N′-(3-Chloro­benzyl­idene)-4-hy­droxy­benzohydrazide

Saad, S.M.; Fatima, I.; Perveen, S.; Khan, K.M.; Yousuf, S.

doi:10.1107/S1600536812048325

organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3499

doi:10.1107/S1600536812048325

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N′-(3-Chlorobenzylidene)-4-hydroxybenzohydrazide

Syed Muhammad Saad,^a Itrat Fatima,^a Shahnaz Perveen,^b Khalid M. Khan ^a and Sammer Yousuf ^a ^*

^aH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan, and ^bPCSIR Labortories Complex, Karachi, Shahrah-e-Dr. Salmuzzaman Siddiqui, Karachi 75280, Pakistan
^*Correspondence e-mail: dr.sammer.yousuf@gmail.com

(Received 22 November 2012; accepted 25 November 2012; online 30 November 2012)

The molecule of the title compound, C₁₄H₁₁ClN₂O₂ adopts an E conformation of the azomethine double bond and the dihedral angle between the benzene rings is 38.96 (13)°. In the crystal, molecules are linked by N—H⋯O and O—H⋯O (with the ketone O atom as acceptor) and C—H⋯O (with the hydroxy O atom as acceptor) hydrogen bonds, forming a three-dimensional network.

Related literature

For a related structure and background to the chemistry of the N-acylhydrazone unit, see: Taha et al. (2012 ). For a related structure, see: Hao (2009 ).

Experimental

Crystal data

C₁₄H₁₁ClN₂O₂
M_r = 274.70
Orthorhombic, P n a 2₁
a = 9.0900 (8) Å
b = 9.9396 (9) Å
c = 13.8615 (12) Å
V = 1252.40 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 293 K
0.27 × 0.11 × 0.10 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.923, T_max = 0.970
6999 measured reflections
2274 independent reflections
1980 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.081
S = 1.02
2274 reflections
180 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack (1983 ), 1060 Friedel pairs
Flack parameter: 0.12 (9)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1ⁱ	0.84 (2)	2.20 (2)	3.026 (3)	169 (3)
O2—H2B⋯O1ⁱⁱ	0.79 (3)	2.01 (3)	2.739 (3)	154 (3)
C4—H4A⋯O2ⁱⁱⁱ	0.93	2.55	3.216 (3)	128
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ ; (ii) $[-x+2, -y+1, z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-1]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812048325/hb6997sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812048325/hb6997Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812048325/hb6997Isup3.cml

checkCIF report

Comment top

As part of our ongoing studies of the N-acylhydrazone moiety (Taha et al., 2012), we now describe the structure of the title compound, which is similar to that of the previously published N'-(2-Chlorobenzylidene)-4-hydroxybenzohydrazide (Hao, 2009) with the difference that 2-chlorobenzne ring is replaced by 3-chlorophenyl ring (C1–C6). In the crystal, N2—H2A···O1, O2—H2B···O1,and C4—H4A···O2 hydrogen bonds link the moleucles into a three-dimensional-network (Table 2 and Fig. 2).

Related literature top

For a related structure and background to the chemistry of the N-acylhydrazone unit, see: Taha et al. (2012). For a related structure, see: Hao (2009).

Experimental top

The title compound was synthesized by refluxing a mixture of 3-chlorobenzaldehyde (2 mmol, 0.23 ml), methanol (20 ml) and 3 drops of acetic acid. 4-hydroxybenzohydrazide (2 mmol, 0.304 g) was added into above mentioned mixture at ambient temperature and refluxed for 3 h with vigorous stirring. Progress of the reaction mixture was monitored by thin layer chromatography. After the completion of the reaction (TLC Analysis), the solvent of the reaction mixture was slowly evaporated at room temperature by keeping it in an open atmosphere in order to obtained colourless blocks (0.44 g, 80.3% yield).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at 30% probability level.
	Fig. 2. The crystal packing of the title compound I. Only hydrogen atoms involved in hydrogen bonding are shown.

