Ba2InBiSe5 crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one Se(1), one Se(3), two equivalent Se(2), two equivalent Se(4), and two equivalent Se(5) atoms. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one Se(3), one Se(5), two equivalent Se(1), two equivalent Se(2), and two equivalent Se(4) atoms. In(1) is bonded to one Se(2), one Se(5), and two equivalent Se(3) atoms to form corner-sharing InSe4 tetrahedra. Bi(1) is bonded in a 6-coordinate geometry to one Se(3), one Se(4), two equivalent Se(1), and two equivalent Se(5) atoms. There are five inequivalent Se sites. In the first Se site, Se(1) is bonded to one Ba(1), two equivalent Ba(2), and two equivalent Bi(1) atoms to form SeBa3Bi2 trigonal bipyramids that share corners with two equivalent Se(5)Ba3InBi2 octahedra, corners with two equivalent Se(4)Ba4Bi square pyramids, corners with four equivalent Se(2)Ba4In square pyramids, edges with three equivalent Se(5)Ba3InBi2 octahedra,  an edgeedge with one Se(2)Ba4In square pyramid, edges with three equivalent Se(4)Ba4Bi square pyramids, and edges with two equivalent Se(1)Ba3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 11°. In the second Se site, Se(2) is bonded to two equivalent Ba(1), two equivalent Ba(2), and one In(1) atom to form SeBa4In square pyramids that share corners with four equivalent Se(5)Ba3InBi2 octahedra, corners with four equivalent Se(4)Ba4Bi square pyramids, corners with four equivalent Se(1)Ba3Bi2 trigonal bipyramids, edges with two equivalent Se(4)Ba4Bi square pyramids, edges with two equivalent Se(2)Ba4In square pyramids,  an edgeedge with one Se(1)Ba3Bi2 trigonal bipyramid, and  a faceface with one Se(5)Ba3InBi2 octahedra. The corner-sharing octahedral tilt angles range from 41-65°. In the third Se site, Se(3) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), two equivalent In(1), and one Bi(1) atom. In the fourth Se site, Se(4) is bonded to two equivalent Ba(1), two equivalent Ba(2), and one Bi(1) atom to form SeBa4Bi square pyramids that share corners with two equivalent Se(5)Ba3InBi2 octahedra, corners with four equivalent Se(2)Ba4In square pyramids, corners with two equivalent Se(1)Ba3Bi2 trigonal bipyramids, edges with three equivalent Se(5)Ba3InBi2 octahedra, edges with two equivalent Se(4)Ba4Bi square pyramids, edges with two equivalent Se(2)Ba4In square pyramids, and edges with three equivalent Se(1)Ba3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 33°. In the fifth Se site, Se(5) is bonded to one Ba(2), two equivalent Ba(1), one In(1), and two equivalent Bi(1) atoms to form distorted SeBa3InBi2 octahedra that share corners with two equivalent Se(4)Ba4Bi square pyramids, corners with four equivalent Se(2)Ba4In square pyramids, corners with two equivalent Se(1)Ba3Bi2 trigonal bipyramids, edges with two equivalent Se(5)Ba3InBi2 octahedra, edges with three equivalent Se(4)Ba4Bi square pyramids, edges with three equivalent Se(1)Ba3Bi2 trigonal bipyramids, and  a faceface with one Se(2)Ba4In square pyramid.
