391

The crystal structure of the monoclinic pyroxenes.

By
B. E. Warren and J. Biscoe,
Massachusetts Institute of Technology, Cambridge, Mass.
(With 1 figure and 1 plate.)

I. Introduction.
The monoclinic pyroxenes form an important and well defined
group of meta-silicates with very characteristic chemical composition
and prismatic character. The more important members of this group
are listed below, together with the ideal chemical composition1).

Table I.
R e p r e s e n t a t i v e monoclinic pyroxeneç.
Diopside CaMg(Si03)2
Hedenbergite CaFe(Si03)2
Augite (Ca, Na) (Mg, Fe, Al) (Si, Al)20„
Clino-enstatite . . . . MgSi03
Acmite NaFe(Si03)2
Jadeite NaAl(Si03)2
Spodumene LiAl(Si03)2
Wollastonite CaSi03
Pectolite HNaCa2(Si03)3

Of these nine substances, diopside is the only one for which a complete
X-ray structure analysis has been made 2 ). In the present paper it is
intended to make a qualitative survey of the entire group, with a view
to determining to what extent the diopside structure can be considered
as the typical structure of the monoclinic pyroxenes 3 ).

1 ) The classification is that given in standard works such as D a η a's Textbook

of Mineralogy.
2) The structure of diopside CaMg (Si03)2. B. W a r r e n and W. L a w r e n c e
B r a g g , Z. Krist. 69, 168. 1928.
3) In an early work by W y c k o f f , Merwin and W a s h i n g t o n , a comparison
was made of powder photographs of a number of pyroxenes. With the possible
exception of spodumene our results are in general agreement with this earlier work.
Am. J . Sci. 10, 382. 1925.

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It will turn out that in chemical composition and X-ray diffraction

pattern the first six substances are so simply related that one can without
hesitation assume the type structure to be that of diopside.
With spodumene it is not a priori certain that one can make such an
assumption. The axial ratio in spodumene is appreciably different from
that of the other pyroxenes, and furthermore the replacement of Ca
by Li is not a typical isomorphous replacement. For this reason we
have made a more complete analysis of spodumene, making use of a few
quantitative intensity measurements. The type structure is found to be
that of diopside, but with certain appreciable distortions.
Wollastonite and pectolite are found to have unit cells wholly differ-
ent from those of the other pyroxenes. The X-ray oscillation photographs
from these substances show clearly that the true symmetry is triclinic,
not monoclinic as has been generally assumed. The complete structure
determination of wollastonite and pectolite has not yet been completed,
but the qualitative data are sufficient to show definitely that these two
substances do not belong in the general group of monoclinic pyroxenes
with diopside as the type structure.

II. Structure of diopside.

The structure of diopside CaMg(Si03)2 has been determined rigor-
ously by means of quantitative X-ray intensity measurements. A sum-
mary will be given here of the more important features in the structure,
but for complete details reference should be made to the original paper 1 ).
a = 9.71 Â
b = 8.89 Α β = 74° 10'.
c = 5.24 Â
Space group G\h side centered on {a b) with four molecules CaMg-
(Si03)2 in the unit cell.
The coordinates of the atoms in the diopside structure are given in

Table II, the coordinates being expressed both in degrees ^ = 360°j

and in decimal parts of the axial lengths. The origin of coordinates is
a symmetry center in the G\ h space group.
Fig. 1 is a projection of the diopside structure on the plane (010).
The figures within the circles give the Y coordinates of the atoms in decimal
parts of the length of the "6" axis. The calcium and magnesium atoms
are situated on the 2 fold rotation axes, with Ca surrounded by 8 oxygens
1) The structure of diopside, 1. c.

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 The crystal structure oí the monoclinic pyroxenes. 393

Table II.
A t o m i c c o o r d i n a t e s in diopside.

