Canadian Mineralogist
Vol.23, pp. 3542 (1985)
OCCURRENCE
AND CRYSTALSTRUCTURE
OF KIPUSHITE,A NEW COPPER-ZINCPHOSPHATEFROM KIPUSHI,ZAIRE
PAUL PIRET
Belgium
Loborotoirede chimiephysiqueet de uistallographiede I'Universit{, B 1348Louvain-la-Neuve,
MICHEL DELIENS
Ddpartementde gdotogieet de mindralogie,Musderoyal de I'Afique cenirale,B 1980Tenuren,Belgium
JACQUELINE PIRET.MEUNIER
Belgium
Laboratoirede chimiephysiqueet de cristallographiede I'Universitd,B 1348Louvain-la-Neuve,
de poudre[d en
du diagramme
sjx raieslesplusintenses
2.554(90)(r32),
A(r)(hkt)l sont: 4.03(100X300,121),
I 36,036,060),
2.970(60)(32r,r30),I .13I (60b)(723,
Kipushiteoccursin the oxidation zoneof the depositof
chiLa composition
12.2(50xlm)
et3.386(50X122,221,311).
Kipushi, southernShaba,Zaire, in associationwith other
: CuO43.0'
6lectronique
Ala micfosonde
secondaryminerals of Cu, Zn and Pb. It appears as miqued6termin€e
l1'1,
H2O(parthermogravim6trie)
ZnO24,4,P2Os20.9,
aggregatesof subparallelplisms or, rarely, asisolated { I I 1}
donnela formule6[(Cu,Zn)O].P
prismselongatedalong [101],emeraldgreenin color, trans- toIal99.4V0,
zOs.AHzO.
maisvariede1.1
parentto translucent,optics : biaxial (-), 2V = 23" (calc,), LerapportCu:Znmoyenestde1.8/1.0,
par diffractionX
a 1.693(2),P 1.738(2)afi 7 l.74AQ). It is monocolinic d 2,6. La structurea 6t6 d€termin6e
deuxfeuil(R = 0.05pour1252rdflexions).
Ellecomporte
P21/c, with a 12.197Q),b 9.156Q), c 10.667(2)A, I
96.77{2)',Z:4, density3.904(catc.)and 3.80 (meas.) lets mixtes d'octaddres et de t6trabdres
et un feuilletdetdtrabdres
g/cm'. The stlongestsix reflectionsin the X-ray powder t(Cu.Zn).(OH){(H'O)PO4l2+
Les feuilletssontunispar lessommets
pattern[d in A0)(r&0] are 4.03(100)(3oo,r21)!2.ss4(90)[zn1oH;Pon1z=.
PO4et ZnO3(OH)et par desliai(r32), 2.970(60)(32
1,l 30), 1.53I (60bX723,
I 36,036,060), communsauxtdtraedres
12.2(50X100)
An electron- sons hydrogbne.La formule structurales'6crit
and 3.386(50)(122,221,311).
microprobeanalysisgaveCuO 43.0,ZnO 24,4, P205 20.9, (Cu,Zn)5Zn(OH)6(H2OXPO)2.
ABSTRACT
H2O (by thermogravimetry)ll.l, total 99.490,yieldingthe
formula 6[(Cu,Zn)O].PzOs.AHzO.
The'Cu:Zn ratio is
equalto 1.8:1,0(meanvalue);it rangesfrom l.l to 2.6.
The crystalstructurewasdeterminedby X-ray diffraction
(R = 0.05 for 1252 reflections). It consists of two
sheets containing octahedra and tetrahedra in
units and one sheetof tetra[(Cu,Zn)5(OH)5(H2O)PO4]2+
hedra [Zn(OH)POa]'-. The sheetsare connectedby shared
apical oxygen atoms of POa and ZnO3(OH) tetrahedra
and by hydrogen bonds. The structural formula is
(Cu,Zn)5Zn(OH)6(H2OXPO|2.
description
Mots-clds:
kipushite,cuivre,zinc,phosphate,
min6ralogique,
structurecristalline,Zaiie.
INTRODUCTION
The Kipushi depositis located about 30 km southwest of Lubumbashi, southernShaba, Zaite, neat
the border with Zambia. The metallic oreshavebeen
worked for more than sixty years.The mineralization consistsof Zn, Pb, Cu and Fe sulfides with
Keywords: kipushite, copper, zinc, phosphate,mineralo- accessoryGa, Ge, Mo, W and V. It occursin the
gical description,crystal sfucture, Zaire.
dolomite and schist-dolomite seriesof the Lower
Kundelunguian(PrecambrianID. The mineralizaSoMMAIRE
tion is mainly located along a transversefault that
cuts the flank of an asyrnmetricanticline. A comLa kipushite se ttouve associded des mindraux secon- plete descriptionof the geologyand the mineralogy
dairesde cuiwe, de zinc et de plomb dansla zone d'oxyof the Kipushi deposithas beengiven by Intiomale
dation du gisementde Kipushi, Shabam6ridional, Zaire. & Oosterbosh(1974).
