Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680200096X/dn6012sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680200096X/dn6012Isup2.hkl |
CCDC reference: 182630
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.040
- wR factor = 0.103
- Data-to-parameter ratio = 16.9
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 28.91 From the CIF: _reflns_number_total 4046 Count of symmetry unique reflns 2709 Completeness (_total/calc) 149.35% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1337 Fraction of Friedel pairs measured 0.494 Are heavy atom types Z>Si present yes WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure
Colourless crystals, shaped as square platelets, were obtained by evaporation of an ethanol solution.
Data collection: DENZO (Otwinowski & Minor, 1997); cell refinement: DENZO; data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: PLATON (Spek, 1990).
Fig. 1. ORTEPII (Johnson, 1976) drawing of (1). 1S and 2R correspond to atoms C15 and C14, respectively. |
C20H25NO4S | F(000) = 800 |
Mr = 375.47 | Dx = 1.272 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: C 2y | Cell parameters from 8349 reflections |
a = 10.147 (2) Å | θ = 2.9–28.9° |
b = 10.938 (2) Å | µ = 0.19 mm−1 |
c = 17.681 (3) Å | T = 293 K |
β = 92.65 (3)° | Needle, colourless |
V = 1960.3 (6) Å3 | 0.39 × 0.22 × 0.19 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 3702 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.041 |
Graphite monochromator | θmax = 28.9°, θmin = 2.9° |
ϕ scans | h = −12→13 |
8349 measured reflections | k = −14→13 |
4046 independent reflections | l = −23→20 |
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)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.103 | w = 1/[σ2(Fo2) + (0.0493P)2 + 0.4741P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
4046 reflections | Δρmax = 0.17 e Å−3 |
239 parameters | Δρmin = −0.17 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.06 (7) |
C20H25NO4S | V = 1960.3 (6) Å3 |
Mr = 375.47 | Z = 4 |
Monoclinic, C2 | Mo Kα radiation |
a = 10.147 (2) Å | µ = 0.19 mm−1 |
b = 10.938 (2) Å | T = 293 K |
c = 17.681 (3) Å | 0.39 × 0.22 × 0.19 mm |
β = 92.65 (3)° |
Nonius KappaCCD diffractometer | 3702 reflections with I > 2σ(I) |
8349 measured reflections | Rint = 0.041 |
4046 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.103 | Δρmax = 0.17 e Å−3 |
S = 1.05 | Δρmin = −0.17 e Å−3 |
4046 reflections | Absolute structure: Flack (1983) |
239 parameters | Absolute structure parameter: 0.06 (7) |
1 restraint |
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 | 1.3268 (3) | 0.7722 (4) | 1.02333 (16) | 0.0939 (12) | |
H1A | 1.3804 | 0.7271 | 0.9898 | 0.141* | |
H1B | 1.2812 | 0.7164 | 1.0548 | 0.141* | |
H1C | 1.3818 | 0.8251 | 1.0545 | 0.141* | |
O2 | 1.23340 (19) | 0.8436 (2) | 0.98017 (11) | 0.0843 (6) | |
