Table 2 Crystallographic data for [VVO(Hm)(L)]ؒ¹C6H6
References
¯
²
1 D. C. Crans, R. A. Felty, O. P. Anderson and M. M. Miller, Inorg.
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Formula
M
Crystal size/mm
Crystal system
Space group
a/Å
b/Å
c/Å
C21H27NO10V
504.37
0.3 × 0.4 × 0.3
Monoclinic
P21
9.789(3)
18.534(5)
13.689(4)
91.64(2)
2483(1)
4
1.349
295
0.452
4381
4060 (0.036)
2828
449
0.0649, 0.1396
0.457, Ϫ0.288
β/Њ
U/Å3
Z
Dc/Mg mϪ3
T/K
µ/mmϪ1
Reflections collected
Unique reflections (Rint
Reflections with [I > 2σ(I)]
Parameters refined
)
R1, wR2 [I > 2σ(I)]
Maximum, minimum ∆ρ/e ÅϪ3
6 R. N. Lindquist, L. J. Lynn, jun. and G. E. Lienhar, J. Am. Chem.
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ed. N. D. Chasteen, Kluwer, Dordrecht, 1990.
(d, J = 20, HB(11)), 8.49 (s, H(12)), 7.50 (d, J = 7.2, H(14)), 6.96
(t, J = 8.4, H(15)), 7.59 (t, J = 9.9, H(16)) and 6.90 (d, J = 8.1,
51
3ϩ
2ϩ
₁
H(17)). V NMR [CDCl3]: δϪ544. E (VO –VO couple) in
₂
CH2Cl2–CH3CN(1:1): Ϫ0.25 V (irr).
9 A. F. Nour-Eldeen, M. M. Craig and M. J. Gresser, J. Biol. Chem.,
1985, 260, 6836.
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Res., 1996, 289, 39.
Complex [VVO(Hr)(L)]. Yield: 0.13 g (82%) (Found: C, 45.67;
H, 4.70; N, 3.30. Calc. for C16H20NO9V: C, 45.60; H, 4.75; N,
3.33%). UV/VIS [Me2SO, λmax/nm (ε/dm3 molϪ1 cmϪ1)]:
500(516) and 340(4925). IR (KBr, cmϪ1): 982 (V᎐O), 1305 (CO ,
᎐
2
sym), 1623 (CO2, asym), 1700 (CO2, asym) and 3130 (very br,
OH). 1H NMR [(CD3)2SO]: δ 4.27 (s, H(1)), 3.97 (m, H(2)), 5.42
(dd, J = 3.4, 8.2, H(3)), 3.34 (m, H(4), H(5)), 3.39 (s, 1-OMe),
3.33 (s, 5-OMe), 7.12 (d, J = 3.6, OH; ‘disappears’ on shaking
with D2O), 5.12 (d, J = 19.0, HA(11)), 4.56 (d, J = 20.7, HB(11)),
8.90 (s, H(12)), 7.62 (d, J = 7.2, H(14)), 7.02 (t, J = 7.2, H(15)),
7.70 (t, J = 6.9, H(16)) and 6.93 (d, J = 8.4, H(17)). 51V NMR
16 S. J. Angus-Dunne, R. J. Batchelor, A. S. Tracey and F. W. B.
Einstein, J. Am. Chem. Soc., 1995, 117, 5292.
17 B. Zhang, S. Zhang and K. Wang, J. Chem. Soc., Dalton Trans.,
1996, 3257.
3ϩ
[(CD3)2SO]: δ Ϫ543. E (VO –VO2ϩ couple) in Me2SO: Ϫ0.28 V
₁
₂
(irr).
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31, 2841.
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Carrano, Inorg. Chem., 1992, 31, 2029.
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for Chemists, Wiley, New York, 1974, p. 212.
Crystallography
Crystals of [VVO(Hm)(L)]ؒ¹C6H6 were grown by slow diffusion
¯
²
of hexane into benzene solution. Data were collected by the
ω-scan technique on a Siemens R3m/V four-circle diffract-
ometer with graphite-monochromated Mo-Kα radiation (λ
0.71073 Å). Two check reflections displayed no intensity reduc-
tion. All calculations were done using the SHELXTL pro-
grams.31 The structure was solved by direct methods and refined
by full-matrix least squares on F2. Data were corrected for
Lorentz-polarisation effects and empirical absorption correc-
tions were done on the basis of azimuthal scans of six
reflections.32 Metal, nitrogen, oxygen and all the carbohydrate
carbon atoms were made anisotropic. A few of the hydrogens
were directly located and the remaining included in calculated
positions. Significant crystal data are listed in Table 2.
CCDC reference number 186/1492.
graphic files in .cif format.
27 G. K. Lahiri, S. Bhattacharya, B. K. Ghosh and A. Chakravorty,
Inorg. Chem., 1987, 26, 4324.
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29 W. M. Ho, H. N. C. Wong, L. Navailles, C. Destrade, H. T. Naguyen
and N. Isaert, Tetrahedron, 1995, 50, 7373.
Acknowledgements
30 K. Takeo and M. Kawaguchi, J. Carbohydr. Chem., 1993, 12, 1045.
31 G. M. Sheldrick, SHELXTL, version 5.03, Siemens Analytical
Instruments Inc., Madison, WI, 1994.
32 A. C. T. North, D. C. Phillips and F. S. Mathews, Acta Crystallogr.,
Sect. A, 1968, 24, 351.
Financial support received from the Indian National Science
Academy, the Department of Science and Technology and the
Council of Scientific and Industrial Research, New Delhi
is acknowledged, as is affiliation to the Jawaharlal Nehru
Centre for Advance Scientific Research, Bangalore. We thank
Professors N. Ray, G. K. Lahiri and Dr A. Choudhury for their
help.
Paper 9/02632K
2540
J. Chem. Soc., Dalton Trans., 1999, 2537–2540