3,6-Dichloro-N-(4,6-dichloro­pyrimidin-2-yl)picolinamide

Zhang, S.-S.; Zhuang, Y.; Yin, X.-H.; Zhao, K.; Lin, C.-W.

doi:10.1107/S1600536808010325

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o871

doi:10.1107/S1600536808010325

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3,6-Dichloro-N-(4,6-dichloropyrimidin-2-yl)picolinamide

Shan-Shan Zhang,^a Yue Zhuang,^a Xian-Hong Yin,^a ^* Kai Zhao ^b and Cui-Wu Lin ^b

^aCollege of Chemistry and Ecological Engineering, Guangxi University for Nationalities, Nanning 530006, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Guangxi University, Nanning 530006, People's Republic of China
^*Correspondence e-mail: yxhphd@163.com

(Received 1 March 2008; accepted 15 April 2008; online 18 April 2008)

In the title compound, C₁₀H₄Cl₄N₄O, the pyridine and pyrimidine rings are nearly perpendicular to each other, the dihedral angle between them being 86.60 (10)°. In the crystal structure, the N and O atoms in the amide group are involved in intermolecular hydrogen bonds, forming a one-dimensional chain along the c axis.

Related literature

For related literature, see: Liu et al. (2005 ); Śladowska et al. (1999 ).

Experimental

Crystal data

C₁₀H₄Cl₄N₄O
M_r = 337.97
Monoclinic, P 2₁ /c
a = 10.9313 (13) Å
b = 13.3682 (14) Å
c = 9.3846 (10) Å
β = 112.576 (1)°
V = 1266.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.93 mm⁻¹
T = 293 (2) K
0.48 × 0.43 × 0.40 mm

Data collection

Bruker SMART 1000 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.648, T_max = 0.690
15165 measured reflections
2494 independent reflections
2132 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.096
S = 1.02
2494 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.09	2.937 (2)	170
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808010325/is2279sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808010325/is2279Isup2.hkl

checkCIF report

Comment top

The chemical and pharmacological properties of acid amides have been investigated extensively, owing to their chelating ability with metal ions and to their pltentially beneficial chemical and biological activities (Liu et al., 2005; Śladowska et al., 1999). As part of our studies of the synthesis and characterization of these compounds, we report here the synthesis and crystal structure of 3,6-dichloro-N-(4,6-dichloropyrimidin-2-yl)picolinamide. The C=O bond length is 1.208 (3) Å, indicating that the molecule is in the keto form. In the crystal structure, intermolecular N—H···O hydrogen bonds link the molecules into extended chains (Table 1 and Fig. 2). The dihedral angle between the two rings is 86.60 (10)°, which is close to 90 °. The two rings are nearly perpendicular to one another, which keeps the steric effects between these rings least.

Related literature top

For related literature, see: Liu et al. (2005); Śladowska et al. (1999).

Experimental top

A solution of 3,6-dichloropicolinoyl chloride (10 mmol) in 50 ml ethanol was added to a solution of 4,6-dichloropyrimidin-2-amine (10 mmol) in 10 ml ethanol. The reaction mixture was refluxed for 1 h with stirring. Then the resulting pale yellow precipitate was obtained by filtration, washed several times with ethanol and dried in vacuo (yield 90%). Analysis calculated for C₁₀H₄Cl₄N₄O: C 35.54, H 1.19, Cl 41.96, N 16.58, O 4.73%; found: C 35.51, H 1.21, Cl 41.90, N 16.58, O 4.79%. A methanol solution of the title compound was slowly evaporated and white crystals were obtained after one weeks.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. Crystal packing of the title compound, showing the hydrogen bonds as dashed lines.

