organic compounds
Ê
to 1.473 (4) A]; these bond lengths are 1.249 (4) and
[
Table 1
Selected geometric parameters (A, ).
Ê
ꢀ
Ê
.431 (4) A, respectively, in azobenzene with no disorder
Harada et al., 1997). The N1 N2, N1ÐC1 and N2ÐC7
1
(
C1ÐN1
C3ÐCl1
C7ÐC8
C7ÐC12
C7ÐN2
C8ÐC9
C9ÐC13
1.429 (3)
1.743 (2)
1.367 (3)
1.413 (3)
1.414 (2)
1.408 (3)
1.411 (3)
C9ÐC10
C10ÐO1
C10ÐC11
C11ÐC12
C13ÐN3
C14ÐN3
N1ÐN2
1.436 (3)
1.286 (2)
1.426 (3)
1.360 (3)
1.298 (3)
1.470 (2)
1.256 (2)
Ê
bonds in (I) are 1.256 (2), 1.429 (3) and 1.414 (2) A, respec-
tively, indicating that there is no orientational disorder. The
two phenyl rings are planar but not coplanar with one another.
The dihedral angle, ꢀ , between the mean planes of the
1
ꢀ
chlorophenyl ring and the CÐNÐNÐC bridge is 11.6 (3) ,
and the angle, ꢀ , between the planes of the CÐNÐNÐC link
2
C6ÐC1ÐC2
C6ÐC1ÐN1
C2ÐC1ÐN1
C8ÐC7ÐC12
C8ÐC7ÐN2
120.2 (2)
116.2 (2)
123.59 (19)
119.23 (18)
115.82 (18)
C12ÐC7ÐN2
O1ÐC10ÐC9
N3ÐC13ÐC9
N3ÐC14ÐC17
C13ÐN3ÐC14
124.94 (18)
121.02 (18)
124.52 (19)
111.44 (15)
126.55 (18)
ꢀ
and the salicylidene ring is 8.9 (3) . The angle, ꢀ , between the
3
planes of the chlorophenyl and salicylidene rings is
ꢀ ꢀ
0.47 (10) , which is equal to the sum of ꢀ and ꢀ [20.5 (3) ].
1 2
2
This value of ꢀ is a little larger than those in (E)-azobenzenes
3
ꢀ
(
5±15 ; Brown, 1966). Atoms C1 and C7 are angularly asym-
C10ÐC9ÐC13ÐN3
� 0.6 (3)
C1ÐN1ÐN2ÐC7
� 177.64 (17)
metric (Table 1). This asymmetry seems to be caused by the
tendency of the azo system to be partially coplanar with the
aromatic rings because of the ꢁ-conjugation and steric
hindrance involving both the C2ÐH2 group with N2 and the
C12ÐH12 group with N1. The same angular asymmetry
occurs for atoms C13, N3 and C14 because of their asymmetric
coordination, and so the N3ÐC13ÐC9, C13ÐN3ÐC14 and
N3ÐC14ÐC17 angles are larger according to their optimal
hybridization degree.
Table 2
Hydrogen-bonding geometry (A, ).
Ê
ꢀ
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
N3ÐH33Á Á ÁO1
O2ÐH21Á Á ÁO1
O3ÐH31Á Á ÁO2
O4ÐH41Á Á ÁO3
0.86 (3)
0.83 (2)
0.78 (2)
0.98 (2)
1.93 (2)
1.78 (2)
1.89 (2)
1.81 (2)
2.639 (2)
2.610 (2)
2.655 (2)
2.780 (2)
139 (2)
i
172.2 (8)
166.1 (17)
167.1 (11)
ii
iii
In addition to the intramolecular hydrogen bond, molecules
of (I) are linked by intermolecular OÐHÁ Á ÁO hydrogen bonds
into a three-dimensional network (Fig. 2 and Table 2). There is
3
1
Symmetry codes: (i) 2 � x; 1 � y; 1 � z; (ii) 2 � x; 1 � y; 2 � z; (iii) x; 2 � y; z � 2
.
Ê
also a ꢁ±ring interaction [3.318 (19) A] between C12ÐH12
3
1
and the salicylidene ring at (x, � y + , z + ).
