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Logo of actae2this articlesearchopen accesssubmitActa Crystallographica Section E: Crystallographic CommunicationsActa Crystallographica Section E: Crystallographic Communications
 
Acta Crystallogr E Crystallogr Commun. 2016 April 1; 72(Pt 4): 467–469.
Published online 2016 March 8. doi:  10.1107/S2056989016003686
PMCID: PMC4910326

Crystal structure of (E,E)-2′,4′-di­hydroxy­aceto­phenone azine di­methyl­formamide disolvate

Abstract

In the title compound {systematic name: 4,4′-[1,1′-(hydrazinediyl­idene)bis­(ethan-1-yl-1-yl­idene)]bis­(benzene-1,3-diol)}, C16H16N2O4·2C3H7NO, the (E,E)-2′,4′-di­hydroxy­aceto­phenone azine mol­ecule is centrosymmetric, the mid-point of the N—N bond being located on an inversion centre. All the non-H atoms of the azine mol­ecule are approximately coplanar, the maximum deviation being 0.017 (2) Å. An intra­molecular O—H(...)N hydrogen bond occurs between the azine N atom and the hy­droxy group. In the crystal, azine and di­methyl­formamide solvent mol­ecules are linked by O—H(...)O hydrogen bonds.

Keywords: crystal structure, hydrogen bond, (E,E)-2′,4′-di­hydroxy­aceto­phenone azine

Chemical context  

Hydrazones are important compounds due to their possible applications in material and coordination chemistry. Fluorescence properties of hydrazones have been reported (Qin et al., 2009  ). Many organometallic compounds containing acyl­hydrazone ligands have also been synthesized for their potential magneto-chemical properties (Guo et al., 2010  ). In particular, they have received increasing inter­est for their biological activity as anti­oxidants (Kitaev et al., 1970  ), and their anti­microbial (Ramamohan et al., 1995  ) and anti­viral properties (El-Tabl et al., 2008  ; Rollas & Küçükgüzel, 2007  ).

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Object name is e-72-00467-scheme1.jpg

Although 2′,4′-di­hydroxy­aceto­phenone azine has been pre­pared and studied as a fluorescent probe, its structure has not been reported. As a part of our studies on synthesis and structural peculiarities of Schiff base ligands derived from 2′,4′-di­hydroxy­aceto­phenone and hydrazine, we determined the structure of the title compound, (E,E)-2′,4′-di­hydroxy­aceto­phenone azine di­methyl­formamide disolvate, (I).

Structural commentary  

The mol­ecular structure of the title compound is depicted in Fig. 1  . The asymmetric unit contains one half-mol­ecule of (E,E)-2′,4′-di­hydroxy­aceto­phenone azine and one dimethylformamide (DMF) mol­ecule. The complete azine mol­ecule is centrosymmetric and exists in an E,E configuration with respect to the two C=N bonds. The N1—C2 bond length of 1.301 (3) Å shows double-bond character. The C—O bond lengths [1.349 (3) and 1.358 (3) Å] are comparable with similar bonds in related structures (Chantrapromma et al., 2011  ; Tai et al., 2008  ). All the non-H atoms of the azine mol­ecule are approximately coplanar. The nine atoms (i.e. N1, C1 and C2, and the six C atoms in the benzene ring) are essentially planar, with a mean deviation of 0.0024 Å. Each hy­droxy group is nearly coplanar with its attached benzene ring; the r.m.s. deviation is 0.0045 Å for the seven non-H atoms. Intra­molecular O—H(...)N hydrogen bonds exist in the azine mol­ecule (Table 1  ).

Figure 1
The mol­ecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Only one DMF solvent molecule is shown. [Symmetry code: (i) −x + 1, − ...
Table 1
Hydrogen-bond geometry (Å, °)

Supra­molecular features  

In the crystal of (I), inter­molecular O—H(...)O hydrogen bonds exist between azine mol­ecules and DMF mol­ecules (Table 1  and Fig. 2  ).

Figure 2
The crystal packing of the title compound. Hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) x − 1, y + 1, ...

