(E)-2,4-Di­bromo-6-(hydrazinylidenemeth­yl)phenol

Bhat, R.A.; Kumar, D.; Ganaie, J.A.; Butcher, R.J.; Gupta, S.K.

doi:10.1107/S2414314617013864

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 10| October 2017| x171386

https://doi.org/10.1107/S2414314617013864

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(E)-2,4-Dibromo-6-(hydrazinylidenemethyl)phenol

Rayees A. Bhat,^a D. Kumar,^a Javeed A. Ganaie,^b Ray J. Butcher ^c and Sushil K. Gupta ^b ^*

^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

Edited by J. Simpson, University of Otago, New Zealand (Received 24 September 2017; accepted 26 September 2017; online 6 October 2017)

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 Schiff bases are of great interest due to their ability to behave as non-innocent ligands (Arion 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 Schiff bases (Gupta et al., 2015 ), we have synthesized the title compound and determined its crystal structure.

The 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.

Table 1
Hydrogen-bond geometry (Å, °)

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.

Figure 1
The molecular structure of the title compound, showing 50% probability displacement ellipsoids. The intramolecular O—H⋯N hydrogen bond forming an S(6) ring motif is shown as a dashed line.

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 crystal structure 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.

Figure 2
The crystal packing of the title compound, viewed along the b axis. Dashed lines indicate intermolecular N—H⋯Br and N—H⋯O hydrogen bonds.

Figure 3
π–π contacts for the title compound (symmetry codes: 1545.01 = x, y − 1, z; 1565.01 = x, y + 1, z).

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%.

Figure 4
A reaction scheme showing the synthesis of the title compound.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₇H₆Br₂N₂O
M_r	293.96
Crystal system, space group	Monoclinic, I2/a
Temperature (K)	295
a, b, c (Å)	18.020 (2), 3.9253 (4), 24.933 (2)
β (°)	94.259 (8)
V (Å³)	1758.7 (3)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	9.17
Crystal size (mm)	0.5 × 0.2 × 0.1

Data collection
Diffractometer	Rigaku XtaLAB Mini II CCD
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku, 2017 )
T_min, T_max	0.230, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10326, 1613, 1282
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.104, 1.14
No. of reflections	1613
No. of parameters	113
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.57
Computer programs: CrysAlis PRO (Rigaku, 2017), SHELXT (Sheldrick, 2015a ), SHELXL2017 (Sheldrick, 2015b ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1576511

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617013864/sj4134sup1.cif

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

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku, 2017); cell refinement: 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).

(E)-2,4-Dibromo-6-(hydrazinylidenemethyl)phenol top

Crystal data top

C₇H₆Br₂N₂O	F(000) = 1120
M_r = 293.96	D_x = 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

Data collection top

Rigaku XtaLAB Mini II CCD diffractometer	1282 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	R_int = 0.070
ω scans	θ_max = 25.4°, θ_min = 3.3°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku, 2017)	h = −21→21
T_min = 0.230, T_max = 1.000	k = −4→4
10326 measured reflections	l = −30→30
1613 independent reflections

Refinement top

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(F_o²) + (0.0459P)² + 6.910P] where P = (F_o² + 2F_c²)/3
S = 1.14	(Δ/σ)_max = 0.001
1613 reflections	Δρ_max = 0.56 e Å⁻³
113 parameters	Δρ_min = −0.57 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.

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