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Acta Cryst. (1952). 5, 691

Setting a single crystal by non-equatorial X - r a y reflexions. By A. L. MACKAY, Birlcbeclc College

Research Laboratory, 21 Torrington Square, London W.C.1, England (Received 24 May 1952 and in revised form 14 June 1952)
N o r m a l X - r a y m e t h o d s of o r i e n t i n g a c r y s t a l to r o t a t e a c c u r a t e l y a b o u t a p r i n c i p a l s y m m e t r y axis fail w h e n n o reflexions in t h e e q u a t o r i a l l a y e r line c a n be i d e n t i f i e d . A r e v i e w of m e t h o d s h i t h e r t o p u b l i s h e d is i n c l u d e d in a c o m p r e h e n s i v e p a p e r b y J e f f e r y (1949) b u t to m e e t a particular problem, not covered by methods discussed b y J e f f e r y , a t e c h n i q u e w a s d e v e l o p e d w h i c h has a w i d e r applicability. I t w a s n e c e s s a r y t o set a c r y s t a l of a l a m e l l a r m i n e r a l to r o t a t e a c c u r a t e l y a b o u t t h e sixfold axis p e r p e n d i c u l a r t o t h e l a m e l l a e . F r o m t h e e x t e r n a l f o r m this c o u l d e a s i l y be d o n e to w i t h i n 5 , b u t as t h e h e x a g o n a l u n i t cell h a d d i m e n s i o n s a - - - - 9 . 7 a n d c----133 tk it w a s q u i t e impossible to i d e n t i f y e q u a t o r i a l reflexions. As t h e r o w lines w e r e well s e p a r a t e d t h e following m e t h o d w a s u s e d . T h r e e 5-oscillation p h o t o g r a p h s w e r e t a k e n on t h e s a m e film a t e x a c t l y 120 i n t e r v a l s of a z i m u t h (using a U n i c a m s i n g l e - c r y s t a l X - r a y g o n i o m e t e r ) . To e n a b l e t h e s e t h r e e s u p e r i m p o s e d p h o t o g r a p h s to be d i s t i n g u i s h e d , t h e c a s s e t t e w a s r o t a t e d b y a b o u t 2 t o e a c h side of its n o r m a l p o s i t i o n so t h a t t h e t h r e e e q u i v a l e n t r o w lines a p p e a r e d side b y side. W h e n e x a c t l y set to r o t a t e a b o u t t h e h e x a d axis, c o r r e s p o n d i n g f e a t u r e s on t h e t h r e e r o w lines lie a t t h e s a m e d i s t a n c e f r o m t h e e q u a t o r of t h e p h o t o g r a p h , b u t w h e n m i s - s e t t h e i r r e l a t i v e displacem e n t s give t h e c o r r e c t i o n s n e c e s s a r y . S u p p o s e a~, a 2 a n d aa w e r e t h e a n g u l a r d i s t a n c e s of t h r e e e q u i v a l e n t r e c i p r o c a l - l a t t i c e v e c t o r s f r o m Che axis of r o t a t i o n . T h e d i s t a n c e s y~, Y2 a n d Yz of t h e corres p o n d i n g r e f l e x i o n s f r o m a n e q u a t o r i a l line s c r i b e d on t h e film w e r e m e a s u r e d as a c c u r a t e l y as possible a n d ~1, ~2 a n d ~3 w e r e o b t a i n e d f r o m ~----y(r2-~y2)-. ~ for t h e p a r t i c u l a r r o w line u s e d w a s c a l c u l a t e d or m e a s u r e d a n d h e n c e , f r o m cot a ~-- ~/~, al, a2 a n d a a w e r e f o u n d . As t h e differences of a v a l u e s a r e s m a l l (less t h a n 5), a n d as i n f i n i t e s i m a l r o t a t i o n s c a n be t r e a t e d as v e c t o r s , t h e r e s u l t a n t of t h r e e v e c t o r s of m a g n i t u d e s ( 9 0 - - a l ) , (90--c~) a n d (90--aa) s p a c e d 120 a p a r t g a v e t h e m a g n i t u d e a n d d i r e c t i o n of t h e n e c e s s a r y c o r r e c t i o n . T h e d i r e c t i o n of this c o r r e c t i o n was k n o w n to ~2 f r o m t h e oscillation r a n g e . T h e a n g u l a r c o r r e c t i o n w a s r e s o l v e d i n t o t w o c o m p o n e n t s parallel to t h e t w o arcs. A d d i n g t h e v e c t o r s , r e l a t i n g t h e m to t h e p o s i t i o n s of t h e arcs, a n d r e s o l v i n g t h e r e s u l t a n t c o r r e c t i o n parallel to t h e arcs w e r e d o n e g r a p h i c a l l y . If t h e initial s e t t i n g of t h e l o w e r a r c w e r e far f r o m zero, c o r r e c t i o n for t h e tilt of t h e u p p e r a r c w o u l d h a v e to be a p p l i e d , b e i n g f o u n d b y solving a s p h e r i c a l t r i a n g l e . T h e c o r r e c t i o n s o b t a i n e d are n o t e x a c t a n d t w o a p p l i c a t i o n s are n e c e s s a r y for s e t t i n g to 0.1. T h e m e t h o d c a n of course be u s e d for o t h e r t h a n sixfold axes if t h e r o t a t i o n i n t e r v a l s are c h o s e n a p p r o p r i a t e l y .

