188 C23H22N4OTS2
Fig. 2. Molecula packing iewed down he b axis.
The glycosyl o sion angle C(2)--N(1)-C(1')--O(4')
is --74.2 (2) °. The suga pucke is in a wis ed o m,
C(4')-endo-C(3')-exo,
wi h pseudo o a ion angle P
= 220.9 o as de ined by Al ona & Sunda alingam (1972).
A simila con o ma ion is also obse ed in 8,2'-
O-cycloadenosine (P=217.5 °) and in 8,2'-S-cyclo-
5'-AMP (P= 232.7°).
The molecula packing is illus a ed in Fig. 2. A
hyd ogen bond is obse ed be ween 0(5') and N(3) in
he neighbou ing molecule ela ed by he 21 sc ew axis.
Re e ences
ALTONA, C. & SUNDARALINGAM~ M. (1972).
J. Am. Chem. Soc.
94,
8205-8212.
ASHIDA, T. (1979).
HBLSV. The Uni e sal C ys allog aphic
Compu ing Sys em-Osaka.
Lib a y o P og ams, Compu ing
Cen e , Osaka Uni .
In e na ional Tables o X- ay C ys allog aphy
(1974). Vol. IV.
Bi mingham: Kynoch P ess.
JOHNSON, C. K. (1976).
ORTEPII.
Repo ORNL-5138. Oak
Ridge Na ional Labo a o y, Tennessee.
KITAMURA, K., MIZL NO, H., SUGIO, S., OKABE, N., IKEHARA, M. &
ToM A, K. (1983).
Ac a C ys .
C39, 1551-1553.
MAIN, P.,
HULL, S.
E., LESSINGER, L., GERMAIN, G.,
DECLERCQ,
J.-P. & WOOLFSON, M. M. (1978).
MULTAN78. A Sys em o
Compu e P og ams o he Au oma ic Solu ion o C ys al
S uc u es om X- ay Di ac ion Da a.
Uni s. o Yo k,
England, and Lou ain, Belgium.
NEIDLE, S., TAYLOR, G. L. & COWLING, P. C.
(1979).
Ac a C ys .
B35, 708-712.
TANAKA, K., FuJn, S., FUJIWARA, T. & TOMITA, K. (1979).
Ac a
C ys .
B35, 929-933.
Ac a C ys .
(1984). C40, 188-190
S uc u e o l-(p-E hoxyphenyl)-1,3-dihyd o-3-phenyl-2H-benzimidazole-2- hione,
C2IHlaN2OS
BY A. CRIADO, A. CONDE AND R. M.~,RQUEZ
Depa amen o de Op ica y Secci6n de F sica del Cen o Coo dinado de CSIC, Uni e sidad de Se illa, Spain
(Recei ed
18
Ap il
1983;
accep ed
21
Sep embe
1983)
Abs ac . M =346-4, o ho hombic, P212121, a=
7.600(1), b= 11.132(2), c=20.767
(3)A,
=
1756.9(5)A 3, z=4,
Dx=1.31Mgm
-3, 2(CuKc )
=.1.5418/k, /~= 1.67mm -1, F(000)=728, T=
300 K. Final R = 0.049 o 1531 obse ed independen
e lec ions. The benzimid~zole bicycle is quasi-plana ,
he dihed al angle be ween he wo used ings being
1.6 (2) °. The unsubs i u ed phenyl ing is plana while
he phenyl ing wi h he e hoxy subs i uen de ia es
signi ican ly om he expec ed plana con o ma ion.
In oduc ion. The c ys al s uc u e o he i le com-
pound has been de e mined as pa o a sys ema ic
s uc u al analysis o imidazole C-nucleosides syn-
hesized in he O ganic Chemis y Depa men o his
Uni e si y. Recen ly, we ha e epo ed (C iado, Conde
& M~ quez, 1983) he s uc u e o he i s disubs i u ed
(a bo h N a oms) imidazole C-nucleoside.
