Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100012300/gs1111sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100012300/gs1111IIIsup2.hkl |
CCDC reference: 156158
A solution of 3-amino-5-methylpyrazole (3.1 mmol) and dimedone (3.1 mmol) in ethanol (5 ml) was heated to reflux for 30 min. Cooling the solution to room temperature afforded yellow crystals of (III) which were filtered out, washed with fresh ethanol and dried. Suitable crystals for X-ray diffraction were obtained after recrystallization from ethanol (yield 75%, m.p. 516–518 K). Analysis calculated for C12H17N3O: C 65.73, H 7.81, N 19.16%; found C 65.53, H 7.75, N 19.29%.
H atoms were treated as riding, with C—H 0.93–0.99 Å and N—H 0.88 Å. Since no atom heavier than O was present in the structure, the absolute structure could not be determined and Friedel pairs were merged. The disordered atoms of the cyclohexenone ring were refined using the following restraints. All bonds involving C10, C11, C12, C13 and C14 of the major component and C10', C11', C12', C13' and C14' of the minor component were given a DFIX restraint (SHELXL97; Sheldrick, 1997) with a target value of 1.54 (2) Å, and the C7—C12 and C7—C12' bonds were given a DFIX of 1.52 (2) Å, these being the `normal' bond lengths for the two types of C—C bond present, according to Ladd & Palmer (1994). These restraints were designed to bring the minor component bond lengths into line with those of the major component without putting too large a restraint on the major component bonds. The cyclohexenone ring atoms C10 (C10') to C12 (C12') were allowed to refine anisotropically but with the atomic displacement parameters constrained to be equal. A similar but separate constraint was applied to the methyl atoms attached to the cyclohexenone ring.
Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97; molecular graphics: PLATON (Spek, 2000); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).
C12H17N3O | Dx = 1.160 Mg m−3 |
Mr = 219.29 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pna21 | Cell parameters from 1515 reflections |
a = 12.5130 (3) Å | θ = 3.3–27.4° |
b = 9.4275 (3) Å | µ = 0.08 mm−1 |
c = 10.6441 (3) Å | T = 150 K |
V = 1255.65 (6) Å3 | Plate, colourless |
Z = 4 | 0.25 × 0.15 × 0.05 mm |
F(000) = 472 |
Nonius KAPPA CCD diffractometer | 1515 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 1360 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
