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Acta Cryst. (2009). E65, m477    [ doi:10.1107/S1600536809011702 ]

Bis(2,3-dimethylbutane-2,3-diamine)nickel(II) dinitrate monohydrate

S.-X. Li, L.-K. Zou, B. Xie, J. Wang and J.-Z. Li

Abstract top

In the title compound, [Ni(C6H16N2)2](NO3)2·H2O, the bis(2,3-dimethylbutane-2,3-diamine)nickel(II) complex cation possesses a relatively undistorted square-planar geometry about the Ni atom, which lies on an inversion centre and is coordinated by four N atoms from two symmetry-related 2,3-diamino-2,3-dimethylbutane (tmen) ligands. The amine groups are N-H...O hydrogen bonded to the nitrate anions, which are, in turn, linked by interstitial water molecules lying on a twofold axis. The infinite zigzag chains thus formed along [001] are further connected to each other by N-H...O hydrogen bonds towards the water molecules, forming layers of two-dimensional hydrogen-bonded arrays.

Comment top

The crystal structures of [Ni(tmen)2]Cl2.2H2O and [Ni(tmen)2](tca)2 (where tmen is 2,3-diamino-2,3-dimethylbutane, tca is tricloroacetate) have been described by Aranda et al. (1977) and Beltran et al. (1978) respectively. Our interest into the Ni and Co complexs of tmen is based on their potential use as efficient mimic models of natural enzymes for phosphate hydrolysis (Cheng et al. 2002). In this work the crystal structure of the title molecule [Ni(tmen)2](NO3)2.H2O is reported.

In the title compound, the NiII atom exhibits a relatively undistorted square-planar geometry (Fig.1), which lies on an inversion centre and is coordinated by four N atoms from two tmen ligands, with Ni—N interatomic distances of 1.890 (3)–1.898 (3) Å and N—Ni—N bond angles of 85.56 (14)–94.44 (14)°. All the other bond lengths and angles in the complex are generally within normal ranges (Allen et al., 1987).

A striking feature of this compound resides in its zigzag chain structure formed through hydrogen bonds, with a solvate water molecule lying on a two fold axis, as depicted in Fig.2. The amine groups are N—H···O hydrogen bonding to the nitrate anions which are in turn linked by interstitial water molecules. The zigzag structure is composed of (tmen ligand) N—H···O (nitrate anion) and (water molecule) O—H···O (nitrate anion) hydrogen bonds (Table 1). The N—H···O distances for the hydrogen bonding of the tmen ligand and the nitrate anion range from 2.936 (7) to 3.048 (7) Å in the chain. Both O—H···O hydrogen bonds for the uncoordinated water molecule are 2.824 (6) Å. The thus formed infinite zigzag chains along [001] are further connected with each other by N—H···O hydrogen bonds towards the water molecules to form layers of two-dimensional hydrogen bonded arrays, as shown in Fig.3.

Related literature top

For general background, see: Cheng et al. (2002). For related structures, see: Aranda et al. (1977); Beltran et al. (1978). For bond-length data, see Allen et al. (1987).

Experimental top

2,3-Diamino-2,3-dimethylbutane (tmen) (0.232 g, 2 mmol) and Ni(NO3)2.6H2O (0.291 g, 1 mmol) were dissolved in 20 ml distilled water, the solution was filtrated and the filtrate was kept at room temperature for six months after which yellow to green crystals suitable for X-ray diffraction studies were obtained, yield 37%. Selected infrared spectral (KBr) data (cm-1): ν[O—H] = 3399.9, ν[N—H] = 3187.1 and 3093.7, ν[N—O] = 1384.8, δ[N—H] = 1601.2.

