Structure of l'-(p-Bromophenyl)-3'-ethyl- 1',3t,4',5 t -tetrahydro- 1,2-¢~• deoxy-D-glyeero-Dgu/ a-heptofuranoso[ 1,2-d]imidazole-2'-thione,* C16H21BrN2OsS

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