Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104032925/sk1789sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104032925/sk1789Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104032925/sk1789IIsup3.hkl |
CCDC references: 264800; 264801
A mixture of indole-3-carboxaldehyde (0.290 g, 2 mmol) and thiophene-3-acetonitrile (0.247 g, 2 mmol) was dissolved in piperidine (5 ml) and the solution was refluxed for 5 h. The cooled reaction mixture was poured on to crushed ice (50 g), and the yellow solid that separated was collected by filtration, washed with water and dried Crystallization from methanol gave (I) as a yellow flakes, which were suitable for X-ray analysis. 1H NMR (CDCl3): δ 7.16–7.26 (m, 2H), 7.51 (d, 1H), 7.68–7.70 (m, 3H), 8.55 (d, 1H), 8.16 (s, 1H), 8.30 (s, 1H), 12.00 (s, 1H). 13C NMR (CDCl3): δ 98.5, 110.3, 112.1, 118.6, 119.6, 120.3, 120.9, 122.5, 124.6, 126.4, 126.9, 127.8, 133.2, 135.6, 136.5. A mixture of 1-(4-tert-butylbenzyl)indole-3-carboxaldehyde (0. 583 g, 2 mmol) and thiophene-3-acetonitrile (0.247 g, 2 mmol) was dissolved in 5% sodium methoxide in methanol (10 ml) and the solution was refluxed for 2 h. The cooled reaction mixture was poured on to crushed ice, and the yellow solid that separated was collected by filtration and dried. Crystallization from methanol afforded yellow needles of (II) suitable for X-ray analysis.1H NMR (CDCl3): δ 1.29 (s, 9H), 5.38 (s, 2H), 7.12 (d, 2H), 7.25–7.38 (m, 5H), 7.40 (d, 2H), 7.47 (t, 1H), 7.76–7.79 (m, 2H), 8.37 (s, 1H). 13C NMR (CDCl3): δ 31.6, 34.8, 50.9, 100.3, 110.9, 118.3, 120.1, 121.2, 121.3, 123.3, 124.2, 125.9, 126.7, 127.2, 128.3, 129.9, 131.9, 133.3, 136.2, 137.1, 151.1.
H atoms were found in difference Fourier maps, and were subsequently positioned geometrically and treated with appropriate riding models. For (I), distances to parent atoms of 0.95 and 0.88 Å for C—H and N—H bonds, respectively, were used. In (II), C—H bonds in the disordered tert-butyl group were fixed at 0.98 Å, while for non-disordered parts of the molecule, the H-atom postions were allowed to refine along the riding-model C—H vector. [Should refined values have s.u. values?]
Data collection: COLLECT (Nonius, 1999) for (I); APEX2 (Bruker–Nonius, 2004) for (II). Cell refinement: SCALEPACK (Otwinowski & Minor, 1997) for (I); APEX2 for (II). Data reduction: DENZO–SMN (Otwinowski & Minor, 1997) for (I); APEX2 for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Sheldrick, 1995). Software used to prepare material for publication: SHELX97-2 (Sheldrick, 1997) and local procedures for (I); SHELX97 and local procedures for (II).
C15H10N2S | F(000) = 520 |
Mr = 250.31 | Dx = 1.393 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5185 reflections |
a = 12.8530 (2) Å | θ = 1.0–27.5° |
b = 5.6020 (6) Å | µ = 0.25 mm−1 |
c = 16.5980 (8) Å | T = 90 K |
β = 93.241 (2)° | Thin plate, yellow |
V = 1193.19 (14) Å3 | 0.40 × 0.15 × 0.02 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 2713 independent reflections |
Radiation source: fine-focus sealed tube | 1853 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.087 |
Detector resolution: 18 pixels mm-1 | θmax = 27.4°, θmin = 1.6° |
ω scans at fixed χ = 55° | h = −16→16 |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | k = −7→7 |
Tmin = 0.894, Tmax = 0.995 | l = −21→21 |
9660 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0528P)2 + 0.2991P] where P = (Fo2 + 2Fc2)/3 |
2713 reflections | (Δ/σ)max = 0.016 |
189 parameters | Δρmax = 0.38 e Å−3 |
136 restraints | Δρmin = −0.28 e Å−3 |
C15H10N2S | V = 1193.19 (14) Å3 |
Mr = 250.31 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.8530 (2) Å | µ = 0.25 mm−1 |
b = 5.6020 (6) Å | T = 90 K |
c = 16.5980 (8) Å | 0.40 × 0.15 × 0.02 mm |
β = 93.241 (2)° |
Nonius KappaCCD diffractometer | 2713 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 1853 reflections with I > 2σ(I) |
Tmin = 0.894, Tmax = 0.995 | Rint = 0.087 |
