Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103029639/bm1552sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103029639/bm1552Isup2.hkl |
CCDC reference: 235330
The title compound was prepared by Paal-Knorr ring-closure reaction of 1,4-di(2-thienyl)-1,4-butanedione with benzyl amine (see Scheme). The synthesis of both species has been described previously (e.g. Just et al., 2002), but for completeness we include here improved experimental details of the ring-closure reaction. The procedure detailed below gives a much higher yield, together with better purity, than that described by Just et al. (2002). A 100 ml round-bottomed flask was charged with 1,4-di(2-thienyl)-1,4-butanedione (1.1 g, 4.4 mmol), toluene (50 ml) and glacial acetic acid (5 ml). Benzylamine (1.85 g, 17 mmol) was added dropwise to this solution. The flask was equipped with a Dean-Stark apparatus and the reaction was stirred at reflux overnight with the constant removal of water by azeotropic distillation. The reaction mixture was concentrated in vacuo and the residue dissolved in dichloromethane. This solution was washed with aqueous sodium bicarbonate and saturated aqueous sodium chloride. The organic solution was dried over MgSO4 and the solvent removed in vacuo. The brown solid was purified using silica gel chromatography with hexane:dichloromethane (3:1) as eluent, to afford (I) in 88% yield as a white solid, which was crystallized from hot hexane to yield colourless crystals.
AUTHOR: Specify temperature for spectra acquisition, if available:
Spectroscopic analysis: 1H NMR (400 MHz, CDCl3, ??? K, δ, p.p.m.): 5.29 (2H, S, CH2), 6.39 (2H, S), 6.70 (2H, dd, J = 1.2 Hz and 3.6 Hz), 6.83 (2H, dd, J = 3.6 Hz and 5.0 Hz), 6.88 (2H, m, ArH), 7.10 (2H, dd, J = 1.2 Hz and 5.0 Hz), 7.20 (3H, m, ArH).
H atoms were placed in geometrically calculated positions (with aryl C—H distances of 0.95 Å and aliphatic C—H distances of 0.99 Å) and refined using a riding model with Uiso(H) = 1.2Ueq(C). Positional disorder (twofold ring rotation about common atoms C121 and C221) was modelled with restraints to geometric and anisotropic displacement parameters, to give refined occupancies of 0.553 (3) for S122/C123—C125, 0.447 (3) for S127/C128—C130, 0.690 (3) for S222/C223—C225 and 0.310 (3) for S227/C228—C230.
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.
C19H15NS2 | F(000) = 1344 |
Mr = 321.44 | Dx = 1.37 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 9139 reflections |
a = 16.8050 (8) Å | θ = 2.2–29.0° |
b = 10.0004 (5) Å | µ = 0.34 mm−1 |
c = 18.6253 (9) Å | T = 150 K |
β = 95.241 (2)° | Block, colourless |
V = 3117.0 (3) Å3 | 0.68 × 0.35 × 0.16 mm |
Z = 8 |
Bruker SMART1000 CCD area-detector diffractometer | 5517 reflections with I > 2σ(I) |
ω rotation with narrow frames scans | Rint = 0.030 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | θmax = 29.0°, θmin = 2.2° |
Tmin = 0.803, Tmax = 0.948 | h = −22→22 |
26998 measured reflections | k = −13→13 |
7546 independent reflections | l = −24→24 |
Refinement on F2 | 382 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.046 | w = 1/[σ2(Fo2) + (0.066P)2 + 1.513P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.134 | (Δ/σ)max = 0.001 |
S = 1.04 | Δρmax = 0.73 e Å−3 |
7546 reflections | Δρmin = −0.40 e Å−3 |
471 parameters |
C19H15NS2 | V = 3117.0 (3) Å3 |
Mr = 321.44 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.8050 (8) Å | µ = 0.34 mm−1 |
b = 10.0004 (5) Å | T = 150 K |
