N-(3-Chloro-phen-yl)-3-nitro-pyridin-2-amine.

Abstract

The dihedral angle between the benzene and pyridyl rings in the title compound, C(11)H(8)ClN(3)O(2), is 22.65 (10)°, indicating a twisted mol-ecule. The amine H and nitro O atoms form a donor-acceptor pair for an intra-molecular 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 inter-actions that lead to undulating supra-molecular chains along [101]. These are connected into sheets by π-π inter-actions occurring between the benzene rings and between the pyridine rings of translationally related mol-ecules along the b axis [centroid-centroid distances = length of b axis = 3.7157 (2) Å].

Full text

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N-(3-Chlorophenyl)-3-nitropyridin-2-
amine
Aina Mardia Akhmad Aznan,aZanariah Abdullah,a‡
Seik Weng Nga,band Edward R. T. Tiekinka*
aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia,
andbChemistry 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
Key indicators: single-crystal X-ray study; T = 100 K; mean ?(C–C) = 0.003 A ˚;
R factor = 0.041; wR factor = 0.119; data-to-parameter ratio = 12.5.
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–acceptorpairfor an
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 ?–?
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) A˚].
intramolecularN—H???O
Related literature
For the structure of a related pyrimidine amine derivative, see:
Aznan Akhmad et al. (2010).
Experimental
Crystal data
C11H8ClN3O2
Mr= 249.65
Monoclinic, P2=n
a = 15.8781 (10) A˚
b = 3.7157 (2) A˚
c = 18.0651 (13) A˚
? = 102.252 (6)?
V = 1041.53 (11) A˚3
Z = 4
Cu K? radiation
? = 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)
Tmin= 0.566, Tmax= 0.910
3341 measured reflections
1971 independent reflections
1684 reflections with I > 2?(I)
Rint= 0.026
Refinement
R[F2> 2?(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
??max= 0.25 e A˚?3
??min= ?0.34 e A˚?3
Table 1
Hydrogen-bond geometry (A˚,?).
D—H???A
N1—H1n???O1
C9—H9???Cl1i
Symmetry code: (i) x ?1
D—HH???AD???AD—H???A
0.88 (3)
0.95
1.94 (3)
2.79
2.647 (2)
3.665 (2)
137 (2)
153
2;?y þ 1;z ?1
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).
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.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: HB6466).
References
Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England.
Aznan Akhmad, M. A., Abdullah, Z., Fairuz, Z. A., Ng, S. W. & Tiekink,
E. R. T. (2010). Acta Cryst. E66, o2400.
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
organic compounds
o3076
Aznan et al.
doi:10.1107/S1600536811044011
Acta Cryst. (2011). E67, o3076
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368
‡ Additional correspondence author, e-mail: zana@um.edu.my.

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supplementary materials

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supplementary materials
sup-1
Acta Cryst. (2011). E67, o3076 [ doi:10.1107/S1600536811044011 ]
N-(3-Chlorophenyl)-3-nitropyridin-2-amine
A. M. A. Aznan, Z. Abdullah, S. W. Ng and E. R. T. Tiekink
Comment
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 occur-
ring 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.
Experimental
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.
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 Uiso(H) set to 1.2Uequiv(C). The N-bound H-atom was located in a difference Fourier map and
its position and Uiso refined.
Figures
Fig. 1. The molecular structure of (I) showing displacement ellipsoids at the 50% probability
level.

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supplementary materials
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Fig. 2. Undulating supramolecular chain along [101] in (I) sustained by C—H···Cl interac-
tions, 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
Crystal data
C11H8ClN3O2
F(000) = 512
Dx = 1.592 Mg m−3
Cu Kα radiation, λ = 1.54184 Å
Cell parameters from 1441 reflections
θ = 2.9–74.2°
µ = 3.21 mm−1
T = 100 K
Prism, orange
Mr = 249.65
Monoclinic, P2/n
Hall symbol: -P 2yac
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
0.20 × 0.05 × 0.03 mm
Data collection
Agilent SuperNova Dual
diffractometer with an Atlas detector
Radiation source: SuperNova (Cu) X-ray Source
Mirror
Detector resolution: 10.4041 pixels mm-1
ω scan
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2010)
Tmin = 0.566, Tmax = 0.910
3341 measured reflections
1971 independent reflections
1684 reflections with I > 2σ(I)
Rint = 0.026
θmax = 70.0°, θmin = 3.4°
h = −19→16
k = −4→2
l = −22→20

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Refinement
Refinement on F2
Primary atom site location: structure-invariant direct
methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring
sites
H atoms treated by a mixture of independent and
constrained refinement
w = 1/[σ2(Fo2) + (0.0688P)2 + 0.3527P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.25 e Å−3
Δρmin = −0.34 e Å−3
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.041
wR(F2) = 0.119
S = 1.06
1971 reflections
158 parameters
0 restraints
Special details
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, convention-
al 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)
x
0.78774 (3)
0.66072 (10)
0.54073 (10)
0.68353 (11)
0.55898 (11)
0.58523 (12)
0.74388 (13)
0.73308 (13)
0.6815
0.80060 (14)
0.87682 (14)
0.9216
0.88592 (14)
0.9376
0.82038 (14)
0.8274
0.59821 (13)
y
0.02226 (14)
0.4237 (5)
0.6787 (5)
0.1981 (5)
0.1975 (5)
0.5144 (5)
0.0748 (6)
0.1013 (5)
0.1947
−0.0138 (5)
−0.1519 (6)
−0.2272
−0.1769 (6)
−0.2719
−0.0648 (6)
−0.0828
0.2730 (5)
z
0.66591 (3)
0.23466 (9)
0.18194 (9)
0.37651 (10)
0.42492 (9)
0.23471 (10)
0.44066 (12)
0.51495 (12)
0.5261
0.57217 (12)
0.55902 (13)
0.5997
0.48458 (12)
0.4738
0.42579 (13)
0.3750
0.36741 (11)
Uiso*/Ueq
0.02816 (19)
0.0357 (4)
0.0348 (4)
0.0227 (4)
0.0221 (4)
0.0259 (4)
0.0217 (4)
0.0214 (4)
0.026*
0.0225 (5)
0.0258 (5)
0.031*
0.0268 (5)
0.032*
0.0245 (5)
0.029*
0.0205 (4)
Cl1
O1
O2
N1
N2
N3
C1
C2
H2
C3
C4
H4
C5
H5
C6
H6
C7