(E)-4-[4-(Dimethyl­amino)styr­yl]-1-methyl­pyridinium 4-bromo­benzene­sulfonate

Chantrapromma, S.; Jansrisewangwong, P.; Musor, R.; Fun, H.-K.

doi:10.1107/S1600536808043547

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Pages o217-o218

doi:10.1107/S1600536808043547

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(E)-4-[4-(Dimethylamino)styryl]-1-methylpyridinium 4-bromobenzenesulfonate †

Suchada Chantrapromma,^a ^* Patcharaporn Jansrisewangwong,^a Rusmeenee Musor ^a and Hoong-Kun Fun ^b ‡

^aCrystal Materials Research Unit, Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand, and ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: suchada.c@psu.ac.th

(Received 11 November 2008; accepted 22 December 2008; online 8 January 2009)

In the title compound, C₁₆H₁₉N₂⁺·C₆H₄BrO₃S⁻, the cation is nearly planar, with a dihedral angle of 3.19 (15)° between the pyridinium and the dimethylaminophenyl rings, and exists in the trans configuration. In the crystal packing, the cations and anions are linked into chains parallel to the c axis. These chains are stacked along the b axis. The crystal is stabilized by weak C—H⋯O and C—H⋯π interactions, and a π–π interaction is also observed with a Cg⋯Cg distance of 3.5675 (19) Å.

Related literature

For background to NLO materials research, see: Chia et al. (1995 ); Sato et al. (1999 ); Nogi et al. (2000 ); Otero et al. (2002 ); Dittrich et al. (2003 ). For related structures, see, for example: Adachi et al. (1999 ); Chantrapromma et al. (2006 ; 2008 ); Jagannathan et al. (2007 ); Ogawa et al. (2008 ); Rahman et al. (2003 ); Yang et al. (2007 ). For comparison bond lengths, see Allen et al. (1987 ).

Experimental

Crystal data

C₁₆H₁₉N₂⁺·C₆H₄BrO₃S⁻
M_r = 475.39
Monoclinic, C c
a = 10.3712 (4) Å
b = 10.9937 (5) Å
c = 17.9027 (8) Å
β = 92.442 (3)°
V = 2039.37 (15) Å³
Z = 4
Mo Kα radiation
μ = 2.15 mm⁻¹
T = 100.0 (1) K
0.49 × 0.31 × 0.11 mm

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.414, T_max = 0.787
13146 measured reflections
6479 independent reflections
4811 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.097
S = 1.02
6479 reflections
265 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 1.01 e Å⁻³
Δρ_min = −1.38 e Å⁻³
Absolute structure: Flack (1983 ), 1997 Friedel pairs
Flack parameter: 0.024 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O1ⁱ	0.93	2.44	3.366 (4)	175
C4—H4A⋯O2ⁱⁱ	0.93	2.45	3.375 (4)	175
C6—H6A⋯O3ⁱⁱⁱ	0.93	2.44	3.175 (4)	136
C7—H7A⋯O2ⁱⁱ	0.93	2.36	3.285 (4)	173
C14—H14C⋯O3ⁱ	0.96	2.36	3.304 (4)	168
C15—H15A⋯O2	0.96	2.57	3.515 (4)	168
C19—H19A⋯O1^iv	0.93	2.47	3.306 (4)	149
C3—H3A⋯Cg3ⁱⁱ	0.93	2.76	3.601 (4)	151
C14—H14B⋯Cg2^v	0.96	2.55	3.468 (4)	161
Symmetry codes: (i) $[x-1, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (v) x-1, y, z. Cg2 and Cg3 are the centroids of the C8–C13 and C17–C22 rings.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808043547/pk2136sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808043547/pk2136Isup2.hkl

checkCIF report

Comment top

Organic crystals with extensive conjugated π systems are attractive candidates for non-linear optic (NLO) studies because of their large NLO coefficients (Chia et al., 1995; Dittrich et al., 2003; Otero et al., 2002; Nogi et al., 2000; Sato et al., 1999). 4-N,N-dimethylamino-4'-N'-methyl-stilbazolium tosylate (DAST) is one such promising NLO material (Adachi et al., 1999). Previous studies (Dittrich et al., 2003; Nogi et al., 2000; Sato et al., 1999) have shown that DAST and its analogues exhibit second-order non-linear optical properties. To investigate the effect of counter anion on the NLO properties of DAST, the title compound was prepared by changing the counter anion from 4-toluenesulfonate in DAST to 4-bromobenzenesulfonate. The title compound is found to crystallize with the non-centrosymmetric space group Cc and therefore has second order nonlinear optical properties.

