J. inorll, nucl. Chem., 1970, Vol. 32, pp. 1427 to 1441. Pergamon Press.

Printed in Great Britain

EFFECTIVE IONIC RADII AND

CRYSTAL CHEMISTRY
R. D. S H A N N O N and C. T. PREWITT
Central Research Department. Experimental Station, E. 1. du Pont de Nemours and Co., Wilmington,
Delaware 19898

(Received 8 September 1969)

A ~ t r a c t - T w o types of structure stability fields can be constructed using effective ionic radii. Type I
plots of rz 3 vs. unit cell volume of MX, or MnM'qXs compounds are approximately linear and can be
used to help predict the radii of certain cations and the effects of high pressure on structure. Type Ii
plots of ru vs. ru, for MpM'qX, compounds are used to systematize structure types, to predict possible
new compounds, and to predict effects of high pressure on structure. Deviations of Type 1 plots from
linearity frequently indicate errors in unit cell dimensions (ABO2 delafossite series), deviations from
stoichiometry (VO and TiO), special bonding characteristics (PdCoO2), or change in cation co-
ordination (rare earth orthoferrites). Deviations of ZnFz and MgF2 from the ruffle fluoride plots are
not understood. Crystal structure refinements in conjunction with effective ionic radii can sometimes
be used to provide information about valence, cation coordination, and electron spin. lnteratomic
distances in AgO are consistent only with square planar coordinated Ag + and the composition
Ag+Ag~+O2. Cobalt-oxygen distances in PdCoO~ are consistent only with trivalent low-spin cobalt.

1. I N T R O D U C T I O N
CORRELATIONS between ionic size and the structure and properties of crystals
have been pointed out by many investigators. Goldschmidt[ 1,2] and Pauling[3]
found that the ratio, p, of the cation radius to the anion radius determined to a
large degree the CN of the cation and thereby the structure type. Wells [4] and
others[5, 6] have expanded this concept extensively by showing how cation-
anion polyhedra can be ordered in space to derive specific structures. Although it
must be recognized that other properties of the ions such as polarizability[l],
electronegativity[2], and nonspherical electron distribution[7] are also important,
ionic size has been shown to be a major factor in determining structure type
especially in ionic compounds.
This strong correlation between ionic size and structure led to the concept of
structure stability fields which allow prediction of the formation of isotypic
compounds. Goldschmidt's rules for isomorphous substitution[l] are also based
on ionic size considerations, and ionic size considerations led Matthias to predict
1. V. M. Goldschmidt, T. Barth. G. Lunde and W. H. Zachariasen, Skr. norske Vidensk-Akad.
1, Mat.-Nat. KI., No. 2.
2. V. M. Goldschmidt, Geochemistry, p. 86. Clarendon Press, Oxford (1954).
3. L. Pauling, The Nature of the Chemical Bond, p. 540. Cornell University Press, New York
(1960).
4. A. F. Wells, Structural Inorganic Chemistry, p. 93. Clarendon Press, Oxford (1962).
5. A. Magnrli,J. inorg, nucl. Chem. 2,330 (1956).
6. L. Kihlborg, Ark. Kemi21, 471 (1963).
7. L. E. Orgel, An Introduction to Transition Metal Chemistry: Ligand Field Theory. Methuen,
London (1960).
1427
1428 R.D. S H A N N O N and C. T. P R E W I T T

ferroelectricity in LiNbOz and NaNbOz[8]. Thus, ionic radii as originally

developed by Goldschmidt[1], Pauling[9], Zachariasen[10], and Ahrens[ll]
were shown to be useful to the crystal chemist.
However, beyond these uses mentioned above, the traditional sets of ionic
radii were inadequate. The tables listed radii only for octahedral coordination,
did not take into account the effects of electronic spin state, and lacked values for
numerous ions. Furthermore, the traditional sets of ionic radii did not result in a
linear relationship between cationic volume and unit cell volume for isotypic
series of compounds. Consequently a new set of "effective" ionic radii was
derived to correct these deficiencies [ 12]. These radii can be used in synthesis to
predict isomorphous substitution, and with the aid of structure stability fields and
radii-volume plots, can be used to predict isotypic compounds. The radii have also
proved valuable in the interpretation of crystallographic data. Experimental
interatomic distances can be evaluated in light of interatomic distances calculated
from the table. This comparison can frequently provide information about
valence, electronic spin state, and coordination number of the cation. Finally,
radii-volume plots can be used to evaluate the accuracy of cell dimension data.

