Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807042638/om2157sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807042638/om2157Isup2.hkl |
CCDC reference: 663704
Key indicators
- Single-crystal X-ray study
- T = 90 K
- Mean (C-C) = 0.002 Å
- Disorder in main residue
- R factor = 0.033
- wR factor = 0.088
- Data-to-parameter ratio = 11.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT301_ALERT_3_C Main Residue Disorder ......................... 16.00 Perc. PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C11 - C17 ... 1.43 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 162
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: Allen (2002); Bacelo et al. (1997); Beddoes et al. (1986); Mason et al. (2003); Sonar et al. (2004); Wilson (1992); Zarza et al. (1988).
The title compound was prepared according to the previously reported procedure of Sonar et al. (2004). Recrystallization from methanol afforded yellow colored needles. 1H NMR (DMSO-d6, p.p.m.): δ 7.22–7.30 (m, 4H), 7.41 (d, 2H), 7.55 (dd, 1H), 7.71 (s, 3H), 8.10 (dd, 1H), 8.15 (s, 1H), 8.45 (s, 1H). 13C NMR (DMSO-d6, p.p.m.): δ 48.90, 99.19, 110.27, 110.89, 119.09, 119.39, 120.82, 121.32, 122.93, 124.69, 127.66, 127.90, 128.55, 128.87, 129.34, 132.10, 132.45, 135.46, 136.18, 136.46.
H atoms were found in difference Fourier maps and subsequently placed in idealized positions with contrained C—H distances of 0.95 Å and Uiso(H) values set to 1.2Ueq of the attached C atom. The thienyl group was disordered by a 180° rotation over two positions about the C11—C12 bond with occupancy factors of 0.65:0.35, as is common in this type of compound. Refinement of this disorder model required a number of restraints to maintain the similarity and the integrity of the thienyl groups. The restraints used in SHXLEL were:
SAME - helps to maintain similar bond lengths and angles between specified atoms.
SIMU - helps to ensure that the equivalent Uiso of the specified atoms remain similar.
DELU - restrains the components of anisotropic displacement parameters along bonds between specified atoms so that they do not change by any large amount from one atom to the next.
We have synthesized a series of novel substituted aryl/heteroaryl-2-(thienyl) acrylonitriles and evaluated them for anticancer activity. The title compound was prepared by the base-catalyzed reaction of 1-(4-chlorobenzyl)indole-3- carboxaldehyde with thiophene-3-acetonitrile and recrystallization of the product from methanol to afford yellow needles. In order to confirm the double bond geometry in the title compound, and to obtain more detailed information of the structural conformation of the molecule, its X-ray structure determination has been carried out.
X-ray crystallography confirmed the molecular structure and atom connectivity for the title compound. In the title molecule the double bond connecting the indole and thiophene moieties has the Z-geometry. The indole ring is nearly planar with bond distances and bond angles comparable with those reported for other indole derivatives (Mason et al., 2003; Zarza et al., 1988). In the molecule, atom N1 lies slightly [0.0640 (16) Å] out of the plane of connecting atoms C2, C9, and C19, the sum of the angles about N1 being 359.36 (13)°. In a previous study, 21 structurally related indole analogues were analyzed (Beddoes et al., 1986) (available in the Cambridge Structural Database; Allen, 2002), and the sum of the three angles around the N atom were determined, to assess planarity. It was found that only two of the 21 compounds had values that were outside the range 359.0–360°, the farthest value from the perfectly planar situation being 357.2°. This is in general agreement with our current observation with the title compound. The plane of the 4-chlorophenyl group is twisted well out of the plane of the indole ring and makes a dihedral angle of 79.81 (4)°. There is an asymmetry of the exocyclic angles at C20 [C19—C20—C21 = 123.19 (14)° and C19—C20—C25 =117.73 (14)°].