9660 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 136 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.38 e Å−3 |
2713 reflections | Δρmin = −0.28 e Å−3 |
189 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.72944 (16) | 0.1775 (4) | 0.47492 (11) | 0.0224 (5) | |
C2 | 0.65449 (17) | 0.3510 (4) | 0.45807 (11) | 0.0247 (5) | |
H2 | 0.5878 | 0.3555 | 0.4799 | 0.030* | |
N1 | 0.69046 (14) | 0.5137 (3) | 0.40562 (10) | 0.0257 (4) | |
H1 | 0.6554 | 0.6386 | 0.3868 | 0.031* | |
C3 | 0.78990 (17) | 0.4539 (4) | 0.38638 (11) | 0.0232 (5) | |
C4 | 0.85793 (18) | 0.5673 (4) | 0.33621 (12) | 0.0264 (5) | |
H4 | 0.8390 | 0.7110 | 0.3087 | 0.032* | |
C5 | 0.95412 (18) | 0.4621 (4) | 0.32812 (12) | 0.0283 (5) | |
H5 | 1.0028 | 0.5361 | 0.2951 | 0.034* | |
C6 | 0.98117 (17) | 0.2478 (4) | 0.36782 (12) | 0.0277 (5) | |
H6 | 1.0472 | 0.1777 | 0.3602 | 0.033* | |
C7 | 0.91365 (16) | 0.1373 (4) | 0.41765 (11) | 0.0239 (5) | |
H7 | 0.9327 | −0.0074 | 0.4444 | 0.029* | |
C8 | 0.81688 (16) | 0.2417 (4) | 0.42797 (11) | 0.0222 (5) | |
C9 | 0.73007 (17) | −0.0200 (4) | 0.52985 (11) | 0.0231 (5) | |
H9 | 0.7870 | −0.1268 | 0.5261 | 0.028* | |
C10 | 0.66219 (16) | −0.0783 (4) | 0.58636 (11) | 0.0225 (5) | |
C11 | 0.6771 (3) | −0.2792 (7) | 0.64428 (17) | 0.0212 (5) | 0.944 (2) |
C12 | 0.7566 (4) | −0.4554 (8) | 0.6410 (2) | 0.0223 (5) | 0.944 (2) |
H12 | 0.8043 | −0.4601 | 0.5993 | 0.027* | 0.944 (2) |
C13 | 0.7587 (3) | −0.6163 (7) | 0.7023 (2) | 0.0263 (8) | 0.944 (2) |
H13 | 0.8069 | −0.7441 | 0.7094 | 0.032* | 0.944 (2) |
S1 | 0.65880 (5) | −0.55147 (12) | 0.76607 (3) | 0.0247 (2) | 0.944 (2) |
C14 | 0.6180 (3) | −0.3140 (5) | 0.70967 (16) | 0.0234 (6) | 0.944 (2) |
H14 | 0.5606 | −0.2160 | 0.7219 | 0.028* | 0.944 (2) |
C11' | 0.677 (6) | −0.251 (11) | 0.631 (3) | 0.0222 (14) | 0.056 (2) |
C12' | 0.617 (4) | −0.258 (8) | 0.700 (3) | 0.0223 (17)* | 0.056 (2) |
H12' | 0.5545 | −0.1700 | 0.7048 | 0.027* | 0.056 (2) |
C13' | 0.658 (3) | −0.401 (6) | 0.7596 (18) | 0.0240 (19)* | 0.056 (2) |
H13' | 0.6460 | −0.3904 | 0.8154 | 0.029* | 0.056 (2) |
S1' | 0.7385 (14) | −0.612 (4) | 0.7148 (11) | 0.0280 (15)* | 0.056 (2) |
C14' | 0.750 (7) | −0.432 (13) | 0.634 (4) | 0.0233 (15)* | 0.056 (2) |
H14' | 0.8012 | −0.4525 | 0.5951 | 0.028* | 0.056 (2) |
C15 | 0.57075 (17) | 0.0648 (4) | 0.59562 (11) | 0.0226 (5) | |
N2 | 0.49674 (14) | 0.1743 (3) | 0.60393 (10) | 0.0290 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0268 (12) | 0.0266 (12) | 0.0140 (9) | −0.0006 (10) | 0.0029 (9) | −0.0013 (9) |
C2 | 0.0295 (13) | 0.0303 (13) | 0.0145 (9) | 0.0001 (10) | 0.0024 (9) | −0.0003 (9) |
N1 | 0.0311 (11) | 0.0279 (11) | 0.0181 (8) | 0.0043 (8) | 0.0027 (8) | 0.0026 (7) |
C3 | 0.0283 (12) | 0.0264 (12) | 0.0148 (9) | −0.0014 (10) | 0.0007 (9) | −0.0023 (9) |
C4 | 0.0355 (13) | 0.0257 (12) | 0.0179 (10) | −0.0018 (11) | 0.0003 (9) | 0.0019 (9) |
C5 | 0.0303 (13) | 0.0343 (13) | 0.0204 (10) | −0.0047 (11) | 0.0028 (9) | −0.0009 (10) |
C6 | 0.0247 (12) | 0.0358 (13) | 0.0224 (10) | 0.0003 (10) | 0.0003 (9) | −0.0022 (10) |
C7 | 0.0270 (12) | 0.0275 (12) | 0.0169 (9) | 0.0002 (10) | −0.0010 (9) | 0.0010 (9) |
C8 | 0.0248 (12) | 0.0286 (12) | 0.0131 (9) | −0.0012 (10) | −0.0001 (8) | −0.0028 (9) |
C9 | 0.0252 (12) | 0.0280 (12) | 0.0161 (9) | 0.0018 (9) | 0.0013 (8) | −0.0022 (9) |
C10 | 0.0266 (12) | 0.0259 (12) | 0.0149 (9) | −0.0018 (9) | −0.0005 (8) | −0.0028 (9) |
C11 | 0.0234 (11) | 0.0269 (13) | 0.0132 (12) | −0.0007 (10) | 0.0004 (11) | −0.0002 (9) |
C12 | 0.0229 (13) | 0.0289 (14) | 0.0153 (11) | −0.0018 (10) | 0.0021 (11) | −0.0020 (9) |
C13 | 0.0205 (16) | 0.0365 (14) | 0.0230 (14) | 0.0010 (12) | 0.0093 (11) | −0.0067 (11) |
S1 | 0.0281 (4) | 0.0301 (4) | 0.0163 (3) | −0.0002 (3) | 0.0032 (2) | 0.0030 (3) |
C14 | 0.0265 (11) | 0.0262 (14) | 0.0176 (11) | 0.0021 (11) | 0.0021 (9) | 0.0019 (10) |
C11' | 0.023 (2) | 0.026 (2) | 0.018 (2) | 0.000 (2) | 0.002 (2) | −0.001 (2) |
