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organic compounds
2-Bromomethyl-N-isopropyl-7,8-dimethoxy-1,2-dihydro-1,3-oxazolo[3,2-a]quinoline-4-carboxamide
aSTC "Institute for Single Crystals", National Academy of Sciences of Ukraine, 60 Lenina ave., Kharkiv 61001, Ukraine, and bNational University of Pharmacy, 4 Blyukhera ave., Kharkiv 61002, Ukraine
*Correspondence e-mail: sveta@xray.isc.kharkov.com
In the title compound, C18H21BrN2O5, conjugation between the π-donating N—C—O fragment and the π-withdrawing carbonyl group results in considerable redistribution of the electron density within the dihydropyridinol ring. This effect is also promoted by the formation of an intramolecular N—H⋯O hydrogen bond. The five-membered heterocycle is disordered over two envelope conformations in a 0.35:0.65 ratio.
Related literature
For related literature, see: Ukrainets et al. (2007a,b
); Bürgi & Dunitz (1994
); Hutcheon & James (1977
).
Experimental
Crystal data
|
Refinement
|
|
Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell CrysAlis RED (Oxford Diffraction, 2005
); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXTL (Sheldrick, 2008
); program(s) used to refine structure: SHELXTL; molecular graphics: XP (Siemens, 1998
); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536808013378/kp2166sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808013378/kp2166Isup2.hkl
To a stirred solution of the 1-allyl-4-hydroxy-6,7-dimethoxy-2-oxo- 1,2-dihydroquinoline-3-carboxylic acid isopropylamide (3.46 g, 10.0 mmol) in acetic acid (70 ml) was added bromine (0.52 ml, 10.0 mmol) (the solution turned to be colourless). The mixture was diluted with water. The precipitate formed was filtered off, washed with cold water and dried. Yield 3.95 g (93%). m.p. 542–544 K.
All hydrogen atoms were calculated geometrically and included in the
in the riding motion approximation with Uiso constrained to be 1.5 times Ueq of the for the methyl groups and 1.2 times Ueq of the for the other atoms. During the O-Csp3 and Csp3-Csp3 bonds in the disordered fragment were constrained to 1.44 (1) Å and 1.54 (1) Å, respectively.Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell
CrysAlis RED (Oxford Diffraction, 2005); data reduction: CrysAlis RED (Oxford Diffraction, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: XP (Siemens, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C18H21BrN2O5 | Z = 2 |
Mr = 425.28 | F(000) = 436 |
Triclinic, P1 | Dx = 1.576 Mg m−3 |
a = 8.736 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.968 (2) Å | Cell parameters from 2385 reflections |
