Synthesis and characterisation of [XeF5]3[Ti 4F19] containing a discrete [Ti4F 19]3- anion

Article abstract of DOI:10.1002/ejic.200900628

The complex [XeF₅]₃[Ti₄F₁₉] was prepared by reaction of XeF₂, TiF₄ and UV-irradiated elemental fluorine in anhydrous hydrogen fluoride as the solvent. The crystal structure of [XeF₅

Full text of DOI:10.1002/ejic.200900628

FULL PAPER
DOI: 10.1002/ejic.200900628
Synthesis and Characterisation of [XeF5]3[Ti4F19] Containing a Discrete
[Ti4F19]3– Anion
Zoran Mazej*[a] and Evgeny Goreshnik[a]
Keywords: Titanium / Xenon / Fluorine / Structure elucidation / Vibrational spectroscopy
The complex [XeF5]3[Ti4F19] was prepared by reaction of
XeF2, TiF4 and UV-irradiated elemental fluorine in anhy-
drous hydrogen fluoride as the solvent. The crystal structure
only two µ3-[TiF6] octahedra share three apexes with three
other [TiF6] units. Each of the remaining two µ2-[TiF6] octahe-
dra shares only two vertices with two of the above-men-
tioned µ3-[TiF6] moieties. The Raman spectrum of [XeF5]3-
of [XeF5]3[Ti4F19] consists of [XeF5]+ cations and discrete
3–
[Ti4F19
]
anions. The [XeF5] units have usual slightly dis-
[Ti4F19] is in agreement with the presence of [XeF5]+ cations
3–
torted pseudo-octahedral symmetry. Contrary to the pre- and [Ti4F19
viously reported [Ti4F18
2– anion, where each TiF6 octahedron
shares three apexes with three other octahedra, in [Ti4F19]3–, Germany, 2009)
]
anions.
]
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
in the highest oxidation state.[3–8] Reactions between dif-
Introduction
ferent starting mol ratios of XeF2 and TiF4 were investi-
gated [n(XeF2)/n(TiF4) = 4:1, 3:1, 2:1, 1:1, 1:2, 1:3]. To ob-
tain a definitive answer as to whether the isolated products
are single phases or mixtures of different ones, the isolated
solids were dissolved in aHF and recrystallised. Although
different kinds of crystals were observed, all attempts re-
sulted so far only in the determination of the crystal struc-
ture of 3XeF6·4TiF4. The synthesis of 3XeF6·4TiF4 was
later achieved by the photochemical fluorination of a XeF2/
TiF4 mixture with a mol ratio of XeF2/TiF4 = 3:4 in aHF.
The crystal structure of 3XeF6·4TiF4 consists of [XeF5]+
cations and previously unknown discrete [Ti4F19]3– anions.
The compound 3XeF6·4TiF4 is therefore formulated as
[XeF5]3[Ti4F19]. There are three crystallographically non-
equivalent [XeF5]+ cations in the crystal structure of [XeF5]3-
[Ti4F19]. All three [XeF5] units have well-known, slightly
distorted pseudo-octahedral symmetry,[9] where the axial
Xe–Fax distances [Xe1–F13 1.820(5) Å, Xe2–F23
The reaction between TiF4 and an excess amount of
XeF6 at ambient temperature yields (XeF6)4·TiF4.[1] The
latter releases XeF6 under dynamic vacuum at 40 °C to give
XeF6·TiF4, which decomposes further at 65 °C into XeF6
and XeF6·2TiF4.[1] The compositions of the obtained
phases were determined by elemental chemical analysis.[1]
Their infrared spectra and magnetic susceptibilities were
also reported.[1] Because no structural data on these com-
pounds is known, a systematic study was undertaken to
achieve a better understanding of the possible phases in the
XeF6/TiF4 system and to investigate the nature of the iso-
lated products {i.e., [XeF5]+, [Xe2F11]+ or mixed [XeF5]+-
[Xe2F11]+ salts and the composition of the anionic part:
x–
[TinF4n+x
]
(n, x Ն 1)}.
