N′-(5-Bromo-2-methoxy­benzyl­idene)-3,4-methyl­enedioxy­benzohydrazide

Sang, Y.-L.; Lin, X.-S.

doi:10.1107/S1600536809022818

organic compounds

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Volume 65| Part 7| July 2009| Page o1636

doi:10.1107/S1600536809022818

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N′-(5-Bromo-2-methoxybenzylidene)-3,4-methylenedioxybenzohydrazide

Ya-Li Sang ^a ^* and Xue-Song Lin ^a

^aDepartment of Chemistry, Chifeng University, Chifeng 024001, People's Republic of China
^*Correspondence e-mail: sangyali0814@126.com

(Received 9 June 2009; accepted 13 June 2009; online 20 June 2009)

In the title molecule, C₁₆H₁₃BrN₂O₄, the two benzene rings form a dihedral angle of 74.9 (2)°. In the crystal, molecules are linked via intermolecular N—H⋯O hydrogen bonds into chains propagating along the c axis.

Related literature

For the biological activity of hydrazone derivatives, see: Khattab (2005 ); Küçükgüzel et al. (2003 ); Cukurovali et al. (2006 ). For the crystal structures of related compounds, see: Fun et al. (2008 ); Wei et al. (2009 ); Khaledi et al. (2008 ); Yang et al. (2008 ).

Experimental

Crystal data

C₁₆H₁₃BrN₂O₄
M_r = 377.19
Monoclinic, P 2₁ /c
a = 12.678 (1) Å
b = 16.217 (2) Å
c = 7.846 (2) Å
β = 104.804 (3)°
V = 1559.6 (5) Å³
Z = 4
Mo Kα radiation
μ = 2.66 mm⁻¹
T = 298 K
0.30 × 0.28 × 0.27 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.503, T_max = 0.534 (expected range = 0.460–0.488)
8368 measured reflections
3110 independent reflections
1932 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.096
S = 1.04
3110 reflections
212 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2ⁱ	0.89 (3)	1.96 (3)	2.841 (3)	168 (3)
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809022818/cv2572sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809022818/cv2572Isup2.hkl

checkCIF report

Comment top

Hydrazone compounds have been widely investigated due to their interesting biological properties, such as antibacterial and antitumor activities (Khattab, 2005; Küçükgüzel et al., 2003; Cukurovali et al., 2006). Recently, a number of crystal structures of hydrazone derivatives have been reported (Fun et al., 2008; Wei et al., 2009; Khaledi et al., 2008; Yang et al., 2008). In this paper, the crystal structure of the title new hydrazone compound is reported.

The molecular structure of the title compound is shown inFig. 1. The molecule adopts an E configuration with respect to the C═N bond. The dihedral angle between the two substituted benzene rings is 74.9 (2)°.

In the crystal, the molecules are linked via intermolecular N—H···O hydrogen bonds (Table 1) into chains propagated along c axis.

Related literature top

For the biological activity of hydrazone derivatives, see: Khattab (2005); Küçükgüzel et al. (2003); Cukurovali et al. (2006). For the crystal structures of related compounds, see: Fun et al. (2008); Wei et al. (2009); Khaledi et al. (2008); Yang et al. (2008).

Experimental top

3,4-(Methylenedioxy)benzohydrazide (1.0 mmol, 180.2 mg) and 5-bromo-2-methoxybenzaldehyde (1.0 mmol, 215.0 mg) were mixed and refluxed in ethanol (50 ml). The mixture was stirred for 1 h to give a clear colorless solution. Colourless crystals of the title compound were formed by slow evaporation of the solution in air.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structures of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.

