113 8 C 24H29B N209 S
posi ional molecula pa ame e s a e lowe when mole-
cula lexibili y is included, bu a highe alue o he
o e all molecula o a ion is obse ed in his case. The
o sional angles o selec ed molecula agmen s show
in some cases ( he e hyl g oup and wo o he ace yl
chains) a la ge de ia ion o he expe imen al alues
bu inclusion o he Coulombic e m does no app eci-
ably imp o e he i . These disc epancies be ween
expe imen al and heo e ical pa ame e s o molecula
sub o a ions and he abo e-ci ed cell expansion could
be a ibu ed o limi a ions o he o ce- ield app oach,
in pa icula he assumed ans e abili y o po en ial
pa ame e s.
The au ho s hank P o esso J. A. Galbis-P6 ez o
supplying he c ys als and o help ul discussion on
chemical aspec s and P o esso A. L6pez-Cas o o
collec ing he di ac ome e da a. The p esen wo k is
pa o a esea ch p ojec suppo ed by he CAICYT o
he Spanish Go e nmen .
Re e ences
BURGOS, E. & BONADEO, H. (1977). Chem. Phys. Le . 49,
475-478.
CONDE, C. F., MILl.AN, M., CONDE, A. & MARQUEZ, R. (1985a).
Ac a C ys . C41, 277-280.
CONDE, C. F., MIL~, M., CONDE, A. & M.~RQUEZ, R. (1985b).
Ac a C ys . C41, 1658-1662.
CREMER, D. & POPLE, J. A. (1975). J. Am. Chem. Soc. 97,
1354-1358.
ESTRADA, M. D., CONDE, A. & M.~.RQUEZ, R. (1983). Ac a C ys .
C39, 1418-1421.
ESTRADA, M. D., CONDE, A. & MARQUEZ, R. (1984). Ac a C ys .
C40, 898-901.
ESTRADA, M. D., CONDE, A. & M~,RQUEZ, R. (1986). Ac a C ys .
C42, 454-457.
GALmS-P mEZ, J. A., PALACIOS-ALBAR1L~N, J. C., JIMI~NEZ-
REQUEJO, J. L. & AVALOS-GONZ.~LEZ, M. (1984). Ca bohyd .
Res. 129, 131-142.
GOVERS, H. A. J. (1975). Ac a C ys . A31, 380-385.
HAMILTON, W. C. (1959). Ac a C ys . 12, 609-601.
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 .)
JOHNSON, C. K. (1965). ORTEP. Repo ORNL-3794. Oak Ridge
Na ional Labo a o y, Tennessee.
MASON, A. & KREEVOY, M. M. (1955). J. Am. Chem. Soc. 77,
5808-5814.
MIRSKAYA, K. V. (1973). Te ahed on, 29, 679-682.
MURRAY-RUST, P. & MOTHERWELL, S. (1978). Ac a C ys . B34,
2534-2546.
NARDELLI, M. (1983). Ac a C ys . C39, 1141-1142.
SKORCZYCK, R. (1976). Ac a C ys . A32, 447-452.
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.
TAYLOR, R. & KE ~ARD, O. (1982). J. Am. Chem. Soc. 104,
5063-5070.
WILLIAMS, D. E. (1972a). Ac a C ys . A28, 84-88.
WIL JAMS, D. E. (1972b). Ac a C ys . A28, 629-635.
WILLIAMS, D. E. (1974). Ac a C ys . A30, 71-77.
Ac a C ys .
(1987). C43, 1138-1142
S uc u e o 5-( l-D-Glucopy anosyl)ba bi u ic Acid T ihyd a e*
BY M. MILLAN, C. F.
CONDE,
A. CONDE AND R. M,~RQUEZ
Depa amen o de Op ica y Seccidn de F[sica del Cen o Coo dinado del CSIC, Uni e sidad de Se illa, Spain
(Recei ed 17 Sep embe 1985; accep ed 6 Janua y 1987)
Abs ac . C10H15N3OT.3H20 , M = 343.3, monoclinic,
P21, a = 10.883 (3), b = 12.497 (20), c =
10.553 (4) A, = 91.05 (3) °, V= 1435 (2) A 3, Z=4,
D m=1.57(2), D x=l.589Mgm
-3, MoK~ 2=
0.7107/~, / = 0.13 mm -~, F(000) = 728, T= 300 K,
R = 0.064 o 2692 obse ed independen e lexions.
