You are on page 1of 7

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 cally distinct but chemically mostly equivalent polymeric oc-
1
the reaction of Ni(NH3)2X2 with NiX2 at 350 °C in a steel tahedra double chains 1 [NiX3/3X2/2(NH3)] (X = Cl, Br) run-
autoclave. The crystal structures were determined by X-ray ning along the short b-axis. The octahedra NiX5NH3 share
powder diffraction using synchrotron radiation and refined common edges therein.
by Rietveld methods. Ni(NH3)Cl2 and Ni(NH3)Br2 are iso- The crystal structures of the ammines Ni(NH3)mX2 with
typic and crystallize in the space group I2/m with Z = 8 and m = 1, 2, 6 can be derived from that of the halides NiX2
for Ni(NH3)Cl2: a = 14.8976(3) A Ê , b = 3.56251(6) A
Ê, c= (X = Cl, Br) by successive fragmentation of its CdCl2 like
13.9229(3) AÊ , b = 106.301(1)°; Ni(NH3)Br2: a = 15.5764(1) AÊ, layers by NH3.
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- Keywords: Nickel; Nickel ammine halides; Crystal structure

Die Kristallstruktur von Ni(NH3)Cl2 und Ni(NH3)Br2


InhaltsuÈbersicht. Ni(NH3)Cl2 und Ni(NH3)Br2 wurden durch Die Kristallstruktur enthaÈlt zwei kristallographisch inaÈqui-
Reaktion von Ni(NH3)2X2 mit NiX2 bei 350 °C in einem valente, chemisch jedoch im wesentlichen gleichwertige po-
Stahlautoklav hergestellt. Mit Synchrotronstrahlung erhal- lymere Oktaederdoppelketten 11 [NiX3/3X2/2(NH3)] (X = Cl,
tene RoÈntgenpulverdiffraktogramme wurden mit Rietveld- Br), die entlang der kurzen b-Achse verlaufen. Die Okta-
methoden ausgewertet. Ni(NH3)Cl2 und Ni(NH3)Br2 sind eder NiX5NH3 sind kantenverknuÈpft.
isotyp. Die Struktur ist im Raumgruppentyp I2/m mit Z = 8 Die Kristallstrukturen der Ammine Ni(NH3)mX2 mit
zu beschreiben mit Ni(NH3)Cl2: a = 14,8976(3) A Ê, b= m = 1, 2, 6 lassen sich vom wasserfreien Halogenid NiX2
3,56251(6) AÊ , c = 13,9229(3) A
Ê , b = 106,301(1)°; Ni(NH3)Br2: (X = Cl, Br) dadurch herleiten, daû seine CdCl2-artigen
a = 15,5764(1) A Ê , b = 3,74346(3) A Ê , c = 14,4224(1) A
Ê , b= Schichten sukzessive durch NH3 fragmentiert werden.
105,894(1)°.

Introduction stricts the topological variety of ammines. Therefore,


ammines are well suited for systematic structural stu-
Ammines of the general composition M(NH3)nXm dies as e. g. performed on Al(NH3)nCl3 with n = 1, 2,
must be regarded as solvates of a salt MXm. In most 3, 5, 6 [2±5].
cases discrete solvation numbers n exist. These can Furthermore, the rotational dynamics of the NH3
e. g. be determined by measuring the decomposition molecules fixed by coordinative bonds to metal atoms,
pressures over the solids as a function of n and tem- often accompanied by order-disorder transformations
perature. Many of such studies were carried out in the (e. g. in hexaammine metal(II) halides [6]) were exten-
early 20th century and summarized by Jander, Spandau sively studied. One important aspect in these studies
and Addison [1]. is the role of hydrogen bonds N±H ´ ´ ´ X in ammines
Ammines are of interest for several reasons. First of [7].
all, details of the stepwise solvation of a salt by NH3 For the group of ammines with M = Mg, Mn, Fe,
are of interest. In contrast to water NH3 cannot serve Co, Ni (with m = 2) and X = Cl, Br, I strong similari-
as a bridging ligand between two metal atoms. This re- ties are found as the different systems show similar
sets of solvation numbers with n £ 6: n = 1, 2, 6 for
* Prof. Dr. H. Jacobs,
Fachbereiche Chemie der UniversitaÈt, 1)
Lehrstuhl fuÈr Anorganische Chemie I, Present address: MPI fuÈr Metallforschung, Seestraûe 92,
D-44221 Dortmund D-70174 Stuttgart, Germany

