2‐Bromo‐5‐methoxy‐N′‐[(E)‐(2‐nitrophenyl)methylene]benzohydrazide

TLDR: In this paper, the title compound, C15H12BrN3O4, a Schiff base, is described and the crystal packing is stabilized by N −H⋯O hydrogen bonds.

Abstract: Geometric parameters of the title compound, C15H12BrN3O4, a Schiff base, are in the usual ranges. There are two mol­ecules in the asymmetric unit, differing in the dihedral angles between the aromatic rings and the central CO—NH—N=C unit. Furthermore, the Car—Car—O—CH3 torsion angles differ by almost 180°. The crystal packing is stabilized by N—H⋯O hydrogen bonds.

Figures

Fig. 2

Fig. 1

Table 1 Hydrogen-bond geometry (Å, ).

Full text

2-Bromo-5-methoxy-N
000
-[(E)-(2-nitro-
phenyl)methylene]benzohydrazide
H. S. Yathirajan,
a
B. K. Sarojini,
b
B. Narayana,
c
K. Sunil
c
and Michael Bolte
d
*
a
Department of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore
570 006, India,
b
Department of Chemistry, P. A. College of Engineering,
Nadupadavu, Mangalore 574 153, India,
c
Department of Studies in Chemistry,
Mangalore University, Mangalagangotri 574 199, India, and
d
Institut fu
¨
r
Anorganische Chemie, J. W. Goethe-Universita
¨
t Frankfurt, Max-von-Laue-Strasse 7,
60438 Frankfurt/Main, Germany
Correspondence e-mail: bolte@chemie.uni-frankfurt.de
Received 19 April 2007; accepted 24 April 2007
Key indicators: single-crystal X-ray study; T = 173 K; mean (C–C) = 0.003 A
˚
;
R factor = 0.037; wR factor = 0.091; data-to-parameter ratio = 16.4.
Geometric parameters of the title compound, C
15
H
12
BrN
3
O
4
,
a Schiff base, are in the usual ranges. There are two molecules
in the asymmetric unit, differing in the dihedral angles
between the aromatic rings and the central CO—NH—N
C
unit. Furthermore, the C
ar
—C
ar
—O—CH
3
torsion angles
differ by almost 180

. The crystal packing is stabilized by
N—HO hydrogen bonds.
Related literature
For related structures, see: He et al. (2005), Zhen et al.
(2005a,b), Diao et al. (2005). For related literature, see: El-
Masry et al. (2000); Pandey et al. (1999); Singh et al. (1988);
Hodnett et al. (1970); Desai et al. (2001); Aydog
˘
an et al. (2001);
Taggi et al. (2002).
Experimental
Crystal data
C
15
H
12
BrN
3
O
4
M
r
= 378.19
Triclinic, P
1
a = 8.1611 (6) A
˚
b = 9.0279 (6) A
˚
c = 21.3467 (15) A
˚
 = 85.585 (6)

 = 89.441 (6)

 = 75.912 (5)

V = 1520.88 (18) A
˚
3
Z =4
Mo K radiation
 = 2.73 mm
1
T = 173 (2) K
0.36  0.33  0.32 mm
Data collection
Stoe IPDSII two-circle
diffractometer
Absorption correction: multi-scan
(MULABS; Spek, 2003;
Blessing, 1995)
T
min
= 0.401, T
max
= 0.426
22860 measured reflections
7003 independent reflections
5849 reflections with I >2(I)
R
int
= 0.061
Refinement
R[F
2
>2(F
2
)] = 0.037
wR(F
2
) = 0.091
S = 1.01
7003 reflections
426 parameters
H atoms treated by a mixture of
independent and constrained
refinement