Deviations from the ideal bond-angle geometry around the Csp2 atoms of the double bond are observed. The bond angles C2=C3—C10, C3—C10=C11, and C12—C11—C17 [129.95 (14), 129.61 (14), and 114.47 (13)°, respectively] are distorted because of strain induced by the double bond linking the indole and thiophene rings. The vinyl group bearing the three substituents has a double bond length of 1.352 (2) Å and is significantly longer than that observed in the disubstituted vinyl group of 2-styrylbenzimidazoles (1.304 (4) Å; Bacelo et al., 1997). Furthermore, the C3—C10 bond length [1.431 (2) Å] is slightly shorter than a Car—Csp2 single bond (Wilson, 1992). The C2=C3—C10=C11, C3—C10=C11—C12, and C10=C11—C12=C16 torsion angles [4.7 (3), 178.75 (15), and -179.2 (8), respectively] show that the non-H atoms of the indole and thiophene rings are nearly coplanar. The 2-thienyl group exhibits rotational disorder over two sets of sites corresponding to 180° about the C11—C12 bond with occupancy factors of 0.65:0.35.
For related literature, see: Allen (2002); Bacelo et al. (1997); Beddoes et al. (1986); Mason et al. (2003); Sonar et al. (2004); Wilson (1992); Zarza et al. (1988).
Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: APEX2 (Bruker, 2006); 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: SHELXL97 (Sheldrick, 1997) and local procedures.
C22H15ClN2S | F(000) = 776 |
Mr = 374.87 | Dx = 1.424 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2yn | Cell parameters from 9856 reflections |
a = 16.8531 (11) Å | θ = 3.3–69.6° |
b = 5.5629 (4) Å | µ = 3.10 mm−1 |
c = 18.7889 (13) Å | T = 90 K |
β = 96.877 (2)° | Needle, yellow |
V = 1748.8 (2) Å3 | 0.25 × 0.02 × 0.01 mm |
Z = 4 |
Bruker X8 Proteum diffractometer | 3248 independent reflections |
Radiation source: fine-focus rotating anode | 3020 reflections with I > 2σ(I) |
Graded multilayer optics monochromator | Rint = 0.040 |
Detector resolution: 18 pixels mm-1 | θmax = 69.7°, θmin = 3.3° |
φ and ω scans | h = −20→20 |
Absorption correction: multi-scan (SADABS in APEX2; Bruker, 2006) | k = −4→6 |
Tmin = 0.657, Tmax = 0.970 | l = −22→22 |
24522 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)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.088 | w = 1/[σ2(Fo2) + (0.0351P)2 + 1.6245P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.007 |
3248 reflections | Δρmax = 0.34 e Å−3 |
273 parameters | Δρmin = −0.32 e Å−3 |
162 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00051 (14) |
C22H15ClN2S | V = 1748.8 (2) Å3 |
Mr = 374.87 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 16.8531 (11) Å | µ = 3.10 mm−1 |
b = 5.5629 (4) Å | T = 90 K |
c = 18.7889 (13) Å | 0.25 × 0.02 × 0.01 mm |
β = 96.877 (2)° |
Bruker X8 Proteum diffractometer | 3248 independent reflections |
Absorption correction: multi-scan (SADABS in APEX2; Bruker, 2006) | 3020 reflections with I > 2σ(I) |