Results and Discussion
Instead of XeF6, we used XeF2 as a starting material and 1.811(5) Å, Xe3–F33 1.822(5) Å] are slightly shorter than
as precursor for the in situ preparation of XeF6. The XeF2/ the equatorial [Xe1–Feq 1.834(5)–1.847(5) Å, Xe2–Feq
TiF4 mixtures could be prepared in the requested molar 1.826(5)–1.852(5) Å, Xe3–Feq 1.838(5)–1.849(5) Å] dis-
ratios and loaded into reaction vessels in a dry box; mean- tances. Each of the [XeF5] units makes further contacts
while, XeF6 could be added onto TiF4 only by condensation with the fluorine atoms of three [Ti4F19]3– anions, where
in a vacuum system.[2] XeF2 was converted into XeF6 by Xe1···F 2.568, 2.664, 2.694 and 2.812 Å; Xe3···F 2.559,
photochemical reaction with UV-irradiated elemental fluor- 2.594 and 2.610 Å and Xe2···F 2.470, 2.707 and 2.712 Å,
ine in anhydrous hydrogen fluoride (aHF) as a solvent. This with the next closest F(–Xe2) being at 3.146 Å. The sum of
method is very convenient for the preparation of some bi- the Xe···F van der Waals radii is 3.63 Å.[10] Although the
nary and ternary fluorides in which the transition metal is number and strength of these contacts is not the same for
all three [XeF5] units, they all show the same feature. The
anionic fluorine atoms involved in these contacts are ar-
[a] Jozef Stefan Institute,
ˇ
ranged symmetrically around the pseudo-fourfold axis of
the [XeF5] unit (i.e., around the sterically active nonbond-
ing valence-electron pair of Xe).
Jamova 39, SI-1000 Ljubljana, Slovenia
Fax: +386-1-477-3155,
E-mail: zoran.mazej@ijs.si
Eur. J. Inorg. Chem. 2009, 4503–4506
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4503

Z. Mazej, E. Goreshnik
FULL PAPER
The most interesting feature of the determined crystal
structure of [XeF5]3[Ti4F19] is the presence of [Ti4F19]3–
anions. The compounds containing isolated [TiF6]2–,[11]
[Ti2F11]3–,[12] [Ti2F10]2–[13,14] and [Ti4F18]2–[15,16] or poly-
[19]
meric ([Ti7F30]2–)n,[17] ([Ti8F33]–)n,[18] ([TiF5]–)n
and
[16]
([Ti2F9]–)n
anions are known. Contrary to a literature
statement,[15] the discrete [TiF7]3– anion is not known.
Fluorides of the type A3TiF7 (A = Rb+, Cs+, [NH4]+)[20]
contain [TiF6]2– anions and “free” fluoride ions[21] and are
better formulated as A3F(TiF6).[22]
The previously known [Ti4F18]2– anion[15,16] consists of
four [TiF6] octahedra that are associated by corners in or-
der to built a tetrahedron of octahedra. In this way, Ti
atoms are situated at the vertices of a tetrahedron (with
nonbonding Ti···Ti distances in the 3.829–3.875 Å range
and Ti···Ti···Ti angles around 60°),[15,16] connected by six
bridging fluorine atoms and capped by three terminal fluor-
ine atoms each (Figure 1a).
Figure 2. The [Ti4F19]3– anion and three crystallographically inde-
pendent [XeF5]+ cations (ellipsoids are drawn at 40% probability).
Selected distances [Å] and angles [°], cations: Xe–Fax, Xe1–F13
1.820(5), Xe2–F23 1.811(5), Xe3–F33 1.822(5); Xe–Feq, Xe1–F14
1.834(5), Xe1–F15 1.841(5), Xe1–F12 1.841(5), Xe1–F11 1.847(5),
Xe2–F21 1.826(5), Xe2–F22 1.839(5), Xe2–F25 1.849(5), Xe2–F24
1.852(5), Xe3–F34 1.838(5), Xe3–F32 1.843(5), Xe3–F35 1.844(5),
Xe3–F31 1.849(5); anions: av Ti–Ft 1.742 Å, av Ti–Fb 1.975 Å;
Ti2–F3–Ti4 155.8(2), Ti1–F5–Ti2 152.7(3), Ti3–F6–Ti4 147.8(2),
Ti1–F8–Ti4 150.4(2), Ti1–F9–Ti3 149.1(3).
Figure 1. [Ti4F18]2– (a) and [Ti4F19]3– (b) anions, each comprising
four [TiF6] octahedra.
