(E)-N′-(4-Hy­droxy­benzyl­idene)-2-nitro­benzohydrazide

In the title compound, C₁₄H₁₁N₃O₄, the two benzene rings form a dihedral angle of 45.3 (3)°. The nitro group is twisted out of the attached ring by a dihedral angle of 37.5 (3)°. In the crystal structure, mol­ecules are linked into a two-dimensional network parallel to (100) by O—H...O and N—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.048
• wR factor = 0.125
• Data-to-parameter ratio = 8.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       3.13 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N3
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..          5
PLAT731_ALERT_1_C Bond    Calc     0.90(4), Rep   0.900(10) ......       4.00 su-Ra
              N2   -H2A     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.90(4), Rep   0.900(10) ......       4.00 su-Ra
              N2   -H2A     1.555   1.555
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         15

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           26.60
           From the CIF: _reflns_number_total               1602
           Count of symmetry unique reflns         1616
           Completeness (_total/calc)             99.13%
           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
   6 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Considerable attention has been focused on hydrazones and their medicinal applications (Hillmer et al., 2010; Zhu et al., 2009; Jimenez-Pulido et al., 2008; Raj et al., 2007; Zhong et al., 2007). The study on the crystal structures of such compounds is of particular interest (Khaledi et al., 2009; Warad et al., 2009; Back et al., 2009; Vijayakumar et al., 2009). We report herein the crystal structure of the title new hydrazone.

In the title molecule (Fig. 1), the dihedral angle between the two benzene rings is 45.3 (3)°, indicating that the molecule is twisted. The dihedral angle between the N3/O3/O4 nitro group and the C9–C14 benzene ring is 37.5 (3)°. All the bond lengths are comparable to those observed in related structures (Cao, 2009; Xu et al., 2009; Shafiq et al., 2009).

In the crystal structure, molecules are linked through O—H···O and N—H···O hydrogen bonds, to form a two-dimensional network parallel to the (100) (Fig. 2 and Table 1).

Related literature

For the medicinal applications of hydrazone compounds, see: Hillmer et al. (2010); Zhu et al. (2009); Jimenez-Pulido et al. (2008); Raj et al. (2007); Zhong et al. (2007). For the crystal structures of hydrazones, see: Khaledi et al. (2009); Warad et al. (2009); Back et al. (2009); Vijayakumar et al. (2009). For related structures, see: Cao (2009); Xu et al. (2009); Shafiq et al. (2009).

S2. Experimental

The title compound was prepared by the condensation reaction of 4-hydroxybenzaldehyde (0.05 mol, 6 g) and 2-nitrobenzohydrazide (0.05 mol, 9 g) in anhydrous methanol (200 ml) at ambient temperature. Colourless block-shaped single crystals suitable for X-ray structure determination were obtained by slow evaporation of the methanol solution for a period of 8 d.

S3. Refinement

Atom H2A was located in a difference map and refined isotropically, with the N–H distance restrained to 0.90 (1) Å [U_iso(H2) = 0.08 Ų]. The remaining H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C–H distances of 0.93 Å, O–H distance of 0.82 Å, and with U_iso(H) = 1.2U_eq(C) and 1.5U_eq(O). In the absence of significant anomalous dispersion effects, Friedel pairs were averaged.

Computing details

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

Figures

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen atoms are shown as spheres of arbitrary radius.
	Fig. 2. The molecular packing of the title compound, viewed along the a axis. Hydrogen bonds are shown as dashed lines. Hydrogen atoms not involved in hydrogen bonding have been omitted.

