2-(4-Bromo­phen­yl)acetohydrazide

Ahmad, S.; Jabbar, A.; Hussain, M.T.; Tahir, M.N.

doi:10.1107/S1600536812027006

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2269

https://doi.org/10.1107/S1600536812027006

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2-(4-Bromophenyl)acetohydrazide

Shakeel Ahmad,^a Abdul Jabbar,^a Muhammad Tahir Hussain ^b and M. Nawaz Tahir ^c ^*

^aDepartment of Chemistry, Government College University, Faisalabad 38000, Pakistan, ^bDepartment of Applied Sciences, National Textile University, Faisalabad 37610, Pakistan, and ^cUniversity of Sargodha, Department of Physics, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 14 May 2012; accepted 14 June 2012; online 30 June 2012)

In the title compound, C₈H₉BrN₂O, the 1-bromo-4-methylbenzene group and the formic hydrazide moiety [r.m.s. deviations of 0.0129 and 0.0038 Å] are oriented at a dihedral angle of 80.66 (11)°. In the crystal, molecules are linked via strong N—H⋯O hydrogen bonds, leading to the formation of chains in the [010] direction. These chains are linked via weaker N—H⋯N and N—H⋯O hydrogen bonds, with R₂²(7) and R₃²(7) ring motifs, forming a two-dimensional network parallel to (001).

Related literature

For background literature and the crystal structure of 2-chlorobenzohydrazide, see: Ahmad et al. (2012 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₈H₉BrN₂O
M_r = 229.07
Monoclinic, P 2₁
a = 6.0798 (2) Å
b = 4.8565 (1) Å
c = 15.1126 (5) Å
β = 98.003 (2)°
V = 441.88 (2) Å³
Z = 2
Mo Kα radiation
μ = 4.60 mm⁻¹
T = 296 K
0.36 × 0.23 × 0.22 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.298, T_max = 0.366
4331 measured reflections
1814 independent reflections
1677 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.059
S = 1.06
1814 reflections
115 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.47 e Å⁻³
Absolute structure: Flack (1983 ), 583 Friedel pairs
Flack parameter: 0.007 (11)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.02	2.863 (3)	165
N2—H2A⋯N2ⁱⁱ	0.84 (4)	2.37 (4)	3.192 (4)	167 (3)
N2—H2B⋯O1ⁱⁱⁱ	0.73 (3)	2.59 (4)	3.230 (3)	147 (4)
Symmetry codes: (i) x, y+1, z; (ii) $[-x-1, y-{\script{1\over 2}}, -z+1]$ ; (iii) $[-x, y+{\script{1\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812027006/su2429sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812027006/su2429Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812027006/su2429Isup3.cml

checkCIF report

Comment top

Recently, we have reported the crystal structure of 2-chlorobenzohydrazide (Ahmad et al., 2012). In continuation of this work we have synthesized the title compound, a hydrazide derivative, and report herein on its crystal structure.

In the title molecule, Fig. 1, the 1-bromo-4-methylbenzene group A (C1–C7/Br1) and the formic hydrazide moiety B (O1/C8/N1/N2) are planar with r. m. s. deviations of 0.0129 Å and 0.0038 Å, respectively. The dihedral angle between these mean planes, A/B, is 80.66 (11)°.

In the crystal, molecules are linked via N—H···O hydrogen bonds to form one-dimensional polymeric chains along [010]. These chains are linked via N-H···N and N-H..O hydrogen bonds to form a two-dimensional polymeric network in (001). The hydrogen bonds give rise to R₂²(7) and R₃²(7) ring motifs (Bernstein et al., 1995; Table 1 and Fig. 2).

Related literature top

For background literature and the crystal structure of 2-chlorobenzohydrazide, see: Ahmad et al. (2012). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

2-(4-Bromophenyl)acetic acid (4.42 g, 0.022 mol) was converted to methyl 2-(4-bromophenyl)acetate by refluxing in methanol (25 ml) in the presence of catalytic amount of sulfuric acid. This ester was then converted into the title compound by refluxing with hydrazine hydrate (80%, 10 ml) in dry methanol. The title compound was purified by recrystallization from dry methanol, giving colourless rod-like crystals [M.p. 438–439 K].

Structure description top

For background literature and the crystal structure of 2-chlorobenzohydrazide, see: Ahmad et al. (2012). For graph-set notation, see: Bernstein et al. (1995).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title molecule with the atom numbering. The displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view along the a axis of the crystal packing of the title compound. The two-dimensional hydrogen bonded network extends in the plane (001). Hydrogen bonds are shown as dashed lines - see Table 1 for details.

