TY  - JOUR
T1  - Crystal Structure and Hirshfeld Surface Analysis of a Heterometallic Hofmann-Type-Like Compound
TT  - Heterometalik Hofmann Tipi Benzeri Bir Bileşiğin Kristal Yapısı ve Hirshfeld Yüzey Analizi
AU  - Şahin, Zarife Sibel
AU  - Kartal, Zeki
PY  - 2024
DA  - June
DO  - 10.33484/sinopfbd.1370598
JF  - Sinop Üniversitesi Fen Bilimleri Dergisi
JO  - Sinop Uni J Nat Sci
PB  - Sinop Üniversitesi
WT  - DergiPark
SN  - 2536-4383
SP  - 72
EP  - 95
VL  - 9
IS  - 1
LA  - en
AB  - In this study; a new heterometallic compound defined by the open formula [Cd(H2O)2Ni(CN)4]4[Cd(H2O)4Ni(CN)4]5 was synthesized in crystal form. Consisting of components such as water molecules, [Ni(CN)4]2− anions, and cadmium transition metal atoms, this new crystal structure has no analogues which might have been previously obtained, even with other transition metal atoms. It is a new compound and a unique example of a crystal. The structural properties of this heterometallic compound have been characterized by single crystal X-ray diffraction spectroscopy (SC-XRD), FT-IR spectroscopy, thermal analysis and elemental analysis methods. According to the data obtained from the SC-XRD technique, this heterometallic compound has a monoclinic crystal system and a C2/c space group. The asymmetric unit of this compound consists of five Cd(II) ions, five Ni(II) ions, eighteen cyanide ligands, and fourteen coordinated water ligand molecules. In addition, theoretical calculations have been made with the Gaussian 03 program in order to obtain more information about this heterometallic Hofmann-type-like compound. The chemical properties of this new compound have been calculated using its HOMO and LUMO values and the natural bond orbital (NBO) analyses. In addition, Hirshfeld surface analysis of the asymmetric unit of this compound has been performed with the CrystalExplorer program. As a result of the Hirshfeld surface analysis, extensive information has been obtained about the weak intramolecular and intermolecular forces that form this new crystalline compound.
KW  - Hofmann-type-like compound
KW  - SC-XRD analysis
KW  - FT-IR spectroscopy
KW  - theoretical calculations
KW  - Hirshfeld surface analysis
N2  - Bu çalışmada; açık formül [Cd(H2O)2Ni(CN)4]4[Cd(H2O)4Ni(CN)4]5 ile tanımlanan yeni bir heterometalik bileşik, kristal formda sentezlendi. Su molekülleri, [Ni(CN)4]2− anyonları ve kadmiyum geçiş metali atomları gibi bileşenlerden oluşan bu yeni kristal yapının, diğer geçiş metali atomlarıyla bile daha önce elde edilmiş olabilecek hiçbir analogu yoktur. Yeni bir bileşik ve kristalin eşsiz bir örneğidir. Bu heterometalik bileşiğin yapısal özellikleri, tek kristal X-ışını kırınım spektroskopisi (SC-XRD), FT-IR spektroskopisi, termal analiz ve elementel analiz yöntemleriyle karakterize edilmiştir. SC-XRD tekniğinden elde edilen verilere göre bu heterometalik bileşik, monoklinik kristal sistemine ve C2/c uzay grubuna sahiptir. Bu bileşiğin asimetrik birimi beş Cd(II) iyonu, beş Ni(II) iyonu, on sekiz siyanür ligandı ve on dört koordineli su ligandı molekülünden oluşur. Ayrıca bu heterometalik Hofmann tipi bileşik hakkında daha fazla bilgi edinmek amacıyla Gaussian 03 programı ile teorik hesaplamalar yapılmıştır. Bu yeni bileşiğin kimyasal özellikleri, HOMO ve LUMO değerleri ve doğal bağ yörünge (NBO) analizleri kullanılarak hesaplandı. Ayrıca bu bileşiğin asimetrik biriminin Hirshfeld yüzey analizi CrystalExplorer programı ile yapılmıştır. Hirshfeld yüzey analizi sonucunda bu yeni kristal bileşiği oluşturan zayıf molekül içi ve moleküller arası kuvvetler hakkında kapsamlı bilgiler elde edildi.
