organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Bis[(E)-1-methyl-4-styrylpyridinium] 4-bromo­benzene­sulfonate iodide

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 16 April 2010; accepted 11 May 2010; online 15 May 2010)

In the title compound, 2C14H14N+·C6H4BrO3S·I, two crystallographically independent cations exist in an E configuration with respect to the C=C ethenyl bond. One cation is approximately planar, whereas the other is twisted slightly, the dihedral angles between the pyridinium and phenyl rings of each cation being 0.96 (15) and 7.05 (16)°. In the crystal structure, the cations are stacked in an anti­parallel manner along the a axis through weak C—H⋯π inter­actions and ππ inter­actions, with centroid–centroid distances of 3.5544 (19) and 3.699 (2) Å. The 4-bromobenzene­sulfonate anions and the cations are linked together by weak C—H⋯O inter­actions. A short Br⋯I contact [3.6373 (4) Å] and C—H⋯I interactions are also observed.

Related literature

For bond-length data, see: Allen et al. (1987[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.]). For background to non-linear optical materials research, see: Chia et al. (1995[Chia, W.-L., Chen, C.-N. & Sheu, H.-J. (1995). Mater. Res. Bull. 30, 1421-1430.]); Pan et al. (1996[Pan, F., Wong, M. S., Bosshard, C. & Gunter, P. (1996). Adv. Mater. 8, 592-596.]); Prasad & Williams (1991[Prasad, P. N. & Williams, D. J. (1991). Introduction to Nonlinear Optical Effects in Molecules and Polymers. New York: Wiley.]). For related structures, see: Chantrapromma et al. (2006[Chantrapromma, S., Ruanwas, P., Fun, H.-K. & Patil, P. S. (2006). Acta Cryst. E62, o5494-o5496.]); Fun, Chanawanno & Chantrapromma (2009a[Fun, H.-K., Chanawanno, K. & Chantrapromma, S. (2009a). Acta Cryst. E65, o1554-o1555.],b[Fun, H.-K., Chanawanno, K. & Chantrapromma, S. (2009b). Acta Cryst. E65, o1934-o1935.]): Fun, Surasit et al. (2009[Fun, H.-K., Surasit, C., Chanawanno, K. & Chantrapromma, S. (2009). Acta Cryst. E65, o2633-o2634.]). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986[Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105-107.]).

[Scheme 1]

Experimental

Crystal data
  • 2C14H14N+·C6H4BrO3S·I

  • Mr = 755.49

  • Monoclinic, P 21 /c

  • a = 7.7766 (2) Å

  • b = 32.2737 (9) Å

  • c = 12.8009 (4) Å

  • β = 96.097 (2)°

  • V = 3194.59 (16) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 2.36 mm−1

  • T = 100 K

  • 0.50 × 0.14 × 0.05 mm

Data collection
  • Bruker APEXII CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.383, Tmax = 0.889

  • 42790 measured reflections

  • 9275 independent reflections

  • 7161 reflections with I > 2σ(I)

  • Rint = 0.054

Refinement
  • R[F2 > 2σ(F2)] = 0.042

  • wR(F2) = 0.089

  • S = 1.03

  • 9275 reflections

  • 381 parameters

  • H-atom parameters constrained

  • Δρmax = 1.96 e Å−3

  • Δρmin = −1.13 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 and Cg4 are the centroids of the C8A–C13A and C8B–C13B phenyl rings, respectively.

D—H⋯A D—H H⋯A DA D—H⋯A
C2A—H2AA⋯O2i 0.93 2.45 3.253 (3) 144
C3A—H3AA⋯O1 0.93 2.47 3.189 (3) 134
C2B—H2BA⋯O2ii 0.93 2.24 3.169 (4) 177
C4B—H4BA⋯O3 0.93 2.49 3.328 (4) 151
C11A—H11A⋯O1iii 0.93 2.51 3.390 (4) 159
C7B—H7BA⋯O3 0.93 2.50 3.314 (4) 146
C14A—H14C⋯O1 0.96 2.44 3.171 (4) 133
C14B—H14D⋯O3ii 0.96 2.46 3.365 (4) 157
C1A—H1AA⋯I1i 0.93 3.26 3.841 (3) 123
C1B—H1BA⋯I1ii 0.93 3.35 3.787 (3) 111
C17—H17A⋯I1iv 0.93 3.10 3.863 (3) 141
C14A—H14ACg2v 0.96 2.72 3.475 (3) 136
C14B—H14ECg4vi 0.96 2.73 3.520 (3) 140
Symmetry codes: (i) -x+1, -y, -z+1; (ii) [x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]; (iii) x+1, y, z+1; (iv) x, y, z+1; (v) -x+1, -y, -z+2; (vi) [x+1, -y-{\script{1\over 2}}, z-{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Comment top