C15 | 0.0301 (13) | 0.0259 (12) | 0.0118 (9) | −0.0027 (11) | 0.0013 (9) | 0.0004 (9) |
N2 | 0.0308 (12) | 0.0351 (12) | 0.0214 (9) | 0.0031 (9) | 0.0049 (8) | 0.0015 (8) |
C1—C2 | 1.386 (3) | C10—C15 | 1.438 (3) |
C1—C9 | 1.433 (3) | C10—C11 | 1.485 (3) |
C1—C8 | 1.449 (3) | C11—C14 | 1.374 (3) |
C2—N1 | 1.359 (3) | C11—C12 | 1.424 (3) |
C2—H2 | 0.9500 | C12—C13 | 1.359 (4) |
N1—C3 | 1.376 (3) | C12—H12 | 0.9500 |
N1—H1 | 0.8800 | C13—S1 | 1.748 (3) |
C3—C4 | 1.394 (3) | C13—H13 | 0.9500 |
C3—C8 | 1.408 (3) | S1—C14 | 1.693 (2) |
C4—C5 | 1.383 (3) | C14—H14 | 0.9500 |
C4—H4 | 0.9500 | C11'—C14' | 1.378 (10) |
C5—C6 | 1.403 (3) | C11'—C12' | 1.427 (10) |
C5—H5 | 0.9500 | C12'—C13' | 1.355 (11) |
C6—C7 | 1.379 (3) | C12'—H12' | 0.9500 |
C6—H6 | 0.9500 | C13'—S1' | 1.759 (10) |
C7—C8 | 1.394 (3) | C13'—H13' | 0.9500 |
C7—H7 | 0.9500 | S1'—C14' | 1.696 (10) |
C9—C10 | 1.356 (3) | C14'—H14' | 0.9500 |
C9—H9 | 0.9500 | C15—N2 | 1.147 (3) |
C10—C11' | 1.23 (2) | ||
C2—C1—C9 | 130.43 (19) | C11'—C10—C15 | 119 (3) |
C2—C1—C8 | 105.62 (18) | C9—C10—C15 | 120.07 (19) |
C9—C1—C8 | 123.84 (19) | C9—C10—C11 | 124.4 (2) |
N1—C2—C1 | 109.98 (19) | C15—C10—C11 | 115.4 (2) |
N1—C2—H2 | 125.0 | C14—C11—C12 | 111.23 (19) |
C1—C2—H2 | 125.0 | C14—C11—C10 | 124.2 (2) |
C2—N1—C3 | 109.84 (17) | C12—C11—C10 | 124.5 (2) |
C2—N1—H1 | 125.1 | C13—C12—C11 | 114.5 (2) |
C3—N1—H1 | 125.1 | C13—C12—H12 | 122.7 |
N1—C3—C4 | 130.5 (2) | C11—C12—H12 | 122.7 |
N1—C3—C8 | 107.33 (17) | C12—C13—S1 | 109.4 (2) |
C4—C3—C8 | 122.1 (2) | C12—C13—H13 | 125.3 |
C5—C4—C3 | 117.3 (2) | S1—C13—H13 | 125.3 |
C5—C4—H4 | 121.4 | C14—S1—C13 | 92.51 (16) |
C3—C4—H4 | 121.4 | C11—C14—S1 | 112.37 (18) |
C4—C5—C6 | 121.2 (2) | C11—C14—H14 | 123.8 |
C4—C5—H5 | 119.4 | S1—C14—H14 | 123.8 |
C6—C5—H5 | 119.4 | C10—C11'—C14' | 133 (4) |
C7—C6—C5 | 121.2 (2) | C10—C11'—C12' | 116 (4) |
C7—C6—H6 | 119.4 | C14'—C11'—C12' | 110.5 (10) |
C5—C6—H6 | 119.4 | C13'—C12'—C11' | 113.3 (13) |
C6—C7—C8 | 118.8 (2) | C13'—C12'—H12' | 123.3 |
C6—C7—H7 | 120.6 | C11'—C12'—H12' | 123.3 |
C8—C7—H7 | 120.6 | C12'—C13'—S1' | 107.8 (12) |
C7—C8—C3 | 119.39 (19) | C12'—C13'—H13' | 126.1 |
C7—C8—C1 | 133.4 (2) | S1'—C13'—H13' | 126.1 |
C3—C8—C1 | 107.22 (18) | C14'—S1'—C13' | 90.9 (9) |
C10—C9—C1 | 130.2 (2) | C11'—C14'—S1' | 112.0 (11) |
C10—C9—H9 | 114.9 | C11'—C14'—H14' | 124.0 |
C1—C9—H9 | 114.9 | S1'—C14'—H14' | 124.0 |
C11'—C10—C9 | 121 (3) | N2—C15—C10 | 178.3 (2) |
C9—C1—C2—N1 | 175.73 (19) | C1—C9—C10—C11 | −174.7 (3) |
C8—C1—C2—N1 | −0.5 (2) | C9—C10—C11—C14 | 168.7 (3) |
C1—C2—N1—C3 | −0.2 (2) | C15—C10—C11—C14 | −8.5 (5) |
C2—N1—C3—C4 | −179.3 (2) | C9—C10—C11—C12 | −9.0 (6) |
C2—N1—C3—C8 | 0.8 (2) | C15—C10—C11—C12 | 173.8 (4) |
N1—C3—C4—C5 | −179.5 (2) | C14—C11—C12—C13 | −0.9 (6) |
C8—C3—C4—C5 | 0.4 (3) | C10—C11—C12—C13 | 177.1 (5) |
C3—C4—C5—C6 | 1.0 (3) | C11—C12—C13—S1 | 0.6 (6) |
C4—C5—C6—C7 | −1.4 (3) | C12—C13—S1—C14 | −0.1 (4) |
C5—C6—C7—C8 | 0.2 (3) | C12—C11—C14—S1 | 0.8 (5) |
C6—C7—C8—C3 | 1.1 (3) | C10—C11—C14—S1 | −177.2 (3) |
C6—C7—C8—C1 | −179.5 (2) | C13—S1—C14—C11 | −0.4 (3) |
N1—C3—C8—C7 | 178.44 (17) | C9—C10—C11'—C14' | −7 (13) |
C4—C3—C8—C7 | −1.5 (3) | C15—C10—C11'—C14' | 174 (9) |
N1—C3—C8—C1 | −1.1 (2) | C9—C10—C11'—C12' | 164 (4) |
C4—C3—C8—C1 | 178.97 (18) | C15—C10—C11'—C12' | −15 (9) |
C2—C1—C8—C7 | −178.5 (2) | C10—C11'—C12'—C13' | −160 (7) |
C9—C1—C8—C7 | 5.0 (3) | C14'—C11'—C12'—C13' | 13 (9) |
C2—C1—C8—C3 | 1.0 (2) | C11'—C12'—C13'—S1' | −23 (6) |
C9—C1—C8—C3 | −175.56 (18) | C12'—C13'—S1'—C14' | 22 (5) |
C2—C1—C9—C10 | −7.4 (4) | C10—C11'—C14'—S1' | 175 (9) |
C8—C1—C9—C10 | 168.2 (2) | C12'—C11'—C14'—S1' | 4 (10) |
C1—C9—C10—C11' | −177 (5) | C13'—S1'—C14'—C11' | −15 (8) |
C1—C9—C10—C15 | 2.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N2i | 0.88 | 2.23 | 2.971 (3) | 141 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
C26H24N2S | F(000) = 1680 |
Mr = 396.53 | Dx = 1.212 Mg m−3 |
