2Sb18S29: A novel three-dimensional framework thioantimonate(III) templated by [Ni(phen)3] complexes

Article abstract of DOI:10.1021/ic202246q

A novel thioantimonate(III), namely, [Ni(phen)₃] ₂Sb₁₈S₂₉ (1; phen = 1,10-phenanthroline), has been solvothermally synthesized. Its structure features a three-dimensional framework with the largest channels in thioantimonates. The chiral [Ni(phen)₃]²⁺ cations and the Sb:S ratio (1:1.611) in 1 are unique among those in the reported thioantimonates. The thermal stability, optical properties, and electric conductivity as well as the theoretical band structure and density of state of 1 have also been studied.

Full text of DOI:10.1021/ic202246q

Communication
pubs.acs.org/IC
[
Ni(phen) ] Sb S : A Novel Three-Dimensional Framework
3 2 18 29
Thioantimonate(III) Templated by [Ni(phen) ] Complexes
3
Ke-Zhao Du,†,‡ Mei-Ling Feng, Long-Hua Li, Bing Hu, Zu-Ju Ma, Peng Wang, Jian-Rong Li,†
†
†
†
†,‡
†,‡
Yu-Long Wang,†,‡ Guo-Dong Zou, and Xiao-Ying Huang*
†,‡
,†
†State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences,
Fuzhou, Fujian 350002, People's Republic of China
‡
Graduate School of the Chinese Academy of Sciences, Beijing 100049, People's Republic of China
*
S Supporting Information
(
phen) ] Sb S (1), which represents the first polar 3D
3 2 18 29
ABSTRACT: A novel thioantimonate(III), namely, [Ni-
phen) ] Sb S (1; phen = 1,10-phenanthroline), has
thioantimonate with the largest channels filled with two distinct
arrays of [M(phen)3]2+ complexes. Significantly, the first
utilization of [M(phen)3]2+ as templates and the Sb:S ratio
(
3
2
18 29
been solvothermally synthesized. Its structure features a
three-dimensional framework with the largest channels in
(
1:1.611) of 1 are unique among those in the reported
2
+
thioantimonates. The chiral [Ni(phen)3] cations and the
Sb:S ratio (1:1.611) in 1 are unique among those in the
reported thioantimonates. The thermal stability, optical
properties, and electric conductivity as well as the
theoretical band structure and density of state of 1 have
also been studied.
thioantimonates.
Compound 1 was obtained from a mixture of Ni-
(
CH COO) ·4H O, Sb S , S, and phen·H O in a molar ratio
3 2 2 2 3 2
of 1:1:3:1, 3 mL of ethanolamine, and 1 mL of H O, which was
2
sealed in a stainless steel reactor with a 20-mL Teflon liner and
kept at 170 °C for 7 days. The product consisted of red clubbed
crystals of 1 and a small amount of black powder. During
synthesis, the templating cation was formed in situ.
etal chalcogenides have attracted much attention in
Single-crystal X-ray crystallography reveals that 1 belongs to
11
M
recent years owing to their potential applications in
the polar space group P21. Its structure features a 3D
framework with two-dimensional channels filled with the chiral
1 2
areas such as fast-ion conductivity, ion exchange, and tunable
3
electronic and optical properties. The research on
2+
[Ni(phen) ] cations. In the asymmetric unit of 1, there are 18
3
thioantimonates(III) has been very fruitful in the past 2
decades because the stereochemical effect of the lone pair of
crystallographically independent Sb atoms, 29 S atoms, and 2
2+
[Ni(phen)3] complexes. Except for Sb1 and Sb2, the other 16
4
III
electrons and the wide range of coordination numbers of Sb
Sb atoms all are coordinated to 3 S atoms to form SbS3
trigonal-pyramidal geometries, with the Sb−S distances ranging
from 2.336(3) to 2.539(2) Å. Whereas both Sb1 and Sb2 are
four-coordinated, with two short [2.423(2)−2.478(2) Å] and
two long [2.616(2)−2.868(2) Å] Sb−S bonds, similar to those
in the {Sb S } rings of the previously reported compound-
s.
