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A new one-dimensional platinum mixed-valence complex with nonhalogen bridging ligands, namely catena-poly[[[bis­(ethane-1,2-diamine-[kappa]2N,N')platinum(II)]-[mu]-thio­cyanato-[kappa]2S:S-[bis(ethane-1,2-diamine-[kappa]2N,N')platinum(IV)]-[mu]-thio­cyanato-[kappa]2S:S] tetra­kis­(perchlorate)], {[Pt2(SCN)2(C2H8N2)4](ClO4)4}n, has been isolated. The PtII and PtIV atoms are located on centres of inversion and are stacked alternately, linked by the S atoms of the thio­cyanate ligands, forming an infinite one-dimensional chain. The PtIV-S and PtII...S distances are 2.3933 (10) and 3.4705 (10) Å, respectively, and the PtIV-S...PtII angle is 171.97 (4)°. The introduction of nonhalogen atoms as bridging ligands in this complex extends the chemical modifications possible for controlling the amplitude of the charge-density wave (CDW) state in one-dimensional mixed-valence complexes. The structure of a discrete PtIV thio­cyan­ate compound, bis­(ethane-1,2-diamine-[kappa]2N,N')bis­(thio­cyanato-[kappa]S)platinum(IV) bis­(perchlorate) 1.5-hydrate, [Pt(SCN)2(C4H8N2)2](ClO4)2·1.5H2O, has monoclinic (C2) sym­metry. Two S-bound thio­cyanate ligands are located in trans positions, with an S-Pt-S angle of 177.56 (3)°.
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