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Acta Cryst. (2007). E63, m2925    [ doi:10.1107/S1600536807055043 ]

Poly[[triaquasesqui-[mu]2-oxalato-terbium(III)] methanol solvate]

Z. Rong-Hua and L. Han-Guo

Abstract top

In the title complex, {[Tb(C2O4)1.5(H2O)3]·CH3OH}n, each TbIII atom is coordinated by six O atoms from three oxalate ligands and three water molecules, and displays a tricapped-trigonal prismatic geometry. The oxalate groups link the metal ions, forming layers perpendicular to the c axis that can be described via topological analysis as a three-connected (63) sheet. O-H...O hydrogen bonds from the water and methanol molecules to the oxalate ions further interconnect the layers, forming a supramolecular network.

Comment top

Molecular self-assembly of supramolecular architectures has received much attention during recent decades (Zeng et al., 2007; Moulton & Zaworotko, 2001). The structures and properties of such systems depend on the coordination and geometric preferences of both the central metal ions and the bridging building blocks, as well as the influence of weaker non-covalent interactions, such as hydrogen bonds and π-π stacking interactions. Recently, we obtained the title coordination polymer, which was synthesized under hydrothermal conditions.

As illustrated in Fig. 1, in the structure of the title compound each TbIII centre is in a tri-capped-trigonal prismatic geometry, defined by six carboxyl O atoms from three oxalate ligands and three water molecules. The oxalate ligands link the TbIII ions to form a smooth layer perpendicular to the c axis in which the shortest Tb···Tb separation is 6.210 (3) Å. These layers are connected through O—H···O hydrogen bonding (Table 1) involving the coordinating water and the methanol molecules as donors and acceptors, forming a three-dimensional supramolecular network (Fig. 2). The individual layers formed by the oxalate and metal ions form a motif which, via topological analysis, can be described as a 3-connected (63) sheet (Fig. 3).

Related literature top

For related literature, see: Brandenburg & Putz, (2006); Moulton & Zaworotko (2001); Zeng et al., (2007).

Experimental top

A mixture of Tb4O7 (0.189 g; 0.25 mmol), oxalic acid (0.135 g; 1.5 mmol), water and methanol (3 ml: 7 mL mixture) and HClO4 (0.385 mmol) was stirred vigorously for 20 min and then sealed in a Teflon-lined stainless-steel autoclave (20 ml, capacity). The autoclave was heated to and maintained at 433 K for 7 days, and then cooled to room temperature at 5 K h−1 to obtain the crystals.

Refinement top

Water H atoms were tentatively located in difference Fourier maps and were refined with distance restraints of O–H = 0.82 Å and H···H = 1.29 Å, each within a standard deviation of 0.01 Å; with Uiso(H) = 1.5 Ueq(O,). H atoms on the methanol molecule were placed at calculated positions and were treated as riding on the parent C atoms with C—H = 0.96 Å, and O—H = 0.82 Å, with Uiso(H) = 1.5 Ueq(O,C).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004); Diamond (Brandenburg & Putz, 2006); software used to prepare material for publication: SHELXTL (Bruker, 2004).

