Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101014913/gg1082sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101014913/gg1082Isup2.hkl |
CCDC reference: 175115
For related literature, see: Bell & Ackerman (1990); Bernstein et al. (1995); Bristol-Meyers & Co (1973); Cannon et al. (2001a, 2001b, 2001c, 2001d); Crenshaw et al. (1976, 1978); Farghaly et al. (1989); Gatta et al. (1991); Gein Stein, Biel & Singh (1970); Smirnoff & Crenshaw (1977); Spek (2000).
A solution of 4-(4-chlorophenyl)-3,7,7-trimethyl-4,7,8,9-tetrahydro-2H- pyrazolo[3,4-b]quinolin-5(6H)-one (2.0 mmol) and 3-dimethylamino-4-nitropropiophenone (2.0 mmol) in absolute ethanol (15 ml) was refluxed for 50 min, and the resulting precipitate was filtered, washed with ethanol, dried and recrystallized from ethanol. Compound (I) was obtained as orange crystals (m.p. 466 K, yield 82%), from which suitable ones were selected for X-ray diffraction. Analysis calculated for C28H28ClN4O4: C 64.80, H 5.24, N 10.80%; found: C,64.87, H 5.16, N 10.73.
H atoms on N9 and O1A were located on a difference map; all others were placed in calculated positions. All H atoms were treated as riding, with C—H = 0.95–1.00 Å, N—H = 0.92 Å and O—H 1.05 Å. Those attached to atom C2A were calculated as six half H atoms.
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 PRPKAPPA (Ferguson, 1999).
C28H27ClN4O4·C2H6O | Dx = 1.34 Mg m−3 |
Mr = 565.05 | Melting point: 466 K |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
a = 23.6298 (6) Å | Cell parameters from 5677 reflections |
b = 9.6215 (3) Å | θ = 3.1–27.5° |
c = 14.2657 (4) Å | µ = 0.18 mm−1 |
β = 120.2930 (16)° | T = 150 K |
V = 2800.51 (14) Å3 | Block, orange |
Z = 4 | 0.30 × 0.14 × 0.14 mm |
F(000) = 1192 |
Nonius KappaCCD area-detector diffractometer | 5677 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 4821 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.04 |
ϕ and ω scans with κ offsets | θmax = 27.5°, θmin = 3.1° |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | h = −27→30 |
Tmin = 0.947, Tmax = 0.975 | k = −11→12 |
11553 measured reflections | l = −18→18 |
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)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.098 | w = 1/[σ2(Fo2) + (0.0495P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.001 |
5677 reflections | Δρmax = 0.24 e Å−3 |
365 parameters | Δρmin = −0.27 e Å−3 |
2 restraints | Absolute structure: Flack (1983), 3212 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.03 (5) |
