4-Hydr­oxy-N′-[(E)-(2-hydroxy­phen­yl)methyl­idene]benzohydrazide

In the title compound, C₁₄H₁₂N₂O₃, the dihedral angle between the two benzene rings is 21.70 (4)°. An intra­molecular O—H...N hydrogen bond generates an S(6) ring motif. In the crystal structure, the mol­ecules are linked by inter­molecular O—H...O, N—H...O and C—H...O hydrogen bonds into a three-dimensional framework.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C)= 0.001 Å
• R factor = 0.044
• wR factor = 0.138
• Data-to-parameter ratio = 28.2

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S1. Comment

The chemical properties of hydrazone derivatives have been intensively investigated in several research fields mainly due to their facile synthesis, tuneable electronic and steric properties, and good chelating ability (Pelizzi & Pelizzi, 1980). Some derivatives of the title compound, (I), were used for the determination of glucose (Lever et al., 1972). These compounds crystallize in the E conformation (Shan et al., 2003; Fun et al., 1996; Naidu et al., 1996), and isomeric compounds have also been prepared (Ferguson et al., 2005). We report here the crystal structure of the title compound, (I).

The bond lengths and angles in (I) have normal values (Allen et al., 1987) and are comparable to those in a related structure (Lyubchova et al., 1995). The molecule is slightly twisted about C6—C7 bond, with diheral angle between the two benzene rings (C1—C6 and C9—C14) being 21.70 (4)°. The hydroxyl groups at C3 and C14 lie almost coplanar to the benzene rings to which they are attached, with out-of-plane distances for O1 and O3 atoms of 0.018 (1) and 0.024 (1) Å, respectively.

An intramolecular O3—H3A···N2 interaction (Table 1 and Fig. 1) generates an S(6) ring motif (Bernstein et al., 1995). In the crystal structure, the molecules are linked by intermolecular O—H···O, N—H···O and C—H···O type hydrogen bonds into a three-dimensional framework (Fig. 2).

Related literature

For hydrogen-bond motifs, see: Bernstein et al. (1995). For bond-length data, see: Allen et al. (1987). For related structures, see: Lyubchova et al. (1995); Ferguson et al. (2005); Fun et al. (1996); Lever (1972); Mani Naidu et al. (1996); Pelizzi & Pelizzi (1980); Shan et al. (2003).

S2. Experimental

A solution of salicylaldehyde (122 mg, 1 mmol) in methanol (10 m) was added dropwise to a methanol solution (10 ml) of 4-hydroxybenzhydrazide (136 mg, 1 mmol) and the mixture was refluxed for 2 h. The resulting solution was evaporated on a steam bath to 5 ml and cooled to room temperature. Yellow crystals of (I) suitable for X-ray diffraction separated out and were filtered off, then washed with 5 ml of cooled methanol and dried in air.

S3. Refinement

H atoms on N and O atoms were located in a difference map and refined isotropically [N—H = 0.88 (2) Å and O—H = 0.88 (2)–0.89 (2) Å]. The remaining H atoms were positioned geometrically and treated as riding, with C—H = 0.93 Å and 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 atomic numbering. The dashed line indicates a hydrogen bond.
	Fig. 2. The crystal packing of (I), viewed down the b axis. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted.

4-Hydroxy-N'-[(E)-(2-hydroxyphenyl)methylidene]benzohydrazide

Crystal data

C14H12N2O3	F(000) = 536
Mr = 256.26	Dx = 1.440 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5136 reflections
a = 13.5978 (5) Å	θ = 1.6–35.0°
b = 8.0656 (3) Å	µ = 0.10 mm^−1
c = 11.4128 (4) Å	T = 100 K
β = 109.238 (2)°	Block, colourless
V = 1181.80 (8) Å^3	0.41 × 0.21 × 0.09 mm
Z = 4