ϕ and ω scans with κ offsets | θmax = 27.4°, θmin = 3.3° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | h = −16→15 |
Tmin = 0.981, Tmax = 0.996 | k = −12→12 |
13142 measured reflections | l = −13→13 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0676P)2 + 0.3673P] where P = (Fo2 + 2Fc2)/3 |
1515 reflections | (Δ/σ)max < 0.001 |
148 parameters | Δρmax = 0.31 e Å−3 |
11 restraints | Δρmin = −0.34 e Å−3 |
C12H17N3O | V = 1255.65 (6) Å3 |
Mr = 219.29 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 12.5130 (3) Å | µ = 0.08 mm−1 |
b = 9.4275 (3) Å | T = 150 K |
c = 10.6441 (3) Å | 0.25 × 0.15 × 0.05 mm |
Nonius KAPPA CCD diffractometer | 1515 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | 1360 reflections with I > 2σ(I) |
Tmin = 0.981, Tmax = 0.996 | Rint = 0.042 |
13142 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 11 restraints |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.31 e Å−3 |
1515 reflections | Δρmin = −0.34 e Å−3 |
148 parameters |
Geometry. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) − 2.7701 (0.0422) x + 7.2001 (0.0036) y + 6.4544 (0.0139) z = 4.6699 (0.0407) * −0.0068 (0.0013) N6 * 0.0061 (0.0016) C7 * 0.0070 (0.0019) C8 * −0.0050 (0.0016) C9 * −0.0013 (0.0013) O91 Rms deviation of fitted atoms = 0.0057 − 2.7142 (0.0146) x + 9.0870 (0.0031) y + 1.6446 (0.0140) z = 3.5242 (0.0179) Angle to previous plane (with approximate e.s.d.) = 28.61 (0.12) * −0.0026 (0.0016) N1 * 0.0005 (0.0016) C2 * 0.0018 (0.0015) C3 * −0.0034 (0.0014) C4 * 0.0037 (0.0014) N5 Rms deviation of fitted atoms = 0.0027 − 1.8613 (0.0243) x + 7.1034 (0.0088) y + 6.8167 (0.0125) z = 5.5504 (0.0210) Angle to previous plane (with approximate e.s.d.) = 30.96 (0.13) * −0.0327 (0.0021) C7 * 0.0353 (0.0018) C8 * −0.0186 (0.0022) C9 * 0.0014 (0.0018) C10_a * 0.0145 (0.0017) C12_a −0.6414 (0.0067) C11_a Rms deviation of fitted atoms = 0.0240 − 5.4354 (0.0637) x + 6.8601 (0.0262) y + 5.6505 (0.0412) z = 2.0087 (0.0690) Angle to previous plane (with approximate e.s.d.) = 17.66 (0.42) * 0.0317 (0.0049) C7 * −0.0863 (0.0028) C8 * 0.0923 (0.0052) C9 * −0.0482 (0.0046) C10' * 0.0105 (0.0045) C12' 0.5580 (0.0197) C11' Rms deviation of fitted atoms = 0.0623 |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
N1 | 1.10964 (16) | 0.6399 (2) | 0.4368 (2) | 0.0290 (5) | |
C2 | 1.1109 (2) | 0.6181 (3) | 0.5613 (2) | 0.0301 (6) | |
C21 | 1.2104 (2) | 0.6322 (4) | 0.6382 (3) | 0.0458 (8) | |
C3 | 1.0084 (2) | 0.5815 (3) | 0.5951 (2) | 0.0279 (5) | |
