2348 CONFORMATION DE LA N-ACETYL-L-PROLYL-D-LACTYL-METHYLAMIDE
CHANDRASEKARAN, R., LAKSHMINARAYANAN,
A. V.,
PAN-
DYA, U. V. & RAMACHANDRAN, G. N.
(1973).
Biochim.
Biophys. Ac a,
303, 14-27.
GERMAIN, G., MAIN, P. & WOOLFSON, M. M. (1970).
Ac a
C ys .
B26, 274-285.
IUPAC-IUB COMMISSION ON BIOLOGICAL NOMENCLATURE
(1970).
Biochemis y,
9, 3471-3479.
LECOMTE, C., AUBRY, A., PROTAS,
J., BOUSSARD, G. &
MARRAUD,
M. (1974).
Ac a C ys .
A pa ai e.
PINKERTON, M., STEINRAUF, L. K. ~ DAWKINS, P. (1969).
Biochim. Biophys. Res. Commun.
35, 512-518.
TICHY, M. (1965).
Ad ances in O ganic Chemis y: Me hods
and Resul s,
Vol. 5, edi 6 pa R. A.
RAPHAEL,
E C.
TAYLOR,
H.
WYNBERG,
p. 115. New Yo k: John Wiley.
Ac a C ys .
(1974). B30, 2348
The C ys al and Molecula S uc u e o
1-p-Chlo ophenyl-4-( -a-e y h o u anosyl)-4-imidazoline-2- hione
BY S.
PI~REZ-GARRIDO,
A. CONDE AND
R.
M/~RQUEZ
Depa amen o de Op ica, Secci6n de Fisica del Depa amen o de In es igaciones Fisicas Quimicas
(Cen o Coo dinado del C.S.I.C.), Uni e sidad de Se illa, Spain
(Recei ed 8 Ap il
1974;
accep ed
20
May
1974)
The i le compound, CISOsN2C~sH~3, he de ini i e o mula o which has been es ablished by X- ay s uc u -
al analysis, is o ho hombic, space g oup P2~2121 wi h a= 7.806 (5), b= 29.417 (13) and c= 5-921 (5) A,
Z--4. The s uc u e has been sol ed by di ec me hods wi h
MULTAN
and e ined aniso opically
(R=0"073) by a me hod o block-diagonal leas -squa es wi h 861 independen e lexions measu ed
on a di ac ome e (Cu Ke adia ion). The dihed al angle be ween he phenyl and imidazoline ings
is 50 °. The u anose ing is pucke ed so ha C(10) de ia es om he mean plane h ough he o he
suga - ing a oms and he dihed al angle be ween he imidazoline and he u anose ings is 95 °. The
packing o he s uc u e is e ec ed by hyd ogen bonds.
In oduc ion
The c ys al s uc u e o he i le compound has been
de e mined as pa o a esea ch p og amme on imid-
azole C-nucleosides and glucimidazole de i a i es. P e-
ious esea ch has in ol ed he X- ay s uc u al de-
e mina ion o 4-( l-D-e y h o u anosyl)imidazoline-2-
hione (P6 ez-Ga ido, Ldpez-Cas o & M i quez,
1973).
Recen ly, in he Depa amen o de Quimica O gS.nica
o his Uni e si y, a se ies o 1-a yl(alkyl)-4-(D-
e y h o u anosyl)imidazoline-2- hione compounds
ha e been p epa ed. In he p epa a ion o he i le
compound, 1-chlo ophenyl-4,5-(D-gluco u ano)imida-
zolidine-2- hione (I) was e luxed in i luo ace ic acid
o gi e 1-chlo ophelayl-4-D-a abino- e ahyd oxybu yl-
imidazoline-2- hione (II). Howe e , he chemical anal-
ysis
o he p oduc indica ed he composi ion o he
c ys al o be C1OSaN2ClaHla, which is consis en wi h
1-chlo ophenyl-4-(D-e y h o u anosyl)imidazoline-2-
hione (III) (Ga cia-GonzS.lez, Fe n~indez-Bola ios &
Fuen es-Mo a, 1972; Fe nS.ndez-Bola ios, Fuen es &
P ade a de Fuen es, 1974). The dehyd a ion o (ll)
in his p ocess and he epime iza ion o he hyd oxyl
g oups 1 and 4 o he polyolic chain a e di icul o
es ablish chemically and an X- ay analysis has con-
sequen ly been unde aken o de e mine de ini i ely
he o mula o he compound.
H. OH
'', O
HOCH=~
--q
HN~c= S
(1)
R=p-CI-CsH4
CH~N~R .,,R
II /c=s
CH~ N...
