Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100004522/qa0263sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100004522/qa0263Isup2.hkl |
CCDC reference: 145648
4-Oxo-4H-1-benzopyran-2-carboxylate (9.8 mmol, 2 g) methyl ester and hydroxycarbamoyl chloride (12 mmol) were mixed in anhydrous benzene (30 ml). The mixture was stirred, with regular addition of triethylamine (4 ml), for 15 min. After 2 h, the triethylamine chlorohydrate was eliminated and the solvent evaporated. The residue was then recrystallized from methanol.
All H atoms were initially located by difference Fourier synthesis. Subsequently, their positions were idealized and constrained to ride on their parent atoms with C—H(aromatic) = 0.95 or C—H(methyl) = 0.98 Å, and fixed individual displacement parameters [U(H) = 1.5Ueq(Cmethyl) or U(H) = 1.2Ueq(C)]. The hydroxyl H atom was refined freely.
Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
C19H15NO6 | F(000) = 736 |
Mr = 353.32 | Dx = 1.443 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.172 (1) Å | Cell parameters from 8192 reflections |
b = 9.337 (1) Å | θ = 1–25° |
c = 15.634 (1) Å | µ = 0.11 mm−1 |
β = 94.10 (1)° | T = 173 K |
V = 1626.7 (2) Å3 | Block, light yellow |
Z = 4 | 0.60 × 0.50 × 0.30 mm |
Siemens CCD three-circle diffractometer | 4240 independent reflections |
Radiation source: fine-focus sealed tube | 3444 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω scans | θmax = 29.6°, θmin = 2.2° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −15→15 |
Tmin = 0.938, Tmax = 0.968 | k = −12→12 |
32334 measured reflections | l = −21→21 |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0507P)2 + 0.677P] where P = (Fo2 + 2Fc2)/3 |
4240 reflections | (Δ/σ)max < 0.001 |
239 parameters | Δρmax = 0.62 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C19H15NO6 | V = 1626.7 (2) Å3 |
Mr = 353.32 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.172 (1) Å | µ = 0.11 mm−1 |
b = 9.337 (1) Å | T = 173 K |
c = 15.634 (1) Å | 0.60 × 0.50 × 0.30 mm |
β = 94.10 (1)° |
Siemens CCD three-circle diffractometer | 4240 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 3444 reflections with I > 2σ(I) |
Tmin = 0.938, Tmax = 0.968 | Rint = 0.030 |
32334 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.105 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.62 e Å−3 |
4240 reflections | Δρmin = −0.24 e Å−3 |
239 parameters |
Experimental. The data collection nominally covered a sphere of reciprocal space, by a combination of seven sets of exposures; each set had a different ϕ angle for the crystal and each exposure covered 0.3° in ω. The crystal-to-detector distance was 4.5 cm. Coverage of the unique set is complete to at least 26.4° in θ. Crystal decay was monitored by repeating the initial frames at the end of data collection and analyzing the duplicate reflections. |
