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The molecules of 8-methyl-7,10-diphenyl-5
H-benzo[
h]pyrazolo[3,4-
b]quinoline-5,6(10
H)-dione, C
27H
17N
3O
2, (I), are weakly linked into chains by a single C—H
O hydrogen bond, and these chains are linked into sheets by a π–π stacking interaction involving pyridyl and aryl rings. In 8-methyl-7-(4-methylphenyl)-10-phenyl-5
H-benzo[
h]pyrazolo[3,4-
b]quinoline-5,6(10
H)-dione, C
28H
19N
3O
2, (II), the molecules are linked into a three-dimensional framework structure by a combination of C—H
N, C—H
O and C—H
π(arene) hydrogen bonds, together with a π–π stacking interaction analogous to that in (I).
Supporting information
CCDC references: 782541; 782542
An intimate mixture containing 1 mmole of each of
naphthalene-1,2,4(3H)-trione, 5-amino-3-methyl-1-phenylpyrazole and the
appropriate aldehyde [benzaldehyde for (I) or 4-tolualdehyde for (II)] was
irradiated in a microwave oven in the absence of solvent for 3 min. The solids
obtained were purified by recrystallization from ethanol, and crystals
suitable for single-crystal X-ray diffraction were grown by slow evaporation
of solutions in dimethylformamide. Analysis for (I): orange, yield 85%, m.p.
545–546 K; MS m/z (%) = 415 (M+, 19), 386 (100), 77
(6). Analysis for (II): red, yield 85%, m.p. 546–547 K; MS m/z
(%) = 429 (M+, 24), 414 (15), 400 (100) 386 (95).
All H atoms were located in difference maps and subsequently treated as riding
atoms in geometrically idealised positions, with C—H = 0.95 (aromatic) or
0.98 Å (methyl) and with Uiso(H) = kUeq(C), where k
= 1.5 for the methyl groups, which were permitted to rotate but not to tilt,
and 1.2 for all other H atoms.
For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (I); SIR2004 (Burla et al., 2005) for (II). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
(I) Benzo[
h]pyrazolo[3,4-
b]quinoline-5,6(10
H)-dione
top
Crystal data top
C27H17N3O2 | F(000) = 864 |
Mr = 415.44 | Dx = 1.452 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4362 reflections |
a = 15.436 (5) Å | θ = 2.7–27.5° |
b = 13.622 (7) Å | µ = 0.09 mm−1 |
c = 9.359 (5) Å | T = 120 K |
β = 105.00 (4)° | Needle, orange |
V = 1900.9 (16) Å3 | 0.27 × 0.12 × 0.10 mm |
Z = 4 | |
Data collection top
Bruker Nonius KappaCCD area-detector diffractometer | 3532 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2660 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
Detector resolution: 9.091 pixels mm-1 | θmax = 25.5°, θmin = 2.7° |
ϕ and ω scans | h = −18→18 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −16→16 |
Tmin = 0.956, Tmax = 0.991 | l = −11→11 |
20384 measured reflections | |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0389P)2 + 0.9212P] where P = (Fo2 + 2Fc2)/3 |
3532 reflections | (Δ/σ)max = 0.001 |
290 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
Crystal data top
C27H17N3O2 | V = 1900.9 (16) Å3 |
Mr = 415.44 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.436 (5) Å | µ = 0.09 mm−1 |
b = 13.622 (7) Å | T = 120 K |
c = 9.359 (5) Å | 0.27 × 0.12 × 0.10 mm |
β = 105.00 (4)° | |
Data collection top
Bruker Nonius KappaCCD area-detector diffractometer | 3532 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2660 reflections with I > 2σ(I) |
Tmin = 0.956, Tmax = 0.991 | Rint = 0.050 |
20384 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.20 e Å−3 |
3532 reflections | Δρmin = −0.24 e Å−3 |
290 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.18866 (13) | 0.07396 (14) | 0.1177 (2) | 0.0224 (5) | |
H1 | 0.2344 | 0.0704 | 0.2078 | 0.027* | |
C2 | 0.14831 (13) | −0.01084 (15) | 0.0535 (2) | 0.0243 (5) | |
H2 | 0.1659 | −0.0722 | 0.1002 | 0.029* | |
C3 | 0.08228 (13) | −0.00755 (15) | −0.0786 (2) | 0.0235 (5) | |
H3 | 0.0536 | −0.0661 | −0.1216 | 0.028* | |
C4 | 0.05887 (13) | 0.08114 (15) | −0.1467 (2) | 0.0219 (5) | |
H4 | 0.0150 | 0.0837 | −0.2389 | 0.026* | |
C4a | 0.09843 (12) | 0.16690 (14) | −0.0828 (2) | 0.0183 (4) | |
C5 | 0.07115 (12) | 0.26049 (15) | −0.1561 (2) | 0.0202 (4) | |
C6 | 0.10862 (13) | 0.35493 (14) | −0.0756 (2) | 0.0201 (4) | |
C6a | 0.18043 (12) | 0.34854 (14) | 0.0626 (2) | 0.0167 (4) | |
C7 | 0.22149 (12) | 0.43295 (14) | 0.1325 (2) | 0.0179 (4) | |
C7a | 0.28336 (12) | 0.41913 (14) | 0.2681 (2) | 0.0176 (4) | |
C8 | 0.33993 (12) | 0.48015 (14) | 0.3764 (2) | 0.0183 (4) | |
N9 | 0.38774 (10) | 0.42754 (11) | 0.48466 (17) | 0.0201 (4) | |
N10 | 0.36500 (10) | 0.33074 (11) | 0.45314 (16) | 0.0176 (4) | |
