Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802001617/tk6052sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802001617/tk6052Isup2.hkl |
CCDC reference: 182626
The title compound was prepared by base-catalyzed hydrolysis of the parent ethyl ester, as previously described (Greatrex et al., 2002). Crystals suitable for X-ray analysis were grown by slow evaporation from a CH2Cl2/hexane (1:1) solution of the compound.
Data collection: COLLECT (Nonius BV, 1997-2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C19H16O5 | Dx = 1.364 Mg m−3 |
Mr = 324.32 | Melting point = 130–132 K |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 30.0282 (4) Å | Cell parameters from 20303 reflections |
b = 8.9226 (1) Å | θ = 3.4–28.3° |
c = 12.1979 (2) Å | µ = 0.10 mm−1 |
β = 104.884 (1)° | T = 123 K |
V = 3158.52 (8) Å3 | Prismatic, colourless |
Z = 8 | 0.27 × 0.13 × 0.1 mm |
F(000) = 1360 |
Nonius KappaCCD diffractometer | Rint = 0.037 |
CCD–rotation images, thick slices scans | θmax = 28.3°, θmin = 3.4° |
21591 measured reflections | h = −40→40 |
3871 independent reflections | k = −11→11 |
3023 reflections with I > 2σ(I) | l = −16→15 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.045 | w = 1/[σ2(Fo2) + (0.033P)2 + 2.4814P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.096 | (Δ/σ)max < 0.001 |
S = 1.03 | Δρmax = 0.25 e Å−3 |
3871 reflections | Δρmin = −0.21 e Å−3 |
218 parameters |
C19H16O5 | V = 3158.52 (8) Å3 |
Mr = 324.32 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 30.0282 (4) Å | µ = 0.10 mm−1 |
b = 8.9226 (1) Å | T = 123 K |
c = 12.1979 (2) Å | 0.27 × 0.13 × 0.1 mm |
β = 104.884 (1)° |
Nonius KappaCCD diffractometer | 3023 reflections with I > 2σ(I) |
21591 measured reflections | Rint = 0.037 |
3871 independent reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.096 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.25 e Å−3 |
3871 reflections | Δρmin = −0.21 e Å−3 |
218 parameters |
Experimental. m.p. 130–132°C decomp. IR(nujol) 1783, 1711, 1678, 1457, 1377, 1336, 1300, 1267 cm-1. 1H n.m.r. (300 MHz, CDCl3): δ 2.67 (dd,J=9.3, 18.6 Hz, 1H), 3.26 (dd,J=5.1, 18.6 Hz, 1H), 3.64 (d,J=10.8 Hz, 1H), 3.90, (dddd,J=5.1, 7.8, 9.3, 10.8 Hz, 1H), 6.14 (d,J=7.8 Hz, 1H), 7.12–7.14 (m,2H), 7.31–7.36 (m,3H), 7.42–7.44 (m,2H), 7.51–7.57 (m,1H), 7.74–7.77 (m,2H). MS (M+,%) 324 (M.+, 12), 280 (10), 252 (18), 174 (15), 146 (28), 120 (25), 105 (100), 77 (52). Anal. Calcd. for C19H16O5: C, 70.36; H, 4.97%. Found C, 70.31; H, 4.90%. |
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. |
x | y | z | Uiso*/Ueq | ||
O2 | 0.02622 (3) | 0.06044 (11) | 0.61898 (8) | 0.0237 (2) | |
O3 | 0.05222 (3) | 0.43059 (11) | 0.51859 (9) | 0.0310 (3) | |
