Clays and Clay Minerals, Vol. 42, No. 1, 46-52, 1994.

R E F I N E M E N T OF T H E N A C R I T E S T R U C T U R E

HONG ZHENG AND STURGES W. BAILEY

Department of Geology and Geophysics, University of Wisconsin
1215 W. Dayton Street, Madison, Wisconsin 53706

A b s t r a c t - - Nacrite crystals from a vug within a matrix ofdickite at Red Mountain near Silverton, Colorado,
have a = 8.906(2), b = 5.146(1), c = 15.664(3)/~,,/3 = 113.58(3) ~ V = 657.9(3)/~3, and space group Cc.
The structure was solved by direct methods to determine phase angles, followed by electron density maps
to locate all atoms. Refinement by least-squares ceased at R = 4.5%. Each 7/~ layer has structural detail
very similar to those of dickite and kaolinite, although nacrite stacking is based on - a / 3 interlayer shifts
along the 8.9 ]k axis (with octahedral cations alternating between the I and II sites in successive layers),
whereas dickite and kaolinite are based on shifts of - a / 3 along the 5.1 ~ axis (with octahedral cations
in the same set of sites in each layer). The angle of tetrahedral rotation is 7.8 ~ and the octahedral counter-
rotations are 7.6 ~ and 8.1~ The H + protons were located on DED maps. The inner 0..H1 vector points
exactly toward the vacant octahedron and is depressed - 1 8 . 6 ~ away from the level of the octahedral
cations. All three surface OH groups have 0...H vectors at 50 ~ to 66 ~ to (001), although OH2 may not
participate in interlayer hydrogen bonding. All three interlayer O H - H - O contacts are bent to angles
between 132 ~ and 141 ~ and form contacts between 2.94 and 3.12/~,. The interlayer separation of 2.915
/k is slightly larger than in dickite, interpreted as due to a less favorable meshing of the oxygen and
hydroxyl surfaces in nacrite--a direct consequence of layer shifts along the 8.9/~ axis.
Key Words--Bond lengths, Crystal structure, Hydrogen bonds, Nacrite, Refinement, Tetrahedral rotation.

INTRODUCTION T h e s t r u c t u r e f o r m e d in this m a n n e r h a s the X a n d Y