0108-2701/84/010188-03501.50
The i le compound (I) has been ob ained
(Fe nb.ndez-Bola ios, Fuen es-Mo a & Fe n indez-
Bola ios Guzmhn, 1983a) om he p- oluene-
sul ona e o 4-( l-D-e y h o u anosyl)-l-(p-e hoxyphen-
yl)-l,3-dihyd o-3-phenyl-2H-imidazole-2- hione (Fe -
nimdez-Bola ios, Fuen es-Mo a & Fe nhndez-Bola ios
Guzm~m, 1983b) using a eac ion simila o ha o
Tipson & Cohen (1965). This syn hesis is he i s
case o nucleoside a oma iza ion.
s
C2H 5
(I)
© 1984 In e na ional Union o C ys allog aphy
A. CRIADO, A. CONDE AND R. M/~RQUEZ 189
Expe imen al. Needle-shaped colo less c ys als,
0.05 ×0.06x0.14mm, kindly supplied by P o-
esso Fe n indez-Bola ios o he O ganic Chemis y
Depa men o his Uni e si y; p elimina y s udies
showed o ho hombic symme y, sys ema ic absences
consis en wi h P212~2~. Philips PW 1100 ou -ci cle
compu e -con olled di ac ome e , g aphi e-mono-
ch oma ed adia ion. Uni -cell pa ame e s om leas -
squa es e inemen o ~ alues o 33 e lec ions. 1729
e lec ions wi h 0<65 ° (h<9, k< 14, l<25)
measu ed, 09-20 scan mode, 1531 wi h I> 2o(1)
X
conside ed obse ed. Two e e ence e lec ions mon- s 52527(18)
i o ed pe iodically, in ensi y changes less han 2%. 0(I) -4101(48)
Lo en z and pola iza ion co ec ions, none o ab- N(1) 52808(54)
N(2) 73068 (55)
so p ion o ex inc ion e ec s. Weigh ed angen - c(1) 59232(63)
o mula e inemen (MULTAN78, Main, Hull, Les- c(2) 62185(64)
singe , Ge main, Decle cq & Wool son, 1978) o 180 c(3) 75071 (67)
c(4) 86847 (76)
e lec ions wi h E> 1.5. Full.ma ix leas -squa es c(5) 85689(85)
e inemen o 281 pa ame e s based on F o o e all c(6) 72880(88)
C(7) 61161 (75)
obse ed e lec ions (CR YLSQ o XRAY70, S ewa , c(8) 37658 (65)
Kundell & Baldwin, 1970). Fou ie di e ence syn hesis c(9) 37768 (70)
up o sin0/2= 0.7,~-~ ga e all H-a om posi ions; a
c(1o)
23521
(75)
C(I 1) 9032 (68)
leas -squa es e inemen in a mixed mode including H c(12) 8414 (67)
a oms, each one wi h an iso opic empe a u e ac o c(13) 23083 (72)
equal o ha o he a ached skele on a om, ga e c(14) -20360(76)
c(15) -32549 (77)
R--R,= 0.049. Las -cycle pa ame e shi s less han c(16) 84187 (65)
0.34, a e age 0.1a. Final di e ence Fou ie map c(17) 101124(72)
c(18) 112177 (73)
excu sions --0.25 <Ap < 0.35 e A -~. A omic sca - c(19) 105956(72)
e ing ac o s om In e na ional Tables o X- ay c(20) 88844(83)
C ys allog aphy (1974). Weigh ing scheme in he o m c(21) 77897 (77)
1/a2(I) based on coun ing s a is ics.
Discussion. Final a omic coo dina es and equi alen
iso opic empe a u e ac o s (Hamil on, 1959) a e
gi en in Table 1.* Bond leng hs and angles o he
non-H a oms a e gi en in Fig. 1. The C-H dis ances
ange om 0.95 o 1.19/k, wi h a mean alue o
1.08 (6) A,.
Benzimidazole ing. Bond dis ances and angles in he
imidazole ing a e in good ag eemen wi h he epo ed
alues o imidazole-2- hione compounds (Conde,
L pez-Cas o & M i quez, 1978; C iado e al., 1983)
showing no app eciable dis o ion due o he bicycle
o ma ion. Only he C(2)-C(3) bond dis ance is
somewha long in compa ison wi h he mean alue
[ 1.345 (5)/k] o he o emen ioned compounds. The ing
keeps i s plana ea u e and he a omic de ia ion~ om
he leas -squa es plane h ough he i e a oms a e
wi hin he s anda d de ia ions (Z z = 0.72). The benzene
ing, on he con a y, shows an app eciable dis o ion
om plana i y (Zz= 27.39,), wi h a oms whose dis ance
* Lis s o s uc u e ac o s, aniso opic he mal pa ame e s,
H-a om coo dina es and leas -squa es-planes' da a ha e been
deposi ed wi h he B i ish Lib a y Lending Di ision as Supplemen-
a y Publica ion No. SUP 38889 (1"2' pp.). Copies may be ob ained
h ough The Execu i e Sec e a y, In e na ional Union o C ys al-
log aphy, 5 Abbey Squa e, Ches e CH 1 2HU, England.