As shown in Figure 1a, the Sb(9−16)S
interconnected by sharing of the corners to form a {Sb
(R1), whereas another similar {Sb } ring (R2) consisting of
from 3 to 6 can lead to large structural and compositional
5
diversities of thioantimonates(III). Despite many
4
,6
thioantimonates(III) reported, relatively little progress has
been made on the preparation of the three-dimensional (3D)
framework thioantimonates(III) when taking no account of the
7
2 2
weaker secondary Sb−S interactions. Thus far, only a few 3D
6i,7c,d
7a
thioantimonates have been reported, including K Sb S ,
2
4 7
7
b
7c,d
3
trigonal pyramids are
[
[
(
Ni(aepa) ]Sb S , [M(en) ][Sb S ] (M = Co, Ni),
2 4 7 3 12 19
7e 7e
S } ring
8 8
cyclamH ][Sb S ], [Ni(cyclam)][Sb S ], and [Co-
2
4
7
4 7
7e
S
8 8
cyclam)] [cyclamH ] [Sb S ] (0.08 ≤ x ≤ 0.74).
x
2 1−x
4 7
Sb9, Sb(11−13), Sb(15−18), and eight S atoms is also
observed that shares three SbS units with R1. The alternating
arrangements of the two types of {Sb S } rings result in a one-
dimensional (1D) ribbon ([Sb S ] ) along the a axis
On the other hand, usually 3D framework chalcogenides are
3
constructed in the presence of organic amines or metal
complexes as templates or structure-directing agents. It has
been reported that metal (M)-phen/bpy (bpy = 2,2′-
bipyridine) complexes are optically active species, and
integration of such optically active species into the chalcogenide
structures can improve the absorption band structure of the
8
8
6
n−
1
0 18 n
(
Figure 1a). The Sb1S and Sb2S units share one edge (S4 and
4 4
S6), forming a trans-[Sb S ] dimer (Figure 1b). Interconnec-
tions of 1D ribbons of [Sb S ]
bridging [Sb S ] dimers along the c axis lead to a [Sb S ]
layer along the ac plane by sharing four S atoms (S2, S3, S7,
2
6
6n−
by the tetradentate
10 18 n
4n‑
8
2 6 12 20 n
materials. Some chalcogenides templated by M-phen/bpy
8
,9
complexes have been isolated. However, thus far, there is no
report on ultilization of the M-phen complex as templates in
the synthesis of chalcoantimonate(III). Only several inorganic−
organic hybrid manganese thioantimonate compounds were
synthesized, in which the phen directly enters the thioantim-
and S10; Figure 1c). The new eight-membered {Sb S } rings
8
8
(
R3) are observed in the layer because of the [Sb S ] dimers
2 6
3−
bridging 1D ribbons. In addition, two [Sb S ] semicubes
3
6
II
10
onate moiety by chelation to the Mn ion. Here we report on
the synthesis, crystal structure, and characterization of [Ni-
Received: October 17, 2011
Published: March 22, 2012
©
2012 American Chemical Society
3926
dx.doi.org/10.1021/ic202246q | Inorg. Chem. 2012, 51, 3926−3928

Inorganic Chemistry
Communication
Figure 2. Solid-state optical absorption spectrum of 1.
the absorption edge of 1 compared with that in the known low-
dimensional thioantimonates containing metal complexes, such
6
b
6f
as [Ni(dap) ]Sb S (2.44 eV), [Ni(en) ]Sb S (2.49 eV),
3
4
7
3
2 4
6f
and [Ni(en) ]Sb S (2.62 eV).
3
4 7
To further investigate the electronic structure of 1, the band
structure and density of state (DOS) calculations for 1 have
been studied. The methodology used for the band structure
calculations is described in the SI. Compound 1 has a direct
band gap of around 1.12 eV, which is significantly smaller than
the experimental value (2.16 eV). As is well-known, the
generalized gradient approximation does not accurately
describe the eigenvalues of the electronic states, which often
causes quantitative underestimation of the band gaps for
13
semiconductors and insulators. In the DOS curve (Figure S5
in the SI), the conduction bands in the energy range of 0−1.5
eV above the Fermi level (the Fermi level is set at 0.0 eV) are
mainly contributed by Ni 3d, C 2p, and N 2p states, and the
states (1.5−4.5 eV) are dominated by Sb 5p, S 3p, C 2p, and N
6
n−
Figure 1. (a) 1D ribbon of [Sb S ] . (b) trans-[Sb S ] dimer. (c)
10
18
n
2 6
4
n−
[
Sb S ]
layer. (d) [Sb S ] unit. (e) 3D framework of 1 viewed
along the a axis. (f) [Ni(phen)3] cations in the channel.