C28H27ClN4O4·C2H6O | V = 2800.51 (14) Å3 |
Mr = 565.05 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 23.6298 (6) Å | µ = 0.18 mm−1 |
b = 9.6215 (3) Å | T = 150 K |
c = 14.2657 (4) Å | 0.30 × 0.14 × 0.14 mm |
β = 120.2930 (16)° |
Nonius KappaCCD area-detector diffractometer | 5677 independent reflections |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 4821 reflections with I > 2σ(I) |
Tmin = 0.947, Tmax = 0.975 | Rint = 0.04 |
11553 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.098 | Δρmax = 0.24 e Å−3 |
S = 1.00 | Δρmin = −0.27 e Å−3 |
5677 reflections | Absolute structure: Flack (1983), 3212 Friedel pairs |
365 parameters | Absolute structure parameter: 0.03 (5) |
2 restraints |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
N1 | 0.89438 (9) | 0.20346 (19) | 0.84225 (14) | 0.0202 (4) | |
C11 | 0.89995 (12) | 0.1996 (2) | 0.94874 (18) | 0.0216 (5) | |
C12 | 0.85271 (12) | 0.3010 (2) | 0.95531 (18) | 0.0228 (5) | |
C13 | 0.85921 (11) | 0.3050 (2) | 1.06560 (17) | 0.0206 (5) | |
O133 | 0.89835 (8) | 0.23116 (17) | 1.13971 (13) | 0.0274 (4) | |
C131 | 0.81675 (12) | 0.4049 (2) | 1.08372 (18) | 0.0217 (5) | |
C132 | 0.82133 (13) | 0.4052 (2) | 1.18466 (19) | 0.0263 (6) | |
C133 | 0.78476 (13) | 0.4981 (3) | 1.20700 (18) | 0.0281 (6) | |
C134 | 0.74471 (12) | 0.5915 (2) | 1.12706 (19) | 0.0240 (5) | |
N13 | 0.70767 (10) | 0.6933 (2) | 1.15138 (17) | 0.0305 (5) | |
O11 | 0.68257 (9) | 0.79102 (19) | 1.08941 (16) | 0.0369 (4) | |
O12 | 0.70387 (9) | 0.6748 (2) | 1.23412 (14) | 0.0409 (5) | |
C135 | 0.73805 (13) | 0.5915 (3) | 1.0259 (2) | 0.0274 (6) | |
C136 | 0.77391 (12) | 0.4964 (3) | 1.00400 (18) | 0.0257 (5) | |
N2 | 0.85070 (9) | 0.1171 (2) | 0.76075 (15) | 0.0206 (4) | |
C3 | 0.85750 (11) | 0.1469 (2) | 0.67517 (17) | 0.0199 (5) | |
C31 | 0.81786 (12) | 0.0718 (3) | 0.57003 (18) | 0.0254 (5) | |
C3a | 0.90445 (11) | 0.2518 (2) | 0.69987 (16) | 0.0180 (5) | |
C4 | 0.93151 (11) | 0.3198 (2) | 0.63608 (17) | 0.0178 (5) | |
C41 | 0.96523 (11) | 0.2159 (2) | 0.59909 (17) | 0.0165 (4) | |
C42 | 1.01761 (12) | 0.1363 (2) | 0.67326 (18) | 0.0209 (5) | |
C43 | 1.04852 (12) | 0.0425 (2) | 0.63972 (18) | 0.0217 (5) | |
C44 | 1.02560 (11) | 0.0292 (2) | 0.52926 (18) | 0.0198 (5) | |
Cl4 | 1.06286 (3) | −0.09124 (6) | 0.48634 (4) | 0.02874 (15) | |
C45 | 0.97350 (12) | 0.1061 (2) | 0.45389 (17) | 0.0214 (5) | |
C46 | 0.94360 (12) | 0.1994 (2) | 0.48954 (18) | 0.0207 (5) | |
C4a | 0.97781 (11) | 0.4366 (2) | 0.70570 (17) | 0.0178 (5) | |