Organic molecules are promising candidates for the nonlinear optical (NLO) applications. Stilbene derivatives, especially the pyridinium stilbenes with Donor-π-Acceptor system, were recognized as a good organic NLO chromophore (Chia et al., 1995; Pan et al., 1996). We previously reported the systhesis and crystal structure of bis[(E)-1-methyl-4-styrylpyridinium] 4-chlorobenzenesulfonate iodide (I), a pyridinium stilbene derivative, which crystallizes in noncentrosymmetric P21 space group and exhibits second-order NLO properties (Fun et al., 2009; Prasad & Williams, 1991). In this work, the title compound (II) was synthesized by changing the 4-chlorobenzenesulfonate anionic part in (I) to the 4-bromobenzenesulfonate to study the different NLO properties. By changing this, it was found that the title compound (II) crystallizes in centrosymmetric P21/c space group and does not show second-order NLO properties.

The title molecule consists of two C14H14N+(A and B), one C6H4BrO3S- and one I- ions (Fig. 1), the two cations exist in an E configuration with respect to the C6C7 ethenyl bond with the torsion angle of C6–C7–C8–C9 = 179.9 (3)° in molecule A [178.5 (3)° in molecule B]. One cation [molecule A] is planar while the other [molecule B] is slightly twisted, with the dihedral angles between the pyridinium and phenyl rings of the cation being 0.96 (15) and 7.05 (16)°, respectively. The two cations lie nearly on the same plane but in anti-parallel fashion with the dihedral angle between the planes through the whole molecule of cations being 4.01 (8)°. The anion is equally inclined with respect to the cations with the dihedral angles between the benzene ring of the anion and the pyridinium rings of the two cations being 82.20 (14) [molecule A] and 82.19 (15)° [molecule B], respectively. The bond distances in both cations and anion have normal values (Allen et al., 1987) and comparable with the closely related compounds (Fun et al., 2009a,b; Fun et al., 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 cations are stacked in an antiparallel manner along the a axis. The anions and I- ions are located in interstitial spaces between the cations, and the ions linked together through weak C—H···O, C—H···I and C—H···π interactions (Table 1) forming a 3D network. The crystal structure is further stabilized by ππ interactions with the distances of Cg1···Cg2vi = 3.5544 (19) Å and Cg3···Cg4ii, vii = 3.699 (2) Å [(vi) = 2-x, -y, 2-z; (vii) = x, 1/2-y, =1/2+z; Cg1, Cg2, Cg3 and Cg4 are the centroids of C1A–C5A/N1A, C8A–C13A, C1B–C5B/N1B and C8B–C13B, respectively]. In addition the crystal structure also shows short C···O [3.169 (4)–3.365 (4) Å] and Br···I [3.6373 (4) Å] contacts.

Related literature top

For bond-length data, see: Allen et al. (1987). For background to non-linear optical materials research, see: Chia et al. (1995); Pan et al. (1996); Prasad & Williams (1991). For related structures, see: Chantrapromma et al. (2006); Fun et al. (2009a,b): Fun et al. (2009). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

(E)-1-methyl-4-styrylpyridinium iodide (compound A, 0.19 g, 0.58 mmol) which was prepared according the previous method (Fun et al., 2009) was mixed with silver (I) 4-bromobenzenesulfonate (0.20 g, 0.58 mmol) (Chantrapromma et al., 2006) in methanol solution and stirred for 30 minutes. The precipitate of silver iodide which formed was filtered and the filtrate was evaporated to give the title compound as an orange solid. Orange needle-shaped single crystals of the title compound suitable for x-ray structure determination were recrystallized from methanol by slow evaporation at room temperature over a week (m.p. 472–473 K).

Refinement top

All H atoms were positioned geometrically and allowed to ride on their parent atoms, with d(C—H) = 0.93 Å for aromatic and CH and 0.96 Å for CH3 atoms. The Uiso(H) values were constrained to be 1.5Ueq of the carrier atom for methyl H atoms and 1.2Ueq for the remaining H atoms. A rotating group model was used for the methyl groups. The highest residual electron density peak is located at 0.78 Å from I1 and the deepest hole is located at 0.70 Å from I1.

Structure description top

Organic molecules are promising candidates for the nonlinear optical (NLO) applications. Stilbene derivatives, especially the pyridinium stilbenes with Donor-π-Acceptor system, were recognized as a good organic NLO chromophore (Chia et al., 1995; Pan et al., 1996). We previously reported the systhesis and crystal structure of bis[(E)-1-methyl-4-styrylpyridinium] 4-chlorobenzenesulfonate iodide (I), a pyridinium stilbene derivative, which crystallizes in noncentrosymmetric P21 space group and exhibits second-order NLO properties (Fun et al., 2009; Prasad & Williams, 1991). In this work, the title compound (II) was synthesized by changing the 4-chlorobenzenesulfonate anionic part in (I) to the 4-bromobenzenesulfonate to study the different NLO properties. By changing this, it was found that the title compound (II) crystallizes in centrosymmetric P21/c space group and does not show second-order NLO properties.

