The molecular structures of ethyl 5-amino-3-(4,6-dimethylpyrimidin-2-ylamino)-1-methyl-1
H-pyrazole-4-carboxylate, C
13H
18N
6O
2, (I), and ethyl 5-amino-3-(4,6-dimethylpyrimidin-2-ylamino)-1-(2-nitrophenylsulfonyl)-1
H-pyrazole-4-carboxylate, C
18H
19N
7O
6S, (II), have been determined. There are two intramolecular N—H
O bonds and one intermolecular N—H
O hydrogen bond in (I). The rings formed by the N—H
O hydrogen bonds are almost planar. In (II), three intramolecular N—H
O hydrogen bonds exist.
Supporting information
CCDC references: 273042; 273043
Ethyl 3-(4,6-dimethylpyrimidin-2-ylamino)-5-amino-1H-pyrazole-4-carboxylate (0.69 g, 2.5 mmol) and anhydrous kalium carbonate (0.41 g, 3 mmol) were mixed in acetone (30 ml) and kept in ice-cold conditions. A solution of 2-nitrobenzene-1-sulfonyl chloride (0.66 g, 3 mmol) in acetone (5 ml) was added dropwise with stirring for 10 min. The mixture was stirred at room temperature overnight, and then the solvent was evaporated to dryness in a vacuum. The residue was washed with water. The resulting pale-yellow precipitate was filtered off and recrystallized from ethanol, and well shaped crystals of (II) were obtained. Compound (I) was synthesized using the same procedure, except that dimethyl sulfate was used as a starting material, and the product was purified by silica column chromatography (eluant ethyl acetate/petroleum ether 1:5) and recrystallized from ethanol. Crystals of (I) and (II) suitable for single-crystal X-ray diffraction were selected directly from the sample as prepared.
H atoms attached to C atoms were included in calculated positions and treated as riding atoms using SHELXL97 default parameters [C—H = 0.93, 0.96 or 0.97 Å and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C). For (I), the H atoms of atoms N3 and N6 were located from difference Fourier maps and refined isotropically, with the N—H distance restrained to 0.86 (1) Å. For (II), the H atoms of atoms N3 and N4 were located from difference Fourier maps and refined isotropically with the N—H distance restrained to 0.87 (1).
For both compounds, data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.
(I) Ethyl 5-amino-3-(4,6-dimethylpyrimidin-2-ylamino)-1-methyl-1
H- pyrazole-4-carboxylate
top
Crystal data top
C13H18N6O2 | Dx = 1.261 Mg m−3 |
Mr = 290.33 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 825 reflections |
a = 7.5466 (15) Å | θ = 2.4–25.5° |
b = 9.042 (2) Å | µ = 0.09 mm−1 |
c = 22.412 (8) Å | T = 293 K |
V = 1529.3 (7) Å3 | Prism, yellow |
Z = 4 | 0.38 × 0.30 × 0.20 mm |
F(000) = 616 | |
Data collection top
Bruker Smart 1000 CCD area detector diffractometer | 1629 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.048 |
Graphite monochromator | θmax = 26.5°, θmin = 2.4° |
ϕ and ω scans | h = −5→9 |
7861 measured reflections | k = −11→11 |
1836 independent reflections | l = −28→22 |
Refinement top
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)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.101 | w = 1/[σ2(Fo2) + (0.0529P)2 + 0.2041P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
1836 reflections | Δρmax = 0.17 e Å−3 |
204 parameters | Δρmin = −0.13 e Å−3 |
3 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.014 (2) |
Crystal data top
C13H18N6O2 | V = 1529.3 (7) Å3 |
Mr = 290.33 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.5466 (15) Å | µ = 0.09 mm−1 |
b = 9.042 (2) Å | T = 293 K |
c = 22.412 (8) Å | 0.38 × 0.30 × 0.20 mm |
Data collection top
Bruker Smart 1000 CCD area detector diffractometer | 1629 reflections with I > 2σ(I) |
7861 measured reflections | Rint = 0.048 |
1836 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | 3 restraints |
wR(F2) = 0.101 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.17 e Å−3 |
