Di-μ-chlorido-dichlorido-bis{μ-6,6′-dimethoxy-2,2′-[o-phenylenebis(nitrilomethylidyne)]diphenolato}dilead(II)dizinc(II) N,N′-dimethyl­formamide disolvate

Hailong Wang; Daopeng Zhang; Li-Fang Zhang

doi:10.1107/S1600536808032704

. 2008 Oct 15;64(Pt 11):m1408–m1409. doi: 10.1107/S1600536808032704

Di-μ-chlorido-dichlorido-bis{μ-6,6′-dimethoxy-2,2′-[o-phenylenebis(nitrilomethylidyne)]diphenolato}dilead(II)dizinc(II) N,N′-dimethylformamide disolvate

Hailong Wang ^a, Daopeng Zhang ^a, Li-Fang Zhang ^a,^*

PMCID: PMC2959539 PMID: 21580858

Abstract

The title compound, [Pb₂Zn₂(C₂₂H₁₈N₂O₄)₂Cl₄]·2C₃H₇NO, was synthesized using a step-by-step method and has a slipped sandwich configuration. The coordination environment of the Zn²⁺ ion is distorted square-pyramidal and it is coordinated by N₂O₂ of the Schiff base ligand and chloride; each Pb²⁺ ion is coordinated by the four 6,6′-dimethoxy-2,2′-[o-phenylenebis(nitrilomethylidyne)]diphenolate (L) O atoms and two chloride ions. The Zn^IIPb^II dinuclear unit, through an inversion-symmetry operation, forms a tetrameric complex with double chloride bridges.

Related literature

For related literature, see: Karlin (1993 ▶); Korupoju et al. (2000 ▶); Lo et al. (2004 ▶); Ni et al. (2005 ▶); Sui et al. (2007 ▶); Ward (2007 ▶).

Experimental

Crystal data

[Pb₂Zn₂(C₂₂H₁₈N₂O₄)₂Cl₄]·2C₃H₇NO
M _r = 1581.88
Monoclinic,
a = 7.4955 (6) Å
b = 32.119 (3) Å
c = 11.2366 (9) Å
β = 95.729 (2)°
V = 2691.7 (4) Å³
Z = 2
Mo Kα radiation
μ = 7.38 mm⁻¹
T = 295 (2) K
0.20 × 0.15 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.320, T _max = 0.526 (expected range = 0.291–0.478)
13373 measured reflections
4719 independent reflections
3176 reflections with I > 2σ(I)
R _int = 0.063

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.066
S = 0.93
4719 reflections
336 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: XP in SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808032704/kp2192sup1.cif

e-64-m1408-sup1.cif^{(22.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808032704/kp2192Isup2.hkl

e-64-m1408-Isup2.hkl^{(226.5KB, hkl)}

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

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

N1—Zn1	2.062 (5)
N2—Zn1	2.064 (5)
O1—Pb1	2.720 (5)
O2—Zn1	2.026 (4)
O2—Pb1	2.408 (4)
O3—Zn1	2.025 (4)
O3—Pb1	2.386 (4)
O4—Pb1	2.690 (5)
Zn1—Cl1	2.2544 (18)
Pb1—Cl2	2.6138 (18)

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O3—Zn1—O2	80.49 (16)
O3—Zn1—N1	144.11 (18)
O2—Zn1—N1	88.19 (18)
O3—Zn1—N2	88.00 (18)
O2—Zn1—N2	141.06 (18)
N1—Zn1—N2	79.7 (2)
O3—Zn1—Cl1	107.95 (13)
O2—Zn1—Cl1	108.74 (13)
N1—Zn1—Cl1	107.94 (14)
N2—Zn1—Cl1	110.20 (15)
O3—Pb1—O2	66.18 (14)
O3—Pb1—Cl2	89.13 (11)
O2—Pb1—Cl2	91.86 (10)
O3—Pb1—O4	61.20 (14)
O2—Pb1—O4	127.37 (14)
Cl2—Pb1—O4	88.05 (11)
O3—Pb1—O1	126.94 (14)
O2—Pb1—O1	60.79 (14)
Cl2—Pb1—O1	94.14 (12)
O4—Pb1—O1	171.53 (14)

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Acknowledgments

This work was supported by the Natural Science Foundation of China and the Post-Doctoral Innovation Project of Shandong Province.

supplementary crystallographic information

Comment

Heterometallic complexes have been intensively studied owing to their unique physical and chemical properties (Ward et al., 2007 and Ni et al., 2005). In addition, these compounds exist at the active sites of many metalloenzymes and play important roles in biological systems (Karlin, 1993). It is necessary to extend the application of heterometallic compounds. Herein, a novel heterometallic tetranuclear (Zn^IIPb^II)₂ compound has been obtained using step-by-step method and its structure is depcited.

The compound I is a tetranuclear neutral complex with a slipped sandwich configuration (Fig. 1). Each Zn(II) is coordinated in a square-pyramidal geometry with the basal square formed by two nitrogen atoms and two oxygen atoms from L ligand, with the apical position occupied by terminal chlorine atom. The coordination environment of each Pb(II) is a distorted octahedral geometry composed of four oxygen atoms from ligand and two bridging chlorine atoms. Zn(II) and Pb(II) are connected via two bridging oxygen atoms of the ligand, and two Pb(II) atoms are connected by two bridging chlorine atoms. The bond lengths of Zn—O, Zn—N and Zn—Cl are normal (Korupoju et al., 2000). Through π-π interaction between the rings C9—C14 and C16—C21 [symmetry code; (i) -1 + x, y, z] with centroid distance of 3.730 (3) /A [Cg1··· Cg2ⁱ ] the discrete tetranuclear (Zn^IIPb^II)₂ units forms a supramolecular structure (Fig. 2).

Experimental

The H₂L ligand and complex ZnL was synthesized according to the literature (Lo et al., 2004; Sui et al. 2007). Synthesis of the compound I was obtained by allowing the mixure of ZnL (0.088 g, 0.2 mmol) and PbCl₂.2H₂O(0.063 g, 0.2 mmol) to be refluxed in the DMF solution, cooled down to room temperature, then filtered, and suitable yellow crystals were obtained by slow evaporation of the filtrate at room temperature (yield: about 45%).