c = 10.588 (3) Å | θ = 4–32° |
α = 86.90 (2)° | µ = 2.33 mm−1 |
β = 80.90 (2)° | T = 100 K |
γ = 80.04 (2)° | Plate, colourless |
V = 896.4 (4) Å3 | 0.60 × 0.40 × 0.10 mm |
Oxford Diffraction Xcalibur3 diffractometer | 3105 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 2701 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.089 |
Detector resolution: 16.1827 pixels mm-1 | θmax = 25.0°, θmin = 3.3° |
ω scans | h = −10→10 |
Absorption correction: analytical (Alcock, 1970) | k = −11→11 |
Tmin = 0.287, Tmax = 0.793 | l = −12→12 |
6292 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)] = 0.066 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.171 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0978P)2 + 1.3451P] where P = (Fo2 + 2Fc2)/3 |
3105 reflections | (Δ/σ)max < 0.001 |
258 parameters | Δρmax = 1.76 e Å−3 |
6 restraints | Δρmin = −0.88 e Å−3 |
C18H21BrN2O5 | γ = 80.04 (2)° |
Mr = 425.28 | V = 896.4 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.736 (2) Å | Mo Kα radiation |
b = 9.968 (2) Å | µ = 2.33 mm−1 |
c = 10.588 (3) Å | T = 100 K |
α = 86.90 (2)° | 0.60 × 0.40 × 0.10 mm |
β = 80.90 (2)° |
Oxford Diffraction Xcalibur3 diffractometer | 3105 independent reflections |
Absorption correction: analytical (Alcock, 1970) | 2701 reflections with I > 2σ(I) |
Tmin = 0.287, Tmax = 0.793 | Rint = 0.089 |
6292 measured reflections |
R[F2 > 2σ(F2)] = 0.066 | 6 restraints |
wR(F2) = 0.171 | H-atom parameters constrained |
S = 1.05 | Δρmax = 1.76 e Å−3 |
3105 reflections | Δρmin = −0.88 e Å−3 |
258 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Br1 | 0.34636 (6) | 0.06689 (5) | 0.11180 (4) | 0.0383 (2) | |
N1 | 0.2519 (5) | 0.3824 (4) | 0.4324 (3) | 0.0265 (8) | |
N2 | −0.0961 (4) | 0.3493 (4) | 0.8290 (3) | 0.0225 (8) | |
H2A | −0.0854 | 0.4337 | 0.8407 | 0.027* | |
O1 | 0.1378 (4) | 0.2004 (3) | 0.4688 (3) | 0.0292 (7) | |
O2 | −0.0441 (4) | 0.1744 (3) | 0.6927 (3) | 0.0308 (8) | |
O3 | 0.0389 (4) | 0.5646 (3) | 0.7631 (3) | 0.0298 (7) | |
O4 | 0.3952 (4) | 0.8815 (3) | 0.5332 (3) | 0.0256 (7) | |
O5 | 0.5279 (4) | 0.7664 (3) | 0.3238 (3) | 0.0262 (7) | |
C1 | 0.2878 (5) | 0.5081 (4) | 0.4564 (4) | 0.0222 (9) | |
C2 | 0.3940 (5) | 0.5707 (4) | 0.3692 (4) | 0.0228 (9) | |
H2B | 0.4432 | 0.5282 | 0.2916 | 0.027* | |
C3 | 0.4256 (5) | 0.6961 (4) | 0.3988 (4) | 0.0216 (9) | |
C4 | 0.3527 (5) | 0.7586 (4) | 0.5161 (4) | 0.0233 (9) | |
C5 | 0.2488 (5) | 0.6966 (4) | 0.5983 (4) | 0.0243 (9) | |
H5A | 0.1987 | 0.7400 | 0.6753 | 0.029* | |
C6 | 0.2142 (5) | 0.5693 (4) | 0.5715 (4) | 0.0226 (9) | |
C7 | 0.1030 (5) | 0.5046 (5) | 0.6613 (4) | 0.0237 (9) | |
