A merican M ineralogist, Vo lume62,page s 34I -345, I 977

minerals in sulfide andmetallicbonds The crystalstructure of heazlewoodite,

M. E. Flrsr Onlario of Geology,Uniuersityof Western Department London,Ontario, Canada

Abstract Heazlewoodite(NisSz)is rhombohedral, spacegroup R32, with unit cell parametersa : 4.0821(5)A, a : 89.475(9)"and one formula unit per unit cell. The crystal structure of its synthetic equivalent (aNi3Sr) has been confirmed with X-ray powder intensity data (FeKa are deflnitely radiation, I = 1.937A) and refined to aweighted residualindex of 0.058..There 'bonds' per four similar Ni-Ni Ni atom, which is at variancewith the theoreticaltreatment of and Prewitt and Rajamani. However, this treatment is shown not to be applicableto sulfides, possiblereasonsfor this are discussed.

ment might be basedon an incorrect assumption.The present study is an attempt to resolve both the misHeazlewoodite(Nissr) is rhombohedral with space and givings on the crystal structure of heazlewoodite group R32. The unit cell is dimensionally nearly Pearson's and the structure between the inconsistency cubic, having a : 4.080 A, a = 89.43' (Peacock, 1947), and contains one formula unit of Nissr. The valencerule. crystal structure of its synthetic equivalent (aNiaSz) Experimental was determined by Westgren (1938) from qualitative The crystal-structure investigation was rnade on X-ray powder intensity data and has Ni atoms in the synthetic aNi3Sr, using X-ray powder diffraction 3e equipoint position with y : 0.25 and S atoms in precession camera the 2c equipoint position with x : 0.25. The S atoms data. A preliminary single-crystal from the type form a slightly distorted body-centeredcubic array, investigationon natural heazlewoodite and the Ni atoms occupy distorted tetrahedral inter- locality, Trial Harbour, Tasmania, had shown that the crystallite mosaic spread in this material was far stices.In addition to its four S neighbors, each Ni atom has four nearestneighbor Ni atoms, two at 2.48 too great for the collection of meaningful intensity A a n d t w o a t 2 . 5 1 A . T h e s e N i - N i d i s t a n c e sa r e data. On zero-levelprecessionfilms, reflections are similar to that in metallic Ni, and Hulliger (1968), rotated or spreadaboutthe film center by as much as Fleet (1972),and Prewitt and Rajamani (1974a)have 30o. However, the reflections are otherwise sharp, argued that they indicate a significant degreeof me- showing no tendencyto be diffuse along radial directallic bonding in heazlewoodite. Each S atom is tions or lattice rows, and thus giving no indication of coordinated to six Ni atoms. Ni.SSe, NirSer, and disorder or lack of crystal perfectionin the individual (Ni,Co)rS, also crystallize-with the heazlewoodite crystaflites. This investigation on natural heazlespacegroup woodite also confirmed that the accepted s t r u c t u r e( H u l l i g e r , 1 9 6 8 ) . Recently, however, in spite of a qualitative con- (R32) is consistent with the diffraction symmetry. firmation by Peacock (194'l), several authors have The systematic absencesare just those associated questioned the correctnessof Westgren's structure with a rhombohedral unit cell indexed with hexdetermination. Pearson (1972) suggestedthat the agonal axes, giving the possible space group R32, heazlewoodite structure requires confirmation by R3m, ind R3rn. However, R3m and'R3m are inconsingle-crystal methods. Furthermore, Prewitt and sistent with the heazlewoodite structure (see DisRajamani (1974a) have noted that the structure is cussion section). inconsistentwith their modification of Pearson'svaSynthetic aNigSz was prepared by heating about lencerule for intermetalliccompounds,although they L0 g of a stoichiometricmixture of Ni spongeand S tube at 700'C for do admit the possibility that their theoretical argu- crystalsin an evacuatedsilica-glass Introduction
341

