Self-assembly of [Cu(CN) 4] 3− ions with cationic {Me 3Sn} + or {Me 2Sn(CH 2) 3SnMe 2} 2+ fragments in the presence of a nBu 4N + template

Abstract

As described earlier, solutions of n Bu 4NCl and K 3[Cu(CN) 4] react with Et 3SnCl to zeolite-like [(Bu 4N)(Et 3Sn) 2Cu(CN) 4] ( 1), but with Me 3SnCl exclusively to [(Bu 4N)(Me 3Sn)Cu 2(CN) 4] ( 2), the crystal structure of which is reported here for the first time. The n Bu 4N + guest ions of 2 are accommodated between planar, negatively charged layers, wherein three-coordinated Cu(I) ions are interlinked by CN and CN·SnMe 3·NC bridges (2:1). The slightly modified new homologue of 2: [( n Bu 4N){Me 2Sn(CH 2) 3SnMe 2} 0.5Cu 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 13C, 15N and 119Sn. A three-dimensional host framework is postulated to encapsulate the n Bu 4N + guest of 3, the Sn atoms of adjacent layers being therein tied pair-wise together by trimethylene tethers, (CH 2) 3. For further comparison, the solid-state NMR data of the new coordination polymer [{Me 2Sn(CH 2) 3SnMe 2} 0.5Au(CN) 2] ( 5) are also presented.