Crystal Structure of Ni(NH3)Cl2 and Ni(NH3)Br2
A. Leineweber1), H. Jacobs*
Dortmund, Lehrstuhl fuÈr Anorganische Chemie I, Fachbereich Chemie der UniversitaÈt
H. Ehrenberg
Darmstadt, Institute for Materials Science, Darmstadt University of Technology
Received April 19th, 2000.
Abstract. Ni(NH3)Cl2 and Ni(NH3)Br2 were prepared by
the reaction of Ni(NH3)2X2 with NiX2 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(NH3)Cl2 and Ni(NH3)Br2 are iso-
typic and crystallize in the space group I2/m with Z = 8 and
for Ni(NH3)Cl2: a = 14.8976(3) A Ê , b = 3.56251(6) A
Ê, c=
13.9229(3) AÊ , b = 106.301(1)°; Ni(NH3)Br2: a = 15.5764(1) AÊ,
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-
Die Kristallstruktur von Ni(NH3)Cl2 und Ni(NH3)Br2
InhaltsuÈbersicht. Ni(NH3)Cl2 und Ni(NH3)Br2 wurden durch
Reaktion von Ni(NH3)2X2 mit NiX2 bei 350 °C in einem
Stahlautoklav hergestellt. Mit Synchrotronstrahlung erhal-
tene RoÈntgenpulverdiffraktogramme wurden mit Rietveld-
methoden ausgewertet. Ni(NH3)Cl2 und Ni(NH3)Br2 sind
isotyp. Die Struktur ist im Raumgruppentyp I2/m mit Z = 8
zu beschreiben mit Ni(NH3)Cl2: a = 14,8976(3) A Ê, b=
3,56251(6) AÊ , c = 13,9229(3) A
Ê , b = 106,301(1)°; Ni(NH3)Br2:
a = 15,5764(1) A Ê , b = 3,74346(3) A Ê , c = 14,4224(1) A
Ê , b=
105,894(1)°.
Introduction
Ammines of the general composition M(NH3)nXm
must be regarded as solvates of a salt MXm. 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 20th 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 NH3
are of interest. In contrast to water NH3 cannot serve
as a bridging ligand between two metal atoms. This re-
* Prof. Dr. H. Jacobs,
Fachbereiche Chemie der UniversitaÈt,
Lehrstuhl fuÈr Anorganische Chemie I,
D-44221 Dortmund
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
cally distinct but chemically mostly equivalent polymeric oc-
1
tahedra double chains 1 [NiX3/3X2/2(NH3)] (X = Cl, Br) run-
ning along the short b-axis. The octahedra NiX5NH3 share
common edges therein.
The crystal structures of the ammines Ni(NH3)mX2 with
m = 1, 2, 6 can be derived from that of the halides NiX2
(X = Cl, Br) by successive fragmentation of its CdCl2 like
layers by NH3.
Keywords: Nickel; Nickel ammine halides; Crystal structure
Die Kristallstruktur enthaÈlt zwei kristallographisch inaÈqui-
valente, chemisch jedoch im wesentlichen gleichwertige po-
lymere Oktaederdoppelketten 11 [NiX3/3X2/2(NH3)] (X = Cl,
Br), die entlang der kurzen b-Achse verlaufen. Die Okta-
eder NiX5NH3 sind kantenverknuÈpft.
Die Kristallstrukturen der Ammine Ni(NH3)mX2 mit
m = 1, 2, 6 lassen sich vom wasserfreien Halogenid NiX2
(X = Cl, Br) dadurch herleiten, daû seine CdCl2-artigen
Schichten sukzessive durch NH3 fragmentiert werden.
stricts the topological variety of ammines. Therefore,
ammines are well suited for systematic structural stu-
dies as e. g. performed on Al(NH3)nCl3 with n = 1, 2,
3, 5, 6 [2±5].
Furthermore, the rotational dynamics of the NH3
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
1)
Present address: MPI fuÈr Metallforschung, Seestraûe 92,
D-70174 Stuttgart, Germany
Crystal Structure of Ni(NH3)Cl2 and Ni(NH3)Br2
X = Cl, Br and n = 2, 6 for X = I [1]. This suggests che-
mical and crystallographic similarities for a certain
solvation number. In fact, all hexaammines are isotypic
at ambient temperatures. M(NH3)62+ and X± are ar-
ranged in the motif of a CaF2 type structure as investi-
gated by X-ray [8±10] and neutron [11] diffraction. A
series of the diammines was studied [12] with special
emphasis on Mg(NH3)2X2 [13] and Ni(NH3)2X2 [14]
with X = Cl, Br, I. At ambient temperatures these ma-
terials crystallize in either of two types of structures,
the Cd(NH3)2Cl2 [15] or the Mg(NH3)2Br2 [13] type.
Both contain polymeric chains 1 1
[MX4/2(NH3)2] of
edge-sharing octahedra. They differ only in their ªsec-
ondaryº structure. For Ni(NH3)2X2 [14] with X = Br, I
two modifications exist with structure types cited
above.
No crystal structure determination for a monoam-
mine chloride or bromide of the above mentioned ser-
ies of metals M2+ has yet been published. Cell para-
meters were derived from powder diffraction patterns
for Mn(NH3)Cl2 [16] (tetragonal a = 11.25 A Ê,
Ê
c = 4.95 A, Z = 6 or rhombohedral a = 5.99 A, Ê rubber ring between two metal rings. This sample holder was
a = 48°30', Z = 4) and for Ni(NH3)Cl2 [17] (hexagonal,
Ê , c = 8.21 A
Ê , Z = 6).
a = 8.70 A
In this paper we report on the crystal structures of
two monoammines, Ni(NH3)Cl2 and Ni(NH3)Br2,
based on X-ray powder diffraction studies using syn-
