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

Li, W.-J.; Han, H.-F.

doi:10.1107/S2056989016003686

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 72| Part 4| April 2016| Pages 467-469

https://doi.org/10.1107/S2056989016003686

Open

access

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

Wen-Juan Li ^a and Hong-Fei Han ^a ^*

^aDepartment of Chemistry, Taiyuan Normal University, Taiyuan 030031, People's Republic of China
^*Correspondence e-mail: hfhan001@163.com

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 25 February 2016; accepted 3 March 2016; online 8 March 2016)

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.

CCDC reference: 1457201

1. 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 ).

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).

2. 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).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.82	2.543 (2)	147
O2—H2⋯O3ⁱ	0.82	1.84	2.649 (3)	171
Symmetry code: (i) x-1, y+1, z.

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, −y + 1, −z + 1.]

3. 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, z.]

4. 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 ).

5. 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).

6. 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

Crystal data
Chemical formula	C₁₆H₁₆N₂O₄·2C₃H₇NO
M_r	446.50
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	298
a, b, c (Å)	6.1616 (7), 7.3109 (8), 13.4537 (15)
α, β, γ (°)	96.771 (1), 103.049 (2), 96.607 (1)
V (Å³)	579.96 (11)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.48 × 0.43 × 0.21

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996 )
T_min, T_max	0.956, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	2902, 2001, 1313
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.187, 1.02
No. of reflections	2001
No. of parameters	149
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.25
Computer programs: SMART and SAINT (Bruker, 2007 ), SHELXS97, SHELXL97 and SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC reference: 1457201

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989016003686/xu5885sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016003686/xu5885Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989016003686/xu5885Isup3.cml

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).

4,4'-[1,1'-(Hydrazinediylidene)bis(ethan-1-yl-1-ylidene)]bis(benzene-1,3-diol) top

Crystal data top

C₁₆H₁₆N₂O₄·2C₃H₇NO	Z = 1
M_r = 446.50	F(000) = 238
Triclinic, P1	D_x = 1.278 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.1616 (7) Å	Cell parameters from 1119 reflections
b = 7.3109 (8) Å	θ = 3.0–26.5°
c = 13.4537 (15) Å	µ = 0.09 mm⁻¹
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 top

Bruker SMART CCD area-detector diffractometer	2001 independent reflections
Radiation source: fine-focus sealed tube	1313 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
phi and ω scans	θ_max = 25.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→7
T_min = 0.956, T_max = 0.981	k = −8→7
2902 measured reflections	l = −15→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.055	H-atom parameters constrained
wR(F²) = 0.187	w = 1/[σ²(F_o²) + (0.1079P)² + 0.0859P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2001 reflections	Δρ_max = 0.28 e Å⁻³
149 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.17 (2)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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

	x	y	z	U_iso*/U_eq
N1	0.4279 (3)	0.5237 (2)	0.53085 (13)	0.0391 (5)
N2	0.5727 (4)	0.1587 (3)	0.91556 (16)	0.0566 (6)
O1	0.2575 (3)	0.7659 (2)	0.62846 (12)	0.0537 (5)
H1	0.3372	0.7270	0.5919	0.081*
O2	−0.2843 (3)	0.5582 (3)	0.80524 (14)	0.0679 (6)
H2	−0.2793	0.6712	0.8190	0.102*
O3	0.7469 (4)	−0.0813 (3)	0.87057 (18)	0.0899 (8)
C1	0.3219 (5)	0.1857 (3)	0.5203 (2)	0.0574 (7)
H1A	0.2229	0.1462	0.4531	0.086*
H1B	0.2779	0.1098	0.5681	0.086*
H1C	0.4737	0.1732	0.5172	0.086*
C2	0.3080 (3)	0.3858 (3)	0.55569 (15)	0.0374 (6)
C3	0.1542 (3)	0.4334 (3)	0.62014 (15)	0.0368 (6)
C4	0.1368 (4)	0.6208 (3)	0.65420 (16)	0.0403 (6)
C5	−0.0090 (4)	0.6624 (3)	0.71594 (16)	0.0458 (6)
H5	−0.0180	0.7861	0.7380	0.055*
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	−0.2153	0.2431	0.7316	0.063*
C8	0.0176 (4)	0.2968 (3)	0.65154 (17)	0.0472 (6)
H8	0.0249	0.1723	0.6304	0.057*
C9	0.5795 (5)	−0.0016 (5)	0.8617 (2)	0.0696 (9)
H9	0.4489	−0.0589	0.8136	0.084*
C10	0.7669 (5)	0.2551 (5)	0.9909 (2)	0.0808 (9)
H10A	0.8729	0.1706	1.0084	0.121*
H10B	0.7228	0.3039	1.0516	0.121*
H10C	0.8355	0.3556	0.9632	0.121*
C11	0.3699 (5)	0.2460 (5)	0.8988 (3)	0.0889 (10)
H11A	0.2480	0.1611	0.8530	0.133*
H11B	0.3951	0.3568	0.8687	0.133*
H11C	0.3324	0.2778	0.9635	0.133*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0427 (11)	0.0333 (11)	0.0416 (10)	0.0063 (8)	0.0117 (8)	0.0035 (8)
N2	0.0545 (13)	0.0620 (15)	0.0553 (12)	0.0128 (11)	0.0150 (10)	0.0088 (11)
O1	0.0704 (11)	0.0331 (10)	0.0647 (11)	0.0015 (8)	0.0367 (9)	0.0024 (7)
O2	0.0738 (13)	0.0718 (14)	0.0713 (12)	0.0124 (10)	0.0428 (10)	0.0122 (10)
O3	0.0897 (16)	0.0827 (17)	0.1017 (17)	0.0266 (14)	0.0354 (13)	−0.0059 (13)
C1	0.0708 (17)	0.0345 (14)	0.0745 (17)	0.0076 (12)	0.0332 (14)	0.0080 (12)
C2	0.0380 (12)	0.0337 (12)	0.0377 (11)	0.0037 (9)	0.0037 (9)	0.0065 (9)
C3	0.0383 (12)	0.0346 (12)	0.0351 (11)	0.0028 (9)	0.0048 (9)	0.0057 (9)
C4	0.0450 (13)	0.0378 (13)	0.0364 (11)	0.0024 (10)	0.0078 (10)	0.0064 (9)
C5	0.0532 (14)	0.0414 (14)	0.0427 (12)	0.0066 (11)	0.0136 (11)	0.0020 (10)
C6	0.0451 (13)	0.0583 (16)	0.0411 (12)	0.0065 (11)	0.0120 (10)	0.0081 (11)
C7	0.0548 (15)	0.0502 (16)	0.0561 (15)	−0.0022 (12)	0.0199 (12)	0.0155 (11)
C8	0.0539 (14)	0.0385 (14)	0.0497 (13)	0.0031 (11)	0.0137 (11)	0.0102 (10)
C9	0.0675 (19)	0.081 (2)	0.0575 (16)	−0.0021 (16)	0.0183 (14)	0.0061 (15)
C10	0.078 (2)	0.075 (2)	0.078 (2)	0.0069 (17)	0.0043 (17)	0.0000 (16)
C11	0.069 (2)	0.102 (3)	0.102 (2)	0.0268 (19)	0.0191 (18)	0.032 (2)

