A Unique Layered Cu-formate Hydrate of Cu(HCOO) 2·1/3H2O: Structures, Dehydration, and Thermal and Magnetic Properties

doi:10.1007/s40242-022-1457-7

Abstract

Abstract: Anew layered Cu-formate hydrate of Cu(HCOO)₂·1/3H₂O is unique in its water content and the strongly waved (4,4) Cu-formate layers held by interlayer weak axial Cu-O_formate bonds and O-H_water···O_formate hydrogen bonds. The crystal is in orthorhombic space group Pbcn, with cell parameters at 80 K:a=7.9777(2) Å, b=7.3656(2) Å, c=21.0317(5) Å(1 Å=10⁻¹ nm), and V=1235.83(5) Å³. The Cu²⁺ ions are in the environments of a square pyramid and elongated octahedron, in a ratio of 1/2 within the structure. In the layer, Cu²⁺ ions are connected by anti-anti formates via short basal Cu-O bonds. The structure remains unchanged until the dehydration that produces the layered anhydrous β-Cu(HCOO)₂, and the possible transformation mechanism, supported by diffraction evidence, is the reorganization of the Cu-O_formate bonds across the parent layers after dehydration. The two phases exhibit anisotropic thermal expansion behaviors closely relevant to the transverse thermal vibrations of the constituents. Cu(HCOO)₂·1/3H₂O is a 2-dimensional Heisenberg antiferromagnet, and exhibits a global spin-canted antiferromagnetism with the Néel temperature of 32.1 K. This is not only higher than that of the magnetically denser β-Cu(HCOO)₂, but also the highest among the copper formate frameworks.

Key words: Copper formate, Layered structure, Dehydration, Thermal expansion, Magnetism

FAN Huimin, WANG Bingwu, WANG Zheming, GAO Song. A Unique Layered Cu-formate Hydrate of Cu(HCOO) ₂·1/3H₂O: Structures, Dehydration, and Thermal and Magnetic Properties[J]. Chemical Research in Chinese Universities, 2022, 38(1): 107-116.

