metal-organic compounds
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Poly[aqua(μ2-oxalato)(4-oxidopyridinium)erbium(II)]
aCollege of Science, Guang Dong Ocean University, Zhanjiang 524088, People's Republic of China, bCollege of Science, Guang Dong Ocean University, Zhanjiang 524088, People's Republic of China, and cCollege of Chemistry, South China University of Technology, Guangzhou 510640, People's Republic of China
*Correspondence e-mail: songwd60@126.com
The title complex, [Er(C5H5NO)(C2O4)(H2O)]n, is a new erbium polymer based on oxalate and 4-oxidopyridinium ligands. The ErII center is coordinated by six O atoms from three oxalate ligands, one O atom from a 4-oxidopyridinium ligand and one water molecule, and displays a distorted square-antiprismatic coordination geometry. The oxalate ligands are both chelating and bridging, and link ErII ions, forming Er–oxalate layers in which the attached water and 4-oxidopyridinium units point alternately up and down. A mirror plane passes through the Er atom, one C, the oxide O and two oxalate O atoms. The layers are assembled into a three-dimensional supramolecular network via intermolecular hydrogen bonding and π–π stacking interactions [centroid–centroid distances of 3.587 (2) Å between parallel pyridinium rings]. Both the water molecule and the 4-oxidopyridinium ligand are disordered over two sites in a 1:1 ratio.
Related literature
For related literature, see: Yaghi et al. (1998, 2003); Serre et al. (2004); James (2003).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2004); cell SAINT (Bruker, 2004); 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
10.1107/S1600536808009380/zl2097sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808009380/zl2097Isup2.hkl
A mixture of Er2O3 (0.5 mmol), oxalic acid (1 mmol), 4-hydroxypyridine (1 mmol) and H2O (10 ml) was placed in a 23 ml Teflon reactor, which was heated to 433 K for three days and then cooled to room temperature at a rate of 10 K h-1. The crystals obtained were washed with water and dryed in air.
In the initial
with disorder not taken into account both the water molecule and the 4-oxidopyridinium moiety showed significantly elongated thermal ellipsoids indicating disorder, and they were thus refined as being disordered over two positions across a crystallographic mirror plane perpendicular to the b-axis. The ADPs of the disordered atoms were restrained to be close to isotropic and those of equivalent atoms were set to be identical. Carbon-bound H atoms were placed in calculated positions and were treated as riding on the parent C atoms with C—H = 0.93 Å, N—H = 0.86 Å and with Uiso(H) = 1.2 Ueq(C, N); Water H atoms were tentatively located in difference Fourier maps and were refined with distance restraints of O–H = 0.85 Å and H···H = 1.39 Å, each within a standard deviation of 0.01 Å, and with Uiso(H) = 1.5 Ueq(O).Data collection: APEX2 (Bruker, 2004); cell
SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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).[Er(C5H5NO)(C2O4)(H2O)] | F(000) = 776 |
Mr = 412.41 | Dx = 2.407 Mg m−3 |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2y | Cell parameters from 8000 reflections |
a = 16.8649 (2) Å | θ = 1.7–26.0° |
b = 11.1863 (2) Å | µ = 7.41 mm−1 |
c = 6.5152 (1) Å | T = 296 K |
β = 112.213 (1)° | Block, white |
V = 1137.91 (3) Å3 | 0.21 × 0.19 × 0.13 mm |
Z = 4 |
Bruker APEXII area-detector diffractometer | 1365 independent reflections |
