Structure of 1,3-Dihydro-4-[(2R)-2,5-dihydro-2-furyl]-3-phenyl-l-(p-tolyl)-2H-imidazole- 2-thione, C20HlsN2OS

1215 Ac a C ys . (1985). C41, 1215-1217 S uc u e o 1,3-Dihyd o-4-[(2R)-2,5-dihyd o-2- u yl]-3-phenyl-l-(p- olyl)-2H-imidazole- 2- hione, C20HlsN2OS BY A. CRIADO, A. CONDE AND R. MARQUEZ Depa amen o de Op ica y Cen o Coo dinado de CSIC, Facul ad de F sica, Uni e sidad de Se illa, Spain (Recei ed 2 Janua y 1985; accep ed 1 Ap il 1985) Abs ac . M =334.4, o ho hombic, P212~2 ~, a= 9.366(4), b=20.616(5), c=9.137(4)A, V= 1764 (1) A 3, Z = 4, D x = 1.26 Mg m -3, 2(Mo Ka) = 0.7107 A, g = 0.18 mm -~, F(000) = 704, T= 300 K, inal R--0.056 (wR =0.052) o 1979 obse ed e lec ions [I > 2a(/)]. The u anose ing is app oxi- ma ely plana because o he double bond, 1.289 (9) A, which a ec s he con o ma ion o he ing. The dihed al angle be ween he u anose and imidazole leas -squa es planes is 69.9 (2) °. A possible C--H...O hyd ogen bond has been de ec ed in ol ing C and O a oms in he u anose ing, gi ing in ini e helical chains along [001 ]. In oduc ion. The i le compound (I) has been ob ained by he eac ion o 1,3-dihyd o-4-(2,3-di-O- osyl- l-D- e y h o u anosyl)-3-phenyl- 1-(p- olyl)-2H-imidazole-2- hione wi h sodium iodide and zinc powde in dime hyl- o mamide. A s udy wi h he ~H NMR echnique in solu ion showed an app oxima e plana con o ma ion o he u yl ing (Fe n indez-Bola ios Guzm~n, 1984), in ag eemen wi h he solid-s a e esul s om X- ay da a. CH 3 o (I) The numbe o dihyd o u yl he e ocycles s udied is e y small, and his is one o he i s (dihyd o- u yl)dihyd oimidazole-2- hione compounds s udied (see also Mo eno, L6pez-Cas o & M~ quez, 1985). Bo h compounds o m pa o a wide esea ch p ojec in ol ing he syn hesis and s uc u al analysis o imidazole C-nucleosides (C iado, Conde & M i quez, 1983; Conde, L6pez-Cas o & M i quez, 1978). Expe imen al. Da k-yellow pa allelepiped c ys als sup- plied 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 0108-2701/85/081215-03501.50 s udies consis en wi h o ho hombic symme y; space g oup P212121 om sys ema ic absences. En a -Nonius CAD-4 di ac ome e , g aphi e-monoch oma ed adia ion. C ys al 0.15 x 0.39 x 0.80 mm. Uni -cell pa ame e s om leas -squa es i o 25 e lec ions, 7 </9 < 16 °. 2877 e lec ions wi h 0 < 30 ° (0<h<13, 0<k<28, 0<l<12) measu ed. 09-20 scan mode. 1979 e lec ions wi h I > 2o(1) obse ed. In ensi y changes in wo e e ence e lec ions less han 2%. Lo en z and pola iza ion co ec ions. No ab- so p ion o ex inc ion e ec s conside ed. Weigh ed angen - o mula e inemen (MULTAN80; Main, Fiske, Hull, Lessinge , Ge main, Decle cq & Wool son, 1980) o 246 e lec ions wi h E > 1.5. Full-ma ix leas - squa es e inemen o 217 pa ame e s based on F o wi h obse ed e lec ions (CRYLSQ o XRA Y70; S ewa , Kundell & Baldwin, 1970). A Fou ie di e ence syn hesis ga e he H-a om posi ions; leas -squa es e inemen in a mixed mode wi h iso opic empe a u e ac o s o H a oms hose o he a ached non-H a oms ga e wR = 0.052 (R = 0.056). Weigh ing scheme 1/0 "2(/) om coun ing s a is ics. Final-cycle pa ame e shi s less han 0.15a, a e age 0.07(7. S= 1.89 o 271 a iables. Final di e ence Fou ie excu sions -0.25 < Ap < 0.30 e A -3. A omic sca e ing ac o s om In e na ional Tables o X- ay C ys allog aphy (1974). Absolu e con igu a ion om chemical in o ma ion. Discussion. Final a omic coo dina es and equi alen iso opic he mal pa ame e s (Hamil on, 1956) o non-H a oms a e gi en in Table 1.