C--N H II /C=S
HOCH O C ~N H
,
HCOH
I
HCOH
I
CH=OH
(III)
(iz)
Expe imen al
C ys als o 1-p-chlo ophenyl-4-(~-D-e y h o u anosyl)-
4-imidazoline-2- hione we e supplied by P o esso J.
Fe nS.ndez-Bola ios o his Uni e si y (Depa amen o
de Quimica O g~inica).They a ecolou less needle-shaped
p isms, elonga ed along c. Ro a ion and Weissenbe g
pho og aphs we e used o de e mine he space g oup
and app oxima e uni -cell dimensions; mo e accu a e
alues we e calcula ed by a leas -squa es ea men o
S. P15,REZ-GARRIDO, A. CONDE AND R. M,/,.RQUEZ 2349
(O,x,q)) angles o 15 e lexions measu ed on an au o-
ma ed di ac ome e .
C ys al da a
a = 7.806(5) A
b =29.417(13)
c = 5.921(5)
Din= 1"53(2) g cm -3
Dx= 1"53 g cm -a
V= 1358"86 A 3
Z=4
F(000) = 960
p(Cu K~) = 39"46 cm - 1
A c ys al 0.05 x 0.03 x 0.021 mm was chosen o col-
lec in ensi ies up o 0< 50 ° on an au oma ed on-line
Siemens AED single-c ys al di ac ome e using Ni-
il e ed Cu Ke adia ion and he o9-20 scanning me hod.
861 independen e lexions we e eco ded, 293 o which,
ha ing I<2~ (1), we e conside ed as unobse ed. The
in ensi y o a s anda d e lexion was measu ed pe iod-
ically and subsequen ly used o scaling bu no signi i-
can change was obse ed in i s in ensi y du ing he da a
collec ion. The s uc u e ampli udes we e co ec ed
o Lo en z and pola iza ion e ec s, bu no abso p ion
co ec ions we e applied.
Solu ion and e inemen o he s uc u e
App oxima e absolu e scale and empe a u e ac o s
we e ob ained by Wilson's (1942) me hod. Fo he
Table 1. Re lexions used in he s a ing se , wi h phases
in adians
h k 1 ~o
0 3 5 ~z/2
0 3 2 1 /2
1 10 2
z /4
0 26 0 0
0 2 2 c
0 13 4 ~z/2
4 11 0 0 c
1 19 1 + e/4, +3z /4
Table 2. Final a omic ac ional coo dina es ( x 10
4)
wi h
es ima ed s anda d de ia ions in pa en heses
x/a y/b z/c
C1 4631 (6) 3007 (1) -813 (8)
S 6838 (5) 1134 (1) 5821 (8)
O(1) 365 (14) 334 (3) 8303 (16)
0(2) 2665 (13) 577 (3) 12075 (18)
0(3) 269 (14) 47 (3) 13830 (18)
N(1) 3546 (14) 1484 (3) 5600 (23)
N(2) 3774 (15) 874 (3) 7665 (23)
C(I) 4324 (20) 2555 (5) 1098 (26)
C(2) 3543 (21) 2652 (4) 3141 (26)
C(3) 3293 (20) 2288 (4) 4725 (27)
C(4) 3928 (21) 1850 (4) 4016 (27)
C(5) 4694 (21) 1760 (5) 1873 (26)
C(6) 4990 (21) 2123 (4) 450 (24)
C(7) 4694 (20) 1171 (4) 6271 (25)
C(8) 1890 (21) 1405 (5) 6333 (24)
C(9) 2041 (20) 1024 (5) 7752 (26)
C(10) 691 (20) 805 (5) 9083 (27)
C(11) 955 (20) 738 (5) 11646 (25)
C(12) -406 (21) 373 (5) 12217 (25)
C(13) -800 (22) 141 (5) 9871 (28)
solu ion o he phase p oblem no malized s uc u e
ac o s IEnk~l we e calcula ed. The alues o he s a is i-
cal a e ages (IEI) and (IE z- l I) we e 0.83 and 0.90
espec i ely.
The s uc u e was sol ed by mul isolu ion angen -
o mula e inemen (Ge main, Main & Wool son,
1971) o 170 e lexions wi h E> 1.30. Some di icul y
was expe ienced in ob aining a di ec solu ion om he
128 o iginal se s in which 20 di e en se s wi h he
same ABS FOM we e encoun e ed.