References

[1] Zhao Y. H., Liu S., Xiong L. H., Fan H. M., Wang B. W., Jiang S. D., Wang Z. M., Gao S., Sci. Sin. Chim., 2021, 51, 410
[2] Li W., Stroppa A., Wang Z. M., Gao S., Hybrid Organic-Inorganic Perovskites, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2020
[3] Wang Z. M., Hu K. L., Gao S., Kobayashi H., Adv. Mater., 2010, 22, 1526
[4] Shang R., Chen S., Wang Z. M., Gao S.; Ed.:Macgillivray L. R., Lukehart C. M., Metal-Organic Framework Materials, John Wiley & Sons, Ltd., Chichester, 2014
[5] Shang R., Chen S., Hu K. L., Jiang Z. C., Wang B. W., Kurmoo M., Wang Z. M., Gao S., APL Mater., 2014, 2, 124104
[6] Jain P., Ramachandran V., Clark R. J., Zhou H. D., Toby B. H., Dalal N. S., Kroto H. W., Cheetham A. K., J. Am. Chem. Soc., 2009, 131, 13625
[7] Gómez-Aguirre L. C., Pato-Doldán B., Mira J., Castro-García S., Señarís-Rodríguez M. A., Sánchez-Andújar M., Singleton J., Zapf V. S., J. Am. Chem. Soc., 2016, 138, 1122
[8] Xu G. C., Zhang W., Ma X. M., Chen Y. H., Zhang L., Cai H. L., Wang Z. M., Xiong R. G., Gao S., J. Am. Chem. Soc., 2011, 133, 14948
[9] Cañadillas-Delgado L., Fabelo O., Rodríguez-Velamazán J. A., Lemée-Cailleau M. H., Mason S. A., Pardo E., Lloret F., Zhao J. P., Bu X. H., Simonet V., Colin C. V., Rodríguez-Carvajal J., J. Am. Chem. Soc., 2012, 134, 19772
[10] Please see, references
[47]-
[63] for MFD and
[64]-
[72] for MFL cited in
[4], in order to avoid long list for many literatures published for MFD and MFL.
[11] Zhang L. L., Shen B., Zhao J. P., Gao S. H., Liu F. C., Chin. J. Struct. Chem., 2019, 38, 1963
[12] Overgaard J., Rentschler E., Timco G. A., Larsen F. K., ChemPhysChem, 2004, 5, 1755
[13] Wang X. Y., Wang Z. M., Gao S., Chem. Commun., 2007, 1127
[14] Li Z. X., Zhao J. P., Sañudo E. C., Ma H., Pan Z. D., Zeng Y. F., Bu X. H., Inorg. Chem., 2009, 48, 11601
[15] Yu Y., Shang R., Chen S., Wang B. W., Wang Z. M., Gao S., Chem. Eur. J., 2017, 23, 9857
[16] Liu S., Wang B. W., Wang Z. M., Gao S., Dalton Trans., 2018, 47, 11925
[17] Chen S., Shang R., Wang B.W., Wang Z. M., Gao S., APL Mater., 2018, 6, 114205
[18] Krasil'nikov V. N., Zhukov V. P., Chulkov E. V., Baklanova I. V., Kellerman D. G., Gyrdasova О. I., Dyachkova Т. V., Tyutyunnik А. P., J. Alloy. Compd., 2020, 845, 156208
[19] Martin R. L., Waterman H., J. Chem. Soc., 1959, 1359
[20] Sapiña F., Burgos M., Escrivá E., Folgado J. V., Marcos D., Beltrán A., Beltrán D., Inorg. Chem., 1993, 32, 4337
[21] Inoue M., Kubo M., Inorg. Chem., 1970, 9, 2310
[22] Samarasekere P., Wang X., Jacobson A. J., Tapp J., Möller A., Inorg. Chem., 2014, 53, 244
[23] Kiriyama H., Kitahama K., Acta Cryst., 1976, B32, 330
[24] Yamamoto Y., Matsuura M., Haseda T., J. Phys. Soc. Jpn., 1976, 40, 1300
[25] Bukowska-Strzyżewska M., Acta Cryst. 1965, 19, 357
[26] Kay M. I., Almodova I., Kaplan S. F., Acta Cryst., 1968, B24, 1312
[27] Flippen R. B., Friedberg S. A., J. Chem. Phys., 1963, 38, 2652
[28] Wagner G. R., Schumacher R. T., Friedberg S. A., Phys. Rev., 1960, 150, 226
[29] Nakamura E., Adachi M., Akishige Y., Asahi T., Deguchi K., Furukawa T., Gesi K., Hasebe K., Hikita T., Ishibashi Y., Iwata Y., Komukae M., Mitsui T., Nakatani N., Nozaki R., Osaka T., Shiozaki Y., Takezoe H., Yagi T., Ferroelectrics and Related Substances, Springer-Verlag, Berlin, 2006
[30] Shang R., Chen S., Wang Z. M., Gao S., Chem. Eur. J., 2014, 20, 15872
