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Journal of the Chilean Chemical Society

On-line version ISSN 0717-9707

J. Chil. Chem. Soc. vol.61 no.3 Concepción Sept. 2016

http://dx.doi.org/10.4067/S0717-97072016000300008 

 

FORMATION OF 2D SHEETS THROUGH HH INTERACTION IN THE CRYSTAL PACKING OF 1,2-BIS(3-BROMOBENZYLIDENE)HYDRAZNE

 

SADIF A. SHIRVAN,* FEREYDOON KHAZALI, SARA HAYDARI DEZFULI, AND ALI BORSALANI

Department of Chemistry, Omidiyeh Branch, Islamic Azad University, Omidiyeh, Iran
* e-mail: s.shirvan2015@gmail.com


ABSTRACT

The title compound was prepared by condensation of 3-bromobenzaldehyde and hydrazine hydrate in absolute ethyl alcohol and in the presence of sulfuric acid. The title Schiff base compound, C14H10Br2N2, crystallizes with one half-molecule in the asymmetric unit in P21/c monoclinic space group. The mid-point of the N-N bond (1.412(13) Å) lies on an inversion center. The molecular skeleton is approximately planar. In the crystal packing of this complex, neighboring molecules are linked to each other by H...H intermolecular interactions to form 2D sheets.


 

INTRODUCTION

Schiff bases have received more attention in recent years due to various promising applications such as antimicrobial,1-2 antifungal,3 antitumor reagents. 4 Moreover, Schiff bases are used as substrates in the preparation of number of industrial and biologically active compounds via ring closure, cycloaddition and replacement reactions. Schiff bases have also been employed as ligands for complexation of metal ions.5 Also, a wide numbers of papers have focused on the metal complexes of Schiff bases in the field of coordination, biological and material chemistry.6-8 These compounds also suitable for NLO (nonlinear optically active) materials.9 In this regard, crystal structure of eight mono-halogenated symmetrical bis(x-halobenzylidene)hydrazine have been reported. In ortho-position, chloro,10 bromo11 and iodo12 substituents have been studied previously. From meta-position derivatives, only iodinated complex has been reported,13 while crystal structure of all four para-halogenated are determined crystallographically.14-17 From these series, herein, we report the synthesis and crystal structure of bis(3-bromobenzylidene)hydrazine, 1, Scheme 1, for the first time.

 

Scheme 1. Molecular structure of
bis(3-bromobenzylidene)hydrazine, 1.

 

EXPERIMENTAL

Materials and Physical Methods

3-bromobenzaldehyde, hydrazine hydrate and other materials were purchased from Merck and used as received. Elemental analysis was performed using a Heraeus CHN-O Rapid analyzer. Melting point was obtained by a Kofler Heizbank Rechart type 7841 melting point apparatus.

Synthesis

A mixture of 3-bromobenzaldehyde (7.4 g, 0.04 mol) and hydrazine hydrate (1.0 ml, 0.02 mol) in 25 ml of absolute ethyl alcohol containing 2 drops of 4 M sulfuric acid was refluxed for about 5 h. On cooling, yellow precipitate formed that was filtered off. Suitable crystals for X-ray diffraction measurement were obtained by slow evaporation from ethyl alcohol over one week (yield 065.0%). Analysis for C14H10F2N2: Found (calculated): C 68.65 (68.85), H 4.18 (4.13), N 11.35% (11.47%).

Crystal structure determination

The X-ray diffraction measurement was made on a Bruker APEX II CCD (Karlsruhe, Germany) area detector diffractometer at 120 K and with Mo-Ka radiation, graphite monochromator, λ = 0.71073Å. The structure of 1 was solved by SHELX-97 and absorption correction was done using the SADABS programs.18 Data collection, cell refinement, and data reduction was done by APEX II,18 SAINT, SHELXTL, 19 PLATON,20 and MERCURY21 softwares.

RESULTS AND DISCUSSION

The molecular structure of the compounds 1 was determined by X-ray crystallographic analysis. The crystallographic data and refinement parameters are listed in Table 1. The ORTEP diagram of molecular structure and packing are shown in Figures 1 and 2.

 

Table 1. Crystallographic and structure refinement
data for 1.

 

Figure 1. The labeled diagram of 1. Thermal
ellipsoids are at 30% probability level. Symmetry code:
(a) -x+1,-y+1,-z.

 

Figure 2. A side view representation of 1, showing
the presence of CH...HC interactions, in generation
of 2D sheets.

