N′-(5-Chloro-2-hydroxy­benzyl­idene)-4-hydroxy­benzohydrazide

Qiu, X.-Y.

doi:10.1107/S160053680901215X

organic compounds

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Volume 65| Part 5| May 2009| Page o975

doi:10.1107/S160053680901215X

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N′-(5-Chloro-2-hydroxybenzylidene)-4-hydroxybenzohydrazide

Xiao-Yang Qiu ^a ^*

^aDepartment of Chemistry, Shangqiu Normal University, Shangqiu 476000, People's Republic of China
^*Correspondence e-mail: xiaoyang_qiu@126.com

(Received 30 March 2009; accepted 1 April 2009; online 8 April 2009)

The title Schiff base compound, C₁₄H₁₁ClN₂O₃, was prepared by the reaction of 5-chlorosalicylaldehyde and 4-hydroxybenzohydrazide. The molecule exists in a trans configuration with respect to the methylidene group. The dihedral angle between the two benzene rings is 40.1 (2)°. An intramolecular O—H⋯N hydrogen bond helps to stabilize the molecular conformation. In the crystal structure, molecules are linked into a three-dimensional network by intermolecular N—H⋯O and O—H⋯O hydrogen bonds.

Related literature

For the biological properties of hydrazone compounds, see: Bedia et al. (2006 ); Rollas et al. (2002 ); Fun et al. (2008 ). For the structures of hydrazone compounds we have reported previously, see: Qiu, Fang et al. (2006 ); Qiu, Luo et al., (2006a ,b ); Qiu, Xu et al. (2006 ). For bond-length data, see: Allen et al. (1987 ). For related structures see: Singh et al. (2007 ); Narayana et al. (2007 ); Cui et al. (2007 ); Diao et al. (2008 ).

Experimental

Crystal data

C₁₄H₁₁ClN₂O₃
M_r = 290.70
Orthorhombic, P n a 2₁
a = 9.423 (1) Å
b = 9.839 (1) Å
c = 13.770 (1) Å
V = 1276.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 298 K
0.17 × 0.15 × 0.15 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.950, T_max = 0.955
7398 measured reflections
2231 independent reflections
2144 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.071
S = 1.06
2231 reflections
187 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.32 e Å⁻³
Absolute structure: Flack (1983 ), 784 Friedel pairs
Flack parameter: −0.01 (6)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2ⁱ	0.892 (10)	2.121 (11)	3.0065 (18)	172 (3)
O3—H3⋯O2ⁱⁱ	0.82	1.98	2.7479 (19)	157
O1—H1⋯N1	0.82	1.89	2.6057 (19)	145
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (ii) $[-x+2, -y, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680901215X/sj2605sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680901215X/sj2605Isup2.hkl

checkCIF report

Comment top

Hyrazone compounds, derived from the reaction of aldehydes with hydrazides, have been widely studied due to their excellent biological properties (Bedia et al., 2006; Rollas et al., 2002; Fun et al., 2008). Recently, we have reported several Schiff base hydrazone compounds (Qiu, Fang et al., 2006; Qiu, Luo et al., 2006a,b; Qiu, Xu et al., 2006), and we report herein the crystal structure of the new title compound, (I), Fig. 1.

The molecule in (I) exists in a trans configuration with respect to the methylidene group. The dihedral angle between the two benzene rings is 40.1 (2)°. The bond lengths in (I) are found to have normal values (Allen et al., 1987) and are comparable to the values found in similar compounds (Singh et al., 2007; Narayana et al., 2007; Cui et al., 2007; Diao et al., 2008).

An intramolecular O–H···N hydrogen bond (Table 1) helps to stabilize the molecular conformation. In the crystal structure, molecules are linked into a three-dimensional network by intermolecular N–H···O and O–H···O hydrogen bonds (Table 1 and Fig. 2).

Related literature top

For the biological properties of hydrazone compounds, see: Bedia et al. (2006); Rollas et al. (2002); Fun et al. (2008). For the structures of hydrazone compounds we have reported previously, see: Qiu, Fang et al. (2006); Qiu, Luo et al., (2006a,b); Qiu, Xu et al. (2006). For bond-length data, see: Allen et al. (1987). For related structures see: Singh et al. (2007); Narayana et al. (2007); Cui et al. (2007); Diao et al. (2008).

