4-Methoxy­benzohydrazide

Ashiq, U.; Jamal, R.A.; Tahir, M.N.; Yousuf, S.; Khan, I.U.

doi:10.1107/S1600536809021345

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1551

doi:10.1107/S1600536809021345

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4-Methoxybenzohydrazide

Uzma Ashiq,^a ^* Rifat Ara Jamal,^a Muhammad Nawaz Tahir,^b Sammer Yousuf ^c and Islam Ullah Khan ^d

^aDepartment of Chemistry, University of Karachi, Karachi 75270, Pakistan, ^bDepartment of Physics, University of Sargodah, Sagodah, Pakistan, ^cHEJ Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan, and ^dDepartment of Chemistry, Government College University, Lahore, Pakistan
^*Correspondence e-mail: uzzmma@yahoo.com

(Received 28 May 2009; accepted 4 June 2009; online 10 June 2009)

The title compound, C₈H₁₀N₂O₂, is stabilized by three intermolecular hydrogen bonds of the N—H⋯O and N—H⋯N types. Two intramolecular interactions of the N—H⋯O and C—H⋯O types are also observed.

Related literature

For related structures see: Ashiq, Jamal et al. (2008 ); Jamal et al. (2008 ), Kallel et al. (1992 ); Saraogi et al. (2002 ); For the biological activity of hydrazides, see: Ara et al. (2007 ); Ashiq, Ara et al. (2008 ); El-Emam et al. (2004 ); Maqsood et al. (2006 ).

Experimental

Crystal data

C₈H₁₀N₂O₂
M_r = 166.18
Orthorhombic, P 2₁ 2₁ 2₁
a = 3.9887 (1) Å
b = 6.1487 (2) Å
c = 32.8919 (9) Å
V = 806.68 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.22 × 0.12 × 0.10 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.979, T_max = 0.992
17597 measured reflections
1288 independent reflections
1052 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.147
S = 1.03
1288 reflections
119 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2ⁱ	0.83 (4)	2.16 (4)	2.961 (3)	162 (3)
N2—H2A⋯O1	0.92 (5)	2.42 (4)	2.729 (2)	100 (3)
N2—H2A⋯O1ⁱⁱ	0.92 (5)	2.44 (4)	3.026 (2)	122 (3)
N2—H2B⋯O1ⁱⁱⁱ	0.93 (4)	2.07 (4)	2.991 (2)	170 (4)
C7—H7⋯O1	0.93	2.47	2.781 (3)	100
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{5\over 2}}, -z]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{5\over 2}}, -z]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809021345/pv2163sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809021345/pv2163Isup2.hkl

checkCIF report

Comment top

Hydrazides are known to have different biological activities and have been used for the synthesis of various heterocyclic compounds (El-Emam et al., 2004). The title compound was found to be antileishmanial, antibacterial and antifungal (Maqsood et al., 2006). Vanadium complex of the title compound was found to ba a good inhibitor of urease (Ara et al., 2007) and alpha-glucosidase (Ashiq, Ara et al., 2008). In order to study the biological behaviour of 4-methoxybenzhydrazide and to investigate the change in activity due to complexation with vanadium center, we have synthesized (I) and report its crystal structure in this paper. The structures of benzhydrazide (Kallel et al., 1992), para-chloro (Saraogi et al., 2002), para-bromo (Ashiq, Jamal et al., 2008) and para-iodo (Jamal et al., 2008) analogues of (I) have already been reported.

The crystal structure of the title compound is presented in Fig. 1. The bond distances and bond angles in (I) are similar to the corresponding distances and angles reported in the structures quoted above. The phenyl group (C2—C7) and hydrazide moiety, O1/N1/N2/C1, in (I) are each planar with a dihedral angle between their least square planes being 7.08 (14)%. In the crystal structure, the molecules of I are linked by the N1—H1···N2, N2—H2A···O1 and N2—H2B···O1 intermolecular hydrogen bonds to form chains (details are given in Table 1, Fig 2). The geometry of 4-methoxybenzhydrazide is stabilized by N2—H2A···O1 and C7—H7···O1 intramolecular hydrogen interactions.

Related literature top

For related structures see: Ashiq, Jamal et al. (2008); Jamal et al. (2008), Kallel et al. (1992); Saraogi et al. (2002); For the biological activity of hydrazides, see: Ara et al. (2007); Ashiq, Ara et al. (2008); El-Emam et al. (2004); Maqsood et al. (2006).

Experimental top

All reagent-grade chemicals were obtained from Aldrich and Sigma Chemical companies and were used without further purification. To a solution of ethyl-4-methoxybenzoate (3.6 g, 20 mmol) in 75 ml ethanol, hydrazine hydrate (5.0 ml, 100 mmol) was added. The mixture was refluxed for 5 h and a solid was obtained upon removal of the solvent by rotary evaporation. The resulting solid was washed with hexane to afford 4-methoxybenzhydrazide (yield 64%). (Maqsood et al., 2006).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: sAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at 50% probability level. The dashed lines indicates the intramolecular interactions.
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown by dashed lines.

