The Crystal and Molecular Structure of 1-p-Chlorophenyl-4-(tt-a-erythrofuranosyl)-4-imidazoline-2-thione

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.