CsCoF3 crystallizes in the monoclinic C2/m space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to one F(4), two equivalent F(2), three equivalent F(3), and six equivalent F(1) atoms to form distorted CsF12 cuboctahedra that share corners with nine equivalent Cs(1)F12 cuboctahedra, corners with three equivalent Co(1)F6 octahedra, faces with three equivalent Cs(1)F12 cuboctahedra, faces with four equivalent Cs(2)F12 cuboctahedra, faces with three equivalent Co(2)F6 octahedra, and faces with four equivalent Co(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. In the second Cs site, Cs(2) is bonded to two equivalent F(3), two equivalent F(4), four equivalent F(1), and four equivalent F(2) atoms to form CsF12 cuboctahedra that share corners with six equivalent Cs(2)F12 cuboctahedra, corners with six equivalent Co(2)F6 octahedra, faces with eight equivalent Cs(1)F12 cuboctahedra, and faces with six equivalent Co(1)F6 octahedra. The corner-sharing octahedral tilt angles are 9°. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form CoF6 octahedra that share corners with three equivalent Cs(1)F12 cuboctahedra, corners with three equivalent Co(1)F6 octahedra, faces with three equivalent Cs(2)F12 cuboctahedra, faces with four equivalent Cs(1)F12 cuboctahedra, and  a faceface with one Co(2)F6 octahedra. The corner-sharing octahedra are not tilted. In the second Co site, Co(2) is bonded to two equivalent F(3) and four equivalent F(1) atoms to form CoF6 octahedra that share corners with six equivalent Cs(2)F12 cuboctahedra, faces with six equivalent Cs(1)F12 cuboctahedra, and faces with two equivalent Co(1)F6 octahedra. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted L-shaped geometry to one Cs(2), three equivalent Cs(1), one Co(1), and one Co(2) atom. In the second F site, F(2) is bonded in a distorted linear geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Co(1) atoms. In the third F site, F(3) is bonded in a distorted L-shaped geometry to one Cs(2), three equivalent Cs(1), one Co(1), and one Co(2) atom. In the fourth F site, F(4) is bonded in a distorted linear geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Co(1) atoms.
CsCoF3 crystallizes in the monoclinic C2/m space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to one F(4), two equivalent F(2), three equivalent F(3), and six equivalent F(1) atoms to form distorted CsF12 cuboctahedra that share corners with nine equivalent Cs(1)F12 cuboctahedra, corners with three equivalent Co(1)F6 octahedra, faces with three equivalent Cs(1)F12 cuboctahedra, faces with four equivalent Cs(2)F12 cuboctahedra, faces with three equivalent Co(2)F6 octahedra, and faces with four equivalent Co(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. The Cs(1)-F(4) bond length is 3.22 Å. Both Cs(1)-F(2) bond lengths are 3.21 Å. There are two shorter (3.12 Å) and one longer (3.13 Å) Cs(1)-F(3) bond length. There are two shorter (3.10 Å) and four longer (3.13 Å) Cs(1)-F(1) bond lengths. In the second Cs site, Cs(2) is bonded to two equivalent F(3), two equivalent F(4), four equivalent F(1), and four equivalent F(2) atoms to form CsF12 cuboctahedra that share corners with six equivalent Cs(2)F12 cuboctahedra, corners with six equivalent Co(2)F6 octahedra, faces with eight equivalent Cs(1)F12 cuboctahedra, and faces with six equivalent Co(1)F6 octahedra. The corner-sharing octahedral tilt angles are 9°. Both Cs(2)-F(3) bond lengths are 3.14 Å. Both Cs(2)-F(4) bond lengths are 3.09 Å. All Cs(2)-F(1) bond lengths are 3.15 Å. All Cs(2)-F(2) bond lengths are 3.09 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form CoF6 octahedra that share corners with three equivalent Cs(1)F12 cuboctahedra, corners with three equivalent Co(1)F6 octahedra, faces with three equivalent Cs(2)F12 cuboctahedra, faces with four equivalent Cs(1)F12 cuboctahedra, and  a faceface with one Co(2)F6 octahedra. The corner-sharing octahedra are not tilted. The Co(1)-F(3) bond length is 2.07 Å. The Co(1)-F(4) bond length is 2.05 Å. Both Co(1)-F(1) bond lengths are 2.09 Å. Both Co(1)-F(2) bond lengths are 2.05 Å. In the second Co site, Co(2) is bonded to two equivalent F(3) and four equivalent F(1) atoms to form CoF6 octahedra that share corners with six equivalent Cs(2)F12 cuboctahedra, faces with six equivalent Cs(1)F12 cuboctahedra, and faces with two equivalent Co(1)F6 octahedra. Both Co(2)-F(3) bond lengths are 2.05 Å. All Co(2)-F(1) bond lengths are 2.03 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted L-shaped geometry to one Cs(2), three equivalent Cs(1), one Co(1), and one Co(2) atom. In the second F site, F(2) is bonded in a distorted linear geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Co(1) atoms. In the third F site, F(3) is bonded in a distorted L-shaped geometry to one Cs(2), three equivalent Cs(1), one Co(1), and one Co(2) atom. In the fourth F site, F(4) is bonded in a distorted linear geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Co(1) atoms.