Extending the time: Solvothermal syntheses, crystal structures, and properties of two non-isostructural thioantimonates with the composition [Mn(tren)]Sb2S4

Article abstract of DOI:10.1021/ic0519739

The two novel compounds, [Mn(tren)]Sb₂S₄ (1 and 2), were obtained by the reaction of elemental Mn, Sb, and S in aqueous solutions of tren (tren = tris(2-aminoethyl)amine, C₆H₁₈N₄) after different reaction times. Compound 1 is formed up to a reaction time of 13 d, and an extension of the reaction time leads to the formation of 2. Both compounds crystallize in monoclinic space groups (1, P2₁/c, 2, C2/c). In 1, the two unique SbS₃ trigonal pyramids share a common S atom to form a Sb₂S₅ unit. Two S atoms of this group have a bond to Mn²⁺ yielding a MnSb₂S₃ heteroring in the boat conformation. The Sb₂S₅ moieties are joined via common corners into the final undulated _∞¹[Sb ₂S₄]^2- anion which is directed along [001]. The structure of 2 contains the [Mn(tren)]²⁺ ion, one SbS₃ pyramid, and a SbS₄ unit. Two symmetry-related SbS₄ groups share an edge, forming a Sb₂S₆ group containing a Sb ₂S₂ ring. This group is joined via corners to two SbS ₃ pyramids on both sides producing a Sb₄S₄ ring. The Sb₂S₂ and Sb₄S₄ rings are condensed into the final _∞¹[Sb₂S ₄]^2- anion which runs along [010]. The [Mn(tren)] groups are bound to the thioantimonate(III) backbone on opposite sides of the Sb ₄S₄ ring, and a small MnSbS₂ ring is formed. In both structures, weak S...H bonds are found which may contribute to the stability of the materials. The two compounds decompose in one step upon heating, and only MnS and Sb₂S₃ could be identified as the crystalline part of the decomposition products. Both compounds can also be prepared under solvothermal conditions using MnSb₂S₄ as starting material. Compounds 1 and 2 are obtained from this ternary material in a high yield.

Full text of DOI:10.1021/ic0519739

Inorg. Chem. 2006, 45, 3726−3731
Extending the Time: Solvothermal Syntheses, Crystal Structures, and
Properties of Two Non-isostructural Thioantimonates with the
Composition [Mn(tren)]Sb S4
2
Michael Schaefer, Daniel Kurowski,‡ Arno Pfitzner,‡ Christian Na
†
1
ther,† Zomaje Rejai,† Karina Mo
1
ller,†
†
,†
Nancy Ziegler, and Wolfgang Bensch*
Institut f u¨ r Anorganische Chemie, Christian-Albrechts-UniVersit a¨ t Kiel, Olshausenstrasse 40,
D-24098 Kiel, Germany, and Institut f u¨ r Anorganische Chemie, UniVersit a¨ t Regensburg,
UniVersit a¨ tsstrasse 31, 93040 Regensburg
Received November 15, 2005
The two novel compounds, [Mn(tren)]Sb
in aqueous solutions of tren (tren tris(2-aminoethyl)amine, C
is formed up to a reaction time of 13 d, and an extension of the reaction time leads to the formation of 2. Both
2
S
4
(1 and 2), were obtained by the reaction of elemental Mn, Sb, and S
)
6 18 4
H N ) after different reaction times. Compound 1
compounds crystallize in monoclinic space groups (1, P2
share a common S atom to form a Sb
1
/c; 2, C2/c). In 1, the two unique SbS
3
trigonal pyramids
+
S
2 5
unit. Two S atoms of this group have a bond to Mn2 yielding a MnSb
S
2 3
heteroring in the boat conformation. The Sb
2
S
5
moieties are joined via common corners into the final undulated
1
]2 anion which is directed along [001]. The structure of 2 contains the [Mn(tren)]2 ion, one SbS
unit. Two symmetry-related SbS groups share an edge, forming a Sb group containing a Sb
pyramids on both sides producing a Sb ring. The Sb and
]2 anion which runs along [010]. The [Mn(tren)] groups are bound
ring, and a small MnSbS ring is formed. In both
structures, weak S‚‚‚H bonds are found which may contribute to the stability of the materials. The two compounds
decompose in one step upon heating, and only MnS and Sb could be identified as the crystalline part of the
-
+
[
Sb S
2 4
3
pyramid,
∞
and a SbS
4
4
S
2 6
2 2
S
ring. This group is joined via corners to two SbS
3
-
S
4 4
2 2
S
1
Sb
4
S
4
rings are condensed into the final ∞[Sb
2
S
4
to the thioantimonate(III) backbone on opposite sides of the Sb
4
S
4
2
2 3
S
2 4
decomposition products. Both compounds can also be prepared under solvothermal conditions using MnSb S as
starting material. Compounds 1 and 2 are obtained from this ternary material in a high yield.
