2-[(E)-2-(1H-Indol-3-yl)ethen­yl]-1-methyl­pyridinium 4-chloro­benzene­sulfonate

Kobkeatthawin, T.; Chantrapromma, S.; Fun, H.-K.

doi:10.1107/S1600536809029547

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Pages o2045-o2046

doi:10.1107/S1600536809029547

Open

access

2-[(E)-2-(1H-Indol-3-yl)ethenyl]-1-methylpyridinium 4-chlorobenzenesulfonate †

Thawanrat Kobkeatthawin,^a Suchada Chantrapromma ^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 15 July 2009; accepted 24 July 2009; online 31 July 2009)

In the title compound, C₁₆H₁₅N₂⁺·C₆H₄ClO₃S⁻, the cation exists in an E configuration with respect to the central C=C bond and is approximately planar, with a dihedral angle of 2.95 (5)° between the pyridinium and indole rings. The mean plane of the π-conjugated system of the cation and the benzene ring of the anion are inclined to each other at a dihedral angle of 69.65 (4)°. In the crystal packing, the cations are stacked in an antiparallel manner along the a axis, resulting in a π–π interaction with a centroid–centroid distance of 3.5889 (7) Å. The anions are linked into a chain along the a axis by weak C—H⋯O interactions. The cations are linked with the anions into a three-dimensional network by N—H⋯O hydrogen bonds and weak C—H⋯O interactions. There are also short O⋯Cl [3.1272 (10) Å] and C⋯O [3.1432 (14)–3.3753 (14) Å] contacts. The crystal structure is further stabilized by C—H⋯π interactions.

Related literature

For bond-length data, see: Allen et al. (1987 ). For background to non-linear optical materials research, see: Ogawa et al. (2008 ); Weir et al. (2003 ); Yang et al. (2007 ). For related structures, see: Chanawanno et al. (2008 ); Chantrapromma et al. (2006 , 2007 , 2008 , 2009 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₁₆H₁₅N₂⁺·C₆H₄ClO₃S⁻
M_r = 426.91
Monoclinic, P 2₁ /c
a = 7.4891 (1) Å
b = 13.1650 (1) Å
c = 20.3428 (2) Å
β = 98.801 (1)°
V = 1982.06 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 100 K
0.34 × 0.28 × 0.19 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.899, T_max = 0.942
39049 measured reflections
8706 independent reflections
7032 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.110
S = 1.05
8706 reflections
267 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.88 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O1ⁱ	0.891 (18)	1.864 (19)	2.7541 (14)	176.2 (18)
C1—H1A⋯O3	0.93	2.53	3.2380 (14)	133
C7—H7A⋯O2ⁱⁱ	0.93	2.59	3.3067 (14)	134
C14—H14A⋯O2ⁱⁱⁱ	0.93	2.52	3.2605 (14)	137
C16—H16C⋯O2ⁱⁱⁱ	0.96	2.37	3.2645 (15)	156
C19—H19A⋯O1^iv	0.93	2.30	3.1432 (14)	151
C21—H21A⋯O3ⁱⁱⁱ	0.93	2.55	3.1885 (14)	127
C4—H4A⋯Cg3^v	0.93	2.85	3.5956 (11)	138
C16—H16A⋯Cg1^vi	0.96	2.72	3.4622 (12)	134
C16—H16B⋯Cg3	0.96	2.67	3.5533 (11)	153
Symmetry codes: (i) -x, -y+1, -z+1; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) x+1, y, z; (v) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vi) -x+1, -y+1, -z+1. Cg1 and Cg3 are the centroids of the N2/C8–C9/C10/C15 and C10–C15 rings, respectively.

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, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809029547/is2441sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809029547/is2441Isup2.hkl

checkCIF report

Comment top

Molecules with extensive conjugated π systems are attractive candidates for non-linear optical (NLO) studies (Ogawa et al., 2008; Weir et al., 2003; Yang et al., 2007). However a molecule with extensive conjugated π systems does not always exhibit second order NLO properties unless the alignment of these molecules is in a noncentrosymmetric space group in the crystal. In our NLO research we have solved a number of crystal structures of pyridinium salt derivatives (Chanawanno et al., 2008; Chantrapromma et al., 2006, 2007, 2008, 2009) which we attempt to examine in details of the relationship between their crystal packings and the NLO properties. We herein report the crystal structure of the title compound (I) which is iso-structure and iso-packing with 2-[(E)-2(1H-Indol-3-yl)ethenyl]-1-methylpyridinium 4-bromobenzenesulfonate (Chantrapromma et al., 2009).

