Department of Chemistry, Tulane University, New Orleans, LA 70118. I Department ..... 7F. A. Cotton and G. Wilkinson,. Advanced. Inorganic. Chemistry,. 5th ed.
Synthesis
and Structural
Characterization
of
Tris(dimethyldithiocarbamate)indium(III), In[S2CN(CH3)2]3
Eric
B. Clark *'t, Marc Aloysius
Keywords:
E. Fanwick
of Chemistry,
Center, MS 302-1, Cleveland,
Cleveland
State University,
Cleveland,
of Chemistry,
Tulane University,
New Orleans,
I Department
of Chemistry,
Purdue University,
West Lafayette,
indium, dithiocarbamate,
to whom coorespondance
t,
OH 44135
* Department
tetraalkylkthiuram,
photovoltaics,
Authors
Phillip
F. Hepp *'_, and Stan A. Duraj *'§
"NASA Lewis Research *Department
L. Breen*'*,
should be addressed.
MOCVD
OH 44115 LA
70118
IN 4790
tetraalkyldithiocarbamate,
Synthesis
and Structural
Characterization
of
Tris(dimethyldithiocarbamate)indium(III), In[S2CN(CH3)2]3
Eric
B. Clark *'t, Marc Aloysius
L. Breen*'*,
Phillip
F. Hepp *'_, and Stan
E. Fanwick
_,
A. Duraj t'_
'NASA Lewis Research Center, MS 302-1, Cleveland, OH 44135 tDepartment of Chemistry, Cleveland State University, Cleveland, OH 44115 * Department of Chemistry, Tulane University, New Orleans, LA 70118 I Department of Chemistry, Purdue University, West Lafayette, IN 47907
Abstract
The synthesis mepy
(4-mepy
and structure
of the indium
= 4-methylpyridine),
dithiocarbamate,
is described.
Indium
metal
tetramethylthiuramdisulfide
in 4-methylpyridine
at 25°C to form
indium(III)
in yields
exceeding
60%.
geometry.
The compound
molecule
dithiocarbamate
with a distorted-octahedral
2) space
group
with a = 9.282(1)/_,
70.21(1)
°, y= 85.84(1)
b = 10.081(1)
°, Z = 2, V (tl, 3) = 1057.3(3),
t Authors to whom coorespondance
should be addressed.
In[S2CN(CH3)213*1/2 was oxidized
4-
by
a new, homoleptic
In[S2CN(CH3)2]
3 exists
crystallizes
as a discrete
in the P 1 (No.
_, c = 12.502
_, ct= 73.91
R = 0.046,
and Rw = 0.061.
(1) °, _ =
Introduction
Numerous
applications
semiconductors. many
Photoelectrical
electronic
devices
such
demonstrate
the
or electrical
properties
as solar
cells,
transistors
[e. g. CdE (E = S, Se, or Te),
are grown
by metalorganic
using
highly-toxic
routes
also
and pyrophoric
for growing
cost and allow
thin films
deposition
be beneficial
precursor desired
if two
semiconductors
sulfides
into thin-film materials
or more
variety
of the
compounds
9'1°. These
semiconductors
upon
is great
at relatively
desired
diodes, these
(e.g.
new
to reduce
plastics).
contained
will readily
films
in discovering
flexible
are
and
temperatures
low temperatures
elements
which
at high
interest
in
in the
decompose
It can same
to form
the
stoichiometry.
are under
compounds
light-emitting
MOCVD,
of substrates
are needed
with the proper
dithiocarbamates
There
materials
are important
active
contain
investigation
metal-sulfur
precursor
as MOCVD bonds
decomposition
which
precursors
to
are incorporated
and sublimation
of the new
., have been
studied 6 and
onto a substrate. Many
homoleptic,
several
synthetic
include
the reaction
chlorides sodium
of these
chalcogenide
2 (Q = S or Se)] _5. Often
deposition,
precursors.
metal
materials
detectors,
CulnQ
vapor
of
of these
infrared
GaS,
on a broader
1'2'5. Therefore,
Metal metal
chemical
significance
routes
metal
dithiocarbamates,
have been
of CS 2 with metal
with CS 2 in the presence dithiocarbamate
and more
direct
devised
for their preparation.
amide
of amines,
salts 7. Additionally,
M(S2CNR2)
complexes
(M(NR2).),
and the direct reactions
A few such examples the reaction
reaction
with metal
of metal powders
of metal
halides
offer
with
a simple
approach.