Introduction
Mn atom bonds two 2 N and 4 S atoms. The amines point
into the empty space between successive layers, and the
interlayer interactions are weak and of the van der Waals
type. A spectacular compound with composition [Mn-
During the past few years we demonstrated that Mn2 is
a very good candidate to be incorporated into thioantimonate-
+
(
III) anionic frameworks: examples are the series of
(
C
6
H
18
N
4
)]
erometallic [Mn
tetrahedra and SbS
4
Mn
2
Sb
4
S
12 contains the formerly unknown het-
1
-3
2 2 5
compounds with composition Mn Sb S ‚L (L ) amine).
2
Sb
4
S
12] core which is constructed by MnS
4
In these compounds Mn, Sb, and S atoms form heterocubanes
which are joined into a neutral layered structure. One of the
two independent Mn atoms is surrounded in a severely
distorted octahedral environment of 6 S atoms, and the other
3
pyramids being linked via common
4
2+
6 18 4
corners and edges. The [Mn(C H N )] cations are located
at the periphery of the core and are bound to the [Mn
unit via two S atoms. Interesting examples are the two new
neutral thioantimonates(III) [Mn(tren)] Sb (tren ) tris-
2-aminoethyl)amine, C ) and [Mn(tren)]
In the former compound trigonal SbS
2 4 12
Sb S ]
2
2 5
S
*
To whom correspondence should be addressed. Fax: +49-(0)431-880-
5
(
H N
6 18 4
2 2 4 10
Mn Sb S .
1
520. E-mail: wbensch@ac.uni-kiel.de.
†
pyramids are con-
nected via common corners to give the tetradentate [Sb S ]
2 5
Christian-Albrechts-Universit a¨ t Kiel.
Universit a¨ t Regensburg.
3
‡
4-
(1) Bensch, W.; Schur, M. Eur. J. Solid State Inorg. Chem. 1996, 33,
1
149.
(
(
2) Schur, M.; N a¨ ther, C.; Bensch, W. Z. Naturforsch. 2001, 56b, 79.
3) Engelke, L.; St a¨ hler, R.; Schur, M.; N a¨ ther, C.; Bensch, W.; P o¨ ttgen,
R.; M o¨ ller, M. H. Z. Naturforsch. 2004, 59b, 869.
(4) Schaefer, M.; N a¨ ther, C.; Bensch, W. Solid State Sci. 2003, 5, 1135.
(5) Schaefer, M.; N a¨ ther, C.; Lehnert, N.; Bensch, W. Inorg. Chem. 2004,
43, 2914.
3726 Inorganic Chemistry, Vol. 45, No. 9, 2006
10.1021/ic0519739 CCC: $33.50
© 2006 American Chemical Society
Published on Web 04/06/2006

2 4
Thioantimonates with the Composition [Mn(tren)]Sb S
anion of which four S atoms have bonds to the manganese
atoms of the [Mn(tren)]2+ ions. A remarkable feature is the
comparably large angle of 134° around the S atom joining
the two Sb atoms. In the structure of the second compound,
Structure Determination. The intensity data were collected with
an Imaging Plate diffraction system (Fa. Stoe). The raw intensities
were treated in the usual way and were corrected for absorption
9
10
effects using X-Red and X-Shape. The structures were solved
11
with direct methods using SHELXS-97, and structure refinement
4 3
MnS tetrahedra and SbS pyramids are linked via common
2
12
was performed against F using SHELXL-97. All non-hydrogen
atoms except some of the disordered carbon atoms were refined
anisotropically. The hydrogen atoms were positioned with idealized
geometry and were refined isotropically using a riding model. Three
carbon atoms of the ligand in compound 1 are disordered and were
refined using a split model with anisotropic displacement factors
for the major occupied atoms (sof ) 0.8) and isotropic displacement
factors for the minor occupied atoms (sof ) 0.2). In 2, some carbon
atoms of the ligand are disordered and were refined anisotropically
using a split model (sof ) 0.65: 0.35). Crystal data, results of the
structure refinement, and bond lengths and angles are found in
Tables 1 and 2.
