NaV5MoO15 crystallizes in the monoclinic Cm space group. Na(1) is bonded in a 7-coordinate geometry to one O(10), two equivalent O(12), two equivalent O(13), and two equivalent O(7) atoms. There are five inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(1), one O(12), one O(3), and two equivalent O(2) atoms. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(13), one O(2), one O(4), and two equivalent O(1) atoms. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(15), one O(3), one O(5), one O(7), and two equivalent O(6) atoms. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to one O(14), one O(4), one O(6), one O(8), and two equivalent O(5) atoms. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(10), one O(3), one O(5), one O(9), and two equivalent O(14) atoms. Mo(1) is bonded in a 6-coordinate geometry to one O(11), one O(4), one O(6), one O(9), and two equivalent O(15) atoms. There are fifteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one V(1) and two equivalent V(2) atoms. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one V(2) and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(1), one V(3), and one V(5) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(2), one V(4), and one Mo(1) atom. In the fifth O site, O(5) is bonded to one V(3), one V(5), and two equivalent V(4) atoms to form distorted OV4 trigonal pyramids that share corners with two equivalent O(5)V4 trigonal pyramids and edges with two equivalent O(6)V3Mo tetrahedra. In the sixth O site, O(6) is bonded to one V(4), two equivalent V(3), and one Mo(1) atom to form distorted OV3Mo tetrahedra that share corners with two equivalent O(6)V3Mo tetrahedra and edges with two equivalent O(5)V4 trigonal pyramids. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to two equivalent Na(1) and one V(3) 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 linear geometry to one V(5) and one Mo(1) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one V(5) atom. In the eleventh O site, O(11) is bonded in a single-bond geometry to one Mo(1) atom. In the twelfth O site, O(12) is bonded in a single-bond geometry to two equivalent Na(1) and one V(1) atom. In the thirteenth O site, O(13) is bonded in a distorted single-bond geometry to two equivalent Na(1) and one V(2) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one V(4) and two equivalent V(5) atoms. In the fifteenth O site, O(15) is bonded in a distorted trigonal non-coplanar geometry to one V(3) and two equivalent Mo(1) atoms.
NaV5MoO15 crystallizes in the monoclinic Cm space group. Na(1) is bonded in a 7-coordinate geometry to one O(10), two equivalent O(12), two equivalent O(13), and two equivalent O(7) atoms. The Na(1)-O(10) bond length is 2.36 Å. Both Na(1)-O(12) bond lengths are 2.82 Å. Both Na(1)-O(13) bond lengths are 2.54 Å. Both Na(1)-O(7) bond lengths are 2.59 Å. There are five inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(1), one O(12), one O(3), and two equivalent O(2) atoms. The V(1)-O(1) bond length is 2.01 Å. The V(1)-O(12) bond length is 1.62 Å. The V(1)-O(3) bond length is 1.81 Å. Both V(1)-O(2) bond lengths are 1.95 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(13), one O(2), one O(4), and two equivalent O(1) atoms. The V(2)-O(13) bond length is 1.63 Å. The V(2)-O(2) bond length is 1.98 Å. The V(2)-O(4) bond length is 1.81 Å. Both V(2)-O(1) bond lengths are 1.94 Å. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(15), one O(3), one O(5), one O(7), and two equivalent O(6) atoms. The V(3)-O(15) bond length is 2.09 Å. The V(3)-O(3) bond length is 2.00 Å. The V(3)-O(5) bond length is 2.33 Å. The V(3)-O(7) bond length is 1.65 Å. Both V(3)-O(6) bond lengths are 1.97 Å. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to one O(14), one O(4), one O(6), one O(8), and two equivalent O(5) atoms. The V(4)-O(14) bond length is 1.90 Å. The V(4)-O(4) bond length is 2.05 Å. The V(4)-O(6) bond length is 2.32 Å. The V(4)-O(8) bond length is 1.61 Å. Both V(4)-O(5) bond lengths are 1.93 Å. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(10), one O(3), one O(5), one O(9), and two equivalent O(14) atoms. The V(5)-O(10) bond length is 1.65 Å. The V(5)-O(3) bond length is 2.06 Å. The V(5)-O(5) bond length is 2.37 Å. The V(5)-O(9) bond length is 2.01 Å. Both V(5)-O(14) bond lengths are 1.98 Å. Mo(1) is bonded in a 6-coordinate geometry to one O(11), one O(4), one O(6), one O(9), and two equivalent O(15) atoms. The Mo(1)-O(11) bond length is 1.72 Å. The Mo(1)-O(4) bond length is 2.27 Å. The Mo(1)-O(6) bond length is 2.21 Å. The Mo(1)-O(9) bond length is 1.79 Å. Both Mo(1)-O(15) bond lengths are 1.95 Å. There are fifteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one V(1) and two equivalent V(2) atoms. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one V(2) and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(1), one V(3), and one V(5) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(2), one V(4), and one Mo(1) atom. In the fifth O site, O(5) is bonded to one V(3), one V(5), and two equivalent V(4) atoms to form distorted OV4 trigonal pyramids that share corners with two equivalent O(5)V4 trigonal pyramids and edges with two equivalent O(6)V3Mo tetrahedra. In the sixth O site, O(6) is bonded to one V(4), two equivalent V(3), and one Mo(1) atom to form distorted OV3Mo tetrahedra that share corners with two equivalent O(6)V3Mo tetrahedra and edges with two equivalent O(5)V4 trigonal pyramids. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to two equivalent Na(1) and one V(3) 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 linear geometry to one V(5) and one Mo(1) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one V(5) atom. In the eleventh O site, O(11) is bonded in a single-bond geometry to one Mo(1) atom. In the twelfth O site, O(12) is bonded in a single-bond geometry to two equivalent Na(1) and one V(1) atom. In the thirteenth O site, O(13) is bonded in a distorted single-bond geometry to two equivalent Na(1) and one V(2) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one V(4) and two equivalent V(5) atoms. In the fifteenth O site, O(15) is bonded in a distorted trigonal non-coplanar geometry to one V(3) and two equivalent Mo(1) atoms.