Database survey  

A search of Cambridge Structural Database (Groom & Allen, 2014  ) for aceto­phenone azine gave 105 hits (excluding organometallics). There are four reported crystal structures of aceto­phenone azine containing hy­droxy groups at the 2-position of benzene rings: (E,E)-2,2′-(1,1′-azinodi­ethyl­idyne)di­phenol (Tai et al., 2008  ), (E,E)-4,4′-di­chloro-2,2′-(1,1′-azinodi­ethyl­idyne)diphenol (Chang et al., 2007  ), (E,E)-3,3′-dieth­oxy-2,2′-(1,1′-azinodi­ethyl­idyne)diphenol (Fayos et al., 1980  ) and (E,E)-4,4′-dimeth­oxy-2,2′-(1,1′-azinodi­ethyl­idyne)diphenol (Zhang et al., 2008  ).

Synthesis and crystallization  

A mixture of 2′,4′-di­hydroxy­aceto­phenone (3.06 g, 20 mmol), hydrazine sulfate (1.28 g, 10 mmol) and tri­ethyl­amine (3.03 g, 30 mmol) in ethanol (40 ml) was heated under reflux for 24 h. After cooling, the precipitate was filtrated and washed with water to afford a yellow solid. Crystals of the title compound suitable for X-ray diffraction were obtained by slow evaporation of a solution of the solid in DMF at room temperature for 5 d (yield 1.20 g, 75%; m.p: 484–485 K). 1H NMR (300 MHz, CDCl3): δ 13.59 (s, 2H, OH), 10.14 (s, 2H, OH), 7.58–7.61 (d, 2H, ArH), 6.37–6.41 (d, 2H, ArH), 6.30–6.31 (s, 2H, ArH), 3.34 (d, 6H, CH3).

Refinement  

Crystal data, data collection and structure refinement details are summarized in Table 2  . H atoms were placed geometrically (C—H = 0.93–0.96 Å and O—H = 0.82 Å) and refined as riding, with U iso(H) = 1.2U eq(C) for aromatic H atoms or 1.5U eq(C,O) for methyl and hy­droxy groups.

Table 2
Experimental details

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016003686/xu5885sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016003686/xu5885Isup2.hkl

CCDC reference: 1457201

Additional supporting information: crystallographic information; 3D view; checkCIF report

Acknowledgments

Financial support from the Natural Science Foundation of Shanxi Province (No. 2013011011-4) is gratefully acknowledged.

supplementary crystallographic information

Crystal data

C16H16N2O4·2C3H7NOZ = 1
Mr = 446.50F(000) = 238
Triclinic, P1Dx = 1.278 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.1616 (7) ÅCell parameters from 1119 reflections
b = 7.3109 (8) Åθ = 3.0–26.5°
c = 13.4537 (15) ŵ = 0.09 mm1
α = 96.771 (1)°T = 298 K
β = 103.049 (2)°Block, colorless
γ = 96.607 (1)°0.48 × 0.43 × 0.21 mm
V = 579.96 (11) Å3

Data collection

Bruker SMART CCD area-detector diffractometer2001 independent reflections
Radiation source: fine-focus sealed tube1313 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
phi and ω scansθmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −6→7
Tmin = 0.956, Tmax = 0.981k = −8→7
2902 measured reflectionsl = −15→15

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055H-atom parameters constrained
wR(F2) = 0.187w = 1/[σ2(Fo2) + (0.1079P)2 + 0.0859P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
2001 reflectionsΔρmax = 0.28 e Å3
149 parametersΔρmin = −0.25 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.17 (2)

