1-D to 3-D lanthanide coordination polymers constructed from 5-aminoisophthalic acid and oxalic acid

Article abstract of DOI:10.1016/j.inoche.2012.05.040

Three lanthanide metal organic frameworks (MOFs) with mixed carboxylates of 5-aminoisophthalic acid (H₂AIP) and oxalic acid (H₂OX), namely [Yb(AIP)(OX)_0.5(H₂O)₃] _n·H₂O (1), [Tb(H

Full text of DOI:10.1016/j.inoche.2012.05.040

Inorganic Chemistry Communications 23 (2012) 25–30
Contents lists available at SciVerse ScienceDirect
Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
1-D to 3-D lanthanide coordination polymers constructed from 5-aminoisophthalic
acid and oxalic acid
Hong-Guang Jin, Yuan-Zhao Yan, Jing Li, Zhi-Gang Gu, Jin-Hao Chen, Yi-Ting Liu, Zhi-Peng Zheng,
⁎
Qing-Guang Zhan, Yue-Peng Cai
School of Chemistry and Environment, South China Normal University, PR China
Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, Guangzhou 510006, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Three lanthanide metal organic frameworks (MOFs) with mixed carboxylates of 5-aminoisophthalic acid
(H2AIP) and oxalic acid (H2OX), namely [Yb(AIP)(OX)0.5(H2O)3]n·H2O (1), [Tb(HAIP)(OX)(H2O)]n (2), and
{[Er(AIP)(OX)0.5(H2O)]·H2O}n (3) were obtained by hydrothermal reactions and characterized by elemental
analysis, IR spectra and thermogravimetric analysis, as well as single crystal X-ray diffraction. These frame-
works exhibit three typical structural features: complex 1 possesses one-dimensional ladder-like chain, 2
has two-dimensional layer, and 3 is three-dimensional framework. Moreover, the fluorescent property of 2
is also investigated.
Received 30 March 2012
Accepted 22 May 2012
Available online 15 June 2012
Keywords:
Lanthanide metal organic frameworks
Mixed-carboxylates
Fluorescence
© 2012 Published by Elsevier B.V.
Metal organic frameworks (MOFs) have been developed extremely
rapidly over the past decade due to their intriguing network topologies
and promising applications in many aspects such as catalysis, lumines-
cence, gas storage, selective adsorption and magnetic devices [1,2]. As
compared with the fruitful reports of d-block transition metal coordina-
tion polymers, the assembly of lanthanide coordination networks has
had an upsurge of interest in recent years. Rare earth organic coordina-
tion compounds have been extensively utilized in high-performance
luminescent devices, optics, and other functional materials because of
their electronic, optical, and chemical characteristics arising from the
4f electronic shells [3,4].
Considering that the lanthanide ions have high affinities for
hard donor atoms like oxygen of carboxylic groups, benzene–
polycarboxylate ligands are often used to link the nodes of the single
metal ions in lanthanide metal–organic frameworks (LMOFs) with
fascinating architectures [5,6]. To construct novel architectures, various
functional groups such as nitro, amine, sulfonate, and hydroxyl groups
have been attached to benzene–polycarboxylate ligands [7–9], for ex-
ample, 5-aminoisophthalic acid (H2AIP) as one very representative li-
gand. In present work, we assemble different dimensional lanthanide
frameworks based on 5-aminoisophthalic acid (H2AIP), in which its
two carboxylic groups may be completely or partially deprotonated,
resulting in rich coordination modes to the lanthanide ions. Meanwhile,
its amino group can act as the hydrogen-bond acceptor/donor to form
hydrogen bonds with the adjacent units, which is often useful for the
formation of stable frameworks. On the other hand, oxalate anion is a
very good bridging ligand that can form stable chelated five-
membered rings with metal cations [10], contributing to formation of
diverse metal–organic frameworks. Based on the above-mentioned ad-
vantages, 5-aminoisophthalic acid (H2AIP) and oxalic acid (H2OX) are
regarded as mixed-carboxylate ligands, we get three lanthanide coordi-
nation polymers with variable dimensions from 1-D, 2-D to 3-D under
hydrothermal conditions (Scheme 1). To the best of our knowledge,
the reports on lanthanide complexes containing the mixed ligands of
H2AIP and H2OX are still very rare so far [11,12].
