4-Hydroxy-N′-(2-hydroxy­benzyl­idene)­benzohydrazide

In the title mol­ecule, C₁₄H₁₂N₂O₃, the –N—C(=O)– and 2-(imino­meth­yl)phenol fragments are almost coplanar, with an r.m.s. deviation of 0.0308 Å. The dihedral angle between the mean planes of p-phenol and N′-(2-hydroxy­benzyl­idene)formohydrazide is 20.95 (7)°. Inter­molecular O—H...O hydrogen bonds link the mol­ecules into zigzag chains running along the b axis. Weak inter­molecular N—H...O hydrogen bonds stabilize these chains into a three-dimensional packing.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.058
• wR factor = 0.127
• Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found



Alert level A
DIFF020_ALERT_1_A  _diffrn_standards_interval_count and
            _diffrn_standards_interval_time are missing. Number of measurements
            between standards or time (min) between standards.

Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         48 Perc.
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3

   1 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   3 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
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

The chemistry of aroylhydrazone compounds have recently attracted great interest(Xue et al., 2006), owing to their biological activities (Yang & Pan, 2004) and potential chelating functions (Qiu et al., 2006). We report here the synthesis and crystal structure of the title compound (I), obtained by the condensation of salicylhydrazide with 4-Hydroxybenzohydrazine.

The molecule structure of (I) is shown in Fig. 1. The N1, C7, O1 fragment is almost coplanar with the 2-(iminomethyl)phenol (C8—C13, O3, C14, N2) with an r.m.s. deviation of 0.0309 Å. The dihedral angle between the phenol (C1—C6, O2) and N'-(2-hydroxybenzylidene) formohydrazide (C8—C13, O3, C14, N2, N1, C7, O1) is 20.95 (7)°. There are one intramolecular hydrogen bond (O3—H03A···N2) and two intermolecular hydrogen bonds (O2—H02A···O1ⁱ (i: -x, y - 1/2, -z + 3/2) and N1—H1N···O3ⁱ (i: x, -y + 1/2, z - 1/2)) (Table 1). The intermolecular O—H···O hydrogen bonds link the molecules into zigzag chains running along the b axis. The weak intermolecular N—H···O hydrogen bonds stabilize the chains into a three-dimensional packing. (Fig. 2).

Related literature

The chemistry of aroylhydrazone compounds, their biological activities and potential chelating functions were recently discussed by Xue & Liu (2006), Yang & Pan (2004) and Qiu et al. (2006), respectively.

S2. Experimental

An equimolar mixture of salicylhydrazide (15 mmol) and 4-Hydroxybenzohydrazine (15 mmol) in ethanol was refluxed in a round-bottomed flask for about 3 h. The resulting precipitate was collected by filtration and washed with methanol and diethylether. The product (0.0358 g) was dissolved in methanol (15 ml), and kept at room temperature for 8 d to obtain yellow single crystals.

S3. Refinement

Atoms H02A, H03A and H1N were located on a difference Fourier map and refined isotropically with bond restraints O—H =0.85 (2) Å and N—H =0.86 (2) Å. All other H atoms were positioned geometrically and treated as riding [C—H =0.93Å and U_iso(H)=1.2Ueq(C)].

Computing details

Data collection: TEXRAY (Molecular Structure Corporation, 1999); cell refinement: TEXRAY; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and 50% probability displacement ellipsoids. The intramolecular hydrogen bonds are shown as dashed lines.
	Fig. 2. Packing diagram of (I), viewed down the b axis, showing hydrogen-bonded three-dimensional network. Hydrogen bonds are indicated by dashed lines.

N'-(2-hydroxybenzylidene)-4-hydroxybenzohydrazide

Crystal data

C14H12N2O3	F(000) = 536
Mr = 256.26	Dx = 1.404 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ybc	Cell parameters from 6169 reflections
a = 13.583 (8) Å	θ = 3.1–27.5°
b = 8.237 (4) Å	µ = 0.10 mm^−1
c = 11.499 (8) Å	T = 293 K
β = 109.53 (2)°	Needle, yellow
V = 1212.5 (13) Å^3	0.26 × 0.10 × 0.08 mm
Z = 4

Data collection

Rigaku Weissenberg IP diffractometer	2776 independent reflections
Radiation source: rotor target	1342 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.096
ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (TEXRAY; Molecular Structure Corporation, 1999)	h = −17→17
Tmin = 0.988, Tmax = 0.992	k = −10→9
11461 measured reflections	l = −14→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.058	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.127	w = 1/[σ^2(Fo^2) + (0.0481P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max < 0.001
2776 reflections	Δρmax = 0.18 e Å^−3
185 parameters	Δρmin = −0.19 e Å^−3
3 restraints	Extinction correction: SHELXL (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0057 (16)

