Phase Equilibria

J Am Caam Soc, 1 5 [ 6 ] 1416-22 (1992)

Crystal Structures of CasCr3012 and CasCr2SiO12, the

Chromium Analogs of SiI icocarnotite
Keith T. Adendorff, Johan P. R. de Villiers,+ and Gert J. Kruger
Departments of Geology and Chemistry, Rand Afrikaans University,
Johannesburg, 2000, Republic of South Africa

The crystal structures of Ca5Cr3OI2and Ca5Cr1.8Si1.2OI2,
the chromium analogues of silicocarnotite, Ca5P2SiOl2,
have been determined. Both compounds were grown at
1250°C and analyzed by electron microprobe analysis.
Diffraction data collection was done on spherically ground
crystals which are both orthorhombic with space group
Pnma. Charge-balance requirements as well as site-
occupancy refinement of the Si-containing compound point
strongly to the presence of both tetravalent and hexavalent
chromium in tetrahedral sites. The Si is located together
with tetravalent C r in a general position, whereas the
hexavalent C r is situated on a mirror plane. The calcium
atoms are located in seven-, eight-, and nine-coordinated
sites. The presence of vacant channels of 3.5 A diameter
perpendicular to (100) is a feature of this structural type.
Its relation to the apatite and glaserite structures is also
shown. [Key words: crystal structure, calcium, chromium,
silicates, synthesis.]
I. Introduction

G. C. Ulmer-contributing editor
T HE two compounds CasCr3012and CasCrzSiO12form part
of a solid-solution series in the system Ca-Cr-Si-0
in air. Figure 1 shows the solidus diagram of this system
projected onto the Cao-Cr2O3-SiOz ternary join.' The so-
Manuscript No. 196408. Received September 10, 1991; approved Febru- lution between the above two compounds is clearly indicated.
ary 27, 1991.
GJK supported by the South African Council for Scientific and Industrial The investigation reported here forms part of a study of the
Research. fundamental chemistry of the lime-chromite roasting reaction
+Author to whom corres ondence should be addressed, at the followin
address: Council for MineraPTechnology, Private Bag X3015, Randburg, 212f which is being considered as an alternative to the soda-ash
South Africa. process for the production of chromium chemicals.

caoy- " Y " _. -

-.
-a

Fig. 1. Solidus phase diagram of the system CaO-Cr oxide-SO2 in air.

141 6
June 1992 Crystal Structure5 of Cu5CriO12and CujCr2SiOl 1417

Table I. Crystal Data for Ca5Cr3OI2and Ca5Cr~.8Sil.zOlz The synthesized crystals were separatcd from the flux and
Data Type Ca, Cr?0I 2 CdTCrl XSll?OI2
ground into spherical shapes for structure analysis. The compo-
sitions of the crystals were determined by elcctron microprobc
CaO 50.14 53.04 analysis, using CaSi03 and Cr203 as standards, and are given
Cr203 49.88 3 1.42
SiO, 0.02 14.09 together with the crystal dimensions and other data in Tablc I.
Unit cell data of both crystals werc determined u s h g
a (4) 6.733(2)4 6.725(4)$ graphite-monochromated M o K a radiation ( A = 0.7107 A)
('$1
bc (A)
Space group
::::;$]
Pnmu
10.249((12)
15.812 4)
Pnmu
and angular measurements of 25 reflections on a single-crystal
diffractometer (PW 1 100, Philips, Eindhoven, Netherlands).
Pcalc 3.251 3.167 The intensities of the set of reflections from CasCr30t2were
Pobs 3.28 3.06 collected up to a maximum angle of 28"O and those from
p (cm-I), M o K a 52.014 42.948 Ca5Crl.&12012up to 23"O with the w/2B scan technique.
Crystal diameter (mm) 0.21 0.17 The backgrounds were measured at the ends of each scan
RFI 0.041 0.035
~~
range. The systematic absences dcfincd either orthorhombic
Rw 0.035 0.032 space group Pnma or Pn2,a, the former being used for
Total No. of reflections 1797 928 successful structure analysis. Lorentz-polarization corrections
No. of observed were applied to the reflection data and, since the sizes of
reflections 1578 790 the spherical crystals were sufficiently small ( p R = 0.55 and
' R F = ZIFohsl - IFcalcl/ZIFobsl.'RW = ZW[(IFohsI - I ~ C ~ I C ~ ) ~ / ~ 0.37,
W rcspectivcly), no absorption corrections were necessary.
(Fob,)2](i'2).W = l / d , where c2is obtaincd from counting statistics. "The figures The structure of CaSCr301zwas solved by direct methods
in parentheses represent the standard deviations of the values preceding them.
and refined by full-matrix least-squares methods using
the crystallographic program SHELX7h2 The structure of
CasCrl,xSil,zOlz is isomorphous to that of CaSCr3OI2and was
refined with the program RFINE4,' which allows occupancy
11. Experimental Procedure refinement constrained by the observed chemical composition.
Scattering factors for Ca2+, Cr3+, and ncutral Si and 0,
Single crystals of Ca5Cr3OI2and CasCri #Sil*OI2were syn- corrected for anomalous dispersion, were uscd. Refinement
thesized using CaO, CrzOs, and S i 0 2 (obtained by the firing proceedcd normally using anisotropic thermal parameters for
of silicic acid), all calcined at 1300°C, as starting materials. all atoms. In the case of CasCri.sSit.201z, the relative occu-
The charges were prereacted at 1250°C for 24 h, quenched, pancies of Si (and Cr) in both tetrahedral sites were also
and ground. The crystals of C a S C r l 8 S i l 2 O I were
2 grown refined by simultaneous constraint of the sum of the individual
with the addition of 10% flux (22.5% NaF, 27.5% CaF2, occupancies in each site to one, and the total amount of Si and
and 50% B203).The Ca5Cr3Ol2crystals were grown without Cr in the sites according to the ratio imposed by the overall
any addition of flux. Both charges were reacted in platinum chemical composition as described by Finger and P r i n ~ e .A~
crucibles for 6 days starting at 1250°C and cooled at a rate final-difference Fourier map did not reveal significant residual
of lO"C/h. electron density.