The compounds 1–3 were obtained by the reactions of Ln(NO3)3
(Ln=Yb(1), Tb(2) and Er(3)), 5-aminoisophthalic acid, oxalic acid
and H2O in hydrothermal condition at 160 °C for 3 days [13]. The molec-
ular formula of three complexes 1–3 were identified by elemental anal-
ysis, IR and X-ray diffraction. In the IR spectra of 1–3, the strong and
broad absorption bands in the range of 3250–3510 cm−1 are assigned
as the characteristic peak of O\H vibration from the water molecules
and uncoordinated carboxylic \COOH group. Moreover, its IR spectrum
also shows characteristic bands of carboxyl groups at near 1569 cm−1
for the asymmetric stretching and at near 1401 cm−1 for the symmetric
stretching [14].
Compound 1 crystallizes in P-1 space group [15], while its asymmet-
ric unit contains one Yb3+ ion, one AIP2− ligand, half an OX2− ligand,
three coordinated water molecules and one free water molecule. Each
YbIII atom is coordinated by eight oxygen atoms, among which three ox-
ygen atoms (O5,O6,O9) from three coordinated water molecules, three
oxygen atoms (O1c,O2c,O4) from two AIP2− ligands and the other two
oxygen atoms (O7,O8b) from one OX2− ligand to form a distorted
bicapped trigonal prism coordination geometry (Fig. 1a). The Yb\O
average distance is 2.327 Å (ranging from 2.259 to 2.398 Å) (Table
S1), which are similar to the reported Yb\O bond distances in other
⁎
Corresponding author. Tel.: +86 020 39310383; fax: +86 020 39310187.
E-mail address: ypcai8@yahoo.com (Y.-P. Cai).
1387-7003/$ – see front matter © 2012 Published by Elsevier B.V.
doi:10.1016/j.inoche.2012.05.040

26
H.-G. Jin et al. / Inorganic Chemistry Communications 23 (2012) 25–30
Scheme 1. Construction of three compounds 1–3 based on ligands H2AIP and H2OX.
Fig. 1. In compound 1, a) coordination environment of YbIII center and the binding fashions of ligands AIP2− and OX2−; b) the 1-D ladder-like chain along b-axis; c) the simplified 1-D
ladder-like chain. Symmetric codes: a) x,-1+y,z; b) 2-x,1-y,1-z; c) x,1+y,z.

H.-G. Jin et al. / Inorganic Chemistry Communications 23 (2012) 25–30
27
Fig. 2. For compound 2, a) coordination environment of TbIII center and the binding fashions of ligands HAIP− and OX2−; b) 2-D layer in bc plane; c) the simplified 2-D layer. Symmetric
codes: a) 0.5-x,0.5+y,0.5-z; b) -x,2-y,-z; c) x,-1+y,z; d) 0.5-x,-0.5+y,0.5-z; e) –x,1-y,-z; f) x,1+y,z.
Ln3+ carboxylate complexes observed in the reported papers [16].
In compound 1, one carboxylate group of AIP2− is monodentated to
Yb3+ ion and the other one is chelated to another Yb3+ ion, resulting
in the formation of 1-D [Yb(AIP)(H2O)3]n chain. And then two parallel
1-D chains are connected into 1-D ladder-like chain by μ2-OX2−
bridging ligand as shown in Fig. 1b–c. Meanwhile, through inter-chain
hydrogen bonding O(N) \H···O interactions (Table S2), a 3-D supra-
molecular network is assembled as depicted in Figure S1.
and one coordinated water molecule. Each TbIII atom is coordinated
by nine oxygen atoms, in which one oxygen atom (O5) from one coor-
dinated water molecule, four oxygen atoms (O1c, O2b, O3, O4) from
two HAIP− ligands and the other four ones (O6, O7, O8a, O9a) from
two OX2− ligands to form a distorted tricapped trigonal prism geometry
(see Fig. 2a). The Tb\O average distance is 2.452 Å (ranging from 2.338
to 2.549 Å) (Table S2), which is similar to our previous reported Tb\O
bond distances [3(c)]. In compound 2, each HAIP− has μ3-linking fash-
ion to link three TbIII atoms, in which one carboxylic group is μ2-bridged
to two TbIII atoms and the other is chelated to another TbIII atom. Similar
Compound 2 crystallizes in C2/c space group [15], its asymmetric
unit contains one Tb3+ ion, one HAIP− ligand, half an OX2− ligand,

28
H.-G. Jin et al. / Inorganic Chemistry Communications 23 (2012) 25–30
Fig. 3. In compound 3, a) coordination environment of ErIII center and the binding fashions of ligands AIP2− and OX2−;b) The 3-D pillar-layer framework viewed along b axis; c) the
simplified 3-D pillar-layer framework. Symmetric codes: a) 0.5-x,-y,z; b) x,y,-1+z; c) 1-x,-y,-z; d) x,0.5-y,0.5-z; e) 1-x,0.5+y,0.5+z; f) x,y,1+z.
