CaMn8(OF)8 crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 7-coordinate geometry to one O(1), one O(2), two equivalent O(7), one F(3), one F(6), and one F(7) atom. There are eight inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), one O(6), one O(8), one F(1), one F(2), and one F(8) atom to form a mixture of corner and edge-sharing MnO3F3 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. In the second Mn site, Mn(2) is bonded to one O(1), one O(4), one O(8), one F(1), one F(4), and one F(6) atom to form MnO3F3 octahedra that share corners with four equivalent Mn(6)O3F3 octahedra,  a cornercorner with one Mn(3)O3F tetrahedra, corners with four equivalent Mn(7)O3F2 trigonal bipyramids, and  an edgeedge with one Mn(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 42-51°. In the third Mn site, Mn(3) is bonded to one O(1), one O(2), one O(7), and one F(3) atom to form distorted MnO3F tetrahedra that share  a cornercorner with one Mn(2)O3F3 octahedra,  a cornercorner with one Mn(4)O3F3 octahedra, and corners with two equivalent Mn(7)O3F2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 49-52°. In the fourth Mn site, Mn(4) is bonded to one O(2), one O(3), one O(5), one F(5), one F(7), and one F(8) atom to form MnO3F3 octahedra that share corners with four equivalent Mn(8)O3F3 octahedra,  a cornercorner with one Mn(3)O3F tetrahedra, and  an edgeedge with one Mn(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 42-54°. In the fifth Mn site, Mn(5) is bonded in a 6-coordinate geometry to one O(2), one O(5), one O(7), one F(3), one F(5), and one F(7) atom. In the sixth Mn site, Mn(6) is bonded to one O(4), one O(6), one O(8), one F(1), one F(2), and one F(4) atom to form MnO3F3 octahedra that share corners with four equivalent Mn(1)O3F3 octahedra, corners with four equivalent Mn(2)O3F3 octahedra,  an edgeedge with one Mn(8)O3F3 octahedra, and  an edgeedge with one Mn(7)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 42-53°. In the seventh Mn site, Mn(7) is bonded to one O(1), one O(4), one O(7), one F(4), and one F(6) atom to form MnO3F2 trigonal bipyramids that share corners with four equivalent Mn(2)O3F3 octahedra, corners with two equivalent Mn(3)O3F tetrahedra, and  an edgeedge with one Mn(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 41-59°. In the eighth Mn site, Mn(8) is bonded to one O(3), one O(5), one O(6), one F(2), one F(5), and one F(8) atom to form a mixture of corner and edge-sharing MnO3F3 octahedra. The corner-sharing octahedral tilt angles range from 42-54°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Ca(1), one Mn(2), one Mn(3), and one Mn(7) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Ca(1), one Mn(3), one Mn(4), and one Mn(5) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Mn(1), one Mn(4), and one Mn(8) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Mn(2), one Mn(6), and one Mn(7) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Mn(4), one Mn(5), and one Mn(8) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Mn(1), one Mn(6), and one Mn(8) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to two equivalent Ca(1), one Mn(3), one Mn(5), and one Mn(7) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(6) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Mn(1), one Mn(2), and one Mn(6) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Mn(1), one Mn(6), and one Mn(8) atom. In the third F site, F(3) is bonded in a 2-coordinate geometry to one Ca(1), one Mn(3), and one Mn(5) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Mn(2), one Mn(6), and one Mn(7) atom. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one Mn(4), one Mn(5), and one Mn(8) atom. In the sixth F site, F(6) is bonded in a distorted T-shaped geometry to one Ca(1), one Mn(2), and one Mn(7) atom. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one Ca(1), one Mn(4), and one Mn(5) atom. In the eighth F site, F(8) is bonded in a distorted T-shaped geometry to one Mn(1), one Mn(4), and one Mn(8) atom.
