THE AMERICAN

MTNERALOGIST, VOL,56, MAY_JUNE,

1971

THE STRUCTURE OF ZIRCON: A COMPARISON WITH GARNET Knrrn RouNSow, G. V. Grsns, eNn P. H. Rrnnr, Departmentof Geological, Sci,ences. Virginia PolytechnicInstitute and State g, U niaersity, Blacksbur V irgi,nia 2406I
Aesrn,{cr 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 positional 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 extending 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-coordinated 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.

INrnonucrtoN Zircon, ZrSiO+,occurs as an accessorymineral in granitic and syenitic igneousrocks and is a common detrital componentof sedimentaryrocks. Its relativelv high density and resistance weatheringhave contributed to 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 twodimensional 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 threedimensionalrefinement,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 782

STRUCTURE OF ZIRCON

783

a non-metamict zircon using three-dimensional data but they did not give cell dimensions bond lenqthsfor either srrucrure. or
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 nonmetamict. 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 'fhe 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 radiation 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 's ir(obs) | thereby making {zerAF2) essentially independent of magnitude of the individual 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. 'Ihe finalpositional and thermal parameters are given in Tables 1 and 3. The interatomic distances and bond angles are listed in Table 2.

DtscussroN The principal structural unit in zircon is a chain of alternating edgesharing 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, lNo EqurvalnNr PAnauntnns, ANrsomoprc'Irlrpnr-a.tunn Iracrors, Isornoprc Tpupnrerurc Facrons lon ZrncoN

Atom Zr si o

r 0.O O.75 0.0 0.7s 0.0 0.125 0.62s

0"2

9sa

\tz

9n

Fzt

(equ1v../

0 . 0 0 0 9 6 ( 8 ) 0 . 0 0 0 9 6 ( 8 )0 . 0 0 1 2 ( 1 ) 0 . 0 3 0.0014(1) 0 0014(1) 0.0027(3) 0.0

0.0 0.0

0.0 0.0

0 . 2 3( 1 ) 0 . 4 5( 2 )

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.

784

ROBINSON, GIBBS, AND RIBBE 'Insrn 2.Ixtrn,lrourc
S'iOa Tetrohe.d.ron

Drsrancns (A) ,l-ltl Axcr,rs (Drcntns) rN Zrncor

si-o
04 Distances

t4l'
(2)r 2.43O 121 (2) t412.7s2
Mear' 2.645

( r.622r)b
Angles at Si

o-o o-o

( e7.01) (8) 116.06

to9.7r
2 . 2 6 8( t )

ZrO s T rian gutra+D oilec ahedron

Zr-o(L) zr-o(B)

t4l t4l

(r) 2.r3r
2.200
Anglesat Zr 6 4 . 8( 1 ) 80.41(2)

Mean 04 Distances

o(A)-o(A')l2l 2.430(2)t (r) o(A)-(B) t8l 2.8+2 o(A)-o(B) t4l 2.494(2)d o(B)-o(B') 3 . 0 7| ( 2 ) t41
M:an 2.770 Catio n-C atio n Dis tances 3.626 (2) Zr -Zr'

(s) 6e.00 (r) 92.23
78.77
Angles ot o*ygen

Zr -Si Zr'-Si

(2) 2.eer
3 . 6 2 6( 2 )

s 1 1 1 . 0(2 ) (6) ee.17 (s) 14e.81

[]" Multiplicity. 0b Estimated standard deviations refer to the last decimal place. t Edge shared between tetrahedron and dodecahedron. d Edge shared between two dodecahedra. ol AND ORTENTATToNS PnrNcrp,c'r Axns Tesr-n 3. Mecrrruup ol rrm TrrenuAl ErLrPSorDs Angle (') with respect to:

Atom Axis

rms displacement A

Si rr
f9

(s), o.Oss (6) 0.Oss
(4) 0.070 ( 0 . 0 7 23 ) (3) 0.083 (3) 0.0e2

0 0 90 90 90 0

90 90 90 9 r. 4( r 3. 7 ) r . 4( r 3 . 7 ) 90

90 90 0

(3.4)

Orr
r2 rl

1.4(13.6) 8 8 . 6( 1 3 . ) 7 90

u Estimated standard deviations are in parentheses.

STRUCTUKE OF ZIRCON

78s

z

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 character. 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 account 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.

STRUCTURE OF ZIRCON

787

5t
(\I

o o)

Zr'

G6\
Zr
Frc. 4. The coordination, interatomic distances and angles for oxygen.

