4-Methyl-N-(3-methyl­phen­yl)pyridin-2-amine

Fairuz, Z.A.; Aiyub, Z.; Abdullah, Z.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536811044059

organic compounds

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Volume 67| Part 11| November 2011| Page o3078

doi:10.1107/S1600536811044059

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4-Methyl-N-(3-methylphenyl)pyridin-2-amine

Zainal Abidin Fairuz,^a Zaharah Aiyub,^a Zanariah Abdullah,^a ‡ Seik Weng Ng ^a,^b and Edward R. T. Tiekink ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^bChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 24 October 2011; accepted 24 October 2011; online 29 October 2011)

The title amine, C₁₃H₁₄N₂, is twisted with a dihedral angle between the rings of 60.07 (9)°. The amine N—H group and pyridine N atom are syn allowing for the formation of centrosymmetric eight-membered {⋯HNCN}₂ synthons via N—H⋯N hydrogen bonds. The two-molecule aggregates are sustained in the three-dimensional crystal packing via C—H⋯π and π–π interactions [centroid–centroid distance for pyridyl rings = 3.7535 (12) Å]

Related literature

For a copper(II) paddle-wheel complex containing the title molecule as a ligand, see: Fairuz et al. (2010 ).

Experimental

Crystal data

C₁₃H₁₄N₂
M_r = 198.26
Triclinic, $[P \overline 1]$
a = 7.1802 (9) Å
b = 7.6509 (10) Å
c = 10.8120 (14) Å
α = 106.957 (2)°
β = 91.859 (2)°
γ = 95.720 (2)°
V = 564.12 (13) Å³
Z = 2
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 293 K
0.20 × 0.18 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.986, T_max = 0.993
7262 measured reflections
2581 independent reflections
1694 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.168
S = 1.02
2581 reflections
142 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are centroids of the N2,C1–C5 and C7–C12 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1n⋯N2ⁱ	0.87 (1)	2.12 (1)	2.978 (2)	172 (2)
C6—H6b⋯Cg1ⁱⁱ	0.96	2.73	3.624 (3)	155
C13—H13b⋯Cg2ⁱⁱⁱ	0.96	2.74	3.612 (2)	151
C13—H13c⋯Cg2^iv	0.96	2.88	3.642 (2)	137
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+2, -y+2, -z+1; (iii) -x+2, -y+2, -z+2; (iv) -x+1, -y+2, -z+2.

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811044059/hg5117sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811044059/hg5117Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811044059/hg5117Isup3.cml

checkCIF report

Comment top

The title amine, (I), has been observed to coordinate Cu^II in a paddle-wheel motif (Fairuz et al., 2010). Herein, the crystal and molecular structure of the amine is described.

The dihedral angle between the pyridyl and benzene rings in (I), Fig. 1, is 60.07 (9)°, indicating a twisted conformation. The amine-NH and pyridyl-N atoms are syn. This latter feature allows for the formation of centrosymmetric eight-membered {···HNCN}₂ synthons via N—H···N hydrogen bonds, Fig. 2 and Table 1. The two-molecule aggregates are connected into a layer in the ab plane via C—H···π(pyridyl) interactions, Table 1, and π–π interactions occurring between pyridyl rings [3.7535 (12) Å for symmetry operation 2 - x, 1 - y, 1 - z], Fig. 3. The benzene rings project out of the layers allowing for their inter-digitation along the c axis via C—H···π interactions, Fig. 4 and Table 1.

Related literature top

For a copper(II) paddle-wheel complex containing the title molecule as a ligand, see: Fairuz et al. (2010).

Experimental top

2-Chloro-4-methylpyridine (1.0 ml, 1.14 mmol) and m-toluidine (1.24 ml, 1.14 mmol) were refluxed for 4 h. The suspension was cooled, taken up in water (15 ml) and then extracted with diethyl ether (3 x 10 ml). The organic layer was washed with water (3 x 10 ml) and dried over anhydrous sodium sulfate. Evaporation of diethyl ether gave a dark-brown solid and recrystallization from its ethanol solution gave pure colourless crystals.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 35% probability level.
	Fig. 2. Two molecule aggregates in (I) mediated by N—H···N hydrogen bonding, shown as blue dashed lines.
	Fig. 3. Layers in the ab plane in (I) sustained by N—H···N hydrogen bonding, C—H···π(pyridyl) and π–π interactions shown as blue, orange and purple dashed lines, respectively.
	Fig. 4. Unit-cell contents for (I) shown in projection down the b axis highlighting the inter-digitation of layers. The N—H···N hydrogen bonding, C—H···π(pyridyl) and π–π interactions are shown as blue, orange and purple dashed lines, respectively.

