233

Aeta tryst. (1949). 2, 233

The Crystal and Molecular Structure of Naphthalene. I. X-ray Measurements

B Y S. C. ABRAHAMS; J. I~ONTEATH ROBERTSON AND J. G. WHITE
The University, Glasgow W. 2, Scotland

(Received 13 April 1949)

A comprehensive X - r a y investigation of the crystal structure of n a p h t h a l e n e is described, in which

all the reflexions t h a t lie within the reach of Cu Kc~ radiation have been examined. Moving-film
photographic m e t h o d s a n d visual estimates of intensities by i n d e p e n d e n t observers were employed.
F r o m the results a total of 644 structure factozs out of a possible 832 have been evaluated, giving
I29 structure factors per a t o m of the asymmetric unit. F r o m the earlier two-dimensional approxi-
m a t i o n to the n a p h t h a l e n e structure it has been possible to assign phase constants to 612 of the
factors w i t h reasonable certainty. These results form the basis of a n e w three-dimensional deter-
m i n a t i o n of t h e structure which is described in P a r t II.

1. Introduction obtained as projections of the crystal structure, also

Naphthalene a n d anthracene were among the first failed to give any reliable picture of the electron dis-
organic substances to be studied by the X-ray method, gribution in the regions between the carbon atoms,
and the early measurements of Sir William Bragg (1921, because the degree of resolution of the various atoms
1927, 1928) on these crystals gave a clear indication of differed in different parts of the projections.
the existence of molecules of about the shape and size In the present papers we describe a redetermination
to be expected from the chemical evidence, and also of the naphthalene structure which employs all the X-
showed how these molecules could be accommodated ray reflexions that can be observed with copper radia-
in the unit cells of the crystals. Later work based on. tion at room temperature. Special methods have been
optical and magnetic measurements as well as on X-ray employed to preserve the volatile crystals during the
data (Banerjee, 1930 a, b; Robertson, 1930) gave the long exposures which are necessary, and from the
positions and dimensions of the molecules more pre- measurements a total of 644 structure factors have
cisely, and finally the structures were determined in been evaluated out of a possible 832 which lie within
detail from a complete survey of all the axial zones by the range of Cu K a radiation. Calculations employing
the application of the double Fourier series method the previously determined structure (Robertson, 1933 b)
(gobertson, 1933 a, b). as a first approximation have led to a reliable deter-
The results of this last investigation showed that mination of the phase constants for just over 600 of
in naphthalene the carbon atoms are arranged very these structure factors. The utilization of these
accurately in the form of two regular, planar hexagonal measurements in a new structure determination by the
rings. Ten out of the fifteen co-ordinates which deter- triple Fourier series method is described in Part II.
mine the positions of the carbon atoms could be
measured directly from the electron-density maps, and 2. Crystal data
the other five values could be inferred with reasonable The lattice constants were redetermined by means of
certainty. The average C--C distance (radius of the carefully calibrated oscillation and moving-film photo-
hexagon) was obtained as 1.4I A., and the individual graphs. The new values, given below, differ only
C-C distances were placed at between 1.40 and 1-44 A. slightly from the earlier measurements (Bragg, 1921;
These findings were in accord with theoretical ex- Robertson, 1933b). Naphthalene, C10Hs; M, 128.2;
pectations. The average C--C distance of 1.41 A. was m.p. 80"2° C.; d, calc. 1.172, found 1.152. Monoclinic
a little less than the graphite vMue of 1.42 A. and a prismatic,
little greater than the benzene value of 1.39 A. Both a = 8.235 + 0.005, b = 6.003 + 0.010,
theoretical calculations (Pauling, Brockway & Beach,
c = 8.658 _+0.010 A., /? = 122 ° 55' +_5'.
1935) and chemical properties indicated that the bond
lengths in different parts of the molecule might vary Absent spectra, (hO1) when h is odd; (0/c0) when k is
slightly from the average value. The experimental odd. Space group, C52wP21/a. Two molecules per unit
results, however, were not capable of giving any cell. Molecular symmetry, centre. Volume of the unit
reliable measure of this variation, apart from a slight cell, 361.7 A. a. Absorption coefficient for X-rays,
indication that the central C-C bond might be rather A= 1.54 A., #=6.05 cm. -1. TotM number of electrons
longer than the others. The electron-density maps, per unit cell = F(000) = 136.
234 T H E C R Y S T A L AND M O L E C U L A R S T R U C T U R E OF N A P H T H A L E N E . I

