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The crystal structure of the 4-phenylpyridine adduct of vanadylbisacetylacetonate
INORG.
NUCL.
CHEM.
LETTERS
Vol.
8, pp.
109-112,
1972.
Pergamon
Press.
Printed in Great Britain.
THE CRYSTAL STRUCTURE OF THE 4-PHENYLPYRIDINE ADDUCT OF VANADYLBISACETYLACETONATE
M.R. Caira, J.M. Haigh and L.R. Nassimbeni. Department of Chemistry, University of Cape Town, South Africa. (Received 29 O c t o ~ r 1 ~ I )
The reaction between vanadylbisacetylacetonate and various bases B, yields adducts of the type [VO(ACA)2.B] where B is R-C5H4 N.
Haigh I has examined
the far infrared spectra of fourteen variously substituted pyridine adducts of VO(ACA)2, having general formula [VO(ACA)2.R-C5H4 N] with R = 4-C02C2H5, 4-COC6H5, 4-C6H5, 3,5-di-CH 3, 4-C2H5, 3-NH 2, 4-t-C4H9, 4-N(CH3)2,4-NH2, 4-CN, H, 4-n-C3H7, 4-CH3, 3,4-di-CH 3.
For nine of these complexes, v V=O is lowered
from the parent acetylacetonate by 42 ~ 4 cm -I and for five of them v V=O is lowered by 29 ~ 4 cm -I
The four V-O sensitive modes in the far infrared region
all occurred at approximately the same frequencies in the smaller group of adducts.
However, in the larger group of nine adducts, extra peaks appeared at
552, 435 and 335 cm
-I
These were attributed to a reduction of the degree of
symmetry of these complexes.
It was therefore suggested that these adducts exist
as cis- and trans- isomers with the structures shown in figure I.
"g"
o
I
cis
trans
~.~j~-R
On the basis of the above argument, the adduct in which B = 4-phenylpyridine was predicted to have the cis-configuration. We have elucidated the structure of the latter adduct by X-ray diffraction.
109
b
e®®
Q
Z ,,-/
,,,,1
t~
m
[]
Z
2
t"
z
m
Vol. 8, No. 1
T H E 4 - P H E N Y L P Y R I D I N E ADDUCT O F V A N A D Y L B I S A C E T Y L A C E T O N A T E
Crystal data : M = 420.1;
monoclinic crystals with a = 24-29 ~, b = 8.14 ~,
c = 21.66 ~, B = 71"4 ° Dm = 1-36, Dc = 1.37 g cm -3, Z = 8. either C2/c or C c.
111
The space group was
The space group C2/c was chosen after inspection of a three
dimensional Patterson map and the subsequent structure analysis and refinement vindicated this choice.
The intensity data were collected on Weissenberg
photographs and were estimated visually.
1412 independent reflections were
measured and the structure was solved by standard Patterson and Fourier techniques Full matrix least squares refinement with anisotropic temperature factors applied to all the atoms gave an R factor of 0-106. The structure of the adduct is shown in figure 2.
The bond lengths are given in ~.
As pred!cted by Haigh, the molecule has the cis-configuration. asymmetric and there are four enantiomorphous pairs in the unit cell.
It is The length
of the vanadyl bond, V = 0 is 1.58 ~ 0.01 ~, compared with values of 1.56 ~ 0.01 and 1.57 ~ 0.01 for V = 0 in VO(ACA) 2 itself. 2'3 dium atom is approximately octahedral.
The coordination of the vana-
Atoms 05, 03, N and 04 define a plane,
but the vanadium atom is situated on the same side of the plane as the vanadyl oxygen 01, at a distance of 0-22~ from the plane.
While the chelate ring
containing the atoms V, 02, CI, C2, C 3 and 03 is virtually planar, this is not true for the second chelate ring.
In the latter ring, the plane containing the
atoms V, 04, 05 intersects the plane containing the atoms 04, C6, C7, C 8 and 05 at an angle of 161.5 ° .
Th s is shown in figure 3.
fig.3 C8 05~ °
c2
~ 7 ._
~,~ x= 1 7 9 - 0 ° o
y= 161.5
112
THE 4-PHENYLPYRID1NE
ADDUCT OF VANADYLBISACETYLACETONATE
Vol. 8, No. 1
Acknowledgements: We thank the C.S.I.R. and the University of Cape Town for research grants.
REFERENCES
I.
J.M. HAIGH, Ph.D. Thesis, University of Cape Town (1970)
2.
R.P. DODGE, D.H. TEMPLETON, and A. ZALKIN, J.Chem.Phys.
3.
P. HON, R. BELFORD, and C.E PFLUGER, J.Chem.Phys.
35, I, 55 (1961)
43, 9, 3111 (1965)
NUCL.
