Gd5CuBi3 crystallizes in the orthorhombic Amm2 space group. There are five inequivalent Gd sites. In the first Gd site, Gd(1) is bonded to two equivalent Cu(1), one Bi(1), two equivalent Bi(3), and two equivalent Bi(4) atoms to form a mixture of distorted edge, face, and corner-sharing GdCu2Bi5 pentagonal bipyramids. In the second Gd site, Gd(2) is bonded to two equivalent Cu(1), one Bi(2), two equivalent Bi(3), and two equivalent Bi(4) atoms to form a mixture of distorted edge, face, and corner-sharing GdCu2Bi5 pentagonal bipyramids. In the third Gd site, Gd(3) is bonded in a 6-coordinate geometry to one Bi(1), one Bi(2), two equivalent Bi(3), and two equivalent Bi(4) atoms. In the fourth Gd site, Gd(4) is bonded to two equivalent Cu(1), one Bi(2), two equivalent Bi(1), and two equivalent Bi(4) atoms to form a mixture of distorted edge, face, and corner-sharing GdCu2Bi5 pentagonal bipyramids. In the fifth Gd site, Gd(5) is bonded to two equivalent Cu(1), one Bi(1), two equivalent Bi(2), and two equivalent Bi(3) atoms to form a mixture of distorted edge, face, and corner-sharing GdCu2Bi5 pentagonal bipyramids. Cu(1) is bonded to one Gd(4), one Gd(5), two equivalent Gd(1), and two equivalent Gd(2) atoms to form face-sharing CuGd6 octahedra. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 9-coordinate geometry to one Gd(5), two equivalent Gd(1), two equivalent Gd(4), and four equivalent Gd(3) atoms. In the second Bi site, Bi(2) is bonded in a 9-coordinate geometry to one Gd(4), two equivalent Gd(2), two equivalent Gd(5), and four equivalent Gd(3) atoms. In the third Bi site, Bi(3) is bonded in a 9-coordinate geometry to one Gd(5), two equivalent Gd(1), two equivalent Gd(2), and four equivalent Gd(3) atoms. In the fourth Bi site, Bi(4) is bonded in a 9-coordinate geometry to one Gd(4), two equivalent Gd(1), two equivalent Gd(2), and four equivalent Gd(3) atoms.
Gd5CuBi3 crystallizes in the orthorhombic Amm2 space group. There are five inequivalent Gd sites. In the first Gd site, Gd(1) is bonded to two equivalent Cu(1), one Bi(1), two equivalent Bi(3), and two equivalent Bi(4) atoms to form a mixture of distorted edge, face, and corner-sharing GdCu2Bi5 pentagonal bipyramids. Both Gd(1)-Cu(1) bond lengths are 2.85 Å. The Gd(1)-Bi(1) bond length is 3.21 Å. There is one shorter (3.20 Å) and one longer (3.40 Å) Gd(1)-Bi(3) bond length. Both Gd(1)-Bi(4) bond lengths are 3.50 Å. In the second Gd site, Gd(2) is bonded to two equivalent Cu(1), one Bi(2), two equivalent Bi(3), and two equivalent Bi(4) atoms to form a mixture of distorted edge, face, and corner-sharing GdCu2Bi5 pentagonal bipyramids. Both Gd(2)-Cu(1) bond lengths are 2.86 Å. The Gd(2)-Bi(2) bond length is 3.19 Å. Both Gd(2)-Bi(3) bond lengths are 3.50 Å. There is one shorter (3.19 Å) and one longer (3.41 Å) Gd(2)-Bi(4) bond length. In the third Gd site, Gd(3) is bonded in a 6-coordinate geometry to one Bi(1), one Bi(2), two equivalent Bi(3), and two equivalent Bi(4) atoms. The Gd(3)-Bi(1) bond length is 3.33 Å. The Gd(3)-Bi(2) bond length is 3.34 Å. There is one shorter (3.33 Å) and one longer (3.34 Å) Gd(3)-Bi(3) bond length. There is one shorter (3.32 Å) and one longer (3.34 Å) Gd(3)-Bi(4) bond length. In the fourth Gd site, Gd(4) is bonded to two equivalent Cu(1), one Bi(2), two equivalent Bi(1), and two equivalent Bi(4) atoms to form a mixture of distorted edge, face, and corner-sharing GdCu2Bi5 pentagonal bipyramids. Both Gd(4)-Cu(1) bond lengths are 2.88 Å. The Gd(4)-Bi(2) bond length is 3.38 Å. Both Gd(4)-Bi(1) bond lengths are 3.47 Å. Both Gd(4)-Bi(4) bond lengths are 3.22 Å. In the fifth Gd site, Gd(5) is bonded to two equivalent Cu(1), one Bi(1), two equivalent Bi(2), and two equivalent Bi(3) atoms to form a mixture of distorted edge, face, and corner-sharing GdCu2Bi5 pentagonal bipyramids. Both Gd(5)-Cu(1) bond lengths are 2.87 Å. The Gd(5)-Bi(1) bond length is 3.40 Å. Both Gd(5)-Bi(2) bond lengths are 3.48 Å. Both Gd(5)-Bi(3) bond lengths are 3.21 Å. Cu(1) is bonded to one Gd(4), one Gd(5), two equivalent Gd(1), and two equivalent Gd(2) atoms to form face-sharing CuGd6 octahedra. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 9-coordinate geometry to one Gd(5), two equivalent Gd(1), two equivalent Gd(4), and four equivalent Gd(3) atoms. In the second Bi site, Bi(2) is bonded in a 9-coordinate geometry to one Gd(4), two equivalent Gd(2), two equivalent Gd(5), and four equivalent Gd(3) atoms. In the third Bi site, Bi(3) is bonded in a 9-coordinate geometry to one Gd(5), two equivalent Gd(1), two equivalent Gd(2), and four equivalent Gd(3) atoms. In the fourth Bi site, Bi(4) is bonded in a 9-coordinate geometry to one Gd(4), two equivalent Gd(1), two equivalent Gd(2), and four equivalent Gd(3) atoms.