The title molecule consists of two C14H14N+(A and B), one C6H4BrO3S- and one I- ions (Fig. 1), the two cations exist in an E configuration with respect to the C6C7 ethenyl bond with the torsion angle of C6–C7–C8–C9 = 179.9 (3)° in molecule A [178.5 (3)° in molecule B]. One cation [molecule A] is planar while the other [molecule B] is slightly twisted, with the dihedral angles between the pyridinium and phenyl rings of the cation being 0.96 (15) and 7.05 (16)°, respectively. The two cations lie nearly on the same plane but in anti-parallel fashion with the dihedral angle between the planes through the whole molecule of cations being 4.01 (8)°. The anion is equally inclined with respect to the cations with the dihedral angles between the benzene ring of the anion and the pyridinium rings of the two cations being 82.20 (14) [molecule A] and 82.19 (15)° [molecule B], respectively. The bond distances in both cations and anion have normal values (Allen et al., 1987) and comparable with the closely related compounds (Fun et al., 2009a,b; Fun et al., 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 cations are stacked in an antiparallel manner along the a axis. The anions and I- ions are located in interstitial spaces between the cations, and the ions linked together through weak C—H···O, C—H···I and C—H···π interactions (Table 1) forming a 3D network. The crystal structure is further stabilized by ππ interactions with the distances of Cg1···Cg2vi = 3.5544 (19) Å and Cg3···Cg4ii, vii = 3.699 (2) Å [(vi) = 2-x, -y, 2-z; (vii) = x, 1/2-y, =1/2+z; Cg1, Cg2, Cg3 and Cg4 are the centroids of C1A–C5A/N1A, C8A–C13A, C1B–C5B/N1B and C8B–C13B, respectively]. In addition the crystal structure also shows short C···O [3.169 (4)–3.365 (4) Å] and Br···I [3.6373 (4) Å] contacts.

For bond-length data, see: Allen et al. (1987). For background to non-linear optical materials research, see: Chia et al. (1995); Pan et al. (1996); Prasad & Williams (1991). For related structures, see: Chantrapromma et al. (2006); Fun et al. (2009a,b): Fun et al. (2009). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

