Supporting Information

 Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2016

The Annulation of Vinyl Azides with Potassium Ethyl

Xanthogenate: A Straightforward Synthesis of
Thiazole-2(3H)-thiones
Kandasamy Rajaguru, Arumugam Mariappan, Shanmugam Muthusubramanian,* and
Nattamai Bhuvanesh
Supporting Information

S1
Table of contents Page No

Experimental section S4
Characterization data of compounds 1, 3 and 7 S5
1
H & 13C NMR spectra of compound 1a S15
1
H & 13C NMR spectra of compound 1c S17
1
H & 13C NMR spectra of compound 1f S19
1 13
H& C NMR spectra of compound 1h S21
1
H & 13C NMR spectra of compound 1i S23
1
H & 13C NMR spectra of compound 1j S25
1
H & 13C NMR spectra of compound 1k S27
1
H & 13C NMR spectra of compound 1m S29
1
H & 13C NMR spectra of compound 1n S31
1 13
H& C NMR spectra of compound 1o S33
1
H & 13C NMR spectra of compound 1p S35
1
H & 13C NMR spectra of compound 3a S37
1
H & 13C NMR spectra of compound 3b S39
1
H & 13C NMR spectra of compound 3c S41
1
H & 13C NMR spectra of compound 3d S43
1 13
H& C NMR spectra of compound 3e S45
1
H & 13C NMR spectra of compound 3f S47
1
H & 13C NMR spectra of compound 3g S49

S2
1
H & 13C NMR spectra of compound 3h S51
1
H & 13C NMR spectra of compound 3i S53
1
H & 13C NMR spectra of compound 3j S55
1 13
H& C NMR spectra of compound 3k S57
1
H &13C NMR spectra of compound 3l S59
1
H & 13C NMR spectra of compound 3m S61
1
H & 13C NMR spectra of compound 3n S63
1
H & 13C NMR spectra of compound 3o S65
1 13
H& C NMR spectra of compound 3p S67
1 13
H& C NMR spectra of compound 7a S69
1
H & 13C NMR spectra of compound 7b S71
X-ray Crystallographic Data of Compound 3a S73

S3
 Experimental Section

General Remarks: Nuclear Magnetic Resonance (1H and 13C NMR) spectra were recorded on a 300 MHz spectrometer in CDCl3 using TMS as
an internal standard. Chemical shifts are reported in parts per million (), coupling constants (J values) are reported in Hertz (Hz) and spin
13
multiplicities are indicated by the following symbols: s (singlet), d (doublet), t (triplet), p (pentad), m (multiplet). C NMR spectra were
routinely run with broadband decoupling. Pre coated silica gel on aluminium plates (Merck) were used for TLC analysis with a mixture of
petroleum ether (60–80 oC) and ethyl acetate as eluent. Elemental analyses were performed on a Perkin Elmer 2400 Series II Elemental CHNS
analyser. Mass spectra were recorded in LCQ Fleet spectrometer, Thermo Fisher Instruments Limited, US. Electrospray ionization spectrometry
(ESI-MS) analysis was performed in the positive ion and negative ion mode on a liquid chromatography ion trap.

General procedure for the synthesis α-azido chalcone 1: To a stirred suspension of chalcone (1.0 mmol) and NaN3 (1.5 mmol) in acetonitrile
(2.5 mL) was added ceric ammonium nitrate (2.5 mmol) in acetonitrile (10 mL) at 0° C under N2 atm. and the mixture was stirred at room
temperature. After the reaction completion the reaction mixture was quenched with water and extracted with ethyl acetate. The combined
organic layers were washed with water and brine, dried over anhydrous Na2SO4 and concentrated in vacuum and the resulting residue was
dissolved in acetone (2.5 mL) and added with anhydrous CH3COO-Na+ (1.5 mmol). The mixture was stirred at room temperature for 12 hrs and
quenched with water and extracted with ethyl acetate. The combined organic layers were washed with water and brine, dried over anhydrous
Na2SO4 and concentrated in vacuum. The resulting residue was purified by column chromatography on 60-120 silica gel (2-5% ethyl acetate in
hexane) to give α-azido chalcone 1 as a solid.

A typical procedure for the synthesis of Thiazole-2(3H)-thiones 3: In a 10 mL quartz vial -azido chalcone 1 (0.10 mmol), potassium ethyl
xanthogenate 2 (0.30 mmol), were added in PEG-400 (3 mL) and the vial was heated at 50 oC for 1h. The reaction was monitored by TLC
chromatography using petroleum ether : ethyl acetate mixture (5:5) as eluent. After the completion of the reaction, the reaction was cooled to

S4
room temperature and ice cooled water was added. The precipitate obtained was filtered, dried in vacuum and recrystallized from ethanol to
afford 3.

Characterization data of compounds 1, 3 and 7

(Z)-2-Azido-1-(4-bromophenyl)-3-(2-chloro-3,4-dimethoxyphenyl)prop-2-en-1-one (1a)
Isolated as yellow solid; mp: 65-66 oC; IR (KBr): 679, 1092, 1679, 2116, 2834, 3054 cm-1; 1H NMR (300 MHz,
CDCl3) δ 8.15 (d, J = 8.9 Hz, 1H), 7.71 (d, J = 8.6 Hz, 2H), 7.66 (d, J = 8.6 Hz, 2H), 6.91 (d, J = 9.0 Hz, 1H), 6.87
13
(s, 1H), 3.94 (s, 3H), 3.84 (s, 3H). C NMR (75 MHz, CDCl3) δ 190.8, 154.5, 145.4, 135.2, 133.0, 131.6, 131.1,
129.6, 127.7, 126.7, 125.3, 124.1, 109.9, 60.4, 55.9. ESI-MS m/z calcd for C17H13BrClN3O3: [M]+ 422.66; Found:
[M-28]+ 394.12. Anal. Calcd for C17H13BrClN3O3: C, 48.31; H, 3.10; N, 9.94%. Found: C, 48.36; H, 3.13; N,
9.91%.
(Z)-1,3-Di([1,1'-biphenyl]-4-yl)-2-azidoprop-2-en-1-one (1c)
Isolated as off white solid; mp: 53-55 oC; IR (KBr): 1674, 2112, 3034 cm-1; 1H NMR (300 MHz, CDCl3) δ 7.93 –
7.87 (m, 4H), 7.70 – 7.62 (m, 8H), 7.52 – 7.37 (m, 6H), 6.56 (s, 1H). 13C NMR (75 MHz, CDCl3) δ 191.4, 145.3,
142.1, 139.9, 139.5, 135.2, 133.5, 132.1, 131.1, 130.2, 129.0, 128.9, 128.8, 128.2, 127.7, 127.1, 127.0, 126.9,
126.8. ESI-MS m/z calcd for C27H19N3O: [M]+ 401.47; Found: [M-28]+ 373.28. Anal. Calcd for C27H19N3O: C,
80.78; H, 4.77; N, 10.47%. Found: C, 80.83; H, 4.74; N, 10.49%.
(Z)-2-Azido-1-(4-chlorophenyl)-3-(2,4-dimethoxyphenyl)prop-2-en-1-one (1f)
Isolated as yellow solid; mp: 72-73 oC; IR (KBr): 1084, 1678, 2118, 2838, 3048 cm-1; 1H NMR (300 MHz, CDCl3)
δ 8.33 (d, J = 8.7 Hz, 1H), 7.39 (d, J = 5.6 Hz, 4H), 6.92 (s, 1H), 6.53 (d, J = 7.7 Hz, 1H), 6.36 (s, 1H), 3.87 (s,
13
3H), 3.81 (s, 3H). C NMR (75 MHz, CDCl3) δ 190.9, 162.5, 159.2, 131.9, 131.0, 130.9, 128.9, 128.6, 128.5,

