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Acta Crystallogr Sect E Struct Rep Online. 2008 May 1; 64(Pt 5): o905.
Published online 2008 April 26. doi:  10.1107/S1600536808011318
PMCID: PMC2961071

2,2′-(1,1′-Azinodiethyl­idyne)diphenol

Abstract

In the title mol­ecule, C16H16N2O2, the C—N bond lengths are 1.295 (5) and 1.300 (5) Å, which suggests that they are double bonds. The structure is stabilized by intra­molecular O—H(...)N and C—H(...)N, and inter­molecular C—H(...)O hydrogen-bond inter­actions.

Related literature

For related literature, see: Tai et al. (2003 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o905-scheme1.jpg

Experimental

Crystal data

  • C16H16N2O2
  • M r = 268.31
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o905-efi1.jpg
  • a = 6.3358 (8) Å
  • b = 13.5625 (10) Å
  • c = 15.9956 (15) Å
  • V = 1374.5 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 298 (2) K
  • 0.38 × 0.15 × 0.14 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.968, T max = 0.988
  • 7170 measured reflections
  • 1422 independent reflections
  • 849 reflections with I > 2σ(I)
  • R int = 0.044

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.128
  • S = 1.08
  • 1422 reflections
  • 181 parameters
  • H-atom parameters constrained
  • Δρmax = 0.15 e Å−3
  • Δρmin = −0.14 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808011318/at2562sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808011318/at2562Isup2.hkl

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

Acknowledgments

The authors thank the National Natural Science Foundation of China (20671073), the Natural Science Foundation of Shandong (Y2007B60) and the Science and Technology Foundation of Weifang and Weifang University for research grants.

supplementary crystallographic information

Comment

As part of our ongoing studies of the coordination chemistry of Schiffbase ligands (Tai et al., 2003), we now report the synthesis and structure of the title compound, (I), (Fig. 1).

In the molecule of (I), both C2—N1 [1.295 (5) Å], and C10—N2 [1.300 (5) Å] are close to double-bond separations, indicating that the Lewis structure shown in the scheme is only an approximation to the electron distribution in the molecule. Otherwise, the geometrical parameters for (I) are normal. The structure is stabilized by intramolecular O—H···N and C—H···N, and intermolecular C—H···O hydrogen bonding interactions.

Experimental

2 mmol of 2'-Hhydroxyacetophenone (2 mmol) was added to a solution of hydrazide (1 mmol) in 10 ml of 95% ethanol. The mixture was continuously stirred for 3 h at refluxing temperature, evaporating some ethanol, then, upon cooling, the solid product was collected by filtration and dried in vacuo (yield 58%). Clear blocks of (I) were obtained by evaporation from a methanol solution after 6 days.

Refinement

The H atoms were placed geometrically (C—H = 0.93–0.96 Å, O—H = 0.82 Å) and refined as riding with Uiso(H) = 1.2Ueq(aromatic C) or 1.5Ueq(methyl C, hydroxyl O).

Figures

Fig. 1.
The molecular structure of (I) showing 30% displacement ellipsoids.

Crystal data

C16H16N2O2F000 = 568
Mr = 268.31Dx = 1.297 Mg m3
Orthorhombic, P212121Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 1489 reflections
a = 6.3358 (8) Åθ = 2.9–20.4º
b = 13.5625 (10) ŵ = 0.09 mm1
c = 15.9956 (15) ÅT = 298 (2) K
V = 1374.5 (2) Å3Block, colourless
Z = 40.38 × 0.15 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer1422 independent reflections
Radiation source: fine-focus sealed tube849 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.044
T = 298(2) Kθmax = 25.0º
[var phi] and ω scansθmin = 2.0º
Absorption correction: multi-scan(SADABS; Bruker, 2000)h = −7→7
Tmin = 0.968, Tmax = 0.988k = −16→13
7170 measured reflectionsl = −17→19