3. Experimental measurements Table 1. Layer lines recorded a ~ dimensions

of specimen
Preservation of crystal specimens Dimensions of crystal specimen (mn~..)
In this work it was necessary" to make a complete Layer l i n e Cross-sectionx length along rotation axis
survey of all the reflexions within the range of Cu K a 0kl
lbll 0.13 × 0.39 × 0.39
radiation (h= 1.542 A.). This was carried out by photo-
graphic, methods, using small crystals (0.1-0.2 rag.) l/el |
2hl ~ 0.24 × 0.53 × 0.79
completely immersed in a uniform X-ray beam. 3kl J
Naphthalene is so volatile that crystals of this size, hOl}
placed in the open, disappear within an hour or two. hll 0.31 × 0-71 × 0.95
For the work on hand it was necessary to preserve the
h2l
h31 0.28 × 0.61 × 0.90
specimens for periods of up to 2 weeks. Several hk0]
methods were tried, but the most effective consisted hkl /
in mounting the specimen on an extremely fine glass hh2, 0.94 × 1-05 x 0.16
hie3
fibre inside a thin gelatin capsule, about 15 mm. in hk4)
length and 5 mm. in diameter. The capsules (size 2, hhl ]
manufactured by Messrs Parke, Davis and Co., h,h+l,l|
Detroit) were of very uniform thickness (0.12 mm.), and h, h ~ 2, l~ 0.26 × 0.61 × 1-00
h,h~3, l|
so "did not introduce appreciable intensity errors due h,h~4, l)
to absorption of the X-ray beam. Some powdered h,h+ l,l[
h,h+2,1~ 0.31 x 0.53 × 1.20
naphthalene was kept in the base of the capsule, which
was' sealed off with Apiezon Sealing Compound Q. h,h+_4, l • 0.44 × 0.50 × 1.30
The capsule and crystal could then be mounted and set Three sets of correction factors were applied to the
in the usual manner on the goniometer arcs. Crystals intensities: (a) The normal Lorentz and polarization
so mounted could be preserved on an accurate setting factors. (b) Absorption corrections to allow for the
for several weeks. shape of the crystal specimen. These were made very
approximately by evaluating a mean path length for
Intensity measurements and corrections the ray through the specimen for each reflexion. As the
The photographic surveys were carried out almost coefficient for naphthalene is small ( # = 6"05 cm. -1 for
entirely by moving-film methods, with an instrument A-- 1.54 A.) this rough correction is probably sufficient.
of the equi-inclination Weissenberg type. This method (c) A geometrical correction factor applied to all re-
was preferred to that of the oscillation photograph, not flexions other than those on equatorial layer lines, to
only in giving a more reliable correlation between allow for the angular velocity of rotation of the plane
certain sets of reflexions, but especially because it through the reflecting angle. For the equi-inclination
permits the background around each reflexion to be Weissenberg type of camera employed, the factors
reduced to a minimum by careful adjustment of the described by Tunell (1939) were used.
screens. The structure factors were calculated from the in-
A consideration Of the points which lie within the tensities by the usual formula for mosaic-type crystals,
limiting sphere of the reciprocal lattice for naphthalene and placed on the absolute scale previously deter-
showed that all the reflexions could be recorded on mined (Robertson, 1933b). The structure factors for
conveniently accessible layer lines from rotation about planes whose reflexions appeared on different layer
the [100], [010], [001] and [110] axes. A list of the lines and which came from different crystal specimens
layer lines recorded, with dimensions of the crystal were correlated by reflexions common to the different
specimens employed, is given in Table 1. sets. The final values chosen were the average of the
A fairly reliable set of structure factors for the axial different sets after correlation, for each reflexion
zones in naphthalene have already been determined frequently, occurred in several different sets examined.
on an absolute scale (Robertson, 1933b). For the When variations occurred among very strong re-
present extended survey, the method of visual esti- flexions, the highest value was generally adopted, in
mation by two independent observers was adopted. view of the possibilities of extinction errors.
The multiple-film t,echnique (Robertson, '1943) was When the structure factors of reflexions which
used to correlate the strong and weak reflexions, the appeared on two or more different layer lines, given by
extreme range being about 5000 to 1. Kodak Industrex different crystals, were correlated and compared, it was
Type D film was used,'for which the reduction factor found that the discrepancy was frequently of the order
from film to film (separated by two thicknesses of the of 10%. The system adopted for estimating the in-
inner black paper wrapping) was determined by photo- tensities was generally good enough to provide F values
meter measurement as 3-1 for Cu K a radiation. Using correct to within about 5 %. There is, therefore, some
this method, independent estimates of the various apparent lack of constancy in the determination of the
intensities generally agreed to better than 10 %. F values which may be due to variations in crystal
 S. C. A B R A H A M S , J. M O N T E A T H ROBERTSON AND J . G. W H I T E 235

t y p e or t o i n a d e q u a t e c o r r e c t i o n s for a b s o r p t i o n . T h e ~ c c u r a t e fit for o t h e r c r y s t a l s w h e r e t h e t e m p e r a t u r e