The [Ti4F19]3– anion also consists of four [TiF6] octahe-
dra that are associated in a manner different from that in
[Ti4F18]2–. Two µ3-[TiF6] octahedra sharing a joint apex
(Figure 1b, octahedra in the middle) are additionally
bridged by two µ2-[TiF6] units. The nonbonding Ti···Ti dis-
tances (3.791–3.865 Å) are in the same range as those in
[Ti4F18]2–. Only the Ti···Ti distance between the Ti atoms
Figure 3. Packing diagram of [XeF5]3[Ti4F19].
Vibrational Spectra
The Raman spectrum of [XeF5]3[Ti4F19] is shown in Fig-
belonging to the two µ2-[TiF6] units is much longer ure 4 with additional details given in Table 1.
(4.946 Å). The [Ti4F19]3– anion and three crystallographi-
The Raman spectra recorded for the powdered sample
cally independent [XeF5]+ cations and numbering scheme obtained by synthesis and the Raman spectra recorded for
adopted are given in Figure 2. The packing diagram is de- the single crystals of [XeF5]3[Ti4F19] were essentially iden-
picted in Figure 3.
tical. The bands above 700 cm–1 could be readily assigned
The Ti–Ft [Ft: terminal fluorine atom; 1.747(5)– to the vibration of the anion. The band at 742 cm–1 belongs
1.839(5) Å] and Ti–Fb [Fb: bridging fluorine atom; to the symmetric in-phase terminal Ti–F stretching mode,
1.935(4)–2.044(4) Å] bond lengths in [XeF5]3[Ti4F19] are where the frequency of the band increases with increasing
comparable to those found for [Ti4F18]2– salts [Ti–Ft content of TiF4 and decreasing charge of the anion {i.e.,
1.752(4)–1.783(4) Å; Ti–Fb 1.959(4)–2.019(4) Å],[15,16] and [TiF6]2– ≈600,[27] [Ti2F10]2– 703,[27] ([TiF5]–)n 724,[19]
both sets of distances are in agreement with those pre- [Ti4F18]2– ≈746,[15,16] ([Ti2F9]–)n ≈753,[16] ([Ti7F30]2–)n
viously observed in various TiIV fluoride complexes.[23,24] 765,[17] [Ti3F13]– 770,[27] [Ti6F25]– 784[27] and ([TiF4])n
Some of the Ti–Ft distances (1.795–1.839 Å) are slightly 807 cm–1[27]}. The assignments below 700 cm–1 were done
elongated due to weak Ft···Xe interactions (2.470–2.721 Å). by comparison with the literature data for the [XeF5]+ cat-
4504
www.eurjic.org
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2009, 4503–4506

[XeF5]3[Ti4F19] Containing a Discrete [Ti4F19]3– Anion
susceptible to moisture and react with water to form XeO3, a com-
pound that easily detonates.[33] For treatment of HF injuries see
reference.[34]
Reagents: The compound TiF4 was synthesised by the reaction of
TiCl3 (Aldrich, 99.999%) and elemental fluorine in aHF. The X-
ray powder diffraction pattern and Raman spectrum of isolated
TiF4 were in agreement with the literature data.[35,36] Xenon difluo-
ride was prepared by the photochemical reaction between Xe and
F2 at ambient temperature.[37]
Raman Spectroscopy: Raman spectra were recorded with a Reni-
shaw Raman Imaging Microscope System 1000 by using a He–Ne
laser with a wavelength of 632.8 nm.
Figure 4. Raman spectrum of [XeF5]3[Ti4F19].
X-ray Powder Diffraction Patterns: X-ray powder diffraction pat-
terns were obtained by using the Debye–Scherrer technique with
Ni-filtered Cu-Kα radiation. Samples were loaded into quartz capil-
laries (0.3 mm) in a dry box. Intensities were estimated visually.
Table 1. Raman data [cm–1] of [XeF5]3[Ti4F19] together with litera-
ture data for [XeF5][AsF6], [XeF5]2[PdF6] and [XeF5][RuF6].[25,26]
[XeF5]3[Ti4F19]
[XeF5][AsF6] [XeF5]2[PdF6] [XeF5][RuF6] Assignments
Synthesis of [XeF5]3[Ti4F19]: In a dry-box, a sample of XeF2
(1.20 mmol) and TiF4 (1.60 mmol) were loaded into a FEP (tetra-
fluoroethylene–hexafluoropropylene) reaction vessel. aHF (8 mL)
was condensed onto the solid at 77 K, and the reaction mixture
was brought to ambient temperature. Fluorine was slowly added at
ambient temperature to a pressure of 6 bar in the reaction vessel.
