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Vdocuments - MX Crystal Structure of Ninh3cl2 and Ninh3br2
Vdocuments - MX Crystal Structure of Ninh3cl2 and Ninh3br2
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
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
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
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).
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.
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.
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.
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