2-[(E)-2-(4-Hy­droxy-3-meth­oxy­phen­yl)ethen­yl]-1-methylpyridinium 4-bromo­benzene­sulfonate monohydrate

Chantrapromma, S.; Boonnak, N.; Jindawong, B.; Fun, H.-K.

doi:10.1107/S1600536813031917

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 12| December 2013| Pages o1851-o1852

doi:10.1107/S1600536813031917

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2-[(E)-2-(4-Hydroxy-3-methoxyphenyl)ethenyl]-1-methylpyridinium 4-bromobenzenesulfonate monohydrate

Suchada Chantrapromma,^a ^*‡ Nawong Boonnak,^b Boonwasana Jindawong ^a and Hoong-Kun Fun ^c §

^aDepartment of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand, ^bFaculty of Traditional Thai Medicine, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand, and ^cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: suchada.c@psu.ac.th

(Received 16 November 2013; accepted 22 November 2013; online 30 November 2013)

The title salt crystallized as the monohydrate C₁₅H₁₆NO₂⁺·C₆H₄BrSO₃⁻·H₂O. The cation exists in an E conformation with respect to the ethynyl bond and is essentially planar, with a dihedral angle of 6.52 (14)° between the pyridinium and the benzene rings. The hydroxy and methoxy substituents are coplanar with the benzene ring to which they are attached, with an r.m.s. deviation of 0.0116 (3) Å for the nine non-H atoms [C_methyl—O—C—C torsion angle = −0.8 (4)°]. In the crystal, the cations and anions are stacked by π–π interactions, with centroid–centroid distances of 3.7818 (19) and 3.9004 (17) Å. The cations, anions and water molecules are linked by O—H⋯O hydrogen bonds and weak C—H⋯O interactions, forming a three-dimensional network.

CCDC reference: 293059

Related literature

For applications of stilbene derivatives, see: Chanawanno et al. (2010 ); Frombaum et al. (2012 ); Hussain et al. (2009 ); Jindawong et al. (2005 ); Kobkeatthawin et al. (2009 ); Li et al. (2013 ); Ruanwas et al. (2010 ). For related structures, see, Chanawanno et al. (2009 ); Chantrapromma et al. (2013 ); Fun et al. (2011 ). For bond-length data, see: Allen et al. (1987 ) and for hydrogen-bond motifs, see: Bernstein et al. (1995 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer, (1986 ).

Experimental

Crystal data

C₁₅H₁₆NO₂⁺·C₆H₄BrO₃S⁻·H₂O
M_r = 496.37
Triclinic, $[P \overline 1]$
a = 9.8201 (13) Å
b = 10.3315 (14) Å
c = 12.4914 (17) Å
α = 99.898 (2)°
β = 111.134 (2)°
γ = 107.042 (2)°
V = 1074.1 (3) Å³
Z = 2
Mo Kα radiation
μ = 2.05 mm⁻¹
T = 100 K
0.59 × 0.15 × 0.14 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.378, T_max = 0.768
11172 measured reflections
4186 independent reflections
3356 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.113
S = 1.05
4186 reflections
281 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.93 e Å⁻³
Δρ_min = −0.94 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1O2⋯O1Wⁱ	0.82	1.88	2.685 (4)	169
O1W—H2W1⋯O4ⁱⁱ	0.81 (5)	2.03 (5)	2.834 (4)	172 (5)
O1W—H1W1⋯O3ⁱⁱⁱ	0.81 (4)	1.99 (5)	2.793 (5)	173 (5)
C1—H1A⋯O5^iv	0.93	2.57	3.491 (4)	170
C2—H2A⋯O1^v	0.93	2.51	3.440 (4)	176
C2—H2A⋯O2^v	0.93	2.60	3.183 (4)	121
C3—H3A⋯O2^v	0.93	2.54	3.160 (4)	124
C14—H14A⋯O4^iv	0.96	2.54	3.448 (5)	158
Symmetry codes: (i) x-1, y, z-1; (ii) x-1, y, z; (iii) -x+1, -y, -z+1; (iv) -x+2, -y+1, -z+1; (v) x+1, y+1, 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, PLATON (Spek, 2009 ), Mercury (Macrae et al., 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 293059

