Ba2In2O5 crystallizes in the orthorhombic Aem2 space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to one O(4), one O(5), one O(6), two equivalent O(2), two equivalent O(3), and two equivalent O(7) atoms. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to one O(4), one O(5), two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(8) atoms. In the third Ba site, Ba(3) is bonded in a 9-coordinate geometry to one O(4), one O(5), one O(6), two equivalent O(2), two equivalent O(3), and two equivalent O(7) atoms. In the fourth Ba site, Ba(4) is bonded in a 9-coordinate geometry to one O(4), two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(8) atoms. There are four inequivalent In sites. In the first In site, In(1) is bonded to one O(1), two equivalent O(3), and two equivalent O(5) atoms to form InO5 trigonal bipyramids that share corners with two equivalent In(4)O6 octahedra,  a cornercorner with one In(2)O5 trigonal bipyramid, and corners with two equivalent In(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 5°. In the second In site, In(2) is bonded to one O(1), two equivalent O(2), and two equivalent O(6) atoms to form corner-sharing InO5 trigonal bipyramids. In the third In site, In(3) is bonded in a square co-planar geometry to one O(7), one O(8), and two equivalent O(2) atoms. In the fourth In site, In(4) is bonded to one O(7), one O(8), two equivalent O(3), and two equivalent O(4) atoms to form InO6 octahedra that share corners with two equivalent In(4)O6 octahedra and corners with two equivalent In(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 13°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ba(2), two equivalent Ba(4), one In(1), and one In(2) atom to form distorted OBa4In2 octahedra that share corners with four equivalent O(3)Ba4In2 octahedra, corners with four equivalent O(8)Ba4In2 octahedra, corners with two equivalent O(6)Ba2In2 tetrahedra, edges with two equivalent O(1)Ba4In2 octahedra, edges with two equivalent O(8)Ba4In2 octahedra, and faces with two equivalent O(3)Ba4In2 octahedra. The corner-sharing octahedral tilt angles range from 8-61°. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(4), one In(2), and one In(3) atom. In the third O site, O(3) is bonded to one Ba(1), one Ba(2), one Ba(3), one Ba(4), one In(1), and one In(4) atom to form distorted OBa4In2 octahedra that share corners with two equivalent O(1)Ba4In2 octahedra, corners with two equivalent O(3)Ba4In2 octahedra, corners with two equivalent O(7)Ba4In2 octahedra, corners with two equivalent O(8)Ba4In2 octahedra, corners with two equivalent O(6)Ba2In2 tetrahedra, edges with two equivalent O(3)Ba4In2 octahedra,  a faceface with one O(1)Ba4In2 octahedra,  a faceface with one O(7)Ba4In2 octahedra, and  a faceface with one O(8)Ba4In2 octahedra. The corner-sharing octahedral tilt angles range from 2-61°. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(4), and two equivalent In(4) atoms. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), and two equivalent In(1) atoms. In the sixth O site, O(6) is bonded to one Ba(1), one Ba(3), and two equivalent In(2) atoms to form distorted OBa2In2 tetrahedra that share corners with two equivalent O(1)Ba4In2 octahedra, corners with four equivalent O(3)Ba4In2 octahedra, corners with four equivalent O(7)Ba4In2 octahedra, and corners with two equivalent O(6)Ba2In2 tetrahedra. The corner-sharing octahedral tilt angles range from 56-71°. In the seventh O site, O(7) is bonded to two equivalent Ba(1), two equivalent Ba(3), one In(3), and one In(4) atom to form distorted OBa4In2 octahedra that share corners with two equivalent O(8)Ba4In2 octahedra, corners with four equivalent O(3)Ba4In2 octahedra, corners with four equivalent O(6)Ba2In2 tetrahedra, edges with two equivalent O(7)Ba4In2 octahedra, and faces with two equivalent O(3)Ba4In2 octahedra. The corner-sharing octahedral tilt angles range from 0-58°. In the eighth O site, O(8) is bonded to two equivalent Ba(2), two equivalent Ba(4), one In(3), and one In(4) atom to form a mixture of distorted edge, face, and corner-sharing OBa4In2 octahedra. The corner-sharing octahedral tilt angles range from 0-55°.
