organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

N-(4-Methyl-2-pyrid­yl)-p-toluidine

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[Fairuz, Z. A., Aiyub, Z., Abdullah, Z. & Ng, S. W. (2008). Acta Cryst. E64, o2441.]).

[Scheme 1]

Experimental

Crystal data
  • C13H14N2

  • Mr = 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)

  • Rint = 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

  • Δρmax = 0.17 e Å−3

  • Δρmin = −0.13 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). publCIF. In preparation.]).

Supporting information


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.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C–H 0.93–0.96 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2–1.5U(C). The amino H-atom was located in a difference Fourier map, and was refined with a distance restraint of N–H 0.86±0.01 Å; its temperature factor was refined.

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
[Figure 1] 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
C13H14N2F(000) = 424
Mr = 198.26Dx = 1.188 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2289 reflections
a = 10.9385 (11) Åθ = 2.5–28.1°
b = 7.5708 (8) ŵ = 0.07 mm1
c = 13.4372 (14) ÅT = 295 K
β = 95.246 (2)°Irregular block, colorless
V = 1108.1 (2) Å30.45 × 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 tubeRint = 0.024
Graphite monochromatorθmax = 27.5°, θmin = 2.3°
ω scansh = 1413
6758 measured reflectionsk = 99
2528 independent reflectionsl = 1417
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.142 w = 1/[σ2(Fo2) + (0.0692P)2 + 0.1529P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
2528 reflectionsΔρmax = 0.17 e Å3
143 parametersΔρmin = 0.13 e Å3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.044 (6)
Crystal data top
C13H14N2V = 1108.1 (2) Å3
Mr = 198.26Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.9385 (11) ŵ = 0.07 mm1
b = 7.5708 (8) ÅT = 295 K
c = 13.4372 (14) Å0.45 × 0.40 × 0.30 mm
β = 95.246 (2)°
Data collection top
Bruker SMART APEX
diffractometer
1797 reflections with I > 2σ(I)
6758 measured reflectionsRint = 0.024
2528 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0431 restraint
wR(F2) = 0.142H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.17 e Å3
2528 reflectionsΔρmin = 0.13 e Å3
143 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.51269 (11)0.54344 (19)0.64065 (9)0.0571 (4)
H10.4682 (13)0.546 (2)0.5832 (8)0.063 (5)*
N20.66732 (12)0.46482 (18)0.54571 (9)0.0554 (4)
C10.78715 (15)0.4383 (2)0.53779 (12)0.0642 (5)
H1A0.81070.40720.47540.077*
C20.87740 (14)0.4535 (2)0.61487 (13)0.0619 (4)
H20.95880.42880.60520.074*
C30.84502 (13)0.50645 (19)0.70755 (11)0.0490 (4)
C40.72299 (13)0.53940 (19)0.71698 (11)0.0471 (3)
H40.69850.57880.77760.056*
C50.63566 (13)0.51384 (18)0.63552 (10)0.0458 (3)
C60.93890 (14)0.5264 (2)0.79563 (12)0.0607 (4)
H6A0.91680.62390.83600.091*
H6B1.01800.54790.77250.091*
H6C0.94180.42010.83470.091*
C70.45006 (12)0.55349 (19)0.72722 (10)0.0447 (3)
C80.35038 (12)0.6665 (2)0.72803 (11)0.0516 (4)
H80.32940.73850.67310.062*
C90.28208 (13)0.6735 (2)0.80914 (11)0.0547 (4)
H90.21530.74980.80770.066*
C100.31070 (13)0.5694 (2)0.89293 (11)0.0526 (4)
C110.41089 (13)0.4573 (2)0.89151 (11)0.0502 (4)
H110.43220.38600.94670.060*
C120.47974 (13)0.44843 (19)0.81091 (10)0.0477 (4)
H120.54640.37190.81240.057*
C130.23520 (17)0.5750 (3)0.98106 (13)0.0757 (5)
H13A0.16310.64520.96460.113*
H13B0.28290.62621.03730.113*
H13C0.21150.45720.99740.113*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0418 (7)0.0866 (10)0.0424 (7)0.0084 (6)0.0001 (5)0.0006 (6)