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
[Figure 1] Fig. 1. The molecular structure of the title compound, with 50% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. The crystal packing of the title compound viewed down the a axis. Weak C—H···O and C—H···I interactions are shown as dashed lines.
Bis[(E)-1-methyl-4-styrylpyridinium] 4-bromobenzenesulfonate iodide top
Crystal data top
2C14H14N+·C6H4BrO3S·IF(000) = 1512
Mr = 755.49Dx = 1.571 Mg m3
Monoclinic, P21/cMelting point = 472–473 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 7.7766 (2) ÅCell parameters from 9275 reflections
b = 32.2737 (9) Åθ = 1.3–30.0°
c = 12.8009 (4) ŵ = 2.36 mm1
β = 96.097 (2)°T = 100 K
V = 3194.59 (16) Å3Needle, orange
Z = 40.50 × 0.14 × 0.05 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
9275 independent reflections
Radiation source: sealed tube7161 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.054
φ and ω scansθmax = 30.0°, θmin = 1.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
h = 1010
Tmin = 0.383, Tmax = 0.889k = 4545
42790 measured reflectionsl = 1818
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0271P)2 + 6.2363P]
where P = (Fo2 + 2Fc2)/3
9275 reflections(Δ/σ)max = 0.001
381 parametersΔρmax = 1.96 e Å3
0 restraintsΔρmin = 1.13 e Å3
Crystal data top
2C14H14N+·C6H4BrO3S·IV = 3194.59 (16) Å3
Mr = 755.49Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.7766 (2) ŵ = 2.36 mm1
b = 32.2737 (9) ÅT = 100 K
c = 12.8009 (4) Å0.50 × 0.14 × 0.05 mm
β = 96.097 (2)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
9275 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
7161 reflections with I > 2σ(I)
Tmin = 0.383, Tmax = 0.889Rint = 0.054
42790 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.089H-atom parameters constrained
S = 1.03Δρmax = 1.96 e Å3
9275 reflectionsΔρmin = 1.13 e Å3
381 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
xyzUiso*/Ueq
I10.60308 (3)0.140711 (6)0.018059 (15)0.02340 (6)
Br11.22595 (4)0.122562 (10)0.83018 (3)0.02557 (8)
S10.51213 (10)0.11278 (2)0.52311 (5)0.01778 (14)
O10.4366 (3)0.07387 (7)0.55369 (17)0.0263 (5)
O20.5601 (3)0.11252 (7)0.41576 (16)0.0247 (5)
O30.4107 (3)0.14897 (7)0.54613 (17)0.0244 (5)
N1A0.4474 (3)0.01295 (8)0.72887 (19)0.0188 (5)
C1A0.6113 (4)0.04541 (10)0.8712 (2)0.0247 (7)
H1AA0.65220.06970.90440.030*
C2A0.5079 (4)0.04764 (9)0.7787 (2)0.0216 (6)
H2AA0.47870.07340.74950.026*
C3A0.4852 (4)0.02476 (10)0.7710 (2)0.0226 (6)
H3AA0.44140.04840.73630.027*
C4A0.5875 (4)0.02843 (10)0.8645 (2)0.0241 (7)
H4AA0.61120.05450.89330.029*
C5A0.6568 (4)0.00702 (11)0.9171 (2)0.0244 (7)
C6A0.7692 (5)0.00622 (11)1.0150 (3)0.0282 (7)
H6AA0.80830.03151.04330.034*
C7A0.8207 (4)0.02818 (11)1.0675 (2)0.0268 (7)
H7AA0.78120.05331.03860.032*
C8A0.9350 (4)0.02981 (10)1.1676 (2)0.0237 (6)
C9A0.9766 (4)0.06887 (10)1.2096 (3)0.0265 (7)
H9AA0.93340.09251.17430.032*
C10A1.0815 (5)0.07282 (11)1.3031 (3)0.0310 (8)
H10A1.10780.09911.33020.037*
C11A1.1479 (5)0.03825 (11)1.3571 (3)0.0302 (8)
H11A1.21980.04121.41950.036*
C12A1.1059 (5)0.00100 (11)1.3169 (3)0.0296 (7)
H12A1.14790.02451.35330.036*
C13A1.0021 (4)0.00511 (10)1.2230 (2)0.0250 (7)
H13A0.97640.03141.19610.030*
C14A0.3408 (4)0.01642 (10)0.6261 (2)0.0235 (6)
H14A0.24550.03480.63260.035*
H14B0.41030.02710.57460.035*
H14C0.29740.01040.60450.035*
N2B0.5060 (3)0.26563 (8)0.85716 (19)0.0202 (5)
C1B0.3607 (5)0.30099 (11)0.7133 (2)0.0276 (7)