O1 | 0.09404 (3) | −0.00993 (10) | 0.59291 (7) | 0.0211 (2) | |
O5 | 0.19441 (3) | 0.20465 (11) | 0.45237 (8) | 0.0264 (2) | |
O4 | −0.01351 (3) | 0.31388 (11) | 0.43670 (10) | 0.0364 (3) | |
H4 | −0.0251 | 0.3952 | 0.4503 | 0.055* | |
C6' | 0.18191 (4) | 0.32455 (14) | 0.27511 (11) | 0.0192 (3) | |
C7 | 0.12161 (5) | −0.09861 (15) | 0.43314 (11) | 0.0223 (3) | |
C8' | 0.16888 (5) | 0.42504 (16) | 0.08592 (12) | 0.0259 (3) | |
H8' | 0.1496 | 0.4375 | 0.0115 | 0.031* | |
C2 | 0.05491 (5) | 0.07121 (14) | 0.56675 (11) | 0.0196 (3) | |
C3 | 0.05476 (4) | 0.17228 (14) | 0.46548 (11) | 0.0185 (3) | |
H3 | 0.0377 | 0.121 | 0.3941 | 0.022* | |
C6 | 0.03137 (4) | 0.31961 (15) | 0.47628 (11) | 0.0204 (3) | |
C4 | 0.10582 (4) | 0.18119 (14) | 0.46827 (11) | 0.0184 (3) | |
H4a | 0.1202 | 0.2594 | 0.5251 | 0.022* | |
C5' | 0.16628 (5) | 0.24622 (14) | 0.36648 (11) | 0.0197 (3) | |
C5 | 0.12375 (5) | 0.02611 (15) | 0.51819 (11) | 0.0203 (3) | |
H5 | 0.1562 | 0.037 | 0.565 | 0.024* | |
C12 | 0.08136 (5) | −0.17789 (16) | 0.38821 (11) | 0.0257 (3) | |
H12 | 0.0544 | −0.1559 | 0.4123 | 0.031* | |
C4' | 0.11532 (4) | 0.22346 (15) | 0.35525 (11) | 0.0192 (3) | |
H4'1 | 0.1036 | 0.1432 | 0.2992 | 0.023* | |
H4'2 | 0.0985 | 0.3169 | 0.3267 | 0.023* | |
C10 | 0.11918 (7) | −0.32168 (18) | 0.27205 (13) | 0.0385 (4) | |
H10 | 0.1182 | −0.397 | 0.2164 | 0.046* | |
C11' | 0.22634 (5) | 0.38428 (16) | 0.30194 (12) | 0.0237 (3) | |
H11' | 0.2463 | 0.3683 | 0.3752 | 0.028* | |
C8 | 0.16096 (6) | −0.13375 (17) | 0.39779 (14) | 0.0318 (4) | |
H8 | 0.1889 | −0.0817 | 0.4292 | 0.038* | |
C9' | 0.21256 (5) | 0.48722 (17) | 0.11422 (12) | 0.0289 (3) | |
H9' | 0.2229 | 0.5441 | 0.0597 | 0.035* | |
C7' | 0.15318 (5) | 0.34436 (15) | 0.16621 (11) | 0.0219 (3) | |
H7' | 0.123 | 0.3029 | 0.147 | 0.026* | |
C9 | 0.15950 (6) | −0.24448 (18) | 0.31686 (14) | 0.0398 (4) | |
H9 | 0.1863 | −0.267 | 0.2924 | 0.048* | |
C10' | 0.24141 (5) | 0.46674 (17) | 0.22220 (12) | 0.0282 (3) | |
H10' | 0.2714 | 0.5092 | 0.2413 | 0.034* | |
C11 | 0.08033 (6) | −0.28965 (17) | 0.30798 (13) | 0.0339 (4) | |
H11 | 0.0527 | −0.3441 | 0.2779 | 0.041* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.0238 (5) | 0.0242 (5) | 0.0270 (5) | −0.0034 (4) | 0.0138 (4) | −0.0045 (4) |
O3 | 0.0198 (5) | 0.0178 (5) | 0.0540 (7) | 0.0015 (4) | 0.0070 (5) | −0.0065 (5) |
O1 | 0.0231 (5) | 0.0205 (5) | 0.0231 (5) | 0.0037 (4) | 0.0118 (4) | 0.0025 (4) |
O5 | 0.0204 (5) | 0.0321 (6) | 0.0260 (5) | −0.0007 (4) | 0.0047 (4) | 0.0068 (4) |
O4 | 0.0182 (5) | 0.0223 (6) | 0.0654 (8) | 0.0037 (4) | 0.0045 (5) | −0.0123 (5) |
C6' | 0.0201 (7) | 0.0163 (6) | 0.0236 (7) | 0.0026 (5) | 0.0099 (5) | −0.0004 (5) |
