898
Ac a C ys .
(1984). C40, 898-901
•
S uc u e o l'-(p-B omophenyl)-3'-e hyl- 1',3 ,4',5 - e ahyd o-
1,2-¢~deoxy-D-glyee o-D-
gu/a-hep o u anoso[ 1,2-d]imidazole-2'- hione,* C16H21B N2OsS
BY M. D. ESTRADA, A. CONDE AND R. MARQUEZ
Depa amen o de F sica del Es ado S6lido, Facul ad de F sica, Uni e sidad de Se illa, Spain
(Recei ed
14
Sep embe
1983;
accep ed 1 Feb ua y
1984)
Abs ac .
M
= 433.3, monoclinic, P21, a = 6.924 (3),
b=8.661 (1), c=15.039(3)A, #=96.92(3) ° , =
895.3 (4) A a, Z= 2, D, = 1.598 (5), Dx=
1.607 Mg m -a, Mo Ka, 2 = 0.7107/k, # = 2.42 mm -1,
F(000) = 444, T = 300 K, R = 0.039 o 2038 ob-
se ed independen e lexions. The suga ing adop s a
4E con o ma ion and he dihed al angle in he bicycle
is 49.0 (2) °. In e molecula hyd ogen bonds link he
molecules o o m a h ee-dimensional ne wo k.
In oduc ion.
The s uc u e de e mina ion o he i le
compound (I) was unde aken as pa o a con inuing
esea ch p ojec in his labo a o y in ol ing
glucimidazoles and imidazole C-nucleosides. Com-
pounds ob ained by eac ion o 2-deoxy-2-e hyl(p opyl)-
aminohexose(hep ose) wi h a yl (alkyl) iso hiocyan-
a es (Ga cia Gonzalez, Galbis-Pd ez, Fe nandez-
Ga cia-Hie o & Fe n indez-Bola ios, 1979; Galbis-
Pd ez, Pin o Co aliza, Rom~n-Gal in & Gomdz-
Guilldn, 1979) ha e been s udied in o de o es ablish
he con o ma ional de ails o he molecule in he solid
s a e. Recen ly, we ha e epo ed he c ys al s uc u e
o l'-(p-b omophenyl)-3'-e hyl- 1 ',3',4',5'- e ahyd o-
1,2-dideoxy-o-glyce o-L-gluco-hep o u anoso[
1,2-d]im-
idazole-2'- hione (Es ada, Conde & M~quez,
1983). The i le compound has been p epa ed (Galbis-
Pd ez, Palacios, Jimdnez-Requejo, A alos &
Fe nb.ndez-Bola ios, 1983) by condensa ion o 2-amino-
2-deoxy-D-glyce o-D-gluco-hep ose
wi h a yl iso hio-
cyana e (Galbis-P6 ez
e aL,
1979) and sepa a ed by
ac ioned c ys alliza ion. I s chemical na u e was
es ablished om elemen al analysis and spec oscopic
da a and he X- ay analysis was ca ied ou o de ine i s
s uc u e and con o ma ion.
B
H OH /~
""' H
0
HOH2C
~ N
(I) C2H5
* IUPAC name: 6-~-b omophenyl)-4-e hyl-3-hyd oxy-2-(1,2,3-
ihyd oxyp opyl)-2,3,3a,5,6,6a-hexahyd o u o[2,3-d]imidazo]e-
5 (4H)- hione.
0108-2701/84/050'898-04501.50
Expedmen al.
Single c ys als in he o m o p isms
elonga ed along [001] p epa ed in he O ganic Chemis-
y Depa men o he Uni e si y o Ex emadu a and
kindly supplied by P o esso J. Galbis.
D m
by lo a ion
me hod. C ys al 0.06 x 0.08 x 0.13 mm. Uni -cell
pa ame e s by leas squa es om 23 e lexions, 5 <
0 < 20 °. En a -Nonius CAD-4 di ac ome e ,
g aphi e monoch oma o , 20 < 60 ° (Ihl < 9, k < 12,
l<21), 09-20 scan mode. Th ee s anda d e lexions
(200, 020, 023): a ia ion in in ensi y less han 3% o
mean alue. 2855 independen e lexions measu ed, 817
conside ed unobse ed [I < 2 (/)]. Lo en z and
pola iza ion co ec ion, no co ec ion o abso p ion
(#R ~ 0.2) o ex inc ion. Pa e son unc ion and hea y-
a om me hod wi h he ini ial se o phases based on
B -a om posi ion. Full-ma ix leas -squa es e inemen
on F, aniso opic. Di e ence Fou ie syn hesis e ealed
he 21 H-a om posi ions; iso opic empe a u e ac o
o each H se equal o ha o he a om bonded o i .
