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 Na-2[Pt(L)(2)] [L = 1,2-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 P2(1)/c with a = 15.616(11), b = 20.481(14), c = 12.910(9) Angstrom, beta = 103.298(11)degrees, V = 4018(5) Angstrom(3), Z = 2 and R-1 (wR(2)) = 0.0390 (0.0808). 2 crystallizes in the triclinic, space group P (1) over bar with a = 8.360(3), b = 12.892(5), c = 12.899(5) Angstrom, alpha = 115.472 (5), beta = 106.053(6)degrees, gamma = 91.981(6)degrees, V = 1187.2(8) Angstrom(3), Z = 1 and R-1 (wR(2)) = 0.0365 (0.0775). The [Na(N15C5)(2)](+) sandwich complex cations of 1 are assembled into a novel 1D zigzag chain by alternating pi-pi stacking interactions and the resulting cationic chains are linked into a 21) network by the bridging [Pt(mnt)(2)](2-) complex anions through weak C-H...S hydrogen bonds. For 2, the [Na(N15C5)](+) mono-capped complex cations act as the bridges linking the [Pt(i-mnt)(2)](2-) anions into a 1D infinite chain through Na-N bonds and S...C and S...pi interactions are observed in the chain. (C) 2004 Elsevier B.V. All rights reserved.