H1BA0.32480.32600.68210.033*
C2B0.4540 (4)0.30119 (10)0.8096 (2)0.0235 (6)
H2BA0.48200.32630.84280.028*
C3B0.4697 (4)0.22869 (10)0.8097 (3)0.0251 (7)
H3BA0.50700.20420.84330.030*
C4B0.3775 (5)0.22730 (11)0.7119 (3)0.0280 (7)
H4BA0.35410.20190.67930.034*
C5B0.3181 (4)0.26401 (11)0.6607 (2)0.0250 (7)
C6B0.2169 (5)0.26553 (11)0.5576 (3)0.0284 (7)
H6BA0.18930.29140.52830.034*
C7B0.1624 (4)0.23200 (11)0.5035 (3)0.0261 (7)
H7BA0.19380.20650.53340.031*
C8B0.0572 (4)0.23131 (11)0.4009 (2)0.0247 (7)
C9B0.0042 (5)0.19256 (11)0.3613 (3)0.0298 (7)
H9BA0.03900.16880.39890.036*
C10B0.0981 (5)0.18892 (11)0.2678 (3)0.0315 (8)
H10B0.13330.16280.24310.038*
C11B0.1495 (4)0.22374 (11)0.2099 (3)0.0277 (7)
H11B0.21800.22110.14610.033*
C12B0.0986 (5)0.26285 (11)0.2471 (3)0.0283 (7)
H12B0.13330.28640.20850.034*
C13B0.0040 (4)0.26660 (11)0.3422 (3)0.0273 (7)
H13B0.03780.29270.36720.033*
C14B0.6078 (4)0.26654 (11)0.9611 (2)0.0266 (7)
H14D0.56000.28691.00460.040*
H14E0.72560.27360.95290.040*
H14F0.60410.23980.99340.040*
C150.7120 (4)0.11668 (9)0.6057 (2)0.0179 (6)
C160.7080 (4)0.12213 (9)0.7132 (2)0.0202 (6)
H16A0.60250.12470.74050.024*
C170.8612 (4)0.12368 (10)0.7799 (2)0.0225 (6)
H17A0.85930.12710.85190.027*
C181.0171 (4)0.12006 (9)0.7367 (2)0.0215 (6)
C191.0250 (4)0.11501 (10)0.6301 (3)0.0250 (7)
H19A1.13080.11280.60280.030*
C200.8692 (4)0.11333 (10)0.5645 (2)0.0236 (6)
H20A0.87120.10990.49250.028*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.02846 (11)0.02210 (10)0.01938 (9)0.00045 (9)0.00141 (7)0.00226 (8)
Br10.01741 (15)0.02441 (16)0.03402 (17)0.00048 (12)0.00127 (13)0.00088 (13)
S10.0203 (4)0.0160 (3)0.0170 (3)0.0016 (3)0.0017 (3)0.0009 (2)
O10.0293 (12)0.0253 (12)0.0232 (11)0.0098 (10)0.0021 (9)0.0048 (9)
O20.0305 (13)0.0245 (11)0.0192 (10)0.0025 (10)0.0034 (9)0.0011 (8)
O30.0225 (11)0.0252 (12)0.0257 (11)0.0038 (9)0.0034 (9)0.0014 (9)
N1A0.0190 (13)0.0197 (12)0.0184 (11)0.0002 (10)0.0050 (10)0.0004 (9)
C1A0.0283 (17)0.0236 (16)0.0229 (15)0.0029 (13)0.0063 (13)0.0022 (12)
C2A0.0225 (16)0.0165 (14)0.0267 (15)0.0006 (12)0.0073 (13)0.0007 (11)
C3A0.0265 (17)0.0196 (15)0.0230 (14)0.0011 (12)0.0082 (13)0.0003 (11)
C4A0.0281 (17)0.0240 (16)0.0213 (14)0.0066 (13)0.0073 (13)0.0046 (12)
C5A0.0232 (16)0.0335 (18)0.0173 (13)0.0032 (14)0.0058 (12)0.0010 (12)
C6A0.0312 (19)0.0277 (17)0.0255 (15)0.0004 (14)0.0028 (14)0.0011 (13)
C7A0.0270 (17)0.0295 (17)0.0242 (15)0.0037 (14)0.0044 (13)0.0007 (13)
C8A0.0193 (15)0.0313 (17)0.0208 (14)0.0019 (13)0.0038 (12)0.0038 (12)
C9A0.0256 (17)0.0268 (16)0.0268 (15)0.0067 (14)0.0015 (13)0.0033 (13)
C10A0.0314 (19)0.0281 (18)0.0326 (17)0.0040 (15)0.0009 (15)0.0076 (14)
C11A0.0258 (17)0.041 (2)0.0224 (15)0.0006 (15)0.0038 (13)0.0034 (14)
C12A0.0277 (18)0.0294 (18)0.0318 (17)0.0023 (14)0.0031 (15)0.0080 (14)
C13A0.0239 (16)0.0255 (16)0.0267 (15)0.0037 (13)0.0072 (13)0.0045 (12)
C14A0.0262 (17)0.0244 (16)0.0195 (14)0.0014 (13)0.0003 (12)0.0020 (11)
N2B0.0190 (13)0.0242 (13)0.0176 (11)0.0011 (10)0.0033 (10)0.0016 (10)
C1B0.0317 (18)0.0278 (17)0.0237 (15)0.0020 (14)0.0050 (14)0.0039 (13)
C2B0.0249 (16)0.0193 (15)0.0270 (15)0.0008 (13)0.0060 (13)0.0002 (12)
C3B0.0280 (17)0.0206 (15)0.0276 (16)0.0001 (13)0.0064 (13)0.0009 (12)
C4B0.0305 (18)0.0276 (17)0.0266 (16)0.0058 (14)0.0062 (14)0.0090 (13)
C5B0.0212 (16)0.0358 (18)0.0192 (14)0.0014 (14)0.0070 (12)0.0018 (12)
C6B0.0339 (19)0.0273 (17)0.0237 (15)0.0020 (14)0.0017 (14)0.0015 (13)