θ, 03 X Y Ζ

Calcium . . . . 0° —110° 90° .00 —.31 .25

Magnesium . . . 0 30 90 .00 .08 .25
Silicon 76 148 85 .21 .41 .24
Oxygen 0¡ . . . 136 145 50 .38 .40 .14
Oxygen 0 2 . . . 51 90 115 .14 .25 .32
Oxygen 0 3 . . . 56 173 0 .16 .48 .00

Fig. 1. Projection of diopside structure on (010).

and Mg by 6 oxygens. Each silicon is surrounded tetrahedrally by 4 oxy-

gens. In each tetrahedron two of the oxygens are shared with neighboring
tetrahedra in such a way as to build up endless chains of silicon-oxygen
tetrahedra. These endless chains lie parallel to the " c " axis of the crystal,
and are shown in fig. 1 by the series of lines connecting silicon and
oxygen.

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394 Β. Ε. Warren and J. Biscoe

III. Comparison with diopside.

On Plate I are shown "c" axis rotation photographs of Diopside,
augite, acmite and spodumene. The general similarity in appearance
is evident. The "c" axis translations as measured from the layer line
spacings are practically identical.

Diopside c = 5.24 Â
Augite 5.24 A
Acmite 5.26 Â
Spodumene 5.24 Á.

A u g i t e . The "c" axis rotation photograph of augite was made with

a specimen from Boreslau, Bohemia. The complete similarity in ap-
pearance to the rotation photograph of diopside both in position and in-
tensity of the spots indicates that the augite structure is essentially,
that of diopside.
A c m i t e . The rotation photograph of acmite is seen to be identical
to that of diopside as regards position of the spots. The intensities of
the spots differ appreciably, as should of course be expected, since the
acmite structure is derived from that of diopside by replacing Mg by Fe
and Ca by Na. The scattering power of Fe is considerably greater than
that of Mg, while Na is less than Ca. Making this substitution, and
using the same atomic coordinates in both structures, it is found t h a t
the calculated amplitudes differ in exactly the same way as do the ob-
served intensities on the rotation photographs. A few of these calculated
amplitudes for the (h k 0) spectra are given below in Table III. On the
"c" axis rotation photographs these (h k 0) reflections lie on the equator.

Table III.
C o m p a r i s o n of c a l c u l a t e d a m p l i t u d e a n d o b s e r v e d i n t e n s i t y
f o r (hk 0) s p e c t r a of d i o p s i d e a n d a c m i t e .

Diopside Acmite
sin θ
Cale. F Obs. Int. Cale. F Obs. Int.

110 .055 — 4.8 y.w + 44.8 M

200 .078 — 7.4 V.W + 10.6 V.W
020 .080 + 24.6 W + 76,6 M
220 .112 — 72.6 S — 34.0 W.M
310 .125 + 77.2 v.s + 119.7 V.S
130 .130 + 14.6 y.w — 4.2 V.W
400 .153 + 17.6 w + 37.6 W

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 The crystal structure of the monoclinic pyroxenes. 395

Table I I I (continuation).
Diopside Acmite
sin θ
Cale. F Obs. Int. Cale. F Obs. Int.

040 .162 + 1.0 W — 20.5 W

330 .170 + 85.3 M.S + 69.7 W.M
420 .175 — 7.5 W + 23.7 W
240 .180 + 0.3 W — 20.2 W
510 .200 — 70.0 M.S — 36,0 w
150 .206 — 86.0 S — 99.0 s

In the above table the dependence of the intensity on multiplicity

and sin θ has been neglected as unnecessary for a qualitative comparison.
It is seen that the observed intensities vary in exactly the same way as
do the calculated amplitudes, so that one may conclude that the acmite
structure is essentially that of diopside, with Na replacing Ca and Fe
replacing Mg.
Spodumene. The " c " axis rotation photograph of spodumene
differs somewhat from that of diopside both in position and intensity
of the spots. For this reason a more thorough analysis of the structure
seemed necessary.
The axial lengths were determined in the usual way from rotation
photographs about the three principal axes.

