CaCe4Si3O13 crystallizes in the monoclinic P2_1 space group. Ca(1) is bonded in a 9-coordinate geometry to one O(1), one O(11), one O(12), one O(13), one O(2), one O(3), one O(7), one O(8), and one O(9) atom. There are four inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 9-coordinate geometry to one O(1), one O(11), one O(12), one O(13), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. In the second Ce site, Ce(2) is bonded in a 7-coordinate geometry to one O(10), one O(13), one O(2), one O(4), one O(6), one O(7), and one O(9) atom. In the third Ce site, Ce(3) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(3), one O(4), one O(5), one O(7), and one O(8) atom. In the fourth Ce site, Ce(4) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(12), one O(5), one O(6), one O(8), and one O(9) atom. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded in a tetrahedral geometry to one O(1), one O(11), one O(4), and one O(7) atom. In the second Si site, Si(2) is bonded in a tetrahedral geometry to one O(12), one O(2), one O(5), and one O(8) atom. In the third Si site, Si(3) is bonded in a tetrahedral geometry to one O(13), one O(3), one O(6), and one O(9) atom. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Ca(1), one Ce(1), one Ce(4), and one Si(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Ca(1), one Ce(1), one Ce(2), and one Si(2) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Ca(1), one Ce(1), one Ce(3), and one Si(3) atom. In the fourth O site, O(4) is bonded in a 1-coordinate geometry to one Ce(1), one Ce(2), one Ce(3), and one Si(1) atom. In the fifth O site, O(5) is bonded in a 1-coordinate geometry to one Ce(1), one Ce(3), one Ce(4), and one Si(2) atom. In the sixth O site, O(6) is bonded in a 1-coordinate geometry to one Ce(1), one Ce(2), one Ce(4), and one Si(3) atom. In the seventh O site, O(7) is bonded in a 1-coordinate geometry to one Ca(1), one Ce(2), one Ce(3), and one Si(1) atom. In the eighth O site, O(8) is bonded in a 1-coordinate geometry to one Ca(1), one Ce(3), one Ce(4), and one Si(2) atom. In the ninth O site, O(9) is bonded in a 1-coordinate geometry to one Ca(1), one Ce(2), one Ce(4), and one Si(3) atom. In the tenth O site, O(10) is bonded in a trigonal planar geometry to one Ce(2), one Ce(3), and one Ce(4) atom. In the eleventh O site, O(11) is bonded to one Ca(1), one Ce(1), one Ce(3), and one Si(1) atom to form distorted edge-sharing OCaCe2Si tetrahedra. In the twelfth O site, O(12) is bonded to one Ca(1), one Ce(1), one Ce(4), and one Si(2) atom to form distorted edge-sharing OCaCe2Si tetrahedra. In the thirteenth O site, O(13) is bonded to one Ca(1), one Ce(1), one Ce(2), and one Si(3) atom to form distorted edge-sharing OCaCe2Si tetrahedra.
CaCe4Si3O13 crystallizes in the monoclinic P2_1 space group. Ca(1) is bonded in a 9-coordinate geometry to one O(1), one O(11), one O(12), one O(13), one O(2), one O(3), one O(7), one O(8), and one O(9) atom. The Ca(1)-O(1) bond length is 2.44 Å. The Ca(1)-O(11) bond length is 2.52 Å. The Ca(1)-O(12) bond length is 2.52 Å. The Ca(1)-O(13) bond length is 2.51 Å. The Ca(1)-O(2) bond length is 2.44 Å. The Ca(1)-O(3) bond length is 2.44 Å. The Ca(1)-O(7) bond length is 2.94 Å. The Ca(1)-O(8) bond length is 2.94 Å. The Ca(1)-O(9) bond length is 2.94 Å. There are four inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 9-coordinate geometry to one O(1), one O(11), one O(12), one O(13), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The Ce(1)-O(1) bond length is 2.44 Å. The Ce(1)-O(11) bond length is 2.51 Å. The Ce(1)-O(12) bond length is 2.51 Å. The Ce(1)-O(13) bond length is 2.51 Å. The Ce(1)-O(2) bond length is 2.44 Å. The Ce(1)-O(3) bond length is 