Ca5(PdP)6 crystallizes in the orthorhombic Pmma space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one Pd(2), one Pd(3), one Pd(4), two equivalent Pd(1), one P(1), two equivalent P(2), two equivalent P(4), and two equivalent P(6) atoms to form CaP7Pd5 cuboctahedra that share edges with four equivalent Ca(3)P6Pd6 cuboctahedra, edges with four equivalent Ca(1)P7Pd5 cuboctahedra, faces with two equivalent Ca(3)P6Pd6 cuboctahedra, and faces with four equivalent Ca(1)P7Pd5 cuboctahedra. In the second Ca site, Ca(2) is bonded in a 14-coordinate geometry to two equivalent Pd(2), two equivalent Pd(4), two equivalent Pd(5), two equivalent Pd(6), one P(2), one P(4), two equivalent P(3), and two equivalent P(5) atoms. In the third Ca site, Ca(3) is bonded to two equivalent Pd(1), four equivalent Pd(3), two equivalent P(6), and four equivalent P(1) atoms to form CaP6Pd6 cuboctahedra that share edges with four equivalent Ca(3)P6Pd6 cuboctahedra, edges with eight equivalent Ca(1)P7Pd5 cuboctahedra, faces with four equivalent Ca(3)P6Pd6 cuboctahedra, and faces with four equivalent Ca(1)P7Pd5 cuboctahedra. There are six inequivalent Pd sites. In the first Pd site, Pd(1) is bonded in a 9-coordinate geometry to two equivalent Ca(3), four equivalent Ca(1), one P(4), and two equivalent P(1) atoms. In the second Pd site, Pd(2) is bonded in a 9-coordinate geometry to two equivalent Ca(1), four equivalent Ca(2), one P(5), and two equivalent P(4) atoms. In the third Pd site, Pd(3) is bonded in a 9-coordinate geometry to two equivalent Ca(1), four equivalent Ca(3), one P(1), and two equivalent P(6) atoms. In the fourth Pd site, Pd(4) is bonded in a 9-coordinate geometry to two equivalent Ca(1), four equivalent Ca(2), one P(3), and two equivalent P(2) atoms. In the fifth Pd site, Pd(5) is bonded to four equivalent Ca(2), four equivalent Pd(6), two equivalent P(3), and two equivalent P(5) atoms to form a mixture of distorted corner and face-sharing PdCa4P4Pd4 cuboctahedra. In the sixth Pd site, Pd(6) is bonded to four equivalent Ca(2), four equivalent Pd(5), two equivalent P(3), and two equivalent P(5) atoms to form a mixture of distorted corner and face-sharing PdCa4P4Pd4 cuboctahedra. There are six inequivalent P sites. In the first P site, P(1) is bonded in a 9-coordinate geometry to two equivalent Ca(1), four equivalent Ca(3), one Pd(3), and two equivalent Pd(1) atoms. In the second P site, P(2) is bonded in a 9-coordinate geometry to two equivalent Ca(2), four equivalent Ca(1), two equivalent Pd(4), and one P(6) atom. In the third P site, P(3) is bonded in a 9-coordinate geometry to four equivalent Ca(2), one Pd(4), two equivalent Pd(5), and two equivalent Pd(6) atoms. In the fourth P site, P(4) is bonded in a 9-coordinate geometry to two equivalent Ca(2), four equivalent Ca(1), one Pd(1), and two equivalent Pd(2) atoms. In the fifth P site, P(5) is bonded in a 9-coordinate geometry to four equivalent Ca(2), one Pd(2), two equivalent Pd(5), and two equivalent Pd(6) atoms. In the sixth P site, P(6) is bonded in a 9-coordinate geometry to two equivalent Ca(3), four equivalent Ca(1), two equivalent Pd(3), and one P(2) atom.