(E)-N'-(4-Hydroxybenzylidene)-2-nitrobenzohydrazide

Crystal data

C14H11N3O4	F(000) = 592
Mr = 285.26	Dx = 1.429 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 633 reflections
a = 7.720 (2) Å	θ = 2.5–24.5°
b = 11.398 (3) Å	µ = 0.11 mm^−1
c = 15.072 (5) Å	T = 298 K
V = 1326.3 (7) Å^3	Block, colourless
Z = 4	0.20 × 0.18 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1602 independent reflections
Radiation source: fine-focus sealed tube	961 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.085
ω scans	θmax = 26.6°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→9
Tmin = 0.979, Tmax = 0.981	k = −14→13
7745 measured reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0542P)^2] where P = (Fo^2 + 2Fc^2)/3
1602 reflections	(Δ/σ)max = 0.001
194 parameters	Δρmax = 0.25 e Å^−3
1 restraint	Δρmin = −0.18 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
N1	0.1071 (5)	0.7318 (3)	1.03691 (19)	0.0490 (10)
N2	0.1251 (5)	0.7909 (3)	0.9568 (2)	0.0486 (9)
N3	0.2475 (6)	1.1354 (4)	0.9364 (3)	0.0729 (13)
O1	0.1478 (4)	0.3516 (2)	1.34410 (16)	0.0478 (8)
H1	0.0826	0.3784	1.3820	0.072*
O2	0.0109 (4)	0.9556 (2)	1.01482 (16)	0.0498 (8)
O3	0.3197 (5)	1.0807 (4)	0.9939 (2)	0.0846 (12)
O4	0.2255 (9)	1.2411 (4)	0.9389 (3)	0.151 (2)
C1	0.1311 (5)	0.5519 (3)	1.1159 (2)	0.0386 (9)
C2	0.0734 (5)	0.5986 (3)	1.1956 (2)	0.0415 (10)
H2	0.0306	0.6749	1.1971	0.050*
C3	0.0787 (5)	0.5334 (3)	1.2728 (3)	0.0411 (10)
H3	0.0418	0.5657	1.3262	0.049*
C4	0.1396 (5)	0.4197 (3)	1.2695 (2)	0.0362 (9)
C5	0.1956 (5)	0.3714 (3)	1.1908 (3)	0.0428 (10)
H5	0.2367	0.2948	1.1892	0.051*
C6	0.1902 (5)	0.4375 (3)	1.1148 (2)	0.0428 (10)
H6	0.2271	0.4047	1.0616	0.051*
C7	0.1348 (6)	0.6220 (4)	1.0351 (2)	0.0452 (10)
H7	0.1579	0.5856	0.9812	0.054*
C8	0.0819 (5)	0.9035 (3)	0.9539 (2)	0.0406 (10)
C9	0.1145 (5)	0.9615 (3)	0.8660 (2)	0.0385 (9)
C10	0.1817 (6)	1.0730 (4)	0.8584 (3)	0.0470 (11)
C11	0.1996 (6)	1.1296 (4)	0.7788 (3)	0.0570 (12)
H11	0.2446	1.2052	0.7762	0.068*
C12	0.1495 (7)	1.0721 (5)	0.7024 (3)	0.0649 (14)
H12	0.1618	1.1088	0.6477	0.078*
C13	0.0821 (6)	0.9617 (4)	0.7068 (3)	0.0609 (13)
H13	0.0495	0.9228	0.6552	0.073*
C14	0.0624 (5)	0.9078 (4)	0.7889 (2)	0.0468 (11)
H14	0.0127	0.8336	0.7917	0.056*
H2A	0.189 (5)	0.755 (4)	0.915 (2)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.076 (3)	0.0396 (19)	0.0313 (18)	0.0082 (19)	0.0090 (19)	0.0098 (15)
N2	0.073 (3)	0.040 (2)	0.0327 (19)	0.008 (2)	0.016 (2)	0.0108 (15)
N3	0.095 (4)	0.056 (3)	0.067 (3)	−0.013 (3)	0.011 (3)	−0.006 (2)
O1	0.065 (2)	0.0454 (16)	0.0334 (15)	0.0081 (15)	0.0097 (14)	0.0069 (12)
O2	0.068 (2)	0.0442 (16)	0.0377 (15)	0.0063 (16)	0.0144 (15)	−0.0023 (13)
O3	0.087 (3)	0.112 (3)	0.055 (2)	−0.020 (3)	−0.0063 (19)	−0.009 (2)
O4	0.262 (7)	0.056 (3)	0.133 (4)	−0.013 (3)	−0.004 (4)	−0.027 (3)
C1	0.049 (2)	0.033 (2)	0.034 (2)	0.001 (2)	0.0034 (19)	0.0029 (16)
C2	0.055 (3)	0.035 (2)	0.034 (2)	0.006 (2)	0.0031 (19)	0.0018 (17)
C3	0.051 (3)	0.041 (2)	0.032 (2)	0.002 (2)	0.0087 (18)	−0.0002 (18)
C4	0.041 (2)	0.038 (2)	0.0303 (19)	−0.007 (2)	0.0019 (18)	0.0099 (17)
C5	0.057 (3)	0.031 (2)	0.041 (2)	0.002 (2)	−0.001 (2)	−0.0005 (18)
C6	0.056 (3)	0.041 (2)	0.032 (2)	0.000 (2)	0.0040 (18)	−0.0034 (18)
C7	0.059 (3)	0.046 (2)	0.031 (2)	0.003 (2)	0.005 (2)	0.0022 (17)
C8	0.050 (3)	0.039 (2)	0.033 (2)	0.001 (2)	0.0062 (19)	0.0045 (18)
C9	0.047 (2)	0.034 (2)	0.034 (2)	0.009 (2)	0.0043 (19)	−0.0001 (17)
C10	0.053 (3)	0.044 (2)	0.043 (2)	0.008 (2)	0.008 (2)	0.001 (2)
C11	0.060 (3)	0.045 (3)	0.067 (3)	−0.003 (2)	0.013 (2)	0.019 (2)
C12	0.073 (3)	0.072 (3)	0.049 (3)	0.017 (3)	0.011 (3)	0.030 (3)
C13	0.073 (3)	0.074 (3)	0.036 (3)	0.013 (3)	0.000 (2)	0.004 (2)
C14	0.056 (3)	0.045 (2)	0.039 (2)	0.003 (2)	0.0006 (19)	0.0037 (19)