Radiation source: fine-focus sealed tube | 1341 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ϕ and ω scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −21→18 |
Tmin = 0.241, Tmax = 0.392 | k = −14→14 |
7274 measured reflections | l = −8→8 |
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)] = 0.014 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.16 | w = 1/[σ2(Fo2) + (0.019P)2 + 1.5595P] where P = (Fo2 + 2Fc2)/3 |
1365 reflections | (Δ/σ)max = 0.001 |
105 parameters | Δρmax = 0.53 e Å−3 |
39 restraints | Δρmin = −0.88 e Å−3 |
[Er(C5H5NO)(C2O4)(H2O)] | V = 1137.91 (3) Å3 |
Mr = 412.41 | Z = 4 |
Monoclinic, C2/m | Mo Kα radiation |
a = 16.8649 (2) Å | µ = 7.41 mm−1 |
b = 11.1863 (2) Å | T = 296 K |
c = 6.5152 (1) Å | 0.21 × 0.19 × 0.13 mm |
β = 112.213 (1)° |
Bruker APEXII area-detector diffractometer | 1365 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1341 reflections with I > 2σ(I) |
Tmin = 0.241, Tmax = 0.392 | Rint = 0.022 |
7274 measured reflections |
R[F2 > 2σ(F2)] = 0.014 | 39 restraints |
wR(F2) = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.16 | Δρmax = 0.53 e Å−3 |
1365 reflections | Δρmin = −0.88 e Å−3 |
105 parameters |
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 | Occ. (<1) | |
N1 | −0.02721 (14) | 0.4755 (4) | 0.2392 (5) | 0.0325 (18) | 0.50 |
H6 | −0.0815 | 0.4701 | 0.2056 | 0.039* | 0.50 |
C1 | 0.0218 (3) | 0.3724 (4) | 0.2667 (9) | 0.0358 (13) | 0.50 |
H1 | −0.0041 | 0.2977 | 0.2487 | 0.043* | 0.50 |
C2 | 0.1096 (3) | 0.3811 (8) | 0.3210 (9) | 0.0381 (10) | 0.50 |
H2 | 0.1425 | 0.3121 | 0.3394 | 0.046* | 0.50 |
C3 | 0.14844 (16) | 0.4927 (10) | 0.3478 (5) | 0.0326 (13) | 0.50 |
C4 | 0.0994 (4) | 0.5958 (8) | 0.3203 (9) | 0.0381 (10) | 0.50 |
H4 | 0.1254 | 0.6705 | 0.3383 | 0.046* | 0.50 |
C5 | 0.0116 (4) | 0.5871 (4) | 0.2660 (9) | 0.0358 (13) | 0.50 |
H5 | −0.0212 | 0.6561 | 0.2476 | 0.043* | 0.50 |
O1W | 0.3241 (2) | 0.4753 (8) | −0.1619 (6) | 0.040 (3) | 0.50 |
H1W | 0.358 (4) | 0.438 (6) | −0.200 (10) | 0.060* | 0.50 |
H2W | 0.291 (4) | 0.506 (8) | −0.276 (7) | 0.060* | 0.50 |
C6 | 0.20541 (15) | 0.2749 (2) | −0.0746 (4) | 0.0252 (5) | |
C7 | 0.4856 (2) | 0.5000 | 0.5987 (5) | 0.0212 (6) | |
Er1 | 0.311393 (8) | 0.5000 | 0.17883 (2) | 0.01752 (6) | |
O1 | 0.23010 (16) | 0.5000 | 0.3883 (4) | 0.0347 (6) | |
O2 | 0.40635 (16) | 0.5000 | 0.5514 (4) | 0.0313 (6) | |
O3 | 0.54305 (16) | 0.5000 | 0.7871 (4) | 0.0324 (6) | |
O4 | 0.19303 (11) | 0.38280 (16) | −0.0507 (3) | 0.0313 (4) | |
O5 | 0.15399 (12) | 0.20337 (17) | −0.2053 (3) | 0.0338 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0174 (18) | 0.056 (6) | 0.0245 (17) | −0.0017 (19) | 0.0082 (14) | −0.0025 (18) |
C1 | 0.0264 (18) | 0.052 (4) | 0.0305 (15) | −0.0077 (17) | 0.0121 (13) | −0.0001 (17) |
C2 | 0.0235 (17) | 0.059 (3) | 0.0322 (15) | −0.011 (2) | 0.0107 (13) | 0.005 (2) |
C3 | 0.0204 (19) | 0.062 (4) | 0.0147 (15) | 0.008 (5) | 0.0055 (14) | −0.008 (5) |
C4 | 0.0235 (17) | 0.059 (3) | 0.0322 (15) | −0.011 (2) | 0.0107 (13) | 0.005 (2) |
C5 | 0.0264 (18) | 0.052 (4) | 0.0305 (15) | −0.0077 (17) | 0.0121 (13) | −0.0001 (17) |
O1W | 0.0155 (15) | 0.089 (9) | 0.0155 (13) | 0.001 (2) | 0.0049 (11) | 0.002 (2) |
C6 | 0.0150 (12) | 0.0301 (11) | 0.0257 (12) | 0.0024 (9) | 0.0021 (10) | −0.0033 (9) |
C7 | 0.0120 (15) | 0.0322 (16) | 0.0177 (14) | 0.000 | 0.0036 (12) | 0.000 |
Er1 | 0.00977 (9) | 0.02597 (9) | 0.01457 (8) | 0.000 | 0.00206 (6) | 0.000 |
O1 | 0.0134 (12) | 0.0683 (19) | 0.0206 (12) | 0.000 | 0.0044 (10) | 0.000 |
