organic compounds
2,2′-(1,1′-Azinodiethylidyne)diphenol
aDepartment of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China, and bWeifang Institute of Supervision and Inspection of Product Quality, Weifang 261061, People's Republic of China
*Correspondence e-mail: taixishi@lzu.edu.cn
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.
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); data reduction: SAINT; 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
10.1107/S1600536808011318/at2562sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808011318/at2562Isup2.hkl
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.
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).
Data collection: SMART (Bruker, 2000); cell
SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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).C16H16N2O2 | F(000) = 568 |
Mr = 268.31 | Dx = 1.297 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 1489 reflections |
a = 6.3358 (8) Å | θ = 2.9–20.4° |
b = 13.5625 (10) Å | µ = 0.09 mm−1 |
c = 15.9956 (15) Å | T = 298 K |
V = 1374.5 (2) Å3 | Block, colourless |
Z = 4 | 0.38 × 0.15 × 0.14 mm |
Bruker SMART CCD area-detector diffractometer | 1422 independent reflections |
Radiation source: fine-focus sealed tube | 849 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −7→7 |
Tmin = 0.968, Tmax = 0.988 | k = −16→13 |
7170 measured reflections | l = −17→19 |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0468P)2 + 0.4138P] where P = (Fo2 + 2Fc2)/3 |
1422 reflections | (Δ/σ)max < 0.001 |
181 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.14 e Å−3 |
C16H16N2O2 | V = 1374.5 (2) Å3 |
Mr = 268.31 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.3358 (8) Å | µ = 0.09 mm−1 |
b = 13.5625 (10) Å | T = 298 K |
c = 15.9956 (15) Å | 0.38 × 0.15 × 0.14 mm |
Bruker SMART CCD area-detector diffractometer | 1422 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 849 reflections with I > 2σ(I) |
Tmin = 0.968, Tmax = 0.988 | Rint = 0.044 |
7170 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.15 e Å−3 |
1422 reflections | Δρmin = −0.14 e Å−3 |
181 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.5862 (6) | 0.4828 (2) | 0.5963 (2) | 0.0489 (9) | |
N2 | 0.4075 (6) | 0.4685 (2) | 0.6456 (2) | 0.0486 (9) | |
O1 | 0.8168 (6) | 0.4367 (2) | 0.47328 (19) | 0.0824 (11) | |
H1 | 0.7174 | 0.4320 | 0.5059 | 0.124* | |
O2 | 0.1570 (5) | 0.5228 (2) | 0.75976 (17) | 0.0670 (9) | |
H2 | 0.2602 | 0.5259 | 0.7290 | 0.101* | |
