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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1453–o1454.
Published online 2008 July 9. doi:  10.1107/S1600536808020734
PMCID: PMC2962084

1-Methyl-2-[(E)-2-(2-thien­yl)ethen­yl]quinolinium iodide1

Abstract

In the title compound, C16H14NS+·I, the cation has an E configuration about the C=C double bond of the ethyl­ene unit. The dihedral angle between the thio­phene ring and the quinolinium ring system is 11.67 (11)°. A weak C—H(...)S intra­molecular inter­action involving the thio­phene ring generates an S(5) ring motif. In the crystal structure, the iodide ion, located between the cations arranged in an anti­parallel manner, forms weak C—H(...)I inter­actions. The crystal structure is further stabilized by a π–π inter­action between the thio­phene and pyridine rings; the centroid–centroid distance is 3.6818 (13) Å.

Related literature

For bond lengths, see: Allen et al. (1987 [triangle]). For related literature on hydrogen-bond motifs, see: Bernstein et al. (1995 [triangle]). For related structures, see, for example: Chantrapromma et al. (2006 [triangle], 2008 [triangle]); Chantrapromma, Jindawong & Fun (2007 [triangle]); Chantrapromma, Jindawong, Fun & Patil (2007 [triangle]). For background literature on non-linear optical properties, see, for example: Chou et al. (1996 [triangle]); Dittrich et al. (2003 [triangle]); Drost et al. (1995 [triangle]); Morley (1991 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1453-scheme1.jpg

Experimental

Crystal data

  • C16H14NS+·I
  • M r = 379.25
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1453-efi1.jpg
  • a = 7.8243 (1) Å
  • b = 9.6906 (1) Å
  • c = 10.7633 (2) Å
  • α = 97.521 (1)°
  • β = 95.338 (1)°
  • γ = 112.758 (1)°
  • V = 736.82 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 2.30 mm−1
  • T = 100.0 (1) K
  • 0.58 × 0.28 × 0.14 mm

Data collection

  • Bruker SMART APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.346, T max = 0.725
  • 17060 measured reflections
  • 4261 independent reflections
  • 4118 reflections with I > 2σ(I)
  • R int = 0.018

Refinement

  • R[F 2 > 2σ(F 2)] = 0.022
  • wR(F 2) = 0.059
  • S = 1.10
  • 4261 reflections
  • 173 parameters
  • H-atom parameters constrained
  • Δρmax = 1.50 e Å−3
  • Δρmin = −0.90 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 [triangle]); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808020734/is2311sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808020734/is2311Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The Center for Innovation in Chemistry: Postgraduate Education and Research Program in Chemistry (PERCH-CIC), Commission on Higher Education, Ministry of Education and the Graduate School, Prince of Songkla University are gratefully acknowledged for providing financial support to PR. The authors thank the Prince of Songkla University for a research grant and also the Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

The design and synthesis of conjugated compounds to search for second-order nonlinear optic (NLO) materials have generated extensive interest. From previous reports, both molecular orbital calculations (Morley, 1991) and experimental studies (Drost et al., 1995) have revealed that the products of dipole moment and molecular hyperpolarizability (υβ) of thiophene-containing conjugated moieties are superior to that of benzene analogues. Based on this reason we have previously studied the compound containing thiophene unit, namely, 1-methyl-4-[(E)-2-(2-thienyl)ethenyl]-pyridinium 4-chlorobenzenesulfonate (Chantrapromma et al., 2008). In this paper we have synthesized the title compound which was designed by the replacement of the cationic 3-hydroxy-4-methoxyphenyl ring that is present in a compound possessing second-harmonic-generation (SHG) properties, 2-[(E)-2-(3-hydroxy-4-methoxyphenyl)ethenyl]-1methylquinolinium, iodide monohydrate (Chantrapromma, Jindawong, Fun & Patil, 2007) by the thiophene unit. Herein we report the synthesis and crystal structure of the title compound.

The asymmetric unit of the title compound (Fig. 1) consists of the C16H14NS+ cation and I- ion. The cation exists in the E configuration with respect to the C10═C11 double bond [1.350 (3) Å] and is almost planar with the interplanar angle between the quinolinium and the thiophene ring being 11.67 (11)° and the torsion angles C9–C10–C11–C12 = -178.56 (17)°. The ethenyl unit is co-planar with the thiophene ring as can be indicated by the torsion angles C10–C11–C12–C13 = -179.42 (18)° and C10–C11–C12–S1 = 1.4 (3)°. It is slightly deviated from the quinolinium ring with the torsion angle C8–C9–C10–C11 = -14.2 (3)°. The atom S1 of the thiophene ring contributes to the C—H···S intramolecular weak interaction (Fig. 1 and Table 1) forming S(5) ring motifs (Bernstein et al., 1995). The bond lengths and angles are normal (Allen et al., 1987) and are comparable with closely related structures (Chantrapromma et al., 2006, 2008; Chantrapromma, Jindawong & Fun, 2007; Chantrapromma, Jindawong, Fun & Patil, 2007).

