Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801001465/na6037sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801001465/na6037Isup2.hkl |
CCDC reference: 159751
A solution of 5-aminopyrazole (1 mmol), dimedone (1 mmol) and 4-methoxybenzaldehyde (1 mmol) in 15 ml of absolute ethanol were heated to reflux for 20–50 min (thin-layer chromatography control). The reaction mixture was cooled and the solid corresponding to the title compound was filtered off, washed with ethanol, dried and recrystallized from ethanol to afford suitable crystals for diffraction (61% yield, m.p. 570 K).
H atoms were treated as riding atoms with C—H = 0.95–1.00 Å and N—H = 0.88 Å. In the disordered groups, each of the in the pairs C4/C420, C44/C424 and O44/O424 were given equal ADPs. The C4–C41 and C420–C421 bonds were fixed at 1.520 (5) Å. All other parameters in the groups were allowed to refine freely. Although there are some variations from normal phenyl bonds in the minor component, these lie within 3σ of the expected values so no further action was taken.
Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek, 2000); software used to prepare material for publication: SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).
C20H23N3O2 | Dx = 1.271 Mg m−3 |
Mr = 337.41 | Melting point: 570 K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 8.5820 (3) Å | Cell parameters from 3956 reflections |
b = 14.7031 (5) Å | θ = 2.0–27.5° |
c = 14.5369 (8) Å | µ = 0.08 mm−1 |
β = 106.0610 (15)° | T = 150 K |
V = 1762.70 (13) Å3 | Prism, colourless |
Z = 4 | 0.38 × 0.24 × 0.18 mm |
F(000) = 720 |
KappaCCD diffractometer | 3956 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 2662 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ϕ and ω scans with κ offsets | θmax = 27.5°, θmin = 2.0° |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | h = −11→10 |
Tmin = 0.969, Tmax = 0.985 | k = −18→16 |
11320 measured reflections | l = −15→18 |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0655P)2 + 0.4575P] where P = (Fo2 + 2Fc2)/3 |
3956 reflections | (Δ/σ)max = 0.002 |
289 parameters | Δρmax = 0.28 e Å−3 |
2 restraints | Δρmin = −0.30 e Å−3 |
C20H23N3O2 | V = 1762.70 (13) Å3 |
Mr = 337.41 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.5820 (3) Å | µ = 0.08 mm−1 |
b = 14.7031 (5) Å | T = 150 K |
c = 14.5369 (8) Å | 0.38 × 0.24 × 0.18 mm |
β = 106.0610 (15)° |
KappaCCD diffractometer | 3956 independent reflections |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 2662 reflections with I > 2σ(I) |
Tmin = 0.969, Tmax = 0.985 | Rint = 0.029 |
11320 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 2 restraints |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.28 e Å−3 |