max
= 0.99 e A
˚
3

min
= 0.82 e A
˚
3
Table 1
Hydrogen-bond geometry (A
˚
,

).
D—HAD—H HADAD—HA
N1—H1O1A
i
0.86 (3) 2.09 (3) 2.863 (2) 149 (3)
N1A—H1AO1 0.89 (3) 2.00 (3) 2.872 (3) 165 (3)
Symmetry code: (i) x  1; y; z.
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-
AREA; data reduction: X-AREA; program(s) used to solve structure:
SHELXS97 (Sheldrick, 1997); program(s) used to refine structure:
SHELXL97 (Sheldrick, 1997); molecular graphics: XP in
SHELXTL-Plus (Sheldrick, 1991); software used to prepare material
for publication: SHELXL97.
KS thanks the Department of Studies in Chemistry,
Mangalore University for research facilities.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: AT2279).
References
Aydog
˘
an, F., O
¨
cal, N., Turgut, Z. & Yolac¸an, C. (2001). Bull. Korean Chem.
Soc. 22, 476–480.
Blessing, R. H. (1995). Acta Cryst. A51, 33–38.
Desai, S. B., Desai, P. B. & Desai, K. R. (2001). Heterocycl. Commun. 7, 83–90.
Diao, C.-H., Yu, M., Chen, X., Jing, Z.-L. & Deng, Q.-L. (2005). Acta Cryst.
E61, o3500–o3501.
El-Masry, A. H., Fahmy, H. H. & Abdelwahed, S. H. A. (2000). Molecules, 5,
1429-1438.
He, Y.-Z. & Liu, D.-Z. (2005). Acta Cryst. E61, o3855–o3856.
Hodnett, E. M. & Dunn, W. J. (1970). J. Med. Chem. 13, 768–770.
Pandey, S. N., Sriram, D., Nath, G. & De Clercq, E. (1999). Il Farmaco, 54, 624–
628.
Sheldrick, G. M. (1991). SHELXTL-Plus. Release 4.1. Siemens Analytical
X-ray Instruments Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
Go
¨
ttingen, Germany.
Singh, W. M. & Dash, B. C. (1988). Pesticides, 22, 33–37.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.
Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany.
Taggi, A. E., Hafez, A. M., Wack, H., Young, B., Ferraris, D. & Lectka, T.
(2002). J. Am. Chem. Soc. 124, 6626–6635.
Zhen, X.-L. & Han, J.-R. (2005a). Acta Cryst. E61, o4282–o4284.
Zhen, X.-L. & Han, J.-R. (2005b). Acta Cryst. E61, o4360–o4361.
organic compounds
Acta Cryst. (2007). E63, o2719 doi:10.1107/S1600536807020375 # 2007 International Union of Crystallography o2719
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

supplementary materials

supplementary materials
sup-1
Acta Cryst. (2007). E63, o2719 [ doi:10.1107/S1600536807020375 ]
2-Bromo-5-methoxy-N'-[(E)-(2-nitrophenyl)methylene]benzohydrazide
H. S. Yathirajan, B. K. Sarojini, B. Narayana, K. Sunil and M. Bolte
Comment
Schiff bases are used as substrates in the preparation of number of industrial and biologically active compounds via ring
closure, cycloaddition and replacement reactions. Moreover, Schiff bases are also known to have biological activities such
as antimicrobial, antifungal, antitumor and as herbicides. Schiff bases have also been employed as ligands for complexation
of metal ions. On the industrial scale, they have wide range of applications such as dyes and pigments. A new Schiff base,
C
15
H
12
BrN
3
O
4
, was synthesized and its crystal structure is reported.
There are two molecules in the asymmetric unit differing in the dihedral angles between the aromatic rings and the central
CO—NH—N=C unit [N2—C2—C21—C22 = 159.2 (2)°, N2A—C2A—C21A—C22A = -169.3 (2)°, O1—C1—C11—C12
= 74.2 (3)° and O1A—C1A—C11A—C12A = 104.5 (3)°]. The crystal packing is stabilized by N—H···O hydrogen bonds.
Experimental
A mixture of 2-bromo-5-methoxybenzohydrazide (1.22 g, 0.005 mol) and 2-nitrobenzaldehyde (0.75 g, 0.005 mol) in 25 ml
of absolute ethanol containing 2 drops of 4 M sulfuric acid was refluxed for about 3 hours. On cooling, the solid separated
was filtered and recrystallized from a mixture of (5:5) DMF & acetone (m.p.: 486-488 K). Analysis for C
15
H
12
BrN
3
O
4
:
Found (Calculated): C : 47.56 (47.64); H:3.14 (3.20); N:11.04% (11.11%).
Refinement
All H atoms were found in a difference map, and the ones of the NH groups were refined freely. The rest H atoms were
refined using a riding model with C
aromatic
—H = 0.95 Å, C
methyl
—H = 0.98Å or C
methylene
—H = 0.99Å and U
iso
(H) =
1.2U
eq
(C) or U
iso
(H) = 1.5U
eq
(C
methyl
). The methyl group was allowed to rotate but not to tip.
Figures
Fig. 1. Perspective view of molecule one in the asymmetric unit of the title compound with
the atom numbering; displacement ellipsoids are at the 50% probability level.
Fig. 2. Perspective view of molecule two in the asymmetric unit of the title compound with
the atom numbering; displacement ellipsoids are at the 50% probability level.

