1,1′-Dimethyl-4,4′-(2,4-di-1-naphthyl­cyclo­butane-1,3-di­yl)dipyridinium–(E)-1-methyl-4-[2-(1-naphth­yl)vin­yl]pyridinium–4-amino­benzene­sulfonate–water (0.25/1.50/2/2)

Fun, H.-K.; Chanawanno, K.; Chantrapromma, S.

doi:10.1107/S1600536809029730

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Pages o2048-o2049

doi:10.1107/S1600536809029730

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1,1′-Dimethyl-4,4′-(2,4-di-1-naphthylcyclobutane-1,3-diyl)dipyridinium–(E)-1-methyl-4-[2-(1-naphthyl)vinyl]pyridinium–4-aminobenzenesulfonate–water (0.25/1.50/2/2)

Hoong-Kun Fun,^a ^*‡ Kullapa Chanawanno ^b and Suchada Chantrapromma ^b §

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bCrystal Materials Research Unit, Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand
^*Correspondence e-mail: hkfun@usm.my

(Received 6 July 2009; accepted 27 July 2009; online 31 July 2009)

In the title compound, 1.5C₁₈H₁₆N⁺·0.25C₃₆H₃₂N₂²⁺·2C₆H₆NO₃S⁻·2H₂O, the monocation exists in the E configuration with respect to the ethenyl C=C double bond and is almost planar, the dihedral angles between the pyridinium and the fused six-membered rings being 3.1 (7) and 3.8 (8)°. The dication lies about an inversion centre. In the crystal, the dication occupies almost the same site occupied by monocations at (x, y, z) and (−x, 1 − y, 1 − z). The anions and water molecules are linked into a chain along the a axis by O—H⋯O and N—H⋯O hydrogen bonds. The structure is further stabilized by C—H⋯O hydrogen bonds and π–π interactions between pyridinium and benzene rings, with centroid–centroid distances in the range 3.516 (9)–3.553 (8) Å. The crystal is a twin with twin law, TWIN $[\overline{1}]$ 0 0 0 $[\overline{1}]$ 0 1 0 1. The monocation and dication are disordered with fractional site occupancy ratio of 0.75:0.25.

Related literature

For bond-length data, see: Allen et al. (1987 ). For background to non-linear optical materials, see: Williams (1984 ). For related structures, see: Chantrapromma et al. (2009 ); Fun et al. (2009 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer, (1986 ).

Experimental

Crystal data

1.5C₁₈H₁₆N⁺·0.25C₃₆H₃₂N₂²⁺·2C₆H₆NO₃S⁻·2H₂O
M_r = 873.04
Monoclinic, P 2₁ /c
a = 6.6352 (4) Å
b = 14.8824 (8) Å
c = 20.9347 (13) Å
β = 97.921 (3)°
V = 2047.5 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 100 K
0.52 × 0.13 × 0.07 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.906, T_max = 0.986
21302 measured reflections
4099 independent reflections
3550 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.097
wR(F²) = 0.275
S = 1.07
4099 reflections
440 parameters
300 restraints
H-atom parameters constrained
Δρ_max = 1.20 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O3	0.84	2.01	2.831 (7)	164
O1W—H2W1⋯O1ⁱ	0.84	2.04	2.853 (6)	164
N2—H2B⋯O1ⁱⁱ	0.86	2.23	3.018 (6)	153
N2—H2C⋯O2ⁱⁱⁱ	0.86	2.23	2.991 (6)	147
C18—H18A⋯O1W	0.96	2.52	3.448 (13)	163
C18—H18B⋯O1W^iv	0.96	2.21	3.168 (13)	173
Symmetry codes: (i) x-1, y, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) -x, -y, -z+1.

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/S1600536809029730/ci2847sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809029730/ci2847Isup2.hkl

checkCIF report

Comment top

The important requirement of NLO material is that the molecules have to align in noncentrosymmetric space group in the crystal (Williams, 1984). So the X-ray structure determination is a very important procedure to find out whether the compound is NLO active. During the course of our NLO research, we have previously reported crystal structures of (E)-1-methyl-4-[2-(2-naphthyl)vinyl]pyridinium iodide (I) (Fun et al., 2009) and (E)-1-methyl-4-[2-(1-naphthyl)vinyl]pyridinium 4-bromobenzenesulfonate (II) (Chantrapromma et al., 2009). These compounds were prepared by extending conjugated π-system which is a popular strategy to design NLO materials. In order to study the relation and effect of anions to the NLO properties, we attempted to synthesize (E)-1-methyl-4-[2-(2-naphthyl)vinyl]pyridinium 4-aminobenzenesulfonate (III) by replacing the iodide anion in (I) by 4-aminobenzenesulfonate. However, we got a co-crystal of the [2+2] cycloaddition product of (E)-1-methyl-4-[2-(2-naphthyl)vinyl]pyridinium with (III). The title compound crystallizes in the monoclinic centrosymmetric space group P2₁/c, indicating that the second-order NLO properties are not present.

