organic compounds
(Z)-2-[Methoxy(phenyl)methylidene]-3,4,5-trimethyl-2,3-dihydro-1,3-thiazole
aLudwig-Maximilians-Universität, Department, Butenandtstrasse 5–13, 81377 München, Germany
*Correspondence e-mail: pemay@cup.uni-muenchen.de
In the title compound, C14H17NOS, the plane defined by the bridging methylene C atom and its three substituents makes dihedral angles of 14.37 (8)° with the heterocycle and 26.17 (8)° with the phenyl ring, while the dihedral angle between the heterocycle and the phenyl ring is 36.29 (7)°. In the crystal, molecules are linked by C—H⋯π contacts.
Related literature
For chemical background, see: Ukai et al. (1943); Enders et al. (2007); Biju et al. (2011); Breslow (1958). For a related structure, see: Reisser et al. (2003).
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR99 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536812034137/su2484sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812034137/su2484Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812034137/su2484Isup3.cml
A solution of 2-(methoxy(phenyl)methyl)-3,4,5-trimethylthiazolium trifluoromethanesulfonate (397 mg, 1.00 mmol) in THF (6 ml) was added dropwise to a stirred suspension of NaH (36 mg, 1.5 mmol) in dry THF (5 ml) at -20 °C under nitrogen, and the reaction mixture was allowed to stir for 36 h in the dark. After warming to room temperature, the solvent was removed under vacuum, and the residue was suspended in dry toluene (20 ml) and filtered through a celite pad under nitrogen. Then the solvent was evaporated to give 205 mg (0.829 mmol, 83%) of the title compound as 2:1 mixture of Z:E isomers. Crystals of the title compound suitable for X-ray
were grown by slow evaporation of a solution in n-pentane under nitrogen.The C-bound H atoms were included in calculated positions and treated as riding atoms: C-H = 0.95 and 0.98 Å for CH and CH3 -atoms, respectively, with Uiso(H) = k × Ueq(C), where k = 1.5 for CH3 H atoms and = 1.2 for other H atoms. The methyl groups were allowed to rotate along the C–X bonds (X = C, O, N) to best fit the experimental electron density.
Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell
CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SIR99 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C14H17NOS | F(000) = 528 |
Mr = 247.36 | Dx = 1.263 (1) Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4082 reflections |
a = 15.9660 (7) Å | θ = 4.5–26.2° |
b = 6.8902 (3) Å | µ = 0.23 mm−1 |
c = 12.1520 (6) Å | T = 173 K |
β = 103.381 (5)° | Block, yellow |
V = 1300.54 (10) Å3 | 0.35 × 0.25 × 0.17 mm |
Z = 4 |
Oxford Diffraction Xcalibur diffractometer | 2637 independent reflections |
Radiation source: fine-focus sealed tube | 2023 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
Detector resolution: 15.9809 pixels mm-1 | θmax = 26.3°, θmin = 4.5° |
ω scans | h = −19→18 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | k = −7→8 |
Tmin = 0.953, Tmax = 1.000 | l = −13→15 |
9041 measured reflections |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0601P)2] where P = (Fo2 + 2Fc2)/3 |
2637 reflections | (Δ/σ)max < 0.001 |
158 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C14H17NOS | V = 1300.54 (10) Å3 |
