Formation of 2D sheets through H?H interaction in the crystal packing of 1,2-bis(3-bromobenzylidene)hydrazne

Article abstract of DOI:10.4067/S0717-97072016000300008

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) ?) 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.

Full text of DOI:10.4067/S0717-97072016000300008

J. Chil. Chem. Soc., 61, Nº 3 (2016)
FORMATION OF 2D SHEETS THROUGH H…H 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
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
RESULTS AND DISCUSSION
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.
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.
Formula
C14H10Br2N2
366.04
Formula weight
Temperature /K
120(2)
Wavelength λ/Å
0.71073
Monoclinic
P21/c
Crystal system
Space Group
a/Å
3.8867(5)
14.8312(14)
11.2322(15)
90
b/Å
c/Å
α/°
β/°
91.716(10)
90
γ/°
Volume/Å3
647.18(13)
2
Z
Scheme 1. Molecular structure of bis(3-bromobenzylidene)hydrazine, 1.
Density (calc.) /g cm-1
θ ranges for data collection
F(000)
1.878
EXPERIMENTAL
2.75-27.00
356
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.
Absorption coefficient mm-1
Index ranges
6.244
-4 ≤ h ≤ 4
-17 ≤ k ≤ 18
-14 ≤ l ≤ 14
1395, (0.0912)
99.4
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%).
Unique data (Rint)
Completeness to theta
Parameters, restrains
82,0
Final R1, wR2 (Obs. data)
Final R1, wR2 (All data)
Goodness of fit on F2 (S)
Largest diff peak and hole/e.Å-3
0.0423, 0.1011
0.0498, 0.1102
1.061
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-Kα
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.
0.512, -0.500
e-mail: s.shirvan2015@gmail.com
3049

J. Chil. Chem. Soc., 61, Nº 3 (2016)
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)C6H4Br-para.16 The two benzene rings are
also in trans configuration with respect to C7–N1 and C7A–N1Abonds 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.
Figure 1. The labeled diagram of 1. Thermal ellipsoids are at 30%
probability level. Symmetry code: (a) -x+1,-y+1,-z.
Table 2. Bond distances (Å) and bond angles (°) for 1.
C2-Br1
C6-C7
1.897(8)
1.480(11)
1.272(11)
1.412(13)
119.5(6)
118.5(6)
C6-C7-Br1
C7-N1-N1i
122.0(8)
110.3(8)
172.2(9)
-180.0(8)
-180.0(8)
C7-N1
C5-C6-C7-N1
C6-C7-N1-N1i
C7-N1-N1i-C7i
N1-N1i
C1-C2-Br1
C3-C2-Br1
(i) Symmetry code: -x+1,-y+1,-z
Table 3. Geometrical parameters of H…H interaction in compound 1.
D
(H´-
D´)
d
d
D-H…
H´-D´ (D…H)
d
<(DH <(DH Symmetry
(H…
H´)
(D…
D´)
H´)
H´)
Code
C1-
H1…
H4-C4
-1+x,
3/2-y,
-1/2+z
4.10
(1)
0.93
0.93
2.412
147
148
Figure 2. A side view representation of 1, showing the presence of CH...
HC interactions, in generation of 2D sheets.
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).
2. S. N. Pandeya, D. Sriram, G., Nath, E. De Clercq, Farmaco 54, 624,
(1999).
3. W. M. Singh, B. C. Dash, Pesticides, 22, 33, (1988).
4. E. M. Hodnett, W. J. Dunn, J. Med. Chem. 13, 768, (1970).
5. F. Aydogan, N. Ocal, Z. Turgut, C. Yolacan, Bull. Korean Chem. Soc. 22,
476, (2001).
6. S. –Y. Liu, Y. –P. Ma, Z. –L. You, J. Chil. Chem. 56, 535, (2011).
7. N. Alizadeh, S. Ershad, H. Naeimi, H. Sharghi, M. Shamsipur, Pol. J.
Chem. 73, 915, (1999).
8. L. Shi, W. –J. Mao, Y. Yang, H. –L. Zhu, J. Cooord. Chem. 62, 3471,
(2009).
9. A. A. Alemi, B. Shaabani, Acta Chim. Slov. 47, 363, (2000).
10. C. –N. Zhang, Y. –F. Zheng, Acta Crystallogr. E64, o36, (2008).
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.
3050

J. Chil. Chem. Soc., 61, Nº 3 (2016)
11. L. Wang, Q. Su, Q. Wu, W. Gao, Y. Mu, Compt. Rend. Chim. 15, 463,
17. C. R. Ojala, W. H. Ojala, D. Britton, C. J. Cramer, Acta Crystallogr. C63,
518, (2007).
(2012).
12. J. L. Wardell, J. N. Low, C. Glidewell, Acta Crystallogr. E62, o1565,
18. M. Sheldrick, SADABS, Bruker AXS, Madison, WI, USA, (1998).
19. Bruker SMART and SAINT. Bruker AXS Inc., Madison,WI, USA, (1998).
20. G. M. Sheldrick, Acta Crystallogr, A64, 112, (2008).
21. Mercury 1.4.1, Copyright Cambridge Crystallographic Data Center, 12
Union Road, Cambridge CB2 1EZ, UK, (2001).
(2006).
13. W. H. Ojala, T. M. Arola, N. Herrera, B. Balidemaj, C. R. Ojala, Acta
Crystallogr. E63, o207, (2007).
14. M. Odabasoglu, O. Buyukgungor, K. Sunil, B. Narayana, Acta Crystallogr.
E63, o4145, (2007).
15. P. –W. Zheng, W. Wang, X. –M. Duan, Acta Crystallogr. E61, o3020,
22. L. –Z. Xu, H. -Z., Xu, S. –H. Yang, C. L. Li, K. Zhou, Acta Cryst. E61,
o31, (2005).
(2005).
23. S. L. Liu, Y. Chen, J. F. Dai, H. W. Liu, Chin. J. Synth. Chem. 12, 219,
(2004).
24. A. Sengul, N. Karadayi, O. Buyukgungor, Acta Cryst. C60, o507, (2004).
16. J. Marignan, J. L. Galigne, J. Falgueirettes. Acta Crystallogr. B28, 93,
(1972).
3051