organic compounds
The five-membered ring in the title compound, C19H19NO3S, is almost planar. The cis configuration of the ring substituents and the absolute configuration determination confirm the proposed mechanism of the stereospecific synthesis.
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802010759/bt6155sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802010759/bt6155Isup2.hkl |
CCDC reference: 189906
Key indicators
- Single-crystal X-ray study
- T = 160 K
- Mean (C-C) = 0.003 Å
- R factor = 0.030
- wR factor = 0.079
- Data-to-parameter ratio = 15.4
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
ABSTM_02 Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.750 0.928 Tmin' and Tmax expected: 0.901 0.936 RR' = 0.839 Please check that your absorption correction is appropriate. General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 28.70 From the CIF: _reflns_number_total 3382 Count of symmetry unique reflns 2536 Completeness (_total/calc) 133.36% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 846 Fraction of Friedel pairs measured 0.334 Are heavy atom types Z>Si present yes WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
Computing details top
Data collection: SMART (Siemens, 1995); cell refinement: local programs; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXTL (Sheldrick, 1994); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.
(4S,5S)-2-Benzyloxy-4-methyl-5-(4-tolylthiocarbonyl)oxazoline top
Crystal data top
C19H19NO3S | F(000) = 360 |
Mr = 341.41 | Dx = 1.266 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.9010 (9) Å | Cell parameters from 6005 reflections |
b = 5.7705 (4) Å | θ = 2.7–28.7° |
c = 13.7964 (10) Å | µ = 0.20 mm−1 |
β = 109.043 (2)° | T = 160 K |
V = 895.61 (11) Å3 | Rectangular block, colourless |
Z = 2 | 0.52 × 0.40 × 0.34 mm |
Data collection top
Siemens SMART 1K CCD diffractometer | 3382 independent reflections |
Radiation source: sealed tube | 3203 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
Detector resolution: 8.192 pixels mm-1 | θmax = 28.7°, θmin = 1.8° |
ω rotation with narrow frames scans | h = −15→15 |
Absorption correction: multi-scan (XPREP in SHELXTL; Sheldrick, 1994) | k = −6→7 |
Tmin = 0.750, Tmax = 0.928 | l = −17→18 |
6725 measured reflections |
Refinement top
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)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.079 | w = 1/[σ2(Fo2) + (0.0493P)2 + 0.0826P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
3382 reflections | Δρmax = 0.21 e Å−3 |
219 parameters | Δρmin = −0.19 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 1056 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.08 (6) |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | ||