Elle se pr6senteen agr6gatsde prismessubparalldleso_u,
The thicknessof the weatheredzone extendedto
rarement,en prismesisolds{l1l} allongdssuivant[01],
100metresin depth; this zone has now been
about
de couleur vert 6meraude,ffansparentsi translucides.Optique : biaxe(-), ZV = 23' (calcul6),a l.693Q), 9 1.738Q) completelymined out. The most abundantminerals
et 1 l.74AQ).Systdmemonoclinique,groupespartalP21/c, of that zonewerecerussite,malachite,smithsonite,
aveca l2.l97Q), b 9.156Q),c 10.667(2)A, B 96.77(2)"et hemimorphite, cuprite and hematite,with a rich a$soZ:4. Densit9 : 3.904 (calcul6e)et 3.80 (measur6e).Les ciation of accessory
Cu-Zn-Pb-Fe phosphates'car-
35
36
THE CANADIAN MINERALOGIST
TaELE l.
g.['[,GI{y DlcrA !!R VESmtrrE
V€ze\dt6
lbd€t.i€I
r
+ ?no
lclo
Pzos
V€E\dte
rdllsltl
fm
45
38.20
37.A2
37.34
25.05
26.69
2s.b
23.64
24.94
64.25
64.51
62,54
64.08
on.*]
18.93
18.43
9.Ol
19.01
19.90
16.22
14.3I
Bzos
b.44
ro.41
H:O
16.82
16.87
w.
r7.o5
o. ll
D&slq'
9/@3
3.2
3r2
3.38
3.34
Reftacl!re
tudle
fc
Aral<e
"E*llq
o.65
^_
,r"n
lo.6
Data
ardkeLte
23
1
G'o
zno
AND IEE IDEICTICAI]MTNRAL SEIES
(6)
: @Lbl1c
J I Z
3.53
5t4
5 : J
3.@
1.640
1.618
r.658
1.622
1.695
r.658
710 (+)
38.5" (+)
p^/a,
r.63-r..64
Z = 4[qrr.s
Z!tr.,
)
po"(cs)r.2lz4 ao 9.828(3),bo ro,224(3),co 7.532(3).i., ro3.r8(2)o
B
(@1c.) 3.38 9/@3.
r&lty
I : tl@tl€l
ocrq,@ltl@ for (Ch,Zo)!(poq) (d{)3.29rO,
(1930, 1932). 3 : Sctraf
2 , zslsy
(1880) rit}l cptl@t
(1921). 4 : hkaba!&sb1 & r@sda (1921). 5 : Brrtgsrbedr
e et az. lJ974i.
Ftc. l. Aggregatesof kipushite prisms.
bonates, silicates, sulfates and vanadates. The
holotype specimenof kipushite is registeredin the
mineralogicalcollection of the Museeroyal de I'Afrique centrale(No. 14.026).A cotype existsin a private collection. The mineralogical associationof
kipushite includes pseudomalachitein dark blue
nodules, earthy pale greenmalachite, blue and green
hemimorphite, colorless sticks of pyromorphite,
ultramarine crystallinemassesof veszelyite,yellow
and olive green cnrsts of vauquelinite, acicular
crystals clusters of libethenite, quartz and iron
oxides.
Gf:Zs = 3r2.
data of r@
(1922. 6 : 6r
VESZELYITE
AND IDENTICAL
MINERALSpsclgs
Data on the hydrated phosphatesof copper and
zinc belonging to the (Cu,Zn)3POa(OH)r.rHrO
group are summarizedby Palacheet ql. (1951).Nl
these minerals are generally well crystallized and
transparentto translucent.Their color variesfrom
ultramarine blue to bluish green.The first description published pertained to veszelyite from
Moravicza in Roumania (Schrauf 1880);the composition publishedshowsa considerableamount of
As (10.4190As2Or).Half a centurylater, two additional descriptions were.published: an unnamed
mineral from Broken Hill in Zambia (Mennell &
Spencer1920),and arakawaitefrom the Arakawa
mine, Japan(Wakabayashi& Komadal92l). Ohashi
(1924) showed that arakawaite is similar to the
unnamed mineral from Broken Hill. Buttgenbach
(1927)studiedseveralcrystalsfrom Prince Leopold
mine, Kipushi, southernShaba,Zaire; he gavethese
crystalslhe preliminary name "kipushite" in order
to facilitate their descriptionand their comparison
with similar species. Nevertheless,he regarded
"kipushite" as identical to the unnamed mineral
from Broken Hill and very closeto arakawaiteand
veszelyite,with which it would constitutean isomorphous series.Zsivny (1930,1932)reinvestigatedthe
type material from Moravicza; his new chemical
analysisshowedthat thereis no arsenicin veszelyite
and, for that reason, the similarity between
veszelyite,the unnamedmineral from Broken Hill,
arakawaite and the Cu-Zn phosphatefrom Kipushi
was established.The only difference concernsthe
Cu:Zn ratio. Zsivny (1932) retained the name
veszelyitebecauseof chronologicalpriority. Berry
(1948)calculatedthe unit-cell constantsand gavethe
spacegroup of veszelyitefrom Moravicza. Ghoseet
ol. (1974)studiedthe crystalstructureof a specimen
from Arakawa and showedthe existenceof a new
type of sheetstructure. Chemicaland optical data,
as well asthe densitiesgivenby the various authors,
are summarizedin Table 1. CrystalloCraphicdata of
Ghoseel al. (1974)are also shown in Table l.