C4 | 0.95073 (18) | 0.5843 (2) | 0.4815 (2) | 0.0240 (5) | |
N5 | 1.01159 (17) | 0.6207 (2) | 0.3848 (2) | 0.0292 (5) | |
N6 | 0.84220 (15) | 0.5633 (2) | 0.45551 (19) | 0.0260 (4) | |
C7 | 0.77125 (18) | 0.4823 (2) | 0.5174 (2) | 0.0262 (5) | |
C8 | 0.79550 (19) | 0.4000 (3) | 0.6198 (2) | 0.0271 (5) | |
C9 | 0.7170 (2) | 0.3153 (3) | 0.6787 (2) | 0.0307 (6) | |
O91 | 0.74012 (15) | 0.2407 (2) | 0.77250 (19) | 0.0410 (5) | |
C10 | 0.6014 (3) | 0.3270 (4) | 0.6379 (4) | 0.0314 (6) | 0.760 (5) |
C11 | 0.5903 (3) | 0.3668 (4) | 0.4991 (4) | 0.0314 (6) | 0.760 (5) |
C12 | 0.6578 (3) | 0.5002 (4) | 0.4748 (4) | 0.0314 (6) | 0.760 (5) |
C13 | 0.4732 (4) | 0.4009 (5) | 0.4714 (5) | 0.0482 (8) | 0.760 (5) |
C14 | 0.6256 (3) | 0.2456 (5) | 0.4150 (4) | 0.0482 (8) | 0.760 (5) |
C10' | 0.6147 (9) | 0.2726 (14) | 0.6074 (12) | 0.0314 (6) | 0.240 (5) |
C12' | 0.6653 (7) | 0.4544 (14) | 0.4457 (11) | 0.0314 (6) | 0.240 (5) |
C11' | 0.5716 (10) | 0.3953 (12) | 0.5242 (12) | 0.0314 (6) | 0.240 (5) |
C13' | 0.4790 (12) | 0.3483 (19) | 0.4385 (15) | 0.0482 (8) | 0.240 (5) |
C14' | 0.5378 (10) | 0.5157 (14) | 0.6122 (12) | 0.0482 (8) | 0.240 (5) |
H1 | 1.1665 | 0.6642 | 0.3932 | 0.035* | |
H21A | 1.2644 | 0.6846 | 0.5902 | 0.069* | |
H21B | 1.2379 | 0.5377 | 0.6589 | 0.069* | |
H21C | 1.1942 | 0.6837 | 0.7159 | 0.069* | |
H3 | 0.9824 | 0.5594 | 0.6767 | 0.033* | |
H6 | 0.8171 | 0.6093 | 0.3899 | 0.031* | |
H8 | 0.8664 | 0.4000 | 0.6516 | 0.033* | |
H10A | 0.5652 | 0.3998 | 0.6897 | 0.038* | 0.760 (5) |
H10B | 0.5652 | 0.2352 | 0.6528 | 0.038* | 0.760 (5) |
H12A | 0.6570 | 0.5218 | 0.3838 | 0.038* | 0.760 (5) |
H12B | 0.6254 | 0.5816 | 0.5195 | 0.038* | 0.760 (5) |
H13A | 0.4653 | 0.4261 | 0.3825 | 0.072* | 0.760 (5) |
H13B | 0.4502 | 0.4809 | 0.5237 | 0.072* | 0.760 (5) |
H13C | 0.4290 | 0.3178 | 0.4902 | 0.072* | 0.760 (5) |
H14A | 0.5785 | 0.1638 | 0.4282 | 0.072* | 0.760 (5) |
H14B | 0.6993 | 0.2191 | 0.4356 | 0.072* | 0.760 (5) |
H14C | 0.6217 | 0.2755 | 0.3270 | 0.072* | 0.760 (5) |
H10C | 0.5590 | 0.2447 | 0.6686 | 0.038* | 0.240 (5) |
H10D | 0.6302 | 0.1894 | 0.5536 | 0.038* | 0.240 (5) |
H12C | 0.6419 | 0.5446 | 0.4067 | 0.038* | 0.240 (5) |
H12D | 0.6802 | 0.3868 | 0.3767 | 0.038* | 0.240 (5) |
H13D | 0.4162 | 0.3264 | 0.4900 | 0.072* | 0.240 (5) |
H13E | 0.5003 | 0.2637 | 0.3913 | 0.072* | 0.240 (5) |
H13F | 0.4615 | 0.4250 | 0.3798 | 0.072* | 0.240 (5) |
H14D | 0.5083 | 0.5940 | 0.5626 | 0.072* | 0.240 (5) |
H14E | 0.6001 | 0.5491 | 0.6595 | 0.072* | 0.240 (5) |