Figures top
[Figure 1] Fig. 1. The structure of the title compound, showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level. Symmetry codes: (i)-x, −y, −z; (ii)-x, −y, 1 − z; (iii)1 − x, −y, 1 − z.
[Figure 2] Fig. 2. View of the supramolecular network of the title structure.
[Figure 3] Fig. 3. Illustration of the topological (63) motif of the layered structure.
Poly[[triaquasesqui-µ2-oxalato-terbium(III)] methanol solvate] top
Crystal data top
[Tb(C2O4)1.5(H2O)3]·CH4OF000 = 716
Mr = 377.04Dx = 2.609 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -p 2ybcCell parameters from 2200 reflections
a = 10.8284 (2) Åθ = 2.1–27.5º
b = 9.8002 (2) ŵ = 7.41 mm−1
c = 9.88460 (10) ÅT = 296 (2) K
β = 113.7740 (10)ºBlocky, colorless
V = 959.95 (3) Å30.21 × 0.18 × 0.16 mm
Z = 4
Data collection top
Bruker APEX-II area-detector
diffractometer		2196 independent reflections
Radiation source: fine-focus sealed tube1901 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.030
T = 296(2) Kθmax = 27.5º
φ and ω scanθmin = 2.1º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −13→14
Tmin = 0.231, Tmax = 0.308k = −12→10
9378 measured reflectionsl = −12→12
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.022H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.046  w = 1/[σ2(Fo2) + (0.0203P)2 + 0.2004P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
2196 reflectionsΔρmax = 0.60 e Å−3
156 parametersΔρmin = −0.81 e Å−3
9 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Tb(C2O4)1.5(H2O)3]·CH4OV = 959.95 (3) Å3
Mr = 377.04Z = 4
Monoclinic, P21/cMo Kα
a = 10.8284 (2) ŵ = 7.41 mm−1
b = 9.8002 (2) ÅT = 296 (2) K
c = 9.88460 (10) Å0.21 × 0.18 × 0.16 mm
β = 113.7740 (10)º
Data collection top
Bruker APEX-II area-detector
diffractometer		2196 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1901 reflections with I > 2σ(I)
Tmin = 0.231, Tmax = 0.308Rint = 0.030
9378 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0229 restraints
wR(F2) = 0.046H atoms treated by a mixture of
independent and constrained refinement
S = 1.06Δρmax = 0.60 e Å−3
2196 reflectionsΔρmin = −0.81 e Å−3
156 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
xyzUiso*/Ueq
C10.0535 (4)0.0300 (4)0.5707 (4)0.0192 (8)
C20.4991 (4)0.0507 (3)0.5581 (4)0.0164 (8)
C30.0337 (4)−0.0697 (4)0.0043 (4)0.0175 (8)
C40.4073 (6)0.5977 (6)0.3276 (6)0.0630 (16)
H4A0.46980.62340.42490.094*
H4B0.42400.50500.30850.094*
H4C0.31670.60580.32110.094*
O10.1573 (3)0.0771 (3)0.5630 (3)0.0253 (6)
O20.0265 (3)0.0275 (3)0.6839 (3)0.0234 (6)
O30.3887 (2)0.1093 (3)0.5326 (3)0.0235 (6)