37
KIPUSHITE, A NEW COPPER-ZINC PHOSPHATE FROM ZAIRE
THs Usr oF THENauB Krpusnrrn
As the identity of the mineral from Kipushi studied
by Buttgenbach(1927)with veszelyiteis established,
the provisional namekipushite usedby that author
is free for another mineral. We apply this name to
the new Cu-Zn phosphatedescribedin this paper.
The name of the Kipushi mine, famous for its rich
mineralogicalassociations,will then appearin the
literature applied to a well-defined and unique
mineral species.
The description(17/ l) and the name(14,/4)of the
mineral havebeenapprovedby the Commissionon
New Minerals and Mineral Names, IMA (September 1983).
MonpHotocy ANDPHySIcALPRopERTIEs
Kipushite is emeraldgreenin color, with a pale
blue streak; it is transparentto translucentand has
a vitreousluster. It appearsasmore or lesselongate
aggregatesof prismsup to 3 mm @ig. l) or, rarely,
as isolatedprismatic crystalsup to 0.3 mm @ig. 2),
of which lateral faces are uneven and rounded.
Prisms{ I 11} areelongatealong[0T] andterminated
principally by (100).The other often-presentforms
are {102}, {012} and {llT}. The measurable
angles
betweenvectorsare:(1ll)A(IlTl 10t.0", (l I l)A(100)
56.9'. Thereare no distinct cleavages,and the fracture is uneven.The Mohs hardnessis approximately
4. Density is 3.8 (measuredin Clerici solution) and
3.904 g/ cm3(calculated).
The mineral is biaxial negativewith a small 2Z(not
measured;23o calculated)and the indicesofrefraction (sodium D line) are: a 1,693Q) (colorless),0
1.738(2)(blue) and .y 1.740Q)@right blue). Sign of
elongationand optical orientation were not determined owing to the lack of cleavage.
Cugurcal Covtposrrrox
Quantitative chemical analysis by electron
microprobe(Centred'analysepar microsondepour
UIBLE 2.
Itr{E CUEqI(aI
Ftc. 2. Two stereoscopicviews of a kipushite crystal.
Lat€ral faces (ideallzed):{ll1}, lozenge:(100f kite:
(192),trapezes:(lll) and (lll), triansles:(012)and
(0r2).
les Sciencesde la terre, Laboratoire de p6trographie,
Universit6 Catholique de Louvain; J. Wautier,
analyst)hasbeencarried out with the following standards: Cu2O for copper, willemite for zinc, and
apatite for phosphorus.Water wasmeasuredby thermogravimetry (Stoneapparatuswith Cahn balance).
The resultsare given in Table 2. The TGA curve in
Figure 3 showsthe loss of structural water between
320 and 450'C. The formula is (Cu,
with Cu:Zn : 1.80:1.The
Zn)6@O)2(OH)6.H2O,
Cu:Zn ratio is not fixed in this mineral species;it
variesbetween2,6:l and l. l: I in the grainsanalyzed.
CC!.4P6ITTOT\I CF KIPTFIITE,
AS DEEFMIND
BY E;KARON
MICROPrctsE
36.4 48.3 48.O 36.3 3s.2 36.5 35.5
45.8 48.o 47.3 48.4 42.9 45.4 48.4
43.O
3.77
44.L
7,tfi
3r.o 19.4 2L.9 34.O h.2
21.3 r8.5 L9.5 n.5 25.r 20.9 r8.5
24.4
2.O9
25.L
P^Oz)
20.8 20.8 n.8
29.6 3L.6
22.L 2L.3 20.5 2L.O
n.8 2L.r n.7 2r.3 n.4 20.6 n.7
D2W
I ant 2 : elqErlrental-
\€lght
p€roecttages of tuo cletals.
crdan ratlo for ll atcEns of oq|g€n 1n tie
(PO.)z(O[I)6.H2O
w,i t h G : : Z n = 1 . 8 : 1 .
anhld:ous part.
n.9
1.O3
b.4
tt.r,
99.4
4.30
ro.4
[email protected]
4 : rcle'
3 : rean rralues (Hzo bv theumgraqiuetr/).
(wt. E o:<ides) for (QlrZn) e
5 : eq:ected ocryosltlon
38
THE CANADIAN MINERALOGIST
wt:t"
11.06
f
i
0
5
t0
15
F
I.8
500
300
200
Frc. 3. Resultsof thermogravimetricanalysisof kipushite.
Kc = 0.1873. The value of l-(Kp/Kq) is 0.010'
which is consideredin the "superior" category.
