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Structural systematics and conformational analyses of an isomer grid of nine tolyl-N-pyridinylcarbamates

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Abstract

A 3 × 3 isomer grid of nine Methylphenyl-N-pyridinylcarbamates (CxxM) is reported with seven CxxM crystal structures at 294 K (xx = pp, pm, po, mp, op, om, oo; x = para-, meta-, ortho), where Cx = pyridinyl ring (as C5NH4NH-) and xM is representative of –C(=O)OC6H4CH3. All seven carbamate crystal structures aggregate via N–H…N intermolecular interactions with the three CpxM carbamates having C(6) zigzag chains, CmpM with C(5) zigzag chains and three ortho-pyridine CoxM structures as hydrogen-bonded dimers with graph set \(R_{2}^{2}\) (8) and augmented by flanking C–H…O contacts. The CpoM crystal structure crystallises with 0.25 CHCl3 per carbamate molecule and solvent channels aligning along the a-axis direction. Conformational analyses of the nine minimised CxxM structures in gas phase are detailed for comparisons with the solid-state structures and demonstrate similarities between both structural methods. The modelling results also demonstrate the problems associated with pendant ortho-groups sterically clashing in the CmoM and CooM structures and methods to find a reasonable estimate of the CxxM conformational landscape.

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Acknowledgments

This research was funded by the Programme for Research in Third Level Institutions (PRTLI) Cycle 4 (Ireland) and co-funded through the European Regional Development Fund (ERDF), part of the European Union Structural Funds Programme (ESF) 2007–2013. The Irish Centre for High End Computing (ICHEC) is thanked for support and assistance with the computational calculations (http://www.ichec.ie).

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Authors and Affiliations

  1. School of Chemical Sciences, Dublin City University, Dublin 9, Ireland

    Pavle Mocilac & John F. Gallagher

  2. Faculté des Sciences et Technologies, Université de Lorraine, Boulevard des Aiguelettes, BP 70239, 54506, Vandoeuvre-dès-Nancy, France

    John F. Gallagher

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  1. Pavle Mocilac
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  2. John F. Gallagher
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Correspondence to John F. Gallagher.

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John F. Gallagher: On sabbatical leave at CRM2.

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Mocilac, P., Gallagher, J.F. Structural systematics and conformational analyses of an isomer grid of nine tolyl-N-pyridinylcarbamates. Struct Chem 28, 697–708 (2017). https://doi.org/10.1007/s11224-016-0851-5

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  • DOI: https://doi.org/10.1007/s11224-016-0851-5

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