A. J. G E D D E S AND IN PART D.

A K R I G G 3171

ions to provide reasonable coordination distances. In ESTRADA-O, S., GOMEZ-LOUERO, C. & MONTAL, M. (1972).
view of the close-packed nature of the observed struc- Bioenergetics, 3, 417-428.
ture this m a y not be an energetically favoured process, GERMAIN, G., MAIN, P. t~ WOOLFSON, M. M. (1971). Acta
in which case the ion would probably prefer to lie Cryst. A27, 368-376.
HAMILL, R. L., HIGGINS, C. E., BOAZ, H. E. & GORMAN, M.
closer to either the triad of MePh carbonyl O atoms or (1969). Tetrahedron Lett. pp. 4255-4258.
to the triad of H y l v carbonyl O atoms and there would HAMILTON, J. A., STEINRAUF, L. K. & BRADEN, B. (1975).
then be no good reason for choosing the inside rather Biochem. Biophys. Res. Commun. 64, 151-156.
than the outside of the cavity. At the m o m e n t there IUPAC-IUB COMMISSIONON BIOCHEMICALNOMENCLATURE
does not seem to be any experimental evidence for a (1970). J. Mol. Biol. 52, 1-17.
significant covalent contribution to the M + . . . O bond IVANOV, V. T., EVSTRATOV, A. V., SUMSKAYA,L. V., MEL-
which might cause the ion to prefer to be outside the NIK, E. I., CHUMBURIDZE,T. S., PORTNOVA, S. L., BALA-
cavity. SHOVA,T. A. & OVCHINNIKOV,YU. A. (1973). FEBS Lett.
36, 65-71.
Finally, we note that the crystal structure conforma-
KITAIGORODSKY, A. I. (1965). Acta Cryst. 18, 585-590.
tion of uncomplexed Bv crystallized from n-heptane MUELLER, P. & RUDIN, D. O. (1967). Biochem. Biophys.
is similar to that proposed by spectroscopic studies for Res. Commun. 26, 398-404.
Bv in polar solvents. The p r e d o m i n a n t environment of OVCHINNIKOV, Yu. A., IVANOV, V. T., EVSTRATOV, A. V.,
the molecule in the crystal is non-polar, with only 1 to MIKHALEVA, I. I., BYSTROV, V. F., PORTNOVA, S. L.,
2 molecules of water for each Bv molecule. The struc- BALASHOVA, T. A., MESHCHERYAKOVA, E. N. t~ TUL-
ture described would seem to be a likely candidate for the CHINSKY, V. M. (1974). Int. J. Peptide Protein Res. 6,
uncomplexed molecule within biological membranes. 465-498.
OVCHINNIKOV, Yu. A., IVANOV, V. T. & MIKHALEVA, I. I.
(1971). Tetrahedron Lett. 159-162.
I thank Dr Larry Steinrauf for suggesting the prob-
POPOV, E. M., PLETNEV, B. Z., EVSTRATOV,A. V., IVANOV,
lem and providing the material, the Indiana Univer- V. T. t~ OVCHINNIKOV,YU. A. (1970). Khim. Prir. Soedin.
sity Medical Centre for support over the period during 5, 616-622.
which the crystals were grown, the Leeds University PRINCE, R.. C., CROFTS, A. R. • STEINRAUF, L. K. (1974).
C o m p u t i n g Laboratory for facilities, Dr Bernard Shel- Biochem. Biophys. Res. Commun. 59, 697-703.
drick for help with data collection, and the M RC and ROESKE, R. W., ISAAC, S., KING, T. E. & STEINRAUF, L. K.
SRC for supporting the crystallographic studies. (1974). Biochem. Biophys. Res. Commun. 57, 554-
561.
STEWART, J. M., KRUGER, G. J., AMMON,H. L., DICKINSON,
References C. & HALL, S. R. (1972). The X-RAY system - version
DICKERSON, R. E. & GELS, I. (1969). In The Structure and of June 1972, Tech. Rep. TR-192. Computer Science
Action of Proteins. New York: Harper & Row. Center, Univ. of Maryland, College Park, Maryland.
DORSCHNER, E. & LARD',', H. (1968). Antimicrobial Agents YAFUSO, M., FREEMAN,A. R., STEINRAUF,L. K. & ROESKE,
Ann. pp. 11-19. R. W. (1974). Fed. Proc. Abstr. 33, 1258.

