K4Mn3F12 crystallizes in the tetragonal I4_1/amd space group. K(1) is bonded to two equivalent F(1), two equivalent F(2), four equivalent F(3), and four equivalent F(4) atoms to form distorted KF12 cuboctahedra that share corners with twelve equivalent K(1)F12 cuboctahedra, faces with six equivalent K(1)F12 cuboctahedra, faces with two equivalent Mn(1)F6 octahedra, and faces with four equivalent Mn(2)F6 octahedra. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent F(2) and four equivalent F(4) atoms to form MnF6 octahedra that share corners with six equivalent Mn(2)F6 octahedra and faces with eight equivalent K(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second Mn site, Mn(2) is bonded to one F(1), one F(2), two equivalent F(3), and two equivalent F(4) atoms to form MnF6 octahedra that share corners with three equivalent Mn(1)F6 octahedra and faces with eight equivalent K(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-2°. There are four inequivalent F sites. In the first F site, F(2) is bonded in a linear geometry to four equivalent K(1), one Mn(1), and one Mn(2) atom. In the second F site, F(3) is bonded in a distorted single-bond geometry to four equivalent K(1) and one Mn(2) atom. In the third F site, F(4) is bonded in a distorted linear geometry to four equivalent K(1), one Mn(1), and one Mn(2) atom. In the fourth F site, F(1) is bonded in a distorted single-bond geometry to four equivalent K(1) and one Mn(2) atom.
K4Mn3F12 crystallizes in the tetragonal I4_1/amd space group. K(1) is bonded to two equivalent F(1), two equivalent F(2), four equivalent F(3), and four equivalent F(4) atoms to form distorted KF12 cuboctahedra that share corners with twelve equivalent K(1)F12 cuboctahedra, faces with six equivalent K(1)F12 cuboctahedra, faces with two equivalent Mn(1)F6 octahedra, and faces with four equivalent Mn(2)F6 octahedra. Both K(1)-F(1) bond lengths are 2.79 Å. Both K(1)-F(2) bond lengths are 3.10 Å. There are two shorter (2.84 Å) and two longer (2.86 Å) K(1)-F(3) bond lengths. There are two shorter (2.97 Å) and two longer (3.02 Å) K(1)-F(4) bond lengths. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent F(2) and four equivalent F(4) atoms to form MnF6 octahedra that share corners with six equivalent Mn(2)F6 octahedra and faces with eight equivalent K(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-2°. Both Mn(1)-F(2) bond lengths are 2.05 Å. All Mn(1)-F(4) bond lengths are 2.05 Å. In the second Mn site, Mn(2) is bonded to one F(1), one F(2), two equivalent F(3), and two equivalent F(4) atoms to form MnF6 octahedra that share corners with three equivalent Mn(1)F6 octahedra and faces with eight equivalent K(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-2°. The Mn(2)-F(1) bond length is 1.87 Å. The Mn(2)-F(2) bond length is 1.92 Å. Both Mn(2)-F(3) bond lengths are 1.84 Å. Both Mn(2)-F(4) bond lengths are 2.10 Å. There are four inequivalent F sites. In the first F site, F(2) is bonded in a linear geometry to four equivalent K(1), one Mn(1), and one Mn(2) atom. In the second F site, F(3) is bonded in a distorted single-bond geometry to four equivalent K(1) and one Mn(2) atom. In the third F site, F(4) is bonded in a distorted linear geometry to four equivalent K(1), one Mn(1), and one Mn(2) atom. In the fourth F site, F(1) is bonded in a distorted single-bond geometry to four equivalent K(1) and one Mn(2) atom.