N-[(E)-4-Bromo­benzyl­idene]-3,4-di­methyl­aniline

Sun, L.-X.; Zhu, L.-Z.; Wang, J.-K.

doi:10.1107/S1600536813008143

organic compounds

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N-[(E)-4-Bromobenzylidene]-3,4-dimethylaniline

Li-Xia Sun,^a ^* Ling-Zhi Zhu ^a and Jun-Kai Wang ^a

^aCollege of Materials Science & Engineering, China Jiliang University, Hangzhou 310018, People's Republic of China
^*Correspondence e-mail: nanocrystal11@163.com

(Received 24 March 2013; accepted 25 March 2013; online 5 April 2013)

In the title compound, C₁₅H₁₄BrN, the dihedral angle between the benzene rings is 6.4 (2)° and the molecule has an E conformation about the C=N bond. In the crystal, molecules are linked by C—H⋯π interactions, forming two-dimensional networks lying parallel to (001).

Related literature

Schiff bases derivatives have many pharmaceutical activities. For their antifungal properties, see: Aziz et al. (2010 ), for their radical scavenging activity, see: Lu et al. (2012 ), for their inhibition of enzyme activity, see: Schmidt et al. (2009 ) and for their antibacterial activity, see: Shi et al. (2010 ). For related structures, see: Sun et al. (2011a ,b ); Guo et al. (2011 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₅H₁₄BrN
M_r = 288.18
Orthorhombic, P b c n
a = 14.868 (7) Å
b = 6.161 (3) Å
c = 28.609 (13) Å
V = 2621 (2) Å³
Z = 8
Mo Kα radiation
μ = 3.11 mm⁻¹
T = 296 K
0.22 × 0.19 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.547, T_max = 0.670
17312 measured reflections
2445 independent reflections
1438 reflections with I > 2σ(I)
R_int = 0.090

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.148
S = 1.03
2445 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C1–C6 and C8–C13 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯Cg1ⁱ	0.93	2.99	3.773 (5)	143
C12—H12⋯Cg2ⁱⁱ	0.93	2.77	3.507 (5)	137
Symmetry codes: (i) $[-x, y, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); 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: https://doi.org/10.1107/S1600536813008143/su2579sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813008143/su2579Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813008143/su2579Isup3.cml

checkCIF report

Comment top

Schiff base ligands have received much attention during past years. They have many pharmaceutical activities, such as antifungal effects (Aziz et al., 2010), radical scavenging activity (Lu et al., 2012), inhibition of enzyme activity (Schmidt et al., 2009), antibacterial activities (Shi et al., 2010). We report herein on the crystal structure of the new title Schiff base compound.

In the title molecule, Fig. 1, the bond lengths (Allen et al., 1987) and angles are normal and comparable to the values observed in similar compounds (Sun et al., 2011a,b; Guo et al., 2011). The dihedral angle between the two aromatic rings in the Schiff base molecule is 6.4 (2) °, indicating that two these rings are approximatively coplanar. The molecule has an E conformation about the C7═N1 bond.

In the crystal, molecules are linked by C-H···π interactions (Table 1).

Related literature top

Schiff bases derivatives have many pharmaceutical activities. For their antifungal properties, see: Aziz et al. (2010), for their radical scavenging activity, see: Lu et al. (2012), for their inhibition of enzyme activity, see: Schmidt et al. (2009) and for their antibacterial activity, see: Shi et al. (2010). For related structures, see: Sun et al. (2011a,b); Guo et al. (2011). For standard bond lengths, see: Allen et al. (1987).

Experimental top

A mixture of 4-bromobenzaldehyde (5 mmol), 3,4-dimethylaniline (5 mmol) and methanol (50 ml) was refluxed for 6 h. It was then allowed to cool and was filtered. Recrystallization of the crude product from methanol yielded yellow block-like crystals.

Structure description top

In the crystal, molecules are linked by C-H···π interactions (Table 1).

