5-Nitro­salicylaldehyde benzoyl­hydrazone

Ali, H.M.; Puvaneswary, S.; Ng, S.W.

doi:10.1107/S1600536805030497

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5-Nitrosalicylaldehyde benzoylhydrazone

H. M. Ali, S. Puvaneswary and S. W. Ng

Nearly planar molecules of the title compound, C₁₁H₁₁N₃O₄, are linked by O—H

O hydrogen bonds to form zigzag chains along the c axis; adjacent chains are, in turn, linked by weaker N—H

O hydrogen bonds to form layers perpendicular to the a axis of the orthorhombic unit cell.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805030497/lh6505sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805030497/lh6505Isup2.hkl Contains datablock I

CCDC reference: 287638

checkCIF report

Key indicators

Single-crystal X-ray study
T = 295 K
Mean (C-C) = 0.004 Å
R factor = 0.035
wR factor = 0.113
Data-to-parameter ratio = 7.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) .....       7.46
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT731_ALERT_1_C Bond    Calc     0.86(3), Rep   0.850(10) ......       3.00 su-Rat
              O1   -H1O     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.86(3), Rep   0.850(10) ......       3.00 su-Rat
              O1   -H1O     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.85(3), Rep   1.860(10) ......       3.00 su-Rat
              H1O  -O4      1.555   3.564

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.04
           From the CIF: _reflns_number_total               1478
           Count of symmetry unique reflns         1482
           Completeness (_total/calc)             99.73%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no

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

   4 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

Comment top

The crystal structure of salicylaldehyde benzoylhydrazone features an intramolecular hydrogen bond between the donor OH group of the salicylaldehyde moiety and the acceptor ═N–NH— group of the benzhydrazidyl moiety (Lyubchova et al., 1995); the short hydrogen bond permits the amino nitrogen of the ═N–NH– unit to interact with the –C═O– unit of an adjacent molecule. Such a hydrogen-bonding scheme is also found in 5-chlorosalicylaldehyde benzoylhydrazone (Ali et al., 2005).

In the title compound, (I), the much stronger electron-withdrawing nitro group reduces the donor ability of the OH group, and in 5-nitrosalicylaldehyde benzoylhydrazone (Fig. 1), the salicylaldehyde portion is rotated so that its OH group forms an intermolecular hydrogen bond with the amide O atom of an adjacent molecule, the hydrogen bond giving rise to a chain motif (Fig. 2). In contrast, the hydrogen bonds involving the amine N atom are weaker (Table 2); these N—H···O bonds lead to the formation of layers.

Experimental top

Benzhydrazide (0.16 g, 1.2 mmol) and 5-nitrosalicylaldehyde (0.20 g, 1.2 mol) were refluxed in ethanol (20 ml) for 2 h. The solvent was removed and the product recrystallized from pyridine.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. ORTEPII (Johnson, 1976) plot of (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as spheres of arbitrary radii.
	Fig. 2. ORTEPII (Johnson, 1976) of the hydrogen-bonded (dashed lines) chain structure in (I). The weaker N—H···O interactions that link adjacent chains into layers are not shown.

5-Nitrosalicylaldehyde benzoylhydrazone top

Crystal data top

C₁₄H₁₁N₃O₄	F(000) = 592
M_r = 285.26	D_x = 1.496 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 2819 reflections
a = 30.224 (2) Å	θ = 2.3–26.7°
b = 4.8017 (3) Å	µ = 0.11 mm⁻¹
c = 8.7257 (6) Å	T = 295 K
V = 1266.3 (2) Å³	Plate, yellow
Z = 4	0.39 × 0.30 × 0.09 mm

Data collection top

Bruker SMART area-detector diffractometer	1226 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.030
Graphite monochromator	θ_max = 27.0°, θ_min = 1.4°
ϕ and ω scans	h = −38→36
7031 measured reflections	k = −5→6
1478 independent reflections	l = −11→11

