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Two Achiral Isomers of Chloronitropyridine Crystallize as Polar Materials with Different Molecular Packing Motifs Based on Similar Intermolecular Interactions

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Abstract

The molecular structures of two of the ten possible isomers of chloronitropyridine have been studied by spectroscopic techniques and single crystal X-ray diffraction. The structures of 2-chloro-4-nitropyridine (1) [monoclinic, Pc, a = 3.7711(14) Å, b = 8.919(3) Å, c = 9.324(3) Å, β = 99.506(5)°] and 5-chloro-2-nitropyridine (2) [triclinic, P1, a = 3.7559(13) Å, b = 6.071(2) Å, c = 6.939(2) Å, α = 85.703(5)°, β = 89.619(5)°, γ = 75.189(5)°] reveal that the isomers crystallize in non-centrosymmetric space groups with different molecular packing motifs based on similar intermolecular interactions. Each compound packs into molecular sheets via short chlorine–oxygen contacts and C–H⋯X (X = O, N) interactions of the nitro oxygen atoms and the pyridine nitrogen atom. The sheets further pack with an offset face-to-face π-stacking geometrical arrangement of the aromatic rings to form the three-dimensional structures. Achiral 2-chloro-4-nitropyridine (1) crystallizes as a polar material in the non-centrosymmetric and non-enantiomorphous space group Pc while the isomeric achiral compound 5-chloro-2-nitropyridine (2) forms a polar material that approximates inversion symmetry in the non-centrosymmetric enantiomorphous space group P1.

Graphical Abstract

The molecular structures of achiral 2-chloro-4-nitropyridine and 5-chloro-2-nitropyridine have been studied by X-ray diffraction revealing that they crystallize as polar materials. The structures have different packing motifs based on similar intermolecular interactions consisting of π-stacked molecular sheets formed by chlorine–oxygen contacts and C–H⋯X (X = O, N) interactions.

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Acknowledgements

The authors thank Vassar College for supporting this work and gratefully acknowledge support for the X-ray diffraction and NMR facilities at Vassar College from the National Science Foundation under Grant Nos. 0521237 and 1526982, respectively. Thanks to Dr. Karen Wovkulich for instrumentation support and a reviewer for generous and helpful comments. Alexander Preneta is acknowledged for providing some spectroscopic data on (1).

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  1. Department of Chemistry, Vassar College, Poughkeepsie, NY, 12604, USA

    Haley Merritt & Joseph M. Tanski

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  1. Haley Merritt
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  2. Joseph M. Tanski
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Correspondence to Joseph M. Tanski.

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Merritt, H., Tanski, J.M. Two Achiral Isomers of Chloronitropyridine Crystallize as Polar Materials with Different Molecular Packing Motifs Based on Similar Intermolecular Interactions. J Chem Crystallogr 48, 109–116 (2018). https://doi.org/10.1007/s10870-018-0717-3

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