c = 18.6253 (9) Å | 0.68 × 0.35 × 0.16 mm |
β = 95.241 (2)° |
Bruker SMART1000 CCD area-detector diffractometer | 7546 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 5517 reflections with I > 2σ(I) |
Tmin = 0.803, Tmax = 0.948 | Rint = 0.030 |
26998 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 382 restraints |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.73 e Å−3 |
7546 reflections | Δρmin = −0.40 e Å−3 |
471 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
N11 | 0.02386 (8) | 0.09395 (14) | 0.24590 (8) | 0.0210 (3) | |
C12 | 0.09110 (10) | 0.13438 (17) | 0.28883 (9) | 0.0217 (3) | |
C13 | 0.14025 (10) | 0.20173 (17) | 0.24549 (10) | 0.0235 (4) | |
H13 | 0.1909 | 0.2398 | 0.2605 | 0.028* | |
C14 | 0.10178 (10) | 0.20372 (17) | 0.17524 (10) | 0.0229 (4) | |
H14 | 0.1217 | 0.2439 | 0.1343 | 0.027* | |
C15 | 0.03000 (10) | 0.13713 (17) | 0.17609 (9) | 0.0218 (3) | |
C111 | 0.10612 (10) | 0.10082 (17) | 0.36509 (9) | 0.0235 (4) | |
S112 | 0.19839 (3) | 0.03555 (6) | 0.39538 (3) | 0.03988 (15) | |
C113 | 0.17449 (12) | 0.0288 (2) | 0.48280 (11) | 0.0389 (5) | |
H113 | 0.2096 | −0.0021 | 0.5222 | 0.047* | |
C114 | 0.09906 (12) | 0.07297 (19) | 0.48862 (10) | 0.0307 (4) | |
H114 | 0.0751 | 0.076 | 0.5329 | 0.037* | |
C115 | 0.05970 (11) | 0.11428 (19) | 0.42155 (10) | 0.0281 (4) | |
H115 | 0.0066 | 0.1478 | 0.4163 | 0.034* | |
C121 | −0.03013 (10) | 0.11264 (18) | 0.11590 (9) | 0.0275 (4) | |
S122 | −0.0669 (3) | 0.2349 (3) | 0.0639 (2) | 0.0385 (5) | 0.553 (3) |
C123 | −0.1212 (8) | 0.1289 (7) | 0.0061 (6) | 0.047 (2) | 0.553 (3) |
H123 | −0.1546 | 0.1571 | −0.035 | 0.056* | 0.553 (3) |
C124 | −0.1103 (7) | −0.0020 (7) | 0.0268 (5) | 0.0461 (18) | 0.553 (3) |
H124 | −0.1338 | −0.0762 | 0.001 | 0.055* | 0.553 (3) |
C125 | −0.0588 (9) | −0.0125 (7) | 0.0924 (7) | 0.039 (3) | 0.553 (3) |
H125 | −0.0459 | −0.0942 | 0.1168 | 0.046* | 0.553 (3) |
S127 | −0.0611 (3) | −0.0330 (3) | 0.0813 (2) | 0.0352 (6) | 0.447 (3) |
C128 | −0.1197 (7) | 0.0356 (7) | 0.0104 (5) | 0.0337 (19) | 0.447 (3) |
H128 | −0.1516 | −0.0139 | −0.0251 | 0.04* | 0.447 (3) |
C129 | −0.1139 (11) | 0.1721 (8) | 0.0125 (8) | 0.0339 (17) | 0.447 (3) |
H129 | −0.1416 | 0.2297 | −0.0218 | 0.041* | 0.447 (3) |
C130 | −0.0612 (12) | 0.2186 (8) | 0.0728 (8) | 0.031 (3) | 0.447 (3) |
H130 | −0.0489 | 0.31 | 0.0821 | 0.037* | 0.447 (3) |
C131 | −0.10840 (9) | 0.12647 (17) | 0.29444 (9) | 0.0202 (3) | |
C132 | −0.17584 (10) | 0.07502 (18) | 0.32347 (9) | 0.0228 (3) | |
H132 | −0.1811 | −0.0188 | 0.3293 | 0.027* | |
C133 | −0.23508 (10) | 0.15971 (19) | 0.34376 (9) | 0.0250 (4) | |
H133 | −0.2808 | 0.1237 | 0.3632 | 0.03* | |
C134 | −0.22773 (10) | 0.29697 (19) | 0.33581 (9) | 0.0259 (4) | |
H134 | −0.2682 | 0.3551 | 0.3499 | 0.031* | |
C135 | −0.16104 (11) | 0.34889 (18) | 0.30721 (10) | 0.0280 (4) | |
H135 | −0.1557 | 0.4428 | 0.3017 | 0.034* | |
C136 | −0.10181 (10) | 0.26359 (18) | 0.28661 (10) | 0.0254 (4) | |
H136 | −0.0563 | 0.2999 | 0.2669 | 0.03* | |
C137 | −0.04616 (10) | 0.02959 (17) | 0.27145 (10) | 0.0230 (4) | |
H13A | −0.0285 | −0.0287 | 0.3129 | 0.028* | |
H13B | −0.0712 | −0.0282 | 0.2326 | 0.028* | |
N21 | 0.48059 (8) | 0.18857 (14) | 0.25315 (8) | 0.0221 (3) | |
C22 | 0.41229 (10) | 0.14526 (17) | 0.21273 (9) | 0.0229 (4) | |
C23 | 0.36516 (11) | 0.08058 (18) | 0.25881 (10) | 0.0260 (4) | |
H23 | 0.3142 | 0.0418 | 0.2459 | 0.031* | |
C24 | 0.40587 (10) | 0.08227 (17) | 0.32819 (10) | 0.0252 (4) | |
