N-(3-Chloro­phen­yl)-3-nitro­pyridin-2-amine

Aznan, A.M.A.; Abdullah, Z.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536811044011

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o3076

doi:10.1107/S1600536811044011

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N-(3-Chlorophenyl)-3-nitropyridin-2-amine

Aina Mardia Akhmad Aznan,^a Zanariah Abdullah,^a ‡ Seik Weng Ng ^a,^b and Edward R. T. Tiekink ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^bChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 19 October 2011; accepted 23 October 2011; online 29 October 2011)

The dihedral angle between the benzene and pyridyl rings in the title compound, C₁₁H₈ClN₃O₂, is 22.65 (10)°, indicating a twisted molecule. The amine H and nitro O atoms form a donor–acceptor pair for an intramolecular N—H⋯O hydrogen bond so that the nitro group is almost coplanar with the pyridine ring to which it is connected [O—N—C—C torsion angle = 7.4 (3)°]. The pyridine N and Cl atoms are approximately syn. The crystal packing features C—H⋯Cl interactions that lead to undulating supramolecular chains along [101]. These are connected into sheets by π–π interactions occurring between the benzene rings and between the pyridine rings of translationally related molecules along the b axis [centroid–centroid distances = length of b axis = 3.7157 (2) Å].

Related literature

For the structure of a related pyrimidine amine derivative, see: Aznan Akhmad et al. (2010 ).

Experimental

Crystal data

C₁₁H₈ClN₃O₂
M_r = 249.65
Monoclinic, P 2/n
a = 15.8781 (10) Å
b = 3.7157 (2) Å
c = 18.0651 (13) Å
β = 102.252 (6)°
V = 1041.53 (11) Å³
Z = 4
Cu Kα radiation
μ = 3.21 mm⁻¹
T = 100 K
0.20 × 0.05 × 0.03 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.566, T_max = 0.910
3341 measured reflections
1971 independent reflections
1684 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.119
S = 1.06
1971 reflections
158 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1n⋯O1	0.88 (3)	1.94 (3)	2.647 (2)	137 (2)
C9—H9⋯Cl1ⁱ	0.95	2.79	3.665 (2)	153
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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: 10.1107/S1600536811044011/hb6466sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811044011/hb6466Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811044011/hb6466Isup3.cml

checkCIF report

Comment top

The title compound, (I), was investigated in connection with our ongoing crystallographic studies of pyrimidine derivatives (Aznan Akhmad et al., 2010).

The molecule of (I), is twisted as seen in the value of the dihedral angle formed between the benzene and pyridyl rings of 22.65 (10)°. The nitro group is close to being co-planar with the pyridyl ring to which it is connected; the O1—N3—C8—C7 torsion angle is 7.4 (3)°. This conformation is stabilized by an intramolecular N1—H1n···O1 hydrogen bond, Table 1. The pyridine-N2 and m-Cl atoms are approximately syn.

In the crystal structure, C—H···Cl interactions, Table 1, lead to supramolecular chains with an undulating topology along [101], Fig. 2. These stack along the b axis, Fig. 3, whereby the components of the stacks are linked by π–π interactions occurring between translationally related benzene rings and between translationally related pyridyl rings with centroid···centroid distances corresponding to the b axis, i.e. = 3.7157 (2) Å, Fig. 4.

Related literature top

For the structure of a related pyrimidine amine derivative, see: Aznan Akhmad et al. (2010).

Experimental top

2-Chloro-3-nitro-pyridine (0.5 g, 0.00315 mol) and m-chloroaniline (0.3311 ml, 0.00315 mol) were refluxed in ethanol (5 ml) for 4 h at 385 K. The mixture was cooled and the obtained residue dissolved in a minimum volume of water (10 ml) and extracted with ether (3 x 10 ml). The ethereal layer was washed with water and dried over anhydrous sodium sulfate. Evaporation gave a reddish solid and recrystallization using diethyl ether yielded dark-orange prisms after one day. M.pt.: 406–409 K.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); 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 50% probability level.
	Fig. 2. Undulating supramolecular chain along [101] in (I) sustained by C—H···Cl interactions, shown as orange dashed lines.
	Fig. 3. Unit-cell contents for (I) shown in projection down the b axis highlighting the stacking of chains. The C—H···Cl interactions are shown as orange dashed lines.
	Fig. 4. Stacking of chains highlighting the π–π interactions shown as purple dashed lines. The C—H···Cl interactions are shown as orange dashed lines.