Tmin = 0.657, Tmax = 0.970 | Rint = 0.040 |
24522 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 162 restraints |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.34 e Å−3 |
3248 reflections | Δρmin = −0.32 e Å−3 |
273 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 > 2σ(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) | |
N1 | 0.60215 (8) | 0.8954 (2) | 0.37437 (7) | 0.0171 (3) | |
C2 | 0.55429 (9) | 0.6994 (3) | 0.37495 (8) | 0.0170 (3) | |
H2 | 0.5312 | 0.6435 | 0.4156 | 0.020* | |
C3 | 0.54388 (9) | 0.5928 (3) | 0.30821 (8) | 0.0164 (3) | |
C4 | 0.58888 (9) | 0.7374 (3) | 0.26350 (8) | 0.0168 (3) | |
C5 | 0.60044 (9) | 0.7306 (3) | 0.19122 (8) | 0.0203 (3) | |
H5 | 0.5783 | 0.6044 | 0.1611 | 0.024* | |
C6 | 0.64460 (10) | 0.9105 (3) | 0.16452 (9) | 0.0229 (4) | |
H6 | 0.6524 | 0.9082 | 0.1153 | 0.027* | |
C7 | 0.67814 (10) | 1.0960 (3) | 0.20821 (9) | 0.0223 (3) | |
H7 | 0.7082 | 1.2176 | 0.1881 | 0.027* | |
C8 | 0.66845 (9) | 1.1062 (3) | 0.27981 (9) | 0.0200 (3) | |
H8 | 0.6915 | 1.2314 | 0.3098 | 0.024* | |
C9 | 0.62347 (9) | 0.9253 (3) | 0.30613 (8) | 0.0168 (3) | |
C10 | 0.49692 (9) | 0.3884 (3) | 0.28348 (8) | 0.0171 (3) | |
H10 | 0.5021 | 0.3391 | 0.2358 | 0.021* | |
C11 | 0.44630 (9) | 0.2549 (3) | 0.31782 (8) | 0.0168 (3) | |
C12 | 0.39941 (9) | 0.0499 (3) | 0.28704 (8) | 0.0181 (3) | 0.652 (2) |
C13 | 0.4007 (10) | −0.034 (2) | 0.2194 (7) | 0.0193 (13) | 0.652 (2) |
H13 | 0.4324 | 0.0366 | 0.1864 | 0.023* | 0.652 (2) |
S14 | 0.33986 (9) | −0.2784 (3) | 0.19900 (6) | 0.0198 (3) | 0.652 (2) |
C15 | 0.3100 (7) | −0.266 (2) | 0.2821 (6) | 0.0279 (18) | 0.652 (2) |
H15 | 0.2722 | −0.3744 | 0.2979 | 0.034* | 0.652 (2) |
C16 | 0.3446 (8) | −0.0911 (19) | 0.3232 (6) | 0.0187 (12) | 0.652 (2) |
H16 | 0.3343 | −0.0623 | 0.3711 | 0.022* | 0.652 (2) |
C12' | 0.39941 (9) | 0.0499 (3) | 0.28704 (8) | 0.0181 (3) | 0.348 (2) |
C13' | 0.4009 (19) | −0.059 (4) | 0.2181 (13) | 0.020 (2) | 0.348 (2) |
H13' | 0.4334 | −0.0094 | 0.1827 | 0.024* | 0.348 (2) |
C14' | 0.3494 (8) | −0.239 (2) | 0.2119 (6) | 0.029 (2) | 0.348 (2) |
H14' | 0.3407 | −0.3328 | 0.1695 | 0.034* | 0.348 (2) |
S15' | 0.2997 (3) | −0.2935 (10) | 0.2838 (2) | 0.0211 (7) | 0.348 (2) |
C16' | 0.3492 (16) | −0.058 (4) | 0.3271 (11) | 0.020 (2) | 0.348 (2) |
H16' | 0.3420 | −0.0087 | 0.3743 | 0.024* | 0.348 (2) |
C17 | 0.43384 (9) | 0.3125 (3) | 0.38978 (8) | 0.0189 (3) | |
N18 | 0.42323 (8) | 0.3528 (3) | 0.44772 (7) | 0.0243 (3) | |
C19 | 0.61814 (9) | 1.0662 (3) | 0.43239 (8) | 0.0185 (3) | |
H19A | 0.5852 | 1.0225 | 0.4707 | 0.022* | |
H19B | 0.6006 | 1.2273 | 0.4144 | 0.022* | |
C20 | 0.70410 (9) | 1.0828 (3) | 0.46485 (8) | 0.0171 (3) | |
C21 | 0.75987 (10) | 0.9063 (3) | 0.45686 (8) | 0.0207 (3) | |
H21 | 0.7445 | 0.7671 | 0.4293 | 0.025* | |
