The title compound, C
20H
23N
3O
2, has a supramolecular structure of hydrogen bonding comprising N—H
O bonds which form a series of anti-parallel
C(8), chains linked together by N—H
N
R22(8) base-paired motifs which together form corrugated sheets containing
R66(34) rings. This is one of a series of four substituted 3,7,7-trimethyl-4,7,8,9-tetrahydro-2
H-pyrazolo[3,4-
b]quinolin-5(6
H)-one compounds which all have identical supramolecular structures.
Supporting information
CCDC reference: 159751
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.002 Å
- Disorder in main residue
- R factor = 0.053
- wR factor = 0.141
- Data-to-parameter ratio = 13.7
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level B:
PLAT_301 Alert B Main residue disorder ........................ 26.00 Perc.
| Author response: ...see _publ_section_exptl_refinement for details
|
General Notes
FORMU_01 There is a discrepancy between the atom counts in the
_chemical_formula_sum and the formula from the _atom_site* data.
Atom count from _chemical_formula_sum:C20 H23 N3 O2
Atom count from the _atom_site data: C20 H23.06 N3 O2
CELLZ_01
From the CIF: _cell_formula_units_Z 4
From the CIF: _chemical_formula_sum C20 H23 N3 O2
TEST: Compare cell contents of formula and atom_site data
atom Z*formula cif sites diff
C 80.00 80.00 0.00
H 92.00 92.24 -0.24
N 12.00 12.00 0.00
O 8.00 8.00 0.00
Difference between formula and atom_site contents detected.
ALERT: check formula stoichiometry or atom site occupancies.
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
0 Alert Level C = Please check
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).
3,7,7-Trimethyl-4-(4-methoxyphenyl)-4,7,8,9-tetrahydro-2
H-pyrazolo[3,4-
b]- quinolin-5(6
H)-one (4).
top
Crystal data top
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 | |
Data collection top
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 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)] = 0.053 | 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 |
Crystal data top
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)° | |
Data collection top
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 | |
Refinement top
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 | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | 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* | |
Atomic displacement parameters (Å2) top | 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) |
Geometric parameters (Å, º) top
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) | | |
Hydrogen-bond geometry (Å, º) top
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 |
Selected geometric parameters (Å, º) topN1—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) | | |
Hydrogen-bond geometry (Å, º) top
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.