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This paper deals with a coupled Hartree system with Hardy-Littlewood-Sobolev critical exponent \begin{equation*} \begin{cases} -Δu+(V_1(x)+λ_1)u=μ_1(|x|^{-4}*u^{2})u+β(|x|^{-4}*v^{2})u, \ \ &x\in R^N, -Δv+(V_2(x)+λ_2)v=μ_2(|x|^{-4}*v^{2})v+β(|x|^{-4}u^{2})v, \ \ &x\in R^N, \end{cases} \end{equation} where , , with , are nonnegative functions and , , are positive constants. Such system arises from mathematical models in Bose-Einstein condensates theory and nonlinear optics. By variational methods combined with degree theory, we prove some results about the existence and multiplicity of high energy positive solutions under the hypothesis

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