o v e r a l l a c c u r a c y o f t h e F v a l u e s m a y p e r h a p s be f a c t o r will i n g e n e r a l b e d i f f e r e n t .
p l a c e d a t b e t w e e n 5 a n d 10 % .
T a b l e 2. 3*o values for naphthalene at 20 ° C. including
temperature factors
Determination of phase constants
h = 1.54 A. Maximum-- 100 for sin 0 = 0.
The values of the structure factor finally determined sin 0 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
a r e s h o w n i n T a b l e 3, u n d e r ' F m e a s . ' . T h e p h a s e con-
0.0 97 96 94 92 90 88 87 85
stants of these structure factors were next calculated 0.1 82 81 79 77 74 73 71 69 66 64
o n t h e basis of t h e p r e v i o u s s t r u c t u r e d e t e r m i n a t i o n b y 0.2 62 60 58 56 54 53 51 49 48 46
t h e d o u b l e F o u r i e r series m e t h o d ( R o b e r t s o n , 1933b). 0.3 45 43 42 40 39 38 37 35 34 32
0.4 31 30 29 28 27 26 25 24 23 22
F r o m t h e s e r e s u l t s t h e signs o b t a i n e d for 612 o f t h e 0.5 21 21 20 19 18 18 17 16 16 15
644 o b s e r v e d F v a l u e s w e r e c o n s i d e r e d t o b e r e a s o n a b l y 0.6 15 14 14 13 13 13 12 12 12 I1
c e r t a i n , a n d t h e s e 612 v a l u e s w e r e a c c o r d i n g l y e m - 0.7 10 10 10 10 9 9 8 8 8 7
0.8 7 7 7 7 7 6 6 5 5 5
p l o y e d as coefficients i n t h e t r i p l e F o u r i e r series in- O.9 4 4 4 4 4 4 3 3 3 2
v e s t i g a t i o n w h i c h is d e s c r i b e d i n P a r t I I . T h e re-
m a i n i n g 32 F v a l u e s , all s m a l l , a n d for w h i c h t h e The agreement between the observed and finally
g e o m e t r i c M s t r u c t u r e f a c t o r s w e r e all less t h a n 2 % o f c a l c u l a t e d F v a l u e s o n t h i s basis, e x p r e s s e d as
t h e p o s s i b l e m a x i m u m (for all a t o m s i n p h a s e ) , w e r e Z {I Fracas. I - [ Fcalc. [}
e x c l u d e d f r o m t h e t r i p l e F o u r i e r s u m m a t i o n s us u n -
reliable. These F values are marked with an asterisk is 16"8 % for all t h e s t r u c t u r e f a c t o r s . P a r t o f t h i s
i n T a b l e 3. d i s c r e p a n c y will be d u e t o e r r o r s i n t h e m e a s u r e d F
F r o m t h e final c o - o r d i n a t e s o b t a i n e d as a r e s u l t o f values, but a substantial portion must be attributed to
the investigation described in Part II, the structure l a c k o f s p h e r i c a l s y m m e t r y i n t h e a t o m i c e l e c t r o n dis-
factors have been recalculated, and these values are t r i b u t i o n s , t o t h e b r i d g e v a l u e s for t h e d e n s i t y i n t h e
l i s t e d i n T a b l e 3 u n d e r 'Fcalo.'. F r o m t h i s final re- aromatic rings, and to the hydrogen atoms.
c a l c u l a t i o n of t h e s t r u c t u r e f a c t o r s it w a s f o u n d t h a t
six o f t h e t e r m s i n c l u d e d i n t h e F o u r i e r s y n t h e s i s h a d References
c h a n g e d i n sign. T h e v a l u e s i n v o l v e d a r e g e n e r a l l y BANERJEE, K . (1930 a). Indian J. Phys. 4, 557.
s m a l l , a n d a r e m a r k e d w i t h a d o u b l e a s t e r i s k i n T a b l e 3. BA~ERJEE, K . (1930 b). Nature, Lend., 125, 456.
F o r t h e final e v a l u a t i o n of t h e s t r u c t u r e f a c t o r s a n BRAGS, W . H . (1921). Prec. Phys. Soc. 34, 33.
e m p i r i c a l s c a t t e r i n g c u r v e for c a r b o n w a s e m p l o y e d BRAQG, W . H . (1927). Z. Krystallogr. 66, 22.
which gave the best average correlation between the BRAGG, W . H . (1928). Nature, Lend., 121, 327.
observed and calculated F values. This curve was
PAULING, L., BROCKWAY, L. O. & BEACH, J . Y. (1935).
J. Amer. Chem. Soc. 57, 2705.
f o u n d t o differ s o m e w h a t f r o m t h e f c c u r v e p r e v i o u s l y
ROBERTSON, J. M. (1930). Nature, Lend., 125, 456.
e m p l o y e d ( R o b e r t s o n , 1935 a, b), w h i c h w a s b a s e d m a i n l y ROBERTSON, J. M. (1933 a). Prec. Roy. Soc. A, 140, 79.
on measurements from anthracene and graphite. The ROBERTSO~, J. M. (1933 b). Prec. Roy. Soc. A, 142, 674.
n e w f c v a l u e s a r e g i v e n i n T a b l e 2, a n d it s h o u l d b e ROBERTSO~, J. M. (1935 a). Prec. Roy. Soc. A, 150, 106.
n o t e d t h a t t h e y a r e d e s i g n e d s p e c i f i c a l l y for n a p h t h a - ROBERTSON, J. M. (1935 b). Prec. Roy. Soc. A, 150, 110.
l e n e a t 20 ° C. a n d i n c l u d e t h e t e m p e r a t u r e f a c t o r . I t ROBERTSON, J. M. (1943). J. Sci. Instrum. 20, 175.
is n o t t o b e e x p e c t e d t h a t t h e y will g i v e a n e q u a l l y TUh~ELL, G. (1939). Amer. Min. 24, 448.

T a b l e 3, Measured and calculated value of t he naphthalene structure factors

* Values omitted from the Fourier synthesis.
** Values included in the Fourier synthesis with incorrect sign.
h~ Fm~. F~,c. hkl Fmea~. /~10. hkl Fm.... F=Io. hkl F .... Fc~,c.
001 33"5 + 35"0 207 2"6 -- 3"1 406 1"3 -- 1"1 604 0.9 + 0.2
002 18"2 -- 17"5 206 3"4 -- 4"4 405 1"2" + 0"5 603 4-3 -- 3.3
003 22.4 + 16"0 205 1"1 -- 0"6 404 < 1"4 + 1"0 602 1.9 -- 1.0
004 16'5 + 13"0 204 6"1 + 6"2 403 1'7 + 2'6 601 < 1.5 + 1.6
0O5 1.6 -- 1"8 203 16"8 + 16"2 402 5"7 + 6"2 60i 8.7 -- 7.8
006 2.7 -- 4.0 202 5"5 + 4"3 40I 1"2 -- 1"8 60~ 3.6 -- 3.4
007 3.9 -- 4.9 201 4"9 -- 3" 1 40i 2"9 + 5"7 603 3.3 + 2.3
008 1.3 -- 1.7 20i 37"5 +44"0 40~ 6"2 - 4"9 60g: 11.7 + 9.7
009 < 1.4 + 1.0 20~ 17"3 -- 17"8 40~ 1.0" -- 1.8 603 3.9 + 3-4
020 14.7 -- 11.8 203 0"6* -- 2"0 40~ 9.4 + 10.6 606 1-9 -- 2.7
040 0.8 + 2.3 20~ 8"7 +10'5 403 3.9 - 3.4 60? 11.2 + 9.9
060 < 1.6 + 1.7 205 3"2 -- 4"2 406 1-0" + 0.2 608 12.3 + ll.0
200 43.9 +47.3 20~ 1"2 + 0"6 40? 13"3 + 13.3 609 < 1.4 -- 0.2
400 4.6 -- 6-4 207 3"5 + 3"6 408 6.6 + 6.7 6,0,]-0 1.4 -- 1-2
600 6.2 -- 5.3 20~ 1.5 -- 0.7 409 2.2 -- 1-2 6.0.]-i 2.1 + 1.5
800 1.3" -- 0.3 209 < 1.3 + 0.8 4,0, ]-0 2.2 + 1.6 801 < 1.3 + 0.3
208 < 1-4 + 0.4 2,0.1-O 1.8 + 1.5 4.0.1T < 1.0 + 1-5 80i 5.7 -- 4-7
236 THE CRYSTAL AND MOLECULAR STRUCT,URE OF NAPHTHALENE. I

