2-Hydr­oxy-5-nitro­benzaldehyde phenyl­hydrazone

In the title compound, C₁₃H₁₁N₃O₃, the mol­ecule is essentially planar, the dihedral angle between the benzene rings being 5.31 (10)°. The nitro group meta to the phenyl­hydrazone substituent is almost coplanar with the ring to which it is attached, with a dihedral angle of 3.09 (12)° between the plane of the nitro group and the phenol ring plane. In the crystal structure, inter­molecular N—H...O and C—H...O inter­actions inter­connect the mol­ecules into a three-dimensional framework. In addition, the crystal packing is stabilized by weak π–π inter­actions [centroid–centroid distance = 3.7279 (11) Å].

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C)= 0.003 Å
• R factor = 0.068
• wR factor = 0.152
• Data-to-parameter ratio = 19.3

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S1. Comment

Several phenylhydrazone derivatives have been reported and were found to have versatile coordinating abilities towards different metal ions (Raj et al., 2006). Some of these compounds were used as monitors or detectors for formaldehyde (Suliman et al., 2001) and are also used to determine airbone aldehydes and ketones (Vogel et al., 2000). Phenylhydrazone and nitrophenylhydrazone derivatives have also been synthesized in our laboratory in order to investigate their structures and analytical application. The title compound (I) whose structure is reported here, (Fig. 1) is one of the series of related phenylhdrazone derivatives that we have prepared; the X-ray structures of two of this series have been studied previously (Tameem et al., 2006; Tameem et al., 2007).

The bond lengths and angles in (I) have normal values (Allen et al., 1987) and are comparable with those in the related structures (Shan et al., 2003; Shan et al., 2004). The molecule is essentially planar with the dihedral angle between the two benzene rings (C1—C6 and C8—C13) being 5.31 (10)°. The nitro group in the title compound, benzaldehyde 2-nitro-5-hydroxyphenylhydrazone, is attached at C10, meta to the phenylhydrazone substituent in the phenol ring [torsion angle of O2—N3—C10—C11 = -2.7 (3)°]. However, the corresponding nitro group in salicylaldehyde 4-nitrophenylhydrazone (Shan et al., 2003) is attached at C4 in para-position to the hydrazone group [torsion angle of O1—N1—C4—C5 = -6.2 (5)°].

An intramolecular O1—H1B···N2 interaction (Table 1 and Figure 1) generates an S(6) ring motif (Bernstein et al., 1995). In the crystal structure, the molecules are linked by intermolecular N1—H1C···O3ⁱ and C9—H9A···O1ⁱⁱ interactions into a three-dimensional framework (Figure 2). In addition, the crystal packing is stabilized by weak intermolecular π···π interactions involving the C8—C13 (Centroid Cg1) benzene ring with a Cg1···Cg1ⁱⁱⁱ distance of 3.7279 (11)Å [symmetry code: (iii) 1 - x, 2 - y, -z].

Related literature

For related literature on hydrogen-bond motifs, see Bernstein et al. (1995) and on values of bond lengths and angles, see Allen et al. (1987). For related structures, see Shan et al. (2003); Shan et al. (2004); Tameem et al., 2006; Tameem et al., 2007. For related literature, see: Raj & Kurup (2006); Suliman & Soma (2002); Vogel et al. (2000).

S2. Experimental

The title compound (I) was prepared by the slow addition of phenylhydrazine (350 mg, 3.2 mmol) dissolved in 5 ml concentrated sulfuric acid to a 2-hydroxy-5-nitrobenzaldehyde (540 mg, 3.2 mmol) dissloved in 20 ml of 95% ethanol. The mixture was stirred for 15 min, and then left to stand at room temperature form 30 min. The resulting product was filtered off and washed with 20 ml 95% ethanol and an orange powder product was collected. Crystals suitable for X-ray diffraction analysis were grown by the slow evaporation of a saturated solution of the resultant product in ethanol.

