organic compounds
Ethyl 5-bromo-9-ethoxy-2-oxo-2H-pyrano[2,3-g]quinoline-8-carboxylate
aInstituto de Química, Departamento de Química Inorgânica, Universidade Federal Fluminense, Outeiro de São João Batista s/n, Campus do Valonguinho–Centro, Niterói, RJ 24020-150, Brazil, bDepartment of Chemistry, College of Physical Sciences, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland, cDepartamento de Química Inorgânica, Instituto de Química, Universidade Federal do Rio de Janeiro, 21945-970 Rio de Janeiro, RJ, Brazil, and dLaboratory of Organic Synthesis of Far-Manguinhos/FIOCRUZ, R. Sizenando Nabuco, 100 Manguinhos, 21041-250 Rio de Janeiro, RJ, Brazil
*Correspondence e-mail: j.skakle@abdn.ac.uk
The title compound, C17H14BrNO5, was studied as part of a study on the biological properties of pyranoquinoline derivatives. Alkylation of the parent pyranoquinoline was shown to have occurred at the carbonyl rather than the amino site. The molecules are linked by a C—H⋯O hydrogen bond forming C(5) chains along [001].
Comment
As part of a study on the synthesis and biological activities of pyranoquinoline derivatives (da Matta et al., 2000; de Oliveira, 2003), alkylation of compound (1) (see scheme) using EtBr was carried out. Compound (1) contains two potential reaction sites, viz. the carbonyl and amino sites. While NMR spectroscopy strongly indicated that bromination had occurred predominantly at the carbonyl site to give the pyranoquinoline derivative (2), confirmation was sought using X-ray crystallography.
Structural analysis confirmed that alkylation had indeed occurred at the carbonyl site (Fig. 1). The pyranoquinoline ring system in (2) was confirmed.
Hydrogen bonding occurs via C9—H9⋯O11i [C9⋯O11i = 3.367 (4) Å and C9—H9⋯O11i = 148°; symmetry code: (i) 1 − x, −y, z − ], leading to C(5) chains (Bernstein et al., 1995) along [001] (Fig. 2).
The compound is isostructural with the chloro analogue (de Oliveira et al., 2006).
Experimental
The title compound was obtained from the reaction between EtBr and (1) in DMF solution in the presence of K2CO3 (de Oliveira, 2003). Pure product (2) was obtained from the reaction mixture by using hexane–ethyl acetate as the (gradient 1:4 to 1:1). Crystals suitable for X-ray crystallography were grown from ethyl acetate (67% yield; m.p. 409–410 K).
Crystal data
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All H atoms were located in difference maps and then treated as riding atoms, with C—H distances of 0.95 (aromatic) or 0.96 Å (methyl) and Uiso(H) values of 1.2Ueq(C) (aromatic) or 1.5Ueq(C) (methyl). PLATON (Spek, 2003) was used for the hydrogen-bonding analysis.
Data collection: SMART (Bruker, 1998); cell SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CIFTAB (Sheldrick, 1997).
