metal-organic compounds
Poly[[tetraaquadi-μ4-fumarato-μ2-oxalato-dierbium(III)] tetrahydrate]
aKey Laboratory of Energy Resources and Chemical Engineering, Ningxia University, Yinchuan 750021, Ningxia, People's Republic of China, and bCollege of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, Ningxia, People's Republic of China
*Correspondence e-mail: yangqf@nxu.edu.cn
The title compound, {[Er2(C4H2O4)2(C2O4)(H2O)4]·4H2O}n, was synthesized by the reaction of erbium nitrate hexahydrate with fumaric acid and oxalic acid under hydrothermal conditions. The Er3+ cation (site symmetry ..2) is eight-coordinated by six O atoms from four fumarate anions (site symmetry ..2) and one bidentate oxalate anion (site symmetry 222), and by two water molecules. The complex exhibits a three-dimensional structure consisting of oxalate pillared Er–fumarate layers with channels occupied by coordinating and lattice water molecules. The three-dimensional structure features by Owater—H⋯O hydrogen bonds involving both the coordinating and lattice water molecules.
Related literature
For lanthanide–metal complexes containing fumarate ligands, see: Zhang et al. (2006). For lanthanide-containing structures with metal-organic frameworks and two different flexible carboxylate ligands, see: Zhang et al. (2008); Zhu et al. (2007).
Experimental
Crystal data
|
Refinement
|
Data collection: SMART (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Supporting information
https://doi.org/10.1107/S160053681205026X/hg5272sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681205026X/hg5272Isup2.hkl
A mixture of fumaric acid (0.058 g, 0.50 mmol), oxalic acid (0.063 g, 0.50 mmol) and erbium nitrate hexahydrate (0.230 g, 0.50 mmol) in distilled water (15 ml) was stirred fully in air, and then sealed in 25 ml Teflon-lined stainless steel container, which was heated firstly at 403 K for 2 days and then at 443 K for 1 day. The pink block product, I, was crystallized upon cooling to 273 K.
The H atoms attached to carbon were positioned geometrically and treated as riding on their parent atoms, with C—H 0.93. The hydrogen atoms of the water molecules were located in difference maps and refined by using the 'DFIX' command with O—H = 0.85 (2)Å with Uiso(H) = 1.5Uiso(O).
In recent years, lanthanide metal-organic compounds have been of great interest due to their fascinating structures and potential applications in magnetism, luminescence, catalysis, gas storage and separation. Multitopic carboxylates have received considerable study due to their availability and potential for allowing for the tailored design of such frameworks. As we know, fumaric acid is a unique ligand with a relatively small, conjugated middle part and versatile coordination modes. A large number of lanthanide metal complexes containing fumarate ligands have been reported, see: Zhang et al. (2006). And lanthanide-containing MOFs with two different flexible carboxylate ligands are less developed, see: Zhang et al.(2008); Zhu et al.(2007). In this paper, we report the synthesis and structure of a new metal-organic compound constructed from fumarate ligands coordinated to Er atoms in the presence of oxalate ligands.
In the title compound I, Er1 is eight-coordinated with four O atoms from four fumarate ligands (O2iii, O1iv, O2, O1v, (iii), 1.25 - x, 0.25 - y, z; (iv) 1.5 - x, 0.5 - y, 1 - z; (v) -0.25 + x, -0.25 + y, 1 - z), two O atoms from one oxalate ligand (O3 and O3iii) and two water molecules (O4 and O4iii) (Fig. 1). The Er—O bond lengths are between 2.273 (3)–2.428 (3) Å. The Er atoms are linked through bridging carboxyl groups of fumarate ligands to form two-dimensional Er–fum layers in the ab plane (Fig. 2). Along the c direction, the Er-fum layers are pillared by the oxalic acid resulting in a three-dimensional structure. The framework contains approximately 6.2 Å×11.1 Å rectangular channels along the [100] direction. These channels are occupied by coordinated and free water molecules (Fig. 3). The three-dimensional structure is stabilized by Owater—H···O hydrogen bonds involving both the coordinated and free water molecules.