3956 reflections | Δρmin = −0.30 e Å−3 |
289 parameters |
Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm (Fox & Holmes, 1966) which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. no transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
N1 | 0.96978 (18) | 0.49548 (9) | 0.87356 (10) | 0.0255 (4) | |
N2 | 0.93258 (18) | 0.50561 (9) | 0.77707 (10) | 0.0249 (4) | |
C3 | 0.8362 (2) | 0.43944 (12) | 0.72831 (13) | 0.0244 (4) | |
C31 | 0.7756 (3) | 0.44108 (14) | 0.62201 (14) | 0.0348 (5) | |
C3A | 0.8090 (2) | 0.38006 (11) | 0.79599 (12) | 0.0223 (4) | |
C4A | 0.6997 (2) | 0.27021 (11) | 0.88876 (12) | 0.0215 (4) | |
C4 | 0.7353 (10) | 0.2850 (5) | 0.7912 (7) | 0.0263 (6) | 0.65 |
C41 | 0.8440 (6) | 0.2109 (3) | 0.7696 (3) | 0.0211 (11) | 0.65 |
C42 | 0.8013 (4) | 0.1640 (2) | 0.6848 (2) | 0.0263 (6) | 0.65 |
C43 | 0.8989 (12) | 0.0964 (9) | 0.6615 (10) | 0.024 (2) | 0.65 |
C44 | 1.0489 (4) | 0.0785 (2) | 0.7300 (2) | 0.0259 (7) | 0.65 |
C45 | 1.0950 (4) | 0.12531 (19) | 0.8160 (2) | 0.0291 (7) | 0.65 |
C46 | 0.9925 (4) | 0.1902 (2) | 0.8356 (3) | 0.0261 (7) | 0.65 |
C47 | 1.1192 (12) | −0.0368 (6) | 0.6313 (5) | 0.0367 (13) | 0.65 |
O44 | 1.1610 (3) | 0.01536 (14) | 0.71755 (15) | 0.0354 (5) | 0.65 |
C420 | 0.7103 (15) | 0.2958 (8) | 0.7904 (10) | 0.0128 (16) | 0.35 |
O424 | 0.9848 (5) | 0.0242 (2) | 0.6046 (3) | 0.0354 (5) | 0.35 |
C421 | 0.7838 (9) | 0.2220 (6) | 0.7422 (6) | 0.0177 (19) | 0.35 |
C422 | 0.7256 (6) | 0.2043 (3) | 0.6442 (4) | 0.0215 (11) | 0.35 |
C423 | 0.7955 (6) | 0.1383 (3) | 0.6000 (4) | 0.0212 (11) | 0.35 |
C424 | 0.936 (3) | 0.0882 (17) | 0.6586 (19) | 0.023 (3) | 0.35 |
C425 | 0.9869 (8) | 0.1032 (4) | 0.7527 (4) | 0.0259 (13) | 0.35 |
C426 | 0.9144 (9) | 0.1709 (5) | 0.7944 (5) | 0.0230 (13) | 0.35 |
C427 | 1.106 (2) | −0.0355 (13) | 0.6578 (11) | 0.0367 (13) | 0.35 |
C5 | 0.5831 (2) | 0.20123 (11) | 0.89343 (13) | 0.0223 (4) | |
O51 | 0.50282 (15) | 0.16087 (8) | 0.82068 (9) | 0.0282 (3) | |
C6 | 0.5555 (2) | 0.17944 (12) | 0.98899 (13) | 0.0260 (4) | |
C7 | 0.7037 (2) | 0.19394 (11) | 1.07461 (13) | 0.0245 (4) | |
C71 | 0.6596 (3) | 0.18323 (13) | 1.16879 (14) | 0.0318 (5) | |
C72 | 0.8362 (2) | 0.12516 (12) | 1.07198 (14) | 0.0309 (5) | |
C8 | 0.7618 (2) | 0.29165 (11) | 1.06745 (12) | 0.0252 (4) | |
C8A | 0.7827 (2) | 0.31422 (11) | 0.97077 (13) | 0.0223 (4) | |
C9A | 0.8924 (2) | 0.41878 (11) | 0.88289 (12) | 0.0221 (4) | |
N9 | 0.88769 (18) | 0.38308 (9) | 0.97035 (10) | 0.0248 (4) | |
H2 | 0.9681 | 0.5511 | 0.7491 | 0.030* | |
H31A | 0.7698 | 0.3788 | 0.5973 | 0.052* | |
H31B | 0.8497 | 0.4770 | 0.5959 | 0.052* | |
H31C | 0.6674 | 0.4686 | 0.6028 | 0.052* | |