Experimental top

The title compound was prepared by the Schiff base condensation of equimolar amounts (0.5 mmol each) of 5-chlorosalicylaldehyde and 4-hydroxybenzohydrazide in methanol (20 ml). Excess methanol was removed from the reaction mixture by distillation. The colourless solid was filtered and dried in air. Colourless block-shaped crystals suitable for X-ray diffraction were obtained from a methanol solution.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The crystal packing of (I), viewed along the b axis with hydrogen bonds drawn as dashed lines.

N'-(5-Chloro-2-hydroxybenzylidene)-4-hydroxybenzohydrazide top

Crystal data top

C₁₄H₁₁ClN₂O₃	F(000) = 600
M_r = 290.70	D_x = 1.513 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 4763 reflections
a = 9.423 (1) Å	θ = 2.5–30.6°
b = 9.839 (1) Å	µ = 0.31 mm⁻¹
c = 13.770 (1) Å	T = 298 K
V = 1276.7 (2) Å³	Block, colourless
Z = 4	0.17 × 0.15 × 0.15 mm

Data collection top

Bruker SMART CCD diffractometer	2231 independent reflections
Radiation source: fine-focus sealed tube	2144 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 27.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→11
T_min = 0.950, T_max = 0.955	k = −12→12
7398 measured reflections	l = −17→11

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.026	w = 1/[σ²(F_o²) + (0.0409P)² + 0.1827P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.071	(Δ/σ)_max = 0.001
S = 1.06	Δρ_max = 0.21 e Å⁻³
2231 reflections	Δρ_min = −0.32 e Å⁻³
187 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.034 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 784 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.01 (6)

Crystal data top

C₁₄H₁₁ClN₂O₃	V = 1276.7 (2) Å³
M_r = 290.70	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 9.423 (1) Å	µ = 0.31 mm⁻¹
b = 9.839 (1) Å	T = 298 K
c = 13.770 (1) Å	0.17 × 0.15 × 0.15 mm

Data collection top

Bruker SMART CCD diffractometer	2231 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2144 reflections with I > 2σ(I)
T_min = 0.950, T_max = 0.955	R_int = 0.022
7398 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.071	Δρ_max = 0.21 e Å⁻³
S = 1.06	Δρ_min = −0.32 e Å⁻³
2231 reflections	Absolute structure: Flack (1983), 784 Friedel pairs
187 parameters	Absolute structure parameter: −0.01 (6)
2 restraints

