Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109053554/sk3356sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109053554/sk3356Isup2.hkl |
CCDC reference: 765481
A mixture of 1-(6-aminobenzo[1,3]dioxol-5-yl)ethanone (0.50 g, 2.8 mmol) and 2-oxo-1,2-dihydroquinoline-3-carbaldehyde (0.48 g, 2.8 mmol) in ethanol (10 ml) containing 20% (w/v) aqueous sodium hydroxide solution (0.5 ml) was heated under reflux for 10 min. The mixture was cooled to ambient temperature, and the resulting solid precipitate was collected by filtration, washed successively with ethanol (3 ml) and water (3 ml), and then dried under reduced pressure to give the title compound, (I), in 55% yield. Dark-red crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in air, of a solution of (I) in dimethylformamide (m.p. 524 K). EIMS (70 eV), m/z (%) 334 (12 [M+]), 333 (62 [M - 1]), 190 (23, [M - C9H6N]. Analysis, found: C 68.3, H 4.1, N 8.3%; C19H14N2O4 requires: C 68.3, H 4.2 N 8.4%.
All H atoms were located in difference maps. The coordinates of the H atoms bonded to N16 were refined without restraint, with Uiso(H) = 1.2Ueq(N), giving N—H distances of 0.89 (2) and 0.91 (2) Å, and a sum of bond angles at N16 of ca 349°. The remaining H atoms were treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aromatic or alkenyl) or 0.99 Å (CH2) and N—H = 0.88 Å, and with Uiso(H) = 1.2Ueq(carrier).
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: SIR2004 (Burla et al., 2005); 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).
C19H14N2O4 | Z = 2 |
Mr = 334.32 | F(000) = 348 |
Triclinic, P1 | Dx = 1.525 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.7799 (2) Å | Cell parameters from 2858 reflections |
b = 9.9485 (3) Å | θ = 3.1–26.1° |
c = 13.0849 (5) Å | µ = 0.11 mm−1 |
α = 83.343 (2)° | T = 120 K |
β = 86.652 (2)° | Block, red |
γ = 77.128 (2)° | 0.10 × 0.06 × 0.06 mm |
V = 728.13 (4) Å3 |
Bruker Nonius KappaCCD area-detector diffractometer | 2858 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2377 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
Detector resolution: 9.091 pixels mm-1 | θmax = 26.1°, θmin = 3.1° |
ϕ and ω scans | h = −7→6 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −12→11 |
Tmin = 0.989, Tmax = 0.994 | l = −16→16 |
9539 measured reflections |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.112 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.047P)2 + 0.3719P] where P = (Fo2 + 2Fc2)/3 |
2858 reflections | (Δ/σ)max = 0.001 |