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 | ||
O1 | 0.11072 (8) | 0.56803 (9) | 0.46782 (5) | 0.02328 (19) | |
N2 | 0.09198 (10) | 0.46596 (11) | 0.40241 (7) | 0.0242 (2) | |
C3 | 0.13993 (10) | 0.34628 (13) | 0.43272 (8) | 0.0200 (2) | |
C4 | 0.19088 (10) | 0.36469 (13) | 0.51856 (7) | 0.0190 (2) | |
C5 | 0.16866 (10) | 0.50341 (13) | 0.53603 (7) | 0.0197 (2) | |
C31 | 0.13220 (11) | 0.21589 (13) | 0.38037 (8) | 0.0210 (2) | |
C32 | 0.11327 (11) | 0.08298 (14) | 0.41719 (8) | 0.0242 (3) | |
H32 | 0.1120 | 0.0756 | 0.4777 | 0.029* | |
C33 | 0.09623 (12) | −0.03908 (14) | 0.36723 (8) | 0.0257 (3) | |
H33 | 0.0833 | −0.1292 | 0.3932 | 0.031* | |
C34 | 0.09826 (11) | −0.02814 (14) | 0.27864 (8) | 0.0252 (3) | |
O34 | 0.08039 (10) | −0.13909 (10) | 0.22331 (6) | 0.0343 (2) | |
C341 | 0.05452 (15) | −0.27574 (16) | 0.25924 (11) | 0.0388 (4) | |
H34A | 0.0440 | −0.3469 | 0.2132 | 0.058* | |
H34B | −0.0193 | −0.2692 | 0.2893 | 0.058* | |
H34C | 0.1212 | −0.3046 | 0.2997 | 0.058* | |
C35 | 0.11917 (13) | 0.10421 (15) | 0.24126 (9) | 0.0297 (3) | |
H35 | 0.1220 | 0.1113 | 0.1808 | 0.036* | |
C36 | 0.13577 (12) | 0.22469 (14) | 0.29142 (8) | 0.0264 (3) | |
H36 | 0.1498 | 0.3145 | 0.2653 | 0.032* | |
C41 | 0.25978 (10) | 0.25752 (12) | 0.57350 (7) | 0.0190 (2) | |
O41 | 0.21027 (8) | 0.19354 (10) | 0.62963 (6) | 0.0263 (2) | |
C42 | 0.38471 (10) | 0.23101 (13) | 0.55552 (8) | 0.0200 (2) | |
C43 | 0.45438 (11) | 0.13130 (13) | 0.60461 (8) | 0.0214 (2) | |
O43 | 0.41246 (9) | 0.05940 (11) | 0.67068 (6) | 0.0296 (2) | |
H43 | 0.334 (2) | 0.085 (2) | 0.6720 (14) | 0.061 (6)* | |
C44 | 0.57243 (12) | 0.10453 (14) | 0.58578 (8) | 0.0258 (3) | |
H44 | 0.6198 | 0.0377 | 0.6192 | 0.031* | |
C45 | 0.62035 (12) | 0.17488 (16) | 0.51894 (9) | 0.0312 (3) | |
H45 | 0.7009 | 0.1562 | 0.5065 | 0.037* | |
C46 | 0.55246 (13) | 0.27316 (17) | 0.46922 (9) | 0.0344 (3) | |
H46 | 0.5862 | 0.3206 | 0.4229 | 0.041* | |
C47 | 0.43640 (12) | 0.30104 (15) | 0.48766 (9) | 0.0283 (3) | |
H47 | 0.3903 | 0.3687 | 0.4540 | 0.034* | |
C51 | 0.19609 (10) | 0.58840 (13) | 0.61493 (8) | 0.0206 (2) | |
O51 | 0.24608 (9) | 0.53740 (10) | 0.67821 (6) | 0.0290 (2) | |
O52 | 0.16074 (8) | 0.72334 (9) | 0.60444 (6) | 0.02342 (19) | |
C53 | 0.18341 (12) | 0.81617 (14) | 0.67821 (9) | 0.0277 (3) | |
H53A | 0.1538 | 0.9127 | 0.6641 | 0.042* | |
H53B | 0.2699 | 0.8201 | 0.6938 | 0.042* | |
H52C | 0.1419 | 0.7785 | 0.7266 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0286 (4) | 0.0200 (4) | 0.0206 (4) | 0.0034 (3) | −0.0024 (3) | −0.0010 (3) |
