(CaAl2Si4O12)2(Cl2)3 crystallizes in the monoclinic Cm space group. The structure consists of two chlorane molecules inside a CaAl2Si4O12 framework. In the CaAl2Si4O12 framework, there are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 5-coordinate geometry to one O(12), two equivalent O(1), and two equivalent O(11) atoms. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to one O(14), one O(4), two equivalent O(13), and two equivalent O(3) atoms. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(1), one O(10), one O(11), and one O(5) atom to form AlO4 tetrahedra that share  a cornercorner with one Al(2)O4 tetrahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  a cornercorner with one Si(4)O4 tetrahedra. In the second Al site, Al(2) is bonded to one O(1), one O(12), one O(7), and one O(8) atom to form AlO4 tetrahedra that share  a cornercorner with one Al(1)O4 tetrahedra,  a cornercorner with one Al(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and  a cornercorner with one Si(4)O4 tetrahedra. There are four inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(11), one O(2), one O(6), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Al(1)O4 tetrahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  a cornercorner with one Si(3)O4 tetrahedra. In the second Si site, Si(2) is bonded to one O(10), one O(13), one O(3), and one O(6) atom to form SiO4 tetrahedra that share  a cornercorner with one Al(1)O4 tetrahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and  a cornercorner with one Si(4)O4 tetrahedra. In the third Si site, Si(3) is bonded to one O(14), one O(3), one O(7), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Al(2)O4 tetrahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  a cornercorner with one Si(3)O4 tetrahedra. In the fourth Si site, Si(4) is bonded to one O(13), one O(4), one O(5), and one O(8) atom to form SiO4 tetrahedra that share  a cornercorner with one Al(1)O4 tetrahedra,  a cornercorner with one Al(2)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  a cornercorner with one Si(4)O4 tetrahedra. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Ca(1), one Al(1), and one Al(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to two equivalent Si(1) atoms. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Ca(2), one Si(2), and one Si(3) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Ca(2) and two equivalent Si(4) atoms. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Al(1) and one Si(4) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Al(2) and one Si(3) atom. In the eighth O site, O(8) is bonded in a linear geometry to one Al(2) and one Si(4) atom. In the ninth O site, O(9) is bonded in a linear geometry to one Si(1) and one Si(3) atom. In the tenth O site, O(10) is bonded in a linear geometry to one Al(1) and one Si(2) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Ca(1), one Al(1), and one Si(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1) and two equivalent Al(2) atoms. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Ca(2), one Si(2), and one Si(4) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Ca(2) and two equivalent Si(3) atoms.
(CaAl2Si4O12)2(Cl2)3 crystallizes in the monoclinic Cm space group. The structure consists of two chlorane molecules inside a CaAl2Si4O12 framework. In the CaAl2Si4O12 framework, there are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 5-coordinate geometry to one O(12), two equivalent O(1), and two equivalent O(11) atoms. The Ca(1)-O(12) bond length is 2.20 Å. Both Ca(1)-O(1) bond lengths are 2.62 Å. Both Ca(1)-O(11) bond lengths are 2.50 Å. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to one O(14), one O(4), two equivalent O(13), and two equivalent O(3) atoms. The Ca(2)-O(14) bond length is 2.45 Å. The Ca(2)-O(4) bond length is 2.66 Å. Both Ca(2)-O(13) bond lengths are 2.32 Å. Both Ca(2)-O(3) bond lengths are 2.97 Å. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(1), one O(10), one O(11), and one O(5) atom to form AlO4 tetrahedra that share  a cornercorner with one Al(2)O4 tetrahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  a cornercorner with one Si(4)O4 tetrahedra. The Al(1)-O(1) bond length is 1.73 Å. The Al(1)-O(10) bond length is 1.74 Å. The Al(1)-O(11) bond length is 1.83 Å. The Al(1)-O(5) bond length is 1.72 Å. In the second Al site, Al(2) is bonded to one O(1), one O(12), one O(7), and one O(8) atom to form AlO4 tetrahedra that share  a cornercorner with one Al(1)O4 tetrahedra,  a cornercorner with one Al(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and  a cornercorner with one Si(4)O4 tetrahedra. The Al(2)-O(1) bond length is 1.76 Å. The Al(2)-O(12) bond length is 1.75 Å. The Al(2)-O(7) bond length is 1.75 Å. The Al(2)-O(8) bond length is 1.74 Å. There are four inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(11), one O(2), one O(6), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Al(1)O4 tetrahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  a cornercorner with one Si(3)O4 tetrahedra. The Si(1)-O(11) bond length is 1.63 Å. The Si(1)-O(2) bond length is 1.64 Å. The Si(1)-O(6) bond length is 1.63 Å. The Si(1)-O(9) bond length is 1.63 Å. In the second Si site, Si(2) is bonded to one O(10), one O(13), one O(3), and one O(6) atom to form SiO4 tetrahedra that share  a cornercorner with one Al(1)O4 tetrahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and  a cornercorner with one Si(4)O4 tetrahedra. The Si(2)-O(10) bond length is 1.57 Å. The Si(2)-O(13) bond length is 1.68 Å. The Si(2)-O(3) bond length is 1.65 Å. The Si(2)-O(6) bond length is 1.63 Å. In the third Si site, Si(3) is bonded to one O(14), one O(3), one O(7), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Al(2)O4 tetrahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  a cornercorner with one Si(3)O4 tetrahedra. The Si(3)-O(14) bond length is 1.70 Å. The Si(3)-O(3) bond length is 1.65 Å. The Si(3)-O(7) bond length is 1.58 Å. The Si(3)-O(9) bond length is 1.62 Å. In the fourth Si site, Si(4) is bonded to one O(13), one O(4), one O(5), and one O(8) atom to form SiO4 tetrahedra that share  a cornercorner with one Al(1)O4 tetrahedra,  a cornercorner with one Al(2)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  a cornercorner with one Si(4)O4 tetrahedra. The Si(4)-O(13) bond length is 1.71 Å. The Si(4)-O(4) bond length is 1.66 Å. The Si(4)-O(5) bond length is 1.58 Å. The Si(4)-O(8) bond length is 1.58 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Ca(1), one Al(1), and one Al(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to two equivalent Si(1) atoms. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Ca(2), one Si(2), and one Si(3) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Ca(2) and two equivalent Si(4) atoms. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Al(1) and one Si(4) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Al(2) and one Si(3) atom. In the eighth O site, O(8) is bonded in a linear geometry to one Al(2) and one Si(4) atom. In the ninth O site, O(9) is bonded in a linear geometry to one Si(1) and one Si(3) atom. In the tenth O site, O(10) is bonded in a linear geometry to one Al(1) and one Si(2) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Ca(1), one Al(1), and one Si(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1) and two equivalent Al(2) atoms. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Ca(2), one Si(2), and one Si(4) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Ca(2) and two equivalent Si(3) atoms.