H14F | 0.4834 | 0.4809 | 0.6708 | 0.072* | 0.240 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0253 (10) | 0.0349 (11) | 0.0268 (11) | −0.0070 (8) | 0.0009 (8) | −0.0010 (9) |
C2 | 0.0356 (14) | 0.0276 (12) | 0.0270 (13) | −0.0040 (10) | −0.0045 (11) | 0.0035 (10) |
C21 | 0.0385 (15) | 0.0589 (19) | 0.0400 (16) | −0.0139 (13) | −0.0125 (13) | 0.0093 (15) |
C3 | 0.0312 (12) | 0.0311 (12) | 0.0213 (12) | −0.0056 (9) | 0.0009 (10) | 0.0029 (10) |
C4 | 0.0282 (11) | 0.0203 (10) | 0.0233 (11) | −0.0007 (8) | 0.0021 (10) | 0.0019 (9) |
N5 | 0.0293 (10) | 0.0327 (10) | 0.0256 (10) | −0.0064 (9) | 0.0017 (9) | 0.0023 (9) |
N6 | 0.0268 (10) | 0.0274 (10) | 0.0237 (10) | 0.0016 (7) | −0.0007 (8) | 0.0091 (8) |
C7 | 0.0270 (11) | 0.0268 (11) | 0.0247 (12) | −0.0013 (9) | 0.0006 (9) | 0.0048 (9) |
C8 | 0.0253 (11) | 0.0294 (11) | 0.0267 (13) | −0.0035 (9) | −0.0021 (10) | 0.0069 (10) |
C9 | 0.0289 (12) | 0.0367 (13) | 0.0264 (12) | −0.0071 (10) | −0.0043 (10) | 0.0087 (11) |
O91 | 0.0418 (10) | 0.0488 (12) | 0.0324 (10) | −0.0190 (9) | −0.0115 (9) | 0.0214 (9) |
C10 | 0.0276 (9) | 0.0347 (14) | 0.0319 (13) | −0.0034 (9) | −0.0014 (8) | 0.0113 (10) |
C11 | 0.0276 (9) | 0.0347 (14) | 0.0319 (13) | −0.0034 (9) | −0.0014 (8) | 0.0113 (10) |
C12 | 0.0276 (9) | 0.0347 (14) | 0.0319 (13) | −0.0034 (9) | −0.0014 (8) | 0.0113 (10) |
C13 | 0.0458 (14) | 0.058 (2) | 0.0410 (17) | −0.0188 (15) | −0.0101 (13) | 0.0110 (14) |
C14 | 0.0458 (14) | 0.058 (2) | 0.0410 (17) | −0.0188 (15) | −0.0101 (13) | 0.0110 (14) |
C10' | 0.0276 (9) | 0.0347 (14) | 0.0319 (13) | −0.0034 (9) | −0.0014 (8) | 0.0113 (10) |
C12' | 0.0276 (9) | 0.0347 (14) | 0.0319 (13) | −0.0034 (9) | −0.0014 (8) | 0.0113 (10) |
C11' | 0.0276 (9) | 0.0347 (14) | 0.0319 (13) | −0.0034 (9) | −0.0014 (8) | 0.0113 (10) |
C13' | 0.0458 (14) | 0.058 (2) | 0.0410 (17) | −0.0188 (15) | −0.0101 (13) | 0.0110 (14) |
C14' | 0.0458 (14) | 0.058 (2) | 0.0410 (17) | −0.0188 (15) | −0.0101 (13) | 0.0110 (14) |
N1—C2 | 1.342 (3) | C11—C14 | 1.517 (6) |
N1—N5 | 1.358 (3) | C11—C13 | 1.530 (6) |
N1—H1 | 0.8800 | C11—C12 | 1.537 (5) |
C2—C3 | 1.376 (4) | C12—H12A | 0.9900 |
C2—C21 | 1.497 (4) | C12—H12B | 0.9900 |
C21—H21A | 0.9800 | C13—H13A | 0.9800 |
C21—H21B | 0.9800 | C13—H13B | 0.9800 |
C21—H21C | 0.9800 | C13—H13C | 0.9800 |
C3—C4 | 1.409 (4) | C14—H14A | 0.9800 |
C3—H3 | 0.9500 | C14—H14B | 0.9800 |
C4—N5 | 1.326 (3) | C14—H14C | 0.9800 |
C4—N6 | 1.400 (3) | C10'—C11' | 1.554 (14) |