Metal
thiocarbamates
have
dithiocarbamate
in organic
solvents
been prepared
from metal
such as chloroform,
powders
dimethyl
and sodium
sulfoxide
(DMSO)
and
ethanol8. However,previousattemptsto reactthemetalsdirectlywith tetraalkylthiuram havebeenunsuccessful,with oneexception.Bis(dibutyldithiocarbamate)copper(II) was synthesizedthroughthe combinationof tetrabutylthiuramdisulfideandcopperpowderin chloroform,but this reactionproceededthrougha photochemicalpathway9. By utilizing thestronglybasic,coordinatingsolvent,4-methylpyridine,we havebeenableto prepare bothdivalent(M = Ni andCu) andtrivalent(M = Fe,Co, andIn) metalthiocarbamates _°at roomtemperatureby non-photochemical means.The previouslyunreported In(S2CN(CH3)2) 3is describedherein.
Experimental
General. atmospheres
Air and moisture-sensitive
employing
standard
Solids
were manipulated
train.
Solvents
Solutions powder
were
transferred
was obtained
through
stochiometric ambient
was filtered
Chemicals
further
the oxidation
and washed
equipped
and/or
inert
from Aldrich
vacuum
ketyl prior
MA), Chemical
line.
with an HE-493
syringes.
(Newburyport,
to use.
The indium
while
dri-
metal
the
Co. (Milwaukee,
WI).
purification.
of indium
The dialkyldithiocarbamate metal
of tetramethylthiuramdisulfide for several
under
and a double-manifold
benzophenone
steel cannula
of In[S2CN(CH3)z]3.
amounts
temperature
Strem
were handled
drybox
from sodium
was purchased
Both were used without
prepared
distilled
techniques
Atmospheres
via stainless
from
tetramethylthiuramdisulfide
Preparation
Schlenk
in a Vacuum
were freshly
materials
days,
under
powder
(0.50
was typically
g, 4.3 mmol)
in 35 mL of 4-methylpyridine
Argon _°. The dark brown
with 150 mL of hexane.
by
Yields
exceeded
at
or black precipitate
60% of crude
product.
\G.,
X-Ray Crystal Data Collection. A c_k
of InCI2HIsN3S6, havingdimensionsof
0"
0.50 x 0.38 x 0.34 mm, was mounted examination
and data collection
0.71073/_)
with a graphite Cell constants
least-squares range Data
crystal,
support
triclinic
incident
(See Table
21 < 0 < 23*, measured an empirical
measured; moderate
the width crystal
formula
determined
beam matrix
angles
controlled
at half-height There
(k =
omega
were obtained
scans
slit method
[Insert
I]
of centering.
volume
intense
angle
absences;
in the
for the
the calculated
of several
no systematic
from
of 25 reflections
The calculated
was 0.72 ° with a take-off were
source
axis diffract.meter
diagonal
For Z = 2 and F. W. = 514.53,
and polarization
corrections
coefficient
is 16.7 cm _ for M, K_ radiation.
the method
of Walker
from 0.811
to 1.000 with an average
Calculations Enraf-MolEN
revealed.
kappa
Preliminary
density
reflections
is were
of 3.0 ° indicating
the space
group
was
to be P "] (No. 2).
Lorentz
SHELX-86
K_, radiation
for data collection
I), using the setting
quality,
orientation.
monochromator.
of InS6N3.sC12H21.5.
on crystal
quality.
with a M.
by the computer
cell was V = 1057.3/_.
