(E)-6-Chloro-N′-(3,5-dichloro-2-hydroxy­benzyl­idene)­nicotinohydrazide

Ren, C.

doi:10.1107/S1600536809007272

organic compounds

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Volume 65| Part 4| April 2009| Page o678

doi:10.1107/S1600536809007272

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(E)-6-Chloro-N′-(3,5-dichloro-2-hydroxybenzylidene)nicotinohydrazide

Chun-yan Ren ^a ^*

^aCollege of Chemistry and Pharmacy, Qingdao Agricultural University, Shandong 266109, People's Republic of China
^*Correspondence e-mail: furbear01@163.com

(Received 26 February 2009; accepted 27 February 2009; online 6 March 2009)

The title Schiff base compound, C₁₃H₈Cl₃N₃O₂, was synthesized by the condensation reaction of 3,5-dichlorosalicylaldehyde with 6-chloronicotinic acid hydrazide in 95% ethanol. The molecule is nearly planar, with a dihedral angle of 1.9 (2)° between the aromatic ring planes, and an intramolecular O—H⋯N hydrogen bond is observed. In the crystal, the molecules are connected by intermolecular N—H⋯O hydrogen bonds into infinite chains propagating in [100].

Related literature

For general background, see: Kim et al. (2005 ); Fan et al. (2007 ). For background on the biological activities of Schiff bases, see: Ren et al. (2002 ); Takeuchi et al. (1998 ). For a related structure, see: Zhi (2008 ). For reference structural data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₃H₈Cl₃N₃O₂
M_r = 344.57
Monoclinic, P 2₁ /c
a = 4.8920 (10) Å
b = 18.014 (4) Å
c = 16.112 (3) Å
β = 97.90 (3)°
V = 1406.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.66 mm⁻¹
T = 298 K
0.27 × 0.23 × 0.23 mm

Data collection

Siemens SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Siemens, 1996 ) T_min = 0.842, T_max = 0.864
7275 measured reflections
2478 independent reflections
1323 reflections with I > 2σ(I)
R_int = 0.078

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.114
S = 1.01
2478 reflections
191 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2ⁱ	0.86	2.20	2.930 (4)	142
O1—H1⋯N1	0.82	1.82	2.540 (4)	147
Symmetry code: (i) x+1, y, z.

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); 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 global, I. DOI: 10.1107/S1600536809007272/hb2920sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809007272/hb2920Isup2.hkl

checkCIF report

Comment top

Schiff base compounds have been widely investigated over a century (Fan et al., 2007; Kim et al., 2005). Some of the complexes derived from Schiff bases have been found to have pharmacological and antitumor properties (Ren et al., 2002; Takeuchi, et al., 1998). In this paper, the crystal structure of the title compound, (I), a new Schiff base compound derived from the condensation reaction of 3,5-dichlorosalicylaldehyde with 6-chloronicotinic acid hydrazide is reported.

The molecule of (I) displays a trans configuration with respect to the C=N and C—N bonds (Fig. 1). All the bond lengths are within normal ranges (Allen et al., 1987), and are comparable to those in the related compound 6-chloro-N'-(2-hydroxy-1-naphthylmethylene)nicotinohydrazide (Zhi 2008). The Schiff base molecule is nearly planar, with a dihedral angle between the benzene ring and the pyridine ring of 1.9 (2)°. An intramolecular O—H···N hydrogen bond is observed. The molecules are connected via intermolecular N—H···O hydrogen bonds into infinite chains along the a axis (Table 1, Fig. 2).

Related literature top

For general background, see: Kim et al. (2005); Fan et al. (2007). For background on the biological activities of Schiff bases, see: Ren et al. (2002); Takeuchi et al. (1998). For a related structure, see: Zhi (2008). For reference structural data, see: Allen et al. (1987).