N6—C7 | 1.343 (3) | C10'—H10C | 0.9900 |
N6—H6 | 0.8800 | C10'—H10D | 0.9900 |
C7—C8 | 1.372 (3) | C12'—C11' | 1.544 (15) |
C7—C12 | 1.500 (4) | C12'—H12C | 0.9900 |
C7—C12' | 1.553 (8) | C12'—H12D | 0.9900 |
C8—C9 | 1.413 (3) | C11'—C14' | 1.531 (15) |
C8—H8 | 0.9500 | C11'—C13' | 1.539 (15) |
C9—O91 | 1.255 (3) | C13'—H13D | 0.9800 |
C9—C10 | 1.515 (4) | C13'—H13E | 0.9800 |
C9—C10' | 1.542 (12) | C13'—H13F | 0.9800 |
C10—C11 | 1.530 (5) | C14'—H14D | 0.9800 |
C10—H10A | 0.9900 | C14'—H14E | 0.9800 |
C10—H10B | 0.9900 | C14'—H14F | 0.9800 |
C2—N1—N5 | 113.1 (2) | C14—C11—C10 | 111.0 (3) |
C2—N1—H1 | 123.4 | C14—C11—C13 | 108.9 (4) |
N5—N1—H1 | 123.4 | C10—C11—C13 | 108.9 (4) |
N1—C2—C3 | 106.6 (2) | C14—C11—C12 | 110.9 (3) |
N1—C2—C21 | 122.5 (3) | C10—C11—C12 | 108.3 (4) |
C3—C2—C21 | 130.9 (3) | C13—C11—C12 | 108.7 (3) |
C2—C21—H21A | 109.5 | C7—C12—C11 | 112.1 (3) |
C2—C21—H21B | 109.5 | C7—C12—H12A | 109.2 |
H21A—C21—H21B | 109.5 | C11—C12—H12A | 109.2 |
C2—C21—H21C | 109.5 | C7—C12—H12B | 109.2 |
H21A—C21—H21C | 109.5 | C11—C12—H12B | 109.2 |
H21B—C21—H21C | 109.5 | H12A—C12—H12B | 107.9 |
C2—C3—C4 | 104.4 (2) | C9—C10'—C11' | 112.0 (9) |
C2—C3—H3 | 127.8 | C9—C10'—H10C | 109.2 |
C4—C3—H3 | 127.8 | C11'—C10'—H10C | 109.2 |
N5—C4—N6 | 116.1 (2) | C9—C10'—H10D | 109.2 |
N5—C4—C3 | 112.1 (2) | C11'—C10'—H10D | 109.2 |
N6—C4—C3 | 131.6 (2) | H10C—C10'—H10D | 107.9 |
C4—N5—N1 | 103.7 (2) | C11'—C12'—C7 | 116.3 (9) |
C7—N6—C4 | 128.6 (2) | C11'—C12'—H12C | 108.2 |
C7—N6—H6 | 115.7 | C7—C12'—H12C | 108.2 |
C4—N6—H6 | 115.7 | C11'—C12'—H12D | 108.2 |
N6—C7—C8 | 124.4 (2) | C7—C12'—H12D | 108.2 |
N6—C7—C12 | 114.4 (2) | H12C—C12'—H12D | 107.4 |
C8—C7—C12 | 120.9 (2) | C14'—C11'—C13' | 111.6 (11) |
N6—C7—C12' | 114.8 (5) | C14'—C11'—C12' | 105.9 (10) |
C8—C7—C12' | 118.9 (5) | C13'—C11'—C12' | 110.8 (11) |
C12—C7—C12' | 20.3 (5) | C14'—C11'—C10' | 107.4 (11) |
C7—C8—C9 | 121.2 (2) | C13'—C11'—C10' | 112.6 (12) |
C7—C8—H8 | 119.4 | C12'—C11'—C10' | 108.3 (10) |
C9—C8—H8 | 119.4 | C11'—C13'—H13D | 109.5 |
O91—C9—C8 | 120.7 (2) | C11'—C13'—H13E | 109.5 |
O91—C9—C10 | 119.3 (2) | H13D—C13'—H13E | 109.5 |
C8—C9—C10 | 119.7 (2) | C11'—C13'—H13F | 109.5 |
O91—C9—C10' | 115.9 (5) | H13D—C13'—H13F | 109.5 |
C8—C9—C10' | 120.4 (5) | H13E—C13'—H13F | 109.5 |
C10—C9—C10' | 23.8 (5) | C11'—C14'—H14D | 109.5 |
C9—C10—C11 | 112.4 (3) | C11'—C14'—H14E | 109.5 |
C9—C10—H10A | 109.1 | H14D—C14'—H14E | 109.5 |
C11—C10—H10A | 109.1 | C11'—C14'—H14F | 109.5 |
