Poly[[tetra­aqua­tris­(μ3-hexane-1,6-di­carboxyl­ato)diterbium(III)] 0.25-hydrate]

Li, F.-F.; Zhang, H.-J.; Zhang, L.-N.

doi:10.1107/S1600536811007719

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page m412

doi:10.1107/S1600536811007719

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Poly[[tetraaquatris(μ₃-hexane-1,6-dicarboxylato)diterbium(III)] 0.25-hydrate]

Fei-Fei Li,^a ^* Hui-Ju Zhang ^a and Li-Na Zhang ^a

^aDepartment of Physics and Chemistry, Henan Polytechnic University, Jiaozuo, Henan 454000, People's Republic of China
^*Correspondence e-mail: lifeifei@hpu.edu.cn

(Received 16 February 2011; accepted 1 March 2011; online 9 March 2011)

In the title terbium coordination polymer, {[Tb₂(C₆H₈O₄)₃(H₂O)₄]·0.25H₂O}_n, the Tb^III atom is nine-coordinated, forming a TbO₉ polyhedra. Furthermore, two symmetric TbO₉ polyhedra share their edges, forming Tb₂O₁₆ dimers, which are linked by adipate bridges into a layered structure. Intermolecular O—H⋯O hydrogen bonds link these layers into a three-dimensional network. One of the C atoms of the adipate ligand is disordered over two positions with site-occupancy factors of 0.622 (9) and 0.378 (9). The structure also contains a disordered molecule of water of hydration, lying close to a special position, with partial occupancy.

Related literature

For background to coordination polymers, see: Moulton & Zaworotko (2001 ); Wood & Thompson (2007 ). For the structures of rare earth--adipate compounds, see: Dimos et al. (2002 ); Duan et al. (2004 ); Kim et al. (2004 ); Kiritsis et al. (1998 ). For isotypic La(III) and Dy(III) structures, see: Kim et al. (2004); Lill et al. (2005 ).

Experimental

Crystal data

[Tb₂(C₆H₈O₄)₃(H₂O)₄]·0.25H₂O
M_r = 826.78
Monoclinic, P 2₁ /c
a = 11.603 (6) Å
b = 13.886 (7) Å
c = 8.969 (4) Å
β = 111.017 (7)°
V = 1348.9 (11) Å³
Z = 2
Mo Kα radiation
μ = 5.27 mm⁻¹
T = 298 K
0.25 × 0.05 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T_min = 0.352, T_max = 0.779
7908 measured reflections
2335 independent reflections
2008 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.066
S = 1.06
2335 reflections
176 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.89 e Å⁻³
Δρ_min = −1.85 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H3⋯O4ⁱ	0.97	1.83	2.764 (4)	160
O8—H4⋯O5ⁱⁱ	0.92	1.78	2.691 (4)	170
O7—H1⋯O2ⁱ	0.91	1.75	2.657 (4)	170
O7—H2⋯O3ⁱⁱⁱ	0.98	1.81	2.682 (4)	146
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z+1.

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811007719/pv2390sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811007719/pv2390Isup2.hkl

checkCIF report

Comment top

In recent years, a great interest has been focused on the crystal engineering of novel coordination polymers, not only due to their intriguing topological structures but also potential application as functional materials in areas such as ion exchange, catalysis, optics, gas separation/storage and sensing (Moulton & Zaworotko, 2001; Wood & Thompson, 2007). The RE-adipate (RE = rare earth metal) system has been examined extensively owing to the rich structural diversity of this family of materials. A great many of compounds have been reported which exhibit structure types ranging from 1-D chain to 2-D layer and 3-D framework topologies (Dimos et al., 2002; Duan et al., 2004; Kim et al., 2004; Kiritsis et al., 1998). Arguably much of this diversity is related to the flexibility of the aliphatic dicarboxylic backbone. In this paper, we report the hydrothermal synthesis and single-crystal X-ray diffraction analysis of a novel Tb-adipate compound, which is isotypic with La(III) (Kim et al., 2004) and Dy(III) (Lill et al., 2005) analogous complexes.

The crystal structure of the title complex consists of nine oxygen atoms coordinated to Tb(III) (Fig. 1) of which seven oxygen atoms are from four adipate ligands and two from two independent coordinated water molecules. Two symmetric TbO₉ polyhedra share their edges to form a Tb₂O₁₆ dimeric unit about an inversion centet. These dimers are further linked through adipate anions to form a two-dimensional layer perpendicular to (010) (Fig. 2).

