b
_:: (..
The Crystal
and Molecular
Structure
of
Acetatochlorobis(4-methylpyridine)oxovanadium John D. Schupp Department
of Chemistry,
and Stan A. Duraj*
Cleveland
State
Robert Department
of Science,
Mount
Group,
Department
NASA
St. Mary's
Glenn
of Chemistry,
University,
Cleveland,
OH
44115
M. Richman*
Aloysius Thin-Film
(IV)
College,
Emmitsburg,
MD
21727
F. Hepp*
Research
Center,
Phillip
E. Fanwick
Purdue
University,
Cleveland,
West Lafayette,
OH
IN
44135
47907
Abstract The crystal
and molecular
CH3CsH4N)2,
has been determined
crystallizes
in the space
= 99.73(1),
_ = 91.41(1),
vanadium monomeric
is a highly
group
VOCI(O2CCH3)(4-
by single-crystal
diffraction.
The material
b = 8.023(1),
c = 14.841(2)
Pl(#2)
The coordination The molecule
(IV) carboxylate.
to these
x-ray
with a = 7.822(2),
octahedron.
of oxovanadium
correspondence
of the title compound,
and y = 117.13(1).
distorted
oxovanadium
for the preparation
* - Address
structure
A generalized
geometry
is remarkable synthetic
around for being
strategy
A, ¢t
the a
is proposed
(IV) monomers.
authors.
This report is a preprint of an article submitted to a journal for publication. Because of changes that may be made before tbrmal publication, this preprint is made available with the understanding that it will not be cited or reproduced without the permission of the author.
Introduction Oxovanadium(IV) maybethe moststablediatomicion been
thoroughly
studied)
the bioinorganic carboxylates
because
chemistry might
Metal
The discovery
carboxylates
ligand. 5 Indeed,
abundance
of oligomeric
and polymeric
symmetry,
rather
length
oxovanadium
a unidentate that seems
oxovanadium
than the expected
bridge
monomeric
characterized.
(IV) carboxylate
.6 Cotton,
of 1.626(6)
groups
Two
structure,
times.
interest
in
ligand,
or
that vanadium
sites ofperoxidases.
since ancient
it is the latter mode
is V3(O)3(THF)(C6HsCO2)6
benzoate
been known
have
4
They are interesting ligand,
a bidentate
to be responsible
(IV) carboxylates
for the
that have been
58
The only other
bond
for the active
so its complexes
2'3 has spurred
It has also been suggested
may exist as a counterion,
a bridging
reported.
models
have
the carboxylate
of two vanadoenzymes
of vanadium.
be good
known,
4'9
the result
A, while
et. al. found
D3h. The V30
oxovanadium
atoms,
while
the first oxovanadium carboxylate
precipitated
from
characterized
has virtual
core is unsymmetrical,
(V) carboxylates
of bidentate
structurally
that this trimer
the other two are 2.344(7)
pairs of vanadium
We report
that has been
C2v
with one V-O
A and 2.452(6)
A.
Five
the sixth is unidentate. have been structurally
(IV) carboxylate
with a monomeric
coordination.
Experimental Synthesis The complex attempt to prepare
indium-vanadium
with 0.30 g (1.3 retool)
ofindium(III)
and 0.60 g (7.3 mmol)
of sodium
removed
from the drybox,
4-methylpyridine clusters.
In a drybox,
chloride, acetate.
and connected
solution
as a by-product
a Schlenk
0.28 g (1.8 mmol)
The Schlenk
tube was charged
of vanadium(III)
chloride,
tube was fitted with a septum,
to a double-manifold
2
of an
vacuum
line.
Underanincreasedflow of argon,25mL (260mmol) of methylpyridine
was
methylpyridine,
added
and while
rapid stream
of argon,
then stirred
to the Schlenk stirring,
the septum
at room
temperature
argon,
the reaction
tube via a syringe.
Upon
the color of the solution was replaced
which
distilled
4-
addition
turned
with a glass
for 9 days during
freshly
dark
stopper.
of the 4-
purple.
Under
The solution
time the solution
a
was
remained
dark
purple. Under purple
filtrate
freshly
distilled
was concentrated
was collected vacuum
mixture
hexane.
to one-half
Precipitation
on a glass frit, washed
Crystal
65%)
through
the original
celite.
volume
of the light purple
The resultant
and stirred
crude
with a 20 mL aliquot
for 12 h. Recrystallization
(1.2 mmol,
was filtered
product
with 30 mL of
occurred.
of fresh hexane,
from 4-methylpyridine/hexane
dark
(25/50
The solid
and dried under a v/v) yielded
0.4 g
of the title compound.
