Tris(propane-1,2-diamine-κ2N,N′)nickel(II) tetra­cyanidonickelate(II)

Kuchár, J.; Černák, J.

doi:10.1107/S1600536807068420

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Pages m324-m325

doi:10.1107/S1600536807068420

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Tris(propane-1,2-diamine-κ²N,N′)nickel(II) tetracyanidonickelate(II)

Juraj Kuchár ^a and Juraj Černák ^a ^*

^aDepartment of Inorganic Chemistry, Institute of Chemistry, P. J. Šafárik University, Moyzesova 11, 041 54 Košice, Slovakia
^*Correspondence e-mail: juraj.kuchar@upjs.sk

(Received 20 November 2007; accepted 25 December 2007; online 9 January 2008)

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, P n m a
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[F² > 2σ(F²)] = 0.037
wR(F²) = 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

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)

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
Symmetry codes: (i) -x+1, -y, -z; (ii) $[-x+1, y+{\script{1\over 2}}, -z]$ ; (iii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iv) x-1, y, z.

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).

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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).

Experimental top

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.

Computing details top

Data collection: EXPOSE in IPDS (Stoe & Cie, 1999); cell refinement: CELL in IPDS (Stoe & Cie, 1999); data reduction: INTEGRATE in IPDS (Stoe & Cie, 1999); 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).

Figures top

Fig. 1. View of the complex cation and complex anion of the title compound. The thermal ellipsoids are drawn at 30% probability level. The disordered positions in the complex cation are shown with light colors (i: x, 0.5 - y, z).

Tris(propane-1,2-diamine-κ²N,N')nickel(II) tetracyanidonickelate(II) top

Crystal data top

[Ni(C₃H₁₀N₂)₃][Ni(CN)₄]	F(000) = 936
M_r = 443.89	D_x = 1.392 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 1308 reflections
a = 9.7310 (12) Å	θ = 4.6–30.5°
b = 13.3770 (14) Å	µ = 1.79 mm⁻¹
c = 16.275 (3) Å	T = 193 K
V = 2118.5 (5) Å³	Needle, light-violet
Z = 4	0.5 × 0.1 × 0.1 mm

Data collection top

Stoe IPDS diffractometer	1947 independent reflections
Radiation source: fine-focus sealed tube	1401 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
Detector resolution: 150 pixels mm^-1	θ_max = 25.0°, θ_min = 2.9°
ϕ scans	h = −11→11
Absorption correction: gaussian (XPREP in SHELXTL; Siemens, 1996)	k = −15→15
T_min = 0.580, T_max = 0.815	l = −19→19
14468 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 0.92	w = 1/[σ²(F_o²) + (0.0714P)²] where P = (F_o² + 2F_c²)/3
1947 reflections	(Δ/σ)_max < 0.001
183 parameters	Δρ_max = 0.52 e Å⁻³
12 restraints	Δρ_min = −0.60 e Å⁻³

Crystal data top

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

Data collection top

Stoe IPDS diffractometer	1947 independent reflections
Absorption correction: gaussian (XPREP in SHELXTL; Siemens, 1996)	1401 reflections with I > 2σ(I)
T_min = 0.580, T_max = 0.815	R_int = 0.052
14468 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	12 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 0.92	Δρ_max = 0.52 e Å⁻³
1947 reflections	Δρ_min = −0.60 e Å⁻³
183 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni1	0.79310 (7)	0.2500	0.07496 (4)	0.0430 (2)
C1	0.8878 (6)	0.2500	0.1736 (4)	0.0505 (13)
N1	0.9497 (6)	0.2500	0.2336 (3)	0.0711 (14)
C2	0.7945 (5)	0.1112 (3)	0.0757 (3)	0.0605 (10)
N2	0.7977 (6)	0.0261 (3)	0.0772 (3)	0.0972 (15)
C3	0.6984 (5)	0.2500	−0.0248 (4)	0.0554 (14)
N3	0.6348 (6)	0.2500	−0.0840 (4)	0.0746 (15)
Ni2	0.26627 (6)	0.2500	0.03265 (4)	0.0396 (2)
C4	0.0955 (5)	0.2500	−0.1180 (3)	0.0644 (15)
H4C	0.0649	0.3200	−0.1066	0.077*	0.50
C5	0.2431 (5)	0.2500	−0.1451 (4)	0.0757 (18)
H5C	0.2799	0.1810	−0.1461	0.091*	0.50
H5D	0.2517	0.2790	−0.2008	0.091*	0.50
C6	0.3879 (5)	0.0651 (3)	0.0946 (3)	0.099 (2)
H6C	0.4498	0.0986	0.1343	0.119*	0.50
H6D	0.4220	−0.0039	0.0862	0.119*	0.50
H6E	0.4497	0.0288	0.1327	0.119*	0.50
H6F	0.3922	0.0328	0.0400	0.119*	0.50
C7	0.2450 (5)	0.0615 (3)	0.1294 (3)	0.0876 (16)
H7C	0.1813	0.0302	0.0886	0.105*	0.50
H7D	0.2619	0.1215	0.1646	0.105*	0.50
C8	0.0056 (10)	0.2045 (7)	−0.1810 (6)	0.083 (3)	0.50
H8C	0.0391	0.1373	−0.1942	0.124*	0.50
H8D	0.0067	0.2458	−0.2307	0.124*	0.50
H8E	−0.0885	0.2001	−0.1599	0.124*	0.50
N4	0.1011 (6)	0.1921 (4)	−0.0397 (3)	0.0509 (14)	0.50
H4A	0.1155	0.1254	−0.0506	0.061*	0.50
H4B	0.0195	0.1984	−0.0117	0.061*	0.50
N5	0.3194 (6)	0.3121 (4)	−0.0839 (3)	0.0475 (14)	0.50
H5A	0.2927	0.3780	−0.0871	0.057*	0.50
H5B	0.4126	0.3082	−0.0927	0.057*	0.50
N6	0.3911 (6)	0.1202 (4)	0.0147 (3)	0.0515 (15)	0.50
H6A	0.3562	0.0811	−0.0268	0.062*	0.50
H6B	0.4796	0.1381	0.0015	0.062*	0.50
N7	0.2107 (6)	0.1694 (3)	0.1391 (4)	0.0539 (15)	0.50
H7A	0.2568	0.1949	0.1838	0.065*	0.50
H7B	0.1180	0.1763	0.1484	0.065*	0.50
C9	0.258 (3)	−0.0030 (11)	0.2011 (7)	0.073 (6)	0.42 (3)
H9C	0.3260	0.0252	0.2390	0.109*	0.42 (3)
H9D	0.2877	−0.0698	0.1837	0.109*	0.42 (3)
H9E	0.1689	−0.0080	0.2290	0.109*	0.42 (3)
N8	0.4263 (6)	0.3269 (3)	0.0947 (4)	0.0507 (14)	0.50
H8A	0.4347	0.3038	0.1478	0.061*	0.50
H8B	0.5087	0.3175	0.0681	0.061*	0.50
N9	0.1551 (6)	0.3770 (4)	0.0749 (4)	0.0532 (15)	0.50
H9A	0.1265	0.4146	0.0308	0.064*	0.50
H9B	0.0785	0.3565	0.1035	0.064*	0.50
C10	0.181 (3)	0.5209 (10)	0.174 (2)	0.086 (7)	0.38 (3)
H10A	0.2265	0.5288	0.2274	0.130*	0.38 (3)
H10B	0.0836	0.5067	0.1822	0.130*	0.38 (3)
H10C	0.1915	0.5827	0.1422	0.130*	0.38 (3)
C11	0.445 (3)	0.023 (2)	0.1699 (11)	0.138 (15)	0.20
H11A	0.5445	0.0147	0.1636	0.207*	0.20
H11B	0.4024	−0.0415	0.1811	0.207*	0.20
H11C	0.4268	0.0690	0.2158	0.207*	0.20

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0430 (4)	0.0313 (3)	0.0547 (4)	0.000	0.0079 (3)	0.000
C1	0.054 (3)	0.038 (2)	0.060 (4)	0.000	0.017 (3)	0.000
N1	0.074 (4)	0.085 (4)	0.054 (3)	0.000	0.005 (3)	0.000
C2	0.073 (3)	0.041 (2)	0.068 (3)	−0.0044 (18)	0.004 (2)	−0.0087 (18)
N2	0.152 (5)	0.0341 (18)	0.106 (4)	−0.005 (2)	−0.001 (3)	−0.0084 (19)
C3	0.040 (3)	0.061 (3)	0.065 (4)	0.000	0.012 (3)	0.000
N3	0.053 (3)	0.101 (4)	0.070 (4)	0.000	0.000 (3)	0.000
Ni2	0.0426 (4)	0.0279 (3)	0.0484 (4)	0.000	0.0071 (3)	0.000
C4	0.057 (3)	0.067 (4)	0.069 (4)	0.000	−0.006 (3)	0.000
C5	0.065 (4)	0.110 (5)	0.052 (3)	0.000	−0.002 (3)	0.000
C6	0.080 (4)	0.053 (3)	0.164 (6)	0.005 (2)	−0.028 (4)	0.043 (3)
C7	0.103 (4)	0.066 (3)	0.094 (4)	−0.021 (3)	−0.016 (3)	0.041 (3)
C8	0.067 (6)	0.099 (7)	0.082 (6)	−0.007 (5)	−0.011 (6)	−0.005 (5)
N4	0.052 (4)	0.041 (3)	0.060 (4)	0.000 (3)	0.009 (3)	0.009 (3)
N5	0.050 (3)	0.034 (3)	0.058 (4)	0.002 (2)	0.008 (3)	0.004 (3)
N6	0.052 (4)	0.032 (3)	0.071 (4)	0.001 (2)	0.008 (3)	−0.003 (3)
N7	0.049 (3)	0.053 (3)	0.059 (4)	0.005 (3)	0.005 (3)	0.007 (3)
C9	0.108 (16)	0.044 (6)	0.066 (7)	−0.002 (7)	0.019 (7)	0.018 (5)
N8	0.054 (3)	0.046 (3)	0.052 (4)	−0.002 (3)	0.014 (3)	−0.004 (3)
N9	0.055 (4)	0.036 (3)	0.068 (4)	0.001 (3)	0.017 (3)	0.000 (3)
C10	0.083 (12)	0.061 (8)	0.115 (15)	0.020 (8)	0.008 (13)	−0.006 (8)
C11	0.11 (2)	0.20 (4)	0.10 (3)	−0.07 (3)	0.032 (19)	−0.08 (3)

Geometric parameters (Å, º) top

Ni1—C1	1.852 (7)	C7—C10ⁱ	1.457 (7)
Ni1—C2ⁱ	1.856 (4)	C7—C9	1.457 (7)
Ni1—C2	1.856 (4)	C7—N7	1.490 (3)
Ni1—C3	1.866 (7)	C7—N9ⁱ	1.493 (3)
C1—N1	1.147 (7)	C7—H7C	1.0000
C2—N2	1.139 (5)	C7—H7D	1.0000
C3—N3	1.145 (8)	C8—H8C	0.9800
Ni2—N7ⁱ	2.112 (6)	C8—H8D	0.9800
Ni2—N7	2.112 (6)	C8—H8E	0.9800
Ni2—N8	2.122 (6)	N4—H4A	0.9200
Ni2—N8ⁱ	2.122 (6)	N4—H4B	0.9200
Ni2—N9ⁱ	2.128 (6)	N5—H5A	0.9200
Ni2—N9	2.128 (6)	N5—H5B	0.9200
Ni2—N5ⁱ	2.135 (6)	N6—H6A	0.9200
Ni2—N5	2.135 (6)	N6—H6B	0.9200
Ni2—N4	2.137 (6)	N7—H7A	0.9200
Ni2—N4ⁱ	2.137 (6)	N7—H7B	0.9200
Ni2—N6ⁱ	2.139 (5)	C9—H9C	0.9800
Ni2—N6	2.139 (5)	C9—H9D	0.9800
C4—C8	1.480 (10)	C9—H9E	0.9800
C4—N4	1.492 (3)	N8—C6ⁱ	1.492 (3)
C4—C5	1.503 (6)	N8—H8A	0.9200
C4—H4C	1.0000	N8—H8B	0.9200
C5—N5	1.494 (3)	N9—C7ⁱ	1.493 (3)
C5—H5C	0.9900	N9—H9A	0.9200
C5—H5D	0.9900	N9—H9B	0.9200
C6—C11	1.457 (7)	C10—C7ⁱ	1.457 (7)
C6—N6	1.495 (3)	C10—H10A	0.9800
C6—C7	1.503 (6)	C10—H10B	0.9800
C6—H6C	0.9900	C10—H10C	0.9800
C6—H6D	0.9900	C11—H11A	0.9800
C6—H6E	0.9900	C11—H11B	0.9800
C6—H6F	0.9900	C11—H11C	0.9800

C1—Ni1—C2ⁱ	89.46 (14)	C9—C7—C6	103.9 (11)
C1—Ni1—C2	89.46 (14)	N7—C7—C6	102.5 (4)
C2ⁱ—Ni1—C2	178.9 (3)	N9ⁱ—C7—C6	107.5 (4)
C1—Ni1—C3	179.7 (2)	C9—C7—H7C	109.7
C2ⁱ—Ni1—C3	90.54 (14)	N7—C7—H7C	109.7
C2—Ni1—C3	90.54 (14)	C6—C7—H7C	109.7
N1—C1—Ni1	178.2 (5)	C10ⁱ—C7—H7D	113.2
N2—C2—Ni1	178.6 (5)	C4—C8—H8C	109.5
N3—C3—Ni1	176.9 (5)	C4—C8—H8D	109.5
N7—Ni2—N8	92.6 (2)	H8C—C8—H8D	109.5
N7ⁱ—Ni2—N8ⁱ	92.6 (2)	C4—C8—H8E	109.5
N7ⁱ—Ni2—N9ⁱ	90.7 (2)	H8C—C8—H8E	109.5
N8ⁱ—Ni2—N9ⁱ	80.36 (19)	H8D—C8—H8E	109.5
N7—Ni2—N9	90.7 (2)	C4—N4—Ni2	108.0 (3)
N8—Ni2—N9	80.36 (19)	C4—N4—H4A	110.1
N8ⁱ—Ni2—N5ⁱ	93.3 (2)	Ni2—N4—H4A	110.1
N9ⁱ—Ni2—N5ⁱ	95.7 (2)	C4—N4—H4B	110.1
N8—Ni2—N5	93.3 (2)	Ni2—N4—H4B	110.1
N9—Ni2—N5	95.7 (2)	H4A—N4—H4B	108.4
N7—Ni2—N4	94.3 (2)	C5—N5—Ni2	104.8 (3)
N8—Ni2—N4	171.73 (19)	C5—N5—H5A	110.8
N9—Ni2—N4	94.9 (2)	Ni2—N5—H5A	110.8
N5—Ni2—N4	80.42 (19)	C5—N5—H5B	110.8
N7ⁱ—Ni2—N4ⁱ	94.3 (2)	Ni2—N5—H5B	110.8
N8ⁱ—Ni2—N4ⁱ	171.73 (19)	H5A—N5—H5B	108.9
N9ⁱ—Ni2—N4ⁱ	94.9 (2)	C6—N6—Ni2	105.7 (3)
N5ⁱ—Ni2—N4ⁱ	80.42 (19)	C6—N6—H6A	110.6
N7ⁱ—Ni2—N6ⁱ	80.95 (19)	Ni2—N6—H6A	110.6
N8ⁱ—Ni2—N6ⁱ	92.4 (2)	C6—N6—H6B	110.6
N9ⁱ—Ni2—N6ⁱ	168.7 (2)	Ni2—N6—H6B	110.6
N5ⁱ—Ni2—N6ⁱ	93.3 (2)	H6F—N6—H6B	108.4
N4ⁱ—Ni2—N6ⁱ	93.3 (2)	H6A—N6—H6B	108.7
N7—Ni2—N6	80.95 (19)	C7—N7—Ni2	110.5 (4)
N8—Ni2—N6	92.4 (2)	C7—N7—H7A	109.5
N9—Ni2—N6	168.7 (2)	Ni2—N7—H7A	109.5
N5—Ni2—N6	93.3 (2)	C7—N7—H7B	109.5
N4—Ni2—N6	93.3 (2)	Ni2—N7—H7B	109.5
C8—C4—N4	113.6 (5)	H7A—N7—H7B	108.1
C8—C4—C5	111.2 (5)	C7—C9—H9C	109.5
N4—C4—C5	102.5 (4)	C7—C9—H9D	109.5
C8—C4—H4C	109.8	C7—C9—H9E	109.5
N4—C4—H4C	109.8	C6ⁱ—N8—Ni2	106.6 (4)
C5—C4—H4C	109.8	C6ⁱ—N8—H8A	110.4
N5—C5—C4	106.2 (4)	Ni2—N8—H8A	110.4
N5—C5—H5C	110.5	C6ⁱ—N8—H8B	110.4
C4—C5—H5C	110.5	Ni2—N8—H8B	110.4
N5—C5—H5D	110.5	H8A—N8—H8B	108.6
C4—C5—H5D	110.5	C7ⁱ—N9—Ni2	109.5 (3)
H5C—C5—H5D	108.7	C7ⁱ—N9—H9A	109.8
C11—C6—N6	155.9 (13)	Ni2—N9—H9A	109.8
C11—C6—C7	91.4 (13)	C7ⁱ—N9—H9B	109.8
N6—C6—C7	111.3 (4)	Ni2—N9—H9B	109.8
N6—C6—H6C	109.4	H9A—N9—H9B	108.2
C7—C6—H6C	109.4	C7ⁱ—C10—H10A	109.5
N6—C6—H6D	109.4	C7ⁱ—C10—H10B	109.5
C7—C6—H6D	109.4	H10A—C10—H10B	109.5
H6C—C6—H6D	108.0	C7ⁱ—C10—H10C	109.5
C7—C6—H6E	108.1	H10A—C10—H10C	109.5
C7—C6—H6F	111.3	H10B—C10—H10C	109.5
H6E—C6—H6F	108.8	C6—C11—H11A	109.5
C9—C7—N7	120.5 (7)	C6—C11—H11B	109.5
C10ⁱ—C7—N9ⁱ	117.6 (14)	H6E—C11—H11B	108.6
C10ⁱ—C7—C6	127.2 (9)	C6—C11—H11C	109.5

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N2ⁱⁱ	0.92	2.24	3.140 (7)	167
N5—H5A···N2ⁱⁱⁱ	0.92	2.17	3.083 (6)	169
N5—H5B···N3	0.92	2.30	3.180 (8)	159
N6—H6A···N2ⁱⁱ	0.92	2.23	3.073 (7)	152
N6—H6B···N3	0.92	2.54	3.349 (7)	147
N7—H7A···N1^iv	0.92	2.42	3.295 (8)	158
N7—H7B···N1^v	0.92	2.36	3.159 (7)	145
N8—H8A···N1^iv	0.92	2.07	2.985 (8)	179
N9—H9A···N2ⁱⁱⁱ	0.92	2.42	3.212 (8)	144

Symmetry codes: (ii) −x+1, −y, −z; (iii) −x+1, y+1/2, −z; (iv) x−1/2, y, −z+1/2; (v) x−1, y, z.

Experimental details

Crystal data
Chemical formula	[Ni(C₃H₁₀N₂)₃][Ni(CN)₄]
M_r	443.89
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	193
a, b, c (Å)	9.7310 (12), 13.3770 (14), 16.275 (3)
V (Å³)	2118.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.79
Crystal size (mm)	0.5 × 0.1 × 0.1

Data collection
Diffractometer	Stoe IPDS diffractometer
Absorption correction	Gaussian (XPREP in SHELXTL; Siemens, 1996)
T_min, T_max	0.580, 0.815
No. of measured, independent and observed [I > 2σ(I)] reflections	14468, 1947, 1401
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.100, 0.92
No. of reflections	1947
No. of parameters	183
No. of restraints	12
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.60

Computer programs: EXPOSE in IPDS (Stoe & Cie, 1999), CELL in IPDS (Stoe & Cie, 1999), INTEGRATE in IPDS (Stoe & Cie, 1999), SHELXS97 (Sheldrick, 1997), PARST (Nardelli, 1983) and SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2004), SHELXL97 (Sheldrick, 1997).

Selected bond lengths (Å) top

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N2ⁱ	0.92	2.24	3.140 (7)	166.6
N5—H5A···N2ⁱⁱ	0.92	2.17	3.083 (6)	169.4
N5—H5B···N3	0.92	2.30	3.180 (8)	159.3
N6—H6A···N2ⁱ	0.92	2.23	3.073 (7)	152.1
N6—H6B···N3	0.92	2.54	3.349 (7)	147.0
N7—H7A···N1ⁱⁱⁱ	0.92	2.42	3.295 (8)	158.2
N7—H7B···N1^iv	0.92	2.36	3.159 (7)	145.0
N8—H8A···N1ⁱⁱⁱ	0.92	2.07	2.985 (8)	178.7
N9—H9A···N2ⁱⁱ	0.92	2.42	3.212 (8)	144.3

Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1, y+1/2, −z; (iii) x−1/2, y, −z+1/2; (iv) x−1, y, z.

Acknowledgements

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.

References

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