Ce4(RhSi3)3 crystallizes in the orthorhombic Pmm2 space group. There are four inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 14-coordinate geometry to four equivalent Rh(2), two equivalent Si(2), two equivalent Si(5), two equivalent Si(7), and four equivalent Si(3) atoms. In the second Ce site, Ce(2) is bonded in a 14-coordinate geometry to four equivalent Rh(3), two equivalent Si(1), two equivalent Si(6), two equivalent Si(8), and four equivalent Si(4) atoms. In the third Ce site, Ce(3) is bonded in a 14-coordinate geometry to two equivalent Si(4), two equivalent Si(5), two equivalent Si(7), four equivalent Si(1), and four equivalent Si(9) atoms. In the fourth Ce site, Ce(4) is bonded in a 14-coordinate geometry to four equivalent Rh(1), two equivalent Si(3), two equivalent Si(6), two equivalent Si(8), and four equivalent Si(2) atoms. There are three inequivalent Rh sites. In the first Rh site, Rh(1) is bonded in a 5-coordinate geometry to four equivalent Ce(4), one Si(2), two equivalent Si(6), and two equivalent Si(8) atoms. In the second Rh site, Rh(2) is bonded in a 5-coordinate geometry to four equivalent Ce(1), one Si(3), two equivalent Si(5), and two equivalent Si(7) atoms. In the third Rh site, Rh(3) is bonded in a 5-coordinate geometry to four equivalent Ce(2), one Si(4), two equivalent Si(6), and two equivalent Si(8) atoms. There are nine inequivalent Si sites. In the first Si site, Si(1) is bonded in a 9-coordinate geometry to two equivalent Ce(2), four equivalent Ce(3), one Si(9), and two equivalent Si(4) atoms. In the second Si site, Si(2) is bonded in a distorted single-bond geometry to two equivalent Ce(1), four equivalent Ce(4), one Rh(1), and two equivalent Si(3) atoms. In the third Si site, Si(3) is bonded in a distorted single-bond geometry to two equivalent Ce(4), four equivalent Ce(1), one Rh(2), and two equivalent Si(2) atoms. In the fourth Si site, Si(4) is bonded in a distorted single-bond geometry to two equivalent Ce(3), four equivalent Ce(2), one Rh(3), and two equivalent Si(1) atoms. In the fifth Si site, Si(5) is bonded in a distorted bent 120 degrees geometry to two equivalent Ce(1), two equivalent Ce(3), two equivalent Rh(2), and two equivalent Si(9) atoms. In the sixth Si site, Si(6) is bonded in a 4-coordinate geometry to two equivalent Ce(2), two equivalent Ce(4), two equivalent Rh(1), and two equivalent Rh(3) atoms. In the seventh Si site, Si(7) is bonded in a distorted bent 120 degrees geometry to two equivalent Ce(1), two equivalent Ce(3), two equivalent Rh(2), and two equivalent Si(9) atoms. In the eighth Si site, Si(8) is bonded in a 4-coordinate geometry to two equivalent Ce(2), two equivalent Ce(4), two equivalent Rh(1), and two equivalent Rh(3) atoms. In the ninth Si site, Si(9) is bonded in a 9-coordinate geometry to four equivalent Ce(3), one Si(1), two equivalent Si(5), and two equivalent Si(7) atoms.
