N-(4-Chloro­phen­yl)-4-methyl­pyridin-2-amine

Fairuz, Z.A.; Aiyub, Z.; Abdullah, Z.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536810030138

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o2186

https://doi.org/10.1107/S1600536810030138

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N-(4-Chlorophenyl)-4-methylpyridin-2-amine

Zainal A. Fairuz,^a Zaharah Aiyub,^a Zanariah Abdullah,^a ‡ Seik Weng Ng ^a and Edward R. T. Tiekink ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 28 July 2010; accepted 29 July 2010; online 31 July 2010)

In the title compound, C₁₂H₁₁ClN₂, the dihedral angle between the benzene and pyridyl rings is 48.03 (8)°. Twists are also evident in the molecule, in particular about the N_a–C_b (a = amine and b = benzene) bond [C—N—C—C = −144.79 (18)°]. In the crystal, inversion dimers linked by pairs of N—H⋯N hydrogen bonds result in the formation of eight-membered {⋯NCNH}₂ synthons [or R₂²(8) loops].

Related literature

For background to the fluorescence properties of compounds related to the title compound, see: Kawai et al. (2001 ); Abdullah (2005 ).

Experimental

Crystal data

C₁₂H₁₁ClN₂
M_r = 218.68
Monoclinic, P 2₁ /n
a = 15.9335 (15) Å
b = 4.0651 (4) Å
c = 17.0153 (16) Å
β = 98.755 (1)°
V = 1089.26 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 293 K
0.30 × 0.30 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.776, T_max = 0.862
9785 measured reflections
2509 independent reflections
1886 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.132
S = 1.04
2509 reflections
141 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2n⋯N1ⁱ	0.86 (1)	2.19 (1)	3.029 (2)	167 (2)
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810030138/hb5582sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810030138/hb5582Isup2.hkl

checkCIF report

Comment top

The title compound, (I), was investigated in the context of potential fluorescence properties (Kawai et al. 2001; Abdullah, 2005). The molecular structure of (I), Fig. 1, shows that the molecule is non-planar as seen in the dihedral angle of 48.03 (8) ° formed between the benzene and pyridyl rings, and in the twists about the central N–C bonds, i.e. the C7–N2–C1–N1 and C1–N2–C7–C8 torsion angles are -167.92 (17) and -144.79 (18) °, respectively. The amine-H and pyridine-N atoms are orientated in the same direction, an arrangement that facilitates the formation of N–H···N hydrogen bonds. Thus, centrosymmetrically related molecules are linked via N–H···N hydrogen bonds that lead to eight-membered {···NCNH}₂ synthons, Table 1. The dimeric aggregates stack along the b axis, Fig. 2.

Related literature top

For background to the fluorescence properties of compounds related to the title compound, see: Kawai et al. (2001); Abdullah (2005).

Experimental top

2-Chloro-4-methylpyridine (1.0 ml, 1.14 mmol) was added to 4-chloroaniline (1.4543 g, 1.14 mmol) and heated for 2 h. The mixture was cooled and dissolved water (15 ml), extracted with diethyl ether (3 × 10 ml), washed with water (3 × 10 ml), and then dried over anhydrous sodium sulfate. Evaporation of the solvent gave a gray solid. Recrystallization from ethanol yielded colourless blocks of (I).

Structure description top

For background to the fluorescence properties of compounds related to the title compound, see: Kawai et al. (2001); Abdullah (2005).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I) showing displacement ellipsoids at the 35% probability level.
	Fig. 2. Unit-cell contents shown in projection down the b axis in (I). The N–H···N hydrogen bonding is shown as orange dashed lines.

N-(4-Chlorophenyl)-4-methylpyridin-2-amine top

Crystal data top

C₁₂H₁₁ClN₂	F(000) = 456
M_r = 218.68	D_x = 1.333 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2763 reflections
a = 15.9335 (15) Å	θ = 2.4–25.7°
b = 4.0651 (4) Å	µ = 0.32 mm⁻¹
c = 17.0153 (16) Å	T = 293 K
β = 98.755 (1)°	Block, colourless
V = 1089.26 (18) Å³	0.30 × 0.30 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	2509 independent reflections
Radiation source: fine-focus sealed tube	1886 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω scans	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −20→19
T_min = 0.776, T_max = 0.862	k = −5→5
9785 measured reflections	l = −22→20

