镍氨配合物Ni(NH3)Cl2和Ni(NH3)Br2的晶体结构研究
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"这篇学术论文探讨了Ni(NH3)Cl2和Ni(NH3)Br2两种化合物的晶体结构，它们是通过镍氨盐Ni(NH3)2X2与镍卤化物NiX2在350°C高温下反应生成的。这两种化合物在I2/m空间群中结晶，具有相同的晶体类型，晶胞参数有所不同。Ni(NH3)Cl2的晶胞参数为a=14.8976(3)Å, b=3.56251(6)Å, c=13.9229(3)Å, β=106.301(1)°，而Ni(NH3)Br2的相应参数为a=15.5764(1)Å, b=3.74346(3)Å, c=14.4224(1)Å, β=105.894(1)°。晶体结构是通过同步辐射的X射线粉末衍射技术确定，并用Rietveld方法进行精炼。
这两种物质的晶体结构主要由两个化学上几乎等价但晶体学上不同的多聚八面体双链组成，这些八面体沿短b轴方向排列。每个八面体NiX5NH3共享边缘，形成了连续的链状结构。X代表卤素离子Cl或Br。
论文还提到，这些氨镍卤化物的晶体结构可以衍生自不同氨配位数m（m=1,2,6）的氨镍配合物Ni(NH3)mX2。这表明，氨分子的数量和种类对镍的配位环境以及整体晶体结构有显著影响。通过比较这些结构，可以深入理解配位化学中的结构-性质关系，特别是在过渡金属配合物领域。这些研究结果对于合成新型功能材料、催化剂设计以及理解化学反应机理具有重要意义。
此外，使用同步辐射的X射线粉末衍射技术是确定复杂晶体结构的强大工具，它能够提供高分辨率的数据，使得研究人员能够精确地分析和理解这些晶体的微细结构。Rietveld精炼方法则是一种处理粉末衍射数据的有效手段，它可以用来确定晶体结构参数，包括原子的位置、晶胞参数以及晶格动力学效应。
这篇论文详细研究了Ni(NH3)Cl2和Ni(NH3)Br2的晶体结构，揭示了它们的结构特性，这对进一步研究过渡金属配合物的结构多样性及其在化学、材料科学等领域的应用提供了宝贵的信息。"
Crystal Structure of Ni(NH
3
)Cl
2
and Ni(NH
3
)Br
2
A. Leineweber
1)
, H. Jacobs*
Dortmund, Lehrstuhl fuÈ r Anorganische Chemie I, Fachbereich Chemie der UniversitaÈt
H. Ehrenberg
Darmstadt, Institute for Materials Science, Darmstadt University of Technology
Received April 19th, 2000.
Abstract. Ni(NH
3
)Cl
2
and Ni(NH
3
)Br
2
were prepared by
the reaction of Ni(NH
3
)
2
X
2
with NiX
2
at 350 °C in a steel
autoclave. The crystal structures were determined by X-ray
powder diffraction using synchrotron radiation and refined
by Rietveld methods. Ni(NH
3
)Cl
2
and Ni(NH
3
)Br
2
are iso-
typic and crystallize in the space group I2/m with Z = 8 and
for Ni(NH
3
)Cl
2
: a = 14.8976(3) A
Ê
, b = 3.56251(6) A
Ê
, c =
13.9229(3) A
Ê
, b = 106.301(1)°; Ni(NH
3
)Br
2
: a = 15.5764(1) A
Ê
,
b = 3.74346(3) A
Ê
, c = 14.4224(1) A
Ê
, b = 105.894(1)°.
The crystal structures are built up by two crystallographi-
cally distinct but chemically mostly equivalent polymeric oc-
tahedra double chains
1
1
[NiX
3/3
X
2/2
(NH
3
)] (X = Cl, Br) run-
ning along the short b-axis. The octahedra NiX
5
NH
3
share
common edges therein.
