organic compounds
2-[(E)-2-(4-Methoxyphenyl)ethenyl]-1-methylpyridinium iodide
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
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
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Data collection: APEX2 (Bruker, 2004); cell 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
10.1107/S1600536813031929/hb7162sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536813031929/hb7162Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536813031929/hb7162Isup3.cml
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
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).All hydrogen atoms were fixed geometrically (C—H 0.93–0.98 Å) and refined as riding, with Uiso(H) = 1.2–1.5 Ueq(C).
Data collection: APEX2 (Bruker, 2004); cell
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).C15H16NO+·I− | Z = 2 |
Mr = 353.19 | F(000) = 348 |
Triclinic, P1 | Dx = 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 |
Bruker APEXII CCD diffractometer | 2470 independent reflections |
Radiation source: fine-focus sealed tube | 2363 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
phi and ω scans | θmax = 25.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −8→6 |
Tmin = 0.613, Tmax = 0.737 | k = −10→10 |
8523 measured reflections | l = −12→14 |
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(Fo2) + (0.0211P)2 + 0.414P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
2470 reflections | Δρmax = 0.31 e Å−3 |
165 parameters | Δρmin = −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) |
C15H16NO+·I− | γ = 103.781 (2)° |
Mr = 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)° |
Bruker APEXII CCD diffractometer | 2470 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 2363 reflections with I > 2σ(I) |
Tmin = 0.613, Tmax = 0.737 | Rint = 0.024 |
8523 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 0 restraints |
wR(F2) = 0.052 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.31 e Å−3 |
2470 reflections | Δρmin = −0.59 e Å−3 |
165 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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) |
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. |
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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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).