Structure of l-(p-Ethoxyphenyl)-1,3-dihydro-3-phenyl-2H-benzimidazole-2-thione, C2IHlaN2OS

188 C23H22N4OTS2 Fig. 2. Molecula packing iewed down he b axis. The glycosyl o sion angle C(2)--N(1)-C(1')--O(4') is --74.2 (2) °. The suga pucke is in a wis ed o m, C(4')-endo-C(3')-exo, wi h pseudo o a ion angle P = 220.9 o as de ined by Al ona & Sunda alingam (1972). A simila con o ma ion is also obse ed in 8,2'- O-cycloadenosine (P=217.5 °) and in 8,2'-S-cyclo- 5'-AMP (P= 232.7°). The molecula packing is illus a ed in Fig. 2. A hyd ogen bond is obse ed be ween 0(5') and N(3) in he neighbou ing molecule ela ed by he 21 sc ew axis. Re e ences ALTONA, C. & SUNDARALINGAM~ M. (1972). J. Am. Chem. Soc. 94, 8205-8212. ASHIDA, T. (1979). HBLSV. The Uni e sal C ys allog aphic Compu ing Sys em-Osaka. Lib a y o P og ams, Compu ing Cen e , Osaka Uni . In e na ional Tables o X- ay C ys allog aphy (1974). Vol. IV. Bi mingham: Kynoch P ess. JOHNSON, C. K. (1976). ORTEPII. Repo ORNL-5138. Oak Ridge Na ional Labo a o y, Tennessee. KITAMURA, K., MIZL NO, H., SUGIO, S., OKABE, N., IKEHARA, M. & ToM A, K. (1983). Ac a C ys . C39, 1551-1553. MAIN, P., HULL, S. E., LESSINGER, L., GERMAIN, G., DECLERCQ, J.-P. & WOOLFSON, M. M. (1978). MULTAN78. 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. NEIDLE, S., TAYLOR, G. L. & COWLING, P. C. (1979). Ac a C ys . B35, 708-712. TANAKA, K., FuJn, S., FUJIWARA, T. & TOMITA, K. (1979). Ac a C ys . B35, 929-933. Ac a C ys . (1984). C40, 188-190 S uc u e o l-(p-E hoxyphenyl)-1,3-dihyd o-3-phenyl-2H-benzimidazole-2- hione, C2IHlaN2OS BY A. CRIADO, A. CONDE AND R. M.~,RQUEZ Depa amen o de Op ica y Secci6n de F sica del Cen o Coo dinado de CSIC, Uni e sidad de Se illa, Spain (Recei ed 18 Ap il 1983; accep ed 21 Sep embe 1983) Abs ac . M =346-4, o ho hombic, P212121, a= 7.600(1), b= 11.132(2), c=20.767 (3)A, = 1756.9(5)A 3, z=4, Dx=1.31Mgm -3, 2(CuKc ) =.1.5418/k, /~= 1.67mm -1, F(000)=728, T= 300 K. Final R = 0.049 o 1531 obse ed independen e lec ions. The benzimid~zole bicycle is quasi-plana , he dihed al angle be ween he wo used ings being 1.6 (2) °. The unsubs i u ed phenyl ing is plana while he phenyl ing wi h he e hoxy subs i uen de ia es signi ican ly om he expec ed plana con o ma ion. In oduc ion. The c ys al s uc u e o he i le com- pound has been de e mined as pa o a sys ema ic s uc u al analysis o imidazole C-nucleosides syn- hesized in he O ganic Chemis y Depa men o his Uni e si y. Recen ly, we ha e epo ed (C iado, Conde & M~ quez, 1983) he s uc u e o he i s disubs i u ed (a bo h N a oms) imidazole C-nucleoside. 