4-{2-[4-(Dimethyl­amino)­phen­yl]ethen­yl}-1-methyl­pyridinium 3,5-dicarb­oxy­benzene­sulfonate methanol monosolvate

Li, L.; Cui, H.; Yang, Z.; Tao, X.; Yang, H.

doi:10.1107/S1600536811054419

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o281

doi:10.1107/S1600536811054419

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4-{2-[4-(Dimethylamino)phenyl]ethenyl}-1-methylpyridinium 3,5-dicarboxybenzenesulfonate methanol monosolvate

Liang Li,^a Huijuan Cui,^a Zhou Yang,^a ^* Xutang Tao ^b and Huai Yang ^a

^aDepartment of Materials Physics and Chemistry, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, People's Republic of China, and ^bState Key Laboratory of Crystal Materials, Shandong University, Jinan, 250100, People's Republic of China
^*Correspondence e-mail: yangz@ustb.edu.cn

(Received 28 October 2011; accepted 18 December 2011; online 7 January 2012)

In the crystal structure of the title solvated salt, C₁₆H₁₉N₂⁺·C₈H₅O₇S⁻·CH₃OH, the anions and the methanol solvent molecules are linked by O—H⋯O hydrogen bonds. The cations and anions are packed as alternate layers parallel to (11 $[\overline2]$ ). The crystal structure is further stabilized by a π–π interaction between the pyridinium and benzene rings of the cations, with a centroid–centroid distance of 3.5492 (4) Å.

Related literature

The title compound was synthesized as part of our continuing research on the nonlinear optical properties of DAS (4-N,N-dimethylamino-4′-N′-methylstilbazolium) derivatives. For the synthesis, see: Okada et al. (1990 ). For background to non-linear optical materials, see: Bosshard et al. (1995 ); Nalwa & Miyata (1997 ); Yang, Mutter et al. (2007 ); Ruiz et al. (2006 ). For the effects of different substituents of benzene sulfonate on its non-linear optical properties, see: Okada et al. (2003 ); Yang, Wörle et al. (2007 ); Ogawa et al. (2008 ), Yang et al. (2005 ). For standard bond-lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₆H₁₉N₂⁺·C₈H₅O₇S⁻·CH₄O
M_r = 516.55
Triclinic, $[P \overline 1]$
a = 7.5277 (12) Å
b = 10.5517 (17) Å
c = 16.467 (3) Å
α = 106.750 (7)°
β = 97.504 (8)°
γ = 100.273 (8)°
V = 1209.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 173 K
0.45 × 0.31 × 0.22 mm

Data collection

Rigaku Saturn724+ CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ) T_min = 0.629, T_max = 1.000
15622 measured reflections
5523 independent reflections
5192 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.116
S = 1.13
5523 reflections
332 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O6ⁱ	0.84	1.89	2.6796 (18)	156
O4—H4A⋯O8ⁱⁱ	0.84	1.79	2.6156 (18)	168
O8—H8⋯O7ⁱⁱⁱ	0.84	1.86	2.6897 (18)	169
Symmetry codes: (i) -x, -y+1, -z+2; (ii) -x, -y, -z+1; (iii) x+1, y, z.

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811054419/ez2270sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811054419/ez2270Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811054419/ez2270Isup3.cdx

Supporting information file. DOI: 10.1107/S1600536811054419/ez2270Isup4.cml

checkCIF report

Comment top

During the last three decades, nonlinear optical materials have been of considerable interest for their potential applications such as frequency conversion, electro-optic modulation and THz generation (Bosshard et al., 1995; Nalwa & Miyata, 1997; Yang, Mutter et al., 2007). In order to create efficient NLO materials, both the molecular and bulk properties must be optimized (Yang et al., 2005; Ruiz et al., 2006; Yang, Wörle et al., 2007). The title compound was synthesized as part of our continuing research on the nonlinear optical properties of DAS (4-N, N-dimethylamino-4'-N'-methyl-stilbazolium) derivatives.

Fig. 1 illustrates the molecular structure of the title compound together with the atomic numbering scheme. The unit cell of the title compound contains two asymmetric units, each consisting of one C₁₆H₁₉N₂⁺ cation, one C₈H₅O₇S^- anion and one methanol molecule. The bond distances and angles in both the cation and anion are in normal ranges (Allen et al., 1987). In the crystal structure, atoms O4, O6, O7 and O8 of the anion are involved in O—H···O interactions. The cations and anions are stacked in a parallel manner and form alternating layers parallel to the (112) plane. The crystal structure is further stabilized by a π···π interaction between the pyridinium and C3–C8 benzene rings with a centroid–centroid distance of 3.5492 (4) Å, which combine with the intermolecular O—H···O interactions to form a three-dimensional network.