2-(4-Bromophenyl)acetohydrazide top

Crystal data top

C₈H₉BrN₂O	F(000) = 228
M_r = 229.07	D_x = 1.722 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1677 reflections
a = 6.0798 (2) Å	θ = 2.7–28.3°
b = 4.8565 (1) Å	µ = 4.60 mm⁻¹
c = 15.1126 (5) Å	T = 296 K
β = 98.003 (2)°	Rod, colourless
V = 441.88 (2) Å³	0.36 × 0.23 × 0.22 mm
Z = 2

Data collection top

Bruker Kappa APEXII CCD diffractometer	1814 independent reflections
Radiation source: fine-focus sealed tube	1677 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 7.50 pixels mm^-1	θ_max = 28.3°, θ_min = 2.7°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −6→4
T_min = 0.298, T_max = 0.366	l = −20→20
4331 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.059	w = 1/[σ²(F_o²) + (0.024P)²] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1814 reflections	Δρ_max = 0.44 e Å⁻³
115 parameters	Δρ_min = −0.47 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 583 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.007 (11)

Crystal data top

C₈H₉BrN₂O	V = 441.88 (2) Å³
M_r = 229.07	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.0798 (2) Å	µ = 4.60 mm⁻¹
b = 4.8565 (1) Å	T = 296 K
c = 15.1126 (5) Å	0.36 × 0.23 × 0.22 mm
β = 98.003 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	1814 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1677 reflections with I > 2σ(I)
T_min = 0.298, T_max = 0.366	R_int = 0.023
4331 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.059	Δρ_max = 0.44 e Å⁻³
S = 1.06	Δρ_min = −0.47 e Å⁻³
1814 reflections	Absolute structure: Flack (1983), 583 Friedel pairs
115 parameters	Absolute structure parameter: 0.007 (11)
1 restraint

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Br1	0.42290 (4)	0.23371 (7)	0.07962 (1)	0.0435 (1)
O1	−0.1520 (3)	0.7065 (5)	0.38909 (13)	0.0457 (6)
N1	−0.2370 (4)	1.1385 (4)	0.42196 (15)	0.0364 (7)
N2	−0.3296 (5)	1.0741 (6)	0.49999 (17)	0.0420 (8)
C1	0.2739 (4)	0.4860 (5)	0.14603 (16)	0.0315 (8)
C2	0.0587 (5)	0.5632 (6)	0.11262 (19)	0.0395 (9)
C3	−0.0499 (4)	0.7519 (8)	0.16041 (16)	0.0407 (8)
C4	0.0518 (5)	0.8638 (5)	0.23979 (17)	0.0362 (8)
C5	0.2669 (5)	0.7798 (7)	0.27159 (17)	0.0416 (12)
C6	0.3788 (5)	0.5900 (6)	0.22578 (17)	0.0381 (8)
C7	−0.0693 (6)	1.0694 (6)	0.2896 (2)	0.0494 (10)
C8	−0.1528 (4)	0.9529 (5)	0.37211 (16)	0.0289 (7)
H1	−0.23523	1.30826	0.40587	0.0437*
H2	−0.01156	0.49007	0.05918	0.0474*
H2A	−0.416 (5)	0.940 (8)	0.491 (2)	0.0503*
H2B	−0.230 (6)	1.040 (8)	0.531 (2)	0.0503*
H3	−0.19442	0.80410	0.13848	0.0488*
H5	0.33752	0.85271	0.32499	0.0500*
H6	0.52191	0.53407	0.24842	0.0457*
H7A	−0.19487	1.14063	0.24952	0.0591*
H7B	0.02941	1.22250	0.30749	0.0591*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0503 (2)	0.0403 (2)	0.0433 (1)	0.0101 (2)	0.0184 (1)	−0.0001 (2)
O1	0.0663 (11)	0.0214 (11)	0.0547 (10)	0.0035 (12)	0.0269 (9)	0.0049 (11)
N1	0.0533 (14)	0.0226 (11)	0.0367 (11)	0.0007 (9)	0.0184 (10)	0.0019 (8)
N2	0.0511 (16)	0.0378 (14)	0.0407 (14)	0.0000 (12)	0.0193 (12)	−0.0020 (11)
C1	0.0367 (13)	0.0284 (14)	0.0315 (12)	0.0012 (10)	0.0123 (10)	0.0007 (10)
C2	0.0393 (14)	0.0426 (17)	0.0356 (13)	0.0034 (12)	0.0021 (12)	−0.0016 (12)
C3	0.0373 (11)	0.0407 (16)	0.0442 (12)	0.0084 (16)	0.0063 (10)	0.0062 (17)
C4	0.0523 (16)	0.0247 (13)	0.0352 (13)	0.0029 (11)	0.0185 (12)	0.0034 (10)
C5	0.0488 (14)	0.044 (3)	0.0321 (11)	−0.0038 (14)	0.0061 (11)	−0.0051 (12)
C6	0.0344 (14)	0.0440 (16)	0.0355 (13)	0.0028 (12)	0.0040 (12)	0.0009 (12)
C7	0.077 (2)	0.0298 (16)	0.0479 (17)	0.0083 (15)	0.0319 (16)	0.0057 (13)
C8	0.0312 (12)	0.0221 (13)	0.0338 (12)	0.0001 (10)	0.0064 (10)	−0.0008 (9)