Figure 1 shows the asymmetric unit of (I) which consists of a C₁₆H₁₅N₂⁺ cation and a C₆H₄ClO₃S^- anion. The cation exists in the E configuration with respect to the C6═C7 double bond [1.3567 (14) Å] and is essentially planar with the dihedral angle between the pyridinium and indole rings being 2.96 (5)° and the torsion angles C4–C5–C6–C7 = -1.21 (17)° and C6–C7–C8–C15 = -176.40 (11)°. The indole ring system is planar with the maximum deviation of 0.014 (1) Å for atom C8. The mean planes through π-conjugated systems of the cation and the anion are inclined to each other with an interplanar angle of 69.65 (4)°. The methyl group is co-planar with the attached N1/C1–C5 ring. The bond lengths in (I) are in normal ranges (Allen et al., 1987) and are comparable with those in related structures (Chanawanno et al., 2008; Chantrapromma et al., 2006, 2007, 2008, 2009).

In the crystal packing (Fig. 2), all O atoms of the sulfonate group are involved in weak C—H···O interactions (Table 1). The arrangement of the cations and anions is interesting (Fig. 2). The cations are stacked in an antiparallel manner along the a axis resulting in a π–π interaction with the distance Cg₁···Cg₂ = 3.5889 (7) Å (symmetry code: -x, -y, -z). The anions are linked together into chains by weak C—H···O interactions along the same direction. The cations are linked to the anions into a three dimensional network by N—H···O hydrogen bonds and weak C—H···O interactions (Table 1). There are O···Cl [3.1272 (10) Å] and C···O [3.1432 (14)–3.3753 (14) Å] short contacts. The crystal structure is further stabilized by C—H···π interactions (Table 1); Cg₁, Cg₂ and Cg₃ are the centroids of the N2/C8–C9/C10/C15, N1/C1–C5 and C10–C15 rings, respectively.

Related literature top

For bond-length data, see: Allen et al. (1987). For background to non-linear optical materials research, see: Ogawa et al. (2008); Weir et al. (2003); Yang et al. (2007). For related structures, see, for example: Chanawanno et al. (2008); Chantrapromma et al. (2006, 2007, 2008, 2009). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986). Cg1, Cg2 and Cg3 are the centroids of the N2/C8–C9/C10/C15, N1/C1–C5 and C10–C15 rings, respectively.

Experimental top

The title compound was synthesized by disolving silver(I) p-chlorobenzenesulfonate (Chantrapromma et al., 2006) (0.20 g, 0.67 mmol) in methanol (20 ml) which upon heating was added a solution of 2-[(E)-2-(1H-Indol-3-yl)ethenyl]-1-methylpyridinium iodide (Chantrapromma et al., 2009) (0.24 g, 0.67 mmol) in hot methanol (30 ml). The mixture turned yellow and cloudy immediately. After stirring for 0.5 hr, the precipitate of silver iodide which formed was filtered and the filtrate was evaporated to give an orange gum. Yellow block-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 after a few weeks (m.p. 457-459 K).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (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, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The crystal packing of the title compound viewed down the b axis. Hydrogen bonds are shown as dashed lines.

