Copper(I) Pseudohalide Coordination Polymers containing Macrocyclic Methylcycloarsoxane (CH3AsO)n (n = 4, 5) or 1, 7‐Dithia‐18‐crown‐6 Bridging Units. Kupfer(I)‐Pseudohalogenid‐haltige Koordinationspolymere mit den Makrozyklen Methylcycloarsoxan (CH3AsO)n (n = 4, 5) oder 1, 7‐Dithia‐18‐Krone‐6 als Brückenliganden

Treatment of an acetonitrile solution of CuCN with methylcycloarsoxane (CH3AsO)n at 110 °C affords the coordination polymer [CuCN{cyclo-(CH3AsO)4}] (1), in which infinite CuCN zigzag chains are linked by μ-As1, As3 cyclotetramers (CH3AsO)4 into an open 3-D framework. Under similar solvothermal conditions, reaction of CuSCN with (CH3AsO)n in the presence of KSCN leads to metal-mediated ring expansion of the cyclo-arsoxane to yield the complex [{K[cyclo-(CH3AsO)5]2}Cu(NCS)2] (2). This contains discrete [Cu(NCS-κN)2{cyclo-(CH3AsO)5κAs}2]— anions that bridge κ10O coordinated potassium cations into infinite chains. In contrast, the structure directing role of the [K(1, 7DT18C6)2]+ sandwich building units for the solvothermal product [{K(1, 7DT18C6)2}Cu6(CN)7] (3) (1, 7DT18C6 = 1, 7-dithia-18-crown-6) leads to formation of an open [{Cu6(CN)7}—] framework. Individual [K(1, 7DT18C6)2]+ moieties bridge Cu Atoms in a μ-S1, S7 mode and are encapsulated within the large [Cu26(CN)28]2— cages of the cyanocuprate(I) network.