Special details

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
C1	0.17334 (16)	−0.0018 (3)	0.2802 (2)	0.0383 (6)
C2	0.18908 (18)	−0.0299 (3)	0.1686 (2)	0.0507 (7)
H2A	0.2472	0.0144	0.1549	0.061*
C3	0.11982 (18)	−0.1225 (3)	0.0780 (2)	0.0545 (7)
H3A	0.1313	−0.1397	0.0036	0.065*
C4	0.03341 (17)	−0.1898 (3)	0.0972 (2)	0.0434 (6)
C5	0.01702 (17)	−0.1645 (3)	0.2085 (2)	0.0451 (6)
H5A	−0.0407	−0.2101	0.2223	0.054*
C6	0.08618 (16)	−0.0720 (3)	0.2981 (2)	0.0412 (6)
H6A	0.0747	−0.0558	0.3726	0.049*
C7	0.24335 (16)	0.0966 (3)	0.3817 (2)	0.0385 (6)
C8	0.57374 (16)	0.3308 (3)	0.5743 (2)	0.0358 (6)
C9	0.54584 (18)	0.4014 (3)	0.6690 (2)	0.0397 (6)
C10	0.6200 (2)	0.4887 (3)	0.7614 (2)	0.0506 (7)
H10A	0.6017	0.5362	0.8247	0.061*
C11	0.7198 (2)	0.5046 (3)	0.7592 (3)	0.0550 (7)
H11A	0.7689	0.5620	0.8218	0.066*
C12	0.7483 (2)	0.4377 (3)	0.6669 (3)	0.0554 (8)
H12A	0.8160	0.4507	0.6658	0.067*
C13	0.67605 (17)	0.3508 (3)	0.5753 (2)	0.0472 (7)
H13A	0.6958	0.3044	0.5127	0.057*
C14	0.50090 (17)	0.2387 (3)	0.4760 (2)	0.0388 (6)
H14A	0.5217	0.1984	0.4123	0.047*
O1	0.21602 (11)	0.1535 (2)	0.46486 (16)	0.0491 (5)
O2	−0.03193 (14)	−0.2793 (2)	0.00421 (18)	0.0579 (5)
H02A	−0.087 (2)	−0.303 (4)	0.021 (3)	0.118 (14)*
O3	0.44705 (14)	0.3907 (2)	0.67470 (18)	0.0525 (5)
H03A	0.4119 (18)	0.337 (3)	0.612 (2)	0.058 (9)*
N1	0.34201 (14)	0.1221 (3)	0.3811 (2)	0.0424 (5)
H1N	0.3640 (18)	0.088 (3)	0.322 (2)	0.057 (8)*
N2	0.40823 (14)	0.2122 (2)	0.47586 (17)	0.0381 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0326 (12)	0.0429 (14)	0.0403 (15)	0.0015 (11)	0.0134 (11)	0.0067 (12)
C2	0.0384 (13)	0.0720 (18)	0.0465 (17)	−0.0132 (13)	0.0206 (12)	−0.0032 (15)
C3	0.0463 (14)	0.080 (2)	0.0426 (16)	−0.0140 (14)	0.0224 (12)	−0.0061 (15)
C4	0.0363 (13)	0.0486 (15)	0.0448 (16)	−0.0020 (12)	0.0131 (11)	−0.0029 (13)
C5	0.0373 (13)	0.0503 (15)	0.0538 (18)	−0.0060 (12)	0.0233 (12)	−0.0014 (14)
C6	0.0388 (13)	0.0471 (14)	0.0412 (15)	0.0002 (11)	0.0178 (11)	0.0024 (12)
C7	0.0340 (12)	0.0462 (14)	0.0360 (15)	0.0008 (11)	0.0128 (11)	0.0070 (12)
C8	0.0359 (12)	0.0409 (13)	0.0309 (13)	0.0018 (11)	0.0115 (10)	0.0002 (11)
C9	0.0452 (13)	0.0423 (13)	0.0363 (15)	0.0036 (12)	0.0199 (11)	0.0059 (12)
C10	0.0715 (18)	0.0478 (15)	0.0346 (16)	−0.0013 (14)	0.0204 (14)	−0.0052 (13)
C11	0.0545 (16)	0.0611 (17)	0.0409 (16)	−0.0129 (14)	0.0046 (13)	−0.0038 (14)
C12	0.0444 (14)	0.0650 (18)	0.0537 (19)	−0.0068 (14)	0.0121 (14)	−0.0076 (15)
C13	0.0384 (13)	0.0575 (16)	0.0466 (16)	−0.0038 (12)	0.0155 (12)	−0.0084 (13)
C14	0.0386 (13)	0.0450 (14)	0.0366 (15)	−0.0008 (11)	0.0175 (11)	−0.0044 (11)
O1	0.0383 (9)	0.0713 (12)	0.0406 (11)	−0.0005 (8)	0.0169 (8)	−0.0042 (9)
O2	0.0492 (11)	0.0751 (13)	0.0523 (13)	−0.0176 (10)	0.0208 (10)	−0.0174 (10)
O3	0.0529 (11)	0.0667 (13)	0.0468 (12)	−0.0032 (10)	0.0287 (9)	−0.0084 (11)
N1	0.0357 (11)	0.0536 (13)	0.0392 (13)	−0.0056 (10)	0.0144 (10)	−0.0074 (11)
N2	0.0350 (10)	0.0467 (12)	0.0324 (11)	−0.0026 (9)	0.0111 (9)	−0.0012 (10)

