1,2-Bis(3-hydroxy­benzyl­idene)diazane

Zhu, L.; Zhao, X.-H.

doi:10.1107/S1600536809027652

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1929

doi:10.1107/S1600536809027652

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1,2-Bis(3-hydroxybenzylidene)diazane

Ling Zhu ^a and Xin-Hua Zhao ^b ^*

^aSchool of Chemistry and Life Science, Maoming University, Maoming 525000, People's Republic of China, and ^bSchool of Public Health, Guangdong Pharmaceutical University, Guangzhou 510006, People's Republic of China
^*Correspondence e-mail: zhaoxh_gpu@163.com

(Received 9 July 2009; accepted 14 July 2009; online 18 July 2009)

The asymmetric unit of the title compound, C₁₄H₁₂N₂O₂, which was synthesized unexpectedly by refluxing an ethanolic solution of isonicotinic hydrazide and 3-hydroxybenzaldehyde, contains one half-molecule with the center of the N—N bond lying on a crystallographic center of inversion. In the crystal structure, molecules are linked by intermolecular O—H⋯N hydrogen bonds into an infinite layer structure parallel to (110).

Related literature

For general background to salicyclic aldehyde complexes, see: Zelewsky & von Knof (1999 ); Alam et al. (2003 ).

Experimental

Crystal data

C₁₄H₁₂N₂O₂
M_r = 240.26
Monoclinic, P 2₁ /n
a = 4.883 (2) Å
b = 8.212 (3) Å
c = 14.575 (6) Å
β = 95.267 (6)°
V = 582.0 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.12 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.989, T_max = 0.993
4234 measured reflections
1079 independent reflections
814 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.185
S = 1.00
1079 reflections
83 parameters
H-atom parameters not refined
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H2⋯N1ⁱ	0.82	2.03	2.811 (3)	159
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809027652/im2128sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809027652/im2128Isup2.hkl

checkCIF report

Comment top

The synthesis of complexes consisting of ligands derived from salicylic aldehyde has attracted continuous research interest not only with regard to their appealing structural and topological novelty, but also due to their unusual optical, electronic, magnetic and catalytic properties as well as their potential medical application (Zelewsky et al. 1999; Alam et al. 2003). In the present paper, we describe the synthesis and structural characterization of N,N'-di(3-hydroxybenzylidene)-hydrazine.

As shown in Fig. 1, the asymmetrical unit contains one half of the molecule. The center of the N-N bond represents a crystallographic center of inversion. One intermolecular hydrogen bond O(1)—H(2)···N(1) (2.811 (3) Å) is observed in the crystal structure leading to infinite layers of molecules (Fig. 2).

Related literature top

For general background to salicyclic aldehyde complexes, see: Zelewsky et al. (1999); Alam et al. (2003).

Experimental top

An ethanolic solution of isonicotinic hydrazide (10 mmol) and 3-hydroxybenzaldehyde (10 mmol) refluxed for five hours. After filtration a yellow powder was obtained. Suitable crystals for X-ray diffraction were obtained by recrystallization from dichloromethane. Anal. Calc. for C₁₄H₁₂N₂O₂: C 69.92, H 4.99, N 9.99%; Found: C 69.89, H 4.79, N 9.78.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), drawn with 50% probability displacement ellipsoids.
	Fig. 2. Three-dimensional network formed by hydrogen bonds (dashed lines).

1,2-Bis(3-hydroxybenzylidene)diazane top

Crystal data top

C₁₄H₁₂N₂O₂	F(000) = 252
M_r = 240.26	D_x = 1.371 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1079 reflections
a = 4.883 (2) Å	θ = 2.8–25.5°
b = 8.212 (3) Å	µ = 0.09 mm⁻¹
c = 14.575 (6) Å	T = 295 K
β = 95.267 (6)°	Block, yellow
V = 582.0 (4) Å³	0.12 × 0.10 × 0.08 mm
Z = 2

