4-[2-(4-But­oxy­phen­yl)ethen­yl]-1-methyl­pyridinium tosylate

Kumar, M.K.; Margret, S.M.; Chakkaravarthi, G.; Velmurugan, D.; Kumar, R.M.

doi:10.1107/S1600536813009616

organic compounds

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Volume 69| Part 5| May 2013| Page o709

https://doi.org/10.1107/S1600536813009616

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4-[2-(4-Butoxyphenyl)ethenyl]-1-methylpyridinium tosylate

M. Krishna Kumar,^a S. Mabel Margret,^a G. Chakkaravarthi,^b ^* D. Velmurugan ^c and R. Mohan Kumar ^a ^*

^aDepartment of Physics, Presidency College, Chennai 600 005, India, ^bDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India, and ^cCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Maraimalai Campus, Chennai 600 025, India
^*Correspondence e-mail: chakkaravarthi_2005@yahoo.com, mohan66@hotmail.com

(Received 7 April 2013; accepted 8 April 2013; online 13 April 2013)

In the title molecular salt, C₁₈H₂₂NO⁺·C₇H₇O₃S⁻, the dihedral angle between the aromatic rings in the cation is 10.00 (9)°; its alkyl side chain adopts an extended conformation. In the crystal, weak C—H⋯O and π–π [centroid–centroid distance = 3.7658 (17) Å] interactions link the components, generating a three-dimensional network.

Related literature

For molecular compounds with non-linear optical properties, see: Nalwa & Miyata (1997 ). For related structures, see: Krishnakumar et al. (2012 ); Sivakumar et al.(2012 ).

Experimental

Crystal data

C₁₈H₂₂NO⁺·C₇H₇O₃S⁻
M_r = 439.55
Monoclinic, P 2₁ /n
a = 9.0884 (6) Å
b = 6.4559 (5) Å
c = 39.827 (3) Å
β = 95.404 (3)°
V = 2326.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 295 K
0.28 × 0.24 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.954, T_max = 0.967
20608 measured reflections
5629 independent reflections
4258 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.069
wR(F²) = 0.160
S = 1.16
5629 reflections
291 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O4ⁱ	0.93	2.33	3.210 (3)	158
C4—H4⋯O3ⁱⁱ	0.93	2.56	3.412 (3)	153
C6—H6B⋯O3ⁱⁱⁱ	0.96	2.57	3.470 (4)	157
C8—H8⋯O3ⁱⁱ	0.93	2.55	3.418 (3)	156
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536813009616/hb7067sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813009616/hb7067Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813009616/hb7067Isup3.cml

checkCIF report

Comment top

In continuation of our studies of molecular compounds with potential non-linear optical properties, which could be used in optoelectronic and photonic devices (Nalwa & Miyata, 1997), we herewith report the crystal structure of the title compound, (I), (Fig. 1).

The geometric parameters of the cation and anion in (I) are comparable to those in previously reported structures (Krishnakumar et al., 2012; Sivakumar et al., 2012). The benzene ring and pyridinium ring makes a dihedral angle of 10.00 (9)°. in the cation.

In the crystal, the anions and cations are linked by weak C—H···O (Table 1 & Fig. 2) and π···π [Cg1···Cg2 (1/2+x,-1/2-y,1/2+z) = 3.7658 (17)Å; Cg1 and Cg2 are the centroids of the N1/C1-C5 and C9-C14 rings, respectively] interactions.

Related literature top

For molecular compounds with non-linear optical properties, see: Nalwa & Miyata (1997). For related structures, see: Krishnakumar et al. (2012); Sivakumar et al.(2012).

Experimental top

The 4-butoxy-4'-N'-methyl stilbazolium tosylate was synthesized by the condensation reaction. The stoichiometric amount of reagents 4-picoline (4.65 g, 5 mmol), methyl p-toluenesulfonate (9.31 g, 5 mmol), and p-butoxybenzaldehyde (8.64 ml, 5 mmol) were refluxed 20 hours in the presence of piperidine. Colourless blocks of (I) were grown by slow evaporation of a methanol solution.

Structure description top

For molecular compounds with non-linear optical properties, see: Nalwa & Miyata (1997). For related structures, see: Krishnakumar et al. (2012); Sivakumar et al.(2012).