N a c r i t e is t h e r a r e s t o f t h e k a o l i n p o l y m o r p h s . Bailey
a n d T y l e r (1960) listed 16 o c c u r r e n c e s k n o w n to t h e m
at t h a t t i m e , n o t all o f w h i c h h a d b e e n c o n f i r m e d by
X - r a y study. Since t h e n at least 20 a d d i t i o n a l occur-
rences, w i t h X - r a y c o n f i r m a t i o n , h a v e b e e n r e p o r t e d
in t h e literature. N a c r i t e usually is c o n s i d e r e d as a high
temperature kaolin polymorph, and most occurrences
s u p p o r t a h y d r o t h e r m a l or p n e u m a t o l y t i c origin. M a -
r u m o (1989) collected oxygen i s o t o p e d a t a t h a t i n d i -
c a t e d i n c r e a s i n g t e m p e r a t u r e o f f o r m a t i o n in the o r d e r
kaolinite, dickite, nacrite, a n d p y r o p h y l l i t e for clays in
K u r o k o d e p o s i t s in n o r t h e r n J a p a n . U s h a t i n s k i y et al.
(1973) a n d B i i h m a n n (1988); h o w e v e r , d e s c r i b e d na-
crite in s e d i m e n t s , w h e r e a n a u t h i g e n i c or l o w - t e m -
p e r a t u r e ( < 80~ h y d r o t h e r m a l origin was p o s t u l a t e d .
P e r m y a k o v (1936) s y n t h e s i z e d n a c r i t e at 300~176
a n d 2 8 5 - 3 0 0 a t m o s p h e r e s . T h i s is t h e only successful
s y n t h e s i s o f n a c r i t e k n o w n to us t h a t h a s b e e n c o n -
f i r m e d by X - r a y s t u d y o f t h e p r o d u c t .
H e n d r i c k s (1939) was t h e first to d e t e r m i n e the cor-
rect stacking o f k a o l i n layers in nacrite. H e used single
crystals o f n a c r i t e f r o m P i k e ' s Peak, C o l o r a d o , to out-
line a six-layer cell w i t h c -~ 43 ~ a n d a p p r o x i m a t e
s y m m e t r y R 3c. T h i s m e a n t t h a t t h e a t o m i c c o o c d i n a t e s
in t h e u p p e r five layers c o u l d b e d e r i v e d f r o m t h o s e o f
t h e first layer b y o p e r a t i o n o f t h e r h o m b o h e d r a l s y m -
m e t r y e l e m e n t s . T h e actual s y m m e t r y was l o w e r e d to
m o n o c l i n i c Cc d u e to partial filling o f the 18 general
p o s i t i o n s o f R 3 c b y o n l y 12 o c t a h e d r a l A1 ions, a n d
t h e cell was slightly d i s t o r t e d to give a 3 angle o f 90~ '.
Copyright 9 1994, The Clay Minerals Society
axes i n t e r c h a n g e d r e l a t i v e to t h e i r usual d e s i g n a t i o n s
in layer silicates, a n d e v e r y layer is shifted by a/3 in
t h e s a m e d i r e c t i o n ( + or - ) a l o n g t h e 8.9 A repeat.
E v e r y o t h e r layer is r o t a t e d b y 180 ~ H e n d r i c k s p o i n t e d
o u t t h a t the layers were b o n d e d across the i n t e r l a y e r
space b y " h y d r o x y l b o n d s " ( n o w t e r m e d long h y d r o g e n
b o n d s ) in w h i c h surface O H g r o u p s p a i r e d closely w i t h
basal oxygens o f the n e x t layer, a n d he e m p h a s i z e d t h e
i m p o r t a n c e o f such b o n d i n g in t h e p o l y m o r p h i s m o f
t h e kaolin m i n e r a l s . T h i s s t r u c t u r e is q u i t e different
f r o m t h e f o u r - l a y e r s t r u c t u r e with/3 = 91~ ' p r o p o s e d
by G r u n e r (1933) for n a c r i t e f r o m B r a n d , Saxony, o n
t h e basis o f X - r a y p o w d e r data. G r u n e r r e c o g n i z e d the
180 ~ r o t a t i o n o f a l t e r n a t e layers, b u t n o t the inter-
c h a n g e o f t h e X a n d Y axes.
N e w n h a m (1961) r e c o g n i z e d t h a t t h e r e were o n l y
two different k i n d s o f layers in t h e H e n d r i c k s ' s t r u c t u r e
o f n a c r i t e a n d t h a t it c o u l d be d e s c r i b e d as a t w o - l a y e r
s t r u c t u r e w i t h a larger/3 angle o f 100 ~ H e d e r i v e d 36
ways to s u p e r i m p o s e two k a o l i n layers to give long
i n t e r l a y e r h y d r o g e n b o n d s ; 12 o f these a s s e m b l a g e s
h a v e the least c a t i o n - c a t i o n r e p u l s i o n across t h e inter-
layer space. B u t the t w o - l a y e r s t r u c t u r e s o f dickite a n d
n a c r i t e were j u d g e d t h e m o s t stable b e c a u s e they were
t h e only o n e s in w h i c h t h e g r o o v e s a n d ridges o f t h e
layer surfaces d u e to d i o c t a h e d r a l d i s t o r t i o n s w o u l d
m e s h across the i n t e r l a y e r space. K a o l i n i t e h a s a less