Refinement top

H atoms on C and N atoms were fixed geometrically and constrained to ride on their parent atoms, with C—H = 0.96 Å (methyl) and N—H = 0.90 Å, and with Uiso(H) = 1.2Ueq(N) or Uiso(H) = 1.5Ueq(C). The water H atoms were determined with difference Fourier syntheses and refined isotropically.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 20% probability level. H atoms are represented as small spheres of arbitrary radii. [Symmetry code: (ii) -x + 1,-y, -z].
[Figure 2] Fig. 2. A view of the zigzag chain with hydrogen bonds shown as dashed lines, H atoms on the C atoms have been omitted for the sake of clarity.
[Figure 3] Fig. 3. A view of the two-dimensional hydrogen bonded array with hydrogen bonds shown as dashed lines. H atoms on the C atoms have been omitted for the sake of clarity.
Bis(2,3-dimethylbutane-2,3-diamine)nickel(II) dinitrate monohydrate top
Crystal data top
[Ni(C6H16N2)2](NO3)2·H2OF(000) = 928
Mr = 433.14Dx = 1.398 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 20 reflections
a = 21.788 (3) Åθ = 4.4–7.1°
b = 7.892 (3) ŵ = 0.99 mm−1
c = 13.997 (4) ÅT = 292 K
β = 121.26 (3)°Block, yellow-green
V = 2057.4 (12) Å30.50 × 0.46 × 0.40 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer		1314 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.020
graphiteθmax = 25.5°, θmin = 2.2°
ω/2θ scansh = −26→22
Absorption correction: for a sphere
(PLATON; Spek, 2009)		k = −3→9
Tmin = 0.638, Tmax = 0.694l = −16→16
2099 measured reflections3 standard reflections every 100 reflections
1895 independent reflections intensity decay: 0.8%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.054H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.165 w = 1/[σ2(Fo2) + (0.0951P)2 + 1.294P]
where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
1895 reflectionsΔρmax = 0.96 e Å−3
129 parametersΔρmin = −0.65 e Å−3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0084 (13)
Crystal data top
[Ni(C6H16N2)2](NO3)2·H2OV = 2057.4 (12) Å3
Mr = 433.14Z = 4
Monoclinic, C2/cMo Kα radiation
a = 21.788 (3) ŵ = 0.99 mm−1
b = 7.892 (3) ÅT = 292 K
c = 13.997 (4) Å0.50 × 0.46 × 0.40 mm
β = 121.26 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		1314 reflections with I > 2σ(I)
Absorption correction: for a sphere
(PLATON; Spek, 2009)		Rint = 0.020
Tmin = 0.638, Tmax = 0.694θmax = 25.5°
2099 measured reflections3 standard reflections every 100 reflections
1895 independent reflections intensity decay: 0.8%
Refinement top
R[F2 > 2σ(F2)] = 0.054H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.165Δρmax = 0.96 e Å−3
S = 1.09Δρmin = −0.65 e Å−3
1895 reflectionsAbsolute structure: ?
129 parametersFlack parameter: ?
1 restraintRogers parameter: ?
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
xyzUiso*/Ueq
Ni10.50000.00000.00000.0472 (3)
N10.57151 (17)−0.1127 (5)−0.0139 (3)0.0616 (10)
H1A0.5944−0.18690.04280.074*
H1B0.5503−0.1720−0.07810.074*
N20.56062 (17)0.1927 (5)0.0399 (3)0.0605 (9)
H2A0.54150.2668−0.01720.073*
H2B0.56290.24380.09920.073*
C10.6937 (2)−0.0917 (8)0.0195 (5)0.0874 (17)
H1C0.7082−0.15570.08630.131*
H1D0.7311−0.01340.03280.131*
H1E0.6851−0.1674−0.03990.131*
C20.6254 (2)0.0057 (6)−0.0131 (4)0.0668 (12)
C30.6356 (2)0.1470 (6)0.0685 (4)0.0668 (13)
C40.6736 (3)0.3029 (7)0.0615 (5)0.0790 (14)
H4A0.71930.27100.07250.119*
H4B0.68050.38220.11820.119*
H4C0.64490.3543−0.01080.119*
C50.5928 (3)0.0831 (9)−0.1304 (4)0.0931 (17)
H5A0.5753−0.0059−0.18510.140*
H5B0.62880.1469−0.13450.140*
H5C0.55380.1566−0.14480.140*
C60.6758 (3)0.0776 (9)0.1912 (4)0.0881 (17)
H6A0.6539−0.02640.19370.132*
H6B0.67290.15940.23950.132*
H6C0.72530.05740.21550.132*
O10.6199 (3)0.4468 (7)0.2673 (5)0.1304 (19)
O20.5352 (3)0.5668 (9)0.1343 (6)0.163 (3)
