1469

Acta Cryst. (1970). B26, 1469

The Crystal Strueture of CazFe2Os and its Relation to the
Nuclear Eleetrie Field Gradient at the Iron Sites

BY ALAN A. COLVILLE
Department of Geology, California State College at Los Angeles, Los Angeles, Californ~t 90032, U.S.A.

(Received 23 October 1969)

Single-crystal counter data have been used to refine (R = 0.034) the crystal structure of Ca2Fe2Os, which
belongs to space group Pcmn (Dl~)with a=5.599 (1), b= 14.771 (2), c= 5.429 (1)A, and four formula
units per unit cell. In agreement with Grant's results of Fe3+ ion nuclear electric field gradient measure-
ments, the oxygen octahedra and tetrahedra about the Fe3+ ions are both markedly distorted, primarily
along the b axis. The thermal vibrations are anisotropic with the greatest vibration amplitudes directed
away from the strong bonds.

Introduction Recent investigations by Grant (1969) on the nu-

Dicalcium ferrite, CazFe2Os, is an end-member of the
solid solution series CazFez-zAlz05. The name brown-
millerite has been given to natural and synthetic mater-
ial with 0.66 < x < 1.38 and space group Icmm. For a
comprehensive review of the crystal chemistry of
CazFe205 and solid solutions see Geller, Grant & Gon-
set (1969). The most probable space group, Pcmn, and
the general atomic arrangement for dicalcium ferrite
were determined first by Bertaut, Blum & Sagni6res
(1959). The structure consists of perovskite-like layers
of oxygen octahedra connected along the b axis by
single chains of tetrahedra centered at b = ¼ (see Fig. 1).
Bertaut et al. found the octahedra to be essentially
regular and the tetrahedra to be distorted only by a
large tetrahedral angle (not given) that results in a
large 0(2)-0(2) length of 3.43 A, directed along the
b axis. A similar structure was proposed by Biissem
(1937, 1938) for brownmillerite.
clear electric field gradient (EFG) in the system
CazFez-zAlz05 provide evidence that the charge dis-
tribution surrounding the Fe 3+ sites is remarkably
asymmetric. 57Fe M0ssbauer spectroscopy shows that
CazFe205 and related solid solutions have exception-
ally large quadrupole splittings for Fe 3+ ion-contain-
ing materials. In CazFe205 the peak separations, AEQ,
at the octahedral and tetrahedral sites are 1.40 and
1-38 mm.sec respectively. Single-crystal specimens of
CazFe205 were used to determine the orientation of
the principal axes of the EFG at both Fe 3~- ion sites.
The space group symmetry restrictions on the EFG par-
ameters are the same as those of the thermal vibration
parameters. In Ca2FezOs, the octahedral Fe 3+ ion is on
an inversion center (at 0 0 0) and thus there are no
restrictions on the EFG; the tetrahedral Fe 3+ ion is
on a mirror plane of symmetry (at y = ¼) and one prin-
cipal axis of the EFG must be perpendicular to the
plane of symmetry. Grant concludes that at the octa-
hedral site the principal axis corresponding to the
largest EFG component, Vzz, is approximately along
the b axis (experimental error 20 °) and at the tetra-
hedral site is exactly parallel to the b axis.
This paper reports the refinement of the crystal struc-
ture of CazFe205 and compares the results with those
of the EFG measurements.

Experimental
The crystal used for this study was grown by Mr L. D.
c Fullmer using the Czochralski technique and was from
the same batch as that used for the single-crystal M6ss-
bauer work. The single crystal used for the collection
of intensities was a sphere with diameter 0.27 mm ob-
b tained with a sphere grinder similar to one designed
by Bond (1959).
The reflection absences allow two space groups,
Pcmn (centric) and Pc21n (non-centric); the final pre-
cision of the refinement corroborates the choice of
Fig. 1. S t r u c t u r e o f C a 2 F e 2 0 5 s h o w i n g F e - O f r a m e w o r k . Pcmn originally made by Bertaut et al. (1959).