Crystallographic data (excluding structure factors) for the
structures reported in this paper have been deposited with the
Cambridge Crystallographic Data Centre as supplementary publica-
tions CCDC185044 (2) and CCDC 600580 (1). Copies of the data
can be obtained free of charge on application to CCDC, 12 Union
Road, Cambridge CB21EZ, UK (fax (+44)1223-336-033;
e-mail: deposit@ccdc.cam.ac.uk).
corners and edges to form a new heterometallic [Mn
2
Sb
4
S
10
]
core. The [Mn(tren)]2 cations are located at the periphery
+
and are bound to the central core via two S atoms. Finally,
the new compounds [TM(tren)]Sb S were prepared with TM
4 7
2
+
2+
2+
2+ 6
)
Mn , Fe , Co , and Zn . In these isostructural
2-
compounds, the [Sb
4
7
S ]
anions are composed of three SbS
unit which share edges and
). The Sb moieties and
pyramids are joined in an alternating fashion, yielding
3
trigonal pyramids and one SbS
corners to form semicubes (Sb
4
3
S
4
3 4
S
SbS
3
1
∞
2-
the [Sb
4
S
7
] anionic chain. Weaker Sb-S bonding inter-
actions between neighbored chains lead to the formation of
layers within the (001) plane. The layers contain pockets
that are occupied by the cations. The TM2 ions are in a
trigonal bipyramidal environment of four N atoms of the tren
ligand and one S atom of the thioantimonate(III) anion.
Most syntheses are performed using the elements or binary
+
compounds as staring materials. Very recently we demon-
strated that the reaction of the ternary compound MnSb
7
2
S
4
X-ray Powder Diffractometry. The X-ray powder patterns were
recorded on a Stoe Stadi-P diffractometer (Cu KR1 radiation, λ )
with dien (dien ) diethylenetriamine) yielded the new
thioantimonate(III) [Mn(dien) ]Sb ‚0.5H O which was not
accessible by using the elements as educts. [Mn(dien)
Sb ‚0.5H O was obtained phase pure in high yields which
encouraged us to perform more syntheses with MnSb as
1.540598 Å) in transmission geometry.
2
S
4 7
2
8
Thermoanalytical Measurements. Thermal investigations were
2
]-
performed on a Netzsch STA-409CD DTA-TG measurement
device. All measurements were corrected for buoyancy and current
effects. They were performed using a heating rate of 4 K/min in
S
4 7
2
2 4
S
starting material. Here, we report on the synthesis, crystal
structures, and properties of the two novel thioantimonate-
Al
5 mL/min; purity 99.999%; sample weight 11.9 (1) and 15.1 mg
2)).
2 3
O crucibles under a dynamic nitrogen atmosphere (flow rate
7
(
(III) compounds with the composition [Mn(tren)]Sb
2 4
S .
Experimental Section
Results and Discussion
Synthesis. The title compounds were synthesized under solvo-
thermal conditions from elemental manganese (54.9 mg, 1 mmol),
antimony (243.5 mg, 2 mmol), and sulfur (128.3 mg, 4 mmol) in
Crystal Structures. In the two new compounds, [Mn-
(
2 4
tren)]Sb S (1 and 2), all atoms are in general positions.