O2 | 0.0111 (11) | 0.0639 (18) | 0.0177 (11) | 0.000 | 0.0041 (9) | 0.000 |
O3 | 0.0122 (12) | 0.0645 (18) | 0.0186 (12) | 0.000 | 0.0038 (10) | 0.000 |
O4 | 0.0161 (9) | 0.0284 (8) | 0.0392 (10) | 0.0039 (7) | −0.0011 (8) | −0.0073 (7) |
O5 | 0.0187 (9) | 0.0307 (9) | 0.0374 (10) | 0.0035 (8) | −0.0058 (7) | −0.0064 (8) |
N1—C1 | 1.3900 | C6—O5 | 1.249 (3) |
N1—C5 | 1.3900 | C6—C6i | 1.553 (5) |
N1—H6 | 0.8600 | C7—O3 | 1.243 (4) |
C1—C2 | 1.3900 | C7—O2 | 1.253 (4) |
C1—H1 | 0.9300 | C7—C7ii | 1.537 (6) |
C2—C3 | 1.3900 | Er1—O1 | 2.271 (3) |
C2—H2 | 0.9300 | Er1—O1Wiii | 2.326 (3) |
C3—O1 | 1.303 (3) | Er1—O5i | 2.3388 (19) |
C3—C4 | 1.3900 | Er1—O5iv | 2.3388 (19) |
C4—C5 | 1.3900 | Er1—O2 | 2.349 (2) |
C4—H4 | 0.9300 | Er1—O3ii | 2.380 (2) |
C5—H5 | 0.9300 | Er1—O4 | 2.3839 (17) |
O1W—Er1 | 2.326 (3) | Er1—O4iii | 2.3839 (17) |
O1W—H1W | 0.818 (10) | O1—C3iii | 1.303 (4) |
O1W—H2W | 0.818 (10) | O3—Er1ii | 2.380 (2) |
C6—O4 | 1.245 (3) | O5—Er1i | 2.3388 (19) |
C1—N1—C5 | 120.0 | O1W—Er1—O5iv | 94.3 (2) |
C1—N1—H6 | 120.0 | O5i—Er1—O5iv | 153.17 (9) |
C5—N1—H6 | 120.0 | O1—Er1—O2 | 73.12 (9) |
C2—C1—N1 | 120.0 | O1Wiii—Er1—O2 | 135.51 (11) |
C2—C1—H1 | 120.0 | O1W—Er1—O2 | 135.51 (11) |
N1—C1—H1 | 120.0 | O5i—Er1—O2 | 82.54 (5) |
C1—C2—C3 | 120.0 | O5iv—Er1—O2 | 82.54 (5) |
C1—C2—H2 | 120.0 | O1—Er1—O3ii | 141.24 (9) |
C3—C2—H2 | 120.0 | O1Wiii—Er1—O3ii | 67.96 (11) |
O1—C3—C4 | 120.4 (7) | O1W—Er1—O3ii | 67.96 (11) |
O1—C3—C2 | 119.5 (7) | O5i—Er1—O3ii | 76.89 (5) |
C4—C3—C2 | 120.0 | O5iv—Er1—O3ii | 76.89 (5) |
C5—C4—C3 | 120.0 | O2—Er1—O3ii | 68.12 (8) |
C5—C4—H4 | 120.0 | O1—Er1—O4 | 79.89 (7) |
C3—C4—H4 | 120.0 | O1Wiii—Er1—O4 | 79.87 (16) |
C4—C5—N1 | 120.0 | O1W—Er1—O4 | 72.16 (15) |
C4—C5—H5 | 120.0 | O5i—Er1—O4 | 68.77 (6) |
N1—C5—H5 | 120.0 | O5iv—Er1—O4 | 135.04 (6) |
Er1—O1W—H1W | 133 (5) | O2—Er1—O4 | 136.92 (6) |
Er1—O1W—H2W | 123 (4) | O3ii—Er1—O4 | 130.40 (6) |
H1W—O1W—H2W | 104.2 (17) | O1—Er1—O4iii | 79.89 (7) |
O4—C6—O5 | 126.9 (2) | O1Wiii—Er1—O4iii | 72.16 (15) |
O4—C6—C6i | 116.0 (3) | O1W—Er1—O4iii | 79.87 (16) |
O5—C6—C6i | 117.1 (3) | O5i—Er1—O4iii | 135.04 (6) |
O3—C7—O2 | 127.1 (3) | O5iv—Er1—O4iii | 68.77 (6) |
O3—C7—C7ii | 116.8 (4) | O2—Er1—O4iii | 136.92 (6) |
O2—C7—C7ii | 116.0 (4) | O3ii—Er1—O4iii | 130.40 (6) |
O1—Er1—O1Wiii | 150.24 (12) | O4—Er1—O4iii | 66.72 (8) |
O1—Er1—O1W | 150.24 (12) | C3—O1—Er1 | 135.2 (2) |
O1Wiii—Er1—O1W | 13.6 (5) | C3iii—O1—Er1 | 135.2 (2) |
O1—Er1—O5i | 98.41 (5) | C7—O2—Er1 | 120.1 (2) |
O1Wiii—Er1—O5i | 94.3 (2) | C7—O3—Er1ii | 118.9 (2) |
O1W—Er1—O5i | 81.0 (2) | C6—O4—Er1 | 118.12 (15) |
O1—Er1—O5iv | 98.41 (5) | C6—O5—Er1i | 118.91 (16) |
O1Wiii—Er1—O5iv | 81.0 (2) |
Symmetry codes: (i) −x+1/2, −y+1/2, −z; (ii) −x+1, −y+1, −z+1; (iii) x, −y+1, z; (iv) −x+1/2, y+1/2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H2W···O1v | 0.82 (1) | 2.03 (4) | 2.769 (4) | 149 (8) |
O1W—H1W···O2v | 0.82 (1) | 2.18 (6) | 2.729 (4) | 124 (6) |
N1—H6···O4vi | 0.86 | 2.41 | 3.041 (3) | 130 |
N1—H6···O4vii | 0.86 | 2.02 | 2.794 (3) | 150 |
Symmetry codes: (v) x, y, z−1; (vi) −x, −y+1, −z; (vii) −x, y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Er(C5H5NO)(C2O4)(H2O)] |
Mr | 412.41 |
Crystal system, space group | Monoclinic, C2/m |
Temperature (K) | 296 |
a, b, c (Å) | 16.8649 (2), 11.1863 (2), 6.5152 (1) |
β (°) | 112.213 (1) |
V (Å3) | 1137.91 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 7.41 |