1836 reflections | Δρmin = −0.13 e Å−3 |
204 parameters | |
Special details top
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 | Uiso*/Ueq | |
N1 | 1.1476 (3) | 0.0360 (2) | 0.14949 (8) | 0.0443 (5) | |
N2 | 0.9392 (3) | −0.0621 (2) | 0.07917 (9) | 0.0510 (5) | |
N3 | 0.8989 (3) | 0.1682 (2) | 0.11810 (8) | 0.0444 (5) | |
H3 | 0.801 (2) | 0.168 (3) | 0.0981 (10) | 0.053* | |
N4 | 1.0657 (2) | 0.3276 (2) | 0.18130 (8) | 0.0416 (4) | |
N5 | 1.0323 (3) | 0.4665 (2) | 0.20579 (8) | 0.0418 (4) | |
N6 | 0.8102 (3) | 0.6522 (3) | 0.20842 (10) | 0.0528 (6) | |
H6A | 0.840 (4) | 0.678 (3) | 0.2439 (6) | 0.063* | |
H6B | 0.7034 (19) | 0.672 (3) | 0.1975 (11) | 0.063* | |
O1 | 0.5761 (2) | 0.30987 (19) | 0.09362 (7) | 0.0466 (4) | |
O2 | 0.5227 (2) | 0.5323 (2) | 0.13480 (9) | 0.0638 (5) | |
C1 | 1.2426 (3) | −0.0891 (3) | 0.14458 (11) | 0.0483 (6) | |
C2 | 1.1893 (4) | −0.2033 (3) | 0.10863 (11) | 0.0557 (7) | |
H2 | 1.2557 | −0.2897 | 0.1059 | 0.067* | |
C3 | 1.0336 (4) | −0.1864 (3) | 0.07637 (11) | 0.0558 (7) | |
C4 | 1.0024 (3) | 0.0425 (3) | 0.11612 (9) | 0.0391 (5) | |
C5 | 0.9224 (3) | 0.2980 (2) | 0.14997 (9) | 0.0361 (5) | |
C6 | 0.7943 (3) | 0.4123 (3) | 0.15343 (9) | 0.0386 (5) | |
C7 | 0.8723 (3) | 0.5186 (3) | 0.19083 (9) | 0.0396 (5) | |
C8 | 0.6205 (3) | 0.4271 (3) | 0.12755 (10) | 0.0415 (5) | |
C9 | 0.4022 (3) | 0.3112 (3) | 0.06501 (12) | 0.0554 (7) | |
H9A | 0.3898 | 0.3977 | 0.0398 | 0.066* | |
H9B | 0.3090 | 0.3127 | 0.0948 | 0.066* | |
C10 | 0.3915 (4) | 0.1735 (3) | 0.02862 (11) | 0.0615 (7) | |
H10A | 0.4766 | 0.1782 | −0.0032 | 0.092* | |
H10B | 0.2746 | 0.1643 | 0.0122 | 0.092* | |
H10C | 0.4164 | 0.0895 | 0.0534 | 0.092* | |
C11 | 1.4110 (4) | −0.0949 (4) | 0.17995 (16) | 0.0745 (9) | |
H11A | 1.4533 | 0.0038 | 0.1868 | 0.112* | |
H11B | 1.4986 | −0.1498 | 0.1582 | 0.112* | |
H11C | 1.3891 | −0.1425 | 0.2175 | 0.112* | |
C12 | 0.9660 (6) | −0.3055 (4) | 0.03575 (16) | 0.0945 (12) | |
H12A | 0.8399 | −0.3141 | 0.0401 | 0.142* | |
H12B | 1.0208 | −0.3979 | 0.0460 | 0.142* | |
H12C | 0.9941 | −0.2809 | −0.0048 | 0.142* | |
C13 | 1.1718 (3) | 0.5367 (3) | 0.23903 (11) | 0.0508 (6) | |
H13A | 1.1445 | 0.6396 | 0.2442 | 0.076* | |
H13B | 1.2815 | 0.5270 | 0.2177 | 0.076* | |
H13C | 1.1825 | 0.4904 | 0.2774 | 0.076* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0425 (10) | 0.0417 (10) | 0.0485 (9) | 0.0101 (9) | −0.0048 (8) | −0.0047 (9) |
N2 | 0.0598 (12) | 0.0428 (11) | 0.0503 (10) | 0.0072 (10) | −0.0097 (10) | −0.0087 (9) |
N3 | 0.0455 (10) | 0.0396 (10) | 0.0481 (10) | 0.0110 (9) | −0.0131 (9) | −0.0077 (9) |
N4 | 0.0399 (9) | 0.0376 (10) | 0.0473 (10) | 0.0077 (9) | −0.0062 (8) | −0.0038 (9) |
N5 | 0.0407 (10) | 0.0383 (10) | 0.0465 (9) | 0.0058 (9) | −0.0066 (8) | −0.0046 (9) |
N6 | 0.0534 (12) | 0.0457 (12) | 0.0593 (12) | 0.0161 (10) | −0.0136 (10) | −0.0129 (11) |
O1 | 0.0377 (8) | 0.0501 (10) | 0.0522 (9) | 0.0099 (8) | −0.0099 (7) | −0.0109 (8) |
O2 | 0.0513 (10) | 0.0586 (11) | 0.0815 (12) | 0.0239 (10) | −0.0181 (9) | −0.0221 (10) |
C1 | 0.0482 (13) | 0.0443 (13) | 0.0524 (13) | 0.0129 (12) | 0.0007 (11) | −0.0010 (11) |
C2 | 0.0676 (16) | 0.0391 (13) | 0.0602 (14) | 0.0181 (13) | 0.0014 (13) | −0.0042 (12) |
C3 | 0.0743 (17) | 0.0391 (13) | 0.0539 (13) | 0.0060 (13) | −0.0018 (14) | −0.0076 (11) |
C4 | 0.0439 (11) | 0.0345 (10) | 0.0388 (10) | 0.0045 (10) | 0.0000 (9) | −0.0006 (9) |
C5 | 0.0386 (10) | 0.0345 (11) | 0.0352 (9) | 0.0055 (9) | −0.0013 (8) | 0.0009 (8) |
C6 | 0.0411 (11) | 0.0377 (11) | 0.0371 (10) | 0.0056 (10) | −0.0031 (9) | −0.0020 (9) |
C7 | 0.0413 (11) | 0.0384 (12) | 0.0391 (10) | 0.0070 (10) | −0.0022 (10) | 0.0001 (9) |
C8 | 0.0392 (11) | 0.0425 (12) | 0.0428 (11) | 0.0083 (10) | −0.0037 (10) | −0.0035 (10) |