Supporting information
https://doi.org/10.1107/S1600536806007148/wk2003sup1.cif
contains datablocks global, 2. DOI:Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S1600536806007148/wk20032sup2.hkl
Data collection: SMART (Bruker, 1998); cell
SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CIFTAB (Sheldrick, 1997).C17H14BrNO5 | F(000) = 792 |
Mr = 392.20 | Dx = 1.628 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 4263 reflections |
a = 7.2542 (8) Å | θ = 3.5–25.3° |
b = 19.542 (2) Å | µ = 2.60 mm−1 |
c = 11.2855 (11) Å | T = 291 K |
V = 1599.9 (3) Å3 | Prism, pale yellow |
Z = 4 | 0.42 × 0.22 × 0.11 mm |
Bruker SMART 1000 CCD area-detector diffractometer | 5296 independent reflections |
Radiation source: fine-focus sealed tube | 2737 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
ω scans | θmax = 32.5°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −10→10 |
Tmin = 0.549, Tmax = 0.752 | k = −27→29 |
15681 measured reflections | l = −17→14 |
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)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.069 | w = 1/[σ2(Fo2) + (0.034P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.80 | (Δ/σ)max < 0.001 |
5296 reflections | Δρmax = 0.35 e Å−3 |
219 parameters | Δρmin = −0.29 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.013 (7) |
Experimental. IR (KBr, cm-1): 2977, 1749, 1718, 1624, 1590, 1340, 1300. 1H NMR (DMSO-d6, 300 MHz): δ 1.51 (t, J = 7.2 Hz, 3H), 1.58 (t, J = 6.9 Hz, 3H), 4.43 (q, J = 6.9 Hz, 2H), 4.54 (q, J = 7.2 Hz, 2H), 6.89 (d, J = 9.9 Hz, 1H), 8.12 (s, 1H), 8.47 (d, J = 9.9 Hz, 1H), 9.19 (s, 1H). 13C NMR (DMSO-d6, 75 MHz): δ 14.1, 15.6, 61.9, 72.5, 108.7, 114.7, 120.7, 123.0, 15.1, 125.6, 142.1, 143.5, 150.7, 152.2, 158.7, 162.3, 164.4. |
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 | ||
C1 | 0.5465 (4) | 0.26565 (12) | 0.79440 (19) | 0.0403 (5) | |
C2 | 0.5712 (4) | 0.32561 (14) | 0.8664 (2) | 0.0431 (6) | |
O2 | 0.6179 (3) | 0.31203 (10) | 0.97852 (13) | 0.0573 (5) | |
C21 | 0.7329 (4) | 0.35662 (13) | 1.0487 (2) | 0.0532 (7) | |
H21A | 0.6590 | 0.3919 | 1.0861 | 0.064* | |
H21B | 0.8252 | 0.3784 | 0.9993 | 0.064* | |
C22 | 0.8232 (5) | 0.31265 (16) | 1.1406 (3) | 0.0746 (8) | |
H22A | 0.7308 | 0.2938 | 1.1920 | 0.112* | |
H22B | 0.9076 | 0.3398 | 1.1862 | 0.112* | |
H22C | 0.8890 | 0.2762 | 1.1024 | 0.112* | |
C3 | 0.5449 (4) | 0.38935 (12) | 0.8149 (2) | 0.0444 (6) | |
C31 | 0.5426 (4) | 0.45529 (14) | 0.8793 (2) | 0.0521 (7) | |
O31 | 0.6127 (3) | 0.50489 (9) | 0.81235 (17) | 0.0669 (6) | |