Mr = 247.36 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.9660 (7) Å | µ = 0.23 mm−1 |
b = 6.8902 (3) Å | T = 173 K |
c = 12.1520 (6) Å | 0.35 × 0.25 × 0.17 mm |
β = 103.381 (5)° |
Oxford Diffraction Xcalibur diffractometer | 2637 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 2023 reflections with I > 2σ(I) |
Tmin = 0.953, Tmax = 1.000 | Rint = 0.029 |
9041 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.29 e Å−3 |
2637 reflections | Δρmin = −0.19 e Å−3 |
158 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 > 2σ(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 | ||
S1 | 0.39851 (3) | 0.51962 (7) | 0.17439 (4) | 0.03514 (16) | |
O1 | 0.33687 (7) | 0.25112 (16) | 0.31574 (8) | 0.0298 (3) | |
N1 | 0.23682 (8) | 0.61091 (19) | 0.10461 (10) | 0.0248 (3) | |
C1 | 0.36863 (11) | 0.7059 (3) | 0.07369 (13) | 0.0314 (4) | |
C2 | 0.28401 (11) | 0.7353 (2) | 0.04813 (12) | 0.0282 (4) | |
C3 | 0.28957 (10) | 0.4751 (2) | 0.17383 (12) | 0.0229 (3) | |
C4 | 0.26767 (9) | 0.3291 (2) | 0.23561 (12) | 0.0227 (3) | |
C5 | 0.18289 (9) | 0.2433 (2) | 0.22982 (12) | 0.0213 (3) | |
C6 | 0.11844 (10) | 0.2412 (2) | 0.12977 (12) | 0.0246 (3) | |
H6 | 0.1286 | 0.3031 | 0.0642 | 0.030* | |
C7 | 0.04027 (10) | 0.1508 (2) | 0.12457 (13) | 0.0271 (4) | |
H7 | −0.0027 | 0.1525 | 0.0559 | 0.033* | |
C8 | 0.02412 (10) | 0.0577 (2) | 0.21848 (14) | 0.0297 (4) | |
H8 | −0.0297 | −0.0040 | 0.2149 | 0.036* | |
C9 | 0.08769 (11) | 0.0561 (2) | 0.31769 (13) | 0.0294 (4) | |
H9 | 0.0775 | −0.0084 | 0.3824 | 0.035* | |
C10 | 0.16563 (10) | 0.1466 (2) | 0.32384 (12) | 0.0252 (3) | |
H10 | 0.2083 | 0.1435 | 0.3928 | 0.030* | |
C11 | 0.43748 (12) | 0.8120 (3) | 0.03234 (16) | 0.0437 (5) | |
H11A | 0.4110 | 0.9126 | −0.0216 | 0.065* | |
H11B | 0.4689 | 0.7204 | −0.0049 | 0.065* | |
H11C | 0.4775 | 0.8725 | 0.0966 | 0.065* | |
C12 | 0.23515 (12) | 0.8848 (3) | −0.03065 (15) | 0.0425 (5) | |
H12A | 0.2160 | 0.9881 | 0.0133 | 0.064* | |
H12B | 0.1849 | 0.8242 | −0.0806 | 0.064* | |
H12C | 0.2725 | 0.9401 | −0.0762 | 0.064* | |
C13 | 0.15990 (10) | 0.6830 (2) | 0.13668 (13) | 0.0288 (4) | |
H13A | 0.1086 | 0.6296 | 0.0853 | 0.043* | |
H13B | 0.1585 | 0.8250 | 0.1319 | 0.043* | |
H13C | 0.1610 | 0.6429 | 0.2144 | 0.043* | |
C14 | 0.35969 (12) | 0.0583 (3) | 0.28898 (16) | 0.0424 (5) | |
H14A | 0.3103 | −0.0282 | 0.2843 | 0.064* | |
H14B | 0.4082 | 0.0121 | 0.3482 | 0.064* | |
H14C | 0.3762 | 0.0594 | 0.2162 | 0.064* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0248 (2) | 0.0356 (3) | 0.0462 (3) | −0.00279 (18) | 0.01062 (19) | 0.00815 (19) |
O1 | 0.0287 (6) | 0.0251 (7) | 0.0319 (6) | 0.0017 (5) | −0.0005 (5) | 0.0051 (5) |
N1 | 0.0293 (7) | 0.0198 (7) | 0.0265 (7) | 0.0006 (6) | 0.0094 (5) | 0.0047 (5) |
C1 | 0.0376 (10) | 0.0279 (9) | 0.0311 (9) | −0.0085 (8) | 0.0129 (7) | −0.0003 (7) |
C2 | 0.0385 (10) | 0.0235 (9) | 0.0241 (8) | −0.0066 (7) | 0.0105 (7) | 0.0006 (6) |
C3 | 0.0223 (8) | 0.0220 (8) | 0.0247 (8) | 0.0002 (6) | 0.0061 (6) | −0.0015 (6) |
C4 | 0.0235 (8) | 0.0203 (8) | 0.0237 (8) | 0.0030 (6) | 0.0040 (6) | 0.0014 (6) |
C5 | 0.0249 (8) | 0.0150 (8) | 0.0247 (8) | 0.0017 (6) | 0.0074 (6) | −0.0015 (6) |
C6 | 0.0311 (9) | 0.0179 (8) | 0.0261 (8) | 0.0042 (7) | 0.0091 (6) | 0.0005 (6) |
