固态结构：AsCl5和SbCl5的晶体研究

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"Solid State Structures of AsCl5 and SbCl5" 本文是一篇关于AsCl5（砷五氯化物）和SbCl5（锑五氯化物）固态结构的学术论文，作者是Silvia Haupt和Konrad Seppelt，来自柏林自由大学的化学研究所。文章于2001年9月25日接收。在固态下，AsCl5呈现一个三棱锥形结构，其中As-Cl键的等价键长为210.6和211.9 picometers（pm），非等价键长为220.7 pm，空间群为Pmmn，晶格参数为a = 706.2(1) pm，b = 760.3(2) pm，c = 623.3(1) pm。这种结构表明AsCl5分子在固态中具有对称性的排列，形成一个稳定的三棱锥形网络。另一方面，SbCl5存在两种不同的形态。在254.1°C以上，它也呈现三棱锥形结构，Sb-Cl等价键长为227.0 pm，非等价键长为233.3 pm，空间群为P63/mmc，晶格参数为a = 741.4(1) pm，c = 799.0(2) pm。然而，在254.1°C以下，SbCl5经历可逆转变，形成一个双氯桥联的二聚体，这个结构由共享边缘的两个八面体组成，空间群为P21/c，晶格参数为a = 952.4(1) pm，b = 1189.9(1) pm，c = 1219.7(1) pm，β = 108.27(1)度。有趣的是，当存在水时，AsCl5的形成受到阻碍，可能是因为水与AsCl5反应或影响其结晶过程。文章还提到了两种含有八面体离子的盐，这暗示了在不同条件下AsCl5或SbCl5可以与其他物质形成复合物或衍生物。这篇论文的研究对于理解AsCl5和SbCl5的化学性质、它们在固态下的稳定性和可能的反应路径具有重要意义。此外，这些结构信息对于材料科学、无机化学以及晶体工程等领域都具有参考价值，特别是对于设计新的功能材料或催化剂时，了解这些化合物的精确结构是至关重要的。

Artikel

Solid State Structures of AsCl

and SbCl

Silvia Haupt and Konrad Seppelt*

Berlin, Institut für Chemie der Freien Universität

Received September 25

, 2001.

Abstract. Arsenic pentachloride has a trigonal bipyramidal struc-

ture in the solid state with As-Cl

5 210.6,211.9 pm, As-Cl

220.7 pm, space group Pmmn, a 5 706.2 (1); b 5 760.3 (2), c 5

623.3 (1) pm. Antimony pentachloride exists in two modifications:

above 2 54.1°C it is also trigonal bipyramidal with Sb-Cl

5 227.0

and Sb-Cl

5 233.3 pm, space group P6

/mmc, a 5 741.4 (1),

c 5 799.0(2)pm. Below 254.1°C it changes reversibly into a double

chlorine bridged dimer resulting in an edge shared double octa-

hedral structure, space group P2

/c, a 5 952.4 (1), b 5 1189.9 (1),

c 5 1219.7 (1) pm, β 5108,27 (1): In presence of water the forma-

tion of AsCl

is hindered, two salts containing the octahedral anion

Die Festkörperstrukturen von AsCl

und von SbCl

Inhaltsübersicht. Arsenpentachlorid ist im festen Zustand trigonal-

bipyramidal aufgebaut, As-Cl

5 210.6, 211.9 pm und As-Cl

220.7 pm, Raumgruppe Pmmn, a 5 706.2 (1), b 5 760.3 (2), c 5

623.3 (1) pm. Antimonpentachlorid kommt in zwei Modifikationen

vor: oberhalb 254.1°C ist es ebenfalls trigonal-bipyramidal aufge-

baut, Sb-Cl

äq

5 227.0 und Sb-Cl

233.3 pm, Raumgruppe

/mmc, a 5 741.4 (1), c 5 794.0 (2) pm. Unterhalb 2 54.1°C

lagert es sich reversibel um in ein doppelt chlorverbrücktes Dimer

mit einer kantenverknüpften doppeloktahedrischen Struktur,

Raumgruppe P2

/c, a5 952.4 (1), b 5 1189.9 (1), c 5 1219.7 (1)