to compound 1, OX2− anion in 2 via μ2-bridging manner connects two
TbIII atoms to form 1-D zigzag earth-metal oxalic chain. And then
these chains are further hinged by reverse arranged μ3-HAIP− to form
a 2-D layer-like structure, stabilized by intra-layer hydrogen bonding
C\H···O interaction (Fig. 2b). In order to simplify connectivity be-
tween ligands and metals in 2, the ligands HAIP− and OX2− may be reg-
arded as tripod-like 3-connector and linear 2-connector, respectively.
Such framework in 2 can be simplified into 2-D layer as described in
Fig. 2c. It is noteworthy that interlayer hydrogen bonds O(N)\H···O
promote the formation of 3-D supramolecular network and further
benefit the stability of the framework in 2 (Table S2 and Figure S2).
Compound 3 crystallizes in Pnna space group [15], and its asymmetric
unit contains one Er3+ ion, one AIP2− ligand, half an OX2− ligand, one co-
ordinated water molecule and one free water molecule. Each ErIII atom is
coordinated by eight oxygen atoms, in which one oxygen atom (O5) from
one coordinated water molecule, five oxygen atoms (O1b, O2d, O3, O4,

H.-G. Jin et al. / Inorganic Chemistry Communications 23 (2012) 25–30
29
O4c) from three AIP2− ligands and the other two (O6, O7a) from one OX2
− ligand to form a distorted bicapped trigonal prism coordination geom-
etry (Fig. 3a). The Er\O average distance is 2.360 Å (ranging from 2.207
to 2.605 Å) (Table S2), which is similar to the reported Er\O bond dis-
tances [3(c)]. In compound 3, one carboxylate group of AIP2− is μ2-
bridged to two Er3+ ions and the other one adopts μ2-η1:η2 mode to
bridge another two Er3+ ions, resulting in the formation of 2-D layer-
like structure (Figure S3). From Figure S3, obviously, 2-D layer is also
viewed as the repeated arrangement of four edge-sharing multi-
membered rings (namely one four-membered R4Er2O2, two sixteen-
of Guangdong Province (grant no. 2010B031100018), the N.S.F. of
Guangdong Province (grant no. 9251063101000006) and Science and in-
formation Technology of Guangzhou Municipal (grant no. 11S72090055).
Appendix A. Supplementary material
X-ray crystallographic file in CIF format for compound 1 is avail-
able in supporting material section. The CCDC reference numbers
are 862867, 862868 and 862869 for compounds 1, 2 and 3, respec-
tively. Copy of the data can be obtained free of charge on application
to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [Fax: int code
+44(1223)336-033; E-mail: deposit@ccdc.cam.ac.uk]. Supplementa-
ry data to this article can be found online at http://dx.doi.org/10.
1016/j.inoche.2012.05.040.
membered R16Er2O4C10, and one eight-membered R8
rings) in bc
Er2O4C2
plane. Similarly, through μ2-bridging coordination interaction of OX2−
ions, these 2-D layers are further assembled into a 3-D pillar-layer frame-
work as indicated in Fig. 3b. To better understand the structure of 3, the
simplified analysis approach was employed, which is standard procedure
for reducing multidimensional structures to a simple node-and-linker. As
discussed above, each Er3+ in 3 is connected to four AIP2− and one OX2−
ligand, each AIP2−/OX2− ion bridges four/two Er3+ centers. If four-
References
[1] (a) B. Moulton, M.J. Zaworotko, From molecules to crystal engineering: supra-
molecular isomerism and polymorphism in network solids, Chem. Rev. 101
(2001) 1629;
(b) K. Uemura, S. Kitagawa, K. Fukui, K. Saito, A contrivance for a dynamic porous
framework: cooperative guest adsorption based on square grids connected by
amide\amide hydrogen bonds, J. Am. Chem. Soc. 126 (2004) 3817;
(c) M. Eddaoudi, J. Kim, N. Rosi, D.T. Vodak, J. Wachter, M. O'Keeffe, O.M. Yaghi,
Rigid and flexible: a highly porous metal–organic framework with unusual
guest-dependent dynamic behavior, Science 295 (2002) 469.