In the crystal packing (Fig. 2), the I- ion is in between each pair of the two antiparallel cations and is linked with the cations through weak C—H···I interactions. The crystal is stabilized by weak C—H···S and C—H···I interactions (Table 1). A π–π interaction was observed with the Cg1···Cg2 distance of 3.6818 (13) Å; Cg1i and Cg2i are the centroids of the S1/C12–C15 and N1/C1/C6–C9 rings, respectively [symmetry code: (i): 1 - x, 1 - y, 1 - z]. The perpendicular distances of Cg2 onto the plane of the S1/C12–C15 ring and Cg1 onto the plane of the N1/C1/C6–C9 ring are 3.200 and 3.500Å, respectively

Experimental

2-(2-Thiophenestyryl)-1-methylquinilinium iodide was synthesized by mixing a solution (1:1:1 molar ratio) of 1,2-dimethylquinolinium iodide (2.00 g, 7.0 mmol), 2-thiophenecarboxaldehyde (0.64 ml, 7.0 mmol) and piperidine (0.69 ml, 7.0 mmol) in hot methanol (40 ml). The resulting solution was refluxed for 5 hr under a nitrogen atmosphere. The resultant solid was filtered off and washed with diethyl ether. Brown block-shaped single crystals of the title compound suitable for x-ray structure determination were obtained after recrystalization from methanol by slow evaporation of the solvent at room temperature after a few weeks.

Refinement

All H atoms were placed in calculated positions (C—H = 0.93–0.96 Å) and were refined as riding, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). A rotating group model was used for the methyl group. The highest residual electron density peak is located at 0.75 Å from atom I1 and the deepest hole is located at 0.38 Å from atom S1.

Figures

Fig. 1.
The title compound showing 50% probability displacement ellipsoids and the atom-numbering scheme. The weak C—H···S intramolecular interaction was drawn as a dashed line.
Fig. 2.
The packing diagram of the title structure, viewed approximately along the b axis. Weak C—H···I interactions were drawn as dashed lines.

Crystal data

C16H14NS+·IZ = 2
Mr = 379.25F000 = 372
Triclinic, P1Dx = 1.709 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 7.8243 (1) ÅCell parameters from 4261 reflections
b = 9.6906 (1) Åθ = 2.3–30.0º
c = 10.7633 (2) ŵ = 2.30 mm1
α = 97.521 (1)ºT = 100.0 (1) K
β = 95.338 (1)ºBlock, brown
γ = 112.758 (1)º0.58 × 0.28 × 0.14 mm
V = 736.817 (18) Å3

Data collection

Bruker SMART APEXII CCD area-detector diffractometer4261 independent reflections
Radiation source: fine-focus sealed tube4118 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.018
Detector resolution: 8.33 pixels mm-1θmax = 30.0º
T = 100.0(1) Kθmin = 2.3º
ω scansh = −11→11
Absorption correction: multi-scan(SADABS; Bruker, 2005)k = −13→13
Tmin = 0.346, Tmax = 0.725l = −15→15
17060 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.022H-atom parameters constrained
wR(F2) = 0.059  w = 1/[σ2(Fo2) + (0.0282P)2 + 0.8519P] where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.002
4261 reflectionsΔρmax = 1.50 e Å3
173 parametersΔρmin = −0.89 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

Experimental. The low-temparture data was collected with the Oxford Cryosystem Cobra low-temperature attachment.
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)

