KWCl6 crystallizes in the monoclinic C2/c space group. K(1) is bonded to four equivalent Cl(1), four equivalent Cl(2), and four equivalent Cl(3) atoms to form distorted KCl12 cuboctahedra that share corners with four equivalent K(1)Cl12 cuboctahedra, corners with two equivalent W(1)Cl6 octahedra, edges with four equivalent K(1)Cl12 cuboctahedra, edges with two equivalent W(1)Cl6 octahedra, and faces with two equivalent W(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 45°. W(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form WCl6 octahedra that share corners with two equivalent K(1)Cl12 cuboctahedra, edges with two equivalent K(1)Cl12 cuboctahedra, and faces with two equivalent K(1)Cl12 cuboctahedra. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to two equivalent K(1) and one W(1) atom. In the second Cl site, Cl(2) is bonded in a 3-coordinate geometry to two equivalent K(1) and one W(1) atom. In the third Cl site, Cl(3) is bonded in a 3-coordinate geometry to two equivalent K(1) and one W(1) atom.
KWCl6 crystallizes in the monoclinic C2/c space group. K(1) is bonded to four equivalent Cl(1), four equivalent Cl(2), and four equivalent Cl(3) atoms to form distorted KCl12 cuboctahedra that share corners with four equivalent K(1)Cl12 cuboctahedra, corners with two equivalent W(1)Cl6 octahedra, edges with four equivalent K(1)Cl12 cuboctahedra, edges with two equivalent W(1)Cl6 octahedra, and faces with two equivalent W(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 45°. There are two shorter (3.54 Å) and two longer (3.74 Å) K(1)-Cl(1) bond lengths. There are two shorter (3.42 Å) and two longer (3.53 Å) K(1)-Cl(2) bond lengths. There are two shorter (3.42 Å) and two longer (3.52 Å) K(1)-Cl(3) bond lengths. W(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form WCl6 octahedra that share corners with two equivalent K(1)Cl12 cuboctahedra, edges with two equivalent K(1)Cl12 cuboctahedra, and faces with two equivalent K(1)Cl12 cuboctahedra. Both W(1)-Cl(1) bond lengths are 2.32 Å. Both W(1)-Cl(2) bond lengths are 2.35 Å. Both W(1)-Cl(3) bond lengths are 2.34 Å. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to two equivalent K(1) and one W(1) atom. In the second Cl site, Cl(2) is bonded in a 3-coordinate geometry to two equivalent K(1) and one W(1) atom. In the third Cl site, Cl(3) is bonded in a 3-coordinate geometry to two equivalent K(1) and one W(1) atom.