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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2441.
Published online 2008 November 26. doi:  10.1107/S1600536808037306
PMCID: PMC2960016

N-(2-Pyrid­yl)-4-toluidine

Abstract

There are two mol­ecules in the asymmetric unit of the title compound, C12H12N2, with dihedral angles between the aromatic rings of 48.35 (12) and 51.02 (12)°. In the crystal structure, both mol­ecules form inversion dimers, linked by pairs of N—H(...)N hydrogen bonds.

Related literature

For the crystal structure of N-(2-pyrid­yl)aniline, see: Polamo et al. (1997 [triangle])

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Object name is e-64-o2441-scheme1.jpg

Experimental

Crystal data

  • C12H12N2
  • M r = 184.24
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2441-efi1.jpg
  • a = 18.2260 (7) Å
  • b = 10.5680 (3) Å
  • c = 10.6005 (3) Å
  • β = 95.364 (2)°
  • V = 2032.9 (1) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.07 mm−1
  • T = 100 (2) K
  • 0.30 × 0.10 × 0.05 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: none
  • 18430 measured reflections
  • 4676 independent reflections
  • 2774 reflections with I > 2σ(I)
  • R int = 0.066

Refinement

  • R[F 2 > 2σ(F 2)] = 0.070
  • wR(F 2) = 0.206
  • S = 1.01
  • 4676 reflections
  • 263 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.64 e Å−3
  • Δρmin = −0.31 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808037306/sg2278sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037306/sg2278Isup2.hkl

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

Acknowledgments

We thank the University of Malaya for supporting this study (grant Nos. FS 358/2008 A and FP 067/2006 A).

supplementary crystallographic information

Comment

There are two molecules in the asymmetric unit (Fig. 1) of the title compound, C12H12N2, with dihedral angles between the aromatic rings of 48.35 (12)° and 51.02 (12)°. In the crystal, both molecules form inversion dimers, linked by pairs of N—H···N hydrogen bonds (Table 1). For the related crystal structure of N-(2-pyridyl)aniline, see: Polamo et al. (1997)

Experimental

Chloropyridine (0.5 ml, 0.5 mmol) and 4-toluidine (0.6 g, 0.5 mmol) were heated at 423–433 K for 3 h. The solid was dissolved in water. The compound was extracted with ether. The ether extract was dried over sodium sulfate. The solvent was evaporated and the product recrystallized from ethanol to yield colorless prisms of (I) among some unidentified dark brown materials.

Refinement

The carbon-bound H-atoms were placed in calculated positions (C—H = 0.95–0.98 Å) and refined as riding with U(H) = 1.2–1.5U(C). The amino H-atom was located in a difference map, and was refined with a distance restraint of N–H 0.88±0.01 Å.

The highest difference peak is 1.0Å from C18 and deepest difference hole is 0.7Å from C18.

Figures

Fig. 1.
The molecular structure of (I), with displacement ellipsoids at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C12H12N2F000 = 784
Mr = 184.24Dx = 1.204 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1819 reflections
a = 18.2260 (7) Åθ = 2.2–24.4º
b = 10.5680 (3) ŵ = 0.07 mm1
c = 10.6005 (3) ÅT = 100 (2) K
β = 95.364 (2)ºPrism, colorless
V = 2032.9 (1) Å30.30 × 0.10 × 0.05 mm
Z = 8

Data collection

Bruker SMART APEX diffractometer2774 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.066
Monochromator: graphiteθmax = 27.5º
T = 100(2) Kθmin = 1.1º
ω scansh = −23→23
Absorption correction: Nonek = −13→13
18430 measured reflectionsl = −13→13
4676 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.070H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.206  w = 1/[σ2(Fo2) + (0.0922P)2 + 1.1608P] where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.001
4676 reflectionsΔρmax = 0.64 e Å3
263 parametersΔρmin = −0.31 e Å3
2 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