N'-(3-Chlorobenzylidene)-4-hydroxybenzohydrazide top

Crystal data top

C₁₄H₁₁ClN₂O₂	D_x = 1.457 Mg m⁻³
M_r = 274.70	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna2₁	Cell parameters from 1415 reflections
a = 9.0900 (8) Å	θ = 2.5–23.8°
b = 9.9396 (9) Å	µ = 0.30 mm⁻¹
c = 13.8615 (12) Å	T = 293 K
V = 1252.40 (19) Å³	Block, colorles
Z = 4	0.27 × 0.11 × 0.10 mm
F(000) = 568

Data collection top

Bruker SMART APEX CCD diffractometer	2274 independent reflections
Radiation source: fine-focus sealed tube	1980 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ω scan	θ_max = 25.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→11
T_min = 0.923, T_max = 0.970	k = −10→12
6999 measured reflections	l = −15→16

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)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.081	w = 1/[σ²(F_o²) + (0.0383P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2274 reflections	Δρ_max = 0.21 e Å⁻³
180 parameters	Δρ_min = −0.20 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1060 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.12 (9)

Crystal data top

C₁₄H₁₁ClN₂O₂	V = 1252.40 (19) Å³
M_r = 274.70	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 9.0900 (8) Å	µ = 0.30 mm⁻¹
b = 9.9396 (9) Å	T = 293 K
c = 13.8615 (12) Å	0.27 × 0.11 × 0.10 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2274 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1980 reflections with I > 2σ(I)
T_min = 0.923, T_max = 0.970	R_int = 0.037
6999 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.081	Δρ_max = 0.21 e Å⁻³
S = 1.02	Δρ_min = −0.20 e Å⁻³
2274 reflections	Absolute structure: Flack (1983), 1060 Friedel pairs
180 parameters	Absolute structure parameter: 0.12 (9)
1 restraint