C10a | 0.30141 (12) | 0.32368 (14) | 0.32175 (19) | 0.0166 (4) | |
N11 | 0.26435 (10) | 0.24204 (11) | 0.25631 (16) | 0.0171 (4) | |
C11a | 0.20458 (12) | 0.25521 (14) | 0.1266 (2) | 0.0168 (4) | |
C11b | 0.16368 (12) | 0.16430 (14) | 0.0532 (2) | 0.0181 (4) | |
O5 | 0.01937 (9) | 0.26745 (10) | −0.27699 (15) | 0.0292 (4) | |
O6 | 0.07557 (10) | 0.43118 (10) | −0.12861 (16) | 0.0330 (4) | |
C71 | 0.20660 (12) | 0.53259 (13) | 0.0665 (2) | 0.0170 (4) | |
C72 | 0.25772 (13) | 0.56324 (14) | −0.0264 (2) | 0.0228 (5) | |
H72 | 0.3005 | 0.5199 | −0.0491 | 0.027* | |
C73 | 0.24702 (14) | 0.65614 (15) | −0.0864 (2) | 0.0256 (5) | |
H73 | 0.2825 | 0.6767 | −0.1500 | 0.031* | |
C74 | 0.18520 (13) | 0.71907 (15) | −0.0543 (2) | 0.0252 (5) | |
H74 | 0.1770 | 0.7828 | −0.0969 | 0.030* | |
C75 | 0.13539 (14) | 0.68938 (15) | 0.0396 (2) | 0.0274 (5) | |
H75 | 0.0932 | 0.7332 | 0.0630 | 0.033* | |
C76 | 0.14587 (13) | 0.59683 (15) | 0.1000 (2) | 0.0243 (5) | |
H76 | 0.1111 | 0.5771 | 0.1652 | 0.029* | |
C81 | 0.34914 (14) | 0.58829 (14) | 0.3799 (2) | 0.0273 (5) | |
H81A | 0.3028 | 0.6172 | 0.4212 | 0.041* | |
H81B | 0.3423 | 0.6129 | 0.2792 | 0.041* | |
H81C | 0.4085 | 0.6064 | 0.4416 | 0.041* | |
C101 | 0.41376 (12) | 0.25805 (14) | 0.5484 (2) | 0.0183 (4) | |
C102 | 0.47052 (13) | 0.28651 (15) | 0.6822 (2) | 0.0228 (5) | |
H102 | 0.4743 | 0.3536 | 0.7106 | 0.027* | |
C103 | 0.52150 (13) | 0.21724 (16) | 0.7738 (2) | 0.0270 (5) | |
H103 | 0.5611 | 0.2372 | 0.8647 | 0.032* | |
C104 | 0.51585 (13) | 0.11986 (16) | 0.7355 (2) | 0.0263 (5) | |
H104 | 0.5514 | 0.0724 | 0.7989 | 0.032* | |
C105 | 0.45781 (13) | 0.09189 (15) | 0.6037 (2) | 0.0254 (5) | |
H105 | 0.4525 | 0.0244 | 0.5776 | 0.030* | |
C106 | 0.40722 (13) | 0.16023 (15) | 0.5090 (2) | 0.0226 (5) | |
H106 | 0.3683 | 0.1401 | 0.4176 | 0.027* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0269 (11) | 0.0199 (11) | 0.0187 (10) | 0.0007 (9) | 0.0025 (8) | −0.0016 (8) |
C2 | 0.0320 (11) | 0.0170 (11) | 0.0241 (11) | 0.0000 (9) | 0.0078 (9) | −0.0018 (9) |
C3 | 0.0284 (11) | 0.0203 (11) | 0.0234 (11) | −0.0065 (9) | 0.0098 (9) | −0.0067 (9) |
C4 | 0.0221 (10) | 0.0256 (12) | 0.0182 (10) | −0.0031 (9) | 0.0056 (8) | −0.0040 (9) |
C4a | 0.0190 (10) | 0.0212 (11) | 0.0153 (10) | −0.0022 (8) | 0.0057 (8) | −0.0018 (8) |
C5 | 0.0187 (10) | 0.0241 (11) | 0.0177 (10) | −0.0023 (8) | 0.0047 (8) | −0.0010 (8) |
C6 | 0.0219 (10) | 0.0184 (11) | 0.0196 (10) | −0.0006 (8) | 0.0047 (8) | 0.0035 (8) |
C6a | 0.0170 (9) | 0.0179 (11) | 0.0151 (9) | −0.0007 (8) | 0.0039 (8) | 0.0006 (8) |
C7 | 0.0180 (10) | 0.0193 (11) | 0.0165 (10) | 0.0006 (8) | 0.0047 (8) | 0.0007 (8) |
C7a | 0.0187 (9) | 0.0172 (10) | 0.0177 (10) | −0.0013 (8) | 0.0060 (8) | −0.0008 (8) |
C8 | 0.0200 (10) | 0.0172 (10) | 0.0167 (10) | 0.0003 (8) | 0.0032 (8) | −0.0003 (8) |
N9 | 0.0241 (9) | 0.0156 (9) | 0.0189 (9) | −0.0024 (7) | 0.0026 (7) | −0.0031 (7) |
N10 | 0.0215 (8) | 0.0143 (9) | 0.0149 (8) | −0.0007 (7) | 0.0006 (7) | −0.0008 (7) |
C10a | 0.0174 (9) | 0.0174 (10) | 0.0139 (9) | −0.0004 (8) | 0.0023 (8) | 0.0015 (8) |
N11 | 0.0187 (8) | 0.0161 (9) | 0.0156 (8) | −0.0019 (7) | 0.0028 (7) | −0.0008 (7) |
C11a | 0.0183 (9) | 0.0167 (11) | 0.0164 (10) | −0.0004 (8) | 0.0063 (8) | −0.0004 (8) |
C11b | 0.0198 (10) | 0.0173 (10) | 0.0185 (10) | −0.0018 (8) | 0.0072 (8) | −0.0015 (8) |
O5 | 0.0310 (8) | 0.0292 (9) | 0.0209 (8) | −0.0027 (7) | −0.0050 (6) | 0.0008 (6) |
O6 | 0.0385 (9) | 0.0220 (9) | 0.0291 (8) | 0.0004 (7) | −0.0081 (7) | 0.0030 (7) |
C71 | 0.0197 (9) | 0.0146 (10) | 0.0137 (9) | −0.0038 (8) | −0.0011 (8) | −0.0001 (8) |
C72 | 0.0252 (11) | 0.0197 (11) | 0.0236 (11) | 0.0010 (9) | 0.0067 (9) | −0.0008 (9) |
C73 | 0.0309 (11) | 0.0209 (11) | 0.0272 (11) | −0.0021 (9) | 0.0117 (9) | 0.0048 (9) |
C74 | 0.0304 (11) | 0.0175 (11) | 0.0256 (11) | −0.0009 (9) | 0.0033 (9) | 0.0047 (9) |
C75 | 0.0294 (11) | 0.0227 (12) | 0.0302 (12) | 0.0059 (9) | 0.0078 (9) | 0.0030 (9) |
C76 | 0.0281 (11) | 0.0242 (12) | 0.0223 (11) | 0.0020 (9) | 0.0095 (9) | 0.0041 (9) |
C81 | 0.0331 (12) | 0.0180 (11) | 0.0265 (11) | −0.0035 (9) | −0.0001 (9) | −0.0020 (9) |
C101 | 0.0176 (9) | 0.0204 (11) | 0.0171 (10) | 0.0000 (8) | 0.0052 (8) | 0.0023 (8) |
C102 | 0.0255 (10) | 0.0214 (11) | 0.0205 (10) | −0.0001 (9) | 0.0043 (8) | −0.0018 (9) |
C103 | 0.0254 (11) | 0.0342 (13) | 0.0177 (11) | 0.0021 (10) | −0.0010 (9) | 0.0012 (9) |
