A Novel Huge Diamond‐like Three‐fold Interpenetrated Network of CuI and Crown Ether

The quest for mercury sensitive ion exchangers results in a diamondlike network (1). This is in contrast to the similar well known 44 network described by Rottgers 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) A three times the b axis.