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

X = Cl, Br and n = 2, 6 for X = I [1]. This suggests che- week. This method follows in principle a procedure
mical and crystallographic similarities for a certain which was applied previously to obtain Ni(NH3)Cl2
solvation number. In fact, all hexaammines are isotypic [21].
at ambient temperatures. M(NH3)62+ and X± are ar-
The materials were examined by ªconventionalº Guinier
ranged in the motif of a CaF2 type structure as investi- film methods and X-ray powder diffractometry (Sie-
gated by X-ray [8±10] and neutron [11] diffraction. A mens D500, CuKa radiation). However, severe overlap of
series of the diammines was studied [12] with special reflections did not allow a convincing indexing of the com-
emphasis on Mg(NH3)2X2 [13] and Ni(NH3)2X2 [14] plicated diffraction patterns.
with X = Cl, Br, I. At ambient temperatures these ma- Due to the difficulties with conventional X-ray powder
terials crystallize in either of two types of structures, diffraction data we performed high resolution powder dif-
the Cd(NH3)2Cl2 [15] or the Mg(NH3)2Br2 [13] type. fractometry with synchrotron radiation. The experiments
Both contain polymeric chains 1 1
[MX4/2(NH3)2] of were carried out on the diffractometer at the beamline B2,
edge-sharing octahedra. They differ only in their ªsec- situated at a bending magnet of the storage ring DORIS III,
HASYLAB, Hamburg.
ondaryº structure. For Ni(NH3)2X2 [14] with X = Br, I
Ni(NH3)Cl2 was examined in Debye-Scherrer geometry
two modifications exist with structure types cited using a secondary monochromator. The diameter of the ca-
above. pillary was R = 0.5 mm and the wavelength was 1.5409 A Ê.
No crystal structure determination for a monoam- Based on an assumed packing efficiency of 50% a numerical
mine chloride or bromide of the above mentioned ser- treatment of absorption effects was applied.
ies of metals M2+ has yet been published. Cell para- Ni(NH3)Br2 was examined in transmission geometry in
meters were derived from powder diffraction patterns the form of a thin layer of the material between CaptonÒ
for Mn(NH3)Cl2 [16] (tetragonal a = 11.25 A Ê, foil fixed by some high vacuum grease and tightened by a
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, rotated during the measurements in order to improve pow-
Ê , c = 8.21 A
Ê , Z = 6). der statistics. Again a secondary monochromator was used.
a = 8.70 A
In this paper we report on the crystal structures of
two monoammines, Ni(NH3)Cl2 and Ni(NH3)Br2, Evaluation of X-ray Diffraction Data, Structure
based on X-ray powder diffraction studies using syn- Solution, and Rietveld Refinement
chrotron radiation. Composition and thermodynamic The diffraction patterns of our samples Ni(NH3)Cl2 and
data of these particular monoammines as well as of Ni(NH3)Br2 taken on the Guinier camera or on a ªconven-
the corresponding hexa- and diammines have been tionalº powder diffractometer already revealed additional
published previously [18, 19]. 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
Preparation and X-ray Diffraction Studies diammines. However, we became aware of the presence of
Ni metal in the sample of Ni(NH3)Cl2 only after the crystal
Hexaammine nickel halides show slow exchange of structure of the ammine chloride was solved.
NH3 by H2O indicated by a change of colour from In the course of the synchrotron radiation measurement
deep blue to green. Therefore, they were kept in of Ni(NH3)Br2 broad reflections appeared that were not pre-
closed containers. All other ammines and the pure ha- sent in previous measurements on that particular sample.
lides are even more sensitive to moisture and were The new reflections increased in intensity with measuring
handled under inert conditions [20]. time and were assigned to NH4Br.
Crystalline products of Ni(NH3)6X2 with X = Cl Considering the reflections of the impurity phases, the re-
sidual reflections were attributed to the monoammine
and Br were prepared from NiCl2 ´ 6 H2O (puri-
phases. The reflection positions suggested that the monoam-
ty > 97%, Merck), NiBr2 (99%, Aldrich), NH4Cl mines are isotypic. However, the previously proposed unit
(> 99.8%, Merck), NH4Br (> 99%, Aldrich) and NH3 cells for Mn(NH3)Cl2 and Ni(NH3)Cl2 [16, 17] could not be
gas (99.999%, Messer-Griesheim) as described pre- successfully used for the indexing of our patterns.
viously [14]. The hexaammines were placed into a The diffraction patterns taken with synchrotron radiation
glass tube attached to dynamic vacuum (p < 0.1 Torr). (Figure 1 and 2) were indexed using the program ITO [24].
Slow increase of temperature to 120 °C yields Body-centred monoclinic [25] unit cells (compare Table 1 for
Ni(NH3)2X2 [14]. Care must be taken to avoid a vigor- final values from Rietveld refinement) resulted for both
ous evolution of gas. Further increase of tempera- monoammine nickel halides.
tures up to 300 °C finally yields the pure halides. Both The crystal structures of Ni(NH3)X2 were derived by geo-
metric considerations taking into account possible similari-
diammine halides and the pure halides were character-
ties with the crystal structure of Cd(H2O)Cl2 [26].
ized by X-ray diffraction on the basis of Guinier film A final and convincing structural model was set up in the
patterns (FR552, Enraf Nonius, CuKa1 radiation) space group I2/m. The diffraction patterns taken with syn-
[14]. chrotron radiation were analysed by Rietveld refinement
Ni(NH3)2X2 and NiX2 were mixed in an 1 : 1 molar using the GSAS package of programs [27]. For both cases
ratio and heated in a steel autoclave at 350 °C for one multi-phase refinements were performed considering