Reference JEFFERY, J . W . (1949). Acta Cryst. 2, 15.

Acta Cryst. (1952). 5, 691

The direct-inspection method in s y s t e m s with a principal axis of s y m m e t r y . By FAUSTO G.

FVMI, Institute of Theoretical Physics, University of Milan, Milan, Italy

(Received 21 April 1952)

T h e d i r e c t - i n s p e c t i o n m e t h o d (Ftuni, 1952a)* c a n be u s e d to obtain directly t h e i n d e p e n d e n t c o m p o n e n t s of t e n s o r p r o p e r t i e s of m a t t e r o n l y for s y m m e t r y g r o u p s in w h i c h o n e c a n f i n d C a r t e s i a n o r t h o g o n a l c o o r d i n a t e s t h a t do n o t t r a n s f o r m i n t o l i n e a r c o m b i n a t i o n s of t h e m s e l v e s u n d e r the independent symmetry elements. The Cartesian orthogonal reference frames usually applied for groups w i t h a p r i n c i p a l axis Cn(n ~ 3) (zllto t h e axis, x a n d y / to it) s a t i s f y this c o n d i t i o n o n l y for n ~ 4, b u t t h e r e are o t h e r f r a m e s w h i c h allow d i r e c t i n s p e c t i o n in * In this paper 3 {a) is somewhat too condensed to be completely clear. Equations (9) and (10), like equations (6) and (7), are relations between equations (3); when written fully, equation (9) reads Table 1 Finite groups with a principal axis Cn(n ~ 3) n even n odd Generating elements Possible choices of x and y besides Cn

Y^[

/C~
/

Dn
~y

Dn Cn,.
Cnh

c~
~.
(Th

xllc',
yz![~,.

yllC;
zx][at.
Any

~/ ,
Y
X

~h

q~--> y C;

Dnh

Dnh Cni nnd

C2, (lh i C~, i

xl]C~ y[[C 2
Any

~_..
X

txyz~ tyzx-~ tzxy= txzy-~ tyxz= tzyx.

The last sentence of 3 (a) states the identity of the scheme of independent components of the axial and polar third-order tensors for s y m m e t r y 0 with the scheme of the axial thirdorder tensor for s y m m e t r y T d.

C;

xilC~

YlIC~

2/>

l~

C~ = binary axis J_ Cn; av(ah) : i ---- inversion.

s y m m e t r y plane]](_l_)Cn;

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+
%
I I

-~
~+~

.~

~.
1

NI
t

{s..
I++ ,.~ I ++ I

~ ea -~++
I +~

I +

tt~.
t f
I
I

I +

2,,I
..--

I+~

i ~' -~

- ~ I ~
i

++

~%+
I I +

t ~g +
I

t
oo

~2
% l,i % t + %,
I

i:I
0

+ %
0

L)

ID

'

~o

+ .~ + + t %

I T '*'% ~ %
I ~l~l~

+ ~1~+
o

~+++
I

+++

+
i

+ t

a: .T r : SS
~+1
I

o,..i

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T a b l e 3. Fourth-order tensor pq(p, q---- 1, 2, 3, 4, 5, 6) Polar, axial Polar Axial Polar ^ Axial Axial Polar .4~xial Axial Axial Polar
^

Axial

Axial

C1
Any

Ca, Cai Ca Car D3, Dad z]lCa zl!C3 z;lCa xllC~ yzl!a~ zllC3
11 12 13 14 15 16 12 11 13 -14 -- 15
-- 16

xllC

C3v C3h,C6, C~h C6 C3h z l l C s zJlCa,Ce zJlC6 zllC~ zllC~ yzllav

0 0 0 0 15 16 0 0 0 0 -- 15
-- 16

Da

Dsh

C6v D6,D6)~,D3h

De

C6v

zllO;
0 0 0 14 0 0 0 0 0 --14 0 0 0 0 0 0 0 0 41 --41 0 0 0 0 0 0 0 0 0 41 0 0 0 0 14 0

zllC.

