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

The lamellar coordination polymer (2)(infinity)[CuI(1,10DT18C6)] (1) (1,10D T18C6 = 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 gr oup 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 chara cteristic building units. Performing the reaction in the presence of an equ imolar quantity of alkali metal halide MI (M+ = Na+, K+) in acetonitrile so lution at 100 degrees C leads to formation of ion-ligating iodocuprate(I)-b ased two-dimensional coordination networks in (2)(infinity)[{Na(CH3CN)} {Cu 5I6(1,10DT18C6)}] (2) and (2)(infinity)[K{Cu4I5(1,10DT18C6)(2)}] (3). Both anionic frameworks contain characteristic iodocuprate(I) chains that are br idged in a mu-S1,S10 manner by 1,10DT18C6 macrocycles, However, the structu re-directing influence of the alkali metal cation manifests itself in both the connectivity pattern and the stoichiometry of the resulting CuI-based n etwork. 2 is chiral and crystallizes in the monoclinic space group P2(1) wi th 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 3 018 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, th e lamellar coordination networks of 2 retain their integrity up to 230 degr ees C before loss of their bridging thiacrown ethers. (C) 2000 Academic Pre ss.