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Supramolecular architectures in o-carboranyl alcohols bearing N-aromatic rings: syntheses, crystal structures and melting points correlation

Supramolecular architectures in o-carboranyl alcohols bearing N-aromatic rings: syntheses, crystal structures and melting points correlation
Supramolecular architectures in o-carboranyl alcohols bearing N-aromatic rings: syntheses, crystal structures and melting points correlation
The syntheses of new o-carboranyl alcohols bearing N-aromatic rings, 1-[R(hydroxy)methyl]-2-methyl-1,2-dicarba-closo-dodecaborane (R = 6-methyl-2-pyridyl 1b, 3-pyridyl 1c, 2-quinolyl 1e, 4-quinolyl 1f), 1-[R(hydroxy)methyl]-1,2-dicarba-closo-dodecaborane (R = 2-pyridyl 2a, 6-methyl-2-pyridyl 2b, 3-pyridyl 2c, 4-pyridyl 2d, 2-quinolyl 2e, 4-quinolyl 2f)), are reported. The crystal structures of all compounds, except that for 1b, are reported and compared with those related compounds previously synthesized by us (1-[R(hydroxy) methyl]-2-methyl-1,2-dicarba-closo-dodecaborane (R = 2-pyridyl 1a, 4-pyridyl 1d)). We provide an analysis of these compounds by means of X-ray crystallography, NMR/IR spectroscopies, thermal analyses and gas phase calculations in the context of crystal engineering. The results show that the crystal packings of these alcohols are dominated by the supramolecular O-H center dot center dot center dot N heterosynthon, but also include other weaker interactions such as C-H center dot center dot center dot O hydrogen bonds, H center dot center dot center dot H contacts and some degree of (C center dot center dot center dot B)-H center dot center dot center dot pi interactions. There are four types of O-H center dot center dot center dot N hydrogen bonded chains, two giving rise to high melting point compounds (1c, 1d, 1f, 2c, 2d, and 2f) and two affording lower melting point compounds (1a, 2a and 2b). The lowest melting compounds (1e and 2e) show no such infinite O-H center dot center dot center dot N hydrogen bonding networks and only intramolecular O-H center dot center dot center dot N hydrogen bonds. We correlate the presence of the infinite O-H center dot center dot center dot N hydrogen bonding network in the crystal structure for the pyridine derivatives with their melting points. Gas phase calculations show that the energy for the O-H center dot center dot center dot N interactions in hydrogen bonded dimers is in the range 4-8 kcal mol(-1)
1466-8033
5788-5806
Di Salvo, Florencia
e6d3739a-5387-4003-af7d-97429c4c8bd2
Camargo, Beatriz
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García, Yolanda
87ac6642-a6a3-4388-9d87-66bda59090b5
Teixidor, Francesc
d24b81b5-5d82-42ca-bd30-fd9c73d0ee68
Viñas, Clara
636b5d2e-fefb-4e83-93df-9615eee8e771
Planas, José Giner
98b21b50-1c21-4265-bd3c-67afe28ef652
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Di Salvo, Florencia
e6d3739a-5387-4003-af7d-97429c4c8bd2
Camargo, Beatriz
90f064f7-e1ac-46b1-9166-d1cca4b0288a
García, Yolanda
87ac6642-a6a3-4388-9d87-66bda59090b5
Teixidor, Francesc
d24b81b5-5d82-42ca-bd30-fd9c73d0ee68
Viñas, Clara
636b5d2e-fefb-4e83-93df-9615eee8e771
Planas, José Giner
98b21b50-1c21-4265-bd3c-67afe28ef652
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da

Di Salvo, Florencia, Camargo, Beatriz, García, Yolanda, Teixidor, Francesc, Viñas, Clara, Planas, José Giner, Light, Mark E. and Hursthouse, Michael B. (2011) Supramolecular architectures in o-carboranyl alcohols bearing N-aromatic rings: syntheses, crystal structures and melting points correlation. CrystEngComm, 13 (19), 5788-5806. (doi:10.1039/c1ce05449j).

Record type: Article

Abstract

The syntheses of new o-carboranyl alcohols bearing N-aromatic rings, 1-[R(hydroxy)methyl]-2-methyl-1,2-dicarba-closo-dodecaborane (R = 6-methyl-2-pyridyl 1b, 3-pyridyl 1c, 2-quinolyl 1e, 4-quinolyl 1f), 1-[R(hydroxy)methyl]-1,2-dicarba-closo-dodecaborane (R = 2-pyridyl 2a, 6-methyl-2-pyridyl 2b, 3-pyridyl 2c, 4-pyridyl 2d, 2-quinolyl 2e, 4-quinolyl 2f)), are reported. The crystal structures of all compounds, except that for 1b, are reported and compared with those related compounds previously synthesized by us (1-[R(hydroxy) methyl]-2-methyl-1,2-dicarba-closo-dodecaborane (R = 2-pyridyl 1a, 4-pyridyl 1d)). We provide an analysis of these compounds by means of X-ray crystallography, NMR/IR spectroscopies, thermal analyses and gas phase calculations in the context of crystal engineering. The results show that the crystal packings of these alcohols are dominated by the supramolecular O-H center dot center dot center dot N heterosynthon, but also include other weaker interactions such as C-H center dot center dot center dot O hydrogen bonds, H center dot center dot center dot H contacts and some degree of (C center dot center dot center dot B)-H center dot center dot center dot pi interactions. There are four types of O-H center dot center dot center dot N hydrogen bonded chains, two giving rise to high melting point compounds (1c, 1d, 1f, 2c, 2d, and 2f) and two affording lower melting point compounds (1a, 2a and 2b). The lowest melting compounds (1e and 2e) show no such infinite O-H center dot center dot center dot N hydrogen bonding networks and only intramolecular O-H center dot center dot center dot N hydrogen bonds. We correlate the presence of the infinite O-H center dot center dot center dot N hydrogen bonding network in the crystal structure for the pyridine derivatives with their melting points. Gas phase calculations show that the energy for the O-H center dot center dot center dot N interactions in hydrogen bonded dimers is in the range 4-8 kcal mol(-1)

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Published date: 2011
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow

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Local EPrints ID: 347437
URI: http://eprints.soton.ac.uk/id/eprint/347437
ISSN: 1466-8033
PURE UUID: 47421c15-cb33-42cf-8c85-629b0d0385d3
ORCID for Mark E. Light: ORCID iD orcid.org/0000-0002-0585-0843

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Date deposited: 01 Feb 2013 15:00
Last modified: 15 Mar 2024 03:01

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Contributors

Author: Florencia Di Salvo
Author: Beatriz Camargo
Author: Yolanda García
Author: Francesc Teixidor
Author: Clara Viñas
Author: José Giner Planas
Author: Mark E. Light ORCID iD

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