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141-164
For complex rocks in which the structure of minerals, rather than their chemical composition, changes
with progressive evolution of the system, it makes sense to try and monitor such an evolving system
through the progressive change in the crystal structures of the constituent phases. In effect, the
paragenetic sequences of minerals in such complex environments should be related to the crystal
structures of the constituent minerals, in order to consider variations in structure topology, we need to
organize crystal structures into hierarchical schemes, using the hypothesis that structures may be
hierarchically ordered according to the polymerization of the coordination polyhedra with higher bond-
strengths. Structural units are organized according to the mode of polymerization: unconnected
polyhedra, clusters, chains, sheets and frameworks.
The bond-valence structure of (OH) and (H20) shows that on one side, (OH) and H20 are strong
Lewis bases; on the other side, they are weak Lewis acids. As a result, a very important role of both
(OH) and (H20) is to prevent polymerization of the structural unit in specific directions. Thus, the
dimensionatity of the structural unit is controlled primarily by the amount and role of hydrogen in the
structure. The way in which we have formulated these ideas also allows development of a predictive
framework within which specific aspects of the chemistry and structure of phosphates can be considered.
This approach to mineral structure, applied via the idea of a structural unit, can play a major role in
developing structural hierarchies in order to bring about some sort of order to the plethora of hydroxy-
hydrated-phosphate structures. Furthermore, by combining the idea of binary structural representation
with bond-valence theory, we see the eventual possibility of predicting stoichiometry and structural
characteristics of these minerals, particularly those in complex low-temperature hydrothermal
environments.
(b) I I
I
I
STABLEOVER WIDE RANGES OF
I
PRESSURE& TEMPERATURE
V !
BECAUSE I (ii) COMPLEX ENVIRONMENTS I
VVV I
STRUCTURE CAN GEOMETRICALLYADJUST
TO EXTENSIVETHERMAL EXPANSIONAND
ELASTIC COMPRESSION HIGHLY FRACTIONATEDPEGMATITES
I I
CHEMICAL SEDIMENTS FROM SALINES
BRINES (e,g. SABKAHS)
CAN ADJUST CHEMICAL COMPOSITIONTO
ACCOMMODATE MAJOR CHANGES IN BULK
ROCK CHEMISTRY WEATHERING ZONES OVER SULPHIDE
ORE-BODIES
I SOILS
SMALL NUMBERINOFRocKPHASES
(MINERALS) I I
I
I EASILYANALYSED BY REVERSIBLE I (i) LARGENUMBER OF COMPLEX MINERALS
THERMODYNAMICS I (ii) MANY DIFFERENTCHEMICAL TYPES OF MINERALS
(e.g. SILICATES, SULPHATES, ARSENATES)
(iii] DOMINATEDBY NON-EQUILIBRIUMPROCESSES
FIG. 1. (a) The behaviour of rock-forming minerals as a function of temperature, pressure and composition; (b) the
behaviour of non-rock-forming minerals as a function of temperature, pressure and composition.
but they often contain minerals of several The non-rock-forming, or exotic, minerals
different chemical types (e.g. phosphates, sili- occur as accessory minerals in common rocks,
cates, oxides, sulphates, sulphides and sulpho- or as constituents of what we can call complex
salts); such systems tend to resist the conventional environmetlts, represented by such rock-types as
approach to petrologic interpretation. highly fractionated pegmatites, sabkahs, weath-
In this regard, it is useful to contrast the ering zones over sulphide ore-bodies, etc. These
mineralogy of such environments with that are characterized by a large number of complex
observed in common rocks such as granites, minerals, and the presence of many different types
basalts, limestones or amphibolites. Common of minerals. Their formation is dominated by non-
rocks consist of a small number of rock-forming equilibrium precesses. These rocks consist of
minerals that adjust their chemistry and structural large numbers of minerals that adjust their
state in response to changing conditions. Thus we structure; i.e. break down to form new minerals,
can follow petrologic history (Fig. 2a) through in response to even small changes in ambient
changes in mineral chemistry as a function of conditions. Thus for complex rocks, in which
progressive crystallization. structure rather than chemistry changes with
142
PHOSPHATE STRUCTURES A N D CHEMISTRY
(a)
I coooo.,,oc.s I I I
I I
I I I I
V
THROUGH
V
THROUGH
VV VV
CHANGES IN MINERAL CHEMISTRY CHANGES IN CRYSTAL STRUCTURE
AS A FUNCTION OF PROGRESSIVE AS A FUNCTION OF PROGRESSIVE
CRYSTALLIZATION CRYSTALLIZATION
FIG. 2. (a) The role of rock-forming minerals in petrology; (b) the suggested role of non-rock-forming minerals in
petrology.
progressive evolution of the system, it makes approximately where H20 groups are stable as
sense to try and monitor such an evolving system ligands to the transition metals.
through the progressive change in crystal Pegmatite phosphates are usually confined to
structure (Fig. 2b). In effect, the paragenetic well-zoned and very coarse granitic pegmatites
sequences of minerals in such environments where the primary phosphate phases crystallized
should be related to the crystal structures of the toward, or in the core of, the pegmatite (Fig. 4),
constituent minerals. Phosphates generally occur as pods in the core.