Acta Cryst. (1976). B32, 3171

The Crystal and Molecular Structure of 2,4-Dinitrophenol
BY TATSUIKI KAGAWA, RYOICHI KAWAI, SETSUO KASHINO AND MASAO HAISA
Department of Chemistry, Faculty of Science, Okayama University, Tsushima, Okayama 700, Japan

(Received 31 March 1976; accepted 30 April 1976)

The crystal structure of 2,4-dinitrophenol has been determined from visually estimated Cu K0c X-ray
data. The crystals are orthorhombic, space group P212121, with a = 6.106 (6), b = 23.24 (2), c= 5.168 (5)/~
and Z = 4. The structure was solved by the Patterson method and refined by block-diagonal least-squares
calculations to R=0.076 for 768 non-zero reflexions. The molecules related by an a translation are
stacked to form a column. The columns are held together by an interaction between the phenolic and
nitro groups [O. • • H 2.23 ,~,] of the molecules related by a twofold screw axis along the c axis, to form
a sheet parallel to (010). The sheets are stacked along the b axis by van der Waals interactions. The
molecule is nearly planar and the o-quinonoid nature of the benzene ring is remarkable. The phenolic
C-O bond length 1-331 (7) ,~, is appreciably shortened. The geometry of the intramolecular hydrogen
bonding between the phenolic and o-nitro groups is similar to that of the other o-nitrophenols [O. • •O
2-593 (7)/~, O - H . . . O 130 (6) °, H . . . O 1.89 (7) A].
Introduction Kashino & Haisa, 1976), the structure of 2,4-dinitro-
phenol, the prototype of 'uncouplers' of oxidative
As part of a p r o g r a m m e of studies on the crystal and phosphorylation (White, Handler & Smith, 1973), has
molecular structures of substituted phenols (Kawai, been studied by X-ray analysis. The main object of
3172 THE CRYSTAL AND MOLECULAR STRUCTURE OF 2,4-DINITROPHENOL

this w o r k is to study the g e o m e t r y o f i n t r a m o l e c u l a r and isotropic ones for the H atoms. The weighting
h y d r o g e n b o n d i n g in o-nitrophenols, especially those scheme a d o p t e d was w = 1.0 for 0 < IFol <- 5-0, and w =
having low acidity (pK,) values (Andersen & Andersen, (5.0/lFo[) 2 for IFol > 5.0. The final R value was 0.076 for
1975), a n d the molecular stacking a n d overlapping in 768 non-zero reflexions.*
the crystals. The a t o m i c scattering factors were t a k e n f r o m
International Tables .for X-ray Crystallography (1962).
Experimental
The c o m p u t a t i o n was carried out on an N E A C 2200-
2, 4-D in itr o p h en o l crystallizes f r o m an ethanol solution 500 c o m p u t e r at the O k a y a m a University C o m p u t e r
as yellow plates parallel to (010), elongated along [100] Center. The p r o g r a m s used were H B L S - 5 and D A P H
a n d b o u n d e d by {100} a n d {001}. (Ashida, 1973).

Crystal data
2,4-Dinitrophenol, C6HaNzOs, M . W . 184"1; m.p. * A list of structure factors has been deposited with the
1 1 2 - 1 1 3 ° C ; o r t h o r h o m b i c , a = 6 . 1 0 6 (6), b = 2 3 - 2 4 (2), British Library Lending Division as Supplementary Publica-
tion No. SUP 31888 (4 pp.). Copies may be obtained through
c = 5 . 1 6 8 (5).~,, V = 7 3 3 ( 1 ) A 3, D x = 1 " 6 6 7 for Z = 4 , The Executive Secretary, International Union of Crystallog-
D,, = 1.67 g c m - 3 (by flotation in a q u e o u s K I solution); raphy, 13 White Friars, Chester CH1 1NZ, England.
/~(Cu Ks) = 8.1 c m - 1, F(000) = 376; systematic absences
h00, h = o d d ; OkO, k = o d d ; 00/, l = o d d ; space g r o u p
P212t21.
Crystals with dimensions 0.6 × 0.2 z 0.5 and 0.3 ×
0.2 x 0.3 m m in glass capillaries were used to obtain
Weissenberg p h o t o g r a p h s for the layers Okl to 4kl and
hkO to hk4 respectively. Intensities were visually
estimated a n d corrected for Lorentz a n d polarization
factors a n d for spot shape. A total of 768 independent
reflexions ( 7 5 . 4 % of the total accessible in the Cu 2"926
sphere) were placed on an absolute scale by m e a n s of
a Wilson plot ( B = 5.1 A-').
...zL...~ ~~--z---or
S t r u c t u r e d e t e r m i n a t i o n and r e f i n e m e n t

