K5Mo4O14F crystallizes in the monoclinic C2/c space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 8-coordinate geometry to one O(3), one O(6), one O(7), two equivalent O(4), and three equivalent O(5) atoms. In the second K site, K(2) is bonded in a 10-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(7), and four equivalent O(3) atoms. In the third K site, K(3) is bonded in a 9-coordinate geometry to one O(5), one O(7), two equivalent O(2), two equivalent O(4), two equivalent O(6), and one F(1) atom. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in a tetrahedral geometry to one O(1), one O(5), one O(6), and one O(7) atom. In the second Mo site, Mo(2) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), two equivalent O(1), and one F(1) atom. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one K(2), one Mo(1), and two equivalent Mo(2) atoms. In the second O site, O(2) is bonded in a distorted single-bond geometry to one K(2), two equivalent K(3), and one Mo(2) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one K(1), two equivalent K(2), and one Mo(2) atom. In the fourth O site, O(4) is bonded in a 1-coordinate geometry to two equivalent K(1), two equivalent K(3), and one Mo(2) atom. In the fifth O site, O(5) is bonded in a 1-coordinate geometry to one K(3), three equivalent K(1), and one Mo(1) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one K(1), two equivalent K(3), and one Mo(1) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one K(1), one K(2), one K(3), and one Mo(1) atom. F(1) is bonded in a distorted trigonal pyramidal geometry to two equivalent K(3) and two equivalent Mo(2) atoms.
K5Mo4O14F crystallizes in the monoclinic C2/c space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 8-coordinate geometry to one O(3), one O(6), one O(7), two equivalent O(4), and three equivalent O(5) atoms. The K(1)-O(3) bond length is 2.71 Å. The K(1)-O(6) bond length is 3.09 Å. The K(1)-O(7) bond length is 3.32 Å. There is one shorter (2.81 Å) and one longer (3.10 Å) K(1)-O(4) bond length. There are a spread of K(1)-O(5) bond distances ranging from 2.87-3.33 Å. In the second K site, K(2) is bonded in a 10-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(7), and four equivalent O(3) atoms. Both K(2)-O(1) bond lengths are 2.98 Å. Both K(2)-O(2) bond lengths are 3.26 Å. Both K(2)-O(7) bond lengths are 3.00 Å. There are two shorter (2.68 Å) and two longer (3.00 Å) K(2)-O(3) bond lengths. In the third K site, K(3) is bonded in a 9-coordinate geometry to one O(5), one O(7), two equivalent O(2), two equivalent O(4), two equivalent O(6), and one F(1) atom. The K(3)-O(5) bond length is 3.04 Å. The K(3)-O(7) bond length is 3.22 Å. There is one shorter (2.80 Å) and one longer (2.88 Å) K(3)-O(2) bond length. There is one shorter (3.00 Å) and one longer (3.06 Å) K(3)-O(4) bond length. There is one shorter (2.86 Å) and one longer (2.94 Å) K(3)-O(6) bond length. The K(3)-F(1) bond length is 2.81 Å. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in a tetrahedral geometry to one O(1), one O(5), one O(6), and one O(7) atom. The Mo(1)-O(1) bond length is 1.92 Å. The Mo(1)-O(5) bond length is 1.78 Å. The Mo(1)-O(6) bond length is 1.78 Å. The Mo(1)-O(7) bond length is 1.77 Å. In the second Mo site, Mo(2) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), two equivalent O(1), and one F(1) atom. The Mo(2)-O(2) bond length is 1.77 Å. The Mo(2)-O(3) bond length is 1.77 Å. The Mo(2)-O(4) bond length is 1.79 Å. There is one shorter (2.22 Å) and one longer (2.23 Å) Mo(2)-O(1) bond length. The Mo(2)-F(1) bond length is 2.24 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one K(2), one Mo(1), and two equivalent Mo(2) atoms. In the second O site, O(2) is bonded in a distorted single-bond geometry to one K(2), two equivalent K(3), and one Mo(2) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one K(1), two equivalent K(2), and one Mo(2) atom. In the fourth O site, O(4) is bonded in a 1-coordinate geometry to two equivalent K(1), two equivalent K(3), and one Mo(2) atom. In the fifth O site, O(5) is bonded in a 1-coordinate geometry to one K(3), three equivalent K(1), and one Mo(1) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one K(1), two equivalent K(3), and one Mo(1) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one K(1), one K(2), one K(3), and one Mo(1) atom. F(1) is bonded in a distorted trigonal pyramidal geometry to two equivalent K(3) and two equivalent Mo(2) atoms.