2,6-Bis[(2-hydr-oxy-3-methoxy-benzyl-idene)hydrazinocarbon-yl]pyridine monohydrate

Article abstract of DOI:10.1107/S0108270107021920

In the title compound, C23H19N5O6·H2O, the two components are linked into complex chains by a combination of two independent O - H...O and two independent N - H...O hydrogen bonds. The complex chains are linked into a two-dimensional sheet network via π-π

Full text of DOI:10.1107/S0108270107021920

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
In compound (I), the two hydrazine components (N2ÐN3
and N4ÐN5) have essentially planar coordinations, and the
NÐN bond distances (Table 1) have values typical for
ISSN 0108-2701
hydrazine, with both N atoms having a planar coordination
Ê
[
mean value = 1.401 (3) A; Allen et al., 1987]. The fragments
C5ÐC6( O1)ÐN2ÐN3, C1ÐC15( O4)ÐN4ÐN5, C8Ð
C7ÐN3ÐN2 and C17ÐC16ÐN5ÐN4 are essentially planar,
as shown by the key torsion angles. The dihedral angles
between pyridine ring A and the two benzene rings, B and C,
2
,6-Bis[(2-hydroxy-3-methoxybenzyl-
idene)hydrazinocarbonyl]pyridine
monohydrate
ꢀ
are 17.6 (1) and 17.72 (9) , respectively. The dihedral angle
ꢀ
between the two benzene rings is 33.48 (9) .
Within the selected asymmetric unit (Fig. 1), two hydroxyl
Zhi-Feng Li,* Ping Wang, Qian Zhang, Zao-Ming Chen and
Chun-Xiang Wang
O atoms (O2 and O5) act as hydrogen-bond donors, via atoms
H2 and H5, respectively, to atoms N3 and N5, thereby
1
1
School of Materials and Chemical Engineering, Jiangxi University of Science and
Technology, Ganzhou 341000, People's Republic of China
Correspondence e-mail: jxlzfeng@yahoo.com.cn
generating intramolecular hydrogen bonds of R (6) motif
(Bernstein et al., 1995). Hydrazine atoms N2 and N4 act as
hydrogen-bond acceptors, forming intermolecular hydrogen
1
1
bonds of R (10) motifs to water atom O7. The solvent water
Received 31 March 2007
Accepted 3 May 2007
Online 31 May 2007
molecule O7 also donates two H atoms to carboxyl atoms O1
and O4 of two different molecules to form relatively strong
OÐHÁ Á ÁO hydrogen bonds.
In the title compound, C H N O ÁH O, the two components
2
3
19
5
6
2
Through the two intermolecular OÐHÁ Á ÁO hydrogen
bonds and two NÐHÁ Á ÁO hydrogen bonds to water molecules,
compound (I) is linked into a one-dimensional chain along the
are linked into complex chains by a combination of two
independent OÐHÁ Á ÁO and two independent NÐHÁ Á ÁO
hydrogen bonds. The complex chains are linked into a two-
dimensional sheet network via ꢀ±ꢀ stacking interactions and
CÐHÁ Á ÁO hydrogen bonds.
[010] direction (Fig. 2). It is noteworthy that ꢀ±ꢀ stacking
interactions play an important role in building the one-
Comment
As part of our synthetic study of Schiff base systems, we are
now focusing on the synthesis of propeller-shaped amido-
containing organic compounds, which are important multi-
dentate ligands for the construction of coordination com-
plexes with metal centres (Wang et al., 2005). In 1985, 5-H-
substituted 2,6-bis(salicylidenehydrazinocarbonyl)pyridine as
a potential mono-, di- and tri-nucleating ligand towards uranyl
ions (Paolucci et al., 1985) was reported. More recently, a
series of 5-substituted 2,6-bis(salicylidenehydrazinocarbonyl)-
pyridine ligands (see scheme) and their copper(II) complexes
have been reported (Chen et al., 1996, 1997). However, the
researchers only paid attention to the synthesis of their
coordination complexes, and did not report the crystal struc-
tures of the organic ligands. In this report, we have synthesized
Figure 1
A view of the title compound, showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 30% probability level and H
atoms are shown as small spheres of arbitrary radii. Dashed lines indicate
hydrogen bonds.
the title 3-methoxy derivative with a propeller shape, (I), and
describe its crystal structure. For convenience, we denote the
benzene ring containing atom C8 as B, the benzene ring
containing atom C17 as C and the pyridine ring as A.
Figure 2
The one-dimensional chain structure of (I). Dashed lines indicate
hydrogen bonds.
Acta Cryst. (2007). C63, o369±o370
DOI: 10.1107/S0108270107021920
# 2007 International Union of Crystallography o369

