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R dp&orris@us. itm.com/~354936Daniel P. Morris Copies: [T 

*DER ARKXV FOBR KEKX VOL 5 

JTHOR Aurivillus, B. f 

\GE 39-EOA 

\Y 

3AR 1952 

dSN 03656128 

)DEN BLKJ>2/17/05_0365-6128_307395 

flBCKSUM 00090130048007110 

QjLING 888 

2RVTCE RBGDLAR 

3NF- # BESG090130048-1 

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3MMENT 



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FEB. 22. 2 0 05^1 0:41 AM Mai 



)6ATE-IE INFO EXPRESS 



ARKIV FOR KEMI Band 5 nr 4 



NO. 4214 P. 2/10 



Communicated 14 May 1952 by Abttb Wbstgbxct 



The structure of BiaNb0 5 F and isomorphous compounds 

By BENCT , AuRTVTLUtJS 



With 1 figure in the text 



X-ray studies made previously on the compounds CaBi^NbaO^, Bi 4 Ti 3 0 12 and 
> BaBi 4 Ti 4 0 15 (1) showed that they have very similar structures. The symmetry is 
. tetragonal or pseudotetragonal, and the structures are each built up of quadratic 
"Bi a O a layers alternating with perovsMte layers, the latter having different heights 
in the three different cases. The generalized formula for the compounds might be 
written Me a O a (Me m - X fimOsm+i) where Me' is the 12 coordinated metal atominthe 
perovskite layers and R the 6 coordinated atom. The* formulae for the above com- 
pounds, Bi a 0 2 (CaNb a 0 7 ), Bi a O 2 (Bi 2 Ti 3 O 10 ) and Bi 2 O a [(BaBi a ) TiAsl thus have m 
: values of 2, 3 and 4. The simplest case, m-1, would correspond to the formula 
ifc a O a (RO J and to a structure built up of Me 2 0 3 layers and layers of jB0 6 octahedra 
each octahedron sharing four corners. Compounds of this type have, however, not 
been successfully synthesized as yet. 

The present paper deals with the compounds Bi 3 Nb0 6 F, Bi 2 TaO B F and Bi 2 Ti0 4 F 2 , 
which correspond to the simplest case, m = 1 above, except that some of the Q atoms 
are replaced by F atoms. The formulae of the compounds might thus be written: 
Bi 8 (0, F) 2 Nb(0, F) 4 etc. 

Preparation, powder photographs and analyses 

BiaNbOjF: When a mixture of BiF 3 and Nb a 0 5 in the mol ratio 4 : 1 was heated 
in adr at 800° C for a short time, a few single crystals (very thin plates) were obtained. 
Powder photographs of this sample indicated a tetragonal unit cell with the same 
cell dimensions as would be expected for the above general type when m = L The 
best conditions for the formation of this phase were then studied by heating 2.5 g 
mixtures (2BiF 8 + 1 /aNb a 0 5 ) in air at. 640° C, this low temperature being chosen to 
reduce the volatility of the BiF s . The reaction times were varied from 5-40 hours, 
and powder photographs were taken of each product. For reaction times of 7—15 
hours the lines of the above tetragonal phase predominated in the powder photographs, 
the few extra lines were very weak (see Table 1). 

The fluorine content was found to vary from 4.0 % (7 hours) to 2.4 % (15 hours), 
whereas the calculated value for Bi 2 Nb0 5 F is 3.2 %. No variation in the size of the 
cell with the fluorine content was found, and it therefore seems probable that the 
composition of the phase is constant and that the observed variation in the F content 
is due to the presence of small impurities which are not visible in the powder photo- 

39 



BEST AVAILABLE COPY 



FEB. 22. 2005 10:41AM Ma i I^FOGATE-IE INFO EXPRESS 



MO. 4214 



B ' A * W ™* ^ "rue*™ ofBi^F and isomorpkous compounds 
O Table 1 

O - Powder photograph of Bi 8 NbOgF (sample with 2.8 % F) 