a = 9.50 Á
b = 8.30 Á β = 6 9 ° 40'.
c = 5.24 Á

Space group C\h with 4 molecules LiAl(Si03)2 in the unit cell. Altho
the unit cell of spodumene is similar to that of diopside it is seen that the
axes a and b and the angle β are all appreciably smaller. It is this small
change in the shape of the unit cell which is responsible for the difference
in position of the spots on the rotation photograph of spodumene. It is
also in part responsible for the difference in appearance of powder patterns
of spodumene and diopside reported by R. W. G. W y c k o f f 1 ) .
To test whether the atomic arrangement in spodumene is similar
to that in diopside, a preliminary spodumene structure was assumed
using the same coordinates as in diopside and replacing Ca by Li and
Mg by Al. Calculated amplitudes from this assumed structure were
then compared with the observed intensities given by oscillation photo-

1) R. W. G. W y c k o f f , Struct, of cryst., p. 417.

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396 Β. Ε. Warren and J. Biscoe

graphs and spectrometer measurements. The amplitudes calculated with

these preliminary coordinates were found to be in sufficiently good agree-
ment to show t h a t the atomic arrangement in spodumene was essentially
the same as in diopside. By then making slight changes in the coordinates,
the agreement was made quite satisfactory. In Table IV are given the
final coordinates arrived at in this way.

Table IV.
Atomic c o o r d i n a t e s in s p o d u m e n e . O r i g i n a symmetry
c e n t e r as i n d i o p s i d e .
K Ζ
! 01 θ2 03 * 1
Li . . 0° —110° 90° .00 —.31 .25
Al . . 0 31 90 .00 .09 .25
Si . . 74 147 90 .21 .41 ¡ .25
Oi . . 140 146 50 .39 .41 ! .14
0, .
.
.
.
47
52
90
175
115
0
.13
.14
.25 1
.49
.32
.00
03

The Θ1 and 0 3 coordinates of lithium are fixed by symmetry con-

ditions but the θ 2 coordinate must be considered as uncertain due to the
small scattering power of lithium.
A set of quantitative intensity measurements were made with the
ionization spectrometer for the (Ä00) and. (OA; 0) planes. In Table Y is
given a comparison of calculated and measured amplitude F for these
two sets of planes, together with a qualitative comparison from rotation
photographs of a few (hkO) and (hOl) spectra.

Table Y.
Comparison of c a l c u l a t e d a n d m e a s u r e d a m p l i t u d e s F for
spodumene1).
sin θ ρ Χ 10« ± F meas. ± F cale.

200 .079 47.6 28 33

400 .159 48.7 40 42
600 .238 46.7 49 48
800 .318 17.8 35 32
1000 .397 24.2 49 50
1200 .477 7.3 31 30
1400 .556 8.8 37 31

1) ρ = - γ - is the measured integrated reflection. F is the amplitude per unit

cell expressed in electron units.

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 The crystal structure of the monoclinic pyroxenes. 397

Table V (continuation).
sin θ ρ X 10e ± F meas. ± F calc.

020 .086 267 69 70

040 .171 2.6 10 15
060 .257 208 107 102
080 .342 1.5 11 10
0100 .428 31.6 58 48
0120 .514 16.4 48 46
0140 .599 small small 9
0160 .684 5.8 36 21
110 .058 M 14
220 .117 M 21
310 .129 V.S 103
130 .134 M. S 29
002 .144 V.S 104
004 .288 S 77
202 .189 s 71
404 .378 M.S 43

Each silicon is tetrahedrally surrounded by four oxygens with an

average Si—O distance of 1.60 Â. Lithium and aluminium are each sur-
rounded by six oxygens with average distances Li—O = 2.26 À and
Al—O = 2.07 Â. In diopside calcium is surrounded by 8 oxygens, while
in spodumene the lithium is surrounded by only six. This same slight
rearrangement of the oxygens about the calcium position must also
take place in the clino-enstatite structure Mg2Si206, where the calcium
is replaced by magnesium in octahetral coordination.
The "c" axis in spodumene is identical in length to "c" in diopside,
due no doubt to the silicon oxygen chains in the two structures being
the same. That the "a" and "b" axes in spodumene are appreciably
shortened is due to the substitution of the smaller atoms Li Al for Ca Mg,
allowing the silicon oxygen chains to pack somewhat closer together.
IV. Chemical composition of monoclinic pyroxenes.
From the X-ray comparison of augite, acmite and spodumene given
in the preceding section, we may reasonably conclude that diopside,
hedenbergite, augite, clino-enstatite, acmite, jadeite, and spodumene
are all monoclinic pyroxenes with diopside as the type structure. In
chemical composition these seven substances seem to come under two
main groups 1 )

