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Crystal Structures of Hexameric and Dimeric Complexes of Lithioisobutyrophenone

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Abstract

The crystal structures of two unsolvated hexameric complexes and one N,N,N′,N′-tetramethyl-1,2-ethanediamine (TMEDA)-solvated dimeric complex of the lithium enolate of 2-methyl-1-phenyl-1-propanone (lithioisobutyrophenone, LiIBP) are reported. The unsolvated LiIBP complexes crystallize from benzene-d 6 to yield two different types of crystals that have similar structures: one in the triclinic space group P-1 with a = 10.7944(7), b = 11.9350(8), c = 12.0956(8) Å; α = 117.5560(10), β = 100.8090(10), γ = 92.3030(10)° and Z = 1 and a second in the monoclinic space group C2/c with a = 17.6011(11), b = 14.7389(9), c = 21.0943(13) Å; β = 105.2510(10)° and Z = 4. The two LiIBP hexamers differ slightly in the conformations of the enolate moieties around the Li6O6 core. The hexamer in both the triclinic as well as the monoclinic polymorph is located on a crystallographic inversion center that each generates the other half of the cluster. The TMEDA-solvated LiIBP dimer crystallizes from hexanes in the monoclinic space group C2/c with a = 11.8472(6), b = 14.8268(7), c = 19.2719(9) Å; β = 98.8480(10)° and Z = 4. The center of the dimer is located on a crystallographic C2 axis. These complexes represent only the second reported crystal structures of either an unsolvated hexamer or a solvated dimer of a lithium enolate of a simple monocarbonyl ketone.

Graphical Abstract

The X-ray crystal structures of two unsolvated hexameric and one N,N,N′,N′-tetramethyl-1,2-ethanediamine (TMEDA)-solvated complexes of the lithium enolate of 2-methyl-1-phenyl-1-propanone (lithioisobutyrophenone, LiIBP) are reported.

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Acknowledgements

The authors wish to thank John Carroll University, the John Huntington Foundation for Education, and the George Codrington Charitable Foundation for financial support of this research. The X-ray diffractometer was funded by NSF Grant 0087210, Ohio Board of Regents Grant CAP-491, and by Youngstown State University.

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Authors and Affiliations

  1. Department of Chemistry, John Carroll University, 20700 North Park Blvd, University Heights, OH, 44118, USA

    Michael A. Nichols & Christina M. Leposa

  2. Department of Chemistry, Youngstown State University, Youngstown, OH, 44555, USA

    Allen D. Hunter & Matthias Zeller

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  1. Michael A. Nichols
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  2. Christina M. Leposa
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  3. Allen D. Hunter
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  4. Matthias Zeller
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Correspondence to Michael A. Nichols.

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Nichols, M.A., Leposa, C.M., Hunter, A.D. et al. Crystal Structures of Hexameric and Dimeric Complexes of Lithioisobutyrophenone. J Chem Crystallogr 37, 825–829 (2007). https://doi.org/10.1007/s10870-007-9255-0

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