The compound p esen s a zwi e ionic s uc u e in
which he nega i e cha ge is delocalized in he sys em
o med by he wo ca bonyl g oups a C4 and C6 and
he ca bon a om C5 o he ba bi u ic ing. In he wo
independen molecules in he asymme ic uni he
py anose ing adop s
a 4C 1
con o ma ion and he
dihed al angles be ween he py anose and ba bi u ic
* Ba bi u ic acid is 2,4,6(1H,3H,5H)-py imidine ione.
0108-2701/87/061138-05501.50
ings o he wo molecules a e 80.9 (3) and 90-3 (3) ° .
The molecules a e linked by an ex ensi e h ee-
dimensional hyd ogen-bonding ne wo k, in ol ing he
wa e hyd a ion molecules, which s abilize he c ys al
s uc u e.
In oduc ion. The s uc u e de e mina ion o he i le
compound (II) was unde aken as pa o a con inuing
p ojec on con o ma ional de ails o C-nucleosides in
he solid s a e. An easy syn hesis o C-nucleoside
de i a i es o ba bi u ic acids by eac ion o aldoses
wi h he ba bi u ic acid has been epo ed (A alos-
Gonz ilez, 1981; Galbis-P6 ez, A alos-Gonz/dez,
Jim~nez-Requejo & Palacios-Alba i.n, 1983). In his
way, he eac ion o ba bi u ic acid wi h ~glucose
© 1987 In e na ional Union o C ys allog aphy
M. MILLAN, C. F. CONDE, A. CONDE AND R. M,ARQUEZ 1139
yields he acyclic C-glycoside (I) o i s cyclic analogue
(II) by dehyd a ion o he suga side chain. A e
ace yla ion, he cyclic o m was es ablished om
spec al da a (UV, IR and ~H NMR). Fo he
non-ace yla ed compound he acyclic o m was ini ially
supposed and an X- ay analysis was sugges ed o
elucida e he molecula o m; inally, he cyclic C-
nucleoside s uc u e was es ablished. The X- ay s uc-
u e o he analogous 5- l-D-galac opy anosyl-l,3-di-
me hylba bi u ic acid monohyd a e has been epo ed
(Mill~m, Conde, Conde & M/ quez, 1985) and he
cyclic o m was also es ablished in ha X- ay analysis.
log aphic p og ams o he
XRAY70
sys em (S ewa ,
Kundell & Baldwin, 1970) used h oughou .*
Discussion. F ac ional a omic coo dina es and equi a-
len iso opic empe a u e ac o s (Hamil on, 1959) o
non-hyd ogen a oms a e gi en in Table 1. A p ojec ion
o he molecule A wi h le e ing is shown in Fig. 1. Bond
leng hs and angles in ol ing non-hyd ogen a oms a e
shown in Table 2. Fo bonds in ol ing H a oms, he
mean alues ound a e 1.07 (4),/k o C-H dis ances,
0.93 (5)/~ o O--H bond leng hs and 1.08 (3)/~ o
N--H dis ances.
O
H .~N,~ N H
0 0 I
H H
COH O. /N-~
/O
HO-C-H HO o "Y, "T"
H-C-NH 3 HO N.~ " -
I
HO-C-H H " O
I
H-C-OH
I
H-C-OH
I
CH~OH
(I) (II)
* 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
43704 (29 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.
Table 1.
A omic coo dina es and equi alen
iso opic
Expe imen al. C ys als o he i le compound, p epa ed Molecule A
as p e iously desc ibed in he O ganic Chemis y C l
c2
Depa men o he Uni e si y o Ex emadu a, we e
c3
kindly supplied by P o esso J. Galbis. Colou less
c4
c5
c ys als in he o m o p isms elonga ed along [001 ].
D m
c6 C7
by lo a ion me hod. C ys al 0.04 x 0.14 x 0.17 mm.
c8
En a -Nonius CAD-4 di ac ome e equipped wi h
c9
c10
g aphi e monoch oma o ; cell dimensions ob ained n~
om 25 e lexions in he ange 2 < ~< 20 ° . To al o n2 N3
3768
independen e lexions (--14 <h
_< 14,
0 < k < ol
o2
15,
0 <l_< 16) measu ed in he 2 < 0<30 ° ange o3
using o. --20 scan echnique. Th ee s anda d e lexions o4 o5
(600, 060, 006) moni o ed; a ia ion in in ensi y less o6
han 4% o mean alues. 1076 e lexions conside ed as o7
unobse ed [I < 2o (/)]. No co ec ion o abso p ion o Molecule a
ex inc ion. S uc u e sol ed by di ec me hods using
Cll
c21
MULTAN80
(Main, Fiske, Hull, Lessinge , Ge main,
c31
Decle cq & Wool son, 1980). The absolu e con igu a-
c41
c51
ion was assumed on he basis o he con igu a ions o
c61
he compounds used in he syn hesis. Full-ma ix c71 c81
leas -squa es e inemen ; unc ion minimized c91
~w(IFol -
I F c I) 2 wi h weigh ing scheme based on he c101nll
s a is ical coun c i e ion (w =
1/ 2).