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: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing of (I), viewed down [010]. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted.

4-[2-(4-Butoxyphenyl)ethenyl]-1-methylpyridinium 4-methylbenzenesulfonate top

Crystal data top

C₁₈H₂₂NO⁺·C₇H₇O₃S⁻	F(000) = 936
M_r = 439.55	D_x = 1.255 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4259 reflections
a = 9.0884 (6) Å	θ = 2.0–28.3°
b = 6.4559 (5) Å	µ = 0.17 mm⁻¹
c = 39.827 (3) Å	T = 295 K
β = 95.404 (3)°	Block, colourless
V = 2326.4 (2) Å³	0.28 × 0.24 × 0.20 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	5629 independent reflections
Radiation source: fine-focus sealed tube	4258 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω and φ scan	θ_max = 28.3°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.954, T_max = 0.967	k = −8→8
20608 measured reflections	l = −53→53

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)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.160	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ²(F_o²) + (0.0359P)² + 2.0379P] where P = (F_o² + 2F_c²)/3
5629 reflections	(Δ/σ)_max < 0.001
291 parameters	Δρ_max = 0.23 e Å⁻³
2 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

C₁₈H₂₂NO⁺·C₇H₇O₃S⁻	V = 2326.4 (2) Å³
M_r = 439.55	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.0884 (6) Å	µ = 0.17 mm⁻¹
b = 6.4559 (5) Å	T = 295 K
c = 39.827 (3) Å	0.28 × 0.24 × 0.20 mm
β = 95.404 (3)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	5629 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4258 reflections with I > 2σ(I)
T_min = 0.954, T_max = 0.967	R_int = 0.028
20608 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.069	2 restraints
wR(F²) = 0.160	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	Δρ_max = 0.23 e Å⁻³
5629 reflections	Δρ_min = −0.39 e Å⁻³
291 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
S1	0.50367 (7)	0.31025 (11)	0.192843 (17)	0.04861 (19)
O1	0.5412 (3)	1.3940 (4)	0.42984 (6)	0.0809 (7)
O2	0.5079 (3)	0.5330 (3)	0.19010 (6)	0.0789 (7)
O3	0.6435 (2)	0.2208 (4)	0.20606 (5)	0.0640 (6)
O4	0.3804 (2)	0.2348 (4)	0.20972 (5)	0.0664 (6)
N1	0.4977 (2)	0.0292 (3)	0.27689 (5)	0.0469 (5)
C1	0.3694 (3)	0.0849 (5)	0.28821 (7)	0.0573 (7)
H1	0.2863	0.0023	0.2833	0.069*
C2	0.3587 (3)	0.2596 (5)	0.30663 (7)	0.0575 (7)
H2	0.2683	0.2937	0.3144	0.069*
C3	0.4789 (3)	0.3888 (4)	0.31426 (6)	0.0466 (6)
C4	0.6110 (3)	0.3277 (5)	0.30151 (7)	0.0503 (6)
H4	0.6949	0.4097	0.3055	0.060*
C5	0.6177 (3)	0.1500 (4)	0.28339 (7)	0.0500 (6)
H5	0.7066	0.1114	0.2754	0.060*
C6	0.5076 (4)	−0.1583 (5)	0.25612 (7)	0.0612 (8)
H6A	0.4267	−0.2491	0.2596	0.092*
H6B	0.5993	−0.2279	0.2625	0.092*
H6C	0.5031	−0.1200	0.2328	0.092*
C7	0.4653 (3)	0.5724 (5)	0.33512 (7)	0.0556 (7)
H7	0.3736	0.5967	0.3429	0.067*
C8	0.5707 (3)	0.7068 (5)	0.34388 (7)	0.0519 (7)
H8	0.6614	0.6843	0.3354	0.062*
C9	0.5600 (3)	0.8877 (5)	0.36552 (6)	0.0497 (6)
C10	0.4379 (3)	0.9313 (6)	0.38288 (8)	0.0700 (9)
H10	0.3564	0.8437	0.3803	0.084*
C11	0.4343 (4)	1.0995 (6)	0.40360 (9)	0.0765 (10)
H11	0.3508	1.1248	0.4148	0.092*
C12	0.5539 (3)	1.2327 (5)	0.40816 (7)	0.0607 (8)
C13	0.6756 (3)	1.1942 (5)	0.39102 (8)	0.0653 (8)
H13	0.7565	1.2829	0.3935	0.078*
C14	0.6773 (3)	1.0237 (5)	0.37012 (7)	0.0580 (7)
H14	0.7605	0.9996	0.3587	0.070*
C15	0.6659 (4)	1.5244 (6)	0.43681 (8)	0.0738 (9)
H15A	0.6903	1.5913	0.4162	0.089*