For lanthanide–metal complexes containing fumarate ligands, see: Zhang et al. (2006). For lanthanide-containing structures with metal-organic frameworks and two different flexible carboxylate ligands, see: Zhang et al. (2008); Zhu et al. (2007).
Data collection: SMART (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).[Er2(C4H2O4)2(C2O4)(H2O)4]·4H2O | Dx = 2.621 Mg m−3 |
Mr = 794.78 | Melting point: not measured K |
Orthorhombic, Fddd | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -F 2uv 2vw | Cell parameters from 9875 reflections |
a = 9.6016 (19) Å | θ = 3.0–27.5° |
b = 15.701 (3) Å | µ = 8.38 mm−1 |
c = 26.722 (5) Å | T = 293 K |
V = 4028.5 (14) Å3 | Block, pink |
Z = 8 | 0.19 × 0.16 × 0.13 mm |
F(000) = 3008 |
Bruker SMART APEX CCD diffractometer | 1162 independent reflections |
Radiation source: fine-focus sealed tube | 1088 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
Detector resolution: 9.00cm pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ω scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | k = −20→20 |
Tmin = 0.305, Tmax = 0.402 | l = −34→31 |
9284 measured reflections |
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)] = 0.018 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.045 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0186P)2 + 60.2587P] where P = (Fo2 + 2Fc2)/3 |
1162 reflections | (Δ/σ)max = 0.003 |
74 parameters | Δρmax = 0.51 e Å−3 |
0 restraints | Δρmin = −1.04 e Å−3 |
[Er2(C4H2O4)2(C2O4)(H2O)4]·4H2O | V = 4028.5 (14) Å3 |
Mr = 794.78 | Z = 8 |
Orthorhombic, Fddd | Mo Kα radiation |
a = 9.6016 (19) Å | µ = 8.38 mm−1 |
b = 15.701 (3) Å | T = 293 K |
c = 26.722 (5) Å | 0.19 × 0.16 × 0.13 mm |
Bruker SMART APEX CCD diffractometer | 1162 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 1088 reflections with I > 2σ(I) |
Tmin = 0.305, Tmax = 0.402 | Rint = 0.022 |
9284 measured reflections |
R[F2 > 2σ(F2)] = 0.018 | 0 restraints |
wR(F2) = 0.045 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0186P)2 + 60.2587P] where P = (Fo2 + 2Fc2)/3 |
1162 reflections | Δρmax = 0.51 e Å−3 |
74 parameters | Δρmin = −1.04 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.9358 (4) | 0.1660 (2) | 0.52974 (13) | 0.0167 (6) | |
C2 | 1.0906 (4) | 0.1604 (3) | 0.53278 (16) | 0.0268 (8) | |
H2 | 1.1407 | 0.2110 | 0.5348 | 0.032* | |
C3 | 0.6250 | 0.0756 (3) | 0.6250 | 0.0150 (8) | |
Er1 | 0.6250 | 0.1250 | 0.508677 (7) | 0.01528 (8) | |
O1 | 0.8868 (3) | 0.23742 (16) | 0.51740 (10) | 0.0237 (5) | |
O2 | 0.8597 (3) | 0.10210 (16) | 0.53731 (11) | 0.0239 (5) | |
O3 | 0.6164 (3) | 0.04009 (15) | 0.58332 (9) | 0.0190 (5) | |
O4 | 0.4757 (3) | 0.12267 (15) | 0.43533 (9) | 0.0256 (5) | |
H4A | 0.3985 | 0.1447 | 0.4440 | 0.031* | |
H4B | 0.4595 | 0.0706 | 0.4288 | 0.031* | |
O5 | 0.5533 (3) | 0.20049 (15) | 0.34370 (9) | 0.0859 (16) | |
H5A | 0.5298 | 0.1769 | 0.3711 | 0.103* | |
H5B | 0.5661 | 0.2534 | 0.3485 | 0.129* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0141 (15) | 0.0186 (16) | 0.0173 (16) | 0.0032 (13) | −0.0010 (13) | 0.0001 (13) |