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813031917/sj5370sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813031917/sj5370Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813031917/sj5370Isup3.cml

checkCIF report

Comment top

Stilbene-based compounds have been reported to possess a wide range of biological activities including antibacterial (Chanawanno et al., 2010) and antioxidant (Frombaum et al., 2012) activities and also non-linear optical (Ruanwas et al., 2010) and fluorescent properties (Li et al., 2013). We have previously reported several crystal structures and applications of stilbene derivatives (Chanawanno et al., 2009; 2010, Kobkeatthawin et al., 2009, Ruanwas et al., 2010). Due to these interesting properties, the title pyridinium-stilbene salt, (I), was synthesized. We report herein the synthesis and crystal structure of (I).

The asymmetric unit of (I) consists of a C₁₅H₁₆NO₂⁺ cation, a C₆H₄BrSO₃^- anion and an H₂O molecule (Fig. 1). The cation exists in an E configuration with respect to the C6 ═C7 double bond [1.318 (4) Å] and the C5—C6—C7—C8 torsion angle is -178.0 (3)°. The cation is essentially planar with a dihedral angle between the pyridinium and benzene rings of the cation being 6.52 (14)°. The hydroxy and methoxy substituents lie close to the plane of the C8–C13 benzene ring with the r.m.s. deviation of 0.0116 (3) Å for the nine non-H atoms and with the torsion angle C15–O1–C10–C9 = -0.8 (4)°. All bond lengths (Allen et al., 1987) in both the cation and anion are normal and compare well with those found in closely related structures (Chanawanno et al., 2009; Chantrapromma et al., 2013; Fun et al., 2011).

In the crystal packing (Fig. 2), weak C2—H2A···O1 and C3—H3A···O2 interactions (Table 1) link together two inversely-related adjacent cations, generating an R₂²(8) ring motif (Bernstein et al., 1995). The O1W—H1W1···O3 and O1W—H2W1···O4 hydrogen bonds (Table 1) linked between two water molecules and two anions forming an R₂⁴(12) ring motif. The cations, anions and water molecules are further linked through intermolecular O–H···O hydrogen bonds and weak C—H···O interactions into a three dimensional network (Fig. 2 and Table 1). π–π interactions with distances Cg₁···Cg₃^vi = 3.7818 (19) Å and Cg₂···Cg₃ⁱⁱ = 3.9004 (17) Å were observed (Fig. 3); Cg₁, Cg₂ and Cg₃ are the centroids of C1–C5/N1, C8–C13 and C16–C21 rings, respectively [symmetry code (vi) = 1 - x, 1 - y, 1 - z].

Related literature top

For applications of stilbene derivatives, see: Chanawanno et al. (2010); Frombaum et al. (2012); Hussain et al. (2009); Jindawong et al. (2005); Kobkeatthawin et al. (2009); Li et al. (2013); Ruanwas et al. (2010). For related structures, see, Chanawanno et al. (2009); Chantrapromma et al. (2013); Fun et al. (2011). For bond-length data, see: Allen et al. (1987) and for hydrogen-bond motifs, see: Bernstein et al. (1995). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer, (1986).

Experimental top

1-Methyl-2-[(E)-2-(3-methoxy-4-hydroxyphenyl)ethenyl]pyridinium iodide (compound A) was prepared by mixing a solution (1:1:1 molar ratio) of 1,2-dimethylpyridinium iodide (3.02 g, 12.84 mmol), vanillin (4-hydroxy-3-methoxybenzaldehyde, 1.95 g, 12.82 mmol) and piperidine (1.09 g, 12.80 mmol). The resulting solution was refluxed for 3 h under a nitrogen atmosphere. The solid which formed was filtered, washed with diethylether and recrystallized from methanol, to give brown crystals of compound A (2.69 g, 57% yield Mp. 526–527 K). Thereafter, the title compound was synthesized by mixing a solution of compound A (0.21 g, 0.58 mmol) in hot methanol (60 ml) and a solution of silver (I) 4-bromobenzenesulfonate (Jindawong et al., 2005), (0.20 g, 0.58 mmol) in hot methanol (40 ml). Upon mixing, a yellow precipitate of silver iodide was immediately formed which was removed by filtration and the orange filtrate was evaporated under reduced pressure to yield the title compound as an orange solid (0.27 g, 91% yield). Orange block-shaped single crystals of the title compound suitable for X-ray structure determination were recrystallized from methanol by slow evaporation of the solvent at room temperature over several days, Mp. 490–491 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), PLATON (Spek, 2009), Mercury (Macrae et al., 2006) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. The crystal packing of the title compound viewed approximately along the b axis. Only H atoms involved in O—H···O hydrogen bonds and weak C—H···O interactions are shown for clarity. Hydrogen bonds are drawn as dashed lines.
	Fig. 3. π–π interactions between aromatic rings of the cations and anions.

