Monohalogenated ferrocenes C5H5FeC5H4X(X= Cl, Br and I) and a second polymorph of C5H5FeC5H4I

Abstract

The structures of the three title monosubstituted ferrocenes, namely 1-chloroferrocene, [Fe(C(5)H(5))(C(5)H(4)Cl)], (I), 1-bromoferrocene, [Fe(C(5)H(5))(C(5)H(4)Br)], (II), and 1-iodoferrocene, [Fe(C(5)H(5))(C(5)H(4)I)], (III), were determined at 100 K. The chloro- and bromoferrocenes are isomorphous crystals. The new triclinic polymorph [space group P-1, Z = 4, T = 100 K, V = 943.8 (4) A(3)] of iodoferrocene, (III), and the previously reported monoclinic polymorph of (III) [Laus, Wurst & Schottenberger (2005). Z. Kristallogr. New Cryst. Struct. 220, 229-230; space group Pc, Z = 4, T = 100 K, V = 924.9 A(3)] were obtained by crystallization from ethanolic solutions at 253 and 303 K, respectively. All four phases contain two independent molecules in the unit cell. The relative orientations of the cyclopentadienyl (Cp) rings are eclipsed and staggered in the independent molecules of (I) and (II), while (III) demonstrates only an eclipsed conformation. The triclinic and monoclinic polymorphs of (III) contain nonbonded intermolecular I...I contacts, causing different packing modes. In the triclinic form of (III), the molecules are arranged in zigzag tetramers, while in the monoclinic form the molecules are arranged in zigzag chains along the a axis. Crystallographic data for (III), along with the computed lattice energies of the two polymorphs, suggest that the monoclinic form is more stable.