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Polymorphism for a novel phosphoramidate; NMR and X-ray crystallography

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Abstract

New phosphoramidates with formula 3-NC5H4C(O)NHP(O)XY (X=Y=Cl (1), X=Y=NH–C(CH3)3 (2a,2b), X=Y=N(C4H9)2 (3), X=Cl, Y=N(C2H5)2 (4) were synthesized and characterized by IR, 1H-, 13C-, 31P-NMR spectroscopy and CHN elemental analysis. Surprisingly, the reaction of compound 2a with LaCl3, 7H2O in 3:1 M ratio leads to a polymorph of this compound (2b). NMR spectra indicate that 2 J(PNHamide) in 2b (7.0 Hz) is very much greater than in 2a (4.1 Hz), while δ(31P) values are identical for both of them. In IR spectra, υ(P=O) is weaker but υ(C=O) is stronger in 2a than in 2b. The structures of 2a, 2b were determined by X-ray crystallography. These compounds form centrosymmetric dimers via two intermolecular P=O……H–N hydrogen bonds. Strong intermolecular N–H…N, N–H…O and weak C–H…O hydrogen bonds lead to a three-dimensional polymeric cluster in the 2a while intermolecular strong N–H……N and weak C–H……O hydrogen bonds form a two-dimensional polymeric chain in 2b.

Graphical Abstract

New phosphoramidates were synthesized and characterized by 1H, 13C, 31P NMR and IR spectroscopy and elemental analysis. Surprisingly, the crystal structures of two polymorph compounds were determined using X-ray crystallography. These compounds have differences in their IR and NMR spectra as well as in their crystal structures. They form polymeric chains via intermolecular hydrogen bonds.

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Acknowledgement

We would like to thank the Research Council of Tarbiat Modares University the financial support of this work.

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Authors and Affiliations

  1. Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran

    Khodayar Gholivand

  2. Department of Biology, Islamic Azad University, Garmsar branch, Garmsar, Iran

    Farzaneh Afshar

  3. Department of Chemistry, Amirkabir University of Technology, P. O. Box 159163-4311, Tehran, Iran

    Zahra Shariatinia

  4. Department of Chemistry, Science and Research Branch, Islamic Azad University (IAU), P.O. Box 14515-775, Tehran, Iran

    Karim Zare

  5. Department of Chemistry, Shahid Beheshty University, Tehran, Iran

    Karim Zare

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  1. Khodayar Gholivand
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  2. Farzaneh Afshar
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  3. Zahra Shariatinia
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  4. Karim Zare
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Correspondence to Khodayar Gholivand.

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Gholivand, K., Afshar, F., Shariatinia, Z. et al. Polymorphism for a novel phosphoramidate; NMR and X-ray crystallography. Struct Chem 21, 629–636 (2010). https://doi.org/10.1007/s11224-010-9592-z

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  • DOI: https://doi.org/10.1007/s11224-010-9592-z

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