2-[(E)-2-(4-Hydroxy-3-methoxyphenyl)ethenyl]-1-methylpyridinium 4-bromobenzenesulfonate monohydrate top

Crystal data top

C₁₅H₁₆NO₂⁺·C₆H₄BrO₃S⁻·H₂O	Z = 2
M_r = 496.37	F(000) = 508
Triclinic, P1	D_x = 1.535 Mg m⁻³
Hall symbol: -P 1	Melting point = 490–491 K
a = 9.8201 (13) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.3315 (14) Å	Cell parameters from 4186 reflections
c = 12.4914 (17) Å	θ = 1.8–26.0°
α = 99.898 (2)°	µ = 2.05 mm⁻¹
β = 111.134 (2)°	T = 100 K
γ = 107.042 (2)°	Block, orange
V = 1074.1 (3) Å³	0.59 × 0.15 × 0.14 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	4186 independent reflections
Radiation source: sealed tube	3356 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −12→12
T_min = 0.378, T_max = 0.768	k = −12→12
11172 measured reflections	l = −15→15

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0432P)² + 0.8763P] where P = (F_o² + 2F_c²)/3
4186 reflections	(Δ/σ)_max = 0.001
281 parameters	Δρ_max = 0.93 e Å⁻³
0 restraints	Δρ_min = −0.94 e Å⁻³