3,6-Dichloro-N-(4,6-dichloropyrimidin-2-yl)picolinamide top

Crystal data top

C₁₀H₄Cl₄N₄O	F(000) = 672
M_r = 337.97	D_x = 1.773 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5203 reflections
a = 10.9313 (13) Å	θ = 2.5–27.9°
b = 13.3682 (14) Å	µ = 0.93 mm⁻¹
c = 9.3846 (10) Å	T = 293 K
β = 112.576 (1)°	Block, colorless
V = 1266.3 (2) Å³	0.48 × 0.43 × 0.40 mm
Z = 4

Data collection top

Bruker SMART 1000 diffractometer	2494 independent reflections
Radiation source: fine-focus sealed tube	2132 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.648, T_max = 0.690	k = −14→16
15165 measured reflections	l = −11→11

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.054P)² + 0.512P] where P = (F_o² + 2F_c²)/3
2494 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₀H₄Cl₄N₄O	V = 1266.3 (2) Å³
M_r = 337.97	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.9313 (13) Å	µ = 0.93 mm⁻¹
b = 13.3682 (14) Å	T = 293 K
c = 9.3846 (10) Å	0.48 × 0.43 × 0.40 mm
β = 112.576 (1)°

Data collection top

Bruker SMART 1000 diffractometer	2494 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2132 reflections with I > 2σ(I)
T_min = 0.648, T_max = 0.690	R_int = 0.032
15165 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.02	Δρ_max = 0.34 e Å⁻³
2494 reflections	Δρ_min = −0.30 e Å⁻³
172 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	0.35795 (6)	0.27703 (5)	−0.13818 (7)	0.05603 (19)
Cl2	0.62475 (7)	0.54097 (5)	0.43365 (8)	0.0654 (2)
Cl3	1.09988 (5)	0.21157 (5)	−0.02538 (7)	0.05207 (18)
Cl4	1.02903 (6)	−0.06103 (4)	0.35461 (7)	0.05590 (19)
N1	0.74081 (16)	0.23149 (13)	0.16663 (19)	0.0373 (4)
H1	0.7257	0.2261	0.2497	0.045*
N2	0.62326 (16)	0.40893 (13)	0.23044 (19)	0.0391 (4)
N3	0.87749 (16)	0.09425 (12)	0.24523 (19)	0.0365 (4)
N4	0.90814 (16)	0.21391 (12)	0.07244 (19)	0.0345 (4)
O1	0.65761 (15)	0.30109 (12)	−0.07433 (17)	0.0477 (4)
C1	0.65957 (19)	0.29263 (15)	0.0547 (2)	0.0343 (4)