C104 | 0.0246 (11) | 0.0295 (12) | 0.0226 (11) | 0.0058 (9) | 0.0020 (9) | 0.0069 (9) |
C105 | 0.0290 (11) | 0.0199 (11) | 0.0270 (11) | 0.0018 (9) | 0.0068 (9) | 0.0033 (9) |
C106 | 0.0242 (10) | 0.0231 (12) | 0.0181 (10) | −0.0019 (9) | 0.0012 (8) | 0.0003 (8) |
Geometric parameters (Å, º) top
C1—C2 | 1.375 (3) | N11—C11a | 1.333 (2) |
C1—C11b | 1.381 (3) | C11a—C11b | 1.476 (3) |
C1—H1 | 0.9500 | C71—C76 | 1.377 (3) |
C2—C3 | 1.385 (3) | C71—C72 | 1.381 (3) |
C2—H2 | 0.9500 | C72—C73 | 1.377 (3) |
C3—C4 | 1.370 (3) | C72—H72 | 0.9500 |
C3—H3 | 0.9500 | C73—C74 | 1.373 (3) |
C4—C4a | 1.381 (3) | C73—H73 | 0.9500 |
C4—H4 | 0.9500 | C74—C75 | 1.369 (3) |
C4a—C11b | 1.404 (3) | C74—H74 | 0.9500 |
C4a—C5 | 1.457 (3) | C75—C76 | 1.374 (3) |
C5—O5 | 1.208 (2) | C75—H75 | 0.9500 |
C5—C6 | 1.527 (3) | C76—H76 | 0.9500 |
C6—O6 | 1.206 (2) | C81—H81A | 0.9800 |
C6—C6a | 1.472 (3) | C81—H81B | 0.9800 |
C6a—C7 | 1.392 (3) | C81—H81C | 0.9800 |
C6a—C11a | 1.414 (3) | C101—C106 | 1.379 (3) |
C7—C7a | 1.389 (3) | C101—C102 | 1.385 (3) |
C7—C71 | 1.485 (3) | C102—C103 | 1.377 (3) |
C7a—C10a | 1.396 (3) | C102—H102 | 0.9500 |
C7a—C8 | 1.423 (3) | C103—C104 | 1.371 (3) |
C8—N9 | 1.303 (2) | C103—H103 | 0.9500 |
C8—C81 | 1.479 (3) | C104—C105 | 1.377 (3) |
N9—N10 | 1.377 (2) | C104—H104 | 0.9500 |
N10—C10a | 1.364 (2) | C105—C106 | 1.380 (3) |
N10—C101 | 1.412 (2) | C105—H105 | 0.9500 |
C10a—N11 | 1.326 (2) | C106—H106 | 0.9500 |
| | | |
C2—C1—C11b | 120.93 (18) | C1—C11b—C11a | 120.44 (17) |
C2—C1—H1 | 119.5 | C4a—C11b—C11a | 121.37 (17) |
C11b—C1—H1 | 119.5 | C76—C71—C72 | 119.02 (18) |
C1—C2—C3 | 120.57 (19) | C76—C71—C7 | 121.80 (18) |
C1—C2—H2 | 119.7 | C72—C71—C7 | 119.12 (17) |
C3—C2—H2 | 119.7 | C73—C72—C71 | 120.42 (19) |
C4—C3—C2 | 119.24 (18) | C73—C72—H72 | 119.8 |
C4—C3—H3 | 120.4 | C71—C72—H72 | 119.8 |
C2—C3—H3 | 120.4 | C74—C73—C72 | 120.1 (2) |
C3—C4—C4a | 120.71 (18) | C74—C73—H73 | 119.9 |
C3—C4—H4 | 119.6 | C72—C73—H73 | 119.9 |
C4a—C4—H4 | 119.6 | C75—C74—C73 | 119.56 (19) |
C4—C4a—C11b | 120.30 (18) | C75—C74—H74 | 120.2 |
C4—C4a—C5 | 119.64 (17) | C73—C74—H74 | 120.2 |
C11b—C4a—C5 | 120.05 (17) | C74—C75—C76 | 120.6 (2) |
O5—C5—C4a | 123.37 (18) | C74—C75—H75 | 119.7 |
O5—C5—C6 | 118.06 (18) | C76—C75—H75 | 119.7 |
C4a—C5—C6 | 118.57 (16) | C75—C76—C71 | 120.24 (19) |
O6—C6—C6a | 123.70 (18) | C75—C76—H76 | 119.9 |
O6—C6—C5 | 117.16 (17) | C71—C76—H76 | 119.9 |
C6a—C6—C5 | 119.12 (16) | C8—C81—H81A | 109.5 |
C7—C6a—C11a | 120.35 (17) | C8—C81—H81B | 109.5 |
C7—C6a—C6 | 120.80 (17) | H81A—C81—H81B | 109.5 |
C11a—C6a—C6 | 118.80 (16) | C8—C81—H81C | 109.5 |
C7a—C7—C6a | 116.06 (17) | H81A—C81—H81C | 109.5 |
C7a—C7—C71 | 120.00 (16) | H81B—C81—H81C | 109.5 |
C6a—C7—C71 | 123.82 (16) | C106—C101—C102 | 119.85 (18) |
C7—C7a—C10a | 118.75 (17) | C106—C101—N10 | 121.21 (17) |
C7—C7a—C8 | 136.21 (18) | C102—C101—N10 | 118.92 (18) |
C10a—C7a—C8 | 105.02 (16) | C103—C102—C101 | 119.8 (2) |
N9—C8—C7a | 110.65 (17) | C103—C102—H102 | 120.1 |
N9—C8—C81 | 119.91 (17) | C101—C102—H102 | 120.1 |
C7a—C8—C81 | 129.44 (17) | C104—C103—C102 | 120.85 (19) |
C8—N9—N10 | 107.37 (15) | C104—C103—H103 | 119.6 |
C10a—N10—N9 | 110.17 (14) | C102—C103—H103 | 119.6 |
C10a—N10—C101 | 131.41 (16) | C103—C104—C105 | 118.97 (19) |
N9—N10—C101 | 118.13 (15) | C103—C104—H104 | 120.5 |
N11—C10a—N10 | 126.83 (17) | C105—C104—H104 | 120.5 |
N11—C10a—C7a | 126.38 (16) | C104—C105—C106 | 121.2 (2) |
N10—C10a—C7a | 106.79 (16) | C104—C105—H105 | 119.4 |
C10a—N11—C11a | 114.95 (16) | C106—C105—H105 | 119.4 |
N11—C11a—C6a | 123.47 (17) | C101—C106—C105 | 119.32 (19) |
N11—C11a—C11b | 115.00 (16) | C101—C106—H106 | 120.3 |
C6a—C11a—C11b | 121.53 (16) | C105—C106—H106 | 120.3 |
C1—C11b—C4a | 118.19 (17) | | |
| | | |
C11b—C1—C2—C3 | 0.8 (3) | C7a—C10a—N11—C11a | 0.2 (3) |
C1—C2—C3—C4 | 1.4 (3) | C10a—N11—C11a—C6a | −0.9 (3) |
C2—C3—C4—C4a | −1.9 (3) | C10a—N11—C11a—C11b | 179.65 (16) |
C3—C4—C4a—C11b | 0.2 (3) | C7—C6a—C11a—N11 | 2.0 (3) |
C3—C4—C4a—C5 | −178.85 (18) | C6—C6a—C11a—N11 | −175.36 (17) |
C4—C4a—C5—O5 | −5.4 (3) | C7—C6a—C11a—C11b | −178.58 (17) |
C11b—C4a—C5—O5 | 175.54 (18) | C6—C6a—C11a—C11b | 4.0 (3) |
C4—C4a—C5—C6 | 173.69 (17) | C2—C1—C11b—C4a | −2.5 (3) |
C11b—C4a—C5—C6 | −5.4 (3) | C2—C1—C11b—C11a | 177.23 (19) |
O5—C5—C6—O6 | 9.4 (3) | C4—C4a—C11b—C1 | 2.0 (3) |
C4a—C5—C6—O6 | −169.71 (19) | C5—C4a—C11b—C1 | −178.95 (18) |
O5—C5—C6—C6a | −172.12 (18) | C4—C4a—C11b—C11a | −177.73 (17) |