0fK radxafaon XorK a =2.2909 A ' 



-Q 

a 



CO 

a> 



10< ■ sin* 0 C 



'calo 10* -ein» a 0 bs 



I 0 3 
006 
110 
112 
105 



114 

008 

116 
200 
202 

r 109 
k 00 10 

118 

21 3 



1319 
1708 
1784 
1974 
2078 



IdHa 



1332 
1711 
1796 
1969 
2083 



10 
11 

12 



206 

215 
• 1 1 

1 0 

00 

220 

222 

301 
/219 
\2 0 10 

3 03 

1 1 12 

226 
flO 13 
\310 

3 12 

306 
0 0 14 



2643 

3036 

3492 
3568 
3768 

4734 \ 
4743/ 
4820 
4888 



5276 

6647 

6527 

6631 

6830 

7137 

7327 

8076 

8303 \ 

8311/ 

8456 

8614 

8846 

89081 

8921/ 

9111 

9216 

9297 



2547 

2785' 

3033 

3093 

3490 

3667 

3754 

3808 

4737 

4827 
4891 



st 
m 
in 

WW 

vw 



w 
vw 
st 
st 
vw 
vw 

st 

w 

st 



5292 
5658 
6529 
6630 
6841 
7139 
7330 
8C80 

8304 

8466 
8611 
8844 

8919 

9119 
9195 
9292 



m 
w 

vw 
w 
w 
w 

vw 

WW 

st 

m 
m 
m 

m 

vw 
vw 
vw 



The values calculated for BijNbOjF are: 

Bi: §8.6, Nb: 15.2%, F: 3.2%. 
Ixom ttese figures it seems probable that *e formula of the compound is Bi^F. 

wSelrthe P 3«p^^ "»? T y M No analysis 

mobium and tantalumXS^tuX Z£Z&Zr * ~* 
40 




*3 



Fig. 1. C 



Bl a Ti( 

2:1 (tota 
photograj 
assuming 
the same 
phase are 
of the mi 
variation 
are 7.8 % 
fluorine a 
of BL>Nb( 
Bi fl Ti0 4 F a 

Method 
withNaO] 
(3).Thedi 



Bisniut) 
*as deterr 
precipitate 
as such. 



The dim( 
"with f ocusi 



FEB. 22. 2005MO:41AM 



Ma 



P) 




1 I^GATE-IE INFO EXPRESS 



NO. 4214 P. 



akktv f6r kemi. Bd 5 nr 4 




o 



the heating, . 
swing values 
2 ±0.6% K 



sBiaNbOaP. 

No analysis 
JNb0 8 F and 



One half of the unit cell of Bx^NbOgF. A denotes the region of Nb (O, F) 4 ootahedra 
and B the Bi 4 (0,F) a layers. 



Bi 2 Ti0 4 F a : Mixtures of bismuth fluoride and titanium oxide in the mol ratio 
2:1 (total 2.3 g) were heated in air at 640° for various lengths of thime. The powder 
photographs obtained from samples heated for 3 or 5 hours could be interpreted by 
assuming a mixture of BiOF (2) and a phase whose cell dimensions were nearly 
the same as those of BiaNbOjF. (See Table % where the reflexions from the BiOF 
phase are designated by 6 and those from the other phase by a). The fluorine contents 
of the mixed samples were found to be 6.4 % (5 hours) and 8.4 % (3 hours) but no 
variation of the cell size with the fluorine content was found. The calculated values 
are 7.8 % for BiOF and 6.7 % for Bi ? Ti0 4 F 2 . From the original Bi/Ti ratio, from the 
fluorine analysis and from the similarity of the powder photographs with those 
of BiaNbOgF (Tables 1 and 2), it was concluded that the formula of the phase is 
Bi a Ti0 4 F a . 

Methods of analysis: Fluorine. The samples were first decomposed by fusing 
with NaOH, and were then distilled with Hd0 4 as described by Willakd and Winter 
(3). The distillate was titrated with Th(NO a ) 4 using Na-alizarinsulphonate as indicator. 