Fu he leas -squa es e inemen including he posi ional
pa ame e s o he H a oms and anomalous-dispe sion
co ec ions o B and S a omic sca e ing ac o s
(In e na ional Tables o X- ay C ys allog aphy,
1974)
"-,s'~,J,..,'y /
2 "~ 013)
015) V
Fig. 1. Bond leng hs (.~) and angles (o) in he molecule. (S anda d
de ia ions a e in he anges 0.006-0.010A and 0.41-0.60%
espec i ely.)
© 1984 In e na ional Union o C ys allog aphy
M. D. ESTRADA, A. CONDE AND R. M/~RQUEZ 899
Table 1.
A omic coo dina es
(x 104)
and equi alen
iso opic empe a u e ac o s
Ueq =
]~i~'jUlja* a*jal. lj
cos (a , aj) (x 103).
x y z Ueq(A 2)
B 8953 (1) 0 57 (5) 54 (< 1)
S 4655 (2) -6296 (2) -2391 (1) 36 (1)
O(1) 263 (5) -1949 (5) -2955 (3) 32 (1)
0(2) -707 (6) -4450 (5) -4227 (3) 35 (1)
0(3) -2427 (6) 272 (6) -3888 (3) 43 (1)
0(4) -4409 (7) -724 (6) -5485 (3) 44 (2)
0(5) -7587 (6) -2267 (6) -4841 (3) 42 (2)
N(I) 2613 (6) -3648 (6) -2162 (3) 27 (1)
N(2) 822 (7) -5679 (6) -2619 (4) 32 (2)
C(I) 2658 (7) -5187 (7) -2380 (3) 27 (2)
C(2) 599 (7) -3065 (7) -2257 (4) 27 (2)
C(3) -594 (7) -4494 (7) -2568 (4) 27 (2)
C(4) -1683 (7) -4000 (7) -3492 (4) 27 (2)
C(5) -1722 (7) -2263 (7) -3357 (4) 28 (2)
C(6) -2224 (8) -1280 (8) -4182 (4) 29 (2)
C(7) -4093 (8) -1798 (7) -4764 (4) 30 (2)
C(8) -5874 (8) -1820 (9) -4257 (4) 7 (2)
C(9) 4114 (7) -2808 (7) -1645 (4) 1 (2)
C(10) 4287 (8) -1242 (8) -1791 (4) 1 (2)
C(11) 5708 (9) -389 (7) -1284 (4) 1 (2)
C(12) 6922 (8) -1119 (8) -622 (4) 1 (2)
C(13) 6742 (9) -2673 (8) -449 (4) 0 (2)
C(14) 5315 (8) -3529 (8) -955 (4) 34 (2)
C(15) 253 (9) -7267 (8) -2855 (4) 37 (2)
C(16) -3 (11) -8214 (9) -2044 (5) 49 (2)
educed
R w
o 0.051 (R =0.049); weigh ing scheme
based on a s a is ical coun c i e ion (w= 1/o2).
(A/ )ma x = 0.3. S = 1.09 o 289 e ined pa ame e s.
Final di e ence syn hesis showed 0.35 >
Ap >
-0.25 e A -3. The enan iomo phic o m o he mol-
ecule was conside ed and he inal R w alue was
0.041 (R =0.039). The applica ion o he 3 es
(Hamil on, 1965) indica es ha he second enan-
iomo ph is co ec [3 =Rw(1)/Rw(2) = 1.244;
3~,~749, 0.00~ ~_1.002] and, he e o e, can be e ained as
he absolu e con igu a ion. C ys allog aphic p og ams
o he
XRA Y70
sys em (S ewa , Kundell & Baldwin,
1970) used h oughou .