1
2
20
n
6 11
2+
2
p, while the valence bands from −1.5 eV to the Fermi level are
derived from Sb 5p and S 3p. Therefore, the band gap of
constructed of three SbS trigonal pyramids (Sb(3−5)S and
compound 1 is primarily the result of the charge-transfer
3
3
4−
Sb(6−8)S , respectively) are connected into a [Sb S ] unit by
transition from the anion [Sb18
S
29
]
to the cation [Ni-
] . This is similar to that previously reported for
sulfides containing transition-metal-phen (or bipy) complex-
3
6 11
2+
sharing the S29 atom (Figure 1d). Then the [Sb S ] units
(phen)
3
6
11
4n−
acting as linkers further cross-link the [Sb S ]
layers into a
1
2 20 n
4n−
8d,e
3
D [Sb S ]
8 29 n
anionic network (Figure 1e).
es,
but it is quite different from the observation that the
1
Viewed along the a axis, the 3D anionic network reveals large
optical band gap of antimony sulfides depends more on the
density of the anionic framework (measured by the number of
1
D channels consisting of 48-membered ring {Sb S } (Figure
2
4 24
6a
S1 in the Supporting Information, SI) with dimensions of
approximately 18 × 8.5 Å (Figure 1e). To the best of our
knowledge, such 1D channels are the largest in the known 3D
thioantimonates. The channels are occupied by two distinct
Sb metal atoms per 1000 Å). To further understand the origin
of the optical band gap, we also did theoretical band structure
6c
and DOS calculations of [Ni(dien) ]Sb S10 for comparison,
2 6
which possesses a framework density and a band gap similar to
those of 1. The results (Figures S7 and S8 in the SI) show that
the band gap of [Ni(dien) ]Sb S mainly depends on the
2
+
arrays of [Ni(phen)3] cationic complexes. It is worth noting
that there is only one reported example of an open-framework
2
6 10
2
n−
chalcogenide featuring the [Cd S (SC H ) ]
anionic
network that is templated by M-phen complexes ([Fe-
states of the atoms in the anionic framework, while C, N, and H
contribute little, in contrast to that in the title compound.
Clearly, M-phen in 1 as an optically active species can tune the
optical absorption of the material.
3
2
14
6
5 38 n
+
2+ 8f
(
phen)3]2 and [Ru(phen) ] ). The two crystallographically
3
2
+
distinct [Ni(phen)3] complexes represent Δ(Ni1) and
Λ(Ni2) configurations (Figure 1f), respectively, which are
The room-temperature resistance for 1 is 39.36 kΩ (Figure
7d
similar to those in [Co(en) ][Sb S ] and [M(dap) ]InSb S
3 7
3). When the dimensions are taken into account, the electrical
3
12 19
3
1
2
−3
−1
(
M = Co, Ni). Moreover, another type of channel (15.6 × 9.5
conductivity is 2.9 × 10 S·cm .
Å) with a narrow waist is found along the c axis (Figure S2 in
Simultaneous thermogravimetric analysis (TGA−DSC;
Figure S10 in the SI) from 30 to 460 °C on the powder
(7.669 mg) of compound 1 indicated that it was stable up to
280 °C and then decomposed in one step with a total weight
loss of 23.69%, which was mostly attributed to the removal of
six phen molecules per formula (theoretical weight loss of
25.03%). Interestingly, when 1 was heated up to 850 °C,
hexagonal NiSb, which is a potential Li-ion battery anode
material and is technologically important in secondary high-
the SI). From the topological point of view, the 3D network of
1
2
3
1
(
is pcu (4 ·6 ) topology built upon a six-connected net
Figure S4 in the SI). Furthermore, the [Ni(phen)3]2+
complexes form weak C−H···S hydrogen bonds with the S
atoms of the 3D anionic network (Figure S3 in the SI).