C22 | 0.83803 (10) | 0.9300 (3) | 0.48858 (9) | 0.0245 (4) | |
H22 | 0.8764 | 0.8087 | 0.4828 | 0.029* | |
C23 | 0.85917 (10) | 1.1319 (3) | 0.52860 (8) | 0.0240 (4) | |
C24 | 0.80456 (10) | 1.3088 (3) | 0.53802 (9) | 0.0244 (4) | |
H24 | 0.8199 | 1.4461 | 0.5665 | 0.029* | |
C25 | 0.72715 (10) | 1.2843 (3) | 0.50554 (8) | 0.0211 (3) | |
H25 | 0.6892 | 1.4070 | 0.5111 | 0.025* | |
Cl1 | 0.95722 (3) | 1.16827 (10) | 0.56800 (2) | 0.03730 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0194 (7) | 0.0150 (6) | 0.0176 (6) | −0.0007 (5) | 0.0048 (5) | 0.0005 (5) |
C2 | 0.0160 (7) | 0.0160 (7) | 0.0197 (7) | 0.0016 (6) | 0.0048 (6) | 0.0040 (6) |
C3 | 0.0159 (7) | 0.0166 (7) | 0.0172 (7) | 0.0013 (6) | 0.0033 (6) | 0.0033 (6) |
C4 | 0.0147 (7) | 0.0156 (7) | 0.0206 (8) | 0.0024 (6) | 0.0037 (6) | 0.0032 (6) |
C5 | 0.0205 (8) | 0.0209 (8) | 0.0199 (8) | −0.0004 (6) | 0.0045 (6) | 0.0003 (6) |
C6 | 0.0237 (8) | 0.0262 (9) | 0.0201 (8) | 0.0006 (7) | 0.0084 (6) | 0.0032 (7) |
C7 | 0.0216 (8) | 0.0190 (8) | 0.0280 (8) | −0.0007 (6) | 0.0102 (6) | 0.0056 (7) |
C8 | 0.0181 (8) | 0.0165 (8) | 0.0261 (8) | −0.0002 (6) | 0.0059 (6) | 0.0006 (6) |
C9 | 0.0157 (7) | 0.0158 (7) | 0.0194 (7) | 0.0030 (6) | 0.0045 (6) | 0.0027 (6) |
C10 | 0.0176 (7) | 0.0174 (8) | 0.0166 (7) | 0.0024 (6) | 0.0027 (6) | 0.0021 (6) |
C11 | 0.0163 (7) | 0.0175 (8) | 0.0165 (7) | 0.0024 (6) | 0.0020 (6) | 0.0034 (6) |
C12 | 0.0159 (7) | 0.0159 (7) | 0.0220 (8) | 0.0019 (6) | 0.0007 (6) | 0.0049 (6) |
C13 | 0.020 (2) | 0.013 (3) | 0.024 (2) | −0.002 (2) | 0.0019 (17) | 0.0015 (17) |
S14 | 0.0220 (5) | 0.0171 (5) | 0.0203 (5) | −0.0011 (3) | 0.0023 (4) | −0.0002 (3) |
C15 | 0.026 (3) | 0.021 (3) | 0.037 (3) | −0.001 (2) | 0.006 (2) | 0.0089 (19) |
C16 | 0.017 (2) | 0.017 (3) | 0.023 (2) | −0.0039 (18) | 0.0053 (18) | 0.0060 (17) |
C12' | 0.0159 (7) | 0.0159 (7) | 0.0220 (8) | 0.0019 (6) | 0.0007 (6) | 0.0049 (6) |
C13' | 0.021 (3) | 0.020 (4) | 0.020 (3) | 0.007 (3) | 0.004 (3) | −0.002 (3) |
C14' | 0.027 (3) | 0.026 (4) | 0.030 (3) | 0.008 (3) | −0.004 (3) | −0.006 (3) |
S15' | 0.0206 (12) | 0.0173 (12) | 0.0253 (10) | −0.0030 (9) | 0.0021 (7) | 0.0016 (8) |
C16' | 0.019 (4) | 0.015 (4) | 0.026 (3) | −0.002 (3) | −0.004 (3) | 0.003 (3) |
C17 | 0.0153 (7) | 0.0180 (8) | 0.0236 (9) | −0.0007 (6) | 0.0035 (6) | 0.0052 (6) |
N18 | 0.0234 (7) | 0.0283 (8) | 0.0223 (7) | −0.0017 (6) | 0.0064 (6) | 0.0031 (6) |
C19 | 0.0205 (8) | 0.0154 (7) | 0.0203 (8) | 0.0012 (6) | 0.0056 (6) | −0.0010 (6) |
C20 | 0.0215 (8) | 0.0157 (7) | 0.0149 (7) | 0.0005 (6) | 0.0059 (6) | 0.0030 (6) |
C21 | 0.0239 (8) | 0.0181 (8) | 0.0205 (8) | 0.0023 (6) | 0.0046 (6) | −0.0013 (6) |
C22 | 0.0246 (9) | 0.0265 (9) | 0.0231 (8) | 0.0092 (7) | 0.0059 (6) | 0.0003 (7) |
C23 | 0.0212 (8) | 0.0346 (10) | 0.0165 (7) | 0.0019 (7) | 0.0032 (6) | −0.0002 (7) |
