Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803017446/lh6096sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803017446/lh60962sup2.hkl |
CCDC reference: 222860
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.040
- wR factor = 0.116
- Data-to-parameter ratio = 15.4
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low ..... 0.96
1 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion
Solvents were dried and distilled under an inert atmosphere. The starting thiazole, (1), was prepared from thioacetamide and 2-bromo-1-phenylpropanone using th procedure of Hantch (1889). The reaction was carried out under an inert atmosphere (dry Argon). The 1H NMR spectrum of (2) was recorded on a Bruker AMX-400. The melting point was determined on a hot-stage Boëtius apparatus. BuLi in C6H14 (6 ml, 1.6 M solution) was added to a solution of thiazole (1) (1 g, 5.3 mmol) in 20 ml Et2O/4 ml C4H8O for 10 min at 203 K (dry CO2/C6H6). Benzaldehyde (0.67 g, 6 mmol) in 2 ml of C4H8O was added dropwise to the reaction mixture after 30 min of stirring at 203 K. Then 10 ml of 1 M aqueous citric acid was added after 30 min of stirring and the reaction mixture was left to warm to room temperature, then it was washed with water and brine, dried under Na2SO4 and filtered. Solvent was evaporated in vacuo and 20 ml of C6H14 was added to the resulting yellow oil, after 15 min of heating the mixture was cooled, yielding 0.5 g (60%) of a white precipitate. The product was recrystallized from CH2Cl2/C6H14, m.p. 363–365 K. 1H NMR (CDCl3, 400 MHz, p.p.m.): 7.64 (d, 2H, Ph), 7.43 (t, 4H, Ph), 7,35 (t, 3H, Ph), 7.28 (d, 1H, Ph), 5.19 (dd, 1H, CH), 3.30 (dd, 1H, CH2, J = 4.5 MHz), 3.25 (dd, 1H, CH2, J = 8.5 MHz), 2.53 (s, 3H, CH3).
The hydroxyl H atom was refined isotropically to give an O—H bond length of 0.87 (3) Å. H atoms bonded to C atoms were included in calculated positions and included in the refinement in riding-motion approximation (C—H = 0.93–0.98 Å), with Uiso = 1.2Ueq (1.5Ueq for methyl) of the carrier atom.
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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, 2003) and PLUTON97 (Spek, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 2003).
C18H17NOS | F(000) = 624 |
Mr = 295.39 | Dx = 1.292 Mg m−3 |
Monoclinic, P21/c | Melting point = 363–365 K |
Hall symbol: -P 2ybc | Cu Kα radiation, λ = 1.54180 Å |
a = 6.2820 (9) Å | Cell parameters from 25 reflections |
b = 28.836 (4) Å | θ = 33–35° |
c = 8.4583 (13) Å | µ = 1.86 mm−1 |
β = 97.56 (1)° | T = 293 K |
V = 1518.9 (4) Å3 | Prism, colourless |
Z = 4 | 0.30 × 0.30 × 0.30 mm |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.021 |
Radiation source: fine-focus sealed tube | θmax = 74.9°, θmin = 3.1° |
