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N-(2-Pyrid­yl)-4-toluidine

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

(Received 19 October 2008; accepted 11 November 2008; online 26 November 2008)

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[Polamo, M., Repo, T. & Leskela, M. (1997). Acta Chem. Scand. 51, 325-329.])

[Scheme 1]

Experimental

Crystal data
  • C12H12N2

  • Mr = 184.24

  • Monoclinic, P 21 /c

  • 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)

  • Rint = 0.066

Refinement
  • R[F2 > 2σ(F2)] = 0.070

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1n⋯N2i 0.88 (1) 2.06 (1) 2.944 (3) 174 (3)
N3—H3n⋯N4ii 0.91 (1) 2.08 (2) 2.949 (3) 159 (3)
Symmetry codes: (i) -x, -y+1, -z; (ii) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). 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, 2008[Westrip, S. P. (2008). publCIF. In preparation.]).

Supporting information


Comment top

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)

Related literature top

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

Experimental top

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 top

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.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with displacement ellipsoids at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
N-(2-Pyridyl)-4-toluidine top
Crystal data top
C12H12N2F(000) = 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 = 2.2–24.4°
b = 10.5680 (3) ŵ = 0.07 mm1
c = 10.6005 (3) ÅT = 100 K
β = 95.364 (2)°Prism, colorless
V = 2032.9 (1) Å30.30 × 0.10 × 0.05 mm
Z = 8
Data collection top
Bruker SMART APEX
diffractometer
2774 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.066
Graphite monochromatorθmax = 27.5°, θmin = 1.1°
ω scansh = 2323
18430 measured reflectionsk = 1313
4676 independent reflectionsl = 1313
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.070Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.206H atoms treated by a mixture of independent and constrained refinement
S = 1.01 w = 1/[σ2(Fo2) + (0.0922P)2 + 1.1608P]
where P = (Fo2 + 2Fc2)/3
4676 reflections(Δ/σ)max = 0.001
263 parametersΔρmax = 0.64 e Å3
2 restraintsΔρmin = 0.31 e Å3
Crystal data top
C12H12N2V = 2032.9 (1) Å3
Mr = 184.24Z = 8
Monoclinic, P21/cMo Kα radiation
a = 18.2260 (7) ŵ = 0.07 mm1
b = 10.5680 (3) ÅT = 100 K
c = 10.6005 (3) Å0.30 × 0.10 × 0.05 mm
β = 95.364 (2)°
Data collection top
Bruker SMART APEX
diffractometer
2774 reflections with I > 2σ(I)
18430 measured reflectionsRint = 0.066
4676 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0702 restraints
wR(F2) = 0.206H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.64 e Å3
4676 reflectionsΔρmin = 0.31 e Å3
263 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.09908 (12)0.46043 (18)0.0668 (2)0.0267 (5)
N20.01070 (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)
H7A0.41660.58220.03500.063*
H7B0.42130.43250.05550.063*
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*
C110.01855 (16)0.2121 (2)0.2684 (3)0.0377 (7)
H110.04820.15660.31260.045*
C120.04948 (16)0.2946 (2)0.1783 (3)0.0340 (6)
H120.10160.29550.16240.041*
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) top
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, º) top
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—C1448.6 (4)
C8—N1—C1—C6144.6 (2)C20—N3—C13—C18135.1 (3)
C6—C1—C2—C31.5 (4)C18—C13—C14—C152.0 (4)
N1—C1—C2—C3177.9 (2)N3—C13—C14—C15178.4 (2)
C1—C2—C3—C40.7 (4)C13—C14—C15—C161.1 (4)
C2—C3—C4—C51.0 (4)C14—C15—C16—C170.7 (4)
C2—C3—C4—C7178.3 (2)C14—C15—C16—C19179.9 (3)
C3—C4—C5—C61.9 (4)C15—C16—C17—C181.4 (4)
C7—C4—C5—C6177.4 (2)C19—C16—C17—C18179.2 (2)
C4—C5—C6—C11.1 (4)C16—C17—C18—C130.4 (4)
C2—C1—C6—C50.6 (4)C14—C13—C18—C171.3 (4)
N1—C1—C6—C5177.2 (2)N3—C13—C18—C17177.8 (2)
C12—N2—C8—N1177.6 (2)C24—N4—C20—N3177.5 (2)
C12—N2—C8—C90.2 (3)C24—N4—C20—C210.7 (4)
C1—N1—C8—N2166.9 (2)C13—N3—C20—N4176.3 (2)
C1—N1—C8—C915.8 (4)C13—N3—C20—C215.5 (4)
N2—C8—C9—C100.7 (4)N4—C20—C21—C220.5 (4)
N1—C8—C9—C10177.8 (2)N3—C20—C21—C22177.5 (2)
C8—C9—C10—C110.3 (4)C20—C21—C22—C230.1 (4)
C9—C10—C11—C120.4 (4)C21—C22—C23—C240.6 (4)
C8—N2—C12—C110.6 (4)C20—N4—C24—C230.2 (4)
C10—C11—C12—N20.9 (4)C22—C23—C24—N40.5 (4)
Hydrogen-bond geometry (Å, º) top
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.

Experimental details

Crystal data
Chemical formulaC12H12N2
Mr184.24
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)18.2260 (7), 10.5680 (3), 10.6005 (3)
β (°) 95.364 (2)
V3)2032.9 (1)
Z8
Radiation typeMo Kα
µ (mm1)0.07
Crystal size (mm)0.30 × 0.10 × 0.05
Data collection
DiffractometerBruker SMART APEX
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
18430, 4676, 2774
Rint0.066
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.070, 0.206, 1.01
No. of reflections4676
No. of parameters263
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.64, 0.31

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top
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.
 

Acknowledgements

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

References

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