C24 | 0.0277 (9) | 0.0253 (9) | 0.0203 (8) | −0.0006 (7) | 0.0036 (7) | −0.0057 (7) |
C25 | 0.0231 (8) | 0.0194 (8) | 0.0217 (8) | 0.0032 (6) | 0.0057 (6) | −0.0010 (6) |
Cl1 | 0.0219 (2) | 0.0607 (3) | 0.0282 (2) | 0.0056 (2) | −0.00151 (16) | −0.0154 (2) |
N1—C2 | 1.357 (2) | S14—C15 | 1.698 (10) |
N1—C9 | 1.3823 (19) | C15—C16 | 1.334 (15) |
N1—C19 | 1.447 (2) | C15—H15 | 0.9500 |
C2—C3 | 1.379 (2) | C16—H16 | 0.9500 |
C2—H2 | 0.9500 | C13'—C14' | 1.32 (2) |
C3—C10 | 1.431 (2) | C13'—H13' | 0.9500 |
C3—C4 | 1.442 (2) | C14'—S15' | 1.701 (11) |
C4—C5 | 1.395 (2) | C14'—H14' | 0.9500 |
C4—C9 | 1.401 (2) | S15'—C16' | 1.707 (17) |
C5—C6 | 1.377 (2) | C16'—H16' | 0.9500 |
C5—H5 | 0.9500 | C17—N18 | 1.146 (2) |
C6—C7 | 1.396 (2) | C19—C20 | 1.506 (2) |
C6—H6 | 0.9500 | C19—H19A | 0.9900 |
C7—C8 | 1.375 (2) | C19—H19B | 0.9900 |
C7—H7 | 0.9500 | C20—C21 | 1.380 (2) |
C8—C9 | 1.386 (2) | C20—C25 | 1.386 (2) |
C8—H8 | 0.9500 | C21—C22 | 1.385 (2) |
C10—C11 | 1.352 (2) | C21—H21 | 0.9500 |
C10—H10 | 0.9500 | C22—C23 | 1.375 (3) |
C11—C17 | 1.429 (2) | C22—H22 | 0.9500 |
C11—C12 | 1.466 (2) | C23—C24 | 1.373 (2) |
C12—C13 | 1.355 (11) | C23—Cl1 | 1.7397 (17) |
C12—C16 | 1.442 (9) | C24—C25 | 1.379 (2) |
C13—S14 | 1.721 (10) | C24—H24 | 0.9500 |
C13—H13 | 0.9500 | C25—H25 | 0.9500 |
C2—N1—C9 | 108.95 (13) | C15—S14—C13 | 89.9 (5) |
C2—N1—C19 | 125.38 (13) | C16—C15—S14 | 113.8 (8) |
C9—N1—C19 | 125.03 (13) | C16—C15—H15 | 123.1 |
N1—C2—C3 | 110.44 (13) | S14—C15—H15 | 123.1 |
N1—C2—H2 | 124.8 | C15—C16—C12 | 112.7 (8) |
C3—C2—H2 | 124.8 | C15—C16—H16 | 123.7 |
C2—C3—C10 | 129.95 (14) | C12—C16—H16 | 123.7 |
C2—C3—C4 | 105.73 (13) | C14'—C13'—H13' | 125.8 |
C10—C3—C4 | 124.27 (14) | C13'—C14'—S15' | 116.6 (11) |
C5—C4—C9 | 118.68 (14) | C13'—C14'—H14' | 121.7 |
C5—C4—C3 | 134.10 (15) | S15'—C14'—H14' | 121.7 |
C9—C4—C3 | 107.15 (13) | C14'—S15'—C16' | 88.9 (8) |
C6—C5—C4 | 118.64 (15) | S15'—C16'—H16' | 123.8 |
C6—C5—H5 | 120.7 | N18—C17—C11 | 178.23 (17) |
C4—C5—H5 | 120.7 | N1—C19—C20 | 115.37 (13) |
C5—C6—C7 | 121.44 (15) | N1—C19—H19A | 108.4 |
C5—C6—H6 | 119.3 | C20—C19—H19A | 108.4 |
C7—C6—H6 | 119.3 | N1—C19—H19B | 108.4 |
C8—C7—C6 | 121.23 (15) | C20—C19—H19B | 108.4 |
C8—C7—H7 | 119.4 | H19A—C19—H19B | 107.5 |
C6—C7—H7 | 119.4 | C21—C20—C25 | 119.08 (15) |
C7—C8—C9 | 116.95 (15) | C21—C20—C19 | 123.19 (14) |
C7—C8—H8 | 121.5 | C25—C20—C19 | 117.73 (14) |
C9—C8—H8 | 121.5 | C20—C21—C22 | 120.70 (15) |
N1—C9—C8 | 129.21 (15) | C20—C21—H21 | 119.7 |
N1—C9—C4 | 107.71 (13) | C22—C21—H21 | 119.7 |
C8—C9—C4 | 123.06 (14) | C23—C22—C21 | 118.93 (15) |
C11—C10—C3 | 129.61 (14) | C23—C22—H22 | 120.5 |
C11—C10—H10 | 115.2 | C21—C22—H22 | 120.5 |
C3—C10—H10 | 115.2 | C24—C23—C22 | 121.48 (16) |
C10—C11—C17 | 120.07 (14) | C24—C23—Cl1 | 118.61 (14) |
C10—C11—C12 | 125.45 (14) | C22—C23—Cl1 | 119.90 (13) |
C17—C11—C12 | 114.47 (13) | C23—C24—C25 | 119.02 (16) |