C4a—C5—C6—C6a | 8.8 (3) | C5—C4a—C11b—C11a | 1.3 (3) |
O6—C6—C6a—C7 | −7.0 (3) | N11—C11a—C11b—C1 | −0.8 (3) |
C5—C6—C6a—C7 | 174.59 (17) | C6a—C11a—C11b—C1 | 179.73 (19) |
O6—C6—C6a—C11a | 170.34 (19) | N11—C11a—C11b—C4a | 178.86 (17) |
C5—C6—C6a—C11a | −8.0 (3) | C6a—C11a—C11b—C4a | −0.6 (3) |
C11a—C6a—C7—C7a | −2.3 (3) | C7a—C7—C71—C76 | −87.0 (2) |
C6—C6a—C7—C7a | 175.09 (17) | C6a—C7—C71—C76 | 96.9 (2) |
C11a—C6a—C7—C71 | 173.92 (18) | C7a—C7—C71—C72 | 90.2 (2) |
C6—C6a—C7—C71 | −8.7 (3) | C6a—C7—C71—C72 | −85.8 (2) |
C6a—C7—C7a—C10a | 1.6 (3) | C76—C71—C72—C73 | −1.0 (3) |
C71—C7—C7a—C10a | −174.75 (18) | C7—C71—C72—C73 | −178.34 (17) |
C6a—C7—C7a—C8 | −179.9 (2) | C71—C72—C73—C74 | −0.1 (3) |
C71—C7—C7a—C8 | 3.7 (3) | C72—C73—C74—C75 | 1.1 (3) |
C7—C7a—C8—N9 | −178.4 (2) | C73—C74—C75—C76 | −0.9 (3) |
C10a—C7a—C8—N9 | 0.2 (2) | C74—C75—C76—C71 | −0.2 (3) |
C7—C7a—C8—C81 | 2.1 (4) | C72—C71—C76—C75 | 1.2 (3) |
C10a—C7a—C8—C81 | −179.3 (2) | C7—C71—C76—C75 | 178.42 (18) |
C7a—C8—N9—N10 | −0.1 (2) | C10a—N10—C101—C106 | 6.1 (3) |
C81—C8—N9—N10 | 179.43 (17) | N9—N10—C101—C106 | −167.10 (18) |
C8—N9—N10—C10a | 0.0 (2) | C10a—N10—C101—C102 | −175.39 (19) |
C8—N9—N10—C101 | 174.58 (16) | N9—N10—C101—C102 | 11.4 (3) |
N9—N10—C10a—N11 | 179.44 (18) | C106—C101—C102—C103 | 1.3 (3) |
C101—N10—C10a—N11 | 5.8 (3) | N10—C101—C102—C103 | −177.24 (18) |
N9—N10—C10a—C7a | 0.1 (2) | C101—C102—C103—C104 | −1.0 (3) |
C101—N10—C10a—C7a | −173.49 (18) | C102—C103—C104—C105 | −0.3 (3) |
C7—C7a—C10a—N11 | −0.6 (3) | C103—C104—C105—C106 | 1.5 (3) |
C8—C7a—C10a—N11 | −179.52 (18) | C102—C101—C106—C105 | −0.2 (3) |
C7—C7a—C10a—N10 | 178.73 (16) | N10—C101—C106—C105 | 178.32 (18) |
C8—C7a—C10a—N10 | −0.2 (2) | C104—C105—C106—C101 | −1.2 (3) |
N10—C10a—N11—C11a | −178.97 (18) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O5i | 0.95 | 2.60 | 3.548 (3) | 176 |
Symmetry code: (i) −x, y−1/2, −z−1/2. |
(II) 8-methyl-7-(4-methylphenyl)-10-phenyl-5
H-
benzo[
h]pyrazolo[3,4-
b]quinoline-5,6(10
H)-dione
top
Crystal data top
C28H19N3O2 | Z = 2 |
Mr = 429.46 | F(000) = 448 |
Triclinic, P1 | Dx = 1.380 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.9952 (15) Å | Cell parameters from 4751 reflections |
b = 9.6201 (15) Å | θ = 2.5–27.5° |
c = 12.537 (4) Å | µ = 0.09 mm−1 |
α = 98.72 (2)° | T = 120 K |
β = 103.31 (2)° | Plate, red |
γ = 95.48 (2)° | 0.39 × 0.34 × 0.10 mm |
V = 1033.9 (4) Å3 | |
Data collection top
Bruker Nonius KappaCCD area-detector diffractometer | 3849 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2820 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.056 |
Detector resolution: 9.091 pixels mm-1 | θmax = 25.5°, θmin = 2.5° |
ϕ and ω scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −11→11 |
Tmin = 0.963, Tmax = 0.991 | l = −15→15 |
24512 measured reflections | |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0423P)2 + 0.5407P] where P = (Fo2 + 2Fc2)/3 |
3849 reflections | (Δ/σ)max = 0.001 |
300 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
Crystal data top
C28H19N3O2 | γ = 95.48 (2)° |
Mr = 429.46 | V = 1033.9 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.9952 (15) Å | Mo Kα radiation |
b = 9.6201 (15) Å | µ = 0.09 mm−1 |
c = 12.537 (4) Å | T = 120 K |
α = 98.72 (2)° | 0.39 × 0.34 × 0.10 mm |
β = 103.31 (2)° | |
Data collection top
Bruker Nonius KappaCCD area-detector diffractometer | 3849 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2820 reflections with I > 2σ(I) |
Tmin = 0.963, Tmax = 0.991 | Rint = 0.056 |
24512 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.24 e Å−3 |
3849 reflections | Δρmin = −0.29 e Å−3 |
300 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.9610 (2) | 0.6597 (2) | 0.65223 (17) | 0.0219 (5) | |
H1 | 0.9387 | 0.6117 | 0.7088 | 0.026* | |
C2 | 1.0739 (2) | 0.7756 (2) | 0.68022 (19) | 0.0263 (5) | |
H2 | 1.1294 | 0.8062 | 0.7558 | 0.032* | |
C3 | 1.1072 (2) | 0.8477 (2) | 0.59955 (19) | 0.0273 (5) | |
H3 | 1.1838 | 0.9286 | 0.6194 | 0.033* | |
C4 | 1.0285 (2) | 0.8014 (2) | 0.49077 (19) | 0.0258 (5) | |
H4 | 1.0513 | 0.8501 | 0.4347 | 0.031* | |
C4a | 0.9160 (2) | 0.6842 (2) | 0.46170 (17) | 0.0206 (5) | |
C5 | 0.8370 (2) | 0.6349 (2) | 0.34442 (18) | 0.0224 (5) | |
C6 | 0.7215 (2) | 0.4989 (2) | 0.31300 (17) | 0.0206 (5) | |
C6a | 0.6728 (2) | 0.4377 (2) | 0.40217 (16) | 0.0177 (4) | |
C7 | 0.5548 (2) | 0.3228 (2) | 0.37848 (16) | 0.0170 (4) | |
C7a | 0.5266 (2) | 0.2687 (2) | 0.46976 (16) | 0.0177 (4) | |
