N,N′-Disalicyloylhydrazine

Chen, Y.-T.; Li, D.-C.; Wang, D.-Q.; Zhu, Y.-H.

doi:10.1107/S160053680706312X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o120

https://doi.org/10.1107/S160053680706312X

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N,N′-Disalicyloylhydrazine

Yu-Ting Chen,^a,^b Da-Cheng Li,^a ^* Da-Qi Wang ^a and Yue-Hua Zhu ^c

^aSchool of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, People's Republic of China, ^bDepartment of Chemistry, Dezhou University, Dezhou 253023, People's Republic of China, and ^cSchool of Materials Science and Engineering, Liaocheng University, Liaocheng 252059, People's Republic of China
^*Correspondence e-mail: dougroup@163.com

(Received 21 November 2007; accepted 25 November 2007; online 6 December 2007)

The approximately planar molecule of the title compound, C₁₄H₁₂N₂O₄, is centrosymmetric and has an E configuration with respect to the N—N bond. This compound adopts the ketoamine form with C=O and C—N distances of 1.233 (3) and 1.331 (4) Å, respectively. Adjacent molecules are assembled into a two-dimensional supramolecular structure parallel to the (101) plane via intermolecular O—H⋯O hydrogen bonds.

Related literature

For metallacrowns with unsymmetrical aroylhydrazone ligands, see: John et al. (2006 ); Dou et al. (2006 ). For the crystal structure of an iron compound with N,N′-bis-picolinoyl hydrazine, see: Bernhardt et al. (2005 ). For the preparation of 2-acetyl-2-hydroxynaphthohydrazide, see: Liu et al. (2006 ).

Experimental

Crystal data

C₁₄H₁₂N₂O₄
M_r = 272.26
Monoclinic, P 2₁ /n
a = 8.3816 (18) Å
b = 6.2909 (15) Å
c = 12.376 (2) Å
β = 105.463 (2)°
V = 628.9 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 298 (2) K
0.18 × 0.15 × 0.14 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.981, T_max = 0.985
3082 measured reflections
1102 independent reflections
618 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.163
S = 1.03
1102 reflections
92 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱⁱ	0.82	1.81	2.617 (3)	166
N1—H1⋯O2	0.86	1.89	2.580 (3)	136
Symmetry code: (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053680706312X/si2060sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680706312X/si2060Isup2.hkl

checkCIF report

Comment top

Aroylhydrazine ligands have recently gained the increasing concern due to their quite interesting chemical activities (John et al., 2006; Dou et al., 2006). However, most of the studies are focused on unsymmetrical aroylhydrazine, while symmetrical diaroylhydrazines receive much less attention (Bernhardt et al., 2005). In order to explore the impact of the structural character of symmetrical ligands on the properties of the complexes, the title compound, was synthesized by the self-combination of salicyloylhydrazine on the acidic environment.

The title molecule has crystallographic inversion symmetry (Fig. 1) and goes near to co-planar with the mean deviation of 0.0584Å from the least-squares plane of all non-hydrogen atoms. An E configuration with respect to the N—N bond is observed. The distance of C1—O1 is 1.233 (3) Å, typical of a double bond, whereas the distances of C1—N1 and N1—N1ⁱ at 1.331 (4)Å and 1.373 (4) Å, respectively are typical for a single bond (Table. 1), which is in agreement with that of the analogous compound (Liu et al., 2006), suggesting this diaroylhydrazine exists in the ketoamino form. All oxygen atoms in the title compound participate in intermolecular H-bond interactions with their neighbors, leading to one molecule bound with four molecules through O—H···O interactions. The dihedral angle of two adjacent molecules linked by O—H···O hydrogen bond is 65.7°. In such a recognition pattern, the two-dimensional network structure is assembled parallel to the (1 0 1) plane, as shown in Fig. 2.

Related literature top

For metallacrowns with unsymmetrical aroylhydrazone ligands, see: John et al. (2006); Dou et al. (2006). For the crystal structure of a iron compound with N,N'-bis-picolinoyl hydrazine, see: Bernhardt et al. (2005). For the preparation of 2-acetyl-2-hydroxynaphthohydrazide, see: Liu et al. (2006).

