organic compounds
(E)-2,4-Dibromo-6-(hydrazinylidenemethyl)phenol
aDepartment of Chemistry, Govt. Model Science College, Jiwaji University, Gwalior 474 011, India, bSchool of Studies in Chemistry, Jiwaji University, Gwalior 47011, India, and cDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
*Correspondence e-mail: skggwr@gmail.com
The title compound, C7H6Br2N2O, was obtained from a condensation reaction of 3,5-dibromo-2-hydroxybenzaldehyde and hydrazine hydrate. The molecule is approximately planar, the largest deviation from the mean plane through all of the non-H atoms being 0.053 (1) Å. The molecular conformation is stabilized by an intramolecular O—H⋯N hydrogen bond, generating an S(6) ring motif. In the crystal, intermolecular N—H⋯Br and N—H⋯O hydrogen bonds link the molecules, forming chains parallel to the b axis. Molecules are further linked by π–π stacking interactions, with centroid–centroid distances of 3.925 (3)–3.926 (3) Å, forming a three-dimensional network.
Keywords: crystal structure; hydrazonomethyl derivative; π–π interactions.
CCDC reference: 1576511
Structure description
Hydrazine-based et al., 1997; Knof et al., 1993; Mukhopadhyay & Pal, 2009). These compounds also play an important role in the development of photomolecular devices, as probes for biological macromolecules and in organic synthesis (Boyer et al., 2010; Samojlowicz et al., 2009; Nagaraju et al., 2012). The crystal structures of related compounds, such as 2-(hydrazonomethyl)phenol (Shang et al., 2009), 2-ethoxy-4-{[(2-nitrophenyl)hydrazono]methyl}phenol (Yin et al., 2009) and 2-ethoxy-4-[2-(3-nitrophenyl)hydrazonomethyl]phenol (Chen et al., 2009), have been reported. As part of our studies of the coordination chemistry of (Gupta et al., 2015), we have synthesized the title compound and determined its crystal structure.
are of great interest due to their ability to behave as non-innocent ligands (ArionThe molecular structure of the title complex is shown in Fig. 1. The whole molecule is almost planar, with the largest deviation from the mean plane through all of the non-H atoms in the molecule being 0.053 (1) Å for atom Br2A. The molecular conformation is stabilized by an intramolecular O1A—H1A⋯N1A hydrogen bond (Table 1), generating an S(6) ring motif (Bernstein et al., 1995). This also contributes to the planarity of the molecule.
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Intermolecular N2A—H2AB⋯Br1A and N2A—H2AB⋯O1A hydrogen bonds link the molecules, forming a chain parallel to the b axis (Fig. 2 and Table 1). Molecules in the are also linked by intermolecular π–π stacking interactions [Cg1⋯Cg1(x, y − 1, z) = 3.926 (3) Å and Cg1⋯Cg1(x, y + 1, z) = 3.925 (3) Å; Cg1 is the centroid of the C1A–C6A ring] (Fig. 3). These contacts combine with the classical hydrogen bonds to generate a three-dimensional network.
Synthesis and crystallization
A hot ethanolic solution of hydrazine hydrate (0.25 g, 0.005 mol) was added dropwise to a hot stirred solution of 3,5-dibromo-2-hydroxybenzaldehyde (1.22 g, 0.005 mol) in ethanol (Fig. 4). The resulting solution was heated under reflux for 3 h. The solution was allowed to cool to ambient temperature. Slow evaporation of the solvent resulted in yellow plate-like crystals of the title compound suitable for X-ray analysis after 8 d (yield: 1.05 g, 80%; m.p. 436–438 K). Analysis calculated for C7H6Br2N2O: C 28.60, H 2.05, N 9.53%; found: C 28.36, H 2.02, N 9.63%.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1576511
