474 4-OXOPYRIDO[ 1,2-a] PYRIMIDIN- 1 -IUM-2-O LA TE
I
Fig. 3. P ojec ion o he c ys al s uc u e down he b axis. Black
ci cles: N a oms, double ci cles: O a oms. The do ed lines
ep esen he hyd ogen-bonding sys em.
1.345 (2) and N(5)-C(10) 1-355 (2)A (Fig. 2) ha e
alues cha ac e is ic o C-N pa ial double bonds.
In e na ional Tables o X- ay C ys allog aphy (1962)
gi es 1.352 (5)A o such bonds. The e is a signi ican
di e ence be ween he bonds C(2)-O(2) 1.251 (2) and
C(4)-O(4) 1.228 (2) A; his may be because 0(2) and
0(4) a e in ol ed in a s ong and a weak in e molecula
hyd ogen bond, espec i ely.
The c ys al s uc u e is s abilized by pai s o
hyd ogen bonds g ouped a ound cen es o symme y
(Fig. 3). Two ypes o hyd ogen bonds occu : s ong
linea N(1)-H(1)...O(2) bonds and weak ben C(6)-
H(1)...O(4) bonds; he o me ag ees well wi h he
obse a ion ha s ong N-H...O hyd ogen bonds
p e e a linea o nea ly linea a angemen (Taylo ,
Kenna d & Ve sichel, 1984). The hyd ogen-bond
dimensions a e: N(1)-H(1) 1.00(3), H(1)-..O(2)
1.70 (3), N(1)...O(2) 2.698 (2) A, N(1)-H(1)...O(2)
179(3)°; and C(6)-H(6) 0.97(3), H(6)...O(4)
2.33 (3), C(6)...O(4) 3.180(2)A, C(6)-H(6)...O(4)
146(3) ° .
Financial suppo om he Danish Na u al Science
Resea ch Council and Thomas B. Th iges Founda ion
o he pu chase o he X- ay di ac ion equipmen is
g a e ully acknowledged.
Re e ences
DVORTS.~K, P., RESOFSZKI, G., HUHN, M., ZALA, NTAI,
L. & Kiss,
A. I. (1976). Te ahed on, 32,,2117-2120.
In e na ional Tables o X- ay C ys allog aphy (1962). Vol. III.
Bi mingham: Kynoch P ess. (P esen dis ibu o D. Reidel,
Do d ech .)
In e na ional Tables o X- ay C ys allog aphy (1974). Voi. IV, pp.
99, 149. Bi mingham: Kynoch P ess. (P esen dis ibu o D.
Reidel, Do d ech .)
KATRITZKY, A. R. & WARING, A. J. (1962). J. Chem. Soc. pp.
1544-1548.
MAIN, P., FISKE, S. J., HULL, S. E., LESSINGER, L., GERMAIN, G.,
DECLERCQ, J.-P. & WOOLFSON, M. M. (1980).
MULTAN80. A
Sys em o Compu e P og ams o he Au oma ie Solu ion o
Co's al S uc u es om X- ay Di ac ion Da a. Uni s. o Yo k,
England, and Lou ain, Belgium.
SNYDER, H. R. & ROBINSON, M. M. (1952). J. Am. Chem. Soc. 74,
4910-4916.
STEWART, J. M., MACHIN,
P. A.,
DICKINSON, C. W., AMMON,
H. L.,
HECK, H. & FLACK, H. (1976). The
XRA
Y76 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. & VERSICHEL, W. (1984). Ac a C ys .
B40, 280-288.
TSCHITSCHIBAB1N, A. E. (1924). Be . D sch. Chem. Ges. 57,
1168-1172.
URBAN, R., GROSJEAN, F. & ARNOLD, W. (1970).
Hel . Chim.
A c a, 53, 905-922.
Ac a C ys . (1985). C41,474-476
3-E hoxy-5,6,7,8- e ahyd o- l-hyd oxyisoquinoline-4-ea boni ile,
C12H14N202
BY S. SALISI AND J. L. BRIANSO
Depa amen o de C is alog a ia y Mine alogia, Uni e sidad Au 6noma de Ba celona, Bella e a (Ba celona),
Spain
AND X. SOLANS AND M. FONT-ALTABA
Depa amen o de C is alog a a y Mine alog{a, Uni e sidad de Ba celona, G an Via 585, Ba celona 08007,
Spain
(Recei ed 3 May
1984;
accep ed 17 July
1984)
Abs ac .