O1 | 0.77056 (9) | 0.15718 (19) | 0.88474 (9) | 0.0315 (3) | |
C1 | 0.80856 (12) | 0.3805 (3) | 0.90228 (10) | 0.0250 (3) | |
N1 | 0.75829 (11) | 0.5210 (2) | 0.94457 (9) | 0.0281 (3) | |
C2 | 0.66024 (12) | 0.3912 (3) | 0.96289 (10) | 0.0257 (3) | |
H2 | 0.6778 | 0.3730 | 1.0385 | 0.031* | |
C3 | 0.66524 (12) | 0.1468 (3) | 0.91457 (11) | 0.0263 (3) | |
H3 | 0.6751 | 0.0242 | 0.9679 | 0.032* | |
C4 | 0.55805 (12) | 0.0917 (3) | 0.82225 (10) | 0.0251 (3) | |
O2 | 0.46249 (9) | 0.0483 (2) | 0.83037 (8) | 0.0302 (2) | |
C5 | 0.54399 (14) | 0.5225 (3) | 0.91859 (12) | 0.0322 (3) | |
H5A | 0.5506 | 0.6741 | 0.9520 | 0.048* | |
H5B | 0.4794 | 0.4339 | 0.9305 | 0.048* | |
H5C | 0.5270 | 0.5441 | 0.8447 | 0.048* | |
O3 | 0.90081 (9) | 0.4140 (2) | 0.86971 (8) | 0.0291 (2) | |
C6 | 0.95440 (14) | 0.6417 (3) | 0.89320 (13) | 0.0330 (3) | |
H6A | 0.9910 | 0.6609 | 0.9683 | 0.040* | |
H6B | 0.8935 | 0.7637 | 0.8673 | 0.040* | |
C7 | 1.04768 (13) | 0.6597 (3) | 0.84150 (11) | 0.0269 (3) | |
C8 | 1.12865 (13) | 0.4826 (3) | 0.84919 (11) | 0.0290 (3) | |
H8 | 1.1265 | 0.3482 | 0.8883 | 0.035* | |
C9 | 1.21306 (14) | 0.5010 (3) | 0.79981 (12) | 0.0341 (4) | |
H9 | 1.2676 | 0.3781 | 0.8040 | 0.041* | |
C10 | 1.21756 (15) | 0.7000 (4) | 0.74417 (13) | 0.0385 (4) | |
H10 | 1.2753 | 0.7133 | 0.7105 | 0.046* | |
C11 | 1.13857 (17) | 0.8765 (4) | 0.73799 (13) | 0.0416 (4) | |
H11 | 1.1424 | 1.0130 | 0.7007 | 0.050* | |
C12 | 1.05275 (15) | 0.8572 (3) | 0.78591 (13) | 0.0357 (4) | |
H12 | 0.9976 | 0.9794 | 0.7805 | 0.043* | |
S1 | 0.58788 (4) | 0.10061 (8) | 0.70389 (3) | 0.03961 (12) | |
C13 | 0.44347 (16) | 0.0351 (3) | 0.61861 (12) | 0.0352 (4) | |
C14 | 0.42437 (18) | −0.1741 (4) | 0.56673 (13) | 0.0411 (4) | |
H14 | 0.4875 | −0.2821 | 0.5772 | 0.049* | |
C15 | 0.3119 (2) | −0.2245 (4) | 0.49909 (13) | 0.0472 (5) | |
H15 | 0.2988 | −0.3679 | 0.4633 | 0.057* | |
C16 | 0.2187 (2) | −0.0705 (4) | 0.48289 (13) | 0.0482 (5) | |
C17 | 0.23960 (19) | 0.1389 (4) | 0.53491 (13) | 0.0484 (5) | |
H17 | 0.1765 | 0.2470 | 0.5242 | 0.058* | |
C18 | 0.35148 (17) | 0.1930 (3) | 0.60242 (13) | 0.0413 (4) | |
H18 | 0.3649 | 0.3375 | 0.6373 | 0.050* | |
C19 | 0.0957 (2) | −0.1310 (6) | 0.41158 (18) | 0.0787 (9) | |
H19A | 0.0615 | −0.2533 | 0.4426 | 0.118* | |
H19B | 0.1011 | −0.1857 | 0.3460 | 0.118* | |
H19C | 0.0449 | 0.0068 | 0.4000 | 0.118* |
Atomic displacement parameters (Å2) top
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0203 (5) | 0.0217 (6) | 0.0542 (6) | −0.0026 (4) | 0.0147 (5) | −0.0020 (5) |
C1 | 0.0183 (6) | 0.0241 (7) | 0.0298 (7) | −0.0029 (6) | 0.0039 (5) | 0.0012 (6) |
N1 | 0.0252 (6) | 0.0276 (7) | 0.0327 (6) | −0.0077 (6) | 0.0111 (5) | −0.0042 (5) |
C2 | 0.0243 (7) | 0.0251 (8) | 0.0282 (6) | −0.0056 (6) | 0.0093 (6) | 0.0000 (6) |
C3 | 0.0198 (6) | 0.0237 (8) | 0.0358 (7) | −0.0032 (6) | 0.0096 (5) | 0.0038 (6) |