Di e ence Fou ie n21 n31
syn hesis e ealed he H-a om posi ions; iso opic o~
empe a u e ac o o each equal o ha o he a om o2~ O31
bonded o i . Fu he leas squa es including posi ional o4~ o5~
pa ame e s o he H a oms. A inal con e gence o6.
A/a
< 0.03 ( o non-hyd ogen a oms) wi h R = 0.064, o7~
wR
=0.073, S = 2.2 o 541 a iables e ined. Max.
and min. alues in inal di e ence densi y map 0.35 and
-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).
Calcula ions ca ied ou on a Uni ac 1100; c ys al-
he mal pa ame e s
Ueq
= ~ ~'i ~i a ~ a~ a ia jcos
(a i. a j).
x y z
0.5868 (10)
0.7982 (9)
0.8420 (8)
0.7631 (8)
0.9755 (7)
0.9954 (9)
1.1304 (8)
1.1945 (8)
1.1657 (8)
1.2277 (10)
0.6388 (7)
0-6702 (8)
0.9366 (7)
0-4793 (7)
0.8615 (7)
0.7956 (6)
• 0365 (6)
• 2012 (7)
-3186 (7)
• 1430 (7)
0.7144 (9)
0-9205 (9)
0.9692 (8)
0.8881 (8)
• 0994 (8)
• 1172 (7)
• 2526 (8)
• 3198 (8)
• 2961 (7)
• 3589 (lO)
0.7654 (7)
0.7947 (8)
1.0560 (7)
0.6043 (6)
0.9830 (7)
0.9202 (6)
1.1665 (6)
1.3303 (6)
1.4439 (6)
1.2718 (6)
0.8315 (11) 0.8174 (10)
0.8652 (11) 0.8946 (9)
0.7926 (1 I) 0.8078 (9)
0.7475 (11) 0.7180(9)
0.7626 (11) 0.8158 (8)
0.6415 (11) 0.8233 (8)
0.6123 (10) 0.8237 (8)
0.6681 (I 1) 0.7143 (9)
0.7884 (11) 0.7212 (10)
0.8532 (11) 0.6178 (10)
0.7683 (11) 0.7271 (8)
0.8813 (10) 0.8966 (8)
0.6021 (10) 0.9420 (8)
0.8423 (11) 0.8249 (9)
0.9174 (10) 0.9727 (8)
0.6859 (9) 0.6291 (6)
0.8038 (9) 0.7081 (6)
0.8038 (9) 0.4954 (7)
0.6430 (10) 0.7250 (8)
0-5000 0.8102 (7)
0.0615 (11) 0.6741 (9)
0.0410 (11) 0.5907 (9)
0.1062 (10) 0.6887 (8)
0.1454 (11) 0.7821 (9)
0.1394 (10) 0.6854 (8)
0.2588 (I0) 0.6657 (8)
0.2874 (I0) 0.6595 (9)
0.2456 (I 1) 0.7771 (9)
0.1254 (10) 0.7887 (8)
0.0717 (11) 0.8981 (10)
0.1196(10) 0.7688(8)
0.0200 (I0) 0.5892 (8)
0.2926 (10) 0.5456 (8)
0.0463 (10) 0.6637 (7)
0.0045 (9) 0.5014 (7)
0.2028 (9) 0.8741 (7)
0.1078 (9) 0.7974 (6)
0.1223 (10) 1.0144 (7)
0.2730 (10) 0.7647 (8)
0.3982 (8) 0.6379 (7)
Wa e molecules
O8 0.4718 (7) 0.7032 (10) 0.5264 (8)
09 0.3793 (8) 0.7517 (12) 1.0469 (9)
O10 0.4551 (8) 0.5010(11) 0.8810(9)
O12 0.5055 (7) 0.4240 (11) 0.5360 (8)
OI3 0.8091 (9) 0.3979 (10) 0.8952 (10)
O14 0.7237 (9) 0.4726 (10) 0.6584 (9)
Ue,(A ~ x 103)
30 (3)
26 (3)
21 (2)
23 (3)
20 (2)
23 (3)
21 (2)
23 (3)
26 (3)
31 (3)
29 (3)
29 (3)
27 (2)
43 (3)
40 (3)
28 (2)
26 (2)
34 (2)
39 (3)
3O (2)
25 (3)
23 (3)
21 (2)
22 (3)
21 (2)
20 (2)
22 (3)
21 (2)
21 (3)
30 (3)
26 (2)
28 (3)
26 (2)
34 (2)
30 (2)
28 (2)
23 (2)
32 (2)
38 (3)
24 (2)
40 (3)
51 (3)
50 (3)
41 (3)
48 (3)
48 (3)