2
2
Data collection
Stoe Stadi-4 diffractometer
scans
h = � 21 ! 21
!
k = � 11 ! 0
Experimental
6
3
2
136 measured re¯ections
005 independent re¯ections
314 re¯ections with I > 2ꢅ(I)
l = � 11 ! 11
2 standard re¯ections
frequency: 120 min
intensity decay: 2%
A mixture of 3-chloroaniline (1.275 g, 10 mmol), water (50 ml) and
concentrated hydrochloric acid (2.5 ml, 30 mmol) was heated with
stirring until a clear solution was obtained. This solution was cooled
to 273±278 K and a solution of sodium nitrite (0.96 g, 14 mmol) in
water was added dropwise while the temperature was maintained
below 278 K. The resulting mixture was stirred for 30 min in an ice
bath. Salicylaldehyde (1.22 g, 10 mmol) solution (pH 9) was gradually
added to a cooled solution of 3-chlorobenzenediazonium chloride,
prepared as described above, and the resulting mixture was stirred at
R
int = 0.020
ꢀ
ꢀ
max = 25.0
Re®nement
2
2
2
o
2
Re®nement on F
2
w = 1/[ꢅ (F ) + (0.0496P)
2
R[F > 2ꢅ(F )] = 0.037
wR(F ) = 0.104
S = 1.06
+ 0.5398P]
where P = (F + 2F )/3
o c
2
2
2
(Á/ꢅ)max < 0.001
273±278 K for 60 min in an ice bath. The product was recrystallized
Ê
� 3
Áꢆmax = 0.50 e A
3
2
005 re¯ections
65 parameters
Áꢆmin = � 0.27 e AÊ
�
3
from ethyl alcohol to obtain solid 5-(3-chlorophenylazo)salicyl-
aldehyde (m.p. 400±402 K). To a solution of this solid (1.302 g,
H atoms treated by a mixture of
independent and constrained
re®nement
5
mmol) in butan-1-ol (75 ml) was added a solution of tris(hydroxy-
methyl)aminomethane (0.605 g, 5 mmol) in butan-1-ol (25 ml). The
mixture was stirred under re¯ux and the water produced in the
reaction was distilled out. The resulting orange precipitate was
The H atoms attached to atoms O2, O3 and O4 were re®ned using
a riding model, with OÐH distances free to re®ne and Uiso values
equal to 1.2Ueq of the parent atom. The H atoms attached to atoms
C15, C16 and C17 were re®ned using a riding model, with CÐH
®ltered off and recrystallized from ethyl alcohol. Crystals of (I) were
obtained after 2 d by slow evaporation from acetonitrile (yield 90%;
m.p. 455±457 K).
Ê
distances of 0.96 A. H atoms bonded to the other C atoms and to N3
were re®ned isotropically. The calculated CÐH bond lengths were in
Ê
the range 0.89 (3)±0.98 (2) A.
Crystal data
�
3
C
17
3
H18ClN O
4
D
x
= 1.415 Mg m
M
r
= 363.79
Mo Kꢃ radiation
Monoclinic, P2 =c
Cell parameters from 100
re¯ections
Data collection: STADI4 (Stoe & Cie, 1996); cell re®nement:
STADI4; data reduction: X-RED (Stoe & Cie, 1996); program(s)
used to solve structure: SHELXS97 (Sheldrick, 1997); program(s)
used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular
graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to
prepare material for publication: WinGX (Farrugia, 1998).
1
Ê
a = 18.418 (4) A
Ê
b = 9.821 (2) A
ꢀ
ꢀ = 3.0±25.0
ꢄ = 0.25 mm
T = 295 K
Ê
c = 9.5020 (19) A
� 1
ꢀ
ꢂ = 96.64 (3)
V = 1707.2 (6) A
Z = 4
Ê
3
Prism, orange
0.40 Â 0.30 Â 0.10 mm
Acta Cryst. (2003). C59, o234±o236
Mustafa Odaba sÎ o gÏ lu et al.
ꢁ
C H18ClN O
17 3 4
o235