A C 26B - 6
1470 THE CRYSTAL STRUCTURE OF CazFe205

The cell constants, obtained from the powder data The 413 non-zero, non-equivalent reflections were
of Smith (1962), and the calculated density are: collected to sin 0=0-5 and include only those that
a =5-559 (1) b=14.771 (2) c=5.429 (1)/k were sufficiently above background to make a con-
V= 448.99 .&3 tribution to the least-squares treatment. The structure
Z=4 was refined with the Busing, Martin & Levy (1962)
least-squares program. The starting positional param-
Calculated density, 4.02 g.cm -3. eters were those of Bertaut et al. (1959); the isotropic
The crystal was mounted on the c axis and 413 inten- temperature factors were set at 0-5 A z for the metal
sities were collected for six levels using Zr-filtered ions and 1.0 A 2 for the .oxygen ions. Atomic scatter-
Mo Kc~ radiation and a single-crystal diffractometer ing factors were taken from the tabulation of Ibers
equipped with a scintillation counter. For each reflec- (1962) and corrected for the real part of anomalous
tion the counter was fixed and the crystal was rotated dispersion using the values of Cromer (1965). In the
through the angle ~0 at 0.5 deg.min -1. The peaks were initial refinement all parameters including a single scale
recorded on a strip chart and integrated with a disc- factor were varied. The low and high amplitude Fobs
type planimeter. Each peak was integrated twice and were weighted slightly lower using a scheme similar to
the values averaged. The intensities were corrected for that of Cruickshank (1965).
absorption and Lp factors using a program similar to After three cycles of refinement the R value was
one by Lovell & Van den Hende (1961) which utilizes 0.066. Five low-angle, tdgh-intensity reflections pre-
correction tables computed by Bond (1959). sumably affected by extinction were removed from the
calculation and the remaining 408 intensities were used
Table 1. Observed and calculated structure amplitudes throughout the subsequent computations. After four
used in the refinement
r, k i ,n ~, ro.'~. real. r~s. rclle
12~., ,IZ.~ ~ e 16.:~ -i~.~ 26.5 -26.~
~.8 ~.9 7 e .", .o 51 . ~ 51.1
-21.0 ~.4 64.0 64.1
2"2,1 26.3 I 9 2~.o 2~.9 ,6 n4.C, 46. I
29,7 ~.$,4 4 9 21 ..: 34.5 ~.1
16 16.B -t6.4
~ , o 2S.9 2~.4 , io 76.6 37.-" ~.0
-7ti.7 41 16 I'~.8
i o 25.2 -23.9 2 Io 2o+1 3-~.a -~9.0
,9.~ 5 17 ':<I cu.9
~,++o 109.7 121.~ :~ IO .~'). ") <'+'.9 o ,e ~,~ J7.6
.'0.7
~0.0
22.6
-~9.0
71.7 72.7 4 io ,:..,# it,.2 2 , ~.e
71.6 -71.6 9 io 2~,.0 2a.5 ~,~l e 20.9 2~.0
40.9
35.6
59.4
-~4.1
1 127.~ -t~5.e 7 Io 49o2 67.$ t'.7.8
76.5 -77.9 i ii 27.9 21.~ -2a.2
-2~.e 19.5 .i B.I~
7 ~ ~ 44.1 -,~~..6 i i+ it)1.5 io5.2 (,7..', • -6~.6 17.9 -~.o
o ~ 92.9 e8.9 2 i~ 19+7 t9.5 -.m.9 .: 27.1 27.,
i~.4 -3,.i i 12 ~r.9 7~.0 1~.
6 4 o • ~7.~ -,t6.3
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~m" 5~.I 54.S
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94+4 97.~ 4 15 1,7.2 26.~ 28,0
67.:' 5 -:O.6
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o 6 o 87.2 59.~ 5S,~ 6 .~9. ~, Y~.5
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~2.0 5,1.... ~.5 6 21 ..~ 22.S
~.1 :,5.7 z 1~, a2.-- -.:1 . s ~ 2 91.1 5.'.5
S6.0 a6.0 ,I I~ ~.~ ;++i -72.1
-+t,.9 ,=2.~ 42.6 7 21 ..l 21.o
5 7 o ~6.6 -~6.6 6 15 .;~.~ '~7.7 -~9..'- r.,s.n -64.l
5 7 o 17..: 19.1 I 16 26.0 77.], 5 -2S.a 7
"1 7 o 29.0 2`].i $ 16 $(,+t~ le.`5 -19.0
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28.a
~.7
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s
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85.5 g, ~2.6
109.0
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~.I.I ~.~ 6 o ;l .o 5 4 75. 70.~
61.a 2 4 .',. ~ ,'0.7 76.1
,21oOoo 114.2
':,9.1
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2
4
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Ic.6 le.2 I 5 77.e 7S.2 2n.9 ~ .9
6 10 94.$ 92.2 2 85..5 ~8.5 2 :'9.e ~9.6 9
18.1 -19.8 5 26.7 ~.9 ,'~.4
28.0 1 5 16.7 IB.~ 9 2a .8 -el.a
~.9 -92.9 4 2 5e.~ %.7 4 29.1 28.9 I0 eg.~ 87.9
4.6.4 -'=7.5 5 56.7 56.5 22.5 -2~.7 I0 2:).2 I.q.7
H =S.2 -4~..';' 6 z 2 07_+ S~.l 19.0 -~9.1 ~o £'6.8 6~..~
ioi ..: 96.e o ,~.a n~,.7 1 6 ~.7 80.7 tO 55.2 5¢,4
2 12 0

