1,3-Benzothia­zolium tetra­chlorido­aurate(III) tetra­hydro­furan solvate

Tesfamariam K Hagos; Stefan D Nogai; Liliana Dobrzańska; Stephanie Cronje; Helgard G Raubenheimer

doi:10.1107/S1600536809003572

. 2009 Feb 6;65(Pt 3):m255–m256. doi: 10.1107/S1600536809003572

1,3-Benzothiazolium tetrachloridoaurate(III) tetrahydrofuran solvate

Tesfamariam K Hagos ^a, Stefan D Nogai ^a, Liliana Dobrzańska ^a,^*, Stephanie Cronje ^a, Helgard G Raubenheimer ^a

PMCID: PMC2968643 PMID: 21582047

Abstract

In the crystal structure of the title ionic compound (C₇H₆NS)[AuCl₄]·C₄H₈O, the [AuCl₄]⁻ anion shows a typical square-planar geometry. Numerous weak C—H⋯Cl hydrogen bonds between [AuCl₄]⁻ and the 1,3-benzothiazolium units form layers comprised of 24-membered rings in which hydrogen-bonded tetrahydrofuran (THF) solvent molecules are accommodated. C—H⋯Cl interactions between THF and [AuCl₄]⁻ from adjacent layers result in bilayers. These are further stabilized by π–π interactions between the thiazole and benzene rings [centroid–centroid distance = 3.971 (3) Å], resulting in the formation of a three-dimensional supramolecular assembly.

Related literature

For background, see: Hagos et al. (2008 ▶). For related compounds, see: Huynh et al. (2006 ▶); Yen et al. (2006 ▶, 2008 ▶). For bond-length data, see Adé et al. (2004 ▶); Asaji et al. (2004 ▶); Makotchenko et al. (2006 ▶). For related literature, see: Brammer et al. (2001 ▶).

Experimental

Crystal data

(C₇H₆NS)[AuCl₄]·C₄H₈O
M _r = 547.06
Triclinic,
a = 7.3213 (7) Å
b = 10.3498 (10) Å
c = 11.8783 (12) Å
α = 99.331 (1)°
β = 107.579 (1)°
γ = 104.483 (2)°
V = 802.75 (14) Å³
Z = 2
Mo Kα radiation
μ = 9.95 mm⁻¹
T = 100 (2) K
0.30 × 0.20 × 0.10 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T _min = 0.101, T _max = 0.371
4957 measured reflections
3504 independent reflections
3325 reflections with I > 2σ(I)
R _int = 0.013

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.064
S = 1.05
3504 reflections
175 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 2.27 e Å⁻³
Δρ_min = −1.00 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour 2001 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809003572/ng2541sup1.cif

e-65-0m255-sup1.cif^{(17.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809003572/ng2541Isup2.hkl

e-65-0m255-Isup2.hkl^{(171.8KB, 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
N6—H6⋯O14	0.86 (5)	1.87 (5)	2.728 (5)	177 (6)
C5—H5⋯Cl2ⁱ	0.95	2.65	3.588 (5)	170
C8—H8⋯Cl4	0.95	2.93	3.447 (5)	116
C9—H9⋯Cl4	0.95	3.00	3.498 (5)	114
C10—H10⋯Cl2ⁱⁱ	0.95	2.96	3.541 (6)	121
C11—H11⋯Cl2ⁱⁱ	0.95	2.90	3.498 (5)	122
C11—H11⋯Cl3ⁱⁱ	0.95	2.77	3.639 (5)	154
C15—H15B⋯Cl1ⁱⁱⁱ	0.99	3.02	3.922 (6)	153
C18—H18A⋯Cl4ⁱⁱⁱ	0.99	2.91	3.547 (6)	123

Open in a new tab

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

Acknowledgments

The authors thank the National Research Foundation of South Africa and the University of Stellenbosch for financial support.

supplementary crystallographic information

Comment

During the course of ongoing studies on the reactions of gold(III) compounds with heterocycles, we have isolated the title ionic compound (I) with a structure resembling that of a 1,3-dimesitylimidazolinium tetrachloro-gold(III) dichloromethane solvate reported earlier (Hagos et al. 2008). The asymmetric unit (Fig. 1) consists of a 1,3-benzothiazolium cation, a tetrachloro-gold(III) anion and a tetrahydrofuran molecule. The structural parameters associated with the 1,3-benzothiazolium moiety agree well with reported values, see for example 3-(2-propenyl)-1,3-benzothiazolium bromide (Huynh et al. 2006), N-benzyl-1,3-benzothiazolium bromide (Yen et al. 2006) and 3-n-propyl-1,3-benzothiazolium bromide monohydrate (Yen et al. 2008). The anionic part displays a typical square-planar geometry around Au and the Au—Cl distances compare well with previously reported values (Adé et al., 2004; Asaji et al., 2004; Makotchenko et al., 2006). All Cl atoms of [AuCl₄]^- complex participate in the formation of weak C—H···Cl hydrogen bonds (Table 1). Atoms Cl2, Cl3 and Cl4 interact with the 1,3-benzothiazolium cation forming layers consisting of R⁵₆(24) rings in which tetrahydrofuran molecules are incorporated by forming hydrogen bonds O6—H6···N14 with a distance of 2.728 (5) Å (Fig. 2). Further C—H···Cl interactions between THF and [AuCl₄]^- from neighbouring layers (C15—H15B···Cl1 and C18—H18A···Cl4) form pillar-like connections between them, leading to the formation of bilayers. The latter are propagated along [100] by π-π interactions between thiazole and benzene rings [symmetry operation: 1 - x, 1 - y, 2 - z, centroid-centroid distance = 3.971 (3) Å], resulting in a three-dimensional assembly (Fig. 3).

Experimental

1,3-Benzothiazole (0.10 g, 0.76 mmol) in acetonitrile (5 ml) was treated with HAuCl₄^.4H₂O (0.31 g, 0.76 mmol) in water (5 ml) at room temperature (2.5 h). The reaction mixture was stripped of solvent and extracted with a mixture of dichloromethane and THF (1:1, 150 ml). Then the solvent was removed under reduced pressure to yield a yellow residue. Orange crystals suitable for single-crystal X-ray analysis were obtained from a THF solution layered with n-pentane at 253 K.