The asymmetric unit of the title compound (Fig. 1), consists of the C₁₆H₁₉N₂⁺ cation and C₆H₄BrO₃S^- anion. The cation exists in the E configuration with respect to the C6=C7 double bond [1.342 (5) Å] and the cation is nearly planar as indicated by the dihedral angle between the pyridinium and the dimethylaminophenyl rings 3.19 (15)°, and by the torsion angles C4–C5–C6–C7 = 1.0 (5)° and C6–C7–C8–C13 = 2.4 (5)°. Both methyl groups of the dimethylamino group are co-planar with the C8–C13 ring with the torsion angle C15—N2–C11–C10 of 2.3 (5)° and C16–N2–C11–C12 = 1.5 (5)°. The relative arrangement of cation and anion is shown by the angles between the mean plane of the 4-bromophenyl ring and those of the pyridinium and dimethylaminophenyl systems which are 74.81 (16)° and 77.99 (16)°, respectively. The bond lengths and angles are normal (Allen et al., 1987) and the cation bond lengths and angles are comparable with related structures (Chantrapromma et al., 2008).

In the crystal packing, all O atoms of sulfonate group are involved in weak C—H···O interactions (Table 1). The cations and anions are linked by weak C—H···O interactions into chains along the c axis and these chains are stacked along the b axis (Fig. 2). The crystal structure is further stabilized by a C—H···π interactions (Table 1). π–π interactions with the distance Cg₁···Cg₂ = 3.5675 (19) Å (symmetry code -1/2 + x, -1/2 + y, z and 1/2 + x, 1/2 + y, z) are observed; Cg₁, Cg₂ and Cg₃ are the centroids of the N1/C1–C5, C8–C13 and C17–C22 rings.

Related literature top

For background to NLO materials research, see: Chia et al., (1995); Sato et al., (1999); Nogi et al., (2000); Otero et al., (2002); Dittrich et al., (2003). For related structures, see for example, Adachi et al. (1999); Chantrapromma et al. (2006; 2008); Jagannathan et al. (2007); Ogawa et al. (2008); Rahman et al. (2003) and Yang et al. (2007). For comparison bond lengths, see Allen et al. (1987). Cg2 and Cg3 are the centroids of the C8–C13 and C17–C22 rings.

Experimental top

(E)-4-[4-(Dimethylamino)styryl]-1-methylpyridinium iodide (compound A) was synthesized by mixing a solution (1:1:1 molar ratio) of 1,4-dimethylpyridinium iodide (2.00 g, 8.5 mmol), 4-dimethylaminobenzaldehyde (1.27 g, 8.5 mmol) and piperidine (0.84 ml, 8.5 mmol) in hot methanol (50 ml). The resulting solution was refluxed for 3 h under a nitrogen atmosphere. The resultant solid was filtered off, washed with diethylether to give red solid of compound A (2.86 g, 92%), Mp. 536–537 K). Silver(I) p-bromobenzenesulfonate (compound B) was synthesized according to our previously reported procedure (Chantrapromma et al., 2006). The title compound was synthesized by mixing compound A (0.20 g, 0.5 mmol) in hot methanol (25 ml) and a solution of compound B (0.17 g, 0.5 mmol) in hot methanol (50 ml). The mixture immediately yielded a grey precipitate of silver iodide. After stirring the mixture for 30 min, the precipitate of silver iodide was removed and the resulting solution was evaporated yielding a red solid. Red plate-shaped single crystals of the title compound suitable for x-ray structure determination were recrystalized from methanol by slow evaporation of the solvent at room temperature over several days, Mp. 536–537 K.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008)and PLATON (Spek, 2003).

Figures top

	Fig. 1. The asymmetric unit showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. Crystal packing viewed along the a axis. The weak C—H···O interactions are drawn as dashed lines.

