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

Reyes-Martínez, R.; Carballo, R.M.; Mena-Rejón, G.J.; Hernández-Ortega, S.; Cáceres-Castillo, D.

doi:10.1107/S1600536814015360

metal-organic compounds

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doi:10.1107/S1600536814015360

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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 and David Cáceres-Castillo ^a ^*

^aFacultad de Química, Universidad Autónoma de Yucatán, Calle 41 No. 421, Col. Industrial, CP97150, Mérida, Yucatán, Mexico, and ^bInstituto de Química, Universidad Nacional Autónoma de México, Circuito exterior, Ciudad Universitaria, México, DF, 04510, Mexico
^*Correspondence e-mail: david.caceres@uady.mx

Edited by T. J. Prior, University of Hull, England (Received 18 June 2014; accepted 1 July 2014; online 11 July 2014)

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.

CCDC reference: 1011353

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 ).

Experimental

Crystal data

(C₉H₉N₂S)₂[PdCl₄]
M_r = 602.68
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.020
wR(F²) = 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

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)
Symmetry codes: (i) -x+2, -y, -z+2; (ii) x+1, y, z.

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 ).

Supporting information

CCDC reference: 1011353

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

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

checkCIF report

Introduction top

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).

Experimental top

Synthesis and crystallization top

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.

Refinement top

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.

Results and discussion top

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).

Related literature top

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 protonated structures, see: Form et al. (1974); Jin et al. (2011, 2013). For the crystal structure of non-protonated thiazole, see: Au-Alvarez et al. (1999).

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); 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 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure of title compound with displacement ellipsoids at the 40% probability. Hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Linear arrangement due hydrogen bond patterns in crystal structure of the title compound.

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

Crystal data top

(C₉H₉N₂S)₂[PdCl₄]	Z = 1
M_r = 602.68	F(000) = 300
Triclinic, P1	D_x = 1.784 Mg m⁻³
a = 7.2880 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.9214 (3) Å	Cell parameters from 4506 reflections
c = 9.8192 (3) Å	θ = 2.4–25.4°
α = 66.258 (1)°	µ = 1.50 mm⁻¹
β = 73.778 (1)°	T = 298 K
γ = 84.468 (1)°	Prism, brown
V = 561.04 (3) Å³	0.46 × 0.28 × 0.21 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	1982 reflections with I > 2σ(I)
Detector resolution: 0.83 pixels mm^-1	R_int = 0.026
ω scans	θ_max = 25.4°, θ_min = 2.4°
Absorption correction: analytical (SADABS; Bruker, 2012)	h = −8→8
T_min = 0.658, T_max = 0.842	k = −10→10
4857 measured reflections	l = −11→11
2060 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.020	w = 1/[σ²(F_o²) + (0.027P)² + 0.0969P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.051	(Δ/σ)_max < 0.001
S = 1.11	Δρ_max = 0.26 e Å⁻³
2060 reflections	Δρ_min = −0.30 e Å⁻³
143 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
3 restraints	Extinction coefficient: 0.015 (2)