232 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C19H14N2O4 | γ = 77.128 (2)° |
Mr = 334.32 | V = 728.13 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.7799 (2) Å | Mo Kα radiation |
b = 9.9485 (3) Å | µ = 0.11 mm−1 |
c = 13.0849 (5) Å | T = 120 K |
α = 83.343 (2)° | 0.10 × 0.06 × 0.06 mm |
β = 86.652 (2)° |
Bruker Nonius KappaCCD area-detector diffractometer | 2858 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2377 reflections with I > 2σ(I) |
Tmin = 0.989, Tmax = 0.994 | Rint = 0.033 |
9539 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.112 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.23 e Å−3 |
2858 reflections | Δρmin = −0.24 e Å−3 |
232 parameters |
x | y | z | Uiso*/Ueq | ||
C1 | 0.4679 (3) | 0.35681 (16) | 0.28016 (12) | 0.0202 (3) | |
O1 | 0.6323 (2) | 0.25307 (11) | 0.29335 (9) | 0.0263 (3) | |
C2 | 0.2513 (3) | 0.36683 (16) | 0.34788 (12) | 0.0201 (3) | |
H2 | 0.1277 | 0.4479 | 0.3411 | 0.024* | |
C3 | 0.2306 (3) | 0.26117 (16) | 0.41869 (12) | 0.0204 (3) | |
H3 | 0.3612 | 0.1837 | 0.4220 | 0.024* | |
O11 | 0.5005 (2) | 0.80979 (12) | −0.01246 (9) | 0.0296 (3) | |
C12 | 0.2516 (3) | 0.87584 (17) | −0.01063 (13) | 0.0284 (4) | |
H12A | 0.2306 | 0.9742 | 0.0019 | 0.034* | |
H12B | 0.1824 | 0.8726 | −0.0775 | 0.034* | |
O13 | 0.1356 (2) | 0.80294 (11) | 0.07047 (9) | 0.0278 (3) | |
C13a | 0.3034 (3) | 0.68551 (16) | 0.10278 (12) | 0.0206 (3) | |
C14 | 0.2805 (3) | 0.58113 (16) | 0.17678 (12) | 0.0198 (3) | |
H14 | 0.1331 | 0.5815 | 0.2130 | 0.024* | |
C15 | 0.4821 (3) | 0.47068 (15) | 0.19914 (11) | 0.0188 (3) | |
C16 | 0.7002 (3) | 0.47498 (16) | 0.14383 (12) | 0.0200 (3) | |
C17 | 0.7196 (3) | 0.59005 (16) | 0.07181 (12) | 0.0220 (4) | |
H17 | 0.8671 | 0.5970 | 0.0379 | 0.026* | |
C17a | 0.5198 (3) | 0.69051 (16) | 0.05271 (12) | 0.0212 (3) | |
N16 | 0.8976 (3) | 0.36867 (15) | 0.15665 (11) | 0.0239 (3) | |
H16A | 1.038 (4) | 0.3888 (19) | 0.1399 (14) | 0.029* | |
H16B | 0.887 (3) | 0.307 (2) | 0.2128 (15) | 0.029* | |
N31 | −0.3581 (2) | 0.33571 (13) | 0.56186 (10) | 0.0199 (3) | |
H31 | −0.4889 | 0.4008 | 0.5635 | 0.024* | |
C32 | −0.1853 (3) | 0.35897 (15) | 0.49073 (11) | 0.0192 (3) | |
O32 | −0.21982 (19) | 0.46824 (11) | 0.43087 (8) | 0.0228 (3) | |
C33 | 0.0333 (3) | 0.25025 (16) | 0.49099 (11) | 0.0189 (3) | |
C34 | 0.0485 (3) | 0.13472 (16) | 0.56019 (12) | 0.0201 (3) | |
H34 | 0.1895 | 0.0642 | 0.5597 | 0.024* | |
C34a | −0.1377 (3) | 0.11534 (16) | 0.63298 (12) | 0.0194 (3) | |
C35 | −0.1241 (3) | −0.00296 (16) | 0.70490 (12) | 0.0237 (4) | |
H35 | 0.0171 | −0.0736 | 0.7079 | 0.028* | |
