Crystal structure of hexaaqua-bis(pyridine-2,6-dicarboxylato)-oxalato-diytterbium(III) pentahydrate, Yb2(H2O)6(C7H3NO4)2(C2O4) · 5H2O

Xun Feng*, Xin-Ge Shi, Qian Sun and Wen-Wei Zhu

Luoyang Normal University, College of Chemistry and Chemical Engineering, Luoyang 471022, Henan, P. R. China

Received January 15, 2010, accepted and available on-line February 25, 2010; CCDC no. 1267/2922

AbstractC16H28N2O23Yb2, monoclinic, C12/c1 (no. 15),a = 23.126(6) Å, b = 18.174(4) Å, c = 7.840(2) Å,* = 94.090(3)°, V = 3286.7 Å3, Z = 4, Rgt(F) = 0.028,wRref(F

2) = 0.070, T = 296 K.

Source of materialThe mixture of 2,6-pyridinedicarboxylic acid (H2pydc, 0.0342 g,0.2.mmol) and (NH4)2C2O4.·.H2O (0.0584 g, 0.4 mmol) in anaqueous solution (10 mL) of NaOH (0.008 g, 0.2 mmol) wasadded to the aqueous solution (10 mL) of Yb(NO3)3.·.6H2O(0.190 g, 0.4 mmol), and the pH value was adjusted to 3 with0.2.M nitric acid solution. After stirring for 10 min in air the mix-ture was placed into 25 mL Teflon-lined autoclave and heated un-der autogenous pressure at 160 °C for 72 h. The autoclave wascooled over a period of 12 h at a rate 5 °C/h. After the mixture wasslowly cooled to room temperature, colourless crystals were ob-tained. The products are stable in air and insoluble in water (yield0.017 g, 37 % based on Yb). IR data are available in the CIF.

DiscussionCarboxylate ligands play an important role in constructing novelmetal-organic frameworks (MOFs) based on lanthanides in coor-dination chemistry. They usually adopt diverse coordinationmodes such as terminal monodentate, chelating to one metal cen-ter, bridging bidentate in syn-syn, syn-anti, or anti-anti configura-tions to two metal centers [1-3]. Recently, some studies on di- andmulti-carboxyl ligands or multi-functional carboxyl-containingligands incorporating other coordination groups, such as N, Shave been reported [4,5]. Among them imidazole di- or multi-carboxylate have been intensively employed to provide a greatvariety of topological architectures [6,7]. On the other hand, oxa-late ligand has been proven to be a good candidate for pillar ligand

due to its various bridging abilities and strong coordination tometals to form 2D and 3D moderately robust networks exhibitingtunable ferro- or antiferromagnetic exchanges [8]. In contrast to alarge number of lanthanide complexes containing only rigid orflexible multicarboxylate ligands, the rare homogeneous con-structions involving nitrogen-heterocyclic carboxylate ions andoxalate ligand always only can be obtained from the in situ reac-tion, in which the multi- or dicarboxylic acid were decomposedinto C2O4 [9,10].The asymmetric unit of the title complex consists of two Yb(III)cations, two pydc2– ligands, one bridging oxalate group, six coor-dinated water molecules and five lattice water molecules. TheYb(III) is octa-coordinated with two oxygen atoms from themultichelating oxalate ligands, two oxygen atoms from the che-lating carboxylate group of bpyc2– ligand and three oxygen atomsfrom water molecules, as well as the nitrogen atom from thepyridyl ring, respectively. The Yb(III) exhibits a distorted[YbO8] trigonal dodecahedral coordination polyhedron. Thebond lengths of Yb—O range from 2.286(3) to 2.348(3) Å, whichare comparable to the distances observed in Yb(III) complexeswith similar coordination spheres [11,12]. The oxalate anion actsas tetradentate bridge pillar to connect two adjacent Yb1 andYb1A ions in a anti-anti mode, and thus affords a dimer unit withthe Yb···Yb separation of 6.069 Å. The pydc2– ligand forms twofive-membered Yb/N/C/C/O rings, as the ligands based on thegemdiol or the hemiacetal forms of di-2-pyridincarboxylate orketone have been observed in numerous ligation modes. Hydro-gen-bond interactions are observed: O10–H7W···O2 [2.768(5) Å,144.8°], O10–H8W···O2 [2.733(5) Å, 158.5°], O9–H6W···O10[2.801(3) Å, 164.2°], O9–H5W···O12 [2.677(5) Å, 166.7°],O8–H4W · · ·O4 [2.664(4) Å , 168.2°]; O8–H3W · · ·O11[2.701(5).Å, 179.1°], O7–H2W···O1 [2.741(4) Å, 153.4°],O7–H1W···O11 [2.993(7) Å, 129.1°]. The complex can also beconsidered as a three-dimensional supramolecular architecture,built via strong intermolecular hydrogen-bond interactions.