S3. Refinement

The H atoms on the N and O atoms were located in a difference map and refined isotropically, with N—H = 0.85 (2)Å and O—H = 0.85 (3) Å. The remaining H atoms were positioned geometrically and treated as riding, with C—H = 0.93Å and the U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids and the atom numbering. A dashed line indicates an intramolecular hydrogen bond.
	Fig. 2. The crystal packing of (I), viewed down the c axis. The intermolecular N—H···O and C—H···O hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted.

2-Hydroxy-5-nitrobenzaldehyde phenylhydrazone

Crystal data

C13H11N3O3	F(000) = 536
Mr = 257.25	Dx = 1.441 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2685 reflections
a = 12.9019 (5) Å	θ = 1.7–30.2°
b = 7.9909 (3) Å	µ = 0.11 mm^−1
c = 12.5323 (5) Å	T = 100 K
β = 113.418 (2)°	Plate, orange
V = 1185.63 (8) Å^3	0.35 × 0.29 × 0.03 mm
Z = 4

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer	3480 independent reflections
Radiation source: fine-focus sealed tube	2265 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
Detector resolution: 8.33 pixels mm^-1	θmax = 30.2°, θmin = 1.7°
ω scans	h = −18→16
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −9→11
Tmin = 0.939, Tmax = 0.997	l = −16→17
12742 measured reflections

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.152	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0569P)^2 + 0.5968P] where P = (Fo^2 + 2Fc^2)/3
3480 reflections	(Δ/σ)max < 0.001
180 parameters	Δρmax = 0.42 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