chrotron radiation. Composition and thermodynamic
data of these particular monoammines as well as of
the corresponding hexa- and diammines have been
published previously [18, 19].
Preparation and X-ray Diffraction Studies
Hexaammine nickel halides show slow exchange of
NH3 by H2O indicated by a change of colour from
deep blue to green. Therefore, they were kept in
closed containers. All other ammines and the pure ha-
lides are even more sensitive to moisture and were
handled under inert conditions [20].
Crystalline products of Ni(NH3)6X2 with X = Cl
and Br were prepared from NiCl2 ´ 6 H2O (puri-
ty > 97%, Merck), NiBr2 (99%, Aldrich), NH4Cl
(> 99.8%, Merck), NH4Br (> 99%, Aldrich) and NH3
gas (99.999%, Messer-Griesheim) as described pre-
viously [14]. The hexaammines were placed into a
glass tube attached to dynamic vacuum (p < 0.1 Torr).
Slow increase of temperature to 120 °C yields
Ni(NH3)2X2 [14]. Care must be taken to avoid a vigor-
ous evolution of gas. Further increase of tempera-
tures up to 300 °C finally yields the pure halides. Both
diammine halides and the pure halides were character-
ized by X-ray diffraction on the basis of Guinier film
patterns (FR552, Enraf Nonius, CuKa1 radiation)
[14].
Ni(NH3)2X2 and NiX2 were mixed in an 1 : 1 molar
ratio and heated in a steel autoclave at 350 °C for one
Z. Anorg. Allg. Chem. 2000, 626, 2146±2152
week. This method follows in principle a procedure
which was applied previously to obtain Ni(NH3)Cl2
[21].
The materials were examined by ªconventionalº Guinier
film methods and X-ray powder diffractometry (Sie-
mens D500, CuKa radiation). However, severe overlap of
reflections did not allow a convincing indexing of the com-
plicated diffraction patterns.
Due to the difficulties with conventional X-ray powder
diffraction data we performed high resolution powder dif-
fractometry with synchrotron radiation. The experiments
were carried out on the diffractometer at the beamline B2,
situated at a bending magnet of the storage ring DORIS III,
HASYLAB, Hamburg.
Ni(NH3)Cl2 was examined in Debye-Scherrer geometry
using a secondary monochromator. The diameter of the ca-
pillary was R = 0.5 mm and the wavelength was 1.5409 A Ê.
Based on an assumed packing efficiency of 50% a numerical
treatment of absorption effects was applied.
Ni(NH3)Br2 was examined in transmission geometry in
the form of a thin layer of the material between CaptonÒ
foil fixed by some high vacuum grease and tightened by a
rotated during the measurements in order to improve pow-
der statistics. Again a secondary monochromator was used.
Evaluation of X-ray Diffraction Data, Structure
Solution, and Rietveld Refinement
The diffraction patterns of our samples Ni(NH3)Cl2 and
Ni(NH3)Br2 taken on the Guinier camera or on a ªconven-
tionalº powder diffractometer already revealed additional
reflections either of NiX2 [22, 23] or of Ni(NH3)2X2 [14].
Both samples selected for the measurements with synchro-
tron radiation contained slight amounts of the corresponding
diammines. However, we became aware of the presence of
Ni metal in the sample of Ni(NH3)Cl2 only after the crystal
structure of the ammine chloride was solved.
In the course of the synchrotron radiation measurement
of Ni(NH3)Br2 broad reflections appeared that were not pre-
sent in previous measurements on that particular sample.
The new reflections increased in intensity with measuring
time and were assigned to NH4Br.
Considering the reflections of the impurity phases, the re-
sidual reflections were attributed to the monoammine
phases. The reflection positions suggested that the monoam-
mines are isotypic. However, the previously proposed unit
cells for Mn(NH3)Cl2 and Ni(NH3)Cl2 [16, 17] could not be
successfully used for the indexing of our patterns.
The diffraction patterns taken with synchrotron radiation
(Figure 1 and 2) were indexed using the program ITO [24].
Body-centred monoclinic [25] unit cells (compare Table 1 for
final values from Rietveld refinement) resulted for both
monoammine nickel halides.
The crystal structures of Ni(NH3)X2 were derived by geo-
metric considerations taking into account possible similari-
ties with the crystal structure of Cd(H2O)Cl2 [26].
A final and convincing structural model was set up in the
space group I2/m. The diffraction patterns taken with syn-
chrotron radiation were analysed by Rietveld refinement
using the GSAS package of programs [27]. For both cases
multi-phase refinements were performed considering
2147
 A. Leineweber, H. Jacobs, H. Ehrenberg

