(E)-N′-(5-Chloro-2-hydroxy­benzyl­idene)-2-nitro­benzohydrazide

Abstract

In the title Schiff base compound, C₁₄H₁₀ClN₃O₄, the mol­ecule adopts an E geometry with respect to the C=N bond and an intra­molecular O—H⋯N hydrogen bond is present. The benzene rings form a dihedral angle of 73.4 (2)°. In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds occur.

Related literature

For a related structure and background, see: Qian & Qu (2009 ▶).

Experimental

Crystal data

• C₁₄H₁₀ClN₃O₄

• M _r = 319.70

• Triclinic,

• a = 7.353 (1) Å

• b = 10.005 (2) Å

• c = 10.273 (2) Å

• α = 93.393 (3)°

• β = 108.144 (3)°

• γ = 98.886 (4)°

• V = 704.9 (2) ų

• Z = 2

• Mo Kα radiation

• μ = 0.29 mm⁻¹

• T = 298 K

• 0.23 × 0.20 × 0.20 mm

Data collection

• Bruker SMART CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.936, T _max = 0.944

• 4324 measured reflections

• 3004 independent reflections

• 2237 reflections with I > 2σ(I)

• R _int = 0.013

Refinement

• R[F ² > 2σ(F ²)] = 0.046

• wR(F ²) = 0.122

• S = 1.02

• 3004 reflections

• 203 parameters

• 1 restraint

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

• Δρ_max = 0.30 e Å⁻³

• Δρ_min = −0.44 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

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—H1⋯N1	0.82	1.94	2.657 (2)	145
N2—H2⋯O2i	0.902 (10)	1.966 (11)	2.863 (2)	173 (3)

Symmetry code: (i) .

supplementary crystallographic information

Comment

As part of our ongoing studies of Schiff bases (Qian & Qu, 2009), we now report the synthsis and structure of the title compound, (I), (Fig. 1).

In the title compound, the Schiff base molecule adopts an E geometry with respect to the CN bond, as shown in Fig. 1. There forms an intramolecular O—H···N hydrogen bond. The two benzene rings forms a dihedral angle of 73.4 (2)°. The dihedral angle between the O3/N3/O4 plane and the C9—C14 benzene ring is 23.2 (2)°. In the crystal structure, the adjacent two Schiff base molecules are linked through intermolecular N—H···O hydrogen bonds (Table 1) to form a dimer (Fig. 2).

Experimental

2-Nitrobenzohydrazide (1 mmol, 0.181 g) and 5-chlorosalicylaldehyde (1 mmol, 0.156 g) were dissolved in anhydrous methanol (15 ml). The mixture was stirred for several minutes at room temperature. The product was isolated and recrystallized from methanol, colorless blocks of (I) were obtained after a week.

Refinement

The imino H atom was located in a difference map and its positional parameters were refined with a fixed isotropic thermal parameter of 0.08 Ų. Other H atoms were positioned geometrically and refined as riding with C—H = 0.93 Å, O—H = 0.82 Å, and with U_iso(H) = 1.2U_eq(C) and 1.5U_eq(O).

Figures

Fig. 1.

The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonding is shown by dashed lines.

Fig. 2.

The molecular packing of (I), viewed along the b axis. Hydrogen bonding is shown in dashed lines.

Crystal data

C14H10ClN3O4	Z = 2
Mr = 319.70	F(000) = 328
Triclinic, P1	Dx = 1.506 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.353 (1) Å	Cell parameters from 1356 reflections
b = 10.005 (2) Å	θ = 2.4–25.6°
c = 10.273 (2) Å	µ = 0.29 mm−1
α = 93.393 (3)°	T = 298 K
β = 108.144 (3)°	Block, colorless
γ = 98.886 (4)°	0.23 × 0.20 × 0.20 mm
V = 704.9 (2) Å3

Data collection

Bruker SMART CCD diffractometer	3004 independent reflections
Radiation source: fine-focus sealed tube	2237 reflections with I > 2σ(I)
graphite	Rint = 0.013
ω scans	θmax = 27.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→9
Tmin = 0.936, Tmax = 0.944	k = −9→12
4324 measured reflections	l = −13→12