O32 | 0.4762 (3) | 0.46482 (10) | 0.97594 (16) | 0.0718 (6) | |
C32 | 0.5945 (5) | 0.57525 (15) | 0.8543 (3) | 0.0793 (10) | |
H32A | 0.6574 | 0.5808 | 0.9296 | 0.095* | |
H32B | 0.4656 | 0.5869 | 0.8650 | 0.095* | |
C33 | 0.6788 (6) | 0.61979 (16) | 0.7632 (3) | 0.0887 (11) | |
H33A | 0.8093 | 0.6118 | 0.7606 | 0.133* | |
H33B | 0.6559 | 0.6669 | 0.7826 | 0.133* | |
H33C | 0.6260 | 0.6096 | 0.6872 | 0.133* | |
C4 | 0.4998 (4) | 0.38994 (13) | 0.6918 (2) | 0.0476 (6) | |
H4 | 0.4916 | 0.4327 | 0.6559 | 0.057* | |
N5 | 0.4691 (3) | 0.33752 (10) | 0.62482 (17) | 0.0463 (5) | |
C6 | 0.4915 (3) | 0.27423 (11) | 0.67461 (19) | 0.0389 (5) | |
C7 | 0.4597 (3) | 0.21492 (13) | 0.6070 (2) | 0.0432 (6) | |
Br7 | 0.38160 (3) | 0.224825 (12) | 0.44876 (3) | 0.05827 (9) | |
C8 | 0.4855 (3) | 0.14966 (13) | 0.6517 (2) | 0.0424 (5) | |
C9 | 0.4568 (4) | 0.08662 (15) | 0.5862 (2) | 0.0555 (7) | |
H9 | 0.4138 | 0.0882 | 0.5086 | 0.067* | |
C10 | 0.4920 (4) | 0.02688 (15) | 0.6370 (3) | 0.0621 (8) | |
H10 | 0.4719 | −0.0128 | 0.5934 | 0.075* | |
C11 | 0.5597 (4) | 0.02044 (16) | 0.7560 (3) | 0.0585 (7) | |
O11 | 0.6006 (4) | −0.03111 (11) | 0.8062 (2) | 0.0831 (7) | |
O12 | 0.5771 (3) | 0.08092 (9) | 0.81977 (15) | 0.0539 (5) | |
C13 | 0.5460 (3) | 0.14392 (12) | 0.7696 (2) | 0.0427 (6) | |
C14 | 0.5759 (3) | 0.19997 (13) | 0.8405 (2) | 0.0447 (6) | |
H14 | 0.6153 | 0.1944 | 0.9183 | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0370 (12) | 0.0495 (15) | 0.0342 (12) | −0.0018 (11) | −0.0001 (10) | 0.0032 (10) |
C2 | 0.0450 (16) | 0.0529 (17) | 0.0314 (13) | −0.0058 (12) | 0.0022 (10) | −0.0016 (11) |
O2 | 0.0836 (14) | 0.0540 (10) | 0.0344 (11) | −0.0195 (10) | −0.0123 (8) | 0.0045 (7) |
C21 | 0.067 (2) | 0.0550 (16) | 0.0381 (13) | −0.0098 (14) | −0.0046 (12) | −0.0074 (11) |
C22 | 0.090 (2) | 0.082 (2) | 0.0516 (16) | −0.0017 (19) | −0.0200 (16) | 0.0001 (15) |
C3 | 0.0458 (14) | 0.0496 (16) | 0.0377 (13) | −0.0007 (12) | 0.0012 (11) | −0.0010 (11) |
C31 | 0.0584 (18) | 0.0506 (18) | 0.0473 (17) | 0.0066 (13) | −0.0022 (13) | −0.0035 (13) |
O31 | 0.0949 (16) | 0.0458 (11) | 0.0599 (12) | −0.0074 (11) | 0.0144 (10) | −0.0113 (9) |
O32 | 0.0991 (17) | 0.0641 (12) | 0.0522 (13) | 0.0133 (12) | 0.0118 (10) | −0.0052 (9) |
C32 | 0.113 (3) | 0.0495 (17) | 0.075 (2) | −0.0023 (18) | 0.007 (2) | −0.0234 (15) |
C33 | 0.118 (3) | 0.0493 (18) | 0.099 (3) | −0.007 (2) | −0.004 (2) | −0.0037 (18) |
C4 | 0.0507 (17) | 0.0478 (15) | 0.0444 (13) | 0.0039 (12) | −0.0004 (11) | 0.0029 (12) |
N5 | 0.0532 (13) | 0.0467 (13) | 0.0390 (11) | 0.0026 (10) | −0.0036 (10) | 0.0027 (9) |
