N,N'-Bis(4-hydroxy­benzyl­idene)hydrazine

The crystal structure of the title compound, C₁₄H₁₂N₂O₂, is stabilized by inter­molecular hydrogen-bonding inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 153 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.046
• wR factor = 0.147
• Data-to-parameter ratio = 16.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT417_ALERT_2_B Short Inter D-H..H-D       H1O    ..  H2O     ..       1.11 Ang.

Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT755_ALERT_4_C D-H     Calc     0.84000, Rep    0.84(10) ......  Senseless su
              O1   -H1O     1.555   1.555
PLAT755_ALERT_4_C D-H     Calc     0.84000, Rep    0.84(10) ......  Senseless su
              O1   -H1O     1.555   1.555
PLAT755_ALERT_4_C D-H     Calc     0.84000, Rep    0.84(10) ......  Senseless su
              O2   -H2O     1.555   1.555
PLAT755_ALERT_4_C D-H     Calc     0.84000, Rep    0.84(10) ......  Senseless su
              O2   -H2O     1.555   1.555
PLAT756_ALERT_4_C H...A   Calc     1.11000, Rep    1.11(10) ......  Senseless su
              H1O  -H2O     1.555   1.666
PLAT756_ALERT_4_C H...A   Calc     1.94000, Rep    1.94(10) ......  Senseless su
              H1O  -O2      1.555   1.666
PLAT756_ALERT_4_C H...A   Calc     1.11000, Rep    1.11(10) ......  Senseless su
              H2O  -H1O     1.555   1.444
PLAT756_ALERT_4_C H...A   Calc     1.93000, Rep    1.93(10) ......  Senseless su
              H2O  -O1      1.555   1.444
PLAT757_ALERT_4_C D...A   Calc     1.93000, Rep  1.9303(16) ......  Senseless su
              O1   -H2O     1.555   1.666
PLAT757_ALERT_4_C D...A   Calc     1.94000, Rep  1.9393(15) ......  Senseless su
              O2   -H1O     1.555   1.444

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
  12 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
  10 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Acylhydrazones have been extensively investigated in recent years, as they are associated with various biological activities (Buu-Hoi et al.,1953). Furthermore, it also has interesting analytical properties (Singh et al., 1982) and can be used as ligands in orgamometallic catalysts (Lal et al., 1997). 2,2'-Azinodi-2-hydroxytoluene and N,N'-bis(4-chlorobenzylidene)hydrazine have been reported by Xu et al., 1994 and Zheng et al., 2005, respectively.

The molecular structure of the title compound (Fig. 1) contains intermolecular hydrogen bond [O1—H1O···O2 = 2.7302 (16) Å](Table 2), leading to an one-dimensional chain. Interesting another chain was hydrogen-bonded reversely to the chain through the other type of intermolecular hydrogen bond [O1—H10···N1 = 2.7590 (14) Å]. Thus, the structure can be attributted to a two dimensional framework (Fig.2). Two types of hydrogen bonds make the structure stabilize.

Related literature

For related literature, see: Buu-Hoi et al., (1953); Lal et al. (1997); Singh et al. (1982); Xu et al. (1994); Zheng et al. (2005).

S2. Experimental

The mixture of 4-hydroxybenzaldehyde (0.244 g) in 20 ml me thanol and hydrazine (0.146 g) in 40 ml me thanol was stirred 2 h with refluxing. The yellow produce was isolated by filtration, washed with diethyl ether and dried at room temperature for a yield of 0.15 g (53%). Analysis found (calculated) for the title compound (%): C 69.51(69.99); H 4.72(5.03); N 10.93 (11.66); O 14.84(13.32).

S3. Refinement

The H atoms attached to the parent C were geometrically fixed with, and were treated as riding atoms, whereas the H atoms attached to the parent O atom were located from difference maps and were refined freely. The H atoms were positioned geometrically, with C—H = 0.95 - 0.99 Å, and refined as riding with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of the molecule of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The packing structure of the title compound viewed down the a axis showing the molecular.

