X-ray structure at 150 K of the Polar Alkyl Mesogenic Compound 7CBB:4-Cyanobiphenyl-4′-heptylbiphenyl Carboxylate

Journal article


Gupta, S.,, Choudhury, T,, Kumar Das, M., Lisgarten, D., Cockcroft, J.C., Palmer, R. A. and Lisgarten, J. N. 2020. X-ray structure at 150 K of the Polar Alkyl Mesogenic Compound 7CBB:4-Cyanobiphenyl-4′-heptylbiphenyl Carboxylate. Journal of Chemical Crystallography. pp. 3-13.
AuthorsGupta, S.,, Choudhury, T,, Kumar Das, M., Lisgarten, D., Cockcroft, J.C., Palmer, R. A. and Lisgarten, J. N.
Abstract

Abstract
The compound under study 7CBB consists of two biphenyl moieties A–B and C–D linked by a carboxylate group. Ring Aterminates in a 4-cyano group and C–D is linked to the terminal alkyl chain. A previously reported room temperature determination of the crystal structure employing MoKα X-radiation was thought to contain serious errors in describing the alkyl chain as being disordered. The X-ray structure factors were not deposited with this published structure and as a consequence two new X-ray data sets have been collected: (1) using MoKα radiation at room temperature 295 K (a repeat of the previous study) and (2) using CuKα radiation at 150 K in an attempt, which proved successful, to improve the overall quality of the structure determination. The corrected MoKα structure and the CuKα structure both reported here have enabled the previous errors to be identified, concluding that there is no disorder in the alkyl chain. The alkyl chain in the MoKα structure at 295 K was found to have anisotropic thermal factors slightly exaggerated with respect to the remainder of the structure. However,this effect is not observed in the CuKα structure at 150 K, all anisotropic thermal factors including those in the alkyl chain being reduced to cover a much smaller overall range of values. Consequently, it can be concluded that the effect observed in the alkyl chain at 295 K is merely one of a thermal nature, not one of disorder. There are no unusual bond lengths or angles present. The biphenyl moieties are planar within 0.035 Å and 0.020 Å respectively. The dihedral angles of all ring pairs have been calculated. Calculation of intermolecular distances between molecules related by a centre of symmetry reveals the existence of a number of van-der Waals interactions. The H-bonding motif typical of crystal structures of cyanobiphenyl compounds is observed. The molecular packing mode corresponds to that of a precursor of the smectic phase.

Graphic Abstract
The alkyl chain thermal ellipsoids for 7CBB (a) the Mo RT structure are noticeably exaggerated compared to those for the remainder of the structure, an effect which is not present in (b) the Cu LT structure (Drawn with Ortep/Raster (Barnes in J Appl Cryst 30:568, 1997; Merritt and Bacon in Methods Enzymol 277:505–524, 1997)). It may be concluded therefore that in the Mo RT structure this is a thermal effect and cannot be explained in terms of static disorder.

KeywordsPolar properties; X-ray crystal structure; Smectic phase ; Structure–property relationships
Year2020
JournalJournal of Chemical Crystallography
Journal citationpp. 3-13
PublisherSpringer Nature
ISSN1074-1542
Digital Object Identifier (DOI)doi:doi:10.1007/s10870-020-00826-5
Official URLhttps://doi.org/10.1007/s10870-020-00826-5
Publication dates
Print25 Feb 2020
Publication process dates
Accepted20 Feb 2020
Deposited18 May 2020
Accepted author manuscript
Supplemental file
References

1.
Dabrowski R, Pye K, Przedmojski J, Pura B (1985) Mol Cryst Liq Cryst 129:169–190
CAS
Article
Google Scholar
2.
Haldar S, Mandal PK, Prathap SJ, Guru Row TN, Dabrowski R (2009) Mol Cryst Liq Cryst 503:99–111
CAS
Article
Google Scholar
3.
Barnes CL (1997) J Appl Cryst 30:568
CAS
Article
Google Scholar
4.
Merritt EA, Bacon DJ (1997) Methods Enzymol 277:505–524
CAS
Article
Google Scholar
5.
Dolomanov OV, Bourhis LJ, Gildea RJ, Howard JAK, Puschmann H (2009) J Appl Crystallogr 42:339–341
CAS
Article
Google Scholar
6.
Sheldrick GM (2008) Acta Cryst A64:112–122
Article
Google Scholar
7.
Sheldrick GM (1997) (Release 97-2) University of Gottingen, Germany
8.
Farrugia LJ (1999) J Appl Cryst 32:837–838
CAS
Article
Google Scholar
9.
Nardelli M (1983) Comput Chem 7:95–98
CAS
Article
Google Scholar
10.
Nardelli M (1995) J Appl Cryst 28:659
CAS
Article
Google Scholar
11.
Spek AL (1990) Acta Crystallogr A 46:C34
Google Scholar
12.
Ladd MFC, Palmer RA (2013) Springer, New York
13.
Systèmes D (2016) San Diego, 2016
14.
Bruno IJ, Cole JC, Edgington PR, Kessler MK, Macrae CF, McCabe P, Pearson J, Taylor R (2002) Acta Cryst B58:389–397
CAS
Article
Google Scholar
15.
Desiraju GR (1995) Angew Chem Int Ed Engl 34:2311–2327
CAS
Article
Google Scholar
16.
Centore R, Causà M (2018) Cryst Growth Des 18:3535–3543
CAS
Article
Google Scholar
17.
Kitaigorodski AI (1973) Academic Press. New York
18.
Chandrasekhar S (1992) Liquid crystals. Cambridge University Press, Cambridge
Google Scholar
19.
Bryan RF, Forcier PG (1980) Mol Cryst Liq Cryst 60:133–152
CAS
Article
Google Scholar
20.
Brodzik M, Dabrowski R, Przedmojski J (1995) J Phys II France 5:1805–1817
CAS
Article
Google Scholar
21.
Brownsey GJ, Leadbetter AJ (1980) Phys Rev Lett 44:1608–1612
CAS
Article
Google Scholar
22.
Urban S, Novotna E, Kresse H and Dabrowski R (1995) Proc SPIE 2372, Liquid Crystals: Materials Science and Applications
23.
Dabrowski R, Czupryński K, Przedmojski J, Baran J, Jadzyn J, Czechowski G (1994) Mol Cryst Liq Cryst 249:51–59
CAS

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