O40.6077 (3)0.0669 (3)0.6689 (3)0.0219 (6)
O50.1274 (3)−0.1003 (3)0.1245 (3)0.0247 (6)
O6−0.0103 (2)−0.1420 (3)−0.1111 (2)0.0227 (6)
H5W0.270 (3)0.2601 (15)0.180 (4)0.034*
H2W0.131 (4)0.345 (2)0.325 (3)0.034*
H1W0.200 (4)0.307 (3)0.4602 (15)0.034*
H3W0.150 (2)−0.219 (4)0.438 (4)0.034*
H6W0.3747 (11)0.182 (3)0.223 (4)0.034*
H4W0.270 (2)−0.184 (4)0.5270 (19)0.034*
O70.4246 (3)0.6869 (3)0.2191 (3)0.0414 (8)
H70.40620.76550.23260.062*
O1W0.1664 (3)0.2778 (3)0.3756 (3)0.0340 (7)
O2W0.2145 (3)−0.1722 (3)0.4416 (3)0.0316 (7)
O3W0.2913 (3)0.1790 (3)0.1933 (3)0.0282 (7)
Tb10.189510 (16)0.046207 (17)0.329650 (15)0.01138 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.019 (2)0.016 (2)0.0237 (18)−0.0033 (17)0.0098 (17)−0.0037 (15)
C20.014 (2)0.015 (2)0.0195 (17)0.0010 (17)0.0060 (15)0.0049 (14)
C30.014 (2)0.020 (2)0.0195 (17)0.0011 (17)0.0078 (15)0.0015 (15)
C40.083 (5)0.055 (4)0.056 (3)−0.004 (3)0.033 (3)−0.012 (3)
O10.0203 (16)0.0317 (17)0.0262 (13)−0.0102 (13)0.0117 (12)−0.0084 (12)
O20.0227 (16)0.0303 (18)0.0177 (12)−0.0068 (13)0.0087 (12)−0.0037 (11)
O30.0173 (15)0.0262 (16)0.0238 (12)0.0025 (13)0.0051 (11)−0.0064 (12)
O40.0143 (14)0.0256 (17)0.0209 (12)0.0038 (12)0.0021 (11)−0.0023 (11)
O50.0224 (16)0.0263 (16)0.0178 (12)0.0075 (13)0.0004 (11)−0.0007 (11)
O60.0264 (16)0.0205 (15)0.0180 (12)−0.0005 (13)0.0056 (11)−0.0048 (11)
O70.044 (2)0.037 (2)0.0373 (16)0.0060 (17)0.0095 (15)−0.0110 (15)
O1W0.049 (2)0.0232 (17)0.0186 (12)0.0133 (15)0.0021 (13)0.0009 (12)
O2W0.0266 (17)0.035 (2)0.0298 (14)−0.0039 (15)0.0079 (13)0.0091 (13)
O3W0.0255 (16)0.0258 (17)0.0341 (15)0.0032 (13)0.0129 (14)0.0088 (13)
Tb10.00966 (10)0.01277 (11)0.01034 (8)−0.00022 (8)0.00259 (7)−0.00001 (6)
Geometric parameters (Å, °) top
C1—O11.246 (4)O4—Tb1ii2.455 (3)
C1—O21.266 (4)O5—Tb12.351 (2)
C1—C1i1.529 (7)O6—Tb1iii2.436 (2)
C2—O41.252 (4)O7—H70.8200
C2—O31.257 (4)O1W—Tb12.348 (3)
C2—C2ii1.526 (7)O1W—H2W0.821 (10)
C3—O51.249 (4)O1W—H1W0.818 (10)
C3—O61.262 (4)O2W—Tb12.374 (3)
C3—C3iii1.535 (7)O2W—H3W0.825 (10)
C4—O71.453 (6)O2W—H4W0.825 (10)
C4—H4A0.9600O3W—Tb12.434 (3)
C4—H4B0.9600O3W—H5W0.824 (10)
C4—H4C0.9600O3W—H6W0.830 (10)
O1—Tb12.486 (2)Tb1—O2i2.400 (3)
O2—Tb1i2.400 (3)Tb1—O6iii2.436 (2)
O3—Tb12.360 (2)Tb1—O4ii2.455 (3)
O1—C1—O2126.7 (3)O1W—Tb1—O2W141.49 (10)
O1—C1—C1i117.2 (4)O5—Tb1—O2W77.91 (9)
O2—C1—C1i116.1 (4)O3—Tb1—O2W86.94 (10)
O4—C2—O3126.8 (3)O1W—Tb1—O2i97.15 (10)
O4—C2—C2ii116.6 (4)O5—Tb1—O2i80.49 (9)
O3—C2—C2ii116.5 (4)O3—Tb1—O2i131.49 (8)
O5—C3—O6126.2 (3)O2W—Tb1—O2i71.34 (9)
O5—C3—C3iii116.9 (4)O1W—Tb1—O3W72.39 (10)
O6—C3—C3iii116.8 (4)O5—Tb1—O3W83.37 (9)