t3
",~+.1
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-65.1
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(a)
57. i t~ 5,~.a r,5.r
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24.6 24.1 7 2 3~.7 -~s.e, 6 25.2 :~2.1 I] 19.$ 21 .-"
7 I~ 2~.7
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~ 7 ~9..'. i+
,69.~ -~9.S ~ 2 11.8 -~2.~ ~. I -~.2 i i~ I~.7 -I~., +
89.I 8~.~ 4 19.1 ~1.9 31 .g l~ 2-<+ 2.:.'.
16 0 ~.~ ~.~ ~ " ~1 .~ -15.a
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~.r+,
~ 7
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~5.-~
-m.9
35.0
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~0.0 ~ .,~ i 2,.i. .~7.~' ~2,a -5l . z o
le .~ .~ 19,~ 19.fl ~ 11 17.1 ~6+1
46.2 47.7 .5 n~.~ ~.7 4
~1.6 ~e.S -:~.6
.22,6
. . . . . . 72.6 ~ ,
.5 i ....
~0.9 'CO,.~ i 9 .:.; , e 0(3)I
$7,5 -~9.6 6 9 2 22.4 -.'~ .4 5 9 17.~ 2~.7 2"..~
i00.0 9,1.~ 7 ~ , 1.5.c 17.n 47.1 ...... ,~ 26.+7 -27.~
;m.o 79. i e ~ 2 2a., -Z+.O 2 to (2.~, ~.o.~ 2~.8 25.a
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o 1~..I 19.9 22.t i+-+ ~.e ~.2.,

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........
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7
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,~l.e ,~I+2 (b)
4 7 . . . . . . . . - ~+~.9 g , 1116 6 .... 51.7 5 o 2e.o -2~.6 12
8+77 67.1
}1.4 -~1.7 o 14 2
45..3
"lP.0 -~.~ 2 i -'-9.7 ..... ,,I t~.7 +,';.4
76.6
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713.6
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o
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27.0
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5 :,~..~
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Fig. 2. The interatomic distances (a) and the interatornic angles
40.0 ~9.~ i i`5 26.~ -,~7.4 2 2 a1.5 J5.7 17 (b) for the octahedron and the tetrahedron in Ca2Fe2Os.
 ALAN A. C O L V I L L E 1471

