K3(TcCl4)2 crystallizes in the monoclinic C2 space group. There are five inequivalent K sites. In the first K site, K(1) is bonded in a 9-coordinate geometry to one Cl(1), one Cl(10), one Cl(11), one Cl(12), one Cl(3), one Cl(4), one Cl(7), and two equivalent Cl(6) atoms. In the second K site, K(2) is bonded in a 9-coordinate geometry to one Cl(10), one Cl(11), one Cl(12), one Cl(4), one Cl(8), two equivalent Cl(2), and two equivalent Cl(5) atoms. In the third K site, K(3) is bonded in a 9-coordinate geometry to one Cl(1), one Cl(10), one Cl(11), one Cl(12), one Cl(3), one Cl(4), one Cl(5), one Cl(6), and one Cl(9) atom. In the fourth K site, K(4) is bonded in a 6-coordinate geometry to one Cl(1), one Cl(10), one Cl(12), one Cl(2), one Cl(4), and one Cl(6) atom. In the fifth K site, K(5) is bonded in a 6-coordinate geometry to two equivalent Cl(11), two equivalent Cl(3), and two equivalent Cl(5) atoms. There are three inequivalent Tc sites. In the first Tc site, Tc(1) is bonded in a 5-coordinate geometry to one Tc(3), one Cl(1), one Cl(10), one Cl(4), and one Cl(7) atom. In the second Tc site, Tc(2) is bonded in a 5-coordinate geometry to one Tc(2), one Cl(11), one Cl(2), one Cl(5), and one Cl(8) atom. In the third Tc site, Tc(3) is bonded in a 5-coordinate geometry to one Tc(1), one Cl(12), one Cl(3), one Cl(6), and one Cl(9) atom. There are twelve inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 4-coordinate geometry to one K(1), one K(3), one K(4), and one Tc(1) atom. In the second Cl site, Cl(2) is bonded in a 4-coordinate geometry to one K(4), two equivalent K(2), and one Tc(2) atom. In the third Cl site, Cl(3) is bonded in a 4-coordinate geometry to one K(1), one K(3), one K(5), and one Tc(3) atom. In the fourth Cl site, Cl(4) is bonded to one K(1), one K(2), one K(3), one K(4), and one Tc(1) atom to form a mixture of distorted edge and corner-sharing ClK4Tc square pyramids. In the fifth Cl site, Cl(5) is bonded to one K(3), one K(5), two equivalent K(2), and one Tc(2) atom to form a mixture of distorted edge and corner-sharing ClK4Tc square pyramids. In the sixth Cl site, Cl(6) is bonded to one K(3), one K(4), two equivalent K(1), and one Tc(3) atom to form a mixture of distorted edge and corner-sharing ClK4Tc square pyramids. In the seventh Cl site, Cl(7) is bonded in a distorted single-bond geometry to one K(1) and one Tc(1) atom. In the eighth Cl site, Cl(8) is bonded in a distorted single-bond geometry to one K(2) and one Tc(2) atom. In the ninth Cl site, Cl(9) is bonded in a distorted single-bond geometry to one K(3) and one Tc(3) atom. In the tenth Cl site, Cl(10) is bonded in a 5-coordinate geometry to one K(1), one K(2), one K(3), one K(4), and one Tc(1) atom. In the eleventh Cl site, Cl(11) is bonded in a 5-coordinate geometry to one K(1), one K(2), one K(3), one K(5), and one Tc(2) atom. In the twelfth Cl site, Cl(12) is bonded in a 5-coordinate geometry to one K(1), one K(2), one K(3), one K(4), and one Tc(3) atom.
