(E)-N′-(5-Bromo-2-hy­droxy-3-meth­oxy­benzyl­idene)-2-hy­droxy­benzohydrazide monohydrate

Abstract

The organic molecule of the title hydrate, C₁₅H₁₃BrN₂O₄·H₂O, is roughly planar, with a mean deviation of 0.0939 (2) Å. The dihedral angle between the two aromatic rings is 8.2 (3)°. Intra­molecular O—H⋯N and O—H⋯O hydrogen bonds are observed. In the crystal, N—H⋯O(water) and O(water)—H⋯O hydrogen bonds lead to a three-dimensional network.

Related literature  

For related structures, see: Lu (2008 ▶); Nie (2008 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental  

Crystal data  

• C₁₅H₁₃BrN₂O₄·H₂O

• M _r = 383.20

• Orthorhombic,

• a = 6.3822 (13) Å

• b = 14.142 (3) Å

• c = 17.470 (4) Å

• V = 1576.8 (6) ų

• Z = 4

• Mo Kα radiation

• μ = 2.63 mm⁻¹

• T = 296 K

• 0.38 × 0.26 × 0.20 mm

Data collection  

• Bruker SMART 1K CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.444, T _max = 0.590

• 9336 measured reflections

• 3658 independent reflections

• 2060 reflections with I > 2σ(I)

• R _int = 0.066

Refinement  

• R[F ² > 2σ(F ²)] = 0.045

• wR(F ²) = 0.131

• S = 0.90

• 3658 reflections

• 217 parameters

• 3 restraints

• H-atom parameters constrained

• Δρ_max = 0.33 e Å⁻³

• Δρ_min = −0.48 e Å⁻³

• Absolute structure: Flack (1983 ▶), 1411 Friedel pairs

• Flack parameter: 0.008 (15)

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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: SHELXTL and local programs.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812024816/fk2062Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯N1	0.82	1.95	2.657 (5)	144
N2—H2B⋯O1W i	0.86	2.09	2.921 (5)	164
O4—H4A⋯O3	0.82	1.80	2.527 (5)	147
O1W—H2W⋯O4ii	0.84	2.05	2.855 (6)	161
O1W—H1W⋯O3iii	0.85	2.06	2.823 (5)	148

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

Hydrazones attract the interest of researchers due to their various biological activities viz. anticancer, anti-HIV, anthelmintic, antimycobacterial, anti-inflammatory, antidiabetic, antimicrobial, trypanocidal as well antimalarial activities. Here we report the crystal structure of the novel hydrazone title compound (Fig. 1). Bond lengths are in the range of expected values (Allen et al., 1987) and are comparable to those observed from similar compounds (Lu, 2008; Nie, 2008). Intramolecular as well as intermolecular N—H···O and O—H···O hydrogen bonds are observed (Table 1), the intermolecular ones lead to a three-dimensional network of the hydrazone with water molecules (Fig. 2). The latter stems from non-dried acetonitrile.

Experimental

2-Hydroxybenzohydrazide (152.2 mg, 1.0 mmol) was added to a solution of 5-bromo-2-hydroxy-3-methoxybenzaldehyde (231.5 mg, 1.0 mmol) in absolute ethanol (10 ml) and heated to reflux for 2 h. A pale yellow solid that precipitated from the reaction mixture was collected by filtration, dried on open air and then recrystallized from acetonitrile to give pale yellow crystals, yield 69.3%.

Refinement

Hydroxy H atoms were located in a difference-Fourier synthesis and were refined as idealized rotating hydroxyl groups, with O—H = 0.82 Å and U_iso(H) = 1.5 U_eq(O). Water H atoms were located in a difference-Fourier synthesis and refined with constraint O—H = 0.82 Å, H···H distance 1.35 Å and U_iso(H) = 1.5 U_eq(O). Other H atoms were positioned geometrically and refined using a riding model with N—H = 0.86 Å, C—H = 0.93–0.96 Å and with U_iso(H) = 1.2 (1.5 for methyl groups) times U_eq(C/N).