Related literature top

The title compound was synthesized as part of our continuing research on the nonlinear optical properties of DAS (4-N,N-dimethylamino-4'-N'-methylstilbazolium) derivatives. For the synthesis, see: Okada et al. (1990). For background to non-linear optical materials, see: Bosshard et al. (1995); Nalwa & Miyata (1997); Yang, Mutter et al. (2007); Ruiz et al. (2006). For the effects of different substituents of benzene sulfonate on its non-linear optical properties, see: Okada et al. (2003); Yang, Wörle et al. (2007); Ogawa et al. (2008), Yang et al. (2005). For standard bond-lengths, see: Allen et al. (1987).

Experimental top

4-{2-[4-(Dimethylamino)phenyl]ethenyl}-1-methylpyridinium 3,5-dicarboxybenzenesulfonate was prepared by the metathesization of 4-N,N-dimethylamino-4'-N'-methyl-stilbazolium iodide (Okada et al., 1990) with the sodium salt of the 3,5-dicarboxybenzenesulfonic acid. The title compound was then recrystallized from methanol to get high purity material for crystal growth. 4-{2-[4-(Dimethylamino)phenyl]ethenyl}-1-methylpyridinium 3,5-dicarboxybenzenesulfonate: yield 72%; ¹H-NMR (400 MHz, DMSO-d₆): 8.67 (d, 2H, J= 6.8Hz, C₅H₄N), 8.39 (s, 1H, C₆H₃SO₃^-), 8.34 (d, 2H, C₆H₃SO₃^-), 8.03(d, 2H, J= 6.8Hz, C₅H₄N), 7.91 (d, 1H, J= 16.0Hz, CH), 7.59(d, 2H, J= 8.4Hz, C₆H₃SO₃^-), 7.17 (d, 1H, J= 16.0Hz, CH), 6.79 (d, 2H, J= 8.8Hz, C₆H₄), 4.16 (s, 3H, NMe), 3.01 (s, 6H, NMe₂). C, H, N analysis calcd. for C₂₄H₂₄N₂O₇S: C 59.49, H 4.99, N 5.78; found: C 59.39, H 5.02, N 5.79. Crystals were obtained by slow cooling method from 45°C to room temperature in methanol.

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound showing the atom numbering scheme and 50% probability displacement ellipsoids.
	Fig. 2. A packing diagram of the title compound showing the hydrogen bonds as dashed lines.

4-{2-[4-(Dimethylamino)phenyl]ethenyl}-1-methylpyridinium 3,5-dicarboxybenzenesulfonate methanol monosolvate top

Crystal data top

C₁₆H₁₉N₂⁺·C₈H₅O₇S⁻·CH₄O	Z = 2
M_r = 516.55	F(000) = 544
Triclinic, P1	D_x = 1.419 Mg m⁻³
a = 7.5277 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.5517 (17) Å	Cell parameters from 4222 reflections
c = 16.467 (3) Å	θ = 1.3–27.5°
α = 106.750 (7)°	µ = 0.19 mm⁻¹
β = 97.504 (8)°	T = 173 K
γ = 100.273 (8)°	Block, red
V = 1209.2 (3) Å³	0.45 × 0.31 × 0.22 mm

Data collection top

Rigaku Saturn724+ CCD diffractometer	5523 independent reflections
Radiation source: fine-focus sealed tube	5192 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.5°, θ_min = 2.8°
ω scans at fixed χ = 45°	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	k = −13→13
T_min = 0.629, T_max = 1.000	l = −21→21
15622 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0477P)² + 0.4666P] where P = (F_o² + 2F_c²)/3
5523 reflections	(Δ/σ)_max = 0.001
332 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₁₆H₁₉N₂⁺·C₈H₅O₇S⁻·CH₄O	γ = 100.273 (8)°
M_r = 516.55	V = 1209.2 (3) Å³
Triclinic, P1	Z = 2
a = 7.5277 (12) Å	Mo Kα radiation
b = 10.5517 (17) Å	µ = 0.19 mm⁻¹
c = 16.467 (3) Å	T = 173 K
α = 106.750 (7)°	0.45 × 0.31 × 0.22 mm
β = 97.504 (8)°

