BaCa2In6O12 crystallizes in the trigonal P3 space group. Ba(1) is bonded in a 9-coordinate geometry to three equivalent O(3) and six equivalent O(4) atoms. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 6-coordinate geometry to six equivalent O(2) atoms. In the second Ca site, Ca(2) is bonded to six equivalent O(1) atoms to form distorted CaO6 pentagonal pyramids that share corners with six equivalent In(1)O6 octahedra, corners with six equivalent In(2)O6 octahedra, edges with three equivalent In(2)O6 octahedra, and faces with two equivalent Ca(2)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 24-74°. There are two inequivalent In sites. In the first In site, In(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form InO6 octahedra that share corners with four equivalent In(2)O6 octahedra, corners with two equivalent Ca(2)O6 pentagonal pyramids, edges with two equivalent In(1)O6 octahedra, and edges with two equivalent In(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-57°. In the second In site, In(2) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form InO6 octahedra that share corners with four equivalent In(1)O6 octahedra, corners with two equivalent Ca(2)O6 pentagonal pyramids, edges with two equivalent In(1)O6 octahedra, edges with two equivalent In(2)O6 octahedra, and  an edgeedge with one Ca(2)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 54-57°. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ca(2), one In(1), and two equivalent In(2) atoms to form a mixture of edge and corner-sharing OCa2In3 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Ca(1), one In(2), and two equivalent In(1) atoms to form a mixture of edge and corner-sharing OCa2In3 trigonal bipyramids. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Ba(1), one In(1), and two equivalent In(2) atoms. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent Ba(1), one In(2), and two equivalent In(1) atoms.
BaCa2In6O12 crystallizes in the trigonal P3 space group. Ba(1) is bonded in a 9-coordinate geometry to three equivalent O(3) and six equivalent O(4) atoms. All Ba(1)-O(3) bond lengths are 2.72 Å. There are three shorter (2.90 Å) and three longer (3.18 Å) Ba(1)-O(4) bond lengths. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 6-coordinate geometry to six equivalent O(2) atoms. All Ca(1)-O(2) bond lengths are 2.43 Å. In the second Ca site, Ca(2) is bonded to six equivalent O(1) atoms to form distorted CaO6 pentagonal pyramids that share corners with six equivalent In(1)O6 octahedra, corners with six equivalent In(2)O6 octahedra, edges with three equivalent In(2)O6 octahedra, and faces with two equivalent Ca(2)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 24-74°. There are three shorter (2.41 Å) and three longer (2.42 Å) Ca(2)-O(1) bond lengths. There are two inequivalent In sites. In the first In site, In(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form InO6 octahedra that share corners with four equivalent In(2)O6 octahedra, corners with two equivalent Ca(2)O6 pentagonal pyramids, edges with two equivalent In(1)O6 octahedra, and edges with two equivalent In(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-57°. The In(1)-O(1) bond length is 2.22 Å. The In(1)-O(3) bond length is 2.20 Å. There is one shorter (2.28 Å) and one longer (2.29 Å) In(1)-O(2) bond length. There is one shorter (2.20 Å) and one longer (2.22 Å) In(1)-O(4) bond length. In the second In site, In(2) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form InO6 octahedra that share corners with four equivalent In(1)O6 octahedra, corners with two equivalent Ca(2)O6 pentagonal pyramids, edges with two equivalent In(1)O6 octahedra, edges with two equivalent In(2)O6 octahedra, and  an edgeedge with one Ca(2)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 54-57°. The In(2)-O(2) bond length is 2.21 Å. The In(2)-O(4) bond length is 2.22 Å. There is one shorter (2.30 Å) and one longer (2.31 Å) In(2)-O(1) bond length. There is one shorter (2.16 Å) and one longer (2.17 Å) In(2)-O(3) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ca(2), one In(1), and two equivalent In(2) atoms to form a mixture of edge and corner-sharing OCa2In3 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Ca(1), one In(2), and two equivalent In(1) atoms to form a mixture of edge and corner-sharing OCa2In3 trigonal bipyramids. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Ba(1), one In(1), and two equivalent In(2) atoms. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent Ba(1), one In(2), and two equivalent In(1) atoms.