Ca2Au10Bi3 crystallizes in the trigonal R3m space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 16-coordinate geometry to three equivalent Au(2), three equivalent Au(6), six equivalent Au(1), one Bi(4), and three equivalent Bi(5) atoms. In the second Ca site, Ca(2) is bonded in a 16-coordinate geometry to three equivalent Au(3), three equivalent Au(7), six equivalent Au(2), one Bi(5), and three equivalent Bi(3) atoms. In the third Ca site, Ca(3) is bonded in a 16-coordinate geometry to three equivalent Au(4), three equivalent Au(8), six equivalent Au(3), one Bi(3), and three equivalent Bi(2) atoms. In the fourth Ca site, Ca(4) is bonded in a 16-coordinate geometry to three equivalent Au(5), three equivalent Au(9), six equivalent Au(4), one Bi(2), and three equivalent Bi(1) atoms. There are ten inequivalent Au sites. In the first Au site, Au(1) is bonded to two equivalent Ca(1), one Au(10), one Au(6), four equivalent Au(1), one Bi(5), one Bi(6), and two equivalent Bi(4) atoms to form AuCa2Bi4Au6 cuboctahedra that share corners with two equivalent Au(10)Bi6Au6 cuboctahedra, corners with two equivalent Au(6)Ca3Bi3Au6 cuboctahedra, corners with four equivalent Au(1)Ca2Bi4Au6 cuboctahedra, corners with five equivalent Au(2)Ca3Bi3Au6 cuboctahedra, corners with five equivalent Au(5)CaBi5Au6 cuboctahedra, edges with two equivalent Au(1)Ca2Bi4Au6 cuboctahedra, edges with two equivalent Au(2)Ca3Bi3Au6 cuboctahedra, edges with two equivalent Au(5)CaBi5Au6 cuboctahedra, faces with two equivalent Au(2)Ca3Bi3Au6 cuboctahedra, faces with two equivalent Au(5)CaBi5Au6 cuboctahedra, faces with three equivalent Au(10)Bi6Au6 cuboctahedra, faces with three equivalent Au(6)Ca3Bi3Au6 cuboctahedra, and faces with eight equivalent Au(1)Ca2Bi4Au6 cuboctahedra. In the second Au site, Au(2) is bonded to one Ca(1), two equivalent Ca(2), one Au(6), one Au(7), four equivalent Au(2), one Bi(3), and two equivalent Bi(5) atoms to form AuCa3Bi3Au6 cuboctahedra that share corners with two equivalent Au(6)Ca3Bi3Au6 cuboctahedra, corners with two equivalent Au(7)Ca3Bi3Au6 cuboctahedra, corners with four equivalent Au(2)Ca3Bi3Au6 cuboctahedra, corners with five equivalent Au(1)Ca2Bi4Au6 cuboctahedra, corners with five equivalent Au(3)Ca3Bi3Au6 cuboctahedra, edges with two equivalent Au(1)Ca2Bi4Au6 cuboctahedra, edges with two equivalent Au(2)Ca3Bi3Au6 cuboctahedra, edges with two equivalent Au(3)Ca3Bi3Au6 cuboctahedra, faces with two equivalent Au(1)Ca2Bi4Au6 cuboctahedra, faces with two equivalent Au(3)Ca3Bi3Au6 cuboctahedra, faces with three equivalent Au(6)Ca3Bi3Au6 cuboctahedra, faces with three equivalent Au(7)Ca3Bi3Au6 cuboctahedra, and faces with eight equivalent Au(2)Ca3Bi3Au6 cuboctahedra. In the third Au site, Au(3) is bonded to one Ca(2), two equivalent Ca(3), one Au(7), one Au(8), four equivalent Au(3), one Bi(2), and two equivalent Bi(3) atoms to form a mixture of face, corner, and edge-sharing AuCa3Bi3Au6 cuboctahedra. In the fourth Au site, Au(4) is bonded to one Ca(3), two equivalent Ca(4), one Au(8), one Au(9), four equivalent Au(4), one Bi(1), and two equivalent Bi(2) atoms to form