Growth In a drybox,
Schlenk
a Schlenk
tube was fitted
with a septum,
double-manifold
vacuum
methylpyridine
was added
18 h at room dark purple approximately septum
line.
temperature. solution.
vacuum
line.
suitable
for x-ray disc,
983(m),
814(s),
Under
During
The solution
After
analysis,
cm'l):
from the drybox,
an increased
flow of argon,
was filtered
651(w).
through
were observed 1620(s),
and the Schlenk temperature,
concentrated positive
tube disconnected
blocky-type
at the hexane/4-methylpyridine 1502(m),
1458(s),
to a
25 mL of 4-
dissolved
Under
The
and connected
The solution
celite,
with 30 mL of hexane.
days at room
3067(w),
tube via a syringe.
this time the solid completely
with a glass stopper several
with 0.4 g of the title compound.
removed
to the Schlenk
12 mL, and layered
was replaced
IR (KBr
tube was charged
1210(w),
purple
was stirred producing
for a
to pressure,
the
from the crystals, interface.
1060(sh),
1013(m),
X-ray
Crystallography A blue chunk
of C 14H17CIN203
0.30 mm was mounted orientation
matrix
in a glass capillary
for data collection
setting
angles
omega
scans of several
of 25 reflections intense
systematic
the space
absences;
The data were
from
all of which
the data.
The linear
absorption
based
coefficients
The structure remaining
atoms
were located refined.
were located
method
was
Scattering effects
factors
using
were included
1725 reflections in the refinements.
of Walker
the structure
factor
and
parameter
agreement
factors
as defined,
quality,
at half-height
was
were no
the co -20 scan technique. reflections
were
were applied
for Mo K a radiation.
An empirical
and Stuart l° was applied.
program
Fourier
calculations
value
of 0.889.
where
z1 The
Hydrogen
but their positions
least-squares
Relative
SHELX-86.
syntheses.
to
atoms
were not
the function
as per the Killean
and Lawrence
1.0.12
taken from Cromer
The final cycle
(largest
using the
corrections
solution
difference
in full-matrix
intensities
converged
on crystal
There
A total of 2117
is 7.7/cm
in Fc; 14 the values
having
quality.
and polarization
in succeeding
was refined
were
refinement,
from 0.784 to 1.000 with an average
to the structure
of 0.020
the width
and an
to be P i (#2).
_:w(IFol - IFcl)2 and the weight w is defined
with terms
Cell constants
of 293 + 1 K using
Lorentz
on the method
ranged
and added
good crystal
was determined
coefficient
was solved
The structure
minimized
unique.
of 0.35 x 0.31 x
from least-squares
1 to 16o/min (in omega).
were
orientation.
were measured;
at a temperature
absorption
correction
transmission
group
dimensions
19 < 0 < 22 °. As a check
of 3.0 o indicating
collected
The scan rate varied
were obtained
reflections
angle
approximate
in a random
in the range
0.490 with a take-off
collected,
V having
greater
and Waber. 13 Anomalous
for f and f' were those than 3.0 times their
of refinement
included
of Cromer.
standard
190 variable
in equations
4
(1) and (2).
15 Only the
deviation parameters
shift was 0.03 times the esd) with unweighted respectively
dispersion
were used and
and weighted
R = El
Fo - Fe I/E
Rw = _/(Zw
Results
and
13= 91.41(1),
numbering
scheme
are given
in Tables
shows
!,7,16,17
electron
partial Bond
angles
length
Recent
is completely
having
triple
angles
ranging
are shown
oxygen
structure
1. Bond
defined
by O(1), V(1),
of the vanadyl
moiety
ab initio calculations localized
bond
lengths
cell
A, o_ = and
and bond angles
in the metal
O(31),
is 1.582(2)/_.,
dx2.y2
orbital
ligands
103 ° to 110 ° are most common around
is 98.2 o, O(1)-V(1)-N(11)
1010 are typical
ligand.
which
confirm
Ignoring
the
there
is very
atom,
O(32),
C(31),
and C(32).
is quite
that the unpaired
and suggest
pyridines
that range
are smaller
in 5-coordinate in 6-coordination, in our complex.
