X-ray Structure of a (o-ga/acto-Pentaacetoxypentyl)pyrazoline

LUDWIG SCHLICKSUPP, DAVID A. QUINCY AND N. R. NATALE 1563 by he C a om [C(5)] ha is bound o he es e g oup. The o ien a ion o he es e g oup wi h espec o he benzene ing would be expec ed o be an i- o synpe iplana because only hese wo con- o ma ions would allow esonance o he ca bonyl g oup wi h he benzene sys em. I is ound ha he es e g oup is ou o plane by 103 (1) ° and hus is no s abilized by esonance. This is con i med by he bond leng hs o he ca bonyl C o O [C(8)--O(2)] and o he ing C [C(8)--C(5)], which a e 1.19 (1) and 1.50 (1)A, espec i ely. Bo h bond leng hs a e ypical o a C--O double bond and a C--C single bond. The ou -o -plane o ien a ion o he es e g oup wi h espec o he benzene ing mus be due o s e ic hind ance by he wo bulky g oups, he py olidine ing and he C1 a om, which a e o ho o he es e g oup. A ela i ely sho bond leng h o a 1.34 ,~ is shown by he C(8)---O(1) single bond. In 3-hyd oxy-5- phenylisoxazole he C--O single bond showed he same dis ance (Ma ongiu, Biagini & Ca mas, 1969). C(9) and C(10) ha e unusually la ge he mal pa am- e e s, and sligh posi ional diso de may explain he unusually sho C(9)--C(10) dis ance o 1.447 (8) ,~. The Nicole R3/m X- ay di ac ome e and c ys- allog aphic compu ing sys em a Washing on S a e Uni e si y we e pu chased wi h unds p o ided by he Na ional Science Founda ion (G an CHE-8408407) and he Boeing Co po a ion. The au ho s hank D Roge Wille o Washing on S a e Uni e si y o echnical assis ance and he M. J. Mu dock Cha i a- ble T us o Resea ch Co po a ion and he Na ional Ins i u es o Heal h (Biomedical Resea ch Suppo G an No. 2-S07-RR07170-06) o inancial suppo . Re e ences CAMPANA, C. F., SHEPARD, D. F. & LITCHMAN, W. M. (1980). Ino g. Chem. 20, 4039--4043. HARRIS, R. L. N., HUPPATZ, J. L. & PHILLIPS, J. N. (1975). J. Aus . Chem. 30, 2213-2217. In e na ional Tables o X- ay C ys allog aphy (1974). Vol. IV, pp. 55, 99. Bi mingham: Kynoch P ess. (P esen dis ibu o Kluwe Academic Publishe s, Do d ech .) MCMURRY, J. E. (1973). O g. Syn h. 53, 59-62. MARONGIU, G., BIAGINI, S. & CARMAS, M. (1969). Ac a C ys . B25, 2108-2112. NATALE, N. R. (1982). Te ahed on Le . pp. 5009-5012. NATALE, N. R., MCKENNA, J. I., NIOU, C.-S., BORTH, M. L. & HOPE, H. (1985). J. O g. Chem. 50, 5660-5666. QUINCY, D. A. & NATALE, N. R. (1985). Unpublished obse a- ions. SCHLESSINGER, R. H., Doss, M. A. & RICHARDSON, S. (1986). J. Am. Chem. Soc. 108, 3112-3113. SHELDRmK, G. M. (1984). SHELXTL Use s Manual, e ision 4.1. Nicole XRD Co po a ion, Madison, Wisconsin, USA. Ac a C ys . (1989). C45, 1563-1565 X- ay S uc u e o a (D-galac o-Pen aace oxypen yl)py azoline BY C. F. CONDE AND A. CONDE Depa amen o de Fisica de la Ma e ia Condensada, Ins i u o de Ciencias de Ma e iales, Uni e sidad de Se illa-CSIC. Apa ado 1065, 41080 Se illa, Spain (Recei ed 9 Decembe 1988; accep ed 9 Feb ua y 1989) Abs ac . 