Geometric parameters (Å, º)

C1—C2	1.389 (4)	C8—C14	1.443 (3)
C1—C6	1.393 (3)	C9—O3	1.368 (3)
C1—C7	1.477 (3)	C9—C10	1.395 (3)
C2—C3	1.377 (3)	C10—C11	1.370 (4)
C2—H2A	0.9300	C10—H10A	0.9300
C3—C4	1.381 (3)	C11—C12	1.362 (4)
C3—H3A	0.9300	C11—H11A	0.9300
C4—O2	1.356 (3)	C12—C13	1.377 (3)
C4—C5	1.386 (3)	C12—H12A	0.9300
C5—C6	1.370 (3)	C13—H13A	0.9300
C5—H5A	0.9300	C14—N2	1.277 (3)
C6—H6A	0.9300	C14—H14A	0.9300
C7—O1	1.229 (3)	O2—H02A	0.851 (18)
C7—N1	1.359 (3)	O3—H03A	0.847 (17)
C8—C9	1.394 (3)	N1—N2	1.376 (3)
C8—C13	1.396 (3)	N1—H1N	0.875 (17)
C2—C1—C6	117.9 (2)	O3—C9—C8	122.5 (2)
C2—C1—C7	124.3 (2)	O3—C9—C10	117.8 (2)
C6—C1—C7	117.8 (2)	C8—C9—C10	119.6 (2)
C3—C2—C1	121.0 (2)	C11—C10—C9	120.1 (3)
C3—C2—H2A	119.5	C11—C10—H10A	119.9
C1—C2—H2A	119.5	C9—C10—H10A	119.9
C2—C3—C4	120.2 (3)	C12—C11—C10	121.1 (2)
C2—C3—H3A	119.9	C12—C11—H11A	119.4
C4—C3—H3A	119.9	C10—C11—H11A	119.4
O2—C4—C3	117.3 (2)	C11—C12—C13	119.4 (3)
O2—C4—C5	123.0 (2)	C11—C12—H12A	120.3
C3—C4—C5	119.7 (2)	C13—C12—H12A	120.3
C6—C5—C4	119.8 (2)	C12—C13—C8	121.4 (3)
C6—C5—H5A	120.1	C12—C13—H13A	119.3
C4—C5—H5A	120.1	C8—C13—H13A	119.3
C5—C6—C1	121.5 (2)	N2—C14—C8	120.6 (2)
C5—C6—H6A	119.3	N2—C14—H14A	119.7
C1—C6—H6A	119.3	C8—C14—H14A	119.7
O1—C7—N1	120.0 (2)	C4—O2—H02A	110 (3)
O1—C7—C1	122.8 (2)	C9—O3—H03A	105.8 (19)
N1—C7—C1	117.1 (2)	C7—N1—N2	117.6 (2)
C9—C8—C13	118.3 (2)	C7—N1—H1N	123.3 (16)
C9—C8—C14	122.4 (2)	N2—N1—H1N	119.0 (16)
C13—C8—C14	119.2 (2)	C14—N2—N1	118.5 (2)
C6—C1—C2—C3	0.9 (4)	C13—C8—C9—C10	−0.2 (3)
C7—C1—C2—C3	−179.6 (2)	C14—C8—C9—C10	179.9 (2)
C1—C2—C3—C4	−0.3 (4)	O3—C9—C10—C11	−179.2 (2)
C2—C3—C4—O2	179.8 (2)	C8—C9—C10—C11	−0.2 (4)
C2—C3—C4—C5	−0.3 (4)	C9—C10—C11—C12	0.7 (4)
O2—C4—C5—C6	−179.7 (2)	C10—C11—C12—C13	−0.9 (4)
C3—C4—C5—C6	0.5 (4)	C11—C12—C13—C8	0.6 (4)
C4—C5—C6—C1	0.1 (4)	C9—C8—C13—C12	0.0 (4)
C2—C1—C6—C5	−0.8 (3)	C14—C8—C13—C12	179.9 (2)
C7—C1—C6—C5	179.7 (2)	C9—C8—C14—N2	−3.3 (4)
C2—C1—C7—O1	161.2 (2)	C13—C8—C14—N2	176.8 (2)
C6—C1—C7—O1	−19.3 (3)	O1—C7—N1—N2	0.1 (3)
C2—C1—C7—N1	−19.4 (3)	C1—C7—N1—N2	−179.32 (19)
C6—C1—C7—N1	160.1 (2)	C8—C14—N2—N1	−179.2 (2)
C13—C8—C9—O3	178.8 (2)	C7—N1—N2—C14	−179.3 (2)
C14—C8—C9—O3	−1.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H02A···O1^i	0.85 (2)	1.85 (2)	2.698 (3)	172 (4)
O3—H03A···N2	0.85 (2)	1.86 (2)	2.620 (3)	149 (3)
N1—H1N···O3^ii	0.88 (2)	2.33 (2)	3.153 (3)	156 (2)

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