A success ul s a ing se was ob ained. The i s
h ee e lexions in Table 1 we e used o ix he o igin
and he enan iomo ph. The 0,26,0 and 022 e lexions
had a p obabili y P> 0.9 and, he e o e, we e consid-
e ed as known phases. F om hese and wo app opia e
symbolic phases, eigh phase se s we e gene a ed. Fou
had an ABS FOM o 1"22. The E map based on 170
Table 3. The mal pa ame e s ( × 102 lk z) wi h es ima ed s anda d de ia ions #l pa en heses
I 2 ~,2 2 ~2 2 ~2 ~ ~.
Aniso opic he mal pa ame e s ale in he o m: exp [-~(BHh a" + B22k b" +B33l c" + 2B, zhka"b " + 2B~3hla*c* + 2Bz3klb*c*)].
Bll B22 B33 Bl2 BI3 923
CI 650 (26) 246 (16) 332 (20) -90 (19) -21 (27) 77 (18)
S 225 (18) 272 (17) 418 (22) -3 (17) -9 (25) 67 (20)
O(1) 427 (57) 191 (40) 220 (49) -41 (43) 8 (50) -74 (37)
0(2) 280 (53) 380 (50) 334 (55) -79 (48) -148 (51) 4 (48)
0(3) 493 (57) 200 (40) 340 (54) 59 (46) -25 (62) 47 (42)
N(I) 221 (58) 109 (46) 335 (65) -19 (44) --86 (61) 28 (53)
N(2) 248 (59) 75 (46) 424 (71) --40 (48) 74 (63) --8 (49)
C(1) 362 (84) 308 (69) 183 (71) -50 (66) -83 (86) 25 (63)
C(2) 364 (91) 205 (64) 185 (74) -50 (66) -56 (73) 9 (60)
C(3) 333 (79) 201 (61) 300 (84) -31 (65) -102 (86) 75 (60)
C(4) 478 (83) 202 (62) 163 (69) 84 (66) -73 (84) 113 (62)
C(5) 388 (86) 156 (58) 286 (79) 16 (65) - 17 (78) - 109 (58)
C(6) 410 (79) 200 (59) 145 (66) -18 (67) 0 (80) -81 (55)
C(7) 353 (79) 208 (60) 216 (74) 31 (66) -35 (79) -142 (60)
C(8) 426 (86) 310 (69) 87 (72) -215 (77) -61 (77) -43 (56)
C(9) 315 (82) 252 (73) 280 (80) -142 (67) 118 (83) -62 (63)
C(10) 395 (78) 285 (68) 227 (73) 37 (64) 25 (89) -119 (68)
C(11) 194 (69) 320 (68) 231 (76) 105 (63) 30 (69) 60 (62)
C(12) 395 (91) 221 (62) 205 (72) -61 (68) 139 (81) -8 (60)
C(13) 425 (90) 324 (73) 349 (91) -235 (72) 144 (80) -84 68)
2350 1 -p-CHLOROPHENYL-4-(~X-D-ERYTHROFURANOSYL)-4-I MIDAZOLINE-2-TH IONE
e lexions calcula ed o hese se s co esponded o
he same s uc u e wi h o igin ansla ion. The E map
ga e di ec ly he posi ions o he whole s uc u e
(excluding he hyd ogen a oms) as well as se e al
Table
4.
Obse ed and calcula ed s uc u e ac o s
The columns a e in he o de
h, k, I, Fo
and F~.
+'+i! :i! +,+i +:!!.:i! "? i:!i
!ii !!!
i:!! !i! ',i! !!i! !!+ ii+
::+: :;: ::: :+'+: ::: :++: :::
,;,
,:
....................
i',! i.'i+! ;II ! I*)! ii!i !I? i:ii.iil ill I,! i :!;i':ii
iiii:ii:: :,!:: ::i:: !- i:.i :,ii i!!!i
ii?i i!
!!ill!i! +!? i!+:i "iii i!i
II" 3 '',',' ,+Z +117 .+ "~I' ,;'+ I'?. : .+,;: ~1o I': 3 .:g'+ "2 lq : .l~: "1
+++ ++i i++ +?+ ++i ++i i+++ +++ +++
i,++
+++ +++ ++++ ++i +++
i i!iiil iii i ;i i ii :i!i i+!i;ili :,ii i+ii .ili
+'i+ +i+i ++++++i !++ ++++i++ i+ +++:+++ +++ ++++i++ :++
+',~
I : :~ l:: +'11 I :b+;
++; +",~
.I': ,b + :I; I .11~ "1 : l I .111
'~++
+, io i l, + u. ~ + i i.+ l.s ~ . i • i~ z <, , i e~o .-,o ~ ,, i ~
+++ +++ +++ +:+ :+++ +++ ++++ +++ +++ ++++ +++ +++ ++++ +++
++i
,+ .............. + ..................