S5
 124.6, 115.1, 104.7, 97.8, 55.5, 55.4. ESI-MS m/z calcd for C17H14ClN3O3: [M]+ 343.77; Found: [M-28]+ 315.18.
Anal. Calcd for: C, 59.40; H, 4.11; N, 12.22%. Found: C, 59.44; H, 4.17; N, 12.25%.
(Z)-2-Azido-3-(3,4-dimethoxyphenyl)-1-(thiophen-2-yl)prop-2-en-1-one (1h)
Isolated as yellow solid; mp: 88-90 oC; IR (KBr): 1681, 2122, 2831, 3094 cm-1; 1H NMR (300 MHz, CDCl3) δ 7.75
(d, J = 5.0 Hz, 2H), 7.56 (s, 1H), 7.36 (d, J = 8.4 Hz, 1H), 7.19 (dd, J = 6.2, 2.5 Hz, 1H), 6.89 (d, J = 8.4 Hz, 1H),
13
6.74 (s, 1H), 3.94 (s, 6H). C NMR (75 MHz, CDCl3) δ 182.6, 150.3, 148.5, 141.6, 134.0, 131.7, 127.8, 126.8,
126.1, 124.9, 112.8, 110.7, 110.3, 55.8, 55.8. ESI-MS m/z calcd for C15H13N3O3S: [M]+ 315.35; Found: [M-28]+
287.22. Anal. Calcd for C15H13N3O3S: C, 57.13; H, 4.16; N, 13.33; S, 10.17 %. Found: C, 57.18; H, 4.11; N, 13.37;
S, 10.20 %.
(Z)-2-Azido-1-(4-bromophenyl)-3-(2,4-dichlorophenyl)prop-2-en-1-one (1i)
Isolated as white solid; mp: 61-62 oC; IR (KBr): 671, 1082, 1686, 2104, 3048 cm-1; 1H NMR (300 MHz, CDCl3) δ
8.28 (d, J = 8.6 Hz, 1H), 7.73 (d, J = 6.8 Hz, 2H), 7.67 (d, J = 8.6 Hz, 2H), 7.43 (s, 1H), 7.32 (d, J = 8.7 Hz, 1H),
6.77 (s, 1H). 13C NMR (75 MHz, CDCl3) δ 188.8, 143.8, 139.4, 136.2, 133.5, 132.2, 129.8,* 128.9, 125.0, 121.8,
119.2, 116.3. ESI-MS m/z calcd for C15H8BrCl2N3O: [M]+ 397.05; Found: [M-28]+ 369.12. Anal. Calcd for
C15H8BrCl2N3O: C, 45.38; H, 2.03; N, 10.58%. Found: C, 45.34; H, 2.07; N, 10.63%. (* Two carbons are merged).
(Z)-2-Azido-3-(4-methoxyphenyl)-1-(p-tolyl)prop-2-en-1-one (1j)
Isolated as pale yellow solid; mp: 57-59 oC; IR (KBr): 1438, 1685, 2119, 2826, 3046 cm-1; 1H NMR (300 MHz,
CDCl3) δ 7.79 (d, J = 8.8 Hz, 2H), 7.68 (d, J = 8.1 Hz, 2H), 7.27 (d, J = 9.0 Hz 2H), 6.91 (d, J = 8.8 Hz, 2H), 6.44
(s, 1H), 3.84 (s, 3H), 2.44 (s, 3H). 13C NMR (75 MHz, DMSO) δ 191.9, 160.6, 143.2, 134.3, 132.4, 131.8, 129.7,
129.7, 129.1, 126.0, 113.9, 55.3, 21.6. ESI-MS m/z calcd for C17H15N3O2: [M]+ 293.33; Found: [M-28]+ 265.18.
Anal. Calcd for C17H15N3O2: C, 69.61; H, 5.15; N, 14.33%. Found: C, 69.66; H, 5.17; N, 14.36%.

S6
(Z)-2-Aazido-3-(2,4-dichlorophenyl)-1-(naphthalen-1-yl)prop-2-en-1-one (1k)
Isolated as off-white solid; mp: 75-77 oC; IR (KBr):1085, 1683, 2113, 3055 cm-1; 1H NMR (300 MHz, CDCl3) δ
8.29 (d, J = 8.6 Hz, 1H), 7.98 – 7.91 (m, 5H), 7.67 – 7.58 (m, 4H), 6.88 (s, 1H). 13C NMR (75 MHz, CDCl3) δ
189.4, 138.9, 135.1, 133.0, 131.9, 131.7, 131.5, 129.9, 129.3, 129.2, 128.6, 128.5, 127.7, 127.4, 127.0, 126.9,
125.2, 124.2, 122.8. ESI-MS m/z calcd for C19H11Cl2N3O: [M]+ 368.22; Found: [M-28]+ 340.12. Anal. Calcd for
C19H11Cl2N3O: C, 61.98; H, 3.01; N, 11.41%. Found: C, 61.94; H, 3.06; N, 11.44%.
Isopropyl (Z)-2-azido-3-(4-chlorophenyl)acrylate (1m)
Isolated as white solid; mp: 49-50 oC; IR (KBr): 1078, 1153, 1671, 2113, 3038 cm-1; 1H NMR (300 MHz, CDCl3) δ
7.76 (d, J = 9.0 Hz, 2H), 7.35 (d, J = 8.6 Hz, 2H), 6.82 (s, 1H), 5.25 – 5.17 (m, 1H), 1.38 (d, J = 6.3 Hz, 6H). 13C
NMR (75 MHz, CDCl3) δ 162.6, 134.7, 131.5, 128.9, 128.4, 126.1, 123.2, 70.3, 21.6. ESI-MS m/z calcd for
C12H12ClN3O2: [M]+ 265.70; Found: [M-28]+ 237.56. Anal. Calcd for C12H12ClN3O2: C, 54.25; H, 4.55; N, 15.82%.
Found: C, 54.27; H, 4.59; N, 15.86%.
sec-Butyl (Z)-2-azido-3-(4-chlorophenyl)acrylate (1n)
Isolated as white solid; mp: 41-43 oC; IR (KBr): 1091, 1469, 1678, 2128, 3051 cm-1; 1H NMR (300 MHz, CDCl3) δ
7.76 (d, J = 8.6 Hz, 2H), 7.34 (d, J = 8.6 Hz, 2H), 6.83 (s, 1H), 5.12 – 5.01 (m, 1H), 1.77 – 1.66 (m, 2H), 1.34 (d, J
= 6.3 Hz, 3H), 0.97 (t, J = 7.5 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 162.7, 134.8, 131.6, 128.9, 128.4, 126.1,
123.1, 74.8, 28.6, 19.2, 9.6. ESI-MS m/z calcd for C13H14ClN3O2: [M]+ 279.72; Found: [M-28]+ 251.18. Anal.
Calcd for C13H14ClN3O2: C, 55.82; H, 5.04; N, 15.02%. Found: C, 55.86; H, 5.09; N, 15.04%.