zllC3 yzll~

zllC~ zllCs, c.
11 12 13 0 0 0 12 ll 13 0 0 0 31 31 33 0 0 0 0 0 0 44 0 0 0 0 0 0 44 0 0 0 0 0 0 (11--12)

zJlo; zllCe

zllc~ yzlla~
0 0 0 0 0 16 0 0 0 0 0 --16 0 0 0 0 0 0 0 0 0 0 45 0 0 0 0 --45 0 0 --16 16 0 0 0 0

11 12 13 14 15 16 21 22 23 24 25 26 31 32 33 34 35 36 41 42 43 44 45 46 51 52 53 54 55 56 61 62 63 64 65 66

ll 12 13 14 0 0 12 11 13 - 14 0
0

11 12 13 0 0 16 12 11 13 0 0
-- 16

0 0 0 14 15 0 0 0 0 -14 -- 15
0

31 31 33 0 0 0 41 --41 0 44 45 46 --46 46 0 --45 44 41

-- 16

31 31 33 0 0 0 41 --41 0 44 0 0 0 0 0 0 44 41
0

0 0 0 0 0 0 0 0 0 0 45 46 --46 46 0 --45 0 0
-- 16

31 31 33 0 0 0 0 0 0 44 45 0 0 0 0 --45 44 0
-- 16

0 0 0 0 0 0 41 --41 0 0 0 46 --46 46 0 0 0 41
0

16
0

0
0

16
0

16
0

0
0

--15 14 (11--12)

0 14 ~(11--12)

--15 0 0

0 0 (11--12)

--15 14 0

The a x i a l t e n s o r v a n i s h e s i d e n t i e a l l y for symmetries Cai, Dad, C6h and D6h. Ca, C3i a n d Car. T h e r e m a i n i n g g r o u p s w i t h a p r i n c i p a l axis c a n n o t be t r e a t e d d i r e c t l y b y t h i s m e t h o d . D i r e c t i n s p e c t i o n c a n be u s e d , h o w e v e r , to derive t h e i n d e p e n d e n t t e n s o r c o m p o n e n t s in all g r o u p s w i t h a p r i n c i p a l axis f r o m t h e i n d e p e n d e n t c o m p o n e n t s in t h e c o r r e s p o n d i n g g r o u p Cn. I n d e e d , t h e u s u a l C a r t e s i a n o r t h o g o n M c o o r d i n a t e s w i t h zllOn do n o t t r a n s f o r m i n t o l i n e a r c o m b i n a t i o n s of t h e m s e l v e s u n d e r t h e g e n e r a t i n g e l e m e n t s t o be a d d e d to t h e g r o u p Cn t o o b t a i n t h e o t h e r g r o u p s w i t h t h e s a m e p r i n c i p a l axis, if one fixes p r o p e r l y x a n d y (Table 1). T h e i n d e p e n d e n t C a r t e s i a n o r t h o g o n a l c o m p o n e n t s in t h e g r o u p s Cn c a n be o b t a i n e d b y i m p o s i n g i n v a r i a n c e o n e a c h c o m p o n e n t ( H e r m a n n , I934), c o n v e n i e n t l y replaced by the corresponding coordinate product (Fumi 1952 a ; J u r e t s c h k e 1952) : in t h e e q u i v a l e n t t f r a m e s w i t h z llCn, t h e a l g e b r a is f a i r l y s i m p l e since o n l y x a n d y t r a n s f o r m a m o n g e a c h o t h e r . Ob- v i o u s l y t h e s c h e m e for s y m m e t r y C6 c a n a l w a y s be o b t a i n e d b y d i r e c t ins p e c t i o n of t h e s c h e m e for s y m m e t r y C a since C6 is e q u i v a l e n t t o Csh for p o l a r p r o p e r t i e s of e v e n o r d e r or for a x i a l p r o p e r t i e s of o d d o r d e r , a n d it c a n n o t distinguish polar a n d axial properties. As a s i m p l e a p p l i c a t i o n w e t r e a t h e r e a (polar or axiat) t The reference frames which are not distinguishable in their relations to the s y m m e t r y elements of a given group are equivalent for it.