Monoclinic, C2/c | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -C 2yc | Cell parameters from 6982 reflections |
a = 25.4535 (4) Å | θ = 1.0–68.1° |
b = 6.2152 (1) Å | µ = 1.41 mm−1 |
c = 28.1787 (4) Å | T = 90 K |
β = 102.797 (1)° | Lath, yellow |
V = 4347.10 (12) Å3 | 0.25 × 0.10 × 0.02 mm |
Z = 8 |
Nonius KappaCCD diffractometer | 3907 independent reflections |
Radiation source: fine-focus rotating anode | 3478 reflections with I > 2σ(I) |
Multilayer optics monochromator | Rint = 0.044 |
Detector resolution: 18 pixels mm-1 | θmax = 68.1°, θmin = 3.2° |
ω and ϕ scans | h = −24→30 |
Absorption correction: multi-scan (APEX2; Bruker–Nonius, 2004) | k = −7→5 |
Tmin = 0.660, Tmax = 0.972 | l = −33→31 |
15461 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.116 | w = 1/[σ2(Fo2) + (0.0599P)2 + 3.3516P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
3907 reflections | Δρmax = 0.31 e Å−3 |
311 parameters | Δρmin = −0.32 e Å−3 |
6 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00033 (6) |
C26H24N2S | V = 4347.10 (12) Å3 |
Mr = 396.53 | Z = 8 |
Monoclinic, C2/c | Cu Kα radiation |
a = 25.4535 (4) Å | µ = 1.41 mm−1 |
b = 6.2152 (1) Å | T = 90 K |
c = 28.1787 (4) Å | 0.25 × 0.10 × 0.02 mm |
β = 102.797 (1)° |
Nonius KappaCCD diffractometer | 3907 independent reflections |
Absorption correction: multi-scan (APEX2; Bruker–Nonius, 2004) | 3478 reflections with I > 2σ(I) |
Tmin = 0.660, Tmax = 0.972 | Rint = 0.044 |
15461 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 6 restraints |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.31 e Å−3 |
3907 reflections | Δρmin = −0.32 e Å−3 |
311 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1 | 0.182748 (18) | 1.46421 (7) | 0.208550 (15) | 0.03383 (17) | |
N1 | 0.08062 (5) | 0.3612 (2) | 0.34047 (5) | 0.0240 (3) | |
N2 | 0.04436 (6) | 0.8446 (2) | 0.21452 (5) | 0.0326 (3) | |
C1 | 0.13027 (6) | 0.6542 (2) | 0.33268 (5) | 0.0231 (3) | |
C2 | 0.08208 (6) | 0.5480 (2) | 0.31558 (6) | 0.0240 (3) | |
H2 | 0.0535 (6) | 0.5991 (11) | 0.2897 (5) | 0.029* | |
C3 | 0.12828 (6) | 0.3395 (3) | 0.37508 (5) | 0.0235 (3) | |
C4 | 0.14615 (7) | 0.1692 (3) | 0.40660 (6) | 0.0286 (4) | |
H4 | 0.1242 (5) | 0.050 (3) | 0.40847 (7) | 0.034* | |
C5 | 0.19803 (7) | 0.1846 (3) | 0.43514 (6) | 0.0342 (4) | |
H5 | 0.2127 (3) | 0.065 (3) | 0.4577 (5) | 0.041* | |
C6 | 0.23007 (8) | 0.3654 (3) | 0.43269 (6) | 0.0351 (4) | |
H6 | 0.2650 (9) | 0.3722 (4) | 0.4529 (5) | 0.042* | |
C7 | 0.21200 (7) | 0.5336 (3) | 0.40158 (6) | 0.0294 (4) | |
H7 | 0.2349 (5) | 0.659 (3) | 0.40037 (6) | 0.035* | |
C8 | 0.16015 (6) | 0.5216 (3) | 0.37164 (5) | 0.0237 (3) | |
C9 | 0.15173 (6) | 0.8450 (2) | 0.31503 (5) | 0.0230 (3) | |
H9 | 0.1848 (7) | 0.8984 (11) | 0.3353 (4) | 0.028* | |
C10 | 0.13244 (6) | 0.9608 (2) | 0.27411 (6) | 0.0231 (3) | |
C11 | 0.15858 (6) | 1.1522 (2) | 0.25939 (6) | 0.0239 (3) | |
C12 | 0.20362 (6) | 1.2602 (3) | 0.28918 (6) | 0.0249 (3) | |
H12 | 0.2202 (3) | 1.2164 (9) | 0.3224 (7) | 0.030* | |
C13 | 0.22110 (7) | 1.4312 (3) | 0.26637 (6) | 0.0274 (4) | |
H13 | 0.2497 (7) | 1.517 (2) | 0.2802 (3) | 0.033* | |
C14 | 0.14313 (7) | 1.2478 (3) | 0.21452 (6) | 0.0300 (4) | |
H14 | 0.1136 (7) | 1.1990 (11) | 0.1895 (6) | 0.036* | |
C15 | 0.08350 (6) | 0.8949 (2) | 0.24114 (6) | 0.0244 (3) | |
C16 | 0.03474 (6) | 0.2145 (3) | 0.33407 (6) | 0.0270 (4) | |
H16A | 0.04802 (19) | 0.067 (2) | 0.33802 (7) | 0.032* | |
H16B | 0.0130 (3) | 0.2294 (3) | 0.3010 (5) | 0.032* | |
C17 | −0.00048 (6) | 0.2561 (3) | 0.36982 (6) | 0.0247 (3) | |
C18 | −0.02480 (7) | 0.4549 (3) | 0.37141 (6) | 0.0313 (4) | |
H18 | −0.01861 (16) | 0.566 (3) | 0.3505 (5) | 0.038* | |
C19 | −0.05796 (7) | 0.4930 (3) | 0.40328 (6) | 0.0306 (4) | |
H19 | −0.0741 (4) | 0.629 (3) | 0.40329 (6) | 0.037* | |
C20 | −0.06802 (6) | 0.3364 (3) | 0.43528 (6) | 0.0277 (4) | |
C21 | −0.04364 (8) | 0.1379 (3) | 0.43295 (8) | 0.0404 (5) | |
H21 | −0.04960 (18) | 0.027 (3) | 0.4538 (6) | 0.048* | |