Crystal data top

C₁₅H₁₆NO₂⁺·C₆H₄BrO₃S⁻·H₂O	γ = 107.042 (2)°
M_r = 496.37	V = 1074.1 (3) Å³
Triclinic, P1	Z = 2
a = 9.8201 (13) Å	Mo Kα radiation
b = 10.3315 (14) Å	µ = 2.05 mm⁻¹
c = 12.4914 (17) Å	T = 100 K
α = 99.898 (2)°	0.59 × 0.15 × 0.14 mm
β = 111.134 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	4186 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3356 reflections with I > 2σ(I)
T_min = 0.378, T_max = 0.768	R_int = 0.021
11172 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.93 e Å⁻³
4186 reflections	Δρ_min = −0.94 e Å⁻³
281 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 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	0.41562 (5)	0.27735 (5)	0.15160 (5)	0.0940 (2)
S1	1.07185 (8)	0.19371 (9)	0.35750 (8)	0.0644 (2)
O1	−0.2430 (2)	0.1320 (2)	−0.12616 (19)	0.0664 (6)
O2	−0.4997 (2)	0.1780 (2)	−0.22714 (18)	0.0617 (5)
H1O2	−0.5807	0.1942	−0.2456	0.092*
O3	1.0331 (3)	0.0475 (3)	0.3536 (3)	0.1036 (10)
O4	1.1634 (3)	0.2910 (3)	0.4784 (2)	0.1020 (9)
O5	1.1441 (3)	0.2289 (3)	0.2791 (3)	0.0922 (8)
N1	0.3889 (2)	0.6912 (2)	0.43554 (19)	0.0449 (5)
C1	0.4991 (3)	0.7901 (3)	0.5431 (2)	0.0542 (7)
H1A	0.5957	0.7823	0.5812	0.065*
C2	0.4719 (4)	0.8995 (3)	0.5961 (3)	0.0566 (7)
H2A	0.5483	0.9660	0.6698	0.068*
C3	0.3287 (4)	0.9101 (3)	0.5387 (3)	0.0586 (7)
H3A	0.3080	0.9848	0.5732	0.070*
C4	0.2177 (3)	0.8115 (3)	0.4318 (3)	0.0555 (7)
H4A	0.1215	0.8199	0.3936	0.067*
C5	0.2451 (3)	0.6974 (3)	0.3778 (2)	0.0455 (6)
C6	0.1282 (3)	0.5869 (3)	0.2659 (2)	0.0478 (6)
H6A	0.1532	0.5114	0.2388	0.057*
C7	−0.0113 (3)	0.5867 (3)	0.2003 (2)	0.0492 (6)
H7A	−0.0320	0.6648	0.2281	0.059*
C8	−0.1367 (3)	0.4785 (3)	0.0895 (2)	0.0435 (6)
C9	−0.1236 (3)	0.3541 (3)	0.0378 (2)	0.0443 (6)
H9A	−0.0318	0.3384	0.0750	0.053*
C10	−0.2452 (3)	0.2549 (3)	−0.0674 (2)	0.0446 (6)
C11	−0.3846 (3)	0.2778 (3)	−0.1224 (2)	0.0446 (6)
C12	−0.3978 (3)	0.3996 (3)	−0.0715 (2)	0.0484 (6)
H12A	−0.4902	0.4148	−0.1079	0.058*
C13	−0.2746 (3)	0.4999 (3)	0.0333 (2)	0.0513 (6)
H13A	−0.2843	0.5825	0.0665	0.062*
C14	0.4288 (3)	0.5777 (3)	0.3817 (3)	0.0575 (7)
H14A	0.5370	0.5939	0.4304	0.086*
H14B	0.4148	0.5782	0.3017	0.086*
H14C	0.3607	0.4871	0.3780	0.086*
C15	−0.1033 (4)	0.1044 (4)	−0.0758 (3)	0.0733 (10)
H15A	−0.1162	0.0160	−0.1260	0.110*
H15B	−0.0847	0.0984	0.0038	0.110*
H15C	−0.0147	0.1802	−0.0712	0.110*
C16	0.8901 (3)	0.2169 (3)	0.3001 (2)	0.0474 (6)
C17	0.8818 (4)	0.3438 (3)	0.3475 (3)	0.0577 (7)
H17A	0.9713	0.4164	0.4103	0.069*
C18	0.7421 (4)	0.3636 (3)	0.3025 (3)	0.0649 (8)
H18A	0.7365	0.4492	0.3339	0.078*
C19	0.6110 (3)	0.2548 (3)	0.2102 (3)	0.0568 (7)