Discussion. F ac ional a omic coo dina es and equi -
alen iso opic empe a u e ac o s (Hamil on, 1959) o
non-hyd ogen a oms a e gi en in Table 1.* Bond
leng hs and angles in ol ing non-hyd ogen a oms a e
shown in Fig. 1. C-H bond dis ances ange om
0.83 (9) o 1.15 (9)A wi h an a e age alue o
1.03(9)A. The a e age O-H bond leng h is
0.92 (9) A.
Molecula geome y
Values o bond leng hs and angles in he
imidazolidine ing a e simila o hose epo ed in o he
* Lis s o s uc u e ac o s, aniso opic he mal pa ame e s and
H-a om pa ame e s 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 39192
(14 pp.). Copies may be ob ained h ough The Execu i e Sec e a y,
In e na ional Union o C ys allog aphy, 5 Abbey Squa e, Ches e
CH 1 2HU, England.
analogous compounds (Conde, Be nie & M~ quez,
1980; Es ada, Conde & M~ quez, 1983). The ypical
asymme y o in acyclic N-C bonds, due o he
con ibu ion o he di e en esonance o ms o he
hiou ea sys ems (Valle, Cojazzi, Busse i & Mammi
1970; Es ada, Conde & M~ quez, 1983), is obse ed.
The ing is plana as indica ed by he
Z(d/a) 2
alue o
0.94 0 2 a 95% 5.59).
Bond leng hs and angles in he u anosyl ing a e
simila o hose obse ed in analogous compounds
p e iously s udied and he ypical asymme y o he
endocyclic bonds O(1)-C(2) and O(1)-C(5) due o
anome ic e ec s is obse ed. The gluco u anose ing is
no plana as expec ed. In e ms o he ing-pucke ing
coo dina es (C eme & Pople, 1975) he ampli ude and
phase magni udes a e Q=0.462(5)A and ~0=
145.2 (6) ° o he sequence O(1)-C(2)-C(3)-C(4)-
C(5) and he esul ing con o ma ion is 4E. The
asymme y pa ame e o Duax, Weeks & Roh e (1976)
is
AC s
[C(5)] =0.014 (3) °. This pucke ing mode is
di e en om he wis con o ma ion ound in a
ecen ly epo ed analogous compound (Es ada,
Conde & M~ quez, 1983) bu i is simila o hose o
o he analogous compounds (Conde, L6pez-Cas o &
M~ quez, 1978). The small alue o he C(4)-C(3)-
C(2)-O(1) o sion angle [-2.4 (5)°], cha ac e is ic o
hese compounds, is a ibu ed o dis o ion o he
u anosyl ing due o he ing usion.
The wo ings in he bicycle show a
cis
o m o
coupling as illus a ed in Fig. 2 in which I and #1 a e
p ojec ed alency angles and ,8, 7 and 6 o sion angles.
The ela ion l = y de i ed o a
cis
usion in ol ing only
e na y o qua e na y C a oms (Geise, Al ona &
Rome s, 1967) holds in his case. As obse ed in
analogous compounds (Conde, L6pez-Cas o & Mh -
quez, 1978; Conde, Be nie & Mh quez, 1980; Es ada,
Conde & M~ quez, 1983) he bonds o he C(2) and
C(3) ca bon a oms a e nea ly eclipsed. The dihed al
angle be ween he leas -squa es planes o he
imidazolidine and u anosyl ings is 49.3 (3) °. This
alue is smalle han hose ound o simila compounds
(~ 70°). In he phenyl ing, he a omic de ia ions om
he leas -squa es plane h ough he ing a oms a e
H(C3)
+
y 24151 {~!~[I - 04151
- 1204151 ~~.. N(1)
Fig. 2. Newman p ojec ion along C(2)-C(3), illus a ing he ing
usion (angles in deg).
900 C
I6H21B N2OsS
s a is ically signi ican :
~.(A/o') 2=
19.30 (Z 2 a 95%
7.81); howe e , his dis o ion is p obably no eal.
The phenyl ing is ma kedly wis ed wi h espec o
he imidazolidine plane. The dihed al angle be ween he
leas -squa es planes h ough he phenyl and
imidazolidine ings is 45.0 (2) °. Values in he ange
60-80 ° o his dihed al angle ha e been ound in
simila compounds, excep o he alue o 15.1 (6) °
obse ed in he case o l'-phenyl-l',3',4',5'- e a-
hyd o- 1,2-dideoxygluco u anoso [ 1,2-d]imidazol-2-one
(Conde, Be nie & Mh quez, 1980) and may indica e a
signi ican con ibu ion o in amolecula in e ac ion.