Their complexity arises from the fact that, after
consolidation, the primary phosphates stew in
Pegmatitic phosphates
residual aqueous fluids. This results in a large
There are several hundred accredited phosphate number of oxidation and exchange reactions,
minerals, and their most common occurrence is in generating a series of phosphate minerals of
highly fraetionated granitic pegmatites. Thus [ increasing structural and chemical complexity
will concentrate primarily on this specific with decreasing temperature.
enviromnent. Fisher (1958) described the phos- Figure 5 shows a selection of minerals and
phates as "mineralogical step-children" and as "a reactions that can take place. With amblygonite-
pain in the neck"; however, he also arranged the montebrasite as the primary phosphate, there is
phosphates in a paragenetic sequence for pegma- no possibility of oxidation, and hence we just get
tites, and the scheme shown in Fig. 3 essentially cation and anion exchange with the fluid
encapsulates his findings. Fisher emphasized the (Moore, 1973). Removal of Li and addition of
correlation between position in the paragenetic other alkali and alkaline-earth cations produce
sequence and the amount of H20 in the mineral such a l u m i n o p h o s p h a t e s as l a c r o i x i t e
formula. [NaAI(PO4)F], morinite [NaCa2A12(PO4)2
Moore (1973) attached temperature estimates (F,OH)5(H20)2], bertossaite [(Li,Na)2CaAI4
to this diagram, varying from about 750~ for the (PO4)2(OH,F)4] and the ubiquitous apatite.
primary phosphates such as triphylite and With triphylite-lithiophilite as the primary
amblygonite, to about 100"C for mitridatite and phosphate, we now have the possibility of
vivianite. The broken line at 200~ indicates oxidation of both Fe and Mn, as well as the
143
F.C. HAWTHORNE
A f t e r D J F i s h e r & PB M o o r e
F[o. 3. Generalized paragenetic sequence of phosphate minerals in pegmatites (from Moore, 1973).
same cation- and anion-exchange reactions as with oxidation produces such minerals as
operative for amblygonite-montebrasite. Cation ferrisicklerite-sicklerite [Li(Fe3-,Mn~+)PO4],
exchange with little or no oxidation gives rise to heterosite-purpurite [(Fe 3 ,Mn3+)PO4] and the
some extremely complicated minerals such as minerals of the alluaudite group, which, in turn,
t r i p l o i d i t e - w o l f e i t e [(Mn2+,Fe 2 ,Mg,Ca)2 produce a plethora of structurally and chemically
(PO4)(F,OH)], griphite [Na4Ca(,(Mn,Fe2~,Mg)l~) complex phosphate minerals (Fig. 5). Thus we
Li2Ala(PO4)e4 (F,OH)8] and w h i t l o c k i t e have a rich hierarchy of secondary phosphates
[Ca9(Mg,Fe2+)(PO4)dPO3OH)] in the metaso- developed. It is the complexity of these
matic zone and a large family of hydrothermally parageneses that challenge our understanding
reworked phosphates (Fig. 5). Cation exchange of geochemical processes.
144
PHOSPHATE S T R U C T U R E S A N D CHEMISTRY
~ J,.~F1~-E]:]~
~ ~ ~ ~~~~' ~ - ~
:~-~x--- core - margin
(tourmaline, I:~ryl.-
spoaumene)
core (Q)
F~o. 4. The generalized structure of a zoned granitic pegmatite (from Cern~, 1982).
145
E C. HAWTHORNE
PB Moore
~ 2 0 % of the mean value. This mean value is tivity is a measure of electrophilic strength, and
characteristic of that particular cation (Fig. 6). its correlation with the characteristic bond-
Phosphorus, pS+, is always in tetrahedral coordi- valence indicates that the latter is a measure of
nation in minerals; the mean bond-valence is thus the Lewis-Acid strength of the cation. Thus we
equal to the Pauling bond-strength of 1.25 vu can define the Lewis-acid strength of a cation as
(valence units). For ferrous iron, Fe 2+, the the average bond-valence to that cation. We can
observed coordination numbers vary from [4] to define the Lewis-base strength of an anion in the
[8], with [4] and [5] more common than [7] or [8]; same way.
averaging over a large number of crystal These definitions of Lewis acid and base
structures gives the mean bond-valence 0.40 ru. strengths lead to a specific criterion for chemical
As mean bond-valence conelates with ionic bonding, the valence-matching principle: the
size and charge, it should vary systematically Lewis-acid strength of the cation must closely
throughout the periodic table, and this is indeed match the Lewis-base strength of the anion
the case. (Fig. 8). If they don't match, a structure is not
stable or does not form. This is essentially the
chemical analogue of the handshaking principle in
Lewis-ocid and lewis-base strengths
combinatorial mathematics.
Characteristic bond-valence also correlates well This definition of Lewis basicity is not very
with electronegativity (Fig. 7). Now electronega- useful for simple anions, as they show too great a
146
PHOSPHATE STRUCTURES A N D CHEMISTRY
VALENCE-MATCHINGPRINCIPLE
I CHARACTERISTIC BOND-VALENCES I
I LEWISBASICITYOF ~ - - ~ H q LEWISACIDITY OF I
STRUCTURALUNIT INTERSTITIALCATIONS
PHOSPHORUS: Always [4J-coordinated.
