N′-(5-Bromo-2-methoxy­benzyl­idene)-2-methoxy­benzohydrazide

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

doi:10.1107/S1600536809022971

organic compounds

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Volume 65| Part 7| July 2009| Page o1649

doi:10.1107/S1600536809022971

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N′-(5-Bromo-2-methoxybenzylidene)-2-methoxybenzohydrazide

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

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

(Received 13 June 2009; accepted 15 June 2009; online 20 June 2009)

The title hydrazone compound, C₁₆H₁₅BrN₂O₃, adopts an E configuration about the C=N double bond. The molecule is twisted, the dihedral angle between the two substituted benzene rings being 22.0 (2)°. In the crystal structure, molecules are linked through intermolecular N—H⋯O hydrogen bonds, forming chains along the c axis.

Related literature

For the biological properties of the hydrazone compounds, see: Khattab et al. (2005 ); Küçükgüzel et al. (2003 ); Çukurovalı et al. (2006 ). For the structures of hydrazone derivatives, see: Fun et al. (2008 ); Wei et al. (2009 ); Khaledi et al. (2008 ); Yang et al. (2008 ). For reference structural data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₆H₁₅BrN₂O₃
M_r = 363.21
Monoclinic, P 2₁ /c
a = 13.3286 (3) Å
b = 11.4816 (3) Å
c = 10.1233 (2) Å
β = 99.128 (1)°
V = 1529.59 (6) Å³
Z = 4
Mo Kα radiation
μ = 2.70 mm⁻¹
T = 298 K
0.20 × 0.18 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.614, T_max = 0.642
9188 measured reflections
3323 independent reflections
2281 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.096
S = 1.01
3323 reflections
204 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2ⁱ	0.894 (10)	2.179 (19)	2.997 (3)	152 (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/S1600536809022971/at2816sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809022971/at2816Isup2.hkl

checkCIF report

Comment top

Hydrazone and Schiff base compounds derived from the reaction of aldehydes with hydrazides have been widely investigated both for their crystal structures and biological properties (Khattab et al., 2005; Küçükgüzel et al., 2003; Çukurovalı et al., 2006). In the last few years, a large number of hydrazone derivatives have been reported (Fun et al., 2008; Wei et al., 2009; Khaledi et al., 2008; Yang et al., 2008). However, the hydrazone compounds derived the 5-bromo-2-methoxybenzaldehyde have never been reported. In this paper, the crystal structure of the title new hydrazone compound, (I), derived from the reaction of 5-bromo-2-methoxybenzaldehyde and 2-methoxybenzohydrazide, is reported.

The molecular structure of (I) is shown as Fig. 1. The molecule adopts an E configuration about the C═N double bond. The molecule is twisted about the C8—N1—N2—C9 moiety, with the dihedral angle between the C1—C6 and C10—C15 benzene rings of 22.0 (2)°. All the bond lengths are within normal values (Allen et al., 1987).

In the crystal structure of the compound, molecules are linked through intermolecular N–H···O hydrogen bonds (Table 1), forming chains along the c axis, as shown in Fig. 2.

Related literature top

For the biological properties of the hydrazone compounds, see: Khattab et al. (2005); Küçükgüzel et al. (2003); Çukurovalı et al. (2006). For the structures of hydrazone derivatives, see: Fun et al. (2008); Wei et al. (2009); Khaledi et al. (2008); Yang et al. (2008). For the reference structural data, see: Allen et al. (1987).

Experimental top

5-Bromo-2-methoxybenzaldehyde (1.0 mmol, 215.0 mg) and 2-methoxybenzohydrazide (1.0 mmol, 166.2 mg) were mixed and refluxed in methanol (50 ml). The mixture was stirred for 1 h to give a clear colourless solution. Colourless crystals of (I) were formed by slow evaporation of the solution in air for a few days.

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 structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The crystal packing of (I). Hydrogen atoms not involved in hydrogen bonding have been omitted. Intermolecular hydrogen bonds are shown as dashed lines.