2+
The Mn ions are located in a distorted octahedral environ-
ment of four N atoms of the tren ligand and two S atoms of
5
1
mL of a tren/H
2
O solution (50%). The mixtures were heated at
40 °C for 7 days (1) and 33 days (2) in Teflon-lined steel
1
∞
2
-
the [Sb
S
2 4
]
anions (Figures 1 and 2). The Mn-N bonds
autoclaves with an inner volume of approximately 30 mL. The
products consisting of dark orange (1) and red-orange (2) colored
crystals with a polyhedral shape were filtered off, washed with
distilled water, and dried in air. The yield was about 80% for 1
and 40% for 2.
range from 2.240(3) to 2.375(3) Å in 1 and from 2.235(3)
to 2.350(3) Å in 2. The Mn-S bond lengths are 2.5181(9)
and 2.7494(10) Å in 1 and 2.4774(10) and 2.7947(9) Å in 2
(Table 2). As expected the longer Mn-N distances are on
the opposite side of the short Mn-S bond (Table 2).4
,5,14,15
Both compounds were also obtained using MnSb
.468 mmol) in 5 mL of an 90% aqueous solution of tris(2-
2
S
4
(200 mg,
7
0
3
In 1, two SbS trigonal pyramids share a common S atom
aminoethyl)amine (yield of 65-70%). The only byproduct of the
procedure presented above was elemental antimony which was
detected in the X-ray powder patterns.
to form a Sb S unit. Two S atoms of this group have a bond
2
5
2+
to Mn yielding a MnSb
mation (Figures 1 and 2). The Sb
common corners into the final undulated [Sb
2
S
3
heteroring in the boat confor-
2 5
S
moieties are joined via
1
2-
Long time experiments from 7 to 33 d were performed using
the first synthetic procedure to determine the time when compound
2 4
S ]
anion
∞
(
Figure 2) which is directed along [001]. Otherwise, the
1
disappears and compound 2 is formed.
CHNS analysis: calcd. C 12.58, H 3.17, N 9.78, S 22.39; found
2) C 12.30, H 2.97, N 9.63, S 22.36; found (1) C 12.35, H 3.05,
N 9.69, S 22.03.
(
9) X-Red32, version 1.11; Stoe & Cie GmbH: Darmstadt, Germany, 1998.
(
(10) X-Shape, version 1.03; Stoe & Cie GmbH: Darmstadt, Germany, 1998.
11) Sheldrick, G. M. SHELXS-97; University G o¨ ttingen: G o¨ ttingen,
Germany, 1997.
(
(12) Sheldrick, G. M. SHELXL-97; University G o¨ ttingen: G o¨ ttingen,
Germany, 1997.
(6) Schaefer, M.; St a¨ hler, R.; Kiebach, W.-R.; N a¨ ther, C.; Bensch, W. Z.
Anorg. Allg. Chem. 2004, 630, 1816.
(13) Hagen, K. S.; Amstrong, W. H.; Hope, H. Inorg. Chem. 1988, 27,
969.
(14) Ellermeier, J.; Bensch, W. Trans. Met. Chem. 2002, 27, 763.
(15) Laskowski, E. J.; Hendricksen, D. N. Inorg. Chem. 1978, 17, 457.
(
(
7) Pfitzner, A.; Kurowski, D. Z. Kristallogr. 2000, 215, 373.
8) Schaefer, M.; Kurowski, D.; Pfitzner, A.; N a¨ ther, C.; Bensch, W. Acta
Crystallogr. 2004, E60, m183.
Inorganic Chemistry, Vol. 45, No. 9, 2006 3727

Schaefer et al.
