Crystal Structure of Indialite the Ii

Crystal Structure of Indialite the Ii

Canadidn Mineralogist Vol. 15, pp. 4349 (1977) THEPOLYMORPHISMOF GORDIERITE: II. THECRYSTALSTRUCTURE OF INDIALITE E. P. MEAGHER Department of Geological Sciences,Unlversity of British Columbia, vancouver S, 8.C., CanadaV6T lws G. V. GIBBS Department of Geological Sciences,Virginia Polytechnic Institute and State University, Blacksburg,Virginia 24061 U.S.A. Ansrnecr INrnooucttoN . A least-squar€s refinement of typeJocality india- The earliest quantitative information on the lito [Mgr.eoFeo.6d,l4.r1si4.8gO1P 6 / mcc; a 9.800(3), c "; phase relations of cordierite was provided by 9.345(3)Al shows rtre Iz tetrahedra in tle six-mem- a combined microscopic and thermal study of bered ring of the framework to be significantly the system MgO-AlrOu-SiOz by Rankin & smaller than the linking I tetrahedra. By compari- Mer- son of (I-O> data for cordierite the contents of win (1918) who discovered two forms of Mgz these tetrahedra are estimated to be ([: 0.72 N, AlnSisOre,referred to as cu and #, forms. Th" p 0.28 Si; 7l: 0.30 ,4'1,0,70 Si). Because the Al con- form was considered to be a metastable prod- tent of the f1 tetrahedra differs significantly from uct because, after crystallization from glass at 1.0, the order-disorder changes in cordierite involve temperatures below 950oC, it transformed ir- all the tetrahedral atoms in the framework rather reversibly upon heating to the c form and be- tlan just those in the six-membered ring. The de- cause repeated attempts to transform the c form of long-range order estimated with €ree tle Bragg- to the p form at temperatures below 950'C Williams equation is 0.38. The constraints of P6/mcc symmetry permit a range of intermediate structufal failed. On the other hand, the <r form was found states, and a domain structure is consitlered in terms to possessa well-defined stability field and crys- of the Al, Si contents of the tetrahedra. tallized as six-sided prisms. A conoscopis exam- Statistically 'nearly featureless Fourier (F,-F") maps indicate an absence ination of this material yielded or quite of atoms in the structural channels parallel to the uniaxial negative interference figures" indicating c axis. hexagonal or quasi-hexagonal symmetry. Al- though the paucity of data on natural cordierite Souuann precluded a definitive comparison between it and the a and p, forms, the physical properties La structure de I'indialite du gisement type of the a form were found to be similar to those [Mgr.aoFeo.uaAla.gSiE.arOraiP6/mcc; a 9.800(3), c of the natural material. 9.345(3)Al, affin6e par moindres carr6s, r6v6le que Ies t6traddres 7r des anneaux hexagoiaux de Ia Crystallographic, optical and chemical data charpente sont nettement plus petits que les t6- subsequently obtained for natural cordierite traddres Z1 intercalaires. En comparant aux don- showed the mineral to be orthorhombic and to q?-O) n6es de la cordi6rite, on estime la ppula- possessa crystal structure similar to that of hexa- tion des t6traddres: 0.72N, 0.28Si en ?r; 0.30,4,1, gonal beryl (Fig. 1; Gossner & Mussgnug 1928; 0.70Si en ?s. Comme la teneur eri Al des t6fiaedres Tr diffdre qotablement de 1.0, les changements or- Takane & Takeuchi 1936; Bystriim 7942; Folins- dre-d6sordre, dans la cordi6rite, impliquent tous les bee 1941).A later study of the polymorphism of atomes t6tracoordonn6s de la charpente et non pas cordierite using optical and powder diffracto- seulement ceux des anneaux. Ir degr6 d'ordre d meter data led Miyashiro & Iiyama (1954) to Iongue distance, estim6 au moyen de l'6quation de assert that the a form is truly hexagon'al and Bragg-Williams, est 6gal i 0.38. Irs contraintes im- therefore distinct from natural orthorhombic pos€es par le groupe spatial permettent toute une cordierite. A natural analogue of the a form was s6rie d'6tats structuraux interm6diaires, €t une struc- subsequently discovered in the fused sediments ture en domaines est concevable en fonction de la of the Bok'aro coalfield, India, and named india- population (Al,Si) des t6tra0dres. Irs s6ries diff6- rences (Fo-F.), statistiquement sans relief, indiquent lite (Miyashiro & Iiyama 1954). Although the I'absence d'atomes dans les tunnels structuraux pa- structural relationship between indialite and cor- ralldles i l'axe c. dierite was unknown, it was recognized that (Iraduit par la R6daction) indialite is a hexagonal polymorph of Mg"AIr 43 44 TTIE CANADIAN MINERALOGIST Frc. 1.. The structure of indialite (eft, c-axis projection) compared with an idealized drawing of the structure of low cordierite (righl c-axis projectioa). Iq the indialite structure, ?1 sites are Si-rich and Iz are Al-rich. In the low cordierite structure, full 7! Is circles are Si and open ?r, 72 circles are Al. SisOre{Fig. 1; Miyashiro & Iiyama 1954; Miya- The present study of indialite was undertaken shiro ef al. 1955). Miyashiro (1957) has since to clarify the polymorphism of cordierite by de- suggestedan Al,Si order-disorder transformation termining whetler indialite is truly hexagonal, between cordierite and indialite, analogous to or dimensionally hexagonal but with a lower that exhibited between the alkali feldspars low symmetry and whether the order-disorder microcline and high sanidine. The transforma- changes involve 1 A1 and 5 Si atcvmsin a six- tion in cordierite was assumed to involve the dis- membered ring or 4 Al and 5 Si atoms in the tribution of 1 Al and 5 Si atoms in a six-mem- AlaSLOa tetrahedral framework (Meagher & bered ring; the remaining a Al atoms were as- Gibbs 1965; Meagher 1967). sumed to occupy the tetrahedra outside the ring and not to be involved in the order-disorder B><pnnrraENter. change. Miyashiro reasoned tlat a disordered configuration of Al and Si in the ring would re- The specimenof indialite usedin this investiga- sult in a hexagonal symmetry for indialite. On tion was collected from paralava formed during the other hand, a partly or completely ordered fusion of shale and sandstone by a burning coal configuration would produce the symmetry cf seam in the Bokaro coalfield, India (specimen orthorhombic cordierite. However, a refinement +23 / 95 L of Fermor's collection-Fermor (191 8). of the structure of an orthorhombic cordierite Its chemical composition was determined with from Guilford, Conn. (Gibbs 1966) suggests im ARL-SEMQ automated electron microprobe that the order-disorder transformation involves utilizing the data corection routine of Bence & the distribution of all of the tetrahedral atoms in Albee (1968). The results of the analysis are a continuous AloSiuOtr tetrahedral framework listed in Table 1. A measurementof the specific instead of just the arrangement of L Al and 5 Si gravity of indialite was not attempted besause atorns in a six-membered ring. Moreover, the it contains minute unidentified inclusions; how- tetrahedral atoms were found to be completely ever,. its density crlculated from the unit-cell ordered within the limits of error with A1- and dontents and cell edgesis 2.59 glcc. $i-ssafdning tefrahedra in perfect alternation Single-crystal Weissenberg and precession in all directions except for two Si-containing photographs revealed systematic absences of tetrahedra that share a common oxygen in the the type: hhl, l=2n*I and hhl, I=2n{1, con- six-membered ring (Gibbs L966i Cohen et aI. sistent c.ith space gxoups P6cc and P6/ mcc. T\e 1977). unit-cell parameters determined by least-squares CRYSTAL STRUCTIJRE OF INDIALITE 45 'I. TABTE CHEI.{ICALAND PHYSICAL DATA FOR INDTALITE RsnNsrvrnr.Ir oxlde: Mso Feo* At203 St02 The refinement of indialite was carried out .lo0,4g [elght %: 9.3 7.8 34.7 48.6 Tota.t: in space group P6/ mcc because of the apparent structural relationship between indialite, beryl Unit cell content and low cordierite. Starting atomic positional nornnlized to 18 oxygens: ?[HSl.4OFe0, Sll. 6C14. t t Ag0lA] parameters for indialite were obtained by trans- formation of the refine.d positional parameters group: Space P6,hcc Calculated denslty: 2.59 g/cc for Haddam cordierite (Meagher 1967) to a hexagonal basis. Cell dinenslons: a . 9.900(3)l c . 9.3a5(3)l The structure refinement was calculated with qn-l an IBM 360/67 using p: 14.9 Radlation/filter: Mo/Zr a modified version of the full-matrix least-squares program ORFIS (Bu- Crystalslze: 0.14x 0.10x 0.06mn sing ef al.1964). Scattering curves from the In- ternational Tables for X-ray Ctystallography llumberobserved feflectlons: l6g (L962) were modified for half ionization and corrected for tle real part of the anomalous dis- R " r(lFol-ircl)/rlFol. o.oqz persion. Unobserved reflections were not in- cluded in the refinement and the weighting . tu{ (x w(lrol - lrcl)ztrwFo2)l/2. 0.061 scheme of Hanson (f965) was applied. Because the Al,Si distribution in the framework was ini- i Total Fe assuniedferrous tially unknown, the atoms at the Tr and Tz tetra- hedral sites were assigned a random distribution scattering curve of 4/9 N + 5/9 Si in the first few cycles of refinements of precision back-reflection Weissen- of the refinement a model based on isotropic temperature coefficients. berg data (c 9.8000(3),c 9.345Q)A) compaf,ewell factor with those determined by Miyashiro et al. (1955) Upon convergence of the refinement (weighted b 9.812, c 9.351A). R-index = 0.085) tetrahedral Al,Si contents were In order to critically 4nalyze the dilfrastion estimated from the a"-O) bond lengths (de- symmetry of indialite, intensity data were col- tails of this procedure are given in Discussion lected on the basis of an orthorhombic cell Section).

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