C5 | 1.00230 (11) | 0.5276 (2) | 0.65364 (17) | 0.0181 (5) | |
O5 | 0.98308 (8) | 0.51332 (16) | 0.55532 (11) | 0.0239 (4) | |
C6 | 1.04798 (12) | 0.6457 (2) | 0.71622 (18) | 0.0230 (5) | |
C7 | 1.08601 (12) | 0.6270 (2) | 0.83932 (18) | 0.0230 (5) | |
C71 | 1.11769 (14) | 0.7664 (3) | 0.8925 (2) | 0.0301 (6) | |
C72 | 1.13858 (13) | 0.5163 (3) | 0.8729 (2) | 0.0332 (6) | |
C8 | 1.03685 (12) | 0.5848 (2) | 0.87447 (18) | 0.0232 (5) | |
C8a | 0.99454 (11) | 0.4638 (2) | 0.81104 (16) | 0.0184 (5) | |
N9 | 0.97083 (10) | 0.38750 (18) | 0.86433 (14) | 0.0196 (4) | |
C9a | 0.92577 (11) | 0.2843 (2) | 0.80607 (17) | 0.0182 (5) | |
O1A | 0.79130 (9) | −0.12932 (19) | 0.79244 (14) | 0.0376 (5) | |
C1A | 0.72545 (15) | −0.1122 (3) | 0.7110 (2) | 0.0455 (8) | |
C2A | 0.68370 (15) | −0.2230 (3) | 0.7226 (3) | 0.0437 (7) | |
H11A | 0.9454 | 0.2233 | 1.0051 | 0.026* | |
H11B | 0.8906 | 0.1043 | 0.9634 | 0.026* | |
H12A | 0.8607 | 0.3953 | 0.9367 | 0.027* | |
H12B | 0.8073 | 0.2744 | 0.9009 | 0.027* | |
H132 | 0.8497 | 0.3414 | 1.2389 | 0.032* | |
H133 | 0.7871 | 0.4975 | 1.2755 | 0.034* | |
H135 | 0.7095 | 0.6554 | 0.9719 | 0.033* | |
H136 | 0.7692 | 0.4936 | 0.9338 | 0.031* | |
H31A | 0.7891 | 0.0043 | 0.5771 | 0.038* | |
H31B | 0.8472 | 0.0230 | 0.5513 | 0.038* | |
H31C | 0.7912 | 0.1387 | 0.5127 | 0.038* | |
H4 | 0.8942 | 0.3627 | 0.5699 | 0.021* | |
H42 | 1.0327 | 0.1461 | 0.7485 | 0.025* | |
H43 | 1.0846 | −0.0114 | 0.6912 | 0.026* | |
H45 | 0.9581 | 0.0956 | 0.3786 | 0.026* | |
H46 | 0.9076 | 0.2531 | 0.4378 | 0.025* | |
H6A | 1.0220 | 0.7324 | 0.6989 | 0.028* | |
H6B | 1.0798 | 0.6575 | 0.6909 | 0.028* | |
H71A | 1.1422 | 0.7555 | 0.9716 | 0.045* | |
H71B | 1.0835 | 0.8367 | 0.8722 | 0.045* | |
H71C | 1.1476 | 0.7957 | 0.8675 | 0.045* | |
H72A | 1.1183 | 0.4286 | 0.8365 | 0.050* | |
H72B | 1.1609 | 0.5032 | 0.9517 | 0.050* | |
H72C | 1.1705 | 0.5457 | 0.8521 | 0.050* | |
H8A | 1.0612 | 0.5603 | 0.9525 | 0.028* | |
H8B | 1.0084 | 0.6653 | 0.8653 | 0.028* | |
H9 | 0.9744 | 0.4044 | 0.9307 | 0.024* | |
H1A | 0.8102 | −0.0369 | 0.7797 | 0.045* | |
H1A1 | 0.7214 | −0.1195 | 0.6387 | 0.055* | |
H1A2 | 0.7100 | −0.0188 | 0.7172 | 0.055* | |
H2A1 | 0.6376 | −0.2088 | 0.6672 | 0.066* | 0.50 |
H2A2 | 0.6886 | −0.2167 | 0.7949 | 0.066* | 0.50 |
H2A3 | 0.6979 | −0.3150 | 0.7132 | 0.066* | 0.50 |
H2A4 | 0.7118 | −0.2849 | 0.7830 | 0.066* | 0.50 |
H2A5 | 0.6608 | −0.2770 | 0.6553 | 0.066* | 0.50 |