(E)-4-[4-(Dimethylamino)styryl]-1-methylpyridinium 4-bromobenzenesulfonate top

Crystal data top

C₁₆H₁₉N₂⁺·C₆H₄BrO₃S⁻	F(000) = 976
M_r = 475.39	D_x = 1.548 Mg m⁻³
Monoclinic, Cc	Melting point = 536–537 K
Hall symbol: C -2yc	Mo Kα radiation, λ = 0.71073 Å
a = 10.3712 (4) Å	Cell parameters from 6479 reflections
b = 10.9937 (5) Å	θ = 2.7–35.0°
c = 17.9027 (8) Å	µ = 2.15 mm⁻¹
β = 92.442 (3)°	T = 100 K
V = 2039.37 (15) Å³	Plate, red
Z = 4	0.49 × 0.31 × 0.11 mm

Data collection top

Bruker SMART APEX2 CCD area-detector diffractometer	6479 independent reflections
Radiation source: fine-focus sealed tube	4811 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
Detector resolution: 8.33 pixels mm^-1	θ_max = 35.0°, θ_min = 2.7°
ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −17→14
T_min = 0.414, T_max = 0.787	l = −28→19
13146 measured reflections

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)] = 0.046	H-atom parameters constrained
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.022P)² + 0.6614P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
6479 reflections	Δρ_max = 1.01 e Å⁻³
265 parameters	Δρ_min = −1.38 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 1997 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.024 (7)

Crystal data top

C₁₆H₁₉N₂⁺·C₆H₄BrO₃S⁻	V = 2039.37 (15) Å³
M_r = 475.39	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 10.3712 (4) Å	µ = 2.15 mm⁻¹
b = 10.9937 (5) Å	T = 100 K
c = 17.9027 (8) Å	0.49 × 0.31 × 0.11 mm
β = 92.442 (3)°

Data collection top

Bruker SMART APEX2 CCD area-detector diffractometer	6479 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	4811 reflections with I > 2σ(I)
T_min = 0.414, T_max = 0.787	R_int = 0.043
13146 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.097	Δρ_max = 1.01 e Å⁻³
S = 1.02	Δρ_min = −1.38 e Å⁻³
6479 reflections	Absolute structure: Flack (1983), 1997 Friedel pairs
265 parameters	Absolute structure parameter: 0.024 (7)
2 restraints

Special details top

Experimental. The low-temperature data was collected with the Oxford Cryosystem Cobra low-temperature attachment.

