Chemistry Letters 2000
563
counter anion as mentioned above. The formation of the poly-
meric structure in the SbF6 salts may be attributed to a non-
-
coordinating property of the SbF6 anion, weak Lewis basicity
of acetonitrile used as a solvent, and crystal packing efficiency.
References and Notes
1
2
3
4
M. Mathew, A. J. Carty, and G. J. Palenik, J. Am. Chem.
Soc., 92, 3197 (1970).
A. Hills, D. L. Hughes, G. J. Leigh, and J. R. Sanders, J.
Chem. Soc., Dalton Trans., 1991, 61.
L. Banci, A. Bencini, A. Dei, and D. Gatteschi, Inorg.
Chim. Acta, 84, L11 (1984).
a) J. A. Bonadies, W. M. Butler, V. L. Pecoraro, and C. J.
Carrano, Inorg. Chem., 26, 1218 (1987). b) M.
Tsuchimoto and S. Ohba, Acta Cryst. Sect. C, 55,
IUC9900008 (1999).
…
…
…
…
…
chain represented as V1A=O2A V1B’=O2B’ (V=O units
5
6
K. Nakajima, K. Kojima, M. Kojima, and J. Fujita, Bull.
Chem. Soc. Jpn., 63, 2620 (1990).
…
enclosed by parallelograms) and V1A’=O2A V1B=O2B
(V=O units enclosed by circles).
The structure of the complex cation in the linear chain of
(II) in one of the orientations (V=O units enclosed by parallelo-
grams) is shown in Figure 3. The molecule has a distorted octa-
[VO(5-MeOsalen)(H2O)]NO3·H2O: Anal. Found: C, 44.01;
H, 4.45; N, 8.70%. Calcd for C18H22N3O10V: C, 44.00; H,
4.51; N, 8.55%. [VO(salen)(H2O)]NO3·H2O : Anal.
Found: C, 44.73; H, 4.10; N, 9.91%. Calcd for
C16H18N3O8V: C, 44.56; H, 4.21; N, 9.74%.
7
Crystal data: C18H22N3O10V1, M = 491.33, monoclinic,
space group P21/c (no. 14), a = 24.718(4), b = 16.919(3), c
= 10.295(3) Å, β = 101.88(2)°, U = 4212(1) Å3, Z = 8, Dc =
1.549 g cm-3, µ(MoKα)= 0.532 mm-1, crystal size = 0.60 ×
0.50 × 0.10 mm, 10212 reflections measured, 9670 unique
reflections. Refinement was based on F with Rw = [Σ w
(|Fo| - |Fc|)2/Σw|Fo|2]1/2, w-1 = σ2(|Fo|) + 0.00119|Fo|2,
against all the 9670 reflections. The R value (Σ||Fo| -
|Fc||/Σ|Fo|) was 0.041 for the 6329 reflections with I >
2σ(I). The Rw value was 0.067.
8
9
[VO(5-MeOsalen)]SbF6: Anal. Found: C, 34.27; H, 2.79;
N, 4.65%. Calcd for C18H18N2O5F6Sb1V: C, 34.37; H,
2.88; N, 4.45%. [VO(salen)] SbF6: Anal. Found: C, 33.92;
H, 2.36; N, 5.01%. Calcd for C16H14N2O3F6Sb1V: C,
33.78; H, 2.48; N, 4.92%.
K. Nakajima, M. Kojima, M. Tsuchimoto, Y. Yoshikawa,
and J. Fujita, Chem. Lett., 1994, 1593.
10 M. Tsuchimoto, G. Hoshina, R. Uemura, K. Nakajima, M.
Kojima, and S. Ohba, in preparation.
hedral geometry with weak coordination of the oxo ligand of
the adjacent molecule at the sixth position. However, the V=O
distances in (II) (1.577(2) and 1.571(2) Å) are a little shorter
than those in (I) (1.584(2) and 1.587(2) Å), although the V=O
stretching band of (II) is largely shifted to lower energy than
that of (I). The short V=O distances in (II) may be an artifact
due to the positional disorder of the vanadium atom. In any
11 M. Tsuchimoto, R. Kasahara, K. Nakajima, M. Kojima,
and S. Ohba, Polyhedron, 18, 3035 (1999).
12 Crystal data: C18H18N2O5F6Sb1V1, M = 629.03, triclinic,
-
space group P1 (no. 2), a = 11.653(1), b = 13.159(2), c =
7.659(2) Å, α = 103.02(2), β = 98.67(1), γ = 91.10(1)°, U =
1129.5(4) Å3, Z = 2, Dc = 1.849 g cm-3, µ(MoKα)= 1.689
mm-1, crystal size = 0.50 × 0.50 × 0.10 mm, 5432 reflec-
…
case, the V V distance and the V=O stretching frequecy of (II)
tions measured, 5171 unique reflections. Refinement was
2 2
(3.83 Å and 878 cm-1) indicate that the complex has a linear
based on F2 with Rw = [Σ w (Fo2 - Fc ) /Σw(Fo2)2]1/2, w-1
=
V
V
2
2
2
V =O V =O chain structure in which the V=O units are
a little more weakly bonded to each other than those of
σ2(Fo ) + (0.0203P)2 + 4.7006P, where P = (Fo + 2Fc )/3
…
…
…
against all the 5171 reflections. The R value [Σ(Fo2 - Fc )
2 2
-1
1
[VO(salpn)]( V V distance: 3.78 Å, ν(V=O): 854 cm ).
/Σw(Fo)2]1/2 was 0.058 for the 4608 reflections with I >
2σ(I). The Rw value was 0.134.
…
Polymeric [VO(Xsalen)]SbF6 were prepared from
monomeric [VO(Xsalen)(H2O)]NO3·H2O by changing the