AuCa3Bi3Au6 cuboctahedra that share corners with two equivalent Au(8)Ca3Bi3Au6 cuboctahedra, corners with two equivalent Au(9)Ca3Bi3Au6 cuboctahedra, corners with four equivalent Au(4)Ca3Bi3Au6 cuboctahedra, corners with five equivalent Au(3)Ca3Bi3Au6 cuboctahedra, corners with five equivalent Au(5)CaBi5Au6 cuboctahedra, edges with two equivalent Au(3)Ca3Bi3Au6 cuboctahedra, edges with two equivalent Au(4)Ca3Bi3Au6 cuboctahedra, edges with two equivalent Au(5)CaBi5Au6 cuboctahedra, faces with two equivalent Au(3)Ca3Bi3Au6 cuboctahedra, faces with two equivalent Au(5)CaBi5Au6 cuboctahedra, faces with three equivalent Au(8)Ca3Bi3Au6 cuboctahedra, faces with three equivalent Au(9)Ca3Bi3Au6 cuboctahedra, and faces with eight equivalent Au(4)Ca3Bi3Au6 cuboctahedra. In the fifth Au site, Au(5) is bonded to one Ca(4), one Au(10), one Au(9), four equivalent Au(5), one Bi(4), two equivalent Bi(1), and two equivalent Bi(6) atoms to form AuCaBi5Au6 cuboctahedra that share corners with two equivalent Au(10)Bi6Au6 cuboctahedra, corners with two equivalent Au(9)Ca3Bi3Au6 cuboctahedra, corners with four equivalent Au(5)CaBi5Au6 cuboctahedra, corners with five equivalent Au(1)Ca2Bi4Au6 cuboctahedra, corners with five equivalent Au(4)Ca3Bi3Au6 cuboctahedra, edges with two equivalent Au(1)Ca2Bi4Au6 cuboctahedra, edges with two equivalent Au(4)Ca3Bi3Au6 cuboctahedra, edges with two equivalent Au(5)CaBi5Au6 cuboctahedra, faces with two equivalent Au(1)Ca2Bi4Au6 cuboctahedra, faces with two equivalent Au(4)Ca3Bi3Au6 cuboctahedra, faces with three equivalent Au(10)Bi6Au6 cuboctahedra, faces with three equivalent Au(9)Ca3Bi3Au6 cuboctahedra, and faces with eight equivalent Au(5)CaBi5Au6 cuboctahedra. In the sixth Au site, Au(6) is bonded to three equivalent Ca(1), three equivalent Au(1), three equivalent Au(2), and three equivalent Bi(5) atoms to form AuCa3Bi3Au6 cuboctahedra that share corners with three equivalent Au(10)Bi6Au6 cuboctahedra, corners with three equivalent Au(7)Ca3Bi3Au6 cuboctahedra, corners with six equivalent Au(1)Ca2Bi4Au6 cuboctahedra, corners with six equivalent Au(2)Ca3Bi3Au6 cuboctahedra, edges with six equivalent Au(6)Ca3Bi3Au6 cuboctahedra, faces with nine equivalent Au(1)Ca2Bi4Au6 cuboctahedra, and faces with nine equivalent Au(2)Ca3Bi3Au6 cuboctahedra. In the seventh Au site, Au(7) is bonded to three equivalent Ca(2), three equivalent Au(2), three equivalent Au(3), and three equivalent Bi(3) atoms to form a mixture of face, corner, and edge-sharing AuCa3Bi3Au6 cuboctahedra. In the eighth Au site, Au(8) is bonded to three equivalent Ca(3), three equivalent Au(3), three equivalent Au(4), and three equivalent Bi(2) atoms to form a mixture of face, corner, and edge-sharing AuCa3Bi3Au6 cuboctahedra. In the ninth Au site, Au(9) is bonded to three equivalent Ca(4), three equivalent Au(4), three equivalent Au(5), and three equivalent Bi(1) atoms to form AuCa3Bi3Au6 cuboctahedra that share corners with three equivalent Au(10)Bi6Au6 cuboctahedra, corners with three equivalent Au(8)Ca3Bi3Au6 cuboctahedra, corners with six equivalent Au(4)Ca3Bi3Au6 cuboctahedra, corners with