1-(3,5-Dime hyl-3-ni o-l-py azolin-4-yl)- pen a-O-ace yl-D-galac o-pen i ol, C20H29N3O12, M = 503.5, o ho hombic, P212~21, a = 14.471 (9), b = 14.518 (3), c = 12.028 (2) ,~, V = 2527-0 (1.7)/k 3, Z = 4, Dx = 1-323 Mg m -3, a(Mo Kce) = 0.7107/~, /z =0.10mm -~, F(000) = 1064, oom empe a u e, inal wR = 0.035 o 1836 obse ed e lexions. Bond dis ances and angles a e all wi hin he expec ed anges. The py azoline ing exhibi s app oxima e mi o symme y and a pucke ing ampli ude o 0.244 (6))~. To sion angles o he ace oxy g oups wi h he suga chain ange om 33 o 72 ° . C ys al cohesion is mainly due o an de Waals in e ac ions bu he e a e wo in e molecula hyd ogen bonds linking molecules ela ed by sc ew axes along [100] and [001]. In oduc ion. The s uc u e de e mina ion o 1-(3,5- dime hyl-3-ni o- 1 -py azolin-4-yl)-pen a- O-ace yl-o- galac o-pen i ol was unde aken as pa o a con inuing esea ch p ojec on C-nucleosides and p ecu so s. The i le compound was p epa ed as an in e media e p oduc in he syn hesis o (pen a- ace oxypen yl)py azoles (III) wi h he suga ni oole ins (I) as dipola ophiles. Ini ially, he cyclo- addi ions ga e he py azolines (II), which we e a oma ized O he py azoles (Mance a, Rod iguez, Ro e & Galbis, 1988). The s e eochemis y was 0108-2701/89/101563-03503.00 © 1989 In e na ional Union o C ys allog aphy 1564 C2oH29N3OI2 en a i ely assigned on he basis o chemical and spec oscopic da a and an X- ay s udy o he i le compound was sugges ed o con i m he p oposed con igu a ion. NO2 N ---N G °2 13 R + RCHN 2 • Ac O--I_oA c CH2OAc CH2OAc (I) H ,,e" H C /I (11) G=Me R R =Me CH2OAc (ill) Expe imen al. Single c ys als in he o m o colou less needles elonga ed along [001] p epa ed in he O ganic and Pha maceu ical Chemis y Depa - men o he Uni e si y o Se illa. Cell pa ame e s we e e ined by leas -squa es calcula ions om 25 e lexions wi h 5<0<20 ° on an En a -Nonius CAD-4 di ac ome e . In ensi y da a om a c ys al o dimensions 0.20 x 0.15 x 0-30 mm we e collec ed up o sinO/A = 0.60/k -1 wi h an o~--20 scan using g aphi e-monoch oma ed MoKa adia ion. Two e lexions (413, 343) moni o ed pe iodically du ing da a collec ion showed ha he c ys al was s able o X- ays. Index anges o unique da a we e 0_< h _< 17, 0 ___ k_< 17, 0 _< 1___ 14. 2476 e lexions we e collec ed o which 1836 unique e lexions we e conside ed obse ed [1>2o(/)]. The s uc u e was sol ed by di ec me hods using MULTAN80 (Main e al., 1980). All he H a oms we e loca ed om a di e ence Fou ie map. Full-ma ix leas -squa es e inemen wi h non-H a oms e ined aniso opically and H a oms iso opically con e ged a R = 0.048 and wR = 0.035, S (goodness o i ) = 1.38. The unc- ion minimized was Y~w(IFol-lFcl) 2 whe e w= 1/o~(F). Maximum shi /e.s.d, a io o non-H a oms =0-02. Residual elec on densi ies in he inal di e ence Fou ie map we e wi hin 0.20 and -0.25 e A -3. The a omic sca e ing ac o s we e om In e na ional Tables o X- ay C ys allog aphy (1974). C ys allog aphic p og ams o he XRAY76 sys em (S ewa , Machin, Dickinson, Ammon, Heck & Hack, 1976) we e used h oughou . Discussion. The inal posi ional and equi alen iso- opic he mal pa ame e s o he non-H a oms a e Table 1. A omic coo dina es and he mal pa ame e s (A 2 × 103) U~q = ]Y~,Y.j U~a*aTa,.aj.cos(a, aj). x y z U~ O11 0.7034 (4) 0.0799 (5) 0.4340 (4) llO O) O12 0-5870 (3) 0.1282 (4) 0.3367 (6) 125 (3) O41 0.9479 (2) 0.1552 (2) 0.1666 (3) 38 (1) 042 0.9541 (3) 0.0878 (3) -04)011 (4) 82 (3) O51 0.8581 (2) 0.2748 (2) 0.3043 (3) 39 (1) 052 0.7195 (3) 0.2937 (3) 0.3777 (3) 74 (2) O61 0.8288 (2) 0-2989(2) 0.0060 (3) 37 (1) 062 0.9735 (3) 0.3119 (4) -0.0542 (4) 83 (2) 071 