Ca4Ir8P7 crystallizes in the monoclinic P2_1/m space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 15-coordinate geometry to one Ir(4), one Ir(5), two equivalent Ir(2), two equivalent Ir(7), three equivalent Ir(1), two equivalent P(1), two equivalent P(4), and two equivalent P(7) atoms. In the second Ca site, Ca(2) is bonded in a 15-coordinate geometry to one Ir(3), one Ir(7), two equivalent Ir(2), two equivalent Ir(8), three equivalent Ir(5), two equivalent P(2), two equivalent P(6), and two equivalent P(7) atoms. In the third Ca site, Ca(3) is bonded in a 14-coordinate geometry to one Ir(4), one Ir(8), two equivalent Ir(2), three equivalent Ir(3), one P(5), two equivalent P(2), two equivalent P(3), and two equivalent P(4) atoms. In the fourth Ca site, Ca(4) is bonded in a 1-coordinate geometry to one Ir(1), one Ir(8), two equivalent Ir(4), one P(6), two equivalent P(1), two equivalent P(3), and two equivalent P(5) atoms. There are eight inequivalent Ir sites. In the first Ir site, Ir(1) is bonded to one Ca(4), three equivalent Ca(1), two equivalent Ir(1), two equivalent Ir(4), one P(4), and three equivalent P(1) atoms to form distorted face-sharing IrCa4P4Ir4 cuboctahedra. In the second Ir site, Ir(2) is bonded in a 9-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), two equivalent Ca(3), one P(2), one P(4), and one P(7) atom. In the third Ir site, Ir(3) is bonded to one Ca(2), three equivalent Ca(3), two equivalent Ir(3), two equivalent Ir(8), one P(3), and three equivalent P(2) atoms to form distorted face-sharing IrCa4P4Ir4 cuboctahedra. In the fourth Ir site, Ir(4) is bonded in a 10-coordinate geometry to one Ca(1), one Ca(3), two equivalent Ca(4), two equivalent Ir(1), one P(1), one P(5), and two equivalent P(4) atoms. In the fifth Ir site, Ir(5) is bonded in a 12-coordinate geometry to one Ca(1), three equivalent Ca(2), two equivalent Ir(5), two equivalent Ir(7), one P(6), and three equivalent P(7) atoms. In the sixth Ir site, Ir(6) is bonded in a 4-coordinate geometry to one P(3) and three equivalent P(5) atoms. In the seventh Ir site, Ir(7) is bonded in a 7-coordinate geometry to one Ca(2), two equivalent Ca(1), two equivalent Ir(5), one P(1), one P(7), and two equivalent P(6) atoms. In the eighth Ir site, Ir(8) is bonded in a 10-coordinate geometry to one Ca(3), one Ca(4), two equivalent Ca(2), two equivalent Ir(3), one P(2), one P(6), and two equivalent P(3) atoms. There are seven inequivalent P sites. In the first P site, P(1) is bonded in a 9-coordinate geometry to two equivalent Ca(1), two equivalent Ca(4), one Ir(4), one Ir(7), and three equivalent Ir(1) atoms. In the second P site, P(2) is bonded in a 9-coordinate geometry to two equivalent Ca(2), two equivalent Ca(3), one Ir(2), one Ir(8), and three equivalent Ir(3) atoms. In the third P site, P(3) is bonded in a 8-coordinate geometry to two equivalent Ca(3), two equivalent Ca(4), one Ir(3), one Ir(6), and two equivalent Ir(8) atoms. In the fourth P site, P(4) is bonded in a 8-coordinate geometry to two equivalent Ca(1), two equivalent Ca(3), one Ir(1), one Ir(2), and two equivalent Ir(4) atoms. In the fifth P site, P(5) is bonded in a 7-coordinate geometry to one Ca(3), two equivalent Ca(4), one Ir(4), and three equivalent Ir(6) atoms. In the sixth P site, P(6) is bonded in a 7-coordinate geometry to one Ca(4), two equivalent Ca(2), one Ir(5), one Ir(8), and two equivalent Ir(7) atoms. In the seventh P site, P(7) is bonded in a 9-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one Ir(2), one Ir(7), and three equivalent Ir(5) atoms.
