Abstract
C60H76N18O32Nd2, monoclinic, P21/c (no. 14), a = 10.609(5) Å, b = 31.215(5) Å, c = 12.407(4) Å, β = 116.54(3)°, V = 3676(2) Å3, Z = 2, Rgt(F) = 0.0450, wRref(F2) = 0.0910, T = 293(2) K.
A part of the title crystal structure is shown in the figure. Tables 1 and 2 contain details of the measurement method and a list of the atoms including atomic coordinates and displacement parameters.
Data collection and handling.
| Crystal: | Black strip Size 0.30 × 0.21 × 0.13 mm |
| Wavelength: | Mo Kα radiation (0.71073 Å) |
| μ: | 15.0 cm−1 |
| Diffractometer, scan mode: | Bruker FRAMBO, φ and ω |
| 2θmax, completeness: | 50°, >99% |
| N(hkl)measured, N(hkl)unique, Rint: | 13629, 6487, 0.033 |
| Criterion for Iobs, N(hkl)gt: | Iobs > 2 σ(Iobs), 5973 |
| N(param)refined: | 485 |
| Programs: | Bruker programs [8], SHELX [9] |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).
| Atom | x | y | z | Uiso*/Ueq |
|---|---|---|---|---|
| C1 | 0.6989(6) | −0.3015(2) | 0.8046(6) | 0.0537(17) |
| H1 | 0.7121 | −0.3142 | 0.8766 | 0.064* |
| C2 | 0.7100(6) | −0.25793(19) | 0.8025(5) | 0.0420(14) |
| H2 | 0.7324 | −0.2418 | 0.8717 | 0.050* |
| C3 | 0.6514(6) | −0.30765(19) | 0.6084(6) | 0.0500(15) |
| H3 | 0.6330 | −0.3246 | 0.5413 | 0.060* |
| C4 | 0.6572(5) | −0.26392(18) | 0.5964(5) | 0.0378(13) |
| H4 | 0.6410 | −0.2519 | 0.5228 | 0.045* |
| C5 | 0.6872(5) | −0.23834(17) | 0.6953(4) | 0.0295(11) |
| C6 | 0.6912(5) | −0.19162(16) | 0.6839(4) | 0.0261(11) |
| C7 | 0.6769(5) | −0.13177(17) | 0.6036(4) | 0.0279(11) |
| C8 | 0.6543(6) | −0.09452(16) | 0.5250(4) | 0.0335(12) |
| H8A | 0.5542 | −0.0884 | 0.4843 | 0.040* |
| H8B | 0.6837 | −0.1020 | 0.4637 | 0.040* |
| C9 | 0.7319(6) | −0.05405(17) | 0.5889(4) | 0.0336(12) |
| H9A | 0.7222 | −0.0329 | 0.5285 | 0.040* |
| H9B | 0.8313 | −0.0607 | 0.6337 | 0.040* |
| C10 | 0.6811(5) | −0.03434(15) | 0.6752(4) | 0.0249(10) |
| C11 | 0.6490(5) | 0.31857(17) | 1.1899(4) | 0.0315(12) |
| H11 | 0.6382 | 0.3305 | 1.1177 | 0.038* |
| C12 | 0.6351(5) | 0.27499(16) | 1.1953(4) | 0.0287(11) |
| H12 | 0.6147 | 0.2582 | 1.1276 | 0.034* |
| C13 | 0.6945(5) | 0.32589(16) | 1.3869(4) | 0.0319(12) |
| H13 | 0.7151 | 0.3433 | 1.4536 | 0.038* |
| C14 | 0.6836(5) | 0.28278(16) | 1.3997(4) | 0.0283(11) |
| H14 | 0.6975 | 0.2714 | 1.4735 | 0.034* |
