5. Experimental Part
5.24. X-Ray Data
Table 26a: Crystal data and structure refinement details of compounds 76b, 35b, and 35d.a
76b 35b 35d
Empirical formula C16H12N4O2S2 C16H17N3S2 C16H17N3O2S2
Formula weight 356.42 315.46 347.46
Temperature 110.00(10) K 107(1) K 107.3(8) K
Wavelength 0.71073 Å 0.71073 Å 0.71073 Å
Crystal system Monoclinic Triclinic Orthorhombic
Space group P21/c P 1¯ Pbca
Unit cell dimensions a = 14.6245(7) Å a = 7.5232(4) Å a = 10.9331(3) Å b = 11.2068(5) Å b = 9.6954(6) Å b = 15.9220(5) Å c = 9.9963(5) Å c = 21.6674(13) Å c = 18.4077(6) Å = 79.452(5)° = 104.715(5)° = 88.826(5)° = 81.922(5)° Volume 1584.60(14) Å3 1538.28(16) Å3 3204.35(17) Å3 Z 4 4 8 Density (calculated) 1.494 Mg/m3 1.362 Mg/m3 1.440 Mg/m3 Absorption coefficient 0.353 mm–1 0.343 mm–1 0.345 mm–1 F(000) 736 664 1456 Crystal size 0.4 x 0.2 x 0.2 mm3 0.4 x 0.3 x 0.2 mm3 0.4 x 0.4 x 0.1 mm3
Theta range for data
collection 3.37 to 26.00° 2.89 to 25.50° 2.89 to 25.49° Index ranges –18 ≤ h ≤ 18, –13 ≤ k ≤ 13, –11 ≤ l ≤ 12 –9 ≤ h ≤ 8, –11 ≤ k ≤ 11, –21 ≤ l ≤ 26 –11 ≤ h ≤ 13, –19 ≤ k ≤ 19, –22 ≤ l ≤ 22 Reflections collected 6298 11327 20787 Independent reflections 3092 [R int = 0.0247] 5686 [Rint = 0.0251] 2986 [Rint = 0.0308] Completeness to Thetamax 99.1 % 99.5 % 99.8 %
Absorption correction Semi-empirical from equivalents Semi-empirical from equivalents Semi-empirical from equivalents Max. and min.
transmission 1 and 0.98730 1 and 0. 95663 1 and 0.91457
Refinement method Full-matrix least-squares on F2 Full-matrix least-squares on F2 Full-matrix least-squares on F2
Data / restraints /
parameters 3092 / 0 / 219 5686 / 0 / 387 2986 / 0 / 223
Table 26b: Crystal data and structure refinement details of compounds 107b, and 122c.a 107b Picrate of 122c Empirical formula C27H29N3O2S2 C22H25N5O9S Formula weight 491.65 535.53 Temperature 110 K 110 K Wavelength 0.71073 Å 1.54184 Å
Crystal system Monoclinic Triclinic
Space group P21/n P 1¯
Unit cell dimensions a = 17.5686(6) Å a = 7.2402(4) Å b = 7.9831(3) Å b = 11.3934(5) Å c = 18.1888(6) Å c = 15.1933(8) Å = 94.143(4)° = 100.044(3)° = 95.077(4)° = 99.874(4)° Volume 2511.92(15) Å3 1225.00(11) Å3 Z 4 2 Density (calculated) 1.300 Mg/m3 1.452 Mg/m3 Absorption coefficient 0.241 mm–1 1.725 mm–1 F(000) 1040 560 Crystal size 0.4 x 0.3 x 0.2 mm3 0.35 x 0.2 x 0.05 mm3
Theta range for data
collection 2.954 to 24.999° 2.932 to 65.493° Index ranges –19 ≤ h ≤ 20, –9 ≤ k ≤ 9, –20 ≤ l ≤ 21 –5 ≤ h ≤ 8, –13 ≤ k ≤ 13, –17 ≤ l ≤ 17 Reflections collected 10552 7152 Independent reflections 4414 [R int = 0.0338] 4217 [Rint = 0.0179] Completeness to Thetamax 99.6 % 99.8 %
Absorption correction Semi-empirical from equivalents Semi-empirical from equivalents Max. and min.