1140 Ci0 HI5NaO7.3H20
In he glucopy anose ing he mean alues o he
C-C and C-O bond leng hs a e 1.527 (10) and
1.423(11)A, espec i ely, o molecule A, and
1.522 (5) and 1.433 (10) A, espec i ely, o molecule
B, in ag eemen wi h he mean alues 1.522 (2) and
1.426 (2)A ob ained om 57 py anose compounds
(Ohanessian, Longchambon & A ene, 1978). The mean
alue o he endocyclic C-C-C angles is 110.1 (9) °
o molecule A and 110.0 (9) ° o molecule B, in
ag eemen wi h an
sp 3
hyb idiza ion o he C a oms.
The angles O4-C9-C10 and C8-C9-C10 show a
di e ence o 5.2 (13) ° and he analogous di e ence o
molecule B is 6.8 (12) °, bo h alues in he ange 5-9 °
epo ed o oligosaccha ides. This angula dis o ion is
due o in e ac ions be ween he subs i uen s a C8 and
C9.
The glucopy anose ing adop s a 4C 1 con o ma ion
as in mos D-py anoses. In e ms o ing-pucke ing
coo dina es (C eme & Pople, 1975) he alues o he
ampli ude-phase pai
(q2, P2)
and pucke ing coo dina e
q3 o molecule A a e 0.078
(9)A,
--34 (8) ° and
0.588 (9) A [Q = 0.593 (9) A and 0= 7.6 (9) °] o he
sequence O4-C5-C6-C7-C8-C9. The co e-
sponding alues o molecule B a e q2
=
0.032 (10) A,
p2 =-49 (18) ° and q3 = 0.588 (9) A [Q = 0.589 (9) A
and 0= 3.1 (10) °] o he analogous sequence. The
asymme y pa ame e s o Na delli (1983) a e
ACs(04)
- 0.031 (5),
ACs(C5)
= 0.062 (5),
ACs(C6) =
0.031 (5), AC2(O4-C9)=0.001 (4), AC2(C5-O4)=
0.004 (4), AC2(C6-C5 ) =0.004 (4) o molecule A
and ACs(041)=O.O17
(5),
ACs(C51)=0.027
(5),
ACs(C61) = 0.011 (5), ACs(O41--C91) = 0.004
(4),
AC2(C51-O41) = 0.021 (4), AC2(C61-C51) =
0.018 (4) o molecule B.
The mean alues o he in acyclic o sion angles a e
58.5 (8) ° o molecule A and 58.4 (8) ° o molecule B
[ alues ange om 50.5 (12) o 67.9 (11) ° and om
54.4 (11) o 64.1 (11) °, espec i ely; he smalles alue
being abou C6-C7 and he la ges alue abou
C9-O4 o molecule A and simila ly o molecule B].
As obse ed gene ally in py anose ings, a g ea e
pucke ing occu s abou he C5-O4, O4-C9 and
C8-C9 bonds and a smalle pucke ing abou C5-C6,
C6-C7 and C7-C8 bonds in compa ison wi h he
o sional angle o 55 ° in cyclohexane. Howe e , o
cl0
O5 C91~i~O4 ~ C 3.~ '~li~ N2
o7(,.3
Fig. 1. A p ojec ion o molecule A wi h le e ing.
molecule B, he o sion angle abou C51-C61 is
sligh ly g ea e han 55 o.
The o sion angles C8-C9-C10-O5 = 51.0 (13)
and O4-C9-C10-O5 = -69-9 (12) ° o molecule A,
and he co esponding alues o 54.8(13) and
-67.7 (12) ° o molecule B, indica e a
gauche-gauche
con o ma ion o he exocyclic bond in bo h molecules.
