Aluminum, gallium and indium thiobenzoates: Synthesis, characterization and crystal structures

Article abstract of DOI:10.1080/17415993.2015.1025073

Compounds R₂M[S(O)CPh] [where R = ^tBu, M = Al (1); R = ^tBu, M = Ga (2); R = Me, M = Ga (3)] have been synthesized in reactions of R₃M with thiobenzoic acid in a 1:1 molar ratio of reagents. The reaction of Me

Full text of DOI:10.1080/17415993.2015.1025073

This article was downloaded by: [Fudan University]
On: 11 May 2015, At: 06:47
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Journal of Sulfur Chemistry
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gsrp20
Aluminum, gallium and indium
thiobenzoates: synthesis,
characterization and crystal structures
Eliza Jaśkowskaa, Łukasz Dobrzyckib, Patryk Rzepińskib & Wanda
Ziemkowskaa
a Faculty of Chemistry, Warsaw University of Technology,
Noakowskiego 3, 00-664, Warsaw, Poland
b Department of Chemistry, University of Warsaw, Pasteura 1,
02-093, Warsaw, Poland
Published online: 09 Apr 2015.
Click for updates
To cite this article: Eliza Jaśkowska, Łukasz Dobrzycki, Patryk Rzepiński & Wanda Ziemkowska
(2015) Aluminum, gallium and indium thiobenzoates: synthesis, characterization and crystal
structures, Journal of Sulfur Chemistry, 36:3, 326-339, DOI: 10.1080/17415993.2015.1025073
To link to this article: http://dx.doi.org/10.1080/17415993.2015.1025073
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &

Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions

Journal of Sulfur Chemistry, 2015
Vol. 36, No. 3, 326–339, http://dx.doi.org/10.1080/17415993.2015.1025073
Aluminum, gallium and indium thiobenzoates: synthesis,
characterization and crystal structures
Eliza Jas´kowskaa, Łukasz Dobrzyckib, Patryk Rzepin´skib and Wanda Ziemkowskaa∗
aFaculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664, Warsaw, Poland;
bDepartment of Chemistry, University of Warsaw, Pasteura 1, 02-093, Warsaw, Poland
(Received 3 January 2015; accepted 27 February 2015)
t
t
Compounds R2M[S(O)CPh] [where R = Bu, M = Al (1); R = Bu, M = Ga (2); R = Me, M = Ga
(3)] have been synthesized in reactions of R3M with thiobenzoic acid in a 1:1 molar ratio of reagents. The
reaction of Me3Ga with three equivalents of thiobenzoic acid yielded the compound Ga[S(O)CPh]3 (4),
in which thiobenzoate moieties act as bidentate SO ligands. In the presence of Et3N, InCl3 reacted with
thiobenzoic acid with formation of an ionic compound {In[S(O)CPh]4}−(HNEt3)+ (5). The thiobenzoate
ligands are bonded with the metallic center via the sulfur atoms only. The compounds 4 and 5 have
been structurally and thermally studied. The thermal decomposition pathways of compounds 4 and 5 are
proposed.
Keywords: aluminum; gallium; indium; thiobenzoic acid; thermogravimetry
1. Introduction
Over the last two decades, significant attention has been focused on group 13 elements, par-
ticularly Ga and In, with sulfur ligands due to their relevance as metal precursors for metal
sulfides,[1–15] biologically active compounds [16–18] and catalysts for polymerization.[19,20]
Among these complexes, gallium and indium dithiocarbamates and dithiocarboxylates have been
reported as source precursors for metal sulfide thin films and nano particles.[1,7–9,12–14] In con-
trast to the numerous literature data consisting of characterization and applications of gallium
and indium dithiocarbamates and dithiocarboxylates, the number of reports on group 13 thiocar-
boxylates is sparse. Dialkyl aluminum-, gallium and indium thioacetates published in 1971 by
Weidlein [21] are the first thiocarboxylates. They were obtained by the reaction of the trialkyls
*Corresponding author. Email: ziemk@ch.pw.edu.pl
© 2015 Taylor & Francis