C20	0.6163 (3)	0.1274 (3)	0.1621 (3)	0.0547 (7)
H20A	0.5259	0.0546	0.1002	0.066*
C21	0.7575 (3)	0.1089 (3)	0.2070 (2)	0.0519 (6)
H21A	0.7633	0.0238	0.1744	0.062*
O1W	0.2172 (3)	0.1988 (3)	0.6854 (3)	0.0753 (7)
H2W1	0.196 (5)	0.217 (5)	0.622 (4)	0.093 (16)*
H1W1	0.148 (5)	0.124 (4)	0.671 (3)	0.079 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0699 (3)	0.1027 (3)	0.1419 (4)	0.0567 (2)	0.0504 (3)	0.0641 (3)
S1	0.0390 (4)	0.0670 (5)	0.0786 (6)	0.0186 (3)	0.0175 (4)	0.0237 (4)
O1	0.0524 (11)	0.0487 (11)	0.0694 (13)	0.0257 (9)	0.0008 (10)	−0.0031 (10)
O2	0.0436 (10)	0.0497 (11)	0.0594 (12)	0.0154 (9)	−0.0018 (9)	−0.0002 (9)
O3	0.0558 (14)	0.0819 (17)	0.171 (3)	0.0330 (13)	0.0319 (16)	0.0612 (19)
O4	0.0677 (16)	0.118 (2)	0.0798 (18)	0.0354 (16)	−0.0017 (14)	0.0105 (16)
O5	0.0644 (15)	0.112 (2)	0.122 (2)	0.0398 (15)	0.0553 (16)	0.0469 (18)
N1	0.0371 (11)	0.0485 (12)	0.0416 (12)	0.0127 (9)	0.0123 (9)	0.0139 (10)
C1	0.0380 (14)	0.0643 (18)	0.0439 (15)	0.0100 (13)	0.0079 (12)	0.0178 (13)
C2	0.0526 (16)	0.0527 (16)	0.0403 (15)	0.0047 (13)	0.0113 (13)	0.0048 (12)
C3	0.0587 (18)	0.0557 (17)	0.0496 (16)	0.0162 (14)	0.0207 (14)	0.0056 (13)
C4	0.0462 (15)	0.0586 (17)	0.0508 (16)	0.0210 (13)	0.0139 (13)	0.0065 (13)
C5	0.0386 (13)	0.0493 (15)	0.0412 (14)	0.0135 (11)	0.0133 (11)	0.0125 (11)
C6	0.0393 (13)	0.0471 (14)	0.0441 (14)	0.0154 (11)	0.0103 (11)	0.0042 (11)
C7	0.0467 (14)	0.0477 (15)	0.0440 (14)	0.0187 (12)	0.0133 (12)	0.0062 (12)
C8	0.0391 (13)	0.0471 (14)	0.0377 (13)	0.0163 (11)	0.0118 (11)	0.0092 (11)
C9	0.0344 (12)	0.0466 (14)	0.0454 (14)	0.0168 (11)	0.0097 (11)	0.0137 (11)
C10	0.0416 (13)	0.0389 (13)	0.0461 (14)	0.0150 (11)	0.0130 (11)	0.0107 (11)
C11	0.0362 (12)	0.0407 (13)	0.0424 (14)	0.0091 (10)	0.0075 (11)	0.0104 (11)
C12	0.0361 (13)	0.0537 (15)	0.0470 (15)	0.0202 (12)	0.0092 (11)	0.0110 (12)
C13	0.0462 (15)	0.0524 (15)	0.0478 (15)	0.0246 (12)	0.0124 (12)	0.0063 (12)
C14	0.0448 (15)	0.0613 (17)	0.0609 (18)	0.0240 (13)	0.0149 (13)	0.0182 (14)
C15	0.0608 (19)	0.0602 (19)	0.084 (2)	0.0365 (16)	0.0133 (17)	0.0043 (17)
C16	0.0414 (13)	0.0529 (15)	0.0481 (15)	0.0163 (12)	0.0204 (12)	0.0178 (12)
C17	0.0547 (17)	0.0511 (16)	0.0597 (18)	0.0130 (13)	0.0259 (15)	0.0107 (14)
C18	0.070 (2)	0.0483 (16)	0.089 (2)	0.0268 (15)	0.0453 (19)	0.0212 (16)
C19	0.0525 (16)	0.0658 (19)	0.0734 (19)	0.0317 (15)	0.0359 (15)	0.0370 (16)
C20	0.0464 (15)	0.0619 (17)	0.0501 (16)	0.0190 (13)	0.0174 (13)	0.0159 (13)
C21	0.0498 (15)	0.0536 (16)	0.0513 (16)	0.0227 (13)	0.0217 (13)	0.0098 (13)
O1W	0.0510 (14)	0.0705 (17)	0.0782 (19)	0.0190 (13)	0.0064 (12)	0.0174 (14)