Table 3 (cont.)
hkl -Fm~. -Fca~c. hkl .Fm~. .F~¢. hkl 1~,~,~. P~ac. hkl .F,,e~" FC~e.
80~ 3"3 -- 2"4 312 0.6* + 0.6 816 < 1.0 + 0.4 323 6.9 -- 6.7
80~. 1"8 + 1"7 313 6.9** + 4-5 817 2.6 -- 2.4 322 1.3" + 1.0
80,i: 6"3 + 4"6 31,~ 15"7 + 13.8 5.2 5.0
81~ -- 321 0.8 + 1.8
805 6"1 + 4"7 315 1.5" 0 810 2.3 -- 2-1 32] 15.1 --16-9
806 < 1"7 + 1"6 316 2"5 + 2.4 8,1,i0 0.6 + 0.6 32~ 2-7 + 3.2
809 1"9 + 0"5 319 8.0 + 6.8 91i 2.6 -- 1.6 32~ 8.3 + 9.3
80g 6.5 + 5.6 31~ < 1"0 -- 0"1 91~ 0.9 -- 0.7 32~ 2.3 -- 2.3
80~ 1-2 + 1.3 310 1.0 -- 1.0 915 O.8 -- O.2 325 6.9 -- 6.8
8,0,i-0 1-4 -- 1.5 3,1 ,i-O 1.5 + 1.2 914 < 0.9 -- 0.8 326 2.2 + 1-0
10,0,~ < 1.2 + 0.5 416 < 0.9 + 0.2 915 0.9 + 1.2 329 6-5 + 6.8
I0,0,~ < 1.2 + 0.2 415 0.9 + 1.6 916 < 1.0 + 0.2 32~ 2-O + 3.0
10,0,5 < 1.2 + 0.6 414 3.0 -- 2.7 919 < 1.2 -- 1.3 320 0.6 -- 0-9
10,0,6 < 1.2 + 0.7 413 8.0 -- 7.3 91~ 1.5 + 1.4 3,2,]-0 0.9 + 0-4
lO,O3 < 1.2 -- 1.1 412 3.4 -- 2.6 910 1.4 + 1.2 426 < 0.9 -- 0"7
lO,O,g < 1.2 -- 0.4 411 1.0 + 1.0 9,1,]-0 0.7 -- 0.3 425 0.7 + 0.4
lO,O,0 < 1 . 2 -- 0.1 41i 23.5 - - 23.5 10,1,$ 0.8 + 0.3 424 4.3 -- 4-4
011 6.4 + 6.7 412 3.0 -- 3.5 10,1,~ 2.9 -- 1.3 423 3.8 -- 4"6
012 3.8 + 4.1 413 11.7 +12.8 10,1,5 3"0 -- 1.3 422 1.8 + 2-3
013 6.7 " + 4.7 41~: 5.0 + 4.2 10 1,6 <0.9 -- 0.1 421 2.8 -- 2-6
014 9.4 + 7-6 415 2.5 -- 3.4 10,1,7 < 0.9 -- 0"3 42i 14.2 +13.2
015 1.4 + 2.8 416 2.9 + 3.0 10,1,8 2.7 -- 2.0 42] 7.0 + 7-6
016 4.1 -- 4.4 419 8.4 + 8.0 021 15-8 -- 14.3 423 1.5 + 1-4
017 3.5 -- 3.8 41~ 3.9 + 3.6 022 5.3 + 2.4 42~ 10.0 + 9.6
018 0.7* -- 0.4 • 410 0.9 0.9 023 11.2 + 10.8
--
425 4.6 + 4-8
019 < 1-1 -- 0.4 4,1,]-0 0.7 , - - 0.6 024 4.0 -- 4.0 426 1.4" -- 1-1
1,10 37.0 +45.0 515 < 1-0 + 0-1 025 1.4"* -- 0.8 427 <0.9 -- 0.2
210 28.9 --31-0 514 1.4 -- 1.2 026 8.2 + 8.4 42~ 2-7 -- 2.5
310 5.4 + 5.0 513 2.0 -- 2-6 027 2.5 + 2.3 42~ 1.3 -- "1.6
410 14.4 --14.2 512 1-5 + 2.0
510
028 0-9 -- 1.1 4,2,i-0 1-1 + 0.9
4.7 -- 4.2 511 1.1 + 0.6 029 < 0-9 + 0.5 525 0.7 + 0.7
610 1.6 -- 1.5 51i 3"0 + 2"9 120 13.2 -- 13.5 524 1.5 -- 1.0
710 1.3 -- 1.4 51~ 3.5 + 3.5 220 6.9 -- 7.0 523 4.9 -- 5-0
810 < 1.4 + 0.3 • 5 1 ~ 1.6 + 0.9 320 15.0 -- 15.1 522 3.4 -- 2-2
118 0.7* "-- 0.1 51~ 10.2 + 9.1 420 2.3 -- 1.5 521 1.8 + 2-8
117 2.0 -- 1.6 515 1.9 + 2.1 520 3.1 -- 3.4 52i 14.3 --11-5
116 0.9 + 0.2 516 1.4 -- 2.3 620 < 1.3 -- 1.2 52] 6.4 -- 5.3
115 1.0" + 0.1 519 7.1 + 6.9 720 < 1.2 -- 0.2 52:] 1.0"* -- 2.4