C6 | 0.0360 (13) | 0.0481 (14) | 0.0326 (11) | −0.0006 (12) | 0.0013 (9) | −0.0032 (11) |
C7 | 0.0403 (13) | 0.0601 (17) | 0.0292 (11) | 0.0006 (12) | 0.0008 (9) | −0.0018 (10) |
Br7 | 0.06948 (16) | 0.06983 (14) | 0.03550 (11) | −0.00117 (13) | −0.01183 (16) | −0.00210 (16) |
C8 | 0.0418 (14) | 0.0484 (15) | 0.0370 (12) | −0.0008 (11) | 0.0052 (10) | −0.0030 (10) |
C9 | 0.0608 (17) | 0.0620 (18) | 0.0438 (15) | −0.0048 (15) | 0.0020 (13) | −0.0078 (13) |
C10 | 0.078 (2) | 0.0468 (18) | 0.0613 (18) | −0.0034 (16) | 0.0012 (16) | −0.0107 (14) |
C11 | 0.0665 (19) | 0.0496 (17) | 0.0595 (17) | −0.0031 (15) | 0.0010 (15) | −0.0029 (14) |
O11 | 0.115 (2) | 0.0488 (13) | 0.0849 (16) | 0.0071 (13) | −0.0164 (13) | 0.0045 (12) |
O12 | 0.0656 (13) | 0.0456 (10) | 0.0505 (11) | −0.0022 (9) | −0.0056 (8) | 0.0022 (8) |
C13 | 0.0406 (13) | 0.0495 (15) | 0.0380 (13) | −0.0019 (11) | 0.0012 (10) | 0.0079 (11) |
C14 | 0.0477 (16) | 0.0516 (14) | 0.0349 (12) | −0.0052 (12) | −0.0031 (10) | 0.0038 (11) |
C1—C14 | 1.401 (3) | C33—H33A | 0.9600 |
C1—C6 | 1.419 (3) | C33—H33B | 0.9600 |
C1—C2 | 1.437 (3) | C33—H33C | 0.9600 |
C2—O2 | 1.336 (3) | C4—N5 | 1.292 (3) |
C2—C3 | 1.388 (3) | C4—H4 | 0.9300 |
O2—C21 | 1.443 (3) | N5—C6 | 1.368 (3) |
C21—C22 | 1.497 (4) | C6—C7 | 1.407 (3) |
C21—H21A | 0.9700 | C7—C8 | 1.384 (3) |
C21—H21B | 0.9700 | C7—Br7 | 1.883 (2) |
C22—H22A | 0.9600 | C8—C13 | 1.406 (3) |
C22—H22B | 0.9600 | C8—C9 | 1.452 (4) |
C22—H22C | 0.9600 | C9—C10 | 1.326 (4) |
C3—C4 | 1.427 (3) | C9—H9 | 0.9300 |
C3—C31 | 1.480 (3) | C10—C11 | 1.435 (4) |
C31—O32 | 1.206 (3) | C10—H10 | 0.9300 |
C31—O31 | 1.330 (3) | C11—O11 | 1.193 (3) |
O31—C32 | 1.460 (3) | C11—O12 | 1.390 (3) |
C32—C33 | 1.480 (5) | O12—C13 | 1.374 (3) |
C32—H32A | 0.9700 | C13—C14 | 1.373 (3) |
C32—H32B | 0.9700 | C14—H14 | 0.9300 |
C14—C1—C6 | 120.3 (2) | H33A—C33—H33B | 109.5 |
C14—C1—C2 | 121.2 (2) | C32—C33—H33C | 109.5 |
C6—C1—C2 | 118.5 (2) | H33A—C33—H33C | 109.5 |
O2—C2—C3 | 127.6 (2) | H33B—C33—H33C | 109.5 |
O2—C2—C1 | 113.9 (2) | N5—C4—C3 | 127.0 (2) |
C3—C2—C1 | 118.5 (2) | N5—C4—H4 | 116.5 |
C2—O2—C21 | 123.1 (2) | C3—C4—H4 | 116.5 |
O2—C21—C22 | 106.6 (2) | C4—N5—C6 | 117.1 (2) |
O2—C21—H21A | 110.4 | N5—C6—C7 | 120.2 (2) |
C22—C21—H21A | 110.4 | N5—C6—C1 | 122.1 (2) |
O2—C21—H21B | 110.4 | C7—C6—C1 | 117.7 (2) |
C22—C21—H21B | 110.4 | C8—C7—C6 | 122.6 (2) |
H21A—C21—H21B | 108.6 | C8—C7—Br7 | 118.76 (18) |
C21—C22—H22A | 109.5 | C6—C7—Br7 | 118.63 (18) |
C21—C22—H22B | 109.5 | C7—C8—C13 | 117.4 (2) |