C9-atom of the adipate ligand was disordered over two sites with site occupancy factors 0.622 (9) and 0.378 (9). The structure also contains a disordered molecule of water of hydration lying close to a special position with partial occupancy.

Related literature top

For background to coordination polymers, see: Moulton & Zaworotko (2001); Wood & Thompson (2007). For the structures of rare earth--adipate compounds, see: Dimos et al. (2002); Duan et al. (2004); Kim et al. (2004); Kiritsis et al. (1998). For the structures of isotypic La(III) and Dy(III) compounds, see: Kim et al. (2004); Lill et al. (2005).

Experimental top

Colorless prismatic single crystals of the title complex were obtained using hydrothermal methods in a sealed 20 ml Teflon-lined Parr bomb. TbCl₃ ^. 6H₂O (0.2 g), adipic acid (0.1 g) and H₂O (10 ml) were placed in the bomb and sealed. The bomb was then heated under autogenous pressure for 7 d at 433 K and finally cooled to room temperature. Upon opening the bomb, a few single crystals was obtained for X-ray single-crystal diffraction analysis.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of part of the title structure. Ellipsoids are drwan at the 50% probability level. Symmetry code: (i) 2 - x, -y, 2 - z (ii) 1 - x, -y, 1 - z; (iii) -1 + x, y, z.]
	Fig. 2. A view of the unit cell along the b-aixs of the title compound. showing TbO₉ polyhedra and the adipate ligands (represented by lines).

Poly[[tetraaquatris(µ₃-hexane-1,6-dicarboxylato)diterbium(III)] 0.25-hydrate] top

Crystal data top

[Tb₂(C₆H₈O₄)₃(H₂O)₄]·0.25H₂O	F(000) = 801
M_r = 826.78	D_x = 2.036 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5053 reflections
a = 11.603 (6) Å	θ = 2.4–28.4°
b = 13.886 (7) Å	µ = 5.27 mm⁻¹
c = 8.969 (4) Å	T = 298 K
β = 111.017 (7)°	Prism, colourless
V = 1348.9 (11) Å³	0.25 × 0.05 × 0.05 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	2335 independent reflections
Radiation source: fine-focus sealed tube	2008 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.352, T_max = 0.779	k = −16→16
7908 measured reflections	l = −10→10

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.066	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0379P)²] where P = (F_o² + 2F_c²)/3
2335 reflections	(Δ/σ)_max = 0.001
176 parameters	Δρ_max = 0.89 e Å⁻³
6 restraints	Δρ_min = −1.85 e Å⁻³

Crystal data top

[Tb₂(C₆H₈O₄)₃(H₂O)₄]·0.25H₂O	V = 1348.9 (11) Å³
M_r = 826.78	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.603 (6) Å	µ = 5.27 mm⁻¹
b = 13.886 (7) Å	T = 298 K
c = 8.969 (4) Å	0.25 × 0.05 × 0.05 mm
β = 111.017 (7)°

