2-[(E)-2-(4-Meth­oxy­phen­yl)ethen­yl]-1-methyl­pyridinium iodide

Senthil, K.; Kalainathan, S.; RubanKumar, A.; Ramkumar, V.; Podder, J.

doi:10.1107/S1600536813031929

organic compounds

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Volume 69| Part 12| December 2013| Page o1848

doi:10.1107/S1600536813031929

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2-[(E)-2-(4-Methoxyphenyl)ethenyl]-1-methylpyridinium iodide

K. Senthil,^a S. Kalainathan,^a A. RubanKumar,^a V. Ramkumar ^b and Jiban Podder ^c ^*

^aCentre for Crystal Growth, School of Advanced Sciences, VIT University, Vellore, Tamil Nadu, India, ^bDepartment of Chemistry, IIT Madras, Chennai 600 036, TamilNadu, India, and ^cDepartment of Physics, Bangladesh University of Engineering and Technology, Dhaka 1000, Bangladesh
^*Correspondence e-mail: jpodder59@gmail.com

(Received 13 November 2013; accepted 22 November 2013; online 30 November 2013)

In the title molecular salt, C₁₆H₁₀NO⁺·I⁻, the dihedral angle between the pyridinium and benzene rings is 6.61 (8)°. In the crystal, the cation is linked to the anion by a C—H⋯I interaction arising from the activated aromatic C atom adjacent to the N⁺ cation.

CCDC reference: 973302

Related literature

For background to organic non-linear optical materials, see: Jagannathan et al. (2007 ); Williams (1984 ). For a related structure, see: Chantrapromma et al. (2010 ).

Experimental

Crystal data

C₁₅H₁₆NO⁺·I⁻
M_r = 353.19
Triclinic, $[P \overline 1]$
a = 7.1760 (3) Å
b = 8.6895 (4) Å
c = 12.1555 (6) Å
α = 92.645 (2)°
β = 92.115 (2)°
γ = 103.781 (2)°
V = 734.47 (6) Å³
Z = 2
Mo Kα radiation
μ = 2.17 mm⁻¹
T = 298 K
0.25 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.613, T_max = 0.737
8523 measured reflections
2470 independent reflections
2363 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.020
wR(F²) = 0.052
S = 1.09
2470 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯I1ⁱ	0.93	2.96	3.872 (3)	168
Symmetry code: (i) x-1, y-1, z.

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 973302

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813031929/hb7162sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813031929/hb7162Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813031929/hb7162Isup3.cml

checkCIF report

Comment top

In recent years, the design of new organic nonlinear optical (NLO) materials have been studied (e.g. Jagannathan et al., 2007). As part of our stuies in this area, the title pyridinium derivative compound was synthesized,. It crystallizes in the centrosymmetric Pī triclinic space group, so it does not exhibit second-order nonlinear optical properties (Williams, 1984).

The cation is essentially planar and exist in E configuration. The dihedral angle between the pyridinium and benzene rings is 6.16 (8)°. Bond lengths and angles are comparable with those for closely related structure (Chantrapromma et al., 2010). In the crystal, the cation is linked to the anion by a C—H···I interaction (Table 1).

Related literature top

For background to organic non-linear optical materials, see: Jagannathan et al. (2007); Williams (1984). For a related structure, see: Chantrapromma et al. (2010).

Experimental top

The title compound was prepared by mixing 1:1 molar ratio of solutions of 1,2-dimethylpyridinium iodide (7.052 g, 30 mmol), 4-methoxy benzaldehyde (3.7 ml, 30 mmol) and piperidine (5 drops) in hot methanol (20 ml). The resulting mixture was refluxed at 60°C for 8 h to give yellowish crystalline product, which was filtered off and washed with diethyl ether and dried. Yellow needle-shaped single crystals of the title compound suitable for X-ray structure determination were obtained by recrystallization (three times) from methanol–acetonitrile (1:1) mixture by slow evaporation of the solvent at ambient temperature over several days (m.p. 514–516 K).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. ORTEP of the molecule with atoms represented as 30% probability ellipsoids.

