1-Methyl-4-[(E)-2-(2-thien­yl)ethen­yl]pyridinium 4-chloro­benzene­sulfonate†

In the title compound, C₁₂H₁₂NS⁺·C₆H₄ClO₃S⁻, the cation is almost planar and exists in the E configuration. The cations and anions form alternate layers parallel to the ab plane. Within each layer, both cations and anions form chains directed along the b axis. The mol­ecules are inter­connected by weak C—H⋯O inter­actions into a three-dimensional network. The crystal structure is further stabilized by C—H⋯π inter­actions involving the thio­phene ring. The sulfonate and thio­phene groups are involved in weak intra­molecular C—H⋯O and C—H⋯S inter­actions, respectively. The latter intra­molecular hydrogen bonds produce S(5) ring motifs.

Related literature

For bond lengths and angles, see Allen (2002); Allen et al. (1987). For related literature on hydrogen-bond motifs, see Bernstein et al. (1995). For related structures, see for example Chantrapromma et al. (2005, 2006a,b, 2007a,b,c,d); Drost et al. (1995); Jindawong et al. (2005); Subramaniyan et al. (2003).

Experimental

Crystal data

• C₁₂H₁₂NS⁺·C₆H₄ClO₃S⁻

• M_r = 393.91

• Monoclinic, P 2₁ /c

• a = 7.3532 (1) Å

• b = 14.0250 (2) Å

• c = 18.3755 (2) Å

• β = 111.232 (1)°

• V = 1766.41 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 0.47 mm⁻¹

• T = 100.0 (1) K

• 0.49 × 0.22 × 0.18 mm

Data collection

• Bruker SMART APEX2 CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2005) T_min = 0.883, T_max = 0.919

• 23692 measured reflections

• 4688 independent reflections

• 3913 reflections with I > 2σ(I)

• R_int = 0.037

Refinement

• R[F² > 2σ(F²)] = 0.037

• wR(F²) = 0.094

• S = 1.06

• 4688 reflections

• 227 parameters

• H-atom parameters constrained

• Δρ_max = 0.57 e Å⁻³

• Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the S1/C8–C11 thiophene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯O3^i	0.93	2.31	3.211 (2)	164
C6—H6A⋯S1	0.93	2.84	3.228 (2)	106
C7—H7A⋯O1^ii	0.93	2.39	3.266 (2)	157
C9—H9A⋯O3^ii	0.93	2.58	3.495 (2)	166
C10—H10A⋯O2^iii	0.93	2.39	3.302 (2)	167
C11—H11A⋯O2^iv	0.93	2.55	3.063 (2)	115
C12—H12C⋯O2^i	0.96	2.39	3.334 (2)	168
C17—H17A⋯O2^iv	0.93	2.41	3.318 (2)	166
C18—H18A⋯O3	0.93	2.51	2.892 (2)	105
C12—H12B⋯Cg1^i	0.96	2.69	3.515 (2)	144
Symmetry codes: (i) -x+2, -y+2, -z+1; (ii) ; (iii) -x+2, -y+1, -z+1; (iv) x-1, y, z.

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); 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

S1. Comment

Molecules with extended π systems have been extensively used in attempts to obtain materials with non-linear optical (NLO) properties. Organic crystal with the required conjugated π electrons are attractive candidates because of the large NLO coefficients. In our research for second-order NLO materials, we have previously synthesized and crystallized several organic ionic salts of pyridinium and quinolinium derivatives to study their non-linear optical properties (Chantrapromma et al., 2005; 2006a; 2006b; 2007a; 2007b; 2007c; 2007 d; Jindawong et al., 2005). An earlier study carried out by Drost et al. (1995) has revealed that the products of the dipole moment and the molecular hyperpolarizability (β) of thiophene-containing conjugated moieties are larger than those of the phenyl analogues. Based on this reason, we have synthesized the title compound which was designed by replacement of the cationic phenyl ring by the thiophene ring that is present in 4-(4'-Hydroxy-3'-methoxystyryl)-1-methylpyridinium 4-chlorobenzenesulfonate (Chantrapromma et al., 2005).