Graphite monochromator | h = −7→7 |
non–profiled ω/2θ scans | k = 0→36 |
3201 measured reflections | l = 0→9 |
2997 independent reflections | 1 standard reflections every 226 reflections |
2613 reflections with I > 2σ(I) | intensity decay: 2% |
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)] = 0.040 | Hydrogen site location: mixed |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0712P)2 + 0.2241P] where P = (Fo2 + 2Fc2)/3 |
2997 reflections | (Δ/σ)max = 0.001 |
195 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C18H17NOS | V = 1518.9 (4) Å3 |
Mr = 295.39 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 6.2820 (9) Å | µ = 1.86 mm−1 |
b = 28.836 (4) Å | T = 293 K |
c = 8.4583 (13) Å | 0.30 × 0.30 × 0.30 mm |
β = 97.56 (1)° |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.021 |
3201 measured reflections | 1 standard reflections every 226 reflections |
2997 independent reflections | intensity decay: 2% |
2613 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.31 e Å−3 |
2997 reflections | Δρmin = −0.28 e Å−3 |
195 parameters |
x | y | z | Uiso*/Ueq | ||
S1 | 0.19563 (7) | 0.255774 (14) | 0.65532 (5) | 0.04718 (15) | |
C2 | −0.0259 (3) | 0.24689 (5) | 0.74978 (19) | 0.0427 (3) | |
N3 | −0.0604 (2) | 0.20369 (4) | 0.78171 (15) | 0.0437 (3) | |
C4 | 0.0931 (3) | 0.17445 (5) | 0.72955 (18) | 0.0416 (3) | |
C5 | 0.2457 (3) | 0.19688 (6) | 0.65539 (19) | 0.0446 (4) | |
C51 | 0.4275 (3) | 0.18051 (7) | 0.5717 (3) | 0.0624 (5) | |
H51A | 0.5372 | 0.1672 | 0.6480 | 0.094* | |
H51B | 0.4858 | 0.2063 | 0.5198 | 0.094* | |
H51C | 0.3760 | 0.1576 | 0.4938 | 0.094* | |
C6 | 0.0732 (3) | 0.12400 (6) | 0.7571 (2) | 0.0469 (4) | |
C7 | 0.2287 (4) | 0.09247 (7) | 0.7252 (3) | 0.0769 (7) | |
H7 | 0.3513 | 0.1030 | 0.6858 | 0.092* | |
C8 | 0.2042 (5) | 0.04542 (8) | 0.7512 (4) | 0.0927 (8) | |
H8 | 0.3108 | 0.0249 | 0.7292 | 0.111* | |
C9 | 0.0251 (5) | 0.02857 (7) | 0.8090 (3) | 0.0785 (7) | |
H9 | 0.0081 | −0.0031 | 0.8239 | 0.094* | |
C10 | −0.1288 (4) | 0.05941 (7) | 0.8445 (3) | 0.0697 (6) | |
H10 | −0.2492 | 0.0486 | 0.8861 | 0.084* | |
C11 | −0.1059 (3) | 0.10649 (6) | 0.8187 (2) | 0.0548 (4) | |
H11 | −0.2120 | 0.1268 | 0.8429 | 0.066* | |
C12 | −0.1643 (3) | 0.28628 (6) | 0.7933 (2) | 0.0487 (4) | |
H12A | −0.0935 | 0.3014 | 0.8883 | 0.058* | |
H12B | −0.2995 | 0.2739 | 0.8182 | 0.058* | |
C13 | −0.2100 (3) | 0.32240 (5) | 0.65984 (18) | 0.0430 (3) | |
H13 | −0.0731 | 0.3334 | 0.6301 | 0.052* | |
O13 | −0.3284 (2) | 0.30059 (4) | 0.52548 (15) | 0.0536 (3) | |
H131 | −0.245 (5) | 0.2997 (11) | 0.451 (4) | 0.120 (11)* | |
C14 | −0.3319 (3) | 0.36340 (5) | 0.71575 (19) | 0.0435 (4) | |
C15 | −0.2379 (3) | 0.39113 (6) | 0.8397 (2) | 0.0563 (4) | |
H15 | −0.0985 | 0.3850 | 0.8869 | 0.068* | |
