(Benzoato-κ2 O,O′)(5,5,7,12,12,14-hexa­methyl-1,4,8,11-tetra­azacyclo­tetra­decane-κ4 N,N′,N′′,N′′′)nickel(II) perchlorate monohydrate

Guang-Chuan Ou; Min Zhang; Xian-You Yuan

doi:10.1107/S1600536808020564

. 2008 Jul 9;64(Pt 8):m1010. doi: 10.1107/S1600536808020564

(Benzoato-κ² O,O′)(5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ⁴ N,N′,N′′,N′′′)nickel(II) perchlorate monohydrate

Guang-Chuan Ou ^a,^*, Min Zhang ^a, Xian-You Yuan ^a

PMCID: PMC2961933 PMID: 21203004

Abstract

The Ni atom in the title salt, [Ni(C₇H₅O₂)(C₁₆H₃₆N₄)]ClO₄·H₂O, is in a six-coordinate octahedral geometry. The metal atom is chelated by the carboxylate group, and the macrocyclic ligand adopts a folded configuration. The cation, anion and water molecules engage in hydrogen bonding to form a layer structure.

Related literature

For related literature, see: Jiang et al. (2005 ▶); Ou et al. (2008 ▶).

Experimental

Crystal data

[Ni(C₇H₅O₂)(C₁₆H₃₆N₄)]ClO₄·H₂O
M _r = 581.77
Monoclinic,
a = 15.1239 (14) Å
b = 8.9351 (8) Å
c = 20.9918 (19) Å
β = 102.414 (2)°
V = 2770.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.84 mm⁻¹
T = 173 (2) K
0.48 × 0.40 × 0.21 mm

Data collection

Bruker SMART diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.688, T _max = 0.843
15892 measured reflections
6007 independent reflections
4802 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.121
S = 1.10
6007 reflections
337 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808020564/ng2469sup1.cif

e-64-m1010-sup1.cif^{(29.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808020564/ng2469Isup2.hkl

e-64-m1010-Isup2.hkl^{(294.1KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Ni1—N4	2.0859 (19)
Ni1—N2	2.1053 (18)
Ni1—N3	2.117 (2)
Ni1—N1	2.1333 (19)
Ni1—O1	2.1379 (17)
Ni1—O2	2.1698 (16)

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O1—Ni1—O2

61.52 (6)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1W	0.93	2.16	3.080 (3)	168
O1W—H1D⋯O6	0.844 (19)	2.12 (3)	2.934 (4)	162 (6)
O1W—H1E⋯O2	0.86 (2)	2.18 (4)	2.931 (3)	146 (5)

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Acknowledgments

This work was supported financially by the Foundation for University Key Teachers of the Education Department of Hunan Province, and the Key Subject Construction Project of Hunan Province (grant No. 2006-180).

supplementary crystallographic information

Comment

It's important to control the geometries of ML²⁺ [M = Ni(II), Co(II), Cu(II)] with cis- or trans-conformation, since they form different structures and show different properties (Jiang et al., 2005). A racemic nickel(II) complex with cis-conformation can be separated to two enantiomers by the reactions of [Ni(rac-L)]²⁺ with chiral amino acid such as phenylalanine (Ou et al., 2008). Then we employ no chiral benzoic acid as separation reagent, but the result of experiment indicate a racemic complex of [Ni(rac-L)(bz)(ClO₄)]H₂O is obtained instead of two enantiomers. In the asymmetric unit of (I), contains one [Ni(rac-L)(bz)]⁺ cation, one [ClO₄]^- anion and one water molecule. As illustrated in Fig.1, The six-coordinated Ni²⁺ of [Ni(rac-L)(bz)]⁺ cation display a distorted octahedral geometry by coordination with four N atoms of macrocyclic ligand L in a folded configuration, and two carboxylate oxygen atoms of benzoic acid in cis-position. The Ni—N distances ranging from 2.086 (19) to 2.133 (19) Å, are slight shorter than the Ni—O distance [2.138 (17) to 2.170 (16) Å] (Table 1). Neighbouring cations and anions are discrete, connected to each other through two intermolecular hydrogen bond (Table 2), water and oxygen atom of benzoato anion, and water and oxygen atom of [ClO₄]^- anion (See Fig. 2).

Experimental

benzoic acid (H₂bz, 0.122 g, 1 mmol) was mixed with NaOH (0.040 g, 1 mmol) dissolved in 10 ml of water. To this solution was added [Ni(rac-L)](ClO₄)₂ (0.541 g, 1 mmol) dissolved in a minimum amount of CH₃CN. The solution was left to stand at room temperature and blue crystals formed after several weeks(yield 53%).