4-Chloro-2-[(E)-(2-chloro­phen­yl)imino­meth­yl]phenol

Zhang, X.

doi:10.1107/S1600536809003924

organic compounds

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Volume 65| Part 3| March 2009| Page o512

doi:10.1107/S1600536809003924

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4-Chloro-2-[(E)-(2-chlorophenyl)iminomethyl]phenol

Xinli Zhang ^a ^*

^aDepartment of Chemistry, Baoji University of Arts and Science, Baoji, Shaanxi 721007, People's Republic of China
^*Correspondence e-mail: zhangxinli6008@163.com

(Received 3 January 2009; accepted 2 February 2009; online 11 February 2009)

The title compound, C₁₃H₉Cl₂NO, was crystallized from a methanol solution of 5-chlorosalicylaldehyde and o-chloroaniline. The molecule displays a trans configuration with respect to the imine C=N double bond. The N atom is involved in an intramolecular O—H⋯N hydrogen bond. The two aromatic rings are essentially coplanar, the dihedral angle between them being 7.1 (1)°. A C—H⋯π interaction is present in the crystal.

Related literature

For the biological properties of Schiff bases containing O and N atoms, see: Antony et al. (1999 ); Lumme & Elo (1984 ); Yao et al. (1999 ). For its chemical behaviour, see: Ueno et al. (2006 ).

Experimental

Crystal data

C₁₃H₉Cl₂NO
M_r = 266.11
Orthorhombic, P b c a
a = 7.2693 (13) Å
b = 13.0037 (19) Å
c = 25.2711 (16) Å
V = 2388.8 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.52 mm⁻¹
T = 298 (2) K
0.50 × 0.48 × 0.47 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Siemens, 1996 ) T_min = 0.780, T_max = 0.791
11102 measured reflections
2103 independent reflections
1496 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.099
S = 1.08
2103 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.87	2.603 (3)	147
C11—H11⋯Cg1ⁱ	0.93	2.97	3.549 (3)	122
Symmetry code: (i) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ . Cg1 is the centroid of C8–C13 phenyl ring.

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 I, global. DOI: 10.1107/S1600536809003924/bq2118sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809003924/bq2118Isup2.hkl

checkCIF report

Comment top

The Schiff base containing some O and N atoms is a new important biological ligand and it shows some interesting biological properties, such as antibacterial, antiphlogistic, anticancer and high catalytic activities (Antony et al., 1999; Lumme & Elo et al., 1984; Yao et al., 1999), so the chemical behavior of the Schiff base has drawn our attention (Ueno et al., 2006). Our research emphasis is focused on the synthesis of the Schiff base. Then, a new crystal structure of the title compound, (I), is reported here.

The molecular structure of (I) are illustrated in Fig. 1. In the structure of (I), the whole molecule is essentially planar with a 7.1 (2)° dihedral angle between the two phenyl rings. The C1═N1 bond distance [1.277 (3)Å] is shorter than the standart 1.28Å value of C═N double bond, indicating a delocalization of π-electron density across the phenyl ring. In addition to the intramolecular O-H..N hydrogen bond, there is also an intermolecular C-H..π interaction (Table 1.)

Related literature top

For the biological properties of Schiff bases containing O and N atoms, see: Antony et al. (1999); Lumme & Elo (1984); Yao et al. (1999). For its chemical behaviour, see: Ueno et al. (2006). Cg1 is the centroid of C8–C13 phenyl ring.

Experimental top

A solution of 5-chlorosalicylaldehyde (0.1 mmol, 15.7 mg) in methanol (10 ml) was added dropwise to the methanol (10 ml) solution of o-chloroaniline (0.1 mmol, 12.8 mg) with stirring. The mixture was stirred at room temperature for one hour and then filtered. After allowing the filtrate to stand in air for 3 d, yellow block-shaped crystals of the title compound were formed in slow evaporation of the solvent. The crystals were collected, washed with methanol and dried in a vacuum desiccator using anhydrous CaCl₂ (yield 60%).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART (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 structure of the title compound with 30% probability ellipsoids. The dashed line represents hydrogen bond.