C8 | 0.4176 (2) | 0.1652 (2) | 0.49021 (17) | 0.0193 (4) | |
N9 | 0.44275 (19) | 0.16209 (17) | 0.59741 (14) | 0.0210 (4) | |
N10 | 0.56876 (18) | 0.26179 (17) | 0.64982 (13) | 0.0198 (4) | |
C10a | 0.6198 (2) | 0.3282 (2) | 0.57511 (16) | 0.0178 (4) | |
N11 | 0.73338 (18) | 0.43559 (17) | 0.60024 (13) | 0.0184 (4) | |
C11a | 0.7570 (2) | 0.4905 (2) | 0.51363 (16) | 0.0167 (4) | |
C11b | 0.8799 (2) | 0.6126 (2) | 0.54274 (17) | 0.0186 (4) | |
O5 | 0.86105 (18) | 0.69482 (17) | 0.27081 (13) | 0.0350 (4) | |
O6 | 0.67912 (18) | 0.44708 (17) | 0.21569 (12) | 0.0316 (4) | |
C71 | 0.4629 (2) | 0.2586 (2) | 0.26496 (16) | 0.0185 (4) | |
C72 | 0.3617 (2) | 0.3317 (2) | 0.20237 (17) | 0.0248 (5) | |
H72 | 0.3511 | 0.4262 | 0.2320 | 0.030* | |
C73 | 0.2763 (3) | 0.2693 (2) | 0.09771 (18) | 0.0291 (5) | |
H73 | 0.2070 | 0.3213 | 0.0559 | 0.035* | |
C74 | 0.2890 (3) | 0.1323 (2) | 0.05197 (18) | 0.0291 (5) | |
C75 | 0.3892 (3) | 0.0597 (2) | 0.11532 (18) | 0.0305 (5) | |
H75 | 0.3996 | −0.0348 | 0.0857 | 0.037* | |
C76 | 0.4745 (2) | 0.1206 (2) | 0.22043 (18) | 0.0263 (5) | |
H76 | 0.5420 | 0.0677 | 0.2629 | 0.032* | |
C81 | 0.2879 (2) | 0.0682 (2) | 0.41112 (18) | 0.0255 (5) | |
H81A | 0.3286 | −0.0050 | 0.3670 | 0.038* | |
H81B | 0.2264 | 0.1223 | 0.3613 | 0.038* | |
H81C | 0.2229 | 0.0233 | 0.4527 | 0.038* | |
C101 | 0.6328 (2) | 0.2841 (2) | 0.76675 (16) | 0.0195 (5) | |
C102 | 0.5387 (2) | 0.2976 (2) | 0.83908 (17) | 0.0235 (5) | |
H102 | 0.4297 | 0.2844 | 0.8116 | 0.028* | |
C103 | 0.6049 (3) | 0.3303 (2) | 0.95193 (18) | 0.0283 (5) | |
H103 | 0.5415 | 0.3399 | 1.0029 | 0.034* | |
C104 | 0.7628 (3) | 0.3494 (2) | 0.99096 (19) | 0.0328 (6) | |
H104 | 0.8083 | 0.3739 | 1.0688 | 0.039* | |
C105 | 0.8547 (3) | 0.3328 (3) | 0.91751 (19) | 0.0327 (6) | |
H105 | 0.9636 | 0.3446 | 0.9450 | 0.039* | |
C106 | 0.7904 (2) | 0.2993 (2) | 0.80472 (18) | 0.0258 (5) | |
H106 | 0.8538 | 0.2869 | 0.7539 | 0.031* | |
C77 | 0.1978 (3) | 0.0647 (3) | −0.0633 (2) | 0.0451 (7) | |
H77A | 0.2593 | 0.0022 | −0.0986 | 0.068* | |
H77B | 0.1717 | 0.1387 | −0.1075 | 0.068* | |
H77C | 0.1029 | 0.0091 | −0.0590 | 0.068* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0205 (11) | 0.0208 (11) | 0.0229 (12) | 0.0011 (9) | 0.0043 (9) | 0.0017 (9) |
C2 | 0.0235 (12) | 0.0243 (12) | 0.0268 (12) | 0.0025 (10) | 0.0021 (9) | −0.0021 (10) |
C3 | 0.0196 (11) | 0.0196 (11) | 0.0392 (14) | −0.0037 (9) | 0.0048 (10) | 0.0022 (10) |
C4 | 0.0216 (11) | 0.0233 (12) | 0.0329 (13) | 0.0014 (10) | 0.0065 (10) | 0.0081 (10) |
C4a | 0.0161 (10) | 0.0195 (11) | 0.0265 (12) | 0.0026 (9) | 0.0066 (9) | 0.0032 (9) |
C5 | 0.0190 (11) | 0.0234 (12) | 0.0270 (12) | 0.0031 (9) | 0.0079 (9) | 0.0082 (10) |
C6 | 0.0180 (11) | 0.0219 (11) | 0.0222 (12) | 0.0042 (9) | 0.0047 (9) | 0.0047 (9) |
C6a | 0.0185 (11) | 0.0169 (10) | 0.0174 (11) | 0.0028 (9) | 0.0047 (8) | 0.0019 (9) |
C7 | 0.0174 (10) | 0.0146 (10) | 0.0190 (11) | 0.0051 (8) | 0.0044 (8) | 0.0011 (8) |
C7a | 0.0167 (10) | 0.0162 (10) | 0.0198 (11) | 0.0040 (8) | 0.0042 (8) | 0.0013 (9) |
C8 | 0.0189 (11) | 0.0166 (10) | 0.0225 (11) | 0.0035 (9) | 0.0053 (9) | 0.0028 (9) |
N9 | 0.0199 (9) | 0.0181 (9) | 0.0246 (10) | 0.0003 (8) | 0.0053 (8) | 0.0044 (8) |
N10 | 0.0206 (9) | 0.0195 (9) | 0.0179 (9) | −0.0018 (8) | 0.0035 (7) | 0.0041 (7) |
C10a | 0.0191 (11) | 0.0164 (10) | 0.0181 (11) | 0.0039 (9) | 0.0049 (8) | 0.0026 (9) |
N11 | 0.0177 (9) | 0.0186 (9) | 0.0185 (9) | 0.0015 (7) | 0.0044 (7) | 0.0027 (7) |
C11a | 0.0165 (10) | 0.0158 (10) | 0.0189 (11) | 0.0054 (8) | 0.0065 (8) | 0.0012 (8) |
C11b | 0.0160 (10) | 0.0160 (10) | 0.0229 (11) | 0.0032 (8) | 0.0046 (9) | 0.0005 (9) |
O5 | 0.0345 (9) | 0.0405 (10) | 0.0296 (9) | −0.0080 (8) | 0.0065 (7) | 0.0153 (8) |
O6 | 0.0365 (9) | 0.0366 (10) | 0.0182 (9) | −0.0058 (7) | 0.0060 (7) | 0.0019 (7) |
C71 | 0.0174 (10) | 0.0198 (11) | 0.0169 (11) | −0.0016 (9) | 0.0040 (8) | 0.0019 (9) |
C72 | 0.0248 (12) | 0.0193 (11) | 0.0270 (12) | 0.0050 (9) | 0.0018 (10) | 0.0003 (9) |
C73 | 0.0290 (13) | 0.0298 (13) | 0.0237 (12) | 0.0058 (10) | −0.0030 (10) | 0.0032 (10) |
C74 | 0.0309 (13) | 0.0285 (13) | 0.0219 (12) | −0.0008 (10) | 0.0001 (10) | −0.0006 (10) |
C75 | 0.0423 (14) | 0.0197 (12) | 0.0240 (12) | 0.0042 (10) | 0.0029 (11) | −0.0050 (10) |
C76 | 0.0311 (12) | 0.0208 (11) | 0.0238 (12) | 0.0051 (10) | 0.0001 (10) | 0.0036 (9) |
C81 | 0.0242 (12) | 0.0222 (12) | 0.0277 (12) | −0.0037 (10) | 0.0045 (10) | 0.0042 (10) |