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
N10.4279 (3)0.5237 (2)0.53085 (13)0.0391 (5)
N20.5727 (4)0.1587 (3)0.91556 (16)0.0566 (6)
O10.2575 (3)0.7659 (2)0.62846 (12)0.0537 (5)
H10.33720.72700.59190.081*
O2−0.2843 (3)0.5582 (3)0.80524 (14)0.0679 (6)
H2−0.27930.67120.81900.102*
O30.7469 (4)−0.0813 (3)0.87057 (18)0.0899 (8)
C10.3219 (5)0.1857 (3)0.5203 (2)0.0574 (7)
H1A0.22290.14620.45310.086*
H1B0.27790.10980.56810.086*
H1C0.47370.17320.51720.086*
C20.3080 (3)0.3858 (3)0.55569 (15)0.0374 (6)
C30.1542 (3)0.4334 (3)0.62014 (15)0.0368 (6)
C40.1368 (4)0.6208 (3)0.65420 (16)0.0403 (6)
C5−0.0090 (4)0.6624 (3)0.71594 (16)0.0458 (6)
H5−0.01800.78610.73800.055*
C6−0.1404 (4)0.5221 (4)0.74482 (17)0.0479 (6)
C7−0.1270 (4)0.3382 (4)0.71238 (18)0.0528 (7)
H7−0.21530.24310.73160.063*
C80.0176 (4)0.2968 (3)0.65154 (17)0.0472 (6)
H80.02490.17230.63040.057*
C90.5795 (5)−0.0016 (5)0.8617 (2)0.0696 (9)
H90.4489−0.05890.81360.084*
C100.7669 (5)0.2551 (5)0.9909 (2)0.0808 (9)
H10A0.87290.17061.00840.121*
H10B0.72280.30391.05160.121*
H10C0.83550.35560.96320.121*
C110.3699 (5)0.2460 (5)0.8988 (3)0.0889 (10)
H11A0.24800.16110.85300.133*
H11B0.39510.35680.86870.133*
H11C0.33240.27780.96350.133*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0427 (11)0.0333 (11)0.0416 (10)0.0063 (8)0.0117 (8)0.0035 (8)
N20.0545 (13)0.0620 (15)0.0553 (12)0.0128 (11)0.0150 (10)0.0088 (11)
O10.0704 (11)0.0331 (10)0.0647 (11)0.0015 (8)0.0367 (9)0.0024 (7)
O20.0738 (13)0.0718 (14)0.0713 (12)0.0124 (10)0.0428 (10)0.0122 (10)
O30.0897 (16)0.0827 (17)0.1017 (17)0.0266 (14)0.0354 (13)−0.0059 (13)
C10.0708 (17)0.0345 (14)0.0745 (17)0.0076 (12)0.0332 (14)0.0080 (12)
C20.0380 (12)0.0337 (12)0.0377 (11)0.0037 (9)0.0037 (9)0.0065 (9)
C30.0383 (12)0.0346 (12)0.0351 (11)0.0028 (9)0.0048 (9)0.0057 (9)
C40.0450 (13)0.0378 (13)0.0364 (11)0.0024 (10)0.0078 (10)0.0064 (9)
C50.0532 (14)0.0414 (14)0.0427 (12)0.0066 (11)0.0136 (11)0.0020 (10)
C60.0451 (13)0.0583 (16)0.0411 (12)0.0065 (11)0.0120 (10)0.0081 (11)
C70.0548 (15)0.0502 (16)0.0561 (15)−0.0022 (12)0.0199 (12)0.0155 (11)
C80.0539 (14)0.0385 (14)0.0497 (13)0.0031 (11)0.0137 (11)0.0102 (10)
C90.0675 (19)0.081 (2)0.0575 (16)−0.0021 (16)0.0183 (14)0.0061 (15)
C100.078 (2)0.075 (2)0.078 (2)0.0069 (17)0.0043 (17)0.0000 (16)
C110.069 (2)0.102 (3)0.102 (2)0.0268 (19)0.0191 (18)0.032 (2)

Geometric parameters (Å, º)