A 400 W medium pressure mercury lamp (Baird and Tatlock, Lon-
don, Type 400 LQ) was used as the UV source. After 6 d, volatiles
were pumped off at 77 K and a new portion of fluorine was added.
The reaction mixture was left stirring for 22 d at ambient tempera-
ture. A clear yellowish solution was obtained above an insoluble
material. Volatiles were slowly pumped off at ambient temperature
for 2 h, leaving behind a colourless solid. The final mass of the
isolated solid was 0.501 mg (calcd. for [XeF5]3[Ti4F19] 0.500 mg).
The Raman spectrum was recorded, the X-ray powder diffraction
diagram was taken and a chemical analysis was obtained {[XeF5]3-
[Ti4F19] (1231.35): calcd. for Ti 15.56; found Ti 15.0}.
742(30)
710(5)
680(sh.)[a]
670(25, sh.)
659(58)
[Ti4F19]3–
[Ti4F19]3–
664(5), sh.
661(30)
671(29)
629(100)
623(5), sh.
676(3)
677(9)
664(1), sh.
670(22)
606(68)
600(10), sh.
[XeF5]+, ν7(E)
[XeF5]+, ν7(E)
[XeF5]+, ν1(A1)
[XeF5]+, ν2(A1)
[XeF5]+, ν4(B1)
[Ti4F19]3–
660(5), sh.
653(100)
590(71)
606(20)
606(100)
582(12, sh.)
516(2, sh.)
489(4)
418(5)
412(6)
368(3)
310(8)
284(5)
250(Ͻ1)
231(2)
[Ti4F19]3–
[Ti4F19]3–
412(6)
407(6)
425(3)
396(3)
416(4)
416(4)
[XeF5]+, ν8(E)
[XeF5]+, ν8(E)
[Ti4F19]3–
296(15)
309(10)
312(2)
[XeF5]+, ν3(A1)
[Ti4F19]3–
255(1)
240(0+)
214(4)
[XeF5]+, ν6(B2)
[XeF5]+, ν5(B1)
[XeF5]+, ν9(B)
230(4)
[230]
236(1)
215(2)
[a] sh. = shoulder.
Crystal Growth of [XeF5]3[Ti4F19]: Single crystals growth of [XeF5]3-
[Ti4F19] was carried out in a T-shaped apparatus consisting of two
FEP tubes (19 mm. o.d., and 6 mm. o.d.). [XeF5]3[Ti4F19] (approxi-
mately 150 mg) was loaded into the wider arm of the crystallisation
vessel in the dry box. aHF (≈3 mL) was then condensed onto the
starting material at 77 K. The crystallisation mixture was brought
up to ambient temperature, and the clear colourless solution was
decanted into the narrower arm. Evaporation of the solvent from
this solution was carried out by maintaining a temperature gradient
corresponding to about 10 K between both tubes for 5 weeks. The
result of this treatment was to slowly condense the aHF from the
narrower tube into the wider tube, leaving behind the crystals. Se-
lected single crystals of [XeF5]3[Ti4F19] were placed inside 0.3-mm
quartz capillaries in a dry box and their Raman spectra recorded.
ion. The possibility that some of the cation vibrational
bands overlap with the anionic ones could not be com-
pletely excluded.
Conclusions
In spite of a large number of existing compounds in the
XeF6/MF4 (M = transition element) system,[28] reports
about the crystal structures of the corresponding [XeF5]+
salts are limited to M = Pd, Ni and Cr. The crystal structure
of [XeF5]2[MF6] (M = Pd,[29] Ni[30]) consists of [XeF5]+ and
[MF6]2– entities. The main structural features of XeF5CrF5
are infinite [CrF5]– chains of [CrF6] octahedra and [XeF5]+
cations[31] {the crystal structure of (XeF5CrF5)4·XeF4 was
also reported[32]}. The crystal structure of [XeF5]3[Ti4F19]
differs from the previously described ones and represents a
unique case containing discrete [M4F19]3– anions.