C7 | 0.0282 (8) | 0.0173 (7) | 0.0246 (7) | 0.0080 (5) | 0.0128 (6) | 0.0063 (5) |
C8' | 0.0326 (8) | 0.0251 (7) | 0.0217 (7) | 0.0045 (6) | 0.0100 (6) | 0.0013 (6) |
C2 | 0.0206 (7) | 0.0155 (6) | 0.0233 (7) | −0.0009 (5) | 0.0071 (5) | −0.0044 (5) |
C3 | 0.0174 (7) | 0.0158 (6) | 0.0238 (7) | 0.0001 (5) | 0.0079 (5) | −0.0003 (5) |
C6 | 0.0191 (7) | 0.0191 (7) | 0.0255 (7) | 0.0011 (5) | 0.0100 (5) | 0.0026 (5) |
C4 | 0.0178 (6) | 0.0155 (6) | 0.0232 (7) | 0.0013 (5) | 0.0079 (5) | −0.0009 (5) |
C5' | 0.0207 (7) | 0.0159 (6) | 0.0235 (7) | 0.0010 (5) | 0.0074 (5) | −0.0009 (5) |
C5 | 0.0193 (7) | 0.0215 (7) | 0.0229 (7) | 0.0039 (5) | 0.0102 (5) | 0.0039 (5) |
C12 | 0.0301 (8) | 0.0220 (7) | 0.0255 (7) | 0.0082 (6) | 0.0082 (6) | 0.0013 (6) |
C4' | 0.0187 (7) | 0.0176 (6) | 0.0222 (7) | 0.0010 (5) | 0.0072 (5) | 0.0019 (5) |
C10 | 0.0689 (12) | 0.0233 (8) | 0.0283 (8) | 0.0163 (8) | 0.0218 (8) | 0.0034 (6) |
C11' | 0.0206 (7) | 0.0254 (7) | 0.0265 (7) | 0.0018 (6) | 0.0089 (6) | 0.0014 (6) |
C8 | 0.0367 (9) | 0.0226 (7) | 0.0443 (9) | 0.0075 (6) | 0.0253 (7) | 0.0065 (6) |
C9' | 0.0342 (8) | 0.0273 (8) | 0.0313 (8) | 0.0029 (6) | 0.0198 (7) | 0.0072 (6) |
C7' | 0.0233 (7) | 0.0191 (7) | 0.0247 (7) | 0.0014 (5) | 0.0085 (6) | −0.0026 (5) |
C9 | 0.0574 (12) | 0.0270 (8) | 0.0485 (10) | 0.0171 (8) | 0.0382 (9) | 0.0085 (7) |
C10' | 0.0234 (7) | 0.0283 (8) | 0.0364 (8) | −0.0015 (6) | 0.0138 (6) | 0.0033 (6) |
C11 | 0.0478 (10) | 0.0234 (8) | 0.0278 (8) | 0.0077 (7) | 0.0050 (7) | 0.0005 (6) |
O2—C2 | 1.1996 (16) | C4—C5 | 1.5514 (18) |
O3—C6 | 1.2137 (16) | C4—H4a | 1 |
O1—C2 | 1.3470 (16) | C5'—C4' | 1.5143 (18) |
O1—C5 | 1.4653 (15) | C5—H5 | 1 |
O5—C5' | 1.2224 (16) | C12—C11 | 1.392 (2) |
O4—C6 | 1.3106 (16) | C12—H12 | 0.95 |
O4—H4 | 0.84 | C4'—H4'1 | 0.99 |
C6'—C11' | 1.3953 (19) | C4'—H4'2 | 0.99 |
C6'—C7' | 1.3970 (18) | C10—C11 | 1.377 (2) |
C6'—C5' | 1.4900 (18) | C10—C9 | 1.378 (3) |
C7—C12 | 1.386 (2) | C10—H10 | 0.95 |
C7—C8 | 1.3934 (19) | C11'—C10' | 1.3850 (19) |
C7—C5 | 1.5115 (19) | C11'—H11' | 0.95 |
C8'—C9' | 1.384 (2) | C8—C9 | 1.389 (2) |
C8'—C7' | 1.3917 (19) | C8—H8 | 0.95 |
C8'—H8' | 0.95 | C9'—C10' | 1.390 (2) |
C2—C3 | 1.5285 (18) | C9'—H9' | 0.95 |
C3—C6 | 1.5120 (18) | C7'—H7' | 0.95 |
C3—C4 | 1.5269 (17) | C9—H9 | 0.95 |
C3—H3 | 1 | C10'—H10' | 0.95 |
C4—C4' | 1.5252 (18) | C11—H11 | 0.95 |
C2—O1—C5 | 111.60 (10) | C7—C5—H5 | 109.1 |
C6—O4—H4 | 109.5 | C4—C5—H5 | 109.1 |
C11'—C6'—C7' | 119.64 (12) | C7—C12—C11 | 120.20 (14) |
C11'—C6'—C5' | 118.02 (12) | C7—C12—H12 | 119.9 |
C7'—C6'—C5' | 122.30 (12) | C11—C12—H12 | 119.9 |
C12—C7—C8 | 119.04 (13) | C5'—C4'—C4 | 111.76 (10) |