The crystal structures of the ammines Ni(NH
3
)
m
X
2
with
m = 1, 2, 6 can be derived from that of the halides NiX
2
(X = Cl, Br) by successive fragmentation of its CdCl
2
like
layers by NH
3
.
Keywords: Nickel; Nickel ammine halides; Crystal structure
Die Kristallstruktur von Ni(NH
3
)Cl
2
und Ni(NH
3
)Br
2
Inhaltsu
È
bersicht. Ni(NH
3
)Cl
2
und Ni(NH
3
)Br
2
wurden durch
Reaktion von Ni(NH
3
)
2
X
2
mit NiX
2
bei 350 °C in einem
Stahlautoklav hergestellt. Mit Synchrotronstrahlung erhal-
tene RoÈntgenpulverdiffraktogramme wurden mit Rietveld-
methoden ausgewertet. Ni(NH
3
)Cl
2
und Ni(NH
3
)Br
2
sind
isotyp. Die Struktur ist im Raumgruppentyp I2/m mit Z =8
zu beschreiben mit Ni(NH
3
)Cl
2
: a = 14,8976(3) A
Ê
, b =
3,56251(6) A
Ê
, c = 13,9229(3) A
Ê
, b = 106,301(1)°; Ni(NH
3
)Br
2
:
a = 15,5764(1) A
Ê
, b = 3,74346(3) A
Ê
, c = 14,4224(1) A
Ê
, b =
105,894(1)°.
Die Kristallstruktur enthaÈlt zwei kristallographisch inaÈqui-
valente, chemisch jedoch im wesentlichen gleichwertige po-
lymere Oktaederdoppelketten
1
1
[NiX
3/3
X
2/2
(NH
3
)] (X = Cl,
Br), die entlang der kurzen b-Achse verlaufen. Die Okta-
eder NiX
5
NH
3
sind kantenverknuÈ pft.
Die Kristallstrukturen der Ammine Ni(NH
3
)
m
X
2
mit
m = 1, 2, 6 lassen sich vom wasserfreien Halogenid NiX
2
(X = Cl, Br) dadurch herleiten, daû seine CdCl
2
-artigen
Schichten sukzessive durch NH
3
fragmentiert werden.
Introduction
Ammines of the general composition M(NH
3
)
n
X
m
must be regarded as solvates of a salt MX
m
. In most
cases discrete solvation numbers n exist. These can
e. g. be determined by measuring the decomposition
pressures over the solids as a function of n and tem-
perature. Many of such studies were carried out in the
early 20
th
century and summarized by Jander, Spandau
and Addison [1].
Ammines are of interest for several reasons. First of
all, details of the stepwise solvation of a salt by NH
3
are of interest. In contrast to water NH
3
cannot serve
as a bridging ligand between two metal atoms. This re-
stricts the topological variety of ammines. Therefore,
ammines are well suited for systematic structural stu-
dies as e. g. performed on Al(NH
3
)
n
Cl
3
with n =1, 2,
3, 5, 6 [2±5].
Furthermore, the rotational dynamics of the NH
3
molecules fixed by coordinative bonds to metal atoms,
often accompanied by order-disorder transformations
(e. g. in hexaammine metal(II) halides [6]) were exten-
sively studied. One important aspect in these studies
is the role of hydrogen bonds N±H ´ ´ ´ X in ammines
[7].
For the group of ammines with M = Mg, Mn, Fe,
Co, Ni (with m = 2) and X = Cl, Br, I strong similari-
ties are found as the different systems show similar
sets of solvation numbers with n £ 6: n = 1, 2, 6 for
2146 Ó WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000 0044±2313/00/6262146±2152 $ 17.50+.50/0 Z. Anorg. Allg. Chem. 2000, 626, 2146±2152
1)
Present address: MPI fuÈ r Metallforschung, Seestraûe 92,
D-70174 Stuttgart, Germany
* Prof. Dr. H. Jacobs,
Fachbereiche Chemie der UniversitaÈt,
Lehrstuhl fuÈr Anorganische Chemie I,
D-44221 Dortmund
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