Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802006736/na6155sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802006736/na61553sup2.hkl |
CCDC reference: 185798
Key indicators
- Single-crystal X-ray study
- T = 143 K
- Mean (C-C) = 0.005 Å
- R factor = 0.053
- wR factor = 0.110
- Data-to-parameter ratio = 10.3
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.52 From the CIF: _reflns_number_total 2895 Count of symmetry unique reflns 2900 Completeness (_total/calc) 99.83% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
For the preparation of compound (3), n-BuLi (1.6M in hexane, 0.0033 mol) was added to a solution of 1,2-dimethoxybenzene (0.414 g, 0.003 mol) in dry tetrahydrofuran (THF; 15 ml) at 273 K. In order to complete the ortho-lithiation of 1,2-dimethoxybenzene, the solution was allowed to stand at room temperature for 20 h. After cooling to 273 K, (2S)-2-(1,3-dioxo-1,3-dihydroisoindol-2-yl)-N,N-diethylpropanamide, (2) (R1 = R2 = Et) (0.822 g, 0.003 mol), was added. The mixture was allowed to react at room temperature for 2 h, was then hydrolyzed with water (about 2 ml) and extracted twice with Et2O. The combined organic layers were washed with dilute hydrochloric acid (1 M), dried with Na2SO4 and concentrated under vacuum. The remainder was dissolved in a small amount of hexane/ethyl acetate (1:1). After standing in the open air overnight, the product crystallized in analytically pure form; a crystal suitable for X-ray measurements was selected directly from the main product without further recrystallization. M.p. 455–456 K; [α]20D +189.5°; 1H NMR (CDCl3, p.p.m., δ): 1.09 (m, 6H, 2CH3CH2), 1.38 (t, J = 7.2 Hz, 3H, CH3—CH), 2.90 (s, 3H, CH3O), 3.44 (m, 4H, 2CH3CH2), 3.74 (s, 3H, CH3O), 5.44 (q, J = 7.2 Hz, 1H, CH), 6.87–7.83 (m, 7H, C6H4, C6H3), 8.17 (s, 1H, OH); 13C NMR (CDCl3, p.p.m., δ): 12.8 (CH), 14.1 (CH3), 15.1 (CH3), 41.5 (CH2), 43.0 (CH2), 50.2 (CH), 55.7 (CH3), 59.0 (CH3), 88.7 (C), 112.9 (CH), 120.3 (CH), 121.7 (CH), 122.2 (CH), 123.2 (CH), 128.1 (CH), 130.0 (C), 135.6 (C), 136.6 (CH), 146.2 (C), 151.7 (C), 152.7 (C), 169.3 (C), 174.2 (C). Spectral data for 2-[2-(2,3-dimethoxyphenyl)-1-methyl-2-oxoethyl]isoindole-1,3-dione, (4): 1H NMR (CDCl3, p.p.m., δ): 1.15 (t, J = 7.2 Hz, 3H), 3.54 (s, 3H), 3.75 (s, 3H), 4.01 (q, J = 7.2 Hz, 1H), 6.78–8.05 (m, 7H); [α]20D +0.55°, i.e. partially racemized.
The hydroxyl H atom was refined freely. Methyl H atoms were identified in difference syntheses, idealized and refined as rigid groups allowed to rotate but not tip. Other H atoms were included using a riding model. No Friedel opposite reflections were measured because the Friedel differences must be insignificant. The Flack parameter is therefore indeterminate. To improve stability of refinement, the displacement factors were restrained using the SHELXL commands DELU and SIMU.
Data collection: DIF4 (Stoe & Cie, 1992); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.