C22 | −0.01080 (8) | 0.0983 (3) | 0.40076 (7) | 0.0368 (4) | |
H22 | 0.0055 (4) | −0.046 (3) | 0.40000 (7) | 0.044* | |
C23 | −0.10521 (7) | 0.3802 (3) | 0.47028 (6) | 0.0316 (4) | |
C24 | −0.1100 (3) | 0.6166 (6) | 0.4806 (2) | 0.0713 (17) | 0.668 (6) |
H24A | −0.1322 | 0.6355 | 0.5046 | 0.107* | 0.668 (6) |
H24B | −0.1268 | 0.6914 | 0.4504 | 0.107* | 0.668 (6) |
H24C | −0.0740 | 0.6766 | 0.4935 | 0.107* | 0.668 (6) |
C25 | −0.15889 (13) | 0.2873 (9) | 0.44882 (15) | 0.0698 (18) | 0.668 (6) |
H25A | −0.1833 | 0.3141 | 0.4706 | 0.105* | 0.668 (6) |
H25B | −0.1554 | 0.1319 | 0.4445 | 0.105* | 0.668 (6) |
H25C | −0.1734 | 0.3546 | 0.4172 | 0.105* | 0.668 (6) |
C26 | −0.08204 (16) | 0.2743 (7) | 0.52094 (11) | 0.0584 (13) | 0.668 (6) |
H26A | −0.0461 | 0.3325 | 0.5346 | 0.088* | 0.668 (6) |
H26B | −0.0796 | 0.1182 | 0.5170 | 0.088* | 0.668 (6) |
H26C | −0.1059 | 0.3058 | 0.5430 | 0.088* | 0.668 (6) |
C24' | −0.1267 (4) | 0.1812 (11) | 0.4882 (4) | 0.084 (5) | 0.332 (6) |
H24D | −0.0980 | 0.1092 | 0.5117 | 0.126* | 0.332 (6) |
H24E | −0.1403 | 0.0845 | 0.4608 | 0.126* | 0.332 (6) |
H24F | −0.1562 | 0.2186 | 0.5040 | 0.126* | 0.332 (6) |
C25' | −0.0784 (4) | 0.5309 (18) | 0.5066 (3) | 0.069 (3) | 0.332 (6) |
H25D | −0.0667 | 0.6565 | 0.4906 | 0.103* | 0.332 (6) |
H25E | −0.0469 | 0.4616 | 0.5273 | 0.103* | 0.332 (6) |
H25F | −0.1033 | 0.5768 | 0.5267 | 0.103* | 0.332 (6) |
C26' | −0.1584 (3) | 0.5017 (19) | 0.4404 (3) | 0.071 (3) | 0.332 (6) |
H26D | −0.1846 | 0.5155 | 0.4611 | 0.107* | 0.332 (6) |
H26E | −0.1744 | 0.4183 | 0.4113 | 0.107* | 0.332 (6) |
H26F | −0.1486 | 0.6451 | 0.4308 | 0.107* | 0.332 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0337 (3) | 0.0314 (3) | 0.0364 (3) | −0.00411 (17) | 0.00773 (18) | 0.00610 (17) |
N1 | 0.0215 (7) | 0.0256 (7) | 0.0257 (6) | −0.0032 (5) | 0.0069 (5) | −0.0024 (5) |
N2 | 0.0302 (8) | 0.0306 (8) | 0.0338 (8) | −0.0010 (6) | 0.0002 (6) | 0.0009 (6) |
C1 | 0.0207 (7) | 0.0251 (8) | 0.0242 (7) | 0.0006 (6) | 0.0067 (6) | −0.0035 (6) |
C2 | 0.0203 (8) | 0.0255 (8) | 0.0264 (8) | 0.0002 (6) | 0.0056 (6) | −0.0004 (6) |
C3 | 0.0239 (8) | 0.0276 (8) | 0.0202 (7) | −0.0002 (6) | 0.0076 (6) | −0.0039 (6) |
C4 | 0.0357 (9) | 0.0289 (8) | 0.0227 (8) | −0.0028 (7) | 0.0098 (7) | −0.0011 (6) |
C5 | 0.0408 (10) | 0.0387 (10) | 0.0212 (8) | 0.0038 (8) | 0.0029 (7) | 0.0029 (7) |
C6 | 0.0318 (9) | 0.0459 (11) | 0.0242 (8) | −0.0007 (8) | −0.0010 (7) | −0.0014 (7) |
C7 | 0.0269 (9) | 0.0368 (9) | 0.0235 (8) | −0.0053 (7) | 0.0036 (6) | −0.0033 (7) |
C8 | 0.0232 (8) | 0.0275 (8) | 0.0216 (7) | −0.0009 (6) | 0.0078 (6) | −0.0048 (6) |
C9 | 0.0184 (7) | 0.0247 (8) | 0.0263 (8) | −0.0008 (6) | 0.0062 (6) | −0.0048 (6) |
C10 | 0.0193 (8) | 0.0227 (7) | 0.0283 (8) | 0.0011 (6) | 0.0073 (6) | −0.0040 (6) |
C11 | 0.0201 (8) | 0.0230 (8) | 0.0303 (8) | 0.0025 (6) | 0.0093 (6) | −0.0022 (6) |
C12 | 0.0227 (8) | 0.0247 (8) | 0.0287 (8) | 0.0007 (6) | 0.0086 (6) | −0.0033 (6) |
C13 | 0.0248 (8) | 0.0264 (8) | 0.0334 (8) | −0.0011 (7) | 0.0118 (7) | −0.0030 (7) |
C14 | 0.0261 (8) | 0.0309 (9) | 0.0321 (8) | −0.0006 (7) | 0.0042 (7) | 0.0009 (7) |
C15 | 0.0252 (8) | 0.0210 (7) | 0.0272 (8) | 0.0007 (6) | 0.0063 (7) | 0.0011 (6) |
C16 | 0.0254 (8) | 0.0280 (8) | 0.0281 (8) | −0.0071 (7) | 0.0074 (7) | −0.0045 (6) |
C17 | 0.0200 (8) | 0.0269 (8) | 0.0265 (8) | −0.0056 (6) | 0.0038 (6) | −0.0041 (6) |
C18 | 0.0329 (9) | 0.0327 (9) | 0.0294 (8) | 0.0020 (7) | 0.0090 (7) | 0.0062 (7) |
C19 | 0.0290 (9) | 0.0297 (9) | 0.0329 (9) | 0.0058 (7) | 0.0065 (7) | 0.0011 (7) |
C20 | 0.0219 (8) | 0.0302 (9) | 0.0318 (8) | −0.0061 (7) | 0.0077 (7) | −0.0044 (7) |
C21 | 0.0507 (12) | 0.0263 (9) | 0.0540 (11) | −0.0021 (8) | 0.0326 (10) | 0.0046 (8) |
C22 | 0.0417 (11) | 0.0240 (9) | 0.0515 (11) | 0.0005 (8) | 0.0252 (9) | 0.0016 (8) |
C23 | 0.0256 (8) | 0.0347 (9) | 0.0372 (9) | −0.0032 (7) | 0.0128 (7) | −0.0048 (7) |
C24 | 0.104 (4) | 0.044 (2) | 0.090 (3) | 0.008 (2) | 0.072 (3) | −0.002 (2) |