CR  - OpenStax, Chemistry. OpenStax CNX. Jun 20, 2016 http://cnx.org/contents/85abf193-2bd2-4908-8563-90b8a7ac8df6@9.311.
CR  - The Materials Project (2020). Materials Data on K2Ni(CN)4 by Materials Project. United States. https://doi.org/10.17188/1307699
CR  - Hofmann, K. A. & Küspert, F. (1897). Verbindungen von kohlenwasserstoffen mit metallsalzen. Zeitschrift Für Anorganische Chemie, 15(1), 204-207. http:/doi.org/10.1002/zaac.18970150118
CR  - Hagan, M. (1962). Clathrate Inclusion Compounds. Reinhold Publishing Corporation, Chapman & Hall Ltd., New York. p. 5
CR  - Iwamoto, T. (1984). Inclusion Compounds, Vol. 1, Chapter 2 (Eds. J. L. Atwood, J. E. D. Davies, and D. D. MacNicol). Academic Press, London, p. 29.
CR  - Türköz, D., Kartal, Z., & Bahçeli, S. (2004). Ft-Ir Spectroscopic Study Of Co(1-Propanethiol)2Ni(CN)4·Benzene Clathrate. Zeitschrift Für Naturforschung A, 59, 7-8. http:/doi.org/10.1515/zna-2004-7-819
CR  - Kartal, Z. (2005). IR spectroscopic study of M (benzoic acid)2Ni(CN)4.(1,4-dioxane) clathrate (M = Ni, Cd and Co). Zeitschrift für Naturforschung A, 60(A), 469-472. http:/doi.org/10.1515/zna-2005-0613
CR  - Kartal, Z., Parlak, C., Şentürk, Ş., Aytekin, M. T. & Şenyel, M. (2007). FT-IR Spectroscopic Study of the Hofmann-Td-type Clathrates: Ni(1,9- diaminononane)Mʹ(CN)4⋅2G (Mʹ = Cd or Hg, G = Benzene, 1,2-Dichlorobenzene or 1,4-Dichlorobenzene). Croatica Chemica Acta, 80(1), 9-15. https://hrcak.srce.hr/12805
CR  - Kartal, Z. (2009). FT-IR spectroscopic study on some Hofmann-type clathrates: M(p-Benzoquinone)Ni(CN)4·2G (M = Mn, Co, Ni or Hg; G = Aniline). Journal of Molecular Structure, 938(1-3), 70–75. http:/doi.org/10.1016/j.molstruc.2009.09.005
CR  - Kartal, Z. & Sayın, E. (2011). FTIR spectroscopic and thermal study of M(Cyclohexanethiol)2Ni(CN)4.(1,4-dioxane) clathrate (M = Mn, Co, Ni and Cd). Journal of Molecular Structure, 994, 170-178. http:/doi.org/10.1016/j.molstruc.2011.03.014
CR  - Kartal, Z. (2012). Vibrational spectroscopic investigation on some M(Benzonitrile)2Ni(CN)4 complexes (M = Ni, Zn, Cd and Hg). Brazilian Journal of Physics, 42, 6-13. http:/doi.org/10.1007/s13538-011-0054-x
CR  - Kartal, Z. & Türk, T. (2021). FT-IR spectroscopic and thermal study of M(1,6-hexanedithiol) Ni(CN)4.2(1,4-dioxane) clathrate(M = Mn, Co, Ni and Cd). Journal of Molecular Structure, 1014, 74-80. http:/doi.org/10.1016/j.molstruc.2012.01.031
CR  - Kartal, Z. (2016). Synthesis, spectroscopic, thermal and structural properties of [M(3-aminopyridine)2Ni(μ-CN)2(CN)2]n [M(II) = Co and Cu] heteropolynuclear cyano-bridged complexes. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 152, 577–583. http:/doi.org/10.1016/j.saa.2014.12.117