This
gg
con o ma ion is no he mos equen adop ed
o py anoses (gg: 37.6%;
g:
2.7%;
g :
59.5%)
(Longchambon, Ohanessian, A enel & Newman,
1975); he
gauche
angles di e om he ideal alue o
60 ° by less han 10 °.
In he ba bi u ic moie y he mean alues o he
endocyclic N--C bond leng hs a e 1.383 (12)A o
molecule A and 1.371(12) A o molecule B in
ag eemen wi h hose epo ed o ba bi u ic acid
de i a i es (C a en, Vizzini & Rod igues, 1969;
Shimizu, Nishigaki, Nakai & Osaki, 1982).
Table 2.
Bond leng hs
Molecule
A
C1-N1
C I-N2
CI-OI
C2-C3
C2-N2
C2-O2
C3-C4
C3-C5
C4-N 1
C4-O3
C5-C6
C5-O4
C6-C7
C6--N3
C7-C8
C7-O7
C8-C9
C8-O6
C9-C10
C9-O4
CI0-O5
N2-C 1-O 1
NI-CI-O1
N1--C1--N2
N2-C2-O2
C3-C2-O2
C3-C2-N2
C2-C3-C5
C2-C3-C4
C4-C3-C5
C3-C4-O3
C3-C4-N l
N 1-C4-O3
C3-C5-O4
C3-C5-C6
C6-C5-O4
C5-C6-N3
C5-C6-C7
C7--C6--N3
C6-C7--O7
C6-C7-C8
C8-C7-O7
C7-C8-O6
C7-C8-C9
C9-C8-O6
C8-C9-O4
C8-C9-C l0
C 10-C9-O4
C9-CI0-O5
C l-N 1-C4
C 1-N2-C2
C5-O4-C9
(A)
and angles (0)
123.6 (ll) N21--CI l--Ol I 121.5 (10)
122.3 (ll) Nll-Cll-Oll 122-9 (10)
114-l (9) Nl l-Cl l-N21 115-6 (9)
116.7 (10) N21-C21-O21 I17.9 (9)
126-1 (9) C31-C21-O21 123.8 (9)
117.2 (9) C3 I-C21-N21 118-2 (9)
118.2 (9)
C21-C31-C51
119-5 (8)
120.3 (9) C21-C31-C41 118-5 (8)
121.5 (9) C41-C31-C51 121-8 (9)
125.1 (9) C31-C41-O31 124.5 (8)
118.0 (9) C31-C41-NI I 117.5 (9)
116.8 (8) N 11 -C41-031 118-0 (8)
109.2 (7) C31-C51-O41 112-2 (8)
112.6 (8) C31-C51-C61 113-8 (8)
109.4 (9) C61-C51-O41 108-6 (9)
107.8 (9) C51-C6 l-N31 I09-9 (9)
112.0 (10) C51-C61-C71 111-3 (10)
110.3 (8) C71-C61-N31 108.5 (7)
109.5 (8) C61-C71--O71 112-5 (8)
110.1 (8) C61-C71-C81 109-7 (8)
109.2 (8) C81-C71-O71 113.3 (8)
107.0 (8) C71-C81-O61 106-8 (8)
108-3 (8) C71-C81-C91 108.9 (8)
114.5 (I0) C91-C81-O61 114.3 (10)
109.2 (10) C81-C91-O41 108.9 (10)
113-1 (9) CSI-C91-CI01 115.4 (9)
107-9 (9) C l0 I-C91-O41 108.6 (8)
109.1 (10) C91-CI01-O51 111-4(10)
125.0 (9) CII-NI 1-C41 125.9 (9)
124.8 (10) CI I-N21-C21 124.2 (9)
110.3 (7) C51-O41-C91 113-1 (7)
Molecule
B
1.368 (16) Cl l-Nll 1.346 (15)
1.371 (15) CI l-N21 1.365 (14)
1-182 (13) C 1 l-Ol I 1.216 (12)
1.380 (16) C21--C31 1.412 (15)
• 409 (13) C21-N21 1.393 (13)
• 248 (14) C21-O21 1.258 (13)
• 386 (14) C31-C41 1-422 (14)
• 502 (12) C31-C51 1-478 (13)
• 383 (12) C41--NII 1.378 (12)
• 268 (14) C41--O31 1-252 (14)
• 530 (19) C5 l-C61 1.520 (18)
• 423 (12) C51--O41 1-433 (l l)
• 514 (13) C61-C71 1.519 (12)
• 500 (13) C61-N31 1-482 (12)
• 528 (14) C71-C81 1.521 (13)
• 417 (13) C71-O71 1.420 (17)
1.538 (19) C81-C91 1.530 (18)
1.389 (12) C81-O61 1-402 (11)
1.526 (16) C91-C101 1.490 (15)
1.423 (11) C91-O41 1.432 (10)