:
...... ,+~ , .,,. ,i
+++'
I "+'~.+ B: .++7 : " '+~
,?+' +++++
l+'+ ',+,:
++,+; ',
+q,+ ,11 :,% .Id +,h
+'!i i}1!~ !'!i !i! !~! ;'!! i!! ?! i!! !!?!!i
!?! ii!+!!
+?+ ++i +++ I++ +++ +++ ++ +++ +++ ! +i +++ ++
Ig+, : .b+. + +++~ 111 : .;~ :~ '..': I .11: '1++ 'o+", : .,+?°+ ++++~ +~g++ I .l~?, ':I
:g++ I P:++ :I+ + ::: I R:
*.'+;
++:++ ', .+,:;
'++: :,g : ";" +++: :,+ I "+"+~ +;1
o 1¢~ I )00 .+++1 + I. I S.~ .~ u i1 , 10, ..+ o i+ , . i + +} o ii i • i . s5
o io i +~+ ~+i o . + oi~ ,.i o o , .++ ,,', o , i ,,++ +~,• o + i i,~++ Izo.
• ~ : 10++ ioi, . . i ++i ,,0 + • , .o, .io o . ~ +s, .++ o i i • o, i+
o o ? • i++ ++, + i , l.~ ..l o + + ,., o+,, o , + i•., li o o + ¢ i ,: los
o • ? 3+9 lls o + + +o+ +o+ u i • I++ Poo o o ..+ i+i ilO o q 2 131 I+4
I',~++ ;b' ;;: :',+' ~ ~l~ ;:: :I +, : .,b + 2: ::: ++ .i:: +~++ :',: ++ +~++.+
~g:
o ;~o ? • i+o i+?? o +1 i io+ 1+i o .d • ¢.+ ebo o l • 3' + l+~+ @ ¢% i • |+i ii+
o is + i + i + o e+ + i++ i.+ o . • • u, .,o i ,+~ • • i.,, ,,i i..~,., lol +oo
] l~ i + • l.) + .% i i. i~ ).b lOO i i. ~, .ll .io i i• • 30, 2a,= i ii z 1oo 47.l)z
i io e ,co ~,,o i . a -..z ,~ i o • ,., x,o x , ¢ l~,, ll¢ i ~ e 108 I~
I S ~ +I~ ..+ + . e i+~ i.+ i i . .... ,e i • e io+ +,, i i ." .,+ ++o
i o P + ,., ++. + o ,+ l,o lo ,, i + ,+~ .++ + •., i., i+. + + e~ ,+) ,.e.
,~ ; .~ l++ l, + ,+,I + ~+'?+
;l:
:,+ +
:': ++++'
~,+ +, .;+++'
+:+'
+,+ +~ +l ~,
+%+:
z i,, . ,
• ,, g.~:: ':++ ~; ~
~;~ ~+++' +++'i ++
.~++++ ,~I
++~+ ++
. +'++
+:; ++':
g .ll:
11~
I ,, z )+,e ]~+ .+ ~ .. .I io. , ~ . ..+ ,o; ~ , z z~,o <,~. ) • • +o. )~,,.
3 3 i' II+ 11' .I 2 + 3+9 31,3 3 i c • Ill .0 l U • ¢c'+ ++b + 0 ? O+ el
: I ;.I,+, ,+3 : +, ++ ;++1 ;:~ : + + .+:: '+1 : : ; :17 ++ :,3 ++ I+' %+
u z • zo~ zol • iz ,+ ~.o ~.+++ ~ iJ • . e~, eJ,, ~ i. ,. +.e .,.o ~ Is z i~,.+ i..i
.+', + I:+ ,:: :g ++ :Ill '+++ :+': ++
.1::
;+ +': ++ :I~: 3+ + 1,+: ++ "11+'
,11
,'11 ,+ ;g: :3: "".,+
++ I++~ ,I+' ~11 ."
"1;: 1:: ,+11 ~ 2+ + ~b ++': ~ .,q~ +~+:
s • . .,~ +.'a '+ .+ " I)0 ~+' ~ ~ e ."" ++'I S • ." .'J' e+ , " " • I'+ I~
". + .~ eS* a"~ +' e • I+) I+1' + + • I+" '++ S + ,+ • U' Sl + O ." 11" IS+
' ++ "+I ++'++ : +, + :I++ + :l ~ I ++ .,++; +i. : : ++ "b. ° ,+; :,I ++ .13: ~
~, ii .. • i..0 ~e +, i.. <~ i.<+ l~O • ~.+ • • i+~ io+ +, i+ e • l.O ii +, i~ e • i,~i *o
T , .. • 1+++ i).. ~ +., • 11+ uo , s • • ,.. io+, i . e • i+', .+ , i I • 1.1,+ le+
T ? + • ISO 9+ I * l+o 30 ' 0 + • I+'+ 1o1~ + II ) • 13s lip + IO J • llg .$
+++: +[ ,++
+++'i++
:++ ++ +i++ '++ ++i:+++
;++ +++:+++
,++
+:+} ..........................................