Ca4Ir8P7 crystallizes in the monoclinic P2_1/m space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 15-coordinate geometry to one Ir(4), one Ir(5), two equivalent Ir(2), two equivalent Ir(7), three equivalent Ir(1), two equivalent P(1), two equivalent P(4), and two equivalent P(7) atoms. The Ca(1)-Ir(4) bond length is 3.06 Å. The Ca(1)-Ir(5) bond length is 3.06 Å. Both Ca(1)-Ir(2) bond lengths are 3.12 Å. Both Ca(1)-Ir(7) bond lengths are 3.14 Å. There is one shorter (3.16 Å) and two longer (3.22 Å) Ca(1)-Ir(1) bond lengths. Both Ca(1)-P(1) bond lengths are 3.06 Å. Both Ca(1)-P(4) bond lengths are 2.99 Å. Both Ca(1)-P(7) bond lengths are 2.97 Å. In the second Ca site, Ca(2) is bonded in a 15-coordinate geometry to one Ir(3), one Ir(7), two equivalent Ir(2), two equivalent Ir(8), three equivalent Ir(5), two equivalent P(2), two equivalent P(6), and two equivalent P(7) atoms. The Ca(2)-Ir(3) bond length is 3.14 Å. The Ca(2)-Ir(7) bond length is 3.21 Å. Both Ca(2)-Ir(2) bond lengths are 3.02 Å. Both Ca(2)-Ir(8) bond lengths are 3.16 Å. There is one shorter (3.13 Å) and two longer (3.28 Å) Ca(2)-Ir(5) bond lengths. Both Ca(2)-P(2) bond lengths are 3.02 Å. Both Ca(2)-P(6) bond lengths are 3.01 Å. Both Ca(2)-P(7) bond lengths are 3.02 Å. In the third Ca site, Ca(3) is bonded in a 14-coordinate geometry to one Ir(4), one Ir(8), two equivalent Ir(2), three equivalent Ir(3), one P(5), two equivalent P(2), two equivalent P(3), and two equivalent P(4) atoms. The Ca(3)-Ir(4) bond length is 3.27 Å. The Ca(3)-Ir(8) bond length is 3.21 Å. Both Ca(3)-Ir(2) bond lengths are 3.10 Å. There are two shorter (3.30 Å) and one longer (3.36 Å) Ca(3)-Ir(3) bond length. The Ca(3)-P(5) bond length is 2.87 Å. Both Ca(3)-P(2) bond lengths are 3.13 Å. Both Ca(3)-P(3) bond lengths are 3.18 Å. Both Ca(3)-P(4) bond lengths are 3.26 Å. In the fourth Ca site, Ca(4) is bonded in a 1-coordinate geometry to one Ir(1), one Ir(8), two equivalent Ir(4), one P(6), two equivalent P(1), two equivalent P(3), and two equivalent P(5) atoms. The Ca(4)-Ir(1) bond length is 3.40 Å. The Ca(4)-Ir(8) bond length is 3.21 Å. Both Ca(4)-Ir(4) bond lengths are 3.08 Å. The Ca(4)-P(6) bond length is 2.74 Å. Both Ca(4)-P(1) bond lengths are 3.35 Å. Both Ca(4)-P(3) bond lengths are 3.40 Å. Both Ca(4)-P(5) bond lengths are 3.01 Å. There are eight inequivalent Ir sites. In the first Ir site, Ir(1) is bonded to one Ca(4), three equivalent Ca(1), two equivalent Ir(1), two equivalent Ir(4), one P(4), and three equivalent P(1) atoms to form distorted face-sharing IrCa4P4Ir4 cuboctahedra. Both Ir(1)-Ir(1) bond lengths are 2.77 Å. Both Ir(1)-Ir(4) bond lengths are 2.80 Å. The Ir(1)-P(4) bond length is 2.38 Å. There are two shorter (2.40 Å) and one longer (2.47 Å) Ir(1)-P(1) bond length. In the second Ir site, Ir(2) is bonded in a 9-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), two equivalent Ca(3), one