one V(4), and two equivalent V(11) atoms to form distorted corner-sharing OV4 trigonal pyramids. In the twenty-sixth O site, O(26) is bonded in a distorted T-shaped geometry to one V(11) and two equivalent V(12) atoms.