C23H28N2O5 | Dx = 1.225 Mg m−3 |
Mr = 412.47 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 52 reflections |
a = 10.921 (2) Å | θ = 10–11.5° |
b = 12.905 (3) Å | µ = 0.09 mm−1 |
c = 15.868 (4) Å | T = 143 K |
V = 2236.4 (9) Å3 | Flattened octahedron, colourless |
Z = 4 | 0.4 × 0.4 × 0.3 mm |
F(000) = 880 |
Stoe STADI-4 diffractometer | Rint = 0.000 |
Radiation source: fine-focus sealed tube | θmax = 27.5°, θmin = 3.0° |
Graphite monochromator | h = −14→0 |
ω/θ scans | k = −16→0 |
2895 measured reflections | l = −20→0 |
2895 independent reflections | 3 standard reflections every 60 min |
2188 reflections with I > 2σ(I) | intensity decay: 1% |
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)] = 0.053 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.110 | w = 1/[σ2(Fo2) + (0.0301P)2 + 0.7278P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max < 0.001 |
2895 reflections | Δρmax = 0.19 e Å−3 |
281 parameters | Δρmin = −0.18 e Å−3 |
271 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0069 (8) |
C23H28N2O5 | V = 2236.4 (9) Å3 |
Mr = 412.47 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 10.921 (2) Å | µ = 0.09 mm−1 |
b = 12.905 (3) Å | T = 143 K |
c = 15.868 (4) Å | 0.4 × 0.4 × 0.3 mm |
Stoe STADI-4 diffractometer | Rint = 0.000 |
2895 measured reflections | 3 standard reflections every 60 min |
2895 independent reflections | intensity decay: 1% |
2188 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.053 | 271 restraints |
wR(F2) = 0.110 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | Δρmax = 0.19 e Å−3 |
2895 reflections | Δρmin = −0.18 e Å−3 |
281 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 | ||
C1 | 0.2121 (3) | 0.3099 (2) | 0.50412 (18) | 0.0278 (7) | |
H1 | 0.1664 | 0.2550 | 0.5356 | 0.033* | |
C2 | 0.1212 (3) | 0.3668 (3) | 0.4477 (2) | 0.0346 (7) | |
H2A | 0.0574 | 0.3987 | 0.4825 | 0.042* | |
H2B | 0.0836 | 0.3176 | 0.4084 | 0.042* | |
H2C | 0.1642 | 0.4207 | 0.4158 | 0.042* | |
C3 | 0.3104 (3) | 0.2563 (2) | 0.44967 (19) | 0.0316 (7) | |
C4 | 0.3776 (3) | 0.1148 (3) | 0.3612 (2) | 0.0471 (9) | |
H4A | 0.3797 | 0.0390 | 0.3710 | 0.056* | |
H4B | 0.4600 | 0.1427 | 0.3737 | 0.056* | |
C5 | 0.3470 (4) | 0.1352 (4) | 0.2703 (2) | 0.0620 (12) | |
H5A | 0.2634 | 0.1115 | 0.2586 | 0.074* | |
H5B | 0.4046 | 0.0978 | 0.2340 | 0.074* | |
H5C | 0.3529 | 0.2097 | 0.2589 | 0.074* | |
C6 | 0.1828 (3) | 0.0975 (3) | 0.4426 (2) | 0.0449 (9) | |
H6A | 0.1579 | 0.0550 | 0.3935 | 0.054* | |
H6B | 0.1131 | 0.1428 | 0.4577 | 0.054* | |
C7 | 0.2113 (4) | 0.0263 (3) | 0.5165 (3) | 0.0613 (12) | |
H7A | 0.2814 | −0.0178 | 0.5024 | 0.074* | |
H7B | 0.1399 | −0.0173 | 0.5285 | 0.074* | |