Experimental top

3,5-Dichlorosalicylaldehyde (0.1 mmol, 19.0 mg) and 6-chloronicotinic acid hydrazide (0.1 mmol, 17.1 mg) were dissolved in a 95% ethanol solution (10 ml). The mixture was stirred at room temperature to give a clear colorless solution. Light yellow blocks of (I) were formed by gradual evaporation of the solvent over a period of five days at room temperature.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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 displacement ellipsoids drawn at the 30% probability level. The dashed lines indicate hydrogen bonds.
	Fig. 2. The infinite chains structure formed via hydrogen bonds, H atoms have been omitted for clarity. The dashed lines indicate the connections between the donor and acceptor atoms of the hydrogen bonds.

(E)-6-Chloro-N'-(3,5-dichloro-2- hydroxybenzylidene)nicotinohydrazide top

Crystal data top

C₁₃H₈Cl₃N₃O₂	F(000) = 696
M_r = 344.57	D_x = 1.627 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 669 reflections
a = 4.892 (1) Å	θ = 2.6–18.8°
b = 18.014 (4) Å	µ = 0.66 mm⁻¹
c = 16.112 (3) Å	T = 298 K
β = 97.90 (3)°	Block, light yellow
V = 1406.4 (5) Å³	0.27 × 0.23 × 0.23 mm
Z = 4

Data collection top

Siemens SMART CCD diffractometer	2478 independent reflections
Radiation source: fine-focus sealed tube	1323 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.078
ϕ and ω scans	θ_max = 25.1°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Siemens, 1996)	h = −5→5
T_min = 0.842, T_max = 0.864	k = −15→21
7275 measured reflections	l = −19→15

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0343P)² + 0.2069P] where P = (F_o² + 2F_c²)/3
2478 reflections	(Δ/σ)_max = 0.001
191 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₁₃H₈Cl₃N₃O₂	V = 1406.4 (5) Å³
M_r = 344.57	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.892 (1) Å	µ = 0.66 mm⁻¹
b = 18.014 (4) Å	T = 298 K
c = 16.112 (3) Å	0.27 × 0.23 × 0.23 mm
β = 97.90 (3)°

