Inorganic Chemistry Communications 14 (2011) 884–888
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Inorganic Chemistry Communications
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / i n o c h e
A new hydrazine-bridged thioantimonate Mn2Sb4S8(N2H4)2: Synthesis, structure,
optical and magnetic properties
Yi Liu a, Yufeng Tian b, FengXia Wei a, Michael Ser Chong Ping a, Chuanwei Huang a, Freddy Boey a,
Christian Kloc a, Lang Chen a, Tom Wu b, Qichun Zhang a,⁎
a
b
School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore
Division of Physics and Applied Physics, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore
a r t i c l e
i n f o
Article history:
Received 23 January 2011
Accepted 8 March 2011
Available online 15 March 2011
Keywords:
Chalcogenide
Crystal structure
Solvothermal synthesis
Magnetic property
Optical properties
a b s t r a c t
A new thioantimonate [Mn2Sb4S8(N2H4)2] (1) was solvothermally synthesized by reacting Mn and Sb2S3 with
S in hydrazine monohydrate solution. The single crystal structure analysis revealed that all Mn sites adopt
distorted octahedral shapes and all Sb sites have either four-fold coordinated SbS4 configurations or square
pyramidal SbS5 geometry. These polyhedra units are interconnected into two-dimensional layers via the
sharing S atoms. These layers are further bridged into a novel three-dimensional framework by intra- and
inter-layer hydrazine ligands. The compound 1 is a semiconductor with a band gap of 1.59 eV and displays
paramagnetic behavior at high temperature and switches to antiferromagnetic ordering at 40 K.
© 2011 Elsevier B.V. All rights reserved.
The integration of crystalline chalcogenides with organic molecules (including metal complexes) not only results in various
interesting structures but also generates unusual physicochemical
properties, such as photocatalysts [1], gas separation [2], nonlinear
optics [3], photoluminescence [4], photoconductors [5], ion exchangers [6], porous materials [7], and magnetism [8]. Among the various
organic molecules, organic structure-directing agents are more
interesting because these molecules can act as different roles (e.g.
template, charge-balance species, bridging ligands, solvents or their
combination) during the crystal growth or in the final products [9–
18]. However, finding a good organic structure-directing agent with
multi-function to prepare new chalcogenides is challenging.
Among the various organic structure-directing agents for producing chalcogenides, hydrazine has already shown several characteristics such as basic, strongly reducing, coordination aptitude, and an
excellent solvent for chalcogenides. These amazing factors make
hydrazine more exciting as a solvent to prepare novel porous
crystalline chalcogenide materials via solvo(hydro)thermal method
[19–22].
Recently, two chalcogenides Mn 2 SnS 4 (N 2 H 4 ) 2 [20] and
Mn2Sb2S5(N2H4)3 [21] (the first example of Mn/pnictide-hydrizane
chalcogenides) have been synthesized under hydrazine-hydrothermal
condition. Continuing on this research direction through changing the
ratios of reactants and heating profiles, we discovered a novel three-
⁎ Corresponding author. Fax: +65 67909081.
E-mail address: [email protected] (Q. Zhang).
1387-7003/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2011.03.019
dimensional hydrazine-bridged thioantimonates [Mn2Sb4S8(N2H4)2]
(1), which is the second example to extend metal-hydrizane chalcogenide chemistry towards Mn/pnictide-hydrizane chalcogenides. We
reported here the synthesis, crystal structure, thermogravimetric
analysis, and X-ray powder diffraction analysis of [Mn2Sb4S8(N2H4)2]
(1) together with its optical and magnetic behaviours.
The compound 1 was prepared by reacting Mn and Sb2S3 with S
in N2H4/H2O (1:1) at 160 °C for 6 days (Fig. S1, Attention: hydrazine
monohydrate is highly toxic and may cause explosive) [23]. The X-ray
powder diffraction pattern of 1 agrees with the one simulated from
the single-crystal diffraction analysis (Fig. S2). The calculated Mn/Sb/S
atomic ratio from the single-crystal structure analysis is in agreement
with energy-dispersive X-ray spectroscopy analysis Mn/Sb/S in 1
(EDS, Fig. S3).
Single-crystal X-ray diffraction analysis reveals that the new
―
compound 1 crystallizes in the triclinic space group P 1 (No. 2)
and features a three-dimensional (3D) framework, where a neutral
two-dimensional (2D) layer parallel to the ab plane are bridged by
H2N-NH2 molecules. The asymmetric unit of 1 contains two
crystallographically independent Mn sites, four Sb sites, eight S
sites, and two H2N-NH2 neutral molecules (Fig. 1). Because all H2NNH2 molecules are neutral in the framework of 1, the formal oxidation
states of Mn/Sb/S can be assigned as 2+/3+/2−, respectively.