Data collection top

Rigaku Saturn724+ CCD diffractometer	5523 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	5192 reflections with I > 2σ(I)
T_min = 0.629, T_max = 1.000	R_int = 0.037
15622 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.13	Δρ_max = 0.33 e Å⁻³
5523 reflections	Δρ_min = −0.33 e Å⁻³
332 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
S1	−0.38860 (5)	0.41490 (4)	0.77513 (3)	0.02588 (12)
O1	0.1455 (2)	0.37615 (12)	0.99887 (8)	0.0390 (3)
H1	0.2036	0.3798	1.0470	0.059*
O2	0.1780 (2)	0.16194 (13)	0.96041 (8)	0.0420 (3)
O3	−0.09373 (18)	−0.12371 (12)	0.64695 (8)	0.0350 (3)
O4	−0.28863 (18)	−0.04200 (13)	0.57227 (8)	0.0346 (3)
H4A	−0.2926	−0.1141	0.5327	0.052*
O5	−0.55084 (17)	0.36035 (13)	0.80299 (9)	0.0374 (3)
O6	−0.28648 (18)	0.54879 (12)	0.83184 (8)	0.0347 (3)
O7	−0.42469 (17)	0.41121 (12)	0.68482 (8)	0.0332 (3)
O8	0.2880 (2)	0.24475 (14)	0.56382 (8)	0.0436 (4)
H8	0.3854	0.2890	0.5993	0.065*
N1	0.3505 (2)	−0.25772 (15)	0.60065 (10)	0.0338 (3)
N2	0.9237 (2)	0.38403 (14)	1.25311 (10)	0.0313 (3)
C1	0.4220 (3)	−0.37550 (19)	0.56160 (13)	0.0406 (4)
H1C	0.3964	−0.4424	0.5918	0.061*
H1A	0.5552	−0.3472	0.5662	0.061*
H1B	0.3626	−0.4162	0.5006	0.061*
C2	0.2606 (3)	−0.1979 (2)	0.54209 (12)	0.0401 (4)
H2B	0.3443	−0.1152	0.5424	0.060*
H2A	0.1488	−0.1752	0.5610	0.060*
H2C	0.2280	−0.2631	0.4835	0.060*
C3	0.4215 (2)	−0.18111 (16)	0.68546 (11)	0.0261 (3)
C4	0.3830 (2)	−0.05246 (17)	0.72159 (11)	0.0281 (3)
H4	0.3044	−0.0190	0.6870	0.034*
C5	0.4577 (2)	0.02533 (16)	0.80627 (11)	0.0271 (3)
H5	0.4301	0.1116	0.8288	0.033*
C6	0.5736 (2)	−0.02072 (16)	0.85963 (11)	0.0271 (3)
C7	0.6059 (2)	−0.15028 (17)	0.82433 (11)	0.0297 (4)
H7	0.6799	−0.1853	0.8599	0.036*
C8	0.5340 (2)	−0.22835 (16)	0.73985 (11)	0.0297 (4)
H8A	0.5606	−0.3151	0.7180	0.036*
C9	0.6622 (2)	0.05654 (17)	0.94810 (11)	0.0290 (4)
H9	0.7296	0.0107	0.9785	0.035*
C10	0.6608 (2)	0.18460 (17)	0.99228 (11)	0.0296 (4)
H10	0.5937	0.2334	0.9642	0.036*
C11	0.7569 (2)	0.25224 (17)	1.08083 (11)	0.0282 (3)
C12	0.7411 (2)	0.38370 (18)	1.12496 (12)	0.0325 (4)
H12	0.6721	0.4299	1.0956	0.039*
C13	0.8239 (2)	0.44591 (18)	1.20961 (12)	0.0333 (4)
H13	0.8107	0.5347	1.2384	0.040*
C14	0.9459 (3)	0.25904 (18)	1.21244 (12)	0.0351 (4)
H14	1.0186	0.2166	1.2432	0.042*
C15	0.8659 (2)	0.19230 (17)	1.12795 (12)	0.0333 (4)
H15	0.8840	0.1044	1.1006	0.040*
C16	1.0116 (3)	0.4516 (2)	1.34462 (12)	0.0421 (5)
H16B	0.9368	0.5113	1.3731	0.063*
H16C	1.1346	0.5056	1.3485	0.063*
H16A	1.0221	0.3828	1.3732	0.063*
C17	0.1147 (2)	0.25092 (16)	0.94444 (11)	0.0280 (3)
C18	−0.1751 (2)	−0.03581 (16)	0.64270 (10)	0.0256 (3)
C19	−0.0110 (2)	0.23178 (16)	0.86173 (10)	0.0242 (3)
C20	−0.1150 (2)	0.32637 (15)	0.85514 (10)	0.0242 (3)
H20	−0.1007	0.4069	0.9023	0.029*
C21	−0.2395 (2)	0.30264 (15)	0.77944 (10)	0.0231 (3)
C22	−0.2594 (2)	0.18634 (15)	0.70939 (10)	0.0241 (3)
H22	−0.3434	0.1714	0.6574	0.029*
