4-Hydroxy­benzohydrazide

Jamal, R.A.; Ashiq, U.; Arshad, M.N.; Maqsood, Z.T.; Khan, I.U.

doi:10.1107/S1600536809025094

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1764

doi:10.1107/S1600536809025094

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4-Hydroxybenzohydrazide

Rifat Ara Jamal,^a ^* Uzma Ashiq,^a Muhammad Nadeem Arshad,^b Zahida Tasneem Maqsood ^a and Islam Ullah Khan ^b

^aDepartment of Chemistry, University of Karachi, Karachi 75270, Pakistan, and ^bDepartment of Chemistry, Government College University, Lahore, Pakistan
^*Correspondence e-mail: rifat_jamal@yahoo.com

(Received 17 June 2009; accepted 29 June 2009; online 4 July 2009)

In the title compound, C₇H₈N₂O₂, the mean planes of the benzene ring and the planar hydrazide group are inclined at 25.75 (6)° with respect to each other. The structure is stabilized by intermolecular N—H⋯O and O—H⋯N hydrogen bonds.

Related literature

For related structures see: Ashiq, Jamal et al. (2008 , 2009 ); Hanif et al. (2007 ); 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 ); Maqsood et al. (2006 ).

Experimental

Crystal data

C₇H₈N₂O₂
M_r = 152.15
Monoclinic, P 2₁ /c
a = 5.0587 (2) Å
b = 17.2149 (9) Å
c = 7.8178 (5) Å
β = 93.489 (2)°
V = 679.55 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.32 × 0.18 × 0.12 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.965, T_max = 0.992
7324 measured reflections
1697 independent reflections
1348 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.118
S = 1.06
1697 reflections
107 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.86	2.13	2.9243 (14)	153
O1—H1A⋯N2ⁱⁱ	0.82	1.98	2.7852 (16)	174
N2—H12⋯O1ⁱⁱⁱ	0.89 (2)	2.37 (2)	3.223 (2)	160
N2—H22⋯O2^iv	0.90 (2)	2.22 (2)	3.056 (2)	155
Symmetry codes: (i) x+1, y, z; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) -x+1, -y+1, -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/S1600536809025094/pv2171sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809025094/pv2171Isup2.hkl

checkCIF report

Comment top

Hydrazides are known to have different biological activities (Ashiq, Ara et al., 2008; Ara et al., 2007). In order to study the biological activity of 4-hydroxybenzohydrazide, we undertook the synthesis of the title compound, (I), and report its crystal structure in this paper. The title compound was found to be antifungal (Maqsood et al., 2006). The crystal structures of benzhydrazide (Kallel et al., 1992), para-chloro (Saraogi et al., 2002), para-bromo (Ashiq, Jamal et al., 2008), para-iodo (Jamal et al., 2008) and para-methoxy (Ashiq, Jamal et al., 2009) analogues of (I) have already been reported. The structure of (I) is isomorphous with its 3-hydroxy analogue (Hanif et al., 2007).

The molecular structure of (I) has been 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. In (I), the mean-planes of the benzene ring (C1–C6) and planar hydrazide group (N1/N2/O2/C7) are inclined at 25.75 (6)° with respect to each other. The molecular packing diagram (Fig. 2) shows the presence of four intermolecular hydrogen bonds of the type N—H···O and O—H···N (details are given in Table 1).

Related literature top

For related structures see: Ashiq, Jamal et al. (2008, 2009); Hanif et al. (2007); 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); 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-hydroxybenzoate (3.32 g, 20 mmol) in 75 ml e thanol, 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-hydroxybenzohydrazide (yield 65%) (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. ORTEP plot of the title compound with the ellipsoids drawn at the 50% probability level.
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown by dashed lines.