Data collection top

Siemens SMART CCD diffractometer	2478 independent reflections
Absorption correction: multi-scan (SADABS; Siemens, 1996)	1323 reflections with I > 2σ(I)
T_min = 0.842, T_max = 0.864	R_int = 0.078
7275 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.01	Δρ_max = 0.25 e Å⁻³
2478 reflections	Δρ_min = −0.40 e Å⁻³
191 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
Cl1	0.3842 (2)	0.62724 (6)	0.45177 (7)	0.0534 (3)
Cl2	1.2166 (3)	0.50424 (7)	0.65897 (7)	0.0651 (4)
Cl3	1.2331 (3)	1.28010 (7)	0.69130 (8)	0.0698 (4)
N1	0.9665 (7)	0.8466 (2)	0.6071 (2)	0.0471 (9)
N2	1.0608 (7)	0.91708 (18)	0.6266 (2)	0.0474 (9)
H2	1.2318	0.9261	0.6437	0.057*
O1	0.6119 (6)	0.76626 (15)	0.51866 (18)	0.0542 (8)
H1	0.6800	0.8046	0.5397	0.081*
O2	0.6214 (6)	0.95721 (16)	0.59872 (19)	0.0619 (9)
C1	1.0059 (8)	0.7165 (2)	0.6081 (2)	0.0408 (10)
C2	0.7633 (8)	0.7076 (2)	0.5502 (2)	0.0399 (10)
C3	0.6750 (8)	0.6374 (2)	0.5262 (2)	0.0411 (11)
C4	0.8115 (8)	0.5751 (2)	0.5595 (3)	0.0455 (11)
H4	0.7479	0.5280	0.5428	0.055*
C5	1.0456 (9)	0.5834 (2)	0.6182 (3)	0.0461 (11)
C6	1.1444 (9)	0.6532 (2)	0.6417 (3)	0.0450 (11)
H6	1.3036	0.6581	0.6801	0.054*
C7	1.1106 (9)	0.7906 (3)	0.6314 (2)	0.0452 (11)
H7	1.2817	0.7964	0.6639	0.054*
C8	0.8673 (9)	0.9716 (2)	0.6171 (3)	0.0450 (11)
C9	0.9672 (8)	1.0483 (2)	0.6324 (3)	0.0410 (10)
C10	0.8110 (9)	1.1062 (2)	0.5936 (3)	0.0506 (12)
H10	0.6519	1.0962	0.5566	0.061*
C11	0.8935 (9)	1.1786 (3)	0.6102 (3)	0.0543 (12)
H11	0.7949	1.2183	0.5842	0.065*
C12	1.1270 (9)	1.1895 (2)	0.6666 (3)	0.0477 (12)
N3	1.2807 (7)	1.1365 (2)	0.7059 (2)	0.0502 (10)
C13	1.1988 (9)	1.0670 (2)	0.6874 (3)	0.0493 (11)
H13	1.3051	1.0285	0.7133	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0452 (7)	0.0496 (7)	0.0632 (8)	−0.0075 (6)	0.0002 (5)	−0.0027 (6)
Cl2	0.0715 (9)	0.0529 (8)	0.0676 (8)	0.0141 (7)	−0.0015 (6)	0.0027 (6)
Cl3	0.0842 (10)	0.0520 (8)	0.0722 (9)	−0.0184 (7)	0.0071 (7)	−0.0060 (7)
N1	0.040 (2)	0.040 (2)	0.062 (3)	−0.0058 (19)	0.0091 (18)	−0.0038 (19)
N2	0.036 (2)	0.037 (2)	0.067 (3)	−0.0058 (19)	−0.0010 (18)	−0.0074 (19)
O1	0.0454 (19)	0.045 (2)	0.069 (2)	−0.0041 (16)	−0.0032 (15)	−0.0010 (16)
O2	0.0317 (19)	0.060 (2)	0.092 (2)	−0.0082 (16)	0.0027 (16)	−0.0115 (18)
C1	0.030 (2)	0.045 (3)	0.048 (3)	−0.004 (2)	0.010 (2)	−0.005 (2)
C2	0.034 (3)	0.035 (3)	0.050 (3)	−0.002 (2)	0.005 (2)	−0.001 (2)
C3	0.030 (2)	0.049 (3)	0.043 (3)	−0.002 (2)	0.0032 (19)	0.000 (2)
C4	0.048 (3)	0.038 (3)	0.053 (3)	−0.005 (2)	0.016 (2)	−0.003 (2)
C5	0.048 (3)	0.047 (3)	0.044 (3)	0.006 (2)	0.010 (2)	0.002 (2)
C6	0.041 (3)	0.049 (3)	0.045 (3)	0.005 (2)	0.007 (2)	−0.004 (2)
C7	0.035 (3)	0.053 (3)	0.048 (3)	−0.007 (2)	0.006 (2)	−0.008 (2)
C8	0.040 (3)	0.046 (3)	0.049 (3)	−0.008 (2)	0.006 (2)	−0.005 (2)
C9	0.033 (3)	0.041 (3)	0.049 (3)	−0.005 (2)	0.006 (2)	−0.005 (2)
C10	0.041 (3)	0.053 (3)	0.055 (3)	−0.008 (2)	−0.001 (2)	−0.001 (2)
C11	0.053 (3)	0.048 (3)	0.061 (3)	−0.003 (2)	0.003 (2)	0.006 (2)
C12	0.052 (3)	0.046 (3)	0.047 (3)	−0.015 (2)	0.013 (2)	−0.001 (2)
N3	0.043 (2)	0.048 (3)	0.057 (2)	−0.004 (2)	−0.0001 (18)	−0.006 (2)
C13	0.043 (3)	0.044 (3)	0.061 (3)	−0.002 (2)	0.004 (2)	−0.006 (2)