CoNaperrsrLrrYINDEX
The compatibility index Mandarino 1981)was calculatedfrom the following data: formula 3.86Cup,
2 . 1 4Z n O , P 2 O 54, H 2 O ;M : 6 9 5 . 2 ; Z : l l 8 3 A 3 ;
D"a":3.904 g/cm3; n: 1.7?-4;Kp = 0.1855and
TABI,E
3.
X-RAY
hkl
dcalc
dobe
lc)o
ol.l
rrT
200
2ro
rrz
211
r2o
202
3oo
r2f
2O2
3ro
t2,r
6.93
6.22
6.06
5.o5
a.44 1
4.39
4.28 1
4.24
4.o4 r
4.o3 '
X.77
3.69
t2.2
6.92
6.t8
6.06
5.O5
I
122
zzL
3r1
r13
3rZ
32T
130
3r2
4rT
roa
r32
f,.4oo\
r.r/yl
3-377'
3.271
3. 196
2 . 9 8 2|
2,959'
2.887
|
2.856'
2,6s3
2.552
33O
3r3
422
304
2. 435
|
2.425'
2.372
2.345
. ^-^,
U4.6 @ DblescbEffi
FFed @-s1rlglFcysbl.
lntensltls.
PONDER PATTERN OF TIPUSEITE
rvig
*1
4oa
i . ' J
52r
r42
3.76
3.69
loo
r3a
034
3
20
4(J4
r.roo
3.274
3. r98
30
2.97o
60
2,868
30b
o53
2?654
2-554
40
722
2.X65
2.340
306
504
630
90
r36
036
o60
2. 4XO
2'L2r z.rtt
25
I
2. r L 6 '
2'os71 z.oeo 30
',
2.O54
2.or4
I
2.oo2
|
2.m
r.936
1.986
r.868
1.841
L'739
1
r.732 ',
1.6e2
)
1. 69r
'I
r.684
r.635 |
Lazel
I
1.598
r.537
I
r. s:s
|
r . s 2 8I
L.526
8
r.489
20
t- 4go
mE,
c{d
lffisftf@.
I
3
2 , 2 O 4 2. r 9 9
2.rs? 2.156 40
|
to
40
25
dobe
d."1.
2.oo7
15
1.936
r.886
1.862
r.837
40
8
15
lO
r.tzt
15
r.688
lsb
t,azs
lo
r.598
lO
,. ur,
6ob
r. a8l
10
T
|
t
radiatio,
Ni fi1td,
d(!kl)
ih A, vt@Aly
iJdode
esttmda
DATA
X-RAY-DT NACTION
Powder data, which are given in Table 3, are not
similar to other listed data. The hkl indices were
assignedin accordancewith the measuredsinglecrystal-diffractometerintensities. Cell parameters
and spacegroup weredeterminedfrom Weissenberg
and precession photographs. Parameters were
refined by least squaresusing fifteen reflections
measuredon a 4-circlediffractometer. Kipushite is
monoclinic, space grpup P21/c, a l2.l97Q), b
A, I 96J7(2)o; Z = 4.
9.156(2),c 10.667(2)
Cnvsrar-SrnucruRE DETERMINATIoN
The intensity of all reflectionswith 20 < 50' was
measuredusing a SyntexP2l four-cilcle diffractomfrom
eter, Mo.l(curadiation O = 0.71069A), <,r-scan
-1. I o to + l. I o. Of the 2084independentreflections
collected. 1252 are classified as observed
U > 2.5o(Dl.Becauseof the smalldimensions(< 0.1
mm) of the irregularly shapedcrystallinefragment
chosenfor data collection and the low value of p
(10.9mm-t), no absorptioncorrectionwas applied.
The structurewas solvedby the Pattersonmethod.
As the superpositionmethod gavepoor resultsowing
to the numerouscoincidencesbetweeninteratomic
vectors,the following processwas used. All peaks
that could correspondto 2x,2y,22 (for Cu andZn)
werelocated,startingfrom Harker peaks0, Vz+2y,
t/z andZx, Yz,t/z+22.The co-ordinates
xi, !i, Ziof
all possibleCu and Zn positionswerethus obtained.
They were grouped in pairs. For each group' coordinatesand temperaturefactors were refined by
least squares.Then a difference-Fourierserieswas
39
KIPUSHITE, A NEW COPPER-ZINC PHOSPHATE FROM ZAIRE
calculated,and the one or two largest peakswere
assumedto be atoms and introduced in the leastsquaresrefinement. The examination of R values
and, aboveall, of temperaturefactors (which may
not becometoo small, too largeor too different from
eachother) led to the choiceat this stageof a good
partial solution. The other atoms (Cu, Zn, P, O)
werethen easilyfound with the aid of successive
Fourier seriesand least-squaresrefinement.