Journal of Sulfur Chemistry 327
with equivalent amounts of thiocarboxylic acid. On the basis of spectroscopic data the struc-
ture of dimethyl aluminum thioacetate was proposed as a dimer with the central eight-membered
Al2O2C2S2 ring skeleton, whereas the corresponding Ga and In derivatives were monomeric
with four-membered MSCO rings.
According to our knowledge, there are several structurally characterized group 13 thiocar-
boxylates. The first example of a structurally characterized gallium thiocarboxylate compound
is methylgallium tioacetate Ga(SCOMe)2Me(dmpy) (where dmpy = 3,5-dimethylpyridine)
obtained in the reaction of Me3Ga with thioacetic acid in the presence of dmpy.[15] In the solid
state, the Ga center is tetrahedrally coordinated by two S atoms, one C atom from the methyl
group and one N atom from neutral dmpy. The X-ray structural determination of diethylindium
thioacetate showed the polymeric complex [Et2In(SCOCH3)]n, in which the thioacetate ligand
chelates through both S and O atoms and the O atom is also bridging two In centers, resulting in
five-coordinate metal centers.[22] The second structurally characterized indium compound is the
ionic complex [Hdmpy]+[In(SCOCH3)4]−, synthesized by the reaction of Et3In with an excess
of thioacetic acid followed by addition of dmpy.[2] The molecular structure of the compound
shows that the In center is tetrahedrally coordinated by four monodentate S-bonded thioacetic
ligands. Similarly, reactions of InCl3 with thiobenzoic acid in the presence of Et3N proceeded
with formation of (Et3NH)[In(SC(O)Ph)4]·H2O [23] and (Et3NH)[In(SC(O)Ph)4].[24]
Following our interest on group 13 carboxylates,[25,26] benzoxaborolates [27] and
amidates,[28,29] herein, we report the synthesis and structures of aluminum, gallium and indium
t
thiobenzoates. We show that reactions of R3M (R = Bu, Me; M = Al, Ga) with thiobenzoic acid
in a 1:1 molar ratio proceed with formation of monomeric R2M[S(O)CPh] complexes, whereas
in the reaction of Me3Ga with thiobenzoic acid in a 1:3 molar ratio the product Ga[S(O)CPh]3
was formed. We reinvestigated the compound (Et3NH)[In(SC(O)Ph)4], reported by Nöth and
Gupta in 1996,[24] to characterize it structurally and thermally and deposit crystal data in the
Cambridge Crystallographic Data Centre.
2. Results and discussion
The treatment of thiobenzoic acid with one molar equivalent of R3M produces the compounds
t
t
R2M[S(O)CPh] (where R = Bu, M = Al (1); R = Bu, M = Ga (2); R = Me, M = Ga (3)) as
shown in Scheme 1. The pure compounds, obtained as yellow liquids after distillation from the
post-reaction mixtures, were examined by NMR spectroscopy and molecular weight measure-
ments. In the 1H NMR spectra, integration ratios of signals of aromatic protons and protons of
alkyl groups bonded to metal atoms, indicate one aromatic ring per two R groups. According
to molecular weight measurements, thiobenzoates 1–3 are monomeric, which is in contrast to
dimeric dialkylaluminum and -gallium carboxylates.[30–32] Based on NMR spectra and molec-
ular weight measurements, compounds 1–3 consist of a metal atom bonded to two alkyl groups
and thiobenzoate moiety acting as a bidentate OS ligand.
t
We found that in the presence of an excess of thiobenzoic acid Bu3M (M = Al, Ga) reacts
only with one equivalent of the acid to form 1 and 2 complexes, whereas the reaction of Me3Ga
with three equivalents of thiobenzoic acid leads to a formation of the crystalline compound
Ga[S(O)CPh]3 (4) (Scheme 1). The molecular and crystal structure of the compound was deter-
mined on the basis of X-ray diffraction studies and is shown in Figures 1 and 2, respectively.
The crystal data as well as the details of the data collection and refinement are listed in Table 1.
A molecule of 4 consists of a central hexacoordinate gallium atom bonded to three thioben-
zoate moieties acting as bifunctional SO ligands and differing in bond lengths and angles from
each other. The coordination sphere geometry of the gallium atom is a distorted tetragonal

328 E. Jas´kowska et al.
R
R
M
O
LH
S
- RH
M = Al, R = tBu (1)
M = Ga, R = tBu (2)
M = Ga, R = Me (3)
R3M
O
O
S
3 LH
Ga
O
S
- 3 RH (R = Me)
S
O
4
SH
LH =
Scheme 1. Reactions of thiobenzoic acid with R3M (R = Me, tBu; M = Al, Ga).
bipyramidal geometry. Values of the following angles are similar: S(1)–Ga(1)–(O2) 157.45 (4),
O(1)–Ga(1)–S(3) 156.39(4) and O(3)–Ga(1)–S(2) 160.45(4). It indicates that not only can the
O(3) and S(2) atoms occupy the axial positions of the bipyramid, but also S(1) and O(2) as
well as O(1) and S(3) atoms can be regarded as atoms in the axial positions of the bipyra-
mid. In comparison with Ga(SCOMe)2Me(dmpy) the only structurally characterized gallium
thiocarboxylate,[15] the Ga–S bonds in 4 [2.371(1)–2.380(1) Å] are about 0.1 Å longer than in
those compounds. The sums of the angles about the C(1), C(8) and C(15) atoms ꢀ(C) 360.0°
show a sp2 hybridization of these atoms. Four-membered GaSCO rings are twisted in rela-
tion to aromatic rings, which is manifested by torsional angles C(3)–C(2)–C(1)–O(1) − 7.6(3),
C(7)–C(2)–C(1)–S(1)−8.1(3), S(2)–C(8)–C(9)–C(14) 6.4(3), O(2)–C(8)–C(9)–C(10) 5.9(3),
C(23)–C(16)–C(15)–O(3) 175.5(2), C(17)–C(16)–C(15)–S(3)− 179.3(2).
The ionic compound {In[S(O)CPh]4}−[HN(C2H5)3]+ (5) was synthesized in the reaction of
1
InCl3 with thiobenzoic acid in the presence of Et3N (Scheme 2). The H NMR spectrum of 5
reveals three multiplets of aromatic protons at 8.08, 7.46 and 7.34 ppm, quartet and triplet at
3.24 and 1.21 of ethyl group protons. On the basis of the integration ratio of the aromatic protons
and the ethyl group protons, we found that in the molecules there are four thiobenzoate moieties
per one molecule of NEt3.
The molecular structure of 5 depicted in Figure 3 is similar to that reported in [24]. The crystal
data as well as the details of the data collection and refinement are listed in Table 1. S–C–O
angles in monodentate thiobenzoate ligands in 5 [from 121.1(1) to 122.8(1)°] are significantly
bigger than those in bidentate ligands in 4 [from 116.5(1)° to 116.9(1)°]. Very probably, it is