2. SYNTHESIS OF S O L I D S O L U T I O N S A N D ISOTYPIC C O M P O U N D S
A. Isomorphism
Formation of solid solutions and isotypic compounds depends to a large
degree on matching the sizes and polarizabilities of ions in environments of
similar coordination[l]. Synthesis of solid-solution systems requires more rigid
criteria than synthesis of isotypic compounds. Thus GeO2 (rutile) and PbO2
(rutile) are isotypic but do not form solid solutions because of size differences.
Goldschmidt's empirical rule [ 1] is that solid solutions between MO and M ' O can
be prepared only if there is no more than 15 per cent difference between ionic
radii of M and M'. It is not necessary that the end members be isotypic (and the
substituting ion may even differ in oxidation state) provided some means of charge
compensation can occur. For example, CaO and Yb203 form a solid solution
at the CaO end with Yb ~+ ions being compensated by cation vacancies[13].
Although similar size and polarizability indicate the possibility of forming a solid
solution, this does not always assure success. In the SnO2-IrO2 system[14],
SnO2 and IrO2 are isotypic compounds whose cation radii differ by only 8 per
cent, but there is no evidence of solid solubility on the SnO2 side. Thus, the
chemist is forced to rely on ionic size as a necessary but insufficient criterion for
solid solution. To this end the new table of effective ionic radii should be a more
practical guide than previous tables for two reasons: (1) the radii in this table
agree better with experimental interatomic distances and relative unit cell-volume

8. B. Matthias, Phase Transitions in Ferroelectrics In Phase Transformations in Solids, p. 335.

Wiley, New York (1951).
9. L. Pauling, J.Am. chem. Soc. 49, 765 (1927).
10. W. H. Zachariasen, Z. Kristallogr. 80, 137 ( 1931).
11. L. H. Ahrens, Geochim. cosmochim.Acta 2, 155 (1952).
12. R. D. Shannon and C. T. Prewitt,Acta crystallogr. B25, 925 (1969).
13. T. L. Barry and R. Roy,J.Am. ceram. Soc. 50, 105 (1967).
14. C. L. McDaniel and S. J. Schneider, J. Res. natn. Bur. Stand. 71A, 119 (1967).
 Effective ionic radii and crystal structure 1429

relationships and (2) the table allows comparison of radii of ions with similar
coordination numbers.

B. Structure stability fields

Synthesis of isotypic compounds, i.e., isostructural compounds, is facilitated
by the use of structure stability fields. These diagrams are made by plotting unit
cell volumes vs. ru a for MX, compounds (type I) or rM vs. rM, for M~M'qXs com-
pounds (type I I). Thus. the radii allow a systematization of structure types that is
useful to the crystal chemist. A number of stability fields of both type I and type I I
have been prepared for use in synthesis work and are shown in Figs. 1-10.

1. Type I stability fields

A type I stability field is shown for MO (rocksalt) in Fig. 1. Similar stability
fields have been shown for MO2 (rutile)[15], and M2Oa (corundum)[16] com-
pounds. We have chosen diagrams for each of these three simple structure types
to illustrate the general principle. Similar stability fields (Figs. 3-10) can be
prepared (1) for any series of isotypic compounds or (2) for any group of com-
pounds having the same cation-anion ratio.
The rocksalt structure has a wide stability field and one can generally assume
that divalent ions having a radius between 0.70 and 1.15/~ will form rocksalt
structures. ZnO, an informative exception, has, under normal pressures, the
zincite structure featuring WZn2+ ions*. Such a structure exhibiting tetrahedral
coordination would not be expected to form on the basis of ionic size considera-
tions and can only be explained by the tendency of Zn ~+ to form covalent bonds

I I I 1 I I i I I I I I
140

130 ROCKSALT MO . /

120

I10 / c oe /
V 'dd
IOC

90

8(;

7C MN%~; V *Ti
I I ~ I I I I I I I I I
•:50 ,40 -50 -60 -70 "80 -90 1-00 I-I0 ¥20 1.30 1"40 1.50

Fig. 1. Stability field for MO rocksalt structure.