2-[(E)-2-(1H-Indol-3-yl)ethenyl]-1-methylpyridinium 4-chlorobenzenesulfonate top

Crystal data top

C₁₆H₁₅N₂⁺·C₆H₄ClO₃S⁻	F(000) = 888
M_r = 426.91	D_x = 1.431 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 457–459 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.4891 (1) Å	Cell parameters from 8706 reflections
b = 13.1650 (1) Å	θ = 1.8–35.0°
c = 20.3428 (2) Å	µ = 0.33 mm⁻¹
β = 98.801 (1)°	T = 100 K
V = 1982.06 (4) Å³	Block, yellow
Z = 4	0.34 × 0.28 × 0.19 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	8706 independent reflections
Radiation source: sealed tube	7032 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 35.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −12→12
T_min = 0.899, T_max = 0.942	k = −21→16
39049 measured reflections	l = −32→32

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0515P)² + 0.614P] where P = (F_o² + 2F_c²)/3
8706 reflections	(Δ/σ)_max = 0.001
267 parameters	Δρ_max = 0.88 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

C₁₆H₁₅N₂⁺·C₆H₄ClO₃S⁻	V = 1982.06 (4) Å³
M_r = 426.91	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.4891 (1) Å	µ = 0.33 mm⁻¹
b = 13.1650 (1) Å	T = 100 K
c = 20.3428 (2) Å	0.34 × 0.28 × 0.19 mm
β = 98.801 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	8706 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	7032 reflections with I > 2σ(I)
T_min = 0.899, T_max = 0.942	R_int = 0.034
39049 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.88 e Å⁻³
8706 reflections	Δρ_min = −0.41 e Å⁻³
267 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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
Cl1	0.55212 (4)	0.54773 (2)	0.181673 (15)	0.02519 (7)
S1	−0.02841 (3)	0.876545 (19)	0.222068 (12)	0.01458 (6)
O1	−0.17202 (11)	0.82466 (7)	0.24875 (5)	0.02482 (17)
O2	−0.08774 (12)	0.92193 (7)	0.15750 (4)	0.02477 (17)
O3	0.07291 (12)	0.94718 (7)	0.26916 (5)	0.02529 (18)
N1	0.23969 (12)	0.71072 (7)	0.41746 (4)	0.01633 (15)
N2	0.22567 (13)	0.29591 (8)	0.64537 (5)	0.02030 (17)
H1N2	0.208 (2)	0.2594 (15)	0.6807 (9)	0.037 (5)*
C1	0.21569 (15)	0.80936 (9)	0.39837 (5)	0.02025 (19)
H1A	0.2359	0.8283	0.3561	0.024*
C2	0.16256 (16)	0.88143 (9)	0.43974 (6)	0.0221 (2)
H2A	0.1455	0.9485	0.4259	0.026*
C3	0.13459 (16)	0.85187 (9)	0.50329 (6)	0.0224 (2)
H3A	0.1008	0.8997	0.5327	0.027*
C4	0.15718 (15)	0.75206 (9)	0.52220 (5)	0.02003 (19)
H4A	0.1374	0.7328	0.5645	0.024*
C5	0.20982 (14)	0.67805 (8)	0.47878 (5)	0.01632 (17)
C6	0.23338 (15)	0.57173 (8)	0.49536 (5)	0.01806 (18)
H6A	0.2706	0.5282	0.4641	0.022*
C7	0.20377 (14)	0.53228 (8)	0.55435 (5)	0.01702 (17)
H7A	0.1680	0.5777	0.5848	0.020*
C8	0.22168 (14)	0.42820 (8)	0.57473 (5)	0.01636 (17)
C9	0.19715 (15)	0.39707 (9)	0.63827 (5)	0.01877 (18)
H9A	0.1657	0.4398	0.6711	0.023*
C10	0.26815 (14)	0.25655 (8)	0.58670 (5)	0.01868 (18)
C11	0.30803 (16)	0.15650 (9)	0.57189 (6)	0.0239 (2)
H11A	0.3097	0.1050	0.6033	0.029*
C12	0.34503 (17)	0.13712 (10)	0.50843 (7)	0.0270 (2)
H12A	0.3731	0.0713	0.4969	0.032*
