(E)-N′-(3,5-Dibromo-2-hydroxy­benzyl­idene)-2-nitro­benzohydrazide methanol solvate

Qian, H.-Y.; Qu, D.-P.

doi:10.1107/S160053680903311X

organic compounds

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Volume 65| Part 9| September 2009| Page o2237

doi:10.1107/S160053680903311X

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(E)-N′-(3,5-Dibromo-2-hydroxybenzylidene)-2-nitrobenzohydrazide methanol solvate

Heng-Yu Qian ^a ^* and Da-Ping Qu ^b

^aKey Laboratory of Surface and Interface Science of Henan, School of Material & Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou 450002, People's Republic of China, and ^bDepartment of Chemistry, Dalian Teacher College, Dalian 116000, People's Republic of China
^*Correspondence e-mail: hengyu_qian@126.com

(Received 19 August 2009; accepted 19 August 2009; online 26 August 2009)

In the title compound, C₁₄H₉Br₂N₃O₄·CH₃OH, the Schiff base molecule adopts an E geometry with respect to the C=N bond and the benzene rings are oriented at a dihedral angle of 45.3 (2)°. An intramolecular O—H⋯N hydrogen bond helps to establish the conformation. In the crystal, the methanol solvent molecule is linked to the Schiff base molecule through an O—H⋯O hydrogen bond and intermolecular N—H⋯O hydrogen bonds link the components to form layers parallel to the bc direction.

Related literature

For our previous work in this area, see: Yin, Qian et al. (2007 ); Yin, Guo et al. (2007 ); Qian et al. (2009 ).

Experimental

Crystal data

C₁₄H₉Br₂N₃O₄·CH₄O
M_r = 475.10
Monoclinic, C 2/c
a = 18.981 (1) Å
b = 10.054 (2) Å
c = 19.746 (2) Å
β = 110.974 (2)°
V = 3518.6 (8) Å³
Z = 8
Mo Kα radiation
μ = 4.64 mm⁻¹
T = 298 K
0.18 × 0.17 × 0.16 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.490, T_max = 0.524
10461 measured reflections
3784 independent reflections
2670 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.094
S = 1.02
3784 reflections
232 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.87	2.587 (3)	146
O5—H5⋯O2	0.82	1.94	2.735 (4)	165
N2—H2⋯O5ⁱ	0.893 (10)	1.958 (13)	2.840 (3)	169 (4)
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680903311X/hb5053sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680903311X/hb5053Isup2.hkl

checkCIF report

Comment top

As part of our ongoing studies of Schiff bases (Yin, Qian et al., 2007; Yin, Guo et al., 2007; Qian et al., 2009), we now report the synthesis and structure of the title compound, (I), (Fig. 1).

The Schiff base molecule adopts an E geometry with respect to the C=N bond, and there forms an intramolecular O—H···N hydrogen bond. The two benzene rings forms a dihedral angle of 45.3 (2)°. The dihedral angle between the O3/N3/O4 plane and the C9—C14 benzene ring is 37.1 (2)°. The methanol molecule is linked to the Schiff base molecule through the O—H···O hydrogen bond (Table 1). In the crystal structure, molecules are linked through intermolecular N—H···O hydrogen bonds (Table 1) to form layers parallel to the bc direction (Fig. 2).

Related literature top

For our previous work in this area, see: Yin, Qian et al. (2007); Yin, Guo et al. (2007); Qian et al. (2009).

Experimental top

2-Nitrobenzohydrazide (1 mmol, 0.181 g) and 3,5-dibromosalicylaldehyde (1 mmol, 0.280 g) were dissolved in anhydrous methanol (15 ml). The mixture was stirred for several minutes at room temperature. The product was isolated and recrystallized from methanol, colourless blocks of (I) were obtained after five days.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonding is shown as dashed lines.
	Fig. 2. The molecular packing of the title compound, viewed along the b axis. Hydrogen bonding is shown in dashed lines.