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(Z)-2-Azido-3-(4-chlorophenyl)-1-morpholinoprop-2-en-1-one (1o)
Isolated as off-white solid; mp: 68-70 oC; IR (KBr): 1086, 1648, 2117, 2814, 3039 cm-1; 1H NMR (300 MHz,
CDCl3) δ 7.44 (s, 4H), 7.38 (s, 1H), 3.81 – 3.72 (m, 8H). 13C NMR (75 MHz, CDCl3) δ 164.5, 136.0, 132.4, 129.3,
129.2, 128.8, 128.7, 66.4, 42.8. ESI-MS m/z calcd for C13H13ClN4O2: [M]+ 292.72; Found: [M-28]+ 264.11. Anal.
Calcd for C13H13ClN4O2: C, 53.34; H, 4.48; N, 19.14%. Found: C, 53.39; H, 4.52; N, 19.17%.
(2Z,2'Z)-3,3'-(1,4-Phenylene)bis(2-azido-1-(4-chlorophenyl)prop-2-en-1-one) (1p)
Isolated as pale yellow solid; mp: 121-122 oC; IR (KBr): 1079, 1644, 2124, 3064 cm-1; 1H NMR (300 MHz,
CDCl3) δ 7.98 (d, J = 7.2 Hz, 2H), 7.89 – 7.83 (m, 4H), 7.77 (d, J = 8.3 Hz, 2H), 7.67 (d, J = 8.3 Hz, 2H), 7.50 (d, J
= 5.3 Hz, 4H). 13C NMR (75 MHz, CDCl3) δ 180.2, 139.4, 136.3, 132.2, 131.0, 130.7, 129.9, 128.9, 128.6. ESI-MS
m/z calcd for C24H14Cl2N6O2: [M]+ 489.32; Found: [M-56]+ 433.25. Anal. Calcd for C24H14Cl2N6O2: C, 58.91; H,
2.88; N, 17.18%. Found: C, 58.96; H, 2.84; N, 17.23%.
(4-Bromophenyl)(5-(2-chloro-3,4-dimethoxyphenyl)-2-thioxo-2,3-dihydrothiazol-4-yl)methanone (3a)
Isolated as yellow solid; mp: 147-148 oC; IR (KBr) 3094, 2971, 1672, 1253, 1171, 1118, 1054, 810, 679 cm-1; 1H
NMR (300 MHz, CDCl3) δ 10.49 (s, 1H), 7.34 (d, J = 8.5 Hz, 2H), 7.28 (d, J = 5.1 Hz, 2H), 6.81 (d, J = 8.6 Hz,
1H), 6.62 (d, J = 8.6 Hz, 1H), 3.84 (s, 3H), 3.70 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 187.9, 182.9, 155.1, 145.9,
136.4, 134.9, 134.0, 130.9, 130.4, 128.1, 127.8, 127.4, 120.4, 110.6, 60.5, 56.2. ESI-MS m/z calcd for
C18H13BrClNO3S2: [M]+ 470.78; Found: [M+ - H] 469.84. Anal. Calcd for C18H13BrClNO3S2: C, 45.92; H, 2.78;
N, 2.98; S, 13.62 %. Found: C, 45.96; H, 2.74; N, 2.99; S, 13.65 %.

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(4-Chlorophenyl)(2-thioxo-5-(p-tolyl)-2,3-dihydrothiazol-4-yl)methanone (3b)
Isolated as yellow solid; mp: 186 -188 oC; IR (KBr) 3024, 2875, 1647, 1177, 1112, 1085, 810 cm-1; 1H NMR (300
MHz, CDCl3) δ 10.77 (s, 1H), 7.46 (d, J = 8.5 Hz, 2H), 7.11 (d, J = 8.5 Hz, 2H), 6.94 (d, J = 1.4 Hz, 4H), 2.27 (s,
13
3H). C NMR (75 MHz, CDCl3) δ 187.5, 183.2, 133.5, 132.7, 130.8, 130.6, 129.5, 129.4, 129.3, 129.1, 128.4,
128.1, 21.2. ESI-MS m/z calcd for C17H12ClNOS2: [M]+ 345.86; Found: [M+ - H] 344.05. Anal. Calcd for
C17H12ClNOS2: C, 59.04; H, 3.50; N, 4.05; S, 18.54 %. Found: C, 59.08; H, 3.53; N, 4.07; S, 18.59 %.
[1,1'-Biphenyl]-4-yl(5-([1,1'-biphenyl]-4-yl)-2-thioxo-2,3-dihydrothiazol-4-yl)methanone (3c)
Isolated as yellow solid; mp: 219-220 oC; IR (KBr) 3042, 2974, 1817, 1669, 1147, 1124 cm-1; 1H NMR (300
MHz, CDCl3) δ 10.29 (s, 1H), 7.56 (d, J = 9.0 Hz, 2H), 7.48 – 7.32 (m, 14H), 7.14 (d, J = 8.2 Hz, 2H). 13C NMR
(75 MHz, CDCl3) δ 187.4, 183.7, 146.1, 142.8, 139.4, 133.7, 133.2, 129.9, 128.8, 128.3, 128.0, 127.7, 127.2,
127.0, 126.7. ESI-MS m/z calcd for C28H19NOS2: [M]+ 449.59; Found: [M+ - H] 448.11. Anal. Calcd for
C28H19NOS2: C, 74.80; H, 4.26; N, 3.12; S, 14.26 %. Found: C, 74.84; H, 4.29; N, 3.15; S, 14.28 %.

(4-Methoxyphenyl)(5-(4-nitrophenyl)-2-thioxo-2,3-dihydrothiazol-4-yl)methanone (3d)
Isolated as yellow solid; mp: 181-182 oC; IR (KBr) 3072, 2980, 1659, 1509, 1255, 1181, 1110, 812 cm-1; 1H
NMR (300 MHz, CDCl3) δ 7.58 (d, J = 9.0 Hz, 2H), 7.33 (d, J = 8.2 Hz, 2H), 7.05 (d, J = 7.3 Hz, 2H), 6.66 (d, J
= 8.8 Hz, 2H), 3.77 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 186.8, 182.6, 164.6, 147.6, 139.7, 135.4, 132.9, 132.2,
129.9, 127.2, 123.8, 113.9, 55.55. ESI-MS m/z calcd for C17H12N2O4S2: [M]+ 372.41; Found: [M+ - H] 371.82.
Anal. Calcd for C17H12N2O4S2: C, 54.83; H, 3.25; N, 7.52; S, 17.22 %. Found: C, 54.86; H, 3.29; N, 7.54; S,
17.28 %.

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Phenyl(5-phenyl-2-thioxo-2,3-dihydrothiazol-4-yl)methanone (3e)
Isolated as yellow solid; mp: 146-147 oC; IR (KBr) 3082, 2981, 1815, 1671, 1143, 1128 cm-1; 1H NMR (300
MHz, CDCl3) δ 7.52 (d, J = 8.0 Hz, 2H), 7.48 – 7.29 (m, 4H), 7.17 – 7.07 (m, 4H). 13C NMR (75 MHz, CDCl3) δ
187.5, 184.2, 139.7, 135.1, 133.2, 133.0, 129.7, 129.5, 129.4, 128.9, 128.6, 128.1. ESI-MS m/z calcd for
C16H11NOS2: [M]+ 297.39; Found: [M+ - H] 296.01. Anal. Calcd for C16H11NOS2: C, 64.62; H, 3.73; N, 4.71; S,
21.56%. Found: C, 64.67; H, 3.75; N, 4.73; S, 21.57 %.
(4-Chlorophenyl)(5-(2,4-dimethoxyphenyl)-2-thioxo-2,3-dihydrothiazol-4-yl)methanone (3f)
Isolated as yellow solid; mp: 177-179 oC; IR (KBr) 3073, 2975, 1678, 1259, 1173, 1128, 1055, 811 cm-1; 1H
NMR (300 MHz, CDCl3) δ 10.25 (s, 1H), 7.47 (d, J = 8.6 Hz, 2H), 7.12 (d, J = 8.5 Hz, 2H), 6.98 (d, J = 8.5 Hz,
1H), 6.33 (dd, J = 8.4, 2.3 Hz, 1H), 6.11 (d, J = 2.2 Hz, 1H), 3.75 (s, 3H), 3.53 (s, 3H). 13C NMR (75 MHz,
CDCl3) δ 187. 9, 183.1, 162.9, 157.1, 139.2, 135.6, 133.7, 133.3, 131.9, 130.2, 128.0, 110.7, 105.3, 98.5, 55.6,
55.0. ESI-MS m/z calcd for C18H14ClNO3S2: [M]+ 391.88; Found: [M+ - H] 389.99. Anal. Calcd for
C18H14ClNO3S2: C, 55.17; H, 3.60; N, 3.57; S, 16.36 %. Found: C, 55.21; H, 3.66; N, 3.53; S, 16.39%.
(5-(4-Bromophenyl)-2-thioxo-2,3-dihydrothiazol-4-yl)(4-chlorophenyl)methanone (3g)
Isolated as yellow solid; mp: 201-202 oC; IR (KBr) 3018, 2944, 1664, 1175, 1113, 1067, 814, 695 cm-1; 1H NMR
(300 MHz, CDCl3) δ 9.25 (s, 1H), 7.47 (d, J = 8.9 Hz, 2H), 7.28 (d, J = 5.2 Hz, 2H), 7.17 (d, J = 10.9 Hz, 2H),
6.93 (d, J = 7.7 Hz, 2H). 13C NMR (75 MHz, CDCl3) δ 187.2, 183.8, 139.5, 133.7, 131.2, 130.9, 130.4, 130.2,
129.9, 128.0, 127.8, 122.6. ESI-MS m/z calcd for C16H9BrClNOS2: [M]+ 410.73; Found: [M+ - H] 409.95. Anal.
Calcd for C16H9BrClNOS2: C, 46.79; H, 2.21; N, 3.41; S, 15.61%. Found: C, 46.75; H, 2.26; N, 3.43; S, 15.67 %.

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(5-(3,4-Dimethoxyphenyl)-2-thioxo-2,3-dihydrothiazol-4-yl)(thiophen-2-yl)methanone (3h)
Isolated as yellow solid; mp: 173-175 oC; IR (KBr) 3199, 2972, 1684, 1258, 1168, 1139, 937 cm-1; 1H NMR (300
MHz, CDCl3) δ 10.23 (s, 1H), 7.60 (d, J = 4.9 Hz, 1H), 7.27 (s, 1H), 6.88 (dd, J = 8.3, 2.0 Hz, 1H), 6.84 – 6.81
(m, 1H), 6.77 (d, J = 8.3 Hz, 1H), 6.61 (d, J = 1.9 Hz, 1H), 3.86 (s, 3H), 3.65 (s, 3H). 13C NMR (75 MHz, CDCl3)
δ 187.2, 175.9, 150.7, 149.2, 140.5, 138.0, 135.6, 132.2, 128.1, 122.2, 121.6, 112.6, 111.4, 55.9, 55.9. ESI-MS
m/z calcd for C16H13NO3S3: [M]+ 363.46; Found: [M+ - H] 361.99. Anal. Calcd for C16H13NO3S3: C, 52.87; H,
3.61; N, 3.85; S, 26.46 %. Found: C, 52.91; H, 3.67; N, 3.83; S, 26.48 %.
(4-Bromophenyl)(5-(2,4-dichlorophenyl)-2-thioxo-2,3-dihydrothiazol-4-yl)methanone (3i)
Isolated as yellow solid; mp: 188-189 oC; IR (KBr) 3148, 3065, 1668, 1175, 1139, 1066, 804, 684 cm-1; 1H NMR
(300 MHz, CDCl3) δ 9.06 (s, 1H), 7.35 (s, 1H), 7.33 (s, 1H), 7.32 – 7.31 (m, 1H), 7.26 (s, 2H), 7.04 (s, 2H). 13C
NMR (75 MHz, CDCl3) δ 187.8, 183.8, 135.9, 134.7, 134.4, 133.0, 131.1, 130.8, 130.4, 130.2, 129.4, 128.2,
126.9, 125.3. ESI-MS m/z calcd for C16H8BrCl2NOS2: [M]+ 445.17; Found: [M+ - H] 444.02. Anal. Calcd for
C16H8BrCl2NOS2: C, 43.17; H, 1.81; N, 3.15; S, 14.40 %. Found: C, 43.13; H, 1.86; N, 3.12; S, 14.45 %.

(5-(4-Methoxyphenyl)-2-thioxo-2,3-dihydrothiazol-4-yl)(p-tolyl)methanone (3j)
Isolated as yellow solid; mp: 131-132 oC; IR (KBr) 3078, 2965, 1685, 1264, 1178, 1118, 1054, 931 cm-1; 1H
NMR (300 MHz, CDCl3) δ 10.47 (s, 1H), 7.45 (d, J = 8.1 Hz, 2H), 6.98 (t, J = 8.7 Hz, 4H), 6.64 (d, J = 8.7 Hz,
2H), 3.73 (s, 3H), 2.28 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 187.2, 184.1, 160.6, 144.4, 139.2, 132.6, 132.3,
130.8, 129.7, 128.8, 121.1, 114.0, 55.3, 21.6. ESI-MS m/z calcd for C18H15NO2S2: [M]+ 341.44; Found:[M+ - H]
340.32. Anal. Calcd for C18H15NO2S2: C, 63.32; H, 4.43; N, 4.10; S, 18.78 %. Found: C, 63.35; H, 4.47; N, 4.12;
S, 18.74%.

S11
(5-(2,4-Dichlorophenyl)-2-thioxo-2,3-dihydrothiazol-4-yl)(naphthalen-1-yl)methanone (3k)
o
Isolated as yellow solid; mp: 177-178 C; IR (KBr) 3077, 2972, 1828, 1677, 1169, 1122, 1053, 806 cm-1; 1H
NMR (300 MHz, CDCl3) δ 9.08 (s, 1H), 8.00 (s, 1H), 7.76 (d, J = 8.0 Hz, 1H), 7.71 – 7.65 (m, 2H), 7.60 – 7.47
(m, 3H), 7.05 – 6.95 (m, 2H), 6.81 (d, J = 8.3 Hz, 1H). 13C NMR (75 MHz, CDCl3) δ 188.7, 184.7, 135.3, 134.8,
134.2, 132.9, 132.8, 131.2, 131.1, 130.7, 129.2, 128.6, 128.5, 128.4, 127.8, 127.4, 126.7, 126.6, 124.8, 123.9.
ESI-MS m/z calcd for C20H11Cl2NOS2: [M]+ 416.33; Found: [M+ - H] 415.18. Anal. Calcd for C20H11Cl2NOS2: C,
57.70; H, 2.66; N, 3.36; S, 15.40%. Found: C, 57.76; H, 2.68; N, 3.33; S, 15.45%.
Ethyl 5-phenyl-2-thioxo-2,3-dihydrothiazole-4-carboxylate (3l)
Isolated as yellow solid; mp: 167-169 oC; IR (KBr) 3035, 2978, 2244, 1816, 1683, 1171, 1097, 1061 cm-1; 1H
NMR (300 MHz, CDCl3) δ 10.74 (s, 1H), 7.48 – 7.40 (m, 5H), 4.27 (q, J = 7.1 Hz, 2H), 1.22 (t, J = 7.1 Hz, 3H).
13
C NMR (75 MHz, CDCl3) δ 187.0, 156.9, 140.4, 129.9, 129.5, 128.4, 128.2, 125.7, 62.3, 13.8. ESI-MS m/z
calcd for C12H11NO2S2: [M]+ 265.35; Found: [M+ - H] 264.02. Anal. Calcd for C12H11NO2S2: C, 54.32; H, 4.18;
N, 5.28; S, 24.16 %. Found: C, 54.35; H, 4.22; N, 5.23; S, 24.18 %.
Isopropyl 5-(4-chlorophenyl)-2-thioxo-2,3-dihydrothiazole-4-carboxylate (3m)
Isolated as yellow solid; mp: 125-126 oC; IR (KBr) 3049, 2978, 2244, 1695, 1177, 1093, 1058, 813 cm-1; 1H
NMR (300 MHz, CDCl3) δ 10.61 (s, 1H), 7.40 (d, J = 0.6 Hz, 4H), 5.14 (dt, J = 12.5, 6.2 Hz, 1H), 1.23 (d, J = 6.3
Hz, 6H). 13C NMR (75 MHz, CDCl3) δ 186.9, 156.3, 138.7, 136.2, 131.0, 128.6, 126.9, 126.1, 71.0, 21.6. ESI-MS
m/z calcd for C13H12ClNO2S2: [M]+ 313.81; Found: [M+ - H] 312.12. Anal. Calcd for C13H12ClNO2S2: C, 49.76;
H, 3.85; N, 4.46; S, 20.43 %. Found: C, 49.77; H, 3.89; N, 4.42; S, 20.48%.

S12
sec-Butyl 5-(4-chlorophenyl)-2-thioxo-2,3-dihydrothiazole-4-carboxylate (3n)
Isolated as yellow solid; mp: 112-114 oC; IR (KBr) 3079, 2972, 2237, 1686, 1168, 1101, 1052, 803 cm-1; 1H
NMR (300 MHz, CDCl3) δ 7.42 – 7.29 (m, 4H), 4.96 (dt, J = 12.4, 6.2 Hz, 1H), 1.68 – 1.53 (m, 2H), 1.26 (d, J =
4.4 Hz, 3H), 0.94 – 0.84 (m, 3H). 13C NMR (75 MHz, CDCl3) δ 199.7, 167.5, 136.4, 134.5, 130.9, 129.1, 128.7,
128.4, 75.6, 28.4, 19.1, 9.4. ESI-MS m/z calcd for C14H14ClNO2S2: [M]+ 327.84; Found: [M+ - H] 326.32. Anal.
Calcd for C14H14ClNO2S2: C, 51.29; H, 4.30; N, 4.27; S, 19.56 %. Found: C, 51.32; H, 4.35; N, 4.23; S, 19.58 %.
(5-(4-Chlorophenyl)-2-thioxo-2,3-dihydrothiazol-4-yl)(morpholino)methanone (3o)
Isolated as yellow solid; mp: 191-192 oC; IR (KBr) 3071, 2967, 2241, 1696, 1172, 1096, 1055, 813 cm-1; 1H
NMR (300 MHz, CDCl3) δ 9.99 (s, 1H), 7.34 – 7.28 (m, 4H), 3.48 – 3.39 (m, 4H), 3.21 – 3.14 (m, 4H). 13C NMR
(75 MHz, CDCl3) δ 189.2, 164.8, 135.4, 131.7, 128.8, 128.3, 128.2, 127.1, 65.7, 44.8. ESI-MS m/z calcd for
C14H13ClN2O2S2: [M]+ 340.84; Found: [M+ - H] 339.44. Anal. Calcd for C14H13ClN2O2S2: C, 49.34; H, 3.84; N,
8.22; S, 18.81%. Found: C, 49.37; H, 3.89; N, 8.23; S, 18.86%.

(1,4-Phenylenebis(2-thioxo-2,3-dihydrothiazole-5,4-diyl))bis((4-chlorophenyl)methanone) (3p)
Isolated as yellow solid; mp: 226-228 oC; IR (KBr) 3087, 2977, 1825, 1679, 1164, 1131, 1055, 816 cm-1;
1
H NMR (300 MHz, CDCl3) δ 13.54 (s, 2H), 7.95 (d, J = 7.7 Hz, 2H), 7.62 (d, J = 8.2 Hz, 2H), 7.45 (d, J
= 12.0 Hz, 6H), 7.23 – 7.14 (m, 2H). 13C NMR (75 MHz, CDCl3) δ 196.2, 188.2, 142.9, 130.6, 129.5,
129.1, 128.5, 128.3, 127.9, 127.4. ESI-MS m/z calcd for C26H14Cl2N2O2S4: [M]+ 585.55; Found: [M+ -
2H] 583.18 . Anal. Calcd for C26H14Cl2N2O2S4: C, 53.33; H, 2.41; N, 4.78; S, 21.90 %. Found: C, 53.36;
H, 2.43; N, 4.75; S, 21.94 %.

S13
 (5-(4-Bromophenyl)-2-(prop-2-yn-1-ylthio)thiazol-4-yl)(4-chlorophenyl)methanone (7a)
Isolated as pale orange solid; mp: 102-103 oC; IR (KBr) 3318, 3011, 2941, 1667, 1422, 1171, 1121,
1062, 802, 693 cm-1; 1H NMR (300 MHz, CDCl3) δ 7.72 (d, J = 8.5 Hz, 2H), 7.26 (d, J = 11.8, Hz, 4H),
6.98 (d, J = 8.4 Hz, 2H), 4.75 (d, J = 2.4 Hz, 2H), 2.06 (t, J = 2.3 Hz, 1H). 13C NMR (75 MHz, CDCl3) δ
185.9, 140.6, 134.3, 134.3, 131.8, 131.7, 131.1, 130.2, 129.6, 128.9, 128.8, 123.5, 77.6, 73.8, 32.9. ESI-
MS m/z calcd for C19H11BrClNOS2: [M]+ 448.78; Found: [M+H]+ 449.55. Anal. Calcd for
C19H11BrClNOS2: C, 50.85; H, 2.47; N, 3.12; S, 14.29 %. Found: C, 50.88; H, 2.43; N, 3.16; S, 14.24 %.
(Disulfanediylbis(5-(4-bromophenyl)thiazole-2,4-diyl))bis((4-chlorophenyl)methanone) (7b)
Isolated as dark yellow solid; mp: 219-220 oC; IR (KBr) 3027, 2953, 1669, 1168, 1115, 1069, 814, 718,
698 cm-1; 1H NMR (300 MHz, DMSO) δ 7.57 (d, J = 8.4 Hz, 2H), 7.47 – 7.27 (m, 12H), 7.02 (d, J = 8.4
13
Hz, 2H). C NMR (75 MHz, DMSO) δ 184.8, 169.4, 138.5, 134.8, 131.9, 131.6, 131.4, 131.3, 131.2,
128.8, 128.6, 122.6. ESI-MS m/z calcd for C32H16Br2Cl2N2O2S4: [M]+ 819.44; Found: [M+H]+ 820.12.
Anal. Calcd for C32H16Br2Cl2N2O2S4: C, 46.90; H, 1.97; N, 3.42; S, 15.65 %. Found: C, 46.96; H, 1.93;
N, 3.46; S, 15.69 %.

S14
Fig 1. 1H NMR spectrum of compound 1a
S15
Fig 2. 13C NMR spectrum of compound 1a
S16
Fig 3. 1H NMR spectrum of compound 1c
S17
Fig 4. 13C NMR spectrum of compound 1c
S18
Fig 5. 1H NMR spectrum of compound 1f
S19
Fig 6. 13C NMR spectrum of compound 1f
S20
Fig 7. 1H NMR spectrum of compound 1h
S21
Fig 8. 13C NMR spectrum of compound 1h
S22
Fig 9. 1H NMR spectrum of compound 1i
S23
Fig 10. 13C NMR spectrum of compound 1i
S24
Fig 11. 1H NMR spectrum of compound 1j
S25
Fig 12. 13C NMR spectrum of compound 1j
S26
Fig 13. 1H NMR spectrum of compound 1k

S27
Fig14. 13C NMR spectrum of compound 1k
S28
Fig15. 1H NMR spectrum of compound 1m
S29
Fig 16. 13C NMR spectrum of compound 1m
S30
Fig 17. 1H NMR spectrum of compound 1n
S31
Fig 18. 13C NMR spectrum of compound 1n
S32
Fig 19. 1H NMR spectrum of compound 1o
S33
Fig 20. 13C NMR spectrum of compound 1o
S34
Fig 21. 1H NMR spectrum of compound 1p
S35
Fig 22. 13C NMR spectrum of compound 1p
S36
Fig 23. 1H NMR spectrum of compound 3a
S37
Fig 24. 13C NMR spectrum of compound 3a
S38
Fig 25. 1H NMR spectrum of compound 3b
S39
Fig 26. 13C NMR spectrum of compound 3b
S40
Fig 27. 1H NMR spectrum of compound 3c
S41
Fig 28. 13C NMR spectrum of compound 3c
S42
Fig 29. 1H NMR spectrum of compound 3d
S43
Fig 30. 13C NMR spectrum of compound 3d
S44
Fig 31. 1H NMR spectrum of compound 3e
S45
Fig 32. 13C NMR spectrum of compound 3e
S46
Fig 33. 1H NMR spectrum of compound 3f
S47
Fig 34. 13C NMR spectrum of compound 3f
S48
Fig 35. 1H NMR spectrum of compound 3g
S49
Fig 36. 13C NMR spectrum of compound 3g
S50
Fig 37. 1H NMR spectrum of compound 3h
S51
Fig 38. 13C NMR spectrum of compound 3h
S52
Fig 39. 1H NMR spectrum of compound 3i
S53
Fig 40. 13C NMR spectrum of compound 3i
S54
Fig 41. 1H NMR spectrum of compound 3j
S55
Fig 42. 13C NMR spectrum of compound 3j
S56
Fig 43. 1H NMR spectrum of compound 3k
S57
Fig 44. 13C NMR spectrum of compound 3k
S58
Fig 45. 1H NMR spectrum of compound 3l
S59
Fig 46. 13C NMR spectrum of compound 3l
S60
Fig 47. 1H NMR spectrum of compound 3m
S61
Fig 48. 13C NMR spectrum of compound 3m
S62
Fig 49. 1H NMR spectrum of compound 3n
S63
Fig 50. 13C NMR spectrum of compound 3n
S64
Fig 51. 1H NMR spectrum of compound 3o
S65
Fig 52. 13C NMR spectrum of compound 3o
S66
Fig 53. 1H NMR spectrum of compound 3p
S67
Fig 54. 13C NMR spectrum of compound 3p
S68
Fig 55. 1H NMR spectrum of compound 7a
S69
Fig 56. 13C NMR spectrum of compound 7a
S70
Fig 57. 1H NMR spectrum of compound 7b
S71
Fig 58. 13C NMR spectrum of compound 7b
S72
X-ray analysis of compound
3a

S73
Table 1. Crystal data and structure refinement for SMB_KR_151219_Q_Thiazole5.
Identification code thiazole5
Empirical formula C18 H13 Br Cl N O3 S2
Formula weight 470.77
Temperature 100.0 K
Wavelength 0.71073 Å
Crystal system Monoclinic
Space group C 1 2/c 1
Unit cell dimensions a = 28.7355(10) Å = 90°.
b = 9.6150(3) Å = 104.703(2)°.
c = 13.6916(5) Å  = 90°.
Volume 3659.0(2) Å3
Z 8
Density (calculated) 1.709 Mg/m3
Absorption coefficient 2.640 mm-1
F(000) 1888
Crystal size 0.538 x 0.516 x 0.404 mm3
Theta range for data collection 2.611 to 28.330°.
Index ranges -38<=h<=38, -12<=k<=12, -18<=l<=18
Reflections collected 43622
Independent reflections 4561 [R(int) = 0.0522]
Completeness to theta = 25.242° 99.8 %
Absorption correction Semi-empirical from equivalents
Max. and min. transmission 0.7457 and 0.5149
Refinement method Full-matrix least-squares on F2

S74
Data / restraints / parameters 4561 / 0 / 237
Goodness-of-fit on F2 1.057
Final R indices [I>2sigma(I)] R1 = 0.0260, wR2 = 0.0524
R indices (all data) R1 = 0.0338, wR2 = 0.0550
Extinction coefficient n/a
Largest diff. peak and hole 0.417 and -0.445 e.Å-3

S75
Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103)
for SMB_KR_151219_Q_Thiazole5. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor.
________________________________________________________________________________
x y z U(eq)
________________________________________________________________________________
Br(1) 4277(1) 8404(1) 5935(1) 18(1)
Cl(1) 3406(1) 3952(1) 1962(1) 14(1)
S(1) 3494(1) 562(1) 2727(1) 12(1)
S(2) 4139(1) -1639(1) 2257(1) 14(1)
O(1) 4869(1) 1592(1) 5443(1) 14(1)
O(2) 2426(1) 5995(1) 4152(1) 12(1)
O(3) 2696(1) 5841(1) 2419(1) 12(1)
N(1) 4360(1) 369(1) 3690(1) 10(1)
C(1) 4195(1) 1561(2) 4074(1) 9(1)
C(2) 3722(1) 1830(2) 3631(1) 9(1)
C(3) 4044(1) -283(2) 2933(1) 10(1)
C(4) 4536(1) 2268(2) 4926(1) 9(1)
C(5) 4469(1) 3760(2) 5136(1) 10(1)
C(6) 4588(1) 4200(2) 6140(1) 11(1)
C(7) 4520(1) 5576(2) 6373(1) 13(1)
C(8) 4356(1) 6517(2) 5597(1) 12(1)
C(9) 4257(1) 6121(2) 4593(1) 12(1)
C(10) 4308(1) 4728(2) 4367(1) 10(1)
C(11) 3398(1) 2934(2) 3810(1) 9(1)
C(12) 3252(1) 3001(2) 4704(1) 10(1)

S76
C(13) 2928(1) 4005(2) 4849(1) 10(1)
C(14) 2746(1) 4975(2) 4097(1) 9(1)
C(15) 2890(1) 4939(2) 3189(1) 9(1)
C(16) 3213(1) 3924(2) 3064(1) 9(1)
C(17) 2184(1) 5896(2) 4945(1) 17(1)
C(18) 2925(1) 7179(2) 2540(1) 18(1)
________________________________________________________________________________

S77
Table 3. Bond lengths [Å] and angles [°] for SMB_KR_151219_Q_Thiazole5.
_____________________________________________________
Br(1)-C(8) 1.9000(16)
Cl(1)-C(16) 1.7354(17)
S(1)-C(2) 1.7431(17)
S(1)-C(3) 1.7345(17)
S(2)-C(3) 1.6611(17)
O(1)-C(4) 1.225(2)
O(2)-C(14) 1.3586(19)
O(2)-C(17) 1.434(2)
O(3)-C(15) 1.3708(19)
O(3)-C(18) 1.436(2)
N(1)-H(1) 0.8800
N(1)-C(1) 1.393(2)
N(1)-C(3) 1.348(2)
C(1)-C(2) 1.366(2)
C(1)-C(4) 1.483(2)
C(2)-C(11) 1.473(2)
C(4)-C(5) 1.486(2)
C(5)-C(6) 1.395(2)
C(5)-C(10) 1.393(2)
C(6)-H(6) 0.9500
C(6)-C(7) 1.386(2)
C(7)-H(7) 0.9500
C(7)-C(8) 1.384(2)

S78
C(8)-C(9) 1.385(2)
C(9)-H(9) 0.9500
C(9)-C(10) 1.391(2)
C(10)-H(10) 0.9500
C(11)-C(12) 1.393(2)
C(11)-C(16) 1.399(2)
C(12)-H(12) 0.9500
C(12)-C(13) 1.389(2)
C(13)-H(13) 0.9500
C(13)-C(14) 1.390(2)
C(14)-C(15) 1.408(2)
C(15)-C(16) 1.386(2)
C(17)-H(17A) 0.9800
C(17)-H(17B) 0.9800
C(17)-H(17C) 0.9800
C(18)-H(18A) 0.9800
C(18)-H(18B) 0.9800
C(18)-H(18C) 0.9800

C(3)-S(1)-C(2) 92.86(8)
C(14)-O(2)-C(17) 117.31(13)
C(15)-O(3)-C(18) 113.12(13)
C(1)-N(1)-H(1) 121.7
C(3)-N(1)-H(1) 121.7
C(3)-N(1)-C(1) 116.51(14)

S79
N(1)-C(1)-C(4) 117.01(14)
C(2)-C(1)-N(1) 112.57(14)
C(2)-C(1)-C(4) 130.25(15)
C(1)-C(2)-S(1) 109.57(12)
C(1)-C(2)-C(11) 131.52(15)
C(11)-C(2)-S(1) 118.89(12)
S(2)-C(3)-S(1) 123.34(10)
N(1)-C(3)-S(1) 108.37(12)
N(1)-C(3)-S(2) 128.28(13)
O(1)-C(4)-C(1) 118.36(15)
O(1)-C(4)-C(5) 121.41(15)
C(1)-C(4)-C(5) 120.23(14)
C(6)-C(5)-C(4) 118.18(15)
C(10)-C(5)-C(4) 122.18(15)
C(10)-C(5)-C(6) 119.60(15)
C(5)-C(6)-H(6) 119.9
C(7)-C(6)-C(5) 120.13(16)
C(7)-C(6)-H(6) 119.9
C(6)-C(7)-H(7) 120.4
C(8)-C(7)-C(6) 119.21(16)
C(8)-C(7)-H(7) 120.4
C(7)-C(8)-Br(1) 118.42(13)
C(7)-C(8)-C(9) 121.77(16)
C(9)-C(8)-Br(1) 119.80(13)
C(8)-C(9)-H(9) 120.7

S80
C(8)-C(9)-C(10) 118.60(16)
C(10)-C(9)-H(9) 120.7
C(5)-C(10)-H(10) 119.7
C(9)-C(10)-C(5) 120.56(16)
C(9)-C(10)-H(10) 119.7
C(12)-C(11)-C(2) 121.62(15)
C(12)-C(11)-C(16) 117.78(15)
C(16)-C(11)-C(2) 120.56(15)
C(11)-C(12)-H(12) 119.3
C(13)-C(12)-C(11) 121.39(15)
C(13)-C(12)-H(12) 119.3
C(12)-C(13)-H(13) 120.0
C(12)-C(13)-C(14) 119.99(15)
C(14)-C(13)-H(13) 120.0
O(2)-C(14)-C(13) 125.18(15)
O(2)-C(14)-C(15) 114.98(14)
C(13)-C(14)-C(15) 119.84(15)
O(3)-C(15)-C(14) 120.65(14)
O(3)-C(15)-C(16) 120.34(15)
C(16)-C(15)-C(14) 118.91(15)
C(11)-C(16)-Cl(1) 119.96(13)
C(15)-C(16)-Cl(1) 117.89(13)
C(15)-C(16)-C(11) 122.09(15)
O(2)-C(17)-H(17A) 109.5
O(2)-C(17)-H(17B) 109.5

S81
O(2)-C(17)-H(17C) 109.5
H(17A)-C(17)-H(17B) 109.5
H(17A)-C(17)-H(17C) 109.5
H(17B)-C(17)-H(17C) 109.5
O(3)-C(18)-H(18A) 109.5
O(3)-C(18)-H(18B) 109.5
O(3)-C(18)-H(18C) 109.5
H(18A)-C(18)-H(18B) 109.5
H(18A)-C(18)-H(18C) 109.5
H(18B)-C(18)-H(18C) 109.5
_____________________________________________________________
Symmetry transformations used to generate equivalent atoms:

S82
Table 4. Anisotropic displacement parameters (Å2x 103) for SMB_KR_151219_Q_Thiazole5. The anisotropic displacement factor exponent takes the form: -22[
h2 a*2U11 + ... + 2 h k a* b* U12 ]
______________________________________________________________________________
U11 U22 U33 U23 U13 U12
______________________________________________________________________________
Br(1) 24(1) 9(1) 26(1) -4(1) 14(1) 0(1)
Cl(1) 16(1) 16(1) 10(1) 4(1) 7(1) 6(1)
S(1) 10(1) 10(1) 12(1) -2(1) -1(1) 2(1)
S(2) 18(1) 12(1) 13(1) -4(1) 4(1) 3(1)
O(1) 11(1) 13(1) 14(1) 1(1) 0(1) 3(1)
O(2) 12(1) 12(1) 14(1) -1(1) 6(1) 4(1)
O(3) 13(1) 10(1) 12(1) 4(1) 0(1) 3(1)
N(1) 8(1) 9(1) 11(1) 0(1) 2(1) 3(1)
C(1) 11(1) 6(1) 10(1) 1(1) 3(1) 1(1)
C(2) 11(1) 7(1) 8(1) 1(1) 2(1) 1(1)
C(3) 13(1) 9(1) 11(1) 2(1) 5(1) 2(1)
C(4) 8(1) 9(1) 10(1) 1(1) 4(1) 0(1)
C(5) 7(1) 10(1) 12(1) 0(1) 3(1) -1(1)
C(6) 9(1) 13(1) 11(1) 2(1) 2(1) -2(1)
C(7) 12(1) 15(1) 12(1) -3(1) 5(1) -4(1)
C(8) 10(1) 8(1) 20(1) -3(1) 8(1) -2(1)
C(9) 12(1) 10(1) 15(1) 3(1) 4(1) 0(1)
C(10) 10(1) 11(1) 10(1) 0(1) 3(1) 0(1)
C(11) 8(1) 7(1) 11(1) 0(1) 1(1) 0(1)
C(12) 11(1) 9(1) 10(1) 1(1) 1(1) -1(1)

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C(13) 12(1) 10(1) 9(1) -2(1) 2(1) -2(1)
C(14) 6(1) 7(1) 13(1) -3(1) 1(1) -1(1)
C(15) 8(1) 8(1) 9(1) 1(1) 0(1) 0(1)
C(16) 9(1) 10(1) 9(1) -1(1) 2(1) 0(1)
C(17) 16(1) 19(1) 20(1) -4(1) 10(1) 2(1)
C(18) 24(1) 11(1) 21(1) 5(1) 8(1) 1(1)
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Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3)
for SMB_KR_151219_Q_Thiazole5.
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x y z U(eq)
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H(1) 4655 59 3930 11

H(6) 4715 3555 6666 13
H(7) 4586 5870 7057 15
H(9) 4157 6788 4069 14
H(10) 4233 4433 3682 12
H(12) 3376 2347 5225 12
H(13) 2831 4028 5463 12
H(17A) 1944 6639 4868 26
H(17B) 2418 5988 5600 26
H(17C) 2023 4991 4908 26
H(18A) 2785 7759 1950 27
H(18B) 3270 7064 2602 27
H(18C) 2877 7628 3149 27
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Table 6. Torsion angles [°] for SMB_KR_151219_Q_Thiazole5.
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Br(1)-C(8)-C(9)-C(10) -178.65(12)
S(1)-C(2)-C(11)-C(12) 110.44(16)
S(1)-C(2)-C(11)-C(16) -67.14(19)
O(1)-C(4)-C(5)-C(6) -35.1(2)
O(1)-C(4)-C(5)-C(10) 142.78(17)
O(2)-C(14)-C(15)-O(3) -3.1(2)
O(2)-C(14)-C(15)-C(16) -179.46(14)
O(3)-C(15)-C(16)-Cl(1) 6.5(2)
O(3)-C(15)-C(16)-C(11) -176.26(15)
N(1)-C(1)-C(2)-S(1) -0.21(18)
N(1)-C(1)-C(2)-C(11) 178.22(16)
N(1)-C(1)-C(4)-O(1) -22.3(2)
N(1)-C(1)-C(4)-C(5) 157.68(15)
C(1)-N(1)-C(3)-S(1) -3.87(18)
C(1)-N(1)-C(3)-S(2) 174.70(13)
C(1)-C(2)-C(11)-C(12) -67.9(3)
C(1)-C(2)-C(11)-C(16) 114.5(2)
C(1)-C(4)-C(5)-C(6) 144.91(16)
C(1)-C(4)-C(5)-C(10) -37.2(2)
C(2)-S(1)-C(3)-S(2) -175.59(11)
C(2)-S(1)-C(3)-N(1) 3.07(13)
C(2)-C(1)-C(4)-O(1) 152.54(17)
C(2)-C(1)-C(4)-C(5) -27.5(3)

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C(2)-C(11)-C(12)-C(13) -176.89(15)
C(2)-C(11)-C(16)-Cl(1) -5.7(2)
C(2)-C(11)-C(16)-C(15) 177.08(15)
C(3)-S(1)-C(2)-C(1) -1.65(13)
C(3)-S(1)-C(2)-C(11) 179.70(13)
C(3)-N(1)-C(1)-C(2) 2.8(2)
C(3)-N(1)-C(1)-C(4) 178.48(14)
C(4)-C(1)-C(2)-S(1) -175.21(14)
C(4)-C(1)-C(2)-C(11) 3.2(3)
C(4)-C(5)-C(6)-C(7) -178.40(15)
C(4)-C(5)-C(10)-C(9) -179.00(15)
C(5)-C(6)-C(7)-C(8) -3.1(3)
C(6)-C(5)-C(10)-C(9) -1.1(2)
C(6)-C(7)-C(8)-Br(1) -178.89(12)
C(6)-C(7)-C(8)-C(9) 0.0(3)
C(7)-C(8)-C(9)-C(10) 2.5(3)
C(8)-C(9)-C(10)-C(5) -1.9(3)
C(10)-C(5)-C(6)-C(7) 3.6(2)
C(11)-C(12)-C(13)-C(14) -0.4(2)
C(12)-C(11)-C(16)-Cl(1) 176.60(12)
C(12)-C(11)-C(16)-C(15) -0.6(2)
C(12)-C(13)-C(14)-O(2) 179.58(15)
C(12)-C(13)-C(14)-C(15) 0.0(2)
C(13)-C(14)-C(15)-O(3) 176.58(14)
C(13)-C(14)-C(15)-C(16) 0.2(2)

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C(14)-C(15)-C(16)-Cl(1) -177.13(12)
C(14)-C(15)-C(16)-C(11) 0.1(2)
C(16)-C(11)-C(12)-C(13) 0.8(2)
C(17)-O(2)-C(14)-C(13) -13.5(2)
C(17)-O(2)-C(14)-C(15) 166.15(14)
C(18)-O(3)-C(15)-C(14) 83.14(19)
C(18)-O(3)-C(15)-C(16) -100.53(18)
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Symmetry transformations used to generate equivalent atoms:

Table 7. Hydrogen bonds for SMB_KR_151219_Q_Thiazole5 [Å and °].

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D-H...A d(D-H) d(H...A) d(D...A) <(DHA)
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N(1)-H(1)...O(1)#1 0.88 2.13 2.9214(18) 149.7
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Symmetry transformations used to generate equivalent atoms:
#1 -x+1,-y,-z+1

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