 

As it is clear from Figure 1, in the solid state, the molecule of 1 possesses a crystallographically imposed center of symmetry at the mid-point of the N—N bond. So, the asymmetric unit of the compound is composed of one half of the molecule. The C=N-N=C linkage is planar. The N-N bond [1.412(13) Å], Table 2, is slightly longer than in related azine compounds.22-24 The C=N-N angle [110.3(8)°], Table 2, is significantly smaller than the ideal sp2 value of 120°, as a consequence of repulsion between the nitrogen lone pairs and the adjacent C=N bond. The imino group in this compound is nearly coplanar with the two benzene rings (C5-C6-C7-N1: 172.2(9)°), Table 2, with similar torsion angles in comparison with compounds ortho-BrC6H4(CH=N-N=HC)C6H4Br-ortho11 and para-BrC6H4(CH=N-N=HC)C6H(Br-para.16 The two benzene rings are also in trans configuration with respect to C7-N1 and C7A-N1A bonds relative to N1-N1A. In the crystal packing of this complex, neighboring molecules are linked to each other by H...H intermolecular interactions to form 2D sheets, Figure 2, Table 3. The H...H distance between adjacent molecules is 2.412 Å. In the packing of this complex, the overall supramolecular structure results from the head-to-tail π...π interactions between adjacent phenyl rings from neighbouring 2D sheets with ring centroid-to-centroid distances of 3.887(8) Å, Figure 3.

 

Table 2. Bond distances (Å) and bond angles (°) for 1.

(i) Symmetry code: -x+1,-y+1,-z

 

Table 3. Geometrical parameters of H...H interaction in
compound 1.

 

Figure 3. A representation of part of 1, in a-direction,
showing the formation of overall supramolecular structure
from the linkage of neighbouring molecules, through
head-to-tail π...π interactions.

 

SUPPORTING INFORMATION

CCDC-1418738 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge at http://www.ccdc.cam.ac.uk/const/retrieving.html or from the Cambridge Crystallographic Data Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-336033 or e-mail: deposit@ccdc.cam.ac.uk.

ACKNOWLEDGEMENT

We would like to thank the Graduate Study Councils of Islamic Azad University, Omidiyeh Branch, for financial support.

 

REFERENCES

1. A. H. El-masry, H. H., Fahmy, S. H. A. Abdelwahed, Molecules 5, 1429, (2000).         [ Links ]

2. S. N. Pandeya, D. Sriram, G., Nath, E. De Clercq, Farmaco 54, 624, (1999).         [ Links ]

3. W. M. Singh, B. C. Dash, Pesticides, 22, 33, (1988).         [ Links ]

4. E. M. Hodnett, W. J. Dunn, J. Med. Chem. 13, 768, (1970).         [ Links ]

5. F. Aydogan, N. Ocal, Z. Turgut, C. Yolacan, Bull. Korean Chem. Soc. 22, 476, (2001).         [ Links ]

6. S. -Y. Liu, Y. -P. Ma, Z. -L. You, J. Chil. Chem. 56, 535, (2011).         [ Links ]

7. N. Alizadeh, S. Ershad, H. Naeimi, H. Sharghi, M. Shamsipur, Pol. J. Chem. 73, 915, (1999).         [ Links ]

8. L. Shi, W. -J. Mao, Y. Yang, H. -L. Zhu, J. Cooord. Chem. 62, 3471, (2009).         [ Links ]

9. A. A. Alemi, B. Shaabani, Acta Chim. Slov. 47, 363, (2000).         [ Links ]

10. C. -N. Zhang, Y. -F. Zheng, Acta Crystallogr. E64, o36, (2008).         [ Links ]

11. L. Wang, Q. Su, Q. Wu, W. Gao, Y. Mu, Compt. Rend. Chim. 15, 463, (2012).         [ Links ]

12. J. L. Wardell, J. N. Low, C. Glidewell, Acta Crystallogr. E62, o1565, (2006).         [ Links ]

13. W. H. Ojala, T. M. Arola, N. Herrera, B. Balidemaj, C. R. Ojala, Acta Crystallogr. E63, o207, (2007).         [ Links ]

14. M. Odabasoglu, O. Buyukgungor, K. Sunil, B. Narayana, Acta Crystallogr. E63, o4145, (2007).         [ Links ]

15. P. -W. Zheng, W. Wang, X. -M. Duan, Acta Crystallogr. E61, o3020, (2005).         [ Links ]

16. J. Marignan, J. L. Galigne, J. Falgueirettes. Acta Crystallogr. B28, 93, (1972).         [ Links ]

17. C. R. Ojala, W. H. Ojala, D. Britton, C. J. Cramer, Acta Crystallogr. C63, 518, (2007).         [ Links ]

18. M. Sheldrick, SADABS, Bruker AXS, Madison, WI, USA, (1998).         [ Links ]

19. Bruker SMART and SAINT. Bruker AXS Inc., Madison,WI, USA, (1998).         [ Links ]

20. G. M. Sheldrick, Acta Crystallogr, A64, 112, (2008).         [ Links ]

21. Mercury 1.4.1, Copyright Cambridge Crystallographic Data Center, 12 Union Road, Cambridge CB2 1EZ, UK, (2001).         [ Links ]

22. L. -Z. Xu, H. -Z., Xu, S. -H. Yang, C. L. Li, K. Zhou, Acta Cryst. E61, o31, (2005).         [ Links ]

23. S. L. Liu, Y. Chen, J. F. Dai, H. W. Liu, Chin. J. Synth. Chem. 12, 219, (2004).         [ Links ]

24. A. Sengul, N. Karadayi, O. Buyukgungor, Acta Cryst. C60, o507, (2004).         [ Links ]

 

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