is 93.5 o, and O(1)-V(1)-N(21)
by 4-methylpyridine
with the conclusions of substituted
Cl(1),
due to both the
strong
V-O bonding
character.18
angle of 107.8 ° falls within
The adoption
geometry,
at the vanadium
on V O(acac)2
from the VO axis to equatorial
from
from octahedral
on local symmetry
V(1)-CI(1)
number
c = 14.841(2)
and the small bite of the acetate
16'17 and angles
consistent
b = 8.023(I),
in Figure
distortion
complexes,
O(31)
in Table I. The triclinic
V = 811.4 _3. The molecular
significant
of symmetry
The VO bond typical.
(2)
II and III.
rings and focusing
a plane
are given
are: a = 7.822(2),
7 = 117.13(1),
from the vanadyl
methylpyridine nearly
volume
of the compound
The molecule bonding
(Fo - Fc) 2 / ]_w Fo 2) = 0.050
date for the title compound
and calculated
99.73(1),
(1)
Discussion
Crystallographic parameters
Fo = 0.038
of Caira,
ligands
of positions
et. al., who inferred
were coordinating
than usual.
While
oxovanadium
(IV)
bond
19 only the O(1)By contrast,
O(1)-V(I)-
is 94.0 o. cis to the vanadyl from
in cis positions
infrared
oxygen
evidence
in VO(acac)2
is
that a
adducts.
2°
Oneacetateoxygen-- 0(32) -- is trans 0(31)
--
is cis.
bonds
to identical
2.044(3)A
Vanadium
bonds
cis ligands
and V(1)-O(32)
angle
to trans ligands
bond
in the V(1)-O(31)-C(31) the idealized
spans
positions
while
about
the case here,
the other
0.2A longer
where
than
V(1)-O(31)
is
is 2.237(3)A. angle of 60.3(1) o is substantially
of 90 ° due to the strain
below
oxygen,
are typically
(19), and that is indeed
The O(31)-V(1)-O(32) octahedral
to the vanadyl
of the four-membered
and V(1)-O(32)-C(31)
the ideal
This strain
also shows
of 95.2(2) ° and 86.7(2) °, well
bidentate
cis and trans to the oxo group.
98.4(3) o, and 83.4(3) ° , respectively.
ring.
bond angles
sp 2 angle of 120 o. Vivanco's
below
acetate
The comparable
of oxovanadium bond
angles
(V) also
are 58.4(1) o,
9
Conclusions The other oxovanadium are known
or thought
combining
3 mmol
Based
to be polynuclear,
VC13e3THF
on low magnetic
oxovanadium
of the acid. 8 Patel,
moments,
for oxovanadium
VO(SO4)
with 20 mmol
Cotton,
susceptibilities,
and anhydride
that have been structurally
with 9 mmol
(IV) carboxylates
with the acid excess
(IV) carboxylates
in toluene
sodium
Casey
prepared
benzoate
or DMF,
by heating
or by solvolysis
prepared
also because
by combining
Then carboxylates solvent vanadyl
why did our compound form polynuclear
4-methylpyridine. oxygen
can only happen
halobenzoate
Oligomerization
or carboxylate
oxygen
if the second
vanadium
6
structure
for
(IV) oxide with a large of low magnetic
l0 mmol
of
7
m methanol/water.
form as a monomer
complexes?
by
chloride.
vanadium of VOCl3
•
of sodium
trimer
an oligormeric
hydrated
the same structure,
(IV) halobenzoates
a vanadium in methylene
et. al. proposed
either
et. al. suggested
et, al, obtained
characterized
Perhaps
when because
probably
on the vanadium
requires
other oxovanadium it formed
has an open coordination
6
in the coordinating
nucleophilic
atom of another
(IV)
attack molecule,
position.
of a but that
The negatively
chargedoxygen,
chloride,
4-methylpyridine solvent,
must
an equilibrium
unsaturated.
Thus,
and acetate come
nucleophilic
addition
position,
thus inhibiting
bridging
ligand,
virtually
but this dimer
coordinating
subsequent
et. al.
coordinatively
They prepared
was converted
strategy
to the monomer
for the preparation Oxovanadium
leaving
reactivity.
however,
susceptible
to further
can tie up a sixth coordinating
In the absence
toward
of vanadyl
(IV) commonly
the vanadium
of a large
excess
of the
monomer.