N1—C21.301 (3)C3—C41.417 (3)
N1—N1i1.391 (3)C4—C51.389 (3)
N2—C91.313 (4)C5—C61.380 (3)
N2—C101.430 (4)C5—H50.9300
N2—C111.453 (3)C6—C71.381 (3)
O1—C41.349 (3)C7—C81.374 (3)
O1—H10.8200C7—H70.9300
O2—C61.358 (3)C8—H80.9300
O2—H20.8200C9—H90.9300
O3—C91.232 (3)C10—H10A0.9600
C1—C21.503 (3)C10—H10B0.9600
C1—H1A0.9600C10—H10C0.9600
C1—H1B0.9600C11—H11A0.9600
C1—H1C0.9600C11—H11B0.9600
C2—C31.465 (3)C11—H11C0.9600
C3—C81.396 (3)
C2—N1—N1i116.3 (2)O2—C6—C5122.1 (2)
C9—N2—C10120.9 (2)O2—C6—C7118.0 (2)
C9—N2—C11121.2 (3)C5—C6—C7119.9 (2)
C10—N2—C11117.9 (3)C8—C7—C6119.6 (2)
C4—O1—H1109.5C8—C7—H7120.2
C6—O2—H2109.5C6—C7—H7120.2
C2—C1—H1A109.5C7—C8—C3122.9 (2)
C2—C1—H1B109.5C7—C8—H8118.6
H1A—C1—H1B109.5C3—C8—H8118.6
C2—C1—H1C109.5O3—C9—N2124.5 (3)
H1A—C1—H1C109.5O3—C9—H9117.8
H1B—C1—H1C109.5N2—C9—H9117.8
N1—C2—C3116.96 (19)N2—C10—H10A109.5
N1—C2—C1122.62 (19)N2—C10—H10B109.5
C3—C2—C1120.4 (2)H10A—C10—H10B109.5
C8—C3—C4116.5 (2)N2—C10—H10C109.5
C8—C3—C2121.9 (2)H10A—C10—H10C109.5
C4—C3—C2121.6 (2)H10B—C10—H10C109.5
O1—C4—C5117.0 (2)N2—C11—H11A109.5
O1—C4—C3122.42 (19)N2—C11—H11B109.5
C5—C4—C3120.6 (2)H11A—C11—H11B109.5
C6—C5—C4120.7 (2)N2—C11—H11C109.5
C6—C5—H5119.7H11A—C11—H11C109.5
C4—C5—H5119.7H11B—C11—H11C109.5
N1i—N1—C2—C3−179.63 (19)C3—C4—C5—C6−0.3 (3)
N1i—N1—C2—C1−0.1 (3)C4—C5—C6—O2179.9 (2)
N1—C2—C3—C8−179.94 (18)C4—C5—C6—C70.2 (3)
C1—C2—C3—C80.5 (3)O2—C6—C7—C8−179.7 (2)
N1—C2—C3—C4−0.2 (3)C5—C6—C7—C80.0 (4)
C1—C2—C3—C4−179.69 (19)C6—C7—C8—C3−0.1 (4)
C8—C3—C4—O1−179.28 (19)C4—C3—C8—C7−0.1 (3)
C2—C3—C4—O10.9 (3)C2—C3—C8—C7179.7 (2)
C8—C3—C4—C50.3 (3)C10—N2—C9—O30.1 (4)
C2—C3—C4—C5−179.47 (19)C11—N2—C9—O3178.5 (3)
O1—C4—C5—C6179.3 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.822.543 (2)147
O2—H2···O3ii0.821.842.649 (3)171

Symmetry code: (ii) x−1, y+1, z.

References

  • Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chang, J.-G., He, G.-F. & Li, Y.-F. (2007). Acta Cryst. E63, o3982.
  • Chantrapromma, S., Jansrisewangwong, P., Chanawanno, K. & Fun, H.-K. (2011). Acta Cryst. E67, o2221–o2222. [PMC free article] [PubMed]
  • El-Tabl, A. S., El-Saied, F. A., Plass, W. & Al-Hakimi, A. N. (2008). Spectrochim. Acta A Mol. Biomol. Spectrosc. 71, 90–99. [PubMed]
  • Fayos, J., Martínez-Ripoll, M., García-Mina, M. C., Gonzalez-Martínez, J. & Arrese, F. (1980). Acta Cryst. B36, 1952–1953.
  • Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671. [PubMed]
  • Guo, Y.-N., Xu, G.-F., Gamez, P., Zhao, L., Lin, S.-Y., Deng, R., Tang, J.-K. & Zhang, H.-J. (2010). J. Am. Chem. Soc. 132, 8538–8539. [PubMed]
  • Kitaev, Y. P., Buzykin, B. I. & Troepol’skaya, T. V. (1970). Russ. Chem. Rev. 39, 441–456.
  • Qin, D.-D., Yang, Z.-Y. & Qi, G.-F. (2009). Spectrochim. Acta A Mol. Biomol. Spectrosc. 74, 415–420. [PubMed]
  • Ramamohan, L., Shikkargol, R. K., Angadi, S. D. & Kulkarni, V. H. (1995). Asian J. Pure Appl. Chem. 1, 86–89.
  • Rollas, S. & Küçükgüzel, Ş. G. (2007). Molecules, 12, 1910–1939. [PubMed]
  • Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Tai, X.-S., Xu, J., Feng, Y.-M. & Liang, Z.-P. (2008). Acta Cryst. E64, o905. [PMC free article] [PubMed]
  • Zhang, J.-H., Dong, W.-L., Ge, Y.-Q. & Zhao, B.-X. (2008). Acta Cryst. E64, o166.

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