Crystal Structure Determination: Crystals were immersed in perflu-
orinated oil (Perfluorodecalin, ABCR, 98%) in the dry box, se-
lected under a microscope and transferred into the cold nitrogen
stream of the diffractometer. Crystal data for [XeF5]3[Ti4F19]: Mt
= 1231.4 gmol–1, space group P21/c (No. 14), crystal system mono-
clinic, a = 12.0866(5) Å, b = 9.5615(3) Å, c = 21.0377(8) Å, β =
96.301(2)°, V = 2416.6(2) Å3, Z = 4, ρcalcd. = 3.385 gcm–3, T =
200 K. Data collection: Rigaku AFC7S diffractometer equipped
with a Mercury CCD area detector by using graphite monochro-
mated Mo-Kα radiation (λ = 0.71069). Reflections collected: 19129,
independent reflections: 5533 (Rint = 0.0463), observed reflections
[IϾ2σ(I)]: 4846, µ = 5.663 mm–1. Structural analysis and refine-
ment: The structure was solved by direct methods with the use of
the SIR-92[38] program (program package TeXsan[39]) and refined
Experimental Section
CAUTION: Anhydrous HF and some fluorides are highly toxic
and must be handled in a well-ventilated hood and protective cloth-
ing must be worn at all times! XeF6 and all of its products are
Eur. J. Inorg. Chem. 2009, 4503–4506
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
4505

Z. Mazej, E. Goreshnik
FULL PAPER
with SHELXL-97[40] software, implemented in the program pack-
age WinGX.[41] The figures were prepared using DIAMOND 3.1[42]
and Balls & Sticks.[43] Refinement method: Full matrix least-
squares on F2. Data-to-parameter ratio: 5533:371. Final R indices:
R1 = 0.0543 [IϾ2σ(I)], wR2 = 0.1417 [IϾ2σ(I)], R1 = 0.0615 (all
data), wR2 = 0.1539 (all data), GOF on F2 = 1.2, largest difference
peak/hole: 2.992/–1.984 eÅ–3. Further details of the crystal-struc-
ture investigation may be obtained from the Fachinformationszen-
trum Karlsruhe, 76344 Eggenstein-Leopoldshafen, Germany, on
quoting the depository number CSD-420743.
[15] A. Decken, H. D. B. Jenkins, C. Knapp, G. B. Nikiforov, J.
Passmore, J. M. Rautiainen, Angew. Chem. Int. Ed. 2005, 44,
7958–7961.
[16] Z. Mazej, E. Goreshnik, Inorg. Chem. 2009, 48, 6918–6923.
[17] B. G. Müller, J. Fluorine Chem. 1981, 17, 489–499.
[18] H. Bialowons, B. G. Müller, Z. Anorg. Allg. Chem. 1995, 621,
1223–1226.
[19] S. Cohen, H. Selig, J. Fluorine Chem. 1982, 20, 349–356.
[20] B. Hofmann, R. Hoppe, Z. Anorg. Allg. Chem. 1979, 458, 151–
162.
[21] D. Babel, A. Tressaud, “Crystal Chemistry of Fluorides” in
Inorganic Solid Fluorides, Chemistry and Physics (Ed.: P. Hag-
enmuller), Academic Press, Orlando, 1985, pp. 175–178.
[22] R. Hoppe, Angew. Chem. Int. Ed. Engl. 1981, 20, 63–87.
[23] H. W. Roesky, I. Haiduc, J. Chem. Soc., Dalton Trans. 1999,
2249–2264.
Acknowledgments
[24] E. F. Murphy, R. Murugavel, H. W. Roesky, Chem. Rev. 1997,
The authors gratefully acknowledge the Slovenian Research Ag-
ency (ARRS) for financial support of the present study within the
research program P1-0045 Inorganic Chemistry and Technology.
97, 3425–3468.
[25] C. J. Adams, N. Bartlett, Isr. J. Chem. 1978, 17, 114–125.
[26] Sh. Sh. Nabiev, Russ. J. Inorg. Chem. 1995, 40, 1936–1943.
[27] K. O. Christe, C. J. Schack, Inorg. Chem. 1977, 16, 353–359.
ˇ
[28] B. Zemva in Encyclopedia of Inorganic Chemistry (Eds.: R. B.
King), John Wiley & Sons, Chichester, 1994, vol. 5, pp. 2660–
ˇ
[1]
[2]
B. Zemva, J. Slivnik, M. Bohinc, J. Inorg. Nucl. Chem. 1976,
2680.
38, 73–74.
