Self-assembly of [Cu(CN)4]3- ions with cationic {Me3Sn}+ or {Me2Sn(CH2)3SnMe2}2+ fragments in the presence of a nBu4N+ template

As described earlier. solutions of "Bu4NCl and K-3[Cu(CN)(4)] react with Et3SnCl to zeolite-like [(Bu4N)(Et3Sn)(2)Cu(CN)(4)] (1), but with Me3SnCl exclusively to [(Bu4N)(Me3Sn)Cu-2(CN)(4)] (2), the crystal structure of which is reported here for the first time. The "Bu4N+ guest ions of 2 are accommodated between planar, negatively charged layers, wherein three-coordinated Cu(I) ions are interlinked by CN- and CN . SnMe3. NC bridges (2:1). The slightly modified new homologue of 2: [((Bu4N)-Bu-n)( Me2Sn(CH2)(3)SnMe2)(0.5)Cu-2(CN)(4)] (3). displays an almost identical powder X-ray diffractogram as 2 and, moreover, surprisingly similar solid-state NMR spectra for the nuclei C-13, N-15 and Sn-119. A three-dimensional host framework is postulated to encapsulate the "Bu4N+ guest of 3, the Sn atoms of adjacent layers being therein tied pair-wise together by trimethylene tethers, (CH2)(3). For further comparison, the solid-state NMR data of the new coordination polymer [{Me2Sn(CH2)(3)SnMe2}(0.5)Au(CN)(2)] (5) are also presented. (C) 2001 Elsevier Science B.V. All rights reserved.