Structure of l'-(p-Bromophenyl)-3'-ethyl- 1',3', 4',5'-tetrahydro- 1,2-dideoxy-D-glycero- L-gluco-heptofuranoso[ 1,2-d]imidazole-2'-thione,* C16H21BrN205 S

1418 4-BROMO- 1-(4-NITROPHENYL)-3-PHENYLPYRIDAZINIUM-5-OLATE R R R I R" R" R" R R R' O II I R" R" Cha ge dis ibu ion on he ing leads one o p edic 1,3-dipola cycloaddi ion o double and iple bonds, as ollows: R' 0 I The po en ial 1,3-dipola cha ac e o be aines, such as (II), is as expec ed (Ka i zky & Dennis, 1979). The ype o laye ed packing a angemen (along a wi h an o se o 0.33 A) ound in (IIa) is associa ed wi h ela i ely small in e - ing dihed al angles. Ap- pa en ly, su icien ene gy is gained in his ype o s uc u e ela i e o some hypo he ical a angemen ha ing less plana molecules o o se he inc ease in in amolecula ene gy. Only B ...C(9 ~) 3.373(3), B ...H(9 ~) 3.01 (3) and O(6).-.H(5 ~j) 2.31 (3)A [(i) l--x, l--y, ~; (ii) ~, l--y, l--z] a e conside ably sho e han he sum o he an de Waals adii (B 1.95, C 1.70, N 1.50, O 1.40, H 1.20 A) (Pauling, 1960). Re e ences AMIT, A. G. & HOPE, H. (1966). Ac a Chem. Scand. 20, 835-844. B~LARD, R. E. & NORRIS, E. K. (1975). Ac a C ys . B31, 626-628. BAR, I. & BEm'~STEIN, J. (1981). Ac a C ys . B37, 569-575. CARISTI, C., GATTUSO, M., FERLAZZO, A. & STAGNO D'ALCONTRES, G. (1983). Te ahed on Le . 24, 1285-1288. CHANG SUN CHOI & ABEL, J. E. (1972). Ac a C ys . B28, 193-201. CHURCHILL, M. R. (1973). Ino g. Chem. 12, 1213-1214. DEWAR, M. J. S. & SCHMEISING, H. N. (1968). Te ahed on, 11, 96-120. DOMENICANO, A., MAZZEO, P. & VACIAGO, A. (1976). Te ahed on Le . pp. 1029-1032. DOME'N1CANO, A., VACIAGO, A. ~. COULSON, C. A. (1975). Ac a C ys . B31, 221-234. HAMOR, M. J. & HAMOR, T. A. (1978). Ac a C ys . B34, 863-866. In e na ional Tables o X- ay C ys allog aphy (1968). Vol. III, p. 270. Bi mingham: Kynoch P ess. In e na ional Tables o X- ay C ys allog aphy (1974). Vol. IV, pp. 99-101, 149-150. Bi mingham: Kynoch P ess. JOHNSON, C. K. (1965). ORTEP. Repo ORNL-3794. Oak Ridge Na ional Labo a o y, Tennessee. KATRITZKY, A. R. & DENNIS, N. (1979). Recen P og ess in he Cycloaddi ion Reac ions o 3-Oxidopy idinium Be aines and Analogous Compounds in New T ends in He e ocyclic Chemis- y. Ams e dam: Else ie . KELEMEN, J., KORMANY, G. & RIHS, G. (1982). Dyes Pigmen s, 3, 249-27 I. LOFTHUS, A. (1959). Mol. Phys. 2, 367-371. Molecula S uc u es and Dimensions (1972). Vol. A1, edi ed by O. KENNARD, D. G. WATSON, F. H. ALLEN , N. W. ISAACS, W. D. S. MOTHERWELL, R. C. PETTERSEN & W. G. TOWN, p. $2. U ech : Oos hoek. MOREIRAS, D., SOLANS, J., SOLANS, X., MIRAVITLLES, C., GERMAIN, G. & DECLERCQ, J. P. (1981). Ac a C ys . B37, 737-739. PAULING, L. (1960). The Na u e o he Chemical Bond, 3 d ed., p. 260. I haca: Co nell Uni . P ess. TROMBETTI, A. (1968). Can. J. Phys. 46, 1005-101 I. Ac a C ys . (1983). C39, 1418-1421 S uc u e o l'-(p-B omophenyl)-3'-e hyl- 1',3', 4',5'- e ahyd o- 1,2-dideoxy-D-glyce o- L-gluco-hep o u anoso[ 1,2-d]imidazole-2'- hione,* C16H21B N205 S BY M. D. ESTRADA, A. CONDE AND R. M.h, RQUEZ Depa amen o de F sica del Es ado S6lido, Facul ad de F 'sica, Uni e sidad de Se illa, Spain (Recei ed 18 Ap il 1983; accep ed 27 June 1983) Abs ac . M,=433.3, o ho hombic, P2,2~2,, a= 8.466 (2), b .... 