Crystal structure of a mixed-ligand terbium(III) coordination polymer containing oxalate and formate ligands, having a three-dimensional fcu topology

Kittipong, C.; Khemthong, P.; Kielar, F.; Zhou, Y.

doi:10.1107/S205698901502397X

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Volume 72| Part 1| January 2016| Pages 87-91

doi:10.1107/S205698901502397X

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Crystal structure of a mixed-ligand terbium(III) coordination polymer containing oxalate and formate ligands, having a three-dimensional fcu topology

Chainok Kittipong,^a ^* Phailyn Khemthong,^b Filip Kielar ^b and Yan Zhou ^c

^aDepartment of Physics, Faculty of Science and Technology, Thammasat University, Khlong Luang, Pathum Thani, 12120, Thailand, ^bDepartment of Chemistry, Faculty of Science, Naresuan University, Muang, Phitsanulok, 65000, Thailand, and ^cDepartment of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong
^*Correspondence e-mail: kc@tu.ac.th

Edited by G. Smith, Queensland University of Technology, Australia (Received 22 November 2015; accepted 14 December 2015; online 1 January 2016)

The title compound, poly[(μ₃-formato)(μ₄-oxalato)terbium(III)], [Tb(CHO₂)(C₂O₄)]_n, is a three-dimensional coordination polymer, and is isotypic with the La^III, Ce^III and Sm^III analogues. The asymmetric unit contains one Tb^III ion, one formate anion (CHO₂⁻) and half of an oxalate anion (C₂O₄²⁻), the latter being completed by application of inversion symmetry. The Tb^III ion is nine-coordinated in a distorted tricapped trigonal–prismatic manner by two chelating carboxylate groups from two C₂O₄²⁻ ligands, two carboxylate oxygen atoms from another two C₂O₄²⁻ ligands and three oxygen atoms from three CHO₂⁻ ligands, with the Tb—O bond lengths and the O—Tb—O bond angles ranging from 2.4165 (19) to 2.478 (3) Å and 64.53 (6) to 144.49 (4)°, respectively. The CHO₂⁻ and C₂O₄²⁻ anions adopt μ₃-bridging and μ₄-chelating-bridging coordination modes, respectively, linking adjacent Tb^III ions into a three-dimensional 12-connected fcu topology with point symbol (3²⁴.4³⁶.5⁶). The title compound exhibits thermal stability up to 623 K, and also displays strong green photoluminescence in the solid state at room temperature.

Keywords: coordination polymers; crystal structure; lanthanide; luminescence; terbium(III).

CCDC reference: 1436132

1. Chemical context

Owing to their high colour purity, high luminescence quantum yields, narrow bandwidths, relatively long lifetimes and large Stokes shifts arising from 4f orbitals, coordination polymers of lanthanide(III) ions and organic linker ligands have received much attention from chemists during the past decade for the development of fluorescent probes and electroluminescent devices (Hasegawa & Nakanishi, 2015 ). In particular, polymeric Eu^III and Tb^III compounds with a range of organic linker ligands are the most intense emitters among the lanthanide(III) series, and they have been developed extensively as ion sensing and optical materials (Cui et al., 2014 ). Lanthanide(III) ions are known to have a high affinity and preference for hard donor atoms. Thus, dicarboxylic acid ligands containing aliphatic, aromatic and N-heterocyclic moieties have been widely employed in the construction of luminescent lanthanide coordination polymers (So et al., 2015 ). Among the ligands in this class, for instance, terephthalic acid is known to provide an efficient energy transfer to support strong lanthanide(III)-centered luminescent emission via the `antenna effect' (Samuel et al., 2009 ). On the other hand, small rigid planar species with versatile coordination oxygen donor sites such as oxalate, carbonate, nitrate, and formate anions are also a very important class of ligands for the preparation of lanthanide coordination polymers (Hong et al., 2014 ; Gupta et al., 2015 ). These small versatile ligands can bind to metals in different modes, resulting in the formation of multi-dimensional coordination networks with short intermetallic distances, which can aid the energy-transfer process between chromophoric antenna ligands and lanthanide(III) ions (Wang et al., 2012 ). In addition, the oxalate anion has proved to be an efficient sensitizer for lanthanide(III)-based emission (Cheng et al., 2007 ). Recently, many multi-dimensional luminescent lanthanide coordination polymers containing antenna and small rigid planar mixed ligands have been reported (Xu et al., 2013 ; Wang et al., 2013 ). However, only a few compounds with mixed small rigid planar ligands alone have been described in the literature (Zhang et al., 2007 ; Huang et al., 2013 ; Tang et al., 2014 ).