C9 | 0.0371 (12) | 0.0680 (17) | 0.0611 (14) | 0.0053 (13) | −0.0127 (11) | −0.0087 (14) |
C10 | 0.0573 (15) | 0.0725 (19) | 0.0546 (14) | −0.0059 (15) | −0.0089 (12) | −0.0082 (14) |
C11 | 0.0651 (18) | 0.0646 (18) | 0.094 (2) | 0.0301 (16) | −0.0218 (17) | −0.0122 (18) |
C12 | 0.123 (3) | 0.0550 (19) | 0.105 (2) | 0.015 (2) | −0.035 (2) | −0.0359 (18) |
C13 | 0.0418 (12) | 0.0513 (14) | 0.0594 (13) | −0.0018 (12) | −0.0070 (11) | −0.0098 (13) |
Geometric parameters (Å, º) top
N1—C4 | 1.328 (3) | C2—H2 | 0.9300 |
N1—C1 | 1.343 (3) | C3—C12 | 1.500 (4) |
N2—C3 | 1.332 (3) | C5—C6 | 1.417 (3) |
N2—C4 | 1.344 (3) | C6—C7 | 1.404 (3) |
N3—C4 | 1.379 (3) | C6—C8 | 1.440 (3) |
N3—C5 | 1.386 (3) | C9—C10 | 1.490 (4) |
N3—H3 | 0.865 (10) | C9—H9A | 0.9700 |
N4—C5 | 1.317 (3) | C9—H9B | 0.9700 |
N4—N5 | 1.394 (3) | C10—H10A | 0.9600 |
N5—C7 | 1.339 (3) | C10—H10B | 0.9600 |
N5—C13 | 1.437 (3) | C10—H10C | 0.9600 |
N6—C7 | 1.355 (3) | C11—H11A | 0.9600 |
N6—H6A | 0.860 (10) | C11—H11B | 0.9600 |
N6—H6B | 0.860 (10) | C11—H11C | 0.9600 |
O1—C8 | 1.347 (3) | C12—H12A | 0.9600 |
O1—C9 | 1.461 (3) | C12—H12B | 0.9600 |
O2—C8 | 1.215 (3) | C12—H12C | 0.9600 |
C1—C2 | 1.370 (4) | C13—H13A | 0.9600 |
C1—C11 | 1.499 (4) | C13—H13B | 0.9600 |
C2—C3 | 1.389 (4) | C13—H13C | 0.9600 |
| | | |
C4—N1—C1 | 115.6 (2) | O2—C8—O1 | 122.7 (2) |
C3—N2—C4 | 115.7 (2) | O2—C8—C6 | 124.9 (2) |
C4—N3—C5 | 129.94 (18) | O1—C8—C6 | 112.38 (19) |
C4—N3—H3 | 117.6 (19) | O1—C9—C10 | 106.4 (2) |
C5—N3—H3 | 112.4 (18) | O1—C9—H9A | 110.4 |
C5—N4—N5 | 104.14 (17) | C10—C9—H9A | 110.4 |
C7—N5—N4 | 112.42 (18) | O1—C9—H9B | 110.4 |
C7—N5—C13 | 129.4 (2) | C10—C9—H9B | 110.4 |
N4—N5—C13 | 118.03 (19) | H9A—C9—H9B | 108.6 |
C7—N6—H6A | 115 (2) | C9—C10—H10A | 109.5 |
C7—N6—H6B | 115 (2) | C9—C10—H10B | 109.5 |
H6A—N6—H6B | 117 (3) | H10A—C10—H10B | 109.5 |
C8—O1—C9 | 117.70 (18) | C9—C10—H10C | 109.5 |
N1—C1—C2 | 121.8 (2) | H10A—C10—H10C | 109.5 |
N1—C1—C11 | 116.0 (2) | H10B—C10—H10C | 109.5 |
C2—C1—C11 | 122.2 (2) | C1—C11—H11A | 109.5 |
C1—C2—C3 | 118.1 (2) | C1—C11—H11B | 109.5 |
C1—C2—H2 | 120.9 | H11A—C11—H11B | 109.5 |
C3—C2—H2 | 120.9 | C1—C11—H11C | 109.5 |
N2—C3—C2 | 121.4 (2) | H11A—C11—H11C | 109.5 |
N2—C3—C12 | 116.9 (3) | H11B—C11—H11C | 109.5 |
C2—C3—C12 | 121.7 (3) | C3—C12—H12A | 109.5 |
N1—C4—N2 | 127.4 (2) | C3—C12—H12B | 109.5 |
N1—C4—N3 | 119.1 (2) | H12A—C12—H12B | 109.5 |
N2—C4—N3 | 113.49 (19) | C3—C12—H12C | 109.5 |
N4—C5—N3 | 123.49 (19) | H12A—C12—H12C | 109.5 |
N4—C5—C6 | 112.53 (19) | H12B—C12—H12C | 109.5 |
N3—C5—C6 | 123.96 (19) | N5—C13—H13A | 109.5 |
C7—C6—C5 | 104.20 (19) | N5—C13—H13B | 109.5 |
C7—C6—C8 | 124.0 (2) | H13A—C13—H13B | 109.5 |
C5—C6—C8 | 131.8 (2) | N5—C13—H13C | 109.5 |
N5—C7—N6 | 123.6 (2) | H13A—C13—H13C | 109.5 |
N5—C7—C6 | 106.69 (19) | H13B—C13—H13C | 109.5 |
N6—C7—C6 | 129.7 (2) | | |
| | | |
C5—N4—N5—C7 | 1.2 (2) | N4—C5—C6—C7 | −0.1 (3) |
C5—N4—N5—C13 | −174.9 (2) | N3—C5—C6—C7 | 178.8 (2) |
C4—N1—C1—C2 | −1.7 (3) | N4—C5—C6—C8 | −179.3 (2) |
C4—N1—C1—C11 | 177.4 (2) | N3—C5—C6—C8 | −0.3 (4) |
N1—C1—C2—C3 | 0.6 (4) | N4—N5—C7—N6 | −179.0 (2) |
C11—C1—C2—C3 | −178.4 (3) | C13—N5—C7—N6 | −3.5 (4) |
C4—N2—C3—C2 | −1.7 (4) | N4—N5—C7—C6 | −1.3 (2) |
C4—N2—C3—C12 | 179.7 (3) | C13—N5—C7—C6 | 174.2 (2) |
C1—C2—C3—N2 | 1.2 (4) | C5—C6—C7—N5 | 0.9 (2) |
C1—C2—C3—C12 | 179.7 (3) | C8—C6—C7—N5 | −179.9 (2) |
C1—N1—C4—N2 | 1.2 (3) | C5—C6—C7—N6 | 178.4 (2) |
C1—N1—C4—N3 | −179.2 (2) | C8—C6—C7—N6 | −2.4 (4) |
C3—N2—C4—N1 | 0.5 (4) | C9—O1—C8—O2 | −0.3 (3) |
C3—N2—C4—N3 | −179.1 (2) | C9—O1—C8—C6 | 179.7 (2) |
C5—N3—C4—N1 | 1.3 (4) | C7—C6—C8—O2 | 0.3 (4) |
C5—N3—C4—N2 | −179.1 (2) | C5—C6—C8—O2 | 179.3 (2) |
N5—N4—C5—N3 | −179.54 (19) | C7—C6—C8—O1 | −179.7 (2) |