1) The notation is that used by F . M a c h a t s c h k i where X is a cation in

8 fold coordination (Ca, Κ, Na), Y a cation in six fold coordination (Fe, Mg, Al, Li)
and Ζ represents (Si, Al).

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398 Β. Ε. Warren and J. Biscoe

Χ Y Z206
γ Y z 2 o6.
The clino-enstatite and spodumene structures should probably be
considered as belonging to the Y Y Z 2 0 6 group while diopside, heden-
bergite, augite, acmite, and jadeite are to be classed as Χ Υ Z 2 O e com-
pounds. Altho a large number of pyroxene analyses tend toward one
or the other of these two limiting compositions, there are many analyses
of pyroxenes which are intermediate. Accordingly we can not express
the chemical composition of the monoclinic pyroxenes by a single general
formula more closely than as follows

Xm Y2-m (SÍ, Al), (0, OH, F)6

where m tends to be either 1.0 or 0.
Another important feature in the chemical composition of the
pyroxenes is found in the fact that as much as one quarter of the silicon
may be replaced by aluminium. In Tables VI, VII, and VIII are given
three augite analyses illustrating this replacing of Si by Al, and the
variation of "m" in the general formula from the limit 1.0. In the analyses,
the number of cations is calculated on a basis of 6 (0, OH, F).

Tables VI, VII, VIII. Augite analyses calculated on basis

of 6 (O, OH, F).
Table VI.
Augite f r o m T o t e n k ö p f c h e n .

No. Metals
% wt. No. Mol.
on basis 6(0,OH,F)

Si02 48.Ì4 .801 1.81

2.00
Í.19 1
AI& 6.21 .061 .28
1.09
ΛΑ 7.73 .048 .22
FeO 2.52 .035 .08 1.01
MgO 10.31 .256 .58
Ti02 1.36 .017 .04
CaO 22.09 .393 .89
Na^O .71 .011 .05 [0.96
Kfi .43 .005 .02 J
ΛΟ. .12 .001
h20 .31 .017

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 The crystal structure of the monoclinic pyroxenes. 399

Table VII.
Augite from Capverden.

No. Metals
% wt. No. Mol.
on basis 6(0, OH,F)

Si02 40.81 .679 1.53

[2.00
í.47
AI2O3 14.24 .140 .63
1.16
Fe/J3 7.89 .049 .22
1.37
FeO 5.95 .083 .19
MgO 14.35 .356 .80
TiOz 2.06
CaO Ih.ni .285 .64
.69
Na¡0 0.61 .010 .05
KtO —

Hfi —

Table VIII.
Augite from Garzatal.

No. Metals
% wt. No. Mol.
on basis 6(0,OH,F)

Si02 44.11 .734 1.66

• 2.00
f.34
A1203 9.66 .095 .43
1-07
Fez03 4.95 .031 .14
1.17
FeO . . . . . . 5.43 .076 .17
MgO 14.06 .348 .79 2.05
Naß —
ì
CaO 21.92 .390 .88 \ .88
K,0 —
1
H2O —

VI. Augite from Totenköpfchen Doelter Vol. I I 552 no. 9i

VII. Augite from Capverden Vol. I I « 96
VIII. Augite from Garzatal Vol. I I « 99
That silicon may be partly replaced by aluminium and that X (Ca,
Να, Κ) may be less than 1.0 is readily seen from the above analyses.
The analyses fit well enough the general pyroxene formula

-X» Yt-m (Si, Al)2 (0, OH, F)6

where
X = Ca, Να, Κ, Μη
Y = Mg, Fe, Al, Ti, Μη (and in spodumene Li).