Experimental. The data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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
O1	0.48565 (12)	0.68203 (19)	0.15079 (12)	0.0262 (4)
O2	0.84393 (11)	1.10514 (19)	0.05297 (12)	0.0308 (4)
O3	0.73542 (12)	1.0344 (2)	−0.12240 (12)	0.0387 (4)
N1	0.25322 (13)	0.5634 (2)	−0.14691 (14)	0.0231 (4)
N2	0.34887 (12)	0.6265 (2)	−0.06494 (13)	0.0200 (4)
N3	0.76112 (13)	1.0327 (2)	−0.01671 (14)	0.0236 (4)
C1	0.18662 (16)	0.4549 (3)	−0.00323 (16)	0.0236 (4)
H1A	0.2441	0.5097	0.0569	0.028*
C2	0.10905 (17)	0.3587 (3)	0.02002 (18)	0.0289 (5)
H2A	0.1152	0.3485	0.0962	0.035*
C3	0.02226 (17)	0.2773 (3)	−0.06842 (19)	0.0302 (5)
H3A	−0.0287	0.2112	−0.0517	0.036*
C4	0.01232 (17)	0.2953 (3)	−0.18153 (18)	0.0283 (5)
H4A	−0.0467	0.2428	−0.2415	0.034*
C5	0.08898 (16)	0.3903 (2)	−0.20658 (17)	0.0235 (4)
H5A	0.0814	0.4019	−0.2832	0.028*
C6	0.17827 (15)	0.4695 (2)	−0.11688 (16)	0.0205 (4)
C7	0.41932 (15)	0.7005 (2)	−0.09859 (15)	0.0200 (4)
H7A	0.4046	0.7061	−0.1774	0.024*
C8	0.52188 (15)	0.7755 (2)	−0.01390 (15)	0.0184 (4)
C9	0.59248 (15)	0.8645 (2)	−0.05285 (16)	0.0197 (4)
H9A	0.5749	0.8741	−0.1321	0.024*
C10	0.68939 (15)	0.9392 (2)	0.02689 (16)	0.0194 (4)
C11	0.71885 (15)	0.9287 (2)	0.14548 (16)	0.0218 (4)
H11A	0.7842	0.9799	0.1974	0.026*
C12	0.64949 (15)	0.8409 (3)	0.18517 (16)	0.0227 (4)
H12A	0.6684	0.8320	0.2647	0.027*
C13	0.55093 (15)	0.7649 (2)	0.10712 (15)	0.0199 (4)
H1C	0.2504 (16)	0.564 (3)	−0.2155 (19)	0.017 (5)*
H1B	0.431 (2)	0.649 (3)	0.090 (2)	0.051 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0238 (7)	0.0336 (9)	0.0177 (7)	−0.0076 (6)	0.0046 (6)	0.0003 (6)
O2	0.0240 (7)	0.0339 (9)	0.0311 (8)	−0.0097 (6)	0.0073 (6)	−0.0029 (7)
O3	0.0321 (8)	0.0616 (12)	0.0211 (7)	−0.0113 (8)	0.0091 (6)	0.0048 (7)
N1	0.0214 (8)	0.0300 (10)	0.0143 (8)	−0.0056 (7)	0.0033 (6)	−0.0018 (7)
N2	0.0170 (7)	0.0214 (9)	0.0170 (7)	0.0004 (6)	0.0019 (6)	−0.0022 (6)
N3	0.0196 (8)	0.0263 (9)	0.0234 (8)	0.0011 (7)	0.0071 (7)	0.0024 (7)
C1	0.0181 (9)	0.0245 (11)	0.0221 (9)	−0.0020 (8)	0.0016 (7)	−0.0010 (8)
C2	0.0258 (10)	0.0342 (13)	0.0253 (10)	0.0001 (9)	0.0088 (8)	0.0036 (9)
C3	0.0234 (10)	0.0261 (11)	0.0386 (12)	−0.0028 (9)	0.0096 (9)	0.0031 (9)
C4	0.0208 (10)	0.0227 (11)	0.0329 (11)	−0.0031 (8)	0.0017 (8)	−0.0033 (9)
C5	0.0223 (9)	0.0219 (10)	0.0200 (9)	0.0002 (8)	0.0018 (7)	−0.0007 (8)
C6	0.0183 (9)	0.0180 (9)	0.0217 (9)	0.0011 (7)	0.0042 (7)	−0.0002 (8)
C7	0.0188 (9)	0.0231 (10)	0.0147 (8)	0.0021 (8)	0.0030 (7)	−0.0004 (7)
C8	0.0176 (8)	0.0182 (9)	0.0163 (8)	0.0033 (7)	0.0034 (7)	0.0002 (7)
C9	0.0201 (9)	0.0211 (10)	0.0168 (8)	0.0030 (8)	0.0063 (7)	−0.0004 (7)
C10	0.0161 (8)	0.0199 (10)	0.0220 (9)	0.0022 (7)	0.0072 (7)	0.0013 (8)
C11	0.0170 (9)	0.0220 (10)	0.0211 (9)	0.0007 (8)	0.0020 (7)	0.0000 (8)
C12	0.0219 (9)	0.0283 (11)	0.0135 (8)	−0.0001 (8)	0.0025 (7)	0.0004 (8)
C13	0.0194 (9)	0.0206 (10)	0.0183 (9)	0.0021 (8)	0.0062 (7)	0.0017 (7)

Geometric parameters (Å, º)