H24 | 0.3874 | 0.0446 | 0.3705 | 0.03* | |
C25 | 0.47732 (10) | 0.14834 (17) | 0.32396 (9) | 0.0223 (3) | |
C211 | 0.39496 (10) | 0.17118 (18) | 0.13584 (10) | 0.0255 (4) | |
S212 | 0.29760 (3) | 0.20458 (8) | 0.10383 (3) | 0.05036 (18) | |
C213 | 0.32093 (14) | 0.2094 (3) | 0.01638 (12) | 0.0479 (6) | |
H213 | 0.283 | 0.2241 | −0.0238 | 0.058* | |
C214 | 0.39938 (13) | 0.1898 (2) | 0.01132 (11) | 0.0366 (5) | |
H214 | 0.4231 | 0.1904 | −0.0331 | 0.044* | |
C215 | 0.44321 (12) | 0.1682 (2) | 0.07945 (10) | 0.0310 (4) | |
H215 | 0.4993 | 0.1533 | 0.0855 | 0.037* | |
C221 | 0.53882 (10) | 0.17807 (18) | 0.38233 (9) | 0.0254 (4) | |
S222 | 0.57407 (14) | 0.05493 (15) | 0.43932 (10) | 0.0356 (4) | 0.690 (3) |
C223 | 0.6316 (6) | 0.1625 (6) | 0.4943 (5) | 0.0314 (16) | 0.690 (3) |
H223 | 0.6639 | 0.1368 | 0.5366 | 0.038* | 0.690 (3) |
C224 | 0.6241 (6) | 0.2918 (5) | 0.4682 (4) | 0.0342 (11) | 0.690 (3) |
H224 | 0.6522 | 0.366 | 0.4899 | 0.041* | 0.690 (3) |
C225 | 0.5694 (7) | 0.3016 (7) | 0.4052 (5) | 0.043 (2) | 0.690 (3) |
H225 | 0.5554 | 0.3835 | 0.3815 | 0.052* | 0.690 (3) |
S227 | 0.5713 (4) | 0.3316 (5) | 0.4030 (3) | 0.0368 (8) | 0.310 (3) |
C228 | 0.6261 (16) | 0.2775 (14) | 0.4800 (10) | 0.053 (4) | 0.310 (3) |
H228 | 0.6589 | 0.3341 | 0.5113 | 0.063* | 0.310 (3) |
C229 | 0.6169 (14) | 0.1433 (15) | 0.4909 (10) | 0.032 (3) | 0.310 (3) |
H229 | 0.6421 | 0.095 | 0.5306 | 0.038* | 0.310 (3) |
C230 | 0.5641 (12) | 0.0851 (10) | 0.4345 (8) | 0.043 (3) | 0.310 (3) |
H230 | 0.5484 | −0.0062 | 0.4331 | 0.052* | 0.310 (3) |
C231 | 0.61085 (10) | 0.15526 (17) | 0.20101 (9) | 0.0208 (3) | |
C232 | 0.67780 (10) | 0.20711 (18) | 0.17174 (9) | 0.0238 (4) | |
H232 | 0.6834 | 0.3012 | 0.1674 | 0.029* | |
C233 | 0.73618 (11) | 0.1236 (2) | 0.14898 (9) | 0.0282 (4) | |
H233 | 0.7815 | 0.1603 | 0.1292 | 0.034* | |
C234 | 0.72820 (11) | −0.0142 (2) | 0.15512 (10) | 0.0296 (4) | |
H234 | 0.7678 | −0.072 | 0.1391 | 0.036* | |
C235 | 0.66222 (11) | −0.06670 (19) | 0.18477 (11) | 0.0316 (4) | |
H235 | 0.6569 | −0.1608 | 0.1895 | 0.038* | |
C236 | 0.60383 (11) | 0.01780 (18) | 0.20753 (10) | 0.0271 (4) | |
H236 | 0.5588 | −0.019 | 0.2277 | 0.032* | |
C237 | 0.54904 (10) | 0.25211 (17) | 0.22462 (10) | 0.0243 (4) | |
H13C | 0.5751 | 0.312 | 0.2621 | 0.029* | |
H13D | 0.5297 | 0.3083 | 0.1829 | 0.029* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N11 | 0.0193 (7) | 0.0212 (7) | 0.0231 (7) | −0.0014 (5) | 0.0048 (5) | −0.0007 (6) |
C12 | 0.0198 (8) | 0.0186 (8) | 0.0268 (9) | 0.0005 (6) | 0.0025 (6) | −0.0025 (6) |
C13 | 0.0197 (8) | 0.0210 (8) | 0.0300 (9) | −0.0012 (6) | 0.0033 (7) | −0.0005 (7) |
C14 | 0.0219 (8) | 0.0202 (8) | 0.0272 (9) | −0.0003 (6) | 0.0058 (7) | 0.0012 (7) |
C15 | 0.0213 (8) | 0.0209 (8) | 0.0238 (8) | 0.0006 (6) | 0.0049 (6) | −0.0006 (7) |
C111 | 0.0215 (8) | 0.0223 (8) | 0.0268 (9) | −0.0006 (6) | 0.0020 (7) | −0.0015 (7) |
S112 | 0.0234 (2) | 0.0683 (4) | 0.0277 (3) | 0.0086 (2) | 0.00081 (19) | 0.0034 (2) |
C113 | 0.0341 (11) | 0.0565 (14) | 0.0250 (10) | −0.0014 (10) | −0.0029 (8) | 0.0033 (9) |
C114 | 0.0369 (11) | 0.0320 (10) | 0.0235 (9) | −0.0043 (8) | 0.0048 (8) | −0.0029 (7) |
C115 | 0.0274 (9) | 0.0274 (9) | 0.0302 (10) | 0.0036 (7) | 0.0070 (7) | 0.0014 (7) |
C121 | 0.0218 (8) | 0.0371 (10) | 0.0241 (9) | −0.0028 (7) | 0.0048 (7) | −0.0043 (8) |
S122 | 0.0305 (11) | 0.0537 (9) | 0.0308 (9) | 0.0039 (7) | 0.0000 (6) | 0.0215 (7) |
C123 | 0.030 (3) | 0.089 (7) | 0.019 (2) | −0.008 (7) | −0.0049 (18) | −0.007 (5) |