Journal of Sulfur Chemistry 329
C5
C6
C7
C4
C3
C2
C1
O1
S1
S2
Ga1
O3
C17
C15
C14
C18
C20
C9
C8
O2
C13
C12
C19
C16
S3
C10
C23
C11
Figure 1. Molecular structure of C21H15GaO3S3·H2O (4·H2O) with atomic displacement parameters set at the 50%
level. Hydrogen atoms and water molecules have been omitted for clarity. For selected interatomic distances, angles and
torsional angles see Supporting information (Figure 1S).
Figure 2. Molecular packing of 4 drawn along a axis. Circles represent disordered molecules of water. H atoms have
been omitted for clarity.

330 E. Jas´kowska et al.
Table 1. Crystal data and data collection parameters for 4·H2O and 5.
4·H2O
5
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
Space group
a(Å)
b(Å)
c(Å)
α(°)
C21H15GaO3S3·H2O
[C28H20InO4S4]−·[HN(C2H5)3]+
497.23
765.70
100(2)
100(2)
0.71073
Monoclinic
C2/c
23.7175(4)
11.5723(1)
19.2640(3)
90
0.71073
Monoclinic
P1 21/n1
11.6532(6)
19.936(1)
14.5531(7)
90
β(°)
117.399(2)
90
4694.2(1)
8
92.848(2)
90
3376.8(3)
4
γ (°)
V(Å3)
Z
Dcalc(g cm–3
)
1.407
1.506
Absorption coefficient
(mm–1
F(000)
1.462
0.986
)
2016
1568
Crystal size (mm)
ꢁ range for data
collection (°)
0.20 × 0.15 × 0.10
0.12 × 0.14 × 0.17
1.7398–28.6580
2.29–26.00
Index ranges
− 28 ≤ h ≤ 28, − 14 ≤ k ≤ 14,
− 23 ≤ l ≤ 23
− 14 ≤ h ≤ 14, − 24 ≤ k ≤ 24,
− 17 ≤ l ≤ 17
Reflections collected
Independent reflections
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2σ(I)]
R indices (all data)
43,971
54,584
4332 [Rint = 0.0238]
Full-matrix least-squares on F2
4332/0/282
6637 [Rint = 0.0305]
Full-matrix least-squares on F2
6637/0/404
1.062
1.067
R1 = 0.0254, wR2 = 0.0633
R1 = 0.0285, wR2 = 0.0656
0.813 and − 0.408
R1 = 0.0201, wR2 = 0.0454
R1 = 0.0251, wR2 = 0.0474
0.492 and − 0.231
Max/min of residual
electron density
-
O
O
S
O
O
+ 4 Et3N
SH
+
O
Et3NH
S
S
In
InCl3 + 4
- 3 Et3N.HCl
O
S
O
5
Scheme 2. Reaction of thiobenzoic acid with InCl3.
caused by a lack of a strain in the monodentate ligands. The lack of strain is also demonstrated
by torsion of planes consisting of O(2), C(8), S(2) and O(3), C(15), S(3) and O(4), C(22) S(4)
atoms in relation to the proper aromatic rings. In comparison with the torsion of GaSCO planes
in relation to the aromatic rings in 4 [from 0.7(2)° to 8.1(3)°], the proper torsion angles in 5 are
significantly bigger [from 9.8(1)° to 21.4(2)°]. The only exception is the O(1)–C(1)–C(2)–C(3)