Bismuth and Niobium. The samples were brought into solution, and niobium 
was determined as described in Scott's "Standard Methods" (4). Bismuth was first 
precipitated as BigSa, which was then redissolved, converted to Bi 2 O s and weighed 
as such. 

Unit cells and space group 

The dimensions of the unit cells were determined from powder photographs taken 
with focusing cameras of the Phragm6n type (Tables 1 and 2). The radiation used 



41 



FEB, 22.2005 10:41AM Mai l^FOGATE-IE INFO EXPRESS 



NO. 4214 



B. auiuyuxius, The structure ofBi^fbO.F and isomorphous compounds 

Table 2 

(^-2.2909 A), a denotes the Bi a Ti0 4 F a phase and b the BiOF Xse 



hki 



101 
101 

r i 03 

[002 
006 
110 
110 
1 1 2 
105 
102 



114 

1 1 2 
107 
116 
200 
200 
202 
103 

204 
211 

r i o 9 

113 

[00 10 
213 
202 



/206 
\004 

2 15 

212 

104 
/203 
\208 

1 0 11 

2 17 

0 0 12 
/220 
1114 

f 220 
1222 
213 

301 

r 2 1 9 

[20 10 
303 
301 
222 

1 1 12 



phase 



lO*sin*0oalo 



a 
b 
a 
b 
a 
a 
b 
a 
a 
b 



b 
a 
a 
a 
b 
a 
b 

a 
a 

a 
b 
a 
a 
b 



a 

b 

a 

b 

b 

b 

a 

a 

a 

a 

a 

b 

b 

a 

b 



a 
a 
a 
b 
b 
a 



10* Bin*0 O bs 



957 
1270 

1351 \ 

1352 / 
1771 
1816 
1864 
2013 
2138 
2284 



941 
1266 

1354 

1767 
1811 
1858 
1999 
2132 
2288 



lobe 



WW 

m 

st 

m 
m 



w 

w+ 

WW 



2603 

3216 
3319 
3587 
3631 
3728 
3828 
3974 

4418 
4588 

4893) 
4906 > 
4919 J 
4982 
6080 



2601 
3074 
3231 
3320 
3600 
3624 
3744 
3822 
3982 
4352 
4426 
4590 
4674 

4904 

4979 
5084 



m 
vw 

w 
vw 

sb 

St 

w 
w 
w 

WW 
WW 

w 

WW 



St 
St 

w 



6402 \ 
6408 / 
5769 
6012 
6340 
6770 \ 
6779 / 
6860 
6950 
7084 
7262 \ 
7272 J 
7455 \ 
7459 / 
7702 

8210 

8524 \ 

8550 / 

8613 

8736 

8814 

8900 



5416 

6788 
6025 
6353 

6786 

6869 
6960 
7075 

7262 



7456 

7709 
8049 
8210 
8352 

8524 

8603 
8725 
8807 
8900 



m+ 

m 
m 
w 

m 

m 



m 
id 

w 

in 
vw 
vw 
vw 

St 

m 
w 
w 
m 




agrees 
calculi 
Zerc 
was n« 
than 1 
b+k + 
Pow 
and frc 



Bi 2 K 
unit ce 
the mac 
for I od 
tie Pat 
sity val 
We) si 
of othei 
position 
or 000. 
gave th« 
No d€ 
FoxB 
meter. A 
occupy t 
was obti 



42 



FEB. 22. 20055; 10:41AM Mail I^ATE-IE INFO EXPRESS 



NO. 4214 P. 6/10 



idiatioa 
tOB" phase 




akkjv f6h kemi. Bd 5 m 4 
Table 2 (continued) 



hhl 


phase 


10* sin* flcaic 


10* sin 8 0<>te 


lobs 


226 
310 
204 
312 
3 10 
/ 106 
\ 305 


a 
a 

b 
a 
b 
b 
a 


9033 

9078 

9136 

9275 

9319 

9382 \ 

9400 / 


9027 
9072 
9136 
9272 
9319 

9384 


m 
w 
vw 
m 
w 

m 



^ was CViT (Acrx a = 2.2909 A). As mentioned above the powder photographs could 
' -be interpreted by assuming tetragonal unit cells; the cell dimensions are given below. 

