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Knrrn RouNSow, G. V. Grsns, eNn P. H. Rrnnr, Departmentof

Virginia PolytechnicInstitute and State
U niaersity, Blacksburg, V irgi,nia 2406I

An anisotropic refinement of a non-metamict zircon la:6.607(I), c:5.952() A;
ILt/arndi Z:4, p:4.714 gm/cc; R:0.0191 from Kragero, Norway, produced these posi-
tional parameters for oxygen: y:.0661(1); z:.1953(1) The principal structural unit is a
chain of alternating edge-sharing SiO+ tetrahedra andZrOs triangular dodecahedra extend-
ing parallel to c. The chains are joined laterally by edge-sharing ZrOs dodecahedra and are
responsible for zircon's prismatic habit and cleavage, its extreme birefringence and optically
positive character. Similar chains occur in garnet extending in three mutually perpendicular
directions, but they are cross-linked by 106 octahedra as well as by XOs dodecahedra.
Oxygen in zircon is coordinated by one Si at 1.622(1) A and two Zr at 2.131 and 2.268 ^.
The mean bond angle at oxygen is 120o, suggesting that its orbitals are s22 hybridized,
leaving a lone pair available to form a double bond with Si. In garnet oxygen is four-coor-
dinated and the mean bond angle is = 108", suggesting sp3 hybridization with no lone pair-s
available for double bonding. This may explain why the Si-O bond in garnet is =0.02 A
longer than in zircon.
As in garnet, the SiOagroup is a tetragonal bisphenoid elongated parallel to c, and the Si
vibration ellipsoid is prolate in the same direction. Zr vibrates isotropically, but oxygen has
its maximum vibration axis normal to the plane of the coordinating Si and Zr atoms. The
distortions of the ZrOs triangular dodecahedron from an ideal hardsphere model can be
rationalized in terms of cation-cation reoulsion across its shared edEes.

Zircon, ZrSiO+,occurs as an accessorymineral in granitic and syenitic
igneousrocks and is a common detrital componentof sedimentaryrocks.
Its relativelv high density and resistanceto weatheringhave contributed
to its extensiveuse in heavy mineral studies.
The crystal structure of zircon was determined independently by
Vegard (1926), Binks (1926), Hassel (1926), and Wyckoff and Hendricks
(1927). Krstanovi6 (1958) has since refined the structure using two-
dimensional methods and obtained an Si-O bond length of 1.612 A.
White and Gibbs (1967) observed that this bond length was inconsistent
with the SiKB wave-length shift measuredfor twelve minerals with only
Si in tetrahedral coordination. This descrepancyled to the present three-
dimensionalrefinement,which yielded an Si-O bond length of.1.622A in
better agreementwith the value predicted by White and Gibbs. During
the course of our study, Krstanovi6, Djuri6, and Ili6 (1968) reported
refinedoxygen coordinates[o:0.06a(1) ; z:0.t94(l) ] for a metamict and

a non-metamict zircon using three-dimensionaldata but they did not

give cell dimensionsor bond lenqthsfor either srrucrure.

ExprulmnrAl DBt.trr-s
The zircon crystal used in this study was obtained from a syenite in Kragero, Norway.
Sharp diffraction maxima on weissenberg photographs indicate that this specimen is non-
metamict. This is substantiated by the fact that the cell dimensions agree with those given
by Holland and Gottfried (1955) for gem-quatity, unirradiated zircon. Electron microprobe
analysis indicated that the only impurity present in detectable amounts is hafnium (-1
rvt. percent). unit cell parameters are a:6.607(1); c:5.982(l) A, Z:4, p:4714
gm/cc. The space group is l\t/amd. More than 550 non-zero intensities were measured with
an equi-inclination weissenberg single-crystal diffractometer using Nb-filtered Mo radia-
tion and a scintillation counter. The intensities were recorded on a stripchart, integrated
with a planimeter, corected for Lp and, absorption effects and converted to structural
amplitudes. These were submitted to an isotropic least-squares calculation (Busing, Martin,
and Levy, 1962) using the positional parameters for oxygen (0 0, 0.067, 0 198) determined
by Krstanovi6 (1958), where the origin was chosen at 2f m. Form f actors were taken from
the rnternational Tables, vol. rII for Si and o, that for zt'+ was taken from cromer and
Waber (1965) and corrected for the reai part of anomalous dispersion. The lFobs ,s were
weighted according to a schemeproposed by Hanson (1965), and the weights were adjusted
to give approximately equal (uAF2) for ten equally populated groups of increasing
ir(obs) | thereby making {zerAF2) essentially independent of magnitude of the individ-
ual lF(obs) I's
A relatively large number of low angle, high intensity reflections were rejected in the
final refinement because of extinction effects, and the unweighted residual for 498 i 1t(obs) 's
was 0.020 (iveighted R:0.024). The anisotropic refinement reduced R to 0.019 (weighted
R:O.022), and an 1l-factor test (Hamilton, 1965) showed that this relinenent was more
significant than the isotropic one.
finalpositional and thermal parameters are given in Tables 1 and 3. The interatomic
distances and bond angles are listed in Table 2.