C101 | 0.0240 (11) | 0.0160 (10) | 0.0191 (11) | 0.0031 (9) | 0.0052 (9) | 0.0052 (9) |
C102 | 0.0264 (12) | 0.0225 (11) | 0.0237 (12) | 0.0040 (9) | 0.0076 (9) | 0.0082 (9) |
C103 | 0.0377 (14) | 0.0283 (12) | 0.0226 (12) | 0.0061 (10) | 0.0138 (10) | 0.0052 (10) |
C104 | 0.0409 (15) | 0.0354 (14) | 0.0186 (12) | 0.0026 (11) | 0.0029 (10) | 0.0023 (10) |
C105 | 0.0282 (13) | 0.0407 (15) | 0.0259 (13) | 0.0043 (11) | −0.0002 (10) | 0.0067 (11) |
C106 | 0.0260 (12) | 0.0298 (13) | 0.0231 (12) | 0.0066 (10) | 0.0075 (10) | 0.0053 (10) |
C77 | 0.0528 (17) | 0.0422 (16) | 0.0274 (14) | 0.0031 (13) | −0.0083 (12) | −0.0035 (12) |
Geometric parameters (Å, º) top
C1—C2 | 1.378 (3) | C71—C72 | 1.379 (3) |
C1—C11b | 1.382 (3) | C71—C76 | 1.383 (3) |
C1—H1 | 0.9500 | C72—C73 | 1.372 (3) |
C2—C3 | 1.381 (3) | C72—H72 | 0.9500 |
C2—H2 | 0.9500 | C73—C74 | 1.381 (3) |
C3—C4 | 1.368 (3) | C73—H73 | 0.9500 |
C3—H3 | 0.9500 | C74—C75 | 1.375 (3) |
C4—C4a | 1.384 (3) | C74—C77 | 1.500 (3) |
C4—H4 | 0.9500 | C75—C76 | 1.372 (3) |
C4a—C11b | 1.391 (3) | C75—H75 | 0.9500 |
C4a—C5 | 1.461 (3) | C76—H76 | 0.9500 |
C5—O5 | 1.208 (2) | C81—H81A | 0.9800 |
C5—C6 | 1.530 (3) | C81—H81B | 0.9800 |
C6—O6 | 1.203 (2) | C81—H81C | 0.9800 |
C6—C6a | 1.471 (3) | C101—C106 | 1.373 (3) |
C6a—C7 | 1.403 (3) | C101—C102 | 1.377 (3) |
C6a—C11a | 1.417 (3) | C102—C103 | 1.377 (3) |
C7—C7a | 1.391 (3) | C102—H102 | 0.9500 |
C7—C71 | 1.478 (3) | C103—C104 | 1.376 (3) |
C7a—C10a | 1.394 (3) | C103—H103 | 0.9500 |
C7a—C8 | 1.423 (3) | C104—C105 | 1.373 (3) |
C8—N9 | 1.316 (3) | C104—H104 | 0.9500 |
C8—C81 | 1.481 (3) | C105—C106 | 1.374 (3) |
N9—N10 | 1.377 (2) | C105—H105 | 0.9500 |
N10—C10a | 1.349 (2) | C106—H106 | 0.9500 |
N10—C101 | 1.421 (3) | C77—H77A | 0.9800 |
C10a—N11 | 1.327 (3) | C77—H77B | 0.9800 |
N11—C11a | 1.327 (2) | C77—H77C | 0.9800 |
C11a—C11b | 1.474 (3) | | |
| | | |
C2—C1—C11b | 120.6 (2) | C72—C71—C7 | 121.55 (18) |
C2—C1—H1 | 119.7 | C76—C71—C7 | 119.91 (18) |
C11b—C1—H1 | 119.7 | C73—C72—C71 | 120.5 (2) |
C1—C2—C3 | 120.6 (2) | C73—C72—H72 | 119.7 |
C1—C2—H2 | 119.7 | C71—C72—H72 | 119.7 |
C3—C2—H2 | 119.7 | C72—C73—C74 | 121.3 (2) |
C4—C3—C2 | 119.2 (2) | C72—C73—H73 | 119.3 |
C4—C3—H3 | 120.4 | C74—C73—H73 | 119.3 |
C2—C3—H3 | 120.4 | C75—C74—C73 | 117.8 (2) |
C3—C4—C4a | 120.5 (2) | C75—C74—C77 | 120.8 (2) |
C3—C4—H4 | 119.7 | C73—C74—C77 | 121.4 (2) |
C4a—C4—H4 | 119.7 | C76—C75—C74 | 121.5 (2) |
C4—C4a—C11b | 120.56 (19) | C76—C75—H75 | 119.3 |
C4—C4a—C5 | 119.24 (19) | C74—C75—H75 | 119.3 |
C11b—C4a—C5 | 120.19 (18) | C75—C76—C71 | 120.4 (2) |
O5—C5—C4a | 123.05 (19) | C75—C76—H76 | 119.8 |
O5—C5—C6 | 118.45 (19) | C71—C76—H76 | 119.8 |
C4a—C5—C6 | 118.48 (18) | C8—C81—H81A | 109.5 |
O6—C6—C6a | 124.22 (19) | C8—C81—H81B | 109.5 |
O6—C6—C5 | 116.91 (19) | H81A—C81—H81B | 109.5 |
C6a—C6—C5 | 118.84 (18) | C8—C81—H81C | 109.5 |
C7—C6a—C11a | 120.13 (18) | H81A—C81—H81C | 109.5 |
C7—C6a—C6 | 121.61 (18) | H81B—C81—H81C | 109.5 |
C11a—C6a—C6 | 118.07 (18) | C106—C101—C102 | 121.52 (19) |
C7a—C7—C6a | 116.02 (18) | C106—C101—N10 | 118.12 (18) |
C7a—C7—C71 | 119.88 (17) | C102—C101—N10 | 120.27 (18) |
C6a—C7—C71 | 124.10 (18) | C101—C102—C103 | 118.9 (2) |
C7—C7a—C10a | 118.25 (18) | C101—C102—H102 | 120.5 |
C7—C7a—C8 | 137.26 (19) | C103—C102—H102 | 120.5 |
C10a—C7a—C8 | 104.42 (17) | C104—C103—C102 | 120.1 (2) |
N9—C8—C7a | 110.79 (18) | C104—C103—H103 | 120.0 |
N9—C8—C81 | 119.31 (18) | C102—C103—H103 | 120.0 |
C7a—C8—C81 | 129.89 (19) | C105—C104—C103 | 120.1 (2) |
C8—N9—N10 | 106.56 (16) | C105—C104—H104 | 120.0 |
C10a—N10—N9 | 110.62 (16) | C103—C104—H104 | 120.0 |
C10a—N10—C101 | 127.16 (17) | C104—C105—C106 | 120.6 (2) |
N9—N10—C101 | 122.20 (16) | C104—C105—H105 | 119.7 |
N11—C10a—N10 | 125.10 (18) | C106—C105—H105 | 119.7 |
N11—C10a—C7a | 127.22 (19) | C101—C106—C105 | 118.8 (2) |
N10—C10a—C7a | 107.59 (17) | C101—C106—H106 | 120.6 |
C11a—N11—C10a | 114.58 (17) | C105—C106—H106 | 120.6 |
N11—C11a—C6a | 123.74 (18) | C74—C77—H77A | 109.5 |
N11—C11a—C11b | 114.21 (17) | C74—C77—H77B | 109.5 |
C6a—C11a—C11b | 122.05 (18) | H77A—C77—H77B | 109.5 |
C1—C11b—C4a | 118.36 (19) | C74—C77—H77C | 109.5 |
C1—C11b—C11a | 120.39 (19) | H77A—C77—H77C | 109.5 |
C4a—C11b—C11a | 121.24 (18) | H77B—C77—H77C | 109.5 |
C72—C71—C76 | 118.52 (19) | | |
| | | |
C11b—C1—C2—C3 | 0.6 (3) | C10a—N11—C11a—C6a | −2.0 (3) |
C1—C2—C3—C4 | −1.1 (3) | C10a—N11—C11a—C11b | 178.09 (17) |