cycles o f isotropic r e f i n e m e n t the R value was 0.043
a n d a s u b s e q u e n t a n i s o t r o p i c r e f i n e m e n t led to a n R
value o f 0.034. T h e r e was virtually no c h a n g e in
the p o s i t i o n a l p a r a m e t e r s f r o m the i s o t r o p i c to the
a n i s o t r o p i c refinement. U s i n g the final p a r a m e t e r s the
structure a m p l i t u d e s n o t used in the r e f i n e m e n t were
calculated a n d f o u n d to be b e l o w b a c k g r o u n d . T a b l e 1
lists the o b s e r v e d a n d c a l c u l a t e d structure a m p l i t u d e s
used in the refinement. T a b l e 2 lists the p o s i t i o n a l par-
a m e t e r s a n d the a n i s o t r o p i c t h e r m a l p a r a m e t e r s . T a b l e
3 lists the b o n d distances a n d angles c o m p u t e d using
the O R F F E p r o g r a m by Busing, M a r t i n & Levy (1964).
Discussion of the structure
U s i n g the perovskite structure as a p r o t o t y p e , one can

T a b l e 2. Atomic position and thermal parameters for CazFe205

Ca Fe(1) Fe(2) O(1) 0(2) 0(3)
x* 0.0233 (2)]" 0 0.9338 (2) 0.2366 (7) 0.0716 (7) 0.8746 (8)
y 0.1079 (1) 0 ¼ 0.9839 (2) 0.1403 (2) ¼
z 0.4806 (2) 0 0.9459 (2) 0.2632 (8) 0.0234 (8) 0.6005 (9)
flll~ 0.0052 (2) 0.0020 (2) 0.0039 (2) 0.0036 (9) 0.0065 (9) 0.0044 (13)
fl22 0"0005 (1) 0"0008 (3) 0"0004 (1) 0"0009 (1) 0"0004 (1) 0"0002 (2)
fl33 0"0068 (5) 0"0021 (4) 0"0032 (4) 0"0040 (17) 0"0104 (18) 0"0081 (20)
fl12 --0"0002 (1) 0"0002 (1) 0 0"0002 (3) --0"0002 (2) 0
fl13 0"0008 (2) 0"0001 (2) --0"0000 (2) --0"0023 (8) 0"0006 (11) --0"0025 (11)
fl23 0.0004 (1) -0-0001 (1) 0 -0.0004 (4) 0-0004 (3) 0
Site 8(d) 4(a) 4(c) 8(d) 8(d) 4(c)

* Equivalent positions for space group Pcmn are: + x,y, z; ½- x, ½- y, ½+ z; - x, ½+ y, - z; ½+ x, - y, ½- z.

]. Standard errors are in brackets and refer to the last digit.
J; The form of the temperature factor is: exp [ - (h2f111+ k2f122 + 12fl33+ 2hkf112+ 2hlf113+ 2klf123)].

T a b l e 3. Bond lengths and angles f o r Ca2Fe205

Bond lengths
Fe-Fe Octahedron (O-O)
Fe(1)-Fe(l) 3.899 (1) A* 0(1)--0(2) 2.808 (5) x 2
Fe(1 )-Fe(2) 3.723 (1) 0(1)--0(I)1 2-843 (2) x 2
Fe(2)-Fe(2) 3.406 (1) 0(1)--0(1)2 2.719 (2) x 2
0(1)1-0(2) 2"868 (5) x 2
Octahedron [Fe(l)-O] 0(1)2-0(2) 2"708 (2) x 2
Fe(l)-O(l) 1"963 (4) x 2 ./~ 0(1)3-0(2) 2"885 (5) x 2
Fe(1)-O(l)l 1"970 (4) × 2 Mean 2"805
Fe(1)-O(2) 2"115 (3) x 2
Mean 2.016 Tetrahedron (O-O)
O(2)-O(2)1 3-241 (6)/~
Tetrahedron [Fe(2)-O] 0(2)-0(3) 3-019 (6) x 2
Fe(2)-O(2) 1"844 (3) x 2 O(2)-O(3)1 3.007 (5) x 2
Fe(2)-O(3) 1"904 (6) O(3)-O(3)1 3-052 (5)
Fe(2)-O(3) 1 1.920 (4) Mean 3.057
Mean 1.878
Ca-O
Ca-O(1) 2.484 (4) A
-O(I)1 2.483 (4)
-O(1)3 2.427 (4)
Ca-O(2) 2.542 (5)
-0(2)2 2-330 (4)
-0(3) 2.350 (3)
-O(1)2 2.741 (4)
-0(2)1 3.000 (5)
Bond angles
Fe-O-Fe
Fe(1)-O(1)-Fe(1) 164-8 (2) °
Fe(1 )-O(2)-Fe(2) 140.2 (2)
Fe(2)-O(3)-Fe(2) 125.9 (3)
Octahedron Tetrahedron
O(1)--Fe(1)-O(1)l 92.6 (1) ° O(2)-Fe(2)-O(2)1 123"0 (2) o
O(1)--Fe(1)-O(2) 86.9 (1) O(2)-Fe(2)-O(3) 107"3 (2) × 2
O(1)l-Fe(1)-O(2) 89.1 (1) O(2)-Fe(2)-O(3)1 106" 1 (2) × 2
O(3)-Fe(2)-O(3)1 105"9 (2)
* Standard errors are in brackets and refer to last digit.