| C15 | 0.6517(5) | 0.25618(15) | 1.3013(4) | 0.0233(10) |
| C16 | 0.6345(5) | 0.21016(15) | 1.3103(4) | 0.0233(10) |
| C17 | 0.6016(5) | 0.14545(15) | 1.2637(4) | 0.0257(10) |
| C18 | 0.5777(6) | 0.10179(17) | 1.2121(5) | 0.0372(13) |
| H18A | 0.4968 | 0.0894 | 1.2173 | 0.045* |
| H18B | 0.6590 | 0.0842 | 1.2597 | 0.045* |
| C19 | 0.5524(5) | 0.10103(16) | 1.0812(4) | 0.0309(11) |
| H19A | 0.4539 | 0.0946 | 1.0307 | 0.037* |
| H19B | 0.5706 | 0.1294 | 1.0597 | 0.037* |
| C20 | 0.6406(5) | 0.06936(14) | 1.0536(4) | 0.0223(10) |
| C21 | 0.9737(6) | 0.34149(19) | 0.9283(5) | 0.0437(14) |
| H21 | 0.9798 | 0.3498 | 1.0025 | 0.052* |
| C22 | 0.9799(5) | 0.29829(17) | 0.9076(4) | 0.0340(12) |
| H22 | 0.9888 | 0.2782 | 0.9660 | 0.041* |
| C23 | 0.9544(6) | 0.35950(18) | 0.7443(5) | 0.0379(13) |
| H23 | 0.9465 | 0.3803 | 0.6879 | 0.046* |
| C24 | 0.9606(5) | 0.31704(17) | 0.7158(4) | 0.0325(12) |
| H24 | 0.9567 | 0.3097 | 0.6417 | 0.039* |
| C25 | 0.9728(5) | 0.28547(16) | 0.7988(4) | 0.0270(11) |
| C26 | 0.9764(5) | 0.23998(15) | 0.7714(4) | 0.0251(10) |
| C27 | 1.0004(5) | 0.17382(17) | 0.7904(4) | 0.0310(11) |
| C28 | 1.0293(6) | 0.12750(17) | 0.8235(5) | 0.0391(13) |
| H28A | 1.1126 | 0.1189 | 0.8153 | 0.047* |
| H28B | 0.9508 | 0.1106 | 0.7671 | 0.047* |
| C29 | 1.0518(5) | 0.11743(16) | 0.9495(4) | 0.0316(11) |
| H29A | 0.9647 | 0.1218 | 0.9556 | 0.038* |
| H29B | 1.1226 | 0.1364 | 1.0062 | 0.038* |
| C30 | 1.0989(5) | 0.07160(15) | 0.9794(4) | 0.0237(10) |
| N1 | 0.9594(5) | 0.37206(15) | 0.8487(4) | 0.0417(11) |
| N2 | 0.9447(5) | 0.22736(14) | 0.6624(4) | 0.0401(11) |
| N3 | 1.0112(4) | 0.20736(14) | 0.8551(4) | 0.0325(10) |
| N4 | 0.6704(5) | −0.32720(17) | 0.7097(5) | 0.0527(13) |
| N5 | 0.6687(4) | −0.17186(13) | 0.5772(3) | 0.0287(9) |
| N6 | 0.7137(5) | −0.16545(15) | 0.7718(4) | 0.0372(11) |
| N7 | 0.6772(4) | 0.34472(13) | 1.2838(4) | 0.0325(10) |
| N8 | 0.6414(4) | 0.19246(13) | 1.4078(4) | 0.0314(10) |
| N9 | 0.6092(4) | 0.18162(13) | 1.2172(3) | 0.0275(9) |
| Nd1 | 0.78621(2) | 0.016123(7) | 0.95239(2) | 0.01792(9) |
| O1 | 0.6433(3) | 0.03073(10) | 1.0808(3) | 0.0235(7) |
| O2 | 0.7080(4) | 0.08311(11) | 0.9994(3) | 0.0337(8) |
| O3 | 0.7747(3) | −0.01963(11) | 0.7726(3) | 0.0268(7) |
| O4 | 0.5524(3) | −0.03387(12) | 0.6455(3) | 0.0358(9) |
| O5 | 1.0151(3) | 0.04437(10) | 0.9874(3) | 0.0258(7) |
