The transient electronic and molecular structure arising from photoinduced charge transfer in transition metal complexes is studied by X-ray powder diffraction with a 100 fs temporal and atomic spatial resolution. Crystals containing a dense array of Fe(II)-tris(bipyridine) ([Fe(bpy)(3)](2+)) complexes and their PF6- counterions display pronounced changes of electron density that occur within the first 100 fs after two-photon excitation of a small fraction of the [Fe(bpy)(3)](2+) complexes. Transient electron density maps derived from the diffraction data reveal a transfer of electronic charge from the Fe atoms and-so far unknown-from the PF6- counterions to the bipyridine units. Such charge transfer (CT) is connected with changes of the inter-ionic and the Fe-bipyridine distances. An analysis of the electron density maps demonstrates the many-body character of charge transfer which affects approximately 30 complexes around a directly photoexcited one. The many-body behavior is governed by the long-range Coulomb forces in the ionic crystals and described by the concept of electronic polarons. (C) 2013 AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4800223]