The principal structural unit in zircon is a chain of alternating edge-
sharing SiOr tetrahedra and ZrOs triangular dodecahedra extending
parallel to c (Fig. 1). The chains are joined laterally by edge-sharing

T.q.sI,n 1 Postrtoxer, PAnauntnns, ANrsomoprc'Irlrpnr-a.tunn Iracrors,

lNo EqurvalnNr Isornoprc Tpupnrerurc Facrons lon ZrncoN

Atom r 0"2 9sa \tz 9n Fzt


Zr 0.O O.75 0.125 0 . 0 0 0 9 6 ( 8 ) 03 . 0 0 0 9 6 ( 8 )0 . 0 0 1 2 ( 1 ) 0 . 0 0.0 0.0 0 . 2 3( 1 )

si 0.0 0.7s 0.62s 0.0014(1) 0 0014(1) 0.0027(3) 0.0 0.0 0.0 0 . 4 5( 2 )

o 0.0 0.0661(1) 0.19s3(1) 0.0037(2) 0 0031(2) o.oo29(2) 0.0 0.0 _0 0000(2) 0.s3(2)

3 Estinated standard deviations are in parentheses

and refer to the last deciml place.

'Insrn 2.Ixtrn,lrourc Drsrancns (A) ,l-ltl Axcr,rs (Drcntns) rN Zrncor

S'iOa Tetrohe.d.ron
si-o t4l' r . 6 2 2( r ) b

04 Distances Angles at Si
o-o 1212.43O(2)r e 7 . 0( 1 )
o-o t412.7s2(2) 116.06 (8)

Mear' 2.645 to9.7r

ZrO s T rian gutra+D oilecahedron
Zr-o(L) t4l 2 . 2 6 8( t )
zr-o(B) t4l 2.r3r(r)
Mean 2.200

04 Distances Anglesat Zr
o(A)-o(A')l2l 2.430(2)t 6 4 . 8( 1 )
o(A)-(B) t8l 2.8+2 (r) 80.41(2)
o(A)-o(B) t4l 2.494(2)d (s)
o(B)-o(B')t413 . 0 7| ( 2 ) (r)

M:an 2.770 78.77

Catio n-C atio n Dis tances Angles ot o*ygen

Zr -Zr' 3.626 (2) 1 1 1 . 0(2s )
Zr -Si 2.eer(2) ee.17(6)
Zr'-Si 3 . 6 2 6( 2 ) 14e.81 (s)

[]" Multiplicity.
0b Estimated standard deviations refer to the last decimal place.
t Edge shared between tetrahedron and dodecahedron.
d Edge shared between two dodecahedra.

Tesr-n 3. Mecrrruup AND ORTENTATToNS ol PnrNcrp,c'r Axns

ol rrm TrrenuAl ErLrPSorDs

Angle (') with respect to:

Atom rms displacement
Axis A

Si rr (s),
o.Oss 0 90 90
f9 (6)
0.Oss 0 90 90
0.070(4) 90 90 0 (3.4)

Orr 0 . 0 7 2( 3 ) 90 9 r. 4( r 3. 7 ) 1.4(13.6)
r2 0.083(3) 90 r . 4( r 3 . 7 ) 8 8 . 6( 1 3 .7 )
rl 0.0e2(3) 0 90 90

u Estimated standard deviations are in parentheses.