N-(3-Chlorophenyl)-3-nitropyridin-2-amine top

Crystal data top

C₁₁H₈ClN₃O₂	F(000) = 512
M_r = 249.65	D_x = 1.592 Mg m⁻³
Monoclinic, P2/n	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yac	Cell parameters from 1441 reflections
a = 15.8781 (10) Å	θ = 2.9–74.2°
b = 3.7157 (2) Å	µ = 3.21 mm⁻¹
c = 18.0651 (13) Å	T = 100 K
β = 102.252 (6)°	Prism, orange
V = 1041.53 (11) Å³	0.20 × 0.05 × 0.03 mm
Z = 4

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	1971 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	1684 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.026
Detector resolution: 10.4041 pixels mm^-1	θ_max = 70.0°, θ_min = 3.4°
ω scan	h = −19→16
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −4→2
T_min = 0.566, T_max = 0.910	l = −22→20
3341 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0688P)² + 0.3527P] where P = (F_o² + 2F_c²)/3
1971 reflections	(Δ/σ)_max = 0.001
158 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₁H₈ClN₃O₂	V = 1041.53 (11) Å³
M_r = 249.65	Z = 4
Monoclinic, P2/n	Cu Kα radiation
a = 15.8781 (10) Å	µ = 3.21 mm⁻¹
b = 3.7157 (2) Å	T = 100 K
c = 18.0651 (13) Å	0.20 × 0.05 × 0.03 mm
β = 102.252 (6)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	1971 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	1684 reflections with I > 2σ(I)
T_min = 0.566, T_max = 0.910	R_int = 0.026
3341 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.25 e Å⁻³
1971 reflections	Δρ_min = −0.34 e Å⁻³
158 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	0.78774 (3)	0.02226 (14)	0.66591 (3)	0.02816 (19)
O1	0.66072 (10)	0.4237 (5)	0.23466 (9)	0.0357 (4)
O2	0.54073 (10)	0.6787 (5)	0.18194 (9)	0.0348 (4)
N1	0.68353 (11)	0.1981 (5)	0.37651 (10)	0.0227 (4)
N2	0.55898 (11)	0.1975 (5)	0.42492 (9)	0.0221 (4)
N3	0.58523 (12)	0.5144 (5)	0.23471 (10)	0.0259 (4)
C1	0.74388 (13)	0.0748 (6)	0.44066 (12)	0.0217 (4)
C2	0.73308 (13)	0.1013 (5)	0.51495 (12)	0.0214 (4)
H2	0.6815	0.1947	0.5261	0.026*
