(4-Oxido-2-oxo-1,2-dihydro­pyrimidine-5-carboxyl­ato-κ2 O 4,O 5)(4-oxido-2-oxo-1,2-dihydro­pyrimidin-3-ium-5-carboxyl­ato-κ2 O 4,O 5)bis­(1,10-phenanthroline-κ2 N,N′)gadolinium(III) dihydrate

Wei Xiong; Huihui Xing; Yan Su; Zilu Chen

doi:10.1107/S1600536808025713

. 2008 Aug 16;64(Pt 9):m1168–m1169. doi: 10.1107/S1600536808025713

(4-Oxido-2-oxo-1,2-dihydropyrimidine-5-carboxylato-κ² O ⁴,O ⁵)(4-oxido-2-oxo-1,2-dihydropyrimidin-3-ium-5-carboxylato-κ² O ⁴,O ⁵)bis(1,10-phenanthroline-κ² N,N′)gadolinium(III) dihydrate

Wei Xiong ^a, Huihui Xing ^a, Yan Su ^a, Zilu Chen ^a,^*

PMCID: PMC2960513 PMID: 21201615

Abstract

The title compound, [Gd(C₅H₂N₂O₄)(C₅H₃N₂O₄)(C₁₂H₈N₂)₂]·2H₂O, was obtained from a solvothermal reaction of 2,4-dihydroxypyrimidine-5-carboxylic acid (H₃iso), GdCl₃·6H₂O and 1,10-phenanthroline (phen). The Gd^III ion is located on a twofold rotation axis and is coordinated by four N atoms from two chelating phen ligands and four O atoms (5-carboxylate and 4-oxido O atoms) from H₂iso⁻ and Hiso²⁻ ligands. The molecules are linked into a three-dimensional network by N—H⋯O, N—H⋯N and O—H⋯O hydrogen bonds. The H atom involved in an N—H⋯N hydrogen bond is disordered around a twofold rotation axis with half occupancy.

Related literature

For isostructural lanthanide complexes with 2,4-dioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylic acid, see: Sun & Jin (2004a ▶,b ▶); Xing et al. (2008a ▶). For related literature, see: Hueso-Ureña et al. (1993 ▶, 1996 ▶); Baran et al. (1996 ▶); Luo et al. (2002 ▶); Maistralis et al. (1991 ▶, 1992 ▶); Xing et al. (2008b ▶).

Experimental

Crystal data

[Gd(C₅H₂N₂O₄)(C₅H₃N₂O₄)(C₁₂H₈N₂)₂]·2H₂O
M _r = 862.87
Monoclinic,
a = 17.158 (8) Å
b = 14.504 (7) Å
c = 13.197 (7) Å
β = 99.955 (5)°
V = 3235 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.13 mm⁻¹
T = 273 (2) K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T _min = 0.676, T _max = 0.816
9884 measured reflections
3686 independent reflections
3212 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.064
S = 1.05
3686 reflections
240 parameters
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2004 ▶); 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 datablocks global, I. DOI: 10.1107/S1600536808025713/ci2644sup1.cif

e-64-m1168-sup1.cif^{(23.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808025713/ci2644Isup2.hkl

e-64-m1168-Isup2.hkl^{(177.2KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Gd1—O1	2.288 (2)
Gd1—O3	2.344 (2)
Gd1—N3	2.586 (3)
Gd1—N4	2.603 (3)

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O1—Gd1—O1ⁱ	88.22 (11)
O1—Gd1—O3ⁱ	82.54 (8)
O1—Gd1—O3	73.65 (8)
O3ⁱ—Gd1—O3	146.71 (11)
O1—Gd1—N3ⁱ	148.84 (8)
O3—Gd1—N3ⁱ	135.03 (8)
O1—Gd1—N3	105.26 (9)
O3—Gd1—N3	74.86 (8)
O1—Gd1—N4	80.80 (8)
O3—Gd1—N4	122.38 (8)
N3—Gd1—N4	63.39 (8)
O1—Gd1—N4ⁱ	147.64 (8)
O3—Gd1—N4ⁱ	74.79 (8)
N3—Gd1—N4ⁱ	72.83 (8)
N4—Gd1—N4ⁱ	123.04 (11)

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Symmetry code: (i) Inline graphic .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱⁱ	0.86	2.04	2.898 (3)	178
N1—H1⋯O1ⁱⁱ	0.86	2.60	3.160 (4)	124
N2—H2⋯N2ⁱⁱⁱ	0.86	1.81	2.669 (5)	174
O5—H5A⋯O4^iv	0.85	2.14	2.970 (4)	164
O5—H5B⋯O2^v	0.85	2.14	2.985 (4)	173

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

Acknowledgments

The authors thank the Science Foundation of Guangxi Province, China (Guikeqing 0542021), and the Scientific Research Foundation of Guangxi Normal University for financial support.

supplementary crystallographic information

Comment

2,4-Dihydroxypyrimidine-5-carboxylic acid has been extensively used in the preparation of metal complexes because of its versatile coordination modes. It can connect metal ions to form robust networks or some porous coordination polymers. Though various transition metal complexes with 2,4-dihydroxypyrimidine-5-carboxylate have been reported (Maistralis et al., 1991, 1992; Hueso-Ureña et al., 1993, 1996; Baran et al., 1996; Luo et al., 2002; Sun & Jin 2004a), lanthanide complexes are very limited. Only lanthanide complexes of Yb^III, Tb^III, Pr^III, Eu^III, Nd^III and Er^III have been reported (Sun & Jin 2004b; Xing et al.,2008a,b). In this paper, we report a new Gd^III complex, Gd(Hiso)(H₂iso)(phen)₂.2H₂O, (I).

In compound (I), the Gd^III atom is located on a twofold rotation axis and coordinated in a square antiprismatic geometry by four N atoms belonging to two chelating phen ligands and four O atoms from one monovalent and one divalent 2,4-dihydroxypyrimidine-5-carboxylate anions. The Gd—O bond lengths [2.288 (2) and 2.334 (2) Å] are shorter than the Gd—N bond lengths [2.586 (3) and 2.603 (3) Å].

The molecules are linked into a three-dimensional network by N—H···O, N—H···N and O—H···O hydrogen bonds (Table 2).

Experimental

A mixture of 2,4-dihydroxypyrimidine-5-carboxylic acid (0.0312 g, 0.2 mmol), GdCl₃.6H₂O (0.0743 g, 0.2 mmol), phen.H₂O (0.0396 g, 0.2 mmol), NaOH (0.008 g, 0.2 mmol) and water (15 ml) was sealed in a 25 ml Teflon-lined stainless-steel reactor and heated at 383 K for 120 h. It was then cooled over a period of 48 h, light yellow crystals were isolated in 80% yield. Elemental analysis for C₃₄H₂₅GdN₈O₁₀, calculated: C 47.32, H 2.92, N 12.98%; found: C 47.59,H 2.96, N 13.24%.