Introduction

AsCl

was prepared approximately 160 years after the prep-

aration of PCl

and SbCl

[1]. It is unstable with respect to

AsCl

and Cl

. It is now textbook knowledge that the rela-

tive instability of the highest oxidation state of the third

period of main group elements is due to incomplete shield-

ing of the nucleus by the first filled shell of d-electrons. The

relative instability of BrO

and its late preparation is the

other historic example [2]. AsCl

has originally been pre-

pared from AsCl

and Cl

under uv irradiation. The proof

for its existence stems mainly from the characteristic raman

spectrum, which could easily be assigned assuming a trig-

onal bipyramidal (D

) structure [1].

The Raman spectra of dissolved and solid AsCl

are

quite similar, and the conclusion was drawn that solid AsCl

*Prof. Dr. K. Seppelt

Institut für Anorg. und Analyt. Chemie der Freien Universität Berlin

Fabeckstraße 34-36

D-14195 Berlin

FAX: Int. code 1 (30)83854289

e-mail: seppelt@chemie.fu-berlin.de

Z. Anorg. Allg. Chem. 2002, 628,7292734  WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 004422313/02/628/7292734 $ 20.001.50/0

729

AsCl

have been isolated, [(H

)

AsCl

(Cl

)

], space group

C2/c, a5 1416.9 (2), b 5 1316.6 (3), c 5 1215.3 (2) pm, β 5 94.96

(1)°, and [(H

)(AsCl

)·AsOCl

], space group P2

/n, a 5 771.6

(3), b 5 904.5 (3), c 5 2140.7(2)pm, β 5 100.21(1). The AsOCl

moiety in this compound appears as a monomer, in contrast to

pure AsOCl

, which is a doubly oxygen bridged dimer in the

solid state.

Keywords: Arsenic; Antimony; Arsenic pentachloride; Antimony

pentachloride; Crystal structure

pm, β 5 108.27 (1)°. In Gegenwart von Wasser bildet sich kein

AsCl

, dagegen können zwei Salze isoliert werden, die das oktahe-

drische AsCl

enthalten: [(H

)

AsCl

(Cl

)

], Raumgruppe

C2/c, a 5 1416.9 (2), b 5 1316.6 (3), c 5 1215.3 (2) pm,

β 5 94.96 (1)°, und [(H

)(AsCl

)·AsOCl

], Raumgruppe P2

/n,

a 5 771,6 (3), b 5 904.5 (3), c 5 2140.7 (7) pm, β 5 100.21(1)°.

Die AsOCl

Einheit in dieser Verbindung ist monomer, im Gegen-

satz zum doppelt sauerstoffüberbrückten Dimer des reinen AsOCl

im festen Zustand.

will retain the trigonal bipyramidal structure which is

clearly the expected structure for the isolated molecule. The

similarity of the molecular and solid state structure came

as a surprise, since PCl

as a molecule has a trigonal bipyr-

amidal structure [3], but in the solid state it crystallizes as

[(PCl

)(PCl

)] [4]. SbCl

, also trigonal bipyramidal as a

molecule [5], has the same structure in the solid state, ac-

cording to an early x-ray analysis [6]. But changes in the

vibrational, n.q.r, and Sb-Mößbauer spectra at low tem-

peratures have already previously been interpreted as a di-

merisation into [Cl

SbCl

], namely a double chlorine

bridged (two edge sharing octahedral) structure like in

[7, 12]. The aim of the present work has been to

establish the solid state structures of AsCl

and SbCl

with certainty.

Results

AsCl

The original preparation of AsCl

by uv irradiation of

AsCl

/Cl

solutions is easily reproducible, if water and with

this HCl is strictly avoided. This has been outlined before [1].

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