The asymmetric unit of the title compound consists of the C₁₂H₁₂NS⁺ cation and the C₆H₄ClO₃S^- anion. The cation is almost planar and exists in the E configuration with respect to the C6?C7 double bond [1.334 (3) Å]. The cation is almost perpendicular to the anion as is indicated by the angles between the mean planes of the chlorophenyl ring to the pyridinium as well as to the thiophene ring being 87.64 (9)° and 86.73 (9)°, respectively. The dihedral angle between the pyridinium and the thiophene rings is 5.74 (10)°. The ethenyl unit is nearly planar. The torsion angles C4–C5–C6–C7 = -4.3 (3)° and C6–C7–C8–S1 = -1.5 (3)°.

The atom O3 of the sulfonate and the S atom of the thiophene contribute to the C—H···O and C—H···S intramolecular weak interactions (Fig. 1 and Table 1) forming S(5) ring motifs (Bernstein et al., 1995). The bond lengths and angles are normal (Allen et al., 1987) and are comparable with closely related structures (Chantrapromma et al., 2005; 2006b; 2007c; 2007 d).

All the O atoms of 4-chlorobenzenesulfonate anion are involved in the C—H···O weak interactions (Table 1). The cations and anions form alternate layers parallel to the ab plane. Within each respective layer, the ions are interconnected by C—H···O weak interactions and in each respective layer can be distinguished chains directed along the b axis. The alternating layers are separated by 4.282 (2) Å and are further linked into a three dimensional network by C—H···O weak interactions (Table 1). The sulfonate as well as the thiophene are involved in C—H···O and C—H···S intramolecular weak interactions, respectively. These weak hydrogen bonds participate in S(5) ring motifs. The crystal structure is further stabilized by the C12—H12B···π interaction to the thiophene ring C8–C11/S1: C12—H12B=0.96; H12B···Cg1ⁱ=2.692; C12—Cg1ⁱ=3.515 (2) Å; C12—H12B···Cg1ⁱ= 144°. [Cg1ⁱ is the centroid of the S1/C8–C11 thiophene ring (symmetry code: (i): 2 - x, 2 - y, 1 - z).]

A very interesting feature is the short non-bonding contact between Cl1 and O3 that is 2.963 (1) Å long only. A search in the Cambridge Structural Database (version 5.29 and addenda up to 25-th January 2008; Allen, 2002) among the structures which have been flagged with no error or disorder as well as with R-factor < 0.05 and which contained chloro-phenyl with any substituent in the para position showed that the present structure contains an unprecedentedly short contact of this kind. The up-to-now shortest contact of this type was 2.996 (2) Å long and it was observed in MUTDOU [Spiro(2-carbomethoxy-3-(4-chlorophenyl)-5-(S,R)-(cis-1-(4-methoxyphenyl) -3-phenyl-4-oxoazetidin-2-(S,R)-yl)pyrrolidine-4,3¹-chroman-4¹-one)] determined by Subramaniyan et al. (2003).

Related literature

For standard bond lengths and angles, see Allen (2002); Allen et al. (1987). For related literature on hydrogen-bond motifs, see Bernstein et al. (1995). For related structures, see for example Chantrapromma et al. (2005, 2006a,b, 2007a,b,c,d); Drost et al. (1995); Jindawong et al. (2005); Subramaniyan et al. (2003).

S2. Experimental

4-(2-Thiophenestyryl)-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), 2-thiophenecarboxaldehyde (6.00 ml, 8.5 mmol) and piperidine (0.84 ml, 8.5 mmol) in hot methanol (40 ml). The resulting solution was refluxed for 5 h under a nitrogen atmosphere. The resultant solid was filtered off, washed with diethyl ether and recrystallized from methanol. The title compound was synthesized by mixing compound A (0.10 g, 0.3 mmol) in hot methanol (20 ml) and silver(I) 4-chlorobenzenesulfonate (0.08 g, 0.3 mmol) in hot methanol (30 ml). Silver(I) 4-chlorobenzenesulfonate was synthesized according to our previously reported procedure (Chantrapromma et al., 2006b). The mixture immediately yielded a grey solid of silver iodide. After stirring the mixture for ca 30 min, the precipitate of silver iodide was removed and the resulting solution was evaporated and a brown solid was obtained. Brown block-shaped single crystals of the title compound suitable for x-ray structure determination were recrystalized from methanol solvent by slow evaporation of the solvent at room temperature after several days (Mp. 503–505 K).