342

FLEET.'STRUCTURE OF H EAZLEWOODITE

one day and at 450"Cfor threeweeks; the Ni sponge data list contained31 independent reflections, of wasreduced with hydrogenat 900oCbeforeuse.The which 27 had nonzerointensity. unit-cellparameters, determined from a Jagodzinski investigation Crystal structure powdercamera focussing film (FeKa, radiation, tr : A) standardized 1.93597 with silicon,area : 4.0821 was The crystalstructureproposedby Westgren (5) A, a : 89.475(9)", standard deviations in paren- refinedby full-matrix, least-squares using refinement (1941). program RFINE (L. Finger, Geophysical theses, consistent with the data of Peacock LaboraAlso, only heazlewoodite reflections are presenton tory, Washington). the function RFINE minimizes X-ray powder films.Hence F" is the synthesized material is >w(lf.l -lf"l )', wherew is the reflection weight, single-phase, stoichiometric aNi3S2, as would be ex- the observed and F" the calculatedstructurefactor, pected from the available work on thephase relations and calculates a conventional residual index, (for example, of heazlewoodite index Kullerud and Yund, >llr"l-l F"ll/>lF"l, and a weighted residual and Misra and Fleet,1973). 1962, curve for Unfortunately the t>w(lf.l -lFJ)'/>rF?l'/'. The scattering degree ofcrystalperfection wasno better that thanthat of Ni2+wastakenfrom Cromerand Mann (1968), the natural material, and in view of the lack of suc- for S' computed fit from data for a nine-parameter cess of the iodine-vapor (Prewitt in International Tables transport and technique for X-ray Crystallography, and Rajamani,1974b), it was decidedto abandon real and imaginarycomponents of the anomalous furtherattempts to obtainsingle crystals of the requi- dispersion for Ni and S werefrom Crocoefficients sitequality.The reason for the difficulty in obtaining m e r ( 1 9 6 5 ) . good quality singlecrystals of heazlewoodite is unwith nonzerointensityand Using the reflections clear. However,it may be associated with a phase unit isotropic for both Ni and S, thermalparameters gave transformation grown at moder- the unrefined parameters on coolingcrystals positional of Westgren (Prewitt and Rajamani, 1974b),or valuesfor the weightedand conventional ate temperatures residual with the development of therhombohedral distortion indicesof 0.065and 0.063, respectively. Refinement of the pseudocubic for unit cell on coolingto room tem- of the positional parameters on values converged perature,and study of heazlewoodite in a heating the weightedand conventional residualindicesof camera may throw somelight on this problem. residual the weighted 0.058and 0.060,respectively, Finely-ground synthetic aNi3S2 was held in a 0.2 indexbeingsignificant to at the 0.05levelcompared mm diameter glass (Hamilton, parameters capillary tube and irradiated with that for unrefined positional FeKa radiationfor 48 hoursin a 114.6 factors mm diameter 1965). structure The observed and calculated powdercamera.The intensitydata are givenin Table l, and the positional Debye-Scherrer parameters for the crystal-structure wereobtained analysis from are given in Table 2. Refinement of the isotropic the powder film using a Joyce-Loebl reduced the weightedand condensitometer, thermalparameters and were correctedfor Lorentz and polarizationef- ventional respecindices to 0.047and 0.045, residual fects, reflection multiplicityand absorption, for and con- tively. However,the refinedthermalparameters verted to observed structure factors (4). The Ni and S are l.l3(17) and 0.05(26), respectively. Lorentz-polarization may be correction factor used was Clearly,whilstthe valuefor the Ni parameter equated to the expression (l-lcos'20)/(sin'zdcosd), meaningful,that for the S parameterlargely reflects where..0 is the Braggdiffraction angle,and reflection terminalerrors in the data set.This is as expected, multiplicities werethoseof Laueclass with 3m.ln making sinceterminal errors will be more significant the absorption correction, the weightof aNirS, per lighter atoms than heavier ones becauseof the unit volumein the capillary tubewasdetermined, and smallerscattering contributionof the former. The this allowedthe calculation of an effective linearab- low S thermal parameter doesnot reflecteithererror (p) of 280cm-r. Absorption sorptioncoefficient cor- in the assumedchemicalcompositionof aNiaSz, rectionfactors(,4*) wereestimated by graphical in- which is known to a far greateraccuracy than is terpolation from the data for a cylindrical in normallyrequired analysis, or incorrect sample for structural InlernationalTables (see followingsection). Yol. space-groqp assignment for X.ray Crystallography, pR of 2.9.Weights 2,Table5.3.58, usingan effective Discussion proportionately wereassigned to the corresponding positions intensities with X-ray observed since,as a first approximation, Refinement of the structural the uncertainty indexof in the intensitydata must increase powderintensity residual datato a weighted peak/background with decreasing ratio. The final 0.058shouldrepresent adequate of the confirmation