H2A6 | 0.6515 | −0.1787 | 0.7370 | 0.066* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0246 (11) | 0.0219 (10) | 0.0182 (9) | −0.0045 (8) | 0.0139 (9) | −0.0033 (8) |
C11 | 0.0257 (13) | 0.0246 (12) | 0.0191 (11) | −0.0013 (10) | 0.0146 (11) | 0.0000 (9) |
C12 | 0.0240 (13) | 0.0291 (13) | 0.0195 (11) | 0.0006 (10) | 0.0140 (11) | 0.0001 (9) |
C13 | 0.0197 (13) | 0.0241 (12) | 0.0211 (12) | −0.0056 (10) | 0.0126 (11) | −0.0036 (9) |
O133 | 0.0296 (10) | 0.0308 (9) | 0.0238 (8) | 0.0020 (8) | 0.0149 (8) | 0.0024 (7) |
C131 | 0.0233 (13) | 0.0247 (12) | 0.0218 (12) | −0.0077 (10) | 0.0147 (11) | −0.0053 (9) |
C132 | 0.0290 (15) | 0.0274 (13) | 0.0241 (12) | −0.0022 (11) | 0.0147 (12) | −0.0017 (10) |
C133 | 0.0319 (15) | 0.0352 (14) | 0.0218 (12) | −0.0021 (12) | 0.0170 (12) | −0.0042 (10) |
C134 | 0.0213 (13) | 0.0260 (13) | 0.0286 (12) | −0.0049 (10) | 0.0154 (11) | −0.0076 (10) |
N13 | 0.0225 (12) | 0.0341 (13) | 0.0372 (12) | −0.0053 (10) | 0.0168 (10) | −0.0134 (10) |
O11 | 0.0340 (11) | 0.0293 (10) | 0.0523 (12) | −0.0025 (9) | 0.0254 (10) | −0.0058 (9) |
O12 | 0.0305 (11) | 0.0662 (13) | 0.0313 (10) | 0.0037 (10) | 0.0194 (9) | −0.0107 (9) |
C135 | 0.0263 (14) | 0.0317 (14) | 0.0288 (13) | −0.0001 (11) | 0.0173 (12) | 0.0004 (11) |
C136 | 0.0272 (14) | 0.0339 (14) | 0.0207 (12) | −0.0006 (12) | 0.0155 (11) | −0.0013 (10) |
N2 | 0.0177 (10) | 0.0234 (10) | 0.0223 (10) | −0.0010 (8) | 0.0111 (9) | −0.0051 (8) |
C3 | 0.0195 (13) | 0.0199 (11) | 0.0220 (11) | 0.0018 (9) | 0.0117 (10) | −0.0014 (9) |
C31 | 0.0226 (13) | 0.0300 (13) | 0.0217 (11) | −0.0042 (11) | 0.0098 (11) | −0.0060 (10) |
C3a | 0.0169 (12) | 0.0194 (11) | 0.0204 (11) | 0.0016 (9) | 0.0113 (10) | −0.0003 (9) |
C4 | 0.0196 (12) | 0.0183 (11) | 0.0170 (10) | 0.0011 (9) | 0.0104 (10) | −0.0013 (9) |
C41 | 0.0175 (12) | 0.0161 (10) | 0.0191 (11) | −0.0040 (9) | 0.0117 (10) | −0.0013 (8) |
C42 | 0.0235 (13) | 0.0242 (12) | 0.0167 (11) | −0.0010 (10) | 0.0113 (10) | −0.0017 (9) |
C43 | 0.0188 (12) | 0.0234 (12) | 0.0225 (11) | 0.0032 (10) | 0.0102 (10) | 0.0008 (9) |
C44 | 0.0203 (13) | 0.0195 (11) | 0.0247 (12) | −0.0044 (10) | 0.0152 (11) | −0.0053 (9) |
Cl4 | 0.0286 (3) | 0.0284 (3) | 0.0332 (3) | 0.0027 (3) | 0.0185 (3) | −0.0073 (3) |
C45 | 0.0261 (13) | 0.0226 (12) | 0.0162 (11) | −0.0037 (10) | 0.0113 (11) | −0.0040 (9) |
C46 | 0.0207 (13) | 0.0226 (12) | 0.0166 (10) | −0.0012 (10) | 0.0079 (10) | −0.0001 (9) |
C4a | 0.0194 (12) | 0.0184 (11) | 0.0182 (10) | 0.0019 (9) | 0.0112 (10) | −0.0008 (8) |