https://doi.org/10.1107/S2414314617013864/sj4134sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617013864/sj4134Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617013864/sj4134Isup3.cml
Data collection: CrysAlis PRO (Rigaku, 2017); cell
CrysAlis PRO (Rigaku, 2017); data reduction: CrysAlis PRO (Rigaku, 2017); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C7H6Br2N2O | F(000) = 1120 |
Mr = 293.96 | Dx = 2.220 Mg m−3 |
Monoclinic, I2/a | Mo Kα radiation, λ = 0.71073 Å |
a = 18.020 (2) Å | Cell parameters from 5125 reflections |
b = 3.9253 (4) Å | θ = 2.2–30.0° |
c = 24.933 (2) Å | µ = 9.17 mm−1 |
β = 94.259 (8)° | T = 295 K |
V = 1758.7 (3) Å3 | Plate, yellow |
Z = 8 | 0.5 × 0.2 × 0.1 mm |
Rigaku XtaLAB Mini II CCD diffractometer | 1282 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed X-ray tube | Rint = 0.070 |
ω scans | θmax = 25.4°, θmin = 3.3° |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku, 2017) | h = −21→21 |
Tmin = 0.230, Tmax = 1.000 | k = −4→4 |
10326 measured reflections | l = −30→30 |
1613 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.0459P)2 + 6.910P] where P = (Fo2 + 2Fc2)/3 |
S = 1.14 | (Δ/σ)max = 0.001 |
1613 reflections | Δρmax = 0.56 e Å−3 |
113 parameters | Δρmin = −0.57 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Br1A | 0.23412 (4) | 0.47804 (16) | 0.09034 (2) | 0.0453 (2) | |
Br2A | 0.13772 (4) | −0.13520 (18) | 0.27766 (2) | 0.0517 (3) | |
O1A | 0.0732 (3) | 0.3890 (12) | 0.05254 (16) | 0.0461 (11) | |
H1A | 0.029080 | 0.366058 | 0.042689 | 0.035 (18)* | |
N1A | −0.0627 (3) | 0.1941 (14) | 0.05791 (19) | 0.0446 (13) | |
N2A | −0.1345 (3) | 0.1576 (17) | 0.0353 (2) | 0.0541 (15) | |
H2AA | −0.166666 | 0.045254 | 0.051968 | 0.19 (6)* | |
H2AB | −0.147083 | 0.247164 | 0.004444 | 0.08 (3)* | |
C1A | 0.0862 (3) | 0.2597 (15) | 0.1025 (2) | 0.0365 (14) | |
C2A | 0.1570 (4) | 0.2827 (15) | 0.1280 (2) | 0.0385 (15) | |
C3A | 0.1729 (4) | 0.1632 (15) | 0.1793 (2) | 0.0410 (15) | |
H3AA | 0.220759 | 0.181028 | 0.195826 | 0.049* | |
C4A | 0.1169 (4) | 0.0170 (14) | 0.2059 (2) | 0.0383 (14) | |
C5A | 0.0458 (4) | −0.0200 (14) | 0.1816 (2) | 0.0380 (14) | |
H5AA | 0.009054 | −0.125981 | 0.199841 | 0.046* | |
C6A | 0.0296 (3) | 0.1025 (14) | 0.1294 (2) | 0.0356 (14) | |
C7A | −0.0458 (4) | 0.0585 (15) | 0.1036 (2) | 0.0396 (14) | |
H7AA | −0.080992 | −0.067710 | 0.120485 | 0.047* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1A | 0.0412 (4) | 0.0464 (4) | 0.0497 (4) | −0.0024 (3) | 0.0143 (3) | 0.0030 (3) |
Br2A | 0.0606 (5) | 0.0497 (4) | 0.0448 (4) | −0.0013 (4) | 0.0041 (3) | 0.0120 (3) |
O1A | 0.037 (3) | 0.063 (3) | 0.039 (2) | −0.006 (2) | 0.005 (2) | 0.005 (2) |
N1A | 0.039 (4) | 0.056 (3) | 0.040 (3) | −0.002 (3) | 0.009 (2) | −0.005 (3) |
N2A | 0.031 (3) | 0.087 (4) | 0.044 (3) | 0.003 (3) | 0.001 (3) | 0.001 (3) |
C1A | 0.045 (4) | 0.035 (3) | 0.030 (3) | 0.003 (3) | 0.008 (3) | −0.002 (2) |
C2A | 0.046 (4) | 0.030 (3) | 0.041 (3) | 0.002 (3) | 0.015 (3) | −0.002 (3) |
C3A | 0.045 (4) | 0.035 (3) | 0.045 (3) | −0.002 (3) | 0.011 (3) | −0.003 (3) |
C4A | 0.045 (4) | 0.032 (3) | 0.038 (3) | 0.002 (3) | 0.008 (3) | −0.001 (3) |
C5A | 0.041 (4) | 0.032 (3) | 0.043 (3) | −0.003 (3) | 0.013 (3) | −0.001 (3) |
C6A | 0.038 (4) | 0.031 (3) | 0.039 (3) | −0.002 (3) | 0.011 (3) | −0.005 (2) |
C7A | 0.034 (4) | 0.042 (3) | 0.045 (3) | −0.005 (3) | 0.018 (3) | −0.004 (3) |
Br1A—C2A | 1.896 (6) | C1A—C6A | 1.405 (8) |
Br2A—C4A | 1.897 (6) | C2A—C3A | 1.374 (8) |
O1A—C1A | 1.350 (6) | C3A—C4A | 1.373 (8) |
O1A—H1A | 0.8200 | C3A—H3AA | 0.9300 |