N,N'-Bis(4-Hydroxybenzylidene)hydrazine

Crystal data

C14H12N2O2	F(000) = 504
Mr = 240.26	Dx = 1.368 Mg m^−3
Monoclinic, P21/c	Melting point: 528 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 12.587 (3) Å	Cell parameters from 8183 reflections
b = 8.5349 (17) Å	θ = 3.0–27.5°
c = 11.897 (2) Å	µ = 0.09 mm^−1
β = 114.12 (3)°	T = 153 K
V = 1166.6 (4) Å^3	Chip, colourless
Z = 4	0.34 × 0.33 × 0.03 mm

Data collection

Rigaku R-AXIS SPIDER diffractometer	2663 independent reflections
Radiation source: fine-focus sealed tube	2075 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −16→16
Tmin = 0.969, Tmax = 0.997	k = −10→11
10931 measured reflections	l = −15→15

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)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.147	w = 1/[σ^2(Fo^2) + (0.0904P)^2 + 0.38P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.009
2663 reflections	Δρmax = 0.33 e Å^−3
164 parameters	Δρmin = −0.27 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.010 (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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

- 1.0038 (0.0089) x - 6.8322 (0.0048) y + 6.8379 (0.0074) z = 1.7177 (0.0012)

* 0.0000 (0.0011) C9 * 0.0033 (0.0011) C10 * -0.0039 (0.0011) C11 * 0.0012 (0.0011) C12 * 0.0022 (0.0012) C13 * -0.0028 (0.0011) C14

Rms deviation of fitted atoms = 0.0026

1.7154 (0.0212) x - 6.9219 (0.0065) y + 5.5155 (0.0214) z = 1.9752 (0.0035)

Angle to previous plane (with approximate esd) = 12.50 ( 0.18 )

* -0.0847 (0.0007) C7 * -0.0854 (0.0007) C8 * 0.0845 (0.0007) N1 * 0.0856 (0.0007) N2

Rms deviation of fitted atoms = 0.0850

1.6200 (0.0080) x - 6.7985 (0.0046) y + 5.7888 (0.0069) z = 1.9768 (0.0052)

Angle to previous plane (with approximate esd) = 1.56 ( 0.19 )

* 0.0152 (0.0010) C1 * -0.0105 (0.0010) C2 * -0.0041 (0.0010) C3 * 0.0141 (0.0010) C4 * -0.0097 (0.0010) C5 * -0.0049 (0.0010) C6