C13	0.34089 (17)	0.21514 (10)	0.46122 (6)	0.0267 (2)
H13A	0.3646	0.1996	0.4188	0.032*
C14	0.30232 (16)	0.31472 (9)	0.47616 (5)	0.0216 (2)
H14A	0.3001	0.3656	0.4443	0.026*
C15	0.26664 (14)	0.33719 (8)	0.54046 (5)	0.01706 (17)
C16	0.29792 (15)	0.63874 (9)	0.36910 (5)	0.01985 (19)
H16A	0.4080	0.6061	0.3886	0.030*
H16B	0.3178	0.6749	0.3299	0.030*
H16C	0.2058	0.5884	0.3574	0.030*
C17	0.13112 (13)	0.78168 (8)	0.20886 (5)	0.01531 (17)
C18	0.31082 (14)	0.81082 (8)	0.20881 (5)	0.01712 (17)
H18A	0.3442	0.8785	0.2155	0.021*
C19	0.43933 (14)	0.73877 (8)	0.19873 (5)	0.01824 (18)
H19A	0.5587	0.7577	0.1981	0.022*
C20	0.38669 (15)	0.63786 (8)	0.18961 (5)	0.01780 (18)
C21	0.20887 (15)	0.60731 (8)	0.18910 (5)	0.01905 (19)
H21A	0.1764	0.5395	0.1826	0.023*
C22	0.07961 (14)	0.68040 (8)	0.19856 (5)	0.01777 (18)
H22A	−0.0403	0.6615	0.1980	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02721 (14)	0.01858 (13)	0.03119 (14)	0.00623 (10)	0.00897 (10)	0.00183 (10)
S1	0.01485 (10)	0.01459 (11)	0.01460 (10)	0.00137 (8)	0.00322 (7)	0.00272 (8)
O1	0.0196 (4)	0.0241 (4)	0.0330 (4)	−0.0001 (3)	0.0107 (3)	0.0088 (3)
O2	0.0280 (4)	0.0255 (4)	0.0211 (4)	0.0071 (3)	0.0046 (3)	0.0085 (3)
O3	0.0208 (4)	0.0233 (4)	0.0310 (4)	0.0017 (3)	0.0015 (3)	−0.0100 (3)
N1	0.0178 (4)	0.0155 (4)	0.0150 (3)	−0.0022 (3)	0.0004 (3)	0.0002 (3)
N2	0.0231 (4)	0.0187 (4)	0.0190 (4)	−0.0001 (3)	0.0028 (3)	0.0044 (3)
C1	0.0227 (5)	0.0176 (5)	0.0196 (4)	−0.0029 (4)	0.0003 (4)	0.0032 (4)
C2	0.0240 (5)	0.0156 (5)	0.0254 (5)	0.0000 (4)	0.0000 (4)	0.0021 (4)
C3	0.0244 (5)	0.0175 (5)	0.0247 (5)	0.0024 (4)	0.0019 (4)	−0.0031 (4)
C4	0.0238 (5)	0.0181 (5)	0.0182 (4)	0.0022 (4)	0.0034 (4)	−0.0008 (4)
C5	0.0177 (4)	0.0162 (4)	0.0147 (4)	−0.0002 (3)	0.0015 (3)	0.0006 (3)
C6	0.0227 (5)	0.0150 (4)	0.0169 (4)	0.0016 (4)	0.0045 (3)	0.0001 (3)
C7	0.0190 (4)	0.0159 (4)	0.0159 (4)	0.0005 (3)	0.0022 (3)	0.0000 (3)
C8	0.0179 (4)	0.0157 (4)	0.0153 (4)	0.0004 (3)	0.0019 (3)	0.0012 (3)
C9	0.0201 (4)	0.0190 (5)	0.0172 (4)	0.0010 (4)	0.0029 (3)	0.0014 (3)
C10	0.0171 (4)	0.0167 (5)	0.0217 (4)	0.0002 (3)	0.0010 (3)	0.0016 (4)
C11	0.0210 (5)	0.0156 (5)	0.0338 (6)	0.0004 (4)	0.0006 (4)	0.0016 (4)
C12	0.0237 (5)	0.0184 (5)	0.0384 (6)	0.0017 (4)	0.0032 (5)	−0.0064 (5)
C13	0.0275 (6)	0.0241 (6)	0.0290 (5)	−0.0001 (4)	0.0063 (4)	−0.0089 (4)
C14	0.0248 (5)	0.0203 (5)	0.0200 (4)	−0.0011 (4)	0.0043 (4)	−0.0030 (4)
C15	0.0168 (4)	0.0162 (5)	0.0178 (4)	0.0005 (3)	0.0015 (3)	−0.0002 (3)
C16	0.0238 (5)	0.0205 (5)	0.0155 (4)	−0.0021 (4)	0.0036 (3)	−0.0015 (3)
C17	0.0163 (4)	0.0144 (4)	0.0151 (4)	−0.0010 (3)	0.0019 (3)	0.0016 (3)
C18	0.0177 (4)	0.0146 (4)	0.0190 (4)	−0.0014 (3)	0.0027 (3)	−0.0003 (3)
C19	0.0167 (4)	0.0172 (5)	0.0208 (4)	−0.0007 (3)	0.0028 (3)	−0.0002 (3)
C20	0.0209 (4)	0.0155 (4)	0.0174 (4)	0.0029 (4)	0.0041 (3)	0.0007 (3)
C21	0.0240 (5)	0.0133 (4)	0.0205 (4)	−0.0016 (4)	0.0053 (4)	−0.0005 (3)
C22	0.0191 (4)	0.0154 (4)	0.0189 (4)	−0.0038 (3)	0.0032 (3)	0.0002 (3)

