Ca10Si3S3(O12F)2 crystallizes in the hexagonal P-6 space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(3), one O(5), two equivalent O(1), two equivalent O(2), and one F(1) atom to form distorted CaO6F pentagonal bipyramids that share corners with two equivalent Ca(1)O6F pentagonal bipyramids, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent S(1)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. In the second Ca site, Ca(2) is bonded in a 7-coordinate geometry to one O(4), one O(6), two equivalent O(1), two equivalent O(2), and one F(2) atom. In the third Ca site, Ca(3) is bonded in a 9-coordinate geometry to three equivalent O(2), three equivalent O(4), and three equivalent O(5) atoms. In the fourth Ca site, Ca(4) is bonded in a 9-coordinate geometry to three equivalent O(1), three equivalent O(3), and three equivalent O(6) atoms. Si(1) is bonded to one O(3), one O(5), and two equivalent O(1) atoms to form SiO4 tetrahedra that share corners with two equivalent Ca(1)O6F pentagonal bipyramids and  an edgeedge with one Ca(1)O6F pentagonal bipyramid. S(1) is bonded to one O(4), one O(6), and two equivalent O(2) atoms to form SO4 tetrahedra that share corners with two equivalent Ca(1)O6F pentagonal bipyramids. There are six inequivalent O sites. In the first O site, O(5) is bonded in a 4-coordinate geometry to one Ca(1), two equivalent Ca(3), and one Si(1) atom. In the second O site, O(6) is bonded in a distorted single-bond geometry to one Ca(2), two equivalent Ca(4), and one S(1) atom. In the third O site, O(1) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Ca(4), and one Si(1) atom. In the fourth O site, O(2) is bonded in a 1-coordinate geometry to one Ca(1), one Ca(2), one Ca(3), and one S(1) atom. In the fifth O site, O(3) is bonded to one Ca(1), two equivalent Ca(4), and one Si(1) atom to form distorted edge-sharing OCa3Si tetrahedra. In the sixth O site, O(4) is bonded to one Ca(2), two equivalent Ca(3), and one S(1) atom to form distorted edge-sharing OCa3S tetrahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to three equivalent Ca(1) atoms. In the second F site, F(2) is bonded in a trigonal planar geometry to three equivalent Ca(2) atoms.
Ca10Si3S3(O12F)2 crystallizes in the hexagonal P-6 space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(3), one O(5), two equivalent O(1), two equivalent O(2), and one F(1) atom to form distorted CaO6F pentagonal bipyramids that share corners with two equivalent Ca(1)O6F pentagonal bipyramids, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent S(1)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. The Ca(1)-O(3) bond length is 2.34 Å. The Ca(1)-O(5) bond length is 2.70 Å. Both Ca(1)-O(1) bond lengths are 2.41 Å. Both Ca(1)-O(2) bond lengths are 2.49 Å. The Ca(1)-F(1) bond length is 2.35 Å. In the second Ca site, Ca(2) is bonded in a 7-coordinate geometry to one O(4), one O(6), two equivalent O(1), two equivalent O(2), and one F(2) atom. The Ca(2)-O(4) bond length is 2.48 Å. The Ca(2)-O(6) bond length is 2.84 Å. Both Ca(2)-O(1) bond lengths are 2.29 Å. Both Ca(2)-O(2) bond lengths are 2.61 Å. The Ca(2)-F(2) bond length is 2.32 Å. In the third Ca site, Ca(3) is bonded in a 9-coordinate geometry to three equivalent O(2), three equivalent O(4), and three equivalent O(5) atoms. All Ca(3)-O(2) bond lengths are 2.87 Å. All Ca(3)-O(4) bond lengths are 2.61 Å. All Ca(3)-O(5) bond lengths are 2.30 Å. In the fourth Ca site, Ca(4) is bonded in a 9-coordinate geometry to three equivalent O(1), three equivalent O(3), and three equivalent O(6) atoms. All Ca(4)-O(1) bond lengths are 2.85 Å. All Ca(4)-O(3) bond lengths are 2.38 Å. All Ca(4)-O(6) bond lengths are 2.59 Å. Si(1) is bonded to one O(3), one O(5), and two equivalent O(1) atoms to form SiO4 tetrahedra that share corners with two equivalent Ca(1)O6F pentagonal bipyramids and  an edgeedge with one Ca(1)O6F pentagonal bipyramid. The Si(1)-O(3) bond length is 1.65 Å. The Si(1)-O(5) bond length is 1.64 Å. Both Si(1)-O(1) bond lengths are 1.65 Å. S(1) is bonded to one O(4), one O(6), and two equivalent O(2) atoms to form SO4 tetrahedra that share corners with two equivalent Ca(1)O6F pentagonal bipyramids. The S(1)-O(4) bond length is 1.50 Å. The S(1)-O(6) bond length is 1.49 Å. Both S(1)-O(2) bond lengths are 1.49 Å. There are six inequivalent O sites. In the first O site, O(5) is bonded in a 4-coordinate geometry to one Ca(1), two equivalent Ca(3), and one Si(1) atom. In the second O site, O(6) is bonded in a distorted single-bond geometry to one Ca(2), two equivalent Ca(4), and one S(1) atom. In the third O site, O(1) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Ca(4), and one Si(1) atom. In the fourth O site, O(2) is bonded in a 1-coordinate geometry to one Ca(1), one Ca(2), one Ca(3), and one S(1) atom. In the fifth O site, O(3) is bonded to one Ca(1), two equivalent Ca(4), and one Si(1) atom to form distorted edge-sharing OCa3Si tetrahedra. In the sixth O site, O(4) is bonded to one Ca(2), two equivalent Ca(3), and one S(1) atom to form distorted edge-sharing OCa3S tetrahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to three equivalent Ca(1) atoms. In the second F site, F(2) is bonded in a trigonal planar geometry to three equivalent Ca(2) atoms.