i..+ , ,~. ) i). i,+.+ • +o., +..,+ 1.i + i+ ) • u,s +~. , I* + I.+, ++
. I, + .+i,, e~,+ + ~.., I s I+,+ .1, + •+. ,.. + ~. + 11, +0 . ++ ) • i.+ +oi
:'+, I J+': ?.: :", ++ .l;l *+.~ :'++ +' +++' + . + : .+ I ,%++ ,%'+, : + I : ~ ,%+
+' ; I I+: l++; I ; I "+ +:: + ; ++ C++I +++: I,; I I+~ +;.' I,+ I +.,~:l
i l; I • i++ IO+ J i. i (?i? ~1+ 3 i+ J • llg +s ~ z, + • i j+ elj i Pl 3 • i~.i iol
+ ++' I +%" +':i
,'+: I
"l.'+ h': ,',++' I
•
l++. + '+',~ ~+++, I
• ++l
+ +' ++' I '+++ +oq
E I$ 3 • II L) ++ • I+ ) 151 J+. e I.+ .+ 10. ~'oJ Z 11 l lu' I0+ i II + I + ¢1)
+ lO ) IbV I+~ • + J 1+o ++o <. o J I + I+% ~. l 4 + 5 •. o + + + I++ i+~)
• s + • ~.++ ~oo • . ++ ,+e. e.*' • , + e-+ .'+. -" . + ,+o+ +I + ~ -~ I.+ I.."
+ 0 , .I++ +0: + ++ I I++ ;;+' + I "+;; %': ; I .'3' '+.+ I ,' I .l+: 11~
1 9 ]
10P ~+ i 10
J .~0 ~g i ii J 3 + 3++ ! l~ i ,?hi
,~l+ I 1+1 1 1 +6
~06
I I+ ~ 119 "130 I I~ + ¢]P +.1 i i+ • •++ Z~L i i 3 z ++ ¢)+ l 18 3 • I+'+ IPI
+' ++
I "B:
,:++
: ~+i I "IY,
,+++ o + +;
+ 11+ l+; : ,+,~ I .1+1
,I~ o++, I
:+T :+l
!',! !: iii iii ! ! !; iii i i i . i ! i i i: ili ',ii i:i i. !ii iii
.......... ~ : .~ll 'I ' ++ : :'d; ~ ~. '~ : "Y+.: +:~ ' : : .,%+: ll
+:++
j++ !!P +:++'++P
',++ +:++
;++
++
+:++:++~
,++
+:++++++ ++
I + + lid lql
h
l- . • i+% l,,i i I + I)l Ill I 4b + l Ill +I , IS . I Ill I00
+ ," + • ~e- +I+' • ,+ . " ,,'. 0+ .' ,.. I+. I'' + U
. ~0+
i.,. + ,0 + +el e++
, . + • i ~
•, .,
. .
i., eu , , . • ,,+ ,+ + ,, . • ~el ,, ++ s + i'- l+i
i . + • u. ,+ J , . l+. ,11 + • . ,+• i++, + I . e++ ~e+ + o . • +..o i..
. o + • ,)+ +,i . i - is+ .+i . • . ~.+ ,*+ + , . • i.- +,e . . + • i.++ i*
. s . .,+ ,+, .... u) ,,+ . , . •.+ e•+ . + . +e. ,,+ . + - i++ i+,
• io . • i.i u. . ,i . • 1., .. . ,, . • 1.. ++ . i+ . • ,.. ,co • i.. +. i,.
. i., • i~. is+. ~ io . • i * +~ ~ . . • I~.. i.,~ s • . i.~ ,+~ . , . • ~s+ le,
s b k I+o I++ • + • li+ I.+ • + + I+• 1++ ~. • • • i+1 ++ +i ? + li i+i
s i +, ~+. i++ '+ + . • i~+ .. . + + • i,, ~,o + ,:., +.o i.+ . I + • +el ,+
+~•+++~+
++:, I++
++ ++++,
i++',++ ++i:, ++i:+i i++, .+?+',++
." io s • u~ I~s , + • ..i~ i++ + . ~ ~.~ i~+ .. , ,, i.. i~. • ,, • • i~, i.~
., s s • i,+,, .~ ,+ . + • i+o .o + + + • i++ .e e + . ++, +.+ • i • i++ ,.+
+ . + • le, leo + o + i+) .+. ~ i + • i+. 1~ i , +, • i., +o I + + ,~. ,++
11+ s ,..,, ,., + 1. , .~ ,+. , ,..+ 1.. i.,. o ,, . 1~. o. o ,e . • u. +.
o ii • l+l i+ +c, l:, + loO ¢ l a + .) i.• l.+ 0 a • • i + • o l • • ill ..
o+ ~ .