H7C | 0.2308 | 0.0681 | 0.5663 | 0.074* | |
C11 | 0.3881 (3) | 0.5027 (2) | 0.63213 (18) | 0.0282 (6) | |
C12 | 0.4005 (3) | 0.4114 (3) | 0.67604 (19) | 0.0301 (7) | |
C13 | 0.4696 (3) | 0.4056 (3) | 0.7496 (2) | 0.0395 (8) | |
H13 | 0.4785 | 0.3422 | 0.7794 | 0.047* | |
C14 | 0.5250 (3) | 0.4957 (3) | 0.7777 (2) | 0.0475 (9) | |
H14 | 0.5719 | 0.4946 | 0.8281 | 0.057* | |
C15 | 0.5129 (3) | 0.5872 (3) | 0.7330 (2) | 0.0465 (9) | |
H15 | 0.5534 | 0.6477 | 0.7527 | 0.056* | |
C16 | 0.4427 (3) | 0.5925 (3) | 0.6599 (2) | 0.0378 (8) | |
H16 | 0.4329 | 0.6560 | 0.6303 | 0.045* | |
C17 | 0.3083 (3) | 0.4862 (2) | 0.55451 (18) | 0.0270 (6) | |
C18 | 0.3322 (3) | 0.3296 (2) | 0.63104 (18) | 0.0267 (7) | |
C21 | 0.2016 (3) | 0.5627 (2) | 0.55357 (19) | 0.0282 (6) | |
C22 | 0.1213 (3) | 0.5684 (2) | 0.62133 (19) | 0.0288 (7) | |
C23 | 0.0268 (3) | 0.6424 (3) | 0.6209 (2) | 0.0387 (8) | |
C24 | 0.0181 (3) | 0.7127 (3) | 0.5553 (2) | 0.0488 (9) | |
H24 | −0.0436 | 0.7646 | 0.5560 | 0.059* | |
C25 | 0.0991 (4) | 0.7074 (3) | 0.4892 (2) | 0.0528 (10) | |
H25 | 0.0927 | 0.7555 | 0.4441 | 0.063* | |
C26 | 0.1894 (3) | 0.6330 (3) | 0.4877 (2) | 0.0412 (8) | |
H26 | 0.2440 | 0.6297 | 0.4411 | 0.049* | |
C27 | 0.1520 (4) | 0.5374 (3) | 0.76851 (19) | 0.0453 (10) | |
H27A | 0.2206 | 0.5864 | 0.7671 | 0.054* | |
H27B | 0.1715 | 0.4803 | 0.8070 | 0.054* | |
H27C | 0.0781 | 0.5731 | 0.7882 | 0.054* | |
C28 | −0.1497 (4) | 0.7099 (4) | 0.6912 (3) | 0.0775 (15) | |
H28A | −0.1166 | 0.7805 | 0.6930 | 0.093* | |
H28B | −0.1992 | 0.6974 | 0.7417 | 0.093* | |
H28C | −0.2008 | 0.7017 | 0.6409 | 0.093* | |
N1 | 0.2730 (2) | 0.37620 (19) | 0.56566 (15) | 0.0251 (5) | |
N2 | 0.2880 (3) | 0.1622 (2) | 0.41888 (17) | 0.0370 (7) | |
O1 | 0.4070 (2) | 0.30355 (18) | 0.43292 (14) | 0.0382 (6) | |
O2 | 0.3777 (2) | 0.4995 (2) | 0.47987 (13) | 0.0344 (5) | |
H2 | 0.394 (4) | 0.432 (3) | 0.463 (3) | 0.083 (16)* | |
O3 | 0.3280 (2) | 0.23709 (16) | 0.64681 (14) | 0.0378 (6) | |
O4 | 0.13140 (19) | 0.49712 (17) | 0.68540 (12) | 0.0310 (5) | |
O5 | −0.0513 (2) | 0.63737 (19) | 0.68843 (16) | 0.0472 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0255 (15) | 0.0316 (16) | 0.0264 (15) | −0.0004 (14) | −0.0033 (13) | −0.0038 (13) |
C2 | 0.0283 (16) | 0.0437 (18) | 0.0318 (16) | 0.0033 (15) | −0.0057 (15) | −0.0038 (15) |
C3 | 0.0294 (16) | 0.0384 (17) | 0.0269 (15) | 0.0045 (15) | −0.0036 (15) | −0.0033 (14) |
C4 | 0.040 (2) | 0.048 (2) | 0.053 (2) | 0.0086 (19) | −0.0002 (19) | −0.0218 (18) |
C5 | 0.055 (3) | 0.082 (3) | 0.049 (2) | 0.003 (3) | 0.007 (2) | −0.018 (2) |
C6 | 0.0379 (18) | 0.0425 (19) | 0.054 (2) | −0.0066 (17) | −0.0081 (19) | −0.0157 (18) |
