Tetra­chlorido(1,10-phenanthroline-κ2 N,N′)platinum(IV) monohydrate

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

doi:10.1107/S1600536809002694

. 2009 Jan 28;65(Pt 2):m230. doi: 10.1107/S1600536809002694

Tetrachlorido(1,10-phenanthroline-κ² N,N′)platinum(IV) monohydrate

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

PMCID: PMC2968294 PMID: 21581820

Abstract

In the title complex, [PtCl₄(C₁₂H₈N₂)]·H₂O, the Pt⁴⁺ ion is six-coordinated in a distorted octahedral environment by two N atoms of a 1,10-phenanthroline ligand and by four Cl atoms. As a result of the different trans effects of the N and Cl atoms, the Pt—Cl bonds trans to the N atom are slightly shorter than those trans to the Cl atom. The compound displays intermolecular π–π interactions between the six-membered rings, with a centroid–centroid distance of 3.834 Å. There are also weak intramolecular C—H⋯Cl hydrogen bonds. According to the IR spectrum, solvent water was present in the crystal, but owing to the high thermal motion of the uncoordinated O atom, the H atoms could not be detected.

Related literature

For details of some other Pt–phenanthroline complexes, see: Buse et al. (1977 ▶); Fanizzi et al. (1996 ▶). For related Pt–bipyridine complexes, see: Hambley (1986 ▶); Hojjat Kashani et al. (2008 ▶).

Experimental

Crystal data

[PtCl₄(C₁₂H₈N₂)]·H₂O
M _r = 535.11
Orthorhombic,
a = 14.8481 (19) Å
b = 12.4079 (16) Å
c = 17.379 (2) Å
V = 3201.8 (7) Å³
Z = 8
Mo Kα radiation
μ = 9.43 mm⁻¹
T = 293 (2) K
0.25 × 0.08 × 0.06 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.418, T _max = 0.568
18465 measured reflections
3521 independent reflections
2414 reflections with I > 2σ(I)
R _int = 0.047

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.141
S = 1.02
3521 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 1.41 e Å⁻³
Δρ_min = −0.56 e Å⁻³

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 ▶) and PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809002694/fj2191sup1.cif

e-65-0m230-sup1.cif^{(18.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809002694/fj2191Isup2.hkl

e-65-0m230-Isup2.hkl^{(172.8KB, 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
C1—H1⋯Cl2	0.93	2.72	3.298 (10)	121
C10—H10⋯Cl1	0.93	2.74	3.306 (10)	121

Open in a new tab

Acknowledgments

This work was supported by a Korea Research Foundation grant funded by the Korean Government (MOEHRD) (grant No. KRF-2007-412-J02001).

supplementary crystallographic information

Comment

The asymmetric unit of the title compound, [PtCl₄(C₁₂H₈N₂)].H₂O, contains a neutral Pt^IV complex and a water molecule (Fig. 1 and 2). In the complex, the Pt⁴⁺ ion is six-coordinated in a distorted octahedral environment by two N atoms of the 1,10-phenanthroline ligand and four Cl atoms. The main contribution to the distortion is the tight N1—Pt1—N2 chelate angle (80.1 (2)°), which result in non-linear trans axes (<Cl1—Pt1—N1 = 174.0 (2)°, <Cl2—Pt1—N2 = 173.9 (2)° and <Cl3—Pt1—Cl4 = 176.84 (10)°). As a result of the different trans effects of the N and Cl atoms, the Pt—Cl bonds trans to the N atom (lengths: 2.317 (3) and 2.320 (2) Å) are slightly shorter than bond lengths to mutually trans Cl atoms (lengths: 2.343 (3) and 2.335 (3) Å). The compound displays intermolecular π-π interactions between six-membered rings, with a shortest centroid-centroid distance of 3.834 Å and with a dihedral angle between the ring planes of 1.48°. There are also weak intramolecular C—H···Cl hydrogen bonds (Table 1). According to the IR spectrum, water was present in the crystal.

Experimental

To a solution of K₂PtCl₆ (0.3002 g, 0.618 mmol) in H₂O (20 ml) was added 1,10-phenanthroline (0.1108 g, 0.615 mmol) in MeOH (10 ml), and stirred for 3 h at room temperature. The formed precipitate was separated by filtration and washed with water and MeOH and dried under vacuum, to give a yellow powder (0.1655 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH₂Cl₂ solution. IR (KBr): 3424 cm^-1 (broad).