1.455 (14) C 101-O51 1.419 (14)
M. MILLAN, C. F. CONDE, A. CONDE AND R. M/~RQUEZ 1141
Howe e , he alues o he in acyclic C-C dis-
ances [mean alues o 1.383 (13) and 1.417 (14)/L
espec i ely, o molecules A and B] a e signi ican ly
sho e han hose epo ed o ba bi u ic acid
de i a i es, e ealing an app eciable double-bond
cha ac e . In a alence-bond desc ip ion, based on he
use o Pauling's o mula (Pauling, 1960), he pe cen -
age o double-bond cha ac e comes o 57% and 36%
espec i ely (C-C: 1.504, C=C: 1.334/~). On he
o he hand, he mean alues o he bond dis ances
O2-C2 and O3-C4 a e 1.258 (14) and 1.255 (13)/~,
espec i ely, o molecules A and B, bo h highe han
he adop ed alue o C=O. The esul ing pe cen age o
double-bond cha ac e is 65% and 67%, espec i ely
(C-O: 1.43, C=O: 1.21/~). These ea u es a e
consis en wi h he esonance o ms:
o~-N--~ O O ~ N -,..~O O,,~ N ~. O
~IN~.H ~-~N~H ~L~N~H
O O 0
(a) (b) (c)
Table 3.
Possible hyd ogen bonds
X-H...Y X-H X...Y H...Y LX-H...Y
O9-HO91...O1 0.91 (5)/~ 2.84 (1) ,/~ 2.03 (6)/~ 148 (6) °
OI3-HO132...O14 0-89 (5) 2.81 (1) 2.02 (6) 147 (6)
O13-HOI31...O31 0.90 (7) 2.73 (2) 1.89 (7) 154 (5)
O14-HO141 ...03 0.96 (7) 2-80 (2) 2.00 (8) 139 (4)
O14-HO142...O12 0.95 (5) 2.75 (1) 1.86 (6) 156 (6)
O71 HO71---O7 0-96 (6) 2.64 (1) 1.68 (6) 175 (5)
NI-HNI...O8 1.07 (6) 2.88 (1) 1.84 (6) 165 (5)
O10-HO102-..O5 P 0-88(6) 2.98(I) 2.16(6) 154(5)
N3-HN31---O51 * 1.09(6) 2-96 (1) 1-90 (5) 161 (5)
N3-HN32...O3 P 1.11 (6) 2.77(1) 1.68(6) 163(5)
O5-HO5..-OI4" 0.89 (7) 2.79 (2) 1.91 (7) 172 (5)
N31-HN313...O21" I. 13 (7) 2.73 (2) 1.68 (7) 150 (5)
O6-HO6...O8 "~ 1.03 (6) 2-80 (1) 1.85 (6) 153 (5)
O9-HO92.-.O13 ~ 0.84 (7) 2.82 (2) 2.16 (6) 135 (6)
N2-HN2...OI0 ~ 1.03 (6) 3.12 (I) 2-12 (6) 165 (5)
O51-HO51 ...O10' 0-92 (6) 2.98 (1) 2.07 (6) 167 (5)
O7-HO7..-O2' 0.89 (6) 2-51 (1) 1.67 (6) 157 (5)
O61-HO61...O9' 0.98 (5) 2.75 (1) 1.79 (5) 165 (7)
N31-HN312...O5" 1-06 (6) 2.83 (1) 1.86 (6) 149 (5)
N21-HN21...O71 ~j 1.07 (6) 2.92 (1) 1-87 (6) 164 (5)
N3 I-HN311..-O3 ~ 1.07 (6) 2.81 (l) 1.79 (6) 158 (5)
O8-HO81...OI 1 ~ 0.93 (6) 2.91 (I) 2.01 (6) 162 (5)
Ol2-HOl21..-Ol I " 0.94 (7) 2.85 (I) 1-96 (6) 156 (6)
O8-HO82...O12 ~" 1-00 (7) 2.85 (2) 1.99 (8) 142 (4)
OI0-HOI01...O6 ~"~ 0.94 (6) 2.82 (I) 1.93 (6) 160 (5)
O12-HO122...O71 ~"~ 0.90 (6) 2-80 (1) 1.94 (5) 159 (5)
N I I-HN 1 I..-O9 ~ 1-07 (6) 3.02 (2) 2.00 (7) 158 (5)
Symme y code: none
x, y, z;
(i) -x+2,
y+½,
-z+2; (ii) -x+2,
y+½, -z+ 1 ;
(iii)
x+l,y, z;
(i ) -x+ 1,y+½, z+2; ( )
-x+2,y-½,
-z+2; ( i)
-x+2,y-½,
-z + 1; ( ii) -x+ 1, y+ ½, -z + 1; ( iii) x-1, y, z; (ix) -x+ 1, y-½, -z + 2.
