Tris(1,10-phenanthroline-5,6-dione-κ2 N,N′)zinc bis­(perchlorate) acetonitrile monosolvate

Jing Zhao; Heng Zhang; Zhaozhi Zhang; Haiyan Zhao; Guoyi Zhu

doi:10.1107/S1600536811037081

. 2011 Sep 30;67(Pt 10):m1422–m1423. doi: 10.1107/S1600536811037081

Tris(1,10-phenanthroline-5,6-dione-κ² N,N′)zinc bis(perchlorate) acetonitrile monosolvate

Jing Zhao ^a, Heng Zhang ^b, Zhaozhi Zhang ^c, Haiyan Zhao ^d, Guoyi Zhu ^a,^*

PMCID: PMC3201451 PMID: 22064769

Abstract

In the title compound, [Zn(C₁₂H₆N₂O₂)₃](ClO₄)₂·CH₃CN, the Zn^II atom is coordinated by six N atoms from three chelating 1,10-phenanthroline-5,6-dione ligands in a distorted octahedral environment. In the crystal, intermolecular C—H⋯O hydrogen bonds and O⋯π and N⋯π interactions [O⋯centroid distances = 2.907 (5) and 2.843 (7) Å; N⋯centroid distance = 2.861 (10) Å] link the complex cations, perchlorate anions and acetonitrile solvent molecules into a three-dimensional network.

Related literature

For the coordination chemistry of 1,10-phenanthroline-5,6-dione, see: Brechin et al. (2008 ▶); Khalaji et al. (2007 ▶); Ma et al. (2010 ▶); Rezvani et al. (2010 ▶). For the biological and electrochemical properties of transition metal complexes with 1,10-phenanthroline-5,6-dione, see: Boghaei & Asl (2007 ▶); Goss & Abruna (1985 ▶); Kou et al. (2009 ▶).

Experimental

Crystal data

[Zn(C₁₂H₆N₂O₂)₃](ClO₄)₂·C₂H₃N
M _r = 935.91
Orthorhombic,
a = 13.446 (6) Å
b = 14.125 (6) Å
c = 20.483 (8) Å
V = 3890 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.85 mm⁻¹
T = 296 K
0.30 × 0.12 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.785, T _max = 0.905
23200 measured reflections
9569 independent reflections
5533 reflections with I > 2σ(I)
R _int = 0.079

Refinement

R[F ² > 2σ(F ²)] = 0.075
wR(F ²) = 0.220
S = 0.97
9569 reflections
562 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.16 e Å⁻³
Δρ_min = −0.39 e Å⁻³
Absolute structure: Flack (1983 ▶), 4095 Friedel pairs
Flack parameter: 0.12 (2)

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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 datablock(s) I, global. DOI: 10.1107/S1600536811037081/hy2471sup1.cif

e-67-m1422-sup1.cif^{(25.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037081/hy2471Isup2.hkl

e-67-m1422-Isup2.hkl^{(468KB, hkl)}

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
C1—H14⋯O13ⁱ	0.93	2.51	3.238 (9)	135
C2—H15⋯O3ⁱⁱ	0.93	2.58	3.030 (13)	110
C10—H12⋯O7ⁱⁱⁱ	0.93	2.59	3.513 (14)	170
C25—H17⋯O4ⁱⁱ	0.93	2.51	3.136 (15)	125
C24—H26⋯O2^iv	0.93	2.36	3.036 (10)	129
C34—H7⋯O9^v	0.93	2.47	3.302 (12)	150
C38—H38A⋯O3^vi	0.96	2.51	2.995 (16)	112
C38—H38B⋯O13^vii	0.96	2.51	3.436 (19)	163

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

Acknowledgments

This work was supported by the Youth Foundation of Hebei Normal University (No. L2006Q20).

supplementary crystallographic information

Comment

The coordination chemistry of the chelating ligand 1,10-phenanthroline-5,6-dione has been examined in several studies (Khalaji et al., 2007; Ma et al., 2010; Rezvani et al., 2010). Carrying an O-quinone and N-pyridine moiety to form stable complexes with a wide variety of metal ions, this ligand is considered to have many interesting biological and electrochemical properties (Boghaei & Asl, 2007; Goss & Abruna, 1985; Kou et al., 2009). As far as we know, 1,10-phenanthroline-5,6-dione usually binds to metals through its imine N atoms, in some cases both the N and O donors are used simultaneously (Brechin et al., 2008). In this paper, we report the crystal structure of the title compound in the hope of exploring some spectroscopic properties of d¹⁰ metal complexes.

The title compound consists of a [Zn(C₁₂H₆N₂O₂)₃]²⁺ complex cations, two perchlorate anions and an acetonitrile solvent molecule. As shown in Fig. 1, three bidentate 1,10-phenanthroline-5,6-dione ligands are coordinated to the Zn^II atom solely via two N atoms. The coordination geometry around the Zn^II atom is distorted octahedral, with bite angles of 76.88 (18)–77.9 (2)° for the three bidentate ligands. The cis bond angles at the Zn^II atom fall in the range of 76.85 (18)–100.0 (2)° and the trans bond angles are 164.96 (17), 170.57 (18) and 173.9 (2)°, suggesting a significant deviation from a perfect octahedral coordination. The Zn—N bond lengths range from 2.117 (5) to 2.202 (5) Å, with an average of 2.158 (5) Å. There is no strong hydrogen bond in the crystal, as shown in Fig. 2. Weak intermolecular C—H···O hydrogen bonds (Table 1) and O···π and N···π interactions [O···centroid distances = 2.907 (5) and 2.843 (7) Å, N···centroid distance = 2.861 (10) Å] link the complex molecules, perchlorate anions and acetonitrile solvent molecules into a three-dimensional network.

Experimental

The title compound was prepared by adding a solution of Zn(ClO₄)₂.2H₂O (28.2 mg, 0.1 mmol) in 3 ml acetonitrile to a solution containing 1,10-phenanthroline-5,6-dione (63.1 mg, 0.3 mmol) in 12 ml acetonitrile. The mixture was stirred at room temperature for 5 h and then filtered. Yellow crystals suitable for X-ray diffraction were obtained by slow evaporation of the solvent after two days. They were collected by filtration, washed with diethyl ether and dried in air.