C3 | 1.1409 (2) | 0.7825 (3) | 0.93751 (12) | 0.0573 (6) | |
C4 | 1.1338 (2) | 0.6592 (3) | 0.93133 (12) | 0.0584 (6) | |
H4 | 1.1945 | 0.6101 | 0.9582 | 0.070* | |
C5 | 1.0353 (2) | 0.6061 (2) | 0.88469 (13) | 0.0553 (5) | |
H5 | 1.0321 | 0.5215 | 0.8795 | 0.066* | |
C6 | 0.9424 (2) | 0.6776 (2) | 0.84599 (11) | 0.0477 (5) | |
C7 | 0.9515 (2) | 0.8019 (2) | 0.85406 (13) | 0.0578 (6) | |
H7 | 0.8898 | 0.8518 | 0.8287 | 0.069* | |
C8 | 1.0493 (3) | 0.8539 (3) | 0.89861 (15) | 0.0660 (6) | |
H8 | 1.0540 | 0.9386 | 0.9028 | 0.079* | |
C9 | 0.8398 (2) | 0.6166 (2) | 0.79962 (12) | 0.0534 (5) | |
H9 | 0.8540 | 0.5346 | 0.7887 | 0.064* | |
C10 | 0.7286 (2) | 0.6648 (2) | 0.77133 (11) | 0.0521 (5) | |
H10 | 0.7109 | 0.7472 | 0.7791 | 0.063* | |
C11 | 0.6335 (2) | 0.5895 (2) | 0.72791 (12) | 0.0541 (5) | |
O12 | 0.66000 (19) | 0.49286 (19) | 0.69955 (12) | 0.0879 (7) | |
N13 | 0.50551 (15) | 0.63475 (15) | 0.71772 (8) | 0.0423 (3) | |
C14 | 0.40516 (19) | 0.55650 (18) | 0.68117 (11) | 0.0457 (4) | |
H14 | 0.3958 | 0.4816 | 0.7109 | 0.055* | |
C15 | 0.27490 (16) | 0.62867 (18) | 0.67917 (9) | 0.0396 (4) | |
C16 | 0.27552 (17) | 0.7149 (3) | 0.74609 (10) | 0.0514 (4) | |
H16A | 0.2160 | 0.6857 | 0.7835 | 0.062* | |
H16B | 0.2473 | 0.7959 | 0.7298 | 0.062* | |
S17 | 0.43934 (4) | 0.71974 (5) | 0.78517 (2) | 0.04551 (13) | |
O18 | 0.49290 (18) | 0.83859 (17) | 0.78486 (13) | 0.0785 (6) | |
O19 | 0.44912 (19) | 0.6546 (2) | 0.85471 (8) | 0.0822 (6) | |
C20 | 0.4216 (2) | 0.5236 (3) | 0.59777 (13) | 0.0697 (8) | |
H20A | 0.4941 | 0.5682 | 0.5770 | 0.084* | |
H20B | 0.4359 | 0.4366 | 0.5915 | 0.084* | |
C21 | 0.2898 (2) | 0.5631 (2) | 0.56135 (12) | 0.0611 (6) | |
H21 | 0.2886 | 0.5666 | 0.5059 | 0.073* | |
C22 | 0.1823 (3) | 0.4834 (3) | 0.59213 (18) | 0.0826 (9) | |
H22A | 0.2089 | 0.3982 | 0.5938 | 0.099* | |
H22B | 0.1009 | 0.4908 | 0.5615 | 0.099* | |
C23 | 0.1663 (3) | 0.5339 (3) | 0.67194 (17) | 0.0704 (7) | |
H23A | 0.0801 | 0.5708 | 0.6766 | 0.084* | |
H23B | 0.1786 | 0.4703 | 0.7099 | 0.084* | |
C24 | 0.26874 (19) | 0.68725 (19) | 0.59920 (10) | 0.0485 (5) | |
C25 | 0.1357 (3) | 0.7450 (3) | 0.57794 (15) | 0.0752 (9) | |
H25A | 0.1363 | 0.7760 | 0.5272 | 0.113* | |
H25B | 0.1193 | 0.8108 | 0.6122 | 0.113* | |
H25C | 0.0675 | 0.6846 | 0.5811 | 0.113* | |
C26 | 0.3725 (3) | 0.7834 (3) | 0.58594 (14) | 0.0751 (8) | |
H26A | 0.3555 | 0.8545 | 0.6158 | 0.113* | |
H26B | 0.3697 | 0.8052 | 0.5333 | 0.113* | |
H26C | 0.4582 | 0.7514 | 0.6003 | 0.113* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0533 (13) | 0.162 (3) | 0.0636 (14) | −0.0045 (17) | −0.0212 (11) | −0.0253 (17) |
O2 | 0.0649 (11) | 0.1136 (17) | 0.0722 (12) | −0.0205 (12) | −0.0191 (8) | −0.0138 (11) |
C3 | 0.0452 (11) | 0.0858 (18) | 0.0405 (10) | −0.0125 (11) | −0.0021 (8) | −0.0051 (10) |