and con i m a zwi e ionic s uc u e o he compound
in which he nega i e cha ge is delocalized in he sys em
o med by he wo ca bonyls a C2 and C4 and he
ca bon a om C3 o he ba bi u ic ing o molecule A,
and he co esponding a oms o molecule B. This
s uc u e had been p oposed on he basis o IR spec a
showing bands associa ed wi h he +NH 3 g oup
(~3000 and ~1600cm -1) (Galbis-P6 ez, A alos-
Gonz/dez, Jim+nez-Requejo & Palacios-Alba /m,
1983).
"/'o6 ~ ¢~ c8 lO5..~
TM
• "
.
*
1061 "
*
.~ 07~ cT~X-"---Yc91
• ClOo5 / J,,
~ ~--
"
"
"
.~ ~ / ~o.~ 9~-F' ,s~;Y "-'-~
°~~-~ ~ o.13~..~ "
Ol,
"C1~/N1A " ' " " O!1
• l - 08 ~., 012 I " *
• o~ 1 ,~
°l°" / I
"
"
09 . J~
" Io
d
o
Fig. 2. A iew o he s uc u e along [001].
The ing adop s a small boa de o ma ion in molecule
A [Y(A/a)2=31.4,
Z 2 a 95%= 7.8] and a small
wis -boa de o ma ion in molecule
B [Y(A/a) 2
-- 10.0,
Z 2 a 95% = 7.8]. The dihed al angle be ween py anose
and ba bi u ic ings is 80.9 (3) ° o molecule A and
90.3 (3) ° o molecule B.
C ys al packing
Fig. 2 shows a iew along [001] o he s uc u e,
s abilized by an ex ended h ee-dimensional hyd ogen-
bonding ne wo k in which wa e molecules a e in ol-
ed. The packing o he s uc u e consis o chains o
molecules along [001]. These chains consis o a
sequence o molecules A and B al e na ing and aligned
head- o- ail, each molecule being linked o i s neigh-
bou s by hyd ogen bonds.
The wa e molecules a e loca ed be ween hese
chains and in ol ed in hyd ogen bonds linking he
neighbou ing chains. The chains a e joined oge he
no only by he wa e molecules, bu also by he 07-
HO7...O2 (-x+2, y-½, -z+2) and N21-H21...O71
(-x+2, y-½, -z+ 1) bonds o gi e a h ee-dimensional
ex ended packing scheme. De ails o he geome y o
he possible hyd ogen bonds a e gi en in Table 3.
Values o he H...O dis ance o he O-H...O
bonds a e in he ange 1.67-2.16 A and alues o he
O--H...O angle ag ee wi h he s a is ical esul (Allen,
Kenna d & Taylo , 1983) ha sho hyd ogen bonds
end o be mo e linea han long ones. Fo he h ee
bonds wi h O...H < 1.81 A he mean alue o he
dono -p o on-accep o angle is 166 (5) °, in ag ee-
men wi h he mean alue 168.4 (9) ° epo ed (Allen,
1142 CIoHlsN3OT.3H20
Kenna d & Taylo , 1983), bu o bonds wi h O...H >
1.81 A he mean alue ound is 150 (3) °, lowe han
he mean alue 165.8 (12) ° epo ed in he abo e-ci ed
s a is ical s udy. Fo he N-H...O bonds he mean
alue o he H...O dis ance is 1.86 (5) A and he mean
N-H-.-O angle is 159 (4) o.
We hank P o esso J. A. Galbis o supplying he
c ys als and o help ul discussions on chemical aspec s
and P o esso A. L6pez Cas o o collec ing he
di ac ion da a. The p esen wo k is pa o a p ojec
suppo ed by a g an o he Comisi6n Aseso a de
In es igaci6n Cien i ica y T6cnica o he Spanish
Go e nmen .
Re e ences
• ALLEN, F. H., KENNARD, O. & TAYLOR, R. (1983). Acc. Chem.
Res. 16, 146-153.
