Z. Kristallogr. NCS 229 (2014) 265-266 / DOI 10.1515/ncrs-2014-0130
265
© 2014 by Walter de Gruyter Berlin/Boston
Refinement of cesium diaquatrichloromanganate(II), CsMnCl3!2(H2O) by
neutron diffraction, Cl3CsH4MnO2
In-Hwan Oh*, I, Je-Eun KimI, Japil KooII and J. M. Sungil ParkI
I
II
Neutron Science Division, Korea Atomic Energy Research Institute, Daejeon, 305-353, Korea
LG Chem Research Park Corp. R&D, Daejeon, 305-380, Korea
Received December 11, 2013, accepted July 11, 2014, available online September 02, 2014, CSD no. 710093
Experimental details
H atoms attached to water molecules were positioned in a
difference fourier map and refined without any restrictions. Due
to the limitation in the 2$ angle, the obtained atomic displacement
parameters are more or less bigger than the expected values. To
deliever the accurate displacement parameters, at least 0.8Å–1 in
sin$/" is needed, although it has no influence on the precision of
the atomic positions [2]. Due to the experimental conditions a
completeness of only 53% has been achieved.
Abstract
Cl3CsH4MnO2, orthorhombic, Pcca (no. 54), a = 9.1197(11) Å,
b = 7.3240(5) Å, c = 11.533(7) Å, V = 770.3 Å3, Z = 4,
Rgt(F) = 0.0694, wRref(F2) = 0.1703, T = 300 K.
Table 1. Data collection and handling.
Crystal:
Wavelength:
%:
Diffractometer, scan mode:
2$max:
N(hkl)measured, N(hkl)unique:
Criterion for Iobs, N(hkl)gt:
N(param)refined:
Programs:
pink rectangles, size 1#2#2 mm
(1.31430 Å)
2.298 cm"1
Four-Circle Diffractometer, #
101.8°
1158, 357
Iobs > 2 !(Iobs), 353
53
SPEC [12], HANASPEC [13],
SHELX [14], DIAMOND [15],
PublCIF [16]
Source of material
A CsMnCl3!2H2O single crystal for this work was supplied by the
Crystal Bank at Pusan National University. The neutron
diffraction structural investigation on CsMnCl3!2H2O crystal at
room temperature was carried out using a large single crystal of
2#2#1 mm3 at the HANARO reactor at Daejeon, Korea. The data
collection was performed on a four-circle diffractometer
equipped with a Ge (311) monochromator with a wavelength of "
= 1.3143 Å. The data refinement was based on the results of a
preceding X-ray diffraction structural analysis at room
temperature [1].
_____________
Discussion
The crystal structure of the one-dimensional antiferromagnetic
cesium diaquatrichloromanganate (II) was investigated by single
crystal neutron diffraction and the positions of the hydrogen atoms were successfully localized by neutron diffraction for the
first time and the positions by X-ray diffraction experiments [1,
3] are verified. The title structure exhibits linear chains along the
a axis linked by chlorido ligands. The O–H!!!Cl hydrogen bonds
build zig-zag chains along a-axis. Mn-octahedra surrounded by
two oxygen atoms and four chlorine atoms are linked by the hydrogen bonds. The water molecules in this structure show an almost ideal geometry. The title compound belongs to so-called
linear-chain antiferromagnets. RbFeCl3!2H2O, CsFeCl3!2H2O
[4], CsCoCl3!2H2O [5] and [(CH3)3NH]CoCl3!2H2O [6] are isomorphic with CsMnCl3!2H2O. These materials attract considerable scientific interest because of their one-dimensional magnetic
characteristics. Among these, CsMnCl3!2H2O is regarded as a
standard example of a one-dimensional Heisenberg antiferromagnet. So far there are many investigations on these linear-chain
antiferromagnets. However, most of investigations did not take
into account the hydrogen atoms and a resulting hydrogen bonding effects on the crystal structure. In this respect, we decided to
investigate the crystal structure of CsMnCl3!2H2O by neutron
single crystal diffraction. The deformed Mn-octahedra are parallel to a-axis and through Cl– ions, linear chains are built. In addition to this, the hydrogen bond O–H1!!!Cl2 also links Mnoctahedra. This hydrogen bond enables the zig-zag chain along aaxis to be stabilized. Between these Mn-octahedra, Cs+ ions locate and Cs+ ions seperate Mn–Cl–Mn linear chains. The crystal
structure in this study is more or less similar to previous reported
results by X-ray investigations, but there exist clear discrepancy
in several bond lengths. It is well known that neutron diffraction
is a unique method which can detect the H/D distribution with
high accuracy. Our experimental results indicate that the H–O–H
angle in this compound is 105.94 degree, close to the ideal value
of free water. Contrary to this, the anhydrous form, CsMnCl3
crystallizes in rhombohedral system [7]. Whereas the anhydrous
crystal is antiferromagnetically ordered at 69K [8], the Néel tem-
* Correspondence author (e-mail: [email protected])
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266
Cl3CsH4MnO2
perature of hydrous crystal is about 4.89K [9]. This compound
shows corner sharing Mn-octahedera through Cl– ions. The hydrogen bonds in this compound caused the tilting of Mnoctahedron towards an adjacent Mn-octahedron. The hydrogen
bond O–H!!!Cl link Mn-octahedra resulting the stabilization of
the zig-zag chain along a-axis. Generally, due to the attractive
forces by hydrogen bonding, the bond distance between Mn2+
ions and Cl– ions, which take part in the hydrogen bond should be
shorter compared to the other chlorido ligand,
which do not participate in any hydrogen bond. In this compound,
Cl1 corresponds to the latter case. But astonishingly, in
CsMnCl3!2(H2O), the distance between Mn2+ ions and the
chlorido ligand not involved in the hydrogen bond is shorter. Because Cl2 is bifurcated, it seems that the attractive forces through
the hydrogen bond canceled each other out. The obtained bond
lengths suggest that the strength of the O–H!!!Cl hydrogen bonds
in the structure can be classified as intermediate [10, 11].
Table 2. Atomic coordinates and displacement parameters (in Å2).
Atom
Site
Cs
Mn
Cl(1)
Cl(2)
O
H(1)
H(2)
4d
4c
4e
8f
8f
8f
8f
x
¼
0
¼
0.0887(4)
0.069(1)
0.025(1)
0.175(2)
y
0
0.468(1)
½
0.2220(3)
0.6838(8)
0.692(1)
0.701(2)
z
0.1459(6)
¼
0.1504(3)
0.3902(2)
0.3703(6)
0.4469(9)
0.386(1)
U11
U22
U33
0.024(9)
0.01(1)
0.018(5)
0.021(4)
0.02(1)
0.05(1)
0.05(2)
0.041(3)
0.034(4)
0.043(2)
0.042(2)
0.050(3)
0.076(5)
0.076(6)
0.020(4)
0.006(5)
0.011(2)
0.011(2)
0.021(5)
0.018(6)
0.041(6)
Acknowledgments. This work was financially supported by the Nuclear &
R&D Programs (NRF-2012M2A2A6004261).
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U12
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"0.005(3)
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