Tb16B4Br23 crystallizes in the monoclinic C2/m space group. There are five inequivalent Tb sites. In the first Tb site, Tb(1) is bonded to one B(1), one Br(2), two equivalent Br(4), and two equivalent Br(6) atoms to form TbBBr5 octahedra that share  a cornercorner with one Tb(5)B3Br3 octahedra, corners with two equivalent Tb(4)B2Br4 octahedra, corners with two equivalent Tb(3)BBr5 octahedra, edges with two equivalent Tb(4)B2Br4 octahedra, edges with two equivalent Tb(2)BBr5 octahedra, and edges with two equivalent Tb(3)BBr5 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. In the second Tb site, Tb(2) is bonded to one B(2), one Br(1), one Br(2), one Br(5), one Br(6), and one Br(7) atom to form TbBBr5 octahedra that share  a cornercorner with one Tb(4)B2Br4 octahedra,  a cornercorner with one Tb(5)B3Br3 octahedra,  a cornercorner with one Tb(2)BBr5 octahedra,  an edgeedge with one Tb(5)B3Br3 octahedra,  an edgeedge with one Tb(1)BBr5 octahedra,  an edgeedge with one Tb(3)BBr5 octahedra, edges with two equivalent Tb(4)B2Br4 octahedra, and edges with two equivalent Tb(2)BBr5 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the third Tb site, Tb(3) is bonded to one B(1), one Br(5), one Br(7), one Br(8), and two equivalent Br(4) atoms to form TbBBr5 octahedra that share  a cornercorner with one Tb(4)B2Br4 octahedra,  a cornercorner with one Tb(1)BBr5 octahedra,  an edgeedge with one Tb(4)B2Br4 octahedra,  an edgeedge with one Tb(5)B3Br3 octahedra,  an edgeedge with one Tb(1)BBr5 octahedra,  an edgeedge with one Tb(2)BBr5 octahedra, and edges with two equivalent Tb(3)BBr5 octahedra. The corner-sharing octahedral tilt angles range from 4-9°. In the fourth Tb site, Tb(4) is bonded to one B(1), one B(2), one Br(3), one Br(7), and two equivalent Br(6) atoms to form distorted TbB2Br4 octahedra that share  a cornercorner with one Tb(4)B2Br4 octahedra,  a cornercorner with one Tb(1)BBr5 octahedra,  a cornercorner with one Tb(2)BBr5 octahedra,  a cornercorner with one Tb(3)BBr5 octahedra,  an edgeedge with one Tb(1)BBr5 octahedra,  an edgeedge with one Tb(3)BBr5 octahedra, edges with two equivalent Tb(4)B2Br4 octahedra, edges with two equivalent Tb(5)B3Br3 octahedra, and edges with two equivalent Tb(2)BBr5 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. In the fifth Tb site, Tb(5) is bonded to one B(1), two equivalent B(2), one Br(3), and two equivalent Br(5) atoms to form TbB3Br3 octahedra that share  a cornercorner with one Tb(1)BBr5 octahedra, corners with two equivalent Tb(2)BBr5 octahedra,  an edgeedge with one Tb(5)B3Br3 octahedra, edges with two equivalent Tb(2)BBr5 octahedra, edges with two equivalent Tb(3)BBr5 octahedra, and edges with four equivalent Tb(4)B2Br4 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. There are two inequivalent B sites. In the first B site, B(1) is bonded to one Tb(1), one Tb(5), two equivalent Tb(3), and two equivalent Tb(4) atoms to form edge-sharing BTb6 octahedra. In the second B site, B(2) is bonded to two equivalent Tb(2), two equivalent Tb(4), and two equivalent Tb(5) atoms to form edge-sharing BTb6 octahedra. There are eight inequivalent Br sites. In the first Br site, Br(1) is bonded in a square co-planar geometry to four equivalent Tb(2) atoms. In the second Br site, Br(2) is bonded in a distorted trigonal non-coplanar geometry to one Tb(1) and two equivalent Tb(2) atoms. In the third Br site, Br(3) is bonded in a 3-coordinate geometry to one Tb(5) and two equivalent Tb(4) atoms. In the fourth Br site, Br(4) is bonded in a T-shaped geometry to one Tb(1) and two equivalent Tb(3) atoms. In the fifth Br site, Br(5) is bonded in a distorted T-shaped geometry to one Tb(2), one Tb(3), and one Tb(5) atom. In the sixth Br site, Br(6) is bonded in a square co-planar geometry to one Tb(1), one Tb(2), and two equivalent Tb(4) atoms. In the seventh Br site, Br(7) is bonded in a distorted T-shaped geometry to one Tb(2), one Tb(3), and one Tb(4) atom. In the eighth Br site, Br(8) is bonded in an L-shaped geometry to two equivalent Tb(3) atoms.