(E)-N'-(3,5-Dibromo-2-hydroxybenzylidene)-2-nitrobenzohydrazide methanol solvate top

Crystal data top

C₁₄H₉Br₂N₃O₄·CH₄O	F(000) = 1872
M_r = 475.10	D_x = 1.794 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3081 reflections
a = 18.981 (1) Å	θ = 2.7–25.0°
b = 10.054 (2) Å	µ = 4.64 mm⁻¹
c = 19.746 (2) Å	T = 298 K
β = 110.974 (2)°	Block, colourless
V = 3518.6 (8) Å³	0.18 × 0.17 × 0.16 mm
Z = 8

Data collection top

Bruker SMART CCD diffractometer	3784 independent reflections
Radiation source: fine-focus sealed tube	2670 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ω scans	θ_max = 26.9°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −24→20
T_min = 0.490, T_max = 0.524	k = −12→12
10461 measured reflections	l = −19→25

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0488P)²] where P = (F_o² + 2F_c²)/3
3784 reflections	(Δ/σ)_max < 0.001
232 parameters	Δρ_max = 0.36 e Å⁻³
1 restraint	Δρ_min = −0.66 e Å⁻³

Crystal data top

C₁₄H₉Br₂N₃O₄·CH₄O	V = 3518.6 (8) Å³
M_r = 475.10	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 18.981 (1) Å	µ = 4.64 mm⁻¹
b = 10.054 (2) Å	T = 298 K
c = 19.746 (2) Å	0.18 × 0.17 × 0.16 mm
β = 110.974 (2)°