Ba2In2O5 crystallizes in the orthorhombic Aem2 space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to one O(4), one O(5), one O(6), two equivalent O(2), two equivalent O(3), and two equivalent O(7) atoms. The Ba(1)-O(4) bond length is 3.18 Å. The Ba(1)-O(5) bond length is 2.71 Å. The Ba(1)-O(6) bond length is 2.83 Å. Both Ba(1)-O(2) bond lengths are 2.87 Å. Both Ba(1)-O(3) bond lengths are 2.90 Å. Both Ba(1)-O(7) bond lengths are 2.97 Å. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to one O(4), one O(5), two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(8) atoms. The Ba(2)-O(4) bond length is 2.77 Å. The Ba(2)-O(5) bond length is 3.34 Å. Both Ba(2)-O(1) bond lengths are 3.02 Å. Both Ba(2)-O(2) bond lengths are 3.32 Å. Both Ba(2)-O(3) bond lengths are 2.88 Å. Both Ba(2)-O(8) bond lengths are 2.97 Å. In the third Ba site, Ba(3) is bonded in a 9-coordinate geometry to one O(4), one O(5), one O(6), two equivalent O(2), two equivalent O(3), and two equivalent O(7) atoms. The Ba(3)-O(4) bond length is 3.09 Å. The Ba(3)-O(5) bond length is 2.70 Å. The Ba(3)-O(6) bond length is 2.72 Å. Both Ba(3)-O(2) bond lengths are 3.12 Å. Both Ba(3)-O(3) bond lengths are 2.86 Å. Both Ba(3)-O(7) bond lengths are 2.95 Å. In the fourth Ba site, Ba(4) is bonded in a 9-coordinate geometry to one O(4), two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(8) atoms. The Ba(4)-O(4) bond length is 2.81 Å. Both Ba(4)-O(1) bond lengths are 3.03 Å. Both Ba(4)-O(2) bond lengths are 3.07 Å. Both Ba(4)-O(3) bond lengths are 2.95 Å. Both Ba(4)-O(8) bond lengths are 2.95 Å. There are four inequivalent In sites. In the first In site, In(1) is bonded to one O(1), two equivalent O(3), and two equivalent O(5) atoms to form InO5 trigonal bipyramids that share corners with two equivalent In(4)O6 octahedra,  a cornercorner with one In(2)O5 trigonal bipyramid, and corners with two equivalent In(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 5°. The In(1)-O(1) bond length is 2.11 Å. Both In(1)-O(3) bond lengths are 2.14 Å. Both In(1)-O(5) bond lengths are 2.14 Å. In the second In site, In(2) is bonded to one O(1), two equivalent O(2), and two equivalent O(6) atoms to form corner-sharing InO5 trigonal bipyramids. The In(2)-O(1) bond length is 2.08 Å. Both In(2)-O(2) bond lengths are 2.23 Å. Both In(2)-O(6) bond lengths are 2.17 Å. In the third In site, In(3) is bonded in a square co-planar geometry to one O(7), one O(8), and two equivalent O(2) atoms. The In(3)-O(7) bond length is 2.09 Å. The In(3)-O(8) bond length is 2.07 Å. Both In(3)-O(2) bond lengths are 2.13 Å. In the fourth In site, In(4) is bonded to one O(7), one O(8), two equivalent O(3), and two equivalent O(4) atoms to form InO6 octahedra that share corners with two equivalent In(4)O6 octahedra and corners with two equivalent In(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 13°. The In(4)-O(7) bond length is 2.24 Å. The In(4)-O(8) bond length is 2.37 Å. Both In(4)-O(3) bond lengths are 2.21 Å. Both In(4)-O(4) bond lengths are 2.06 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ba(2), two equivalent Ba(4), one In(1), and one In(2) atom to form distorted OBa4In2 octahedra that share corners with four equivalent O(3)Ba4In2 octahedra, corners with four equivalent O(8)Ba4In2 octahedra, corners with two equivalent O(6)Ba2In2 tetrahedra, edges with two equivalent O(1)Ba4In2 octahedra, edges with two equivalent O(8)Ba4In2 octahedra, and faces with two equivalent O(3)Ba4In2 octahedra. The corner-sharing octahedral tilt angles range from 8-61°. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(4), one In(2), and one In(3) atom. In the third O site, O(3) is bonded to one Ba(1), one Ba(2), one Ba(3), one Ba(4), one In(1), and one In(4) atom to form distorted OBa4In2 octahedra that share corners with two equivalent O(1)Ba4In2 octahedra, corners with two equivalent O(3)Ba4In2 octahedra, corners with two equivalent O(7)Ba4In2 octahedra, corners with two equivalent O(8)Ba4In2 octahedra, corners with two equivalent O(6)Ba2In2 tetrahedra, edges with two equivalent O(3)Ba4In2 octahedra,  a faceface with one O(1)Ba4In2 octahedra,  a faceface with one O(7)Ba4In2 octahedra, and  a faceface with one O(8)Ba4In2 octahedra. The corner-sharing octahedral tilt angles range from 2-61°. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(4), and two equivalent In(4) atoms. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), and two equivalent In(1) atoms. In the sixth O site, O(6) is bonded to one Ba(1), one Ba(3), and two equivalent In(2) atoms to form distorted OBa2In2 tetrahedra that share corners with two equivalent O(1)Ba4In2 octahedra, corners with four equivalent O(3)Ba4In2 octahedra, corners with four equivalent O(7)Ba4In2 octahedra, and corners with two equivalent O(6)Ba2In2 tetrahedra. The corner-sharing octahedral tilt angles range from 56-71°. In the seventh O site, O(7) is bonded to two equivalent Ba(1), two equivalent Ba(3), one In(3), and one In(4) atom to form distorted OBa4In2 octahedra that share corners with two equivalent O(8)Ba4In2 octahedra, corners with four equivalent O(3)Ba4In2 octahedra, corners with four equivalent O(6)Ba2In2 tetrahedra, edges with two equivalent O(7)Ba4In2 octahedra, and faces with two equivalent O(3)Ba4In2 octahedra. The corner-sharing octahedral tilt angles range from 0-58°. In the eighth O site, O(8) is bonded to two equivalent Ba(2), two equivalent Ba(4), one In(3), and one In(4) atom to form a mixture of distorted edge, face, and corner-sharing OBa4In2 octahedra. The corner-sharing octahedral tilt angles range from 0-55°.