THE CRYSTAL STRUCTURE

of the Modification C of the Sesquioxides of the

Rare Earth Metals, and of Indium and Thallium.
PRE L IMI NARY NOTE

BY

WILLIAM ZACHARIASEN

I
n the present paper are given briefly the results of an X-ray
investigation at the following oxides:Sc�03, Y203, Sm203
Eu203, Gd208, Tb208, Dy203, Ho203, Er208, Tm203, Yb203,
Cp203, In203 and Tl203•
The relations of isomorphism of these compounds have been
described by V. M. GoLDSCHMIDT in publications of the serie:
Geochemische Verteilungsgesetze der Elemente.1 In these papers
professor Goldschmidts results of the X-ray examination (Iattice
dimensions) were given however without any publication of the
large material of experimental data.
The present investigations have been carried out in the
Mineralogical Institute of the University Oslo, partly by Pro­
fessor V. M. GoLDSCHMIDT, partly by the present author.
A complete description of the investigations will be given
in the next future in another publication of the author.
The oxides considered crystallize in a modification given
the name of the "C-modiflcation" of the sesquioxides of the
rare earth metals. (jfr. V. M. GOLDSCHMIDT: Geochem. Ver-

t Geochemische Verteilungsgesetze der Elemente IV. V. M. GoLDSCHMIDT,

F. ULRICH und T. BARTH: Zur Krystallstruktur der Oxyde der seltenen
Erdmetalle. Oslo I 925.
Geochem. Verteil. gesetz. d. EI. V. V. M. GoLDSCHMIDT, T. BARTH
und G. LuNDE: Isomorphie und Polymorphie der Sesquioxyde. Die
Lanthanidenkontraktion und ihre Konsequenzen. Oslo 1925.
 THE C-MODIFICATION OF SESQUIOXIDES 311

teilungsges. d. Elemente IV and V.). Crystallographic, optical as

well as X-ray examinations have shown that the crystals possess
isometric symmetry.
The elementary cube contains 16 molecules R203, which
is in good agreement with the observed densities. As only
2 2 2
even values of h +k +l are observed, the underlying lattice
is body centered.
In order to get further data on the symmetry of the
crystals, Laue photographs were prepared (of Tl203). The
patterns obtained showed hemiedral symmetry, thus excluding
the space groups of the classes Oh, O and Td.
According to the fact that the underlying lattice is body­
centered, only the following space groups are possible: P, P,
Th5 and Th 7•
N one of these space groups however has 32 equivalent
positions, the metal atoms consequently cannot all be equivalent.
This fact naturally makes an accurate determination of the
atomic arrangement very difficult as a large number of different
possibilities involving many parameters must be considered.
A comparison of the powder photographs of the most
light and the most heavy molecule in the series Sc203 -
Tl208 shows that all interference lines except 16, 32, 48, 64 etc
must be due to the metal atoms alone. We therefore have to
place the oxygen atoms in positions fulfilling this condition.
The intensity of the other lines consequently may be used for
determination of the metal lattice.
Ta ble 3 contains all possible arrangements of the metal atoms.

Ta b l e l. Powder Photograph of Cassiopeium Oxide.

& & A2 I nt.

2d 2 in degrees sinzz=(hz+kz+lz)
4a<n2
h k l
obs.

28,7 13,17 0,0520= 6x0,00867 211 0,5

36.4 17,01 0,0856 = 12 X 0,00713 13
40,1 18,86 0,1045= 12x0,00871 222 10
42,0 19,81 0,1148= 16 X 0,00717 [3
43,4 20,50 0,1226= 14x0,00871 321 0,25
46,3 21,95 0,1397 = 16 X 0,00873 400 4,0
41,2 23,40 0,1578 .c 18x0,00877 330 411 0,75
52,J 24,79 0,1759 20x0,00880 420 0,2
312 WILLIAM ZACHARIASEN

