catena-Poly[[(1,10-phenanthroline-κ2 N,N′)copper(II)]-μ-2,2′-iminodibenzoato-κ4 O,O′:O′′,O′′′]

Consuelo Yuste-Vivas; Joana T Coutinho; Laura C J Pereira; Manuela Ramos Silva

doi:10.1107/S1600536813009203

. 2013 Apr 13;69(Pt 5):m255–m256. doi: 10.1107/S1600536813009203

catena-Poly[[(1,10-phenanthroline-κ² N,N′)copper(II)]-μ-2,2′-iminodibenzoato-κ⁴ O,O′:O′′,O′′′]

Consuelo Yuste-Vivas ^a,^*, Joana T Coutinho ^b, Laura C J Pereira ^b, Manuela Ramos Silva ^a

PMCID: PMC3647802 PMID: 23723768

Abstract

The structure of the title compound, [Cu(C₁₄H₉NO₄)(C₁₂H₈N₂)]_n, consists of zigzag polymeric chains along the c axis. The asymmetric unit contains one Cu^II atom which is coordinated by one 2,2′-iminodibenzoate ligand and a one phenanthroline unit. Two intramolecular N—H⋯O hydrogen bonds occur. The supramolecular structure is characterized by weak C—H⋯O hydrogen bonds and π–π stacking interactions, forming a three-dimensional supramolecular network. The shortest centroid–centroid distances between neighbouring phenanthroline aromatic rings and 2,2′-iminodibenzoate rings are 3.684 (1) and 3.640 Å, respectively. The shortest intrachain Cu⋯Cu distance is 7.2885 (9) and the shortest Cu⋯Cu distance between Cu atoms in different chains is 7.1103 (6) Å.

Related literature

For general background to Cu^II low-dimensional polynuclear magnetic materials, see: Fabelo et al. (2009 ▶); Martins et al. (2008a ▶,b ▶); Silva et al. (2001 ▶); Yuste et al. (2007 ▶, 2008 ▶). For structural and coordination information for 2,2′-iminodibenzoic acid, see: Field & Venkataraman (2002 ▶); Gao et al. (2009 ▶); Lin et al. (2006 ▶). graphic file with name e-69-0m255-scheme1.jpg

Experimental

Crystal data

[Cu(C₁₄H₉NO₄)(C₁₂H₈N₂)]
M _r = 498.98
Monoclinic,
a = 31.7536 (6) Å
b = 9.8492 (2) Å
c = 14.4865 (3) Å
β = 113.222 (1)°
V = 4163.56 (14) Å³
Z = 8
Mo Kα radiation
μ = 1.09 mm⁻¹
T = 293 K
0.1 × 0.08 × 0.07 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.898, T _max = 0.971
36778 measured reflections
3976 independent reflections
2900 reflections with I > 2σ(I)
R _int = 0.061

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.089
S = 1.02
3976 reflections
307 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: APEX2 (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012 ▶).

Supplementary Material

Click here for additional data file.^{(32.7KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813009203/bt6890sup1.cif

e-69-0m255-sup1.cif^{(32.7KB, cif)}

Click here for additional data file.^{(191KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813009203/bt6890Isup2.hkl

e-69-0m255-Isup2.hkl^{(191KB, 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
N1—H1⋯O2	0.86	2.07	2.708 (5)	131
N1—H1⋯O3	0.86	2.06	2.701 (5)	130
C17—H17⋯O2ⁱ	0.93	2.55	3.308 (4)	139
C23—H23⋯O3ⁱⁱ	0.93	2.38	3.185 (4)	145

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

Acknowledgments

This work was supported by the Fundo Europeu de Desenvolvimento Regional-QREN-Compete through projects PTDC/FIS/102284/2008 and PEst-C/FIS/UI0036/2011 – Fundação para a Ciência e Tecnologia (FCT).

supplementary crystallographic information

Comment

This work is part of a project of synthesizing low dimensional polynuclear magnetic materials with Copper(II) and oxygen-donors bridging ligands (Fabelo et al., 2009; Martins et al., 2008a; Martins et al., 2008b; Silva et al., 2001; Yuste et al., 2007, 2008).

The target of this work is the use of an aromatic dicarboxylic acid, such as the 2,2'-iminodibenzoic acid, (H₂IDC) and another quelate, known as ''coligand'' that will block some coordination positions of the Copper(II) metal ion, modulating the dimensionality of the resulting compound. (Gao et al., 2009; Lin et al., 2006; Yuste et al., 2008).

The structure of this compound consists of neutral chains of formula [Cu(C₁₄H₉NO₄)(C₁₂H₈N₂)]_n, growing along the c-axis, in a zigzag mode, where the 2,2'-iminodibenzoate (IDC^2-) units act as linkers between two Cu(II) ions, in a bis-bidentate mode, and the phenanthroline molecules are placed out-of-chain. The whole compound adopts a three dimensional supramolecular structure by weak π-π stacking. The shortest intra- and interchain copper···copper distances are 7.2885 (9) Å [Cu1···Cu1ⁱ; (i) = x, 1 - y, -1/2 + z] and 7.1103 (6) Å [Cu1···Cu1^v; (v) = 1/2 - x, 1/2 - y, 1 - z], respectively.

The Copper(II) ion shows a distorted octahedral environment, CuN₂O₄, due to the Jahn-Teller effect. The equatorial positions are occupied by the two nitrogen atoms from the phenanthroline ligand, [N1 and N2], and two oxygen atoms [O1 and O4], from two different carboxylate units of the IDC^2- ligand, varying the distances in a very narrow range of [1.940–2.026 Å]. Another two oxygen atoms [O2 and O3], with bond length values 2.618 (2) and 2.438 (3) Å respectively, are placed in the axial positions. The 2,2'-iminodibenzoate links two neighboring Copper(II) metal ions, being the bite angle 55.19 (11)° [O1—Cu1—O2] and 58.92 (11)° [O3—Cu1ⁱⁱ—O4]. [(ii) = x, -y, -1/2 + z]. The ligand is not planar, with a maximum deviation of 1.472 (5) Å for C10 from the mean plane, being the dihedral angle between the two aromatic rings 52.25 (3)°, which is greater than those already reported (Field et al., 2002; Gao et al., 2009).

Intramolecular hydrogen bond interactions exist inside the 2,2'-iminodibenzoate unit between the nitrogen atom [N1] from the amino group and two oxygen atoms [O2 and O3] from the carboxylate groups. The intermolecular π-π stacking interaction exists in between two aromatic rings of two neighbor phenantrolines and also between the aromatic rings of two neighbor 2,2'-iminodibenzoate moieties. These weak π-π interactions, stabilize the crystal structure of the complex. The shortest distances 'centroid-to-centroid' between neighbor aromatic ring of two phenantrolines and two neighbor 2,2'-iminodibenzoate are 3.684 (1) and 3.640 Å respectively.

Experimental

All the reagents, phenanthroline, 2,2'-Iminodibenzoic acid, and the metallic salt Cu(NO₃)₂.3H₂O, were purchased from commercial sources and used as received with no further purifications.

An aqueous solution containing Cu(NO₃)₂.3H₂O (1 mmol, 0.0242 g), Iminodibenzoic acid (1 mmol, 0.0257 g) and phenanthroline, ((2 mmol, 0.0361 g), was stirred during 30 minutes and placed in a 25 mL Teflon-lined autoclave and then heated at 120°C during 48 h. Dark green crystals were obtained by filtration, washed with water and dried in air. Ca. 36% yield based on Cu.