P(2), one P(4), and one P(7) atom. The Ir(2)-P(2) bond length is 2.34 Å. The Ir(2)-P(4) bond length is 2.27 Å. The Ir(2)-P(7) bond length is 2.35 Å. In the third Ir site, Ir(3) is bonded to one Ca(2), three equivalent Ca(3), two equivalent Ir(3), two equivalent Ir(8), one P(3), and three equivalent P(2) atoms to form distorted face-sharing IrCa4P4Ir4 cuboctahedra. Both Ir(3)-Ir(3) bond lengths are 2.81 Å. Both Ir(3)-Ir(8) bond lengths are 2.78 Å. The Ir(3)-P(3) bond length is 2.45 Å. There is one shorter (2.38 Å) and two longer (2.40 Å) Ir(3)-P(2) bond lengths. In the fourth Ir site, Ir(4) is bonded in a 10-coordinate geometry to one Ca(1), one Ca(3), two equivalent Ca(4), two equivalent Ir(1), one P(1), one P(5), and two equivalent P(4) atoms. The Ir(4)-P(1) bond length is 2.42 Å. The Ir(4)-P(5) bond length is 2.30 Å. Both Ir(4)-P(4) bond lengths are 2.31 Å. In the fifth Ir site, Ir(5) is bonded in a 12-coordinate geometry to one Ca(1), three equivalent Ca(2), two equivalent Ir(5), two equivalent Ir(7), one P(6), and three equivalent P(7) atoms. Both Ir(5)-Ir(5) bond lengths are 2.78 Å. Both Ir(5)-Ir(7) bond lengths are 2.83 Å. The Ir(5)-P(6) bond length is 2.35 Å. There are two shorter (2.37 Å) and one longer (2.46 Å) Ir(5)-P(7) bond length. In the sixth Ir site, Ir(6) is bonded in a 4-coordinate geometry to one P(3) and three equivalent P(5) atoms. The Ir(6)-P(3) bond length is 2.29 Å. There is one shorter (2.34 Å) and two longer (2.35 Å) Ir(6)-P(5) bond lengths. In the seventh Ir site, Ir(7) is bonded in a 7-coordinate geometry to one Ca(2), two equivalent Ca(1), two equivalent Ir(5), one P(1), one P(7), and two equivalent P(6) atoms. The Ir(7)-P(1) bond length is 2.31 Å. The Ir(7)-P(7) bond length is 2.44 Å. Both Ir(7)-P(6) bond lengths are 2.35 Å. In the eighth Ir site, Ir(8) is bonded in a 10-coordinate geometry to one Ca(3), one Ca(4), two equivalent Ca(2), two equivalent Ir(3), one P(2), one P(6), and two equivalent P(3) atoms. The Ir(8)-P(2) bond length is 2.42 Å. The Ir(8)-P(6) bond length is 2.31 Å. Both Ir(8)-P(3) bond lengths are 2.31 Å. There are seven inequivalent P sites. In the first P site, P(1) is bonded in a 9-coordinate geometry to two equivalent Ca(1), two equivalent Ca(4), one Ir(4), one Ir(7), and three equivalent Ir(1) atoms. In the second P site, P(2) is bonded in a 9-coordinate geometry to two equivalent Ca(2), two equivalent Ca(3), one Ir(2), one Ir(8), and three equivalent Ir(3) atoms. In the third P site, P(3) is bonded in a 8-coordinate geometry to two equivalent Ca(3), two equivalent Ca(4), one Ir(3), one Ir(6), and two equivalent Ir(8) atoms. In the fourth P site, P(4) is bonded in a 8-coordinate geometry to two equivalent Ca(1), two equivalent Ca(3), one Ir(1), one Ir(2), and two equivalent Ir(4) atoms. In the fifth P site, P(5) is bonded in a 7-coordinate geometry to one Ca(3), two equivalent Ca(4), one Ir(4), and three equivalent Ir(6) atoms. In the sixth P site, P(6) is bonded in a 7-coordinate geometry to one Ca(4), two equivalent Ca(2), one Ir(5), one Ir(8), and two equivalent Ir(7) atoms. In the seventh P site, P(7) is bonded in a 9-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one Ir(2), one Ir(7), and three equivalent Ir(5) atoms.