C2 | 0.0159 (17) | 0.0232 (18) | 0.041 (2) | −0.0021 (14) | 0.0015 (15) | −0.0025 (17) |
C3 | 0.0133 (19) | 0.013 (2) | 0.019 (2) | 0.000 | −0.0012 (19) | 0.000 |
Er1 | 0.01765 (12) | 0.01422 (11) | 0.01396 (11) | 0.00560 (8) | 0.000 | 0.000 |
O1 | 0.0239 (13) | 0.0200 (12) | 0.0270 (13) | 0.0067 (10) | 0.0003 (11) | 0.0045 (10) |
O2 | 0.0168 (12) | 0.0205 (12) | 0.0344 (14) | 0.0009 (10) | 0.0001 (11) | 0.0027 (11) |
O3 | 0.0269 (13) | 0.0139 (11) | 0.0161 (11) | −0.0003 (10) | −0.0015 (10) | −0.0010 (9) |
O4 | 0.0296 (13) | 0.0215 (12) | 0.0256 (13) | −0.0017 (11) | −0.0040 (11) | 0.0002 (11) |
O5 | 0.099 (4) | 0.076 (3) | 0.082 (3) | −0.011 (3) | 0.012 (3) | 0.037 (3) |
C1—O2 | 1.258 (4) | Er1—O3 | 2.401 (2) |
C1—O1 | 1.260 (4) | Er1—O2 | 2.407 (3) |
C1—C2 | 1.491 (5) | Er1—O2iii | 2.407 (3) |
C2—C2i | 1.294 (8) | Er1—O4 | 2.428 (2) |
C2—H2 | 0.9300 | Er1—O4iii | 2.428 (2) |
C3—O3 | 1.249 (3) | O1—Er1iv | 2.273 (3) |
C3—O3ii | 1.249 (3) | O4—H4A | 0.8500 |
C3—C3iii | 1.550 (9) | O4—H4B | 0.8499 |
Er1—O1iv | 2.273 (3) | O5—H5A | 0.8500 |
Er1—O1v | 2.273 (3) | O5—H5B | 0.8500 |
Er1—O3iii | 2.401 (2) | ||
O2—C1—O1 | 122.4 (3) | O3—Er1—O2iii | 77.67 (9) |
O2—C1—C2 | 121.5 (3) | O2—Er1—O2iii | 142.93 (13) |
O1—C1—C2 | 116.0 (3) | O1iv—Er1—O4 | 74.78 (9) |
C2i—C2—C1 | 124.0 (5) | O1v—Er1—O4 | 76.55 (9) |
C2i—C2—H2 | 118.0 | O3iii—Er1—O4 | 134.38 (9) |
C1—C2—H2 | 118.0 | O3—Er1—O4 | 129.93 (8) |
O3—C3—O3ii | 126.9 (4) | O2—Er1—O4 | 143.80 (9) |
O3—C3—C3iii | 116.6 (2) | O2iii—Er1—O4 | 72.91 (9) |
O3ii—C3—C3iii | 116.6 (2) | O1iv—Er1—O4iii | 76.55 (9) |
O1iv—Er1—O1v | 144.28 (13) | O1v—Er1—O4iii | 74.78 (9) |
O1iv—Er1—O3iii | 74.25 (9) | O3iii—Er1—O4iii | 129.93 (8) |
O1v—Er1—O3iii | 141.35 (9) | O3—Er1—O4iii | 134.38 (9) |
O1iv—Er1—O3 | 141.35 (9) | O2—Er1—O4iii | 72.91 (9) |
O1v—Er1—O3 | 74.25 (9) | O2iii—Er1—O4iii | 143.80 (9) |
O3iii—Er1—O3 | 67.62 (11) | O4—Er1—O4iii | 72.38 (12) |
O1iv—Er1—O2 | 106.62 (9) | C1—O1—Er1iv | 160.8 (3) |
O1v—Er1—O2 | 84.78 (9) | C1—O2—Er1 | 111.9 (2) |
O3iii—Er1—O2 | 77.67 (9) | C3—O3—Er1 | 119.4 (2) |
O3—Er1—O2 | 71.66 (9) | Er1—O4—H4A | 106.7 |
O1iv—Er1—O2iii | 84.78 (9) | Er1—O4—H4B | 106.7 |
O1v—Er1—O2iii | 106.62 (9) | H4A—O4—H4B | 106.7 |
O3iii—Er1—O2iii | 71.66 (9) | H5A—O5—H5B | 109.5 |
Symmetry codes: (i) −x+9/4, −y+1/4, z; (ii) −x+5/4, y, −z+5/4; (iii) −x+5/4, −y+1/4, z; (iv) −x+3/2, −y+1/2, −z+1; (v) x−1/4, y−1/4, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4A···O5vi | 0.85 | 2.35 | 3.045 (5) | 139 |
O4—H4B···O3vii | 0.85 | 1.91 | 2.750 (3) | 168 |
O5—H5A···O4 | 0.85 | 1.99 | 2.836 | 180 |
O5—H5B···O2viii | 0.85 | 2.36 | 2.938 (4) | 125 |
Symmetry codes: (vi) −x+3/4, y, −z+3/4; (vii) −x+1, −y, −z+1; (viii) −x+3/2, y+1/4, z−1/4. |
Experimental details
Crystal data | |
Chemical formula | [Er2(C4H2O4)2(C2O4)(H2O)4]·4H2O |
Mr | 794.78 |
Crystal system, space group | Orthorhombic, Fddd |
