N-[(E)-4-Bromo­benzyl­idene]-2,3-di­methyl­aniline

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

doi:10.1107/S1600536813008088

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 5| May 2013| Page o630

https://doi.org/10.1107/S1600536813008088

Open

access

N-[(E)-4-Bromobenzylidene]-2,3-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 22 March 2013; accepted 24 March 2013; online 5 April 2013)

The title compound, C₁₅H₁₄BrN, has an E conformation about the C=N bond and the dihedral angle between the benzene rings is 50.7 (2)°. In the crystal, molecules are linked via C—H⋯π interactions, forming columns propagating along [010].

Related literature

Schiff base derivativies have many pharmaceutical activities. For their antifungal effects, 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
Monoclinic, P 2₁ /n
a = 12.945 (9) Å
b = 7.857 (5) Å
c = 14.497 (10) Å
β = 113.384 (8)°
V = 1353.3 (16) Å³
Z = 4
Mo Kα radiation
μ = 3.02 mm⁻¹
T = 296 K
0.25 × 0.20 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.519, T_max = 0.598
5865 measured reflections
2525 independent reflections
1154 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.112
S = 0.94
2525 reflections
157 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯Cg2ⁱ	0.93	2.99	3.830 (6)	151
C15—H15B⋯Cg1ⁱⁱ	0.96	2.99	3.781 (6)	140
Symmetry codes: (i) -x, -y+2, -z+1; (ii) -x, -y+1, -z+1.

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/S1600536813008088/su2578sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813008088/su2578Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813008088/su2578Isup3.cml

checkCIF report

Comment top

Schiff base ligands have received much more attention during the 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), and antibacterial activities (Shi et al., 2010). We report herein on the crystal structure of a new 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 molecule has an E conformation about the C7═N1 bond and is twisted with the dihedral angle between the two aromatic rings being 50.7 (2) °.

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

Related literature top

Schiff base derivativies have many pharmaceutical activities. For their antifungal effects, 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), 2,3-dimethylaniline (5 mmol) and methanol (50 ml) was refluxed for 6 h. The mixture was then allowed to cool and filtered. Recrystallization of the crude product from methanol yielded yellow block-like crystals.

Structure description top

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

Schiff base derivativies have many pharmaceutical activities. For their antifungal effects, 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]-2,3-dimethylaniline top

Crystal data top

C₁₅H₁₄BrN	F(000) = 584
M_r = 288.18	D_x = 1.414 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2505 reflections
a = 12.945 (9) Å	θ = 2.7–25.5°
b = 7.857 (5) Å	µ = 3.02 mm⁻¹
c = 14.497 (10) Å	T = 296 K
β = 113.384 (8)°	Block, yellow
V = 1353.3 (16) Å³	0.25 × 0.20 × 0.19 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2525 independent reflections
Radiation source: fine-focus sealed tube	1154 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
φ and ω scans	θ_max = 25.5°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→10
T_min = 0.519, T_max = 0.598	k = −9→7
5865 measured reflections	l = −15→17

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)] = 0.042	H-atom parameters constrained
wR(F²) = 0.112	w = 1/[σ²(F_o²) + (0.0477P)²] where P = (F_o² + 2F_c²)/3
S = 0.94	(Δ/σ)_max < 0.001
2525 reflections	Δρ_max = 0.35 e Å⁻³
157 parameters	Δρ_min = −0.25 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: 0.0298 (19)

Crystal data top

C₁₅H₁₄BrN	V = 1353.3 (16) Å³
M_r = 288.18	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.945 (9) Å	µ = 3.02 mm⁻¹
b = 7.857 (5) Å	T = 296 K
c = 14.497 (10) Å	0.25 × 0.20 × 0.19 mm
β = 113.384 (8)°