six equivalent Au(5)CaBi5Au6 cuboctahedra, edges with six equivalent Au(9)Ca3Bi3Au6 cuboctahedra, faces with nine equivalent Au(4)Ca3Bi3Au6 cuboctahedra, and faces with nine equivalent Au(5)CaBi5Au6 cuboctahedra. In the tenth Au site, Au(10) is bonded to three equivalent Au(1), three equivalent Au(5), three equivalent Bi(4), and three equivalent Bi(6) atoms to form AuBi6Au6 cuboctahedra that share corners with three equivalent Au(6)Ca3Bi3Au6 cuboctahedra, corners with three equivalent Au(9)Ca3Bi3Au6 cuboctahedra, corners with six equivalent Au(1)Ca2Bi4Au6 cuboctahedra, corners with six equivalent Au(5)CaBi5Au6 cuboctahedra, edges with six equivalent Au(10)Bi6Au6 cuboctahedra, faces with nine equivalent Au(1)Ca2Bi4Au6 cuboctahedra, and faces with nine equivalent Au(5)CaBi5Au6 cuboctahedra. There are six inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 16-coordinate geometry to three equivalent Ca(4), three equivalent Au(4), three equivalent Au(9), six equivalent Au(5), and one Bi(6) atom. In the second Bi site, Bi(2) is bonded in a 16-coordinate geometry to one Ca(4), three equivalent Ca(3), three equivalent Au(3), three equivalent Au(8), and six equivalent Au(4) atoms. In the third Bi site, Bi(3) is bonded in a 16-coordinate geometry to one Ca(3), three equivalent Ca(2), three equivalent Au(2), three equivalent Au(7), and six equivalent Au(3) atoms. In the fourth Bi site, Bi(4) is bonded in a 16-coordinate geometry to one Ca(1), three equivalent Au(10), three equivalent Au(5), six equivalent Au(1), and three equivalent Bi(6) atoms. In the fifth Bi site, Bi(5) is bonded in a 16-coordinate geometry to one Ca(2), three equivalent Ca(1), three equivalent Au(1), three equivalent Au(6), and six equivalent Au(2) atoms. In the sixth Bi site, Bi(6) is bonded in a 16-coordinate geometry to three equivalent Au(1), three equivalent Au(10), six equivalent Au(5), one Bi(1), and three equivalent Bi(4) atoms.
Ca2Au10Bi3 crystallizes in the trigonal R3m space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 16-coordinate geometry to three equivalent Au(2), three equivalent Au(6), six equivalent Au(1), one Bi(4), and three equivalent Bi(5) atoms. All Ca(1)-Au(2) bond lengths are 3.36 Å. All Ca(1)-Au(6) bond lengths are 3.34 Å. All Ca(1)-Au(1) bond lengths are 3.34 Å. The Ca(1)-Bi(4) bond length is 3.61 Å. All Ca(1)-Bi(5) bond lengths are 3.49 Å. In the second Ca site, Ca(2) is bonded in a 16-coordinate geometry to three equivalent Au(3), three equivalent Au(7), six equivalent Au(2), one Bi(5), and three equivalent Bi(3) atoms. All Ca(2)-Au(3) bond lengths are 3.37 Å. All Ca(2)-Au(7) bond lengths are 3.34 Å. All Ca(2)-Au(2) bond lengths are 3.35 Å. The Ca(2)-Bi(5) bond length is 3.51 Å. All Ca(2)-Bi(3) bond lengths are 3.50 Å. In the third Ca site, Ca(3) is bonded in a 16-coordinate geometry to three equivalent Au(4), three equivalent Au(8), six equivalent Au(3), one Bi(3), and three equivalent Bi(2) atoms. All Ca(3)-Au(4) bond lengths are 3.40 Å. All Ca(3)-Au(8) bond lengths are 3.34 Å. All Ca(3)-Au(3) bond lengths are 3.34 Å. The Ca(3)-Bi(3) bond length is 3.49 Å. All