Solid State Sciences

t. 1, 1999, p. 365-312

Crystal structure and magnetic properties of a one

dimensional complex oxide Ca3NiMnOh
G.V. BAZUEV, V.G. ZUBKOV, I.F. BERGER and T.I. ARBUZOVA
Institute of Solid State Chemistry, Ural Branch of the Russian Academy of Sciences,
Ekaterinburg, 6202 19, Russia

(G. F., received May 14, 1999; accepted September 3, 1999.)

ABSTRAC’I’. - The results of structural refinements and magnetic propertics of

one-dimensional oxide CaxNiMnOh are presented. The structure of CaXNiMnOh was
solved by Rietveld analysis of powder neutron date in space group R-3c with
a=9.1227(9) A, c=10.5811(17) A, 2=6 (type of K&dC4,). Infinite chains of Mn06
octahedra and (Ni,Mn)Os trigonal prisms sharing faces run parallel to the c axis. The
chains are separated by Ca2’ cations, which are located in a distorted square antiprismatic
environment. Magnetic susceptibility obeys the Curie-Weiss law at 300-600 K with bff
value 5.00 pu consistent with the valence cationic combination NiZi-Mn4’. MagJletic
measurements display the antiferromagnetic ordering in Ca3NiMnOs at 16 K.

INTRODUCTION

Compounds with low-dimensional crystal structure have attracted

widespread attention of researchers owing to characteristic for these
materials of highly anisotropic physical properties. Among similar
compounds are a complex oxides of the platinum metals with general
formula A3A’Pt(Ir)06, where A=Ca,Sr and A’=Cu,Ni,Zn [l-3], with one
dimensional crystal structure type of K&dClb. The structures of
A3A’Pt(Ir)06 compounds consists of infinite chains of alternating face-
sharing PI(Ir)06 octahedra and Ni(Zn)Oe trigonal prisms or CuO4 square
planes. Each chain is surrounded by six parallel one-dimensional
neighboring chains which contain alkaline-earth elements.
The compounds under consideration have interesting magnetic
properties including antiferromagnetism, ferromagnetism and a combination
Solid State Sciences, 1293-2558/99/6/O 1999 &itions scientifiques et mkdicales Elsevier SAS. All rights reserved.
366 G.V.BAZUEV etal.

of ferromagnetic coupling within the chains and antiferromagnetic coupling

between the chains. It is found [2] that magnetic properties depend strongly
on the number of unpaired d-electrons on the transition metal atoms
constituting the one-dimensional chains.
We recently reported on new complex oxides Ca&MnOb (A=Cu, Ni and
Zn) with crystal structure of type K4CdClc, [4,.5]. It is shown that manganese
as a Mn4’ cation is located in the octahedral positions and cooper and zinc
as a Cu2’ and Zn2’ arc located in the trigonal prisms in Ca&uMn06 and
Ca3ZnMn06. However the results of magnetic susceptibility studies of
CajNiMn06 at 2-300 K cLannot be explained on base cationic combination
Ni*+-Mn4+. In present paper we report the crystal structure of CasNiMn06 at
295 K and magnetic properties at 2-600 K.

EXPERIMENTAL

The carbonate CaC03 (99.9%) and oxides Mr-102 and NiO containing
not less than 99.9% of the main substance as a initial reagents for the
synthesis Ca3NiMn06 have been used.
To obtain the aforesaid required compound the solid state reactions
method has been applied. Being pressed in pellets, the initial mixture was
first annealed in the air at the temperature of 95O’C for 30 h and then at
125OOC for 12 h.
The phase composition of the annealed products was examined by X-
ray powder diffraction analysis using Cu Ka radition with the aid of the
STAIN-P (STOE) automatic diffractometer. The unit cell dimensions were
determined by the least-squares method. The polycrystalline silicon
(a=5.4307595P\) was used as an internal standard in determining the
interplanar distances.
The structural refinements of CajNiMnOG were carried out on the base
of X-ray powder patterns, obtained by STADI-P (STOE, Germany)
automatic diffraclometer by stepwise scanning (20n=1So, 20,=5’, ~=30 min,
CuK, radiation) in standard transmission mode, having use of position-
sensitive detector (PSD). Powder neutron diffraction data were collected
from 10 to 110’ 28 with a step interval A28=0.1. The neutron wavelength
was 1.5147A. Rietveld’s method of full-profile analysis of neutron powder

