N′-(3-Bromo-5-chloro-2-hydroxy­benzyl­idine)-2-hydroxy­benzohydrazide

Abstract

In the approximately planar title mol­ecule, C₁₄H₁₀BrClN₃O₂, the dihedral angle between the aromatic ring planes is 5.79 (12)°. The conformation is stabilized by intra­molecular O—H⋯N and N—H⋯O hydrogen bonds and an inter­molecular O—H⋯O link leads to chains in the crystal propagating in [001].

Related literature

For similar Schiff bases, see: Hu et al. (2005 ▶); Wu et al. (2006 ▶); Yehye et al. (2008a ▶,b ▶).

Experimental

Crystal data

• C₁₄H₁₀BrClN₂O₃

• M _r = 369.60

• Monoclinic,

• a = 15.8387 (3) Å

• b = 6.9319 (1) Å

• c = 12.9951 (3) Å

• β = 106.461 (1)°

• V = 1368.28 (5) ų

• Z = 4

• Mo Kα radiation

• μ = 3.21 mm⁻¹

• T = 100 (2) K

• 0.30 × 0.20 × 0.05 mm

Data collection

• Bruker SMART APEX CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.446, T _max = 0.856

• 12350 measured reflections

• 3136 independent reflections

• 2545 reflections with I > 2σ(I)

• R _int = 0.038

Refinement

• R[F ² > 2σ(F ²)] = 0.029

• wR(F ²) = 0.077

• S = 1.02

• 3136 reflections

• 202 parameters

• 3 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.43 e Å⁻³

• Δρ_min = −0.41 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2008 ▶).

Supplementary Material

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
O1—H1o⋯O2i	0.83 (1)	1.76 (1)	2.591 (2)	175 (3)
O3—H3o⋯N2	0.84 (1)	1.88 (2)	2.632 (3)	149 (3)
N1—H1n⋯O1	0.87 (1)	1.90 (2)	2.614 (3)	139 (2)

Symmetry code: (i) .

supplementary crystallographic information

Comment

In the approximately planar title molecule, (I), (Fig. 1) the dihedral angle between the aromatic ring planes is 5.79 (12)°. The conformation is stabilised by intramolecular O—H···N and N—H···O hydrogen bonds and an intermolecular O—H···O link leads to chains in the crystal (Table 1).

Experimental

2-Hydroxybenzohydrazide(0.60 g, 4 mmol) and 3-bromo-5-chloro-2-ydroxybenzaldehyde (0.94 g, 4 mmol) were heated in ethanol (30 ml) for 2 h. The solvent was removed by evaporation and the resulting solid was recrystallized from ethanol to yield yellow plates of (I).

Refinement

The carbon-bound H-atoms were placed in calculated positions (C–H = 0.95 Å) and refined as riding with U(H) = 1.2U(C). The oxygen- and nitrogen-bound H-atoms were located in a difference map, and were refined with distance restraints of O–H 0.84±0.01 and N–H 0.88±0.01 Å. Their U_iso values were freely refined.

Figures

Fig. 1.

The molecular structure of (I) with atoms shown at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radiius.

Crystal data

C14H10BrClN2O3	F000 = 736
Mr = 369.60	Dx = 1.794 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3691 reflections
a = 15.8387 (3) Å	θ = 3.2–28.2º
b = 6.9319 (1) Å	µ = 3.21 mm−1
c = 12.9951 (3) Å	T = 100 (2) K
β = 106.461 (1)º	Plate, yellow
V = 1368.28 (5) Å3	0.30 × 0.20 × 0.05 mm
Z = 4

Data collection

Bruker SMART APEX CCD diffractometer	3136 independent reflections
Radiation source: fine-focus sealed tube	2545 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.038
T = 100(2) K	θmax = 27.5º
ω scans	θmin = 1.3º
Absorption correction: Multi-scan(SADABS; Sheldrick, 1996)	h = −20→20
Tmin = 0.446, Tmax = 0.856	k = −9→8
12350 measured reflections	l = −16→16