Trial coordinates for the n o n - H a t o m s were obtained

f r o m a s h a r p e n e d P a t t e r s o n map. Block-diagonal
least-squares refinements with isotropic a n d then
anisotropic t h e r m a l p a r a m e t e r s reduced R f r o m 0.32 to
0.10. A t this stage, a difference F o u r i e r m a p revealed Fig. 1. Projection of the crystal structure viewed down the a
all the H atoms. All the positional p a r a m e t e r s in the axis. Broken lines show intermolecular contacts. Symmetry
code: (i) x,y,z; (ii) 1 +x,y,z; (iii) x,y, 1 +z; (iv)l +x,y, 1 +z;
final cycles o f refinement were included along with (v) ½--x,--y,--½+z; (vi) -- ½-- x, -- y, ½+z; (vii) 12+x,~-J-
anisotropic t h e r m a l p a r a m e t e r s for the n o n - H a t o m s y, --z.

Table 1. Final atomic parameters

Positional and thermal parameters for the non-H atoms are × 104 with their e.s.d.'s in parentheses. Positional parameters for
the H atoms are × 103. The flu's are defined by: exp (-h2p~t-kZ~22-12B33-hkfl~-hlp~3-klf123).
x y z /~,, /~22 /~33 /~,~ /~,3 /~=
0(1) - 1777 (6) 914 (2) 1291 (9) 295 (11) 19.9 (0.7) 568 (18) - 2 8 (5) - 132 (29) 13 (6)
0(2) -1194 (8) 186 (2) 5032 (10) 464 (16) 28.6 (0.9) 634 (22) - 1 0 2 (7) - 0 (35) 57 (8)
0(3) 1509 (8) 264 (2) 7621 (8) 464 (15) 22.0 (0.7) 442 (16) 10 (6) - 3 (30) 55 (6)
0(4) 6880 (8) 1741 (2) 6494 (10) 414 (14) 35.6 (1.1) 511 (19) - 5 7 (7) -493 (33) 53 (8)
0(5) 6737 (7) 2306 (2) 3245 (9) 347 (12) 21.8 (0.7) 521 (17) - 6 3 (5) - 1 (28) 15 (6)
N(1) 492 (8) 425 (2) 5773 (8) 352 (14) 16.8 (0.9) 384 (16) - 17 (5) 78 (29) 12 (6)
N(2) 6000 (7) 1913 (2) 4561 (8) 235 (I 1) 20.0 (0.8) 387 (16) - 2 2 (5) - 14 (26) - I0 (6)
C(1) 105 (9) 1127 (2) 2168 (10) 245 (13) 18.0 (0.9) 345 (18) - 1 (6) 2 (28) - 2 2 (7)
C(2) 1271 (8) 911 (2) 4296 (9) 268 (14) 14.6 (0-7) 310 (16) - 1 2 (6) 101 (28) - 5 (6)
C(3) 3231 (8) 1168 (2) 5074 (9) 257 (12) 15.7 (0.7) 308 (I 6) - 1 (6) - 20 (28) 4 (6)
C(4) 3972 (8) 1636 (2) 3728 (10) 220 (12) 15.8 (0.7) 334 (16) - 5 (5) 21 (28) - 10 (6)
C(5) 2856 (9) 1856 (2) 1627 (10) 303 (15) 15.9 (0.8) 331 (18) - 3 (6) - 6 5 (30) 10 (7)
C(6) 948 (9) 1603 (2) 859 (10) 280 (14) 18.0 (0-8) 354 (19) 9 (6) - 125 (31) 2 (7)
X y Z Biso (,~2) x y z Bi~o (/~2)
H(1) - 2 1 3 (12) 55 (3) 196 (14) 4.3 (1.6) H(3) 340 (11) 219 (3) 71 (13) 3-7 (1-4)
H(2) 397 (9) 103 (2) 682 (11) 2.4 (1.2) H(4) 13 (9) 172 (2) - 5 7 (10) 2.0 (1-2)
 T. K A G A W A , R. K A W A I , S. K A S H I N O AND M. H A I S A 3173

