Allotropes and Polymorphs
B. D. Sharma
Los Angeles Pierce College, Woodland Hills, CA 91371
and
California State University Los Angeles, Los Angeles, CA 90032
The term “allotropes” is used differently by different au-
thors (1-7, 9, 13) and by the same author to have different
meanings (4, 7, 8, 10, 12, 14, 15). Furthermore, the terms
“allotropes” and “polymorphs” seem to have taken on the
same meaning (1, 4, 5,11,15).
The term “allotropy” was introduced by J. J. Berzelius
(16) in 1841 to distinguish the differences of different forms
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of carbon, sulfur, and silicon known to Berzelius from the
differences in compounds covered under the term “isomer-
ism”. Furthermore, Berzelius (16) believed that isomerism
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of compounds was not only due to the different positions of
atoms but also could be due to the existence of allotropic
forms of an element in isomeric compounds. For example,
according to Berzelius (16) crystalline FeS2 existed as two
isomers, one “pyrites” and the other “marcasite”, in which
sulfur was in different allotropic forms.
Our concept of “allotropes”, though confusing (1-15), is
not that of Berzelius. In the 1980’s the term “allotropes” is
defined, among others, “as the different forms of the same
element in the same physical state”. This implies that liquid
oxygen is not an allotrope of gaseous ozone. Some authors
simply give examples of allotropes and do not define the
term. Crystalline rhombic sulfur is an allotrope of crystalline
monoclinic sulfur, and gaseous oxygen is an allotrope of
gaseous ozone. In the first case it is the same discrete molec-
ular unit in two different crystalline forms that are allo-
tropes, and in the second case it is the distinctly different
discrete molecular units that are allotropes.
E. Mitscherlich (17) in 1822-1823 introduced the term
“dimorphs” to describe two different crystal forms of the
same substance, in particular the rhombic and monoclinic
crystalline forms of sulfur. The term “polymorphs” in chem-
istry is an extension of the term “dimorphs”. The term
“polymorphs” is also misused in that distinctly different
compounds have been called polymorphs. The term “poly-
morphs” has in fact become all-encompassing through its
application to different crystalline forms of an element or a
compound with different atomic arrangements. This fails to
take into account the different discrete molecular units and
different chemical bonding.
At times polymeric compounds have been discussed un-
der the term “allotropy” as in the case of metaldehyde, and
paraldehyde in relation with acetaldehyde. The varied inter-
pretations of the terms “allotropy”, “polymorphy”, “allo-
tropes”, “polymorphs”, “allotropism”, and “polymorphism”
over the years since 1822 and 1841 will be presented in a
historical review.
It is obvious that the term “allotropes” came to be used
long before the advent of structure determination by diffrac-
tion and spectroscopic methods. Today we are able to study
in detail the internal structure of matter, which sheds light
upon the differences not only of crystal forms but also of
differences of constitution of units making up the same
matter. Furthermore, the same matter can exist in different
states and have different units. It is of paramount impor-
tance to take note of our understanding of the participation
in different types of chemical bonding by the atoms of the
same element in different matter and the same matter.
In order that these facts be taken into consideration the
404 Journal of Chemical Education
terms “allotropes” and “polymorphs” need to be redefined.
We suggest the following.
the different forms of the same element in
Allotropes means
which the chemical bonding between atoms of the same element is
different and may have different discrete molecular units, irre-
spective of the state.
Polymorphs means the different crystal forms, belonging to the
same or different crystal systems, in which the identical units of
the same element or the identical units of the same compound, or
the identical ionic formulas or identical repeating units are
packed differently.
For the definitions of the crystal systems see refs 18 and 19.
It is understood that different conformations of the same
units of an element do not qualify as allotropes. These can be
described as conformational isomers. The crystals of confor-
mational isomers though can be defined as polymorphs. For
compounds in solid state with no discrete molecular units
but with the same elemental composition, if the two crystal
forms (even if the crystals belong to the same crystal system)
show different chemical bonding, then these are distinctly
different compounds. Different hydrates of a specific com-
pound are distinct from each other and their crystals are not
polymorphs.
Thermodynamic equilibrium involving allotropes is ac-
companied by breaking and remaking of different chemical
bonds, irrespective of states involved. For polymorphs there
is necessarily heterogeneous phase equilibrium accompa-
nied by packing rearrangement only.
In an attempt to reinforce the concepts of the above defi-
nitions, we present specific examples. Table 1 presents some
examples of allotropes, and Table 2 gives a few examples of
polymorphs. The naming of chemical substances in Tables 1
and 2 follows the recommendations of IUPAC (20) and, in
addition, other well-known names are provided.
Some Remarks about the Tables
All substances in Table 1 are elements, regardless of state.
In Table 2 we have both elements and compounds in solid
state. Trig means trigonal crystal system which is the same
as rhombohedral crystal system. See Sharma (18) and Scho-
maker and Lingafelter (19) for definitions and names of
crystal systems.
It is noteworthy that in Table 1 one can substitute dia-
mond (hex) for diamond (cub) or substitute graphite (trig)
for graphite (hex) but cannot substitute graphite (trig) for
diamond (cub) and cannot substitute diamond (hex) for
graphite (hex) to keep the meaning of allotropes in accord
with the definition given above. The substitution of either
graphite for either diamond in Table 2 is not in accord with
the above stated definition of polymorphs. Either graphite is
an allotrope of either diamond. In Table 2 the two diamonds
are polymorphs as are the two graphites. Gaseous C2 is an
allotrope of either diamond and either graphite. Gaseous C2
cannot be a polymorph. Similar arguments apply to other
elements listed in Table 1 and Table 2.
In Table 1 the list of allotropes of sulfur is not exhaustive.
Some other allotropes (regardless of state) are S3, S4, S5, S7,
S9, S10, Sis, and S*. Note that these are not just polymers of S
 Table 1. Some Examples of Allotropes