The optical absorption spectrum (Figure 2) of compound 1
indicates a sharp absorption edge at about 2.16 eV, which is
consistent with its red color. There is a noticeable red shift of
3
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Inorganic Chemistry
Communication
Inorg. Chem. 2004, 43, 2914−2921. (f) Stephan, H.-O.; Kanatzidis, M.
G. Inorg. Chem. 1997, 36, 6050−6057. (g) Ko, Y. H.; Tan, K. M.;
Parise, J. B.; Darovsky, A. Chem. Mater. 1996, 8, 493−496. (h) Parise,
J. B.; Ko, Y. H. Chem. Mater. 1992, 4, 1446−1450. (i) Volk, K.;
Bickert, P.; Kolmer, R.; Schafer, H. Z. Naturforsch. B 1979, 34, 380−
3
(
(
2
82.
7) (a) Graf, H. A.; Schafer, H. Z. Naturforsch. B 1972, 27b, 735.
b) Seidlhofer, B.; Djamil, J.; Nather, C.; Bensch, W. Cryst. Growth Des.
̈
011, 11, 5554−5560. (c) Lees, R. J. E.; Powell, A. V.; Chippindale, A.
M. J. Phys. Chem. Solids 2007, 68, 1215−1219. (d) Vaqueiro, P.;
Chippindale, A. M.; Powell, A. V. Inorg. Chem. 2004, 43, 7963−7965.
(e) Powell, A. V.; Lees, R. J. E.; Chippindale, A. M. Inorg. Chem. 2006,
Figure 3. Room-temperature conductivity for 1.
45, 4261−4267.
(
8) (a) Zhang, Y.-P.; Zhang, X.; Mu, W.-Q.; Luo, W.; Bian, G.-Q.;
14
temperature batteries, could be identified in the powder X-ray
diffraction pattern of the residues (Figure S12 in the SI).
In summary, we have presented solvothermal synthesis,
crystal structure, thermal stability, optical and electric
conductivity, and theoretical calculations of a polar 3D
Zhu, Q.-Y.; Dai, J. Dalton Trans. 2011, 40, 9746−9751. (b) Zhang, X.;
Luo, W.; Zhang, Y.-P.; Jiang, J.-B.; Zhu, Q.-Y.; Dai, J. Inorg. Chem.
2
011, 50, 6972−6978. (c) Zhao, J.; Liang, J.-L.; Chen, J.-F.; Pan, Y.-L.;
Zhang, Y.; Jia, D.-X. Inorg. Chem. 2011, 50, 2288−2293. (d) Jiang, J.-
B.; Bian, G.-Q.; Zhang, Y.-P.; Luo, W.; Zhu, Q.-Y.; Dai, J. Dalton Trans.
2
011, 40, 9551−9556. (e) Liu, G.-N.; Guo, G.-C.; Chen, F.; Guo, S.-
(neglecting secondary Sb−S interactions) thioantimonate 1
P.; Jiang, X.-M.; Yang, C.; Wang, M.-S.; Wu, M.-F.; Huang, J.-S.
CrystEngComm 2010, 12, 4035−4037. (f) Zheng, N.-F.; Lu, H.-W.; Bu,
X.-H.; Feng, P.-Y. J. Am. Chem. Soc. 2006, 128, 4528−4529.
with the largest channels, a unique Sb:S ratio (1:1.611), and
metal-phen-templating cations. The results of the calculations
indicate that the band gap of compound 1 is likely determined
by the conduction band edge of cations and the valence band
edge of anions. Further studies will focus on the synthesis and
structure−property relationship of 3D chalcoantimonates
templated by various M-phen (or bipy, M = transition-metal
ions) .
(9) (a) Jia, D.; Zhao, J.; Pan, Y.; Tang, W.; Wu, B.; Zhang, Y. Inorg.
Chem. 2011, 50, 7195−7201. (b) Lei, Z.-X.; Zhu, Q.-Y.; Zhang, X.;
Luo, W.; Mu, W.-Q.; Dai, J. Inorg. Chem. 2010, 49, 4385−4387.
(
10) (a) Lin, Z.-E.; Bu, X.-H.; Feng, P.-Y. Microporous Mesoporous
Mater. 2010, 132, 328−334. (b) Wang, X.; Sheng, T.-L.; Hu, S.-M.; Fu,
R.-B.; Wu, X.-T. Inorg. Chem. Commun. 2009, 12, 399−401.
