(E)-4-Chloro-N-[(E)-2-methyl-3-phenyl­allyl­idene]aniline

Khalaji, A.D.; Simpson, J.

doi:10.1107/S1600536809001871

organic compounds

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Volume 65| Part 2| February 2009| Page o362

doi:10.1107/S1600536809001871

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(E)-4-Chloro-N-[(E)-2-methyl-3-phenylallylidene]aniline

Aliakbar D. Khalaji ^a and Jim Simpson ^b ^*

^aDepartment of Science, Gorgan University of Agricultural Sciences and Natural Resources, Gorgan, Iran, and ^bDepartment of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand
^*Correspondence e-mail: jsimpson@alkali.otago.ac.nz

(Received 13 January 2009; accepted 15 January 2009; online 23 January 2009)

The title Schiff base compound, C₁₆H₁₄ClN, adopts E configurations with respect to both the C=C and C=N bonds. The dihedral angle between the two aromatic rings is 53.27 (4)°, while the plane through the C=C—C=N system is inclined at 9.06 (8)° to the benzene ring and 44.92 (5)° to the chlorobenzene ring. In the crystal structure, weak C—H⋯Cl and C—H⋯N hydrogen bonds stack the molecules down the a axis.

Related literature

For background to the use of Schiff bases as ligands see: Khalaji et al. (2008a ,b ); and for their bio-activity, see: Karthikeyan et al. (2006 ); Xiong et al. (2008 ); Sriram et al. (2006 ). For related structures, see: Khalaji et al. (2007 ); Khalaji & Harrison (2008 ); Khalaji et al. (2008c ). For reference structural data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₆H₁₄ClN
M_r = 255.73
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.2486 (10) Å
b = 11.6637 (17) Å
c = 15.598 (2) Å
V = 1318.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 89 (2) K
0.36 × 0.24 × 0.03 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ) T_min = 0.841, T_max = 0.992
21077 measured reflections
4077 independent reflections
3517 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.109
S = 1.06
4077 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.36 e Å⁻³
Absolute structure: Flack (1983 ), 1742 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
C7—H7⋯N1ⁱ	0.95	2.67	3.524 (2)	150
C13—H13⋯Cl1ⁱⁱ	0.95	2.92	3.7311 (17)	144
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+2]$ .

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 and SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and TITAN (Hunter & Simpson, 1999 ); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 ), PLATON (Spek, 2003 ) and publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809001871/pk2147sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809001871/pk2147Isup2.hkl

checkCIF report

Comment top

Schiff-bases are well known chelating ligands in coordination chemistry (Khalaji et al., 2008a,b), and exhibit a wide range of biological activities (Karthikeyan et al., 2006) including anti-HIV activity (Xiong et al., 2008; Sriram et al., 2006). As a continuation of our work on the synthesis and structural characterization of Schiff-base compounds (Khalaji et al., 2007; Khalaji & Harrison, 2008; Khalaji et al., 2008c), we report here the structure of the title compound, C₁₆H₁₄NCl, (I), Fig 1.

The title Schiff-base compound, C₁₆H₁₄NCl, adopts E configurations with respect to both the C2=C4 and C1=N1 bonds. Bond lengths in the molecule are normal (Allen, et al., 1987) and similar to those found in related compounds (Khalaji et al., 2007; Khalaji & Harrison, 2008; Khalaji et al., 2008c). The dihedral angle between the two aromatic rings is 53.27 (4)° while the plane through the C2=C4–C1=N1 system is inclined at 9.06 (8)° to the C5···C10 ring and 44.92 (5)° to the C11···C16 ring.

In the crystal structure, weak C13—H13···Cl1 and C7—H7···N1 hydrogen bonds stack the molecules down the a axis.

Related literature top

For background to the use of Schiff bases as ligands see: Khalaji et al. (2008a,b); and for their bio-activity, see: Karthikeyan et al. (2006); Xiong et al. (2008); Sriram et al. (2006). For related structures, see: Khalaji et al. (2007); Khalaji & Harrison (2008); Khalaji et al. (2008c). For reference structural data, see: Allen et al. (1987).