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
Cl1	0.75369 (7)	0.98855 (8)	0.02100 (8)	0.0540 (2)
O1	1.15017 (17)	0.62769 (17)	0.54009 (13)	0.0374 (4)
O2	0.8459 (2)	0.6183 (2)	0.95100 (14)	0.0518 (6)
H2B	0.874 (4)	0.549 (3)	0.971 (2)	0.059 (11)*
N1	1.0036 (2)	0.7862 (2)	0.41778 (15)	0.0339 (5)
N2	0.9609 (2)	0.7697 (2)	0.51292 (16)	0.0340 (5)
H2A	0.878 (3)	0.799 (2)	0.529 (2)	0.032 (7)*
C1	0.8540 (3)	0.9246 (3)	0.19819 (17)	0.0353 (6)
H1B	0.7633	0.9546	0.2206	0.042*
C2	0.8869 (3)	0.9307 (3)	0.10113 (19)	0.0359 (6)
C3	1.0208 (3)	0.8895 (3)	0.06536 (19)	0.0391 (7)
H3A	1.0407	0.8931	−0.0004	0.047*
C4	1.1252 (3)	0.8426 (3)	0.1302 (2)	0.0437 (7)
H4A	1.2175	0.8169	0.1078	0.052*
C5	1.0943 (3)	0.8336 (3)	0.2265 (2)	0.0405 (7)
H5A	1.1654	0.8008	0.2686	0.049*
C6	0.9579 (3)	0.8729 (2)	0.26244 (17)	0.0317 (6)
C7	0.9198 (3)	0.8545 (2)	0.36386 (18)	0.0354 (6)
H7A	0.8344	0.8927	0.3887	0.043*
C8	1.0415 (3)	0.6900 (2)	0.57049 (19)	0.0307 (6)
C9	0.9925 (2)	0.6764 (2)	0.67131 (18)	0.0301 (6)
C10	1.0357 (3)	0.5631 (3)	0.72305 (19)	0.0349 (6)
H10A	1.0971	0.5003	0.6938	0.042*
C11	0.9897 (3)	0.5416 (3)	0.81628 (18)	0.0357 (6)
H11A	1.0196	0.4651	0.8496	0.043*
C12	0.8986 (3)	0.6348 (3)	0.85996 (18)	0.0364 (6)
C13	0.8576 (3)	0.7497 (3)	0.81142 (19)	0.0446 (7)
H13A	0.7991	0.8137	0.8419	0.053*
C14	0.9029 (3)	0.7698 (3)	0.71824 (18)	0.0400 (6)
H14A	0.8735	0.8471	0.6857	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0529 (4)	0.0712 (5)	0.0378 (4)	0.0143 (4)	−0.0044 (4)	0.0075 (4)
O1	0.0349 (9)	0.0442 (10)	0.0330 (11)	0.0057 (8)	0.0062 (8)	−0.0020 (8)
O2	0.0712 (14)	0.0554 (15)	0.0289 (12)	0.0118 (11)	0.0139 (10)	0.0100 (11)
N1	0.0393 (12)	0.0384 (12)	0.0240 (12)	−0.0034 (10)	0.0052 (9)	0.0007 (9)
N2	0.0333 (11)	0.0452 (13)	0.0237 (12)	0.0008 (10)	0.0092 (11)	0.0022 (11)
C1	0.0346 (13)	0.0401 (15)	0.0311 (16)	0.0029 (12)	0.0072 (11)	0.0000 (11)
C2	0.0440 (15)	0.0345 (15)	0.0292 (15)	0.0000 (11)	−0.0006 (12)	0.0019 (11)
C3	0.0500 (16)	0.0418 (16)	0.0255 (15)	0.0020 (13)	0.0134 (12)	0.0053 (12)
C4	0.0408 (15)	0.0499 (18)	0.0403 (19)	0.0084 (13)	0.0128 (13)	0.0071 (14)
C5	0.0395 (14)	0.0500 (17)	0.0321 (16)	0.0065 (13)	0.0040 (12)	0.0058 (13)
C6	0.0386 (14)	0.0308 (14)	0.0257 (15)	−0.0007 (11)	0.0042 (11)	0.0033 (12)
C7	0.0364 (14)	0.0384 (16)	0.0315 (16)	0.0025 (12)	0.0065 (12)	−0.0004 (13)
C8	0.0299 (12)	0.0322 (14)	0.0299 (15)	−0.0051 (11)	−0.0001 (10)	−0.0018 (11)
C9	0.0295 (13)	0.0356 (15)	0.0252 (15)	−0.0020 (11)	−0.0003 (10)	−0.0020 (11)
C10	0.0355 (13)	0.0359 (15)	0.0332 (16)	0.0057 (12)	0.0009 (12)	−0.0021 (12)
C11	0.0401 (14)	0.0357 (16)	0.0313 (16)	0.0039 (12)	−0.0037 (12)	0.0073 (12)
C12	0.0380 (14)	0.0457 (17)	0.0253 (15)	−0.0034 (12)	0.0009 (12)	0.0010 (13)
C13	0.0578 (17)	0.0432 (16)	0.0327 (16)	0.0138 (13)	0.0094 (13)	−0.0026 (14)
C14	0.0520 (16)	0.0368 (15)	0.0311 (16)	0.0105 (13)	0.0046 (12)	0.0051 (12)

Geometric parameters (Å, º) top

Cl1—C2	1.741 (3)	C5—C6	1.392 (3)
O1—C8	1.240 (3)	C5—H5A	0.9300
O2—C12	1.359 (3)	C6—C7	1.460 (3)
O2—H2B	0.79 (3)	C7—H7A	0.9300
N1—C7	1.265 (3)	C8—C9	1.473 (3)
N1—N2	1.384 (3)	C9—C10	1.392 (3)
N2—C8	1.342 (3)	C9—C14	1.396 (3)
N2—H2A	0.84 (2)	C10—C11	1.375 (3)
C1—C2	1.380 (3)	C10—H10A	0.9300
C1—C6	1.396 (3)	C11—C12	1.382 (4)
C1—H1B	0.9300	C11—H11A	0.9300
C2—C3	1.376 (3)	C12—C13	1.377 (4)
C3—C4	1.388 (4)	C13—C14	1.370 (4)
C3—H3A	0.9300	C13—H13A	0.9300
C4—C5	1.368 (4)	C14—H14A	0.9300
C4—H4A	0.9300