C8 | 0.0756 (5) | 0.3709 (4) | 0.6301 (4) | 0.0223 (9) | |
C9 | 0.1530 (5) | 0.3193 (4) | 0.5138 (4) | 0.0239 (9) | |
C10A | 0.1932 (13) | 0.2038 (11) | 0.3329 (6) | 0.034 (4) | 0.352 (14) |
H10A | 0.1049 | 0.2361 | 0.2832 | 0.041* | 0.352 (14) |
C12A | 0.2721 (17) | 0.0571 (12) | 0.2995 (14) | 0.034 (4) | 0.352 (14) |
H12A | 0.1958 | −0.0067 | 0.3198 | 0.040* | 0.352 (14) |
H12B | 0.3614 | 0.0269 | 0.3471 | 0.040* | 0.352 (14) |
C10B | 0.2633 (7) | 0.1653 (5) | 0.3608 (5) | 0.0207 (18) | 0.648 (14) |
H10B | 0.3527 | 0.0973 | 0.3854 | 0.025* | 0.648 (14) |
C12B | 0.1808 (8) | 0.1107 (7) | 0.2615 (5) | 0.0202 (19) | 0.648 (14) |
H12C | 0.0939 | 0.1804 | 0.2379 | 0.024* | 0.648 (14) |
H12D | 0.1376 | 0.0282 | 0.2954 | 0.024* | 0.648 (14) |
C11 | 0.3126 (5) | 0.3038 (4) | 0.3165 (4) | 0.0264 (10) | |
H11B | 0.4217 | 0.2559 | 0.3170 | 0.032* | 0.352 (14) |
H11A | 0.3070 | 0.3614 | 0.2376 | 0.032* | 0.352 (14) |
H11C | 0.4281 | 0.2960 | 0.2944 | 0.032* | 0.648 (14) |
H11D | 0.2623 | 0.3439 | 0.2425 | 0.032* | 0.648 (14) |
C13 | −0.0266 (5) | 0.2875 (4) | 0.7177 (4) | 0.0219 (9) | |
C14 | −0.1879 (5) | 0.2772 (5) | 0.9286 (4) | 0.0259 (9) | |
H14A | −0.2515 | 0.2222 | 0.8880 | 0.031* | |
C15 | −0.2986 (6) | 0.3822 (5) | 1.0142 (5) | 0.0344 (11) | |
H15A | −0.3679 | 0.4416 | 0.9627 | 0.052* | |
H15B | −0.2369 | 0.4371 | 1.0534 | 0.052* | |
H15C | −0.3621 | 0.3353 | 1.0813 | 0.052* | |
C16 | −0.0800 (7) | 0.1829 (6) | 1.0052 (5) | 0.0425 (13) | |
H16A | −0.0101 | 0.1164 | 0.9485 | 0.064* | |
H16B | −0.1428 | 0.1350 | 1.0720 | 0.064* | |
H16C | −0.0169 | 0.2362 | 1.0449 | 0.064* | |
C17 | 0.3101 (5) | 0.9556 (4) | 0.6430 (4) | 0.0260 (9) | |
H17A | 0.3497 | 1.0412 | 0.6470 | 0.039* | |
H17B | 0.3248 | 0.9005 | 0.7210 | 0.039* | |
H17C | 0.1980 | 0.9754 | 0.6356 | 0.039* | |
C18 | 0.6008 (5) | 0.7119 (5) | 0.2022 (4) | 0.0263 (9) | |
H18A | 0.6710 | 0.7723 | 0.1586 | 0.039* | |
H18B | 0.5196 | 0.7050 | 0.1499 | 0.039* | |
H18C | 0.6615 | 0.6213 | 0.2151 | 0.039* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0475 (4) | 0.0419 (4) | 0.0227 (3) | −0.0146 (2) | 0.0145 (2) | −0.0105 (2) |
N1 | 0.030 (2) | 0.033 (2) | 0.0146 (17) | −0.0092 (15) | 0.0090 (15) | −0.0082 (15) |
N2 | 0.0215 (18) | 0.0273 (19) | 0.0159 (17) | −0.0045 (14) | 0.0062 (14) | −0.0004 (14) |
O1 | 0.0334 (18) | 0.0305 (17) | 0.0208 (16) | −0.0113 (13) | 0.0137 (13) | −0.0070 (13) |
O2 | 0.0341 (18) | 0.0302 (17) | 0.0258 (16) | −0.0107 (13) | 0.0104 (14) | −0.0068 (13) |
O3 | 0.0322 (17) | 0.0343 (17) | 0.0224 (16) | −0.0134 (13) | 0.0074 (14) | −0.0053 (13) |