4-Methyl-N-(3-methylphenyl)pyridin-2-amine top

Crystal data top

C₁₃H₁₄N₂	Z = 2
M_r = 198.26	F(000) = 212
Triclinic, P1	D_x = 1.167 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1802 (9) Å	Cell parameters from 1537 reflections
b = 7.6509 (10) Å	θ = 2.8–24.2°
c = 10.8120 (14) Å	µ = 0.07 mm⁻¹
α = 106.957 (2)°	T = 293 K
β = 91.859 (2)°	Prism, colourless
γ = 95.720 (2)°	0.20 × 0.18 × 0.10 mm
V = 564.12 (13) Å³

Data collection top

Bruker SMART APEX diffractometer	2581 independent reflections
Radiation source: fine-focus sealed tube	1694 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 27.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→9
T_min = 0.986, T_max = 0.993	k = −9→9
7262 measured reflections	l = −12→14

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.168	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0822P)² + 0.1088P] where P = (F_o² + 2F_c²)/3
2581 reflections	(Δ/σ)_max < 0.001
142 parameters	Δρ_max = 0.24 e Å⁻³
1 restraint	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₃H₁₄N₂	γ = 95.720 (2)°
M_r = 198.26	V = 564.12 (13) Å³
Triclinic, P1	Z = 2
a = 7.1802 (9) Å	Mo Kα radiation
b = 7.6509 (10) Å	µ = 0.07 mm⁻¹
c = 10.8120 (14) Å	T = 293 K
α = 106.957 (2)°	0.20 × 0.18 × 0.10 mm
β = 91.859 (2)°

Data collection top

Bruker SMART APEX diffractometer	2581 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1694 reflections with I > 2σ(I)
T_min = 0.986, T_max = 0.993	R_int = 0.029
7262 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	1 restraint
wR(F²) = 0.168	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.24 e Å⁻³
2581 reflections	Δρ_min = −0.19 e Å⁻³
142 parameters