C3	0.80060 (14)	−0.0138 (5)	0.57217 (12)	0.0225 (5)
C4	0.87682 (14)	−0.1519 (6)	0.55902 (13)	0.0258 (5)
H4	0.9216	−0.2272	0.5997	0.031*
C5	0.88592 (14)	−0.1769 (6)	0.48458 (12)	0.0268 (5)
H5	0.9376	−0.2719	0.4738	0.032*
C6	0.82038 (14)	−0.0648 (6)	0.42579 (13)	0.0245 (5)
H6	0.8274	−0.0828	0.3750	0.029*
C7	0.59821 (13)	0.2730 (5)	0.36741 (11)	0.0205 (4)
C8	0.54874 (14)	0.4251 (6)	0.29929 (11)	0.0213 (4)
C9	0.46195 (14)	0.4956 (5)	0.29291 (12)	0.0228 (5)
H9	0.4289	0.5972	0.2477	0.027*
C10	0.42391 (13)	0.4171 (6)	0.35261 (12)	0.0237 (5)
H10	0.3646	0.4644	0.3500	0.028*
C11	0.47531 (13)	0.2665 (6)	0.41660 (11)	0.0239 (5)
H11	0.4489	0.2081	0.4576	0.029*
H1n	0.7042 (17)	0.237 (8)	0.3359 (15)	0.041 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0287 (3)	0.0341 (3)	0.0202 (3)	−0.0026 (2)	0.0018 (2)	0.0004 (2)
O1	0.0280 (8)	0.0557 (11)	0.0255 (9)	0.0049 (8)	0.0110 (7)	0.0076 (8)
O2	0.0308 (8)	0.0474 (10)	0.0249 (9)	0.0005 (8)	0.0030 (7)	0.0135 (8)
N1	0.0213 (8)	0.0297 (9)	0.0180 (9)	0.0012 (7)	0.0060 (7)	0.0031 (8)
N2	0.0238 (9)	0.0234 (8)	0.0194 (9)	−0.0014 (7)	0.0054 (7)	−0.0001 (7)
N3	0.0267 (10)	0.0301 (10)	0.0214 (10)	−0.0029 (8)	0.0061 (8)	0.0015 (8)
C1	0.0215 (10)	0.0202 (9)	0.0225 (11)	−0.0019 (8)	0.0025 (8)	0.0005 (8)
C2	0.0207 (10)	0.0193 (9)	0.0242 (11)	−0.0010 (8)	0.0049 (8)	0.0001 (8)
C3	0.0249 (10)	0.0184 (10)	0.0229 (11)	−0.0052 (8)	0.0020 (8)	−0.0003 (8)
C4	0.0230 (10)	0.0223 (10)	0.0294 (12)	0.0000 (9)	−0.0007 (8)	0.0018 (9)
C5	0.0221 (10)	0.0254 (10)	0.0327 (12)	0.0026 (9)	0.0055 (9)	−0.0006 (9)
C6	0.0257 (11)	0.0232 (10)	0.0256 (11)	−0.0004 (9)	0.0078 (9)	−0.0021 (8)
C7	0.0215 (10)	0.0186 (9)	0.0217 (10)	−0.0008 (8)	0.0057 (8)	−0.0017 (8)
C8	0.0255 (10)	0.0211 (9)	0.0177 (10)	−0.0020 (8)	0.0056 (8)	0.0004 (8)
C9	0.0231 (10)	0.0211 (10)	0.0224 (11)	0.0002 (8)	0.0008 (8)	−0.0001 (8)
C10	0.0198 (10)	0.0239 (10)	0.0275 (11)	−0.0005 (8)	0.0055 (8)	−0.0036 (9)
C11	0.0259 (10)	0.0243 (11)	0.0234 (11)	−0.0028 (9)	0.0097 (8)	−0.0026 (9)