Crystal data top

(C₉H₉N₂S)₂[PdCl₄]	γ = 84.468 (1)°
M_r = 602.68	V = 561.04 (3) Å³
Triclinic, P1	Z = 1
a = 7.2880 (2) Å	Mo Kα radiation
b = 8.9214 (3) Å	µ = 1.50 mm⁻¹
c = 9.8192 (3) Å	T = 298 K
α = 66.258 (1)°	0.46 × 0.28 × 0.21 mm
β = 73.778 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2060 independent reflections
Absorption correction: analytical (SADABS; Bruker, 2012)	1982 reflections with I > 2σ(I)
T_min = 0.658, T_max = 0.842	R_int = 0.026
4857 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	3 restraints
wR(F²) = 0.051	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.26 e Å⁻³
2060 reflections	Δρ_min = −0.30 e Å⁻³
143 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Pd	0.5000	0.0000	1.0000	0.03103 (10)
Cl1	0.54163 (7)	0.23160 (6)	0.77534 (6)	0.04971 (15)
Cl2	0.78000 (7)	−0.10267 (6)	0.89335 (6)	0.04577 (14)
N1	0.9774 (2)	0.2276 (2)	0.56952 (19)	0.0382 (4)
H1	0.8651 (19)	0.185 (3)	0.628 (2)	0.046*
C2	1.1103 (3)	0.2483 (2)	0.6301 (2)	0.0380 (4)
N2	1.0983 (3)	0.1821 (2)	0.7791 (2)	0.0527 (5)
H2A	1.203 (2)	0.195 (3)	0.804 (3)	0.063*
H2B	1.001 (3)	0.112 (3)	0.837 (3)	0.063*
S3	1.29130 (7)	0.37696 (7)	0.49056 (6)	0.04726 (15)
C4	1.1739 (3)	0.4022 (3)	0.3520 (2)	0.0459 (5)
H4	1.2196	0.4690	0.2481	0.055*
C5	1.0096 (3)	0.3149 (2)	0.4107 (2)	0.0365 (4)
C6	0.8732 (3)	0.3009 (2)	0.3309 (2)	0.0374 (4)
C7	0.8497 (3)	0.4318 (3)	0.2005 (2)	0.0484 (5)
H7	0.9175	0.5291	0.1660	0.058*
C8	0.7259 (4)	0.4194 (3)	0.1206 (3)	0.0572 (6)
H8	0.7096	0.5087	0.0340	0.069*
C9	0.6278 (4)	0.2758 (3)	0.1694 (3)	0.0585 (6)
H9	0.5474	0.2666	0.1143	0.070*
C10	0.6482 (3)	0.1453 (3)	0.2995 (3)	0.0576 (6)
H10	0.5800	0.0484	0.3328	0.069*
C11	0.7696 (3)	0.1563 (3)	0.3820 (3)	0.0475 (5)
H11	0.7815	0.0678	0.4707	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd	0.02640 (13)	0.03439 (14)	0.03019 (13)	−0.00791 (8)	−0.00582 (8)	−0.00981 (9)
Cl1	0.0358 (3)	0.0484 (3)	0.0431 (3)	−0.0070 (2)	−0.0057 (2)	0.0025 (2)
Cl2	0.0345 (3)	0.0472 (3)	0.0495 (3)	−0.0033 (2)	−0.0015 (2)	−0.0183 (2)
N1	0.0298 (8)	0.0420 (9)	0.0380 (9)	−0.0078 (7)	−0.0058 (7)	−0.0112 (7)
C2	0.0326 (9)	0.0374 (10)	0.0416 (11)	−0.0027 (8)	−0.0092 (8)	−0.0129 (8)
N2	0.0494 (11)	0.0594 (12)	0.0434 (10)	−0.0154 (9)	−0.0169 (9)	−0.0074 (9)
S3	0.0326 (3)	0.0601 (3)	0.0447 (3)	−0.0143 (2)	−0.0069 (2)	−0.0151 (2)
C4	0.0387 (11)	0.0584 (13)	0.0365 (10)	−0.0118 (9)	−0.0051 (9)	−0.0147 (9)
C5	0.0321 (9)	0.0394 (10)	0.0376 (10)	−0.0008 (8)	−0.0062 (8)	−0.0164 (8)
C6	0.0329 (9)	0.0436 (10)	0.0393 (10)	0.0001 (8)	−0.0064 (8)	−0.0217 (9)
C7	0.0532 (13)	0.0504 (12)	0.0449 (12)	−0.0054 (10)	−0.0144 (10)	−0.0197 (10)
C8	0.0645 (15)	0.0669 (15)	0.0498 (13)	0.0047 (12)	−0.0254 (12)	−0.0265 (12)
C9	0.0519 (14)	0.0780 (17)	0.0680 (16)	0.0034 (12)	−0.0260 (12)	−0.0449 (14)
C10	0.0501 (13)	0.0593 (14)	0.0773 (17)	−0.0071 (11)	−0.0169 (12)	−0.0389 (13)
C11	0.0427 (11)	0.0453 (11)	0.0573 (13)	−0.0019 (9)	−0.0134 (10)	−0.0223 (10)

Geometric parameters (Å, º) top

Pd—Cl1	2.3031 (5)	C4—H4	0.9300
Pd—Cl1ⁱ	2.3031 (5)	C5—C6	1.468 (3)
Pd—Cl2ⁱ	2.3061 (5)	C6—C7	1.383 (3)
Pd—Cl2	2.3061 (5)	C6—C11	1.393 (3)
N1—C2	1.331 (2)	C7—C8	1.388 (3)
N1—C5	1.395 (3)	C7—H7	0.9300
N1—H1	0.876 (10)	C8—C9	1.369 (4)
C2—N2	1.319 (3)	C8—H8	0.9300
C2—S3	1.7179 (19)	C9—C10	1.373 (4)
N2—H2A	0.894 (10)	C9—H9	0.9300
N2—H2B	0.887 (10)	C10—C11	1.389 (3)
S3—C4	1.733 (2)	C10—H10	0.9300
C4—C5	1.343 (3)	C11—H11	0.9300

Cl1—Pd—Cl1ⁱ	180.0	C4—C5—C6	129.09 (18)
Cl1—Pd—Cl2ⁱ	90.134 (19)	N1—C5—C6	120.10 (17)
Cl1ⁱ—Pd—Cl2ⁱ	89.866 (19)	C7—C6—C11	119.06 (19)
Cl1—Pd—Cl2	89.866 (19)	C7—C6—C5	119.70 (18)
Cl1ⁱ—Pd—Cl2	90.134 (19)	C11—C6—C5	121.22 (19)
Cl2ⁱ—Pd—Cl2	180.00 (2)	C6—C7—C8	120.7 (2)
C2—N1—C5	115.25 (16)	C6—C7—H7	119.7
C2—N1—H1	120.8 (15)	C8—C7—H7	119.7
C5—N1—H1	121.9 (15)	C9—C8—C7	120.0 (2)
N2—C2—N1	123.49 (18)	C9—C8—H8	120.0
N2—C2—S3	125.28 (16)	C7—C8—H8	120.0
N1—C2—S3	111.19 (14)	C8—C9—C10	120.0 (2)
C2—N2—H2A	114.7 (17)	C8—C9—H9	120.0
C2—N2—H2B	115.3 (18)	C10—C9—H9	120.0
H2A—N2—H2B	128 (2)	C9—C10—C11	120.7 (2)
C2—S3—C4	90.03 (10)	C9—C10—H10	119.6
C5—C4—S3	112.71 (16)	C11—C10—H10	119.6
C5—C4—H4	123.6	C10—C11—C6	119.5 (2)
S3—C4—H4	123.6	C10—C11—H11	120.2
C4—C5—N1	110.80 (17)	C6—C11—H11	120.2

Symmetry code: (i) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

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···Cl2ⁱⁱ	0.89 (1)	2.78 (2)	3.3572 (19)	123 (2)
N2—H2A···Cl1ⁱⁱⁱ	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)

Symmetry codes: (ii) −x+2, −y, −z+2; (iii) x+1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···Cl2	0.887 (10)	2.412 (15)	3.237 (2)	155 (2)
N2—H2A···Cl2ⁱ	0.894 (10)	2.78 (2)	3.3572 (19)	123 (2)
N2—H2A···Cl1ⁱⁱ	0.894 (10)	2.442 (14)	3.291 (2)	159 (2)
N1—H1···Cl2	0.876 (10)	2.786 (19)	3.4028 (17)	128.6 (18)
N1—H1···Cl1	0.876 (10)	2.492 (15)	3.2593 (17)	146.5 (19)

Symmetry codes: (i) −x+2, −y, −z+2; (ii) x+1, y, z.

Acknowledgements

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

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Volume 70| Part 8| August 2014| Page m295

doi:10.1107/S1600536814015360

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