Table 1 Details of X-ray powder diffractometry and subse-

quent Rietveld refinement for monoammine nickel(II) ha-
lides

Formula Ni(NH3)Cl2 Ni(NH3)Br2

Formula weight (g ´ mol±1) 146.63 235.53
Diffractometer diffractometer at beamline B2 at a bending
magnet of the storage ring DORIS III,
HASYLAB, Hamburg
Scattering geometry Debye-Scherrer, transmission,
analyzer analyzer
Wavelength (A Ê) 1.5409 1.5289
2 h range (°) 6.00±57.20 7.00±48.04
48.37±57.85a)
2 h stepwidth (in °) 0.008 0.008
Space group I 2/m (No. 12) I 2/m (No. 12)
Cell parametersb) a (A Ê) 14.8976(3) 15.5764(1)
b (AÊ) 3.56251(6) 3.74346(3)
c (AÊ) 13.9229(3) 14.4224(1)
Fig. 1 X-ray diffraction pattern of Ni(NH3)Cl2 recorded on b (°) 106.301(1) 105.894(1)
the diffractometer at the beamline B2 (Synchrotron radia- Volume V (A Ê 3), Z 709.22(3), 8 808.81(1), 8
tion source DORIS, HASYLAB, Hamburg, k = 1.5409 A Ê ). Calculated density (g ´ cm±3) 2.75 3.87
Profile parameters 4 8
Reflection markers: Ni, Ni(NH3)2Cl2, Ni(NH3)Cl2 (from top Background parameters 4 6
to bottom). (+ 4 fixed back-
ground points)
Structural parameters 17 17
Minority phases present Ni(NH3)2Cl2 Ni(NH3)2Br2
(Cmmm) (Pbam)
(4 profile para- (2 profile para-
meters) meters)
content: 12 wt% content: 9 wt%
Ni (Fm 3 m) NH4Br (Pm 3 m)
(1 profile parameter) (4 profile para-
content: 4 wt% meters)
content: 7 wt%
No. of reflections 156 199
RP/wRP 0.098/0.125 0.111/0.142
R(F2) (F2 ³ r(F2)) 0.080 0.104
(123 reflections) (140 reflections)
a)
The region around the reflection (020) was excluded during the refine-
ment.
b)
The standard deviations of cell parameters do not take into account
the errors of the value of the wave lengths.

