Ba4Tm6O13 crystallizes in the orthorhombic Iba2 space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to one O(3), one O(5), two equivalent O(4), two equivalent O(7), and three equivalent O(2) atoms. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one O(2), one O(6), two equivalent O(4), two equivalent O(7), and three equivalent O(5) atoms. There are three inequivalent Tm sites. In the first Tm site, Tm(1) is bonded to one O(2), two equivalent O(1), and two equivalent O(3) atoms to form distorted TmO5 trigonal bipyramids that share  a cornercorner with one Tm(2)O6 octahedra, corners with two equivalent Tm(1)O5 trigonal bipyramids, corners with two equivalent Tm(3)O5 trigonal bipyramids, and edges with three equivalent Tm(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 8°. In the second Tm site, Tm(2) is bonded to one O(2), one O(5), two equivalent O(4), and two equivalent O(7) atoms to form TmO6 octahedra that share corners with four equivalent Tm(2)O6 octahedra,  a cornercorner with one Tm(1)O5 trigonal bipyramid, and  a cornercorner with one Tm(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 5°. In the third Tm site, Tm(3) is bonded to one O(3), one O(5), and three equivalent O(6) atoms to form distorted TmO5 trigonal bipyramids that share  a cornercorner with one Tm(2)O6 octahedra, corners with two equivalent Tm(1)O5 trigonal bipyramids, corners with four equivalent Tm(3)O5 trigonal bipyramids, and  an edgeedge with one Tm(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 11°. There are seven inequivalent O sites. In the first O site, O(1) is bonded to four equivalent Tm(1) atoms to form distorted OTm4 trigonal pyramids that share corners with four equivalent O(3)BaTm3 trigonal pyramids, edges with two equivalent O(3)BaTm3 trigonal pyramids, and edges with two equivalent O(1)Tm4 trigonal pyramids. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Ba(2), three equivalent Ba(1), one Tm(1), and one Tm(2) atom. In the third O site, O(3) is bonded to one Ba(1), one Tm(3), and two equivalent Tm(1) atoms to form distorted OBaTm3 trigonal pyramids that share corners with two equivalent O(4)Ba4Tm2 octahedra, corners with two equivalent O(7)Ba4Tm2 octahedra, corners with three equivalent O(6)BaTm3 tetrahedra, corners with two equivalent O(3)BaTm3 trigonal pyramids, corners with two equivalent O(1)Tm4 trigonal pyramids, and  an edgeedge with one O(1)Tm4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 27-71°. In the fourth O site, O(4) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Tm(2) atoms to form distorted OBa4Tm2 octahedra that share corners with two equivalent O(7)Ba4Tm2 octahedra, corners with two equivalent O(6)BaTm3 tetrahedra, corners with two equivalent O(3)BaTm3 trigonal pyramids, edges with two equivalent O(7)Ba4Tm2 octahedra, faces with two equivalent O(4)Ba4Tm2 octahedra, and faces with two equivalent O(7)Ba4Tm2 octahedra. The corner-sharing octahedral tilt angles range from 3-4°. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Ba(1), three equivalent Ba(2), one Tm(2), and one Tm(3) atom. In the sixth O site, O(6) is bonded to one Ba(2) and three equivalent Tm(3) atoms to form distorted OBaTm3 tetrahedra that share corners with two equivalent O(4)Ba4Tm2 octahedra, corners with two equivalent O(7)Ba4Tm2 octahedra, corners with four equivalent O(6)BaTm3 tetrahedra, corners with three equivalent O(3)BaTm3 trigonal pyramids, and  an edgeedge with one O(6)BaTm3 tetrahedra. The corner-sharing octahedral tilt angles range from 27-69°. In the seventh O site, O(7) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Tm(2) atoms to form distorted OBa4Tm2 octahedra that share corners with two equivalent O(4)Ba4Tm2 octahedra, corners with two equivalent O(6)BaTm3 tetrahedra, corners with two equivalent O(3)BaTm3 trigonal pyramids, edges with two equivalent O(4)Ba4Tm2 octahedra, faces with two equivalent O(4)Ba4Tm2 octahedra, and faces with two equivalent O(7)Ba4Tm2 octahedra. The corner-sharing octahedral tilt angles range from 3-4°.