C36 | −0.3125 (3) | −0.01683 (16) | 0.77048 (12) | 0.0259 (4) | |
H36 | −0.3025 | −0.0973 | 0.8182 | 0.031* | |
C37 | −0.5210 (3) | 0.08794 (17) | 0.76722 (12) | 0.0244 (4) | |
H37 | −0.6517 | 0.0774 | 0.8126 | 0.029* | |
C38 | −0.5377 (3) | 0.20550 (16) | 0.69906 (12) | 0.0217 (3) | |
H38 | −0.6782 | 0.2766 | 0.6979 | 0.026* | |
C38a | −0.3461 (3) | 0.21947 (15) | 0.63141 (11) | 0.0187 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0210 (8) | 0.0194 (8) | 0.0201 (8) | −0.0045 (6) | −0.0002 (6) | −0.0022 (6) |
O1 | 0.0224 (6) | 0.0210 (6) | 0.0312 (6) | −0.0007 (5) | 0.0039 (5) | 0.0046 (5) |
C2 | 0.0200 (8) | 0.0194 (8) | 0.0200 (8) | −0.0030 (6) | −0.0005 (6) | −0.0009 (6) |
C3 | 0.0196 (8) | 0.0191 (8) | 0.0210 (8) | −0.0013 (6) | −0.0009 (6) | −0.0017 (6) |
O11 | 0.0299 (6) | 0.0267 (6) | 0.0280 (6) | −0.0048 (5) | 0.0036 (5) | 0.0097 (5) |
C12 | 0.0297 (9) | 0.0248 (9) | 0.0282 (9) | −0.0058 (7) | −0.0008 (7) | 0.0069 (7) |
O13 | 0.0257 (6) | 0.0222 (6) | 0.0310 (7) | −0.0015 (5) | 0.0005 (5) | 0.0086 (5) |
C13a | 0.0211 (8) | 0.0192 (8) | 0.0206 (8) | −0.0027 (6) | −0.0031 (6) | −0.0008 (6) |
C14 | 0.0195 (8) | 0.0208 (8) | 0.0195 (8) | −0.0062 (6) | 0.0011 (6) | −0.0014 (6) |
C15 | 0.0204 (8) | 0.0185 (8) | 0.0181 (8) | −0.0060 (6) | −0.0003 (6) | −0.0017 (6) |
C16 | 0.0206 (8) | 0.0222 (8) | 0.0174 (8) | −0.0046 (6) | 0.0003 (6) | −0.0034 (6) |
C17 | 0.0226 (8) | 0.0261 (8) | 0.0176 (8) | −0.0076 (7) | 0.0035 (6) | −0.0009 (6) |
C17a | 0.0274 (8) | 0.0208 (8) | 0.0161 (7) | −0.0090 (7) | 0.0011 (6) | 0.0016 (6) |
N16 | 0.0188 (7) | 0.0248 (7) | 0.0257 (7) | −0.0035 (6) | 0.0040 (6) | 0.0027 (6) |
N31 | 0.0189 (7) | 0.0180 (7) | 0.0202 (7) | −0.0010 (5) | 0.0022 (5) | 0.0014 (5) |
C32 | 0.0216 (8) | 0.0188 (7) | 0.0167 (7) | −0.0040 (6) | −0.0016 (6) | 0.0001 (6) |
O32 | 0.0231 (6) | 0.0187 (6) | 0.0225 (6) | −0.0003 (5) | 0.0027 (5) | 0.0045 (4) |
C33 | 0.0207 (8) | 0.0186 (7) | 0.0174 (7) | −0.0042 (6) | −0.0007 (6) | −0.0018 (6) |
C34 | 0.0205 (8) | 0.0179 (7) | 0.0204 (8) | −0.0008 (6) | −0.0021 (6) | −0.0021 (6) |
C34a | 0.0232 (8) | 0.0176 (7) | 0.0175 (7) | −0.0041 (6) | −0.0013 (6) | −0.0026 (6) |
C35 | 0.0282 (9) | 0.0189 (8) | 0.0220 (8) | −0.0023 (7) | 0.0002 (7) | 0.0009 (6) |
C36 | 0.0363 (10) | 0.0199 (8) | 0.0212 (8) | −0.0086 (7) | 0.0012 (7) | 0.0030 (6) |
C37 | 0.0283 (9) | 0.0261 (8) | 0.0207 (8) | −0.0114 (7) | 0.0053 (7) | −0.0026 (6) |
C38 | 0.0218 (8) | 0.0232 (8) | 0.0201 (8) | −0.0051 (7) | 0.0013 (6) | −0.0025 (6) |
