N'-(5-Bromo-2-hydr-oxy-3-methoxy-benzyl-idene)-4-hydr-oxy-3-methoxy-benzohydrazide dihydrate.

In the title compound, C(16)H(15)BrN(2)O(5)·2H(2)O, the dihedral angle between the two aromatic rings is 2.9 (2)° and an intra-molecular O-H⋯N hydrogen bond is observed. One of the water mol-ecule is disordered over two positions, with occupancies of 0.83 (3) and 0.17 (3). In the crystal structure, mol-ecules are linked into a three-dimensional network by inter-molecular O-H⋯O, O-H⋯(O,O), O-H⋯N and N-H⋯O hydrogen bonds. π-π inter-actions involving Br-substituted benzene rings, with a centroid-centroid distance of 3.552 (3) Å are also observed.

Related literature

For related structures, see: Lu et al. (2008a ▶,b ▶,c ▶); Abdul Alhadi et al. (2009 ▶); Mohd Lair et al. (2009 ▶); Narayana et al. (2007 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C16H15BrN2O5·2H2O

M = 431.24

Monoclinic,

a = 9.262 (2) Å

b = 8.679 (2) Å

c = 24.289 (5) Å

β = 112.42 (3)°

V = 1804.9 (8) Å3

Z = 4

Mo Kα radiation

μ = 2.32 mm−1

T = 298 K

0.23 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.618, T max = 0.654

14447 measured reflections

3897 independent reflections

1997 reflections with I > 2σ(I)

R int = 0.074

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.135

S = 1.02

3897 reflections

261 parameters

20 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.53 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809033522/ci2888sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033522/ci2888Isup2.hkl

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

C16H15BrN2O5·2H2O	F(000) = 880
Mr = 431.24	Dx = 1.587 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1489 reflections
a = 9.262 (2) Å	θ = 2.4–24.5°
b = 8.679 (2) Å	µ = 2.32 mm−1
c = 24.289 (5) Å	T = 298 K
β = 112.42 (3)°	Block, colourless
V = 1804.9 (8) Å3	0.23 × 0.20 × 0.20 mm
Z = 4

Bruker APEXII CCD area-detector diffractometer	3897 independent reflections
Radiation source: fine-focus sealed tube	1997 reflections with I > 2σ(I)
graphite	Rint = 0.074
ω scans	θmax = 27.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −11→11
Tmin = 0.618, Tmax = 0.654	k = −11→11
14447 measured reflections	l = −30→30

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + 0.9035P] where P = (Fo2 + 2Fc2)/3
3897 reflections	(Δ/σ)max = 0.001
261 parameters	Δρmax = 0.32 e Å−3
20 restraints	Δρmin = −0.53 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br1	0.61788 (6)	−0.03732 (7)	−0.13511 (3)	0.0778 (3)
O1	0.3146 (3)	0.3022 (4)	0.00769 (14)	0.0605 (9)
H1	0.3776	0.3517	0.0351	0.091*
O2	0.1468 (3)	0.1263 (4)	−0.07827 (14)	0.0692 (10)
O3	0.4712 (3)	0.5527 (4)	0.14385 (13)	0.0601 (8)
O4	1.1183 (3)	0.7762 (3)	0.28824 (13)	0.0570 (8)
O5	0.9838 (3)	0.9110 (3)	0.35146 (13)	0.0504 (8)
H5	0.9305	0.9520	0.3676	0.076*
N1	0.5836 (4)	0.4024 (4)	0.07415 (15)	0.0448 (9)
N2	0.6775 (4)	0.4898 (4)	0.12135 (14)	0.0446 (9)
H2	0.7808	0.4791	0.1320	0.054*
C1	0.5494 (5)	0.2381 (5)	−0.00796 (18)	0.0422 (10)
C2	0.3905 (5)	0.2269 (5)	−0.02205 (19)	0.0450 (10)
C3	0.3019 (5)	0.1318 (5)	−0.06863 (19)	0.0483 (11)
C4	0.3704 (5)	0.0548 (5)	−0.10141 (19)	0.0516 (11)
H4	0.3102	−0.0075	−0.1330	0.062*
C5	0.5288 (5)	0.0694 (5)	−0.08767 (19)	0.0515 (11)
C6	0.6186 (5)	0.1586 (5)	−0.04129 (18)	0.0477 (11)
H6	0.7255	0.1665	−0.0319	0.057*
C7	0.6451 (5)	0.3319 (5)	0.04189 (19)	0.0476 (11)
H7	0.7516	0.3412	0.0506	0.057*
C8	0.6112 (5)	0.5611 (5)	0.15561 (18)	0.0434 (10)
C9	0.7141 (4)	0.6511 (4)	0.20645 (17)	0.0392 (10)
C10	0.8737 (5)	0.6677 (4)	0.22134 (18)	0.0421 (10)
H10	0.9213	0.6195	0.1985	0.050*
C11	0.9612 (4)	0.7545 (4)	0.26950 (18)	0.0395 (10)
C12	0.8909 (5)	0.8267 (4)	0.30448 (17)	0.0389 (10)
C13	0.7334 (5)	0.8129 (5)	0.28971 (18)	0.0468 (11)
H13	0.6856	0.8622	0.3123	0.056*
C14	0.6469 (5)	0.7260 (5)	0.24137 (19)	0.0476 (11)
H14	0.5400	0.7168	0.2316	0.057*
C15	0.0554 (6)	0.0149 (6)	−0.1176 (2)	0.0779 (16)
H15A	0.0466	0.0389	−0.1573	0.117*
H15B	−0.0468	0.0134	−0.1161	0.117*
H15C	0.1033	−0.0844	−0.1063	0.117*
C16	1.1985 (5)	0.7209 (6)	0.2527 (2)	0.0680 (14)
H16A	1.1888	0.6109	0.2493	0.102*
H16B	1.3069	0.7484	0.2709	0.102*
H16C	1.1539	0.7662	0.2137	0.102*
O6A	0.1601 (5)	0.5145 (11)	0.0818 (2)	0.061 (3)	0.83 (3)
H6A	0.248 (2)	0.553 (4)	0.1037 (19)	0.091*
H6B	0.108 (4)	0.591 (4)	0.0621 (18)	0.091*
O6B	0.161 (3)	0.596 (5)	0.0998 (16)	0.071 (10)	0.17 (3)
O7	−0.0002 (3)	0.2697 (5)	0.00144 (17)	0.0817 (11)
H7A	0.055 (5)	0.327 (6)	0.0300 (19)	0.123*
H7B	0.059 (5)	0.221 (6)	−0.012 (2)	0.123*