Geometric parameters (Å, º) top

Br1—C1	1.893 (2)	C4—C5	1.390 (4)
O1—C8	1.224 (3)	C4—C7	1.503 (4)
N1—N2	1.411 (4)	C5—C6	1.387 (4)
N1—C8	1.323 (3)	C7—C8	1.520 (4)
N1—H1	0.8600	C2—H2	0.9300
N2—H2B	0.73 (3)	C3—H3	0.9300
N2—H2A	0.84 (4)	C5—H5	0.9300
C1—C2	1.387 (4)	C6—H6	0.9300
C1—C6	1.379 (4)	C7—H7A	0.9700
C2—C3	1.389 (4)	C7—H7B	0.9700
C3—C4	1.382 (4)

N2—N1—C8	123.8 (2)	O1—C8—C7	123.0 (2)
C8—N1—H1	118.00	N1—C8—C7	114.4 (2)
N2—N1—H1	118.00	O1—C8—N1	122.5 (2)
N1—N2—H2B	101 (3)	C1—C2—H2	121.00
H2A—N2—H2B	112 (4)	C3—C2—H2	121.00
N1—N2—H2A	111 (2)	C2—C3—H3	119.00
Br1—C1—C2	118.61 (19)	C4—C3—H3	119.00
Br1—C1—C6	120.2 (2)	C4—C5—H5	119.00
C2—C1—C6	121.2 (2)	C6—C5—H5	119.00
C1—C2—C3	118.8 (2)	C1—C6—H6	121.00
C2—C3—C4	121.5 (3)	C5—C6—H6	121.00
C3—C4—C7	120.3 (3)	C4—C7—H7A	109.00
C3—C4—C5	118.1 (3)	C4—C7—H7B	109.00
C5—C4—C7	121.6 (3)	C8—C7—H7A	109.00
C4—C5—C6	121.7 (3)	C8—C7—H7B	109.00
C1—C6—C5	118.7 (3)	H7A—C7—H7B	108.00
C4—C7—C8	114.0 (2)

N2—N1—C8—O1	1.3 (4)	C2—C3—C4—C7	179.5 (3)
N2—N1—C8—C7	178.1 (3)	C3—C4—C5—C6	0.1 (4)
Br1—C1—C2—C3	−178.9 (2)	C7—C4—C5—C6	179.9 (3)
C6—C1—C2—C3	1.0 (4)	C3—C4—C7—C8	104.7 (3)
Br1—C1—C6—C5	178.4 (2)	C5—C4—C7—C8	−75.1 (4)
C2—C1—C6—C5	−1.5 (4)	C4—C5—C6—C1	1.0 (4)
C1—C2—C3—C4	0.2 (5)	C4—C7—C8—O1	−10.6 (4)
C2—C3—C4—C5	−0.7 (4)	C4—C7—C8—N1	172.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.02	2.863 (3)	165
N2—H2A···N2ⁱⁱ	0.84 (4)	2.37 (4)	3.192 (4)	167 (3)
N2—H2B···O1ⁱⁱⁱ	0.73 (3)	2.59 (4)	3.230 (3)	147 (4)

Symmetry codes: (i) x, y+1, z; (ii) −x−1, y−1/2, −z+1; (iii) −x, y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₈H₉BrN₂O
M_r	229.07
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	6.0798 (2), 4.8565 (1), 15.1126 (5)
β (°)	98.003 (2)
V (Å³)	441.88 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.60
Crystal size (mm)	0.36 × 0.23 × 0.22

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.298, 0.366
No. of measured, independent and observed [I > 2σ(I)] reflections	4331, 1814, 1677
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.059, 1.06
No. of reflections	1814
No. of parameters	115
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.47
Absolute structure	Flack (1983), 583 Friedel pairs
Absolute structure parameter	0.007 (11)

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.02	2.863 (3)	165
N2—H2A···N2ⁱⁱ	0.84 (4)	2.37 (4)	3.192 (4)	167 (3)
N2—H2B···O1ⁱⁱⁱ	0.73 (3)	2.59 (4)	3.230 (3)	147 (4)

Symmetry codes: (i) x, y+1, z; (ii) −x−1, y−1/2, −z+1; (iii) −x, y+1/2, −z+1.

Acknowledgements

The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. The authors also acknowledge the technical support provided by Syed Muhammad Hussain Rizvi of Bana International, Karachi, Pakistan.

References

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