{ * a (A) c(A) 

BiaNb0 5 F 3.835 16,63 

Bi a Ta0 6 F 3.829 16.64 

Bi a Ti0 4 F 3 3.802 16.33 

The errors in these figures are estimated to be ±0.1 %. 

The observed density was 8.0 fox Bi a Nb0 6 F (preparation with 2.8% F), which 
. agrees fairly well with the assumption of 2 formula units per unit cell, giving a 
- calculated density of 8.26. 

Zero and first order Weissenberg photographs around the a axis were taken. There 
was nothing in the Weissenberg photographs to indicate a Laue symmetry lower 
than D u — ijmmm. The only extinctions found were that A, k, I were absent for 
h+k+l odd, which is characteristic of the space groups Cj„ Z)L Did and DlL 

Powder photographs only wexe taken of the compounds Bi 2 TaO B F and Bi a Ti0 4 F 2 , 
and from these it was concluded that these substances are isomorphous with Bi a NbO B F. 

Positions of the metal atoms 

Bi a Nb0 5 F: With 2 formula units per unit cell there are 4 Bi and 2 Nb atoms per 
unit cell. The intensities of the spots in the Weissenberg photographs seemed in 
the main to depend only on the I values. Thus for I even fooi^m^ Aoi e ^°- 
for I odd: I 10I I 2 u = hoi etc - With these intensity values a good approximation of 
the Patterson-Harker function along 00 z could be obtained by using only the inten- 
sity values of h 0 1 and h 1 1. The Patterson-Harker function thus calculated (not given 
here) showed only one, big, maximum, at 2=0.34. This maximum, and the absence 
of others, could be explained only by assuming that 4 Bi atoms are situated at the 
positions ±002 with 2=0.17 or 2 = 0.33, and the Nb atoms at the positions 00| 
or 000. Arbitrarily choosing 000 as the position for Nb; trial and error calculations 
gave the value 0.325 for the Bi parameter. 

No determination of % B \ was made for Bl^TaOaF, 

For Bi 2 Ti0 4 F 2 the powder photograph data weTe used to determine the Bi para- 
meter. Assuming the Ti atoms to be situated at 000 and the O and the P atoms to 
occupy the same positions as given below for BiaNb0 6 F, the value z B i =0,327 ±0.006 
was obtained from trial and error calculations. 



43 



FEB. 22. 2005 10:41AM Mai l^FOGATE-IE INFO EXPRESS 



NO. 4214 



7/1 osr- 



B. AimxynxxTTS, The structure ofBi^l,O s F and isomorphous compounds 



CL 

o 
O 

JQ 

■= 
O 

"t/5 



Weisaenberg photographs 0 f 



Zero layer 




I 
1 
3 
5 
7 
9 

1 1 

13 
15 
1 7 
19 



-icalo 




-fcalo 


•fobs 


7 


w 


1 


vw 


270 


vst 


42 


w 


40 


w 


8 


vw 


1 




0.2 




76 


m 


30 


vw 


18 


w 


10 


vw 


3 


vw 


3 


vw 


20 


m 


19 


m 


12 


w 




H 


w j 







Positions of the 0 and the F atoms 
dilation fe£ °l* frl" 4 146 * * -T* C - 0Uld n0t be «M« from the 

the remains 4 (0,1) aioxns, ( 0} ^ at £e p^W ofi it " * 0nly I00m f °' 
44 




1 1 



The co- 



The pro 
ties for tl 
derived as 



The line 
.indicated I 
the agreeir 



; 
I 



Tt 

photographs 




Mail ^)GATE-IE INFO EXPRESS 



NO. 4214 P. 