C124 | 0.029 (3) | 0.072 (4) | 0.036 (4) | −0.007 (4) | −0.003 (2) | −0.012 (3) |
C125 | 0.033 (3) | 0.047 (4) | 0.035 (4) | −0.002 (3) | −0.005 (3) | −0.010 (3) |
S127 | 0.0381 (11) | 0.0295 (8) | 0.0381 (12) | −0.0078 (7) | 0.0035 (9) | −0.0109 (8) |
C128 | 0.026 (3) | 0.044 (4) | 0.030 (5) | 0.000 (4) | −0.004 (3) | −0.014 (4) |
C129 | 0.032 (5) | 0.045 (4) | 0.024 (4) | −0.004 (4) | −0.003 (2) | −0.004 (3) |
C130 | 0.026 (4) | 0.041 (4) | 0.023 (5) | 0.000 (4) | −0.010 (3) | 0.005 (3) |
C131 | 0.0180 (8) | 0.0227 (8) | 0.0199 (8) | −0.0023 (6) | 0.0020 (6) | 0.0002 (6) |
C132 | 0.0220 (8) | 0.0242 (8) | 0.0221 (8) | −0.0031 (7) | 0.0018 (6) | 0.0045 (7) |
C133 | 0.0199 (8) | 0.0342 (10) | 0.0211 (8) | −0.0028 (7) | 0.0031 (6) | 0.0036 (7) |
C134 | 0.0217 (8) | 0.0324 (10) | 0.0236 (9) | 0.0052 (7) | 0.0015 (7) | 0.0000 (7) |
C135 | 0.0283 (9) | 0.0223 (9) | 0.0336 (10) | −0.0004 (7) | 0.0035 (7) | 0.0009 (7) |
C136 | 0.0228 (9) | 0.0240 (9) | 0.0301 (9) | −0.0038 (7) | 0.0064 (7) | 0.0013 (7) |
C137 | 0.0219 (8) | 0.0203 (8) | 0.0274 (9) | −0.0036 (6) | 0.0057 (7) | 0.0005 (7) |
N21 | 0.0207 (7) | 0.0205 (7) | 0.0257 (7) | −0.0009 (5) | 0.0044 (6) | 0.0000 (6) |
C22 | 0.0204 (8) | 0.0207 (8) | 0.0278 (9) | 0.0002 (6) | 0.0030 (7) | −0.0029 (7) |
C23 | 0.0220 (8) | 0.0225 (9) | 0.0342 (10) | −0.0020 (7) | 0.0066 (7) | −0.0018 (7) |
C24 | 0.0257 (9) | 0.0215 (8) | 0.0296 (9) | −0.0014 (7) | 0.0087 (7) | −0.0003 (7) |
C25 | 0.0248 (8) | 0.0193 (8) | 0.0234 (8) | 0.0015 (6) | 0.0058 (7) | −0.0007 (6) |
C211 | 0.0220 (8) | 0.0255 (9) | 0.0289 (9) | 0.0001 (7) | 0.0022 (7) | −0.0016 (7) |
S212 | 0.0252 (3) | 0.0905 (5) | 0.0347 (3) | 0.0078 (3) | −0.0006 (2) | −0.0032 (3) |
C213 | 0.0405 (12) | 0.0711 (17) | 0.0303 (11) | 0.0043 (11) | −0.0068 (9) | −0.0002 (11) |
C214 | 0.0404 (11) | 0.0432 (12) | 0.0266 (10) | −0.0010 (9) | 0.0045 (8) | 0.0025 (9) |
C215 | 0.0308 (10) | 0.0343 (10) | 0.0279 (10) | 0.0014 (8) | 0.0030 (8) | 0.0021 (8) |
C221 | 0.0219 (8) | 0.0297 (9) | 0.0253 (9) | 0.0020 (7) | 0.0063 (7) | −0.0004 (7) |
S222 | 0.0361 (7) | 0.0400 (6) | 0.0313 (5) | 0.0041 (5) | 0.0065 (4) | 0.0098 (4) |
C223 | 0.019 (4) | 0.051 (3) | 0.023 (2) | −0.001 (2) | −0.0015 (19) | −0.004 (2) |
C224 | 0.029 (3) | 0.043 (2) | 0.031 (3) | −0.0046 (19) | 0.0047 (18) | −0.0067 (17) |
C225 | 0.033 (3) | 0.050 (4) | 0.048 (3) | −0.005 (3) | 0.005 (2) | 0.001 (3) |
S227 | 0.0339 (15) | 0.0465 (17) | 0.0298 (14) | −0.0148 (13) | 0.0015 (10) | −0.0058 (11) |
C228 | 0.036 (7) | 0.094 (8) | 0.027 (6) | −0.017 (7) | −0.006 (5) | −0.001 (5) |
C229 | 0.018 (7) | 0.056 (6) | 0.022 (5) | −0.014 (4) | 0.005 (3) | 0.007 (4) |
C230 | 0.034 (6) | 0.059 (7) | 0.037 (6) | 0.008 (6) | 0.002 (4) | −0.017 (5) |
C231 | 0.0194 (8) | 0.0247 (9) | 0.0181 (8) | −0.0029 (6) | 0.0001 (6) | −0.0003 (6) |
C232 | 0.0213 (8) | 0.0289 (9) | 0.0213 (8) | −0.0038 (7) | 0.0017 (6) | 0.0035 (7) |
C233 | 0.0218 (9) | 0.0402 (11) | 0.0228 (9) | −0.0030 (7) | 0.0040 (7) | 0.0027 (8) |
C234 | 0.0242 (9) | 0.0364 (10) | 0.0282 (9) | 0.0051 (7) | 0.0023 (7) | −0.0035 (8) |
C235 | 0.0294 (10) | 0.0259 (9) | 0.0396 (11) | −0.0008 (7) | 0.0040 (8) | −0.0017 (8) |
C236 | 0.0228 (9) | 0.0237 (9) | 0.0354 (10) | −0.0041 (7) | 0.0063 (7) | 0.0012 (7) |
C237 | 0.0238 (9) | 0.0210 (8) | 0.0289 (9) | −0.0034 (7) | 0.0065 (7) | 0.0016 (7) |
N11—C12 | 1.384 (2) | C134—H134 | 0.95 |
N11—C15 | 1.383 (2) | C135—H135 | 0.95 |