Ba2InBiSe5 crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one Se(1), one Se(3), two equivalent Se(2), two equivalent Se(4), and two equivalent Se(5) atoms. The Ba(1)-Se(1) bond length is 3.32 Å. The Ba(1)-Se(3) bond length is 3.55 Å. Both Ba(1)-Se(2) bond lengths are 3.37 Å. Both Ba(1)-Se(4) bond lengths are 3.35 Å. Both Ba(1)-Se(5) bond lengths are 3.58 Å. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one Se(3), one Se(5), two equivalent Se(1), two equivalent Se(2), and two equivalent Se(4) atoms. The Ba(2)-Se(3) bond length is 3.80 Å. The Ba(2)-Se(5) bond length is 3.66 Å. Both Ba(2)-Se(1) bond lengths are 3.39 Å. Both Ba(2)-Se(2) bond lengths are 3.31 Å. Both Ba(2)-Se(4) bond lengths are 3.37 Å. In(1) is bonded to one Se(2), one Se(5), and two equivalent Se(3) atoms to form corner-sharing InSe4 tetrahedra. The In(1)-Se(2) bond length is 2.58 Å. The In(1)-Se(5) bond length is 2.70 Å. Both In(1)-Se(3) bond lengths are 2.67 Å. Bi(1) is bonded in a 6-coordinate geometry to one Se(3), one Se(4), two equivalent Se(1), and two equivalent Se(5) atoms. The Bi(1)-Se(3) bond length is 3.36 Å. The Bi(1)-Se(4) bond length is 2.76 Å. Both Bi(1)-Se(1) bond lengths are 2.93 Å. Both Bi(1)-Se(5) bond lengths are 3.08 Å. There are five inequivalent Se sites. In the first Se site, Se(1) is bonded to one Ba(1), two equivalent Ba(2), and two equivalent Bi(1) atoms to form SeBa3Bi2 trigonal bipyramids that share corners with two equivalent Se(5)Ba3InBi2 octahedra, corners with two equivalent Se(4)Ba4Bi square pyramids, corners with four equivalent Se(2)Ba4In square pyramids, edges with three equivalent Se(5)Ba3InBi2 octahedra,  an edgeedge with one Se(2)Ba4In square pyramid, edges with three equivalent Se(4)Ba4Bi square pyramids, and edges with two equivalent Se(1)Ba3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 11°. In the second Se site, Se(2) is bonded to two equivalent Ba(1), two equivalent Ba(2), and one In(1) atom to form SeBa4In square pyramids that share corners with four equivalent Se(5)Ba3InBi2 octahedra, corners with four equivalent Se(4)Ba4Bi square pyramids, corners with four equivalent Se(1)Ba3Bi2 trigonal bipyramids, edges with two equivalent Se(4)Ba4Bi square pyramids, edges with two equivalent Se(2)Ba4In square pyramids,  an edgeedge with one Se(1)Ba3Bi2 trigonal bipyramid, and  a faceface with one Se(5)Ba3InBi2 octahedra. The corner-sharing octahedral tilt angles range from 41-65°. In the third Se site, Se(3) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), two equivalent In(1), and one Bi(1) atom. In the fourth Se site, Se(4) is bonded to two equivalent Ba(1), two equivalent Ba(2), and one Bi(1) atom to form SeBa4Bi square pyramids that share corners with two equivalent Se(5)Ba3InBi2 octahedra, corners with four equivalent Se(2)Ba4In square pyramids, corners with two equivalent Se(1)Ba3Bi2 trigonal bipyramids, edges with three equivalent Se(5)Ba3InBi2 octahedra, edges with two equivalent Se(4)Ba4Bi square pyramids, edges with two equivalent Se(2)Ba4In square pyramids, and edges with three equivalent Se(1)Ba3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 33°. In the fifth Se site, Se(5) is bonded to one Ba(2), two equivalent Ba(1), one In(1), and two equivalent Bi(1) atoms to form distorted SeBa3InBi2 octahedra that share corners with two equivalent Se(4)Ba4Bi square pyramids, corners with four equivalent Se(2)Ba4In square pyramids, corners with two equivalent Se(1)Ba3Bi2 trigonal bipyramids, edges with two equivalent Se(5)Ba3InBi2 octahedra, edges with three equivalent Se(4)Ba4Bi square pyramids, edges with three equivalent Se(1)Ba3Bi2 trigonal bipyramids, and  a faceface with one Se(2)Ba4In square pyramid.