Fig. 2 X-ray diffraction pattern of Ni(NH3)Br2 taken on

the diffractometer at the beamline B2 (Synchrotron radia-
tion source DORIS, HASYLAB, Hamburg, k = 1.5289 A Ê ).
The region around the reflection (020) was excluded during
the refinement. Reflection markers: NH4Br, Ni(NH3)2Br2,
Ni(NH3)Br2 (from top to bottom).
Ni(NH3)Cl2, Ni(NH3)2Cl2 (Cmmm) [14] and Ni (Fm 3 m)
[28] resp. Ni(NH3)Br2, a-Ni(NH3)2Br2 (Pbam) [14] and
NH4Br (Pm 3 m) [29]. For the impurity phases the positional
parameters were taken from literature and were not refined.
The background was fitted using shifted Chebyshev polyno-
mials with additional fixed background points for
Ni(NH3)Cl2. The reflection profiles of the phases were indi-
vidually fitted by a Simpson's rule integration of pseudo-
Voigt function [30, 31] with correction for asymmetry as im-
plemented in GSAS. For the monoammine phases anisotro-
pic broadening of the reflections was considered. Free re-
finement of the structural and thermal parameters without
consideration of H atoms gave negative thermal parameters
for the N atoms. This was already observed for diammine
nickel chloride and bromide [14] and solved by introducing
H on idealized sites. The same procedure was applied here.
We modelled a disordered distribution of 3 H atoms on
4 sites given by a square (a' = 1.1 A Ê ) with four equidistant
Ê from N.
positions (occupancy 3/4) in a distance of 0.85 A
This is the same geometry we applied for the nickel di-
ammine halides [14] and is constructed using soft constraints.
Due to the low maximum diffraction angles we just con-
sidered one thermal parameter for all non-H atoms and
twice that value for H in the final refinements.
Some differences between observed and calculated reflec-
tion intensities were observed for the Rietveld fit of
Ni(NH3)Br2 (Figure 2). Especially the reflection (020) as the
first reflection (0k0) is observed far to strong. The way of
sample preparation ± a thin layer of Ni(NH3)Br2 powder be-
tween CaptonÒ foil ± may suggest preferred orientation.
However, no convincing model was found. We excluded the
reflection (020) during the refinement in order to avoid the
influences of wrong reflection intensity on the refinement.
Test refinements of powder diffraction data obtained using
Bragg-Brentano geometry and CuKa radiation did not show
any discrepancies for the reflection (020).
Details of data collection and Rietveld refinements are
summarized in Table 1. The final atomic sites and the ther-
mal parameters are given in Table 2, and selected distances
in Table 3.

2148 Z. Anorg. Allg. Chem. 2000, 626, 2146±2152

Crystal Structure of Ni(NH3)Cl2 and Ni(NH3)Br2

Table 2 Refined positional and thermal parameters of

Ni(NH3)Cl2 and Ni(NH3)Br2 (I2/m; normal: X = Cl, italics:
X = Br); sites listed separately for the two crystallographi-
cally different octahedral double chains ± see text