Experimental top

The salicyloylhydrazine(6.08 g, 40 mmol) was added to the solution of ice acetic acid(3 ml) in methanol(20 ml). After refluxed for three hours, the mixture was filtrated. Then colorless needle crystals suitable for X-ray diffraction were obtained by vaporizing the filtrate at room temperature. Yield: 4.23 g, 77.76%. m.p.: 565–567 K. Anal. for C₁₄H₁₂N₂O₄: Calc. C, 61.76; H, 4.44; N, 10.29; Found: C, 61.52; H, 4.51; N, 10.28%. The No. of CCDC: 614757.

Structure description top

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. Symmetry code (i): -x + 2,-y + 1,-z + 1
	Fig. 2. Two-dimensional network of the compound. Symmetry code (ii): x + 1/2, -y + 3/2, z + 1/2.

N,N'-Disalicyloylhydrazine top

Crystal data top

C₁₄H₁₂N₂O₄	F(000) = 284
M_r = 272.26	D_x = 1.438 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 678 reflections
a = 8.3816 (18) Å	θ = 2.6–25.5°
b = 6.2909 (15) Å	µ = 0.11 mm⁻¹
c = 12.376 (2) Å	T = 298 K
β = 105.463 (2)°	Block, colorless
V = 628.9 (2) Å³	0.18 × 0.15 × 0.14 mm
Z = 2

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	1102 independent reflections
Radiation source: fine-focus sealed tube	618 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
φ and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.981, T_max = 0.985	k = −7→7
3082 measured reflections	l = −6→14

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.163	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0827P)² + 0.0895P] where P = (F_o² + 2F_c²)/3
1102 reflections	(Δ/σ)_max < 0.001
92 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₄H₁₂N₂O₄	V = 628.9 (2) Å³
M_r = 272.26	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.3816 (18) Å	µ = 0.11 mm⁻¹
b = 6.2909 (15) Å	T = 298 K
c = 12.376 (2) Å	0.18 × 0.15 × 0.14 mm
β = 105.463 (2)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	1102 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	618 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.985	R_int = 0.042
3082 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.163	H-atom parameters constrained
S = 1.03	Δρ_max = 0.30 e Å⁻³
1102 reflections	Δρ_min = −0.19 e Å⁻³
92 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
N1	0.9962 (3)	0.5894 (4)	0.53095 (19)	0.0462 (7)
H1	1.0781	0.6229	0.5867	0.055*
O1	0.7444 (2)	0.6612 (3)	0.42420 (17)	0.0576 (7)
O2	1.1131 (3)	0.8180 (4)	0.70745 (18)	0.0696 (8)
H2	1.1607	0.8443	0.7730	0.104*
C1	0.8612 (4)	0.7109 (5)	0.5042 (2)	0.0419 (8)
C2	0.8605 (3)	0.9011 (4)	0.5739 (2)	0.0372 (7)
C3	0.9807 (3)	0.9503 (5)	0.6721 (2)	0.0419 (7)
C4	0.9670 (4)	1.1325 (5)	0.7318 (3)	0.0502 (9)
H4	1.0485	1.1646	0.7971	0.060*
C5	0.8344 (4)	1.2655 (6)	0.6953 (3)	0.0550 (9)
H5	0.8257	1.3872	0.7360	0.066*
C6	0.7137 (4)	1.2198 (5)	0.5984 (3)	0.0550 (9)
H6	0.6238	1.3105	0.5737	0.066*
C7	0.7265 (3)	1.0410 (5)	0.5388 (3)	0.0475 (8)
H7	0.6446	1.0114	0.4734	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0449 (14)	0.0496 (16)	0.0396 (15)	−0.0013 (12)	0.0033 (12)	−0.0122 (11)
O1	0.0524 (13)	0.0698 (16)	0.0397 (12)	−0.0048 (11)	−0.0066 (10)	−0.0061 (11)
O2	0.0648 (16)	0.0800 (17)	0.0481 (14)	0.0250 (13)	−0.0125 (11)	−0.0230 (13)
C1	0.0430 (18)	0.0471 (18)	0.0336 (15)	−0.0016 (14)	0.0067 (14)	0.0045 (14)
C2	0.0375 (16)	0.0409 (17)	0.0357 (16)	−0.0006 (13)	0.0141 (13)	0.0018 (13)
C3	0.0370 (15)	0.0487 (17)	0.0384 (16)	0.0066 (14)	0.0073 (13)	−0.0016 (15)
C4	0.0476 (19)	0.056 (2)	0.0465 (18)	−0.0038 (16)	0.0127 (15)	−0.0124 (16)
C5	0.063 (2)	0.0485 (19)	0.061 (2)	−0.0016 (17)	0.0303 (19)	−0.0077 (17)
C6	0.054 (2)	0.050 (2)	0.065 (2)	0.0137 (16)	0.0226 (18)	0.0076 (18)
C7	0.0389 (16)	0.055 (2)	0.0465 (18)	0.0052 (15)	0.0079 (14)	0.0074 (16)

