2-Amino-6-methyl-1,3-benzothia­zole–deca­nedioic acid (2/1)

Xiang-Jun Shi; Zhi-Chao Wang; Qiang Chen; Xiao-Jun Zhao

doi:10.1107/S1600536809031857

. 2009 Aug 19;65(Pt 9):o2188. doi: 10.1107/S1600536809031857

2-Amino-6-methyl-1,3-benzothiazole–decanedioic acid (2/1)

Xiang-Jun Shi ^a, Zhi-Chao Wang ^a, Qiang Chen ^a, Xiao-Jun Zhao ^a,^*

PMCID: PMC2970063 PMID: 21577592

Abstract

Co-crystallization of 2-amino-6-methyl-1,3-benzothiazole with decanedioic acid under hydrothermal conditions afforded the title 2:1 co-crystal, 2C₈H₈N₂S·C₁₀H₁₈O₄. The decanedioic acid molecule is located on an inversion centre. In the crystal, intermolecular N—H⋯O and O—H⋯O hydrogen bonds connect the components into a two-dimensional wave-like layer structure extending parallel to (100).

Related literature

For molecular self-assembly and crystal engineering, see: Sun & Cui (2008 ▶); Hunter (1993 ▶); Yang et al. (2005 ▶). For the solid structures and properties of metal complexes of aminobenzothiazole and its derivatives, see: Lynch et al. (1998 ▶, 1999 ▶); Sun & Cui (2008 ▶); Popović et al. (2002 ▶); Antiñolo et al. (2007 ▶); Dong et al. (2002 ▶); Chen et al. (2008 ▶); Zhang et al. (2009 ▶). For the structures of decanedioic acid-based metal complexes and co-crystals, see: Xian et al. (2009 ▶); Braga et al. (2006 ▶); Aakeröy et al. (2007 ▶).

Experimental

Crystal data

2C₈H₈N₂S·C₁₀H₁₈O₄
M _r = 530.71
Monoclinic,
a = 5.3791 (5) Å
b = 21.822 (2) Å
c = 11.9431 (11) Å
β = 91.6660 (10)°
V = 1401.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 293 K
0.32 × 0.24 × 0.22 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.931, T _max = 0.952
7545 measured reflections
2470 independent reflections
1822 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.109
S = 1.05
2470 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and DIAMOND (Brandenburg & Berndt, 1999 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809031857/bt5031sup1.cif

e-65-o2188-sup1.cif^{(18.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809031857/bt5031Isup2.hkl

e-65-o2188-Isup2.hkl^{(121.4KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.78	2.597 (2)	171
N2—H2A⋯O2	0.86	2.09	2.914 (2)	161
N2—H2B⋯O1ⁱ	0.86	2.14	2.954 (2)	157

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors gratefully acknowledge financial support from Tianjin Normal University.

supplementary crystallographic information

Comment

During the past decades, molecular self-/assembly by classical coordination bonds and/or intermolecular non-covalent interactions such as hydrogen-bonding, π···π stacking, electrostatic interactions and so on, has been becoming more and more attractive in biology, biochemistry and new material fields (Sun et al., 2008; Hunter, 1993; Yang et al., 2005).

Acting as one of the excellent building blocks with multiple hydrogen-bonding sites and metal ion binding donors, aminobenzothiazole and its derivatives have been extensively utilized in the new materials, biochemistry and agriculture chemistry, due to the lower toxicity, high biological activity as well as excellent chemical reactivity (Lynch et al., 1998; Lynch et al., 1999; Sun et al., 2008; Popović et al., 2002; Antiñolo et al., 2007; Dong et al., 2002; Chen et al., 2008). On the other hand, the long decanedioic acid with adjustable deprotonated form and flexible aliphatic chain has also exhibited novel functions such as dianion templating (Xian et al., 2009) and heterosynthons with nitrogen-containing compounds (Braga et al., 2006; Aakeröy et al., 2007) in the fields of metal complexes and molecular co-crystals.

Thus, as a continuation of molecular assembly behavior in the solid state, in the present paper, the rigid 2-amino-6-methyl-1,3-benzothiazole (Ambt) and flexible decanedioic acid were selected as building blocks to cocrystallize. As a result, an intermolecular hydrogen bonded adduct, (I), was obtained under the hydrothermal conditions.

As shown in Fig. 1, the asymmetric unit of (I) comprises one neutral Ambt molecule with no crystallographically imposed symmetry and half a decanedioic acid located on a centre of inversion. Obviously, no proton transfer was observed for the neutral cocrystal, which is much different from the 2-aminobenzothiazolium 2,4-dicarboxybenzoate monohydrate (Zhang et al., 2009). The exocyclic amino group of Ambt is roughly coplanar with the benzothiazole ring. Similarily, the carboxylic residues of decanedioic acid are also co-planar with their long aliphatic chain. In the packing structure of I, two pairs of the intermolecuar O1—H1 ···N1 and N2—H2A ···O2 hydrogen-bonding interactions (Table 1) connect the two Ambt molecules and one decanedioic acid.

Experimental

To an aqueous solution of Ambt (40.4 mg, 0.2 mmol) was slowly added an aqueous solution of decanedioic acid (20.2 mg, 0.1 mmol) with constant stirring. After further stirring for about ten minutes, the resulting mixture was sealed in a stainless steel vessel and heated at 140 ^oC for 3 days. After the mixture was cooled to room temperature at a rate of 5 ^oC / h, pale-yellow block-shaped crystals suitable for X-ray diffraction were obtained directly, washed with ethanol and dried in air.Yield: 34% based on Ambt. Anal. calcd for C₁₃H₁₇N₂O₂S: C, 58.84; H, 6.46; N, 10.56%. Found: C, 58.78; H, 6.56; N,10.70%.