C12—C7—C5 | 121.73 (12) | C5'—C4'—H4'1 | 109.3 |
C8—C7—C5 | 119.23 (13) | C4—C4'—H4'1 | 109.3 |
C9'—C8'—C7' | 120.17 (13) | C5'—C4'—H4'2 | 109.3 |
C9'—C8'—H8' | 119.9 | C4—C4'—H4'2 | 109.3 |
C7'—C8'—H8' | 119.9 | H4'1—C4'—H4'2 | 107.9 |
O2—C2—O1 | 122.21 (12) | C11—C10—C9 | 119.97 (15) |
O2—C2—C3 | 128.53 (12) | C11—C10—H10 | 120 |
O1—C2—C3 | 109.26 (10) | C9—C10—H10 | 120 |
C6—C3—C4 | 116.04 (11) | C10'—C11'—C6' | 120.22 (13) |
C6—C3—C2 | 110.34 (10) | C10'—C11'—H11' | 119.9 |
C4—C3—C2 | 102.61 (10) | C6'—C11'—H11' | 119.9 |
C6—C3—H3 | 109.2 | C9—C8—C7 | 120.36 (16) |
C4—C3—H3 | 109.2 | C9—C8—H8 | 119.8 |
C2—C3—H3 | 109.2 | C7—C8—H8 | 119.8 |
O3—C6—O4 | 123.91 (12) | C8'—C9'—C10' | 120.25 (13) |
O3—C6—C3 | 123.09 (12) | C8'—C9'—H9' | 119.9 |
O4—C6—C3 | 113.00 (11) | C10'—C9'—H9' | 119.9 |
C4'—C4—C3 | 114.38 (11) | C8'—C7'—C6' | 119.77 (13) |
C4'—C4—C5 | 116.66 (10) | C8'—C7'—H7' | 120.1 |
C3—C4—C5 | 101.98 (10) | C6'—C7'—H7' | 120.1 |
C4'—C4—H4a | 107.8 | C10—C9—C8 | 120.09 (15) |
C3—C4—H4a | 107.8 | C10—C9—H9 | 120 |
C5—C4—H4a | 107.8 | C8—C9—H9 | 120 |
O5—C5'—C6' | 120.15 (12) | C11'—C10'—C9' | 119.91 (13) |
O5—C5'—C4' | 119.78 (12) | C11'—C10'—H10' | 120 |
C6'—C5'—C4' | 120.03 (11) | C9'—C10'—H10' | 120 |
O1—C5—C7 | 109.89 (11) | C10—C11—C12 | 120.32 (16) |
O1—C5—C4 | 103.57 (10) | C10—C11—H11 | 119.8 |
C7—C5—C4 | 115.97 (11) | C12—C11—H11 | 119.8 |
O1—C5—H5 | 109.1 |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O3i | 0.84 | 1.84 | 2.6782 (14) | 178 |
Symmetry code: (i) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C19H16O5 |
Mr | 324.32 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 123 |
a, b, c (Å) | 30.0282 (4), 8.9226 (1), 12.1979 (2) |
β (°) | 104.884 (1) |
V (Å3) | 3158.52 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.27 × 0.13 × 0.1 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21591, 3871, 3023 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.096, 1.03 |
No. of reflections | 3871 |
No. of parameters | 218 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.25, −0.21 |
Computer programs: COLLECT (Nonius BV, 1997-2000), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O3i | 0.84 | 1.84 | 2.6782 (14) | 178 |
Symmetry code: (i) −x, −y+1, −z+1. |
To establish the stereochemistry about the lactone ring system of (±)-ethyl 2-oxo-4-(2-oxp-2-phenylethyl)-5-phenyltetrahydrofuran-3-carboxylate (Greatrex et al., 2002), the structure of the derived acid, (I), was determined. The molecular structure of (I) is shown in Fig. 1. A centrosymmetric dimer is formed through a strong intermolecular hydrogen bond between centrosymmetrically related carboxylic acid groups (Table 1).