Data collection top

Bruker SMART CCD diffractometer	3784 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2670 reflections with I > 2σ(I)
T_min = 0.490, T_max = 0.524	R_int = 0.041
10461 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	1 restraint
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.36 e Å⁻³
3784 reflections	Δρ_min = −0.66 e Å⁻³
232 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	0.07056 (2)	0.15611 (4)	0.382792 (19)	0.05768 (14)
Br2	0.14655 (2)	0.69346 (4)	0.365230 (19)	0.06064 (15)
O1	0.16461 (14)	0.1962 (2)	0.53986 (11)	0.0507 (6)
H1	0.1901	0.2081	0.5828	0.076*
O2	0.26477 (13)	0.1296 (2)	0.74915 (11)	0.0556 (6)
O3	0.42343 (15)	0.0570 (3)	0.78985 (13)	0.0758 (8)
O4	0.43759 (18)	−0.0577 (3)	0.88592 (14)	0.0873 (9)
O5	0.12161 (14)	0.0782 (2)	0.74447 (13)	0.0640 (7)
H5	0.1605	0.1003	0.7384	0.096*
N1	0.25316 (14)	0.3244 (2)	0.65150 (13)	0.0403 (6)
N2	0.30067 (15)	0.3314 (2)	0.72253 (13)	0.0421 (6)
N3	0.42213 (15)	0.0446 (3)	0.85052 (15)	0.0526 (7)
C1	0.20261 (16)	0.4236 (3)	0.53512 (14)	0.0357 (6)
C2	0.16312 (16)	0.3082 (3)	0.50269 (15)	0.0369 (7)
C3	0.12163 (17)	0.3109 (3)	0.42817 (15)	0.0391 (7)
C4	0.11755 (16)	0.4237 (3)	0.38783 (15)	0.0429 (7)
H4	0.0893	0.4242	0.3384	0.052*
C5	0.15566 (17)	0.5361 (3)	0.42122 (15)	0.0422 (7)
C6	0.19789 (16)	0.5366 (3)	0.49391 (15)	0.0405 (7)
H6	0.2235	0.6133	0.5156	0.049*
C7	0.24867 (16)	0.4255 (3)	0.61175 (15)	0.0390 (7)
H7	0.2753	0.5021	0.6320	0.047*
C8	0.30280 (16)	0.2312 (3)	0.76752 (16)	0.0384 (7)
C9	0.35228 (16)	0.2548 (3)	0.84468 (15)	0.0365 (7)
C10	0.40432 (17)	0.1623 (3)	0.88545 (15)	0.0391 (7)
C11	0.4444 (2)	0.1791 (3)	0.95794 (16)	0.0517 (9)
H11	0.4787	0.1150	0.9840	0.062*
C12	0.4331 (2)	0.2913 (4)	0.99107 (18)	0.0608 (10)
H12	0.4601	0.3039	1.0402	0.073*
C13	0.3827 (2)	0.3856 (4)	0.95328 (18)	0.0622 (10)
H13	0.3756	0.4621	0.9766	0.075*
C14	0.34200 (19)	0.3670 (3)	0.87998 (16)	0.0494 (8)
H14	0.3074	0.4312	0.8544	0.059*
C15	0.0603 (2)	0.1292 (4)	0.6894 (2)	0.0898 (15)
H15A	0.0148	0.0934	0.6928	0.135*
H15B	0.0634	0.1056	0.6435	0.135*
H15C	0.0599	0.2243	0.6937	0.135*
H2	0.3299 (18)	0.403 (2)	0.7369 (19)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0549 (2)	0.0620 (2)	0.0483 (2)	−0.01531 (16)	0.00887 (17)	−0.01568 (16)
Br2	0.0684 (3)	0.0597 (2)	0.0450 (2)	0.00128 (17)	0.00967 (18)	0.02143 (16)
O1	0.0630 (16)	0.0411 (12)	0.0378 (12)	−0.0092 (10)	0.0055 (11)	0.0045 (10)
O2	0.0565 (15)	0.0490 (13)	0.0457 (13)	−0.0159 (11)	−0.0007 (11)	0.0061 (10)
O3	0.095 (2)	0.091 (2)	0.0403 (15)	0.0193 (16)	0.0228 (14)	−0.0040 (13)
O4	0.131 (3)	0.0544 (16)	0.0632 (17)	0.0358 (16)	0.0182 (17)	0.0122 (14)
O5	0.0643 (17)	0.0531 (15)	0.0629 (15)	0.0092 (13)	0.0086 (13)	0.0013 (12)
N1	0.0377 (15)	0.0457 (15)	0.0276 (12)	−0.0015 (10)	−0.0005 (11)	0.0039 (10)
N2	0.0436 (16)	0.0422 (15)	0.0268 (12)	−0.0059 (11)	−0.0041 (11)	0.0071 (11)
N3	0.0528 (18)	0.0576 (18)	0.0380 (16)	0.0095 (13)	0.0051 (13)	0.0014 (13)
C1	0.0332 (17)	0.0404 (16)	0.0293 (14)	−0.0005 (12)	0.0062 (12)	0.0007 (12)
C2	0.0336 (17)	0.0408 (16)	0.0339 (15)	0.0000 (12)	0.0091 (13)	0.0012 (13)
C3	0.0345 (17)	0.0461 (17)	0.0333 (16)	−0.0041 (12)	0.0080 (13)	−0.0061 (13)
C4	0.0366 (18)	0.061 (2)	0.0263 (15)	0.0010 (14)	0.0054 (13)	0.0032 (14)
C5	0.0431 (19)	0.0491 (19)	0.0317 (15)	0.0051 (13)	0.0100 (13)	0.0102 (13)
C6	0.0414 (18)	0.0387 (17)	0.0362 (16)	−0.0008 (13)	0.0075 (13)	0.0038 (13)
C7	0.0398 (18)	0.0382 (16)	0.0313 (15)	−0.0013 (12)	0.0034 (13)	0.0032 (13)
C8	0.0325 (17)	0.0425 (17)	0.0343 (15)	0.0014 (13)	0.0049 (13)	0.0040 (13)
C9	0.0386 (17)	0.0378 (15)	0.0308 (14)	−0.0031 (12)	0.0097 (13)	0.0061 (12)
C10	0.0412 (19)	0.0422 (17)	0.0300 (15)	−0.0001 (12)	0.0078 (13)	0.0036 (12)
C11	0.055 (2)	0.058 (2)	0.0309 (17)	0.0027 (15)	0.0018 (15)	0.0105 (15)
C12	0.081 (3)	0.064 (2)	0.0268 (16)	−0.0072 (19)	0.0065 (17)	−0.0010 (16)
C13	0.093 (3)	0.051 (2)	0.041 (2)	−0.0017 (19)	0.022 (2)	−0.0061 (16)
C14	0.059 (2)	0.0438 (19)	0.0419 (19)	0.0029 (15)	0.0138 (17)	0.0044 (14)
C15	0.080 (3)	0.075 (3)	0.081 (3)	0.018 (2)	−0.013 (3)	−0.005 (2)

Geometric parameters (Å, º) top

Br1—C3	1.882 (3)	C4—C5	1.377 (4)
Br2—C5	1.902 (3)	C4—H4	0.9300
O1—C2	1.338 (3)	C5—C6	1.371 (4)
O1—H1	0.8200	C6—H6	0.9300
O2—C8	1.228 (4)	C7—H7	0.9300
O3—N3	1.214 (3)	C8—C9	1.495 (4)
O4—N3	1.218 (4)	C9—C14	1.376 (5)
O5—C15	1.376 (4)	C9—C10	1.385 (4)
O5—H5	0.8200	C10—C11	1.370 (4)
N1—C7	1.269 (4)	C11—C12	1.359 (5)
N1—N2	1.371 (3)	C11—H11	0.9300
N2—C8	1.335 (4)	C12—C13	1.364 (5)
N2—H2	0.893 (10)	C12—H12	0.9300
N3—C10	1.469 (4)	C13—C14	1.388 (4)
C1—C6	1.382 (4)	C13—H13	0.9300
C1—C2	1.405 (4)	C14—H14	0.9300
C1—C7	1.452 (4)	C15—H15A	0.9600
C2—C3	1.399 (4)	C15—H15B	0.9600
C3—C4	1.372 (4)	C15—H15C	0.9600