xyzUiso*/Ueq
I10.681003 (17)0.790360 (14)0.269777 (12)0.02186 (5)
S10.65928 (8)0.89200 (6)0.69144 (6)0.02828 (11)
N10.0896 (2)0.54762 (17)0.31586 (15)0.0162 (3)
C1−0.0473 (3)0.4405 (2)0.21950 (17)0.0167 (3)
C2−0.1289 (3)0.4838 (2)0.11749 (18)0.0198 (3)
H2A−0.09450.58630.11380.024*
C3−0.2600 (3)0.3734 (2)0.02336 (19)0.0227 (4)
H3A−0.31280.4025−0.04410.027*
C4−0.3158 (3)0.2180 (2)0.02687 (19)0.0227 (4)
H4A−0.40340.1452−0.03820.027*
C5−0.2405 (3)0.1739 (2)0.12667 (19)0.0206 (3)
H5A−0.27810.07110.12970.025*
C6−0.1062 (3)0.2843 (2)0.22486 (18)0.0180 (3)
C7−0.0267 (3)0.2412 (2)0.32868 (18)0.0193 (3)
H7A−0.06860.13910.33570.023*
C80.1112 (3)0.3491 (2)0.41844 (18)0.0180 (3)
H8A0.16440.31980.48550.022*
C90.1745 (2)0.5058 (2)0.41052 (17)0.0161 (3)
C100.3282 (3)0.6203 (2)0.50081 (18)0.0175 (3)
H10A0.38380.71740.48220.021*
C110.3950 (3)0.5929 (2)0.61089 (17)0.0174 (3)
H11A0.33990.49460.62730.021*
C120.5444 (3)0.7036 (2)0.70463 (18)0.0177 (3)
C130.6158 (3)0.6721 (2)0.82202 (19)0.0217 (4)
H13A0.57520.57760.84680.026*
C140.7577 (3)0.8091 (3)0.8930 (2)0.0282 (4)
H14A0.82030.81450.97240.034*
C150.7946 (3)0.9321 (3)0.8350 (2)0.0300 (4)
H15A0.88501.02850.87060.036*
C160.1413 (3)0.7112 (2)0.31385 (19)0.0211 (3)
H16A0.18100.76770.39910.032*
H16B0.03450.72500.27560.032*
H16C0.24180.74710.26550.032*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
I10.02044 (7)0.02041 (7)0.02481 (7)0.00758 (5)0.00089 (5)0.00842 (5)
S10.0287 (3)0.0207 (2)0.0312 (3)0.00775 (19)−0.0017 (2)0.00210 (19)
N10.0151 (7)0.0161 (7)0.0176 (7)0.0066 (5)0.0021 (5)0.0033 (5)
C10.0158 (7)0.0191 (8)0.0165 (8)0.0083 (6)0.0035 (6)0.0031 (6)
C20.0179 (8)0.0227 (9)0.0192 (8)0.0082 (7)0.0029 (6)0.0058 (7)
C30.0202 (8)0.0295 (10)0.0184 (8)0.0101 (7)0.0013 (7)0.0056 (7)
C40.0178 (8)0.0262 (9)0.0197 (8)0.0065 (7)−0.0009 (7)−0.0006 (7)
C50.0188 (8)0.0193 (8)0.0213 (8)0.0068 (7)0.0007 (7)−0.0005 (7)
C60.0161 (8)0.0187 (8)0.0184 (8)0.0068 (6)0.0023 (6)0.0019 (6)
C70.0195 (8)0.0165 (8)0.0217 (8)0.0075 (7)0.0028 (7)0.0028 (6)
C80.0183 (8)0.0177 (8)0.0181 (8)0.0077 (6)0.0017 (6)0.0033 (6)
C90.0153 (7)0.0175 (8)0.0164 (7)0.0074 (6)0.0036 (6)0.0030 (6)
C100.0178 (8)0.0154 (7)0.0188 (8)0.0064 (6)0.0023 (6)0.0021 (6)
C110.0158 (8)0.0173 (8)0.0190 (8)0.0070 (6)0.0026 (6)0.0023 (6)
C120.0168 (8)0.0163 (8)0.0198 (8)0.0069 (6)0.0026 (6)0.0015 (6)
C130.0121 (7)0.0217 (9)0.0238 (9)0.0014 (6)0.0068 (6)−0.0071 (7)
C140.0231 (9)0.0395 (12)0.0201 (9)0.0132 (9)−0.0010 (7)0.0002 (8)
C150.0263 (10)0.0248 (10)0.0295 (11)0.0056 (8)−0.0030 (8)−0.0066 (8)
C160.0219 (9)0.0163 (8)0.0245 (9)0.0075 (7)−0.0003 (7)0.0051 (7)

Geometric parameters (Å, °)