CR  - Kartal, Z. & Yavuz, A. (2018). The synthesis and the spectroscopic, thermal, and structural properties of the M2[(fumarate)Ni(CN)4].2(1,4-dioxane) clathrate (M = Co, Ni, Cd and Hg). Journal of Molecular Structure, 1155, 171-183. http:/doi.org/ 10.1016/j.molstruc.2017.10.107
CR  - Kartal, Z., Şahin, O. & Yavuz, A. (2018). The synthesis of two new Hofmann-type M(3-aminopyridine)2Ni(CN)4 [M = Zn(II)and Cd(II)] complexes and the characterization of their crystal structure by various spectroscopic methods. Journal of Molecular Structure, 1171, 578-586. http:/doi.org/10.1016/j.molstruc.2018.06.042
CR  - Kartal, Z. & Şahin, O. (2021). Synthesis, spectroscopic, thermal, crystal structure prop- erties and characterization of new Hofmann-type-like clathrates with 4-aminopyridine and water. Turkish Journal of Chemistry, 45, 616–633. http:/doi.org/10.3906/ kim- 2011- 29
CR  - Kartal, Z. & Şahin, O. (2021). Synthesis, spectroscopic, thermal, crystal structure prop- erties, and characterization of new Hofmann-Td-type complexes with 3- aminopyridine, Turkish. Journal of Chemistry, 45, 942–955. http:/doi.org/10.3906/kim-2101-32
CR  - Kartal, Z., Şahin, O. & Yavuz, A. (2019). Synthesis of Hofmann-type Zn(H2O)2Ni(CN)4.nG (G = water and 1,4-dioxane) clathrates and the determination of their structural properties by various spectroscopic methods, Turkish Journal of Chemistry, 43(6), 1608–1621. http:/doi.org/10.3906/kim-1906-26
CR  - Kartal, Z. & Şahin, O. (2022). Synthesis of two Hofmann type and Hofmann-type-like compounds in crystal form from 4-aminopyridine and their characterizations by various methods. Journal of Molecular Structure, 1252, 132088. https://doi.org/10.1016/j.molstruc.2021.132088.
CR  - Nakamoto, K. (2009). Infrared and Raman Spectra of Inorganic and Coordination Compounds, Part B, Applications in coordination, organometallic, and bioinorganic chemistry, John Wiley and Sons, Hoboken, New Jersey.
CR  - Smékal, Z., Císařová, I. & Mroziński, J. (2001). Cyano-bridged bimetallic complexes of copper(II) with tetracyanonickelate(II). Crystal structure of [Cu(dpt)Ni(CN)4]. Polyhedron, 20, 3301–3306.http:/ doi.org/10.1016/S0277-5387(01)00942-1
CR  - Sheldrick, G. M. (2008). A short history of SHELX. Acta Crystallographica, A64,112-122. https://doi.org/10.1107/S0108767307043930.
CR  - Sheldrick, G. M. (2015). Crystal structure refinement with SHELXL. Acta Crystallographica, C71, 3-8. http://dx.doi.org/10.1107/S2053229614024218
CR  - APEX2, Bruker AXS Inc. Madison Wisconsin USA (2013).
