4-(4-Hydroxybenzylideneamino)-4H-1,2,4-triazole hemihydrate

Full text of DOI:10.1107/S0108270199014572

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
ISSN 0108-2701
4-(4-Hydroxybenzylideneamino)-4H-
1,2,4-triazole hemihydrate
Figure 1
The structure of (I) showing 50% probability displacement ellipsoids with
the numbering scheme.
Dun-Ru Zhu, Yan Xu, Yong-Jiang Liu, You Song, Yong
Zhang* and Xiao-Zeng You
Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry,
Nanjing University, Nanjing 210093, People's Republic of China
Correspondence e-mail: xyz@nju.edu.cn
Table 2. In the packing of molecules of the title compound, the
water molecules (O1W) lie on crystallographic twofold axes.
Received 18 October 1999
Accepted 9 November 1999
Experimental
The title compound was prepared by condensation of equivalent
amounts of p-hydroxybenzaldehyde and 4-amino-1,2,4-triazole in
ethanol for 5 h (Kitaev et al., 1971). Diffraction-quality crystals were
obtained by recrystallization from ethanol.
In the title compound, 4-(4H-1,2,4-triazol-4-yliminomethyl)-
phenol hemihydrate, C9H8N4OÁ0.5H2O or (I)Á0.5H2O, mol-
ecules of (I) are arranged as layers running along the b axis
through intermolecular OÐHÁ Á ÁN and CÐHÁ Á ÁO hydrogen
bonds. These layers are stabilized by hydrogen-bonded water
molecules to form three-dimensional networks.
Crystal data
3
C9H8N4OÁ0:5H2O
Dx = 1.413 Mg m
Mo Kꢁ radiation
Cell parameters from 36
re¯ections
Mr = 197.20
Monoclinic, C2=c
Ê
Ê
a = 14.134 (2) A
b = 12.491 (2) A
ꢂ = 5.22±9.01ꢁ
ꢃ = 0.102 mm
T = 293 (2) K
1
Comment
Ê
c = 12.063 (2) A
ꢀ = 119.483 (10)ꢁ
The aroyl Schiff bases of 4-amino-1,2,4-triazole have received
considerable attention over the past few decades (Kitaev et al.,
1971; Mazza et al., 1976; Kargin et al., 1988). It is of interest
that some of them are anti-in¯ammatory agents (Gupta &
Bhargava, 1978) and new coccidiostatic drugs (Colautti et al.,
1971). As a continuation of our study on the structure of
Schiff-base-containing substituted 1,2,4-triazole (Shanmuga
Sundara Raj et al., 1999), we report here the title structure, (I).
3
Ê
V = 1854.0 (5) A
Z = 8
Block, colourless
0.30 Â 0.26 Â 0.20 mm
Data collection
Siemens P4 diffractometer
2ꢂ/! scans
Rint = 0.021
ꢂmax = 25ꢁ
Absorption correction: empirical
(North et al., 1968)
Tmin = 0.954, Tmax = 0.968
2043 measured re¯ections
1642 independent re¯ections
1100 re¯ections with I > 2ꢄ(I)
h = 1 ! 16
k = 1 ! 14
l = 14 ! 12
3 standard re¯ections
every 97 re¯ections
intensity decay: 5.84%
Re®nement
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.057
wR(F2) = 0.155
S = 1.166
1637 re¯ections
133 parameters
H atoms treated by a mixture of
independent and constrained
re®nement
w = 1/[ꢄ2(Fo2) + (0.0851P)2
+ 1.2289P]
where P = (Fo2 + 2Fc2)/3
An ORTEPII (Johnson, 1976) diagram of (I) with
numbering scheme is shown in Fig. 1. Compared to 9-(4H-
1,2,4-triazol-4-ylimino)-4,5-diaza¯uorene (Shanmuga Sundara
Raj et al., 1999), molecules of (I) are essentially planar [the
maximum displacement from the least-squares mean plane
(Á/ꢄ)max
Áꢅmax = 0.28 e A
=
0.006
3
Ê
3
Ê
0.21 e A
Áꢅmin
=
Extinction correction: SHELXTL
(Siemens, 1995)
Extinction coef®cient: 0.0022 (6)
Ê
through the whole molecule is 0.073 (2) A for C9]. The bond
lengths and angles observed in the structure are in the normal
ranges. In contrast with 2-(2-hydroxybenzylidene)-1-(2-pico-
loyl)hydrazine hemihydrate (Wang et al., 1998), molecules of
(I) are arranged as layers running along the b axis through
Table 1
Selected geometric parameters (A, ).
ꢁ
Ê
N1ÐC7
N1ÐN2
N2ÐC9
N2ÐC8
N3ÐC8
1.267 (2)
1.409 (2)
1.357 (2)
1.362 (2)
1.304 (3)
N3ÐN4
N4ÐC9
C1ÐO1
C4ÐC7
1.383 (2)
1.302 (2)
1.350 (2)
1.456 (3)
1
1
1
strong intermolecular O1ÐH11Á Á ÁN4(
+ x,
y, + z)
1
2
2
2
2
hydrogen bonds and weak C9ÐH9Á Á ÁO1(12 x,
+ y,
z) ones. These layers are stabilized by water molecules
1
2
to form three-dimensional networks through strong O1WÐ
H1WÁ Á ÁN3 hydrogen bonds and weak C7ÐH7Á Á ÁO1W(x, y,
C7ÐN1ÐN2
C9ÐN2ÐC8
C9ÐN2ÐN1
115.4 (2)
105.7 (2)
122.0 (2)
C8ÐN2ÐN1
O1ÐC1ÐC6
N1ÐC7ÐC4
132.3 (2)
123.0 (2)
122.5 (2)
1
2
+ z) ones. The geometry of these interactions are listed in
ꢀ
242 Dun-Ru Zhu et al. C9H8N4OÁ0.5H2O
Acta Cryst. (2000). C56, 242±243