Fig. 1 shows the molecular structure of the title compound, which consists of one and a half C₁₈H₁₆N⁺ cation, one-quarter of the C₃₆C₃₂N₂²⁺ dication, two C₆H₆NO₃S^- anions and two water molecules. The monocation exists in the E configuration with respect to the C11═C12 double bond (C10—C11—C12—C13 = -179.9 (10)°) and is almost planar with dihedral angles between the pyridinium and C1–C6 and C1/C6–C10 rings being 3.1 (7) and 3.8 (8)°, respectively. The dication lies on an inversion center. The dihedral angle between the pyridinium and two aromatic C1A–C6A and C1A/C6A–C10A rings being 13 (2) and 14 (2)°, respectively, with the C10A–C11A–C12A–C13A torsion angle being -115 (3)°. Bond lengths are in normal ranges (Allen et al., 1987) and comparable with those in related structures (Chantrapromma et al., 2009; Fun et al., 2009).

In the crystal structure, the anions and water molecules are linked into a chain along the a axis by O—H···O and N—H···O hydrogen bonds (Fig.2). The structure is further stabilized by C—H···O hydrogen bonds (Table 1) and π–π interactions between pyridinium and benzene rings [Cg1···Cg2^v = 3.553 (8) Å, Cg1···Cg2^vi = 3.530 (8) Å, Cg1···Cg3^v = 3.550 (9) Å and Cg1···Cg3^vi = 3.516 (9) Å; Cg1, Cg2 and Cg3 are centroids of the N1/C13-C17, C1-C6 and C1/C6-C10 rings, respectively. Symmetry code: (v) -x, 1-y, 1-z; (vi) 1-x, 1-y, 1-z].

Related literature top

For bond-length data, see: Allen et al. (1987). For background to non-linear optical materials, see: Williams (1984). For related structures, see: Chantrapromma et al. (2009); Fun et al. (2009). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer, (1986).

Experimental top

Silver(I) 4-aminobenzenesulfonate (compound A) was prepared by mixing a solution of sulfanilic acid (0.12 g, 0.71 mmol) in hot methanol (50 ml) with a solution of sodium hydroxide (0.03 g, 0.71 mmol) in methanol (30 ml), followed by addition of a solution of silver nitrate (0.12 g, 0.71 mmol) in methanol (30 ml). A colourless solution together with black solid of AgI was obtained which was then filtered. The white solid of compound A was collected after allowing the filtrate to stand in air for a few days. (E)-1-Methyl-4-[2-(1-naphthyl)vinyl]pyridinium iodide (compound B) was prepared by the previous method (Chantrapromma et al., 2009). The yellow solid of compound B (0.27 g, 0.71 mmol) was mixed with compound A (0.20 g, 0.71 mmol) in methanol (100 ml) and stirred for 30 minutes. The precipitate of silver iodide which formed was filtered and the filtrate was evaporated to give a yellow solid product. The yellow solid was repeatedly recrystallized for three times by dissolving the yellow solid in methanol and the solution was heated at 323 K to get a clear solution. The [2+2] cycloaddition of the (E)-1-methyl-4-[2-(1-naphthyl)vinyl]pyridinium occured upon heating. Green needle-shaped single crystals of the title compound suitable for x-ray structure determination were obtained from a methanol solution by slow evaporation at room temperature over a month (m.p. 513-514 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. The dication is shown in open bonds. Unlabelled atoms in the dication are related to the labelled atoms by the symmetry operation (- x, 1 -y, 1 - z). H atoms of cations were omitted for clarity. The monocation and dication have fractional occupancies of 0.75 and 0.25, respectively.

Fig. 2. The crystal packing of the title compound viewed down the b axis. Hydrogen bonds are shown as dashed lines. The monocation with a fractional occupancy of 0.75 is shown while the dication with an occupancy of 0.25 has been omitted for clarity.

1,1'-Dimethyl-4,4'-(2,4-di-1-naphthylcyclobutane-1,3-diyl)dipyridinium– (E)-1-methyl-4-[2-(1-naphthyl)vinyl]pyridinium– 4-aminobenzenesulfonate–water (0.25/1.50/2/2) top

Crystal data top

1.5C₁₈H₁₆N⁺·0.25C₃₆H₃₂N₂²⁺·2C₆H₆NO₃S⁻·2H₂O	F(000) = 920
M_r = 873.04	D_x = 1.416 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 513–514 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 6.6352 (4) Å	Cell parameters from 4099 reflections
b = 14.8824 (8) Å	θ = 1.0–26.0°
c = 20.9347 (13) Å	µ = 0.19 mm⁻¹
β = 97.921 (3)°	T = 100 K
V = 2047.5 (2) Å³	Needle, green
Z = 2	0.52 × 0.13 × 0.07 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	4099 independent reflections
Radiation source: sealed tube	3550 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→8
T_min = 0.906, T_max = 0.986	k = −16→18
21302 measured reflections	l = −25→23

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)] = 0.097	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.275	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.1017P)² + 16.5792P] where P = (F_o² + 2F_c²)/3
4099 reflections	(Δ/σ)_max = 0.001
440 parameters	Δρ_max = 1.20 e Å⁻³
300 restraints	Δρ_min = −0.62 e Å⁻³