Rms deviation of fitted atoms = 0.0106

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	0.72875 (8)	0.61870 (12)	0.87357 (10)	0.0250 (3)
H1O	0.7962	0.6248	0.8759	0.038*
O2	−0.04201 (10)	−0.33486 (15)	−0.09068 (12)	0.0354 (3)
H2O	−0.1107	−0.3454	−0.0975	0.053*
N1	0.36829 (10)	0.16168 (14)	0.46180 (12)	0.0218 (3)
N2	0.32543 (10)	0.06609 (15)	0.35537 (12)	0.0237 (3)
C1	0.66180 (12)	0.52650 (16)	0.77724 (13)	0.0205 (3)
C2	0.54791 (11)	0.48685 (16)	0.75810 (13)	0.0206 (3)
H2	0.5150	0.5274	0.8111	0.025*
C3	0.48322 (12)	0.38881 (16)	0.66218 (14)	0.0210 (3)
H3	0.4062	0.3614	0.6502	0.025*
C4	0.52981 (12)	0.32924 (16)	0.58232 (13)	0.0205 (3)
C5	0.64248 (12)	0.37493 (17)	0.60033 (14)	0.0235 (3)
H5	0.6743	0.3385	0.5452	0.028*
C6	0.70851 (12)	0.47210 (18)	0.69680 (14)	0.0244 (3)
H6	0.7850	0.5014	0.7080	0.029*
C7	0.46655 (12)	0.22489 (16)	0.47989 (14)	0.0222 (3)
H7	0.4999	0.2022	0.4231	0.027*
C8	0.21725 (12)	0.03528 (17)	0.31936 (14)	0.0229 (3)
H8	0.1770	0.0776	0.3647	0.028*
C9	0.15253 (12)	−0.06125 (17)	0.21241 (14)	0.0225 (3)
C10	0.03306 (13)	−0.07915 (18)	0.17746 (15)	0.0261 (3)
H10	−0.0030	−0.0285	0.2239	0.031*
C11	−0.03409 (12)	−0.16936 (18)	0.07641 (15)	0.0267 (4)
H11	−0.1155	−0.1793	0.0533	0.032*
C12	0.01847 (13)	−0.24519 (18)	0.00911 (14)	0.0249 (3)
C13	0.13789 (13)	−0.22885 (19)	0.04311 (15)	0.0281 (4)
H13	0.1738	−0.2808	−0.0029	0.034*
C14	0.20428 (12)	−0.13778 (18)	0.14312 (15)	0.0255 (3)
H14	0.2855	−0.1269	0.1652	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0173 (5)	0.0312 (6)	0.0239 (6)	−0.0057 (4)	0.0056 (4)	−0.0074 (4)
O2	0.0274 (6)	0.0478 (7)	0.0314 (7)	−0.0141 (5)	0.0123 (5)	−0.0180 (5)
N1	0.0228 (6)	0.0218 (6)	0.0169 (6)	−0.0009 (5)	0.0044 (5)	−0.0021 (5)
N2	0.0253 (6)	0.0251 (6)	0.0188 (6)	−0.0023 (5)	0.0070 (5)	−0.0035 (5)
C1	0.0201 (6)	0.0192 (6)	0.0195 (7)	−0.0004 (5)	0.0055 (5)	−0.0003 (5)
C2	0.0199 (6)	0.0216 (7)	0.0213 (7)	−0.0008 (5)	0.0093 (5)	−0.0009 (5)
C3	0.0186 (6)	0.0218 (7)	0.0221 (7)	−0.0021 (5)	0.0081 (5)	0.0000 (5)
C4	0.0219 (6)	0.0199 (7)	0.0184 (7)	−0.0002 (5)	0.0070 (5)	0.0007 (5)
C5	0.0227 (7)	0.0271 (7)	0.0225 (8)	0.0020 (5)	0.0110 (6)	−0.0010 (6)
C6	0.0178 (6)	0.0293 (8)	0.0260 (8)	−0.0024 (5)	0.0088 (6)	−0.0012 (6)
C7	0.0239 (7)	0.0231 (7)	0.0189 (7)	0.0013 (5)	0.0082 (6)	0.0002 (5)
C8	0.0235 (7)	0.0247 (7)	0.0195 (7)	−0.0002 (5)	0.0076 (6)	−0.0015 (6)
C9	0.0227 (7)	0.0235 (7)	0.0196 (7)	−0.0026 (5)	0.0069 (5)	0.0001 (6)
C10	0.0246 (7)	0.0304 (8)	0.0250 (8)	−0.0023 (6)	0.0119 (6)	−0.0038 (6)
C11	0.0203 (7)	0.0324 (8)	0.0268 (8)	−0.0056 (6)	0.0092 (6)	−0.0028 (6)
C12	0.0260 (7)	0.0270 (7)	0.0205 (7)	−0.0073 (6)	0.0082 (6)	−0.0036 (6)
C13	0.0254 (7)	0.0329 (8)	0.0276 (8)	−0.0036 (6)	0.0125 (6)	−0.0077 (6)
C14	0.0199 (6)	0.0293 (8)	0.0265 (8)	−0.0030 (5)	0.0086 (6)	−0.0039 (6)

Geometric parameters (Å, º)