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	0.74914 (6)	0.47741 (5)	1.21657 (5)	0.05224 (15)
N1	0.99352 (15)	0.30628 (14)	0.80967 (10)	0.0316 (3)
N2	0.94949 (14)	0.28112 (13)	0.71621 (12)	0.0319 (3)
O1	1.19292 (14)	0.32175 (17)	0.94031 (11)	0.0504 (4)
H1	1.1598	0.3057	0.8865	0.076*
O2	1.14143 (12)	0.14658 (12)	0.69247 (10)	0.0370 (3)
O3	0.84616 (17)	0.10538 (15)	0.27816 (10)	0.0505 (4)
H3	0.8733	0.0312	0.2583	0.076*
C1	0.94953 (17)	0.38640 (15)	0.96863 (13)	0.0312 (3)
C2	1.08639 (18)	0.35624 (17)	1.00215 (14)	0.0346 (4)
C3	1.1165 (2)	0.36019 (19)	1.10078 (15)	0.0403 (4)
H3A	1.2072	0.3386	1.1225	0.048*
C4	1.0133 (2)	0.39569 (17)	1.16663 (14)	0.0391 (4)
H4	1.0332	0.3960	1.2328	0.047*
C5	0.87956 (19)	0.43088 (17)	1.13363 (14)	0.0362 (4)
C6	0.84744 (18)	0.42738 (18)	1.03619 (14)	0.0352 (4)
H6	0.7573	0.4524	1.0152	0.042*
C7	0.90835 (18)	0.36642 (16)	0.86788 (13)	0.0325 (3)
H7	0.8207	0.3972	0.8459	0.039*
C8	1.03211 (17)	0.20101 (16)	0.65983 (13)	0.0292 (3)
C9	0.98366 (16)	0.17900 (16)	0.55911 (12)	0.0296 (3)
C10	1.03520 (17)	0.06631 (17)	0.50845 (14)	0.0335 (4)
H10	1.0998	0.0084	0.5384	0.040*
C11	0.99177 (18)	0.03955 (17)	0.41486 (14)	0.0350 (4)
H11	1.0265	−0.0361	0.3821	0.042*
C12	0.89604 (19)	0.12597 (18)	0.36973 (13)	0.0352 (4)
C13	0.8457 (2)	0.2394 (2)	0.41833 (15)	0.0450 (5)
H13	0.7826	0.2980	0.3876	0.054*
C14	0.8889 (2)	0.26545 (18)	0.51195 (14)	0.0392 (4)
H14	0.8544	0.3417	0.5441	0.047*
H2	0.8598 (14)	0.303 (3)	0.703 (2)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0578 (3)	0.0676 (3)	0.0313 (2)	0.0148 (2)	0.0054 (2)	−0.0062 (3)
N1	0.0343 (7)	0.0371 (7)	0.0235 (8)	−0.0016 (5)	−0.0046 (6)	−0.0003 (6)
N2	0.0319 (7)	0.0408 (7)	0.0229 (7)	0.0001 (5)	−0.0045 (7)	−0.0009 (6)
O1	0.0365 (7)	0.0791 (10)	0.0354 (8)	0.0131 (7)	−0.0033 (6)	−0.0060 (7)
O2	0.0323 (6)	0.0466 (6)	0.0322 (7)	0.0039 (5)	−0.0061 (5)	0.0025 (5)
O3	0.0679 (10)	0.0545 (8)	0.0289 (8)	0.0089 (6)	−0.0118 (7)	−0.0097 (6)
C1	0.0344 (8)	0.0322 (8)	0.0271 (9)	−0.0001 (6)	−0.0049 (7)	−0.0006 (6)
C2	0.0352 (8)	0.0376 (8)	0.0311 (9)	0.0014 (6)	−0.0033 (8)	−0.0024 (7)
C3	0.0400 (10)	0.0450 (9)	0.0358 (11)	0.0036 (7)	−0.0127 (8)	−0.0025 (8)
C4	0.0531 (11)	0.0398 (8)	0.0244 (9)	0.0025 (7)	−0.0103 (8)	−0.0032 (7)
C5	0.0444 (9)	0.0359 (8)	0.0283 (9)	0.0031 (7)	0.0005 (7)	−0.0044 (7)
C6	0.0350 (8)	0.0406 (8)	0.0300 (9)	0.0035 (7)	−0.0046 (7)	−0.0008 (7)
C7	0.0317 (8)	0.0386 (8)	0.0271 (9)	0.0007 (6)	−0.0056 (7)	0.0011 (7)
C8	0.0298 (8)	0.0318 (7)	0.0261 (9)	−0.0043 (6)	−0.0007 (6)	0.0027 (6)
C9	0.0304 (7)	0.0342 (7)	0.0243 (9)	−0.0013 (6)	0.0003 (6)	0.0019 (6)
C10	0.0309 (8)	0.0371 (8)	0.0327 (10)	0.0039 (6)	−0.0011 (7)	−0.0011 (7)
C11	0.0358 (9)	0.0370 (8)	0.0321 (10)	0.0015 (6)	0.0030 (7)	−0.0058 (7)
C12	0.0392 (9)	0.0426 (9)	0.0239 (9)	−0.0033 (7)	−0.0011 (7)	−0.0004 (7)
C13	0.0593 (12)	0.0446 (9)	0.0311 (10)	0.0158 (8)	−0.0110 (9)	0.0004 (8)
C14	0.0527 (10)	0.0360 (8)	0.0290 (9)	0.0111 (7)	−0.0052 (8)	−0.0040 (7)