N11—C137 | 1.459 (2) | C136—H136 | 0.95 |
C12—C13 | 1.382 (2) | C137—H13B | 0.99 |
C12—C111 | 1.459 (2) | C137—H13A | 0.99 |
C13—C14 | 1.406 (3) | S212—C211 | 1.7221 (18) |
C14—C15 | 1.379 (2) | S212—C213 | 1.710 (2) |
C15—C121 | 1.460 (2) | S222—C223 | 1.720 (9) |
C111—C115 | 1.372 (3) | S222—C221 | 1.697 (2) |
C13—H13 | 0.95 | S227—C221 | 1.663 (6) |
C113—C114 | 1.356 (3) | S227—C228 | 1.72 (2) |
C14—H14 | 0.95 | C211—C215 | 1.385 (3) |
S112—C111 | 1.7288 (18) | C213—C214 | 1.345 (3) |
S112—C113 | 1.714 (2) | C214—C215 | 1.424 (3) |
C114—C115 | 1.421 (3) | C213—H213 | 0.95 |
C113—H113 | 0.95 | C214—H214 | 0.95 |
C114—H114 | 0.95 | C215—H215 | 0.95 |
C115—H115 | 0.95 | C221—C230 | 1.383 (13) |
C121—C130 | 1.401 (12) | C221—C225 | 1.390 (8) |
C121—C125 | 1.397 (9) | C223—C224 | 1.383 (8) |
C123—C124 | 1.372 (10) | C224—C225 | 1.426 (13) |
C124—C125 | 1.435 (17) | C228—C229 | 1.37 (2) |
C128—C129 | 1.369 (11) | C229—C230 | 1.44 (3) |
C129—C130 | 1.44 (2) | C231—C237 | 1.515 (2) |
C131—C132 | 1.398 (2) | C231—C232 | 1.394 (2) |
C131—C136 | 1.385 (2) | C231—C236 | 1.386 (2) |
C131—C137 | 1.516 (2) | C232—C233 | 1.384 (3) |
C132—C133 | 1.386 (2) | C233—C234 | 1.390 (3) |
C133—C134 | 1.387 (3) | C234—C235 | 1.386 (3) |
C134—C135 | 1.385 (3) | C235—C236 | 1.390 (3) |
C135—C136 | 1.391 (3) | C223—H223 | 0.95 |
S122—C121 | 1.645 (4) | C224—H224 | 0.95 |
S122—C123 | 1.713 (11) | C225—H225 | 0.95 |
S127—C121 | 1.657 (4) | C228—H228 | 0.95 |
S127—C128 | 1.717 (10) | C229—H229 | 0.95 |
C123—H123 | 0.95 | C230—H230 | 0.95 |
C124—H124 | 0.95 | C232—H232 | 0.95 |
C125—H125 | 0.95 | C233—H233 | 0.95 |
C128—H128 | 0.95 | C234—H234 | 0.95 |
C129—H129 | 0.95 | C235—H235 | 0.95 |
C130—H130 | 0.95 | C236—H236 | 0.95 |
C132—H132 | 0.95 | C237—H13C | 0.99 |
C133—H133 | 0.95 | C237—H13D | 0.99 |
C12—N11—C137 | 125.52 (15) | N11—C137—H13A | 108.70 |
C15—N11—C137 | 125.19 (14) | N11—C137—H13B | 108.72 |
C12—N11—C15 | 108.96 (14) | C131—C137—H13B | 108.76 |
C25—N21—C237 | 125.15 (14) | C23—C22—C211 | 128.26 (16) |
C22—N21—C25 | 108.92 (14) | N21—C22—C23 | 107.63 (15) |
C22—N21—C237 | 125.57 (15) | N21—C22—C211 | 124.06 (15) |
N11—C12—C13 | 107.76 (15) | C22—C23—C24 | 107.88 (16) |
C13—C12—C111 | 128.42 (16) | C24—C23—H23 | 126.07 |
N11—C12—C111 | 123.71 (15) | C22—C23—H23 | 126.05 |
C12—C13—C14 | 107.58 (15) | C23—C24—H24 | 126.07 |
C13—C14—C15 | 108.11 (16) | C25—C24—H24 | 126.09 |
N11—C15—C14 | 107.58 (15) | C23—C24—C25 | 107.84 (16) |
N11—C15—C121 | 124.32 (15) | N21—C25—C221 | 124.25 (15) |
C14—C15—C121 | 128.10 (16) | C24—C25—C221 | 128.00 (16) |
S112—C111—C115 | 110.04 (13) | N21—C25—C24 | 107.71 (15) |
S112—C111—C12 | 118.35 (13) | C211—S212—C213 | 92.41 (10) |
C12—C111—C115 | 131.59 (16) | C221—S222—C223 | 93.7 (3) |
C111—S112—C113 | 92.51 (9) | C221—S227—C228 | 92.4 (6) |
C114—C113—H113 | 124.28 | S212—C211—C215 | 110.20 (14) |
S112—C113—H113 | 124.31 | C22—C211—C215 | 131.52 (16) |
C113—C114—H114 | 123.56 | S212—C211—C22 | 118.21 (13) |
C115—C114—H114 | 123.61 | S212—C213—C214 | 111.97 (17) |
C111—C115—H115 | 123.39 | C213—C214—C215 | 112.97 (19) |
C114—C115—H115 | 123.42 | C211—C215—C214 | 112.43 (18) |
C14—C13—H13 | 126.25 | S227—C221—C230 | 112.6 (6) |
C12—C13—H13 | 126.17 | C25—C221—C225 | 128.7 (4) |
S112—C113—C114 | 111.41 (15) | C25—C221—C230 | 122.5 (6) |
C15—C14—H14 | 125.90 | S222—C221—C225 | 110.8 (4) |
C113—C114—C115 | 112.83 (17) | S222—C221—C25 | 120.05 (15) |
C13—C14—H14 | 125.99 | S227—C221—C25 | 123.7 (2) |
