BaCaMnF7 crystallizes in the monoclinic P2_1/c space group. Ba(1) is bonded in a 10-coordinate geometry to one F(1), one F(5), two equivalent F(3), two equivalent F(4), two equivalent F(6), and two equivalent F(7) atoms. Ca(1) is bonded to one F(1), one F(2), one F(3), one F(5), one F(6), and one F(7) atom to form distorted CaF6 octahedra that share corners with three equivalent Mn(1)F6 octahedra and  an edgeedge with one Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 54-67°. Mn(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 MnF6 octahedra that share corners with three equivalent Ca(1)F6 octahedra and  an edgeedge with one Ca(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 54-67°. There are seven inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Ba(1), one Ca(1), and one Mn(1) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one Ca(1) and one Mn(1) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to two equivalent Ba(1), one Ca(1), and one Mn(1) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to two equivalent Ba(1) and one Mn(1) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Ba(1), one Ca(1), and one Mn(1) atom. In the sixth F site, F(6) is bonded in a distorted water-like geometry to two equivalent Ba(1), one Ca(1), and one Mn(1) atom. In the seventh F site, F(7) is bonded in a trigonal planar geometry to two equivalent Ba(1) and one Ca(1) atom.
BaCaMnF7 crystallizes in the monoclinic P2_1/c space group. Ba(1) is bonded in a 10-coordinate geometry to one F(1), one F(5), two equivalent F(3), two equivalent F(4), two equivalent F(6), and two equivalent F(7) atoms. The Ba(1)-F(1) bond length is 2.86 Å. The Ba(1)-F(5) bond length is 2.89 Å. There is one shorter (2.83 Å) and one longer (3.13 Å) Ba(1)-F(3) bond length. There is one shorter (2.87 Å) and one longer (2.94 Å) Ba(1)-F(4) bond length. There is one shorter (3.13 Å) and one longer (3.20 Å) Ba(1)-F(6) bond length. There is one shorter (2.61 Å) and one longer (2.64 Å) Ba(1)-F(7) bond length. Ca(1) is bonded to one F(1), one F(2), one F(3), one F(5), one F(6), and one F(7) atom to form distorted CaF6 octahedra that share corners with three equivalent Mn(1)F6 octahedra and  an edgeedge with one Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 54-67°. The Ca(1)-F(1) bond length is 2.22 Å. The Ca(1)-F(2) bond length is 2.29 Å. The Ca(1)-F(3) bond length is 2.37 Å. The Ca(1)-F(5) bond length is 2.34 Å. The Ca(1)-F(6) bond length is 2.30 Å. The Ca(1)-F(7) bond length is 2.17 Å. Mn(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 MnF6 octahedra that share corners with three equivalent Ca(1)F6 octahedra and  an edgeedge with one Ca(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 54-67°. The Mn(1)-F(1) bond length is 2.11 Å. The Mn(1)-F(2) bond length is 1.90 Å. The Mn(1)-F(3) bond length is 2.16 Å. The Mn(1)-F(4) bond length is 1.88 Å. The Mn(1)-F(5) bond length is 1.91 Å. The Mn(1)-F(6) bond length is 1.94 Å. There are seven inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Ba(1), one Ca(1), and one Mn(1) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one Ca(1) and one Mn(1) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to two equivalent Ba(1), one Ca(1), and one Mn(1) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to two equivalent Ba(1) and one Mn(1) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Ba(1), one Ca(1), and one Mn(1) atom. In the sixth F site, F(6) is bonded in a distorted water-like geometry to two equivalent Ba(1), one Ca(1), and one Mn(1) atom. In the seventh F site, F(7) is bonded in a trigonal planar geometry to two equivalent Ba(1) and one Ca(1) atom.