K3(TcCl4)2 crystallizes in the monoclinic C2 space group. There are five inequivalent K sites. In the first K site, K(1) is bonded in a 9-coordinate geometry to one Cl(1), one Cl(10), one Cl(11), one Cl(12), one Cl(3), one Cl(4), one Cl(7), and two equivalent Cl(6) atoms. The K(1)-Cl(1) bond length is 3.37 Å. The K(1)-Cl(10) bond length is 3.12 Å. The K(1)-Cl(11) bond length is 3.36 Å. The K(1)-Cl(12) bond length is 3.37 Å. The K(1)-Cl(3) bond length is 3.32 Å. The K(1)-Cl(4) bond length is 3.22 Å. The K(1)-Cl(7) bond length is 3.40 Å. There is one shorter (3.23 Å) and one longer (3.36 Å) K(1)-Cl(6) bond length. In the second K site, K(2) is bonded in a 9-coordinate geometry to one Cl(10), one Cl(11), one Cl(12), one Cl(4), one Cl(8), two equivalent Cl(2), and two equivalent Cl(5) atoms. The K(2)-Cl(10) bond length is 3.37 Å. The K(2)-Cl(11) bond length is 3.12 Å. The K(2)-Cl(12) bond length is 3.36 Å. The K(2)-Cl(4) bond length is 3.35 Å. The K(2)-Cl(8) bond length is 3.40 Å. There is one shorter (3.32 Å) and one longer (3.37 Å) K(2)-Cl(2) bond length. There is one shorter (3.22 Å) and one longer (3.24 Å) K(2)-Cl(5) bond length. In the third K site, K(3) is bonded in a 9-coordinate geometry to one Cl(1), one Cl(10), one Cl(11), one Cl(12), one Cl(3), one Cl(4), one Cl(5), one Cl(6), and one Cl(9) atom. The K(3)-Cl(1) bond length is 3.32 Å. The K(3)-Cl(10) bond length is 3.35 Å. The K(3)-Cl(11) bond length is 3.38 Å. The K(3)-Cl(12) bond length is 3.12 Å. The K(3)-Cl(3) bond length is 3.37 Å. The K(3)-Cl(4) bond length is 3.24 Å. The K(3)-Cl(5) bond length is 3.35 Å. The K(3)-Cl(6) bond length is 3.22 Å. The K(3)-Cl(9) bond length is 3.40 Å. In the fourth K site, K(4) is bonded in a 6-coordinate geometry to one Cl(1), one Cl(10), one Cl(12), one Cl(2), one Cl(4), and one Cl(6) atom. The K(4)-Cl(1) bond length is 3.17 Å. The K(4)-Cl(10) bond length is 3.29 Å. The K(4)-Cl(12) bond length is 3.29 Å. The K(4)-Cl(2) bond length is 3.17 Å. The K(4)-Cl(4) bond length is 3.20 Å. The K(4)-Cl(6) bond length is 3.21 Å. In the fifth K site, K(5) is bonded in a 6-coordinate geometry to two equivalent Cl(11), two equivalent Cl(3), and two equivalent Cl(5) atoms. Both K(5)-Cl(11) bond lengths are 3.29 Å. Both K(5)-Cl(3) bond lengths are 3.17 Å. Both K(5)-Cl(5) bond lengths are 3.21 Å. There are three inequivalent Tc sites. In the first Tc site, Tc(1) is bonded in a 5-coordinate geometry to one Tc(3), one Cl(1), one Cl(10), one Cl(4), and one Cl(7) atom. The Tc(1)-Tc(3) bond length is 2.12 Å. The Tc(1)-Cl(1) bond length is 2.37 Å. The Tc(1)-Cl(10) bond length is 2.39 Å. The Tc(1)-Cl(4) bond length is 2.40 Å. The Tc(1)-Cl(7) bond length is 2.33 Å. In the second Tc site, Tc(2) is bonded in a 5-coordinate geometry to one Tc(2), one Cl(11), one Cl(2), one Cl(5), and one Cl(8) atom. The Tc(2)-Tc(2) bond length is 2.11 Å. The Tc(2)-Cl(11) bond length is 2.39 Å. The Tc(2)-Cl(2) bond length is 2.37 Å. The Tc(2)-Cl(5) bond length is 2.40 Å. The Tc(2)-Cl(8) bond length is 2.33 Å. In the third Tc site, Tc(3) is bonded in a 5-coordinate geometry to one Tc(1), one Cl(12), one Cl(3), one Cl(6), and one Cl(9) atom. The Tc(3)-Cl(12) bond length is 2.39 Å. The Tc(3)-Cl(3) bond length is 2.37 Å. The Tc(3)-Cl(6) bond length is 2.40 Å. The Tc(3)-Cl(9) bond length is 2.33 Å. There are twelve inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 4-coordinate geometry to one K(1), one K(3), one K(4), and one Tc(1) atom. In the second Cl site, Cl(2) is bonded in a 4-coordinate geometry to one K(4), two equivalent K(2), and one Tc(2) atom. In the third Cl site, Cl(3) is bonded in a 4-coordinate geometry to one K(1), one K(3), one K(5), and one Tc(3) atom. In the fourth Cl site, Cl(4) is bonded to one K(1), one K(2), one K(3), one K(4), and one Tc(1) atom to form a mixture of distorted edge and corner-sharing ClK4Tc square pyramids. In the fifth Cl site, Cl(5) is bonded to one K(3), one K(5), two equivalent K(2), and one Tc(2) atom to form a mixture of distorted edge and corner-sharing ClK4Tc square pyramids. In the sixth Cl site, Cl(6) is bonded to one K(3), one K(4), two equivalent K(1), and one Tc(3) atom to form a mixture of distorted edge and corner-sharing ClK4Tc square pyramids. In the seventh Cl site, Cl(7) is bonded in a distorted single-bond geometry to one K(1) and one Tc(1) atom. In the eighth Cl site, Cl(8) is bonded in a distorted single-bond geometry to one K(2) and one Tc(2) atom. In the ninth Cl site, Cl(9) is bonded in a distorted single-bond geometry to one K(3) and one Tc(3) atom. In the tenth Cl site, Cl(10) is bonded in a 5-coordinate geometry to one K(1), one K(2), one K(3), one K(4), and one Tc(1) atom. In the eleventh Cl site, Cl(11) is bonded in a 5-coordinate geometry to one K(1), one K(2), one K(3), one K(5), and one Tc(2) atom. In the twelfth Cl site, Cl(12) is bonded in a 5-coordinate geometry to one K(1), one K(2), one K(3), one K(4), and one Tc(3) atom.