Element Molecular
Allotrope Name Unit State Crystal System Pertinent Distances Pertinent Angles References

Carbon
diamond (cub) —
solid cubic (fee) C—C = 154.450 pm CCC =
109° 28' 5
graphite (hex) —
solid hexagonal C—C = 142.10 pm CCC =
120° 5
dicarbon C2 gas —
C—C = 124.22 pm —
35-37
'2g spectroscopic
state
Tin
tin (cub) —
solid cubic (fee) Sn—Sn =
281.0 pm SnSnSn = 109° 28' 24, 5
gray tin, rv-tin (below 18 °C)
nonmetallic tin
tin (tetr) —
solid tetragonal (4) Sn—Sn
=
302.2 pm SnSnSn range 94°-149° 25, 5
white tin, (8-tin (18 “C-212 °C) (2)Sn—Sn =
318.2 pm
metallic tin

Phosphorus
tetraphosphorus p4 solid cubic (-77 °C—1-44.1 °C) P—P =
221 pm PPP =
60° 1, 5
liquid —
P—P =
225 pm PPP =
60° 1, 38
gas —
P—P = 221 pm PPP =
60° 1, 39
diphosphorus Pa gas —
P—P =
189.5 pm —

1, 37
red phosphorus —

amorphous — — —

1, 5
solid
black phosphorus P„ solid orthorhombic (2) P—P =
222.4 pm (2) PPP
=
102.1° 1, 5
(1)P—P =
224.4 pm (1) PPP =
96.3°
Hittorf's phosphorus P8 cage solid monoclinic P—P range PPP range 87°-111° 1, 5
Pg cage 220.3-227.8 pm
rhombohedral —
solid rhombohedral P—P within layer PPP average 105° 1, 5
phosphorus (trigonal) 213 pm, interlayer
327 pm
metallic phosphorus —
solid cubic (6) P—P = 237.7 pm PPP =
90° 5

Oxygen
dioxygen 02 solid monoclinic O—O = 115 ± 12 pm — 5
gas —
O—O = 120.74 pm —
37
O—O = 121.07 pm 40
32“ spectroscopic
state
trioxygen o3 gas —
O—O =
127.8 pm OOO =
116,8° 41

Sulfur
disulfur s2 gas —
S—S =
189 pm —
1. 37, 42
cyclo-octasulfur S3 solid orthorhombic S—S =
206.0 pm SSS = 108.0° 1, 5, 26, 43
dihedral = 98.3°
gas —
S—S =
206.0 pm SSS = 108.0° 1, 44
dihedral = 98.3°
cyclohexasulfur S6 solid rhombohedral S—S =
205.7 pm SSS = 102.2° 1. 5, 26
(trigonal) dihedral = 74.5°
gas — —
45
cyclododecasulfur Sl2 solid orthorhombic S—S =
205.3 pm SSS = 106.5° 1, 5, 46
dihedral = 86°
Helium
liquid He-4 (I) —
liquid — — —

28, 29
liquid He-4 (II) —

liquid — — —

28, 29

since the bonding is different in each of the allotropes.
Rhombic and monoclinic crystalline sulfurs are polymorphs
and not allotropes.
Liquid helium-4(I) and liquid helium-4(II) are listed in
Table 1 in view of the different number of closest neighbors,
on the average, of the central helium atom as revealed by
radial distribution functions based on X-ray and neutron
diffraction data.
Spectroscopic Eigenstates as Opposed to Allotropes
Oxygen (O2) can exist in two different spectroscopic eigen-
states (27), namely triplet and singlet, with parallel and
tion are just spectroscopic eigenstates and are not listed in
either Table 1 as allotropes or in Table 2 as polymorphs.
Cubic Close Packing and Hexagonal Close Packing of
Metals
It was pointed out that diamond (cub) is a polymorph of
diamond (hex). This points up the subject of crystallization
of the same metal in cubic close packing and hexagonal close
packing. Cubic close packing, ccp, results in a face-centered
cubic, fee, unit cell. Hexagonal close packing, hep, results in
a hexagonal unit cell. If the axial lengths of the two unit cells
are related as follows,

antiparallel spins of the two unpaired electrons, respective- afcc

=
hex
ly. These are not allotropes. Similarly orthohydrogen (Hj) and
and parahydrogen (H2), with parallel nuclear spins and anti-
parallel nuclear spins, respectively, in any state of aggrega- chei/ahex
= ~
1-633