Both Mn1 and Mn2 sites adopt a distorted octahedral geometry
and coordinate with four S atoms and two N atoms, which come
from two different H2N-NH2 ligands. The octahedral coordination
geometry for Mn sites can also be found in Mn2SnS4(N2H4)2 and
Mn2Sb2S5(N2H4)3 frameworks [20,21]. The bond distances of Mn-S
Y. Liu et al. / Inorganic Chemistry Communications 14 (2011) 884–888
885
Fig. 1. Ball-stick model of the relevant fragments of compound 1.
and Mn-N are in the ranges of 2.512(3)–2.769(3) Å and 2.211(10)–
2.237(15) Å, respectively while the bond angles of S-Mn-S and N-MnS range from 81.05(10) to 174.13(12)° and from 81.7(3) to 175.1(3)°,
respectively. Although there are four Sb sites in this structure, only
two different coordination geometries are observed. The Sb1, Sb2, and
Sb4 sites adopt the same geometry and each site coordinates with five
S atoms to generate a SbS5 square pyramidal geometry while the Sb3
site adopts a SbS4 four-fold coordination geometry. The length of Sb–S
bond in SbS5 square pyramidal geometry ranges from 2.372(3) to
3.145(1) Å while SbS4 four-fold coordination geometry has two short
(2.420(3) and 2.432(3) Å) and two long (2.612(3) and 3.166(2) Å)
Sb–S distances. Interestingly, there are two so-called secondary bonds
with Sb–S distances about 3.160(3) and 3.161(2) Å in square
pyramidal geometry, which are longer than expected for single
bonds and increase the coordination number of Sb atoms in the
structure. Such arrangement follows the principle that the Sb atoms in
most thioantimonate (III) compounds have at least one longer bond
connecting to an additional S atom to complete its coordination
spheres [24].
Inside of the 2D layer substructure, six SbS5 square pyramids and
two SbS4 trigonal bipyramids share S···S edges to form a Sb8S16 unit,
which is further interconnected with each other by S atoms to
construct a one-dimensional (1D) linear chain (Fig. 2a). These chains
are bridged by Mn2S4N2 units via edge-sharing and vertex-sharing to
form a two-dimensional (2D) layer (Fig. 2b). The thickness of Mn/Sb/
S/N layer is about 5.7 Å (Fig. 2c), which is similar to that of the related
material Mn2Sb2S5(N2H4)3 [21]. Along the c axis, these Mn/Sb/S/N
layers overlap each other via inter-layer hydrazine molecules to form
the overall three-dimensional (3D) framework. The H2N-NH2 molecules in compound 1 have two different roles: one serves as the intralayer bridged ligands while the other acts as the inter-layer linkers.
These two types of hydrazine molecules adopting zigzag are located
among the inorganic layers. All these two coordination modes for
hydrazine molecules can be found in Mn2Sb2S5(N2H4)3 and Mn2SnS4
(N2H4)5 frameworks [20,21].
Interestingly, some thioantimonate (III) frameworks (2) with
the same stoichiometry (i.e. M2Sb4S8·L M = Zn, Ni, Co; L = tris(2aminoethyl)amine, diethylenetriamine, and ethylenediamine) have
been reported by Bensch and Kanatzidis groups [25,26], which seem
to be similar to the title compound 1. However, a simple comparison
will suggest that their structural characteristics are very different
from ours. The differences between these two structures are: (a) 1
Fig. 2. (a) Chain in the structure of 1 viewed along the b axis. (b) View of a single layer of
compound 1 along the c axis. (c) View of the three dimensional framework of 1 down
the b axis.
forms a three-dimensional networks through hydrazine-bridged
neighboring Mn2Sb4S8 layers while compound 2 exhibits a zerodimensional discrete molecules or a two-dimensional layered
structure; (b) Mn centers in 1 coordinated with two N atoms and
four S atoms to construct Mn2S4N2 distorted octahedral while 2 has
three different distorted M centered geometries: MS6 octahedral,
MSN4 trigonal bipyramidal and MS4 tetrahedral; (c) the Sb atoms in 1
have two different coordinations: four-fold coordinated SbS4 and
square pyramidal SbS5 while the configurations of Sb atoms in 2 are
either trigonal pyramids SbS3 or four-fold coordinated SbS4; and
(d) the substructure connectivity is different.
The solid state UV–visible absorption for compound 1 has been
measured on the diffuse-reflectance spectra at room temperature
(Fig. S4). It reveals the presence of a steep fundamental absorption
edge in the visible region with an optical gap of 1.59 eV, which is
consistent with the black color of the crystals [27]. This band gap is
smaller than those of binary MnS (3.2 eV) [28], and Mn2Sb2S5(N2H4)3
(2.09 eV) [21], but it is bigger than that of orthorhombic MnSb2S4
(0.77 eV) [29]. In fact, the bandgap of compound 1 is comparable to
that of condensed phase Sb2S3 (1.7–1.9 eV) [30].