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.132	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0689P)² + 0.1992P] where P = (F_o² + 2F_c²)/3
2509 reflections	(Δ/σ)_max < 0.001
141 parameters	Δρ_max = 0.22 e Å⁻³
1 restraint	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₂H₁₁ClN₂	V = 1089.26 (18) Å³
M_r = 218.68	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 15.9335 (15) Å	µ = 0.32 mm⁻¹
b = 4.0651 (4) Å	T = 293 K
c = 17.0153 (16) Å	0.30 × 0.30 × 0.20 mm
β = 98.755 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	2509 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1886 reflections with I > 2σ(I)
T_min = 0.776, T_max = 0.862	R_int = 0.030
9785 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	1 restraint
wR(F²) = 0.132	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.22 e Å⁻³
2509 reflections	Δρ_min = −0.18 e Å⁻³
141 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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Cl1	0.59502 (4)	1.02913 (16)	0.10424 (3)	0.0834 (2)
N1	0.60831 (9)	0.5290 (4)	0.56614 (8)	0.0495 (4)
N2	0.57324 (9)	0.6997 (4)	0.43820 (9)	0.0552 (4)
H2n	0.5222 (7)	0.653 (5)	0.4444 (11)	0.061 (6)*
C1	0.63451 (10)	0.6751 (4)	0.50365 (9)	0.0439 (4)
C2	0.66466 (12)	0.5088 (5)	0.63260 (11)	0.0578 (5)
H2	0.6472	0.4101	0.6767	0.069*
C3	0.74612 (12)	0.6230 (5)	0.64035 (10)	0.0570 (5)
H3	0.7827	0.5985	0.6881	0.068*
C4	0.77369 (11)	0.7769 (4)	0.57556 (10)	0.0498 (4)
C5	0.71648 (10)	0.8019 (4)	0.50667 (10)	0.0461 (4)
H5	0.7323	0.9030	0.4621	0.055*
C6	0.86175 (12)	0.9137 (6)	0.58031 (13)	0.0661 (5)
H6A	0.8620	1.0847	0.5414	0.099*
H6B	0.8999	0.7416	0.5701	0.099*
H6C	0.8797	1.0023	0.6325	0.099*
C7	0.58319 (10)	0.7850 (4)	0.36041 (9)	0.0428 (4)
C8	0.51945 (11)	0.9664 (4)	0.31600 (11)	0.0496 (4)
H8	0.4740	1.0406	0.3396	0.059*
C9	0.52239 (12)	1.0389 (4)	0.23723 (11)	0.0544 (4)
H9	0.4789	1.1588	0.2077	0.065*
C10	0.59014 (12)	0.9323 (4)	0.20290 (10)	0.0493 (4)
C11	0.65418 (11)	0.7545 (4)	0.24569 (10)	0.0481 (4)
H11	0.6998	0.6843	0.2219	0.058*
C12	0.65108 (10)	0.6791 (4)	0.32428 (10)	0.0462 (4)
H12	0.6946	0.5570	0.3532	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1035 (5)	0.0997 (5)	0.0472 (3)	−0.0123 (3)	0.0123 (3)	0.0172 (3)
N1	0.0440 (8)	0.0626 (9)	0.0425 (8)	0.0058 (6)	0.0082 (6)	0.0026 (6)
N2	0.0364 (8)	0.0858 (12)	0.0428 (8)	−0.0052 (7)	0.0048 (6)	0.0083 (7)
C1	0.0414 (8)	0.0494 (9)	0.0409 (8)	0.0059 (7)	0.0061 (6)	−0.0034 (7)
C2	0.0582 (11)	0.0722 (13)	0.0430 (9)	0.0070 (9)	0.0072 (8)	0.0058 (8)
C3	0.0574 (11)	0.0673 (11)	0.0424 (9)	0.0083 (9)	−0.0051 (8)	−0.0042 (8)
C4	0.0481 (9)	0.0476 (9)	0.0515 (10)	0.0039 (7)	0.0006 (7)	−0.0127 (7)
C5	0.0452 (9)	0.0486 (9)	0.0439 (9)	−0.0008 (7)	0.0049 (7)	−0.0019 (7)
C6	0.0535 (11)	0.0693 (12)	0.0705 (13)	−0.0074 (9)	−0.0066 (9)	−0.0119 (10)
C7	0.0379 (8)	0.0485 (9)	0.0409 (8)	−0.0039 (7)	0.0027 (6)	−0.0004 (7)
C8	0.0436 (9)	0.0535 (10)	0.0512 (10)	0.0057 (7)	0.0059 (7)	−0.0012 (7)
C9	0.0539 (10)	0.0521 (10)	0.0541 (10)	0.0051 (8)	−0.0019 (8)	0.0089 (8)
C10	0.0572 (10)	0.0488 (9)	0.0411 (8)	−0.0110 (8)	0.0052 (7)	0.0025 (7)
C11	0.0440 (9)	0.0518 (10)	0.0495 (9)	−0.0053 (7)	0.0101 (7)	−0.0027 (7)
C12	0.0373 (8)	0.0517 (9)	0.0486 (9)	0.0024 (7)	0.0032 (7)	0.0034 (7)

