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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o1934–o1935.
Published online 2009 July 18. doi:  10.1107/S1600536809027810
PMCID: PMC2977224

(E)-1-Methyl-2-styrylpyridinium iodide

Abstract

In the title compound, C14H14N+·I, the cation exists in an E configuration with respect to the ethenyl bond and is slightly twisted, the inter­planar angle between the pyridinium and phenyl rings of the cation being 4.8 (2)°. In the crystal packing, the cations are stacked in an anti­parallel fashion along the a axis by a π–π inter­action involving both pyridinium and phenyl rings; the centroid–centroid distance is 3.542 (3) Å. Each iodide ion is sandwiched between two cations. The cations and iodide anions are linked together by weak C—H(...)I inter­actions, giving rise to ladder-like ribbons along the a axis.

Related literature

For bond-length data, see: Allen et al. (1987 [triangle]). For background to non-linear optical materials research, see: Wenseleers et al. (1998 [triangle]). For related structures, see: Chanawanno et al. (2008 [triangle]); Chantrapromma et al. (2009a [triangle],b [triangle]); Fun et al. (2009 [triangle]). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer, (1986 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1934-scheme1.jpg

Experimental

Crystal data

  • C14H14N+·I
  • M r = 323.16
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1934-efi1.jpg
  • a = 7.0841 (1) Å
  • b = 10.0664 (2) Å
  • c = 19.1771 (3) Å
  • β = 109.017 (1)°
  • V = 1292.91 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.45 mm−1
  • T = 100 K
  • 0.28 × 0.18 × 0.13 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.552, T max = 0.735
  • 15764 measured reflections
  • 3753 independent reflections
  • 3186 reflections with I > 2σ(I)
  • R int = 0.031

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.107
  • S = 1.09
  • 3753 reflections
  • 146 parameters
  • H-atom parameters constrained
  • Δρmax = 1.53 e Å−3
  • Δρmin = −1.30 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; 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, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809027810/wn2338sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809027810/wn2338Isup2.hkl

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

Acknowledgments

The authors thank the Malaysian Government and Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012. KC thanks the Development and Promotion of Science and Technology Talents Project (DPST) for a study grant. SC thanks the Prince of Songkla University for financial support through the Crystal Materials Research Unit.

supplementary crystallographic information

Comment

In the search for new materials capable of nonlinear optical (NLO) applications, many studies have focused on organic molecules containing highly polarizable π-conjugated backbones (Wenseleers et al., 1998). During the course of our screening for NLO active organic compounds, we have previously reported the crystal structures of pyridinium derivatives (Chanawanno et al., 2008; Chantrapromma et al., 2009a,b); Fun et al., 2009). In this paper we report the synthesis of the title compound whose crystal structure was undertaken in order to establish the conformation and crystal packing. The title compound crystallized in centrosymmetric space group P21/c so it does not exhibit second-order nonlinear optical properties.

In the title compound, C14H14N+. I- (Fig. 1), the cation exists in an E configuration with respect to the ethenyl C6═C7 double bond [1.347 (6) Å]; the torsion angle C5–C6–C7–C8 is 178.5 (4)°. The cation is slightly twisted, the interplanar angle between the pyridinium and phenyl rings being 4.8 (2)°. The bond distances in the cation have normal values (Allen et al., 1987) and are comparable with closely related compounds (Chantrapromma et al., 2009a,b; Fun et al., 2009).

In the crystal packing (Fig. 2), the cations are stacked in an antiparallel fashion along the a axis by a π–π interaction with the Cg1···Cg2 distance = 3.542 (3) Å (symmetry code: 2-x, 1-y, 1-z); Cg1 and Cg2 are the centroids of the N1/C1–C5 and C8–C13 rings, respectively. Each iodide ion is sandwiched between two cations. The cations and iodide anions are linked together by weak C—H···I interactions, giving rise to ladder-like ribbons along the a axis (Table 1 and Fig. 2). The crystal structure is stabilized by C—H···I and π–π interactions.

