2-(3-Chloro­anilino)pyridine

Fairuz, Z.A.; Aiyub, Z.; Abdullah, Z.; Ng, S.W.

doi:10.1107/S1600536809019941

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1449

doi:10.1107/S1600536809019941

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2-(3-Chloroanilino)pyridine

Zainal Abidin Fairuz,^a Zaharah Aiyub,^a Zanariah Abdullah ^a and Seik Weng Ng ^a ^*

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

(Received 25 May 2009; accepted 26 May 2009; online 29 May 2009)

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, $[P \overline 1]$
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) Å³
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[F² > 2σ(F²)] = 0.047
wR(F²) = 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

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) -x+1, -y+1, -z+1.

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809019941/tk2464sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809019941/tk2464Isup2.hkl

checkCIF report

Related literature top

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

Experimental top

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.

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, 2009).

Figures top

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.

2-(3-Chloroanilino)pyridine top

Crystal data top

C₁₁H₉ClN₂	Z = 2
M_r = 204.65	F(000) = 212
Triclinic, P1	D_x = 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 top

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

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)] = 0.047	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(F_o²) + (0.0578P)² + 0.8P] where P = (F_o² + 2F_c²)/3
2064 reflections	(Δ/σ)_max = 0.001
131 parameters	Δρ_max = 0.37 e Å⁻³
1 restraint	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₁H₉ClN₂	γ = 88.240 (2)°
M_r = 204.65	V = 473.40 (3) Å³
Triclinic, P1	Z = 2
a = 3.8954 (1) Å	Mo Kα radiation
b = 10.7804 (4) Å	µ = 0.36 mm⁻¹
c = 12.4548 (4) Å	T = 119 K
α = 64.932 (2)°	0.40 × 0.05 × 0.02 mm
β = 88.004 (2)°

Data collection top

Bruker SMART APEX diffractometer	2064 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1807 reflections with I > 2σ(I)
T_min = 0.870, T_max = 0.993	R_int = 0.019
5923 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	1 restraint
wR(F²) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.37 e Å⁻³
2064 reflections	Δρ_min = −0.29 e Å⁻³
131 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₁H₉ClN₂
M_r	204.65
Crystal system, space group	Triclinic, P1
Temperature (K)	119
a, b, c (Å)	3.8954 (1), 10.7804 (4), 12.4548 (4)
α, β, γ (°)	64.932 (2), 88.004 (2), 88.240 (2)
V (Å³)	473.40 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.40 × 0.05 × 0.02

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.870, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	5923, 2064, 1807
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.133, 1.07
No. of reflections	2064
No. of parameters	131
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)	0.37, −0.29

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

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) −x+1, −y+1, −z+1.

Acknowledgements

We thank the University of Malaya for supporting this study (FS314/2008 C, RG027/09AFR).

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fairuz, M. Z. A., Aiyub, Z., Abdullah, Z. & Ng, S. W. (2008). Acta Cryst. E64, o1800. Web of Science CSD 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. (2009). publCIF. In preparation. Google Scholar