O4 | 0.0254 (16) | 0.0266 (15) | 0.0233 (16) | −0.0063 (12) | 0.0047 (13) | −0.0056 (13) |
O5 | 0.0280 (16) | 0.0304 (16) | 0.0191 (15) | −0.0113 (13) | 0.0077 (13) | −0.0023 (12) |
C1 | 0.020 (2) | 0.027 (2) | 0.019 (2) | −0.0027 (16) | −0.0005 (17) | −0.0025 (17) |
C2 | 0.020 (2) | 0.031 (2) | 0.0145 (19) | −0.0028 (16) | 0.0039 (16) | −0.0006 (17) |
C3 | 0.018 (2) | 0.029 (2) | 0.016 (2) | −0.0027 (16) | 0.0026 (16) | 0.0019 (17) |
C4 | 0.020 (2) | 0.028 (2) | 0.021 (2) | −0.0046 (16) | −0.0007 (17) | −0.0006 (17) |
C5 | 0.023 (2) | 0.027 (2) | 0.021 (2) | −0.0021 (16) | 0.0023 (17) | −0.0060 (17) |
C6 | 0.018 (2) | 0.030 (2) | 0.018 (2) | −0.0022 (16) | 0.0017 (17) | −0.0033 (17) |
C7 | 0.021 (2) | 0.031 (2) | 0.018 (2) | −0.0030 (16) | −0.0004 (17) | −0.0033 (17) |
C8 | 0.023 (2) | 0.031 (2) | 0.0118 (19) | −0.0037 (16) | 0.0018 (17) | −0.0010 (16) |
C9 | 0.023 (2) | 0.028 (2) | 0.021 (2) | −0.0063 (17) | −0.0005 (18) | −0.0028 (17) |
C10A | 0.029 (9) | 0.038 (9) | 0.034 (9) | −0.010 (7) | 0.002 (7) | 0.003 (7) |
C12A | 0.030 (8) | 0.040 (9) | 0.031 (8) | −0.011 (7) | 0.002 (6) | −0.017 (6) |
C10B | 0.020 (4) | 0.020 (4) | 0.018 (4) | 0.002 (3) | 0.003 (3) | 0.003 (3) |
C12B | 0.016 (4) | 0.031 (4) | 0.016 (3) | −0.013 (3) | 0.002 (3) | −0.004 (3) |
C11 | 0.028 (2) | 0.032 (2) | 0.018 (2) | −0.0109 (18) | 0.0104 (18) | −0.0082 (18) |
C13 | 0.017 (2) | 0.027 (2) | 0.019 (2) | −0.0014 (16) | 0.0020 (17) | −0.0020 (17) |
C14 | 0.025 (2) | 0.032 (2) | 0.018 (2) | −0.0069 (18) | 0.0061 (18) | −0.0017 (17) |
C15 | 0.028 (2) | 0.040 (3) | 0.030 (3) | −0.002 (2) | 0.009 (2) | −0.005 (2) |
C16 | 0.048 (3) | 0.038 (3) | 0.031 (3) | 0.006 (2) | 0.008 (2) | 0.006 (2) |
C17 | 0.025 (2) | 0.027 (2) | 0.024 (2) | −0.0041 (17) | 0.0018 (18) | −0.0041 (18) |
C18 | 0.023 (2) | 0.035 (2) | 0.019 (2) | −0.0080 (18) | 0.0050 (18) | 0.0002 (18) |
Br1—C12B | 1.981 (6) | C10A—C12A | 1.539 (5) |
Br1—C12A | 1.99 (1) | C10A—C11 | 1.547 (5) |
N1—C9 | 1.334 (6) | C10A—H10A | 1.000 |
N1—C1 | 1.388 (6) | C12A—H12A | 0.990 |
N1—C11 | 1.469 (5) | C12A—H12B | 0.990 |
N2—C13 | 1.363 (5) | C10B—C12B | 1.535 (5) |
N2—C14 | 1.457 (5) | C10B—C11 | 1.544 (4) |
N2—H2A | 0.880 | C10B—H10B | 1.000 |
O1—C9 | 1.336 (5) | C12B—H12C | 0.990 |
O1—C10A | 1.445 (5) | C12B—H12D | 0.990 |
O1—C10B | 1.465 (4) | C11—H11B | 0.990 |
O2—C13 | 1.212 (5) | C11—H11A | 0.990 |
O3—C7 | 1.263 (5) | C11—H11C | 0.990 |
O4—C4 | 1.369 (5) | C11—H11D | 0.990 |
O4—C17 | 1.442 (5) | C14—C16 | 1.511 (7) |
O5—C3 | 1.361 (5) | C14—C15 | 1.525 (6) |
O5—C18 | 1.433 (5) | C14—H14A | 1.000 |
C1—C6 | 1.403 (6) | C15—H15A | 0.980 |
C1—C2 | 1.403 (6) | C15—H15B | 0.980 |