C38a | 0.0235 (8) | 0.0176 (7) | 0.0158 (7) | −0.0065 (6) | −0.0015 (6) | −0.0014 (6) |
O11—C17a | 1.3657 (18) | C17—H17 | 0.9500 |
O11—C12 | 1.442 (2) | N16—H16A | 0.89 (2) |
C12—O13 | 1.434 (2) | N16—H16B | 0.91 (2) |
C12—H12A | 0.9900 | N31—C32 | 1.364 (2) |
C12—H12B | 0.9900 | N31—H31 | 0.8800 |
O13—C13a | 1.3832 (19) | C32—C33 | 1.469 (2) |
C13a—C14 | 1.359 (2) | C33—C34 | 1.368 (2) |
C14—C15 | 1.430 (2) | C34—C34a | 1.426 (2) |
C14—H14 | 0.9500 | C34—H34 | 0.9500 |
C15—C16 | 1.423 (2) | C34a—C35 | 1.410 (2) |
C16—C17 | 1.416 (2) | C35—C36 | 1.368 (2) |
C17—C17a | 1.363 (2) | C35—H35 | 0.9500 |
C13a—C17a | 1.386 (2) | C36—C37 | 1.406 (2) |
C16—N16 | 1.375 (2) | C36—H36 | 0.9500 |
C15—C1 | 1.472 (2) | C37—C38 | 1.375 (2) |
C1—O1 | 1.2403 (19) | C37—H37 | 0.9500 |
C1—C2 | 1.483 (2) | C38—C38a | 1.398 (2) |
C2—C3 | 1.340 (2) | C38—H38 | 0.9500 |
C2—H2 | 0.9500 | C38a—N31 | 1.3777 (19) |
C3—C33 | 1.453 (2) | C34a—C38a | 1.403 (2) |
C3—H3 | 0.9500 | C32—O32 | 1.2488 (18) |
O1—C1—C15 | 121.80 (14) | O11—C17a—C13a | 110.22 (14) |
O1—C1—C2 | 119.23 (14) | C16—N16—H16A | 117.4 (12) |
C15—C1—C2 | 118.97 (13) | C16—N16—H16B | 113.9 (12) |
C3—C2—C1 | 119.74 (14) | H16A—N16—H16B | 118.1 (17) |
C3—C2—H2 | 120.1 | C32—N31—C38a | 125.85 (13) |
C1—C2—H2 | 120.1 | C32—N31—H31 | 117.1 |
C2—C3—C33 | 128.11 (14) | C38a—N31—H31 | 117.1 |
C2—C3—H3 | 115.9 | O32—C32—N31 | 119.54 (14) |
C33—C3—H3 | 115.9 | O32—C32—C33 | 124.36 (14) |
C17a—O11—C12 | 105.71 (12) | N31—C32—C33 | 116.10 (13) |
O13—C12—O11 | 107.92 (12) | C34—C33—C3 | 119.49 (14) |
O13—C12—H12A | 110.1 | C34—C33—C32 | 118.69 (14) |
O11—C12—H12A | 110.1 | C3—C33—C32 | 121.81 (13) |
O13—C12—H12B | 110.1 | C33—C34—C34a | 123.01 (14) |
O11—C12—H12B | 110.1 | C33—C34—H34 | 118.5 |
H12A—C12—H12B | 108.4 | C34a—C34—H34 | 118.5 |
C13a—O13—C12 | 105.42 (12) | C38a—C34a—C35 | 118.71 (15) |
C14—C13a—O13 | 128.65 (14) | C38a—C34a—C34 | 117.71 (14) |
C14—C13a—C17a | 121.43 (14) | C35—C34a—C34 | 123.58 (14) |
O13—C13a—C17a | 109.77 (13) | C36—C35—C34a | 120.51 (15) |
C13a—C14—C15 | 118.86 (14) | C36—C35—H35 | 119.7 |
C13a—C14—H14 | 120.6 | C34a—C35—H35 | 119.7 |
C15—C14—H14 | 120.6 | C35—C36—C37 | 120.04 (14) |
C16—C15—C14 | 118.74 (14) | C35—C36—H36 | 120.0 |
C16—C15—C1 | 120.27 (14) | C37—C36—H36 | 120.0 |
C14—C15—C1 | 120.96 (14) | C38—C37—C36 | 120.70 (15) |
N16—C16—C17 | 117.54 (14) | C38—C37—H37 | 119.7 |
N16—C16—C15 | 122.06 (14) | C36—C37—H37 | 119.7 |
C17—C16—C15 | 120.40 (14) | C37—C38—C38a | 119.39 (15) |
C17a—C17—C16 | 117.81 (14) | C37—C38—H38 | 120.3 |
