2-(4-Bromo­phen­yl)acetohydrazide

Abstract

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 R ₂ ²(7) and R ₃ ²(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,

• a = 6.0798 (2) Å

• b = 4.8565 (1) Å

• c = 15.1126 (5) Å

• β = 98.003 (2)°

• V = 441.88 (2) ų

• 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[F ² > 2σ(F ²)] = 0.023

• wR(F ²) = 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)

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812027006/su2429Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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).

Experimental

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].

Refinement

The coordinates of the H-atoms of the NH₂ group were refined with U_iso(H) = 1.2U_eq(N). The remainder of the H-atoms were included in calculated positions and treated as riding atoms: N–H = 0.86 Å, C–H = 0.93–0.97 Å, with U_iso(H) = 1.2U_eq(N,C).

Figures

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.

Crystal data

C8H9BrN2O	F(000) = 228
Mr = 229.07	Dx = 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

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

Refinement

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(Fo2) + (0.024P)2] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
1814 reflections	Δρmax = 0.44 e Å−3
115 parameters	Δρmin = −0.47 e Å−3
1 restraint	Absolute structure: Flack (1983), 583 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.007 (11)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.