N2 | 0.0295 (5) | 0.0216 (5) | 0.0209 (5) | 0.0022 (4) | −0.0018 (4) | −0.0025 (4) |
C3 | 0.0192 (5) | 0.0214 (6) | 0.0196 (5) | 0.0007 (4) | 0.0020 (4) | 0.0006 (4) |
C4 | 0.0175 (5) | 0.0208 (5) | 0.0188 (5) | 0.0002 (4) | 0.0028 (4) | −0.0004 (4) |
C5 | 0.0188 (5) | 0.0207 (5) | 0.0198 (5) | 0.0008 (4) | 0.0014 (4) | 0.0014 (4) |
C31 | 0.0198 (5) | 0.0219 (6) | 0.0210 (6) | 0.0011 (4) | 0.0002 (4) | −0.0021 (5) |
C32 | 0.0280 (6) | 0.0246 (6) | 0.0198 (6) | 0.0007 (5) | −0.0003 (5) | −0.0001 (5) |
C33 | 0.0295 (6) | 0.0209 (6) | 0.0265 (6) | 0.0002 (5) | 0.0006 (5) | 0.0000 (5) |
C34 | 0.0253 (6) | 0.0236 (6) | 0.0264 (6) | 0.0020 (5) | −0.0004 (5) | −0.0069 (5) |
O34 | 0.0478 (6) | 0.0251 (5) | 0.0297 (5) | −0.0005 (4) | 0.0005 (4) | −0.0098 (4) |
C341 | 0.0454 (9) | 0.0258 (7) | 0.0460 (9) | −0.0072 (6) | 0.0098 (7) | −0.0110 (6) |
C35 | 0.0399 (7) | 0.0291 (7) | 0.0202 (6) | 0.0011 (6) | 0.0029 (5) | −0.0027 (5) |
C36 | 0.0333 (7) | 0.0232 (6) | 0.0230 (6) | 0.0000 (5) | 0.0031 (5) | 0.0012 (5) |
C41 | 0.0219 (5) | 0.0179 (5) | 0.0171 (5) | −0.0002 (4) | 0.0006 (4) | −0.0019 (4) |
O41 | 0.0260 (5) | 0.0287 (5) | 0.0248 (4) | 0.0021 (4) | 0.0064 (4) | 0.0074 (4) |
C42 | 0.0205 (5) | 0.0201 (5) | 0.0195 (5) | 0.0005 (4) | 0.0014 (4) | 0.0005 (4) |
C43 | 0.0250 (6) | 0.0202 (5) | 0.0191 (5) | 0.0012 (5) | 0.0015 (4) | −0.0003 (4) |
O43 | 0.0297 (5) | 0.0307 (5) | 0.0291 (5) | 0.0070 (4) | 0.0071 (4) | 0.0129 (4) |
C44 | 0.0248 (6) | 0.0270 (6) | 0.0255 (6) | 0.0062 (5) | −0.0003 (5) | 0.0016 (5) |
C45 | 0.0220 (6) | 0.0404 (8) | 0.0316 (7) | 0.0049 (5) | 0.0054 (5) | 0.0027 (6) |
C46 | 0.0262 (7) | 0.0466 (8) | 0.0313 (7) | 0.0015 (6) | 0.0078 (5) | 0.0133 (6) |
C47 | 0.0255 (6) | 0.0331 (7) | 0.0266 (6) | 0.0032 (5) | 0.0031 (5) | 0.0107 (5) |
C51 | 0.0197 (5) | 0.0201 (5) | 0.0224 (6) | −0.0011 (4) | 0.0034 (4) | −0.0003 (4) |
O51 | 0.0374 (5) | 0.0269 (5) | 0.0218 (4) | 0.0035 (4) | −0.0037 (4) | 0.0000 (4) |
O52 | 0.0278 (4) | 0.0188 (4) | 0.0233 (4) | 0.0009 (3) | −0.0004 (3) | −0.0030 (3) |
C53 | 0.0318 (7) | 0.0232 (6) | 0.0280 (6) | −0.0008 (5) | 0.0013 (5) | −0.0075 (5) |
O1—C5 | 1.3497 (14) | O34—C341 | 1.4319 (18) |
O1—N2 | 1.4025 (13) | C35—C36 | 1.3762 (19) |
N2—C3 | 1.3130 (16) | C41—O41 | 1.2257 (15) |
C3—C4 | 1.4301 (16) | C41—C42 | 1.4644 (16) |
C3—C31 | 1.4661 (17) | C42—C47 | 1.4050 (17) |
C4—C5 | 1.3504 (17) | C42—C43 | 1.4057 (17) |
C4—C41 | 1.4957 (16) | C43—O43 | 1.3440 (15) |
C5—C51 | 1.4803 (17) | C43—C44 | 1.3943 (18) |
C31—C32 | 1.3905 (18) | C44—C45 | 1.3748 (19) |
C31—C36 | 1.3965 (17) | C45—C46 | 1.392 (2) |
C32—C33 | 1.3871 (18) | C46—C47 | 1.3732 (19) |
C33—C34 | 1.3906 (18) | C51—O51 | 1.1992 (15) |
C34—O34 | 1.3552 (15) | C51—O52 | 1.3271 (15) |