* Bond angles and dis ances o non-H a oms a e shown in Table 2. The C-H bond dis ances ange om 0.85 (6) o 1.09 (6) A, wi h a mean alue o 0.95 (6) A. Phenyl g oups. The alue o he C-C bond leng h is 1.384 (8) A in he N(1)-phenyl ing and 1.383 (8) A in he N(2)-phenyl ing. The a e age C-C-C bond angle is 120.0 (5) ° in bo h ings. The sligh de ia ion om * 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 42176 (15 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. © 1985 In e na ional Union o C ys allog aphy 1216 C20HlsN2OS Table 1. Posi ional pa ame e s (x 10 4) and equi alen iso opic he mal pa ame e s (×10 3) o he non-H a oms, wi h e.s.d.'s in pa en heses Ueq = ~ZiZjUua, aj ai.a J. x y z Ueq(/~, 2) S 6374 (1) 1653 (I) 7572 (l) 51 (1) O 6996 (4) 4369 (2) 6564 (5) 76 (2) N(1) 7743 (5) 2330 (2) 5412 (4) 48 (1) N(2) 7358 (4) 2903 (2) 7362 (4) 42 (1) C(1) 7151 (5) 2293 (2) 6790 (5) 39 (1) C(2) 8254 (6) 2948 (2) 5147 (5) 52 (2) C(3) 8012 (5) 3310 (2) 6347 (5) 44 (1) C(4) 8311 (6) 4016 (2) 6604 (6) 51 (2) C(5) 7013 (8) 4795 (3) 5298 (9) 89 (3) C(6) 8504 (8) 4746 (3) 4732 (7) 75 (2) C(7) 9218 (6) 4311 (3) 5432 (7) 60 (2) C(8) 6887 (5) 3100 (2) 8802 (5) 39 (1) C(9) 7908 (6) 3237 (3) 9859 (5) 52 (2) C(10) 7452 (7) 3472 (3) 11224 (6) 65 (2) C(I 1) 6018 (8) 3539 (3) 11497 (6) 68 (2) C(12) 5026 (6) 3380 (3) 10459 (7) 66 (2) C(13) 5459 (5) 3163 (3) 9080 (6) 55 (2) C(14) 7679 (5) 1831 (2) 4316 (5) 43 (1) C(15) 8419 (6) 1266 (3) 4472 (5) 58 (2) C(16) 8350 (7) 796 (6) 3388 (6) 63 (2) C(17) 7508 (6) 890 (2) 2146 (6) 54 (2) C(18) 6785 (6) 1471 (3) 1994 (6) 57 (2) C(19) 6864 (5) 1945 (2) 3065 (6) 50 (2) C(20) 7438 (8) 377 (3) 978 (7) 86 (3) Table 2. Bond dis ances (A) and angles (o) wi h e.s.d.'s in pa en heses S-C(1) 1.677 (5) C(8)-C(9) 1.389 (7) O-C(4) 1.431 (6) C(8)-C(13) 1.368 (7) O-C(5) 1.452 (9) C(9)-C(10) 1.404 (8) N(1)--C(1) 1.378 (6) C(10)-C(11) 1.373 (9) N(1)--C(2) 1.383 (6) C(1 I)--C(12) 1.368 (9) N(I)--C(14) 1.435 (6) C(12)-C(13) 1.397 (8) N(2)-C(1) 1.375 (6) C(14)-C(15) 1.364 (7) N(2)-C(3) 1.392 (6) C(14)-C(19) 1.394 (7) N(2)--C(8) 1.446 (6) C(15)-C(16) 1.386 (8) C(2)--C(3) 1.345 (7) C(16)-C(17) 1.396 (8) C(3)--C(4) 1.501 (7) C(17)--C(18) 1.383 (8) C(4)-C(7) 1.497 (8) C(17)-C(20) 1.505 (8) C(5)--C(6) 1.492 (9) C(18)-C(19) 1.384 (7) C(6)-C(7) 1.289 (9) C(4)--O-C(5) 108.6 (5) C(4)-C(7)-C(6) 110.1 (5) C(2)--N(1)--C(14) 123.5 (4) N(2)-C(8)-C(13) 119.6 (4) C(1)--N(I)-C(14) 125.6 (4) N(2)-C(8)-C(9) 118.7 (4) C(1)-N(1)-C(2) 110.4 (4) C(9)-C(8)-C(13) 121.6 (5) C(3)-N(2)-C(8) 124.8 (4) C(8)-C(9)-C(10) 118.6 (5) C(I)--N(2)-C(8) 124.0 (4) C(9)-C(10)-C(1 I) 119.6 (5) C(1)-N(2)-C(3) 111.1 (4) C(I0)-C(11)-C(12) 121.0(6) N(1)--C(1)-N(2) 103.9 (4) C(11)-C(12)-C(13) 120.3 (5) S-C(1)-N(2) 128.5 (4) C(8)-C(13)--C(12) 118.8 (5) S-C(I)--N(1) 127.6 (4) N(1)-C(14)-C(19) 118.3 (4) N(1)--C(2)-C(3) 108.1 (4) N(1)-C(14)-C(15) 121.2 (4) N(2)--C(3)--C(2) 106.4 (4) C(15)--C(14)--C(19) 120.5 (4) C(2)-C(3)-C(4) 129.3 (4) C(14)-C(15)-C(16) 119.9 (5) N(2)--C(3)--C(4) 124.2 (4) C(15)--C(16)-C(17) 120.6 (5) O-C(4)-C(3) 109-2 (4) C(16)-C(17)-C(20) 120.2 (5) C(3)-C(4)-C(7) 112.9 (4) C(16)--C(17)-C(18) 118.6 (5) O-C(4)-C(7) 105.3 (4) C(18)-C(17)-C(20) 121.1 (5) O-C(5)-C(6) 104.2 (6) C(17)-C(18)-C(19) 120.9 (5) C(5)-C(6)-C(7) 111.I (6) C(14)-C(19)-C(18) 119.4 (5) heo e ical plana i y [Z(A/a) 2 13.27 and 19.75, espec i ely] could no be eal. The dihed al angles be ween he N(1)- and N(2)-phenyl ings and he imidazole ing a e 64.6 (2) and 69.7 (2) ° espec i ely, bo h wi hin he ange 60-80 ° usually ound o he phenyl-imidazole sub o a ion. The wo a ached a oms N(1) and N(2) a e a 0.004 (4) and 0.082 (4)A om he espec i e ing leas -squa es planes. Imidazole ing. The obse ed alue o he C-S bond leng h is 1.677(5)A, a li le sho e han he 1.694 (3) A in e hylene hiou ea (Ba aglia, Bonama ini Co adi & Na delli, 1984), ha ing pa ial double-bond cha ac e , a cha ac e is ic ea u e in hese compounds. Bond leng hs and angles a e simila o hose ound in p e ious compounds (C iado, Conde & M i quez, 1983; Conde, L6pez-Cas o & M i quez, 1978). The ing de ia es e y sligh ly om heo e ical plana i y [~(A/ ) 2 = 16.83; 2~ 2 a 95% is 5.99] and he maximum a omic displacemen om he leas -squa es plane is 0.012 (5) ,/k. The h ee a ached a oms C(4), C(14) and C(8) a e a 0.070 (5), 0.129 (5) and 0.020 (4) A om he bes plane. Fu yl ing. The u yl ing has a special con o ma ion as a consequence o he p esence o he C(6)=C(7) bond, which s ongly a ec s he geome y o he ing. The C(6)=C(7) double-bond leng h is 1.289 (9)A, qui e simila o ha ound o 1,3-dihyd o-4-[(2S)- 2,5-dihyd o-2- u yl]-3-me hyl-l-(p- olyl)-2H-imidazole- 2- hione, 1.297 (7)A (Mo eno, L6pez-Cas o & M~- quez, 1985), bu signi ican ly sho e han he no mal C=C bond leng h o 1.337 (6) A (In e na ional Tables o X- ay C ys allog aphy, 1962). Bonds o a simila leng h ha e been ound p e iously [1.31 (2)A (Galloy & Wa son, 1983); 1.295 (6)A (Mazha -ul-Haque, Ahmed & Ho ne, 1983)]. The endocyclic bonds O-C(4) 1.431 (6) and O-C(5) 1.452 (9),& show he ypical asymme y due o anome ic e ec s. The a e age C-C single bond is 1.494 (9) A. Bond-angle alues o he ing a e: C(4)-O-C(5) 108.6(5), O-C-C 104.8(5) a . and C-C-C 110.6 (6) ° a . Bond leng hs and angles a e in ag ee- men wi h hose ound in he abo e-men ioned com- pound. The ing is app oxima ely plana and he maximum a omic de ia ion om he leas -squa es plane is 0.068 (7) A [~.(A/ ) 2 = 202.11]. In e ms o ing- pucke ing coo dina es (C eme & Pople, 1975) he ampli ude phase magni udes a e Q = 0.079 (6)A and p= 171 (5) ° o he sequence O-C(4)-C(7)-C(6)- C(5). The dihed al angle be ween he imidazole and u yl leas -squa es planes is 69.9 (2) °, di e ing om he 99.1 (2) ° ound o he abo e-men ioned com- pound. The glycosidic angle O-C(4)--C(3)-C(2) (Sunda alingam, 1969) is 105.6 (6) ° and co esponds o he syn con igu a ion (Pullman, 1976). C ys alpacking. Fig. 1 shows he con en s o he uni cell iewed along ¢. Packing is due o he hyd ogen bond C(6)-H(6)...O(~-x, l-y, --~+z). Each A. CRIADO, A. CONDE