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400 Β. Ε. Warren and J. Biscoe

Y. Wollastonite and pectolite.

Wollastonite and pectolite are often classed among the monoclinic
pyroxenes, but from the X-ray diffraction study given below it is readily
seen that there is no close connection to this group. The size and shape
of the unit cell of wollastonite and pectolite is quite different from that
of the monoclinic pyroxenes, and furthermore the "b" axis oscillation
photographs show conclusively that the true symmetry is triclinic, not
monolinic as has been generally supposed.
Plate Ha shows a "b" axis rotation photograph of pectolite. The
complexity of the pattern relative to the pyroxene patterns is very evident.
On plates l i b and lie are shown 15° "b" axis oscillation photographs of
pectolite and wollastonite. If the crystals were really monoclinic, the
oscillation patterns should show a reflection plane symmetry across the
equator. The lack of this reflection plane symmetry, and the triclinic
character of the lattice are readily seen on the two oscillation photographs.
From rotation photographs about the various axes and from a complete
set of 15° "6" axis oscillation photographs the dimensions of the unit
cell are found to be as follows:
Wollastonite1)
a = 7.88 Á
b = 7.27 Á 6 molecules CaS'¡03 per unit cell,
c = 7.03 Â
a = 90°
ß = 95° 16'
γ = 103°25'
Pectolite2)
a = 7.91 Á
b = 7.08 Â 2 molecules HNaCa2(Si03)3
c = 7.05 Â per unit cell.
a = 90°
β = 95° 10'
γ = 103° 0'

From the crystallographic measurements schizolite HNa(Ca, Mn)2-

Si309 has been shown to be triclinic. It is interesting to note that the
new axial ratio and angles for the triclinic cell of pectolite are very closely
related to those which have been given for the triclinic crystal schizolite.
The only appreciable difference is a doubling of the "c" axis in schizolite.
1) Wollastonite from Chiapas, Mexico.
2) Pectolite from Giellebekk near Oslo.

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 The crystal structure of the monoclinic pyroxenes. 401

Schizolite HNa(Ca, Mn)2(Si03)3 (Dana)

a: b: c = 1.106: 1: 1.986 a = 90° 11' β = 94°46' γ = 103°7'
Pectolite HNaCa2(Si03)3
a-.b-.c = 1.115: 1 : .995 a = 90° β = 95°10' γ = 103°0'
Altho wollastonite and pectolite are definitely triclinic they have
a most unusual and pronounced pseudo-monoclinic symmetry. The
angle γ is such that the 410 direction, which has always been taken as
the direction of the "a" axis, seems to make exactly 90° with the "b"
axis. What is even more striking is the fact that on the complete set
of "6" axis oscillation photographs all the spots on the even layer lines
show perfect monoclinic symmetry, both as regards position and intensity
of spots. This means that altho wollastonite and pectolite are triclinic,
if the lattice were translated by an amount δ/2 and superimposed upon
itself the resulting configuration would have true monoclinic symmetry.
The structure determination of wollastonite and pectolite has not yet
been completed, but the results will certainly be of the greatest interest
in explaining this curious pseudo-symmetry.

VI. Summary and conclusions.

From X-ray diffraction study and consideration of chemical com-
position it is shown that the representative substances diopside, heden-
bergite, augite, clino-enstatite, acmite, jadeite, and spodumene are all
very similar in crystal structure. These substances may be taken as
representative of the monoclinic pyroxene group with diopside as the
type structure. The chemical composition is represented by the general
formula Xm Y2_.m (Si, Al)2 (0, OH, F)e where X = (Ca, Να, Κ), Y =
(Mg, Fe, Al, Ti, Li) and m tends to be 1.0 or 0.
Wollastonite and pectolite are shown to have unit cells wholly differ-
ent from those in the monoclinic pyroxene group. The true symmetry
of the structures is found to be triclinic rather than monoclinic as had
been generally supposed. The structures of these substances are de-
finitely different, and there appears to be no reason why they should be
classed with the monolinic pyroxenes.

Cambridge, Mass., U. S. Α., July 10 th , 1931.

Received July 25 th , 1931.

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