(E)-N-[(6-Bromo­pyridin-2-yl)methyl­idene]-4-methyl­aniline

Abstract

The title compound, C₁₃H₁₁BrN₂, a Schiff base obtained from 6-bromo­picolinaldehyde and p-toluidine, has an E configuration about the C=N bond. The dihedral angle between the benzene and pyridine rings is 30.4 (1)°.

Related literature

For Schiff base complexes with transition metals, see: Burkhardt & Plass (2008 ▶); Keypour et al. (2011 ▶); Tarafder et al. (2002 ▶). For their complexing ability towards toxic metals, see: Kocyigit et al. (2010 ▶);

Experimental

Crystal data

• C₁₃H₁₁BrN₂

• M _r = 275.15

• Orthorhombic,

• a = 13.542 (3) Å

• b = 6.1544 (15) Å

• c = 27.620 (7) Å

• V = 2301.9 (10) ų

• Z = 8

• Mo Kα radiation

• μ = 3.54 mm⁻¹

• T = 113 K

• 0.20 × 0.08 × 0.04 mm

Data collection

• Rigaku Saturn724 CCD diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002 ▶) T _min = 0.538, T _max = 0.871

• 21379 measured reflections

• 2750 independent reflections

• 2251 reflections with I > 2σ(I)

• R _int = 0.044

Refinement

• R[F ² > 2σ(F ²)] = 0.040

• wR(F ²) = 0.104

• S = 1.08

• 2750 reflections

• 146 parameters

• H-atom parameters constrained

• Δρ_max = 0.91 e Å⁻³

• Δρ_min = −0.66 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2002 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Crystal Impact, 2009 ▶); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2006 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811031825/ld2022Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

Schiff bases have played an important role in the development of coordination chemistry as they readily form stable complexes with most of the transition metals (Burkhardt & Plass, 2008; Keypour, et al., 2011; Tarafder, et al., 2002). They show important properties, e.g. an ability to reversibly bind oxygen, catalytic activity in hydrogenation of olefins, transfer of amino group, photochromic properties and complexing ability towards toxic metals (Kocyigit et al., 2010). In this paper, the structure of the new Schiff base derived from condensation of 6-bromopicolinaldehyde with p-toluidine is reported. The molecule of the title compound, Fig. 1, possesses an E configuration about the C6=N2 bond.

Experimental

The solution of 6-bromopicolinaldehyde and p-toluidine in methanol was refluxed for 2 h, and then the crude product was isolated by filtration and recrystallized from methanol to yield yellowish title compound. Finally, the title compound was dissolved in a small amount of methanol and the solution was kept for 5 days at ambient temperature to give rise to yellowish block-like crystals on slowly evaporating the solvent.

Refinement

The hydrogen atoms were positioned geometrically (C—H=0.93–0.98 Å) and refined using a riding model, with U_iso(H)=1.2 or 1.5U_eq(C) (methyl group). The methyl group position was rotationally optimized (AFIX 137)

Figures

Fig. 1.

The molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.

Crystal data

C13H11BrN2	Dx = 1.588 Mg m−3
Mr = 275.15	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 6762 reflections
a = 13.542 (3) Å	θ = 2.1–28.0°
b = 6.1544 (15) Å	µ = 3.54 mm−1
c = 27.620 (7) Å	T = 113 K
V = 2301.9 (10) Å3	Prism, colorless
Z = 8	0.20 × 0.08 × 0.04 mm
F(000) = 1104

Data collection

Rigaku Saturn724 CCD diffractometer	2750 independent reflections
Radiation source: rotating anode	2251 reflections with I > 2σ(I)
multilayer	Rint = 0.044
Detector resolution: 14.22 pixels mm-1	θmax = 27.9°, θmin = 2.1°
ω and φ scans	h = −17→17
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002)	k = −7→8
Tmin = 0.538, Tmax = 0.871	l = −36→36
21379 measured reflections