2-[(E)-2-(4-Methoxyphenyl)ethenyl]-1-methylpyridinium iodide top

Crystal data top

C₁₅H₁₆NO⁺·I⁻	Z = 2
M_r = 353.19	F(000) = 348
Triclinic, P1	D_x = 1.597 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1760 (3) Å	Cell parameters from 8234 reflections
b = 8.6895 (4) Å	θ = 2.4–28.4°
c = 12.1555 (6) Å	µ = 2.17 mm⁻¹
α = 92.645 (2)°	T = 298 K
β = 92.115 (2)°	Slab, yellow
γ = 103.781 (2)°	0.25 × 0.20 × 0.15 mm
V = 734.47 (6) Å³

Data collection top

Bruker APEXII CCD diffractometer	2470 independent reflections
Radiation source: fine-focus sealed tube	2363 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
phi and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −8→6
T_min = 0.613, T_max = 0.737	k = −10→10
8523 measured reflections	l = −12→14

Refinement top

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)] = 0.020	H-atom parameters constrained
wR(F²) = 0.052	w = 1/[σ²(F_o²) + (0.0211P)² + 0.414P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
2470 reflections	Δρ_max = 0.31 e Å⁻³
165 parameters	Δρ_min = −0.59 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0288 (14)

Crystal data top

C₁₅H₁₆NO⁺·I⁻	γ = 103.781 (2)°
M_r = 353.19	V = 734.47 (6) Å³
Triclinic, P1	Z = 2
a = 7.1760 (3) Å	Mo Kα radiation
b = 8.6895 (4) Å	µ = 2.17 mm⁻¹
c = 12.1555 (6) Å	T = 298 K
α = 92.645 (2)°	0.25 × 0.20 × 0.15 mm
β = 92.115 (2)°

Data collection top

Bruker APEXII CCD diffractometer	2470 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2363 reflections with I > 2σ(I)
T_min = 0.613, T_max = 0.737	R_int = 0.024
8523 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	0 restraints
wR(F²) = 0.052	H-atom parameters constrained
S = 1.09	Δρ_max = 0.31 e Å⁻³
2470 reflections	Δρ_min = −0.59 e Å⁻³
165 parameters

