Solvothermal synthesis and crystal structure of poly((μ 3-2-amino-1,3-benzenedicarboxylato-κ 4 O:O′,O″,O‴)-bis(μ 4-2-amino-1,3-benzenedicarboxylato-κ 5 O:O:O′,O″,O‴)-(N,N-dimethylformamide)-aqua-di-europium(III)-N,N-dimethylformamide solvate, C30H31N5O7Eu2
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Ruan-Xiang Liu
Abstract
C30H31N5O7Eu2, orthorhombic, Pna21 (no. 34), a = 18.1766(8) Å, b = 11.0796(5) Å, c = 16.5109(6) Å, V = 3325.1(2) Å3, Z = 4, R gt (F) = 0.0230, wR ref (F 2) = 0.0611, T = 150(2) K.
Table 1 contains the crystallographic data. The list of the atoms including atomic coordinates and displacement parameters can be found in the cif-file attached to this article.
Data collection and handling.
| Crystal: | Block, colourless |
| Wavelength: | Mo Kα radiation (0.71073 Å) |
| μ: | 0.5 mm−1 |
| Diffractometer, scan mode: | Bruker SMART, ω-scans |
| θ max, completeness: | 26,4°, > 99 % |
| N(hkl)measured , N(hkl)unique, R int: | 40066, 6704, 0.049 |
| Criterion for I obs, N(hkl)gt: | I obs > 2 σ(I obs), 6,370 |
| N(param)refined: | 476 |
| Programs: | Bruker programs, 1 Olex2, 2 Shelx 3 , 4 |
1 Source of materials
2–Amino-1,3-benzenedicarboxylic acid (0.2 mmol) and europium nitrate hexahydrate (0.1 mmol) were placed in a reactor lined with polytetrafluoroethylene, then 10 mL DMF (N,N-dimethylformamide) were added. The reaction was carried out in an oven at 393 K for 72 h before natural cooling. After cooling, the crystals were filtered, washed with anhydrous ethanol and dried at room temperature to obtain the colorless target europium organic framework material with a yield of 89.2 % (based on 2-amino-1,3-benzenedicarboxylic acid).
2 Experimental details
The structure was solved by Direct Methods with the SHELXS-2018 program. All H-atoms from C and N atoms were positioned with idealized geometry and refined isotropically (U iso(H) = 1.2U eq(C), 1.2U eq(N) or 1.5U eq(O)) using a riding model with C–H = 0.950 and N–H = 0.880 Å for 2-amino-1,3-benzenedicarboxylate, C–H = 0.950, 0.979, 0.980, and 0.981 Å for DMF molecules, O–H = 0.870 Å, respectively.
3 Comment
To date, some crystal structures based on 2-amino-1,3-benzenedicarboxylic acid, 5 its salts, 6 and transition metal complexes such as UO2 2+, 7 , 8 Mn(II), 9 Cu(II), 10 , 11 and Cd(II) 12 have been reported. However, no corresponding lanthanide complexes or lanthanide-organic frameworks (LnOFs) have been reported anywhere. A number of 5-amino-1,3-benzenedicarboxylate sometimes act as co-ligands with acetate, oxalate and other carboxylate-containing ligands, or neutral nitrogen-containing ligands, such as 1,10-phenanthroline based LnOFs have been reported. 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 Almost all of them were synthesised under hydrothermal conditions, except the 5-amino-2,4,6-triiodoisophthalate-based LnOFs by reacting starting materials in DMF solution. 21 Therefore, we apply for a new europium-organic framework with the formula C30H31N5O15Eu2 under solvothermal condition by choosing 2-amino-1,3-phthalate as the linker.
As shown in the Figure, the asymmetric unit of the title compound consists of three fully deprotonated 2-amino-1,3-benzenedicarboxylate ligands, one coordinated DMF molecule, one coordinated water molecule, and one crystalline DMF molecule and two Eu2+. The 2-amino-1,3-benzenedicarboxylate ligand adopts three types of coordinate modes, by which the 2-amino-1,3-benzenedicarboxylate ligands connect three Eu(III) atoms (two Eu1 and one Eu2), four Eu(III) atoms (two Eu1 and two Eu2), and three Eu(III) atoms (two Eu1 and one Eu2), respectively. From the Figure, we can see that it contains two crystallographically independent Eu(III), named Eu1 and Eu2, respectively. Eu1 is coordinated with eight O atoms from six 2-amino-1,3-benzenedicarboxylate ligands, while Eu2 is coordinated with six O atoms from five 2-amino-1,3-benzenedicarboxylate ligands, one O atom from one DMF molecule and one O atom from one water molecule to generate an eight-coordination environment. The bond lengths of Eu1–O12, Eu1–O13, Eu1–O14, Eu1–O10A, Eu1–O11A (code A: 1−x, −y, 0.5+z), Eu1–O15, Eu1–O5B (code B: −0.5+x, 0.5−y, z, Eu1–O6C (code C: 1.5−x, −0.5+y, −0.5+z) are 2.4747(49), 2.3912(53), 2.3226(53), 2.4594(52), 2.5801(38), 2.3587(48), 2.4272(47), and 2.3451(50) Å; while the bond lengths of Eu2–O1, Eu2–O4, Eu2–O9, Eu2–O2C, Eu2–O3C, Eu2–O6D, Eu2–O7D, Eu2– O11 (code E: 1.5−x, −0.5+y, 0.5+z) are 2.3345(52), 2.2829(53), 2.2834(54), 2.4613(52), 2.4507(55), 2.6475(54), 2.4566(53) and 2.4176(44) Å respectively, which are comparable with the reported values for its analogues. 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 As demonstrated in the figure, Eu1 and Eu2 are bridged by three 2-amino-1,3-benzenedicarboxylate ligands to form a di–Eu(III)cluster, which are further connected by 2-amino-1,3-benzenedicarboxylate ligands to generate a 3D europium-organic framework, showing one-dimensional channels along the a direction (see the right part of the figure). In addition, the coordinated DMF and the crystalline DMF molecules are filled in the channels of the structure.
Acknowledgments
We are grateful for financial support from Postgraduate Education Reform and Quality Improvement Project of Henan Province (YJS2023JD65).
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