C7 | 0.056 (3) | 0.051 (2) | 0.077 (3) | −0.009 (2) | −0.002 (2) | 0.005 (2) |
C11 | 0.0227 (15) | 0.0335 (15) | 0.0285 (14) | 0.0045 (14) | 0.0036 (13) | −0.0057 (14) |
C12 | 0.0248 (16) | 0.0384 (17) | 0.0270 (15) | 0.0035 (14) | −0.0002 (13) | −0.0026 (14) |
C13 | 0.0353 (19) | 0.054 (2) | 0.0297 (16) | 0.0070 (18) | −0.0094 (16) | −0.0046 (16) |
C14 | 0.0337 (19) | 0.070 (2) | 0.0391 (19) | 0.005 (2) | −0.0097 (16) | −0.0171 (19) |
C15 | 0.0342 (19) | 0.056 (2) | 0.049 (2) | −0.0083 (19) | 0.0006 (18) | −0.0192 (19) |
C16 | 0.0335 (18) | 0.0383 (18) | 0.0417 (19) | −0.0062 (16) | 0.0007 (16) | −0.0054 (16) |
C17 | 0.0288 (15) | 0.0284 (15) | 0.0238 (13) | −0.0001 (13) | 0.0049 (13) | 0.0021 (13) |
C18 | 0.0239 (15) | 0.0326 (16) | 0.0236 (14) | 0.0037 (14) | −0.0006 (13) | 0.0003 (13) |
C21 | 0.0314 (16) | 0.0264 (14) | 0.0269 (14) | 0.0020 (13) | −0.0015 (14) | −0.0009 (13) |
C22 | 0.0283 (16) | 0.0291 (15) | 0.0289 (15) | −0.0006 (14) | −0.0030 (14) | −0.0019 (13) |
C23 | 0.0318 (17) | 0.0415 (19) | 0.0428 (18) | 0.0011 (16) | 0.0027 (16) | −0.0052 (16) |
C24 | 0.042 (2) | 0.0429 (19) | 0.061 (2) | 0.0169 (18) | −0.002 (2) | 0.0082 (19) |
C25 | 0.052 (2) | 0.053 (2) | 0.054 (2) | 0.014 (2) | 0.001 (2) | 0.024 (2) |
C26 | 0.039 (2) | 0.0441 (19) | 0.0400 (18) | 0.0040 (17) | 0.0040 (17) | 0.0130 (16) |
C27 | 0.053 (3) | 0.055 (2) | 0.0282 (17) | 0.003 (2) | 0.0005 (17) | −0.0058 (16) |
C28 | 0.051 (3) | 0.077 (3) | 0.105 (4) | 0.027 (3) | 0.024 (3) | −0.004 (3) |
N1 | 0.0270 (12) | 0.0279 (13) | 0.0204 (12) | −0.0003 (11) | −0.0018 (11) | −0.0002 (11) |
N2 | 0.0328 (15) | 0.0399 (15) | 0.0383 (15) | 0.0026 (13) | −0.0001 (13) | −0.0105 (13) |
O1 | 0.0322 (12) | 0.0416 (13) | 0.0410 (13) | −0.0014 (11) | 0.0079 (11) | −0.0072 (11) |
O2 | 0.0371 (13) | 0.0374 (12) | 0.0285 (11) | 0.0004 (12) | 0.0108 (10) | 0.0043 (11) |
O3 | 0.0454 (14) | 0.0316 (12) | 0.0365 (12) | 0.0024 (11) | −0.0065 (11) | 0.0062 (10) |
O4 | 0.0319 (12) | 0.0353 (11) | 0.0259 (10) | 0.0000 (11) | 0.0019 (9) | −0.0010 (10) |
O5 | 0.0394 (14) | 0.0505 (15) | 0.0519 (14) | 0.0111 (13) | 0.0115 (12) | −0.0074 (13) |
C1—N1 | 1.459 (4) | C14—C15 | 1.384 (5) |
C1—C2 | 1.526 (4) | C14—H14 | 0.9500 |
C1—C3 | 1.542 (4) | C15—C16 | 1.391 (5) |
C1—H1 | 1.0000 | C15—H15 | 0.9500 |
C2—H2A | 0.9800 | C16—H16 | 0.9500 |
C2—H2B | 0.9800 | C17—O2 | 1.416 (3) |
C2—H2C | 0.9800 | C17—N1 | 1.481 (4) |
C3—O1 | 1.247 (4) | C17—C21 | 1.528 (4) |
C3—N2 | 1.332 (4) | C18—O3 | 1.221 (3) |
C4—N2 | 1.472 (4) | C18—N1 | 1.362 (4) |
C4—C5 | 1.505 (5) | C21—C22 | 1.389 (4) |
C4—H4A | 0.9900 | C21—C26 | 1.391 (4) |
