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Analysis of P–O–C, P–S–C and P–O–P angles: a database survey completed with four new X-ray crystal structures

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Abstract

Four new crystal structures, P(O)(OC6H5)2(NHNHC6H5) (I), P(S)(OCH3)2(NHCH(CH3)2) (II), P(S)(OCH3)2(NH-cyclo-C5H9) (III) and [2–Cl–C6H4CH2NH3]2[(CH3S)P(O)(O)–O–P(O)(O)(SCH3)] (IV) were studied. The P–O–C angles were analyzed, considering phosphoryl compound (I) and thiophosphoryl compounds (II) and (III) and their analogous structures deposited in the Cambridge Structural Database (CSD), including 282 P(O)(O)2(N) structures (706 P–O–C angles) and 186 P(S)(O)2(N) structures (518 P–O–C angles) with at least one P–O–C angle. The maximum populations of P–O–C angles are within 120°–122° in both P(O)(O)2(N) and P(S)(O)2(N) families of structures, confirming the hybridization state close to sp 2 for the oxygen atom of P–O–C. A survey on the CSD resulted in 11 P(O)(O)2(S–C) structures (11 P–S–C angles), and the structure (IV) belonging to this family of compounds is the first diffraction study of a salt with a (S)P(O)(O)–O–P(O)(O)(S) skeleton in the anion component. For the P–S–C angles, the maximum population was found in the range of 100°–104° showing the angles within those related to unhybridized pure p orbitals (p 3) and hybridized sp 3 for the sulfur atom of P–S–C. The analysis of 187 P(O)–O–P(O) structures (with no restriction on the other two atoms attached to phosphorus) including 538 P–O–P angles yielded the maximum population of P–O–P angles within 132°–134°, showing the more pronounced “s” character of the orbital (with respect to the sp 2 and toward sp) for the oxygen atom at the P–O–P moiety.

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Acknowledgments

Financial support of this work by Zanjan Branch, Islamic Azad University is gratefully acknowledged. The X-ray part of the work was carried out with the support of X-ray Diffraction and Bio-SAXS Core Facility of CEITEC, and the ASTRA lab established within the Operation program Prague Competitiveness—project CZ.2.16/3.1.00/24510.

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Authors and Affiliations

  1. Department of Chemistry, Zanjan Branch, Islamic Azad University, Zanjan, Iran

    Fahimeh Sabbaghi

  2. Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad, Iran

    Mehrdad Pourayoubi

  3. Institute of Physics AS CR, v.v.i., Na Slovance 2, 182 21, Prague 8, Czech Republic

    Michal Dušek, Václav Eigner & Monika Kučeráková

  4. Department of Chemistry, Payame Noor University, Zanjan, Iran

    Sahar Bayat

  5. Department of Chemistry, University of Pittsburgh, Pittsburgh, PA, 15260, USA

    Krishnan Damodaran

  6. Department of Chemistry, Masaryk University, Kotlarska 2, 61137, Brno, Czech Republic

    Marek Nečas

  7. CEITEC - Central European Institute of Technology, Masaryk University, Kamenice 5, 62500, Brno, Czech Republic

    Marek Nečas

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  1. Fahimeh Sabbaghi
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Correspondence to Fahimeh Sabbaghi.

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Sabbaghi, F., Pourayoubi, M., Dušek, M. et al. Analysis of P–O–C, P–S–C and P–O–P angles: a database survey completed with four new X-ray crystal structures. Struct Chem 27, 1831–1844 (2016). https://doi.org/10.1007/s11224-016-0809-7

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  • DOI: https://doi.org/10.1007/s11224-016-0809-7

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