1.62 g/cm 3. As a check
in a random
CAD 4 computer-controlled
and an orientation
refinement
fiber
were performed
on an Enraf-Nonius
equipped
on a glass
were
applied
An empirical
and Stuart _x was applied. value
were performed
12. The crystal j3. Using
Table
the Patterson
The remaining
atoms
computer.
was solved
heavy-atom were
found
absorption transmission
The linear
absorption
correction
based
coefficients
Refinement
with the structure
method, in succeeding
the position difference
was done using solution
program
of the In atom Fourier
on
ranged
of 0.938.
on a VAX
structure
Relative
to the data.
was
syntheses.
"(,
Hydrogen
atoms
were added
to the structure
factor
calculations
but their positions
were not
refined.
Results
and
Discussion
This group has successfully dithiocarbamates
reacted
tetraalkylthiuram
with Fe, Co, Ni, Cu, and In metal [Insert
Synthesis
of the title compound
the introduction
of impurities,
since
powders
Scheme
is straightforward only metal
disulfides
to form homoleptic
(See Scheme
1).
1] and offers
powders
a high degree
of control over
and the tetraalkyldithiocarbamate
are used. The unit cell of the title compound dithiocarbamate
molecules
consists
and one half a formula
of an In 3÷ cation weight
ligated
by three
of 4-methylpyridine
(See Figure
1). [Insert In[S2CN(CH3)2]
3 has a distorted
for this compound
Figure
octahedral
geometry.
the ethyl C(31)
distances
analog
structure
of the methyl
N-C bonds components
their calculated Sulfur general
and angles
Table
bond
distances
and angles
II]
for In[S2CN(CH3)2]3
of this compound
bond lengths
comparable
Selected
appear in Table II. [Insert
Bond
1]
TM.
On average,
compound
of the ethyl are comparable
are very similar
the N(12)-C(11),
are slightly
compound, between
1.329/_,.
shorter
to those
N(22)-C(21) at 1.313/_
within
for
and N(32)-
than the
The rest of the values
both analogs
reported
statistical
for similar deviation
of
values. to metal bond
categories.
angles
The bidentate,
around ligand
the pseudo-octahedral to metal
bite angles
metal range
center
fit into three
from S(31)-In-S(32
=
-
68.91(6)
° to S(21)-In-S(22)
90 ° over the range angles
for sulfurs
over the range
= 69.67(6)*.
of S(11)-In-S(31) arranged
trans
of S( 12)-In-S(21
The cis, sulfur
= 91.63(6)*
bond
to S(11)-In-S(22)
to one another ) = 154.94(7)*
to metal
with respect
angles
deviate
= 105.88(7)*.
the metal
to S(22)-In-S(31)
deviate
from
Bond from
180*
= 161.87(7)*.
Conclusion
We have oxidation
described
of indium
powder
solvent.
Dithiocarbamates
material
for a number
octahedron
a simple
in detail
synthesis
to a metal
with tetramethylthiuramdisulfide are excellent
of applications.
and only the second
described
one-step
precursors
in a basic
to metal
The structure
dithiocarbamate
sulfides,
indium
coordinating
an important
of In[S2CN(CH3)2]
structurally-characterized
by
class
of
3, a distorted
dithiocarbamate,
was
herein.
Acknowledgments
A. F. H. (Director's NCC3-318),
S. A. D. (NCC3-162),
acknowledge Andrew prints
Discretionary
support
Barron
from NASA
of Rice University,
Fund),
D. G. H. (NASA
P. E. F. (NCC3-246) Lewis
Research
Agreement
and M. L. B. (NCC3-457)
Center
and Paul O'Brien
Cooperative
and Kent State.
of Imperial
College,
We thank London
for pre-
of their work.
References P. O'Brien,
J. R. Walsh,
167, 133 (1996).
I. M. Watson,
L. Hart,
and S. R. P. Silva,
J. of Cryst.
Profs.
Growth
/
2T. TrindadeandP. O'Brien, Chem. 3 T. L. Chu,
9, 523 (1997).
S. S. Chu, S. T. Ang and M. K. Mantravadi,
4 L. L. Kazmerski D. Meakin
of Mat.
and S. Wagner,
(Academic
5 A. N. Maclnnes,
in Current
Press, London,
M. B. Power,
1985),
A. F. Barron,
Topics
Solar
Cells
21, 73 (1987).
in Photovoltaics,
ed. by T. J. Coutts,
J.
p. 41. P. P. Jenkins
and A. F. Hepp,
Appl.
