Ca3TiAl2Si3O13F2 crystallizes in the triclinic P-1 space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 7-coordinate geometry to one O(13), one O(2), one O(5), one O(6), one O(8), one O(9), and one F(1) atom. In the second Ca site, Ca(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(4), one O(6), two equivalent O(7), and one F(2) atom. In the third Ca site, Ca(3) is bonded in a 7-coordinate geometry to one O(11), one O(12), one O(13), one O(3), one O(5), and two equivalent O(10) atoms. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(10), two equivalent O(11), and two equivalent O(12) atoms to form TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, and corners with two equivalent Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 38°. In the second Ti site, Ti(2) is bonded to two equivalent O(11), two equivalent O(13), and two equivalent O(9) atoms to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra and corners with four equivalent Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 38°. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(2), one O(4), one O(6), one O(8), one F(1), and one F(2) atom to form AlO4F2 octahedra that share corners with two equivalent Al(2)O4F2 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and corners with two equivalent Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-37°. In the second Al site, Al(2) is bonded to one O(1), one O(3), one O(5), one O(7), one F(1), and one F(2) atom to form AlO4F2 octahedra that share corners with two equivalent Al(1)O4F2 octahedra, corners with two equivalent Si(1)O4 tetrahedra, and corners with two equivalent Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-37°. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(12), one O(2), one O(3), and one O(5) atom to form SiO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Al(1)O4F2 octahedra, and corners with two equivalent Al(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 34-52°. In the second Si site, Si(2) is bonded to one O(1), one O(4), one O(6), and one O(7) atom to form SiO4 tetrahedra that share corners with two equivalent Al(1)O4F2 octahedra and corners with two equivalent Al(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 34-52°. In the third Si site, Si(3) is bonded to one O(10), one O(13), one O(8), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Al(1)O4F2 octahedra, and corners with two equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-53°. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Ca(2), one Al(2), and one Si(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Al(1), and one Si(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Ca(3), one Al(2), and one Si(1) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Ca(2), one Al(1), and one Si(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(3), one Al(2), and one Si(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Al(1), and one Si(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to two equivalent Ca(2), one Al(2), and one Si(2) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Ca(1), one Al(1), and one Si(3) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Ca(1), one Ti(2), and one Si(3) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to two equivalent Ca(3), one Ti(1), and one Si(3) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Ca(3), one Ti(1), and one Ti(2) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one Ca(3), one Ti(1), and one Si(1) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(3), one Ti(2), and one Si(3) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Ca(1), one Al(1), and one Al(2) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Ca(2), one Al(1), and one Al(2) atom.
Ca3TiAl2Si3O13F2 crystallizes in the triclinic P-1 space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 7-coordinate geometry to one O(13), one O(2), one O(5), one O(6), one O(8), one O(9), and one F(1) atom. The Ca(1)-O(13) bond length is 2.41 Å. The Ca(1)-O(2) bond length is 2.64 Å. The Ca(1)-O(5) bond length is 2.59 Å. The Ca(1)-O(6) bond length is 2.41 Å. The Ca(1)-O(8) bond length is 2.36 Å. The Ca(1)-O(9) bond length is 2.37 Å. The Ca(1)-F(1) bond length is 2.30 Å. In the second Ca site, Ca(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(4), one O(6), two equivalent O(7), and one F(2) atom. The Ca(2)-O(1) bond length is 2.35 Å. The Ca(2)-O(2) bond length is 2.41 Å. The Ca(2)-O(4) bond length is 2.36 Å. The Ca(2)-O(6) bond length is 2.59 Å. There is one shorter (2.42 Å) and one longer (2.64 Å) Ca(2)-O(7) bond length. The Ca(2)-F(2) bond length is 2.30 Å. In the third Ca site, Ca(3) is bonded in a 7-coordinate geometry to one O(11), one O(12), one O(13), one O(3), one O(5), and two equivalent O(10) atoms. The Ca(3)-O(11) bond length is 2.27 Å. The Ca(3)-O(12) bond length is 2.40 Å. The Ca(3)-O(13) bond length is 2.60 Å. The Ca(3)-O(3) bond length is 2.41 Å. The Ca(3)-O(5) bond length is 2.44 Å. There is one shorter (2.47 Å) and one longer (2.60 Å) Ca(3)-O(10) bond length. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(10), two equivalent O(11), and two equivalent O(12) atoms to form TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, and corners with two equivalent Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 38°. Both Ti(1)-O(10) bond lengths are 2.03 Å. Both Ti(1)-O(11) bond lengths are 1.87 Å. Both Ti(1)-O(12) bond lengths are 1.99 Å. In the second Ti site, Ti(2) is bonded to two equivalent O(11), two equivalent O(13), and two equivalent O(9) atoms to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra and corners with four equivalent Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 38°. Both Ti(2)-O(11) bond lengths are 1.87 Å. Both Ti(2)-O(13) bond lengths are 2.03 Å. Both Ti(2)-O(9) bond lengths are 1.99 Å. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(2), one O(4), one O(6), one O(8), one F(1), and one F(2) atom to form AlO4F2 octahedra that share corners with two equivalent Al(2)O4F2 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and corners with two equivalent Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-37°. The Al(1)-O(2) bond length is 1.93 Å. The Al(1)-O(4) bond length is 1.88 Å. The Al(1)-O(6) bond length is 1.93 Å. The Al(1)-O(8) bond length is 1.89 Å. The Al(1)-F(1) bond length is 1.86 Å. The Al(1)-F(2) bond length is 1.86 Å. In the second Al site, Al(2) is bonded to one O(1), one O(3), one O(5), one O(7), one F(1), and one F(2) atom to form AlO4F2 octahedra that share corners with two equivalent Al(1)O4F2 octahedra, corners with two equivalent Si(1)O4 tetrahedra, and corners with two equivalent Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-37°. The Al(2)-O(1) bond length is 1.90 Å. The Al(2)-O(3) bond length is 1.89 Å. The Al(2)-O(5) bond length is 1.93 Å. The Al(2)-O(7) bond length is 1.93 Å. The Al(2)-F(1) bond length is 1.87 Å. The Al(2)-F(2) bond length is 1.87 Å. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(12), one O(2), one O(3), and one O(5) atom to form SiO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Al(1)O4F2 octahedra, and corners with two equivalent Al(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 34-52°. The Si(1)-O(12) bond length is 1.65 Å. The Si(1)-O(2) bond length is 1.66 Å. The Si(1)-O(3) bond length is 1.65 Å. The Si(1)-O(5) bond length is 1.66 Å. In the second Si site, Si(2) is bonded to one O(1), one O(4), one O(6), and one O(7) atom to form SiO4 tetrahedra that share corners with two equivalent Al(1)O4F2 octahedra and corners with two equivalent Al(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 34-52°. The Si(2)-O(1) bond length is 1.65 Å. The Si(2)-O(4) bond length is 1.65 Å. The Si(2)-O(6) bond length is 1.66 Å. The Si(2)-O(7) bond length is 1.66 Å. In the third Si site, Si(3) is bonded to one O(10), one O(13), one O(8), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Al(1)O4F2 octahedra, and corners with two equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-53°. The Si(3)-O(10) bond length is 1.65 Å. The Si(3)-O(13) bond length is 1.65 Å. The Si(3)-O(8) bond length is 1.64 Å. The Si(3)-O(9) bond length is 1.65 Å. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Ca(2), one Al(2), and one Si(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Al(1), and one Si(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Ca(3), one Al(2), and one Si(1) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Ca(2), one Al(1), and one Si(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(3), one Al(2), and one Si(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Al(1), and one Si(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to two equivalent Ca(2), one Al(2), and one Si(2) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Ca(1), one Al(1), and one Si(3) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Ca(1), one Ti(2), and one Si(3) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to two equivalent Ca(3), one Ti(1), and one Si(3) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Ca(3), one Ti(1), and one Ti(2) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one Ca(3), one Ti(1), and one Si(1) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(3), one Ti(2), and one Si(3) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Ca(1), one Al(1), and one Al(2) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Ca(2), one Al(1), and one Al(2) atom.