H4 | 0.6302 | 0.2844 | 0.7398 | 0.032* | 0.65 |
H42 | 0.7008 | 0.1779 | 0.6398 | 0.032* | 0.65 |
H43 | 0.8662 | 0.0641 | 0.6026 | 0.029* | 0.65 |
H45 | 1.1963 | 0.1129 | 0.8611 | 0.035* | 0.65 |
H46 | 1.0233 | 0.2215 | 0.8951 | 0.031* | 0.65 |
H17A | 1.2152 | −0.0694 | 0.6248 | 0.055* | 0.33 |
H17B | 1.0794 | 0.0039 | 0.5764 | 0.055* | 0.33 |
H17C | 1.0343 | −0.0806 | 0.6335 | 0.055* | 0.33 |
H17D | 1.0041 | −0.0280 | 0.5983 | 0.055* | 0.33 |
H17E | 1.1399 | −0.1013 | 0.6467 | 0.055* | 0.33 |
H17F | 1.1850 | −0.0168 | 0.5897 | 0.055* | 0.33 |
H420 | 0.5982 | 0.3087 | 0.7493 | 0.015* | 0.35 |
H422 | 0.6360 | 0.2382 | 0.6069 | 0.026* | 0.35 |
H423 | 0.7537 | 0.1260 | 0.5336 | 0.025* | 0.35 |
H425 | 1.0730 | 0.0679 | 0.7914 | 0.031* | 0.35 |
H426 | 0.9560 | 0.1823 | 0.8611 | 0.028* | 0.35 |
H27G | 1.1354 | −0.0792 | 0.6143 | 0.055* | 0.18 |
H27H | 1.0654 | −0.0683 | 0.7050 | 0.055* | 0.18 |
H27I | 1.2026 | −0.0003 | 0.6908 | 0.055* | 0.18 |
H27J | 1.1336 | −0.0194 | 0.7258 | 0.055* | 0.18 |
H27K | 1.2035 | −0.0303 | 0.6351 | 0.055* | 0.18 |
H27L | 1.0663 | −0.0982 | 0.6492 | 0.055* | 0.18 |
H6A | 0.5208 | 0.1152 | 0.9885 | 0.031* | |
H6B | 0.4657 | 0.2179 | 0.9975 | 0.031* | |
H71A | 0.7532 | 0.1995 | 1.2222 | 0.048* | |
H71B | 0.6289 | 0.1200 | 1.1759 | 0.048* | |
H71C | 0.5684 | 0.2234 | 1.1687 | 0.048* | |
H72A | 0.8675 | 0.1328 | 1.0125 | 0.046* | |
H72B | 0.7952 | 0.0633 | 1.0749 | 0.046* | |
H72C | 0.9309 | 0.1353 | 1.1269 | 0.046* | |
H8A | 0.6825 | 0.3344 | 1.0818 | 0.030* | |
H8B | 0.8667 | 0.3006 | 1.1165 | 0.030* | |
H9 | 0.9512 | 0.4045 | 1.0242 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0316 (9) | 0.0218 (8) | 0.0238 (9) | −0.0019 (6) | 0.0089 (7) | 0.0022 (6) |
N2 | 0.0310 (9) | 0.0211 (7) | 0.0244 (9) | −0.0009 (6) | 0.0104 (7) | 0.0026 (6) |
C3 | 0.0251 (10) | 0.0244 (9) | 0.0248 (10) | 0.0014 (7) | 0.0089 (8) | 0.0002 (7) |
C31 | 0.0405 (12) | 0.0388 (11) | 0.0254 (11) | −0.0068 (9) | 0.0094 (9) | 0.0023 (8) |
C3A | 0.0254 (9) | 0.0209 (9) | 0.0215 (10) | −0.0006 (7) | 0.0078 (8) | −0.0001 (7) |
C4A | 0.0252 (9) | 0.0198 (9) | 0.0210 (10) | 0.0000 (7) | 0.0089 (7) | −0.0009 (7) |
C4 | 0.0264 (15) | 0.0275 (15) | 0.0258 (15) | −0.0055 (12) | 0.0087 (12) | −0.0036 (13) |
C41 | 0.025 (3) | 0.021 (2) | 0.019 (3) | −0.003 (2) | 0.009 (2) | 0.000 (2) |
C42 | 0.0264 (15) | 0.0275 (15) | 0.0258 (15) | −0.0055 (12) | 0.0087 (12) | −0.0036 (13) |
C43 | 0.018 (5) | 0.026 (3) | 0.030 (3) | −0.004 (3) | 0.010 (3) | −0.007 (2) |
C44 | 0.0303 (19) | 0.0201 (15) | 0.0309 (19) | −0.0009 (14) | 0.0147 (16) | −0.0009 (13) |
C45 | 0.0282 (16) | 0.0302 (16) | 0.0273 (17) | 0.0027 (13) | 0.0048 (14) | 0.0020 (12) |
