In the title compound, C
15H
17NO
6, the formation of an intramolecular O—H
O resonance-assisted hydrogen bond extends the delocalization of the electronic system beyond the two quinoline fused rings.
Supporting information
CCDC reference: 221709
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.002 Å
- R factor = 0.041
- wR factor = 0.116
- Data-to-parameter ratio = 14.9
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
REFLT_03
From the CIF: _diffrn_reflns_theta_max 30.39
From the CIF: _reflns_number_total 3978
TEST2: Reflns within _diffrn_reflns_theta_max
Count of symmetry unique reflns 4253
Completeness (_total/calc) 93.53%
Alert C: < 95% complete
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
Data collection: SMART-NT (Bruker, 1998); cell refinement: SMART-NT; data reduction: SAINT-NT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL-NT (Bruker, 1998).
3-ethoxycarbonyl-4-hydroxy-6-methoxymethyleneoxy-1-methyl-2-quinolone
top
Crystal data top
C15H17NO6 | F(000) = 648 |
Mr = 307.30 | Dx = 1.445 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 755 reflections |
a = 11.558 (3) Å | θ = 13.7–24.3° |
b = 10.476 (2) Å | µ = 0.11 mm−1 |
c = 11.750 (2) Å | T = 100 K |
β = 98.823 (3)° | Irregular shape, colourless |
V = 1405.9 (5) Å3 | 0.36 × 0.26 × 0.18 mm |
Z = 4 | |
Data collection top
Bruker SMART 1K CCD diffractometer | 2908 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.037 |
Graphite monochromator | θmax = 30.4°, θmin = 1.8° |
ω scans | h = −16→15 |
16953 measured reflections | k = −14→14 |
3978 independent reflections | l = −16→16 |
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)] = 0.041 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.116 | All H-atom parameters refined |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0632P)2 + 0.3584P] where P = (Fo2 + 2Fc2)/3 |
3978 reflections | (Δ/σ)max < 0.001 |
267 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
Special details top
Experimental. The data collection nominally covered a full sphere of reciprocal space, by a
combination of 5 sets of ω scans each set at different φ and/or 2θ angles
and each scan (20 s exposure) covering 0.3° in ω. Crystal to detector
distance 4.51 cm. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | −0.10217 (9) | 0.49877 (10) | 0.31837 (9) | 0.0167 (2) | |
C2 | −0.17015 (11) | 0.41122 (12) | 0.36837 (10) | 0.0170 (2) | |
C3 | −0.10626 (11) | 0.31269 (12) | 0.44051 (10) | 0.0162 (2) | |