Material data (excluding
deposited
structure
with the Cambridge
factors)
for the structures
Crystallographic
Data Center
publication
no. CCDC
xxxxxx.
Copies
of the data can be obtained,
application
to CCDC,
12 Union
Road,
Cambridge
or e-mail:
is the
9
solvent,
is pushed
no molecules
a
blocked.
of Vivanco
synthetic
the equilibrium
Crystallographic have been
that leaves
with 5-coordination,
The use of a strongly
to be very labile, so that means
But if 4-methylpyridine
that tend to form oligomers.
electroneutrality
Supplementary
the attack.
is effectively
of pyridine.
a generalized
with ligands
achieves attack.
in toluene,
upon
This suggests
attack
are unlikely
with the observations
(mesityl)3V-O-V(mesityl)3
monomers
off to permit
will be established
This is consistent
(mes)2VO(py)2
ligands
CB2
in this paper as supplementary
free of charge,
on
1EZ, UK, (fax: +44 1223 336033
[email protected]).
Acknowledgment We gratefully support Glenn
acknowledge
through
grants
NCC3-162
Research
Center
Director's
the National (SAD),
Aeronautics
NCC3-720
Discretionary
Fund
7
and Space
(RMM (AFH).
Administration
and PEF)
for its
and the NASA
References 1.
J. Selbin,
2.
E. de Boer,
3.
Rev. 65, 153, (1965).
Y. van Kooyk,
Acta,
869, 48, (1986).
R.L.
Robson,
Postgate,
4.
Chem.
R. R. Eady,
Nature
D. Rehder,
M. G. M. Tromp, H. Plat, and R. Wever,
T. H. Richardson,
(London)
W. Priebsch,
322,388,
R. W. Miller,
Biochim.
M. Hawkins,
Biophys.
and J. R.
(1986).
and M. von Oeynhausen,
Angew.
Chem.
Intl. Ed. Engl. 28,
1221, (1989).
5.
R.C.
Mehrotra
and R. Bohra,
6.
F.A.
Cotton,
7.
K.S.
Patel and O. A. Odunola,
8.
A.T.
Casey,
G. E. Lewis,
Metal
Carboxylates.
and G. N. Mott,
B. S. Morris,
Synth.
Inorg.
React.
E. Sinn, andJ.
(Academic
Chem.
Inorg.
Press,
21, 3127,
Met.-Org.
K. Thackeray,
New
York,
1983).
(1982).
Chem.
Aust. J. Chem,
20, 681, (1990).
25, 1195,
(1972).
9.
M. Vivanco,
J. Ruiz,
C. Floriani,
A. Chiesi-Villa,
and C. Rizzoli,
Organometallics
12,
1802, (1993).
10. N. Walker
and D. Stuart,
11. G. M. Sheldrick, fur Anorganische
12. R. C. G. Killean
Acta
Crystallogr.
A39,
158, (1983).
SHELX-86,
Program
for the Crystal
Chemie
der Universitat
Gottingen,
and J. L. Lawrence,
Acta
Crystallogr.
Structure F.R.G.,
B25,
Determination 1986).
1750, (1969).
(Institut
13.D. T. CromerandJ. T. Waber,International (The Kynoch
14. J. A. Ibers
(The Kynoch
16. J. C. Dutton,
Press,
G. Lanza,
Crystallogr.
England,
Inorg.
Crystallography,
Vo/./V.
2.2B.
17, 781, (1964).
Tables for X-Ray
Crystallography,
Vol. IV.
1974), Table 2.3.1.
m_d K. S. Murray,
A. Gulino,
S. Dutta,
1974), Table
International
Birmingham,
G. D. Fallon,
19. J. Chakravarty,
lnorg.
Chem.
27, 34, (1988).
Chem. 9, 130, (1970).
andI.
S. K. Chandra,
Fragala,
Inorg.
Chem.
35, 3885,
P. Basu, and A. Chakravorty,
(1996).
Inorg.
Chem.
(1993).
20. M. R. Caira, (1972).
England,
Acta
and J. T. Waber,
and D. L. Weaver,
18. S. Di Bella,
32, 4249,
Birmingham,
and W. C. Hamilton,
15. D. T. Cromer
17. D. Bruins
Press,
Tables for X-Ray
J. M. Haigh,
and L. R. Nassimbeni,
J. lnorg.
NucI.
Chem.
34, 3171,
Table
I.