Experimental

The title compound was prepared by mixing 1:1:1 molar ratio solutions of 1,2-dimethylpyridinium iodide (2 g, 8.5 mmol), benzaldehyde (0.86 ml, 8.5 mmol) and piperidine (0.84 ml, 8.5 mmol) in methanol (40 ml). The resulting solution was refluxed for 5 hours under a nitrogen atmosphere. A pale yellow solid of the resulting compound was formed, this was then filtered and washed with diethyl ether. Yellow needle-shaped single crystals of the title compound suitable for x-ray structure determination were recrystallized from methanol by slow evaporation at room temperature after several weeks, Mp. 505-506 K. Details of the stability of the temperature controller used in the data collection have been published earlier (Cosier & Glazer, 1986).

Refinement

All H atoms were positioned geometrically and allowed to ride on their parent atoms, with d(C-H) = 0.93 Å for aromatic C and CH and 0.96 Å for CH3 atoms. The Uiso values were constrained to be 1.5Ueq of the carrier atom for methyl H atoms and 1.2Ueq for the remaining H atoms. A rotating group model was used for the methyl groups. The highest residual electron density peak is located at 0.75 Å from I1 and the deepest hole is located at 0.67 Å from I1.

Figures

Fig. 1.
The molecular structure of the title compound, with 50% probability displacement ellipsoids and the atom-numbering scheme. Hydrogen atoms are drawn as spheres of arbitrary radius.
Fig. 2.
The crystal packing of the title compound, viewed down the b axis. Weak C—H···I interactions are shown as dashed lines.

Crystal data

C14H14N+·IF(000) = 632
Mr = 323.16Dx = 1.660 Mg m3
Monoclinic, P21/cMelting point = 505–506 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 7.0841 (1) ÅCell parameters from 3753 reflections
b = 10.0664 (2) Åθ = 2.3–30.0°
c = 19.1771 (3) ŵ = 2.45 mm1
β = 109.017 (1)°T = 100 K
V = 1292.91 (4) Å3Block, pale yellow
Z = 40.28 × 0.18 × 0.13 mm

Data collection

Bruker APEXII CCD area-detector diffractometer3753 independent reflections
Radiation source: sealed tube3186 reflections with I > 2σ(I)
graphiteRint = 0.031
[var phi] and ω scansθmax = 30.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −8→9
Tmin = 0.552, Tmax = 0.735k = −14→14
15764 measured reflectionsl = −26→26