C46 | 0.0304 (19) | 0.0266 (17) | 0.0225 (18) | 0.0026 (14) | 0.0095 (15) | −0.0025 (13) |
C47 | 0.043 (2) | 0.0323 (12) | 0.040 (5) | 0.0062 (12) | 0.022 (3) | −0.006 (3) |
O44 | 0.0403 (11) | 0.0314 (10) | 0.0356 (11) | 0.0097 (8) | 0.0125 (9) | −0.0046 (8) |
C420 | 0.021 (5) | 0.009 (3) | 0.011 (3) | 0.005 (2) | 0.009 (3) | −0.002 (2) |
O424 | 0.0403 (11) | 0.0314 (10) | 0.0356 (11) | 0.0097 (8) | 0.0125 (9) | −0.0046 (8) |
C421 | 0.015 (5) | 0.018 (3) | 0.020 (5) | −0.002 (3) | 0.006 (3) | −0.001 (3) |
C422 | 0.022 (3) | 0.019 (2) | 0.021 (3) | 0.001 (2) | 0.002 (2) | 0.005 (2) |
C423 | 0.027 (3) | 0.022 (2) | 0.016 (3) | −0.001 (2) | 0.008 (2) | −0.005 (2) |
C424 | 0.013 (7) | 0.020 (4) | 0.039 (6) | 0.009 (4) | 0.014 (5) | 0.011 (4) |
C425 | 0.031 (4) | 0.022 (3) | 0.028 (4) | 0.009 (3) | 0.014 (3) | 0.005 (2) |
C426 | 0.022 (4) | 0.029 (4) | 0.015 (3) | −0.002 (3) | −0.001 (3) | 0.002 (3) |
C427 | 0.043 (2) | 0.0323 (12) | 0.040 (5) | 0.0062 (12) | 0.022 (3) | −0.006 (3) |
C5 | 0.0213 (9) | 0.0194 (8) | 0.0270 (10) | 0.0036 (7) | 0.0080 (8) | −0.0015 (7) |
O51 | 0.0279 (7) | 0.0267 (7) | 0.0297 (8) | −0.0049 (5) | 0.0077 (6) | −0.0066 (5) |
C6 | 0.0301 (10) | 0.0231 (9) | 0.0277 (10) | −0.0026 (7) | 0.0126 (8) | −0.0005 (7) |
C7 | 0.0311 (10) | 0.0210 (9) | 0.0240 (10) | 0.0006 (7) | 0.0123 (8) | 0.0001 (7) |
C71 | 0.0429 (12) | 0.0279 (10) | 0.0281 (11) | −0.0014 (9) | 0.0156 (9) | 0.0022 (8) |
C72 | 0.0372 (11) | 0.0253 (10) | 0.0311 (11) | 0.0051 (8) | 0.0110 (9) | 0.0002 (8) |
C8 | 0.0343 (11) | 0.0210 (9) | 0.0217 (10) | −0.0014 (8) | 0.0098 (8) | −0.0027 (7) |
C8A | 0.0255 (10) | 0.0176 (8) | 0.0248 (10) | 0.0023 (7) | 0.0087 (8) | 0.0002 (7) |
C9A | 0.0251 (9) | 0.0175 (8) | 0.0236 (10) | 0.0010 (7) | 0.0069 (8) | 0.0001 (7) |
N9 | 0.0316 (9) | 0.0219 (7) | 0.0189 (8) | −0.0061 (6) | 0.0036 (6) | −0.0014 (6) |
N1—C9A | 1.335 (2) | O424—C424 | 1.37 (2) |
N1—N2 | 1.358 (2) | O424—C427 | 1.42 (2) |
N2—C3 | 1.345 (2) | C421—C426 | 1.388 (8) |
N2—H2 | 0.8800 | C421—C422 | 1.398 (10) |
C3—C3A | 1.383 (2) | C422—C423 | 1.388 (7) |
C3—C31 | 1.488 (3) | C422—H422 | 0.9500 |
C31—H31A | 0.9800 | C423—C424 | 1.47 (2) |
C31—H31B | 0.9800 | C423—H423 | 0.9500 |
C31—H31C | 0.9800 | C424—C425 | 1.33 (3) |
C3A—C9A | 1.390 (2) | C425—C426 | 1.398 (9) |
C3A—C420 | 1.490 (15) | C425—H425 | 0.9500 |
C3A—C4 | 1.528 (9) | C426—H426 | 0.9500 |
C4A—C8A | 1.370 (2) | C427—H27G | 0.9800 |
C4A—C5 | 1.439 (2) | C427—H27H | 0.9800 |
C4A—C420 | 1.505 (14) | C427—H27I | 0.9800 |
C4A—C4 | 1.547 (10) | C427—H27J | 0.9800 |
C4—C41 | 1.521 (4) | C427—H27K | 0.9800 |
C4—H4 | 1.0000 | C427—H27L | 0.9800 |
C41—C42 | 1.371 (5) | C5—O51 | 1.242 (2) |
C41—C46 | 1.401 (5) | C5—C6 | 1.507 (2) |
