合成与计算：抗银(III)氯化二叠氮化物SbCl(N3)2的结构特征
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本文是一篇发表于2000年9月的学术论文，由Thomas M. Klapötke、Heinrich Noeth、Thomas Schuett和Marcus Warchold四位作者共同完成，他们来自德国慕尼黑路德维希-马克西米利安大学化学系。研究的焦点是合成、表征、晶体结构以及通过混合密度泛函理论（hybrid DFT）计算的一种新型化合物——Antimony(III) Chloride Diazide (SbCl(N3)2)。
在实验部分，研究人员通过将两当量的钠叠氮化物与SbCl3在二氯甲烷中反应来制备SbCl(N3)2。这表明合成方法涉及一种配位化学反应，其中叠氮化钠提供电子对与氯化锑形成配合物。
晶体结构分析是研究的核心，结果显示SbCl(N3)2晶体属于单斜晶系（monoclinic space group C2/c），其晶格参数为a=11.694(4) Å, b=7.751(4) Å, c=12.241(5) Å, β=100.45(1)°，每个晶胞中含有8个分子单元。这种结构揭示了SbCl(N3)2分子之间的相互作用，形成了链状结构。
为了进一步理解这种化合物的性质，作者利用了Raman光谱和红外光谱技术，测量了分子的振动频率，并将其与计算结果进行了比较。通过这种方式，他们能够精确地确定化合物中各个原子振动模式的特性，这对于理解化合物的物理和化学性质至关重要。
混合密度泛函理论（hybrid DFT）是一种计算化学工具，它结合了基础的DFT方法与经验的hartree-fock（HF）成分，以提高对复杂体系的预测准确性。在这项研究中，作者利用这一技术对SbCl(N3)2的结构和性质进行了计算机模拟，这些计算结果与实验证据相结合，提供了深入的结构理解。
关键词：Antimony（锑）、Azides（叠氮化物）、Crystal structure（晶体结构）、Hybrid DFT（混合密度泛函理论）。这项工作不仅有助于理解Antimony(III) Chloride Diazide的独特性质，还为设计和合成类似的化合物以及理论预测提供了有价值的数据和方法。
Synthesis, Characterization, Crystal Structure, and hybrid DFT Computation
of Antimony(III) Chloride Diazide, SbCl(N
3
)
2
Thomas M. Klapo
È
tke*, Heinrich No
È
th, Thomas Schu
È
tt, and Marcus Warchold
Munich, Department of Chemistry, Ludwig-Maximilians University
Received September 11th, 2000.
Abstract. SbCl(N
3
)
2
was synthesized by the reaction of two
equivalents of sodium azide with SbCl
3
in CH
2
Cl
2
.The
structure of the compound was determined by X-ray struc-
ture determination. SbCl(N
3
)
2
crystallizes in the monoclinic
space group C2/c with a = 11.694(4), b = 7.751(4) and
c = 12.241(5) A
Ê
, b = 100.45(1)°, with 8 formula units per unit
cell. The SbCl(N
3
)
2
molecules show interactions to form
chains. The frequencies obtained by Raman and infrared
spectroscopy were assigned to the normal modes of the
SbCl(N
3
)
2
molecules in comparison with computational re-
sults.
Keywords: Antimony; Azides; Crystal structure; hybrid DFT
Synthese, Charakterisierung, Kristallstruktur und hybrid-DFT-Berechnung
von Antimon(III)-chlorid-diazid, SbCl(N
3
)
2
Inhaltsu
È
bersicht. SbCl(N
3
)
2
wurde durch die Umsetzung von
zwei Øquivalenten Natriumazid mit SbCl
3
in CH
2
Cl
2
synthe-
tisiert. Die Struktur der Verbindung wurde durch RoÈntgen-
strukturanalyse bestimmt. SbCl(N
3
)
2
kristallisiert in der mo-
noklinen Raumgruppe C2/c mit den Gitterkonstanten
a = 11.694(4), b = 7.751(4) und c = 12.241(5) A
Ê
, b = 100.45(1)°,
mit 8 Formeleinheiten in der Elementarzelle. Die SbCl(N
3
)
2
-
MolekuÈ le bilden Ketten durch zwischenmolekulare Wechsel-
wirkungen. Die durch Raman- und Infrarot-Spektroskopie
erhaltenen Banden wurden den Normalschwingungen der
SbCl(N
3
)
2
-MolekuÈ le zugeordnet und mit berechneten Ergeb-
nissen verglichen.
Introduction
Recently we have been studying the reactions of var-
ious group 15 elements with silver azide, sodium azide
or trimethylsilyl azide [1±4]. In 1996 we reported on
the synthesis of the first binary antimony azide species
Sb(N
3
)
3
[5]. However we were unable to grow suitable
crystals for X-ray diffraction of Sb(N
3
)
3
. The structural
characterization of antimony azide species was so far
only possible when organic ligands were present, except
for the ternary antimony(V) species (SbCl
4
N
3
)
2
[6].
The structure of the molecules {[(PN
t
Bu)
2
(N
t
Bu)
2
]-
SbN
3
} [7], [(CH
3
)
3
SbN
3
]
2
O [8], Me
2
SbN
3
[9] and
[(C
6
H
5
)
3
SbN
3
]
2
O [10] could be solved by X-ray diffrac-
tion. The weak crystallization tendency of Sb(N
3
)
3
prompted us to find a better crystallizing antimony
azide species having a minor azide content. Here we re-
port on the synthesis, the spectroscopic properties and
the crystal structure of the first mixed halide pseudoha-
lide antimony(III) species, SbCl(N
3
)
2
.
Results and Discussion
SbCl(N
3
)
2
was prepared by the reaction of two
equivalents of sodium azide with SbCl
3
in CH
2
Cl
2
at
room temperature. After filtration and removing the
solvent under dynamic vacuum a colorless solid
remained. Recrystallization from the same solvent at
±30 °C gave single crystals suitable for the X-ray
measurements.
Crystal Structure of SbCl(N
3
)
2
The crystal structure at ±90 °C reveals that SbCl(N
3
)
2
forms isolated molecules in which the antimony atom
including the lone pair of electron is surrounded in a
pyramidal fashion by two nitrogen atoms and one
chlorine atom. The N1±Sb±N4 angle is 90.5(3)°, the
N1±Sb±Cl1 angle is 91.0(2)° and the N4±Sb±Cl1 angle
is 88.7(2)°. The molecular unit is shown in Fig. 1. Ta-
ble 1 shows the experimental and calculated bond
lengths and angles of the SbCl(N
3
)
2
unit. The Sb±N
distances (2.15 A
Ê
) are in good agreement with the
reported Sb±N distances of other antimony azides
[6±10].
The azide ligands in SbCl(N
3
)
2
are different. One
azide unit shows a ªnormalº behavior with an N4±N5
distance of 1.22(1) A
Ê
and an N5±N6 distance of
1.13(1) A
Ê
, while the other azide unit shows unrealistic
Z. Anorg. Allg. Chem. 2001, 627, 81±84 Ó WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001 0044±2313/01/62781±84 $ 17.50+.50/0 81
* Prof. Dr. Thomas M. KlapoÈ tke,
Department of Chemistry, Ludwig-Maximilians-University,
Butenandtstr. 5±13 (D),
D-81377 Munich, Germany
e-mail: tmk@cup.uni-muenchen.de
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