C111—C115—C114 | 113.19 (17) | S222—C223—C224 | 110.3 (7) |
C15—C121—C130 | 120.6 (6) | C223—C224—C225 | 112.6 (7) |
S127—C121—C130 | 110.8 (6) | C221—C225—C224 | 112.6 (6) |
S122—C121—C125 | 112.4 (5) | S227—C228—C229 | 111.9 (15) |
S127—C121—C15 | 128.09 (19) | C228—C229—C230 | 111.1 (16) |
C15—C121—C125 | 125.9 (5) | C221—C230—C229 | 111.8 (10) |
S122—C121—C15 | 121.60 (19) | C232—C231—C236 | 118.77 (16) |
S122—C123—C124 | 111.3 (8) | C236—C231—C237 | 122.87 (15) |
S122—C123—H123 | 124.35 | C232—C231—C237 | 118.36 (15) |
C124—C123—H123 | 124.31 | C231—C232—C233 | 121.01 (17) |
C123—C124—C125 | 111.3 (8) | C232—C233—C234 | 119.77 (17) |
C123—C124—H124 | 124.35 | C233—C234—C235 | 119.66 (17) |
C125—C124—H124 | 124.32 | C234—C235—C236 | 120.25 (18) |
C121—C125—C124 | 111.4 (7) | C231—C236—C235 | 120.54 (17) |
S127—C128—C129 | 110.0 (9) | N21—C237—C231 | 114.36 (14) |
C121—S127—C128 | 94.9 (3) | S212—C213—H213 | 124.01 |
C128—C129—C130 | 112.4 (11) | C214—C213—H213 | 124.02 |
C121—C130—C129 | 111.9 (7) | C213—C214—H214 | 123.49 |
C136—C131—C137 | 122.64 (15) | C215—C214—H214 | 123.54 |
C132—C131—C136 | 118.74 (15) | C211—C215—H215 | 123.81 |
C132—C131—C137 | 118.61 (15) | C214—C215—H215 | 123.76 |
C131—C132—C133 | 120.58 (16) | S222—C223—H223 | 124.87 |
C132—C133—C134 | 120.16 (16) | C224—C223—H223 | 124.82 |
C133—C134—C135 | 119.67 (16) | C223—C224—H224 | 123.71 |
C134—C135—C136 | 120.04 (17) | C225—C224—H224 | 123.67 |
C131—C136—C135 | 120.81 (16) | C221—C225—H225 | 123.72 |
N11—C137—C131 | 114.09 (14) | C224—C225—H225 | 123.73 |
C121—S122—C123 | 93.4 (3) | S227—C228—H228 | 124.06 |
C124—C125—H125 | 124.30 | C229—C228—H228 | 124.03 |
C121—C125—H125 | 124.29 | C228—C229—H229 | 124.47 |
C129—C128—H128 | 124.96 | C230—C229—H229 | 124.44 |
S127—C128—H128 | 125.03 | C221—C230—H230 | 124.05 |
C130—C129—H129 | 123.82 | C229—C230—H230 | 124.16 |
C128—C129—H129 | 123.80 | C233—C232—H232 | 119.55 |
C129—C130—H130 | 124.08 | C231—C232—H232 | 119.44 |
C121—C130—H130 | 124.05 | C232—C233—H233 | 120.11 |
C133—C132—H132 | 119.74 | C234—C233—H233 | 120.12 |
C131—C132—H132 | 119.68 | C235—C234—H234 | 120.23 |
C132—C133—H133 | 119.91 | C233—C234—H234 | 120.11 |
C134—C133—H133 | 119.93 | C236—C235—H235 | 119.92 |
C135—C134—H134 | 120.12 | C234—C235—H235 | 119.83 |
C133—C134—H134 | 120.21 | C231—C236—H236 | 119.77 |
C136—C135—H135 | 119.96 | C235—C236—H236 | 119.70 |
C134—C135—H135 | 120.00 | H13C—C237—H13D | 107.60 |
C131—C136—H136 | 119.61 | N21—C237—H13C | 108.64 |
C135—C136—H136 | 119.58 | N21—C237—H13D | 108.70 |
H13A—C137—H13B | 107.65 | C231—C237—H13C | 108.68 |
C131—C137—H13A | 108.73 | C231—C237—H13D | 108.66 |
C15—N11—C137—C131 | −85.7 (2) | H133—C133—C134—C135 | −179.79 |
C137—N11—C12—C13 | −174.48 (15) | C133—C134—C135—H135 | −179.94 |
C12—N11—C15—C121 | 180.00 (16) | H134—C134—C135—C136 | 179.98 |
C12—N11—C15—C14 | 0.58 (19) | H134—C134—C135—H135 | 0.06 |
C15—N11—C12—C111 | −177.22 (16) | C134—C135—C136—H136 | 179.82 |
C137—N11—C12—C111 | 9.1 (3) | H135—C135—C136—H136 | −0.25 |
C137—N11—C15—C121 | −6.3 (3) | H135—C135—C136—C131 | 179.79 |
C15—N11—C12—C13 | −0.83 (19) | C25—N21—C237—C231 | 85.5 (2) |
C137—N11—C15—C14 | 174.26 (15) | C22—N21—C25—C24 | −1.36 (19) |
C12—N11—C137—C131 | 87.0 (2) | C25—N21—C22—C211 | 179.21 (16) |
N11—C12—C111—C115 | −51.4 (3) | C25—N21—C22—C23 | 1.49 (19) |
C111—C12—C13—C14 | 176.91 (17) | C22—N21—C25—C221 | −179.08 (16) |
N11—C12—C111—S112 | 130.50 (15) | C22—N21—C237—C231 | −86.8 (2) |
