Ca3Au14Bi crystallizes in the trigonal P3m1 space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 16-coordinate geometry to one Au(2), three equivalent Au(1), three equivalent Au(4), three equivalent Au(7), and six equivalent Au(5) atoms. In the second Ca site, Ca(2) is bonded in a 16-coordinate geometry to three equivalent Au(2), three equivalent Au(5), three equivalent Au(8), six equivalent Au(3), and one Bi(1) atom. In the third Ca site, Ca(3) is bonded in a 16-coordinate geometry to one Au(1), three equivalent Au(3), three equivalent Au(6), six equivalent Au(4), and three equivalent Bi(1) atoms. There are eight inequivalent Au sites. In the first Au site, Au(1) is bonded to one Ca(3), three equivalent Ca(1), three equivalent Au(5), three equivalent Au(7), and six equivalent Au(4) atoms to form distorted AuCa4Au12 tetrahedra that share corners with three equivalent Au(7)Ca3Au9 cuboctahedra, corners with three equivalent Au(3)Ca3Bi2Au7 cuboctahedra, faces with three equivalent Au(7)Ca3Au9 cuboctahedra, faces with three equivalent Au(6)Ca3Bi3Au6 cuboctahedra, faces with three equivalent Au(2)Ca4Au12 tetrahedra, and faces with six equivalent Au(1)Ca4Au12 tetrahedra. In the second Au site, Au(2) is bonded to one Ca(1), three equivalent Ca(2), three equivalent Au(3), three equivalent Au(8), and six equivalent Au(5) atoms to form distorted AuCa4Au12 tetrahedra that share corners with six equivalent Au(3)Ca3Bi2Au7 cuboctahedra,  a faceface with one Au(6)Ca3Bi3Au6 cuboctahedra, faces with three equivalent Au(7)Ca3Au9 cuboctahedra, faces with nine equivalent Au(3)Ca3Bi2Au7 cuboctahedra, faces with three equivalent Au(1)Ca4Au12 tetrahedra, and faces with six equivalent Au(2)Ca4Au12 tetrahedra. In the third Au site, Au(3) is bonded to one Ca(3), two equivalent Ca(2), one Au(2), one Au(6), one Au(8), four equivalent Au(3), and two equivalent Bi(1) atoms to form distorted AuCa3Bi2Au7 cuboctahedra that share corners with two equivalent Au(6)Ca3Bi3Au6 cuboctahedra, corners with four equivalent Au(3)Ca3Bi2Au7 cuboctahedra,  a cornercorner with one Au(1)Ca4Au12 tetrahedra, corners with two equivalent Au(2)Ca4Au12 tetrahedra, edges with two equivalent Au(3)Ca3Bi2Au7 cuboctahedra, faces with three equivalent Au(6)Ca3Bi3Au6 cuboctahedra, faces with eight equivalent Au(3)Ca3Bi2Au7 cuboctahedra, and faces with three equivalent Au(2)Ca4Au12 tetrahedra. In the fourth Au site, Au(4) is bonded in a 12-coordinate geometry to one Ca(1), two equivalent Ca(3), one Au(6), one Au(7), two equivalent Au(1), four equivalent Au(4), and one Bi(1) atom. In the fifth Au site, Au(5) is bonded in a 12-coordinate geometry to one Ca(2), two equivalent Ca(1), one Au(1), one Au(7), one Au(8), two equivalent Au(2), and four equivalent Au(5) atoms. In the sixth Au site, Au(6) is bonded to three equivalent Ca(3), three equivalent Au(3), three equivalent Au(4), and three equivalent Bi(1) atoms to form AuCa3Bi3Au6 cuboctahedra that share corners with three equivalent Au(7)Ca3Au9 cuboctahedra, corners with six equivalent Au(3)Ca3Bi2Au7 cuboctahedra, edges with six equivalent Au(6)Ca3Bi3Au6 cuboctahedra, faces with nine equivalent Au(3)Ca3Bi2Au7 cuboctahedra,  a faceface with one Au(2)Ca4Au12 