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
Br1	0.36598 (3)	0.77042 (3)	0.68824 (2)	0.02730 (9)
S1	0.98401 (6)	0.80532 (7)	0.66253 (5)	0.01869 (16)
O1	1.0332 (2)	0.6820 (2)	0.65917 (15)	0.0260 (5)
O2	1.0299 (2)	0.8717 (2)	0.72875 (14)	0.0264 (5)
O3	0.9990 (2)	0.8740 (2)	0.59428 (14)	0.0275 (5)
N1	0.1505 (2)	0.3126 (2)	0.93738 (17)	0.0235 (6)
N2	1.1241 (3)	0.6429 (3)	0.91479 (17)	0.0288 (6)
C1	0.3252 (3)	0.3957 (3)	1.0096 (2)	0.0267 (7)
H1A	0.3595	0.4215	1.0557	0.032*
C2	0.2023 (3)	0.3507 (3)	1.0041 (2)	0.0248 (7)
H2A	0.1538	0.3462	1.0466	0.030*
C3	0.2213 (3)	0.3179 (3)	0.8760 (2)	0.0230 (7)
H3A	0.1854	0.2908	0.8305	0.028*
C4	0.3442 (3)	0.3621 (3)	0.8789 (2)	0.0238 (7)
H4A	0.3909	0.3646	0.8357	0.029*
C5	0.4003 (3)	0.4034 (3)	0.9463 (2)	0.0231 (7)
C6	0.5317 (3)	0.4507 (3)	0.9554 (2)	0.0265 (8)
H6A	0.5609	0.4749	1.0029	0.032*
C7	0.6126 (3)	0.4612 (3)	0.8992 (2)	0.0231 (7)
H7A	0.5821	0.4373	0.8519	0.028*
C8	0.7443 (3)	0.5069 (3)	0.9063 (2)	0.0238 (7)
C9	0.8152 (3)	0.5165 (3)	0.84225 (19)	0.0224 (7)
H9A	0.7775	0.4917	0.7967	0.027*
C10	0.9406 (3)	0.5618 (3)	0.8439 (2)	0.0229 (7)
H10A	0.9842	0.5690	0.7998	0.027*
C11	1.0015 (3)	0.5969 (3)	0.9124 (2)	0.0225 (7)
C12	0.9307 (3)	0.5851 (3)	0.9777 (2)	0.0260 (7)
H12A	0.9690	0.6066	1.0237	0.031*
C13	0.8055 (3)	0.5421 (3)	0.9742 (2)	0.0250 (7)
H13A	0.7608	0.5363	1.0179	0.030*
C14	0.0170 (3)	0.2686 (3)	0.9326 (2)	0.0298 (8)
H14A	0.0039	0.2197	0.8885	0.045*
H14B	−0.0409	0.3367	0.9302	0.045*
H14C	0.0007	0.2206	0.9760	0.045*
C15	1.1928 (3)	0.6611 (3)	0.8465 (2)	0.0295 (8)
H15A	1.1404	0.7084	0.8119	0.044*
H15B	1.2110	0.5835	0.8246	0.044*
H15C	1.2722	0.7032	0.8579	0.044*
C16	1.1872 (3)	0.6788 (3)	0.9852 (2)	0.0304 (8)
H16A	1.1782	0.6151	1.0213	0.046*
H16B	1.1480	0.7518	1.0030	0.046*
H16C	1.2771	0.6932	0.9781	0.046*
C17	0.8138 (3)	0.7927 (3)	0.6710 (2)	0.0176 (6)
C18	0.7402 (3)	0.8978 (3)	0.6780 (2)	0.0192 (7)
H18A	0.7809	0.9732	0.6797	0.023*
C19	0.6080 (3)	0.8917 (3)	0.6823 (2)	0.0209 (7)
H19A	0.5594	0.9624	0.6858	0.025*
C20	0.5489 (3)	0.7790 (3)	0.6814 (2)	0.0207 (6)
C21	0.6187 (3)	0.6722 (3)	0.6750 (2)	0.0220 (7)
H21A	0.5774	0.5970	0.6743	0.026*
C22	0.7524 (3)	0.6800 (3)	0.6696 (2)	0.0191 (7)
H22A	0.8008	0.6094	0.6649	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01676 (11)	0.03575 (17)	0.02948 (18)	−0.00106 (18)	0.00199 (10)	−0.0056 (2)
S1	0.0163 (3)	0.0187 (4)	0.0211 (4)	0.0010 (2)	0.0013 (3)	0.0020 (3)
O1	0.0167 (9)	0.0242 (12)	0.0375 (16)	−0.0007 (8)	0.0055 (10)	0.0016 (11)
O2	0.0198 (10)	0.0342 (13)	0.0251 (14)	−0.0022 (9)	−0.0010 (9)	−0.0054 (11)
O3	0.0247 (10)	0.0308 (13)	0.0270 (14)	−0.0007 (9)	0.0021 (9)	0.0068 (10)
N1	0.0221 (12)	0.0201 (13)	0.0287 (18)	0.0065 (10)	0.0035 (12)	0.0037 (12)
N2	0.0305 (13)	0.0347 (16)	0.0212 (16)	−0.0087 (12)	0.0001 (12)	−0.0013 (14)
C1	0.0304 (15)	0.0215 (16)	0.028 (2)	0.0070 (12)	−0.0003 (14)	−0.0023 (14)
C2	0.0302 (15)	0.0235 (16)	0.0210 (19)	0.0080 (12)	0.0049 (14)	0.0013 (14)
C3	0.0269 (14)	0.0220 (16)	0.0197 (19)	0.0052 (12)	−0.0011 (13)	0.0028 (13)
C4	0.0249 (14)	0.0245 (16)	0.0223 (19)	0.0063 (12)	0.0044 (12)	0.0034 (14)
C5	0.0235 (13)	0.0176 (14)	0.0285 (19)	0.0062 (11)	0.0033 (13)	0.0004 (14)
C6	0.0229 (14)	0.0271 (17)	0.030 (2)	0.0064 (12)	0.0001 (14)	−0.0039 (15)
C7	0.0247 (14)	0.0203 (15)	0.0240 (19)	0.0036 (11)	−0.0007 (13)	−0.0008 (13)
C8	0.0245 (14)	0.0215 (15)	0.025 (2)	0.0047 (11)	0.0022 (13)	−0.0003 (14)
C9	0.0281 (14)	0.0203 (15)	0.0185 (18)	0.0035 (11)	−0.0031 (13)	−0.0020 (13)
C10	0.0265 (14)	0.0208 (15)	0.0214 (19)	0.0036 (11)	0.0017 (13)	−0.0004 (13)
C11	0.0284 (14)	0.0164 (14)	0.0228 (19)	0.0018 (11)	0.0008 (13)	0.0023 (13)
C12	0.0308 (15)	0.0245 (17)	0.0224 (19)	0.0005 (12)	−0.0014 (14)	−0.0009 (14)
C13	0.0277 (15)	0.0258 (16)	0.0217 (19)	0.0003 (12)	0.0023 (13)	−0.0035 (14)
C14	0.0250 (14)	0.0274 (16)	0.037 (2)	0.0018 (13)	0.0038 (14)	0.0079 (16)
C15	0.0299 (15)	0.0315 (18)	0.027 (2)	−0.0053 (13)	−0.0018 (14)	0.0038 (16)
C16	0.0354 (17)	0.0309 (18)	0.024 (2)	−0.0066 (14)	−0.0055 (15)	−0.0007 (16)
C17	0.0174 (12)	0.0168 (14)	0.0186 (18)	0.0008 (10)	0.0004 (12)	−0.0001 (12)
C18	0.0182 (12)	0.0177 (16)	0.0215 (19)	−0.0021 (11)	0.0002 (12)	−0.0015 (13)
C19	0.0229 (14)	0.0202 (16)	0.0197 (18)	0.0029 (11)	0.0012 (12)	−0.0028 (13)
C20	0.0167 (12)	0.0293 (16)	0.0160 (17)	0.0013 (12)	0.0003 (11)	−0.0020 (14)
C21	0.0230 (14)	0.0181 (16)	0.025 (2)	−0.0009 (11)	−0.0009 (13)	−0.0004 (14)
C22	0.0226 (14)	0.0150 (15)	0.0197 (19)	0.0036 (11)	−0.0001 (13)	0.0039 (13)

