Hexakis(cyanogen)zinc(II) Hexafluoridoarsenate
Table 3. FT-Raman spectra of [Zn(NCCN)6][AsF6]2 (1), References
[Ni(NCCN)x][AsF6]2 (2) and pure liquid cyanogen (3).
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Z. Anorg. Allg. Chem. 2001, 627, 1582.
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Valkonen, P. Rademacher, K. Kowski, J. Chem. Soc., Dalton
Trans. 1992, 537.
(1)
(2)
liquid (CN)2 Assignment
a)
a)
b)
2366s, 2333vw
2369s, 2331vw
2327vs
849
ν(CϵN)
ν(CϪC)
ν(AsF6
884
682
511
369
162
892
684
512
369
174
Ϫ
)
)
505
δ(CϪC)
Ϫ
δ(AsF6
lattice vibration
[6] H. W. Roesky, H. Hofmann, J. Schimkowiak, P. G. Jones, K.
Meyer-Bäse, G. M. Sheldrick, Angew. Chem. 1985, 97, 403; An-
gew. Chem. Int. Ed. Engl. 1985, 24, 417.
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rick, Z. Naturforsch., Teil B 1988, 43, 949.
[8] B. Corian, M. Basato, G. Favero, P. Rosano, Inorg. Chim. Acta
1984, 85, L27-L30.
a) (1) and (2) have only one strong band in the CϵN stretching
region, instead of two bands expected for the coordinated and un-
coordinated CN moieties of the (CN)2 molecule, tentatively indica-
ting a vibrational coupling of the two CN groups [5]. b) Compara-
ble with [Cd(AsF6)2(NCCN)2 (SO2)]n ν(CϵN) 2388 cmϪ1 [7] and
[Ag(NCCN)2]n [AsF6]n ν(CϵN) 2356 cmϪ1, further bands at 872,
688, 510, 370 cmϪ1 [6].
[9] A. B. Elkins, Chemistry of Industrial Toxicology, p. 93. John
Wiley and Sons, Inc., New York 1950.
[10] J. Beck, F. Steden, A. Reich, H. Fölsing, Z. Anorg. Allg. Chem.
2003, 629, 1073.
[11] G. Brauer, Handbuch der Präparativen Anorganischen Chemie,
3rd ed., Ferdinand Enke Verlag, Stuttgart, 1975, p. 629.
[12] H. W. Roesky, M. Thomas, J. W. Bats, H. Fuess, J. Chem. Soc.,
Dalton Trans. 1983, 1891.
indication for the same octahedral coordination sphere
around the Ni2ϩ cation. The ν(CϵN) stretching mode
appears at 2369 cmϪ1 and is shifted 42 cmϪ1 to higher wave
numbers compared to uncoordinated cyanogen. The bands
in the spectra of 1 and 2 at 682, 684 and 369 cmϪ1 can be
assigned to the stretching and deformation modes of the
[AsF6]Ϫ anions. The lower point symmetry of the anions
compared to the ideal octahedral symmetry does not cause
a splitting of bands what shows that the distortions of the
octahedral anions are minute. Table 3 summarizes the ob-
served Raman frequencies and the tentative assignment
which is based on literature data [5, 25].
[13] J. Beck, F. Steden, M. Zink, Z. Anorg. Allg. Chem. 2006, 623,
1227.
[14] G. M. Sheldrick, SHELX97 [Includes SHELXS97,
SHELXL97, CIFTAB] Ϫ Programs for Crystal Structure
Analysis (Release 97Ϫ2). Universität Göttingen, Germany,
1998.
[15] Z. Otwinowski, W. Minor, Program SCALEPACK, Macromo-
lec. Crystallogr. A 1997, 276, 307.
[16] Detailed crystallographic data can be obtained from the Fach-
informationszentrum Karlsruhe by quoting the deposit number,
the names of the authors and the literature citation. Details
about inquiries are given on www.fizinformationsdienste.de.
[17] Diamond, Program for Crystal Structure Visualization, Crystal
Impact Comp., Bonn, Germany, 2005.
[18] J. Beck, M. Zink, Z. Anorg. Allg. Chem. 2009, 635, 692.
[19] I. Leban, D. Gantar, B. Frlec, D. R. Russell Jr., H. Holloway,
Acta Crystallogr., Sect. C 1987, 43, 1888.
Conclusions
[Zn(NCCN)6][AsF6]2 (1) and the respective nickel-con-
taining compound 2 can be obtained by ligand exchange
reactions from [M(SO2)6][AsF6]2 (M ϭ Zn, Ni). Compound
1 is the first example of a metal complex compound in
which the metal cation is homoleptically coordinated by
cyanogen ligands. Both compounds show characteristic
Raman bands, especially the ν(CϵN) stretching mode of
the (CN)2 ligands which are shifted to higher wavenumbers.
The close similarity of the Raman spectra of 2 and 1 is an
indication of an identical coordination environment.
[20] W. W. Brennessel, N. R. Brooks, M. P. Mehn, L. Que Jr., V. G.
Young Jr., Acta Crystallogr., Sect. E 2001, 57, m545.
[21] Ö. N. Akkus, A. Decken, C. Knapp, J. Passmore, J. Chem.
¸
Crystallogr. 2006, 36, 321.
[22] A. S. Parkes, R. E. Hughes, Acta Crystallogr. 1963, 16, 734.
[23] C. R. Bailey, S. C. Carson, J. Chem. Phys. 1939, 7, 859.
[24] K. Nakamoto, Infrared and Raman Spectra of Inorganic and
Coordination Compounds, 4th ed., Wiley, New York, Chiches-
ter, Brisbane, Toronto, Singapore, 1986.
[25] J. Weidlein, U. Müller, K. Dehnicke, Schwingungsspektroskopie,
Georg Thieme, Stuttgart, New York, 1982.
Acknowledgement
We thank Dr. J. Daniels for encouraging help with the isolation of
crystals at low temperature and for the recording of the diffraction
data set.
Received: July 18, 2008
Published Online: April 3, 2009
Z. Anorg. Allg. Chem. 2009, 687Ϫ691
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
691