N5—N4—C5—C6 | −0.6 (2) | C5—C6—C8—O1 | −0.8 (3) |
C4—N3—C5—N4 | 6.7 (4) | C8—O1—C9—C10 | 177.5 (2) |
C4—N3—C5—C6 | −172.1 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O1 | 0.87 (1) | 2.13 (2) | 2.806 (2) | 135 (2) |
N6—H6A···N4i | 0.86 (1) | 2.27 (2) | 3.082 (3) | 158 (3) |
N6—H6B···O2 | 0.86 (1) | 2.33 (2) | 2.933 (3) | 128 (3) |
Symmetry code: (i) −x+2, y+1/2, −z+1/2. |
(II) 5-amino-3-(4,6-dimethylpyrimidin-2-ylamino)-1-(2-nitrophenylsulfonyl)-1
H- pyrazole-4-carboxylate
top
Crystal data top
C18H19N7O6S | F(000) = 960 |
Mr = 461.46 | Dx = 1.471 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.536 (2) Å | Cell parameters from 965 reflections |
b = 13.715 (3) Å | θ = 2.9–25.0° |
c = 14.443 (3) Å | µ = 0.21 mm−1 |
β = 93.570 (8)° | T = 293 K |
V = 2083.1 (7) Å3 | Prism, yellow |
Z = 4 | 0.30 × 0.25 × 0.20 mm |
Data collection top
Bruker Smart 1000 CCD area detector diffractometer | 4118 independent reflections |
Radiation source: fine-focus sealed tube | 2700 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ϕ and ω scans | θmax = 26.3°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→13 |
Tmin = 0.920, Tmax = 0.960 | k = −17→15 |
9353 measured reflections | l = −17→17 |
Refinement top
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)] = 0.050 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.134 | w = 1/[σ2(Fo2) + (0.064P)2 + 0.3838P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
4118 reflections | Δρmax = 0.28 e Å−3 |
299 parameters | Δρmin = −0.28 e Å−3 |
3 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0039 (7) |
Crystal data top
C18H19N7O6S | V = 2083.1 (7) Å3 |
Mr = 461.46 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.536 (2) Å | µ = 0.21 mm−1 |
b = 13.715 (3) Å | T = 293 K |
c = 14.443 (3) Å | 0.30 × 0.25 × 0.20 mm |
β = 93.570 (8)° | |
Data collection top
Bruker Smart 1000 CCD area detector diffractometer | 4118 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2700 reflections with I > 2σ(I) |
Tmin = 0.920, Tmax = 0.960 | Rint = 0.033 |
9353 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 3 restraints |
wR(F2) = 0.134 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.28 e Å−3 |
4118 reflections | Δρmin = −0.28 e Å−3 |
299 parameters | |
Special details top
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 | Uiso*/Ueq | |
S1 | 0.57284 (6) | 0.12638 (5) | 0.22549 (5) | 0.0438 (2) | |
N1 | 0.69234 (18) | 0.05903 (14) | 0.26817 (14) | 0.0425 (5) | |
N2 | 0.78835 (19) | 0.10974 (14) | 0.32040 (14) | 0.0430 (5) | |
N3 | 0.6384 (2) | −0.10196 (16) | 0.21611 (17) | 0.0499 (6) | |
H3A | 0.575 (2) | −0.0796 (19) | 0.1806 (17) | 0.060* | |
H3B | 0.664 (3) | −0.1613 (10) | 0.215 (2) | 0.060* | |
N4 | 0.98180 (19) | 0.05405 (15) | 0.39663 (16) | 0.0474 (6) | |
H4A | 1.025 (2) | 0.0004 (12) | 0.4048 (19) | 0.057* | |
N5 | 0.9867 (2) | 0.22207 (15) | 0.40477 (14) | 0.0445 (5) | |
N6 | 1.16411 (19) | 0.12307 (16) | 0.45559 (15) | 0.0497 (6) | |
N7 | 0.6725 (3) | 0.11561 (18) | 0.02380 (18) | 0.0617 (7) | |
O1 | 0.49884 (15) | 0.06442 (13) | 0.16489 (13) | 0.0533 (5) | |
O2 | 0.51682 (18) | 0.17169 (15) | 0.30025 (14) | 0.0630 (6) | |
O3 | 1.00872 (17) | −0.14395 (13) | 0.36592 (14) | 0.0579 (5) | |
O4 | 0.84198 (16) | −0.22107 (12) | 0.29616 (12) | 0.0469 (5) | |
O5 | 0.7269 (3) | 0.04895 (16) | 0.06355 (17) | 0.0845 (8) | |
O6 | 0.6219 (3) | 0.11078 (19) | −0.05265 (18) | 0.1118 (11) | |
C1 | 0.7172 (2) | −0.03886 (17) | 0.26109 (16) | 0.0366 (6) | |
C2 | 0.8317 (2) | −0.05307 (17) | 0.31064 (16) | 0.0369 (6) | |
C3 | 0.8694 (2) | 0.04090 (17) | 0.34392 (16) | 0.0374 (6) | |
C4 | 1.0454 (2) | 0.13825 (18) | 0.41982 (17) | 0.0408 (6) | |
C5 | 1.0572 (3) | 0.30159 (19) | 0.42412 (18) | 0.0499 (7) | |