C2—C3 | 1.387 (6) | C15—H15C | 0.980 |
C2—H2B | 0.950 | C16—H16A | 0.980 |
C3—C4 | 1.426 (6) | C16—H16B | 0.980 |
C4—C5 | 1.360 (6) | C16—H16C | 0.980 |
C5—C6 | 1.408 (6) | C17—H17A | 0.980 |
C5—H5A | 0.950 | C17—H17B | 0.980 |
C6—C7 | 1.456 (6) | C17—H17C | 0.980 |
C7—C8 | 1.458 (6) | C18—H18A | 0.980 |
C8—C9 | 1.386 (6) | C18—H18B | 0.980 |
C8—C13 | 1.503 (6) | C18—H18C | 0.980 |
C9—N1—C1 | 122.8 (4) | C10B—C12B—H12C | 110.7 |
C9—N1—C11 | 111.5 (3) | Br1—C12B—H12C | 110.7 |
C1—N1—C11 | 125.6 (3) | C10B—C12B—H12D | 110.7 |
C13—N2—C14 | 120.8 (4) | Br1—C12B—H12D | 110.7 |
C13—N2—H2A | 119.6 | H12C—C12B—H12D | 108.8 |
C14—N2—H2A | 119.6 | N1—C11—C10B | 100.3 (3) |
C9—O1—C10A | 107.1 (4) | N1—C11—C10A | 98.6 (4) |
C9—O1—C10B | 108.5 (3) | N1—C11—H11B | 112.0 |
C4—O4—C17 | 115.8 (3) | C10B—C11—H11B | 85.6 |
C3—O5—C18 | 118.0 (3) | C10A—C11—H11B | 112.0 |
N1—C1—C6 | 117.2 (4) | N1—C11—H11A | 112.0 |
N1—C1—C2 | 121.3 (4) | C10B—C11—H11A | 134.1 |
C6—C1—C2 | 121.5 (4) | C10A—C11—H11A | 112.0 |
C3—C2—C1 | 118.6 (4) | H11B—C11—H11A | 109.7 |
C3—C2—H2B | 120.7 | N1—C11—H11C | 111.7 |
C1—C2—H2B | 120.7 | C10B—C11—H11C | 111.7 |
O5—C3—C2 | 124.4 (4) | C10A—C11—H11C | 135.7 |
O5—C3—C4 | 115.1 (4) | H11A—C11—H11C | 86.1 |
C2—C3—C4 | 120.4 (4) | N1—C11—H11D | 111.7 |
C5—C4—O4 | 125.9 (4) | C10B—C11—H11D | 111.7 |
C5—C4—C3 | 119.9 (4) | C10A—C11—H11D | 86.6 |
O4—C4—C3 | 114.2 (4) | H11B—C11—H11D | 128.5 |
C4—C5—C6 | 121.2 (4) | H11C—C11—H11D | 109.5 |
C4—C5—H5A | 119.4 | O2—C13—N2 | 122.8 (4) |
C6—C5—H5A | 119.4 | O2—C13—C8 | 123.1 (4) |
C1—C6—C5 | 118.4 (4) | N2—C13—C8 | 114.2 (4) |
C1—C6—C7 | 121.4 (4) | N2—C14—C16 | 110.1 (4) |
C5—C6—C7 | 120.2 (4) | N2—C14—C15 | 108.4 (4) |
O3—C7—C6 | 118.9 (4) | C16—C14—C15 | 110.9 (4) |
O3—C7—C8 | 123.4 (4) | N2—C14—H14A | 109.1 |
C6—C7—C8 | 117.7 (4) | C16—C14—H14A | 109.1 |
C9—C8—C7 | 116.5 (4) | C15—C14—H14A | 109.1 |
C9—C8—C13 | 119.8 (4) | C14—C15—H15A | 109.5 |
C7—C8—C13 | 123.7 (4) | C14—C15—H15B | 109.5 |
N1—C9—O1 | 111.4 (4) | H15A—C15—H15B | 109.5 |
N1—C9—C8 | 124.2 (4) | C14—C15—H15C | 109.5 |
O1—C9—C8 | 124.4 (4) | H15A—C15—H15C | 109.5 |
O1—C10A—C12A | 105.8 (8) | H15B—C15—H15C | 109.5 |
O1—C10A—C11 | 104.2 (4) | C14—C16—H16A | 109.5 |
C12A—C10A—C11 | 112.4 (9) | C14—C16—H16B | 109.5 |
O1—C10A—H10A | 111.4 | H16A—C16—H16B | 109.5 |
C12A—C10A—H10A | 111.4 | C14—C16—H16C | 109.5 |
C11—C10A—H10A | 111.4 | H16A—C16—H16C | 109.5 |
C10A—C12A—Br1 | 104.3 (8) | H16B—C16—H16C | 109.5 |
C10A—C12A—H12A | 110.9 | O4—C17—H17A | 109.5 |
Br1—C12A—H12A | 110.9 | O4—C17—H17B | 109.5 |
C10A—C12A—H12B | 110.9 | H17A—C17—H17B | 109.5 |