C13—C12—C111—S112 | −45.1 (2) | C237—N21—C25—C24 | −174.73 (15) |
C13—C12—C111—C115 | 133.0 (2) | C237—N21—C22—C211 | −7.5 (3) |
N11—C12—C13—C14 | 0.74 (19) | C237—N21—C22—C23 | 174.83 (15) |
C12—C13—C14—C15 | −0.4 (2) | C237—N21—C25—C221 | 7.5 (3) |
C13—C14—C15—C121 | −179.50 (17) | N21—C22—C211—S212 | −142.31 (15) |
C13—C14—C15—N11 | −0.12 (19) | C211—C22—C23—C24 | −178.64 (17) |
N11—C15—C121—C125 | −56.6 (8) | C23—C22—C211—C215 | −141.5 (2) |
C14—C15—C121—C125 | 122.7 (7) | C23—C22—C211—S212 | 34.9 (3) |
C14—C15—C121—S122 | −52.6 (3) | N21—C22—C23—C24 | −1.1 (2) |
N11—C15—C121—S122 | 128.1 (2) | N21—C22—C211—C215 | 41.3 (3) |
C12—C111—C115—H115 | 2.28 | C22—C23—C24—C25 | 0.2 (2) |
S112—C111—C115—H115 | −179.50 | C23—C24—C25—N21 | 0.69 (19) |
C111—S112—C113—H113 | −179.42 | C23—C24—C25—C221 | 178.31 (17) |
H113—C113—C114—C115 | 179.57 | N21—C25—C221—C225 | 55.6 (6) |
H113—C113—C114—H114 | −0.39 | N21—C25—C221—S222 | −132.44 (17) |
S112—C113—C114—H114 | 179.52 | C24—C25—C221—S222 | 50.3 (3) |
C113—C114—C115—H115 | 179.98 | C24—C25—C221—C225 | −121.7 (6) |
H114—C114—C115—H115 | −0.04 | S212—C211—C215—C214 | −1.5 (2) |
H114—C114—C115—C111 | 180.00 | C22—C211—C215—C214 | 175.10 (19) |
C15—C121—C125—H125 | 7.06 | C213—S212—C211—C22 | −175.46 (17) |
S122—C121—C125—H125 | −177.26 | C211—S212—C213—C214 | −1.4 (2) |
C121—S122—C123—H123 | 179.45 | C213—S212—C211—C215 | 1.66 (17) |
H123—C123—C124—C125 | −177.88 | C223—S222—C221—C225 | −0.9 (6) |
H123—C123—C124—H124 | 2.16 | C221—S222—C223—C224 | −0.7 (7) |
S122—C123—C124—H124 | −177.87 | C223—S222—C221—C25 | −174.2 (4) |
H124—C124—C125—C121 | 176.94 | S212—C213—C214—C215 | 0.8 (3) |
H124—C124—C125—H125 | −3.15 | C213—C214—C215—C211 | 0.5 (3) |
C123—C124—C125—H125 | 176.89 | S222—C221—C225—C224 | 2.3 (9) |
C136—C131—C137—H13B | −116.90 | C25—C221—C225—C224 | 174.8 (5) |
C132—C131—C137—H13B | 61.88 | S222—C223—C224—C225 | 2.1 (11) |
C137—C131—C136—H136 | −1.15 | C223—C224—C225—C221 | −2.8 (12) |
C137—C131—C132—H132 | 1.36 | C236—C231—C237—N21 | −1.4 (2) |
C132—C131—C137—H13A | −55.08 | C232—C231—C236—C235 | −0.5 (3) |
C136—C131—C132—H132 | −179.81 | C236—C231—C232—C233 | 0.5 (3) |
C136—C131—C137—H13A | 126.14 | C232—C231—C237—N21 | 178.85 (15) |
C132—C131—C136—H136 | −179.93 | C237—C231—C236—C235 | 179.79 (17) |
H132—C132—C133—C134 | 179.65 | C237—C231—C232—C233 | −179.79 (16) |
H132—C132—C133—H133 | −0.28 | C231—C232—C233—C234 | 0.1 (3) |
C131—C132—C133—H133 | 179.67 | C232—C233—C234—C235 | −0.7 (3) |
H133—C133—C134—H134 | 0.21 | C233—C234—C235—C236 | 0.7 (3) |
C132—C133—C134—H134 | −179.73 | C234—C235—C236—C231 | −0.1 (3) |
Experimental details
Crystal data | |
Chemical formula | C19H15NS2 |
Mr | 321.44 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 16.8050 (8), 10.0004 (5), 18.6253 (9) |
β (°) | 95.241 (2) |
V (Å3) | 3117.0 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.34 |
Crystal size (mm) | 0.68 × 0.35 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART1000 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.803, 0.948 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26998, 7546, 5517 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.683 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.134, 1.04 |
No. of reflections | 7546 |
No. of parameters | 471 |
No. of restraints | 382 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.73, −0.40 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Sheldrick, 2001), SHELXTL and local programs.