C25 | 0.0272 (17) | 0.127 (5) | 0.060 (2) | −0.025 (2) | 0.0211 (16) | −0.032 (3) |
C26 | 0.063 (2) | 0.080 (3) | 0.0378 (17) | 0.024 (2) | 0.0237 (16) | 0.0063 (17) |
C24' | 0.122 (10) | 0.039 (4) | 0.131 (10) | 0.005 (4) | 0.113 (10) | 0.012 (4) |
C25' | 0.054 (5) | 0.108 (8) | 0.055 (5) | −0.023 (5) | 0.034 (4) | −0.049 (5) |
C26' | 0.042 (4) | 0.116 (9) | 0.064 (5) | 0.035 (5) | 0.031 (4) | 0.024 (5) |
S1—C14 | 1.7117 (18) | C17—C18 | 1.387 (2) |
S1—C13 | 1.7161 (18) | C18—C19 | 1.382 (2) |
N1—C2 | 1.361 (2) | C18—H18 | 0.9430 |
N1—C3 | 1.384 (2) | C19—C20 | 1.389 (2) |
N1—C16 | 1.461 (2) | C19—H19 | 0.9373 |
N2—C15 | 1.150 (2) | C20—C21 | 1.389 (3) |
C1—C2 | 1.382 (2) | C20—C23 | 1.535 (2) |
C1—C9 | 1.440 (2) | C21—C22 | 1.385 (3) |
C1—C8 | 1.447 (2) | C21—H21 | 0.9378 |
C2—H2 | 0.9632 | C22—H22 | 0.9894 |
C3—C4 | 1.392 (2) | C23—C25' | 1.443 (7) |
C3—C8 | 1.408 (2) | C23—C25 | 1.483 (4) |
C4—C5 | 1.389 (3) | C23—C24' | 1.486 (6) |
C4—H4 | 0.9368 | C23—C24 | 1.508 (4) |
C5—C6 | 1.399 (3) | C23—C26 | 1.564 (4) |
C5—H5 | 0.9950 | C23—C26' | 1.615 (7) |
C6—C7 | 1.376 (3) | C24—H24A | 0.9800 |
C6—H6 | 0.9442 | C24—H24B | 0.9800 |
C7—C8 | 1.402 (2) | C24—H24C | 0.9800 |
C7—H7 | 0.9785 | C25—H25A | 0.9800 |
C9—C10 | 1.356 (2) | C25—H25B | 0.9800 |
C9—H9 | 0.9649 | C25—H25C | 0.9800 |
C10—C15 | 1.439 (2) | C26—H26A | 0.9800 |
C10—C11 | 1.467 (2) | C26—H26B | 0.9800 |
C11—C14 | 1.373 (2) | C26—H26C | 0.9800 |
C11—C12 | 1.429 (2) | C24'—H24D | 0.9800 |
C12—C13 | 1.366 (2) | C24'—H24E | 0.9800 |
C12—H12 | 0.9770 | C24'—H24F | 0.9800 |
C13—H13 | 0.9188 | C25'—H25D | 0.9800 |
C14—H14 | 0.9590 | C25'—H25E | 0.9800 |
C16—C17 | 1.512 (2) | C25'—H25F | 0.9800 |
C16—H16A | 0.9770 | C26'—H26D | 0.9800 |
C16—H16B | 0.9770 | C26'—H26E | 0.9800 |
C17—C22 | 1.376 (2) | C26'—H26F | 0.9800 |
C14—S1—C13 | 92.08 (8) | C18—C19—C20 | 121.92 (16) |
C2—N1—C3 | 109.04 (13) | C18—C19—H19 | 119.0 |
C2—N1—C16 | 125.51 (13) | C20—C19—H19 | 119.0 |
C3—N1—C16 | 125.32 (13) | C19—C20—C21 | 116.31 (16) |
C2—C1—C9 | 130.42 (15) | C19—C20—C23 | 121.44 (15) |
C2—C1—C8 | 105.62 (14) | C21—C20—C23 | 122.23 (15) |
C9—C1—C8 | 123.74 (14) | C22—C21—C20 | 121.96 (17) |
N1—C2—C1 | 110.56 (14) | C22—C21—H21 | 119.0 |
N1—C2—H2 | 124.7 | C20—C21—H21 | 119.0 |
C1—C2—H2 | 124.7 | C17—C22—C21 | 121.08 (17) |
N1—C3—C4 | 129.41 (15) | C17—C22—H22 | 119.5 |
N1—C3—C8 | 107.56 (13) | C21—C22—H22 | 119.5 |
C4—C3—C8 | 122.91 (15) | C25'—C23—C25 | 142.2 (4) |
C5—C4—C3 | 116.84 (16) | C25'—C23—C24' | 116.8 (6) |
C5—C4—H4 | 121.6 | C25—C23—C24' | 55.9 (5) |
C3—C4—H4 | 121.6 | C25—C23—C24 | 110.6 (3) |
C4—C5—C6 | 121.10 (16) | C24'—C23—C24 | 133.9 (3) |
C4—C5—H5 | 119.4 | C25'—C23—C20 | 108.0 (3) |
C6—C5—H5 | 119.4 | C25—C23—C20 | 108.21 (18) |
C7—C6—C5 | 121.67 (16) | C24'—C23—C20 | 113.4 (3) |
C7—C6—H6 | 119.2 | C24—C23—C20 | 112.59 (19) |
C5—C6—H6 | 119.2 | C25'—C23—C26 | 66.5 (5) |
C6—C7—C8 | 118.71 (16) | C25—C23—C26 | 109.6 (3) |
C6—C7—H7 | 120.6 | C24'—C23—C26 | 55.4 (5) |
C8—C7—H7 | 120.6 | C24—C23—C26 | 105.3 (3) |
C7—C8—C3 | 118.75 (15) | C20—C23—C26 | 110.51 (17) |
C7—C8—C1 | 133.87 (15) | C25'—C23—C26' | 106.1 (6) |
C3—C8—C1 | 107.21 (13) | C25—C23—C26' | 51.6 (4) |
C10—C9—C1 | 129.60 (15) | C24'—C23—C26' | 103.7 (6) |
C10—C9—H9 | 115.2 | C24—C23—C26' | 63.3 (5) |
C1—C9—H9 | 115.2 | C20—C23—C26' | 108.3 (3) |
C9—C10—C15 | 119.79 (14) | C26—C23—C26' | 140.8 (3) |
C9—C10—C11 | 124.71 (14) | C23—C24—H24A | 109.5 |
C15—C10—C11 | 115.49 (13) | C23—C24—H24B | 109.5 |
C14—C11—C12 | 111.50 (14) | C23—C24—H24C | 109.5 |
C14—C11—C10 | 123.76 (14) | C23—C25—H25A | 109.5 |
C12—C11—C10 | 124.73 (14) | C23—C25—H25B | 109.5 |
C13—C12—C11 | 113.04 (15) | C23—C25—H25C | 109.5 |
C13—C12—H12 | 123.5 | C23—C26—H26A | 109.5 |
C11—C12—H12 | 123.5 | C23—C26—H26B | 109.5 |
C12—C13—S1 | 111.33 (13) | C23—C26—H26C | 109.5 |
C12—C13—H13 | 124.3 | C23—C24'—H24D | 109.5 |
S1—C13—H13 | 124.3 | C23—C24'—H24E | 109.5 |