[29] K. Leary, D. H. Templeton, A. Zalkin, N. Bartlett, Inorg.
Chem. 1973, 12, 1726–1730.
Using XeF2 or XeF6 is a matter of choice. The use of XeF2,
which also requires the accompaniment of elemental fluorine
and repeated UV photolyses, instead of XeF6 results in longer
reaction times.
O. Graudejus, S. H. Elder, G. M. Lucier, C. Shen, N. Bartlett,
Inorg. Chem. 1999, 38, 2503–2509.
G. M. Lucier, J. M. Whalen, N. Bartlett, J. Fluorine Chem.
1998, 89, 101–104.
J. M. Whalen, G. M. Lucier, L. Chacón, N. Bartlett, J. Fluorine
Chem. 1998, 88, 107–110.
Z. Mazej, J. Fluorine Chem. 2002, 114, 75–80.
Z. Mazej, J. Fluorine Chem. 2002, 118, 127–129.
ˇ
[30] A. Jesih, K. Lutar, I. Leban, B. Zemva, Eur. J. Solid State,
Inorg. Chem. 1991, 28, 829–840.
ˇ
[31] K. Lutar, H. Borrmann, B. Zemva, Inorg. Chem. 1998, 37,
[3]
[4]
[5]
3002–3006.
ˇ
[32] K. Lutar, I. Leban, T. Ogrin, B. Zemva, Eur. J. Solid State,
Inorg. Chem. 1992, 29, 713–727.
[33] S. M. Williamson, C. W. Koch, Science 1963, 139, 1046–1047.
[34] D. Peters, R. Miethchen, J. Fluorine Chem. 1996, 79, 161–165.
[35] K. O. Christe, C. J. Schack, Inorg. Chem. 1977, 16, 353–359.
[36] H. Bialowons, M. Müller, B. G. Müller, Z. Anorg. Allg. Chem.
1995, 621, 1227–1231.
[6]
[7]
ˇ
[37] A. Smalc, K. Lutar in Inorganic Syntheses (Ed.: R. N. Grimes),
[8] Z. Mazej, E. Goreshnik, Eur. J. Inorg. Chem. 2008, 1795–1812.
[9] H. Selig, J. H. Holloway, Top. Curr. Chem. 1984, 124, 33–90.
[10] A. Bondi, J. Phys. Chem. 1964, 68, 441–451.
[11] R. J. H. Clark, D. C. Bradley, P. Thornton, “The Chemistry of
Titanium, Zirconium and Hafnium” in Comprehensive Inor-
ganic Chemistry (Eds.: J. C. Bailar Jr, H. J. Emeléus, Sir R. Ny-
holm, A. F. Trotman-Dickenson), Pergamon Press, Oxford,
1973, pp. 415–416.
[12] L. Q. Tang, M. S. Dadachov, X. D. Zou, Z. Kristallogr. New
Cryst. Struct. 2001, 216, 387–388.
[13] M. S. Dadachov, L. Q. Tang, X.-D. Zou, Z. Kristallogr. New
Cryst. Struct. 2000, 215, 605–606.
Wiley, New York, 1992, vol. 29, p. 1.
[38] A. Altomare, M. Cascarano, C. Giacovazzo, A. Guagliardi, J.
Appl. Crystallogr. 1993, 26, 343–350.
[39] Molecular Structure Corporation, teXsan for Windows: Single
Crystal Structure Analysis Software, version 1.06, The Wood-
lands, TX, USA, 1997–1999.
[40] G. M. Sheldrick, Acta Crystallogr., Sect. A 2008, 64, 112–122.
[41] L. J. Farrugia, J. Appl. Crystallogr. 1999, 32, 837–838.
[42] DIAMOND v3.1, Crystal Impact GbR, Bonn, Germany, 2004–
2005.
[43] T. C. Ozawa, S. J. Kang, J. Appl. Crystallogr. 2004, 37, 679;
Balls & Sticks: Easy-to-Use Structure Visualization and Anima-
tion Creating Program (http://www.softbug.com/toycrate/bs/).
Received: August 5, 2009
[14] H. Akutsu, K. Ozeki, T. Ozaki, K. Nozawa, M. Kinoshita, K.
Kozawa, T. Uchida, Bull. Chem. Soc. Jpn. 1996, 69, 1869–1873.
Published Online: September 8, 2009
4506
www.eurjic.org
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2009, 4503–4506