organic compounds
dimensional chains into two-dimensional layers parallel to
(
Table 1
Selected geometric parameters (A, ).
Ê
ꢀ
100) (Fig. 3). In the chains, the molecules are antiparallel to
each other and the pyridine ring A at (x, y, z) is sandwiched by
benzene rings B at (1 � x, � y, 1 � z) and C at (1 � x, 1 � y,
N2ÐN3
1.373 (2)
N4ÐN5
1.371 (3)
1
3
� z). The mean interplanar distances are 3.697 (3) and
C5ÐC6ÐN2ÐN3
C8ÐC7ÐN3ÐN2
176.31 (17)
179.90 (18)
C1ÐC15ÐN4ÐN5
C17ÐC16ÐN5ÐN4
168.92 (16)
176.45 (16)
Ê
.749 (3) A, respectively, indicating ef®cient ꢀ±ꢀ stacking
interactions. Between adjacent chains, the benzene ring plane
C at (x, y, z) is antiparallel to benzene ring C at (1 � x, 1 � y,
Ê
z), with an interplanar distance of 3.492 (3) A. Additional
Table 2
Hydrogen-bond geometry (A, ).
�
Ê
ꢀ
CÐHÁ Á ÁO hydrogen bonds (Table 2) help to stabilize the layer
structure.
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
O2ÐH2Á Á ÁN3
N2ÐH2BÁ Á ÁO7
N4ÐH4BÁ Á ÁO7
O5ÐH5Á Á ÁN5
O7ÐH7BÁ Á ÁO1
O7ÐH7CÁ Á ÁO4
0.82
0.89
0.89
0.82
0.82
0.82
0.96
1.90
2.30
2.25
1.87
2.04
2.12
2.56
2.613 (2)
3.035 (2)
3.097 (2)
2.593 (2)
2.848 (2)
2.875 (2)
3.258 (3)
146
139
160
146
170
154
130
i
ii
iii
C14ÐH14BÁ Á ÁO5
Symmetry codes: (i) � x ‡ 1; � y; � z ‡ 1; (ii) � x ‡ 1; � y ‡ 1; � z ‡ 1; (iii) x ‡ 1, y � 1,
z ‡ 1.
C-bound H atoms were positioned geometrically (CÐH = 0.93±
Ê
.96 A) and re®ned as riding [Uiso(H) = 1.2Ueq(C) or 1.2Ueq(methyl
0
Figure 3
C)]. N-bound H atoms were found in difference maps, relocated in
The two-dimensional layer structure of (I). Dashed lines indicate
hydrogen bonds. H atoms attached to C atoms have been omitted for
clarity.
Ê
idealized positions (NÐH = 0.89 A) and re®ned as riding [Uiso(H) =
1.2Ueq(N)]. Water and hydroxyl H atoms were found in difference
Ê
maps, relocated in idealized positions (OÐH = 0.82 A) and re®ned as
riding atoms [Uiso(H) = 1.2Ueq(O)].
Experimental
Data collection: SMART (Bruker, 2004); cell re®nement: SAINT
Bruker, 2004); data reduction: SAINT; program(s) used to solve
For the preparation of 2,6-bis(hydrazinocarbonyl)pyridine, diethyl
pyridine-2,6-dicarboxylate (1.95 g, 10 mmol) and hydrazine hydrate
(
structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne
structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
SHELXTL (Bruker, 2004); software used to prepare material for
publication: SHELXTL.
(
(
10 ml, 85%) were reacted in a 100 ml reaction ¯ask in chloroform
60 ml). The product was recrystallized from a large amount of
water as colourless needles (75% yield). For the preparation of
2
,6-bis[(2-hydroxy-3-methoxybenzylidene)hydrazinocarbonyl]pyridine,
,6-bis(hydrazinocarbonyl)pyridine (1.95 g, 10 mmol), 2-hydroxy-3-
2
This work was supported by Jiangxi Provincial Natural
Science Foundation (grant No. 0620018), Jiangxi Provincial
Educational Foundation (grant No. 2005-146) and Jiangxi
University of Science and Technology Doctoral Foundation
methoxybenzaldehyde (3.04 g, 20 mmol) and p-toluenesulfonic acid
as catalyst were added to a 100 ml reaction ¯ask with ethanol (60 ml).
The mixture was stirred with a magnetic stirrer and re¯uxed for about
3
h. After ®ltration and removal of the ethanol by rotary evaporation,
(grant No. 2003-1).
the crude product was obtained and this was recrystallized from
methanol (85% yield).
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: AV3088). Services for accessing these data are
described at the back of the journal.
Crystal data
ꢀ
C
23
H
21
N
5
O
6
ÁH
2
O
ꢃ = 92.42 (3)
Ê
3
M = 481.46
Triclinic, P1
r
V = 1122.6 (4) A
Z = 2
Ê
Ê
a = 10.184 (2) A
Mo Kꢁ radiation
References
� 1
b = 10.842 (1) A
ꢄ = 0.11 mm
T = 291 (2) K
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Ê
c = 11.034 (2) A
ꢀ
ꢁ
= 98.72 (3)
0.30 Â 0.20 Â 0.20 mm
ꢀ
ꢂ = 110.42 (2)
Data collection
(
Version 5.10). Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker SMART APEXII CCD
area-detector diffractometer
Absorption correction: multi-scan
5277 measured re¯ections
5177 independent re¯ections
4150 re¯ections with I > 2ꢅ(I)
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(
T
SADABS; Sheldrick, 2003)
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Re®nement
2
2
R[F > 2ꢅ(F )] = 0.053
wR(F ) = 0.139
317 parameters
H-atom parameters constrained
2
Ê
� 3
S = 1.00
5
Áꢆmax = 0.21 e A
Wang, C.-X., Du, C.-X., Li, Y.-H. & Wu, Y.-J. (2005). Inorg. Chem. Commun. 8,
379±381.
Áꢆmin = � 0.20 e AÊ
� 3
177 re¯ections
ꢁ
o370 Li et al.
23 21
C H N
5 6 2
O ÁH O
Acta Cryst. (2007). C63, o369±o370