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The title compound, C15H11NS, contains a thio­phene ring and a quinoline moiety connected by an ethyl­ene bridge, which shows a trans configuration. The thio­phene ring is disordered over two sites by rotation about the exocyclic C-C bond.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803010572/lh6061sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803010572/lh6061Isup2.hkl
Contains datablock I

CCDC reference: 217441

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.046
  • wR factor = 0.109
  • Data-to-parameter ratio = 15.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes

REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.18 From the CIF: _reflns_number_total 2438 Count of symmetry unique reflns 1571 Completeness (_total/calc) 155.19% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 867 Fraction of Friedel pairs measured 0.552 Are heavy atom types Z>Si present yes Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.

Comment top

Many synthetic antimalaric products, like chloroquinine (Joule et al., 1995, and references therein), possess a skeleton based on the quinolenic moiety. Most of these products are active in biological processes (Zouhiri et al., 2000). Moreover, bichromophors containing two or more quinoline molecules linked by hydrocarbon channels are known as active chelatants of metallic ions (Wong & Wong, 1996). Bichromophors containing the quinoline nucleus (Radhakrishnan et al., 1995; Wang & Ho, 1997) or naphthalene (Arai & Tokumaru, 1993) exibit the same behaviour as those containing pyridine (Favaro et al., 1973) or benzene derivatives (Létard et al., 1993; Lewis & Yang, 1997). Furthermore, the photophysical aspect of styrylquinoline derivatives is still attracting attention of many researchers (Arai et al., 1994).

Based on the acidic characteristic of methyl protons in the 2-position of pyridine and quinoline, we have adapted the condensation reaction of 2-picoline on benzaldehyde referring to the conventional synthetic method reported in the literature (Wang & Ho, 1997). This process results in quinolenic olefins by means of condensation of 2-methylquinoline on different kind of aldehydes. All products obtained by this reaction have a trans configuration. We did check this result by our numerous other spectroscopical investigations, mainly IR, mass and NMR (1H and 13C), notably by the study of the chemical displacements of the ethylic protons by 1H NMR as by IR absorption bands of the deformations out of the ethylenic double bond. On the other hand, we concluded on the same conformation when we studied the crystal structure of trans-1-(2-quinolyl)-2-(2-thienyl)ethylene and trans-bis(4-quinolyl)ethylene (Jerdioui et al., 1999). We decribe here the synthesis and X-ray crystal structure analysis of the title compound, (I). The crystal data are in agreement with the spectroscopical investigations, particularly the molecular conformation. The present study will allow us to understand more deeply the influence of the thienyl group on the behaviour of this derivative, both at its ground and exited state.

The thiophene ring and the quinoline moiety are nearly coplanar, the dihedral angle between them is 13.4 (1)°. The ethylenic double bond is trans-configured.

Experimental top

2 g (13.9 mmol) of 2-methylquinoline, 2.6 ml of anhydrous acetic acid and 2.6 ml of acetic acid were mixed in a 100 ml flask crowned by a refrigerant. After heating to 333 K, we added 17 mmol of thienaldehyde. The mixture was then heated at 393 K for 2 h, the evolution of the reaction being followed by CCM [please define]. After cooling to room temperature, we neutralized the solution with CaCO3. The extraction was realised by dichloromethane. Elimination of the solvent produced a yellow solid, which was then recrystallized in a mixture of equimolar hexane/dichloromethane, to yield yellowish crystals in the form of plates.

Refinement top

The thiophene ring is disordered. The resolution of the data did not allow two distinct positions for the S and C atoms to be distinguished. Only one peak was found for each atom in the difference map. Thus, a C and an S atom were refined sharing the same position and the same displacement parameters and just refining the site-occupation factor of the respecitve C and S atoms in order to determine the ratio of the different orientations, which turned out to be 0.820 (3) to 0.180 (3). All H atoms except those of the disordered atoms were located by difference Fourier synthesis and refined with fixed individual displacement parameters [Uiso(H) = 1.2Ueq(C)] using a riding model with C—H = 0.95 Å.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Sheldrick, 1991).

