Bis(2,2′-bipyridine-κ2 N,N′)dichlorido­platinum(IV) dichloride monohydrate

Nam-Ho Kim; In-Chul Hwang; Kwang Ha

doi:10.1107/S1600536809000725

. 2009 Jan 14;65(Pt 2):m180. doi: 10.1107/S1600536809000725

Bis(2,2′-bipyridine-κ² N,N′)dichloridoplatinum(IV) dichloride monohydrate

Nam-Ho Kim ^a, In-Chul Hwang ^b, Kwang Ha ^a,^*

PMCID: PMC2968269 PMID: 21581784

Abstract

In the title complex, [PtCl₂(C₁₀H₈N₂)₂]Cl₂·H₂O, the Pt⁴⁺ ion is six-coordinated in a distorted octahedral environment by four N atoms from the two 2,2′-bipyridine ligands and two Cl atoms. As a result of the different trans influences of the N and Cl atoms, the Pt—N bonds trans to the Cl atom are slightly longer than those trans to the N atom. The compound displays intermolecular hydrogen bonding between the water molecule and the Cl anions. There are intermolecular π–π interactions between adjacent pyridine rings, with a centroid–centroid distance of 3.962 Å.

Related literature

For related literature, see: Hambley (1986 ▶); Hojjat Kashani et al. (2008 ▶).

Experimental

Crystal data

[PtCl₂(C₁₀H₈N₂)₂]Cl₂·H₂O
M _r = 667.27
Orthorhombic,
a = 11.1345 (12) Å
b = 11.5867 (12) Å
c = 17.0873 (19) Å
V = 2204.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 6.87 mm⁻¹
T = 293 (2) K
0.35 × 0.20 × 0.15 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.251, T _max = 0.357
12649 measured reflections
4462 independent reflections
4284 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.016
wR(F ²) = 0.038
S = 0.84
4462 reflections
271 parameters
H-atom parameters constrained
Δρ_max = 0.95 e Å⁻³
Δρ_min = −0.53 e Å⁻³
Absolute structure: Flack (1983 ▶), 1901 Friedel pairs
Flack parameter: −0.006 (4)

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809000725/bt2846sup1.cif

e-65-0m180-sup1.cif^{(22.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809000725/bt2846Isup2.hkl

e-65-0m180-Isup2.hkl^{(218.6KB, 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
O1—H1A⋯Cl3ⁱ	1.033	2.21	3.150 (3)	149.79 (16)
O1—H1B⋯Cl4ⁱⁱ	0.924	2.31	3.139 (3)	149.3 (2)

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

Acknowledgments

This work was supported by the Korea Research Foundation (2006–353-C00028).

supplementary crystallographic information

Comment

In the title complex, [PtCl₂(C₁₀H₈N₂)₂]Cl₂.H₂O, the central Pt⁴⁺ ion is six-coordinated in a distorted octahedral environment by four N atoms from the two 2,2'-bipyridine ligands and two Cl atoms (Fig. 1). The main contributions to the distortion are the tight N—Pt—N chelate angles (80.33 (10)° and 80.30 (10)°), which result in non-linear trans axes (<Cl1—Pt1—N1 = 176.73 (7)°, <Cl2—Pt1—N4 = 176.91 (7)° and <N2—Pt1—N3 = 176.52 (10)°).

Because of the different trans influences of the N and Cl atoms, the Pt—N bonds trans to the Cl atom (lengths: 2.040 (2) and 2.037 (3) Å) are slightly longer than those trans to the N atom (lengths: 2.029 (2) and 2.028 (2) Å).

The compound displays intermolecular hydrogen bonding between the solvent H₂O molecule and the Cl anions (Table 1). There is also an intermolecular π-π interaction between the pyridine ring containing N1 and the one containg N3 at 1/2+x,1/2-y,-z, with a centroid-centroid distance of 3.962 Å and with a dihedral angle between the ring planes of 20.3°.

Experimental

To a solution of K₂PtCl₆ (0.3068 g, 0.631 mmol) in H₂O (20 ml) was added 2,2'-bipyridine (0.0971 g, 0.622 mmol) in MeOH (10 ml), and stirred for 2 h under heating. The formed precipitate was separated by filtration and washed with water and MeOH and dried under vacuum, to give a yellow powder (0.1185 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH₂Cl₂ solution.