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Crystal Systems and General Chemistry

B. D. Sharma
California State University, Los Angeles, Los Angeles, CA 90032 and Los Angeles Pierce College, Woodland Hills, CA 91371

Crystal chemistry is a subject of great importance (1,2)and,


with good reasons. some asvects of this tooic are included in
chemistry. The
of thi; subject invariably
includes either a table or eraohics of c m t a l svswms alone with
axial length and interaxial angle relatfouships. In the a&ence
of svmmetrv considerations. the relationshiv of axial leneths
a n d interaxial angles for each crystal system can he ;isleading.
We present the definitions of each crystal system from the
point of minimum symmetry inherent in each crystal system
relating the packing of the chemical motif in the three-dimensional array and the consequence of the same toward the
interaxial angles and axial length ratios. For detailed and
precise discussion from a crystallographic point of view the
reader is referred to texts on crystallography and physical
chemistry ( 3 , 4 , 5 ) .

Tricllnlc System
The symmetry of a triclinic system is either just onefold
rotation axis or just center of symmetw. These svmmetrv
elements place no restrictionson~either<heinteraxial angles
or axial lengths. 'l'hus, the unit cell for a triclinic system can
have any value of interaxial angles and any ratio of axial
lengths, as long as a parallelepiped is defined. This, obviously,
includes a unit cell with a = b = c and a = 0= y = 90,which
defines a cube. Just because we have defined a cube does not
mean that we have a cubic system. In general, though, the unit
cell of real crystals belonging to triclinic system is such that
there is no specific relationship between axial lengths and
between interaxial angles, a consequence of the nature of the
chemical motif packed in the three-dimensional array exhibiting either just onefold rotation axis or just center of
symmetry.
Monocllnlc Svstem
This system requires either just one mirror plane or just
a single twofold rotation axis. Either of these svmmetrv ronditions demand one axis normal to the otheitwo, thus restricting two interaxial angles to a value of exactly 90.
However, there is no restriction as to the ratio of axial lengths.
Once again a unit cell with a = b = c and a = 0= y = 90 is
fully compatible with a monoclinic system.
Orlhorhombic System
Any packing of a chemical motif in a three-dimensional
array that exhibits just three mutually perpendicular twofold
rotation axes as a minimum symmetry belongs to the orthorhombic system. By the very befinitidn of th6 orthorhomhic
systrm it is clear that the three interaxial angles of the unit
parallelepiped must he exactly 90,hut there is no restriction
upon the axial length ratios. Therefore, aunit cell with a = b
= c and a = 0= y = 90" is an acceptable example of an orthorhombic system as long as the symmetry of the packing

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Journal of Chemical Education

conforms to the minimum of three mutually perpendicular


twofold rotation axes.
Tetragonal Syslem
This system requires the presence of a single fourfold
rotation axis as a minimum symmetry. Under this condition
all three interaxial angles are 90" and the two axes in the plane
perpendicular to the fourfold axis equal in length, hut the axis
coinciding with the fourfold axis can have any length. This
does not exclude the unit cell with a = b = c and a = B = y =
90" from the tetragonal system.
Rhombohedral System
Four body diagonals of the parallelepiped exhihiting
threefold rotation axis characteristics define a rhombohedral
system. No other symmetry is necessary. The intersection of
the body-diagonals may he a t any angle. This results in the
interaxial angles to he equal to each other and the axial lengths
to be equal to each other. Thus, the rhombohedra1 system
demands a unit cell with a = b = c and a = 0= y.
Hexagonal System
The three-dimensional array of chemical motif exhibiting
just single sixfold rotation axis results in a hexagonal system.
The angle between axes perpendicular to sixfold rotation axis
is necessarily 120, and these two axes are equal in length.
However, the axis exhibiting sixfold rotation axis character
can be of any length. Note that a unit cell with a = b = c and
y = 120' and a = = 90 is also compatible with triclinic or
monoclinic systems, if symmetry criteria are not used.
A Correct Relatfonshlp of lnteraxlal Angles and Axial Length

Ratlos for Seven Crystal Systems


unit Cell

Crystal
System

Interaxial Angles*

a:b:y
Triclinic

Monoclinic

NOResbictions, other than the


requirement of forming a
Parallelepiped
a = y = 90'; Pany value less
than 180' and greater
than'0

Onhorhombic
Tetragonal

a = b = y = 90'
a=b=r=goa

Rhombohedra1
Hexagonal

a = 8=y
y=120:a=8=900

Cubic

a=b=r=goO

Axial
Lenglhs
a:b:c
No Restrictions

No Restrictions

NOResnictions
a = b:
c any value
a=b=c
a= b
cany value
a=b=c

f ~ n g l ea is oppohne a: angle 6 is appmile b: angle y is oppooite c: For monociinic


System b axis is the symmetry axis: For tetragonal and hexagonal oystem c axis is me
symmetry axis.

Cubic System
The minimum symmetry requirements are four body diagonals of the parallelepiped intersecting each other at angles
of 70' 32' and 109' 28' and have the characteristics of threefold rotation. These automaticallv lead to three mutually
perpendicular rwufold rotation axes which in turn intersect
the threefold rutution axes a t an nnrlc uiSJ0 44'. This leads
to a unit cell with a = b = e and a =-p = r = 90. It is worth
emphasizing that a unit cell defining a cube does not necessarily belong to the cubic system even though a crystal belonging to the cubic system has a unit cell that is a cube, which
may or may not have fourfold rotation axes as a part of the
symmetry required for a cubic system.
Therefore, we wish to emphasize that axial ratios and interaxial angles of unit cells for crystal systems are the conse-

quence of symmetry inherent in the crystal that relates the


chemical motif in a three-dimensional array, along with the
nature of the chemical motif.
In the tnhle on the previous page we presmt il ct~rrrctreIationshiu of interaxial angles and axial leneth ratios fur the
seven cr&al systems, an&e keep in mindihe symmetry of
each crystal system.
Literature Cited
(1) Psuling, I. .. "The Nature of the Chemical Bond." 3rd Ed.. Comell University Press,
Ithses, 1960.
(21 Gmy. H. B., "Chemical Bonds." W.A. Benjamin lnc, 1973, pp. 181-222.
(31 '"International Tables for X-rsr Cwtsllograph~: Kymoch P r e , Binngham, England,

19R9,ValI.

(41 Glurker, J. P. and T~eblmd.K. N..''Crystal Stmctm Anal*


k Primer" Oxfad
Univenity Preas,N.Y., 1912.
(51 Mwre. W. J., "Physid Chemistry,' 4th Ed.. hontice-Hall lnc., Englewuod CIiW, New
Jersey. 1972. pp. &?3-837.

Volume 59 Number 9 September 1982

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