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107H-atom parameters constrained
S = 1.09w = 1/[σ2(Fo2) + (0.037P)2 + 4.8574P] where P = (Fo2 + 2Fc2)/3
3753 reflections(Δ/σ)max < 0.001
146 parametersΔρmax = 1.53 e Å3
0 restraintsΔρmin = −1.30 e Å3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
I10.70838 (4)0.18319 (3)0.382571 (14)0.03436 (10)
N10.6191 (5)0.7789 (4)0.45127 (18)0.0298 (7)
C10.5059 (6)0.8350 (4)0.3870 (2)0.0327 (8)
H1A0.48300.92610.38510.039*
C20.4245 (6)0.7599 (5)0.3248 (2)0.0332 (8)
H2A0.34630.79930.28110.040*
C30.4607 (6)0.6242 (4)0.3281 (2)0.0305 (8)
H3A0.40940.57180.28630.037*
C40.5727 (6)0.5682 (4)0.3936 (2)0.0316 (8)
H4A0.59580.47720.39620.038*
C50.6529 (7)0.6466 (4)0.4568 (2)0.0328 (8)
C60.7642 (7)0.5934 (4)0.5286 (2)0.0346 (9)
H6A0.79460.64930.56940.041*
C70.8250 (6)0.4660 (5)0.5384 (2)0.0350 (9)
H7A0.78850.41310.49640.042*
C80.9420 (6)0.4001 (4)0.6074 (2)0.0272 (7)
C90.9771 (6)0.2630 (4)0.6079 (2)0.0299 (8)
H9A0.93100.21510.56410.036*
C101.0797 (6)0.1984 (4)0.6727 (3)0.0335 (9)
H10A1.10080.10730.67240.040*
C111.1507 (7)0.2682 (5)0.7377 (2)0.0365 (9)
H11A1.22250.22470.78100.044*
C121.1146 (7)0.4048 (5)0.7385 (2)0.0341 (9)
H12A1.15900.45160.78260.041*
C131.0130 (6)0.4704 (4)0.6736 (2)0.0291 (8)
H13A0.99200.56150.67420.035*
C140.7074 (7)0.8689 (5)0.5147 (2)0.0364 (9)
H14A0.84690.84920.53670.055*
H14B0.64090.85640.55050.055*
H14C0.69170.95930.49800.055*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
I10.04036 (17)0.03000 (15)0.02839 (14)0.00091 (11)0.00527 (11)−0.00118 (10)
N10.0326 (17)0.0315 (17)0.0280 (15)−0.0039 (14)0.0137 (14)−0.0016 (13)
C10.0287 (19)0.034 (2)0.036 (2)0.0047 (16)0.0115 (16)0.0009 (16)
C20.0278 (19)0.040 (2)0.0309 (19)0.0078 (17)0.0080 (16)0.0005 (17)
C30.0273 (18)0.037 (2)0.0278 (17)−0.0012 (16)0.0093 (15)−0.0019 (16)
C40.035 (2)0.028 (2)0.0306 (18)−0.0052 (16)0.0094 (16)0.0010 (15)
C50.038 (2)0.0277 (19)0.0304 (19)−0.0067 (16)0.0087 (17)0.0050 (15)
C60.037 (2)0.032 (2)0.035 (2)0.0006 (17)0.0126 (17)0.0000 (16)
C70.037 (2)0.033 (2)0.035 (2)−0.0014 (17)0.0115 (17)0.0006 (17)
C80.0288 (18)0.0266 (18)0.0270 (16)−0.0042 (15)0.0100 (14)0.0036 (14)
C90.0308 (19)0.0301 (19)0.0333 (19)−0.0038 (16)0.0166 (16)−0.0037 (15)
C100.031 (2)0.0222 (18)0.047 (2)0.0010 (15)0.0130 (18)0.0064 (16)
C110.033 (2)0.036 (2)0.036 (2)−0.0011 (18)0.0055 (17)0.0119 (18)
C120.037 (2)0.038 (2)0.0268 (18)−0.0043 (18)0.0097 (16)−0.0017 (16)
C130.0315 (19)0.0222 (17)0.0345 (19)0.0014 (15)0.0118 (16)0.0002 (14)
C140.047 (2)0.030 (2)0.032 (2)−0.0036 (19)0.0130 (18)−0.0053 (16)

Geometric parameters (Å, °)

