2-Chloro-N-[4-(dimethyl­amino)benzyl­idene]aniline

Li, J.; Liang, Z.-P.; Tai, X.-S.

doi:10.1107/S1600536808036386

organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2319

doi:10.1107/S1600536808036386

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2-Chloro-N-[4-(dimethylamino)benzylidene]aniline

Jian Li,^a ^* Zu-Pei Liang ^a and Xi-Shi Tai ^a

^aDepartment of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: zupeiliang@163.com

(Received 30 August 2008; accepted 6 November 2008; online 13 November 2008)

In the title molecule, C₁₅H₁₅ClN₂, the dihedral angle between the aromatic is 64.1 (2)°.

Related literature

For a related compound, see: You et al. (2004 ).

Experimental

Crystal data

C₁₅H₁₅ClN₂
M_r = 258.74
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.7301 (8) Å
b = 12.2016 (18) Å
c = 14.047 (2) Å
V = 1325.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 298 (2) K
0.45 × 0.38 × 0.30 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.888, T_max = 0.923
5507 measured reflections
2318 independent reflections
1391 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.105
S = 1.02
2318 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.18 e Å⁻³
Absolute structure: Flack (1983 ), 1358 Friedel pairs
Flack parameter: −0.07 (10)

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); 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/S1600536808036386/lh2690sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808036386/lh2690Isup2.hkl

checkCIF report

Comment top

Schiff base compounds have been used as fine chemicals and medical substrates and they are important ligands in coordination chemistry due to their ease of preparation and their ability to be modified both electronically and sterically. In this paper, the structure of the title compound, (I), is reported. The molecular structure of (I) is illustrated in Fig. 1. The bond lengths and angles in the title molecule are similar to the related compound 4-chloro-N-[4-(dimethylamino)benzylidene]aniline (You et al., 2004). The 4-(Dimethylamino)benzylidene system is nearly planar to within 0.035 (3) A°. 2-Chlorobenzenamine system is nearly planar to within 0.060 (3) A°. The dihedral angle between these two systems is 67.0 (2) °.

Related literature top

For a related compound, see: You et al. (2004).

Experimental top

A mixture of 4-(dimethylamino)benzaldehyde (0.01 mol) and 2-chlorobenzenamine (0.01 mol) in ethanol (10 ml) was refluxed for 2 h. After cooling, filtration and drying, the title compound was obtained. 10 mg of (I) were dissolved in 15 ml of ethanol, and the solution was kept at room temperature for 5 d. Natural evaporation gave light yellow single crystals of the title compound, suitable for X-ray analysis.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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), drawn with 30% probability ellipsoids.

2-Chloro-N-[4-(dimethylamino)benzylidene]aniline top

Crystal data top

C₁₅H₁₅ClN₂	F(000) = 544
M_r = 258.74	D_x = 1.297 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1182 reflections
a = 7.7301 (8) Å	θ = 2.9–20.1°
b = 12.2016 (18) Å	µ = 0.27 mm⁻¹
c = 14.047 (2) Å	T = 298 K
V = 1325.0 (3) Å³	Block, light yellow
Z = 4	0.45 × 0.38 × 0.30 mm

Data collection top

Bruker SMART CCD diffractometer	2318 independent reflections
Radiation source: fine-focus sealed tube	1391 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −9→9
T_min = 0.888, T_max = 0.923	k = −14→13
5507 measured reflections	l = −9→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)] = 0.045	H-atom parameters constrained
wR(F²) = 0.105	w = 1/[σ²(F_o²) + (0.0377P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2318 reflections	Δρ_max = 0.18 e Å⁻³
165 parameters	Δρ_min = −0.18 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1358 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.07 (10)

Crystal data top

C₁₅H₁₅ClN₂	V = 1325.0 (3) Å³
M_r = 258.74	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.7301 (8) Å	µ = 0.27 mm⁻¹
b = 12.2016 (18) Å	T = 298 K
c = 14.047 (2) Å	0.45 × 0.38 × 0.30 mm