C16 | −0.3506 (4) | 0.42802 (6) | 0.8939 (3) | 0.0681 (6) | |
H16 | −0.2873 | 0.4461 | 0.9782 | 0.082* | |
C17 | −0.5552 (4) | 0.43789 (7) | 0.8236 (3) | 0.0726 (6) | |
H17 | −0.6302 | 0.4627 | 0.8599 | 0.087* | |
C18 | −0.6485 (4) | 0.41098 (7) | 0.6993 (3) | 0.0700 (6) | |
H18 | −0.7867 | 0.4177 | 0.6511 | 0.084* | |
C19 | −0.5378 (3) | 0.37382 (6) | 0.6453 (2) | 0.0542 (4) | |
H19 | −0.6024 | 0.3558 | 0.5612 | 0.065* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0458 (2) | 0.0460 (2) | 0.0502 (3) | −0.00075 (15) | 0.00793 (17) | 0.00383 (15) |
C2 | 0.0485 (9) | 0.0444 (8) | 0.0350 (8) | 0.0036 (6) | 0.0053 (6) | 0.0006 (6) |
N3 | 0.0491 (8) | 0.0443 (7) | 0.0382 (7) | 0.0037 (5) | 0.0073 (5) | 0.0024 (5) |
C4 | 0.0434 (8) | 0.0445 (8) | 0.0353 (8) | 0.0032 (6) | −0.0014 (6) | −0.0013 (6) |
C5 | 0.0389 (8) | 0.0483 (8) | 0.0459 (9) | 0.0036 (6) | 0.0028 (6) | 0.0004 (6) |
C51 | 0.0518 (11) | 0.0669 (11) | 0.0716 (13) | 0.0124 (8) | 0.0198 (9) | 0.0054 (9) |
C6 | 0.0538 (9) | 0.0433 (8) | 0.0415 (9) | 0.0008 (7) | −0.0021 (7) | −0.0014 (6) |
C7 | 0.0830 (16) | 0.0504 (11) | 0.1026 (18) | 0.0092 (10) | 0.0316 (13) | 0.0003 (11) |
C8 | 0.112 (2) | 0.0480 (11) | 0.121 (2) | 0.0168 (12) | 0.0294 (18) | −0.0004 (12) |
C9 | 0.1070 (19) | 0.0427 (10) | 0.0818 (16) | −0.0022 (11) | −0.0028 (13) | 0.0043 (9) |
C10 | 0.0777 (14) | 0.0571 (11) | 0.0712 (14) | −0.0136 (10) | −0.0019 (11) | 0.0117 (9) |
C11 | 0.0567 (11) | 0.0521 (9) | 0.0538 (11) | −0.0023 (8) | 0.0009 (8) | 0.0040 (7) |
C12 | 0.0601 (10) | 0.0460 (8) | 0.0415 (9) | 0.0098 (7) | 0.0118 (7) | 0.0033 (6) |
C13 | 0.0443 (8) | 0.0465 (8) | 0.0380 (8) | −0.0002 (6) | 0.0053 (6) | 0.0010 (6) |
O13 | 0.0552 (7) | 0.0640 (7) | 0.0415 (7) | 0.0000 (6) | 0.0058 (5) | −0.0089 (5) |
C14 | 0.0515 (9) | 0.0414 (7) | 0.0379 (9) | 0.0009 (6) | 0.0072 (6) | 0.0057 (6) |
C15 | 0.0660 (12) | 0.0471 (9) | 0.0536 (11) | 0.0001 (8) | −0.0005 (8) | −0.0018 (7) |
C16 | 0.0993 (17) | 0.0458 (9) | 0.0575 (12) | 0.0015 (10) | 0.0041 (11) | −0.0067 (8) |
C17 | 0.0948 (17) | 0.0489 (10) | 0.0765 (15) | 0.0208 (10) | 0.0198 (12) | 0.0010 (9) |
C18 | 0.0676 (13) | 0.0589 (11) | 0.0825 (15) | 0.0205 (10) | 0.0057 (11) | 0.0048 (10) |
C19 | 0.0551 (10) | 0.0500 (9) | 0.0554 (11) | 0.0067 (7) | −0.0007 (8) | 0.0025 (7) |
S1—C2 | 1.7126 (17) | C10—H10 | 0.9300 |
S1—C5 | 1.7270 (16) | C11—H11 | 0.9300 |
C2—N3 | 1.299 (2) | C12—C13 | 1.535 (2) |
C2—C12 | 1.505 (2) | C12—H12A | 0.9700 |
N3—C4 | 1.395 (2) | C12—H12B | 0.9700 |
C4—C5 | 1.375 (2) | C13—O13 | 1.4203 (19) |
C4—C6 | 1.481 (2) | C13—C14 | 1.517 (2) |
C5—C51 | 1.497 (2) | C13—H13 | 0.9800 |
C51—H51A | 0.9600 | O13—H131 | 0.87 (3) |
C51—H51B | 0.9600 | C14—C19 | 1.385 (2) |
C51—H51C | 0.9600 | C14—C15 | 1.388 (2) |