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difmap and geom
R[F2 > 2σ(F2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.077	w = 1/[σ2(Fo2) + (0.0353P)2 + 1.3959P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.001
3136 reflections	Δρmax = 0.43 e Å−3
202 parameters	Δρmin = −0.41 e Å−3
3 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.145097 (18)	0.43521 (4)	0.04463 (2)	0.02196 (9)
Cl1	−0.04591 (4)	0.45367 (9)	0.33930 (5)	0.01932 (14)
O1	0.48671 (11)	0.8436 (3)	0.72174 (14)	0.0186 (4)
H1O	0.495 (2)	0.837 (5)	0.7879 (9)	0.033 (9)*
O2	0.52114 (12)	0.6952 (3)	0.42779 (14)	0.0224 (4)
O3	0.28679 (12)	0.5844 (3)	0.23371 (14)	0.0184 (4)
H3O	0.3254 (15)	0.616 (4)	0.2897 (15)	0.027 (9)*
N1	0.42237 (13)	0.7471 (3)	0.52022 (16)	0.0142 (4)
H1N	0.4157 (17)	0.778 (4)	0.5825 (12)	0.015 (7)*
N2	0.35545 (13)	0.6804 (3)	0.43620 (16)	0.0154 (4)
C1	0.56768 (15)	0.8577 (4)	0.70555 (19)	0.0140 (5)
C2	0.64075 (16)	0.9151 (4)	0.7881 (2)	0.0163 (5)
H2	0.6343	0.9445	0.8569	0.020*
C3	0.72242 (16)	0.9295 (4)	0.7702 (2)	0.0171 (5)
H3	0.7720	0.9670	0.8271	0.021*
C4	0.73279 (16)	0.8897 (4)	0.6701 (2)	0.0174 (5)
H4	0.7890	0.9010	0.6581	0.021*
C5	0.66035 (16)	0.8333 (4)	0.5875 (2)	0.0158 (5)
H5	0.6674	0.8061	0.5187	0.019*
C6	0.57684 (15)	0.8157 (3)	0.60395 (19)	0.0131 (5)
C7	0.50521 (16)	0.7480 (3)	0.51062 (19)	0.0149 (5)
C8	0.27901 (16)	0.6691 (4)	0.4507 (2)	0.0154 (5)
H8	0.2706	0.7070	0.5174	0.018*
C9	0.20470 (16)	0.5978 (3)	0.3648 (2)	0.0155 (5)
C10	0.21190 (16)	0.5580 (3)	0.2611 (2)	0.0153 (5)
C11	0.13777 (17)	0.4882 (4)	0.1845 (2)	0.0162 (5)
C12	0.05895 (16)	0.4549 (3)	0.2073 (2)	0.0169 (5)
H12	0.0095	0.4062	0.1538	0.020*
C13	0.05363 (16)	0.4941 (4)	0.3096 (2)	0.0163 (5)
C14	0.12487 (17)	0.5652 (3)	0.3880 (2)	0.0171 (5)
H14	0.1197	0.5921	0.4577	0.020*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br1	0.02322 (15)	0.02735 (15)	0.01301 (13)	−0.00167 (11)	0.00141 (10)	−0.00143 (11)
Cl1	0.0119 (3)	0.0207 (3)	0.0259 (3)	−0.0026 (2)	0.0063 (2)	−0.0016 (3)
O1	0.0127 (9)	0.0334 (10)	0.0096 (8)	−0.0027 (8)	0.0032 (7)	−0.0009 (8)
O2	0.0184 (9)	0.0369 (11)	0.0111 (9)	0.0009 (8)	0.0027 (7)	−0.0044 (8)
O3	0.0149 (9)	0.0247 (10)	0.0149 (9)	−0.0035 (7)	0.0029 (7)	−0.0025 (8)
N1	0.0129 (10)	0.0201 (11)	0.0079 (10)	−0.0002 (8)	0.0000 (8)	−0.0028 (8)
N2	0.0148 (10)	0.0162 (10)	0.0113 (10)	0.0002 (8)	−0.0027 (8)	−0.0009 (8)
C1	0.0124 (12)	0.0151 (12)	0.0136 (12)	0.0003 (9)	0.0020 (9)	0.0018 (10)
C2	0.0162 (12)	0.0192 (12)	0.0122 (12)	−0.0016 (10)	0.0018 (10)	−0.0003 (10)
C3	0.0131 (12)	0.0181 (12)	0.0176 (12)	−0.0002 (10)	0.0000 (10)	0.0005 (11)
C4	0.0127 (12)	0.0188 (13)	0.0209 (13)	0.0007 (10)	0.0052 (10)	0.0017 (10)
C5	0.0167 (12)	0.0163 (12)	0.0150 (12)	0.0017 (10)	0.0054 (10)	0.0012 (10)
C6	0.0137 (11)	0.0127 (11)	0.0113 (11)	0.0010 (9)	0.0008 (9)	0.0021 (9)
C7	0.0168 (12)	0.0151 (11)	0.0116 (12)	0.0017 (10)	0.0018 (10)	0.0028 (10)
C8	0.0170 (12)	0.0144 (12)	0.0124 (11)	0.0013 (10)	0.0005 (10)	−0.0014 (10)
C9	0.0140 (12)	0.0147 (12)	0.0157 (12)	0.0005 (9)	0.0009 (10)	−0.0004 (10)
C10	0.0144 (12)	0.0133 (12)	0.0177 (12)	0.0022 (9)	0.0038 (10)	0.0040 (10)
C11	0.0185 (13)	0.0147 (11)	0.0132 (12)	0.0014 (10)	0.0011 (10)	0.0004 (10)
C12	0.0140 (12)	0.0152 (12)	0.0175 (13)	−0.0008 (10)	−0.0021 (10)	−0.0002 (10)
C13	0.0126 (12)	0.0132 (11)	0.0224 (13)	0.0007 (9)	0.0038 (10)	0.0010 (10)
C14	0.0188 (12)	0.0150 (12)	0.0166 (12)	0.0020 (10)	0.0037 (10)	0.0003 (10)

Geometric parameters (Å, °)

