supporting information


Acta Cryst. (2007). E63, o3823    [ doi:10.1107/S1600536807040111 ]

(E)-N'-(3,5-Dibromo-2-hydroxy­benzyl­idene)-4-methoxy­benzohydrazide

Z.-C. Bai and Z.-L. Jing

Abstract top

In the crystal structure of the title compound, C15H12Br2N2O3, the dihedral angle between the two ring planes is 11.40 (5)°. An intra­molecular O-H...N hydrogen bond stabilizes the mol­ecular structure. The mol­ecules are linked via weak inter­molecular N-H...O hydrogen bonding, forming an extended supra­molecular arrangement.

Comment top

In order to establish control over the preparation of crystalline solid materials so that their architecture and properties are predictable (Belloni et al., 2005; Tynan et al., 2005; Parashar et al., 1988), the synthesis of new and designed crystal structures has become a major strand of modern chemistry. Metal complexes based on Schiff bases have attracted much attention because they can be utilized as model compounds of the active centres in various proteins and enzymes (Kahwa et al., 1986; Santos et al., 2001). As part of an investigation of the coordination properties of Schiff bases functioning as ligands, we report the synthesis and structure of the title compound, (I).

In the structure of the title molecule (I) (Fig. 1), the geometric parameters are normal. The first benzene ring system (C1—C6) is planar, with an r.m.s. deviation for fitted atoms of 0.0071 (3) Å and the r.m.s. deviation for the other benzene group (C9—C14) is 0.0046 (2) Å. The dihedral angle between the two planes is 168.60 (5)°.

An intramolecular O—H···N hydrogen bond stabilizes the molecular structure. The molecules are linked via weak intermolecular N—H···O hydrogen bond, forming an extented supramolecular arrangement, as illustrated in Fig. 2 and Table. 1.

Related literature top

For general background, see: Belloni et al. (2005); Kahwa et al. (1986); Parashar et al. (1988); Santos et al. (2001); Tynan et al. (2005).

Experimental top

An anhydrous ethanol solution (50 ml) of 4-methoxybenzohydrazide(1.66 g, 10 mmol) was added to an anhydrous ethanol solution (50 ml) of 3,5-dibromo-2-hydroxybenzaldehyde (2.77 g, 10 mmol), and the mixture was stirred at 350 K for 6 h under N2, whereupon a red precipitate appeared. The product was isolated, recrystallized from anhydrous ethanol and then dried in vacuo to give pure compound (I) in 85% yield. Red single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an anhydrous ethanol solution.