27. 136 (5), c - 7.776 (5) A, V = 1786(1)A3, Z=4, D,,,= 1.60(l),Dx= 1.61Mgm -3, *IUPAC name: 6(pb omophcnyl) 4-e hyl-3hyd oxy 2(1,2,3 ihyd oxyp opyl)-2,3,3a,5,6,6a-hex ahyd o u ol 2,3-dlimidazole- 5(4H) hionc. 0108-2701/83/101418-04501.50 Mo Ka, 2 = 0.7107 A, a = 2.42 mm-', F(000) = 888, 300 K, R =0.045 o 1 196 obse ed independen e lex- ions. The suga ing adop s a 4T 3 con o ma ion and he dihed al angle in he bicycle is 72-2(4) ° . In e - molecula hyd ogen bonds link molecules ela ed by a sc ew axis o gi e helical chains pa allel o 1001 I. % 1983 In e na ional Union o C ys allog aphy M. D. ESTRADA, A. CONDE AND R. MARQUEZ 1419 In oduc ion. The s uc u e de e mina ion o he i le o XRAY70 (S ewa , Kundell & Baldwin, 1970) used compound h oughou .* B H x h, OH HOH2C ,~ ~ N C H OH "2 5 * Lis s o s uc u e ac o s and aniso opic he mal 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 38693 (17 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 CHI 2HU, England. was unde aken as pa o a wide esea ch p ojec in ol ing compounds ob ained by eac ion o 2-deoxy- 2-e hyl(p opyl)aminohexose(hep ose) wi h a yl (alkyl) iso hiocyana es (Ga cia Gonzalez, Galbis-P6 ez, Fe nandez-Ga cia-Hie o & Fe n indez-Bola ios, 1979; B Galbis-P6 ez, Pin o Co aliza, Rom in-Gal in & Gom6z- s Guill~n, 1979), whose p incipal aim is o es ablish hecon- o(1) o ma ional de ails o he molecula s uc u e in he solid o(2) 0(3) s a e. The u anoid s uc u e o he suga moie ies o 0(4) hese compounds is now well con i med (Conde, L6pez- 0(5) Cas o & M i quez, 1978). The i le compound has N(I) N(2) been p epa ed (Galbis-P6 ez, Palacios, Jim6nez- c(1) Requejo, A alos & Fe n indez-Bola ios, 1983) by c(2) condensa ion o 2-amino-2-deoxy-o-glyce o-L-gluco- c(3) c(4) hep ose (Galbis-P6 ez, Pin o Co aliza, Rom in-Gal in c(5) & Gom6z-Guill6n, 1979) and ac ioned c ys alliza ion c(6) C(7) sepa a ion. I s chemical na u e was es ablished om c(8) elemen al analysis and spec oscopic da a and he c(9) X- ay analysis was ca ied ou o de ine he s uc u al C(lO) c(11) de ails, c(12) C(13) C(14) c(15) C(16) Expe imen 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; c ys al 0.07 x 0.09 × 0.12 mm, uni -cell pa ame e s by leas squa es om 44 e lexions, En a -Nonius CAD-4 di ac ome e , 20~a~ = 60 ° (h < 11, k < 38, l< 10), 09--20 scan, h ee e lexions moni o ed, a ia ion less han 1% o mean in ensi y, 2961 indepen- den e lexions measu ed, 1765 unobse ed, I < 2a(/), Lo en z-pola iza ion bu no abso p ion ( iR ~ 0.2) o ex inc ion co ec ions; s uc u e sol ed by Pa e son unc ion and hea y-a om me hod wi h ini ial se o phases based on he B -a om posi on; ull-ma ix leas -squa es e inemen on F, aniso opic; di e ence Fou ie syn hesis (calcula ed up o sin 0/2 = 0.5 A -~) e ealed 21 H-a om posi ions; iso opic empe a u e ac o o each H a om equal o ha o he a om bonded o i , u he e inemen including H posi ional pa ame e s