The thermogravimetric analysis (TGA, Fig. S5) was performed from
30 °C to 900 °C under a N2 atmosphere. There is no weight loss up to
269 °C, which indicates that no free solvent molecule is present in the
886
Y. Liu et al. / Inorganic Chemistry Communications 14 (2011) 884–888
pnictide-hydrazine chalcogenide family. The extension of this work to
other inorganic systems could enrich metal-hydrazine chalcogenide
chemistry and the related research is underway.
Acknowledgement
Financial support from the AcRF Tier 1 (RG 18/09) from MOE is
gratefully acknowledged.
Appendix A. Supplementary material
Supplementary data related to this article can be found online at
doi: 10.1016/j.inoche.2011.03.019.
References
Fig. 3. Plot of 1/χM vs temperature (T) for compound 1. Inset: magnetization (M) as a
function of magnetic field (H).
structure. Then a steep and significant weight loss (∼7.01%) was
observed between 269 and 301 °C, which is attributed to the
vaporization of two types of coordinated hydrazine molecules
(Calcd: 7.01%).
Infrared spectroscopy (IR, Fig. S6) show a number of absorptions
between 3220 and 3118 cm− 1, which are from N-H stretching. The
peaks at 1578 and 1557 cm− 1 can be assigned to the bond bending of
N-H while the signals at 1180 and 1117 cm− 1 are come from NH2
rocking. In addition, the peak at 956 cm− 1 could belong to N-N
stretching, which is a typical region for the compounds containing
bridging H2N-NH2 molecules [20,21].
Magnetic property for compound 1 (Fig. 3) has been studied at a
field of 5000 Oe with the temperature range of 5–300 K. The
temperature dependent field cooled (FC) magnetization curve implies
that there is a second-order phase transition from paramagnetic
phase to anti-ferromagnetic one with the Néel temperature (TN)
about 40.5 K [31]. The observed overlapping zero field cooled (ZFC)
and field cooled (FC) magnetization curves reveal no spin glass
transition appears below 300 K. The temperature-dependent magnetic susceptibility in the temperature range of 50–300 K was fit by a
least-squares method using the Curie–Weiss equation χM = C/(T − θ),
where χM is the magnetic susceptibility, C is the Curie constant and θ
is the Weiss constant. The effective magnetic moment (μeff) can be
calculated by the equation μeff = (7.997 C)1/2μB. The parameters obtained from fitting are as follows: Curie constant, C = 8.97 emu K/mol;
Weiss temperature, θ = − 77.28 K. The negative θ value indicates that
a considerably stronger antiferromagnetic couple dominates the
exchange between the magnetic Mn ions (the nearest distance
between Mn ions is 3.88 Å). The effective magnetic moment (μeff) for
one Mn2+ ion in the compound 1 is 4.24μB, which is in agreement
with high spin Mn2+ configuration known from MnS and MnS2 [29b].
Magnetization (M) as a function of the applied field (H) at different
temperatures is shown in inset of Fig. 3. A linear increase in the
magnetization is observed for compound 1, agreeing with an
antiferromagnetic ordering below 40.5 K.
In this study, we have successfully synthesized one new threedimensional hybrid metal sulfide framework, [Mn2Sb4S8(N2H4)2] 1,
with hydrazine molecules acting as intra-layer and inter-layer
bridging ligands. The optical band gap of compound 1 is about
1.59 eV, which suggests that it is a semiconductor and is comparable
to some efficient photovoltaic materials, such as CdTe (1.5 eV) and
GaAs (1.4 eV). Magnetic susceptibility measurements demonstrate
that the magnetic Mn2+ species in the present compound adopt high
spin configurations at high temperature. At the same time, there
might be a paramagnetic to antiferromagnetic transition at low
temperature. This compound is the second example in the Mn/
[1] (a) Z.Y. Zhang, J. Zhang, T. Wu, X.H. Bu, P.Y. Feng, Three-dimensional open
framework built from Cu-S icosahedral clusters and its photocatalytic
property, J. Am. Chem. Soc. 130 (2008) 15238–15239;
(b) N.F. Zheng, X.H. Bu, H. Vu, P.Y. Feng, Open-framework chalcogenides as
visible-light photocatalyst for hydrogen generation from water, Angew.
Chem. Int. Ed. 44 (2005) 5299–5303;
(c) N.F. Zheng, X.H. Bu, P.Y. Feng, Two-dimensional organization of [ZnGe3S9
(H2O)]4– supertetrahedral clusters templated by a metal complex, Chem.