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

xyzUiso*/Ueq
N10.09908 (12)0.46043 (18)0.0668 (2)0.0267 (5)
N2−0.01070 (12)0.37392 (18)0.11163 (19)0.0279 (5)
N30.40746 (13)0.5526 (2)0.5578 (2)0.0350 (6)
N40.52478 (13)0.60957 (18)0.62565 (19)0.0317 (5)
C10.17505 (14)0.4657 (2)0.0530 (2)0.0258 (5)
C20.21791 (14)0.3582 (2)0.0393 (2)0.0293 (6)
H20.19620.27660.04180.035*
C30.29141 (14)0.3698 (3)0.0221 (3)0.0337 (6)
H30.31980.29540.01380.040*
C40.32560 (15)0.4877 (3)0.0164 (3)0.0334 (6)
C50.28179 (15)0.5943 (2)0.0269 (3)0.0340 (6)
H50.30310.67590.02080.041*
C60.20817 (15)0.5841 (2)0.0460 (2)0.0312 (6)
H00.17980.65850.05430.037*
C70.40666 (16)0.4993 (3)0.0012 (3)0.0419 (7)
H7A0.41660.5822−0.03500.063*
H7B0.42130.4325−0.05550.063*
H7C0.43480.49070.08410.063*
C80.06324 (14)0.3732 (2)0.1354 (2)0.0269 (6)
C90.09904 (15)0.2931 (2)0.2268 (2)0.0311 (6)
H90.15120.29440.24310.037*
C100.05715 (17)0.2127 (2)0.2923 (3)0.0371 (7)
H100.08040.15730.35440.045*
C11−0.01855 (16)0.2121 (2)0.2684 (3)0.0377 (7)
H11−0.04820.15660.31260.045*
C12−0.04948 (16)0.2946 (2)0.1783 (3)0.0340 (6)
H12−0.10160.29550.16240.041*
C130.32986 (15)0.5449 (2)0.5522 (3)0.0324 (6)
C140.29295 (16)0.5298 (3)0.6599 (3)0.0377 (7)
H140.31990.52650.74100.045*
C150.21749 (16)0.5196 (3)0.6495 (3)0.0379 (7)
H150.19310.51080.72440.045*
C160.17531 (15)0.5217 (2)0.5326 (3)0.0342 (6)
C170.21226 (16)0.5333 (2)0.4247 (3)0.0343 (6)
H170.18530.53310.34360.041*
C180.28849 (16)0.5451 (2)0.4344 (3)0.0357 (7)
H180.31290.55360.35950.043*
C190.09289 (16)0.5105 (3)0.5244 (3)0.0446 (7)
H19A0.07530.46630.44610.067*
H19B0.07100.59510.52440.067*
H19C0.07860.46260.59750.067*
C200.45389 (16)0.6270 (2)0.6362 (2)0.0318 (6)
C210.42898 (18)0.7175 (2)0.7187 (3)0.0388 (7)
H210.37790.72880.72610.047*
C220.48103 (17)0.7898 (2)0.7891 (3)0.0391 (7)
H220.46530.85160.84580.047*
C230.55493 (18)0.7741 (2)0.7787 (3)0.0412 (7)
H230.59080.82420.82640.049*
C240.57493 (18)0.6821 (2)0.6957 (3)0.0404 (7)
H240.62580.66900.68740.049*
H1N0.0699 (14)0.510 (2)0.017 (2)0.047 (9)*