Data collection top

Bruker SMART CCD diffractometer	2318 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1391 reflections with I > 2σ(I)
T_min = 0.888, T_max = 0.923	R_int = 0.054
5507 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.105	Δρ_max = 0.18 e Å⁻³
S = 1.02	Δρ_min = −0.18 e Å⁻³
2318 reflections	Absolute structure: Flack (1983), 1358 Friedel pairs
165 parameters	Absolute structure parameter: −0.07 (10)
0 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	1.22788 (14)	1.11816 (8)	−0.13149 (7)	0.0753 (4)
N1	0.9918 (4)	0.9322 (2)	−0.09661 (18)	0.0513 (8)
N2	0.8770 (4)	0.7449 (2)	0.32629 (18)	0.0555 (8)
C1	1.0238 (4)	0.8391 (3)	−0.0595 (2)	0.0477 (9)
H1	1.0788	0.7861	−0.0962	0.057*
C2	0.9776 (4)	0.8127 (2)	0.0381 (2)	0.0436 (9)
C3	0.8837 (4)	0.8839 (3)	0.0949 (2)	0.0460 (9)
H3	0.8439	0.9491	0.0686	0.055*
C4	0.8472 (5)	0.8618 (3)	0.1884 (2)	0.0478 (9)
H4	0.7815	0.9112	0.2235	0.057*
C5	0.9077 (4)	0.7656 (3)	0.2319 (2)	0.0441 (9)
C6	0.9993 (5)	0.6920 (3)	0.1744 (2)	0.0498 (9)
H6	1.0379	0.6261	0.2002	0.060*
C7	1.0331 (5)	0.7156 (3)	0.0807 (2)	0.0510 (10)
H7	1.0949	0.6652	0.0445	0.061*
C8	0.7854 (5)	0.8221 (3)	0.3849 (2)	0.0719 (12)
H8A	0.8528	0.8878	0.3913	0.108*
H8B	0.7660	0.7908	0.4467	0.108*
H8C	0.6763	0.8394	0.3559	0.108*
C9	0.9648 (5)	0.6548 (3)	0.3736 (2)	0.0671 (11)
H9A	0.9342	0.5870	0.3432	0.101*
H9B	0.9305	0.6524	0.4393	0.101*
H9C	1.0876	0.6654	0.3696	0.101*
C10	1.0315 (5)	0.9502 (3)	−0.1928 (2)	0.0452 (9)
C11	1.1315 (4)	1.0405 (3)	−0.2197 (2)	0.0481 (9)
C12	1.1594 (5)	1.0664 (3)	−0.3137 (2)	0.0595 (10)
H12	1.2266	1.1269	−0.3298	0.071*
C13	1.0873 (5)	1.0020 (3)	−0.3841 (3)	0.0654 (11)
H13	1.1042	1.0197	−0.4478	0.078*
C14	0.9911 (5)	0.9125 (3)	−0.3600 (3)	0.0661 (11)
H14	0.9451	0.8682	−0.4075	0.079*
C15	0.9612 (5)	0.8869 (3)	−0.2650 (2)	0.0587 (10)
H15	0.8932	0.8266	−0.2497	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0818 (8)	0.0730 (7)	0.0711 (6)	−0.0204 (6)	−0.0003 (6)	−0.0069 (5)
N1	0.060 (2)	0.0516 (17)	0.0423 (16)	−0.0012 (18)	0.0060 (16)	0.0035 (14)
N2	0.053 (2)	0.069 (2)	0.0440 (17)	0.0048 (18)	0.0025 (15)	0.0064 (15)
C1	0.048 (3)	0.050 (2)	0.045 (2)	−0.0014 (19)	−0.0003 (19)	−0.0074 (17)
C2	0.046 (2)	0.0450 (19)	0.0397 (19)	−0.0033 (19)	0.0012 (18)	−0.0035 (16)
C3	0.049 (2)	0.0394 (18)	0.049 (2)	0.0003 (19)	−0.0047 (17)	0.0001 (18)
C4	0.050 (2)	0.048 (2)	0.045 (2)	0.0075 (17)	0.0021 (18)	−0.0034 (17)
C5	0.042 (2)	0.052 (2)	0.0386 (19)	−0.0057 (18)	−0.0011 (17)	−0.0029 (18)
C6	0.057 (3)	0.0407 (19)	0.051 (2)	0.005 (2)	−0.003 (2)	0.0055 (17)
C7	0.056 (3)	0.049 (2)	0.048 (2)	0.0044 (19)	0.0023 (19)	−0.0053 (18)
C8	0.076 (3)	0.095 (3)	0.045 (2)	0.004 (3)	0.012 (2)	−0.002 (2)
C9	0.062 (3)	0.078 (3)	0.061 (2)	−0.007 (2)	−0.004 (2)	0.024 (2)
C10	0.047 (2)	0.046 (2)	0.043 (2)	0.0044 (19)	0.0025 (19)	0.0001 (17)
C11	0.047 (2)	0.050 (2)	0.047 (2)	0.0046 (19)	0.0041 (19)	0.0020 (17)
C12	0.058 (3)	0.063 (2)	0.058 (2)	−0.002 (2)	0.014 (2)	0.009 (2)
C13	0.069 (3)	0.081 (3)	0.046 (2)	0.019 (2)	0.008 (2)	0.008 (2)
C14	0.068 (3)	0.080 (3)	0.050 (2)	0.007 (3)	−0.006 (2)	−0.007 (2)
C15	0.062 (3)	0.057 (2)	0.057 (2)	−0.003 (2)	0.000 (2)	−0.001 (2)

