2,3-Dimethyl-N-[(E)-4-nitro­benzyl­idene]aniline

Tariq, M.I.; Ahmad, S.; Tahir, M.N.; Sarfaraz, M.; Hussain, I.

doi:10.1107/S160053681001932X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1561

doi:10.1107/S160053681001932X

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2,3-Dimethyl-N-[(E)-4-nitrobenzylidene]aniline

Muhammad Ilyas Tariq,^a Shahbaz Ahmad,^a M. Nawaz Tahir,^b ^* Muhammad Sarfaraz ^a and Ishtiaq Hussain ^a

^aDepartment of Chemistry, University of Sargodha, Sargodha, Pakistan, and ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 22 May 2010; accepted 23 May 2010; online 5 June 2010)

In the title compound, C₁₅H₁₄N₂O₂, the aromatic rings are oriented at a dihedral angle of 24.52 (5)°. The dihedral angle between the nitro group and its parent benzene ring is 9.22 (16)°. In the crystal, molecules interact through aromatic π—π stacking interactions [centroid–centroid separations = 3.8158 (14) and 3.9139 (14) Å].

Related literature

For structural systematics of related compounds, see: Harada et al. (2004 ).

Experimental

Crystal data

C₁₅H₁₄N₂O₂
M_r = 254.28
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.1969 (5) Å
b = 11.8023 (7) Å
c = 15.3721 (8) Å
V = 1305.71 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.32 × 0.14 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.986, T_max = 0.987
13172 measured reflections
1917 independent reflections
1253 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.111
S = 1.02
1917 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681001932X/hb5464sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681001932X/hb5464Isup2.hkl

checkCIF report

Comment top

Torsional, vibration and central bond length of N-benzylideneanilines (Harada et al., 2004) has been studied for seven compounds at different temperatures. The title compound (I, Fig. 1) is another example due to change of substitutions at both phenyl rings for which the same study can be undertaken. The title compound has been prepared for derivatization.

The molecules of (I) are essentially monomeric having no intra or inter-molecular H-bondings. The phenyl rings A (C1—C6) and B (C10—C15) are planar with r. m. s. deviation of 0.0065 and 0.0022 Å respectively. The dihedral angle between A/B is 24.52 (5)°. The nitro group C (O1/N2/O2) is oriented at 9.22 (16)° with the parent phenyl ring. It is to be noted that the nitro substituated phenyl ring B has smaller bond lengths [1.365 (3)–1.387 (3) Å], whereas the 2,3-dimethyl substituated ring has longer bond lengths 1.373 (3)—1.401 (3) Å. The value of C═N bond length at room temperature for (I) is 1.262 (3) Å which is in compatible with the studies of Harada et al., 2004. The molecules are stabilized due to π—π interactions between the centroids of phenyl rings with separation of 3.8158 (14) and 3.9139 (14) Å.

Related literature top

For structural systematics of related compounds, see: Harada et al. (2004).

Experimental top

Equimolar quantities of 2,3-dimethylaniline and 4-nitro benzaldehyde were refluxed in methanol for 15 minutes resulting in yellow color precipitates. The contents of the flask were dried at room temperature and washed with methanol and ethanol, respectively. The washed crude material affoarded yellow needles of (I) in the solution of diethyl ether at room temperature by slow evaporation after 24 h.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

Fig. 1. View of (I) with displacement ellipsoids drawn at the 50% probability level.