AVALOS-GONZALEZ, M. (1981). Doc o al Thesis. Uni . o
Ex emadu a, Spain.
CRAVEN, B. M., V~z m, E. A. & RODmGUES, M. M. (1969). Ac a
C ys . B25, 1978-1993.
CREMER, D. & POPLE, J. A. (1975). J. Am. Chem. Soc. 97,
1354-1358.
GALBIS-PI~REZ, J. A., AVALOS-GONZ.~LEZ, M., JIMI~NEZ-REQUEJO,
J. L. & PALACIOS-ALBARR~,N, J. C. (1983). Ca bohyd . Res. 124,
C15-C17.
HAMILTON, W. C. (1959). Ac a C ys . 12, 609-610.
In e na ional Tables o X- ay C ys allog aphy (1974). Voi. IV.
Bi mingham: Kynoch P ess. (P esen dis ibu o D. Reidel,
Do d ech .)
LONGCHAMBON, F., OHANESSIAN, J. AVENEL, D. & NEWMAN, A.
(1975). Ac a C ys . B31, 2623-2627.
MAIN, P., FISKE, S., HULL, S. E., LESSINGER, L., GERMAIN, P.,
DECLERCQ, J.-P. & WOOI2SON, 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.
MILL~N, M., CONDE, C. F., CONDE, A. & M.~RQUEZ, R. (1985).
Ac a C ys . C41, 274-277.
NARDELLI, M. (1983). Ac a C ys . C39, 1141-1142.
OHANESSlAN, J., LONGCHAMaON, F. & ARENE, C. (1978). Ac a
C ys . B34, 3666-3671.
PAULING, L. (1960). The Na u e o he Chemical Bond. I haca:
Co nell Uni . P ess.
SmMIZU, N., NISHIGAKI, S., NAKAI, Y. & OSAKI, K. (1982). Ac a
C ys . B38, 2309-2311.
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.
Ac a C ys .
(1987). C43, 1142-1145
l,l',3,3'-Te akis(dime hylamino)-4H,4'H-4,4'-biisoquinolyldiium Dipe ehlo a e (II) and
l,l',3,3'-Te alds(dime hylamino)-4,4'-biisoquinolyl (III)
BY PETER F. LInDLEY AND ADmAL R. WALTON
Depa men o C ys allog aphy, Bi kbeck College, Male S ., London WC1E 7HX, England
GERHARD V. BoYo AND GEORGE A. NICOLAOU
Depa men o Chemis y, King's College London, Kensing on Campus, London W8 7AH, England
AND OLE HAMMERICH
Depa men o Gene al and O ganic Chemis y, The H. C. O s ed Ins i u e, 21 O0 Copenhagen, Denma k
(Recei ed 14 Oc obe 1986; accep ed 19 Janua y 1987)
Abs ac . (II): C26H34N2+.2C104,
M =
629.5, mono-
clinic,
I2/a,
a=14.580(1), b=10.760(1), c=
18.634 (1) A, l = 90.693 (3) °, U= 2923.1 (4)/k 3, Z
=4,
Dx=l.43Mgm
-3, CuK~ 2=1.54178 /~,
# = 2.381 mm -1, F(000) = 1320, T= 293 (1) K, R =
0-068 o 2606 unique e lec ions. (III):
C26H32N6,
M =428"6, monoclinic,
P2j/c,
a=9.844 (9), b=
10.580 (9), c = 24.355 (21) A, l= 109.860 (8) °, U
=2386(4), 3 , Z=4, D x=l.19Mgm -3, CuKa,
; = 1.54178/k, a = 0.496 mm -1, F(000) = 920, T=
293 (1)K, R = 0.055 o 4056 unique e lec ions. The
symme y- ela ed hal es o he ca ion in (II) a e
0108-2701/87/061142-04501.50
nea ly pa allel and a e joined by an excep ionally
long [1.597 (2)/~] bond; in he conjuga e base (III) his
bond is 1.496 (7)/~, he no mal leng h o a single bond
be ween spZ-hyb idized C a oms, and he planes o he
hal es o he molecule o m a dihed al angle o
62.8(3) ° .
In oduc ion. The wo k epo ed he ein a ose om an
in es iga ion in o he chemis y o he eadily a ailable
1,3-bis (dime hylamino)isoquinolines (I). Oxida i e
dime iza ion o (I) wi h aqueous sil e pe chlo a e
o cyclic ol amme y esul ed in he o ma ion
© 1987 In e na ional Union o C ys allog aphy