Table 1. Selected Data of Data Collection and Refinement Results for
Compounds 1 and 2
Table 2: Selected Bond Lengths (Å) and Angles (deg) in Compounds
1 and 2a
compound 1
compound 1b
empirical formula
fw
temp
wavelength
cryst syst
space group
unit cell dimensions
C6H18MnN4S4Sb2
Mn-N(2)
2.240(3)
2.256(3)
Mn-N(3)
2.279(3)
2.375(3)
2.7494(10)
2.3556(8)
2.4699(7)
2.5591(8)
-
1
572.92 (g mol
293(2) K
)
Mn-N(4)
Mn-N(1)
Mn-S(1)
2.5181(9)
2.3737(7)
2.4282(7)
2.4693(8)
2.5591(8)
Mn-S(4)
0.71073 Å
monoclinic
P21/c
Sb(1)-S(1)
Sb(1)-S(2)
Sb(1)-S(3)
S(2)-Sb(2B)
Sb(2)-S(4)
Sb(2)-S(3)
Sb(2)-S(2A)
a ) 10.1611(6) Å
b ) 15.2439(12) Å
c ) 11.2964(6) Å
â ) 112.808(6)°
N(2)-Mn-N(4)
N(2)-Mn-N(3)
N(4)-Mn-N(3)
N(2)-Mn-N(1)
N(4)-Mn-N(1)
N(3)-Mn-N(1)
N(2)-Mn-S(1)
S(1)-Sb(1)-S(2)
S(1)-Sb(1)-S(3)
S(2)-Sb(1)-S(3)
144.20(11)
90.48(12)
98.88(12)
74.37(10)
74.89(10)
75.00(11)
123.17(8)
107.66(3)
95.26(3)
N(4)-Mn-S(1)
N(3)-Mn-S(1)
N(1)-Mn-S(1)
N(2)-Mn-S(4)
N(4)-Mn-S(4)
N(3)-Mn-S(4)
N(1)-Mn-S(4)
S(1)-Mn-S(4)
S(4)-Sb(2)-S(3)
S(4)-Sb(2)-S(2A)
S(3)-Sb(2)-S(2A)
90.90(8)
93.31(9)
159.62(7)
81.60(9)
87.12(8)
172.02(9)
101.73(8)
91.86(3)
102.68(3)
96.89(3)
87.13(3)
3
vol
Z
1612.94(18) Å
4
3
density (calcd)
abs coeff
F(000)
cryst size
θ range
index ranges
2.359 Mg/m
-
1
4.599 mm
1092
3
0.12 × 0.08 × 0.06 mm
2.37-28.14°.
90.24(3)
-13 e h e 13
-
20 e k e 20
14 e l e 14
-
compound 2c
2.235(3)
2.267(3)
2.7947(9)
2.4048(8)
2.4312(8)
2.5046(8)
2.4234(8)
2.4018(12)
reflns collected
independent reflns
17 043
Mn-N(3)
Mn-N(4)
2.284(3)
2.350(3)
3749 [R(int) ) 0.0283]
Mn-N(2)
Mn-N(1)
completeness to θ ) 28.14°
refinement method
data/restraints/params
94.8%
full-matrix least-squares on F2
Mn-S(1)
Mn-S(2)
2.4774(10)
2.4018(12)
2.4234(8)
2.6143(9)
2.8564(8)
Sb(1)-S(1)
Sb(1)-S(2)
Sb(1)-S(3)
S(3)-Sb(2B)
S(4)-Sb(2A)
Sb(2)-S(4A)
Sb(2)-S(3B)
Sb(2)-S(4)
Sb(2)-S(1)
3749/0/167
1.054
2
GOF on F
final R indices [I > 2σ(I)]
R1 ) 0.0259
wR2 ) 0.0692
R1 ) 0.0294
wR2 ) 0.0711
0.0016(3)
R indices (all data)
N(3)-Mn-N(2)
N(3)-Mn-N(4)
N(2)-Mn-N(4)
N(3)-Mn-N(1)
N(2)-Mn-N(1)
N(4)-Mn-N(1)
N(3)-Mn-S(2)
N(2)-Mn-S(2)
S(1)-Sb(1)-S(2)
S(1)-Sb(1)-S(3)
S(2)-Sb(1)-S(3)
93.27(11) N(4)-Mn-S(2)
100.37(12) N(1)-Mn-S(2)
143.71(12) N(3)-Mn-S(1)
76.91(11) N(2)-Mn-S(1)
75.87(12) N(4)-Mn-S(1)
74.78(12) N(1)-Mn-S(1)
100.02(9)
109.14(9)
95.34(3)
100.41(3)
90.02(3)
101.41(9)
174.41(9)
173.48(9)
81.24(7)
82.31(8)
98.23(8)
85.17(3)
175.83(3)
84.65(2)
102.33(3)
121.16(3)
91.39(3)
extinction coeff
largest diff. peak and hole
-
3
0.955 and -0.946 e Å
compound 2
empirical formula
fw
temp
wavelength
cryst syst
space group
unit cell dimensions
C6H18MnN4S4Sb2
572.92
293(2) K
0.71073 Å
monoclinic
S(2)-Mn-S(1)
S(4)-Sb(2)-S(1)
Sb(1)-S(1)-Mn
Sb(1)-S(1)-Sb(2)
Mn-S(1)-Sb(2)
Sb(1)-S(2)-Mn
C2/c
a ) 23.4380(12) Å
b ) 8.8525(7) Å
c ) 19.1565(10) Å
â ) 122.788(5)°
S(4A)-Sb(2)-S(3B) 100.86(4)
S(4A)-Sb(2)-S(4)
S(3B)-Sb(2)-S(4)
S(4A)-Sb(2)-S(1)
S(3B)-Sb(2)-S(1)
88.08(3)
88.92(3)
87.86(3)
90.90(2)
Sb(2B)-S(3)-Sb(1) 106.78(3)
Sb(2A)-S(4)-Sb(2) 91.92(3)
3
vol
Z
3341.4(4) Å
8
3
density (calcd)
abs coeff
F(000)
cryst size
θ range
index ranges
2.278 Mg/m
4.440 mm
2184
a
Estimated standard deviations are given in parentheses. b Symmetry
-
1
transformation codes: A x, -y + 1/2, z - 1/2; B x, -y + 1/2, z + 1/2.