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 CRYSTAL STRUCTURE AND MAGNETIC PROPERTIES 367

diffraction patterns (version DBW 4.1) was used. The methodical

peculiarities of the accumulated data making use of long PSD and creating
experimental diffraction files on its basis have been considered earlier [6].
Oxygen content in the sample of Ca3NiMnOh was determined by TG
analysis in a H2 gas flow at 9OO’C. It has been taken into account that Ni in
products of restoration appeared as metal and Mn was restored up to Mn2’.
The oxygen stoichiometry ofthe CasNiMn06 sample was found to be 6.012.
Magnetic properties were measured using a Quantum Design MPMS
superconducting quantum interference device (SQUID) magnetometer at
temperatures from 2 to 320 K. Measurements were carry out in magnetic
fields 4 Oe and 8.9 kOe after cooling the samples in measuring magnetic
field. Magnetic susceptibility x in the high temperature range from 77 to
600 K was measured in a magnetic field with intensity 4,5 kOe according to
Faraday’s method. The error in x determination did not exceed *2%.

RESULTS AND DISCUSSION

The crystal structure of CqNiMnOh is closely related to Sr3NiIrOG [3]

and was refined in the space group R-3c with a hexagonal unit cell
(a=9.1227(9)A and c=10.5811(17)A, z=6). Analysis of the powder XRD
pattcm showed that in addition to the Ca3NiMn06 there is some minor
amount of NiO impurity phase in the sample. In spite of the achievement of
the global minimum the calculations on the base of X-ray powder
diffraction data failed to solve the problem of the localization of Ni and Mn

TABLE 1. Atomic positions, isotropic thermal parameters Biso

and occupancy of Ca3NiMir06

ATOM x/a y/b ZJC b.w, .A2 occupancy

Ca: 18e 0,3625 (3) O:O l/4 0,72 (5) 0,5
Mn: 6b 0,O 090 030 0321 (5) OJ666
Ni: 6a 0,O o,o l/4 0,68 (4) 0,1533(8)
Mn: 6a 0,O (40 l/4 0,68 (4) 0,0133(8)
0: 36f 0,179O (2) 0,0276 (2) 0,1082(l) 0,66 (4) I,0
Ru,=2,96%, %t=5.59%, I&=5.93%

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 G.V. BAZUEV et al.

32.5 55 77.5 100

2Theta
Fig.]. Neutron Rietveld analysis for Ca3NiMn06 at 295 K showing the observed,
calculated and difference patterns. The peaks lnarked by asterisk correspond to NiO.

in view of proximity atomic scattering factors for these elements. At the

sametime the neutron diffraction refinements of Ca3NiMn06 (Table 1) have
unequivocally confirmed the location of ions in the positions: Ca - 18e; Mn
- 6b; Ni - 6a; 0 - 36f. It was found that 8% Mn occupiesthe 6a positions in
the Ca3NiMn06 also. By this means, the refmed chemical composition of
the complex oxide is Ca3Nio.92Mnl,0s06.As a result, small peaks of NiO
oxide were found as impurity on the X-ray and neutron powder diffraction
patterns. The observed, calculated and difference neutron powder
diffraction of Ca3NiMn06 at 295 K are shown in Fig. 1.
The Table 2 lists the selectedbond distancesin polyhedra from neutron
refinements. The values of the Ni-0 distance, 2.137 A and Mn-0 distance,
1.905 A, are similar to those found in the literature in analogouscompounds
of N?+and Mn4+cations - Sr3NiPt06 (2.18OA [2J), perovskite j3-SrMnOj
(1.903A [7]) and P-Sr2Mn04 (1.894A [Xl).
One feature of oxides with one-dimensional crystal structure type
&CdC&, is the presenceof short metal-metal distances.It is seenfrom Table
2 that in Ca3NiMn06 short Mn-Ni distance is equal to 2.645 A. However
this compound is not expected to contain direct metal-metal bonds within

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 CRYSTAL STRUCTURE AND MAGNETIC PROPERTIES 369

the chains. The resistivity measurements that indicate that Ca3NiMn06 is an

insulator are in accord with this assumption.

TABLE 2. Selected bond distances for Ca3NiMnOh from refinement of neutron

Atoms Bond distances, A Atoms Bond distances, A

Ca - 20 2.354(3) MI-I- 60 1.905 (1)

- 20 2.443(2) - 2Ni 2.645
- 20 2.464(l) - 6Ca 3.047( 1)
- 20 2.638(3) Ni - 60 2.137(l)
- 2Mil 3.047(l) - 2Mn 2.645
- Ni 3.307(3) - 3Ca 3.307(3)
- 6Ca 3.409( 1) - 6Ca 3.409( 1)

. The chain structure of Ca3NiMnOb is shown in Fig.2. The (Ni,Mn)06

trigonal prisms and Mn06 octahedra share common faces forming one-
dimensional chains that run along the crystallographic c-direction in the
structure. These chains are separated by eight coordinated Ca atoms, which
are in a distorted square antiprismatic environment.