Experimental top

The title compound was prepared in 76% yield from 4-chloroaniline and α-methylcinnamaldehyde as reported elsewhere (Khalaji et al. 2007) and recrystallized from methanol.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006) and SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and TITAN (Hunter & Simpson, 1999); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004), PLATON (Spek, 2003) and publCIF (Westrip, 2009).

Figures top

	Fig. 1. The structure of (I) with displacement ellipsoids for the non-hydrogen atoms drawn at the 50% probability level.
	Fig. 2. Crystal packing of (I) viewed down the a axis with hydrogen bonds drawn as dashed lines. H atoms not involved in hydrogen bonding have been omitted.

(E)-4-Chloro-N-[(E)-2-methyl-3-phenylallylidene]aniline top

Crystal data top

C₁₆H₁₄ClN	F(000) = 536
M_r = 255.73	D_x = 1.288 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5396 reflections
a = 7.2486 (10) Å	θ = 2.6–28.8°
b = 11.6637 (17) Å	µ = 0.27 mm⁻¹
c = 15.598 (2) Å	T = 89 K
V = 1318.7 (3) Å³	Rectangular plate, pale yellow
Z = 4	0.36 × 0.24 × 0.03 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	4077 independent reflections
Radiation source: fine-focus sealed tube	3517 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
ω scans	θ_max = 30.7°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −10→10
T_min = 0.841, T_max = 0.992	k = −16→16
21077 measured reflections	l = −21→22

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)] = 0.039	H-atom parameters constrained
wR(F²) = 0.109	w = 1/[σ²(F_o²) + (0.0649P)²] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
4077 reflections	Δρ_max = 0.30 e Å⁻³
164 parameters	Δρ_min = −0.36 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1742 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (6)