114 2..9 + 2.8 51~ 5.O + 6.1 820 1.1 -- 0.8 52~ 1.4 -- 0.6
113 11.3 +12-2 510. 2.3 -- 1-6 128 0.6 + 0.4 523 5.1 -- 4-3
112 3.3 -- 4.2 5,1,1--(i 0-7 + 0.4. 127 1.7 -- 1-9 526 2.0 1.7
--
111 8.9 -- 5.7 5,1,iT < 1.0 + 0.9 126 3.9 -- 3.4
lli 529 1.3 +
0.9
19.5 +23-5 614 < 0.8 - 0-8 125 4-2 -- 3.0
11~ 52g 1.6 +
1.7
12.6 --11.8 613 4.3 - 4.2 124 4-5 -- 4.1 520 < 0.9 +
0.9
113 14-8 +12-6 612 4.4 - 3.6 123 4.0 -- 4-8 5,2,1-U 1.0 +
0-2
11~ 12.2 +12.8 611 0.8 + 0.4 122 1.5 -- 1-3
113 624 < 0.7 -- 0-5
1.0" + 0.2 61i 6.1 - 5.7 121 7"5 -- 7.2 623 0.8 - - 1.2
116 3.4 + 6.0 61] 1.1 - 1.4 12i 2.3* - - 2.1 622 < 0.3 + 1-7
119 1-3 + 0.8 615 3.6 + 4.7 12~ 11.8 + 9.9 621 1.5 + 1-2
11~ 1.9 -- 1.7 61~ 2.7 + 3.5 123 9.2 + 6.2 62i 7.7 + 6.4
110 0.8 + 0.8 615 1.0 + 0.5 12~ 1.2 -- 2.4 62~ 8.3 + 7-8
218 < 0.9 -- 0-1 61~ < 1.0 + 0-2 125 1-2 -- 0.9 62~ 3.3 -- 4.3
217 0.9* -- 0.1 " 619 1.2 - 0.5 126 7-8 + 6"1 62,i 1.7 , -- 1.9
216 0.9 + 0.9 61g 1.4 - 1.4 129 6.2 + 6"6 623 3.2 + 3.9
215 1.0 + 2.0 610 0.9 - 1.1 12~ 1.0" + 0.2
214 626 1.6 - 1.9
2.2* -- 1.1 6,1,1---0 < 1.0 - 1.0 120 1.4 -- 0.6 629 2.4 - 3.6
213 4.0 -- 2-9 6,1,]--f < 0.8 - 0.4 227 < 1.0 -- 0.4 62~ 1.9 - 1.6
212 2.2 + 3.4 713 < 1.3 - 1.4 226 3"8 + 3.9 620 1-1 - 0.9
211 1.3 -- 1.0 712 1.3 - 1.2
21i 28.1 --32.0
225 1.3 + 1.3 6,2,1--6 2.0 + 1-0
711 0.8 + 1.8 224 8"4 -- 8.1 722 2-0 -- 1.4
21~ 1.1" -- 0.5 71i 2-6 - 2.8 223 2-2 2.3
-- 721 < 1.4 -- 0-7
21~ 6.9 + 6.7 71] 1.0 + 0.6 222 3.1 +* 3"5
21~ 72i 3.5 -- 2.9
10.0 -- 7.9 713 < 1.0 + 0.3 221 11.5 -- 12-0 72~ 4.2 -- 3.3
213 6.2 -- 6.2 71~ 2.7 + 2.3 22i 4.0 + 4.7 723 2-9 -- 3.0
216 - 8-4 + 7.3 713 2.9 + 3.3 22~ 1"9 + 2.7 724 3.6 -- 2.8
219 10.2 +10.2 716 1.9 - 2.4 22:] 16.3 + 15.2 723 2.2 -- 1-6
21~ 2.2 + 2.5 719 1.7 + 1.0 22~ 12.2 +11-0 726 1.5 -- 0.7
210 1.1 -- 0.8 718 5.5 + 5-6 9.23 1.1 + 1.0 729 2-2 -- 2-2
2,1,I0 0.9 + 0.9 710 0.8 + 0-7 226 4.9 + 5.5 72~ 2-5 -- 2.0
317 0.7 -- 0.9. 7,1 1-0 0.7 -- 0.2 229 4.6 + 3.4 720 1.3 + 1.4
316 1.1 -- 1.2 7,1,'iT < 0.7 + 0.9 22~ 2.5 -- 2.4 7,2,i-0 2.0 + 1.0
315 1.0" -- 0.1 811 <0.7 + 0.1 220 1.3"* -- 0.5 821 1.1 + 0.9
314 2.0 -- O.8 81i < 0.8 + 0.6 2,2,1--0 0"6* + 0.1 82i < 1.2 + 0.1
313 3-2 + 3.5 81] 0.9 + 1.5 327 0"7 -- 0.6 822 2.1 + 3.1
312 5.0 + 4.4 813 < 1.0 + 0"7 326 < 0.8 -- 0.2 823 2.8 -- 2.2
311 6.5 -- 7-2 81~ 2.3 - - 2.0 325 1.6 -- 0.7 82~ 4.8 -- 5.6
31i 20.3 +21.0 815 1"8 -- 1"2 324 5.6 -- 5.1 825 < 1-2 + 0.5
 S. C. ABRAHAMS, J. MONTEATH ROBERTSON AND J. G. WHITE 237

