2,2′-[2,4-Bis(naphthalen-1-yl)cyclo­butane-1,3-di­yl]bis­(1-methyl­pyridinium) bis­(4-chloro­benzene­sulfonate): thermal-induced [2 + 2] cyclo­addition reaction of a heterostilbene

Suchada Chantrapromma; Kullapa Chanawanno; Nawong Boonnak; Hoong-Kun Fun

doi:10.1107/S160053681400645X

. 2014 Apr 2;70(Pt 5):o510–o511. doi: 10.1107/S160053681400645X

2,2′-[2,4-Bis(naphthalen-1-yl)cyclobutane-1,3-diyl]bis(1-methylpyridinium) bis(4-chlorobenzenesulfonate): thermal-induced [2 + 2] cycloaddition reaction of a heterostilbene

Suchada Chantrapromma ^a,^*,^‡, Kullapa Chanawanno ^a, Nawong Boonnak ^b, Hoong-Kun Fun ^c,^§

PMCID: PMC4011255 PMID: 24860326

Abstract

The asymmetric unit of the title salt, C₃₆H₃₂N₂ ²⁺·2C₆H₄ClO₃S⁻, consists of one anion and one half-cation, the other half being generated by inversion symmetry. The dihedral angle between the pyridinium ring and the napthalene ring system in the asymmetric unit is 42.86 (6)°. In the crystal, cations and anions are linked by weak C—H⋯O interactions into chains along [010]. Adjacent chains are further arranged in an antiparallel manner into sheets parallel to the bc plane. π–π interactions are observed involving the cations, with centroid–centroid distances of 3.7664 (8) and 3.8553 (8) Å.

Related literature

For background to stibene and [2 + 2] photodimerization, see: Chanawanno et al. (2010 ▶); Chantrapromma et al. (2007 ▶); Papaefstathiou et al. (2002 ▶); Ruanwas et al. (2010 ▶); Yayli et al. (2004 ▶); Zhang et al. (2013 ▶). For related structures, see: Chantrapromma et al. (2012 ▶); Fun, Chanawanno & Chantrapromma (2009 ▶); Fun, Surasit et al. (2009 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶). graphic file with name e-70-0o510-scheme1.jpg

Experimental

Crystal data

C₃₆H₃₂N₂ ²⁺·2C₆H₄ClO₃S⁻
M _r = 875.86
Triclinic,
a = 7.5488 (3) Å
b = 11.1899 (4) Å
c = 12.3853 (5) Å
α = 79.904 (2)°
β = 75.964 (2)°
γ = 89.266 (2)°
V = 998.76 (7) Å³
Z = 1
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 100 K
0.56 × 0.50 × 0.21 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.837, T _max = 0.936
35475 measured reflections
5817 independent reflections
4977 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.115
S = 1.09
5817 reflections
351 parameters
All H-atom parameters refined
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.74 e Å⁻³

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 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681400645X/rz5110sup1.cif

e-70-0o510-sup1.cif^{(30.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681400645X/rz5110Isup2.hkl

e-70-0o510-Isup2.hkl^{(284.8KB, hkl)}

Click here for additional data file.^{(29B, cml)}

Supporting information file. DOI: 10.1107/S160053681400645X/rz5110Isup3.cml

CCDC reference: 993267

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg4 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O3	0.97 (2)	2.51 (2)	3.3762 (18)	147.9 (18)
C17—H17⋯O2ⁱ	0.974 (17)	2.506 (18)	3.3001 (18)	138.6 (13)
C20—H20⋯O2	0.97 (2)	2.20 (2)	3.1329 (18)	160.5 (19)
C23—H23⋯O1ⁱⁱ	0.94 (2)	2.41 (2)	3.1554 (17)	135.8 (18)
C24—H24B⋯O1ⁱⁱ	0.95 (2)	2.57 (2)	3.2009 (18)	124.3 (16)
C9—H9⋯Cg4ⁱⁱⁱ	1.00 (2)	2.98 (2)	3.4790 (16)	112.1 (16)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors thank the Department of Chemistry, Faculty of Science, Prince of Songkla University, for the research facility and extend their appreciation to the Malaysian Government and Universiti Sains Malaysia for APEX DE2012 grant No. 1002/PFIZIK/910323.

supplementary crystallographic information

1. Comment

Stilbene derivatives have been reported to exhibit non-linear optical (NLO) property (Ruanwas et al., 2010) and antibacterial activity (Chanawanno et al., 2010). It has been known that [2 + 2] photodimerization of stilbenes to yield cyclobutane can occur (Papaefstathiou et al., 2002). In our cases, the [2 + 2] cycloaddition of heterostilbene derivatives was carried out in solution by thermal-induced cycloaddition reaction, and we have previously reported the crystal structures of some of these derivatives (Chantrapromma et al., 2012; Fun, Chanawanno & Chantrapromma, 2009; Fun, Surasit et al., 2009). The title compound (I) was obtained by the cycloaddition of trans-heterostilbene to give a syn head-to-tail product (Yayli et al., 2004; Zhang et al., 2013). We report herein the synthesis and crystal structure of (I).

The asymmetric unit of (I), C₃₆H₃₂N₂²⁺·2(C₆H₄ClO₃S^-), consists of one half of a cation and one anion. The cation lies on an inversion center and the other half is generated by the symmetry operator 2-x, 1-y, 2-z (Fig. 1). The napthalene (C7–C16) moiety is planar with a r.m.s. of 0.0183 (2) Å. The dihedral angle between the pyridinium ring (N1/C19–C23) and the napthalene ring system is 42.86 (6)°. The steroisomer of (I) is syn head-to-tail (Yayli et al., 2004). The cyclobutane ring makes dihedral angles of 85.61 (8) and 52.8 (6)° with the pyridinium and naphthalene rings, respectively. The bond lengths are in normal ranges (Allen et al., 1987) and comparable with those found in closely related structures (Chantrapromma et al., 2012; Fun, Surasit et al., 2009; Fun, Chanawanno & Chantrapromma (2009).

The crystal packing of (I) is shown in Fig. 2. The cations and anions are alternatively arranged and linked into chains along the [0 1 0] direction through C—H···O weak interactions (Table 1). Adjacent chains are arranged in a anti-parallel manner into sheets parallel to the (1 0 0) plane. π···π interactions are present with distances of Cg₁···Cg₂ = 3.8553 (8) Å and Cg₁···Cg₃ = 3.7664 (8) Å; Cg₁, Cg₂ and Cg₃ are the centroids of the N1/C19–C23, C7–C10/C15/C16 and C10–C15 rings, respectively (Fig. 3). C—H···π weak interactions are also observed (Table 1).

2. Experimental

A solution of (E)-1-methyl-2-[2-(1-naphthyl)vinyl)pyridinium iodide (0.25 g, 0.67 mmol) in CH₃OH (20 ml) was mixed (1:1 molar ratio) with a solution of silver(I) 4-chlorobenzenesulfonate (0.20 g, 0.67 mmol) (Chantrapromma et al., 2007) in CH₃OH (80 ml) and stirred for 30 min. 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 CH₃OH and the solution was heated at 323 K to get a clear solution. The [2 + 2] cycloaddition of (E)-1-methyl-2-[2-(1-naphthyl)vinyl)pyridinium occurred upon heating. Yellow plate-shaped single crystals of the title compound suitable for X-ray structure determination were obtained after recrystallization in CH₃OH by slow evaporation of the solvent at room temperature after a few weeks.