The crystal structure of layered metal IrTe2 is determined using single-crystal x-ray diffraction. At T=220 K, it exhibits Ir and Te dimers forming a valence-bond crystal. Electronic structure calculations reveal an intriguing quasi-two-dimensional electronic state, with planes of reduced density of states cutting diagonally through the Ir and Te layers. These planes are formed by the Ir and Te dimers, which exhibit a signature of covalent bonding character development. Evidence for significant charge disproportionation among the dimerized and non-dimerized Ir (charge order) is also presented.