C12—O2—H2B	109 (2)	N1—C7—H7A	120.2
C7—N1—N2	117.2 (2)	C6—C7—H7A	120.2
C8—N2—N1	118.9 (2)	O1—C8—N2	121.9 (2)
C8—N2—H2A	122.6 (19)	O1—C8—C9	121.2 (2)
N1—N2—H2A	117.6 (19)	N2—C8—C9	117.0 (2)
C2—C1—C6	119.4 (2)	C10—C9—C14	117.6 (2)
C2—C1—H1B	120.3	C10—C9—C8	118.6 (2)
C6—C1—H1B	120.3	C14—C9—C8	123.9 (2)
C3—C2—C1	122.0 (2)	C11—C10—C9	121.6 (2)
C3—C2—Cl1	118.9 (2)	C11—C10—H10A	119.2
C1—C2—Cl1	119.1 (2)	C9—C10—H10A	119.2
C2—C3—C4	118.1 (2)	C10—C11—C12	119.3 (2)
C2—C3—H3A	120.9	C10—C11—H11A	120.3
C4—C3—H3A	120.9	C12—C11—H11A	120.3
C5—C4—C3	120.9 (2)	O2—C12—C13	117.2 (2)
C5—C4—H4A	119.6	O2—C12—C11	122.5 (2)
C3—C4—H4A	119.6	C13—C12—C11	120.3 (2)
C4—C5—C6	120.9 (3)	C14—C13—C12	120.0 (2)
C4—C5—H5A	119.5	C14—C13—H13A	120.0
C6—C5—H5A	119.5	C12—C13—H13A	120.0
C5—C6—C1	118.5 (2)	C13—C14—C9	121.1 (2)
C5—C6—C7	121.4 (2)	C13—C14—H14A	119.4
C1—C6—C7	120.0 (2)	C9—C14—H14A	119.4
N1—C7—C6	119.6 (2)

C7—N1—N2—C8	175.3 (2)	N1—N2—C8—C9	179.5 (2)
C6—C1—C2—C3	−1.2 (4)	O1—C8—C9—C10	−21.1 (3)
C6—C1—C2—Cl1	177.28 (19)	N2—C8—C9—C10	157.1 (2)
C1—C2—C3—C4	−1.0 (4)	O1—C8—C9—C14	159.9 (2)
Cl1—C2—C3—C4	−179.4 (2)	N2—C8—C9—C14	−21.9 (3)
C2—C3—C4—C5	2.0 (4)	C14—C9—C10—C11	1.4 (4)
C3—C4—C5—C6	−0.8 (4)	C8—C9—C10—C11	−177.6 (2)
C4—C5—C6—C1	−1.4 (4)	C9—C10—C11—C12	−0.1 (4)
C4—C5—C6—C7	175.4 (3)	C10—C11—C12—O2	178.3 (2)
C2—C1—C6—C5	2.3 (4)	C10—C11—C12—C13	−1.7 (4)
C2—C1—C6—C7	−174.4 (2)	O2—C12—C13—C14	−177.8 (3)
N2—N1—C7—C6	−178.8 (2)	C11—C12—C13—C14	2.3 (4)
C5—C6—C7—N1	−9.2 (4)	C12—C13—C14—C9	−1.0 (4)
C1—C6—C7—N1	167.4 (2)	C10—C9—C14—C13	−0.8 (4)
N1—N2—C8—O1	−2.3 (3)	C8—C9—C14—C13	178.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.84 (2)	2.20 (2)	3.026 (3)	169 (3)
O2—H2B···O1ⁱⁱ	0.79 (3)	2.01 (3)	2.739 (3)	154 (3)
C4—H4A···O2ⁱⁱⁱ	0.93	2.55	3.216 (3)	128

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁ClN₂O₂
M_r	274.70
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	293
a, b, c (Å)	9.0900 (8), 9.9396 (9), 13.8615 (12)
V (Å³)	1252.40 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.27 × 0.11 × 0.10

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.923, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	6999, 2274, 1980
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.081, 1.02
No. of reflections	2274
No. of parameters	180
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)	0.21, −0.20
Absolute structure	Flack (1983), 1060 Friedel pairs
Absolute structure parameter	0.12 (9)

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.84 (2)	2.20 (2)	3.026 (3)	169 (3)
O2—H2B···O1ⁱⁱ	0.79 (3)	2.01 (3)	2.739 (3)	154 (3)
C4—H4A···O2ⁱⁱⁱ	0.93	2.55	3.216 (3)	128

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

Acknowledgements

The authors are thankful to the Higher Education Commission (HEC) Pakistan (project No. 20–2073) and Pakistan Academy of Sciences (PAS) for their financial support.

References

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