o he leas -squa es plane is g ea e han h ee s anda d
de ia ions. The a e age C-C bond leng h in he ing is
1.389 (7)A and C-C-C angle is 120.0 (5) °. The
whole bicycle is quasi-plana , he dihed al angle
be ween he imidazole and benzene leas -squa es planes
being 1.6 (2) ° .
Table 1. Posi ional pa ame e s (x l0 s) and equi alen
iso opic he mal pa ame e s (x 104) o he non-H
a oms wi h e.s.d. 's in pa en heses
y z U~,(M)
10175 (13) -2312"9 (6) 450 (4)
-27848 (31) -11181 (18) 501 ('12)
3744 (34) -10470 (19) 365 (12)
16914 (35) -13045 (19) 365 (13)
10275 (44) -15567 (22) 371 (14)
6115 (41) -4873 (22) 351 (15)
14402 (41) -6487 (23) 362 (15)
18824 (47) "2034 (25) 475 (18)
14255 (53) 4187 (27) 549 (20)
5597 (52) 5804 (26) 542 (20)
1292 (45) 1287 (24) 430 (16)
-4036 (42) -10742 (23) 372 (15)
-14158 (46) -14696 (25) 432 (16)
-21796 (45) -14697 (26) 447 (17)
-19503 (44) -10830 (24) 394 (15)
-9217 (47) -6999 (23) 411 (15)
-1425 (45) -7045 (25) 404 (16)
-25485 (55) -7782 (31) 568 (21)
-35714 (56) -9505 (32) 577 (21)
24958 (46) -16586 (23) 377 (15)
21513 (47) -18020 (26) 465 (18)
29465 (54) -21276 (28) 542 (20)
40733 (53) -23039 (28) 536 (19)
43990 (52) -21639 (32) 608 (22)
36129 (48) -18433 (30) 531 (20)
Gi9)
el .e- **,,-I=
@ ~ ~ -~/ ,2,0
~,o'
c~,),~B;),,,~ "
, 00
115.1 ~ _~./"'~
105. 7 '~'~(C(l ,)
C( 51
Fig. 1. Bond leng hs (A) and angles (o) in he molecule. S anda d
de ia ions a e below 0.009 A and 0.6 °.
190 C21HIsN2OS
The dihed al angles o med by he imidazole ing and
he wo bound phenyl ings a e 73.7 (2) ° o he
N(2)-a ached ing and 61.4 (2) ° o he N(1)-a ached
ing, bo h alues being simila o hose encoun e ed in
he analogous compounds s udied p e iously, anging
om 60 o 80 ° . The o sional angles desc ibing he
bonding a e C(1)-N(1)-C(8)-C(9)=63.5 (6) and
C ( 1 )-N(2)-C ( 16)-C (21) = 75.2 (7)0, espec i ely.
PhenyI ings.
The N(2)-a ached phenyl ing is
plana , wi h a omic de ia ions om he mean plane
wi hin he s anda d de ia ions (Z 2 = 4.52). The a e age
C-C bond leng h is 1.385 (8)A and he mean
C-C-C angle is 120.0 (5) °. The N(1)-a ached phenyl
ing, on he con a y, de ia es signi ican ly om he
expec ed plana con o ma ion (Z2= 29.07), wi h an
a e age C-C bond leng h o 1.390 (7) A and C-C-C
angle o 120.0
(5) ° .
The e hoxy g oup exhibi s asymme y in he C(10)-
C(ll)-O(1)= 115.1 (5) and C(12)-C(II)-O(1)=
124.4 (5) ° angles, a common ea u e o he phenoxy
g oup (Domiano, Na delli, Balsamo, Macchia &
Macchia, 1979).
Fig. 2 shows a iew o he uni cell along he b axis.
No e idence o hyd ogen bonds exis s and no
in e molecula con ac s app eciably sho e han he
sum o he an de Waals adii ha e been de ec ed.