membered ring R4
is seen as one node, similar to 2, the ligands
Er2O2
AIP2− and OX2− in 3 may be also regarded as tripod-like 3-connector
and linear 2-connector, respectively. On the basis of those connecting
fashions, the structure of 3 can be simplified into a 3-D pillar-layer net-
work (Fig. 3c).
The thermal stability of compounds 1–3 is examined and their TGA
curves were shown in Figure S4. The experiment was performed on
samples consisting of numerous single crystals of the compound
under N2 atmosphere with a heating rate of 10 °C/min. The crystals of
1 showed the first endothermic weight loss of 15.26% between 80 and
212 °C, corresponding to the removal of three coordinated water mole-
cules and one free water molecule (calc. 15.38%) from one formula unit.
And then the second weight loss above 362 °C corresponds to the de-
composition of the coordination network. For 2, the first step of weight
loss (observed 3.93%, calculated 4.05%) below 196 °C was assigned to
the liberation of coordinated water molecule, and just then the frame-
work was followed by a plateau of stability to 335 °C. When the temper-
ature increased, the organic ligands started to decompose and the
framework collapses. For 3, the first endothermic weight loss (observed
7.43%, calculated 7.60%) around 165 °C, corresponding to the removal of
one free and one coordinated water molecules from one formula unit,
just then the framework was stable to 465 °C. Similarly, when the tem-
perature continuously increased, the organic ligands started to decom-
pose and the framework collapses.
The solid-state luminescence property of compound 2 was investi-
gated at room temperature. The emission spectra of the compound 2
(Figure S5), obtained with excitation wavelength of 315 nm, are com-
posed of emission lines typical for Tb(III). The emission at 490, 543,
585 and 623 nm is attributed to the characteristic emission of 5D4 and
7FJ (J=6, 5 and 4, 3) transitions of the Tb3+ ion. The green emission of
the 5D4→ 7F5 transition and the blue mission of the 5D4→ 7F6 transition
have stronger intensities than the other two emissions of 5D4→7F4 and
5D4→7 F3. The room temperature fluorescent lifetime of the terbium
complex was determined to be 97µs which is reasonable considering
the effect of the coordinated water molecules on quenching the excited
state.
[2] (a) S.S.Y. Chui, S.M.F. Lo, J.P.H. Charmant, G. Orpen, I.D. Williams, A chemically
functionalizable nanoporous material [Cu3(TMA)2(H2O)3]n, Science 283
(1999) 1148;
(b) K. Barthelet, J. Marrot, D. Riou, G. Ferey, A breathing hybrid organic–inorganic
solid with very large pores and high magnetic characteristics, Angew. Chem.
Int. Ed. 41 (2002) 281;
(c) S. Kitagawa, R. Kitaura, S.I. Noro, Functional porous coordination polymers,
Angew. Chem. Int. Ed. 43 (2004) 2334.
[3] (a) G.J.C. Buunzli, C. Piguet, Coordination-induced formation of one-dimensional
nanostructures of europium benzene-1,3,5-tricarboxylate and its solid-state
thermal transformation, Chem. Rev. 102 (2002) 1897;
(b) H. Tsukube, S. Shinoda, Lanthanide complexes in molecular recognition and
chirality sensing of biological substrates, Chem. Rev. 102 (2002) 2389;
(c) M.-S. Liu, Q.-Y. Yu, Y.-P. Cai, C.-Y. Su, X.-M. Lin, X.-X. Zhou, J.-W. Cai, One-, two-,
and three-dimensional lanthanide complexes constructed from pyridine-2,6-
dicarboxylic acid and oxalic acid ligands, Cryst. Growth Des. 8 (2008) 4083.