Refinement top

The N-bound H atom was located in a difference Fourier map and refined freely. C-bound H atoms were included in calculated positions, with C—H = 0.93–0.96 Å, and refined using a riding model, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures top
[Figure 1] Fig. 1. The structure of the title molecule (I). Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The crystal packing of (I). Hydrogen bonds are indicated by dashed lines.
(E)-N'-(3,5-Dibromo-2-hydroxybenzylidene)-4-methoxybenzohydrazide top
Crystal data top
C15H12Br2N2O3F(000) = 840
Mr = 428.07Dx = 1.808 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2240 reflections
a = 18.701 (4) Åθ = 2.6–24.4°
b = 8.8269 (17) ŵ = 5.17 mm1
c = 9.6106 (18) ÅT = 294 K
β = 97.571 (3)°Block, red
V = 1572.6 (5) Å30.20 × 0.16 × 0.06 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
3199 independent reflections
Radiation source: fine-focus sealed tube2125 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.050
ϕ and ω scansθmax = 26.4°, θmin = 1.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 2323
Tmin = 0.425, Tmax = 0.747k = 1010
8720 measured reflectionsl = 1012
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0681P)2]
where P = (Fo2 + 2Fc2)/3
3199 reflections(Δ/σ)max < 0.001
208 parametersΔρmax = 0.41 e Å3
2 restraintsΔρmin = 0.71 e Å3
Crystal data top
C15H12Br2N2O3V = 1572.6 (5) Å3
Mr = 428.07Z = 4
Monoclinic, P21/cMo Kα radiation
a = 18.701 (4) ŵ = 5.17 mm1
b = 8.8269 (17) ÅT = 294 K
c = 9.6106 (18) Å0.20 × 0.16 × 0.06 mm
β = 97.571 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3199 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2125 reflections with I > 2σ(I)
Tmin = 0.425, Tmax = 0.747Rint = 0.050
8720 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0402 restraints
wR(F2) = 0.130H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.41 e Å3
3199 reflectionsΔρmin = 0.71 e Å3
208 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
xyzUiso*/Ueq
Br10.07397 (3)0.32116 (6)0.13724 (6)0.0652 (2)
Br20.08446 (3)0.69466 (6)0.61765 (6)0.0599 (2)
N10.35157 (18)0.3267 (4)0.4140 (4)0.0409 (9)
N20.42226 (19)0.2971 (4)0.4625 (4)0.0402 (9)
H20.433 (2)0.306 (4)0.547 (3)0.038 (12)*
O10.23327 (18)0.2858 (4)0.2409 (3)0.0502 (8)
H10.2757 (16)0.273 (5)0.270 (5)0.060 (16)*
O20.43775 (15)0.1678 (3)0.2649 (3)0.0485 (8)
O30.75077 (17)0.1069 (4)0.6158 (3)0.0589 (9)
C10.2017 (2)0.3777 (5)0.3273 (4)0.0367 (9)
C20.1287 (2)0.4105 (4)0.2970 (4)0.0392 (10)
C30.0937 (2)0.5058 (5)0.3800 (4)0.0423 (10)
H30.04510.52830.35610.051*
C40.1324 (2)0.5673 (4)0.4994 (4)0.0399 (10)
C50.2038 (2)0.5347 (4)0.5354 (4)0.0413 (10)
H50.22870.57560.61690.050*
C60.2399 (2)0.4404 (4)0.4505 (4)0.0366 (10)
C70.3156 (2)0.4061 (5)0.4935 (4)0.0421 (11)
H70.33820.44170.57920.051*
C80.4624 (2)0.2125 (5)0.3822 (4)0.0368 (9)
C90.5380 (2)0.1835 (4)0.4464 (4)0.0346 (9)
C100.5767 (2)0.0680 (4)0.3907 (4)0.0382 (10)
H100.55420.01000.31680.046*
C110.6475 (2)0.0386 (5)0.4434 (4)0.0419 (10)
H110.67250.03830.40430.050*
C120.6816 (2)0.1230 (5)0.5542 (4)0.0429 (10)
C130.6424 (2)0.2362 (6)0.6113 (5)0.0520 (12)
H130.66450.29240.68700.062*
C140.5722 (2)0.2668 (5)0.5587 (5)0.0488 (11)
H140.54740.34360.59820.059*
C150.7983 (3)0.0133 (6)0.5473 (5)0.0610 (13)
H15A0.78320.09050.55010.091*
H15B0.84660.02300.59450.091*
H15C0.79690.04490.45130.091*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0543 (3)0.0859 (4)0.0525 (3)0.0181 (3)0.0040 (2)0.0166 (3)
Br20.0501 (3)0.0648 (4)0.0654 (4)0.0094 (2)0.0096 (3)0.0154 (2)
N10.0360 (19)0.050 (2)0.0366 (19)0.0031 (16)0.0034 (16)0.0062 (16)
N20.037 (2)0.053 (2)0.0295 (19)0.0076 (17)0.0023 (16)0.0011 (17)
O10.049 (2)0.060 (2)0.0400 (18)0.0066 (17)0.0004 (16)0.0089 (15)
O20.0429 (17)0.073 (2)0.0280 (16)0.0033 (15)0.0012 (13)0.0036 (14)
O30.0439 (19)0.081 (2)0.049 (2)0.0173 (17)0.0041 (16)0.0098 (18)
C10.041 (2)0.041 (2)0.029 (2)0.0017 (19)0.0061 (19)0.0015 (18)
C20.038 (2)0.045 (3)0.032 (2)0.0066 (19)0.0043 (19)0.0015 (18)
C30.034 (2)0.044 (2)0.048 (3)0.005 (2)0.002 (2)0.004 (2)