Ca(3)-Bi(2) bond lengths are 3.49 Å. In the fourth Ca site, Ca(4) is bonded in a 16-coordinate geometry to three equivalent Au(5), three equivalent Au(9), six equivalent Au(4), one Bi(2), and three equivalent Bi(1) atoms. All Ca(4)-Au(5) bond lengths are 3.37 Å. All Ca(4)-Au(9) bond lengths are 3.35 Å. All Ca(4)-Au(4) bond lengths are 3.32 Å. The Ca(4)-Bi(2) bond length is 3.51 Å. All Ca(4)-Bi(1) bond lengths are 3.54 Å. There are ten inequivalent Au sites. In the first Au site, Au(1) is bonded to two equivalent Ca(1), one Au(10), one Au(6), four equivalent Au(1), one Bi(5), one Bi(6), and two equivalent Bi(4) atoms to form AuCa2Bi4Au6 cuboctahedra that share corners with two equivalent Au(10)Bi6Au6 cuboctahedra, corners with two equivalent Au(6)Ca3Bi3Au6 cuboctahedra, corners with four equivalent Au(1)Ca2Bi4Au6 cuboctahedra, corners with five equivalent Au(2)Ca3Bi3Au6 cuboctahedra, corners with five equivalent Au(5)CaBi5Au6 cuboctahedra, edges with two equivalent Au(1)Ca2Bi4Au6 cuboctahedra, edges with two equivalent Au(2)Ca3Bi3Au6 cuboctahedra, edges with two equivalent Au(5)CaBi5Au6 cuboctahedra, faces with two equivalent Au(2)Ca3Bi3Au6 cuboctahedra, faces with two equivalent Au(5)CaBi5Au6 cuboctahedra, faces with three equivalent Au(10)Bi6Au6 cuboctahedra, faces with three equivalent Au(6)Ca3Bi3Au6 cuboctahedra, and faces with eight equivalent Au(1)Ca2Bi4Au6 cuboctahedra. The Au(1)-Au(10) bond length is 2.88 Å. The Au(1)-Au(6) bond length is 2.85 Å. All Au(1)-Au(1) bond lengths are 2.85 Å. The Au(1)-Bi(5) bond length is 3.35 Å. The Au(1)-Bi(6) bond length is 3.37 Å. Both Au(1)-Bi(4) bond lengths are 3.40 Å. In the second Au site, Au(2) is bonded to one Ca(1), two equivalent Ca(2), one Au(6), one Au(7), four equivalent Au(2), one Bi(3), and two equivalent Bi(5) atoms to form AuCa3Bi3Au6 cuboctahedra that share corners with two equivalent Au(6)Ca3Bi3Au6 cuboctahedra, corners with two equivalent Au(7)Ca3Bi3Au6 cuboctahedra, corners with four equivalent Au(2)Ca3Bi3Au6 cuboctahedra, corners with five equivalent Au(1)Ca2Bi4Au6 cuboctahedra, corners with five equivalent Au(3)Ca3Bi3Au6 cuboctahedra, edges with two equivalent Au(1)Ca2Bi4Au6 cuboctahedra, edges with two equivalent Au(2)Ca3Bi3Au6 cuboctahedra, edges with two equivalent Au(3)Ca3Bi3Au6 cuboctahedra, faces with two equivalent Au(1)Ca2Bi4Au6 cuboctahedra, faces with two equivalent Au(3)Ca3Bi3Au6 cuboctahedra, faces with three equivalent Au(6)Ca3Bi3Au6 cuboctahedra, faces with three equivalent Au(7)Ca3Bi3Au6 cuboctahedra, and faces with eight equivalent Au(2)Ca3Bi3Au6 cuboctahedra. The Au(2)-Au(6) bond length is 2.87 Å. The Au(2)-Au(7) bond length is 2.86 Å. There are two shorter (2.84 Å) and two longer (2.86 Å) Au(2)-Au(2) bond lengths. The Au(2)-Bi(3) bond length is 3.39 Å. Both Au(2)-Bi(5) bond lengths are 3.35 Å. In the third Au site, Au(3) is bonded to one Ca(2), two equivalent Ca(3), one Au(7), one Au(8), four equivalent Au(3), one Bi(2), and two equivalent Bi(3) atoms to form a mixture of face, corner, and edge-sharing AuCa3Bi3Au6 cuboctahedra. The Au(3)-Au(7) bond length is 2.88 Å. The Au(3)-Au(8) bond length is 