Herein, we report the synthesis and structure of a terbium(III) coordination polymer containing formate and oxalate mixed ligands, [Tb(CHO₂)(C₂O₄)]_n, (I), having a three-dimensional 12-connected fcu topology with point symbol (3²⁴.4³⁶.5⁶). The thermal stability and luminescent properties of compound (I) have also been investigated.

2. Structural commentary

Single crystal X-ray diffraction analysis revealed that (I) is isotypic in the orthorhombic Pnma space group with the La^III, Ce^III and Sm^III analogues (Romero et al., 1996 ). The asymmetric unit contains one Tb^III ion, one formate anion, and half of an oxalate anion. As shown in Fig. 1, each Tb^III ion is nine-coordinated in a distorted tricapped trigonal prismatic manner (Fig. 1) by two chelating carboxylate groups from two oxalate ligands, two carboxylate oxygen atoms from another two oxalate ligands and three oxygen atoms from three formate ligands, with the O—Tb—O bond angles ranging from 64.53 (6) to 144.49 (4)°. The Tb—O bond lengths in (I) are in the range of 2.4165 (19) to 2.478 (3) Å (Table 1), which is in good agreement with the reported distances for other Tb^III complexes containing oxygen donor ligands (Cheng et al., 2007; Zhu et al., 2007 ). All of the bond lengths and bond angles in the formate and oxalate anions are also within normal ranges (Rossin et al., 2012 ; Hong et al., 2014; Gupta et al., 2015). The coordination modes of the formate and oxalate ligands in (I) (Fig. 2) are commonly observed in lanthanide coordination polymers (Zhang et al., 2007; Rossin et al., 2012).

Table 1
Selected bond lengths (Å)

Tb1—O1	2.417 (3)	Tb1—O4^iv	2.4370 (18)
Tb1—O1ⁱ	2.478 (3)	Tb1—O4^v	2.4651 (17)
Tb1—O2ⁱⁱ	2.437 (3)	Tb1—O4^vi	2.4370 (17)
Tb1—O3ⁱⁱⁱ	2.4165 (19)	Tb1—O4^vii	2.4651 (17)
Tb1—O3	2.4165 (19)
Symmetry codes: (i) $[x-{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z]$ ; (iv) -x, -y+1, -z+1; (v) $[-x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (vi) $[-x, y+{\script{1\over 2}}, -z+1]$ ; (vii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 1
Coordination environment of the Tb^III ion in (I)

. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. For symmetry codes, see Table 1

Figure 2
A view of the two-dimensional terbium-formate network in (I)

, showing the monolayer structure projected in the ac plane. The dashed lines indicate the intralayer C—H⋯O hydrogen bonds (Table 2

As shown in Fig. 2, each formate anion adopts a μ₃-bridging coordination mode connecting three Tb^III ions, forming a two-dimensional (2-D) layer in the ac plane. In the 2-D terbium-formate monolayer, the Tb1⋯Tb1 separations along the formate ligands in syn–anti and anti–anti O1,O2-bridging coordination modes (Rossin et al., 2012) are 6.1567 (3) and 6.6021 (2) Å, respectively. The adjacent 2-D monolayers are stacked in an –ABA– sequence running perpendicular to the b axis with an interlayer spacing of ca 5.3 Å (Fig. 3). The oxalate ligand adopts a μ₄-chelating-bridging coordination mode, linking four Tb^III ions along the a axis to form a three-dimensional (3-D) terbium–oxalate open framework (Fig. 3). The Tb1⋯Tb1 distance via the formate O1- and oxalate O4-bridging ligands is 3.8309 (2) Å with the Tb1—O1—Tb1 and Tb1—O4—Tb1 bond angles being 103.00 (9) and 102.79 (6)°, respectively. On the other hand, the channels in the 3-D open framework have an approximate rhombic shape with a Tb1⋯Tb1 separation of 6.2670 (2) Å, and are cross-linked parallel to the c axis by bridging formate ligands as shown in Fig. 4. The presence of guest molecules in the lattice as well as the formation of interpenetrated networks of (I) are thus prevented. Furthermore, the topology of the network in (I) was analysed using TOPOS (Blatov et al., 2000 ). As schematically depicted in Fig. 5, the overall framework can be defined as a 12-connected fcu topology with point symbol (3²⁴.4³⁶.5⁶) by linking each adjacent layer of Tb^III atoms via formate and oxalate ligands.