l l l
S· j, � Int.
2d 2 in degrees sin2 -z lh2 : k2 + F) 2 h k l
obs.
4a,.,
&

53,6 25,59 0,1867 � 26 X 0,00718 13

54.5 26,09 O,1935 c� 22 X 0,00880 332 0,5
57,0 27,29 0,2103=24 x0,00876 422 o, l
59,5 28,54 0,2283 = 26 X 0,00878 510 431 1,5
Q
59,9 28,74 0,2312 � 32 X 0,00723 t-'
6l,4 30,98 0,2649 �c 30 X 0,00883 521 0,5
66,55 32,06 0,2818= 32 x0,00881 44 0 10
63,9 33,23 0,3003 = 34 X 0,00883 530 433 0,5
� 36 x0,00884 6 11 532
71,1 34,32 O' 3181 1,5
44 X 0,00723 �
73,0 35,27 0,3338=38 0,00878 600,442 1,25
0
74,8 36, 17 0,3483 � 48 X 0,00726 ,,
75,3 36,42 0,3524 = 40 X 0,00881 620 0,25
17,4 37,47 0,3701 =42x0,00881 54 1 1,0
79,45 38,48 0,3873 c 44 X 0,00880 622 10
81,5 39,51 0,4048 •·· 46 X 0,00880 631 1,5
83,5 4 0,51 0,4214 48 x0,00879 44 4 2,0
85,55 4 1,54 0,4397 ·�50 X 0,008/9 710 550 54 3 0,75
86,5 42,01 0,4 479 = 62 X 0,00726 �
87,8 42,65 0,459J 52 X 0,00883 640 0,25
88,3 42,90 0,4634 - 64 X 0,00724 i3
89,8 4 3,65 0,4765 • 54 X 0,00882 721 e33 552 1,5
91,7 4 4,60 0,4931. 56x0,00881 6�2 1,0
96,6 o
47,05 0,5358 = 74 x, 0,00724 ,o

97,7 47,59 0,5450. 62 X O,OC879 732 651 1,5

98,0 47,74 0,5477 � 76 X 0,00721 �
99,8 48,64 0,5634 � 64 X 0,0088() 800 2,0
_ 80 X 0,00725
101,7 49,59 () ' 5797 13 2,5
... 66 X 0,00878 811 74 1 554
103,9 50,69 0,5986 - 68 X 0,00880 820 644 1,0
105,9 51,68 0,6156 70> 0,00879 653 1,25
107,9 52,68 0,6325 72 0,00877 822 660 0,75
110,0 53,73 0,6500 ·= 74 < 0,00878 831 750 743 2,5
112,1 54,78 0,6674 c• 76 > 0,00878 662 5
113,5 55,48 0,6784 = 94 7 0,00722 i3
115,2 56,32 0,6924 = 96 X 0,00721 i3
116,4 56,92 0,7020 = 80 X 0,00878 840 4
118,8 58,12 0,7210 c 82 X 0,00879 910 833 0,5
120,9 59.17 0,7373 = 84 x. 0,00878 84 2 0,5
123,0 60,22 0,7533 = 86 X 0,00876 �21 761 655 1,5
127,9 62,66 0, 7892 = 90 X 0,00877 ['30 851 754 1,5

Fe radiation. Camera diameter 57,45 mm- a,"= 10,33 Å.

 THE C-MODIFICA TJON OF SESQUIOXIDES 313

T a b l e 2. Lattice Constants 1.

i=tu-= �nr=�
-
compound -- Compoun d-
s

Sc20s 9,79 Dy20s 10,63

Y20s 10,6) Ho20a 10,5S
ln20a 10,12 Er20a 10,54
Sm203 10,S5 Tm20a 10,52
Eu20s IO,S4 Yb203 10,39
Gd20s 10,79 Cp20a 10,37
Tb20, 10,70 Tl203 10,57

T a b l e 3. Possible arrangements of the 32 metal atoms2.

Th7 p
l. 24+S a)24e+Si; b)24e+Se l. 24-iSb
I l. 16e + 16e I l. 12c+ 12c+Sb
I l l. 16e+Se +Si II l. Sb+Sb+Sb-tSb

Th" T'
24d+ Se
l. l. 24+Sa
24d+6e+2a
I l. I l. 24+6e + 2a
16d + 16d
II l . I ll. 12+12+S a) 12a,-12a+Sa
IV. 16d+Se + 6e+2a b) 12a+12b+Sa
V. 12+12 +S a) 12a+12a�-se C) 12b+ l2b+Sa
b) 12a+ 12b+Se IV. 12-:-12+6 --2
c) 12b + 12b-:-Se a) 12a -t 12a+6e+ 2a
VI. 12-'-12-'-6-r-2 b) 12a+12b+6e+2a
a) 12a+l2a+6e+2a c)12b+12b+6e+2a
b) 12a+ 12b+6e+2a V. Sa + Sa -1- Sa + Sa
c) 12b 12b + 6e -1- 2a VI Sa-�8a-i- Sa+6e + 2a

As a member of these alternatives has needed very careful

and extensive examinations, the discussion will not be given in
this preliminary note. It shall be mentioned that I have suc­
ceeded in proving that only the arrangement P, Il is compatible
with the observed intensities.
N ow the val u es of the parameters involved have to be
determined.
At this place a characteristic property of the structure
shall be mentioned. As the predominating lines in the powder
photographs are reflections from the faces 222, 400, 440, 622,
444, 800 etc. (i. e. second order reflections from Ill, 200, 220,

l jfr. Geochemische Verteilungsgesetze der Elemente IV und V.