S1—C151.697 (2)C7—H7A0.9300
S1—C121.7273 (19)C8—C91.421 (2)
N1—C91.354 (2)C8—H8A0.9300
N1—C11.397 (2)C9—C101.446 (3)
N1—C161.481 (2)C10—C111.350 (3)
C1—C21.410 (3)C10—H10A0.9300
C1—C61.413 (3)C11—C121.436 (3)
C2—C31.377 (3)C11—H11A0.9300
C2—H2A0.9300C12—C131.450 (3)
C3—C41.403 (3)C13—C141.420 (3)
C3—H3A0.9300C13—H13A0.9300
C4—C51.371 (3)C14—C151.361 (4)
C4—H4A0.9300C14—H14A0.9300
C5—C61.412 (3)C15—H15A0.9300
C5—H5A0.9300C16—H16A0.9600
C6—C71.415 (3)C16—H16B0.9600
C7—C81.364 (3)C16—H16C0.9600
C15—S1—C1291.58 (11)N1—C9—C8119.08 (16)
C9—N1—C1121.89 (16)N1—C9—C10119.79 (16)
C9—N1—C16119.57 (16)C8—C9—C10121.13 (17)
C1—N1—C16118.53 (15)C11—C10—C9123.13 (17)
N1—C1—C2121.92 (17)C11—C10—H10A118.4
N1—C1—C6118.98 (16)C9—C10—H10A118.4
C2—C1—C6119.09 (17)C10—C11—C12125.11 (17)
C3—C2—C1119.54 (18)C10—C11—H11A117.4
C3—C2—H2A120.2C12—C11—H11A117.4
C1—C2—H2A120.2C11—C12—C13124.49 (17)
C2—C3—C4121.53 (19)C11—C12—S1123.74 (15)
C2—C3—H3A119.2C13—C12—S1111.77 (14)
C4—C3—H3A119.2C14—C13—C12108.83 (19)
C5—C4—C3119.69 (18)C14—C13—H13A125.6
C5—C4—H4A120.2C12—C13—H13A125.6
C3—C4—H4A120.2C15—C14—C13114.4 (2)
C4—C5—C6120.20 (18)C15—C14—H14A122.8
C4—C5—H5A119.9C13—C14—H14A122.8
C6—C5—H5A119.9C14—C15—S1113.38 (17)
C5—C6—C1119.91 (18)C14—C15—H15A123.3
C5—C6—C7121.09 (17)S1—C15—H15A123.3
C1—C6—C7118.99 (17)N1—C16—H16A109.5
C8—C7—C6120.12 (17)N1—C16—H16B109.5
C8—C7—H7A119.9H16A—C16—H16B109.5
C6—C7—H7A119.9N1—C16—H16C109.5
C7—C8—C9120.69 (18)H16A—C16—H16C109.5
C7—C8—H8A119.7H16B—C16—H16C109.5
C9—C8—H8A119.7
C9—N1—C1—C2−176.75 (17)C1—N1—C9—C8−5.6 (3)
C16—N1—C1—C23.6 (3)C16—N1—C9—C8173.99 (16)
C9—N1—C1—C63.5 (3)C1—N1—C9—C10173.83 (16)
C16—N1—C1—C6−176.05 (16)C16—N1—C9—C10−6.6 (2)
N1—C1—C2—C3178.41 (17)C7—C8—C9—N13.2 (3)
C6—C1—C2—C3−1.9 (3)C7—C8—C9—C10−176.23 (17)
C1—C2—C3—C40.5 (3)N1—C9—C10—C11166.39 (17)
C2—C3—C4—C50.8 (3)C8—C9—C10—C11−14.2 (3)
C3—C4—C5—C6−0.6 (3)C9—C10—C11—C12−178.56 (17)
C4—C5—C6—C1−0.8 (3)C10—C11—C12—C13−179.42 (18)
C4—C5—C6—C7−179.96 (18)C10—C11—C12—S11.4 (3)
N1—C1—C6—C5−178.25 (16)C15—S1—C12—C11178.33 (17)
C2—C1—C6—C52.0 (3)C15—S1—C12—C13−0.98 (15)
N1—C1—C6—C70.9 (3)C11—C12—C13—C14−177.85 (18)
C2—C1—C6—C7−178.77 (17)S1—C12—C13—C141.5 (2)
C5—C6—C7—C8175.96 (18)C12—C13—C14—C15−1.3 (3)
C1—C6—C7—C8−3.2 (3)C13—C14—C15—S10.6 (3)
C6—C7—C8—C91.2 (3)C12—S1—C15—C140.22 (19)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C10—H10A···S10.932.803.189 (2)106
C11—H11A···I1i0.933.063.934 (2)157
C16—H16B···I1ii0.963.063.962 (2)156

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z.

Footnotes

1This paper is dedicated to the late Her Royal Highness Princess Galyani Vadhana Krom Luang Naradhiwas Rajanagarindra for her patronage of science in Thailand.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS2311).

References

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