Figure 3
The terbium-formate layered structure viewed along the c axis.

Figure 4
A perspective view along the a axis of the three-dimensional framework.

Figure 5
Schematic representation of the 12-connected fcu topology in (I)

The infrared spectrum of (I) was collected from a polycrystalline sample pelletized with KBr, in the range 4000–400 cm⁻¹. This spectrum indicates the presence of the carboxylate groups of the ligands by appearance of the strong absorption bands at 1630 and 1315 cm⁻¹ for the asymmetric (ν_asymCOO⁻) and the symmetric (ν_symCOO⁻) carboxylate vibrations, respectively (Deacon & Phillips, 1980 ). To examine the thermal stability of (I), thermogravimetric analysis was performed on a polycrystalline sample under a nitrogen atmosphere in the temperature range of 303–1273 K. There is no weight loss before 623 K due to the stability of the fcu-type 3-D frameworks. The decomposition of the framework, however, occurred rapidly at temperatures above 628 K.

The photoluminescence properties of (I) were investigated in the solid state at room temperature. The emission spectrum is shown in Fig. 6. The emission spectrum upon excitation at 305 nm exhibits the characteristic f–f transitions of Tb^III ions (Bünzli, 2010 ). The emission peaks at 487, 543, 585, and 617 nm can be assigned to the ⁵D₄ → ⁷F_J (J = 6, 5, 4, 3) transitions, respectively. The most intense transition is ⁵D₄ → ⁷F₅, which implies the emitted light is green. The emission lifetime of (I) is 1.79 ms.

Figure 6
The solid-state emission spectrum of (I)

at room temperature.

3. Supramolecular features

The two-dimensional terbium-formate monolayers are stabilized by weak intra-layer C1—H1⋯O2^viii hydrogen bonds giving S(7) graph-set motifs (Bernstein et al., 1995 ), in which each formate anion acts as a donor and acceptor for one hydrogen bond (Table 2, Fig. 2).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O2^viii	0.93	2.15	3.051 (5)	164
Symmetry code: (viii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+{\script{1\over 2}}]$ .

4. Database survey

A search of the Cambridge Structural Database (Groom & Allen, 2014 ) for lanthanide coordination polymers containing mixed oxalate and formate ligands gave four hits (RIFQIG, RIFRED, RIFRIH; Romero et al., 1996; RIFQIG01; Tan et al., 2009 ), which are isotypic with the title compound (I) as previously mentioned. The structures involving oxalate and acetate analogues have also been reported (AZOCIC; Di et al., 2011 ; Gutkowski et al., 2011 ; SOPPIX; Zhang et al., 2009 ; VORBUA; Koner & Goldberg, 2009 ).

5. Synthesis and crystallization

All reagents were of analytical grade and were used as obtained from commercial sources without further purification. Synthesis of (I): TbCl₃·6H₂O (0.187 g, 0.5 mmol), oxalic acid (0.045 g, 0.5 mmol), Na₂CO₃ (0.011 g, 0.1 mmol), and a mixture (1:1 v/v) of N,N′-dimethylformamide (DMF) and water (6 ml) was sealed in a 23 ml Teflon-lined stainless steel vessel and heated under autogenous pressure at 463 K for two days. After the reactor was cooled to room temperature, colorless block-shaped crystals were filtered off and dried in air. Yield: 0.118 g (63% based on the Tb^III source). Analysis (%) calculated for C₃HO₆Tb (291.96): C, 12.34; H, 0.35%. Found: C, 12.40; H, 0.33%. IR (KBr, cm⁻¹): 2823 (w), 2491 (w), 1630 (s), 1440 (w), 1315 (s), 1022 (m), 914 (w), 795 (s), 611 (w), 492 (s), 408 (w).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The formate H atom was found in a difference electron-density map and was refined using a riding-model approximation, with C—H = 0.93 Å and with U_iso(H) = 1.2U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	[Tb(CHO₂)(C₂O₄)]
M_r	291.96
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	296
a, b, c (Å)	7.0138 (3), 10.6077 (4), 6.6021 (2)
V (Å³)	491.20 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	14.36
Crystal size (mm)	0.2 × 0.12 × 0.08

Data collection
Diffractometer	Bruker D8 QUEST CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.655, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	6517, 638, 594
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.012, 0.025, 1.10
No. of reflections	638
No. of parameters	52
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.75, −0.63
Computer programs: APEX2 and SAINT (Bruker, 2014), SHELXS2014 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ), publCIF (Westrip, 2010 ) and enCIFer (Allen et al., 2004 ).