Geometric parameters (Å, º) top

Cl1—C10	1.7376 (18)	C6—H6A	0.9600
N1—C2	1.335 (2)	C6—H6B	0.9600
N1—C1	1.339 (2)	C6—H6C	0.9600
N2—C1	1.368 (2)	C7—C8	1.383 (2)
N2—C7	1.400 (2)	C7—C12	1.391 (2)
N2—H2n	0.857 (9)	C8—C9	1.380 (2)
C1—C5	1.398 (2)	C8—H8	0.9300
C2—C3	1.366 (3)	C9—C10	1.373 (3)
C2—H2	0.9300	C9—H9	0.9300
C3—C4	1.396 (3)	C10—C11	1.367 (2)
C3—H3	0.9300	C11—C12	1.380 (2)
C4—C5	1.375 (2)	C11—H11	0.9300
C4—C6	1.500 (3)	C12—H12	0.9300
C5—H5	0.9300

C2—N1—C1	116.69 (15)	C4—C6—H6C	109.5
C1—N2—C7	128.17 (14)	H6A—C6—H6C	109.5
C1—N2—H2n	117.2 (13)	H6B—C6—H6C	109.5
C7—N2—H2n	114.6 (13)	C8—C7—C12	118.64 (15)
N1—C1—N2	114.12 (15)	C8—C7—N2	117.97 (15)
N1—C1—C5	122.47 (15)	C12—C7—N2	123.27 (15)
N2—C1—C5	123.36 (15)	C9—C8—C7	120.91 (16)
N1—C2—C3	124.59 (18)	C9—C8—H8	119.5
N1—C2—H2	117.7	C7—C8—H8	119.5
C3—C2—H2	117.7	C10—C9—C8	119.40 (16)
C2—C3—C4	119.00 (16)	C10—C9—H9	120.3
C2—C3—H3	120.5	C8—C9—H9	120.3
C4—C3—H3	120.5	C11—C10—C9	120.77 (16)
C5—C4—C3	117.32 (16)	C11—C10—Cl1	119.67 (14)
C5—C4—C6	120.81 (17)	C9—C10—Cl1	119.55 (14)
C3—C4—C6	121.87 (16)	C10—C11—C12	119.99 (16)
C4—C5—C1	119.92 (16)	C10—C11—H11	120.0
C4—C5—H5	120.0	C12—C11—H11	120.0
C1—C5—H5	120.0	C11—C12—C7	120.28 (15)
C4—C6—H6A	109.5	C11—C12—H12	119.9
C4—C6—H6B	109.5	C7—C12—H12	119.9
H6A—C6—H6B	109.5

C2—N1—C1—N2	−177.70 (15)	C1—N2—C7—C8	−144.79 (18)
C2—N1—C1—C5	0.0 (2)	C1—N2—C7—C12	39.4 (3)
C7—N2—C1—N1	−167.92 (17)	C12—C7—C8—C9	0.6 (3)
C7—N2—C1—C5	14.4 (3)	N2—C7—C8—C9	−175.42 (16)
C1—N1—C2—C3	−0.7 (3)	C7—C8—C9—C10	−0.8 (3)
N1—C2—C3—C4	1.0 (3)	C8—C9—C10—C11	0.3 (3)
C2—C3—C4—C5	−0.6 (3)	C8—C9—C10—Cl1	−178.88 (14)
C2—C3—C4—C6	178.85 (18)	C9—C10—C11—C12	0.2 (3)
C3—C4—C5—C1	−0.1 (2)	Cl1—C10—C11—C12	179.44 (13)
C6—C4—C5—C1	−179.50 (17)	C10—C11—C12—C7	−0.4 (3)
N1—C1—C5—C4	0.4 (3)	C8—C7—C12—C11	−0.1 (2)
N2—C1—C5—C4	177.85 (16)	N2—C7—C12—C11	175.77 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2n···N1ⁱ	0.86 (1)	2.19 (1)	3.029 (2)	167 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₁ClN₂
M_r	218.68
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	15.9335 (15), 4.0651 (4), 17.0153 (16)
β (°)	98.755 (1)
V (Å³)	1089.26 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.30 × 0.30 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.776, 0.862
No. of measured, independent and observed [I > 2σ(I)] reflections	9785, 2509, 1886
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.132, 1.04
No. of reflections	2509
No. of parameters	141
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)	0.22, −0.18

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2n···N1ⁱ	0.857 (9)	2.189 (11)	3.029 (2)	166.5 (18)

Symmetry code: (i) −x+1, −y+1, −z+1.

Footnotes

‡Additional correspondence author, e-mail: zana@um.edu.my.

Acknowledgements

AZ thanks the Ministry of Higher Education, Malaysia, for research grants (RG027/09AFR and PS374/2009B). The authors are also grateful to the University of Malaya for support of the crystallographic facility.

References

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