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References

fourth-order tensor pq(p, q = 1, 2, 3, 4, 5, 6) in all trigonal a n d h e x a g o n a l groups: an higher order tensor is t r e a t e d elsewhere (Fumi, 1952b). The equations of invariance for s y m m e t r y Ca are o b t a i n e d in Table 2: for instance, t h e e q u a t i o n for t h e z~yz c o m p o n e n t reads zgyz = -W3z~zx-z~yz. Direct inspection of t h e c o m m o n scheme for s y m m e t r y ~a (Table 3) gives t h e schemes of t h e polar a n d of t h e axial tensor pq for s y m m e t r i e s Cav(av, x -+ --x, y -+ y, z -+ z) a n d Csa(ah, x -+ x, y -+ y, z - ~ - - z ) ; for t h e polar tensor, t h e i n d e p e n d e n t comp o n e n t s for s y m m e t r y C a which are odd in x or in z vanish in Ca, a n d in Can respectively, while for t h e axial tensor these c o m p o n e n t s are t h e only non-vanishing ones. Direct inspection of the c o m m o n scheme for symmet r y C6 yields in a similar fashion t h e schemes for symm e t r y C6v, a n d direct inspection of t h e c o m m o n scheme for s y m m e t r y D s provides t h e scheme of t h e axial tensor for s y m m e t r y Dsa. The i n d e p e n d e n t c o m p o n e n t s of t h e axial tensor coincide with those of t h e polar tensor for s y m m e t r y D~, as for t h e other groups which do

BHAGAV~VrAM, S. (1942). Proc. Indian Acad. Sci. A, 16, 359. BOND, W. L. (1943). Bell Syst. Tech. J. 22, 1. FUMI, F . G . (1952a). Acta Cryst. 5, 44. FuMe, F . G . (1952b). Phys. Rev. 86, 561. ]~ERMANN, C. (1934), Z. Krystallogr. 89, 32. JUR~.TSCHKE, H. (1952). Acta C~yst. 5, 148. MAso~, W. P. (1950). Bell Syst. Tech. J. 29, 184. SzIvEssY, G. (1929). Handbuch der Physilc, 21, 832.

ActaCryst. (1952). 5, 694

Globulite units in protein crystals?* B y DOROTHY WRINCH, Department of Physics, Smith College,

Northampton, Mass., U. S., A.

(Received 21 April 1952)

I t has recently been r e m a r k e d (Wrinch, 1952a) t h a t certain findings regarding residue n u m b e r s favor the possibility t h a t t h e horse hemoglobin a n d m y o g l o b i n structures a n d t h e insulin a n d ribonuclease structures are particles m a d e u p of various c o m p l e m e n t s of molecules in various arrays, all t h e molecules h a v i n g skeletons of NCC polymers of similar type. I n this n o t e we s t u d y this hypothesis in the light of certain i n t e n s i t y d a t a o b t a i n e d in X - r a y crystal studies which are recorded in the literature (Perutz, 1949; Boyes-Watson, D a v i d s o n & Perutz, 1947; K e n d r e w , 1950). I n particular we look for evidence for or against t h e hypothesis (Wrinch, 1937) t h a t such skeletons, if present, are globulite (and indeed cage-like) in character, n o t differing grossly in dimensions in various directions. For t h e monoclinic horse m e t h e m o g l o b i n crystal, t h e m e a n i n t e n s i t y curve as a function of distance from t h e origin (Perutz, 1949) a n d t h e (hOl) intensities (BoyesW a t s o n et al., 1947) are recorded. To test t h e globulite hypothesis, or a n y other hypothesis as to shape, it is of course fruitless to s t u d y the m e a n i n t e n s i t y curve in isolation. H o w e v e r t h e (hOl) intensities t h r o w light on the situation, w h e n studied in conjunction w i t h it. P e r u t z ' s (1949) m e a n i n t e n s i t y curve (small curve in Fig. 1) represents t h e spherical smoothing of all t h e intensities. Let us t h e n construct, from t h e (hOl) intensities, t h e m e a n i n t e n s i t y c u r v e as a function of distance from the origin, t h u s circularly smoothing these co-planar intensities (last curve of Fig. 1). We r e m a r k t h a t sufficiently far from t h e origin there is a general resemblance b e t w e e n t h e two curves. B o t h descend from relatively high values to a m i n i m u m at c. 0.17 A -1 a n d b o t h s u b s e q u e n t l y develop a m a x i m u m at c. 0.22 A -1. So far as it goes, this situation is in accord w i t h the hypothesis t h a t the * This work is supported by the Office of Naval Research.

sl
o 10 5 0 10 5 0 10

10

0"1

0"2

0"3

0"4.

h-,

Fig. 1. Inset curve." Perutz's means intensity curve for the horse methemoglobin crystal as a function of distance from the center (Perutz, 1949). Lowest curve: the circularly smoothed intensity function for the same crystal, calculated from the given (hOl) intensities (Boyes-Watson e$ al., 1947). Upper four curves: the circularly smoothed intensity functions for the horse myoglobin crystal calculated from the given intensities on central planes normal to a, c, c" and b respectively (Kendrew, 1950}.