-'- bond-valence = 5/4 = 1.25 v.u. +- small amount
Great variability of 0 2- b a s e - s t r e n g t h
>,1-0-
>
:}
~0"5"
LU
/ 9
0"5 1"0 1-5 FIG. 9. The Lewis base strength for both simple [ 0 2 - ]
Lewis Acid Strength and complex [(PO4) 3 ] anions in apatite; the starred
circle is S, the dotted sphere is O, the dotted tetrahedron
FIG. 7. Electronegativity as a function of Lewis acid is the (PO4) 3 oxyanion, and the sad/happy faces are Na;
strength for simple cations (from Brown, 1992). the bond-valence values are shown in valence units.
147
F.C. HAWTHORNE
Ca is 0.27 vu; these match up, and apatite is a HIGHER BOND-VALENCE POLYHEDRA LINK
stable mineral.
The important point to make here is that this
+
analysis is a p r i o r i . Unlike Pauling's rules and the FBB: FUNDAMENTAL BUILDING BLOCK
Brown-Shannon bond-valence curves, we do not
need to have a stable arrangement formed before
we can examine it; with these ideas on Lewis
I
REPEATED/POLYMERIZED
acid/base strength, we have predictive power9
I
STRUCTURAL UNIT
Binary structural representation
Hawthorne (1983) has proposed that crystal r
structures may be h i e r a r c h i c a l l y ordered
USUALLY AN ANIONIC ARRAY
according to the polymerization of the coordina-
tion polyhedra with higher bond-strengths. We
can summarize the basis of this hierarchical LINKED BY INTERSTITIAL CATIONS
organization of structure in the following way
(Fig. 10): higher bond-valence polyhedra link to
r
form a strongly-bonded cluster of coordination CRYSTAL STRUCTURE ]
polyhedra that constitutes the fundamental
building block of the mineral. This cluster is
repeated, often polymerized, to form the structural FIG. l 0. Conceptual formation of a crystal structure; this
unit, a complex anionic array whose excess idea is the basis of organizing crystal structures
charge is balanced by the presence of large low- hierarchically according to the polymerization of
valence interstitial cations. coordination polyhedra of higher bond-strengths.
STRUCTURAL UNIT
: b- . P"
STRUCTURAL UNIT
I T M ~1
Fl(~. 11. The crystal structure of goedkenite portrayed to emphasize the binary representation as a structural unit and
interstitial cations; (PO4) tetrahedra are dotted, (Alqb6) octahedra are dashed, Sr is shown as unshaded circles.
148
PHOSPHATE STRUCTURES AND CHEMISTRY
FI~ 12. The structural units [M(TO4)2qb2]and [M(FO4)2~],and the phosphate, arsenate and vanadate minerals based
on these structural units; note the difference in interstitial-cation type between the two groups of minerals.
149
EC. HAWTHORNE
written as [M(TO4)2d~]. Phosphate, arsenate and structures are formed with these species as
vanadate minerals with this type of structural unit interstitial cations (Fig. 12). Thus it is the
are listed in Fig. 12; the interstitial cation is Pb 2+ matching of the acid and base strengths of the
or Sr in these minerals. For both structural units of interstitial cations and the structural unit that
Fig. 12, the electroneutrality principle requires accounts for such contrasting interstitial-cation
only that the interstitial cation(s) be a single chemistry in the minerals with different structural
divalent cation or two monovalent cations. units.
However, only divalent interstitial cations occur,
and there is complete chemical ordering: only Ca
Water of hydration in minerals
occurs with the [M(TO4)2d?2] structural unit and
only Pb 2+ or Sr occurs with the [M(TO4)2da] Next, let us look at the role of H20 in minerals,
structural unit. Both structural units show a wide and ask the question "Why are some minerals
range in chemistry, and these minerals are not hydrated whereas others are not, and what
restricted to any particular paragenesis, so why is controls the degree of hydration?"
there such an extreme ordering of the interstitial Figure 13 shows the bond-valence structure
cations? There must be another mechanism, in around an H20 group. A cation bonds to the
addition to the electroneutrality principle, control- O-anion with a particular bond-valence. The
ling this aspect of structural chemistry. We find remaining bond-valence requirements of the
the answer in the valence-matching principle. O-anion are satisfied by the associated H-atoms,
Consider first the structural unit [M(TO4)(D2 and the bond-valence requirements of the H-
such as occurs in the mineral collinsite, atoms are met by H-bonds with adjacent anions.
Ca2[Mg(PO4)2(H20)2]. There are eight O-anions Note that the valences of the H-bonds are exactly
and two H20 groups in the structural unit. For an half that of the M - O bond. The H20 group is
anion coordination number of [4] for O and three acting as a bond-valence transformer, causing one
for (H20) of the structural unit (Hawthorne, bond to be split into two weaker bonds.