	U11	U22	U33	U12	U13	U23
Br1	0.0656 (4)	0.0946 (5)	0.0795 (4)	0.0048 (3)	0.0346 (3)	−0.0224 (3)
O1	0.0426 (18)	0.072 (2)	0.063 (2)	−0.0067 (16)	0.0166 (16)	−0.0216 (17)
O2	0.0376 (18)	0.089 (2)	0.078 (2)	−0.0146 (18)	0.0190 (17)	−0.030 (2)
O3	0.0332 (17)	0.078 (2)	0.064 (2)	−0.0127 (16)	0.0128 (15)	−0.0105 (17)
O4	0.0299 (16)	0.070 (2)	0.069 (2)	−0.0099 (15)	0.0168 (15)	−0.0251 (16)
O5	0.0427 (17)	0.058 (2)	0.0527 (19)	−0.0048 (15)	0.0208 (15)	−0.0106 (15)
N1	0.038 (2)	0.045 (2)	0.042 (2)	−0.0051 (17)	0.0047 (17)	0.0042 (17)
N2	0.0273 (17)	0.053 (2)	0.045 (2)	−0.0014 (16)	0.0042 (16)	−0.0033 (17)
C1	0.037 (2)	0.042 (3)	0.044 (3)	0.002 (2)	0.011 (2)	0.003 (2)
C2	0.045 (3)	0.042 (3)	0.049 (3)	0.002 (2)	0.019 (2)	0.000 (2)
C3	0.037 (2)	0.049 (3)	0.056 (3)	−0.002 (2)	0.015 (2)	−0.006 (2)
C4	0.051 (3)	0.048 (3)	0.050 (3)	−0.003 (2)	0.013 (2)	−0.008 (2)
C5	0.051 (3)	0.050 (3)	0.049 (3)	0.002 (2)	0.014 (2)	0.000 (2)
C6	0.037 (2)	0.058 (3)	0.047 (3)	0.001 (2)	0.015 (2)	0.005 (2)
C7	0.036 (2)	0.052 (3)	0.048 (3)	−0.001 (2)	0.009 (2)	0.007 (2)
C8	0.034 (2)	0.049 (3)	0.041 (2)	−0.003 (2)	0.007 (2)	0.010 (2)
C9	0.032 (2)	0.041 (2)	0.041 (2)	−0.0017 (18)	0.0101 (19)	0.0039 (19)
C10	0.041 (2)	0.039 (3)	0.046 (3)	0.0000 (19)	0.017 (2)	−0.003 (2)
C11	0.032 (2)	0.038 (2)	0.049 (3)	−0.0019 (19)	0.016 (2)	−0.001 (2)
C12	0.037 (2)	0.039 (2)	0.038 (2)	−0.0026 (19)	0.011 (2)	0.0047 (19)
C13	0.038 (2)	0.056 (3)	0.049 (3)	−0.004 (2)	0.019 (2)	−0.004 (2)
C14	0.032 (2)	0.055 (3)	0.057 (3)	−0.002 (2)	0.018 (2)	0.005 (2)
C15	0.049 (3)	0.082 (4)	0.092 (4)	−0.018 (3)	0.016 (3)	−0.016 (3)
C16	0.040 (3)	0.087 (4)	0.084 (4)	0.003 (3)	0.031 (3)	−0.023 (3)
O6A	0.037 (3)	0.081 (5)	0.056 (3)	−0.009 (2)	0.010 (2)	0.009 (3)
O6B	0.062 (12)	0.077 (14)	0.074 (13)	0.001 (8)	0.025 (9)	0.026 (8)
O7	0.048 (2)	0.112 (3)	0.083 (3)	0.000 (2)	0.0222 (18)	−0.002 (2)