*The Roman numeral at the upper left of the ion refers to the cation coordination.
15. R. D. Shannon, Solid. St. Comm. 6, 139 (1968).
16. C.T. Prewitt, R. D. Shannon, D. B. Rogers and A. W. Sleight, Inorg. Chem. 8, 1985 (1969).
1430 ~ R.D. S H A N N O N and C. T. P R E W I T T

" ¢N o C' I - •CUBIC 6:6~6

r"t a L i F e O r T [ T R A G O N A L 6:8:6
0 a Nar-~-RHOM8OHEDRAL 6 : 6 : 6
• C u F e O i - DE.LAF'OSSiTE 2:6:4
li K FeOl= - O R T H O R H O M B I C 8:4:6
I l l ,8-NeFeOt-ORTHORHOMBIC 4 : 4 : 4
~ ~::~,0 , 4 f f MISCELLANEOUS
- B i 3+ 0
bOO-

0"90- .yS*
o
/ o
//
-~d 2÷ ,/ Cl Li FeOz
_Mn2 ÷ / Q
0.80- .in3 + // • r~ 0 o
//
//
/
-SC3+ // • r-1 o o o im

0 ' 7 0 - "Ni 2÷ (
I O~ NO FeOz
L T i 3÷ I o
I-Rh a ÷ - , I • • •
L Me'if • t~
8 o
I-Go';
E.Cr 3
~|
=
• I o 8
Q
O'~OTZnZ+ i Cu FeOz
rNp" I, DELAFOSSITE 0 ~IF
AI 3÷ I •
--Co3÷ LS L I Ill • o
0"50- -=Fe3÷ L. . . . . . . . ~ El

8G03 ÷ m5 mm Im IBI Im

No F e O z KFe02
0.40-
-ZAI3+ gl~ mn im IB IW

=p,÷
Ba2"
N*" IK* Re Cs*
0.30 i
•c°. q . 5'" ,I , 1 -- I
a~o o.~o 0.6o o.~o o.~o o.~o L0o ,.io &o ~.~o 1.40 1.50 1.60

r,, (,~)

Fig. 2. Stability fields for MM'O2 compounds.

to four near neighbors using s p a hybrid orbitals. High-pressure synthesis presum-

ably forces Zn 2+ into octahedral coordination [ 18]. Thus, construction of stability
fields will occasionally suggest the use of high pressure in forcing the adoption of
a particular structure predictable by ionic size considerations.
Other compounds containing cations whose radii are either too small or too
large for a certain structure and which thereby lie outside the stability field can
also be made to fall inside the stability field by the use of high pressure. An
example is the stability field of the MO2 rutile structure[12]. At pressures of
100 kbar, SiO2, normally a [vsi4+ structure, can be prepared as stishovite with

17. R. D. Shannon, SolidSt. Comm. 4, 629 (1966).

18. C. H. Bates, W. B. White and R. Roy, Science 137, 993 (1962).
 , , Ipo /
82 i i ,
180 FLUORITE MO 2

so RUTILE MF2 Mne,//~

76 V
V74 /
16(: /" Np R"
Pu.,/eCe
72 G.
=:

7o / / ~ Co
150
6a / eZn .

,e ? / 140
• MQ Hf / T b ?,
64

Zr
I I I 130 II I I I. I I I
•40 , ~0 "60 • 60 .70 -80 .90 1,00 1.10 1.20 1-~0
62 .30
r3 r ~ ('~1~)

Fig. 3. rM3 vs. U n i t cell v o l u m e for the MF~ rutile structure. Fig. 4. r~ a vs. Unit cell v o l u m e for the MO~ fluorite structure.
 b~
! i i I I
. . . . . . , Nd/
/
330 2c/O
TYSONITE MF3 130¢
C RARE EARTH M203 SSm/~/
3211 ~p /Eo
Gd

1200
.o/O b p
~,o f', =
>.
Z
1100 Z
V30¢ Sme/ ©
V Z

• Eu
IOOO .m

"0

Ho
900
21111~
800 I I I I I I I
I I l I I - 20 • 30 - 40 • 50 • 60 -70 -80 -90 ~00
27C .70 .60 .90 I'00 1"10 1'20
r3 r$

Fig. 5. ru 3 vs. Unit cell v o l u m e for the MF3 tysonite structure. Fig. 6. ru a vs. U n i t cell v o l u m e for the M2Oa C rare-earth structure.
 160 I I I
I i

15o DELAFOSSITE MM'O 2

Rh 02._
150 -
145

AgCrC
rn
140 hO 2 / AgCr02_ ,<
14( -

.Fe02
CuRh02~
Ag
135
==
AOAI02"// // ~FC"G°Ot
130 /~ 13( - Cu C r 02 J A g C o O 2-
E.
u~
125 . /
Pdcoo~j p.
~ d CoO 2 a
12C -