C34—C35 | 1.3938 (19) | O52—C53 | 1.4504 (15) |
C5—O1—N2 | 108.08 (9) | C36—C35—C34 | 120.37 (12) |
C3—N2—O1 | 106.23 (9) | C35—C36—C31 | 120.47 (12) |
N2—C3—C4 | 111.16 (10) | O41—C41—C42 | 122.69 (11) |
N2—C3—C31 | 119.93 (11) | O41—C41—C4 | 119.81 (11) |
C4—C3—C31 | 128.86 (11) | C42—C41—C4 | 117.48 (10) |
C5—C4—C3 | 103.80 (10) | C47—C42—C43 | 118.62 (11) |
C5—C4—C41 | 128.32 (11) | C47—C42—C41 | 121.00 (11) |
C3—C4—C41 | 127.76 (11) | C43—C42—C41 | 120.35 (11) |
O1—C5—C4 | 110.71 (10) | O43—C43—C44 | 117.36 (11) |
O1—C5—C51 | 118.54 (10) | O43—C43—C42 | 122.73 (11) |
C4—C5—C51 | 130.74 (11) | C44—C43—C42 | 119.91 (11) |
C32—C31—C36 | 118.74 (11) | C45—C44—C43 | 120.03 (12) |
C32—C31—C3 | 120.97 (11) | C44—C45—C46 | 120.88 (12) |
C36—C31—C3 | 120.16 (11) | C47—C46—C45 | 119.52 (13) |
C33—C32—C31 | 121.25 (11) | C46—C47—C42 | 121.03 (12) |
C32—C33—C34 | 119.29 (12) | O51—C51—O52 | 126.57 (11) |
O34—C34—C33 | 124.58 (12) | O51—C51—C5 | 122.07 (11) |
O34—C34—C35 | 115.57 (12) | O52—C51—C5 | 111.34 (10) |
C33—C34—C35 | 119.86 (12) | C51—O52—C53 | 115.82 (10) |
C34—O34—C341 | 117.09 (11) | ||
C5—O1—N2—C3 | −0.82 (13) | C32—C31—C36—C35 | 0.9 (2) |
O1—N2—C3—C4 | 0.35 (13) | C3—C31—C36—C35 | −174.90 (12) |
O1—N2—C3—C31 | 178.10 (10) | C5—C4—C41—O41 | 82.87 (16) |
N2—C3—C4—C5 | 0.24 (13) | C3—C4—C41—O41 | −101.70 (15) |
C31—C3—C4—C5 | −177.26 (12) | C5—C4—C41—C42 | −98.80 (15) |
N2—C3—C4—C41 | −176.07 (11) | C3—C4—C41—C42 | 76.63 (15) |
C31—C3—C4—C41 | 6.4 (2) | O41—C41—C42—C47 | 176.60 (12) |
N2—O1—C5—C4 | 1.01 (13) | C4—C41—C42—C47 | −1.68 (17) |
N2—O1—C5—C51 | −178.34 (10) | O41—C41—C42—C43 | −1.54 (18) |
C3—C4—C5—O1 | −0.77 (13) | C4—C41—C42—C43 | −179.82 (11) |
C41—C4—C5—O1 | 175.51 (11) | C47—C42—C43—O43 | 179.95 (12) |
C3—C4—C5—C51 | 178.48 (12) | C41—C42—C43—O43 | −1.87 (18) |
C41—C4—C5—C51 | −5.2 (2) | C47—C42—C43—C44 | 0.42 (18) |
N2—C3—C31—C32 | −141.56 (13) | C41—C42—C43—C44 | 178.60 (11) |
C4—C3—C31—C32 | 35.75 (19) | O43—C43—C44—C45 | −179.98 (12) |
N2—C3—C31—C36 | 34.14 (18) | C42—C43—C44—C45 | −0.4 (2) |
C4—C3—C31—C36 | −148.55 (13) | C43—C44—C45—C46 | −0.1 (2) |
C36—C31—C32—C33 | −1.01 (19) | C44—C45—C46—C47 | 0.5 (2) |
C3—C31—C32—C33 | 174.75 (12) | C45—C46—C47—C42 | −0.5 (2) |
C31—C32—C33—C34 | 0.1 (2) | C43—C42—C47—C46 | 0.1 (2) |
C32—C33—C34—O34 | −178.63 (12) | C41—C42—C47—C46 | −178.11 (13) |
C32—C33—C34—C35 | 1.0 (2) | O1—C5—C51—O51 | 179.12 (11) |
C33—C34—O34—C341 | 1.76 (19) | C4—C5—C51—O51 | −0.1 (2) |
C35—C34—O34—C341 | −177.90 (13) | O1—C5—C51—O52 | −2.12 (15) |
O34—C34—C35—C36 | 178.54 (12) | C4—C5—C51—O52 | 178.68 (12) |
C33—C34—C35—C36 | −1.1 (2) | O51—C51—O52—C53 | −1.35 (18) |
C34—C35—C36—C31 | 0.2 (2) | C5—C51—O52—C53 | 179.96 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