Temperature (K) | 293 |
a, b, c (Å) | 9.6016 (19), 15.701 (3), 26.722 (5) |
V (Å3) | 4028.5 (14) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 8.38 |
Crystal size (mm) | 0.19 × 0.16 × 0.13 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.305, 0.402 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9284, 1162, 1088 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.018, 0.045, 1.11 |
No. of reflections | 1162 |
No. of parameters | 74 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0186P)2 + 60.2587P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.51, −1.04 |
Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4A···O5i | 0.85 | 2.35 | 3.045 (5) | 138.8 |
O4—H4B···O3ii | 0.85 | 1.91 | 2.750 (3) | 168.1 |
O5—H5A···O4 | 0.85 | 1.99 | 2.836 | 179.5 |
O5—H5B···O2iii | 0.85 | 2.36 | 2.938 (4) | 125.4 |
Symmetry codes: (i) −x+3/4, y, −z+3/4; (ii) −x+1, −y, −z+1; (iii) −x+3/2, y+1/4, z−1/4. |
Acknowledgements
This work was supported by the Natural Science Foundation of Ningxia Hui Autonomous Region (No. NZ1150).
References
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In recent years, lanthanide metal-organic compounds have been of great interest due to their fascinating structures and potential applications in magnetism, luminescence, catalysis, gas storage and separation. Multitopic carboxylates have received considerable study due to their availability and potential for allowing for the tailored design of such frameworks. As we know, fumaric acid is a unique ligand with a relatively small, conjugated middle part and versatile coordination modes. A large number of lanthanide metal complexes containing fumarate ligands have been reported, see: Zhang et al. (2006). And lanthanide-containing MOFs with two different flexible carboxylate ligands are less developed, see: Zhang et al.(2008); Zhu et al.(2007). In this paper, we report the synthesis and structure of a new metal-organic compound constructed from fumarate ligands coordinated to Er atoms in the presence of oxalate ligands.
In the title compound I, Er1 is eight-coordinated with four O atoms from four fumarate ligands (O2iii, O1iv, O2, O1v, (iii), 1.25 - x, 0.25 - y, z; (iv) 1.5 - x, 0.5 - y, 1 - z; (v) -0.25 + x, -0.25 + y, 1 - z), two O atoms from one oxalate ligand (O3 and O3iii) and two water molecules (O4 and O4iii) (Fig. 1). The Er—O bond lengths are between 2.273 (3)–2.428 (3) Å. The Er atoms are linked through bridging carboxyl groups of fumarate ligands to form two-dimensional Er–fum layers in the ab plane (Fig. 2). Along the c direction, the Er-fum layers are pillared by the oxalic acid resulting in a three-dimensional structure. The framework contains approximately 6.2 Å×11.1 Å rectangular channels along the [100] direction. These channels are occupied by coordinated and free water molecules (Fig. 3). The three-dimensional structure is stabilized by Owater—H···O hydrogen bonds involving both the coordinated and free water molecules.