C5 | 0.0223 (12) | 0.0173 (11) | 0.0172 (11) | 0.0044 (9) | 0.0119 (10) | 0.0019 (8) |
O5 | 0.0329 (10) | 0.0232 (8) | 0.0191 (8) | 0.0009 (7) | 0.0158 (8) | 0.0015 (7) |
C6 | 0.0248 (13) | 0.0233 (12) | 0.0228 (12) | −0.0051 (10) | 0.0134 (11) | 0.0003 (10) |
C7 | 0.0230 (13) | 0.0248 (12) | 0.0214 (11) | −0.0054 (10) | 0.0114 (11) | −0.0023 (9) |
C71 | 0.0360 (15) | 0.0330 (14) | 0.0239 (12) | −0.0110 (12) | 0.0171 (12) | −0.0045 (10) |
C72 | 0.0245 (14) | 0.0376 (15) | 0.0310 (13) | 0.0026 (12) | 0.0092 (12) | 0.0040 (12) |
C8 | 0.0295 (14) | 0.0225 (12) | 0.0199 (11) | −0.0047 (10) | 0.0140 (11) | −0.0029 (9) |
C8a | 0.0200 (12) | 0.0185 (11) | 0.0186 (11) | 0.0033 (10) | 0.0111 (10) | 0.0030 (9) |
N9 | 0.0275 (11) | 0.0215 (10) | 0.0144 (9) | −0.0035 (8) | 0.0139 (9) | −0.0025 (7) |
C9a | 0.0187 (12) | 0.0200 (11) | 0.0181 (10) | 0.0005 (9) | 0.0108 (10) | −0.0011 (9) |
O1A | 0.0351 (12) | 0.0364 (10) | 0.0334 (10) | −0.0086 (9) | 0.0113 (9) | 0.0020 (8) |
C1A | 0.0377 (18) | 0.0539 (19) | 0.0383 (16) | −0.0098 (14) | 0.0143 (14) | 0.0097 (13) |
C2A | 0.0441 (19) | 0.0423 (17) | 0.0548 (17) | −0.0079 (14) | 0.0324 (16) | −0.0034 (14) |
N1—N2 | 1.377 (3) | C43—H43 | 0.9500 |
N1—C9a | 1.345 (3) | C44—C45 | 1.372 (3) |
N1—C11 | 1.458 (3) | C44—Cl4 | 1.743 (2) |
N2—C3 | 1.340 (3) | C45—C46 | 1.388 (3) |
C3—C3a | 1.407 (3) | C45—H45 | 0.9500 |
C3—C31 | 1.494 (3) | C46—H46 | 0.9500 |
C3a—C9a | 1.370 (3) | C4a—C8a | 1.372 (3) |
N13—O11 | 1.220 (3) | C4a—C5 | 1.445 (3) |
N13—O12 | 1.241 (3) | C5—O5 | 1.245 (2) |
N13—C134 | 1.467 (3) | C5—C6 | 1.510 (3) |
C11—C12 | 1.520 (3) | C6—C7 | 1.527 (3) |
C11—H11A | 0.9900 | C6—H6A | 0.9900 |
C11—H11B | 0.9900 | C6—H6B | 0.9900 |
C12—C13 | 1.502 (3) | C7—C72 | 1.519 (4) |
C12—H12A | 0.9900 | C7—C8 | 1.534 (3) |
C12—H12B | 0.9900 | C7—C71 | 1.537 (3) |
C13—O133 | 1.221 (3) | C71—H71A | 0.9800 |
C13—C131 | 1.503 (3) | C71—H71B | 0.9800 |
C131—C132 | 1.388 (3) | C71—H71C | 0.9800 |
C131—C136 | 1.389 (4) | C72—H72A | 0.9800 |
C132—C133 | 1.387 (3) | C72—H72B | 0.9800 |
C132—H132 | 0.9500 | C72—H72C | 0.9800 |
C133—C134 | 1.384 (3) | C8—C8a | 1.504 (3) |
C133—H133 | 0.9500 | C8—H8A | 0.9900 |
C134—C135 | 1.371 (3) | C8—H8B | 0.9900 |
C135—C136 | 1.386 (3) | C8a—N9 | 1.364 (3) |
C135—H135 | 0.9500 | N9—C9a | 1.385 (3) |
C136—H136 | 0.9500 | N9—H9 | 0.9216 |
C31—H31A | 0.9800 | O1A—C1A | 1.405 (4) |
C31—H31B | 0.9800 | O1A—H1A | 1.0514 |
C31—H31C | 0.9800 | C1A—C2A | 1.518 (4) |
C3a—C4 | 1.500 (3) | C1A—H1A1 | 0.9900 |
C4—C41 | 1.528 (3) | C1A—H1A2 | 0.9900 |