Ce4(RhSi3)3 crystallizes in the orthorhombic Pmm2 space group. There are four inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 14-coordinate geometry to four equivalent Rh(2), two equivalent Si(2), two equivalent Si(5), two equivalent Si(7), and four equivalent Si(3) atoms. All Ce(1)-Rh(2) bond lengths are 3.29 Å. Both Ce(1)-Si(2) bond lengths are 3.09 Å. Both Ce(1)-Si(5) bond lengths are 3.26 Å. Both Ce(1)-Si(7) bond lengths are 3.24 Å. All Ce(1)-Si(3) bond lengths are 3.13 Å. In the second Ce site, Ce(2) is bonded in a 14-coordinate geometry to four equivalent Rh(3), two equivalent Si(1), two equivalent Si(6), two equivalent Si(8), and four equivalent Si(4) atoms. All Ce(2)-Rh(3) bond lengths are 3.21 Å. Both Ce(2)-Si(1) bond lengths are 3.10 Å. Both Ce(2)-Si(6) bond lengths are 3.22 Å. Both Ce(2)-Si(8) bond lengths are 3.19 Å. All Ce(2)-Si(4) bond lengths are 3.18 Å. In the third Ce site, Ce(3) is bonded in a 14-coordinate geometry to two equivalent Si(4), two equivalent Si(5), two equivalent Si(7), four equivalent Si(1), and four equivalent Si(9) atoms. Both Ce(3)-Si(4) bond lengths are 3.25 Å. Both Ce(3)-Si(5) bond lengths are 3.12 Å. Both Ce(3)-Si(7) bond lengths are 3.15 Å. All Ce(3)-Si(1) bond lengths are 3.26 Å. All Ce(3)-Si(9) bond lengths are 3.12 Å. In the fourth Ce site, Ce(4) is bonded in a 14-coordinate geometry to four equivalent Rh(1), two equivalent Si(3), two equivalent Si(6), two equivalent Si(8), and four equivalent Si(2) atoms. All Ce(4)-Rh(1) bond lengths are 3.21 Å. Both Ce(4)-Si(3) bond lengths are 3.21 Å. Both Ce(4)-Si(6) bond lengths are 3.19 Å. Both Ce(4)-Si(8) bond lengths are 3.22 Å. All Ce(4)-Si(2) bond lengths are 3.19 Å. There are three inequivalent Rh sites. In the first Rh site, Rh(1) is bonded in a 5-coordinate geometry to four equivalent Ce(4), one Si(2), two equivalent Si(6), and two equivalent Si(8) atoms. The Rh(1)-Si(2) bond length is 2.37 Å. Both Rh(1)-Si(6) bond lengths are 2.42 Å. Both Rh(1)-Si(8) bond lengths are 2.42 Å. In the second Rh site, Rh(2) is bonded in a 5-coordinate geometry to four equivalent Ce(1), one Si(3), two equivalent Si(5), and two equivalent Si(7) atoms. The Rh(2)-Si(3) bond length is 2.41 Å. Both Rh(2)-Si(5) bond lengths are 2.35 Å. Both Rh(2)-Si(7) bond lengths are 2.35 Å. In the third Rh site, Rh(3) is bonded in a 5-coordinate geometry to four equivalent Ce(2), one Si(4), two equivalent Si(6), and two equivalent Si(8) atoms. The Rh(3)-Si(4) bond length is 2.35 Å. Both Rh(3)-Si(6) bond lengths are 2.42 Å. Both Rh(3)-Si(8) bond lengths are 2.42 Å. There are nine inequivalent Si sites. In the first Si site, Si(1) is bonded in a 9-coordinate geometry to two equivalent Ce(2), four equivalent Ce(3), one Si(9), and two equivalent Si(4) atoms. The Si(1)-Si(9) bond length is 2.31 Å. Both Si(1)-Si(4) bond lengths are 2.38 Å. In the second Si site, Si(2) is bonded in a distorted single-bond geometry to two equivalent Ce(1), four equivalent Ce(4), one Rh(1), and two equivalent Si(3) atoms. Both Si(2)-Si(3) bond lengths are 2.45 Å. In the third Si site, Si(3) is bonded in a distorted single-bond geometry to two equivalent Ce(4), four equivalent Ce(1), one Rh(2), and two equivalent Si(2) atoms. In the fourth Si site, Si(4) is bonded in a distorted single-bond geometry to two equivalent Ce(3), four equivalent Ce(2), one Rh(3), and two equivalent Si(1) atoms. In the fifth Si site, Si(5) is bonded in a distorted bent 120 degrees geometry to two equivalent Ce(1), two equivalent Ce(3), two equivalent Rh(2), and two equivalent Si(9) atoms. Both Si(5)-Si(9) bond lengths are 2.50 Å. In the sixth Si site, Si(6) is bonded in a 4-coordinate geometry to two equivalent Ce(2), two equivalent Ce(4), two equivalent Rh(1), and two equivalent Rh(3) atoms. In the seventh Si site, Si(7) is bonded in a distorted bent 120 degrees geometry to two equivalent Ce(1), two equivalent Ce(3), two equivalent Rh(2), and two equivalent Si(9) atoms. Both Si(7)-Si(9) bond lengths are 2.51 Å. In the eighth Si site, Si(8) is bonded in a 4-coordinate geometry to two equivalent Ce(2), two equivalent Ce(4), two equivalent Rh(1), and two equivalent Rh(3) atoms. In the ninth Si site, Si(9) is bonded in a 9-coordinate geometry to four equivalent Ce(3), one Si(1), two equivalent Si(5), and two equivalent Si(7) atoms.