Geometric parameters (Å, º) top

Cl1—C5	1.7391 (19)	C4—C5	1.384 (3)
N1—C7	1.279 (2)	C4—H4	0.9300
N1—N2	1.375 (2)	C5—C6	1.376 (3)
N2—C8	1.353 (2)	C6—H6	0.9300
N2—H2	0.892 (10)	C7—H7	0.9300
O1—C2	1.359 (2)	C8—C9	1.476 (2)
O1—H1	0.8200	C9—C14	1.394 (2)
O2—C8	1.245 (2)	C9—C10	1.397 (2)
O3—C12	1.361 (2)	C10—C11	1.378 (3)
O3—H3	0.8200	C10—H10	0.9300
C1—C6	1.398 (2)	C11—C12	1.387 (2)
C1—C2	1.402 (2)	C11—H11	0.9300
C1—C7	1.454 (2)	C12—C13	1.385 (3)
C2—C3	1.388 (3)	C13—C14	1.376 (3)
C3—C4	1.374 (3)	C13—H13	0.9300
C3—H3A	0.9300	C14—H14	0.9300

C7—N1—N2	118.72 (14)	N1—C7—C1	119.54 (15)
C8—N2—N1	117.94 (13)	N1—C7—H7	120.2
C8—N2—H2	125 (2)	C1—C7—H7	120.2
N1—N2—H2	116 (2)	O2—C8—N2	121.31 (16)
C2—O1—H1	109.5	O2—C8—C9	122.14 (15)
C12—O3—H3	109.5	N2—C8—C9	116.53 (14)
C6—C1—C2	118.37 (16)	C14—C9—C10	118.32 (16)
C6—C1—C7	119.37 (15)	C14—C9—C8	123.12 (15)
C2—C1—C7	122.09 (16)	C10—C9—C8	118.56 (14)
O1—C2—C3	117.99 (16)	C11—C10—C9	121.03 (16)
O1—C2—C1	121.73 (17)	C11—C10—H10	119.5
C3—C2—C1	120.28 (16)	C9—C10—H10	119.5
C4—C3—C2	120.55 (16)	C10—C11—C12	119.69 (16)
C4—C3—H3A	119.7	C10—C11—H11	120.2
C2—C3—H3A	119.7	C12—C11—H11	120.2
C3—C4—C5	119.41 (17)	O3—C12—C13	116.71 (16)
C3—C4—H4	120.3	O3—C12—C11	123.28 (16)
C5—C4—H4	120.3	C13—C12—C11	120.01 (17)
C6—C5—C4	120.95 (18)	C14—C13—C12	120.13 (17)
C6—C5—Cl1	119.44 (14)	C14—C13—H13	119.9
C4—C5—Cl1	119.59 (15)	C12—C13—H13	119.9
C5—C6—C1	120.32 (16)	C13—C14—C9	120.80 (16)
C5—C6—H6	119.8	C13—C14—H14	119.6
C1—C6—H6	119.8	C9—C14—H14	119.6

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱ	0.89 (1)	2.12 (1)	3.0065 (18)	172 (3)
O3—H3···O2ⁱⁱ	0.82	1.98	2.7479 (19)	157
O1—H1···N1	0.82	1.89	2.6057 (19)	145

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁ClN₂O₃
M_r	290.70
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	298
a, b, c (Å)	9.423 (1), 9.839 (1), 13.770 (1)
V (Å³)	1276.7 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.17 × 0.15 × 0.15

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.950, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections	7398, 2231, 2144
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.071, 1.06
No. of reflections	2231
No. of parameters	187
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.32
Absolute structure	Flack (1983), 784 Friedel pairs
Absolute structure parameter	−0.01 (6)

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), 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—H2···O2ⁱ	0.892 (10)	2.121 (11)	3.0065 (18)	172 (3)
O3—H3···O2ⁱⁱ	0.82	1.98	2.7479 (19)	156.8
O1—H1···N1	0.82	1.89	2.6057 (19)	145.2

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

Acknowledgements

The author acknowledges the Natural Science Foundation of the Education Office of Anhui Province (Project No. 2009 A150020).

References

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