Geometric parameters (Å, º) top

Br1—C19	1.892 (3)	C8—C9	1.398 (4)
S1—O3	1.433 (3)	C9—C10	1.375 (4)
S1—O5	1.438 (3)	C9—H9A	0.9300
S1—O4	1.438 (3)	C10—C11	1.404 (4)
S1—C16	1.773 (3)	C11—C12	1.373 (4)
O1—C10	1.363 (3)	C12—C13	1.382 (4)
O1—C15	1.425 (3)	C12—H12A	0.9300
O2—C11	1.356 (3)	C13—H13A	0.9300
O2—H1O2	0.8200	C14—H14A	0.9600
N1—C1	1.360 (3)	C14—H14B	0.9600
N1—C5	1.361 (3)	C14—H14C	0.9600
N1—C14	1.473 (4)	C15—H15A	0.9600
C1—C2	1.355 (4)	C15—H15B	0.9600
C1—H1A	0.9300	C15—H15C	0.9600
C2—C3	1.376 (4)	C16—C21	1.380 (4)
C2—H2A	0.9300	C16—C17	1.381 (4)
C3—C4	1.357 (4)	C17—C18	1.373 (4)
C3—H3A	0.9300	C17—H17A	0.9300
C4—C5	1.400 (4)	C18—C19	1.374 (5)
C4—H4A	0.9300	C18—H18A	0.9300
C5—C6	1.449 (4)	C19—C20	1.374 (4)
C6—C7	1.318 (4)	C20—C21	1.380 (4)
C6—H6A	0.9300	C20—H20A	0.9300
C7—C8	1.454 (4)	C21—H21A	0.9300
C7—H7A	0.9300	O1W—H2W1	0.81 (4)
C8—C13	1.385 (4)	O1W—H1W1	0.80 (4)

O3—S1—O5	112.54 (19)	O2—C11—C12	122.9 (2)
O3—S1—O4	112.9 (2)	O2—C11—C10	117.3 (2)
O5—S1—O4	112.02 (19)	C12—C11—C10	119.8 (2)
O3—S1—C16	106.57 (14)	C11—C12—C13	120.4 (2)
O5—S1—C16	105.90 (14)	C11—C12—H12A	119.8
O4—S1—C16	106.35 (15)	C13—C12—H12A	119.8
C10—O1—C15	117.7 (2)	C12—C13—C8	120.6 (2)
C11—O2—H1O2	109.5	C12—C13—H13A	119.7
C1—N1—C5	121.0 (2)	C8—C13—H13A	119.7
C1—N1—C14	118.6 (2)	N1—C14—H14A	109.5
C5—N1—C14	120.4 (2)	N1—C14—H14B	109.5
C2—C1—N1	121.7 (3)	H14A—C14—H14B	109.5
C2—C1—H1A	119.1	N1—C14—H14C	109.5
N1—C1—H1A	119.1	H14A—C14—H14C	109.5
C1—C2—C3	118.6 (3)	H14B—C14—H14C	109.5
C1—C2—H2A	120.7	O1—C15—H15A	109.5
C3—C2—H2A	120.7	O1—C15—H15B	109.5
C4—C3—C2	120.1 (3)	H15A—C15—H15B	109.5
C4—C3—H3A	120.0	O1—C15—H15C	109.5
C2—C3—H3A	120.0	H15A—C15—H15C	109.5
C3—C4—C5	121.3 (3)	H15B—C15—H15C	109.5
C3—C4—H4A	119.4	C21—C16—C17	120.0 (3)
C5—C4—H4A	119.4	C21—C16—S1	120.0 (2)
N1—C5—C4	117.3 (2)	C17—C16—S1	120.0 (2)
N1—C5—C6	119.4 (2)	C18—C17—C16	120.4 (3)
C4—C5—C6	123.3 (2)	C18—C17—H17A	119.8
C7—C6—C5	124.1 (3)	C16—C17—H17A	119.8
C7—C6—H6A	118.0	C17—C18—C19	118.9 (3)
C5—C6—H6A	118.0	C17—C18—H18A	120.6
C6—C7—C8	127.6 (3)	C19—C18—H18A	120.6
C6—C7—H7A	116.2	C18—C19—C20	121.7 (3)
C8—C7—H7A	116.2	C18—C19—Br1	119.4 (2)
C13—C8—C9	118.9 (2)	C20—C19—Br1	118.8 (2)
C13—C8—C7	118.4 (2)	C19—C20—C21	119.1 (3)
C9—C8—C7	122.7 (2)	C19—C20—H20A	120.5
C10—C9—C8	120.7 (2)	C21—C20—H20A	120.5
C10—C9—H9A	119.7	C16—C21—C20	119.9 (3)
C8—C9—H9A	119.7	C16—C21—H21A	120.0
O1—C10—C9	125.3 (2)	C20—C21—H21A	120.0
O1—C10—C11	115.1 (2)	H2W1—O1W—H1W1	105 (4)
C9—C10—C11	119.6 (2)