S3. Refinement

All the hydrogen atoms could have been discerned in the difference Fourier map. Nevertheless, all the H atoms attached to the carbon atoms were constrained in a riding motion approximation with C_aryl—H=0.93 and C_methyl—H=0.968 Å. The U_iso values were constrained to be 1.5U_eq of the carrier atom for methyl H atoms and 1.2U_eq for the remaining H atoms. A rotating group model was used for the methyl groups. The highest residual electron density peak is located at 0.75 Å from C8 and the deepest hole is located at 0.50 Å from S1.

Computing details

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

	Fig. 1. The title molecules showing 50% probability displacement ellipsoids and the atom-numbering scheme. The intramolecular C—H···O and C—H···S weak interactions are drawn as dashed lines.
	Fig. 2. The packing diagram of the title structure viewed along the a axis. The weak C—H···O and C—H···S interactions are drawn as dashed lines.

1-Methyl-4-[(E)-2-(2-thienyl)ethenyl]pyridinium 4-chlorobenzenesulfonate

Crystal data

C12H12NS^+·C6H4ClO3S^−	F(000) = 816
Mr = 393.91	Dx = 1.481 Mg m^−3
Monoclinic, P21/c	Melting point = 503–505 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.3532 (1) Å	Cell parameters from 4688 reflections
b = 14.0250 (2) Å	θ = 1.9–29.0°
c = 18.3755 (2) Å	µ = 0.47 mm^−1
β = 111.232 (1)°	T = 100 K
V = 1766.41 (4) Å^3	Block, brown
Z = 4	0.49 × 0.22 × 0.18 mm

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer	4688 independent reflections
Radiation source: fine-focus sealed tube	3913 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
Detector resolution: 8.33 pixels mm^-1	θmax = 29.0°, θmin = 1.9°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −19→19
Tmin = 0.883, Tmax = 0.919	l = −21→25
23692 measured reflections

Refinement

Refinement on F^2	Primary atom site location: difference Fourier map
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: difference Fourier map
wR(F^2) = 0.094	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0415P)^2 + 1.1208P] where P = (Fo^2 + 2Fc^2)/3
4688 reflections	(Δ/σ)max = 0.001
227 parameters	Δρmax = 0.57 e Å^−3
0 restraints	Δρmin = −0.42 e Å^−3
63 constraints