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

	x	y	z	U_iso*/U_eq
C1	−0.1445 (4)	0.0480 (3)	0.8878 (2)	0.0494 (6)
H1	−0.2582	−0.0296	0.8742	0.059*
C2	−0.1376 (4)	0.1673 (3)	0.9651 (2)	0.0560 (7)
H2	−0.2451	0.1722	1.0043	0.067*
C3	0.0321 (5)	0.2809 (3)	0.9843 (2)	0.0598 (7)
H3	0.0397	0.3633	1.0372	0.072*
C4	0.1896 (4)	0.2736 (3)	0.9260 (2)	0.0537 (6)
H4	0.3039	0.3503	0.9400	0.064*
C5	0.1799 (4)	0.1513 (3)	0.84555 (19)	0.0419 (5)
C6	0.3386 (4)	0.1382 (3)	0.7790 (2)	0.0468 (6)
H6	0.3297	0.0432	0.7383	0.056*
C7	0.4961 (4)	0.2531 (3)	0.7722 (2)	0.0460 (5)
H7	0.5055	0.3449	0.8167	0.055*
C8	0.6550 (3)	0.2503 (3)	0.7027 (2)	0.0422 (5)
C9	0.8189 (4)	0.3743 (3)	0.7121 (2)	0.0497 (6)
H9	0.8233	0.4583	0.7632	0.060*
C10	0.9754 (4)	0.3779 (3)	0.6488 (2)	0.0497 (6)
H10	1.0838	0.4618	0.6580	0.060*
C11	0.9687 (4)	0.2554 (3)	0.5718 (2)	0.0497 (6)
C13	0.8062 (4)	0.1296 (3)	0.5607 (3)	0.0622 (7)
H13	0.8019	0.0465	0.5088	0.075*
C14	0.6536 (4)	0.1264 (3)	0.6246 (2)	0.0549 (6)
H14	0.5470	0.0408	0.6163	0.066*
C15	1.2825 (4)	0.3695 (4)	0.5113 (3)	0.0652 (8)
H15A	1.2501	0.4670	0.4943	0.098*
H15B	1.3708	0.3459	0.4594	0.098*
H15C	1.3410	0.3800	0.5845	0.098*
C16	−0.0104 (4)	−0.0956 (3)	0.7487 (2)	0.0561 (7)
H16A	−0.1383	−0.1617	0.7491	0.084*
H16B	0.0805	−0.1563	0.7676	0.084*
H16C	0.0128	−0.0567	0.6766	0.084*
N1	0.0107 (3)	0.0400 (2)	0.83019 (16)	0.0409 (4)
O1	1.1126 (3)	0.2441 (3)	0.50511 (19)	0.0726 (6)
I1	0.43035 (2)	0.689767 (18)	0.803640 (16)	0.05847 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0449 (13)	0.0580 (14)	0.0471 (14)	0.0149 (11)	0.0023 (11)	0.0090 (11)
C2	0.0638 (17)	0.0679 (16)	0.0428 (14)	0.0267 (14)	0.0105 (12)	0.0086 (12)
C3	0.085 (2)	0.0533 (15)	0.0434 (14)	0.0208 (14)	0.0134 (14)	0.0002 (11)
C4	0.0653 (16)	0.0454 (13)	0.0461 (14)	0.0048 (12)	0.0071 (12)	0.0004 (11)
C5	0.0502 (13)	0.0407 (11)	0.0355 (12)	0.0111 (10)	0.0015 (10)	0.0082 (9)
C6	0.0512 (14)	0.0437 (12)	0.0445 (13)	0.0096 (11)	0.0032 (11)	−0.0003 (10)
C7	0.0524 (14)	0.0402 (12)	0.0460 (14)	0.0123 (10)	0.0012 (11)	0.0025 (10)
C8	0.0435 (12)	0.0410 (11)	0.0425 (13)	0.0114 (10)	−0.0032 (10)	0.0045 (9)
C9	0.0563 (15)	0.0415 (12)	0.0475 (14)	0.0053 (11)	0.0016 (12)	−0.0025 (10)
C10	0.0460 (13)	0.0471 (13)	0.0510 (15)	0.0022 (10)	−0.0012 (11)	0.0014 (11)
C11	0.0401 (13)	0.0570 (14)	0.0507 (15)	0.0100 (11)	−0.0010 (11)	−0.0012 (11)
C13	0.0506 (15)	0.0616 (16)	0.0677 (19)	0.0053 (13)	0.0024 (13)	−0.0226 (14)
C14	0.0422 (13)	0.0537 (14)	0.0620 (17)	0.0012 (11)	−0.0002 (12)	−0.0104 (12)
C15	0.0443 (15)	0.0802 (19)	0.0671 (19)	0.0053 (14)	0.0059 (13)	0.0111 (15)
C16	0.0487 (14)	0.0548 (14)	0.0596 (17)	0.0057 (12)	0.0012 (12)	−0.0122 (12)
N1	0.0442 (11)	0.0444 (10)	0.0349 (10)	0.0125 (8)	−0.0016 (8)	0.0045 (8)
O1	0.0491 (11)	0.0816 (14)	0.0795 (15)	0.0041 (10)	0.0153 (10)	−0.0219 (11)
I1	0.04875 (13)	0.04564 (12)	0.07815 (17)	0.00721 (8)	0.00877 (9)	−0.00920 (8)

Geometric parameters (Å, º) top

C1—N1	1.351 (3)	C9—C10	1.380 (4)
C1—C2	1.357 (4)	C9—H9	0.9300
C1—H1	0.9300	C10—C11	1.375 (4)
C2—C3	1.377 (4)	C10—H10	0.9300
C2—H2	0.9300	C11—O1	1.355 (3)
C3—C4	1.369 (4)	C11—C13	1.393 (4)
C3—H3	0.9300	C13—C14	1.362 (4)
C4—C5	1.397 (4)	C13—H13	0.9300
C4—H4	0.9300	C14—H14	0.9300
C5—N1	1.361 (3)	C15—O1	1.426 (3)
C5—C6	1.445 (3)	C15—H15A	0.9600
C6—C7	1.326 (4)	C15—H15B	0.9600
C6—H6	0.9300	C15—H15C	0.9600
C7—C8	1.448 (4)	C16—N1	1.479 (3)
C7—H7	0.9300	C16—H16A	0.9600
C8—C9	1.390 (3)	C16—H16B	0.9600
C8—C14	1.400 (4)	C16—H16C	0.9600