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.128  w = 1/[σ2(Fo2) + (0.0468P)2 + 0.4138P] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
1422 reflectionsΔρmax = 0.15 e Å3
181 parametersΔρmin = −0.14 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
N10.5862 (6)0.4828 (2)0.5963 (2)0.0489 (9)
N20.4075 (6)0.4685 (2)0.6456 (2)0.0486 (9)
O10.8168 (6)0.4367 (2)0.47328 (19)0.0824 (11)
H10.71740.43200.50590.124*
O20.1570 (5)0.5228 (2)0.75976 (17)0.0670 (9)
H20.26020.52590.72900.101*
C10.6514 (8)0.6288 (3)0.6846 (3)0.0719 (14)
H1A0.50900.61830.70310.108*
H1B0.66650.69530.66490.108*
H1C0.74680.61770.73020.108*
C20.7010 (7)0.5586 (3)0.6150 (2)0.0472 (10)
C30.8877 (7)0.5753 (3)0.5630 (2)0.0487 (11)
C40.9357 (8)0.5152 (3)0.4941 (3)0.0605 (13)
C51.1111 (9)0.5351 (4)0.4453 (3)0.0779 (16)
H51.14170.49510.39960.093*
C61.2395 (9)0.6130 (4)0.4636 (3)0.0778 (15)
H61.35700.62540.43040.093*
C71.1973 (8)0.6727 (4)0.5301 (3)0.0698 (14)
H71.28480.72590.54220.084*
C81.0243 (7)0.6535 (3)0.5790 (3)0.0589 (12)
H80.99730.69420.62460.071*
C90.3515 (10)0.3201 (3)0.5599 (3)0.0861 (17)
H9A0.45460.34970.52370.129*
H9B0.22700.30460.52830.129*
H9C0.40840.26080.58360.129*
C100.2963 (7)0.3905 (3)0.6284 (2)0.0502 (11)
C110.1087 (7)0.3741 (3)0.6796 (3)0.0500 (11)
C120.0460 (7)0.4402 (3)0.7423 (3)0.0542 (11)
C13−0.1329 (8)0.4228 (4)0.7893 (3)0.0651 (13)
H13−0.17050.46690.83120.078*
C14−0.2557 (9)0.3416 (4)0.7750 (3)0.0766 (15)
H14−0.37690.33100.80650.092*
C15−0.1990 (9)0.2764 (3)0.7141 (3)0.0762 (15)
H15−0.28240.22120.70410.091*
C16−0.0201 (8)0.2914 (3)0.6674 (3)0.0668 (13)
H160.01650.24560.62670.080*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.044 (2)0.052 (2)0.051 (2)0.0052 (18)0.0000 (18)−0.0005 (16)
N20.046 (2)0.047 (2)0.053 (2)0.0031 (18)−0.0032 (18)0.0000 (16)
O10.093 (3)0.084 (2)0.070 (2)−0.013 (2)0.021 (2)−0.0175 (17)
O20.070 (2)0.0691 (19)0.0615 (19)−0.0107 (19)0.0074 (18)−0.0083 (15)
C10.062 (3)0.067 (3)0.087 (3)−0.006 (3)0.012 (3)−0.017 (3)
C20.049 (3)0.044 (2)0.049 (2)0.010 (2)−0.004 (2)−0.0004 (18)
C30.048 (3)0.052 (2)0.047 (2)0.009 (2)−0.005 (2)0.006 (2)
C40.068 (4)0.062 (3)0.052 (3)−0.001 (3)0.001 (3)0.005 (2)
C50.087 (4)0.092 (4)0.054 (3)0.005 (4)0.020 (3)0.004 (3)
C60.063 (3)0.094 (4)0.076 (4)0.000 (3)0.019 (3)0.019 (3)
C70.056 (3)0.076 (3)0.076 (3)−0.003 (3)0.003 (3)0.017 (3)
C80.053 (3)0.063 (3)0.061 (3)0.003 (3)−0.004 (3)0.005 (2)
C90.079 (4)0.072 (3)0.107 (4)−0.013 (3)0.020 (3)−0.035 (3)
C100.045 (3)0.047 (2)0.058 (3)0.004 (2)−0.004 (2)−0.002 (2)
C110.049 (3)0.045 (2)0.056 (3)0.001 (2)−0.009 (2)0.006 (2)
C120.055 (3)0.054 (3)0.054 (3)0.001 (2)−0.006 (2)0.015 (2)
C130.063 (3)0.070 (3)0.063 (3)0.005 (3)0.002 (3)0.015 (3)
C140.068 (3)0.081 (3)0.081 (4)−0.002 (3)0.009 (3)0.031 (3)
C150.067 (4)0.068 (3)0.094 (4)−0.019 (3)−0.004 (3)0.023 (3)
C160.068 (3)0.057 (3)0.075 (3)−0.005 (3)−0.009 (3)0.003 (2)

Geometric parameters (Å, °)