Results and discussion

93(6)
Crystal structure
114(3)~124(4)
The final atomic parameters with their estimated
s t a n d a r d deviations are listed in Table 1. The crystal ¢, -~ • ~21.1(5)~20(4)//0.97(7) ',
0"9 4 ( 7 ) A ~ 1 " 3 3 1 ( 7 ) ~ ~ ',
structure viewed down the a axis is illustrated in Fig. 1.
The molecules related by an a translation are stacked
," ,/ \
by a dipole-dipole interaction between the phenolic
and nitro groups as shown in Fig. 2, to form a column " / l -- / IZ 2.1t5)~ 119"1(5) /
along the a axis. The molecular overlapping is less than
in 2-nitro-4-chlorophenol (Kawai, Kashino & Haisa, ,,)," ~ ~ , ~ , ~ z ~ . , c ~ )
1976). The columns are held together by an interaction ~%o~c~ /'"°'~' "W /
between the atoms 0 ( 2 ) and H(1 vi) of the molecules /, 2o=.
related by a twofold screw axis along the c axis to form
a sheet parallel to (010). The 0 ( 2 ) . . . H(1 vi) distance is /'-71 2.44(6)
..........
2.23 A but the angle 0 ( 2 ) . . . H ( l V i ) - O ( 1 v~) is 129 °, so 1.199(7) ...... @. . . . . .
that the interaction c a n n o t be described as a bifurcated
hydrogen bond. Such a situation has been discussed for
7-glycine (J6nsson & Kvick, 1972). The contact is Fig. 3. Bond lengths (/~,) and bond angles (°), with their
closer than the similar contact in 2-nitro-4-chlorophen- e.s.d.'s in parentheses.
ol [ O . . . H ( O 2 'v) 2.45 ,A,, O ( 1 ) . . . H(O2i~)-O(2 ~v) 124 °,
O ( 1 ) . . . O(2i0 3.029/~], hence the higher melting point.
Table 2. The least-squares planes and displacements (~)
of the atoms from the planes
x, Y and Z refer to the crystallographic axes in ~. Atoms
with an asterisk were used for the calculation of the plane.
(I) Benzene ring
0.5110X- 0.6073 Y - 0.6084Z+ 2.2387-- 0
C(1)* -0"001 O(1) -0"012 N(2) --0"024
C(2)* -0"002 0(2) 0-022 H(I) 0.18
C(3)* 0"004 0(3) -0"059 H(2) -0.13
C(4)* -0-003 0(4) -0.113 H(3) -0.01
C(5)* - 0.001 0(5) 0.066 H(4) 0.03
C(6)* 0.003 N(1) -0.022
(II) 4-Nitro group
0.5259x- 0.6563 Y - 0.541 o z + 2.2624 = 0
"-" : "" . ,.3 ii 0(4)* 0.001 N(2)* -0.004 C(3) 0.101
" " ! T 0(5)* 0.001 C(4)* 0.001 C(5) -0.105
(III) 2-Nitro group
!
0.5377X- 0.6113 Y - 0"5807Z+ 2-1684 = 0
/ 0(2)* 0"002 N(1)* -0.006 C(1) -0.049
<3.4,50 /
" 3.14 0(3)* 0"002 C(2)* 0.002 C(3) 0.048
.."3.207
(IV) Chelate ring
"~o -:" " z' .3 iii 0.5516X-O.5879Y-O.5917Z+ 2.1651 =0
Fig 2. The molecular overlapping and stacking, together with O(1)* -0.077 C(1)* -0.003 C(3) 0.107
inter-ring spacing (A,) and intermolecular distances (/~,). 0(2)* - 0.030 C(2)* 0.034 C(6) 0.032
The symmetry code is given in the legend of Fig. 1. N(1)* --0.015 H(1)* 0.10