Figures

Fig. 1.

The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

Fig. 2.

The crystal packing, viewed along the a axis, showing the hydrogen bonds as dashed lines.

Crystal data

C15H13BrN2O4·H2O	F(000) = 776
Mr = 383.20	Dx = 1.614 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2451 reflections
a = 6.3822 (13) Å	θ = 1.9–26.6°
b = 14.142 (3) Å	µ = 2.63 mm−1
c = 17.470 (4) Å	T = 296 K
V = 1576.8 (6) Å3	Stick, colourless
Z = 4	0.38 × 0.26 × 0.20 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer	3658 independent reflections
Radiation source: fine-focus sealed tube	2060 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.066
thin–slice ω scans	θmax = 28.2°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −8→5
Tmin = 0.444, Tmax = 0.590	k = −18→18
9336 measured reflections	l = −21→19

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045	H-atom parameters constrained
wR(F2) = 0.131	w = 1/[σ2(Fo2) + (0.0557P)2] where P = (Fo2 + 2Fc2)/3
S = 0.90	(Δ/σ)max = 0.001
3658 reflections	Δρmax = 0.33 e Å−3
217 parameters	Δρmin = −0.48 e Å−3
3 restraints	Absolute structure: Flack (1983), 1411 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.008 (15)

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	0.17855 (11)	1.17225 (4)	0.99142 (4)	0.0780 (3)
O1	0.2998 (5)	0.8130 (2)	0.9293 (2)	0.0454 (9)
O3	1.1945 (6)	0.8459 (2)	0.7425 (2)	0.0524 (10)
O2	0.6469 (5)	0.8437 (2)	0.8561 (2)	0.0476 (9)
H2A	0.7579	0.8596	0.8362	0.071*
C6	0.6271 (8)	1.0123 (4)	0.8788 (3)	0.0370 (12)
C10	1.4183 (7)	0.9660 (3)	0.6933 (3)	0.0343 (12)
C3	0.2568 (8)	0.9790 (4)	0.9594 (3)	0.0392 (12)
H3A	0.1357	0.9684	0.9878	0.047*
N1	0.9280 (6)	0.9674 (3)	0.8055 (2)	0.0394 (11)
C11	1.4638 (8)	1.0619 (4)	0.6803 (3)	0.0463 (14)
H11A	1.3713	1.1075	0.6983	0.056*
C8	0.8180 (8)	1.0329 (4)	0.8369 (3)	0.0431 (13)
H8A	0.8621	1.0953	0.8327	0.052*
C15	1.5614 (8)	0.9000 (4)	0.6654 (3)	0.0410 (13)
C2	0.3633 (7)	0.9045 (4)	0.9263 (3)	0.0355 (11)
C9	1.2306 (8)	0.9322 (4)	0.7355 (3)	0.0387 (12)
N2	1.1036 (6)	0.9967 (3)	0.7668 (2)	0.0397 (11)
H2B	1.1315	1.0560	0.7627	0.048*
C14	1.7394 (8)	0.9297 (4)	0.6256 (3)	0.0521 (15)
H14A	1.8342	0.8852	0.6071	0.063*
O4	1.5336 (6)	0.8046 (2)	0.6757 (2)	0.0526 (10)