FLEET,'STRUCTURE OF HEAZLEWOODITE

343

parameters for synthetic Table2. Positional correctness of Westgren's structure for aNirS, and, (standard in parentheses) deviations heazlewoodite hence,for heazlewoodite. Heazlewoodite has so few atomsper unit cell(oneformulaunit of NiBS2) that an incorrectlypositionedatom in the structurewould Atom Equipoint Pos i ti on give an anomalously high residual index.It follows group for heazlewoodite that the correctspace is the 3e 1 / 2 0 . 2 4 7 ( 2 ) -v Ni accepted one, R32. R3ru doesnot allow a similar x x 5ZC 0 . 2 s( s3 ) structure. R3m, with S in 2c and Ni in 69 equipoint positions, would allow a disordered heazlewoodite structure, but this alsowouldgivea significantly high residual indexand hasprohibitively shortNi-Ni dis- one end and threenonbonded Ni atomsat the other. (2.04 tances A, 1.44 and the A). Ni-S bond distances The two nonequivalent The heazlewoodite structure is basedon a body- two nonequivalent in the reshort Ni-Ni distances centered cubic array of S atoms with Ni atomsin fined structureare not significantly differentfrom the (near-tetrahedral) threeofthe twelve sphenoidal sites respective in the ideal dimenequivalent distances per unit cell.The ordered arrangement of Ni atomsin sionally-cubic However,the S-Ni-S bond structure. the ideal structureis shown in Figure l. The NiSr anglesassociated are all shorter with sharededges 'tetrahedra' givingriseto four short than the ideal values, share four edges, with some which is consistent per Ni atom. As mentioned Ni-Ni distances edge-reearlier, degree between the polyhedral of repulsion the structure doesnot permit disordering of the Ni latedNi atoms. atoms. in heazlewoodite are The short Ni-Ni distances (2.492 Selected bond distances andbond angles with some only slightlygreater Ni for metallic than that is comparitivedata for the ideal,dimensionally cubic A). and if interatomic in thesematerials distance structure are givenin Table 3. In the refinedstruc- correlatible they would haveto with bond strength, ture, the S environment about eachNi atom is still be regarded to full metallicbonds.A as equivalent decidedly sphenoidal, but the four Ni atoms com- structure refinement based on single-crystaldata, pleting the nearest-neighbor have been Ni coordinationpoly- which may not be realized until advances hedron do not even approximate would reduce to a tetrahedral made in crystal-growing techniques, The S coordination polyedronis a disdisposition. tortedtrigonalprism,with threebonded Ni atomsat

Table l. Observed andcalculated structure factorsfor synthetic heazlewoodite

00 t0
u -l

tt I -t 0 't 0 0 0 -t 1t 1 -t -t -l 20
u -a

22.0 0.0 45.2 57.4 22.5

24.s 1.4 4 7. 1 62.0 20.5

-t

21-2 310 3 0 -l 3' I I 3 | -l 3 -t -l 222 2 2-2 320 3 0-2 321 3 2 -1

J 5 | -l -a -t

t5.B 15.8 26.1 0.0 9.8 13.2 40.3 2 1. 6 22.5 25.0 26.9 .7 36 2s.2 37.0 24.8 42.3

t5.l 15.8 28.5 1.8 il.4 14.8 40.4 25.8 25.1 26 .1 27 .4 33.6 24.3 34.4 22.7 43.5

39.6 38.0 4t.5 43.4 4 t. I 4 0 . 5 4 8 .5 4 7. 1 37.0 35.4 0.0 1.2 0 . 0 1. 7 55 .9 '11 .816.7 t5.l

?1 00

400

Fig. l. Ideal, dimensionally cubic structure of heazlewoodite showing the body centeredcubic array of S atoms and distribution of the short Ni-Ni distances:open circles; S atoms: full circles; Ni y = 3A,z = 3A. atoms: unit cell origin on S atom at x = 3/e,

FLEET,' STRUCTU RE OF H EAZLEWOO DITE Table 3. Interatomic distances(A) and bond angles(degrees)in synthetic heazlewoodite (standard deviations in parentheses)with some comparative data for the ideal undistorted structure (d : 4.0821 A)

Bond

Bond Multiplicity

Distance

Ideal Distance

B o n dA n g l e

B o n dA n g l e Multiplicity

Angle

ldea'l Angle

N i- S

-s'

-Ni' -Ni'' S-S'

