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Acta Cryst. (2008). E64, m235-m236    [ doi:10.1107/S1600536807066913 ]

Tris(propane-1,2-diamine-[kappa]2N,N')nickel(II) tetracyanidoplatinate(II)

I. Potocnák, M. Vavra, D. Steinborn and C. Wagner

Abstract top

In the title compound, [Ni(C3H10N2)3][Pt(CN)4], the [Pt(CN)4]2- anion with the environment of the PtII atom, lying on a mirror plane, is square planar, whereas the NiII 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 [Delta]([delta][delta][delta]) and [Delta]([lambda][lambda][lambda]) 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.

Comment top

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 NiII 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 NiII 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).

Related literature top

For related literature on compounds with [Ni(1,2-diaminopropane)3]2+ cations, see: Behrens et al. (2003) for Sn2S64-; 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 top

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.

Refinement top

H atoms were positioned geometrically and refined as riding atoms, with N—H = 0.90 Å, C—H = 0.97Å (CH2), 0.98Å (CH) and Uiso(H) = 1.2Ueq(C,N) and with C—H = 0.96Å (CH3) and Uiso(H) = 1.5Ueq(C). The highest residual electron density and the deepest hole were found 1.01 and 0.88 Å from the Pt atom, respectively.

Computing details top

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 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The structures of the cation and anion in the title compound. Displacement ellipsoids are drawn at the 40% probability level. Coloured atoms and black bonds show the Δ(δδδ) configuration whereas transparent atoms and bonds represent the Δ(λλλ) configuration of the [Ni(pn)3]2+ cation. Hydrogen atoms are ommited for clarity. [Symmetry code: (i) x, 1/2 - y, z.]
Tris(propane-1,2-diamine-κ2N,N')nickel(II) tetracyanidoplatinate(II) top
Crystal data top
[Ni(C3H10N2)3][Pt(CN)4]F000 = 1136
Mr = 580.27Dx = 1.762 Mg m−3
Orthorhombic, PnmaMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 8000 reflections
a = 9.8206 (18) Åθ = 2.4–25.9º
b = 13.694 (2) ŵ = 7.27 mm−1
c = 16.261 (3) ÅT = 220 K
V = 2186.8 (7) Å3Needle, pink
Z = 40.38 × 0.11 × 0.06 mm
Data collection top
Stoe IPDS
diffractometer		2197 independent reflections
Radiation source: fine-focus sealed tube1807 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.088
T = 220 Kθmax = 25.9º
φ scansθmin = 2.4º
Absorption correction: numerical
(IPDS FACE; Stoe & Cie, 1999)		h = −12→12
Tmin = 0.104, Tmax = 0.446k = −16→16
15408 measured reflectionsl = −19→19
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.085  w = 1/[σ2(Fo2) + (0.0507P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2197 reflectionsΔρmax = 1.23 e Å−3
160 parametersΔρmin = −1.92 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Ni(C3H10N2)3][Pt(CN)4]V = 2186.8 (7) Å3