2,3-Dimethyl-N-[(E)-4-nitrobenzylidene]aniline top

Crystal data top

C₁₅H₁₄N₂O₂	F(000) = 536
M_r = 254.28	D_x = 1.294 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1334 reflections
a = 7.1969 (5) Å	θ = 2.1–25.4°
b = 11.8023 (7) Å	µ = 0.09 mm⁻¹
c = 15.3721 (8) Å	T = 296 K
V = 1305.71 (14) Å³	Needle, yellow
Z = 4	0.32 × 0.14 × 0.14 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1917 independent reflections
Radiation source: fine-focus sealed tube	1253 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
Detector resolution: 7.40 pixels mm^-1	θ_max = 28.6°, θ_min = 2.2°
ω scans	h = −8→9
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −15→15
T_min = 0.986, T_max = 0.987	l = −20→20
13172 measured reflections

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0482P)² + 0.0883P] where P = (F_o² + 2F_c²)/3
1917 reflections	(Δ/σ)_max < 0.001
174 parameters	Δρ_max = 0.12 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₅H₁₄N₂O₂	V = 1305.71 (14) Å³
M_r = 254.28	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.1969 (5) Å	µ = 0.09 mm⁻¹
b = 11.8023 (7) Å	T = 296 K
c = 15.3721 (8) Å	0.32 × 0.14 × 0.14 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1917 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1253 reflections with I > 2σ(I)
T_min = 0.986, T_max = 0.987	R_int = 0.057
13172 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.02	Δρ_max = 0.12 e Å⁻³
1917 reflections	Δρ_min = −0.14 e Å⁻³
174 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
O1	0.1409 (4)	−0.19301 (18)	0.70198 (14)	0.0997 (9)
O2	0.1083 (4)	−0.06237 (19)	0.79842 (12)	0.0941 (9)
N1	0.1128 (3)	0.34130 (16)	0.47092 (11)	0.0485 (7)
N2	0.1253 (3)	−0.0943 (2)	0.72311 (16)	0.0684 (9)
C1	0.1231 (3)	0.42218 (18)	0.40278 (13)	0.0457 (7)
C2	0.1509 (3)	0.5351 (2)	0.42653 (14)	0.0488 (8)
C3	0.1581 (4)	0.61833 (19)	0.36160 (15)	0.0549 (8)
C4	0.1353 (4)	0.5864 (2)	0.27595 (17)	0.0624 (10)
C5	0.1052 (4)	0.4755 (2)	0.25272 (16)	0.0650 (10)
C6	0.0972 (4)	0.3935 (2)	0.31593 (14)	0.0550 (8)
C7	0.1768 (4)	0.5654 (2)	0.52133 (14)	0.0679 (10)
C8	0.1878 (5)	0.7409 (2)	0.38401 (19)	0.0820 (13)
C9	0.1573 (4)	0.23940 (19)	0.45751 (14)	0.0495 (8)
C10	0.1434 (3)	0.15342 (18)	0.52625 (14)	0.0448 (7)