Journal of Sulfur Chemistry 331
Figure 3. Molecular structure of [C28H20InO4S4]−·[HN(C2H5)3]+ (5) with atomic displacement parameters set at the
50% level. Hydrogen atoms (besides the hydrogen atom bonded to the nitrogen atom) have been omitted for clarity. For
selected interatomic distances, angles and torsional angles see Supporting information (Figure 2S).
torsion angle [5.8(2)°], which is comparable with those of compound 4. Very probably, presence
of the O(1)H(1N)–N(1A) hydrogen bond introduced more steric strain.
The views along a and c axes demonstrate a laminar crystal structure of 5 (for the view along
c axis see Figure 4(a)); however the intramolecular atom distances that are roughly estimated
as 10 Å (Figure 4(b)) indicate no bonds between layers. The view along b axis shows channels,
in which intramolecular atom distances are approximately from 7 to 10 Å (Figures 5(a) 5(b)).
Recently, group 13 carboxylates have been attracting attention owing to their usefulness as metal
organic frameworks (MOFs). Although pore sizes of 5 and known MOFs like MIL-53 (channel
dimensions of 8.5 × 8.5 Å2) [33] and WUT-1 (cavities of 6.2 and 10.4 Å diameters) [34] are
similar, it is difficult to consider compound 5 as a potential MOF.
The thermogravimetric (TG) curve of complex 5 in argon atmosphere was considered to
decompose in two steps (Figure 6) (Scheme 3). The first step of decomposition occurred between
180°C and 250°C, where 63.80% of the initial mass was lost. This step was attributed to the loss
of Et3N, three molecules of C6H5CO and one C6H6 (theoretical 64.61%). The last step of decom-
position indicated a loss of 7.78% of the initial mass. This corresponded to the expulsion of
C(O)S (theoretical 7.83%). The residue obtained afterwards (28.42%) gave a non-stoichiometric
composition InS3 (theoretical 27.54%). The thermogravimetric curve of complex 4 indicated
decomposition as a multistep process (Figure 7) (Scheme 4). The first two steps occurred between
room temperature and 200°C and corresponded to a loss of solvents and water. In the next steps,
between 200°C and 500°C, three moieties of C6H5CO corresponding to the loss of 59.45% of the
initial mass were eliminated (theoretical 59.85%). Similar to the decomposition of 5, the residue
after decomposition of 4 manifests a non-stoichiometric composition GaS3.
In conclusion, this work presents the synthesis and characterization of group 13 thioben-
t
t
zoates. The compounds R2M[S(O)CPh] [where R = Bu, M = Al (1); R = Bu, M = Ga (2);

332 E. Jas´kowska et al.
(a)
(b)
Figure 4. Crystal structure of 5. (a) View along the c axis showing laminar structure of the compound. (b) Inter-
molecular atom distances (Å) between layers: C(6A)–C(12) 13.49, C(5)–C(12) 10.59, C(25)–C(20) 13.20, In–In 19.93,
C(4)–C(11) 10.71.
R = Me, M = Ga (3)] are liquids. Molecular weight measurements revealed the monomeric
structure of the compounds. The reaction of Me3Ga with three equivalents of thiobenzoic acid
led to a formation of the crystalline compound Ga[S(O)CPh]3 (4), whereas the ionic compound
{In[S(O)CPh]4}−[HN(C2H5)3]+ (5) was synthesized in the reaction of InCl3 with thiobenzoic

Journal of Sulfur Chemistry 333
(a)
(b)
Figure 5. Crystal structure of 5. (a) View along the b axis showing channel structure of the compound. (b) Inter-
molecular atom distances (Å) estimating a channel size: In(1)–In(1A) 14.55, In(1)–In(1B) 11.65, C(4A)–C(6) 10.32,
C(13)–C(19) 7.75.

334 E. Jas´kowska et al.
Figure 6. DSC (dashed line) and TGA (solid line) curves of compound 5.
Figure 7. DSC (dashed line) and TGA (solid line) curves of compound 4.
acid in the presence of Et3N. An analysis of the crystal structure showed that compound 5 can
be considered as a porous material, probably a potential MOF.
3. Experimental
3.1. Materials and instrumentation
All manipulations were carried out using standard Schlenk techniques under inert gas atmo-
sphere. Solvents (n-C6H14 and C6H6) were distilled over the blue benzophenone-K complex,