N'-(5-Bromo-2-methoxybenzylidene)-2-methoxybenzohydrazide top

Crystal data top

C₁₆H₁₅BrN₂O₃	F(000) = 736
M_r = 363.21	D_x = 1.577 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2540 reflections
a = 13.3286 (3) Å	θ = 2.4–27.4°
b = 11.4816 (3) Å	µ = 2.70 mm⁻¹
c = 10.1233 (2) Å	T = 298 K
β = 99.128 (1)°	Block, colourless
V = 1529.59 (6) Å³	0.20 × 0.18 × 0.18 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	3323 independent reflections
Radiation source: fine-focus sealed tube	2281 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω scans	θ_max = 27.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→15
T_min = 0.614, T_max = 0.642	k = −14→12
9188 measured reflections	l = −12→12

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0398P)² + 1.0409P] where P = (F_o² + 2F_c²)/3
3323 reflections	(Δ/σ)_max < 0.001
204 parameters	Δρ_max = 0.65 e Å⁻³
1 restraint	Δρ_min = −0.69 e Å⁻³

Crystal data top

C₁₆H₁₅BrN₂O₃	V = 1529.59 (6) Å³
M_r = 363.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.3286 (3) Å	µ = 2.70 mm⁻¹
b = 11.4816 (3) Å	T = 298 K
c = 10.1233 (2) Å	0.20 × 0.18 × 0.18 mm
β = 99.128 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3323 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2281 reflections with I > 2σ(I)
T_min = 0.614, T_max = 0.642	R_int = 0.025
9188 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	1 restraint
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.65 e Å⁻³
3323 reflections	Δρ_min = −0.69 e Å⁻³
204 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	0.36301 (2)	1.06194 (4)	0.08660 (4)	0.07080 (16)
O1	0.67425 (14)	1.12056 (19)	0.5818 (2)	0.0511 (5)
O2	0.80411 (13)	0.73514 (17)	0.15200 (18)	0.0419 (5)
O3	1.01119 (14)	0.80174 (18)	0.4696 (2)	0.0497 (5)
N1	0.72756 (15)	0.88017 (18)	0.3201 (2)	0.0327 (5)
N2	0.80859 (15)	0.80683 (19)	0.3608 (2)	0.0322 (5)
C1	0.61419 (18)	1.0218 (2)	0.3825 (3)	0.0335 (6)
C2	0.60017 (19)	1.1107 (2)	0.4729 (3)	0.0377 (6)
C3	0.5157 (2)	1.1822 (2)	0.4485 (3)	0.0447 (7)
H3	0.5068	1.2409	0.5089	0.054*
C4	0.4447 (2)	1.1667 (3)	0.3350 (3)	0.0484 (7)
H4	0.3873	1.2138	0.3194	0.058*
C5	0.4594 (2)	1.0810 (3)	0.2451 (3)	0.0438 (7)
C6	0.54289 (19)	1.0089 (2)	0.2674 (3)	0.0383 (6)
H6	0.5516	0.9515	0.2054	0.046*
C7	0.6646 (3)	1.2090 (3)	0.6772 (4)	0.0734 (11)
H7A	0.6630	1.2839	0.6347	0.110*
H7B	0.7214	1.2054	0.7483	0.110*
H7C	0.6027	1.1974	0.7129	0.110*
C8	0.70088 (18)	0.9428 (2)	0.4122 (3)	0.0340 (6)
