The compound [{Pt4(en)4(NHCOtBu)4}{Tl(18-crown-6)}2](PF6)6 has been synthesized by a simple one-pot multicomponent reaction. Its structure was determined by X-ray single crystal diffraction analysis. The cation of the compound consists of one linearly arranged [Pt4(en)4(NHCOtBu)4]4+ chain and two [Tl(18-crown-6)]+ ions located at the two ends of the platinum chain. The complex crystallizes in a triclinic P1 with a=1.060 5(1), b =1.252 3(1), c=2.015(2) nm, α=107.430(2)°, β=91.032(2)°, γ=101.910(2)°, V=2.489 6(4) nm3, Z=2, R1=0.0744, wR2(I>2σ(I))=0.222 5, S=1.062. CCDC: 294083.
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