C7B0.0240 (16)0.0291 (17)0.0255 (15)0.0025 (14)0.0033 (13)0.0006 (13)
C8B0.0162 (15)0.0366 (18)0.0216 (14)0.0009 (13)0.0033 (12)0.0024 (13)
C9B0.0295 (18)0.0304 (18)0.0290 (16)0.0077 (15)0.0002 (14)0.0013 (14)
C10B0.0330 (19)0.0252 (17)0.0354 (18)0.0026 (15)0.0007 (15)0.0064 (14)
C11B0.0250 (17)0.0336 (18)0.0235 (15)0.0006 (14)0.0024 (13)0.0058 (13)
C12B0.0286 (18)0.0271 (17)0.0287 (16)0.0003 (14)0.0009 (14)0.0030 (13)
C13B0.0256 (17)0.0286 (17)0.0278 (16)0.0066 (14)0.0041 (14)0.0057 (13)
C14B0.0240 (17)0.0354 (18)0.0197 (14)0.0006 (14)0.0002 (13)0.0017 (13)
C150.0182 (14)0.0139 (13)0.0217 (13)0.0001 (11)0.0025 (11)0.0005 (10)
C160.0153 (14)0.0228 (15)0.0229 (14)0.0004 (12)0.0040 (11)0.0009 (11)
C170.0223 (15)0.0237 (15)0.0216 (14)0.0004 (13)0.0028 (12)0.0012 (12)
C180.0169 (14)0.0197 (15)0.0275 (15)0.0005 (12)0.0007 (12)0.0001 (11)
C190.0174 (15)0.0269 (16)0.0321 (16)0.0002 (13)0.0082 (13)0.0007 (13)
C200.0262 (17)0.0231 (15)0.0228 (14)0.0004 (13)0.0088 (13)0.0011 (12)
Geometric parameters (Å, º) top
Br1—C181.914 (3)C1B—C2B1.363 (4)
S1—O31.457 (2)C1B—C5B1.392 (5)
S1—O11.457 (2)C1B—H1BA0.9300
S1—O21.462 (2)C2B—H2BA0.9300
S1—C151.789 (3)C3B—C4B1.376 (4)
N1A—C2A1.348 (4)C3B—H3BA0.9300
N1A—C3A1.351 (4)C4B—C5B1.407 (5)
N1A—C14A1.483 (4)C4B—H4BA0.9300
C1A—C2A1.361 (4)C5B—C6B1.465 (4)
C1A—C5A1.400 (5)C6B—C7B1.330 (5)
C1A—H1AA0.9300C6B—H6BA0.9300
C2A—H2AA0.9300C7B—C8B1.472 (4)
C3A—C4A1.370 (4)C7B—H7BA0.9300
C3A—H3AA0.9300C8B—C9B1.395 (5)
C4A—C5A1.406 (5)C8B—C13B1.402 (5)
C4A—H4AA0.9300C9B—C10B1.370 (5)
C5A—C6A1.449 (4)C9B—H9BA0.9300
C6A—C7A1.337 (5)C10B—C11B1.382 (5)
C6A—H6AA0.9300C10B—H10B0.9300
C7A—C8A1.481 (4)C11B—C12B1.392 (5)
C7A—H7AA0.9300C11B—H11B0.9300
C8A—C9A1.395 (5)C12B—C13B1.388 (4)
C8A—C13A1.402 (5)C12B—H12B0.9300
C9A—C10A1.381 (4)C13B—H13B0.9300
C9A—H9AA0.9300C14B—H14D0.9600
C10A—C11A1.383 (5)C14B—H14E0.9600
C10A—H10A0.9300C14B—H14F0.9600
C11A—C12A1.393 (5)C15—C201.386 (4)
C11A—H11A0.9300C15—C161.390 (4)
C12A—C13A1.381 (5)C16—C171.391 (4)
C12A—H12A0.9300C16—H16A0.9300
C13A—H13A0.9300C17—C181.390 (4)
C14A—H14A0.9600C17—H17A0.9300
C14A—H14B0.9600C18—C191.382 (4)
C14A—H14C0.9600C19—C201.401 (4)
N2B—C2B1.341 (4)C19—H19A0.9300
N2B—C3B1.354 (4)C20—H20A0.9300
N2B—C14B1.474 (4)
O3—S1—O1113.20 (14)N2B—C2B—C1B120.8 (3)
O3—S1—O2113.12 (13)N2B—C2B—H2BA119.6
O1—S1—O2113.44 (13)C1B—C2B—H2BA119.6
O3—S1—C15106.21 (13)N2B—C3B—C4B120.0 (3)
O1—S1—C15104.57 (13)N2B—C3B—H3BA120.0
O2—S1—C15105.29 (14)C4B—C3B—H3BA120.0
C2A—N1A—C3A120.6 (3)C3B—C4B—C5B120.6 (3)
C2A—N1A—C14A119.4 (3)C3B—C4B—H4BA119.7
C3A—N1A—C14A120.0 (3)C5B—C4B—H4BA119.7
C2A—C1A—C5A120.7 (3)C1B—C5B—C4B116.6 (3)
C2A—C1A—H1AA119.6C1B—C5B—C6B119.0 (3)
C5A—C1A—H1AA119.6C4B—C5B—C6B124.5 (3)
N1A—C2A—C1A120.8 (3)C7B—C6B—C5B123.6 (3)
N1A—C2A—H2AA119.6C7B—C6B—H6BA118.2
C1A—C2A—H2AA119.6C5B—C6B—H6BA118.2
N1A—C3A—C4A120.6 (3)C6B—C7B—C8B126.4 (3)
N1A—C3A—H3AA119.7C6B—C7B—H7BA116.8
C4A—C3A—H3AA119.7C8B—C7B—H7BA116.8
C3A—C4A—C5A120.4 (3)C9B—C8B—C13B118.3 (3)
C3A—C4A—H4AA119.8C9B—C8B—C7B116.9 (3)
C5A—C4A—H4AA119.8C13B—C8B—C7B124.7 (3)
C1A—C5A—C4A116.9 (3)C10B—C9B—C8B121.1 (3)
C1A—C5A—C6A118.7 (3)C10B—C9B—H9BA119.5
C4A—C5A—C6A124.4 (3)C8B—C9B—H9BA119.5
C7A—C6A—C5A124.8 (3)C9B—C10B—C11B120.5 (3)
C7A—C6A—H6AA117.6C9B—C10B—H10B119.8
C5A—C6A—H6AA117.6C11B—C10B—H10B119.8
C6A—C7A—C8A125.8 (3)C10B—C11B—C12B119.9 (3)
C6A—C7A—H7AA117.1C10B—C11B—H11B120.1
C8A—C7A—H7AA117.1C12B—C11B—H11B120.1
