Bis(2-amino-4-phenyl-1,3-thia-zol-3-ium) tetra-chlorido-palladate(II).

The title compound, (C9H9N2S)2[PdCl4], consists of two monoprotonated 2-amino-4-phenyl-1,3-thia-zole molecules and one tetra-chlorido-palladate 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 inter-actions lead to hydrogen-bonded tapes of cations and anions along [100].

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 = 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

Δρmax = 0.26 e Å−3

Δρmin = −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 ▶).

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

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

CCDC reference: 1011353

Additional supporting information: crystallographic information; 3D view; checkCIF report

(C9H9N2S)2[PdCl4]	Z = 1
Mr = 602.68	F(000) = 300
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.027P)2 + 0.0969P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.051	(Δ/σ)max < 0.001
S = 1.11	Δρmax = 0.26 e Å−3
2060 reflections	Δρmin = −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)

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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

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)

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) ; (ii) .