Data collection top

Bruker APEXII CCD diffractometer	2525 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1154 reflections with I > 2σ(I)
T_min = 0.519, T_max = 0.598	R_int = 0.058
5865 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 0.94	Δρ_max = 0.35 e Å⁻³
2525 reflections	Δρ_min = −0.25 e Å⁻³
157 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
Br1	0.07853 (5)	0.88838 (7)	0.11686 (4)	0.0919 (4)
C1	0.0611 (4)	0.8732 (5)	0.3942 (3)	0.0581 (13)
H1	0.0091	0.9056	0.4205	0.070*
C2	0.0362 (4)	0.8999 (5)	0.2939 (3)	0.0643 (13)
H2	−0.0315	0.9504	0.2529	0.077*
C3	0.1122 (5)	0.8513 (5)	0.2554 (3)	0.0547 (12)
C4	0.2111 (4)	0.7767 (7)	0.3137 (4)	0.0736 (15)
H4	0.2616	0.7431	0.2860	0.088*
C5	0.2363 (4)	0.7508 (6)	0.4154 (3)	0.0682 (15)
H5	0.3042	0.7002	0.4557	0.082*
C6	0.1617 (4)	0.7992 (5)	0.4572 (3)	0.0477 (11)
C7	0.1882 (4)	0.7675 (5)	0.5637 (3)	0.0513 (12)
H7	0.2592	0.7258	0.6036	0.062*
C8	0.1554 (4)	0.7691 (5)	0.7095 (3)	0.0434 (11)
C9	0.2578 (4)	0.8290 (6)	0.7761 (3)	0.0582 (13)
H9	0.3060	0.8842	0.7525	0.070*
C10	0.2887 (4)	0.8071 (7)	0.8781 (3)	0.0713 (14)
H10	0.3586	0.8452	0.9231	0.086*
C11	0.2169 (4)	0.7295 (6)	0.9130 (3)	0.0602 (13)
H11	0.2382	0.7163	0.9818	0.072*
C12	0.1130 (4)	0.6702 (5)	0.8474 (3)	0.0500 (12)
C13	0.0802 (3)	0.6918 (5)	0.7437 (3)	0.0449 (11)
C14	0.0371 (4)	0.5812 (6)	0.8890 (4)	0.0776 (16)
H14A	0.0750	0.5718	0.9607	0.116*
H14B	0.0191	0.4695	0.8602	0.116*
H14C	−0.0309	0.6457	0.8726	0.116*
C15	−0.0326 (4)	0.6292 (6)	0.6700 (3)	0.0758 (15)
H15A	−0.0869	0.6384	0.6995	0.114*
H15B	−0.0262	0.5124	0.6535	0.114*
H15C	−0.0564	0.6970	0.6100	0.114*
N1	0.1199 (3)	0.7938 (4)	0.6039 (2)	0.0501 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.1350 (6)	0.0914 (5)	0.0529 (3)	−0.0264 (4)	0.0410 (3)	0.0038 (3)
C1	0.064 (3)	0.061 (3)	0.052 (3)	0.015 (3)	0.025 (3)	0.005 (2)
C2	0.075 (4)	0.054 (3)	0.061 (3)	0.021 (3)	0.024 (3)	0.008 (3)
C3	0.069 (3)	0.050 (3)	0.044 (2)	−0.006 (3)	0.023 (3)	0.005 (2)
C4	0.069 (4)	0.104 (4)	0.061 (3)	−0.012 (3)	0.039 (3)	−0.015 (3)
C5	0.051 (3)	0.095 (4)	0.060 (3)	0.013 (3)	0.024 (3)	0.000 (3)
C6	0.051 (3)	0.047 (3)	0.048 (3)	−0.001 (2)	0.023 (2)	−0.001 (2)
C7	0.058 (3)	0.047 (3)	0.050 (3)	0.002 (2)	0.022 (3)	0.000 (2)
C8	0.047 (3)	0.034 (3)	0.049 (3)	0.004 (2)	0.018 (2)	0.001 (2)
C9	0.062 (3)	0.055 (3)	0.063 (3)	−0.015 (3)	0.030 (3)	−0.005 (2)
C10	0.065 (3)	0.089 (4)	0.057 (3)	−0.024 (3)	0.021 (3)	−0.020 (3)
C11	0.072 (4)	0.066 (4)	0.044 (3)	−0.004 (3)	0.024 (3)	−0.002 (2)
C12	0.062 (3)	0.043 (3)	0.053 (3)	0.002 (2)	0.032 (3)	0.003 (2)
C13	0.051 (3)	0.037 (3)	0.046 (2)	0.002 (2)	0.018 (2)	−0.005 (2)
C14	0.093 (4)	0.080 (4)	0.070 (3)	−0.008 (3)	0.042 (3)	0.009 (3)
C15	0.059 (3)	0.100 (4)	0.062 (3)	−0.015 (3)	0.018 (3)	−0.005 (3)
N1	0.061 (2)	0.048 (2)	0.048 (2)	0.004 (2)	0.028 (2)	0.0032 (17)