H15B	0.7504	1.4430	0.4457	0.089*
C16	0.6299 (5)	1.6859 (6)	0.46230 (9)	0.0851 (11)
H16A	0.5430	1.7627	0.4535	0.102*
H16B	0.6073	1.6175	0.4829	0.102*
C17	0.7561 (6)	1.8339 (7)	0.47022 (10)	0.1014 (14)
H17A	0.7817	1.8957	0.4493	0.122*
H17B	0.8414	1.7567	0.4799	0.122*
C18	0.7232 (7)	2.0047 (8)	0.49432 (12)	0.133 (2)
H18A	0.6429	2.0875	0.4844	0.199*
H18B	0.8093	2.0900	0.4989	0.199*
H18C	0.6967	1.9451	0.5150	0.199*
C19	0.4720 (2)	0.2172 (4)	0.15089 (6)	0.0428 (6)
C20	0.4479 (4)	0.3501 (5)	0.12436 (8)	0.0613 (8)
C21	0.4179 (4)	0.2789 (6)	0.09167 (8)	0.0700 (9)
H21	0.4026	0.3738	0.0741	0.084*
C22	0.4105 (4)	0.0713 (6)	0.08467 (8)	0.0687 (9)
C23	0.4372 (4)	−0.0616 (5)	0.11138 (9)	0.0737 (10)
C24	0.4687 (3)	0.0078 (5)	0.14422 (8)	0.0597 (8)
H24	0.4875	−0.0869	0.1617	0.072*
C25	0.3715 (5)	−0.0092 (8)	0.04919 (10)	0.1049 (14)
H25A	0.4179	−0.1412	0.0467	0.157*
H25B	0.4056	0.0868	0.0332	0.157*
H25C	0.2663	−0.0243	0.0451	0.157*
H23	0.435 (4)	−0.2033 (19)	0.1073 (8)	0.083 (11)*
H20	0.449 (3)	0.489 (2)	0.1308 (8)	0.071 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0408 (3)	0.0486 (4)	0.0569 (4)	0.0088 (3)	0.0075 (3)	0.0052 (3)
O1	0.0891 (17)	0.0787 (17)	0.0752 (15)	0.0093 (14)	0.0099 (12)	−0.0245 (13)
O2	0.1106 (19)	0.0453 (13)	0.0813 (15)	0.0024 (13)	0.0112 (13)	−0.0055 (11)
O3	0.0428 (10)	0.0851 (16)	0.0633 (12)	0.0141 (10)	0.0009 (8)	0.0020 (11)
O4	0.0463 (10)	0.0839 (16)	0.0715 (13)	0.0134 (11)	0.0189 (9)	0.0157 (12)
N1	0.0499 (12)	0.0433 (13)	0.0469 (11)	−0.0035 (10)	0.0009 (9)	0.0074 (10)
C1	0.0428 (14)	0.0621 (19)	0.0664 (17)	−0.0118 (14)	0.0022 (12)	0.0051 (16)
C2	0.0379 (13)	0.069 (2)	0.0667 (17)	−0.0022 (13)	0.0094 (12)	0.0010 (16)
C3	0.0433 (13)	0.0479 (15)	0.0486 (13)	0.0010 (12)	0.0046 (10)	0.0079 (12)
C4	0.0405 (12)	0.0525 (16)	0.0580 (15)	−0.0096 (12)	0.0058 (11)	−0.0002 (14)
C5	0.0413 (13)	0.0511 (17)	0.0586 (15)	−0.0037 (12)	0.0104 (11)	0.0030 (13)
C6	0.078 (2)	0.0452 (16)	0.0594 (16)	−0.0041 (15)	−0.0014 (14)	−0.0017 (14)
C7	0.0431 (14)	0.0617 (19)	0.0630 (16)	0.0058 (14)	0.0108 (12)	0.0020 (15)
C8	0.0455 (13)	0.0559 (17)	0.0548 (15)	0.0068 (13)	0.0072 (11)	0.0052 (14)
C9	0.0495 (14)	0.0526 (17)	0.0469 (13)	0.0107 (13)	0.0044 (11)	0.0026 (13)
C10	0.0547 (17)	0.080 (2)	0.077 (2)	−0.0043 (17)	0.0136 (15)	−0.0155 (19)
C11	0.0638 (19)	0.091 (3)	0.077 (2)	0.0096 (19)	0.0193 (16)	−0.020 (2)
C12	0.0690 (19)	0.061 (2)	0.0519 (15)	0.0182 (16)	0.0064 (13)	−0.0063 (14)
C13	0.0618 (17)	0.066 (2)	0.0682 (18)	−0.0005 (16)	0.0069 (14)	−0.0090 (17)
C14	0.0527 (16)	0.0624 (19)	0.0605 (16)	0.0072 (14)	0.0129 (13)	−0.0060 (15)
C15	0.095 (3)	0.062 (2)	0.0630 (19)	0.009 (2)	0.0010 (17)	−0.0061 (17)
C16	0.123 (3)	0.069 (2)	0.0623 (19)	0.018 (2)	0.000 (2)	−0.0104 (18)
C17	0.154 (4)	0.078 (3)	0.070 (2)	−0.001 (3)	0.001 (2)	−0.010 (2)
C18	0.208 (6)	0.091 (3)	0.095 (3)	0.000 (4)	−0.008 (3)	−0.029 (3)
C19	0.0328 (11)	0.0383 (14)	0.0576 (14)	0.0006 (10)	0.0062 (10)	0.0095 (12)
C20	0.0727 (19)	0.0432 (17)	0.0667 (18)	0.0019 (15)	−0.0003 (15)	0.0114 (15)
C21	0.080 (2)	0.067 (2)	0.0604 (18)	−0.0054 (18)	−0.0040 (15)	0.0238 (17)
C22	0.069 (2)	0.071 (2)	0.0651 (19)	−0.0089 (18)	0.0039 (15)	−0.0003 (18)
C23	0.097 (3)	0.0449 (19)	0.077 (2)	−0.0071 (18)	−0.0009 (19)	−0.0015 (17)
C24	0.0704 (19)	0.0421 (16)	0.0659 (18)	−0.0007 (14)	0.0022 (14)	0.0145 (14)
C25	0.133 (4)	0.104 (3)	0.075 (2)	−0.023 (3)	−0.003 (2)	−0.011 (2)