The au ho s hank P o esso Fe nandez-Bola ios. o
supplying he c ys als and he s a o he Ins i u o
'Rocasolano' o CSIC (Mad id) o collec ing he
di ac ome e da a. The p esen wo k o ms pa o a
wide esea ch p ojec suppo ed by he Go e nmen
h ough he 'Comisi6n Aseso a de In es igaci6n Cien-
i ica y T6cnica'.
1~I/4 1,1/4
,..,c(181
[ •
/
C(19)(~ 4~C( 17)~, al ,,
/
cCI( 154 'I/4 'I/4
Fig. 2. Uni cell iewed along he b axis.
Re e ences
CONDE, A., LOPEZ-CASTRO, A. & MARQUEZ, R. (1978).
Re .
Ibe oam. C is alog . Mine . Me alogen.
1, 23-26.
CRIADO, A., CONDE, A. & MARQUEZ, R. (1983).
Ac a C ys .
C39,
122-125.
DOMIANO, P., NARDELL , M., BALSAMO, A., MACCHIA, B. &
MACCI- IA, F. (1979).
Ac a C ys .
B35, 1363-1372.
FERNANDEZ-BOLA~OS, J., FUENTES-MOTA, J. & FERNANDEZ-
BOLAg OS GUZ ~N, J. (1983a).
Ca bohyd . Res.
To be published.
FERNANDEZ-BOLA~OS, J., FUENTES-MOTA, J. & FERNA , DEZ-
BOLA~OS GUZMAN, J. (1983b).
An. Qu m.
To be published.
HAMILTON, W. C. (1959).
Ac a C ys .
12, 609-610.
In e na ional Tables o X- ay C ys allog aphy
(1974). Vol. IV.
Bi mingham: Kynoch P ess.
MAIN, P., HULL, S. E., LESSINGER, L., GERMAIN, G., DECLERCQ,
J.-P. & WOOLFSON, M. M. (1978).
MULTAN78. A Sys em o
Compu e P og ams o he Au oma ic Solu ion o C ys al
S uc u es om X- ay Di ac ion Da a.
Uni s. o Yo k,
England, and Lou ain, Belgium.
STEWART, J. M., KUNDELL, F. A. & BALDWIN, J. C. (1970). The
XRAY70 sys em. Compu e Science Cen e , Uni . o Ma yland,
College Pa k, Ma yland.
TlPSON, R. S. & COHEN, A. (1965).
Ca bohyd . Res.
1, 338-340.
Ac a C ys .
(1984). C40, 190-193
2-(l,3-Di hiol-2-ylidene)-4-eyclopen ene- 1,3-dione,
CaH40282,
and 2-(l,3-Benzodi hiol-
2-ylidene)cyclohexanone,
CI3H12OS 2
BY WILLIAM H.
WATSON, JEAN GALLOY AND DAVID A. GROSSIE
FASTBIOS Labo a o y, Depa men o Chemis y, Texas Ch is ian Uni e si y, Fo Wo h, TX
76129,
USA
AND Juzo NAKAYAMA
Depa men o Chemis y, Facul y o Science, Sai ama Uni e si y, U awa, Sai ama
338,
Japan
(Recei ed
22
July
1983;
accep ed
22
Sep embe
1983)
Abs ac .
C8H40252
(2),
M =
196.25, o ho hombic,
Pnma,
a = 18.080 (2), b = 1 I. 102 (I), c =
3.8904 (4) A, V= 780.9 (1) A 3, z= 4, Dx=
1-67Mgm -3, CuKa, 2=1.54178A, #=5.549
mm -l, F(000)=400, oom empe a u e, R =0.046
based on 597 unique e lec ions. CI3HI:OS 2 (3),
M
0108-2701/84/010190-04501.50
= 248.24, monoclinic,
P21/c,
a= 6.459 (1), b=
14-263 (3), c= 13.514 (4)A, l--- 112.16 (2) ° , V=
1153.0 (6) A 3, Z = 4,
D x
= 1.43 Mg m -3, Cu Kc , #
= 3.90 mm -x, F(000) = 520, oom empe a u e, R =
0.074 based on 1429 unique e lec ions. Compound (2)
is plana excep o a sligh 2 ° old along he S.-.S line.
© 1984 In e na ional Union o C ys allog aphy