| O6 | 0.9420(3) | 0.02067(12) | 1.1728(3) | 0.0359(9) |
| H602 | 0.9292 | 0.0025 | 1.2169 | 0.043* |
| H601 | 1.0310 | 0.0230 | 1.1986 | 0.043* |
| O7 | 0.7809(3) | −0.06107(11) | 1.0058(3) | 0.0322(8) |
| O8 | 0.5322(3) | 0.00401(10) | 0.8326(3) | 0.0269(7) |
| H801 | 0.5052 | −0.0014 | 0.7580 | 0.032* |
| H802 | 0.4721 | −0.0071 | 0.8522 | 0.032* |
| O9 | 0.7208(4) | 0.06714(11) | 0.7830(3) | 0.0334(8) |
| H901 | 0.7079 | 0.0937 | 0.7867 | 0.040* |
| H902 | 0.7140 | 0.0576 | 0.7207 | 0.040* |
| O10 | 0.9605(4) | 0.18269(12) | 0.6738(3) | 0.0443(10) |
| O11 | 0.6200(4) | 0.14871(11) | 1.3781(3) | 0.0330(8) |
| O12 | 0.7056(4) | −0.12473(11) | 0.7207(3) | 0.0359(8) |
| O2W | 0.2986(4) | −0.05661(14) | 0.4456(3) | 0.0492(10)* |
| H201 | 0.3658 | −0.0503 | 0.5136 | 0.059* |
| H202 | 0.2824 | −0.0833 | 0.4458 | 0.059* |
| O1W | 0.6578(4) | −0.08209(15) | 0.2532(4) | 0.0589(11)* |
| H101 | 0.5918 | −0.0652 | 0.2097 | 0.071* |
| H102 | 0.6350 | −0.1071 | 0.2243 | 0.071* |
| O4W | 1.1023(4) | −0.05369(14) | 1.5509(3) | 0.0519(10)* |
| H401 | 1.1069 | −0.0311 | 1.6048 | 0.062* |
| H402 | 1.0675 | −0.0723 | 1.5899 | 0.062* |
| O3W | 1.1177(4) | 0.02561(14) | 1.6642(4) | 0.0571(11)* |
| H302 | 1.0697 | 0.0384 | 1.6663 | 0.069* |
| H301 | 1.2036 | 0.0445 | 1.7044 | 0.069* |
Source of material
3-(3-Pyridin-4-yl-[1,2,4]oxadiazol-5-yl)-propionic acid (HL) is easily available by a literature known synthesis [1]. A solution of ammonia (0.5 M) was added dropwise to a methanol (15 mL) solution of HL (3 mmol), resulting in a transparent solution. A methanol (15 mL) solution of acetate dihydrate (1.5 mmol) was added into the resulting solution and stirred for 3 h, resulting in a suspension. A methanol (15 mL) solution of neodymium chloride hexahydrate (1 mmol) was added into the resulting suspension and stirred for 8 h. The suspension was filtered and diethyl ether was allowed to diffuse slowly into the solution of the filtrate. Black crystals were obtained in about 3 weeks.
Experimental details
H atoms bound to C atoms were placed in calculated positions and treated as mixed on their parent atoms, with C—H = 0.93 or 0.97 Å and Uiso(H) = 1.2 or 1.5 Ueq(C). H atoms of water molecule were initially found in the difference Fourier map and were refined with restraint as O—H = 0.85 Å.