N'-(5-Bromo-2-methoxybenzylidene)-3,4-methylenedioxybenzohydrazide top

Crystal data top

C₁₆H₁₃BrN₂O₄	F(000) = 760
M_r = 377.19	D_x = 1.606 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2058 reflections
a = 12.678 (1) Å	θ = 2.5–24.5°
b = 16.217 (2) Å	µ = 2.66 mm⁻¹
c = 7.846 (2) Å	T = 298 K
β = 104.804 (3)°	Block, colourless
V = 1559.6 (5) Å³	0.30 × 0.28 × 0.27 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	3110 independent reflections
Radiation source: fine-focus sealed tube	1932 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω scans	θ_max = 26.2°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→15
T_min = 0.503, T_max = 0.534	k = −19→19
8368 measured reflections	l = −9→4

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0397P)² + 0.3363P] where P = (F_o² + 2F_c²)/3
3110 reflections	(Δ/σ)_max < 0.001
212 parameters	Δρ_max = 0.26 e Å⁻³
1 restraint	Δρ_min = −0.47 e Å⁻³

Crystal data top

C₁₆H₁₃BrN₂O₄	V = 1559.6 (5) Å³
M_r = 377.19	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.678 (1) Å	µ = 2.66 mm⁻¹
b = 16.217 (2) Å	T = 298 K
c = 7.846 (2) Å	0.30 × 0.28 × 0.27 mm
β = 104.804 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3110 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1932 reflections with I > 2σ(I)
T_min = 0.503, T_max = 0.534	R_int = 0.032
8368 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	1 restraint
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.26 e Å⁻³
3110 reflections	Δρ_min = −0.47 e Å⁻³
212 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² 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 (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.79365 (3)	0.77734 (2)	0.01187 (6)	0.08050 (19)
O1	0.47896 (16)	0.98772 (12)	0.2718 (3)	0.0551 (6)
O2	0.23491 (16)	0.66086 (12)	−0.0682 (3)	0.0495 (5)
O3	−0.13891 (18)	0.56492 (16)	0.0073 (3)	0.0777 (7)
O4	−0.1167 (2)	0.54766 (14)	0.3048 (4)	0.0750 (7)
N1	0.38458 (18)	0.76267 (14)	0.1294 (3)	0.0420 (6)
N2	0.29501 (19)	0.73440 (14)	0.1821 (3)	0.0427 (6)
C1	0.5282 (2)	0.86061 (18)	0.1769 (4)	0.0426 (7)
C2	0.5525 (2)	0.94368 (18)	0.2108 (4)	0.0434 (7)
C3	0.6454 (2)	0.9767 (2)	0.1762 (4)	0.0542 (8)
H3	0.6603	1.0327	0.1944	0.065*
C4	0.7157 (3)	0.9274 (2)	0.1152 (4)	0.0561 (8)
H4	0.7787	0.9498	0.0939	0.067*
C5	0.6934 (2)	0.8455 (2)	0.0857 (4)	0.0504 (8)
C6	0.6000 (2)	0.81226 (19)	0.1145 (4)	0.0482 (8)
H6	0.5848	0.7566	0.0918	0.058*
C7	0.4292 (2)	0.82617 (17)	0.2101 (4)	0.0423 (7)
H7	0.3982	0.8514	0.2922	0.051*
