[μ-(4S,5S,15S,16S)-10,21-Di-tert-butyl-4,5,15,16-tetra­phenyl-3,6,14,17-tetra­aza­tricyclo­[17.3.1.18,12]tetra­cosa-1(23),8,10,12(24),19,21-hexa­ene-23,24-diolato-κ8 N 3,N 6,O 23,O 24:N 14 N 17,O 23,O 24]bis­[(acetato-κO)zinc(II)] ethanol disolvate

Li-Jing Fan; Jian-Fang Ma; Jie Liu

doi:10.1107/S1600536809021990

. 2009 Jun 17;65(Pt 7):m777–m778. doi: 10.1107/S1600536809021990

[μ-(4S,5S,15S,16S)-10,21-Di-tert-butyl-4,5,15,16-tetraphenyl-3,6,14,17-tetraazatricyclo[17.3.1.1^8,12]tetracosa-1(23),8,10,12(24),19,21-hexaene-23,24-diolato-κ⁸ N ³,N ⁶,O ²³,O ²⁴:N ¹⁴ N ¹⁷,O ²³,O ²⁴]bis[(acetato-κO)zinc(II)] ethanol disolvate

Li-Jing Fan ^a,^*, Jian-Fang Ma ^a, Jie Liu ^a

PMCID: PMC2969517 PMID: 21582707

Abstract

In the title compound, [Zn₂(C₃₆H₄₂N₄O₂)(CH₃COO)₂]·2CH₃CH₂OH, a centrosymmetric dinuclear zinc macrocyclic complex is accompanied by two half-occupied ethanol solvent molecues resulting in a 1:2 macrocycle–solvent composition. The Zn^II atom has a square-pyramidal geometry arising from an N₂O₃ donor set, being coordinated by two N atoms and two O atoms from the macrocyclic ligand in the equatorial sites and one O atom from an acetate anion in the apical site. The two Zn^II atoms are linked by two phenolate O atoms, generating a four-membered Zn₂O₂ ring at the centre of the macrocycle. The tert-butyl group shows rotational disorder over two sets of sites in a 0.552 (12):0.448 (12) ratio. In the crystal, N—H⋯O and O—H⋯O hydrogen bonds are seen and a short intramolecular C—H⋯O contact occurs.

Related literature

For background to the biochemistry of zinc compounds, see: Lipscomb & Straeter (1996 ▶); Burley et al. (1990 ▶); Roderick & Mathews (1993 ▶); Bazzicalupi et al. (1997 ▶). For related structures, see: Dutta et al. (2005 ▶); Liu et al. (2007 ▶). For further synthetic details, see: Tian et al. (1999 ▶).

Experimental

Crystal data

[Zn₂(C₃₆H₄₂N₄O₂)(C₂H₃O₂)₂]·2C₂H₆O
M _r = 903.70
Triclinic,
a = 9.0566 (3) Å
b = 10.8410 (5) Å
c = 14.2828 (5) Å
α = 71.246 (4)°
β = 86.514 (3)°
γ = 78.362 (3)°
V = 1300.56 (9) Å³
Z = 1
Mo Kα radiation
μ = 0.97 mm⁻¹
T = 293 K
0.45 × 0.25 × 0.20 mm

Data collection

Oxford Diffraction Gemini R Ultra diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 ▶) T _min = 0.748, T _max = 0.824
11846 measured reflections
6368 independent reflections
4133 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.077
wR(F ²) = 0.253
S = 1.05
6368 reflections
285 parameters
655 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.15 e Å⁻³
Δρ_min = −0.77 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809021990/hb2961sup1.cif

e-65-0m777-sup1.cif^{(24.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809021990/hb2961Isup2.hkl

e-65-0m777-Isup2.hkl^{(305.4KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Zn1—O1	2.025 (5)
Zn1—O3	2.033 (4)
Zn1—O3ⁱ	2.043 (4)
Zn1—N2	2.100 (5)
Zn1—N1	2.104 (5)

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Symmetry code: (i) Inline graphic .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O2	0.97	2.45	3.246 (10)	139
N1—H1N⋯O4	0.86 (7)	2.23 (7)	2.952 (9)	141 (6)
N2—H2N⋯O5ⁱⁱ	0.87 (4)	2.13 (4)	2.999 (9)	175 (4)
O4—H4⋯O2ⁱⁱⁱ	0.82	2.06	2.768 (10)	145
O5—H5⋯O1^iv	0.82	1.92	2.700 (9)	159

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

Acknowledgments

The authors thank the National Natural Science Foundation of China (No. 20471014), the Program for New Century Excellent Talents in Chinese Universities (NCET-05–0320), the Fok Ying Tung Education Foundation and the Analysis and Testing Foundation of Northeast Normal University for support.

supplementary crystallographic information

Comment

Zinc is an essential element for all forms of life and plays a critical role in various functions, both structural and catalytic, in proteins and enzymes (Lipscomb et al.,1996; Burley et al.,1990; Roderick & Mathews, 1993). In addition, some synthetic dinuclear zinc(II) compounds appears to have functions in dephosphorylation (Bazzicalupi et al.,1997). As part of out studies in this area, the title compound, (I), a new dinuclear zinc(II) compound has been synthesized, and its structure is reported here (Fig. 1).

The complete macrocycle is generated by a crystallographic inversion centre The coordination environment around zinc is a square-pyramid with two N atoms and two O atoms from the macrocyclic (C₃₆H₄₄N₄O₂) ligand occupying the basal positions and one O atom from a acetate anion occupying the apical position. The two zinc atoms are bridged by two phenolate O atoms to generate a four-membered Zn₂O₂ring. The Zn—O and Zn—N distances are normal (Dutta et al., 2005).

Experimental

To a stirred methanol (30 ml) suspension of the schiff base C₃₆H₄₀N₄O₂ (0.5 mmol), which was synthesized by the methods reported previously (Tian et al., 1999), was added solid NaBH₄ (0.5 g, 13 mmol) in small portions. Over a period of 0.5 h when the red solid material gradually went into solution, and eventually an amorphous yellow mass precipitated. After 1 h, the formed yellow powder products (H₂L) were filtrated off and washed thoroughly with water and ethanol, and dried in avacuum (yield 54%).

The title compound was prepared by reaction between the ligand (H₂L) and zinc acetate. A mixture of H₂L (0.108 g, 0.2 mmol) and Zn(OAc)₂.6H₂O (0.117 g, 0.4 mmol) in ethanol (20 ml) was heated with stirring to yield a clear pale yellow solution. Filtration and cooling to room temperature resulted in formation of a crystalline precipitate. Recrystallization by slow evaporation of an ethanol solution of the compound resulted in well-formed yellow blocks of (I) (yield 46%).