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

	x	y	z	U_iso*/U_eq
N1	0.6599 (2)	0.6400 (2)	0.64600 (14)	0.0512 (4)
H1n	0.561 (2)	0.563 (2)	0.6173 (18)	0.061 (6)*
N2	0.7026 (2)	0.6004 (2)	0.43224 (13)	0.0445 (4)
C1	0.7759 (2)	0.6687 (2)	0.55430 (15)	0.0384 (4)
C2	0.9589 (2)	0.7569 (2)	0.58388 (16)	0.0424 (4)
H2	1.0056	0.8030	0.6698	0.051*
C3	1.0702 (3)	0.7759 (2)	0.48638 (18)	0.0452 (4)
C4	0.9924 (3)	0.7063 (3)	0.35997 (18)	0.0537 (5)
H4	1.0613	0.7182	0.2909	0.064*
C5	0.8129 (3)	0.6199 (3)	0.33856 (17)	0.0530 (5)
H5	0.7643	0.5716	0.2532	0.064*
C6	1.2683 (3)	0.8666 (3)	0.5154 (2)	0.0616 (6)
H6A	1.3222	0.8406	0.5897	0.092*
H6B	1.2691	0.9972	0.5331	0.092*
H6C	1.3405	0.8202	0.4422	0.092*
C7	0.6915 (2)	0.7151 (2)	0.78132 (15)	0.0408 (4)
C8	0.6745 (3)	0.6003 (3)	0.85864 (17)	0.0483 (5)
H8	0.6491	0.4739	0.8210	0.058*
C9	0.6951 (3)	0.6721 (3)	0.99134 (19)	0.0592 (5)
H9	0.6829	0.5941	1.0431	0.071*
C10	0.7336 (3)	0.8593 (3)	1.04803 (18)	0.0580 (5)
H10	0.7490	0.9063	1.1378	0.070*
C11	0.7494 (2)	0.9777 (3)	0.97289 (18)	0.0488 (5)
C12	0.7282 (2)	0.9038 (2)	0.83984 (17)	0.0460 (4)
H12	0.7386	0.9821	0.7881	0.055*
C13	0.7845 (3)	1.1821 (3)	1.0352 (2)	0.0708 (7)
H13A	0.7804	1.2436	0.9696	0.106*
H13B	0.9056	1.2125	1.0811	0.106*
H13C	0.6897	1.2207	1.0947	0.106*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0469 (9)	0.0642 (10)	0.0337 (8)	−0.0178 (8)	−0.0010 (7)	0.0089 (7)
N2	0.0478 (9)	0.0479 (8)	0.0344 (8)	−0.0035 (6)	−0.0010 (6)	0.0105 (6)
C1	0.0425 (9)	0.0371 (8)	0.0336 (9)	−0.0011 (7)	0.0002 (7)	0.0094 (6)
C2	0.0412 (10)	0.0439 (9)	0.0389 (9)	−0.0001 (7)	−0.0010 (7)	0.0094 (7)
C3	0.0429 (10)	0.0388 (8)	0.0555 (11)	0.0066 (7)	0.0092 (8)	0.0151 (8)
C4	0.0577 (12)	0.0583 (11)	0.0470 (11)	0.0047 (9)	0.0167 (9)	0.0178 (9)
C5	0.0619 (13)	0.0587 (11)	0.0353 (9)	0.0010 (9)	0.0038 (9)	0.0109 (8)
C6	0.0429 (11)	0.0623 (12)	0.0786 (15)	−0.0001 (9)	0.0112 (10)	0.0204 (11)
C7	0.0333 (9)	0.0509 (10)	0.0349 (9)	−0.0009 (7)	0.0007 (7)	0.0094 (7)
C8	0.0512 (11)	0.0478 (10)	0.0446 (10)	−0.0004 (8)	0.0034 (8)	0.0135 (8)
C9	0.0670 (14)	0.0693 (13)	0.0443 (11)	0.0016 (10)	0.0031 (9)	0.0237 (10)
C10	0.0566 (12)	0.0755 (14)	0.0339 (9)	0.0037 (10)	0.0018 (8)	0.0050 (9)
C11	0.0356 (9)	0.0530 (10)	0.0483 (11)	0.0067 (8)	−0.0004 (8)	0.0001 (8)
C12	0.0434 (10)	0.0478 (10)	0.0466 (10)	0.0020 (7)	−0.0014 (8)	0.0153 (8)
C13	0.0576 (13)	0.0582 (12)	0.0774 (15)	0.0090 (10)	−0.0050 (11)	−0.0096 (11)

Geometric parameters (Å, º) top

N1—C1	1.367 (2)	C6—H6C	0.9600
N1—C7	1.409 (2)	C7—C8	1.378 (2)
N1—H1n	0.865 (10)	C7—C12	1.391 (2)
N2—C1	1.338 (2)	C8—C9	1.376 (3)
N2—C5	1.339 (2)	C8—H8	0.9300
C1—C2	1.398 (2)	C9—C10	1.378 (3)
C2—C3	1.375 (2)	C9—H9	0.9300
C2—H2	0.9300	C10—C11	1.382 (3)
C3—C4	1.389 (3)	C10—H10	0.9300
C3—C6	1.500 (3)	C11—C12	1.381 (2)
C4—C5	1.368 (3)	C11—C13	1.503 (3)
C4—H4	0.9300	C12—H12	0.9300
C5—H5	0.9300	C13—H13A	0.9600
C6—H6A	0.9600	C13—H13B	0.9600
C6—H6B	0.9600	C13—H13C	0.9600

