Intramolecular dehydrofluorinative coupling of pentamethylcyclopentadienyl and phosphines bearing polyfluoroaryl substituents occurs readily in cationic complexes of rhodium [ 1, 2 ] and iridium [ 2, 3 ], especially in cases where the phosphine moiety is a component of a chelating ligand. <...> Here we report the structure of an iridium complex, [(u5-C5Me5)IrCl{xP,xS-(C6F5)2PC6H4SMe-2}]BF4 (1), which undergoes intramolecular dehydrofluorinative coupling [ 3 ], and which also crystallizes as a conglomerate. <...> Diffraction data of a single crystal were collected at 153(2) K on a Bruker SMART diffractometer using the SAINT-NT [ 6 ] software with graphite-monochromated MoKh radiation. <...> Crystallographic and refinement data are given in Table 1. <...> Empirical absorption corrections were applied using SADABS [ 8 ]. <...> The structure was solved using direct methods and refined with the programme package SHELXTL [ 9 ]. <...> The non-hydrogen atoms were refined with anisotropic thermal parameters. <...> Hydrogen atom positions were added, and idealized positions and a riding model with fixed thermal parameters (Uij) 1.2Ueq for the atom to which they are bonded (1.5 for CH3)) were used for subsequent refinements. <...> These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033. © Bellabarba R.M., Nieuwenhuyzen M., Saunders G.C., 2013 . 408 – 410 . 2013. . 54, 2 Crystallographic data and refinement parameters for compound 1 Parameter Value Empirical formula Molecular mass Wavelength, Е Crystal system Space group a, b, c, Е V, Е3; Z dcalc, gcm–3 , mm–1 F(000) Crystal size, mm data collection range, deg. <...> Salt 1 crystallized as a conglomerate in the non-centrosymmetric space group P212121. <...> The structure of the SIr, SS stereoisomer was determined (Fig. 1). <...> The cation shows the expected three-legged piano stool geometry about the iridium atom, which is a stereogenic centre. <...> The angles at iridium are within the ranges of those reported for [(u5-C5Me5)IrCl(PS)]0/1+, except for Cp*—Ir—P (136.7(2 <...>