C4—H4B | 0.9900 | C22—O4 | 1.375 (4) |
C5—H5A | 0.9800 | C22—C23 | 1.406 (4) |
C5—H5B | 0.9800 | C23—O5 | 1.371 (4) |
C5—H5C | 0.9800 | C23—C24 | 1.384 (5) |
C6—N2 | 1.469 (4) | C24—C25 | 1.374 (5) |
C6—C7 | 1.522 (5) | C24—H24 | 0.9500 |
C6—H6A | 0.9900 | C25—C26 | 1.377 (5) |
C6—H6B | 0.9900 | C25—H25 | 0.9500 |
C7—H7A | 0.9800 | C26—H26 | 0.9500 |
C7—H7B | 0.9800 | C27—O4 | 1.436 (4) |
C7—H7C | 0.9800 | C27—H27A | 0.9800 |
C11—C12 | 1.376 (4) | C27—H27B | 0.9800 |
C11—C16 | 1.376 (4) | C27—H27C | 0.9800 |
C11—C17 | 1.523 (4) | C28—O5 | 1.426 (4) |
C12—C13 | 1.392 (4) | C28—H28A | 0.9800 |
C12—C18 | 1.476 (4) | C28—H28B | 0.9800 |
C13—C14 | 1.384 (5) | C28—H28C | 0.9800 |
C13—H13 | 0.9500 | O2—H2 | 0.94 (4) |
N1—C1—C2 | 114.0 (2) | C16—C15—H15 | 119.3 |
N1—C1—C3 | 108.7 (2) | C11—C16—C15 | 117.7 (3) |
C2—C1—C3 | 109.9 (2) | C11—C16—H16 | 121.2 |
N1—C1—H1 | 108.0 | C15—C16—H16 | 121.2 |
C2—C1—H1 | 108.0 | O2—C17—N1 | 110.8 (2) |
C3—C1—H1 | 108.0 | O2—C17—C11 | 110.7 (2) |
C1—C2—H2A | 109.5 | N1—C17—C11 | 100.7 (2) |
C1—C2—H2B | 109.5 | O2—C17—C21 | 108.7 (2) |
H2A—C2—H2B | 109.5 | N1—C17—C21 | 114.9 (2) |
C1—C2—H2C | 109.5 | C11—C17—C21 | 110.7 (2) |
H2A—C2—H2C | 109.5 | O3—C18—N1 | 124.8 (3) |
H2B—C2—H2C | 109.5 | O3—C18—C12 | 128.2 (3) |
O1—C3—N2 | 121.5 (3) | N1—C18—C12 | 107.0 (3) |
O1—C3—C1 | 119.3 (3) | C22—C21—C26 | 119.2 (3) |
N2—C3—C1 | 119.1 (3) | C22—C21—C17 | 120.6 (3) |
N2—C4—C5 | 112.0 (3) | C26—C21—C17 | 120.1 (3) |
N2—C4—H4A | 109.2 | O4—C22—C21 | 119.1 (3) |
C5—C4—H4A | 109.2 | O4—C22—C23 | 121.1 (3) |
N2—C4—H4B | 109.2 | C21—C22—C23 | 119.7 (3) |
C5—C4—H4B | 109.2 | O5—C23—C24 | 125.2 (3) |
H4A—C4—H4B | 107.9 | O5—C23—C22 | 114.9 (3) |
C4—C5—H5A | 109.5 | C24—C23—C22 | 120.0 (3) |
C4—C5—H5B | 109.5 | C25—C24—C23 | 119.8 (3) |
H5A—C5—H5B | 109.5 | C25—C24—H24 | 120.1 |
C4—C5—H5C | 109.5 | C23—C24—H24 | 120.1 |
H5A—C5—H5C | 109.5 | C24—C25—C26 | 120.7 (3) |
H5B—C5—H5C | 109.5 | C24—C25—H25 | 119.7 |
N2—C6—C7 | 112.4 (3) | C26—C25—H25 | 119.7 |
N2—C6—H6A | 109.1 | C25—C26—C21 | 120.6 (3) |
C7—C6—H6A | 109.1 | C25—C26—H26 | 119.7 |
N2—C6—H6B | 109.1 | C21—C26—H26 | 119.7 |
C7—C6—H6B | 109.1 | O4—C27—H27A | 109.5 |
H6A—C6—H6B | 107.9 | O4—C27—H27B | 109.5 |
C6—C7—H7A | 109.5 | H27A—C27—H27B | 109.5 |
C6—C7—H7B | 109.5 | O4—C27—H27C | 109.5 |
H7A—C7—H7B | 109.5 | H27A—C27—H27C | 109.5 |
C6—C7—H7C | 109.5 | H27B—C27—H27C | 109.5 |
H7A—C7—H7C | 109.5 | O5—C28—H28A | 109.5 |
H7B—C7—H7C | 109.5 | O5—C28—H28B | 109.5 |
C12—C11—C16 | 121.1 (3) | H28A—C28—H28B | 109.5 |
C12—C11—C17 | 110.2 (3) | O5—C28—H28C | 109.5 |
C16—C11—C17 | 128.7 (3) | H28A—C28—H28C | 109.5 |
