The quest for mercury sensitive ion exchangers results in a diamondlike network $^{3}_{\infty}\rm [(CUI)_{2}(1,10DT18C6)]$ (1). This is in contrast to the similar well known 44 network $^{2}_{\infty}\rm [(CUI)(1,10DT18C6)]$ described by Röttgers and Sheldrick [1] a 3D strucutre. 1 is accessible by treatment of CuI with 1,10‐dithia‐18‐crown‐6 in acetonitrile solution in a sealed glass tube in the presence of HgI, but it doesn't contain mercury at all. It seems that either the presence of mercury salts or the excess of iodine ions plays a catalytic role, which is not clarified yet. The main building blocks of 1 are distorted cubes of CuI, which are linked with crown ether rods to give an adamantanlike structure. The space inside the diamondlike network is filled by interpenetration with in sum three similar networks. The longest distance between oppositely CuI cubes in the adamantanlike building block is with 44.796(9) Å three times the b axis.

CuI‐based coordination polymers with 1, 2‐ethanedithiol, 3, 6‐dioxa‐1, 8‐octanedithiol and 3‐oxa‐1, 5‐pentanedinitrile as respectively μ‐S, S′ and μ‐N, N′ bridging ligands have been prepared by reaction of CuI with the appropriate alkane derivative in acetonitrile. [Cu(HSCH2CH2SH)2]I (1) contains 44 cationic nets, [(CuI)2(HSCH2CH2OCH2CH2OCH2CH2SH)] (2) neutral layers in which stairlike CuI double chains are linked by dithiol spacers. In contrast to these 2D polymers, [CuI(NCCH2CH2OCH2CH2CN)] (3) and [(CuI)4(NCCH2CH2OCH2CH2CN)2] (4) both contain infinite chains with respectively (CuI)2 rings and distorted (CuI)4 cubes as building units. Solvothermal reaction of CuI with the thiacrown ether 1, 4, 10‐trithia‐15‐crown‐5 (1, 4, 10TT15C5) in acetonitrile affords the lamellar coordination polymer [(CuI)3(1, 4, 10TT15C5)] (7) in which copper atoms of individual CuI double chains are bridged in a μ‐S1, S4 manner. The third sulphur atom S10 of the thiacrown ether coordinates a copper(I) atom from a parallel chain to generate a 2D network.

Key indicatorsSingle-crystal X-ray study T = 293 K Mean '(C±C) = 0.003 A Ê R factor = 0.043 wR factor = 0.100 Data-to-parameter ratio = 11.3For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

Treatment of an acetonitrile solution of CuI with 1, 7‐dithia‐18‐crown‐6 (1, 7‐DT18C6) at 100°C affords the coordination polymer 1[(CuI)2(1, 7‐DT18C6)2] (1) in which 1, 7‐DT18C6 ligands bridge (CuI)2 rings into double chains. 1D polymers of the type 1[M{(Cu3I4)(1, 7‐DT18C6)}] (M = K, 2; M = Cs, 3) can be isolated under similar conditions in the presence of respectively KI and CsI. Both contain bridging heptacyclic [Cu6I8]2— units but crystallise in different space groups, namely P1 and C2/m. The cesium cation of 3 is markedly displaced from the best plane through the thiacrown ether donor atoms. Reaction of 1, 7‐DT18C6 with CuSCN in the presence of NaSCN yields 2[{Na(CH3CN)2} {(CuSCN)2(1, 7‐DT18C6)}][Cu(SCN)2] (4), in which 1[(CuSCN)2] double chains are linked through macrocycles into sheets. Infinite 1[{Cu(SCN)2}—] chains compensate the charge of the Na+ cations. Complex 1 can imbibe 0.90 mol CsNO3 per mol of 1, 7‐DT18C6 pairs.

The complex [Hg(SCN)2(1, 10DT18C6)] (1) contains discrete Hg(SCN)2 units, whose Hg atoms lie at the centre of a 1, 10‐dithia‐18‐crown‐6 (1, 10DT18C6) macrocycle. The essentially linear coordination of Hg in Hg(SCN)2 is extended to hexagonal bipyramidal by weak Hg—S bonds of length 3.003(2)Å to the thiacrown ether S atoms and by four additional secondary Hg—O interactions. Solvothermal reaction of CuCN and HgCl2 with 1, 10DT18C6 in acetonitrile at 100 °C affords  ∞3[(CuCN)4{Hg(CN)2(1, 10DT18C6)}] (2). Zigzag CuCN chains in this complex are linked by 1, 10DT18C6 ligands in a μ‐S1, S10 bridging manner into layers. These, in their turn, are connected through μ‐[Hg(CN)2] units into interpenetrating 3D frameworks, in which the Hg atoms are surrounded by coordinating thiacrown ether macrocycles.  ∞3[K(Cu3I4)(1, 7, 13TT18C6)]·CH3CN (3) can be prepared by treatment of KI and CuI with 1, 7, 3‐trithia‐18‐crown‐6 (1, 7, 13TT18C6) in acetonitrile at 100 °C and contains anionic layers in which broken cube [Cu3I4]— building units connect three adjacent thiacrown ether ligands. Individual layers are linked into a 3D network by the K+ counter cations.