O43—H43···O51i | 0.91 (2) | 2.61 (2) | 3.0593 (14) | 111.7 (16) |
O43—H43···O41 | 0.91 (2) | 1.80 (2) | 2.6221 (13) | 149 (2) |
Symmetry code: (i) −x+1/2, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C19H15NO6 |
Mr | 353.32 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 11.172 (1), 9.337 (1), 15.634 (1) |
β (°) | 94.10 (1) |
V (Å3) | 1626.7 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.60 × 0.50 × 0.30 |
Data collection | |
Diffractometer | Siemens CCD three-circle diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.938, 0.968 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32334, 4240, 3444 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.694 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.105, 1.02 |
No. of reflections | 4240 |
No. of parameters | 239 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.62, −0.24 |
Computer programs: SMART (Siemens, 1995), SMART, SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
O43—H43···O51i | 0.91 (2) | 2.61 (2) | 3.0593 (14) | 111.7 (16) |
O43—H43···O41 | 0.91 (2) | 1.80 (2) | 2.6221 (13) | 149 (2) |
Symmetry code: (i) −x+1/2, y−1/2, −z+3/2. |
In one of our research fields, the dipole–dipolarophile approach has been investigated. In the case of dipolar 1,3-cycloadditions, we have studied the reaction of diarylnitrilimines with dipolarophile derivatives of lindanone (Kerbal et al., 1988), titralone (Theobald et al., 1990) or lisochromanone (Kerbal et al., 1990). Recently, our research has been focused on the reaction of arylnitriloxides with isoquinoline arylidines (Badri et al., 1999). We are trying to extend this research to the behaviour of new heterocyclic dipolarophiles, particularly that of esters of 4-Oxo-4H-1-benzopyrancarboxylate with arylnitriloxides. However, the isoxazolinic cycloadducts obtained so far seem to transform to more stable isoxazole products due to the opening of the pyronic cycle. Since NMR spectroscopy did not provide sufficient information about the regiochemistry of the reaction product we have carried out the X-ray structure analysis of the title compound, (I). The isoxazole ring of the title compound is planar (r.m.s. deviation = 0.004 Å) with the methoxycarbonyl moiety coplanar to it. The phenyl ring at C3 encloses an angle of 35.55 (3)° with the isoxazole ring. The other phenyl ring is nearly perpendicular [77.44 (5)°] to the isoxazole ring. An intramolecular hydrogen bond is formed between the hydroxyl group attached to a phenyl ring and a carbonyl O atom, so that a new six-membered ring is formed. Furthermore, there is a short intermolecular contact between the ester carbonyl O atom (O51) and the hydroxyl group.