Geometry and bond-length alternation in nonlinear optical materials. I. Standard parameters in two precursors.

2-{3-Cyano-4-[4-(N-formylanilino)-trans-1,3-butadienyl]-5,5-dimethyl-2,5-dihydrofuran-2-ylidene}propanedinitrile, C(22)H(18)N(4)O(2), (I), and 2-{3-cyano-4-[6-(N-formylanilino)-trans,trans-1,3,5-hexatrienyl]-5,5-dimethyl-2,5-dihydrofuran-2-ylidene}propanedinitrile, C(24)H(20)N(4)O(2), (II), show the alternating single/double-bond behaviour of push-pull chromophores. In the two structures, the planar polyene chains are twisted with respect to the furanylidene ring by 18.2 (2) and 12.4 (2) degrees , respectively. Comparison with structures of related and parent molecules shows subtle but consistent bond-length variations consistent with charge-delocalized structures. Crystal cohesion is provided by various sets of hydrogen bonds, viz. C-H(methyl)...N(cyano) and bifurcated (C=C-H)(2)...O=C in (I), and C-H(methyl/phenyl)...O and C=C-H...N(cyano) in (II).