C2—O1—H1	109.5	C1—C7—H7	119.5
C15—O5—H5	109.5	O2—C8—N2	123.8 (3)
C7—N1—N2	117.7 (2)	O2—C8—C9	121.4 (3)
C8—N2—N1	119.6 (2)	N2—C8—C9	114.6 (3)
C8—N2—H2	122 (2)	C14—C9—C10	117.2 (3)
N1—N2—H2	118 (2)	C14—C9—C8	119.7 (3)
O3—N3—O4	124.6 (3)	C10—C9—C8	122.9 (3)
O3—N3—C10	118.0 (3)	C11—C10—C9	122.6 (3)
O4—N3—C10	117.3 (3)	C11—C10—N3	117.0 (3)
C6—C1—C2	120.0 (3)	C9—C10—N3	120.3 (3)
C6—C1—C7	119.4 (3)	C12—C11—C10	118.7 (3)
C2—C1—C7	120.7 (3)	C12—C11—H11	120.6
O1—C2—C3	119.1 (3)	C10—C11—H11	120.6
O1—C2—C1	122.8 (2)	C11—C12—C13	121.0 (3)
C3—C2—C1	118.1 (3)	C11—C12—H12	119.5
C4—C3—C2	121.4 (3)	C13—C12—H12	119.5
C4—C3—Br1	119.6 (2)	C12—C13—C14	119.8 (3)
C2—C3—Br1	119.0 (2)	C12—C13—H13	120.1
C3—C4—C5	119.3 (3)	C14—C13—H13	120.1
C3—C4—H4	120.3	C9—C14—C13	120.8 (3)
C5—C4—H4	120.3	C9—C14—H14	119.6
C6—C5—C4	121.0 (3)	C13—C14—H14	119.6
C6—C5—Br2	120.2 (2)	O5—C15—H15A	109.5
C4—C5—Br2	118.8 (2)	O5—C15—H15B	109.5
C5—C6—C1	120.3 (3)	H15A—C15—H15B	109.5
C5—C6—H6	119.9	O5—C15—H15C	109.5
C1—C6—H6	119.9	H15A—C15—H15C	109.5
N1—C7—C1	121.1 (3)	H15B—C15—H15C	109.5
N1—C7—H7	119.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.87	2.587 (3)	146
O5—H5···O2	0.82	1.94	2.735 (4)	165
N2—H2···O5ⁱ	0.89 (1)	1.96 (1)	2.840 (3)	169 (4)

Symmetry code: (i) −x+1/2, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₉Br₂N₃O₄·CH₄O
M_r	475.10
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	18.981 (1), 10.054 (2), 19.746 (2)
β (°)	110.974 (2)
V (Å³)	3518.6 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	4.64
Crystal size (mm)	0.18 × 0.17 × 0.16

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.490, 0.524
No. of measured, independent and observed [I > 2σ(I)] reflections	10461, 3784, 2670
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.637

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.094, 1.02
No. of reflections	3784
No. of parameters	232
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)	0.36, −0.66

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.87	2.587 (3)	146
O5—H5···O2	0.82	1.94	2.735 (4)	165
N2—H2···O5ⁱ	0.893 (10)	1.958 (13)	2.840 (3)	169 (4)

Symmetry code: (i) −x+1/2, y+1/2, −z+3/2.

References

Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Qian, H., Yin, Z. & Yao, Z. (2009). Acta Cryst. E65, o2155. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yin, Z., Guo, S., Qian, H. & Feng, Y. (2007). Acta Cryst. E63, o4407. Web of Science CSD CrossRef IUCr Journals Google Scholar
Yin, Z.-G., Qian, H.-Y., Jie, H. & Yu-Li, F. (2007). Acta Cryst. E63, o4406. Web of Science CSD CrossRef IUCr Journals Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(E)-N′-(3,5-Di­bromo-2-hy­droxy­benzyl­­idene)-2-nitro­benzohydrazide methanol solvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds

(E)-N′-(3,5-Dibromo-2-hydroxybenzylidene)-2-nitrobenzohydrazide methanol solvate