H4A	1.4234	0.7953	0.6986	0.079*
C4	0.3336 (9)	1.0699 (4)	0.9496 (3)	0.0431 (13)
C7	0.5520 (8)	0.9207 (4)	0.8869 (3)	0.0377 (12)
C13	1.7743 (9)	1.0233 (4)	0.6138 (3)	0.0546 (16)
H13A	1.8916	1.0424	0.5863	0.066*
C5	0.5154 (9)	1.0869 (4)	0.9111 (3)	0.0463 (14)
H5A	0.5650	1.1484	0.9063	0.056*
C1	0.1150 (8)	0.7915 (4)	0.9715 (4)	0.0597 (17)
H1B	0.0880	0.7248	0.9688	0.090*
H1C	−0.0015	0.8254	0.9501	0.090*
H1D	0.1338	0.8098	1.0240	0.090*
C12	1.6383 (9)	1.0900 (4)	0.6421 (3)	0.0520 (15)
H12A	1.6656	1.1540	0.6351	0.062*
O1W	0.1142 (6)	0.2032 (3)	0.7660 (3)	0.0683 (13)
H2W	0.2215	0.2368	0.7723	0.102*
H1W	0.0225	0.2390	0.7451	0.102*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br1	0.0908 (5)	0.0470 (3)	0.0962 (6)	0.0036 (3)	0.0521 (4)	−0.0121 (4)
O1	0.040 (2)	0.039 (2)	0.057 (2)	−0.0034 (18)	0.0170 (18)	0.0032 (17)
O3	0.041 (2)	0.041 (2)	0.075 (3)	−0.0072 (18)	0.0064 (19)	0.0060 (18)
O2	0.038 (2)	0.046 (2)	0.059 (2)	0.0063 (18)	0.0169 (18)	0.0016 (18)
C6	0.030 (3)	0.047 (3)	0.034 (3)	−0.004 (2)	0.002 (2)	0.000 (2)
C10	0.023 (3)	0.041 (3)	0.039 (3)	0.000 (2)	0.001 (2)	0.002 (2)
C3	0.035 (3)	0.044 (3)	0.039 (3)	−0.001 (2)	0.009 (2)	0.002 (2)
N1	0.026 (2)	0.050 (3)	0.042 (3)	−0.005 (2)	0.0054 (19)	0.007 (2)
C11	0.041 (3)	0.045 (3)	0.053 (4)	0.004 (3)	0.008 (3)	0.004 (3)
C8	0.035 (3)	0.047 (3)	0.047 (3)	−0.007 (3)	0.003 (3)	0.005 (2)
C15	0.034 (3)	0.043 (3)	0.046 (3)	−0.001 (3)	−0.001 (2)	−0.006 (3)
C2	0.031 (3)	0.040 (3)	0.036 (3)	0.001 (2)	0.003 (2)	0.003 (2)
C9	0.032 (3)	0.045 (3)	0.038 (3)	−0.001 (2)	−0.002 (2)	0.003 (2)
N2	0.031 (2)	0.042 (3)	0.046 (3)	−0.003 (2)	0.010 (2)	0.004 (2)
C14	0.036 (3)	0.074 (5)	0.046 (3)	0.008 (3)	0.009 (3)	−0.003 (3)
O4	0.049 (2)	0.043 (2)	0.065 (3)	0.0035 (18)	0.0088 (19)	−0.0034 (19)
C4	0.045 (3)	0.043 (3)	0.041 (3)	−0.005 (3)	0.008 (3)	−0.006 (2)
C7	0.035 (3)	0.044 (3)	0.034 (3)	0.004 (2)	0.002 (2)	−0.001 (2)
C13	0.043 (4)	0.068 (4)	0.053 (4)	−0.007 (3)	0.013 (3)	0.016 (3)
C5	0.054 (4)	0.034 (3)	0.051 (4)	−0.006 (3)	0.012 (3)	−0.005 (3)
C1	0.044 (3)	0.055 (4)	0.080 (4)	−0.007 (3)	0.018 (3)	0.007 (3)
C12	0.042 (3)	0.057 (4)	0.057 (4)	−0.002 (3)	0.013 (3)	0.013 (3)
O1W	0.046 (2)	0.040 (2)	0.119 (4)	0.0026 (18)	0.003 (2)	−0.005 (2)

Geometric parameters (Å, º)