Br1—C12A—H12B | 110.9 | O4—C17—H17C | 109.5 |
H12A—C12A—H12B | 108.9 | H17A—C17—H17C | 109.5 |
O1—C10B—C12B | 104.0 (4) | H17B—C17—H17C | 109.5 |
O1—C10B—C11 | 103.4 (3) | O5—C18—H18A | 109.5 |
C12B—C10B—C11 | 111.4 (5) | O5—C18—H18B | 109.5 |
O1—C10B—H10B | 112.4 | H18A—C18—H18B | 109.5 |
C12B—C10B—H10B | 112.4 | O5—C18—H18C | 109.5 |
C11—C10B—H10B | 112.4 | H18A—C18—H18C | 109.5 |
C10B—C12B—Br1 | 105.1 (4) | H18B—C18—H18C | 109.5 |
C9—N1—C1—C6 | −0.5 (7) | C1—N1—C9—C8 | 0.0 (7) |
C11—N1—C1—C6 | 178.1 (4) | C11—N1—C9—C8 | −178.8 (4) |
C9—N1—C1—C2 | 179.2 (4) | C10A—O1—C9—N1 | −18.1 (7) |
C11—N1—C1—C2 | −2.2 (7) | C10B—O1—C9—N1 | 13.6 (5) |
N1—C1—C2—C3 | −179.7 (4) | C10A—O1—C9—C8 | 161.7 (7) |
C6—C1—C2—C3 | −0.1 (7) | C10B—O1—C9—C8 | −166.6 (5) |
C18—O5—C3—C2 | 4.1 (6) | C7—C8—C9—N1 | 1.7 (7) |
C18—O5—C3—C4 | −177.6 (4) | C13—C8—C9—N1 | −176.6 (4) |
C1—C2—C3—O5 | 178.9 (4) | C7—C8—C9—O1 | −178.1 (4) |
C1—C2—C3—C4 | 0.7 (6) | C13—C8—C9—O1 | 3.6 (7) |
C17—O4—C4—C5 | −6.1 (6) | C9—O1—C10A—C12A | 145.3 (7) |
C17—O4—C4—C3 | 172.8 (4) | C9—O1—C10A—C11 | 26.6 (9) |
O5—C3—C4—C5 | −179.8 (4) | O1—C10A—C12A—Br1 | −180.0 (6) |
C2—C3—C4—C5 | −1.4 (7) | C11—C10A—C12A—Br1 | −66.9 (9) |
O5—C3—C4—O4 | 1.2 (6) | C9—O1—C10B—C12B | −138.0 (5) |
C2—C3—C4—O4 | 179.6 (4) | C9—O1—C10B—C11 | −21.5 (5) |
O4—C4—C5—C6 | −179.6 (4) | O1—C10B—C12B—Br1 | 178.5 (3) |
C3—C4—C5—C6 | 1.6 (7) | C11—C10B—C12B—Br1 | 67.7 (5) |
N1—C1—C6—C5 | 179.8 (4) | C9—N1—C11—C10B | −13.9 (5) |
C2—C1—C6—C5 | 0.2 (7) | C1—N1—C11—C10B | 167.4 (5) |
N1—C1—C6—C7 | −0.9 (6) | C9—N1—C11—C10A | 14.8 (7) |
C2—C1—C6—C7 | 179.5 (4) | C1—N1—C11—C10A | −164.0 (6) |
C4—C5—C6—C1 | −0.9 (7) | O1—C10B—C11—N1 | 20.3 (5) |
C4—C5—C6—C7 | 179.8 (4) | C12B—C10B—C11—N1 | 131.5 (5) |
C1—C6—C7—O3 | −179.4 (4) | O1—C10A—C11—N1 | −24.0 (8) |
C5—C6—C7—O3 | −0.1 (7) | C12A—C10A—C11—N1 | −138.1 (8) |
C1—C6—C7—C8 | 2.6 (6) | C14—N2—C13—O2 | 4.3 (7) |
C5—C6—C7—C8 | −178.2 (4) | C14—N2—C13—C8 | −174.8 (4) |
O3—C7—C8—C9 | 179.1 (4) | C9—C8—C13—O2 | 0.9 (7) |
C6—C7—C8—C9 | −2.9 (6) | C7—C8—C13—O2 | −177.3 (4) |
O3—C7—C8—C13 | −2.6 (7) | C9—C8—C13—N2 | 180.0 (4) |
C6—C7—C8—C13 | 175.4 (4) | C7—C8—C13—N2 | 1.7 (6) |
C1—N1—C9—O1 | 179.8 (4) | C13—N2—C14—C16 | 79.8 (5) |
C11—N1—C9—O1 | 1.0 (5) | C13—N2—C14—C15 | −158.7 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O3 | 0.88 | 1.91 | 2.634 (5) | 138 |
C10A—H10A···O3i | 1.00 | 2.23 | 3.042 | 137 |
C12A—H12A···O2ii | 0.99 | 2.33 | 3.289 | 164 |
C12A—H12B···O4iii | 0.99 | 2.41 | 3.173 | 134 |
C12B—H12D···O2ii | 0.99 | 2.30 | 3.253 | 162 |
