2-(3-Chloro­anilino)pyridine

Abstract

In the title compound, C₁₁H₉ClN, the dihedral angle between the aromatic ring planes is 44.2 (1)° and the bridging C—N—C bond angle is 127.60 (19)°. The amino N—H grouping makes a hydrogen bond to the pyridyl N atom of an adjacent mol­ecule across a center of inversion, generating a hydrogen-bonded dimer.

Related literature

For the crystal structure of the 4-chloro derivative, see: Fairuz et al. (2008 ▶).

Experimental

Crystal data

• C₁₁H₉ClN₂

• M _r = 204.65

• Triclinic,

• a = 3.8954 (1) Å

• b = 10.7804 (4) Å

• c = 12.4548 (4) Å

• α = 64.932 (2)°

• β = 88.004 (2)°

• γ = 88.240 (2)°

• V = 473.40 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 0.36 mm⁻¹

• T = 119 K

• 0.40 × 0.05 × 0.02 mm

Data collection

• Bruker SMART APEX diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.870, T _max = 0.993

• 5923 measured reflections

• 2064 independent reflections

• 1807 reflections with I > 2σ(I)

• R _int = 0.019

Refinement

• R[F ² > 2σ(F ²)] = 0.047

• wR(F ²) = 0.133

• S = 1.07

• 2064 reflections

• 131 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.37 e Å⁻³

• Δρ_min = −0.29 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; 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, 2009 ▶).

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2i	0.88 (1)	2.18 (1)	3.042 (3)	167 (3)

Symmetry code: (i) .

supplementary crystallographic information

Experimental

2-Chloropyridine (0.5 ml, 5.28 mmol) and 3-chloroaniline (0.67 g, 5.28 mmol) were heated at 423–433 K for 3 h. The solid was dissolved in water and extracted with ether. The ether extract was dried over sodium sulfate. The solvent was evaporated and the product recrystallized from ethanol to yield pale-purple crystals.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 Å) and were included in the refinement in the riding model approximation with U(H) fixed at 1.2U(C). The amino H-atom was located in a difference Fourier map and was refined with a distance restraint of N–H 0.88±0.01 Å; the isotropic temperature factor were refined.

Figures

Fig. 1.

Thermal ellipsoid plot (Barbour, 2001) of the hydrogen-bonded (dashed lines) centrosymmetric dimer {C11H9ClN2}2 with molecules drawn at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C11H9ClN2	Z = 2
Mr = 204.65	F(000) = 212
Triclinic, P1	Dx = 1.436 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 3.8954 (1) Å	Cell parameters from 1691 reflections
b = 10.7804 (4) Å	θ = 3.2–27.7°
c = 12.4548 (4) Å	µ = 0.36 mm−1
α = 64.932 (2)°	T = 119 K
β = 88.004 (2)°	Prism, pale purple
γ = 88.240 (2)°	0.40 × 0.05 × 0.02 mm
V = 473.40 (3) Å3

Data collection

Bruker SMART APEX diffractometer	2064 independent reflections
Radiation source: fine-focus sealed tube	1807 reflections with I > 2σ(I)
graphite	Rint = 0.019
ω scans	θmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→5
Tmin = 0.870, Tmax = 0.993	k = −13→14
5923 measured reflections	l = −16→16

Refinement

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0578P)2 + 0.8P] where P = (Fo2 + 2Fc2)/3
2064 reflections	(Δ/σ)max = 0.001
131 parameters	Δρmax = 0.37 e Å−3
1 restraint	Δρmin = −0.29 e Å−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Cl1	0.67761 (16)	−0.15289 (6)	0.94724 (5)	0.0242 (2)
N1	0.7040 (6)	0.3450 (2)	0.62528 (17)	0.0224 (5)
H1	0.654 (8)	0.390 (3)	0.5500 (11)	0.024 (7)*
N2	0.5081 (5)	0.5439 (2)	0.63195 (17)	0.0207 (4)
C1	0.4688 (6)	0.6248 (2)	0.6895 (2)	0.0215 (5)
H1A	0.3597	0.7118	0.6492	0.026*
C2	0.5768 (7)	0.5897 (3)	0.8032 (2)	0.0237 (5)
H2	0.5413	0.6501	0.8404	0.028*
C3	0.7401 (7)	0.4624 (2)	0.8620 (2)	0.0230 (5)
H3	0.8192	0.4351	0.9402	0.028*
C4	0.7861 (6)	0.3767 (2)	0.8060 (2)	0.0206 (5)
H4	0.8982	0.2901	0.8443	0.025*
C5	0.6623 (6)	0.4211 (2)	0.69013 (19)	0.0186 (5)
C6	0.8088 (6)	0.2076 (2)	0.6660 (2)	0.0185 (5)
C7	0.7102 (6)	0.1066 (2)	0.77788 (19)	0.0179 (5)
H7	0.5747	0.1306	0.8314	0.022*
C8	0.8122 (6)	−0.0275 (2)	0.80912 (19)	0.0179 (5)
C9	1.0038 (6)	−0.0685 (2)	0.7336 (2)	0.0209 (5)
H9	1.0677	−0.1619	0.7565	0.025*
C10	1.0995 (6)	0.0324 (3)	0.6223 (2)	0.0225 (5)
H10	1.2316	0.0075	0.5687	0.027*
C11	1.0045 (6)	0.1685 (2)	0.5891 (2)	0.0201 (5)
H11	1.0731	0.2357	0.5132	0.024*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0325 (4)	0.0186 (3)	0.0169 (3)	−0.0002 (2)	−0.0003 (2)	−0.0032 (2)
N1	0.0351 (12)	0.0172 (10)	0.0128 (9)	0.0037 (8)	−0.0029 (8)	−0.0044 (8)
N2	0.0263 (11)	0.0173 (9)	0.0156 (9)	0.0010 (8)	0.0006 (8)	−0.0043 (7)
C1	0.0234 (12)	0.0194 (11)	0.0205 (11)	0.0009 (9)	0.0027 (9)	−0.0076 (9)
C2	0.0287 (13)	0.0228 (12)	0.0222 (12)	−0.0034 (10)	0.0036 (10)	−0.0119 (10)
C3	0.0297 (13)	0.0224 (12)	0.0158 (11)	−0.0051 (10)	−0.0008 (9)	−0.0069 (9)
C4	0.0225 (12)	0.0183 (11)	0.0194 (11)	−0.0007 (9)	−0.0038 (9)	−0.0061 (9)
C5	0.0227 (12)	0.0169 (11)	0.0135 (10)	−0.0034 (9)	0.0011 (8)	−0.0038 (8)
C6	0.0192 (11)	0.0185 (11)	0.0173 (11)	0.0007 (9)	−0.0028 (8)	−0.0071 (9)
C7	0.0191 (11)	0.0204 (11)	0.0139 (10)	0.0021 (9)	−0.0005 (8)	−0.0070 (9)
C8	0.0198 (11)	0.0166 (10)	0.0139 (10)	−0.0013 (8)	−0.0022 (8)	−0.0029 (8)
C9	0.0227 (12)	0.0180 (11)	0.0224 (11)	0.0032 (9)	−0.0038 (9)	−0.0091 (9)
C10	0.0209 (12)	0.0286 (13)	0.0201 (11)	0.0026 (9)	−0.0002 (9)	−0.0126 (10)
C11	0.0202 (12)	0.0244 (12)	0.0145 (10)	−0.0011 (9)	−0.0004 (8)	−0.0071 (9)

