Na2CoCl4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form NaCl6 octahedra that share corners with four equivalent Na(2)Cl6 octahedra, corners with two equivalent Co(1)Cl4 tetrahedra, edges with two equivalent Na(1)Cl6 octahedra, edges with two equivalent Na(2)Cl6 octahedra, and edges with two equivalent Co(1)Cl4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-61°. In the second Na site, Na(2) is bonded to one Cl(2), one Cl(3), and four equivalent Cl(1) atoms to form NaCl6 octahedra that share corners with four equivalent Na(1)Cl6 octahedra, corners with four equivalent Na(2)Cl6 octahedra, corners with four equivalent Co(1)Cl4 tetrahedra, edges with two equivalent Na(1)Cl6 octahedra, and  an edgeedge with one Co(1)Cl4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-61°. Co(1) is bonded to one Cl(2), one Cl(3), and two equivalent Cl(1) atoms to form CoCl4 tetrahedra that share corners with two equivalent Na(1)Cl6 octahedra, corners with four equivalent Na(2)Cl6 octahedra,  an edgeedge with one Na(2)Cl6 octahedra, and edges with two equivalent Na(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 56-60°. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a rectangular see-saw-like geometry to one Na(1), two equivalent Na(2), and one Co(1) atom. In the second Cl site, Cl(2) is bonded to one Na(2), two equivalent Na(1), and one Co(1) atom to form distorted corner-sharing ClNa3Co trigonal pyramids. In the third Cl site, Cl(3) is bonded in a rectangular see-saw-like geometry to one Na(2), two equivalent Na(1), and one Co(1) atom.
Na2CoCl4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form NaCl6 octahedra that share corners with four equivalent Na(2)Cl6 octahedra, corners with two equivalent Co(1)Cl4 tetrahedra, edges with two equivalent Na(1)Cl6 octahedra, edges with two equivalent Na(2)Cl6 octahedra, and edges with two equivalent Co(1)Cl4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-61°. Both Na(1)-Cl(1) bond lengths are 2.80 Å. Both Na(1)-Cl(2) bond lengths are 2.81 Å. Both Na(1)-Cl(3) bond lengths are 2.76 Å. In the second Na site, Na(2) is bonded to one Cl(2), one Cl(3), and four equivalent Cl(1) atoms to form NaCl6 octahedra that share corners with four equivalent Na(1)Cl6 octahedra, corners with four equivalent Na(2)Cl6 octahedra, corners with four equivalent Co(1)Cl4 tetrahedra, edges with two equivalent Na(1)Cl6 octahedra, and  an edgeedge with one Co(1)Cl4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-61°. The Na(2)-Cl(2) bond length is 2.82 Å. The Na(2)-Cl(3) bond length is 2.76 Å. There are two shorter (2.78 Å) and two longer (2.87 Å) Na(2)-Cl(1) bond lengths. Co(1) is bonded to one Cl(2), one Cl(3), and two equivalent Cl(1) atoms to form CoCl4 tetrahedra that share corners with two equivalent Na(1)Cl6 octahedra, corners with four equivalent Na(2)Cl6 octahedra,  an edgeedge with one Na(2)Cl6 octahedra, and edges with two equivalent Na(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 56-60°. The Co(1)-Cl(2) bond length is 2.25 Å. The Co(1)-Cl(3) bond length is 2.28 Å. Both Co(1)-Cl(1) bond lengths are 2.27 Å. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a rectangular see-saw-like geometry to one Na(1), two equivalent Na(2), and one Co(1) atom. In the second Cl site, Cl(2) is bonded to one Na(2), two equivalent Na(1), and one Co(1) atom to form distorted corner-sharing ClNa3Co trigonal pyramids. In the third Cl site, Cl(3) is bonded in a rectangular see-saw-like geometry to one Na(2), two equivalent Na(1), and one Co(1) atom.