Crystal data top

1.5C₁₈H₁₆N⁺·0.25C₃₆H₃₂N₂²⁺·2C₆H₆NO₃S⁻·2H₂O	V = 2047.5 (2) Å³
M_r = 873.04	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.6352 (4) Å	µ = 0.19 mm⁻¹
b = 14.8824 (8) Å	T = 100 K
c = 20.9347 (13) Å	0.52 × 0.13 × 0.07 mm
β = 97.921 (3)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	4099 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3550 reflections with I > 2σ(I)
T_min = 0.906, T_max = 0.986	R_int = 0.044
21302 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.097	300 restraints
wR(F²) = 0.275	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.1017P)² + 16.5792P] where P = (F_o² + 2F_c²)/3
4099 reflections	Δρ_max = 1.20 e Å⁻³
440 parameters	Δρ_min = −0.62 e Å⁻³

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	Occ. (<1)
S1	0.3679 (2)	0.09002 (8)	0.28289 (6)	0.0218 (3)
O1	0.5862 (6)	0.0903 (2)	0.28680 (19)	0.0275 (9)
O2	0.2700 (6)	0.0497 (3)	0.2232 (2)	0.0298 (9)
O3	0.2958 (7)	0.0516 (3)	0.3399 (2)	0.0352 (10)
N2	0.1545 (7)	0.4776 (3)	0.2898 (2)	0.0245 (10)
H2B	0.2400	0.5174	0.2807	0.029*
H2C	0.0426	0.4940	0.3028	0.029*
C19	0.2965 (8)	0.2043 (3)	0.2812 (2)	0.0197 (10)
C20	0.4260 (8)	0.2701 (4)	0.2610 (2)	0.0227 (11)
H20	0.5461	0.2529	0.2461	0.027*
C21	0.3758 (8)	0.3600 (4)	0.2630 (3)	0.0226 (11)
H21	0.4642	0.4028	0.2501	0.027*
C22	0.1966 (8)	0.3877 (3)	0.2838 (2)	0.0197 (10)
C23	0.0644 (8)	0.3219 (4)	0.3019 (2)	0.0212 (11)
H23	−0.0585	0.3393	0.3148	0.025*
C24	0.1135 (8)	0.2316 (4)	0.3009 (2)	0.0224 (11)
H24	0.0242	0.1889	0.3134	0.027*
N1	0.2543 (17)	0.1774 (6)	0.5190 (5)	0.024 (2)	0.75
C1	0.2403 (16)	0.6807 (6)	0.4633 (4)	0.0197 (19)	0.75
C2	0.2154 (18)	0.6500 (6)	0.3985 (4)	0.0223 (17)	0.75
H2	0.2124	0.5866	0.3900	0.027*	0.75
C3	0.1902 (17)	0.7092 (5)	0.3482 (5)	0.0228 (19)	0.75
H3	0.1750	0.6867	0.3048	0.027*	0.75
C4	0.191 (2)	0.8026 (7)	0.3597 (5)	0.025 (3)	0.75
H4	0.1721	0.8437	0.3240	0.030*	0.75
C5	0.215 (3)	0.8344 (7)	0.4214 (6)	0.028 (3)	0.75
H5	0.2177	0.8980	0.4290	0.033*	0.75
C6	0.240 (3)	0.7748 (6)	0.4755 (5)	0.022 (2)	0.75
C7	0.264 (4)	0.8077 (7)	0.5393 (6)	0.025 (3)	0.75
H7	0.2570	0.8712	0.5468	0.030*	0.75
C8	0.294 (3)	0.7491 (7)	0.5904 (5)	0.021 (2)	0.75
H8	0.3159	0.7714	0.6338	0.026*	0.75
C9	0.294 (2)	0.6548 (7)	0.5788 (4)	0.020 (2)	0.75
H9	0.3097	0.6144	0.6149	0.024*	0.75
C10	0.269 (2)	0.6203 (6)	0.5185 (4)	0.025 (2)	0.75
C11	0.2690 (12)	0.5210 (5)	0.5082 (4)	0.0316 (18)	0.75
H11	0.2690	0.5006	0.4647	0.038*	0.75
C12	0.2670 (11)	0.4559 (5)	0.5546 (4)	0.0280 (16)	0.75
H12	0.2651	0.4745	0.5984	0.034*	0.75
C13	0.2678 (15)	0.3597 (6)	0.5405 (4)	0.032 (2)	0.75
C14	0.2476 (19)	0.3249 (8)	0.4777 (5)	0.027 (3)	0.75
H14	0.2419	0.3647	0.4414	0.032*	0.75
C15	0.239 (3)	0.2339 (7)	0.4682 (6)	0.026 (3)	0.75