ARKTV FOB KEMI. Bd 5 HT 4 



Hb0 6 F Cu K a radiation 



either from the 
arity in the re- 
ef ore treated as 
ae 0 and the F 
F for which z B i 

3d by a regular 
-(0, F)=*2.0 A. 
only if 4(0, F) 
thz-0.12, and 
listance (0,F)- 
is only room for 



First layer 



hk 



1 1 



31 





lot* 


IcaXc 


lo s 


210 


vst ' 


36 


w 


17 


w 


4 


WW 


11 


w 


2 




110 


m 


33 


w 


27 


vw 


9 


vw 


2 


WW 


1 




21 


■ m 


20 


w 


14 ' 


w 


20 


w 


6 


w 


17 


w 


19 


m 






58 


8t 









hk 


01 




21 




41 


I 




2calc 


Jobs 


ioalo 


Jobs 


Joalo Jobs 


I 




7 




2 


vw 


1 WW 


3 




270 


vst 


74 


m 


33 w 


5 




40 


m 


13 


w 


7 — 


7 




1 




0.3 




0.2 — 


9 




76 


vst 


40 


w 


63 w 


1 1 




18 


m 


12 


WW 


61 w 


13 




3 


vw 


3 


vw 




16 




20 


m 


19 


m 




1 7 




12 


w 


19 


m 




19 




14 


w 









The coordination and distances in A. will be: 



Bi-4(0, F),=2.29 
Bi-4(0,F) 1 =2.9 
(0,F) 8 -4(0,F) 8 =2.71 
(0,F) 1 -4(0,F) 8 =2.9 



Nb-2(0,F) X = 2:0 

Nb-4(0, F) 2 =1.92 

(0,F) s -4(0,F) a =2.71 

(0^-4(0,^=2.8 



The proposed structure ia given in the summary. Calculated and observed intensi- 
ties for the reflexions in the Weissenberg photographs are given in Table 3. Jcaic is 
derived as follows: 



•?ealc s 



1 + CO8 8 20 

16OO-sin20 



•F 2 where F^Xf cos 2ji(hx+ ky+lz). 



The lines of maximum absorption in the Weissenberg photographs (see 5) are 
indicated by dotted lines in Table 3. If the absorption effects are taken into account, 
the agreement between calculated and observed intensities is quite good. 



45 



FEB. 22. 2005 10:41AM Mai 



ATE-IE INFO EXPRESS 



NO. 42 14. ^P. 9/1 Of" 



Q. 

O 

O 

n 

■= 
o 

"to 

d) 




B. a^trivillius, The structure of Bi^NbO^F and isomorphous compounds 

Discussion of the structure 

Even if the (0, F)i atoms (see above) are assumed to occupy such a positio^ 
that the distance Bi-4 (0, F) x is as small as possible [z (0, F^O.15, (0, Fw^^ r 
(0,^8=2.5,^-2(0^)^2.5,81-4(0^)^2.7], the distance BiHt (0, F) x ^pfe^ 
still be much longer than the distance Bi— 4 (0, F) 3 . It therefore seems ' 
propriate to describe the structure of Bi 2 Nb0 6 F as being built up of Bi 2 (0, pi' 
layers alternating with octahedral layers having the composition Nb (0, F) 4 , botfH 
layers being perpendicular to the o-axis. It might be pointed out that the sfanictureoS 
of Bi 2 (0, F) a Nb (O, F) 4 is basically of the same type as the et X x structures", Me z 0jgk 
previously investigated bySiLiirei (6). Thus the octahedral sheets Nb(0, F) 4 correspond^ 
to single layers of halogen atoms, X, in Me^O^X. >$if 

Ml 

Discussion of the distribution of the O and the F atoms 

As seen above, the distance Bi-4(0, F) 3 is 2.29 A for Bi 2 Nb0 5 F. For Bi 2 Ti0 4 t 3 '5 
the corresponding distance' is calculated to be 2.26 + 0.06 A. These distances are %f 
very nearly the same as the corresponding distances, Bi-4 0, within the BijO^S 
layers of oilier bismuth oxicompounds (6). This need not, however, necessarily meaa .fi 
that the Bi 2 (0, F) 2 layers (see the figure) are free from F atoms, since compounds £ 
with Bi 2 (0, F) 2 layers which certainly contain F atoms have not been investigated £ 
hitherto, and thus the distances within such layers are unknown. 