supplementary materials
sup-2
2-Bromo-5-methoxy-N'-[(E)-(2-nitrophenyl)methylene]benzohydrazide
Crystal data
C
15
H
12
BrN
3
O
4
Z = 4
M
r
= 378.19
F
000
= 760
Triclinic, P1
D
x
= 1.652 Mg m
−3
Hall symbol: -P 1
Mo Kα radiation
λ = 0.71073 Å
a = 8.1611 (6) Å
Cell parameters from 21874 reflections
b = 9.0279 (6) Å
θ = 2.5–26.8º
c = 21.3467 (15) Å
µ = 2.73 mm
−1
α = 85.585 (6)º
T = 173 (2) K
β = 89.441 (6)º Block, colourless
γ = 75.912 (5)º 0.36 × 0.33 × 0.32 mm
V = 1520.88 (18) Å
3
Data collection
Stoe IPDSII two-circle
diffractometer
7003 independent reflections
Radiation source: fine-focus sealed tube
5849 reflections with I > 2σ(I)
Monochromator: graphite
R
int
= 0.061
T = 173(2) K
θ
max
= 27.6º
ω scans
θ
min
= 2.6º
Absorption correction: multi-scan
(MULABS; Spek, 2003; Blessing, 1995)
h = −10→10
T
min
= 0.401, T
max
= 0.426
k = −11→11
22860 measured reflections
l = −27→27
Refinement
Refinement on F
2
H atoms treated by a mixture of
independent and constrained refinement
Least-squares matrix: full
w = 1/[σ
2
(F
o
2
) + (0.0556P)
2
+ 0.1348P]
where P = (F
o
2
+ 2F
c
2
)/3
R[F
2
> 2σ(F
2
)] = 0.037
(Δ/σ)
max
= 0.001
wR(F
2
) = 0.091
Δρ
max
= 0.99 e Å
−3
S = 1.01
Δρ
min
= −0.82 e Å
−3
7003 reflections
Extinction correction: SHELXL97,
Fc
*
=kFc[1+0.001xFc
2
λ
3
/sin(2θ)]
-1/4
426 parameters Extinction coefficient: 0.0124 (9)
Primary atom site location: structure-invariant direct
methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring
sites

supplementary materials
sup-3
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The
cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds
in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used
for estimating esds involving l.s. planes.
Refinement. Refinement of F
2
against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F
2
, convention-
al R-factors R are based on F, with F set to zero for negative F
2
. The threshold expression of F
2
> 2sigma(F
2
) is used only for calculat-
ing R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F
2
are statistically about twice
as large as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å
2
)
x y z
U
iso
*/U
eq
Br1 0.57284 (3) 0.71784 (3) 0.426996 (11) 0.02848 (8)
C1 0.5711 (3) 0.7471 (3) 0.27886 (10) 0.0187 (4)
O1 0.7255 (2) 0.7090 (2) 0.27580 (9) 0.0286 (4)
N1 0.4720 (2) 0.8821 (2) 0.25625 (9) 0.0196 (4)
H1 0.366 (4) 0.904 (3) 0.2649 (13) 0.019 (7)*
N2 0.5393 (2) 0.9885 (2) 0.22119 (8) 0.0183 (4)
C2 0.4284 (3) 1.1108 (3) 0.20414 (10) 0.0187 (4)
H2 0.3140 1.1220 0.2163 0.022*
C11 0.4685 (3) 0.6411 (2) 0.30862 (10) 0.0179 (4)
C12 0.4638 (3) 0.6110 (3) 0.37360 (10) 0.0202 (4)
C13 0.3702 (3) 0.5126 (3) 0.39970 (11) 0.0234 (5)
H13 0.3714 0.4899 0.4439 0.028*
C14 0.2756 (3) 0.4475 (3) 0.36165 (11) 0.0240 (5)
H14 0.2112 0.3807 0.3797 0.029*
C15 0.2745 (3) 0.4802 (3) 0.29653 (11) 0.0220 (4)
C16 0.3741 (3) 0.5756 (3) 0.27024 (10) 0.0208 (4)
H16 0.3768 0.5953 0.2259 0.025*
O17 0.1820 (2) 0.4259 (2) 0.25485 (9) 0.0311 (4)
C17 0.0475 (3) 0.3619 (3) 0.27988 (14) 0.0342 (6)
H17A 0.0946 0.2731 0.3093 0.051*
H17B −0.0110 0.3297 0.2454 0.051*
H17C −0.0326 0.4393 0.3020 0.051*
C21 0.4792 (3) 1.2352 (3) 0.16530 (10) 0.0181 (4)
C22 0.3661 (3) 1.3493 (3) 0.12820 (10) 0.0189 (4)
C23 0.4140 (3) 1.4700 (3) 0.09437 (11) 0.0249 (5)
H23 0.3337 1.5450 0.0696 0.030*
C24 0.5812 (3) 1.4787 (3) 0.09743 (12) 0.0287 (5)
H24 0.6163 1.5600 0.0747 0.034*
C25 0.6968 (3) 1.3684 (3) 0.13376 (12) 0.0273 (5)
H25 0.8108 1.3752 0.1362 0.033*
C26 0.6471 (3) 1.2473 (3) 0.16684 (10) 0.0221 (4)
H26 0.7286 1.1718 0.1909 0.027*
N22 0.1860 (2) 1.3483 (2) 0.12283 (9) 0.0221 (4)