H15	0.2190	0.2103	0.4251	0.031*	0.75
C16	0.274 (2)	0.2081 (7)	0.5799 (5)	0.028 (3)	0.75
H16	0.2816	0.1666	0.6153	0.034*	0.75
C17	0.2813 (15)	0.2983 (7)	0.5916 (4)	0.025 (2)	0.75
H17	0.2945	0.3197	0.6352	0.030*	0.75
C18	0.259 (2)	0.0794 (7)	0.5068 (6)	0.035 (3)	0.75
H18A	0.1841	0.0665	0.4652	0.053*	0.75
H18B	0.1984	0.0482	0.5395	0.053*	0.75
H18C	0.3974	0.0602	0.5078	0.053*	0.75
N1A	0.285 (6)	0.1907 (16)	0.5264 (14)	0.018 (5)	0.25
C1A	0.239 (4)	0.6868 (16)	0.4553 (14)	0.024 (4)	0.25
C2A	0.208 (6)	0.6680 (19)	0.3881 (14)	0.0223 (17)	0.25
H2A	0.1985	0.6086	0.3742	0.027*	0.25
C3A	0.193 (5)	0.735 (2)	0.3437 (15)	0.0228 (19)	0.25
H3A	0.1732	0.7209	0.3000	0.027*	0.25
C4A	0.206 (7)	0.826 (2)	0.3629 (17)	0.024 (5)	0.25
H4A	0.1959	0.8710	0.3320	0.028*	0.25
C5A	0.233 (10)	0.8472 (19)	0.4267 (17)	0.023 (6)	0.25
H5A	0.2386	0.9073	0.4390	0.028*	0.25
C6A	0.254 (11)	0.7784 (17)	0.4752 (15)	0.025 (5)	0.25
C7A	0.285 (12)	0.801 (2)	0.5412 (16)	0.025 (6)	0.25
H7A	0.2940	0.8613	0.5538	0.030*	0.25
C8A	0.300 (10)	0.734 (2)	0.5867 (16)	0.026 (6)	0.25
H8A	0.3174	0.7491	0.6303	0.031*	0.25
C9A	0.290 (8)	0.643 (2)	0.5675 (15)	0.026 (6)	0.25
H9A	0.3136	0.5984	0.5990	0.031*	0.25
C10A	0.248 (7)	0.6176 (16)	0.5052 (15)	0.025 (5)	0.25
C11A	0.138 (4)	0.5304 (12)	0.4899 (10)	0.026 (4)	0.25
H11A	0.2028	0.5009	0.4561	0.031*	0.25
C12A	0.108 (3)	0.4637 (11)	0.5361 (9)	0.023 (3)	0.25
H12A	0.1363	0.4886	0.5797	0.028*	0.25
C13A	0.204 (4)	0.3737 (12)	0.5336 (10)	0.014 (4)	0.25
C14A	0.208 (5)	0.3306 (17)	0.4740 (11)	0.012 (5)	0.25
H14A	0.1831	0.3634	0.4359	0.015*	0.25
C15A	0.247 (8)	0.2405 (17)	0.4719 (14)	0.016 (6)	0.25
H15A	0.2481	0.2128	0.4322	0.019*	0.25
C16A	0.284 (6)	0.2299 (17)	0.5844 (13)	0.012 (5)	0.25
H16A	0.3106	0.1956	0.6218	0.014*	0.25
C17A	0.244 (4)	0.3190 (16)	0.5887 (11)	0.011 (5)	0.25
H17A	0.2423	0.3446	0.6292	0.014*	0.25
C18A	0.300 (6)	0.0916 (17)	0.5214 (19)	0.033 (8)	0.25
H18D	0.3278	0.0661	0.5639	0.049*	0.25
H18E	0.4090	0.0766	0.4974	0.049*	0.25
H18F	0.1747	0.0680	0.4998	0.049*	0.25
O1W	−0.0921 (7)	0.0188 (3)	0.3769 (2)	0.0447 (12)
H1W1	0.0098	0.0320	0.3590	0.067*
H2W1	−0.1996	0.0310	0.3525	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0227 (7)	0.0165 (6)	0.0267 (7)	0.0017 (5)	0.0054 (5)	0.0013 (5)
O1	0.034 (2)	0.0158 (18)	0.032 (2)	0.0041 (16)	0.0041 (17)	−0.0007 (16)
O2	0.031 (2)	0.022 (2)	0.035 (2)	−0.0017 (16)	0.0011 (17)	−0.0079 (17)
O3	0.049 (3)	0.025 (2)	0.034 (2)	0.0064 (18)	0.015 (2)	0.0102 (18)
N2	0.028 (2)	0.014 (2)	0.033 (2)	0.0018 (18)	0.008 (2)	−0.0024 (18)
C19	0.019 (2)	0.021 (3)	0.018 (2)	0.000 (2)	0.0002 (19)	0.001 (2)
C20	0.021 (3)	0.026 (3)	0.022 (3)	0.001 (2)	0.006 (2)	0.001 (2)
C21	0.022 (3)	0.021 (3)	0.025 (3)	−0.003 (2)	0.003 (2)	0.005 (2)