f a v o r a b l e interface b e t w e e n layers. R a d o s l o v i c h (1963)
p o i n t e d o u t t h a t t h e dickite s t r u c t u r e s h o u l d b e m o r e
stable t h a n t h a t o f n a c r i t e b e c a u s e it m i n i m i z e s the
46
 Vol. 42, No. 1, 1994 Refinement of the nacrite structure
a n g u l a r s t r a i n o n each o f t h e t h r e e d i r e c t e d i n t e r l a y e r
O . . . H v e c t o r s , w h i c h ideally s h o u l d be c o p l a n a r w i t h
t h e t w o closest A P + c a t i o n n e i g h b o r s . In n a c r i t e o n l y
o n e o f t h e basal oxygens (03) is located so it c a n p a i r
u p ideally w i t h a d i r e c t e d h y d r o g e n b o n d o f this type.
T h e o t h e r two b a s a l oxygens (01 a n d 02) are located
so t h a t t h e actual b o n d s m u s t b e nearly at right angles
to t h e ideal d i r e c t e d b o n d s , a n d this m u s t affect t h e
n a c r i t e stability adversely. T h i s difference in g e o m e t r y
o f t h e O - O H b o n d s is d u e to t h e difference in the
i n t e r l a y e r shift d i r e c t i o n s (along t h e 5.1 A axis in dick-
ire a n d a l o n g t h e 8.9 ,~ axis in nacrite).
Bailey (1963) c o n f i r m e d t h e v a l i d i t y o f t h e t w o - l a y e r
s t r u c t u r e o f n a c r i t e a n d r e c o m m e n d e d u s i n g a B angle
o f ~ 114 ~ so t h a t + Z p o i n t s in t h e s a m e d i r e c t i o n in
p l a n v i e w as t h e i n t e r l a y e r shifts. T h e s e q u e n c e o f lay-
ers is t h a t o f t h e s t a n d a r d 6R p o l y t y p e (later d e s i g n a t e d
6R~) d e r i v e d b y Bailey (1969) for t r i o c t a h e d r a l 1:1 lay-
er silicates. T h e o c t a h e d r a l v a c a n c y a l t e r n a t e s in ad-
j a c e n t layers b e t w e e n t h e B a n d C sites o n o p p o s i t e
sides o f the p s e u d o - m i r r o r p l a n e o f e a c h layer, t a k i n g
i n t o a c c o u n t the 180 ~ r o t a t i o n o f a l t e r n a t e layers
( e q u i v a l e n t to a l t e r n a t e o c c u p a t i o n o f t h e 1 a n d II sets
o f p o s s i b l e o c t a h e d r a l sites). It is this o r d e r e d p a t t e r n
o f o c t a h e d r a l c a t i o n s a n d v a c a n c i e s t h a t reduces t h e
s y m m e t r y f r o m t h e ideal r h o m b o h e d r a l R 3 c to m o n o -
clinic C c a n d allows c h o i c e o f a s m a l l e r t w o - l a y e r cell.
B l o u n t et al. (1969) m a d e t h e first r e f i n e m e n t o f t h e
t w o - l a y e r s t r u c t u r e o f nacrite, u s i n g t h e W e i s s e n b e r g
film t e c h n i q u e o n crystals f r o m P i k e ' s Peak, C o l o r a d o .
C o m p l e t e r e f i n e m e n t was i n h i b i t e d (R = 10%) b e c a u s e
o f t h e p r e s e n c e o f o u t - o f - s t e p d o m a i n s in w h i c h t h e
i n t e r l a y e r shifts were in the w r o n g d i r e c t i o n ( + a / 3 in-
s t e a d o f - a / 3 ) . Z v y a g i n et al. (1972) also refined t h e
s t r u c t u r e (R = 12%) u s i n g h i g h - v o l t a g e e l e c t r o n dif-
f r a c t i o n in t h e o b l i q u e t e x t u r e m o d e o n fine-grained
n a c r i t e f r o m the w e s t e r n T r a n s b a i k a l region o f t h e
U.S.S.R. T h e i r s t r u c t u r e differed slightly f r o m t h a t o f
B l o u n t et al. (1969) in t h e c o o r d i n a t e s o f several a t o m s
and, m o r e i m p o r t a n t l y , in a s m a l l e r t e t r a h e d r a l r o t a -
t i o n angle o f 3.2 ~ r e l a t i v e to 7.3 ~. T h e y a t t r i b u t e d the
s m a l l e r angle to t h e c o u n t e r a t t r a c t i o n o f the basal ox-
ygens b y o c t a h e d r a l c a t i o n s in t h e a d j a c e n t layer.
T h i s p a p e r r e p o r t s a n e w r e f i n e m e n t o f n a c r i t e using
a n a u t o m a t e d single-crystal X - r a y diffractometer. T h e
p u r p o s e s o f the s t u d y were to a c h i e v e h i g h e r accuracy
in a t o m i c c o o r d i n a t e s so t h a t t h e d i s c r e p a n c i e s b e t w e e n
t h e two p r e v i o u s r e f i n e m e n t s c o u l d b e r e s o l v e d and, i f
possible, to locate H + p r o t o n s a s s o c i a t e d w i t h the O H
groups. T h e n a c r i t e u s e d was f r o m a p r e v i o u s l y u n r e -
p o r t e d o c c u r r e n c e w i t h i n vugs o f a h y d r o t h e r m a l dick-
ite d e p o s i t at R e d M o u n t a i n n e a r S i l v e r t o n , C o l o r a d o .