C2—C3—C4—C4a | 0.5 (3) | C7—C6a—C11a—N11 | 1.3 (3) |
C3—C4—C4a—C11b | 0.7 (3) | C6—C6a—C11a—N11 | −173.76 (17) |
C3—C4—C4a—C5 | −178.3 (2) | C7—C6a—C11a—C11b | −178.79 (17) |
C4—C4a—C5—O5 | −2.8 (3) | C6—C6a—C11a—C11b | 6.1 (3) |
C11b—C4a—C5—O5 | 178.20 (19) | C2—C1—C11b—C4a | 0.5 (3) |
C4—C4a—C5—C6 | 175.60 (18) | C2—C1—C11b—C11a | −178.69 (18) |
C11b—C4a—C5—C6 | −3.4 (3) | C4—C4a—C11b—C1 | −1.2 (3) |
O5—C5—C6—O6 | 11.4 (3) | C5—C4a—C11b—C1 | 177.77 (19) |
C4a—C5—C6—O6 | −167.14 (19) | C4—C4a—C11b—C11a | 178.01 (18) |
O5—C5—C6—C6a | −170.39 (19) | C5—C4a—C11b—C11a | −3.0 (3) |
C4a—C5—C6—C6a | 11.1 (3) | N11—C11a—C11b—C1 | 0.9 (3) |
O6—C6—C6a—C7 | −9.2 (3) | C6a—C11a—C11b—C1 | −179.05 (19) |
C5—C6—C6a—C7 | 172.72 (18) | N11—C11a—C11b—C4a | −178.34 (18) |
O6—C6—C6a—C11a | 165.83 (19) | C6a—C11a—C11b—C4a | 1.8 (3) |
C5—C6—C6a—C11a | −12.3 (3) | C7a—C7—C71—C72 | 113.0 (2) |
C11a—C6a—C7—C7a | 0.9 (3) | C6a—C7—C71—C72 | −67.4 (3) |
C6—C6a—C7—C7a | 175.84 (17) | C7a—C7—C71—C76 | −65.3 (3) |
C11a—C6a—C7—C71 | −178.68 (18) | C6a—C7—C71—C76 | 114.3 (2) |
C6—C6a—C7—C71 | −3.8 (3) | C76—C71—C72—C73 | −0.9 (3) |
C6a—C7—C7a—C10a | −2.2 (3) | C7—C71—C72—C73 | −179.2 (2) |
C71—C7—C7a—C10a | 177.39 (18) | C71—C72—C73—C74 | −0.1 (3) |
C6a—C7—C7a—C8 | 174.3 (2) | C72—C73—C74—C75 | 0.6 (3) |
C71—C7—C7a—C8 | −6.1 (4) | C72—C73—C74—C77 | −178.9 (2) |
C7—C7a—C8—N9 | −177.1 (2) | C73—C74—C75—C76 | −0.2 (4) |
C10a—C7a—C8—N9 | −0.2 (2) | C77—C74—C75—C76 | 179.3 (2) |
C7—C7a—C8—C81 | 2.5 (4) | C74—C75—C76—C71 | −0.8 (3) |
C10a—C7a—C8—C81 | 179.4 (2) | C72—C71—C76—C75 | 1.3 (3) |
C7a—C8—N9—N10 | −0.5 (2) | C7—C71—C76—C75 | 179.7 (2) |
C81—C8—N9—N10 | 179.87 (17) | C10a—N10—C101—C106 | −42.3 (3) |
C8—N9—N10—C10a | 1.1 (2) | N9—N10—C101—C106 | 136.1 (2) |
C8—N9—N10—C101 | −177.63 (18) | C10a—N10—C101—C102 | 134.3 (2) |
N9—N10—C10a—N11 | 175.64 (17) | N9—N10—C101—C102 | −47.3 (3) |
C101—N10—C10a—N11 | −5.8 (3) | C106—C101—C102—C103 | 1.6 (3) |
N9—N10—C10a—C7a | −1.2 (2) | N10—C101—C102—C103 | −174.89 (18) |
C101—N10—C10a—C7a | 177.39 (18) | C101—C102—C103—C104 | 0.1 (3) |
C7—C7a—C10a—N11 | 1.7 (3) | C102—C103—C104—C105 | −1.3 (3) |
C8—C7a—C10a—N11 | −175.90 (19) | C103—C104—C105—C106 | 1.0 (4) |
C7—C7a—C10a—N10 | 178.43 (17) | C102—C101—C106—C105 | −1.9 (3) |
C8—C7a—C10a—N10 | 0.9 (2) | N10—C101—C106—C105 | 174.61 (19) |
N10—C10a—N11—C11a | −175.71 (18) | C104—C105—C106—C101 | 0.7 (3) |
C7a—C10a—N11—C11a | 0.5 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C72—H72···N11i | 0.95 | 2.62 | 3.395 (3) | 139 |
C104—H104···O6ii | 0.95 | 2.45 | 3.114 (3) | 127 |
C75—H75···Cgiii | 0.95 | 2.89 | 3.636 (2) | 136 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y, z+1; (iii) −x+1, −y, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C27H17N3O2 | C28H19N3O2 |
Mr | 415.44 | 429.46 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 15.436 (5), 13.622 (7), 9.359 (5) | 8.9952 (15), 9.6201 (15), 12.537 (4) |
α, β, γ (°) | 90, 105.00 (4), 90 | 98.72 (2), 103.31 (2), 95.48 (2) |
V (Å3) | 1900.9 (16) | 1033.9 (4) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.09 |
Crystal size (mm) | 0.27 × 0.12 × 0.10 | 0.39 × 0.34 × 0.10 |
|
Data collection |
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.956, 0.991 | 0.963, 0.991 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20384, 3532, 2660 | 24512, 3849, 2820 |
Rint | 0.050 | 0.056 |
(sin θ/λ)max (Å−1) | 0.606 | 0.606 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.106, 1.11 | 0.052, 0.115, 1.08 |
No. of reflections | 3532 | 3849 |
No. of parameters | 290 | 300 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.24 | 0.24, −0.29 |
Comparison of selected geometric parameters (Å, °) in (I) and (II) topParameter | (I) | (II) |
C5—C6 | 1.527 (3) | 1.530 (3) |
C7a—C8 | 1.423 (3) | 1.423 (3) |
C8—N9 | 1.303 (2) | 1.316 (3) |
N9—N10 | 1.377 (2) | 1.377 (2) |
N10—C10a | 1.364 (2) | 1.349 (2) |
C10a—C7a | 1.396 (3) | 1.394 (3) |
| | |
C6a—C7—C71—C72 | -85.8 (2) | -67.4 (3) |
N9—N10—C101—C102 | 11.4 (3) | -47.3 (3) |
O5—C5—C6—O6 | 9.4 (3) | 11.4 (3) |
Comparison of hydrogen-bond parameters (Å, °) in (I) and (II) topCompound | D—H···A | D—H | H···A | D···A | D—H···A |
(I) | C3—H3···O5i | 0.95 | 2.60 | 3.548 (3) | 176 |
(II) | C72—H72···N11ii | 0.95 | 2.62 | 3.395 (3) | 139 |
| C104—H104···O6iii | 0.95 | 2.45 | 3.114 (3) | 127 |
| C75—H75···Cgiv | 0.95 | 2.89 | 3.636 (2) | 168 |
Cg represents the centroid of the C101–C106 ring.