2 Nomenclature corresponding to R. W. G. WYCKOFF: The a n al ytica l ex­
pression of the resuits of the theory of space-groups. Washington 1922.
314 WILLIAM ZACHARIASEN

311, 222, 400 etc.), the unit cell may be divided in eight small
cubes, each of them nearly being a face centered cubic lattice.
The parameters consequently must obtain values which nearly
place them in special positions. The three parameters involved
8b (t), 12c (u) and 12c (v) therefore only differ very little from
the following figures: t= 1/4, u=o and v=1/z.
It looks very probable that the parameter t is exactly equal
to 0, 25. The values of u and v can be determined by means

�------/'! -·

Il p
o � u
� >l
o
• i'/ j
� 8
* • -:1 '�}
Fig. l . Fig. 2.
The arrangement o f the oxygen The tetrahedral arrangement
atoms round a metal atom. of the metal atoms round an
oxygen atom .

of table 4. (Intensities corresponding to Tl�03 where the oxygen

atoms may be put out of consideration). Consecutively we put
u= 0,021 (7, SO) v=0,542 (195°).

T a b l e 4. Determination of the Parameters.

u jv lntensity

in are measure 42 46
l 48

5" 190° 32 61 135

5' 195° 66 78 107
se 200° 70 73 76
7,5) 195" 37 51 99
100 190° 26 48 l 17
10 ° 195° 75 114 90
100 200° 92 103 62

Observed l l ,O l l ,4 l 2,5
 THE C-MODIFICATl ON OF SESQUIOXIDES 315

Table 5 shows the exellent agreement between calculated

and observed intensities. (The intensities were registered by
photometer).
As formerly mentioned the oxygen atom� only contribute
to the reflections from 400, 440, 444, 800, 840 etc. For reflec­
2
tions where h2+k +12 is an odd multiplum of 16, the amplitude
of the oxygen Iattice is opposite to that of the metal lattice; for
reflections where h 2 +k2 + J2 is an even multiplum of 16, the
oxygen atoms and the metal atoms are acting together.
The 48 oxygen atoms consequently have to be divided
in two classes of 24 equivalent positions, each of them being
located by three parameters x y z (x1y1z1; X2Y2Z2).
In order to get approximative agreement with the observed
data we must assume X1=y1=X2=1/s and Z1=y2=z2=3/s.
More exact values cannot be obtained by means of intensity
measurements; but going out from the hypothesis that an
oxygen atom has the same distance from the four surround-

Ta b l e 5. Calculated Intensities.

Intensity Intensity
h2 _ _ k2+J2 h2+k2+J'
calc. l obs. calc. l obs.

6 1,1 0,5 50 0,9 0,75

-
8 0,7 52 0,5 0,5
--
10 0,1 54 1,4 1,5
12 18,1 10 56 0,7 1,0
--
14 1,2 0,25 58 0.2
16 9,8 5,0 62 1,5 1.5
lR 1,3 1,0 64 1,6 1,5
20 0,2 0,2 66 1,6 2,51
22 0,3 0,5 68 0,9 1,0
24 0,2 0,1 70 1,1 1,25
26 1,8 1,5 72 0,6 0,75
30 0,7 0,5 74 1,9 2,51
32 8,2 8,0 76 4,2 6,0
-
34 0,9 0,5 78 0,4
36 0,2 1,51 80 4,1 5,0
38 1,4 1,5 82 0,5 0,5
40 0,4 0,25 84 0,5 0,5
42 1,1 1,0 86 l 1,8 1,5
--

l
44 ,10,7 10 b8 0,1
46 1,5 1,5 90 1,5 1,5
48 3,0 2,5 94 1,0 1,51

t Coincidence with �-lines.

316 WILLIAM ZACHARIASEN: THE C-MODIFICAl'ION

ing metal atoms, I succeeded in determinating the following

values:
X 1 =0,125 y1 �-= 0 135
, z1=0,395
x2= 0,100 Y-�=0,358 Z2=0,373

These figures give the atomic distances: Sc-0= 2,18 Å,

Y-0=2,36 Å, Sm-0=2,42 Å.
When we regard one eighth cube of the whole unit cell,
the analogy to the fluorspar arrangement is evident. The metal
atoms form a distorted face centered lattice. while oxygen
atoms occupy approximatively six of the eight positions of the
fluorine atoms.
Each metal atom consequently is surrounded by six oxygen
atoms at the same distance, and each oxygen atom by four
metal atoms forming a nearl y regular tetrahedron.
I am indebted very much to Professor V. M. GoLDSCHMIDT
for his kind help an advice during the extensive calculations.

Oslo, Mineralogical Institute of University

january 11th, 1927.

Printed February 26th, 1927.