C1—N1—C7	126.61 (15)	C8—C7—C12	118.87 (16)
C1—N1—H1n	115.9 (14)	C8—C7—N1	119.37 (16)
C7—N1—H1n	117.4 (14)	C12—C7—N1	121.64 (16)
C1—N2—C5	116.93 (15)	C7—C8—C9	120.19 (17)
N2—C1—N1	114.66 (15)	C7—C8—H8	119.9
N2—C1—C2	122.02 (15)	C9—C8—H8	119.9
N1—C1—C2	123.28 (15)	C8—C9—C10	120.34 (19)
C3—C2—C1	120.26 (16)	C8—C9—H9	119.8
C3—C2—H2	119.9	C10—C9—H9	119.8
C1—C2—H2	119.9	C9—C10—C11	120.69 (18)
C2—C3—C4	117.35 (17)	C9—C10—H10	119.7
C2—C3—C6	121.26 (18)	C11—C10—H10	119.7
C4—C3—C6	121.38 (17)	C12—C11—C10	118.37 (17)
C5—C4—C3	119.02 (17)	C12—C11—C13	121.09 (19)
C5—C4—H4	120.5	C10—C11—C13	120.52 (18)
C3—C4—H4	120.5	C11—C12—C7	121.52 (17)
N2—C5—C4	124.40 (17)	C11—C12—H12	119.2
N2—C5—H5	117.8	C7—C12—H12	119.2
C4—C5—H5	117.8	C11—C13—H13A	109.5
C3—C6—H6A	109.5	C11—C13—H13B	109.5
C3—C6—H6B	109.5	H13A—C13—H13B	109.5
H6A—C6—H6B	109.5	C11—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—N1	−177.95 (16)	C1—N1—C7—C8	−129.1 (2)
C5—N2—C1—C2	0.1 (2)	C1—N1—C7—C12	54.9 (3)
C7—N1—C1—N2	−171.86 (17)	C12—C7—C8—C9	−0.5 (3)
C7—N1—C1—C2	10.1 (3)	N1—C7—C8—C9	−176.57 (17)
N2—C1—C2—C3	0.0 (3)	C7—C8—C9—C10	−0.3 (3)
N1—C1—C2—C3	177.81 (16)	C8—C9—C10—C11	0.9 (3)
C1—C2—C3—C4	0.7 (3)	C9—C10—C11—C12	−0.8 (3)
C1—C2—C3—C6	−178.78 (16)	C9—C10—C11—C13	177.77 (19)
C2—C3—C4—C5	−1.4 (3)	C10—C11—C12—C7	0.0 (3)
C6—C3—C4—C5	178.08 (18)	C13—C11—C12—C7	−178.52 (17)
C1—N2—C5—C4	−0.9 (3)	C8—C7—C12—C11	0.6 (3)
C3—C4—C5—N2	1.6 (3)	N1—C7—C12—C11	176.60 (16)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are centroids of the N2,C1–C5 and C7–C12 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···N2ⁱ	0.87 (1)	2.12 (1)	2.978 (2)	172 (2)
C6—H6b···Cg1ⁱⁱ	0.96	2.73	3.624 (3)	155
C13—H13b···Cg2ⁱⁱⁱ	0.96	2.74	3.612 (2)	151
C13—H13c···Cg2^iv	0.96	2.88	3.642 (2)	137

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₄N₂
M_r	198.26
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.1802 (9), 7.6509 (10), 10.8120 (14)
α, β, γ (°)	106.957 (2), 91.859 (2), 95.720 (2)
V (Å³)	564.12 (13)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.20 × 0.18 × 0.10

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.986, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	7262, 2581, 1694
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.168, 1.02
No. of reflections	2581
No. of parameters	142
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)	0.24, −0.19

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are centroids of the N2,C1–C5 and C7–C12 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···N2ⁱ	0.865 (10)	2.120 (10)	2.978 (2)	171.6 (19)
C6—H6b···Cg1ⁱⁱ	0.96	2.73	3.624 (3)	155
C13—H13b···Cg2ⁱⁱⁱ	0.96	2.74	3.612 (2)	151
C13—H13c···Cg2^iv	0.96	2.88	3.642 (2)	137

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

Footnotes

‡Additional correspondence author, e-mail: zana@um.edu.my.

Acknowledgements

We thank the University of Malaya (grant No. FP001/2010 A) for supporting this study.

References

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fairuz, Z. A., Aiyub, Z., Abdullah, Z. & Ng, S. W. (2010). Acta Cryst. E66, m165. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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