Table 3 (cont.)
hkl .Fm~. .F~. hkZ rm~ Fc~,c hkl Fme~. Fealv" hkl -Fr~ea~. -Fcale.
828 < 1.1 -- 0.2 333 1.8 -- 1.8 937 < 0"6 - - . 0"7 543 0"8 + 1"0
82~ 1.5 -- 2.3 334 2.0 + 3.6 936 < 0"6 - - 0"3 542 1"8 -- 1"4
826 < 0.9 + 0-1 335 3.3 - 2-7 041 3"3 - - 2"5 541 3"7 -- 3"6
820 < 0.9 + 0.8 338 2.7 -- 2.4 042 1"6 - - 0"6 54i 1"3 + 2"3
8,2,1U <0.7 + 0 6 337 < 0.8 -- 0.4 043 0"9 + 2"5 542 < 1"3 + 0"2
92i 0.8 - 0.4 336 1.8 -- 1-5 044 7"0" - - 5"5 543 6.0 -- 5-4
• 922 <0.9 + 0-1 330 1.3 + 04 045 5"4 - - 6"2 544 2.7 -- 2-8
923 1.3 - 1.1 3,3,Y0 0.4 + 0.6 046 0"7 - - 0"2 545 2.3 + 2.6
924 4.8 - 3.0 435 1.4 - 1.5 047 < 0"7 - - 0"6 546 1.0 + 0.5
92~ 2.6 - 1.8 434 1.4 - 1.2 048 < 0.7 - - 0.6 54~ 1.1 -- 1.8
928 < 1-2 + 0.7 433 2.0 - 1.2 140 1.0 + 0.8 548 1.1 + 0.3
929 < 1.2 - 1.2 432 1.5 - 0.4 240 < 1.0 - - 0.9 54§ 0.9 + 0.6
926 3.3 - 2.4 43I < 1.0 + 0.9 340 < 1.0 + 0.7 642 1.6 + 0.2
920 0.8 - 1.0 43i 1.0 + 0.6 440 1.0 - - 2.2 641 0.7 -- 0.5
10,2,,~ 3.0 - 2.0 43~ 0.8 -- 0.9 540 1.5 - - 1.6 64] 1.1 -- 0.1
10,2,5 < 1.1 - 0.5 433 5.5 -- 5.8 640 2.0 - - 2.5 64~ 2.1 -- 0.7
10,2,8 < 1.1 + 0.5 43,~ 4.8 -- 4.0 740. 0.9 - - 0.6 64~ 5.7 - 5.5
10,2,7 < 1.0 -- 0.6 433 2.4 -- 1.9 147 2.7 - - 0.4 64~ 1.1 -- 1.2
10,2,~ < 1.0 + 0.4 438 2.5 -- 4.1 146 < 1.0 + 0.4 645 2.1 + 2.7
031 13.7 - - 12.1 439 1-9 -- 2.3 145 1.2 - - 1.1 646 0.8 -- 0.5
032 8.0 - - 7.5 43~ 1.1 + 1.2 144 3.3 -- 2.5 649 < 0.8 -- 0.3
033 7"8 - - 6.5 430 1.2 + 1.3 143 3.8 -- 1.4 64~ < 0.8 -- 1.1
034 8"9 - - 8.2 4,3,ru 0.5 + 0.7 142 1.8 - - 1.2 64~ < 0-8 -- 0.8
035 6.8 -- 5.7 534 <0.4 + 0.1 141 3.3 - - 3.8 741 0.7 -- 0.5
036 3.2 - - 2.5 533 0.5 - 1.2 14i 5.8 + 5.1 74i 1.0 - O.5
037 1.3 - - 1.2 532 0.8 + 1.7 142 3.0 -- 3.8 74~ 1.1 -- 0.7
038 < 1.0 + 0.1 531 1.1 - 1.1 143 2.9 - - 3.3 74~ 1.3 -- 0.5
130 10.0 - - 10.2 53i 5.3 + 5.6 14,~ 6.0 + 4.1 744 1.3 + 1.4
230 1.6" - - 0.5 532 1.3 + 1.1 143 4.6 + 3.9 745 1.1 -- 0.6
330 4.3 - - 3.7 533 8.9 - 9.2 148 1"1 - - 1"6 746 < 1-0 -- 0.8
430 < 1.1 -- 0.3 53~ 0.7 -- 0.5 14~ 1.0 -- 1"3 749 < I-0 -- 0.9
530 1.1 - - 2.7 533 4.1 + 4.7 146 1"1 + 1"0 74~ < 0.8 + 0.6
630 0.9 - - 0.7 538 1.3 -- 1.3 246 0"5 + 1.0 74§ < 0.8 + 0.3
730 1.4 - - 2.7 539 3.1 -- 3.0 245 2.4 + 1"0 84i < 0.8 -- 0.3
830 0.6 - - 0.6 536 2.1 -- 2.0 244 1"9 -- 2-2 84~ 1.9 + 1,9
138 < 0.6 - - 0.5 530 0.8* -- 0.1 243 < 1"5 + 1.8 84~ 1.2 + 0.5
137 0.6 - - 0.1 5,3,Yff 1.3 + 1-3 242 5"0 + 2.9 844 0.8 -- 0.6
136 5.8 + 5.6 633 < 0.8 + 0.5 241 1"5" + 0'4 845 1-9 + 1.8
135 1.1 - - 1-3 632 < 0.7 -- 0.3 24[ 5"5 - - 3"6 848 1.2 + 1.0
134 9.8 - - 9.9 631 0.5** -- 0.2 24~ 10"5 -- 10"2 84~ < 1.0 -- 0.3
133 3.0 4- 2.6 63i 3.6 -- 3.3 243 4-5 --5"8 84~ < 0.8 -- 0.1
132 10.8 + 9.3 632 6.1 -- 4.9 244: 4"7 - - 2.7 94~ < 0.9 + 0.3
131 6-5 - - 5.3 63~ 7.5 -- 6.5 243 9"9 - - 9"0 945 < 0-9 -- 0.3
13i 8.9 -- 8.4 63~ 6.7 -- 5.9 248 5"1 - - 4"2 948 < 0.9 -- 0.9
13~ 0.6* + 1.1 633 3.7 -- 2-5 249 < 1.0 + 0.4 051 3.1 + 4-6
133 8"8 + 8-1 638 2.7 -- 2.8 2461 < 1.0 - - 0.4 052 6.3 + 5-2
13~ 5.2 --6.7 639 2.1 -- 2.1 249 < 0.7 + 0.3 O53 1-8 + 1.9
133 7"8 -- 7.3 636 1.3 + 1.4 345 < 1.0 - - 1.2 054 < 2.3 -- 0.3
138 2.7 + 3.2 630 2.1 + 1.9 344 0.9 + 0.7 055 < 2.0 + 2-5
139 1.5 + 1.9 6,3,T~ 0.8 + 0.8 343 < 1.1 + 0.I 056 <2.0 + 1.2
136 1.7 - - 1.7 732 0.7 + 0.8 342 4.4 - - 3.4 057 < 1.8 -- 0.9
130 0.4 + 0.5 731 1.2 - 0.2 341 4.2 -- 5.2 150 1.3 + 3.4
237 1-0 - - 0.8 73i 2.7 + 2.6 34i 5.2 + 5.7 250 <0.9 -- 1.0
236 3.3 - - 3.2 73~ 4.7 + 5.3 342 1.8 -- 2.6 350 0.9 -t- 0.1
235 5.1 - - 4.7 733 4.0 - 4.6 343 8-7 - - 8.6 450 2.5 -- 2.5
234 6.1 - - 5.7 73,~ 5.2 -- 5.2 34,~ 1.2 + 1.7 550 1.3 -- 0.6
233 5.7 - - 5-7 733 3.2 + 3.3 343 6.8 + 6.2 650 0.9 -- 1.1
232 4.6 - - 2.7 738 1.7 + 2.1 348 1.4 - - 0.9 156 < 0.8 + 0.4
231 5.3 - - 4.0 739 2.4 -- 2-2 349 2.0 - - 2.7 155 < 0.8 -- 0.5
23i 9.7 + 9.5 736 1.7 -- 1.5 346 1.1 + 1-2 154 0.8 + 0.4
232 5.4 + 6.6 730 0-7 - 0.6 ! 340 1.2 + 1.2 153 0.7 + 0.8
233 0.8* + 0.6 7,3,TU 1.0 + 0.8 445 < 1.0 + 1.5 152 6.1 -- 5.5
234 2.9 + 3.4 83i 2.7 -- 1.8 444 2.0 + 1-3 151 4.6 -- 5.2
23~ 2.7 + 2-0 83~ 4-6 -- 3-1 443 0.9 + 0.4 15i 3.8 -- 3.3
238 1.0 - - 2.1 833 4.6 -- 3.2 442 2.2 + 2.2 15] 10.2 -- 9.1
237 < 0.8 -- 0"6 834 4.7 -- 2.7 441 1.0* - - 1.4 153 3.3 -- 1.3
236 <0.8 + 0.1 833 2.2 -- 1.2 44i 2.7 - - 1.5 154. 1.0 + 0.8
230 0.5 + 0.1 838 0.9 -- 0.5 442 9.8 - - 9.0 153 3.2 - 3.0
336 2.1 + 1.9 839 < 0.9 -- 0.6 443 9-3 - - 8.5 158 1.8 - 1.2
335 3.4 + 2.7 836 < 0.9 + 0.4 444 1.9" - - 0.5 157 < 0.8 -- 0.1
334 4.O - - 4.7 83~ < 0.9 + 0-9 443 4.0 -- 2.6 255 3.3 + 2.8
333 3.0 -- 2.6 932 1.8 + 1.9 448 5.1 - - 4.3 254 2.8 + 2.3
332 4.5 + 5.4 933 0.5 + 0.5 449 < 1.3 + 0.1 253 < 1.1 -- 0.4
331 0.9 - - 1-3 934 2-2 - 2.3 446 < 1.0 + 0.4 252 1.9 -- 0.7
33i 0.8* + 0.9 933 < 0.5 + 0.2 440 < 0.8 + 0.1 251 < 1.1 + 0.4
33~ 5.6 - - 5.9 938 1.3 + 1.4 544 0-4 + O.4 25i 1.5 -- 3.0
238 THE CRYSTAL AND MOLECULAR STRUCTURE OF NAPHTHALENE. 1