0.7276 (2) 0.4241 (2) 0.1464 (3) 39 (11 072 0.7322 (3) 0-5085 (3) 0.3032 (3) 73 (2) 081 0.8549 (3) 0.5805 (3) 0.0970 (3) 47 (2) 082 0.9849 (3) 0.6179 (3) 0.0056 (4) 82 (2) NI 0.7776 (4) -0.0815 (3) 0.2382 (5) 66 (2) N2 0.7030 (4) -0.0435 (3) 0.2555 (5) 64 (2) Nil 0.6620 (4) 0.0931 (4) 0.3463 (6) 73 (3) CI 0.7095 (4) 0.0593 (4) 0.2396 (5) 47 (2) C-'2 0.8148 (4) 0.0800 (4) 0.2445 (5) 36 (2) C3 0.8531 (4) -0.0162 (4) 0.2128 (5) 44 (2) C4 0.8475 (4) 0.1554 (4) 0.1645 (5) 34 (2) C5 0.8187 (4) 0.2526 (4) 0.1966 (5) 29 (2) C6 0-8580 (4) 0.3246 (4) 0.1175 (5) 30 (2) C7 0.8269 (4) 0.4219 (4) 0-1416 (5) 33 (2) C8 0.8622 (5) 0.4879 (4) 0.0534 (5) 46 (2) C ll 0.6584 (5) 0.0830 (6) O. 1366 (9) 89 (4) C31 0.9366 (6) -0.0456 (5) 0.2806 (9) 83 (4) C41 0.9916 (4) 0.1219 (5) 0.0751 (6) 55 (3) (242 1.0941 (5) 0-1365 (7) 0.0878 (7) 76 (4) C51 0.8013 (5) 0.2944 (5) 0.3887 (5) 48 (3) C52 0.8500 (6) 0.3177 (7) 0-4900 (7) 88 (4) C61 0.8955 (5) 0.2946 (4) -0.0732 (5) 51 (3) C62 0.8558 (6) 0.2671 (6) -0.1820 (6) 72 (3) C71 0.6886 (4) 0.4695 (4) 0-2347 (5) 45 (2) C72 0.5857 (5) 0.4601 (6) 0-2330 (7) 73 (3) C81 0.9215 (5) 0.6404 (4) 0.0632 (6) 52 (3) C82 0.9036 (6) 0.7351 (5) 0.1006 (6) 65 (3) 012 N1 C52(~.1 ~" 15 071~C 062 Fig. 1. An ORTEP iew o he molecule wi h a om labelling. gi en in Table 1.* An ORTEP (Johnson, 1965) plo o he molecule wi h a omic labelling is displayed in Fig. 1. Bond leng hs and angles in ol ing non-H a oms a e lis ed in Table 2 and he alues a e all wi hin he expec ed anges. The pucke ing o he py azoline ing can be desc ibed (C eme & Pople, 1975) by a pucke ing * 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 Documen Supply Cen e as Supplemen a y Publica ion No. SUP 51944 (13 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 CH1 2HU, England. C. F. CONDE AND A. CONDE 1565 Table 2. Bond dis ances (A) and angles (°) in ol ing non-H a oms 062--C61 1.179 (9) C62--C61 1.484 (10) C61--061 1.358 (8) 082--C81 !.195 (9) C31--C3 1.519 (I 1) C82--C81 1.470 (10) C4--041 1.453 (6) C4--C5 1.521 (8) C4--C2 1.532 (8) 05 I--C5 i !.337 (7) O51---C5 1.452 (6) O71---C7 1.440 (6) O71-----C71 1.371 (7) C6----O61 1.454 (7) C6--C7 1.511 (8) C6--C5 1.524 (8) C7--C8 1.517 (8) O41---C41 1-359 (8) C51--O52 1.191 (8) C51--C52 !.448 (ll) C8----<)81 1.447 (7) O81---C81 1.361 (8) C3---C2 !.550 (8) C3---NI 1.478 (8) C42--C41 1.507 (10) C2--C1 1.553 (8) C41--O42 1.174 (8) NI--N2 1.230 (7) O72---C71 1.182 (7) C72--C71 1.495 (9) CI--N2 i.507 (7) CI--NI I 1.536 (10) C1----CI 1 !.484 (12) NI I--O11 1.229 (9) NI 1--OI2 1.204 (8) 062--C61--C62 126-8 (7) C62--C61--061 110.8 (6) 062--C61--061 122-3 (6) C5---C4--C2 !14.7 (5) 041---C4---C2 107.3 (4) 041------C4------C5 105.7 (4) C51--O51--C5 118"9 (4) C7---O71---C71 116"9 (4) C7--C6---C5 !14-2 (5) O61--C6-----C5 106.9 (4) O61---C6--C7 109-3 (4) C61--O61---C6 116.8 (4) O71---C7---C6 109.0 (4) C6----C7---C8 110.9 (5) O71--C7--C8 110.5 (4) C4--O41---C41 116-9 (4) O51--C51--C52 112"9 (6) O51--C51--O52 121.7 (6) O52---C5 I---C52 125.4 (6) 051 ---C5---C6 105"0 (4) C4----C5----C6 112.0 (5) C4----C5--O51 109-0 (4) C7---C8----<)81 108"0 (5) C8---O81---C81 115-6 (5) C31--C3--N1 107.3 (5) C31---C3---C2 113.9 (5) C2--C3--Ni 105.3 (5) C4--C2--C3 112.2 (5) C3--C2--CI 99.6 (4) C4--C2--Ci 114.7 (5) O41--C41--C42 109.0 (6) C42--C41--O42 126.4 (6) O41---C41---O42 124.6 (6) C3--NI--N2 113"3 (5) C2--CI--C! i 11g.3 (6) C2---CI--NI 1 110.2 (5) C2---CI--N2 104.4 (5) NI I---CI---CI 1 113-6 (6) N2--CI--CI 1 107-7 (5) N2--CI--NI 1 100.5 (5) NI--N2--CI I I 1.6 (5) O72--C71--C72 125.8 (6) O71--C71--C72 li0.8 (5) O71--C71--O72 123'4 (5) C82--C8 i--<)8 i I i 2.4 (6) O82--C81 --08 i ! 