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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3098–o3099.
Published online 2010 November 6. doi:  10.1107/S1600536810043254
PMCID: PMC3011747

1-Methyl-2-[(E)-2,4,5-trimeth­oxy­styr­yl]­pyridinium iodide1

Abstract

In the title compound, C17H20NO3 +·I, the cation exists in the E configuration. The pyridinium and benzene rings are close to coplanar, with a dihedral angle of 7.43 (12)° between them. The three meth­oxy groups of 2,4,5-trimeth­oxy­phenyl are essentially coplanar with the benzene plane, with C—O—C—C torsion angles of 1.0 (3), −1.9 (3) and 3.6 (3)°. A weak intra­molecular C—H(...)O inter­action generates an S(6) ring motif. In the crystal, the cations are stacked in columns in an anti­parallel manner along the a axis through π–π inter­actions, with a centroid–centroid distance of 3.7714 (16) Å. The iodide anion is situated between the columns and linked to the cation by a weak C—H(...)I inter­action.

Related literature

For bond-length data, see: Allen et al. (1987 [triangle]). For related literature on hydrogen-bond motifs, see: Bernstein et al. (1995 [triangle]). For background to nonlinear optical properties and applications of pyridinium and quinolinium derivatives, see: Chanawanno et al. (2010 [triangle]); Chantrapromma et al. (2010 [triangle]); Ruanwas et al. (2010 [triangle]); Williams (1984 [triangle]). For related structures, see: Chanawanno et al. (2008 [triangle]); Fun et al. (2009 [triangle]); Kaewmanee et al. (2010 [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-66-o3098-scheme1.jpg

Experimental

Crystal data

  • C17H20NO3 +·I
  • M r = 413.24
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3098-efi1.jpg
  • a = 8.9109 (1) Å
  • b = 10.3551 (1) Å
  • c = 10.8201 (2) Å
  • α = 113.382 (1)°
  • β = 109.243 (1)°
  • γ = 96.831 (1)°
  • V = 828.51 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.94 mm−1
  • T = 100 K
  • 0.37 × 0.32 × 0.18 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.534, T max = 0.720
  • 29408 measured reflections
  • 4827 independent reflections
  • 4686 reflections with I > 2σ(I)
  • R int = 0.024

Refinement

  • R[F 2 > 2σ(F 2)] = 0.028
  • wR(F 2) = 0.084
  • S = 1.14
  • 4827 reflections
  • 203 parameters
  • H-atom parameters constrained
  • Δρmax = 1.85 e Å−3
  • Δρmin = −0.33 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/S1600536810043254/is2612sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810043254/is2612Isup2.hkl

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

Acknowledgments

CM thanks the Development and Promotion of Science and Technology Talents Project for a study grant. Financial support from the Prince of Songkla University is acknowledged. The authors also thank Universiti Sains Malaysia for the research university grant No. 1001/PFIZIK/811160.

supplementary crystallographic information

Comment

We have previously synthesized several pyridinium and quinolinium derivatives to study their antibacterial activities and non-linear optical (NLO) properties (Chanawanno et al., 2008, 2010; Chantrapromma et al., 2010; Fun et al., 2009; Ruanwas et al., 2010). During the course of antibacterial activities and NLO properties of synthetic compounds, the title pyridinium derivative was synthesized and its single crystal x-ray structural study was undertaken in order to establish the conformation of the various groups and the space group. The title compound (I) crystallized in the centrosymmetric triclinic P-1 space group and therefore (I) does not exhibit second order NLO properties (Williams, 1984). In addition (I) was also tested for antibacterial activities against the Bacillus subtilis, Enterococcus faecalis, Staphylococcus aureus, Methicillin-Resistant Staphylococcus aureus, Vancomycin-Resistant Enterococcus faecalis, Pseudomonas aeruginosa, Salmonella typhi and Shigella sonnei, and found inactive. Herein the crystal structure of (I) is reported.

