A one-dimensional ladder-like coordination polymer: poly[[hexa­aqua­bis(μ-5-nitro­benzene-1,3-dicarboxyl­ato-κ3 O,O′,O′′)(μ-oxalato-κ4 O,O′:O′′,O′′′)diyttrium(III)] trihydrate]

Zhong Fu; Ying Lin; Yun-You Zhou; Hong-Tao Zhang

doi:10.1107/S1600536807064306

. 2007 Dec 6;64(Pt 1):m120–m121. doi: 10.1107/S1600536807064306

A one-dimensional ladder-like coordination polymer: poly[[hexaaquabis(μ-5-nitrobenzene-1,3-dicarboxylato-κ³ O,O′,O′′)(μ-oxalato-κ⁴ O,O′:O′′,O′′′)diyttrium(III)] trihydrate]

Zhong Fu ^a, Ying Lin ^a, Yun-You Zhou ^a, Hong-Tao Zhang ^a,^*

PMCID: PMC2915072 PMID: 21200480

Abstract

In the crystal structure of the title one-dimensional coordination polymer, [Y₂(C₈H₃NO₆)₂(C₂O₄)(H₂O)₆]·3H₂O, each Y^III ion is bridged to its neighbours by two 5-nitrobenzene-1,3-dicarboxylate (nbdc) dianions and one oxalate dianion (located on an inversion centre) to form a ladder-like polymeric structure. The two carboxylate groups of nbdc assume different modes of coordination, one is chelating whereas the other is monodentate. Three water molecules coordinate to the Y^III ion to complete an eight-coordinate distorted dodecahedral geometry. The ladder-like polymers are assembled together by hydrogen bonding and π–π stacking [centrio–centriod distance = 3.819 (9) Å] in the crystal structure.

Related literature

For general background, see: Biradha (2003 ▶); Braga et al. (2005 ▶); Burrows et al. (2003 ▶); Kongshaug & Fjellvag (2006 ▶); Moulton & Zaworotko (2001 ▶); Ohmori et al. (2004 ▶); Tang et al. (2006 ▶); Janiak (2003 ▶). For related structures, see: Thomas et al. (2002 ▶); Nordell et al. (2003 ▶); Janiak (2000 ▶). For related literature, see: Ren et al. (2006 ▶); Si et al. (2004 ▶).

Experimental

Crystal data

[Y₂(C₈H₃NO₆)₂(C₂O₄)(H₂O)₆]·3H₂O
M _r = 846.21
Triclinic,
a = 7.4270 (15) Å
b = 9.2070 (18) Å
c = 11.522 (2) Å
α = 74.16 (3)°
β = 71.76 (3)°
γ = 80.01 (2)°
V = 716.5 (3) Å³
Z = 1
Mo Kα radiation
μ = 4.14 mm⁻¹
T = 298 (2) K
0.20 × 0.15 × 0.12 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (XCAD4; Harms & Wocadlo, 1995 ▶) T _min = 0.48, T _max = 0.60
3018 measured reflections
2785 independent reflections
2260 reflections with I > 2σ(I)
R _int = 0.097
3 standard reflections every 200 reflections intensity decay: 1.0%

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.112
S = 1.05
2785 reflections
220 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL (Sheldrick, 2000 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807064306/xu2377sup1.cif

e-64-0m120-sup1.cif^{(20.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807064306/xu2377Isup2.hkl

e-64-0m120-Isup2.hkl^{(136.7KB, hkl)}

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

Table 1. Selected bond lengths (Å).

O1—Y	2.414 (4)
O2—Y	2.424 (4)
O3—Yⁱ	2.299 (3)
O7—Yⁱⁱ	2.365 (3)
O8—Y	2.361 (3)
O9—Y	2.314 (4)
O10—Y	2.336 (4)
O11—Y	2.311 (4)

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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
O9—H9A⋯O2ⁱⁱⁱ	0.85	2.14	2.735 (5)	127
O9—H9B⋯O4^iv	0.85	2.07	2.726 (5)	134
O10—H10A⋯O6ⁱⁱⁱ	0.85	2.36	3.115 (7)	148
O10—H10B⋯O12ⁱⁱ	0.85	2.30	2.778 (6)	116
O10—H10B⋯O12ⁱⁱ	0.85	2.30	2.778 (6)	116
O11—H11A⋯O4^v	0.85	2.09	2.694 (5)	127
O11—H11B⋯O5^vi	0.85	2.57	2.987 (6)	111
O11—H11B⋯O7^vii	0.85	2.23	2.784 (5)	123
O12—H12A⋯O1	0.85	2.11	2.841 (6)	144
O12—H12B⋯O10ⁱ	0.85	2.21	2.953 (6)	147

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

Acknowledgments

This work was funded by the Doctoral Research Launch Foundation of Anhui Normal University and the Youth Research Foundation of Anhui Normal University (grant No. 2006xqn64).

supplementary crystallographic information

Comment

There is an intense research interest for the crystal engineering of coordination polymers owing to their intriguing molecular topologies, such as molecular grids, ladders, rings, diamondoids and honeycombs, and potential applications as functional materials (Biradha, 2003; Braga et al., 2005; Janiak, 2003; Ohmori et al., 2004). In order to construct the infinite structure, plentiful multidentate organic ligands are used to bridge metal ions (Moulton & Zaworotko, 2001). Among them, V-shape molecules, such as isophthalic acid and 5-amino-isophthalic acid, have received much attention because such a molecular geometry can result in unexpected structure comparing with that constructed by linear ligands (Burrows et al., 2003; Tang et al., 2006; Kongshaug & Fjellvag, 2006; Si et al., 2004; Ren et al., 2006). Herein, we present a novel ladder-like coordination polymer (I): Y₂(C₈H₃NO₆)₂(C₂O₄)(H₂O)₆.3(H₂O), in which metal ions are bridged by a V-shape ligand, 5-nitrobenzene-1,3-dicarboxylate (5-nitroisophthalate, abbreviated as 5-NIP), and oxalate ligands.

As shown in Figure 1, the Y(III) ion adopts an eight-coordinate geometry which may be described as a distorted dodecahedron (Table 1): it is bounded to three water oxygen atoms (O9, O10 and O11) and five carboxylate oxygen atoms, in which O1, O2 and O3ⁱⁱⁱ [symmetry code: (iii) x, y - 1, z] are from two 5-NIP ligands and O7ⁱ, O8 [symmetry code: (i) 1 - x, -y, 1 - z] are from one oxalate ligand. The H13A/O13/H13B water molecule has a fractional site occupancy of 0.50. The ligand 5-NIP chelates the Y(III) ion via its O1/C1/O2 carboxylate group, while its another O3/C8/O4 carboxylate group coordinates to a symmetry related Y(III) ion in monodentate fashion via the atom O3. The O5/N1/O6 nitro group is almost coplanar with the phenyl ring (C2/C3/C4/C5/C6/C7). The O1/C1/O2 carboxylate group is slightly twisted from the phenyl ring with the dihedral angel of 10.26 (41)° based on the phenyl (C2/C3/C4/C5/C6/C7) and the carboxyl (O1/C1/O2) planes. The O3/C8/O4 carboxylate group is out of the phenyl plane with the dihedral angel of 44.41 (36)° based on the phenyl (C2/C3/C4/C5/C6/C7) and the carboxyl (O3/C8/O4) planes. Both two carboxylate groups of the oxalate ligand bridge two symmetry related Y(III) ions in η¹:η¹:µ₂ mode. The oxalate is almost perpendicular to the phenyl plane of 5-NIP with the dihedral angel of 87.42 (26)° based on the phenyl (C2/C3/C4/C5/C6/C7) and the oxalate (O7/C9/O8/C9ⁱ/O7ⁱ/O8ⁱ) [symmetry code: (i) 1 - x, -y, 1 - z] planes. The bond distance of two sp² C9—C9ⁱ [symmetry code: (i) 1 - x, -y, 1 - z] in oxalate is elongated similar with other coordination compounds containing oxalate (Thomas et al., 2002; Nordell et al., 2003). Thus, the ligands 5-NIP link the neighbouring Y(III) ions in the head-to-tail mode to construct an infinite zigzag chain which runs along the b axis direction. Two adjacent zigzag chains are connected via oxalate bridging in the c axis direction to form a ladder-like structure with a grid of 9.207 (11)Å × 6.138 (17)Å based on the intra-ladder intervals of Yttrium (III) ions.

(Burrows et al., 2003; Tang et al., 2006; Kongshaug & Fjellvag, 2006).

All ladders are assembled together through a number of hydrogen bonding (Table 2) between 5-NIP carboxyl O atoms (O1, O2 and O4), nitro O atoms (O5 and O6), oxalate O7 atom and coordination water O atoms (O9, O10 and O11) as well as lattice water molecules (O12 and O13). Among them, H10A and H11B atoms are involved in a three-centered hydrogen bond, respectively. Moreover, the center-center distance between two adjacent phenyl rings of the different ladders is 3.819 (9) Å. It indicates the presence of π-π staking between two adjacent inter-ladder 5-NIP (Janiak et al., 2000). Therefore all ladders are packing via hydrogen bonding and the π-π interactions in the crystal.

Experimental

Y₂O₃ (22.5 mg, 0.10 mmol), 5-nitro-isophthalic acid (42.2 mg, 0.20 mmol) and Na₂C₂O₄ (26.8 mg, 0.20 mmol) were dissolved in 13 ml water. The mixture was placed in a Teflon-lined stainless steel vessel (25 ml). The vessel was sealed and heated at 443 K for 1 week, then cooled to room temperature. Colorless block crystals were collected by filtration, followed by washing with water and ethanol in 45% yield (38.5 mg). The crystals becam opaque when exposed for a long time in air.