C11	0.1832 (3)	0.04156 (19)	0.50760 (15)	0.0525 (8)
C12	0.1753 (4)	−0.0397 (2)	0.57139 (15)	0.0551 (9)
C13	0.1287 (3)	−0.0075 (2)	0.65402 (14)	0.0500 (8)
C14	0.0878 (3)	0.1021 (2)	0.67504 (15)	0.0523 (8)
C15	0.0953 (3)	0.18289 (19)	0.61064 (14)	0.0496 (8)
H4	0.14039	0.64145	0.23274	0.0748*
H5	0.09027	0.45617	0.19450	0.0779*
H6	0.07448	0.31854	0.30059	0.0659*
H7A	0.09112	0.62429	0.53696	0.1016*
H7B	0.30167	0.59128	0.53059	0.1016*
H7C	0.15399	0.49972	0.55663	0.1016*
H8A	0.18433	0.78558	0.33184	0.1229*
H8B	0.30655	0.74981	0.41166	0.1229*
H8C	0.09161	0.76571	0.42285	0.1229*
H9	0.20007	0.21822	0.40278	0.0594*
H11	0.21572	0.02105	0.45120	0.0630*
H12	0.20116	−0.11509	0.55867	0.0661*
H14	0.05543	0.12165	0.73165	0.0627*
H15	0.06802	0.25797	0.62382	0.0596*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.131 (2)	0.0586 (12)	0.1094 (16)	0.0005 (15)	0.0004 (17)	0.0307 (12)
O2	0.1205 (19)	0.1055 (16)	0.0563 (11)	−0.0025 (15)	−0.0044 (13)	0.0275 (12)
N1	0.0509 (12)	0.0484 (11)	0.0463 (11)	0.0052 (10)	0.0029 (10)	0.0042 (9)
N2	0.0614 (15)	0.0707 (16)	0.0731 (16)	−0.0068 (14)	−0.0072 (13)	0.0266 (13)
C1	0.0431 (14)	0.0477 (12)	0.0463 (12)	0.0035 (11)	0.0067 (11)	0.0043 (10)
C2	0.0454 (15)	0.0529 (13)	0.0482 (12)	0.0020 (12)	0.0069 (11)	0.0015 (11)
C3	0.0515 (16)	0.0504 (13)	0.0628 (15)	0.0051 (12)	0.0070 (12)	0.0082 (11)
C4	0.0660 (19)	0.0615 (16)	0.0596 (16)	0.0045 (15)	0.0068 (14)	0.0193 (13)
C5	0.079 (2)	0.0708 (17)	0.0453 (12)	0.0029 (16)	0.0008 (14)	0.0040 (12)
C6	0.0614 (16)	0.0526 (14)	0.0509 (14)	0.0027 (13)	0.0009 (13)	−0.0010 (12)
C7	0.081 (2)	0.0651 (16)	0.0577 (14)	−0.0020 (16)	0.0041 (14)	−0.0097 (13)
C8	0.105 (3)	0.0539 (15)	0.087 (2)	−0.0044 (18)	0.009 (2)	0.0079 (15)
C9	0.0467 (15)	0.0539 (13)	0.0479 (12)	0.0039 (12)	0.0081 (12)	0.0010 (11)
C10	0.0406 (13)	0.0467 (12)	0.0471 (13)	0.0009 (11)	0.0030 (11)	0.0026 (10)
C11	0.0578 (16)	0.0514 (13)	0.0483 (12)	0.0057 (12)	0.0043 (11)	−0.0031 (11)
C12	0.0608 (17)	0.0424 (12)	0.0621 (15)	0.0015 (12)	0.0011 (13)	0.0007 (11)
C13	0.0436 (14)	0.0550 (14)	0.0515 (12)	−0.0029 (12)	−0.0050 (12)	0.0116 (11)
C14	0.0521 (15)	0.0601 (16)	0.0447 (12)	0.0018 (13)	−0.0007 (11)	0.0014 (12)
C15	0.0521 (15)	0.0456 (12)	0.0512 (13)	0.0046 (12)	0.0015 (12)	0.0005 (11)