C17—H17A···O5iv | 0.98 | 2.41 | 3.380 | 172 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y, −z+1; (iii) x, y−1, z; (iv) −x+1, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C18H21BrN2O5 |
Mr | 425.28 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 8.736 (2), 9.968 (2), 10.588 (3) |
α, β, γ (°) | 86.90 (2), 80.90 (2), 80.04 (2) |
V (Å3) | 896.4 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.33 |
Crystal size (mm) | 0.60 × 0.40 × 0.10 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur3 diffractometer |
Absorption correction | Analytical (Alcock, 1970) |
Tmin, Tmax | 0.287, 0.793 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6292, 3105, 2701 |
Rint | 0.089 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.066, 0.171, 1.05 |
No. of reflections | 3105 |
No. of parameters | 258 |
No. of restraints | 6 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.76, −0.88 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2005), CrysAlis RED (Oxford Diffraction, 2005), SHELXTL (Sheldrick, 2008), XP (Siemens, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O3 | 0.88 | 1.91 | 2.634 (5) | 138.4 |
C10A—H10A···O3i | 1.00 | 2.23 | 3.042 | 136.9 |
C12A—H12A···O2ii | 0.99 | 2.33 | 3.289 | 163.5 |
C12A—H12B···O4iii | 0.99 | 2.41 | 3.173 | 133.6 |
C12B—H12D···O2ii | 0.99 | 2.30 | 3.253 | 162.1 |
C17—H17A···O5iv | 0.98 | 2.41 | 3.380 | 171.8 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y, −z+1; (iii) x, y−1, z; (iv) −x+1, −y+2, −z+1. |
References
Alcock, N. W. (1970). Crystallographic Computing, edited by F. R. Ahmed, S. R. Hall & C. P. Huber, p. 271. Copenhagen: Munksgaard. Google Scholar
Bürgi, H.-B. & Dunitz, J. D. (1994). Structure Correlation, Vol. 2, pp. 767–784. Weinheim: VCH. Google Scholar
Hutcheon, W. L. B. & James, M. N. G. (1977). Acta Cryst. B33, 2228–2232. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Oxford Diffraction (2005). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, Oxfordshire, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1998). XP. Siemens Analytical X-ray Division Inc., Karlsruhe, Germany. Google Scholar
Ukrainets, I. V., Bereznyakova, L. V., Turov, A. V. & Shihkina, S. V. (2007a). Khim. Geterotsikl. Soedin. pp. 1034–1042. Google Scholar
Ukrainets, I. V., Sidorenko, L. V., Gorokhova, O. V., Shishkina, S. V. & Turov, A. V. (2007b). Khim. Geterotsikl. Soedin. pp. 736–749. Google Scholar