C6—C7 | 1.387 (3) | C15—C16 | 1.389 (3) |
C6—C11 | 1.395 (3) | C15—H15 | 0.9300 |
C7—C8 | 1.386 (3) | C16—C17 | 1.373 (4) |
C7—H7 | 0.9300 | C16—H16 | 0.9300 |
C8—C9 | 1.373 (4) | C17—C18 | 1.375 (3) |
C8—H8 | 0.9300 | C17—H17 | 0.9300 |
C9—C10 | 1.375 (4) | C18—C19 | 1.387 (3) |
C9—H9 | 0.9300 | C18—H18 | 0.9300 |
C10—C11 | 1.385 (3) | C19—H19 | 0.9300 |
C2—S1—C5 | 90.68 (8) | C10—C11—H11 | 119.4 |
N3—C2—C12 | 123.73 (15) | C6—C11—H11 | 119.4 |
N3—C2—S1 | 114.11 (12) | C2—C12—C13 | 112.99 (13) |
C12—C2—S1 | 122.16 (12) | C2—C12—H12A | 109.0 |
C2—N3—C4 | 111.88 (14) | C13—C12—H12A | 109.0 |
C5—C4—N3 | 114.35 (14) | C2—C12—H12B | 109.0 |
C5—C4—C6 | 127.76 (15) | C13—C12—H12B | 109.0 |
N3—C4—C6 | 117.89 (15) | H12A—C12—H12B | 107.8 |
C4—C5—C51 | 133.52 (16) | O13—C13—C14 | 111.21 (13) |
C4—C5—S1 | 108.97 (12) | O13—C13—C12 | 108.40 (13) |
C51—C5—S1 | 117.41 (13) | C14—C13—C12 | 110.66 (12) |
C5—C51—H51A | 109.5 | O13—C13—H13 | 108.8 |
C5—C51—H51B | 109.5 | C14—C13—H13 | 108.8 |
H51A—C51—H51B | 109.5 | C12—C13—H13 | 108.8 |
C5—C51—H51C | 109.5 | C13—O13—H131 | 107 (2) |
H51A—C51—H51C | 109.5 | C19—C14—C15 | 118.74 (16) |
H51B—C51—H51C | 109.5 | C19—C14—C13 | 121.07 (15) |
C7—C6—C11 | 117.30 (17) | C15—C14—C13 | 120.19 (15) |
C7—C6—C4 | 122.51 (17) | C14—C15—C16 | 120.40 (19) |
C11—C6—C4 | 120.19 (16) | C14—C15—H15 | 119.8 |
C8—C7—C6 | 121.0 (2) | C16—C15—H15 | 119.8 |
C8—C7—H7 | 119.5 | C17—C16—C15 | 120.3 (2) |
C6—C7—H7 | 119.5 | C17—C16—H16 | 119.8 |
C9—C8—C7 | 121.1 (2) | C15—C16—H16 | 119.8 |
C9—C8—H8 | 119.5 | C16—C17—C18 | 119.68 (19) |
C7—C8—H8 | 119.5 | C16—C17—H17 | 120.2 |
C8—C9—C10 | 118.8 (2) | C18—C17—H17 | 120.2 |
C8—C9—H9 | 120.6 | C17—C18—C19 | 120.4 (2) |
C10—C9—H9 | 120.6 | C17—C18—H18 | 119.8 |
C9—C10—C11 | 120.6 (2) | C19—C18—H18 | 119.8 |
C9—C10—H10 | 119.7 | C14—C19—C18 | 120.43 (19) |
C11—C10—H10 | 119.7 | C14—C19—H19 | 119.8 |
C10—C11—C6 | 121.2 (2) | C18—C19—H19 | 119.8 |
D—H···A | D—H | H···A | D···A | D—H···A |
O13—H131···N3i | 0.87 (4) | 1.96 (4) | 2.831 (2) | 179 (3) |
Symmetry code: (i) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C18H17NOS |
Mr | 295.39 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 6.2820 (9), 28.836 (4), 8.4583 (13) |
β (°) | 97.56 (1) |
V (Å3) | 1518.9 (4) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 1.86 |
Crystal size (mm) | 0.30 × 0.30 × 0.30 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3201, 2997, 2613 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.116, 1.05 |
No. of reflections | 2997 |
No. of parameters | 195 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.31, −0.28 |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 2003) and PLUTON97 (Spek, 1997), WinGX publication routines (Farrugia, 2003).
