organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

N,N′-Disalicyloylhydrazine

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[John, R. P., Park, J., Moon, D., Lee, K. & Lah, M. S. (2006). Chem. Commun. pp. 3699-3701.]); Dou et al. (2006[Dou, J. M., Liu, M. L., Li, D. C. & Wang, D. Q. (2006). Eur. J. Inorg. Chem. 23, 4866-4871.]). For the crystal structure of an iron compound with N,N′-bis-picolinoyl hydrazine, see: Bernhardt et al. (2005[Bernhardt, P. V., Chin, P., Sharpe, P. C., Wang, J. C. & Richardson, D. R. (2005). Biol. Inorg. Chem. 10, 761-777.]). For the preparation of 2-acetyl-2-hydroxy­naphthohydrazide, see: Liu et al. (2006[Liu, M.-L., Dou, J.-M., Li, D.-C. & Wang, D.-Q. (2006). Acta Cryst. E62, o1009-o1010.]).

[Scheme 1]

Experimental

Crystal data
  • C14H12N2O4

  • Mr = 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.981, Tmax = 0.985

  • 3082 measured reflections

  • 1102 independent reflections

  • 618 reflections with I > 2σ(I)

  • Rint = 0.042

Refinement
  • R[F2 > 2σ(F2)] = 0.047

  • wR(F2) = 0.163

  • S = 1.03

  • 1102 reflections

  • 92 parameters

  • H-atom parameters constrained

  • Δρmax = 0.30 e Å−3

  • Δρmin = −0.19 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); cell refinement: SMART; data reduction: SAINT (Siemens, 1996[Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a[Sheldrick, G. M. (1997a). SHELXL97 and SHELXS97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a[Sheldrick, G. M. (1997a). SHELXL97 and SHELXS97. University of Göttingen, Germany.]); molecular graphics: SHELXTL (Sheldrick, 1997b[Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.]); software used to prepare material for publication: SHELXTL.

Supporting information


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.

Refinement top

The H atoms on the ligands were allowed to ride on their parent atoms with C(sp2 hybrid)-H distances of 0.93 Å and Uiso(H)=1.2Ueq(C).

Structure description 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.

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).