C17a—C17—H17 | 121.1 | C38a—C38—H38 | 120.3 |
C16—C17—H17 | 121.1 | N31—C38a—C38 | 120.73 (14) |
C17—C17a—O11 | 127.16 (15) | N31—C38a—C34a | 118.62 (14) |
C17—C17a—C13a | 122.58 (14) | C38—C38a—C34a | 120.65 (14) |
O1—C1—C2—C3 | −3.4 (2) | C1—C2—C3—C33 | −179.29 (14) |
C17a—O11—C12—O13 | 9.62 (17) | C2—C3—C33—C32 | 3.3 (3) |
O11—C12—O13—C13a | −9.42 (17) | C3—C2—C1—C15 | 176.75 (14) |
C12—O13—C13a—C17a | 5.76 (17) | C2—C1—C15—C14 | −7.9 (2) |
O13—C13a—C14—C15 | −178.41 (15) | C12—O13—C13a—C14 | −178.72 (16) |
C17a—C13a—C14—C15 | −3.3 (2) | C12—O11—C17a—C17 | 176.21 (16) |
C13a—C14—C15—C16 | 0.7 (2) | O32—C32—C33—C34 | −179.55 (15) |
C13a—C14—C15—C1 | 178.64 (14) | N31—C32—C33—C34 | 0.7 (2) |
O1—C1—C15—C16 | −9.8 (2) | O32—C32—C33—C3 | −0.8 (2) |
C2—C1—C15—C16 | 170.02 (14) | N31—C32—C33—C3 | 179.41 (13) |
O1—C1—C15—C14 | 172.27 (15) | C3—C33—C34—C34a | −179.41 (14) |
C14—C15—C16—N16 | −176.04 (14) | C32—C33—C34—C34a | −0.6 (2) |
C1—C15—C16—N16 | 6.0 (2) | C33—C34—C34a—C38a | 1.1 (2) |
C14—C15—C16—C17 | 3.1 (2) | C33—C34—C34a—C35 | −179.78 (15) |
C1—C15—C16—C17 | −174.81 (13) | C38a—C34a—C35—C36 | 1.2 (2) |
N16—C16—C17—C17a | 174.87 (14) | C34—C34a—C35—C36 | −177.92 (15) |
C15—C16—C17—C17a | −4.3 (2) | C34a—C35—C36—C37 | −0.7 (2) |
C16—C17—C17a—O11 | 179.15 (14) | C35—C36—C37—C38 | −0.5 (2) |
C16—C17—C17a—C13a | 1.8 (2) | C36—C37—C38—C38a | 1.0 (2) |
C12—O11—C17a—C13a | −6.14 (18) | C32—N31—C38a—C38 | −178.25 (14) |
C14—C13a—C17a—C17 | 2.1 (3) | C32—N31—C38a—C34a | 1.7 (2) |
O13—C13a—C17a—C17 | 178.04 (14) | C37—C38—C38a—N31 | 179.64 (14) |
C14—C13a—C17a—O11 | −175.64 (14) | C37—C38—C38a—C34a | −0.3 (2) |
O13—C13a—C17a—O11 | 0.26 (18) | C35—C34a—C38a—N31 | 179.27 (14) |
C38a—N31—C32—O32 | 178.93 (14) | C34—C34a—C38a—N31 | −1.5 (2) |
C38a—N31—C32—C33 | −1.3 (2) | C35—C34a—C38a—C38 | −0.7 (2) |
C2—C3—C33—C34 | −177.95 (15) | C34—C34a—C38a—C38 | 178.47 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
N16—H16B···O1 | 0.91 (2) | 1.90 (2) | 2.620 (2) | 135 (2) |
N31—H31···O32i | 0.88 | 1.89 | 2.768 (2) | 176 |
C35—H35···O1ii | 0.95 | 2.38 | 3.334 (2) | 177 |
Symmetry codes: (i) −x−1, −y+1, −z+1; (ii) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C19H14N2O4 |
Mr | 334.32 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 120 |
a, b, c (Å) | 5.7799 (2), 9.9485 (3), 13.0849 (5) |
α, β, γ (°) | 83.343 (2), 86.652 (2), 77.128 (2) |
V (Å3) | 728.13 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.10 × 0.06 × 0.06 |
Data collection | |