Geometric parameters (Å, º) top

Cl1—C20	1.7407 (11)	C8—C15	1.4515 (15)
S1—O1	1.4480 (8)	C9—H9A	0.9300
S1—O2	1.4495 (8)	C10—C11	1.3937 (16)
S1—O3	1.4615 (9)	C10—C15	1.4172 (15)
S1—C17	1.7769 (11)	C11—C12	1.3848 (19)
N1—C1	1.3595 (14)	C11—H11A	0.9300
N1—C5	1.3699 (13)	C12—C13	1.4033 (19)
N1—C16	1.4790 (14)	C12—H12A	0.9300
N2—C9	1.3531 (15)	C13—C14	1.3862 (17)
N2—C10	1.3823 (15)	C13—H13A	0.9300
N2—H1N2	0.891 (18)	C14—C15	1.4060 (15)
C1—C2	1.3673 (17)	C14—H14A	0.9300
C1—H1A	0.9300	C16—H16A	0.9600
C2—C3	1.3961 (17)	C16—H16B	0.9600
C2—H2A	0.9300	C16—H16C	0.9600
C3—C4	1.3723 (16)	C17—C22	1.3949 (15)
C3—H3A	0.9300	C17—C18	1.3996 (14)
C4—C5	1.4111 (15)	C18—C19	1.3887 (15)
C4—H4A	0.9300	C18—H18A	0.9300
C5—C6	1.4442 (15)	C19—C20	1.3901 (15)
C6—C7	1.3567 (14)	C19—H19A	0.9300
C6—H6A	0.9300	C20—C21	1.3896 (16)
C7—C8	1.4318 (15)	C21—C22	1.3990 (15)
C7—H7A	0.9300	C21—H21A	0.9300
C8—C9	1.3947 (14)	C22—H22A	0.9300

