(1RS,2RS)-4,4′-(1-Aza­niumyl-2-hy­droxy­ethane-1,2-di­yl)dipyridinium tetra­chlorido­platinate(II) chloride

José J Campos-Gaxiola; Jorge L Almaral-Sanchez; Adriana Cruz-Enríquez; Herbert Höpfl; Miguel Parra-Hake

doi:10.1107/S160053681300425X

. 2013 Feb 20;69(Pt 3):m157–m158. doi: 10.1107/S160053681300425X

(1RS,2RS)-4,4′-(1-Azaniumyl-2-hydroxyethane-1,2-diyl)dipyridinium tetrachloridoplatinate(II) chloride

José J Campos-Gaxiola ^a,^*, Jorge L Almaral-Sanchez ^a, Adriana Cruz-Enríquez ^a, Herbert Höpfl ^b, Miguel Parra-Hake ^c

PMCID: PMC3588516 PMID: 23476502

Abstract

The title compound, (C₁₂H₁₆N₃O)[PtCl₄]Cl, consists of a 4,4′-(1-azaniumyl-2-hydroxyethane-1,2-diyl)dipyridinium trication, a square-planar tetrachloridoplatinate(II) dianion and a chloride ion. In the cation, the pyridinium rings attached to the central 1-azaniumyl-2-hydroxyethane fragment have an anti conformation, as indicated by the central C—C—C—C torsion angle of −166.5 (6)°, and they are inclined to one another by 63.5 (4)°. In the crystal, the cations and anions are linked through N—H⋯Cl and O—H⋯Cl hydrogen bonds. There are also π–π contacts [centroid–centroid distances = 3.671 (4) and 3.851 (4) Å] and a number of C—H⋯Cl interactions present, consolidating the formation of a three-dimensional supramolecular structure.

Related literature

For potential applications of organic-inorganic hybrid materials with magnetic, optical and electrical properties, see: Yao et al. (2010 ▶); Sanchez et al. (2011 ▶); Pardo et al. (2011 ▶); Piecha et al. (2012 ▶). For related tetrachloroplatinate(II) compounds, see: Fusi et al. (2012 ▶); Adarsh et al. (2010 ▶); Campos-Gaxiola et al. (2010 ▶); Adams et al. (2005 ▶). For the synthesis of the title ligand, see: Campos-Gaxiola et al. (2012 ▶). graphic file with name e-69-0m157-scheme1.jpg

Experimental

Crystal data

(C₁₂H₁₆N₃O)[PtCl₄]Cl
M _r = 590.62
Triclinic,
a = 7.636 (2) Å
b = 8.082 (2) Å
c = 14.599 (4) Å
α = 88.689 (4)°
β = 84.240 (4)°
γ = 70.148 (4)°
V = 843.1 (4) Å³
Z = 2
Mo Kα radiation
μ = 9.12 mm⁻¹
T = 100 K
0.50 × 0.26 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.092, T _max = 0.408
5093 measured reflections
2911 independent reflections
2726 reflections with I > 2σ(I)
R _int = 0.043

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.091
S = 1.05
2911 reflections
217 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 2.34 e Å⁻³
Δρ_min = −1.98 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT-Plus-NT (Bruker 2001 ▶); data reduction: SAINT-Plus-NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(19.9KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681300425X/su2560sup1.cif

e-69-0m157-sup1.cif^{(19.9KB, cif)}

Click here for additional data file.^{(142.9KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681300425X/su2560Isup2.hkl

e-69-0m157-Isup2.hkl^{(142.9KB, 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—H1′⋯Cl1ⁱ	0.84 (6)	2.49 (7)	3.250 (6)	152 (6)
N1—H1A⋯Cl5ⁱⁱ	0.86 (7)	2.32 (6)	3.148 (6)	162 (7)
N1—H1B⋯Cl5ⁱⁱⁱ	0.86 (5)	2.30 (6)	3.097 (7)	154 (7)
N1—H1C⋯Cl2	0.86 (5)	2.50 (5)	3.214 (6)	141 (6)
N1—H1C⋯Cl3	0.86 (5)	2.58 (7)	3.242 (6)	134 (6)
N2—H2′⋯Cl5^iv	0.84 (4)	2.45 (7)	3.088 (6)	134 (7)
N2—H2′⋯Cl5^v	0.84 (4)	2.69 (6)	3.272 (6)	128 (7)
N3—H3′⋯Cl1^vi	0.84 (6)	2.50 (6)	3.275 (6)	155 (6)
N3—H3′⋯Cl4^vi	0.84 (6)	2.72 (7)	3.286 (7)	127 (7)
C1—H1⋯Cl1^vii	0.98	2.71	3.660 (8)	163
C5—H5⋯Cl3ⁱⁱⁱ	0.93	2.71	3.604 (8)	162
C10—H10⋯Cl3ⁱ	0.93	2.73	3.459 (8)	136
C10—H10⋯Cl5^v	0.93	2.74	3.308 (7)	120
C11—H11⋯Cl2^viii	0.93	2.64	3.449 (8)	145

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .

Acknowledgments

This work was supported financially by the Universidad Autónoma de Sinaloa (PROFAPI 2012/032).

supplementary crystallographic information

Comment

Hydrogen bond based organic–inorganic hybrid materials are receiving continuous interest because of their structural, magnetic, optical and electrical properties (Yao et al. 2010; Sanchez et al. 2011; Pardo et al. 2011 and Piecha et al. 2012). An interesting approach for the preparation of such materials consists in the utilization of supramolecular synthons containing charge-assisted N⁺–H···^-Cl hydrogen bonds, through which organic cations and anionic metal complexes are linked to form crystalline organic–inorganic hybrid solids (Fusi et al. 2012; Adarsh et al. 2010; Campos-Gaxiola et al. 2010, and Adams et al. 2005). As a further contribution we report herein the crystal structure of the title compound.

The molecular structure of the title compound is illustrated in Fig. 1. The asymmetric unit consists of one threefold charged organic cation in a general position, one independent [PtCl₄]^2- dianion, and one chloride atom (Fig 1). In the cation, the pyridinium rings attached to the central 2-ammoniumethanol fragment show anti conformation, as indicated by the C8—C1—C2—C3 torsion angle of -166.5 (6)°. The pyridinium rings form a dihedral angle of 63.5 (4)°. The Pt atom is embedded in a square-planar coordination environment with Pt—Cl distances ranging from 2.2999 (17) to 2.3127 (18) Å.

In the crystal, the cations and anions are linked by charge-assisted N⁺—H···^-Cl, O—H···^-Cl hydrogen bonds (Table 1). There are also a number of C—H···Cl contacts and π—π interactions present, consolidating the formation of the three-dimensional supramolecular structure (Table 1 and Fig 2). The π—π interactions are parallel slipped interactions involving inversion related pyridinium rings, Cg1 = N2/C8-C12 and Cg2 = N3/C3-C7 [Cg1···Cg1ⁱ = 3.851 (4); normal distance 3.487 (3) Å; slippage 1.634 Å; symmetry code: (i) -x, -y+2, -z: Cg2···Cg2ⁱⁱ = 3.671 (4) Å; normal distance 3.460 (3) Å; slippage 1.225 Å; symmetry code: (ii) -x, -y+1, -z].

Experimental

The organic entities in the title compound are a product of partial hydrolysis starting from 2,4,5-tris(pyridin-4-yl)-4,5-dihydro-1,3-oxazole, which was synthesized according to a previously reported procedure (Campos-Gaxiola et al., 2012). For the preparation of the platinum compound, a solution of 2,4,5-tris(pyridin-4-yl)-4,5-dihydro-1,3-oxazole (0.05 g, 0.16 mmol) in methanol and concentrated HCl (37%, 3 ml) was added dropwise to a stirring solution of potassium tetrachloroplatinate (0.06 g, 0.16 mmol) in water (5 ml). The resulting yellow solution was stirred for 40 Min at 323 K, whereupon the solution was left to evaporate slowly at room temperature. After two weeks, yellow crystals were isolated [Yield: 45%]. Spectroscopic and other analytical data for the title compound are available in the archived CIF.