Compound Wyckoff x y z fOCC Ê2

uISO/A
Atom site

chain 1
Ni(1) 4i 0.3486(4) 0 0.3323(4) 1 0.034(1)
0.3492(3) 0 0.3316(3) 1 0.0041(8)
[2] a)
X(1 a) 4i 0.1368(5) 0 0.0515(5) 1 = u(Ni)
0.1385(2) 0 0.0455(2) 1 = u(Ni)
X(1 b)[3] a) 4i 0.1788(5) 0 0.2923(6) 1 = u(Ni)
0.1760(2) 0 0.2983(2) 1 = u(Ni)
N(1) 4i 0.483(1) 0 0.340(2) 1 = u(Ni)
0.478(1) 0 0.341(1) 1 = u(Ni)
1
H(1 a) b)
8j 0.511 0.154 0.385 3/4 = 2 u(Ni) Fig. 3 Octahedral double chains 1 [NiX3/3X2/2(NH3)] resp.
0.507 0.147 0.383 3/4 = 2 u(Ni) 1
H(1 b)b) 8j 0.501 0.155 0.303 3/4 = 2 u(Ni) 1 [CdCl Cl
3/3 2/2 (OH 2 )] as present in Ni(NH3)X2 resp.
0.493 0.147 0.304 3/4 = 2 u(Ni) Cd(H2O)Cl2 with X = Cl, Br. H atoms are not shown.
chain 2
Ni(2) 4i 0.3338(4) 0 0.8480(4) 1 = u(Ni)
0.3320(3) 0 0.8488(3) 1 = u(Ni)
X(2 a) [2] a)
4i 0.0593(5) 0 0.6484(6) 1 = u(Ni) This indicates that the CaptonÒ sample holder was
0.0540(2) 0 0.6487(2) 1 = u(Ni)
X(2 b)[3] a) 4i 0.2791(5) 0 0.6634(5) 1 = u(Ni) not completely tight. Ni(NH3)Cl2 was measured in a
0.2839(2) 0 0.6605(2) 1 = u(Ni) glass capillary without any hydrolysis.
N(2) 4i 0.360(1) 0 0.994(1) 1 = u(Ni)
0.357(1) 0 0.992(1) 1 = u(Ni) Ni(NH3)Cl2 and Ni(NH3)Br2 are isotypic and crys-
b)
H(2 a) 8j 0.331
0.324
0.155
0.147
0.017
0.013
3/4
3/4
= 2 u(Ni)
= 2 u(Ni)
tallize in a yet unknown structure type. We will refer
H(2 b) b)
8j 0.406 0.155 0.019 3/4 = 2 u(Ni) to it as the Ni(NH3)Cl2 type. The main structural fea-
0.396 0.148 0.020 3/4 = 2 u(Ni) 1
tures are octahedra double chains 1 [NiX3/3X2/2(NH3)]
a)
Superscript indicates coordination number by Ni. (Figure 3) which run along the b-axis of the monocli-
b)
Constraints: see text. nic unit cell. The structure contains two crystallographi-
cally different chains. They are, however, very similar
Table 3 Selected distances Ê)
(A in Ni(NH3)Cl2 and in terms of intra-chain bond distances. The two sorts
Ni(NH3)Br2 of chains run along the two inequivalent 21 screw axes
of I2/m with all non-H atoms situated on mirror
Distances Ni(NH3)Cl2 Ni(NH3)Br2
planes. Therefore, the chains have a rod symmetry of
chain 1 21/m. Figure 4 shows a projection of the chains onto
Ni±
2 ´ X[2] a) 2.375(6) 2.549(4)
(010). The ellipses indicate the packing scheme of the
1 ´ X[3] a) 2.432(8) 2.608(5) crystallographically inequivalent chains.
2 ´ X[3] a) 2.439(7) 2.601(4) The presence of two crystallographically distinct
1´N 1.97(2) 1.97(2)
chains may suggest the presence of a missed higher
chain 2 symmetry than I2/m. However, the inter-chain con-
Ni± tacts to X atoms in the coordination spheres of the
2 ´ X[2] a) Ê
2.381(6) A 2.576(4)
1 ´ X[3] a) Ê
2.468(8) A 2.611(5) two different N atoms as given in Figure 5 are essen-
2 ´ X[3] a) Ê
2.424(6) A 2.579(4) tially different.
1´N 1.96(2) 2.00(2)
On calculated positions we included H of the NH3
a)
Superscript indicates coordination number by Ni. groups in the Rietveld refinement. However, this
only takes into account the integral scattering contri-
bution and avoids systematic errors in the structure
refinement. We cannot draw conclusions about the
Discussion real distribution of H on the basis of our X-ray pow-
der diffraction data. However, the NH3 molecules are
The presence of the free halide or the diammine ha- most probably dynamically disordered at ambient
lide may be explained by preparative problems asso- temperatures as they are in the corresponding com-
ciated with the route of synthesis chosen. It has to be pounds Ni(N(H,D)3)6X2 with X = Cl [10], Br [11] as
mentioned that the starting materials were very fine well as in Co(ND3)2Cl2 and Mg(ND3)2Br2 [12] which
powders and had to be handled under inert condi- are isotypic to the corresponding compounds
tions. Ni(NH3)2X2. Especially the diammines with chains
Ammonium bromide, as formed during the diffrac- 1
1 [MX4/2(NH3)2] show a very similar arrangement of
tion experiment of Ni(NH3)Br2 may be regarded as a the NH3 groups arranged like a row of ªpropellersº
product of a hydrolysis reaction along a chain of edge-sharing octahedra (Figure 3
Ni(NH3)Br2 + H2O ® ªNiOHBrº (not observed) + NH4Br. and 6).

Z. Anorg. Allg. Chem. 2000, 626, 2146±2152 2149

 A. Leineweber, H. Jacobs, H. Ehrenberg

Fig. 4 Projection of the structure of Ni(NH3)X2 with X = Cl, Br on (010). Ellipses indicate the packing of the two sorts of crystal-
lographically distinct chains 11 [NiX3/3X2/2(NH3)]. Straight lines: chain 1, broken lines: chain 2. N atoms are labelled for clarity.

Fig. 5 Coordination spheres of N(1) (left) and N(2) (right) in Ni(NH3)Br2 (intra- and inter-chain contacts). The two N sites
and, therefore, the two octahedral double chains are essentially different by their inter-chain contacts, whereas they are chemi-
cally quite similar.

