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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o120.
Published online 2007 December 6. doi:  10.1107/S160053680706312X
PMCID: PMC2915190

N,N′-Disalicyloylhydrazine

Abstract

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

An external file that holds a picture, illustration, etc.
Object name is e-64-0o120-scheme1.jpg

Experimental

Crystal data

  • C14H12N2O4
  • M r = 272.26
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o120-efi4.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.047
  • wR(F 2) = 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

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Structure factors: contains datablocks I. DOI: 10.1107/S160053680706312X/si2060Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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

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).

Figures

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.

Crystal data

C14H12N2O4F000 = 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 = 2.6–25.5º
b = 6.2909 (15) ŵ = 0.11 mm1
c = 12.376 (2) ÅT = 298 (2) K
β = 105.463 (2)ºBlock, colorless
V = 628.9 (2) Å30.18 × 0.15 × 0.14 mm
Z = 2

Data collection

Bruker SMART 1000 CCD area-detector diffractometer1102 independent reflections
Radiation source: fine-focus sealed tube618 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.042
T = 298(2) Kθmax = 25.0º
[var phi] and ω scansθmin = 2.6º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −9→9
Tmin = 0.981, Tmax = 0.985k = −7→7
3082 measured reflectionsl = −6→14

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.163  w = 1/[σ2(Fo2) + (0.0827P)2 + 0.0895P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
1102 reflectionsΔρmax = 0.30 e Å3
92 parametersΔρmin = −0.19 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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 (Å2)

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)

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, °)

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—C4−179.4 (3)
N1i—N1—C1—C2−180.0 (3)O2—C3—C4—C5179.4 (3)
O1—C1—C2—C3172.2 (3)C2—C3—C4—C50.5 (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—C70.1 (5)
N1—C1—C2—C7173.3 (3)C5—C6—C7—C20.1 (5)
C7—C2—C3—O2−179.3 (3)C3—C2—C7—C60.1 (4)
C1—C2—C3—O21.7 (4)C1—C2—C7—C6179.1 (3)
C7—C2—C3—C4−0.4 (4)

Symmetry codes: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

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 codes: (ii) x+1/2, −y+3/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2060).

References

  • Bernhardt, P. V., Chin, P., Sharpe, P. C., Wang, J. C. & Richardson, D. R. (2005). Biol. Inorg. Chem.10, 761–777. [PubMed]
  • Dou, J. M., Liu, M. L., Li, D. C. & Wang, D. Q. (2006). Eur. J. Inorg. Chem.23, 4866–4871.
  • John, R. P., Park, J., Moon, D., Lee, K. & Lah, M. S. (2006). Chem. Commun. pp. 3699–3701. [PubMed]
  • Liu, M.-L., Dou, J.-M., Li, D.-C. & Wang, D.-Q. (2006). Acta Cryst. E62, o1009–o1010.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (1997a). SHELXL97 and SHELXS97 University of Göttingen, Germany.
  • Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Siemens (1996). SMART and SAINT Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

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