Ca5(PdP)6 crystallizes in the orthorhombic Pmma space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one Pd(2), one Pd(3), one Pd(4), two equivalent Pd(1), one P(1), two equivalent P(2), two equivalent P(4), and two equivalent P(6) atoms to form CaP7Pd5 cuboctahedra that share edges with four equivalent Ca(3)P6Pd6 cuboctahedra, edges with four equivalent Ca(1)P7Pd5 cuboctahedra, faces with two equivalent Ca(3)P6Pd6 cuboctahedra, and faces with four equivalent Ca(1)P7Pd5 cuboctahedra. The Ca(1)-Pd(2) bond length is 3.09 Å. The Ca(1)-Pd(3) bond length is 3.05 Å. The Ca(1)-Pd(4) bond length is 3.11 Å. Both Ca(1)-Pd(1) bond lengths are 3.09 Å. The Ca(1)-P(1) bond length is 3.10 Å. Both Ca(1)-P(2) bond lengths are 3.16 Å. Both Ca(1)-P(4) bond lengths are 3.10 Å. Both Ca(1)-P(6) bond lengths are 3.13 Å. In the second Ca site, Ca(2) is bonded in a 14-coordinate geometry to two equivalent Pd(2), two equivalent Pd(4), two equivalent Pd(5), two equivalent Pd(6), one P(2), one P(4), two equivalent P(3), and two equivalent P(5) atoms. Both Ca(2)-Pd(2) bond lengths are 3.14 Å. Both Ca(2)-Pd(4) bond lengths are 3.19 Å. There is one shorter (3.21 Å) and one longer (3.23 Å) Ca(2)-Pd(5) bond length. Both Ca(2)-Pd(6) bond lengths are 3.21 Å. The Ca(2)-P(2) bond length is 3.20 Å. The Ca(2)-P(4) bond length is 3.14 Å. Both Ca(2)-P(3) bond lengths are 3.09 Å. Both Ca(2)-P(5) bond lengths are 3.09 Å. In the third Ca site, Ca(3) is bonded to two equivalent Pd(1), four equivalent Pd(3), two equivalent P(6), and four equivalent P(1) atoms to form CaP6Pd6 cuboctahedra that share edges with four equivalent Ca(3)P6Pd6 cuboctahedra, edges with eight equivalent Ca(1)P7Pd5 cuboctahedra, faces with four equivalent Ca(3)P6Pd6 cuboctahedra, and faces with four equivalent Ca(1)P7Pd5 cuboctahedra. Both Ca(3)-Pd(1) bond lengths are 3.09 Å. All Ca(3)-Pd(3) bond lengths are 3.17 Å. Both Ca(3)-P(6) bond lengths are 3.18 Å. All Ca(3)-P(1) bond lengths are 3.10 Å. There are six inequivalent Pd sites. In the first Pd site, Pd(1) is bonded in a 9-coordinate geometry to two equivalent Ca(3), four equivalent Ca(1), one P(4), and two equivalent P(1) atoms. The Pd(1)-P(4) bond length is 2.38 Å. Both Pd(1)-P(1) bond lengths are 2.37 Å. In the second Pd site, Pd(2) is bonded in a 9-coordinate geometry to two equivalent Ca(1), four equivalent Ca(2), one P(5), and two equivalent P(4) atoms. The Pd(2)-P(5) bond length is 2.32 Å. Both Pd(2)-P(4) bond lengths are 2.35 Å. In the third Pd site, Pd(3) is bonded in a 9-coordinate geometry to two equivalent Ca(1), four equivalent Ca(3), one P(1), and two equivalent P(6) atoms. The Pd(3)-P(1) bond length is 2.39 Å. Both Pd(3)-P(6) bond lengths are 2.34 Å. In the fourth Pd site, Pd(4) is bonded in a 9-coordinate geometry to two equivalent Ca(1), four equivalent Ca(2), one P(3), and two equivalent P(2) atoms. The Pd(4)-P(3) bond length is 2.35 Å. Both Pd(4)-P(2) bond lengths are 2.33 Å. In the fifth Pd site, Pd(5) is bonded to four equivalent Ca(2), four equivalent Pd(6), two equivalent P(3), and two equivalent P(5) atoms to form a mixture of distorted corner and face-sharing PdCa4P4Pd4 cuboctahedra. All Pd(5)-Pd(6) bond lengths are 2.90 Å. Both Pd(5)-P(3) bond lengths are 2.48 Å. Both Pd(5)-P(5) bond lengths are 2.47 Å. In the sixth Pd site, Pd(6) is bonded to four equivalent Ca(2), four equivalent Pd(5), two equivalent P(3), and two equivalent P(5) atoms to form a mixture of distorted corner and face-sharing PdCa4P4Pd4 cuboctahedra. Both Pd(6)-P(3) bond lengths are 2.51 Å. Both Pd(6)-P(5) bond lengths are 2.47 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded in a 9-coordinate geometry to two equivalent Ca(1), four equivalent Ca(3), one Pd(3), and two equivalent Pd(1) atoms. In the second P site, P(2) is bonded in a 9-coordinate geometry to two equivalent Ca(2), four equivalent Ca(1), two equivalent Pd(4), and one P(6) atom. The P(2)-P(6) bond length is 2.20 Å. In the third P site, P(3) is bonded in a 9-coordinate geometry to four equivalent Ca(2), one Pd(4), two equivalent Pd(5), and two equivalent Pd(6) atoms. In the fourth P site, P(4) is bonded in a 9-coordinate geometry to two equivalent Ca(2), four equivalent Ca(1), one Pd(1), and two equivalent Pd(2) atoms. In the fifth P site, P(5) is bonded in a 9-coordinate geometry to four equivalent Ca(2), one Pd(2), two equivalent Pd(5), and two equivalent Pd(6) atoms. In the sixth P site, P(6) is bonded in a 9-coordinate geometry to two equivalent Ca(3), four equivalent Ca(1), two equivalent Pd(3), and one P(2) atom.