Refinement

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.0529P)2] where P = (Fo2 + 2Fc2)/3
2750 reflections	(Δ/σ)max = 0.002
146 parameters	Δρmax = 0.91 e Å−3
0 restraints	Δρmin = −0.66 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.38420 (2)	0.10293 (5)	0.750452 (7)	0.03018 (13)
N1	0.38367 (13)	0.1724 (3)	0.65201 (6)	0.0218 (4)
N2	0.38262 (12)	0.2660 (3)	0.52490 (7)	0.0219 (4)
C1	0.37666 (14)	0.2783 (4)	0.69322 (8)	0.0215 (5)
C2	0.36569 (15)	0.5001 (4)	0.69829 (8)	0.0247 (5)
H2	0.3618	0.5667	0.7293	0.030*
C3	0.36066 (16)	0.6208 (4)	0.65619 (9)	0.0250 (5)
H3	0.3531	0.7742	0.6576	0.030*
C4	0.36681 (14)	0.5157 (4)	0.61200 (8)	0.0224 (5)
H4	0.3629	0.5959	0.5827	0.027*
C5	0.37868 (14)	0.2921 (4)	0.61109 (8)	0.0209 (5)
C6	0.38647 (15)	0.1703 (4)	0.56563 (8)	0.0221 (5)
H6	0.3945	0.0171	0.5666	0.027*
C7	0.38278 (14)	0.1445 (4)	0.48137 (8)	0.0219 (5)
C8	0.41670 (16)	0.2481 (4)	0.43969 (7)	0.0234 (5)
H8	0.4428	0.3912	0.4417	0.028*
C9	0.41266 (17)	0.1437 (4)	0.39534 (8)	0.0272 (5)
H9	0.4372	0.2151	0.3673	0.033*
C10	0.37303 (14)	−0.0649 (4)	0.39118 (9)	0.0228 (5)
C11	0.33938 (16)	−0.1659 (4)	0.43272 (8)	0.0246 (5)
H11	0.3123	−0.3079	0.4305	0.030*
C12	0.34413 (15)	−0.0651 (4)	0.47738 (8)	0.0224 (5)
H12	0.3211	−0.1387	0.5054	0.027*
C14	0.36452 (17)	−0.1756 (5)	0.34244 (9)	0.0332 (6)
H14A	0.2966	−0.1623	0.3305	0.050*
H14B	0.3816	−0.3296	0.3458	0.050*
H14C	0.4098	−0.1065	0.3195	0.050*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br1	0.0412 (2)	0.0310 (2)	0.01834 (17)	0.00145 (10)	−0.00218 (9)	0.00303 (9)
N1	0.0239 (10)	0.0212 (11)	0.0203 (10)	0.0009 (7)	−0.0008 (7)	0.0006 (8)
N2	0.0218 (10)	0.0232 (12)	0.0207 (10)	−0.0010 (8)	0.0013 (7)	−0.0021 (8)
C1	0.0207 (11)	0.0236 (13)	0.0202 (11)	−0.0007 (9)	−0.0009 (8)	0.0007 (9)
C2	0.0257 (12)	0.0267 (14)	0.0217 (12)	−0.0008 (9)	0.0000 (9)	−0.0063 (10)
C3	0.0302 (13)	0.0200 (13)	0.0247 (13)	0.0017 (9)	−0.0008 (9)	−0.0018 (10)
C4	0.0251 (11)	0.0218 (14)	0.0203 (12)	0.0004 (9)	0.0011 (8)	0.0012 (10)
C5	0.0180 (11)	0.0243 (13)	0.0203 (11)	0.0000 (9)	0.0000 (7)	0.0003 (10)
C6	0.0234 (11)	0.0196 (13)	0.0234 (12)	0.0022 (9)	−0.0011 (8)	−0.0026 (9)
C7	0.0177 (11)	0.0277 (14)	0.0202 (12)	0.0034 (9)	−0.0005 (8)	−0.0002 (9)
C8	0.0229 (11)	0.0228 (13)	0.0246 (11)	−0.0002 (9)	0.0027 (9)	0.0034 (9)
C9	0.0245 (12)	0.0361 (15)	0.0209 (11)	−0.0004 (10)	0.0042 (9)	0.0034 (10)
C10	0.0182 (11)	0.0300 (14)	0.0201 (12)	0.0019 (9)	−0.0004 (8)	−0.0048 (10)
C11	0.0223 (11)	0.0236 (13)	0.0279 (12)	−0.0002 (9)	−0.0030 (9)	−0.0026 (9)
C12	0.0226 (11)	0.0231 (13)	0.0214 (11)	−0.0010 (9)	−0.0011 (8)	0.0028 (9)
C14	0.0325 (14)	0.0452 (17)	0.0220 (13)	−0.0019 (11)	−0.0001 (9)	−0.0088 (12)