C7 | 0.0268 (8) | 0.0195 (8) | 0.0326 (9) | 0.0032 (7) | 0.0019 (7) | −0.0051 (6) |
C8 | 0.0269 (9) | 0.0205 (9) | 0.0437 (10) | −0.0023 (7) | 0.0119 (7) | −0.0036 (7) |
C9 | 0.0379 (10) | 0.0217 (9) | 0.0324 (9) | −0.0027 (7) | 0.0161 (7) | 0.0013 (7) |
C10 | 0.0311 (9) | 0.0211 (8) | 0.0237 (8) | −0.0003 (7) | 0.0070 (6) | 0.0000 (6) |
C11 | 0.0455 (11) | 0.0442 (12) | 0.0455 (10) | −0.0170 (9) | 0.0192 (9) | 0.0017 (9) |
C12 | 0.0496 (11) | 0.0405 (12) | 0.0375 (10) | −0.0028 (9) | 0.0103 (8) | 0.0157 (8) |
C13 | 0.0321 (9) | 0.0225 (9) | 0.0330 (9) | 0.0036 (7) | 0.0101 (7) | 0.0026 (7) |
C14 | 0.0347 (10) | 0.0302 (11) | 0.0598 (12) | 0.0092 (8) | 0.0059 (9) | 0.0059 (9) |
S1—C1 | 1.7614 (17) | C8—C9 | 1.385 (2) |
S1—C3 | 1.7646 (16) | C8—H8 | 0.9500 |
O1—C4 | 1.3999 (17) | C9—C10 | 1.378 (2) |
O1—C14 | 1.435 (2) | C9—H9 | 0.9500 |
N1—C3 | 1.402 (2) | C10—H10 | 0.9500 |
N1—C2 | 1.4186 (19) | C11—H11A | 0.9800 |
N1—C13 | 1.4589 (19) | C11—H11B | 0.9800 |
C1—C2 | 1.330 (2) | C11—H11C | 0.9800 |
C1—C11 | 1.500 (2) | C12—H12A | 0.9800 |
C2—C12 | 1.497 (2) | C12—H12B | 0.9800 |
C3—C4 | 1.349 (2) | C12—H12C | 0.9800 |
C4—C5 | 1.464 (2) | C13—H13A | 0.9800 |
C5—C6 | 1.399 (2) | C13—H13B | 0.9800 |
C5—C10 | 1.404 (2) | C13—H13C | 0.9800 |
C6—C7 | 1.383 (2) | C14—H14A | 0.9800 |
C6—H6 | 0.9500 | C14—H14B | 0.9800 |
C7—C8 | 1.384 (2) | C14—H14C | 0.9800 |
C7—H7 | 0.9500 | ||
C1—S1—C3 | 90.90 (8) | C10—C9—H9 | 119.5 |
C4—O1—C14 | 113.50 (12) | C8—C9—H9 | 119.5 |
C3—N1—C2 | 112.39 (13) | C9—C10—C5 | 121.03 (14) |
C3—N1—C13 | 119.55 (12) | C9—C10—H10 | 119.5 |
C2—N1—C13 | 119.85 (13) | C5—C10—H10 | 119.5 |
C2—C1—C11 | 129.13 (16) | C1—C11—H11A | 109.5 |
C2—C1—S1 | 111.73 (12) | C1—C11—H11B | 109.5 |
C11—C1—S1 | 119.09 (13) | H11A—C11—H11B | 109.5 |
C1—C2—N1 | 114.82 (15) | C1—C11—H11C | 109.5 |
C1—C2—C12 | 127.22 (15) | H11A—C11—H11C | 109.5 |
N1—C2—C12 | 117.94 (15) | H11B—C11—H11C | 109.5 |
C4—C3—N1 | 129.40 (14) | C2—C12—H12A | 109.5 |
C4—C3—S1 | 120.65 (12) | C2—C12—H12B | 109.5 |
N1—C3—S1 | 109.95 (11) | H12A—C12—H12B | 109.5 |
C3—C4—O1 | 114.14 (13) | C2—C12—H12C | 109.5 |
C3—C4—C5 | 129.08 (13) | H12A—C12—H12C | 109.5 |
O1—C4—C5 | 116.78 (12) | H12B—C12—H12C | 109.5 |
C6—C5—C10 | 117.31 (14) | N1—C13—H13A | 109.5 |
C6—C5—C4 | 122.12 (13) | N1—C13—H13B | 109.5 |
C10—C5—C4 | 120.40 (13) | H13A—C13—H13B | 109.5 |
C7—C6—C5 | 121.24 (14) | N1—C13—H13C | 109.5 |
C7—C6—H6 | 119.4 | H13A—C13—H13C | 109.5 |
C5—C6—H6 | 119.4 | H13B—C13—H13C | 109.5 |
C6—C7—C8 | 120.62 (14) | O1—C14—H14A | 109.5 |
C6—C7—H7 | 119.7 | O1—C14—H14B | 109.5 |
C8—C7—H7 | 119.7 | H14A—C14—H14B | 109.5 |
C7—C8—C9 | 118.86 (15) | O1—C14—H14C | 109.5 |
C7—C8—H8 | 120.6 | H14A—C14—H14C | 109.5 |
C9—C8—H8 | 120.6 | H14B—C14—H14C | 109.5 |
C10—C9—C8 | 120.94 (14) | ||
C3—S1—C1—C2 | 3.05 (13) | S1—C3—C4—O1 | 13.63 (19) |
C3—S1—C1—C11 | −179.13 (14) | N1—C3—C4—C5 | 14.8 (3) |
C11—C1—C2—N1 | −178.57 (16) | S1—C3—C4—C5 | −166.26 (12) |
S1—C1—C2—N1 | −1.02 (18) | C14—O1—C4—C3 | −110.21 (16) |
C11—C1—C2—C12 | 0.3 (3) | C14—O1—C4—C5 | 69.70 (17) |
S1—C1—C2—C12 | 177.82 (15) | C3—C4—C5—C6 | 28.4 (2) |
C3—N1—C2—C1 | −2.3 (2) | O1—C4—C5—C6 | −151.44 (14) |