[31] Shang R., Chen S., Wang B. W., Wang Z. M., Gao S., Angew. Chem. Int. Ed., 2016, 55, 2097
[32] Wang Z. X., Jain P., Choi K. Y., van Tol J., Cheetham A. K., Kroto H. W., Koo H. J., Zhou, H. D., Hwang J., Choi E. S., Whangbo M. H., Dalal N. S., Phys. Rev. B, 2013, 87, 224406
[33] Baker P. J., Lancaster T., Franke, I., Hayes W., Blundell S. J., Pratt F. L., Jain P., Wang Z. M., Kurmoo M., Phys. Rev. B, 2010, 82, 012407
[34] Hu K. L., Kurmoo M., Wang Z. M., Gao S., Chem. Eur. J., 2009, 15, 12050
[35] Li M. Y., Kurmoo, M., Wang Z. M., Gao, S., Chem. Asian J., 2011, 6, 3084
[36] Shang R., Chen S., Hu K. L., Wang B. W., Wang Z. M., Gao S., Chem. Eur. J., 2016, 22, 6199
[37] Burger N., Fuess H., Solid State Commun., 1980, 34, 699
[38] Barclay G. A., Kennard C. H. L., J. Chem. Soc., 1961, 3289
[39] Manson J. L., Lancaster T., Chapon L. C., Blundell S. J., Schlueter J. A., Brooks M. L., Pratt F. L., Nygren C. L., Qualls J. S., Inorg. Chem., 2005, 44, 989
[40] Manson J. L., Lecher J. G., Gu J., Geiser U., Schlueter J. A., Henning R., Wang X. P., Schultz A. J., Koo H. J., Whangbo M. H., Dalton Trans., 2003, 2905
[41] Carter III R. O., Poindexter B. D., Weber W. H., Vib. Spectrosc., 1991, 2, 125
[42] CrysAlisPro software, Rigaku Oxford Diffraction, Tokyo, 2020
[43] Sheldrick G. M., SHELX-97, PC version, University of Göttingen, Göttingen, 1997
[44] Materials Studio v4.4, Accelrys Software Inc., San Diego, 2008
[45] Mulay L. N., Boudreaux E. A., Theory and Applications of Molecular Diamagnetism, John Wiley & Sons Inc., New York, 1976
[46] Young R. A., The Rietveld Method, Oxford University Press, New York, 1993
[47] Galwey A. K., Jamieson D. M., J. Phys. Chem., 1974, 78, 2664
[48] Günter J. R., J. Solid State. Chem., 1980, 35, 43
[49] Heyns A. M., Range K. J., J. Mol. Struct., 1987, 162, 57
[50] Shang R., Xu G. C., Wang Z. M., Gao S., Chem. Eur. J., 2014, 20, 1146
[51] Chen S., Shang R., Hu K. L., Wang Z. M., Gao S., Inorg. Chem. Front., 2014, 1, 83
[52] Zhao Y. H., Liu S., Wang B. W., Wang Z. M., Gao S., Chem. Eur. J., 2019, 25, 9303
[53] Zhao T. M., Chen S., Shang R., Wang B. W., Wang Z. M., Gao S., Inorg. Chem., 2016, 55, 10075
[54] Xiong L. H., Zhao T. M., Wang B. W., Wang Z. M., Gao S., APL Mater., 2021, 9, 021112
[55] Chapman K. W., Chupas P. J., Kepert C. J., J. Am. Chem. Soc., 2005, 127, 15630
[56] Goodwin A. L., Calleja M., Conterio M. J., Dove M. T., Evans J. S. O., Keen D. A., Peters L., Tucker M. G., Science, 2008, 319, 794
[57] Lock N., Wu Y., Christensen M., Cameron L. J., Peterson V. K., Bridgeman A. J., Kepert C. J., Iversen B. B., J. Phys. Chem. C, 2010, 114, 16181
[58] Wu Y., Kobayashi A., Halder G. J., Peterson V. K., Chapman K. W., Lock N., Southon P. D., Kepert C. J., Angew. Chem., 2008, 120, 9061
[59] Evans J. S. O., J. Chem. Soc., Dalton Trans., 1999, 3317
[60] Miller W., Smith C. W., Mackenzie D. S., Evans K. E., J. Mater. Sci., 2009, 44, 5441
[61] Takenaka K., Sci. Technol. Adv. Mater., 2012, 13, 013001
[62] Navarro R.; Ed.:de Jongh L. J., Magnetic Properties of Layered Transition Metal Compounds, Kluwer Academic Publishers, Dordrecht, 1990
[63] Ruiz E., Alvarez S., Alemany P., Chem. Commun., 1998, 2767
[64] Miller J. S., Drillion M., Magnetism:Molecules to Materials II, Wiley-VCH Verlag GmbH, Weinheim, 2001

A Unique Layered Cu-formate Hydrate of Cu(HCOO) ₂·1/3H₂O: Structures, Dehydration, and Thermal and Magnetic Properties

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