Geometric parameters (Å, º) top

Br1—C20	1.909 (3)	C9—H9A	0.9300
S1—O3	1.450 (3)	C10—C11	1.409 (5)
S1—O1	1.451 (2)	C10—H10A	0.9300
S1—O2	1.455 (2)	C11—C12	1.413 (5)
S1—C17	1.784 (3)	C12—C13	1.380 (4)
N1—C3	1.349 (4)	C12—H12A	0.9300
N1—C2	1.355 (4)	C13—H13A	0.9300
N1—C14	1.466 (4)	C14—H14A	0.9600
N2—C11	1.367 (4)	C14—H14B	0.9600
N2—C16	1.451 (4)	C14—H14C	0.9600
N2—C15	1.455 (5)	C15—H15A	0.9600
C1—C2	1.367 (5)	C15—H15B	0.9600
C1—C5	1.405 (5)	C15—H15C	0.9600
C1—H1A	0.9300	C16—H16A	0.9600
C2—H2A	0.9300	C16—H16B	0.9600
C3—C4	1.363 (4)	C16—H16C	0.9600
C3—H3A	0.9300	C17—C18	1.392 (4)
C4—C5	1.393 (5)	C17—C22	1.393 (4)
C4—H4A	0.9300	C18—C19	1.378 (4)
C5—C6	1.461 (4)	C18—H18A	0.9300
C6—C7	1.342 (5)	C19—C20	1.382 (5)
C6—H6A	0.9300	C19—H19A	0.9300
C7—C8	1.455 (4)	C20—C21	1.387 (5)
C7—H7A	0.9300	C21—C22	1.396 (4)
C8—C9	1.393 (5)	C21—H21A	0.9300
C8—C13	1.402 (5)	C22—H22A	0.9300
C9—C10	1.391 (4)

