2-(1,2-Dihydro-2-oxopyridin-3-yl)-1,3-benzothia­zol-3-ium bromide monohydrate

Kim Potgieter; Thomas Gerber; Richard Betz

doi:10.1107/S1600536811022847

. 2011 Jun 18;67(Pt 7):o1697. doi: 10.1107/S1600536811022847

2-(1,2-Dihydro-2-oxopyridin-3-yl)-1,3-benzothiazol-3-ium bromide monohydrate

Kim Potgieter ^a, Thomas Gerber ^a, Richard Betz ^a,^*

PMCID: PMC3151859 PMID: 21837094

Abstract

The title hydrated molecular salt, C₁₂H₉N₂OS⁺·Br⁻·H₂O, the aza-substituted six-membered ring is present as its keto tautomer instead of its aromatic tautomer. The dihedral angle between the fused ring system and the pyridinone ring in the cation is 6.91 (6)°. In the crystal, bifurcated N—H⋯(O,Br) and O—H⋯Br hydrogen bonds and S⋯O contacts [S⋯O = 3.0526 (10) Å] connect the components into a three-dimensional network. The closest centroid–centroid distance between two π-systems is 3.7420 (7) Å between two benzene rings.

Related literature

For the crystal structure of 2-(o-hydroxyphenyl)benzothiazole, see: Stenson (1970 ▶); Aydin et al. (1999 ▶); Jia & Jin (2009 ▶). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶). For our continuing efforts to create new radio-pharmaceuticals, see: Gerber et al. (2011 ▶).

Experimental

Crystal data

C₁₂H₉N₂OS⁺·Br⁻·H₂O
M _r = 327.20
Triclinic,
a = 5.6480 (2) Å
b = 9.9900 (3) Å
c = 11.2070 (3) Å
α = 88.808 (1)°
β = 83.098 (1)°
γ = 87.914 (1)°
V = 627.25 (3) Å³
Z = 2
Mo Kα radiation
μ = 3.44 mm⁻¹
T = 100 K
0.54 × 0.32 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.825, T _max = 1.000
11074 measured reflections
3084 independent reflections
3004 reflections with I > 2σ(I)
R _int = 0.015

Refinement

R[F ² > 2σ(F ²)] = 0.016
wR(F ²) = 0.042
S = 1.07
3084 reflections
179 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811022847/yk2012sup1.cif

e-67-o1697-sup1.cif^{(16.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811022847/yk2012Isup3.hkl

e-67-o1697-Isup3.hkl^{(151.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811022847/yk2012Isup4.cdx

Supplementary material file. DOI: 10.1107/S1600536811022847/yk2012Isup4.cml

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
N1—H71⋯Br1	0.89 (2)	2.40 (2)	3.2708 (10)	168.2 (17)
N2—H72⋯O90ⁱ	0.832 (19)	1.930 (19)	2.7390 (15)	163.6 (17)
O90—H901⋯Br1	0.81 (2)	2.55 (2)	3.3485 (11)	170 (2)
O90—H902⋯Br1ⁱⁱ	0.85 (2)	2.49 (2)	3.3360 (10)	176 (2)

Open in a new tab

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

Acknowledgments

The authors thank Ms Dakota Neil-Schutte for helpful discussions.

supplementary crystallographic information

Comment

In our continuous efforts to create new radio-pharmaceuticals (Gerber et al., 2011), we attempted the coordination reaction of a bidentate ligand towards a rhenium(V) precursor upon which a crystalline reaction product was obtained. The crystal structure analysis showed the unintentional synthesis of a protonated derivative of the ligand. The structure of 2-(o-hydroxyphenyl)benzothiazole is apparent in the literature (Stenson, 1970; Aydin et al., 1999; Jia & Jin, 2009).

In the molecule, the – possible – hydroxy-pyridine moiety is present as its keto-tautomer. Protonation took place on the nitrogen atom of the five-membered heterocyclic subunit. The molecule is essentially flat, the least-squares planes defined by the ring atoms of the benzothiazol moiety and the ring atoms of the hydroxy-pyridine tautomer enclose an angle of only 6.91 (6) °. One molecule of solvent water is present in the crystal structure (Fig. 1).

In the crystal structure, hydrogen bonds as well as S···O contacts (whose range falls by more than 0.2 Å below the sum of van-der-Waals radii of the respective atoms) are present. While the hydrogen bonds originating from the solvent water as well as the protonated nitrogen atom of the five-membered heterocyclic subunit exclusively have the bromide anion as acceptor, the water molecule's oxygen atom serves as acceptor for the hydrogen atom of the intracyclic NH group in the six-membered heterocycle. The pattern formed by the water molecules connecting the bromide anions is reminiscent of a parallelogram (Fig. 2). The S···O contacts give rise to the formation of centrosymmetric dimers. In total, the components of the crystal structure are connected to a three-dimensional network. In terms of graph-set analysis (Etter et al., 1990; Bernstein et al., 1995), the descriptor for the hydrogen bonding system is DDDD on the unitary level. The parallelogram shaped pattern necessitates a R⁴₂(8) descriptor on the binary level. The description of the S···O contacts is possible by a R²₂(10) descriptor on the unitary level. The closest intercentroid distance between two π-systems was found at 3.7420 (7) Å and was observed between two phenyl-moieties.

The packing of the title compound is shown in Figure 3.

Experimental

The compound was unintentionally obtained upon reacting ReOBr₃(PPh₃)₂ and the unprotonated title compound in methanol. Crystals suitable for the X-ray diffraction study were obtained upon free evaporation of the solvent at room temperature in the course of three days.