Tris(propane-1,2-diamine-κ2 N,N′)nickel(II) tetra­cyanidoplatinate(II)

Ivan Potočňák; Martin Vavra; Dirk Steinborn; Christoph Wagner

doi:10.1107/S1600536807066913

. 2007 Dec 21;64(Pt 1):m235–m236. doi: 10.1107/S1600536807066913

Tris(propane-1,2-diamine-κ² N,N′)nickel(II) tetracyanidoplatinate(II)

Ivan Potočňák ^a,^*, Martin Vavra ^a, Dirk Steinborn ^b, Christoph Wagner ^b

PMCID: PMC2915156 PMID: 21200578

Abstract

In the title compound, [Ni(C₃H₁₀N₂)₃][Pt(CN)₄], the [Pt(CN)₄]²⁻ anion with the environment of the Pt^II atom, lying on a mirror plane, is square planar, whereas the Ni^II atom in the [Ni(C₃N₂H₁₀)₃]²⁺ cation, also lying on a mirror plane, has a slightly distorted octahedral coordination geometry. Three chiral 1,2-diaminopropane molecules, which are disordered equally over two sets of positions, adopt Δ(δδδ) and Δ(λλλ) configurations. The average Ni—N and Pt—C bond lengths are 2.131 (10) and 1.988 (10) Å, respectively. The cations and anions are connected by N—H⋯N hydrogen bonds.

Related literature

For related literature on compounds with [Ni(1,2-diaminopropane)₃]²⁺ cations, see: Behrens et al. (2003 ▶) for Sn₂S₆ ⁴⁻; Kuchár & Černák (2008 ▶) for [Ni(CN)₄]²⁻; Lin et al. (2005 ▶) for [H₃Ge₁₄NiO₂₇]⁴⁻; Nasanen et al. (1964 ▶) for ClO₄ ⁻; Saha et al. (2005 ▶) for [Fe(CN)₅NO]²⁻.

Experimental

Crystal data

[Ni(C₃H₁₀N₂)₃][Pt(CN)₄]
M _r = 580.27
Orthorhombic,
a = 9.8206 (18) Å
b = 13.694 (2) Å
c = 16.261 (3) Å
V = 2186.8 (7) Å³
Z = 4
Mo Kα radiation
μ = 7.27 mm⁻¹
T = 220 K
0.38 × 0.11 × 0.06 mm

Data collection

Stoe IPDS diffractometer
Absorption correction: numerical (IPDS FACE; Stoe & Cie, 1999 ▶) T _min = 0.104, T _max = 0.446
15408 measured reflections
2197 independent reflections
1807 reflections with I > 2σ(I)
R _int = 0.088

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.085
S = 1.04
2197 reflections
160 parameters
H-atom parameters constrained
Δρ_max = 1.23 e Å⁻³
Δρ_min = −1.92 e Å⁻³

Data collection: IPDS EXPOSE (Stoe & Cie, 1999 ▶); cell refinement: IPDS CELL (Stoe & Cie, 1999 ▶); data reduction: IPDS INTEGRATE (Stoe & Cie, 1999 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: DIAMOND (Brandenburg, 2001 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807066913/hy2111sup1.cif

e-64-0m235-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807066913/hy2111Isup2.hkl

e-64-0m235-Isup2.hkl^{(105.9KB, hkl)}

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

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

Pt—C1	1.958 (10)
Pt—C2	1.995 (11)
Pt—C3	1.999 (9)
Ni—N21ⁱ	2.118 (9)
Ni—N10	2.127 (9)
Ni—N30	2.122 (10)
Ni—N40	2.137 (9)
Ni—N11ⁱ	2.142 (10)
Ni—N20	2.142 (10)

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C1—Pt—C2	179.4 (3)
C1—Pt—C3	89.5 (2)
C2—Pt—C3	90.5 (2)
C3ⁱ—Pt—C3	178.8 (4)
N21ⁱ—Ni—N10	171.3 (4)
N21ⁱ—Ni—N30	93.3 (4)
N10—Ni—N30	93.3 (4)
N21ⁱ—Ni—N40	91.7 (4)
N10—Ni—N40	95.0 (4)
N30—Ni—N40	80.8 (4)
N21ⁱ—Ni—N11ⁱ	80.5 (4)
N10—Ni—N11ⁱ	93.3 (4)
N30—Ni—N11ⁱ	94.4 (4)
N40—Ni—N11ⁱ	170.6 (4)
N21ⁱ—Ni—N20	93.8 (4)
N10—Ni—N20	80.4 (4)
N30—Ni—N20	170.1 (4)
N40—Ni—N20	92.2 (4)
N11ⁱ—Ni—N20	93.5 (4)

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Symmetry code: (i) Inline graphic .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N21—H21F⋯N2	0.90	2.51	3.311 (12)	148
N40—H40A⋯N2	0.90	2.30	3.160 (14)	160
N10—H10B⋯N3ⁱⁱ	0.90	2.40	3.193 (13)	148
N21—H21E⋯N3ⁱⁱ	0.90	2.24	3.066 (13)	152
N40—H40B⋯N3ⁱⁱ	0.90	2.21	3.098 (12)	169
N11—H11C⋯N1ⁱⁱⁱ	0.90	2.48	3.342 (13)	159
N20—H20B⋯N1ⁱⁱⁱ	0.90	2.11	3.005 (12)	174
N11—H11D⋯N1^iv	0.90	2.46	3.242 (13)	145
N30—H30B⋯N3^v	0.90	2.31	3.191 (11)	166

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

Acknowledgments

This work was supported by the Slovak Grant Agency VEGA (grant No. 1/2470/05), and by APVT (grant No. 20-005204). MV thanks DAAD for financial support and the hospitality of Martin Luther University.

supplementary crystallographic information

Comment

The title compound, [Ni(pn)₃][Pt(CN)₄] (pn = 1,2-diaminopropane) has been prepared by a chance within our studies on the role of hydrogen bonds as possible exchange paths for magnetic interactions in low-dimensional compounds. The compound consists of discrete [Ni(pn)₃]²⁺ cations and [Pt(CN)₄]^2- anions (Fig. 1). Selected bond lengths and angles are given in Table 1. The Ni^II atom is coordinated by six N atoms of three racemic pn ligands, which are disordered over two sets of positions, with site occupancies of 0.50 (except methylene and methine C atoms), thus forming Δ(δδδ) and Δ(λλλ) configurations. Moreover, a mirror plane passes through the tetracyanoplatinate anion (N1, C1, Pt, C2 and N2 atoms) and the [Ni(pn)₃]²⁺ cation (Ni, C31 and C41 atoms). The coordination geometry around the Ni^II atom can be described as octahedral. The two N atoms occupying axial positions form an angle of 170.6 (4)° and the Ni—N bond distances range from 2.118 (9)–2.142 (10)Å [mean bond length is 2.131 (10) Å], in good agreement with the values reported of other [Ni(pn)₃]²⁺ complexes (Behrens et al., 2003; Kuchár & Černák, 2008; Saha et al., 2005). Octahedral coordination geometry around the Ni atom was observed also in other compounds with [Ni(pn)₃]²⁺ cation (Nasanen et al., 1964; Lin et al., 2005). The square-planar geometry of [Pt(CN)₄]^2- is in good agreement with those of the previous studies with average Pt—C bond lengths of 1.988 (10) Å. The structure is stabilized also by the N—H···N hydrogen bonds between the cations and anions (Table 2).

Experimental

The title compound were prepared by a chance during our attempts to prepare chain-like [Ni(pn)₂][Pt(CN)₄] compound suitable for magnetic studies. A mixture of a 10 ml aqueous solution of NiSO₄.6H₂O (0.132 g, 0.5 mmol) and pn (0.086 ml, 1.0 mmol) was stirred for 30 min and a 10 ml aqueous solution of K₂[Pt(CN)₄].3H₂O (0.216 g, 0.5 mmol) was added. The pink precipitate thus formed was dissolved by addition of a concentrated solution of ammonia (20 ml). After few days, pink crystals of the title compound were filtered off and dried in air.