Table 3. The 0 . . . 0 contact (/~,), torsion angles z (°) and bond angles (o)
characteristic of the intramolecular hydrogen bonding of o-nitrophenols
(a) (b) (c) (d) (e) (f)
O(1)... 0(2) 2.546 2.557 2-558 2.587 2-593 2.599
T[H(1)-O(1)-C(1)-C(2)] 1.9 -4-2 13.6 -5-3 -13.5 -5.7
r[O(I)-C(1)-C(2)-N(1)] -2-3 0.9 - 1-7 -0.1 -0.4 0.2
r[C(1)-C(2)-N(1)-O(2)] 3.6 - 0.8 - 4.6 - 0.2 3.2 - 8.6
C(2)-C(I)-O(1) 125.0 123.8 124.8 125-5 124.9 125.5
N(1)-C(2)-C(I) 119-7 120-9 120.1 120.6 121.8 120.7
References: (a) n-Molecular compound anthracene-picric acid (Herbstein & Kaftory, 1976). (b) 2,6-Dinitrophenol (Iwasaki,
Sato & Aihara, 1976). (c) 2-Chloro-4,6-dinitrophenol (Andersen & Andersen, 1975). (d) 2-Nitro-4-chlorophenol (Kawai,
Kashino & Haisa, 1976). (e) 2,4-Dinitrophenol (this work). (f) 2-Bromo-4,6-dinitrophenol (Neustadt & Cagle, 1975).
3174 THE CRYSTAL AND MOLECULAR STRUCTURE OF 2 , 4 - D I N I T R O P H E N O L

C-O bond length (A)