O30.6359 (3)0.6686 (7)0.1958 (5)0.1408 (19)
N30.5972 (3)0.5628 (7)0.1999 (5)0.0856 (13)
OW0.50000.2793 (8)0.25000.115 (2)
HW10.540 (4)0.342 (12)0.271 (10)0.26 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0355 (4)0.0458 (4)0.0616 (5)−0.0018 (3)0.0261 (3)−0.0082 (4)
N10.0446 (18)0.061 (2)0.085 (3)0.0038 (16)0.0371 (18)−0.0057 (19)
N20.0505 (19)0.0500 (19)0.085 (3)−0.0051 (15)0.0379 (19)−0.0108 (19)
C10.051 (3)0.102 (4)0.120 (5)0.010 (3)0.053 (3)−0.003 (4)
C20.047 (2)0.081 (3)0.080 (3)−0.005 (2)0.038 (2)−0.001 (3)
C30.043 (2)0.073 (3)0.084 (3)−0.010 (2)0.033 (2)−0.009 (3)
C40.063 (3)0.080 (3)0.095 (4)−0.023 (3)0.042 (3)−0.001 (3)
C50.087 (4)0.125 (5)0.071 (3)−0.017 (4)0.044 (3)0.001 (4)
C60.062 (3)0.120 (5)0.066 (3)−0.016 (3)0.022 (3)0.006 (3)
O10.097 (3)0.123 (4)0.154 (5)0.028 (3)0.053 (3)0.068 (4)
O20.104 (4)0.145 (4)0.174 (6)0.009 (4)0.024 (4)0.071 (4)
O30.143 (4)0.101 (4)0.188 (6)−0.010 (3)0.093 (4)0.025 (4)
N30.087 (3)0.061 (3)0.117 (4)0.012 (3)0.059 (3)0.000 (3)
OW0.151 (7)0.076 (4)0.142 (6)0.0000.093 (6)0.000
Geometric parameters (Å, °) top
Ni1—N11.890 (3)C3—C41.513 (6)
Ni1—N1i1.890 (3)C3—C61.567 (7)
Ni1—N21.898 (3)C4—H4A0.9600
Ni1—N2i1.898 (3)C4—H4B0.9600
N1—C21.496 (5)C4—H4C0.9600
N1—H1A0.9000C5—H5A0.9600
N1—H1B0.9000C5—H5B0.9600
N2—C31.510 (5)C5—H5C0.9600
N2—H2A0.9000C6—H6A0.9600
N2—H2B0.9000C6—H6B0.9600
C1—C21.520 (6)C6—H6C0.9600
C1—H1C0.9600O1—N31.220 (7)
C1—H1D0.9600O2—N31.176 (6)
C1—H1E0.9600O3—N31.209 (6)
C2—C31.528 (7)OW—HW10.91 (11)
C2—C51.537 (7)
N1—Ni1—N1i180.0C3—C2—C5108.4 (4)
N1—Ni1—N285.56 (14)N2—C3—C4110.0 (4)
N1i—Ni1—N294.44 (14)N2—C3—C2105.0 (3)
N1—Ni1—N2i94.44 (14)C4—C3—C2114.7 (4)
N1i—Ni1—N2i85.56 (14)N2—C3—C6106.6 (4)
N2—Ni1—N2i180.0C4—C3—C6110.0 (4)
C2—N1—Ni1113.0 (3)C2—C3—C6110.2 (4)
C2—N1—H1A109.0C3—C4—H4A109.5
Ni1—N1—H1A109.0C3—C4—H4B109.5
C2—N1—H1B109.0H4A—C4—H4B109.5
Ni1—N1—H1B109.0C3—C4—H4C109.5
H1A—N1—H1B107.8H4A—C4—H4C109.5
C3—N2—Ni1112.2 (3)H4B—C4—H4C109.5
C3—N2—H2A109.2C2—C5—H5A109.5
Ni1—N2—H2A109.2C2—C5—H5B109.5
C3—N2—H2B109.2H5A—C5—H5B109.5
Ni1—N2—H2B109.2C2—C5—H5C109.5
H2A—N2—H2B107.9H5A—C5—H5C109.5
C2—C1—H1C109.5H5B—C5—H5C109.5
C2—C1—H1D109.5C3—C6—H6A109.5
H1C—C1—H1D109.5C3—C6—H6B109.5
C2—C1—H1E109.5H6A—C6—H6B109.5
H1C—C1—H1E109.5C3—C6—H6C109.5
H1D—C1—H1E109.5H6A—C6—H6C109.5
N1—C2—C1109.2 (4)H6B—C6—H6C109.5
N1—C2—C3105.7 (4)O2—N3—O3119.4 (7)
C1—C2—C3113.9 (4)O2—N3—O1117.7 (6)
N1—C2—C5108.3 (4)O3—N3—O1122.8 (6)
C1—C2—C5111.1 (5)
N2—Ni1—N1—C2−12.6 (3)N1—C2—C3—N2−44.8 (5)
N2i—Ni1—N1—C2167.4 (3)C1—C2—C3—N2−164.7 (4)
N1—Ni1—N2—C3−14.8 (3)C5—C2—C3—N271.2 (4)
N1i—Ni1—N2—C3165.2 (3)N1—C2—C3—C4−165.6 (4)
Ni1—N1—C2—C1158.7 (4)C1—C2—C3—C474.5 (6)
Ni1—N1—C2—C335.8 (4)C5—C2—C3—C4−49.7 (5)
Ni1—N1—C2—C5−80.2 (4)N1—C2—C3—C669.7 (4)
Ni1—N2—C3—C4161.1 (3)C1—C2—C3—C6−50.2 (5)
Ni1—N2—C3—C237.2 (4)C5—C2—C3—C6−174.4 (4)
Ni1—N2—C3—C6−79.8 (4)
Symmetry codes: (i) −x+1, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3ii0.902.173.048 (7)166
N1—H1B···OWi0.902.233.120 (5)170
N2—H2A···O2iii0.902.092.936 (7)157
OW—HW1···O10.91 (11)1.95 (11)2.824 (6)160 (12)
OW—HW1···O20.91 (11)2.57 (11)3.106 (8)118 (9)
Symmetry codes: (ii) x, y−1, z; (i) −x+1, −y, −z; (iii) −x+1, −y+1, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3i0.902.173.048 (7)166
N1—H1B···OWii0.902.233.120 (5)170
N2—H2A···O2iii0.902.092.936 (7)157
OW—HW1···O10.91 (11)1.95 (11)2.824 (6)160 (12)
OW—HW1···O20.91 (11)2.57 (11)3.106 (8)118 (9)
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y, −z; (iii) −x+1, −y+1, −z.
Acknowledgements top

Financial assistance from the Education Department of Sichuan Province, People's Republic of China (Project Nos. 2005 A146 and 07ZA161) is gratefully acknowledged.

references
References top

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