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer	5185 independent reflections
Radiation source: fine-focus sealed tube	4394 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
Detector resolution: 8.33 pixels mm^-1	θmax = 35.0°, θmin = 1.6°
ω scans	h = −21→21
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −12→12
Tmin = 0.878, Tmax = 0.991	l = −18→18
34050 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0831P)^2 + 0.2009P] where P = (Fo^2 + 2Fc^2)/3
5185 reflections	(Δ/σ)max = 0.001
184 parameters	Δρmax = 0.54 e Å^−3
0 restraints	Δρmin = −0.29 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	−0.03503 (5)	1.28061 (9)	0.00201 (6)	0.01848 (13)
O2	0.21825 (4)	0.84194 (9)	0.46567 (5)	0.01660 (13)
O3	0.44856 (5)	0.60515 (9)	0.67431 (6)	0.01678 (13)
N1	0.34439 (5)	0.87903 (9)	0.38035 (6)	0.01407 (13)
N2	0.41034 (5)	0.78729 (9)	0.47462 (6)	0.01335 (13)
C1	0.08643 (6)	1.07094 (10)	0.29951 (7)	0.01423 (14)
H1A	0.0755	1.0531	0.3748	0.017*
C2	0.01575 (6)	1.16534 (11)	0.20889 (7)	0.01492 (14)
H2A	−0.0419	1.2111	0.2235	0.018*
C3	0.03152 (6)	1.19150 (11)	0.09501 (7)	0.01459 (14)
C4	0.11898 (6)	1.12422 (12)	0.07450 (7)	0.01746 (15)
H4A	0.1299	1.1425	−0.0007	0.021*
C5	0.18981 (6)	1.03015 (12)	0.16573 (7)	0.01678 (15)
H5A	0.2479	0.9857	0.1513	0.020*
C6	0.17425 (5)	1.00178 (10)	0.27965 (7)	0.01306 (13)
C7	0.24494 (5)	0.90150 (10)	0.38087 (7)	0.01272 (13)
C8	0.50372 (6)	0.76244 (10)	0.47417 (7)	0.01381 (14)
H8A	0.5245	0.8046	0.4102	0.017*
C9	0.57653 (5)	0.66847 (10)	0.57382 (6)	0.01236 (13)
C10	0.67930 (6)	0.64939 (11)	0.57431 (7)	0.01548 (14)
H10A	0.6988	0.6968	0.5110	0.019*
C11	0.75215 (6)	0.56124 (12)	0.66729 (8)	0.01823 (16)
H11A	0.8199	0.5492	0.6663	0.022*
C12	0.72291 (6)	0.49078 (12)	0.76224 (7)	0.01814 (15)
H12A	0.7717	0.4326	0.8254	0.022*
C13	0.62144 (6)	0.50647 (11)	0.76368 (7)	0.01626 (15)
H13A	0.6027	0.4582	0.8273	0.020*
C14	0.54761 (6)	0.59453 (10)	0.66996 (7)	0.01319 (13)
H1B	−0.0923 (12)	1.303 (2)	0.0209 (14)	0.029 (4)*
H1C	0.3652 (12)	0.914 (2)	0.3191 (15)	0.034 (4)*
H3A	0.4105 (13)	0.661 (2)	0.6095 (17)	0.043 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0146 (2)	0.0239 (3)	0.0172 (3)	0.0055 (2)	0.00550 (19)	0.0054 (2)
O2	0.0139 (2)	0.0230 (3)	0.0136 (2)	0.0001 (2)	0.00554 (18)	0.0013 (2)
O3	0.0159 (2)	0.0211 (3)	0.0160 (2)	0.0003 (2)	0.0088 (2)	0.0024 (2)
N1	0.0115 (2)	0.0174 (3)	0.0135 (3)	0.0025 (2)	0.0044 (2)	0.0030 (2)
N2	0.0123 (2)	0.0151 (3)	0.0123 (2)	0.0016 (2)	0.0036 (2)	0.0009 (2)
C1	0.0130 (3)	0.0159 (3)	0.0149 (3)	0.0005 (2)	0.0061 (2)	−0.0003 (2)
C2	0.0127 (3)	0.0164 (3)	0.0166 (3)	0.0021 (2)	0.0061 (2)	0.0014 (3)
C3	0.0124 (3)	0.0161 (3)	0.0151 (3)	0.0006 (2)	0.0043 (2)	0.0007 (2)
C4	0.0150 (3)	0.0244 (4)	0.0143 (3)	0.0047 (3)	0.0067 (2)	0.0022 (3)
C5	0.0140 (3)	0.0226 (4)	0.0148 (3)	0.0044 (3)	0.0061 (2)	0.0012 (3)
C6	0.0113 (3)	0.0149 (3)	0.0129 (3)	0.0008 (2)	0.0039 (2)	−0.0002 (2)
C7	0.0112 (3)	0.0144 (3)	0.0123 (3)	0.0002 (2)	0.0035 (2)	−0.0018 (2)
C8	0.0132 (3)	0.0161 (3)	0.0127 (3)	0.0010 (2)	0.0049 (2)	0.0020 (2)
C9	0.0121 (3)	0.0134 (3)	0.0115 (3)	0.0003 (2)	0.0038 (2)	0.0009 (2)
C10	0.0127 (3)	0.0190 (4)	0.0153 (3)	0.0013 (3)	0.0053 (2)	0.0029 (3)
C11	0.0142 (3)	0.0215 (4)	0.0180 (3)	0.0028 (3)	0.0039 (2)	0.0033 (3)
C12	0.0192 (3)	0.0190 (4)	0.0140 (3)	0.0036 (3)	0.0025 (2)	0.0024 (3)
C13	0.0206 (3)	0.0160 (3)	0.0127 (3)	0.0020 (3)	0.0063 (2)	0.0020 (2)
C14	0.0149 (3)	0.0133 (3)	0.0124 (3)	0.0000 (2)	0.0059 (2)	−0.0007 (2)

Geometric parameters (Å, º)

