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We study some basic properties of such Lie groups through the left-symmetric product on its Lie algebra defined by the connection.    The classification problem of such structures is known for dimensions less than 4. The case of dimension 4 when the group is nilpotent is carried out in this paper. As an application of this classification one can easily determine all the possible left-invariant complete flat pseudo-Riemannian structures on the simply connected nilpotent Lie groups of dimension \\(\\leq 4.\\)    This classification especially reveals that there are two isomorphism classes of complete left-invariant flat structures such that they do not contain any pure translations when they are viewed as simple transitive actions on \\({\\mathbb{R}}^ n\\) by affine 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