Zeitschrift für Kristallographie - New Crystal Structures 212, 8 3 - 8 4 83

© by R. Oldenbourg Verlag, München 1997

Crystal structure of potassium tris(oxalato)ferrate(III) trihydrate doped

R. Wartchow
Universität Hannover, Institut für Anorganische Chemie, Callinstr. 9, D-30167 Hannover, Germany

Received September 27, 19%, transferred to 2nd update of database ICSD in 1997, CSD-No. 402647

013'
assumed a disorder for 0(15) too. But in spite of the large aniso-
tropic displacement parameters of 0(15) the lowering of the
occupation factor of this atom did not improve the refinement
here.
The next highest difference peak located between 0(13) and
0(14) may indicate a hydrogen atom but no further hydrogen
atoms could be detected. The third difference peak corresponds
to Taylor's Ow(3*). Both peaks were not considered here in the
refinement. The setting of the structure agrees with ref. 2 but
differs from that of other authors: For comparison the data of ref.
3 and 5 have to be transformed by 1/2—x, y, 1/2-z or origin-shifted
by 1/2, 1/2, 0, those of ref. 4 transformed by x, l/2-y, ζ or
origin-shifted by 0, 0, 1/2. On large crystals the following faces
were observed: {0,1,0}, {1,1,0} and {1,1,1}. The crystals are
elongated in the c-direction and are flat in the ¿»-direction.

K2 K1
Table 1. Parameters used for the X-ray data collection

Source of material: The preparation of two phases of a trisox- Crystal: yellow-green crystal of irregular shape.
alatoferrate(III) is described in ref. 1. Sodium oxalate was size 0.08 χ 0.13 χ 0.23 mm
added to favour the formation of the cubic anhydrous phase. Wavelength: Mo Ka radiation (0.71073 Â)
μ: 19.00 cm"1
But crystals of the monoclinic trihydrate were formed, too. Diffractoraeter: Siemens-Stoe
They contain sodium only as an impurity. An ICP-AES analysis Scan mode: oV20, learnt profile
yielded for the cations the relation Fe : Κ : Na = 1:2.93(5) : 0.12(2) Tmtasurement' 298 Κ
in the trihydrate. 46.1°
The crystal structure of the sodium-doped trihydrate is the same N(hJcl)un¡iue: 2118
Criterion for 70: /o > 2 σ(/ο)
as that of the pure potassium compound (see ref. 2). The refine- N(param)rcfim<r· 232
ment of the oxygen positions of the water molecules is much Programs: SHELXL-93, PLATON, X-RED, X-SHAPE
improved. The disorder which seems to be present in this class of
compounds (see refs. 3, 4, 5) is observed in the title compound,
too, at least in part: The occupation factor of K(3) is less than 1
and a difference peak is observed in the channel of the water Table 2. Final atomic coordinates and displacement parameters (in Â2)
molecules (0(13), 0(14), 0(15) near 0(15)). The channel axis
running through 3/4,1/4,1/2 in the c-direction is marked by a Atom Site Occ. l/te
dashed line in the figure. The position of the difference peak was
used to put the sodium atom on it with a refined occupation factor Na(l) 4e 0.107(4) 0.871(3) 0.264(1) 0.390(2) 0.038(6)
of 0.1. In this model it is unsatisfactory that the distance between
Na(l) and 0(15) is too short (1.6 Â). Taylor (see ref. 3) therefore

Table 3. Final atomic coordinates and displacement parameters (in Â2)

Atom Site Occ. X y ζ Un Un t/33 Un Un Un

Fe(l) 0.2639(1) 0.13078(4) 0.2506(1) 0.0251(4) 0.0223(4) 0.0261(4) -0.0003(4) 0.0088(3) -0.0010(5)
K(l) 4e 0.4749(2) -0.07395(7) 0.1621(1) 0.0330(7) 0.0372(9) 0.035(1) 0.0013(7) 0.0126(7) 0.0038(7)
K(2) Ae 0.0391(2) -0.07804(8) 0.3374(2) 0.0291(7) 0.053(1) 0.037(1) -0.0019(7) 0.0130(7) -0.0022(8)
Unauthenticated
Download Date | 6/16/17 6:28 PM
84 K2.9Nao.iFe(C20 4 )3 • 3H2Û

Table 3. (Continued)