Geometric parameters (Å, °)

Br1—C1	1.917 (2)	C7—C8	1.394 (3)
N1—C1	1.316 (3)	C7—C12	1.397 (3)
N1—C5	1.351 (3)	C8—C9	1.384 (3)
N2—C6	1.271 (3)	C8—H8	0.9500
N2—C7	1.416 (3)	C9—C10	1.397 (3)
C1—C2	1.380 (3)	C9—H9	0.9500
C2—C3	1.382 (3)	C10—C11	1.382 (3)
C2—H2	0.9500	C10—C14	1.513 (3)
C3—C4	1.384 (3)	C11—C12	1.382 (3)
C3—H3	0.9500	C11—H11	0.9500
C4—C5	1.386 (4)	C12—H12	0.9500
C4—H4	0.9500	C14—H14A	0.9800
C5—C6	1.466 (3)	C14—H14B	0.9800
C6—H6	0.9500	C14—H14C	0.9800
C1—N1—C5	116.7 (2)	C12—C7—N2	123.7 (2)
C6—N2—C7	120.5 (2)	C9—C8—C7	120.4 (2)
N1—C1—C2	125.9 (2)	C9—C8—H8	119.8
N1—C1—Br1	115.50 (17)	C7—C8—H8	119.8
C2—C1—Br1	118.63 (17)	C8—C9—C10	121.0 (2)
C1—C2—C3	116.8 (2)	C8—C9—H9	119.5
C1—C2—H2	121.6	C10—C9—H9	119.5
C3—C2—H2	121.6	C11—C10—C9	118.2 (2)
C2—C3—C4	119.2 (2)	C11—C10—C14	120.8 (2)
C2—C3—H3	120.4	C9—C10—C14	121.1 (2)
C4—C3—H3	120.4	C10—C11—C12	121.6 (2)
C3—C4—C5	119.1 (2)	C10—C11—H11	119.2
C3—C4—H4	120.4	C12—C11—H11	119.2
C5—C4—H4	120.4	C11—C12—C7	120.1 (2)
N1—C5—C4	122.2 (2)	C11—C12—H12	119.9
N1—C5—C6	115.7 (2)	C7—C12—H12	119.9
C4—C5—C6	122.1 (2)	C10—C14—H14A	109.5
N2—C6—C5	121.2 (2)	C10—C14—H14B	109.5
N2—C6—H6	119.4	H14A—C14—H14B	109.5
C5—C6—H6	119.4	C10—C14—H14C	109.5
C8—C7—C12	118.7 (2)	H14A—C14—H14C	109.5
C8—C7—N2	117.4 (2)	H14B—C14—H14C	109.5
C5—N1—C1—C2	−0.7 (3)	C6—N2—C7—C8	−155.5 (2)
C5—N1—C1—Br1	−179.94 (14)	C6—N2—C7—C12	29.6 (3)
N1—C1—C2—C3	0.7 (3)	C12—C7—C8—C9	−0.5 (3)
Br1—C1—C2—C3	179.93 (15)	N2—C7—C8—C9	−175.66 (19)
C1—C2—C3—C4	−0.1 (3)	C7—C8—C9—C10	1.2 (3)
C2—C3—C4—C5	−0.5 (3)	C8—C9—C10—C11	−1.0 (3)
C1—N1—C5—C4	0.0 (3)	C8—C9—C10—C14	177.4 (2)
C1—N1—C5—C6	−179.88 (17)	C9—C10—C11—C12	0.1 (3)
C3—C4—C5—N1	0.6 (3)	C14—C10—C11—C12	−178.3 (2)
C3—C4—C5—C6	−179.54 (19)	C10—C11—C12—C7	0.6 (3)
C7—N2—C6—C5	−175.22 (17)	C8—C7—C12—C11	−0.4 (3)
N1—C5—C6—N2	179.92 (19)	N2—C7—C12—C11	174.45 (19)
C4—C5—C6—N2	0.0 (3)