Symmetry codes: (i) -x, y + 1/2, -z - 1/2; (ii) -x + 1, -y + 1, -z + 1;
(iii) x, y, z + 1; (iv) -x + 1, -y, -z + 1. |
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We are interested in the synthesis and biological properties of new pyrazolo[3,4-b]quinoline derivatives, some of which have exhibited parasiticidic properties (Bristol–Meyers Co., 1973), bactericidal activity (Farghaly et al., 1989) and vasodilator properties (Bell & Ackerman, 1990), while some have been evaluated for enzymatic inhibitory activity (Gatta et al., 1991). We have directed much of our work in this area towards the synthesis of such compounds using three-component reactions between 5-aminopyrazoles, aromatic aldehydes and ketones containing active methylene units. Here we report the structures of two closely-related benzo[h]pyrazolo[3,4-b]quinoline-5,6(10H)-diones, namely 8-methyl-7,10-diphenyl-5H-benzo[h]pyrazolo[3,4-b]quinoline-5,6(10H)-dione, (I), and 8-methyl-7-(4-methylphenyl)-10-phenyl-5H-benzo[h]pyrazolo[3,4-b]quinoline-5,6(10H)-dione, (II) (Figs. 1 and 2), which were prepared using naphthalene-1,2,4(3H)-trione as the methylene-active ketone component (see scheme). It turned out that these structure determinations were essential for the unambiguous identification of these compounds, because it was not possible using the normal spectroscopic techniques to determine the regiochemistry of the synthetic reactions and, in particular, to distinguish thereby between the benzo[h]pyrazolo[3,4-b]quinolinedione structures actually formed and the possible isomeric benzo[g]pyrazolo[3,4-b]quinolinediones, which had been expected on the basis of a recent report (Chen et al., 2008).
Although the constitutions of (I) and (II) differ only in the presence of a 4-methyl substituent in the C71–C76 aryl ring in (II), nonetheless these two compounds crystallise in different crystal systems, monoclinic and triclinic, respectively. They also exhibit very different modes of supramolecular aggregation, in the form of sheets built from π-stacked hydrogen-bonded chains in (I) compared with a complex three-dimensional framework structure in (II). On the other hand, the corresponding intramolecular bond distances are very similar in the two compounds with, in each case, a long C5—C6 bond between the two adjacent carbonyl groups (Table 1), as is typical for such structural units (Allen et al., 1987). There is clear evidence for bond fixation in the pyrazole ring, with typical aromatic-type delocalisation in the pyridine ring and in the terminal carbocyclic ring of the fused ring system (cf. scheme).
The only significant differences between the molecular structures of (I) and (II) are to be found in their conformations, as defined by the torsion angles (Table 1) defining the orientations of the two pendent aryl rings relative to the fused polycyclic core of the molecules. In both compounds, the carbocyclic ring (C4a/C5/C6/C6a/C11a/C11b) is slightly distorted towards an envelope conformation, folded across the line C5···C6a, slightly more markedly in (II) than in (I): in (I), the maximum deviation from the mean plane described by the ring atoms is 0.046 (2) Å for atom C6, but in (II), the maximum deviation is 0.072 (2) Å, again for atom C6. This ring distortion is reflected in, and possibly caused by, the non-parallel orientation of the two carbonyl groups (Table 1), itself probably resulting from the mutual repulsion of the two negatively polarised O atoms.
The crystal structure of (I) contains just one rather weak C—H···O hydrogen bond, while intermolecular C—H···N and C—H···π interactions are absent. The hydrogen bond links molecules which are related by the 21 screw axis along (0, y, -1/4) into a C(6) (Bernstein et al., 1995) chain running parallel to the [010] direction (Fig. 3). Chains of this type are linked into sheets by means of a π–π stacking interaction. The pyridine ring of the molecule at (x, y, z), which forms part of the C(6) chain along (0, y, -1/4), makes a dihedral angle of only 2.66 (2)° with the C101–C106 aryl ring in the molecule at (x, 1/2 - y, -1/2 + z), which itself forms part of the C(6) chain along (0, y, -3/4). The interplanar spacing between these two rings is ca 3.38 Å, with a ring-centroid separation of 3.601 (2) Å, corresponding to a ring-centroid offset of ca 1.28 Å. In this manner, the reference chain along (0, y, -1/4) is linked to the two adjacent chains along (0, y, -3/4) and (0, y, 1/4), so forming a sheet of π-stacked hydrogen-bonded chains lying parallel to (100) (Fig. 3).
The three-dimensional framework structure of (II) is built from a combination of C—H···N, C—H···O and C—H···π(arene) hydrogen bonds (Table 2), together with a π–π stacking interaction similar to that found in (I). Despite the complexity of the framework, its formation can readily be analysed using the sub-structure approach (Ferguson et al., 1998a,b; Gregson et al., 2000). In particular, an inversion-related pair of C—H···N hydrogen bonds (Table 2) links an inversion-related pair of molecules into a cyclic centrosymmetric R22(14) dimer centred at (1/2, 1/2, 1/2). This finite zero-dimensional sub-structural fragment can be regarded as the key building block in the overall structure, as the other three interactions, acting individually, link dimers of this type to form three distinct one-dimensional sub-structures. It is convenient to consider the actions of each of the other three intermolecular interactions in turn, both when acting alone and when acting to link the R22(14) dimers.
When acting alone, the C—H···O hydrogen bond links molecules related by translation to form a C(12) chain running parallel to the [001] direction. When acting in concert with the C—H···N hydrogen bond, the C—H···O interaction links R22(14) dimers into a chain of rings along [001] in which R22(14) rings centred at (1/2, 1/2, 1/2 + n), where n represents an integer, alternate with R44(30) rings centred at (1/2, 1/2, n), where n again represents an integer (Fig. 4). The C—H···π(arene) hydrogen bond links the molecules at (x, y, z) and (1 - x, 1 - y, 1 - z) into a centrosymmetric dimer and, in combination with the C—H···N hydrogen bond, it generates a chain of centrosymmetric rings running parallel to the [010] direction, with R22(14) rings built from paired C—H···N hydrogen bonds centred at (1/2, 1/2 + n, 1/2) alternating with rings built from paired C—H···π(arene) hydrogen bonds centred at (1/2, n, 1/2), where in both cases n represents an integer (Fig. 5). The pyridine ring of the molecule at (x, y, z) and the fused aryl ring of the molecule at (2 - x, 1 - y, 1 - z) are almost parallel, with a dihedral angle between their mean planes of only 3.36 (2)°. The ring-centroid separation is 3.723 (2) Å and the interplanar spacing is ca 3.42 °, corresponding to a ring-centroid offset of ca 1.47 Å. The effect of this π–π stacking interaction is to link the hydrogen-bonded R22(14) dimers into a π-stacked chain of dimers running parallel to the [100] direction (Fig. 6).
In the structure of (II) it is thus possible to identify three distinct sub-structural chains along [100], [010] and [001], respectively, each utilising a different pair of direction-specific intermolecular interactions. The combination of these three sub-structural motifs generates a three-dimensional framework structure of considerable complexity.
Thus, the notional replacement of a single H atom in (I) by a methyl group in (II) is associated with a change in crystal system, with differences in the overall molecular conformations, in particular the dihedral angles between the polycyclic ring system and the pendent rings (cf. Table 1), and with a major change in the supramolecular aggregation and the molecular packing. The direction-specific intermolecular forces which influence the molecular arrangements in the structures of (I) and (II) are comparatively weak, and the interpretation and prediction of crystal structures dominated by such forces, as opposed to the much stronger forces between charged entities, remains problematic, especially in molecules such as those of (I) and (II) having some degree of conformational flexibility (Day et al., 2009). Any attempt to provide a simple explanation for the observed differences between the structures of (I) and (II) is likely, at the present stage, to be entirely speculative.