H3N0.4165 (16)0.495 (2)0.498 (2)0.045 (9)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0326 (12)0.0186 (10)0.0293 (12)0.0017 (9)0.0053 (9)0.0041 (8)
N20.0344 (12)0.0213 (10)0.0291 (12)0.0011 (9)0.0080 (9)0.0022 (8)
N30.0438 (14)0.0293 (12)0.0327 (13)−0.0009 (10)0.0075 (11)−0.0068 (10)
N40.0537 (15)0.0173 (10)0.0240 (11)−0.0013 (10)0.0032 (10)−0.0002 (8)
C10.0341 (14)0.0227 (12)0.0206 (12)−0.0018 (10)0.0022 (10)−0.0012 (9)
C20.0361 (15)0.0211 (12)0.0302 (14)−0.0005 (11)0.0012 (11)−0.0006 (10)
C30.0340 (15)0.0325 (14)0.0342 (15)0.0038 (12)0.0006 (12)0.0000 (11)
C40.0347 (15)0.0372 (15)0.0279 (14)−0.0031 (12)0.0015 (11)0.0026 (11)
C50.0437 (17)0.0266 (13)0.0316 (15)−0.0074 (12)0.0022 (12)0.0034 (11)
C60.0413 (16)0.0220 (12)0.0306 (14)−0.0002 (11)0.0043 (12)0.0015 (10)
C70.0378 (17)0.0472 (17)0.0410 (17)−0.0038 (13)0.0053 (13)0.0045 (13)
C80.0414 (15)0.0165 (11)0.0237 (13)−0.0001 (10)0.0077 (11)−0.0019 (9)
C90.0399 (16)0.0256 (13)0.0273 (14)−0.0003 (11)0.0009 (11)0.0009 (10)
C100.0548 (19)0.0287 (14)0.0280 (15)−0.0006 (13)0.0046 (13)0.0070 (11)
C110.0512 (18)0.0289 (14)0.0342 (16)−0.0050 (13)0.0112 (13)0.0072 (11)
C120.0413 (16)0.0302 (14)0.0320 (15)−0.0034 (12)0.0103 (12)0.0034 (11)
C130.0402 (16)0.0240 (13)0.0331 (15)0.0023 (11)0.0033 (12)−0.0010 (11)
C140.0434 (17)0.0361 (15)0.0338 (15)0.0017 (13)0.0043 (13)0.0060 (12)
C150.0438 (17)0.0321 (14)0.0383 (16)0.0028 (12)0.0069 (13)0.0044 (12)
C160.0366 (16)0.0218 (12)0.0449 (17)0.0031 (11)0.0083 (13)−0.0004 (11)
C170.0455 (17)0.0228 (13)0.0350 (15)0.0008 (12)0.0056 (12)0.0003 (11)
C180.0477 (17)0.0266 (14)0.0343 (15)−0.0010 (12)0.0112 (13)−0.0005 (11)
C190.0379 (17)0.0482 (18)0.0481 (19)0.0053 (14)0.0067 (14)0.0015 (14)
C200.0491 (17)0.0213 (12)0.0253 (14)−0.0014 (11)0.0044 (12)0.0031 (10)
C210.0591 (19)0.0267 (14)0.0309 (15)−0.0007 (13)0.0052 (13)−0.0021 (11)
C220.065 (2)0.0221 (13)0.0298 (15)0.0027 (13)0.0000 (14)−0.0040 (11)
C230.069 (2)0.0218 (13)0.0313 (16)0.0038 (13)−0.0040 (14)−0.0044 (11)
C240.0553 (19)0.0253 (13)0.0404 (17)0.0010 (13)0.0025 (14)−0.0005 (12)