tetrahedra, and faces with three equivalent Au(1)Ca4Au12 tetrahedra. In the seventh Au site, Au(7) is bonded to three equivalent Ca(1), three equivalent Au(1), three equivalent Au(4), and three equivalent Au(5) atoms to form distorted AuCa3Au9 cuboctahedra that share corners with three equivalent Au(6)Ca3Bi3Au6 cuboctahedra, corners with three equivalent Au(1)Ca4Au12 tetrahedra, edges with six equivalent Au(7)Ca3Au9 cuboctahedra, faces with three equivalent Au(1)Ca4Au12 tetrahedra, and faces with three equivalent Au(2)Ca4Au12 tetrahedra. In the eighth Au site, Au(8) is bonded in a 12-coordinate geometry to three equivalent Ca(2), three equivalent Au(2), three equivalent Au(3), and three equivalent Au(5) atoms. Bi(1) is bonded in a 16-coordinate geometry to one Ca(2), three equivalent Ca(3), three equivalent Au(4), three equivalent Au(6), and six equivalent Au(3) atoms.
Ca3Au14Bi crystallizes in the trigonal P3m1 space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 16-coordinate geometry to one Au(2), three equivalent Au(1), three equivalent Au(4), three equivalent Au(7), and six equivalent Au(5) atoms. The Ca(1)-Au(2) bond length is 3.39 Å. All Ca(1)-Au(1) bond lengths are 3.37 Å. All Ca(1)-Au(4) bond lengths are 3.22 Å. All Ca(1)-Au(7) bond lengths are 3.24 Å. All Ca(1)-Au(5) bond lengths are 3.25 Å. In the second Ca site, Ca(2) is bonded in a 16-coordinate geometry to three equivalent Au(2), three equivalent Au(5), three equivalent Au(8), six equivalent Au(3), and one Bi(1) atom. All Ca(2)-Au(2) bond lengths are 3.38 Å. All Ca(2)-Au(5) bond lengths are 3.21 Å. All Ca(2)-Au(8) bond lengths are 3.24 Å. All Ca(2)-Au(3) bond lengths are 3.28 Å. The Ca(2)-Bi(1) bond length is 3.48 Å. In the third Ca site, Ca(3) is bonded in a 16-coordinate geometry to one Au(1), three equivalent Au(3), three equivalent Au(6), six equivalent Au(4), and three equivalent Bi(1) atoms. The Ca(3)-Au(1) bond length is 3.38 Å. All Ca(3)-Au(3) bond lengths are 3.48 Å. All Ca(3)-Au(6) bond lengths are 3.27 Å. All Ca(3)-Au(4) bond lengths are 3.22 Å. All Ca(3)-Bi(1) bond lengths are 3.47 Å. There are eight inequivalent Au sites. In the first Au site, Au(1) is bonded to one Ca(3), three equivalent Ca(1), three equivalent Au(5), three equivalent Au(7), and six equivalent Au(4) atoms to form distorted AuCa4Au12 tetrahedra that share corners with three equivalent Au(7)Ca3Au9 cuboctahedra, corners with three equivalent Au(3)Ca3Bi2Au7 cuboctahedra, faces with three equivalent Au(7)Ca3Au9 cuboctahedra, faces with three equivalent Au(6)Ca3Bi3Au6 cuboctahedra, faces with three equivalent Au(2)Ca4Au12 tetrahedra, and faces with six equivalent Au(1)Ca4Au12 tetrahedra. All Au(1)-Au(5) bond lengths are 3.20 Å. All Au(1)-Au(7) bond lengths are 3.24 Å. All Au(1)-Au(4) bond lengths are 3.26 Å. In the second Au site, Au(2) is bonded to one Ca(1), three equivalent Ca(2), three equivalent Au(3), three equivalent Au(8), and six equivalent Au(5) atoms to form distorted AuCa4Au12 tetrahedra that share corners with six equivalent Au(3)Ca3Bi2Au7 cuboctahedra,  a faceface with one Au(6)Ca3Bi3Au6 cuboctahedra, faces with three equivalent Au(7)Ca3Au9 cuboctahedra, faces with nine equivalent Au(3)Ca3Bi2Au7 