Tb16B4Br23 crystallizes in the monoclinic C2/m space group. There are five inequivalent Tb sites. In the first Tb site, Tb(1) is bonded to one B(1), one Br(2), two equivalent Br(4), and two equivalent Br(6) atoms to form TbBBr5 octahedra that share  a cornercorner with one Tb(5)B3Br3 octahedra, corners with two equivalent Tb(4)B2Br4 octahedra, corners with two equivalent Tb(3)BBr5 octahedra, edges with two equivalent Tb(4)B2Br4 octahedra, edges with two equivalent Tb(2)BBr5 octahedra, and edges with two equivalent Tb(3)BBr5 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. The Tb(1)-B(1) bond length is 2.48 Å. The Tb(1)-Br(2) bond length is 3.01 Å. Both Tb(1)-Br(4) bond lengths are 2.85 Å. Both Tb(1)-Br(6) bond lengths are 2.93 Å. In the second Tb site, Tb(2) is bonded to one B(2), one Br(1), one Br(2), one Br(5), one Br(6), and one Br(7) atom to form TbBBr5 octahedra that share  a cornercorner with one Tb(4)B2Br4 octahedra,  a cornercorner with one Tb(5)B3Br3 octahedra,  a cornercorner with one Tb(2)BBr5 octahedra,  an edgeedge with one Tb(5)B3Br3 octahedra,  an edgeedge with one Tb(1)BBr5 octahedra,  an edgeedge with one Tb(3)BBr5 octahedra, edges with two equivalent Tb(4)B2Br4 octahedra, and edges with two equivalent Tb(2)BBr5 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. The Tb(2)-B(2) bond length is 2.46 Å. The Tb(2)-Br(1) bond length is 2.96 Å. The Tb(2)-Br(2) bond length is 3.05 Å. The Tb(2)-Br(5) bond length is 2.82 Å. The Tb(2)-Br(6) bond length is 2.93 Å. The Tb(2)-Br(7) bond length is 2.86 Å. In the third Tb site, Tb(3) is bonded to one B(1), one Br(5), one Br(7), one Br(8), and two equivalent Br(4) atoms to form TbBBr5 octahedra that share  a cornercorner with one Tb(4)B2Br4 octahedra,  a cornercorner with one Tb(1)BBr5 octahedra,  an edgeedge with one Tb(4)B2Br4 octahedra,  an edgeedge with one Tb(5)B3Br3 octahedra,  an edgeedge with one Tb(1)BBr5 octahedra,  an edgeedge with one Tb(2)BBr5 octahedra, and edges with two equivalent Tb(3)BBr5 octahedra. The corner-sharing octahedral tilt angles range from 4-9°. The Tb(3)-B(1) bond length is 2.50 Å. The Tb(3)-Br(5) bond length is 2.86 Å. The Tb(3)-Br(7) bond length is 2.90 Å. The Tb(3)-Br(8) bond length is 2.80 Å. There is one shorter (2.89 Å) and one longer (3.11 Å) Tb(3)-Br(4) bond length. In the fourth Tb site, Tb(4) is bonded to one B(1), one B(2), one Br(3), one Br(7), and two equivalent Br(6) atoms to form distorted TbB2Br4 octahedra that share  a cornercorner with one Tb(4)B2Br4 octahedra,  a cornercorner with one Tb(1)BBr5 octahedra,  a cornercorner with one Tb(2)BBr5 octahedra,  a cornercorner with one Tb(3)BBr5 octahedra,  an edgeedge with one Tb(1)BBr5 octahedra,  an edgeedge with one Tb(3)BBr5 octahedra, edges with two equivalent Tb(4)B2Br4 octahedra, edges with two equivalent Tb(5)B3Br3 octahedra, and edges with two equivalent Tb(2)BBr5 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. The Tb(4)-B(1) bond length is 2.66 Å. The Tb(4)-B(2) bond length is 2.56 Å. The Tb(4)-Br(3) bond length is 2.88 Å. The Tb(4)-Br(7) bond length is 2.95 Å. There is one shorter (3.07 Å) and one longer (3.09 Å) Tb(4)-Br(6) bond length. In the fifth Tb site, Tb(5) is bonded to one B(1), two equivalent B(2), one Br(3), and two equivalent Br(5) atoms to form TbB3Br3 octahedra that share  a cornercorner with one Tb(1)BBr5 octahedra, corners with two equivalent Tb(2)BBr5 octahedra,  an edgeedge with one Tb(5)B3Br3 octahedra, edges with two equivalent Tb(2)BBr5 octahedra, edges with two equivalent Tb(3)BBr5 octahedra, and edges with four equivalent Tb(4)B2Br4 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. The Tb(5)-B(1) bond length is 2.78 Å. Both Tb(5)-B(2) bond lengths are 2.73 Å. The Tb(5)-Br(3) bond length is 2.99 Å. Both Tb(5)-Br(5) bond lengths are 3.04 Å. There are two inequivalent B sites. In the first B site, B(1) is bonded to one Tb(1), one Tb(5), two equivalent Tb(3), and two equivalent Tb(4) atoms to form edge-sharing BTb6 octahedra. In the second B site, B(2) is bonded to two equivalent Tb(2), two equivalent Tb(4), and two equivalent Tb(5) atoms to form edge-sharing BTb6 octahedra. There are eight inequivalent Br sites. In the first Br site, Br(1) is bonded in a square co-planar geometry to four equivalent Tb(2) atoms. In the second Br site, Br(2) is bonded in a distorted trigonal non-coplanar geometry to one Tb(1) and two equivalent Tb(2) atoms. In the third Br site, Br(3) is bonded in a 3-coordinate geometry to one Tb(5) and two equivalent Tb(4) atoms. In the fourth Br site, Br(4) is bonded in a T-shaped geometry to one Tb(1) and two equivalent Tb(3) atoms. In the fifth Br site, Br(5) is bonded in a distorted T-shaped geometry to one Tb(2), one Tb(3), and one Tb(5) atom. In the sixth Br site, Br(6) is bonded in a square co-planar geometry to one Tb(1), one Tb(2), and two equivalent Tb(4) atoms. In the seventh Br site, Br(7) is bonded in a distorted T-shaped geometry to one Tb(2), one Tb(3), and one Tb(4) atom. In the eighth Br site, Br(8) is bonded in an L-shaped geometry to two equivalent Tb(3) atoms.