1994), the anions of the structural unit require Consider the mineral metavauxite,
thirty-eight bonds to them from their coordinating Fe 2+ [Al(PO4)(OH)(H20)]2(H20)6 (Fig. 14); the
cations. The number of cation-oxygen bonds
implicit in the formula [Mg(PO4)2(H20):] is
twenty-two, six Mgd2 bonds, two times four (a)
P - O bonds and two times four H - O bonds.
The difference between the number of bonds
required (38) and the number of bonds implicit in MC) "
the coordination polyhedra of the
[Mg(PO4)2(H20)2] structural unit (22) must be
made up by bonds to the interstitial cations. This
difference is sixteen. As the structural unit has a
charge of 4 - and requires sixteen bonds to fulfil
its anion-coordination requirements, the Lewis
basicity of the structural unit is 4/16 0.25 vu. (b)
This matches closely with the Lewis acidity of Ca
at 0.27 vu; this satisfies the valence-matching
principle and stable structures will form.
Although Pb 2+, Sr and Na2 or K2 satisfy the
electroneutrality requirement, their Lewis acid- M9
ities (Pb 2+ = 0.20 vu, Sr = 0.20 vu, Na = 0.17 vu,
K - 0.13 vu) do not match the Lewis basicity of -O.oo......,
the [M2+(5+TO4)qb2] structural unit and stable ta Vl2 .....@
structures do not form.
Consider next the structural unit [M(TO4)2qb],
such as occurs in vauquelinite, Pb2[Cu(PO4) F~. 13. The bond-valence structure around (a) an anion
(CrO4)(OH)]. The Lewis basicity of the structural (X) bonded to a cation (with a bond valence v); (b) an
unit is 4/(3616) - 0.20 vu. This matches closely (H20) group consisting of an oxygen (X) and two H-
with the Lewis acidities of Pb 2§ and St, and stable atoms (small black circles).
150
PHOSPHATESTRUCTURESAND CHEMISTRY
151
F. C. H A W T H O R N E
TABLE 1. M T ~ n and MT2qbn minerals based on isolated Mqb6 octahedra and T~)4 tetrahedra
References: (1) Sudarsanan and Young (1969); (2) Abbona et al. (1984); (3) Catti et al. (1977); (4)
Ferraris and Franchini-AngeIa (1974)
152
PHOSPHATE STRUCTURES A N D CHEMISTRY
TABLE 2. M T ~ n and MT2OOn minerals based on isolated [M(T~4)d?n] and [(M(Td24)2(bn)m] dusters.
References: (1) Catti et al. (1979); (2) Khan and Baur (1972); Hawthorne (1979)
(a) (c)
(b)
~ ""C" ........
.....L ~ .... " .,, .:;:<..
F,,l~ a -----!~1
Fig. 15. Structural arrangements in selected phosphate minerals based on finite polyhedral clusters: (a) anapaite; (b)
schertelite; (c) morinite; phosphate tetrahedra are dot-shaded, octahedra are dash-shaded.
153
E C. HAWTHORNE
The structural unit of anapaite has a Lewis forming a stable mineral. The possibilities Na5
basicity of 0.28 vu; this matches the Lewis acidity and CaNa3 have charges of 5 but aggregate
of Ca, and hence anapaite has Ca as its interstitial Lewis acidities of 0.17 and 0.20 vu, respectively,
cation. The structural unit of schertelite is and hence cannot satisfy the valence-matching
somewhat more complicated than anapaite, and principle.
indicates how to treat OH. The bonds needed by
the anions of the structural unit are 6 x 4 (for O
Infinite-chain minerals
atoms) + 3 x 6 (for OH and H20 groups) = 42;
the bonds provided by the cations of the structural Selected minerals from this class are given in
unit a r e 4 x 2 ( P ) + 6 ( M g ) + 2 x 10(H)=34. Table 3, and the corresponding structural units are
The additional bonds needed = 42 - 34 = 8 and shown in Fig. 16. Childrenite and eosphorite are
the charge on the structural unit - 2 - ; the isostructural and have the [M(TO4)~3] chain
resulting Lewis basicity = 2/8 = 0.25 vu, which (Fig. 16a) as their structural unit. In this chain,
corresponds to the Lewis acidity of (NH4) , the M~6 octahedra link through trans vertices to form
interstitial cation in schertelite. Morinite is also an an [Mc~5] unit that is further linked by tetrahedra
instructive example as it demonstrates the in a staggered arrangement along the length of the
difference between F and OH, and shows how chain. The [M(TO4)2d~2] chain (Fig. 16b) is the
to deal with multiple interstitial cations. The basis of several families of phosphate, arsenate
bonds needed are 8 x 4 ( O a t o m s ) + 6 x 3 (F, and sulphate minerals, specifically cassidyite and
OH and H20) = 50, the bonds present are 2 x 6 c o l l i n s i t e ( m e m b e r s o f the t a l m e s s i t e ,
(AI) + 2 x 4 (P) + 5 x 2 (H) = 38, and the charge Ca2[Mg(AsO4)2(H20)2], group) and fairfieldite
on the structural unit is 5-; hence the Lewis and messelite (members of the fairfieldite group).