Atom Site Occ. χ y ζ Un t/22 t/33 Un l/|3 t/23

K(3) 4e 0.893(4) 0.7580(2) 0.08683(7) 0.2557(2) 0.0433(9) 0.0436(9) 0.0389(9) -0.0013(9) 0.0171(7) -0.003(1)
C(l) 4e 0.0286(8) 0.0870(3) 0.0014(7) 0.028(4) 0.029(4) 0.030(4) -0.008(3) 0.014(3) 0.007(3)
C(2) 4e 0.2147(8) 0.0551(3) 0.0117(7) 0.034(4) 0.018(3) 0.034(5) -0.007(3) 0.013(3) 0.002(3)
C(3) 4e 0.2765(7) 0.0582(3) 0.4868(6) 0.027(3) 0.014(3) 0.032(4) -0.001(3) 0.014(3) -0.004(3)
C(4) 4e 0.4759(8) 0.0779(3) 0.4993(7) 0.029(3) 0.019(3) 0.028(4) 0.002(3) 0.010(3) -0.005(3)
C(5) 4e 0.2397(8) 0.2702(3) 0.2946(6) 0.042(4) 0.027(4) 0.036(4) 0.006(3) 0.002(3) -0.005(3)
C(6) 4e 0.3708(8) 0.2625(3) 0.2101(6) 0.053(4) 0.037(4) 0.029(4) -0.009(4) 0.010(3) 0.004(3)
0(1) 4e 0.0299(5) 0.1233(2) 0.1052(4) 0.025(2) 0.041(3) 0.029(3) 0.005(2) 0.006(2) -0.008(2)
0(2) 4e -0.1011(5) 0.0770(2) -0.0981(4) 0.029(2) 0.062(3) 0.029(3) -0.009(2) 0.007(2) -0.004(2)
0(3) 4e 0.3374(5) 0.0655(2) 0.1261(4) 0.026(2) 0.028(2) 0.032(3) 0.003(2) 0.010(2) -0.004(2)
0(4) 4e 0.2356(5) 0.0229(2) -0.0835(4) 0.047(3) 0.032(3) 0.033(3) -0.003(2) 0.022(2) -0.008(2)
0(5) 4e 0.1623(5) 0.0732(2) 0.3723(4) 0.019(2) 0.034(3) 0.030(3) 0.000(2) 0.005(2) 0.006(2)
0(6) 4e 0.2412(5) 0.0301(2) 0.5817(4) 0.037(2) 0.037(3) 0.033(3) 0.001(2) 0.019(2) 0.004(2)
CX7) 4e 0.4929(5) 0.1101(2) 0.3966(4) 0.020(2) 0.035(3) 0.029(3) -0.001(2) 0.008(2) 0.005(2)
0(8) 4e 0.5982(5) 0.0615(2) 0.5999(4) 0.025(2) 0.036(2) 0.026(3) 0.003(2) 0.002(2) -0.004(2)
0(9) 4e 0.1828(5) 0.2138(2) 0.3269(4) 0.040(2) 0.024(2) 0.046(3) -0.001(2) 0.020(2) -0.003(2)
0(10) 4e 0.1984(7) 0.3257(2) 0.3234(5) 0.079(4) 0.029(3) 0.068(4) 0.010(3) 0.022(3) -0.007(3)
0(11) 4e 0.3937(6) 0.2019(2) 0.1774(4) 0.064(3) 0.021(2) 0.044(3) -0.010(2) 0.029(2) -0.003(2)
0(12) 4e 0.4454(8) 0.3116(2) 0.1792(5) 0.121(5) 0.036(3) 0.072(4) -0.029(3) 0.053(4) -0.008(3)
0(13) - 4e 0.6233(7) 0.1696(3) 0.0294(5) 0.091(4) 0.101(5) 0.063(4) 0.011(4) 0.025(3) -0.022(3)
0(14) 4e 0.7928(7) 0.2890(3) 0.1646(6) 0.080(4) 0.071(4) 0.102(4) -0.002(3) 0.032(3) 0.004(4)
0(15) 4e 0.9061(8) 0.3133(3) -0.0608(7) 0.089(4) 0.121(6) 0.130(6) 0.025(4) 0.065(4) 0.053(5)

Acknowledgments. This work was supported by Prof. Dr. M. Binnewies. The 4. Lis, T.; Matuszewski, J.: Structure of Potassium Tris(oxalato)manga-
ICP-AES analysis was performed by Dr. A. Seubert. Computing facilities of nate(III) Trihydrate. Acta Crystallogr. B36 (1980) 1938-1940.
RRZN (Hannover) were used. 5. Merrachi, E. H.; Mentzen, B. F.; Chassagneux, F.: Etude cristallochimique
comparative de trisoxalatometallates (Œ) de cations monovalents. Rev.
References Chim. Min. 24 (1987) 427-445.
6. Sheldrick, G. M: SHELXL-93. Program for crystal structure refinement.
1. Wartchow, R.: Crystal structure of potassium sodium A-tris(oxalato)-fer- University of Göttingen, Germany 1993.
rale(III), K2jNaojFe(C204)3. Z. Kristallogr. 212 (1997) 57. 7. Spek, A. L.: PLATON, an integrated tool for the analysis of the results
2. Herpin, P: Structure cristalline des trioxalates de potassium. Bull. Soc. of a single crystal structure determination. Acta Crystallogr. A46 Suppl.
Franc. Miner. Crist. 81 (1958) 245-256. (1990) C-34.
3. Taylor, D.: The Crystal Structures of Potassium Tris(oxalato)-chromate(Iir) 8. Fa. Stoe: X-RED, X-SHAPE, program packages for processing the data
and -aluminate(ni) Trihydrate : a Reinvestigation. Aust. J. Chem. 31 (1978) collected with the STOE STADI4 or IPDS diffiractometer. Darmstadt,
1455-1462. Germany 1996.

Unauthenticated
Download Date | 6/16/17 6:28 PM