C22	0.030 (3)	0.018 (2)	0.010 (2)	0.001 (2)	−0.0016 (19)	0.0020 (18)
C23	0.021 (3)	0.024 (3)	0.020 (2)	0.003 (2)	0.007 (2)	0.000 (2)
C24	0.022 (3)	0.027 (3)	0.019 (2)	−0.001 (2)	0.002 (2)	0.000 (2)
N1	0.019 (5)	0.024 (4)	0.027 (4)	−0.009 (3)	0.001 (3)	−0.002 (3)
C1	0.014 (3)	0.025 (4)	0.020 (4)	−0.003 (3)	0.003 (3)	−0.007 (3)
C2	0.020 (3)	0.024 (4)	0.023 (4)	0.001 (3)	0.003 (3)	−0.002 (3)
C3	0.023 (3)	0.027 (5)	0.019 (3)	−0.003 (4)	0.002 (2)	−0.001 (4)
C4	0.021 (5)	0.032 (7)	0.021 (4)	0.000 (5)	−0.002 (3)	0.001 (4)
C5	0.029 (6)	0.025 (5)	0.028 (5)	0.001 (5)	0.000 (4)	−0.004 (4)
C6	0.014 (5)	0.027 (4)	0.027 (4)	0.002 (3)	0.002 (3)	−0.004 (3)
C7	0.029 (8)	0.016 (4)	0.029 (5)	0.001 (4)	0.004 (4)	−0.004 (3)
C8	0.020 (4)	0.016 (5)	0.026 (4)	0.000 (4)	−0.001 (3)	−0.010 (3)
C9	0.022 (4)	0.022 (5)	0.019 (4)	0.002 (3)	0.007 (4)	−0.007 (3)
C10	0.027 (5)	0.026 (4)	0.022 (6)	−0.003 (3)	0.006 (4)	−0.008 (3)
C11	0.029 (4)	0.040 (5)	0.024 (4)	0.008 (3)	−0.004 (3)	−0.004 (3)
C12	0.020 (4)	0.041 (4)	0.023 (4)	0.002 (3)	0.000 (3)	0.000 (3)
C13	0.034 (5)	0.031 (5)	0.027 (5)	0.015 (4)	−0.010 (4)	−0.001 (4)
C14	0.026 (7)	0.032 (5)	0.022 (4)	0.006 (4)	0.000 (4)	0.001 (4)
C15	0.020 (5)	0.033 (5)	0.023 (5)	−0.004 (4)	0.002 (4)	−0.005 (4)
C16	0.021 (5)	0.033 (6)	0.030 (5)	−0.004 (5)	0.005 (4)	0.002 (4)
C17	0.021 (5)	0.034 (7)	0.019 (4)	0.012 (4)	−0.001 (3)	0.001 (4)
C18	0.044 (7)	0.026 (5)	0.034 (6)	−0.007 (4)	−0.002 (5)	−0.002 (4)
N1A	0.018 (7)	0.017 (7)	0.020 (7)	−0.003 (6)	0.001 (5)	0.000 (5)
C1A	0.023 (6)	0.026 (6)	0.024 (6)	0.001 (5)	0.004 (5)	0.001 (5)
C2A	0.020 (3)	0.024 (4)	0.023 (4)	0.001 (3)	0.003 (3)	−0.002 (3)
C3A	0.023 (3)	0.027 (5)	0.019 (3)	−0.003 (4)	0.002 (2)	−0.001 (4)
C4A	0.022 (7)	0.026 (7)	0.022 (7)	−0.001 (6)	0.002 (5)	0.001 (6)
C5A	0.023 (7)	0.027 (8)	0.019 (8)	0.000 (6)	0.003 (6)	−0.001 (6)
C6A	0.024 (7)	0.026 (7)	0.024 (7)	0.001 (6)	0.004 (6)	0.000 (6)
C7A	0.026 (8)	0.025 (8)	0.025 (8)	0.000 (6)	0.004 (6)	0.000 (6)
C8A	0.024 (8)	0.026 (8)	0.028 (8)	−0.001 (6)	0.004 (6)	0.002 (6)
C9A	0.025 (8)	0.026 (8)	0.026 (8)	−0.002 (6)	0.004 (6)	0.002 (6)
C10A	0.025 (6)	0.029 (7)	0.023 (6)	−0.002 (5)	0.004 (5)	−0.003 (5)
C11A	0.026 (6)	0.027 (6)	0.025 (6)	−0.001 (5)	0.003 (5)	−0.001 (5)
C12A	0.025 (6)	0.025 (6)	0.021 (6)	0.002 (5)	0.005 (5)	0.001 (5)
C13A	0.016 (6)	0.013 (6)	0.014 (6)	0.002 (5)	0.005 (5)	0.006 (5)
C14A	0.012 (7)	0.012 (7)	0.013 (7)	−0.003 (5)	0.004 (5)	0.003 (6)
C15A	0.015 (8)	0.017 (8)	0.016 (8)	−0.003 (6)	0.001 (6)	0.002 (6)
C16A	0.010 (7)	0.014 (8)	0.012 (7)	0.002 (6)	0.003 (5)	0.004 (5)
C17A	0.012 (7)	0.010 (7)	0.012 (7)	0.004 (6)	0.001 (5)	0.004 (5)
C18A	0.031 (11)	0.033 (11)	0.034 (11)	−0.010 (8)	0.006 (8)	−0.007 (8)
O1W	0.041 (3)	0.061 (3)	0.034 (2)	0.017 (2)	0.012 (2)	0.015 (2)