C23	−0.1550 (2)	0.09165 (15)	0.71595 (10)	0.0236 (3)
C24	−0.0322 (2)	0.11394 (16)	0.79225 (10)	0.0248 (3)
H24	0.0373	0.0487	0.7970	0.030*
C25	0.1596 (3)	0.19091 (19)	0.60747 (12)	0.0368 (4)
H25A	0.1064	0.0948	0.5753	0.055*
H25C	0.0616	0.2410	0.6118	0.055*
H25B	0.2218	0.1996	0.6656	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0280 (2)	0.02105 (19)	0.0269 (2)	0.00778 (15)	−0.00144 (16)	0.00678 (15)
O1	0.0533 (8)	0.0281 (6)	0.0274 (6)	0.0160 (6)	−0.0121 (6)	0.0009 (5)
O2	0.0555 (8)	0.0343 (7)	0.0324 (7)	0.0236 (6)	−0.0088 (6)	0.0042 (5)
O3	0.0403 (7)	0.0317 (6)	0.0295 (6)	0.0159 (5)	0.0021 (5)	0.0017 (5)
O4	0.0414 (7)	0.0339 (7)	0.0227 (6)	0.0112 (6)	−0.0017 (5)	0.0020 (5)
O5	0.0325 (7)	0.0365 (7)	0.0499 (8)	0.0159 (5)	0.0121 (6)	0.0171 (6)
O6	0.0427 (7)	0.0219 (6)	0.0335 (7)	0.0094 (5)	−0.0085 (6)	0.0055 (5)
O7	0.0386 (7)	0.0299 (6)	0.0284 (6)	0.0083 (5)	−0.0059 (5)	0.0101 (5)
O8	0.0445 (8)	0.0437 (8)	0.0262 (6)	−0.0102 (6)	0.0031 (6)	0.0001 (6)
N1	0.0385 (8)	0.0296 (7)	0.0305 (8)	0.0129 (6)	0.0022 (6)	0.0042 (6)
N2	0.0292 (7)	0.0294 (7)	0.0306 (8)	0.0019 (6)	0.0038 (6)	0.0064 (6)
C1	0.0514 (12)	0.0325 (9)	0.0338 (10)	0.0152 (8)	0.0048 (9)	0.0027 (8)
C2	0.0436 (11)	0.0466 (11)	0.0281 (9)	0.0186 (9)	0.0003 (8)	0.0065 (8)
C3	0.0260 (8)	0.0239 (8)	0.0274 (8)	0.0048 (6)	0.0058 (7)	0.0069 (6)
C4	0.0286 (8)	0.0272 (8)	0.0318 (9)	0.0102 (7)	0.0061 (7)	0.0123 (7)
C5	0.0296 (8)	0.0230 (7)	0.0304 (8)	0.0079 (6)	0.0096 (7)	0.0081 (6)
C6	0.0276 (8)	0.0269 (8)	0.0280 (8)	0.0048 (6)	0.0079 (7)	0.0106 (6)
C7	0.0327 (9)	0.0301 (8)	0.0303 (9)	0.0107 (7)	0.0057 (7)	0.0135 (7)
C8	0.0356 (9)	0.0229 (8)	0.0337 (9)	0.0106 (7)	0.0096 (7)	0.0101 (7)
C9	0.0304 (9)	0.0297 (8)	0.0295 (9)	0.0072 (7)	0.0074 (7)	0.0126 (7)
C10	0.0294 (9)	0.0298 (8)	0.0323 (9)	0.0080 (7)	0.0067 (7)	0.0130 (7)
C11	0.0261 (8)	0.0284 (8)	0.0300 (9)	0.0032 (6)	0.0085 (7)	0.0095 (7)
C12	0.0320 (9)	0.0296 (8)	0.0368 (9)	0.0092 (7)	0.0046 (7)	0.0118 (7)
C13	0.0320 (9)	0.0267 (8)	0.0389 (10)	0.0072 (7)	0.0067 (8)	0.0066 (7)
C14	0.0360 (10)	0.0310 (9)	0.0374 (10)	0.0089 (7)	0.0017 (8)	0.0114 (7)
C15	0.0385 (10)	0.0257 (8)	0.0345 (9)	0.0098 (7)	0.0058 (8)	0.0071 (7)
C16	0.0416 (11)	0.0423 (11)	0.0315 (10)	0.0009 (9)	0.0004 (8)	0.0034 (8)
C17	0.0295 (8)	0.0271 (8)	0.0267 (8)	0.0116 (7)	0.0024 (7)	0.0057 (6)
C18	0.0243 (8)	0.0284 (8)	0.0229 (8)	0.0049 (6)	0.0049 (6)	0.0070 (6)
C19	0.0246 (8)	0.0247 (7)	0.0233 (8)	0.0066 (6)	0.0040 (6)	0.0075 (6)
C20	0.0266 (8)	0.0209 (7)	0.0240 (8)	0.0051 (6)	0.0039 (6)	0.0062 (6)
C21	0.0229 (7)	0.0216 (7)	0.0261 (8)	0.0057 (6)	0.0044 (6)	0.0094 (6)
C22	0.0238 (8)	0.0256 (8)	0.0226 (7)	0.0050 (6)	0.0030 (6)	0.0082 (6)
C23	0.0237 (7)	0.0238 (7)	0.0230 (8)	0.0051 (6)	0.0061 (6)	0.0067 (6)
C24	0.0261 (8)	0.0250 (7)	0.0251 (8)	0.0096 (6)	0.0056 (6)	0.0080 (6)
C25	0.0352 (10)	0.0354 (9)	0.0347 (10)	0.0039 (8)	0.0056 (8)	0.0062 (8)

