MnFeF5(H2O)2 crystallizes in the monoclinic Cm space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(3), two equivalent F(4), and two equivalent F(6) atoms to form MnO2F4 octahedra that share corners with four equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles are 47°. In the second Mn site, Mn(2) is bonded to one O(2), one O(4), two equivalent F(3), and two equivalent F(5) atoms to form MnO2F4 octahedra that share corners with four equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles are 47°. Fe(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form FeF6 octahedra that share corners with two equivalent Mn(1)O2F4 octahedra, corners with two equivalent Mn(2)O2F4 octahedra, and corners with two equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 28-47°. There are three inequivalent H sites. In the first H site, H(1,3) is bonded in a single-bond geometry to one O(1) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(2) atom. In the third H site, H(4) is bonded in a single-bond geometry to one O(4) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted water-like geometry to one Mn(1) and two equivalent H(1,3) atoms. In the second O site, O(2) is bonded in a distorted water-like geometry to one Mn(2) and two equivalent H(2) atoms. In the third O site, O(3) is bonded in a distorted water-like geometry to one Mn(1) and two equivalent H(1,3) atoms. In the fourth O site, O(4) is bonded in a distorted water-like geometry to one Mn(2) and two equivalent H(4) atoms. There are six inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to two equivalent Fe(1) atoms. In the second F site, F(2) is bonded in a bent 150 degrees geometry to two equivalent Fe(1) atoms. In the third F site, F(3) is bonded in a distorted bent 120 degrees geometry to one Mn(2) and one Fe(1) atom. In the fourth F site, F(4) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one Fe(1) atom. In the fifth F site, F(5) is bonded in a distorted bent 120 degrees geometry to one Mn(2) and one Fe(1) atom. In the sixth F site, F(6) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one Fe(1) atom.
MnFeF5(H2O)2 crystallizes in the monoclinic Cm space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(3), two equivalent F(4), and two equivalent F(6) atoms to form MnO2F4 octahedra that share corners with four equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles are 47°. The Mn(1)-O(1) bond length is 2.17 Å. The Mn(1)-O(3) bond length is 2.16 Å. Both Mn(1)-F(4) bond lengths are 2.16 Å. Both Mn(1)-F(6) bond lengths are 2.16 Å. In the second Mn site, Mn(2) is bonded to one O(2), one O(4), two equivalent F(3), and two equivalent F(5) atoms to form MnO2F4 octahedra that share corners with four equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles are 47°. The Mn(2)-O(2) bond length is 2.17 Å. The Mn(2)-O(4) bond length is 2.18 Å. Both Mn(2)-F(3) bond lengths are 2.15 Å. Both Mn(2)-F(5) bond lengths are 2.16 Å. Fe(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form FeF6 octahedra that share corners with two equivalent Mn(1)O2F4 octahedra, corners with two equivalent Mn(2)O2F4 octahedra, and corners with two equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 28-47°. The Fe(1)-F(1) bond length is 1.98 Å. The Fe(1)-F(2) bond length is 1.98 Å. The Fe(1)-F(3) bond length is 1.96 Å. The Fe(1)-F(4) bond length is 1.95 Å. The Fe(1)-F(5) bond length is 1.96 Å. The Fe(1)-F(6) bond length is 1.95 Å. There are three inequivalent H sites. In the first H site, H(1,3) is bonded in a single-bond geometry to one O(1) atom. The H(1,3)-O(1) bond length is 0.98 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(2) atom. The H(2)-O(2) bond length is 0.98 Å. In the third H site, H(4) is bonded in a single-bond geometry to one O(4) atom. The H(4)-O(4) bond length is 0.98 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted water-like geometry to one Mn(1) and two equivalent H(1,3) atoms. In the second O site, O(2) is bonded in a distorted water-like geometry to one Mn(2) and two equivalent H(2) atoms. In the third O site, O(3) is bonded in a distorted water-like geometry to one Mn(1) and two equivalent H(1,3) atoms. Both O(3)-H(1,3) bond lengths are 0.98 Å. In the fourth O site, O(4) is bonded in a distorted water-like geometry to one Mn(2) and two equivalent H(4) atoms. There are six inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to two equivalent Fe(1) atoms. In the second F site, F(2) is bonded in a bent 150 degrees geometry to two equivalent Fe(1) atoms. In the third F site, F(3) is bonded in a distorted bent 120 degrees geometry to one Mn(2) and one Fe(1) atom. In the fourth F site, F(4) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one Fe(1) atom. In the fifth F site, F(5) is bonded in a distorted bent 120 degrees geometry to one Mn(2) and one Fe(1) atom. In the sixth F site, F(6) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one Fe(1) atom.