4-Chloro-2-[(E)-(2-chlorophenyl)iminomethyl]phenol top

Crystal data top

C₁₃H₉Cl₂NO	F(000) = 1088
M_r = 266.11	D_x = 1.480 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3178 reflections
a = 7.2693 (13) Å	θ = 2.9–26.3°
b = 13.0037 (19) Å	µ = 0.52 mm⁻¹
c = 25.2711 (16) Å	T = 298 K
V = 2388.8 (6) Å³	Block, yellow
Z = 8	0.50 × 0.48 × 0.47 mm

Data collection top

Siemens SMART CCD area-detector diffractometer	2103 independent reflections
Radiation source: fine-focus sealed tube	1496 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Siemens, 1996)	h = −8→8
T_min = 0.780, T_max = 0.791	k = −15→11
11102 measured reflections	l = −30→29

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-atom parameters constrained
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0287P)² + 1.7853P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2103 reflections	Δρ_max = 0.20 e Å⁻³
155 parameters	Δρ_min = −0.22 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: 0.0069 (6)

Crystal data top

C₁₃H₉Cl₂NO	V = 2388.8 (6) Å³
M_r = 266.11	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 7.2693 (13) Å	µ = 0.52 mm⁻¹
b = 13.0037 (19) Å	T = 298 K
c = 25.2711 (16) Å	0.50 × 0.48 × 0.47 mm

Data collection top

Siemens SMART CCD area-detector diffractometer	2103 independent reflections
Absorption correction: multi-scan (SADABS; Siemens, 1996)	1496 reflections with I > 2σ(I)
T_min = 0.780, T_max = 0.791	R_int = 0.041
11102 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.08	Δρ_max = 0.20 e Å⁻³
2103 reflections	Δρ_min = −0.22 e Å⁻³
155 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	0.07629 (12)	1.13163 (6)	1.12839 (3)	0.0653 (3)
Cl2	0.41980 (14)	0.79479 (6)	0.83555 (3)	0.0760 (3)
N1	0.3625 (3)	0.96742 (15)	0.90783 (8)	0.0407 (5)
O1	0.2932 (4)	0.81908 (14)	0.97404 (8)	0.0734 (7)
H1	0.3252	0.8457	0.9461	0.110*
C1	0.3120 (3)	1.03135 (19)	0.94334 (9)	0.0396 (6)
H1A	0.3132	1.1013	0.9357	0.048*
C2	0.2530 (3)	0.99774 (18)	0.99498 (9)	0.0366 (6)
C3	0.2445 (4)	0.89294 (19)	1.00872 (10)	0.0482 (7)