Frc. 1. The chains of alternating edge-sharing SiOa tetrahedra andZrOs triangular

dodecahedra extending parallel to c and joined laterally by edge-sharing dodecahedra.

dodecahedra(y' Figs. 1 and 2) and are responsiblefor zircon's prismatic

habit and (110) cleavage,its extreme birefringence and optically positive
Similar chains occur in garnet (Fig.3), extending in three mutually
perpendicular directions, but they are cross-linked by ZOo octahedra as
well as by XOs dodecahedra.In zircon octahedral voids are present but
contain no cations. The structural similarities of zircon and garnet ac-
count for their similar hardness,density and high refractive indices.
Fro. 2. The chains of alternating edge-sharing SiOn tetrahedra arrdZrOe dodecahedra
projected on (001) and showing the edgesharing between dodecahedra.

Frc. 3. A comparison of the alternating edge-sharing tetrahedra and

dodecahedra chains in zircon with similar chains in sarnet.



Frc. 4. The coordination, interatomic distances and angles for oxygen.

Orygen'coord,inationand the Si-O bond. The_oxygen in zircon is coor-

dinated in a olanar arrav bv one Si at 1.622A and two Zr at 2.131 and
2.268h (nig. +), and it h*. it, maximun vibration axis normal to this
plane (Table 3). The length of the Si-O bond is similar to the predicted
value of 1.624A for a three-coordinatedoxygen (Brown and Gibbs,
1969).The mean bond angleat oxygenis 120o,suggestingthat its orbitals
are sp2hybridized, leaving a lone pair perpendicular to the planar array
available to form a double bond with Si. In garnet oxygen is four-coor-
dinated by one Si, two { X2+ } cations and one I Z3+] cation, suggestingsy'3
hydridization of the oxygen orbitals, with no lone pairs available for
double bonding (Griffith, 1969). This may explain why the Si-O bond in
garnet (Novak and Gibbs, 1971)is 0.01-0.034 longer than in zircon, but
fails to explain the long Si-O bond of 1.641A in topaz (Ribbe and Gibbs,
1971)where oxygenis three-coordinatedby two Al and one Si.

Cation coordination pol,yhedra.The SiOn group in garnet has site sym-

metry 4=Sq and in zircon42m= Dza,but both are tetragonaldisphenoids

Frc. 5. The Dzatriansular dodecahedron(after Hoard and

Silverton, 1963)for ZrOsin ziicon.

elongated along the S+ axis. In zircon the Si vibration spheroid is prolate

along this axis in conformity with the distortions of the disphenoid (Table
The two O-O edges shared with the ZrOs dodecahedron are short,
2.4304, opposite O-Si-O anglesof 97.0o.The unshared edgesare 0.32A
longer, opposite O-Si-O angles of 116.1" (see Table 2). The Si-Zr re-
pulsion acrossshared edgesprobably accounts for the elongation of the
SiOagroup along a.
The ZrOs polyhedron can best be described as a triangular dodecahed-
ron (Hoard and Silverton, 1963). It has symmetry D2ain contrast to the
dodecahedronin garnet with 222: D2 symmetry. In zircon two edgesare
shared with SiO+ groups and four with other dodecahedra (2.4944).
There are two sets of unshared edges, eight at 2.8424 and four at
3.0714 (seeFigure 5.) Similarly in garnet two edgesare sharedwith SiO+
tetrahedra and four with other dodecahedra,but there are onlv eight un-
shared edges; the remaining four are shared with FO6 octahedra.
There are two non-equivalent Zr-O distances. The Zr-O bonds to the
edges shared between tetrahedra and dodecahedra are both 2.268 A;

those to edgessharedby dodecahedraare 2.131and 2.268A, as are those

to the eight short unsharededges.The bonds to the four long unshared
edgesare 2.Bl h, as expected.There are also two non-equivalent X-O
distances in the dodecahedraof garnet, but two short onesare opposite
the edgesshared by tetrahedra and dodecahedraand two long ones are
opposite the longest unshared edges.The steric details of the dodecahe-
dron in zircon areconsistentwith Pauling's rules, but in garnet such is not
the case(Novak and Gibbs, 1971).An explanationfor this discrepancy
was offered by Gibbs and smith (i965) who concluded that unreasonably
long Z-O bond lengths and short unshared O-O distanceswould result if
Pauling'sruleswere satisfied.

The authors are grateful to the National science Foundation for support from grants
GA-1133 and GA-12702. K. R. was supported in part by a National Defense Education Act


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