C6 | 1.1811 (3) | 0.2942 (2) | 0.45954 (19) | 0.0575 (8) | |
H6 | 1.2296 | 0.3498 | 0.4724 | 0.069* | |
C7 | 1.2319 (3) | 0.2031 (2) | 0.47556 (19) | 0.0544 (7) | |
C8 | 0.9927 (3) | 0.3963 (2) | 0.4053 (3) | 0.0748 (10) | |
H8A | 0.9428 | 0.3927 | 0.3475 | 0.112* | |
H8B | 1.0553 | 0.4469 | 0.4019 | 0.112* | |
H8C | 0.9382 | 0.4107 | 0.4544 | 0.112* | |
C9 | 1.3653 (3) | 0.1879 (3) | 0.5150 (3) | 0.0807 (11) | |
H9A | 1.3683 | 0.1316 | 0.5544 | 0.121* | |
H9B | 1.3925 | 0.2442 | 0.5504 | 0.121* | |
H9C | 1.4205 | 0.1783 | 0.4654 | 0.121* | |
C10 | 0.9035 (2) | −0.14145 (17) | 0.32715 (17) | 0.0401 (6) | |
C11 | 0.9102 (3) | −0.31255 (17) | 0.31087 (19) | 0.0485 (7) | |
H11A | 0.9441 | −0.3175 | 0.3747 | 0.058* | |
H11B | 0.9801 | −0.3166 | 0.2704 | 0.058* | |
C12 | 0.8169 (3) | −0.3917 (2) | 0.2893 (2) | 0.0674 (9) | |
H12A | 0.7532 | −0.3911 | 0.3340 | 0.101* | |
H12B | 0.8599 | −0.4534 | 0.2915 | 0.101* | |
H12C | 0.7773 | −0.3818 | 0.2283 | 0.101* | |
C13 | 0.6420 (2) | 0.21922 (17) | 0.16187 (18) | 0.0403 (6) | |
C14 | 0.6728 (2) | 0.20987 (18) | 0.07062 (19) | 0.0437 (6) | |
C15 | 0.7072 (3) | 0.2879 (2) | 0.0193 (2) | 0.0562 (8) | |
H15 | 0.7267 | 0.2798 | −0.0422 | 0.067* | |
C16 | 0.7128 (3) | 0.3781 (2) | 0.0594 (3) | 0.0672 (9) | |
H16 | 0.7360 | 0.4319 | 0.0251 | 0.081* | |
C17 | 0.6846 (3) | 0.3895 (2) | 0.1487 (3) | 0.0685 (9) | |
H17 | 0.6897 | 0.4511 | 0.1755 | 0.082* | |
C18 | 0.6484 (3) | 0.3110 (2) | 0.2007 (2) | 0.0556 (8) | |
H18 | 0.6283 | 0.3200 | 0.2619 | 0.067* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0326 (3) | 0.0495 (4) | 0.0487 (4) | 0.0019 (3) | −0.0029 (3) | −0.0044 (3) |
N1 | 0.0396 (11) | 0.0392 (11) | 0.0468 (13) | −0.0028 (9) | −0.0129 (10) | −0.0011 (10) |
N2 | 0.0420 (12) | 0.0386 (11) | 0.0466 (13) | −0.0062 (9) | −0.0117 (10) | −0.0036 (10) |
N3 | 0.0478 (13) | 0.0405 (12) | 0.0594 (15) | −0.0054 (11) | −0.0131 (11) | −0.0063 (12) |
N4 | 0.0412 (12) | 0.0415 (12) | 0.0568 (14) | −0.0058 (10) | −0.0177 (11) | 0.0041 (11) |
N5 | 0.0466 (12) | 0.0467 (13) | 0.0397 (13) | −0.0099 (10) | −0.0006 (10) | −0.0022 (10) |
N6 | 0.0386 (12) | 0.0656 (15) | 0.0439 (13) | −0.0117 (11) | −0.0044 (10) | −0.0008 (11) |
N7 | 0.0812 (18) | 0.0550 (16) | 0.0496 (16) | 0.0070 (13) | 0.0089 (14) | −0.0024 (13) |
O1 | 0.0359 (9) | 0.0564 (11) | 0.0654 (13) | −0.0043 (8) | −0.0147 (9) | −0.0069 (10) |
O2 | 0.0536 (12) | 0.0782 (14) | 0.0584 (13) | 0.0090 (10) | 0.0146 (10) | −0.0128 (11) |
O3 | 0.0434 (11) | 0.0542 (11) | 0.0741 (14) | 0.0031 (9) | −0.0126 (10) | −0.0024 (10) |
O4 | 0.0511 (11) | 0.0380 (9) | 0.0502 (11) | 0.0036 (8) | −0.0078 (9) | −0.0019 (8) |
O5 | 0.116 (2) | 0.0569 (13) | 0.0825 (17) | 0.0343 (13) | 0.0214 (15) | 0.0006 (13) |
O6 | 0.187 (3) | 0.0845 (18) | 0.0593 (16) | −0.0117 (18) | −0.0240 (18) | −0.0163 (14) |
C1 | 0.0363 (12) | 0.0388 (13) | 0.0347 (14) | −0.0065 (11) | 0.0023 (10) | −0.0011 (11) |
C2 | 0.0357 (12) | 0.0393 (13) | 0.0355 (13) | −0.0039 (10) | 0.0000 (10) | −0.0004 (11) |
C3 | 0.0374 (13) | 0.0399 (13) | 0.0346 (13) | −0.0066 (11) | −0.0012 (10) | 0.0043 (11) |
C4 | 0.0398 (13) | 0.0480 (15) | 0.0340 (14) | −0.0096 (12) | −0.0032 (11) | 0.0004 (12) |
C5 | 0.0623 (18) | 0.0510 (16) | 0.0374 (15) | −0.0165 (14) | 0.0112 (13) | −0.0056 (13) |
C6 | 0.0574 (18) | 0.069 (2) | 0.0470 (17) | −0.0342 (16) | 0.0098 (14) | −0.0132 (15) |
C7 | 0.0439 (15) | 0.080 (2) | 0.0395 (16) | −0.0207 (15) | 0.0032 (12) | −0.0086 (15) |
C8 | 0.090 (2) | 0.0479 (18) | 0.087 (3) | −0.0164 (16) | 0.014 (2) | −0.0126 (17) |
C9 | 0.0417 (17) | 0.124 (3) | 0.075 (2) | −0.0263 (19) | −0.0085 (15) | −0.008 (2) |
C10 | 0.0426 (14) | 0.0418 (14) | 0.0359 (14) | −0.0037 (11) | 0.0027 (11) | −0.0020 (11) |
C11 | 0.0579 (17) | 0.0429 (14) | 0.0444 (15) | 0.0092 (12) | 0.0018 (13) | 0.0005 (13) |