I n t e r l o c k i n g b o x w o r k s o f t h i n n a c r i t e platelets 0.1 to
1.0 m m in d i a m e t e r w i t h i n s m a l l c a v i t i e s o f a dickite
m a t r i x were f o u n d in two s e p a r a t e m i c r o m o u n t s in t h e
G . L. English collection ( U n i v e r s i t y o f W i s c o n s i n G e -
ology M u s e u m # U . W . 6 0 0 3 / 1 a n d U . W . 6003/2).
47
EXPERIMENTAL METHODS
A n a p p r o x i m a t e l y t r i a n g u l a r section 0.6 x 0.5 x 0.5
m m o n t h e sides a n d 0.01 m m t h i c k was cut f r o m a
larger crystal t a k e n f r o m s p e c i m e n U W # 6 0 0 3 / 1 a n d
u s e d to collect i n t e n s i t y d a t a o n a S i e m e n s P 4 r o t a t i n g
a n o d e single-crystal diffractometer. T h e crystal used
s h o w e d s h a r p optical e x t i n c t i o n a n d n o visible t w i n -
ning. T h e diffraction spots were slightly diffuse b u t
were n o t streaked. D a t a were collected u s i n g t h e r =
100 ~ cell, b u t all results r e p o r t e d here were t r a n s f o r m e d
to t h e preferred/~ = 114 ~ cell o f Bailey (1963), a n d t h e
a t o m d e s i g n a t i o n s are t h e s a m e as t h o s e o f B l o u n t et
al. (1969). T h e t r a n s f o r m e d u n i t cell p a r a m e t e r s are a
= 8.906(2), b = 5.146(1), c = 15.664(3) A, ~ =
113.58(3) ~ a n d V = 657.9(3) ~3, o b t a i n e d b y c e n t e r i n g
12 m e d i u m - a n g l e reflections (20 = 45 ~ to 57 ~ M o K a
r a d i a t i o n ) . T h e s e v a l u e s give c sinr = 14.356 ~ . A
m o r e a c c u r a t e v a l u e o f c sin B = 14.364(1) ~ was o b -
t a i n e d b y e x t r a p o l a t i n g t h e a b s o r p t i o n f u n c t i o n to 0 =
90 ~ for v a l u e s o f ~ d ( 0 0 ~ ) f r o m ~ = 16 to 18 (0 = 59 ~ to
75 ~ w i t h CuKa~ X - r a d i a t i o n ) as m e a s u r e d f r o m a film
p a t t e r n f r o m t h e s a m e crystal m o u n t e d in a D e b y e -
S c h e r r e r c a m e r a o f 114.6 m m d i a m e t e r .
A t o t a l o f 3890 reflections was collected in all o c t a n t s
o u t to 20 = 60 ~ w i t h m o n o c h r o m a t i c M o K a r a d i a t i o n .
A 0-20 scan t e c h n i q u e was u s e d w i t h a s c a n w i d t h o f
2.2 ~ 20 a n d v a r i a b l e s c a n n i n g speeds f r o m 2 ~ to 30 ~ p e r
m i n u t e . T w o s t a n d a r d reflections were c h e c k e d e v e r y
100 reflections to m o n i t o r t h e crystal a n d e l e c t r o n i c
stability. N o i n s t a b i l i t y was f o u n d . T h e d a t a were cor-
r e c t e d for t h e Lp f a c t o r a n d for a b s o r p t i o n u s i n g b o t h
the semi-empirical psi-scan technique and an analyt-
ical s h a p e c o r r e c t i o n , t h e n m e r g e d i n t o 827 m o n o c l i n i c
reflections.
REFINEMENT
Initial a t o m i c c o o r d i n a t e s were d e t e r m i n e d b y d i r e c t
m e t h o d s using p r o g r a m S H E L X T L for p h a s e angle de-
t e r m i n a t i o n , followed b y e l e c t r o n d e n s i t y m a p s to lo-
cate all o f t h e a t o m s . T h e s e a t o m i c c o o r d i n a t e s c o n -
f i r m e d t h e 2-layer s t r u c t u r e o f B l o u n t et al. (1969) a n d
gave a n initial r e s i d u a l R o f 23.5%.
Because o f t h e t h i n n e s s o f the crystal, r e f i n e m e n t was
a t t e m p t e d w i t h d a t a sets in w h i c h a b s o r p t i o n was t a k e n
i n t o a c c o u n t in t h r e e different ways: 1) e m p i r i c a l psi-
s c a n c o r r e c t i o n , 2) t h e o r e t i c a l a n a l y t i c a l s h a p e correc-
t i o n , a n d 3) n o a b s o r p t i o n c o r r e c t i o n , b u t w i t h 30 low-
angle reflections m o s t a p t to b e affected b y a b s o r p t i o n
r e m o v e d f r o m t h e d a t a set. Each d a t a set was refined,
a n d t h e t h e r m a l ellipsoids were p l o t t e d b y p r o g r a m
O R T E P . T h e ellipsoids for the t w o d a t a sets w i t h o u t
a b s o r p t i o n c o r r e c t i o n a n d as c o r r e c t e d b y p s i - s c a n were
m a r k e d l y m o r e elongate parallel to Z * t h a n for t h e
d a t a set c o r r e c t e d b y t h e a n a l y t i c a l s h a p e c o r r e c t i o n .
Because residual a b s o r p t i o n effects were suspected e v e n
in t h e latter d a t a set b e c a u s e o f p a s t e x p e r i e n c e w i t h
48 Zheng and Bailey Clays and Clay Minerals

