The lamellar coordination polymer 2 R [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) A > , ؍ 98.08(3)3, V )7(0.2881؍ A > 3 , Z ؍ 4, R ؍ 0.041, wR 2 ؍ 0.102 for 5480 re6ections 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 1003C leads to formation of ion-ligating iodocuprate
. Both anionic frameworks contain characteristic iodocuprate(I) chains that are bridged in a -S1,S10 manner by 1,10DT18C6 macrocycles. However, the structure-directing in6uence 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) A > , ؍ 92.82(3)3, V ؍ 1647.3(12) A > 3 , Z ؍ 2, R ؍ 0.049, wR 2 ؍ 0.110 for 3018 re6ections. 3 is likewise monoclinic, space group P2/n with a ؍ 11.418(6), b ؍ 12.521(7), and c ؍ 15.398(7) A > , ؍ 96.58(3)3, V ؍ 2187(2) A > 3 , Z ؍ 2, R ؍ 0.064, wR 2 ؍ 0.176 for 3858 re6ections. After losing their coordinated acetonitrile molecules at 1803C, the lamellar coordination networks of 2 retain their integrity up to 2303C before loss of their bridging thiacrown ethers.