4-Hydroxybenzohydrazide top

Crystal data top

C₇H₈N₂O₂	F(000) = 320
M_r = 152.15	D_x = 1.487 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2993 reflections
a = 5.0587 (2) Å	θ = 2.9–28.3°
b = 17.2149 (9) Å	µ = 0.11 mm⁻¹
c = 7.8178 (5) Å	T = 296 K
β = 93.489 (2)°	Needle, colourless
V = 679.55 (6) Å³	0.32 × 0.18 × 0.12 mm
Z = 4

Data collection top

Bruker Kappa APEX2 CCD diffractometer	1697 independent reflections
Radiation source: fine-focus sealed tube	1348 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scans	θ_max = 28.3°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −6→6
T_min = 0.965, T_max = 0.992	k = −22→23
7324 measured reflections	l = −10→9

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0613P)² + 0.1539P] where P = (F_o² + 2F_c²)/3
1697 reflections	(Δ/σ)_max < 0.001
107 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₇H₈N₂O₂	V = 679.55 (6) Å³
M_r = 152.15	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.0587 (2) Å	µ = 0.11 mm⁻¹
b = 17.2149 (9) Å	T = 296 K
c = 7.8178 (5) Å	0.32 × 0.18 × 0.12 mm
β = 93.489 (2)°

Data collection top

Bruker Kappa APEX2 CCD diffractometer	1697 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1348 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.992	R_int = 0.023
7324 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.36 e Å⁻³
1697 reflections	Δρ_min = −0.20 e Å⁻³
107 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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	0.7565 (2)	0.04052 (5)	0.14740 (17)	0.0478 (3)
H1A	0.8946	0.0291	0.2020	0.072*
O2	0.36833 (17)	0.38981 (5)	0.10180 (14)	0.0364 (3)
N1	0.8045 (2)	0.40995 (6)	0.15266 (16)	0.0331 (3)
H1	0.9606	0.3900	0.1554	0.040*
N2	0.7783 (2)	0.49074 (6)	0.1772 (2)	0.0381 (3)
H12	0.647 (4)	0.4969 (10)	0.247 (2)	0.046*
H22	0.736 (3)	0.5124 (10)	0.075 (2)	0.046*
C1	0.6499 (2)	0.27877 (7)	0.12927 (16)	0.0244 (3)
C2	0.4705 (2)	0.22850 (7)	0.04589 (17)	0.0299 (3)
H2	0.3217	0.2486	−0.0145	0.036*
C3	0.5095 (3)	0.14912 (8)	0.05121 (18)	0.0335 (3)
H3	0.3892	0.1161	−0.0066	0.040*
C4	0.7289 (3)	0.11891 (7)	0.14320 (18)	0.0304 (3)
C5	0.9081 (2)	0.16847 (7)	0.22869 (19)	0.0325 (3)
H5	1.0545	0.1484	0.2915	0.039*
C6	0.8685 (2)	0.24751 (7)	0.22038 (18)	0.0307 (3)
H6	0.9904	0.2805	0.2768	0.037*
C7	0.5947 (2)	0.36334 (7)	0.12527 (16)	0.0255 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0407 (6)	0.0216 (5)	0.0792 (9)	0.0012 (4)	−0.0124 (5)	0.0027 (5)
O2	0.0201 (4)	0.0278 (5)	0.0605 (7)	0.0024 (3)	−0.0032 (4)	0.0034 (4)
N1	0.0203 (5)	0.0213 (5)	0.0574 (7)	0.0009 (4)	−0.0008 (5)	−0.0007 (5)
N2	0.0305 (6)	0.0206 (5)	0.0627 (9)	−0.0015 (4)	−0.0020 (6)	0.0009 (5)
C1	0.0202 (5)	0.0231 (5)	0.0299 (6)	0.0007 (4)	0.0011 (4)	0.0016 (5)
C2	0.0238 (6)	0.0277 (6)	0.0372 (7)	−0.0002 (4)	−0.0061 (5)	0.0024 (5)
C3	0.0299 (6)	0.0277 (6)	0.0418 (8)	−0.0046 (5)	−0.0057 (5)	−0.0017 (5)
C4	0.0288 (6)	0.0208 (6)	0.0418 (7)	−0.0002 (5)	0.0037 (5)	0.0024 (5)
C5	0.0240 (6)	0.0274 (6)	0.0450 (8)	0.0033 (5)	−0.0061 (5)	0.0045 (5)
C6	0.0238 (6)	0.0266 (6)	0.0408 (7)	−0.0009 (5)	−0.0067 (5)	−0.0006 (5)
C7	0.0210 (5)	0.0241 (6)	0.0311 (6)	0.0011 (4)	0.0004 (4)	0.0013 (5)