CuCoO
CuCoO
2
114 I I I
I i i 0-1 0-2 0 -3
1150 .Ioo -200 .50O -400

r~,
Fig. 7. r~, 3 vs. Unit cell volume for the MM'O2 delafossite structure. Fig. 8. ru a vs. Unit cell volume for the MM'O2 delafossite structure.
 1434 R . D . SHANNON and C. T. PREWITT

350 i i i I f i I I I I I [

340 ZIRCON MM'O,, ^ v Sn

•.T ~r x~"

330
A~ ~ - ~ o ~
I=/~v~. Tb
,/~o~ ~ Dy
32G ~ o~O
-,o
V 310 *.~Yb
-~Lu
, /
300

290

280

270 I I I 1 I I I I I I 1 I
-04 .08 -12 -16 .20 -24 -28 -32 .36 -40 .44 -48
3
rM'

Fig. 9. rM, ~ vs. Unit cell volume for the M M ' 0 4 zircon structure.

I ! i i i i i i i i i i
550

~.0 OLIVINE MtS|O 4 ~ ~ , ~ (

510 Fe
V
30O

290

280

270 I I I I l I
I .418 I I I I
•3 2 .34 -36 -38 -40 "42 -44 -46 "50 .52 .54 .56 .58

r3

Fig. 10. rM~ VS. Unit cell volume for the M2SiO4olivine structure.

octahedrally coordinated silicon[19]. In this case, the stability field has been
enlarged by forcing smaller cations into the rutile structure with higher coordina-
tion. A further example concerns the M~Oa corundum structure. In2Oa and T12Oa,
normally of the C rare earth structure, can be forced into the corundum struc-
ture[16, 17]. In these transitions no increase in primary coordination occurs, but
a more closely packed oxygen network is produced by taking advantage of the
high compressibility of the large In a÷ and TP + ions. Thus, a stability field has
been enlarged by forcing larger cations into a structure with the same primary
coordination.
19. S. M. Stishov and N. V. Beiov, Dokl. Akad. N a u k S S S R 143, 951 (1962).
 Effective ionic radii and crystal structure 1435

2. Type II stability fields

Stability fields of this type are more complex than type I and frequently cover
a wider variety of structures since both the ratios r,/r,, and r,/rx are important
in determing structure. We will illustrate the principles with (1) stability fields of
structure types adopted by oxides with general formulas MM'O2, MM'O4, and
M2M'O4, and (2) stability fields for the perovskite (MZ+M'3+O~) and pyrochlore
M2a+M~4+Or structures. The construction of such diagrams is frequently difficult
because of the change of CN as ionic size varies. Octahedral radii are generally
used for consistency and because a complete set of radii for other CN's is generally
not available.
The structure field of MM'O2 (Fig. 2), illustrating the use of radii for several
coordinations, contains at least nine structures. Our interest has centered around
one of these structures-the CuFeO2 delafossite structure[20] adopted by
PtCoO~ [21]. This structure is characterized by two-coordinated Pt ions and
six-coordinated Co ions. Since PtCoO2 exhibits unusually high anisotropic
metallic conductivity, efforts were made to synthesize isotypic compounds by
replacing either Pt or Co. Using Fig. 2 it was clear from radii and coordination
considerations that the only possible M ions would be Cu, Ag, Au, and Pd
whereas possible M' ions were transition metal ions whose radii lie between
those of A13+ and Tl z+. The following compounds were successfully synthesized:
PdCoO~, PdCrO2, PdRhO2, AgCoO2, AgGaO~, AgRhO2, AgScO2, AglnO2, and
AgT102 [22].
The two stability fields of MM' 04 [23] and M2M' 04 [24] illustrate the complex-
ity of large-scale structure fields. The MM'O4 diagram is also seen to contain the
rutile structure.
The boundaries to the stability field of the M3+M'3+O3 orthorhombic perov-
skites were defined in 1926 by Goldschmidt[1]. The field points out in a simple
manner the isotypic compounds not yet prepared. It has been shown, as in the
case of MO (rocksalt) and MO~ (rutile), that the stability field could be markedly
enlarged by the use of pressure. Similarly it was possible to force the Ga 3+ ion,
which normally prefers tetrahedral coordination, into the perovskite structure.
Compounds in the series MGaOa from Sm-Lu were prepared by Marezio et
a1.[25]. Furthermore, boundaries of the field were enlarged by the synthesis of
MInO3 compounds (M = Eu, Gd, Dy, and Y), of InCrO3, and InRhO3126].
TIFeO3 and TICrO3 were also prepared at high pressures, presumably by prevent-
ing the decomposition of TIzOa. Once again, the syntheses demonstrate how
stability fields based on effective ionic radii can be used to predict possible new
compounds.
The final example of stability fields is that of the M2Z+M24+Or pyrochlore
structure[27]. Octahedral radii were used for convenience. The entire series of
20. A. Pabst,Am. Miner. 31,539 (1946).
21. C. T. Prewitt, R. D. Shannon and D. B. Rogers, To be published.
22. R. D. Shannon, D. B. Rogers and C. T. Prewitt, To be published.
23. K.S. Vorres, J. chem. Educ. 39, 566 (1962).
24. G. Gattow, Z. anorg, aUg. Chem. 333, 134 (1964).
25. M. Marezio, J. P. Remeika and P. D. Dernier, Mater. Res. Bull. 1,247 (1966).
26. R. D. Shannon, lnorg. Chem. 6, 1474 (1967).
27. R. D. Shannon and A. W. Sleight, Inorg. Chem. 7, 1649 (1968).
1436 R . D . S H A N N O N and C. T. PREWITT