4-Methoxybenzohydrazide top

Crystal data top

C₈H₁₀N₂O₂	F(000) = 352
M_r = 166.18	D_x = 1.368 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1288 reflections
a = 3.9887 (1) Å	θ = 1.2–28.7°
b = 6.1487 (2) Å	µ = 0.10 mm⁻¹
c = 32.8919 (9) Å	T = 296 K
V = 806.68 (4) Å³	Needle, colourless
Z = 4	0.22 × 0.12 × 0.10 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1288 independent reflections
Radiation source: fine-focus sealed tube	1052 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Detector resolution: 7.40 pixels mm^-1	θ_max = 28.7°, θ_min = 1.2°
ω scans	h = −5→5
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −8→8
T_min = 0.979, T_max = 0.992	l = −44→44
17597 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)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.147	w = 1/[σ²(F_o²) + (0.1097P)² + 0.027P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
1288 reflections	Δρ_max = 0.39 e Å⁻³
119 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.058 (15)

Crystal data top

C₈H₁₀N₂O₂	V = 806.68 (4) Å³
M_r = 166.18	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 3.9887 (1) Å	µ = 0.10 mm⁻¹
b = 6.1487 (2) Å	T = 296 K
c = 32.8919 (9) Å	0.22 × 0.12 × 0.10 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1288 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1052 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.992	R_int = 0.035
17597 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.147	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.39 e Å⁻³
1288 reflections	Δρ_min = −0.24 e Å⁻³
119 parameters

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
O1	0.9709 (4)	1.2503 (3)	0.05610 (4)	0.0459 (5)
O2	0.2810 (5)	0.8530 (3)	0.21180 (5)	0.0600 (6)
N1	0.8024 (5)	0.9374 (3)	0.02782 (5)	0.0384 (5)
N2	0.9644 (5)	0.9802 (3)	−0.00972 (5)	0.0376 (5)
C1	0.8272 (5)	1.0744 (3)	0.05921 (5)	0.0320 (5)
C2	0.6754 (5)	1.0039 (3)	0.09850 (5)	0.0325 (5)
C3	0.5396 (7)	0.8001 (4)	0.10519 (6)	0.0427 (6)
C4	0.4053 (6)	0.7433 (4)	0.14251 (6)	0.0436 (7)
C5	0.4061 (6)	0.8925 (4)	0.17369 (6)	0.0415 (6)
C6	0.5410 (8)	1.0960 (4)	0.16743 (6)	0.0505 (8)
C7	0.6748 (6)	1.1507 (4)	0.13034 (7)	0.0441 (7)
C8	0.1357 (9)	0.6492 (5)	0.21996 (8)	0.0627 (10)
H1	0.694 (10)	0.822 (6)	0.0282 (9)	0.0752*
H2A	1.157 (12)	1.055 (6)	−0.0037 (11)	0.0940*
H2B	0.832 (12)	1.068 (6)	−0.0262 (10)	0.0940*
H3	0.53858	0.69896	0.08416	0.0513*
H4	0.31513	0.60542	0.14648	0.0523*
H6	0.54148	1.19702	0.18846	0.0606*
H7	0.76633	1.28832	0.12659	0.0529*
H8A	0.05128	0.64745	0.24729	0.0940*
H8B	0.30181	0.53746	0.21686	0.0940*
H8C	−0.04508	0.62368	0.20129	0.0940*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0595 (10)	0.0336 (8)	0.0445 (8)	−0.0109 (8)	0.0000 (7)	0.0023 (7)
O2	0.0770 (12)	0.0652 (12)	0.0379 (9)	0.0043 (11)	0.0195 (8)	0.0041 (8)
N1	0.0521 (10)	0.0313 (9)	0.0317 (8)	−0.0065 (9)	0.0048 (7)	0.0016 (7)
N2	0.0451 (9)	0.0348 (10)	0.0329 (8)	0.0030 (8)	0.0062 (7)	0.0040 (7)
C1	0.0350 (9)	0.0285 (9)	0.0325 (9)	0.0020 (8)	−0.0038 (7)	0.0031 (8)
C2	0.0352 (9)	0.0317 (9)	0.0306 (9)	0.0028 (8)	−0.0027 (7)	0.0018 (8)
C3	0.0593 (12)	0.0363 (11)	0.0326 (9)	−0.0064 (11)	0.0021 (10)	−0.0029 (8)
C4	0.0544 (12)	0.0384 (12)	0.0379 (10)	−0.0068 (11)	0.0031 (9)	0.0044 (9)
C5	0.0457 (10)	0.0469 (13)	0.0318 (10)	0.0076 (10)	0.0033 (8)	0.0031 (9)
C6	0.0708 (16)	0.0418 (13)	0.0390 (11)	0.0024 (13)	0.0038 (11)	−0.0096 (10)
C7	0.0566 (12)	0.0318 (11)	0.0438 (11)	−0.0025 (11)	0.0022 (11)	−0.0023 (9)
C8	0.0665 (16)	0.0722 (19)	0.0493 (14)	0.0039 (17)	0.0159 (12)	0.0163 (13)