The e hyl g oup is also wis ed wi h espec o he
imidazolidine ing as indica ed by he o sion angle
C(1)--N(2)--C(15)--C(16) = 85.6 (7) °.
C ys al packing
Fig. 3 shows he con en s o he uni cell iewed
down he a axis. The c ys al s uc u e is s abilized by
an ex ensi e h ee-dimensional hyd ogen-bonding ne -
wo k. Molecules a e linked o o m chains pa allel o
[1001 by O(2)-H(O2)...O(5)(x+l, y, z) hyd ogen
bonds and chains pa allel o [010] by C(15)-
H(151)...O(3)(x, y-l, z) hyd ogen bonds. Also, each
molecule is linked o h ee nea es neighbou s ela ed by
a wo old sc ew axis by O(5)-H(O5)...O(2)(-x-1,
y+~, -z-l), O(4)-H(O4)...S(-x, y+½,-z-I) and
C(4)-H(4)...O(4)(-x-1, y-½, -z-I) hyd ogen
bonds. De ails o hese hyd ogen bonds a e gi en in
Table 2.
Fo he wo O-H...O con ac s lis ed in Table 2 he
alues o he d pa ame e , de ined as he di e ence
be ween he sum o he an de Waals adii and he
in e a omic dis ance (Taylo & Kenna d, 1982), a e
0.36 and 0.66/k espec i ely, bo h sa is ying he ule
d> 0.3 A, and he O--H...O angles ag ee wi h he
mean alue [165.8 (12) °] o bonds wi h O...H >
1.812 A (Allen, Kenna d & Taylo , 1983) and so can
be desc ibed as hyd ogen bonds. Fo he wo sho
C-H...O in e ac ions shown in Table 2 he d alues
a e bo h close o he limi ing alue d = 0.3; howe e ,
he C(4)--H(4)...O(4) angle is close o he mean alue
~10101
Fig. 3. A iew o he cell down a.
Table 2. Geome y o he hyd ogen bonds
X-H... Y X... Y(/k) X-H(/k) H... Y(A) X-H... y(o)
O(2)-H(O2)..-O(5 s) 3.094 (6) 0.86 (9) 2.34 (9) 182 (8)
C(15)-H(15).--O(3") 3.115 (8) 1.07 (8) 2.43 (9) 120 (6)
O(5)-H(O5)...O(2 "~) 2.986 (7) 0-96 (9) 2.06 (10) 161 (8)
O(4)-H(O4)...S ~ 3.216 (5) 1.03 (9) 2.25 (9) 155 (7)
C(4)-H(4)...O(4 ) 3.304 (7) 0.97 (8) 2.44 (8) 148 (6)
Symme y ans o ma ions: (i)
x+l, y, z; (ii) x,
y-l, z; (iii)
-x-1, y+½,-z-I; (i )--x,Y+½, -z-I; ( )-x-l, y-½,-z-1.
epo ed o he C-H...O hyd ogen bonds (Taylo &
Kenna d, 1982) bu C(15)-H(15)...O(3) is signi i-
can ly smalle . On he o he hand, C (15) is immedia ely
adjacen o an N a om, his ac enhancing he acili y
o pa icipa e in hyd ogen bonds (Taylo & Kenna d,
1982). The impo ance o C-H...O hyd ogen bonds in
he c ys al s uc u es o nucleosides has been
ecognized (Je ey & Maluszynska, 1982). Finally, he
exis ence o sho O-H...S con ac s has been ound in
o he imidazolidine-2- hione compounds (Vega,
He nhndez-Mon is & L6pez-Cas o, 1976; Jim6nez-
Ga ay, Ldpez-Cas o & Mh quez, 1976; C iado, Conde
& M~ quez, 1983) and, pe haps, he nega i e cha -
ac e associa ed wi h he S a om in he esonance o ms
o he hiou ea sys em is impo an in he elec os a ic-
ene gy e m. No o he in e molecula con ac s sig-
ni ican ly sho e han he sums o he an de Waals
adii ha e been de ec ed. The molecula geome y and
c ys al packing we e compu ed by PARST (Na delli,
1983).
