AmericanMineralogist,Volume70,pages1056-1058,1985

Sbrosrsoa Pb-freeanalogueof fiiltippite,Pb3sbssrs

J. SrnvsN SwNNeA.. ANrnoNy J. TeNonlolNo Huco SrrrxrrNr

Materials Science and Engineering

The Uniuersity of Texas, Austin, Texas 78712

Abstract
Bronze colored prisms found in a reaction product when coprecipitatedSbrS. and SbrO.
were heated at 250"C in a saturated NarCO. solution were isostructural with ftilcippite,
Pb3SbrSl5,and have the stoichiometrySbroSrr,a:13.393(1)A, b: lL.7t70$)4, c:
16.737U)4, P:93.763(6)A,Z:4. The structurewas refinedto R:0.062, arR:0.056 for
2893observedreflectionswith anisotropictemperaturefactorsand variableoccupancyfactors
for three Sb atoms.Two of the Sb atoms correspondto the two crystallographicallyindepen-
dent Pb atoms in fiiliippite. The Sb--Sdistancesare of the samelengthsas thosereported for
fiilcippite. The crystal structure of Pb.SbsS* was re-refined using Nuffreld's (1975) data
permitting the occupancyfactorsfor Pb(l), Pb(2)and Sb(3)to vary. The value ofR decreased
signiflcantlyto 0.057from the reported value of 0.061.The Pb(1)site is fully occupiedby Pb,
but the occupancyfactor for P(2) was 7.47(6)and for Sb(3)was 8.70(10)insteadof 8 atoms
per equivalentsitesin the unit cell. Thus the Pb(2) site contains 0.825Pb and 0.175 Sb and
the Sb(3)site has 0.145 Pb an 0.865Sb. The lead-freepolymorph of stibnite is a metastable
phaseat room temperature.

Introduction
In an ongoing program to synthesizeand investigatethe
physical propertiesof oxysulfidecompoundswe attempted
the synthesisof kermesite,Sb2S2O,by the procedurede-
scribed by Baumgardt and Kupcik (1977).Optical exami-
nation ofthe productsofreaction showedthe characteristic
radial aggregatesof needlesof stibnite, Sb2S3,which was
confirmedby powderX-ray diffraction.In addition a major
component consistedof black platelets.A few very small
bronze-coloredprisms were also found but we never ob-
servedcrystalsof SbrSrO in the reaction products. Single
crystal diffraction patternsof the black platesshowedthat
they were orthorhombic,a:53.724, b: Ll.09A, c:
3.8514, Pnam. Whlle this investigation was in progressa
paper appearedby Koyama, et al. (1984) describing the
crystal structure of BirOrS. On the basis of their unit cell suredevery 100 reflectionsand no significantchangein intensities
parametersand resultsof X-ray energydispersiveanalysis
on our crystalswe believethat the black platesare SbrOrS
and that they crystallize with a superstructure of the
Bi2O2S structure in which a - l4c.r The details of this
structure will be published elsewhere.The bronze-colored
prisms were shown by X-ray energydispersiveanalysisto
consistonly of Sb and S in about a 2:3 proportion. We
could not identify this compound and thereforeproceeded
with a crystalstructureanalysis.
' Note addedin proof:Preliminarystructureanalysisindicates Crystallography,1974),convergedto R :0.0615, roR :0.0564 for
sb4sso.
0003{xxx/85/0910-1056$02.00
Experimental
A crystal having an irregular prismatic shapeof volume 0.133
x 10-5 crn3 was selectedfrom a product obtained by coprecipi-
tating SbrS. and SbrO. at pH 9 from a solution of NaOH buf-
fered with borax/HCl. The precipitatewas sealedin a vycor tube
with saturatedNarCO, solution and heatedat 250"Cfor 3 d. The
crystal was mounted on a Krisel Automated Picker diffractometer
equipped with a graphite monochromator, ,l.(MoK"):0.71069A.
The eight equivalent intensities of 20 independent reflections,
25.3< 20 < 29.8', werecarefullycenteredand these160measured
20 values were used in a least squarescalculation to obtain the
lattice parameters, a: 13.393(l)A. b : ll.7l7VQA, c:
16.737(l)L, fl : 93.163(6)". The systematic absences were
hkl:h + k:2n + I, hOI:l : 2n + l, consistentwith Cc and,C2lc
with the latter shown to be correct by the subsequentcrystal
structuredetermination.Intensity data were collectedby a a>scan
at 3.0 deg min-t to 20 <ffi.;4 standardreflectionswere mea-
wasobserved.3829reflections weremeasured, h:0-18, ft:0-16,
-23<l<23.
Intensitieswerecorrectedfor Lorentz, polarization and absorp-
tion with t4: lll crn-1 basedon a Sbr"Suounit cell content.The
minimum and maximum transmissionfactors were 0.33 and 0.50.
Standard deviations o(F2) were calculated from [counting
statistics+ (O.021)21tt2.2893reflectionswere consideredobserved
on the basis that F > 4o(F). The structure was solved by direct
methods which showed all Sb and S positions. Full-matrix least
squaresrefinementon F with co: Alo2(F), A : 2.98,anisotropic
temperaturefactors,variableoccupancyfactorsfor Sb(3)Sb(5)and
Sb(6),scatteringfactor for neutral atoms corrected for real and
imaginary parts of dispersion,(Internatiotnl Tableslor X-Ray
the 2893 observed reflections; (L/o)^",:0.011; maximum and
1056
 SWINNEA ET AL.: Pb-FREEANALOGUE OF FOLdPPI'TE 1057

