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

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.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.040
• wR factor = 0.130
• Data-to-parameter ratio = 15.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C) for methyl H atoms.

Computing details

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

	Fig. 1. The structure of the title molecule (I). Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of (I). Hydrogen bonds are indicated by dashed lines.

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

Crystal data

C15H12Br2N2O3	F(000) = 840
Mr = 428.07	Dx = 1.808 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2240 reflections
a = 18.701 (4) Å	θ = 2.6–24.4°
b = 8.8269 (17) Å	µ = 5.17 mm^−1
c = 9.6106 (18) Å	T = 294 K
β = 97.571 (3)°	Block, red
V = 1572.6 (5) Å^3	0.20 × 0.16 × 0.06 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	3199 independent reflections
Radiation source: fine-focus sealed tube	2125 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
φ and ω scans	θmax = 26.4°, θmin = 1.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −23→23
Tmin = 0.425, Tmax = 0.747	k = −10→10
8720 measured reflections	l = −10→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0681P)^2] where P = (Fo^2 + 2Fc^2)/3
3199 reflections	(Δ/σ)max < 0.001
208 parameters	Δρmax = 0.41 e Å^−3
2 restraints	Δρmin = −0.71 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.07397 (3)	0.32116 (6)	0.13724 (6)	0.0652 (2)
Br2	0.08446 (3)	0.69466 (6)	0.61765 (6)	0.0599 (2)
N1	0.35157 (18)	0.3267 (4)	0.4140 (4)	0.0409 (9)
N2	0.42226 (19)	0.2971 (4)	0.4625 (4)	0.0402 (9)
H2	0.433 (2)	0.306 (4)	0.547 (3)	0.038 (12)*
O1	0.23327 (18)	0.2858 (4)	0.2409 (3)	0.0502 (8)
H1	0.2757 (16)	0.273 (5)	0.270 (5)	0.060 (16)*
O2	0.43775 (15)	0.1678 (3)	0.2649 (3)	0.0485 (8)
O3	0.75077 (17)	0.1069 (4)	0.6158 (3)	0.0589 (9)
C1	0.2017 (2)	0.3777 (5)	0.3273 (4)	0.0367 (9)
C2	0.1287 (2)	0.4105 (4)	0.2970 (4)	0.0392 (10)
C3	0.0937 (2)	0.5058 (5)	0.3800 (4)	0.0423 (10)
H3	0.0451	0.5283	0.3561	0.051*
C4	0.1324 (2)	0.5673 (4)	0.4994 (4)	0.0399 (10)
C5	0.2038 (2)	0.5347 (4)	0.5354 (4)	0.0413 (10)
H5	0.2287	0.5756	0.6169	0.050*
C6	0.2399 (2)	0.4404 (4)	0.4505 (4)	0.0366 (10)