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
[Figure 1] 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
[Figure 2] 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
C14H12N2O4F(000) = 284
Mr = 272.26Dx = 1.438 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 678 reflections
a = 8.3816 (18) Åθ = 2.6–25.5°
b = 6.2909 (15) ŵ = 0.11 mm1
c = 12.376 (2) ÅT = 298 K
β = 105.463 (2)°Block, colorless
V = 628.9 (2) Å30.18 × 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 tube618 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
φ and ω scansθmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 99
Tmin = 0.981, Tmax = 0.985k = 77
3082 measured reflectionsl = 614
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.163H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0827P)2 + 0.0895P]
where P = (Fo2 + 2Fc2)/3
1102 reflections(Δ/σ)max < 0.001
92 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.19 e Å3
Crystal data top
C14H12N2O4V = 628.9 (2) Å3
Mr = 272.26Z = 2
Monoclinic, P21/nMo Kα radiation
a = 8.3816 (18) ŵ = 0.11 mm1
b = 6.2909 (15) ÅT = 298 K
c = 12.376 (2) Å0.18 × 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)
Tmin = 0.981, Tmax = 0.985Rint = 0.042
3082 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.163H-atom parameters constrained
S = 1.03Δρmax = 0.30 e Å3
1102 reflectionsΔρmin = 0.19 e Å3
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
xyzUiso*/Ueq
N10.9962 (3)0.5894 (4)0.53095 (19)0.0462 (7)
H11.07810.62290.58670.055*
O10.7444 (2)0.6612 (3)0.42420 (17)0.0576 (7)
O21.1131 (3)0.8180 (4)0.70745 (18)0.0696 (8)
H21.16070.84430.77300.104*
C10.8612 (4)0.7109 (5)0.5042 (2)0.0419 (8)
C20.8605 (3)0.9011 (4)0.5739 (2)0.0372 (7)
C30.9807 (3)0.9503 (5)0.6721 (2)0.0419 (7)
C40.9670 (4)1.1325 (5)0.7318 (3)0.0502 (9)
H41.04851.16460.79710.060*
C50.8344 (4)1.2655 (6)0.6953 (3)0.0550 (9)
H50.82571.38720.73600.066*
C60.7137 (4)1.2198 (5)0.5984 (3)0.0550 (9)
H60.62381.31050.57370.066*
C70.7265 (3)1.0410 (5)0.5388 (3)0.0475 (8)
H70.64461.01140.47340.057*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0449 (14)0.0496 (16)0.0396 (15)0.0013 (12)0.0033 (12)0.0122 (11)
O10.0524 (13)0.0698 (16)0.0397 (12)0.0048 (11)0.0066 (10)0.0061 (11)
O20.0648 (16)0.0800 (17)0.0481 (14)0.0250 (13)0.0125 (11)0.0230 (13)
C10.0430 (18)0.0471 (18)0.0336 (15)0.0016 (14)0.0067 (14)0.0045 (14)
C20.0375 (16)0.0409 (17)0.0357 (16)0.0006 (13)0.0141 (13)0.0018 (13)
C30.0370 (15)0.0487 (17)0.0384 (16)0.0066 (14)0.0073 (13)0.0016 (15)
C40.0476 (19)0.056 (2)0.0465 (18)0.0038 (16)0.0127 (15)0.0124 (16)
C50.063 (2)0.0485 (19)0.061 (2)0.0016 (17)0.0303 (19)0.0077 (17)
C60.054 (2)0.050 (2)0.065 (2)0.0137 (16)0.0226 (18)0.0076 (18)
C70.0389 (16)0.055 (2)0.0465 (18)0.0052 (15)0.0079 (14)0.0074 (16)
Geometric parameters (Å, º) top
N1—C11.331 (3)C3—C41.384 (4)
N1—N1i1.372 (4)C4—C51.368 (4)
N1—H10.8600C4—H40.9300
O1—C11.233 (3)C5—C61.377 (5)
O2—C31.363 (3)C5—H50.9300
O2—H20.8200C6—C71.365 (4)
C1—C21.476 (4)C6—H60.9300
C2—C31.391 (4)C7—H70.9300
C2—C71.402 (4)
C1—N1—N1i119.7 (3)C5—C4—C3120.4 (3)
C1—N1—H1120.2C5—C4—H4119.8
N1i—N1—H1120.2C3—C4—H4119.8
C3—O2—H2109.5C4—C5—C6120.2 (3)
O1—C1—N1119.6 (3)C4—C5—H5119.9
O1—C1—C2123.3 (3)C6—C5—H5119.9
N1—C1—C2117.1 (2)C7—C6—C5119.8 (3)
C3—C2—C7117.7 (3)C7—C6—H6120.1
C3—C2—C1125.2 (2)C5—C6—H6120.1
C7—C2—C1117.1 (2)C6—C7—C2121.4 (3)
O2—C3—C4120.7 (3)C6—C7—H7119.3
O2—C3—C2118.8 (3)C2—C7—H7119.3
C4—C3—C2120.5 (3)
N1i—N1—C1—O10.1 (5)C1—C2—C3—C4179.4 (3)
N1i—N1—C1—C2180.0 (3)O2—C3—C4—C5179.4 (3)
O1—C1—C2—C3172.2 (3)C2—C3—C4—C50.5 (4)
N1—C1—C2—C37.7 (4)C3—C4—C5—C60.4 (5)
O1—C1—C2—C76.7 (4)C4—C5—C6—C70.1 (5)
N1—C1—C2—C7173.3 (3)C5—C6—C7—C20.1 (5)
C7—C2—C3—O2179.3 (3)C3—C2—C7—C60.1 (4)
C1—C2—C3—O21.7 (4)C1—C2—C7—C6179.1 (3)
C7—C2—C3—C40.4 (4)
Symmetry code: (i) x+2, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1ii0.821.812.617 (3)166
N1—H1···O20.861.892.580 (3)136
Symmetry code: (ii) x+1/2, y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC14H12N2O4
Mr272.26
Crystal system, space groupMonoclinic, P21/n
Temperature (K)298
a, b, c (Å)8.3816 (18), 6.2909 (15), 12.376 (2)
β (°) 105.463 (2)
V3)628.9 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.18 × 0.15 × 0.14
Data collection
DiffractometerBruker SMART 1000 CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.981, 0.985
No. of measured, independent and
observed [I > 2σ(I)] reflections
3082, 1102, 618
Rint0.042
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.163, 1.03
No. of reflections1102
No. of parameters92
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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—C11.331 (3)O1—C11.233 (3)
N1—N1i1.372 (4)O2—C31.363 (3)
C1—N1—N1i119.7 (3)O1—C1—C2123.3 (3)
O1—C1—N1119.6 (3)N1—C1—C2117.1 (2)
Symmetry code: (i) x+2, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1ii0.821.812.617 (3)165.6
N1—H1···O20.861.892.580 (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

First citationBernhardt, P. V., Chin, P., Sharpe, P. C., Wang, J. C. & Richardson, D. R. (2005). Biol. Inorg. Chem. 10, 761–777.  Web of Science CSD CrossRef CAS Google Scholar
First citationDou, J. M., Liu, M. L., Li, D. C. & Wang, D. Q. (2006). Eur. J. Inorg. Chem. 23, 4866–4871.  Web of Science CSD CrossRef Google Scholar
First citationJohn, R. P., Park, J., Moon, D., Lee, K. & Lah, M. S. (2006). Chem. Commun. pp. 3699–3701.  Web of Science CSD CrossRef Google Scholar
First citationLiu, M.-L., Dou, J.-M., Li, D.-C. & Wang, D.-Q. (2006). Acta Cryst. E62, o1009–o1010.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (1997a). SHELXL97 and SHELXS97. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationSiemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.  Google Scholar

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