Figures top
[Figure 1] Fig. 1. A perspective view of the title compound with the atom-numbering scheme. Displacement ellipsoids are at the 50% probability level. Only the main conformation is shown.
(I) top
Crystal data top
C15H11NSF(000) = 496
Mr = 237.31Dx = 1.323 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 512 reflections
a = 6.0100 (12) Åθ = 1–20°
b = 7.8502 (16) ŵ = 0.25 mm1
c = 25.258 (5) ÅT = 173 K
V = 1191.7 (4) Å3Plate, yellow
Z = 40.41 × 0.26 × 0.06 mm
Data collection top
Siemens CCD three-circle
diffractometer
2438 independent reflections
Radiation source: fine-focus sealed tube1882 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.047
ω scansθmax = 27.2°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 77
Tmin = 0.891, Tmax = 0.976k = 99
9574 measured reflectionsl = 3031
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.109 w = 1/[σ2(Fo2) + (0.0462P)2 + 0.4035P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
2438 reflectionsΔρmax = 0.41 e Å3
155 parametersΔρmin = 0.20 e Å3
0 restraintsAbsolute structure: Flack (1983), 962 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.07 (15)
Crystal data top
C15H11NSV = 1191.7 (4) Å3
Mr = 237.31Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.0100 (12) ŵ = 0.25 mm1
b = 7.8502 (16) ÅT = 173 K
c = 25.258 (5) Å0.41 × 0.26 × 0.06 mm
Data collection top
Siemens CCD three-circle
diffractometer
2438 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1882 reflections with I > 2σ(I)
Tmin = 0.891, Tmax = 0.976Rint = 0.047
9574 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.109Δρmax = 0.41 e Å3
S = 1.06Δρmin = 0.20 e Å3
2438 reflectionsAbsolute structure: Flack (1983), 962 Friedel pairs
155 parametersAbsolute structure parameter: 0.07 (15)
0 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
S10.24475 (16)0.18220 (10)0.82079 (3)0.0392 (3)0.820 (3)
C10.24475 (16)0.18220 (10)0.82079 (3)0.0392 (3)0.180 (3)
H10.38400.12780.82640.047*0.180 (3)
C20.1326 (5)0.2866 (4)0.76861 (10)0.0358 (7)
S30.0843 (3)0.3430 (3)0.77941 (8)0.0436 (8)0.180 (3)
C30.0843 (3)0.3430 (3)0.77941 (8)0.0436 (8)0.820 (3)
H30.17770.40230.75530.052*0.820 (3)
C40.1442 (5)0.2966 (4)0.83413 (11)0.0427 (7)
H40.28260.32520.85000.051*
C50.0185 (6)0.2103 (4)0.85912 (11)0.0464 (8)
H50.00710.17030.89450.056*
C60.2477 (6)0.3110 (4)0.71807 (10)0.0404 (6)
H60.18670.39070.69380.049*
C70.4294 (5)0.2301 (4)0.70412 (11)0.0410 (8)
H70.48560.14570.72750.049*
C110.5527 (5)0.2615 (4)0.65442 (10)0.0357 (7)
N110.4713 (4)0.3728 (3)0.61946 (9)0.0339 (6)