Commun. (2005) 2805–2807;
(d) L. Wang, T. Wu, F. Zuo, X. Zhao, X.H. Bu, J.Z. Wu, P.Y. Feng, Assembly of
supertetrahedral T5 copper-indium sulfide clusters into a super-supertetrahedron of infinite order, J. Am. Chem. Soc. 132 (2010) 3283–3285;
(e) P. Vaqueiro, A three-dimensional open-framework indium selenide:
[C7H10N][In9Se14], Inorg. Chem. 47 (2008) 20–22;
(f) P. Vaqueiro, M.L. Romero, [Ga10S16(NC7H9)4]2−: a hybrid supertetrahedral
nanocluster, Chem. Commun. (2007) 3282–3284.
[2] (a) G.S. Armatas, M.G. Kanatzidis, Mesoporous germanium-rich chalcogenido
frameworks with highly polarizable surfaces and relevance to gas separation,
Nat. Mater. 8 (2009) 217–222;
(b) S. Bag, M.G. Kanatzidis, Chalcogels: porous metal-chalcogenide networks
from main-group metal ions. Effect of surface polarizability on selectivity in
gas separation, J. Am. Chem. Soc. 132 (2010) 14951–14959.
[3] (a) Q.C. Zhang, I. Chung, J.I. Jang, J.B. Ketterson, M.G. Kanatzidis, Chalcogenide
chemistry in ionic liquids: nonlinear optical wave-mixing properties of the
double-cubane compound [Sb7S8Br2](AlCl4)3, J. Am. Chem. Soc. 131 (2009)
9896–9897;
(b) Q.C. Zhang, I. Chung, J.I. Jang, J.B. Ketterson, M.G. Kanatzidis, A polar and chiral
indium telluride featuring supertetrahedral T2 clusters and nonlinear optical
second harmonic generation, Chem. Mater. 21 (2009) 12–14;
(c) M.J. Manos, J.I. Jang, J.B. Ketterson, M.G. Kanatzidis, Zn(H2O)4][Zn2Sn3Se9
(MeNH2)]: a robust open framework chalcogenide with a large nonlinear
optical response, Chem. Commun. (2008) 972–974.
[4] (a) Q.C. Zhang, X.H. Bu, L. Han, P.Y. Feng, Two-dimensional indium sulfide
framework constructed from pentasupertetrahedral P1 and supertetrahedral
T2 clusters, Inorg. Chem. 45 (2006) 6684–6687;
(b) Z.E. Lin, X.H. Bu, P.Y. Feng, Two new layered bimetallic sulfides: solvothermal
synthesis, crystal structure, optical and magnetic properties, Microporous
Mesoporous Mater. 132 (2010) 328–334.
[5] Q.C. Zhang, Y. Liu, X.H. Bu, T. Wu, P.Y. Feng, A rare (3,4)-connected chalcogenide
superlattice and its photoelectric effect, Angew. Chem. Int. Ed. 47 (2008) 113–116.
[6] (a) M.J. Manos, N. Ding, M.G. Kanatzidis, Layered metal sulfides: exceptionally
selective agents for radioactive strontium removal, Proc. Nat. Acad. Sci. U.S.A.
105 (2008) 3696–3699;
(b) M.J. Manos, K. Chrissafis, M.G. Kanatzidis, Unique pore selectivity for Cs+ and
exceptionally high NH+
4 exchange capacity of the chalcogenide material K6Sn
[Zn4Sn4S17], J. Am. Chem. Soc. 128 (2006) 8875–8883;
(c) R.C. Zhang, H.G. Yao, S.H. Ji, M.C. Liu, M. Ji, Y.L. An, (H2en)2Cu8Sn3S12: a
trigonal CuS3-based open-framework sulfide with interesting ion-exchange
properties, Chem. Commun. 46 (2010) 4550–4552;
(d) M.L. Feng, D.N. Kong, Z.L. Xie, X.Y. Huang, Three-dimensional chiral
microporous germanium antimony sulfide with ion-exchange properties,
Angew. Chem. Int. Ed. 47 (2008) 8623–8626.
[7] (a) S. Bag, P.N. Trikalitis, P.J. Chupas, G.S. Armatas, M.G. Kanatzidis, Porous
semiconducting gels and aerogels from chalcogenide clusters, Science 317
(2007) 490–493;
(b) N.F. Zheng, X.H. Bu, B. Wang, P.Y. Feng, Microporous and photoluminescent
chalcogenide zeolite analogs, Science 298 (2002) 2366–2369;
(c) N.F. Zheng, X.H. Bu, P.Y. Feng, Penta-supertetrahedral clusters as building
blocks for three-dimensional sulfide superlattice, Angew. Chem. Int. Ed. 43
(2004) 4753–4755.
