catena-Poly[[(2,2′-bipyridine-κ2 N,N′)cadmium]-μ3-4-nitro­phthalato-κ4 O:O′,O′′:O′′′]

Yang Fan; Guo-Min Xu; Hai-Ting Lu; Wei Li

doi:10.1107/S1600536811000468

. 2011 Jan 15;67(Pt 2):m199–m200. doi: 10.1107/S1600536811000468

catena-Poly[[(2,2′-bipyridine-κ² N,N′)cadmium]-μ₃-4-nitrophthalato-κ⁴ O:O′,O′′:O′′′]

Yang Fan ^a, Guo-Min Xu ^b, Hai-Ting Lu ^a, Wei Li ^b,^*

PMCID: PMC3051688 PMID: 21522865

Abstract

In the title polymeric compound, [Cd(C₈H₃NO₆)(C₁₀H₈N₂)]_n, two O atoms from both carboxylate groups of a nitrophthalate anion coordinate to the Cd^II cation, forming a seven-membered chelate ring and two carboxylate O atoms from another two nitrophthalate anions and a 2,2′-bipyridine ligand coordinate to the Cd cation to complete the distorted octahedral coordination geometry. The carboxylate groups of the nitrophthalate anion adopt a syn–anti bridging mode, linking adjacent Cd^II cations and forming a polymeric chain running along the a axis. Weak intra- and intermolecular C—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

For applications of coordination polymers, see: Long & Yaghi (2009 ▶); Kurmoo et al. (2009 ▶); Cheetham et al. (2006 ▶). For related complexes with 4-nitrophthalate ligands, see: Guo & Guo (2007 ▶); Xu et al. (2009 ▶); He et al. (2010 ▶).

Experimental

Crystal data

[Cd(C₈H₃NO₆)(C₁₀H₈N₂)]
M _r = 477.70
Monoclinic,
a = 7.3327 (4) Å
b = 17.3786 (9) Å
c = 13.3859 (7) Å
β = 98.149 (2)°
V = 1688.57 (15) Å³
Z = 4
Mo Kα radiation
μ = 1.34 mm⁻¹
T = 293 K
0.50 × 0.30 × 0.07 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.624, T _max = 0.911
19676 measured reflections
3825 independent reflections
3452 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.022
wR(F ²) = 0.053
S = 1.03
3825 reflections
253 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811000468/xu5128sup1.cif

e-67-0m199-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811000468/xu5128Isup2.hkl

e-67-0m199-Isup2.hkl^{(187.5KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cd1—O1ⁱ	2.2820 (15)
Cd1—O2	2.3165 (14)
Cd1—O3ⁱⁱ	2.3570 (15)
Cd1—O4	2.4753 (16)
Cd1—N2	2.3659 (18)
Cd1—N3	2.3979 (17)

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

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O5ⁱⁱⁱ	0.93	2.49	3.349 (3)	154
C9—H9⋯O3ⁱⁱ	0.93	2.39	3.037 (3)	126
C12—H12⋯O3^iv	0.93	2.56	3.490 (3)	177
C15—H15⋯O3^iv	0.93	2.56	3.493 (3)	176
C18—H18⋯O2ⁱ	0.93	2.43	3.235 (3)	145

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

Acknowledgments

This work was supported by the Science and Technology Foundation of Guizhou Province, China (No. [2008]2216).

supplementary crystallographic information

Comment

The rational design and synthesis of coordination complexes and polymers have attracted considerable attention since they can exhibit various fascinating structure topologies and have potential applications in gas adsorption and magnetism (Long & Yaghi, 2009; Kurmoo et al., 2009). During the past decades, large amount of coordination complexes and polymers have been successfully prepared and reported, in which polycarboxylates have been widely used as bridging ligands to construct coordination complexes and polymers (Cheetham et al., 2006). 4-Nitrophthalic acid is a good candidate in the polycarboxylate family because it has two carboxylate groups that can supply four potential O-donor atoms. However, only a few reports exist of coordination complexes and polymers related to 4-nitrophthalic acid have been published to our knowledge (Guo et al., 2007; Xu et al., 2009; He et al., 2010). In order to enrich the metal-4-nitrophthalate coordination complexes and polymers, we employed this ligand to assemble with cadmium ion in the presence of ancillary 2,2'-bipyridine ligand and obtained the title one-dimensional coordination polymer [Cd(4-nitrophthalate)(2,2'-bpy)]_n.

As shown from Fig. 1, the asymmetric unit of the title compound (I) has a Cd(II) ion, a 4-nitrophthalate and a 2,2'-bipyridine ligand. Cd1 ion has a distorted octahedral coordination environment comprising of two nitrogen atoms from a chelating 2,2'-bipyridine ligand, two oxygen atoms from both of the syn-anti carboxylates of a chelating 4-nitrophthalate ligand and two oxygen atoms from other two syn-anti carboxylates of two different crystallographic symmetric 4-nitrophthalate ligands. Each Cd(II) ion is linked to adjacent two Cd(II) ions by two syn-anti carboxylates from one 4-nitrophthalate ligand and other two syn–anti carboxylates from two different 4-nitrophthalate ligands to form a chained structure along the a axis with alternating Cd···Cd distances of 4.198 (5) and 5.094 (1)Å (Fig. 2).

Experimental

Cd(NO₃)₂.4H₂O (0.25 mmol, 0.077 g), 4-nitrophthalic acid (0.25 mmol, 0.052 g), 2,2'-bipyridine (0.25 mmol, 0.039 g) and NaOH (0.5 mmol, 0.020 g) were well mixed in 8 ml distilled water, and the solution was stirred for 30 min and then transferred into a 23 ml Teflon-lined bomb at 423 K for 3 d and slowly cooled to room temperature. Colorless crystals suitable for X-ray analysis were obtained.