difficulty in measuring the thickness o f very thin crys-

tals, 30 low-angle reflections were r em o v ed from the
~ o o ~ o o oo
latter data set for a final refinement. Only results from
the latter refinement are reported here, but it should
O O O O O O O O O O O O O be noted that the differences in the resulting atomic
II I I I
coordinates and bond lengths for the three refinements
are small--always in the last decimal place reported.
The differences are in the shapes of the thermal ellip-
soids and to a lesser degree in the standard deviations
0 0 0 0 0 0 0 0 0 0 0 0 0 o f atomic coordinates.
0 0 0 0 0 0 0 0 0 0 0 0 0 During refinement the x and z coordinates o f atom
A~2 were held constant while all other parameters were
varied using a modified version of the least-squares
program ORFLS. U n i t weights and half-ionized scat-
tering factors were used throughout. Isotropic temper-
O0 O0 O0 ature factors were used until R declined to 7.9% and
. . . . . . . o. o. q o . .
0 0 0 0 0 0 0 0 0 0 0 0 0 then changed to anisotropic factors. When refinement
I l l I l l i I I
ceased, difference electron density (DED) maps were
flat at all atomic positions. The scattering contributions
o f hydrogen are mainly to the low-angle reflections, so
the 30 reflections deleted during refinement o f the non-
O0 O0 hydrogen atoms were returned to the data set in an
q q q q q q q q q q q q q
attempt to locate the H + protons on D E D sections.
Small positive anomalies o f 0.3 to 0.4 electrons were
E found near the O H groups, which were taken as the
positions o f the H + protons. These positions did not
change when the 30 reflections were removed from the
data set as a check. For comparison purposes, 0.08
o 0 0 ~ 0 0 0 0 0 0 0 0 0 0
o d d o d d o d d d d d d e//~ 3 corresponds to the background value averaged
over the 480 independent points o f one D E D section
chosen to be away from any atomic position. The final
residual R of 4.5% incorporates these H + positions,
which were not refined.
0 0 0 0 0 0 0 0 0 0 0 0 0
q o q q o q q q o q q q q Table 1 lists the final atomic parameters, and Table
0 0 0 0 0 0 0 0 0 0 0 0 0
2 lists the orientations o f the thermal ellipsoids. Table
3 gives calculated bond lengths and angles from pro-
gram ORFFE. Table 4 lists selected structural features
o f nacrite.
~ 0 ~ ~ ~ ~
"7, DISCUSSION
deddddddddddddddd
Ill The bond lengths and angles reported in Table 3 and
the structural features reported in Table 4 are in much
better agreement with those of dickite and other layer
silicate structures than given by either the refinements
O o f Blount et al. (1969) or Zvyagin et aL (1972). The
atomic coordinates cannot be compared directly with
e~
those of the previous authors because x and z o f A 12
were held constant at the values given by the initial
electron density map rather than at either set of prior
~9
published values.
The calculated tetrahedral rotation angle o f 7.8 ~
compares well with the 7.3 ~ angle given for nacrite by
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Blount et al. (1960), but is substantially larger than the
3.2 ~ angle of Zvyagin et al. (1972). The structural de-
tails o f each 7 ~k layer are very similar to those o f the
most recent refinements of dickite and kaolinite, as
< < ~ 0 0 0 0 0 0 0 0 0 = = ~ summarized by Giese (1988). The octahedral cations
Vol. 42, No. 1, 1994 Refinement of the nacrite structure 49