C42—C43 | 1.400 (11) | C6—C7 | 1.528 (3) |
C42—H42 | 0.9500 | C6—H6A | 0.9900 |
C43—C44 | 1.418 (13) | C6—H6B | 0.9900 |
C43—H43 | 0.9500 | C7—C71 | 1.526 (2) |
C44—O44 | 1.384 (4) | C7—C72 | 1.531 (2) |
C44—C45 | 1.386 (4) | C7—C8 | 1.534 (2) |
C45—C46 | 1.381 (4) | C71—H71A | 0.9800 |
C45—H45 | 0.9500 | C71—H71B | 0.9800 |
C46—H46 | 0.9500 | C71—H71C | 0.9800 |
C47—O44 | 1.428 (8) | C72—H72A | 0.9800 |
C47—H17A | 0.9800 | C72—H72B | 0.9800 |
C47—H17B | 0.9800 | C72—H72C | 0.9800 |
C47—H17C | 0.9800 | C8—C8A | 1.502 (2) |
C47—H17D | 0.9800 | C8—H8A | 0.9900 |
C47—H17E | 0.9800 | C8—H8B | 0.9900 |
C47—H17F | 0.9800 | C8A—N9 | 1.357 (2) |
C420—C421 | 1.520 (5) | C9A—N9 | 1.386 (2) |
C420—H420 | 1.0000 | N9—H9 | 0.8800 |
C9A—N1—N2 | 102.49 (14) | C422—C421—C420 | 121.8 (7) |
C3—N2—N1 | 113.55 (14) | C423—C422—C421 | 121.6 (5) |
C3—N2—H2 | 123.2 | C423—C422—H422 | 119.2 |
N1—N2—H2 | 123.2 | C421—C422—H422 | 119.2 |
N2—C3—C3A | 106.38 (15) | C422—C423—C424 | 118.2 (10) |
N2—C3—C31 | 121.52 (16) | C422—C423—H423 | 120.9 |
C3A—C3—C31 | 132.06 (17) | C424—C423—H423 | 120.9 |
C3—C31—H31A | 109.5 | C425—C424—O424 | 129.6 (18) |
C3—C31—H31B | 109.5 | C425—C424—C423 | 119.8 (15) |
H31A—C31—H31B | 109.5 | O424—C424—C423 | 110.3 (18) |
C3—C31—H31C | 109.5 | C424—C425—C426 | 120.2 (11) |
H31A—C31—H31C | 109.5 | C424—C425—H425 | 119.9 |
H31B—C31—H31C | 109.5 | C426—C425—H425 | 119.9 |
C3—C3A—C9A | 104.03 (15) | C421—C426—C425 | 122.5 (7) |
C3—C3A—C420 | 133.7 (5) | C421—C426—H426 | 118.8 |
C9A—C3A—C420 | 122.1 (5) | C425—C426—H426 | 118.8 |
C3—C3A—C4 | 134.0 (4) | O424—C427—H27G | 109.5 |
C9A—C3A—C4 | 121.3 (4) | O424—C427—H27H | 109.5 |
C420—C3A—C4 | 10.0 (5) | H27G—C427—H27H | 109.5 |
C8A—C4A—C5 | 119.51 (16) | O424—C427—H27I | 109.5 |
C8A—C4A—C420 | 123.7 (6) | H27G—C427—H27I | 109.5 |
C5—C4A—C420 | 116.5 (6) | H27H—C427—H27I | 109.5 |
C8A—C4A—C4 | 123.0 (4) | O424—C427—H27J | 109.5 |
C5—C4A—C4 | 117.3 (4) | H27G—C427—H27J | 141.1 |
C420—C4A—C4 | 9.8 (5) | H27H—C427—H27J | 56.3 |
C41—C4—C3A | 113.2 (6) | H27I—C427—H27J | 56.3 |
C41—C4—C4A | 112.2 (6) | O424—C427—H27K | 109.5 |
C3A—C4—C4A | 105.7 (5) | H27G—C427—H27K | 56.3 |
C41—C4—H4 | 108.5 | H27H—C427—H27K | 141.1 |
C3A—C4—H4 | 108.5 | H27I—C427—H27K | 56.3 |
C4A—C4—H4 | 108.5 | H27J—C427—H27K | 109.5 |
C42—C41—C46 | 118.2 (4) | O424—C427—H27L | 109.5 |
C42—C41—C4 | 121.3 (5) | H27G—C427—H27L | 56.3 |
C46—C41—C4 | 120.5 (4) | H27H—C427—H27L | 56.3 |
C41—C42—C43 | 123.1 (6) | H27I—C427—H27L | 141.1 |
C41—C42—H42 | 118.4 | H27J—C427—H27L | 109.5 |
C43—C42—H42 | 118.4 | H27K—C427—H27L | 109.5 |
C42—C43—C44 | 116.7 (9) | O51—C5—C4A | 121.73 (16) |
C42—C43—H43 | 121.6 | O51—C5—C6 | 119.43 (16) |