C120.6003 (4)0.4096 (3)0.57595 (10)0.0289 (6)
C130.5235 (5)0.5300 (4)0.53933 (11)0.0388 (7)
H130.38200.58140.54430.047*
C140.6492 (6)0.5740 (4)0.49668 (12)0.0459 (8)
H140.59400.65590.47230.055*
C150.8588 (6)0.5009 (4)0.48811 (11)0.0440 (8)
H150.94450.53300.45810.053*
C160.9399 (5)0.3823 (4)0.52325 (10)0.0364 (7)
H161.08190.33240.51750.044*
C170.8130 (4)0.3345 (3)0.56778 (10)0.0279 (6)
C180.8857 (5)0.2142 (3)0.60548 (10)0.0374 (7)
H181.02470.15830.60090.045*
C190.7591 (5)0.1785 (4)0.64777 (10)0.0395 (6)
H190.80810.09750.67320.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0476 (5)0.0405 (5)0.0296 (4)0.0103 (5)0.0020 (4)0.0042 (4)
C10.0476 (5)0.0405 (5)0.0296 (4)0.0103 (5)0.0020 (4)0.0042 (4)
C20.0426 (18)0.0320 (15)0.0328 (14)0.0075 (14)0.0018 (12)0.0056 (12)
S30.0455 (14)0.0485 (14)0.0369 (11)0.0018 (11)0.0041 (9)0.0030 (9)
C30.0455 (14)0.0485 (14)0.0369 (11)0.0018 (11)0.0041 (9)0.0030 (9)
C40.0409 (17)0.0425 (17)0.0448 (16)0.0033 (15)0.0093 (13)0.0074 (14)
C50.069 (2)0.0368 (18)0.0337 (15)0.0011 (17)0.0097 (15)0.0026 (13)
C60.0440 (17)0.0343 (14)0.0430 (14)0.0042 (18)0.0095 (16)0.0022 (12)
C70.0443 (19)0.0361 (17)0.0426 (16)0.0037 (15)0.0037 (14)0.0031 (14)
C110.0458 (18)0.0335 (15)0.0277 (14)0.0101 (13)0.0035 (13)0.0006 (12)
N110.0282 (13)0.0367 (14)0.0369 (13)0.0050 (10)0.0040 (10)0.0121 (11)
C120.0278 (15)0.0270 (13)0.0319 (14)0.0046 (12)0.0037 (12)0.0065 (11)
C130.0377 (18)0.0345 (17)0.0442 (16)0.0019 (13)0.0099 (14)0.0032 (13)
C140.057 (2)0.0388 (17)0.0415 (17)0.0002 (17)0.0062 (16)0.0095 (15)
C150.058 (2)0.0442 (18)0.0299 (15)0.0172 (17)0.0084 (15)0.0009 (14)
C160.0349 (17)0.0383 (16)0.0362 (15)0.0047 (14)0.0040 (13)0.0116 (13)
C170.0288 (15)0.0261 (13)0.0287 (12)0.0006 (11)0.0027 (10)0.0065 (12)
C180.0369 (17)0.0345 (16)0.0407 (15)0.0026 (14)0.0087 (14)0.0044 (13)
C190.0478 (17)0.0383 (15)0.0326 (13)0.0019 (18)0.0071 (15)0.0020 (13)
Geometric parameters (Å, º) top
S1—C51.684 (3)N11—C121.375 (3)
S1—C21.692 (3)C12—C131.401 (4)
S1—H10.95C12—C171.422 (4)
C2—S31.404 (3)C13—C141.360 (4)
C2—C61.465 (4)C13—H130.95
S3—C41.474 (3)C14—C151.401 (5)
S3—H30.9501C14—H140.95
C4—C51.346 (4)C15—C161.376 (4)
C4—H40.95C15—H150.95
C5—H50.9502C16—C171.410 (4)
C6—C71.312 (4)C16—H160.95
C6—H60.95C17—C181.411 (4)
C7—C111.478 (4)C18—C191.341 (4)
C7—H70.95C18—H180.95
C11—N111.335 (3)C19—H190.95
C11—C191.411 (4)
C5—S1—C293.59 (16)N11—C12—C13118.9 (3)
C5—S1—H1133.2N11—C12—C17122.4 (2)
C2—S1—H1133.2C13—C12—C17118.7 (3)
S3—C2—C6124.5 (3)C14—C13—C12120.7 (3)
S3—C2—S1111.81 (19)C14—C13—H13119.6