are closer to the upper OH plane than to the lower Table 2. Shape and orientation of thermal ellipsoids.
O,OH plane, and the upper and lower anion triads of RMS Angles with respect to
the octahedra are counterrotated by 7.6 ~ and 8.1 ~ re- Atom displacement
Axis (A) X Y Z
spectively, as a consequence of shortening of shared
edges. The shared diagonal octahedral edges around AI(1) R1 0.102(5) 169(14) 79(14) 65(6)
R2 0.110(5) 79(14) 14(2) 88(12)
A11 and A I2 average 2.383/~ vs. 2.845 ~ for unshared R3 0.133(4) 90(6) 82(7) 155(6)
diagonal edges and 2.781 .~ for the lateral edges. The AI(2) RI 0.091(5) 171(12) 99(13) 64(4)
lateral edges around the vacant octahedron average R2 0.105(5) 99(13) 10(2) 83(7)
3.409 ~. The tetrahedra are tilted because of these R3 0.147(4) 94(3) 86(4) 153(3)
latter large edges, elevating basal oxygen 01 by 0.215 Si(1) R1 0.084(5) 99(10) 171(20) 86(9)
R2 0.093(5) 10(1) 99(20) 117(4)
/k above the level of 02 and 03. This elevated 01 is R3 0.147(3) 94(3) 90(2) 153(3)
paired with an elevated OH2 across the interlayer space, Si(2) R1 0.093(5) 97(6) 173(16) 88(8)
but the three surface OH groups are more nearly co- R2 0.104(4) 8(5) 97(16) 117(5)
planar than in dickite. It should be noted that the OH2- R3 0.135(3) 93(5) 88(4) 153(5)
01 separation is the largest of the three interlayer bond O(1) R1 0.09 I(1 I) 127(8) 39(4) 84(6)
R2 0.142(8) 38(6) 52(9) 108(24)
contacts (Table 3), and the participation of OH2 in R3 0.156(8) 84(9) 97(16) 161(23)
hydrogen bonding is controversial. 0(2) R1 0.095(11) 117(12) 153(12) 77(8)
Zheng and Bailey (1989) compared the results of R2 0.130(8) 151(21) 63(11) 60(9)
locating H protons in chlorites by X-ray diffraction R3 0.157(7) 100(12) 89(8) 147(12)
0(3) R1 0.102(9) 167(14) 102(16) 71(10)
using DED maps relative to the more accurate neutron R2 0.128(9) 99(17) 25(5) 107(26)
diffraction method. They concluded that, in some cases, R3 0.142(8) 81(10) 112(16) 154(20)
the X-ray results are within 0.05 to 0.10 ,~ of the neu- 0(4) R1 0.067(13) 157(16) 112(17) 72(6)
tron results, but, in other cases, the excess electron R2 0.082(12) 113(17) 23(7) 82(13)
densities are probably artifacts. In the present study of R3 0.158(7) 86(4) 90(5) 161(4)
0(5) R1 0.083(12) 141(7) 129(7) 69(6)
nacrite, the O..H distances determined within the four R2 0.140(8) 61(8) 122(17) 63(13)
hydroxyls are between 0.70 and 0.76 ~ , which are R3 0.149(8) 66(7) 125(17) 145(32)
shorter than the generally accepted values (0.95 to 1.0 OH(l) RI 0.095(11) 131(12) 41(12) 74(10)
9~). The three surface hydroxyls have H..O interlayer R2 0.127(9) 133(13) 126(3) 48(I 1)
R3 0.160(7) 109(9) 106(9) 134(10)
contacts between 2.331 and 2.535 ,~; their OH-H--O OH(2) RI 0.108(10) 42.3(9) 50(15) 118(12)
angles are between 132 ~ and 141 ~ and their contacts R2 0.135(9) 121(18) 43(7) 52(13)
with the basal oxygens are between 2.944 and 3.117 R3 0.150(8) 115(17) 76(21) 129(21)
(Table 3). The O..H bonds from the surface hydroxyls OH(3) RI 0.109(10) 127(17) 38(8) 79(12)
are oriented between 50 ~ to 66* from the (001) plane, R2 0.124(9) 39(8) 53(8) 99(2 I)
R3 0.142(8) 80(17) 87(16) 166(16)
whereas O..H from the inner hydroxyl points exactly OH(4) RI 0.119(9) 58(16) 113(28) 155(12)
towards the vacant octahedron in plan view but is de- R2 0.125(9) 34(5) 66(17) 89(22)
pressed 18.6* away from the octahedral sheet into the R3 0.152(9) 99(14) 34(5) 115(12)
tetrahedral sheet.
Figure 1 shows the projections onto (001) of the H +
positions for nacrite as determined in this study rela- culated H2-01 distance of 2.60 A was just equal to the
tive to the theoretical positions determined by Giese sum of the van der Waals radii of hydrogen and oxygen
and Datta (1973) by minimization of the total electro- and considerably larger than the 2.02 ,~ distance cal-
static energy using the non-hydrogen atomic positions culated for the other two H - O contacts; and 3) the
of Blount e t a L (1969). The experimental points in point involving OH2 on a plot of the two A 1 - O H - H
projection all lie about 0.35 ~ from the theoretical angles vs. one another fell on the 45 ~ line indicating
points. Much of this difference is due to the O...H equality of the angles and, thus, non bonding. The
distances of 0.70 to 0.76 ~ found within each hydroxyl authors state that the two A I - O H - H angles hypothet-
in this study instead of the more realistic value of 0.97 ically should be equal unless there are outside influ-
,~ used by Giese and Datta for their calculations. These ences, such as hydrogen bonding. Giese (1973) later
shorter distances automatically increase the H - O dis- concluded that H2 makes a very small contribution to
tances to the acceptor oxygens and increase the O H - the interlayer bonding on the basis of a small decrease
H - O angles. in slope of a plot of Coulomb energy vs. interlayer
Giese and Datta (1973) believed OH2 did not par- distance when OH2 is replaced by F in the calculations.
ticipate in interlayer hydrogen bonding in nacrite be- It should be noted that the theoretical m i n i m u m energy
cause 1) the O...H2 vector from OH2 was calculated positions for the H + protons undoubtedly would change
to have m i n i m u m electrostatic energy when oriented somewhat if calculated on the basis of the more ac-
at 38* to (001) relative to values of 79 ~ and 73 ~ cal- curate non-hydrogen atomic positions determined in
culated for O...H3 and O...H4, respectively; 2) the cal- the present study.
50 Zheng and Bailey Clays and Clay Minerals