Crystal data top

C₁₆H₁₄ClN	V = 1318.7 (3) Å³
M_r = 255.73	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.2486 (10) Å	µ = 0.27 mm⁻¹
b = 11.6637 (17) Å	T = 89 K
c = 15.598 (2) Å	0.36 × 0.24 × 0.03 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	4077 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	3517 reflections with I > 2σ(I)
T_min = 0.841, T_max = 0.992	R_int = 0.058
21077 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.109	Δρ_max = 0.30 e Å⁻³
S = 1.06	Δρ_min = −0.36 e Å⁻³
4077 reflections	Absolute structure: Flack (1983), 1742 Friedel pairs
164 parameters	Absolute structure parameter: 0.01 (6)
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
N1	0.5152 (2)	0.52967 (12)	0.68870 (9)	0.0202 (3)
C1	0.4972 (2)	0.61272 (13)	0.63497 (9)	0.0183 (3)
H1	0.4550	0.6848	0.6553	0.022*
C2	0.5394 (2)	0.60026 (13)	0.54384 (9)	0.0172 (3)
C3	0.6040 (3)	0.48397 (13)	0.51348 (10)	0.0224 (3)
H3A	0.5303	0.4601	0.4639	0.034*
H3B	0.5892	0.4280	0.5598	0.034*
H3C	0.7343	0.4884	0.4970	0.034*
C4	0.5161 (2)	0.69557 (13)	0.49535 (10)	0.0178 (3)
H4	0.4725	0.7602	0.5264	0.021*
C5	0.5458 (2)	0.71712 (13)	0.40389 (10)	0.0166 (3)
C6	0.6332 (3)	0.64156 (14)	0.34605 (10)	0.0227 (3)
H6	0.6771	0.5695	0.3659	0.027*
C7	0.6560 (2)	0.67119 (14)	0.26031 (10)	0.0228 (3)
H7	0.7151	0.6192	0.2223	0.027*
C8	0.5931 (2)	0.77606 (14)	0.22974 (10)	0.0228 (3)
H8	0.6072	0.7953	0.1709	0.027*
C9	0.5089 (3)	0.85283 (15)	0.28615 (11)	0.0243 (4)
H9	0.4672	0.9252	0.2660	0.029*
C10	0.4861 (2)	0.82324 (14)	0.37165 (10)	0.0205 (3)
H10	0.4286	0.8762	0.4094	0.025*
C11	0.4819 (2)	0.55276 (13)	0.77639 (10)	0.0182 (3)
C12	0.5526 (2)	0.64996 (13)	0.81773 (10)	0.0203 (3)
H12	0.6233	0.7040	0.7862	0.024*
C13	0.5200 (2)	0.66792 (13)	0.90454 (10)	0.0207 (3)
H13	0.5671	0.7342	0.9323	0.025*
C14	0.4183 (2)	0.58807 (13)	0.94995 (10)	0.0193 (3)
Cl1	0.38085 (6)	0.60910 (4)	1.05938 (2)	0.02595 (11)
C15	0.3494 (2)	0.48964 (13)	0.91081 (11)	0.0206 (3)
H15	0.2800	0.4354	0.9428	0.025*
C16	0.3841 (2)	0.47222 (13)	0.82400 (10)	0.0199 (3)
H16	0.3404	0.4045	0.7969	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0204 (7)	0.0212 (6)	0.0190 (6)	0.0000 (5)	0.0007 (5)	0.0002 (5)
C1	0.0174 (7)	0.0186 (6)	0.0189 (7)	0.0011 (6)	0.0001 (6)	−0.0018 (6)
C2	0.0162 (7)	0.0171 (6)	0.0182 (7)	0.0014 (6)	−0.0009 (5)	−0.0021 (6)
C3	0.0278 (9)	0.0173 (6)	0.0222 (8)	0.0029 (7)	0.0032 (7)	−0.0004 (6)
C4	0.0186 (8)	0.0163 (7)	0.0185 (7)	0.0000 (6)	0.0011 (6)	−0.0038 (5)
C5	0.0145 (7)	0.0161 (6)	0.0191 (7)	−0.0025 (6)	0.0003 (6)	−0.0018 (5)
C6	0.0291 (9)	0.0164 (6)	0.0225 (8)	0.0000 (7)	0.0035 (7)	−0.0014 (5)
C7	0.0280 (9)	0.0206 (7)	0.0199 (7)	−0.0031 (7)	0.0053 (6)	−0.0036 (6)
C8	0.0244 (9)	0.0264 (7)	0.0175 (7)	−0.0045 (7)	−0.0010 (6)	0.0008 (6)
C9	0.0257 (9)	0.0238 (7)	0.0233 (8)	0.0035 (7)	0.0006 (7)	0.0054 (6)
C10	0.0204 (8)	0.0198 (7)	0.0213 (7)	0.0028 (6)	0.0019 (6)	0.0004 (6)
C11	0.0174 (7)	0.0190 (7)	0.0183 (7)	0.0034 (6)	−0.0007 (6)	0.0014 (6)
C12	0.0209 (8)	0.0183 (6)	0.0218 (7)	−0.0003 (6)	−0.0028 (6)	0.0042 (6)
C13	0.0233 (8)	0.0174 (7)	0.0214 (7)	−0.0008 (6)	−0.0039 (6)	−0.0012 (6)
C14	0.0181 (7)	0.0217 (7)	0.0180 (7)	0.0051 (6)	−0.0004 (6)	0.0021 (6)
Cl1	0.0302 (2)	0.02978 (19)	0.01791 (17)	0.00604 (18)	0.00123 (15)	−0.00069 (15)
C15	0.0197 (8)	0.0196 (7)	0.0225 (7)	0.0009 (6)	0.0016 (6)	0.0030 (6)
C16	0.0199 (8)	0.0172 (6)	0.0228 (7)	0.0000 (6)	−0.0005 (6)	−0.0006 (6)