Geometric parameters (Å, º) top

O1—N2	1.215 (3)	C12—C13	1.368 (3)
O2—N2	1.224 (3)	C13—C14	1.365 (3)
N1—C1	1.419 (3)	C14—C15	1.376 (3)
N1—C9	1.262 (3)	C4—H4	0.9300
N2—C13	1.476 (3)	C5—H5	0.9300
C1—C2	1.396 (3)	C6—H6	0.9300
C1—C6	1.390 (3)	C7—H7A	0.9600
C2—C3	1.401 (3)	C7—H7B	0.9600
C2—C7	1.512 (3)	C7—H7C	0.9600
C3—C4	1.379 (3)	C8—H8A	0.9600
C3—C8	1.502 (3)	C8—H8B	0.9600
C4—C5	1.374 (3)	C8—H8C	0.9600
C5—C6	1.373 (3)	C9—H9	0.9300
C9—C10	1.468 (3)	C11—H11	0.9300
C10—C11	1.381 (3)	C12—H12	0.9300
C10—C15	1.387 (3)	C14—H14	0.9300
C11—C12	1.373 (3)	C15—H15	0.9300

C1—N1—C9	120.49 (18)	C5—C4—H4	119.00
O1—N2—O2	123.9 (2)	C4—C5—H5	120.00
O1—N2—C13	118.2 (2)	C6—C5—H5	120.00
O2—N2—C13	118.0 (2)	C1—C6—H6	120.00
N1—C1—C2	117.16 (18)	C5—C6—H6	120.00
N1—C1—C6	122.56 (19)	C2—C7—H7A	109.00
C2—C1—C6	120.2 (2)	C2—C7—H7B	109.00
C1—C2—C3	119.2 (2)	C2—C7—H7C	109.00
C1—C2—C7	119.7 (2)	H7A—C7—H7B	110.00
C3—C2—C7	121.1 (2)	H7A—C7—H7C	109.00
C2—C3—C4	118.9 (2)	H7B—C7—H7C	109.00
C2—C3—C8	121.1 (2)	C3—C8—H8A	109.00
C4—C3—C8	119.9 (2)	C3—C8—H8B	109.00
C3—C4—C5	121.8 (2)	C3—C8—H8C	109.00
C4—C5—C6	119.6 (2)	H8A—C8—H8B	109.00
C1—C6—C5	120.2 (2)	H8A—C8—H8C	109.00
N1—C9—C10	121.6 (2)	H8B—C8—H8C	109.00
C9—C10—C11	119.8 (2)	N1—C9—H9	119.00
C9—C10—C15	121.1 (2)	C10—C9—H9	119.00
C11—C10—C15	119.1 (2)	C10—C11—H11	120.00
C10—C11—C12	120.7 (2)	C12—C11—H11	120.00
C11—C12—C13	118.7 (2)	C11—C12—H12	121.00
N2—C13—C12	118.7 (2)	C13—C12—H12	121.00
N2—C13—C14	118.9 (2)	C13—C14—H14	121.00
C12—C13—C14	122.4 (2)	C15—C14—H14	121.00
C13—C14—C15	118.6 (2)	C10—C15—H15	120.00
C10—C15—C14	120.6 (2)	C14—C15—H15	120.00
C3—C4—H4	119.00

C9—N1—C1—C2	−153.3 (2)	C2—C3—C4—C5	0.2 (4)
C9—N1—C1—C6	30.1 (4)	C8—C3—C4—C5	−179.1 (3)
C1—N1—C9—C10	−178.4 (2)	C3—C4—C5—C6	0.1 (4)
O1—N2—C13—C12	−9.2 (3)	C4—C5—C6—C1	−1.3 (4)
O1—N2—C13—C14	171.7 (2)	N1—C9—C10—C11	176.3 (2)
O2—N2—C13—C12	170.3 (3)	N1—C9—C10—C15	−5.4 (4)
O2—N2—C13—C14	−8.8 (3)	C9—C10—C11—C12	178.5 (2)
N1—C1—C2—C3	−178.7 (2)	C15—C10—C11—C12	0.1 (3)
N1—C1—C2—C7	2.6 (3)	C9—C10—C15—C14	−178.2 (2)
C6—C1—C2—C3	−2.0 (3)	C11—C10—C15—C14	0.2 (3)
C6—C1—C2—C7	179.3 (2)	C10—C11—C12—C13	−0.5 (4)
N1—C1—C6—C5	178.8 (2)	C11—C12—C13—N2	−178.3 (2)
C2—C1—C6—C5	2.3 (4)	C11—C12—C13—C14	0.8 (4)
C1—C2—C3—C4	0.8 (4)	N2—C13—C14—C15	178.6 (2)
C1—C2—C3—C8	−180.0 (3)	C12—C13—C14—C15	−0.5 (3)
C7—C2—C3—C4	179.4 (2)	C13—C14—C15—C10	0.0 (3)
C7—C2—C3—C8	−1.3 (4)

Experimental details

Crystal data
Chemical formula	C₁₅H₁₄N₂O₂
M_r	254.28
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	7.1969 (5), 11.8023 (7), 15.3721 (8)
V (Å³)	1305.71 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.32 × 0.14 × 0.14

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.986, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	13172, 1917, 1253
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.674

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.111, 1.02
No. of reflections	1917
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.14

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Acknowledgements

The authors acknowledge the provision of funds for the purchase of diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan.

References

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