O7—C4—H4A109.5O3—Tb1—O3W82.42 (9)
O7—C4—H4B109.5O2W—Tb1—O3W138.43 (10)
H4A—C4—H4B109.5O2i—Tb1—O3W141.16 (9)
O7—C4—H4C109.5O1W—Tb1—O6iii71.95 (8)
H4A—C4—H4C109.5O5—Tb1—O6iii67.79 (8)
H4B—C4—H4C109.5O3—Tb1—O6iii141.38 (9)
C1—O1—Tb1118.6 (2)O2W—Tb1—O6iii131.37 (9)
C1—O2—Tb1i121.6 (2)O2i—Tb1—O6iii69.88 (8)
C2—O3—Tb1121.4 (2)O3W—Tb1—O6iii71.32 (9)
C2—O4—Tb1ii118.0 (2)O1W—Tb1—O4ii126.88 (10)
C3—O5—Tb1120.9 (2)O5—Tb1—O4ii70.92 (8)
C3—O6—Tb1iii117.4 (2)O3—Tb1—O4ii66.71 (8)
C4—O7—H7109.5O2W—Tb1—O4ii69.91 (9)
Tb1—O1W—H2W136 (2)O2i—Tb1—O4ii135.56 (9)
Tb1—O1W—H1W120 (2)O3W—Tb1—O4ii68.96 (9)
H2W—O1W—H1W104.0 (16)O6iii—Tb1—O4ii124.77 (8)
Tb1—O2W—H3W123 (3)O1W—Tb1—O168.74 (9)
Tb1—O2W—H4W120 (3)O5—Tb1—O1140.93 (9)
H3W—O2W—H4W103.0 (16)O3—Tb1—O166.50 (8)
Tb1—O3W—H5W116 (3)O2W—Tb1—O173.13 (9)
Tb1—O3W—H6W120 (3)O2i—Tb1—O165.82 (8)
H5W—O3W—H6W102.2 (16)O3W—Tb1—O1135.47 (9)
O1W—Tb1—O5137.87 (9)O6iii—Tb1—O1114.59 (8)
O1W—Tb1—O373.41 (10)O4ii—Tb1—O1120.61 (8)
O5—Tb1—O3137.62 (9)
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y, −z+1; (iii) −x, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3W—H5W···O1iv0.824 (10)2.056 (18)2.823 (4)155 (4)
O3W—H5W···O3iv0.824 (10)2.63 (3)3.048 (4)113 (3)
O1W—H2W···O2iv0.821 (10)1.876 (11)2.685 (4)168 (4)
O2W—H3W···O6v0.825 (10)2.102 (13)2.913 (4)168 (4)
O2W—H3W···O5v0.825 (10)2.64 (3)3.240 (4)131 (3)
O3W—H6W···O7vi0.830 (10)2.011 (11)2.841 (4)176 (4)
O2W—H4W···O7vii0.825 (10)1.960 (11)2.774 (4)168 (3)
O1W—H1W···O3Wvii0.818 (10)2.114 (12)2.906 (4)163 (3)
O7—H7···O4viii0.821.952.735 (4)161
Symmetry codes: (iv) x, −y+1/2, z−1/2; (v) x, −y−1/2, z+1/2; (vi) −x+1, y−1/2, −z+1/2; (vii) x, −y+1/2, z+1/2; (viii) −x+1, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3W—H5W···O1i0.824 (10)2.056 (18)2.823 (4)155 (4)
O3W—H5W···O3i0.824 (10)2.63 (3)3.048 (4)113 (3)
O1W—H2W···O2i0.821 (10)1.876 (11)2.685 (4)168 (4)
O2W—H3W···O6ii0.825 (10)2.102 (13)2.913 (4)168 (4)
O2W—H3W···O5ii0.825 (10)2.64 (3)3.240 (4)131 (3)
O3W—H6W···O7iii0.830 (10)2.011 (11)2.841 (4)176 (4)
O2W—H4W···O7iv0.825 (10)1.960 (11)2.774 (4)168 (3)
O1W—H1W···O3Wiv0.818 (10)2.114 (12)2.906 (4)163 (3)
O7—H7···O4v0.821.952.735 (4)161
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y−1/2, z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) x, −y+1/2, z+1/2; (v) −x+1, −y+1, −z+1.
Acknowledgements top

The authors thank South China Normal University for supporting this study.

references
References top

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Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.

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