CsTc3(Se2Br)2 crystallizes in the monoclinic P2_1/c space group. Cs(1) is bonded in a 10-coordinate geometry to one Se(4), two equivalent Se(1), two equivalent Se(2), two equivalent Br(2), and three equivalent Br(1) atoms. There are three inequivalent Tc sites. In the first Tc site, Tc(1) is bonded to one Se(1), one Se(2), one Se(3), one Se(4), and one Br(1) atom to form distorted TcSe4Br square pyramids that share  a cornercorner with one Tc(3)Se5 square pyramid, edges with two equivalent Tc(2)Se4Br square pyramids, and edges with two equivalent Tc(3)Se5 square pyramids. In the second Tc site, Tc(2) is bonded to one Se(1), one Se(2), one Se(3), one Se(4), and one Br(2) atom to form distorted TcSe4Br square pyramids that share  a cornercorner with one Tc(3)Se5 square pyramid, edges with two equivalent Tc(1)Se4Br square pyramids, and edges with two equivalent Tc(3)Se5 square pyramids. In the third Tc site, Tc(3) is bonded to one Se(1), one Se(2), one Se(4), and two equivalent Se(3) atoms to form distorted TcSe5 square pyramids that share  a cornercorner with one Tc(1)Se4Br square pyramid,  a cornercorner with one Tc(2)Se4Br square pyramid,  an edgeedge with one Tc(3)Se5 square pyramid, edges with two equivalent Tc(1)Se4Br square pyramids, and edges with two equivalent Tc(2)Se4Br square pyramids. There are four inequivalent Se sites. In the first Se site, Se(1) is bonded in a 5-coordinate geometry to two equivalent Cs(1), one Tc(1), one Tc(2), and one Tc(3) atom. In the second Se site, Se(2) is bonded in a 3-coordinate geometry to two equivalent Cs(1), one Tc(1), one Tc(2), and one Tc(3) atom. In the third Se site, Se(3) is bonded in a distorted rectangular see-saw-like geometry to one Tc(1), one Tc(2), and two equivalent Tc(3) atoms. In the fourth Se site, Se(4) is bonded in a 4-coordinate geometry to one Cs(1), one Tc(1), one Tc(2), and one Tc(3) atom. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Cs(1) and one Tc(1) atom. In the second Br site, Br(2) is bonded in a 3-coordinate geometry to two equivalent Cs(1) and one Tc(2) atom.
CsTc3(Se2Br)2 crystallizes in the monoclinic P2_1/c space group. Cs(1) is bonded in a 10-coordinate geometry to one Se(4), two equivalent Se(1), two equivalent Se(2), two equivalent Br(2), and three equivalent Br(1) atoms. The Cs(1)-Se(4) bond length is 3.78 Å. There is one shorter (3.85 Å) and one longer (4.13 Å) Cs(1)-Se(1) bond length. There is one shorter (4.05 Å) and one longer (4.32 Å) Cs(1)-Se(2) bond length. There is one shorter (3.76 Å) and one longer (4.02 Å) Cs(1)-Br(2) bond length. There are a spread of Cs(1)-Br(1) bond distances ranging from 3.75-3.84 Å. There are three inequivalent Tc sites. In the first Tc site, Tc(1) is bonded to one Se(1), one Se(2), one Se(3), one Se(4), and one Br(1) atom to form distorted TcSe4Br square pyramids that share  a cornercorner with one Tc(3)Se5 square pyramid, edges with two equivalent Tc(2)Se4Br square pyramids, and edges with two equivalent Tc(3)Se5 square pyramids. The Tc(1)-Se(1) bond length is 2.51 Å. The Tc(1)-Se(2) bond length is 2.52 Å. The Tc(1)-Se(3) bond length is 2.54 Å. The Tc(1)-Se(4) bond length is 2.53 Å. The Tc(1)-Br(1) bond length is 2.62 Å. In the second Tc site, Tc(2) is bonded to one Se(1), one Se(2), one Se(3), one Se(4), and one Br(2) atom to form distorted TcSe4Br square pyramids that share  a cornercorner with one Tc(3)Se5 square pyramid, edges with two equivalent Tc(1)Se4Br square pyramids, and edges with two equivalent Tc(3)Se5 square pyramids. The Tc(2)-Se(1) bond length is 2.52 Å. The Tc(2)-Se(2) bond length is 2.51 Å. The Tc(2)-Se(3) bond length is 2.53 Å. The Tc(2)-Se(4) bond length is 2.52 Å. The Tc(2)-Br(2) bond length is 2.60 Å. In the third Tc site, Tc(3) is bonded to one Se(1), one Se(2), one Se(4), and two equivalent Se(3) atoms to form distorted TcSe5 square pyramids that share  a cornercorner with one Tc(1)Se4Br square pyramid,  a cornercorner with one Tc(2)Se4Br square pyramid,  an edgeedge with one Tc(3)Se5 square pyramid, edges with two equivalent Tc(1)Se4Br square pyramids, and edges with two equivalent Tc(2)Se4Br square pyramids. The Tc(3)-Se(1) bond length is 2.51 Å. The Tc(3)-Se(2) bond length is 2.51 Å. The Tc(3)-Se(4) bond length is 2.53 Å. There is one shorter (2.61 Å) and one longer (2.66 Å) Tc(3)-Se(3) bond length. There are four inequivalent Se sites. In the first Se site, Se(1) is bonded in a 5-coordinate geometry to two equivalent Cs(1), one Tc(1), one Tc(2), and one Tc(3) atom. In the second Se site, Se(2) is bonded in a 3-coordinate geometry to two equivalent Cs(1), one Tc(1), one Tc(2), and one Tc(3) atom. In the third Se site, Se(3) is bonded in a distorted rectangular see-saw-like geometry to one Tc(1), one Tc(2), and two equivalent Tc(3) atoms. In the fourth Se site, Se(4) is bonded in a 4-coordinate geometry to one Cs(1), one Tc(1), one Tc(2), and one Tc(3) atom. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Cs(1) and one Tc(1) atom. In the second Br site, Br(2) is bonded in a 3-coordinate geometry to two equivalent Cs(1) and one Tc(2) atom.