N-(4-Methyl-2-pyrid­yl)-p-toluidine

Fairuz, Z.A.; Aiyub, Z.; Abdullah, Z.; Ng, S.W.

doi:10.1107/S160053680905586X

organic compounds

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Volume 66| Part 2| February 2010| Page o371

https://doi.org/10.1107/S160053680905586X

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N-(4-Methyl-2-pyridyl)-p-toluidine

Zainal Abidin Fairuz,^a Zaharah Aiyub,^a Zanariah Abdullah ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 12 December 2009; accepted 30 December 2009; online 16 January 2010)

In the title compound, C₁₃H₁₄N₂, the dihedral angle between the aromatic rings is 48.1 (1)° and the bridging C—N—C bond angle is 127.24 (12)°. In the crystal, intermolecular N—H⋯N hydrogen bonding about a center of inversion generates a hydrogen-bonded dimer.

Related literature

For the structure of N-(2-pyridyl)-4-toluidine, see: Fairuz et al. (2008 ).

Experimental

Crystal data

C₁₃H₁₄N₂
M_r = 198.26
Monoclinic, P 2₁ /n
a = 10.9385 (11) Å
b = 7.5708 (8) Å
c = 13.4372 (14) Å
β = 95.246 (2)°
V = 1108.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 295 K
0.45 × 0.40 × 0.30 mm

Data collection

Bruker SMART APEX diffractometer
6758 measured reflections
2528 independent reflections
1797 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.142
S = 1.05
2528 reflections
143 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2ⁱ	0.87 (1)	2.18 (1)	3.041 (2)	170 (2)
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053680905586X/xu2710sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680905586X/xu2710Isup2.hkl

checkCIF report

Related literature top

For N-(2-pyridyl)-4-toluidine, see: Fairuz et al. (2008).

Experimental top

2-Chloro-4-methylpyridine (1 ml, 0.01 mol) and p-toluidine (1.2 g, 0.01 mol) were heated for 4 h. The product was dissolved in water and the solution extracted with ether. The ether extract was dried over sodium sulfate. Evaporation of the solvent gave large blocks of dark brown crystals. The crystals, when the outer parts were removed, were colorless.

Structure description top

For N-(2-pyridyl)-4-toluidine, see: Fairuz et al. (2008).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of the hydrogen-bonded C₁₃H₁₄N₂ at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. Dashed lines denote hydrogen bonds.

N-(4-Methyl-2-pyridyl)-p-toluidine top

Crystal data top

C₁₃H₁₄N₂	F(000) = 424
M_r = 198.26	D_x = 1.188 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2289 reflections
a = 10.9385 (11) Å	θ = 2.5–28.1°
b = 7.5708 (8) Å	µ = 0.07 mm⁻¹
c = 13.4372 (14) Å	T = 295 K
β = 95.246 (2)°	Irregular block, colorless
V = 1108.1 (2) Å³	0.45 × 0.40 × 0.30 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	1797 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.024
Graphite monochromator	θ_max = 27.5°, θ_min = 2.3°
ω scans	h = −14→13
6758 measured reflections	k = −9→9
2528 independent reflections	l = −14→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)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.142	w = 1/[σ²(F_o²) + (0.0692P)² + 0.1529P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
2528 reflections	Δρ_max = 0.17 e Å⁻³
143 parameters	Δρ_min = −0.13 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.044 (6)

Crystal data top

C₁₃H₁₄N₂	V = 1108.1 (2) Å³
M_r = 198.26	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.9385 (11) Å	µ = 0.07 mm⁻¹
b = 7.5708 (8) Å	T = 295 K
c = 13.4372 (14) Å	0.45 × 0.40 × 0.30 mm
β = 95.246 (2)°