Geometric parameters (Å, °)

N1—C81.376 (3)C10—C111.379 (4)
N1—C11.407 (3)C10—H100.9500
N1—H1N0.884 (10)C11—C121.375 (4)
N2—C121.340 (3)C11—H110.9500
N2—C81.348 (3)C12—H120.9500
N3—C201.376 (3)C13—C141.388 (4)
N3—C131.412 (3)C13—C181.398 (4)
N3—H3N0.911 (10)C14—C151.374 (4)
N4—C201.320 (3)C14—H140.9500
N4—C241.359 (3)C15—C161.396 (4)
C1—C21.393 (3)C15—H150.9500
C1—C61.395 (3)C16—C171.385 (4)
C2—C31.374 (4)C16—C191.501 (4)
C2—H20.9500C17—C181.389 (4)
C3—C41.397 (4)C17—H170.9500
C3—H30.9500C18—H180.9500
C4—C51.391 (4)C19—H19A0.9800
C4—C71.506 (4)C19—H19B0.9800
C5—C61.380 (4)C19—H19C0.9800
C5—H50.9500C20—C211.400 (4)
C6—H00.9500C21—C221.381 (4)
C7—H7A0.9800C21—H210.9500
C7—H7B0.9800C22—C231.372 (4)
C7—H7C0.9800C22—H220.9500
C8—C91.400 (3)C23—C241.382 (4)
C9—C101.374 (4)C23—H230.9500
C9—H90.9500C24—H240.9500
C8—N1—C1127.0 (2)C10—C11—H11121.2
C8—N1—H1N115 (2)N2—C12—C11124.1 (3)
C1—N1—H1N117 (2)N2—C12—H12117.9
C12—N2—C8117.7 (2)C11—C12—H12117.9
C20—N3—C13128.0 (2)C14—C13—C18118.2 (3)
C20—N3—H3N131.8 (19)C14—C13—N3122.2 (3)
C13—N3—H3N100.2 (19)C18—C13—N3119.5 (2)
C20—N4—C24119.2 (2)C15—C14—C13120.1 (3)
C2—C1—C6118.4 (2)C15—C14—H14119.9
C2—C1—N1123.1 (2)C13—C14—H14119.9
C6—C1—N1118.4 (2)C14—C15—C16122.3 (3)
C3—C2—C1120.3 (2)C14—C15—H15118.8
C3—C2—H2119.9C16—C15—H15118.8
C1—C2—H2119.9C17—C16—C15117.7 (3)
C2—C3—C4122.0 (2)C17—C16—C19121.4 (3)
C2—C3—H3119.0C15—C16—C19121.0 (3)
C4—C3—H3119.0C16—C17—C18120.5 (3)
C5—C4—C3117.2 (2)C16—C17—H17119.8
C5—C4—C7121.3 (2)C18—C17—H17119.8
C3—C4—C7121.5 (3)C17—C18—C13121.2 (3)
C6—C5—C4121.5 (2)C17—C18—H18119.4
C6—C5—H5119.3C13—C18—H18119.4
C4—C5—H5119.3C16—C19—H19A109.5
C5—C6—C1120.6 (2)C16—C19—H19B109.5
C5—C6—H0119.7H19A—C19—H19B109.5
C1—C6—H0119.7C16—C19—H19C109.5
C4—C7—H7A109.5H19A—C19—H19C109.5
C4—C7—H7B109.5H19B—C19—H19C109.5
H7A—C7—H7B109.5N4—C20—N3114.9 (2)
C4—C7—H7C109.5N4—C20—C21121.7 (3)
H7A—C7—H7C109.5N3—C20—C21123.4 (3)
H7B—C7—H7C109.5C22—C21—C20118.0 (3)
N2—C8—N1114.4 (2)C22—C21—H21121.0
N2—C8—C9121.7 (2)C20—C21—H21121.0
N1—C8—C9123.8 (2)C23—C22—C21121.3 (3)
C10—C9—C8118.6 (3)C23—C22—H22119.4
C10—C9—H9120.7C21—C22—H22119.4
C8—C9—H9120.7C22—C23—C24117.1 (3)
C9—C10—C11120.3 (3)C22—C23—H23121.4
C9—C10—H10119.9C24—C23—H23121.4
C11—C10—H10119.9N4—C24—C23122.7 (3)
C12—C11—C10117.6 (2)N4—C24—H24118.7
C12—C11—H11121.2C23—C24—H24118.7
C8—N1—C1—C239.0 (4)C20—N3—C13—C14−48.6 (4)
C8—N1—C1—C6−144.6 (2)C20—N3—C13—C18135.1 (3)
C6—C1—C2—C31.5 (4)C18—C13—C14—C15−2.0 (4)
N1—C1—C2—C3177.9 (2)N3—C13—C14—C15−178.4 (2)
C1—C2—C3—C4−0.7 (4)C13—C14—C15—C161.1 (4)
C2—C3—C4—C5−1.0 (4)C14—C15—C16—C170.7 (4)
C2—C3—C4—C7178.3 (2)C14—C15—C16—C19−179.9 (3)
C3—C4—C5—C61.9 (4)C15—C16—C17—C18−1.4 (4)
C7—C4—C5—C6−177.4 (2)C19—C16—C17—C18179.2 (2)
C4—C5—C6—C1−1.1 (4)C16—C17—C18—C130.4 (4)
C2—C1—C6—C5−0.6 (4)C14—C13—C18—C171.3 (4)
N1—C1—C6—C5−177.2 (2)N3—C13—C18—C17177.8 (2)
C12—N2—C8—N1−177.6 (2)C24—N4—C20—N3177.5 (2)
C12—N2—C8—C9−0.2 (3)C24—N4—C20—C21−0.7 (4)
C1—N1—C8—N2−166.9 (2)C13—N3—C20—N4176.3 (2)
C1—N1—C8—C915.8 (4)C13—N3—C20—C21−5.5 (4)
N2—C8—C9—C100.7 (4)N4—C20—C21—C220.5 (4)
N1—C8—C9—C10177.8 (2)N3—C20—C21—C22−177.5 (2)
C8—C9—C10—C11−0.3 (4)C20—C21—C22—C230.1 (4)
C9—C10—C11—C12−0.4 (4)C21—C22—C23—C24−0.6 (4)
C8—N2—C12—C11−0.6 (4)C20—N4—C24—C230.2 (4)
C10—C11—C12—N20.9 (4)C22—C23—C24—N40.5 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1n···N2i0.88 (1)2.06 (1)2.944 (3)174 (3)
N3—H3n···N4ii0.91 (1)2.08 (2)2.949 (3)159 (3)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SG2278).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Polamo, M., Repo, T. & Leskela, M. (1997). Acta Chem. Scand.51, 325–329.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2008). publCIF In preparation.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography