K2CoCl4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent K sites. In the first K site, K(1) is bonded to one Cl(1), two equivalent Cl(2), two equivalent Cl(3), and two equivalent Cl(4) atoms to form KCl7 pentagonal bipyramids that share corners with two equivalent K(1)Cl7 pentagonal bipyramids, corners with five equivalent Co(1)Cl4 tetrahedra, edges with two equivalent K(1)Cl7 pentagonal bipyramids, and  an edgeedge with one Co(1)Cl4 tetrahedra. In the second K site, K(2) is bonded in a 7-coordinate geometry to one Cl(4), two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms. Co(1) is bonded to one Cl(1), one Cl(2), one Cl(3), and one Cl(4) atom to form CoCl4 tetrahedra that share corners with five equivalent K(1)Cl7 pentagonal bipyramids and  an edgeedge with one K(1)Cl7 pentagonal bipyramid. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to one K(1), two equivalent K(2), and one Co(1) atom to form distorted edge-sharing ClK3Co trigonal pyramids. In the second Cl site, Cl(2) is bonded in a 5-coordinate geometry to two equivalent K(1), two equivalent K(2), and one Co(1) atom. In the third Cl site, Cl(3) is bonded in a 5-coordinate geometry to two equivalent K(1), two equivalent K(2), and one Co(1) atom. In the fourth Cl site, Cl(4) is bonded in a distorted rectangular see-saw-like geometry to one K(2), two equivalent K(1), and one Co(1) atom.
K2CoCl4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent K sites. In the first K site, K(1) is bonded to one Cl(1), two equivalent Cl(2), two equivalent Cl(3), and two equivalent Cl(4) atoms to form KCl7 pentagonal bipyramids that share corners with two equivalent K(1)Cl7 pentagonal bipyramids, corners with five equivalent Co(1)Cl4 tetrahedra, edges with two equivalent K(1)Cl7 pentagonal bipyramids, and  an edgeedge with one Co(1)Cl4 tetrahedra. The K(1)-Cl(1) bond length is 3.11 Å. There is one shorter (3.11 Å) and one longer (3.23 Å) K(1)-Cl(2) bond length. There is one shorter (3.31 Å) and one longer (3.46 Å) K(1)-Cl(3) bond length. There is one shorter (3.13 Å) and one longer (3.26 Å) K(1)-Cl(4) bond length. In the second K site, K(2) is bonded in a 7-coordinate geometry to one Cl(4), two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms. The K(2)-Cl(4) bond length is 3.28 Å. There is one shorter (3.16 Å) and one longer (3.25 Å) K(2)-Cl(1) bond length. There is one shorter (3.19 Å) and one longer (3.37 Å) K(2)-Cl(2) bond length. There is one shorter (3.15 Å) and one longer (3.25 Å) K(2)-Cl(3) bond length. Co(1) is bonded to one Cl(1), one Cl(2), one Cl(3), and one Cl(4) atom to form CoCl4 tetrahedra that share corners with five equivalent K(1)Cl7 pentagonal bipyramids and  an edgeedge with one K(1)Cl7 pentagonal bipyramid. The Co(1)-Cl(1) bond length is 2.25 Å. The Co(1)-Cl(2) bond length is 2.27 Å. The Co(1)-Cl(3) bond length is 2.25 Å. The Co(1)-Cl(4) bond length is 2.27 Å. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to one K(1), two equivalent K(2), and one Co(1) atom to form distorted edge-sharing ClK3Co trigonal pyramids. In the second Cl site, Cl(2) is bonded in a 5-coordinate geometry to two equivalent K(1), two equivalent K(2), and one Co(1) atom. In the third Cl site, Cl(3) is bonded in a 5-coordinate geometry to two equivalent K(1), two equivalent K(2), and one Co(1) atom. In the fourth Cl site, Cl(4) is bonded in a distorted rectangular see-saw-like geometry to one K(2), two equivalent K(1), and one Co(1) atom.