CHEM.
LETTERS
Vol.
8, pp.
109-112,
1972.
Pergamon
Press.
Printed in Great Britain.
THE CRYSTAL STRUCTURE OF THE 4-PHENYLPYRIDINE ADDUCT OF VANADYLBISACETYLACETONATE
M.R. Caira, J.M. Haigh and L.R. Nassimbeni. Department of Chemistry, University of Cape Town, South Africa. (Received 29 O c t o ~ r 1 ~ I )
The reaction between vanadylbisacetylacetonate and various bases B, yields adducts of the type [VO(ACA)2.B] where B is R-C5H4 N.
Haigh I has examined
the far infrared spectra of fourteen variously substituted pyridine adducts of VO(ACA)2, having general formula [VO(ACA)2.R-C5H4 N] with R = 4-C02C2H5, 4-COC6H5, 4-C6H5, 3,5-di-CH 3, 4-C2H5, 3-NH 2, 4-t-C4H9, 4-N(CH3)2,4-NH2, 4-CN, H, 4-n-C3H7, 4-CH3, 3,4-di-CH 3.
For nine of these complexes, v V=O is lowered
from the parent acetylacetonate by 42 ~ 4 cm -I and for five of them v V=O is lowered by 29 ~ 4 cm -I
The four V-O sensitive modes in the far infrared region
all occurred at approximately the same frequencies in the smaller group of adducts.
However, in the larger group of nine adducts, extra peaks appeared at
552, 435 and 335 cm
-I
These were attributed to a reduction of the degree of
symmetry of these complexes.
It was therefore suggested that these adducts exist
as cis- and trans- isomers with the structures shown in figure I.
"g"
o
I
cis
trans
~.~j~-R
On the basis of the above argument, the adduct in which B = 4-phenylpyridine was predicted to have the cis-configuration. We have elucidated the structure of the latter adduct by X-ray diffraction.
109
b
e®®
Q
Z ,,-/
,,,,1
t~
m
[]
Z
2
t"
z
m
Vol. 8, No. 1
T H E 4 - P H E N Y L P Y R I D I N E ADDUCT O F V A N A D Y L B I S A C E T Y L A C E T O N A T E
Crystal data : M = 420.1;
monoclinic crystals with a = 24-29 ~, b = 8.14 ~,
c = 21.66 ~, B = 71"4 ° Dm = 1-36, Dc = 1.37 g cm -3, Z = 8. either C2/c or C c.
111
The space group was
The space group C2/c was chosen after inspection of a three
dimensional Patterson map and the subsequent structure analysis and refinement vindicated this choice.
The intensity data were collected on Weissenberg
photographs and were estimated visually.
1412 independent reflections were
measured and the structure was solved by standard Patterson and Fourier techniques Full matrix least squares refinement with anisotropic temperature factors applied to all the atoms gave an R factor of 0-106. The structure of the adduct is shown in figure 2.
The bond lengths are given in ~.
As pred!cted by Haigh, the molecule has the cis-configuration. asymmetric and there are four enantiomorphous pairs in the unit cell.
It is The length
of the vanadyl bond, V = 0 is 1.58 ~ 0.01 ~, compared with values of 1.56 ~ 0.01 and 1.57 ~ 0.01 for V = 0 in VO(ACA) 2 itself. 2'3 dium atom is approximately octahedral.
The coordination of the vana-
Atoms 05, 03, N and 04 define a plane,
but the vanadium atom is situated on the same side of the plane as the vanadyl oxygen 01, at a distance of 0-22~ from the plane.
While the chelate ring
containing the atoms V, 02, CI, C2, C 3 and 03 is virtually planar, this is not true for the second chelate ring.
In the latter ring, the plane containing the
atoms V, 04, 05 intersects the plane containing the atoms 04, C6, C7, C 8 and 05 at an angle of 161.5 ° .
Th s is shown in figure 3.
fig.3 C8 05~ °
c2
~ 7 ._
~,~ x= 1 7 9 - 0 ° o
y= 161.5
112
THE 4-PHENYLPYRID1NE
ADDUCT OF VANADYLBISACETYLACETONATE
Vol. 8, No. 1
Acknowledgements: We thank the C.S.I.R. and the University of Cape Town for research grants.
REFERENCES
I.
J.M. HAIGH, Ph.D. Thesis, University of Cape Town (1970)
2.
R.P. DODGE, D.H. TEMPLETON, and A. ZALKIN, J.Chem.Phys.
3.
P. HON, R. BELFORD, and C.E PFLUGER, J.Chem.Phys.
35, I, 55 (1961)
43, 9, 3111 (1965)