Orygen'coord,inationand the Si-O bond. The_oxygen in zircon is coordinated 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, that its orbitals suggesting 1969).The mean bond angleat oxygenis 120o, are sp2hybridized, leaving a lone pair perpendicular to the planar array available to form a double bond with Si. In garnet oxygen is four-coordinated 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, by 1971)where oxygenis three-coordinated two Al and one Si. The SiOn group in garnet has site symCation coordination pol,yhedra. but both are tetragonaldisphenoids metry 4=Sq and in zircon42m= Dza,

788

ROBINSON, GIBBS, AND KIBBE

(after Hoard and Frc. 5. The Dzatriansular dodecahedron 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

3). 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 repulsion acrossshared edgesprobably accounts for the elongation of the SiOagroup along a. The ZrOs polyhedron can best be described as a triangular dodecahedron (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 edges are sharedwith SiO+ tetrahedra and four with other dodecahedra,but there are onlv eight unshared 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;

OF STRUCTURE ZIRCON

789

are those to edgessharedby dodecahedra 2.131and 2.268A, as are those edges.The bonds to the four long unshared to the eight short 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 dodecahedron 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.
ACKNOW LEDGE\,ENTS

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 fellowship. RBrrnnNcns Bwrs, W. (1926) The crystalline state of zircon. Minerol' Mag.2l, 176' Bno'rvw, G. E., ,r,No G. V. Grnns (1969) Oxygen coordination and the Si-O bond' Amer' M iner al,.54, 1528-1539. BusrNe, W. R., K. O. MennN, and H. A. Lnv.Y (1962) ORFLS, a Fortran crystallographic Ieast-squares program. oak Rid.ge Noti,onal, Lab. ltl s. Clearinghouse Fed.. sci.. Tech. InJo.l D oc. ORNL-TM-305. (1964) ORFFE, a Fortran crystallographic function and error program. oak Ridge National Lab.lU.S. Cleari'nghouseFed' Sci' Tech. InJo'l Doc ORNLTM-306' Cnounn, D. T., eNn J. T. Waern (1965) Scattering factors computed frorn relativistic l8' Dirac-Slater Wave Functions. Acta Crystal,l'ogr. 104t-109' Grees, G. V, aNn J. V. Slrrrn (1965) Refinement of the clystal structure of synthetic pyrope. A mu. LI ineral. 50, 2023-2039. Gn6r.rrn, W. P. (1969) Raman studies on rock-forming minerals-Part 1. Orthosilicates and cyclosilicates J. Chem. Soc A,1372-1377 . HeNsoN, A. W (1965) The crystal sfiucture of the azulene, S-trinitro-benzene complex. gr. A cta Cry stal'l'o 19, 19-26. H.eJfrrrox, W. C. (1965) Significance tests on the crystallographic R factor. Acta crystal'logr.18,502-510. Hesspr,, O. (1926) Die Kristallstruktur einiger Verbindungen von der Zusammensetzung MROn-L Zirkon ZrSiOr. Z. Kr is t aIIogr. 63, 247-2 54' Hor.r,exo, H. D , eno D. Gorrntreo (1955) The efiect of nuclear radiation on the structure of zircon. A cta Cr y stdl ogr. q 29 1294. Honno, J. L., lNn J. V. SrrvenroN (1963) Stereochemistry of discrete eight-coordination. 1. Basic Analysis. I nor g. Chem. 2, 235-249. Knsrewovrd, L R. (1958) Redetermination of the oxygen parameters in zircon (zrsioa). 11, Acta Crystal'logr. 89G897. S. Dyunrd, aNo P. ft.ri (1968) Further X-ray study of zircon (a'bstr). Intern. MineraJ. Assoc.,6thGen.M eet.,Prague,p.85. Novrr, G. A., mm G. V. Grsns (1971) The crystal chemistry of the silicate gatnets. Amer. Mdneral'.56,791-825.

790

RABINSON, GLBBS, AND RIBBE

Rrrln, P. H., elro G. V. Gress (1971) The crystal structure of topaz and its relation to physical properties. Amer. M i,neral,.56, 24,30. Vnc,r.to, L. (1926) Results of crystal analysis, Part II, The zircon group. ph.il. Mag., Ser.7, l , 11 5 8 - 11 6 8 . Wrrrrn, E. W., eno G. V. Grnes, (1967) Structural and chemical efiects on the SiKB x-ray line f or silicates . Amer. Mineratr. 52, 985 993. Wvcrorl, R. W. G., ANDS. B. Hr,Nllcrs (1928) Die Kristallstruktur von Zirkon und die Kriterien fiir spezielle Lagen in tetragonalen Raurngruppen. Z . Kri.statrtrogr. 7 3-102. 66, M anuscr,i.pt receild, OctoberI , 1970, accepted,or publi.cati.on,Decem.ber 1970. 4, f