Supporting information

CCDC reference: 1436132

Crystal structure: contains datablock I. DOI: 10.1107/S205698901502397X/zs2356sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S205698901502397X/zs2356Isup2.hkl

Supporting information file. DOI: 10.1107/S205698901502397X/zs2356Isup3.cdx

Supporting information file. DOI: 10.1107/S205698901502397X/zs2356Isup4.docx

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010) and enCIFer (Allen et al., 2004).

Poly[(µ₃-formato)(µ₄-oxalato)terbium(III)] top

Crystal data top

[Tb(CHO₂)(C₂O₄)]	D_x = 3.948 Mg m⁻³
M_r = 291.96	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 3952 reflections
a = 7.0138 (3) Å	θ = 3.6–28.3°
b = 10.6077 (4) Å	µ = 14.36 mm⁻¹
c = 6.6021 (2) Å	T = 296 K
V = 491.20 (3) Å³	Block, colourless
Z = 4	0.2 × 0.12 × 0.08 mm
F(000) = 528

Data collection top

Bruker D8 QUEST CMOS diffractometer	638 independent reflections
Radiation source: microfocus sealed x-ray tube, Incoatec Iµus	594 reflections with I > 2σ(I)
Graphite Double Bounce Multilayer Mirror monochromator	R_int = 0.028
Detector resolution: 10.5 pixels mm^-1	θ_max = 28.3°, θ_min = 3.6°
ω and φ scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −13→14
T_min = 0.655, T_max = 0.746	l = −8→8
6517 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.012	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.025	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0092P)² + 0.8666P] where P = (F_o² + 2F_c²)/3
638 reflections	(Δ/σ)_max = 0.001
52 parameters	Δρ_max = 0.75 e Å⁻³
0 restraints	Δρ_min = −0.63 e Å⁻³

Special details top

Experimental. SADABS-2014 (Bruker, 2014) was used for absorption correction. wR2(int) was 0.0566 before and 0.0416 after correction. The ratio of minimum to maximum transmission is 0.8789. The λ/2 correction factor is 0.00150.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Tb1	0.20226 (2)	0.7500	0.63323 (2)	0.00749 (6)
O1	0.5347 (4)	0.7500	0.5364 (4)	0.0132 (5)
O2	0.5527 (4)	0.7500	0.2000 (4)	0.0237 (7)
O3	0.2384 (3)	0.54490 (18)	0.4786 (3)	0.0186 (4)
O4	0.0873 (3)	0.37671 (16)	0.3522 (3)	0.0120 (4)
C1	0.6227 (6)	0.7500	0.3693 (6)	0.0197 (8)
H1	0.7551	0.7500	0.3761	0.024*
C2	0.0956 (4)	0.4788 (2)	0.4518 (4)	0.0124 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tb1	0.00799 (8)	0.00750 (8)	0.00698 (9)	0.000	−0.00049 (7)	0.000
O1	0.0110 (13)	0.0209 (14)	0.0076 (13)	0.000	0.0013 (10)	0.000
O2	0.0235 (16)	0.0381 (18)	0.0096 (14)	0.000	−0.0010 (12)	0.000
O3	0.0133 (9)	0.0143 (9)	0.0282 (11)	−0.0028 (7)	0.0010 (8)	−0.0093 (9)
O4	0.0136 (8)	0.0093 (8)	0.0131 (9)	−0.0011 (7)	0.0027 (7)	−0.0041 (7)
C1	0.0141 (17)	0.029 (2)	0.016 (2)	0.000	−0.0009 (16)	0.000
C2	0.0151 (12)	0.0112 (11)	0.0109 (12)	0.0003 (10)	−0.0002 (10)	−0.0020 (10)