S1—C2 | 1.7126 (17) | C9—C10 | 1.375 (4) |
S1—C5 | 1.7270 (16) | C10—C11 | 1.385 (3) |
C2—N3 | 1.299 (2) | C12—C13 | 1.535 (2) |
C2—C12 | 1.505 (2) | C13—O13 | 1.4203 (19) |
N3—C4 | 1.395 (2) | C13—C14 | 1.517 (2) |
C4—C5 | 1.375 (2) | O13—H131 | 0.87 (3) |
C4—C6 | 1.481 (2) | C14—C19 | 1.385 (2) |
C5—C51 | 1.497 (2) | C14—C15 | 1.388 (2) |
C6—C7 | 1.387 (3) | C15—C16 | 1.389 (3) |
C6—C11 | 1.395 (3) | C16—C17 | 1.373 (4) |
C7—C8 | 1.386 (3) | C17—C18 | 1.375 (3) |
C8—C9 | 1.373 (4) | C18—C19 | 1.387 (3) |
C2—S1—C5 | 90.68 (8) | C8—C9—C10 | 118.8 (2) |
N3—C2—C12 | 123.73 (15) | C9—C10—C11 | 120.6 (2) |
N3—C2—S1 | 114.11 (12) | C10—C11—C6 | 121.2 (2) |
C12—C2—S1 | 122.16 (12) | C2—C12—C13 | 112.99 (13) |
C2—N3—C4 | 111.88 (14) | O13—C13—C14 | 111.21 (13) |
C5—C4—N3 | 114.35 (14) | O13—C13—C12 | 108.40 (13) |
C5—C4—C6 | 127.76 (15) | C14—C13—C12 | 110.66 (12) |
N3—C4—C6 | 117.89 (15) | C13—O13—H131 | 107 (2) |
C4—C5—C51 | 133.52 (16) | C19—C14—C15 | 118.74 (16) |
C4—C5—S1 | 108.97 (12) | C19—C14—C13 | 121.07 (15) |
C51—C5—S1 | 117.41 (13) | C15—C14—C13 | 120.19 (15) |
C7—C6—C11 | 117.30 (17) | C14—C15—C16 | 120.40 (19) |
C7—C6—C4 | 122.51 (17) | C17—C16—C15 | 120.3 (2) |
C11—C6—C4 | 120.19 (16) | C16—C17—C18 | 119.68 (19) |
C8—C7—C6 | 121.0 (2) | C17—C18—C19 | 120.4 (2) |
C9—C8—C7 | 121.1 (2) | C14—C19—C18 | 120.43 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
O13—H131···N3i | 0.87 (4) | 1.96 (4) | 2.831 (2) | 179 (3) |
Symmetry code: (i) x, −y+1/2, z−1/2. |
The metallation of 2,5-dimethyl-4-phenylthiazole by butyllithium can generate anionic methyl groups at positions 2 and 5. The title structure, (2), is the product metallation and the subsequent reaction of the anion with benzaldehyde and was prepared in according to the Scheme below.
The 5-membered heterocycle (S1/C2/N3/C4/C5) is nearly planar and there is conjugation between it and the phenyl ring (C6–C11), the dihedral angle being 6.83 (11)°. The O13–H131···N3 intermolecular hydrogen bond [H131···N3i = 1.96 (4) Å, O13···N3i = 2.831 (2) Å and O13–H131···N3i = 179 (3)°; symmetry code: (i) x, 1/2 − y, z − 1/2] links the molecules in the crystal into extended chains.