Ba4Tm6O13 crystallizes in the orthorhombic Iba2 space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to one O(3), one O(5), two equivalent O(4), two equivalent O(7), and three equivalent O(2) atoms. The Ba(1)-O(3) bond length is 3.06 Å. The Ba(1)-O(5) bond length is 3.04 Å. There is one shorter (2.79 Å) and one longer (2.91 Å) Ba(1)-O(4) bond length. There is one shorter (2.80 Å) and one longer (2.86 Å) Ba(1)-O(7) bond length. There are a spread of Ba(1)-O(2) bond distances ranging from 2.99-3.31 Å. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one O(2), one O(6), two equivalent O(4), two equivalent O(7), and three equivalent O(5) atoms. The Ba(2)-O(2) bond length is 3.15 Å. The Ba(2)-O(6) bond length is 2.68 Å. There is one shorter (2.77 Å) and one longer (2.91 Å) Ba(2)-O(4) bond length. There is one shorter (2.88 Å) and one longer (2.94 Å) Ba(2)-O(7) bond length. There are a spread of Ba(2)-O(5) bond distances ranging from 2.91-3.21 Å. There are three inequivalent Tm sites. In the first Tm site, Tm(1) is bonded to one O(2), two equivalent O(1), and two equivalent O(3) atoms to form distorted TmO5 trigonal bipyramids that share  a cornercorner with one Tm(2)O6 octahedra, corners with two equivalent Tm(1)O5 trigonal bipyramids, corners with two equivalent Tm(3)O5 trigonal bipyramids, and edges with three equivalent Tm(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 8°. The Tm(1)-O(2) bond length is 2.09 Å. There is one shorter (2.26 Å) and one longer (2.37 Å) Tm(1)-O(1) bond length. There is one shorter (2.22 Å) and one longer (2.23 Å) Tm(1)-O(3) bond length. In the second Tm site, Tm(2) is bonded to one O(2), one O(5), two equivalent O(4), and two equivalent O(7) atoms to form TmO6 octahedra that share corners with four equivalent Tm(2)O6 octahedra,  a cornercorner with one Tm(1)O5 trigonal bipyramid, and  a cornercorner with one Tm(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 5°. The Tm(2)-O(2) bond length is 2.37 Å. The Tm(2)-O(5) bond length is 2.30 Å. Both Tm(2)-O(4) bond lengths are 2.18 Å. There is one shorter (2.15 Å) and one longer (2.16 Å) Tm(2)-O(7) bond length. In the third Tm site, Tm(3) is bonded to one O(3), one O(5), and three equivalent O(6) atoms to form distorted TmO5 trigonal bipyramids that share  a cornercorner with one Tm(2)O6 octahedra, corners with two equivalent Tm(1)O5 trigonal bipyramids, corners with four equivalent Tm(3)O5 trigonal bipyramids, and  an edgeedge with one Tm(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 11°. The Tm(3)-O(3) bond length is 2.27 Å. The Tm(3)-O(5) bond length is 2.10 Å. There are a spread of Tm(3)-O(6) bond distances ranging from 2.20-2.36 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded to four equivalent Tm(1) atoms to form distorted OTm4 trigonal pyramids that share corners with four equivalent O(3)BaTm3 trigonal pyramids, edges with two equivalent O(3)BaTm3 trigonal pyramids, and edges with two equivalent O(1)Tm4 trigonal pyramids. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Ba(2), three equivalent Ba(1), one Tm(1), and one Tm(2) atom. In the third O site, O(3) is bonded to one Ba(1), one Tm(3), and two equivalent Tm(1) atoms to form distorted OBaTm3 trigonal pyramids that share corners with two equivalent O(4)Ba4Tm2 octahedra, corners with two equivalent O(7)Ba4Tm2 octahedra, corners with three equivalent O(6)BaTm3 tetrahedra, corners with two equivalent O(3)BaTm3 trigonal pyramids, corners with two equivalent O(1)Tm4 trigonal pyramids, and  an edgeedge with one O(1)Tm4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 27-71°. In the fourth O site, O(4) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Tm(2) atoms to form distorted OBa4Tm2 octahedra that share corners with two equivalent O(7)Ba4Tm2 octahedra, corners with two equivalent O(6)BaTm3 tetrahedra, corners with two equivalent O(3)BaTm3 trigonal pyramids, edges with two equivalent O(7)Ba4Tm2 octahedra, faces with two equivalent O(4)Ba4Tm2 octahedra, and faces with two equivalent O(7)Ba4Tm2 octahedra. The corner-sharing octahedral tilt angles range from 3-4°. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Ba(1), three equivalent Ba(2), one Tm(2), and one Tm(3) atom. In the sixth O site, O(6) is bonded to one Ba(2) and three equivalent Tm(3) atoms to form distorted OBaTm3 tetrahedra that share corners with two equivalent O(4)Ba4Tm2 octahedra, corners with two equivalent O(7)Ba4Tm2 octahedra, corners with four equivalent O(6)BaTm3 tetrahedra, corners with three equivalent O(3)BaTm3 trigonal pyramids, and  an edgeedge with one O(6)BaTm3 tetrahedra. The corner-sharing octahedral tilt angles range from 27-69°. In the seventh O site, O(7) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Tm(2) atoms to form distorted OBa4Tm2 octahedra that share corners with two equivalent O(4)Ba4Tm2 octahedra, corners with two equivalent O(6)BaTm3 tetrahedra, corners with two equivalent O(3)BaTm3 trigonal pyramids, edges with two equivalent O(4)Ba4Tm2 octahedra, faces with two equivalent O(4)Ba4Tm2 octahedra, and faces with two equivalent O(7)Ba4Tm2 octahedra. The corner-sharing octahedral tilt angles range from 3-4°.