Geometric parameters (Å, º) top

N1—C1	1.331 (3)	C3—C4	1.384 (4)
N1—N1ⁱ	1.372 (4)	C4—C5	1.368 (4)
N1—H1	0.8600	C4—H4	0.9300
O1—C1	1.233 (3)	C5—C6	1.377 (5)
O2—C3	1.363 (3)	C5—H5	0.9300
O2—H2	0.8200	C6—C7	1.365 (4)
C1—C2	1.476 (4)	C6—H6	0.9300
C2—C3	1.391 (4)	C7—H7	0.9300
C2—C7	1.402 (4)

C1—N1—N1ⁱ	119.7 (3)	C5—C4—C3	120.4 (3)
C1—N1—H1	120.2	C5—C4—H4	119.8
N1ⁱ—N1—H1	120.2	C3—C4—H4	119.8
C3—O2—H2	109.5	C4—C5—C6	120.2 (3)
O1—C1—N1	119.6 (3)	C4—C5—H5	119.9
O1—C1—C2	123.3 (3)	C6—C5—H5	119.9
N1—C1—C2	117.1 (2)	C7—C6—C5	119.8 (3)
C3—C2—C7	117.7 (3)	C7—C6—H6	120.1
C3—C2—C1	125.2 (2)	C5—C6—H6	120.1
C7—C2—C1	117.1 (2)	C6—C7—C2	121.4 (3)
O2—C3—C4	120.7 (3)	C6—C7—H7	119.3
O2—C3—C2	118.8 (3)	C2—C7—H7	119.3
C4—C3—C2	120.5 (3)

N1ⁱ—N1—C1—O1	0.1 (5)	C1—C2—C3—C4	−179.4 (3)
N1ⁱ—N1—C1—C2	−180.0 (3)	O2—C3—C4—C5	179.4 (3)
O1—C1—C2—C3	172.2 (3)	C2—C3—C4—C5	0.5 (4)
N1—C1—C2—C3	−7.7 (4)	C3—C4—C5—C6	−0.4 (5)
O1—C1—C2—C7	−6.7 (4)	C4—C5—C6—C7	0.1 (5)
N1—C1—C2—C7	173.3 (3)	C5—C6—C7—C2	0.1 (5)
C7—C2—C3—O2	−179.3 (3)	C3—C2—C7—C6	0.1 (4)
C1—C2—C3—O2	1.7 (4)	C1—C2—C7—C6	179.1 (3)
C7—C2—C3—C4	−0.4 (4)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱⁱ	0.82	1.81	2.617 (3)	166
N1—H1···O2	0.86	1.89	2.580 (3)	136

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂N₂O₄
M_r	272.26
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	8.3816 (18), 6.2909 (15), 12.376 (2)
β (°)	105.463 (2)
V (Å³)	628.9 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.18 × 0.15 × 0.14

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.981, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	3082, 1102, 618
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.163, 1.03
No. of reflections	1102
No. of parameters	92
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.19

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

Selected geometric parameters (Å, º) top

N1—C1	1.331 (3)	O1—C1	1.233 (3)
N1—N1ⁱ	1.372 (4)	O2—C3	1.363 (3)

C1—N1—N1ⁱ	119.7 (3)	O1—C1—C2	123.3 (3)
O1—C1—N1	119.6 (3)	N1—C1—C2	117.1 (2)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱⁱ	0.82	1.81	2.617 (3)	165.6
N1—H1···O2	0.86	1.89	2.580 (3)	135.6

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

Acknowledgements

The authors acknowledge the support of the National Natural Science Foundation of China (20671048).

References

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