Alkali cation ligating iodocuprate(I)-based coordination networks with the thiacrown ether 1,10-dithia-18-crown-6

The lamellar coordination polymer (2)(infinity)[CuI(1,10DT18C6)] (1) (1,10DT18C6 = 1,10-dithia-18-crown-6) may be prepared by reaction of CuI with the thiacrown ether in acetonitrile. 1 crystallizes in the monoclinic space group P2(1)/n with a = 10.764(2), b = 14.317(3), and c = 12.335(3) Angstrom, beta = 98.08(3)degrees, V = 1882.0(7) Angstrom(3), Z = 4, R = 0.041, wR(2) = 0.102 for 5480 reflections and contains (CuI)(2) rhomboid dimers as characteristic building units. Performing the reaction in the presence of an equimolar quantity of alkali metal halide MI (M+ = Na+, K+) in acetonitrile solution at 100 degrees C leads to formation of ion-ligating iodocuprate(I)-based two-dimensional coordination networks in (2)(infinity)[{Na(CH3CN)} {Cu5I6(1,10DT18C6)}] (2) and (2)(infinity)[K{Cu4I5(1,10DT18C6)(2)}] (3). Both anionic frameworks contain characteristic iodocuprate(I) chains that are bridged in a mu-S1,S10 manner by 1,10DT18C6 macrocycles, However, the structure-directing influence of the alkali metal cation manifests itself in both the connectivity pattern and the stoichiometry of the resulting CuI-based network. 2 is chiral and crystallizes in the monoclinic space group P2(1) with a = 10.456(4), b = 13.674(6), and c = 11.535(5) Angstrom, beta = 92.82(3)degrees, V = 1647.3(12) Angstrom(3), Z = 2, R = 0.049, wR(2) = 0.110 for 3018 reflections. 3 is likewise monoclinic, space group P2/n with a = 11.418(6), b = 12.521(7), and c = 15.398(7) Angstrom, beta = 96.58(3)degrees, V = 2187(2) Angstrom(3), Z = 2, R = 0.064, wR(2) = 0.176 for 3858 reflections. After losing their coordinated acetonitrile molecules at 180 degrees C, the lamellar coordination networks of 2 retain their integrity up to 230 degrees C before loss of their bridging thiacrown ethers. (C) 2000 Academic Press.