We are interested in substituted mixed thiophene and pyrrole oligomers as precursors to substituted conducting polymer materials. These materials are of interest as conducting coatings in a range of emergent technologies, including electronic components, electromagnetic screening, sensors and displays.
Although not in itself new, the title compound, (I), exemplifies the Paal-Knorr condensation reaction of a parent dione with a substituted amine. In common with several other research groups (Meeker et al., 1998; von Kieseritzky et al., 2002; Raimundo et al., 2000; Ferraris et al., 1989), we have found this route convenient for the preparation of `trimeric' thiophene-pyrrole-thiophene derivatives substituted at the N atom of the pyrrole ring. This strategy yields centrosymmetric polymer precursors and seeks to minimize the steric influence of the central substituent through addition of the thiophene spacers. \sch
The asymmetric unit of the crystal structure contains two molecules of (I), shown in Figs. 1 and 2, with different orientations of the substituent thiophene rings. In both molecules, the pendant benzene ring of the benzyl group lies in a plane that is almost perpendicular to the plane of the central pyrrole ring. Although the individual heterocyclic rings are essentially planar, the two outer thiophene rings are twisted with respect to the plane of the pyrrole ring. The magnitude of this twisting is not the same for the two independent molecules, such that the S112—C111—C12—N11 and N11—C15—C121—S122 torsion angles are 130.50 (15) and 128.1 (3)°, respectively, and S222—C221—C25—N21 and N21—C22—C211—S212 are −132.44 (18) and −142.31 (15)°, respectively (Table 1). These torsion angles are considerably larger than those in N-methyl-2,5-di(2-thienyl)pyrrole, a similar species with a methyl substituent on the N atom of the pyrrole ring (Ferraris et al., 1989), which has values of −148.9° for S—C—C—N and 151.8° for N—C—C—S. This is consistent with other observations on substituted oligomers of thiophene (Barbarella et al., 1999; Destri et al., 1998; Liao et al., 1994) and phenyl-substituted derivatives of thiophene-pyrrole-thiophene trimers, similar to (I) (Ogura et al., 1999), where increasing the size and proximity of the substituents results in more pronounced torsional twisting. On the other hand, the crystal structure of unsubstituted oligomers of thiophene, for example hexathiophene (Horowitz et al., 1995), shows the rings to be coplanar.
AUTHOR: Some rearrangement at the end of the next paragraph - OK?
The molecules of (I) are arranged in layers such that, along both axes of each layer, the benzyl substituent is orientated alternately above and below the plane of the layer (Fig. 3). The phenyl rings in each row of molecules are all coplanar and the equivalent planes in adjacent rows are parallel. Each layer is populated solely by one of the two molecular configurations observed in the asymmetric unit, such that one layer consists of molecules containing atoms S112 and S122, while the adjacent layer is made up of molecules containing atoms S212 and S222. There is a π–π facial interaction between the phenyl rings of the benzyl substituents in adjacent layers. The corresponding C···C distance between cofacial phenyl rings is 3.80 Å. This packing arrangement is also shown schematically in Fig. 4. There is also twofold rotational disorder of one of the thiophene rings in each molecule. Atoms C121 and C221 are common to each of the two disorder components, the occupancies of which refine to 0.553 (3):0.447 (3) and 0.690 (3):0.310 (3), respectively.
This packing arrangement is quite different from those commonly seen in other derivatives and oligomers of thiophene and pyrrole, where an alternating herring-bone motif is often observed (Horowitz et al., 1995; Liao et al., 1994; Destri et al., 1998; Chen et al., 2002). Indeed, when the phenyl ring interaction is absent, for example in N-methyl-2,5-di(2-thienyl)pyrrole, this type of packing arrangement is adopted (Ferraris et al., 1989). In phenyl derivatives of the dithienylpyrrole moiety (see, for example, Ogura et al., 1999), a packing arrangement is observed that is quite similar to that reported here. However, in that case the phenyl rings are much further apart. In both the phenyl derivatives and the benzyl derivative reported here, the torsion angles between the adjacent heterocycles of the molecule are quite large. Presumably this will render the packing interactions between neighbouring dithienylpyrrole units less favourable compared with molecular geometries in which this backbone moiety is planar.