Data collection top

Bruker APEXII CCD diffractometer	2335 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2008 reflections with I > 2σ(I)
T_min = 0.352, T_max = 0.779	R_int = 0.037
7908 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	6 restraints
wR(F²) = 0.066	H-atom parameters constrained
S = 1.06	Δρ_max = 0.89 e Å⁻³
2335 reflections	Δρ_min = −1.85 e Å⁻³
176 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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	Occ. (<1)
Tb1	0.629324 (17)	0.108556 (13)	0.55754 (2)	0.01822 (10)
O1	0.4353 (3)	0.0374 (2)	0.5851 (3)	0.0239 (7)
O2	0.4828 (3)	0.1849 (2)	0.6661 (4)	0.0350 (8)
O3	0.7081 (3)	−0.0211 (2)	0.7500 (4)	0.0320 (8)
O4	0.7368 (4)	0.1232 (2)	0.8498 (4)	0.0352 (8)
O5	0.7300 (3)	0.1371 (2)	0.3584 (4)	0.0277 (7)
O6	0.8450 (3)	0.0963 (3)	0.5998 (5)	0.0453 (10)
O7	0.4652 (3)	0.1591 (2)	0.3279 (4)	0.0354 (8)
H1	0.4773	0.2153	0.2830	0.053*
H2	0.4046	0.1137	0.2594	0.053*
O8	0.6789 (3)	0.2728 (2)	0.5763 (4)	0.0375 (8)
H3	0.6884	0.3209	0.5031	0.056*
H4	0.7033	0.3077	0.6696	0.056*
C1	0.0666 (4)	0.1439 (5)	0.5747 (7)	0.0464 (14)
H1A	0.0643	0.0808	0.6199	0.056*
H1B	0.0690	0.1913	0.6552	0.056*
C2	0.1850 (4)	0.1522 (4)	0.5390 (7)	0.0398 (13)
H2A	0.1790	0.1117	0.4484	0.048*
H2B	0.1957	0.2183	0.5113	0.048*
C3	0.2943 (5)	0.1221 (4)	0.6808 (7)	0.0349 (12)
H3A	0.2774	0.0600	0.7181	0.042*
H3B	0.3067	0.1683	0.7663	0.042*
C4	0.4110 (4)	0.1151 (3)	0.6439 (6)	0.0242 (10)
C5	0.9490 (4)	0.1579 (4)	0.4326 (6)	0.0351 (12)
H5A	0.9417	0.2252	0.4013	0.042*
H5B	0.9534	0.1203	0.3437	0.042*
C6	0.8359 (5)	0.1287 (3)	0.4661 (6)	0.0286 (11)
C7	0.7559 (4)	0.0338 (3)	0.8668 (5)	0.0242 (10)
C8	0.8394 (4)	−0.0062 (4)	1.0230 (6)	0.0373 (12)
H8A	0.8330	−0.0759	1.0201	0.045*	0.622 (9)
H8B	0.8127	0.0168	1.1074	0.045*	0.622 (9)
H8A'	0.8000	−0.0608	1.0522	0.045*	0.378 (9)
H8B'	0.8548	0.0424	1.1049	0.045*	0.378 (9)
C9	0.9742 (8)	0.0224 (7)	1.0609 (10)	0.0380 (18)	0.622 (9)
H9A	1.0234	0.0009	1.1677	0.046*	0.622 (9)
H9B	0.9804	0.0920	1.0582	0.046*	0.622 (9)
C9'	0.9608 (13)	−0.0416 (11)	1.0113 (17)	0.0380 (18)	0.378 (9)
H9'1	1.0072	−0.0765	1.1078	0.046*	0.378 (9)
H9'2	0.9429	−0.0857	0.9219	0.046*	0.378 (9)
H1O9	0.4920	0.0730	−0.0380	0.046*	0.125
H2O9	0.5400	0.0476	0.1203	0.046*	0.125
O9	0.508 (4)	0.024 (2)	0.026 (5)	0.063 (10)	0.125

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tb1	0.01601 (14)	0.02031 (14)	0.01799 (15)	−0.00133 (8)	0.00566 (10)	0.00041 (8)
O1	0.0267 (16)	0.0223 (15)	0.0254 (18)	0.0007 (14)	0.0126 (14)	−0.0019 (13)
O2	0.0334 (18)	0.0273 (17)	0.051 (2)	−0.0085 (15)	0.0226 (18)	−0.0127 (16)
O3	0.0277 (17)	0.0314 (17)	0.029 (2)	−0.0065 (15)	0.0006 (16)	0.0036 (15)
O4	0.049 (2)	0.0325 (18)	0.0229 (19)	0.0097 (17)	0.0118 (18)	−0.0019 (14)
O5	0.0216 (17)	0.0349 (16)	0.0253 (19)	−0.0041 (14)	0.0069 (15)	0.0031 (14)
O6	0.0211 (18)	0.078 (3)	0.040 (2)	0.0062 (17)	0.0150 (17)	0.0262 (19)
O7	0.0312 (18)	0.0276 (17)	0.035 (2)	−0.0052 (15)	−0.0035 (16)	0.0118 (15)
O8	0.063 (2)	0.0265 (16)	0.028 (2)	−0.0183 (17)	0.0217 (18)	−0.0066 (14)
C1	0.021 (3)	0.074 (4)	0.046 (4)	−0.005 (3)	0.015 (3)	−0.002 (3)
C2	0.020 (2)	0.054 (3)	0.051 (4)	−0.002 (2)	0.019 (3)	−0.001 (3)
C3	0.030 (3)	0.042 (3)	0.039 (3)	−0.003 (2)	0.020 (3)	−0.006 (2)
C4	0.023 (2)	0.031 (3)	0.018 (3)	0.003 (2)	0.005 (2)	0.0017 (18)
C5	0.023 (2)	0.048 (3)	0.036 (3)	−0.003 (2)	0.012 (2)	0.009 (2)
C6	0.025 (3)	0.035 (3)	0.029 (3)	0.001 (2)	0.014 (2)	0.000 (2)
C7	0.015 (2)	0.035 (3)	0.022 (3)	0.000 (2)	0.006 (2)	0.003 (2)
C8	0.034 (3)	0.050 (3)	0.027 (3)	0.003 (2)	0.009 (2)	0.010 (2)
C9	0.035 (4)	0.044 (5)	0.026 (5)	0.015 (4)	−0.001 (3)	0.005 (4)
C9'	0.035 (4)	0.044 (5)	0.026 (5)	0.015 (4)	−0.001 (3)	0.005 (4)
O9	0.062 (12)	0.065 (14)	0.057 (13)	−0.001 (10)	0.014 (9)	0.000 (9)