Refinement top

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ²(F_o²) + (0.0699P)²] where P = (F_o² + 2F_c²)/3
1478 reflections	(Δ/σ)_max = 0.001
198 parameters	Δρ_max = 0.23 e Å⁻³
3 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₄H₁₁N₃O₄	V = 1266.3 (2) Å³
M_r = 285.26	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 30.224 (2) Å	µ = 0.11 mm⁻¹
b = 4.8017 (3) Å	T = 295 K
c = 8.7257 (6) Å	0.39 × 0.30 × 0.09 mm

Data collection top

Bruker SMART area-detector diffractometer	1226 reflections with I > 2σ(I)
7031 measured reflections	R_int = 0.030
1478 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	3 restraints
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	Δρ_max = 0.23 e Å⁻³
1478 reflections	Δρ_min = −0.21 e Å⁻³
198 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.2906 (1)	1.1454 (5)	0.5000 (3)	0.0397 (5)
O2	0.4015 (1)	0.3332 (5)	0.9011 (3)	0.0577 (7)
O3	0.3360 (1)	0.2125 (5)	0.9692 (3)	0.0482 (6)
O4	0.1405 (1)	0.3305 (5)	0.8318 (3)	0.0446 (6)
N1	0.3613 (1)	0.3571 (5)	0.8939 (3)	0.0354 (6)
N2	0.2058 (1)	0.6635 (5)	0.7303 (3)	0.0347 (6)
N3	0.1615 (1)	0.7313 (5)	0.7190 (3)	0.0363 (6)
C1	0.3090 (1)	0.9580 (6)	0.5940 (3)	0.0310 (6)
C2	0.3544 (1)	0.9159 (6)	0.6027 (4)	0.0386 (7)
C3	0.3717 (1)	0.7189 (6)	0.7006 (4)	0.0379 (7)
C4	0.3430 (1)	0.5641 (6)	0.7914 (3)	0.0323 (6)
C5	0.2977 (1)	0.6014 (6)	0.7856 (3)	0.0326 (6)
C6	0.2801 (1)	0.7982 (6)	0.6866 (4)	0.0323 (6)
C7	0.2322 (1)	0.8434 (6)	0.6768 (4)	0.0361 (7)
C8	0.1308 (1)	0.5552 (6)	0.7721 (3)	0.0334 (6)
C9	0.0837 (1)	0.6415 (6)	0.7545 (4)	0.0335 (6)
C10	0.0521 (1)	0.5096 (7)	0.8425 (4)	0.0465 (8)
C11	0.0079 (1)	0.5788 (8)	0.8292 (5)	0.0522 (9)
C12	−0.0049 (1)	0.7793 (8)	0.7268 (5)	0.0518 (9)
C13	0.0261 (1)	0.9103 (8)	0.6383 (5)	0.0527 (9)
C14	0.0702 (1)	0.8433 (6)	0.6504 (4)	0.0437 (8)