Journal of Sulfur Chemistry 335
-
O
O
300 -400 oC
180 -250 oC
S
O
+
O
InS3
InS4CO
Et3NH
In
S
S
- 3 C6H5C(O)
- Et3N
- C(O)S
O
S
O
- C6H6
5
Scheme 3. The decomposition pathways of compound 5.
O
O
S
rt - 200 oC
- H2O
200 - 500 oC
- 3 C6H5CO
.
H2O
Ga[C6H5C(O)S]3
GaS3
Ga
O
S
S
Scheme 4. The decomposition pathways of compound 4.
whereas CH2Cl2 was distilled over P2O5. tBu3Al·OEt2 and tBu3Ga were synthesized as described
1
in the literature.[35,36] H and 13C NMR spectra were obtained on a Mercury-400BB spec-
trometer. Chemical shifts were referenced to the residual proton signals of CDCl3 (7.26 ppm).
13C NMR spectra were acquired at 100.60 MHz (standard: chloroform 13CDCl3, 77.20 ppm).
t
Hydrolysable Bu groups for compound 1 were determined by hydrolysis of the compound
(0.2 g) under argon using HNO3 solution (10% concentrated, 5 cm3) and measurement of the
volume of C4H10. Subsequently, the sample was transformed into Al2O3 by mineralization and
the obtained white solid was dissolved in a diluted water solution of HNO3. The content of alu-
minum was determined by complexation of Al3+ cations with versenate anions using an excess of
the titrated solution of calcium disodium versenate. Then the excess of calcium disodium verse-
nate was titrated by FeCl3 according to the procedure described in [37,38]. Elemental analyses
of compounds 4 and 5 were performed using a Perkin-Elmer 2400 analyzer. Molecular weights
were measured by the cryoscopic method in benzene solutions.
t
t
3.2. Synthesis of R2M[S(O)CPh] [R = Bu, M = Al (1); R = Bu, M = Ga (2); R = Me,
M = Ga (3)]: general procedure
A solution of R3M (5 mmol) in CH2Cl2 (10 cm3) was injected into a solution of thiobenzoic acid
(0.690 g; 5 mmol) in CH2Cl2 (10 cm3) at −76°C. The reaction mixture was allowed to warm
slowly to room temperature. Then the post-reaction mixture was placed in a glass apparatus for
distillation. The pressure was slowly reduced to 10−2 Torr to distill off solvents. Subsequently,

336 E. Jas´kowska et al.
the flask was wrapped up with a heating belt and temperature was slowly increased up to the
moment of beginning of compound deposition on the condenser. The distillate was obtained as
solution of the yellow product (1–3) in solvent. The pure product was isolated in the second
distillation off a solvent from the flask at the temperature of 5°C within 2 h under vacuum (10−2
Torr).
3.3. tBu2Al[S(O)CPh] (1)
1
Yield 80%. H NMR (CDCl3) δ: 8.24 (2H, m, Haromat), 7.70 (1H, m, Haromat), 7.51 (2H, m,
Haromat), 1.05 [18H, s, (CH3)3CAl] ppm. 13C NMR (CDCl3) δ: 221.98 [C(O)S], 135.60, 129.68,
129.11, 128.61 (Caromat), 29.20 [(CH3)3CAl], 16 [(CH3)3CAl, broad] ppm. Elemental anal.
t
t
Found: Al, 9.40; hydrolyzable Bu groups, 41.39; Calcd for C15H23AlOS: Al, 9.71; Bu, 41.01
wt.%. Molecular weight Found: 268; Calcd for tBu2Al[S(O)CPh]: 278 g mol−1
.
3.4. tBu2Ga[S(O)CPh] (2)
Yield 85%. 1H NMR (CDCl3) δ: 8.16 (2H, m, Haromat), 7.63 (1H, m, Haromat), 7.46 (2H,
m, Haromat), 1.19 [18H, s, (CH3)3CGa] ppm. 13C NMR (CDCl3) δ: 219.58 [C(O)S], 136.76,
134.26, 128.46, 128.33 (Caromat), 29.36 [(CH3)3CGa], 27.26 [(CH3)3CGa] ppm. Molecular
weight Found: 315; Calcd for tBu2Ga[S(O)CPh]: 321 g mol−1. Anal. Found: C, 60.05, H, 7.95;
Calcd. for C15H23GaOS: C, 60.44; H, 7.72 (wt%).
3.5. Me2Ga[S(O)CPh] (3)
1
Yield 78%. H NMR (CDCl3) δ: 8.12 (2H, m, Haromat), 7.63 (1H, m, Haromat), 7.45 (2H, m,
Haromat), 0.21 (6H, s, CH3Ga) ppm. 13C NMR (CDCl3) δ: 218.81 [C(O)S], 134.41, 129.21,
128.56, 128.33 (Caromat), −2.60 (CH3Ga) ppm. Molecular weight Found: 248; Calcd for
Me2Ga[S(O)CPh]: 237 g mol−1. Anal. Found: C, 45.25, H, 4.92; Calcd. for C9H11GaOS: C,
45.61; H, 4.65 (wt%).
3.6. Synthesis of Ga[S(O)CPh]3 (4)
A solution of Me3Ga (0.575 g, 5 mmol) in CH2Cl2 (10 cm3) was injected into a solution of
thiobenzoic acid (2.208 g; 16 mmol) in CH2Cl2 (20 cm3) at − 76°C. The reaction mixture was
allowed to warm slowly to room temperature. The solvent was distilled off from the post-reaction
mixture under vacuum, yielding a light yellow solid of 4. n-Hexane (5 cm3) was added to the
solid to form a suspension. Methylene dichloride was slowly injected dropwise to dissolve
the solid. Pure compound 4·H2O was obtained after crystallization from the n-C6H14-CH2Cl2
solution containing 10 mmol of water at 7°C (Yield: 1.390 g, 2.8 mmol, 56%).
1H NMR (CDCl3) δ: 8.14 (2H, m, Haromat), 7.63 (1H, m, Haromat), 7.46 (2H, m, Haromat),
4.60 (broad, H2O) ppm. 13C NMR (CDCl3) δ: 212.33 [C(O)S], 135.19, 134.64, 129.40, 128.32
(Caromat) ppm. FTIR: ν = 3056.6, 2917.8, 2842.6, 1594.8, 1457.9, 1421.3, 1309.4, 1228.4,
1174.4, 970.0, 773.3, 707.7, 678.8, 649.9, 590.11 cm−1. Mp.: 86–90°C. Anal. Found: C, 50.56,
H, 3.62; Calcd. for C21H17GaO4S3: C, 50.68; H, 3.42 (wt%).
3.7. Synthesis of {In[S(O)CPh]4}−[HN(C2H5)3]+ (5)
Compound 5 was synthesized by a similar method as described in [24]. A solution of thioben-
zoic acid (1.173 g, 8.5 mmol) in 7 cm3 of benzene was injected into a suspension of InCl3