Table 3 (cont.)
hkl F,~e~. ,F~ . hlcl Fmeas. Fcalc. hlcl Fmeas" F~¢. hlcl _~,,~. .F~I~.
25~ 6-6 -- 5.4 55~ 4"8 -- 4"2 16i 0"9 -- 0"7 56~: < 0.8 -- 0-5
253 6.0 -- 5"6 559 < i.0 + 0.3 16~ 1"7 -- 1"0 565 < 0.8 + 0.3
254 2.7 + 2:1 55~ 1.1 + 0.4 163 < 0"9 -- 0"3 566 < 0.8 + 0-8
25~ 3.6 + 3.3 651 0.8 - 0.5 16~ 2"7 + O'2 66i <0.4 + 0-1
256 1.1 + 1.0 65i O.8 + O.5 165 0"9 -- 1"5 66~ 0.4 + 0-4
25~ 0"7* + 0.8 65~ 3.4 + 3.4 166 < 0"9 -- 0"9 665 0-4 + 0-4
258 < 0.7 + 0.6 65~ 2.2 + 2.5 264 1"1 + 0"1 66~: < 0.4 + 0.4
355 < 0-8 + 0.5 65~ 0"7* -- 0.2 263 < 0"8 + 0"1 66~ 2-0 -- 1.4
354 < 0.9 + 0.1 655 1.7 + 1.3 262 4"8 -- 3"6 66~ 2.6 -- 2.2
353 < 0.8 + 0.1 65~ 1.3 + 1.8 261 7"4 -- 5"7 071 0.7 -- 0.7
352 0.8 -- 0.5 65q 0.5 + 0"7 26i < 1"0 + 1"0 072 , <0"5 + 0.3
351 2.7 -- 3.1 65~ < 0.5 -- 0"7 26'~ 3"5 -- 3"4 073 < 0.5 + 0-4
35i 1-6 + 1.4 75i < 0.8 -- 0'3 263 0"7 -- 0"9 074 < 0.5 -- 0.6
352 7.9 -- 6.3 75~ < 0.8 -- 0.6 264 < 1"2 + 1"5 170 < 0-6 + 0.6
353 4.3 -- 3-2 75~ < 0.9 -- 0.1 265 < 1"0 + 0"2 270 0-7* + 0.1
35~ 1.0 + 0.9 75,i < 0.9 + 0.3 26~ < 0'8 + 0'4 370 0.6 -- 0.7
3.5~ 5.5 - 4.3 75~ < 1.0 -- 0.5 363 < 0"8 -- 0"4 173 < 0.8 + 0.6
35~ 4.1 -- 3.3 75~ 2.5 -- 2.2 362 1"8 + 0"9 172 < 1.0 -- 0-1
35q < 1.0 + 0.6 75~ < 0.8 -- 0.5 361 2"5 + 1"9 171 1.8 -- 1-4
35~ < 0.9 -- 0.4 85~] < 0.7 + 1.5 36i < 0" 8 + 0"1 17i 1.8 + 0.4
454 0.4 + 0.7 857~ < 0.7 + 0.1 36~ 1"3 + 1"1 17~ < 1-0 -- 1-0
453 < 0.6 -- 0.5 85~ < 0.9 -- .0.9 365 < 0"9 -- 0"5 171] < 0.8 -- 0.4
452 1.8 -- 1.8 85~ < 0.7 -- 0.4 36~ 0"9 + 0"4 177~ < 0 . 8 + 0.1
451 3.6 -- 3.3 061 3.6 -- 4.0 365 0"8 -- 0"6 272 2.3 + 2-0
4 5i O-9 + 1.5 062 7.5 -- 6.7 366 < 0"7 -- 0"4 271 2.1 + 2.2
45~ 0~8 + 1-0 063 1.4 -- 0.6 367 < 0"7 + 0"1 27i 1.9 + 1-0
453 2.8 - 3.2 064 < 2.0 + 1.4 462 0"7 + 0"1 27~ 3.2 + 2-0
45,~ 1.1 + 0.5 065 < 2.0 + 0.5 461 < 0"8 -- 1"0 275 1.3 + 1.2
45~ 5.9 + 3.6 066 < 1.5 + 0.3 46i 1"0 + 1"4 27~ < 0.8 -- 0-8
45~ • 2.5 + 2.0 160 < 1.'0 -- 0.1 46~ O'9 + O'6 371 2-2 -- 1.0
457 < 0.6 + 0.6 260 1.1"* + 0.2 463 < 0'9 -- 0"2 37i O.7 + 1-1
45~ 0.4* + 0.3 360 < 0.9 -- 0.9 464 < 0"9 + 0"7 37~ < 0-7 + 0-2
552 0-4 + 0.5 460 < 0.9 -- 0.7 465 2"5 -- 1"7 37~ < 0.7 -- 0.5
551 1.0 + 0.6 560 <0.9 + 0.1 46~ 1"7 -- 1"6 374 < 0.7 -- 0.3
55i 1.0 -- 0.3 165 <0.9 + 1.2 467 < 0"8 + 0'4 47i < 0.8 -- 0.3
55~ 2.6 -- 2.1 164 < 0.9 + 0.4 561 0"7 + 0"6 47~ < 0.8 + 0.1
55~ 1.8 -- 1.9 163 < 1.0 -- 0.8 56i < 0"8 -- 0"2 473 1.3 + 1-3
55,~ 0.7 + 1.0 162 2.4 + 1.7 562 2"4 + 1"9 47~ < 0.7 -- 0.4
555 3.2 - 2.4 161 2.7 + 1.9 56fi 2"1 + 0"7