C7	0.3156 (2)	0.4061 (5)	0.4935 (4)	0.0421 (11)
H7	0.3382	0.4417	0.5792	0.051*
C8	0.4624 (2)	0.2125 (5)	0.3822 (4)	0.0368 (9)
C9	0.5380 (2)	0.1835 (4)	0.4464 (4)	0.0346 (9)
C10	0.5767 (2)	0.0680 (4)	0.3907 (4)	0.0382 (10)
H10	0.5542	0.0100	0.3168	0.046*
C11	0.6475 (2)	0.0386 (5)	0.4434 (4)	0.0419 (10)
H11	0.6725	−0.0383	0.4043	0.050*
C12	0.6816 (2)	0.1230 (5)	0.5542 (4)	0.0429 (10)
C13	0.6424 (2)	0.2362 (6)	0.6113 (5)	0.0520 (12)
H13	0.6645	0.2924	0.6870	0.062*
C14	0.5722 (2)	0.2668 (5)	0.5587 (5)	0.0488 (11)
H14	0.5474	0.3436	0.5982	0.059*
C15	0.7983 (3)	0.0133 (6)	0.5473 (5)	0.0610 (13)
H15A	0.7832	−0.0905	0.5501	0.091*
H15B	0.8466	0.0230	0.5945	0.091*
H15C	0.7969	0.0449	0.4513	0.091*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0543 (3)	0.0859 (4)	0.0525 (3)	−0.0181 (3)	−0.0040 (2)	−0.0166 (3)
Br2	0.0501 (3)	0.0648 (4)	0.0654 (4)	0.0094 (2)	0.0096 (3)	−0.0154 (2)
N1	0.0360 (19)	0.050 (2)	0.0366 (19)	0.0031 (16)	0.0034 (16)	0.0062 (16)
N2	0.037 (2)	0.053 (2)	0.0295 (19)	0.0076 (17)	−0.0023 (16)	0.0011 (17)
O1	0.049 (2)	0.060 (2)	0.0400 (18)	0.0066 (17)	−0.0004 (16)	−0.0089 (15)
O2	0.0429 (17)	0.073 (2)	0.0280 (16)	−0.0033 (15)	−0.0012 (13)	−0.0036 (14)
O3	0.0439 (19)	0.081 (2)	0.049 (2)	0.0173 (17)	−0.0041 (16)	−0.0098 (18)
C1	0.041 (2)	0.041 (2)	0.029 (2)	−0.0017 (19)	0.0061 (19)	0.0015 (18)
C2	0.038 (2)	0.045 (3)	0.032 (2)	−0.0066 (19)	−0.0043 (19)	0.0015 (18)
C3	0.034 (2)	0.044 (2)	0.048 (3)	−0.005 (2)	0.002 (2)	0.004 (2)
C4	0.039 (2)	0.039 (2)	0.041 (2)	0.0013 (19)	0.005 (2)	0.0008 (18)
C5	0.045 (3)	0.042 (3)	0.035 (2)	−0.004 (2)	0.000 (2)	0.0009 (18)
C6	0.038 (2)	0.040 (2)	0.032 (2)	0.0012 (18)	0.0011 (18)	0.0059 (17)
C7	0.044 (3)	0.049 (3)	0.031 (2)	0.004 (2)	−0.002 (2)	0.0052 (19)
C8	0.039 (2)	0.043 (2)	0.028 (2)	−0.0027 (19)	0.0053 (18)	0.0043 (18)
C9	0.035 (2)	0.042 (2)	0.027 (2)	−0.0031 (18)	0.0043 (17)	0.0023 (17)
C10	0.044 (2)	0.038 (2)	0.032 (2)	0.0026 (19)	0.0035 (19)	0.0018 (18)
C11	0.056 (3)	0.039 (2)	0.032 (2)	0.010 (2)	0.008 (2)	−0.0004 (18)
C12	0.040 (2)	0.050 (3)	0.038 (2)	0.005 (2)	0.007 (2)	0.002 (2)
C13	0.045 (3)	0.064 (3)	0.045 (3)	0.006 (2)	−0.004 (2)	−0.024 (2)
C14	0.045 (3)	0.054 (3)	0.048 (3)	0.002 (2)	0.008 (2)	−0.018 (2)
C15	0.047 (3)	0.075 (3)	0.062 (3)	0.016 (3)	0.012 (3)	0.004 (3)