C8	0.2255 (2)	0.68194 (17)	0.0780 (4)	0.0392 (7)
C9	0.1363 (2)	0.64994 (16)	0.1497 (4)	0.0382 (7)
C10	0.0401 (2)	0.62571 (18)	0.0293 (4)	0.0495 (8)
H10	0.0306	0.6312	−0.0917	0.059*
C11	−0.0387 (2)	0.59384 (18)	0.0980 (5)	0.0490 (8)
C12	−0.0262 (2)	0.58422 (18)	0.2737 (5)	0.0521 (8)
C13	0.0667 (3)	0.6066 (2)	0.3945 (4)	0.0583 (9)
H13	0.0750	0.5994	0.5148	0.070*
C14	0.1485 (2)	0.64061 (18)	0.3280 (4)	0.0480 (7)
H14	0.2131	0.6576	0.4060	0.058*
C15	−0.1939 (3)	0.5446 (2)	0.1383 (6)	0.0819 (12)
H15A	−0.2524	0.5835	0.1351	0.098*
H15B	−0.2250	0.4897	0.1173	0.098*
C16	0.5016 (3)	1.07233 (19)	0.3115 (4)	0.0610 (9)
H16A	0.5691	1.0773	0.4005	0.092*
H16B	0.4437	1.0961	0.3538	0.092*
H16C	0.5073	1.1008	0.2070	0.092*
H2	0.278 (3)	0.7609 (18)	0.271 (3)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0737 (3)	0.0813 (3)	0.1027 (3)	0.0049 (2)	0.0521 (2)	−0.0014 (2)
O1	0.0564 (13)	0.0467 (13)	0.0667 (14)	−0.0076 (10)	0.0240 (12)	−0.0086 (11)
O2	0.0570 (13)	0.0515 (12)	0.0467 (12)	−0.0134 (10)	0.0255 (11)	−0.0098 (10)
O3	0.0461 (14)	0.0882 (18)	0.098 (2)	−0.0217 (13)	0.0169 (14)	−0.0130 (15)
O4	0.0626 (15)	0.0723 (17)	0.105 (2)	−0.0207 (13)	0.0492 (16)	0.0006 (15)
N1	0.0403 (13)	0.0441 (15)	0.0456 (15)	−0.0083 (11)	0.0186 (12)	−0.0008 (12)
N2	0.0427 (14)	0.0452 (14)	0.0465 (15)	−0.0125 (12)	0.0226 (12)	−0.0047 (12)
C1	0.0418 (17)	0.0469 (18)	0.0389 (17)	−0.0100 (14)	0.0097 (14)	0.0029 (14)
C2	0.0441 (17)	0.0469 (18)	0.0390 (17)	−0.0061 (14)	0.0104 (14)	0.0006 (14)
C3	0.0524 (19)	0.0492 (19)	0.062 (2)	−0.0178 (15)	0.0176 (17)	−0.0060 (16)
C4	0.0467 (18)	0.064 (2)	0.061 (2)	−0.0142 (16)	0.0199 (17)	0.0026 (18)
C5	0.0470 (18)	0.056 (2)	0.0521 (19)	−0.0026 (15)	0.0204 (16)	0.0014 (16)
C6	0.0516 (18)	0.0436 (17)	0.0513 (19)	−0.0060 (15)	0.0165 (16)	0.0023 (15)
C7	0.0441 (17)	0.0437 (18)	0.0420 (17)	−0.0062 (14)	0.0164 (14)	−0.0020 (14)
C8	0.0405 (16)	0.0356 (16)	0.0446 (17)	−0.0027 (13)	0.0168 (14)	0.0003 (14)
C9	0.0357 (15)	0.0357 (15)	0.0455 (17)	−0.0015 (12)	0.0148 (14)	0.0006 (14)
C10	0.0450 (18)	0.055 (2)	0.0494 (19)	−0.0050 (15)	0.0141 (16)	−0.0023 (16)
C11	0.0330 (16)	0.0450 (18)	0.069 (2)	−0.0062 (14)	0.0126 (16)	−0.0056 (16)
C12	0.0466 (19)	0.0402 (17)	0.079 (2)	−0.0097 (15)	0.0341 (18)	−0.0024 (17)
C13	0.070 (2)	0.062 (2)	0.052 (2)	−0.0107 (18)	0.0309 (19)	0.0063 (17)
C14	0.0442 (17)	0.0503 (19)	0.0515 (19)	−0.0075 (14)	0.0158 (15)	0.0019 (15)
C15	0.048 (2)	0.075 (3)	0.128 (4)	−0.0163 (19)	0.031 (3)	−0.006 (3)
C16	0.072 (2)	0.047 (2)	0.067 (2)	−0.0021 (17)	0.0240 (19)	−0.0059 (17)