[8] (a) Q.C. Zhang, X.H. Bu, Z.E. Lin, M. Biasini, W.P. Beyemann, P.Y. Feng, Metalcomplex-decorated homochiral heterobimetallic telluride single-stranded
helix, Inorg. Chem. 46 (2007) 7262–7264;
(b) C. Zimmermann, C.E. Anson, F. Weigend, R. Clerac, S. Dehnen, Unusual
syntheses, structures, and electronic properties of compounds containing
Y. Liu et al. / Inorganic Chemistry Communications 14 (2011) 884–888
(c)
[9] (a)
(b)
(c)
(d)
(e)
(f)
(g)
(h)
[10] (a)
(b)
(c)
(d)
[11] (a)
(b)
(c)
[12] (a)
(b)
(c)
(d)
[13] (a)
(b)
(c)
(d)
[14] (a)
(b)
(c)
(d)
[15] (a)
(b)
ternary, T3-type supertetrahedral M/Sn/S anions [M5Sn(μ3-S)4 (SnS4)4]10(M = Zn, Co), Inorg. Chem. 44 (2005) 5686–5695;
S. Dehnen, M. Melullis, A coordination chemistry approach towards ternary
M/14/16 anions, Coord. Chem. Rev. 251 (2007) 1259–1280.
P.Y. Feng, X.H. Bu, N.F. Zheng, The interface chemistry between chalcogenide
clusters and open framework chalcogenides, Acc. Chem. Res. 38 (2005) 293–303;
J. Zhou, J. Dai, G.Q. Bian, C.Y. Li, Solvothermal synthesis of Group 13–15
chalcogenidometalates with chelating organic amines, Coord. Chem. Rev. 253
(2009) 1221–1247;
D.B. Mitzi, Solution processing of chalcogenide semiconductors via dimensional reduction, Adv. Mater. 21 (2009) 3141–3158;
J. Li, Z. Chen, D.M. Proserpio, Low temperature route towards new materials:
solvothermal synthesis of metal chalcogenides in ethylenediamine, Coord.
Chem. Rev. 192 (1999) 707–735;
A.K. Cheetham, G. Férey, T. Loiseau, Open-framework inorganic materials,
Angew. Chem. Int. Ed. 38 (1999) 3268–3292;
W.S. Sheldrick, Network self-assembly patterns in Main Group metal
chalcogenide-based materials, Dalton Trans. (2000) 3041–3052;
W.S. Sheldrick, M. Wachhold, Chalcogenidometalates of the heavier Group 14
and 15 elements, Coord. Chem. Rev. 176 (1998) 211–322;
G.W. Drake, J.W. Kolis, The chemistry of mixed 15/16 Main Group clusters,
Coord. Chem. Rev. 131 (1994) 137–178.
W.P. Su, X.Y. Huang, J. Li, H.X. Fu, Crystal of semiconducting quantum dots
built on covalently bonded T5 [In28Cd6S54]− 12: the largest supertetrahedral
cluster in solid state, J. Am. Chem. Soc. 124 (2002) 12944–12945;
A. Kornienko, T.J. Emge, G.A. Kumar, R.E. Riman, J.G. Brennan, Lanthanide
clusters with internal Ln ions: highly emissive molecules with solid-state
cores, J. Am. Chem. Soc. 127 (2005) 3501–3505;
W.J. Evans, G.W. Rabe, M.A. Ansari, J.W. Ziller, Polynuclear lanthanide
complexes: formation of a selenium-centered Sm6 complex, [{(C5Me5)
Sm}6Se11] Angew, Chem. Int. Ed. 33 (1994) 2110–2111;
Z. Chen, J. Li, F. Chen, D.M. Proserpio, Solvothermal synthesis and crystal
structure of [La(ethylenediamine)4Cl]In2Te4: A 1-D indium telluride, Inorg.
Chem. Acta 273 (1998) 255–258.
H. Ahari, A. Lough, S. Petrov, G.A. Ozin, R.L. Bedard, Modular assembly and
phase study of two- and three-dimensional porous tin(IV) selenides, J. Mater.
Chem. 9 (1999) 1263–1274;
T. Jiang, G.A. Ozin, R.L. Bedard, Nanoporous tin(IV) sulfides: mode of
formation, Adv. Mater. 6 (1994) 860–865;
T. Jiang, G.A. Ozin, New directions in tin sulfide materials chemistry, J. Mater.
Chem. 8 (1998) 1099–1108.