germanates has recently been prepared by the use of high pressure [27]. The same
princple used in the synthesis of stishovite is believed to explain the enlargement
of this field. In addition, Sleight[28, 29] has recently prepared extensive series of
M2PhOT, M2PthOT, and MzPchO7, compounds with the pyrochlore structure
which are in the stability field.
It should be re-emphasized that the stability fields, although useful in predict-
ing new compounds, do not provide an unequivocal guide to synthesis. Factors
other than radii such as site preferences different from that predicted by the
radius ratio (Zn~÷, Ga z+, Li ÷) are frequently important. In another example one
might predict that RF~3÷Mo~4+O7 pyrochlore compounds could be prepared. This
is not the case, however, perhaps because the pyrochlore structure presumably
would not allow the formation of Mo-Mo bonds. These bonds are known to
distort the structure of MoO2 from tetragonal rutile to a monoclinic form.

3. Interpretation of crystallographic data

Effective ionic radii can, with the aid of routine measurements of unit cell
dimensions and more sophisticated crystal structure refinements, be useful in
solving various problems in chemistry and physics. Information can often be
obtained (1) from cell-volume data concerning cation coordination, solid-solution
effects, and the accuracy of cell-volume data itself and (2) from structure refine-
ments concerning valence, electron spin, and cation distribution over different
sites. In this section these uses will be demonstrated by examples taken from the
literature. Some of these data that appeared to conflict with previous theory are
rationalized.

A. Unit cell volume data

It was mentioned in Section 2 that plots of r a vs. unit cell volumes for isotypic
compounds can be used as structure stability fields (type I). Another useful
property is their approximate linearity. We have found that, if accurate cell
dimensions are known, the plots prepared for simple compounds using Table I
are generally linear to a first approximation. This property provides certain
information about compounds that deviate from the line. Figures 1 and 3-10
illustrate plots for numerous types.
Certain plots were chosen to test the assumed linearity. Reliable cell dimen-
sions were obtained for most of the possible compounds in the MO rocksalt-[30],
MO2 rutile- [31], M~Oz corundum-J16], M203 C rare earth-J30], MM'O2
delafossite-[22], and M23+M24+O7 pyrochlore-structure types. When literature
data were considered questionable, cell dimensions were redetermined for
synthetic materials of at least 99.9 per cent purity using a Hiigg-Guinier
camera[16,22,31]. Figures 1 and 3-10 (r a vs. cell volume) show excellent
linearity. On the basis of these results, we assume that such plots are approxi-
mately linear and any large deviation of a compound from linearity reflects some
28. A.W. Sleight, Mater. Res. Bull. 3, 699 (1968).
29. A.W. Sleight, lnorg. Chem. 8, 1807 (1969).
30. R . W . G . Wyckoff, Crystal Structures, Vol. 2. lnterscience, New York (1964).
31. D. B. Rogers, R. D. Shannon, A. W. Sleight andJ. L. Gillson, lnorg. Chem. 8, 841 (1969).
 Effective ionic radii and crystal structure 1437

significant difference in the interatomic forces important for that compound

relative to the rest.
In Fig. 1 showing the rocksalt plot, VO is found to have a unit cell volume far
below that anticipated from the other compounds. Since VO is known to contain
15% cation and anion vacancies[32], this deviation appears quite reasonable.
The refined monoclinic variants of the rutile type, MOO2133], NbO~[34], and
VO~ [35] all fall somewhat below the rutile plot[ 15]. Since these compounds are
known to show metal-metal bonding[36], possibly this bonding is reflected in a
reduced cell volume. The differences are so slight, however, as to make this
conclusion uncertain, especially since assumed metal-metal bonding in corundum-
type V203 and Ti203 [16] does not result in deviation of these two compounds
from the corundum line. Figure 7 shows excellent linearity in rM,3 vs. V for
AgM'Oz, PdM'Oz, and CuM'O~. However, when r u ~ vs. V for MCoO2, MCrO2,
and MRhO2 is plotted (Fig. 8), strong deviations occur for M-~-Pd. These com-
pounds are known to exhibit high metallic conductivity in the Pd layers and are
believed to contain Pd z+ plus a delocalized electron rather than Pd ÷. These
properties are reflected by the radii-volume plots in a reduced cell volume.
An unusual deviation from linearity occurs in the M3+M' 3+O3 plot[37]. In the
GdFeO3 structure[38, 39], the G d 3+ ion is known to be coordinated by 8 oxygens
at an average distance of 2.47 A and 4 oxygens at an average distance of 3.39 A.
Marezio e t a/.[40] have suggested that as the size of the M ions increases, the
average M - - O distance of the first nearest oxygens increases whereas the average
M - - O distance of the 4 second nearest oxygens decreases, thus increasing the
effective coordination number as one moves across the radii-volume plot. The
concave plots may thus reflect the change in the first-nearest and second-nearest
M - - O distances.
Nonlinearity can also reflect inaccurate cell dimensions, as best illustrated by
the MM'O2 plots (Fig. 7). Unit cell volumes taken from Wyckoff[30] and plotted
as crosses in Fig. 7 resulted in large deviations from linearity. Cell dimensions
redetermined on highly crystalline material prepared hydrothermally resulted in
the linear plot. It is therefore felt that radii-volume curves are a reasonably good
test of the internal consistency and/or accuracy of cell dimensions determined on
isotypic series of compounds.
Other deviations have been noted in certain plots. The most outstanding
example is that of ZnF~ and MgF~ in the MFz rutile plot in Fig. 3. Both com-
pounds have unit cell volumes considerably lower than would be predicted. This
behavior remains unexplained at present. Similarly, the deviation of ZrO2 from
the fluorite plot has not been explained.
The radii-volume plots can also be used to predict radii of ions for which no
32. J. B. Goodenough, J. appl. Phys. 39,403 (1968).
33. B. G. Brandt and A. C. Skapski, A cta chem. scand. 21, 661 (1967).
34. B. Marinder, Ark. Kemi 19, 435 (1962).
35. P. Kierkegaard and J. L. Longo, Unpublished data.
36. J. B. Goodenough, Magnetism and the ChemicalBond, l nterscience-Wiley, (1963).
37. C. T. Prewitt and R. D. Shannon, Trans. Am. Crystallog. Assoc. Vol. 5 (1969).
38. S. Geller, J. chem. Phys. 24, 1236 (1956).
39. P. Coppens and M. EibschUtz, Acta Crystallogr. 19, 524 (1965),
40. M. Marezio, J. P. Remeika and P. D. Dernier, lnorg. Chem. 7, 1337 (1968).
1438 R.D. S H A N N O N and C. T. P R E W l T T

structural data exist. If reliable values of unit cell volumes of compounds in an

isotypic series are known, a radius can be taken from the plot for the appropriate
series of compounds. The most reliable values of radii so determined have been
taken from two or more isostructural series. Some examples of effective ionic
radii[12] determined in this way are: octahedral Rh 4÷, Pt 4+, Re 4÷, Os 4÷, W 4÷,
Ta 4+, and Pb 4+ (MO2-rutile)[31]; octahedral Am a+, Np s+, Pu 3+, Ce 3+, and U 3+
(MF3-tysonite); octahedral Fe3+LS and Mn3÷LS (K3Mm(CN)6); and eight
coordinated Sc 3+, In 3+, TI 3+, Tm 3+, Tb 3+, Sm 3+, Pr a+, Nd 3+, and La 3+ (M2Mo'Or-
pyrochlore).
A further use concerns prediction of solid-solution effects. Vegard's Law can
be used to estimate the direction in which cell dimensions change in cases where
the two end members of a system are isotypic. In cases where the end members
have different structures one must rely on a set of ionic radii. An example is
Fe-doped ZnS having the sphalerite structure. Deer et al. state that the increase
in cell dimensions upon substitution of Fe in ZnS is paradoxical[41]. They base
their conclusions on the radii of m&allic Fe and Zn and evidently Fe 3÷ and Zn 2÷.
However, use of Ahren's octahedral radii for Fe 2÷ (0.74 A) and Zn z÷ (0.74 A)
would predict no change in cell dimension whereas use of Pauling's octahedral
radii of Fe z+ (0.76 ,~,) and Zn 2÷ (0.74 A) would predict the observed increase. A
more appropriate set of tetrahedral radii for Fe 2÷ (0.63) and Zn ~+ (0.60) from
Ref. [ 12] also accounts for the observed increase in cell dimensions.
Caution must be used, however, in such predictions. Cell volume data should
be used in conjunction with density data and a consideration of structure defects.
The case of the CaO-Gd203 [42] system illustrates this point. Although the radius
of Gd 3+ < Ca 2÷, the cell volume of Cal-xGdxO increases with x. This was
attributed to the formation of a cation vacancy whose effective radius was
greater than that of Ca 2+.

B. I n t e r a t o m i c distances
In reports of crystal structure refinements, authors usually compare their
observed interatomic distances with those obtained by others and also with
distances given in various compilations of average interatomic distances [43, 44].
Publication generally merits a literature search for the pertinent information, but
often a quick check of the reliability of an interatomic distance is desirable and
here the radii table seems to be of great value. An example where the table could
be used concerns the structure of GdFeO3, originally determined by Geller[37]
and refined by Coppens and Eibschi,itz[38]. In the first paper the average F e - O
distance was given as 1.93 ,~, and in the second paper, 2.01/~. The value from the
table, d(VIFe3+-IvO2-) = 2-025 ,~, shows the latter value to be more reasonable.
A similar situation exists for WGe4+ -- O in the FeGe(OH)6 determined as 1.96 ,~

41. W. A. Deer, R. A. Howie and J. Zussman, Rock Forming Minerals, Vol. V, p. 166. Wiley,
New York (1962).
42. T. L. Barry and R. Roy, Z. Kristallogr. 125, 70 (1967).
43. Tables of lnteratomic Distances and Configuration in Molecules and Ions, Spec. Pubis Chem
Soc. No. 18 (1965).
44. International Tables for X-ray Crystallography, Vol. 11I. Kynoch Press, Birmingham (1962).
 Effective ionic radii and crystal structure 1439

by Strunz and Giglio[45] and as 1-89,g, by Zemann[46]. The table gives

d(VIGe-toO) = 1.90 A.
One would like to be able to explain individual variations of interatomic
distances in a compound, but it is generally not possible to do this with the data
in the table. These variations are a result of distortions in the structure which
must be accounted for by a more sophisticated approach. Even when average
distances are concerned, there are apparently small variations which are not
accounted for in the table. However, there are situations where different crystallo-
graphic sites must be considered separately. In one of these, two or more similar
sites, e.g., tetrahedra, are present but have different cation contents. For example
in the aluminosilicates Si and AI often compete for a particular site in a structure.
Smith and Bailey [47] published curves depicting average tetrahedral distances as
a function of AI content for three classes of silicates; feldspars, sheet structures,
and isolated tetrahedra. Prewitt and Shannon[37] compared these curves with
two- and four-coordinated oxygen curves derived from the radii table. The curves
are comparable except possibly for the Smith and Bailey curve for structures
with isolated tetrahedra. Structures of this type are rare and the only point plotted
by Smith and Bailey for the AI end of this curve was for zunyite. This structure
was refined by Kamb[48] using a limited set of film data and the resulting AI-O
distance of 1.80 ,~ could easily be in error by 0.02 A. Furthermore, since average
Si-O distances vary from one site to another, the curve for four-coordinated
oxygen may not provide exactly the answer required for the AI tetrahedron in
zunyite.
Interatomic distances can frequently be used to obtain information about
other physico-chemical properties of solids, e.g., valence and electron spin.
Several examples illustrate these points.

1. Valence
The chemical composition of a compound often does not permit an unequi-
vocal assessment of the oxidation states of ionic species. It is sometimes possible,
however, with the aid of interatomic distances and ionic radii to determine the
valence. Two examples will illustrate this point: structure refinements of AgO
and PdCoO2.

(a) AgO
This compound was originally thought to be similar to CuO with square
planar-coordinated Ag 2+ ions[49]. However, a neutron diffraction study of AgO
showed the presence of two crystallographically different[50] silver atoms. One
is coordinated by a square planar array of oxygen atoms at distances of 2.01 × 2
and 2.05 × 2. Such an arrangement is typical of square planar coordination around
both d a and d a ions and is consistent with either Ag a+ or Ag2+. The table elimin-

45. H. Strunz and M. Giglio, A cta crystallogr. 14,205 ( 1961 ).

46. J. Zemann, N. Jb. Mineral. Monatsh. 67 (1959).
47. J. V. Smith and S. W. Bafley,Acta crystallogr. 16,801 (1963).
~8. B. Kamb, A cta crystallogr. 13, 15 (1960).
49. V. Scatturin, P. L. Beiion and R, Zannetti, J, inorg, nucl. Chem. 8, 462 (1968).
50. V. Scatturin, P. L. Bellon and A. J. Salkind, J. electrochem. Soc. 108, 819 (1961).
1440 R. D. SHANNON and C. T. PREWITT

ates Ag 2+ since this would give an estimated average distance of 2.10/~ based on
the analogy between VXCu2+and wSQCu2+. The other ion must therefore be Ag ÷.
Its coordination is discussed in the next section.

(b) PdCoO2
PdCoO2 [21,22], was assumed to contain the ionic species Pd z+ and Co s+ on
the basis of the occurrence of other Pd-containing oxides and fluorides. Although
attempts to prepare other isotypic compounds PdFeO~, PdNiO~, PdMnO2,
PdMgO2, and PdZnO2 were unsuccessful, this assumption was still maintained.
A structure analysis, however, showed the cobalt ion to be surrounded octa-
hedrally by oxygen ions at an average distance of 1.907 A, corresponding only to
a WCo3+LS-IVO2- distance (1.905). Furthermore, the Pd ions were found to be
two-coordinated at a distance of 1.973 A which is more compatible with a two-
coordinated dgPd + than with a dSPd 2+. Discovery of the Coa+LS ion led straight-
forwardly to the synthesis of the isotypic compounds PdCrO2 and PdRhOz. The
table thus helped to determine the valence of the cobalt and palladium ions and,
in addition, the spin of Co z+.

2. Electronic spin state

Low-spin ions are smaller than high-spin ions; therefore, interatomic distances
generally allow one to distinguish between spin states without the benefit of
magnetic measurements. The example of PdCoO~ shows how interatomic
distances lead to unequivocal determination of electronic spin. Cell dimensions
of cubic compounds with no structural parameters can also be used. Blasse was
able to infer that r(WCoa+HS) - r(VICr3+) and r(WCo3+LS) w_ r(VlAl 3+) by this
method[51]. Finally, radii inferred from radii-volume plots can provide informa-
tion about spin state.

3. Coordination
A cation coordinated by a specific number of oxygen or fluorine ions is
characterized by an average interatomic distance which generally does not
deviate by more than several hundredths of an angstrom unit from one structure
to another. A larger deviation generally points to a possible error in (1) structure,
(2) valence, or (3) coordination. Several examples from the literature point out
the importance of coordination on interatomic distances.
The example of AgO was mentioned previously. The ion Ag3+ was found to
be square-planar coordinated. The remaining Ag + was reported to be linearly
coordinated by two oxygen ions at a distance of 2.18~[50]. This is a large
deviation from the IIAg+-mO distance of 2.03/~ calculated from effective ionic
radii [ 12]. Further calculation shows Ag ÷ to be coordinated by two further oxygen
ions at a distance of 2.64 giving an average distance of 2.41 which compares
favorably with the IVSQAg+-WO distance of 2.40 A.
Another example is provided by structure determinations on (NH)sPdCI4 and
(NH4)2PdC16152] in which the authors find the Pd-CI distance to be identical in

51. G. Blasse,J. inorg, nucl. Chem. 27,748 (1965).

52. J. D. Bell and T. N. Waters,Acta crystaUogr. 21,440 (1966).
 Effective ionic radii and crystal structure 1441

both the Pd(ll) and Pd(IV) compounds. They express surprise over the identical
distances involving ions of different charge. However, by the use of effective
ionic radii and consideration of coordination the distances are the same: wSQpd2+-
C1 = 2.45 and wpd4+-Cl--- 2.46, assuming r(Cl) = 1-81 A. Although the actual
distances, 2.30 ~,, probably represent foreshortening caused by covalence, the
same distances are predicted for both compounds.
Acknowledgements-The authors would like to express their appreciation to Drs. D. B. Rogers,
A. W. Sleight, and B. L. Chamberland for providing accurate cell dimensions of numerous compounds
and for their continued interest in the topic of ionic size.