C4—C4a | 1.534 (3) | C2A—H2A1 | 0.9800 |
C4—H4 | 1.0000 | C2A—H2A2 | 0.9800 |
C41—C42 | 1.384 (3) | C2A—H2A3 | 0.9800 |
C41—C46 | 1.387 (3) | C2A—H2A4 | 0.9800 |
C42—C43 | 1.389 (3) | C2A—H2A5 | 0.9800 |
C42—H42 | 0.9500 | C2A—H2A6 | 0.9800 |
C43—C44 | 1.390 (3) | ||
C9a—N1—N2 | 110.40 (17) | C45—C46—H46 | 119.3 |
C9a—N1—C11 | 129.60 (19) | C8a—C4a—C5 | 118.6 (2) |
N2—N1—C11 | 119.99 (17) | C8a—C4a—C4 | 124.49 (19) |
N1—C11—C12 | 111.40 (18) | C5—C4a—C4 | 116.83 (18) |
N1—C11—H11A | 109.3 | O5—C5—C4a | 119.9 (2) |
C12—C11—H11A | 109.3 | O5—C5—C6 | 119.67 (19) |
N1—C11—H11B | 109.3 | C4a—C5—C6 | 120.29 (18) |
C12—C11—H11B | 109.3 | C5—C6—C7 | 114.93 (18) |
H11A—C11—H11B | 108.0 | C5—C6—H6A | 108.5 |
C13—C12—C11 | 112.99 (18) | C7—C6—H6A | 108.5 |
C13—C12—H12A | 109.0 | C5—C6—H6B | 108.5 |
C11—C12—H12A | 109.0 | C7—C6—H6B | 108.5 |
C13—C12—H12B | 109.0 | H6A—C6—H6B | 107.5 |
C11—C12—H12B | 109.0 | C72—C7—C6 | 111.0 (2) |
H12A—C12—H12B | 107.8 | C72—C7—C8 | 110.2 (2) |
O133—C13—C12 | 121.6 (2) | C6—C7—C8 | 107.69 (19) |
O133—C13—C131 | 120.19 (19) | C72—C7—C71 | 109.8 (2) |
C12—C13—C131 | 118.16 (19) | C6—C7—C71 | 108.80 (19) |
C132—C131—C136 | 119.4 (2) | C8—C7—C71 | 109.29 (19) |
C132—C131—C13 | 118.0 (2) | C7—C71—H71A | 109.5 |
C136—C131—C13 | 122.6 (2) | C7—C71—H71B | 109.5 |
C133—C132—C131 | 120.5 (2) | H71A—C71—H71B | 109.5 |
C133—C132—H132 | 119.7 | C7—C71—H71C | 109.5 |
C131—C132—H132 | 119.7 | H71A—C71—H71C | 109.5 |
C134—C133—C132 | 118.4 (2) | H71B—C71—H71C | 109.5 |
C134—C133—H133 | 120.8 | C7—C72—H72A | 109.5 |
C132—C133—H133 | 120.8 | C7—C72—H72B | 109.5 |
C135—C134—C133 | 122.4 (2) | H72A—C72—H72B | 109.5 |
C135—C134—N13 | 118.9 (2) | C7—C72—H72C | 109.5 |
C133—C134—N13 | 118.7 (2) | H72A—C72—H72C | 109.5 |
O11—N13—O12 | 123.9 (2) | H72B—C72—H72C | 109.5 |
O11—N13—C134 | 118.2 (2) | C8a—C8—C7 | 113.04 (18) |
O12—N13—C134 | 117.9 (2) | C8a—C8—H8A | 109.0 |
C134—C135—C136 | 118.6 (2) | C7—C8—H8A | 109.0 |
C134—C135—H135 | 120.7 | C8a—C8—H8B | 109.0 |
C136—C135—H135 | 120.7 | C7—C8—H8B | 109.0 |
C135—C136—C131 | 120.7 (2) | H8A—C8—H8B | 107.8 |
C135—C136—H136 | 119.7 | N9—C8a—C4a | 122.4 (2) |
C131—C136—H136 | 119.7 | N9—C8a—C8 | 114.62 (18) |
C3—N2—N1 | 104.89 (18) | C4a—C8a—C8 | 122.90 (19) |
N2—C3—C3a | 111.53 (18) | C8a—N9—C9a | 117.32 (17) |
N2—C3—C31 | 120.6 (2) | C8a—N9—H9 | 128.8 |
C3a—C3—C31 | 127.9 (2) | C9a—N9—H9 | 112.8 |
C3—C31—H31A | 109.5 | N1—C9a—C3a | 109.04 (19) |
C3—C31—H31B | 109.5 | N1—C9a—N9 | 126.19 (18) |