The final difference-Fouriersynthesisshowsonly
a few small peaks; these do not correspondto H
atoms, or to displacementof atomic positions due
to partial substitutionof Cu by Zn. The final R factor is 0.047 for 1252observedreflectionsand 0.092
for all 2084 reflections. A table of calculatedand
observedstructure-factorshasbeendeposited;a copy
may be obtained on request to: Depository of
UnpublishedData, CISTI, National ResearchCoun-
TABLE4. ATOI'rrCCooRDINATES(,rou), S eoUrvArmir(;,r), UlJ(x lO") (;r)
y/B
cul
cuz
cu3
cu4
cu5
zN6
P7
PA
0,
010
0I I
nr2
otf,
016
sr5
0r5
017
0t8
0 19
020
o?1
o22
o23
3307(
2745{
3280(
t259(
3118(
3t6(
,.t4(
42a7(
24Aa(
4..62a
254t(
3821(
1568(
3937(
,755(
L927(
2547(
4t2n<
1792(
3a69(
5r0(
-22I(
-2661
rsperalure
9
f actor
utt
..L4O(
2660(
5454(
1639(
93q94
943t
277\(
412(
4320(
5771(
5A3t(
3929(
2090(
2247(
4146(
rtt4(
7533(
7246<
5953(
-445(
4239(
2943(
1764(
2t
2'
2t
2'
2'
2'
5t
4'
t0)
ll)
Lt)
tl'
13)
L2'
tt)
t3)
tl)
\2'
13)
1t)
tJ)
t2)
l3)
= exp I -2r2
t945<
46tl(
..qat(
1937(
4345a
3355a
tO29(
2010(
3416(
2957(
t052(
266<
950(
2630(
5603(
3572(
4492(
55t5(
5893(
2735(
1707(
-2r0(
1749(
{h2a*2u,
2,
2)
2,
2)
2t
2'
4'
3)
9'
10)
9)
9'
t0)
9)
9)
t0)
9'
9'
tt)
9'
L2)
10,
l0)
r +. . t2
0.93
1.04
O.7a
O.79
0.71
0. ta
0.A9
0.71
O,76
0.96
0.84
0.91
t.66
1.10
0.5A
1.36
0.A'
t.3t
l.9t
O.t4
z,za
L..t7
1.s9
r84(
200(
153(
154(
130(
120(
89(
tl8(
9A(
t33(
143(
L62(
226(
201(
50(
a4(
16f,(
223(
133(
145(
2644
t65(
173(
hka*brur
u33
t0)
9)
9)
9'
9)
9)
tA)
19,
52'
53)
52)
54'
62'
55)
46)
50)
5l)
58'
55'
55'
64'
57)
58)
z)l
TABLE 5. INERAIf,n4IC DISIIAI{CES (standard
cr(l)
ctahedm
E.s.d.
ds,.fatlc
rr2(
143(
106(
9t(
106(
t33(
140(
92(
L77<
167(
59(
95(
178(
tl(
t38(
124(
115(
92(
29tt
974
404(
197(
136(
in
u23
9)
t0)
t0)
9'
10,
9'
2t)
lr)
57,
56)
50)
53)
60)
4a)
52)
53)
52)
53'
a4t
5!'
74t
63)
58)
27(
2<
3(
-9(
-9(
l0(
-4(
22(
L2(
-15(
-34<
57(
18(
Lzt
-39<
-18(
-13(
3t(
-23(
-52(
-240(
76(
9A{
ul3
A'
9t
a,
8'
8)
8)
t7)
t6)
4.1,
45)
46t
46'
52)
47'
44,
53)
48)
50)
60)
46'
got
49'
52'
2L<
-42<
-19(
26(
-1(
5(
-4(
-5(
-4o(
0(
-7(
-22(
971
-21(
-34(
-73(
-lr(
-4(
-924
37(
-130(
-39(
-664
UIz
7'
7''
a)
7'
a)
7)
t5)
t5)
44t
43)
41)
44'
49'
43)
40)
43)
42)
45)
4a)
45)
57)
47'
49'
38(
-8(
-r2(
-r5(
-3(
-8(
-7(
15(
-65(
-27(
-51(
-18(
16<
45(
..A(
9(
-571
2L(
8l(
-t6<
15(
-61(
-94(
10)
9)
9)
9)
8)
a'
16)
17)
43)
.r7,
49)
47)
52'
52)
44t
50)
r.9,
54'
58)
.16'
56)
49)
53'
[ffitj@.
re
rer
O.Of i)
Cu,zn(3) eta})edr.on
cu,zn( ) etahedrcn
qr,zn(s) ctah€dron
c\r,zn(3)-O(19)
o(1o)
o(15)
o(17)
o(9)
o(r8)
.