Geometric parameters (Å, º) top

S1—O1	1.439 (4)	C16—C17	1.363 (12)
S1—O2	1.456 (4)	C16—H16	0.96
S1—O3	1.462 (4)	C17—H17	0.96
S1—C19	1.765 (5)	C18—H18A	0.96
N2—C22	1.376 (7)	C18—H18B	0.96
N2—H2B	0.86	C18—H18C	0.96
N2—H2C	0.86	N1A—C16A	1.348 (17)
C19—C24	1.395 (7)	N1A—C15A	1.354 (16)
C19—C20	1.406 (7)	N1A—C18A	1.484 (18)
C20—C21	1.381 (8)	C1A—C2A	1.421 (16)
C20—H20	0.93	C1A—C6A	1.425 (16)
C21—C22	1.385 (8)	C1A—C10A	1.463 (17)
C21—H21	0.93	C2A—C3A	1.358 (18)
C22—C23	1.401 (7)	C2A—H2A	0.93
C23—C24	1.384 (8)	C3A—C4A	1.407 (19)
C23—H23	0.93	C3A—H3A	0.93
C24—H24	0.93	C4A—C5A	1.361 (18)
N1—C16	1.344 (10)	C4A—H4A	0.93
N1—C15	1.350 (9)	C5A—C6A	1.435 (16)
N1—C18	1.481 (11)	C5A—H5A	0.93
C1—C2	1.419 (9)	C6A—C7A	1.411 (16)
C1—C6	1.423 (9)	C7A—C8A	1.373 (17)
C1—C10	1.457 (10)	C7A—H7A	0.93
C2—C3	1.364 (10)	C8A—C9A	1.422 (18)
C2—H2	0.96	C8A—H8A	0.93
C3—C4	1.411 (11)	C9A—C10A	1.348 (18)
C3—H3	0.96	C9A—H9A	0.93
C4—C5	1.364 (10)	C10A—C11A	1.500 (9)
C4—H4	0.96	C11A—C12A	1.421 (18)
C5—C6	1.431 (9)	C11A—C12Aⁱ	1.65 (3)
C5—H5	0.96	C11A—H11A	0.98
C6—C7	1.411 (9)	C12A—C13A	1.488 (18)
C7—C8	1.373 (10)	C12A—C11Aⁱ	1.65 (3)
C7—H7	0.96	C12A—H12A	0.98
C8—C9	1.424 (10)	C13A—C17A	1.406 (18)
C8—H8	0.96	C13A—C14A	1.407 (16)
C9—C10	1.351 (10)	C14A—C15A	1.368 (17)
C9—H9	0.96	C14A—H14A	0.93
C10—C11	1.493 (11)	C15A—H15A	0.93
C11—C12	1.374 (11)	C16A—C17A	1.359 (19)
C11—H11	0.96	C16A—H16A	0.93
C12—C13	1.462 (11)	C17A—H17A	0.93
C12—H12	0.96	C18A—H18D	0.96
C13—C17	1.401 (11)	C18A—H18E	0.96
C13—C14	1.402 (10)	C18A—H18F	0.96
C14—C15	1.368 (10)	O1W—H1W1	0.84
C14—H14	0.96	O1W—H2W1	0.84
C15—H15	0.96