Crystallographic
Molecular Formula
for
formula
347.70 293
K
Wavelength,
VOCl(O2CMe)(4-pic)2
VCIO3N2C14H17
weight
Temperature,
Space
Data
0.71073
A
group
Pi(#2)
a, A
7.822(2)
b, A
8.023(1)
c, A
14.841(2)
or, deg
99.73(1)
[3, deg
91.41(1)
"t', deg
117.13(1)
V, A 3
811.4(5)
Z
2
dealt, I.t, cm
g/cm 3
1.423
-1
7.66
Crystal
size, mm
0.35 x 0.31 x 0.30
20range,
deg
4.00 - 45.00
Scan method
co - 20
Data
2117
/ parameters
No. obsd.,
1725
I > 3(_(I)
R
0.038
Rw
0.050
GOF
1.603
Max. residual
peak, eA "3
10
0.28
/ 190
Table
II.
Bond
Atom
Distances
in Angstroms
1
Atom
2
for
VOCl(O2CMe)(4-pic)2
Distance
V(1)
CI(1)
2.320(1)
V(1)
O(1)
1.582(2)
V(1)
O(31)
2.044(3)
V(1)
0(32)
2.2"37(3)
V(1)
N(ll)
2.154(3)
V(1)
N(21)
2.124(3)
O(31)
C(31)
1.267(5)
0(32)
C(31)
1.2-51(5)
N(11)
C(12)
1.322(5)
N(11)
C(16)
1.328(5)
N(21)
C(22)
1.338(5)
N(21)
C(26)
1.338(4)
C(31)
C(32)
1.489(6)
c(12)
c(13)
1.371(6)
c(13)
C(14)
1.366(7)
C(14)
C(15)
1.364(6)
C(14)
c(17)
1.501(6)
C(15)
C(16)
1.3'70(6)
C(22)
C(23)
1.369(5)
C(23)
C(24)
1.379(5)
C(24)
C(25)
1.378(5)
C(24)
C(27)
1.,_93(5)
C(25)
C(26)
1.368(5)
ll
Table
III.
Atom
c1(1) Cl(1) c1(1) C1(1) CI(1) O(1) O(1) O(1) O(1) O(31) O(31)
o(31) 0(32) 0(32) N(ll)
v(1) V(1) V(1)
v(1) C(12) V(1)
v(1) C(22) O(31) 0(31) 0(32) N(11) C(12) C(13) C(13) C(15) C(14) N(ll) N(21) C(22) C(23) C(23) C(25) C(24) N(21)
Bond
1
Angles
Atom
in Degrees
2
v(1) v(1) v(1) v(1) v(1) v(1) v(1) v(1) v(1) v(1) v(1) V(1) V(1) V(1) V(1) 0(31) 0(32) N(ll) N(ll) N(ll) N(21) N(21) N(21) C(31) C(31) 0(31) C(12) C(13) C(14) C(14) C(14) C(15) C(16) C(22) C(23) C(24) C(24) C(24) c(25) C(26)
Atom
for
3
VOCl(O2CMe)(4-pic)2
Angle
O(1)
107.8(1)
O(31)
154.04(9)
0(32) N(ll)
93.78(8) 91.29(9)
N(21)
88.82(9)
O(31)
98.2(1)
0(32) N(ll)
158.4(1) 93.5(1)
N(21)
94.0(1)
0(32)
60.3(1) 87.6(1)
N(ll) N(21) N(ll)
88.9(1) 84.9(1)
N(21)
87.3(1)
N(21)
172.1(1)
C(31) C(31)
95.2(2)
C(12)
125.3(3)
C(16) C(16)
118.6(2) 115.8(3)
C(22)
121.5(2)
C(26)
121.9(2)
C(26) 0(32)
116.7(3) 117.8(4)
C(32)
120.2(4)
C(32)
122.0(4)
C(13)
123.3(4)
C(14)
120.5(4)
C(15)
116.4(4)
C(17)
122.2(5)
C(17) C(16)
121.3(5) 119.9(4)
C(15)
123.9(4)
C(23)
123.0(3) 120.6(3)
C(24) C(25)
86.7(2)
116.1(3)
C(27)
122.9(4)
C(27)
121.0(4)
C(26)
120.7(3)
C(25)
123.0(4)
12
0
0
o_,.q
0
¢.) c.)
,.o
E
c_
¢.)
0
