Nearly planar molecules of the title compound, C
11H
11N
3O
4, 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.
Supporting information
CCDC reference: 287638
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
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.
In the absence of significant anomalous dispersion effects, Friedel pairs were merged. C-bound H atoms were placed at calculated positions (C—H = 0.93 Å) and included in the refinement in the riding-model approximation with Uiso(H) values set at 1.2Ueq(C). N– and O-bound H atoms were located in a difference Fourier map and refined with a distance restraint of N—H = O—H = 0.85 (1) Å.
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.
5-Nitrosalicylaldehyde benzoylhydrazone
top
Crystal data top
C14H11N3O4 | F(000) = 592 |
Mr = 285.26 | Dx = 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 | Rint = 0.030 |
Graphite monochromator | θmax = 27.0°, θmin = 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(Fo2) + (0.0699P)2] where P = (Fo2 + 2Fc2)/3 |
1478 reflections | (Δ/σ)max = 0.001 |
198 parameters | Δρmax = 0.23 e Å−3 |
3 restraints | Δρmin = −0.21 e Å−3 |
Crystal data top
C14H11N3O4 | V = 1266.3 (2) Å3 |
Mr = 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 | Rint = 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 | Δρmax = 0.23 e Å−3 |
1478 reflections | Δρmin = −0.21 e Å−3 |
198 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
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 |
Mr | 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 |
Rint | 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 |
Δρmax, Δρmin (e Å−3) | 0.23, −0.21 |
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. |
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.