c
Symmetry transformation codes: A -x + 1, -y + 2, -z; B -x + 1, -y
3
0.11 × 0.08 × 0.06 mm
+
1, -z.
2.52-28.05°.
typical for thioantimonate(III) compounds (Table 2).1
The analysis of the packing and orientation of neighboring
chains yields some interesting results. Along [010], the
[Mn(tren)] ions of neighboring chains show an antiparallel
orientation; along [100], they are oriented in the same
direction (Figure 3), and along [001], they are packed so
that the organic parts are always oriented face-to-face (Figure
-6,16-23
-30 e h e 28
-
11 e k e 11
25 e l e 24
-
reflns collected
independent reflns
15 767
3895
2+
[
R(int) ) 0.0321]
completeness to θ ) 28.05°
refinement method
95.9%
full-matrix least-squares on F2
data/restraints/params
3895/0/191
1.023
2
GOF on F
3
bottom).
final R indices [I>2σ(I)]
R1 ) 0.0243
wR2 ) 0.0591
R1 ) 0.0304
wR2 ) 0.0612
0.00144(7)
The Sb atoms each have one long contact to a S atom in
the chain (Sb(2)-S(1) ) 3.113(3) Å, Sb(1)-S(3) )
R indices (all data)
extinction coeff
largest diff. peak and hole
(
16) Powell, A. V.; Boisi e` re, S.; Chippindale, A. M. Chem. Mater. 2000,
-
3
0.851 and -0.705 e Å
12, 182.
(
(
(
17) Graf, H. A.; Sch a¨ fer, H. Z. Naturforsch. 1972, 27b, 735.
18) Stephan, H.-O.; Kanatzidis, M. G. J. Am. Chem. Soc. 1996, 118, 12226.
19) Wang, X.; Liebau, F. Acta Crystallogr. 1996, B52, 7.
structure may be described as MnSb
nected by S atoms.
2 3
S rings being intercon-
(20) Schaefer, M.; N a¨ ther, C.; Bensch, W. Chem. Mon. 2004, 135, 461.
(
(
21) St a¨ hler, R.; Bensch, W. J. Chem. Soc., Dalton Trans. 2001, 2518.
22) St a¨ hler, R.; N a¨ ther, C.; Bensch, W. Eur. J. Inorg. Chem. 2001, 1835.
The Sb-S bond lengths (range of 2.3556(8)-2.5591(8)
Å) and S-Sb-S angles (range of 87.13(3)-107.66(3)°) are
(23) Volk, K.; Sch a¨ fer, H. Z. Naturforsch. 1979, 34b, 1637.
3728 Inorganic Chemistry, Vol. 45, No. 9, 2006

2 4
Thioantimonates with the Composition [Mn(tren)]Sb S
Figure 1. [Mn(tren)]2 cation and its interconnection with the SbS3
+
pyramids in 1 (top) and the cation together with the SbS3/SbS4 groups in
2
(bottom). Note: Disordered C atoms and H atoms are omitted for clarity.