C11—C14—S1 | 112.06 (13) | H24D—C24'—H24E | 109.5 |
C11—C14—H14 | 124.0 | C23—C24'—H24F | 109.5 |
S1—C14—H14 | 124.0 | H24D—C24'—H24F | 109.5 |
N2—C15—C10 | 179.16 (18) | H24E—C24'—H24F | 109.5 |
N1—C16—C17 | 112.75 (12) | C23—C25'—H25D | 109.5 |
N1—C16—H16A | 109.0 | C23—C25'—H25E | 109.5 |
C17—C16—H16A | 109.0 | H25D—C25'—H25E | 109.5 |
N1—C16—H16B | 109.0 | C23—C25'—H25F | 109.5 |
C17—C16—H16B | 109.0 | H25D—C25'—H25F | 109.5 |
H16A—C16—H16B | 107.8 | H25E—C25'—H25F | 109.5 |
C22—C17—C18 | 117.73 (15) | C23—C26'—H26D | 109.5 |
C22—C17—C16 | 121.66 (15) | C23—C26'—H26E | 109.5 |
C18—C17—C16 | 120.58 (15) | H26D—C26'—H26E | 109.5 |
C19—C18—C17 | 120.98 (16) | C23—C26'—H26F | 109.5 |
C19—C18—H18 | 119.5 | H26D—C26'—H26F | 109.5 |
C17—C18—H18 | 119.5 | H26E—C26'—H26F | 109.5 |
C3—N1—C2—C1 | 0.16 (17) | C10—C11—C12—C13 | 178.48 (14) |
C16—N1—C2—C1 | 176.25 (13) | C11—C12—C13—S1 | 0.43 (17) |
C9—C1—C2—N1 | 173.82 (14) | C14—S1—C13—C12 | −0.25 (13) |
C8—C1—C2—N1 | −0.81 (17) | C12—C11—C14—S1 | 0.24 (18) |
C2—N1—C3—C4 | −175.45 (15) | C10—C11—C14—S1 | −178.69 (12) |
C16—N1—C3—C4 | 8.4 (2) | C13—S1—C14—C11 | 0.00 (13) |
C2—N1—C3—C8 | 0.59 (16) | C2—N1—C16—C17 | −94.63 (17) |
C16—N1—C3—C8 | −175.51 (13) | C3—N1—C16—C17 | 80.84 (18) |
N1—C3—C4—C5 | 175.11 (15) | N1—C16—C17—C22 | −122.63 (17) |
C8—C3—C4—C5 | −0.4 (2) | N1—C16—C17—C18 | 59.2 (2) |
C3—C4—C5—C6 | 1.2 (2) | C22—C17—C18—C19 | 0.4 (3) |
C4—C5—C6—C7 | −0.9 (3) | C16—C17—C18—C19 | 178.65 (15) |
C5—C6—C7—C8 | −0.2 (3) | C17—C18—C19—C20 | 0.7 (3) |
C6—C7—C8—C3 | 0.9 (2) | C18—C19—C20—C21 | −1.1 (3) |
C6—C7—C8—C1 | −173.70 (16) | C18—C19—C20—C23 | −179.62 (16) |
N1—C3—C8—C7 | −177.02 (13) | C19—C20—C21—C22 | 0.4 (3) |
C4—C3—C8—C7 | −0.7 (2) | C23—C20—C21—C22 | 178.97 (18) |
N1—C3—C8—C1 | −1.07 (16) | C18—C17—C22—C21 | −1.0 (3) |
C4—C3—C8—C1 | 175.28 (14) | C16—C17—C22—C21 | −179.25 (17) |
C2—C1—C8—C7 | 176.22 (17) | C20—C21—C22—C17 | 0.6 (3) |
C9—C1—C8—C7 | 1.1 (3) | C19—C20—C23—C25' | −69.7 (6) |
C2—C1—C8—C3 | 1.15 (16) | C21—C20—C23—C25' | 111.8 (6) |
C9—C1—C8—C3 | −173.94 (13) | C19—C20—C23—C25 | 99.3 (3) |
C2—C1—C9—C10 | −6.8 (3) | C21—C20—C23—C25 | −79.2 (3) |
C8—C1—C9—C10 | 167.02 (15) | C19—C20—C23—C24' | 159.2 (6) |
C1—C9—C10—C15 | −0.2 (2) | C21—C20—C23—C24' | −19.3 (6) |
C1—C9—C10—C11 | −178.88 (14) | C19—C20—C23—C24 | −23.2 (4) |
C9—C10—C11—C14 | 169.61 (16) | C21—C20—C23—C24 | 158.3 (3) |
C15—C10—C11—C14 | −9.1 (2) | C19—C20—C23—C26 | −140.7 (2) |
C9—C10—C11—C12 | −9.2 (2) | C21—C20—C23—C26 | 40.8 (3) |
C15—C10—C11—C12 | 172.11 (14) | C19—C20—C23—C26' | 44.7 (5) |
C14—C11—C12—C13 | −0.4 (2) | C21—C20—C23—C26' | −133.7 (5) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C15H10N2S | C26H24N2S |
Mr | 250.31 | 396.53 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, C2/c |
Temperature (K) | 90 | 90 |
a, b, c (Å) | 12.8530 (2), 5.6020 (6), 16.5980 (8) | 25.4535 (4), 6.2152 (1), 28.1787 (4) |
β (°) | 93.241 (2) | 102.797 (1) |
V (Å3) | 1193.19 (14) | 4347.10 (12) |
Z | 4 | 8 |
Radiation type | Mo Kα | Cu Kα |
µ (mm−1) | 0.25 | 1.41 |
Crystal size (mm) | 0.40 × 0.15 × 0.02 | 0.25 × 0.10 × 0.02 |
Data collection | ||
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | Multi-scan (APEX2; Bruker–Nonius, 2004) |
Tmin, Tmax | 0.894, 0.995 | 0.660, 0.972 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9660, 2713, 1853 | 15461, 3907, 3478 |
Rint | 0.087 | 0.044 |
(sin θ/λ)max (Å−1) | 0.648 | 0.602 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.116, 1.03 | 0.043, 0.116, 1.04 |
No. of reflections | 2713 | 3907 |
No. of parameters | 189 | 311 |
No. of restraints | 136 | 6 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.38, −0.28 | 0.31, −0.32 |
Computer programs: COLLECT (Nonius, 1999), APEX2 (Bruker–Nonius, 2004), SCALEPACK (Otwinowski & Minor, 1997), APEX2, DENZO–SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL (Sheldrick, 1995), SHELX97-2 (Sheldrick, 1997) and local procedures, SHELX97 and local procedures.
