Ca11GaSb9 crystallizes in the orthorhombic Iba2 space group. There are six inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one Sb(1), one Sb(2), one Sb(3), one Sb(4), and two equivalent Sb(5) atoms to form distorted corner-sharing CaSb6 octahedra. The corner-sharing octahedral tilt angles range from 36-56°. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to one Sb(2), one Sb(3), one Sb(4), one Sb(5), and two equivalent Sb(1) atoms. In the third Ca site, Ca(3) is bonded in a 6-coordinate geometry to one Sb(3), one Sb(4), two equivalent Sb(2), and two equivalent Sb(5) atoms. In the fourth Ca site, Ca(4) is bonded in a 8-coordinate geometry to one Ga(1), one Sb(1), one Sb(5), two equivalent Sb(2), and three equivalent Sb(3) atoms. In the fifth Ca site, Ca(5) is bonded in a 6-coordinate geometry to two equivalent Sb(1), two equivalent Sb(3), and two equivalent Sb(5) atoms. In the sixth Ca site, Ca(6) is bonded in a 5-coordinate geometry to one Sb(1), one Sb(3), one Sb(4), and two equivalent Sb(2) atoms. Ga(1) is bonded in a 6-coordinate geometry to two equivalent Ca(4), two equivalent Sb(1), and two equivalent Sb(3) atoms. There are five inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 7-coordinate geometry to one Ca(1), one Ca(4), one Ca(5), one Ca(6), two equivalent Ca(2), and one Ga(1) atom. In the second Sb site, Sb(2) is bonded in a 9-coordinate geometry to one Ca(1), one Ca(2), two equivalent Ca(3), two equivalent Ca(4), two equivalent Ca(6), and one Sb(2) atom. In the third Sb site, Sb(3) is bonded in a 9-coordinate geometry to one Ca(1), one Ca(2), one Ca(3), one Ca(5), one Ca(6), three equivalent Ca(4), and one Ga(1) atom. In the fourth Sb site, Sb(4) is bonded in a 8-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), two equivalent Ca(3), and two equivalent Ca(6) atoms. In the fifth Sb site, Sb(5) is bonded in a 7-coordinate geometry to one Ca(2), one Ca(4), one Ca(5), two equivalent Ca(1), and two equivalent Ca(3) atoms.
Ca11GaSb9 crystallizes in the orthorhombic Iba2 space group. There are six inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one Sb(1), one Sb(2), one Sb(3), one Sb(4), and two equivalent Sb(5) atoms to form distorted corner-sharing CaSb6 octahedra. The corner-sharing octahedral tilt angles range from 36-56°. The Ca(1)-Sb(1) bond length is 3.23 Å. The Ca(1)-Sb(2) bond length is 3.10 Å. The Ca(1)-Sb(3) bond length is 3.40 Å. The Ca(1)-Sb(4) bond length is 3.31 Å. There is one shorter (3.05 Å) and one longer (3.22 Å) Ca(1)-Sb(5) bond length. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to one Sb(2), one Sb(3), one Sb(4), one Sb(5), and two equivalent Sb(1) atoms. The Ca(2)-Sb(2) bond length is 3.09 Å. The Ca(2)-Sb(3) bond length is 3.39 Å. The Ca(2)-Sb(4) bond length is 3.40 Å. The Ca(2)-Sb(5) bond length is 3.10 Å. There is one shorter (3.31 Å) and one longer (3.38 Å) Ca(2)-Sb(1) bond length. In the third Ca site, Ca(3) is bonded in a 6-coordinate geometry to one Sb(3), one Sb(4), two equivalent Sb(2), and two equivalent Sb(5) atoms. The Ca(3)-Sb(3) bond length is 3.15 Å. The Ca(3)-Sb(4) bond length is 3.07 Å. Both Ca(3)-Sb(2) bond lengths are 3.46 Å. There is one shorter (3.47 Å) and one longer (3.48 Å) Ca(3)-Sb(5) bond length. In the fourth Ca site, Ca(4) is bonded in a 8-coordinate geometry to one Ga(1), one Sb(1), one Sb(5), two equivalent Sb(2), and three equivalent Sb(3) atoms. The Ca(4)-Ga(1) bond length is 3.35 Å. The Ca(4)-Sb(1) bond length is 3.18 Å. The Ca(4)-Sb(5) bond length is 3.06 Å. There is one shorter (3.57 Å) and one longer (3.73 Å) Ca(4)-Sb(2) bond length. There are a spread of Ca(4)-Sb(3) bond distances ranging from 3.50-3.67 Å. In the fifth Ca site, Ca(5) is bonded in a 6-coordinate geometry to two equivalent Sb(1), two equivalent Sb(3), and two equivalent Sb(5) atoms. Both Ca(5)-Sb(1) bond lengths are 3.29 Å. Both Ca(5)-Sb(3) bond lengths are 3.64 Å. Both Ca(5)-Sb(5) bond lengths are 3.07 Å. In the sixth Ca site, Ca(6) is bonded in a 5-coordinate geometry to one Sb(1), one Sb(3), one Sb(4), and two equivalent Sb(2) atoms. The Ca(6)-Sb(1) bond length is 3.33 Å. The Ca(6)-Sb(3) bond length is 3.19 Å. The Ca(6)-Sb(4) bond length is 3.05 Å. There is one shorter (3.40 Å) and one longer (3.43 Å) Ca(6)-Sb(2) bond length. Ga(1) is bonded in a 6-coordinate geometry to two equivalent Ca(4), two equivalent Sb(1), and two equivalent Sb(3) atoms. Both Ga(1)-Sb(1) bond lengths are 2.78 Å. Both Ga(1)-Sb(3) bond lengths are 2.77 Å. There are five inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 7-coordinate geometry to one Ca(1), one Ca(4), one Ca(5), one Ca(6), two equivalent Ca(2), and one Ga(1) atom. In the second Sb site, Sb(2) is bonded in a 9-coordinate geometry to one Ca(1), one Ca(2), two equivalent Ca(3), two equivalent Ca(4), two equivalent Ca(6), and one Sb(2) atom. The Sb(2)-Sb(2) bond length is 2.86 Å. In the third Sb site, Sb(3) is bonded in a 9-coordinate geometry to one Ca(1), one Ca(2), one Ca(3), one Ca(5), one Ca(6), three equivalent Ca(4), and one Ga(1) atom. In the fourth Sb site, Sb(4) is bonded in a 8-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), two equivalent Ca(3), and two equivalent Ca(6) atoms. In the fifth Sb site, Sb(5) is bonded in a 7-coordinate geometry to one Ca(2), one Ca(4), one Ca(5), two equivalent Ca(1), and two equivalent Ca(3) atoms.