Molecular structure
1"42
Bond lengths and angles are shown in Fig. 3. The
18
least-squares planes and the displacements of the atoms
25
1'40 o 26 21, Qe.~0
from the planes are listed in Table 2. The benzene ring
is planar within 0.004 A and makes dihedral angles of
2.2 and 4.9 ° with the nitro groups at the C(2) and C(4)
"'. positions, respectively, and 2.8 ° with the chelate ring.
I b , j ~ _~2 e11 el3
The o-quinonoid nature of the benzene ring is remark-
012 10 ^ . able, as in 2-nitro-4-chlorophenol and 2-bromo-4,6-
dinitrophenol (Neustadt & Cagle, 1975). The C-N
1"35 bond lengths are rather short but agree well with the
values C(2)-N(1) 1.457, C(4)-N(2) 1.460 A calculated
from the O - N - O angle by the formula proposed by
Kawai, Kashino & Haisa (1976). The C(1)-O(1) length
is appreciably shortened as compared with the normal
phenolic C-O length 1.368 A (Brown, 1959) and agrees
1"30
well with the value expected for a p K , of 4.0 (Kolesnik,
I I !
5 10 14 1974) from the plot of Andersen & Andersen (1975).
pKa Fig. 4 shows the phenolic C(sp~)-O bond lengths of
Fig. 4. The phenolic C(spZ)-O bond lengths vs the pKa values, phenols vs the p K , values based on the complementary
based on the complementary data for the Andersen & data for the Andersen & Andersen plot. Thus the con-
Andersen plot (solid line). Open circles denote ortho sub- traction of the phenolic C-O bond is possibly related to
stituted phenols having intramolecular hydrogen bonding.
References for bond lengths: (1) :r-Molecular compound high conjugation in o-nitrophenols and to the mecha-
anthracene-picric acid (Herbstein & Kaftory, 1976). (2) 2- nism of their uncoupling action.
Bromo-4,6-dinitrophenol (Neustadt & Cagle, 1975). (3) 2,4- The angle C(5)-C(4)-C(3) is close to, and the angles
Dinitrophenol (this work). (4) 2,6-Dinitrophenol (Iwasaki, C(1)-C(2)-C(3) and C(6)-C(1)-C(2) are smaller than
Sato & Aihara, 1976). (5) 2-Nitro-4-chlorophenol (Kawai,
Kashino & Haisa, 1976). (6) Salicylic acid (Sundaralingam & the values predicted from the electronegativity of the
Jensen, 1965). (7) p-Hydroxybenzaldehyde (Iwasaki, Sato & substituents (Domenicano, Mazzeo & Vaciago, 1975).
Aihara, 1973). (8) 3-Hydroxy-4-methoxybenzaldehyde (lwa- On the geometry of intramolecular hydrogen bond-
saki, 1973). (9) p-Hydroxybenzoic acid monohydrate ing in o-nitrophenols, it may generally be said from
(Fukuyama, Ohkura, Kashino & Haisa, 1973). (10) Piper-
idinium p-hydroxybenzoate (Fukuyama, Kashino & Haisa, Table 3 that the O ( 1 ) . - . 0 ( 2 ) contact remains short,
1973). (11)p-Chlorophenol, a-form (Perrin & Michel, the torsion angles about the O(I)-C(1), C(1)-C(2)
1973a). (12) m-Nitrophenol (Pandarese, Ungaretti & Coda, and C(2)-N(1) bonds are relatively small, and the
1975). (13) 2,6-Dimethylphenol (Antona, Longchambon, widening of the bond angles C(2)-C(1)-O(1) and N(1)-
Vandenborre & Becker, 1973). (14) 3,5-Dichlorophenol
(Bavoux & Thozet, 1973). (15) 2,5-Dichlorophenol (Bavoux C(2)-C(1) is significant. The H(I) atom in the present
& Perrin, 1973). (16) 2,6-Dichlorophenol (Bavoux & compound twists appreciably against the C(2) atom
Michel, 1973). (17) m-Aminophenol (De Rango, Brunie, about the C(1)-O(I) bond.
Tsoucaris, Declercq & Germain, 1974). (18) m-Cresol (Bois,
1973). (19) o-Cresol (Bois, 1972). (20) 3,4-Dimethylphenol
(Vandenborre, Gillier-Pandraud, Antona & Becker, 1973). References
(21) p-Chlorophenol, //-form (Perrin & Michel, 1973b). /~kGREN, A. (1956). Svensk Kem. Tidskr. 68, 189-199.
(22) p-Cresol, metastable form (Perrin & Thozet, 1974). ANDERSEN, E. g. ~ ANDERSEN, ]. G. K. (1975). Acta Cryst.
(23) p-Cresol (Bois, 1970). (24) 2,5-Dimethylphenol (Neu- 831,387-390.
man & Gillier-Pandraud, 1973). (25) 2,3-Dimethylphenol
(Neuman & Gillier-Pandraud, 1973). (26) 2-Methyl-3- ANTONA, D., LONGCHAMBON, F., VANDENBORRE, M. T.
bromophenol (Maze-Baudet, 1973). (27) Salicylaldehyde BECKER, P. (1973). Acta Cryst. 829, 1372-1376.
(Bourre-Maladi6re, 1953). (28) Salicylamide (Sasada, ASHIDA, T. (1973). The Universal Crystallographic Com-
Takano & Kakudo, 1964). ThepK, values for salicylaldehyde puting System - Osaka. The Computation Center, Osaka
(27) and salicylamide (28) were taken from ,~gren (1956), Univ.
and those for the other phenols were estimated from the Bgvoux, C. & MICHEL, P. (1973). Acta Cryst. B30, 2043-
table of Brown, McDaniel & Hfifliger (1955). 2045.
BAVOUX,C. & PERmN, M. (1973). Acta Cryst. B29, 666-668.
BAVOUX, C. & THOZET, A. (1973). Aeta Cryst. B29, 2603-
In accordance with the structure, the crystals have 2605.
developed (010) planes. BoIs, C. (1970). Acta Cryst. B26, 2086-2092.
The sheets are stacked along the b axis by weak van Bols, C. (1972). Acta Cryst. B28, 25-31.
der Waals interactions; the shortest contacts are found BoIs, C. (1973). Acta Cryst. B29, 1011-1017.
between the atoms 0 ( 4 ) . . . H(4 iv) and 0 ( 5 ) . . . H(3VJi). BOURRE-MALADI/~RE, P. (1953). C. R. Acad. Sci. Paris, 237,
825-827.
These contacts and 0 ( 4 ) . . . C ( 1 ii) may co-operatively
BROWN, H. C., MCDANIEL, D. H. & H.g.FLIGER, O. (1955).
inhibit the nitro group at the C(4) atom causing it Determination of Organic Structures by Physical Methods,
to undergo torsional librations about the C(4)-N(2) edited by E. A. BRAUDE & F. C. NACHOD, pp. 567-662.
bond. New York: Academic Press.
 T. K A G A W A , R. K A W A I , S. K A S H I N O AND M. H A I S A 3175