C9—C10—H10B | 109.1 | H14D—C14'—H14F | 109.5 |
C11—C10—H10B | 109.1 | H14E—C14'—H14F | 109.5 |
H10A—C10—H10B | 107.9 | ||
N5—N1—C2—C3 | 0.3 (3) | C10'—C9—C10—C11 | −68.3 (12) |
N5—N1—C2—C21 | 179.6 (2) | C9—C10—C11—C14 | 69.7 (4) |
N1—C2—C3—C4 | 0.1 (3) | C9—C10—C11—C13 | −170.5 (3) |
C21—C2—C3—C4 | −179.0 (3) | C9—C10—C11—C12 | −52.4 (5) |
C2—C3—C4—N5 | −0.5 (3) | N6—C7—C12—C11 | 153.5 (3) |
C2—C3—C4—N6 | −176.6 (2) | C8—C7—C12—C11 | −32.7 (5) |
N6—C4—N5—N1 | 177.40 (19) | C12'—C7—C12—C11 | 57.8 (13) |
C3—C4—N5—N1 | 0.7 (3) | C14—C11—C12—C7 | −68.6 (4) |
C2—N1—N5—C4 | −0.6 (3) | C10—C11—C12—C7 | 53.5 (5) |
N5—C4—N6—C7 | 154.4 (2) | C13—C11—C12—C7 | 171.7 (3) |
C3—C4—N6—C7 | −29.7 (4) | O91—C9—C10'—C11' | 160.7 (8) |
C4—N6—C7—C8 | −1.7 (4) | C8—C9—C10'—C11' | −38.9 (12) |
C4—N6—C7—C12 | 171.8 (3) | C10—C9—C10'—C11' | 56.4 (10) |
C4—N6—C7—C12' | −165.9 (6) | N6—C7—C12'—C11' | −165.1 (8) |
N6—C7—C8—C9 | −178.8 (2) | C8—C7—C12'—C11' | 29.8 (13) |
C12—C7—C8—C9 | 8.1 (4) | C12—C7—C12'—C11' | −71.5 (15) |
C12'—C7—C8—C9 | −15.2 (7) | C7—C12'—C11'—C14' | 68.8 (13) |
C7—C8—C9—O91 | −179.9 (3) | C7—C12'—C11'—C13' | −170.1 (10) |
C7—C8—C9—C10 | −6.8 (4) | C7—C12'—C11'—C10' | −46.1 (15) |
C7—C8—C9—C10' | 20.7 (7) | C9—C10'—C11'—C14' | −64.7 (12) |
O91—C9—C10—C11 | −156.5 (3) | C9—C10'—C11'—C13' | 172.1 (10) |
C8—C9—C10—C11 | 30.3 (5) | C9—C10'—C11'—C12' | 49.2 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O91i | 0.88 | 1.95 | 2.804 (3) | 162 |
N6—H6···O91ii | 0.88 | 1.90 | 2.766 (3) | 168 |
Symmetry codes: (i) −x+2, −y+1, z−1/2; (ii) −x+3/2, y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C12H17N3O |
Mr | 219.29 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 150 |
a, b, c (Å) | 12.5130 (3), 9.4275 (3), 10.6441 (3) |
V (Å3) | 1255.65 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.25 × 0.15 × 0.05 |
Data collection | |
Diffractometer | Nonius KAPPA CCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995, 1997) |
Tmin, Tmax | 0.981, 0.996 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13142, 1515, 1360 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.647 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.122, 1.05 |
No. of reflections | 1515 |
No. of parameters | 148 |
No. of restraints | 11 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.34 |
Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO (Otwinowski & Minor, 1997), DENZO, SHELXS97 (Sheldrick, 1997), PLATON (Spek, 2000), SHELXL97 and PRPKAPPA (Ferguson, 1999).
