K5NaV2(MoO5)6 crystallizes in the monoclinic C2/m space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 4-coordinate geometry to four equivalent O(1) and four equivalent O(10) atoms. In the second K site, K(2) is bonded in a 9-coordinate geometry to one O(1), one O(3), one O(4), one O(7), one O(9), two equivalent O(10), and two equivalent O(2) atoms. Na(1) is bonded in a body-centered cubic geometry to two equivalent O(7), two equivalent O(9), and four equivalent O(2) atoms. V(1) is bonded in a 6-coordinate geometry to one O(8), one O(9), two equivalent O(4), and two equivalent O(5) atoms. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms. In the second Mo site, Mo(2) is bonded in a 6-coordinate geometry to one O(5), one O(6), one O(7), one O(8), and two equivalent O(3) atoms. There are ten inequivalent O sites. In the first O site, O(2) is bonded in a 4-coordinate geometry to two equivalent K(2), one Na(1), and one Mo(1) atom. In the second O site, O(3) is bonded in a 3-coordinate geometry to one K(2), one Mo(1), and one Mo(2) atom. In the third O site, O(4) is bonded in a 3-coordinate geometry to one K(2), one V(1), and two equivalent Mo(1) atoms. In the fourth O site, O(5) is bonded in a 5-coordinate geometry to two equivalent V(1), one Mo(2), and two equivalent Mo(1) atoms. In the fifth O site, O(6) is bonded in a single-bond geometry to one Mo(2) atom. In the sixth O site, O(7) is bonded in a distorted single-bond geometry to two equivalent K(2), one Na(1), and one Mo(2) atom. In the seventh O site, O(8) is bonded in a distorted bent 120 degrees geometry to one V(1) and one Mo(2) atom. In the eighth O site, O(9) is bonded in a distorted single-bond geometry to two equivalent K(2), one Na(1), and one V(1) atom. In the ninth O site, O(10) is bonded in a distorted T-shaped geometry to one K(1) and two equivalent K(2) atoms. In the tenth O site, O(1) is bonded in a distorted single-bond geometry to one K(1), one K(2), and one Mo(1) atom.
K5NaV2(MoO5)6 crystallizes in the monoclinic C2/m space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 4-coordinate geometry to four equivalent O(1) and four equivalent O(10) atoms. All K(1)-O(1) bond lengths are 2.90 Å. All K(1)-O(10) bond lengths are 3.34 Å. In the second K site, K(2) is bonded in a 9-coordinate geometry to one O(1), one O(3), one O(4), one O(7), one O(9), two equivalent O(10), and two equivalent O(2) atoms. The K(2)-O(1) bond length is 2.88 Å. The K(2)-O(3) bond length is 2.76 Å. The K(2)-O(4) bond length is 3.28 Å. The K(2)-O(7) bond length is 3.01 Å. The K(2)-O(9) bond length is 2.89 Å. There is one shorter (2.92 Å) and one longer (3.16 Å) K(2)-O(10) bond length. There is one shorter (2.81 Å) and one longer (2.85 Å) K(2)-O(2) bond length. Na(1) is bonded in a body-centered cubic geometry to two equivalent O(7), two equivalent O(9), and four equivalent O(2) atoms. Both Na(1)-O(7) bond lengths are 2.89 Å. Both Na(1)-O(9) bond lengths are 2.55 Å. All Na(1)-O(2) bond lengths are 2.54 Å. V(1) is bonded in a 6-coordinate geometry to one O(8), one O(9), two equivalent O(4), and two equivalent O(5) atoms. The V(1)-O(8) bond length is 1.79 Å. The V(1)-O(9) bond length is 1.66 Å. Both V(1)-O(4) bond lengths are 1.93 Å. There is one shorter (2.09 Å) and one longer (2.36 Å) V(1)-O(5) bond length. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms. The Mo(1)-O(1) bond length is 1.75 Å. The Mo(1)-O(2) bond length is 1.76 Å. The Mo(1)-O(3) bond length is 1.94 Å. The Mo(1)-O(5) bond length is 2.25 Å. There is one shorter (1.99 Å) and one longer (2.37 Å) Mo(1)-O(4) bond length. In the second Mo site, Mo(2) is bonded in a 6-coordinate geometry to one O(5), one O(6), one O(7), one O(8), and two equivalent O(3) atoms. The Mo(2)-O(5) bond length is 2.65 Å. The Mo(2)-O(6) bond length is 1.72 Å. The Mo(2)-O(7) bond length is 1.77 Å. The Mo(2)-O(8) bond length is 2.25 Å. Both Mo(2)-O(3) bond lengths are 1.95 Å. There are ten inequivalent O sites. In the first O site, O(2) is bonded in a 4-coordinate geometry to two equivalent K(2), one Na(1), and one Mo(1) atom. In the second O site, O(3) is bonded in a 3-coordinate geometry to one K(2), one Mo(1), and one Mo(2) atom. In the third O site, O(4) is bonded in a 3-coordinate geometry to one K(2), one V(1), and two equivalent Mo(1) atoms. In the fourth O site, O(5) is bonded in a 5-coordinate geometry to two equivalent V(1), one Mo(2), and two equivalent Mo(1) atoms. In the fifth O site, O(6) is bonded in a single-bond geometry to one Mo(2) atom. In the sixth O site, O(7) is bonded in a distorted single-bond geometry to two equivalent K(2), one Na(1), and one Mo(2) atom. In the seventh O site, O(8) is bonded in a distorted bent 120 degrees geometry to one V(1) and one Mo(2) atom. In the eighth O site, O(9) is bonded in a distorted single-bond geometry to two equivalent K(2), one Na(1), and one V(1) atom. In the ninth O site, O(10) is bonded in a distorted T-shaped geometry to one K(1) and two equivalent K(2) atoms. In the tenth O site, O(1) is bonded in a distorted single-bond geometry to one K(1), one K(2), and one Mo(1) atom.