2.44 Å. The Ce(1)-O(4) bond length is 2.89 Å. The Ce(1)-O(5) bond length is 2.88 Å. The Ce(1)-O(6) bond length is 2.88 Å. In the second Ce site, Ce(2) is bonded in a 7-coordinate geometry to one O(10), one O(13), one O(2), one O(4), one O(6), one O(7), and one O(9) atom. The Ce(2)-O(10) bond length is 2.30 Å. The Ce(2)-O(13) bond length is 2.50 Å. The Ce(2)-O(2) bond length is 2.80 Å. The Ce(2)-O(4) bond length is 2.53 Å. The Ce(2)-O(6) bond length is 2.43 Å. The Ce(2)-O(7) bond length is 2.50 Å. The Ce(2)-O(9) bond length is 2.42 Å. In the third Ce site, Ce(3) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(3), one O(4), one O(5), one O(7), and one O(8) atom. The Ce(3)-O(10) bond length is 2.30 Å. The Ce(3)-O(11) bond length is 2.51 Å. The Ce(3)-O(3) bond length is 2.81 Å. The Ce(3)-O(4) bond length is 2.43 Å. The Ce(3)-O(5) bond length is 2.53 Å. The Ce(3)-O(7) bond length is 2.42 Å. The Ce(3)-O(8) bond length is 2.50 Å. In the fourth Ce site, Ce(4) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(12), one O(5), one O(6), one O(8), and one O(9) atom. The Ce(4)-O(1) bond length is 2.82 Å. The Ce(4)-O(10) bond length is 2.30 Å. The Ce(4)-O(12) bond length is 2.50 Å. The Ce(4)-O(5) bond length is 2.43 Å. The Ce(4)-O(6) bond length is 2.53 Å. The Ce(4)-O(8) bond length is 2.42 Å. The Ce(4)-O(9) bond length is 2.50 Å. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded in a tetrahedral geometry to one O(1), one O(11), one O(4), and one O(7) atom. The Si(1)-O(1) bond length is 1.63 Å. The Si(1)-O(11) bond length is 1.64 Å. The Si(1)-O(4) bond length is 1.65 Å. The Si(1)-O(7) bond length is 1.65 Å. In the second Si site, Si(2) is bonded in a tetrahedral geometry to one O(12), one O(2), one O(5), and one O(8) atom. The Si(2)-O(12) bond length is 1.64 Å. The Si(2)-O(2) bond length is 1.63 Å. The Si(2)-O(5) bond length is 1.66 Å. The Si(2)-O(8) bond length is 1.65 Å. In the third Si site, Si(3) is bonded in a tetrahedral geometry to one O(13), one O(3), one O(6), and one O(9) atom. The Si(3)-O(13) bond length is 1.64 Å. The Si(3)-O(3) bond length is 1.63 Å. The Si(3)-O(6) bond length is 1.65 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 4-coordinate geometry to one Ca(1), one Ce(1), one Ce(4), and one Si(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Ca(1), one Ce(1), one Ce(2), and one Si(2) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Ca(1), one Ce(1), one Ce(3), and one Si(3) atom. In the fourth O site, O(4) is bonded in a 1-coordinate geometry to one Ce(1), one Ce(2), one Ce(3), and one Si(1) atom. In the fifth O site, O(5) is bonded in a 1-coordinate geometry to one Ce(1), one Ce(3), one Ce(4), and one Si(2) atom. In the sixth O site, O(6) is bonded in a 1-coordinate geometry to one Ce(1), one Ce(2), one Ce(4), and one Si(3) atom. In the seventh O site, O(7) is bonded in a 1-coordinate geometry to one Ca(1), one Ce(2), one Ce(3), and one Si(1) atom. In the eighth O site, O(8) is bonded in a 1-coordinate geometry to one Ca(1), one Ce(3), one Ce(4), and one Si(2) atom. In the ninth O site, O(9) is bonded in a 1-coordinate geometry to one Ca(1), one Ce(2), one Ce(4), and one Si(3) atom. In the tenth O site, O(10) is bonded in a trigonal planar geometry to one Ce(2), one Ce(3), and one Ce(4) atom. In the eleventh O site, O(11) is bonded to one Ca(1), one Ce(1), one Ce(3), and one Si(1) atom to form distorted edge-sharing OCaCe2Si tetrahedra. In the twelfth O site, O(12) is bonded to one Ca(1), one Ce(1), one Ce(4), and one Si(2) atom to form distorted edge-sharing OCaCe2Si tetrahedra. In the thirteenth O site, O(13) is bonded to one Ca(1), one Ce(1), one Ce(2), and one Si(3) atom to form distorted edge-sharing OCaCe2Si tetrahedra.