Z. Anorg. Allg. Chem. 2000, 626, 2146±2152 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- 4 sites given by a square (a' = 1.1 A Ê ) with four equidistant
tion source DORIS, HASYLAB, Hamburg, k = 1.5289 A Ê ). Ê from N.
positions (occupancy 3/4) in a distance of 0.85 A
The region around the reflection (020) was excluded during This is the same geometry we applied for the nickel di-
the refinement. Reflection markers: NH4Br, Ni(NH3)2Br2, ammine halides [14] and is constructed using soft constraints.
Ni(NH3)Br2 (from top to bottom). Due to the low maximum diffraction angles we just con-
sidered one thermal parameter for all non-H atoms and
Ni(NH3)Cl2, Ni(NH3)2Cl2 (Cmmm) [14] and Ni (Fm 3 m) twice that value for H in the final refinements.
[28] resp. Ni(NH3)Br2, a-Ni(NH3)2Br2 (Pbam) [14] and Some differences between observed and calculated reflec-
NH4Br (Pm 3 m) [29]. For the impurity phases the positional tion intensities were observed for the Rietveld fit of
parameters were taken from literature and were not refined. Ni(NH3)Br2 (Figure 2). Especially the reflection (020) as the
The background was fitted using shifted Chebyshev polyno- first reflection (0k0) is observed far to strong. The way of
mials with additional fixed background points for sample preparation ± a thin layer of Ni(NH3)Br2 powder be-
Ni(NH3)Cl2. The reflection profiles of the phases were indi- tween CaptonÒ foil ± may suggest preferred orientation.
vidually fitted by a Simpson's rule integration of pseudo- However, no convincing model was found. We excluded the
Voigt function [30, 31] with correction for asymmetry as im- reflection (020) during the refinement in order to avoid the
plemented in GSAS. For the monoammine phases anisotro- influences of wrong reflection intensity on the refinement.
pic broadening of the reflections was considered. Free re- Test refinements of powder diffraction data obtained using
finement of the structural and thermal parameters without Bragg-Brentano geometry and CuKa radiation did not show
consideration of H atoms gave negative thermal parameters any discrepancies for the reflection (020).
for the N atoms. This was already observed for diammine Details of data collection and Rietveld refinements are
nickel chloride and bromide [14] and solved by introducing summarized in Table 1. The final atomic sites and the ther-
H on idealized sites. The same procedure was applied here. mal parameters are given in Table 2, and selected distances
We modelled a disordered distribution of 3 H atoms on 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