Figure 1 shows the asymmetric unit of (I) which consists of a C17H20NO3+ cation and an I- anion. The cation exists in the E configuration with respect to the C6═C7 double bond [1.350 (3) Å] with the torsion angle C5–C6–C7–C8 = -179.5 (2)°. The pyridinium and benzene rings are nearly coplanar with the ethenyl bridge with the dihedral angle between the pyridinium and benzene ring being 7.43 (12)°. The three methoxy groups of the 2,4,5-trimethoxyphenyl are essentially co-planar [C17–O3–C12–C13, C16–O2–C11–C10 and C15–O1–C9–C10 torsion angles of 1.0 (3), -1.9 (3) and 3.6 (3)°, respectively]. An intramolecular C6—H6A···O1 weak interactions generates an S(6) ring motif (Bernstein et al., 1995) which helps to stabilize the planarity of the molecular structure. The methyl units of two methoxy groups at atoms C9 and C11 point towards whereas at atoms C11 and C12 point away from each other (Fig. 1). It is interesting to note that there is steric interaction between the methyl group of 1-methylpyridinium and the methoxy group at atom C9 but the intramolecular C6—H6A···O1 weak interaction which formed the S(6) ring motif is more preferable than the S(5) ring motif comparing to the structure which the 2,4,5-trimethoxyphenyl unit rotate 180° around the C7–C8 bond to form S(5) ring motif of C7—H7A···O1 weak interaction. The bond lengths of cation in (I) are in normal ranges (Allen et al., 1987) and comparable to those in related structures (Chanawanno et al., 2008; Fun et al., 2009; Kaewmanee et al., 2010).

In the crystal packing (Fig. 2), the cations are stacked in an anti-parallel manner along the a axis by π–π interactions with the Cg1···Cg2ii distance of 3.7714 (16) Å [symmetry code: (ii) 1 - x, -y, 1 - z]; Cg1 and Cg2 are the centroids of N1/C1–C5 and C8–C13 rings, respectively. The iodide anions are located in the interstitials of the cations and linked to the cations by C—H···I weak interactions (Table 1).

Experimental

The title compound (I) was prepared by mixing 1:1:1 molar ratio solutions of 1,2-dimethylpyridinium iodide (0.50 g, 2.13 mmol), 2,4,5-trimethoxybenzaldehyde (0.417 g, 2.13 mmol) and piperidine (0.21 ml, 2.13 mmol) in hot methanol (20 ml). The resulting solution was refluxed for 5 hr under a nitrogen atmosphere. The resultant solid which formed was filtered off and washed with diethyl ether. Orange block-shaped single crystals of (I) suitable for x-ray structure determination were recrystallized from methanol by slow evaporation at room temperature over a few weeks (m.p. 544-545 K).

Refinement

All H atoms were positioned geometrically and allowed to ride on their parent atoms, with d(C—H) = 0.93 Å for aromatic 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 1.46 Å from I1 and the deepest hole is located at 1.00 Å from C6.

Figures

Fig. 1.
The molecular structure of the title compound, with 50% probability displacement ellipsoids and the atom-numbering scheme. Hydrogen bond was drawn as dashed line.
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

C17H20NO3+·IZ = 2
Mr = 413.24F(000) = 412
Triclinic, P1Dx = 1.656 Mg m3
Hall symbol: -P 1Melting point = 544–545 K
a = 8.9109 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.3551 (1) ÅCell parameters from 4827 reflections
c = 10.8201 (2) Åθ = 2.2–30.0°
α = 113.382 (1)°µ = 1.94 mm1
β = 109.243 (1)°T = 100 K
γ = 96.831 (1)°Block, orange
V = 828.51 (2) Å30.37 × 0.32 × 0.18 mm

Data collection

Bruker APEXII CCD area-detector diffractometer4827 independent reflections
Radiation source: sealed tube4686 reflections with I > 2σ(I)
graphiteRint = 0.024
[var phi] and ω scansθmax = 30.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −12→12
Tmin = 0.534, Tmax = 0.720k = −14→13
29408 measured reflectionsl = −15→15