Journal of Sulfur Chemistry 337
(0.443 g, 2 mmol) in 15 cm3 of benzene consisting of Et3N (0.909 g, 9 mmol). The reaction mix-
ture became transparent; afterwards a light yellow solid precipitated. The solid was separated by
filtration, dried under vacuum, washed by 5 cm3 of CH3OH and dried again. A crystalline solid
of the pure compound 5 was obtained from an n-C6H14-CH2Cl2 solution (for preparation of
the solution see Section 3.6) at 10°C. (Yield: 1.072 g, 70%.) Mp.: 136–139°C (literature data
1
[24]: 118–119°C). H NMR (CDCl3) δ: 8.08 (8H, m, Haromat), 7.46 (4H, m, Haromat), 7.34 (8H,
m, Haromat), 3.24 (6H, q, CH3CH2N), 1.21 (9H, t, CH3CH2N). 13C NMR (CDCl3) δ: 203.40
C(O)S, 139.37, 132.33. 128.71, 127.88 (Caromat), 46.94 (CH3CH2N), 8.71 (CH3CH2N) ppm.
FTIR: ν = 3093.3, 3062.5, 1598.7, 1569.8, 1444.4, 1396.2, 1303.7, 1199.5, 1164.8, 1074.2,
1024.0, 919.9, 908.3, 835.0, 771.4, 686.5, 648.0 cm−1. Anal. Found: C, 52.90, H, 4.92; Calcd.
for C34H36InNO4S4: C, 53.28; H, 4.70 (wt%).
3.8. Crystallographic data
Single crystal data for 4 and 5 were collected at 100 (2) K using graphite monochromated
Mo/Kα radiation (λ = 0.7107 Å). Experiments were performed on an Xcalibur Opal CCD
k-axis (Oxford Diffraction) and a Bruker D8 VENTURE system equipped with a TRIUMPH
monochromator, respectively. The CrysAlisPro program [39] was used for data collection of 4,
cell refinement, data reduction and the empirical absorption corrections using spherical har-
monics, implemented in a multi-scan scaling algorithm. The structure was solved using direct
methods and refined with the full-matrix least-squares technique using the SHELXS97 and
SHELXL97 programs, respectively,[40] both implemented in the OLEX2 program.[41]
The residual map of electron density showed that apart from the main molecule 4, a disordered
solvent molecule should have also been considered in the crystal structure. Following the reaction
mechanism, selection of solvents and their potential impurities, for example a water molecule,
traces of dichloromethane, hexane or even hydrogen chloride could be taken into account as a
solvent molecule in the crystal structure. The best model was obtained with one water molecule
disordered in seven positions, refined isotropically with no hydrogen atoms attached. However
this choice should be regarded as arbitrary. The atomic scattering factors were taken from the
International Tables. [42]
The structure of 5 was solved and refined using the Bruker SHELXTL Software Package and
the SHELXL-2013 (Sheldrick, 2013) program.
Acknowledgements
The X-ray structures were determined in the Crystallographic Unit of the Physical Chemistry Laboratory at the Chemistry
Department of the University of Warsaw.
Funding
We thank the Warsaw University of Technology for its financial support.
Disclosure statement
No potential conflict of interest was reported by the authors.
Supplemental data
Supplemental data for this article can be accessed at 10.1080/17415993.2015.1025073