Geometric parameters (Å, º) top

Tb1—O8	2.344 (3)	C2—C3	1.498 (7)
Tb1—O7	2.355 (3)	C2—H2A	0.9700
Tb1—O1ⁱ	2.371 (3)	C2—H2B	0.9700
Tb1—O6	2.398 (4)	C3—C4	1.508 (7)
Tb1—O3	2.435 (3)	C3—H3A	0.9700
Tb1—O4	2.474 (4)	C3—H3B	0.9700
Tb1—O2	2.479 (3)	C5—C6	1.503 (6)
Tb1—O5	2.492 (3)	C5—C1ⁱⁱⁱ	1.509 (7)
Tb1—O1	2.550 (3)	C5—H5A	0.9700
Tb1—C6	2.812 (5)	C5—H5B	0.9700
Tb1—C7	2.830 (4)	C7—C8	1.495 (6)
Tb1—C4	2.904 (5)	C8—C9'	1.530 (15)
O1—C4	1.275 (5)	C8—C9	1.530 (10)
O1—Tb1ⁱ	2.371 (3)	C8—H8A	0.9700
O2—C4	1.247 (5)	C8—H8B	0.9700
O3—C7	1.252 (5)	C8—H8A'	0.9684
O4—C7	1.261 (5)	C8—H8B'	0.9664
O5—C6	1.267 (6)	C9—C9^iv	1.551 (17)
O6—C6	1.249 (6)	C9—H9A	0.9700
O7—H1	0.9127	C9—H9B	0.9700
O7—H2	0.9795	C9'—C9'^iv	1.53 (3)
O8—H3	0.9699	C9'—H9'1	0.9700
O8—H4	0.9193	C9'—H9'2	0.9700
C1—C5ⁱⁱ	1.509 (7)	O9—O9^v	0.80 (6)
C1—C2	1.523 (7)	O9—H1O9	0.8634
C1—H1A	0.9700	O9—H2O9	0.8563
C1—H1B	0.9700