Geometric parameters (Å, º)

N1—C7	1.270 (4)	C4—C5	1.377 (5)
N1—N2	1.389 (4)	C5—C6	1.372 (5)
N2—C8	1.327 (5)	C5—H5	0.93
N2—H2A	0.90 (1)	C6—H6	0.93
N3—O3	1.204 (5)	C7—H7	0.93
N3—O4	1.217 (5)	C8—C9	1.501 (5)
N3—C10	1.466 (6)	C9—C14	1.374 (5)
O1—C4	1.368 (4)	C9—C10	1.377 (5)
O1—H1	0.82	C10—C11	1.369 (5)
O2—C8	1.224 (4)	C11—C12	1.379 (6)
C1—C6	1.381 (5)	C11—H11	0.93
C1—C2	1.388 (5)	C12—C13	1.363 (7)
C1—C7	1.457 (5)	C12—H12	0.93
C2—C3	1.381 (5)	C13—C14	1.390 (5)
C2—H2	0.93	C13—H13	0.93
C3—C4	1.380 (5)	C14—H14	0.93
C3—H3	0.93
C7—N1—N2	116.2 (3)	C1—C6—H6	119.4
C8—N2—N1	118.2 (3)	N1—C7—C1	121.3 (3)
C8—N2—H2A	123 (3)	N1—C7—H7	119.3
N1—N2—H2A	117 (3)	C1—C7—H7	119.3
O3—N3—O4	123.7 (5)	O2—C8—N2	123.9 (3)
O3—N3—C10	119.1 (4)	O2—C8—C9	121.5 (3)
O4—N3—C10	117.2 (5)	N2—C8—C9	114.4 (3)
C4—O1—H1	109.5	C14—C9—C10	116.8 (4)
C6—C1—C2	118.6 (3)	C14—C9—C8	120.0 (4)
C6—C1—C7	120.1 (3)	C10—C9—C8	123.0 (3)
C2—C1—C7	121.3 (3)	C11—C10—C9	123.2 (4)
C3—C2—C1	120.9 (3)	C11—C10—N3	116.0 (4)
C3—C2—H2	119.6	C9—C10—N3	120.7 (4)
C1—C2—H2	119.6	C10—C11—C12	118.6 (4)
C4—C3—C2	119.0 (3)	C10—C11—H11	120.7
C4—C3—H3	120.5	C12—C11—H11	120.7
C2—C3—H3	120.5	C13—C12—C11	120.4 (4)
O1—C4—C5	117.8 (3)	C13—C12—H12	119.8
O1—C4—C3	121.3 (3)	C11—C12—H12	119.8
C5—C4—C3	120.9 (3)	C12—C13—C14	119.5 (4)
C6—C5—C4	119.4 (3)	C12—C13—H13	120.2
C6—C5—H5	120.3	C14—C13—H13	120.2
C4—C5—H5	120.3	C9—C14—C13	121.6 (4)
C5—C6—C1	121.2 (4)	C9—C14—H14	119.2
C5—C6—H6	119.4	C13—C14—H14	119.2

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^i	0.82	1.93	2.725 (3)	164
N2—H2A···O1^ii	0.90 (1)	2.05 (2)	2.932 (4)	166 (4)

Symmetry codes: (i) −x, y−1/2, −z+5/2; (ii) −x+1/2, −y+1, z−1/2.