and anomalous dispe sion o B and S (In e na ional Tables o X- ay C ys allog aphy, 1974), wR =0.057, weigh ing scheme based on a s a is ical coun c i e ion; he enan iomo phic o m o he molecule was conside ed and inal wR --0.045 o gi e absolu e con igu a ion; c ys allog aphic p og ams Table 1. A omic coo dina es (x 10 4) and equi alen iso opic empe a u e ac o s (A 2 x 103) = I a* * (ai, a;). Ueq ]~--i~--jUij i aj aia; cos x y z Ueq 1950 (2) 7530 (< 1) 9420 (2) 74 (1) 9034 (3) 6561 (!) 6712 (4) 43 (!) 4969 (7) 5846 (2) 3244 (10) 39 (2) 6459 (8) 5537 (2) 126 (9) 44 (2) 6162 (8) 4576 (2) 2779 (9) 41 (2) 4222 (9) 4921 (2) 5709 (10) 49 (3) 2449 (9) 4318 (2) 2079 (10) 50 (3) 6451 (10) 6462 (3) 4666 (12) 37 (3) 8635 (9) 6152 (3) 3612 (11) 34 (3) 8055 (13) 6383 (3) 4970 (14) 39 (4) 5943 (12) 6267 (3) 3048 (14) 35 (3) 7510 (12) 6097 (3) 2224 (14) 38 (4) 7172 (12) 5559 (3) 1770 (13) 34 (3) 5987 (12) 5420 (3) 3160 (13) 34 (3) 4980(13) 4968(3) 2717(15) 34(3) 3667 (12) 4897 (3) 4048 (15) 41 (4) 2884 (14) 4386 (4) 3800 (14) 47 (4) 5407 (12) 6706 (3) 5822 (14) 33 (3) 5156 (13) 6537 (4) 7461 (15) 39 (4) 4111 (14) 6776(4) 8528(14) 39(3) 3290 (14) 7186 (4) 7923 (14) 41 (4) 3521 (13) 8352 (3) 6293 (15) 46 (4) 4573 (13) 7111 (3) 5219 (14) 40 (4) 10335 (13) 6065 (4) 3349 (16) 48 (4) 11151 (15) 6492(5) 2513(19) 69(5) C( 1 6) ......~,~ ~(1 5) ,% % x.~ 0(2) "*,~.~,,,,~ d o~ ~<.pz ? .-,~> = %'I ~,oz~ ~ ,..~~,,o.~ B 81 0(5) Fig. I. Bond leng hs and angles in he molecule (e.s.d.'s a e in he anges 0.011-0.017 A and 0.8-1-0% espec i ely). 1420 C ,6H21B N2OsS Discussion. F ac ional a omic coo dina es and equi a- len iso opic empe a u e ac o s 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 0.82(10) o 1.17 (10)A wi h an a e age alue o 1.01 (10)A. The a e age O-H bond leng h is 0.79 (ll)A. Bond dis ances and angles in he imidazolidine ing ag ee well wi h he mean alues epo ed o analogous gluco u anoimidazolidine-2- hione compounds (Conde, L6pez-Cas o & M i quez, 1978). Howe e , he N(1)-- C(2) and N(1)-C(1) bond leng hs de ia e signi ican ly om he epo ed mean alues 1.351 (3) and 1.471 (2)A, espec i ely, being close o he alues epo ed o l'-phenyl- l',3',4',5'- e ahyd o- 1,2- dideoxygluco u anoso[ 1,2-d]imidazol-2-one (Conde, Be nie & M i quez, 1980). The obse ed asymme y o he N(1)-C(1) and N(2)-C(1) bonds should indica e ha he esonance o m ~N + w -S ~C~N / is impo an and, pe haps, he subs i u ed g oups a N(1) and N(2) should in luence he esonance sys em. The imidazolidine ing is no plana ; he ing a oms shi signi ican ly om he leas -squa es plane [ he alue o he o al pucke ing ampli ude (C eme & Pople, 1975) is Q = 0.087 (9)A] and his ea u e has no been ound o monosubs i u ed [only a N(1)] gluco u anoimidazolidine compounds. Bond leng hs and angles in he u anosyl ing ag ee wi h mean alues epo ed o hese compounds. The asymme y o he endocyclic bonds O(1)-C(2) and O(1)--C(5), due o anome ic e ec s, obse ed in analogous compounds is di icul o es ablish in his case because o he high e.s.d.'s. The gluco u anose ing is no plana , as shown by he de ia ions om he leas -squa es plane h ough he i e a oms o he ing. 