Data collection top

Bruker SMART APEX diffractometer	1797 reflections with I > 2σ(I)
6758 measured reflections	R_int = 0.024
2528 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	1 restraint
wR(F²) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.17 e Å⁻³
2528 reflections	Δρ_min = −0.13 e Å⁻³
143 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.51269 (11)	0.54344 (19)	0.64065 (9)	0.0571 (4)
H1	0.4682 (13)	0.546 (2)	0.5832 (8)	0.063 (5)*
N2	0.66732 (12)	0.46482 (18)	0.54571 (9)	0.0554 (4)
C1	0.78715 (15)	0.4383 (2)	0.53779 (12)	0.0642 (5)
H1A	0.8107	0.4072	0.4754	0.077*
C2	0.87740 (14)	0.4535 (2)	0.61487 (13)	0.0619 (4)
H2	0.9588	0.4288	0.6052	0.074*
C3	0.84502 (13)	0.50645 (19)	0.70755 (11)	0.0490 (4)
C4	0.72299 (13)	0.53940 (19)	0.71698 (11)	0.0471 (3)
H4	0.6985	0.5788	0.7776	0.056*
C5	0.63566 (13)	0.51384 (18)	0.63552 (10)	0.0458 (3)
C6	0.93890 (14)	0.5264 (2)	0.79563 (12)	0.0607 (4)
H6A	0.9168	0.6239	0.8360	0.091*
H6B	1.0180	0.5479	0.7725	0.091*
H6C	0.9418	0.4201	0.8347	0.091*
C7	0.45006 (12)	0.55349 (19)	0.72722 (10)	0.0447 (3)
C8	0.35038 (12)	0.6665 (2)	0.72803 (11)	0.0516 (4)
H8	0.3294	0.7385	0.6731	0.062*
C9	0.28208 (13)	0.6735 (2)	0.80914 (11)	0.0547 (4)
H9	0.2153	0.7498	0.8077	0.066*
C10	0.31070 (13)	0.5694 (2)	0.89293 (11)	0.0526 (4)
C11	0.41089 (13)	0.4573 (2)	0.89151 (11)	0.0502 (4)
H11	0.4322	0.3860	0.9467	0.060*
C12	0.47974 (13)	0.44843 (19)	0.81091 (10)	0.0477 (4)
H12	0.5464	0.3719	0.8124	0.057*
C13	0.23520 (17)	0.5750 (3)	0.98106 (13)	0.0757 (5)
H13A	0.1631	0.6452	0.9646	0.113*
H13B	0.2829	0.6262	1.0373	0.113*
H13C	0.2115	0.4572	0.9974	0.113*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0418 (7)	0.0866 (10)	0.0424 (7)	0.0084 (6)	0.0001 (5)	0.0006 (6)
N2	0.0492 (7)	0.0675 (8)	0.0496 (7)	0.0037 (6)	0.0048 (5)	−0.0037 (6)
C1	0.0536 (9)	0.0824 (12)	0.0583 (9)	0.0073 (8)	0.0136 (7)	−0.0093 (8)
C2	0.0426 (8)	0.0744 (11)	0.0698 (10)	0.0060 (7)	0.0104 (7)	−0.0040 (8)
C3	0.0433 (8)	0.0435 (8)	0.0599 (9)	−0.0004 (6)	0.0025 (6)	0.0045 (6)
C4	0.0439 (7)	0.0494 (8)	0.0479 (7)	0.0008 (6)	0.0049 (6)	−0.0010 (6)
C5	0.0427 (7)	0.0476 (8)	0.0471 (7)	0.0022 (6)	0.0049 (6)	0.0029 (6)
C6	0.0435 (8)	0.0664 (10)	0.0706 (10)	−0.0005 (7)	−0.0032 (7)	0.0044 (8)
C7	0.0363 (7)	0.0533 (8)	0.0434 (7)	−0.0015 (6)	−0.0023 (5)	−0.0024 (6)
C8	0.0424 (7)	0.0570 (9)	0.0542 (8)	0.0033 (6)	−0.0022 (6)	0.0070 (7)
C9	0.0411 (7)	0.0585 (9)	0.0643 (9)	0.0052 (6)	0.0031 (6)	−0.0040 (7)
C10	0.0452 (8)	0.0625 (9)	0.0500 (8)	−0.0080 (7)	0.0034 (6)	−0.0102 (7)
C11	0.0479 (8)	0.0559 (9)	0.0450 (7)	−0.0082 (6)	−0.0047 (6)	0.0031 (6)
C12	0.0408 (7)	0.0497 (8)	0.0512 (8)	0.0021 (6)	−0.0036 (6)	−0.0022 (6)
C13	0.0698 (11)	0.0969 (14)	0.0623 (10)	−0.0047 (10)	0.0172 (8)	−0.0109 (10)