C4 | 0.0403 (11) | 0.0878 (19) | 0.0460 (10) | 0.0073 (12) | −0.0094 (8) | 0.0048 (11) |
C5 | 0.0423 (10) | 0.0652 (14) | 0.0572 (12) | 0.0096 (10) | −0.0102 (8) | −0.0033 (10) |
C6 | 0.0379 (9) | 0.0621 (13) | 0.0423 (9) | 0.0074 (8) | −0.0058 (7) | −0.0021 (8) |
C7 | 0.0578 (13) | 0.0593 (14) | 0.0550 (12) | 0.0006 (10) | −0.0129 (9) | 0.0082 (9) |
C8 | 0.0652 (15) | 0.0681 (16) | 0.0636 (14) | −0.0120 (13) | −0.0098 (11) | 0.0035 (11) |
C9 | 0.0462 (10) | 0.0588 (13) | 0.0538 (11) | 0.0131 (9) | −0.0128 (8) | −0.0113 (9) |
C10 | 0.0453 (10) | 0.0576 (12) | 0.0522 (10) | 0.0139 (9) | −0.0116 (8) | −0.0099 (9) |
C11 | 0.0485 (11) | 0.0579 (13) | 0.0541 (11) | 0.0218 (10) | −0.0177 (8) | −0.0155 (9) |
O12 | 0.0687 (11) | 0.0830 (13) | 0.1077 (15) | 0.0441 (10) | −0.0444 (10) | −0.0519 (11) |
N13 | 0.0394 (7) | 0.0472 (9) | 0.0390 (7) | 0.0135 (7) | −0.0112 (5) | −0.0105 (6) |
C14 | 0.0495 (10) | 0.0390 (9) | 0.0470 (9) | 0.0092 (8) | −0.0146 (8) | −0.0081 (7) |
C15 | 0.0358 (8) | 0.0448 (9) | 0.0381 (8) | 0.0026 (8) | 0.0001 (6) | −0.0035 (7) |
C16 | 0.0409 (9) | 0.0714 (13) | 0.0416 (8) | 0.0088 (11) | −0.0013 (6) | −0.0124 (10) |
S17 | 0.0451 (2) | 0.0519 (3) | 0.0388 (2) | 0.0096 (2) | −0.00575 (14) | −0.01192 (19) |
O18 | 0.0604 (10) | 0.0479 (10) | 0.1263 (17) | 0.0063 (8) | −0.0043 (9) | −0.0328 (10) |
O19 | 0.0820 (12) | 0.1292 (18) | 0.0347 (7) | 0.0189 (12) | −0.0055 (7) | 0.0101 (9) |
C20 | 0.0538 (12) | 0.0915 (19) | 0.0618 (13) | 0.0322 (12) | −0.0204 (10) | −0.0410 (13) |
C21 | 0.0512 (11) | 0.0839 (17) | 0.0467 (10) | 0.0240 (11) | −0.0157 (8) | −0.0254 (10) |
C22 | 0.0648 (16) | 0.0770 (19) | 0.103 (2) | 0.0007 (14) | −0.0245 (14) | −0.0376 (16) |
C23 | 0.0578 (14) | 0.0703 (17) | 0.0827 (17) | −0.0175 (13) | −0.0009 (11) | −0.0064 (13) |
C24 | 0.0437 (9) | 0.0629 (14) | 0.0378 (8) | 0.0135 (8) | −0.0104 (7) | −0.0010 (7) |
C25 | 0.0654 (14) | 0.086 (2) | 0.0715 (14) | 0.0313 (14) | −0.0302 (11) | −0.0094 (13) |
C26 | 0.0795 (17) | 0.0879 (19) | 0.0575 (13) | −0.0038 (15) | −0.0024 (11) | 0.0305 (13) |
C1—O2 | 1.422 (4) | C14—C20 | 1.534 (3) |
O2—C3 | 1.353 (3) | C14—C15 | 1.538 (3) |
C3—C4 | 1.355 (4) | C15—C16 | 1.513 (3) |
C3—C8 | 1.374 (4) | C15—C23 | 1.514 (3) |
C4—C5 | 1.392 (3) | C15—C24 | 1.551 (2) |
C5—C6 | 1.382 (3) | C16—S17 | 1.7712 (18) |
C6—C7 | 1.370 (3) | S17—O18 | 1.409 (2) |
C6—C9 | 1.457 (3) | S17—O19 | 1.4207 (18) |
C7—C8 | 1.362 (3) | C20—C21 | 1.519 (3) |
C9—C10 | 1.323 (3) | C21—C22 | 1.517 (4) |
C10—C11 | 1.460 (3) | C21—C24 | 1.534 (3) |
C11—O12 | 1.205 (3) | C22—C23 | 1.531 (4) |
C11—N13 | 1.394 (2) | C24—C26 | 1.514 (4) |
N13—C14 | 1.458 (2) | C24—C25 | 1.522 (3) |
N13—S17 | 1.6767 (15) | ||
C3—O2—C1 | 117.1 (3) | C23—C15—C14 | 105.77 (19) |
O2—C3—C4 | 124.7 (3) | C16—C15—C24 | 116.98 (18) |
O2—C3—C8 | 115.8 (3) | C23—C15—C24 | 101.97 (17) |