Geometric parameters (Å, º) top

N1—C2	1.301 (3)	C3—C4	1.417 (3)
N1—N1ⁱ	1.391 (3)	C4—C5	1.389 (3)
N2—C9	1.313 (4)	C5—C6	1.380 (3)
N2—C10	1.430 (4)	C5—H5	0.9300
N2—C11	1.453 (3)	C6—C7	1.381 (3)
O1—C4	1.349 (3)	C7—C8	1.374 (3)
O1—H1	0.8200	C7—H7	0.9300
O2—C6	1.358 (3)	C8—H8	0.9300
O2—H2	0.8200	C9—H9	0.9300
O3—C9	1.232 (3)	C10—H10A	0.9600
C1—C2	1.503 (3)	C10—H10B	0.9600
C1—H1A	0.9600	C10—H10C	0.9600
C1—H1B	0.9600	C11—H11A	0.9600
C1—H1C	0.9600	C11—H11B	0.9600
C2—C3	1.465 (3)	C11—H11C	0.9600
C3—C8	1.396 (3)

C2—N1—N1ⁱ	116.3 (2)	O2—C6—C5	122.1 (2)
C9—N2—C10	120.9 (2)	O2—C6—C7	118.0 (2)
C9—N2—C11	121.2 (3)	C5—C6—C7	119.9 (2)
C10—N2—C11	117.9 (3)	C8—C7—C6	119.6 (2)
C4—O1—H1	109.5	C8—C7—H7	120.2
C6—O2—H2	109.5	C6—C7—H7	120.2
C2—C1—H1A	109.5	C7—C8—C3	122.9 (2)
C2—C1—H1B	109.5	C7—C8—H8	118.6
H1A—C1—H1B	109.5	C3—C8—H8	118.6
C2—C1—H1C	109.5	O3—C9—N2	124.5 (3)
H1A—C1—H1C	109.5	O3—C9—H9	117.8
H1B—C1—H1C	109.5	N2—C9—H9	117.8
N1—C2—C3	116.96 (19)	N2—C10—H10A	109.5
N1—C2—C1	122.62 (19)	N2—C10—H10B	109.5
C3—C2—C1	120.4 (2)	H10A—C10—H10B	109.5
C8—C3—C4	116.5 (2)	N2—C10—H10C	109.5
C8—C3—C2	121.9 (2)	H10A—C10—H10C	109.5
C4—C3—C2	121.6 (2)	H10B—C10—H10C	109.5
O1—C4—C5	117.0 (2)	N2—C11—H11A	109.5
O1—C4—C3	122.42 (19)	N2—C11—H11B	109.5
C5—C4—C3	120.6 (2)	H11A—C11—H11B	109.5
C6—C5—C4	120.7 (2)	N2—C11—H11C	109.5
C6—C5—H5	119.7	H11A—C11—H11C	109.5
C4—C5—H5	119.7	H11B—C11—H11C	109.5

N1ⁱ—N1—C2—C3	−179.63 (19)	C3—C4—C5—C6	−0.3 (3)
N1ⁱ—N1—C2—C1	−0.1 (3)	C4—C5—C6—O2	179.9 (2)
N1—C2—C3—C8	−179.94 (18)	C4—C5—C6—C7	0.2 (3)
C1—C2—C3—C8	0.5 (3)	O2—C6—C7—C8	−179.7 (2)
N1—C2—C3—C4	−0.2 (3)	C5—C6—C7—C8	0.0 (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—O1	0.9 (3)	C2—C3—C8—C7	179.7 (2)
C8—C3—C4—C5	0.3 (3)	C10—N2—C9—O3	0.1 (4)
C2—C3—C4—C5	−179.47 (19)	C11—N2—C9—O3	178.5 (3)
O1—C4—C5—C6	179.3 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.82	2.543 (2)	147
O2—H2···O3ⁱⁱ	0.82	1.84	2.649 (3)	171

Symmetry code: (ii) x−1, y+1, z.

Acknowledgements

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

References

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

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.