C12 | 0.080 (2) | 0.0433 (16) | 0.078 (2) | −0.0008 (15) | −0.0019 (18) | 0.0000 (15) |
C13 | 0.0321 (12) | 0.0410 (13) | 0.0462 (16) | 0.0060 (10) | −0.0093 (11) | −0.0011 (12) |
C14 | 0.0380 (13) | 0.0438 (15) | 0.0482 (17) | 0.0038 (11) | −0.0053 (12) | −0.0016 (12) |
C15 | 0.0470 (16) | 0.0587 (18) | 0.0622 (19) | −0.0011 (13) | −0.0021 (14) | 0.0121 (15) |
C16 | 0.0528 (18) | 0.0546 (19) | 0.093 (3) | −0.0110 (14) | −0.0093 (17) | 0.0148 (19) |
C17 | 0.063 (2) | 0.0428 (17) | 0.097 (3) | −0.0074 (14) | −0.0130 (19) | −0.0106 (18) |
C18 | 0.0525 (17) | 0.0508 (17) | 0.0620 (19) | 0.0052 (13) | −0.0091 (14) | −0.0147 (15) |
Geometric parameters (Å, º) top
S1—O2 | 1.407 (2) | C5—C8 | 1.484 (4) |
S1—O1 | 1.4182 (17) | C6—C7 | 1.373 (4) |
S1—N1 | 1.650 (2) | C6—H6 | 0.9300 |
S1—C13 | 1.755 (3) | C7—C9 | 1.498 (4) |
N1—C1 | 1.373 (3) | C8—H8A | 0.9600 |
N1—N2 | 1.408 (2) | C8—H8B | 0.9600 |
N2—C3 | 1.304 (3) | C8—H8C | 0.9600 |
N3—C1 | 1.339 (3) | C9—H9A | 0.9600 |
N3—H3A | 0.874 (10) | C9—H9B | 0.9600 |
N3—H3B | 0.860 (10) | C9—H9C | 0.9600 |
N4—C4 | 1.366 (3) | C11—C12 | 1.484 (4) |
N4—C3 | 1.380 (3) | C11—H11A | 0.9700 |
N4—H4A | 0.869 (10) | C11—H11B | 0.9700 |
N5—C4 | 1.317 (3) | C12—H12A | 0.9600 |
N5—C5 | 1.339 (3) | C12—H12B | 0.9600 |
N6—C7 | 1.331 (3) | C12—H12C | 0.9600 |
N6—C4 | 1.340 (3) | C13—C18 | 1.378 (3) |
N7—O6 | 1.198 (3) | C13—C14 | 1.383 (4) |
N7—O5 | 1.205 (3) | C14—C15 | 1.364 (4) |
N7—C14 | 1.459 (3) | C15—C16 | 1.366 (4) |
O3—C10 | 1.211 (3) | C15—H15 | 0.9300 |
O4—C10 | 1.333 (3) | C16—C17 | 1.350 (5) |
O4—C11 | 1.455 (3) | C16—H16 | 0.9300 |
C1—C2 | 1.378 (3) | C17—C18 | 1.381 (4) |
C2—C3 | 1.423 (3) | C17—H17 | 0.9300 |
C2—C10 | 1.441 (3) | C18—H18 | 0.9300 |
C5—C6 | 1.376 (4) | | |
| | | |
O2—S1—O1 | 119.83 (12) | C5—C8—H8B | 109.5 |
O2—S1—N1 | 107.90 (12) | H8A—C8—H8B | 109.5 |
O1—S1—N1 | 105.81 (10) | C5—C8—H8C | 109.5 |
O2—S1—C13 | 106.81 (13) | H8A—C8—H8C | 109.5 |
O1—S1—C13 | 110.00 (12) | H8B—C8—H8C | 109.5 |
N1—S1—C13 | 105.64 (11) | C7—C9—H9A | 109.5 |
C1—N1—N2 | 112.89 (18) | C7—C9—H9B | 109.5 |
C1—N1—S1 | 131.64 (16) | H9A—C9—H9B | 109.5 |
N2—N1—S1 | 115.46 (15) | C7—C9—H9C | 109.5 |
C3—N2—N1 | 102.64 (18) | H9A—C9—H9C | 109.5 |
C1—N3—H3A | 119.2 (19) | H9B—C9—H9C | 109.5 |
C1—N3—H3B | 115.7 (19) | O3—C10—O4 | 123.0 (2) |
H3A—N3—H3B | 124 (3) | O3—C10—C2 | 123.8 (2) |
C4—N4—C3 | 129.6 (2) | O4—C10—C2 | 113.2 (2) |
C4—N4—H4A | 116.0 (18) | O4—C11—C12 | 106.6 (2) |
C3—N4—H4A | 112.9 (18) | O4—C11—H11A | 110.4 |
C4—N5—C5 | 115.3 (2) | C12—C11—H11A | 110.4 |
C7—N6—C4 | 115.5 (2) | O4—C11—H11B | 110.4 |
O6—N7—O5 | 124.6 (3) | C12—C11—H11B | 110.4 |
O6—N7—C14 | 117.7 (3) | H11A—C11—H11B | 108.6 |
O5—N7—C14 | 117.7 (2) | C11—C12—H12A | 109.5 |
C10—O4—C11 | 115.60 (19) | C11—C12—H12B | 109.5 |
N3—C1—N1 | 123.5 (2) | H12A—C12—H12B | 109.5 |
N3—C1—C2 | 131.1 (2) | C11—C12—H12C | 109.5 |
N1—C1—C2 | 105.34 (19) | H12A—C12—H12C | 109.5 |
C1—C2—C3 | 105.3 (2) | H12B—C12—H12C | 109.5 |
C1—C2—C10 | 129.7 (2) | C18—C13—C14 | 117.7 (2) |
C3—C2—C10 | 125.0 (2) | C18—C13—S1 | 117.4 (2) |
N2—C3—N4 | 125.1 (2) | C14—C13—S1 | 124.16 (19) |
N2—C3—C2 | 113.8 (2) | C15—C14—C13 | 122.1 (3) |
N4—C3—C2 | 121.1 (2) | C15—C14—N7 | 115.9 (3) |
N5—C4—N6 | 128.1 (2) | C13—C14—N7 | 122.0 (2) |
N5—C4—N4 | 118.6 (2) | C14—C15—C16 | 119.1 (3) |
N6—C4—N4 | 113.3 (2) | C14—C15—H15 | 120.5 |
N5—C5—C6 | 121.2 (3) | C16—C15—H15 | 120.5 |
N5—C5—C8 | 115.7 (3) | C17—C16—C15 | 120.2 (3) |
C6—C5—C8 | 123.1 (3) | C17—C16—H16 | 119.9 |
C7—C6—C5 | 118.7 (3) | C15—C16—H16 | 119.9 |
C7—C6—H6 | 120.6 | C16—C17—C18 | 121.0 (3) |
C5—C6—H6 | 120.6 | C16—C17—H17 | 119.5 |
N6—C7—C6 | 121.0 (2) | C18—C17—H17 | 119.5 |
N6—C7—C9 | 116.5 (3) | C13—C18—C17 | 119.9 (3) |