338 E. Jas´kowska et al.
References
[1] Ghoshal S, Jain VK, Dutta DP, Phadnis PP, Nethaji M. Gallium and indium dithiocarboxylates: Synthesis,
spectroscopic characterization and structure of [MeGa(S2Ctol)2]. J Organomet Chem. 2006;691:5838–5844.
[2] Shang G, Kunze K, Hampden-Smith MJ, Duesler EN. Low-temperature chemical vapor deposition of indium sul-
fide thin films using a novel single-source indium thiocarboxylate compound as precursor. Chem Vap Deposition.
1996;2:242–244.
[3] MacInnes AN, Cleave WM, Barron AR, Power MB, Hepp AF. Metal–Organic chemical vapour deposition of
polycrystalline tetragonal indium sulphide (InS) thin films. Adv Mater Opt Electron. 1992;1:229–233.
[4] Barron AR. Oxide, chalcogenide and related clusters of aluminum, gallium and indium. Comments Inorg Chem.
1993;14:123–153.
[5] Nomura R, Konishi K, Matsuda H. Single-source organometallic chemical vapour deposition process for sulphide
thin films: introduction of a new organometallic precursor BunIn(SPri)2 and preparation of In2S3 thin films. Thin
Solid Films. 1991;198:339–345.
[6] MacInnes AN, Power MB, Barron AR. Chemical vapor deposition of gallium sulfide: phase control by molecular
design. Chem Mater. 1993;5:1344–1351.
[7] Haggata SW, Malik MA, Melevalli M, O’Brien P. Synthesis and characterization of some mixed alkyl thiocarba-
mates of gallium and indium, precursors for III/VI materials: the x-ray single-crystal structures of dimethyl- and
diethylindium diethyldithiocarbamates. Chem Mater. 1995;7:716–724.
[8] O’Brien P, Otway DJ, Walsh JR. Novel precursors for the growth of α-In2S3: trisdialkyldithiocarbamates of indium.
Thin Solid Films. 1998;315:57–61.
[9] Sivagurunathan GS, Ramalingam K, Rizzoli C. Continuous shape measure of electronic effect free steric dis-
tortions in tris(dithiocarbamato)indium(III): synthesis, spectral, electrochemical, single crystal X-ray structural
investigations and BVS calculations on tris(dithiocarbamato)indium(III) complexes. Polyhedron. 2014;72:96–102.
[10] Ghoshal S, Kushwah NP, Pal MK, Jain VK, Nethaji M. Tris(dithiocarboxylato)indium(III): thermal studies and
crystal structure of [In(S2Ctol)3]. J Chem Sci. 2008;120:305–308.
[11] Lazell M, O’Brien P, Otway DJ, Park J-H. Oxide, chalcogenide and related clusters of aluminum, gallium and
indium. J Chem Soc, Dalton Trans. 2000;4479–4486.
[12] Keys A, Bott SG, Barron AR. Single source molecular precursors for the deposition of III/VI chalcogenide
semiconductors by MOCVD and related techniques. Chem Mater. 1999;11:3578–3587.
[13] Haggata SW, Malik MA, Motevalli M, O’Brien P, Knowles JC. Synthesis and characterization of some mixed
alkyl thiocarbamates of gallium and indium, precursors for III/VI materials: the X-ray single-crystal structures of
dimethyl- and diethylindium diethyldithiocarbamates. Chem Mater. 1995;7:716–724.
[14] Afzaal M, Malik MA, O’Brien P. Indium sulfide nanorods from single-source precursor. Chem Commun.
2004;334–335.
[15] Shang G, Hampden-Smith MJ, Duesler EN. Synthesis and characterization of gallium thiocarboxylates as
novel single-source precursors to gallium sulfide thin films by aerosol-assisted CVD. Chem Commun. 1996;
1733–1734.
[16] da Silva JG, Pergigão CCH, Speziali NL, Beraldo H. Chalcone-derived thiosemicarbazones and their zinc(II) and
gallium(III) complexes: spectral studies and antimicrobial activity. J Coord Chem. 2013;66:385–401.
[17] Lessa JA, Soares MA, dos Santos RG, Mendes IC, Salum LB, Daghestani HN, Andricopulo AD, Day BW, Vogt A,
Beraldo H. Gallium(III) complexes with 2-acetylpyridine-derived thiosemicarbazones: antimicrobial and cytotoxic
effects and investigation on the interactions with tubulin. Biometals. 2013;26:151–165.
[18] Ferreira IP, de Lima GM, Paniago EB, Takahashi JA, Pinheiro CB. Synthesis, characterization, and biocide activity
of new dithiocarbamate-based complexes of In(III), Ga(III), and Bi(III) – Part III. J Coord Chem. 2014;67:1097–
1109.
[19] Nakata N, Saito Y, Ishii A. Neutral methyl and cationic aluminum complexes supported by a trans-1,2-
cyclooctanediyl-bridged [OSSO]-type bis(phenolato) ligand: synthesis, structures, and use in catalysis for propy-
lene oxide polymerization. Organometallics. 2014;33:1840–1844.
[20] Postigo L, Maestre MD, Mosquera MEG, Cuenca T, Jimenez G. Aminoarenethiolate aluminum complexes:
synthesis, characterization, and use in L-Lactide polymerization. Organometallics. 2013;32:2618–2624.
[21] Weidlein J. Über dialkylaluminium-, -gallium- und -indium- thiocarboxylate. J Organomet Chem. 1971;32:181–
194.
[22] Hausen HD, Guder HJ. Dialkylindium-thioacetate R2InOSCCH3 (R = CH3,C2H5), darstellung, eigenschaften und
struktur. J Organomet Chem. 1973;57:243–253.
[23] Lin M, Loh KP, Deivaraj TC, Vittal JJ. Heterogeneous reaction route to CuInS2 thin films. Chem Commun.
2002;1400–1401.
[24] Singh P, Bhattacharya S, Gupta VD, Nöth H. Structural studies on indium and tin thiobenzoates. Chem Ber.
1996;129:1093–1098.
[25] Ziemkowska W, Cyran´ski M, Kunicki A. Alkylaluminum derivatives of diphenic acid: novel aluminium carboxy-
lates. Inorg Chem. 2009;48:7006–7008.
[26] Ziemkowska W, Jas´kowska E, Madura I, Zachara J, Zygadło-Monikowska E. Synthesis and structure of diethylalu-
minum malonate: an unusual hexanuclear aluminum complex with malonate trianion ligands. J Organomet Chem.
2012;713:178–181.
[27] Jas´kowska E, Justyniak I, Cyran´ski MK, Adamczyk-Woz´niak A, Sporzyn´ski A, Zygadło-Monikowska E,
Ziemkowska W. Benzoxaborolate ligands in group 13 metal complexes. J Organomet Chem. 2013;732:8–14.