basicity - 5/(50 - 38) = 0.25 vu. So morinite Octahedra of this chain are linked indirectly
needs interstial cations with a total charge of 5 - though pairs of tetrahedra. Each octahedron thus
and an aggregate Lewis acidity of 0.25 vu. The has one pair of trans vertices that do not link to
observed interstitial cations CazNa have an tetrahedra; these vertices are (H20) groups. The
aggregate Lewis acidity of (0.27 x 2 + 0.17)/3 [M(TO4)2d?] chain (Fig. 16c) is the structural unit
= 0.24 vu, closely matching the Lewis basicity in tancoite and the minerals of the jahnsite and
and the charge of the structural unit, and hence segelerite groups (Table 3). Octahedra link
References: (1) Giuseppetti and Tadini (1984); (2) Hansen (1960); (3) White et al. (1967); (4) Brotherton
et al. (1974); (5) Fanfani et al. (1970); (6) Moore and Araki (1974b); (7) Moore and Ito (1978); (8)
Moore and Araki (1977a); Moore et al. (1975); (10) Nichols (1966); (11) Fanfani and Zanazzi (1968).
154
PHOSPHATE STRUCTURES AND CHEMISTRY
<
,:.._.~'-~
<
Fig. 16. Infinite-chain structural units of selected phosphate minerals; (a) [M(~14)(~3]; (b) [M(TO4)2(~2]; (c)
[M(TO4)2c~]; (d) [M(TO4)2d0];legend as in Fig. 15.
through trans vertices to form an [M4~5] chain These chains are found not only in phosphates but
which is then decorated by tetrahedra that link also in many other chemical groups of minerals
adjacent octahedra. This chain is somewhat (Hawthorne, 1985, 1990, 1992, 1994), and it is
similar to the [M(TO4)qb3] chain (Fig. 16a), but notable that they all have a fairly simple
is decorated by twice as many tetrahedra along its connectivity and there is just one type of chain
length. The [M(TO4)zd?] chain of Fig. 16d is the for each type of connectivity between octahedra.
structural unit in a wide variety of sulphate, Graphical enumeration shows that there are ~ 200
chromate, phosphate, arsenate, vanadate and distinct chains based on repeat units of
silicate minerals, including goedkinite, tsumebite [M(TO4)2d~n] and [M2(TO4)4~n]. Few of these
and vauquelinite (Table 3). Although this chain occur in minerals, and by far the most common
has the same stoichiometry as the chain depicted chains of this stoichiometry are those shown in
in Fig. 16c, it is topologically very different. Fig. 16. Although there is only one type of
Octahedra share trans edges to form an [Mqb4] [Jl4(TO4)d~n] chain in phosphates, the larger
chain that is decorated by pairs of tetrahedra families of phosphate-arsenate-vanadate and
arranged en echelon along its length. sulphate-chromate minerals show [M(TO4)d04],
Consider the chains of general stoichiometry [M(~O4)~f)3] and [M(TO4)qb2]chains with connec-
[M(TO4)z~n] (Fig. 16b,c,d). The first chain tivities analogous to those in the [M(TO4)2C~n]
(Fig. 16b) has no linkage between octahedra, the chains. Thus not only does Nature choose a small
second chain (Fig. 16c) has corner-linkage number of fundamental building blocks, she is
between octahedra, and the third chain also very economical in her ways of linking them
(Fig. 16d) has edge-linkage between octahedra. together to form structural units.
155
E C. HAWTHORNE
The structural unit of childrenite and eosphorite constituent of the structural unit, which would be
has a Lewis basicity of 0.29 vu, suggesting that it written as [Al(PO3.5{OH}o.5)2(OH)] with a Lewis
would prefer Ca (Lewis acidity = 0.28 vu) rather basicity of O. 19 vu. This matches exactly with the
than Mn 2§ or Fe 2+ (Lewis basicity ~ 0.33 vu) as Lewis acidity of the interstitial cations Na2Li (=
an interstitial cation. Cassidyite, collinsite, fair- {0.17 x 2 + 0.22}/3 = 0.19 vu). This close
fieldite and messelite have structural units with a correspondence to the valence-matching principle
Lewis basicity of 0.25 vu; the closest match is for the second case suggests that the apparently
with Ca, and Ca is the interstitial cation in all symmetrical H-bond in tancoite may actually be a
these minerals. Tancoite is extremely interesting time-averaged asymmetrical H-bond. The struc-
when examined in this way. There is a tural units of the jahnsite- and segelerite-group
'symmetrical' H-bond in tancoite (Hawthorne, minerals have a Lewis basicity of 0.21 vu,
1985) and this H atom is written as an interstitial whereas the aggregate H20-moderated Lewis
cation in Table 3. In this case, the structural unit is acidity of the interstitial cations is 0.24 vu; note
[AI(PO4)2(OH)] and has a Lewis basicity of 0.21 that additional interstitial (H20) would produce a
vu; taking the Lewis acidity of H as 0.50 vu, the better match between the structural unit and the
aggregate Lewis acidity of the interstitial cations interstitial cations, and the reason why there is not
is (0.17 x 2 +0.22 + 0 . 5 0 ) / 4 - 0.26 vu, n o t i n more interstitial (H20) is not clear. The structural
particularly close agreement with the valence- unit of goedkenite, tsumebite and vauquelinite has
matching principle. However, there is some a Lewis basicity of 0.21 vu, matching closely with
question as to whether a symmetrical H-bond is Sr and Pb as interstitial cations.
