Acta Cryst. (2008). E64, o871 [ doi:10.1107/S1600536808010325 ]
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.
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.
H atoms were positioned geometrically (C—H = 0.93 and N—H = 0.86 Å) and were refined as riding, with Uiso(H) = 1.2Ueq(C, N).
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).
![[Figure 1]](./is2279fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme. |
![[Figure 2]](./is2279fig2thm.gif)
| Fig. 2. Crystal packing of the title compound, showing the hydrogen bonds as dashed lines. |
| C10H4Cl4N4O | F000 = 672 |
| Mr = 337.97 | Dx = 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 = 2.5–27.9º |
| b = 13.3682 (14) Å | µ = 0.93 mm−1 |
| c = 9.3846 (10) Å | T = 293 (2) K |
| β = 112.576 (1)º | Block, colorless |
| V = 1266.3 (2) Å3 | 0.48 × 0.43 × 0.40 mm |
| Z = 4 |
| Bruker SMART 1000 diffractometer | 2494 independent reflections |
| Radiation source: fine-focus sealed tube | 2132 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.032 |
| T = 293(2) K | θmax = 26.0º |
| φ and ω scans | θmin = 2.0º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→13 |
| Tmin = 0.648, Tmax = 0.690 | k = −14→16 |
| 15165 measured reflections | l = −11→11 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
| wR(F2) = 0.096 | w = 1/[σ2(Fo2) + (0.054P)2 + 0.512P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.02 | (Δ/σ)max < 0.001 |
| 2494 reflections | Δρmax = 0.34 e Å−3 |
| 172 parameters | Δρmin = −0.30 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C10H4Cl4N4O | V = 1266.3 (2) Å3 |
| Mr = 337.97 | Z = 4 |
| Monoclinic, P21/c | Mo Kα |
| a = 10.9313 (13) Å | µ = 0.93 mm−1 |
| b = 13.3682 (14) Å | T = 293 (2) K |
| c = 9.3846 (10) Å | 0.48 × 0.43 × 0.40 mm |
| β = 112.576 (1)º |
| Bruker SMART 1000 diffractometer | 2494 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2132 reflections with I > 2σ(I) |
| Tmin = 0.648, Tmax = 0.690 | Rint = 0.032 |
| 15165 measured reflections |
| R[F2 > 2σ(F2)] = 0.033 | 172 parameters |
| wR(F2) = 0.096 | H-atom parameters constrained |
| S = 1.02 | Δρmax = 0.34 e Å−3 |
| 2494 reflections | Δρmin = −0.30 e Å−3 |
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 | 0.35795 (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) |
| 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) |
| 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) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O1i | 0.86 | 2.09 | 2.937 (2) | 170 |
| Symmetry codes: (i) x, −y+1/2, z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O1i | 0.86 | 2.09 | 2.937 (2) | 170 |
| Symmetry codes: (i) x, −y+1/2, z+1/2. |
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).
Liu, W., Li, X., Zhang, B. & Song, M.-P. (2005). J. Org. Chem. 70, 295.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Śladowska, H., Sieklucka-Dziuba, M., Rajtar, G., Sadowski, M. & Kleinrok, Z. (1999). Farmaco, 54, 773-779.
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.