The au ho s hank P o esso Galbis o supplying he
c ys als and D Gu i& ez-Puebla (Uni e si y o
Mad id) o collec ing he da a. The p esen wo k is
pa o a esea ch p ojec suppo ed by he Go e nmen
h ough he 'Comisi6n Aseso a de In cs igaci6n
Cien i ica y T~cnica'.
Re e ences
ALLEN, F. H., KENNARD, O. & TAYLOR, R. (1983). Acc. Chem.
Res. 16, 146-153.
CONDE, A., BERNIER, F. & MARQUEZ, R. (1980). Ac a C ys . B36,
3048-3052.
CONDE, A., LOPEZ-CASTRO, A. & MARQUEZ, R. (1978). Re .
Ibe oam. C ys . Mine . Me alog. 1, 23-36.
CREMER, D. & POPLE, J. A. (1975). J. Am. Chem. Soc. 97,
1354-1358.
CRIADO, A., CONDE, A. & MARQUEZ, R. (1983). Ac a C ys . C39,
122-125.
DUAX, W. L., WEEKS, C. M. & ROHRER, D. C. (1976). Top.
S e eochem. 9, 271-383.
ESTRADA, M. D., CONDE, A. & MARQUEZ, R. (1983). Ac a C ys .
C39, 1418-1421.
GALmS-P ~REZ, J. A., PALAOOS, J. C., JIMI~NEZ-REQUEJO, J. L.,
AVALOS, M. & FERNANDEZ-BOLA ~OS, J. (1983). Unpublished
esul s.
GALmS-P ~REZ, J. A., PINTO CORRALIZA, R. M., ROMAN-GALAN, E.
& GOM~Z-GOILL~N, M. (1979). An. Quim. 75, 387-391.
GARCiA-GONZALEZ, F., GALBIS-PI~REZ, J. A., FERNANDEZ-
GARCIA-HIERRO, J. I. & FERNANDEZ-BOLAI~OS, J. (1979). An
Quim. 75, 1002-1004.
M. D. ESTRADA, A. CONDE AND R. M/~RQUEZ 901
GEISE, H. J., ALTONA, C. & ROMERS, C. (1967).
Te ahed on,
23,
439-463.
HAMILTON, W. C. (1959).
Ac a C ys .
12, 609-610.
HAMILTON, W. C. (1965).
Ac a C ys .
18, 502-510.
In e na ional Tables o X- ay C ys allog aphy
(1974). Vol. IV.
Bi mingham: Kynoch P ess.
JEFFREY, G. A. & MALUSZYNSKA, H. (1982).
In . J. Biol.
Mac omol.
4, 173-185.
JIMENEZ-GARAY, R., LOPEZ-CASTRO, A. & MARQUEZ, R. (1976).
Ac a C ys .
B32, 1367-1371.
NARDELLI, M. (1983).
Compu . Chem.
7, 95-98.
STEWART, J. M., KUNDELL, F. A. & BALDWIN, J. C. (1970). The
XRA Y
sys em. Compu e Science Cen e , Uni . o Ma yland,
College Pa k, Ma yland.
TAYLOR, R. & KENNARD, O. (1982). J.
Am. Chem. Soc.
104,
5063-5070.
VALLE, G., COJAZZI, G., BUSSEY l, V. & MAMMI, M. (1970).
Ac a
C ys .
B26, 468-477.
VEGA, R., HERNANDEZ-MONTIS, V. & L6PEZ-CASTRO, A. (1976).
Ac a C ys .
B32, 1363-1366.
SHORT COMMUNICATIONS
Con ibu ions in ended o publica ion unde his heading should be exp essly so ma ked; hey should no exceed abou 1000
wo ds; hey should be o wa ded in he usual way o he app op ia e Co-edi o ; hey will be published as speedily as
possible.
Ac a C ys .