C13—C12—C16 | 109.8 (4) | C23—C24—H24 | 120.5 |
C13—C12—C11 | 124.6 (4) | C25—C24—H24 | 120.5 |
C16—C12—C11 | 125.6 (4) | C24—C25—C20 | 120.78 (15) |
C12—C13—S14 | 113.8 (7) | C24—C25—H25 | 119.6 |
C12—C13—H13 | 123.1 | C20—C25—H25 | 119.6 |
S14—C13—H13 | 123.1 | ||
C9—N1—C2—C3 | 1.06 (17) | C10—C11—C12—C13 | 0.1 (10) |
C19—N1—C2—C3 | 172.28 (14) | C17—C11—C12—C13 | 178.9 (10) |
N1—C2—C3—C10 | −177.97 (15) | C10—C11—C12—C16 | −179.2 (8) |
N1—C2—C3—C4 | −0.34 (17) | C17—C11—C12—C16 | −0.4 (8) |
C2—C3—C4—C5 | −177.53 (17) | C16—C12—C13—S14 | −1.1 (15) |
C10—C3—C4—C5 | 0.3 (3) | C11—C12—C13—S14 | 179.5 (5) |
C2—C3—C4—C9 | −0.48 (17) | C12—C13—S14—C15 | 1.2 (13) |
C10—C3—C4—C9 | 177.32 (14) | C13—S14—C15—C16 | −0.9 (14) |
C9—C4—C5—C6 | −0.8 (2) | S14—C15—C16—C12 | 0.4 (17) |
C3—C4—C5—C6 | 176.00 (16) | C13—C12—C16—C15 | 0.5 (17) |
C4—C5—C6—C7 | 0.6 (2) | C11—C12—C16—C15 | 179.8 (9) |
C5—C6—C7—C8 | 0.1 (3) | C13'—C14'—S15'—C16' | 1 (2) |
C6—C7—C8—C9 | −0.5 (2) | C2—N1—C19—C20 | 117.63 (16) |
C2—N1—C9—C8 | 176.85 (15) | C9—N1—C19—C20 | −72.53 (19) |
C19—N1—C9—C8 | 5.6 (3) | N1—C19—C20—C21 | −18.7 (2) |
C2—N1—C9—C4 | −1.35 (17) | N1—C19—C20—C25 | 162.34 (13) |
C19—N1—C9—C4 | −172.60 (13) | C25—C20—C21—C22 | −0.4 (2) |
C7—C8—C9—N1 | −177.66 (15) | C19—C20—C21—C22 | −179.32 (14) |
C7—C8—C9—C4 | 0.3 (2) | C20—C21—C22—C23 | 0.4 (2) |
C5—C4—C9—N1 | 178.70 (13) | C21—C22—C23—C24 | 0.4 (3) |
C3—C4—C9—N1 | 1.11 (17) | C21—C22—C23—Cl1 | −179.11 (13) |
C5—C4—C9—C8 | 0.4 (2) | C22—C23—C24—C25 | −1.0 (3) |
C3—C4—C9—C8 | −177.21 (14) | Cl1—C23—C24—C25 | 178.44 (13) |
C2—C3—C10—C11 | 4.7 (3) | C23—C24—C25—C20 | 1.0 (2) |
C4—C3—C10—C11 | −172.51 (15) | C21—C20—C25—C24 | −0.3 (2) |
C3—C10—C11—C17 | 0.0 (3) | C19—C20—C25—C24 | 178.69 (14) |
C3—C10—C11—C12 | 178.75 (15) |
Experimental details
Crystal data | |
Chemical formula | C22H15ClN2S |
Mr | 374.87 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 90 |
a, b, c (Å) | 16.8531 (11), 5.5629 (4), 18.7889 (13) |
β (°) | 96.877 (2) |
V (Å3) | 1748.8 (2) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 3.10 |
Crystal size (mm) | 0.25 × 0.02 × 0.01 |
Data collection | |
Diffractometer | Bruker X8 Proteum |
Absorption correction | Multi-scan (SADABS in APEX2; Bruker, 2006) |
Tmin, Tmax | 0.657, 0.970 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24522, 3248, 3020 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.608 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.088, 1.05 |
No. of reflections | 3248 |
No. of parameters | 273 |
No. of restraints | 162 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.32 |
Computer programs: APEX2 (Bruker, 2006), SHELXS97 (Sheldrick, 1997), XP in SHELXTL (Sheldrick, 1995), SHELXL97 (Sheldrick, 1997) and local procedures.