C44—C43—H43 | 121.6 | C4A—C5—C6 | 118.82 (15) |
O44—C44—C45 | 114.6 (3) | C5—C6—C7 | 114.40 (15) |
O44—C44—C43 | 124.2 (5) | C5—C6—H6A | 108.7 |
C45—C44—C43 | 121.3 (5) | C7—C6—H6A | 108.7 |
C46—C45—C44 | 119.4 (3) | C5—C6—H6B | 108.7 |
C46—C45—H45 | 120.3 | C7—C6—H6B | 108.7 |
C44—C45—H45 | 120.3 | H6A—C6—H6B | 107.6 |
C45—C46—C41 | 121.3 (4) | C71—C7—C6 | 111.07 (15) |
C45—C46—H46 | 119.3 | C71—C7—C72 | 108.94 (15) |
C41—C46—H46 | 119.3 | C6—C7—C72 | 110.14 (15) |
O44—C47—H17A | 109.5 | C71—C7—C8 | 108.89 (14) |
O44—C47—H17B | 109.5 | C6—C7—C8 | 106.77 (14) |
H17A—C47—H17B | 109.5 | C72—C7—C8 | 111.03 (15) |
O44—C47—H17C | 109.5 | C7—C71—H71A | 109.5 |
H17A—C47—H17C | 109.5 | C7—C71—H71B | 109.5 |
H17B—C47—H17C | 109.5 | H71A—C71—H71B | 109.5 |
O44—C47—H17D | 109.5 | C7—C71—H71C | 109.5 |
H17A—C47—H17D | 141.1 | H71A—C71—H71C | 109.5 |
H17B—C47—H17D | 56.3 | H71B—C71—H71C | 109.5 |
H17C—C47—H17D | 56.3 | C7—C72—H72A | 109.5 |
O44—C47—H17E | 109.5 | C7—C72—H72B | 109.5 |
H17A—C47—H17E | 56.3 | H72A—C72—H72B | 109.5 |
H17B—C47—H17E | 141.1 | C7—C72—H72C | 109.5 |
H17C—C47—H17E | 56.3 | H72A—C72—H72C | 109.5 |
H17D—C47—H17E | 109.5 | H72B—C72—H72C | 109.5 |
O44—C47—H17F | 109.5 | C8A—C8—C7 | 113.31 (14) |
H17A—C47—H17F | 56.3 | C8A—C8—H8A | 108.9 |
H17B—C47—H17F | 56.3 | C7—C8—H8A | 108.9 |
H17C—C47—H17F | 141.1 | C8A—C8—H8B | 108.9 |
H17D—C47—H17F | 109.5 | C7—C8—H8B | 108.9 |
H17E—C47—H17F | 109.5 | H8A—C8—H8B | 107.7 |
C44—O44—C47 | 117.4 (4) | N9—C8A—C4A | 122.31 (16) |
C3A—C420—C4A | 109.8 (8) | N9—C8A—C8 | 114.85 (15) |
C3A—C420—C421 | 108.5 (9) | C4A—C8A—C8 | 122.82 (16) |
C4A—C420—C421 | 113.7 (8) | N1—C9A—N9 | 123.69 (15) |
C3A—C420—H420 | 108.3 | N1—C9A—C3A | 113.54 (15) |
C4A—C420—H420 | 108.3 | N9—C9A—C3A | 122.69 (16) |
C421—C420—H420 | 108.3 | C8A—N9—C9A | 118.34 (15) |
C424—O424—C427 | 114.3 (13) | C8A—N9—H9 | 120.8 |
C426—C421—C422 | 117.6 (6) | C9A—N9—H9 | 120.8 |
C426—C421—C420 | 120.6 (8) | ||
C9A—N1—N2—C3 | 0.46 (19) | C4A—C420—C421—C426 | −39.6 (15) |
N1—N2—C3—C3A | −1.1 (2) | C3A—C420—C421—C422 | −95.8 (11) |
N1—N2—C3—C31 | 176.96 (16) | C4A—C420—C421—C422 | 141.8 (9) |
N2—C3—C3A—C9A | 1.26 (19) | C426—C421—C422—C423 | −0.3 (12) |
C31—C3—C3A—C9A | −176.55 (19) | C420—C421—C422—C423 | 178.4 (9) |
N2—C3—C3A—C420 | 177.7 (4) | C421—C422—C423—C424 | −1.2 (13) |
C31—C3—C3A—C420 | −0.1 (5) | C427—O424—C424—C425 | 1 (3) |
N2—C3—C3A—C4 | −168.5 (4) | C427—O424—C424—C423 | −172.4 (13) |
C31—C3—C3A—C4 | 13.7 (5) | C422—C423—C424—C425 | 3 (2) |
C3—C3A—C4—C41 | 72.1 (7) | C422—C423—C424—O424 | 177.9 (10) |
C9A—C3A—C4—C41 | −96.2 (6) | O424—C424—C425—C426 | −177.4 (16) |
C420—C3A—C4—C41 | 166 (5) | C423—C424—C425—C426 | −4 (2) |