Geometric parameters (Å, º) top

O1—C1	1.228 (3)	C3—C4	1.384 (3)
O2—C5	1.371 (3)	C4—C5	1.376 (3)
O2—C8	1.407 (4)	C5—C6	1.378 (4)
N1—N2	1.418 (2)	C6—C7	1.373 (3)
N1—C1	1.336 (2)	C3—H3	0.9300
N1—H1	0.83 (4)	C4—H4	0.9300
N2—H2A	0.92 (5)	C6—H6	0.9300
N2—H2B	0.93 (4)	C7—H7	0.9300
C1—C2	1.492 (2)	C8—H8A	0.9600
C2—C7	1.383 (3)	C8—H8B	0.9600
C2—C3	1.383 (3)	C8—H8C	0.9600

C5—O2—C8	118.84 (19)	O2—C5—C6	116.1 (2)
N2—N1—C1	121.47 (17)	C5—C6—C7	120.5 (2)
C1—N1—H1	124 (2)	C2—C7—C6	120.9 (2)
N2—N1—H1	114 (2)	C2—C3—H3	119.00
N1—N2—H2B	111 (3)	C4—C3—H3	119.00
H2A—N2—H2B	108 (4)	C3—C4—H4	120.00
N1—N2—H2A	107 (2)	C5—C4—H4	120.00
O1—C1—N1	121.69 (17)	C5—C6—H6	120.00
N1—C1—C2	117.14 (17)	C7—C6—H6	120.00
O1—C1—C2	121.17 (16)	C2—C7—H7	120.00
C1—C2—C7	117.86 (18)	C6—C7—H7	120.00
C3—C2—C7	118.06 (18)	O2—C8—H8A	109.00
C1—C2—C3	124.08 (16)	O2—C8—H8B	109.00
C2—C3—C4	121.4 (2)	O2—C8—H8C	109.00
C3—C4—C5	119.5 (2)	H8A—C8—H8B	109.00
O2—C5—C4	124.2 (2)	H8A—C8—H8C	109.00
C4—C5—C6	119.7 (2)	H8B—C8—H8C	109.00

C8—O2—C5—C4	−1.3 (4)	C7—C2—C3—C4	0.2 (4)
C8—O2—C5—C6	179.2 (3)	C1—C2—C7—C6	−179.6 (2)
N2—N1—C1—O1	5.3 (3)	C3—C2—C7—C6	−0.5 (4)
N2—N1—C1—C2	−174.18 (18)	C2—C3—C4—C5	0.1 (4)
O1—C1—C2—C3	−173.4 (2)	C3—C4—C5—O2	−179.7 (2)
O1—C1—C2—C7	5.7 (3)	C3—C4—C5—C6	−0.2 (4)
N1—C1—C2—C3	6.1 (3)	O2—C5—C6—C7	179.6 (2)
N1—C1—C2—C7	−174.9 (2)	C4—C5—C6—C7	−0.1 (4)
C1—C2—C3—C4	179.3 (2)	C5—C6—C7—C2	0.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.83 (4)	2.16 (4)	2.961 (3)	162 (3)
N2—H2A···O1	0.92 (5)	2.42 (4)	2.729 (2)	100 (3)
N2—H2A···O1ⁱⁱ	0.92 (5)	2.44 (4)	3.026 (2)	122 (3)
N2—H2B···O1ⁱⁱⁱ	0.93 (4)	2.07 (4)	2.991 (2)	170 (4)
C7—H7···O1	0.93	2.47	2.781 (3)	100

Symmetry codes: (i) x−1/2, −y+3/2, −z; (ii) x+1/2, −y+5/2, −z; (iii) x−1/2, −y+5/2, −z.

Experimental details

Crystal data
Chemical formula	C₈H₁₀N₂O₂
M_r	166.18
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	3.9887 (1), 6.1487 (2), 32.8919 (9)
V (Å³)	806.68 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.22 × 0.12 × 0.10

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.979, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	17597, 1288, 1052
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.676

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.147, 1.03
No. of reflections	1288
No. of parameters	119
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.24

Computer programs: APEX2 (Bruker, 2007), sAINT (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.83 (4)	2.16 (4)	2.961 (3)	162 (3)
N2—H2A···O1	0.92 (5)	2.42 (4)	2.729 (2)	100 (3)
N2—H2A···O1ⁱⁱ	0.92 (5)	2.44 (4)	3.026 (2)	122 (3)
N2—H2B···O1ⁱⁱⁱ	0.93 (4)	2.07 (4)	2.991 (2)	170 (4)
C7—H7···O1	0.93	2.47	2.781 (3)	100

Symmetry codes: (i) x−1/2, −y+3/2, −z; (ii) x+1/2, −y+5/2, −z; (iii) x−1/2, −y+5/2, −z.

Acknowledgements

The authors thank the Higher Education Commission Pakistan for providing the diffractometer at GCU, Lahore, and BANA International for their support in collecting the crystallographic data.

References

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