For the present it seems therefore best to make no special assumptions as to the $ 
distribution of the 0 and F atoms. 



SUMMARY 

The crystal structure of Bi 2 Nb0 6 F has been investigated by means of Weissenberg " 
and powder photographs. From powder photographs the compounds Bi 2 Ta0 B F and -' 
Bi a Ti0 4 F a have been found to be isomorphous with BiaNb0 5 F. The following struc- 
ture is proposed for BijjNbOgF: 

Dl\—I i/mmm 

(000,B4) + 

2Nb in 2 (a): 000 

4Bi in 4(e): ±00z 
4(0, F) x in 4 (c) : 0*0, £00 
4 (0, F) a in 4 (e) : + 00z 
4(O,F) s in4(d):0H, i<>l 



2=0.325+0.001 
2=0.12+0.01 



The cell dimensions are a = 3.835 A, c = 16.63 A for BigNbOfrF. The positions of 
the metal atoms were determined from the diffraction data, those of the (0, F) 
atoms from space considerations. Although it does not seem improbable that 0 atoms 
alone occupy the positions 0$£, JO J, Bi and O thus forming Bi a 0 B layers as 
in other bismuth oxicompounds, nothing can be definitely stated as to the distribu- 
tion of the 0 and F atoms. 

The structure is built up of quadratic Bi 2 (0, F) a layers alternating with octahedral 
sheets having the composition Nb(0, F) 4 (see figure) and the formula might thus 
be written: Bi 2 (0, F)^^, F) 4 . The structure is formally related to a series of 

46 



rprevio* 
repres€ 

Unh 



rep: 

Mineral. 
Ed. 5 (I 
edited b 
(1937) 4 



.1 



FEB. 22. 2005 10:41AM Mail I^ATE- 



IE INFO EXPRESS 



NO. 4214 P. 10/10 



.ds 



such a position:^ 
-0.15, (0, P) x ^& 
3i-4 (0,1)! wiHH 
•efore seems ap- "■*« 
ip of Bi 2 (0,p)^; 

Nb(0,F) 4> both.>; 
lat the structure .v 

tares", Mefi^fS 
3, F) 4 correspond^ 



abkiy f6r kemi. Bd 5 bt 4 



previously investigated structures of general formula Me 2 0 2 (Me m _ x It m O$ m +i) and 
^presents the simplest case of this series, i.e. m = l. 

University of Stockholm, Institute of Inorganic and Physical Chemistry, May 1952. 

BEFERENOE8. 1. Auxivlllius, B., Arkiv Kemi 2 (1950) 519. — 2. , Arkiv Kemi 

jfineral. QeoL, 26 B (1948) iuo 2.-3. Willard, H. H. and Winter, O. B M lad. Eng. Chem. Anal. 
«d 5 (1933) 7. — 4. Standard Methods of Chemical Analysis by W. W. Scott, fifth edition, 
i edited by N. H. Furman, New York 1925, p. 335 and p. 338. — 5. Wells, A. F„ Z. Krist. 96 
(1937) 451. — 6. Sillen, L. G., Dissert. Stockholm 1940. 



.toms 

'. For Bi a Tib 4 P s : 
se distances are 
rithin the Bi a O a 
lecessarily mean 
ince compounds 
een investigated 

t ptions as to the 



i of Weissenberg 
s Bi a TaO B F and 
following struc- 



The positions of 
le of the (0, F) 
)le that 0 atoms 
Bi a O a layers as 
to the distrihu- 

with octahedral 
mla might thus 
1 to a series of 



a 
o 

o 
o 

a 
< 

O 



Tryckt den 24november 1952 
Uppsala 1952. Almqvifit & WikseUfl Boktryckeri AB 



47