Schiff bases derivatives have many pharmaceutical activities. For their antifungal properties, see: Aziz et al. (2010), for their radical scavenging activity, see: Lu et al. (2012), for their inhibition of enzyme activity, see: Schmidt et al. (2009) and for their antibacterial activity, see: Shi et al. (2010). For related structures, see: Sun et al. (2011a,b); Guo et al. (2011). For standard bond lengths, see: Allen et al. (1987).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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 the title molecule, with atom labelling. The displacement ellipsoids are drawn at the 50% probability level.

N-[(E)-4-Bromobenzylidene]-3,4-dimethylaniline top

Crystal data top

C₁₅H₁₄BrN	F(000) = 1168
M_r = 288.18	D_x = 1.461 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 2443 reflections
a = 14.868 (7) Å	θ = 2.7–25.5°
b = 6.161 (3) Å	µ = 3.11 mm⁻¹
c = 28.609 (13) Å	T = 296 K
V = 2621 (2) Å³	Block, yellow
Z = 8	0.22 × 0.19 × 0.14 mm

Data collection top

Bruker APEXII CCD diffractometer	2445 independent reflections
Radiation source: fine-focus sealed tube	1438 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.090
φ and ω scans	θ_max = 25.5°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→18
T_min = 0.547, T_max = 0.670	k = −7→7
17312 measured reflections	l = −32→34

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.148	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0449P)² + 6.739P] where P = (F_o² + 2F_c²)/3
2445 reflections	(Δ/σ)_max = 0.001
156 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

C₁₅H₁₄BrN	V = 2621 (2) Å³
M_r = 288.18	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 14.868 (7) Å	µ = 3.11 mm⁻¹
b = 6.161 (3) Å	T = 296 K
c = 28.609 (13) Å	0.22 × 0.19 × 0.14 mm