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)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H-atom parameters constrained
S = 1.14w = 1/[σ2(Fo2) + (0.0418P)2 + 1.7349P] where P = (Fo2 + 2Fc2)/3
4827 reflections(Δ/σ)max = 0.001
203 parametersΔρmax = 1.85 e Å3
0 restraintsΔρmin = −0.33 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
I10.63632 (2)0.272468 (17)0.263674 (17)0.01981 (6)
O10.1870 (2)0.19738 (18)0.43228 (18)0.0142 (3)
O20.0422 (2)0.40374 (18)0.85063 (19)0.0141 (3)
O30.1169 (2)0.20276 (19)0.92393 (19)0.0152 (3)
N10.3476 (2)−0.2139 (2)0.1812 (2)0.0116 (3)
C10.3923 (3)−0.3317 (3)0.1060 (3)0.0164 (4)
H1A0.3941−0.34800.01560.020*
C20.4348 (3)−0.4269 (3)0.1614 (3)0.0179 (4)
H2A0.4628−0.50850.10840.022*
C30.4351 (3)−0.3990 (3)0.2983 (3)0.0157 (4)
H3A0.4656−0.46110.33870.019*
C40.3902 (3)−0.2792 (2)0.3738 (2)0.0133 (4)
H4A0.3916−0.26040.46570.016*
C50.3422 (3)−0.1847 (2)0.3140 (2)0.0105 (3)
C60.2895 (3)−0.0589 (2)0.3851 (2)0.0118 (4)
H6A0.27270.00480.34420.014*
C70.2639 (3)−0.0305 (2)0.5083 (2)0.0109 (3)
H7A0.2832−0.09670.54560.013*
C80.2103 (3)0.0895 (2)0.5905 (2)0.0101 (3)
C90.1697 (3)0.2006 (2)0.5538 (2)0.0109 (4)
C100.1146 (3)0.3083 (2)0.6399 (2)0.0117 (4)
H10A0.08870.38140.61480.014*
C110.0984 (3)0.3064 (2)0.7627 (2)0.0111 (4)
C120.1396 (3)0.1966 (2)0.8021 (2)0.0116 (4)
C130.1940 (3)0.0915 (2)0.7170 (2)0.0112 (4)
H13A0.22100.01930.74350.013*
C140.3022 (3)−0.1177 (3)0.1125 (3)0.0177 (4)
H14A0.3121−0.15450.01980.027*
H14B0.3754−0.01980.17710.027*
H14C0.1899−0.11650.09600.027*
C150.1497 (3)0.3104 (3)0.3933 (3)0.0196 (5)
H15A0.17850.30100.31270.029*
H15B0.21240.40490.47690.029*
H15C0.03330.30120.36410.029*
C160.0013 (3)0.5189 (3)0.8167 (3)0.0163 (4)
H16A−0.03560.58040.88690.024*
H16B−0.08550.47690.71890.024*
H16C0.09770.57660.82140.024*
C170.1636 (3)0.0946 (3)0.9660 (3)0.0197 (4)
H17A0.14150.10611.05030.030*
H17B0.27980.10620.99070.030*
H17C0.1008−0.00160.88530.030*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
I10.02761 (10)0.01804 (9)0.01905 (9)0.00876 (6)0.01258 (7)0.01051 (7)
O10.0254 (8)0.0137 (7)0.0124 (7)0.0114 (6)0.0120 (6)0.0092 (6)
O20.0208 (8)0.0128 (7)0.0159 (7)0.0108 (6)0.0126 (6)0.0075 (6)
O30.0240 (8)0.0171 (8)0.0139 (7)0.0115 (6)0.0132 (6)0.0102 (6)
N10.0147 (8)0.0123 (8)0.0100 (8)0.0061 (6)0.0071 (6)0.0052 (7)
C10.0202 (10)0.0179 (10)0.0138 (9)0.0106 (8)0.0107 (8)0.0054 (8)
C20.0220 (11)0.0166 (10)0.0176 (10)0.0115 (8)0.0115 (9)0.0058 (8)
C30.0185 (10)0.0143 (10)0.0189 (10)0.0093 (8)0.0101 (8)0.0089 (8)
C40.0171 (9)0.0136 (9)0.0131 (9)0.0076 (7)0.0082 (8)0.0074 (8)
C50.0117 (8)0.0107 (8)0.0097 (8)0.0043 (7)0.0056 (7)0.0041 (7)
C60.0151 (9)0.0109 (9)0.0110 (9)0.0062 (7)0.0066 (7)0.0049 (7)
C70.0132 (8)0.0101 (8)0.0108 (9)0.0052 (7)0.0060 (7)0.0046 (7)
C80.0122 (8)0.0101 (8)0.0098 (8)0.0048 (7)0.0061 (7)0.0046 (7)
C90.0138 (9)0.0114 (9)0.0093 (8)0.0050 (7)0.0058 (7)0.0052 (7)
C100.0149 (9)0.0111 (9)0.0120 (9)0.0061 (7)0.0070 (7)0.0064 (7)
C110.0122 (8)0.0107 (9)0.0117 (9)0.0053 (7)0.0071 (7)0.0041 (7)
C120.0138 (9)0.0134 (9)0.0109 (9)0.0060 (7)0.0072 (7)0.0066 (7)
C130.0142 (9)0.0115 (9)0.0109 (9)0.0055 (7)0.0066 (7)0.0062 (7)
C140.0277 (11)0.0193 (10)0.0157 (10)0.0122 (9)0.0133 (9)0.0120 (9)
C150.0355 (13)0.0173 (10)0.0165 (10)0.0149 (9)0.0146 (9)0.0125 (9)
C160.0205 (10)0.0128 (9)0.0216 (11)0.0100 (8)0.0128 (9)0.0089 (8)
C170.0298 (12)0.0228 (11)0.0190 (11)0.0142 (10)0.0154 (9)0.0152 (9)

