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The title compound [NiII(phen)3]2[Cu10H2I16] 1 (phen=1,10-phenanthroline, C12H8N2) was hydrothermally synthesized from a simple reaction of CuI–NiCl2·6H2O–phen·H2O–H2O. X-ray analysis revealed that it consists of NiN62+ core cation and decanuclear iodocuprate(I) anion together with two dissociative H+ ions. In anionic unit, the discrete decanuclear iodocuprate(I) is formed by crystallographically independent five monovalent copper atoms and eight iodine atoms via an inversion center. There exist two types of Cu(I) coordination sites; only one copper(I) atom is in a highly distorted triangular planar site, and the other four copper(I) atoms display the tetrahedral geometries. It deserves to be noted that four types of bridging modes of I− ions in which two are ordinary μ2- and μ3-bonding modes can be found. But the other two are the rectangle planar geometry and the novel μ4-bridge like an “umbrella”, and both of them are rather rare in the halocuprates(I). Compound 1 was crystallized in triclinic space group P1¯ with a=11.6861(17), b=14.590(2), c=14.649(2) A˚, α=76.370(2), β=70.830(2), γ=81.320(3)o, R=0.075, and was characterized by elemental analysis, IR spectrum and UV-VIS spectrum. The third-order non-linear optical property of 1 was also investigated and the compound exhibits the reverse saturable absorption and self-defocusing performance. [Copyright &y& Elsevier]