N-(4-Methyl-2-pyrid­yl)-p-toluidine

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

doi:10.1107/S160053680905586X

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

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

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.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680905586X/xu2710sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680905586X/xu2710Isup2.hkl Contains datablock I

CCDC reference: 765143

checkCIF report

Key indicators

Single-crystal X-ray study
T = 295 K
Mean (C-C) = 0.002 Å
R factor = 0.043
wR factor = 0.142
Data-to-parameter ratio = 17.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         11
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          6

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1
PLAT128_ALERT_4_G Non-standard setting of Space-group P21/c   ....      P21/n

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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).