Mr = 580.27Z = 4
Orthorhombic, PnmaMo Kα
a = 9.8206 (18) ŵ = 7.27 mm−1
b = 13.694 (2) ÅT = 220 K
c = 16.261 (3) Å0.38 × 0.11 × 0.06 mm
Data collection top
Stoe IPDS
diffractometer		2197 independent reflections
Absorption correction: numerical
(IPDS FACE; Stoe & Cie, 1999)		1807 reflections with I > 2σ(I)
Tmin = 0.104, Tmax = 0.446Rint = 0.088
15408 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034160 parameters
wR(F2) = 0.085H-atom parameters constrained
S = 1.04Δρmax = 1.23 e Å−3
2197 reflectionsΔρmin = −1.92 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Pt0.20444 (3)0.25000.07418 (2)0.04021 (13)
Ni0.73154 (10)0.25000.02973 (6)0.0368 (2)
C10.1023 (9)0.25000.1776 (5)0.0475 (19)
N10.0397 (9)0.25000.2376 (5)0.072 (2)
C20.3067 (9)0.2500−0.0318 (7)0.058 (2)
N20.3700 (10)0.2500−0.0916 (6)0.079 (3)
C30.2044 (8)0.1040 (6)0.0754 (5)0.069 (2)
N30.2032 (10)0.0220 (4)0.0777 (5)0.106 (3)
C210.6124 (10)0.4305 (6)0.0987 (7)0.104 (3)
H21A0.55310.46420.13700.124*0.50
H21B0.60740.46310.04580.124*0.50
H21C0.58020.49710.09310.124*0.50
H21D0.55360.39670.13720.124*0.50
N100.8434 (11)0.3735 (7)0.0711 (6)0.048 (2)0.50
H10A0.91980.35420.09700.058*0.50
H10B0.86720.41120.02810.058*0.50
N200.5722 (11)0.3283 (7)0.0909 (6)0.051 (2)0.50
H20A0.49450.32380.06170.062*0.50
H20B0.55750.30240.14100.062*0.50
C110.7537 (11)0.4303 (6)0.1294 (6)0.085 (3)
H11A0.74490.38210.17370.101*0.50
H11B0.81560.46210.09050.101*0.50
N110.7811 (10)0.3348 (8)0.1363 (6)0.051 (3)0.50
H11C0.73460.31080.17950.061*0.50
H11D0.87040.32750.14710.061*0.50
N210.6087 (10)0.3743 (6)0.0070 (6)0.048 (2)0.50
H21E0.64450.4121−0.03280.057*0.50
H21F0.52340.3572−0.00710.057*0.50
C310.9053 (10)0.2500−0.1186 (6)0.067 (3)
H310.93570.3170−0.10820.081*0.50
C410.7596 (13)0.2500−0.1515 (6)0.087 (4)
H41A0.72360.1841−0.15470.104*0.50
H41B0.75510.2798−0.20560.104*0.50
N300.8963 (10)0.1956 (7)−0.0412 (6)0.047 (2)0.50
H30A0.97460.2020−0.01280.056*0.50
H30B0.88350.1317−0.05170.056*0.50
N400.6798 (11)0.3121 (7)−0.0867 (6)0.047 (2)0.50
H40A0.58950.3084−0.09560.057*0.50
H40B0.70540.3752−0.08900.057*0.50
C320.9945 (15)0.2029 (13)−0.1810 (9)0.089 (5)0.50
H32A1.08670.2023−0.16150.134*0.50
H32B0.98980.2389−0.23160.134*0.50
H32C0.96440.1371−0.19030.134*0.50
C120.808 (3)0.5133 (17)0.1769 (16)0.101 (7)0.50
H12A0.90030.50030.19220.151*0.50
H12B0.75370.52240.22550.151*0.50
H12C0.80410.57140.14380.151*0.50
C130.721 (3)0.4965 (18)0.2020 (17)0.101 (7)0.50
H13A0.80290.50790.23320.151*0.50
H13B0.65460.46580.23640.151*0.50
H13C0.68670.55760.18210.151*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt0.0384 (2)0.02827 (17)0.0540 (2)0.000−0.00989 (13)0.000
Ni0.0390 (5)0.0239 (5)0.0476 (5)0.000−0.0062 (4)0.000
C10.048 (5)0.040 (4)0.055 (5)0.000−0.006 (4)0.000
N10.073 (6)0.080 (7)0.064 (5)0.000−0.008 (5)0.000
C20.041 (5)0.064 (6)0.068 (6)0.000−0.013 (5)0.000
N20.048 (5)0.117 (9)0.072 (6)0.0000.005 (4)0.000
C30.076 (6)0.057 (5)0.074 (4)0.005 (4)0.001 (4)−0.007 (4)
N30.177 (11)0.016 (3)0.124 (6)0.004 (4)0.013 (5)−0.014 (3)
C210.080 (6)0.044 (4)0.187 (10)0.005 (4)0.037 (7)−0.042 (5)
N100.044 (6)0.033 (5)0.066 (6)−0.005 (4)−0.014 (5)−0.007 (5)
N200.050 (6)0.046 (5)0.057 (6)0.007 (5)−0.007 (5)−0.005 (4)
C110.104 (6)0.053 (5)0.097 (6)−0.021 (5)0.015 (5)−0.033 (4)
N110.053 (7)0.045 (6)0.053 (5)0.000 (5)−0.008 (5)−0.003 (5)
N210.047 (5)0.026 (4)0.070 (6)−0.002 (4)−0.015 (5)−0.001 (4)
C310.055 (6)0.085 (8)0.063 (6)0.0000.007 (5)0.000
C410.065 (6)0.153 (13)0.043 (5)0.0000.006 (5)0.000
N300.047 (6)0.035 (5)0.058 (5)−0.002 (4)−0.011 (4)0.005 (4)
N400.046 (5)0.036 (5)0.059 (6)−0.001 (4)−0.013 (4)0.007 (4)
C320.054 (8)0.124 (15)0.091 (10)0.021 (9)0.018 (8)−0.005 (9)
C120.14 (2)0.057 (9)0.110 (14)0.000 (12)−0.024 (13)−0.020 (9)
C130.14 (2)0.057 (9)0.110 (14)0.000 (12)−0.024 (13)−0.020 (9)
Geometric parameters (Å, °) top
Pt—C11.958 (10)N20—H20B0.9000
Pt—C21.995 (11)C11—N111.340 (13)
Pt—C3i1.999 (9)C11—C131.52 (3)
Pt—C31.999 (9)C11—C121.47 (2)
Ni—N21i2.118 (9)C11—H11A0.9800
Ni—N212.118 (9)C11—H11B0.9800
Ni—N102.127 (9)N11—H11C0.9000
Ni—N10i2.127 (9)N11—H11D0.9000
Ni—N30i2.122 (10)N21—H21E0.9000
Ni—N302.122 (10)N21—H21F0.9000
Ni—N40i2.137 (9)C31—N301.466 (12)
Ni—N402.137 (9)C31—C321.487 (16)
Ni—N112.142 (10)C31—C411.528 (16)
Ni—N11i2.142 (10)C31—H310.9800
Ni—N202.142 (10)C41—N401.565 (13)
Ni—N20i2.142 (10)C41—H41A0.9700
C1—N11.154 (11)C41—H41B0.9700
C2—N21.154 (13)N30—H30A0.9000
C3—N31.124 (11)N30—H30B0.9000
C21—N201.460 (13)N40—H40A0.9000
C21—C111.474 (14)N40—H40B0.9000
C21—N211.679 (13)C32—H32A0.9600
C21—H21A0.9700C32—H32B0.9600
C21—H21B0.9700C32—H32C0.9600
C21—H21C0.9700C12—H12A0.9600
C21—H21D0.9700C12—H12B0.9600
N10—C111.509 (14)C12—H12C0.9600
N10—H10A0.9000C13—H13A0.9600
N10—H10B0.9000C13—H13B0.9600
N20—H20A0.9000C13—H13C0.9600
C1—Pt—C2179.4 (3)N11—C11—C13124.0 (13)
C1—Pt—C3i89.5 (2)C21—C11—C1393.8 (12)
C2—Pt—C3i90.5 (2)C21—C11—C12120.9 (13)
C1—Pt—C389.5 (2)N10—C11—C12121.1 (13)
C2—Pt—C390.5 (2)C21—C11—H11A99.6
C3i—Pt—C3178.8 (4)N10—C11—H11A99.6
N21i—Ni—N10171.3 (4)C12—C11—H11A99.6
N21—Ni—N10i171.3 (4)N11—C11—H11B111.4
N21—Ni—N30i93.3 (4)C21—C11—H11B111.4
N10i—Ni—N30i93.3 (4)C13—C11—H11B111.4
N21i—Ni—N3093.3 (4)C11—N11—Ni114.6 (7)
N10—Ni—N3093.3 (4)C11—N11—H11C108.6
N21—Ni—N40i91.7 (4)Ni—N11—H11C108.6
N10i—Ni—N40i95.0 (4)C11—N11—H11D108.6
N30i—Ni—N40i80.8 (4)Ni—N11—H11D108.6
N21i—Ni—N4091.7 (4)H11C—N11—H11D107.6
N10—Ni—N4095.0 (4)C21—N21—Ni101.6 (6)
N30—Ni—N4080.8 (4)C21—N21—H21E111.5
N21—Ni—N1180.5 (4)Ni—N21—H21E111.5
N10i—Ni—N1193.3 (4)C21—N21—H21F111.5
N30i—Ni—N1194.4 (4)Ni—N21—H21F111.5
N40i—Ni—N11170.6 (4)H21E—N21—H21F109.3
N21i—Ni—N11i80.5 (4)N30—C31—C32113.6 (8)
N10—Ni—N11i93.3 (4)N30—C31—C41104.1 (7)
N30—Ni—N11i94.4 (4)C32—C31—C41108.2 (9)
N40—Ni—N11i170.6 (4)N30—C31—H31110.2
N21i—Ni—N2093.8 (4)C32—C31—H31110.2
N10—Ni—N2080.4 (4)C41—C31—H31110.2
N30—Ni—N20170.1 (4)C31—C41—N40103.5 (7)
N40—Ni—N2092.2 (4)C31—C41—H41A111.1
N11i—Ni—N2093.5 (4)N40—C41—H41A111.1
N21—Ni—N20i93.8 (4)C31—C41—H41B111.1
N10i—Ni—N20i80.4 (4)N40—C41—H41B111.1
N30i—Ni—N20i170.1 (4)H41A—C41—H41B109.0
N40i—Ni—N20i92.2 (4)C31—N30—Ni109.5 (6)
N11—Ni—N20i93.5 (4)C31—N30—H30A109.8
N1—C1—Pt178.6 (8)Ni—N30—H30A109.8
N2—C2—Pt177.6 (8)C31—N30—H30B109.8
N3—C3—Pt178.5 (8)Ni—N30—H30B109.8
N20—C21—C11106.4 (8)H30A—N30—H30B108.2
C11—C21—N21108.7 (7)C41—N40—Ni105.2 (6)
N20—C21—H21A110.4C41—N40—H40A110.7
C11—C21—H21A110.4Ni—N40—H40A110.7
N20—C21—H21B110.4C41—N40—H40B110.7
C11—C21—H21B110.4Ni—N40—H40B110.7
H21A—C21—H21B108.6H40A—N40—H40B108.8
C11—C21—H21C110.0C31—C32—H32A109.5
N21—C21—H21C110.0C31—C32—H32B109.5
C11—C21—H21D110.0H32A—C32—H32B109.5
N21—C21—H21D110.0C31—C32—H32C109.5
H21C—C21—H21D108.3H32A—C32—H32C109.5
C11—N10—Ni107.8 (7)H32B—C32—H32C109.5
C11—N10—H10A110.1C11—C12—H12A109.5
Ni—N10—H10A110.1C11—C12—H12B109.5
C11—N10—H10B110.1H12A—C12—H12B109.5
Ni—N10—H10B110.1C11—C12—H12C109.5
H10A—N10—H10B108.5H12A—C12—H12C109.5
C21—N20—Ni108.8 (7)H12B—C12—H12C109.5
C21—N20—H20A109.9C11—C13—H13A109.5
Ni—N20—H20A109.9C11—C13—H13B109.5
C21—N20—H20B109.9H13A—C13—H13B109.5
Ni—N20—H20B109.9C11—C13—H13C109.5
H20A—N20—H20B108.3H13A—C13—H13C109.5
N11—C11—C21102.7 (8)H13B—C13—H13C109.5
C21—C11—N10109.7 (7)
Symmetry codes: (i) x, −y+1/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N21—H21F···N20.902.513.311 (12)148
N40—H40A···N20.902.303.160 (14)160
N10—H10B···N3ii0.902.403.193 (13)148
N21—H21E···N3ii0.902.243.066 (13)152
N40—H40B···N3ii0.902.213.098 (12)169
N11—H11C···N1iii0.902.483.342 (13)159
N20—H20B···N1iii0.902.113.005 (12)174
N11—H11D···N1iv0.902.463.242 (13)145
N30—H30B···N3v0.902.313.191 (11)166
Symmetry codes: (ii) −x+1, y+1/2, −z; (iii) x+1/2, −y+1/2, −z+1/2; (iv) x+1, y, z; (v) −x+1, −y, −z.
Table 1
Selected geometric parameters (Å, °) top
Pt—C11.958 (10)Ni—N302.122 (10)
Pt—C21.995 (11)Ni—N402.137 (9)
Pt—C31.999 (9)Ni—N11i2.142 (10)
Ni—N21i2.118 (9)Ni—N202.142 (10)
Ni—N102.127 (9)
C1—Pt—C2179.4 (3)N21i—Ni—N11i80.5 (4)
C1—Pt—C389.5 (2)N10—Ni—N11i93.3 (4)
C2—Pt—C390.5 (2)N30—Ni—N11i94.4 (4)
C3i—Pt—C3178.8 (4)N40—Ni—N11i170.6 (4)
N21i—Ni—N10171.3 (4)N21i—Ni—N2093.8 (4)
N21i—Ni—N3093.3 (4)N10—Ni—N2080.4 (4)
N10—Ni—N3093.3 (4)N30—Ni—N20170.1 (4)
N21i—Ni—N4091.7 (4)N40—Ni—N2092.2 (4)
N10—Ni—N4095.0 (4)N11i—Ni—N2093.5 (4)
N30—Ni—N4080.8 (4)
Symmetry codes: (i) x, −y+1/2, z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N21—H21F···N20.902.513.311 (12)148
N40—H40A···N20.902.303.160 (14)160
N10—H10B···N3ii0.902.403.193 (13)148
N21—H21E···N3ii0.902.243.066 (13)152
N40—H40B···N3ii0.902.213.098 (12)169
N11—H11C···N1iii0.902.483.342 (13)159
N20—H20B···N1iii0.902.113.005 (12)174
N11—H11D···N1iv0.902.463.242 (13)145
N30—H30B···N3v0.902.313.191 (11)166
Symmetry codes: (ii) −x+1, y+1/2, −z; (iii) x+1/2, −y+1/2, −z+1/2; (iv) x+1, y, z; (v) −x+1, −y, −z.
Acknowledgements top

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.

references
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