N1—C1—C2	121.2 (2)	C11—C10—H10	120.5
N1—C1—H1	119.4	C9—C10—H10	120.5
C2—C1—H1	119.4	O1—C11—C10	124.9 (2)
C1—C2—C3	118.6 (3)	O1—C11—C13	115.6 (2)
C1—C2—H2	120.7	C10—C11—C13	119.5 (2)
C3—C2—H2	120.7	C14—C13—C11	121.0 (3)
C4—C3—C2	120.5 (3)	C14—C13—H13	119.5
C4—C3—H3	119.8	C11—C13—H13	119.5
C2—C3—H3	119.8	C13—C14—C8	120.9 (2)
C3—C4—C5	120.4 (3)	C13—C14—H14	119.6
C3—C4—H4	119.8	C8—C14—H14	119.6
C5—C4—H4	119.8	O1—C15—H15A	109.5
N1—C5—C4	117.4 (2)	O1—C15—H15B	109.5
N1—C5—C6	119.1 (2)	H15A—C15—H15B	109.5
C4—C5—C6	123.5 (2)	O1—C15—H15C	109.5
C7—C6—C5	124.1 (2)	H15A—C15—H15C	109.5
C7—C6—H6	117.9	H15B—C15—H15C	109.5
C5—C6—H6	117.9	N1—C16—H16A	109.5
C6—C7—C8	126.7 (2)	N1—C16—H16B	109.5
C6—C7—H7	116.6	H16A—C16—H16B	109.5
C8—C7—H7	116.6	N1—C16—H16C	109.5
C9—C8—C14	117.0 (2)	H16A—C16—H16C	109.5
C9—C8—C7	120.0 (2)	H16B—C16—H16C	109.5
C14—C8—C7	123.0 (2)	C1—N1—C5	121.9 (2)
C10—C9—C8	122.7 (2)	C1—N1—C16	117.2 (2)
C10—C9—H9	118.7	C5—N1—C16	120.9 (2)
C8—C9—H9	118.7	C11—O1—C15	118.6 (2)
C11—C10—C9	119.0 (2)

N1—C1—C2—C3	−0.2 (4)	C9—C10—C11—C13	−1.1 (4)
C1—C2—C3—C4	0.3 (4)	O1—C11—C13—C14	178.9 (3)
C2—C3—C4—C5	0.6 (4)	C10—C11—C13—C14	0.2 (5)
C3—C4—C5—N1	−1.5 (4)	C11—C13—C14—C8	0.6 (5)
C3—C4—C5—C6	178.4 (2)	C9—C8—C14—C13	−0.6 (4)
N1—C5—C6—C7	167.1 (2)	C7—C8—C14—C13	179.6 (3)
C4—C5—C6—C7	−12.8 (4)	C2—C1—N1—C5	−0.9 (4)
C5—C6—C7—C8	−176.5 (2)	C2—C1—N1—C16	179.3 (2)
C6—C7—C8—C9	−174.0 (3)	C4—C5—N1—C1	1.7 (3)
C6—C7—C8—C14	5.8 (4)	C6—C5—N1—C1	−178.2 (2)
C14—C8—C9—C10	−0.2 (4)	C4—C5—N1—C16	−178.4 (2)
C7—C8—C9—C10	179.5 (2)	C6—C5—N1—C16	1.6 (3)
C8—C9—C10—C11	1.1 (4)	C10—C11—O1—C15	−2.1 (4)
C9—C10—C11—O1	−179.6 (3)	C13—C11—O1—C15	179.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···I1ⁱ	0.93	2.96	3.872 (3)	168

Symmetry code: (i) x−1, y−1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···I1ⁱ	0.93	2.96	3.872 (3)	168

Symmetry code: (i) x−1, y−1, z.

Acknowledgements

The authors thank the DRDO, Government of India, for financial support. They also thank the VIT University management, Vellore, for their constant support and encouragement and acknowledge the Department of Chemistry, IIT Madras, for the data collection.

References

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