Discussion
Lanthanide-based carboxylate complexes have been found to exhibit anticancer, unusual coordination characteristics, exceptional optical, magnetic properties [2, 3, 4]. They are used as precursors for oxides [5] and may possess fungicidal properties [6]. Lanthanide nitrates have been previously used in the synthethic protocol of such complexes, while little attention has been paid to the use of lanthanide chloride [7]. As a part of our ongoing investigations we report the preparation and crystal structure of the title compound. In the asymmetric unit of title structure, there are four lattice water molecules, and three organic ligands adopting a monodentate mode a chelating mode and a chelating bidentate coordination mode, respectively. Two neighboring NdIII ions form a dimeric structural unit with the Nd1—Nd1 distance of 4.2658(21) Å bridged by two oxygen atoms of two carboxylates. Each Nd(III) is coordinated by three water ligands and six oxygen atoms of four carboxylate ligands, exhibiting a tricapped trigonal prism geometry (see the figure, lattice water molecules are removed for clarity). The Nd—O bond lengths, depending on the nature of the O-atoms, vary from 2.4152(4) to 2.6839(4) Å. The dimeric structural unit is further connected by intermolecular hydrogen bonds.
Funding source: Natural Science Foundation of Liaoning Province
Award Identifier / Grant number: 2013020090
Funding statement: This work is financially supported by the Natural Science Foundation of Liaoning Province (No. 2013020090) and Program of Liaoning Provincial Key Laboratory of Functional Textile Materials Liaoning Province Key Laboratory of Functional Textile Materials.
Acknowledgements:
This work is financially supported by the Natural Science Foundation of Liaoning Province (No. 2013020090) and Program of Liaoning Provincial Key Laboratory of Functional Textile Materials Liaoning Province Key Laboratory of Functional Textile Materials.
References
1. Zhang, F.; Liu, F.; Chen, Q. F.; Dong, M. D.: 3-[3-(Pyridin-3-yl)-1, 2, 4-oxadiazol-5-yl]propanoic acid. Acta Crystallogr. E67 (2011) o193.10.1107/S1600536810051639Search in Google Scholar PubMed PubMed Central
2. Kido, J.; Okamoto, Y.: Organo lanthanide metalcomplexes for electroluminescent materials. Chem. Rev. 102 (2002) 2357–2368.10.1021/cr010448ySearch in Google Scholar PubMed
3. Marques, N.; Sella, A.; Takats, J.: Chemistry of the lanthanides using pyrazolylborate ligands. Chem. Rev. 102 (2002) 2137–2159.10.1021/cr010327ySearch in Google Scholar PubMed
4. Zaleski, C. M.; Depperman, E. C.; Kampf, J. W.; Kirk, M. L.; Pecoraro, V. L.: Synthesis, structure, and magnetic properties of a large lanthanide-transition metal single-molecule magnet. Angew. Chem. Int. Ed. 43 (2004) 3912–3914.10.1002/anie.200454013Search in Google Scholar PubMed
5. Muro, I. G.; Mautner, F. A.; Insausti, M.; Lezama, L.; Arriortua, M. I.; Rojo, T.: Study of the two-dimensional [MM′(C3H2O4)2(H2O)4] (M = Ba, Sr and M′ = Cu, Mn) systems: synthesis, structure, magnetic properties, and thermal decomposition. Inorg. Chem. 37 (1998) 3243–3251.10.1021/ic9800132Search in Google Scholar
6. Wang, L. N.; Liu, X. R.; Wang, C. X.; Yan, L. Y.; Huang, J.: Preparation and thermal analysis of C14H10N4O6 and its complexes with rare earth. Synth. React. Inorg. Met.-Org. Chem. 39 (2009) 619–624.10.1080/15533170903432933Search in Google Scholar
7. Liu, F.; Zhang, Q.; Hou, G. F.; Chen, Q. F.; Chen, P.; Li, G. M.: Synthesis, structures of salen-type 3d-4f heteronuclear metal complexes. J. Inorg. Organomet. Polym. 23 (2013) 1097–1103.10.1007/s10904-013-9893-ySearch in Google Scholar
8. Bruker. APEX2, SAINT and SADABS. Brucker AXS Inc., Madison, Wisconsin, USA, 2009.Search in Google Scholar
9. Sheldrick, G. M.: A short history of SHELX. Acta Crystallogr. A64 (2008) 112–122.10.1107/S0108767307043930Search in Google Scholar PubMed
©2016 Fang Zhang et al., published by De Gruyter.
This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.