2 . 2 7 ( 2 )1 2 . 2 8 2.27(2) J
, E 2 l r \ )I

z 6 I

_ s r| |
s r _ s rI

-s'

2.50 2.51(2)J 4 . 0 8 2(r5 ) 4 ') .08 3.50(2) 3 . 5 0 ( 5 ) ) 3 .5 4

J,5)\Z) J

s-Ni-s' s - N-is ' ' s - N-i s ' ' '' i s' s '- N -

N i ' - N i- N i ' ' Ni'-Ni-Ni''' N i ' - N i- N i ' v Ni"-Ni-Ni"' N i- s - N i ' Ni-s-Ni "' N i- s - N i "

'l .9 2 7. 8( 6) 1 2 6 100.7(3 )) 100.6(e ) )t o t . s r02.6(s)J 108.6(4) es.2(2) 60.0 .e(6) 147 67.2(7\ .o (2 1) 61 72 't .6 (5 . 2 5 5 ,2 . 55,.?55 .255,.255,1.255 .745,-.255,.745 .745,.745,.745

A t o m i cP o s i t i o n s : N i Ni' Ni"
Nir,l

s s' s" sf | |

Ni'" NiV

the estimated standard deviations of the Ni-Ni dis- nides must consider that in heazlewooditethere are tancesand, hence,might show that Ni-Ni' is signifi- four effectivelyequivalentNi-Ni interactionsper Ni cantly shorter than Ni-Ni" (Fig. 2). Nevertheless, the atom. Hence, having establishedthe heazlewoodite bond strengthsassociated with both distanceswould structure, it remains to explain the apparent inconremain effectively the same. Any hypothesis on the sistencybetween it and the modified valencerule of nature of the metal-metal interactions in chalcose- Prewitt and Rajamani (1974a). The valencerule introduced by Mooser and Pearsuggests by Pearson(19'12) son (1960) and discussed that intermetallicvalencecompounds must satisfythe condition (nu I n" lb^ - b")/ N": 8, where r" is the number of s and p valenceelectrons on the ligand atoms (anions), n" is the number on the metal atoms b' is the (cations) lessany unsharedvalenceelectrons, number of electrons involved in forming ligand-ligand bonds, b" is the number of electrons forming metal-metal bonds, and N, is the nurnber of that all ligand-ligand and ligand atoms. It is assumed metal-metal bonds are electron-pair ones. The usefulness of this rule is somewhat limited, and it certainly cannot be usedto confirm a possiblestructural arrangement; for example, Pearson (1972) successfully applied the rule to monoclinicZnP", assumingit to be both polyanionic and polycationic, yet this compound has been shown recently to be only polyanionic(Fleet,1974). Prewitt and Rajamani (1974a) modified the Mooser-Pearsonvalence rule to predict the number of single-bondedmetal bonds (C") per metal atom in Fig. 2. Crystal structure of heazlewoodite showing coordination sulfide compounds. Thus C" : (n^ * n" * C^Nu p o l y h e d r ao f N i a n d S : S a t o m s ; l a r g e o p e n c i r c l e s :N i a t o m s ; s m a l l open circles. 8N^)/N", where n" is redefined as the number of