N1—C21.295 (5)C7—C81.371 (6)
N1—N21.394 (4)C7—H70.9300
N2—C101.300 (5)C8—H80.9300
O1—C41.346 (5)C9—C101.495 (5)
O1—H10.8200C9—H9A0.9600
O2—C121.352 (5)C9—H9B0.9600
O2—H20.8200C9—H9C0.9600
C1—C21.497 (5)C10—C111.460 (6)
C1—H1A0.9600C11—C161.401 (5)
C1—H1B0.9600C11—C121.403 (6)
C1—H1C0.9600C12—C131.380 (6)
C2—C31.464 (5)C13—C141.368 (6)
C3—C81.392 (5)C13—H130.9300
C3—C41.405 (6)C14—C151.364 (6)
C4—C51.385 (7)C14—H140.9300
C5—C61.365 (7)C15—C161.372 (7)
C5—H50.9300C15—H150.9300
C6—C71.364 (6)C16—H160.9300
C6—H60.9300
C2—N1—N2115.8 (3)C7—C8—H8118.8
C10—N2—N1115.7 (3)C3—C8—H8118.8
C4—O1—H1109.5C10—C9—H9A109.5
C12—O2—H2109.5C10—C9—H9B109.5
C2—C1—H1A109.5H9A—C9—H9B109.5
C2—C1—H1B109.5C10—C9—H9C109.5
H1A—C1—H1B109.5H9A—C9—H9C109.5
C2—C1—H1C109.5H9B—C9—H9C109.5
H1A—C1—H1C109.5N2—C10—C11116.5 (4)
H1B—C1—H1C109.5N2—C10—C9123.2 (4)
N1—C2—C3116.5 (4)C11—C10—C9120.3 (4)
N1—C2—C1124.0 (4)C16—C11—C12116.5 (4)
C3—C2—C1119.6 (4)C16—C11—C10121.2 (4)
C8—C3—C4116.8 (4)C12—C11—C10122.3 (4)
C8—C3—C2121.1 (4)O2—C12—C13117.1 (4)
C4—C3—C2122.1 (4)O2—C12—C11122.0 (4)
O1—C4—C5117.6 (4)C13—C12—C11120.9 (4)
O1—C4—C3122.1 (4)C14—C13—C12120.9 (5)
C5—C4—C3120.2 (5)C14—C13—H13119.5
C6—C5—C4120.5 (5)C12—C13—H13119.5
C6—C5—H5119.7C15—C14—C13119.5 (5)
C4—C5—H5119.7C15—C14—H14120.3
C7—C6—C5120.7 (5)C13—C14—H14120.3
C7—C6—H6119.7C14—C15—C16120.6 (5)
C5—C6—H6119.7C14—C15—H15119.7
C6—C7—C8119.3 (5)C16—C15—H15119.7
C6—C7—H7120.4C15—C16—C11121.7 (5)
C8—C7—H7120.4C15—C16—H16119.2
C7—C8—C3122.5 (5)C11—C16—H16119.2
C2—N1—N2—C10−177.9 (4)N1—N2—C10—C11179.9 (3)
N2—N1—C2—C3−179.2 (3)N1—N2—C10—C9−0.6 (6)
N2—N1—C2—C1−0.2 (5)N2—C10—C11—C16−178.7 (4)
N1—C2—C3—C8−178.6 (4)C9—C10—C11—C161.7 (6)
C1—C2—C3—C82.3 (5)N2—C10—C11—C122.2 (5)
N1—C2—C3—C42.7 (5)C9—C10—C11—C12−177.4 (4)
C1—C2—C3—C4−176.4 (4)C16—C11—C12—O2−179.8 (4)
C8—C3—C4—O1179.0 (4)C10—C11—C12—O2−0.7 (6)
C2—C3—C4—O1−2.3 (6)C16—C11—C12—C130.5 (6)
C8—C3—C4—C5−0.3 (6)C10—C11—C12—C13179.6 (4)
C2—C3—C4—C5178.4 (4)O2—C12—C13—C14179.2 (4)
O1—C4—C5—C6−179.2 (4)C11—C12—C13—C14−1.1 (6)
C3—C4—C5—C60.1 (7)C12—C13—C14—C150.8 (7)
C4—C5—C6—C7−0.1 (8)C13—C14—C15—C160.2 (7)
C5—C6—C7—C80.3 (7)C14—C15—C16—C11−0.8 (7)
C6—C7—C8—C3−0.6 (6)C12—C11—C16—C150.5 (6)
C4—C3—C8—C70.6 (6)C10—C11—C16—C15−178.7 (4)
C2—C3—C8—C7−178.2 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.802.529 (5)146
O2—H2···N20.821.802.529 (4)147
C1—H1A···N20.962.322.739 (5)106
C5—H5···O2i0.932.593.403 (6)147
C9—H9A···N10.962.302.724 (6)106

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2562).

References

  • Bruker (2000). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Tai, X.-S., Yin, X.-H., Tan, M.-Y. & Li, Y.-Z. (2003). Acta Cryst. E59, o681–o682.

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