In the diffraction patterns of both compounds the a = 9.25 AÊ , b = 3.78 A

first two observed reflections ± (200) and (002) ± have
a considerably higher FWHM (Full Width at Half
Maximum) than the next reflection (20 2) (the strong-
est reflection, see Figures 1 and 2). This is empirically
modelled by anisotropic reflection profile broadening
improving the fits significantly. We did not analyse in
detail which kind of defects in the considerably aniso-
tropic crystal structure may cause these effects on line
shapes.
The Ni(NH3)Cl2 type structure shows some similari-
ties to the crystal structure of Cd(H2O)Cl2 (Pnma,
Ê , c = 11.89 A
Ê ). The latter also
1
contains octahedral double chains 1 [CdCl3/3Cl2/2(H2O)]
which run along the short b-axis and again are
situated on the 21 screw axis with a rod symmetry
21/m for the non-H atoms. Furthermore, the projec-
tions on (010) schematically given in Figure 7 are very
similar, if black and grey arrows are taken as equiva-
lent. The relation between the two structure types be-
comes obvious by a transformation of the body-
centred to a face-centred monoclinic unit cell of the
Ni(NH3)Cl2 type structures over the diagonals of the
ac-plane to yield aF = 2 ´ 8.65 A Ê , cF = 2 ´ 11.54 A
Ê,

2150 Z. Anorg. Allg. Chem. 2000, 626, 2146±2152

Crystal Structure of Ni(NH3)Cl2 and Ni(NH3)Br2

Fig. 6 Main features of the crystal structures of the known ammines Ni(NH3)mX2 with m = 1, 2, 6 and X = Cl, Br in relation
to the structure of NiX2: A CdCl2 type layer is cut into fragments by the addition of NH3.

Fig. 7 Schematic illustration of the structural differences between Cd(H2O)Cl2 (Pnma, left) and Ni(NH3)Cl2 (I2/m, right),
view along [010]: The octahedral double chains are represented by the symbols of the 21 screw axes with attached black and
grey arrows indicating Ni and N atoms located on the two mirror planes perpendicular to [010] (black and grey, respectively,
mean y = 1/4 and 3/4 for Pnma, y = 0 and 1/2 for I2/m). For Ni(NH3)Cl2 the two crystallographically different 21 screw axes are
indicated by closed and open signs, respectively. In a projection on (010) black and grey arrows become equivalent showing
the similarity of the two structure types. However, the non-equivalence of the 3-dimensional structure caused by different
shifts of the octahedral double chains along [010] becomes obvious by the black and the grey arrows.

Z. Anorg. Allg. Chem. 2000, 626, 2146±2152 2151


bF = 94.0° for Ni(NH3)Cl2 and aF = 2 ´ 9.05 A Ê,
cF = 2 ´ 11.98 AÊ , bF = 94.6° for Ni(NH3)Br2. The differ-
ences between the two structure types are due to the
fact that half of the octahedral double chains present
in Cd(H2O)Cl2 are shifted by b/2 in the Ni(NH3)Cl2
type. This is illustrated schematically in Figure 7. From
that figure it becomes additionally clear, that the in-
equivalence of the octahedral double chains in the
Ni(NH3)Cl2 type is generated by their particular
arrangement but not by structural distortions.
The crystal structures of the known ammines
Ni(NH3)mX2 with m = 1, 2, 6 and X = Cl, Br can all be
derived from that of the halides NiX2 by fragmentiz-
ing its CdCl2 like layers by NH3 molecules. One finds
1 [15] H. MacGillavry, J. M. Bijvoet, Z. Kristallogr. 1936, 94,
octahedral double chains 1 [NiX3/3X2/2(NH3)] for
1 249.
m = 1, single octahedral chains 1 [NiX4/2(NH3)2] for
m = 2 and, finally, a full fragmentation yielding iso-
lated units [Ni(NH3)6]2+ for m = 6 (Figure 6).
Preliminary investigations indicate that
Mg(NH3)Cl2, Mg(NH3)Br2 and Fe(NH3)Cl2 are prob-
ably isostructural with the nickel compounds pre-
sented here.
Acknowledgement: We thank the Fonds der Chemischen In-
dustrie, the Deutsche Forschungsgemeinschaft and the Bun-
desministerium fuÈr Bildung, Wissenschaft, Forschung und
Technologie (JA5DOR) for financial support of this work.
The beamline B2 at HASYLAB is supported by this minis-
try under grant no. O5 SM8RDA.
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