Phys.
Lett. 62, 711 (1993). 6 See the following
extensive
reviews:
D. Coucouvanis,
Prog.
Inor.
Chem.
11,233
(1970);
ibid. 26, 301, (1979). 7 F. A. Cotton Sons,
New
and G. Wilkinson,
York,
1988),
Advanced
Inorganic
Chemistry,
5th ed. (John
M. Sumi,
M. Tanaka
and T. Shono,
Polyhedron
5, 707, (1986).
9 T. Tetsumi,
M. Sumi,
M. Tanaka
and T. Shono,
Polyhedron
4, 1439, (1985).
MRS Symp.
D. G. Hehemann,
Proceedings,
i_ N. Walker
12 Mo l EN, An Interactive
Acta
Ceramics Crystallogr.,
Structure
Solution
E. B. Clark,
W. E. Eckles
H: Non-Oxides A39,
and P. E. Fanwick,
327, 29 (1994).
158 (1983).
Procedure,
Enraf-Nonius,
Delft,
The
(1990).
13 G. M. Sheldrick, Gt_ttingen,
S. A. Duraj,
Covalent
and D. Stuart,
Netherlands
and
p. 252.
8 T. Tetsumi,
10 A. F. Hepp,
Wiley
SHELX-86:
GiSttingen,
Germany,
14 K. Dymock,
G. J. Palenick,
Dalton
28 (1972).
Trans.
program
for crystal
structure
determination,
University
1986. J. Slezak,
C. L. Raston
and A. H. White,
J. Chem.
Soc.,
of
Table I. Molecular
Crystallographic
Data
formula
Formula weight Crystal size (mm) Space group (No.) a (A) b (A) c (A)
(°) o) $((% ,1 Z (g cm 3) _t (cm j) Transmission coefficient 20 Range (°) Scan method dealt
No. unique data No. observed data (1>3_(I)) R_ Rw b
GOF Largest
shift/e,
s. d. final cycle
for In[S2CN(CH3)2]
3.
InS6N3.sC12H21.5 522.03 0.50 x 0.38 x 0.34 P 1 (2) 9.282(1) 10.081(1) 12.502(2) 73.91(1) 70.21(1) 85.84(1) 1057.3(3) 2 1.64 16.52 1.000 - 0.811 4.00 - 45.00 o-20 2757 2373 0.046 0.061 2.191 0.09
Scheme
(1). S
S
II
II
M ° + _[R2NCS-
4 - mepy
> M[(S2CN(CH3)2]n
SCNR2] 25°C
Figure 1. ORTEP drawing of In[S2CN(CH3)2] ellipsoids enclose 50% of electron density.
3 with key
atoms
CS331!
$32(_
(_C11
.-rC$ _
labeled.
The thermal
Table
II.
Selected
bond
distances
(/_) and angles (o) for In[S2CN(CH3)2]3.
Bond
Distance
Atoms
Angle
In-S(11) In-S(12) In-S(21) In-S(22) In-S(31) In-S(32) N(12)-C(11) N(22)-C(21) S(11)-C(11) S(12)-C(11) S(21)-C(21) S(22)-C(21) S(31)-C(31) S(32)-C(31)
2.602(2) 2.583(2) 2.582(2) 2.590(2) 2.600(2) 2.608(2) 1.319(9) 1.308(9) 1.727(7) 1.720(7) 1.724(7) 1.723(7) 1.725(8) 1.713(8)
S(11)-In-S(12) S(11)-In-S(21) S(11)-In-S(22) S(11)-In-S(31) S(11)-In-S(32) In-S(11)-C(11) In-S(12)-C(11) S(11)-C(11)-N(12) S(11)-C(11)-S(12) C(I 1)-N(12)-C(121)
69.62(6) 96.15(6) 105.88(7) 91.83(6) 157.88(7) 85.6(2) 86.4(2) 120.7(6) 118.4(4) 121.8(7)