C4 | 0.0246 (7) | 0.0202 (7) | 0.0316 (6) | −0.0026 (6) | 0.0108 (5) | 0.0015 (6) |
O2 | 0.0217 (5) | 0.0374 (7) | 0.0321 (5) | −0.0073 (5) | 0.0095 (4) | 0.0017 (4) |
C5 | 0.0299 (8) | 0.0275 (8) | 0.0436 (8) | 0.0004 (7) | 0.0181 (7) | 0.0010 (7) |
O3 | 0.0200 (5) | 0.0250 (6) | 0.0444 (6) | −0.0055 (4) | 0.0133 (4) | −0.0044 (5) |
C6 | 0.0303 (8) | 0.0259 (9) | 0.0473 (8) | −0.0099 (7) | 0.0187 (7) | −0.0096 (7) |
C7 | 0.0210 (7) | 0.0276 (8) | 0.0311 (6) | −0.0073 (6) | 0.0070 (5) | −0.0059 (6) |
C8 | 0.0246 (7) | 0.0292 (8) | 0.0308 (7) | −0.0045 (6) | 0.0057 (6) | −0.0003 (6) |
C9 | 0.0212 (7) | 0.0413 (10) | 0.0382 (8) | −0.0029 (7) | 0.0074 (6) | −0.0068 (7) |
C10 | 0.0347 (9) | 0.0465 (11) | 0.0397 (8) | −0.0140 (8) | 0.0196 (7) | −0.0075 (7) |
C11 | 0.0511 (11) | 0.0361 (10) | 0.0418 (9) | −0.0114 (9) | 0.0211 (8) | 0.0037 (8) |
C12 | 0.0352 (9) | 0.0284 (9) | 0.0436 (8) | −0.0018 (7) | 0.0128 (7) | 0.0009 (7) |
S1 | 0.0357 (2) | 0.0519 (3) | 0.0380 (2) | −0.0130 (2) | 0.02127 (17) | −0.00887 (18) |
C13 | 0.0423 (9) | 0.0396 (10) | 0.0272 (7) | −0.0107 (8) | 0.0161 (6) | −0.0032 (6) |
C14 | 0.0535 (11) | 0.0428 (11) | 0.0334 (8) | −0.0082 (9) | 0.0229 (8) | −0.0067 (7) |
C15 | 0.0709 (13) | 0.0446 (11) | 0.0270 (7) | −0.0200 (11) | 0.0170 (8) | −0.0075 (7) |
C16 | 0.0576 (12) | 0.0519 (12) | 0.0263 (8) | −0.0164 (11) | 0.0018 (8) | 0.0079 (7) |
C17 | 0.0514 (11) | 0.0458 (12) | 0.0389 (8) | −0.0018 (10) | 0.0024 (8) | 0.0104 (8) |
C18 | 0.0510 (11) | 0.0360 (10) | 0.0351 (8) | −0.0080 (9) | 0.0118 (8) | −0.0006 (7) |
C19 | 0.0755 (17) | 0.082 (2) | 0.0489 (12) | −0.0262 (16) | −0.0202 (11) | 0.0105 (12) |
Geometric parameters (Å, º) top
O1—C1 | 1.361 (2) | C9—H9 | 0.950 |
O1—C3 | 1.4424 (16) | C9—C10 | 1.392 (3) |
C1—N1 | 1.258 (2) | C10—H10 | 0.950 |
C1—O3 | 1.3292 (17) | C10—C11 | 1.370 (3) |
N1—C2 | 1.4760 (19) | C11—H11 | 0.950 |
C2—H2 | 1.000 | C11—C12 | 1.390 (2) |
C2—C3 | 1.569 (2) | C12—H12 | 0.950 |
C2—C5 | 1.520 (2) | S1—C13 | 1.7781 (18) |
C3—H3 | 1.000 | C13—C14 | 1.384 (3) |
C3—C4 | 1.513 (2) | C13—C18 | 1.385 (3) |
C4—O2 | 1.2048 (16) | C14—H14 | 0.950 |
C4—S1 | 1.7815 (13) | C14—C15 | 1.390 (3) |
C5—H5A | 0.980 | C15—H15 | 0.950 |
C5—H5B | 0.980 | C15—C16 | 1.382 (3) |
C5—H5C | 0.980 | C16—C17 | 1.386 (3) |
O3—C6 | 1.4501 (19) | C16—C19 | 1.514 (3) |
C6—H6A | 0.990 | C17—H17 | 0.950 |
C6—H6B | 0.990 | C17—C18 | 1.389 (3) |
C6—C7 | 1.5061 (19) | C18—H18 | 0.950 |
C7—C8 | 1.385 (2) | C19—H19A | 0.980 |
C7—C12 | 1.386 (2) | C19—H19B | 0.980 |
C8—H8 | 0.950 | C19—H19C | 0.980 |
C8—C9 | 1.390 (2) | ||
C1—O1—C3 | 104.94 (11) | H8—C8—C9 | 119.9 |
O1—C1—N1 | 120.79 (13) | C8—C9—H9 | 120.1 |
O1—C1—O3 | 109.94 (13) | C8—C9—C10 | 119.84 (16) |
N1—C1—O3 | 129.27 (15) | H9—C9—C10 | 120.1 |