Z. Kristallogr. NCS 225 (2010) 275-276 / DOI 10.1524/ncrs.2010.0119 275

© by Oldenbourg Wissenschaftsverlag, München

_____________* Correspondence author (e-mail: fengx@lynu.edu.cn)

Crystal: colorless block, size 0.19 × 0.21 × 0.29 mmWavelength: Mo K+ radiation (0.71073 Å).: 57.43 cm−1

Diffractometer, scan mode: Bruker SMART CCD, #/'2,max: 51°N(hkl)measured, N(hkl)unique: 11658, 3062Criterion for Iobs, N(hkl)gt: Iobs > 2 )(Iobs), 2388N(param)refined: 195Programs: SHELXS-97 [13], SHELXL-97 [14],

SHELXTL [15]

Table 1. Data collection and handling.

Brought to you by | University of ConnecticutAuthenticated | 137.99.31.134

Download Date | 6/3/14 4:38 PM

276 Yb2(H2O)6(C7H3NO4)2(C2O4) · 5H2O

Yb(1) 8f 0.345694(7) 0.22181(1) 0.77755(2) 0.02181(9) 0.0288(1) 0.0338(1) 0.00465(8) 0.00259(7) −0.00150(9)O(1) 8f 0.2789(1) 0.1465(2) 0.8974(4) 0.031(2) 0.034(2) 0.056(2) 0.004(1) 0.013(1) −0.004(2)O(2) 8f 0.2390(1) 0.0367(2) 0.9379(4) 0.040(2) 0.044(2) 0.068(2) −0.011(2) 0.025(2) −0.006(2)O(3) 8f 0.4285(1) 0.1969(2) 0.6328(4) 0.030(2) 0.031(2) 0.041(2) 0.003(1) 0.007(1) −0.001(1)O(4) 8f 0.4921(1) 0.1174(2) 0.5370(4) 0.024(2) 0.042(2) 0.051(2) 0.003(1) 0.013(1) −0.011(2)O(5) 8f 0.2589(1) 0.2853(2) 0.7061(4) 0.038(2) 0.051(2) 0.034(2) 0.019(2) −0.005(1) −0.011(2)O(6) 8f 0.1888(1) 0.3057(2) 0.4995(4) 0.034(2) 0.045(2) 0.039(2) 0.019(1) −0.005(1) −0.011(1)O(7) 8f 0.3227(1) 0.2917(2) 1.0132(4) 0.036(2) 0.060(2) 0.041(2) 0.017(2) −0.001(2) −0.012(2)O(8) 8f 0.4204(1) 0.2113(2) 0.9870(4) 0.036(2) 0.053(2) 0.040(2) 0.014(2) −0.004(1) −0.009(2)O(9) 8f 0.3791(1) 0.3336(2) 0.6940(4) 0.048(2) 0.034(2) 0.083(2) −0.003(2) 0.024(2) 0.004(2)O(10) 8f 0.1683(2) −0.0412(2) 0.7024(5) 0.073(2) 0.053(2) 0.084(3) −0.020(2) 0.036(2) −0.014(2)O(11) 8f 0.4152(3) 0.2743(3) 0.2975(5) 0.273(8) 0.087(4) 0.039(2) 0.001(4) 0.021(4) −0.004(2)O(12) 4e ½ 0.3392(5) ¾ 0.043(4) 0.087(6) 0.59(2) 0 0.041(8) 0N(1) 8f 0.3654(1) 0.0933(2) 0.7483(4) 0.014(2) 0.029(2) 0.030(2) 0.005(1) −0.001(1) −0.003(2)C(1) 8f 0.3286(2) 0.0423(2) 0.8064(5) 0.023(2) 0.032(2) 0.032(2) 0.002(2) 0.002(2) −0.001(2)C(2) 8f 0.3379(2) −0.0320(3) 0.7941(5) 0.034(2) 0.035(3) 0.039(3) −0.007(2) 0.001(2) 0.002(2)C(3) 8f 0.3874(2) −0.0546(3) 0.7197(5) 0.047(3) 0.028(2) 0.036(2) 0.008(2) −0.001(2) −0.004(2)C(4) 8f 0.4254(2) −0.0035(2) 0.6588(5) 0.026(2) 0.040(3) 0.035(2) 0.007(2) 0.000(2) −0.011(2)C(5) 8f 0.4119(2) 0.0704(2) 0.6753(5) 0.019(2) 0.031(2) 0.028(2) 0.003(2) −0.001(2) −0.003(2)C(6) 8f 0.2776(2) 0.0767(3) 0.8872(5) 0.030(2) 0.038(3) 0.036(2) 0.002(2) 0.002(2) −0.003(2)C(7) 8f 0.4477(2) 0.1325(2) 0.6088(5) 0.023(2) 0.036(2) 0.025(2) −0.001(2) −0.004(2) −0.005(2)C(8) 8f 0.2350(2) 0.2765(2) 0.5617(6) 0.031(2) 0.028(2) 0.039(2) 0.003(2) 0.004(2) −0.002(2)

Table 3. Atomic coordinates and displacement parameters (in Å2).

Atom Site x y z U11 U22 U33 U12 U13 U23

H(1W) 8f 0.3279 0.2775 1.1165 0.069H(2W) 8f 0.2869 0.2980 1.0267 0.069H(3W) 8f 0.4191 0.2308 1.0851 0.065H(4W) 8f 0.4490 0.1817 0.9945 0.065H(5W) 8f 0.4152 0.3432 0.7012 0.080H(6W) 8f 0.3694 0.3763 0.7255 0.080H(8W) 8f 0.1961 −0.0465 0.6374 0.103

Table 2. Atomic coordinates and displacement parameters (in Å2).

Atom Site x y z Uiso

Acknowledgments. This work was supported by the National Natural ScienceFoundation of China (grant nos. 20771054 and 20971104), National Scienceand Technology Pillar Program of China (grant no. 2007BAB17B02), and theFoundation of Education Committee of Henan province (grant no.2008A150017).

References

1. Hu, M.; Wang, Q. L.; Xu, G. F.; Zhao, B.; Deng, G. R.; Zhang, Y. H.;Yang, G. M.: Synthesis and characterization of a novel lanthanide coordi-nation polymer with network structure based on [Er4(.3-OH)4]8+ clusterand 2,2'-bipyridine-3,3'-dicarboxylate. Inorg. Chem. Commun. 10 (2007)1177-1182.

2. Ziegelgruber, K. L.; Knope, K. E.; Frisch, M.; Cahill, C. L.: Hydrothermalchemistry of Th(IV) with aromatic dicarboxylates: New framework com-pounds and in situ ligand syntheses. J. Solid State Chem. 181 (2008) 373-381.

3. Feng, X.; Zhao, J.-S.; Wang, L. Y.; Shi, X.-G.: An anion-directedunprecedent three-dimensional array with erbium(III) based on the 2,6-pyridinedicarboxylate. Inorg. Chem. Commun. 12 (2009) 388-391.

4. Luo, F.; Batten, S. R.; Che, Y. X.; Zheng, J. M.: Synthesis, structure, andcharacterization of three series of 3-4f metal-organic frameworks based onrod-shaped and (6,3)-sheet metal carboxylate substructures. Chem. Eur. J.13 (2007) 4948-4955.

5. Ma, S. Q.; Sun, D. F.; Ambrogio, M.; Fillinger, J. A.; Parkin, S.; Zhou, H.-C.: Framework-catenation isomerism in metal-organic frameworks andits impact on hydrogen uptake. J. Am. Chem. Soc. 129 (2007) 1858-1859.

6. Tong, M. L.; Kitagawa, S.; Chang, H. C.; Ohba, M.: Temperature-controlled hydrothermal synthesis of a 2D ferromagnetic coordinationbilayered polymer and a novel 3D network with inorganic Co3(OH)2ferrimagnetic chains. Chem. Commun. (2004) 418-420.

7. Zhang, Z. H.; Song, Y.; Okamura, T.; Hasegawa, Y.; Sun, W.-Y.;Ueyama, N.: Syntheses, structures, near-infrared and visible lumines-cence, and magnetic properties of lanthanide-organic frameworks with animidazole-containing flexible ligand. Inorg. Chem. 45 (2006) 2896-2902.

8. Li, B.; Gu, W.; Zhang, L. Z.; Qu, J.; Ma, Z. P.; Liu, X.; Liao, D. Z.:Ln2(C2O4)2(pyzc)2(H2O)2]n [Ln = Pr (1), Er (2)]: Novel two-dimensionallanthanide coordination polymers with 2-pyrazinecarboxylate and oxa-late. Inorg. Chem. 45 (2006) 10425-10427.

9. Orioli, P.; Bruni, B.; Di Vaira, M.; Messori, L.; Piccioli, F.: Decomposi-tion of ascorbic acid in the presence of cadmium ions leads to formation ofa polymeric cadmium oxalate species with peculiar structural features.Inorg. Chem. 41 (2002 ) 4312-4314.

10. Decurtins, S.; Schmalle, H. W.; Schneuwly, P.; Ensling, J.; Gutlich, P.: AConcept for the Synthesis of 3-Dimensional Homo- and Bimetallic Oxa-late-Bridged Networks [M2(ox)3]n. Structural, Moessbauer, and Mag-netic. Studies in the Field of Molecular-Based Magnets. J. Am. Chem.Soc. 116 (1994) 9521-9528.

11. Shavaleev, N. M.; Pope, S. J. A.; Bell, Z. R.; Faulkner, S.; Ward, M. D.:Sensitized near-infrared emission from complexes of Yb(III), Nd(III) andEr(III) by energy-transfer from covalently attached Pt(II)-based antennaunits. J. Chem. Soc., Dalton Trans. (2003) 808-814.

12. Xu, N.; Yang, Y. O.; Liao, D.-Z.; Jiang, Z.-H.; Yan, S.-P.; Cheng, P.: Syn-thesis and structure of ytterbium(III) complex containing tetrachloro-phthalate dianions. J. Chem. Crystallogr. 36 (2006) 581-585.

13. Sheldrick, G. M.: SHELXS-97. Program for the Solution of Crystal Struc-tures. University of Göttingen, Germany 1997.

14. Sheldrick, G. M.: SHELXL-97. Program for the Refinement of CrystalStructures. University of Göttingen, Germany 1997.

15. Sheldrick, G. M.: SHELXTL. Structure Determination Software Suite.Version 6.14. Bruker AXS, Madison, Wisconsin, USA 2000.

H(7W) 8f 0.1782 −0.0030 0.7758 0.103H(10W) 8f 0.4144 0.2503 0.3877 0.198H(9W) 8f 0.4162 0.3192 0.3175 0.198H(11W) 8f 0.5112 0.3164 0.8380 0.357H(2) 8f 0.3120 −0.0659 0.8343 0.043H(3) 8f 0.3953 −0.1046 0.7104 0.045H(4) 8f 0.4587 −0.0183 0.6086 0.040

Table 2. Continued.

Atom Site x y z Uiso

Brought to you by | University of ConnecticutAuthenticated | 137.99.31.134

Download Date | 6/3/14 4:38 PM