Geometric parameters (Å, º) top

Br1—C5	1.884 (3)	C4—H4	0.9300
O1—C2	1.355 (3)	C5—C6	1.371 (4)
O1—C16	1.420 (4)	C6—H6	0.9300
O2—C8	1.232 (3)	C7—H7	0.9300
O3—C11	1.370 (3)	C8—C9	1.479 (4)
O3—C15	1.420 (4)	C9—C14	1.376 (4)
O4—C12	1.367 (3)	C9—C10	1.395 (4)
O4—C15	1.419 (5)	C10—C11	1.353 (4)
N1—C7	1.264 (3)	C10—H10	0.9300
N1—N2	1.382 (3)	C11—C12	1.356 (4)
N2—C8	1.341 (4)	C12—C13	1.359 (4)
N2—H2	0.89 (3)	C13—C14	1.389 (4)
C1—C6	1.382 (4)	C13—H13	0.9300
C1—C2	1.392 (4)	C14—H14	0.9300
C1—C7	1.458 (4)	C15—H15A	0.9700
C2—C3	1.383 (4)	C15—H15B	0.9700
C3—C4	1.372 (4)	C16—H16A	0.9600
C3—H3	0.9300	C16—H16B	0.9600
C4—C5	1.366 (4)	C16—H16C	0.9600

C2—O1—C16	117.9 (2)	C14—C9—C10	120.5 (3)
C11—O3—C15	105.4 (3)	C14—C9—C8	121.8 (3)
C12—O4—C15	105.3 (3)	C10—C9—C8	117.6 (3)
C7—N1—N2	114.6 (2)	C11—C10—C9	116.4 (3)
C8—N2—N1	119.4 (2)	C11—C10—H10	121.8
C8—N2—H2	122 (2)	C9—C10—H10	121.8
N1—N2—H2	117 (2)	C10—C11—C12	122.9 (3)
C6—C1—C2	118.9 (3)	C10—C11—O3	127.2 (3)
C6—C1—C7	121.4 (3)	C12—C11—O3	109.9 (3)
C2—C1—C7	119.6 (3)	C11—C12—C13	122.2 (3)
O1—C2—C3	124.2 (3)	C11—C12—O4	110.2 (3)
O1—C2—C1	116.1 (2)	C13—C12—O4	127.5 (3)
C3—C2—C1	119.7 (3)	C12—C13—C14	116.2 (3)
C4—C3—C2	120.3 (3)	C12—C13—H13	121.9
C4—C3—H3	119.8	C14—C13—H13	121.9
C2—C3—H3	119.8	C9—C14—C13	121.7 (3)
C5—C4—C3	120.1 (3)	C9—C14—H14	119.2
C5—C4—H4	119.9	C13—C14—H14	119.2
C3—C4—H4	119.9	O4—C15—O3	107.9 (3)
C4—C5—C6	120.3 (3)	O4—C15—H15A	110.1
C4—C5—Br1	119.7 (2)	O3—C15—H15A	110.1
C6—C5—Br1	119.9 (3)	O4—C15—H15B	110.1
C5—C6—C1	120.7 (3)	O3—C15—H15B	110.1
C5—C6—H6	119.7	H15A—C15—H15B	108.4
C1—C6—H6	119.7	O1—C16—H16A	109.5
N1—C7—C1	121.2 (3)	O1—C16—H16B	109.5
N1—C7—H7	119.4	H16A—C16—H16B	109.5
C1—C7—H7	119.4	O1—C16—H16C	109.5
O2—C8—N2	122.5 (2)	H16A—C16—H16C	109.5
O2—C8—C9	121.5 (3)	H16B—C16—H16C	109.5
N2—C8—C9	116.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱ	0.89 (3)	1.96 (3)	2.841 (3)	168 (3)

Symmetry code: (i) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₃BrN₂O₄
M_r	377.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	12.678 (1), 16.217 (2), 7.846 (2)
β (°)	104.804 (3)
V (Å³)	1559.6 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.66
Crystal size (mm)	0.30 × 0.28 × 0.27

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.503, 0.534
No. of measured, independent and observed [I > 2σ(I)] reflections	8368, 3110, 1932
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.621

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.096, 1.04
No. of reflections	3110
No. of parameters	212
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.47

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱ	0.89 (3)	1.96 (3)	2.841 (3)	168 (3)

Symmetry code: (i) x, −y+3/2, z+1/2.

Acknowledgements

We gratefullly acknowledge Chifeng University for the funding of this study.

References

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