[4] (a) D. Ananias, S. Ferdov, F. Almeida Paz, R. SáFerreira, A. Ferreira, F. Geraldes, L. Carlos,
Z. Lin, Photoluminescent layered lanthanide silicate nanoparticles, J. Chem. Mater.
20 (2008) 205;
(b) J. Kido, Y. Okamoto, Organo, lanthanide metal complexes for electrolumines-
cent materials, Chem. Rev. 102 (2002) 2357;
(c) Z. Hong, Nanobelts of semiconducting oxides, Adv. Mater. 13 (2001) 1241;
(d) K. Kuriki, Y. Kolike, A facile solution-phase approach to the synthesis of lumi-
nescent europium methacrylate nanowires and their thermal conversion into
europium oxide nanotubes, Chem. Rev. 102 (2002) 2347.
[5] (a) C. Daiguebonne, N. Kerbellec, K. Bernot, Y. Gerault, A. Deluzet, O. Guillou,
Synthesis, crystal structure, and porosity estimation of hydrated erbium tere-
phthalate coordination polymers, Inorg. Chem. 45 (2006) 5399;
(b) B. Zhao, X.-Y. Chen, P. Cheng, D.-Z. Liao, S.-P. Yan, Z.-H. Jiang, Synthesis, crystal
structure, and porosity estimation of hydrated erbium terephthalate coordi-
nation polymers, J. Am. Chem. Soc. 126 (2004) 15394;
(c) S. Osa, T. Kido, N. Matsumoto, N. Re, A. Pochaba, J. Mrozinski, A tetranuclear
3d–4f single molecule magnet: [CuIILTbIII(hfac)2]2, J. Am. Chem. Soc. 126
(2004) 420421;
(d) A. Mishra, W. Wernsdorfer, K.A. Abboud, G. Christou, Initial observation of mag-
netization hysteresis and quantum tunneling in mixed manganese–lanthanide
single-molecule magnets, J. Am. Chem. Soc. 126 (2004) 15648.
[6] (a) X.-D. Guo, G.-S. Zhu, Z.-Y. Li, Y. Chen, X.-T. Li, S.-L. Qiu, Rare earth coordina-
tion polymers with zeolite topology constructed from 4-connected building
units, Inorg. Chem. 45 (2006) 4065;
In summary, three new organic frameworks based on 5-H2AIP and
H2OX was successfully constructed under hydrothermal conditions.
Single-crystal X-ray diffraction reveals that compounds 1–3 has variable
dimensions from 1-D, 2-D to 3-D, which is probably due to different coor-
dination modes of AIP2−/HAIP− (mode I for 1, mode II for 2 and mode III
for 3 in Scheme 1) and coordination numbers of lanthanide ions in 1–3.
Furthermore, compound 2 has the strong fluorescent property.
(b) X. Feng, J.-S. Zhao, B. Liu, L.-Y. Wang, S.W. Ng, G. Zhang, J.-G. Wang, X.-G. Shi,
Y.-Y. Liu, A series of lanthanide–organic frameworks based on 2-propyl-1h-
imidazole-4,5-dicarboxylate and oxalate: syntheses, structures, luminescence,
and magnetic properties, Cryst. Growth Des. 10 (2010) 1399;
(c) X.-M. Lin, Y. Ying, L. Chen, H.-C. Fang, Z.-Y. Zhou, Q.-G. Zhan, Y.-P. Cai, Synthesis,
crystal structures and photoluminescence of Zn–Ln heterometallic polymers
based on pyridine-2,3-dicarboxylic acid,Inorg, Chem. Commun. 12 (2009) 316;
(d) Y.-P. Cai, Q.-Y. Yu, Z.-Y. Zhou, Z.-J. Hu, H.-C. Fang, N. Wang, Q.-G. Zhan, L. Chen,
C.-Y. Su, Metal-directed assembly of two 2-D 4d–4f coordination polymers
based on elliptical triple-deck cylinders hinged by meso-double helical chains,
CrystEngComm 11 (2009) 1006.
Acknowledgments
[7] (a) J. Tao, X. Yin, Z.B. Wei, R.B. Huang, L.S. Zheng, Hydrothermal syntheses, crys-
tal structures and photoluminescent properties of three metal-cluster based
coordination polymers containing mixed organic ligands, Eur. J. Inorg. Chem.
(2004) 125;
We are grateful to the National Natural Science Foundation of China
(nos. 91122008 and 21071056), Science and Technology Planning Project

30
H.-G. Jin et al. / Inorganic Chemistry Communications 23 (2012) 25–30
(b) J.-W. Ye, P. Zhang, K.-Q. Ye, W.-R. Yin, L. Ye, G.-D. Yang, Y. Wang, Highly ther-
block single crystals of 1–3 (yield: 58% for 1, 44% for 2 and 19% for 3 based on Ln).
Anal.Calcd for 1 YbC9H13NO10 (%): C, 23.33; H, 2.80; N, 3.00. Found: C, 22.87; H,
2.34; N,2.97. IR frequencies (KBr, cm−1): 3442, 1682, 1574, 1509, 1423, 1285, 881,
781, 733, 527. Anal.Calcd for 2 TbC10H8NO9 (%): C, 26.96; H, 1.80; N, 3.15. Found:
C, 26.89; H, 1.89; N, 3.22. IR frequencies (KBr, cm−1): 3486, 1628, 1524, 1517,
1462, 1285, 891,7921, 758, 569. Anal.Calcd for 3 ErC9H9NO8 (%): C, 25.33; H, 2.11;
N, 3.28. Found: C, 25.16; H, 2.29; N, 3.32. IR frequencies (KBr, cm−1): 3475, 1669,
1548, 1511, 1435, 1289, 885, 783, 737, 534.
mal stable zinc complex with unusual (4,8)-connected topology, Inorg. Chem.
Commun. 9 (2006) 744;
(c) Y.-P. Cai, X.-X. Zhou, Z.-Y. Zhou, S.-Z. Zhu, P.K. Thallapally, J. Liu, Single-crystal-
to-single-crystal transformation in a one-dimensional Ag–Eu helical system,
Inorg. Chem. 48 (2009) 6341.
[8] (a) J.-H. Luo, M.-C. Hong, R.-H. Wang, R. Cao, L. Han, D.-Q. Yuan, Z.-Z. Lin, Y.-F.
Zhou, A novel bilayer cobalt(II)–organic framework with nanoscale channels
accommodating large organic molecules, Inorg. Chem. 42 (2003) 4486;
(b) J.H. Luo, M.-C. Hong, R.-H. Wang, R. Cao, L. Han, Z.-Z. Lin, A rare metal–organic
3D architecture with a pseudoprimitive cubic topology with double edges
constructed from a 12-connected SBU, Eur. J. Inorg. Chem. (2003) 2705;
(c) H. Abourahma, B. Moulton, V. Kravtsov, M.J. Zaworotko, Supramolecular isom-
erism in coordination compounds:nanoscale molecular hexagons and chains,
J. Am. Chem. Soc. 124 (2002) 9990;
(d) J.W. Ye, J. Wang, J.Y. Zhang, P. Zhang, Y. Wang, Construction of 2-D lanthanide
coordination frameworks: syntheses, structures and luminescent property,
CrystEngComm 9 (2007) 515.
[9] (a) L.-S. Yan, D.-H. Huang, C.-B. Liu, Poly[µ-5-ammonioiso phthalato-aqua-µ-
oxalato-dysprosium(III)], Acta Crystallogr., Sect. E 65 (2009) m750;
(b) S.P. Chen, Y.X. Ren, F. Fu, S.L. Gao, Formation of oxalate induced by 4,4'-
Bipyridine: Hydrothermal sheses of two erbium coordination polymers, Russ.
J. Coord. Chem. 35 (2009) 157;
(c) S.-F. Si, C.-H. Li, R.-J. Wang, Y.-D. Li, Ternary oxalate-bridged lanthanide com-
plexes from hydrothermal reactions, J. Mol. Struct. 11 (2004) 703.
[10] (a) R. Vaidhyanathan, S. Natarajan, A.K. Cheetham, C.N.R. Rao, Layered tin(II) ox-
alates possessing large apertures, Chem. Mater. 11 (1999) 3636;
[14] X.-M. Lin, H.-C. Fang, Z.-Y. Zhou, L. Chen, J.-W. Zhao, S.-Z. Zhu, Y.-P. Cai, Temper-
ature- and solvent-controlled dimensionality in a zinc 6-(1H-benzoimidazol-2-
yl)pyridinecarboxylate system, CrystEngComm 11 (2009) 847.
[15] Single crystal X-ray diffraction data collections for 1, 2 and 3 were performed on
a Bruker Apex II CCD diffractometer operating at 50 kV and 30 mA using Mo Kα
radiation (λ=0.71073 Å) at 296 K. Data collection and reduction were per-
formed using the SMART and SAINT software [17(a)]. A multi-scan absorption
correction was applied using the SADABS program [17(a)]. The structure was
solved by direct methods and refined by full-matrix least squares on F2 using
the SHELXTL program package [17(b)]. All C-bound H atoms were geometrically
positioned and allowed to ride on their parent atoms and refined isotropically.