Geometric parameters (Å, º) top

N1—C5	1.3716 (18)	C6—H6C	0.9600
N1—C7	1.4051 (18)	C7—C8	1.3867 (19)
N1—H1	0.875 (9)	C7—C12	1.391 (2)
N2—C1	1.340 (2)	C8—C9	1.378 (2)
N2—C5	1.3380 (18)	C8—H8	0.9300
C1—C2	1.369 (2)	C9—C10	1.386 (2)
C1—H1A	0.9300	C9—H9	0.9300
C2—C3	1.385 (2)	C10—C11	1.388 (2)
C2—H2	0.9300	C10—C13	1.505 (2)
C3—C4	1.375 (2)	C11—C12	1.376 (2)
C3—C6	1.502 (2)	C11—H11	0.9300
C4—C5	1.399 (2)	C12—H12	0.9300
C4—H4	0.9300	C13—H13A	0.9600
C6—H6A	0.9600	C13—H13B	0.9600
C6—H6B	0.9600	C13—H13C	0.9600

C5—N1—C7	127.24 (12)	C8—C7—C12	118.16 (13)
C5—N1—H1	115.4 (11)	C8—C7—N1	118.89 (13)
C7—N1—H1	117.1 (11)	C12—C7—N1	122.87 (13)
C1—N2—C5	116.68 (13)	C9—C8—C7	120.90 (13)
N2—C1—C2	124.77 (15)	C9—C8—H8	119.5
N2—C1—H1A	117.6	C7—C8—H8	119.5
C2—C1—H1A	117.6	C8—C9—C10	121.47 (14)
C1—C2—C3	118.61 (14)	C8—C9—H9	119.3
C1—C2—H2	120.7	C10—C9—H9	119.3
C3—C2—H2	120.7	C9—C10—C11	117.16 (14)
C4—C3—C2	117.75 (14)	C9—C10—C13	121.57 (15)
C4—C3—C6	120.58 (14)	C11—C10—C13	121.26 (15)
C2—C3—C6	121.67 (14)	C12—C11—C10	122.03 (14)
C3—C4—C5	120.13 (13)	C12—C11—H11	119.0
C3—C4—H4	119.9	C10—C11—H11	119.0
C5—C4—H4	119.9	C11—C12—C7	120.27 (13)
N2—C5—N1	115.25 (12)	C11—C12—H12	119.9
N2—C5—C4	121.97 (13)	C7—C12—H12	119.9
N1—C5—C4	122.73 (13)	C10—C13—H13A	109.5
C3—C6—H6A	109.5	C10—C13—H13B	109.5
C3—C6—H6B	109.5	H13A—C13—H13B	109.5
H6A—C6—H6B	109.5	C10—C13—H13C	109.5
C3—C6—H6C	109.5	H13A—C13—H13C	109.5
H6A—C6—H6C	109.5	H13B—C13—H13C	109.5
H6B—C6—H6C	109.5

C5—N2—C1—C2	1.7 (3)	C5—N1—C7—C8	146.94 (15)
N2—C1—C2—C3	−2.5 (3)	C5—N1—C7—C12	−36.3 (2)
C1—C2—C3—C4	0.6 (2)	C12—C7—C8—C9	−0.5 (2)
C1—C2—C3—C6	−179.91 (16)	N1—C7—C8—C9	176.39 (13)
C2—C3—C4—C5	2.0 (2)	C7—C8—C9—C10	0.5 (2)
C6—C3—C4—C5	−177.51 (13)	C8—C9—C10—C11	−0.2 (2)
C1—N2—C5—N1	178.72 (14)	C8—C9—C10—C13	−179.16 (15)
C1—N2—C5—C4	1.1 (2)	C9—C10—C11—C12	0.0 (2)
C7—N1—C5—N2	163.28 (14)	C13—C10—C11—C12	178.95 (14)
C7—N1—C5—C4	−19.1 (2)	C10—C11—C12—C7	0.0 (2)
C3—C4—C5—N2	−3.0 (2)	C8—C7—C12—C11	0.3 (2)
C3—C4—C5—N1	179.59 (14)	N1—C7—C12—C11	−176.47 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.87 (1)	2.18 (1)	3.041 (2)	170 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₄N₂
M_r	198.26
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	10.9385 (11), 7.5708 (8), 13.4372 (14)
β (°)	95.246 (2)
V (Å³)	1108.1 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.45 × 0.40 × 0.30

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6758, 2528, 1797
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.142, 1.05
No. of reflections	2528
No. of parameters	143
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.13

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.87 (1)	2.18 (1)	3.041 (2)	170 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

We thank the University of Malaya (grant No. RG027/09AFR, PS374/09 A) for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fairuz, Z. A., Aiyub, Z., Abdullah, Z. & Ng, S. W. (2008). Acta Cryst. E64, o2441. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). publCIF. In preparation. Google Scholar