H31A—C31—H31B | 109.5 | C3a—C9a—N9 | 124.74 (19) |
C3—C31—H31C | 109.5 | C1A—O1A—H1A | 98.5 |
H31A—C31—H31C | 109.5 | O1A—C1A—C2A | 109.7 (2) |
H31B—C31—H31C | 109.5 | O1A—C1A—H1A1 | 109.7 |
C9a—C3a—C3 | 104.13 (18) | C2A—C1A—H1A1 | 109.7 |
C9a—C3a—C4 | 122.7 (2) | O1A—C1A—H1A2 | 109.7 |
C3—C3a—C4 | 133.16 (19) | C2A—C1A—H1A2 | 109.7 |
C3a—C4—C41 | 112.37 (17) | H1A1—C1A—H1A2 | 108.2 |
C3a—C4—C4a | 108.03 (17) | C1A—C2A—H2A1 | 109.5 |
C41—C4—C4a | 112.17 (19) | C1A—C2A—H2A2 | 109.5 |
C3a—C4—H4 | 108.0 | H2A1—C2A—H2A2 | 109.5 |
C41—C4—H4 | 108.0 | C1A—C2A—H2A3 | 109.5 |
C4a—C4—H4 | 108.0 | H2A1—C2A—H2A3 | 109.5 |
C42—C41—C46 | 118.5 (2) | H2A2—C2A—H2A3 | 109.5 |
C42—C41—C4 | 121.23 (19) | C1A—C2A—H2A4 | 109.5 |
C46—C41—C4 | 120.3 (2) | H2A1—C2A—H2A4 | 141.1 |
C41—C42—C43 | 121.3 (2) | H2A2—C2A—H2A4 | 56.3 |
C41—C42—H42 | 119.4 | H2A3—C2A—H2A4 | 56.3 |
C43—C42—H42 | 119.4 | C1A—C2A—H2A5 | 109.5 |
C42—C43—C44 | 118.6 (2) | H2A1—C2A—H2A5 | 56.3 |
C42—C43—H43 | 120.7 | H2A2—C2A—H2A5 | 141.1 |
C44—C43—H43 | 120.7 | H2A3—C2A—H2A5 | 56.3 |
C45—C44—C43 | 121.4 (2) | H2A4—C2A—H2A5 | 109.5 |
C45—C44—Cl4 | 119.71 (17) | C1A—C2A—H2A6 | 109.5 |
C43—C44—Cl4 | 118.84 (17) | H2A1—C2A—H2A6 | 56.3 |
C44—C45—C46 | 118.9 (2) | H2A2—C2A—H2A6 | 56.3 |
C44—C45—H45 | 120.6 | H2A3—C2A—H2A6 | 141.1 |
C46—C45—H45 | 120.6 | H2A4—C2A—H2A6 | 109.5 |
C41—C46—C45 | 121.4 (2) | H2A5—C2A—H2A6 | 109.5 |
C41—C46—H46 | 119.3 |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···N2 | 1.05 | 1.86 | 2.904 (3) | 175 |
N9—H9···O5i | 0.92 | 1.86 | 2.761 (3) | 165 |
C12—H12B···O12ii | 0.99 | 2.45 | 3.344 (4) | 150 |
Symmetry codes: (i) x, −y+1, z+1/2; (ii) x, −y+1, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C28H27ClN4O4·C2H6O |
Mr | 565.05 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 150 |
a, b, c (Å) | 23.6298 (6), 9.6215 (3), 14.2657 (4) |
β (°) | 120.2930 (16) |
V (Å3) | 2800.51 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.18 |
Crystal size (mm) | 0.30 × 0.14 × 0.14 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.947, 0.975 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11553, 5677, 4821 |
Rint | 0.04 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.098, 1.00 |
No. of reflections | 5677 |
No. of parameters | 365 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.27 |
Absolute structure | Flack (1983), 3212 Friedel pairs |
Absolute structure parameter | 0.03 (5) |
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 PRPKAPPA (Ferguson, 1999).