2.86 Å. There are two shorter (2.84 Å) and two longer (2.86 Å) Au(3)-Au(3) bond lengths. The Au(3)-Bi(2) bond length is 3.35 Å. Both Au(3)-Bi(3) bond lengths are 3.34 Å. In the fourth Au site, Au(4) is bonded to one Ca(3), two equivalent Ca(4), one Au(8), one Au(9), four equivalent Au(4), one Bi(1), and two equivalent Bi(2) atoms to form AuCa3Bi3Au6 cuboctahedra that share corners with two equivalent Au(8)Ca3Bi3Au6 cuboctahedra, corners with two equivalent Au(9)Ca3Bi3Au6 cuboctahedra, corners with four equivalent Au(4)Ca3Bi3Au6 cuboctahedra, corners with five equivalent Au(3)Ca3Bi3Au6 cuboctahedra, corners with five equivalent Au(5)CaBi5Au6 cuboctahedra, edges with two equivalent Au(3)Ca3Bi3Au6 cuboctahedra, edges with two equivalent Au(4)Ca3Bi3Au6 cuboctahedra, edges with two equivalent Au(5)CaBi5Au6 cuboctahedra, faces with two equivalent Au(3)Ca3Bi3Au6 cuboctahedra, faces with two equivalent Au(5)CaBi5Au6 cuboctahedra, faces with three equivalent Au(8)Ca3Bi3Au6 cuboctahedra, faces with three equivalent Au(9)Ca3Bi3Au6 cuboctahedra, and faces with eight equivalent Au(4)Ca3Bi3Au6 cuboctahedra. The Au(4)-Au(8) bond length is 2.89 Å. The Au(4)-Au(9) bond length is 2.85 Å. There are two shorter (2.84 Å) and two longer (2.85 Å) Au(4)-Au(4) bond lengths. The Au(4)-Bi(1) bond length is 3.44 Å. Both Au(4)-Bi(2) bond lengths are 3.37 Å. In the fifth Au site, Au(5) is bonded to one Ca(4), one Au(10), one Au(9), four equivalent Au(5), one Bi(4), two equivalent Bi(1), and two equivalent Bi(6) atoms to form AuCaBi5Au6 cuboctahedra that share corners with two equivalent Au(10)Bi6Au6 cuboctahedra, corners with two equivalent Au(9)Ca3Bi3Au6 cuboctahedra, corners with four equivalent Au(5)CaBi5Au6 cuboctahedra, corners with five equivalent Au(1)Ca2Bi4Au6 cuboctahedra, corners with five equivalent Au(4)Ca3Bi3Au6 cuboctahedra, edges with two equivalent Au(1)Ca2Bi4Au6 cuboctahedra, edges with two equivalent Au(4)Ca3Bi3Au6 cuboctahedra, edges with two equivalent Au(5)CaBi5Au6 cuboctahedra, faces with two equivalent Au(1)Ca2Bi4Au6 cuboctahedra, faces with two equivalent Au(4)Ca3Bi3Au6 cuboctahedra, faces with three equivalent Au(10)Bi6Au6 cuboctahedra, faces with three equivalent Au(9)Ca3Bi3Au6 cuboctahedra, and faces with eight equivalent Au(5)CaBi5Au6 cuboctahedra. The Au(5)-Au(10) bond length is 2.90 Å. The Au(5)-Au(9) bond length is 2.86 Å. There are two shorter (2.83 Å) and two longer (2.87 Å) Au(5)-Au(5) bond lengths. The Au(5)-Bi(4) bond length is 3.34 Å. Both Au(5)-Bi(1) bond lengths are 3.28 Å. Both Au(5)-Bi(6) bond lengths are 3.38 Å. In the sixth Au site, Au(6) is bonded to three equivalent Ca(1), three equivalent Au(1), three equivalent Au(2), and three equivalent Bi(5) atoms to form AuCa3Bi3Au6 cuboctahedra that share corners with three equivalent Au(10)Bi6Au6 cuboctahedra, corners with three equivalent Au(7)Ca3Bi3Au6 cuboctahedra, corners with six equivalent Au(1)Ca2Bi4Au6 cuboctahedra, corners with six equivalent Au(2)Ca3Bi3Au6 cuboctahedra, edges with six equivalent Au(6)Ca3Bi3Au6 cuboctahedra, faces with nine equivalent Au(1)Ca2Bi4Au6 cuboctahedra, and faces with nine