C1—C9 | 1.433 (3) | C10—C11 | 1.485 (3) |
C2—N1 | 1.359 (3) | C13—S1 | 1.748 (3) |
C9—C10 | 1.356 (3) | S1—C14 | 1.693 (2) |
C10—C15 | 1.438 (3) | C15—N2 | 1.147 (3) |
C2—C1—C9 | 130.43 (19) | C9—C10—C11 | 124.4 (2) |
C10—C9—C1 | 130.2 (2) | C15—C10—C11 | 115.4 (2) |
C9—C10—C15 | 120.07 (19) | C14—C11—C10 | 124.2 (2) |
C9—C1—C2—N1 | 175.73 (19) | C1—C9—C10—C11 | −174.7 (3) |
C2—C1—C9—C10 | −7.4 (4) | C9—C10—C11—C14 | 168.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N2i | 0.88 | 2.23 | 2.971 (3) | 141 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
S1—C14 | 1.7117 (18) | C1—C9 | 1.440 (2) |
S1—C13 | 1.7161 (18) | C9—C10 | 1.356 (2) |
N1—C2 | 1.361 (2) | C10—C15 | 1.439 (2) |
N2—C15 | 1.150 (2) | C10—C11 | 1.467 (2) |
C2—C1—C9 | 130.42 (15) | C9—C10—C11 | 124.71 (14) |
C10—C9—C1 | 129.60 (15) | C15—C10—C11 | 115.49 (13) |
C9—C10—C15 | 119.79 (14) | C14—C11—C10 | 123.76 (14) |
C9—C1—C2—N1 | 173.82 (14) | C1—C9—C10—C11 | −178.88 (14) |
C2—C1—C9—C10 | −6.8 (3) | C9—C10—C11—C14 | 169.61 (16) |
Acrylonitriles represent an interesting class of biologically active compound. 3-Aryl-substituted 2-[1H(2H)-benzotriazol-1(2)-yl]- acrylonitriles have been shown to possess tuberculostatic activity (Sanna et al., 2000), and (E)-3-(3-Amino-4-methoxyphenyl)-2-(3,4,5- trimethoxyphenyl)acrylonitrile and its analogs show potent antitumor activity (Ohsumi et al., 1998). We have synthesized a series of novel substituted aryl/heteroaryl 2-(thiophen-3-yl)acrylonitriles and evaluated them for antitubercular activity against Mycobacterium tuberculosis H37Rv and for anticancer activity. X-ray crystal analysis of one representative compound showed that the olefinic bond had a Z-geometry (Sonar et al., 2004). The present study is aimed at establishing the effect of bulkier substituents at position 1 of the indole ring on the geometry of the molecule. The title compounds were synthesized by the base-catalyzed condensation reaction of indole-3-carboxaldehyde and 1-(tert-butylbenzyl)-indole-3- caboxaldehyde with thiophene-3-acetonitrile to afford compounds (I) and (II), respectively. The structures of these products were initially identified by NMR spectroscopy. In order to confirm the olefinic bond geometry in these compounds, and to obtain more detailed information of the structural conformation of the molecules, their X-ray structure determination has also been carried out.
X-ray analysis confirmed the molecular structure and atom connectivity for (I) and (II) as illustrated in Figs. 1 and 2. Selected geometric parameters are presented in Tables 1 and 3. For each structure, the indole ring is planar, with bond distances and angles comparable to those reported for other indole derivatives (Mason et al., 2003). In compound (II), the phenyl ring of the 4-tertbutylbenzyl group is orthogonal to the indole ring system, forming a dihedral angle of 75.16 (4)°, and the tert-butyl group is disordered. In both molecules, the olefinic bond connecting the indole and thiophene moieties has a Z geometry. Deviations from the ideal bond-angle geometry around the Csp2 atoms of the double bond are observed. In both molecules, the C9=C10—C15, C9=C10—C11 and C14=C11—C10 bond angles [120.07 (19)/119.79 (14)°, 124.4 (2)/124.71 (14)° and 124.2 (2)/123.76 (14)°, respectively in (I)/(II)] are close to the ideal geometry (120°); however, the C2=C1—C9, C10=C9—C1 and C15=C10—C11 angles [130.43 (19)/130.42 (15)°, 130.2 (2)/129.60 (15)° and 115.4 (2)/115.49 (13)°, respectively in (I)/(II)] are distorted because of strain induced by the double bond linking the indole and thiophene rings. The vinyl group bearing the indole and thiophene rings and the nitrile group in compounds (I) and (II), has a double-bond length of 1.356 (3) Å and is significantly longer than that observed in the disubstituted vinyl group of 2-styrylbenzimidazoles [1.304 (4) Å; Bacelo et al., 1997]. This is evidence of some delocalization in the bridging units of these molecules. Furthermore, the C1—C9, C10—C11 and C10—C15 bond lengths [1.433 (3)/1.440 (2) Å, 1.485 (3)/1.467 (2) Å and 1.438 (3)/1.439 (2) Å, respectively in compounds (I)/(II)] are slightly shorter than a Car—Csp2 single bond (Wilson, 1992). The C2=C1—C9=C10, C1—C9=C10—C11 and C9=C10—C11=C14 torsion angles in (I)/(II) are −7.4 (4)/-6.8 (3)°, −174.7 (3)/-178.88 (14)° and 168.7 (3)/169.61 (16)°, respectively; these values suggest that the indole and thiophene ring planes do not deviate much from the plane of the double bond, facilitating continuous conjugation between the indole and thiophene ring π-electron systems. There is also extensive conjugation beginning at atom C15 and extending to the indole ring. A very small amount of thienyl ring-flip disorder (ca 5.6%) for (I) was observed and modeled, but no such disorder was seen for(II).
The mode of packing of (I), along the b direction, is illustrated in Fig. 3. The H atom attached to atom N1 is involved in an intermolecular hydrogen bond [2.970 (3) Å] with atom N2 of an inversion-related molecule (Table 2), thus forming an infinite chain. In addition to weak non-bonded interactions, van der Waals forces contribute to the stabilization of the crystal structures of (I) and (II).
From the present investigation, it is evident that, irrespective of the size of the substituent on the indole 1-position, the base-catalyzed reaction between thiophene-3-acetonitrile and indole-3-carboxaldehyde leads to the formation of the Z isomer.