Refinement

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0501P)2 + 0.3008P] where P = (Fo2 + 2Fc2)/3
3004 reflections	(Δ/σ)max < 0.001
203 parameters	Δρmax = 0.30 e Å−3
1 restraint	Δρmin = −0.44 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
Cl1	0.54671 (11)	−0.14057 (9)	0.86494 (8)	0.0837 (3)
N1	0.1470 (2)	0.23302 (15)	0.43169 (16)	0.0372 (4)
N2	0.0876 (3)	0.35676 (17)	0.43461 (17)	0.0422 (4)
N3	0.3643 (3)	0.53956 (19)	0.2180 (2)	0.0510 (5)
O1	0.1405 (2)	−0.01201 (16)	0.31361 (15)	0.0534 (4)
H1	0.1202	0.0663	0.3150	0.080*
O2	−0.0068 (3)	0.53476 (15)	0.32927 (15)	0.0574 (5)
O3	0.4103 (3)	0.54714 (19)	0.34314 (18)	0.0735 (5)
O4	0.4446 (3)	0.6178 (2)	0.1575 (2)	0.0898 (7)
C1	0.2638 (3)	0.05581 (19)	0.5597 (2)	0.0383 (4)
C2	0.2290 (3)	−0.0378 (2)	0.4431 (2)	0.0428 (5)
C3	0.2854 (3)	−0.1637 (2)	0.4603 (3)	0.0543 (6)
H3	0.2585	−0.2270	0.3837	0.065*
C4	0.3798 (4)	−0.1956 (2)	0.5886 (3)	0.0615 (7)
H4	0.4185	−0.2796	0.5990	0.074*
C5	0.4176 (3)	−0.1023 (3)	0.7029 (3)	0.0551 (6)
C6	0.3583 (3)	0.0212 (2)	0.6893 (2)	0.0463 (5)
H6	0.3816	0.0820	0.7673	0.056*
C7	0.2062 (3)	0.18811 (19)	0.5484 (2)	0.0377 (4)
H7	0.2125	0.2412	0.6277	0.045*
C8	0.0525 (3)	0.4269 (2)	0.3254 (2)	0.0404 (5)
C9	0.0740 (3)	0.36796 (19)	0.19420 (19)	0.0369 (4)
C10	0.2071 (3)	0.43017 (19)	0.13654 (19)	0.0374 (4)
C11	0.2035 (3)	0.3885 (2)	0.0051 (2)	0.0461 (5)
H11	0.2919	0.4344	−0.0323	0.055*
C12	0.0674 (4)	0.2784 (2)	−0.0695 (2)	0.0529 (6)
H12	0.0638	0.2488	−0.1580	0.063*
C13	−0.0624 (4)	0.2123 (2)	−0.0142 (2)	0.0573 (6)
H13	−0.1526	0.1366	−0.0643	0.069*
C14	−0.0606 (4)	0.2574 (2)	0.1164 (2)	0.0516 (6)
H14	−0.1516	0.2126	0.1522	0.062*
H2	0.072 (4)	0.392 (3)	0.5126 (18)	0.080*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0709 (5)	0.0970 (6)	0.0952 (6)	0.0360 (4)	0.0260 (4)	0.0547 (5)
N1	0.0494 (10)	0.0296 (8)	0.0381 (9)	0.0096 (7)	0.0212 (8)	0.0020 (7)
N2	0.0654 (11)	0.0356 (9)	0.0368 (9)	0.0178 (8)	0.0281 (8)	0.0055 (7)
N3	0.0529 (11)	0.0467 (11)	0.0539 (12)	0.0027 (9)	0.0224 (9)	−0.0015 (9)
O1	0.0639 (10)	0.0449 (9)	0.0481 (9)	0.0110 (8)	0.0156 (8)	−0.0083 (7)
O2	0.1017 (13)	0.0428 (9)	0.0476 (9)	0.0330 (9)	0.0414 (9)	0.0136 (7)
O3	0.0818 (13)	0.0720 (12)	0.0495 (10)	−0.0114 (10)	0.0125 (9)	−0.0109 (9)
O4	0.0946 (15)	0.0820 (14)	0.0882 (14)	−0.0283 (12)	0.0452 (12)	0.0039 (11)
C1	0.0381 (10)	0.0339 (10)	0.0461 (11)	0.0053 (8)	0.0189 (9)	0.0053 (8)
C2	0.0377 (11)	0.0351 (10)	0.0571 (13)	0.0023 (8)	0.0205 (10)	−0.0005 (9)
C3	0.0524 (13)	0.0341 (11)	0.0804 (17)	0.0077 (10)	0.0291 (13)	−0.0022 (11)
C4	0.0554 (14)	0.0390 (12)	0.103 (2)	0.0170 (11)	0.0389 (15)	0.0186 (13)
C5	0.0443 (12)	0.0553 (14)	0.0752 (16)	0.0167 (10)	0.0253 (12)	0.0291 (12)
C6	0.0459 (12)	0.0451 (12)	0.0527 (12)	0.0102 (9)	0.0207 (10)	0.0112 (10)
C7	0.0441 (11)	0.0336 (10)	0.0386 (10)	0.0053 (8)	0.0194 (9)	0.0001 (8)
C8	0.0553 (12)	0.0350 (10)	0.0369 (10)	0.0098 (9)	0.0227 (9)	0.0046 (8)
C9	0.0488 (11)	0.0337 (10)	0.0322 (9)	0.0115 (8)	0.0168 (8)	0.0035 (8)
C10	0.0444 (11)	0.0355 (10)	0.0349 (10)	0.0108 (8)	0.0150 (9)	0.0034 (8)
C11	0.0558 (13)	0.0521 (13)	0.0388 (11)	0.0154 (10)	0.0242 (10)	0.0080 (9)
C12	0.0706 (16)	0.0597 (14)	0.0300 (10)	0.0190 (12)	0.0163 (10)	−0.0004 (10)
C13	0.0663 (15)	0.0525 (14)	0.0424 (12)	−0.0003 (11)	0.0103 (11)	−0.0083 (10)
C14	0.0580 (14)	0.0488 (13)	0.0476 (12)	−0.0015 (10)	0.0229 (11)	−0.0004 (10)