C5—N1—C1—C2	−1.1 (4)	O1—C10—C11—C12	−178.8 (2)
C14—N1—C1—C2	178.2 (3)	C9—C10—C11—C12	0.8 (4)
N1—C1—C2—C3	−0.2 (4)	O2—C11—C12—C13	−177.9 (3)
C1—C2—C3—C4	0.6 (5)	C10—C11—C12—C13	0.1 (4)
C2—C3—C4—C5	0.2 (5)	C11—C12—C13—C8	−0.7 (4)
C1—N1—C5—C4	1.9 (4)	C9—C8—C13—C12	0.5 (4)
C14—N1—C5—C4	−177.4 (3)	C7—C8—C13—C12	−179.4 (3)
C1—N1—C5—C6	−177.4 (2)	O3—S1—C16—C21	−36.2 (3)
C14—N1—C5—C6	3.3 (4)	O5—S1—C16—C21	83.9 (3)
C3—C4—C5—N1	−1.5 (4)	O4—S1—C16—C21	−156.8 (2)
C3—C4—C5—C6	177.8 (3)	O3—S1—C16—C17	144.8 (3)
N1—C5—C6—C7	−176.7 (3)	O5—S1—C16—C17	−95.2 (3)
C4—C5—C6—C7	4.1 (4)	O4—S1—C16—C17	24.2 (3)
C5—C6—C7—C8	−178.0 (3)	C21—C16—C17—C18	0.0 (4)
C6—C7—C8—C13	−179.1 (3)	S1—C16—C17—C18	179.0 (2)
C6—C7—C8—C9	1.0 (5)	C16—C17—C18—C19	0.4 (5)
C13—C8—C9—C10	0.4 (4)	C17—C18—C19—C20	−0.1 (5)
C7—C8—C9—C10	−179.8 (2)	C17—C18—C19—Br1	177.5 (2)
C15—O1—C10—C9	−0.8 (4)	C18—C19—C20—C21	−0.6 (5)
C15—O1—C10—C11	178.8 (3)	Br1—C19—C20—C21	−178.2 (2)
C8—C9—C10—O1	178.6 (3)	C17—C16—C21—C20	−0.7 (4)
C8—C9—C10—C11	−1.0 (4)	S1—C16—C21—C20	−179.7 (2)
O1—C10—C11—O2	−0.8 (4)	C19—C20—C21—C16	1.0 (4)
C9—C10—C11—O2	178.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O2···O1Wⁱ	0.82	1.88	2.685 (4)	169
O1W—H2W1···O4ⁱⁱ	0.81 (5)	2.03 (5)	2.834 (4)	172 (5)
O1W—H1W1···O3ⁱⁱⁱ	0.81 (4)	1.99 (5)	2.793 (5)	173 (5)
C1—H1A···O5^iv	0.93	2.57	3.491 (4)	170
C2—H2A···O1^v	0.93	2.51	3.440 (4)	176
C2—H2A···O2^v	0.93	2.60	3.183 (4)	121
C3—H3A···O2^v	0.93	2.54	3.160 (4)	124
C14—H14A···O4^iv	0.96	2.54	3.448 (5)	158

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O2···O1Wⁱ	0.82	1.88	2.685 (4)	169
O1W—H2W1···O4ⁱⁱ	0.81 (5)	2.03 (5)	2.834 (4)	172 (5)
O1W—H1W1···O3ⁱⁱⁱ	0.81 (4)	1.99 (5)	2.793 (5)	173 (5)
C1—H1A···O5^iv	0.93	2.57	3.491 (4)	170
C2—H2A···O1^v	0.93	2.51	3.440 (4)	176
C2—H2A···O2^v	0.93	2.60	3.183 (4)	121
C3—H3A···O2^v	0.93	2.54	3.160 (4)	124
C14—H14A···O4^iv	0.96	2.54	3.448 (5)	158

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

Footnotes

‡Thomson Reuters ResearcherID: A-5085-2009.

§Additional correspondence author, e-mail: hkfun@usm.my. Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

The authors thank Prince of Songkla University for generous support and also thank the Universiti Sains Malaysia for the APEX DE2012 grant No. 1002/PFIZIK/910323.

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