H1o	0.311 (1)	1.223 (7)	0.447 (4)	0.05 (1)*
H3n	0.153 (1)	0.891 (4)	0.689 (4)	0.04 (1)*
H2	0.3733	1.0215	0.5419	0.046*
H3	0.4021	0.6899	0.7059	0.046*
H5	0.2792	0.4954	0.8476	0.039*
H7	0.2213	1.0043	0.6312	0.043*
H10	0.0607	0.3724	0.9117	0.056*
H11	−0.0131	0.4895	0.8897	0.063*
H12	−0.0346	0.8263	0.7175	0.062*
H13	0.0172	1.0464	0.5690	0.063*
H14	0.0909	0.9331	0.5891	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.038 (1)	0.041 (1)	0.041 (1)	−0.001 (1)	0.002 (1)	0.012 (1)
O2	0.032 (1)	0.070 (2)	0.071 (2)	0.003 (1)	−0.007 (1)	0.025 (2)
O3	0.045 (1)	0.051 (1)	0.048 (1)	0.001 (1)	0.001 (1)	0.020 (1)
O4	0.039 (1)	0.037 (1)	0.058 (1)	0.001 (1)	−0.003 (1)	0.018 (1)
N1	0.037 (1)	0.035 (1)	0.035 (1)	0.002 (1)	−0.001 (1)	0.003 (1)
N2	0.029 (1)	0.034 (1)	0.041 (1)	0.003 (1)	0.000 (1)	0.002 (1)
N3	0.030 (1)	0.030 (1)	0.048 (2)	0.002 (1)	0.001 (1)	0.010 (1)
C1	0.036 (2)	0.027 (1)	0.031 (1)	−0.002 (1)	0.001 (1)	0.000 (1)
C2	0.037 (2)	0.040 (2)	0.039 (1)	−0.006 (1)	0.008 (1)	0.003 (2)
C3	0.030 (2)	0.042 (2)	0.042 (1)	0.000 (1)	0.002 (1)	0.003 (2)
C4	0.033 (1)	0.032 (2)	0.032 (1)	−0.001 (1)	−0.002 (1)	0.000 (1)
C5	0.033 (1)	0.033 (2)	0.032 (1)	−0.005 (1)	0.002 (1)	0.002 (1)
C6	0.031 (1)	0.032 (2)	0.033 (1)	−0.002 (1)	0.001 (1)	0.000 (1)
C7	0.033 (2)	0.035 (2)	0.041 (1)	0.002 (1)	−0.001 (1)	0.006 (1)
C8	0.033 (1)	0.030 (2)	0.036 (1)	−0.001 (1)	−0.001 (1)	0.000 (1)
C9	0.029 (1)	0.035 (2)	0.037 (1)	−0.002 (1)	0.000 (1)	0.001 (1)
C10	0.042 (2)	0.045 (2)	0.053 (1)	0.004 (1)	0.005 (2)	0.015 (2)
C11	0.037 (2)	0.060 (2)	0.060 (2)	−0.001 (2)	0.011 (2)	0.007 (2)
C12	0.032 (2)	0.059 (2)	0.064 (3)	0.007 (1)	−0.001 (2)	−0.006 (2)
C13	0.045 (2)	0.056 (2)	0.057 (2)	0.008 (2)	−0.006 (2)	0.017 (2)
C14	0.036 (2)	0.046 (2)	0.050 (2)	−0.002 (1)	−0.002 (1)	0.013 (2)

