Synthese und Strukturuntersuchungen von Iodocupraten (I). XI. Die Kristallstruktur von Tl₄Cu₂I₆

Abstract

Tetrathallium‐di‐μ‐iodo‐bis(diiodocuprat(I)) Tl4Cu2I6 kann durch Umsetzung von CuI mit TlI in der Schmelze oder durch Hydrothermalsynthese in konzentrierter, wäßriger HI hergestellt werden. Die Kristallstrukturaufklärung von Tl4Cu2I6 (orthorhombisch, Pnnm, a = 919,6(1), b = 955,2(2), c = 933,6(2) pm, Z = 2) ergab, daß die Verbindung zweikernige Anionen [Cu2I6]4− enthält, bei denen zwei CuI4‐Tetraeder über eine gemeinsame Kante verknüpft sind. Die Koordination des TlI mit I− entspricht der im gelben Thalliumiodid.

Dimeric Cu(I) Bromide Species Consisting of Two Edge-Shared Tetrahedra: Crystal Structure of (C8H14N2)2Cu2Br6

“…It is instructive to compare the structure reported here with the structures of the two Cu 2 I 6 4- anions previously reported. The anion in [(py) 2 CH 2 ] 2 Cu 2 I 6 , where (py) 2 CH 2 2+ is the dipyridinemethane cation,6a has a geometry remarkably similar to the geometry of the Cu 2 Br 6 4- anion reported in this study. The bridging Cu−X−Cu angles are 86.67(3)° in the iodide salt, compared to 86.29(5)° for the Br salt.…”

“…Similarly, the bridging geometry is asymmetric, with a difference of 0.169(2) Å compared to 0.239(3) Å in the Br salt. In contrast, the Cu 2 I 6 4- anions in Tl 4 Cu 2 I 6 have a very different structure,6b with symmetric bridges and very acute Cu−I−Cu angles of 60.77(4)°. This difference is presumably due to the difference in the nature of the electrostatic interactions and the hardness associated with the two different cations.…”

“…Two types of dimers based on triangular species have been previously reported: Cu 2 X 4 2- anions formed by edge sharing of two of the triangular anions and Cu 2 X 5 3- anions formed by corner sharing of two such anions . For X = I, two compounds containing Cu 2 I 6 4- anions formed by the edge-sharing of two CuX 4 tetrahedra have been reported …”

Intermolecular Ferromagnetic and Antiferromagnetic Interactions in Halogen-Bridged Copper(I) Imino Nitroxides: Crystal Structures and Magnetic Properties of [CuI(μ-X)(imino nitroxide)]2(X = I or Br)

“…On the other hand, copper(I) halocuprates display a wide variety in structures. These molecules form discrete geometries of varying nuclearity or polymeric extended systems . If organic radicals are introduced into the halocuprate cluster or network, interesting magnetic materials might be obtained.…”

Trimeric Units [Ag3X8]5– with Face‐sharing Polyhedra in the Series Tl2AgX3 (X = Cl, Br, I): Synthesis, Crystal Structure, and Vibrational Spectra

“…TlAgI 2 , [9] InAgI 2 , [9] In 2 AgI 3 (isotypical to Tl 2 AgI 3 ), [9] and Tl 2 CuI 3 (dimers of edge-sharing [CuI 4 ] 3tetrahedra). [10] A special case is Tl 6 Ag 2 I 10 , which represents a polyiodide with [I 4 ] 2units and chains of interconnected [AgI 6 ] 5octahedra. [11] With respect to the binary halides AgX and TlX, there was no analogy expected, because these iodides crystallize in different structures with lower coordination numbers (α-AgI: wurtzite type, CN = 4; TlI, own type, CN = 7) than the corre-ARTICLE sponding isotypical chlorides and bromides (AgCl, AgBr: NaCl type, CN = 6; TlCl, TlBr: CsCl type, CN = 8).…”