Crystal structure of (E)-2-(2-{5-[(2-acet­oxy­eth­yl)(meth­yl)amino]­thio­phen-2-yl}vin­yl)-3-methyl­benzo­thia­zolium iodide monohydrate

Xian-Shun Sun; Ming-Ming Wang; Dan-Dan Li

doi:10.1107/S1600536814020121

. 2014 Sep 13;70(Pt 10):o1104–o1105. doi: 10.1107/S1600536814020121

Crystal structure of (E)-2-(2-{5-[(2-acetoxyethyl)(methyl)amino]thiophen-2-yl}vinyl)-3-methylbenzothiazolium iodide monohydrate

Xian-Shun Sun ^a,^b, Ming-Ming Wang ^a,^b, Dan-Dan Li ^a,^b,^*

PMCID: PMC4257210 PMID: 25484696

Abstract

In the cation of the title hydrated salt, C₁₉H₂₁N₂O₂S₂ ⁺·I⁻·H₂O, the benzothiazolium ring system is approximately planar [maximum deviation = 0.0251 (15) Å], and it makes a small dihedral angle of 1.16 (18)° with the plane of the thiophene ring. In the crystal, the cations, anions and crystalline water molecules are linked by classical O—H⋯O, O—H⋯I and weak C—H⋯O hydrogn bonds, forming a three-dimensional supramolecular network. π–π stacking is observed between parallel thiazole rings of adjacent cations [centroid–centroid distance = 3.5945 (16) Å].

Keywords: crystal structure, benzothiazolium iodide salt, hydrogen bonding

Related literature

Experimental

Crystal data

C₁₉H₂₁N₂O₂S₂ ⁺·I⁻·H₂O
M _r = 518.43
Triclinic,
a = 9.6689 (9) Å
b = 11.1237 (11) Å
c = 11.1693 (11) Å
α = 94.420 (1)°
β = 110.067 (1)°
γ = 99.919 (1)°
V = 1099.40 (18) Å³
Z = 2
Mo Kα radiation
μ = 1.67 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.18 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
8450 measured reflections
4211 independent reflections
3638 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.071
S = 0.97
4211 reflections
247 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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.

Supplementary Material

Crystal structure: contains datablock(s) I, Global. DOI: 10.1107/S1600536814020121/xu5820sup1.cif

e-70-o1104-sup1.cif^{(20.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814020121/xu5820Isup2.hkl

e-70-o1104-Isup2.hkl^{(206.3KB, hkl)}

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S1600536814020121/xu5820fig1.tif

The molecular structure of the title compound (I) showing 30% probability displacement ellipsoids.

CCDC reference: 1023218

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯I1ⁱ	0.85	2.95	3.647 (3)	140
O2—H2C⋯O3ⁱⁱ	0.85	2.35	3.056 (5)	140
C7—H7A⋯O3ⁱ	0.96	2.46	3.364 (5)	157
C19—H19A⋯O2	0.96	2.60	3.554 (6)	173

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

Acknowledgments

This work was supported by the National Natural Science Foundation of China (grant No. 21271004), the Education Committee of Anhui Province, China (grant No. KJ2010A030), and the Undergraduate Innovative Test Program in Anhui University (grant No. 201310357260).

supplementary crystallographic information

S1. Comment

Interest in organic compounds with non-linear optical (NLO) properties is driven by the prospective of their applications in optical information technologies. The most common design of molecules with large NLO-active comprises strong electron-donors and acceptors connected by a π-conjugated system (Hao et al., 2009; Zhou et al., 2011). Besides, the introduction about the highpolarizability of sulfur atoms in thiophene rings leads to a stabilization of the conjugated chain and to excellent charge transport properties. In the title compound (I) (Fig. 1), the benzothiazolium-CH═CH-thiophene part of the molecule is nearly coplanar (plane of CH═CH makes angles of 0.663 (8)° and 0.847 (1)° with the planes of the benzothiazolium and the thiophene rings), while in related benzothiazolium derivatives (Quist et al. 2009), the corresponding angles are 5.61 (18)° and 1.78 (19)°, respectively.

S2. Experimental

A mixture of 2,3-dimethylbenzothiazolium iodide (1 mmol), 5-[(2-hydroxyethyl)methylamino]thiophene-2-carbaldehyde (1 mmol) and acetic anhydride (20 ml) was refluxed for 20 min, than poured into a warm solution of potassium iodide (4 mmol) in water (20 ml). The precipitated product was filtered, washed with water and recrystallized from a methanol/water solution. ¹H NMR: (400 Hz, DMSO-d₆), d(p.p.m.):8.14 (d, 1H), 8.11 (d, 1H), 7.89 (d, 1H), 7.83 (s, 1H), 7.66 (t, 1H), 7.53 (t, 1H), 6.73 (s, 1H), 6.54 (d, 1H), 4.33 (t, 2H), 4.00 (s, 3H), 3.85 (t, 2H), 3.24 (s, 3H), 1.94 (s, 3H).