C9A—C8A—C13A118.2 (3)C13B—C12B—C11B119.7 (3)
C9A—C8A—C7A117.3 (3)C13B—C12B—H12B120.1
C13A—C8A—C7A124.5 (3)C11B—C12B—H12B120.1
C10A—C9A—C8A120.6 (3)C12B—C13B—C8B120.5 (3)
C10A—C9A—H9AA119.7C12B—C13B—H13B119.7
C8A—C9A—H9AA119.7C8B—C13B—H13B119.7
C9A—C10A—C11A120.9 (3)N2B—C14B—H14D109.5
C9A—C10A—H10A119.6N2B—C14B—H14E109.5
C11A—C10A—H10A119.6H14D—C14B—H14E109.5
C10A—C11A—C12A119.3 (3)N2B—C14B—H14F109.5
C10A—C11A—H11A120.4H14D—C14B—H14F109.5
C12A—C11A—H11A120.4H14E—C14B—H14F109.5
C13A—C12A—C11A120.1 (3)C20—C15—C16120.0 (3)
C13A—C12A—H12A120.0C20—C15—S1121.0 (2)
C11A—C12A—H12A120.0C16—C15—S1119.0 (2)
C12A—C13A—C8A121.0 (3)C15—C16—C17120.3 (3)
C12A—C13A—H13A119.5C15—C16—H16A119.9
C8A—C13A—H13A119.5C17—C16—H16A119.9
N1A—C14A—H14A109.5C18—C17—C16118.6 (3)
N1A—C14A—H14B109.5C18—C17—H17A120.7
H14A—C14A—H14B109.5C16—C17—H17A120.7
N1A—C14A—H14C109.5C19—C18—C17122.3 (3)
H14A—C14A—H14C109.5C19—C18—Br1119.9 (2)
H14B—C14A—H14C109.5C17—C18—Br1117.8 (2)
C2B—N2B—C3B120.8 (3)C18—C19—C20118.1 (3)
C2B—N2B—C14B120.0 (3)C18—C19—H19A121.0
C3B—N2B—C14B119.3 (3)C20—C19—H19A121.0
C2B—C1B—C5B121.2 (3)C15—C20—C19120.7 (3)
C2B—C1B—H1BA119.4C15—C20—H20A119.7
C5B—C1B—H1BA119.4C19—C20—H20A119.7
C3A—N1A—C2A—C1A1.4 (5)C3B—C4B—C5B—C1B1.2 (5)
C14A—N1A—C2A—C1A177.6 (3)C3B—C4B—C5B—C6B179.0 (3)
C5A—C1A—C2A—N1A0.2 (5)C1B—C5B—C6B—C7B176.5 (3)
C2A—N1A—C3A—C4A0.8 (5)C4B—C5B—C6B—C7B3.7 (6)
C14A—N1A—C3A—C4A178.2 (3)C5B—C6B—C7B—C8B178.5 (3)
N1A—C3A—C4A—C5A1.0 (5)C6B—C7B—C8B—C9B175.7 (4)
C2A—C1A—C5A—C4A1.5 (5)C6B—C7B—C8B—C13B2.7 (6)
C2A—C1A—C5A—C6A179.2 (3)C13B—C8B—C9B—C10B0.4 (5)
C3A—C4A—C5A—C1A2.1 (5)C7B—C8B—C9B—C10B178.1 (3)
C3A—C4A—C5A—C6A178.6 (3)C8B—C9B—C10B—C11B0.8 (6)
C1A—C5A—C6A—C7A179.1 (3)C9B—C10B—C11B—C12B0.7 (6)
C4A—C5A—C6A—C7A0.1 (6)C10B—C11B—C12B—C13B0.2 (5)
C5A—C6A—C7A—C8A179.9 (3)C11B—C12B—C13B—C8B0.2 (5)
C6A—C7A—C8A—C9A178.9 (4)C9B—C8B—C13B—C12B0.1 (5)
C6A—C7A—C8A—C13A1.7 (6)C7B—C8B—C13B—C12B178.5 (3)
C13A—C8A—C9A—C10A0.1 (5)O3—S1—C15—C20128.7 (3)
C7A—C8A—C9A—C10A179.5 (3)O1—S1—C15—C20111.4 (3)
C8A—C9A—C10A—C11A0.2 (6)O2—S1—C15—C208.4 (3)
C9A—C10A—C11A—C12A0.9 (6)O3—S1—C15—C1652.9 (3)
C10A—C11A—C12A—C13A1.4 (5)O1—S1—C15—C1667.0 (3)
C11A—C12A—C13A—C8A1.1 (5)O2—S1—C15—C16173.2 (2)
C9A—C8A—C13A—C12A0.3 (5)C20—C15—C16—C170.9 (4)
C7A—C8A—C13A—C12A179.0 (3)S1—C15—C16—C17177.5 (2)
C3B—N2B—C2B—C1B1.2 (5)C15—C16—C17—C180.6 (5)
C14B—N2B—C2B—C1B179.6 (3)C16—C17—C18—C190.0 (5)
C5B—C1B—C2B—N2B0.7 (5)C16—C17—C18—Br1179.7 (2)
C2B—N2B—C3B—C4B0.4 (5)C17—C18—C19—C200.3 (5)
C14B—N2B—C3B—C4B178.8 (3)Br1—C18—C19—C20180.0 (2)
N2B—C3B—C4B—C5B0.9 (5)C16—C15—C20—C190.6 (5)
C2B—C1B—C5B—C4B0.5 (5)S1—C15—C20—C19177.8 (2)
C2B—C1B—C5B—C6B179.7 (3)C18—C19—C20—C150.0 (5)
Hydrogen-bond geometry (Å, º) top
Cg2 and Cg4 are the centroids of the C8A–C13A and C8B–C13B phenyl rings, respectively.
D—H···AD—HH···AD···AD—H···A
C2A—H2AA···O2i0.932.453.253 (3)144
C3A—H3AA···O10.932.473.189 (3)134
C2B—H2BA···O2ii0.932.243.169 (4)177
C4B—H4BA···O30.932.493.328 (4)151
C11A—H11A···O1iii0.932.513.390 (4)159
C7B—H7BA···O30.932.503.314 (4)146
C14A—H14C···O10.962.443.171 (4)133
C14B—H14D···O3ii0.962.463.365 (4)157
C1A—H1AA···I1i0.933.263.841 (3)123
C1B—H1BA···I1ii0.933.353.787 (3)111
C17—H17A···I1iv0.933.103.863 (3)141
C14A—H14A···Cg2v0.962.723.475 (3)136
C14B—H14E···Cg4vi0.962.733.520 (3)140
Symmetry codes: (i) x+1, y, z+1; (ii) x, y+1/2, z+1/2; (iii) x+1, y, z+1; (iv) x, y, z+1; (v) x+1, y, z+2; (vi) x+1, y1/2, z1/2.