H8	0.7366	0.9383	0.4988	0.041*
C9	0.84257 (17)	0.7374 (2)	0.2700 (2)	0.0300 (5)
C10	0.93090 (18)	0.6607 (2)	0.3210 (2)	0.0331 (6)
C11	1.01527 (19)	0.6938 (3)	0.4138 (3)	0.0376 (6)
C12	1.0973 (2)	0.6182 (3)	0.4424 (3)	0.0517 (8)
H12	1.1548	0.6414	0.5010	0.062*
C13	1.0941 (3)	0.5100 (3)	0.3852 (3)	0.0588 (9)
H13	1.1493	0.4600	0.4056	0.071*
C14	1.0107 (3)	0.4748 (3)	0.2987 (3)	0.0576 (9)
H14	1.0080	0.4002	0.2626	0.069*
C15	0.9304 (2)	0.5502 (2)	0.2649 (3)	0.0447 (7)
H15	0.8747	0.5267	0.2034	0.054*
C16	1.0993 (2)	0.8449 (4)	0.5536 (4)	0.0690 (10)
H16A	1.1117	0.7995	0.6342	0.103*
H16B	1.0887	0.9248	0.5757	0.103*
H16C	1.1568	0.8395	0.5076	0.103*
H2	0.830 (3)	0.802 (3)	0.4490 (12)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0439 (2)	0.0908 (3)	0.0690 (3)	0.00890 (18)	−0.01763 (15)	0.0059 (2)
O1	0.0405 (11)	0.0619 (14)	0.0490 (12)	0.0068 (10)	0.0010 (9)	−0.0198 (10)
O2	0.0364 (10)	0.0531 (12)	0.0333 (10)	0.0071 (9)	−0.0033 (8)	−0.0053 (9)
O3	0.0324 (10)	0.0606 (14)	0.0520 (12)	0.0012 (9)	−0.0057 (9)	−0.0146 (10)
N1	0.0240 (10)	0.0347 (12)	0.0372 (12)	0.0022 (9)	−0.0016 (8)	0.0008 (10)
N2	0.0280 (10)	0.0361 (12)	0.0309 (11)	0.0053 (9)	−0.0006 (9)	−0.0003 (10)
C1	0.0268 (12)	0.0352 (14)	0.0387 (14)	0.0005 (10)	0.0050 (10)	0.0012 (11)
C2	0.0302 (13)	0.0409 (15)	0.0433 (15)	−0.0017 (12)	0.0103 (11)	0.0002 (12)
C3	0.0411 (15)	0.0387 (17)	0.0570 (19)	0.0061 (13)	0.0161 (14)	−0.0006 (14)
C4	0.0343 (14)	0.0463 (18)	0.066 (2)	0.0095 (13)	0.0111 (14)	0.0104 (15)
C5	0.0279 (13)	0.0518 (18)	0.0496 (17)	−0.0003 (12)	−0.0007 (12)	0.0129 (14)
C6	0.0322 (13)	0.0392 (15)	0.0424 (15)	0.0007 (12)	0.0022 (11)	0.0018 (13)
C7	0.066 (2)	0.086 (3)	0.067 (2)	0.002 (2)	0.0068 (18)	−0.036 (2)
C8	0.0280 (12)	0.0366 (15)	0.0354 (14)	0.0003 (11)	−0.0003 (10)	−0.0040 (12)
C9	0.0254 (11)	0.0327 (14)	0.0316 (13)	−0.0044 (10)	0.0030 (10)	0.0011 (11)
C10	0.0298 (12)	0.0402 (15)	0.0299 (13)	0.0040 (11)	0.0063 (10)	0.0027 (11)
C11	0.0309 (13)	0.0519 (18)	0.0302 (13)	0.0037 (12)	0.0055 (10)	0.0004 (12)
C12	0.0344 (15)	0.076 (2)	0.0432 (17)	0.0123 (15)	0.0004 (12)	0.0061 (16)
C13	0.0533 (19)	0.069 (2)	0.0544 (19)	0.0303 (18)	0.0104 (15)	0.0104 (18)
C14	0.067 (2)	0.0481 (19)	0.057 (2)	0.0191 (17)	0.0089 (17)	−0.0003 (16)
C15	0.0456 (16)	0.0454 (18)	0.0417 (16)	0.0073 (14)	0.0026 (12)	−0.0025 (13)
C16	0.0376 (17)	0.099 (3)	0.066 (2)	−0.0064 (18)	−0.0055 (15)	−0.033 (2)

