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

Juraj Kuchár; Juraj Černák

doi:10.1107/S1600536807068420

. 2008 Jan 9;64(Pt 2):m324–m325. doi: 10.1107/S1600536807068420

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

Juraj Kuchár ^a, Juraj Černák ^a,^*

PMCID: PMC2960350 PMID: 21201293

Abstract

The title compound, [Ni(C₃H₁₀N₂)₃][Ni(CN)₄], is built up of [Ni(pn)₃]²⁺ cations (pn is 1,2-diaminopropane) and [Ni(CN)₄]²⁻ anions. Both Ni^II atoms in the cation and the anion lie on a mirror plane. The respective ions interact through Coulombic forces and through a complex network of hydrogen bonds. Extended disorder associated with the cation has been resolved. The occupancies of the respective disordered positions are 0.4:0.4:0.2.

Related literature

For related literature, see: Paharová et al. (2007 ▶); Rodriguez et al. (1999 ▶); Saha et al. (2005 ▶); Smékal et al. (2001 ▶); Černák et al. (2002 ▶); Bubanec et al. (2004 ▶); Potočňák et al. (2008 ▶).

Experimental

Crystal data

[Ni(C₃H₁₀N₂)₃][Ni(CN)₄]
M _r = 443.89
Orthorhombic,
a = 9.7310 (12) Å
b = 13.3770 (14) Å
c = 16.275 (3) Å
V = 2118.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.79 mm⁻¹
T = 193 (2) K
0.5 × 0.1 × 0.1 mm

Data collection

Stoe IPDS diffractometer
Absorption correction: Gaussian (XPREP in SHELXTL; Siemens, 1996 ▶) T _min = 0.580, T _max = 0.815
14468 measured reflections
1947 independent reflections
1401 reflections with I > 2σ(I)
R _int = 0.052

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.100
S = 0.92
1947 reflections
183 parameters
12 restraints
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Data collection: EXPOSE in IPDS (Stoe & Cie, 1999 ▶); cell refinement: CELL in IPDS; data reduction: INTEGRATE in IPDS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: PARST (Nardelli, 1983 ▶) and SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: DIAMOND (Brandenburg, 2004 ▶); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807068420/bg2155sup1.cif

e-64-0m324-sup1.cif^{(20KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807068420/bg2155Isup2.hkl

e-64-0m324-Isup2.hkl^{(116.7KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Ni1—C1	1.852 (7)
Ni1—C2	1.856 (4)
Ni1—C3	1.866 (7)
Ni2—N7	2.112 (6)
Ni2—N8	2.122 (6)
Ni2—N9	2.128 (6)
Ni2—N5	2.135 (6)
Ni2—N4	2.137 (6)
Ni2—N6	2.139 (5)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯N2ⁱ	0.92	2.24	3.140 (7)	167
N5—H5A⋯N2ⁱⁱ	0.92	2.17	3.083 (6)	169
N5—H5B⋯N3	0.92	2.30	3.180 (8)	159
N6—H6A⋯N2ⁱ	0.92	2.23	3.073 (7)	152
N6—H6B⋯N3	0.92	2.54	3.349 (7)	147
N7—H7A⋯N1ⁱⁱⁱ	0.92	2.42	3.295 (8)	158
N7—H7B⋯N1^iv	0.92	2.36	3.159 (7)	145
N8—H8A⋯N1ⁱⁱⁱ	0.92	2.07	2.985 (8)	179
N9—H9A⋯N2ⁱⁱ	0.92	2.42	3.212 (8)	144

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

Acknowledgments

This work was supported by the Slovak Grant Agency VEGA (grant No. 1/3550/06) and by the APVV (grant No. 20-005204). The authors thank Professor Werner Massa (Phillips Universität, Marburg) for kind permission to use the diffractometer.

supplementary crystallographic information

Comment

The title compound, C₁₃H₃₀N₁₀Ni₂, was studied as part of a broader study of cyanocomplexes viewed as magnetic materials [Černák et al.2002). The complex is ionic and built up of [Ni(pn)₃]²⁺cations (pn: 1,2-diaminopropane) and [Ni(CN)~4~]^2– anions. Other similar ionic compounds with square tetracyanometallates(II) and [M(L—L)₃]²⁺ cations (M = Ni, Zn, Cd; L—L: a chelating ligand), have already been described [Bubanec et al., 2004; Rodriguez et al., 1999; Paharová et al., 2007]. The Pt analogue was described by Potočňák et al. (2008).

The Ni^II atom in the complex cation exhibits pseudo-octahedral coordination by six nitrogen atoms from three chelate bonded pn ligands in gauche conformations. As the nickel atom occupies the position on a mirror plane the chelate bonded ligands are disordered in two positions with half occupancy (Fig. 1). Further disorder associated with the position of the methyl groups bonded to the carbon atom was detected so within the same metallocycle both R and S enantiomers are present with the same occupancy. Moreover, the structure is centrosymmetric so both opposite absolute configurations Λδδλ and Δλλδ of the chiral cations are present in the unit cell in equal quantities. It is worth noting that for the synthesis a racemic mixture of the pn ligand was used. The observed geometrical parameters are close to those observed in [Ni(pn)₃][Fe(CN)₅NO].H₂O [Saha et al., 2005].

The charge of the cation is compensated by a [Ni(CN)₄]^2- anion. The latter is bisected by a mirror plane, leading to a rather regular NiC₄ chromophore. The geometric characteristics are similar to those previously reported [Smékal et al., 2001].

The Ni^II atoms in the respective ions are not connected by covalent bonds, the shortest distance between Ni^II atoms being 8.527 (1) Å. The cations are connected by a complicated system of weak intermolecular hydrogen bonds of the N—H···N≡C—Ni—C≡N···H—N type, in which also the complex anions take part and where the H···N distance range is 2.103–2.488 Å.

Experimental

To 10 ml of a 0.1 M hot solution of NiSO₄.6H₂O (0.262 g, 1 mmol) 0.35 ml of pn (4 mmol) were added under continuous stirring, followed by addition of 10 ml of a 0.1 M warm solution of K₂[Ni(CN)₄].H₂O (1 mmol). The resulting clear solution was left for crystallization at room temperature. Single crystals of the title compound, in the form of light violet needles suitable for X-ray studies, appeared after one day.