Special details

Experimental. The low-temparture 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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.57131 (7)	0.72654 (3)	0.43805 (3)	0.02450 (11)
S2	1.05267 (5)	0.60506 (3)	0.27447 (2)	0.01477 (10)
Cl1	0.37650 (6)	0.31936 (3)	0.25045 (2)	0.02092 (10)
O1	1.09007 (17)	0.58763 (9)	0.20315 (7)	0.0219 (3)
O2	1.21870 (16)	0.58102 (9)	0.34443 (7)	0.0196 (3)
O3	0.97435 (17)	0.69943 (8)	0.27824 (7)	0.0210 (3)
N1	0.8323 (2)	1.24164 (11)	0.49389 (9)	0.0214 (3)
C1	0.6981 (3)	1.10669 (14)	0.41625 (11)	0.0273 (4)
H1A	0.6342	1.0808	0.3669	0.033*
C2	0.7408 (3)	1.20156 (14)	0.42351 (11)	0.0265 (4)
H2A	0.7060	1.2394	0.3790	0.032*
C3	0.8863 (3)	1.18711 (14)	0.55895 (11)	0.0259 (4)
H3A	0.9501	1.2150	0.6075	0.031*
C4	0.8481 (3)	1.09132 (14)	0.55424 (11)	0.0267 (4)
H4A	0.8881	1.0547	0.5995	0.032*
C5	0.7490 (2)	1.04783 (13)	0.48184 (11)	0.0216 (3)
C6	0.6999 (3)	0.94698 (14)	0.47236 (11)	0.0239 (4)
H6A	0.6262	0.9252	0.4226	0.029*
C7	0.7537 (3)	0.88364 (13)	0.53044 (11)	0.0227 (4)
H7A	0.8268	0.9066	0.5799	0.027*
C8	0.7098 (2)	0.78300 (13)	0.52426 (10)	0.0213 (3)
C9	0.7700 (2)	0.72058 (12)	0.58541 (10)	0.0190 (3)
H9A	0.8451	0.7379	0.6363	0.023*
C10	0.7037 (3)	0.62467 (13)	0.56186 (11)	0.0234 (4)
H10A	0.7313	0.5730	0.5958	0.028*
C11	0.5956 (3)	0.61854 (13)	0.48386 (11)	0.0234 (4)
H11A	0.5415	0.5622	0.4586	0.028*
C12	0.8779 (3)	1.34470 (13)	0.50102 (12)	0.0287 (4)
H12A	0.8119	1.3754	0.4518	0.043*
H12B	1.0161	1.3535	0.5159	0.043*
H12C	0.8353	1.3722	0.5400	0.043*
C13	0.8648 (2)	0.52345 (12)	0.27171 (9)	0.0151 (3)
C14	0.8824 (2)	0.42781 (12)	0.25482 (9)	0.0165 (3)
H14A	0.9944	0.4067	0.2475	0.020*
C15	0.7332 (2)	0.36386 (12)	0.24892 (10)	0.0174 (3)
H15A	0.7434	0.3000	0.2372	0.021*
C16	0.5682 (2)	0.39778 (12)	0.26093 (9)	0.0165 (3)
C17	0.5512 (2)	0.49151 (12)	0.28055 (10)	0.0186 (3)
H17A	0.4417	0.5120	0.2902	0.022*
C18	0.7013 (2)	0.55480 (12)	0.28563 (10)	0.0181 (3)