Geometric parameters (Å, °)

O1—C91.362 (2)C7—H7A0.9300
O1—C151.432 (3)C8—C91.407 (3)
O2—C111.358 (2)C8—C131.416 (3)
O2—C161.433 (3)C9—C101.399 (3)
O3—C121.377 (3)C10—C111.391 (3)
O3—C171.423 (3)C10—H10A0.9300
N1—C11.360 (3)C11—C121.411 (3)
N1—C51.366 (3)C12—C131.375 (3)
N1—C141.481 (3)C13—H13A0.9300
C1—C21.372 (3)C14—H14A0.9600
C1—H1A0.9300C14—H14B0.9600
C2—C31.391 (3)C14—H14C0.9600
C2—H2A0.9300C15—H15A0.9600
C3—C41.378 (3)C15—H15B0.9600
C3—H3A0.9300C15—H15C0.9600
C4—C51.406 (3)C16—H16A0.9600
C4—H4A0.9300C16—H16B0.9600
C5—C61.448 (3)C16—H16C0.9600
C6—C71.350 (3)C17—H17A0.9600
C6—H6A0.9300C17—H17B0.9600
C7—C81.451 (3)C17—H17C0.9600
C9—O1—C15118.29 (17)C9—C10—H10A119.8
C11—O2—C16117.54 (18)O2—C11—C10124.67 (19)
C12—O3—C17115.34 (17)O2—C11—C12115.43 (18)
C1—N1—C5122.11 (19)C10—C11—C12119.89 (19)
C1—N1—C14117.39 (19)C13—C12—O3125.15 (19)
C5—N1—C14120.50 (18)C13—C12—C11119.29 (19)
N1—C1—C2121.0 (2)O3—C12—C11115.53 (18)
N1—C1—H1A119.5C12—C13—C8122.16 (19)
C2—C1—H1A119.5C12—C13—H13A118.9
C1—C2—C3118.8 (2)C8—C13—H13A118.9
C1—C2—H2A120.6N1—C14—H14A109.5
C3—C2—H2A120.6N1—C14—H14B109.5
C4—C3—C2119.8 (2)H14A—C14—H14B109.5
C4—C3—H3A120.1N1—C14—H14C109.5
C2—C3—H3A120.1H14A—C14—H14C109.5
C3—C4—C5121.0 (2)H14B—C14—H14C109.5
C3—C4—H4A119.5O1—C15—H15A109.5
C5—C4—H4A119.5O1—C15—H15B109.5
N1—C5—C4117.30 (19)H15A—C15—H15B109.5
N1—C5—C6118.57 (19)O1—C15—H15C109.5
C4—C5—C6124.13 (19)H15A—C15—H15C109.5
C7—C6—C5122.6 (2)H15B—C15—H15C109.5
C7—C6—H6A118.7O2—C16—H16A109.5
C5—C6—H6A118.7O2—C16—H16B109.5
C6—C7—C8128.7 (2)H16A—C16—H16B109.5
C6—C7—H7A115.6O2—C16—H16C109.5
C8—C7—H7A115.6H16A—C16—H16C109.5
C9—C8—C13117.62 (18)H16B—C16—H16C109.5
C9—C8—C7126.06 (19)O3—C17—H17A109.5
C13—C8—C7116.29 (18)O3—C17—H17B109.5
O1—C9—C10122.56 (19)H17A—C17—H17B109.5
O1—C9—C8116.78 (18)O3—C17—H17C109.5
C10—C9—C8120.65 (19)H17A—C17—H17C109.5
C11—C10—C9120.37 (19)H17B—C17—H17C109.5
C11—C10—H10A119.8
C5—N1—C1—C2−0.2 (3)C7—C8—C9—O1−2.0 (3)
C14—N1—C1—C2−179.5 (2)C13—C8—C9—C10−0.3 (3)
N1—C1—C2—C3−1.5 (4)C7—C8—C9—C10178.1 (2)
C1—C2—C3—C41.3 (4)O1—C9—C10—C11179.8 (2)
C2—C3—C4—C50.6 (4)C8—C9—C10—C11−0.3 (3)
C1—N1—C5—C42.0 (3)C16—O2—C11—C10−1.9 (3)
C14—N1—C5—C4−178.8 (2)C16—O2—C11—C12178.99 (19)
C1—N1—C5—C6−178.5 (2)C9—C10—C11—O2−178.3 (2)
C14—N1—C5—C60.6 (3)C9—C10—C11—C120.8 (3)
C3—C4—C5—N1−2.2 (3)C17—O3—C12—C133.6 (3)
C3—C4—C5—C6178.4 (2)C17—O3—C12—C11−178.1 (2)
N1—C5—C6—C7173.0 (2)O2—C11—C12—C13178.53 (19)
C4—C5—C6—C7−7.7 (3)C10—C11—C12—C13−0.6 (3)
C5—C6—C7—C8−179.5 (2)O2—C11—C12—O30.1 (3)
C6—C7—C8—C91.7 (4)C10—C11—C12—O3−179.03 (19)
C6—C7—C8—C13−179.9 (2)O3—C12—C13—C8178.2 (2)
C15—O1—C9—C101.0 (3)C11—C12—C13—C80.0 (3)
C15—O1—C9—C8−178.9 (2)C9—C8—C13—C120.4 (3)
C13—C8—C9—O1179.63 (19)C7—C8—C13—C12−178.1 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C6—H6A···O10.932.192.819 (3)124
C14—H14A···I1i0.963.033.992 (3)177