A C 26B - 6*
1472 THE CRYSTAL STRUCTURE OF CazFe205

derive the structure o f Ca2Fe205 by changing alternate
layers o f o c t a h e d r a into tetrahedra. T w o of the oxygen
a t o m s in each t e t r a h e d r o n are s h a r e d with adjacent
o c t a h e d r a while two are shared with adjacent tetra-
h e d r a , thus f o r m i n g single chains that zigzag parallel
to the e axis (see Fig. 1). W a t a n a b e , Sugimoto, F u k a s e
& H i r o n e (1965) a n d Geller, G r a n t , G o n s e r , Wieder-
sich & E s p in o sa (1966) have p o i n t e d out t h a t the cat-
ions a n d anions in the o c t a h e d r a as well as in the
t e t r a h e d r a occupy positions in Ca2Fe205 similar to
o c t a h e d r a l positions in perovskite. The resultant f r a m e -
w o r k of c o r n e r - s h a r i n g o c t a h e d r a a n d t e t r a h e d r a con-
tains large irregular cavities that are the sites o f the
C a ions.
The results of the refinement (see Table 3) indicate
that both the t e t r a h e d r o n a n d the o c t a h e d r o n are dis-

Table 4. Anisotropic thermal ellipsoids for Ca2Fe205

R.m.s. Angles between ellipsoid axes and cell axes
Axis amplitude Isotropic B a b C
Fe(1) 1 0"096 (2) A t 0"73 (3)/~2 82 (3) ° 8 (3) ° 94 (4) °
2 0.055 (5) 0"24 (4) 124" 83 (9) 35*
3 0"056 (4) 0"25 (3) 35* 93 (18) 55*
Fe(2) 1 0.079 (2) 0"50 (3) 2 (10) 90"0 92 (13)
2 0.069 (5) 0.37 (5) 88 (13) 90.0 2 (lo)
3 0"064 (3) 0"32 (3) 90.0 00.0 90.0
Ca 1 0"107 (3) 0"91 (5) 66 (6) 111 (3) 33 (6)
2 0"088 (2) 0"61 (3) 27 (5) 92 (7) 117 (6)
3 0-072 (3) 0"41 (3) 79 (6) 21 (3) 72 (5)
0(1) 1 0"11 (1) 0"9 (1) 66 (12) 39 (18) 119 (14)
2 0"09 (1) 0"6 (1) 126 (18) 51 (18) 59 (14)
3 0"05 (2) 0"2 (1) 45 (15) 85 (11) 45 (14)
0(2) 1 0-126 (9) 1"3 (2) 81 (17) 82 (7) 11 (11)
2 0"102 (7) 0"8 (1) 12 (15) 100 (11) 97 (16)
3 0"069 (9) 0"4 (1) 82 (10) 13 (9) 99 (7)
0(3) 1 0"12 (2) 1"1 (3) 118 (13) 90"0 29 (13)
2 0.07 (2) 0"4 (2) 28 (13) 90.0 62 (13)
3 0.05 (2) 0.2 (2) 90.0 00.0 90.0
* The orientations of these axes are poorly defined as the cross-section (normal to the principal axis) is approximately a circle.
I" Standard error in brackets refers to the last digit.

