3,3′-[(1E,1′E)-Hydrazine-1,2-diylidenebis(ethan-1-yl-1-yl­idene)]bis­(4-hy­droxy-6-methyl-2H-pyran-2-one)

El Alami, A.; Hamid, S.; El Kihel, A.; Saadi, M.; El Ammari, L.

doi:10.1107/S2414314619013488

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 10| October 2019| x191348

https://doi.org/10.1107/S2414314619013488

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3,3′-[(1E,1′E)-Hydrazine-1,2-diylidenebis(ethan-1-yl-1-ylidene)]bis(4-hydroxy-6-methyl-2H-pyran-2-one)

Abouelhaoul El Alami,^a ^* Sdassi Hamid,^a Abdellatif El Kihel,^a Mohamed Saadi ^b and Lahcen El Ammari ^b

^aLaboratoire de Chimie Bioorganique, Faculté des Sciences, Université Chouaib Doukkali, BP 20, M-24000 El Jadida, Morocco, and ^bLaboratoire de Chimie Appliquée des Matériaux, Centre des Sciences des Matériaux, Faculty of Sciences, Mohammed V University in Rabat, Avenue Ibn Batouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: abouelhaoul12@yahoo.com

Edited by J. Simpson, University of Otago, New Zealand (Received 24 September 2019; accepted 1 October 2019; online 3 October 2019)

The title compound, C₁₆H₁₆N₂O₆, lies about an inversion centre at the mid-point of the N—N bond. The molecule features two intramolecular O—H⋯N and two C—H⋯O hydrogen bonds, each of which forms an S(6) ring motif. In the crystal, molecules are linked by C—H⋯O hydrogen bonds into infinite zigzag chains propagating along the c-axis direction. π–π stacking interactions between the pyrone rings [centroid–centroid distances = 3.975 (2) Å] stack the molecules along b.

Keywords: bispyrone derivative; heterocyclic compounds; crystal structure.

CCDC references: 1956978; 1956978

Structure description

The condensation of primary amine with several lactones has been reported. Ammonia and primary amines react with 2-pyrones to afford the corresponding 2-pyridones (Castillo et al., 1982 ; Wang et al., 1971 ; Djerrari et al., 1993 ; El Kihel et al., 1999 ; Djerrari et al., 2002 ). Other authors have investigated the condensation of bis-nucleophiles with 4-hydroxy-6-methyl-2-pyrone and dehydroacetic acid (3-acetyl-4-hydroxy-6-methyl-2-pyrone) and had to postulate a ring opening of these pyrones to account for the experimental results (El Abbassi et al., 1997 ; Fettouhi et al., 1996 ; El Abbassi et al., 1989 ). Some bis-pyrone derivatives have been reported to be excellent ligands for complexation with ruthenium metal (Venkatachalam et al., 2005 ). The present work reports the synthesis of a bis-pyrone derivative from the condensation of hydrated hydrazine with dehydroacetic acid. The NMR and mass spectra cannot confirm the structure of the product (either a bis-pyrone or a bis-pyridone). In order to establish the structure of this product, single crystals were prepared for X-ray analysis.

The asymmetric unit of the title compound contains half of the molecule with the other half generated by inversion symmetry. Two strong intramolecular hydrogen bonds complete the S(6) ring motifs as shown in Fig. 1. All non-hydrogen atoms of the molecule are almost coplanar, the maximum deviation from the mean plane through all of the non hydrogen atoms being 0.082 (2) Å for atom C1.

Figure 1
The title molecule with the atom-labelling scheme. The intramolecular hydrogen bonds are represented by dashed lines. Displacement ellipsoids are drawn at the 50% probability level.