• P"+ "7.
....................................
spu ious peaks esul ing om he p opaga ion o pa al-
lel in e a omic ec o s•
Se en cycles o leas -squa es block-diagonal e ine-
men wi h iso opic he mal pa ame e s imp o ed
he con en ional R index om 24 o 9-7 %. This alue
d opped o 0.073 a e ou cycles wi h aniso opic
he mal pa ame e s• The shi s in he las cycle o
e inemen we e less han 0.30" o all pa ame e s. The
quan i y minimized was ~wlJFI 2 and uni weigh s we e
used.
A omic sca e ing ac o s o C ome & Mann (1968)
we e used in he calcula ions. Posi ional and he mal
pa ame e s a e quo ed in Tables 2 and 3. The obse ed
and calcula ed s uc u e ac o s a e gi en in Table 4.
Resul s and discussion
This s uc u e analysis was unde aken p ima ily o
de e mine he ing con o ma ion o he molecule in he
solid s a e o assis in unde s anding he eac ion
mechanism in ol ed in o ma ion o he compound
and
o asce ain he compound's de ini i e o mula.
(i) Plana i y in he
molecule
The planes o bes i o he ings in he molecule
and hei a omic displacemen s a e lis ed in Table 5.
Table
5.
Leas -squa es planes h oug h
a ious ings and
de ia ions o he a oms
om he planes
(a) Equa ions o
planes
Each plane is ep esen ed b_y
AX+BY+CZ=D,
whe e
X, Y,Z
a e he coo dina es in A ~e e ed o he c ys al axes.
A B C D
I Phenyl ing 0.8883 0.1976 0.4145 4-7702
II
Imidazoline ing
0.2010 0-5760 0.7923 5.6740
III
Gluco u ane ing 0.7048 -0.6744 0.2199 0.5976
(b) Dis ances in , , o he a oms om he plane
A oms excluded om he calcula ion o he leas -squa es
planes a e deno ed by an as e isk.
Plane I Plane II Plane
III
A om De ia ion A om De ia ion A om De ia ion
C(1) -0"017 N(I)
0"024 C(11) -0"020
C(2) - 0"001 N(2) - 0-005 C(12) 0"030
C(3) 0"002 C(7) -0"025 C(13) - 0.032
C(4) 0.014 C(8) -0"012 O(1) 0.022
C(5) -0"033 C(9) 0.018 C(9)* -0"497
C(6) 0.034 S* 0-051 C(10)* -0.632
CI* -0"011 C(10)* 0"060 0(2)* 1"296
N(1)*- 0"074 0(3)* 1"258
Bo h he phenyl and he imidazoline ings a e plana
wi h mean a omic displacemen s o 0-02 and 0.01 A e-
spec i ely. The dihed al angle be ween he phenyl and
imidazoline ings (~50°), acco ding o he heo y o
Ki aigo odskii (1965), indica es ha he mos impo -
an e m in he con o ma ional ene gy is he po en ial
ene gy• The molecula s abili y o he o ganic c ys als
is eached when he ee ib a ional ene gy, as a sum
S. PI~REZ-GARRIDO, A. CONDE AND R. M/~RQUEZ 2351
o in a- and in e molecula ene gies, co esponds o
a minimum. In subs ances such as hese he ene gies in-
ol ed a e he po en ial ene gy, he esonance ene gy
and he la ice ene gy. The i s e m eaches a mini-
mum when he phenyl ing is pe pendicula o he
imidazoline ing, while he o he wo e ms a ain
minima when he wo ings a e coplana .
The gluco u an ing is no plana , as expec ed. The
C(10) a om is 0.63 ,~ ou o he leas -squa es plane
h ough he o he suga ing a oms whose mean de-
ia ion om he plane is 0.03 ~. The dihed al angle
be ween he imidazoline and suga ings (_~ 95 °) shows
also ha he po en ial ene gy e ms p edomina e
la gely.
The C(9), 0(2) and 0(3) a oms bonded o he gluco-
u an ing de ia e o he same side o he mean plane
h ough he ing; he e o e, his co esponds o an
c~-con igu a ion o he g oup.