transmission 1 and 0.85137 1 and 0.86852
Refinement method Full-matrix least-squares on F2 Full-matrix least-squares on F2
Data / restraints /
parameters 4414 / 1 / 312 4217 / 0 / 342
Goodness-of-fit on F2 1.047 1.060
Final R indicesb
[I > 2sigma(I)]c RwR1 = 0.0411, 2 = 0.0927 RwR1 = 0.0400, 2 = 0.1050
R indices (all data)b,c R1 = 0.0565,
wR2 = 0.0990
R1 = 0.0467,
wR2 = 0.1096
Extinction coefficient n/a n/a
Largest diff. peak and hole 0.289 and –0.288 e.Å–3 0.557 and –0.372 e.Å–3
a Standard uncertainties of the last significant digits are shown in parentheses. b
o c o F F F 1 R . c
2 2 2 2 2 2 ) F ( w ) F F ( w w o c o R with w F g P g P P F F o o c 1 0 2 3 2 2 1 2 2 2 2 ( ) ( ) ; (max( , ) ).5.25. Additional Information on Crystal Growth and X-Ray Diffraction
Yellow, cube-like crystals of thiazole 76b were obtained by evaporation of a chloroform solution containing 76b at 25°C. Crystal structure analysis: data collection was performed at 110.00(10) K with Mo K radiation (= 0.71073 Å) with an Oxford Gemini S diffractometer. Of 6298 collected reflections, 3092 were independent (Rint = 0.0247). The structure was solved by direct methods and refined by full-matrix least-squares methods on F2 with the SHELXTL-97 program package.[83] Crystal data for C
16H12N4O2S2 (76b): M = 356.42 g·mol–1, monoclinic, P2
1/c, a = 14.6245(7), b = 11.2068(5), c = 9.9963(5) Å, β = 104.715(5), V = 1584.60(14) Å3, Z = 4, c = 1.494 g·cm–3, μ = 0.353 mm–1, R1 = 0.0599 (all data), wR2 = 0.1341 (all data) and goodness-of-fit on F2 is 1.033. Crystallographic data incl. bond lengths, bond and torsion angles have been deposited with the Cambridge Crystallographic Data Centre (CCDC-975356).
Colorless, prism-like crystals of thiazole 35b were obtained by evaporation of a dichloromethane/n-hexane solution containing 35b at 25°C. Crystal structure analysis: data collection was performed at 107(1) K with Mo K radiation ( = 0.71073 Å) with an Oxford Gemini S diffractometer. Of 11327 collected reflections, 5686 were independent (Rint = 0.0251). The structure was solved by direct methods and refined by full-matrix least-squares methods on F2 with the SHELXTL-97 program package.[83] Crystal data for C16H17N3S2 (35b):
M = 315.45 g·mol–1, triclinic, P 1¯, a = 7.5232(4), b = 9.6954(6), c = 21.6674(13) Å, = 79.452(5), β = 88.826(5), = 81.922(5), V = 1538.28(16) Å3, Z = 4,
c = 1.362 g·cm–3, μ =
0.343 mm–1, R
1 = 0.0435 (all data), wR2 = 0.0847 (all data) and goodness-of-fit on F2 is 1.039.
Yellow needle-like crystals of thiazole 35d were obtained by evaporation of a dichloromethane/n-hexane solution containing 35d at 25°C. Crystal structure analysis: data collection was performed at 107.3(8) K with Mo K radiation ( = 0.71073 Å) with an Oxford Gemini S diffractometer. Of 20787 collected reflections, 2986 were independent (Rint = 0.0308). The structure was solved by direct methods and refined by full-matrix least-
Figure 26: ORTEP diagram (55% ellipsoid probability) of the molecular structure of thiazole 35d with disorder of C8 (occupation 0.63) to C8’ (0.37).
Colorless, prism-like crystals of thiazole 107b were obtained by recrystallisaton from toluene. Crystal structure analysis: data collection was performed at 110 K with Mo K radiation ( = 0.71073 Å) with an Oxford Gemini S diffractometer. Of 10552 collected reflections, 4414 were independent (Rint = 0.0338). The structure was solved by direct methods and refined by full-matrix least-squares methods on F2 with the SHELXTL-97 program package.[83] Crystal data for C27H29N3O2S2 (107b): M = 491.65 g·mol–1, monoclinic, P21/n, a = 17.5686(6), b = 7.9831(3), c = 18.1888(6) Å, β = 100.044(3), V = 2511.92(15) Å3, Z = 4, c = 1.300 g·cm–3, μ = 0.241 mm–1, R1 = 0.0565 (all data), wR2 = 0.0990 (all data) and goodness-of-fit on F2 is 1.047.
