1. Sulfides
Simple sulfides – based on close-packed sulfur atoms, with metals in void spaces.
Complex sulfides – based on molecular like clusters,
chains or sheets.

2. Simple Sulfides
Sulfides with tetrahedral coordination
Sulfides with octahedral coordination
Sulfides with mixed octahedral and tetrahedral coordination
Sulfides with unusual coordination

3. Sulfides with tetrahedral coordination

4. Sphalerite β-ZnS

5. Sphalerite (β-ZnS) has cubic close-packed sulfur atoms with
Zn in half of the tetrahedral sites. Stacking direction is along
the cube diagonal with ABC stacking sequence producing a
face-centred cubic unit cell.

6. wurtzite
α-ZnS

7. chalcopyrite

8. Chalcopyrite’s structure is tetragonal but consists essentially
of two superimposed sphalerite cell, but differs because of the
two different kinds of atoms, Cu and Fe.

9. Tetrahedrite
Cu12Sb4S13

10. (a) sphalerite
(b) chalcopyrite
(c) tetrahedrite

11. Enargite Cu3AsS4

12. If an oblique lattice has a ≈ b and γ ≈ 120º , a nearly hexagonal primitive lattice
becomes a centred one. A third perpendicular c direction yields a C-centred
orthorhombic lattice.

13. Derivative Structures
Cubic Close-packed
Hexagonal Close-packed
Lonsdaleite
Diamond
Wurtzite α-ZnS
Sphalerite β-ZnS
Enargite Cu3AsS4
Chalcopyrite CuFeS2
Tetrahedrite Cu12Sb4S13

14. The unit cell of sphalerite is analogous to that of diamond in that the sulfur atoms are CCP as the carbon atoms are in diamond. Zinc atoms fit in one-half of the tetrahedral spaces.
The base of the tetragonal cell of chalcopyrite (a = 5.25Å) is very close to the cubic cell edge of sphalerite at (a =5.43Å). The c dimension at 10.32Å is approximately double the sphalerite cell edge.
The unit cell of tetrahedrite is cubic and twice the size of that of sphalerite at a = 10.34Å. It is however a stuffed derivative in that there are more metals than sulfurs
The unit cell of wurtzite is analogous to that of lonsdaleite in that the sulfur atoms are HCP as the carbon atoms are in lonsdaleite. Zinc atoms fit in one-half of the tetrahedral spaces.
Enargite is orthorhombic, but its a-axis is equal to a√3 of wurtzite. The relationship here is one wherein any hexagonal Bravais lattice can be converted to an orthorhombic one.

15. bornite

16. bornite –tarnished
“peacock ore”

17. Sulfides with octahedral coordination

18. pyrrhotite

20. galena
Pyromorphite:Pb5(PO4)3Cl
Galena

21. Sulfides with mixed octahedral and tetrahedral coordination

22. pentlandite
(Ni,Fe)9S8

23. Sulfides with unusual coordination

24. Covellite
CuS

25. Chalcocite Cu2S

26. Cinnabar
Cinnabar
Cinnabar HgS

27. acanthite, Ag2S
pseudomorphous
after argentite

28. molybdenite
MoS2

29. Complex Sulfides Molecular-like clusters Molecular-like chains
Molecular-like sheets

30. Pyrite
pyrite

31. Pyrite
pyrite

32. Cobaltite CoAsS

33. marcasite

34. (b) marcasite
(a) pyrite

35. arsenopyrite

37. More Derivative Structures
Pyrite group - cubic
Marcasite group - orthorhombic
Pyrite FeS2
Marcasite FeS2 -
Cobaltite CoAsS
Arsenopyrite FeAsS
Cobaltite is orthorhombic, but
has nearly equal axis lengths,
hence close to cubic.

38. Skutterudite (Co,Ni)As3

39. CoAs3-x Skutterudite-type structures e.g. M4X12
filled skutterudite RM4X12
Typical compositions are
(Co,Ni,Fe)As3-x so the end-
members NiAs3-x and FeAs3-x
nickel-skutterudite and ferro-
skutterudite also exist
R = La, Ce, Pr, Nd, Nd, Eu (i.e. rare earths
M = Fe, Ru, Os
X = P, As, Sb

40. orpiment
realgar

41. Stibnite
Stibnite Sb2S3

42. Stibnite Sb2S3 The structure is composed of chain-like groups
of Sb (large circles) and S (small circles)

43. Yellow = S, Purple = Bi , Green = Pb, Blue = Cu
bismuthinite
krupkaite
aikinite
Bi2S3
CuPbBi3S6
CuPbBi S3
Yellow = S, Purple = Bi , Green = Pb, Blue = Cu
The aikinite-bismuthinite (CuPbBiS3-Bi2S3) series of ordered derivatives (superstructures) is based on the incremental Bi + vacancy → Pb + Cu substitution (Petříček & Makovicky 2006).
Members of the series include Aikinite, Bismuthinite, Emilite, Friedrichite, Gladite, Krupkaite, Paarite, Pekoite and Salzburgite.

44. Aikinite CuPbBiS3

46. Potosiite
Pb6Sn2FeSb2S14