BROWN, M. G. (1959). Trans. Faraday Soc. 55, 694-701. KOLESNIK, M. I. (1974). Zh. Fiz. Khim. 48, 1114-1118.
DE RANGO, C., BRUNIE, S., TSOUCARIS,G., DECLERCQ,J. P. MAZE-BAUDET, M. (1973). Acta Cryst. B29, 602-614.
& GERMAIN,G. (1974). Cryst. Struct. Commun. 3, 485-487. NEUMAN, A. & GILLIER-PANDRAUD, H. (1973). Acta Cryst.
DOMENICANO, A., MAZZEO, P. & VACIAGO,A. (1975). Acta B29, 1017-1023.
Cryst. A31, S117. NEUSTADT, R. J. & CAGLE. F. W. JR (1975). Acta Cryst.
FUKUYAMA, K., KASrtINO, S. & HAISA, M. (1973). Acta B31, 2727-2729.
Cryst. B29, 2713-2717. PANDARESE, F., UNGARETTI,L. & CODA, A. (1975). Acta
FUKUYAMA, K., OHKURA, K., KASHINO, S. & HAISA, M. Cryst. B31, 2671-2675.
(1973). Bull. Chem. Soc. Japan, 46, 804-808. PERRIN, M. & MICHEL, P. (1973a). Acta Cryst. B29, 253-
HERBSTEIN, F. H. & KAFTORY,M. (1976). Acta Cryst. B32, 258.
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Acta Cryst. (1976). B32, 3175

Structure Cristalline de l'Orthotrithioars~nite Trisodique, Na3AsS3

PAR MARCEL PALAZZI

Laboratoire de Chimie MinOrale Structurale LA 200 (Laboratoire de Physique), FacultO des Sciences
Pharmaceutiques et Biologiques de Paris Luxembourg, 4 avenue de l'Observatoire, 75270 Paris COdex 06, France

(Recu le 12 mai 1976, acceptk le 31 mai 1976)

Na3AsS3 crystallizes in the cubic system with a = 8.566 ,~, space group P213. The structure was solved
and refined to a final R value of 0.032 for 320 independent single-crystal reflexions. The coordination
number of Na is six. The position of the unbound electron pair of As m is found at about 1.25 ,~ from
the As atom.

Introduction pour la d6termination de la structure ont 6t6 obtenus

apr~s fusion et recristallisation du produit en poudre
Apr6s l'6tude des thioars6niates (AsV): anhydre (Palazzi, par la m6thode de Bridgman.
Jaulmes & Laruelle, 1974) et hydrat6s (Palazzi, Na3AsS3 est tras sensible /t l'action de l'eau. De
1976; Jaulmes & Palazzi, 1976), nous avons entrepris couleur marron clair lorsqu'il est maintenu dans une
celle des thioars6nites (Asm). atmosph6re s6che il devient marron fonc6 et se d6com-
En 6tudiant les structures de Na3AsS3 et N a A s S / n o u s pose au contact de l'eau.
cherchons, d'une part, /t connaitre les modes d'en- Afin d'6viter que le monocristal ne se d6compose
chainements des atomes d'arsenic (lin6aire, ramifi6 ou durant les mesures, en pr6sence d'air humide, il est
cyclique), et d'autre part, ~t d6terminer le r61e st6r6o- isol6 dans un capillaire en pyrex, ~ parois tr~s minces,
chimique 6ventuel du doublet solitaire de As ~I~. scell6 aux extr6mit6s.

Pr6paration Donn6es cristallographiques

L'orthotrithioars6nite trisodique, NaaAsS3, a 6t6 pr6- La mesure du param~tre et la d6termination du groupe
par6, pour la premi6re fois, par r6action dans l'6tat spatial ont 6t6 effectu6es ~t partir des diagrammes d'os-
solide entre As2S3 et Na2S dans la proportion de 1 mol cillation, de Weissenberg et de pr6cession avec la ra-
pour 3 (Palazzi, 1972). Le m61ange homog6ne des deux diation Mo Koc. Na3AsS3 cristallise dans le syst~me
sulfures est comprim6 en pastilles et chauff6 sous at- cubique.
mosph6re d'azote ~. 220°C. Les monocristaux utilis6s Les r6flexions observ6es sur les diff6rents clich6s de