Abstract
The title compound, catena-poly[[[bis-(ethyl-enedi-amine-κ2 N,N')platinum(II)]-μ-iodido-[bis-(ethyl-enedi-amine-κ2 N,N')platinum(IV)]-μ-iodido] tetra-(hydrogen sulfate) dihydrate], {[PtII(C2H8N2)2][PtIVI2(C2H8N2)2](HSO4)4·2H2O} n , has a linear chain structure comprising alternating platinum cations with mixed-valent oxidation states of +II/IV. Square-planar [Pt(en)2]2+ cations and elongated octa-hedral trans-[PtI2(en)2]2+ cations (en is ethyl-enedi-amine) are stacked alternately parallel to the b axis, and are bridged by the I ligands. The Pt site of the [PtII/IV(en)2] units is located on a twofold rotation axis. The I site, which is located on the same twofold rotation axis, is equally disordered over two positions. The Pt and I sites form a straight ⋯I-PtIV-I⋯PtII⋯ chain, with PtIV-I bond lengths of 2.7202 (6) and 2.6917 (6) Å, and PtII⋯I contacts of 3.2249 (6) and 3.2534 (6) Å. The mixed-valence state of the Pt site is expressed by the structural parameter δ = (PtIV-I)/(PtII⋯I), with values of 0.843 and 0.827 for the two independent I atoms. In the crystal structure, the cationic columnar structure is stabilized by hydrogen bonds of the type N-H⋯O between the amine groups of the Pt complex chains and the disordered hydrogen sulfate counter anions, and between the amine groups and water mol-ecules of crystallization. In addition, O-H⋯O hydrogen bonds between the hydrogen sulfate anions and water mol-ecules of crystallization and between the hydrogen sulfate anions themselves consolidate the crystal packing.
Highlights
The title compound, catena-poly[[[bis(ethylenediamine-2N,N0)platinum(II)]-iodido-[bis(ethylenediamine-2N,N0)platinum(IV)]--iodido] tetra(hydrogen sulfate) dihydrate], {[PtII(C2H8N2)2][PtIVI2(C2H8N2)2](HSO4)4Á2H2O}n, has a linear chain structure comprising alternating platinum cations with mixed-valent oxidation states of +II/IV
The Pt site of the [PtII/IV(en)2] units is located on a twofold rotation axis
The I site, which is located on the same twofold rotation axis, is disordered over two positions
Summary
The title mixed-valence compound, [PtII(en)2][PtIVI2(en)2](HSO4)4Á2H2O (en is ethylenediamine, C2N2H8), (I), is a member of the family of one-dimensional halogenido-bridged mixed-valence metal complexes, formulated as [MII(AA)2][MIVX2(AA)2]Y4 [MII/MIV = PtII/PtIV; PdII/PdIV; NiII/NiIV; PdII/PtIV; NiII/PtIV; X = Cl, Br, I; AA = NH2(CH2)2NH2, etc.; Y = ClO4À, BF4À, XÀ, etc.], which are often referred to as MX-chains and are typical mixed-valence compounds belonging to class II in the classification of Robin & Day (1967). MX-chains have attracted much interest because of their one-dimensional mixed-valence electron systems, as described in a previous report (Matsushita, 2006). The X-ray structure determination of (I) was performed to gain structural information for MXchains and to compare (I) with chlorido- and bromido-bridged PtII/PtIV mixed-valence complexes with a hydrogen sulfate counter-anion, i.e.
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Free) 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call