C1 | 0.6514 (8) | 0.6288 (3) | 0.6846 (3) | 0.0719 (14) | |
H1A | 0.5090 | 0.6183 | 0.7031 | 0.108* | |
H1B | 0.6665 | 0.6953 | 0.6649 | 0.108* | |
H1C | 0.7468 | 0.6177 | 0.7302 | 0.108* | |
C2 | 0.7010 (7) | 0.5586 (3) | 0.6150 (2) | 0.0472 (10) | |
C3 | 0.8877 (7) | 0.5753 (3) | 0.5630 (2) | 0.0487 (11) | |
C4 | 0.9357 (8) | 0.5152 (3) | 0.4941 (3) | 0.0605 (13) | |
C5 | 1.1111 (9) | 0.5351 (4) | 0.4453 (3) | 0.0779 (16) | |
H5 | 1.1417 | 0.4951 | 0.3996 | 0.093* | |
C6 | 1.2395 (9) | 0.6130 (4) | 0.4636 (3) | 0.0778 (15) | |
H6 | 1.3570 | 0.6254 | 0.4304 | 0.093* | |
C7 | 1.1973 (8) | 0.6727 (4) | 0.5301 (3) | 0.0698 (14) | |
H7 | 1.2848 | 0.7259 | 0.5422 | 0.084* | |
C8 | 1.0243 (7) | 0.6535 (3) | 0.5790 (3) | 0.0589 (12) | |
H8 | 0.9973 | 0.6942 | 0.6246 | 0.071* | |
C9 | 0.3515 (10) | 0.3201 (3) | 0.5599 (3) | 0.0861 (17) | |
H9A | 0.4546 | 0.3497 | 0.5237 | 0.129* | |
H9B | 0.2270 | 0.3046 | 0.5283 | 0.129* | |
H9C | 0.4084 | 0.2608 | 0.5836 | 0.129* | |
C10 | 0.2963 (7) | 0.3905 (3) | 0.6284 (2) | 0.0502 (11) | |
C11 | 0.1087 (7) | 0.3741 (3) | 0.6796 (3) | 0.0500 (11) | |
C12 | 0.0460 (7) | 0.4402 (3) | 0.7423 (3) | 0.0542 (11) | |
C13 | −0.1329 (8) | 0.4228 (4) | 0.7893 (3) | 0.0651 (13) | |
H13 | −0.1705 | 0.4669 | 0.8312 | 0.078* | |
C14 | −0.2557 (9) | 0.3416 (4) | 0.7750 (3) | 0.0766 (15) | |
H14 | −0.3769 | 0.3310 | 0.8065 | 0.092* | |
C15 | −0.1990 (9) | 0.2764 (3) | 0.7141 (3) | 0.0762 (15) | |
H15 | −0.2824 | 0.2212 | 0.7041 | 0.091* | |
C16 | −0.0201 (8) | 0.2914 (3) | 0.6674 (3) | 0.0668 (13) | |
H16 | 0.0165 | 0.2456 | 0.6267 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.044 (2) | 0.052 (2) | 0.051 (2) | 0.0052 (18) | 0.0000 (18) | −0.0005 (16) |
N2 | 0.046 (2) | 0.047 (2) | 0.053 (2) | 0.0031 (18) | −0.0032 (18) | 0.0000 (16) |
O1 | 0.093 (3) | 0.084 (2) | 0.070 (2) | −0.013 (2) | 0.021 (2) | −0.0175 (17) |
O2 | 0.070 (2) | 0.0691 (19) | 0.0615 (19) | −0.0107 (19) | 0.0074 (18) | −0.0083 (15) |
C1 | 0.062 (3) | 0.067 (3) | 0.087 (3) | −0.006 (3) | 0.012 (3) | −0.017 (3) |
C2 | 0.049 (3) | 0.044 (2) | 0.049 (2) | 0.010 (2) | −0.004 (2) | −0.0004 (18) |
C3 | 0.048 (3) | 0.052 (2) | 0.047 (2) | 0.009 (2) | −0.005 (2) | 0.006 (2) |
C4 | 0.068 (4) | 0.062 (3) | 0.052 (3) | −0.001 (3) | 0.001 (3) | 0.005 (2) |
C5 | 0.087 (4) | 0.092 (4) | 0.054 (3) | 0.005 (4) | 0.020 (3) | 0.004 (3) |
C6 | 0.063 (3) | 0.094 (4) | 0.076 (4) | 0.000 (3) | 0.019 (3) | 0.019 (3) |
C7 | 0.056 (3) | 0.076 (3) | 0.076 (3) | −0.003 (3) | 0.003 (3) | 0.017 (3) |
C8 | 0.053 (3) | 0.063 (3) | 0.061 (3) | 0.003 (3) | −0.004 (3) | 0.005 (2) |