cuboctahedra, faces with three equivalent Au(1)Ca4Au12 tetrahedra, and faces with six equivalent Au(2)Ca4Au12 tetrahedra. All Au(2)-Au(3) bond lengths are 3.27 Å. All Au(2)-Au(8) bond lengths are 3.25 Å. All Au(2)-Au(5) bond lengths are 3.24 Å. In the third Au site, Au(3) is bonded to one Ca(3), two equivalent Ca(2), one Au(2), one Au(6), one Au(8), four equivalent Au(3), and two equivalent Bi(1) atoms to form distorted AuCa3Bi2Au7 cuboctahedra that share corners with two equivalent Au(6)Ca3Bi3Au6 cuboctahedra, corners with four equivalent Au(3)Ca3Bi2Au7 cuboctahedra,  a cornercorner with one Au(1)Ca4Au12 tetrahedra, corners with two equivalent Au(2)Ca4Au12 tetrahedra, edges with two equivalent Au(3)Ca3Bi2Au7 cuboctahedra, faces with three equivalent Au(6)Ca3Bi3Au6 cuboctahedra, faces with eight equivalent Au(3)Ca3Bi2Au7 cuboctahedra, and faces with three equivalent Au(2)Ca4Au12 tetrahedra. The Au(3)-Au(6) bond length is 2.87 Å. The Au(3)-Au(8) bond length is 2.79 Å. There are two shorter (2.76 Å) and two longer (2.78 Å) Au(3)-Au(3) bond lengths. Both Au(3)-Bi(1) bond lengths are 3.26 Å. In the fourth Au site, Au(4) is bonded in a 12-coordinate geometry to one Ca(1), two equivalent Ca(3), one Au(6), one Au(7), two equivalent Au(1), four equivalent Au(4), and one Bi(1) atom. The Au(4)-Au(6) bond length is 2.83 Å. The Au(4)-Au(7) bond length is 2.76 Å. There are two shorter (2.76 Å) and two longer (2.77 Å) Au(4)-Au(4) bond lengths. The Au(4)-Bi(1) bond length is 3.41 Å. In the fifth Au site, Au(5) is bonded in a 12-coordinate geometry to one Ca(2), two equivalent Ca(1), one Au(1), one Au(7), one Au(8), two equivalent Au(2), and four equivalent Au(5) atoms. The Au(5)-Au(7) bond length is 2.77 Å. The Au(5)-Au(8) bond length is 2.77 Å. There are two shorter (2.76 Å) and two longer (2.78 Å) Au(5)-Au(5) bond lengths. In the sixth Au site, Au(6) is bonded to three equivalent Ca(3), three equivalent Au(3), three equivalent Au(4), and three equivalent Bi(1) atoms to form AuCa3Bi3Au6 cuboctahedra that share corners with three equivalent Au(7)Ca3Au9 cuboctahedra, corners with six equivalent Au(3)Ca3Bi2Au7 cuboctahedra, edges with six equivalent Au(6)Ca3Bi3Au6 cuboctahedra, faces with nine equivalent Au(3)Ca3Bi2Au7 cuboctahedra,  a faceface with one Au(2)Ca4Au12 tetrahedra, and faces with three equivalent Au(1)Ca4Au12 tetrahedra. All Au(6)-Bi(1) bond lengths are 3.26 Å. In the seventh Au site, Au(7) is bonded to three equivalent Ca(1), three equivalent Au(1), three equivalent Au(4), and three equivalent Au(5) atoms to form distorted AuCa3Au9 cuboctahedra that share corners with three equivalent Au(6)Ca3Bi3Au6 cuboctahedra, corners with three equivalent Au(1)Ca4Au12 tetrahedra, edges with six equivalent Au(7)Ca3Au9 cuboctahedra, faces with three equivalent Au(1)Ca4Au12 tetrahedra, and faces with three equivalent Au(2)Ca4Au12 tetrahedra. In the eighth Au site, Au(8) is bonded in a 12-coordinate geometry to three equivalent Ca(2), three equivalent Au(2), three equivalent Au(3), and three equivalent Au(5) atoms. Bi(1) is bonded in a 16-coordinate geometry to one Ca(2), three equivalent Ca(3), three equivalent Au(4), three equivalent Au(6), and six equivalent Au(3) atoms.