Experimental details

Crystal data
Chemical formula2C14H14N+·C6H4BrO3S·I
Mr755.49
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)7.7766 (2), 32.2737 (9), 12.8009 (4)
β (°) 96.097 (2)
V3)3194.59 (16)
Z4
Radiation typeMo Kα
µ (mm1)2.36
Crystal size (mm)0.50 × 0.14 × 0.05
Data collection
DiffractometerBruker APEXII CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2005)
Tmin, Tmax0.383, 0.889
No. of measured, independent and
observed [I > 2σ(I)] reflections
42790, 9275, 7161
Rint0.054
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.089, 1.03
No. of reflections9275
No. of parameters381
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.96, 1.13

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

Hydrogen-bond geometry (Å, º) top
Cg2 and Cg4 are the centroids of the C8A–C13A and C8B–C13B phenyl rings, respectively.
D—H···AD—HH···AD···AD—H···A
C2A—H2AA···O2i0.932.453.253 (3)144
C3A—H3AA···O10.932.473.189 (3)134
C2B—H2BA···O2ii0.932.243.169 (4)177
C4B—H4BA···O30.932.493.328 (4)151
C11A—H11A···O1iii0.932.513.390 (4)159
C7B—H7BA···O30.932.503.314 (4)146
C14A—H14C···O10.962.443.171 (4)133
C14B—H14D···O3ii0.962.463.365 (4)157
C1A—H1AA···I1i0.933.263.841 (3)123
C1B—H1BA···I1ii0.933.353.787 (3)111
C17—H17A···I1iv0.933.103.863 (3)141
C14A—H14A···Cg2v0.962.723.475 (3)136
C14B—H14E···Cg4vi0.962.733.520 (3)140
Symmetry codes: (i) x+1, y, z+1; (ii) x, y+1/2, z+1/2; (iii) x+1, y, z+1; (iv) x, y, z+1; (v) x+1, y, z+2; (vi) x+1, y1/2, z1/2.
 

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 the Prince of Songkla University for financial support through the Crystal Materials Research Unit. KC thanks the Development and Promotion of Science and Technology Talents Project (DPST) for a fellowship. The authors also thank the Malaysian Government and Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

References

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