C4—C3—C8 | 119.5 (2) | C14—C15—C24 | 103.38 (14) |
C3—C4—C5 | 119.8 (2) | C15—C16—S17 | 107.06 (13) |
C6—C5—C4 | 120.8 (3) | O18—S17—O19 | 117.04 (14) |
C7—C6—C5 | 118.0 (2) | O18—S17—N13 | 109.97 (11) |
C7—C6—C9 | 123.8 (2) | O19—S17—N13 | 108.85 (11) |
C5—C6—C9 | 118.2 (2) | O18—S17—C16 | 112.39 (12) |
C8—C7—C6 | 121.2 (2) | O19—S17—C16 | 110.46 (12) |
C7—C8—C3 | 120.7 (3) | N13—S17—C16 | 96.06 (8) |
C10—C9—C6 | 127.2 (2) | C21—C20—C14 | 102.03 (17) |
C9—C10—C11 | 120.3 (2) | C22—C21—C20 | 108.5 (2) |
O12—C11—N13 | 118.83 (19) | C22—C21—C24 | 103.60 (19) |
O12—C11—C10 | 123.98 (18) | C20—C21—C24 | 101.81 (16) |
N13—C11—C10 | 117.17 (18) | C21—C22—C23 | 103.42 (19) |
C11—N13—C14 | 118.43 (16) | C15—C23—C22 | 102.5 (2) |
C11—N13—S17 | 120.42 (13) | C26—C24—C25 | 106.8 (2) |
C14—N13—S17 | 110.26 (12) | C26—C24—C21 | 115.8 (2) |
N13—C14—C20 | 117.33 (19) | C25—C24—C21 | 113.58 (18) |
N13—C14—C15 | 106.90 (15) | C26—C24—C15 | 115.41 (17) |
C20—C14—C15 | 103.27 (15) | C25—C24—C15 | 113.24 (18) |
C16—C15—C23 | 118.02 (18) | C21—C24—C15 | 91.80 (16) |
C16—C15—C14 | 109.24 (14) |
Experimental details
Crystal data | |
Chemical formula | C20H25NO4S |
Mr | 375.47 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 293 |
a, b, c (Å) | 10.147 (2), 10.938 (2), 17.681 (3) |
β (°) | 92.65 (3) |
V (Å3) | 1960.3 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.19 |
Crystal size (mm) | 0.39 × 0.22 × 0.19 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8349, 4046, 3702 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.680 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.103, 1.05 |
No. of reflections | 4046 |
No. of parameters | 239 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.17 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.06 (7) |
Computer programs: DENZO (Otwinowski & Minor, 1997), DENZO, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), PLATON (Spek, 1990).
The title compound, (1), was prepared by reaction between (E)-4-methoxy-cinnamoyl chloride and the sodium salt of (-)-10,2-camphorsultam (Oppolzer et al., 1992). The starting camphorsultam is a commercial product (1S,2R purum enantiomer) with a specific rotation of -33° in ethylic alcohol for a concentration c = 1. The Mn(OAc)3-induced radical addition of a β-keto ester to (1) gives preferentially a major diastereoisomer of a chiral dihydrofuran possessing two newly formed adjacent stereogenic centres (Garzino et al., 2000). The specific rotation of the synthesized compound is -85.4° in chloroform for a concentration c = 1. The crystal structure of compound (1) was determined by X-ray analysis in order to understand the origin of the facial selectivity of this oxidative addition. It is known that in such radical reactions the transition state resembles the substrate (Curran et al., 1996).