Geometric parameters (Å, °)

Cl1—C8	1.752 (2)	C4—C5	1.411 (3)
N1—C5	1.376 (3)	C4—H4	0.9500
N1—C6	1.400 (3)	C6—C11	1.396 (3)
N1—H1	0.880 (10)	C6—C7	1.406 (3)
N2—C5	1.345 (3)	C7—C8	1.378 (3)
N2—C1	1.346 (3)	C7—H7	0.9500
C1—C2	1.380 (3)	C8—C9	1.386 (3)
C1—H1A	0.9500	C9—C10	1.398 (3)
C2—C3	1.397 (3)	C9—H9	0.9500
C2—H2	0.9500	C10—C11	1.386 (3)
C3—C4	1.378 (3)	C10—H10	0.9500
C3—H3	0.9500	C11—H11	0.9500
C5—N1—C6	127.60 (19)	N1—C6—C11	118.1 (2)
C5—N1—H1	114.3 (19)	N1—C6—C7	123.0 (2)
C6—N1—H1	118.1 (19)	C11—C6—C7	118.8 (2)
C5—N2—C1	117.3 (2)	C8—C7—C6	119.3 (2)
N2—C1—C2	124.2 (2)	C8—C7—H7	120.4
N2—C1—H1A	117.9	C6—C7—H7	120.4
C2—C1—H1A	117.9	C7—C8—C9	122.7 (2)
C1—C2—C3	117.8 (2)	C7—C8—Cl1	118.76 (18)
C1—C2—H2	121.1	C9—C8—Cl1	118.48 (17)
C3—C2—H2	121.1	C8—C9—C10	117.6 (2)
C4—C3—C2	119.7 (2)	C8—C9—H9	121.2
C4—C3—H3	120.1	C10—C9—H9	121.2
C2—C3—H3	120.1	C11—C10—C9	121.0 (2)
C3—C4—C5	118.2 (2)	C11—C10—H10	119.5
C3—C4—H4	120.9	C9—C10—H10	119.5
C5—C4—H4	120.9	C10—C11—C6	120.6 (2)
N2—C5—N1	114.4 (2)	C10—C11—H11	119.7
N2—C5—C4	122.7 (2)	C6—C11—H11	119.7
N1—C5—C4	122.8 (2)
C5—N2—C1—C2	0.2 (4)	C5—N1—C6—C7	37.1 (4)
N2—C1—C2—C3	0.6 (4)	N1—C6—C7—C8	177.1 (2)
C1—C2—C3—C4	−0.4 (4)	C11—C6—C7—C8	0.8 (3)
C2—C3—C4—C5	−0.5 (4)	C6—C7—C8—C9	−1.4 (4)
C1—N2—C5—N1	−178.1 (2)	C6—C7—C8—Cl1	−178.31 (17)
C1—N2—C5—C4	−1.1 (4)	C7—C8—C9—C10	1.1 (4)
C6—N1—C5—N2	−170.1 (2)	Cl1—C8—C9—C10	178.04 (18)
C6—N1—C5—C4	12.9 (4)	C8—C9—C10—C11	−0.2 (4)
C3—C4—C5—N2	1.3 (4)	C9—C10—C11—C6	−0.3 (4)
C3—C4—C5—N1	178.1 (2)	N1—C6—C11—C10	−176.5 (2)
C5—N1—C6—C11	−146.5 (2)	C7—C6—C11—C10	0.1 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2i	0.88 (1)	2.18 (1)	3.042 (3)	167 (3)

Symmetry codes: (i) −x+1, −y+1, −z+1.