Geometric parameters (Å, °)

Cl1—C5	1.738 (3)	C4—C5	1.383 (4)
N1—C7	1.276 (2)	C4—H4	0.9300
N1—N2	1.377 (2)	C5—C6	1.373 (3)
N2—C8	1.336 (2)	C6—H6	0.9300
N2—H2	0.902 (10)	C7—H7	0.9300
N3—O3	1.217 (2)	C8—C9	1.503 (2)
N3—O4	1.221 (2)	C9—C14	1.380 (3)
N3—C10	1.460 (3)	C9—C10	1.383 (3)
O1—C2	1.347 (3)	C10—C11	1.380 (3)
O1—H1	0.8200	C11—C12	1.373 (3)
O2—C8	1.228 (2)	C11—H11	0.9300
C1—C6	1.389 (3)	C12—C13	1.364 (3)
C1—C2	1.407 (3)	C12—H12	0.9300
C1—C7	1.451 (3)	C13—C14	1.385 (3)
C2—C3	1.390 (3)	C13—H13	0.9300
C3—C4	1.367 (4)	C14—H14	0.9300
C3—H3	0.9300
C7—N1—N2	115.34 (15)	C1—C6—H6	119.8
C8—N2—N1	122.02 (15)	N1—C7—C1	121.21 (17)
C8—N2—H2	118.8 (18)	N1—C7—H7	119.4
N1—N2—H2	119.2 (18)	C1—C7—H7	119.4
O3—N3—O4	123.3 (2)	O2—C8—N2	120.66 (17)
O3—N3—C10	118.26 (18)	O2—C8—C9	120.00 (17)
O4—N3—C10	118.47 (19)	N2—C8—C9	119.22 (17)
C2—O1—H1	109.5	C14—C9—C10	117.09 (18)
C6—C1—C2	118.97 (19)	C14—C9—C8	119.38 (18)
C6—C1—C7	119.03 (18)	C10—C9—C8	122.92 (18)
C2—C1—C7	121.99 (18)	C11—C10—C9	122.36 (19)
O1—C2—C3	117.59 (19)	C11—C10—N3	117.72 (18)
O1—C2—C1	122.93 (18)	C9—C10—N3	119.85 (17)
C3—C2—C1	119.5 (2)	C12—C11—C10	119.0 (2)
C4—C3—C2	120.7 (2)	C12—C11—H11	120.5
C4—C3—H3	119.6	C10—C11—H11	120.5
C2—C3—H3	119.6	C13—C12—C11	120.11 (19)
C3—C4—C5	119.7 (2)	C13—C12—H12	119.9
C3—C4—H4	120.1	C11—C12—H12	119.9
C5—C4—H4	120.1	C12—C13—C14	120.3 (2)
C6—C5—C4	120.7 (2)	C12—C13—H13	119.9
C6—C5—Cl1	119.7 (2)	C14—C13—H13	119.9
C4—C5—Cl1	119.51 (19)	C9—C14—C13	121.1 (2)
C5—C6—C1	120.3 (2)	C9—C14—H14	119.4
C5—C6—H6	119.8	C13—C14—H14	119.4

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.94	2.657 (2)	145
N2—H2···O2i	0.90 (1)	1.97 (1)	2.863 (2)	173 (3)

Symmetry codes: (i) −x, −y+1, −z+1.