H18A	0.6920	0.6183	0.2984	0.022*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0255 (2)	0.0248 (2)	0.0196 (2)	−0.00284 (17)	0.00382 (17)	0.00120 (17)
S2	0.01233 (18)	0.01553 (19)	0.01604 (19)	0.00021 (14)	0.00465 (14)	0.00095 (14)
Cl1	0.01861 (19)	0.0189 (2)	0.0272 (2)	−0.00466 (14)	0.01069 (16)	−0.00201 (16)
O1	0.0200 (6)	0.0292 (7)	0.0181 (6)	−0.0020 (5)	0.0090 (5)	0.0007 (5)
O2	0.0144 (5)	0.0239 (6)	0.0174 (6)	0.0000 (4)	0.0022 (5)	0.0013 (5)
O3	0.0181 (6)	0.0143 (6)	0.0314 (7)	−0.0003 (4)	0.0099 (5)	0.0002 (5)
N1	0.0225 (7)	0.0214 (7)	0.0240 (8)	−0.0001 (6)	0.0127 (6)	0.0011 (6)
C1	0.0289 (9)	0.0304 (10)	0.0204 (9)	−0.0058 (8)	0.0063 (7)	−0.0019 (7)
C2	0.0298 (10)	0.0285 (10)	0.0192 (8)	−0.0031 (8)	0.0066 (7)	0.0034 (7)
C3	0.0309 (9)	0.0293 (10)	0.0174 (8)	−0.0016 (8)	0.0085 (7)	−0.0019 (7)
C4	0.0329 (10)	0.0273 (10)	0.0208 (9)	0.0009 (8)	0.0108 (8)	0.0035 (7)
C5	0.0192 (8)	0.0227 (9)	0.0256 (9)	−0.0001 (6)	0.0114 (7)	−0.0001 (7)
C6	0.0219 (8)	0.0285 (9)	0.0209 (8)	−0.0034 (7)	0.0073 (7)	−0.0016 (7)
C7	0.0192 (8)	0.0274 (9)	0.0224 (9)	0.0001 (7)	0.0086 (7)	−0.0019 (7)
C8	0.0181 (8)	0.0239 (9)	0.0227 (8)	−0.0015 (6)	0.0085 (7)	−0.0015 (7)
C9	0.0176 (8)	0.0251 (9)	0.0133 (7)	−0.0012 (6)	0.0045 (6)	0.0008 (6)
C10	0.0219 (8)	0.0249 (9)	0.0220 (9)	−0.0019 (7)	0.0061 (7)	0.0044 (7)
C11	0.0225 (8)	0.0211 (9)	0.0242 (9)	−0.0038 (7)	0.0058 (7)	0.0004 (7)
C12	0.0318 (10)	0.0219 (9)	0.0376 (11)	−0.0020 (8)	0.0186 (9)	−0.0005 (8)
C13	0.0139 (7)	0.0171 (8)	0.0142 (7)	−0.0002 (6)	0.0048 (6)	−0.0002 (6)
C14	0.0145 (7)	0.0190 (8)	0.0170 (8)	0.0024 (6)	0.0068 (6)	−0.0008 (6)
C15	0.0186 (7)	0.0148 (7)	0.0192 (8)	0.0016 (6)	0.0075 (6)	−0.0010 (6)
C16	0.0148 (7)	0.0176 (8)	0.0166 (7)	−0.0027 (6)	0.0051 (6)	0.0008 (6)
C17	0.0148 (7)	0.0180 (8)	0.0249 (9)	0.0018 (6)	0.0094 (7)	0.0001 (6)
C18	0.0182 (8)	0.0148 (8)	0.0217 (8)	0.0011 (6)	0.0078 (6)	−0.0014 (6)