Geometric parameters (Å, º) top

S1—O5	1.4427 (13)	C7—C8	1.375 (2)
S1—O6	1.4572 (12)	C7—H7	0.9500
S1—O7	1.4643 (13)	C8—H8A	0.9500
S1—C21	1.7801 (16)	C9—C10	1.340 (2)
O1—C17	1.325 (2)	C9—H9	0.9500
O1—H1	0.8400	C10—C11	1.449 (2)
O2—C17	1.203 (2)	C10—H10	0.9500
O3—C18	1.212 (2)	C11—C12	1.402 (2)
O4—C18	1.326 (2)	C11—C15	1.406 (2)
O4—H4A	0.8400	C12—C13	1.364 (3)
O8—C25	1.412 (2)	C12—H12	0.9500
O8—H8	0.8400	C13—H13	0.9500
N1—C3	1.375 (2)	C14—C15	1.364 (3)
N1—C1	1.455 (2)	C14—H14	0.9500
N1—C2	1.456 (2)	C15—H15	0.9500
N2—C13	1.345 (2)	C16—H16B	0.9800
N2—C14	1.347 (2)	C16—H16C	0.9800
N2—C16	1.473 (2)	C16—H16A	0.9800
C1—H1C	0.9800	C17—C19	1.493 (2)
C1—H1A	0.9800	C18—C23	1.494 (2)
C1—H1B	0.9800	C19—C20	1.393 (2)
C2—H2B	0.9800	C19—C24	1.394 (2)
C2—H2A	0.9800	C20—C21	1.388 (2)
C2—H2C	0.9800	C20—H20	0.9500
C3—C8	1.406 (2)	C21—C22	1.390 (2)
C3—C4	1.414 (2)	C22—C23	1.396 (2)
C4—C5	1.380 (2)	C22—H22	0.9500
C4—H4	0.9500	C23—C24	1.392 (2)
C5—C6	1.402 (2)	C24—H24	0.9500
C5—H5	0.9500	C25—H25A	0.9800
C6—C7	1.401 (2)	C25—H25C	0.9800
C6—C9	1.449 (2)	C25—H25B	0.9800