0108-2701/84/010188-03501.50 The i le compound (I) has been ob ained (Fe nb.ndez-Bola ios, Fuen es-Mo a & Fe n indez- Bola ios Guzmhn, 1983a) om he p- oluene- sul ona e o 4-( l-D-e y h o u anosyl)-l-(p-e hoxyphen- yl)-l,3-dihyd o-3-phenyl-2H-imidazole-2- hione (Fe - nimdez-Bola ios, Fuen es-Mo a & Fe nhndez-Bola ios Guzm~m, 1983b) using a eac ion simila o ha o Tipson & Cohen (1965). This syn hesis is he i s case o nucleoside a oma iza ion. s C2H 5 (I) © 1984 In e na ional Union o C ys allog aphy A. CRIADO, A. CONDE AND R. M/~RQUEZ 189 Expe imen al. Needle-shaped colo less c ys als, 0.05 ×0.06x0.14mm, kindly supplied 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 s udies showed o ho hombic symme y, sys ema ic absences consis en wi h P212~2~. Philips PW 1100 ou -ci cle compu e -con olled di ac ome e , g aphi e-mono- ch oma ed adia ion. Uni -cell pa ame e s om leas - squa es e inemen o ~ alues o 33 e lec ions. 1729 e lec ions wi h 0<65 ° (h<9, k< 14, l<25) measu ed, 09-20 scan mode, 1531 wi h I> 2o(1) X conside ed obse ed. Two e e ence e lec ions mon- s 52527(18) i o ed pe iodically, in ensi y changes less han 2%. 0(I) -4101(48) Lo en z and pola iza ion co ec ions, none o ab- N(1) 52808(54) N(2) 73068 (55) so p ion o ex inc ion e ec s. Weigh ed angen - c(1) 59232(63) o mula e inemen (MULTAN78, Main, Hull, Les- c(2) 62185(64) singe , Ge main, Decle cq & Wool son, 1978) o 180 c(3) 75071 (67) c(4) 86847 (76) e lec ions wi h E> 1.5. Full.ma ix leas -squa es c(5) 85689(85) e inemen o 281 pa ame e s based on F o o e all c(6) 72880(88) C(7) 61161 (75) obse ed e lec ions (CR YLSQ o XRAY70, S ewa , c(8) 37658 (65) Kundell & Baldwin, 1970). Fou ie di e ence syn hesis c(9) 37768 (70) up o sin0/2= 0.7,~-~ ga e all H-a om posi ions; a c(1o) 23521 (75) C(I 1) 9032 (68) leas -squa es e inemen in a mixed mode including H c(12) 8414 (67) a oms, each one wi h an iso opic empe a u e ac o c(13) 23083 (72) equal o ha o he a ached skele on a om, ga e c(14) -20360(76) c(15) -32549 (77) R--R,= 0.049. Las -cycle pa ame e shi s less han c(16) 84187 (65) 0.34, a e age 0.1a. Final di e ence Fou ie map c(17) 101124(72) c(18) 112177 (73) excu sions --0.25 <Ap < 0.35 e A -~. A omic sca - c(19) 105956(72) e ing ac o s om In e na ional Tables o X- ay c(20) 88844(83) C ys allog aphy (1974). Weigh ing scheme in he o m c(21) 77897 (77) 1/a2(I) based on coun ing s a is ics. Discussion. Final a omic coo dina es and equi alen iso opic empe a u e ac o s (Hamil on, 1959) a e gi en in Table 1.* Bond leng hs and angles o he non-H a oms a e gi en in Fig. 1. The C-H dis ances ange om 0.95 o 1.19/k, wi h a mean alue o 1.08 (6) A,. Benzimidazole ing. Bond dis ances and angles in he imidazole ing a e in good ag eemen wi h he epo ed alues o imidazole-2- hione compounds (Conde, L pez-Cas o & M i quez, 1978; C iado e al., 1983) showing no app eciable dis o ion due o he bicycle o ma ion. Only he C(2)-C(3) bond dis ance is somewha long in compa ison wi h he mean alue [ 1.345 (5)/k] o he o emen ioned compounds. The ing keeps i s plana ea u e and he a omic de ia ion~ om he leas -squa