BaTmCo4O7 crystallizes in the monoclinic Cc space group. Ba(1) is bonded in a 9-coordinate geometry to one O(2), one O(3), one O(4), two equivalent O(5), two equivalent O(6), and two equivalent O(7) atoms. Tm(1) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form TmO6 octahedra that share corners with three equivalent Co(1)O4 tetrahedra, corners with three equivalent Co(2)O4 tetrahedra, corners with three equivalent Co(3)O4 tetrahedra, and corners with three equivalent Co(4)O4 tetrahedra. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(2), one O(6), and one O(7) atom to form CoO4 tetrahedra that share corners with three equivalent Tm(1)O6 octahedra, corners with two equivalent Co(2)O4 tetrahedra, corners with two equivalent Co(3)O4 tetrahedra, and corners with two equivalent Co(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-60°. In the second Co site, Co(2) is bonded to one O(1), one O(3), one O(5), and one O(7) atom to form CoO4 tetrahedra that share corners with three equivalent Tm(1)O6 octahedra, corners with two equivalent Co(1)O4 tetrahedra, corners with two equivalent Co(3)O4 tetrahedra, and corners with two equivalent Co(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-60°. In the third Co site, Co(3) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form CoO4 tetrahedra that share corners with three equivalent Tm(1)O6 octahedra, corners with two equivalent Co(1)O4 tetrahedra, corners with two equivalent Co(2)O4 tetrahedra, and corners with two equivalent Co(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-60°. In the fourth Co site, Co(4) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form CoO4 tetrahedra that share corners with three equivalent Tm(1)O6 octahedra, corners with two equivalent Co(1)O4 tetrahedra, corners with two equivalent Co(2)O4 tetrahedra, and corners with two equivalent Co(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-54°. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Ba(1), one Tm(1), one Co(2), and one Co(3) atom. In the second O site, O(6) is bonded in a distorted trigonal planar geometry to two equivalent Ba(1), one Tm(1), one Co(1), and one Co(3) atom. In the third O site, O(7) is bonded in a distorted trigonal planar geometry to two equivalent Ba(1), one Tm(1), one Co(1), and one Co(2) atom. In the fourth O site, O(1) is bonded in a tetrahedral geometry to one Co(1), one Co(2), one Co(3), and one Co(4) atom. In the fifth O site, O(2) is bonded in a 3-coordinate geometry to one Ba(1), one Tm(1), one Co(1), and one Co(4) atom. In the sixth O site, O(3) is bonded in a 4-coordinate geometry to one Ba(1), one Tm(1), one Co(2), and one Co(4) atom. In the seventh O site, O(4) is bonded in a 4-coordinate geometry to one Ba(1), one Tm(1), one Co(3), and one Co(4) atom.
BaTmCo4O7 crystallizes in the monoclinic Cc space group. Ba(1) is bonded in a 9-coordinate geometry to one O(2), one O(3), one O(4), two equivalent O(5), two equivalent O(6), and two equivalent O(7) atoms. The Ba(1)-O(2) bond length is 2.94 Å. The Ba(1)-O(3) bond length is 2.86 Å. The Ba(1)-O(4) bond length is 2.85 Å. There is one shorter (3.12 Å) and one longer (3.18 Å) Ba(1)-O(5) bond length. There is one shorter (3.14 Å) and one longer (3.20 Å) Ba(1)-O(6) bond length. There is one shorter (3.13 Å) and one longer (3.17 Å) Ba(1)-O(7) bond length. Tm(1) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form TmO6 octahedra that share corners with three equivalent Co(1)O4 tetrahedra, corners with three equivalent Co(2)O4 tetrahedra, corners with three equivalent Co(3)O4 tetrahedra, and corners with three equivalent Co(4)O4 tetrahedra. The Tm(1)-O(2) bond length is 2.31 Å. The Tm(1)-O(3) bond length is 2.31 Å. The Tm(1)-O(4) bond length is 2.30 Å. The Tm(1)-O(5) bond length is 2.20 Å. The Tm(1)-O(6) bond length is 2.20 Å. The Tm(1)-O(7) bond length is 2.21 Å. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(2), one O(6), and one O(7) atom to form CoO4 tetrahedra that share corners with three equivalent Tm(1)O6 octahedra, corners with two equivalent Co(2)O4 tetrahedra, corners with two equivalent Co(3)O4 tetrahedra, and corners with two equivalent Co(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-60°. The Co(1)-O(1) bond length is 2.00 Å. The Co(1)-O(2) bond length is 1.99 Å. The Co(1)-O(6) bond length is 1.95 Å. The Co(1)-O(7) bond length is 1.94 Å. In the second Co site, Co(2) is bonded to one O(1), one O(3), one O(5), and one O(7) atom to form CoO4 tetrahedra that share corners with three equivalent Tm(1)O6 octahedra, corners with two equivalent Co(1)O4 tetrahedra, corners with two equivalent Co(3)O4 tetrahedra, and corners with two equivalent Co(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-60°. The Co(2)-O(1) bond length is 1.99 Å. The Co(2)-O(3) bond length is 2.00 Å. The Co(2)-O(5) bond length is 1.94 Å. The Co(2)-O(7) bond length is 1.95 Å. In the third Co site, Co(3) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form CoO4 tetrahedra that share corners with three equivalent Tm(1)O6 octahedra, corners with two equivalent Co(1)O4 tetrahedra, corners with two equivalent Co(2)O4 tetrahedra, and corners with two equivalent Co(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-60°. The Co(3)-O(1) bond length is 1.99 Å. The Co(3)-O(4) bond length is 1.98 Å. The Co(3)-O(5) bond length is 1.96 Å. The Co(3)-O(6) bond length is 1.94 Å. In the fourth Co site, Co(4) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form CoO4 tetrahedra that share corners with three equivalent Tm(1)O6 octahedra, corners with two equivalent Co(1)O4 tetrahedra, corners with two equivalent Co(2)O4 tetrahedra, and corners with two equivalent Co(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-54°. The Co(4)-O(1) bond length is 1.94 Å. The Co(4)-O(2) bond length is 1.89 Å. The Co(4)-O(3) bond length is 1.87 Å. The Co(4)-O(4) bond length is 1.90 Å. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Ba(1), one Tm(1), one Co(2), and one Co(3) atom. In the second O site, O(6) is bonded in a distorted trigonal planar geometry to two equivalent Ba(1), one Tm(1), one Co(1), and one Co(3) atom. In the third O site, O(7) is bonded in a distorted trigonal planar geometry to two equivalent Ba(1), one Tm(1), one Co(1), and one Co(2) atom. In the fourth O site, O(1) is bonded in a tetrahedral geometry to one Co(1), one Co(2), one Co(3), and one Co(4) atom. In the fifth O site, O(2) is bonded in a 3-coordinate geometry to one Ba(1), one Tm(1), one Co(1), and one Co(4) atom. In the sixth O site, O(3) is bonded in a 4-coordinate geometry to one Ba(1), one Tm(1), one Co(2), and one Co(4) atom. In the seventh O site, O(4) is bonded in a 4-coordinate geometry to one Ba(1), one Tm(1), one Co(3), and one Co(4) atom.