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


A. Leineweber, H. Jacobs, H. Ehrenberg

bF = 94.0° for Ni(NH3)Cl2 and aF = 2 ´ 9.05 A Ê, [8] I. Olovson, Acta Crystallogr. 1965, 18, 889.
cF = 2 ´ 11.98 AÊ , bF = 94.6° for Ni(NH3)Br2. The differ- [9] H. Jacobs, J. Bock, C. StuÈve, J. Less-Common Met. 1987,
ences between the two structure types are due to the 134, 207.
fact that half of the octahedral double chains present [10] R. Eûmann, G. Kreiner, A. Niemann, D. Rechenbach,
A. Schmieding, T. Sichla, U. Zachwieja, H. Jacobs, Z.
in Cd(H2O)Cl2 are shifted by b/2 in the Ni(NH3)Cl2
Anorg. Allg. Chem. 1996, 622, 1161.
type. This is illustrated schematically in Figure 7. From [11] P. Schiebel, A. Hoser, W. Prandl, G. Heger, W. Paulus,
that figure it becomes additionally clear, that the in- P. Schweiss, J. Phys.: Condens. Matter 1994, 6, 10989.
equivalence of the octahedral double chains in the [12] A. Leineweber, M. W. Friedriszik, H. Jacobs, R. Eû-
Ni(NH3)Cl2 type is generated by their particular mann, G. BoÈttger, F. Fauth, P. Fischer, Z. Kristallogr.
arrangement but not by structural distortions. Suppl. 1999, 46.
The crystal structures of the known ammines [13] A. Leineweber, M. W. Friedriszik, H. Jacobs, J. Solid
Ni(NH3)mX2 with m = 1, 2, 6 and X = Cl, Br can all be State Chem. 1999, 147, 229.
derived from that of the halides NiX2 by fragmentiz- [14] A. Leineweber, H. Jacobs, J. Solid State Chem. 2000,
ing its CdCl2 like layers by NH3 molecules. One finds 151, 2000, 152, 381.
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 [16] F. Remy, Rev. Chim. Miner. 1968, 5, 935.
m = 2 and, finally, a full fragmentation yielding iso- [17] R.-G. Lucas, Dissertation, UniversitaÈt Bonn 1954.
lated units [Ni(NH3)6]2+ for m = 6 (Figure 6). [18] W. Biltz, B. Fetkenheuer, Z. Anorg. Allg. Chem. 1913,
Preliminary investigations indicate that 83, 163.
Mg(NH3)Cl2, Mg(NH3)Br2 and Fe(NH3)Cl2 are prob- [19] W. Biltz, B. Fetkenheuer, Z. Anorg. Allg. Chem. 1914,
ably isostructural with the nickel compounds pre- 89, 134.
sented here. [20] H. Jacobs, D. Schmidt, Curr. Top. Mater. Sci. 1982, 8,
379.
Acknowledgement: We thank the Fonds der Chemischen In- [21] G. L. Clark, Am. J. Sci. 1924, 7, 1.
dustrie, the Deutsche Forschungsgemeinschaft and the Bun- [22] A. Ferrari, A. Braibanti, G. Bigliardi, Acta Crystallogr.
desministerium fuÈr Bildung, Wissenschaft, Forschung und 1963, 16, 846.
Technologie (JA5DOR) for financial support of this work. [23] J. A. A. Ketelaar, Z. Kristallogr. 1934, 88, 26.
The beamline B2 at HASYLAB is supported by this minis- [24] J. W. Visser, J. Appl. Crystallogr. 1969, 2, 89.
try under grant no. O5 SM8RDA. [25] An I-centred monoclinic unit cell can be transformed in
a C-centred monoclinic unit cell, which corresponds to
the standard setting according to Th. Hahn (ed.), Intern.
References Tables Crystallogr. Vol. A, Kluwer Academic Publishers,
[1] J. Jander, H. Spandau, C. C. Addison, Chemie in nicht- Dordrecht (1995). The I-centred settings are addition-
waÈûrigen LoÈsungsmitteln, Band 1, Teilband 1: Anorga- ally given.
nische und allgemeine Chemie in fluÈssigem Ammoniak, [26] H. Leligny, J. C. Monier, Acta Crystallogr. Sect. B 1974,
Friedr. Vieweg & Sohn, Braunschweig 1966. 30, 305.
[2] H. Jacobs, B. NoÈcker, Z. Anorg. Allg. Chem. 1992, 614, [27] A. C. Larson, R. B. von Dreele, program: GSAS ± Gen-
25. eral Structure Analysis System, Los Alamos National
[3] H. Jacobs, B. NoÈcker, Z. Anorg. Allg. Chem. 1993, 619, Laboratory, Los Alamos, USA 1994.
73. [28] H. Bohlin, Ann. Phys. (Leipzig) 1920, 61, 421.
[4] B. NoÈcker, Dissertation, UniversitaÈt Dortmund 1991. [29] R. S. Seymour, A. W. Pryor, Acta Crystallogr., Sect. B,
[5] F. O. SchroÈder, Dissertation, UniversitaÈt Dortmund 1970, 26, 1487.
1993. [30] C. J. Howard, J. Appl. Crystallogr. 1982, 15, 615.
[6] L. Asch, G. K. Senoy, J. M. Friedt, J. P. Adloff, R. Klein- [31] P. Thomson, D. E. Cox, J. B. Hastings, J. Appl. Crystal-
berger, J. Chem. Phys. 1975, 62, 2335. logr. 1987, 20, 79.
[7] R. Eûmann, Ch. Mockenhaupt, Spectrochim. Acta A
1992, 52, 1897.

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

You might also like