Poly[[[μ3-5-(pyridine-4-carboxamido)­isophthalato]{μ3-5-[(pyridin-1-ium-4-yl)carbonyl­amino]­isophthalato}­neodymium(III)] dihydrate]

Yi-Fang Deng

doi:10.1107/S1600536811034532

. 2011 Aug 27;67(Pt 9):m1298. doi: 10.1107/S1600536811034532

Poly[[[μ₃-5-(pyridine-4-carboxamido)isophthalato]{μ₃-5-[(pyridin-1-ium-4-yl)carbonylamino]isophthalato}neodymium(III)] dihydrate]

Yi-Fang Deng ^a,^*

PMCID: PMC3200962 PMID: 22058886

Abstract

In the title compound, {[Nd(C₁₄H₉N₂O₅)(C₁₄H₈N₂O₅)]·2H₂O}_n, the Nd^III atom is eight-coordinated as it is surrounded by eight carboxylate O atoms from six ligands in a distorted square-antiprismatic arrangement. The Nd^III atoms are linked by HL ⁻ and L ²⁻ ligands [H₂ L is 5-(pyridine-4-carboxamido)isophthalic acid], forming a bilayer network. The layers are linked into a three-demensional network through N—H⋯O and O—H⋯O hydrogen bonds.

Related literature

For background on transition metal complexes that exhibit one-, two- and three-dimensional frameworks, see: Kitagawa & Kondo (1998 ▶). For high-dimensional lanthanide frameworks, see: Kiritsis et al. (1998 ▶); Zhao et al. (2004 ▶). For coordination capabilities of carboxylate, pyridine and amide groups, see: Huyskens (1977 ▶); Lee & Kumler (1962 ▶); Wang et al. (2007 ▶).

Experimental

Crystal data

[Nd(C₁₄H₉N₂O₅)(C₁₄H₈N₂O₅)]·2H₂O
M _r = 749.73
Monoclinic,
a = 13.4421 (15) Å
b = 13.7754 (17) Å
c = 16.2418 (13) Å
β = 115.813 (4)°
V = 2707.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 2.00 mm⁻¹
T = 291 K
0.18 × 0.16 × 0.12 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ▶) T _min = 0.715, T _max = 0.796
14297 measured reflections
5287 independent reflections
4792 reflections with I > 2σ(I)
R _int = 0.052

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.101
S = 1.07
5287 reflections
406 parameters
H-atom parameters constrained
Δρ_max = 1.83 e Å⁻³
Δρ_min = −1.61 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811034532/ng5214sup1.cif

e-67-m1298-sup1.cif^{(27.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811034532/ng5214Isup2.hkl

e-67-m1298-Isup2.hkl^{(258.9KB, 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
N2—H2⋯O1W	0.86	2.06	2.846 (5)	151
N1—H1⋯O2ⁱ	0.89	1.85	2.725 (4)	171
O1W—H1WA⋯O9ⁱ	0.85	1.89	2.734 (5)	177
O2W—H2WA⋯O10ⁱ	0.85	2.52	3.124 (5)	129
O1W—H1WB⋯O10ⁱⁱ	0.85	2.00	2.845 (5)	171
O2W—H2WA⋯O4ⁱⁱⁱ	0.85	2.36	2.923 (5)	125
O2W—H2WB⋯O1^iv	0.85	2.11	2.957 (4)	178
N4—H4A⋯O2W^v	0.86	2.15	2.953 (5)	156

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

Acknowledgments

This work was supported by Hengyang Bureau of Science and Technology (grant No. 2009 K J29).

supplementary crystallographic information

Comment

In recent years, there has a great deal of interest in synthesizing transition metal complexes that exhibit one-, two- and three-dimensional frameworks (Kitagawa & Kondo, 1998). However, high-dimensional lanthanide frameworks are less common (Kiritsis et al., 1998; Zhao et al., 2004). On the other hand, it is well known that carboxylate and pyridine groups have good coordination capacities as well as the amide group, a group with two different types of hydrogen bonding sites: the –NH moiety that acts as an electron acceptor and a –C=O group that acts as an electron donor (Lee, & Kumler, 1962; Huyskens, 1977; Wang et al., 2007). The study reports a new lanthanide(III) coordination polymer, [Nd(HL)(L)]_n.2nH₂O, (I), with H₂L and Nd(NO₃)₃.6H₂O.

In the title compound, the central Nd^III ion is eight-coordinated by eight O atoms from six ligands, which gives a square antiprismatic geometry (Fig. 1). The carboxyl groups of the two unique L^2- (HL^-) ligands exhibit the same coordination modes: there is a monocarboxylate and a dicarboxylate, i.e., the monocarboxylate group coordinates to one Nd^III atom in µ₁-η¹:η¹-chelate mode and the other dicarboxylate connects two Nd^III atoms in a µ₂-η¹:η¹ bridging mode. The pyridyl groups are free. Based on the coordination modes of the carboxylate groups of L^2- (HL^-), a bilayer network is formed (Fig. 2). Adjacent molecules are linked through N—H···O and O—H···O hydrogen bonds into a three-dimensional network.

Experimental

A mixture of 0.05 mmol Nd(NO₃)₃.6H₂O (21.5 mg. 0.05 mmol), H₂L (28.6 mg, 0.1 mmol), NaOH (6.0 mg, 0.15 mmol), MeOH (4 ml) and H₂O (6 ml) was heated in a 16 ml Teflon-lined reaction vessel at 453 K for 5 days; the mixture was cooled to room temperature over a period of 40 h. The product was collected by filtration, washed with H₂O and air-dried.