O1—C13	1.347 (2)	C4—C5	1.379 (3)
O1—H1B	0.85 (3)	C4—H4A	0.9300
O2—N3	1.224 (2)	C5—C6	1.401 (3)
O3—N3	1.231 (2)	C5—H5A	0.9300
N1—N2	1.351 (2)	C7—C8	1.456 (2)
N1—C6	1.389 (3)	C7—H7A	0.9300
N1—H1C	0.85 (2)	C8—C9	1.389 (3)
N2—C7	1.288 (2)	C8—C13	1.413 (2)
N3—C10	1.454 (2)	C9—C10	1.387 (2)
C1—C2	1.382 (3)	C9—H9A	0.9300
C1—C6	1.390 (3)	C10—C11	1.383 (3)
C1—H1A	0.9300	C11—C12	1.376 (3)
C2—C3	1.385 (3)	C11—H11A	0.9300
C2—H2A	0.9300	C12—C13	1.398 (2)
C3—C4	1.379 (3)	C12—H12A	0.9300
C3—H3A	0.9300
C13—O1—H1B	103.0 (19)	N1—C6—C5	117.75 (17)
N2—N1—C6	121.31 (16)	C1—C6—C5	119.26 (18)
N2—N1—H1C	115.4 (14)	N2—C7—C8	120.37 (17)
C6—N1—H1C	121.6 (14)	N2—C7—H7A	119.8
C7—N2—N1	118.22 (16)	C8—C7—H7A	119.8
O2—N3—O3	123.23 (17)	C9—C8—C13	118.48 (16)
O2—N3—C10	118.71 (16)	C9—C8—C7	119.19 (16)
O3—N3—C10	118.06 (15)	C13—C8—C7	122.30 (17)
C2—C1—C6	119.67 (18)	C10—C9—C8	119.77 (17)
C2—C1—H1A	120.2	C10—C9—H9A	120.1
C6—C1—H1A	120.2	C8—C9—H9A	120.1
C1—C2—C3	121.0 (2)	C11—C10—C9	122.15 (18)
C1—C2—H2A	119.5	C11—C10—N3	119.41 (16)
C3—C2—H2A	119.5	C9—C10—N3	118.44 (17)
C4—C3—C2	119.3 (2)	C12—C11—C10	118.63 (17)
C4—C3—H3A	120.4	C12—C11—H11A	120.7
C2—C3—H3A	120.4	C10—C11—H11A	120.7
C5—C4—C3	120.63 (19)	C11—C12—C13	120.66 (17)
C5—C4—H4A	119.7	C11—C12—H12A	119.7
C3—C4—H4A	119.7	C13—C12—H12A	119.7
C4—C5—C6	120.11 (19)	O1—C13—C12	118.11 (16)
C4—C5—H5A	119.9	O1—C13—C8	121.58 (16)
C6—C5—H5A	119.9	C12—C13—C8	120.31 (18)
N1—C6—C1	122.96 (16)
C6—N1—N2—C7	174.30 (18)	C8—C9—C10—C11	−0.2 (3)
C6—C1—C2—C3	−0.5 (3)	C8—C9—C10—N3	−179.55 (17)
C1—C2—C3—C4	−1.1 (3)	O2—N3—C10—C11	−2.7 (3)
C2—C3—C4—C5	1.3 (3)	O3—N3—C10—C11	177.10 (18)
C3—C4—C5—C6	0.2 (3)	O2—N3—C10—C9	176.73 (17)
N2—N1—C6—C1	10.0 (3)	O3—N3—C10—C9	−3.5 (3)
N2—N1—C6—C5	−171.80 (18)	C9—C10—C11—C12	0.1 (3)
C2—C1—C6—N1	−179.80 (19)	N3—C10—C11—C12	179.47 (17)
C2—C1—C6—C5	2.0 (3)	C10—C11—C12—C13	−0.4 (3)
C4—C5—C6—N1	179.86 (18)	C11—C12—C13—O1	−179.33 (18)
C4—C5—C6—C1	−1.8 (3)	C11—C12—C13—C8	0.8 (3)
N1—N2—C7—C8	177.97 (17)	C9—C8—C13—O1	179.28 (17)
N2—C7—C8—C9	−175.53 (18)	C7—C8—C13—O1	1.1 (3)
N2—C7—C8—C13	2.7 (3)	C9—C8—C13—C12	−0.9 (3)
C13—C8—C9—C10	0.5 (3)	C7—C8—C13—C12	−179.07 (18)
C7—C8—C9—C10	178.80 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···N2	0.85 (2)	1.81 (2)	2.613 (2)	156 (2)
N1—H1C···O3^i	0.85 (2)	2.12 (2)	2.961 (2)	170 (2)
C9—H9A···O1^ii	0.93	2.54	3.430 (2)	161

Symmetry codes: (i) −x+1, y−1/2, −z−1/2; (ii) x, −y+3/2, z−1/2.