Bis(2-amino-4-phenyl-1,3-thia­zol-3-ium) tetra­chlorido­palladate(II)

Reyna Reyes-Martínez; Rubén M Carballo; Gonzalo J Mena-Rejón; Simón Hernández-Ortega; David Cáceres-Castillo

doi:10.1107/S1600536814015360

. 2014 Jul 11;70(Pt 8):m295. doi: 10.1107/S1600536814015360

Bis(2-amino-4-phenyl-1,3-thiazol-3-ium) tetrachloridopalladate(II)

Reyna Reyes-Martínez ^a, Rubén M Carballo ^a, Gonzalo J Mena-Rejón ^a, Simón Hernández-Ortega ^b, David Cáceres-Castillo ^a,^*

PMCID: PMC4158524 PMID: 25249879

Abstract

The title compound, (C₉H₉N₂S)₂[PdCl₄], consists of two monoprotonated 2-amino-4-phenyl-1,3-thiazole molecules and one tetrachloridopalladate anion. The organic molecules exhibit a dihedral angle between the main rings planes of 31.82 (9)°. In the anion, the Pd^II atom is located on a crystallographic centre of symmetry with a square-planar geometry. In the crystal, the anions and cations are connected through bifurcated N—H⋯Cl hydrogen bonds, and these interactions lead to hydrogen-bonded tapes of cations and anions along [100].

Keywords: crystal structure

Related literature

For the potential biological activity of compounds containing thiazole rings, see: Annadurai et al. (2012 ▶); Alam et al. (2011 ▶). For the synthesis of thiazole compounds, see: Cáceres-Castillo et al. (2012 ▶). For similar structures with protonated molecules, see: Form et al. (1974 ▶); Jin et al. (2011 ▶, 2013 ▶). For the crystal structure of non-protonated thiazole, see: Au-Alvarez et al. (1999 ▶). graphic file with name e-70-0m295-scheme1.jpg

Experimental

Crystal data

(C₉H₉N₂S)₂[PdCl₄]
M _r = 602.68
Triclinic,
a = 7.2880 (2) Å
b = 8.9214 (3) Å
c = 9.8192 (3) Å
α = 66.258 (1)°
β = 73.778 (1)°
γ = 84.468 (1)°
V = 561.04 (3) Å³
Z = 1
Mo Kα radiation
μ = 1.50 mm⁻¹
T = 298 K
0.46 × 0.28 × 0.21 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: analytical (SADABS; Bruker, 2012 ▶) T _min = 0.658, T _max = 0.842
4857 measured reflections
2060 independent reflections
1982 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.020
wR(F ²) = 0.051
S = 1.11
2060 reflections
143 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: APEX2 (Bruker, 2012 ▶); cell refinement: SAINT (Bruker, 2012 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814015360/pj2013sup1.cif

e-70-0m295-sup1.cif^{(157.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814015360/pj2013Isup2.hkl

e-70-0m295-Isup2.hkl^{(113.3KB, hkl)}

CCDC reference: 1011353

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
N2—H2B⋯Cl2	0.89 (1)	2.41 (2)	3.237 (2)	155 (2)
N2—H2A⋯Cl2ⁱ	0.89 (1)	2.78 (2)	3.3572 (19)	123 (2)
N2—H2A⋯Cl1ⁱⁱ	0.89 (1)	2.44 (1)	3.291 (2)	159 (2)
N1—H1⋯Cl2	0.88 (1)	2.79 (2)	3.4028 (17)	129 (2)
N1—H1⋯Cl1	0.88 (1)	2.49 (2)	3.2593 (17)	147 (2)

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

Acknowledgments

The authors from the Universidad Autónoma de Yucatán are grateful to Dr Leovigildo Quijano for assistance with the X-ray analysis.

supplementary crystallographic information

S1. Introduction

The thiazole ring system is an important structural motif found in numerous molecules with potential biological activities, for instance; as antiinfective agents (Annadurai et al., 2012; Alam et al., 2011). On the other hand, in recent years there has been a growing interest in organic derivatives of transition metals in order to modify the biological properties of these organic compounds. Thus, in this opportunity we would like to report the crystal structure of bis-(2-amino-4-phenyl-1,3-thiazolium) tetrachloropalladate (II).

S2. Experimental

S2.1. Synthesis and crystallization

The compound 2-amino-4-phenyl-1,3-thiazole was synthesized as reported by our group (Cáceres-Castillo et al., 2012). The PdCl₂ (25 mg, 0.14 mmol) was dissolved in 1 mL of concentrated HCl and then diluted with 5 mL of methanol. To the resulting mixture a methanol (5mL) solution of 2-amino-4-phenyl-1,3-thiazole (50 mg, 0.28 mmol) was added. The reaction mixture was stirred for four hours at room temperature, after which time the resulting solution was allowed to slowly evaporate to produce brown X-ray diffraction quality crystals after few days.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

All H atoms were included in calculated positions (C—H = 0.93 Å), and refined using a riding model with Uiso(H) = 1.2 Ueq of the carrier atom. H atoms on N were located in a Fourier map and refined isotropically with Uiso(H) = 1.2 × Ueq(N).

13 badly-fitted reflections were omitted from the final refinement.

S3. Results and discussion

The title compound, [C₉H₉N₂S]₂[PdCl₄], is centrosymmetric and consists of two monoprotonated 2-amino-4-phenyl-1,3-thiazole molecules and one tetrachloropalladate anion. This compound, crystallized in the triclinic P-1 space group. The asymmetric unit is composed of one monoprotaned 2-amino-4-phenyl-1,3-thiazole and half of the tetrachloropalladate anion, the other half is generated by application of an inversion centre. The dihedral angle between the planes of the phenyl and thiazole rings in the cation is of 31.82 (9)°.This value is larger than those reported in other compounds containing the 2-amino-4-phenyl-1,3-thiazole molecule, protonated (Form et al., 1974; Jin et al., 2013; Jin et al., 2011) or in the free molecule (Au-Alvarez et al., 1999). The angle C2—N1—C5 (115.25 (17)°) is similar in value other salts reported and is longer than that reported for the neutral compound (110.5 °).

The palladium atom of the anion is in a special position (0.5, 0, 1), Wyckoff site 1d, and exhibits a square-planar geometry with Pd—Cl distances of 2.3031 (5) and 2.3061 (6) Å. The cation and the anion are linked by a bifurcate hydrogen bond between the chloride atoms and the hydrogen of the thiazole ring (Figure 1). The NH and NH₂ groups exhibit N—H···Cl hydrogen bonds with the chloride atoms generating a linear arrangement in the orientation [100] (Figure 2).