Symmetry codes: (i) −x+1, −y, −z.

Footnotes

1This paper is dedicated to the late His Majesty King Chulalongkorn (King Rama V) of Thailand for his numerous reforms to modernize the country on the occasion of Chulalongkorn Day (Piyamaharaj Day) which fell on the 23rd October.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS2612).

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.
  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl 34, 1555–1573.
  • Bruker (2005). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chanawanno, K., Chantrapromma, S., Anantapong, T., Kanjana-Opas, A. & Fun, H.-K. (2010). Eur. J. Med. Chem 45, 4199–4208. [PubMed]
  • Chanawanno, K., Chantrapromma, S. & Fun, H.-K. (2008). Acta Cryst. E64, o1882–o1883. [PMC free article] [PubMed]
  • Chantrapromma, S., Chanawanno, K. & Fun, H.-K. (2010). Acta Cryst. E66, o1975–o1976. [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, o1934–o1935. [PMC free article] [PubMed]
  • Kaewmanee, N., Chanawanno, K., Chantrapromma, S. & Fun, H.-K. (2010). Acta Cryst. E66, o2639–o2640. [PMC free article] [PubMed]
  • Ruanwas, P., Kobkeatthawin, T., Chantrapromma, S., Fun, H.-K., Philip, R., Smijesh, N., Padaki, M. & Isloor, A. M. (2010). Synth. Met 160, 819–824.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
  • Williams, D. J. (1984). Angew. Chem. Int. Ed. Engl 23, 690–703.

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