Synthesis, crystal structure and spectral analysis of crown ether platinum bis(dithiolate) complexes [Na(N15C5)2]2[Pt(mnt)2] and [Na(N15C5)]2[Pt(i-mnt)2]

The reactions of 2,3-naphtho-15-crown-5 (N15C5) with Na2[Pt(L)2] [LZ1,2-dicyanoethylene-1,2-dithiolate (mnt) or 1,1-dicyanoethylene- 2,2-dithiolate (i-mnt)] afford two complexes [Na(N15C5)2]2[Pt(mnt)2] (1) and [Na(N15C5)]2[Pt(i-mnt)2] (2). They are characterized by elemental analysis, FT-IR, UV–visible spectra and single crystal X-ray diffraction. 1 crystallizes in the monoclinic, space group P21/c with aZ 15.616(11), bZ20.481(14), cZ12.910(9) A ° , bZ103.298(11)8, VZ4018(5) A ° 3, ZZ2 and R1(wR2)Z0.0390 (0.0808). 2 crystallizes in the triclinic, space group Pı¯ with aZ8.360(3), bZ12.892(5), cZ12.899(5) A ° , aZ115.472 (5), bZ106.053(6)8, gZ91.981(6)8, VZ1187.2(8) A ° 3, ZZ1 and R1(wR2)Z0.0365 (0.0775). The [Na(N15C5)2]C sandwich complex cations of 1 are assembled into a novel 1D zigzag chain by alternating p–p stacking interactions and the resulting cationic chains are linked into a 2D network by the bridging [Pt(mnt)2]2K complex anions through weak C–H/S hydrogen bonds. For 2, the [Na(N15C5)]C mono-capped complex cations act as the bridges linking the [Pt(i-mnt)2]2K anions into a 1D infinite chain through Na–N bonds and S/C and S/p interactions are observed in the chain. q 2004 Elsevier B.V. All rights reserved