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β-Chain Hydrogen-Bonding in 4-Hydroxycoumarins

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Abstract

In the solid state, some 3-substituted 4-hydroxycoumarins β-ketoester enols form infinite translational hydrogen-bonded β-chains with varying degrees of alignment between adjacent delocalized systems. Nine related structures have been studied. At the strongest, intermolecular associations are polar, purely translation neighbors interact essentially along a 717 pm crystallographic repeat with shortened 260 pm intermolecular O·OH-bond contacts. Four distinctive features characterize these structures: (1) moderately delocalized β-ketoester enol structures, (2) translational misalignment angles between oxygen donors and acceptors less than 10°, (3) buttressing intermolecular C–H·O contacts co-planar with and near the intermolecular O–H·O interactions, and (4) fully extended ketoester enol hydrogen-bond (ap-anti-anti) geometries. For non-polar β-chains in related coumarin systems, β-ketoester enol alignments are typically poorer, involve hydrogen-bonding between glide relatives, ap-syn-(anti) geometry, and the intermolecular O·OH-bond contacts are longer.

Graphic Abstract

Substituted 4-hydroxycoumarins related to phenprocoumon can form well-aligned polar translational β-chains between enolones showing resonance assisted Hydrogen-bonding and a 717 pm repeat along a crystallographic axis.

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Acknowledgements

EJV thanks the National Science Foundation (MRI-0618148) for support of crystallographic equipment. Thanks also go to Dr. Verner Schomaker (deceased) of the University of Washington for his encouragement, acumen, persistence and pedagogy with difficult structures.

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Authors and Affiliations

  1. Department of Chemistry, University of Portland, 5000 N. Willamette Blvd., Portland, OR, 97203, USA

    Truc-Vi H. Duong, Todd S. Carroll & Edward J. Valente

  2. Science Programs, Washington State University, Vancouver, WA, 98686, USA

    Daniel S. Bejan

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  1. Truc-Vi H. Duong
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  2. Todd S. Carroll
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Correspondence to Edward J. Valente.

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Duong, TV.H., Carroll, T.S., Bejan, D.S. et al. β-Chain Hydrogen-Bonding in 4-Hydroxycoumarins. J Chem Crystallogr 50, 387–399 (2020). https://doi.org/10.1007/s10870-019-00813-5

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