C9 | 0.079 (4) | 0.072 (3) | 0.107 (4) | −0.013 (3) | 0.020 (3) | −0.035 (3) |
C10 | 0.045 (3) | 0.047 (2) | 0.058 (3) | 0.004 (2) | −0.004 (2) | −0.002 (2) |
C11 | 0.049 (3) | 0.045 (2) | 0.056 (3) | 0.001 (2) | −0.009 (2) | 0.006 (2) |
C12 | 0.055 (3) | 0.054 (3) | 0.054 (3) | 0.001 (2) | −0.006 (2) | 0.015 (2) |
C13 | 0.063 (3) | 0.070 (3) | 0.063 (3) | 0.005 (3) | 0.002 (3) | 0.015 (3) |
C14 | 0.068 (3) | 0.081 (3) | 0.081 (4) | −0.002 (3) | 0.009 (3) | 0.031 (3) |
C15 | 0.067 (4) | 0.068 (3) | 0.094 (4) | −0.019 (3) | −0.004 (3) | 0.023 (3) |
C16 | 0.068 (3) | 0.057 (3) | 0.075 (3) | −0.005 (3) | −0.009 (3) | 0.003 (2) |
N1—C2 | 1.295 (5) | C7—C8 | 1.371 (6) |
N1—N2 | 1.394 (4) | C7—H7 | 0.9300 |
N2—C10 | 1.300 (5) | C8—H8 | 0.9300 |
O1—C4 | 1.346 (5) | C9—C10 | 1.495 (5) |
O1—H1 | 0.8200 | C9—H9A | 0.9600 |
O2—C12 | 1.352 (5) | C9—H9B | 0.9600 |
O2—H2 | 0.8200 | C9—H9C | 0.9600 |
C1—C2 | 1.497 (5) | C10—C11 | 1.460 (6) |
C1—H1A | 0.9600 | C11—C16 | 1.401 (5) |
C1—H1B | 0.9600 | C11—C12 | 1.403 (6) |
C1—H1C | 0.9600 | C12—C13 | 1.380 (6) |
C2—C3 | 1.464 (5) | C13—C14 | 1.368 (6) |
C3—C8 | 1.392 (5) | C13—H13 | 0.9300 |
C3—C4 | 1.405 (6) | C14—C15 | 1.364 (6) |
C4—C5 | 1.385 (7) | C14—H14 | 0.9300 |
C5—C6 | 1.365 (7) | C15—C16 | 1.372 (7) |
C5—H5 | 0.9300 | C15—H15 | 0.9300 |
C6—C7 | 1.364 (6) | C16—H16 | 0.9300 |
C6—H6 | 0.9300 | ||
C2—N1—N2 | 115.8 (3) | C7—C8—H8 | 118.8 |
C10—N2—N1 | 115.7 (3) | C3—C8—H8 | 118.8 |
C4—O1—H1 | 109.5 | C10—C9—H9A | 109.5 |
C12—O2—H2 | 109.5 | C10—C9—H9B | 109.5 |
C2—C1—H1A | 109.5 | H9A—C9—H9B | 109.5 |
C2—C1—H1B | 109.5 | C10—C9—H9C | 109.5 |
H1A—C1—H1B | 109.5 | H9A—C9—H9C | 109.5 |
C2—C1—H1C | 109.5 | H9B—C9—H9C | 109.5 |
H1A—C1—H1C | 109.5 | N2—C10—C11 | 116.5 (4) |
H1B—C1—H1C | 109.5 | N2—C10—C9 | 123.2 (4) |
N1—C2—C3 | 116.5 (4) | C11—C10—C9 | 120.3 (4) |
N1—C2—C1 | 124.0 (4) | C16—C11—C12 | 116.5 (4) |
C3—C2—C1 | 119.6 (4) | C16—C11—C10 | 121.2 (4) |
C8—C3—C4 | 116.8 (4) | C12—C11—C10 | 122.3 (4) |
C8—C3—C2 | 121.1 (4) | O2—C12—C13 | 117.1 (4) |
C4—C3—C2 | 122.1 (4) | O2—C12—C11 | 122.0 (4) |
O1—C4—C5 | 117.6 (4) | C13—C12—C11 | 120.9 (4) |
O1—C4—C3 | 122.1 (4) | C14—C13—C12 | 120.9 (5) |
C5—C4—C3 | 120.2 (5) | C14—C13—H13 | 119.5 |
C6—C5—C4 | 120.5 (5) | C12—C13—H13 | 119.5 |
C6—C5—H5 | 119.7 | C15—C14—C13 | 119.5 (5) |
C4—C5—H5 | 119.7 | C15—C14—H14 | 120.3 |
C7—C6—C5 | 120.7 (5) | C13—C14—H14 | 120.3 |
C7—C6—H6 | 119.7 | C14—C15—C16 | 120.6 (5) |
C5—C6—H6 | 119.7 | C14—C15—H15 | 119.7 |
C6—C7—C8 | 119.3 (5) | C16—C15—H15 | 119.7 |