E. Ruzin, A. Fuchs, S. Dehnen, Fine-tuning of optical properties with salts of
discrete or polymeric, heterobimetallic telluride anions [M4(μ4-Te)(SnTe4)4]10−
(M= Mn, Zn, Cd, Hg) and 3∞{[Hg4(μ4-Te)(SnTe4)3]6−}, Chem. Commun. (2006)
4796–4798;
M. Melullis, R. Clerac, S. Dehnen, Ternary Mn/Ge/Se anions from reactions of
[Ba2(H2O)9][GeSe4]: synthesis and characterization of compounds containing
discrete or polymeric [Mn6Ge4Se17]6− units, Chem. Commun. (2005)
6008–6010;
S. Dehnen, M.K. Brandmayer, Reactivity of chalcogenostannate compounds:
syntheses, crystal structures, and electronic properties of novel compounds
containing discrete ternary anions [MII4(μ4-Se)(SnSe4)4]10- (MII = Zn, Mn),
J. Am. Chem. Soc. 125 (2003) 6618–6619;
C. Zimmermann, M. Melullis, S. Dehnen, Reactivity of chalcogenostannate salts:
unusual synthesis and structure of a compound containing ternary cluster
anions [Co4(μ4-Se)(SnSe4)4]10-, Angew. Chem. Int. Ed. 41 (2002) 4269–4272.
S. Dhingra, M.G. Kanatzidis, Open framework structures based on Se2–
x
fragments: synthesis of (Ph4P)[M(Se6)2] (M = Ga, In, Tl) in molten (Ph4P)2Sex, Science 258 (1992) 1769–1772;
C.C. Wang, R.C. Haushalter, Synthesis and structural characterization of (nBu4N)3AuSn2Te6, Inorg. Chem. 38 (1999) 595–597;
C.C. Wang, R.C. Haushalter, Synthesis and characterization of two new
telluroindates: K6In2Te6·4C2H8N2 and (Ph4P)2In2Te6, Inorg. Chem. 36 (1997)
3806–3807;
S.S. Dhingra, R.C. Haushalter, A novel ternary Zintl anion: synthesis and
structural characterization of the [Cu4SbTe12]3- anion, J. Am. Chem. Soc. 116
(1994) 3651–3654.
C.-W. Park, R.J. Salm, J.A. Ibers, New tellurometalates of gallium and indium: K
[K([18]crown-6)]2[GaTe3] · 2CH3CN and [(NEt4)5][In3Te7] · 0.5 Et2O, Angew.
Chem. Int. Ed. 34 (1995) 1879–1880;
T.M. Martin, P.T. Wood, J.W. Kolis, Synthesis and structure of an [Sb12Se20]4salt: the largest molecular Zintl ion, Inorg. Chem. 33 (1994) 1587–1588;
Z.Q. Wang, G.F. Xu, Y.F. Bi, C. Wang, Preparation of one dimensional group 14
metal sulfides: different roles of metal-amino complexes, Cryst. Eng. Comm
12 (2010) 3703–3707;
D.N. Kong, Z.L. Xie, M.L. Feng, D. Ye, K.Z. Du, J.R. Li, X.Y. Huang, From onedimensional ribbon to three-dimensional microporous framework: the
syntheses, crystal structures, and properties of a series of mercury antimony
chalcogenides, Cryst. Growth Des. 10 (2010) 1364–1372.
Z.H. Fard, L. Xiong, C. Müller, M. Hołyńska, S. Dehnen, Synthesis and reactivity
of functionalized binary and ternary thiometallate complexes [(RT)4S6],
[(RSn)3S4]2−, [(RT)2(CuPPh3)6S6], and [(RSn)6(OMe)6Cu2S6]4− (R = C2H4COOH, CMe2CH2COMe; T = Ge, Sn), Chem. Eur. J. 15 (2009) 6595–6604;
A. Philippidis, T. Bakas, P.N. Trikalitis, (H2NC4H8NCH2CH2NH2)2Zn2Sn2Se7: a
hybrid ternary semiconductor stabilized by amine molecules acting simultaneously as ligands and counterions, Chem. Commun. (2009) 1556–1558;
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
887
(c) J. Zhou, Y. Zhang, G.Q. Bian, C.Y. Li, X.X. Chen, J. Dai, Structural study of
organic-inorganic hybrid thiogallates and selenidogallates in view of effects
of the chelate amines, Cryst. Growth Des. 8 (2008) 2235–2240;
(d) A. Eichhöfer, Thermal properties of [M10Se4(SePh)12(PR3)4] (M = Zn, Cd, Hg)
cluster molecules–synthesis and structure of [Cd32Se 14(SePh)36(L)4];
L = OPPh3, OC4H8, Eur. J. Inorg. Chem. (2005) 1245–1253.
(a) A. Fehlker, R. Blachnik, H. Reuter, [Ga(en)3][Ga3Se7(en)] · H2O: a gallium
chalcogenide with chains of [Ga3Se6Se2/2(en)]3−-bicycles, Z. Anorg. Allg.