Geometric parameters (Å, º) top

Cl1—C3	1.753 (2)	C3—C4	1.381 (3)
O1—N3	1.245 (2)	C4—C5	1.386 (3)
O2—N3	1.222 (2)	C4—H4	0.9500
N1—C7	1.358 (3)	C5—C6	1.384 (3)
N1—C1	1.414 (3)	C5—H5	0.9500
N1—H1n	0.88 (3)	C6—H6	0.9500
N2—C11	1.330 (3)	C7—C8	1.428 (3)
N2—C7	1.349 (3)	C8—C9	1.383 (3)
N3—C8	1.447 (3)	C9—C10	1.374 (3)
C1—C2	1.392 (3)	C9—H9	0.9500
C1—C6	1.398 (3)	C10—C11	1.384 (3)
C2—C3	1.389 (3)	C10—H10	0.9500
C2—H2	0.9500	C11—H11	0.9500

C7—N1—C1	130.58 (17)	C6—C5—H5	119.7
C7—N1—H1n	113.9 (18)	C4—C5—H5	119.7
C1—N1—H1n	115.5 (18)	C5—C6—C1	120.4 (2)
C11—N2—C7	119.09 (18)	C5—C6—H6	119.8
O2—N3—O1	122.13 (18)	C1—C6—H6	119.8
O2—N3—C8	118.63 (18)	N2—C7—N1	118.39 (19)
O1—N3—C8	119.25 (18)	N2—C7—C8	119.10 (18)
C2—C1—C6	120.08 (19)	N1—C7—C8	122.50 (18)
C2—C1—N1	124.51 (19)	C9—C8—C7	120.17 (19)
C6—C1—N1	115.33 (18)	C9—C8—N3	116.86 (19)
C3—C2—C1	117.52 (19)	C7—C8—N3	122.97 (18)
C3—C2—H2	121.2	C10—C9—C8	119.4 (2)
C1—C2—H2	121.2	C10—C9—H9	120.3
C4—C3—C2	123.5 (2)	C8—C9—H9	120.3
C4—C3—Cl1	118.72 (17)	C9—C10—C11	117.50 (19)
C2—C3—Cl1	117.73 (16)	C9—C10—H10	121.3
C3—C4—C5	117.9 (2)	C11—C10—H10	121.3
C3—C4—H4	121.1	N2—C11—C10	124.77 (18)
C5—C4—H4	121.1	N2—C11—H11	117.6
C6—C5—C4	120.5 (2)	C10—C11—H11	117.6

C7—N1—C1—C2	−19.5 (4)	C1—N1—C7—C8	174.6 (2)
C7—N1—C1—C6	163.8 (2)	N2—C7—C8—C9	0.4 (3)
C6—C1—C2—C3	0.2 (3)	N1—C7—C8—C9	179.9 (2)
N1—C1—C2—C3	−176.37 (19)	N2—C7—C8—N3	−179.92 (19)
C1—C2—C3—C4	−0.1 (3)	N1—C7—C8—N3	−0.5 (3)
C1—C2—C3—Cl1	179.50 (15)	O2—N3—C8—C9	7.4 (3)
C2—C3—C4—C5	−0.2 (3)	O1—N3—C8—C9	−172.91 (19)
Cl1—C3—C4—C5	−179.74 (16)	O2—N3—C8—C7	−172.3 (2)
C3—C4—C5—C6	0.3 (3)	O1—N3—C8—C7	7.4 (3)
C4—C5—C6—C1	−0.1 (3)	C7—C8—C9—C10	−0.1 (3)
C2—C1—C6—C5	−0.1 (3)	N3—C8—C9—C10	−179.82 (18)
N1—C1—C6—C5	176.77 (19)	C8—C9—C10—C11	−0.6 (3)
C11—N2—C7—N1	−179.43 (18)	C7—N2—C11—C10	−0.8 (3)
C11—N2—C7—C8	0.0 (3)	C9—C10—C11—N2	1.1 (3)
C1—N1—C7—N2	−5.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···O1	0.88 (3)	1.94 (3)	2.647 (2)	137 (2)
C9—H9···Cl1ⁱ	0.95	2.79	3.665 (2)	153

Symmetry code: (i) x−1/2, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₈ClN₃O₂
M_r	249.65
Crystal system, space group	Monoclinic, P2/n
Temperature (K)	100
a, b, c (Å)	15.8781 (10), 3.7157 (2), 18.0651 (13)
β (°)	102.252 (6)
V (Å³)	1041.53 (11)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	3.21
Crystal size (mm)	0.20 × 0.05 × 0.03

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.566, 0.910
No. of measured, independent and observed [I > 2σ(I)] reflections	3341, 1971, 1684
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.119, 1.06
No. of reflections	1971
No. of parameters	158
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.34

Computer programs: CrysAlis PRO (Agilent, 2010), 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
N1—H1n···O1	0.88 (3)	1.94 (3)	2.647 (2)	137 (2)
C9—H9···Cl1ⁱ	0.95	2.79	3.665 (2)	153

Symmetry code: (i) x−1/2, −y+1, z−1/2.

Footnotes

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

Acknowledgements

The authors thank the Ministry of Higher Education, Malaysia, for research grants (FP047/2008 C & FP001/2010 A to ZA and UMRG125 to ERTT). The authors are also grateful to the University of Malaya for support of the crystallographic facility.

References

Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
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Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
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