Table 3. Bond lengths (/~) and angles (*).

Si 1-O 1 1.610(5) O 1--O2 2.623(8) O 1-Sil-O2 108.7(3)

02 1.617(5) O1-O3 2.583(7) O1 O3 105.9(3)
03 1.626(5) O 1-04 2.678(7) 02 03 106.4(3)
04* 1.601 (5) 02-03 2.597(7) O1 04 113.0(3)
Mean 1.613(2) 02-04 2.662(7) 02 04 111.6(3)
03-04 2.657(6) 03 04 110.8(2)
Mean 2.633(3) Mean 109.4(1)
Si2-0 1 1.604(5) O 1-02 2.593(8) O1-Si2-O2 107.0(3)
02 1.622(5) O1-03 2.629(6) O1 03 109.3(8)
03 1.618(5) O1-05 2.670(7) 02 03 106.0(3)
05* 1.605(5) 02-03 2.583(7) O1 05 112.6(3)
Mean 1.612(2) 02-05 2.654(7) 02 05 110.6(3)
03-05 2.658(7) O3 O5 111.1(2)
Mean 2.631(3) Mean 109.4(1)
Lateral edges Diagonal edges
AI 1--O4 1.991 (5) 04-435 2.764(6) Shared
05 1.942(5) O4-OH 1 2.792(7) O4-43H4 2.389(7) x 2
OH 1 1.923(6) O5--OH 1 2.763(8) O5-OH3 2.390(7) x 2
OH2 1.858(5) OH2-OH3 2.768(8) OH 1--OH2 2.371(7) x 2
OH3 1.857(6) OH2-OH4 2.804(7) Mean 2.383(4)
OH4 1.860(6) OH3-OH4 2.763(8) Unshared
Mean 1.905(2) Mean 2.778(3) O4--OH3 2.862(7) x 2
O5--OH2 2.853(7)x2
OH1--OH4 2.816(7)x2
Mean 2.844(4)
A12--O4 1.945(5) 04--05 2.789(6) Shared
05 1.989(5) O4-4)H 1 2.758(6) O4-4)H4 2.389(7) x 2
OH 1 1.912(5) O5--OH 1 2.772(8) O5--OH3 2.390(7) x 2
OH2 1.867(5) OH2-OH3 2.811 (8) OH 1-OH2 2.371(7) x 2
OH3 1.866(5) OH2--OH4 2.765(8) Mean 2.383(4)
OH4 1.859(5) OH3-OH4 2.779(7) Unshared
Mean 1.906(2) Mean 2.784(3) O4-~H2 2.849(7) x 2
O5--OH4 2.883(7) x 2
OH1--OH3 2.806(8) x 2
Mean 2.846(4)

Vacant octahedron Angles A1-OH-H

lateral edges All Al2

04-05 3.409(7) HI 117,0 120.3

O4-OH 1 3.417(7) H2 128.6 127.1
O5-OH1 3.438(7) H3 107.2 142.5
OH2-OH3 3.377(6) H4 150.5 102.6
OH2-OH4 3.387(8)
OH3--OH4 3.423(8)
Mean 3.409(3)
Interlayer contacts Hydrogen distances Hydrogen angles
O 1-OH2 3.117(7) OH 1..H 1 0.70(6) OH2-H2-O 1 135(3)
O2--OH3 2.951(7) OH2..H2 0.76(12) OH3-H3-O2 132(4)
O3--OH4 2.944(7) H2--O 1 2.535(10) OH4-H4-O3 141(6)
Mean 3.004(4) OH3..H3 0.74(10)
H3--O2 2.400(11) Angle O..H to (001)
OH4..H4 0.74(8) H1 -18.6
H4--O3 2.331 (6) H2 56.8
H3 65.9
H4 50.3

In the present study the e x p e r i m e n t a l position found
for H 2 is such that the angle o f O . . . H 2 to (001 ) increases
f r o m the 38 ~ value o f Giese and D a t t a (1973) to 57 ~
(which m a k e s A 11, A 12, O H 2 , and H 2 a l m o s t exactly
coplanar), and the H2-01 distance decreases to 2.535
(it w o u l d be e v e n shorter i f the O...H2 distance were
0.97 A instead o f 0.76 ,~). T h e two experimental A 1 -
O H 2 - H 2 angles are nearly equal, however, in support
o f the theoretical values o f Giese and Datta (1973).
T h e O...H3 vector found in the present study is tilted
Vol. 42, No. I, 1994 Refinement of the nacrite structure 51

Table 4. Other important structural features.