stable; it is often thought that a double-well
potential will give rise to H hopping rapidly Infinite-sheet minerals
between two asymmetric positions on either site
of the central symmetric position. If this is the Selected minerals from this class are given in
case at any instant, we should consider H as a Table 4, and the corresponding structural units are
References: (1) Sutor (1967); (2) Kampf (1977); (3) Moore (1965); (4) Baur (1969a);
(5) Hawthorne (1988); (6) Moore and Araki (1974a); (7) Baur (1969b); (8) Fanfani et al. (1978); (9) Baur and
Rama Rao (1967); (10) Moore et al. (1976); (11) Moore (1975b); (12) Kampf and Moore (1976); (13) Moore et
al. (1975); (14) Moore et al. (1974); Moore and Araki (1977b); (16) Moore (1974).
156
PHOSPHATESTRUCTURESAND CHEMISTRY
(a) (b)
I.~- a ----.~,.i
(d)
(f)
(e)
i;>
I
(g) (h)
(i)
<,.
<
Fig, 17. Infinite-sheet structural units of selected phosphate minerals: (a) [M(TO4)(~3]; [M2(TO4)2(~5]; (C)--00
[M(TO4)(~2]; (g) [M2(TO4)2(bT]; (h)[M(TO4)~]; (i) [A//(TO4)21~)2], legend as in Fig. 15.
shown in Fig. 17. Newberyite is based on the tetrahedra and octahedra of adjacent clusters to
[M(T~4)~)3] sheet (Fig. 17a) in which tetrahedra form a sheet. There are several sheets with the
and octahedra occupy the vertices of a 63 net and composition [M(TO4)qb2] (Fig. 17c-j), and these
link by sharing comers; each polyhedron shares are structural units for the minerals of the laueite-
three comers with adjacent polyhedra of different group minerals, pseudolaueite, stewartite and
coordination nulnber. Minyulite is based on the metavauxite (Table 4). These sheets are formed
[M2(]"O4)2d05 ] sheet of Fig. 17b, in which the by condensation of corner-sharing octahedral-
[M2(TO4)2q~7] clusters found in morinite tetrahedral chains of the type shown in Fig. 16a
(Fig. 15c) condense via corner-sharing between and c. The tetrahedra cross-link the chains to form
157
F. C. H A W T H O R N E
sheets, and there is much isomeric variation in good fit, but the significance of this is not clear as
this type of linkage (Moore, 1975a). These sheets yet. The structural unit of foggite (Lewis basicity
are linked to form crystals through insular 0.25 vu)matches well with its complex
divalent-metal octahedra, either by direct corner- interstitial cation Ca(H20) with a Lewis acidity
linking to phosphate tetrahedra plus H-bonding, of 0.26 vu. Whitmoreite (Lewis basicity = 0.14
or by H-bonding alone. Again, there is consider- vu) does not match well with its interstitial cations
able potential for stereoisomerism in the ligand (Lewis acidity = 0.20 vu) , and neither does
arrangement of these linking octahedra, but only mitridatite (Lewis basicity = 0.15 vu; Lewis
the trans-corner linkages occur. Whitmoreite is acidity = 0.24 vu). However, olmsteadite (Lewis
based on the [M2(TO4)2(J)7] sheet (Fig. 17g) in basicity = 0.28 vu; Lewis acidity - 0.27 vu) and
which octahedral edge-sharing [M2~0] dimers brianite (Lewis basicity - 0.22 vu; Lewis acidity =
share vertices to form a very open sheet of 0.21 vu) match closely, despite the complexity of
octahedra; these sheets are decorated with their interstitial cations (Table 5).
tetrahedra that occlude the vacancies in the
octahedral sheet. The sheet can also be considered
Infinite-framework minerals
as a condensation of the [M2(TO4)2d27] morinite
cluster (Fig. 15c) (Hawthorne, 1979). Tsumcorite Selected minerals from this class are given in
and bermanite are based on the [M(TO4)~b] sheet Table 5, and the corresponding structural units are
of Fig. 17h, in which chains of edge-sharing shown in Fig. 18. The [M(TO4)d)] framework of
octahedra are cross-linked into a sheet by Fig. 18a is the structural unit of the minerals of
tetrahedra that also bridge along the length of the amblygonite group, the phosphosiderite group,
the chain; note the similarity of the linkage in this the strengite group and the lacroixite group; in
sheet with that in the [M(/~4)2~ ] chain of Fig. addition, it occurs in a wide range of arsenates,
16d. Olmsteadite is based on the [M(TO4)2002] vanadates, sulphates and silicates. Corner-sharing
sheet (Fig. 17i) which consists of eight-membered [Md25] chains extend along the c-axis and are
rings of tetrahedra and octahedra that link to form cross-linked into a framework by sharing corners
a very open sheet. The prominent chains with (PO4) tetrahedra. The resulting interstices
discernable in this sheet do not occur in any may contain alkali and alkaline-earth cations
phosphate minerals, but are found as chain units (Table 5) and may also be vacant, depending on
in chalconthite, liroconite and brassite. the charge on the framework. Jagowerite (Table
The structural unit in newberyite is neutral and 5) is based on the framework of Fig. 18b. Pairs of
hence newberyite has no interstitial cations; the ( A I ~ ) octahedra share an edge to form an
structure is held together by direct H-bonding [M2dplo] cluster, and these dimers share corners
between the sheets. Minyulite has a structural unit with (PO4) tetrahedra in a way that resembles a
with a Lewis basicity of 0.09 vu; of the common fragment of the [M(TO4)2O2] chain in Fig. 16b.