(
11) Crystal data for 1: C H N Ni S Sb , M = 4319.88,
72 48 12 2 29 18
monoclinic, P2 , a = 11.17374(16) Å, b = 41.2997(5) Å, c =
1
ASSOCIATED CONTENT
Supporting Information
Crystallographic data in CIF format, table of hydrogen-bond
data, calculated band structure, elemental analysis, IR, TGA,
and powder X-ray diffraction patterns. This material is available
free of charge via the Internet at http://pubs.acs.org.
3
■
12.37007(19) Å, β = 106.5568(15)°, V = 5471.76(14) Å , Z = 2, D
calc
−3
−1
*
S
= 2.662 g·cm , F(000) = 4004, μ = 5.293 mm , T = 293(2) K, 25504
reflections measured, 17271 unique reflections (Rint = 0.023), 16490
observed reflections [I > 2σ(I)] with R1 (wR2) = 0.0304 (0.0716), R1
(wR2) = 0.0326 (0.0729) (all data), GOF = 1.024. CCDC 847909.
(
(
12) Zhou, J.; An, L.; Zhang, F. Inorg. Chem. 2011, 50, 415−417.
13) (a) Terki, R.; Bertrand, G.; Aourag, H. Microelectron. Eng. 2005,
8
1, 514−523. (b) Okoye, C. M. I. J. Phys. Condens. Mater. 2003, 15,
AUTHOR INFORMATION
Corresponding Author
E-mail: xyhuang@fjirsm.ac.cn.
■
5945−5958. (c) Godby, R. W.; Schluter, M.; Sham, L. J. Phys. Rev. B
1987, 36, 6497−6500.
(14) (a) Kumari, L.; Li, W.-Z.; Huang, J.-Y.; Provencio, P. P. J. Phys.
Chem. C 2010, 114, 9573−9579. (b) Xie, J.; Zhao, X.-B.; Yu, H.-M.;
Qi, H.; Cao, G.-S.; Tu, J.-P. J. Alloys Compd. 2007, 441, 231−235.
*
ACKNOWLEDGMENTS
■
This work was supported by the Knowledge Innovation
Program of the Chinese Academy of Sciences (Grant KJCX2-
YW-H21), the NNSF of China (Grants 20873149 and
2
2
0803081), and the NSF of Fujian Province (Grants
008J0174 and 2010J01056).
REFERENCES
■
(
(
1) Zheng, N.; Bu, X.; Feng, P. Nature 2003, 426, 428−432.
2) (a) Li, J.-R.; Huang, X.-Y. Dalton Trans. 2011, 40, 4387−4390.
b) Feng, M.-L.; Kong, D.-N.; Xie, Z.-L.; Huang, X.-Y. Angew. Chem.,
Int. Ed. 2008, 47, 8623−8626.
3) Zheng, N.; Bu, X.; Wang, B.; Feng, P. Science 2002, 298, 2366−
369.
(
(
2
(
4) Parise, J. B. Science 1991, 251, 293−294.
(
5) (a) Zhou, J.; Dai, J.; Bian, G.-Q.; Li, C.-Y. Coord. Chem. Rev.
2
009, 253, 1221−1247. (b) Sheldrick, W. S.; Wachhold, M. Coord.
Chem. Rev. 1998, 176, 211−322.
6) (a) Powell, A. V.; Lees, R. J. E.; Chippindale, A. M. J. Phys. Chem.
(
Solids 2008, 69, 1000−1006. (b) Zhou, J.; Bian, G.-Q.; Zhang, Y.; Dai,
J.; Cheng, N. Z. Anorg. Allg. Chem. 2007, 633, 2701−2705. (c) Lees, R.
J. E.; Powell, A. V.; Chippindale, A. M. J. Phys. Chem. Solids 2007, 68,
1
215−1219. (d) Schaefer, M.; Kurowski, D.; Pfitzner, A.; Nather, C.;
Rejai, Z.; Moller, K.; Ziegler, N.; Bensch, W. Inorg. Chem. 2006, 45,
726−3731. (e) Schaefer, M.; Nather, C.; Lehnert, N.; Bensch, W.
3
3
928
dx.doi.org/10.1021/ic202246q | Inorg. Chem. 2012, 51, 3926−3928