C13—N1—C2—C1 | 146.04 (15) | C3—C4—C5—C10 | −156.27 (16) |
C3—N1—C2—C12 | 178.72 (14) | O1—C4—C5—C10 | 23.8 (2) |
C13—N1—C2—C12 | −32.9 (2) | C10—C5—C6—C7 | 1.3 (2) |
C2—N1—C3—C4 | −176.49 (15) | C4—C5—C6—C7 | 176.69 (14) |
C13—N1—C3—C4 | 35.0 (2) | C5—C6—C7—C8 | −0.7 (2) |
C2—N1—C3—S1 | 4.49 (15) | C6—C7—C8—C9 | −0.2 (2) |
C13—N1—C3—S1 | −143.98 (12) | C7—C8—C9—C10 | 0.6 (2) |
C1—S1—C3—C4 | 176.64 (13) | C8—C9—C10—C5 | 0.0 (2) |
C1—S1—C3—N1 | −4.25 (11) | C6—C5—C10—C9 | −0.9 (2) |
N1—C3—C4—O1 | −165.29 (14) | C4—C5—C10—C9 | −176.45 (14) |
Cg1 is the centroid of the C5–C10 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···Cg1i | 0.95 | 2.83 | 3.6324 (16) | 142 |
C13—H13B···Cg1ii | 0.98 | 2.74 | 3.5657 (15) | 143 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C14H17NOS |
Mr | 247.36 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 15.9660 (7), 6.8902 (3), 12.1520 (6) |
β (°) | 103.381 (5) |
V (Å3) | 1300.54 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.23 |
Crystal size (mm) | 0.35 × 0.25 × 0.17 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) |
Tmin, Tmax | 0.953, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9041, 2637, 2023 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.624 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.104, 1.08 |
No. of reflections | 2637 |
No. of parameters | 158 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.19 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SIR99 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009).
Cg1 is the centroid of the C5–C10 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···Cg1i | 0.95 | 2.83 | 3.6324 (16) | 142 |
C13—H13B···Cg1ii | 0.98 | 2.74 | 3.5657 (15) | 143 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x, y+1, z. |
Acknowledgements
The authors thank Prof. Thomas M. Klapötke for generous allocation of diffractometer time.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Thiazolium ions (Ukai et al., 1943) are known to catalyze benzoin condensations of aldehydes (Enders et al., 2007; Biju et al., 2011) in presence of a base. An acyl anion equivalent, the so-called Breslow intermediate (Breslow, 1958) was proposed to be the key intermediate of these transformations. To understand the structure of these intermediates we now report the X-ray analysis of the O-methyl-protected Breslow intermediate derived from 3,4,5-trimethylthiazolium ion and benzaldehyde.
The molecular structure of the title compound is shown in Fig. 1. The exocyclic double bond has a length of 1.349 (2) Å which is comparable to that observed for a related structure [1.353 Å; Reisser et al., 2003]. The endocyclic double bond length is 1.330 (2) Å [1.332 Å; Reisser et al., 2003]. The angle sum around the methylene carbon atom, C4, amounts to 360° resulting in a trigonal planar environment of the methylene atom. However, this mean plane (C4/O1/C3/C5) is not coplanar with either the plane of the heterocycle (S1/N1/C1-C3) or the plane of the phenyl ring (C5-C10). The corresponding dihedral angles are 14.37 (8)° and 26.17 (8)°, respectively. The dihedral angle between the heterocycle and the phenyl ring is 36.29 (7)°.
In the crystal, molecules are linked via C–H···π contacts (Table 1 and Fig. 2).