C40.039 (2)0.039 (2)0.041 (2)0.0013 (19)0.005 (2)0.0008 (18)
C50.045 (3)0.042 (3)0.035 (2)0.004 (2)0.000 (2)0.0009 (18)
C60.038 (2)0.040 (2)0.032 (2)0.0012 (18)0.0011 (18)0.0059 (17)
C70.044 (3)0.049 (3)0.031 (2)0.004 (2)0.002 (2)0.0052 (19)
C80.039 (2)0.043 (2)0.028 (2)0.0027 (19)0.0053 (18)0.0043 (18)
C90.035 (2)0.042 (2)0.027 (2)0.0031 (18)0.0043 (17)0.0023 (17)
C100.044 (2)0.038 (2)0.032 (2)0.0026 (19)0.0035 (19)0.0018 (18)
C110.056 (3)0.039 (2)0.032 (2)0.010 (2)0.008 (2)0.0004 (18)
C120.040 (2)0.050 (3)0.038 (2)0.005 (2)0.007 (2)0.002 (2)
C130.045 (3)0.064 (3)0.045 (3)0.006 (2)0.004 (2)0.024 (2)
C140.045 (3)0.054 (3)0.048 (3)0.002 (2)0.008 (2)0.018 (2)
C150.047 (3)0.075 (3)0.062 (3)0.016 (3)0.012 (3)0.004 (3)
Geometric parameters (Å, º) top
Br1—C21.901 (4)C5—H50.9300
Br2—C41.905 (4)C6—C71.452 (6)
N1—C71.291 (5)C7—H70.9300
N1—N21.368 (5)C8—C91.488 (5)
N2—C81.368 (5)C9—C141.391 (6)
N2—H20.81 (3)C9—C101.396 (5)
O1—C11.351 (5)C10—C111.380 (5)
O1—H10.81 (3)C10—H100.9300
O2—C81.226 (5)C11—C121.385 (6)
O3—C121.358 (5)C11—H110.9300
O3—C151.436 (6)C12—C131.393 (6)
C1—C21.388 (5)C13—C141.370 (6)
C1—C61.413 (6)C13—H130.9300
C2—C31.382 (6)C14—H140.9300
C3—C41.384 (6)C15—H15A0.9600
C3—H30.9300C15—H15B0.9600
C4—C51.365 (6)C15—H15C0.9600
C5—C61.400 (6)
C7—N1—N2117.2 (4)O2—C8—N2121.8 (4)
N1—N2—C8119.3 (4)O2—C8—C9123.2 (4)
N1—N2—H2114 (3)N2—C8—C9115.0 (3)
C8—N2—H2123 (3)C14—C9—C10118.4 (4)
C1—O1—H1111 (4)C14—C9—C8123.0 (4)
C12—O3—C15118.2 (4)C10—C9—C8118.6 (4)
O1—C1—C2119.6 (4)C11—C10—C9121.2 (4)
O1—C1—C6122.4 (4)C11—C10—H10119.4
C2—C1—C6118.0 (4)C9—C10—H10119.4
C3—C2—C1122.2 (4)C10—C11—C12120.2 (4)
C3—C2—Br1118.3 (3)C10—C11—H11119.9
C1—C2—Br1119.5 (3)C12—C11—H11119.9
C2—C3—C4118.8 (4)O3—C12—C11126.4 (4)
C2—C3—H3120.6O3—C12—C13115.0 (4)
C4—C3—H3120.6C11—C12—C13118.5 (4)
C5—C4—C3121.0 (4)C14—C13—C12121.5 (4)
C5—C4—Br2119.6 (3)C14—C13—H13119.2
C3—C4—Br2119.4 (3)C12—C13—H13119.2
C4—C5—C6120.5 (4)C13—C14—C9120.2 (4)
C4—C5—H5119.7C13—C14—H14119.9
C6—C5—H5119.7C9—C14—H14119.9
C5—C6—C1119.4 (4)O3—C15—H15A109.5
C5—C6—C7119.0 (4)O3—C15—H15B109.5
C1—C6—C7121.6 (4)H15A—C15—H15B109.5
N1—C7—C6120.6 (4)O3—C15—H15C109.5
N1—C7—H7119.7H15A—C15—H15C109.5
C6—C7—H7119.7H15B—C15—H15C109.5
C7—N1—N2—C8179.6 (4)C1—C6—C7—N15.6 (6)
O1—C1—C2—C3178.8 (4)N1—N2—C8—O23.3 (6)
C6—C1—C2—C32.5 (6)N1—N2—C8—C9178.4 (3)
O1—C1—C2—Br11.6 (5)O2—C8—C9—C14161.3 (4)
C6—C1—C2—Br1177.1 (3)N2—C8—C9—C1416.9 (6)
C1—C2—C3—C41.8 (6)O2—C8—C9—C1018.2 (6)
Br1—C2—C3—C4177.7 (3)N2—C8—C9—C10163.6 (4)
C2—C3—C4—C50.1 (6)C14—C9—C10—C111.3 (6)
C2—C3—C4—Br2178.4 (3)C8—C9—C10—C11178.3 (4)
C3—C4—C5—C61.2 (6)C9—C10—C11—C120.6 (6)
Br2—C4—C5—C6179.5 (3)C15—O3—C12—C1111.8 (7)
C4—C5—C6—C10.5 (6)C15—O3—C12—C13168.5 (4)
C4—C5—C6—C7178.9 (4)C10—C11—C12—O3179.7 (4)
O1—C1—C6—C5180.0 (4)C10—C11—C12—C130.7 (7)
C2—C1—C6—C51.3 (6)O3—C12—C13—C14179.1 (4)
O1—C1—C6—C71.6 (6)C11—C12—C13—C141.2 (7)
C2—C1—C6—C7177.1 (4)C12—C13—C14—C90.5 (8)
N2—N1—C7—C6179.0 (3)C10—C9—C14—C130.7 (7)
C5—C6—C7—N1176.0 (4)C8—C9—C14—C13178.8 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.81 (3)1.91 (4)2.612 (5)145 (5)
N2—H2···O2i0.81 (3)2.10 (3)2.898 (5)169 (4)
Symmetry code: (i) x, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC15H12Br2N2O3
Mr428.07
Crystal system, space groupMonoclinic, P21/c
Temperature (K)294
a, b, c (Å)18.701 (4), 8.8269 (17), 9.6106 (18)
β (°) 97.571 (3)
V3)1572.6 (5)
Z4
Radiation typeMo Kα
µ (mm1)5.17
Crystal size (mm)0.20 × 0.16 × 0.06
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.425, 0.747
No. of measured, independent and
observed [I > 2σ(I)] reflections
8720, 3199, 2125
Rint0.050
(sin θ/λ)max1)0.626
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.130, 1.05
No. of reflections3199
No. of parameters208
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.41, 0.71

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.81 (3)1.91 (4)2.612 (5)145 (5)
N2—H2···O2i0.81 (3)2.10 (3)2.898 (5)169 (4)
Symmetry code: (i) x, y+1/2, z+1/2.
 
Acknowledgements top

(type here to add acknowledgements)