CaMn8(OF)8 crystallizes in the triclinic P1 space group. Ca(1) is bonded in a 7-coordinate geometry to one O(1), one O(2), two equivalent O(7), one F(3), one F(6), and one F(7) atom. The Ca(1)-O(1) bond length is 2.57 Å. The Ca(1)-O(2) bond length is 2.54 Å. There is one shorter (2.27 Å) and one longer (2.63 Å) Ca(1)-O(7) bond length. The Ca(1)-F(3) bond length is 2.16 Å. The Ca(1)-F(6) bond length is 2.28 Å. The Ca(1)-F(7) bond length is 2.24 Å. There are eight inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), one O(6), one O(8), one F(1), one F(2), and one F(8) atom to form a mixture of corner and edge-sharing MnO3F3 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. The Mn(1)-O(3) bond length is 1.94 Å. The Mn(1)-O(6) bond length is 1.99 Å. The Mn(1)-O(8) bond length is 2.00 Å. The Mn(1)-F(1) bond length is 2.21 Å. The Mn(1)-F(2) bond length is 2.05 Å. The Mn(1)-F(8) bond length is 2.26 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(4), one O(8), one F(1), one F(4), and one F(6) atom to form MnO3F3 octahedra that share corners with four equivalent Mn(6)O3F3 octahedra,  a cornercorner with one Mn(3)O3F tetrahedra, corners with four equivalent Mn(7)O3F2 trigonal bipyramids, and  an edgeedge with one Mn(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 42-51°. The Mn(2)-O(1) bond length is 2.08 Å. The Mn(2)-O(4) bond length is 1.96 Å. The Mn(2)-O(8) bond length is 1.98 Å. The Mn(2)-F(1) bond length is 2.20 Å. The Mn(2)-F(4) bond length is 2.04 Å. The Mn(2)-F(6) bond length is 2.29 Å. In the third Mn site, Mn(3) is bonded to one O(1), one O(2), one O(7), and one F(3) atom to form distorted MnO3F tetrahedra that share  a cornercorner with one Mn(2)O3F3 octahedra,  a cornercorner with one Mn(4)O3F3 octahedra, and corners with two equivalent Mn(7)O3F2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 49-52°. The Mn(3)-O(1) bond length is 2.07 Å. The Mn(3)-O(2) bond length is 2.04 Å. The Mn(3)-O(7) bond length is 2.02 Å. The Mn(3)-F(3) bond length is 2.02 Å. In the fourth Mn site, Mn(4) is bonded to one O(2), one O(3), one O(5), one F(5), one F(7), and one F(8) atom to form MnO3F3 octahedra that share corners with four equivalent Mn(8)O3F3 octahedra,  a cornercorner with one Mn(3)O3F tetrahedra, and  an edgeedge with one Mn(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 42-54°. The Mn(4)-O(2) bond length is 2.15 Å. The Mn(4)-O(3) bond length is 2.06 Å. The Mn(4)-O(5) bond length is 1.99 Å. The Mn(4)-F(5) bond length is 2.07 Å. The Mn(4)-F(7) bond length is 2.30 Å. The Mn(4)-F(8) bond length is 2.20 Å. In the fifth Mn site, Mn(5) is bonded in a 6-coordinate geometry to one O(2), one O(5), one O(7), one F(3), one F(5), and one F(7) atom. The Mn(5)-O(2) bond length is 1.91 Å. The Mn(5)-O(5) bond length is 1.91 Å. The Mn(5)-O(7) bond length is 2.15 Å. The Mn(5)-F(3) bond length is 2.66 Å. The Mn(5)-F(5) bond length is 2.08 Å. The Mn(5)-F(7) bond length is 2.00 Å. In the sixth Mn site, Mn(6) is bonded to one O(4), one O(6), one O(8), one F(1), one F(2), and one F(4) atom to form MnO3F3 octahedra that share corners with four equivalent Mn(1)O3F3 octahedra, corners with four equivalent Mn(2)O3F3 octahedra,  an edgeedge with one Mn(8)O3F3 octahedra, and  an edgeedge with one Mn(7)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 42-53°. The Mn(6)-O(4) bond length is 1.99 Å. The Mn(6)-O(6) bond length is 1.93 Å. The Mn(6)-O(8) bond length is 1.99 Å. The Mn(6)-F(1) bond length is 2.11 Å. The Mn(6)-F(2) bond length is 2.14 Å. The Mn(6)-F(4) bond length is 2.28 Å. In the seventh Mn site, Mn(7) is bonded to one O(1), one O(4), one O(7), one F(4), and one F(6) atom to form MnO3F2 trigonal bipyramids that share corners with four equivalent Mn(2)O3F3 octahedra, corners with two equivalent Mn(3)O3F tetrahedra, and  an edgeedge with one Mn(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 41-59°. The Mn(7)-O(1) bond length is 1.93 Å. The Mn(7)-O(4) bond length is 1.91 Å. The Mn(7)-O(7) bond length is 2.07 Å. The Mn(7)-F(4) bond length is 2.07 Å. The Mn(7)-F(6) bond length is 2.03 Å. In the eighth Mn site, Mn(8) is bonded to one O(3), one O(5), one O(6), one F(2), one F(5), and one F(8) atom to form a mixture of corner and edge-sharing MnO3F3 octahedra. The corner-sharing octahedral tilt angles range from 42-54°. The Mn(8)-O(3) bond length is 1.97 Å. The Mn(8)-O(5) bond length is 1.98 Å. The Mn(8)-O(6) bond length is 1.97 Å. The Mn(8)-F(2) bond length is 2.17 Å. The Mn(8)-F(5) bond length is 2.25 Å. The Mn(8)-F(8) bond length is 2.11 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Ca(1), one Mn(2), one Mn(3), and one Mn(7) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Ca(1), one Mn(3), one Mn(4), and one Mn(5) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Mn(1), one Mn(4), and one Mn(8) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Mn(2), one Mn(6), and one Mn(7) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Mn(4), one Mn(5), and one Mn(8) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Mn(1), one Mn(6), and one Mn(8) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to two equivalent Ca(1), one Mn(3), one Mn(5), and one Mn(7) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(6) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Mn(1), one Mn(2), and one Mn(6) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Mn(1), one Mn(6), and one Mn(8) atom. In the third F site, F(3) is bonded in a 2-coordinate geometry to one Ca(1), one Mn(3), and one Mn(5) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Mn(2), one Mn(6), and one Mn(7) atom. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one Mn(4), one Mn(5), and one Mn(8) atom. In the sixth F site, F(6) is bonded in a distorted T-shaped geometry to one Ca(1), one Mn(2), and one Mn(7) atom. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one Ca(1), one Mn(4), and one Mn(5) atom. In the eighth F site, F(8) is bonded in a distorted T-shaped geometry to one Mn(1), one Mn(4), and one Mn(8) atom.