O1—S1—O2	113.07 (5)	C11—C10—C15	123.00 (10)
O1—S1—O3	113.29 (6)	C12—C11—C10	117.11 (11)
O2—S1—O3	112.84 (6)	C12—C11—H11A	121.4
O1—S1—C17	106.28 (5)	C10—C11—H11A	121.4
O2—S1—C17	105.82 (5)	C11—C12—C13	121.10 (11)
O3—S1—C17	104.64 (5)	C11—C12—H12A	119.5
C1—N1—C5	121.81 (9)	C13—C12—H12A	119.5
C1—N1—C16	117.49 (9)	C14—C13—C12	121.72 (11)
C5—N1—C16	120.70 (9)	C14—C13—H13A	119.1
C9—N2—C10	109.27 (9)	C12—C13—H13A	119.1
C9—N2—H1N2	125.2 (12)	C13—C14—C15	118.59 (11)
C10—N2—H1N2	125.2 (12)	C13—C14—H14A	120.7
N1—C1—C2	121.68 (10)	C15—C14—H14A	120.7
N1—C1—H1A	119.2	C14—C15—C10	118.46 (10)
C2—C1—H1A	119.2	C14—C15—C8	135.36 (10)
C1—C2—C3	118.40 (11)	C10—C15—C8	106.17 (9)
C1—C2—H2A	120.8	N1—C16—H16A	109.5
C3—C2—H2A	120.8	N1—C16—H16B	109.5
C4—C3—C2	119.79 (11)	H16A—C16—H16B	109.5
C4—C3—H3A	120.1	N1—C16—H16C	109.5
C2—C3—H3A	120.1	H16A—C16—H16C	109.5
C3—C4—C5	121.33 (10)	H16B—C16—H16C	109.5
C3—C4—H4A	119.3	C22—C17—C18	120.38 (10)
C5—C4—H4A	119.3	C22—C17—S1	121.17 (8)
N1—C5—C4	116.96 (10)	C18—C17—S1	118.44 (8)
N1—C5—C6	119.06 (9)	C19—C18—C17	120.07 (10)
C4—C5—C6	123.98 (9)	C19—C18—H18A	120.0
C7—C6—C5	123.15 (10)	C17—C18—H18A	120.0
C7—C6—H6A	118.4	C18—C19—C20	118.93 (10)
C5—C6—H6A	118.4	C18—C19—H19A	120.5
C6—C7—C8	126.99 (10)	C20—C19—H19A	120.5
C6—C7—H7A	116.5	C21—C20—C19	121.96 (10)
C8—C7—H7A	116.5	C21—C20—Cl1	119.80 (8)
C9—C8—C7	121.99 (10)	C19—C20—Cl1	118.19 (8)
C9—C8—C15	106.00 (9)	C20—C21—C22	118.85 (10)
C7—C8—C15	132.01 (9)	C20—C21—H21A	120.6
N2—C9—C8	110.32 (10)	C22—C21—H21A	120.6
N2—C9—H9A	124.8	C17—C22—C21	119.79 (10)
C8—C9—H9A	124.8	C17—C22—H22A	120.1
N2—C10—C11	128.76 (11)	C21—C22—H22A	120.1
N2—C10—C15	108.23 (10)

C5—N1—C1—C2	0.81 (16)	C13—C14—C15—C10	−1.26 (16)
C16—N1—C1—C2	−179.81 (10)	C13—C14—C15—C8	−179.77 (12)
N1—C1—C2—C3	0.65 (17)	N2—C10—C15—C14	−178.58 (10)
C1—C2—C3—C4	−1.28 (17)	C11—C10—C15—C14	1.74 (16)
C2—C3—C4—C5	0.51 (18)	N2—C10—C15—C8	0.33 (12)
C1—N1—C5—C4	−1.56 (15)	C11—C10—C15—C8	−179.35 (10)
C16—N1—C5—C4	179.08 (9)	C9—C8—C15—C14	177.96 (12)
C1—N1—C5—C6	178.44 (10)	C7—C8—C15—C14	−2.8 (2)
C16—N1—C5—C6	−0.92 (14)	C9—C8—C15—C10	−0.68 (12)
C3—C4—C5—N1	0.90 (16)	C7—C8—C15—C10	178.61 (11)
C3—C4—C5—C6	−179.10 (11)	O1—S1—C17—C22	25.07 (10)
N1—C5—C6—C7	−178.80 (10)	O2—S1—C17—C22	−95.40 (9)
C4—C5—C6—C7	1.21 (17)	O3—S1—C17—C22	145.20 (9)
C5—C6—C7—C8	179.27 (10)	O1—S1—C17—C18	−155.09 (8)
C6—C7—C8—C9	176.40 (11)	O2—S1—C17—C18	84.44 (9)
C6—C7—C8—C15	−2.78 (19)	O3—S1—C17—C18	−34.96 (9)
C10—N2—C9—C8	−0.61 (13)	C22—C17—C18—C19	−0.23 (15)
C7—C8—C9—N2	−178.58 (10)	S1—C17—C18—C19	179.92 (8)
C15—C8—C9—N2	0.79 (12)	C17—C18—C19—C20	−0.80 (15)
C9—N2—C10—C11	179.81 (11)	C18—C19—C20—C21	1.17 (16)
C9—N2—C10—C15	0.15 (12)	C18—C19—C20—Cl1	−176.49 (8)
N2—C10—C11—C12	179.53 (11)	C19—C20—C21—C22	−0.48 (16)
C15—C10—C11—C12	−0.86 (17)	Cl1—C20—C21—C22	177.14 (8)
C10—C11—C12—C13	−0.48 (18)	C18—C17—C22—C21	0.93 (15)
C11—C12—C13—C14	0.92 (19)	S1—C17—C22—C21	−179.23 (8)
C12—C13—C14—C15	−0.01 (18)	C20—C21—C22—C17	−0.57 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O1ⁱ	0.891 (18)	1.864 (19)	2.7541 (14)	176.2 (18)
C1—H1A···O3	0.93	2.53	3.2380 (14)	133
C7—H7A···O2ⁱⁱ	0.93	2.59	3.3067 (14)	134
C14—H14A···O2ⁱⁱⁱ	0.93	2.52	3.2605 (14)	137
C16—H16C···O2ⁱⁱⁱ	0.96	2.37	3.2645 (15)	156
C19—H19A···O1^iv	0.93	2.30	3.1432 (14)	151
C21—H21A···O3ⁱⁱⁱ	0.93	2.55	3.1885 (14)	127
C4—H4A···Cg3^v	0.93	2.85	3.5956 (11)	138
C16—H16A···Cg1^vi	0.96	2.72	3.4622 (12)	134
C16—H16B···Cg3	0.96	2.67	3.5533 (11)	153