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2-Bromomethyl-5-oxo-1,2-dihydro-5H-oxazolo[3,2-a]quinoline-4- carboxylic acids are labile compounds. Therefore, their amidation are not always successful (Ukrainets et al., 2007a; Ukrainets et al., 2007b). However the heterocyclization of the previously synthesized N—R-amides of 1-allyl-4-hydroxy-2-oxo-1,2-dihydroquinoline-3-carboxylic acids was straightforward into the N—R-amides of oxazolo-quinoline-4-carboxylic acids (I) (Scheme 1). In the present paper, we report the crystal structure of the title compound, (I). The benzpyridone fragment and the O1, C11, O5, O4, O3, C13, O2, N2 atoms are cooplanar whithin 0.02 Å. The C7—O3 (1.263 (5) Å) and C8—C9 (1.386 (6) Å) bonds are elongated comparing to the values in the literature (1.210 Å and 1.326 Å; Burgi & Dunitz, 1994) whereas the C9—O1 (1.336 (5) Å) and N1—C9 (1.333 (6) Å) bonds are shorter than their mean values retrieved from the quoted references (1.354 Å and 1.336 Å). Such redistribution of the electron density can be explained by the conjugation interactions between the N1—C9—O1 π-donating fragment and the C7—O3 π-acceptor carbonyl group. Similar effect was observed earlier in related structure (Hucheon & James, 1977). The formation of the N2—H2N···O3 intramolecular hydrogen bond (Table 1) also promotes the elongation of the carbonyl bond. The five-membered heterocycle ring is disodered over two envelope conformations (A and B) with population A:B 35:65%. The deviation of the C10 atom from the mean plane of the remaining atoms of the ring is -0.41 Å in the conformer A and 0.35 Å in B. The bromomethyl substituent in both conformers is in a pseudo-equatorial orientation (the C9—O1—C10—C12 torsion angle is 145.1 (7) %A in A and -138.1 (5) %A in B). The bromine atom is not disordered and it is located in ap-position relatively to the O1—C10 bond in both conformers [the O1—C10—C12—Br1 torsion angle is -179.9 (6) %A (A) and 178.5 (3) %A (B)]. The methoxy groups at the C3 and C4 atoms are almost coplanar to the plane of the aromatic ring (the C18—O5—C3—C2 and C17—O4—C4—C5 torsion angles are 4.2 (6) %A and -6.2 (6) %A, respectively). The isopropyl group has ap-conformation relatively to the C8—C13 bond and it is turned away from the C13—N2 bond (the C14—N2—C13—C8 and C13—N2—C14—H14a torsion angles are 174.7 (4) %A and -40%A, respectively). In the crystal the molecules of the title compound form the three-dimensional network via intermolecular hydrogen bonds (Table 1). The shortened intermolecular contacts H14a···Br1i (i = -x,-y,1 - z) 3.13 Å (van der Waals sum 3.23 Å), H18c···C7ii (ii = 1 - x,1 - y,1 - z) 2.70 Å (2.87 Å), Br1···Br1iii (iii = 1 - x,-y,-z) 3.42 Å (3.94 Å) were observed in the crystal. Stacking interaction between parallel aromatic rings is observed [the shortest C3···C1ii (1 - x,1 - y,1 - z) distance is 3.45 Å].