C6—C7—H7 | 120.4 | C15—C16—C11 | 121.7 (5) |
C8—C7—H7 | 120.4 | C15—C16—H16 | 119.2 |
C7—C8—C3 | 122.5 (5) | C11—C16—H16 | 119.2 |
C2—N1—N2—C10 | −177.9 (4) | N1—N2—C10—C11 | 179.9 (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—C16 | 1.7 (6) |
C1—C2—C3—C8 | 2.3 (5) | N2—C10—C11—C12 | 2.2 (5) |
N1—C2—C3—C4 | 2.7 (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—O1 | 179.0 (4) | C10—C11—C12—O2 | −0.7 (6) |
C2—C3—C4—O1 | −2.3 (6) | C16—C11—C12—C13 | 0.5 (6) |
C8—C3—C4—C5 | −0.3 (6) | C10—C11—C12—C13 | 179.6 (4) |
C2—C3—C4—C5 | 178.4 (4) | O2—C12—C13—C14 | 179.2 (4) |
O1—C4—C5—C6 | −179.2 (4) | C11—C12—C13—C14 | −1.1 (6) |
C3—C4—C5—C6 | 0.1 (7) | C12—C13—C14—C15 | 0.8 (7) |
C4—C5—C6—C7 | −0.1 (8) | C13—C14—C15—C16 | 0.2 (7) |
C5—C6—C7—C8 | 0.3 (7) | C14—C15—C16—C11 | −0.8 (7) |
C6—C7—C8—C3 | −0.6 (6) | C12—C11—C16—C15 | 0.5 (6) |
C4—C3—C8—C7 | 0.6 (6) | C10—C11—C16—C15 | −178.7 (4) |
C2—C3—C8—C7 | −178.2 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.82 | 1.80 | 2.529 (5) | 146 |
O2—H2···N2 | 0.82 | 1.80 | 2.529 (4) | 147 |
C1—H1A···N2 | 0.96 | 2.32 | 2.739 (5) | 106 |
C5—H5···O2i | 0.93 | 2.59 | 3.403 (6) | 147 |
C9—H9A···N1 | 0.96 | 2.30 | 2.724 (6) | 106 |
Symmetry code: (i) −x+3/2, −y+1, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C16H16N2O2 |
Mr | 268.31 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 298 |
a, b, c (Å) | 6.3358 (8), 13.5625 (10), 15.9956 (15) |
V (Å3) | 1374.5 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.38 × 0.15 × 0.14 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.968, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7170, 1422, 849 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.128, 1.08 |
No. of reflections | 1422 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.14 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.82 | 1.80 | 2.529 (5) | 146 |
O2—H2···N2 | 0.82 | 1.80 | 2.529 (4) | 147 |
C1—H1A···N2 | 0.96 | 2.32 | 2.739 (5) | 106 |
C5—H5···O2i | 0.93 | 2.59 | 3.403 (6) | 147 |
C9—H9A···N1 | 0.96 | 2.30 | 2.724 (6) | 106 |
Symmetry code: (i) −x+3/2, −y+1, z−1/2. |
Acknowledgements
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.
References
Bruker (2000). SMART, SAINT and SADABS. 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
Tai, X.-S., Yin, X.-H., Tan, M.-Y. & Li, Y.-Z. (2003). Acta Cryst. E59, o681–o682. Web of Science CSD CrossRef IUCr Journals Google Scholar
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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.