C4A | 0.08094 (10) | 0.39480 (12) | 0.39502 (10) | 0.0159 (2) | |
C4 | 0.01511 (11) | 0.30558 (12) | 0.45308 (10) | 0.0156 (2) | |
C5 | 0.20385 (11) | 0.38476 (12) | 0.40468 (10) | 0.0172 (2) | |
H5 | 0.2407 (14) | 0.3171 (16) | 0.4490 (13) | 0.020 (4)* | |
C6 | 0.26489 (11) | 0.47201 (13) | 0.34883 (11) | 0.0185 (3) | |
C7 | 0.20362 (12) | 0.56976 (13) | 0.28376 (11) | 0.0204 (3) | |
H7 | 0.2476 (16) | 0.6305 (16) | 0.2434 (15) | 0.030 (4)* | |
C8A | 0.01903 (10) | 0.49094 (12) | 0.32839 (10) | 0.0162 (2) | |
C8 | 0.08353 (11) | 0.57944 (13) | 0.27316 (11) | 0.0192 (3) | |
H8 | 0.0435 (14) | 0.6471 (16) | 0.2291 (14) | 0.024 (4)* | |
C9 | −0.16595 (11) | 0.21633 (12) | 0.50186 (10) | 0.0172 (2) | |
O10 | −0.28169 (8) | 0.22102 (9) | 0.48625 (8) | 0.0201 (2) | |
C11 | −0.34014 (12) | 0.12130 (14) | 0.54398 (12) | 0.0219 (3) | |
H11B | −0.2986 (14) | 0.1111 (15) | 0.6211 (14) | 0.021 (4)* | |
H11A | −0.4156 (15) | 0.1570 (16) | 0.5453 (13) | 0.023 (4)* | |
C12 | −0.34791 (13) | −0.00083 (14) | 0.47535 (13) | 0.0259 (3) | |
H12C | −0.3935 (16) | 0.0134 (17) | 0.3985 (16) | 0.031 (4)* | |
H12B | −0.3837 (16) | −0.0683 (18) | 0.5173 (15) | 0.034 (5)* | |
H12A | −0.2683 (17) | −0.0352 (18) | 0.4637 (15) | 0.035 (5)* | |
O13 | −0.11068 (8) | 0.13483 (9) | 0.56458 (8) | 0.0225 (2) | |
O14 | 0.07756 (8) | 0.21692 (9) | 0.51637 (8) | 0.0200 (2) | |
H14 | 0.025 (2) | 0.172 (2) | 0.5492 (18) | 0.051 (6)* | |
O15 | −0.27786 (8) | 0.42042 (10) | 0.35004 (8) | 0.0245 (2) | |
C16 | −0.16336 (12) | 0.60044 (13) | 0.24695 (12) | 0.0202 (3) | |
H16C | −0.1358 (15) | 0.6839 (17) | 0.2792 (14) | 0.025 (4)* | |
H16B | −0.2440 (17) | 0.5932 (17) | 0.2538 (15) | 0.032 (5)* | |
H16A | −0.1508 (14) | 0.5914 (16) | 0.1674 (14) | 0.023 (4)* | |
O17 | 0.38414 (8) | 0.47260 (9) | 0.35095 (8) | 0.0215 (2) | |
C18 | 0.45109 (12) | 0.37448 (13) | 0.41508 (12) | 0.0218 (3) | |
H18B | 0.4336 (14) | 0.3724 (15) | 0.4930 (14) | 0.019 (4)* | |
H18A | 0.5313 (15) | 0.4014 (16) | 0.4119 (14) | 0.026 (4)* | |
O19 | 0.42767 (8) | 0.25349 (9) | 0.36709 (8) | 0.0225 (2) | |
C20 | 0.46905 (14) | 0.23784 (16) | 0.25916 (13) | 0.0278 (3) | |
H20C | 0.4628 (15) | 0.1462 (18) | 0.2392 (15) | 0.028 (4)* | |
H20B | 0.4212 (17) | 0.2879 (18) | 0.2002 (16) | 0.034 (5)* | |
H20A | 0.552 (2) | 0.2680 (19) | 0.2675 (17) | 0.045 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0153 (5) | 0.0181 (5) | 0.0166 (5) | 0.0004 (4) | 0.0021 (4) | 0.0023 (4) |
C2 | 0.0154 (6) | 0.0192 (6) | 0.0161 (5) | −0.0016 (4) | 0.0019 (4) | −0.0008 (4) |