es plane h ough he i e a oms a e wi hin he s anda d de ia ions (Z z = 0.72). The benzene ing, on he con a y, shows an app eciable dis o ion om plana i y (Zz= 27.39,), wi h a oms whose dis ance * Lis s o s uc u e ac o s, aniso opic he mal pa ame e s, H-a om coo dina es and leas -squa es-planes' da a 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 38889 (1"2' pp.). Copies may be ob ained h ough The Execu i e Sec e a y, In e na ional Union o C ys al- log aphy, 5 Abbey Squa e, Ches e CH 1 2HU, England. o he leas -squa es plane is g ea e han h ee s anda d de ia ions. The a e age C-C bond leng h in he ing is 1.389 (7)A and C-C-C angle is 120.0 (5) °. The whole bicycle is quasi-plana , he dihed al angle be ween he imidazole and benzene leas -squa es planes being 1.6 (2) ° . Table 1. Posi ional pa ame e s (x l0 s) and equi alen iso opic he mal pa ame e s (x 104) o he non-H a oms wi h e.s.d. 's in pa en heses y z U~,(M) 10175 (13) -2312"9 (6) 450 (4) -27848 (31) -11181 (18) 501 ('12) 3744 (34) -10470 (19) 365 (12) 16914 (35) -13045 (19) 365 (13) 10275 (44) -15567 (22) 371 (14) 6115 (41) -4873 (22) 351 (15) 14402 (41) -6487 (23) 362 (15) 18824 (47) "2034 (25) 475 (18) 14255 (53) 4187 (27) 549 (20) 5597 (52) 5804 (26) 542 (20) 1292 (45) 1287 (24) 430 (16) -4036 (42) -10742 (23) 372 (15) -14158 (46) -14696 (25) 432 (16) -21796 (45) -14697 (26) 447 (17) -19503 (44) -10830 (24) 394 (15) -9217 (47) -6999 (23) 411 (15) -1425 (45) -7045 (25) 404 (16) -25485 (55) -7782 (31) 568 (21) -35714 (56) -9505 (32) 577 (21) 24958 (46) -16586 (23) 377 (15) 21513 (47) -18020 (26) 465 (18) 29465 (54) -21276 (28) 542 (20) 40733 (53) -23039 (28) 536 (19) 43990 (52) -21639 (32) 608 (22) 36129 (48) -18433 (30) 531 (20) Gi9) el .e- **,,-I= @ ~ ~ -~/ ,2,0 ~,o' c~,),~B;),,,~ " , 00 115.1 ~ _~./"'~ 105. 7 '~'~(C(l ,) C( 51 Fig. 1. Bond leng hs (A) and angles (o) in he molecule. S anda d de ia ions a e below 0.009 A and 0.6 °. 190 C21HIsN2OS The dihed al angles o med by he imidazole ing and he wo bound phenyl ings a e 73.7 (2) ° o he N(2)-a ached ing and 61.4 (2) ° o he N(1)-a ached ing, bo h alues being simila o hose encoun e ed in he analogous compounds s udied p e iously, anging om 60 o 80 ° . The o sional angles desc ibing he bonding a e C(1)-N(1)-C(8)-C(9)=63.5 (6) and C ( 1 )-N(2)-C ( 16)-C (21) = 75.2 (7)0, espec i ely. PhenyI ings. The N(2)-a ached phenyl ing is plana , wi h a omic de ia ions om he mean plane wi hin he s anda d de ia ions (Z 2 = 4.52). The a e age C-C bond leng h is 1.385 (8)A and he mean C-C-C angle is 120.0 (5) °. The N(1)-a ached phenyl ing, on he con a y, de ia es signi ican ly om he expec ed plana con o ma ion (Z2= 29.07), wi h an a e age C-C bond leng h o 1.390 (7) A and C-C-C angle o 120.0 (5) ° . The e hoxy g oup exhibi s asymme y in he C(10)- C(ll)-O(1)= 115.1 (5) and C(12)-C(II)-O(1)= 