Geometric parameters (Å, º)

S1—C11	1.7105 (19)	C7—C8	1.443 (3)
S1—C8	1.7335 (18)	C7—H7A	0.9300
S2—O1	1.4541 (12)	C8—C9	1.366 (2)
S2—O3	1.4550 (12)	C9—C10	1.443 (2)
S2—O2	1.4560 (12)	C9—H9A	0.9300
S2—C13	1.7806 (16)	C10—C11	1.367 (3)
Cl1—C16	1.7428 (16)	C10—H10A	0.9300
N1—C2	1.346 (2)	C11—H11A	0.9300
N1—C3	1.352 (2)	C12—H12A	0.9600
N1—C12	1.479 (2)	C12—H12B	0.9600
C1—C2	1.363 (3)	C12—H12C	0.9600
C1—C5	1.395 (3)	C13—C18	1.388 (2)
C1—H1A	0.9300	C13—C14	1.393 (2)
C2—H2A	0.9300	C14—C15	1.390 (2)
C3—C4	1.369 (3)	C14—H14A	0.9300
C3—H3A	0.9300	C15—C16	1.393 (2)
C4—C5	1.404 (3)	C15—H15A	0.9300
C4—H4A	0.9300	C16—C17	1.381 (2)
C5—C6	1.455 (3)	C17—C18	1.393 (2)
C6—C7	1.334 (3)	C17—H17A	0.9300
C6—H6A	0.9300	C18—H18A	0.9300
C11—S1—C8	91.87 (9)	C8—C9—C10	112.16 (15)
O1—S2—O3	113.77 (7)	C8—C9—H9A	123.9
O1—S2—O2	112.64 (7)	C10—C9—H9A	123.9
O3—S2—O2	112.86 (7)	C11—C10—C9	112.22 (16)
O1—S2—C13	105.32 (7)	C11—C10—H10A	123.9
O3—S2—C13	105.65 (7)	C9—C10—H10A	123.9
O2—S2—C13	105.68 (7)	C10—C11—S1	112.19 (14)
C2—N1—C3	119.87 (16)	C10—C11—H11A	123.9
C2—N1—C12	120.78 (16)	S1—C11—H11A	123.9
C3—N1—C12	119.34 (16)	N1—C12—H12A	109.5
C2—C1—C5	120.86 (18)	N1—C12—H12B	109.5
C2—C1—H1A	119.6	H12A—C12—H12B	109.5
C5—C1—H1A	119.6	N1—C12—H12C	109.5
N1—C2—C1	121.28 (17)	H12A—C12—H12C	109.5
N1—C2—H2A	119.4	H12B—C12—H12C	109.5
C1—C2—H2A	119.4	C18—C13—C14	120.17 (15)
N1—C3—C4	120.76 (17)	C18—C13—S2	120.39 (13)
N1—C3—H3A	119.6	C14—C13—S2	119.44 (12)
C4—C3—H3A	119.6	C15—C14—C13	120.28 (15)
C3—C4—C5	120.70 (17)	C15—C14—H14A	119.9
C3—C4—H4A	119.6	C13—C14—H14A	119.9
C5—C4—H4A	119.6	C14—C15—C16	118.36 (15)
C1—C5—C4	116.51 (17)	C14—C15—H15A	120.8
C1—C5—C6	119.63 (17)	C16—C15—H15A	120.8
C4—C5—C6	123.86 (17)	C17—C16—C15	122.20 (15)
C7—C6—C5	124.26 (17)	C17—C16—Cl1	118.91 (12)
C7—C6—H6A	117.9	C15—C16—Cl1	118.89 (13)
C5—C6—H6A	117.9	C16—C17—C18	118.65 (15)
C6—C7—C8	126.54 (17)	C16—C17—H17A	120.7
C6—C7—H7A	116.7	C18—C17—H17A	120.7
C8—C7—H7A	116.7	C13—C18—C17	120.27 (15)
C9—C8—C7	124.44 (16)	C13—C18—H18A	119.9
C9—C8—S1	111.55 (13)	C17—C18—H18A	119.9
C7—C8—S1	124.01 (14)
C3—N1—C2—C1	1.0 (3)	C8—C9—C10—C11	−0.1 (2)
C12—N1—C2—C1	179.98 (18)	C9—C10—C11—S1	−0.2 (2)
C5—C1—C2—N1	−0.3 (3)	C8—S1—C11—C10	0.36 (15)
C2—N1—C3—C4	−0.4 (3)	O1—S2—C13—C18	−130.91 (14)
C12—N1—C3—C4	−179.30 (17)	O3—S2—C13—C18	−10.19 (16)
N1—C3—C4—C5	−1.1 (3)	O2—S2—C13—C18	109.65 (14)
C2—C1—C5—C4	−1.0 (3)	O1—S2—C13—C14	48.59 (15)
C2—C1—C5—C6	179.41 (18)	O3—S2—C13—C14	169.30 (13)
C3—C4—C5—C1	1.7 (3)	O2—S2—C13—C14	−70.85 (14)
C3—C4—C5—C6	−178.76 (17)	C18—C13—C14—C15	2.4 (2)
C1—C5—C6—C7	175.16 (18)	S2—C13—C14—C15	−177.09 (12)
C4—C5—C6—C7	−4.4 (3)	C13—C14—C15—C16	−0.5 (2)
C5—C6—C7—C8	−179.72 (17)	C14—C15—C16—C17	−1.9 (3)
C6—C7—C8—C9	179.23 (18)	C14—C15—C16—Cl1	177.84 (12)
C6—C7—C8—S1	−1.5 (3)	C15—C16—C17—C18	2.4 (3)
C11—S1—C8—C9	−0.44 (14)	Cl1—C16—C17—C18	−177.33 (13)
C11—S1—C8—C7	−179.82 (15)	C14—C13—C18—C17	−1.9 (2)
C7—C8—C9—C10	179.78 (16)	S2—C13—C18—C17	177.59 (13)
S1—C8—C9—C10	0.40 (19)	C16—C17—C18—C13	−0.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O3^i	0.93	2.31	3.211 (2)	164
C6—H6A···S1	0.93	2.84	3.228 (2)	106
C7—H7A···O1^ii	0.93	2.39	3.266 (2)	157
C9—H9A···O3^ii	0.93	2.59	3.495 (2)	166
C10—H10A···O2^iii	0.93	2.39	3.302 (2)	167
C11—H11A···O2^iv	0.93	2.55	3.063 (2)	115
C12—H12C···O2^i	0.96	2.39	3.334 (2)	168
C17—H17A···O2^iv	0.93	2.41	3.318 (2)	166
C18—H18A···O3	0.93	2.51	2.892 (2)	105
C12—H12B···Cg1^i	0.96	2.69	3.515 (2)	144

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

 

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: [e-mail].