C4	0.1860 (4)	0.8649 (2)	1.05868 (11)	0.0591 (8)
H4	0.1806	0.7956	1.0677	0.071*
C5	0.1357 (4)	0.9376 (2)	1.09521 (11)	0.0519 (7)
H5	0.0972	0.9178	1.1288	0.062*
C6	0.1427 (4)	1.04066 (19)	1.08177 (10)	0.0432 (6)
C7	0.1990 (4)	1.07049 (19)	1.03254 (10)	0.0422 (6)
H7	0.2014	1.1400	1.0239	0.051*
C8	0.4229 (3)	0.99867 (19)	0.85743 (9)	0.0393 (6)
C9	0.4587 (4)	0.9228 (2)	0.82003 (11)	0.0462 (7)
C10	0.5255 (4)	0.9469 (2)	0.77026 (11)	0.0588 (8)
H10	0.5487	0.8949	0.7459	0.071*
C11	0.5574 (4)	1.0476 (3)	0.75699 (12)	0.0627 (8)
H11	0.6026	1.0641	0.7236	0.075*
C12	0.5224 (5)	1.1235 (2)	0.79298 (12)	0.0635 (9)
H12	0.5439	1.1918	0.7839	0.076*
C13	0.4556 (4)	1.1001 (2)	0.84244 (11)	0.0544 (7)
H13	0.4319	1.1529	0.8663	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0859 (6)	0.0587 (5)	0.0515 (4)	0.0011 (4)	0.0102 (4)	−0.0135 (4)
Cl2	0.1089 (8)	0.0424 (4)	0.0766 (6)	−0.0022 (4)	0.0226 (5)	−0.0113 (4)
N1	0.0478 (13)	0.0375 (12)	0.0367 (11)	−0.0015 (10)	−0.0029 (10)	−0.0003 (10)
O1	0.128 (2)	0.0355 (10)	0.0562 (12)	0.0156 (12)	0.0259 (13)	0.0034 (9)
C1	0.0434 (15)	0.0330 (13)	0.0424 (14)	−0.0013 (11)	−0.0043 (12)	0.0023 (12)
C2	0.0385 (13)	0.0335 (12)	0.0377 (13)	−0.0001 (10)	−0.0036 (12)	0.0011 (11)
C3	0.0614 (18)	0.0379 (14)	0.0452 (15)	0.0094 (13)	0.0001 (14)	0.0028 (12)
C4	0.088 (2)	0.0384 (15)	0.0512 (16)	0.0129 (15)	0.0078 (16)	0.0119 (14)
C5	0.0633 (19)	0.0532 (17)	0.0391 (14)	0.0078 (14)	0.0032 (14)	0.0097 (13)
C6	0.0467 (16)	0.0428 (15)	0.0402 (14)	0.0026 (12)	−0.0029 (12)	−0.0038 (12)
C7	0.0481 (16)	0.0343 (13)	0.0443 (15)	−0.0037 (11)	−0.0030 (12)	−0.0001 (11)
C8	0.0390 (14)	0.0436 (14)	0.0353 (13)	−0.0006 (12)	−0.0059 (11)	0.0024 (11)
C9	0.0472 (17)	0.0435 (15)	0.0479 (15)	0.0012 (12)	−0.0004 (13)	−0.0024 (12)
C10	0.060 (2)	0.068 (2)	0.0478 (16)	0.0039 (16)	0.0083 (15)	−0.0077 (15)
C11	0.063 (2)	0.080 (2)	0.0456 (16)	−0.0032 (17)	0.0071 (15)	0.0107 (17)
C12	0.082 (2)	0.0572 (18)	0.0518 (17)	−0.0089 (17)	0.0014 (16)	0.0151 (15)
C13	0.073 (2)	0.0429 (15)	0.0475 (16)	−0.0042 (14)	−0.0005 (15)	0.0022 (13)