Geometric parameters (Å, º) top

Tb1—O1	2.417 (3)	Tb1—O4^vii	2.4651 (17)
Tb1—O1ⁱ	2.478 (3)	O1—C1	1.265 (5)
Tb1—O2ⁱⁱ	2.437 (3)	O2—C1	1.221 (5)
Tb1—O3ⁱⁱⁱ	2.4165 (19)	O3—C2	1.235 (3)
Tb1—O3	2.4165 (19)	O4—C2	1.268 (3)
Tb1—O4^iv	2.4370 (18)	C1—H1	0.9300
Tb1—O4^v	2.4651 (17)	C2—C2^iv	1.551 (5)
Tb1—O4^vi	2.4370 (17)

Tb1^viii—Tb1—Tb1ⁱ	132.533 (9)	O4^vi—Tb1—Tb1^viii	138.32 (4)
O1—Tb1—Tb1^viii	39.06 (6)	O4^v—Tb1—Tb1^viii	38.34 (4)
O1ⁱ—Tb1—Tb1ⁱ	37.94 (6)	O4^vi—Tb1—Tb1ⁱ	38.87 (4)
O1—Tb1—Tb1ⁱ	171.60 (6)	O4^vii—Tb1—Tb1ⁱ	108.19 (4)
O1ⁱ—Tb1—Tb1^viii	94.59 (6)	O4^iv—Tb1—Tb1ⁱ	38.87 (4)
O1—Tb1—O1ⁱ	133.65 (7)	O4^iv—Tb1—Tb1^viii	138.33 (4)
O1—Tb1—O2ⁱⁱ	100.16 (9)	O4^v—Tb1—Tb1ⁱ	108.19 (4)
O1—Tb1—O4^vii	65.01 (6)	O4^vii—Tb1—Tb1^viii	38.34 (4)
O1—Tb1—O4^vi	144.49 (4)	O4^iv—Tb1—O1ⁱ	64.53 (6)
O1—Tb1—O4^v	65.01 (6)	O4^vii—Tb1—O1ⁱ	76.57 (6)
O1—Tb1—O4^iv	144.49 (4)	O4^vi—Tb1—O1ⁱ	64.53 (6)
O2ⁱⁱ—Tb1—Tb1^viii	139.22 (7)	O4^v—Tb1—O1ⁱ	76.57 (6)
O2ⁱⁱ—Tb1—Tb1ⁱ	88.25 (7)	O4^vi—Tb1—O2ⁱⁱ	71.16 (7)
O2ⁱⁱ—Tb1—O1ⁱ	126.19 (9)	O4^iv—Tb1—O2ⁱⁱ	71.16 (7)
O2ⁱⁱ—Tb1—O4^v	141.92 (5)	O4^v—Tb1—O4^vii	66.08 (8)
O2ⁱⁱ—Tb1—O4^vii	141.92 (5)	O4^vi—Tb1—O4^v	140.95 (3)
O3—Tb1—Tb1^viii	94.25 (5)	O4^iv—Tb1—O4^vi	66.94 (8)
O3ⁱⁱⁱ—Tb1—Tb1ⁱ	105.42 (5)	O4^iv—Tb1—O4^v	100.09 (6)
O3ⁱⁱⁱ—Tb1—Tb1^viii	94.25 (5)	O4^vi—Tb1—O4^vii	100.09 (6)
O3—Tb1—Tb1ⁱ	105.42 (5)	O4^iv—Tb1—O4^vii	140.95 (3)
O3—Tb1—O1	77.72 (5)	Tb1—O1—Tb1^viii	103.00 (9)
O3—Tb1—O1ⁱ	114.93 (5)	C1—O1—Tb1^viii	122.4 (2)
O3ⁱⁱⁱ—Tb1—O1ⁱ	114.93 (5)	C1—O1—Tb1	134.6 (2)
O3ⁱⁱⁱ—Tb1—O1	77.72 (5)	C1—O2—Tb1^ix	130.8 (3)
O3—Tb1—O2ⁱⁱ	70.35 (5)	C2—O3—Tb1	119.13 (17)
O3ⁱⁱⁱ—Tb1—O2ⁱⁱ	70.35 (5)	Tb1^iv—O4—Tb1^x	102.79 (6)
O3—Tb1—O3ⁱⁱⁱ	128.40 (10)	C2—O4—Tb1^x	137.90 (16)
O3—Tb1—O4^vii	132.53 (6)	C2—O4—Tb1^iv	119.27 (16)
O3—Tb1—O4^vi	126.90 (6)	O1—C1—H1	116.5
O3ⁱⁱⁱ—Tb1—O4^iv	126.90 (6)	O2—C1—O1	127.1 (4)
O3ⁱⁱⁱ—Tb1—O4^vi	66.88 (6)	O2—C1—H1	116.5
O3ⁱⁱⁱ—Tb1—O4^v	132.52 (6)	O3—C2—O4	126.6 (2)
O3ⁱⁱⁱ—Tb1—O4^vii	72.19 (6)	O3—C2—C2^iv	118.5 (3)
O3—Tb1—O4^v	72.19 (6)	O4—C2—C2^iv	114.9 (3)
O3—Tb1—O4^iv	66.88 (6)

