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X-ray diffraction studies on poly(ferrocenylenedimethylsilylene), PFDMS, indicate a 3D crystalline phase with monoclinic packing of the macromolecules with possible unit cell parameters a ) 13.29 Å, b ) 6.01 Å, c ) 13.9 Å, and γ ) 93.6°. There are two main chains with four monomer units per unit cell, X-ray crystal density F c ) 1.455 g cm -3 , possessing a planar all-trans zigzag conformation of the main chain, helix 2/1. Poly(ferrocenylenedibutylsilylene), PFDBS, also appears to crystallize in a monoclinic lattice with unit cell parameters a ) 11.57 Å, b ) 6.71 Å, c ) 13.6 Å and γ ) 107.1°(two monomer units of one macromolecule per unit cell; X-ray crystal density Fc ) 1.239 g cm -3 ). A particular feature of crystalline PFDMS, and PFDBS, is the coexistence of the 3D monoclinic crystalline phases with mesophases (2D crystals with a hexagonal or tetragonal packing of macromolecules). Upon doping with iodine vapor, the crystalline poly(ferrocenylenedimethylsilylene) converts into a crystalline mixedvalence complex. Doped oriented samples retain the initial orientation of the macromolecules and also give relatively good fiber diffraction patterns. Equatorial reflections on such fiber patterns can be indexed by a 2D monoclinic packing of the complex macromolecules in the (ab) plane with unit cell parameters a ) 10.36 Å, b ) 6.03 Å, and γ ) 90.7°. The values of the a and b dimensions suggest that [I 3]species are placed between macromolecules and along their backbone. Three meridional reflections at 3.0, 4.0, and 6.0 Å yield a fiber repeat equal to 12.0 Å, which probably arises from a one-dimensional order of [I3]arrays.

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