(2,9-Dimethyl-1,10-phenanthroline-κ2 N,N′)bis­(2-meth­oxy­benzoato-κ2 O 1,O 1′)cadmium

Heng Zhang; Pei-Zheng Zhao

doi:10.1107/S1600536812010835

. 2012 Mar 17;68(Pt 4):m443. doi: 10.1107/S1600536812010835

(2,9-Dimethyl-1,10-phenanthroline-κ² N,N′)bis(2-methoxybenzoato-κ² O ¹,O ^1′)cadmium

Heng Zhang ^a, Pei-Zheng Zhao ^a,^*

PMCID: PMC3343841 PMID: 22589815

Abstract

In the title compound, [Cd(C₈H₇O₃)₂(C₁₄H₁₂N₂)], the Cd^II ion is coordinated by two N atoms from a 2,9-dimethyl-1,10-phenanthroline (dmphen) ligand and four O atoms from two 2-methoxybenzoate anions in a distorted octahedral environment. Two O atoms of one bidentate 2-methoxybenzoate ligand are each disordered over two positions, with site-occupancy factors of 0.579 (4) and 0.421 (4). In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming a two-dimensional network lieing parallel to the bc plane. The crystal packing is further stablized by π–π stacking interactions between the dmphen rings of neighboring molecules, with distances between their parallel dmphen ring planes of 3.517 (3) and 3.610 (3) Å.

Related literature

For features of transition metal complexes with 1,10-phenanthroline and their derivatives, see: Dhar et al. (2003 ▶); Mizuno et al. (2002 ▶); Wall et al. (1999 ▶). For related structures, see: Harvey et al. (2000 ▶); Ding et al. (2005 ▶); Cui & Zhang (2011 ▶)

Experimental

Crystal data

[Cd(C₈H₇O₃)₂(C₁₄H₁₂N₂)]
M _r = 622.93
Monoclinic,
a = 16.9045 (12) Å
b = 8.0547 (6) Å
c = 19.3625 (14) Å
β = 101.877 (1)°
V = 2580.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.90 mm⁻¹
T = 296 K
0.48 × 0.26 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.673, T _max = 0.863
18898 measured reflections
4803 independent reflections
4307 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.023
wR(F ²) = 0.060
S = 1.02
4803 reflections
363 parameters
44 restraints
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812010835/bg2438sup1.cif

e-68-0m443-sup1.cif^{(24.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812010835/bg2438Isup2.hkl

e-68-0m443-Isup2.hkl^{(235.3KB, 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
C20—H20⋯O5ⁱ	0.93	2.46	3.312 (3)	152
C17—H17⋯O6ⁱⁱ	0.93	2.60	3.487 (3)	161
C14—H14A⋯O4	0.96	2.45	3.322 (3)	150
C6—H6⋯O5ⁱⁱⁱ	0.93	2.55	3.206 (3)	128

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

Acknowledgments

Financial support from the National Natural Science Foundation of Henan Education Committee (2011 A150018) is gratefully acknowledged.

supplementary crystallographic information

Comment

The transition metal complexes with 1,10-phenanthroline and their derivatives have attracted much attention because of their peculiar features (Dhar et al., 2003; Mizuno et al., 2002; Wall et al., 1999). Some Cd(II)-phenanthroline complexes have been synthesized and their structures were determined (Harvey et al., 2000; Ding et al., 2005; Cui et al., 2011). Recently, we obtained the title Cadmium(II) complex which contains two different kinds of chelating ligands, by reaction of 2,9-dimethyl-1,10-phenanthroline, 2-methoxy-benzoate and cadmium acetate in an ethanol/water mixture. The structure of the title compound, Cd(C₁₄H₁₂N₂)(C₈H₇O₃)₂,(I), is presented below.

The Cd^II ion is coordinated by a bidentate 2,9-dimethyl-1,10-phenanthroline and two bidentate 2-methoxy-benzoate ligands (Fig.1). The CdO₄N₂ unit forms a distorted octahedron geometry. Two O atoms of one bidentate 2-methoxy-benzoate are disordered over two positions, with site occupancy factors of ca 0.579 (4) and 0.421 (4).

In the crystal structure, molecules are linked into a broad one-dimensional framework by C—H···O hydrogen bonds and π-π stacking interactions between the dmphen rings of neighboring molecules, where vicinal aromatic groups present a face-to-face separations of 3.517 (3) and 3.610 (3) Å. (Fig. 2).

Experimental

2,9-dimethyl-1,10-phenanthroline hemihydrate (C₁₄H₁₂N₂.0.5H₂O, 0.1086 g, 0.5 mmol) was dissolved in ethanol (10 ml) and Cd(CH₃COO)₂.2H₂O (0.1333 g, 0.5 mmol) in distilled water (5 ml) were added. This solution was added to a solution of 2-methoxy-benzoic acid (C₈H₈O₃, 0.1522 g, 1 mmol) in ethanol (5 ml). The mixture was stirred at 323 K and then refluxed for 11 h, cooled to room temperature and filtered. Colourless single crystals of (I) appeared over a period of two weeks by slow evaporation of the mixture at room temperature.