alkali and alkaline-earth cations, only K has a Melonjosephite is based on the framework of Fig.
Lewis acidity close to this value (0.13 vu), and K 18c. Octahedra share edges to form [Md24] chains
is the interstitial cation. The minerals of the extending along the c-direction, and the chains are
laueite group, together with stewartite, pseudo- decorated by (PO4) tetrahedra linking vertices of
laueite and metavauxite, all have structural units adjacent octahedra of the chain; this is the
with a Lewis basicity of 0.17 vu. The interstitial [M(TO4)qb] chain of Fig. 16d. Corner-linking
cations in these minerals are the small divalent chains of alternating octahedra and tetrahedra
cations Mg, Fe 2+ and Mn 2+, moderated by their also extend along c, and the two types of chains
coordination by six (H20) groups: 2/(6 x 2) - link by sharing corners and edges to form a
O. 17 vu, an ideal match with the Lewis basicity of framework. Palermoite and bertossaite are based
the structural unit. Strunzite and ferrostrunzite on the framework of Fig. 18d. Pairs of (Al~6)
also have this stoichiometry of structural unit, but octahedra share edges to form [Al2qbl0] dimers
the complex interstitial cation is Mn2+(H20)4 with that then link by sharing vertices to form chains
a Lewis acidity of 2/(6 + 4) = 0.20 vu, still a that extend along the c-direction; these chains are
reasonable match with the Lewis basicity of the linked into a framework by sharing corners with
structural unit. Bermanite has a structural unit (PO4) tetrahedra. Alluaudite is based on the
with a Lewis basicity of 0.14 vu; the interstitial framework of Fig. 18e. Thick sheets of edge-
cation is Mn z+ as moderated by (H20)4 to give a sharing octahedra decorated with tetrahedra
Lewis acidity of 0.20 vu. This is not a particularly extend orthogonal to [010], and are linked by
158
PHOSPHATE STRUCTURES AND CHEMISTRY
References: (1) Kniep and Mootz (1973); (2) Moore (1966); (3) Kniep et al. (1977); (4) Simonov and Belov (1958);
(5) Barn" (1959); (6) Groat et al. (1990); (7) Pajunen and Lahti (1985); (8) Meagher et al. (1974); (9) Kampf and
Moore (1977); (10) Moore and Araki (1975); (11) Moore (1972); (12) Moore (1971); (13) Lindberg and Christ
(1959)
comer-sharing between octahedra and between melonjosephite, bertossaite and palermoite do not
octahedra and tetrahedra. The minerals of the match particularly well. The structural unit in
lazulite group are based on the framework of leucophosphite has a Lewis basicity of 0.09 vu,
Fig. 18f Triplets of octahedra share faces to form and the interstitial K has the lowest Lewis acidity
a strongly bonded trimer (shown shaded black in (0.13 vu) of the common monovalent cations. The
Fig. 18J). These trimers link via corner-sharing alluaudite minerals have a Lewis basicity of 0.06
with (PO4) tetrahedra and by comer-sharing vu, a poor match for interstitial Na (0.17 vu) and
between octahedra. Ca (0.28 vu).
Several groups of structures (e.g. strengite and This lack of agreement with the valence-
metavariscite) have neutral structural units, and matching rule is rather interesting, as it is much
hence no interstitial cations, although they all more prevalent for the framework phosphates
have H20 groups as part of the structural unit. The than for the sheet, chain, etc. phosphates. The
structural units seem to be dominated by the higher the dimensional linkage in the structural
stoichiometry [M(T04)d'.)]. The Lewis basicity for unit, the less compliance the arrangement has to
this stoichiometry is 0.14 vu for M 3+ and ~ = OH, adjust coordination number of the interstitial
0.13 vu f o r m 3+ and # = F, 0.28 vu f o r m 2+ and 0 cation via structural movement or the incorpora-
= OH, and 0.25 vu for M 2+ and cb = F. tion of interstitial H20. At high temperature, such
Amblygonite-montebrasite do not match very problems may be compensated by large thermal
well: Li (= 0.22 vu) va 0.14 vu. However, d i s p l a c e m e n t s . At low t e m p e r a t u r e , this
natromontebrasite, lacroixite, isokite and panas- mechanism will become less effective and the
queraite match quite well. Similarly, jagowerite, structure will tend to be destabilized. Collectively,
t59
F.C . HAWTHORNE
>-
>:,
S
G
._=
r
o
..Q
V
,.-- '~.~--...o - - - ~
v ~
0
,b
v V
160
PHOSPHATE STRUCTURES A N D CHEMISTRY
these issues suggest that framework structures The effect of this on a structural unit is easily
should be replaced by sheet structures, chain apparent. On the Lewis-base side of each group,
structures, etc. with decreasing temperature, as the strong cation-oxygen bond forms part of the
actually is observed in complex pegmatites. A structural unit. On the Lewis-acid side of each
much more extensive examination of these group, the H-bond is too weak to form part of the
aspects of valence matching in complex pegmao structural unit. So we see that both of these groups
titic phosphates seems worthwhile. can attach themselves to a higher-valence cation
and inhibit further polymerization in the structural
unit. Thus a very important role of both (OH) and
Hydrogen as the agent of structural diversity
(H20) is to prevent polymerization of the
Let us examine the bond-valence structure of the structural unit in specific directions. Hence these
(OH) and (H20) groups for the ideal donor and groups essentially control the type of polymeriza-
acceptor bond-valences of 0.8 and 0.2 v u , tion of the structural unit.