CR  - Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). Mercury 4.0: from visualization to analysis, design and prediction. Journal of Applied. Crystalography, 53, 226-235. https://doi.org/10.1107/S1600576719014092
CR  - Şenocak, A., Karadağ, A., Soylu, M. S. & Andac, O. (2015). Two novel cyanido-bridged polymeric complexes with suspension bridge type connections and a series of related complex salts: crystallographic and thermal characterizations. New Journal of Chemistry, 39(5), 3675-3686. https://doi.org/10.1039/C5NJ00071H
CR  - Kurkcuoglu, G. S., Hokelek, T., Aksel, M., Yesilel, O. Z. & Dal, H. (2011). Cyano-Bridged Heteropolynuclear Ni(II), Cu(II) and Cd(II) Complexes, [M(deten) Ni(μ-CN) (CN) ]. Journal of Inorganic and Organometallic Polymers and Materials, 21(3), 602-610. http:/doi.org/10.1007/s10904-011-9494-6
CR  - Kürkçüoğlu, G. S., Sayin, E. & Şahin, O. (2015). Cyanide bridged hetero-metallic polymeric complexes: Syntheses, vibrational spectra, thermal analyses and crystal structures of complexes [M(1,2-dmi)2 Ni(μ-CN)4]n (M = Zn (II) and Cd (II)). Journal of Molecular Structure, 1101, 82-90. https://doi.org/10.1016/j.molstruc.2015.08.013
CR  - Kürkçüoğlu, G. S., Hökelek, T., Yesilel, O. Z. & Aksay, S. (2008). Synthesis, IR spectrum, thermal property and crystal structure of cyano-bridged heteronuclear polymeric complex, [Cd(teta)Ni(mu-CN)(2)(CN)(2)] center dot 2H(2)O. Structural Chemistry, 19(3), 493-499. http:/doi.org/ 10.1007/s11224-008-9309-8
CR  - Paharova, J., Cernak, J., Zak, Z. & Marek, J. (2007). Use of multi-N-donor ligands for preparation of organic–inorganic hybrid materials: Crystal structures of ionic [M(aepn)2][Ni(CN)4]·H2O and polymeric M(aepn)Ni(CN)4 (M=Zn(II), Cd(II); aepn=N-(2-aminoethyl)-1,3-propanediamine). Journal of Molecular Structure, 842, 117-124. http:/doi.org/10.1016/j.molstruc.2006.12.022
CR  - Collins, J. B., Schleyer, P. v. R., Binkley, J. S. & Pople, J. A. (1976) Self-Consistent molecular orbital methods. 17. Geometries and binding energies of second-row molecules. A comparison of three basis sets. Journal of Chemical Physics, 64, 5142-5151. http:/doi.org/10.1063/1.432189
CR  - Frisch,MJ, Trucks,GW, Schlegel,HB, Scuseria,GE, Robb,MA, Cheeseman,JR, Montgomery,JrJA, Vreven,T, Kudin, KN, Burant,JC, Millam,JM, Iyengar,SS, Tomasi,J, Barone,V, Mennucci, B, Cossi, M, Scalmani, G, Rega, N, Petersson, GA, Nakatsuji, H, Hada, M, Ehara, M, Toyota, K, Fukuda, R, Hasegawa, J, Ishida, M, Nakajima, T, Honda, Y, Kitao, O, Nakai,H, Klene,M, Li, X, Knox,JE, Hratchian,HP, Cross,JB, Bakken,V, Adamo,C, Jaramillo,J, Gomperts,R, Stratmann,RE, Yazyev,O, Austin,AJ, Cammi,R, Pomelli,C, Ochterski,JW, Ayala,PY, Morokuma,K, Voth,GA, Salvador,P, Dannenberg,JJ, Zakrzewski,VG, Dapprich,S, Daniels,AD, Strain,MC, Farkas,O, Malick, DK, Rabuck,AD, Raghavachari,K, Foresman,JB, Ortiz,JV, Cui,Q, Baboul,AG, Clifford,S, Cioslowski,J, Stefanov,BB, Liu,G, Liashenko,A, Piskorz,P, Komaromi,I, Martin,RL, Fox,DJ, Keith,T, Al-Laham,MA, Peng,CY, Nanayakkara,A, Challacombe,M, Gill,PMW, Johnson,B, Chen,W, Wong,MW, Gonzalez,C. & Pople,JA. (2004). Gaussian 03 Revision D.01. Gaussian, Inc., Wallingford CT.
CR  - Dennington, R., Keith, T. & Millam, J. (2007). Gauss View, Version 4.1.2. Semichem Inc., Shawnee Mission.
CR  - Becke, A. D. (1993). Density-functional thermochemistry. III. The role of exact exchange. Journal of Chemical Physics, 98, 5648–5652. http:/doi.org/10.1063/1.464913
CR  - Lee, C., Yang, W. & Parr, R. G. (1988). Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Physical Review B, 37, 785–789. http:/doi.org/ 10.1103/PhysRevB.37.785
CR  - Peng, C., Ayala, P. Y., Schlegel, H. B. & Frisch, M. J. (1996). Using redundant internal coordinates to optimize equilibrium geometries and transition states. Journal of Computaional Chemistry, 17, 49–56.