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 = 0.40 (1) A and ~p = 131.9 (9) ° o he sequence O ( 1)-C (2)-C (3)-C (4)-C (5) and he esul ing con o - ma ion 4T 3 is in e media e be ween en elope 4E and wis ~T o ms. The alues o he pseudo- o a ional pa ame e s ,,, and P co espond o one o he zones o high popula ion densi y in he con o ma ional wheel de ined in a s a is ical s udy, pe o med o e a la ge numbe o suga ings (Mu ay-Rus & Mo- he well, 1978). The small alue o he C(4)-C(3)- C(2)-O(1) = 8 (1) ° o sion angle obse ed in his and analogous compounds may be a ibu ed o dis o ion o he u anosyl ing due o he ing usion. The wo ings show a cis o m o coupling (Fig. 2) o which l= 1--6 and 2 =p1--6, 1 and /~1 being p ojec ed alency angles and l, 7 and 6 o sion angles. The ela ion l = 7 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 simila compounds (Conde, L6pez-Cas o & M& quez, 1978), 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 imidazolidine and u anosyl ings is 72.2 (4) °. The phenyl ing, plana as expec ed, and wi h an a e age C-C dis ance o 1.38 (1)A and C-C-C angle o 120 (1) °, o ms a dihed al angle o 56.2 (3) ° wi h he imidazolidine ing. This alue ag ees wi h hose obse ed in analogous compounds s udied p e iously in which he dihed al angle anges om 60 o 80 ° , excep o he alue 15.1 (6) ° obse ed in one case (Conde, Be nie & M& quez, 1980), and may indica e a signi ican con ibu ion o in amolecula in e ac ion. Fig. 3 shows he con en s o he uni cell iewed down he c axis. The s uc u e consis s o helical chains pa allel o [001]. In hese chains each molecule is linked by hyd ogen bonds O(2)..-O(3) (S--x, 1-y,--½ + z) and 0(4)...0(5) (½--x, l--y, ½+z) o wo nea es neighbou s ela ed by a wo old sc ew axis. De ails o he geome y o hese bonds a e: O(2)-H(O2)= 0.91 (12), H(O2)...O(3) = 1.87 (12) A, 0(2)- H(O2)...O(3) = 159 (10) ° and O(4)-H(O4) = 0.74 (12), H(O4)...O(5) = 2.10 (12) A, 0(4)- H(O4)...O(5)= 142(13) °. No o he in e molecula con ac s signi ican ly sho e han he sum o he an de Waals adii ha e been de ec ed. H(C3) I H(C2) ! L- c(2) c 3)) y = 8.5191 7.8( 1 O) k. ~""X "-110.0(8) /*,,~ Fig. 2. Newman p ojec ion along he C(2)-C(3) bond illus a ing he ing usion (angles in deg). Fig. 3. A iew o he cell down he c axis. M. D. ESTRADA, A. CONDE AND R. MARQUEZ 1421 The au ho s hank P o esso Galbis and P o esso Fe n~ndez-Bola ios o supplying he c ys als and D Gu i6 ez-Puebla (Uni e si y o Mad id) o collec ing he da a. The p esen wo k is a pa o a 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 T~cnica. Re e ences 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 is . Mine , Me alog. 1, 23-36. CREMER, D. & POPLE, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358. GALBIS-PI~REZ, J. A., PALACIOS, J. C., JIMI~NEZ-REQUEJO, J. L., AVALOS, M. & FERNANDEZ-BOLA~OS, J. (1983). Unpublished esul s. GALBIS-PEREZ, J. A., PINTO CORRAUZA, R. M., ROMAN-GALAN, E. & GOM/~Z-GUILL~N, M. (1979). An. Quim. 75, 387-391. GARCiA