respectively (Fig. 19). For the (OH) group, the Figure 20 shows the structure of newberyite,
central oxygen receives 0.8 v u from the H, and [Mg(PO3OH)(H20)3. The structural unit is a sheet
hence must receive 1.2 v u from the cations to of coruer-sharing (Mg~6) octahedra and (PO4)
which it is bonded. The H receives 0.8 v u from the tetrahedra, with the polyhedra arranged at the
donor oxygen, and must form a H-bond of vertices of a 63 net. In the (PO4) tetrahedra, three
strength 0.2 v u . Note the very polar nature of of the ligands link to (Mg~6) octahedra within the
the (OH) group. On the oxygen side of the group, sheet. The other ligand is 'tied off' orthogonal to
it accepts ~ 1.2 v u from cations, and functions as the sheet by the fact that the O atom is strongly
an anion. On the H side of the group, it donates bonded to a H-atom (i.e. it is an OH group) which
0.2 v u to an anion, and functions as a cation. then weakly H-bonds to the neighbouring sheet in
Putting this into bond-valence phraseology, on the Y-direction. In the (Mg~6) octahedra, three of
one side, the (OH) group is a strong Lewis base; the ligands link to ( P O 4 ) tetrahedra within the
on the other side, it is a weak Lewis acid. We see sheets. The other ligands are 'tied off' by the fact
the same type of behaviour for the (1-I20) group. that they are (H20) groups; the two H-atoms
On the oxygen side, it is a Lewis base, and on the
H side it is a weaker Lewis acid.
NEWBERYITE: Mg(POsOH)(H20)3
OH jW,,,p Mg
Weak Lewis acid
i ..o, OoO
0.2
!0.2
i
O.21i
C
>
OH H20 >
Strong Lewis base ~----- a ----~
Fig. 19. The bond valence structure around (OH) and
(H20), with bond valences shown in valence units; large Fig. 20. The structure of newberyite, showing the (OH)
unshaded circles: O; small shaded circles: H. and (H20) groups as shaded circles; legend as in Fig. 15.
161
E C. HAWTHORNE
weakly H-bond to the neighbouring sheets in the collinsite is controlled by the number and
Y-direction. Thus the sheet-like nature of the distribution of H-atoms in the structure.
structural unit in newberyite is controlled by the We may summarize the role of H in the
number and distribution of H-atoms in the structural unit as follows: the dimensionaIity of
structure. the structural unit is' controlled primarily by the
Figure 21 shows the structure of collinsite, amount and speciation of H in the structure.
Ca2[Mg(PO4)2(H20)2]. The structural unit is a
chain of comer-sharing (Mg~6) octahedra and
(PO4) tetrahedra. In the (Mg~6) octahedra, four of Conclusion
the ligands link to (PO4)tetrahedra. The othe~ two This approach to mineral structure, applied via the
ligands of the (Mgqb6) octahedra are 'tied off' by idea of a structural unit, can play a major role in
the fact that the O atoms are each strongly bonded developing structural hierarchies in order to bring
to two H-atoms (i.e. they are H20 groups) which about some sort of order to the plethora of
weakly bond to the adjacent chains. The (H20) hydroxy-hydrated-phosphate structures.
groups and their associated H-bonds force the Furthermore, by combining the idea of binary
chains to be separated, hence making room in the structural representation with bond-valence
structure for interstitial Ca atoms. In the (PO4) theory, I think we see the eventual possibility of
groups, two of the ligands link to (Mgcb6) rationalizing and even predicting stoichiometry
octahedra. The remaining two ligands are far and structural characteristics of these minerals,
from adjacent chains by virtue of the neigh- particularly those in complex low-temperature
bouring (H20) groups, and hence cannot link to hydrothermal environments.
other (Mg~6) octahedra; instead, they link to
interstitial Ca atoms and act as H-bond acceptors.
Acknowledgements
Thus the chain-like nature of the structural unit in
I thank Mark Welch for his comments on this
manuscript. This work was supported in entirety
by an Operating Grant of the Natural Sciences and
Engineering Research Council of Canada.
-F "'"'" ";
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162
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164