C3 | 0.0160 (6) | 0.0165 (6) | 0.0162 (5) | −0.0010 (4) | 0.0031 (4) | −0.0002 (4) |
C4A | 0.0161 (6) | 0.0159 (6) | 0.0158 (5) | −0.0012 (4) | 0.0031 (4) | −0.0010 (4) |
C4 | 0.0165 (6) | 0.0155 (6) | 0.0146 (5) | −0.0002 (4) | 0.0018 (4) | −0.0010 (4) |
C5 | 0.0161 (6) | 0.0171 (6) | 0.0182 (5) | −0.0003 (5) | 0.0024 (4) | −0.0003 (5) |
C6 | 0.0142 (6) | 0.0214 (6) | 0.0200 (6) | −0.0018 (5) | 0.0032 (4) | −0.0023 (5) |
C7 | 0.0206 (6) | 0.0206 (6) | 0.0206 (6) | −0.0032 (5) | 0.0056 (5) | 0.0012 (5) |
C8A | 0.0154 (6) | 0.0175 (6) | 0.0157 (5) | −0.0013 (4) | 0.0021 (4) | −0.0022 (4) |
C8 | 0.0188 (6) | 0.0198 (6) | 0.0191 (6) | 0.0000 (5) | 0.0033 (5) | 0.0025 (5) |
C9 | 0.0150 (6) | 0.0193 (6) | 0.0172 (5) | −0.0021 (5) | 0.0027 (4) | −0.0013 (4) |
O10 | 0.0148 (4) | 0.0218 (5) | 0.0239 (4) | −0.0023 (3) | 0.0040 (3) | 0.0041 (4) |
C11 | 0.0156 (6) | 0.0264 (7) | 0.0243 (6) | −0.0024 (5) | 0.0047 (5) | 0.0078 (5) |
C12 | 0.0226 (7) | 0.0257 (7) | 0.0286 (7) | −0.0062 (6) | 0.0012 (5) | 0.0047 (6) |
O13 | 0.0172 (5) | 0.0234 (5) | 0.0264 (5) | −0.0014 (4) | 0.0022 (4) | 0.0073 (4) |
O14 | 0.0159 (4) | 0.0199 (5) | 0.0241 (5) | 0.0000 (4) | 0.0026 (3) | 0.0059 (4) |
O15 | 0.0138 (4) | 0.0290 (5) | 0.0300 (5) | −0.0002 (4) | 0.0006 (4) | 0.0086 (4) |
C16 | 0.0178 (6) | 0.0201 (6) | 0.0224 (6) | 0.0016 (5) | 0.0021 (5) | 0.0046 (5) |
O17 | 0.0137 (4) | 0.0215 (5) | 0.0298 (5) | −0.0016 (3) | 0.0051 (4) | 0.0039 (4) |
C18 | 0.0157 (6) | 0.0249 (7) | 0.0243 (6) | −0.0017 (5) | 0.0013 (5) | 0.0019 (5) |
O19 | 0.0190 (5) | 0.0223 (5) | 0.0269 (5) | −0.0005 (4) | 0.0057 (4) | 0.0030 (4) |
C20 | 0.0247 (7) | 0.0289 (8) | 0.0311 (7) | 0.0017 (6) | 0.0085 (6) | 0.0001 (6) |
Geometric parameters (Å, º) top
O13—C9 | 1.2392 (16) | C9—O10 | 1.3230 (15) |
C9—C3 | 1.4721 (17) | O10—C11 | 1.4657 (15) |
C3—C4 | 1.3899 (17) | C11—C12 | 1.508 (2) |
C4—O14 | 1.3312 (15) | C11—H11B | 0.964 (16) |
N1—C8A | 1.3901 (16) | C11—H11A | 0.951 (17) |
N1—C2 | 1.3948 (16) | C12—H12C | 0.984 (18) |
N1—C16 | 1.4686 (16) | C12—H12B | 0.988 (19) |
C2—O15 | 1.2342 (15) | C12—H12A | 1.016 (19) |
C2—C3 | 1.4619 (17) | O14—H14 | 0.90 (2) |
C4A—C8A | 1.4027 (17) | C16—H16C | 0.986 (18) |
C4A—C5 | 1.4116 (17) | C16—H16B | 0.95 (2) |
C4A—C4 | 1.4412 (17) | C16—H16A | 0.972 (16) |
C5—C6 | 1.3805 (18) | O17—C18 | 1.4298 (16) |
C5—H5 | 0.941 (17) | C18—O19 | 1.3968 (17) |
C6—O17 | 1.3747 (15) | C18—H18B | 0.967 (16) |