Journal of Sulfur Chemistry 339
[28] Ziemkowska W, Kochanowski J, Cyran´ski MK. Synthesis, structures and ꢂ-caprolactone polymerization activity of
aluminum N,N’-dimethyloxalamidates. J Organomet Chem. 2010;695:1205–1209.
[29] Ziemkowska W, Jas´kowska E, Zygadło-Monikowska E, Cyran´ski MK. Reactions of group 13 metal trialkyls with
oxamides. J Organomet Chem. 2011;696:2079–2085.
[30] Bethley CE, Aitken CL, Harlan CJ, Koide Y, Bott SG, Barron AR. Structural characterization of dialkylaluminum
carboxylatyes: model for carboxylate alumoxanes. Organometallics. 1997;16:329–341.
[31] Keys A, Barbarich TJ, Bott SG, Barron AR. tert-Butyl compounds of gallium. J Chem Soc Dalton Trans. 2000;577–
588.
[32] Dickie DA, Choytun DD, Jennings MC, Jenkins HA, Clyburne JAC. A structural study of dimethylaluminum
carboxylate and hydrazonato complexes. J Organomet Chem. 2004;689:2186–2191.
[33] Loiseau T, Serre C, Huguenard C, Fink G, Taulelle F, Henry M, Bataille T, Férey G. A rationale for the large
breathing of the porous aluminum terephthalate (MIL-53) upon hydration. Chem Eur J. 2004;10:1373–1382.
[34] Sokołowski K, Bury W, Justyniak I, Fairen-Jimenez D, Sołtys K, Prochowicz D, Yang S, Schröder M, Lewin´ski J.
Permanent porosity derived from the self-assembly of highly luminescent molecular zinc carbonate nanoclusters.
Angew Chem Int Ed. 2013;52:13414–13418.
[35] Uhl W. Die Reaktion des tert.Butyl-lithiums mit Aluminiumtribromid; Molekülstrukturen von [HAl(CMe3)2]3 und
[LiHAl(CMe3)3]2. Z Anorg Allg Chem. 1989;570:37–53.
[36] Kovar RA, Derr H, Brandau D, Callaway JO. Preparation of organogallium compounds from organolithium
reagents and gallium chloride. Infrared, magnetic resonance, and mass spectral studies of alkylgallium compounds.
Inorg Chem. 1975;14:2809–2814.
[37] Marczenko Z. Odczynniki organiczne w analizie nieorganicznej. Warszawa: PWN; 1959, polish edition.
[38] Milner WG, Woodhead JL. The determination of alumina in silicates (Rocks and Refractories). Anal Chim Acta.
1955;12:127–137.
[39] CrysAlisPro, Agilent Technologies. Version 1.171.35.19 (release 27-10-2011 CrysAlis171.NET), Santa Clara, CA;
2011.
[40] Sheldrick GM. A short history of SHELX. Acta Cryst. 2008;A64:112–122.
[41] Dolomanov OV, Bourhis LJ, Gildea RJ, Howard JAK, Puschmann H. OLEX2: a complete structure solution,
refinement and analysis program. J Appl Cryst. 2009;42:339–341.
[42] Wilson A J C, editor. International tables for crystallography. Dordrecht: Kluwer; 1992, Vol.C.