O1—S1—O2	112.1 (2)	C17—C16—H16	119.9
O1—S1—O3	113.2 (3)	C16—C17—C13	120.6 (8)
O2—S1—O3	112.5 (3)	C16—C17—H17	119.6
O1—S1—C19	105.2 (2)	C13—C17—H17	119.8
O2—S1—C19	107.1 (2)	N1—C18—H18A	109.5
O3—S1—C19	106.0 (2)	N1—C18—H18B	109.5
C22—N2—H2B	120.0	H18A—C18—H18B	109.5
C22—N2—H2C	120.0	N1—C18—H18C	109.5
H2B—N2—H2C	120.0	H18A—C18—H18C	109.5
C24—C19—C20	118.6 (5)	H18B—C18—H18C	109.5
C24—C19—S1	121.1 (4)	C16A—N1A—C15A	120.0 (18)
C20—C19—S1	120.2 (4)	C16A—N1A—C18A	120 (2)
C21—C20—C19	120.4 (5)	C15A—N1A—C18A	119.4 (19)
C21—C20—H20	119.8	C2A—C1A—C6A	118.2 (16)
C19—C20—H20	119.8	C2A—C1A—C10A	123.7 (18)
C20—C21—C22	121.3 (5)	C6A—C1A—C10A	118.0 (16)
C20—C21—H21	119.4	C3A—C2A—C1A	121.3 (19)
C22—C21—H21	119.4	C3A—C2A—H2A	119.4
N2—C22—C21	120.8 (5)	C1A—C2A—H2A	119.4
N2—C22—C23	120.8 (5)	C2A—C3A—C4A	120.9 (19)
C21—C22—C23	118.3 (5)	C2A—C3A—H3A	119.5
C24—C23—C22	121.2 (5)	C4A—C3A—H3A	119.5
C24—C23—H23	119.4	C5A—C4A—C3A	120 (2)
C22—C23—H23	119.4	C5A—C4A—H4A	120.0
C23—C24—C19	120.2 (5)	C3A—C4A—H4A	120.0
C23—C24—H24	119.9	C4A—C5A—C6A	121 (2)
C19—C24—H24	119.9	C4A—C5A—H5A	119.5
C16—N1—C15	121.5 (8)	C6A—C5A—H5A	119.5
C16—N1—C18	119.8 (8)	C7A—C6A—C1A	120.8 (17)
C15—N1—C18	118.6 (8)	C7A—C6A—C5A	120.5 (18)
C2—C1—C6	119.1 (7)	C1A—C6A—C5A	118.6 (16)
C2—C1—C10	123.1 (7)	C8A—C7A—C6A	119.4 (19)
C6—C1—C10	117.8 (7)	C8A—C7A—H7A	120.3
C3—C2—C1	121.0 (7)	C6A—C7A—H7A	120.3
C3—C2—H2	119.7	C7A—C8A—C9A	120 (2)
C1—C2—H2	119.3	C7A—C8A—H8A	119.9
C2—C3—C4	120.5 (7)	C9A—C8A—H8A	119.9
C2—C3—H3	119.4	C10A—C9A—C8A	122 (2)
C4—C3—H3	120.1	C10A—C9A—H9A	118.8
C5—C4—C3	120.1 (8)	C8A—C9A—H9A	118.8
C5—C4—H4	120.0	C9A—C10A—C1A	118.6 (17)
C3—C4—H4	119.9	C9A—C10A—C11A	118 (2)
C4—C5—C6	121.3 (8)	C1A—C10A—C11A	119.0 (18)
C4—C5—H5	119.8	C12A—C11A—C10A	124.7 (17)
C6—C5—H5	118.9	C12A—C11A—C12Aⁱ	91.9 (16)
C7—C6—C1	120.6 (7)	C10A—C11A—C12Aⁱ	117 (2)
C7—C6—C5	121.3 (8)	C12A—C11A—H11A	107.2
C1—C6—C5	118.1 (7)	C10A—C11A—H11A	107.2
C8—C7—C6	120.1 (7)	C12Aⁱ—C11A—H11A	107.2
C8—C7—H7	120.1	C11A—C12A—C13A	120.2 (16)
C6—C7—H7	119.7	C11A—C12A—C11Aⁱ	88.1 (16)
C7—C8—C9	119.8 (7)	C13A—C12A—C11Aⁱ	116.5 (17)
C7—C8—H8	120.3	C11A—C12A—H12A	110.1
C9—C8—H8	119.9	C13A—C12A—H12A	110.1
C10—C9—C8	122.0 (7)	C11Aⁱ—C12A—H12A	110.1
C10—C9—H9	118.9	C17A—C13A—C14A	116.1 (16)
C8—C9—H9	119.1	C17A—C13A—C12A	121.7 (16)
C9—C10—C1	119.6 (7)	C14A—C13A—C12A	120.1 (16)
C9—C10—C11	120.6 (7)	C15A—C14A—C13A	120.1 (18)
C1—C10—C11	119.9 (7)	C15A—C14A—H14A	120.0
C12—C11—C10	126.6 (7)	C13A—C14A—H14A	120.0
C12—C11—H11	116.6	N1A—C15A—C14A	121.6 (19)
C10—C11—H11	116.8	N1A—C15A—H15A	119.2
C11—C12—C13	123.2 (7)	C14A—C15A—H15A	119.2
C11—C12—H12	118.3	N1A—C16A—C17A	120.4 (19)
C13—C12—H12	118.5	N1A—C16A—H16A	119.8
C17—C13—C14	117.6 (8)	C17A—C16A—H16A	119.8
C17—C13—C12	119.1 (8)	C16A—C17A—C13A	121.9 (18)
C14—C13—C12	123.3 (8)	C16A—C17A—H17A	119.1
C15—C14—C13	119.9 (9)	C13A—C17A—H17A	119.1
C15—C14—H14	120.0	N1A—C18A—H18D	109.5
C13—C14—H14	120.0	N1A—C18A—H18E	109.5
N1—C15—C14	120.4 (9)	H18D—C18A—H18E	109.5
N1—C15—H15	119.8	N1A—C18A—H18F	109.5
C14—C15—H15	119.8	H18D—C18A—H18F	109.5
N1—C16—C17	120.1 (8)	H18E—C18A—H18F	109.5
N1—C16—H16	120.1	H1W1—O1W—H2W1	110.2