GONZALEZ, F., GALBIS-P/mEZ, J. A., FERNANDEZ- GARCIA-HmRRO, J. I. & FERNANDEZ-BOLA ~OS, J. (1979). An. Qu m. 75, 1002-1004. GEISE, H. J., ALTONA, C. & ROMERS, C. (1967). Te ahed on, 23, 439-463. In e na ional Tables o X- ay C ys allog aphy (1974). Vol. IV. Bi mingham: Kynoch P ess. MURRAY-RUST, P. & MOTHERWELL, S. (1978). Ac a C ys . B34, 2534-2546. STEWART, J. M., KUNDELL, F. A. & BALDWIN, J. C. (1970). The XRAY70 sys em. Uni . o Ma yland, College Pa k, Ma yland. Ac a C ys . (1983). C39, 1421-1423 S uc u e o (2-E hoxye hyl) ime hylammonium Iodide, CTH lsN O+.I - BY R. BARDI* AND A. M. PIAZZESI Biopolyme Resea ch Cen e, Uni e si y o Padua, Via Ma zolo 1, 35100 Pado a, I aly AND A. DEL PRA ls i u o Chimico Fa maceu ico, Uni e si y o Milan, Viale Ab uzzi 42, 20131 Milano, I aly (Recei ed 7 Ma ch 1983; accep ed 7 June 1983) Abs ac . M =259.1, monoclinic, P21/n, a= 16.060(7), b=13.231(6), c=10.610(6)A, l= 94.8(1) °, Z=8, U=2247(2) A 3, D m= 1.53, D x= 1.532 Mg m -3, 2(Mo Ka) = 0.7107 A,g = 2.84 mm -1, F(000)-- 1024, T= 298 K. Final R = 0.070 o 2477 obse ed e lec ions. The o e all con o ma ion o he ca ions, desc ibed by he o sion angles N-C-C-O, does no ma kedly di e om ha ound in many musca inic agen s. In oduc ion. We ha e pe o med he single-c ys al X- ay analysis o he s uc u e o he i le e hoxy subs i u ed choline iodide, as a pa o an in es iga ion in o he con o ma ional p ope ies o some musca inic agen s, which we a e examining in an a emp o co ela e molecula con o ma ion and biological ac- i i y. The i le compound, which possesses ema kable musca inic ac i i y, has been conside ed in an ex ensi e s uc u e-ac i i y analysis (P a esi, Villa & G ana, 1968; P a esi, Villa, Fe i, De Micheli, G ana, San- agos ino Ba bone, Silipo & Vi o ia, 1981). * To whom co espondence should be add essed. 0108-2701/83/101421-03501.50 Expe imen al. Compound ob ained by condensa ion o po assium e hoxide wi h (dime hylamino)e hyl chlo ide hyd ochlo ide, dis illa ion o esul ing p oduc and subsequen qua e niza ion (P a esi e al., 1968); single c ys als ob ained by slow e apo a ion o a solu ion in absolu e e hanol, unde educed cons an p essu e in a d y a mosphe e. D m measu ed by lo a ion. App oxi- ma e uni -cell pa ame e s es ima ed om p elimina y Weissenbe g and p ecession pho og aphs. P isma ic c ys al .-,0.3 x 0.3 x 0.5 mm. Philips PW 1100 ou - ci cle di ac ome e , g aphi e monoch oma o . Accu - a e uni -cell pa ame e s and c ys al o ien a ion ma ices ( oge he wi h hei es ima ed s anda d e o s) ob ained om leas -squa es e inemen o 20, co, Z and ~o alues o 20 ca e ully cen e ed high-angle (0 ange 15-20 °) e lec ions. 0-20 scan, scan speed 0.03 ° s -1, 20 ange 4-50 ° (-18<h<18, 0<k<15, 0<l<11). Two s anda d e lec ions (311, 3ii) e e y 180 min wi h no signi ican in ensi y a ia ion du ing da a collec ion. 3902 da a measu ed, 2477 wi h I > 30(I), Rin o 216 equi alen e lec ions (only hkO) being 0.062. Lo en z and pola iza ion co ec ions, in ensi ies placed on an absolu e scale by Wilson's me hod, expe imen al © 1983 In e na ional Union o C ys allog aphy