Data collection top

Bruker APEXII CCD area-detector diffractometer	1079 independent reflections
Radiation source: fine-focus sealed tube	814 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −5→5
T_min = 0.989, T_max = 0.993	k = −9→9
4234 measured reflections	l = −17→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.185	H-atom parameters not refined
S = 1.00	w = 1/[σ²(F_o²) + (0.103P)² + 0.3322P] where P = (F_o² + 2F_c²)/3
1079 reflections	(Δ/σ)_max < 0.001
83 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₄H₁₂N₂O₂	V = 582.0 (4) Å³
M_r = 240.26	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.883 (2) Å	µ = 0.09 mm⁻¹
b = 8.212 (3) Å	T = 295 K
c = 14.575 (6) Å	0.12 × 0.10 × 0.08 mm
β = 95.267 (6)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1079 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	814 reflections with I > 2σ(I)
T_min = 0.989, T_max = 0.993	R_int = 0.039
4234 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.185	H-atom parameters not refined
S = 1.00	Δρ_max = 0.62 e Å⁻³
1079 reflections	Δρ_min = −0.23 e Å⁻³
83 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.3137 (6)	0.2100 (3)	0.82062 (17)	0.0364 (7)
H3	0.1725	0.1396	0.7996	0.044*
C2	0.4468 (6)	0.2997 (3)	0.75848 (18)	0.0380 (7)
C3	0.6607 (6)	0.4021 (4)	0.7888 (2)	0.0434 (8)
H6	0.7546	0.4600	0.7467	0.052*
C4	0.7340 (6)	0.4175 (4)	0.8822 (2)	0.0469 (8)
H9	0.8749	0.4882	0.9031	0.056*
C5	0.6000 (6)	0.3292 (4)	0.94433 (19)	0.0414 (8)
H7	0.6516	0.3401	1.0070	0.050*
C6	0.3891 (6)	0.2240 (3)	0.91470 (17)	0.0342 (7)
C7	0.2426 (6)	0.1379 (3)	0.98224 (18)	0.0367 (7)
H4	0.2836	0.1634	1.0441	0.044*
N1	0.0615 (5)	0.0295 (3)	0.96142 (14)	0.0358 (6)
O1	0.3545 (6)	0.2849 (3)	0.66792 (14)	0.0637 (8)
H2	0.4174	0.3590	0.6386	0.096*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0469 (16)	0.0311 (14)	0.0322 (15)	0.0014 (12)	0.0096 (12)	0.0011 (11)
C2	0.0528 (17)	0.0348 (15)	0.0280 (14)	0.0046 (13)	0.0126 (12)	0.0034 (11)
C3	0.0420 (16)	0.0442 (17)	0.0463 (18)	0.0016 (13)	0.0157 (13)	0.0103 (14)
C4	0.0448 (17)	0.0431 (17)	0.0520 (18)	−0.0014 (14)	−0.0003 (14)	0.0064 (14)
C5	0.0475 (17)	0.0418 (17)	0.0343 (15)	0.0059 (14)	0.0004 (13)	0.0027 (12)
C6	0.0413 (15)	0.0338 (15)	0.0286 (13)	0.0092 (12)	0.0095 (11)	0.0029 (11)
C7	0.0501 (17)	0.0369 (16)	0.0241 (13)	0.0076 (13)	0.0085 (12)	0.0016 (11)
N1	0.0514 (14)	0.0354 (12)	0.0228 (11)	0.0081 (11)	0.0150 (9)	0.0040 (9)
O1	0.105 (2)	0.0549 (15)	0.0329 (12)	−0.0206 (14)	0.0170 (12)	0.0046 (10)

Geometric parameters (Å, º) top

C1—C2	1.376 (4)	C4—H9	0.9300
C1—C6	1.392 (4)	C5—C6	1.382 (4)
C1—H3	0.9300	C5—H7	0.9300
C2—O1	1.360 (3)	C6—C7	1.453 (4)
C2—C3	1.382 (4)	C7—N1	1.272 (4)
C3—C4	1.382 (4)	C7—H4	0.9300
C3—H6	0.9300	N1—N1ⁱ	1.409 (4)
C4—C5	1.372 (4)	O1—H2	0.8200

C2—C1—C6	120.4 (3)	C4—C5—C6	120.7 (3)
C2—C1—H3	119.8	C4—C5—H7	119.6
C6—C1—H3	119.8	C6—C5—H7	119.6
O1—C2—C1	117.2 (3)	C5—C6—C1	118.8 (3)
O1—C2—C3	122.5 (3)	C5—C6—C7	119.4 (2)
C1—C2—C3	120.3 (3)	C1—C6—C7	121.7 (3)
C2—C3—C4	119.4 (3)	N1—C7—C6	123.6 (2)
C2—C3—H6	120.3	N1—C7—H4	118.2
C4—C3—H6	120.3	C6—C7—H4	118.2
C5—C4—C3	120.4 (3)	C7—N1—N1ⁱ	112.8 (3)
C5—C4—H9	119.8	C2—O1—H2	109.5
C3—C4—H9	119.8

Symmetry code: (i) −x, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H2···N1ⁱⁱ	0.82	2.03	2.811 (3)	159

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂N₂O₂
M_r	240.26
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	4.883 (2), 8.212 (3), 14.575 (6)
β (°)	95.267 (6)
V (Å³)	582.0 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.989, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	4234, 1079, 814
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.185, 1.00
No. of reflections	1079
No. of parameters	83
H-atom treatment	H-atom parameters not refined
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.23

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H2···N1ⁱ	0.82	2.03	2.811 (3)	158.9

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

Acknowledgements

The authors acknowledge financial support from the scientific research start-up funds of talent introduction in Guangdong Pharmaceutical University.

References

Alam, M. A., Nethaji, M. & Ray, M. (2003). Angew. Chem. Int. Ed. 42, 1940–1942. Web of Science CSD CrossRef CAS Google Scholar
Bruker (2001). SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zelewsky, A. & von Knof, U. (1999). Angew. Chem. Int. Ed. 38, 302–322. Google Scholar