Br1—C5	1.895 (4)	C8—C9	1.465 (5)
O1—C2	1.353 (5)	C9—C10	1.389 (5)
O1—H1	0.82	C9—C14	1.390 (5)
O2—C3	1.365 (5)	C10—C11	1.367 (5)
O2—C15	1.396 (5)	C10—H10	0.93
O3—C8	1.218 (5)	C11—C12	1.400 (5)
O4—C11	1.361 (4)	C12—C13	1.368 (5)
O4—C16	1.421 (5)	C13—C14	1.368 (6)
O5—C12	1.353 (4)	C13—H13	0.93
O5—H5	0.82	C14—H14	0.93
N1—C7	1.286 (5)	C15—H15A	0.96
N1—N2	1.373 (4)	C15—H15B	0.96
N2—C8	1.357 (5)	C15—H15C	0.96
N2—H2	0.90	C16—H16A	0.96
C1—C2	1.382 (5)	C16—H16B	0.96
C1—C6	1.392 (5)	C16—H16C	0.96
C1—C7	1.448 (6)	O6A—O6B	0.83 (4)
C2—C3	1.388 (6)	O6A—H6A	0.851 (10)
C3—C4	1.367 (6)	O6A—H6B	0.853 (10)
C4—C5	1.381 (6)	O6B—H6A	0.856 (10)
C4—H4	0.93	O6B—H6B	0.858 (10)
C5—C6	1.358 (6)	O7—H7A	0.85 (5)
C6—H6	0.93	O7—H7B	0.85 (5)
C7—H7	0.93
C2—O1—H1	109.5	C11—C10—C9	120.3 (4)
C3—O2—C15	117.8 (4)	C11—C10—H10	119.8
C11—O4—C16	119.3 (3)	C9—C10—H10	119.8
C12—O5—H5	109.5	O4—C11—C10	124.8 (4)
C7—N1—N2	119.0 (3)	O4—C11—C12	114.8 (3)
C8—N2—N1	118.3 (3)	C10—C11—C12	120.3 (4)
C8—N2—H2	123.6	O5—C12—C13	122.7 (4)
N1—N2—H2	116.8	O5—C12—C11	117.4 (3)
C2—C1—C6	120.3 (4)	C13—C12—C11	119.9 (4)
C2—C1—C7	120.1 (4)	C14—C13—C12	119.3 (4)
C6—C1—C7	119.6 (4)	C14—C13—H13	120.3
O1—C2—C1	123.7 (4)	C12—C13—H13	120.3
O1—C2—C3	117.2 (4)	C13—C14—C9	122.0 (4)
C1—C2—C3	119.1 (4)	C13—C14—H14	119.0
O2—C3—C4	125.1 (4)	C9—C14—H14	119.0
O2—C3—C2	114.6 (4)	O2—C15—H15A	109.5
C4—C3—C2	120.3 (4)	O2—C15—H15B	109.5
C3—C4—C5	120.0 (4)	H15A—C15—H15B	109.5
C3—C4—H4	120.0	O2—C15—H15C	109.5
C5—C4—H4	120.0	H15A—C15—H15C	109.5
C6—C5—C4	120.7 (4)	H15B—C15—H15C	109.5
C6—C5—Br1	120.8 (3)	O4—C16—H16A	109.5
C4—C5—Br1	118.5 (3)	O4—C16—H16B	109.5
C5—C6—C1	119.5 (4)	H16A—C16—H16B	109.5
C5—C6—H6	120.2	O4—C16—H16C	109.5
C1—C6—H6	120.2	H16A—C16—H16C	109.5
N1—C7—C1	120.3 (4)	H16B—C16—H16C	109.5
N1—C7—H7	119.8	O6B—O6A—H6A	61.2 (18)
C1—C7—H7	119.8	O6B—O6A—H6B	61.3 (17)
O3—C8—N2	121.2 (4)	H6A—O6A—H6B	104 (2)
O3—C8—C9	121.5 (4)	O6A—O6B—H6A	60.6 (18)
N2—C8—C9	117.3 (4)	O6A—O6B—H6B	60.6 (18)
C10—C9—C14	118.2 (4)	H6A—O6B—H6B	103 (2)