Geometric parameters (Å, º) top

N1—C1	1.287 (2)	C8—C9	1.396 (2)
N1—C11	1.415 (2)	C8—H8	0.9500
C1—C2	1.4612 (19)	C9—C10	1.387 (2)
C1—H1	0.9500	C9—H9	0.9500
C2—C4	1.355 (2)	C10—H10	0.9500
C2—C3	1.511 (2)	C11—C16	1.392 (2)
C3—H3A	0.9800	C11—C12	1.401 (2)
C3—H3B	0.9800	C12—C13	1.390 (2)
C3—H3C	0.9800	C12—H12	0.9500
C4—C5	1.464 (2)	C13—C14	1.383 (2)
C4—H4	0.9500	C13—H13	0.9500
C5—C10	1.404 (2)	C14—C15	1.393 (2)
C5—C6	1.412 (2)	C14—Cl1	1.7456 (16)
C6—C7	1.391 (2)	C15—C16	1.392 (2)
C6—H6	0.9500	C15—H15	0.9500
C7—C8	1.390 (2)	C16—H16	0.9500
C7—H7	0.9500

C1—N1—C11	117.96 (14)	C7—C8—H8	120.3
N1—C1—C2	122.50 (14)	C9—C8—H8	120.3
N1—C1—H1	118.8	C10—C9—C8	119.89 (15)
C2—C1—H1	118.8	C10—C9—H9	120.1
C4—C2—C1	115.80 (14)	C8—C9—H9	120.1
C4—C2—C3	126.88 (13)	C9—C10—C5	121.79 (15)
C1—C2—C3	117.32 (13)	C9—C10—H10	119.1
C2—C3—H3A	109.5	C5—C10—H10	119.1
C2—C3—H3B	109.5	C16—C11—C12	119.14 (15)
H3A—C3—H3B	109.5	C16—C11—N1	118.32 (14)
C2—C3—H3C	109.5	C12—C11—N1	122.44 (15)
H3A—C3—H3C	109.5	C13—C12—C11	120.52 (15)
H3B—C3—H3C	109.5	C13—C12—H12	119.7
C2—C4—C5	131.77 (14)	C11—C12—H12	119.7
C2—C4—H4	114.1	C14—C13—C12	119.20 (15)
C5—C4—H4	114.1	C14—C13—H13	120.4
C10—C5—C6	117.38 (14)	C12—C13—H13	120.4
C10—C5—C4	117.05 (14)	C13—C14—C15	121.45 (15)
C6—C5—C4	125.55 (14)	C13—C14—Cl1	119.28 (12)
C7—C6—C5	120.84 (15)	C15—C14—Cl1	119.25 (12)
C7—C6—H6	119.6	C16—C15—C14	118.82 (15)
C5—C6—H6	119.6	C16—C15—H15	120.6
C8—C7—C6	120.63 (15)	C14—C15—H15	120.6
C8—C7—H7	119.7	C11—C16—C15	120.83 (14)
C6—C7—H7	119.7	C11—C16—H16	119.6
C7—C8—C9	119.46 (15)	C15—C16—H16	119.6

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···N1ⁱ	0.95	2.67	3.524 (2)	150
C13—H13···Cl1ⁱⁱ	0.95	2.92	3.7311 (17)	144

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₄ClN
M_r	255.73
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	89
a, b, c (Å)	7.2486 (10), 11.6637 (17), 15.598 (2)
V (Å³)	1318.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.36 × 0.24 × 0.03

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2006)
T_min, T_max	0.841, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	21077, 4077, 3517
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.719

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.109, 1.06
No. of reflections	4077
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.36
Absolute structure	Flack (1983), 1742 Friedel pairs
Absolute structure parameter	0.01 (6)

Computer programs: , APEX2 (Bruker, 2006) and SAINT (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and TITAN (Hunter & Simpson, 1999), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004), PLATON (Spek, 2003) and publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···N1ⁱ	0.95	2.67	3.524 (2)	150.3
C13—H13···Cl1ⁱⁱ	0.95	2.92	3.7311 (17)	144.0

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

Acknowledgements

We thank the University of Otago for purchase of the diffractometer.

References

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