C6—C7 | 1.4030 (19) | C18—H18A | 0.975 (17) |
C7—C8 | 1.3782 (19) | O19—C20 | 1.4318 (17) |
C7—H7 | 0.981 (18) | C20—H20C | 0.988 (18) |
C8A—C8 | 1.4088 (17) | C20—H20B | 0.971 (19) |
C8—H8 | 0.955 (17) | C20—H20A | 1.00 (2) |
| | | |
C8A—N1—C2 | 123.44 (10) | O10—C11—C12 | 110.57 (11) |
C8A—N1—C16 | 118.81 (10) | O10—C11—H11B | 108.4 (9) |
C2—N1—C16 | 117.68 (10) | C12—C11—H11B | 112.9 (10) |
O15—C2—N1 | 119.57 (11) | O10—C11—H11A | 102.5 (10) |
O15—C2—C3 | 124.23 (11) | C12—C11—H11A | 111.3 (10) |
N1—C2—C3 | 116.19 (10) | H11B—C11—H11A | 110.7 (13) |
C4—C3—C2 | 120.75 (11) | C11—C12—H12C | 110.0 (10) |
C4—C3—C9 | 116.90 (11) | C11—C12—H12B | 109.6 (10) |
C2—C3—C9 | 122.35 (11) | H12C—C12—H12B | 111.0 (15) |
C8A—C4A—C5 | 121.29 (11) | C11—C12—H12A | 113.1 (11) |
C8A—C4A—C4 | 117.95 (11) | H12C—C12—H12A | 107.3 (14) |
C5—C4A—C4 | 120.76 (11) | H12B—C12—H12A | 105.7 (15) |
O14—C4—C3 | 123.28 (11) | C4—O14—H14 | 104.7 (14) |
O14—C4—C4A | 115.88 (11) | N1—C16—H16C | 108.9 (10) |
C3—C4—C4A | 120.83 (11) | N1—C16—H16B | 106.7 (11) |
C6—C5—C4A | 119.59 (12) | H16C—C16—H16B | 107.5 (14) |
C6—C5—H5 | 122.7 (10) | N1—C16—H16A | 110.4 (10) |
C4A—C5—H5 | 117.7 (10) | H16C—C16—H16A | 111.7 (14) |
O17—C6—C5 | 125.34 (12) | H16B—C16—H16A | 111.5 (14) |
O17—C6—C7 | 115.31 (11) | C6—O17—C18 | 117.80 (10) |
C5—C6—C7 | 119.36 (12) | O19—C18—O17 | 112.57 (11) |
C8—C7—C6 | 121.34 (12) | O19—C18—H18B | 107.8 (9) |
C8—C7—H7 | 119.9 (11) | O17—C18—H18B | 109.8 (9) |
C6—C7—H7 | 118.7 (11) | O19—C18—H18A | 111.9 (10) |
N1—C8A—C4A | 120.72 (11) | O17—C18—H18A | 102.3 (10) |
N1—C8A—C8 | 121.31 (11) | H18B—C18—H18A | 112.4 (13) |
C4A—C8A—C8 | 117.97 (11) | C18—O19—C20 | 113.02 (11) |
C7—C8—C8A | 120.44 (12) | O19—C20—H20C | 107.4 (10) |
C7—C8—H8 | 120.1 (10) | O19—C20—H20B | 109.8 (11) |
C8A—C8—H8 | 119.5 (10) | H20C—C20—H20B | 110.1 (14) |
O13—C9—O10 | 121.74 (11) | O19—C20—H20A | 108.9 (12) |
O13—C9—C3 | 121.75 (11) | H20C—C20—H20A | 111.3 (15) |
O10—C9—C3 | 116.51 (11) | H20B—C20—H20A | 109.4 (16) |
C9—O10—C11 | 115.93 (10) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O14—H14···O13 | 0.90 (2) | 1.65 (2) | 2.4844 (14) | 153 (2) |
Bond distances (Å) within the RAHB fragment and their expected values
(Bürgi & Dunitz, 1994) topBond | This work | Expected |
O13—C9a | 1.2392 (16) | 1.199 (9) |
C9—C3a | 1.4721 (17) | 1.488 (14) |
C3—C4b | 1.3899 (17) | 1.340 (13) |
C4—O14c | 1.3312 (15) | 1.362 (15) |
Expected values in the fragments: (a) C═C-C(═O)-O-C*;
(b) C═C-C═O; (c) Car-OH. |