N1—C51.352 (5)C7—H7A0.9300
N1—C11.355 (5)C8—C131.397 (5)
N1—C141.481 (5)C8—C91.402 (6)
C1—C21.370 (6)C9—C101.381 (6)
C1—H1A0.9300C9—H9A0.9300
C2—C31.387 (6)C10—C111.376 (6)
C2—H2A0.9300C10—H10A0.9300
C3—C41.369 (6)C11—C121.399 (7)
C3—H3A0.9300C11—H11A0.9300
C4—C51.402 (6)C12—C131.384 (6)
C4—H4A0.9300C12—H12A0.9300
C5—C61.448 (6)C13—H13A0.9300
C6—C71.347 (6)C14—H14A0.9600
C6—H6A0.9300C14—H14B0.9600
C7—C81.470 (6)C14—H14C0.9600
C5—N1—C1121.3 (4)C13—C8—C9118.8 (4)
C5—N1—C14121.4 (4)C13—C8—C7121.3 (4)
C1—N1—C14117.3 (4)C9—C8—C7119.8 (4)
N1—C1—C2121.2 (4)C10—C9—C8120.6 (4)
N1—C1—H1A119.4C10—C9—H9A119.7
C2—C1—H1A119.4C8—C9—H9A119.7
C1—C2—C3119.0 (4)C11—C10—C9120.4 (4)
C1—C2—H2A120.5C11—C10—H10A119.8
C3—C2—H2A120.5C9—C10—H10A119.8
C4—C3—C2119.4 (4)C10—C11—C12119.8 (4)
C4—C3—H3A120.3C10—C11—H11A120.1
C2—C3—H3A120.3C12—C11—H11A120.1
C3—C4—C5120.8 (4)C13—C12—C11120.2 (4)
C3—C4—H4A119.6C13—C12—H12A119.9
C5—C4—H4A119.6C11—C12—H12A119.9
N1—C5—C4118.4 (4)C12—C13—C8120.2 (4)
N1—C5—C6117.8 (4)C12—C13—H13A119.9
C4—C5—C6123.8 (4)C8—C13—H13A119.9
C7—C6—C5122.3 (4)N1—C14—H14A109.5
C7—C6—H6A118.8N1—C14—H14B109.5
C5—C6—H6A118.8H14A—C14—H14B109.5
C6—C7—C8128.1 (4)N1—C14—H14C109.5
C6—C7—H7A116.0H14A—C14—H14C109.5
C8—C7—H7A116.0H14B—C14—H14C109.5
C5—N1—C1—C2−1.3 (6)C4—C5—C6—C710.0 (7)
C14—N1—C1—C2177.6 (4)C5—C6—C7—C8178.5 (4)
N1—C1—C2—C3−0.4 (6)C6—C7—C8—C13−2.8 (7)
C1—C2—C3—C41.4 (6)C6—C7—C8—C9174.6 (4)
C2—C3—C4—C5−0.8 (6)C13—C8—C9—C100.2 (6)
C1—N1—C5—C41.9 (6)C7—C8—C9—C10−177.3 (4)
C14—N1—C5—C4−176.9 (4)C8—C9—C10—C11−0.7 (6)
C1—N1—C5—C6−175.9 (4)C9—C10—C11—C121.5 (7)
C14—N1—C5—C65.3 (6)C10—C11—C12—C13−1.9 (7)
C3—C4—C5—N1−0.8 (6)C11—C12—C13—C81.5 (6)
C3—C4—C5—C6176.8 (4)C9—C8—C13—C12−0.6 (6)
N1—C5—C6—C7−172.4 (4)C7—C8—C13—C12176.9 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C1—H1A···I1i0.933.053.799 (4)139
C14—H14A···I1ii0.963.043.996 (5)173

Symmetry codes: (i) x, y+1, z; (ii) −x+2, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WN2338).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Bruker (2005). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chanawanno, K., Chantrapromma, S. & Fun, H.-K. (2008). Acta Cryst. E64, o1882–o1883. [PMC free article] [PubMed]
  • Chantrapromma, S., Chanawanno, K. & Fun, H.-K. (2009a). Acta Cryst. E65, o1144–o1145. [PMC free article] [PubMed]
  • Chantrapromma, S., Chanawanno, K. & Fun, H.-K. (2009b). Acta Cryst E65, o1884-o1885. [PMC free article] [PubMed]
  • Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst.19, 105–107.
  • Fun, H.-K., Chanawanno, K. & Chantrapromma, S. (2009). Acta Cryst. E65, o1554–o1555. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
  • Wenseleers, W., Gerbrandij, A. W., Goovaerts, E., Garcia, M. H., Robalo, M. P., Mendes, P. J., Rodrigues, J. C. & Dias, A. R. (1998). J. Mater. Chem 8, 925–930.

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