Layering solutions of P(4)S(3) in CH(2)Cl(2) with solutions of CuCl or CuI in CH(3)CN gives the coordination polymers (P(4)S(3))(3)(CuCl)(7) (1), (P(4)S(3))(2)(CuCl)(3) (2), (P(4)S(3))(CuI) (3) and (P(4)S(3))(CuI)(3) (4), respectively, after slow diffusion. The yellow compounds were characterised by elemental analysis, (31)P magic-angle spinning (MAS) NMR spectroscopy and single-crystal X-ray crystallography. The solid-state structures demonstrate the unexpected ligand versatility of the P(4)S(3) molecule, which interacts through two, three, or even all of the phosphorus atoms with copper according to the nature of the copper halide. Compound 1 has a three-dimensional network in which linear and cylindrical infinite CuCl subunits coexist with diatomic CuCl building blocks. For the first time, all four P atoms of the P(4)S(3) cage are involved in coordination with metal atoms. The 3D structure of 2 contains stacks of P(4)S(3) that are interconnected by slightly undulated and planar [CuCl](n) ribbons. Compound 3 is a one-dimensional polymer composed of alternating (CuI)(2) rings and P(4)S(3) bridges. The structure of 4 consists of undulated [CuI](n) layers in which the P(4)S(3) cage functions as a bridge within the layer, as well as a spacer between the layers. The (31)P MAS NMR spectra obtained are in good agreement with the solid-state structures obtained crystallographically. Thus, analytically pure 3 and 4 show singlet peaks that correspond to uncoordinated P and quartets owing to coupling with (63)Cu and (65)Cu, respectively, whereas that of 1 contains quartets according to all-P coordination. The spectrum of 2 was obtained from a sample that still contained 40 % of 1.

The formation of coordination polymers from copper(I) bromide and P4S3, a potentially tetradentate P‐donor bridging ligand, was studied. Whereas (P4S3)3(CuBr)7 (1) formed in excellent yield, (P4S3)(CuBr)3 (2) and (P4S3)(CuBr) (3) crystallized as mixtures. The new compounds were characterized by X‐ray crystallography and solid‐state 31P MAS NMR spectroscopy. The structure of 1 consists of a 3D network of cylindrical (CuBr)n columns, castellated (CuBr)n chains and diatomic CuBr units. These building blocks are linked by tetradentate P4S3 molecules. The structure of 2 comprises undulated (CuBr)n layers, which are intra‐ and interlayer linked by tridentate P4S3 molecules. Compound 3 is a one‐dimensional polymer composed of four‐membered Cu2Br2 rings, which are bridged by the P3 bases of two P4S3 molecules.

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The formation of a new type of organometallic-inorganic hybrid coordination polymer from P 4 S 3 ·W(CO) 5 (1) and CuI has been studied. The structure of {P 4 S 3 ·W(CO) 5 }(CuI) (3) has been verified by the combination of spectroscopic (IR, Raman, 31 P MAS NMR) and X-ray diffraction methods. Theoretical studies of β-P 4 S 3 , P 4 S 3 ·W(CO) 5 (1), 1D-(P 4 S 3 )(CuI) (2), and 3D-(P 4 S 3 )(CuI) 3 (4), which may be considered as poten-

The synthesis and characterization of hybrid polymers combining organic P,PЈ (dppe) or N,NЈ (pyrazine) ligands and inorganic donors (P 4 S 3 ) as cross-linkers between copper(I) halide aggregates is described. As a simple model system the reaction of a mixture of P 4 S 3 , PEt 3 , and CuX (X = Cl, Br, I) was studied. According to X-ray diffraction analysis, pseudotetrahedral monomers [CuX(PEt 3 ) 2 (P 4 S 3 )] (1-3) were formed, in which P 4 S 3 coordinates through the apical phosphorus atom. Layering a mixture of P 4 S 3 , Ph 2 PCH 2 CH 2 PPh 2 (dppe), and toluene with CuCl in MeCN under diffusion conditions gives 1D-[CuCl(dppe)(MeCN)] (6), which contains (Cu 2 Cl 2 ) 2 -(μ-dppe) 2 clusters linked by another dppe ligand. The analogous reaction with CuI gives 1D-[CuI(P 4 S 3 )(dppe)] (7), which is built up of alternating trans-(Cu 2 I 2 )(P 4 S 3 ) 2 units and dppe linkers. Hybrid polymers 2D-[CuX(P 4 S 3 )(dppe)] [X = Br (8), I (9)] are formed if CH 2 Cl 2 is used instead of toluene. The 2D