Geometric parameters (Å, º) top

Br1—C3	1.901 (4)	C8—N1	1.426 (5)
C1—C2	1.375 (6)	C9—C10	1.380 (6)
C1—C6	1.387 (5)	C9—H9	0.9300
C1—H1	0.9300	C10—C11	1.366 (6)
C2—C3	1.365 (6)	C10—H10	0.9300
C2—H2	0.9300	C11—C12	1.383 (6)
C3—C4	1.355 (6)	C11—H11	0.9300
C4—C5	1.393 (6)	C12—C13	1.401 (5)
C4—H4	0.9300	C12—C14	1.513 (6)
C5—C6	1.382 (5)	C13—C15	1.509 (6)
C5—H5	0.9300	C14—H14A	0.9600
C6—C7	1.464 (5)	C14—H14B	0.9600
C7—N1	1.253 (5)	C14—H14C	0.9600
C7—H7	0.9300	C15—H15A	0.9600
C8—C9	1.377 (5)	C15—H15B	0.9600
C8—C13	1.395 (5)	C15—H15C	0.9600

C2—C1—C6	121.6 (4)	C10—C9—H9	120.1
C2—C1—H1	119.2	C11—C10—C9	120.1 (4)
C6—C1—H1	119.2	C11—C10—H10	120.0
C3—C2—C1	119.1 (4)	C9—C10—H10	120.0
C3—C2—H2	120.5	C10—C11—C12	121.0 (4)
C1—C2—H2	120.5	C10—C11—H11	119.5
C4—C3—C2	121.5 (4)	C12—C11—H11	119.5
C4—C3—Br1	119.2 (4)	C11—C12—C13	119.6 (4)
C2—C3—Br1	119.3 (4)	C11—C12—C14	119.3 (4)
C3—C4—C5	119.3 (4)	C13—C12—C14	121.0 (4)
C3—C4—H4	120.4	C8—C13—C12	118.5 (4)
C5—C4—H4	120.4	C8—C13—C15	120.3 (4)
C6—C5—C4	120.9 (4)	C12—C13—C15	121.1 (4)
C6—C5—H5	119.6	C12—C14—H14A	109.5
C4—C5—H5	119.6	C12—C14—H14B	109.5
C5—C6—C1	117.7 (4)	H14A—C14—H14B	109.5
C5—C6—C7	120.2 (4)	C12—C14—H14C	109.5
C1—C6—C7	122.1 (4)	H14A—C14—H14C	109.5
N1—C7—C6	123.3 (4)	H14B—C14—H14C	109.5
N1—C7—H7	118.4	C13—C15—H15A	109.5
C6—C7—H7	118.4	C13—C15—H15B	109.5
C9—C8—C13	120.8 (4)	H15A—C15—H15B	109.5
C9—C8—N1	121.1 (4)	C13—C15—H15C	109.5
C13—C8—N1	117.9 (4)	H15A—C15—H15C	109.5
C8—C9—C10	119.9 (4)	H15B—C15—H15C	109.5
C8—C9—H9	120.1	C7—N1—C8	119.4 (4)