C10—C9—C8	124.1 (4)	H7A—O7—H7B	109 (3)
C14—C9—C8	117.7 (4)
C7—N1—N2—C8	−178.8 (4)	N1—N2—C8—O3	−2.5 (6)
C6—C1—C2—O1	−179.1 (4)	N1—N2—C8—C9	178.8 (3)
C7—C1—C2—O1	1.3 (6)	O3—C8—C9—C10	−178.6 (4)
C6—C1—C2—C3	2.0 (6)	N2—C8—C9—C10	0.2 (6)
C7—C1—C2—C3	−177.6 (4)	O3—C8—C9—C14	0.5 (6)
C15—O2—C3—C4	11.5 (7)	N2—C8—C9—C14	179.2 (3)
C15—O2—C3—C2	−169.8 (4)	C14—C9—C10—C11	0.6 (6)
O1—C2—C3—O2	−0.2 (6)	C8—C9—C10—C11	179.7 (4)
C1—C2—C3—O2	178.8 (4)	C16—O4—C11—C10	7.5 (6)
O1—C2—C3—C4	178.6 (4)	C16—O4—C11—C12	−173.8 (4)
C1—C2—C3—C4	−2.4 (6)	C9—C10—C11—O4	179.1 (4)
O2—C3—C4—C5	179.8 (4)	C9—C10—C11—C12	0.4 (6)
C2—C3—C4—C5	1.1 (7)	O4—C11—C12—O5	1.3 (5)
C3—C4—C5—C6	0.7 (7)	C10—C11—C12—O5	−179.9 (3)
C3—C4—C5—Br1	−179.1 (3)	O4—C11—C12—C13	179.8 (3)
C4—C5—C6—C1	−1.1 (6)	C10—C11—C12—C13	−1.4 (6)
Br1—C5—C6—C1	178.7 (3)	O5—C12—C13—C14	179.7 (4)
C2—C1—C6—C5	−0.2 (6)	C11—C12—C13—C14	1.2 (6)
C7—C1—C6—C5	179.3 (4)	C12—C13—C14—C9	−0.2 (6)
N2—N1—C7—C1	179.6 (3)	C10—C9—C14—C13	−0.8 (6)
C2—C1—C7—N1	1.6 (6)	C8—C9—C14—C13	−179.9 (4)
C6—C1—C7—N1	−178.0 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7B···O1	0.85 (5)	2.34 (5)	2.875 (4)	122 (4)
O7—H7B···O2	0.85 (5)	2.22 (5)	3.027 (5)	159 (5)
O7—H7A···O6A	0.85 (5)	2.06 (2)	2.884 (10)	163 (6)
O6A—H6B···O7i	0.85 (1)	1.91 (4)	2.740 (8)	163 (5)
O6A—H6A···O3	0.85 (1)	1.92 (2)	2.715 (6)	154 (4)
N2—H2···O5ii	0.90	2.14	3.028 (4)	169
O5—H5···O6Biii	0.82	1.85	2.64 (3)	163
O5—H5···O6Aiii	0.82	1.81	2.618 (5)	166
O1—H1···N1	0.82	1.83	2.550 (4)	145

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7B⋯O1	0.85 (5)	2.34 (5)	2.875 (4)	122 (4)
O7—H7B⋯O2	0.85 (5)	2.22 (5)	3.027 (5)	159 (5)
O7—H7A⋯O6A	0.85 (5)	2.06 (2)	2.884 (10)	163 (6)
O6A—H6B⋯O7i	0.85 (1)	1.91 (4)	2.740 (8)	163 (5)
O6A—H6A⋯O3	0.85 (1)	1.92 (2)	2.715 (6)	154 (4)
N2—H2⋯O5ii	0.90	2.14	3.028 (4)	169
O5—H5⋯O6Biii	0.82	1.85	2.64 (3)	163
O5—H5⋯O6Aiii	0.82	1.81	2.618 (5)	166
O1—H1⋯N1	0.82	1.83	2.550 (4)	145

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