Ca
/

Fig.2. The chain structure of Ca3NiMn06 along c-direction. The Mn06 octahedra and
(Ni, Mn)06 trigcmal prisms are shown as polyhedra.

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370 G.V.BAZUEV et&.

The magnetic susceptibility x studies of polycrystalline Ca3NiMn06 in

field of 8.9 kOe indicate magnetic ordering at 16 K (Fig.3). The maximum

“0 3,0
‘;;

* 2,5

20

1,513 ‘,,,17,,

0 50 100 150 200 250 3ixl

T, K

Fig.3. Temperature dependence ofthe magnetic susceptibility of CgNiMnOb at 2-320 K.

of the susceptibility suggests antiferromagnetic coupling between the spins

of cations Mn and Ni at below 16 K. The temperature dependence of x is

-200 -100 0 100 200 300 400 500 600

T, K
Fig.J.Temperature dependence of the magnetic susceptibility of CasNiMnO, al 77-600 K.

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 CRYSTAL STRUCTURE AND MAGNETIC PROPERTIES 371

characterized by a positive deviation from the Curie-Weiss law x=c/(T-8)

already below 300 K. There is a large increase in the susceptibility starting
at 60 K. Magnetic susceptibility x obeys the Curie-Weiss law x=c/(T-8)
(c=3.12 mol-‘, 8=-160 K) from 300 to 600 K. (Fig.4). The effective
magnetic moment bn equals to 5.00~~. The theoretical magnetic moment
for the cationic combination N?+-Mn4+ is 4.8Opn. Taking into account the
rcsulls of structural refinement according to which 8% Mn cations occupy
the Ni positions and considered the manganese at trigonal prismatic
coordination as Mn*+-cation tic is equal 5.01 un. These results seemed to
testify that the Ni2+, Mn4+ and probably the Mn*’ cations are present in the
compound. However it is necessary to explain complex behavior of
magnetic susceptibility below 300 K in this one-dimensional compound. In
our opinion to account for observed peculiarities of magnetic susceptibility
behavior may two assumptions be considered. First assumption is based on
a combined character of magnetic coupling, for example, antiferromagnetic
coupling within the chains and ferromagnetic coupling behveen the chains.
In this situation the temperature dependence of magnetic susceptibility may
be differ from Curie-Weiss low as a result conservation of short order up to
high temperatures. The second assumption is connected with a possible
occurrence of different oxidation states of Ni and Mn cations at low
temperature [4].
The research was supported by Russian Foundation for Basic Research
(project N 98-03-32697).

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372 G.V.BAZUEV et&.

REFERENCES

1. A.TOMASZEWSKA, H.MULLER-BUSCHBAUM, 2. Anorg. Affg. Chemie,

1993,619, p.534.
2. T.N.NGUEN, H.-C zur LOYE, J. SoEidState Chem.,1995,117, p.300.
3. T.N.NGUEN, D.M.GIAQUINTA, H.-C. zur LOYE, Chem.Mater., 1994,N6,
p.1642.
4. G.V.BAZUEV,V.G.ZUBKOV,V.N.KRASILNIKOV, K.N.MIKHALEV,
T.I.ARBUZOVA, Doklady AkademiiNauk, 1998,363, p.634.
5. G.V.BAZUEV, V.N.KRASJLNIKOV,V.G.ZUBKOV, I.F.BERGER:
T.I.ARBUZOVA, Book ofAbstracts of 5-th International Workshop((High-
Temperature Superconductorsand Novel Inorganic Materials Engineering))
(MSUHTSC -~,Muscow, March 1998. p MJ-39.
6. G.V BAZUEV, B.G.GOLOVKIN, V.G. ZUBKOV., A.S.TYUTYUNNIK, ,I.
SolidState Chem., 1994,113, p.132.
7. N.MIZUTANI, A.KITAZAWA, N.ONKUMA, MKATO, Kogyo Kogaku
Zusshi,1970,43, p. 1097.
8. J.-C.BOULOUX, J.-LSOUBEYROUX, G.Le FLEM, PHAGENMULLER, J.
SolidState Chem., 1981,38, p.34.

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