,% Oc,s
@Oc
l,
O( ,"OIsl

OcJ

Ocoz
( )Oct,
Fig. 3. Coordination geometry and thermal vibration ellipsoids for CazFe205.
 A L A N A. C O L V I L L E
torted, in agreement with the results of the EFG meas-
urements of Grant (1969). Fig. 2 illustrates the two
sites and gives the appropriate bond distances and
angles. The octahedron is distorted primarily by elon-
gation along the b axis, the Fe(1)-O(2) distance in this
direction being 2.115 A compared with. 1.963 and
1.970 A for the two bond distances at approximately
right angles to b. The angle between Fe(1)-O(2) and
the b axis is 10.5 ° and O(1) is in a general position such
that the octahedra along [101] are alternated clockwise
and counterclockwise around an axis parallel to c. The
distortion of the tetrahedron can be shown by a com-
parison of the oxygen-oxygen distances: the distance
O(2)-O(2) 1 is 3.241 ,~ (and along b) while the others
are all near 3.01 .A. One tetrahedral angle is 124.0 °,
to be contrasted with the others which average about
106 °. The Fe(2)-O bonds are quite different, with the
shorter bonds (1-844 ,~) being involved in the large
tetrahedral angle and the longer bonds directed along
the chains.
Despite the irregularity of the individual bonds, the
average bond lengths are similar to those in other
Fe3+-coordination polyhedra. For example, in yttrium
iron garnet, Geller & Gilleo (1957) found the octa-
hedral and tetrahedral Fe3+-O distances to be 2.01 and
1.88 A. The calcium sites within the framework are all
crystallographically equivalent; each is surrounded by
an irregular array of eight oxygen ions. Six oxygen ions
lie at a mean Ca-O distance of 2.436 A and two other
oxygen ions lie at distances of 2.741 and 3.000 ,~.
The magnitudes and the orientations of the thermal
ellipsoids with respect to the crystallographic axes are
given in Table 4 and are illustrated in Fig. 3. The prin-
cipal axis corresponding to the largest thermal vibra-
tion for the octahedral Fe 3+ ion is about 8 ° from the
b axis and roughly in the direction of the longest Fe-O
bond distance. Note that the orientations of the other
two principal axes are nearly indeterminate as the
magnitudes of the intermediate and minor axes are
essentially equal. In the tetrahedron the principal axis
corresponding to the largest thermal vibration is along
the a axis and in the mirror plane that bisects the two
shortest bonds [the principal axis almost bisects the
long 0 ( 2 ) - 0 ( 2 ) 1 edge]. The calcium ion thermal vibra-
tion ellipsoid has the principal axis of largest thermal
vibration roughly in the ac plane and rotated +33 °
from the c axis. Again the orientation of the axis of
maximum vibration is away from the strong bonds.
Fig. 3 is a drawing of the ellipsoids of vibration and
the coordination geometry [generated using the 0 R TEP
program by Johnson (1965)].
1473
Summary
The results of this investigation confirm Grant's pre-
dictions from EFG measurements that the coordina-
tion polyhedra of the oxygen atoms surrounding the
Fe 3+ sites should be distorted primarily along the b
axis. In addition, the refinement has yielded reasonable
orientations for the principal axes of the thermal ellip-
soids. This careful analysis of Ca2Fe205 provides a
basis for further crystal structure studies that are under-
way in the system Ca2Fez-zAlzOs.
The author wishes to thank S. Geller for suggesting
this problem, R. W. Grant for several discussions of the
results of his work on the electric field gradient of the
Fe 3+ ions in CazFe205 and M. D. Lind for his aid with
the O R T E P program.
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