Geometric parameters (Å, º) top

Cl1—C11	1.728 (3)	C7—H7	0.9300
N1—C1	1.274 (3)	C8—H8A	0.9600
N1—C10	1.403 (4)	C8—H8B	0.9600
N2—C5	1.371 (4)	C8—H8C	0.9600
N2—C8	1.438 (4)	C9—H9A	0.9600
N2—C9	1.453 (4)	C9—H9B	0.9600
C1—C2	1.453 (4)	C9—H9C	0.9600
C1—H1	0.9300	C10—C15	1.385 (4)
C2—C3	1.385 (4)	C10—C11	1.398 (4)
C2—C7	1.395 (4)	C11—C12	1.376 (4)
C3—C4	1.369 (4)	C12—C13	1.379 (5)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.404 (4)	C13—C14	1.364 (5)
C4—H4	0.9300	C13—H13	0.9300
C5—C6	1.400 (4)	C14—C15	1.390 (4)
C6—C7	1.373 (4)	C14—H14	0.9300
C6—H6	0.9300	C15—H15	0.9300

C1—N1—C10	119.4 (3)	N2—C8—H8C	109.5
C5—N2—C8	121.2 (3)	H8A—C8—H8C	109.5
C5—N2—C9	120.1 (3)	H8B—C8—H8C	109.5
C8—N2—C9	117.6 (3)	N2—C9—H9A	109.5
N1—C1—C2	122.5 (3)	N2—C9—H9B	109.5
N1—C1—H1	118.8	H9A—C9—H9B	109.5
C2—C1—H1	118.8	N2—C9—H9C	109.5
C3—C2—C7	116.5 (3)	H9A—C9—H9C	109.5
C3—C2—C1	122.2 (3)	H9B—C9—H9C	109.5
C7—C2—C1	121.2 (3)	C15—C10—C11	117.3 (3)
C4—C3—C2	122.5 (3)	C15—C10—N1	122.2 (3)
C4—C3—H3	118.7	C11—C10—N1	120.2 (3)
C2—C3—H3	118.7	C12—C11—C10	121.8 (3)
C3—C4—C5	120.9 (3)	C12—C11—Cl1	119.7 (3)
C3—C4—H4	119.6	C10—C11—Cl1	118.5 (3)
C5—C4—H4	119.6	C11—C12—C13	119.6 (3)
N2—C5—C6	121.8 (3)	C11—C12—H12	120.2
N2—C5—C4	121.2 (3)	C13—C12—H12	120.2
C6—C5—C4	117.0 (3)	C14—C13—C12	119.9 (3)
C7—C6—C5	121.0 (3)	C14—C13—H13	120.0
C7—C6—H6	119.5	C12—C13—H13	120.0
C5—C6—H6	119.5	C13—C14—C15	120.6 (4)
C6—C7—C2	122.1 (3)	C13—C14—H14	119.7
C6—C7—H7	119.0	C15—C14—H14	119.7
C2—C7—H7	119.0	C10—C15—C14	120.8 (3)
N2—C8—H8A	109.5	C10—C15—H15	119.6
N2—C8—H8B	109.5	C14—C15—H15	119.6
H8A—C8—H8B	109.5

C10—N1—C1—C2	−176.5 (3)	C3—C2—C7—C6	−1.0 (5)
N1—C1—C2—C3	5.2 (5)	C1—C2—C7—C6	176.2 (3)
N1—C1—C2—C7	−171.9 (3)	C1—N1—C10—C15	58.8 (5)
C7—C2—C3—C4	0.5 (5)	C1—N1—C10—C11	−127.5 (4)
C1—C2—C3—C4	−176.7 (3)	C15—C10—C11—C12	0.1 (5)
C2—C3—C4—C5	1.4 (5)	N1—C10—C11—C12	−173.9 (3)
C8—N2—C5—C6	178.9 (3)	C15—C10—C11—Cl1	−177.6 (2)
C9—N2—C5—C6	10.8 (5)	N1—C10—C11—Cl1	8.4 (4)
C8—N2—C5—C4	−1.6 (5)	C10—C11—C12—C13	0.1 (5)
C9—N2—C5—C4	−169.6 (3)	Cl1—C11—C12—C13	177.7 (3)
C3—C4—C5—N2	177.6 (3)	C11—C12—C13—C14	−1.0 (6)
C3—C4—C5—C6	−2.8 (5)	C12—C13—C14—C15	1.6 (6)
N2—C5—C6—C7	−178.1 (3)	C11—C10—C15—C14	0.6 (5)
C4—C5—C6—C7	2.3 (5)	N1—C10—C15—C14	174.4 (3)
C5—C6—C7—C2	−0.4 (5)	C13—C14—C15—C10	−1.5 (6)

Experimental details

Crystal data
Chemical formula	C₁₅H₁₅ClN₂
M_r	258.74
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	7.7301 (8), 12.2016 (18), 14.047 (2)
V (Å³)	1325.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.45 × 0.38 × 0.30

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.888, 0.923
No. of measured, independent and observed [I > 2σ(I)] reflections	5507, 2318, 1391
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.105, 1.02
No. of reflections	2318
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.18
Absolute structure	Flack (1983), 1358 Friedel pairs
Absolute structure parameter	−0.07 (10)

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the Natural Science Foundation of Shandong Province (No. Y2007B61) and the Natural Science Foundation of Weifang University.

References

Bruker (1997). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
You, X.-L., Lu, C.-R., Zhang, Y. & Zhang, D.-C. (2004). Acta Cryst. C60, o693–o695. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar