upporting Information Cooperative Activating Effect of DM-Tertiary Amine on Elemental ulfur: Direct Access to Thioaurones from 2 -Nitrochalcones under Mild Conditions Thanh Binh Nguyen,* and Pascal Retailleau General information Reagents were obtained from commercial supplier and used without further purification. Analytical thin layer chromatography (TLC) was purchased from Merck KGaA (silica gel 60 F254). Visualization of the chromatogram was performed by UV light (254 nm) or phosphomolybdic acid or vanilline stains. Flash column chromatography was carried out using kieselgel 35-70 µm particle sized silica gel (230-400 mesh). NMR Chemical shifts are reported in (δ) ppm relative to tetramethylsilane (TM) with the residual solvent as internal reference (CDCl 3, δ 7.26 ppm for 1 H and δ 77.0 ppm for 13 C). Data are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet), coupling constants (Hz) and integration. 2 -Nitrochalcones 1 were prepared by Claisen-chmidt condensation of 2 -nitroacetophenones with aromatic aldehydes according to precedent literature report. 1 General procedure for the reaction of 2 -nitrochalcone with elemental sulfur A mixture of 2 -nitrochalcone 1 (0.2 mmol), sulfur (32 mg, 1mmol), triethylethylamine (101 mg, 1mmol) or N-methylpiperidine (99 mg, 1mmol), and DM (78 mg, 1 mmol) was stirred at rt or indicated temperatures (Table 1, chemes 2-3) under an argon atmosphere for 16 h. The residue was directly purified by column chromatography on silica gel (eluent heptane:toluene or toluene:etac) to afford the product 2 as yellow or orange solid. The 1 mmol scale reaction applied for substrate 1a with Et 3 N as a base was performed in the same manner and provided the corresponding thioaurone 2a as a yellow solid (204 mg, 86%). (Z)-2-Benzylidenebenzo[b]thiophen-3(2H)-one (2a) 2 1 Lin, Z.; Hu, Z.; Zhang, X.; Dong, J.; Liu, J.; Chen, D.; Xu, X. rg. Lett. 2017, 19, 5284. I1
Eluent heptane:toluene 9:1 to toluene. Bright yellow solid. 42 mg, 88% in 0.2 mmol scale; 204 mg, 86% in 1 mmol scale. 1 H NMR (300 MHz, CDCl 3 ) δ 7.98-7.93 (m, 2H), 7.73-7.70 (m, 2H), 7.61-7.40 (m, 5H), 7.30 (t, J = 7.4 Hz, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 188.8, 146.3, 135.4, 134.5, 133.7, 131.2, 130.6, 130.4, 130.3, 129.2, 127.2, 125.8, 124.1. (Z)-2-(4-Fluorobenzylidene)benzo[b]thiophen-3(2H)-one (2b) 3 F Eluent heptane:toluene 9:1. Bright yellow solid. 45 mg, 88%. 1 H NMR (300 MHz, CDCl 3 ) δ 7.94 (d, J = 8.0 Hz, 1H), 7.91 (s, 1H), 7.70 (dd, J = 8.5, 5.9 Hz, 1H), 7.59 (t, J = 8.0 Hz, 1H), 7.50 (d, J = 8.0 Hz, 1H), 7.30 (t, J = 8.0 Hz, 1H), 7.18 (t, J = 8.5 Hz, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 188.6, 163.6 (d, J = 254 Hz, 146.0, 135.5, 133.1 (d, J = 8.8 Hz), 132.4, 130.8 (d, J = 2.6 Hz), 130.6, 130.1, 127.3, 125.9, 124.1, 116.5 (d, J = 21.8 Hz). (Z)-2-(2-Chlorobenzylidene)benzo[b]thiophen-3(2H)-one (2c) Cl Eluent heptane:toluene 9:1. Bright yellow solid. 42 mg, 77%. 1 H NMR (300 MHz, CDCl 3 ) δ 8.31 (s, 1H), 7.95-7.92 (m, 1H), 7.81 (dd, J = 7.5, 1.8 Hz, 1H), 7.60-7.55 (m 1H), 7.49-7.45 (m, 2H), 7.41-7.26 (m, 3H). 13 C NMR (75 MHz, CDCl 3 ) δ 188.3, 146.1, 136.7, 135.6, 133.0, 132.8, 131.0, 130.6, 130.5, 130.2, 129.4, 127.4, 127.2, 125.9, 124.1. HRM (EI + ) calcd for C 15 H 10 Cl [M + H] + 273.0141. Found 273.0156. (Z)-2-(4-Chlorobenzylidene)benzo[b]thiophen-3(2H)-one (2d) 4 2 Zheng, G.; Ma, X.; Liu, Y. Dong, B.; Wang, M. Adv. ynth. Catal. 2014, 356, 743. 3 Cabiddu, M. G.; Cabiddu,.; Cadoni, E.; De Montis,.; Fattuoni, C.; Melis,.; Usai, M. ynthesis 2002, 875. I2
Cl Eluent heptane:toluene 9:1. Bright yellow solid. 45 mg, 83%. 1 H NMR (300 MHz, CDCl 3 ) δ 7.94-7.91 (m, 1H), 7.87 (s, 1H), 7.63-7.42 (m, 6H), 7.32-7.27 (m, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 188.8, 146.0, 136.4, 135.7, 133.1, 132.3, 132.2, 131.1, 130.6, 129.6, 127.4, 126.0, 124.2. (Z)-2-(3-Bromobenzylidene)benzo[b]thiophen-3(2H)-one (2e) Br Eluent heptane:toluene 9:1. Bright yellow solid. 56 mg, 88%. 1 H NMR (300 MHz, CDCl 3 ) δ 7.85 (d, J = 8.0 Hz, 1H), 7.76-7.73 (m, 2H), 7.54-7.40 (m, 4H), 7.29-7.18 (m, 2H). 13 C NMR (75 MHz, CDCl 3 ) δ 188.6, 146.0, 136.6, 135.7, 133.6, 133.0, 131.9, 131.7, 130.7, 130.4, 129.5, 127.4, 126.0, 124.2, 123.3. HRM (EI + ) calcd for C 15 H 10 Br [M + H] + 316.9636. Found 316.9647. (Z)-2-(4-Bromobenzylidene)benzo[b]thiophen-3(2H)-one (2f) 5 Br Eluent heptane:toluene 9:1. Bright yellow solid. 57 mg, 90%. 1 H NMR (300 MHz, CDCl 3 ) δ 7.91 (d, J = 8.0 Hz, 1H), 7.84 (s, 1H), 7.60-7.46 (m, 6H), 7.31-7.26 (m, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 188.7, 145.9, 135.7, 133.4, 132.5, 132.4, 132.2, 131.1, 130.5, 127.3, 126.0, 124.8, 124.1. (Z)-2-(2-Methoxybenzylidene)benzo[b]thiophen-3(2H)-one (2g) 4 Pradhan, T. K.; De, A.; Mortier, J. Tetrahedron 2005, 61, 9007. 5 Maerz, B.; Wiedbrauk,.; esterling,.; amoylova, E.; Nenov, A.; Mayer, P.; De Vivie-Riedle, R.; Zinth, W.; Dube, D. Chem. Eur. J. 2014, 20, 13984. I3
Me Eluent toluene. Bright yellow solid. 43 mg, 80%. 1 H NMR (300 MHz, CDCl 3 ) δ 8.45 (s, 1H), 7.96 (d, J = 7.6 Hz, 1H), 7.78 (dd, J = 7.6, 1.5 Hz, 1H), 7.60-7.54 (m, 1H), 7.49 (d, J = 7.6 Hz, 1H), 7.44-7.38 (m, 1H), 7.32-7.27 (m, 1H), 7.08 (t, J = 7.6 Hz, 1H), 6.95 (d, J = 8.0 Hz, 1H), 3.93 (s, 3H). 13 C NMR (75 MHz, CDCl 3 ) δ 188.8, 159.4, 146.4, 135.2, 132.0, 131.0, 130.4, 130.1, 128.7, 127.2, 125.6, 124.0, 123.7, 120.9, 111.2, 55.8. HRM (EI + ) calcd for C 16 H 13 2 [M + H] + 269.0636. Found 269.0625. (Z)-2-(4-Methoxybenzylidene)benzo[b]thiophen-3(2H)-one (2h) 2 Me Eluent toluene. Bright yellow solid. 42 mg, 78%. 1 H NMR (300 MHz, CDCl 3 ) δ 7.94 (d, J = 7.5 Hz, 1H), 7.92 (s, 1H), 7.67 (d, J = 8.7 Hz, 2H), 7.56 (t, J = 7.5 Hz, 1H), 7.51 (d, J = 7.5 Hz, 1H), 7.29 (t, J = 7.5 Hz, 1H), 7.00 (d, J = 8.7 Hz, 2H), 3.87 (s, 3H). 13 C NMR (75 MHz, CDCl 3 ) δ 188.7, 161.4, 146.1, 135.1, 133.8, 133.2, 130.9, 127.9, 127.1, 127.0, 125.6, 124.0, 114.8, 55.6. (Z)-2-(4-(Dimethylamino)benzylidene)benzo[b]thiophen-3(2H)-one (2i) 5 NMe 2 Eluent heptane:etac 5:1. range solid. 43 mg, 77%. 1 H NMR (300 MHz, CDCl 3 ) δ 7.96-7.93 (m, 2H), 7.64-7.49 (m, 4H), 7.30-7.25 (m, 1H), 6.76-6.71 (m, 2H), 3.05 (s, 6H). 13 C NMR (75 MHz, CDCl 3 ) δ 188.4, 151.7, 146.0, 135.4, 134.5, 133.6, 131.6, 126.8, 125.3, 124.8, 123.9, 122.1, 112.1, 40.2. (Z)-N-(4-((3-oxobenzo[b]thiophen-2(3H)-ylidene)methyl)phenyl)acetamide (2j) I4
NHAc Eluent toluene:etac 5:1 to 3:1. Bright yellow solid. 48 mg, 81%. 1 H NMR (300 MHz, DM-d 6 ) δ 10.28 (s, 1H), 7.85 (s, 1H), 7.85 (d, J = 7.4 Hz, 1H), 7.78-7.67 (m, 6H), 7.38 (t, J = 7.4 Hz, 1H), 2.09 (s, 3H). 13 C NMR (75 MHz, CDCl 3 ) δ 187.4, 168.8, 145.0, 141.5, 135.7, 133.0, 132.0, 129.8, 128.1, 127.6, 126.4, 126.0, 124.4, 119.1, 24.2. HRM (EI + ) calcd for C 17 H 14 N 2 [M + H] + 296.0745. Found 296.0754. (Z)-2-(3-Nitrobenzylidene)benzo[b]thiophen-3(2H)-one (2k) N 2 Eluent toluene. Yellow solid. 45 mg, 80%. 1 H NMR (300 MHz, CDCl 3 ) δ 8.55 (t, J = 1.8 Hz, 1H), 8.25-8.22 (m, 1H), 7.98-7.93 (m, 3H), 7.67-7.59 (m, 3H), 7.52 (d, J = 8.0 Hz, 1H), 7.32 (t, J = 7.5 Hz, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 188.5, 145.7, 136.4, 136.3, 136.1, 133.5, 130.3, 130.1, 127.6, 126.4, 125.1, 124.3, 124.3. HRM (EI + ) calcd for C 15 H 10 N 3 [M + H] + 284.0381. Found 284.0387. (Z)-2-(4-Nitrobenzylidene)benzo[b]thiophen-3(2H)-one (2l) N 2 Eluent toluene. Yellow solid. 34 mg, 60%. 1 H NMR (300 MHz, CDCl 3 ) δ 8.32-8.29 (m, 2H), 7.94 (d, J = 7. 6 Hz, 1H), 7.91(s, 1H), 7.83-7.80 (m, 2H), 7.64-7.59 (m, 1H), 7.50 (d, J = 7.6 Hz, 1H), 7.35-7.30 (m, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 188.5, 159.8, 147.8, 145.6, 140.7, 136.2, 134.6, 131.4, 130.1, 127.7, 126.5, 124.4, 124.3. HRM (EI + ) calcd for C 15 H 10 N 3 [M + H] + 284.0381. Found 284.0377. I5
(Z)-2-(4-(Trifluoromethyl)benzylidene)benzo[b]thiophen-3(2H)-one (2m) 3 CF 3 Eluent toluene. Bright yellow solid. 47 mg, 77%. 1 H NMR (300 MHz, CDCl 3 ) δ 7.92 (d, J = 8.4 Hz, 1H), 7.91 (s, 1H), 7.77 (d, J = 8.4 Hz, 2H), 7.70 (d, J = 8.4 Hz, 2H), 7.58 (t, J = 8.4 Hz, 1H), 7.48 (d, J = 8.4 Hz, 1H), 7.30 (t, J = 8.4 Hz, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 188.7, 146.0, 137.9, 135.9, 132.9, 131.5 (q, J = 33 Hz), 131.4, 131.1, 130.3, 127.5, 126.2, 126.1 (q, J = 3.4 Hz), 124.2, 124.0 (q, J = 274 Hz). (Z)-2-(Naphthalen-1-ylmethylene)benzo[b]thiophen-3(2H)-one (2n) Eluent toluene. Bright yellow solid. 50 mg, 87%. 1 H NMR (300 MHz, CDCl 3 ) δ 8.73 (s, 1H), 8.25 (d, J = 8.2 Hz, 1H), 7.98-7.86 (m, 4H), 7.61-7.52 (m, 4H), 7.45 (d, J = 7.4 Hz, 1H), 7.28 (t, J = 7.4 Hz, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 188.4, 146.8, 135.4, 133.9, 133.2, 132.5, 131.6, 131.1, 130.9, 130.2, 129.1, 127.9, 127.3, 127.3, 126.7, 125.7, 125.5, 124.2, 123.8. HRM (EI + ) calcd for C 19 H 13 [M + H] + 289.0687. Found 289.0673. (Z)-2-(Naphthalen-2-ylmethylene)benzo[b]thiophen-3(2H)-one (2o) Eluent toluene. Bright yellow solid. 51 mg, 89%. 1 H NMR (300 MHz, CDCl 3 ) δ 8.21 (s, 1H), 8.13 (s, 1H), 7.99-7.79 (m, 5H), 7.63-7.53 (m, 4H), 7.32 (t, J = 7.4 Hz, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 188.8, 146.3, 135.5, 134.0, 133.9, 133.5, 132.2, 132.1, 130.8, 130.7, 129.0, 129.0, 128.0, 127.9, 127.3, 127.3, 127.1, 125.9, 124.1. HRM (EI + ) calcd for C 19 H 13 [M + H] + 289.0687. Found 289.0682. (Z)-2-(Thiophen-3-ylmethylene)benzo[b]thiophen-3(2H)-one (2p) I6
Eluent toluene. Bright yellow solid. 46 mg, 94%. 1 H NMR (300 MHz, CDCl 3 ) δ 7.97 (s, 1H), 7.95-7.92 (m, 1H), 7.78-7.76 (m, 1H), 7.60-7.42 (m, 4H), 7.32-7.27 (m, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 188.8, 145.8, 136.9, 135.4, 131.1, 130.5, 129.8, 128.9, 127.2, 127.1, 127.0, 125.8, 124.1. HRM (EI + ) calcd for C 13 H 19 2 [M + H] + 245.0095. Found 245.0106. (Z)-2-(Thiophen-2-ylmethylene)benzo[b]thiophen-3(2H)-one (2p) 3 Eluent toluene. Bright yellow solid. 45 mg, 92%. 1 H NMR (300 MHz, CDCl 3 ) δ 8.14 (s, 1H), 7.92 (d, J = 7.4 Hz, 1H), 7.66 (d, J = 5.1 Hz, 1H), 7.60-7.50 (m, 3H), 7.30 (t, J = 6.9 Hz, 1H), 7.21-7.18 (m, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 188.3, 145.7, 139.4, 135.3, 133.8, 131.8, 131.2, 129.1, 128.8, 127.1, 126.1, 125.8, 124.2. (Z)-2-Benzylidene-5,6-dimethoxybenzo[b]thiophen-3(2H)-one (2r) Me Me Ph Eluent toluene:etac 99:1. Yellow solid. 43 mg, 72%. 1 H NMR (300 MHz, CDCl 3 ) δ 7.85 (s, 1H), 7.64-7.61 (m, 2H), 7.45-7.32 (m, 3H), 7.31 (s, 1H), 6.84 (s, 1H), 3.92 (s, 3H), 3.88 (s, 3H). 13 C NMR (75 MHz, CDCl 3 ) δ 187.3, 156.0, 148.3, 140.9, 134.4, 132.8, 131.3, 130.9, 129.9, 129.0, 123.2, 107.8, 105.2, 56.4, 56.2. HRM (EI + ) calcd for C 17 H 15 3 [M + H] + 299.0742. Found 299.0729. (Z)-6-Benzylidenethieno[2',3':4,5]benzo[1,2-d][1,3]dioxol-7(6H)-one (2s) Ph Eluent toluene:etac 99:1. Yellow solid. 43 mg, 76%. I7
1 H NMR (300 MHz, CDCl 3 ) δ 7.86 (s, 1H), 7.64-7.62 (m, 2H), 7.47-7.35 (m, 3H), 7.27 (s, 1H), 6.84 (s, 1H), 6.05 (s, 2H). 13 C NMR (75 MHz, CDCl 3 ) δ 186.9, 154.9, 147.5, 143.1, 134.5, 133.3, 131.2, 131.1, 130.2, 129.2, 125.0, 105.9, 103.7, 102.8. HRM (EI + ) calcd for C 16 H 11 3 [M + H] + 283.0429. Found 283.0416. (2Z,2'Z)-2,2'-(1,4-Phenylenebis(methanylylidene))bis(benzo[b]thiophen-3(2H)-one) (2t) The reaction was performed with 0.1 mmol of 1t. The crude mixture was purified by washing successively with toluene, CH 2 Cl 2 and methanol. The solid residue was separated from the solution by centrifugation the dried under vacuum. range solid. 33 mg, 83%. 1 H NMR (300 MHz, CDCl 3 ) δ 7.99 (d, J = 7.8 Hz, 2H), 7.98 (s, 2H), 7.84 (s, 4H), 7.64 (t, J = 7.8 Hz, 2H), 7.56 (d, J = 7.8 Hz, 2H), 7.35 (t, J = 7.8 Hz, 2H). 13 C NMR: Due to low solubility of the product in most common NMR solvents (DM-d 6, CDCl 3, acetone-d 6 ), we were unable to record its 13 C NMR. HRM (EI + ) calcd for C 24 H 15 2 2 [M + H] + 399.0513. Found 399.0525. (2Z,2'Z)-2,2'-(1,3-Phenylenebis(methanylylidene))bis(benzo[b]thiophen-3(2H)-one) (2u) The reaction was performed with 0.1 mmol of 1u. The product was purified in the same manner for 2t. Yellow solid. 32 mg, 80%. Practically insoluble in most common organic solvents. The NMR analysis was thus impossible. HRM (EI + ) calcd for C 24 H 15 2 2 [M + H] + 399.0513. Found 399.0531. Microanalysis: content calculated for C 24 H 16 N 2 6 16.09%. Found 16.03 %. (Z)-2-(2,4,6-Trimethylbenzylidene)benzo[b]thiophen-3(2H)-one (2v) Me Me Me I8
Eluent heptane:toluene 9:1. Yellow solid. 48 mg, 86%. 1 H NMR (300 MHz, CDCl 3 ) δ 8.07 (s, 1H), 7.96 (d, J = 7.6 Hz, 1H), 7.57 (t, J = 7.6 Hz, 1H),7.40 (d, J = 7.6 Hz, 1H), 7.29 (t, J = 7.6 Hz, 1H), 6.94 (s, 2H), 2.35 (s, 3H), 2.27 (s, 6H). 13 C NMR (75 MHz, CDCl 3 ) δ HRM (EI + ) calcd for C 18 H 17 [M + H] + 281.1000. Found 281.1012. (Z)-2-(Anthracen-9-ylmethylene)benzo[b]thiophen-3(2H)-one (2w) Eluent heptane:toluene 9:1. range solid. 49 mg, 72%. 1 H NMR (300 MHz, CDCl 3 ) δ 8.89 (s, 1H), 8.53 (s, 1H), 8.12-8.02 (m, 5H), 7.58-7.51 (m, 5H), 7.31 (t, J = 8.2 Hz, 1H). 13 C NMR (75 MHz, CDCl 3 ) δ 187.8, 146.8, 139.0, 135.8, 131.8, 131.4, 131.2, 129.5, 129.2, 129.1, 128.9, 127.4, 126.7, 125.8, 125.8, 125.6, 124.2. HRM (EI + ) calcd for C 23 H 15 [M + H] + 339.0844. Found 339.0846. (Z)-2-(2,4,6-Trimethoxybenzylidene)benzo[b]thiophen-3(2H)-one (2x) Me Me Me Eluent heptane:toluene 9:1. Yellow solid. 45 mg, 69%. 1 H NMR (300 MHz, CDCl 3 ) δ 8.28 (s, 1H), 7.84 (d, J = 7.4 Hz, 1H), 7.46 (t, J = 7.4 Hz, 1H), 7.37 (d, J = 7.4 Hz, 1H), 7.17 (t, J = 7.4 Hz, 1H), 6.08 (s, 2H), 3.86 (s, 6H), 3.82 (s, 3H). 13 C NMR (75 MHz, CDCl 3 ) δ 189.1, 164.2, 160.3, 147.0, 134.7, 131.5, 130.6, 128.1, 126.5, 124.7, 123.3, 105.8, 90.5, 55.6, 55.6. HRM (EI + ) calcd for C 18 H 17 4 [M + H] + 329.0848. Found 329.0832. I9
Crystallographic data collection, structure determination and refinement X-ray tructure Determination of 2m: Performed with a RIGAKU XtaLabPro diffractometer equipped with a Mo microfocus sealed tube generator coupled to a double-bounce confocal Max-Flux multilayer optic and a HPAD PILATU3 R 200K detector, on a yellow crystalline thick plate. Data collection and reduction software (CrysalisPro). [1] Crystal data: C 16 H 9 F 3, M 306.29 g.mol 1, 0.520 x 0.210 x 0.060 mm 3, monoclinic, space group: P 2 1 /c, Mo-Kα, 0.71073 Å, T = 293 K, unit cell dimensions: a = 14.8357(19), b = 6.1102(8), c = 15.654(2) Å, β = 106.995(16), V = 1357.1(3) Å 3, Z = 4, D calcd. = 1.499 g.cm 3, absorption μ = 0.268 mm 1, the θ range for data collection was 3.631 30.335, index ranges: -20 h 20, 8 k 5, 22 l 16. Number of reflections collected: 9517; independent reflections: 3576 (R int = 0.0294). The structure was solved by intrinsic phasing methods (HELXT program) [2] tructure refinement was performed by full-matrix least-squares methods (HELXL-2017/1 program) [3] on 218 parameters, weighted refinement: w = 1/[σ 2 (F 2 o ) + (0.0547P) 2 + 0.3136P] with P = [max(f 2 o,0) + 2F 2 o ]/3 and hydrogen atoms located from difference Fourier synthesis and refined isotropically assuming a riding motion model, non-hydrogen atoms improved by anisotropic refinement. Goodness-of-fit on = 1.127, final R indices: R1 = 0.0568, wr2 = 0.1194, the final difference Fourier map showed minimum and maximum values of 0.288 and -0.230 e Å 3, respectively. The CF3 group appears disordered over two positions with site-occupation factors of 0.81(1)/0.19(1) and were refined with distance restraints (HELXL ADI) and enhanced rigid-bond restraint (HELXL RIGU) to maintain physically reasonable displacement ellipsoids. CCDC 1584932 (compound 2m) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. References 1 Rigaku D (2015). CrysAlis PR. Rigaku xford Diffraction, Yarnton, xfordshire, England. 2 heldrick, G. M. (2015). Acta Crystallogr., A71, 3-8. 3 heldrick, G. M. (2015). Acta Crystallogr., C71, 3-8. 4 Rigaku. (2009) CrystalClear-M Expert 2.0 r4 Rigaku Corporation, Tokyo, Japan. 5 pek, A. L. (2009) Acta Crystallogr., D65, 148-155. rtep plot of 2m. Ellipsoids are drawn at 30% of probability and CF3 disorder is not shown I10
Table Identification code 2m Empirical formula C 16 H 9 F 3 Formula weight 306.29 Temperature (K) 293(2) Wavelength (Å) 0.71073 Crystal system, pace group Monoclinic, P2 1 /c Unit cell dimensions a (Å) b c β ( ) 14.8357(19) 6.1102(8) 15.654(2) 106.995(16) Volume (Å 3 ) 1357.1(3) Z, Calculated density (Mg/m 3 ) 4, 1.499 Absorption coefficient (mm -1 ) 0.268 F(000) 624 Crystal size (mm) 0.52 x 0.21 x 0.06 θ range for data collection ( ) 3.631 to 30.335 Limiting indices -20 h 20, -8 k 5, -22 l 16 Reflections collected / unique R(int) 9517 / 3576 0.0294 Completeness to θ full (%) 99.3 Absorption correction emi-empirical from equivalents Max. and min. transmission 1.000 and 0.608 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 3568 / 105 / 218 Goodness-of-fit on F 2 1.048 Final R indices [I>2σ(I)] R1 = 0.0425, wr2 = 0.1119 R indices (all data) R1 = 0.0568, wr2 = 0.1194 Largest diff. peak and hole (e. Å 3 ) 0.288 and -0.230 I11
(Z)-2-Benzylidenebenzo[b]thiophen-3(2H)-one (2a) I12
(Z)-2-(4-Fluorobenzylidene)benzo[b]thiophen-3(2H)-one (2b) F F I13
(Z)-2-(2-Chlorobenzylidene)benzo[b]thiophen-3(2H)-one (2c) Cl Cl I14
(Z)-2-(4-Chlorobenzylidene)benzo[b]thiophen-3(2H)-one (2d) Cl Cl I15
(Z)-2-(3-Bromobenzylidene)benzo[b]thiophen-3(2H)-one (2e) Br Br I16
(Z)-2-(4-Bromobenzylidene)benzo[b]thiophen-3(2H)-one (2f) Br Br I17
(Z)-2-(2-Methoxybenzylidene)benzo[b]thiophen-3(2H)-one (2g) Me Me I18
(Z)-2-(4-Methoxybenzylidene)benzo[b]thiophen-3(2H)-one (2h) Me Me I19
(Z)-2-(4-(Dimethylamino)benzylidene)benzo[b]thiophen-3(2H)-one (2i) NMe 2 NMe 2 I20
(Z)-N-(4-((3-xobenzo[b]thiophen-2(3H)-ylidene)methyl)phenyl)acetamide (2j) NHAc NHAc I21
(Z)-2-(3-Nitrobenzylidene)benzo[b]thiophen-3(2H)-one (2k) N 2 N 2 I22
(Z)-2-(3-Nitrobenzylidene)benzo[b]thiophen-3(2H)-one (2l) N 2 I23
(Z)-2-(4-(trifluoromethyl)benzylidene)benzo[b]thiophen-3(2H)-one (2m) CF 3 CF 3 I24
(Z)-2-(Naphthalen-1-ylmethylene)benzo[b]thiophen-3(2H)-one (2n) I25
(Z)-2-(Naphthalen-2-ylmethylene)benzo[b]thiophen-3(2H)-one (2o) I26
(Z)-2-(Thiophen-3-ylmethylene)benzo[b]thiophen-3(2H)-one (2p) I27
(Z)-2-(Thiophen-2-ylmethylene)benzo[b]thiophen-3(2H)-one (2q) I28
(Z)-2-Benzylidene-5,6-dimethoxybenzo[b]thiophen-3(2H)-one (2r) Me Me Ph Me Me Ph I29
(Z)-6-Benzylidenethieno[2',3':4,5]benzo[1,2-d][1,3]dioxol-7(6H)-one (2s) Ph Ph I30
(2Z,2'Z)-2,2'-(1,4-Phenylenebis(methanylylidene))bis(benzo[b]thiophen-3(2H)-one) (2t) I31
(Z)-2-(2,4,6-Trimethylbenzylidene)benzo[b]thiophen-3(2H)-one (2v) Me Me Me Me Me Me I32
(Z)-2-(Anthracen-9-ylmethylene)benzo[b]thiophen-3(2H)-one (2w) I33
(Z)-2-(2,4,6-Trimethoxybenzylidene)benzo[b]thiophen-3(2H)-one (2x) Me Me Me Me Me Me I34