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.989, 0.994 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9539, 2858, 2377 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.618 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.112, 1.05 |
No. of reflections | 2858 |
No. of parameters | 232 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.23, −0.24 |
Computer programs: COLLECT (Nonius, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
C13a—C14 | 1.359 (2) | N31—C32 | 1.364 (2) |
C14—C15 | 1.430 (2) | C32—C33 | 1.469 (2) |
C15—C16 | 1.423 (2) | C33—C34 | 1.368 (2) |
C16—C17 | 1.416 (2) | C34—C34a | 1.426 (2) |
C17—C17a | 1.363 (2) | C34a—C35 | 1.410 (2) |
C13a—C17a | 1.386 (2) | C35—C36 | 1.368 (2) |
C16—N16 | 1.375 (2) | C36—C37 | 1.406 (2) |
C15—C1 | 1.472 (2) | C37—C38 | 1.375 (2) |
C1—O1 | 1.2403 (19) | C38—C38a | 1.398 (2) |
C1—C2 | 1.483 (2) | C38a—N31 | 1.3777 (19) |
C2—C3 | 1.340 (2) | C34a—C38a | 1.403 (2) |
C3—C33 | 1.453 (2) | C32—O32 | 1.2488 (18) |
C1—C2—C3—C33 | −179.29 (14) | C2—C1—C15—C14 | −7.9 (2) |
C2—C3—C33—C32 | 3.3 (3) | C12—O13—C13a—C14 | −178.72 (16) |
C3—C2—C1—C15 | 176.75 (14) | C12—O11—C17a—C17 | 176.21 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N16—H16B···O1 | 0.91 (2) | 1.90 (2) | 2.620 (2) | 135 (2) |
N31—H31···O32i | 0.88 | 1.89 | 2.768 (2) | 176 |
C35—H35···O1ii | 0.95 | 2.38 | 3.334 (2) | 177 |
Symmetry codes: (i) −x−1, −y+1, −z+1; (ii) −x+1, −y, −z+1. |
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We report here the molecular and supramolecular structure of the title compound, (I) (Fig. 1). Dioxolotetrahydroquinolin-8-one units are found in a number of compounds used as antimitotic and antitumour agents (Prager & Thredgold, 1968; Donnelly & Farell, 1990; Kurasawa et al., 2002; Zhang et al., 2000), and 2-aminochalcones are useful intermediates for the synthesis of such quinolinone derivatives. Several years ago we reported the molecular and supramolecular structures of a number of such 2-aminochalcones (Low, Cobo, Nogueras et al., 2004), compounds (II)–(VI) (see scheme), and of some quinolinones formed by their acid-catalysed cyclization (Low, Cobo, Cuervo et al., 2004). Compound (I), in which the terminal substituted aryl group present in compounds (II)–(VI) has been replaced by a 2-oxoquinolin-3-yl unit, was prepared by a base-catalysed condensation between an acetophenone and an aldehyde, for use as an intermediate in the synthesis of the corresponding dihydroquinolin-8-one by 6-endo intramolecular cyclization (Low, Cobo, Cuervo et al., 2004; Abonía et al., 2008).