Two hydrogen atoms of the coordinated water molecule were located from dif-
ference Fourier maps and a riding model and restrained in idealized positions
and isotropically refined with the O-H and H···H distances restrained to
0.85(1) and 1.43(2) Å, respectively, and Uiso values were set equal to 1.5 Ueq
(parent atom) for water H atoms. Selected bond lengths and angles are given
in Table S1. Crystallographic data for complex 1: C9H13NO10Yb, FW=468.24, Tri-
clinic, Space group P-1 with a=7.4113(10) Å, b=9.2079(12) Å, c=11.5385(15)
Å, α=73.910(2)º, β=72.0980(10)º, γ=75.4480(10)º, V=707.97(16) Å3, Z=2,
F(000)=448, GOF=1.093, R1=0.0293, wR2=0.0786 [I>2σ(I)]. For complex 2:
(b) S. Natarajan, R. Vaidhyanathan, C.N.R. Rao, S. Ayyappan, A.K. Cheetham, New
open-framework zinc oxalates synthesized in the presence of structure-
directing organic amines, Chem. Mater. 11 (1999) 1633;
C
10H8NO9Tb, FW=445.09, Monoclinic, Space group C2/c with a=19.989(3) Å,
b=9.4444(16) Å, c=13.630(2) Å, β=118.293(2)º, V=2265.8(7) Å3, Z=8,
F(000)=1696, GOF=1.027, R1=0.0341, wR2 =0.0661 [I>2σ(I)]. For complex 3:
C9H9NO8Er, FW=426.43, Orthorhombic, Space group Pnna with a=15.275(2) Å,
b=14.163(2) Å, c=10.9756(15) Å, V=2374.4(6) Å3, Z=8, F(000)=1616,
GOF=1.025, R1=0.0365, wR2=0.0808 [I>2σ(I)].
(c) S. Natarajan, R. Vaidhyanathan, C.N.R. Rao, Three-dimensional yttrium oxa-
lates possessing large channels, Chem. Mater. 13 (2001) 185–191.
[11] Y.-C. Qiu, H. Deng, S.-H. Yang, J.-X. Mou, C. Daiguebonne, N. Kerbellec, O. Guillou,
S.R. Batten, Syntheses, crystal structures, and gas storage studies in new three-
dimensional 5-aminoisophthalate praseodymium polymeric complexes, Inorg.
Chem. 48 (2009) 3976.
[12] L.-S. Yan, D.-H. Huang, C.-B. Liu, Poly[5-ammonioisophthalato-aqua–oxalato-
dysprosium(III)], Acta Crystallogr., Sect. E: Struct. Rep. Online E65 (2009) m750.
[13] Synthesis of complexes [Yb(AIP)(OX)0.5(H2O)3]n·H2O (1), [Tb(HAIP)(OX)(H2O)]n
(2), {[Er(AIP)(OX)0.5(H2O)]·H2O}n (3) (H2AIP=5-aminoisophthalic acid and H2
OX=oxalic acid) are as follows: a mixture of 5-aminoisophthalic acid (H2AIP)(
[16] Y.-B. Wang, Z.-M. Wang, C.-H. Yan, L.-P. Jin, Synthesis and characterization of two
novel lanthanide coordination polymers with an open framework based on an
unprecedented [Ln7(μ3-OH)8]13+ cluster, J. Mol. Struct. 692 (2004) 177.
[17] G.M. Sheldrick, SADABS Program for Scaling and Correction of Area Detector Data,
University of Göttingen, Göttingen, Germany, 1996;
(b) Bruker, APEXII software, Version 6.3.1, Bruker AXS Inc., Madison, Wisconsin,
USA, 2004;
0.25 mmol), oxalic acid (0.25 mmol),Ln(NO3) (0.25 mmol), and H2O (15 mL)
G.M. Sheldrick, SHELXL-97, Program for X-ray Crystal Structure Refinement, Uni-
versity of Göttingen, Göttingen, Germany, 1997.
3
was heated to 160 °C for 72 h in a 25 mL Teflonlined stainless-steel autoclave and
was then cooled to room temperature at 10 °C/h−1 to obtain white or pale yellow