N1—N2 | 1.377 (3) | N13—O12 | 1.241 (3) |
N1—C9a | 1.345 (3) | N13—C134 | 1.467 (3) |
N1—C11 | 1.458 (3) | C13—O133 | 1.221 (3) |
N2—C3 | 1.340 (3) | C4a—C5 | 1.445 (3) |
C3—C3a | 1.407 (3) | C5—O5 | 1.245 (2) |
C3a—C9a | 1.370 (3) | C5—C6 | 1.510 (3) |
N13—O11 | 1.220 (3) | ||
C9a—N1—N2 | 110.40 (17) | N2—C3—C3a | 111.53 (18) |
C9a—N1—C11 | 129.60 (19) | C9a—C3a—C3 | 104.13 (18) |
N2—N1—C11 | 119.99 (17) | N1—C9a—C3a | 109.04 (19) |
C3—N2—N1 | 104.89 (18) | N1—C9a—N9 | 126.19 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···N2 | 1.05 | 1.86 | 2.904 (3) | 175 |
N9—H9···O5i | 0.92 | 1.86 | 2.761 (3) | 165 |
C12—H12B···O12ii | 0.99 | 2.45 | 3.344 (4) | 150 |
Symmetry codes: (i) x, −y+1, z+1/2; (ii) x, −y+1, z−1/2. |
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Pyrazolo[3,4-b]quinolines are of interest as possible antiviral agents (Crenshaw et al., 1976, 1978; Smirnoff & Crenshaw, 1977). Some of their derivatives exhibit parasiticidic properties (Bristol-Meyers, 1973) and have been studied as potential antimalarial agents (Gein Stein et al., 1970). Other pyrazolo[3,4-b]quinolines have also shown bactericidal activity (Farghaly et al., 1989) and applications as vasodilators (Bell & Ackerman, 1990), and have even been evaluated for enzymatic inhibitory activity (Gatta et al., 1991). We have previously prepared diverse 4-aryl-3,7,7-trimethyl-4,7,8,9-tetrahydro- 2H-pyrazolo[3,4-b]quinolin-5-(6H)-ones and reported their structures (Cannon et al., 2001a,b,c,d). The present work was undertaken to expand the possible applications of such heterocycles, by using N-alkylation to prepare derivatives from azole systems. Here, we report the structure of the title compound, (I), which was prepared by the easy, efficient and regioselective method described below. \sch
Selected bond lengths and angles for (I) are given in Table 1 and are similar to those reported in the four structures cited above (Cannon et al., 2001a,b,c,d). Fig. 1 depicts a view of the molecule.
Molecules of (I) form C(6) chains (Bernstein et al., 1995) via the N9—H9···O5i hydrogen bond along the c axis by the operation of the c glide plane, as shown in Fig. 2 [symmetry code: (i) x, 1 - y, 1/2 + z]. The molecules in these chains are then linked by weak C12—H12···O12i interactions and this interaction, together with the N9—H9···O5i hydrogen bond, forms an R22(23) ring (Bernstein et al., 1995), as shown in Fig. 3. These linked chains are not connected to the chains related by the C-centring. Pendant hydrogen-bonded ethanol solvent molecules are attached to each molecule of (I). Details of the hydrogen bonding are given in Table 2.
There is significant π–π base-stacking between rings C131—C136 and N9/C8a/C4a/C4/C3a/C9a (at x, -y, 1/2 + z Not 1 - y?), where the distance between centres of gravity is 3.73 Å, the perpendicular distance of the centre of gravity of the former ring from the latter is 3.73 Å, the perpendicular distance of the centre of gravity of the latter from the former is 3.50 Å and the angle between the planes is 2.7°. In addition, ring C131—C136 is involved in π–π stacking with ring N1/N2/C3/C3a/C9a (at x, -y, 1/2 + z Not 1 - y?), where the distance between centres of gravity is 3.76 Å, the perpendicular distance of the centre of gravity of the former from the latter is 3.53 Å, the perpendicular distance of the centre of gravity of the latter from the former is 3.52 Å and the angle between the planes is 0.73°.
This supramolecular structure is different from those reported by Cannon et al. (2001a,b,c,d), which were all similar. This difference is due to the presence of the 2-(4-nitrobenzoyl)ethyl substituent on N1, which locks the 1H form and precludes the presence of an H atom at N2, which is involved in the formation of the supramolecular structures of the crystal structures cited above. In compound (I), the 1H configuration of the heterocyclic system results in an essentially planar pyridine ring, whereas in the published structures, it is intermediate between a boat and an envelope. Examination of the structure with PLATON (Spek, 2000) showed that there were no solvent accessible voids in the crystal lattice apart from that occupied by the solvent molecule.