Crystal Structure of Isotactic Poly((R,S)‑3-methyl-1-pentene)

The synthesis and the crystal structure of isotactic poly­((R,S)-3-methyl-1-pentene) (iP­(R,S)­3MP) are presented. The synthetic strategy based on hydrogenation of isotactic 1,2-poly­(E-3-methyl-1,3-pentadiene) has allowed for the preparation of a purely random copolymer of the two enantiomeric (R)- and (S)-3-methyl-1-pentene monomers. X-ray diffraction analysis and conformational and packing energy calculations have shown that chains of iP­(R,S)­3MP are in 4/1 helical conformation and are packed in a monoclinic unit cell with parameters a = 10.02 Å, b = 18.48 Å, c = 6.87 Å, and γ = 109.9° according to the space group P2₁/b or P2₁. A high degree of disorder is present in the crystals due to the random enchainment of the enantiomeric R and S monomeric units, whose chirality influences the handedness of the helical chains and the conformation assumed by the lateral groups. Disorder in the conformation of the lateral groups is also present. The crystal structure of the random copolymer iP­(R,S)­3MP is different from the tetragonal structure of the pure enantiomer homopolymer iP­(S)­3MP. This is due to different entropic effects, related to the presence of different types of disorder included in the crystals that drive crystallization in different packing modes. The crystal structure of iP­(R,S)­3MP provides an example of the effect of the chirality of side groups on the crystal packing and is an example of symmetry breaking in the structures of polymers.