K3MoCl6 crystallizes in the monoclinic P2_1/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 Cl(1), one Cl(4), one Cl(5), one Cl(6), two equivalent Cl(2), and two equivalent Cl(3) atoms. In the second K site, K(2) is bonded in a 8-coordinate geometry to one Cl(1), one Cl(2), one Cl(4), one Cl(6), two equivalent Cl(3), and two equivalent Cl(5) atoms. In the third K site, K(3) is bonded in a 9-coordinate geometry to one Cl(2), one Cl(5), two equivalent Cl(1), two equivalent Cl(4), and three equivalent Cl(6) atoms. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in an octahedral geometry to two equivalent Cl(1), two equivalent Cl(4), and two equivalent Cl(6) atoms. In the second Mo site, Mo(2) is bonded in an octahedral geometry to two equivalent Cl(2), two equivalent Cl(3), and two equivalent Cl(5) atoms. There are six inequivalent Cl sites. In the first Cl site, Cl(5) is bonded to one K(1), one K(3), two equivalent K(2), and one Mo(2) atom to form a mixture of distorted corner, edge, and face-sharing ClK4Mo trigonal bipyramids. In the second Cl site, Cl(6) is bonded in a 6-coordinate geometry to one K(1), one K(2), three equivalent K(3), and one Mo(1) atom. In the third Cl site, Cl(1) is bonded to one K(1), one K(2), two equivalent K(3), and one Mo(1) atom to form a mixture of distorted corner, edge, and face-sharing ClK4Mo square pyramids. In the fourth Cl site, Cl(2) is bonded in a 5-coordinate geometry to one K(2), one K(3), two equivalent K(1), and one Mo(2) atom. In the fifth Cl site, Cl(3) is bonded to two equivalent K(1), two equivalent K(2), and one Mo(2) atom to form a mixture of distorted corner and edge-sharing ClK4Mo trigonal bipyramids. In the sixth Cl site, Cl(4) is bonded to one K(1), one K(2), two equivalent K(3), and one Mo(1) atom to form a mixture of distorted corner, edge, and face-sharing ClK4Mo square pyramids.
K3MoCl6 crystallizes in the monoclinic P2_1/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 Cl(1), one Cl(4), one Cl(5), one Cl(6), two equivalent Cl(2), and two equivalent Cl(3) atoms. The K(1)-Cl(1) bond length is 3.25 Å. The K(1)-Cl(4) bond length is 3.02 Å. The K(1)-Cl(5) bond length is 3.13 Å. The K(1)-Cl(6) bond length is 3.71 Å. There is one shorter (3.29 Å) and one longer (3.45 Å) K(1)-Cl(2) bond length. Both K(1)-Cl(3) bond lengths are 3.17 Å. In the second K site, K(2) is bonded in a 8-coordinate geometry to one Cl(1), one Cl(2), one Cl(4), one Cl(6), two equivalent Cl(3), and two equivalent Cl(5) atoms. The K(2)-Cl(1) bond length is 3.21 Å. The K(2)-Cl(2) bond length is 3.17 Å. The K(2)-Cl(4) bond length is 3.19 Å. The K(2)-Cl(6) bond length is 3.21 Å. There is one shorter (3.14 Å) and one longer (3.17 Å) K(2)-Cl(3) bond length. There is one shorter (3.28 Å) and one longer (3.44 Å) K(2)-Cl(5) bond length. In the third K site, K(3) is bonded in a 9-coordinate geometry to one Cl(2), one Cl(5), two equivalent Cl(1), two equivalent Cl(4), and three equivalent Cl(6) atoms. The K(3)-Cl(2) bond length is 3.76 Å. The K(3)-Cl(5) bond length is 3.37 Å. There is one shorter (3.26 Å) and one longer (3.37 Å) K(3)-Cl(1) bond length. There is one shorter (3.21 Å) and one longer (3.50 Å) K(3)-Cl(4) bond length. There are a spread of K(3)-Cl(6) bond distances ranging from 3.24-3.49 Å. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in an octahedral geometry to two equivalent Cl(1), two equivalent Cl(4), and two equivalent Cl(6) atoms. Both Mo(1)-Cl(1) bond lengths are 2.44 Å. Both Mo(1)-Cl(4) bond lengths are 2.45 Å. Both Mo(1)-Cl(6) bond lengths are 2.48 Å. In the second Mo site, Mo(2) is bonded in an octahedral geometry to two equivalent Cl(2), two equivalent Cl(3), and two equivalent Cl(5) atoms. Both Mo(2)-Cl(2) bond lengths are 2.46 Å. Both Mo(2)-Cl(3) bond lengths are 2.47 Å. Both Mo(2)-Cl(5) bond lengths are 2.47 Å. There are six inequivalent Cl sites. In the first Cl site, Cl(5) is bonded to one K(1), one K(3), two equivalent K(2), and one Mo(2) atom to form a mixture of distorted corner, edge, and face-sharing ClK4Mo trigonal bipyramids. In the second Cl site, Cl(6) is bonded in a 6-coordinate geometry to one K(1), one K(2), three equivalent K(3), and one Mo(1) atom. In the third Cl site, Cl(1) is bonded to one K(1), one K(2), two equivalent K(3), and one Mo(1) atom to form a mixture of distorted corner, edge, and face-sharing ClK4Mo square pyramids. In the fourth Cl site, Cl(2) is bonded in a 5-coordinate geometry to one K(2), one K(3), two equivalent K(1), and one Mo(2) atom. In the fifth Cl site, Cl(3) is bonded to two equivalent K(1), two equivalent K(2), and one Mo(2) atom to form a mixture of distorted corner and edge-sharing ClK4Mo trigonal bipyramids. In the sixth Cl site, Cl(4) is bonded to one K(1), one K(2), two equivalent K(3), and one Mo(1) atom to form a mixture of distorted corner, edge, and face-sharing ClK4Mo square pyramids.