AND R. M/I, RQUEZ 1217 [ [ ~,,, C " 1 1 Fig. 1. The uni cell iewed along c. B oken lines a e hyd ogen bonds. molecule is linked by a hyd ogen bond o ano he molecule ela ed by a wo old sc ew axis pa allel o e, gi ing ise o in ini e helical chains pa allel o [001]: C(6)-H(6) 0.94 (6), C(6)...O 3.454 (8), H(6)...O 2.66 (6)/~ and C(6)-H(6)...O 143 (5) °. No o he in e molecula con ac s sho e han he sum o he an de Waals adii ha e been de ec ed. This ype o hyd ogen bond linking a C-H g oup wi h an O a om, bo h om he suga ing, is no usual o he imidazole C-nucleosides s udied. I is known ha he ing-O a om is also excluded om he hyd ogen-bonding schemes in py anose c ys al s uc u es (Je ey & Lewis, 1978). The au ho s hank P o esso Fe n/mdez-Bola ios o supplying he c ys als and P o esso L6pez-Cas o o aluable help in he da a-collec ion p ocess. The p esen wo k o ms pa o a wide p og am suppo ed by he Go e nmen h ough he 'Comisidn Aseso a de In- es igaci6n Cien i ica y T6cnica'. Re e ences BATTAGLIA, L. P., BONAMARTINI CORRADI, A. & NARDELLI, M. (1984). C oa . Chem. Ac a, 57, 545-563. CONDE, A., L6PEZ-CASTRO, A. & MARQUEZ, R. (1978). Re . Ibe oam. C is alog . Mine . Me alogen. l, 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. FERnANDEZ-BOLA ~OS GUZMAN, J. (1984). Doc o al hesis, Uni . de Se illa. GALLOY, J. & WATSON, W. H. (1983). Ac a C ys . C39, 348-350. HAMILTON, W. C. (1956). Ac a C ys . 12, 609-610. In e na ional Tables o X- ay C ys allog aphy (1962). Vol. III. Bi mingham: Kynoch P ess. (P esen dis ibu o D. Reidel, Do d ech .) In e na ional Tables o X- ay C ys allog aphy (1974). Vol. IV. Bi mingham: Kynoch P ess. (P esen dis ibu o D. Reidel, Do d ech .) JEFFREY, G. A. & LEWIS, L. (1978). Ca bohyd . Res. 60, 179-182. MAIN, P., FISKE, S. J., HULL, S. E., LESSINGER, L., GERMAIN, G., DECLERCQ, J.-P. & WOOLFSON, M. M. (1980). MULTAN80. 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. MAZHAR-UL-HAQUE, AHMED, J. & HORNE, W. (1983). Ac a C ys . C39, 383-385. MORENO, E., L6PEZ-CASTRO, A. & MARQUEZ, R. (1985). Ac a C ys . C41, 767-769. PULLMAN, B. (1976). Quan um Mechanics o Molecula Con o - ma ions, edi ed by B. PULLMAN, p. 350. London, New Yo k: John Wiley. STEWART, J. M., KUNDELL, F. A. & BALDWIN, J. C. (1970). The XRA YTO sys em. Compu e Science Cen e , Uni . o Ma yland, College Pa k, Ma yland. SUNDARALINGAM, M. (1969). Biopolyme s, 7, 821-860. Ac a C ys . (1985). C41, 1217-1222 S uc u es o Fou De i a i es o 5,7-Dichlo o-2,3-dihyd o-4-~-ni obenzoyl)- 4Hol,4-benzoxazine BY MARY F. GARBAUSKAS AND ELIZABETH A. WILLIAMS Gene al Elec ic Co po a e Resea ch and De elopmen , Schenec ady, NY 12301, USA AND HAROLD W. HEINE Bucknell Uni e si y, Depa men o Chemis y, Lewisbu g, PA 17837, USA (Recei ed 26 Sep embe 1984; accep ed 10 Ap il 1985) Abs ac . Compound (II): 5,7-dichlo o-2-e hoxy-2,3- dihyd o-4-(p-ni obenzoyl)-4H-1,4-benzoxazine, CIT- HIaC12N2Os, M =397, iclinic, P1, a=7.174 (3), 0108-2701/85/081217-06501.50 b = 7.859 (4), c = 16.965 (9) A, a= 85.50 (4), l= 79.27(4), y=71.62(3) °, V=891.7./k 3, Z=2, D x = 1-48 g cm -3, Mo Ka, 2 = 0.71069/k, ,u = 4.0 cm -I, © 1985 In e na ional Union o C ys allog aphy