equivalent Au(2)Ca3Bi3Au6 cuboctahedra. All Au(6)-Bi(5) bond lengths are 3.34 Å. In the seventh Au site, Au(7) is bonded to three equivalent Ca(2), three equivalent Au(2), three equivalent Au(3), and three equivalent Bi(3) atoms to form a mixture of face, corner, and edge-sharing AuCa3Bi3Au6 cuboctahedra. All Au(7)-Bi(3) bond lengths are 3.35 Å. In the eighth Au site, Au(8) is bonded to three equivalent Ca(3), three equivalent Au(3), three equivalent Au(4), and three equivalent Bi(2) atoms to form a mixture of face, corner, and edge-sharing AuCa3Bi3Au6 cuboctahedra. All Au(8)-Bi(2) bond lengths are 3.34 Å. In the ninth Au site, Au(9) is bonded to three equivalent Ca(4), three equivalent Au(4), three equivalent Au(5), and three equivalent Bi(1) atoms to form AuCa3Bi3Au6 cuboctahedra that share corners with three equivalent Au(10)Bi6Au6 cuboctahedra, corners with three equivalent Au(8)Ca3Bi3Au6 cuboctahedra, corners with six equivalent Au(4)Ca3Bi3Au6 cuboctahedra, corners with six equivalent Au(5)CaBi5Au6 cuboctahedra, edges with six equivalent Au(9)Ca3Bi3Au6 cuboctahedra, faces with nine equivalent Au(4)Ca3Bi3Au6 cuboctahedra, and faces with nine equivalent Au(5)CaBi5Au6 cuboctahedra. All Au(9)-Bi(1) bond lengths are 3.36 Å. In the tenth Au site, Au(10) is bonded to three equivalent Au(1), three equivalent Au(5), three equivalent Bi(4), and three equivalent Bi(6) atoms to form AuBi6Au6 cuboctahedra that share corners with three equivalent Au(6)Ca3Bi3Au6 cuboctahedra, corners with three equivalent Au(9)Ca3Bi3Au6 cuboctahedra, corners with six equivalent Au(1)Ca2Bi4Au6 cuboctahedra, corners with six equivalent Au(5)CaBi5Au6 cuboctahedra, edges with six equivalent Au(10)Bi6Au6 cuboctahedra, faces with nine equivalent Au(1)Ca2Bi4Au6 cuboctahedra, and faces with nine equivalent Au(5)CaBi5Au6 cuboctahedra. All Au(10)-Bi(4) bond lengths are 3.33 Å. All Au(10)-Bi(6) bond lengths are 3.34 Å. There are six inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 16-coordinate geometry to three equivalent Ca(4), three equivalent Au(4), three equivalent Au(9), six equivalent Au(5), and one Bi(6) atom. The Bi(1)-Bi(6) bond length is 3.45 Å. In the second Bi site, Bi(2) is bonded in a 16-coordinate geometry to one Ca(4), three equivalent Ca(3), three equivalent Au(3), three equivalent Au(8), and six equivalent Au(4) atoms. In the third Bi site, Bi(3) is bonded in a 16-coordinate geometry to one Ca(3), three equivalent Ca(2), three equivalent Au(2), three equivalent Au(7), and six equivalent Au(3) atoms. In the fourth Bi site, Bi(4) is bonded in a 16-coordinate geometry to one Ca(1), three equivalent Au(10), three equivalent Au(5), six equivalent Au(1), and three equivalent Bi(6) atoms. All Bi(4)-Bi(6) bond lengths are 3.46 Å. In the fifth Bi site, Bi(5) is bonded in a 16-coordinate geometry to one Ca(2), three equivalent Ca(1), three equivalent Au(1), three equivalent Au(6), and six equivalent Au(2) atoms. In the sixth Bi site, Bi(6) is bonded in a 16-coordinate geometry to three equivalent Au(1), three equivalent Au(10), six equivalent Au(5), one Bi(1), and three equivalent Bi(4) atoms.