Table 11. Atomic Parameters in Ca5Cr3012and CasCrl.8Sil.2012

Fractional coordinates and esd's
Atom Equipoint
Atom site 'we fraction Occupancy' X b ) Y b ) zb)
1.ooo -0.37093 5
Cr
Crt
1.000
1.000 0.466(4)
-0.13937 8)
-0.14629114) :::%$] -0.36998191
Sit 0.534(4)
TET 2) Cr 0.500 1.ooo 0.02455 12) 0.75000 0.07729(8)
TET[2) Crt 0.500 0.892(8) 0.02606[20) 0.75000 0.07926(12)
Sit 0.108(8)
Ca(1) 0.500 1.000 -0.46 145(17) 0.75000 -0.1 7453(13)
Ca Ca 0.500 1.ooo -0.45975(26) 0.75000 -0.17883(9)
Ca 1.ooo 1.000 0.12483 10) 0.06725 7)
Ca(2)? Ca 1.000 1.ooo 0.12922[7) 0.0677511 1)
Ca 1.000 1.ooo 0.17939(11) 0.39318 5 ) -0.333 16(7)
Ca(3)
Ca(3)+ Ca 1.000 1.000 0 16690(17) 0.39785[7) -0.33570( 10)
O(1 0 0.500 1.000 0.2741 6 0.7500 0.0839(4)
0 0.500 1.ooo 0.2752[9] 0.7500 0.0843(5)
0 0.500 1.ooo -0.0755(8) 0.7500 -0.0709(5)
0 0.500 1.ooo -0.0755(8) 0.7500 -0.0709(5)
0 1.000 1.000 -0.3126 3 0.5339 1) -0.4858 2
0 1.000 1.000 -0.3140[5] 0.542312) -0.4789[3]
0 1.000 1 .000 -0.2290(4) 0.651l(1) -0.2742(2
0 1.000 1.000 -0.2285(5) 0.6511(2) -0.2764(3]
0 1.000 1.ooo 0.0398(4) 0.6195 2) -0.4657 2)
0 1.000 1.ooo 0.0347(5) 0.6 14512) -0.4586[3)
0 1.000 1.000 -0.0733(4) 0.4920(1) -0.2680 2
0 1.ooo 1.000 -0.0900(5) 0.4941(1) -0.270&]
0 1.000 1.000 -0.0443 4 0.1450 2
0(7)+ 0 1.ooo 1.ooo -0.045 1 !6] 0.1473131
'The second rows of parameter\ describe the \tructure of C.a.jCrl xSil2012 tOLcupdncy of Cr and Sl con%trmed to ddd up l o uluty
1418 Journal of the American Society-Adendorff et al. Vol. 75, No. 6

Table 111. Anisotropic Thermal Parameters? in A' (X lo4) for the Atoms in CasCr3012and CasCr1.8Si1.2012
Atom Atom ui 1 uzz u33 u12 ul3 u23
site type b) (PI b) (fl) (g) (0)

TET( 1) Cr 89(3) - 10(2) 5(2)

TET 1 * Cr,Si 112(h) - 2(5 - 13(5) - 12(5)
TI421 Cr 111(4) 0 - 15(3 0
TET(2)$ Si,Cr ];[ 104(7) 0 -22(6] 0
0
Ca 370 7) 0
Ca 538112) 0 0
Ca 115(3 123(3) 143 3) 6(3) -33 3)
Ca 119(6] 130(6) 186t6) 14(5) -26/5)
Ca 172 3) 145(4) 29(3)
Ca(3)t Ca 22517) 194(6) -23(6)
0
0
0
223 20)
30515)
117(17
196(31] %?!::] 0
0
0
-
-33( 17)
116(30)
-32 15
0
0
0
0(2)* 0 0 -60[26] 0
O(3) 0 115 12) 108 11) - 6(9) - 8(9) -7(10)
0(3If 0 123[19) 73[18) -7(16) 2(15) 7(W
O(4) 0 176 12) 112 11) 117 11) -13(10) 32(10) 18(10)
0 135119) 88117) 99[18) 6(16) 15(16) - l(16)

0 108(11 194(13) 126 12) 21(10) 21(9) -19(10)

0 73( 181 249(21) 114[19) - 12(17) 406) ll(18)

O(6)'
0
0 ;:$;?] 139 12
82tl81
24 10
17[17]
1(10)
-17(16)
26( 10)
-6(16)
O(7) 0 276 14) 116 12) 128(12) -14 10) 36( 11) 4(11)
(47)' 0 434i26) 153t21) 103(19) 4/20) 65(19) -20(17)
+The form of the anisotropic temperature fdctor 13 T = exp - 2 ~ ' ( a * ~ h ~ U+, b*'k2U22
, + c ' 2 / 2 U ~ +3 2a'b'hkUlz + 2a'c'hlUl3 + 26'c'klU23) *The second rows
of parameters for edch atom site d e w i b e the Ftructure of Ca5Crl 2012

Final positional parameters and occupancy

. - values with their 111. Discussion
estimated standard deviations are given in Table 11, and the
anisotropic thermal parameters in Table 111. The interatomic (1) Structural Description
distance's and angles as well as tables of observed and cal- In CasCr3012the structure consists of isolated Cr tetrahedra,
culated structure factors are available from the authors on situated either on a mirror plane or in general positions, and Ca
request. atoms (Fig. 2). In Ca5Cr,xSil.2012, the tetrahedra situated on

0 Ca atom
CacCr3OIlcell
Ca5Cr30110Hcell
K,Na(SO& cell

\
/
>

Fig. 2. A projection along the a axis showing the Ca atoms and Cr tetrahedra in the Ca5Cr3012 structure. The relationship to the cells of
glaserite and apatite are shown. (After Dickens and Brown.)'
June 1992 CrystaI Structures of CasCr.,OI, und Ca5Cr2SiO12 1419

Fig. 3. Stereoscopic illustration of channels perpendicular to the (100) plane of the unit cell. The channels have a diameter of 3.5 A at the
narrowest point. Ca, Cr, and 0 atoms are indicated by large, medium, and small circles, respectively.

Fig. 4. Coordination polyhedra surrounding the Ca ions in CasCr3012: (A) monocapped trigonal prism around Ca(3); (B) bi-
capped trigonal prism around Ca(2); (C) tricapped trigonal prism around Ca( 1).

the mirror plane, TET(2), consist predominantly of chromium,
whereas the tetrahedra in general positions, TET(1), consist of
both chromium and silicon in approximately equal fractions.
The three nonequivalent calcium atoms are coordinated to
nine, eight, and seven oxygen atoms, respectively. Ca(1) is
coordinated to the surrounding oxygen atoms in a tricapped
trigonal prismatic coordination, Ca(2) in a bicapped trigonal
prism, and Ca(3) in a monocapped trigonal prism. Some of
the C a - 0 lengths are, however, rather long, and an alternative
coordination arrangement is possible and is discussed later.
A novel feature of the structure is the presence of empty
channels perpendicular to (loo), as shown in Fig. 3. The
smallest diameter of these chayels, which extend continuously
through the structure, is 3.5 A. The channels are formed by
Ca, Cr, and 0 atoms.
Ca(l), Ca(2), and Ca(3) would be eight, seven, and seven,
respectively (Model 2).
The average bond lengths of these models are compared
in Table IV to those calculated from ionic radii given by
Shannon and PrewitLs Although the average bond lengths
calculated using Model 2 show better correspondence with the
values derived from ionic radii than does Model 1, this is only
marginally the case.
Electrostatic valence balances of cations about anions ac-
cording to the procedure described by Moore and Arakib were
calculated for the two models of C a - 0 coordination and Cr(1)
and Cr(2) valences. These are given in Table V. Based on
the valence calculations in Table V, the choice of the correct

(2) Coordination of Polyhedra

Drawings of the coordination polyhedra surrounding the Table IV. Comparison of Average Bond Distances (A) in
calcium ions are given in Fig. 4. The oxygen atom labels Ca5Cr3OI2for Two C a - 0 Coordination Models
correspond to those given in Table 11. Observed Shannon and Prewitl
Two slightly different polyhedral models can be described,
depending on the maximum C a - 0 distance that is allowed
for coordination. The C a - 0 polyhedra are drawn on the E$]2
Ca(1)"O
1.733
1.699
2.628
Cr4+-0
Cr6+-0
Ca9-0
1.82
1.68
2.56
assumption that Ca(l), Ca(2), and Ca(3) have nine, eight, and
seven coordination respectively (Model 1). However the coor- Ca(I)*-O+ 2.556 CaX-O 2.50
dination numbcrs are open to question, since the Ca(l),O(l) Ca(2)$-0 2.50 CaX-O 2.50
bonds (3.232 A) and the Ca(2)-O(4) bonds (3.269 A) are ca(2)7-o+ 2.447 ca7-0 2.45
significantly longer than the other C a - 0 bonds. This means Ca(3)7-0 2.461 Ca7-O 2.45
that, if we eliminate these longer bonds, the coordination of 'Bond lengths on Ca(l)> Ca(2); and Ca(3); (Model 2).
1420 Journal of the American Society-Adendorff et al. Vol. 75, No. 6

Table V. Electrostatic Valence Balances (2) of Cations about Anions

Cations bonded to oxygen Atom indicated
z
(Model 1) I:
(Model 2 )

0, Cr(2) + Ca(1) + 2Ca(3) 2.29

~r(2)+ + 2Ca(3) 2.07
0 2 Cr(2) + 2Ca(1) + 2Ca(2) 2.44
~r(2)+ + 2Ca(1) + 2Ca(2) 2.57
0 7 Cr(1) + 2Ca(2) + Ca(3) 1.78
Cr(l)+ + 2Ca(2) + Ca(3) 1.85
0, Cr(I) + 2Ca(I) + 2C:a(2) 1.94
Cr(1)' + 2Ca(I) + Ca(2) 1.78
0 5 Cr(1) + Ca(1) + Ca(2) + Ca(3) 1.75
~ r ( i ) ~+ ca(1) + Ca(2) + Ca(3) 1.82
0, Cr(1) + Ca(2) + 2C:a(3) 1.82
Cr(l)+ + Ca(2) + 2Ca(3) 1.85
0 7 Cr(2) + Ca(2) + 2Ca(3) 2.32
~r(2)~ + Ca(2) + 2Ca(3)
__ -
2.35
14.36 14.32
Model 2

model is still inconclusive, with Model 2 giving a marginally
better valence sum (the theoretical valence sum being 14).
It seems, therefore, that an unequivocal choice between the
two models is not possible at this stage. Hence, Model 1 is
retained in the structural description, but it must be stated that
Model 2 is just as feasible. It must also be mentioned that,
in Model 2, 0(1) is now surrounded by only three cations,
which is not a common feature.
The Cr-0 distances of 1.733 and 1.699 A for Cr(1)-0 and
Cr(2)-0 distances compare reasonably well with those derived
from ionic radii given by Shannon and Prewitt' (see Table IV).
(3) Valency of Chromium
From the structural description it is clear that, to main-
tain charge balance in Ca5Cr30t2,Cr(1) must be tetravalent
and Cr(2) hexavalent. This is substantiated further by the
occupancy refinement of the tetrahedral positions TET( 1) and
TET(2) in CaSCrl.xSil zOiz (reflecting Si fractions at TET(1)
and TET(2) of 0.534 and 0.108, respectively). This means
that Si predominates in TET(l), which implies that the Cr
ions in this site must be tetravalent, in order to allow for
isomorphous substitution of Si4+.These results eliminate the
other possibility, i.e., 2 0 " in TET(1) and Si4+in TET(2). The
latter possibility also cannot allow for substitution exceeding
one Si atom per formula unit.
(4) Possible Cation Distribution in Silicocarnotite
The crystal structure of CasCr2SiOlr and CaSP2SiO12'are
similar in many respects. The two phases have the identi-
cal space group (No. 62) with comparable cell dimensions
and crystal structures. The stoichiometry is similar, although
silicocarnotite contains P instead of Cr. If the valency of P is
assumed to be pentavalent, then Si4+ in silicocarnotite should
be positioned on a mirror plane (site 4c) and the P5+ in a
general position (site 86). Hence, Si should occupy different
tetrahedral sites in the two structures. However, the occupancy
of Si in silicocarnotite is still open to question (Ref. 7, p. 7),

Fig. 5. The arrangement of polyhedra in (A) Cr-apatite and (B) CasCr3012. The positions of the Ca and Cr atoms correspond closely, whereas
the oxygen atomic positions do not show correspondence.
June 1992 Crystal Structures of Ca.5Cr.3012and CajCrzSiOlz 1421

Table VI. Comparison between Silicocarnotite and structural units in Cr-apatite (Z = 1/4)" and in the structure of
Apatite Unit Cells (Pnma 0rientation)'O CasCr3012 (x = 0.8). The OH position in apatite corresponds
Silicocarnotite Hydroxyl-apatite Difference (%)
to the 0(1) position in CrSCr3Ol2.
There is a close positional correspondence of the Ca and Cr
a = 6.72 A0 c = 6.88 A 2.4 atoms, which explains the correspondence in the unit-cell sizes
b = 15.47 A a [ & = 16,34 A 5.6 as discussed above. However, the oxygen atomic positions do
c = 10.09 A a2 = 9.43 A 3.5 not show correspondence because of the displacement of the
z = 4 2 = 4 Ca and Cr atoms of CaiCr3Ol2 away from a plane, as is the
V/Z = 262 A3 V / Z = 265 A3 1.1 case in Cr-apatite. It must also be mentioned that the transition
between the two structure types goes via CaO +
Ca3(Cr04)2
(see Fig. 6, from de Villiers et al.') so that a displacive (or
second-order) transformation cannot be possible. One therefore
based on the observed bond lengths of the PO4 and Si04 would not expect correspondence between oxygen atomic
tetrahedra. positions.

(5) Relation to the Apatite Structure

Chromium analogues of apatite were described by Banks
and Jaunarajs,x and the structure of Ca5Cr301z(OH)was deter-
mined by Wilhelmi and Jonsson.' We can compare the struc-
ture type described in this paper to that of chromium apatite.
In describing the silicocarnotite phase (CasP2SiOlz,PDF File
No. 40-393), commonly found in steelmaking slags, Keppler"'
described a geometrical correspondence between the unit cells
of silicocarnotite and hydroxyl-apatite, CaSP3Ol2(0H).The
relatiov is given in Table VI, i.e., that the a axis of apatiJe,
(9.43 A) corresponds to the c axis of silicocarnotite (10.09 A).
This conclusion is supported by a comparison of the two
structures in this common orientation. Figure 5 shows the
(6) Relation to the Glaserite Structure
Some formal relationships between Ca5(P04)2Si04,Caj-
(P04)30H, and K3Na(S04)*, described by Dickens and
Brown,' can be seen from a comparison of their unit cells (as
given in Fig. 2) with the (100) projection of Ca5Cr3Olzatomic
positions. Only the positions of the cations are compared.
Acknowledgments: This paper is published by permission o f the Council
for Mineral Technology (Minkk). We thank thc South Alrican Council for
Scientific and Industrial Research for use ol their data collection and computing
facilities

CaO + liquid

14001

600
CaO 20 40 60 80 CrzO3
CrzOl, To by mass
Fig. 6 . Phase relations in the system CaO-Cr203 in air. (From de Villicrs et d.')
1422 Journal of the American Society-Adendorff et al.
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(1987).
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Earth Chromates (V),” Acta Chem. Scand., 19, 117-84 (1965).
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Neues Jahrb. Mineral. Monatsh, 320 [9] 320 (1968). 0