20.000 (2),
94.31 (2) ° ,
M =218.25, monoclinic, P21/n, a=
b = 6.219 (1), c= 8.794 (1) A, /~=
V= 1090.7 (4) A 3, Z = 4, D x =
1.33gcm -3, 2(MoKO=0.71069~ g=0.86cm -1,
F(000) = 464, T= 298 K. Final R = 0.056 o 1369
obse ed e lec ions. The py idine ing is plana ; wo
0108-2701/85/030474-03501.50 © 1985 In e na ional Union o C ys allog aphy
S. SALISI, J. L. BRIANSO, X. SOLANS AND M. FONT-ALTABA 475
(ca bonyl and ca boni ile) subs i uen s de ia e a he
same side o he plane, while he emaining subs i uen s
de ia e a he o he side. The six-ca bon-membe ed ing
has a skew-boa o m. Bond angles and leng hs a e
simila o hose obse ed in he li e a u e. Enan iome ic
molecules a e hyd ogen-bonded by means o he
ca bonyl O and he N a om o he isoquinoline moie y.
a skew-boa con o ma ion. Enan iome ic molecules
a e hyd ogen-bonded {N(10)-H(N10)...O(161);
d[N(10)...O(16~)] = 2.821 (3), d[H(N10)...O(16~)I =
1-98 (3) ,/~, (i) = 2--x, y, l--z}.
This wo k was sponso ed by he Uni e si y o
Ba celona.
In oduc ion.
The Knoe enagel condensa ion be ween
e hyl 2-oxocyclohexaneca boxyla e and malononi ile
in basic media (Sempe e, 1983) a o ds a eac ion
p oduc di e en om ha ob ained in acid media (Van
de Baan & Bickelhaup , 1968, 1970; Kas u i &
Sha ma, 1975). The molecula s uc u e could no be
comple ely de e mined by IR, NMR, UV and mass
me hods and an X- ay analysis was unde aken o
elucida e he molecula s uc u e and geome y o he
compound.
Expe imen al.
Yellow elonga ed p isms (0.1 x 0.1 ×
0.3 mm). Philips PW-1100 di ac ome e , Mo K ~,
g aphi e monoch oma o , co-scan echnique, cell
pa ame e s om 25 e lec ions (4 <0< 12°). 1395
independen e lec ions wi h 0 _< 25 °, ange
o hkl
= 22
o 22, 0 o 7, 0 o 10; 1369 wi h I>2.Sc (/). No
signi ican a ia ion in in ensi y o h ee s anda d
e lec ions, abso p ion igno ed. Non-H a oms om
MULTANSO
(Main, Fiske, Hull, Lessinge , Ge main,
Decle cq & Wool son, 1980). Iso opic and aniso opic
ull-ma ix leas -squa es e inemen wi h
SHELX76
(Sheld ick, 1976), H om
AF
syn hesis, e ined wi h an
o e all iso opic empe a u e ac o . Func ion
minimized
wlIFol--IFcll 2,
w= [62(Fo)
+
0.0146
I Fol
2]-1; inal R = 0.056, R w = 0.072,
(A/a)ma x
= 1.9 [in U33 o O(11)].
Ap
excu sions = 0.3
[1.24/~ om C(5)] and -0.3 e,~-3, , ' and " om
In e na ional Tables o X- ay C ys allog aphy
(1974).
IBM 4341 compu e .
Discussion. Final a omic pa ame e s a e gi en in Table
1,* bond dis ances and angles in Table 2. Fig. 1 shows a
pe spec i e iew o he molecule.
The de e mina ion o he c ys al s uc u e shows he
posi ions o he subs i uen s. The py idine ing is plana ,
wi h la ges de ia ions om a oms o mean plane
-0.010 (4)/i, in C(1) and 0.010 (4)/~ in C(2). O(16)
and he ca boni ile g oup de ia e o he same side o
he plane [O(16) 0.018 (3) and C(14) 0.038
(4)A],
while he e hoxy g oup and he six-ca bon ing de ia e
o he o he side [O(11) --0.038 (3), C(7) -0.033 (4)
and C(4) -0.033 (4)AI. The six-ca bon ing has
* Lis s o s uc u e ac o s, aniso opic he mal pa ame e s and
H-a om coo dina es 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 39622 (9
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
(x 10 4)
and equi alen
iso op& empe a u e coe icien s
8 2 * *
Beq = ~7
~i~'jUi l " l jai.a j.