Geometric parameters (Å, º) top

S1—O2	1.443 (2)	C12—C13	1.376 (4)
S1—O4	1.445 (2)	C13—C14	1.381 (4)
S1—O3	1.4487 (19)	C13—H13	0.9300
S1—C19	1.773 (3)	C14—H14	0.9300
O1—C12	1.364 (4)	C15—C16	1.512 (5)
O1—C15	1.418 (4)	C15—H15A	0.9700
N1—C1	1.339 (3)	C15—H15B	0.9700
N1—C5	1.346 (3)	C16—C17	1.503 (6)
N1—C6	1.474 (4)	C16—H16A	0.9700
C1—C2	1.354 (4)	C16—H16B	0.9700
C1—H1	0.9300	C17—C18	1.510 (6)
C2—C3	1.385 (4)	C17—H17A	0.9700
C2—H2	0.9300	C17—H17B	0.9700
C3—C4	1.404 (4)	C18—H18A	0.9600
C3—C7	1.459 (4)	C18—H18B	0.9600
C4—C5	1.360 (4)	C18—H18C	0.9600
C4—H4	0.9300	C19—C20	1.363 (4)
C5—H5	0.9300	C19—C24	1.378 (4)
C6—H6A	0.9600	C20—C21	1.383 (5)
C6—H6B	0.9600	C20—H20	0.933 (10)
C6—H6C	0.9600	C21—C22	1.369 (5)
C7—C8	1.315 (4)	C21—H21	0.9300
C7—H7	0.9300	C22—C23	1.370 (5)
C8—C9	1.460 (4)	C22—C25	1.516 (5)
C8—H8	0.9300	C23—C24	1.386 (5)
C9—C14	1.379 (4)	C23—H23	0.930 (10)
C9—C10	1.391 (4)	C24—H24	0.9300
C10—C11	1.366 (5)	C25—H25A	0.9600
C10—H10	0.9300	C25—H25B	0.9600
C11—C12	1.384 (5)	C25—H25C	0.9600
C11—H11	0.9300

