The first example of coexistence of the ketoamino-enolimino forms of diamine Schiff base naphthaldimine parts: The crystal and molecular structure of N,N'-bis(1-naphthaldimine)-o-phenylenediamine chloroform (1/1) solvate at 200 K

Author(s)
Zora Popovic, Vibor Roje, Gordana Pavlovic, Dubravka Matkovic-Calogovic, Gerald Giester
Abstract

The N,N'-bis(1-naphthaldimine)-o-phenylenediamine chloroform (1/1) solvate was prepared from 2-hydroxy-1-naphthaldehyde and 1,2-phenylenediamine in a 2:1 molar ratio and characterized in solution and in the solid state using X-ray single crystal diffractometry, IR and NMR spectroscopy. The structure consists of three structural fragments: two planar, but not coplanar naphthaldimine moieties linked by phenyl ring that derived from o-phenylenediamine. The naphthaldimine fragments contain, along with naphthalene rings, six-membered pseudoaromatic chelate rings, formed by O-HžžžN or N-HžžžO intramolecular hydrogen bonds that retain planarity of the aldimine fragments. This structure is the first example of the coexistence of two different hydrogen bond types within Schiff base molecule, i.e. the one naphthaldimine part exists in the enolimino form (O-HžžžN hydrogen bond of 2.5487(17) A°), while the other exists in the ketoamino form (N-HžžžO hydrogen bond of 2.5706(19) A°). The different hydrogen bond types are related to the different p-electron density distribution within two parts. The amino hydrogen atom forms three-center intramolecular hydrogen bond, which includes the N-HžžžO hydrogen bond of 2.5706(19) A° within the ketoamino part and also the N-HžžžN bond of 2.7238(18) A° linking two naphthaldimine fragments of the molecule. IR and 1H and 13C NMR spectral data are consistent with revealed molecular structure in the solid state. Œ 2001 Elsevier Science B.V. All rights reserved.

Organisation(s)
Department of Mineralogy and Crystallography
External organisation(s)
University of Zagreb
Journal
Journal of Molecular Structure
Volume
597
Pages
39-47
No. of pages
9
ISSN
0022-2860
Publication date
2001
Peer reviewed
Yes
Austrian Fields of Science 2012
1051 Geology, Mineralogy
Portal url
https://ucrisportal.univie.ac.at/en/publications/the-first-example-of-coexistence-of-the-ketoaminoenolimino-forms-of-diamine-schiff-base-naphthaldimine-parts-the-crystal-and-molecular-structure-of-nnbis1naphthaldimineophenylenediamine-chloroform-11-solvate-at-200-k(8fed7b58-f29a-4b10-851e-b0b816b91f16).html