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In this paper we determine all the simply connected non-degenerate CR Lie groups, which are flat with respect to the Cartan connection: in terms of associated Lie algebras, we assert that the only Cartan flat non-degenerate CR Lie algebras are , , , and with its modifications, where is the affine Lie algebra of dimension 2 and is the Heisenberg Lie algebra of dimension . Furthermore, we determine all the (flat and non-flat) non-degenerate CR structures on each of these Lie groups.

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