(ii)
Molecula dimensions
Bond leng hs and angles in he molecule wi h es i-
ma ed s anda d de ia ions a e lis ed in Table 6. Fig. 1
S
C(6)
• "'"' ~
j~O(2)
~C(11)
C(10~O(3y~x
C(12) C(13)
Fig. 1. Molecula con o ma ion.
Fig. 2. Packing o he s uc u e iewed down e.
shows a labelled pe spec i e d awing o he o igin
molecule in he cell.
Table 6.
Bond leng hs (A) and angles (°) wi h es ima ed
s anda d de ia ions
CI--C(1) 1.762 (16)
C(1)-C(2) 1.384 (22)
C(2)-C(3) 1.437 (19)
C(3)-C(4) 1.443 (18)
C(4)-C(5) 1.427 (22)
C(5)-C(6) 1.378 (20)
C(6)-C(1 ) 1.426 (20)
C(4)-N(1) 1.459 (18)
N(1)-C(7) 1.345 (17)
C(7)-S 1.698 (16)
C(7)-N(2) 1-400 (18)
CI--C(1)-C(2) 117.7 (20)
C(1)-C(2)-C(3) 118.5 (26)
C(2)-C(3)-C(4) 115-4 (21)
C(3)-C(4)-C(5) 124-6 (28)
C(4)-C(5)-C(6) 118.0 (26)
C(5)-C(6)-C(1) 117-7 (25)
C(6)-C(1)-C! 116.8 (17)
C(6)-C(1)-C(2) 125.4 (29)
C(3)-C(4)-N(1) 113"7 (19)
C(5)-C(4)-N(1) 121.4 (26)
C(4)-N(1)-C(7) 124.0 (25)
N(1)-C(7)-N(2) 105.0 (17)
N(1)-C(7)-S 130.9 (22)
S C(7)-N(2) 123-9(20)
C(7)-N(2)-C(9) 108.4 (21)
N(2)-C(9)-C(8) 107.8 (20)
N(2)--C(9) 1 "424 (19)
C(9)--C(8) 1.406 (21)
C(8)--N(1) 1"383 (20)
C(9)--C(10) 1 "465 (22)
C(10)-C(11) 1.544 (22)
C(11)-C(12) i'548 (22)
C(12)-C(13) 1.578 (22)
C(I 3)-O(1) 1-418 (19)
C(10)-O(I) 1.482 (17)
C(I 1)-O(2) 1.439 (18)
C(12)-O(3) 1.452 (18)
C(9)--C(8)--N(1) 104-1 (20)
C(8)--N(1)--C(7) 114"5 (24)
C(8)--N(1)--C(4) 121.1 (26)
C(8)--C(9)--C(10) 127.7 (31)
N(2)--C(9)--C(10) 124.5 (28)
C(9)--C(10)-C(11) 119.3 (26)
C(IO)-C(ll)-C(12) 102.2 (19)
C(10)-C(11)-0(2) 109.8 (20)
0(2)--C(11)-C(12) 111.7(21)
C(11)-C(12)-C(13) 104.0 (20)
C(11)-C(12)-O(3) 110.7 (20)
O(3)--C(12)-C(13) I I 1-4 (21)
C(12)-C(13)-O(1) 106.2 (19)
C(13)-O(1)--C(10) 106.3 (20)
O(l)--C(10)-C(ll) 102.1 (17)
O(l)--C(10)-C(9) 111.5 (20)
The a e age bond leng h and angle in he phenyl
ing, 1"42(2) A and 119(3)o espec i ely, a e wi hin he
expec ed anges. The C1 a om is in he plane o he
phenyl ing and he C1-C(1) dis ance o 1.762(16)
ag ees well wi h he C1-C( ing) leng h in phenyl mono-
chlo o de i a i es. The in e - ing dis ance C(4)-N(1)
o 1-459(18) A ag ees wi h a single bond N-C dis ance
and he N(1) a om lies in he phenyl mean plane.
The obse ed alue 1.698(16) A o he bond leng h
S-C(7) is in e media e be ween he S-C single-bond
dis ance o 1.81 A and double-bond alue o 1.59 A.
This pa ial double-bond cha ac e is in ag eemen
wi h he canonical esonance o ms o he hiou ea
sys em and is a no mal ea u e o hese compounds
(Valle, Cojazzi, Buse i & Mammi, 1970; P6 ez-Ga -
ido, L6pez-Cas o & M~i quez, 1973; Jim6nez-Ga ay,
L6pez-Cas o & M~i quez, 1974). The bond dis ances
and angles in he imidazoline ing a e in ag eemen wi h
he alues epo ed in he li e a u e. The a he longe
alue o 1.400(18) A o he C(7)-N(2) bond is wo h
no ing. The e o e, he e is an in amolecula con ac
N(2)-O(2) o 2.886(17) A.