Compound (I) crystallizes with Z' = 1, as do (II), (VI) and the monoclinic polymorph of (III) (Low, Cobo, Nogueras et al., 2004). On the other hand, the triclinic polymorph of (III), and (IV) and (V), all crystallize with Z' = 2. No simple explanation of this behaviour presents itself. Within the molecule of (I), the spacer unit joining the two ring systems adopts an effectively planar all-trans configuration, and the two adjacent rings are almost coplanar with the spacer unit, as shown by the key torsion angles (Table 1). This planarity permits, but not does require, extensive electronic delocalization. The sole exception to the skeletal planarity is found in the dioxolane ring, where atom C12 is modestly displaced by 0.057 (2) Å from the mean plane of this ring, corresponding to an envelope fold across the line O11···O13.
In the aryl ring C13a/C14–C17/C17a, the C13a—C14 and C17—C17a bonds are both significantly shorter than the other four C—C distances in this ring (Table 1). At the same time, the C1—O1 bond is long for its type [mean value (Allen et al., 1987) 1.222 Å] and the C1—C15 bond is short for its type (mean value 1.488 Å). The C15—C16 bond is one of the longer ones in this aryl ring, and the C16—N16 bond is also short for its type (mean value 1.394 Å, lower quartile value 1.385 Å). Similar patterns of distances were observed in the corresponding molecular fragments in compounds (II)-(VI) (Low, Cobo, Nogueras et al., 2004). The C—C distances in the quinoline portion of the molecule provide evidence for bond fixation, as the C35—C36 and C37—C38 bonds are shorter than the other bonds in this carbocyclic ring. These observations, taken as a whole, indicate that the form (Ia) is a significant contributor to the overall electronic structure, in addition to form (I), although there appears to be no electronic delocalization between the two ring systems despite the planarity of the molecular skeleton.
There is an intramolecular hydrogen bond (Table 2) forming an S(6) motif (Bernstein et al., 1995), which may be regarded as charge-assisted (Gilli et al., 1994), but the second N—H bond of the amino group plays no role in the intermolecular hydrogen bonding, as there is no potential acceptor within plausible hydrogen-bonding distance. Instead, the molecules are linked by one N—H···O hydrogen bond, using the quinolinone N—H bond, and one C—H···O hydrogen bond, both almost linear (Table 2), into a chain containing two types of centrosymmetric ring. Rings of R22(8) type built from paired N—H···O hydrogen bonds are centred at (2n - 1/2, -n + 1/2, 1/2), where n represents an integer, and these alternate with R22(18) rings built from paired C—H···O hydrogen bonds and centred at (2n + 1/2, -n, 1/2), where n again represents an integer, so forming a chain running parallel to the [210] direction (Fig. 2).
A single aromatic π–π stacking interaction links, albeit fairly weakly, the hydrogen-bonded chains into a sheet. The rings C13a/C14–C17/C17a in the molecules at (x, y, z) and (1 - x, - y, 1 - z) are strictly parallel, with an interplanar spacing of 3.641 (2) Å. The ring centroid separation is 3.812 (2) Å, corresponding to a ring-centroid offset of 1.131 (2) Å. The effect of this interaction, when propagated by inversion, is to link the chains parallel to [210] into a sheet parallel to (122) (Fig. 2), but there are no direction-specific interactions between adjacent sheets. In this context, it is interesting to note that not only does the amino group play no role in the intermolecular aggregation, but neither do atoms O11 and O13.
The formation of sheets generated by the π-stacking of hydrogen-bonded chains was also observed in (IV) and (VI) (Low, Cobo, Nogueras et al., 2004), although in each of these structures the chains are simple chains of C(7) and C(10) types, as opposed to the chains of rings observed here in (I). In both (II) and the monoclinic polymorph of (III), a combination of N—H···O and C—H···π(arene) hydrogen bonds forms the sheet structures directly, without any π–π stacking. By contrast, in the triclinic polymorph of (III), the structure is built from simple C(8) chains without any π–π stacking, while in (V) the molecules are linked by N—H···O hydrogen bonds into centrosymmetric tetramers. Thus within this series of compounds, (I)–(VI), the hydrogen-bonding can give rise to aggregation in zero, one or two dimensions. This variation, combined with the differing Z' values, points to considerable structural diversity within this series of rather closely related compounds.