Poly[(μ2-1,3-di-4-pyridyl­propane)(μ3-1,3-phenyl­enediacetato)­cadmium]

Dong Liu; Ni-Ya Li

doi:10.1107/S1600536811041432

. 2011 Oct 12;67(Pt 11):m1540. doi: 10.1107/S1600536811041432

Poly[(μ₂-1,3-di-4-pyridylpropane)(μ₃-1,3-phenylenediacetato)cadmium]

Dong Liu ^a,^*, Ni-Ya Li ^a

PMCID: PMC3246964 PMID: 22219784

Abstract

In the title compound, [Cd(C₁₀H₈O₄)(C₁₃H₁₄N₂)]_n, two symmetry-related Cd atoms are bridged by two carboxylate O atoms into a binuclear Cd₂ subunit around an inversion center. The Cd atom has a distorted pentagonal–bipyramidal environment, defined by five O atoms from three different 1,3-phenylendiacetate (1,3-pda) ligands and two N atoms from two 1,3-di-4-pyridylpropane (bpp) ligands. Each Cd₂ subunit is linked to four different Cd₂ subunits by four 1,3-pda ligands and four bpp ligands, forming a two-dimensional network with rhombic grids (12.50 × 12.50 Å²) extending along the ab plane.

Related literature

For a coordination polymer with a similar structure, see: Nagaraja et al. (2010 ▶). For another compound synthesized from the same components as the title compound, see: Zhang et al. (2009 ▶). For Cd—O and Cd—N bond lengths in related structures, see: Clegg et al. (1995 ▶); Tao et al. (2000 ▶).

Experimental

Crystal data

[Cd(C₁₀H₈O₄)(C₁₃H₁₄N₂)]
M _r = 502.84
Orthorhombic,
a = 22.573 (5) Å
b = 10.729 (2) Å
c = 17.024 (3) Å
V = 4123.0 (14) Å³
Z = 8
Mo Kα radiation
μ = 1.09 mm⁻¹
T = 223 K
0.25 × 0.25 × 0.20 mm

Data collection

Rigaku MercuryCCD area-detector diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ▶) T _min = 0.772, T _max = 0.811
13963 measured reflections
4693 independent reflections
3718 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.061
wR(F ²) = 0.108
S = 1.19
4693 reflections
271 parameters
H-atom parameters constrained
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Data collection: CrystalClear (Rigaku, 2001 ▶); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); 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 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811041432/aa2028sup1.cif

e-67-m1540-sup1.cif^{(19.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811041432/aa2028Isup2.hkl

e-67-m1540-Isup2.hkl^{(230KB, hkl)}

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

Acknowledgments

This work was supported by the Research Start-Up Fund for New Staff of Huaibei Normal University (600581).

supplementary crystallographic information

Comment

In view of progress of crystal engineering, the appropriate choice of metal ions and organic building blocks is the most effective and facile method to assemble metal-organic compounds with various structures (Clegg et al., 1995; Nagaraja et al., 2010; Tao et al., 2000). In the past decade, rigid dicaboxylate and dipyridyl ligands have been widely employed as organic linkers to afford coordination polymers (Tao et al., 2000). Recently, flexible dicaboxylate and dipyridyl ligands have also been used to bond with metal ions (Nagaraja et al., 2010). And the complexes assembled by flexible ligands usually exhibit different structures with those of the complexes assembled by rigid ligands. In this work, we employed Cd(NO₃)₂ and two flexible ligands (1,3-phenylendiacetic acid, 1,3-pda, and 1,3-di-4-pyridylpropane, bpp) as our system and obtained the title compound.

As shown in Fig. 1, the symmetry-unique Cd atom is located in a pentagonal-bipyramidal environment, coordinated by five O atoms from three different 1,3-pda ligands at the equatorial sites and two N atoms from two bpp ligands at the axial sites. The Cd1–O [2.302 (3)–2.662 (3) Å] and Cd–N [2.319 (4)–2.320 (4) Å] distances are consistent with those previously observed in the related reported complexes (Clegg et al., 1995; Tao et al., 2000). Two symmetry related Cd atoms (Cd1 and Cd1ⁱ; symmetry code: (i) -x + 1, -y, -z) are bridged by two carboxylate O atoms into a binuclear Cd₂ subunit around an inversion center. Each Cd₂ subunit is linked to four different Cd₂ subunits by four 1,3-pda ligands and four bpp ligands forming a two-dimensional (4,4) network with rhombic grids (12.50 × 12.50 Å²) extending along the ab plane (Fig. 2).

It should be noted that the complex [Cd₂(1,3-pda)₂(bpp)₃]_n (Zhang et al., 2009) was synthesized from the same components as the title compound. However, its structure is completely different.

Experimental

Cd(NO₃)₂^.4H₂O (31 mg, 0.1 mmol), 1,3-phenylenediacetic acid (19 mg, 0.1 mmol), 1,3-di-4-pyridylpropane (20 mg, 0.1 mmol), 1.5 ml of H₂O and 1.5 mL of EtOH were loaded to a 10 mL Pyrex glass tube. The tube was sealed and heated in an oven to 438 K for three days, and then cooled to ambient temperature at a rate of 5 K/h to form colourless blocks of the title compound, which were washed with ethanol and dried in air. Yield: 39 mg (78% yield based on Cd). Anal. calcd. for C₂₃H₂₂CdN₂O₄: C, 54.94; H, 4.41; N, 5.57. Found: C, 55.06; H, 4.22; N, 5.61. IR (KBr, cm^-1): 1606 (s), 1558 (s), 1540 (s), 1418 (m), 1395 (s), 1323 (m), 1217 (m), 1108 (m), 1068 (w), 1016 (m), 960 (s), 879 (m), 834 (s), 782 (s), 724 (s), 610 (m), 556 (s).