22.9 (6) O82--C81--C82 124.6 (6) CI--NI 1--O12 117.3 (7) C1--NI I--<)l I 116.7 (6) Ol I--NI 1--O12 126"0 (7) ampli ude q = 0.244 (6)A and a phase angle q~= -149-9 (14) ° o he sequence C1--C2--C3--N1-- N2. The asymme y pa ame e (Na delli, 1983a) ACs(C2)=0.021 (3) indica es app oxima e mi o symme y in he ing. The i e ace oxy g oups a e plana and hei o - sion angles wi h espec o he main chain a e C2--C4--O41--C41 = 108.1 (5), C4--C5--O51-- C51 = - 119.0 (5), C5--C6 O61--C61 -- - 129.3 (5), C6--C7--O71--C71 -- 132.8 (5) and C7--C8--O81--C81 = 146.7 (5) °. The Newman p ojec ions co esponding o C---C bonds o he chain a e shown in Fig. 2 om which he con ig- u a ion o he suga can be deduced. The c ys al cohesion is mainly due o an de Waals in e ac ions bu wo in e molecula con ac s may be conside ed as hyd ogen bonds. These in e ac- ions a e: C72--H723...O42 (x- ½, - y + ½, - z) link- ing molecules ela ed by a sc ew axis pa allel o [100], and C8--H81...O72 (-x+ 3, -y+ 1, z-J) linking molecules ela ed by a sc ew axis along [001]. De ails o hese con ac s a e: C72--H723 = 1.06 (5), C72..-O42 = 3.448 (9), H723...O42 = 2-44 (6) A, C72--H723...O42 -- 159 (4) ° and C8--H81 -- 1-03 (5), C8...O72 -- 3-306 (8), H81...O72 -- C2 C4 051~ H5 061 ~ H6 041 sa.a 1-60 " H4 J S4 ]-06.3 -051 I Ha I C6 C7 C4---C5 C5~C6 c5 H7 071 H81 a..~j H82 66.6 ~ 84 .e 07, T I H7 C8 081 C6---C7 C7--C8 Fig. 2. Newman p ojec ions h ough he C---C bonds o he suga chain. S anda d de ia ions in o sion angles in ol ing non-H a oms a e in he ange 0.5-0.8 ° . 2.35 (6) A, C8--H81...O72= 154 (4) °. No o he con ac s sa is y he c i e ia o Taylo & Kenna d (1982) o hyd ogen bonds. The molecula geome y and c ys al packing we e compu ed by PARST (Na delli, 1983b). The au ho s hank P o esso J. A. Galbis o supplying he c ys als and o discussions on chemi- cal aspec s, and P o esso A. Lopez-Cas o o col- lec ing he di ac ome e da a. This wo k is pa o a esea ch p ojec suppo ed by he CAICYT o he Spanish Go e nmen and by he CSIC. Re e ences CREMER, D. & POPLE, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358. 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 Kluwe Academic Publishe s, Do d ech .) JOHNSON, C. K. (1965). ORTEP. Repo ORNL-3794. Oak Ridge Na ional Labo a o y, Tennessee, USA. MAIN, P., FISKE, S. J., HULL, S. E., LESSINGER, L., GERMAIN, G., DECLERCQ, J.-P. & WOOLFSON, i. M. (1980). MULTANSO. 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. MANCERA, M., RODRIGUEZ, E., ROFV'E, I. & GALBIS, J. A. (1988). J. O g. Chem. 53, 5648-5651. NARDELLI, M. (1983a). Ac a C ys . C39, 1141-1142. NARDELLI, M. (1983b). Compu . Chem. 7, 95-98. STEWART, J. M., MACHIN, P. A., DICKINSON, C. W., AMMON, H. L., HECK, H. & FLACK, H. (1976). The XRAY76 sys em. Tech. Rep. TR-446. Compu e Science Cen e , Uni . o Ma yland, College Pa k, Ma yland, USA. TAYLOR, R. & KENNARD, O. (1982). J. Am. Chem. Soc. 104, 5063-5070.