C11—C12—C13 | 121.6 (3) | H28B—C28—H28C | 109.5 |
C11—C12—C18 | 108.5 (3) | C18—N1—C1 | 117.8 (2) |
C13—C12—C18 | 129.9 (3) | C18—N1—C17 | 113.0 (2) |
C14—C13—C12 | 117.5 (3) | C1—N1—C17 | 126.9 (2) |
C14—C13—H13 | 121.2 | C3—N2—C6 | 124.6 (3) |
C12—C13—H13 | 121.2 | C3—N2—C4 | 119.0 (3) |
C15—C14—C13 | 120.7 (3) | C6—N2—C4 | 116.3 (3) |
C15—C14—H14 | 119.7 | C17—O2—H2 | 104 (3) |
C13—C14—H14 | 119.7 | C22—O4—C27 | 116.7 (2) |
C14—C15—C16 | 121.4 (3) | C23—O5—C28 | 117.5 (3) |
C14—C15—H15 | 119.3 | ||
N1—C1—C3—O1 | −33.8 (4) | C21—C22—C23—O5 | 176.4 (3) |
C2—C1—C3—O1 | 91.6 (3) | O4—C22—C23—C24 | −179.5 (3) |
N1—C1—C3—N2 | 148.9 (3) | C21—C22—C23—C24 | −3.5 (5) |
C2—C1—C3—N2 | −85.8 (3) | O5—C23—C24—C25 | −177.3 (3) |
C16—C11—C12—C13 | −0.8 (5) | C22—C23—C24—C25 | 2.5 (5) |
C17—C11—C12—C13 | 179.8 (3) | C23—C24—C25—C26 | −0.3 (6) |
C16—C11—C12—C18 | 180.0 (3) | C24—C25—C26—C21 | −0.9 (6) |
C17—C11—C12—C18 | 0.5 (3) | C22—C21—C26—C25 | −0.1 (5) |
C11—C12—C13—C14 | 0.6 (5) | C17—C21—C26—C25 | −175.1 (3) |
C18—C12—C13—C14 | 179.6 (3) | O3—C18—N1—C1 | −7.6 (5) |
C12—C13—C14—C15 | −0.9 (5) | C12—C18—N1—C1 | 171.8 (2) |
C13—C14—C15—C16 | 1.6 (6) | O3—C18—N1—C17 | −171.8 (3) |
C12—C11—C16—C15 | 1.3 (5) | C12—C18—N1—C17 | 7.5 (3) |
C17—C11—C16—C15 | −179.3 (3) | C2—C1—N1—C18 | 164.5 (3) |
C14—C15—C16—C11 | −1.7 (5) | C3—C1—N1—C18 | −72.6 (3) |
C12—C11—C17—O2 | −113.7 (3) | C2—C1—N1—C17 | −33.7 (4) |
C16—C11—C17—O2 | 66.9 (4) | C3—C1—N1—C17 | 89.2 (3) |
C12—C11—C17—N1 | 3.6 (3) | O2—C17—N1—C18 | 110.3 (3) |
C16—C11—C17—N1 | −175.8 (3) | C11—C17—N1—C18 | −6.9 (3) |
C12—C11—C17—C21 | 125.6 (3) | C21—C17—N1—C18 | −125.9 (3) |
C16—C11—C17—C21 | −53.8 (4) | O2—C17—N1—C1 | −52.2 (4) |
C11—C12—C18—O3 | 174.5 (3) | C11—C17—N1—C1 | −169.4 (3) |
C13—C12—C18—O3 | −4.7 (6) | C21—C17—N1—C1 | 71.6 (4) |
C11—C12—C18—N1 | −4.9 (3) | O1—C3—N2—C6 | 173.4 (3) |
C13—C12—C18—N1 | 176.0 (3) | C1—C3—N2—C6 | −9.3 (4) |
O2—C17—C21—C22 | −177.7 (3) | O1—C3—N2—C4 | −2.3 (5) |
N1—C17—C21—C22 | 57.5 (4) | C1—C3—N2—C4 | 175.0 (3) |
C11—C17—C21—C22 | −55.8 (4) | C7—C6—N2—C3 | −91.1 (4) |
O2—C17—C21—C26 | −2.8 (4) | C7—C6—N2—C4 | 84.7 (4) |
N1—C17—C21—C26 | −127.6 (3) | C5—C4—N2—C3 | −93.6 (4) |
C11—C17—C21—C26 | 119.1 (3) | C5—C4—N2—C6 | 90.4 (4) |
C26—C21—C22—O4 | 178.3 (3) | C21—C22—O4—C27 | 121.9 (3) |
C17—C21—C22—O4 | −6.7 (4) | C23—C22—O4—C27 | −62.0 (4) |
C26—C21—C22—C23 | 2.2 (5) | C24—C23—O5—C28 | 0.4 (5) |
C17—C21—C22—C23 | 177.2 (3) | C22—C23—O5—C28 | −179.5 (3) |
O4—C22—C23—O5 | 0.4 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1 | 0.94 (4) | 1.72 (4) | 2.656 (3) | 173 (4) |
C15—H15···O3i | 0.95 | 2.36 | 3.224 (4) | 152 |