N1A—C7A | 1.273 (8) | C4A—C5A | 1.383 (9) |
N1A—N2A | 1.380 (7) | C5A—C6A | 1.398 (8) |
N2A—H2AA | 0.8600 | C5A—H5AA | 0.9300 |
N2A—H2AB | 0.8600 | C6A—C7A | 1.470 (9) |
C1A—C2A | 1.384 (8) | C7A—H7AA | 0.9300 |
C1A—O1A—H1A | 109.5 | C4A—C3A—H3AA | 120.6 |
C7A—N1A—N2A | 118.5 (5) | C3A—C4A—C5A | 121.5 (6) |
N1A—N2A—H2AA | 120.0 | C3A—C4A—Br2A | 119.0 (5) |
N1A—N2A—H2AB | 120.0 | C5A—C4A—Br2A | 119.5 (4) |
H2AA—N2A—H2AB | 120.0 | C4A—C5A—C6A | 119.7 (5) |
O1A—C1A—C2A | 119.3 (5) | C4A—C5A—H5AA | 120.1 |
O1A—C1A—C6A | 121.5 (5) | C6A—C5A—H5AA | 120.1 |
C2A—C1A—C6A | 119.2 (5) | C5A—C6A—C1A | 119.0 (6) |
C3A—C2A—C1A | 121.8 (5) | C5A—C6A—C7A | 119.4 (5) |
C3A—C2A—Br1A | 119.3 (5) | C1A—C6A—C7A | 121.6 (5) |
C1A—C2A—Br1A | 118.9 (4) | N1A—C7A—C6A | 119.6 (5) |
C2A—C3A—C4A | 118.8 (6) | N1A—C7A—H7AA | 120.2 |
C2A—C3A—H3AA | 120.6 | C6A—C7A—H7AA | 120.2 |
O1A—C1A—C2A—C3A | 178.3 (5) | C4A—C5A—C6A—C1A | 0.4 (8) |
C6A—C1A—C2A—C3A | −1.6 (9) | C4A—C5A—C6A—C7A | 179.3 (5) |
O1A—C1A—C2A—Br1A | −2.7 (7) | O1A—C1A—C6A—C5A | −178.6 (5) |
C6A—C1A—C2A—Br1A | 177.4 (4) | C2A—C1A—C6A—C5A | 1.3 (8) |
C1A—C2A—C3A—C4A | 0.1 (9) | O1A—C1A—C6A—C7A | 2.6 (9) |
Br1A—C2A—C3A—C4A | −178.9 (4) | C2A—C1A—C6A—C7A | −177.5 (5) |
C2A—C3A—C4A—C5A | 1.7 (9) | N2A—N1A—C7A—C6A | −178.1 (5) |
C2A—C3A—C4A—Br2A | −178.0 (4) | C5A—C6A—C7A—N1A | 174.2 (6) |
C3A—C4A—C5A—C6A | −2.0 (9) | C1A—C6A—C7A—N1A | −7.0 (9) |
Br2A—C4A—C5A—C6A | 177.8 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···N1A | 0.82 | 1.85 | 2.579 (7) | 147 |
N2A—H2AB···Br1Ai | 0.86 | 2.94 | 3.774 (6) | 163 |
N2A—H2AB···O1Ai | 0.86 | 2.47 | 3.088 (8) | 129 |
Symmetry code: (i) −x, −y+1, −z. |
Acknowledgements
The authors thank Rigaku Corporation of the X-ray Crystallography Facility at the 24th IUCr Congress and General Assembly, Hyderabad, India, for providing the single-crystal X-ray diffraction data, and the Jiwaji University, Gwalior, for a research grant.
References
Arion, V., Wieghardt, K., Weyhermueller, T., Bill, E., Leovac, V. & Rufinska, A. (1997). Inorg. Chem. 36, 661–669. CSD CrossRef CAS Web of Science Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Boyer, J. L., Rochford, J., Tsai, M.-K., Muckerman, J. T. & Fujita, E. (2010). Coord. Chem. Rev. 254, 309–330. Web of Science CrossRef CAS Google Scholar
Chen, J.-Q., Jiang, L., Li, S.-M. & Chen, Y.-Z. (2009). Acta Cryst. E65, o2536. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gupta, S. K., Anjna, C., Sen, N., Butcher, R. J., Jasinski, J. P. & Golen, J. A. (2015). Polyhedron, 89, 219–231. Web of Science CSD CrossRef CAS Google Scholar
Knof, U., Weyhermuller, T., Wolter, T., Wieghardt, K., Bill, E., Butzlaff, C. & Trautwein, A. X. (1993). Angew. Chem. Int. Ed. Engl. 32, 1635–1638. CSD CrossRef Web of Science Google Scholar
Mukhopadhyay, A. & Pal, S. (2009). Eur. J. Inorg. Chem. pp. 4141–4148. Web of Science CSD CrossRef Google Scholar
Nagaraju, K., Raveendran, R., Pal, S. & Pal, S. (2012). Polyhedron, 33, 52–59. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (2017). CrysAlis PRO. Rigaku Americas Corporation, The Woodlands, USA. Google Scholar
Samojlowicz, C., Bieniek, M. & Grela, K. (2009). Chem. Rev. 109, 3708–3742. Web of Science PubMed CAS Google Scholar
Shang, Y.-F., Wang, Q.-M., Zhu, M.-L. & Zhang, Y.-H. (2009). Acta Cryst. E65, o3023. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Yin, Z.-G., Qian, H.-Y., Zhang, C.-X. & Zhu, X.-W. (2009). Acta Cryst. E65, o2575. Web of Science CSD CrossRef IUCr Journals Google Scholar
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