C6—C7—C9 | 122.5 (3) | C13—C18—H18 | 120.0 |
C5—C8—H8A | 109.5 | C17—C18—H18 | 120.0 |
| | | |
O2—S1—N1—C1 | 121.9 (2) | C8—C5—C6—C7 | 179.2 (3) |
O1—S1—N1—C1 | −7.5 (3) | C4—N6—C7—C6 | −0.2 (4) |
C13—S1—N1—C1 | −124.1 (2) | C4—N6—C7—C9 | −179.6 (2) |
O2—S1—N1—N2 | −59.2 (2) | C5—C6—C7—N6 | 1.4 (4) |
O1—S1—N1—N2 | 171.39 (17) | C5—C6—C7—C9 | −179.3 (3) |
C13—S1—N1—N2 | 54.7 (2) | C11—O4—C10—O3 | −0.7 (4) |
C1—N1—N2—C3 | −0.1 (3) | C11—O4—C10—C2 | 179.9 (2) |
S1—N1—N2—C3 | −179.19 (17) | C1—C2—C10—O3 | 173.9 (3) |
N2—N1—C1—N3 | 178.8 (2) | C3—C2—C10—O3 | −5.5 (4) |
S1—N1—C1—N3 | −2.3 (4) | C1—C2—C10—O4 | −6.7 (4) |
N2—N1—C1—C2 | 0.6 (3) | C3—C2—C10—O4 | 173.9 (2) |
S1—N1—C1—C2 | 179.5 (2) | C10—O4—C11—C12 | 168.9 (2) |
N3—C1—C2—C3 | −178.8 (3) | O2—S1—C13—C18 | 9.9 (2) |
N1—C1—C2—C3 | −0.8 (3) | O1—S1—C13—C18 | 141.41 (19) |
N3—C1—C2—C10 | 1.7 (5) | N1—S1—C13—C18 | −104.8 (2) |
N1—C1—C2—C10 | 179.7 (2) | O2—S1—C13—C14 | −160.0 (2) |
N1—N2—C3—N4 | −180.0 (2) | O1—S1—C13—C14 | −28.5 (2) |
N1—N2—C3—C2 | −0.4 (3) | N1—S1—C13—C14 | 85.3 (2) |
C4—N4—C3—N2 | −14.2 (4) | C18—C13—C14—C15 | −0.7 (4) |
C4—N4—C3—C2 | 166.3 (2) | S1—C13—C14—C15 | 169.2 (2) |
C1—C2—C3—N2 | 0.8 (3) | C18—C13—C14—N7 | 178.3 (2) |
C10—C2—C3—N2 | −179.7 (2) | S1—C13—C14—N7 | −11.8 (3) |
C1—C2—C3—N4 | −179.6 (2) | O6—N7—C14—C15 | −47.1 (4) |
C10—C2—C3—N4 | −0.1 (4) | O5—N7—C14—C15 | 130.5 (3) |
C5—N5—C4—N6 | 3.2 (4) | O6—N7—C14—C13 | 133.9 (3) |
C5—N5—C4—N4 | −176.3 (2) | O5—N7—C14—C13 | −48.6 (4) |
C7—N6—C4—N5 | −2.3 (4) | C13—C14—C15—C16 | 0.7 (4) |
C7—N6—C4—N4 | 177.2 (2) | N7—C14—C15—C16 | −178.4 (2) |
C3—N4—C4—N5 | 12.5 (4) | C14—C15—C16—C17 | 0.1 (4) |
C3—N4—C4—N6 | −167.0 (3) | C15—C16—C17—C18 | −0.8 (5) |
C4—N5—C5—C6 | −1.7 (4) | C14—C13—C18—C17 | −0.1 (4) |
C4—N5—C5—C8 | 178.7 (3) | S1—C13—C18—C17 | −170.7 (2) |
N5—C5—C6—C7 | −0.4 (4) | C16—C17—C18—C13 | 0.8 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···O1 | 0.87 (1) | 2.14 (2) | 2.789 (3) | 131 (2) |
N3—H3B···O4 | 0.86 (1) | 2.30 (2) | 2.881 (3) | 125 (2) |
N4—H4A···O3 | 0.87 (1) | 2.06 (2) | 2.769 (3) | 138 (2) |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C13H18N6O2 | C18H19N7O6S |
Mr | 290.33 | 461.46 |
Crystal system, space group | Orthorhombic, P212121 | Monoclinic, P21/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 7.5466 (15), 9.042 (2), 22.412 (8) | 10.536 (2), 13.715 (3), 14.443 (3) |
α, β, γ (°) | 90, 90, 90 | 90, 93.570 (8), 90 |
V (Å3) | 1529.3 (7) | 2083.1 (7) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.21 |
Crystal size (mm) | 0.38 × 0.30 × 0.20 | 0.30 × 0.25 × 0.20 |
|
Data collection |
Diffractometer | Bruker Smart 1000 CCD area detector diffractometer | Bruker Smart 1000 CCD area detector diffractometer |
Absorption correction | – | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | – | 0.920, 0.960 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7861, 1836, 1629 | 9353, 4118, 2700 |
Rint | 0.048 | 0.033 |
(sin θ/λ)max (Å−1) | 0.628 | 0.623 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.101, 1.09 | 0.050, 0.134, 1.04 |
No. of reflections | 1836 | 4118 |
No. of parameters | 204 | 299 |
No. of restraints | 3 | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.17, −0.13 | 0.28, −0.28 |
Selected geometric parameters (Å, º) for (I) topN3—C5 | 1.386 (3) | C5—C6 | 1.417 (3) |
N6—C7 | 1.355 (3) | C6—C7 | 1.404 (3) |
O1—C8 | 1.347 (3) | C6—C8 | 1.440 (3) |
O2—C8 | 1.215 (3) | | |
| | | |
N3—C5—C6 | 123.96 (19) | O2—C8—C6 | 124.9 (2) |
N6—C7—C6 | 129.7 (2) | O1—C8—C6 | 112.38 (19) |
O2—C8—O1 | 122.7 (2) | | |
| | | |
N3—C5—C6—C8 | −0.3 (4) | C7—C6—C8—O2 | 0.3 (4) |
C8—C6—C7—N6 | −2.4 (4) | C5—C6—C8—O1 | −0.8 (3) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O1 | 0.865 (10) | 2.13 (2) | 2.806 (2) | 135 (2) |