o(19)-o(9)
o(17)
o(r8)
o(15)
o(ro)-o(15)
o(18)
o(r7)
o(9)
o
o(15) (18)
o(9)
o ( 1 7 )- o ( 9 )
o(r8)
2.49
2.3O
2.or
2.Ot
r.99
r.93
Or,zn(4)-O(Io)
o(19)
o(2o)
o(rr)
o(r7)
o(r8)
2.41
2.37
2.o5
2.ol
r.96
r.95
ot,zn(5) -o(18)
0(161
o(2o)
o(rr)
o(t2)
o(r7)
2.5o
2.26
2.o5
2.o4
2.@
r.98
3.23
3.17
3.16
2.96
3.39
3.13
2.95
2.8s
2.9L
2.65
2.94
2.72
o(1o)-o(2o)
o(r8)
o(r7)
o(rr)
o(r9)-o(r8)
o(r7)
o(2o)
o(rr)
o(2o)-o(r8)
o(r7)
o(rr) -o(17)
o(r8)
3.55
3.14
2.95
2.92
3.16
3.14
3.o5
3.o3
2.95
2.64
3.or
2.65
o(r8)-o(12)
o(2o')
o(L7)
o(11)
o ( 1 6 )- o ( u )
o(u)
o(2o)
o(r2)
o(2o)-o(r2)
o(r7)
o(rr)-o(u)
o(12)
3.50
2.95
2.72
2.66
3.37
3.23
2.99
2.76
3.o4
2.64
3.o9
2.58
2.94
2.24
2.o3
1.98
r.97
L.97
cu(2)-o(14) 2.73
o(13) 2.r5
o ( 1 9 )- o ( r r )
o(9)
o(r2)
o(r4)
o
o(ro) (12)
o(r4)
o(u)
o(9)
o
o(u) (9)
o(r2)
o(r4)-o(12)
o(9)
3.67
3.41
3.37
3.22
3.34
3.26
2.92
2.85
2.9L
2.58
2.93
2.77
o ( 1 4 )- o ( r 5 )
o(r2)
o(16)
o(9)
o(r9)-o(12)
o(9)
o(16)
o(r5)
o(r5)-o(12)
o(9)
o(16)-o(9)
o(12)
zn(6) tetrahedm
t0,
t0)
t0)
9)
t0)
t0,
2l)
19'
5t)
54'
55)
55)
67)
63)
50)
67'
54t
6l)
6At
57'
66'
61)
7L)
Gl(2) €t:hedrcn
or(r)-o(13)
o(ro)
o(1r)
o(r2)
o(14)
o(9)
zn(6)-o(16) 1.96
o(21) r.91
o(22) r.93
o(23) r.93
o(16)-o(2r) 3.50
o(22',) 3. 13
o(23) 3.r7
o(2r)4(22) 2.97
o(23) 2.89
o(23) 3.16
59(
3a(
t0(
58(
30(
ll5(
104(
56(
l(
594
113(
A2(
24t(
198(
2t(
2A7{
55(
178(
272a
t2t(
L55(
t84(
275(
u(rl,
z.9a
o(r2) 2.o3
o(16) r.99
o(9) 1.9e
3.64
3.o4
2.96
2.77
3.37
3.31
3.lO
2.96
3.10
2.65
3.o2
2.76
P(7) tetrahedmn
P(7)-o(r3) r.53
o(2r) 1.53
o(22',t 1.55
o(23) 1.52
o(r3)-o(2r) 2.49
0(221 2.55
o(23) 2.W
o(2L')4(22) 2.52
o(23) 2-5o
o(22\4(23) 2.45
P(8) tetrahedrcn
P ( 8 )- O ( r O )
o(r4)
o(15)
o(2o)
o(ro)-o(14)
o(r5)
o(2o)
o ( 1 4 )- O ( r 5 )
o(2o)
o(ls) -o(2o)
r.53
r.54
r.56
r.55
2.53
2.5r
2.sr
2.5r
2.5L
2.55
E bGds
(d< 2.95 A)
ro/o\i/rr\
w(ror{lrJ,
a ll
z.az
cs(17)-o(23) 2.85
cH(r8)-o(14) 2.93
szo(19)-o(13) 2.@
-o(22) 2.69
Hzo(19)
o(.r3)-o(19)-o(22) L29o
r19"
o(16)-o(13){(r9)
40
THE CANADIAN MINERALOGIST
IABG
crfil
o(9)
Gt
o.44
6. mm
l2l
6ili)
0.43
dtltat
o.40
o.o4
0.2?
o(r4)
o.44
0.06
o(r5)
0.36
0(16)
O.43
m
SOG X
Daa)
0.r3
o.38
o03)
WIm
7.nr6l 9r7)
E
{.18
o.l8
o(11) o.37
o.43
orttS)
o.43
o(10) o.20
o(r2)
(v.u.)
VmCES
{.o9
o.4r
r.28
0.26
r.25
o.o
0.50
rc{
1.o3
ca
1.18 G
0.44
-o.13
o(r8)
o.5l
o.48
0.rr
-o.D
o(r9)
o (20)
o.u
o.t5
{.34
1.28
o(23)
o.55
r.32
2.r8
5.rc
o.55 \.22
t
1.92
1.93
cur -
2.O3
r.99
r.89
G
820
PON
o.r
2.r3
lor
o.22
r.99
rc.
o.r3
2.O
PON
4.93
(cu,zn).
zn -Pol
zn4Po1
I
t
tl
oHo
1l
oHo
t,/
t/
l c u , z n ) ' ( O ! ), ( l r o ) P o ,
II
II
t/
t/
(cu,zn) r (or) 1 (s.o). +
rt
o10
M
r.@
{.12
1.94
r.22
o.58
ffi
cil of Canada, Ottawa, Ontario KIA 0S2.