Table 1. Atomic and thermalparameters( x 104)for Sb1oS15

Atom utt uzz u33 ul2 ul3 uzg u"q l2 Occupancy

s b ( )l 3 7 s 4 . e ( . 6 ) r 4 5 0 . 4 ( . 8 )'41 69?5E 2 . 2 ( . 5 ) 2 5 7( 4 ) 3 0 8 (5) 2 6 7( 4 ) - 3 6 ( 4) 6 8 (3 ) - r 3 ( 4 ) 275(3)

sb(2) 4 0 e 0 . 8. 6() r8r0.9(.7) Of (l 2lr (4) ?28(41 200(4) 27(3) il (3) l3(3) 2 13 ( 2 )
sb(3) 883.7(r.o) f,zz.Dtl.t, 4 1 4 97 ( . 8 ) 4s2(8) 3 4 2 ( 7 ) 4 5 r( 8 ) -53(5) 238(6) - r4 6 ( 6 ) 4 l e ( 4 ) 6 . 8 2 ( 3 )
'14(3) -2(3) - 2 s ( 3 ) 207 (2)
sb(4) r 4 1 4 . 6 ( . 5 ) tl,aq q( 7\ oJo,o(. ), r60(3) 2 7 e ( 4 l l 8 r( 4 )
sb(5) 3 0 2 6 . 6 ( r) . r 4 4 4 4 . 6 ( r . 4 ) 3 4 0 9s .( . 9) 483(e) 6 0 0 ( l l) 420(e) - r 4 r ( i ) rs4(6) - 2 1 (t 7) 4 e 4s() 6 .r 8 (3 )
sb(6) 0 3 9 7.71 ( 2 6 ) \ 4ei(r8) 434(18) 7e6(25]. 0 -r44(15) 0 5 8 41(2 ) 2 . 3 3 ( ? l
s(l) 3520(3) 44?(31 ?510(2) 574(23) 256(r8) 264(17) -r8(r6) 28(rs) 65(r5) 3 6 5 ( r)
s(2) 0 8r0s(4) z 209(19) 283(23) 297(?31 0 -75(16) 0 2 6 (71 3 )
s(3) 2640(2) 264(3) 3 6 4 2( ) ?40(r4) r99(r5) 317(r7) r8(r2) 54(r2) s5(13) 250(e)
s(4) 1st2(2) 246413) 3 9 5 02( ) 243(r4) 263(r6) 32e(17], -6(13) 34(12\ - e o (r4) 278(e)
s(s) 4656(2) 3640(3) 4619(2) 240(14) 227(15) 255(15) 36(12) 6(il ) -25(r3) 2 4 (1e )
s(6) 284(21 4136(3) 878(2) 2 0 0 r( 3 ) 2 2 6 ( 1 5 1 2 r ( r 4 ) -5(il) -25(r) -55(r2) 2r4(8)
s(7) 732(21 l2e5(3) t 6 7 7( 2 1 243(r4) 257(16) 217(14]. - 3 r ( 1 2 ) 23(il) 22(12) 23s(9)
s(8) 273e(z) 3207(3) r6r8(2) 196(13) 296(r6) 262(151 l4(r2) - 7 5 ( l r) -is(r4) 2s5(e)
T h e a t o m l a b e l i n g f o l l o w s t h a t o f N u f f i e l d w i t h o u r S b ( 5 ) = P b ( 2 )a n d - S ! ( 6 ) = P b ( l ) .
The anisotropic ihernal parameters are of the form: exp[-Zr2(U11a"262igrr6*2y2+Utac*2]2+2UlZa*b*hk+zul3a*c*hl+2u23b*c*kl)].
Ueo=l/3 trace of orthogonalizedUii tensor.
Numbirs in Darentheses are standard deviations.

minimum values of Ap are 5.1 and -4.5 eA-3. Table I contains sponding to those atoms,similarly, had very large temper-
the final parameters and Table 2 contains selected Sb-S bond ature factors and for that reason led us to refine on the
distances. Table 3 contains a listing of F(obs) and F(calc).2 Calcu- occupancyfactors. If the high temperaturecoeflicientsin
lations were carried out with sHELxT6(Sheldrick, 1976), uurmNTS
ftilcippiteare due to refinementwith full occupancyfactors,
(Main, et al., 1978) and n.nore.l (Finger and Prince, 1975).
then it is conceivablethat the stoichiometryof the mineral
Discussion could be approximatelyPbr., !6."Sbr. 7E o.3Sb6S 15. Eden-
harter and Nowacki (1975)provide a chemicalanalysisfor
The unit cell content on the basisof the crystal structure
their specimensobtained by means of an electron probe.
analysiswith full site occupancyfor all atomsis SbonS.oor
On the basis of the reported value for S representingS*
Sb11Sr5,Z:4; the refinementstopped at R : 0.090.
the stoichiometryis Pb2.6Sbr.rS*and calculatedd: 4.77
Three of the Sb atoms,Sb(3)Sb(5)and Sb(6)had unusually g cm-t comparedto d,:5.18 g crn-3. Unfortunately, no
large temperaturefactors and a refinement in which the
measured density is reported. Nuflield (1946) reports a
occupancyfactors for theseatoms were permitted to vary
measuredd : 5.22g cm . 3. The crystalsof Sbr.rSr which
provided reasonablevaluesfor the temperatureparameters
we synthesizedwere so few ar.rdso small that no reliable
and converged to R : 0.062. The stoichiometry became
densitycould be measured.
Sbe.BSls,Z:4. A careful analysisof the coordination
The occurrenceof fiildppite was originally describedby
polyhedra around Sb and their linkagesled us to the con-
DeFinaly and Koch (1929).On the basisof an analysison
clusion that this structure might be similar to that of
some"carefullyselectedcrystals"they derive PbrSb"S,, for
known Sb-Bi-Pb sulfides.An examination of a paper by
fiil<ippite.We recalculatedthe formula on the basisof S*
Wuensch(1979)on superstructuresin sulfide minerals re-
and get Pb2.73Sb7.?BSrr. The reporteddensityobtainedpy-
vealed that the Sbe.rS* was isostructural with fiil<ippite,
knometrically is 5.23 g cm-3. The agreementbetweenthe
Pb3Sb8Sls,the first member of the plagionitegroup of
measuredand X-ray densitiesfor fiiliippite strongly negates
minerals.The phasewhich we synthesizedcorrespondsto a
the vacancymodel for its crystal structure.
lead-free ftildppite with the stoichiometry SbroS* and
The uncertainty in the composition causedus to rein-
there are vacanciesin the correspondingPb and Sb sitesin vestigate the crystal structure of fiildppite using the F
the mineral structure.
Detailed structuresof ftilcippitehave been published by
Edenharter and Nowacki (1975) and Nuflield (1975).A Table 2. Interatomicdisrances(A) for Sblosl5
careful analysisof the temperaturefactors of the atoms of
Pb3Sb8S1s for both publishedstructuresshowsthat Pb(l), s b ()r - s (3 ) 2.622(3') s b ( 4 )- s ( 6 ) 2.4e6(3)
-s(4) 2 . 4 s(r3 ) - s ( 7) 2.462(3)
Pb(2), and Sb(3) (atom labeling correspondsto Nuffreld) -s(6) 2 579(31 -s(8) 2 481(3)
have the largest values.The Sb atoms in our phasecorre-
s b ( 2 -) s ( r) 2.445(41 s b ( 5 )- s ( r ) 2.758(41
s(2) 2.478(3) -s(3) 2.485(4)
2 To obtain a copy of Table 3, order DocumentAM-84-274 s(8) 2.4s0(3) -s(7) 2.741(4)
from the Mineralogical
Societyof America,Business
Offrcr,2000 s b ( 3-)s ( 4 ) 2 692(41 s b ( 6 )- 2 s ( r) 2 . 6 2 3 ( 4 )
-s(5) 2.434(3) -2s(6) 2 773(3)
FloridaAve.,N.W.,Washington, D.C.20009.Please
remit$5.00in -s(7) 2 . 6 5 r( 3 )
advance for the microfiche.
1058 SWINNEA ET AL.: Pb-FREEANALOGUE OF FOLdPPITE
values and parametersreported by Nuffreld (1975).Our
calculation using unit weights results in R :0.06094,
agreeing with Nullield's value of 0.0607; RG : 0.06956
where RG: [Earl Fo- F"l'Eaff;1ttt. We refinedthese
parametersby least squareson F yielding R : 0.06107,
RG :0.06929. We now permitted the occupancyfactors
for Pb(l), Pb(2) and Sb(3)to vary in a least squaresrefine-
ment. The values of R and RG convergedto 0.05731and
0.06619and the occupancyfactors were 3.97(5),7.46(7)and
8.69(10)respectively.The Pb(l) site, thus, is fully occupied
and we now calculateda least squaresrefinementpermit-
ting the occupancyfactors for Pb(2)and Sb(3)to vary. The
refinement convergedto R : 0.05727,RG : 0.06619and
occupancyvaluesPb(2):7.47(6) and Sb(3):8.7(10). A
Hamilton ratio test (lnternational Tables, 1974)using RG
valuesfor Nullield's structure refined with full occupancy,
0.06929,and with the Pb(2)and Sb(3)variableoccupancies,
0.06619, yieldsRr.rnon.o.oo5 : 1.0468as comparedwith the
theoreticalvalue 1.0036at the 0.005significancelevel.
Ideally the Pb(2) and Sb(3)occupancyfactors should be
8. The measureddensity confirms that the stoichiometry
for fiililppite is correct so the explanationfor the apparent
vacancyin the Pb(2)site and excessoccupancyin the Sb(3)
site must be sought in terms of electron density. A "va-
cancy" implies X-ray scattering power less than Pb, i.e.
some of the Pb is replaced by Sb, and "excess"implies
scattering power greater than Sb, i.e. some of the Sb is
replaced by Pb. Conserving the overall stoichiometry
Pb3sbsslj the Pb(2)site contains0.825Pb and 0.175Sb
and the Sb(3)site has 0.145Pb and 0.865Sb. The sums
Pb : 0.970 and Sb : 1.04 are unity within experimental
error, chargebalanceis maintainedon the basisofdivalent
Pb and trivalent Sb and the measuredand X-ray densities
are reconciled.
The stoichiometry Sbe.rS* based on the crystal struc-
ture analysisis SbtoS* within experimentalerror and only
trivalent Sb exists in the structure. The presenceof va-
canciesin the three Sb sitespreserveschargeneutrality.
Numerous experiments to grow larger crystals were
fruitless.When the power to the furnace was shut off and
cooling took placeby heat transferto the environmentthe
productsconsistedof stibnite Sb2S3,Sb2O2Sand a very
few SbtoS* crystals.An experimentin which the furnace
was programmedto cool slowly over a period of 12 h from
25V125"C yielded a product consisting only of Sb2O2S
crystals.We believethat the lead free fiil<ippite,SbtoStr, is
metastableat the temperatureof the experimentand that a
small amount of this polymorph of stibnite is retained
during rapid cooling.
Acknowledgments
This researchwas supportedby the National ScienceFounda-
tion under Grant DMR 8217288and by the R. A. Welch Founda-
tion of Houston, Texas.
References
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Sb2S2O. Journalof CrystalGrowth,37,346-348.
DeFinaly, I. and Koch, S. (1929) Fiiltippite, a new Hungarian
mineral of the plagionite-semseyitegroup. MineralogicalMaga-
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Edenharter,A. and Nowacki, W. (1975)Die Kristallstruktur von
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Manuscript receiued,December 17, 1984;
accepteilfor publication, April 28, 1985.