Geometric parameters (Å, º) top

O1—C1	1.339 (4)	C9—C14	1.390 (4)
O2—N1	1.221 (3)	C10—C11	1.382 (5)
O3—N1	1.225 (3)	C11—C12	1.369 (6)
O4—C8	1.233 (3)	C12—C13	1.367 (5)
N1—C4	1.447 (4)	C13—C14	1.375 (4)
N2—C7	1.266 (4)	O1—H1o	0.85 (1)
N2—N3	1.382 (3)	N3—H3n	0.85 (1)
N3—C8	1.338 (4)	C2—H2	0.93
C1—C2	1.388 (4)	C3—H3	0.93
C1—C6	1.417 (4)	C5—H5	0.93
C2—C3	1.377 (5)	C7—H7	0.93
C3—C4	1.390 (4)	C10—H10	0.93
C4—C5	1.381 (4)	C11—H11	0.93
C5—C6	1.387 (4)	C12—H12	0.93
C6—C7	1.464 (4)	C13—H13	0.93
C8—C9	1.489 (4)	C14—H14	0.93
C9—C10	1.380 (4)

C1—O1—H1o	109 (2)	C9—C10—C11	120.8 (3)
O2—N1—O3	122.8 (3)	C12—C11—C10	119.8 (3)
O2—N1—C4	118.5 (2)	C13—C12—C11	119.9 (3)
O3—N1—C4	118.8 (2)	C12—C13—C14	120.9 (3)
C7—N2—N3	115.2 (2)	C13—C14—C9	119.9 (3)
C8—N3—N2	119.9 (2)	C8—N3—H3n	118 (2)
O1—C1—C2	122.8 (3)	N2—N3—H3n	122 (2)
O1—C1—C6	117.1 (2)	C3—C2—H2	119.7
C2—C1—C6	120.0 (3)	C1—C2—H2	119.7
C3—C2—C1	120.6 (3)	C2—C3—H3	120.5
C2—C3—C4	119.0 (3)	C4—C3—H3	120.5
C5—C4—C3	121.9 (3)	C4—C5—H5	120.2
C5—C4—N1	119.4 (2)	C6—C5—H5	120.2
C3—C4—N1	118.7 (2)	N2—C7—H7	120.0
C4—C5—C6	119.5 (3)	C6—C7—H7	120.0
C5—C6—C1	119.1 (3)	C9—C10—H10	119.6
C5—C6—C7	121.1 (3)	C11—C10—H10	119.6
C1—C6—C7	119.8 (3)	C12—C11—H11	120.1
N2—C7—C6	120.0 (3)	C10—C11—H11	120.1
O4—C8—N3	122.3 (3)	C13—C12—H12	120.0
O4—C8—C9	120.9 (3)	C11—C12—H12	120.0
N3—C8—C9	116.8 (3)	C12—C13—H13	119.6
C10—C9—C14	118.7 (3)	C14—C13—H13	119.6
C10—C9—C8	118.4 (3)	C13—C14—H14	120.0
C14—C9—C8	122.9 (3)	C9—C14—H14	120.0

C7—N2—N3—C8	180.0 (3)	N3—N2—C7—C6	178.1 (3)
O1—C1—C2—C3	−179.5 (3)	C5—C6—C7—N2	−16.5 (5)
C6—C1—C2—C3	0.1 (5)	C1—C6—C7—N2	163.7 (3)
C1—C2—C3—C4	−0.4 (5)	N2—N3—C8—O4	0.0 (4)
C2—C3—C4—C5	0.3 (5)	N2—N3—C8—C9	−179.4 (3)
C2—C3—C4—N1	179.9 (3)	O4—C8—C9—C10	18.2 (4)
O2—N1—C4—C5	−177.7 (3)	N3—C8—C9—C10	−162.4 (3)
O3—N1—C4—C5	2.7 (4)	O4—C8—C9—C14	−160.0 (3)
O2—N1—C4—C3	2.7 (4)	N3—C8—C9—C14	19.4 (4)
O3—N1—C4—C3	−176.9 (3)	C14—C9—C10—C11	−0.8 (5)
C3—C4—C5—C6	0.1 (4)	C8—C9—C10—C11	−179.1 (3)
N1—C4—C5—C6	−179.5 (3)	C9—C10—C11—C12	0.4 (6)
C4—C5—C6—C1	−0.4 (4)	C10—C11—C12—C13	−0.1 (6)
C4—C5—C6—C7	179.8 (3)	C11—C12—C13—C14	0.1 (6)
O1—C1—C6—C5	179.9 (3)	C12—C13—C14—C9	−0.4 (6)
C2—C1—C6—C5	0.2 (4)	C10—C9—C14—C13	0.8 (5)
O1—C1—C6—C7	−0.2 (4)	C8—C9—C14—C13	179.0 (3)
C2—C1—C6—C7	−179.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···O4ⁱ	0.85 (1)	1.86 (1)	2.700 (3)	170 (3)
N3—H3n···O3ⁱ	0.85 (1)	2.48 (2)	3.178 (3)	140 (3)
N3—H3n···O4ⁱⁱ	0.85 (1)	2.48 (3)	3.106 (4)	131 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁N₃O₄
M_r	285.26
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	295
a, b, c (Å)	30.224 (2), 4.8017 (3), 8.7257 (6)
V (Å³)	1266.3 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.39 × 0.30 × 0.09

Data collection
Diffractometer	Bruker SMART area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7031, 1478, 1226
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.640

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.113, 1.17
No. of reflections	1478
No. of parameters	198
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.21

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···O4ⁱ	0.85 (1)	1.86 (1)	2.700 (3)	170 (3)
N3—H3n···O3ⁱ	0.85 (1)	2.48 (2)	3.178 (3)	140 (3)
N3—H3n···O4ⁱⁱ	0.85 (1)	2.48 (3)	3.106 (4)	131 (3)

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

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