O1—S1—C19—C24	−156.2 (4)	C18—N1—C16—C17	176.2 (12)
O2—S1—C19—C24	84.3 (5)	N1—C16—C17—C13	0.3 (16)
O3—S1—C19—C24	−36.0 (5)	C14—C13—C17—C16	−0.3 (15)
O1—S1—C19—C20	22.6 (5)	C12—C13—C17—C16	177.2 (11)
O2—S1—C19—C20	−96.9 (4)	C6A—C1A—C2A—C3A	0 (3)
O3—S1—C19—C20	142.9 (4)	C10A—C1A—C2A—C3A	177 (2)
C24—C19—C20—C21	2.4 (8)	C1A—C2A—C3A—C4A	0 (2)
S1—C19—C20—C21	−176.4 (4)	C2A—C3A—C4A—C5A	0 (5)
C19—C20—C21—C22	−1.1 (8)	C3A—C4A—C5A—C6A	2 (7)
C20—C21—C22—N2	175.5 (5)	C2A—C1A—C6A—C7A	180 (4)
C20—C21—C22—C23	−1.0 (8)	C10A—C1A—C6A—C7A	2 (6)
N2—C22—C23—C24	−174.7 (5)	C2A—C1A—C6A—C5A	1 (6)
C21—C22—C23—C24	1.8 (7)	C10A—C1A—C6A—C5A	−176 (4)
C22—C23—C24—C19	−0.5 (8)	C4A—C5A—C6A—C7A	179 (5)
C20—C19—C24—C23	−1.7 (7)	C4A—C5A—C6A—C1A	−2 (7)
S1—C19—C24—C23	177.2 (4)	C1A—C6A—C7A—C8A	0 (8)
C6—C1—C2—C3	−0.4 (13)	C5A—C6A—C7A—C8A	179 (5)
C10—C1—C2—C3	−179.7 (9)	C6A—C7A—C8A—C9A	1 (8)
C1—C2—C3—C4	0.9 (12)	C7A—C8A—C9A—C10A	−6 (7)
C2—C3—C4—C5	−0.9 (17)	C8A—C9A—C10A—C1A	8 (6)
C3—C4—C5—C6	0 (2)	C8A—C9A—C10A—C11A	−149 (4)
C2—C1—C6—C7	179.9 (13)	C2A—C1A—C10A—C9A	176 (3)
C10—C1—C6—C7	−1 (2)	C6A—C1A—C10A—C9A	−6 (5)
C2—C1—C6—C5	−0.1 (19)	C2A—C1A—C10A—C11A	−27 (4)
C10—C1—C6—C5	179.3 (13)	C6A—C1A—C10A—C11A	151 (4)
C4—C5—C6—C7	−179.9 (16)	C9A—C10A—C11A—C12A	−12 (5)
C4—C5—C6—C1	0 (2)	C1A—C10A—C11A—C12A	−170 (2)
C1—C6—C7—C8	2 (2)	C9A—C10A—C11A—C12Aⁱ	101 (4)
C5—C6—C7—C8	−178.0 (16)	C1A—C10A—C11A—C12Aⁱ	−56 (4)
C6—C7—C8—C9	−2 (2)	C10A—C11A—C12A—C13A	−115 (3)
C7—C8—C9—C10	1 (2)	C12Aⁱ—C11A—C12A—C13A	120 (2)
C8—C9—C10—C1	−0.1 (19)	C10A—C11A—C12A—C11Aⁱ	125 (3)
C8—C9—C10—C11	−179.9 (13)	C12Aⁱ—C11A—C12A—C11Aⁱ	0.000 (2)
C2—C1—C10—C9	179.2 (10)	C11A—C12A—C13A—C17A	156 (2)
C6—C1—C10—C9	−0.2 (17)	C11Aⁱ—C12A—C13A—C17A	−100 (2)
C2—C1—C10—C11	−1.0 (15)	C11A—C12A—C13A—C14A	−41 (3)
C6—C1—C10—C11	179.7 (13)	C11Aⁱ—C12A—C13A—C14A	63 (2)
C9—C10—C11—C12	9.0 (18)	C17A—C13A—C14A—C15A	0.4 (19)
C1—C10—C11—C12	−170.9 (9)	C12A—C13A—C14A—C15A	−163 (3)
C10—C11—C12—C13	−179.9 (10)	C16A—N1A—C15A—C14A	0 (3)
C11—C12—C13—C17	175.2 (8)	C18A—N1A—C15A—C14A	172 (4)
C11—C12—C13—C14	−7.4 (14)	C13A—C14A—C15A—N1A	−1 (3)
C17—C13—C14—C15	0.9 (15)	C15A—N1A—C16A—C17A	0 (3)
C12—C13—C14—C15	−176.6 (12)	C18A—N1A—C16A—C17A	−172 (4)
C16—N1—C15—C14	1.4 (18)	N1A—C16A—C17A—C13A	−1 (4)
C18—N1—C15—C14	−175.7 (13)	C14A—C13A—C17A—C16A	0 (3)
C13—C14—C15—N1	−1.4 (18)	C12A—C13A—C17A—C16A	164 (3)
C15—N1—C16—C17	−0.9 (16)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O3	0.84	2.01	2.831 (7)	164
O1W—H2W1···O1ⁱⁱ	0.84	2.04	2.853 (6)	164
N2—H2B···O1ⁱⁱⁱ	0.86	2.23	3.018 (6)	153
N2—H2C···O2^iv	0.86	2.23	2.991 (6)	147
C18—H18A···O1W	0.96	2.52	3.448 (13)	163
C18—H18B···O1W^v	0.96	2.21	3.168 (13)	173

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

Experimental details

Crystal data
Chemical formula	1.5C₁₈H₁₆N⁺·0.25C₃₆H₃₂N₂²⁺·2C₆H₆NO₃S⁻·2H₂O
M_r	873.04
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	6.6352 (4), 14.8824 (8), 20.9347 (13)
β (°)	97.921 (3)
V (Å³)	2047.5 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.19
Crystal size (mm)	0.52 × 0.13 × 0.07

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.906, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	21302, 4099, 3550
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.097, 0.275, 1.07
No. of reflections	4099
No. of parameters	440
No. of restraints	300
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.1017P)² + 16.5792P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.20, −0.62

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
O1W—H1W1···O3	0.84	2.01	2.831 (7)	164
O1W—H2W1···O1ⁱ	0.84	2.04	2.853 (6)	164
N2—H2B···O1ⁱⁱ	0.86	2.23	3.018 (6)	153
N2—H2C···O2ⁱⁱⁱ	0.86	2.23	2.991 (6)	147
C18—H18A···O1W	0.96	2.52	3.448 (13)	163
C18—H18B···O1W^iv	0.96	2.21	3.168 (13)	173

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Additional correspondence author, e-mail: suchada.c@psu.ac.th. Thomson Reuters ResearcherID: A-5085-2009.

Acknowledgements

The authors thank the Prince of Songkla University for financial support through the Crystal Materials Research Unit and the Malaysian Government and Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012. KC thanks the Development and Promotion of Science and Technology Talents Project (DPST) for a study grant. Partial financial support from the Graduate School, Prince of Songkla University, is gratefully acknowledged.

References

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