H22A—C22—H22B | 109.5 | C7—C8—C9 | 125.2 (2) |
C21—C22—H22C | 109.5 | C13—C8—C9 | 117.3 (2) |
H22A—C22—H22C | 109.5 | C10—C9—C8 | 120.0 (3) |
H22B—C22—H22C | 109.5 | C10—C9—H9 | 120.0 |
C2—C3—C4 | 116.5 (2) | C8—C9—H9 | 120.0 |
C2—C3—C31 | 125.2 (2) | C9—C10—C11 | 123.2 (3) |
C4—C3—C31 | 118.0 (2) | C9—C10—H10 | 118.4 |
O32—C31—O31 | 123.6 (3) | C11—C10—H10 | 118.4 |
O32—C31—C3 | 125.7 (3) | O11—C11—O12 | 116.7 (3) |
O31—C31—C3 | 110.5 (2) | O11—C11—C10 | 127.1 (3) |
C31—O31—C32 | 117.9 (2) | O12—C11—C10 | 116.2 (3) |
O31—C32—C33 | 106.9 (2) | C13—O12—C11 | 122.3 (2) |
O31—C32—H32A | 110.3 | C14—C13—O12 | 116.7 (2) |
C33—C32—H32A | 110.3 | C14—C13—C8 | 122.5 (2) |
O31—C32—H32B | 110.3 | O12—C13—C8 | 120.9 (2) |
C33—C32—H32B | 110.3 | C13—C14—C1 | 119.4 (2) |
H32A—C32—H32B | 108.6 | C13—C14—H14 | 120.3 |
C32—C33—H33A | 109.5 | C1—C14—H14 | 120.3 |
C32—C33—H33B | 109.5 | ||
C14—C1—C2—O2 | −1.9 (4) | C2—C1—C6—C7 | −177.1 (2) |
C6—C1—C2—O2 | 178.2 (2) | N5—C6—C7—C8 | 178.0 (2) |
C14—C1—C2—C3 | 178.3 (2) | C1—C6—C7—C8 | −2.1 (4) |
C6—C1—C2—C3 | −1.6 (4) | N5—C6—C7—Br7 | −1.2 (3) |
C3—C2—O2—C21 | −31.6 (4) | C1—C6—C7—Br7 | 178.68 (18) |
C1—C2—O2—C21 | 148.6 (2) | C6—C7—C8—C13 | 0.0 (4) |
C2—O2—C21—C22 | −154.4 (3) | Br7—C7—C8—C13 | 179.23 (18) |
O2—C2—C3—C4 | 178.4 (3) | C6—C7—C8—C9 | −179.4 (2) |
C1—C2—C3—C4 | −1.8 (4) | Br7—C7—C8—C9 | −0.1 (4) |
O2—C2—C3—C31 | −7.6 (5) | C7—C8—C9—C10 | 177.7 (3) |
C1—C2—C3—C31 | 172.2 (3) | C13—C8—C9—C10 | −1.7 (4) |
C2—C3—C31—O32 | −38.1 (5) | C8—C9—C10—C11 | −0.4 (5) |
C4—C3—C31—O32 | 135.7 (3) | C9—C10—C11—O11 | −177.1 (3) |
C2—C3—C31—O31 | 146.4 (3) | C9—C10—C11—O12 | 3.7 (4) |
C4—C3—C31—O31 | −39.7 (4) | O11—C11—O12—C13 | 175.6 (3) |
O32—C31—O31—C32 | −5.1 (4) | C10—C11—O12—C13 | −5.1 (4) |
C3—C31—O31—C32 | 170.5 (3) | C11—O12—C13—C14 | −177.1 (2) |
C31—O31—C32—C33 | −178.7 (3) | C11—O12—C13—C8 | 3.3 (4) |
C2—C3—C4—N5 | 4.9 (4) | C7—C8—C13—C14 | 1.3 (4) |
C31—C3—C4—N5 | −169.5 (3) | C9—C8—C13—C14 | −179.3 (2) |
C3—C4—N5—C6 | −3.8 (4) | C7—C8—C13—O12 | −179.1 (2) |
C4—N5—C6—C7 | 179.7 (2) | C9—C8—C13—O12 | 0.3 (4) |
C4—N5—C6—C1 | −0.2 (4) | O12—C13—C14—C1 | −179.9 (2) |
C14—C1—C6—N5 | −177.1 (2) | C8—C13—C14—C1 | −0.4 (4) |
C2—C1—C6—N5 | 2.8 (4) | C6—C1—C14—C13 | −1.8 (4) |
C14—C1—C6—C7 | 3.0 (4) | C2—C1—C14—C13 | 178.3 (2) |
Acknowledgements
We thank the University of Aberdeen for funding of the X-ray diffractometer, and acknowledge the use of the EPSRC's Chemical Database Service at Daresbury Laboratory (Fletcher et al., 1996).
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