Ca5(BO3)3F crystallizes in the monoclinic Cm space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 6-coordinate geometry to one O(3), one O(4), two equivalent O(2), and two equivalent O(5) atoms. In the second Ca site, Ca(2) is bonded to one O(5), two equivalent O(3), two equivalent O(4), and one F(1) atom to form CaO5F octahedra that share  a cornercorner with one Ca(2)O5F octahedra, corners with two equivalent Ca(3)O4F2 octahedra, and edges with two equivalent Ca(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 64-76°. In the third Ca site, Ca(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form CaO4F2 octahedra that share corners with four equivalent Ca(2)O5F octahedra and edges with two equivalent Ca(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 64-67°. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(2), one O(4), and one O(5) atom. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1) and two equivalent O(3) atoms. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Ca(3) and one B(2) atom. In the second O site, O(2) is bonded to one Ca(3), two equivalent Ca(1), and one B(1) atom to form distorted OCa3B tetrahedra that share corners with two equivalent O(3)Ca3B tetrahedra, corners with two equivalent F(1)Ca4 tetrahedra, and corners with three equivalent O(2)Ca3B tetrahedra. In the third O site, O(3) is bonded to one Ca(1), two equivalent Ca(2), and one B(2) atom to form distorted OCa3B tetrahedra that share corners with two equivalent O(2)Ca3B tetrahedra, corners with two equivalent F(1)Ca4 tetrahedra, and corners with three equivalent O(3)Ca3B tetrahedra. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Ca(1), two equivalent Ca(2), and one B(1) atom. In the fifth O site, O(5) is bonded in a 1-coordinate geometry to one Ca(2), two equivalent Ca(1), and one B(1) atom. F(1) is bonded to two equivalent Ca(2) and two equivalent Ca(3) atoms to form FCa4 tetrahedra that share corners with two equivalent F(1)Ca4 tetrahedra, corners with four equivalent O(2)Ca3B tetrahedra, and corners with four equivalent O(3)Ca3B tetrahedra.
Ca5(BO3)3F crystallizes in the monoclinic Cm space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 6-coordinate geometry to one O(3), one O(4), two equivalent O(2), and two equivalent O(5) atoms. The Ca(1)-O(3) bond length is 2.35 Å. The Ca(1)-O(4) bond length is 2.50 Å. There is one shorter (2.33 Å) and one longer (2.34 Å) Ca(1)-O(2) bond length. There is one shorter (2.46 Å) and one longer (2.54 Å) Ca(1)-O(5) bond length. In the second Ca site, Ca(2) is bonded to one O(5), two equivalent O(3), two equivalent O(4), and one F(1) atom to form CaO5F octahedra that share  a cornercorner with one Ca(2)O5F octahedra, corners with two equivalent Ca(3)O4F2 octahedra, and edges with two equivalent Ca(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 64-76°. The Ca(2)-O(5) bond length is 2.29 Å. Both Ca(2)-O(3) bond lengths are 2.34 Å. There is one shorter (2.29 Å) and one longer (2.35 Å) Ca(2)-O(4) bond length. The Ca(2)-F(1) bond length is 2.39 Å. In the third Ca site, Ca(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form CaO4F2 octahedra that share corners with four equivalent Ca(2)O5F octahedra and edges with two equivalent Ca(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 64-67°. There is one shorter (2.27 Å) and one longer (2.32 Å) Ca(3)-O(1) bond length. Both Ca(3)-O(2) bond lengths are 2.38 Å. There is one shorter (2.36 Å) and one longer (2.46 Å) Ca(3)-F(1) bond length. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(2), one O(4), and one O(5) atom. The B(1)-O(2) bond length is 1.38 Å. The B(1)-O(4) bond length is 1.38 Å. The B(1)-O(5) bond length is 1.38 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1) and two equivalent O(3) atoms. The B(2)-O(1) bond length is 1.38 Å. Both B(2)-O(3) bond lengths are 1.38 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Ca(3) and one B(2) atom. In the second O site, O(2) is bonded to one Ca(3), two equivalent Ca(1), and one B(1) atom to form distorted OCa3B tetrahedra that share corners with two equivalent O(3)Ca3B tetrahedra, corners with two equivalent F(1)Ca4 tetrahedra, and corners with three equivalent O(2)Ca3B tetrahedra. In the third O site, O(3) is bonded to one Ca(1), two equivalent Ca(2), and one B(2) atom to form distorted OCa3B tetrahedra that share corners with two equivalent O(2)Ca3B tetrahedra, corners with two equivalent F(1)Ca4 tetrahedra, and corners with three equivalent O(3)Ca3B tetrahedra. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Ca(1), two equivalent Ca(2), and one B(1) atom. In the fifth O site, O(5) is bonded in a 1-coordinate geometry to one Ca(2), two equivalent Ca(1), and one B(1) atom. F(1) is bonded to two equivalent Ca(2) and two equivalent Ca(3) atoms to form FCa4 tetrahedra that share corners with two equivalent F(1)Ca4 tetrahedra, corners with four equivalent O(2)Ca3B tetrahedra, and corners with four equivalent O(3)Ca3B tetrahedra.