Bis(2,6-dimethyl­pyridinium) hexa­chlorido­platinate(IV)

Vahid Amani; Rahmatollah Rahimi; Hamid Reza Khavasi

doi:10.1107/S1600536808025257

. 2008 Aug 9;64(Pt 9):m1143–m1144. doi: 10.1107/S1600536808025257

Bis(2,6-dimethylpyridinium) hexachloridoplatinate(IV)

Vahid Amani ^a, Rahmatollah Rahimi ^b, Hamid Reza Khavasi ^a,^*

PMCID: PMC2960473 PMID: 21201599

Abstract

The asymmetric unit of the title compound, (C₇H₁₀N)₂[PtCl₆], contains one independent protonated 2,6-dimethylpyridinium cation and half of a centrosymmetric [PtCl₆]²⁻ anion. The Pt atom has an octahedral coordination. In the crystal structure, intermolecular N—H⋯Cl and C—H⋯Cl hydrogen bonds result in the formation of a supramolecular structure. There is a π–π contact between the pyridine rings [centroid–centroid distance = 4.235 (1) Å].

Related literature

For related literature, see: Abedi et al. (2008 ▶); Bencini et al. (1992 ▶); Bokach et al. (2003 ▶); Bowmaker et al. (1998 ▶); Ciccarese et al. (1998 ▶); Delafontaine et al. (1987 ▶); Effendy et al. (2006 ▶); Hasan et al. (2001 ▶); Hojjat Kashani et al. (2008 ▶); Hu et al. (2003 ▶); Jin et al. (2000 ▶, 2003 ▶, 2006 ▶); Juan et al. (1998 ▶); Kansikas et al. (1994 ▶); Li & Liu (2003 ▶); Rafizadeh et al. (2006 ▶); Terzis & Mentzafos (1983 ▶); Yousefi, Amani & Khavasi (2007 ▶); Yousefi, Ahmadi et al. (2007 ▶); Yousefi et al. (2007a ▶,b ▶); Zordan & Brammer (2004 ▶); Zordan et al. (2005 ▶).

Experimental

Crystal data

(C₇H₁₀N)₂[PtCl₆]
M _r = 624.10
Monoclinic,
a = 9.9142 (12) Å
b = 9.6031 (10) Å
c = 11.3305 (14) Å
β = 107.117 (10)°
V = 1031.0 (2) Å³
Z = 2
Mo Kα radiation
μ = 7.58 mm⁻¹
T = 298 (2) K
0.48 × 0.45 × 0.38 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: numerical (X-SHAPE and X-RED; Stoe & Cie, 2005 ▶)T _min = 0.41, T _max = 0.60
2756 measured reflections
2756 independent reflections
2387 reflections with I > 2σ(I)

Refinement

R[F ² > 2σ(F ²)] = 0.069
wR(F ²) = 0.189
S = 1.10
2756 reflections
111 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.82 e Å⁻³
Δρ_min = −1.09 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808025257/hk2508sup1.cif

e-64-m1143-sup1.cif^{(15.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808025257/hk2508Isup2.hkl

e-64-m1143-Isup2.hkl^{(132.6KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

Pt1—Cl2	2.3161 (16)
Pt1—Cl3	2.3239 (16)
Pt1—Cl1	2.3298 (14)

Open in a new tab

Cl2—Pt1—Cl1	90.25 (6)
Cl2ⁱ—Pt1—Cl1	89.75 (6)
Cl2—Pt1—Cl3ⁱ	90.20 (8)
Cl2—Pt1—Cl3	89.80 (8)
Cl3—Pt1—Cl1ⁱ	89.37 (6)
Cl3—Pt1—Cl1	90.63 (6)

Open in a new tab

Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1D⋯Cl3ⁱⁱ	0.85 (8)	2.45 (8)	3.279 (6)	168 (7)
C1—H1B⋯Cl1ⁱⁱ	0.96	2.83	3.654 (11)	145
C4—H4⋯Cl2ⁱⁱⁱ	0.93	2.71	3.616 (11)	165

Open in a new tab

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

Acknowledgments

We are grateful to Shahid Beheshti University for financial support.

supplementary crystallographic information

Comment

In recent years, there has been considerable interest in proton transfer systems and their structures (Rafizadeh et al., 2006; Yousefi, Amani & Khavasi, 2007; Abedi et al., 2008; Hojjat Kashani et al., 2008). Several proton transfer systems using 2,6-dimethylpyridine, with proton donor molecules, such as [2,6-dmpy.H](NO₃), (II), (Jin et al., 2003), [2,6-dmpy.H]₂[CoCl₄], (III), (Kansikas et al., 1994), [2,6-dmpy.H]Cl, (IV), (Effendy et al., 2006), [2,6-dmpy.H]₃[BiBr₆], (V), (Bowmaker et al., 1998), [2,6-dmpy.H]₂- [O₃CrOCrO₃], (VI), (Jin et al., 2006) and [2,6-dmpy.H][Ph(COOH)(COO)], (VII), (Jin et al., 2000) [2,6-dmpy.H is 2,6-dimethylpyridinium] have been synthesized and characterized by single-crystal X-ray diffraction methods.

There are also several proton transfer systems using H₂[PtCl₆] with proton acceptor molecules, such as [HpyBr-3]₂[PtCl₆].2H₂O, (XIII), and [HpyI-3]₂[PtCl₆].2H₂O, (IX),(Zordan & Brammer, 2004), [BMIM]₂[PtCl₆], (X), and [EMIM]₂[PtCl₆], (XI), (Hasan et al., 2001), {(DABCO)H₂[PtCl₆]}, (XII), (Juan et al., 1998), {p-C₆H₄(CH₂ImMe)₂[PtCl₆]}, (XIII), (Li & Liu, 2003), [het][PtCl₆].2H₂O, (XIV), (Hu et al., 2003), [9-MeGuaH]₂[PtCl₆].2H₂O, (XV), (Terzis & Mentzafos, 1983), [H₁₀[30]aneN₁₀][PtCl₆]₂Cl₆.2H₂O, (XVI), (Bencini et al., 1992), [H₂Me₂ppz][PtCl₆], (XVII), (Ciccarese et al., 1998), [PA]₂[PtCl₆]Cl, (XVIII), (Delafontaine et al., 1987), [DEA]₂[PtCl₆], (XIX), (Bokach et al., 2003), [HpyCl-3]₃[PtCl₆]Cl, (XX), (Zordan et al., 2005), [2,9-dmphen.H]₂- [PtCl₆], (XXI), (Yousefi, Ahmadi et al., 2007), [H₂DA18C6][PtCl₆].2H₂O, (XXII), (Yousefi et al., 2007a) and [TBA]₃[PtCl₆]Cl, (XXIII), (Yousefi et al., 2007b) [where hpy is halo- pyridinium, BMIM⁺ is 1-n-butyl-3-methylimidazolium, EMIM⁺ is 1-ethyl-3-methylimidazolium, DABCO is 1,4-diazabicyclooctane, Im is imidazolium, het is 2-(α-hydroxyethyl) thiamine, 9-MeGuaH is 9-methylguaninium, [H₁₀[30]aneN₁₀] is [C₂₀H₆₀N₁₀]¹⁰⁺ cation, H₂Me₂ppz is N,N'-dimethylpiperazinium, PA is pentane-1,5- diammonium, DEA is diethyl-ammonium, 2,9-dmphen.H is 2,9-dimethyl-1,10 -phenanthrolinium, H₂DA18C6 is 1,10-Diazonia-18-crown-6 and TBA is tribenzylammonium] have been synthesized and characterized by single-crystal X-ray diffraction methods. We report herein the synthesis and crystal structure of the title compound, (I).

The asymmetric unit of (I), (Fig. 1) contains one independent protonated 2,6-di- methylpyridinium cation and half of a centrosymmetric [PtCl₆]^2- anion. The Pt ion has an octahedral coordination. In cation, the bond lengths and angles are in good agreement with the corresponding values in (II) and (IV). In [PtCl₆]^2- anion, the Pt-Cl bond lengths and Cl-Pt-Cl bond angles (Table 1) are also within normal ranges, as in (XXI), (XXII) and (XXIII).

In the crystal structure (Fig. 2), intermolecular N-H···Cl and C-H···Cl hydrogen bonds (Table 2) result in the formation of a supramolecular structure, in which they may be effective in the stabilization of the structure. A π—π contact between A (N1/C2-C6) rings Cg1···Cg1ⁱ [symmetry code: (i) -x, 1 - y, 1 - z, where Cg1 is centroid of the ring A (N1/C2-C6)] further stabilize the structure, with centroid-centroid distance of 4.235 (1) Å.

Experimental

For the preparation of the title compound, a solution of 2,6-dimethylpyridine (0.16 g, 1.48 mmol, 0.17 ml) in methanol (15 ml) was added to a solution of H₂PtCl₆.6H₂O, (0.38 g, 0.74 mmol) in acetonitrile (15 ml) and the resulting yellow solution was stirred for 10 min at 313 K. Then, it was left to evaporate slowly at room temperature. After one week, orange prismatic crystals of were isolated (yield; 0.34 g; 73.6%).