Di-μ-glutarato-κ4 O 1:O 5-bis­[aqua­(1,10-phenanthroline-κ2 N,N′)copper(II)]

Yong-Hong Zhou

doi:10.1107/S1600536811007938

. 2011 Mar 9;67(Pt 4):m411. doi: 10.1107/S1600536811007938

Di-μ-glutarato-κ⁴ O ¹:O ⁵-bis[aqua(1,10-phenanthroline-κ² N,N′)copper(II)]

Yong-Hong Zhou ^a,^*

PMCID: PMC3099891 PMID: 21753943

Abstract

In the centrosymmetric dinuclear title complex, [Cu₂(C₅H₆O₄)₂(C₁₂H₁₈N₂)₂(H₂O)₂], the Cu^II atom displays a distorted square-pyramidal coordination environment with the basal plane occupied by two phenanthroline N atoms and two O atoms from different glutarate dianions while a water molecule is located at the apical position. Of the two water H atoms, one is engaged in an intramolecular hydrogen bond with a free oxygen of the dianion whereas the second is engaged in an intermolecular hydrogen bond, building a corrugated layer parallel to (100). These layers are further connected through π–π stacking interactions involving symmetry-related phenanthroline rings [centroid–centroid distance = 3.5599 (17) and 3.5617 (18) Å], building a three dimensionnal network. C—H⋯π interactions involving the phenanthroline ring system are also observed.

Related literature

For coordination modes of the glutarate anion, see: Ghosh et al. (2007 ▶); Kim et al. (2005 ▶); Rather & Zaworotko (2003 ▶); Zheng et al. (2004 ▶); Vaidhyanathan et al. (2004 ▶); Girginova et al. (2007 ▶).

Experimental

Crystal data

[Cu₂(C₅H₆O₄)₂(C₁₂H₁₈N₂)₂(H₂O)₂]
M _r = 783.72
Monoclinic,
a = 10.2767 (11) Å
b = 10.5935 (14) Å
c = 15.5998 (16) Å
β = 107.114 (1)°
V = 1623.1 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.38 mm⁻¹
T = 298 K
0.26 × 0.25 × 0.23 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T _min = 0.716, T _max = 0.742
7937 measured reflections
2867 independent reflections
2275 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.083
S = 1.07
2867 reflections
226 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶), ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536811007938/dn2661sup1.cif

e-67-0m411-sup1.cif^{(24.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811007938/dn2661Isup2.hkl

e-67-0m411-Isup2.hkl^{(137.9KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the N1,C6–C10 ring

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H51⋯O4	0.89	1.81	2.659 (3)	158
O5—H52⋯O2ⁱ	0.88	1.89	2.762 (3)	169
C2—H2A⋯Cg1ⁱ	0.97	2.88	3.754 (3)	151

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Symmetry code: (i) Inline graphic .

Acknowledgments

The project was supported by the Natural Science Foundation of Anhui Provincial Education Commission (No. KJw2008B65ZC) and the Open Foundation of Anhui Key Laboratory of Energetic Materials (No. KLEM2009004).

supplementary crystallographic information

Comment

For many yeras, there is a growing interest in developing organic-inorganic hybrid materials owing to their intriguing structures, new topologies, and potential applications(Ghosh et al., 2007; Kim et al.,2005). Carboxylic acids have been proved to be versatile functional moieties in generating interesting hybrid materials by interacting with metal ions. The abilities of its anion to metal ions in diverse and unique linking modes can be regarded as a major factor in making the carboxylate function a versatile structure directing moiety.

Metal glutarates are one class of dicarboxylate system which exhibit interesting structural features. Previous investigations have demonstrated that glutaric acid presents interesting behaviors due to its conformational flexibility and coordination diversity (Rather et al., 2003; Zheng et al., 2004; Vaidhyanathan et al., 2004; Girginova et al., 2007). We report here the crystal structure of the title compound.

The title complex, [Cu(C₁₂H₁₈N₂)(C₅H₆O₄)(H₂O)]₂, is a dinuclear compound organized around inversion center. The Cu^II displays a distorted square pyramidal coordination environment (Fig. 1). The basal plane is occupied by two nitrogen atoms of the phenanthroline [Cu—N(1) = 2.014 (2)Å and Cu—N(2) = 2.022 (2) Å] and two O atoms from different glutarate dianions[Cu—O(1) = 1.954 (2)Å and Cu—O(3) = 1.947 (2) Å], whereas one water molecule is located at the apical position at a significantly longer distance[Cu—O(5) = 2.380 (2) Å]. The glutarate dianions act as a bidentate ligand bridging the two Cu^II ions which are separated by 8.476 Å.

There is an intramolecular hydrogen bond involving one H of the water and the O4 oxygen of one dianion within the dinuclear complex. The second H atom of the water is engaged in hydrogen bond interaction with the O2 oxygen atom of symmetry related dinuclear complex building then a corrugated layer parallel to the (1 0 0) plane (Fig. 2, Table 1). The layers are interconnected through π-π stacking involving the symmetry related N1,C6,C7,C8,C9,C10 (A) and N2,C11,C12,C13,C14,C15 (B) phenanthroline rings (Fig. 2, Table 2) building a three dimensional network. The packing is further stabilized by weak C—H···π interaction involving the symmetry related ring A (Table 1).

Experimental

The title complex was prepared by the addition of the stoichiometric amount of CuCl₂ (0.134 g, 1 mmol) to an ethanol solution of glutaric acid (0.264 g, 2 mmol) and 1,10-phenanthroline monohydrate(0.396 g, 2 mmol), the pH was adjusted to ~6 with 0.2 mol.L^-1 KOH solution. The resulting solution was stirred for 30 min at room temperature and then filtered. Blue single crystals were isolated from the solution at room temperature over two weeks.