Figure 2. Backbone of [Mn(tren)]Sb2S4 (1). Note: C, N, H atoms are
omitted for clarity. The atom coding is identical with that in Figure 1.
Figure 3. Two different views of the arrangement of the chains in 1:
top) view along [001] and (bottom) view along [010]. Note: H atoms are
not shown, and the atom coding is that used in Figure 1.
(
3
.257(3) Å). Thus, ψ-trigonal bipyramidal polyhedra result
when the lone electron pair located in the equatorial plane
is taken into account. The presence of five intermolecular
H‚‚‚S distances ranging from 2.630 to 2.963 Å and
N-H‚‚‚S angles between 133.55 and 178.70° indicate weak
hydrogen bonding.
1
∞
]2- anion in 2 is composed of one Sb(1)S
unit. Sb-S bond lengths and
are in the typical range (Table
unit, two longer Sb-S bonds are
observed (2.6143(9) and 2.8564(8) Å) (Table 2) which are
trans to each other with an angle of 175.83(3)°. Such SbS
The [Sb
2
S
4
3
trigonal pyramid and a Sb(2)S
S-Sb-S angles for Sb(1)S
4
3
1
-6,16-23
2
).
In the Sb(2)S
4
Figure 4. Backbone of the chain in compound 2. The C, N, and H atoms
are not displayed. The atom coding is that used in Figure 1.
4
groups are not uncommon and were observed in [Zn(tren)]-
likely occupying the free apical position (i.e., the coordination
polyhedron is a distorted ψ-octahedron). In Figure 5, two
different views of the packing of the chains are shown.
Neighboring chains along [010] are arranged such that the
tren ligand points into pockets which are formed by the
interconnected SbS units (Figure 5, top). In the (010) plane,
4
the chains are arranged in a layerlike fashion (Figure 5,
bottom).
Five short H‚‚‚S distances between 2.610 and 2.818 Å
with corresponding N-H‚‚‚S angles ranging from 140.33
to 166.91° indicate weak hydrogen bonding between adjacent
chains.
20
21
22
Sb
Cs
4
S
8
, [Co(tren)]Sb
4
S
8
, [Fe(dien)
2
]Sb
6
S
10‚0.75 H
2
O, and
23
2+
2 8
Sb S13. The S(1) and S(2) atoms are bound to the Mn
ion forming a MnSbS
Sb(2)S moieties share an edge, forming a Sb
containing a Sb ring. This group is joined via corners to
two Sb(1)S pyramids on both sides yielding a Sb ring.
The Sb and Sb rings are condensed to the final
anion which runs along [010] (Figure 4). The
Mn(tren)] groups are bound to the thioantimonate(III)
backbone on opposite sides of the Sb ring (Figure 4).
2
heteroring. Two symmetry-related
4
2 6
S
group
2 2
S
3
4 4
S
2
S
2
4 4
S
1
∞
2-
[
2 4
Sb S ]
[
4 4
S
The Sb(1) atom has two long contacts to S atoms within
the chain (Sb(1)-S(1)) 3.225(1) Å, Sb(1)-S(4) )
Thioantimonates with the composition [M(amine)]Sb
2 4
S
3.281(1) Å), and the environment may be regarded as a
are rare, and only two other examples exist. In the two-
2
4
distorted rectangular pyramid with the lone electron pair most
dimensional compound [Co(tren)]Sb
S
2 4
the anion is built
Inorganic Chemistry, Vol. 45, No. 9, 2006 3729

Schaefer et al.
Figure 6. DTA, TG, and DTG curves for compound 1 (Tp ) peak
temperature).
1
). In another experiment, some crystals of 2 were added to
the reaction mixture. After 7 days only crystals of compound
were found in the reaction product. When the syntheses
2
are performed in Teflon liners which were formerly used
for the preparation of compound 2 only this material
crystallized. These observations are hints that compound 2
is more stable than 1.
Normally, one would expect that the more stable material
exhibits the higher density. However, this is just a crude rule
and several exceptions are known. The observations for 1
Figure 5. Two different views of the arrangement of the chains in
compound 2: (top) view along [001] and (bottom) view along [010].
