(Acetato-κO)(aqua-κO)(2-{bis­[(3,5-dimethyl-1H-pyrazol-1-yl-κN 2)methyl]amino-κN}ethanol-κO)nickel(II) perchlorate monohydrate

Jia Zhou; Mouhai Shu

doi:10.1107/S1600536812007970

. 2012 Mar 10;68(Pt 4):m399. doi: 10.1107/S1600536812007970

(Acetato-κO)(aqua-κO)(2-{bis[(3,5-dimethyl-1H-pyrazol-1-yl-κN ²)methyl]amino-κN}ethanol-κO)nickel(II) perchlorate monohydrate

Jia Zhou ^a, Mouhai Shu ^a,^*

PMCID: PMC3343810 PMID: 22589784

Abstract

In the structure of the title complex, [Ni(CH₃CO₂)(C₁₄H₂₃N₅O)(H₂O)]ClO₄·H₂O, the Ni^II centre has a distorted octahedral environment defined by one O and three N atoms derived from the tetradentate ligand, and two O atoms, one from a water molecule and the other from an acetate anion. The molecules are connected into a three-dimensional architecture by O—H⋯O hydrogen bonds. The perchlorate anion is disordered over two positions; the major component has a site-occupancy factor of 0.525 (19).

Related literature

For the preparation of the tripodal ligand, see: Malachowski et al. (1992 ▶). For background to hydrolytic enzymes, see: Koike et al. (1995 ▶); Lipscomb & Sträter (1996 ▶). For related structures, see: Shin et al. (2011 ▶); Sundaravel et al. (2011 ▶); Xia et al. (2001 ▶).

Experimental

Crystal data

[Ni(C₂H₃O₂)(C₁₄H₂₃N₅O)(H₂O)]ClO₄·H₂O
M _r = 530.61
Monoclinic,
a = 9.6055 (11) Å
b = 9.9889 (11) Å
c = 24.258 (3) Å
β = 90.284 (2)°
V = 2327.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.00 mm⁻¹
T = 293 K
0.43 × 0.37 × 0.21 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 2003 ▶) T _min = 0.732, T _max = 1.000
13249 measured reflections
5057 independent reflections
2284 reflections with I > 2σ(I)
R _int = 0.082

Refinement

R[F ² > 2σ(F ²)] = 0.059
wR(F ²) = 0.142
S = 0.82
5057 reflections
310 parameters
26 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812007970/tk5060sup1.cif

e-68-0m399-sup1.cif^{(26.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812007970/tk5060Isup2.hkl

e-68-0m399-Isup2.hkl^{(247.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812007970/tk5060Isup3.mol

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H26⋯O3ⁱ	0.86 (1)	1.80 (1)	2.631 (10)	163 (1)
O4—H27⋯O5ⁱⁱ	0.86 (1)	2.03 (1)	2.882 (10)	171 (1)
O4—H28⋯O3	0.86 (1)	1.87 (1)	2.684 (10)	158 (5)
O5—H29⋯O11′	0.86 (1)	1.84 (1)	2.695 (10)	174 (1)
O5—H29⋯O11	0.86 (1)	2.09 (1)	2.940 (10)	168 (1)
O5—H30⋯O12′ⁱⁱⁱ	0.86 (1)	2.59 (1)	3.162 (10)	125 (1)

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

Acknowledgments

The authors thank Professor D.-J. Xu, Zhejiang University, China, for his helpful suggestions.

supplementary crystallographic information

Comment

Zn^II-bound alkoxides, resulting from the deprotonation of the Zn^II-coordinated alcoholic hydroxides in Zn^II-containing enzymes (Lipscomb & Sträter, 1996), usually act as nucleophiles to attack the substrates (e.g. phosphates, CO₂, and carboxy esters). Polyamines with a pendant ethoxyl group can mimic the chemical surroundings of Zn^II in the active site of the Zn^II-containing enzymes (Koike et al., 1995). This encouraged us to investigate the coordination chemistry of transition metal ions with a new ligand containing a N₃O donor set. In this work, N,N-bis(3,5-dimethyl-pyrazol-1-yl-methylene)aminoethanol (Malachowski et al., 1992) was reacted with nickel acetate in the presence of sodium perchlorate to yield the title complex as blue crystals in 68% yield. Related structures have been reported previously (Shin et al., 2011; Sundaravel et al., 2011; Xia et al., 2001).

In the structure, the Ni^II cation has a six-coordinated geometry consisting of three N atoms and an O atom from the organic ligand, and two O atoms from a water molecule and an acetate (Fig. 1). The Ni—N_pyrazolyl bond distances are 2.071 (4) and 2.044 (4) Å, which are shorter than the Ni—N_amino bond length (2.124 (3) Å). The Ni—O_acetate bond distance is 1.999 (3) Å, which is about 0.1 Å shorter than those of Ni—O_alcohol (2.097 (3) Å) and Ni—O_water (2.126 (4) Å). The cis bond angles are deviate from 90° by about 10°, and the trans bond angles deviate from 180° by about 20°. Therefore, the coordination geometry of the Ni^II centre is a distorted octahedron. In the crystal, there are O—H···O hydrogen bonds. The unit contents are illustrated in Fig. 2.

Experimental

A solution of Ni(OAc)₂.4H₂O(0.2 mmol) in 2 ml H₂O was added dropwise to a solution of N,N-bis(3,5-dimethyl-pyrazol-1-yl-methylene-)aminoethanol (0.2 mmol) in 10 ml of methanol. The blue solution was stirred for 30 min and a drop of saturated NaClO₄ solution was added to the mixture. The clear solution in a test tube was left undisturbed. Blue crystals were obtained after a week.