Chem. 625 (1999) 1225–1228;
(b) M. Bujoli-Doeuff, S. Coste, M. Evain, R. Brec, D. Massiot, S. Jobic, Synthesis and
structure of phases containing [Ni3P3S12]3- crown-shaped trimers, New J.
Chem. 26 (2002) 910–914;
(c) S. Dehnen, D. Fenske, [Cu24S12(PMeiPr2)12], [Cu28S14(PtBu2Me)12], [Cu50S25
(PtBu2 Me)16], [Cu70Se35(PtBu2Me)21], [Cu31Se15(SeSiMe3)(PtBu2Me)12] and
[Cu48Se24(PMe2Ph)20]: new sulfur- and selenium-bridged copper clusters,
Chem. Eur. J. 2 (1996) 1407–1416.
X. Wang, T.L. Sheng, S.M. Hu, R.B. Fu, X.T. Wu, Synthesis, structure, and properties
of a new manganese thioantimonate(III), [Mn2(phen)(SbIII
2 S5)]n, Inorg. Chem.
Commun. 12 (2009) 399–401.
(a) N. Pienack, A. Puls, C. Näther, W. Bensch, The layered thiostannate (dienH2)
Cu2Sn2S6: a photoconductive inorganic–organic hybrid compound, Inorg.
Chem. 47 (2008) 9606–9611;
(b) L. Engelke, M. Schaefer, F. Porsch, W. Bensch, In-situ energy-dispersive X-ray
diffraction studies of crystal growth and compound conversion under
solvothermal conditions, Eur. J. Inorg. Chem. 3 (2003) 506–513;
(c) L. Engelke, M. Schaefer, M. Schur, W. Bensh, In situ x-ray diffraction studies of
the crystallization of layered manganese thioantimonates(III) under hydrothermal conditions, Chem. Mater. 13 (2001) 1383–1390;
(d) M. Schur, C. Näther, W. Bensch, Synthesis and crystal structure of Mn2
(C2H5NH2)2Sb2S5 exhibiting a reversible phase transition, Z. Naturforsch. B
56 (2001) 79–84;
(e) W. Bensch, M. Schur, Hydrothermal synthesis and crystal structures of the
novel manganese(II) thioantimonates(III) Mn2Sb2S5(CH3NH2)2 and Mn2Sb2S5(NH2(CH2)3NH2): Layer compounds exhibiting hetero-cubane like building
units, Eur. J. Solid State Inorg. Chem. 33 (1996) 1149–1160.
X.Y. Huang, J. Li, Y. Zhang, A. Mascarenhas, From 1D chain to 3D network: tuning
hybrid II-VI nanostructures and their optical properties, J. Am. Chem. Soc. 125
(2003) 7049–7055.
M.J. Manos, M.G. Kanatzidis, Use of hydrazine in the hydrothermal synthesis of
chalcogenides: the neutral framework material [Mn2SnS4(N2H4)2], Inorg. Chem.
48 (2009) 4658–4660.
Y. Liu, P.D. Kanhere, C.L. Wong, Y.H. Feng, F. Boey, H.Y. Chen, T.J. White, Z. Chen,
Q.C. Zhang, Hydrazine-hydrothermal method to synthesize three-dimensional
chalcogenide framework for photocatalytic hydrogen generation, J. Solid State
Chem. 183 (2010) 2644–2649.
(a) M. Yuan, D.B. Mitzi, Solvent properties of hydrazine in the preparation of
metal chalcogenide bulk materials and films, Dalton Trans. (2009)
6078–6088;
(b) D.B. Mitzi, N4H9Cu7S4: a hydrazinium-based salt with a layered Cu7S-4
framework, Inorg. Chem. 46 (2007) 926–931;
(c) D.B. Mitzi, Synthesis, structure, and thermal properties of soluble hydrazinium
germanium(IV) and tin(IV) selenide salts, Inorg. Chem. 44 (2005) 3755–3761;
(d) M. Yuan, M. Dirmyer, J. Badding, A. Sen, M. Dahlberg, P. Schiffer, Controlled
assembly of zero-, one-, two-, and three-dimensional metal chalcogenide
structures, Inorg. Chem. 46 (2007) 7238–7240.