O3—S1—O1	113.63 (15)	C10—C11—C12	117.7 (3)
O3—S1—O2	112.50 (15)	C13—C12—C11	121.0 (3)
O1—S1—O2	113.53 (14)	C13—C12—H12A	119.5
O3—S1—C17	104.72 (14)	C11—C12—H12A	119.5
O1—S1—C17	106.37 (13)	C12—C13—C8	121.6 (3)
O2—S1—C17	105.09 (15)	C12—C13—H13A	119.2
C3—N1—C2	119.8 (3)	C8—C13—H13A	119.2
C3—N1—C14	120.8 (3)	N1—C14—H14A	109.5
C2—N1—C14	119.4 (3)	N1—C14—H14B	109.5
C11—N2—C16	120.8 (3)	H14A—C14—H14B	109.5
C11—N2—C15	120.8 (3)	N1—C14—H14C	109.5
C16—N2—C15	118.3 (3)	H14A—C14—H14C	109.5
C2—C1—C5	120.8 (3)	H14B—C14—H14C	109.5
C2—C1—H1A	119.6	N2—C15—H15A	109.5
C5—C1—H1A	119.6	N2—C15—H15B	109.5
N1—C2—C1	120.5 (3)	H15A—C15—H15B	109.5
N1—C2—H2A	119.7	N2—C15—H15C	109.5
C1—C2—H2A	119.7	H15A—C15—H15C	109.5
N1—C3—C4	121.6 (3)	H15B—C15—H15C	109.5
N1—C3—H3A	119.2	N2—C16—H16A	109.5
C4—C3—H3A	119.2	N2—C16—H16B	109.5
C3—C4—C5	120.3 (3)	H16A—C16—H16B	109.5
C3—C4—H4A	119.8	N2—C16—H16C	109.5
C5—C4—H4A	119.8	H16A—C16—H16C	109.5
C4—C5—C1	117.0 (3)	H16B—C16—H16C	109.5
C4—C5—C6	124.4 (3)	C18—C17—C22	119.2 (3)
C1—C5—C6	118.6 (3)	C18—C17—S1	119.4 (2)
C7—C6—C5	123.9 (3)	C22—C17—S1	121.4 (2)
C7—C6—H6A	118.1	C19—C18—C17	121.0 (3)
C5—C6—H6A	118.1	C19—C18—H18A	119.5
C6—C7—C8	125.4 (3)	C17—C18—H18A	119.5
C6—C7—H7A	117.3	C18—C19—C20	119.0 (3)
C8—C7—H7A	117.3	C18—C19—H19A	120.5
C9—C8—C13	117.2 (3)	C20—C19—H19A	120.5
C9—C8—C7	118.8 (3)	C19—C20—C21	121.8 (3)
C13—C8—C7	124.0 (3)	C19—C20—Br1	119.0 (2)
C10—C9—C8	122.4 (3)	C21—C20—Br1	119.1 (2)
C10—C9—H9A	118.8	C20—C21—C22	118.5 (3)
C8—C9—H9A	118.8	C20—C21—H21A	120.8
C9—C10—C11	120.0 (3)	C22—C21—H21A	120.8
C9—C10—H10A	120.0	C17—C22—C21	120.5 (3)
C11—C10—H10A	120.0	C17—C22—H22A	119.7
N2—C11—C10	120.7 (3)	C21—C22—H22A	119.7
N2—C11—C12	121.6 (3)