CR  - Stephens, P. J., Devlin, F. J., Chablowski, C. F. & Frisch, M. J. (1994). Ab Initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields. Journal of Physical Chemistry, 98, 11623–11627. https://doi.org/10.1021/j100096a001
CR  - Pearson, P. G. (2005). Chemical hardness and density functional theory. Journal of Chemical Sciences, 117, 5, 369-377. https://doi.org/10.1007/BF02708340
CR  - Parr, R. G. & Pearson, R. G. (1983). Absolute hardness: companion parameter to absolute electronegativity. Journal of American Chemical Society, 105, 26, 7512-7516. https://doi.org/10.1021/ja00364a005
CR  - Mebi, C. A. (2011). DFT study on structure, electronic properties, and reactivity of cis-isomers of [(NC5H4-S)2Fe(CO)2]. Journal of Chemical Sciences, 123, 727–731.https://doi.org/10.1007/s12039-011-0131-2
CR  - Kumar, C. P. & Buddhadev, M. (2003). HSAB principle applied to the time evolution of chemical reactions. Journal of American Chemical Society, 125, 9, 2705-2710. https://doi.org/10.1021/ja0276063
CR  - Nataraj, A., Balachandran, V. & Karthick, T. (2013). Molecular orbital studies (hardness, chemical potential, electrophilicity, and first electron excitation), vibrational investigation and theoretical NBO analysis of 2-hydroxy-5-bromobenzaldehyde by density functional method. Journal of Molecular Structure, 1031, 221–233. http:/doi.org/10.1016/j.molstruc.2012.09.047
CR  - Elusta, M. I., Başaran, M. A. & Kandemirli, F. (2019). Theoretical studies on mild steel corrosion inhibition by 5-substituted 1h-tetrazoles in acidic media. International Journal of Electrochemical Science, 14, 2743 – 2756. http:/doi.org/10.20964/2019.03.46
CR  - Kartal, Z. & Şahin, O. (2022). Synthesis of two Hofmann type and Hofmann-type-like compounds in crystal form from 4-aminopyridine and their characterizations by various methods. Journal of Molecular Structure, 1252, 132088. https://doi.org/10.1016/j.molstruc.2021.132088
CR  - Spackman, P. R., Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Jayatilaka, D. & Spackman, M. A. (2021). CrystalExplorer: a program for Hirshfeld surface analysis, visualization and quantitative analysis of molecular crystals. Journal of Applied Crystalography, 54(3), 1006–1011. http:/doi.org/10.1107/S1600576721002910
CR  - Praprotnik, M., Janežič, D. & Mavri, J. (2004). Temperature dependence of water vibrational spectrum: a molecular Dynamics simulation study. Journal of Physical Chemistry A, 108, 11056-11062. http://doi.org/10.1021/jp046158d
CR  - Carey, D. M. & Korenowski, G. M. (1998). Measurement of the Raman spectrum of liquid water. Journal of Chemical Physics, 108(7), 2669-2675. http://doi.org/10.1063/1.475659
CR  - Zhang, C., Khaliullin, R. Z, Bovi, D., Guidoni, L. & Kühne, T. D. (2013). Vibrational signature of water molecules in asymmetric hydrogen bonding environments. Journal of Physical Chemistry Letters, 4(19), 3245-3250. http://doi.org/10.1021/jz401321x
CR  - Sharpe, A. G. (1976). The Chemistry of Cyano Complexes of the Transition Metals, Academic Press, London.
CR  - McCullough, R. L., Jones, L. H. & Crosby, G. A. (1960). An analysis of the vibrational spectrum of the tetracyanonickelate(II) ion in a crystal lattice, Spectrochimica Acta, 16(8), 929–944. https://doi.org/10.1016/0371-1951(60)80057-4
UR  - https://doi.org/10.33484/sinopfbd.1370598
L1  - http://dergipark.org.tr/tr/download/article-file/3451643
ER  -