O1—C1	1.3615 (17)	C5—H5	0.9500
O1—H1O	0.8400	C6—H6	0.9500
O2—C12	1.3550 (19)	C7—H7	0.9500
O2—H2O	0.8400	C8—C9	1.454 (2)
N1—C7	1.2843 (19)	C8—H8	0.9500
N1—N2	1.4148 (17)	C9—C10	1.395 (2)
N2—C8	1.2767 (19)	C9—C14	1.403 (2)
C1—C6	1.392 (2)	C10—C11	1.386 (2)
C1—C2	1.3982 (18)	C10—H10	0.9500
C2—C3	1.3806 (19)	C11—C12	1.390 (2)
C2—H2	0.9500	C11—H11	0.9500
C3—C4	1.400 (2)	C12—C13	1.395 (2)
C3—H3	0.9500	C13—C14	1.380 (2)
C4—C5	1.400 (2)	C13—H13	0.9500
C4—C7	1.456 (2)	C14—H14	0.9500
C5—C6	1.384 (2)
C1—O1—H1O	109.5	N1—C7—H7	118.1
C12—O2—H2O	109.5	C4—C7—H7	118.1
C7—N1—N2	112.40 (13)	N2—C8—C9	123.35 (14)
C8—N2—N1	112.55 (13)	N2—C8—H8	118.3
O1—C1—C6	118.79 (12)	C9—C8—H8	118.3
O1—C1—C2	121.18 (13)	C10—C9—C14	118.45 (14)
C6—C1—C2	120.02 (13)	C10—C9—C8	118.23 (14)
C3—C2—C1	120.03 (13)	C14—C9—C8	123.31 (13)
C3—C2—H2	120.0	C11—C10—C9	121.35 (14)
C1—C2—H2	120.0	C11—C10—H10	119.3
C2—C3—C4	120.79 (12)	C9—C10—H10	119.3
C2—C3—H3	119.6	C10—C11—C12	119.55 (13)
C4—C3—H3	119.6	C10—C11—H11	120.2
C3—C4—C5	118.28 (13)	C12—C11—H11	120.2
C3—C4—C7	123.55 (13)	O2—C12—C11	122.59 (13)
C5—C4—C7	118.16 (13)	O2—C12—C13	117.62 (14)
C6—C5—C4	121.41 (14)	C11—C12—C13	119.78 (14)
C6—C5—H5	119.3	C14—C13—C12	120.49 (14)
C4—C5—H5	119.3	C14—C13—H13	119.8
C5—C6—C1	119.39 (13)	C12—C13—H13	119.8
C5—C6—H6	120.3	C13—C14—C9	120.37 (13)
C1—C6—H6	120.3	C13—C14—H14	119.8
N1—C7—C4	123.86 (14)	C9—C14—H14	119.8
C7—N1—N2—C8	−163.47 (13)	N1—N2—C8—C9	−179.73 (12)
O1—C1—C2—C3	−177.79 (12)	N2—C8—C9—C10	−176.21 (15)
C6—C1—C2—C3	2.5 (2)	N2—C8—C9—C14	4.1 (2)
C1—C2—C3—C4	−0.7 (2)	C14—C9—C10—C11	−0.4 (2)
C2—C3—C4—C5	−1.6 (2)	C8—C9—C10—C11	179.94 (14)
C2—C3—C4—C7	179.70 (13)	C9—C10—C11—C12	0.8 (2)
C3—C4—C5—C6	2.2 (2)	C10—C11—C12—O2	−179.88 (14)
C7—C4—C5—C6	−179.07 (13)	C10—C11—C12—C13	−0.5 (2)
C4—C5—C6—C1	−0.4 (2)	O2—C12—C13—C14	179.33 (14)
O1—C1—C6—C5	178.33 (13)	C11—C12—C13—C14	0.0 (2)
C2—C1—C6—C5	−1.9 (2)	C12—C13—C14—C9	0.4 (2)
N2—N1—C7—C4	179.69 (12)	C10—C9—C14—C13	−0.2 (2)
C3—C4—C7—N1	−9.1 (2)	C8—C9—C14—C13	179.45 (14)
C5—C4—C7—N1	172.24 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···H2O^i	0.84 (10)	1.11 (10)	1.9303 (16)	163 (1)
O1—H1O···O2^i	0.84 (10)	1.94 (10)	2.7679 (16)	169 (1)
O2—H2O···H1O^ii	0.84 (10)	1.11 (10)	1.9393 (15)	168 (1)
O2—H2O···O1^ii	0.84 (10)	1.93 (10)	2.7679 (16)	175 (1)

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