CsMnF3 is (Cubic) Perovskite-like structured and crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to six equivalent F(1) and six equivalent F(2) atoms to form CsF12 cuboctahedra that share corners with six equivalent Cs(1)F12 cuboctahedra, corners with six equivalent Cs(2)F12 cuboctahedra, faces with six equivalent Cs(2)F12 cuboctahedra, faces with two equivalent Mn(1)F6 octahedra, and faces with six equivalent Mn(2)F6 octahedra. In the second Cs site, Cs(2) is bonded to three equivalent F(2) and nine equivalent F(1) atoms to form CsF12 cuboctahedra that share corners with three equivalent Cs(1)F12 cuboctahedra, corners with six equivalent Cs(2)F12 cuboctahedra, corners with three equivalent Mn(2)F6 octahedra, faces with three equivalent Cs(1)F12 cuboctahedra, faces with four equivalent Cs(2)F12 cuboctahedra, faces with three equivalent Mn(1)F6 octahedra, and faces with four equivalent Mn(2)F6 octahedra. The corner-sharing octahedral tilt angles are 5°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to six equivalent F(1) atoms to form MnF6 octahedra that share corners with six equivalent Mn(2)F6 octahedra, faces with two equivalent Cs(1)F12 cuboctahedra, and faces with six equivalent Cs(2)F12 cuboctahedra. The corner-sharing octahedral tilt angles are 3°. In the second Mn site, Mn(2) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form MnF6 octahedra that share corners with three equivalent Cs(2)F12 cuboctahedra, corners with three equivalent Mn(1)F6 octahedra, faces with three equivalent Cs(1)F12 cuboctahedra, faces with four equivalent Cs(2)F12 cuboctahedra, and  a faceface with one Mn(2)F6 octahedra. The corner-sharing octahedral tilt angles are 3°. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted linear geometry to one Cs(1), three equivalent Cs(2), one Mn(1), and one Mn(2) atom. In the second F site, F(2) is bonded to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Mn(2) atoms to form a mixture of distorted face and corner-sharing FCs4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 9-60°.
CsMnF3 is (Cubic) Perovskite-like structured and crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to six equivalent F(1) and six equivalent F(2) atoms to form CsF12 cuboctahedra that share corners with six equivalent Cs(1)F12 cuboctahedra, corners with six equivalent Cs(2)F12 cuboctahedra, faces with six equivalent Cs(2)F12 cuboctahedra, faces with two equivalent Mn(1)F6 octahedra, and faces with six equivalent Mn(2)F6 octahedra. All Cs(1)-F(1) bond lengths are 3.13 Å. All Cs(1)-F(2) bond lengths are 3.12 Å. In the second Cs site, Cs(2) is bonded to three equivalent F(2) and nine equivalent F(1) atoms to form CsF12 cuboctahedra that share corners with three equivalent Cs(1)F12 cuboctahedra, corners with six equivalent Cs(2)F12 cuboctahedra, corners with three equivalent Mn(2)F6 octahedra, faces with three equivalent Cs(1)F12 cuboctahedra, faces with four equivalent Cs(2)F12 cuboctahedra, faces with three equivalent Mn(1)F6 octahedra, and faces with four equivalent Mn(2)F6 octahedra. The corner-sharing octahedral tilt angles are 5°. All Cs(2)-F(2) bond lengths are 3.07 Å. There are six shorter (3.12 Å) and three longer (3.22 Å) Cs(2)-F(1) bond lengths. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to six equivalent F(1) atoms to form MnF6 octahedra that share corners with six equivalent Mn(2)F6 octahedra, faces with two equivalent Cs(1)F12 cuboctahedra, and faces with six equivalent Cs(2)F12 cuboctahedra. The corner-sharing octahedral tilt angles are 3°. All Mn(1)-F(1) bond lengths are 2.14 Å. In the second Mn site, Mn(2) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form MnF6 octahedra that share corners with three equivalent Cs(2)F12 cuboctahedra, corners with three equivalent Mn(1)F6 octahedra, faces with three equivalent Cs(1)F12 cuboctahedra, faces with four equivalent Cs(2)F12 cuboctahedra, and  a faceface with one Mn(2)F6 octahedra. The corner-sharing octahedral tilt angles are 3°. All Mn(2)-F(1) bond lengths are 2.11 Å. All Mn(2)-F(2) bond lengths are 2.15 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted linear geometry to one Cs(1), three equivalent Cs(2), one Mn(1), and one Mn(2) atom. In the second F site, F(2) is bonded to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Mn(2) atoms to form a mixture of distorted face and corner-sharing FCs4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 9-60°.