O1—C3	1.3524 (10)	C4—H4A	0.93
O1—H1B	0.892 (15)	C5—C6	1.4031 (11)
O2—C7	1.2372 (9)	C5—H5A	0.93
O3—C14	1.3666 (9)	C6—C7	1.4768 (10)
O3—H3A	0.877 (19)	C8—C9	1.4513 (10)
N1—C7	1.3663 (9)	C8—H8A	0.93
N1—N2	1.3687 (9)	C9—C10	1.4040 (10)
N1—H1C	0.884 (16)	C9—C14	1.4137 (10)
N2—C8	1.2872 (9)	C10—C11	1.3857 (11)
C1—C2	1.3849 (11)	C10—H10A	0.93
C1—C6	1.4025 (10)	C11—C12	1.3925 (12)
C1—H1A	0.93	C11—H11A	0.93
C2—C3	1.4012 (11)	C12—C13	1.3911 (11)
C2—H2A	0.93	C12—H12A	0.93
C3—C4	1.3953 (11)	C13—C14	1.3959 (11)
C4—C5	1.3880 (11)	C13—H13A	0.93
C3—O1—H1B	109.3 (10)	O2—C7—N1	119.86 (7)
C14—O3—H3A	108.5 (11)	O2—C7—C6	122.78 (6)
C7—N1—N2	117.47 (6)	N1—C7—C6	117.34 (6)
C7—N1—H1C	122.4 (10)	N2—C8—C9	119.83 (7)
N2—N1—H1C	119.9 (10)	N2—C8—H8A	120.1
C8—N2—N1	118.21 (6)	C9—C8—H8A	120.1
C2—C1—C6	121.08 (7)	C10—C9—C14	118.80 (7)
C2—C1—H1A	119.5	C10—C9—C8	118.78 (7)
C6—C1—H1A	119.5	C14—C9—C8	122.42 (6)
C1—C2—C3	119.66 (7)	C11—C10—C9	121.25 (7)
C1—C2—H2A	120.2	C11—C10—H10A	119.4
C3—C2—H2A	120.2	C9—C10—H10A	119.4
O1—C3—C4	117.51 (7)	C10—C11—C12	119.34 (7)
O1—C3—C2	122.73 (7)	C10—C11—H11A	120.3
C4—C3—C2	119.76 (7)	C12—C11—H11A	120.3
C5—C4—C3	120.39 (7)	C13—C12—C11	120.71 (7)
C5—C4—H4A	119.8	C13—C12—H12A	119.6
C3—C4—H4A	119.8	C11—C12—H12A	119.6
C4—C5—C6	120.33 (7)	C12—C13—C14	120.20 (7)
C4—C5—H5A	119.8	C12—C13—H13A	119.9
C6—C5—H5A	119.8	C14—C13—H13A	119.9
C1—C6—C5	118.77 (7)	O3—C14—C13	118.20 (7)
C1—C6—C7	117.44 (6)	O3—C14—C9	122.09 (7)
C5—C6—C7	123.79 (7)	C13—C14—C9	119.71 (7)
C7—N1—N2—C8	178.74 (7)	C5—C6—C7—N1	20.95 (12)
C6—C1—C2—C3	0.48 (12)	N1—N2—C8—C9	178.82 (7)
C1—C2—C3—O1	179.17 (8)	N2—C8—C9—C10	−177.14 (8)
C1—C2—C3—C4	−0.89 (12)	N2—C8—C9—C14	3.29 (12)
O1—C3—C4—C5	−179.38 (8)	C14—C9—C10—C11	−0.55 (12)
C2—C3—C4—C5	0.67 (13)	C8—C9—C10—C11	179.87 (8)
C3—C4—C5—C6	−0.04 (13)	C9—C10—C11—C12	−0.23 (14)
C2—C1—C6—C5	0.15 (12)	C10—C11—C12—C13	0.75 (14)
C2—C1—C6—C7	−179.41 (7)	C11—C12—C13—C14	−0.48 (13)
C4—C5—C6—C1	−0.37 (13)	C12—C13—C14—O3	179.26 (8)
C4—C5—C6—C7	179.17 (8)	C12—C13—C14—C9	−0.31 (12)
N2—N1—C7—O2	1.13 (11)	C10—C9—C14—O3	−178.74 (7)
N2—N1—C7—C6	179.47 (7)	C8—C9—C14—O3	0.83 (12)
C1—C6—C7—O2	18.77 (12)	C10—C9—C14—C13	0.81 (12)
C5—C6—C7—O2	−160.76 (8)	C8—C9—C14—C13	−179.62 (7)
C1—C6—C7—N1	−159.51 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···N2	0.88 (2)	1.85 (2)	2.616 (1)	146 (2)
O1—H1B···O2^i	0.89 (2)	1.80 (2)	2.682 (1)	171 (2)
N1—H1C···O3^ii	0.88 (2)	2.30 (2)	3.122 (1)	156 (1)
C12—H12A···O2^iii	0.93	2.45	3.176 (1)	134

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