Data collection top

Bruker APEXII CCD diffractometer	2445 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1438 reflections with I > 2σ(I)
T_min = 0.547, T_max = 0.670	R_int = 0.090
17312 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.148	H-atom parameters constrained
S = 1.03	Δρ_max = 0.55 e Å⁻³
2445 reflections	Δρ_min = −0.56 e Å⁻³
156 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 esds 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
Br1	0.12941 (5)	1.15486 (14)	0.55818 (2)	0.0821 (3)
N1	0.1277 (3)	0.5957 (7)	0.76719 (15)	0.0460 (16)
C1	0.1549 (3)	0.7560 (9)	0.6734 (2)	0.0507 (19)
C2	0.1579 (4)	0.8357 (11)	0.6281 (2)	0.058 (2)
C3	0.1256 (3)	1.0405 (10)	0.62021 (17)	0.0460 (19)
C4	0.0911 (4)	1.1681 (10)	0.65516 (19)	0.0533 (19)
C5	0.0907 (4)	1.0843 (9)	0.70019 (19)	0.0523 (19)
C6	0.1210 (3)	0.8791 (9)	0.70960 (18)	0.0417 (17)
C7	0.1164 (3)	0.7919 (9)	0.75771 (19)	0.0470 (19)
C8	0.1253 (3)	0.5192 (8)	0.81399 (16)	0.0387 (16)
C9	0.0878 (3)	0.6300 (8)	0.85173 (18)	0.0430 (17)
C10	0.0929 (3)	0.5490 (9)	0.89694 (18)	0.0440 (17)
C11	0.1357 (3)	0.3504 (9)	0.90483 (19)	0.0477 (17)
C12	0.1714 (3)	0.2393 (9)	0.8668 (2)	0.0477 (19)
C13	0.1656 (3)	0.3213 (8)	0.8222 (2)	0.0443 (17)
C14	0.0523 (5)	0.6765 (11)	0.93710 (19)	0.072 (3)
C15	0.1459 (4)	0.2609 (11)	0.9540 (2)	0.070 (2)
H1	0.17610	0.61680	0.67950	0.0610*
H2	0.18130	0.75260	0.60390	0.0690*
H4	0.06880	1.30610	0.64890	0.0640*
H5	0.06940	1.16980	0.72460	0.0630*
H7	0.10450	0.88760	0.78210	0.0560*
H9	0.05860	0.76120	0.84650	0.0520*
H12	0.19980	0.10660	0.87160	0.0570*
H13	0.18910	0.24250	0.79730	0.0530*
H14A	0.00220	0.59760	0.94980	0.1080*
H14B	0.03200	0.81510	0.92590	0.1080*
H14C	0.09680	0.69750	0.96100	0.1080*
H15A	0.17400	0.36800	0.97350	0.1050*
H15B	0.18250	0.13260	0.95320	0.1050*
H15C	0.08770	0.22570	0.96640	0.1050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0956 (5)	0.1062 (6)	0.0446 (4)	−0.0111 (5)	−0.0052 (3)	0.0232 (4)
N1	0.045 (2)	0.049 (3)	0.044 (3)	−0.001 (2)	−0.001 (2)	0.000 (2)
C1	0.049 (3)	0.044 (3)	0.059 (4)	0.009 (3)	−0.003 (3)	0.004 (3)
C2	0.059 (3)	0.067 (5)	0.047 (4)	0.007 (3)	0.000 (3)	−0.004 (3)
C3	0.044 (3)	0.063 (4)	0.031 (3)	−0.008 (3)	−0.007 (2)	0.009 (3)
C4	0.065 (3)	0.049 (4)	0.046 (3)	−0.002 (3)	−0.008 (3)	0.006 (3)
C5	0.060 (3)	0.052 (4)	0.045 (3)	0.001 (3)	0.001 (3)	−0.004 (3)
C6	0.041 (3)	0.043 (3)	0.041 (3)	−0.007 (3)	−0.001 (2)	−0.001 (2)
C7	0.052 (3)	0.047 (4)	0.042 (3)	−0.003 (3)	−0.007 (2)	−0.005 (3)
C8	0.037 (2)	0.041 (3)	0.038 (3)	−0.003 (3)	−0.002 (2)	0.000 (2)
C9	0.043 (3)	0.037 (3)	0.049 (3)	0.008 (2)	0.001 (2)	0.004 (3)
C10	0.041 (3)	0.042 (3)	0.049 (3)	−0.004 (3)	−0.003 (2)	−0.005 (3)
C11	0.046 (3)	0.047 (3)	0.050 (3)	−0.004 (3)	−0.004 (3)	0.006 (3)
C12	0.036 (3)	0.035 (3)	0.072 (4)	0.005 (2)	−0.002 (3)	0.006 (3)
C13	0.042 (3)	0.039 (3)	0.052 (3)	0.000 (2)	0.003 (2)	−0.003 (3)
C14	0.090 (5)	0.076 (5)	0.050 (4)	0.013 (4)	0.004 (3)	−0.008 (3)
C15	0.075 (4)	0.073 (4)	0.061 (4)	0.012 (3)	−0.002 (3)	0.017 (3)

Geometric parameters (Å, º) top

Br1—C3	1.910 (5)	C11—C15	1.519 (8)
N1—C7	1.250 (7)	C12—C13	1.375 (8)
N1—C8	1.420 (6)	C1—H1	0.9300
C1—C2	1.387 (8)	C2—H2	0.9300
C1—C6	1.379 (8)	C4—H4	0.9300
C2—C3	1.369 (9)	C5—H5	0.9300
C3—C4	1.372 (8)	C7—H7	0.9300
C4—C5	1.388 (8)	C9—H9	0.9300
C5—C6	1.369 (8)	C12—H12	0.9300
C6—C7	1.479 (8)	C13—H13	0.9300
C8—C9	1.394 (7)	C14—H14A	0.9600
C8—C13	1.379 (7)	C14—H14B	0.9600
C9—C10	1.388 (7)	C14—H14C	0.9600
C10—C11	1.398 (8)	C15—H15A	0.9600
C10—C14	1.517 (8)	C15—H15B	0.9600
C11—C12	1.391 (8)	C15—H15C	0.9600

