Structural Chemistry

, Volume 23, Issue 1, pp 287–295 | Cite as

Molecular structure of p-diisocyanobenzene from gas-phase electron diffraction and theoretical calculations and effects of intermolecular interactions in the crystal on the benzene ring geometry

  • Anna Rita Campanelli
  • Aldo DomenicanoEmail author
  • Fabio Ramondo
  • István HargittaiEmail author
Original Research


In this study, the molecular structure of p-diisocyanobenzene has been determined by gas-phase electron diffraction and quantum chemical calculations. The electron diffraction intensities from a previous study by Colapietro et al. (J Mol Struct 125:19–32, 1984) have been reanalyzed using geometrical constraints and initial values of vibrational amplitudes from computations. The equilibrium structure of the molecule has D 2h symmetry, whereas the average geometry in the gaseous phase is best described by a non-planar model of C 2v symmetry. The lowering of symmetry is due to large-amplitude motion of the substituents out of the plane of the benzene ring. The non-planar model has an internal ring angle at the ipso position, ∠aC2–C1–C6 = 120.6 ± 0.2°, about 1° smaller than that from the previous study, but consistent with the quantum chemical calculations. The mean length of the ring C–C bonds and the length of the triple bond are accurately determined as 〈r g(C–C)〉 = 1.398 ± 0.003 Å and r g(NC) = 1.177 ± 0.002 Å, respectively. Comparison with the gaseous isoelectronic molecules p-diethynylbenzene and p-dicyanobenzene shows that the differences in the mean lengths of the ring C–C bonds and in the lengths of the triple bonds determined by electron diffraction are equal or closely similar to the corresponding differences from quantum chemical calculations. The present experimental value of the ipso angle in free p-diisocyanobenzene is slightly, but significantly smaller than that obtained by X-ray crystallography. The difference is confirmed by computational modeling of the crystal structure and appears to be due to –NC···H–C intermolecular interactions in the crystal.


Gas-phase electron diffraction MO calculations p-Diisocyanobenzene p-Dicyanobenzene p-Diethynylbenzene Equilibrium C–C bond distances p-Diisocyanobenzene pentamer Gas–solid structural differences 



This study was supported by the CASPUR Supercomputing Center, Rome, with Standard HPC Grant 2011 (“A combined X-ray absorption spectroscopy, molecular dynamics simulations, and quantum mechanics calculation procedure for the structural characterization of ill-defined systems”).

Supplementary material

11224_2011_9889_MOESM1_ESM.doc (100 kb)
Supplementary material 1 (DOC 100 kb)


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Copyright information

© Springer Science+Business Media, LLC 2011

Authors and Affiliations

  1. 1.Department of ChemistryUniversity of Rome “La Sapienza”RomeItaly
  2. 2.Department of Chemistry, Chemical Engineering and MaterialsUniversity of L’AquilaL’AquilaItaly
  3. 3.Materials Structure and Modeling Research Group of the Hungarian Academy of Sciences and Department of Inorganic and Analytical ChemistryBudapest University of Technology and EconomicsBudapestHungary

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