C1—N1—C2 | 105.93 (14) | C9—C10—H10 | 120.0 |
N1—C2—H2 | 108.9 | C9—C10—C11 | 119.91 (15) |
N1—C2—C3 | 103.97 (11) | H10—C10—C11 | 120.0 |
N1—C2—C5 | 110.19 (13) | C10—C11—H11 | 119.8 |
H2—C2—C3 | 108.9 | C10—C11—C12 | 120.43 (17) |
H2—C2—C5 | 108.9 | H11—C11—C12 | 119.8 |
C3—C2—C5 | 115.65 (13) | C7—C12—C11 | 120.02 (16) |
O1—C3—C2 | 103.94 (11) | C7—C12—H12 | 120.0 |
O1—C3—H3 | 109.6 | C11—C12—H12 | 120.0 |
O1—C3—C4 | 109.94 (11) | C4—S1—C13 | 99.31 (7) |
C2—C3—H3 | 109.6 | S1—C13—C14 | 119.21 (15) |
C2—C3—C4 | 114.07 (13) | S1—C13—C18 | 120.61 (14) |
H3—C3—C4 | 109.6 | C14—C13—C18 | 120.16 (17) |
C3—C4—O2 | 121.84 (12) | C13—C14—H14 | 120.3 |
C3—C4—S1 | 113.58 (9) | C13—C14—C15 | 119.3 (2) |
O2—C4—S1 | 124.58 (11) | H14—C14—C15 | 120.3 |
C2—C5—H5A | 109.5 | C14—C15—H15 | 119.3 |
C2—C5—H5B | 109.5 | C14—C15—C16 | 121.35 (18) |
C2—C5—H5C | 109.5 | H15—C15—C16 | 119.3 |
H5A—C5—H5B | 109.5 | C15—C16—C17 | 118.56 (18) |
H5A—C5—H5C | 109.5 | C15—C16—C19 | 120.8 (2) |
H5B—C5—H5C | 109.5 | C17—C16—C19 | 120.7 (2) |
C1—O3—C6 | 114.08 (12) | C16—C17—H17 | 119.5 |
O3—C6—H6A | 110.3 | C16—C17—C18 | 120.9 (2) |
O3—C6—H6B | 110.3 | H17—C17—C18 | 119.5 |
O3—C6—C7 | 107.15 (12) | C13—C18—C17 | 119.66 (18) |
H6A—C6—H6B | 108.5 | C13—C18—H18 | 120.2 |
H6A—C6—C7 | 110.3 | C17—C18—H18 | 120.2 |
H6B—C6—C7 | 110.3 | C16—C19—H19A | 109.5 |
C6—C7—C8 | 121.00 (14) | C16—C19—H19B | 109.5 |
C6—C7—C12 | 119.38 (14) | C16—C19—H19C | 109.5 |
C8—C7—C12 | 119.62 (14) | H19A—C19—H19B | 109.5 |
C7—C8—H8 | 119.9 | H19A—C19—H19C | 109.5 |
C7—C8—C9 | 120.16 (15) | H19B—C19—H19C | 109.5 |
C3—O1—C1—N1 | 5.39 (18) | C12—C7—C8—C9 | −1.2 (2) |
C3—O1—C1—O3 | −175.19 (11) | C7—C8—C9—C10 | 1.3 (2) |
O1—C1—N1—C2 | −1.42 (18) | C8—C9—C10—C11 | −0.2 (2) |
O3—C1—N1—C2 | 179.28 (14) | C9—C10—C11—C12 | −0.8 (3) |
C1—N1—C2—C3 | −2.87 (15) | C6—C7—C12—C11 | 179.83 (15) |
C1—N1—C2—C5 | −127.40 (14) | C8—C7—C12—C11 | 0.2 (2) |
C1—O1—C3—C2 | −6.31 (14) | C10—C11—C12—C7 | 0.8 (3) |
C1—O1—C3—C4 | 116.17 (13) | C3—C4—S1—C13 | −178.74 (12) |
N1—C2—C3—O1 | 5.71 (14) | O2—C4—S1—C13 | 0.73 (17) |
N1—C2—C3—C4 | −114.00 (13) | C4—S1—C13—C14 | −111.95 (13) |
C5—C2—C3—O1 | 126.64 (12) | C4—S1—C13—C18 | 69.38 (14) |
C5—C2—C3—C4 | 6.93 (17) | S1—C13—C14—C15 | −179.25 (13) |
O1—C3—C4—O2 | 171.41 (14) | C18—C13—C14—C15 | −0.6 (2) |
O1—C3—C4—S1 | −9.11 (16) | C13—C14—C15—C16 | −0.2 (2) |
C2—C3—C4—O2 | −72.31 (19) | C14—C15—C16—C17 | 0.7 (3) |
C2—C3—C4—S1 | 107.17 (12) | C14—C15—C16—C19 | −178.03 (18) |
O1—C1—O3—C6 | −174.87 (12) | C15—C16—C17—C18 | −0.4 (3) |
N1—C1—O3—C6 | 4.5 (2) | C19—C16—C17—C18 | 178.34 (18) |
C1—O3—C6—C7 | −173.95 (12) | S1—C13—C18—C17 | 179.53 (13) |
O3—C6—C7—C8 | −46.97 (18) | C14—C13—C18—C17 | 0.9 (2) |
O3—C6—C7—C12 | 133.39 (15) | C16—C17—C18—C13 | −0.4 (3) |
C6—C7—C8—C9 | 179.14 (14) |