O2—S1—O4	113.47 (14)	C9—C14—C13	122.3 (3)
O2—S1—O3	113.34 (15)	C9—C14—H14	118.8
O4—S1—O3	112.88 (13)	C13—C14—H14	118.8
O2—S1—C19	105.64 (13)	O1—C15—C16	108.8 (3)
O4—S1—C19	105.08 (12)	O1—C15—H15A	109.9
O3—S1—C19	105.44 (12)	C16—C15—H15A	109.9
C12—O1—C15	117.6 (3)	O1—C15—H15B	109.9
C1—N1—C5	119.7 (2)	C16—C15—H15B	109.9
C1—N1—C6	120.7 (2)	H15A—C15—H15B	108.3
C5—N1—C6	119.5 (2)	C17—C16—C15	111.7 (4)
N1—C1—C2	121.0 (3)	C17—C16—H16A	109.3
N1—C1—H1	119.5	C15—C16—H16A	109.3
C2—C1—H1	119.5	C17—C16—H16B	109.3
C1—C2—C3	121.7 (3)	C15—C16—H16B	109.3
C1—C2—H2	119.2	H16A—C16—H16B	107.9
C3—C2—H2	119.2	C16—C17—C18	113.9 (4)
C2—C3—C4	115.8 (3)	C16—C17—H17A	108.8
C2—C3—C7	120.5 (2)	C18—C17—H17A	108.8
C4—C3—C7	123.7 (2)	C16—C17—H17B	108.8
C5—C4—C3	120.8 (2)	C18—C17—H17B	108.8
C5—C4—H4	119.6	H17A—C17—H17B	107.7
C3—C4—H4	119.6	C17—C18—H18A	109.5
N1—C5—C4	121.0 (2)	C17—C18—H18B	109.5
N1—C5—H5	119.5	H18A—C18—H18B	109.5
C4—C5—H5	119.5	C17—C18—H18C	109.5
N1—C6—H6A	109.5	H18A—C18—H18C	109.5
N1—C6—H6B	109.5	H18B—C18—H18C	109.5
H6A—C6—H6B	109.5	C20—C19—C24	118.0 (3)
N1—C6—H6C	109.5	C20—C19—S1	121.1 (2)
H6A—C6—H6C	109.5	C24—C19—S1	120.9 (2)
H6B—C6—H6C	109.5	C19—C20—C21	121.6 (3)
C8—C7—C3	126.0 (3)	C19—C20—H20	113 (2)
C8—C7—H7	117.0	C21—C20—H20	125 (2)
C3—C7—H7	117.0	C22—C21—C20	121.2 (3)
C7—C8—C9	126.6 (3)	C22—C21—H21	119.4
C7—C8—H8	116.7	C20—C21—H21	119.4
C9—C8—H8	116.7	C21—C22—C23	116.9 (3)
C14—C9—C10	116.6 (3)	C21—C22—C25	121.9 (3)
C14—C9—C8	119.6 (2)	C23—C22—C25	121.2 (4)
C10—C9—C8	123.8 (3)	C22—C23—C24	122.4 (3)
C11—C10—C9	121.8 (3)	C22—C23—H23	119 (2)
C11—C10—H10	119.1	C24—C23—H23	119 (2)
C9—C10—H10	119.1	C19—C24—C23	119.8 (3)
C10—C11—C12	120.7 (3)	C19—C24—H24	120.1
C10—C11—H11	119.7	C23—C24—H24	120.1
C12—C11—H11	119.7	C22—C25—H25A	109.5
O1—C12—C13	124.9 (3)	C22—C25—H25B	109.5
O1—C12—C11	116.4 (3)	H25A—C25—H25B	109.5
C13—C12—C11	118.7 (3)	C22—C25—H25C	109.5
C12—C13—C14	119.9 (3)	H25A—C25—H25C	109.5
C12—C13—H13	120.1	H25B—C25—H25C	109.5
C14—C13—H13	120.1