O5—S1—O6	114.32 (8)	C12—C11—C15	116.21 (16)
O5—S1—O7	113.04 (8)	C12—C11—C10	120.18 (16)
O6—S1—O7	111.46 (7)	C15—C11—C10	123.60 (16)
O5—S1—C21	105.50 (7)	C13—C12—C11	120.71 (17)
O6—S1—C21	106.09 (7)	C13—C12—H12	119.6
O7—S1—C21	105.58 (7)	C11—C12—H12	119.6
C17—O1—H1	109.5	N2—C13—C12	121.34 (16)
C18—O4—H4A	109.5	N2—C13—H13	119.3
C25—O8—H8	109.5	C12—C13—H13	119.3
C3—N1—C1	119.25 (15)	N2—C14—C15	121.23 (17)
C3—N1—C2	119.96 (15)	N2—C14—H14	119.4
C1—N1—C2	116.88 (15)	C15—C14—H14	119.4
C13—N2—C14	119.76 (16)	C14—C15—C11	120.71 (16)
C13—N2—C16	120.98 (16)	C14—C15—H15	119.6
C14—N2—C16	119.25 (16)	C11—C15—H15	119.6
N1—C1—H1C	109.5	N2—C16—H16B	109.5
N1—C1—H1A	109.5	N2—C16—H16C	109.5
H1C—C1—H1A	109.5	H16B—C16—H16C	109.5
N1—C1—H1B	109.5	N2—C16—H16A	109.5
H1C—C1—H1B	109.5	H16B—C16—H16A	109.5
H1A—C1—H1B	109.5	H16C—C16—H16A	109.5
N1—C2—H2B	109.5	O2—C17—O1	123.90 (16)
N1—C2—H2A	109.5	O2—C17—C19	123.72 (15)
H2B—C2—H2A	109.5	O1—C17—C19	112.37 (13)
N1—C2—H2C	109.5	O3—C18—O4	123.48 (15)
H2B—C2—H2C	109.5	O3—C18—C23	123.32 (15)
H2A—C2—H2C	109.5	O4—C18—C23	113.19 (14)
N1—C3—C8	121.18 (15)	C20—C19—C24	119.86 (15)
N1—C3—C4	121.36 (15)	C20—C19—C17	120.65 (14)
C8—C3—C4	117.45 (15)	C24—C19—C17	119.37 (14)
C5—C4—C3	121.16 (15)	C21—C20—C19	119.82 (14)
C5—C4—H4	119.4	C21—C20—H20	120.1
C3—C4—H4	119.4	C19—C20—H20	120.1
C4—C5—C6	121.17 (15)	C20—C21—C22	120.65 (14)
C4—C5—H5	119.4	C20—C21—S1	119.61 (12)
C6—C5—H5	119.4	C22—C21—S1	119.54 (12)
C7—C6—C5	117.35 (15)	C21—C22—C23	119.52 (15)
C7—C6—C9	118.11 (15)	C21—C22—H22	120.2
C5—C6—C9	124.54 (15)	C23—C22—H22	120.2
C8—C7—C6	122.09 (16)	C24—C23—C22	120.01 (14)
C8—C7—H7	119.0	C24—C23—C18	118.89 (14)
C6—C7—H7	119.0	C22—C23—C18	121.09 (14)
C7—C8—C3	120.72 (15)	C23—C24—C19	120.12 (15)
C7—C8—H8A	119.6	C23—C24—H24	119.9
C3—C8—H8A	119.6	C19—C24—H24	119.9
C10—C9—C6	128.01 (16)	O8—C25—H25A	109.5
C10—C9—H9	116.0	O8—C25—H25C	109.5
C6—C9—H9	116.0	H25A—C25—H25C	109.5
C9—C10—C11	123.11 (16)	O8—C25—H25B	109.5
C9—C10—H10	118.4	H25A—C25—H25B	109.5
C11—C10—H10	118.4	H25C—C25—H25B	109.5