The program SHELX 76 (Sheldrick l97O wasused
for all calculations, with complex neutral-atom
scattering-functions.Figures5 and 6 weredrawn with
the program ORTEP (Johnson 1965).
1.86 FO.
-o.10
0.47
o(2r)
g(22,
G
r.?2
mr
o.40
0.36
l.o5
r.85
o(17)
0.36
@
r.94
0.lo
l.t8
o.20
l.l2
1.79 FO{
L2A
0.37
t
oF THESrnuct'une
DESCRIPTIoN
The final atomic co-ordinatesand temperatureparametersare given in Table 4. Interatomic distancesare presentedin Table 5. The estimatedbondvalences(v.u.) aregiven in Table 6. They were calculatedusing the constantsof Brown & Wu (1976).
Account was taken of hydrogenbonds (Donnay &
Allmann 1970).The sums of bond valencesshow
clearly the distinction betweenO, OH and HrO.
The structure consists of a sheet of tetrahedra [Zn(POt)OH]]" with two mixed sheets
[(Cu,Zn)s(OH)s(H2O)PO4],2'*which include five
octahedra around (Cu,Zn) and one tetrahedron
around P. Structural diagrams for kipushite and
veszelyiteare given in Figure 4.
1'
Sheet of tetrohedra
Por (ts,o)(or)r (cu,z;) s
zn-Po
l
;
The sheetof tetrahedra(Fig. 5) is very similar to
that in veszelyite(Ghoseet al. 1974),and is built up
of POo and ZnO,(OH) tetrahedrasharing corners.
rl
oiP zn
The P(7)Ootetra.!'redron
is regular. The mean P-O
The mean
A in vpszelyite).
distanceis 1.53A (1.5^4
(al
(b)
O-O distanceis 2.50 A (2.51 A in veszelyite).This
FIc. 4. Structural diagramfor kipushite (a) and veszelyite PO4 tetrahedron shares3 cornerswith ZnO3(OH)
O) with tetrahedral(T), octahedral(O) and mixed (M) tetrahedra, whereasthe fourth corner [O(13)] is
sheets.Centresof symmetry:*
bonded to Cu(2) and, very weakly, to Cu(l).
,/l
oo!
Ftc. 5. Stereoscopicdrawing (Johnson1965)of the sheetof tefahedra in kipushite.
Thin lines indicate H bonds.
KIPUSHITE. A NEW COPPER-ZINC PHOSPHATE FROM ZAIRE
41
Frc. 6. Stereoscopicdrawing (Johnson 1965)of the mixed octahedral-tetrahedral
sheetin kipushite. Thin lines indicate H bonds,
The ZnOr(OH) tetrahedron shows differences
betweendistancesfrom Zn to O or to OH. Means
qre Zn-Q | .g2A 0 .g4X in veszelyire)
,^Zn-OH ) .96
A (1.97A in veszelyite),
o-o 3.01A (3.11A in
veszelyite;for this mean, three erroneousdistances
given by the authors^havebeen corrected),and
(OH)-O 3.27L (3.20A in veszelyite).
This tetrahedron sharesthree cornerswith POotetrahedraand
the fourth tOH(16)l with Cu(2) and Cu(5).
Mixed octahedral - tetrahedral sheets
bly includethe sitesof the l. 14Zn found by chemrcal analysis.
-The salient features of the five octahedra are
shown in Table 7. The two possibleco-ordination
numbers, 5 and 6, are consideredfor Cu(l).
Bonding between sheets
The two mixed sheetsare linked by the common
atom O(10) at the apex of a POagroup. Sheetsof
tetrahedraare linked to mixed sheetsby O(13), at
the apex of the other PO4 tetrahedron, and by
OH(16) at the apex of the ZnO3(OH)tetrahedron.
In addition to thesedirect bonds, there are some
hydrogenbonds(Table5) betweenthe mixedsheets:
OH(18)-O(14), and betweenthe mixed and tetrahedral sheers: oH(9)-o(21), oH(16)-o(13),
OH(17)-o(23), H2o(19)-o(13) and Hzo(r9)-o(22).
The mixed sheets@g. 6) are very compact.They
do not havethe empty cavitiesfound in many other
Cu or Zn phosphatesand sulfates.This explainsthe
relatively high density of kipushite, 3.90 g/cm3,
comparedto 3.42 g/cm3 in veszelyite,for instance.
The P(8)Oa tetrahedron is regglar. Mean distancesareP-O 1.54and O-O 2.52A.It sharesthree
AcrNowLgncEMENTS
cornerseachwith two Cu atoms of the samesheet.
The fourth corner is bonded to three Cu atoms of
The authorsthank R. Van Dooren, who provided
the other mixed sheet.