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₅N₂⁺·C₆H₄ClO₃S⁻
M_r	426.91
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.4891 (1), 13.1650 (1), 20.3428 (2)
β (°)	98.801 (1)
V (Å³)	1982.06 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.34 × 0.28 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.899, 0.942
No. of measured, independent and observed [I > 2σ(I)] reflections	39049, 8706, 7032
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.807

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.110, 1.05
No. of reflections	8706
No. of parameters	267
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.88, −0.41

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O1ⁱ	0.891 (18)	1.864 (19)	2.7541 (14)	176.2 (18)
C1—H1A···O3	0.93	2.53	3.2380 (14)	133
C7—H7A···O2ⁱⁱ	0.93	2.59	3.3067 (14)	134
C14—H14A···O2ⁱⁱⁱ	0.93	2.52	3.2605 (14)	137
C16—H16C···O2ⁱⁱⁱ	0.96	2.37	3.2645 (15)	156
C19—H19A···O1^iv	0.93	2.30	3.1432 (14)	151
C21—H21A···O3ⁱⁱⁱ	0.93	2.55	3.1885 (14)	127
C4—H4A···Cg3^v	0.93	2.85	3.5956 (11)	138
C16—H16A···Cg1^vi	0.96	2.72	3.4622 (12)	134
C16—H16B···Cg3	0.96	2.67	3.5533 (11)	153

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

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 the Prince of Songkla University for financial support through the Crystal Materials Research Unit. The authors also thank Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chanawanno, K., Chantrapromma, S. & Fun, H.-K. (2008). Acta Cryst. E64, o1882–o1883. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chantrapromma, S., Laksana, C., Ruanwas, P. & Fun, H.-K. (2008). Acta Cryst. E64, o574–o575. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chantrapromma, S., Jindawong, B., Fun, H.-K., Patil, P. S. & Karalai, C. (2006). Acta Cryst. E62, o1802–o1804. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chantrapromma, S., Jansrisewangwong, P., Musor, R. & Fun, H.-K. (2009). Acta Cryst. E65, o217–o218. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chantrapromma, S., Suwanwong, T. & Fun, H.-K. (2007). Acta Cryst. E63, o821–o823. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107. CrossRef CAS Web of Science IUCr Journals Google Scholar
Ogawa, J., Okada, S., Glavcheva, Z. & Nakanishi, H. (2008). J. Cryst. Growth, 310, 836–842. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Weir, C. A. M., Hadizad, T., Beaudin, A. M. R. & Wang, Z.-Y. (2003). Tetrahedron Lett. 44, 4697–4700. Web of Science CrossRef CAS Google Scholar
Yang, Z., Wörle, M., Mutter, L., Jazbinsek, M. & Günter, P. (2007). Cryst. Growth Des. 7, 83–86. Web of Science CSD CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.