C2	0.56552 (19)	0.35255 (15)	0.1045 (2)	0.0337 (4)
C3	0.4300 (2)	0.35264 (16)	0.0218 (2)	0.0377 (4)
C4	0.3507 (2)	0.41321 (17)	0.0706 (3)	0.0454 (5)
H4	0.2592	0.4137	0.0178	0.054*
C5	0.4096 (2)	0.47242 (16)	0.1984 (3)	0.0453 (5)
H5	0.3596	0.5148	0.2335	0.054*
C6	0.5450 (2)	0.46693 (16)	0.2728 (2)	0.0409 (5)
C7	0.84622 (18)	0.17692 (14)	0.1588 (2)	0.0326 (4)
C8	1.01267 (19)	0.16221 (16)	0.0782 (2)	0.0356 (4)
C9	1.0576 (2)	0.07605 (16)	0.1624 (2)	0.0410 (5)
H9	1.1317	0.0412	0.1640	0.049*
C10	0.9829 (2)	0.04607 (15)	0.2440 (2)	0.0372 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0484 (3)	0.0739 (4)	0.0436 (3)	−0.0043 (3)	0.0151 (3)	−0.0118 (3)
Cl2	0.0771 (4)	0.0715 (4)	0.0639 (4)	−0.0244 (3)	0.0452 (4)	−0.0292 (3)
Cl3	0.0420 (3)	0.0729 (4)	0.0502 (3)	0.0091 (2)	0.0275 (3)	0.0117 (3)
Cl4	0.0705 (4)	0.0384 (3)	0.0589 (4)	0.0150 (3)	0.0248 (3)	0.0111 (2)
N1	0.0406 (9)	0.0437 (10)	0.0356 (9)	0.0093 (7)	0.0234 (8)	0.0071 (7)
N2	0.0414 (9)	0.0450 (10)	0.0380 (9)	−0.0001 (8)	0.0231 (8)	−0.0001 (8)
N3	0.0422 (9)	0.0331 (9)	0.0357 (9)	0.0000 (7)	0.0166 (7)	0.0004 (7)
N4	0.0349 (8)	0.0366 (9)	0.0352 (9)	0.0011 (7)	0.0170 (7)	−0.0012 (7)
O1	0.0500 (9)	0.0659 (10)	0.0353 (8)	0.0160 (7)	0.0253 (7)	0.0077 (7)
C1	0.0358 (10)	0.0388 (11)	0.0343 (10)	0.0023 (8)	0.0200 (8)	0.0010 (8)
C2	0.0375 (10)	0.0354 (10)	0.0331 (10)	0.0065 (8)	0.0189 (8)	0.0065 (8)
C3	0.0408 (10)	0.0422 (11)	0.0321 (10)	0.0047 (9)	0.0162 (9)	0.0052 (8)
C4	0.0371 (11)	0.0534 (13)	0.0467 (12)	0.0141 (9)	0.0173 (9)	0.0106 (10)
C5	0.0550 (13)	0.0412 (12)	0.0508 (13)	0.0137 (10)	0.0327 (11)	0.0063 (10)
C6	0.0515 (12)	0.0377 (11)	0.0434 (11)	−0.0025 (9)	0.0292 (10)	0.0000 (9)
C7	0.0335 (9)	0.0336 (10)	0.0319 (9)	0.0006 (8)	0.0139 (8)	−0.0026 (8)
C8	0.0329 (9)	0.0437 (11)	0.0310 (9)	−0.0007 (8)	0.0132 (8)	−0.0039 (8)
C9	0.0372 (11)	0.0425 (12)	0.0431 (11)	0.0085 (9)	0.0153 (9)	−0.0033 (9)
C10	0.0421 (11)	0.0321 (10)	0.0331 (10)	0.0042 (8)	0.0098 (9)	−0.0023 (8)

Geometric parameters (Å, º) top

Cl1—C3	1.729 (2)	N4—C7	1.335 (2)
Cl2—C6	1.734 (2)	O1—C1	1.208 (2)
Cl3—C8	1.732 (2)	C1—C2	1.512 (3)
Cl4—C10	1.726 (2)	C2—C3	1.383 (3)
N1—C1	1.358 (3)	C3—C4	1.387 (3)
N1—C7	1.389 (2)	C4—C5	1.373 (3)
N1—H1	0.8600	C4—H4	0.9300
N2—C6	1.323 (3)	C5—C6	1.375 (3)
N2—C2	1.338 (3)	C5—H5	0.9300
N3—C10	1.324 (3)	C8—C9	1.376 (3)
N3—C7	1.335 (3)	C9—C10	1.376 (3)
N4—C8	1.319 (3)	C9—H9	0.9300

C1—N1—C7	125.77 (15)	C4—C5—C6	117.70 (19)
C1—N1—H1	117.1	C4—C5—H5	121.1
C7—N1—H1	117.1	C6—C5—H5	121.1
C6—N2—C2	117.08 (17)	N2—C6—C5	124.9 (2)
C10—N3—C7	114.73 (16)	N2—C6—Cl2	115.41 (16)
C8—N4—C7	114.49 (17)	C5—C6—Cl2	119.64 (16)
O1—C1—N1	125.91 (17)	N4—C7—N3	127.17 (17)
O1—C1—C2	120.51 (18)	N4—C7—N1	117.50 (17)
N1—C1—C2	113.57 (15)	N3—C7—N1	115.27 (16)
N2—C2—C3	122.36 (17)	N4—C8—C9	125.06 (18)
N2—C2—C1	115.17 (17)	N4—C8—Cl3	115.62 (15)
C3—C2—C1	122.40 (18)	C9—C8—Cl3	119.29 (15)
C2—C3—C4	119.07 (19)	C10—C9—C8	113.97 (18)
C2—C3—Cl1	121.29 (15)	C10—C9—H9	123.0
C4—C3—Cl1	119.62 (17)	C8—C9—H9	123.0
C5—C4—C3	118.8 (2)	N3—C10—C9	124.56 (19)
C5—C4—H4	120.6	N3—C10—Cl4	116.92 (16)
C3—C4—H4	120.6	C9—C10—Cl4	118.52 (16)

C7—N1—C1—O1	8.1 (3)	C4—C5—C6—N2	0.1 (3)
C7—N1—C1—C2	−172.25 (18)	C4—C5—C6—Cl2	179.38 (17)
C6—N2—C2—C3	−1.0 (3)	C8—N4—C7—N3	−1.4 (3)
C6—N2—C2—C1	176.22 (17)	C8—N4—C7—N1	175.62 (17)
O1—C1—C2—N2	−124.1 (2)	C10—N3—C7—N4	0.9 (3)
N1—C1—C2—N2	56.2 (2)	C10—N3—C7—N1	−176.17 (17)
O1—C1—C2—C3	53.0 (3)	C1—N1—C7—N4	29.0 (3)
N1—C1—C2—C3	−126.6 (2)	C1—N1—C7—N3	−153.63 (19)
N2—C2—C3—C4	0.0 (3)	C7—N4—C8—C9	0.9 (3)
C1—C2—C3—C4	−176.93 (18)	C7—N4—C8—Cl3	−177.03 (14)
N2—C2—C3—Cl1	−178.64 (15)	N4—C8—C9—C10	−0.1 (3)
C1—C2—C3—Cl1	4.4 (3)	Cl3—C8—C9—C10	177.81 (15)
C2—C3—C4—C5	1.0 (3)	C7—N3—C10—C9	0.1 (3)
Cl1—C3—C4—C5	179.68 (17)	C7—N3—C10—Cl4	179.59 (14)
C3—C4—C5—C6	−1.0 (3)	C8—C9—C10—N3	−0.5 (3)
C2—N2—C6—C5	0.9 (3)	C8—C9—C10—Cl4	−179.95 (15)
C2—N2—C6—Cl2	−178.40 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.09	2.937 (2)	170

Symmetry code: (i) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₄Cl₄N₄O
M_r	337.97
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.9313 (13), 13.3682 (14), 9.3846 (10)
β (°)	112.576 (1)
V (Å³)	1266.3 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.93
Crystal size (mm)	0.48 × 0.43 × 0.40

Data collection
Diffractometer	Bruker SMART 1000 diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.648, 0.690
No. of measured, independent and observed [I > 2σ(I)] reflections	15165, 2494, 2132
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.096, 1.02
No. of reflections	2494
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.30

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.09	2.937 (2)	169.5

Symmetry code: (i) x, −y+1/2, z+1/2.

Acknowledgements

The authors thank the National Natural Science Foundation of China (20761002). This research was sponsored by the fund of the Talent Highland Research Program of Guangxi University (205121), the Science Foundation of the State Ethnic Affairs Commission (07GX05), the Development Foundation Guangxi Research Institute of Chemical Industry and the Science Foundation of Guangxi University for Nationalities (0409032, 0409012, 0509ZD047).

References

Liu, W., Li, X., Zhang, B. & Song, M.-P. (2005). J. Org. Chem. 70, 295. 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
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Śladowska, H., Sieklucka-Dziuba, M., Rajtar, G., Sadowski, M. & Kleinrok, Z. (1999). Farmaco, 54, 773–779. Web of Science PubMed Google Scholar