Geometric parameters (Å, º) top

O1—C4	1.3569 (14)	C1—C7	1.4824 (16)
O1—H1A	0.8200	C2—C3	1.3809 (17)
O2—C7	1.2356 (14)	C2—H2	0.9300
N1—C7	1.3376 (15)	C3—C4	1.3866 (18)
N1—N2	1.4113 (15)	C3—H3	0.9300
N1—H1	0.8600	C4—C5	1.3864 (18)
N2—H12	0.89 (2)	C5—C6	1.3762 (17)
N2—H22	0.90 (2)	C5—H5	0.9300
C1—C6	1.3870 (17)	C6—H6	0.9300
C1—C2	1.3876 (17)

C4—O1—H1A	109.5	C2—C3—H3	120.2
C7—N1—N2	122.18 (10)	C4—C3—H3	120.2
C7—N1—H1	118.9	O1—C4—C5	122.50 (12)
N2—N1—H1	118.9	O1—C4—C3	117.60 (12)
N1—N2—H12	106.3 (11)	C5—C4—C3	119.90 (12)
N1—N2—H22	108.1 (11)	C6—C5—C4	119.78 (12)
H12—N2—H22	110.4 (17)	C6—C5—H5	120.1
C6—C1—C2	118.52 (11)	C4—C5—H5	120.1
C6—C1—C7	122.35 (11)	C5—C6—C1	121.13 (12)
C2—C1—C7	119.05 (11)	C5—C6—H6	119.4
C3—C2—C1	120.98 (12)	C1—C6—H6	119.4
C3—C2—H2	119.5	O2—C7—N1	121.45 (11)
C1—C2—H2	119.5	O2—C7—C1	122.48 (11)
C2—C3—C4	119.68 (12)	N1—C7—C1	116.04 (10)

C6—C1—C2—C3	−0.8 (2)	C2—C1—C6—C5	0.0 (2)
C7—C1—C2—C3	−177.79 (12)	C7—C1—C6—C5	176.81 (12)
C1—C2—C3—C4	1.0 (2)	N2—N1—C7—O2	7.9 (2)
C2—C3—C4—O1	178.80 (12)	N2—N1—C7—C1	−170.63 (12)
C2—C3—C4—C5	−0.2 (2)	C6—C1—C7—O2	−152.94 (13)
O1—C4—C5—C6	−179.61 (13)	C2—C1—C7—O2	23.90 (18)
C3—C4—C5—C6	−0.6 (2)	C6—C1—C7—N1	25.57 (18)
C4—C5—C6—C1	0.8 (2)	C2—C1—C7—N1	−157.60 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.86	2.13	2.9243 (14)	153
O1—H1A···N2ⁱⁱ	0.82	1.98	2.7852 (16)	174
N2—H12···O1ⁱⁱⁱ	0.89 (2)	2.37 (2)	3.223 (2)	160
N2—H22···O2^iv	0.90 (2)	2.22 (2)	3.056 (2)	155

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

Experimental details

Crystal data
Chemical formula	C₇H₈N₂O₂
M_r	152.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	5.0587 (2), 17.2149 (9), 7.8178 (5)
β (°)	93.489 (2)
V (Å³)	679.55 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.32 × 0.18 × 0.12

Data collection
Diffractometer	Bruker Kappa APEX2 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.965, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	7324, 1697, 1348
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.118, 1.06
No. of reflections	1697
No. of parameters	107
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.20

Computer programs: APEX2 (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···O2ⁱ	0.8600	2.129	2.9243 (14)	153
O1—H1A···N2ⁱⁱ	0.8200	1.980	2.7852 (16)	174
N2—H12···O1ⁱⁱⁱ	0.89 (2)	2.37 (2)	3.223 (2)	160
N2—H22···O2^iv	0.90 (2)	2.22 (2)	3.056 (2)	155

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