C3—C3A—C4—C4A | −164.7 (2) | C422—C421—C426—C425 | −0.4 (13) |
C9A—C3A—C4—C4A | 26.9 (5) | C420—C421—C426—C425 | −179.1 (9) |
C420—C3A—C4—C4A | −71 (5) | C424—C425—C426—C421 | 2.7 (16) |
C8A—C4A—C4—C41 | 98.2 (6) | C8A—C4A—C5—O51 | 178.54 (16) |
C5—C4A—C4—C41 | −76.4 (6) | C420—C4A—C5—O51 | 4.4 (4) |
C420—C4A—C4—C41 | −164 (6) | C4—C4A—C5—O51 | −6.6 (3) |
C8A—C4A—C4—C3A | −25.6 (5) | C8A—C4A—C5—C6 | 0.1 (2) |
C5—C4A—C4—C3A | 159.8 (3) | C420—C4A—C5—C6 | −174.0 (3) |
C420—C4A—C4—C3A | 72 (5) | C4—C4A—C5—C6 | 174.9 (3) |
C3A—C4—C41—C42 | −112.6 (6) | O51—C5—C6—C7 | 151.62 (15) |
C4A—C4—C41—C42 | 127.9 (6) | C4A—C5—C6—C7 | −29.9 (2) |
C3A—C4—C41—C46 | 66.2 (8) | C5—C6—C7—C71 | 172.12 (14) |
C4A—C4—C41—C46 | −53.3 (8) | C5—C6—C7—C72 | −67.10 (19) |
C46—C41—C42—C43 | 0.2 (9) | C5—C6—C7—C8 | 53.54 (19) |
C4—C41—C42—C43 | 179.0 (8) | C71—C7—C8—C8A | −170.63 (15) |
C41—C42—C43—C44 | −0.8 (13) | C6—C7—C8—C8A | −50.64 (19) |
C42—C43—C44—O44 | −178.6 (6) | C72—C7—C8—C8A | 69.4 (2) |
C42—C43—C44—C45 | 0.5 (13) | C5—C4A—C8A—N9 | −176.46 (15) |
O44—C44—C45—C46 | 179.7 (3) | C420—C4A—C8A—N9 | −2.8 (4) |
C43—C44—C45—C46 | 0.4 (8) | C4—C4A—C8A—N9 | 9.0 (4) |
C44—C45—C46—C41 | −1.2 (5) | C5—C4A—C8A—C8 | 2.1 (3) |
C42—C41—C46—C45 | 0.9 (6) | C420—C4A—C8A—C8 | 175.8 (4) |
C4—C41—C46—C45 | −177.9 (5) | C4—C4A—C8A—C8 | −172.4 (3) |
C45—C44—O44—C47 | 178.6 (4) | C7—C8—C8A—N9 | −156.14 (15) |
C43—C44—O44—C47 | −2.2 (8) | C7—C8—C8A—C4A | 25.2 (2) |
C3—C3A—C420—C4A | −168.4 (3) | N2—N1—C9A—N9 | −176.35 (15) |
C9A—C3A—C420—C4A | 7.5 (7) | N2—N1—C9A—C3A | 0.42 (19) |
C4—C3A—C420—C4A | 96 (5) | C3—C3A—C9A—N1 | −1.1 (2) |
C3—C3A—C420—C421 | 66.8 (9) | C420—C3A—C9A—N1 | −178.0 (4) |
C9A—C3A—C420—C421 | −117.3 (7) | C4—C3A—C9A—N1 | 170.3 (3) |
C4—C3A—C420—C421 | −29 (4) | C3—C3A—C9A—N9 | 175.73 (15) |
C8A—C4A—C420—C3A | −5.7 (7) | C420—C3A—C9A—N9 | −1.2 (4) |
C5—C4A—C420—C3A | 168.2 (3) | C4—C3A—C9A—N9 | −12.9 (4) |
C4—C4A—C420—C3A | −95 (5) | C4A—C8A—N9—C9A | 9.9 (2) |
C8A—C4A—C420—C421 | 116.0 (8) | C8—C8A—N9—C9A | −168.79 (15) |
C5—C4A—C420—C421 | −70.2 (10) | N1—C9A—N9—C8A | 168.51 (16) |
C4—C4A—C420—C421 | 27 (4) | C3A—C9A—N9—C8A | −8.0 (2) |
C3A—C420—C421—C426 | 82.9 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O51i | 0.88 | 1.96 | 2.824 (2) | 167 |
N9—H9···N1ii | 0.88 | 2.07 | 2.880 (2) | 153 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+2, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C20H23N3O2 |
Mr | 337.41 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 150 |
a, b, c (Å) | 8.5820 (3), 14.7031 (5), 14.5369 (8) |
β (°) | 106.0610 (15) |
V (Å3) | 1762.70 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.38 × 0.24 × 0.18 |