C1—N1—C3—C8	−12.7 (3)	C10—C11—C15—C14	−176.93 (16)
C2—N1—C3—C8	−169.80 (16)	O2—C17—C19—C20	163.92 (17)
C1—N1—C3—C4	167.82 (16)	O1—C17—C19—C20	−14.8 (2)
C2—N1—C3—C4	10.8 (3)	O2—C17—C19—C24	−12.2 (3)
N1—C3—C4—C5	−178.64 (15)	O1—C17—C19—C24	169.03 (15)
C8—C3—C4—C5	1.9 (2)	C24—C19—C20—C21	0.2 (2)
C3—C4—C5—C6	−0.3 (3)	C17—C19—C20—C21	−175.99 (15)
C4—C5—C6—C7	−1.9 (2)	C19—C20—C21—C22	−1.2 (2)
C4—C5—C6—C9	177.82 (16)	C19—C20—C21—S1	173.64 (12)
C5—C6—C7—C8	2.5 (2)	O5—S1—C21—C20	−89.52 (14)
C9—C6—C7—C8	−177.17 (15)	O6—S1—C21—C20	32.14 (15)
C6—C7—C8—C3	−1.0 (3)	O7—S1—C21—C20	150.54 (13)
N1—C3—C8—C7	179.29 (16)	O5—S1—C21—C22	85.32 (14)
C4—C3—C8—C7	−1.2 (2)	O6—S1—C21—C22	−153.02 (13)
C7—C6—C9—C10	174.95 (17)	O7—S1—C21—C22	−34.61 (14)
C5—C6—C9—C10	−4.7 (3)	C20—C21—C22—C23	1.0 (2)
C6—C9—C10—C11	−179.27 (15)	S1—C21—C22—C23	−173.75 (12)
C9—C10—C11—C12	−176.31 (16)	C21—C22—C23—C24	0.0 (2)
C9—C10—C11—C15	2.3 (3)	C21—C22—C23—C18	178.81 (14)
C15—C11—C12—C13	−1.9 (3)	O3—C18—C23—C24	2.3 (2)
C10—C11—C12—C13	176.88 (16)	O4—C18—C23—C24	−176.68 (14)
C14—N2—C13—C12	1.1 (3)	O3—C18—C23—C22	−176.44 (16)
C16—N2—C13—C12	−179.62 (17)	O4—C18—C23—C22	4.5 (2)
C11—C12—C13—N2	0.5 (3)	C22—C23—C24—C19	−1.0 (2)
C13—N2—C14—C15	−1.2 (3)	C18—C23—C24—C19	−179.82 (14)
C16—N2—C14—C15	179.51 (17)	C20—C19—C24—C23	0.9 (2)
N2—C14—C15—C11	−0.3 (3)	C17—C19—C24—C23	177.13 (15)
C12—C11—C15—C14	1.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O6ⁱ	0.84	1.89	2.6796 (18)	156
O4—H4A···O8ⁱⁱ	0.84	1.79	2.6156 (18)	168
O8—H8···O7ⁱⁱⁱ	0.84	1.86	2.6897 (18)	169

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₉N₂⁺·C₈H₅O₇S⁻·CH₄O
M_r	516.55
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	7.5277 (12), 10.5517 (17), 16.467 (3)
α, β, γ (°)	106.750 (7), 97.504 (8), 100.273 (8)
V (Å³)	1209.2 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.19
Crystal size (mm)	0.45 × 0.31 × 0.22

Data collection
Diffractometer	Rigaku Saturn724+ CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2008)
T_min, T_max	0.629, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15622, 5523, 5192
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.116, 1.13
No. of reflections	5523
No. of parameters	332
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.33

Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O6ⁱ	0.84	1.89	2.6796 (18)	155.5
O4—H4A···O8ⁱⁱ	0.84	1.79	2.6156 (18)	168.3
O8—H8···O7ⁱⁱⁱ	0.84	1.86	2.6897 (18)	169.2

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

Acknowledgements

The authors thank the Natural Science Foundation (grant No. 50803005), the Fundamental Research Funds for the Central Universities, the Scientific Research Foundation for Returned Overseas Chinese Scholars and the National Natural Science Fund for Distinguished Young Scholars (grant No. 51025313).

References

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Volume 68| Part 2| February 2012| Page o281

doi:10.1107/S1600536811054419

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

4-{2-[4-(Di­methyl­amino)­phen­yl]ethen­yl}-1-methyl­pyridinium 3,5-dicarb­­oxy­benzene­sulfonate methanol monosolvate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4-{2-[4-(Dimethylamino)phenyl]ethenyl}-1-methylpyridinium 3,5-dicarboxybenzenesulfonate methanol monosolvate