Geometric parameters (Å, º)

Br1—C2	1.901 (4)	C5—H5	0.9300
Br2—C4	1.905 (4)	C6—C7	1.452 (6)
N1—C7	1.291 (5)	C7—H7	0.9300
N1—N2	1.368 (5)	C8—C9	1.488 (5)
N2—C8	1.368 (5)	C9—C14	1.391 (6)
N2—H2	0.81 (3)	C9—C10	1.396 (5)
O1—C1	1.351 (5)	C10—C11	1.380 (5)
O1—H1	0.81 (3)	C10—H10	0.9300
O2—C8	1.226 (5)	C11—C12	1.385 (6)
O3—C12	1.358 (5)	C11—H11	0.9300
O3—C15	1.436 (6)	C12—C13	1.393 (6)
C1—C2	1.388 (5)	C13—C14	1.370 (6)
C1—C6	1.413 (6)	C13—H13	0.9300
C2—C3	1.382 (6)	C14—H14	0.9300
C3—C4	1.384 (6)	C15—H15A	0.9600
C3—H3	0.9300	C15—H15B	0.9600
C4—C5	1.365 (6)	C15—H15C	0.9600
C5—C6	1.400 (6)
C7—N1—N2	117.2 (4)	O2—C8—N2	121.8 (4)
N1—N2—C8	119.3 (4)	O2—C8—C9	123.2 (4)
N1—N2—H2	114 (3)	N2—C8—C9	115.0 (3)
C8—N2—H2	123 (3)	C14—C9—C10	118.4 (4)
C1—O1—H1	111 (4)	C14—C9—C8	123.0 (4)
C12—O3—C15	118.2 (4)	C10—C9—C8	118.6 (4)
O1—C1—C2	119.6 (4)	C11—C10—C9	121.2 (4)
O1—C1—C6	122.4 (4)	C11—C10—H10	119.4
C2—C1—C6	118.0 (4)	C9—C10—H10	119.4
C3—C2—C1	122.2 (4)	C10—C11—C12	120.2 (4)
C3—C2—Br1	118.3 (3)	C10—C11—H11	119.9
C1—C2—Br1	119.5 (3)	C12—C11—H11	119.9
C2—C3—C4	118.8 (4)	O3—C12—C11	126.4 (4)
C2—C3—H3	120.6	O3—C12—C13	115.0 (4)
C4—C3—H3	120.6	C11—C12—C13	118.5 (4)
C5—C4—C3	121.0 (4)	C14—C13—C12	121.5 (4)
C5—C4—Br2	119.6 (3)	C14—C13—H13	119.2
C3—C4—Br2	119.4 (3)	C12—C13—H13	119.2
C4—C5—C6	120.5 (4)	C13—C14—C9	120.2 (4)
C4—C5—H5	119.7	C13—C14—H14	119.9
C6—C5—H5	119.7	C9—C14—H14	119.9
C5—C6—C1	119.4 (4)	O3—C15—H15A	109.5
C5—C6—C7	119.0 (4)	O3—C15—H15B	109.5
C1—C6—C7	121.6 (4)	H15A—C15—H15B	109.5
N1—C7—C6	120.6 (4)	O3—C15—H15C	109.5
N1—C7—H7	119.7	H15A—C15—H15C	109.5
C6—C7—H7	119.7	H15B—C15—H15C	109.5
C7—N1—N2—C8	179.6 (4)	C1—C6—C7—N1	5.6 (6)
O1—C1—C2—C3	−178.8 (4)	N1—N2—C8—O2	3.3 (6)
C6—C1—C2—C3	2.5 (6)	N1—N2—C8—C9	−178.4 (3)
O1—C1—C2—Br1	1.6 (5)	O2—C8—C9—C14	161.3 (4)
C6—C1—C2—Br1	−177.1 (3)	N2—C8—C9—C14	−16.9 (6)
C1—C2—C3—C4	−1.8 (6)	O2—C8—C9—C10	−18.2 (6)
Br1—C2—C3—C4	177.7 (3)	N2—C8—C9—C10	163.6 (4)
C2—C3—C4—C5	−0.1 (6)	C14—C9—C10—C11	−1.3 (6)
C2—C3—C4—Br2	−178.4 (3)	C8—C9—C10—C11	178.3 (4)
C3—C4—C5—C6	1.2 (6)	C9—C10—C11—C12	0.6 (6)
Br2—C4—C5—C6	179.5 (3)	C15—O3—C12—C11	11.8 (7)
C4—C5—C6—C1	−0.5 (6)	C15—O3—C12—C13	−168.5 (4)
C4—C5—C6—C7	−178.9 (4)	C10—C11—C12—O3	−179.7 (4)
O1—C1—C6—C5	−180.0 (4)	C10—C11—C12—C13	0.7 (7)
C2—C1—C6—C5	−1.3 (6)	O3—C12—C13—C14	179.1 (4)
O1—C1—C6—C7	−1.6 (6)	C11—C12—C13—C14	−1.2 (7)
C2—C1—C6—C7	177.1 (4)	C12—C13—C14—C9	0.5 (8)
N2—N1—C7—C6	−179.0 (3)	C10—C9—C14—C13	0.7 (7)
C5—C6—C7—N1	−176.0 (4)	C8—C9—C14—C13	−178.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.81 (3)	1.91 (4)	2.612 (5)	145 (5)
N2—H2···O2^i	0.81 (3)	2.10 (3)	2.898 (5)	169 (4)

Symmetry code: (i) x, −y+1/2, z+1/2.