Crystal size (mm) | 0.21 × 0.19 × 0.13 |
Data collection | |
Diffractometer | Bruker APEXII area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.241, 0.392 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7274, 1365, 1341 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.014, 0.036, 1.16 |
No. of reflections | 1365 |
No. of parameters | 105 |
No. of restraints | 39 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.53, −0.88 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H2W···O1i | 0.818 (10) | 2.03 (4) | 2.769 (4) | 149 (8) |
O1W—H1W···O2i | 0.818 (10) | 2.18 (6) | 2.729 (4) | 124 (6) |
N1—H6···O4ii | 0.86 | 2.41 | 3.041 (3) | 130.2 |
N1—H6···O4iii | 0.86 | 2.02 | 2.794 (3) | 149.6 |
Symmetry codes: (i) x, y, z−1; (ii) −x, −y+1, −z; (iii) −x, y, −z. |
Acknowledgements
The authors thank Guang Dong Ocean University for supporting this study.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The use of multifunctional organic linker molecules to polymerize metal centers into open-framework materials has led to the development of a rich field of chemistry (Yaghi et al., 1998, 2003; Serre et al., 2004; James, 2003) owing to the potential applications of these materials in catalysis, separation, gas storage and molecular recognition. Among such novel open-framework materials, lanthanide oxalates are particularly noteworthy. The wide variety of coordination modes of the oxalate anion permits the use of metal-oxalate units as excellent building blocks to construct a great diversity of frameworks ranging from discrete oligomeric entities to one-, two- and three-dimensional networks. Recently, we obtained the title erbium polymer (I), and its crystal structure is reported here.
The ErII centre in the title compound exhibits a distorted square-antiprismatic coordination geometry, defined by six O atoms from three oxalate ligands, one O atom from the 4-oxidopyridinium ligand and one water molecule (Fig. 1). The oxalate ligands exhibit bidentate O atoms and link to the ErII ions in a bridging mode to adjacent metal centres with Er—Er distances of 6.153 (2) Å and 6.112 (3) Å, respectively, thus forming Er-oxalate layers with the attached water and the 4-oxidopyridinium units that are alternatingly pointing up and down (Fig. 2). The layers are assembled into a three-dimensional supramolecular network via intermolecular O—H···O and N—H···O hydrogen bonding interactions (Table 1) involving the coordinated water molecules, N-protonated 4-hydroxypyridine, the hydroxy O atoms and the oxalate O atoms. They are also stabilized by π-π stacking interactions with centroid to centroid distances of 3.587 (2)A% between parallel pyridinium rings of neighboring complexes (at -x, y, 1 -z). The coordinated water molecule and the 4-oxidopyridinium ligands are located close to a mirror plane perpendicular to the b-axis of the unit cell and are disordered across this plane in a one to one ratio. As stated above the water molecules are engaged in hydrogen bonding to the hydroxide O atom O1 and to oxalate atom O2 (Table 1), and the orientation of the hydrogen O—H···O bond is equivalent but opposite for the two different disordered moieties, thus causing the disorder observed for the water molecule. The hydrogen bond formed by the 4-oxidopyridinium moiety is directed to either of the two symmetry equivalent oxalate oxygen atoms O4 (Table 1), and formation of either of the two H bonds is again responsible for the presence of the disorder observed.