Yellow, needle-like crystals of the picrate of 122c were obtained by evaporation of a dichloromethane/n-hexane solution containing the picrate of 122c at 25°C. Crystal structure analysis: data collection was performed at 110 K with Cu K radiation ( = 1.54184 Å) with an Oxford Gemini S diffractometer. Of 7152 collected reflections, 4217 were independent (Rint = 0.0179). The structure was solved by direct methods and refined by full-matrix least- squares methods on F2 with the SHELXTL-97 program package.[83] Crystal data for C22H25N5O9S (picrate of 122c): M = 535.53 g·mol–1, triclinic, P 1¯, a = 7.2402(4), b =
11.3934(5), c = 15.1933(8) Å, = 94.143(4), β = 95.077(4), = 99.874(4), V = 1225.00(11) Å3, Z = 2, c = 1.452 g·cm–3, μ = 1.725 mm–1, R1 = 0.0467 (all data), wR2 = 0.1096 (all data) and goodness-of-fit on F2 is 1.060.
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7. Appendix
Content
NMR Spectra (in order of increasing compound numbers)
A-2–119
Additional Crystallographic Data (for compounds 35b, 35d, 76b, 107b, 122c)
13C-{1H} NMR Spectrum of N-tert-Butyl-N-isopropyl-5-methylthiazol-2-amine (25c) in CDCl3
13C-{1H} NMR Spectrum of N-[5,5'-Dimethyl-2'H-(2,3'-bithiazol)-2'-ylidene]aniline (35a) in CDCl3
1H NMR Spectrum of 2,6-Dimethyl-N-[5-methyl-3-(5-methylthiazol-2-yl)thiazol-2(3H)- ylidene]aniline (35b) in CDCl3
13C-{1H} NMR Spectrum of 2,6-Dimethyl-N-[5-methyl-3-(5-methylthiazol-2-yl)thiazol- 2(3H)-ylidene]aniline (35b) in CDCl3
1H NMR Spectrum of N-[5,5'-Dimethyl-2'H-(2,3'-bithiazol)-2'-ylidene]-4-methoxyaniline (35c) in CDCl3
13C-{1H} NMR Spectrum of N-[5,5'-Dimethyl-2'H-(2,3'-bithiazol)-2'-ylidene]-4- methoxyaniline (35c) in CDCl3
1H NMR Spectrum of 2,6-Dimethoxy-N-[5-methyl-3-(5-methylthiazol-2-yl)thiazol-2(3H)- ylidene]aniline (35d) in CDCl3
13C-{1H} NMR Spectrum of 2,6-Dimethoxy-N-[5-methyl-3-(5-methylthiazol-2-yl)thiazol- 2(3H)-ylidene]aniline (35d) in CDCl3
13C-{1H} NMR Spectrum of N-(2,6-Dimethylphenyl)-5-methylthiazol-2-amine (68b) in CDCl3
1H NMR Spectrum of N-Isopropyl-N-(4-methoxyphenyl)-5-methylthiazol-2-amine (70b) in CDCl3
13C-{1H} NMR Spectrum of N-Isopropyl-N-(4-methoxyphenyl)-5-methylthiazol-2-amine (70b) in CDCl3
1H NMR Spectrum of N-(2,6-Dimethylphenyl)-N-isopropyl-5-methylthiazol-2-amine (70c) in CDCl3
13C-{1H} NMR Spectrum of N-(2,6-Dimethylphenyl)-N-isopropyl-5-methylthiazol-2-amine (70c) in CDCl3
1H NMR Spectrum of 4-[Isopropyl(4-methoxyphenylamino]-3-methylazete-2(3H)-thione (72) in CDCl3
13C-{1H} NMR Spectrum of 4-[Isopropyl(4-methoxyphenylamino]-3-methylazete-2(3H)- thione (72) in CDCl3
1H NMR Spectrum of 2,2,6,6-Tetramethyl-1-(5-methylthiazol-2-yl)piperidin-4-one (74a) in CDCl3
13C-{1H} NMR Spectrum of 2,2,6,6-Tetramethyl-1-(5-methylthiazol-2-yl)piperidin-4-one (74a) in CDCl3
13C-{1H} NMR Spectrum of 2,2,6,6-Tetramethyl-1-(5-methylthiazol-2-yl)piperidine (74b) in CDCl3
1H NMR Spectrum of 5-Methyl-2-(2,2,6,6-tetramethyl-1,2,3,6-tetrahydropyridin-1-yl)thiazole (74c) in CDCl3
13C-{1H} NMR Spectrum of 5-Methyl-2-(2,2,6,6-tetramethyl-1,2,3,6-tetrahydropyridin-1- yl)thiazole (74c) in CDCl3
13C-{1H} NMR Spectrum of 2-(5-Methylthiazol-2-ylamino)isoindoline-1,3-dione (76a) in CDCl3
1H NMR Spectrum of 2-[Bis(5-methylthiazol-2-yl)amino]isoindoline-1,3-dione (76b) in CDCl3
13C-{1H} NMR Spectrum of 2-[Bis(5-methylthiazol-2-yl)amino]isoindoline-1,3-dione (76b) in CDCl3
13C-{1H} NMR Spectrum of O-Dimethylamino N-propa-1,2-dienylthiocarbamat (78a) in CDCl3 (Naphthalene standard visible!)
1H NMR Spectrum of 2,2,6,6-Tetramethyl-1-[5-(3-nitro-2-phenylpropyl)thiazol-2- yl]piperidin-4-one (83) in CDCl3
13C-{1H} NMR Spectrum of 2,2,6,6-Tetramethyl-1-[5-(3-nitro-2-phenylpropyl)thiazol-2- yl]piperidin-4-one (83) in CDCl3
1H NMR Spectrum of 1-[5-(2-Hydroxy-2-phenylethyl)thiazol-2-yl]-2,2,6,6- tetramethylpiperidin-4-one (85a) in CDCl3
13C-{1H} NMR Spectrum of 1-[5-(2-Hydroxy-2-phenylethyl)thiazol-2-yl]-2,2,6,6- tetramethylpiperidin-4-one (85a) in CDCl3
1H NMR Spectrum of 1-{5-[2-(4-Chlorophenyl)-2-hydroxyethyl]thiazol-2-yl}-2,2,6,6- tetramethylpiperidin-4-one (85b) in CDCl3
13C-{1H} NMR Spectrum of1-{5-[2-(4-Chlorophenyl)-2-hydroxyethyl]thiazol-2-yl}-2,2,6,6- tetramethylpiperidin-4-one (85b) in CDCl3
1H NMR Spectrum of 1-{5-[2-Hydroxy-2-(perfluorophenyl)ethyl]thiazol-2-yl}-2,2,6,6- tetramethylpiperidin-4-one (85c) in CDCl3
13C-{1H} NMR Spectrum of 1-{5-[2-Hydroxy-2-(perfluorophenyl)ethyl]thiazol-2-yl}-2,2,6,6- tetramethylpiperidin-4-one (85c) in CDCl3
1H NMR Spectrum of 1-{5-[2-Hydroxy-2-(4-nitrophenyl)ethyl]thiazol-2-yl}-2,2,6,6- tetramethylpiperidin-4-one (85d) in CDCl3
13C-{1H} NMR Spectrum of 1-{5-[2-Hydroxy-2-(4-nitrophenyl)ethyl]thiazol-2-yl}-2,2,6,6- tetramethylpiperidin-4-one (85d) in CDCl3
1H NMR Spectrum of 1-{5-[2-(2,4-Dinitrophenyl)-2-hydroxyethyl]thiazol-2-yl}-2,2,6,6- tetramethylpiperidin-4-one (85e) in CDCl3
13C-{1H} NMR Spectrum of 1-{5-[2-(2,4-Dinitrophenyl)-2-hydroxyethyl]thiazol-2-yl}- 2,2,6,6-tetramethylpiperidin-4-one (85e) in CDCl3
13C-{1H} NMR Spectrum of 5-(3-Nitro-2-phenylpropyl)-N-phenylthiazol-2-amine (86a) in CDCl3
1H NMR Spectrum of N-(2,6-Dimethylphenyl)-5-(3-nitro-2-phenylpropyl)thiazol-2-amine (86b) in CDCl3
13C-{1H} NMR Spectrum of N-(2,6-Dimethylphenyl)-5-(3-nitro-2-phenylpropyl)thiazol-2- amine (86b) in CDCl3 (Enhancement of weak signal at 170 ppm)