Br1—C11	1.890 (3)	C3—H3	0.9500
Cl1—C13	1.749 (3)	C4—C5	1.387 (4)
O1—C1	1.361 (3)	C4—H4	0.9500
O1—H1O	0.833 (10)	C5—C6	1.404 (3)
O2—C7	1.229 (3)	C5—H5	0.9500
O3—C10	1.344 (3)	C6—C7	1.483 (3)
O3—H3O	0.836 (10)	C8—C9	1.459 (3)
N1—C7	1.353 (3)	C8—H8	0.9500
N1—N2	1.369 (3)	C9—C14	1.399 (4)
N1—H1N	0.872 (10)	C9—C10	1.412 (4)
N2—C8	1.279 (3)	C10—C11	1.393 (3)
C1—C2	1.395 (3)	C11—C12	1.382 (4)
C1—C6	1.399 (3)	C12—C13	1.383 (4)
C2—C3	1.382 (4)	C12—H12	0.9500
C2—H2	0.9500	C13—C14	1.379 (4)
C3—C4	1.384 (4)	C14—H14	0.9500
C1—O1—H1O	106 (2)	O2—C7—N1	121.6 (2)
C10—O3—H3O	107 (2)	O2—C7—C6	120.8 (2)
C7—N1—N2	118.7 (2)	N1—C7—C6	117.6 (2)
C7—N1—H1N	117.4 (18)	N2—C8—C9	120.0 (2)
N2—N1—H1N	123.5 (18)	N2—C8—H8	120.0
C8—N2—N1	117.0 (2)	C9—C8—H8	120.0
O1—C1—C2	121.0 (2)	C14—C9—C10	119.8 (2)
O1—C1—C6	119.0 (2)	C14—C9—C8	118.2 (2)
C2—C1—C6	120.0 (2)	C10—C9—C8	122.0 (2)
C3—C2—C1	120.2 (2)	O3—C10—C11	119.1 (2)
C3—C2—H2	119.9	O3—C10—C9	122.8 (2)
C1—C2—H2	119.9	C11—C10—C9	118.0 (2)
C2—C3—C4	120.7 (2)	C12—C11—C10	122.3 (2)
C2—C3—H3	119.6	C12—C11—Br1	118.63 (19)
C4—C3—H3	119.6	C10—C11—Br1	119.05 (19)
C3—C4—C5	119.4 (2)	C11—C12—C13	118.6 (2)
C3—C4—H4	120.3	C11—C12—H12	120.7
C5—C4—H4	120.3	C13—C12—H12	120.7
C4—C5—C6	121.0 (2)	C14—C13—C12	121.3 (2)
C4—C5—H5	119.5	C14—C13—Cl1	119.6 (2)
C6—C5—H5	119.5	C12—C13—Cl1	119.01 (19)
C1—C6—C5	118.7 (2)	C13—C14—C9	119.9 (2)
C1—C6—C7	125.3 (2)	C13—C14—H14	120.0
C5—C6—C7	116.0 (2)	C9—C14—H14	120.0
C7—N1—N2—C8	175.3 (2)	N2—C8—C9—C14	172.3 (2)
O1—C1—C2—C3	−179.7 (2)	N2—C8—C9—C10	−6.4 (4)
C6—C1—C2—C3	−0.5 (4)	C14—C9—C10—O3	−179.4 (2)
C1—C2—C3—C4	0.8 (4)	C8—C9—C10—O3	−0.7 (4)
C2—C3—C4—C5	−0.6 (4)	C14—C9—C10—C11	0.5 (4)
C3—C4—C5—C6	−0.1 (4)	C8—C9—C10—C11	179.2 (2)
O1—C1—C6—C5	179.1 (2)	O3—C10—C11—C12	179.1 (2)
C2—C1—C6—C5	−0.2 (4)	C9—C10—C11—C12	−0.9 (4)
O1—C1—C6—C7	−2.6 (4)	O3—C10—C11—Br1	−0.5 (3)
C2—C1—C6—C7	178.1 (2)	C9—C10—C11—Br1	179.55 (18)
C4—C5—C6—C1	0.4 (4)	C10—C11—C12—C13	0.6 (4)
C4—C5—C6—C7	−178.0 (2)	Br1—C11—C12—C13	−179.88 (18)
N2—N1—C7—O2	1.8 (4)	C11—C12—C13—C14	0.1 (4)
N2—N1—C7—C6	−178.3 (2)	C11—C12—C13—Cl1	179.70 (19)
C1—C6—C7—O2	−172.2 (2)	C12—C13—C14—C9	−0.5 (4)
C5—C6—C7—O2	6.1 (3)	Cl1—C13—C14—C9	179.98 (18)
C1—C6—C7—N1	7.9 (4)	C10—C9—C14—C13	0.1 (4)
C5—C6—C7—N1	−173.8 (2)	C8—C9—C14—C13	−178.6 (2)
N1—N2—C8—C9	−179.6 (2)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···O2i	0.83 (1)	1.76 (1)	2.591 (2)	175 (3)
O3—H3o···N2	0.84 (1)	1.88 (2)	2.632 (3)	149 (3)
N1—H1n···O1	0.87 (1)	1.90 (2)	2.614 (3)	139 (2)

Symmetry codes: (i) x, −y+3/2, z+1/2.