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The structures of two [2 π  + 2 π ] cycloaddition adducts, [ endo -3- exo -cyano-7-methoxytricyclo[4.2.1.0 2.5 ]-non-7-ene and dimethyl  exo ,  endo -5-aza-tetracyclo-[7.2.1.0 2.8 .0 3.7 ]dodec-10-ene-4,6-dione-10,11-dicarboxylate, were determined and the stereo- and regiochemistry of each molecule was established. One adduct possesses an  endo  ring fusion while the other was found to be  exo . In both structures molecules form centrosymmetric dimers as a result of weak intermolecular, non-bonded interactions of the type C=O…H–C.