3,5-Dichloro-6-methyl-pyridin-2-amine.

In the title compound, C(6)H(6)Cl(2)N(2), intra-molecular N-H⋯Cl and C-H⋯Cl contacts generate five-membered rings, producing S(5) ring motifs. Pairs of inter-molecular N-H⋯N hydrogen bonds link neighbouring mol-ecules into dimers with R(2) (2)(8) ring motifs. In the crystal structure, these dimers are connected by N-H⋯Cl inter-actions and are packed into columns.

Related literature

For details of hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For related literature and applications see, for example: Goswami & Maity (2007 ▶); Taylor et al. (1989 ▶); Taylor & Ray (1988 ▶); Beer et al. (1993 ▶); Goswami et al. (2000 ▶, 2005 ▶); Fun et al. (2008 ▶).

Experimental

Crystal data

C6H6Cl2N2

M = 177.03

Monoclinic,

a = 12.7670 (3) Å

b = 3.8037 (1) Å

c = 15.4129 (3) Å

β = 104.990 (1)°

V = 723.01 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.81 mm−1

T = 100.0 (1) K

0.45 × 0.31 × 0.28 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2005 ▶) T min = 0.711, T max = 0.803

26531 measured reflections

3795 independent reflections

3485 reflections with I > 2˘I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.071

S = 1.11

3795 reflections

115 parameters

All H-atom parameters refined

Δρmax = 0.61 e Å−3

Δρmin = −0.42 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808041366/tk2343sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808041366/tk2343Isup2.hkl

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

C6H6Cl2N2	F(000) = 360
Mr = 177.03	Dx = 1.626 Mg m−3
Monoclinic, P21/n	Melting point: 404 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 12.7670 (3) Å	Cell parameters from 9896 reflections
b = 3.8037 (1) Å	θ = 2.4–40.3°
c = 15.4129 (3) Å	µ = 0.81 mm−1
β = 104.990 (1)°	T = 100 K
V = 723.01 (3) Å3	Block, colourless
Z = 4	0.45 × 0.31 × 0.28 mm

Bruker SMART APEXII CCD area-detector diffractometer	3795 independent reflections
Radiation source: fine-focus sealed tube	3485 reflections with I > 2˘I)
graphite	Rint = 0.026
φ and ω scans	θmax = 37.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −21→21
Tmin = 0.711, Tmax = 0.803	k = −6→6
26531 measured reflections	l = −26→26

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.071	All H-atom parameters refined
S = 1.11	w = 1/[σ2(Fo2) + (0.037P)2 + 0.1631P] where P = (Fo2 + 2Fc2)/3
3795 reflections	(Δ/σ)max = 0.001
115 parameters	Δρmax = 0.61 e Å−3
0 restraints	Δρmin = −0.42 e Å−3

Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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.

	x	y	z	Uiso*/Ueq
Cl1	0.116608 (15)	0.89761 (5)	0.117299 (12)	0.01973 (5)
Cl2	0.150078 (13)	0.32687 (5)	−0.194719 (10)	0.01603 (4)
N1	0.36956 (5)	0.65340 (16)	0.02268 (4)	0.01455 (9)
N2	0.38950 (5)	0.41291 (19)	−0.10983 (4)	0.01738 (11)
H2N1	0.4571 (12)	0.379 (4)	−0.0819 (9)	0.027 (3)*
H1N1	0.3607 (11)	0.284 (4)	−0.1526 (9)	0.025 (3)*
C1	0.32310 (5)	0.51854 (18)	−0.05855 (4)	0.01322 (10)
C2	0.20904 (5)	0.49965 (17)	−0.08923 (4)	0.01321 (10)
C3	0.14544 (5)	0.61633 (18)	−0.03563 (4)	0.01465 (10)
H3	0.0672 (10)	0.605 (3)	−0.0583 (8)	0.022 (3)*
C4	0.19660 (5)	0.75331 (18)	0.04856 (4)	0.01450 (10)
C5	0.30903 (5)	0.77194 (18)	0.07629 (4)	0.01437 (10)
C6	0.37037 (7)	0.9165 (2)	0.16549 (5)	0.02130 (13)
H6C	0.4268 (13)	1.055 (5)	0.1579 (11)	0.041 (4)*
H6B	0.4079 (16)	0.744 (5)	0.2083 (12)	0.061 (5)*
H6A	0.3222 (16)	1.071 (6)	0.1929 (13)	0.065 (6)*

	U11	U22	U33	U12	U13	U23
Cl1	0.02170 (8)	0.02155 (8)	0.01862 (8)	0.00364 (6)	0.01006 (6)	−0.00108 (5)
Cl2	0.01665 (7)	0.01786 (7)	0.01167 (7)	−0.00132 (5)	0.00022 (5)	−0.00081 (5)
N1	0.0143 (2)	0.0174 (2)	0.0113 (2)	−0.00002 (17)	0.00219 (17)	−0.00112 (17)
N2	0.0146 (2)	0.0247 (3)	0.0127 (2)	0.00163 (19)	0.00317 (18)	−0.00292 (19)
C1	0.0136 (2)	0.0146 (2)	0.0110 (2)	0.00045 (18)	0.00251 (18)	0.00056 (18)
C2	0.0140 (2)	0.0139 (2)	0.0108 (2)	−0.00021 (18)	0.00163 (17)	0.00039 (18)
C3	0.0143 (2)	0.0153 (2)	0.0142 (2)	0.00085 (19)	0.00352 (19)	0.0011 (2)
C4	0.0168 (2)	0.0140 (2)	0.0137 (2)	0.0020 (2)	0.00586 (19)	0.00056 (19)
C5	0.0172 (2)	0.0141 (2)	0.0117 (2)	0.00022 (19)	0.00350 (19)	−0.00028 (19)
C6	0.0264 (3)	0.0224 (3)	0.0135 (3)	−0.0011 (3)	0.0023 (2)	−0.0044 (2)

Cl1—C4	1.7396 (7)	C2—C3	1.3733 (9)
Cl2—C2	1.7346 (6)	C3—C4	1.3941 (9)
N1—C1	1.3409 (8)	C3—H3	0.970 (13)
N1—C5	1.3468 (9)	C4—C5	1.3894 (10)
N2—C1	1.3607 (9)	C5—C6	1.4996 (10)
N2—H2N1	0.869 (14)	C6—H6C	0.924 (17)
N2—H1N1	0.828 (14)	C6—H6B	0.96 (2)
C1—C2	1.4118 (9)	C6—H6A	1.02 (2)
C1—N1—C5	121.03 (6)	C5—C4—C3	120.23 (6)
C1—N2—H2N1	116.4 (9)	C5—C4—Cl1	121.27 (5)
C1—N2—H1N1	115.0 (9)	C3—C4—Cl1	118.50 (5)
H2N1—N2—H1N1	119.1 (13)	N1—C5—C4	120.35 (6)
N1—C1—N2	117.62 (6)	N1—C5—C6	116.03 (6)
N1—C1—C2	120.07 (6)	C4—C5—C6	123.62 (6)
N2—C1—C2	122.28 (6)	C5—C6—H6C	109.4 (10)
C3—C2—C1	120.08 (6)	C5—C6—H6B	115.3 (11)
C3—C2—Cl2	120.37 (5)	H6C—C6—H6B	102.0 (15)
C1—C2—Cl2	119.55 (5)	C5—C6—H6A	111.3 (11)
C2—C3—C4	118.24 (6)	H6C—C6—H6A	107.2 (15)
C2—C3—H3	118.9 (7)	H6B—C6—H6A	110.8 (14)
C4—C3—H3	122.8 (7)
C5—N1—C1—N2	178.27 (6)	C2—C3—C4—C5	0.46 (10)
C5—N1—C1—C2	0.13 (10)	C2—C3—C4—Cl1	−179.37 (5)
N1—C1—C2—C3	−0.61 (10)	C1—N1—C5—C4	0.64 (10)
N2—C1—C2—C3	−178.66 (7)	C1—N1—C5—C6	179.98 (6)
N1—C1—C2—Cl2	179.63 (5)	C3—C4—C5—N1	−0.94 (10)
N2—C1—C2—Cl2	1.58 (9)	Cl1—C4—C5—N1	178.89 (5)
C1—C2—C3—C4	0.29 (10)	C3—C4—C5—C6	179.77 (7)
Cl2—C2—C3—C4	−179.95 (5)	Cl1—C4—C5—C6	−0.40 (10)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N1···N1i	0.869 (15)	2.168 (15)	3.0320 (9)	172.8 (13)
N2—H1N1···Cl2	0.828 (14)	2.603 (14)	3.0156 (7)	112.3 (12)
C6—H6A···Cl1	1.02 (2)	2.67 (2)	3.1318 (9)	108.0 (14)
N2—H1N1···Cl2ii	0.828 (14)	2.900 (14)	3.6758 (7)	156.9 (13)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N1⋯N1i	0.869 (15)	2.168 (15)	3.0320 (9)	172.8 (13)
N2—H1N1⋯Cl2	0.828 (14)	2.603 (14)	3.0156 (7)	112.3 (12)
C6—H6A⋯Cl1	1.02 (2)	2.67 (2)	3.1318 (9)	108.0 (14)
N2—H1N1⋯Cl2ii	0.828 (14)	2.900 (14)	3.6758 (7)	156.9 (13)

Symmetry code: (i) .