(1984). C40, 901
S uc u e o 2-amino-3,5-dib omo-N-cyclohexyI-N-me hylbenzeneme hanamlne-salicylic acid (1:1):
co igendum.*
By RICHARD E. MARSH,
A hu Amos Noyes Labo a o y o Chemical Physics, Cali o nia Ins i u e o
Technology, Pasadena, Cali o nia
91125,
USA
(Recei ed 8 Augus
1983;
accep ed 15 Sep embe
1983)
Abs ac
The c ys al s uc u e o C I4H2oB 2N2.C7H603 should be
desc ibed in he monoclinic space g oup
C2/c
a he han he
iclinic P] epo ed by Shimizu, Nishigaki, Nakai & Osaki
[Ac a C ys .
(1983), C39, 891-893].
The c ys al s uc u e o his compound was desc ibed as
iclinic, space g oup Pi, wi h a=29.146(34), b=
9.710 (3), c = 9.719 (9) ,/k, a = 105.18 (5), l= 124.18 (6),
y = 85.99 (6) °, Z = 4 (Shimizu, Nishigaki, Nakai & Osaki,
1983). The ec o s [01i], [011l, [102] de ine a C-cen e ed
cell wi h a' = 15.433, b' = 11.803, c' = 24.306, a' = 89.97,
l'= 99.11, y'= 90.06 °, Z = 8. The co esponding ans-
o ma ions x' = x + ½(y - z), y' = -x + ½(y + z), z' = x lead
o a omic coo dina es ha a e consis en wi h he symme y
o he monoclinic space g oup
C2/c
wi hin he epo ed
unce ain ies. (No ansla ion o o igin is necessa y since, by
e en chance, he cen e o symme y chosen as o igin in he
iclinic desc ip ion co esponds o a con en ional o igin in
C2/c.)
The
C2/c
pa ame e s a e gi en in Table 1.
The c-glide plane o
C2/c
equi es he sys ema ic ex-
inc ion o e lec ions
hk~:
wi h h odd in he iclinic indexing.
*Con ibu ion No. 6876 om he A hu Amos Noyes
Labo a o y o Chemical Physics. This wo k was suppo ed in pa
by Na ional Ins i u es o Heal h Resea ch G an No. GM 16966.
The ela i e e.s.d.'s in he iclinic cell ansla ions a e highly
dispa a e, and since co a iances a e no gi en i is impossible e en
o es ima e app op ia e e.s.d.'s o he monoclinic cell dimensions.
0108-2701/84/050901-01501.50
Table 1.
Coo dina es (x 104) o space g oup C2/c
The P-i coo dina es (Shimizu
e aL,
1983) ha e been a e aged
acco ding o he symme y o
C2/c;
numbe s in squa e b acke s a e
shi s necessa y o achie e his symme y.
x' y' z'
B (l) 61211] 5140 [0] 4352 [0]
B (2) 432 I01 695 Ill 3513 111
C(1) 1077 [21 3766 [12] 2860 [01
C(2) 996 [81 4556 [61 3276 [21
C(3) 760 [10l 4137131 3768121
C(4) 604 [21 3002 [2] 3856 [41
C(5) 673 [6] 2265 [9] 3425 [8]
C(6) 908 141 2623 [31 2935 [4]
N(I) 1164[11 5692 [3] 3220121
C(7) 1299 [4] 4099 [2] 2306 [0]
N(2) 2225 [1] 3768 [1[ 2252 [0l
C(8) 2878 14] 4586 [ll 2543 [2]
C(9) 2363 [6] 3544 [4] 1658 [4]
C(10) 2074 [4] 4540 [0] 1276 [21
C(11) 2233 [2] 4270 [0] 686 [0]
C(12) 1755 [2] 3196 161 469 [2]
C(13) 2055 [21 2215 [21 856 161
C(14) 1917 [21 2448 [21 1454 101
C(15) 384711] 2707 151 3684 121
C(16) 4724 [21 3022 141 3882 121
C(17) 49381101 3469131 4411111
C(18) 4294 [51 3621 151 4736 121
C(19) 3423 [41 3333 [51 4549 101
C(20) 3207 [21 2865 [51 4021101
C(21) 3609111 2233131 3114121
O(1) 2826 [21 2039 [41 2930 I21
0(2) 4222[01 2059 [31 2846 [21
0(3) 5348 [21 2897 [11 3558 101
Re e ence
SHIMIZU, N., NISHIGAKI, S., NAKAI, Y. & OSAKI, K. (1983).
Ac a
C ys .
C39, 891-893.
© 1984 In e na ional Union o C ys allog aphy