organic compounds
Table 2
Hydrogen-bonding geometry (A, ).
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: NA1438). Services for accessing these data are
described at the back of the journal.
ꢁ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
O1ÐH11Á Á ÁN4i
1.01
1.18
1.02
1.10
1.74
2.15
1.89
2.47
2.717 (2)
3.293 (3)
2.898 (2)
3.214 (2)
161
164
169
123
References
C9ÐH9Á Á ÁO1ii
Colautti, A., Ferlauto, R. J., Maurich, V., De Nardo, M., Nisi, C., Rubessa, F. &
Runti, C. (1971). Chim. Ther. 6, 367±379.
Gupta, A. K. & Bhargava, K. P. (1978). Pharmazie, 33, 430±431.
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National
Laboratory, Tennessee, USA.
O1WÐH1WÁ Á ÁN3
C7ÐH7Á Á ÁO1Wiii
1
2
1
2
1
1
2
1
Symmetry codes: (i) x
;
y; 12 ‡ z; (ii)
x; y
;
z; (iii) x; y; 12 ‡ z.
2
2
Kargin, Yu. M., Kitaeva, M. Yu., Latypova, V. Z., Va®na, A. A., Zaripova, R.
M. & Il'yasov, A. V. (1988). Izv. Akad. Nauk SSSR Ser. Khim. 3, 607±611.
Kitaev, Yu. P., Savin, V. I., Zverev, V. V. & Popova, G. V. (1971). Khim.
Geterotsikl. Soedin. 7, 559±564.
Mazza, M., Montanari, L. & Pavanetto, F. (1976). Farmaco Ed. Sci. 31, 334±
344.
Data collection: XSCANS (Siemens, 1994); cell re®nement:
XSCANS; data reduction: SHELXTL (Siemens, 1995); program(s)
used to solve structure: SHELXTL; program(s) used to re®ne
structure: SHELXTL; molecular graphics: SHELXTL; software used
to prepare material for publication: SHELXTL.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351±
359.
Shanmuga Sundara Raj, S., Fun, H.-K., Zhu, D.-R., Jian, F.-F., Zhang, K.-L. &
You, X.-Z. (1999). Acta Cryst. C55, 1526±1528.
Siemens (1994). XSCANS. Version 2.1. Siemens Analytical X-ray Instruments
Inc., Madison, Wisconsin, USA.
Siemens (1995). SHELXTL. Version 5.0. Siemens Analytical X-ray Instru-
ments Inc., Madison, Wisconsin, USA.
Wang, Z.-X., Jian, F.-F., Duan, C.-Y., Bai, Z.-P. & You, X.-Z. (1998). Acta Cryst.
C54, 1927±1929.
This work was funded by a state key project of the
Fundamental Research and the National Nature Science
Foundation of China and Nanjing University Talent Devel-
opment Foundation.
ꢀ
Acta Cryst. (2000). C56, 242±243
Dun-Ru Zhu et al. C9H8N4OÁ0.5H2O 243