Geometric parameters (Å, º) top

Cl1—C6	1.738 (3)	C5—H5	0.9300
Cl2—C9	1.733 (3)	C6—C7	1.366 (3)
N1—C1	1.277 (3)	C7—H7	0.9300
N1—C8	1.407 (3)	C8—C9	1.391 (4)
O1—C3	1.347 (3)	C8—C13	1.393 (4)
O1—H1	0.8200	C9—C10	1.384 (4)
C1—C2	1.441 (3)	C10—C11	1.371 (4)
C1—H1A	0.9300	C10—H10	0.9300
C2—C7	1.397 (3)	C11—C12	1.367 (4)
C2—C3	1.408 (3)	C11—H11	0.9300
C3—C4	1.381 (4)	C12—C13	1.375 (4)
C4—C5	1.371 (4)	C12—H12	0.9300
C4—H4	0.9300	C13—H13	0.9300
C5—C6	1.383 (4)

C1—N1—C8	122.5 (2)	C6—C7—H7	119.6
C3—O1—H1	109.5	C2—C7—H7	119.6
N1—C1—C2	121.6 (2)	C9—C8—C13	117.1 (2)
N1—C1—H1A	119.2	C9—C8—N1	117.9 (2)
C2—C1—H1A	119.2	C13—C8—N1	124.9 (2)
C7—C2—C3	118.4 (2)	C10—C9—C8	121.5 (3)
C7—C2—C1	119.6 (2)	C10—C9—Cl2	118.7 (2)
C3—C2—C1	122.0 (2)	C8—C9—Cl2	119.8 (2)
O1—C3—C4	119.2 (2)	C11—C10—C9	119.9 (3)
O1—C3—C2	121.2 (2)	C11—C10—H10	120.1
C4—C3—C2	119.6 (2)	C9—C10—H10	120.1
C5—C4—C3	121.0 (3)	C12—C11—C10	119.7 (3)
C5—C4—H4	119.5	C12—C11—H11	120.1
C3—C4—H4	119.5	C10—C11—H11	120.1
C4—C5—C6	119.5 (3)	C11—C12—C13	120.7 (3)
C4—C5—H5	120.2	C11—C12—H12	119.6
C6—C5—H5	120.2	C13—C12—H12	119.6
C7—C6—C5	120.6 (2)	C12—C13—C8	121.2 (3)
C7—C6—Cl1	120.5 (2)	C12—C13—H13	119.4
C5—C6—Cl1	118.9 (2)	C8—C13—H13	119.4
C6—C7—C2	120.7 (2)

C8—N1—C1—C2	−179.1 (2)	C1—C2—C7—C6	−179.9 (2)
N1—C1—C2—C7	180.0 (2)	C1—N1—C8—C9	−174.2 (2)
N1—C1—C2—C3	−1.2 (4)	C1—N1—C8—C13	8.1 (4)
C7—C2—C3—O1	179.4 (3)	C13—C8—C9—C10	0.6 (4)
C1—C2—C3—O1	0.6 (4)	N1—C8—C9—C10	−177.4 (3)
C7—C2—C3—C4	−0.8 (4)	C13—C8—C9—Cl2	−179.5 (2)
C1—C2—C3—C4	−179.6 (3)	N1—C8—C9—Cl2	2.5 (3)
O1—C3—C4—C5	179.8 (3)	C8—C9—C10—C11	−0.1 (4)
C2—C3—C4—C5	0.1 (5)	Cl2—C9—C10—C11	180.0 (2)
C3—C4—C5—C6	0.3 (5)	C9—C10—C11—C12	−0.2 (5)
C4—C5—C6—C7	0.1 (4)	C10—C11—C12—C13	0.1 (5)
C4—C5—C6—Cl1	179.4 (2)	C11—C12—C13—C8	0.4 (5)
C5—C6—C7—C2	−0.9 (4)	C9—C8—C13—C12	−0.7 (4)
Cl1—C6—C7—C2	179.8 (2)	N1—C8—C13—C12	177.1 (3)
C3—C2—C7—C6	1.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.87	2.603 (3)	147
C11—H11···Cg1ⁱ	0.93	2.97	3.549 (3)	122

Symmetry code: (i) x−1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₉Cl₂NO
M_r	266.11
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	7.2693 (13), 13.0037 (19), 25.2711 (16)
V (Å³)	2388.8 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.52
Crystal size (mm)	0.50 × 0.48 × 0.47

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Siemens, 1996)
T_min, T_max	0.780, 0.791
No. of measured, independent and observed [I > 2σ(I)] reflections	11102, 2103, 1496
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.099, 1.08
No. of reflections	2103
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.22

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
O1—H1···N1	0.82	1.87	2.603 (3)	147.3
C11—H11···Cg1ⁱ	0.93	2.97	3.549 (3)	122

Symmetry code: (i) x−1/2, y, −z+1/2.

Acknowledgements

This work was supported financially by research project No. 08JZ09 of the Phytochemistry Key Laboratory of Shaanxi Province.

References

Antony, F. M., O'Mahony, R. S. & Joyce, M. W. (1999). Croat. Chem. Acta, 72, 685–703. Google Scholar
Lumme, P. & Elo, H. (1984). Inorg. Chim. Acta, 92, 241–251. CrossRef CAS Web of Science 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
Ueno, T., Yokoi, N., Unno, M., Matsui, T., Tokita, Y., Yamada, M., Ikeda-Saito, M., Nakajima, H. & Watanabe, Y. (2006). PNAS, 103, 9416–9421. Web of Science CrossRef PubMed CAS Google Scholar
Yao, K. M., Li, N., Huang, Q. H., Shen, L.-F. & Yuan, H.-Z. (1999). Sci. China Ser. B Chem. 42, 53–61. Web of Science CrossRef CAS Google Scholar