Parameter Site Val ue

Octahedral distortion RMS (15) AI(I) 9.45

Al(2) 9.43
Octahedral distortion RMS (36) At(l) 5.74
Ai(2) 5.80
Octahedral rotation (0) upper triad 7.62
lower triad 8.13
Octahedral flattening 'I'o, (*) AI(1) 57.4
AI(2) 57.4
Tetrahedral angle r (*) Si(1) 111.8
Si(2) 111.4
Tetrahedral rotation a,e, (*) 7.76
Basal oxygen AZ (A) 0.215
Sheet thickness (/~)
Tetrahedral 2.212
Octahedral 2.055
Interlayer separation (A) 2.915
Interlayer shift -0.353at
B~d~al(*) 112.28

away from acceptor oxygen 02, which is unrealistic.

Experimental point H4 is also unrealistic in that it
deviates in plan view (Figure 1) from a straight line
between O H 4 and 03. The points for OH3 and OH4,
however, both lie well within the fields o f hydrogen
bonding in the A1--OH-H angle plot. The O...H1 vec-
tor is depressed 18.6 ~ below the octahedral sheet and
appears to point in the expected direction (Figure 1),
although the O...H 1 distance is shorter than expected.
The two A I - - O H I - H 1 angles are nearly equal (Table
3).
In summary, the positions for the H + protons found
in this study differ from the theoretical m i n i m u m en-
ergy positions because o f the short O...H distances found
and the deviations of H3 and H4 from the expected
geometry for hydrogen bonds. The peaks interpreted
as H + positions were the only extra D E D peaks near
the O H groups. The e//~ 3 values o f the peaks were H 1
= 0.38, H2 = 0.30, H3 = 0.34, and H4 = 0.40. These
values range from 3.75a to 5.0a, using the average
background value o f 0.08 for a. If the equation o f Ladd
and Palmer (1977, p. 292) is used to calculate the D E D
background, then a(Po) = 0.05, and the H + peaks range
from 6.0a to 8.0~. But these tests only indicate that the
extra D E D peaks are significantly above background,
not that they necessarily represent the true positions
o f the H protons. The presence o f systematic absorp-
tion errors in the data is suspected because of the un-
realistic thermal ellipsoids o f the atoms (see below).
A neutron diffraction refinement is needed to deter-
mine the correct positions o f the H + protons. The H +
positions as determined in the present study, however,
do support the views of Giese and Datta (1973) and
Giese (1973) that OH 2 does not participate appreciably
in interlayer hydrogen bonding. The average interlayer
separation o f 2.915 ,~ (Table 4) is slightly larger than
found in dickite (2.883 to 2.887/~), leading to a slightly
Figure 1. Projection onto (001) of basal oxygens in the tet-
rahedral sheet of the second layer onto the octahedral sheet
of the first layer. Small solid circles are H + positions found
in this study. Small asterisks are theoretical H positions
calculated by Giese and Datta (1973). Small open circles are
centers of the vacant octahedra.
larger d(001). This is interpreted as due to a less fa-
vorable meshing o f the oxygen and hydroxyl surfaces
in nacrite resulting from the positions o f O H 2 and O H 3
relative to 01 and 0 2 - - a direct consequence o f layer
shifts along the 8.9 ,~ axis.
None o f the thermal B~j values proved to be non-
positive definite during refinement, but they are not
believed to represent true thermal motion. For phyl-
losilicates the bridging tetrahedral basal oxygens should
vibrate normal to the Si--O-Si bond. Table 2 shows
this is not the case for the present refinement. The
major axes o f the thermal ellipsoids for the basal ox-
ygens instead are essentially normal to the layer. Sim-
ilar results have been noted in other refinements o f
layer structures involving very thin platelets.
ACKNOWLEDGMENTS
This research was supported in part by National Sci-
ence Foundation grant EAR-8614868 and in part by
grant 17966-AC2-C from the Petroleum Research
Fund, administered by the American Chemical Soci-
ety. We are indebted to the Department o f Chemistry,
University o f Wisconsin-Madison, for use o f their dif-
fraction facilities and to Randy Hayashi for technical
assistance.
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