C3—N1—C2—C1	0.7 (5)	C9—C10—C11—C12	−0.5 (4)
C14—N1—C2—C1	−177.9 (3)	N2—C11—C12—C13	177.9 (3)
C5—C1—C2—N1	0.0 (5)	C10—C11—C12—C13	−0.8 (5)
C2—N1—C3—C4	−0.7 (5)	C11—C12—C13—C8	0.9 (5)
C14—N1—C3—C4	177.9 (3)	C9—C8—C13—C12	0.3 (5)
N1—C3—C4—C5	0.0 (5)	C7—C8—C13—C12	−179.9 (3)
C3—C4—C5—C1	0.7 (4)	O3—S1—C17—C18	−61.5 (3)
C3—C4—C5—C6	179.1 (3)	O1—S1—C17—C18	177.9 (3)
C2—C1—C5—C4	−0.7 (5)	O2—S1—C17—C18	57.2 (3)
C2—C1—C5—C6	−179.2 (3)	O3—S1—C17—C22	117.4 (3)
C4—C5—C6—C7	1.0 (5)	O1—S1—C17—C22	−3.2 (3)
C1—C5—C6—C7	179.4 (3)	O2—S1—C17—C22	−123.8 (3)
C5—C6—C7—C8	−179.5 (3)	C22—C17—C18—C19	−1.0 (5)
C6—C7—C8—C9	−177.8 (3)	S1—C17—C18—C19	178.0 (3)
C6—C7—C8—C13	2.4 (5)	C17—C18—C19—C20	1.5 (5)
C13—C8—C9—C10	−1.7 (5)	C18—C19—C20—C21	−1.1 (5)
C7—C8—C9—C10	178.5 (3)	C18—C19—C20—Br1	179.5 (3)
C8—C9—C10—C11	1.8 (5)	C19—C20—C21—C22	0.2 (5)
C16—N2—C11—C10	−179.9 (3)	Br1—C20—C21—C22	179.6 (3)
C15—N2—C11—C10	2.3 (5)	C18—C17—C22—C21	0.1 (5)
C16—N2—C11—C12	1.5 (5)	S1—C17—C22—C21	−178.9 (3)
C15—N2—C11—C12	−176.4 (3)	C20—C21—C22—C17	0.4 (5)
C9—C10—C11—N2	−179.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1ⁱ	0.93	2.44	3.366 (4)	175
C4—H4A···O2ⁱⁱ	0.93	2.45	3.375 (4)	175
C6—H6A···O3ⁱⁱⁱ	0.93	2.44	3.175 (4)	136
C7—H7A···O2ⁱⁱ	0.93	2.36	3.285 (4)	173
C14—H14C···O3ⁱ	0.96	2.36	3.304 (4)	168
C15—H15A···O2	0.96	2.57	3.515 (4)	168
C19—H19A···O1^iv	0.93	2.47	3.306 (4)	149
C3—H3A···Cg3ⁱⁱ	0.93	2.76	3.601 (4)	151
C14—H14B···Cg2^v	0.96	2.55	3.468 (4)	161
C16—H16A···Cg3^vi	0.93	2.98	3.446 (4)	111

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₉N₂⁺·C₆H₄BrO₃S⁻
M_r	475.39
Crystal system, space group	Monoclinic, Cc
Temperature (K)	100
a, b, c (Å)	10.3712 (4), 10.9937 (5), 17.9027 (8)
β (°)	92.442 (3)
V (Å³)	2039.37 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.15
Crystal size (mm)	0.49 × 0.31 × 0.11

Data collection
Diffractometer	Bruker SMART APEX2 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.414, 0.787
No. of measured, independent and observed [I > 2σ(I)] reflections	13146, 6479, 4811
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.807

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.097, 1.02
No. of reflections	6479
No. of parameters	265
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.01, −1.38
Absolute structure	Flack (1983), 1997 Friedel pairs
Absolute structure parameter	0.024 (7)

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008)and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1ⁱ	0.93	2.44	3.366 (4)	175
C4—H4A···O2ⁱⁱ	0.93	2.45	3.375 (4)	175
C6—H6A···O3ⁱⁱⁱ	0.93	2.44	3.175 (4)	136
C7—H7A···O2ⁱⁱ	0.93	2.36	3.285 (4)	173
C14—H14C···O3ⁱ	0.96	2.36	3.304 (4)	168
C15—H15A···O2	0.96	2.57	3.515 (4)	168
C19—H19A···O1^iv	0.93	2.47	3.306 (4)	149
C3—H3A···Cg3ⁱⁱ	0.93	2.76	3.601 (4)	151
C14—H14B···Cg2^v	0.96	2.55	3.468 (4)	161
C16—H16A···Cg3^vi	0.93	2.98	3.446 (4)	111

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

Footnotes

†This paper is dedicated to the late Her Royal Highness Princess Galyani Vadhana Krom Luang Naradhiwas Rajanagarindra for her patronage of Science in Thailand.

‡Additional correspondence author, e-mail: hkfun@usm.my.

Acknowledgements

The authors thank Prince of Songkla University for a research grant and Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

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