Tb1^viii—Tb1—O1—C1	180.0	O2ⁱⁱ—Tb1—O3—C2	−67.5 (2)
Tb1ⁱ—Tb1—O3—C2	14.9 (2)	O3ⁱⁱⁱ—Tb1—O1—Tb1^viii	112.87 (5)
Tb1^viii—Tb1—O3—C2	151.3 (2)	O3—Tb1—O1—Tb1^viii	−112.87 (5)
Tb1—O1—C1—O2	0.0	O3ⁱⁱⁱ—Tb1—O1—C1	−67.13 (5)
Tb1^viii—O1—C1—O2	180.0	O3—Tb1—O1—C1	67.13 (5)
Tb1^ix—O2—C1—O1	180.0	O3ⁱⁱⁱ—Tb1—O3—C2	−109.9 (2)
Tb1—O3—C2—O4	171.1 (2)	O4^v—Tb1—O1—Tb1^viii	−36.98 (5)
Tb1—O3—C2—C2^iv	−9.4 (4)	O4^vi—Tb1—O1—Tb1^viii	108.29 (11)
Tb1^x—O4—C2—O3	−6.7 (5)	O4^vii—Tb1—O1—Tb1^viii	36.98 (5)
Tb1^iv—O4—C2—O3	170.9 (2)	O4^iv—Tb1—O1—Tb1^viii	−108.29 (11)
Tb1^iv—O4—C2—C2^iv	−8.7 (4)	O4^v—Tb1—O1—C1	143.02 (5)
Tb1^x—O4—C2—C2^iv	173.74 (18)	O4^vi—Tb1—O1—C1	−71.71 (11)
O1ⁱ—Tb1—O1—Tb1^viii	0.0	O4^vii—Tb1—O1—C1	−143.02 (5)
O1ⁱ—Tb1—O1—C1	180.0	O4^iv—Tb1—O1—C1	71.71 (11)
O1ⁱ—Tb1—O3—C2	54.2 (2)	O4^iv—Tb1—O3—C2	9.75 (19)
O1—Tb1—O3—C2	−173.1 (2)	O4^vi—Tb1—O3—C2	−21.7 (2)
O2ⁱⁱ—Tb1—O1—Tb1^viii	180.0	O4^v—Tb1—O3—C2	119.5 (2)
O2ⁱⁱ—Tb1—O1—C1	0.0	O4^vii—Tb1—O3—C2	148.72 (19)

Symmetry codes: (i) x−1/2, y, −z+3/2; (ii) x−1/2, y, −z+1/2; (iii) x, −y+3/2, z; (iv) −x, −y+1, −z+1; (v) −x+1/2, −y+1, z+1/2; (vi) −x, y+1/2, −z+1; (vii) −x+1/2, y+1/2, z+1/2; (viii) x+1/2, y, −z+3/2; (ix) x+1/2, y, −z+1/2; (x) −x+1/2, −y+1, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2^xi	0.93	2.15	3.051 (5)	164

Symmetry code: (xi) x+1/2, −y+3/2, −z+1/2.

Acknowledgements

This research was supported financially by the National Research Council of Thailand through the Thammasat University Research Scholar (No. 216919). We thank Central Scientific Instrument Center (CSIC), Faculty of Science and Technology, Thammasat University, for providing access to the equipment.

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Volume 72| Part 1| January 2016| Pages 87-91

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of a mixed-ligand terbium(III) coordination polymer containing oxalate and formate ligands, having a three-dimensional fcu topology

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

3. Supramolecular features