C6—C1—C2—C3	0.4 (7)	C9—C10—C11—C12	0.6 (8)
C1—C2—C3—C4	0.4 (7)	C10—C11—C12—C13	−0.8 (7)
C1—C2—C3—Br1	−179.8 (3)	C10—C11—C12—C14	178.5 (4)
C2—C3—C4—C5	−0.7 (7)	C9—C8—C13—C12	−2.6 (6)
Br1—C3—C4—C5	179.5 (4)	N1—C8—C13—C12	−178.6 (4)
C3—C4—C5—C6	0.3 (7)	C9—C8—C13—C15	179.0 (4)
C4—C5—C6—C1	0.4 (7)	N1—C8—C13—C15	3.0 (6)
C4—C5—C6—C7	178.6 (4)	C11—C12—C13—C8	1.7 (6)
C2—C1—C6—C5	−0.8 (7)	C14—C12—C13—C8	−177.6 (4)
C2—C1—C6—C7	−178.9 (4)	C11—C12—C13—C15	−179.9 (4)
C5—C6—C7—N1	−173.1 (4)	C14—C12—C13—C15	0.9 (6)
C1—C6—C7—N1	4.9 (7)	C6—C7—N1—C8	−176.2 (4)
C13—C8—C9—C10	2.5 (6)	C9—C8—N1—C7	44.6 (6)
N1—C8—C9—C10	178.4 (4)	C13—C8—N1—C7	−139.3 (4)
C8—C9—C10—C11	−1.5 (7)

Hydrogen-bond geometry (Å, º) top

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

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cg2ⁱ	0.93	2.99	3.830 (6)	151
C15—H15B···Cg1ⁱⁱ	0.96	2.99	3.781 (6)	140

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₄BrN
M_r	288.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	12.945 (9), 7.857 (5), 14.497 (10)
β (°)	113.384 (8)
V (Å³)	1353.3 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.02
Crystal size (mm)	0.25 × 0.20 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.519, 0.598
No. of measured, independent and observed [I > 2σ(I)] reflections	5865, 2525, 1154
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.112, 0.94
No. of reflections	2525
No. of parameters	157
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.25

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 C8–C13 and C1–C6 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cg2ⁱ	0.93	2.99	3.830 (6)	151
C15—H15B···Cg1ⁱⁱ	0.96	2.99	3.781 (6)	140

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

Acknowledgements

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

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Aziz, A. A. A., Salem, A. N. M., Sayed, M. A. & Aboaly, M. M. (2010). J. Mol. Struct. 1010, 130–138. Google Scholar
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Guo, Y., Pan, M.-X., Xiang, H., Liu, W.-H. & Song, Z.-C. (2011). Acta Cryst. E67, o1999. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lu, J., Li, C., Chai, Y.-F., Yang, D.-Y. & Sun, C.-R. (2012). Bioorg. Med. Chem. Lett. 22, 5744–5747. Web of Science CrossRef CAS PubMed Google Scholar
Schmidt, M. F., El-Dahshan, A., Keller, S. & Rademann, J. (2009). Angew. Chem. Int. Ed. 48, 6346–6349. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Gottingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shi, L., Fang, R.-Q., Zhu, Z.-W., Yang, Y., Cheng, K., Zhu, H.-L. & Zhong, W.-Q. (2010). Eur. J. Med. Chem. 45, 4358–4364. Web of Science CrossRef CAS PubMed Google Scholar
Sun, L.-X., Yu, Y.-D. & Wei, G.-Y. (2011a). Acta Cryst. E67, o1564. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sun, L.-X., Yu, Y.-D. & Wei, G.-Y. (2011b). Acta Cryst. E67, o1578. Web of Science CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 5| May 2013| Page o630

https://doi.org/10.1107/S1600536813008088

Open

access