Data collection | |
Diffractometer | KappaCCD diffractometer |
Absorption correction | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.969, 0.985 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11320, 3956, 2662 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.141, 1.03 |
No. of reflections | 3956 |
No. of parameters | 289 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.30 |
Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976) and PLATON (Spek, 2000), SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).
N1—C9A | 1.335 (2) | C8A—N9 | 1.357 (2) |
N1—N2 | 1.358 (2) | C9A—N9 | 1.386 (2) |
N2—C3 | 1.345 (2) | ||
C9A—N1—N2 | 102.49 (14) | C8A—N9—C9A | 118.34 (15) |
C3—N2—N1 | 113.55 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O51i | 0.88 | 1.96 | 2.824 (2) | 167 |
N9—H9···N1ii | 0.88 | 2.07 | 2.880 (2) | 153 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+2, −y+1, −z+2. |
Pyrazolo[3,4-b]quinolines are of interest as possible antiviral agents (Crenshaw et al., 1976, 1978; Smirnoff and Crenshaw, 1977). Some of their derivatives exhibit parasiticidic properties (Bristol-Meyers Co, 1973), and have been studied as potential antimalarial agents (Stein et al., 1970). Some pyrazolo[3,4-b]quinolines have shown bactericidal activity (Farghaly et al., 1989), have also been used as vasodilators (Bell & Ackerman, 1990) and evaluated for enzymatic inhibitory activity (Gatta et al., 1991).
In previous reports (Quiroga, Hormaza et al., 1998; Quiroga, Insuasty et al., 1998), we have reported an efficient and versatile synthesis of novel 4,7,8,9-tetrahydro-pyrimido- and 4,7,8,9-tetrahydropyrazolo[3,4-b]quinolin-5-ones from suitable pyrimidine and pyrazole amines to which dimedone and substituted benzaldehyde afford the ring annelation to quinoline.
Selected bond lengths and angles for the title compound, (I), are given in Table 1 and a view of the molecule is shown in Fig. 1.
The hydrogen-bonding pattern comprises anti-parallel C(8) (N2—H2···O51i) chains linked together by R22(8) (N9–H9···N1ii) base-paired motifs (Bernstein et al., 1995). This combination forms a corrugated sheet which contains R66(34) rings. This is shown in Fig. 2. The details of the hydrogen bonds are given in Table 2.
The 4-methoxyphenyl group was disordered on two sites, with occupancies of 0.65 and 0.35. The group is flipped through nearly 180° about an axis which runs close to the line passing between C4 and C420 and between the C47 and C427 methoxy atoms, the second of each atom pair being in the minor component.
Examination of the structure with PLATON (Spek, 2000) showed that there were no solvent-accessible voids in the crystal lattice.