Acta Cryst. (1949). 2, 238

The Crystal and Molecular Structure of Naphthalene. H. Structure Investigation

by the Triple Fourier Series Method
B Y S. C. A B R ~ A M S , J. M O ~ T E A T H R O B ~ R T S O N AND (IN eART) J . G. WroTE

The University, Glasgow W. 2, Scotland

(Received 13 April 1949)

A t r i p l e F o u r i e r s e r i e s i n v e s t i g a t i o n o f t h e n a p h t h a l e n e s t r u c t u r e is d e s c r i b e d , b a s e d o n t h e 612
s t r u c t u r e f a c t o r s l i s t e d i n P a r t I. T h e s e r i e s f o r t h e e l e c t r o n d e n s i t y h a s b e e n e v a l u a t e d a t 5 4 , 0 0 0
points over the asymmetric crystal unit (half the chemical molecule), and the results are expressed
b y giving a n u m b e r o f sections t h r o u g h s e p a r a t e a t o m s a t different levels, a n d also b y giving a
section through the plane of the molecule. From this map the bond lengths can be determined by
d i r e c t m e a s u r e m e n t a n d a r e f o u n d t o v a r y f r o m 1 . 3 6 A. i n t h e a/? b o n d t o 1.42 A. i n t h e o a b o n d .
T h e / ? f l b o n d a n d t h e c e n t r a l b o n d , oo, a r e b o t h m e a s u r e d a t 1.395 A. T h e s e f i g u r e s a r e p r o b a b l y
c o r r e c t t o w i t h i n ' a b o u t 0.01 A . , a n d a p p e a r t o b e i n r e a s o n a b l y g o o d a g r e e m e n t w i t h t h e l a t e s t
t h e o r e t i c a l c a l c u l a t i o n s . T h e r i n g s a r e also f o u n d t o b e c o p l a n a r t o w i t h i n 0.01 A. T h e b r i d g e v a l u e
of the electron density varies in the different bonds; the electron distribution and the effect of the
hydrogen atoms are briefly discussed.

1. Introduction lone t h a t lie w i t h i n t h e r a n g e o f c o p p e r r a d i a t i o n . The

In Part I we have described the measurement and signs, or phase constants, of 612 of these factors can
l i s t e d t h e v a l u e s o f all t h e s t r u c t u r e f a c t o r s o f n a p h t h a - be determined from the previous approximate structure