N20.0492 (7)0.0675 (8)0.0496 (7)0.0037 (6)0.0048 (5)0.0037 (6)
C10.0536 (9)0.0824 (12)0.0583 (9)0.0073 (8)0.0136 (7)0.0093 (8)
C20.0426 (8)0.0744 (11)0.0698 (10)0.0060 (7)0.0104 (7)0.0040 (8)
C30.0433 (8)0.0435 (8)0.0599 (9)0.0004 (6)0.0025 (6)0.0045 (6)
C40.0439 (7)0.0494 (8)0.0479 (7)0.0008 (6)0.0049 (6)0.0010 (6)
C50.0427 (7)0.0476 (8)0.0471 (7)0.0022 (6)0.0049 (6)0.0029 (6)
C60.0435 (8)0.0664 (10)0.0706 (10)0.0005 (7)0.0032 (7)0.0044 (8)
C70.0363 (7)0.0533 (8)0.0434 (7)0.0015 (6)0.0023 (5)0.0024 (6)
C80.0424 (7)0.0570 (9)0.0542 (8)0.0033 (6)0.0022 (6)0.0070 (7)
C90.0411 (7)0.0585 (9)0.0643 (9)0.0052 (6)0.0031 (6)0.0040 (7)
C100.0452 (8)0.0625 (9)0.0500 (8)0.0080 (7)0.0034 (6)0.0102 (7)
C110.0479 (8)0.0559 (9)0.0450 (7)0.0082 (6)0.0047 (6)0.0031 (6)
C120.0408 (7)0.0497 (8)0.0512 (8)0.0021 (6)0.0036 (6)0.0022 (6)
C130.0698 (11)0.0969 (14)0.0623 (10)0.0047 (10)0.0172 (8)0.0109 (10)
Geometric parameters (Å, º) top
N1—C51.3716 (18)C6—H6C0.9600
N1—C71.4051 (18)C7—C81.3867 (19)
N1—H10.875 (9)C7—C121.391 (2)
N2—C11.340 (2)C8—C91.378 (2)
N2—C51.3380 (18)C8—H80.9300
C1—C21.369 (2)C9—C101.386 (2)
C1—H1A0.9300C9—H90.9300
C2—C31.385 (2)C10—C111.388 (2)
C2—H20.9300C10—C131.505 (2)
C3—C41.375 (2)C11—C121.376 (2)
C3—C61.502 (2)C11—H110.9300
C4—C51.399 (2)C12—H120.9300
C4—H40.9300C13—H13A0.9600
C6—H6A0.9600C13—H13B0.9600
C6—H6B0.9600C13—H13C0.9600
C5—N1—C7127.24 (12)C8—C7—C12118.16 (13)
C5—N1—H1115.4 (11)C8—C7—N1118.89 (13)
C7—N1—H1117.1 (11)C12—C7—N1122.87 (13)
C1—N2—C5116.68 (13)C9—C8—C7120.90 (13)
N2—C1—C2124.77 (15)C9—C8—H8119.5
N2—C1—H1A117.6C7—C8—H8119.5
C2—C1—H1A117.6C8—C9—C10121.47 (14)
C1—C2—C3118.61 (14)C8—C9—H9119.3
C1—C2—H2120.7C10—C9—H9119.3
C3—C2—H2120.7C9—C10—C11117.16 (14)
C4—C3—C2117.75 (14)C9—C10—C13121.57 (15)
C4—C3—C6120.58 (14)C11—C10—C13121.26 (15)
C2—C3—C6121.67 (14)C12—C11—C10122.03 (14)
C3—C4—C5120.13 (13)C12—C11—H11119.0
C3—C4—H4119.9C10—C11—H11119.0
C5—C4—H4119.9C11—C12—C7120.27 (13)
N2—C5—N1115.25 (12)C11—C12—H12119.9
N2—C5—C4121.97 (13)C7—C12—H12119.9
N1—C5—C4122.73 (13)C10—C13—H13A109.5
C3—C6—H6A109.5C10—C13—H13B109.5
C3—C6—H6B109.5H13A—C13—H13B109.5
H6A—C6—H6B109.5C10—C13—H13C109.5
C3—C6—H6C109.5H13A—C13—H13C109.5
H6A—C6—H6C109.5H13B—C13—H13C109.5
H6B—C6—H6C109.5
C5—N2—C1—C21.7 (3)C5—N1—C7—C8146.94 (15)
N2—C1—C2—C32.5 (3)C5—N1—C7—C1236.3 (2)
C1—C2—C3—C40.6 (2)C12—C7—C8—C90.5 (2)
C1—C2—C3—C6179.91 (16)N1—C7—C8—C9176.39 (13)
C2—C3—C4—C52.0 (2)C7—C8—C9—C100.5 (2)
C6—C3—C4—C5177.51 (13)C8—C9—C10—C110.2 (2)
C1—N2—C5—N1178.72 (14)C8—C9—C10—C13179.16 (15)
C1—N2—C5—C41.1 (2)C9—C10—C11—C120.0 (2)
C7—N1—C5—N2163.28 (14)C13—C10—C11—C12178.95 (14)
C7—N1—C5—C419.1 (2)C10—C11—C12—C70.0 (2)
C3—C4—C5—N23.0 (2)C8—C7—C12—C110.3 (2)
C3—C4—C5—N1179.59 (14)N1—C7—C12—C11176.47 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N2i0.87 (1)2.18 (1)3.041 (2)170 (2)
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC13H14N2
Mr198.26
Crystal system, space groupMonoclinic, P21/n
Temperature (K)295
a, b, c (Å)10.9385 (11), 7.5708 (8), 13.4372 (14)
β (°) 95.246 (2)
V3)1108.1 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.07
Crystal size (mm)0.45 × 0.40 × 0.30
Data collection
DiffractometerBruker SMART APEX
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
6758, 2528, 1797
Rint0.024
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.142, 1.05
No. of reflections2528
No. of parameters143
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N1—H1···N2i0.87 (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

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

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.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds