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Acta Cryst. (2007). E63, m2072-m2073    [ doi:10.1107/S1600536807031807 ]

cis-Bis(tricyanomethanido-[kappa]N)[tris(2-aminoethyl)amine-[kappa]4N]nickel(II)

I. Potocnák, G. Lancz, A. Ruzicka and L. Jäger

Abstract top

The crystal structure of the title complex, [Ni(C4N3)2(C6H18N4)], is made up of neutral mononuclear [Ni(tren){C(CN)3}2] units [tren = tris(2-aminoethyl)amine] which are linked through van der Waals interactions and N-H...N hydrogen bonds. The Ni atom has a distorted octahedral coordination environment, bonded to the four tren N atoms [average Ni-N = 2.096 (17) Å] and the two cis-positioned C(CN)3 N atoms [Ni-N = 2.045 (4) and 2.118 (4) Å].

Comment top

The title compound [Ni(tren){C(CN)3}2] (I) has been prepared by a chance during our attempts to prepare compounds suitable for magnetic studies containing a binuclear [Ni(tren)-µ-{C(CN)3}2(tren)Ni]2+ cation. The structure of (I) is made up of neutral [Ni(tren){C(CN)3}2] mononuclear units (Fig. 1). The nickel atom is six-coordinated: six nitrogen atoms from a tetradentate tren ligand and from two monodentate C(CN)3 anionic ligands form a distorted octahedron around the metal atom. The Ni—N(tren) bond lengths [2.096 (17) Å on average] are very close to that of Ni—N(tren) found in other [Ni(tren)X2] complexes with NiN6 chromophore, where X is N(CN)2 [2.11 (3) Å] (Březina et al., 1999), X is NO2 [2.10 (3) Å] (Wen et al., 1998) and X is NCS [2.12 (3) Å] (Santarsiero & Schomaker, 1983) but are shorter than in the first report on this structure [2.18 (5) Å] (Rasmussen, 1959). The N4—Ni1—N1 angle which involves nitrogen atoms from two C(CN)3 anions is nearly 90° but the angles around the nickel atom involving at least one nitrogen atom from the tren are much more deviated from the ideal values because of steric hindrances within the tren ligand.

The molecules of (I) are linked through van der Waals interactions and N—H···N hydrogen bonds involving all amine hydrogen atoms and uncoordinated nitrogen atoms of C(CN)3; those with an N—H···N angle greater than 120° and an H···N distance less than 2.6 Å are given in Table. Through these hydrogen bonds, molecules are interconnected to form a three-dimensional structure as shown in Fig. 2.

Related literature top

Thr first report on the title structure was by Rasmussen (1959). For related [Ni(tren)X2] complexes, see: X = N(CN)2 (Březina et al., 1999); X = NO2 (Wen et al., 1998); X = NCS (Santarsiero & Schomaker, 1983).

Experimental top

The title compound [Ni(tren){C(CN)3}2] (I) has been prepared by a chance during our attempts to prepare compounds suitable for magnetic studies containing a binuclear [Ni(tren)-µ-{C(CN)3}2(tren)Ni]2+ cation. Crystals of (I) were prepared by mixing a 0.1 M aqueous solution of NiSO4 (5 ml) with a 0.45 M aqueous solution of tren (1.2 ml). To the resulting violet solution, 64.6 mg of KC(CN)3 (0.5 mmol) in 20 ml of water was added. Red-violet crystals of (I) appeared after 1 week. The crystals suitable for X-ray analysis were recrystallized from water and were filtered off and dried in air.

Refinement top

The structure was solved by direct method and subsequent Fourier syntheses. Anisotropic thermal parameters were refined for all non-H atoms. All H atoms positions were calculated using the appropriate riding model with isotropic temperature factors being 1.2 times larger than temperature factors of their parent carbon atoms.

Computing details top

Data collection: COLLECT (Nonius, 1998) and DENZO (Otwinowski & Minor, 1997); cell refinement: COLLECT and DENZO; data reduction: COLLECT and DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The structure of (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. Hydrogen bond system (dashed lines) in (I) viewed along the c axis. Methylene groups from the tren ligand are omitted because of clarity.
cis-Bis(tricyanomethanido-κN)[tris(2-aminoethyl)amine-κ4N]nickel(II)) top
Crystal data top
[Ni(C4N3)2(C6H18N4)]F(000) = 800
Mr = 385.07Dx = 1.433 Mg m−3
Orthorhombic, P21212Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2abCell parameters from 13020 reflections
a = 14.4376 (11) Åθ = 1–27.5°
b = 15.2861 (12) ŵ = 1.11 mm−1
c = 8.0888 (6) ÅT = 150 K
V = 1785.2 (2) Å3Block, red-violet
Z = 40.47 × 0.44 × 0.39 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer		3504 independent reflections
Radiation source: fine-focus sealed tube2761 reflections with I > 2σ(I)
graphiteRint = 0.077
Detector resolution: 9.091 pixels mm-1θmax = 26.0°, θmin = 1.9°
φ and ω scans to fill the Ewald sphereh = −17→17
Absorption correction: gaussian integration
(Coppens, 1970)		k = −18→18
Tmin = 0.589, Tmax = 0.672l = −9→9
12191 measured reflections
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)] = 0.041H-atom parameters constrained
wR(F2) = 0.091 w = 1/[σ2(Fo2) + (0.0365P)2 + 0.6801P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
3504 reflectionsΔρmax = 0.34 e Å−3
226 parametersΔρmin = −0.65 e Å−3
0 restraintsAbsolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.005 (19)
Crystal data top
[Ni(C4N3)2(C6H18N4)]V = 1785.2 (2) Å3
Mr = 385.07Z = 4
Orthorhombic, P21212Mo Kα radiation
a = 14.4376 (11) ŵ = 1.11 mm−1
b = 15.2861 (12) ÅT = 150 K
c = 8.0888 (6) Å0.47 × 0.44 × 0.39 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer		3504 independent reflections
Absorption correction: gaussian integration
(Coppens, 1970)		2761 reflections with I > 2σ(I)
Tmin = 0.589, Tmax = 0.672Rint = 0.077
12191 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.091Δρmax = 0.34 e Å−3
S = 1.10Δρmin = −0.65 e Å−3
3504 reflectionsAbsolute structure: Flack (1983), with how many Friedel pairs?
226 parametersFlack parameter: −0.005 (19)
0 restraints
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 > 2σ(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
xyzUiso*/Ueq
N60.2534 (3)0.9161 (2)0.9706 (4)0.0416 (9)
Ni10.08457 (3)0.76671 (3)0.31260 (6)0.02371 (13)
N300.21241 (19)0.75188 (17)0.1877 (4)0.0340 (7)
H30A0.23210.80430.15110.041*
H30B0.25520.73050.25770.041*
N200.0409 (2)0.8673 (2)0.1579 (4)0.0374 (9)
H20A−0.01030.89240.20000.045*
H20B0.08530.90830.15080.045*
N10.1272 (2)0.6611 (2)0.4640 (5)0.0364 (9)
N40.1296 (2)0.8525 (2)0.4893 (4)0.0325 (8)
N10−0.0475 (2)0.7439 (2)0.4137 (4)0.0412 (9)
H10A−0.04200.71590.51110.049*
H10B−0.07640.79510.43170.049*
C40.1484 (3)0.9043 (2)0.5869 (5)0.0246 (8)
C50.1504 (2)1.0555 (2)0.6838 (6)0.0278 (8)
N400.0362 (3)0.6867 (2)0.1225 (4)0.0384 (9)
C60.2168 (3)0.9393 (2)0.8519 (5)0.0292 (9)
N50.1342 (2)1.1284 (2)0.6661 (5)0.0396 (8)
C10.1529 (3)0.6058 (3)0.5481 (6)0.0288 (9)
C80.1717 (2)0.9662 (2)0.7062 (5)0.0264 (8)
C30.2745 (3)0.5457 (2)0.7152 (5)0.0312 (9)
C70.1853 (2)0.5385 (2)0.6483 (4)0.0250 (9)
N20.0849 (3)0.4021 (2)0.6862 (6)0.0684 (13)
C20.1307 (3)0.4627 (3)0.6701 (6)0.0371 (10)
N30.3479 (3)0.5551 (2)0.7663 (5)0.0498 (11)
C22−0.0020 (3)0.7412 (3)−0.0137 (6)0.0605 (14)
H22A0.02090.7189−0.11820.073*
H22B−0.06890.7354−0.01440.073*
C12−0.0379 (3)0.6326 (3)0.1968 (7)0.0486 (12)
H12A−0.01060.58840.26760.058*
H12B−0.07230.60310.11010.058*
C310.2008 (3)0.6913 (3)0.0461 (6)0.0490 (12)
H31A0.25560.65510.03540.059*
H31B0.19380.7248−0.05490.059*
C320.1169 (3)0.6337 (3)0.0701 (6)0.0493 (13)
H32A0.10260.6039−0.03260.059*
H32B0.13020.58980.15330.059*
C11−0.1030 (3)0.6896 (3)0.2970 (7)0.0506 (12)
H11A−0.13840.72720.22390.061*
H11B−0.14600.65320.35830.061*
C210.0215 (5)0.8334 (4)−0.0015 (7)0.0778 (19)
H21A0.07510.8439−0.07090.093*
H21B−0.02950.8668−0.04770.093*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N60.054 (2)0.044 (2)0.027 (2)0.0077 (18)0.0011 (18)0.0044 (17)
Ni10.0241 (2)0.0228 (2)0.0243 (2)0.00161 (19)−0.0009 (2)−0.0035 (2)
N300.0366 (16)0.0288 (19)0.0366 (18)0.0020 (12)0.0076 (16)0.0033 (18)
N200.0310 (17)0.0383 (19)0.043 (2)0.0058 (15)−0.0072 (16)0.0025 (18)
N10.0317 (19)0.033 (2)0.044 (2)−0.0041 (15)0.0032 (17)0.0078 (19)
N40.0374 (19)0.0265 (19)0.034 (2)−0.0008 (15)−0.0053 (16)0.0011 (17)
N100.0303 (16)0.040 (2)0.054 (2)−0.0032 (14)0.0055 (16)−0.0206 (18)
C40.026 (2)0.025 (2)0.023 (2)0.0014 (15)0.0001 (16)0.0043 (18)
C50.0276 (18)0.035 (2)0.021 (2)−0.0020 (15)0.0008 (19)−0.001 (2)
N400.045 (2)0.038 (2)0.032 (2)0.0013 (16)−0.0033 (16)−0.0131 (16)
C60.033 (2)0.027 (2)0.027 (3)0.0026 (16)0.0073 (17)−0.0027 (17)
N50.051 (2)0.0295 (19)0.038 (2)0.0038 (16)−0.0027 (18)0.0054 (18)
C10.028 (2)0.030 (2)0.028 (2)−0.0051 (17)0.0049 (18)−0.003 (2)
C80.037 (2)0.0220 (19)0.020 (2)0.0016 (14)−0.0013 (18)0.0022 (18)
C30.044 (3)0.028 (2)0.022 (2)−0.0044 (17)0.007 (2)0.0047 (18)
C70.033 (2)0.0234 (19)0.019 (2)−0.0063 (15)0.0000 (16)0.0016 (16)
N20.086 (3)0.055 (2)0.064 (3)−0.038 (2)−0.035 (3)0.031 (3)
C20.051 (2)0.037 (2)0.023 (2)−0.0095 (19)−0.016 (2)0.011 (2)
N30.042 (2)0.053 (2)0.054 (3)−0.0079 (18)−0.0077 (18)0.0130 (19)
C220.071 (3)0.068 (4)0.042 (3)0.010 (3)−0.024 (2)−0.013 (3)
C120.044 (2)0.039 (2)0.062 (3)−0.0110 (19)0.000 (3)−0.023 (3)
C310.058 (3)0.047 (3)0.042 (3)0.009 (2)0.022 (2)−0.004 (2)
C320.070 (3)0.041 (3)0.037 (3)0.004 (2)0.011 (2)−0.022 (2)
C110.028 (2)0.052 (3)0.072 (4)−0.0100 (17)0.005 (2)−0.019 (3)
C210.109 (5)0.068 (4)0.057 (4)−0.019 (3)−0.052 (3)0.018 (3)
Geometric parameters (Å, °) top
Ni1—N42.045 (4)N6—C61.152 (5)
Ni1—N202.080 (3)C6—C81.408 (6)
Ni1—N402.085 (3)C1—C71.391 (6)
Ni1—N102.104 (3)C3—N31.146 (5)
Ni1—N302.116 (3)C3—C71.401 (6)
Ni1—N12.118 (4)C7—C21.413 (5)
N30—C311.482 (5)N2—C21.145 (5)
N30—H30A0.9000C22—C211.453 (7)
N30—H30B0.9000C22—H22A0.9700
N20—C211.418 (6)C22—H22B0.9700
N20—H20A0.9000C12—C111.517 (6)
N20—H20B0.9000C12—H12A0.9700
N1—C11.146 (5)C12—H12B0.9700
N4—C41.151 (5)C31—C321.509 (6)
N10—C111.490 (5)C31—H31A0.9700
N10—H10A0.9000C31—H31B0.9700
N10—H10B0.9000C32—H32A0.9700
C4—C81.393 (6)C32—H32B0.9700
C5—N51.148 (4)C11—H11A0.9700
C5—C81.411 (5)C11—H11B0.9700
N40—C121.479 (6)C21—H21A0.9700
N40—C321.482 (5)C21—H21B0.9700
N40—C221.488 (6)
N4—Ni1—N2092.46 (14)C4—C8—C6119.5 (3)
N4—Ni1—N40176.02 (14)C4—C8—C5121.1 (4)
N20—Ni1—N4083.56 (14)C6—C8—C5119.4 (4)
N4—Ni1—N1097.05 (13)N3—C3—C7176.9 (4)
N20—Ni1—N1094.67 (14)C1—C7—C3118.4 (3)
N40—Ni1—N1083.42 (14)C1—C7—C2119.5 (3)
N4—Ni1—N3097.20 (13)C3—C7—C2122.0 (3)
N20—Ni1—N3093.24 (13)N2—C2—C7178.6 (5)
N40—Ni1—N3082.96 (13)C21—C22—N40114.0 (4)
N10—Ni1—N30163.37 (12)C21—C22—H22A108.8
N4—Ni1—N189.55 (13)N40—C22—H22A108.8
N20—Ni1—N1177.99 (14)C21—C22—H22B108.8
N40—Ni1—N194.43 (14)N40—C22—H22B108.8
N10—Ni1—N184.97 (14)H22A—C22—H22B107.7
N30—Ni1—N186.61 (12)N40—C12—C11110.1 (3)
C31—N30—Ni1109.7 (2)N40—C12—H12A109.6
C31—N30—H30A109.7C11—C12—H12A109.6
Ni1—N30—H30A109.7N40—C12—H12B109.6
C31—N30—H30B109.7C11—C12—H12B109.6
Ni1—N30—H30B109.7H12A—C12—H12B108.2
H30A—N30—H30B108.2N30—C31—C32110.9 (4)
C21—N20—Ni1109.7 (3)N30—C31—H31A109.5
C21—N20—H20A109.7C32—C31—H31A109.5
Ni1—N20—H20A109.7N30—C31—H31B109.5
C21—N20—H20B109.7C32—C31—H31B109.5
Ni1—N20—H20B109.7H31A—C31—H31B108.1
H20A—N20—H20B108.2N40—C32—C31110.4 (4)
C1—N1—Ni1177.5 (3)N40—C32—H32A109.6
C4—N4—Ni1174.6 (3)C31—C32—H32A109.6
C11—N10—Ni1109.5 (2)N40—C32—H32B109.6
C11—N10—H10A109.8C31—C32—H32B109.6
Ni1—N10—H10A109.8H32A—C32—H32B108.1
C11—N10—H10B109.8N10—C11—C12109.0 (3)
Ni1—N10—H10B109.8N10—C11—H11A109.9
H10A—N10—H10B108.2C12—C11—H11A109.9
N4—C4—C8179.4 (4)N10—C11—H11B109.9
N5—C5—C8179.1 (4)C12—C11—H11B109.9
C12—N40—C32112.3 (3)H11A—C11—H11B108.3
C12—N40—C22110.3 (4)N20—C21—C22117.5 (4)
C32—N40—C22112.7 (4)N20—C21—H21A107.9
C12—N40—Ni1105.7 (3)C22—C21—H21A107.9
C32—N40—Ni1105.5 (3)N20—C21—H21B107.9
C22—N40—Ni1110.0 (3)C22—C21—H21B107.9
N6—C6—C8179.0 (4)H21A—C21—H21B107.2
N1—C1—C7179.1 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N30—H30A···N6i0.902.273.119 (5)158
N30—H30B···N5ii0.902.323.141 (4)152
N20—H20A···N3iii0.902.223.090 (5)164
N20—H20B···N3iv0.902.533.347 (5)151
N10—H10A···N2v0.902.383.183 (6)149
N10—H10B···N5vi0.902.383.090 (5)136
Symmetry codes: (i) x, y, z−1; (ii) −x+1/2, y−1/2, −z+1; (iii) x−1/2, −y+3/2, −z+1; (iv) −x+1/2, y+1/2, −z+1; (v) −x, −y+1, z; (vi) −x, −y+2, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N30—H30A···N6i0.902.273.119 (5)158
N30—H30B···N5ii0.902.323.141 (4)152
N20—H20A···N3iii0.902.223.090 (5)164
N20—H20B···N3iv0.902.533.347 (5)151
N10—H10A···N2v0.902.383.183 (6)149
N10—H10B···N5vi0.902.383.090 (5)136
Symmetry codes: (i) x, y, z−1; (ii) −x+1/2, y−1/2, −z+1; (iii) x−1/2, −y+3/2, −z+1; (iv) −x+1/2, y+1/2, −z+1; (v) −x, −y+1, z; (vi) −x, −y+2, z.
Acknowledgements top

This work was supported by the Slovak Grant Agency VEGA (grant No. 1/2470/05) and by APVV (grant No. 20–005204).

references
References top

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