FLEET.'STRUCTURE OF H EAZLEWOODITE

345

valenceplus unpaired antibonding d electronson the metal atoms, C" is the number of ligand-ligand bonds per ligand, and N" is the number of metal atoms. Prewitt and Rajamani argue that this modified rule successfullypredicts the number of metal b o n d si n m a c k i n a w i t e[ ( 6 + 6 + 0 - 8 ) / l : 4 ] , c o b a l t pentlandite [(8 x 6 + 8 x 5 + 0 8 x 8)/8 : 3],and = 8)/t 21. Therefore, the millerite K6 + 4 + 0 predicted number of metal bonds in heazlewoodite - 1 6 ) / Z : 2 . 6 7 ] c a s td o u b t o n [(2 x 6 + 3 X 4 + 0 the reliability of the crystal structure determination. However, in the calculations for cobalt pentlahdite the octahedralCo atom cannot be ignored, sincethe S atoms contribute valenceelectronsto the Co;tS o bonds, and hence for the tetrahedral cobalt atoms, C"> 3. Also, where agreement with the rule is obtained no cognisanceis taken of the stereochemical properties of the d orbitals involved. It is assumed that the antibonding 3d orbitals on the metal atoms form the bonding orbitals for the metal bonds. As discussed by Fleet (1973a and b), in studies on maucherite metal-metal interactionsin, respectively, and parkerite, these antibonding orbitals naturally project along or closeto the metal-ligand o bonding directions and are very often poorly disposed spatially to participate in the metal-metal bonds. In contrast, the spatial distribution of the nonbonding set of 3d prbitals will very often allow for end-on overlap to form metal-metal o bonds. However, in many minerals, all of the nonbonding electrons would be paired if the metal-ligand complexeswere isolated, and some of these electrons must be removed for bonding interactionsto take place. Rajamani and Prewitt (1974) and Prewitt and Rajamani Q97aa) assumedthat all of the metallic bonds they discussed were equivalent to single bonds-that is electron-pair bonds. There is, of course,no logical reasonwhy this should be the case, especiallysince this is apparently not a requirement of the metal-ligand o bonds, and metal-metal 'bonds' do show a wide variation in bond length in Prewitt and Rajamani (1974a) have chalcogenides. suggestedthat this assumption might be incorrect and thus be the explanation for the lack of agreement 'observed' number of between the calculated and metal bonds in heazlewoodite. In summary, the modified valence rule has not minerals been demonstratedto apply to chalcogenide in general.The theoreticalbasisfor it is unsound, and

of thus it cannotbe usedasa checkon the reliability of heazlewoodite. the crystalstructure Acknowledgments
This work was supported by a National Research Council of C a n a d a o p e r a t i n g g r a n t . M r . R i c h a r d D . H a l l ( W e s t e r nO n t a r i o ) prepared the synthetic NirS, and Miss Yu-Chi Cheng (Western O n t a r i o ) m a d e t h e u n i t - c e l l p a r a m e t e rd e t e r m i n a t i o n .

References computed corrections dispersion Anomalous D. T. (1965) Cromer, Dirac-Slater wavefunctions. field relativistic from self-consistent ,Acta Crystallogr,18, l'l-23. computed factors X-ray scattering and J. B. Mann (1968) Acta Crystallogr-, wavefunctions. Hartree-Fock from numerical A24. 321-323. of a-Ni'Su.Acta Crystal' The crystalstructure Fleet,M. E. (1972) logr, 828, 1237-1241. (NirrAs,) ,4n (1973a) of maucherite The crystalstructure Mineral, 58,203-210. (NLBirSr),4t2. (1973b) of parkerite The crystalstructure Mineral. 58. 435439. (1974)The crystalstructureof ZnAsr. Acta Crystallogr., 830, t22-126 R on thecrystallographic tests W. C (1965) Significance Hamilton, 18, 502-510. factor.A cta Crystallogr., and of the chalcogenides Hulliger,F. (1963)Crystalchemistry pnictidesof the transition metals.Stucture and Bonding,4, 83-229. andrelated The Ni-S system Kullerud, G. and R. A. Yund (1962) J Petol . J. 126-175. minerals. of compositions ( 1973) Thechemical Misra,K. C and M. E Fleet Econ. Geol-,68, assemblages. and naturalpentlandite synthetic 5 r 8-539. bond in (1960)The chemical Mooser,E. and W. B. Pearson In, A. F. Gibson,F' A. Krciger'and R. E. semiconductors, 5,103-137. in Semiconductors Ed., Progre.s.s Burgess, comand the artificial On heazlewoodite M. A. (1947) Peacock, 5I' 59-69. Series' Geological Studies, poundNisSr.IJniu Toronto of Metals andPhysics Chemistry W. B. (1972)TheCry.stal Pearson, New York. and Alloy.sWiley-lnterscience. and Prewitt,C. T. and V. Rajamani(l97aa) Electroninteractions In, P H. Ribbe, Ed.' Saffide chemicalbonding in sulphides. Notes l, PR-l to Mineral. Soc.Am. Shorl Course Mineralogy, 41. charactergrowthandstructural (1974b)Crystal snfl sulfides.CollectedAbstracts,Int. ization of transition-metal Meeting,Berlin and Regensburg' Minerol Assoc 9th General t29. of V. and C. T. Prewitt(1974)The crystalstructure Rajamani, . millerite.Can.Mineral , 12,253-25'1 allg. Z. anorg' von Ni3Sr. Die Kristallstruktur A. (1938) Westgren, Chem . 239.82-84.

Manuscript receioed,February 27, 1976; accepted for publication, JulY 19, 1976.