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