Volume 64 Number 5 May 1987 405

 Table 2. Some Examples of Polymorphs (State is Necessarily Solid)

Molecular
Pure Substance Unit Crystal
Polymorph Name (Formula) System Pertinent Distances Pertinent Angles References

carbon
diamond (cub) —
cubic (fee) C—C = 154.450 pm CCC = 109° 28' 5
diamond (hex) —

hexagonal (hep) C—C = 154.450 pm CCC = 109° 28' 5, 21-23

carbon
graphite (hex) —

hexagonal C—C = 142.10 pm CCC =

120° 5
graphite (trig) rhombohedral C—C = 142.10 pm CCC = 120° 5
(trigonal)
phosphorus
phosphorus (cub) P4 cubic P—P =
221 pm PPP =
60° 5
/3-white phosphorus (-77-+44.1
0-yellow phosphorus °C)
phosphorus(hex) P4 hexagonal P—P =
221 pm PPP =
60° 5
rv-white phosphorus (below -77 °C)
(¥-yellow phosphorus
oxygen
dioxygen (mon) o2 monocl/nic 0—0 = 115 ± 12 pm —
5, 47
a-oxygen
dioxygen (trig) o2 rhombohedral O—0 =
assumed
120.74 pm —

5. 48
(3-oxygen (trigonal)
dioxygen (cub) o2 cubic — —

5, 49
7-oxygen
sulfur
cyclo-octasulfur Ss orthorhombic s—S = 206.0 pm SSS = 108.0° 1, 5, 26, 43
(rhombic sulfur) dihedral = 98.3°
cyclo-octasulfur Ss monoclinic S—S = 206.0 pm SSS = 108.0° 1, 5, 26,50
(/3-monoclinic sulfur) dihedral = 98.3°
cyclo-octasutfur s8 monoclinic S—S =
206 pm SSS = 107.6° 1, 5, 26. 51
(7-monoclinic sulfur) dihedral = 99.3°
silica
quartz (hex) Si02 hexagonal Si—-O =161 pm OSiO = 109° 28' 1. 52
Q3-quartz) SiOSi = 144°
cristobalite SiOj cubic Si—O = 161 pm OSiO = 109° 28' 1, 53
SiOSi = 144°
calcium carbonate
calcite CaCOs rhombohedral C—O = 128.3 pm —

1, 54, 55
(calcium carbonate trig) (trigonal) coord, no. of Ca2+ = 6
aragonite CaC03 orthorhombic C—O = 128.3 pm 1. 56-58
(calcium carbonate orth) coord, no. 0! Ca2+ = 9
zinc sulfide
zinc sulfide (cub) ZnS cubic each Zn bonded to 4 S SZrtS = 109° 28' 30
zinc-blende and each S bonded to ZnSZn = 109° 28'
sphalerite 4 Zn; Zn—S = 235 pm
zinc sulfide (hex) ZnS hexagonal each Zn bonded to 4 S SZnS = 109° 28' 30
wurtzife and each S bonded to ZnSZn = 109° 28'
4 Zn; Zn—$ = 235 pm
boron nitride3
boron nitride (cub) BN cubic each B bonded to 4 N BNB = 109° 28' 32-34
(zinc-blende type) and each N bonded to 4 B; NBN = 109° 28'
B—N = 156.5 pm
boron nitride (hex) BN hexagonal each B bonded to 4 N BNB = 109° 28' 32-34
(wurtzite type) and each N bonded to 4 B; NBN =
109° 28'
B—N = 156.5 pm

a
Another crystalline form of BN, called the layer hexagonal BN, is known (31). This is not the same as boron nitride tabulated above. The bonding of B to N in this layer hexagonal BN is
completely different from that in either of BN listed above. Each B is bonded to three N, and each N is bonded to three B. B—N = 144.6 pm; NBN angle is 120° and so is the angle BNB. This is
a distinctly different compound from the two BN’s listed above.

then the two structures are polymorphs. Any other relation-
ship of axial lengths allows one to define these structures as
allotropes.
Primitive cubic, body-centered cubic, and face-centered
cubic structures of the same metal are allotropes. In this
triad, fee structure may be replaced by hep structure. If the
axial length of ccp or fee structure is not related to the hep
structure as stated above, then hep structure is a fourth
allotrope even if Chex/atwx = 1-633.
Some General Remarks
The two crystal forms of FeS2, “pyrite”, and “marcasite”,
though not included in Table 2, are polymorphs and not
isomers.
There are innumerable solid organic compounds that
could be listed as examples of polymorphs in Table 2. We
point out just one unusual example of an interesting com-
pound namely, glycylglycine (H^N-CI^-ClOl-NH-CHj-
COJ), which crystallizes, from the same solution (n-propy!

406 Journal of Chemical Education

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