Geometric parameters (Å, º) top

Cl1—C3	1.739 (4)	C4—C5	1.389 (5)
Cl2—C5	1.736 (4)	C4—H4	0.9300
Cl3—C12	1.742 (4)	C5—C6	1.382 (5)
N1—C7	1.263 (5)	C6—H6	0.9300
N1—N2	1.372 (4)	C7—H7	0.9300
N2—C8	1.358 (5)	C8—C9	1.474 (5)
N2—H2	0.8600	C9—C13	1.380 (5)
O1—C2	1.349 (4)	C9—C10	1.391 (5)
O1—H1	0.8200	C10—C11	1.380 (6)
O2—C8	1.227 (5)	C10—H10	0.9300
C1—C6	1.396 (5)	C11—C12	1.373 (6)
C1—C2	1.414 (5)	C11—H11	0.9300
C1—C7	1.460 (5)	C12—N3	1.321 (5)
C2—C3	1.375 (5)	N3—C13	1.337 (5)
C3—C4	1.376 (5)	C13—H13	0.9300

C7—N1—N2	120.9 (4)	N1—C7—C1	119.3 (4)
C8—N2—N1	115.9 (4)	N1—C7—H7	120.3
C8—N2—H2	122.1	C1—C7—H7	120.3
N1—N2—H2	122.1	O2—C8—N2	121.3 (4)
C2—O1—H1	109.5	O2—C8—C9	122.0 (4)
C6—C1—C2	118.8 (4)	N2—C8—C9	116.7 (4)
C6—C1—C7	120.8 (4)	C13—C9—C10	117.2 (4)
C2—C1—C7	120.4 (4)	C13—C9—C8	124.0 (4)
O1—C2—C3	118.6 (4)	C10—C9—C8	118.6 (4)
O1—C2—C1	121.8 (4)	C11—C10—C9	119.6 (4)
C3—C2—C1	119.5 (4)	C11—C10—H10	120.2
C2—C3—C4	121.5 (4)	C9—C10—H10	120.2
C2—C3—Cl1	119.1 (3)	C12—C11—C10	117.3 (4)
C4—C3—Cl1	119.4 (3)	C12—C11—H11	121.4
C3—C4—C5	119.3 (4)	C10—C11—H11	121.4
C3—C4—H4	120.4	N3—C12—C11	125.5 (4)
C5—C4—H4	120.4	N3—C12—Cl3	115.8 (3)
C6—C5—C4	120.6 (4)	C11—C12—Cl3	118.7 (4)
C6—C5—Cl2	120.8 (4)	C12—N3—C13	115.9 (4)
C4—C5—Cl2	118.6 (3)	N3—C13—C9	124.5 (4)
C5—C6—C1	120.3 (4)	N3—C13—H13	117.7
C5—C6—H6	119.9	C9—C13—H13	117.7
C1—C6—H6	119.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱ	0.86	2.20	2.930 (4)	142
O1—H1···N1	0.82	1.82	2.540 (4)	147

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₃H₈Cl₃N₃O₂
M_r	344.57
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	4.892 (1), 18.014 (4), 16.112 (3)
β (°)	97.90 (3)
V (Å³)	1406.4 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.66
Crystal size (mm)	0.27 × 0.23 × 0.23

Data collection
Diffractometer	Siemens SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Siemens, 1996)
T_min, T_max	0.842, 0.864
No. of measured, independent and observed [I > 2σ(I)] reflections	7275, 2478, 1323
R_int	0.078
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.114, 1.01
No. of reflections	2478
No. of parameters	191
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.40

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), 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	0.86	2.20	2.930 (4)	142
O1—H1···N1	0.82	1.82	2.540 (4)	147

Symmetry code: (i) x+1, y, z.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
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Ren, S., Wang, R., Komatsu, K., Bonaz-Krause, P., Zyrianov, Y., McKenna, C. E., Csipke, C., Tokes, Z. A. & Lien, E. J. (2002). J. Med. Chem. 45, 410–419. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART, SAINT and SADABS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Takeuchi, T., Bottcher, A., Quezada, C. M., Simon, M. I., Meade, T. J. & Gray, H. B. (1998). J. Am. Chem. Soc. 120 . 8555–8556. Google Scholar
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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o678

doi:10.1107/S1600536809007272

Open

access