x y z Be,(A 2)
C(I) 9429 (2) 4278 (7) 3231 (5) 2.9 (2)
C(2) 9756 (2) 5778 (7) 2421 (5) 2.8 (2)
C(3) 10452 (2) 5481 (7) 2198 (5) 2.7 (2)
C(4) 10789 (3) 7140 (9) 1248 (7) 3.9 (3)
C(5) 11480 (3) 6340 (12) 777 (9) 5.8 (3)
C(6) 11879 (3) 5213 (10) 1984 (9) 5.5 (3)
C(7) 11525 (2) 3318 (8) 2617 (8) 3.9 (2)
C(8) 10793 (2) 3762 (7) 2818 (5) 2.8 (2)
C(9) 10452 (2) 2215 (7) 3681 (5) 2.8 (2)
N(10) 9771 (2) 2587 (6) 3848 (4) 2.8 (2)
O(I 1) 8775 (1) 4529 (5) 3394 (4) 3.6 (2)
C(12) 8379 (2) 2747 (9) 3893 (8) 4.0 (2)
C(13) 7661 (3) 3453 (11) 3695 (9) 5.1 (3)
C(14) 9385 (2) 7600 (8) 1816 (6) 3.4 (2)
N(15) 9090 (2) 9052 (7) 1331 (6) 4.6 (2)
O(16) 10723 (2) 614 (5) 4298 (4) 3.8 (2)
Table 2.
Bond dis ances (, ~) and angles (o)
C(1)-C(2) 1.378 (4) C(6)-C(7) 1.507 (4)
C(1)-N(10) 1.350 (3) C(7)-C(8) 1.514 (4)
C(1)-O(11) 1.336 (3) C(8)-C(9) 1-439 (4)
C(2)-C(3) 1.433 (4) C(9)-N(10) 1.400 (3)
C(2)-C(14) 1-439 (4) C(9)-O(16) 1.243 (3)
C(3)-C(4) 1.527 (4) O(l l)-C(12) 1.452 (3)
C(3)-C(8) 1.365 (3) C(12)-C(13) 1.500 (4)
C(4)-C(5) 1.557 (4) C(14)-N(15) I. 146 (3)
C(5)-C(6) 1.474 (5)
N(10)-C(1)-C(2) 119.8 (2) C(8)-C(7)-C(6) 112.8 (2)
O(11)-C(1)-C(2) 119.1 (2) C(7)-C(8)-C(3) 123.5 (2)
O(11)-C(I)-N(10) 121.1 (2) C(9)-C(8)-C(3) 120.1 (2)
C(3)-C(2)-C(I) 119.4 (2) C(9)-C(8)-C(7) 116.4 (2)
C(14)-C(2)-C(1) 118.7 (2) N(10)-C(9)-C(8) 116.8 (2)
C(14)-C(2)-C(3) 121.9 (2) O(16)-C(9)-C(8) 124-5 (2)
C(4)-C(3)-C(2) 117.7 (2) O(16)-C(9)-N(I0) 118.7 (2)
C(8)-C(3)-C(2) 120.3 (2) C(9)-N(10)-C(1) 123.5 (2)
C(8)-C(3)-C(4) 121.9 (2) C(12)-O(1 l)-C(1) 120.4 (2)
C(5)-C(4)-C(3) 120-0 (3) C(13)-C(12)-O(ll) 106.3 (3)
C(6)-C(5)-C(4) 113.2 (3) N(15)-C(14)-C(2) 179.8 (1)
C(7)-C(6)-C(5) 114.0 (3)
Fig. 1. View o he molecule, wi h he a bi a y numbe ing o he
a oms.
476 3-ETHOXY-5,6,7,8-TETRAHYDRO- 1-HYDROXYISOQUINOLINE-4-CARB ONITRILE
Re e ences
In e na ional Tables o X- ay C ys allog aphy (1974). Vol. IV, pp.
100, 150. Bi mingham: Kynoch P ess.
KASTURI, T. R. & SHARMA, V. K. (1975). Te ahed on, 31,
527-531.
MAIN, P., FISKE, S. J., HULL, S. E., LESSINGER, L., GERMAIN, G.,
DECLERCQ, J.-P. ~ WOOLFSON, 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.
SEMPERE,
J. (1983). New Syn hesis o Py idol3,4-d]py idazines.
PhD Thesis, IQS., Ba celona, Spain.
SHELDRICK,
G. M. (1976). SHELX76. P og am o c ys al
s uc u e de e mina ion. Uni . o Camb idge, England.
VAN
OER BAAN,
J. L. &
BICKELHAUPT,
F. (1968). Chem. Commun.
pp. 1661-1662.
VAN DER BAAN, J. L. ~ BICKELHAUPT, F. (1970).
Chem. Commun.
pp. 326-327.
