Rb2(TcSe2)3 crystallizes in the monoclinic C2/c space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 6-coordinate geometry to two equivalent Se(3), two equivalent Se(4), and two equivalent Se(6) atoms. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to two equivalent Se(1), two equivalent Se(4), two equivalent Se(5), and two equivalent Se(6) atoms. In the third Rb site, Rb(3) is bonded in a 8-coordinate geometry to one Se(3), one Se(6), two equivalent Se(2), two equivalent Se(4), and two equivalent Se(5) 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 Se(5) atom to form distorted edge-sharing TcSe5 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 Se(6) atom to form a mixture of distorted corner and edge-sharing TcSe5 square pyramids. In the third Tc site, Tc(3) is bonded to one Se(1), one Se(2), one Se(3), one Se(4), and one Se(6) atom to form a mixture of distorted corner and edge-sharing TcSe5 square pyramids. There are six inequivalent Se sites. In the first Se site, Se(1) is bonded in a 4-coordinate geometry to one Rb(2), one Tc(1), one Tc(2), and one Tc(3) atom. In the second Se site, Se(2) is bonded to two equivalent Rb(3), one Tc(1), one Tc(2), and one Tc(3) atom to form distorted edge-sharing SeRb2Tc3 trigonal bipyramids. In the third Se site, Se(3) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(3), one Tc(1), one Tc(2), and one Tc(3) atom. In the fourth Se site, Se(4) is bonded in a 7-coordinate geometry to one Rb(1), one Rb(2), two equivalent Rb(3), one Tc(1), one Tc(2), and one Tc(3) atom. In the fifth Se site, Se(5) is bonded in a 5-coordinate geometry to one Rb(2), two equivalent Rb(3), one Tc(1), and one Se(5) atom. In the sixth Se site, Se(6) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(2), one Rb(3), one Tc(2), and one Tc(3) atom.
Rb2(TcSe2)3 crystallizes in the monoclinic C2/c space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 6-coordinate geometry to two equivalent Se(3), two equivalent Se(4), and two equivalent Se(6) atoms. Both Rb(1)-Se(3) bond lengths are 3.42 Å. Both Rb(1)-Se(4) bond lengths are 3.68 Å. Both Rb(1)-Se(6) bond lengths are 3.41 Å. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to two equivalent Se(1), two equivalent Se(4), two equivalent Se(5), and two equivalent Se(6) atoms. Both Rb(2)-Se(1) bond lengths are 3.36 Å. Both Rb(2)-Se(4) bond lengths are 3.67 Å. Both Rb(2)-Se(5) bond lengths are 3.45 Å. Both Rb(2)-Se(6) bond lengths are 3.43 Å. In the third Rb site, Rb(3) is bonded in a 8-coordinate geometry to one Se(3), one Se(6), two equivalent Se(2), two equivalent Se(4), and two equivalent Se(5) atoms. The Rb(3)-Se(3) bond length is 3.46 Å. The Rb(3)-Se(6) bond length is 3.36 Å. There is one shorter (3.31 Å) and one longer (3.41 Å) Rb(3)-Se(2) bond length. There is one shorter (3.78 Å) and one longer (3.91 Å) Rb(3)-Se(4) bond length. There is one shorter (3.46 Å) and one longer (3.47 Å) Rb(3)-Se(5) bond length. 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 Se(5) atom to form distorted edge-sharing TcSe5 square pyramids. The Tc(1)-Se(1) bond length is 2.50 Å. The Tc(1)-Se(2) bond length is 2.51 Å. The Tc(1)-Se(3) bond length is 2.50 Å. The Tc(1)-Se(4) bond length is 2.55 Å. The Tc(1)-Se(5) bond length is 2.65 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 Se(6) atom to form a mixture of distorted corner and edge-sharing TcSe5 square pyramids. The Tc(2)-Se(1) bond length is 2.53 Å. The Tc(2)-Se(2) bond length is 2.48 Å. The Tc(2)-Se(3) bond length is 2.48 Å. The Tc(2)-Se(4) bond length is 2.53 Å. The Tc(2)-Se(6) bond length is 2.66 Å. In the third Tc site, Tc(3) is bonded to one Se(1), one Se(2), one Se(3), one Se(4), and one Se(6) atom to form a mixture of distorted corner and edge-sharing TcSe5 square pyramids. The Tc(3)-Se(1) bond length is 2.48 Å. The Tc(3)-Se(2) bond length is 2.53 Å. The Tc(3)-Se(3) bond length is 2.51 Å. The Tc(3)-Se(4) bond length is 2.54 Å. The Tc(3)-Se(6) bond length is 2.66 Å. There are six inequivalent Se sites. In the first Se site, Se(1) is bonded in a 4-coordinate geometry to one Rb(2), one Tc(1), one Tc(2), and one Tc(3) atom. In the second Se site, Se(2) is bonded to two equivalent Rb(3), one Tc(1), one Tc(2), and one Tc(3) atom to form distorted edge-sharing SeRb2Tc3 trigonal bipyramids. In the third Se site, Se(3) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(3), one Tc(1), one Tc(2), and one Tc(3) atom. In the fourth Se site, Se(4) is bonded in a 7-coordinate geometry to one Rb(1), one Rb(2), two equivalent Rb(3), one Tc(1), one Tc(2), and one Tc(3) atom. In the fifth Se site, Se(5) is bonded in a 5-coordinate geometry to one Rb(2), two equivalent Rb(3), one Tc(1), and one Se(5) atom. The Se(5)-Se(5) bond length is 2.44 Å. In the sixth Se site, Se(6) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(2), one Rb(3), one Tc(2), and one Tc(3) atom.