C4—N6 | 1.400 (3) | C8—C9 | 1.413 (3) |
N6—C7 | 1.343 (3) | C9—O91 | 1.255 (3) |
C7—C8 | 1.372 (3) | ||
N6—C7—C8—C9 | −178.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O91i | 0.88 | 1.95 | 2.804 (3) | 162 |
N6—H6···O91ii | 0.88 | 1.90 | 2.766 (3) | 168 |
Symmetry codes: (i) −x+2, −y+1, z−1/2; (ii) −x+3/2, y+1/2, z−1/2. |
Recently, we reported the structures of several pyrazolo[3,4-b]pyridines prepared from 3-aminopyrazoles and substituted cyanochalcones (Quiroga et al., 1999). Continuing the study of the reactions of 3-aminopyrazoles as intermediates in the preparation of fused pyrazole heterocycles, we have carried out reactions between these compounds and 1,3-diketones. Pyrazolo[3,4-c]pyridines have been prepared from arylidineaminopyrazoles and 1,3-dicarbonyl derivatives such as dimedone. The title compound, (III), results from the reaction of 3-amino-5-methylpyrazole, (I), on dimedone, (II), as shown in the scheme below. 3-N-substituted diaminopyrazole derivatives have been reported to be a target for neuropeptide Y antagonists (Fumaki, Fukuroda, Kanatani & Ihara, 1996) and hence are used in the treatment of bulimia, obesity and diabetes (Fumaki, Fukuroda, Kanatani, Kanatani & Ihara, 1996) or as an anticonvulsant (Lankau et al., 1999). \sch
The pyrazole ring in (III) is strictly planar with the atoms attached directly to it and shows high aromaticity, although there is a slight suggestion of double-bond character, as shown in the scheme. This arises because, due to the presence of the N6—H fragment attached to C4, there is no delocalization of the lone pair on N6 towards the pyrazole ring; C4—N6 [1.400 (3) Å] is clearly a single bond.
The cyclohexenone ring is disordered, with atoms C10, C11, C12 and C14 occupying two alternate components. The major component has an occupancy of 0.760 (5) and the minor 0.240 (5). In the following description the minor atom names are given in parentheses. The two positions for C13 overlap each other. In both of these components, all atoms except C11 (C11') are nearly coplanar, the maximum and minimum deviations being 0.035 (2) Å for C8 [0.092 (5) Å for C9] and −0.033 (2) Å for C7 [−0.086 (3) Å for C8]. Atom C11 in the major component is 0.641 (7) Å below the plane of the other five atoms and in the minor component 0.56 (2) Å above the plane of the other five atoms. This means that the molecule adopts each of the two possible sofa conformations involving C11 (C11'). The mean planes of these two disordered rings, consisting of the five ring atoms but omitting C11 (C11'), are inclined to one another by 17.7°.
Another structural feature is that the lone pair on N6 is delocalized to the α,β-unsaturated ketone showing amide vinylogous behaviour, as shown by the bond distances [N6—C7 1.343 (3), C7—C8 1.372 (3), C8—C9 1.413 (3) and C9—O91 1.255 (3) Å] and the torsion angle [N6—C7—C8—C9 − 178.8 (2)°]. This π system defined by the mean plane of N6, C7, C8, C9 and O91 is isolated from the pyrazole ring and both planes are inclined to one another at 28.61 (12)°. Selected bond lengths are given in Table 1.
The molecules are linked by two strong N—H···O hydrogen bonds, each involving O91 as an acceptor, to form a three-dimensional network of intersecting infinite chains. Atom O91 at (2 − x, 1 − y, z − 1/2) acts as an acceptor for the donor atom N1, with an N.·O distance of 2.804 (3) Å. Atom O91 at (3/2 − x, 1/2 + y, z − 1/2) acts as an acceptor for atom N6, with an N.·O distance of 2.766 (3) Å. The former gives rise to a primary C(9) motif, which when translated by the screw axis at (1, 1/2, z) gives an infinite spiral chain (Fig. 2). The latter gives a C(6) chain motif, producing an infinite chain running parallel to [011], produced by the action of the n-glide plane at 3/4 along a. Full hydrogen-bond data are given in Table 2.
Examination of the structure with PLATON (Spek, 2000) showed that there were no solvent-accessible voids in the crystal lattice.