Geometric parameters (Å, º) top

Br1—C5	1.902 (3)	C6—H6	0.9300
O1—C2	1.363 (3)	C7—H7A	0.9600
O1—C7	1.421 (4)	C7—H7B	0.9600
O2—C9	1.223 (3)	C7—H7C	0.9600
O3—C11	1.367 (3)	C8—H8	0.9300
O3—C16	1.425 (3)	C9—C10	1.495 (3)
N1—C8	1.273 (3)	C10—C15	1.390 (4)
N1—N2	1.380 (3)	C10—C11	1.398 (3)
N2—C9	1.348 (3)	C11—C12	1.389 (4)
N2—H2	0.894 (10)	C12—C13	1.369 (5)
C1—C6	1.390 (4)	C12—H12	0.9300
C1—C2	1.402 (4)	C13—C14	1.363 (5)
C1—C8	1.462 (3)	C13—H13	0.9300
C2—C3	1.383 (4)	C14—C15	1.377 (4)
C3—C4	1.380 (4)	C14—H14	0.9300
C3—H3	0.9300	C15—H15	0.9300
C4—C5	1.376 (4)	C16—H16A	0.9600
C4—H4	0.9300	C16—H16B	0.9600
C5—C6	1.376 (4)	C16—H16C	0.9600

C2—O1—C7	118.5 (2)	N1—C8—C1	120.2 (2)
C11—O3—C16	118.6 (2)	N1—C8—H8	119.9
C8—N1—N2	115.0 (2)	C1—C8—H8	119.9
C9—N2—N1	119.2 (2)	O2—C9—N2	123.0 (2)
C9—N2—H2	124 (2)	O2—C9—C10	120.7 (2)
N1—N2—H2	116 (2)	N2—C9—C10	116.3 (2)
C6—C1—C2	118.7 (2)	C15—C10—C11	118.3 (2)
C6—C1—C8	121.3 (2)	C15—C10—C9	116.3 (2)
C2—C1—C8	120.0 (2)	C11—C10—C9	125.3 (2)
O1—C2—C3	124.0 (3)	O3—C11—C12	124.2 (3)
O1—C2—C1	115.7 (2)	O3—C11—C10	116.3 (2)
C3—C2—C1	120.3 (3)	C12—C11—C10	119.5 (3)
C4—C3—C2	120.3 (3)	C13—C12—C11	120.5 (3)
C4—C3—H3	119.9	C13—C12—H12	119.7
C2—C3—H3	119.9	C11—C12—H12	119.7
C5—C4—C3	119.5 (3)	C14—C13—C12	120.6 (3)
C5—C4—H4	120.3	C14—C13—H13	119.7
C3—C4—H4	120.3	C12—C13—H13	119.7
C6—C5—C4	121.2 (3)	C13—C14—C15	119.7 (3)
C6—C5—Br1	119.3 (2)	C13—C14—H14	120.1
C4—C5—Br1	119.5 (2)	C15—C14—H14	120.1
C5—C6—C1	120.1 (3)	C14—C15—C10	121.3 (3)
C5—C6—H6	120.0	C14—C15—H15	119.4
C1—C6—H6	120.0	C10—C15—H15	119.4
O1—C7—H7A	109.5	O3—C16—H16A	109.5
O1—C7—H7B	109.5	O3—C16—H16B	109.5
H7A—C7—H7B	109.5	H16A—C16—H16B	109.5
O1—C7—H7C	109.5	O3—C16—H16C	109.5
H7A—C7—H7C	109.5	H16A—C16—H16C	109.5
H7B—C7—H7C	109.5	H16B—C16—H16C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱ	0.89 (1)	2.18 (2)	2.997 (3)	152 (3)

Symmetry code: (i) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₅BrN₂O₃
M_r	363.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	13.3286 (3), 11.4816 (3), 10.1233 (2)
β (°)	99.128 (1)
V (Å³)	1529.59 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.70
Crystal size (mm)	0.20 × 0.18 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.614, 0.642
No. of measured, independent and observed [I > 2σ(I)] reflections	9188, 3323, 2281
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.096, 1.01
No. of reflections	3323
No. of parameters	204
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)	0.65, −0.69

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	0.894 (10)	2.179 (19)	2.997 (3)	152 (3)

Symmetry code: (i) x, −y+3/2, z+1/2.

Acknowledgements

We are gratefully acknowledge Chifeng University for a research funding.

References

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