Ac a C ys . (1985). C41, 476-479
sym-T iphenylcyclop openylium
Hexab omo ellu a e(IV), (C21H15)2[TeB 6]
BY BRANDAN A. BORGIAS, ROBERT C. SCARROW, MARK D. SEIDLER AND WAYNE P. WEINER
Depa men o Chemis y, Uni e si y o Cali o nia, Be keley, Cali o nia 94720, USA
(Recei ed 19 June 1984; accep ed 24 Oc obe 1984)
Abs ac . M = 1141.7, monoclinic, P21/c, a=
13.663(1), b=13.360(1), c=21.718(2)A, l=
93.612(7) ° , V=3956(1)A 3 Z=4, D_=1.92,
Dx= 1.912gem -3, 2(MoKa)=0.71073/(, ~=
67.85 cm -I, F(000)= 2176, oom empe a u e, inal
R = 0-026 o 3500 independen obse ed e lec ions.
The TeB 2- anion is nea ly oc ahed al wi h he Te--B
bonds anging om 2.69 o 2.72 A and he B -Te-B
angles anging om 87.6 o 92.1 ° . The a e age
cyclop openylium C-C bond dis ance is 1.377 ,/k. The
planes o he phenyl ings a e wis ed ela i e o he
plane o he cyclop openylium ing by ca 5 o.
In oduc ion. The geome y o he hexahalo ellu a e
dianion (TeX 6-) has p o oked conside able in e es
(Cla k, McWhinnie, Mallaki, Dance & Jones, 1980). A
dis o ed oc ahed al con igu a ion is p edic ed by
alence shell elec on pai epulsion (VSEPR) heo y
(Gillespie & Nyholm, 1957). Howe e , wo k based on
MO heo y p edic s egula oc ahed al geome y
(Gillespie, 1970; Johns one, Jones & Vasude , 1972).
Se e al 'undis o ed' s uc u es o he TeB 2- anion
ha e been epo ed (B own, 1964; Das & B own, 1966;
Dahan & Le eb e-Soubey an, 1976a; Be g & Nielsen,
1979); howe e , only in he mos ecen s udy we e he
da a co ec ed o abso p ion. In each case he dianion
possesses c ys allog_ aphically imposed poin sym-
me y: 1, m3m, 2, 3 espec i ely. Ano he s uc u e
(Dahan & Le eb e-Soubey an, 1976b) also loca es he
TeB 2- a a posi ion wi h wo old symme y; he
dianion is sligh ly dis o ed possibly due o hyd ogen
bonding in ol ing he B a oms [Te--B dis ances ange
om 2.642 (3) o 2.798 (3) A; B --Te--B angles ange
om 85.7 (1) o 93.0 (1)°]. Se e al TeX 6- (X= C1 o
0108-2701/85/030476-04501.50
I) s uc u es ha e been epo ed bu only one shows a
clea ly dis o ed TeC12- anion (Russo, Valle &
Caloge o, 1980). This is also hyd ogen-bonded o he
ca ion.
The s uc u e o he sym- iphenylcyclop openylium
ca ion (TPCP) has been epo ed by Sunda alingam &
Jensen (1966). The sho cyclop openylium C-C
dis ance obse ed in ha s uc u e [1.373 (5)A] is in
excellen ag eemen wi h he dis ance p edic ed o he
C3H ~- s uc u e
(1.377 A) (Radom, Ha iha an, Pople
& Schleye , 1976). Howe e , he appa en dis o ion o
he phenyl ings (C-C dis ances ange om 1.338 o
1.444 A in a single phenyl ing) is dis u bing.
In his pape we epo he s uc u e o
(TPCP)E[TeB 6]. By collec ing a ela i ely high-angle
da a se , and by accoun ing o abso p ion e ec s, we
hoped o gene a e supe io s uc u es o bo h he
TPCP ca ion and he TeB 62- anion.
Expe imen al. Di ac ion-quali y c ys als supplied by
M Kenne h A. Smi h o he Depa men o Chemis y,
Uni e si y o Cali o nia, Be keley. C ys al densi y
measu ed by lo a ion in oluene/b omo o m. O ange
c ys als, elonga ed pa allelepipeds (0.25 x 0.21 ×
0.18 mm) wi h be elled co ne s.
En a -Nonius CAD-4 di ac ome e . Cell dimen-
sions de e mined using 24 well cen e ed e lec ions wi h
28 < 20 < 40 °. All e lec ions wi h 0.037 < sin0/2 <
0.583A -I (0<h<15, 0<k<15, -25<l<25)
measu ed using m--20 scans wi h ollowing condi ions:
ape u e, e ical 3.0mm, ho izon al (0.55 +
0.35 an0) mm; scan wid h, (2.0 + 1.0 an0)°; back-
g ound, 25% each side o peak scan; p e-scan a e
6.7 ° min-l; addi ional scan i 0.015 < a(1)/(I) < 1,
© 1985 In e na ional Union o C ys allog aphy