In he suga ing he alues o he bond leng hs a e
no mal. As in o he s uc u es, O(1)-C(10) is sligh ly
longe han O(1)-C(13). The alues o he C-C-C,
C-C-O and C-O-C angles in he u anose ing ag ee
wi h hose ound in analogous compounds.
The in amolecula con ac s lis ed in Table 7 may
indica e he p esence o some in amolecula packing.
2352 1-p-CHLOROPHENYL-4-(~-D-ERYTHROFURANOSYL)-4-IMIDAZOLINE-2-TH1ONE
Table 7. ln e a omic con ac s less han he sum o he
an de Waals adii
(a) In amolecula
o(1).-. C(9) 2.437 (18) A
0(2)-- -0(3) 2-647 (14)
0(2).. • N(2) 2.886 (17)
0(2)... C(9) 2.919 (19)
C(3) • • .C(8) 2.975 (20)
(b) In e molecula
O(1).--O(3) (i) 2"781 (14)/~,
N(2)...O(3) (ii) 2-894 (13)
C(8)---C(II) (i) 3.476 (21)
Symme y code:
(i) x,y, -l+z
(ii) ½-x, 37, -½-+z
adjacen molecules a e linked by O-.-O and C...O
hyd ogen bonds.
The au ho s hank P o esso M. Na delli o he
use o an au oma ic di ac ome e a he Is i u o di
Chimica Gene ale ed Ino ganica o Pa ma Uni e si y,
D M. A. Pellinghelli o he aluable sugges ions
du ing he da a collec ion. They also hank P o esso
J. Fe n indez-Bola ios (Depa amen o de Quimica O -
g inica o his Uni e si y) o supplying he c ys als
and o his help ul discussion on he chemical aspec s
and P o esso A. L6pez-Cas o, o his Depa men ,
o he ac i e in e es in and c i icism o his wo k.
The p esen wo k is a pa o a wide esea ch p ojec
suppo ed by a g an o he 'Fundaci6n Juan Ma ch'.
(iii) Molecula packing
Signi ican non-bonded in e ac ions, less han he
sum o he an de Waals adii (Pauling, 1960), a e
gi en in Table 7. Fig. 2 illus a es he packing o he
molecules down e.
The O(1)...O(3) dis ance o 2.781(14) A is in he
ange o O-H. • • O dis ances ound in he li e a u e and
i seems easonable o classi y his con ac as a hyd o-
gen bond. The wo con ac s C(8)... C(1) o 3.476(21) A
and N(2)... 0(3) o 2.894(13) A show signi ican sho -
ening wi h espec o he sum o he co esponding
an de Waals adii and mus be classi ied as de ini e
hyd ogen bonds. The e a e no o he non-bonded dis-
ances less han he sum o he an de Waals adii
in he s uc u e.
The molecules a e s acked in ows, pa allel o e,
ela ed by a N... O hyd ogen bond. Wi hin each ow,
Re e ences
CROMER,
D. T. &
MANN,
J. B. (1968). Ac a C ys . A24,
321-324.
FERN~NDEZ-BOLAi~OS, J., FUENTES, J. & PRADERA DE FUEN-
TES, M. A. (1974). An. Qui e. In he p ess.
GARCiA-GONZ.~LEZ, F., FERN.~NDEZ-BOLA/~OS, J. ~ FUEN-
TES-MOTA,
J. (1972). Ca bohyd. Res. 22, 436-440.
GERMAIN, G., MAIN, P. • WOOLFSON, M. M. (1971). Ac a
C ys . A27, 368-376.
JIMI~NEZ-GARAY, R., LOPEZ-CASTRO, A. & M~RQUEZ, R.
(1974). Ac a C ys . B30, 1801-1805.
KI1-AIGORODSKII,
A. I. (1965). Ac a C ys . 18, 585-590.
PAULING, L. (1960). The Na u e o he Chemical Bond.
I haca: Comell Uni . P ess.
P~REZ-GARRIDO, S., L6PEZ-CASTRO, A. &
M~,RQUEZ,
R.
(1973). An. Fis. 69, 179-188.
VALLE, G., COJAZZI, G., BUSETTI, V. & MAMMI, M. (1970).
Ac a C ys . B26, 468-477.
WILSON, A. J. C. (1942). Na u e, Lond. 150, 151-152.