124.4 (5) ° angles, a common ea u e o he phenoxy g oup (Domiano, Na delli, Balsamo, Macchia & Macchia, 1979). Fig. 2 shows a iew o he uni cell along he b axis. No e idence o hyd ogen bonds exis s and no in e molecula con ac s app eciably sho e han he sum o he an de Waals adii ha e been de ec ed. The au ho s hank P o esso Fe nandez-Bola ios. o supplying he c ys als and he s a o he Ins i u o 'Rocasolano' o CSIC (Mad id) o collec ing he di ac ome e da a. The p esen wo k o ms pa o a wide esea ch p ojec suppo ed by he Go e nmen h ough he 'Comisi6n Aseso a de In es igaci6n Cien- i ica y T6cnica'. 1~I/4 1,1/4 ,..,c(181 [ • / C(19)(~ 4~C( 17)~, al ,, / cCI( 154 'I/4 'I/4 Fig. 2. Uni cell iewed along he b axis. Re e ences CONDE, A., LOPEZ-CASTRO, A. & MARQUEZ, R. (1978). Re . Ibe oam. C is alog . Mine . Me alogen. 1, 23-26. CRIADO, A., CONDE, A. & MARQUEZ, R. (1983). Ac a C ys . C39, 122-125. DOMIANO, P., NARDELL , M., BALSAMO, A., MACCHIA, B. & MACCI- IA, F. (1979). Ac a C ys . B35, 1363-1372. FERNANDEZ-BOLA~OS, J., FUENTES-MOTA, J. & FERNANDEZ- BOLAg OS GUZ ~N, J. (1983a). Ca bohyd . Res. To be published. FERNANDEZ-BOLA~OS, J., FUENTES-MOTA, J. & FERNA , DEZ- BOLA~OS GUZMAN, J. (1983b). An. Qu m. To be published. HAMILTON, W. C. (1959). Ac a C ys . 12, 609-610. In e na ional Tables o X- ay C ys allog aphy (1974). Vol. IV. Bi mingham: Kynoch P ess. MAIN, P., HULL, S. E., LESSINGER, L., GERMAIN, G., DECLERCQ, J.-P. & WOOLFSON, M. M. (1978). MULTAN78. 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. STEWART, J. M., KUNDELL, F. A. & BALDWIN, J. C. (1970). The XRAY70 sys em. Compu e Science Cen e , Uni . o Ma yland, College Pa k, Ma yland. TlPSON, R. S. & COHEN, A. (1965). Ca bohyd . Res. 1, 338-340. Ac a C ys . (1984). C40, 190-193 2-(l,3-Di hiol-2-ylidene)-4-eyclopen ene- 1,3-dione, CaH40282, and 2-(l,3-Benzodi hiol- 2-ylidene)cyclohexanone, CI3H12OS 2 BY WILLIAM H. WATSON, JEAN GALLOY AND DAVID A. GROSSIE FASTBIOS Labo a o y, Depa men o Chemis y, Texas Ch is ian Uni e si y, Fo Wo h, TX 76129, USA AND Juzo NAKAYAMA Depa men o Chemis y, Facul y o Science, Sai ama Uni e si y, U awa, Sai ama 338, Japan (Recei ed 22 July 1983; accep ed 22 Sep embe 1983) Abs ac . C8H40252 (2), M = 196.25, o ho hombic, Pnma, a = 18.080 (2), b = 1 I. 102 (I), c = 3.8904 (4) A, V= 780.9 (1) A 3, z= 4, Dx= 1-67Mgm -3, CuKa, 2=1.54178A, #=5.549 mm -l, F(000)=400, oom empe a u e, R =0.046 based on 597 unique e lec ions. CI3HI:OS 2 (3), M 0108-2701/84/010190-04501.50 = 248.24, monoclinic, P21/c, a= 6.459 (1), b= 14-263 (3), c= 13.514 (4)A, l--- 112.16 (2) ° , V= 1153.0 (6) A 3, Z = 4, D x = 1.43 Mg m -3, Cu Kc , # = 3.90 mm -x, F(000) = 520, oom empe a u e, R = 0.074 based on 1429 unique e lec ions. Compound (2) is plana excep o a sligh 2 ° old along he S.-.S line. © 1984 In e na ional Union o C ys allog aphy