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We have synthesized a series of novel substituted aryl/heteroaryl-2-(thienyl) acrylonitriles and evaluated them for anticancer activity. The title compound was prepared by the base-catalyzed reaction of 1-(4-chlorobenzyl)indole-3- carboxaldehyde with thiophene-3-acetonitrile and recrystallization of the product from methanol to afford yellow needles. In order to confirm the double bond geometry in the title compound, and to obtain more detailed information of the structural conformation of the molecule, its X-ray structure determination has been carried out.
X-ray crystallography confirmed the molecular structure and atom connectivity for the title compound. In the title molecule the double bond connecting the indole and thiophene moieties has the Z-geometry. The indole ring is nearly planar with bond distances and bond angles comparable with those reported for other indole derivatives (Mason et al., 2003; Zarza et al., 1988). In the molecule, atom N1 lies slightly [0.0640 (16) Å] out of the plane of connecting atoms C2, C9, and C19, the sum of the angles about N1 being 359.36 (13)°. In a previous study, 21 structurally related indole analogues were analyzed (Beddoes et al., 1986) (available in the Cambridge Structural Database; Allen, 2002), and the sum of the three angles around the N atom were determined, to assess planarity. It was found that only two of the 21 compounds had values that were outside the range 359.0–360°, the farthest value from the perfectly planar situation being 357.2°. This is in general agreement with our current observation with the title compound. The plane of the 4-chlorophenyl group is twisted well out of the plane of the indole ring and makes a dihedral angle of 79.81 (4)°. There is an asymmetry of the exocyclic angles at C20 [C19—C20—C21 = 123.19 (14)° and C19—C20—C25 =117.73 (14)°].
Deviations from the ideal bond-angle geometry around the Csp2 atoms of the double bond are observed. The bond angles C2=C3—C10, C3—C10=C11, and C12—C11—C17 [129.95 (14), 129.61 (14), and 114.47 (13)°, respectively] are distorted because of strain induced by the double bond linking the indole and thiophene rings. The vinyl group bearing the three substituents has a double bond length of 1.352 (2) Å and is significantly longer than that observed in the disubstituted vinyl group of 2-styrylbenzimidazoles (1.304 (4) Å; Bacelo et al., 1997). Furthermore, the C3—C10 bond length [1.431 (2) Å] is slightly shorter than a Car—Csp2 single bond (Wilson, 1992). The C2=C3—C10=C11, C3—C10=C11—C12, and C10=C11—C12=C16 torsion angles [4.7 (3), 178.75 (15), and -179.2 (8), respectively] show that the non-H atoms of the indole and thiophene rings are nearly coplanar. The 2-thienyl group exhibits rotational disorder over two sets of sites corresponding to 180° about the C11—C12 bond with occupancy factors of 0.65:0.35.