2 4
and 2 agree well with the unusual behavior of MnSb S
which exhibits a high-density high-pressure polymorph,
oP28, first reported in ref 25 and a lower density room-
temperature polymorph, mC28, which is supposed to be more
up from a SbS
the SbS units share a common edge, forming the well-known
Sb heterorings are joined via
heterorings.16 Four Sb
four SbS units yielding a squarelike net with a large Sb10
ring. The cavities of the rings are filled by the [Co(tren)]
3 4
trigonal pyramid and a SbS unit. Two of
4
7
2
S
2
S
2 2
stable.
3
S
10
Another interesting result was obtained with syntheses
which used MnSb S as the starting material. The ratio of
2 4
2
+
24
ions. In [Ni(tren)]Sb
2
S
4
, the anion is composed of two SbS
3
the elements is identical with that found in the products. But
according to the results of X-ray powder diffraction, elemen-
tal Sb was formed as a byproduct clearly indicating that a
redox reaction occurred. It is highly likely that this redox
reaction took place with the amine. During the reaction with
pyramids sharing a common corner to form an one-
dimensional chain. An interesting feature of this compound
is a NiSb
Sb , two pyramidal SbS
give dimeric Sb
2
S
3
ring in the twist conformation. In (CH
groups are linked via an edge to
anions, which are then joined via longer
3 3 2
NH ) -
2
S
4
3
2-
S
2 4
MnSb
MnS
products, only MnN
2
S
4
, the primary building units, SbS
octahedra, must be fully destroyed. In the final
, SbS , and SbS units are observed.
3
pyramids and
Sb-S bonds into one-dimensional chains.
6
Synthetic Aspects. The two new compounds were ob-
tained under identical synthesis conditions but after different
reaction times. This observation demonstrates that under
solvothermal conditions after short reaction times the less
stable material is formed first and the more stable compound
crystallizes at later stages of the reaction . According to our
long-term experiments, compound 1 is formed up to about
4
S
2
3
4
In situ X-ray scattering experiments are under way for a
better understanding of this complex reaction.
Thermal Investigations. The thermal stability of the title
compounds were investigated using simultaneous differential
thermoanalysis (DTA) and thermogravimetry (TG) measure-
2
ments under a N atmosphere. Compound 1 decomposes in
1
3 days, and via the extension of the syntheses beyond this
two steps with a total weight loss of 23.4% which is
accompanied by two endothermic events with peak temper-
time compound 2 is formed. The X-ray powder patterns gave
no hints for the coexistence of the two compounds indepen-
dently of the reaction time. One interesting finding is that
compound 1 has a higher density than compound 2 (Table
atures at T ) 277.4 °C and 295.0 °C (Figure 6). Unfortu-
p
nately, the two thermal reactions are too close, preventing a
more detailed study of the decomposition mechanism. In the
(24) St a¨ hler, R.; Bensch, W. Eur. J. Inorg. Chem. 2001, 3073.
(25) Bente, K.; Edenharter, A. Z. Kristallogr. 1989, 186, 31.
3730 Inorganic Chemistry, Vol. 45, No. 9, 2006

2 4
Thioantimonates with the Composition [Mn(tren)]Sb S
The decomposition of compound 2 starts at approximately
50 °C in one step with a total weight loss of 25.3% which
1
is accompanied by a broad endothermic event at T
p
) 296.0
°
C. The endothermic signal shows a shoulder at the lower
temperature side indicating that the material is decomposed
in two very close steps which cannot be resolved (Figure
7
). Again, the X-ray powder pattern shows only reflections
from MnS and Sb . In both cases, the weight loss can be
2 3
S
attributed to the removal of the tren ligand. The slightly
different values for ∆mexp can be attributed to a contamina-
tion of the decomposition products with small amounts of
C and N.
Acknowledgment. We gratefully acknowledge financial
support from the State of Schleswig-Holstein and the
Deutsche Forschungsgemeinschaft (DFG). We also thank
Inke Jess for the acquisition of the single crystal data and
Uschi Cornelissen for the spectroscopic investigations.
Figure 7. DTA, TG, and DTG curves for compound 2 (Tp ) peak
temperature).
X-ray powder pattern of the gray decomposition product
elemental Sb, MnS, and Sb
S
2 3
could be identified.
IC0519739
Inorganic Chemistry, Vol. 45, No. 9, 2006 3731