Ca5Rh19P12 crystallizes in the hexagonal P-62m space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 16-coordinate geometry to two equivalent Rh(2), two equivalent Rh(3), two equivalent Rh(5), four equivalent Rh(1), two equivalent P(3), and four equivalent P(2) atoms. In the second Ca site, Ca(2) is bonded in a 15-coordinate geometry to three equivalent Rh(1), six equivalent Rh(2), and six equivalent P(1) atoms. There are five inequivalent Rh sites. In the first Rh site, Rh(5) is bonded in a 9-coordinate geometry to six equivalent Ca(1) and three equivalent P(2) atoms. In the second Rh site, Rh(1) is bonded in a 12-coordinate geometry to one Ca(2), two equivalent Ca(1), one Rh(4), two equivalent Rh(2), two equivalent Rh(3), one P(2), one P(3), and two equivalent P(1) atoms. In the third Rh site, Rh(2) is bonded in a 12-coordinate geometry to one Ca(1), two equivalent Ca(2), one Rh(2), two equivalent Rh(1), two equivalent Rh(4), two equivalent P(1), and two equivalent P(3) atoms. In the fourth Rh site, Rh(3) is bonded in a 4-coordinate geometry to two equivalent Ca(1), four equivalent Rh(1), two equivalent P(1), and two equivalent P(2) atoms. In the fifth Rh site, Rh(4) is bonded in a distorted single-bond geometry to two equivalent Rh(1), four equivalent Rh(2), one P(3), and four equivalent P(1) atoms. There are three inequivalent P sites. In the first P site, P(1) is bonded in a 9-coordinate geometry to two equivalent Ca(2), one Rh(3), two equivalent Rh(1), two equivalent Rh(2), and two equivalent Rh(4) atoms. In the second P site, P(2) is bonded in a 9-coordinate geometry to four equivalent Ca(1), one Rh(5), two equivalent Rh(1), and two equivalent Rh(3) atoms. In the third P site, P(3) is bonded in a 9-coordinate geometry to two equivalent Ca(1), one Rh(4), two equivalent Rh(1), and four equivalent Rh(2) atoms.
Ca5Rh19P12 crystallizes in the hexagonal P-62m space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 16-coordinate geometry to two equivalent Rh(2), two equivalent Rh(3), two equivalent Rh(5), four equivalent Rh(1), two equivalent P(3), and four equivalent P(2) atoms. Both Ca(1)-Rh(2) bond lengths are 3.36 Å. Both Ca(1)-Rh(3) bond lengths are 3.17 Å. Both Ca(1)-Rh(5) bond lengths are 3.06 Å. All Ca(1)-Rh(1) bond lengths are 3.16 Å. Both Ca(1)-P(3) bond lengths are 3.04 Å. All Ca(1)-P(2) bond lengths are 3.04 Å. In the second Ca site, Ca(2) is bonded in a 15-coordinate geometry to three equivalent Rh(1), six equivalent Rh(2), and six equivalent P(1) atoms. All Ca(2)-Rh(1) bond lengths are 3.20 Å. All Ca(2)-Rh(2) bond lengths are 3.14 Å. All Ca(2)-P(1) bond lengths are 2.98 Å. There are five inequivalent Rh sites. In the first Rh site, Rh(5) is bonded in a 9-coordinate geometry to six equivalent Ca(1) and three equivalent P(2) atoms. All Rh(5)-P(2) bond lengths are 2.30 Å. In the second Rh site, Rh(1) is bonded in a 12-coordinate geometry to one Ca(2), two equivalent Ca(1), one Rh(4), two equivalent Rh(2), two equivalent Rh(3), one P(2), one P(3), and two equivalent P(1) atoms. The Rh(1)-Rh(4) bond length is 2.91 Å. Both Rh(1)-Rh(2) bond lengths are 2.79 Å. Both Rh(1)-Rh(3) bond lengths are 2.80 Å. The Rh(1)-P(2) bond length is 2.40 Å. The Rh(1)-P(3) bond length is 2.43 Å. Both Rh(1)-P(1) bond lengths are 2.43 Å. In the third Rh site, Rh(2) is bonded in a 12-coordinate geometry to one Ca(1), two equivalent Ca(2), one Rh(2), two equivalent Rh(1), two equivalent Rh(4), two equivalent P(1), and two equivalent P(3) atoms. The Rh(2)-Rh(2) bond length is 2.85 Å. Both Rh(2)-Rh(4) bond lengths are 2.89 Å. There is one shorter (2.31 Å) and one longer (2.39 Å) Rh(2)-P(1) bond length. Both Rh(2)-P(3) bond lengths are 2.54 Å. In the fourth Rh site, Rh(3) is bonded in a 4-coordinate geometry to two equivalent Ca(1), four equivalent Rh(1), two equivalent P(1), and two equivalent P(2) atoms. Both Rh(3)-P(1) bond lengths are 2.35 Å. Both Rh(3)-P(2) bond lengths are 2.36 Å. In the fifth Rh site, Rh(4) is bonded in a distorted single-bond geometry to two equivalent Rh(1), four equivalent Rh(2), one P(3), and four equivalent P(1) atoms. The Rh(4)-P(3) bond length is 2.29 Å. All Rh(4)-P(1) bond lengths are 2.79 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded in a 9-coordinate geometry to two equivalent Ca(2), one Rh(3), two equivalent Rh(1), two equivalent Rh(2), and two equivalent Rh(4) atoms. In the second P site, P(2) is bonded in a 9-coordinate geometry to four equivalent Ca(1), one Rh(5), two equivalent Rh(1), and two equivalent Rh(3) atoms. In the third P site, P(3) is bonded in a 9-coordinate geometry to two equivalent Ca(1), one Rh(4), two equivalent Rh(1), and four equivalent Rh(2) atoms.