C5—N1—C1—C2	−1.1 (4)	C11—C12—C13—C14	−0.9 (5)
C6—N1—C1—C2	−178.4 (3)	C10—C9—C14—C13	0.5 (4)
N1—C1—C2—C3	0.7 (5)	C8—C9—C14—C13	−178.1 (3)
C1—C2—C3—C4	0.4 (4)	C12—C13—C14—C9	0.1 (5)
C1—C2—C3—C7	−177.9 (3)	C12—O1—C15—C16	−177.7 (3)
C2—C3—C4—C5	−1.1 (4)	O1—C15—C16—C17	−178.4 (3)
C7—C3—C4—C5	177.2 (3)	C15—C16—C17—C18	177.2 (3)
C1—N1—C5—C4	0.4 (4)	O2—S1—C19—C20	−4.2 (3)
C6—N1—C5—C4	177.8 (2)	O4—S1—C19—C20	116.1 (2)
C3—C4—C5—N1	0.7 (4)	O3—S1—C19—C20	−124.5 (2)
C2—C3—C7—C8	−179.6 (3)	O2—S1—C19—C24	176.9 (2)
C4—C3—C7—C8	2.2 (5)	O4—S1—C19—C24	−62.8 (2)
C3—C7—C8—C9	−178.1 (3)	O3—S1—C19—C24	56.7 (3)
C7—C8—C9—C14	−174.7 (3)	C24—C19—C20—C21	1.3 (5)
C7—C8—C9—C10	6.8 (5)	S1—C19—C20—C21	−177.7 (3)
C14—C9—C10—C11	−0.4 (5)	C19—C20—C21—C22	0.4 (5)
C8—C9—C10—C11	178.2 (3)	C20—C21—C22—C23	−1.4 (5)
C9—C10—C11—C12	−0.3 (6)	C20—C21—C22—C25	177.4 (3)
C15—O1—C12—C13	−4.1 (5)	C21—C22—C23—C24	0.8 (6)
C15—O1—C12—C11	175.6 (3)	C25—C22—C23—C24	−178.0 (4)
C10—C11—C12—O1	−178.8 (3)	C20—C19—C24—C23	−1.8 (5)
C10—C11—C12—C13	1.0 (5)	S1—C19—C24—C23	177.1 (3)
O1—C12—C13—C14	178.8 (3)	C22—C23—C24—C19	0.8 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O4ⁱ	0.93	2.33	3.210 (3)	158
C4—H4···O3ⁱⁱ	0.93	2.56	3.412 (3)	153
C6—H6B···O3ⁱⁱⁱ	0.96	2.57	3.470 (4)	157
C8—H8···O3ⁱⁱ	0.93	2.55	3.418 (3)	156

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2; (iii) −x+3/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₈H₂₂NO⁺·C₇H₇O₃S⁻
M_r	439.55
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	9.0884 (6), 6.4559 (5), 39.827 (3)
β (°)	95.404 (3)
V (Å³)	2326.4 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.17
Crystal size (mm)	0.28 × 0.24 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.954, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	20608, 5629, 4258
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.069, 0.160, 1.16
No. of reflections	5629
No. of parameters	291
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.39

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O4ⁱ	0.93	2.33	3.210 (3)	158
C4—H4···O3ⁱⁱ	0.93	2.56	3.412 (3)	153
C6—H6B···O3ⁱⁱⁱ	0.96	2.57	3.470 (4)	157
C8—H8···O3ⁱⁱ	0.93	2.55	3.418 (3)	156

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2; (iii) −x+3/2, y−1/2, −z+1/2.

Acknowledgements

MK thanks the Council of Scientific and Industrial Research, New Delhi, India, for financial support (project No. 03 (1200)/11/EMR-II).

References

Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Nalwa, H. S. & Miyata, S. (1997). In Nonlinear Optics of Organic Molecules and Polymers. Boca Raton: CRC Press. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
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Sivakumar, P. K., Krishnakumar, M., Kanagadurai, R., Chakkaravarthi, G. & Mohankumar, R. (2012). Acta Cryst. E68, o3059. CSD CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar