73

The Carudian M ineralo gist

Vol. 34, pp.73-78(1996)

THECRYSTALSTRUCTURE
OF CLINOATACAMITE.
A NEWPOLVMORPHOF Gu2(OH)3Cl

JOELD. GRICE
Research
Divixioq Canadian
Mu*eamof Nature,P.O.Box32143,
Staion "D", Oxawa.OntarioKIP 6P4

JANT. SZYMANSKI
CANMET,Natural ResourcesCarnda" 555Booth Street,Oxawa"Ontario KIA 0GI

JOHNL. JAMBOR
Depannznt of Earth Scientes,Universityof Waerlao, Waerloo, Ontario N2L 3Gl

ABsrRAcr

The crystal structureof clinoatacamite,Cul+(OtI13Cl,hasbeendeterminedand refined to indicesft = 5.2 and wR = 4.9Vo.

The strucfirreis monoclinic,spacegoup nlln(1,4),-wirhcellparametersa6.144(l), r 6.805(l), c9.Ll2(l) A, p SS.SS(:)',
V 375.7(2)A3, and with Z = 4.T\e structureanalysiswas essentialin determfuingthe valencestateof copper(Cu2) and the
number of (OII)- anions in the formula. The structure consists of layen of partly occupid edge-sharingoctahedraof
Jabn-Teller-distortedtCu(OH)4C121 octahedraparallel to (101).This layer is topologically the sameas that in mica. Adjacent
layers of octahedraare offset, suchfhat vacantditesin one sheetalign with occupiedsitesin the neighboringsheet Layersare
linked by individual, slightly Jahn-Teller-distoriedoctahedraof composition[Cu(OH)o]. The structuresof paxatacamite andthe
otherpolymorphsof Cur(OII)3CI,atacamiteandbotanakite,alsoarelayered but they differ from the layeringof clinoatacamite
in topology,compositionand srcss-linkage.

Keywords:clinoatacamite,crystal shucture,layer of ocahedr4 polymorph,Jahn-Tellerdistortion.

SoMr{ens

Nous avonsaffind la structurecristalline de la clinoatacamite,Cua+(OH)3CI, jusqu'i un rdsidu fi de 5.2Vo(wR = 4.9Vo).

Il s'agitdhne structure6saoclinique,^groupespatialP21ln(14), dont les paramdtres r6ticulairessonta 6.1,44(1),,6.805(l),
c9.Il2(I) A, B 99.55(3f, V375.7(2) A3,powZ=4. L'6bauche de la structurea6t6 essentiellepourfixerlavalence du cuivre
(Cu}) et le nombre d'anionsOH- dansla formule chimique. La structureest faite de feuillets paralldlesd (101), compos6s
d'octabdresdifformes [Cu(O[I)aClr] partiellementoccup6s,partageantdesa€tes; cesoctaBdressontdifformesi causede I'effet
de Jahn-Teller. Cesfeuillets sort topologiquementidentiquesh ceux qui caritctdrisentles micas.Les feuillets adjacentssont
d&al6s, de sorteque les lacunesd'un feuillet sontalign6esavecles sitesoccup6sdu feuillet adjacent.Cesfeuillets sontli6s par
des octabdresindividuels de cogposition tCu(OII)61,l€gBrementdifformes, encore A causede I'effet de Jahn-Teller. Les
structtnesde paratacamiteet despolymorphesde Cu2(OtlrCl atacamiteet batallackitepossbdentaussicesfeuillets; toutefois,
elles ditldrent de la structurede la clinoatacamitedansla topologie,la compositionet I'interconnexiondesfeuillets.

Clraduit par la R6daction)

Mots-cl6s:clinoalacamite,stusturg sristalline,feuillet d'octabdres,polymorphe,distorsion,effet de Jahn-Teller.

INTRoDUC"iloN tion of Cu by Zn for stabilization(Jamboret al. 7996).

The crystal-structure analysis reported here was
Clinoatacamite(monoclinic) from Chuquicamat4 undertakenin orderto understandthe crystal-chemical
Chile, has been describedas the third polymorph of relationshipsamongthesefqur mingrals,
Cu3+(OH)3Cl (Jambor et al. 1,996); ulasimite
(orthorhombic) and botallackite (monoclinic) arc the Et<psRtrvENrAL
other polymorphs. Indications arc tlat paratacamite
(rhgmbohedral) is not a fourth polymorph of The small amormtof holotype clinoatacamiteavail-
Cua*(OH)3CI,as this mineral requirespartial substitu- ableprecludedstandardchemicalanalyticaltechniques
74 TIIE CANADIAN MINERAIPGIST

capableof differentiatingthe valencestateof Cu and the four asymmetricunits of reflection data.

the determination of H2O. The structure-analysis
method (Hawthorne& Grice 1990) establishedthese Cnvsrar,-Srnuc"nrnsANALvsrs
quantities; the fonnula is Cua+(Olt)3C1.Electron-
microprobe analysis (Jambor et al. 1996) of the Normalized structure-factor statistics indicate a
material gaveCUO74.7, Cl 16.5,(H2Ofrom structure centrosymmefic space-group.The E-map coordinates
analysis L3.5), sum 104.7, less O = Cl 3.7, lotal were assignedto appropriatescatteringcurves, three
1.01.0 wt.Vo. Zinc and Ni were not detected. Cu. one Cl and three O atoms.This sffucturemodel
Based on O + Cl = 4, the empirical formula is refinedroR=6.8Vo.
Cu1.e6o3.03H3.1tCln.r. The idealformula Cu2(OH)3C1, In the final least-squares refinemen! the siles of all
requiresCUO74.49, Cl 16.60 and HrO 12.66,sum atoms were refined with anisotopic displacement-
L03.75,lessO = CI3.75, total 100 wt.Va.Itis evident factors to final residualsof.R = 5.2Voand wR = 4.9Vo.
that within the limits of experimentalerror,the malerial The addition of an isotopic extinction-correctiondid
studiedis ideal, end-memberclinoatacamite. not improve tle refinement. Owing to tle poor
A crystal fragmentof type clinoatacamitewas used agreementamongsymmetry-relatedreflections,Ra, =
in the collection of X-ray-dilfraction intensity data. l2.lvo.the stacturewassolvedandrefinedin Pl. This
Single-crystal precession photographs indicate the refinement,with isotropic displacement-factors, had a
unique space-groupP21ln (1,4), on the basis of considerablypoorer residual factor, with R = l5.5%o.
systematicabsencesofreflections. Intensity datawere The lower-symmetrystructuremodel was testedusing
collected on a fully automated CAD four-circle MISSYM (Le Page 1987) and found to contain
diffractometer operated at 50 kV, 26 mA, with an apparent symmetry of 211m.This symmetry
graphite-monochromated MoKcr radiation. is consistent with the Cu atomic positions, but
A setof 44 reflectionswas usedto orient the crystal the O atoms obey space-gtoup symmetry P21lle.
andto refine the cell dimensions.Four asymmetricsets Refining the sfiucture rn F2ylrn with an:isotropicdis-
of intensity datawere collectedup to 2Q= 60ousing a placement-factors resultsin residualfactorsR = LL.3Vo
0:20 scan-mode,with scan speedsof approximately and wR -- l3.8Vo, and all of the O atoms have non-
Lolminute. Data pertinent to the collection of the positive definite displacement-factors. Thus it is
intensity dataare given in Table 1. evident that F21ln is the correct space-groupand that
Datareduction,usingthe NRCVAX setof computer the rather poor refinement is attributable to the
programs(Gabe et aI. 1989), included correction for problems inherent in an absorptioncorrection of an
background, sealing, Lorentz and polarization and elongatecrystal fragment. tn the final AF-synthesis,
linear absorption.For the absorptioncorrection,four residual electron densitiesof 2 e-lA3 remained,but
intense diffraction-maxima in the range 25 to 53o none of these could be satisfactorily assignedto H
20 were chosenfor y diffraction-vectorscansafter the atoms. The final positional and displacementpara-
methodof North et al. (L968).Structuredetermination meters for the clinoatacamitesfructure rn P21ln we
and structure refinement were done using of the givenin Table2, and selectedbond-lengthsandangles,
SIIELXTL (Sheldrick 1990) package of computer in Table 3. Observedand calculatedstructure-factors
programs.The i:regular shapeof the crystalprecluded and anisotropic displacement-factors have been
a good absorption-correction, and becamethe limiting submitted to the Depository of Unpublished Data
factor in the structurerefinement.This problem in the CISTI. National ResearchCouncil of CanadaOttawa,
datareductionis evidencedby a mergingR of l2%ofor CanadaK1A 0S2.

TABLE1. CUNOATACAMITE: DATA

STRUCTUREOETERUNAION TABLE2 CUNOATACAMITE:
ATOMICGOORDINATES,
ISOTROPIC
DISPLACEMENT
ldoal fomula: Cu?(Ol03Cl a = B.laa(l) 4 Atom x y z U(A1x'to2 BVsr
Spa@gmup: nlln b ' 6.805(r)4
Crystalstro: 0-14x 0.08x0.04 mm c = 9.112Q)A Cut o 1r2 1n 1.44(4) 1.SE
F .99.55(3)" 000 r.8q4) 2.00
RadJMon.: Mo/graphJte Y.375.7(2) A3 cu3 0.2588(2) 0.A€40) 0.2185(2) 1.55(3) 2.02
tt 11.9mm"' Z-4 o1 02e98(10) 0.2002(10) 0.5470(8) 22(2) 1.18
Tdd rsf. 4186 0.41e0(8) -0.fi4r(8) 0.7w(8) 2.2Q) 124
Mln. transmlsslon 0.037 F unlqua1092 o3 02598(8) 0.8792(8) 0.5372(8) 1.e(4 127
Max. llansmbslon Fo>86(ne74 cl 0.1116(3) -0.0038(3) 0.3ff)E(2) 1.87(0 o.37
Fhal R s 5.2oi
-F,b2natr|fn,
nrrr"Bn(lF,l r"to'(rJt nnalwRe 4.99/.
t Eond-vatenco6urns (%u.)ushg ths paramsto'sol Br6ss & Olcetfo (1991).
 TIIE CRYSTAL STRUCTTJRE
OF CLINOATACAMITE 75

TABLE3, CUNOATACAMITE:
SELECTEDINTERATOMTC (A) AND
DISTANCES
BONDANGLES(O)

cu1 polyhedron Cu2 Dolvhedron cu3 Dolyhedron

Cul.O'l 2.288(6)x2 Cu2-Ol 1.948Q)x2 cu$ol 1.934(8)

Cu1.O2 2.050f0x 2 Cu2-O3 '1.9E7(6)
x2 cu&o2 1.975(5)
Cu1-O3 1.99'l(5)
x2 Cu2-Cl 2.766(2)x2 cu&O2' 1.999(5)
cu3-O3 2.015C0
01-Cu1-O2 74.3(2' 01-Cu2-O3 E3.6(2)x 2 Cu$cl 2.7ffi(2)
Ol-Cu'l-O2' 105.7(2) 01-Cu2-O3' sa.Ae)x2 Cu3-Cl' z.Ec,4,e)
O1-Cu1-O3 75.1Q) 01-Cu2-Cl ss.OQ)x2
O1-Cu1-O3' 10/.s(2) O't-Cu2-Ct 81.0(2)
x2 o'l-culo2 98.2(3)
O2-Cu1-O3 78.5(2) O&Cu2-Cl 8.4(2)x2 o1-cu3-o2' 83.8(3)
O2-Cu1-O3' 141.4Q) O&Cu2-cl' E3.6(2)x 2 01-cu3.cl 100.3(2)
Ol-Cu&cl' 80.2Q)
cl-ol 3,070r0 o2-cu3-o3 79.9(3)
cl-o2 3.0e0(6) o2-cu3-Cl 84.1(1)
ct-o3 3.042(6) o2-Cu3-Cl' 100.6(2)
o2'-Cu$O3 98.3(3)
O2'-Cu$cl 52.8(2)
O2'-CulCl' 82.4(1)
o&cu&Cl 83.4(2)
O$.cu&Cl' 96.3(2)

Dxcp;prroN .qNDDrscussroN that there are three other polymorphsof Cu2(OII)3C1,

OF TI{E STRUCTT]RE
The analysis of the structure of clinoatacamite
permittedthe calculationof bond-valencesumsfor the
various a0omicsites. On the basis of the constantsof
Brese & O'Keeffe (1991), the sums are: Cul 1.98,
ca 2.09,aB 2.02,cl 0,37,01 1.18,02 1.24 and
03 I.n yz. Thesecalculationsallow assignmentof the
correctvalence,Cu2+,to the cation and recognitionof
OL, 02 and03 as (OID- aniens.Jls lesultantsimplest
formula for clinoatacamiteis Cul+(OQrCl with Z = 4,
The low bond-valencesum of the Cl atom is due to
H-bonding. Each Cl atom is H-bonded to all tbree
O atomsatbond distances of 3.(X to 3.09A (Table3r.
Thesebond distancess1esimil2l to the averaeeojl
distance in paratacamite(3.07 A: Heet 1975) and
botallackite(3.21A: Hawthorne1985).
The crystal structure of clinoatacamite may be
describedasmadeoflayers ofpartially occupied,edge-
sharing,Jahn-Teller-distorted[Cu(O]t)aCl2loctahedra
parallel to (101) @ig. 1a). This layer is topologically
the sameas that in mica. Adjacentlayers of octahedra
areoffset suchthat vacautsitesin one sheetalign with
occupied si0esin the neighboring sheet. Layers are
linked by individual, slightly Jahn-Teller-distorted
octahedraof compositiontft(Olt)61 @ig. 1b). Eby &
Hawthorne(1993)classifiedthis type of copperoxysalt
mineral as an infinite framework stucture M = M.
whereM denotesoctahedrallycoordinatedcations,and
the doublehyphendenotesedgesharing.
In addition to clinoatacamite,it has been assumed
and the crystal structure has been solved for each;
atacamite@arise& Hyde 1986), paratacamite(Fleet
1975) and botallackite (Hawtlorne 1985). Like
clinoatacamiteoeach of these structureshas layers of
octahedrabut of differing composition or topology.
Botallackite has a layer of fully occupiedoctahedr4
with composition [Cu(OtI)aCl2] @ie. 2a). Adjacent
layersare H-bondedtogethertbroughhydroxyl donors
and Cl acceptors(Frg. 2b). In atacamite,the layers
of octahedra,and their stacking, resemblethose of
clinoatacamite,but the vacantsitesin the layer corre-
spond to a more distorted oooctagonal" hole @g. 3).
The difference in topology between the layers of
clinoatacamiteand those in atacamiteresults from a
change in composition within the layer. In clino-
atacamite, both octahedra have the composition
[Cu(OH)4Clt, whereasin atacamite,the two octahedra
havethe composition[Cu(OIDaCl2]and tcu(OfD5clrl.
The [Cu(OIDoClr] octahedronin each structure is
(4 + 2)-distort€d,with the Cu{l bondsbeing longer
than the Cu-O bonds; in atacamite, however, the
[Cu(O[I)4C12]octahedronis (4 + 2)-distortedwith two
apical Cl ligands,and the [Cu(OII)5C11]octahedronis
(4 + 2)-distortedwith one apical Cl and one apical O
Iigand. Paratacamitehas the samelayer composition
and topology as clinoatacamite(Fig. 4a). It is the
interlayer, isolated tcu(OfDol octahedronthat differs
in the fwo minerals.In the clinoatacamitesfructure.the
interlayeroctahedronexhibitsa Jahn-Tellerdistortion,
but in paratacamite, one [Cu(OH)6] is axially
compressedwhereasthe other is a regular octahedron
76 THE CANADIAN MINERALOGIST

Frc. 1. The structureofclinoatacamite:(a) (101) projectionshowingthe layerofedge-sharingCu(OII)aC|2octahedra;(b) (010)

projectionshowing(101) layersof Cu(OQaCl2octahedrawith singleCu(Ot!6 octahedracross-linkinglayers.The unit cell
a<cisoutlined.

Gig. b). Eby & Hawthorne(1993) remarkedon this octahedralcoordination.Apparently,the crystalusedin

anomalousoccurrenceof symmetrically bonded Cu.
That parafacamitecontains essentialZn (or another
catio& e.9.,Ni) is snongly suggestedby the fact that all
paratacamitecrystalsstudiedto datecontainsignificant
amountsof Zn or Ni (>2 wt.7o), even those from the
type locality (Jambor et al. 1996). Zinc n a 6-fold
coordination atomic site usually has fairly regular
the stucture determination (Fleet 1975) was not
analyzed,and it is probablethat the structuredoestrot
correspondto a oopure" Cu-bearingcompound.
The indications are that paratacamiteneedsto be
redefined, as it is probably not a polymorph of
Cua(OII)6C12,but a distinct phase of composition
'?arata-
Cu:(Cu,ZnXOtDoClz.In such a case, tile

Fro. 2. The strucfire of botallackite:(a) t1001projection showinga layer of fully occupiededge-sharingoctahedra.(b) t0011
projectionshowing(1@) layering of Cu(OII)nCl, octahedraand H-bondinglhking layers.The unit cell a < D is outlined.
 TI{E CRYSTAL STRUCTUREOF CUNOATACAMITE 7',|

Ftc. 3. The structureofatacamite: (a) (110) projection showing the layer ofedge-sharing Cu(Oll)oCl2octahedra;(b) (001)
projectionshowing(ll0) layeringofCu(Olf)aCl2octahedrawithsingleCu(OI!5CI, octahedracross-linkinglayers.The unit
cellacDisoutlined.

camite" sftucturewould haveZn orderedat the regular
octahedralsite within equipoint position 30. Jambor
et al. (1996) showed that only 2 wt.Vo 7n was
necessaryto stabilizethe rhombohedral(pamtacamite)
structure;thus Zn neednot be the dominantcation in
the 3b site.Sucha redefinitionrequiresapprovalby the
Commissionon New Minerals and Mineral Names.
IMA. It would be appropriate that rhombohedral
Cq(Cu,4XOII)6C12,witha13.65 andc 14.0A, space
group R3, which correspondsto the holotype from
SierraGorda Chile, andfor which the crystalsfructure
was determined by Fleet (L975), be retained to
designatethe mineral paratacamite.If paratacamite
is redefinedin this way, the following may be con-

Flc. 4. The structureofparatacamite:(a) (001) projection showingthe layer of edge-sharingCu(OII)aCI2octahedra;(b) (110)

projectionshowing(@1) layeringof Cu(OH)oCl,octahedraandisolatedCu(OIlu octahedracross-linkinglayers.The c axis
is vertical.
78 TIIB CANADIAN MINERALOGIST

sidered as new minerals: 1) compositionsbetween & Gmcs, J.D. (1990): Crystal-structureanalysis

CulZn,Cu)(OH)6C12and (Cu,ZnLZn(OI06Cl2,which as a chemical analytical method: application to light
elements.Can.Mineral. 28, 693-702.
is the Zn analogueof paratacamite;thesecompositions
correspondto those of minerals from the Kafi Kafi JArvGo&J.L., Durnzac, J.E., Ronmrs, A.C., Gruce,J.D. &
mine, Anaralg han, and Herminia, Chile, with the Szvrrtefsn, J.T. (1996): Clinoatacarnite,a new poly-
latter describedby Kracher & Pertlik (1983); 2) morphof Cu2(OI!3C1,andits relationshipto paratacamite
(Cu,Ni)3N(Olt)6C12,which is the mineral of this and *anarakite".Can,Mineral, 34,6l:72.
compositionfrom the Carr Boyd dsftsl mine (Jambor
et al. 1996), and from Widgiemoolth4 Australia KRAcHR, A. & PRrLI! F. (1983): Zrtrreicher Paratacamit
(Nickel et al.1994). Cu3Zn(OI06C12, aus der Hennina Mine, Siena Gorda
&ile. Ann. Nanrhist. Mus. WienESIL,93-97.
Acrlrowr.Blcelvnl{Ts
LE PAcE,Y. (1987): Computerderivation of the symmetry
elements implied in a structure description. J. AppI.
The financial support of a Research Advisory Crystallogr.n,2&-269.
Committee Grant from the Canadian Museum of
Natureto JDG is gratefirlly acknowledged.The authon . Nrcrs-, E.H., Clom, J.F.M. & Garrnen, B.J. (1994):
appreciatethe carefirl reviews and helpfirl improve- Secondarynickel mineralsfrom Widgiemoolth4 Westem
mentsof the two referees.Drs. PeterBums and Frank Australia.Mineral. Rec. 25, 283-291,302.
Hawthorne,andthe Editor, Dr. RobertMartin.
Nonnr, A.C.T.. Plmrps, D.C. & Mert$ws, F.S. (1968):A
semi-empirical method of absorption conection. Acta
Rsmwcrs
Crystallogr. AU, 35L-359.
Bn$s, N.E. & O'IGEFFE, M. (1991):Bond-valencepara-
Pap.rss,I.B. & Hvps, B.G. (1986):The structureof atacamite
, 192-197
metersfor solids. ActaCrystallognB47 . and its relationship to spinel. Acta Crysnlbgr. C42,
tn7-n80.
F.C.(1993):Structural
EBy,R.I( & Hawrronme, relationsin
copperoxysaltminerals.I. Structuralhrerwchy.Acta SHEIDRIC&G.M. (1990): SHELX|I" a Crystallographic
Crystalbgr.B/,9,28-56. ComputingPackage (revision 4.1). SiemensAnalytical
Instruments,Inc., Madison,Wisconsin.
FL@r,M.E. (1975):The crystalstuctureof paratacamite,
Cur(OH)rCl. gr. 831, 183-187.
ActaCrystalla

GABE,E.J.,LBPAGB,Y., CturuaNn,J.-P.,r .FF,F.L.& Wurrp,

P.S. (1989):NRCVAX - an interactivesystemfor
structure J, AppI.Crystallagr.
analysis. 33,385387.

F.C.(1985):Refinement
Hawrnonrrre, of thecrystalstructure Received August I, 1995, rnised manuscript accepted.
MineralMag.49,87-89.
of botallackite. September2T, 1995.