N6—H6A···N4i | 0.860 (10) | 2.266 (15) | 3.082 (3) | 158 (3) |
N6—H6B···O2 | 0.860 (10) | 2.33 (2) | 2.933 (3) | 128 (3) |
Symmetry code: (i) −x+2, y+1/2, −z+1/2. |
Selected geometric parameters (Å, º) for (II) topS1—O1 | 1.4182 (17) | O3—C10 | 1.211 (3) |
S1—N1 | 1.650 (2) | O4—C10 | 1.333 (3) |
N1—C1 | 1.373 (3) | C1—C2 | 1.378 (3) |
N3—C1 | 1.339 (3) | C2—C10 | 1.441 (3) |
N4—C3 | 1.380 (3) | | |
| | | |
O1—S1—N1 | 105.81 (10) | N4—C3—C2 | 121.1 (2) |
N3—C1—N1 | 123.5 (2) | O3—C10—C2 | 123.8 (2) |
N3—C1—C2 | 131.1 (2) | O4—C10—C2 | 113.2 (2) |
| | | |
O1—S1—N1—C1 | −7.5 (3) | C1—C2—C10—O4 | −6.7 (4) |
S1—N1—C1—N3 | −2.3 (4) | C3—C2—C10—O4 | 173.9 (2) |
N3—C1—C2—C10 | 1.7 (5) | O5—N7—C14—C13 | −48.6 (4) |
C10—C2—C3—N4 | −0.1 (4) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···O1 | 0.874 (10) | 2.14 (2) | 2.789 (3) | 131 (2) |
N3—H3B···O4 | 0.860 (10) | 2.30 (2) | 2.881 (3) | 125 (2) |
N4—H4A···O3 | 0.869 (10) | 2.063 (19) | 2.769 (3) | 138 (2) |
Many pyrazoles and pyrimidines show fungicidal or herbicidal activities (Malhotra et al., 1997; Takao et al., 1994; Ohvchi & Okada, 1998; Kleschick et al., 1992). Some of these kinds of compounds, such as flumetsulam, metosulam and pyrazosulfuron, have been commercialized as agrochemicals. The pyrazole and pyrimidine derivatives have also been investigated extensively in pharmacological applications (Kees et al., 1996; Lesyk et al., 1998). In order to discover further biologically active pyrazole and pyrimidine compounds, a series of novel pyrimidinylaminopyrazole derivatives were designed and synthesized. Some of them showed high fungicidal or herbicidal activity. It has been reported that the position of the acid H atom on a pyrazole ring is not stationary. For example, for 3{5}-substituted pyrazoles, the position of the acid H atom could be correlated with the Hammett σm parameter of the 3{5}-substituent. Substituents with positive σm values prefer the 3-positon, while those with negative σm adopt the 5-position (Lopez et al., 1993; Malcolm et al., 1996). It is possible that the substitution reaction occurs at the two endocyclic N atoms simultaneously, and thus a pair of isomers could be obtained. For instance, when the 4-position substitutents are cyano and ethoxycarbonyl groups, respectively, the ratios of isomer (III) to isomer (IV) are 100:83 and 100:1.13 (Ren et al., 2004). When ethyl 3-(4,6-dimethylpyrimidin-2-ylamino)-5-amino-1H-pyrazole- 4-carboxylate was reacted with methyl iodide and 2-nitrobenzenesulfonyl chloride, only one primary product was obtained in each case, which was found by X-ray determination to be (I) and (II), respectively (Figs. 1 and 2). According to Fig. 2, the nitro group in the ortho-position is twisted by 48.07 (13)° from the plane of the phenyl ring. This tilting of the nitro group avoids unfavourable steric contacts with atom O1 (Jeyakanthan et al., 1999). Similarly, the interplanar angle between the phenyl ring F' and the pyrazole ring A' is 77.08 (9)°. The molecular structure of (II) is stabilized by three N—H···O-type intramolecular hydrogen bonds (Table 4). Rings A', B', C' and D' are not coplanar; the dihedral angles between the the planes of rings B', C' and D' and the palne of the pyrazole ring A' are 2.4 (5), 1.7 (6) and 4.4 (5)°, respectively. The molecular structure of (I) is stabilized by two intramolecular N—H···O hydrogen bonds and one intermolecular N—H···O hydrogen bond (Table 2). The hydrogen bonds of the molecular structure of (I) are longer than the corresponding bonds of (II), but rings A, B and C are almost coplanar. For (I) and (II), the dihedral angles between the pyrimidine ring and the pyrazole ring are 7.9 (2) and 14.1 (1)°, respectively.