C28—H28B···O3ii | 0.98 | 2.32 | 3.244 (5) | 157 |
C4—H4A···O5iii | 0.99 | 2.58 | 3.437 (4) | 145 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x, y+1/2, −z+3/2; (iii) x+1/2, −y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C23H28N2O5 |
Mr | 412.47 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 143 |
a, b, c (Å) | 10.921 (2), 12.905 (3), 15.868 (4) |
V (Å3) | 2236.4 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.4 × 0.4 × 0.3 |
Data collection | |
Diffractometer | Stoe STADI-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2895, 2895, 2188 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.110, 1.12 |
No. of reflections | 2895 |
No. of parameters | 281 |
No. of restraints | 271 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.19, −0.18 |
Computer programs: DIF4 (Stoe & Cie, 1992), DIF4, REDU4 (Stoe & Cie, 1992), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1 | 0.94 (4) | 1.72 (4) | 2.656 (3) | 173 (4) |
C15—H15···O3i | 0.95 | 2.36 | 3.224 (4) | 152 |
C28—H28B···O3ii | 0.98 | 2.32 | 3.244 (5) | 157 |
C4—H4A···O5iii | 0.99 | 2.58 | 3.437 (4) | 145 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x, y+1/2, −z+3/2; (iii) x+1/2, −y+1/2, −z+1. |
In a continuation of our interest in the synthesis of chiral tetrahydroisoquinolines as alkaloid analogues (Faltz et al., 1997; Faltz & Liebscher, 1998), we attempted to synthesize alternative precursors, such as (4), by reaction of o-lithiated 1,2-dimethoxybenzene, (1), with phthalimido-protected alanine amides, (2). The outcome of the reaction depends on the substituents R1 and R2 attached to the amide N atom. If the diethylamide (2) (R1 = R2 = Et) was used, the attack of lithiated (1) occurred at the phthalimido carbonyl group affording (3), whereas the Weinreb amide (2) (R1 = Me, R2 = OMe) reacted at the amide carbonyl group to form the ketone (4). The configuration of the new stereogenic center in (3) was established by this X-ray crystal analysis.
An analogous introduction of organic substituents to the phthalimido group has been reported at phthalimido-substituted α-amino esters (Wittig et al., 1955; Shklyaev et al., 1984; Griesbeck & Oelgemoeller, 1999). These products are of pharmaceutical interest (Dugger et al. 1979).
The structure of (3) is shown in Fig. 1. The molecule displays a linear intramolecular hydrogen bond between the hydroxy group and the carbonyl O atom of the amide moiety. The phthalimide ring system is planar (mean deviation of ninr atoms = 0.019 Å).
Apart from the intramolecular hydrogen bond, two short C—H···O contacts link the molecules to form highly indented layers parallel to the ab plane (Fig. 2).