(a) Synthesis of compound 1: A mixture of Mn (0.5 mmol, 0.0275 g), Sb2S3
(0.5 mmol, 0.1700 g), S (0.75 mmol, 0.024 g), and hydrazine monohydrate (3 mL,
98%) were mixed in a 23 mL Teflon-lined stainless steel autoclave. Attention:
hydrazine monohydrate is highly toxic and may cause explosive. The autoclave
was sealed and heated at 160 °C for 7 days without any disturbing. Then, the
autoclave was taken out and cooled to room temperature at its natural cooling
rate. The black crystals 1 were isolated in 70 % yield (based on Sb2S3),
washed several times with deionized water, acetone, and ethanol, and airdried. The crystals appear to be stable in air for months. (b) Crystal data for
―
compound 1: [Mn2Sb4S8(N2H4)2], Mr = 917.46, Triclinic, space group P 1,
a = 9.4900(19) Å, b = 9.780(2) Å, c = 10.150(2) Å, α = 111.86(3)°, β = 93.33(3)°
γ = 107.82(3)° V = 816.4(3) Å 3 , Z = 2, Dc = 3.732 g m -3 , μ (Mo Kα) =
9.029 mm-1, F(000) = 836, T = 100(2) K. The anisotropic refinement converged
to R1= 0.0526, wR2 =0.1638 for I N 2σ( I ) data. Data collection was performed on
a Bruker APEX II CCD diffractometer (λ = 0.71073 Å). Empirical absorption was
performed, and the structure was solved by direct methods and refined with the
aid of SHELX-TL program package. CCDC reference number: ********. Copy of this
information may be obtained free of charge from the Director, CCDC, 12 Union
Road, Cambridge, CB21EZ, UK (fax: +44–1223–336–033; email: [email protected].
ac.uk or www.ccdc.cam.ac.uk).
(a) J.B. Parise, Y.H. Ko, Novel antimony sulfides: synthesis and X-ray structural
characterization of Sb3S5·N(C3H7)4 and Sb4S7·N2C4H8, Chem. Mater. 4
(1992) 1446–1450;
(b) Y.H. Ko, K.M. Tan, J.B. Parise, A. Darovsky, Synthesis of a novel twodimensional antimony sulfide, [C4H10N]2[Sb8S13]·0.15H2O, and its structure
solution using synchrotron/imaging plate data, Chem. Mater. 8 (1996)
493–496;
(c) H.O. Stephan, M.G. Kanatzidis, Low-dimensional sulfoantimonates with
metal complexes as counterions. Hydrothermal synthesis and properties of
[M(en)3]Sb2S4 (M = Co, Ni) and [M(en)3]Sb4S7 (M = Fe, Ni), Inorg. Chem. 36
(1997) 6050–6057;
888
Y. Liu et al. / Inorganic Chemistry Communications 14 (2011) 884–888
(d) X.Q. Wang, F. Liebau, Synthesis and structure of [CH3NH3]2Sb8S13: a
nanoporous thioantimonate(III) with a two-dimensional channel system,
J. Solid State Chem. 111 (1994) 385–389.
[25] (a) R. Stähler, W. Bensch, Thioantimonate(III) anions acting as bridging ligands in
neutral transition metal complexes: solvothermal synthesis and characterisation of the two novel compounds [Co(C 6 H 18 N 4 )] 2 Sb 4 S 8 and [Co
(C6H18N4)]2Sb2S5 containing [Sb4S8]4- and [Sb2S5]4- anions, Dalton Trans.
(2001) 2518–2522;
(b) W. Bensch, C. Näther, R. Stähler, Solvothermal synthesis of [Ni(C4H13N3)2]2Sb4S8: the first compound with a cyclic [Sb4S8]4− anion, Chem. Commun.
(2001) 477–478;
(c) M. Schaefer, C. Näther, W. Bensch, Solvothermal synthesis, crystal structure,
and properties of the first zinc containing thioantimonate(III) [Zn(tren)]2Sb4S8·0.75 H2O, Monatsh. Chem. 135 (2004).
[26] H.O. Stephan, M.G. Kanatzidis, [Co(en)3]CoSb4S8: a novel non-centrosymmetric
lamellar heterometallic sulfide with large-framework holes, J. Am. Chem. Soc. 118
(1996) 12226–12227.
[27] G. Kortüm, Reflectance Spectroscopy, Springer, New York, 1969.
[28] S.H. Kan, I. Felner, U. Banin, Synthesis, characterization, and magnetic properties
of α-MnS. nanocrystals, Isr. J. Chem. 41 (2001) 55–61.
[29] (a) A. Pfitzner, D. Kurowski, A new modification of MnSb2S4 crystallizing in the
HgBi2S4 structure type, Z. Kristallogr. 215 (2000) 373–376;
(b) S.F. Matar, R. Weihrich, D. Kurowski, A. Pfitzner, V. Eyert, Electronic structure
of the antiferromagnetic semiconductor MnSb2S4, Phys. Rev. B 71 (2005)
23520701–23520709.
[30] S.D. Shutov, V.V. Sobolev, Y.V. Popov, S.N. Shestatskii, Polarization effects in the
reflectivity spectra of orthorhombic crystals Sb2S3 and Sb2Se3, Phys. Status Solidi
31 (1969) K23–K27.
[31] L.D. Landau, E.M. Lifshitz, Statistical Physics, Pergamon, Oxford, 1959.