The five octahedra possessa rather regular the specimenthat formed the subjectof this study.
equatorial square (three OH and one O) around
(Cu,An), with distances(Cu,Zq)-O between1.93and
2.05 A [generalm^ean:2.00 A, 1Cu,Zn;-OH:1.99,
TABTE 7. DESCRIPT]ON OF TFE FIVS (CU,ZN) OCTAIiEDT
(Cu,Zn)-O: 2.03 Al, whereasthe apical distances
vary greatly. Co-ordination around Cu(l) may even
L234
OR PO E2O
Cu Zn P
be consideredas a tetragonal pyramid, the sixth
oxygenatom O(13) being locatedat the llmit of the
( 3 3
5
3
13
cq(r)
co-ordinationsphere[Cu(l)-O(I3) : 2.94A]. As this
4
|
2
rl
{ 3 2
co-ordination is typical of Cu2* (Jahn-Teller
12
4
I
3
Cu(2)
3 3
effect), it is unlikely that any Zn occupiesthis site.
2
12
3 2 I
5
Cu,zn(3)
This situation is also^foundin veszelyite,with disCu,Zn(4)3215212
lances^2.41
ard2.93 A aroundthe first Cu, 2.45 and
I
I
12
5 I
5
Cu,zn(s)
2.47 A around the secondCu. Distopion around
2. rider
of slEled
edFs.
of reid|boB.
l-. Mffi
and rumbe!
Cu(2)is alsoimportant Q.l5 and2.73A); Cu rather
e'
h ard P polybeda.
@@
rit}l
3. Nde!
of slDred
ald H!
bords
foaed
of ffil
O.P, O-h
4. bb1
nunter
lhanZn probably occupiesthis site. The three other
br
Cu(l),
tlo
@
of tlE
by tlE
o.ygen
at@
FoLyhedm.
(5 and 6) @
octahedraare more regular and, therefore, proba@idsed
tst)
.
ordiEtjon
nrml€rs
{e
I
42
THE CANADIAN MINERALOGIST
F.P. & Spercrn, L.J. (1920):Rare zincMBr.rNEr-r-,
coppermineralsfrom the RhodesianBroken Hill
mine,northernRhodesia.Mineral.Mag. 19,69-72.
Bnnnv,L.G. (1948):Structuralcrystallography
of lazulite, scorzaliteand,v*zelytte. Amer. Mineral. 33, 750
and
(abstr.).
Ouasm,R. (1924):On daiton-sulphur,arakawarte
ishikawaite.J. Geol. Soc. Tokyo 31' 166-170.
BnowN,I.D. & Wu, KaNc-Kur (1976): Empirical
parametersfor calculatingcation-oxygenbond Peraqre, C., BnnueN,H. & Fnororr, C. (1951):
Dana'sSystemof Mineralogy.ll (7 th ed.).J. Wiley
valences.Acta Cryst. 832, 1957-1959.
& Sons,New York.
BurrcBNsacH,
H. (1927):Descriptiond'un min€raldu
Z.
Scrneur, A. (1880):Uber Phosphorkupfererze.
Katanga.Bull. Acad. roy, Belgique,Cl. Sci.ll-12,
Krist. Mineral. 4, l-33.
905-913.
REFERENCES
DoNNav,G. & Alr-uaNN,R. (1970):How to recognize SHBrpnrcr,G.M. (1976):Programfor CrystalStructure Determination. University of Cambridge,
6z-, OH- and H2Oin crystalstructuresdetermined
England.
by X-rays. Amer, Minerol. 55, 1003-1015.
Guosn,S., Lso, S.R. & War, C. (1974):Structural WercasavxHI,Y. & Kor'reoa,K. (1921):A phosphate
of copperand zinc from Arakawa mine. J. Geol.
chemistryof copperandzincminerals.l. Veszelyite
(Cu,ZI)2ZnPO4(OH)3.2H2O'
Soc. Tokyo 28, l9l-211.
a noveltype of sheet
structureand crystalchemistryof copper-zincsubZsrvr.rv,V. (1930): Uber den Veszelyitvon Vaskti
stitution. Amer. Mineral. 59, 573-581.
(Moravicza)und seineStellungzum Arakawait und
Iruouarr, M.M. & OosrensosH,
R. (1974):G6ologie
Kipushit. Int. Geol. Congressl1th (SouthAfrica)
et gdochimiedu gisementdeKipushi, Zaire.In Gise2. 438.
mentsStratiformeset ProvincesCuprifbres.Volume
du Centennaire,
Soc.96ol.Belgique,Libge,123-l@.
(1932): tJber den Veszelyit von Vaskd
JonNsorl,
C.R. (1965):ORTEP.Oak RidgeNat.Lab,,
Rep. ORNL-3794.
(Moravicza). Mat. Termts. Ertesitti, Budapest 48,
33l-358.
LansrN,E.S. (1921):Themicroscopic
determination
of
thenonopaque
minerals.U.S.Geol.Sun, Bull.679.
MauoamNo,
J.A. (1981):The Gladstone-Dale
relationship. IV. The compatibilityconceptand its appli
cation.Can. Mineral. 19.441-450.
Received December 19, 1983, revised manusc/ipt
accepted April 2, 1984.