Tm4BO7Cl crystallizes in the monoclinic P2_1/c space group. There are four inequivalent Tm sites. In the first Tm site, Tm(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(6), one O(7), and one Cl(1) atom. In the second Tm site, Tm(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(5), two equivalent O(4), and one Cl(1) atom. In the third Tm site, Tm(3) is bonded in a 7-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one O(7), two equivalent O(1), and one Cl(1) atom. In the fourth Tm site, Tm(4) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), one O(6), one O(7), and two equivalent Cl(1) atoms. B(1) is bonded in a trigonal planar geometry to one O(5), one O(6), and one O(7) atom. There are seven inequivalent O sites. In the first O site, O(3) is bonded to one Tm(1), one Tm(2), one Tm(3), and one Tm(4) atom to form a mixture of corner and edge-sharing OTm4 tetrahedra. In the second O site, O(4) is bonded to one Tm(3), one Tm(4), and two equivalent Tm(2) atoms to form a mixture of corner and edge-sharing OTm4 tetrahedra. In the third O site, O(5) is bonded in a 4-coordinate geometry to one Tm(1), one Tm(2), one Tm(3), and one B(1) atom. In the fourth O site, O(6) is bonded in a distorted trigonal planar geometry to one Tm(1), one Tm(4), and one B(1) atom. In the fifth O site, O(7) is bonded in a distorted single-bond geometry to one Tm(1), one Tm(3), one Tm(4), and one B(1) atom. In the sixth O site, O(1) is bonded to one Tm(1), one Tm(2), and two equivalent Tm(3) atoms to form a mixture of corner and edge-sharing OTm4 tetrahedra. In the seventh O site, O(2) is bonded to one Tm(1), one Tm(2), one Tm(3), and one Tm(4) atom to form a mixture of corner and edge-sharing OTm4 tetrahedra. Cl(1) is bonded in a 5-coordinate geometry to one Tm(1), one Tm(2), one Tm(3), and two equivalent Tm(4) atoms.
Tm4BO7Cl crystallizes in the monoclinic P2_1/c space group. There are four inequivalent Tm sites. In the first Tm site, Tm(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(6), one O(7), and one Cl(1) atom. The Tm(1)-O(1) bond length is 2.20 Å. The Tm(1)-O(2) bond length is 2.26 Å. The Tm(1)-O(3) bond length is 2.29 Å. The Tm(1)-O(5) bond length is 2.26 Å. The Tm(1)-O(6) bond length is 2.22 Å. The Tm(1)-O(7) bond length is 2.32 Å. The Tm(1)-Cl(1) bond length is 3.14 Å. In the second Tm site, Tm(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(5), two equivalent O(4), and one Cl(1) atom. The Tm(2)-O(1) bond length is 2.27 Å. The Tm(2)-O(2) bond length is 2.28 Å. The Tm(2)-O(3) bond length is 2.25 Å. The Tm(2)-O(5) bond length is 2.34 Å. There is one shorter (2.23 Å) and one longer (2.28 Å) Tm(2)-O(4) bond length. The Tm(2)-Cl(1) bond length is 2.93 Å. In the third Tm site, Tm(3) is bonded in a 7-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one O(7), two equivalent O(1), and one Cl(1) atom. The Tm(3)-O(2) bond length is 2.27 Å. The Tm(3)-O(3) bond length is 2.27 Å. The Tm(3)-O(4) bond length is 2.23 Å. The Tm(3)-O(5) bond length is 2.54 Å. The Tm(3)-O(7) bond length is 2.74 Å. There is one shorter (2.25 Å) and one longer (2.29 Å) Tm(3)-O(1) bond length. The Tm(3)-Cl(1) bond length is 3.28 Å. In the fourth Tm site, Tm(4) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), one O(6), one O(7), and two equivalent Cl(1) atoms. The Tm(4)-O(2) bond length is 2.24 Å. The Tm(4)-O(3) bond length is 2.20 Å. The Tm(4)-O(4) bond length is 2.18 Å. The Tm(4)-O(6) bond length is 2.24 Å. The Tm(4)-O(7) bond length is 2.32 Å. There is one shorter (2.84 Å) and one longer (3.26 Å) Tm(4)-Cl(1) bond length. B(1) is bonded in a trigonal planar geometry to one O(5), one O(6), and one O(7) atom. The B(1)-O(5) bond length is 1.38 Å. The B(1)-O(6) bond length is 1.37 Å. The B(1)-O(7) bond length is 1.38 Å. There are seven inequivalent O sites. In the first O site, O(3) is bonded to one Tm(1), one Tm(2), one Tm(3), and one Tm(4) atom to form a mixture of corner and edge-sharing OTm4 tetrahedra. In the second O site, O(4) is bonded to one Tm(3), one Tm(4), and two equivalent Tm(2) atoms to form a mixture of corner and edge-sharing OTm4 tetrahedra. In the third O site, O(5) is bonded in a 4-coordinate geometry to one Tm(1), one Tm(2), one Tm(3), and one B(1) atom. In the fourth O site, O(6) is bonded in a distorted trigonal planar geometry to one Tm(1), one Tm(4), and one B(1) atom. In the fifth O site, O(7) is bonded in a distorted single-bond geometry to one Tm(1), one Tm(3), one Tm(4), and one B(1) atom. In the sixth O site, O(1) is bonded to one Tm(1), one Tm(2), and two equivalent Tm(3) atoms to form a mixture of corner and edge-sharing OTm4 tetrahedra. In the seventh O site, O(2) is bonded to one Tm(1), one Tm(2), one Tm(3), and one Tm(4) atom to form a mixture of corner and edge-sharing OTm4 tetrahedra. Cl(1) is bonded in a 5-coordinate geometry to one Tm(1), one Tm(2), one Tm(3), and two equivalent Tm(4) atoms.