Br1—C4	1.899 (5)	C8—H8A	0.9300
O1—C2	1.356 (6)	C15—O4	1.372 (6)
O1—C1	1.424 (6)	C15—C14	1.396 (7)
O3—C9	1.249 (6)	C2—C7	1.406 (7)
O2—C7	1.357 (6)	C9—N2	1.337 (6)
O2—H2A	0.8200	N2—H2B	0.8600
C6—C7	1.389 (7)	C14—C13	1.358 (8)
C6—C5	1.392 (7)	C14—H14A	0.9300
C6—C8	1.451 (7)	O4—H4A	0.8200
C10—C15	1.394 (7)	C4—C5	1.363 (7)
C10—C11	1.405 (7)	C13—C12	1.374 (8)
C10—C9	1.486 (7)	C13—H13A	0.9300
C3—C2	1.381 (7)	C5—H5A	0.9300
C3—C4	1.386 (7)	C1—H1B	0.9600
C3—H3A	0.9300	C1—H1C	0.9600
N1—C8	1.286 (6)	C1—H1D	0.9600
N1—N2	1.373 (5)	C12—H12A	0.9300
C11—C12	1.357 (7)	O1W—H2W	0.8409
C11—H11A	0.9300	O1W—H1W	0.8548
C2—O1—C1	118.1 (4)	C9—N2—H2B	120.3
C7—O2—H2A	109.5	N1—N2—H2B	120.3
C7—C6—C5	119.3 (5)	C13—C14—C15	120.1 (5)
C7—C6—C8	121.9 (5)	C13—C14—H14A	120.0
C5—C6—C8	118.8 (5)	C15—C14—H14A	120.0
C15—C10—C11	117.0 (5)	C15—O4—H4A	109.5
C15—C10—C9	119.1 (5)	C5—C4—C3	121.7 (5)
C11—C10—C9	123.9 (5)	C5—C4—Br1	119.9 (4)
C2—C3—C4	118.8 (5)	C3—C4—Br1	118.4 (4)
C2—C3—H3A	120.6	O2—C7—C6	123.6 (5)
C4—C3—H3A	120.6	O2—C7—C2	116.5 (5)
C8—N1—N2	116.0 (4)	C6—C7—C2	119.8 (5)
C12—C11—C10	122.1 (5)	C14—C13—C12	120.7 (5)
C12—C11—H11A	118.9	C14—C13—H13A	119.6
C10—C11—H11A	118.9	C12—C13—H13A	119.6
N1—C8—C6	122.0 (5)	C4—C5—C6	120.2 (5)
N1—C8—H8A	119.0	C4—C5—H5A	119.9
C6—C8—H8A	119.0	C6—C5—H5A	119.9
O4—C15—C10	121.8 (5)	O1—C1—H1B	109.5
O4—C15—C14	117.7 (5)	O1—C1—H1C	109.5
C10—C15—C14	120.4 (5)	H1B—C1—H1C	109.5
O1—C2—C3	124.4 (4)	O1—C1—H1D	109.5
O1—C2—C7	115.4 (4)	H1B—C1—H1D	109.5
C3—C2—C7	120.2 (5)	H1C—C1—H1D	109.5
O3—C9—N2	121.0 (5)	C11—C12—C13	119.6 (6)
O3—C9—C10	120.8 (5)	C11—C12—H12A	120.2
N2—C9—C10	118.2 (4)	C13—C12—H12A	120.2
C9—N2—N1	119.3 (4)	H2W—O1W—H1W	106.2

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···N1	0.82	1.95	2.657 (5)	144
N2—H2B···O1Wi	0.86	2.09	2.921 (5)	164
O4—H4A···O3	0.82	1.80	2.527 (5)	147
O1W—H2W···O4ii	0.84	2.05	2.855 (6)	161
O1W—H1W···O3iii	0.85	2.06	2.823 (5)	148

Symmetry codes: (i) x+1, y+1, z; (ii) −x+2, y−1/2, −z+3/2; (iii) −x+1, y−1/2, −z+3/2.