C7—N1—C8	121.5 (5)	C1—C2—H2	121.00
C2—C1—C6	121.3 (5)	C3—C2—H2	121.00
C1—C2—C3	118.0 (5)	C3—C4—H4	121.00
Br1—C3—C2	118.9 (4)	C5—C4—H4	121.00
Br1—C3—C4	118.5 (4)	C4—C5—H5	119.00
C2—C3—C4	122.6 (5)	C6—C5—H5	119.00
C3—C4—C5	117.7 (5)	N1—C7—H7	118.00
C4—C5—C6	121.7 (5)	C6—C7—H7	118.00
C1—C6—C5	118.7 (5)	C8—C9—H9	119.00
C1—C6—C7	121.1 (5)	C10—C9—H9	119.00
C5—C6—C7	120.2 (5)	C11—C12—H12	119.00
N1—C7—C6	123.2 (5)	C13—C12—H12	119.00
N1—C8—C9	125.3 (4)	C8—C13—H13	120.00
N1—C8—C13	116.3 (4)	C12—C13—H13	120.00
C9—C8—C13	118.4 (5)	C10—C14—H14A	109.00
C8—C9—C10	121.6 (5)	C10—C14—H14B	109.00
C9—C10—C11	119.3 (5)	C10—C14—H14C	110.00
C9—C10—C14	119.9 (5)	H14A—C14—H14B	109.00
C11—C10—C14	120.8 (5)	H14A—C14—H14C	109.00
C10—C11—C12	118.6 (5)	H14B—C14—H14C	110.00
C10—C11—C15	120.9 (5)	C11—C15—H15A	109.00
C12—C11—C15	120.5 (5)	C11—C15—H15B	109.00
C11—C12—C13	121.4 (5)	C11—C15—H15C	110.00
C8—C13—C12	120.7 (5)	H15A—C15—H15B	109.00
C2—C1—H1	119.00	H15A—C15—H15C	109.00
C6—C1—H1	119.00	H15B—C15—H15C	109.00

C7—N1—C8—C13	−160.1 (5)	C5—C6—C7—N1	166.9 (5)
C8—N1—C7—C6	178.2 (4)	N1—C8—C9—C10	−176.2 (4)
C7—N1—C8—C9	18.2 (7)	C13—C8—C9—C10	2.1 (7)
C2—C1—C6—C5	−0.6 (8)	N1—C8—C13—C12	176.2 (4)
C6—C1—C2—C3	−0.4 (8)	C9—C8—C13—C12	−2.3 (7)
C2—C1—C6—C7	178.9 (5)	C8—C9—C10—C11	−0.8 (7)
C1—C2—C3—Br1	179.7 (4)	C8—C9—C10—C14	179.1 (5)
C1—C2—C3—C4	0.2 (8)	C9—C10—C11—C12	−0.4 (7)
Br1—C3—C4—C5	−178.6 (4)	C9—C10—C11—C15	177.5 (5)
C2—C3—C4—C5	0.9 (8)	C14—C10—C11—C12	179.7 (5)
C3—C4—C5—C6	−1.9 (9)	C14—C10—C11—C15	−2.4 (7)
C4—C5—C6—C1	1.8 (8)	C10—C11—C12—C13	0.3 (7)
C4—C5—C6—C7	−177.7 (5)	C15—C11—C12—C13	−177.7 (5)
C1—C6—C7—N1	−12.5 (7)	C11—C12—C13—C8	1.1 (7)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C1–C6 and C8–C13 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···Cg1ⁱ	0.93	2.99	3.773 (5)	143
C12—H12···Cg2ⁱⁱ	0.93	2.77	3.507 (5)	137

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₄BrN
M_r	288.18
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	296
a, b, c (Å)	14.868 (7), 6.161 (3), 28.609 (13)
V (Å³)	2621 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.11
Crystal size (mm)	0.22 × 0.19 × 0.14

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.547, 0.670
No. of measured, independent and observed [I > 2σ(I)] reflections	17312, 2445, 1438
R_int	0.090
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.148, 1.03
No. of reflections	2445
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.56

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C1–C6 and C8–C13 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···Cg1ⁱ	0.93	2.99	3.773 (5)	143
C12—H12···Cg2ⁱⁱ	0.93	2.77	3.507 (5)	137

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

Acknowledgements

This project was supported by the Natural Science Foundation of Zhejiang Province of China (grant No. LQ12E01007).

References

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