O8—Tb1—O7	82.75 (12)	H3—O8—H4	100.4
O8—Tb1—O1ⁱ	153.26 (10)	C5ⁱⁱ—C1—C2	115.0 (5)
O7—Tb1—O1ⁱ	77.45 (11)	C5ⁱⁱ—C1—H1A	108.5
O8—Tb1—O6	80.95 (13)	C2—C1—H1A	108.5
O7—Tb1—O6	129.04 (12)	C5ⁱⁱ—C1—H1B	108.5
O1ⁱ—Tb1—O6	97.73 (12)	C2—C1—H1B	108.5
O8—Tb1—O3	130.46 (11)	H1A—C1—H1B	107.5
O7—Tb1—O3	145.14 (10)	C3—C2—C1	110.7 (5)
O1ⁱ—Tb1—O3	73.49 (11)	C3—C2—H2A	109.5
O6—Tb1—O3	74.36 (11)	C1—C2—H2A	109.5
O8—Tb1—O4	80.00 (11)	C3—C2—H2B	109.5
O7—Tb1—O4	147.57 (12)	C1—C2—H2B	109.5
O1ⁱ—Tb1—O4	125.71 (10)	H2A—C2—H2B	108.1
O6—Tb1—O4	74.80 (13)	C2—C3—C4	112.7 (4)
O3—Tb1—O4	52.50 (11)	C2—C3—H3A	109.1
O8—Tb1—O2	74.98 (11)	C4—C3—H3A	109.1
O7—Tb1—O2	76.28 (12)	C2—C3—H3B	109.1
O1ⁱ—Tb1—O2	116.67 (10)	C4—C3—H3B	109.1
O6—Tb1—O2	142.34 (13)	H3A—C3—H3B	107.8
O3—Tb1—O2	100.00 (12)	O2—C4—O1	119.3 (4)
O4—Tb1—O2	72.83 (12)	O2—C4—C3	121.1 (4)
O8—Tb1—O5	74.37 (10)	O1—C4—C3	119.6 (4)
O7—Tb1—O5	76.46 (11)	O2—C4—Tb1	58.0 (2)
O1ⁱ—Tb1—O5	83.58 (10)	O1—C4—Tb1	61.3 (2)
O6—Tb1—O5	52.68 (11)	C3—C4—Tb1	176.8 (3)
O3—Tb1—O5	118.21 (11)	C6—C5—C1ⁱⁱⁱ	112.7 (4)
O4—Tb1—O5	123.96 (12)	C6—C5—H5A	109.1
O2—Tb1—O5	141.00 (11)	C1ⁱⁱⁱ—C5—H5A	109.1
O8—Tb1—O1	124.91 (11)	C6—C5—H5B	109.1
O7—Tb1—O1	74.63 (11)	C1ⁱⁱⁱ—C5—H5B	109.1
O1ⁱ—Tb1—O1	66.54 (11)	H5A—C5—H5B	107.8
O6—Tb1—O1	149.81 (10)	O6—C6—O5	119.3 (4)
O3—Tb1—O1	76.40 (10)	O6—C6—C5	120.7 (5)
O4—Tb1—O1	93.22 (11)	O5—C6—C5	120.0 (4)
O2—Tb1—O1	51.26 (10)	O6—C6—Tb1	58.1 (2)
O5—Tb1—O1	142.02 (10)	O5—C6—Tb1	62.4 (2)
O8—Tb1—C6	73.22 (13)	C5—C6—Tb1	169.0 (4)
O7—Tb1—C6	102.82 (13)	O3—C7—O4	119.5 (4)
O1ⁱ—Tb1—C6	93.75 (12)	O3—C7—C8	120.1 (4)
O6—Tb1—C6	26.24 (13)	O4—C7—C8	120.4 (4)
O3—Tb1—C6	97.93 (13)	O3—C7—Tb1	59.0 (2)
O4—Tb1—C6	98.19 (14)	O4—C7—Tb1	60.9 (2)
O2—Tb1—C6	148.01 (12)	C8—C7—Tb1	171.4 (3)
O5—Tb1—C6	26.77 (12)	C7—C8—C9'	111.0 (6)
O1—Tb1—C6	160.27 (12)	C7—C8—C9	112.3 (5)
O8—Tb1—C7	105.01 (12)	C9'—C8—C9	37.4 (6)
O7—Tb1—C7	159.89 (12)	C7—C8—H8A	109.1
O1ⁱ—Tb1—C7	99.65 (12)	C9'—C8—H8A	75.1
O6—Tb1—C7	70.97 (12)	C9—C8—H8A	109.1
O3—Tb1—C7	26.17 (11)	C7—C8—H8B	109.1
O4—Tb1—C7	26.44 (11)	C9'—C8—H8B	136.0
O2—Tb1—C7	87.70 (12)	C9—C8—H8B	109.1
O5—Tb1—C7	123.31 (11)	H8A—C8—H8B	107.9
O1—Tb1—C7	85.91 (11)	C7—C8—H8A'	109.5
C6—Tb1—C7	97.21 (13)	C9'—C8—H8A'	107.6
O8—Tb1—C4	99.53 (12)	C9—C8—H8A'	133.4
O7—Tb1—C4	73.43 (13)	H8A—C8—H8A'	35.6
O1ⁱ—Tb1—C4	91.91 (11)	H8B—C8—H8A'	74.5
O6—Tb1—C4	157.00 (13)	C7—C8—H8B'	109.5
O3—Tb1—C4	88.60 (12)	C9'—C8—H8B'	110.6
O4—Tb1—C4	82.60 (13)	C9—C8—H8B'	75.7
O2—Tb1—C4	25.24 (10)	H8A—C8—H8B'	135.1
O5—Tb1—C4	149.81 (12)	H8B—C8—H8B'	36.8
O1—Tb1—C4	26.02 (10)	H8A'—C8—H8B'	108.5
C6—Tb1—C4	172.36 (13)	C8—C9—C9^iv	111.2 (9)
C7—Tb1—C4	86.88 (13)	C8—C9—H9A	109.4
C4—O1—Tb1ⁱ	150.7 (3)	C9^iv—C9—H9A	109.4
C4—O1—Tb1	92.7 (3)	C8—C9—H9B	109.4
Tb1ⁱ—O1—Tb1	113.46 (11)	C9^iv—C9—H9B	109.4
C4—O2—Tb1	96.8 (3)	H9A—C9—H9B	108.0
C7—O3—Tb1	94.8 (3)	C9'^iv—C9'—C8	112.0 (14)
C7—O4—Tb1	92.7 (3)	C9'^iv—C9'—H9'1	109.2
C6—O5—Tb1	90.8 (3)	C8—C9'—H9'1	109.2
C6—O6—Tb1	95.7 (3)	C9'^iv—C9'—H9'2	109.2
Tb1—O7—H1	115.9	C8—C9'—H9'2	109.2
Tb1—O7—H2	122.0	H9'1—C9'—H9'2	107.9
H1—O7—H2	117.6	O9^v—O9—H1O9	108.8
Tb1—O8—H3	134.9	O9^v—O9—H2O9	145.0
Tb1—O8—H4	124.4	H1O9—O9—H2O9	105.9

O8—Tb1—O1—C4	−14.2 (3)	O1ⁱ—Tb1—C4—O2	−169.2 (3)
O7—Tb1—O1—C4	−83.6 (3)	O6—Tb1—C4—O2	75.8 (4)
O1ⁱ—Tb1—O1—C4	−166.4 (3)	O3—Tb1—C4—O2	117.4 (3)
O6—Tb1—O1—C4	130.7 (3)	O4—Tb1—C4—O2	65.0 (3)
O3—Tb1—O1—C4	116.0 (3)	O5—Tb1—C4—O2	−88.7 (4)
O4—Tb1—O1—C4	65.8 (3)	O1—Tb1—C4—O2	178.3 (5)
O2—Tb1—O1—C4	0.9 (2)	C7—Tb1—C4—O2	91.2 (3)
O5—Tb1—O1—C4	−125.3 (3)	O8—Tb1—C4—O1	168.2 (2)
C6—Tb1—O1—C4	−168.7 (3)	O7—Tb1—C4—O1	88.8 (3)
C7—Tb1—O1—C4	91.3 (3)	O1ⁱ—Tb1—C4—O1	12.5 (3)
O8—Tb1—O1—Tb1ⁱ	152.16 (12)	O6—Tb1—C4—O1	−102.5 (4)
O7—Tb1—O1—Tb1ⁱ	82.74 (14)	O3—Tb1—C4—O1	−60.9 (2)
O1ⁱ—Tb1—O1—Tb1ⁱ	0.0	O4—Tb1—C4—O1	−113.3 (3)
O6—Tb1—O1—Tb1ⁱ	−63.0 (3)	O2—Tb1—C4—O1	−178.3 (5)
O3—Tb1—O1—Tb1ⁱ	−77.66 (14)	O5—Tb1—C4—O1	93.0 (3)
O4—Tb1—O1—Tb1ⁱ	−127.80 (12)	C7—Tb1—C4—O1	−87.1 (3)
O2—Tb1—O1—Tb1ⁱ	167.3 (2)	Tb1—O6—C6—O5	−12.6 (5)
O5—Tb1—O1—Tb1ⁱ	41.1 (2)	Tb1—O6—C6—C5	167.2 (4)
C6—Tb1—O1—Tb1ⁱ	−2.4 (4)	Tb1—O5—C6—O6	12.0 (5)
C7—Tb1—O1—Tb1ⁱ	−102.37 (14)	Tb1—O5—C6—C5	−167.8 (4)
C4—Tb1—O1—Tb1ⁱ	166.4 (3)	C1ⁱⁱⁱ—C5—C6—O6	−0.4 (7)
O8—Tb1—O2—C4	166.2 (3)	C1ⁱⁱⁱ—C5—C6—O5	179.4 (5)
O7—Tb1—O2—C4	80.2 (3)	C1ⁱⁱⁱ—C5—C6—Tb1	79.9 (19)
O1ⁱ—Tb1—O2—C4	12.1 (3)	O8—Tb1—C6—O6	103.9 (3)
O6—Tb1—O2—C4	−141.7 (3)	O7—Tb1—C6—O6	−177.9 (3)
O3—Tb1—O2—C4	−64.4 (3)	O1ⁱ—Tb1—C6—O6	−99.9 (3)
O4—Tb1—O2—C4	−109.8 (3)	O3—Tb1—C6—O6	−26.1 (3)
O5—Tb1—O2—C4	127.0 (3)	O4—Tb1—C6—O6	27.0 (3)
O1—Tb1—O2—C4	−1.0 (3)	O2—Tb1—C6—O6	97.6 (4)
C6—Tb1—O2—C4	172.5 (3)	O5—Tb1—C6—O6	−167.6 (5)
C7—Tb1—O2—C4	−87.6 (3)	O1—Tb1—C6—O6	−97.7 (4)
O8—Tb1—O3—C7	15.6 (3)	C7—Tb1—C6—O6	0.3 (3)
O7—Tb1—O3—C7	−143.5 (3)	O8—Tb1—C6—O5	−88.5 (3)
O1ⁱ—Tb1—O3—C7	−178.2 (3)	O7—Tb1—C6—O5	−10.2 (3)
O6—Tb1—O3—C7	78.6 (3)	O1ⁱ—Tb1—C6—O5	67.7 (3)
O4—Tb1—O3—C7	−4.0 (2)	O6—Tb1—C6—O5	167.6 (5)
O2—Tb1—O3—C7	−63.2 (3)	O3—Tb1—C6—O5	141.6 (3)
O5—Tb1—O3—C7	108.7 (3)	O4—Tb1—C6—O5	−165.4 (3)
O1—Tb1—O3—C7	−109.0 (3)	O2—Tb1—C6—O5	−94.8 (3)
C6—Tb1—O3—C7	90.2 (3)	O1—Tb1—C6—O5	69.9 (5)
C4—Tb1—O3—C7	−85.8 (3)	C7—Tb1—C6—O5	168.0 (3)
O8—Tb1—O4—C7	−161.0 (3)	O8—Tb1—C6—C5	17.0 (18)
O7—Tb1—O4—C7	140.1 (3)	O7—Tb1—C6—C5	95.2 (19)
O1ⁱ—Tb1—O4—C7	10.9 (3)	O1ⁱ—Tb1—C6—C5	173.2 (19)
O6—Tb1—O4—C7	−77.7 (3)	O6—Tb1—C6—C5	−86.9 (19)
O3—Tb1—O4—C7	4.0 (2)	O3—Tb1—C6—C5	−113.0 (19)
O2—Tb1—O4—C7	121.8 (3)	O4—Tb1—C6—C5	−59.9 (19)
O5—Tb1—O4—C7	−97.6 (3)	O2—Tb1—C6—C5	11 (2)
O1—Tb1—O4—C7	74.1 (3)	O5—Tb1—C6—C5	105.5 (19)
C6—Tb1—O4—C7	−89.7 (3)	O1—Tb1—C6—C5	175.4 (17)
C4—Tb1—O4—C7	97.9 (3)	C7—Tb1—C6—C5	−86.6 (19)
O8—Tb1—O5—C6	83.6 (3)	Tb1—O3—C7—O4	7.2 (4)
O7—Tb1—O5—C6	169.7 (3)	Tb1—O3—C7—C8	−170.0 (3)
O1ⁱ—Tb1—O5—C6	−111.7 (3)	Tb1—O4—C7—O3	−7.1 (4)
O6—Tb1—O5—C6	−6.8 (3)	Tb1—O4—C7—C8	170.2 (4)
O3—Tb1—O5—C6	−44.3 (3)	O8—Tb1—C7—O3	−167.8 (2)
O4—Tb1—O5—C6	17.6 (3)	O7—Tb1—C7—O3	81.6 (4)
O2—Tb1—O5—C6	123.0 (3)	O1ⁱ—Tb1—C7—O3	1.8 (3)
O1—Tb1—O5—C6	−149.0 (3)	O6—Tb1—C7—O3	−93.2 (3)
C7—Tb1—O5—C6	−14.3 (3)	O4—Tb1—C7—O3	172.8 (4)
C4—Tb1—O5—C6	165.6 (3)	O2—Tb1—C7—O3	118.4 (3)
O8—Tb1—O6—C6	−70.2 (3)	O5—Tb1—C7—O3	−86.9 (3)
O7—Tb1—O6—C6	2.7 (4)	O1—Tb1—C7—O3	67.1 (2)
O1ⁱ—Tb1—O6—C6	82.8 (3)	C6—Tb1—C7—O3	−93.3 (3)
O3—Tb1—O6—C6	153.1 (3)	C4—Tb1—C7—O3	93.2 (3)
O4—Tb1—O6—C6	−152.3 (3)	O8—Tb1—C7—O4	19.4 (3)
O2—Tb1—O6—C6	−120.7 (3)	O7—Tb1—C7—O4	−91.2 (4)
O5—Tb1—O6—C6	7.0 (3)	O1ⁱ—Tb1—C7—O4	−171.0 (3)
O1—Tb1—O6—C6	138.3 (3)	O6—Tb1—C7—O4	94.1 (3)
C7—Tb1—O6—C6	−179.7 (3)	O3—Tb1—C7—O4	−172.8 (4)
C4—Tb1—O6—C6	−163.3 (3)	O2—Tb1—C7—O4	−54.4 (3)
C5ⁱⁱ—C1—C2—C3	−171.1 (5)	O5—Tb1—C7—O4	100.3 (3)
C1—C2—C3—C4	171.6 (4)	O1—Tb1—C7—O4	−105.7 (3)
Tb1—O2—C4—O1	1.7 (5)	C6—Tb1—C7—O4	93.9 (3)
Tb1—O2—C4—C3	−176.4 (4)	C4—Tb1—C7—O4	−79.6 (3)
Tb1ⁱ—O1—C4—O2	−155.4 (4)	O3—C7—C8—C9'	69.0 (8)
Tb1—O1—C4—O2	−1.7 (4)	O4—C7—C8—C9'	−108.2 (8)
Tb1ⁱ—O1—C4—C3	22.7 (8)	O3—C7—C8—C9	109.3 (6)
Tb1—O1—C4—C3	176.5 (4)	O4—C7—C8—C9	−67.9 (6)
Tb1ⁱ—O1—C4—Tb1	−153.8 (6)	C7—C8—C9—C9^iv	−65.1 (10)
C2—C3—C4—O2	92.4 (6)	C9'—C8—C9—C9^iv	30.7 (10)
C2—C3—C4—O1	−85.7 (5)	C7—C8—C9'—C9'^iv	68.2 (15)
O8—Tb1—C4—O2	−13.5 (3)	C9—C8—C9'—C9'^iv	−31.4 (10)
O7—Tb1—C4—O2	−92.9 (3)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y, z; (iii) x+1, y, z; (iv) −x+2, −y, −z+2; (v) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H3···O4^vi	0.97	1.83	2.764 (4)	160
O8—H4···O5^vii	0.92	1.78	2.691 (4)	170
O7—H1···O2^vi	0.91	1.75	2.657 (4)	170
O7—H2···O3ⁱ	0.98	1.81	2.682 (4)	146

Symmetry codes: (i) −x+1, −y, −z+1; (vi) x, −y+1/2, z−1/2; (vii) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Tb₂(C₆H₈O₄)₃(H₂O)₄]·0.25H₂O
M_r	826.78
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	11.603 (6), 13.886 (7), 8.969 (4)
β (°)	111.017 (7)
V (Å³)	1348.9 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.27
Crystal size (mm)	0.25 × 0.05 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.352, 0.779
No. of measured, independent and observed [I > 2σ(I)] reflections	7908, 2335, 2008
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.066, 1.06
No. of reflections	2335
No. of parameters	176
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.89, −1.85

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H3···O4ⁱ	0.97	1.83	2.764 (4)	160
O8—H4···O5ⁱⁱ	0.92	1.78	2.691 (4)	170
O7—H1···O2ⁱ	0.91	1.75	2.657 (4)	170
O7—H2···O3ⁱⁱⁱ	0.98	1.81	2.682 (4)	146

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+1/2, z+1/2; (iii) −x+1, −y, −z+1.

Acknowledgements

The authors acknowledge the Doctoral Foundation of Henan Polytechnic University (B648174).

References

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