C6—C2—S1123.7 (2)C12—C13—H13119.6
C2—S3—C4109.3 (2)C13—C14—C15121.2 (3)
C2—S3—H3125.4C13—C14—H14119.4
C4—S3—H3125.3C15—C14—H14119.4
C5—C4—S3112.7 (3)C16—C15—C14119.8 (3)
C5—C4—H4123.8C16—C15—H15120.1
S3—C4—H4123.4C14—C15—H15120.1
C4—C5—S1112.5 (2)C15—C16—C17120.2 (3)
C4—C5—H5123.7C15—C16—H16119.9
S1—C5—H5123.8C17—C16—H16119.9
C7—C6—C2124.3 (3)C16—C17—C18123.3 (2)
C7—C6—H6117.8C16—C17—C12119.4 (2)
C2—C6—H6117.8C18—C17—C12117.3 (2)
C6—C7—C11124.4 (3)C19—C18—C17120.1 (3)
C6—C7—H7117.8C19—C18—H18120.0
C11—C7—H7117.8C17—C18—H18120.0
N11—C11—C19123.1 (2)C18—C19—C11119.8 (2)
N11—C11—C7119.2 (3)C18—C19—H19120.1
C19—C11—C7117.7 (2)C11—C19—H19120.1
C11—N11—C12117.3 (2)
C5—S1—C2—S31.0 (2)N11—C12—C13—C14177.9 (3)
C5—S1—C2—C6179.8 (2)C17—C12—C13—C140.2 (4)
C6—C2—S3—C4179.8 (2)C12—C13—C14—C150.1 (4)
S1—C2—S3—C41.5 (3)C13—C14—C15—C160.0 (4)
C2—S3—C4—C51.4 (3)C14—C15—C16—C170.1 (4)
S3—C4—C5—S10.6 (3)C15—C16—C17—C18179.9 (3)
C2—S1—C5—C40.2 (3)C15—C16—C17—C120.2 (4)
S3—C2—C6—C7165.6 (3)N11—C12—C17—C16177.8 (2)
S1—C2—C6—C713.0 (4)C13—C12—C17—C160.2 (4)
C2—C6—C7—C11176.4 (3)N11—C12—C17—C182.2 (3)
C6—C7—C11—N113.6 (4)C13—C12—C17—C18179.8 (2)
C6—C7—C11—C19172.9 (3)C16—C17—C18—C19178.0 (3)
C19—C11—N11—C121.8 (4)C12—C17—C18—C192.0 (4)
C7—C11—N11—C12174.5 (2)C17—C18—C19—C110.0 (4)
C11—N11—C12—C13177.9 (2)N11—C11—C19—C182.0 (4)
C11—N11—C12—C170.4 (3)C7—C11—C19—C18174.3 (3)

Experimental details

Crystal data
Chemical formulaC15H11NS
Mr237.31
Crystal system, space groupOrthorhombic, P212121
Temperature (K)173
a, b, c (Å)6.0100 (12), 7.8502 (16), 25.258 (5)
V3)1191.7 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.25
Crystal size (mm)0.41 × 0.26 × 0.06
Data collection
DiffractometerSiemens CCD three-circle
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.891, 0.976
No. of measured, independent and
observed [I > 2σ(I)] reflections
9574, 2438, 1882
Rint0.047
(sin θ/λ)max1)0.643
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.109, 1.06
No. of reflections2438
No. of parameters155
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.41, 0.20
Absolute structureFlack (1983), 962 Friedel pairs
Absolute structure parameter0.07 (15)

Computer programs: SMART (Siemens, 1995), SMART, SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Sheldrick, 1991).

Selected geometric parameters (Å, º) top
C2—C61.465 (4)C11—N111.335 (3)
C6—C71.312 (4)N11—C121.375 (3)
C7—C111.478 (4)
C7—C6—C2124.3 (3)C11—N11—C12117.3 (2)
C6—C7—C11124.4 (3)
C2—C6—C7—C11176.4 (3)
 

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