In the crystal, the molecules are linked by C3—H3⋯O3 and C8—H8A⋯O2 hydrogen bonds (Table 1), forming zigzag chains running along the c-axis direction as shown in Fig. 2. In addition, molecules are stacked along b by π–π interactions between the pyridone rings with a centroid–centroid distance of 3.975 (2) Å, Fig. 3.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N1	0.82	1.73	2.4659 (18)	148
C3—H3⋯O3ⁱ	0.93	2.57	3.420 (2)	152
C8—H8A⋯O2ⁱⁱ	0.96	2.55	3.278 (2)	133
C8—H8B⋯O3	0.96	2.05	2.821 (3)	136
Symmetry codes: (i) $[x, -y+1, z-{\script{1\over 2}}]$ ; (ii) $[x, -y, z+{\script{1\over 2}}]$ .

Figure 2
Projection of the title structure along (010), showing molecules connected by hydrogen bonds (dashed cyan lines). For clarity, only H atoms involved in these interactions have been included.

Figure 3
Crystal packing of the title compound showing molecules linked by hydrogen bonds (dashed cyan lines) and π–π interaction (green lines). For clarity, only H atoms involved in these interactions have been included.

Synthesis and crystallization

A mixture of dehydroacetic acid (20 mmol) and hydrazine monohydrate (10 mmol) was heated under reflux in n-butanol (30 ml) for 24 h. The solid was separated by filtration and recrystallized several times from CHCl₃ to give crystals, yield (52.1%).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₁₆N₂O₆
M_r	332.31
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	27.797 (3), 3.9750 (4), 14.4569 (15)
β (°)	110.642 (4)
V (Å³)	1494.8 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.12
Crystal size (mm)	0.32 × 0.25 × 0.19

Data collection
Diffractometer	Bruker D8 VENTURE Super DUO
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.678, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	15395, 1627, 1221
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.148, 1.03
No. of reflections	1627
No. of parameters	112
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.23
Computer programs: APEX3 and SAINT (Bruker, 2016 ), SHELXTL2014 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), WinGX and ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC references: 1956978; 1956978

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619013488/sj4210sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619013488/sj4210Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXTL2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: WinGX and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010).

3,3'-[(1E,1'E)-Hydrazine-1,2-diylidenebis(ethan-1-yl-1-ylidene)]bis(4-hydroxy-6-methyl-2H-pyran-2-one) top

Crystal data top

C₁₆H₁₆N₂O₆	F(000) = 696
M_r = 332.31	D_x = 1.477 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 27.797 (3) Å	Cell parameters from 1626 reflections
b = 3.9750 (4) Å	θ = 3.0–27.1°
c = 14.4569 (15) Å	µ = 0.12 mm⁻¹
β = 110.642 (4)°	T = 296 K
V = 1494.8 (3) Å³	Block, colourless
Z = 4	0.32 × 0.25 × 0.19 mm

Data collection top

Bruker D8 VENTURE Super DUO diffractometer	1627 independent reflections
Radiation source: INCOATEC IµS micro-focus source	1221 reflections with I > 2σ(I)
HELIOS mirror optics monochromator	R_int = 0.043
Detector resolution: 10.4167 pixels mm^-1	θ_max = 27.1°, θ_min = 3.0°
φ and ω scans	h = −34→34
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −5→5
T_min = 0.678, T_max = 0.746	l = −18→18
15395 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.050	w = 1/[σ²(F_o²) + (0.0725P)² + 1.6983P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.148	(Δ/σ)_max = 0.003
S = 1.03	Δρ_max = 0.33 e Å⁻³
1627 reflections	Δρ_min = −0.23 e Å⁻³
112 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.009 (3)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.31666 (5)	0.5614 (4)	0.29992 (10)	0.0404 (4)
O2	0.44045 (5)	0.0821 (4)	0.27764 (9)	0.0486 (5)
H2	0.462232	0.040600	0.331799	0.073*
O3	0.34743 (6)	0.5875 (5)	0.46061 (11)	0.0582 (5)
N1	0.47971 (5)	0.0522 (4)	0.45929 (10)	0.0318 (4)
C1	0.27228 (8)	0.5809 (6)	0.12749 (15)	0.0467 (6)
H1A	0.277478	0.547070	0.065932	0.070*
H1C	0.265360	0.814272	0.134436	0.070*
H1B	0.243653	0.447745	0.128495	0.070*
C2	0.31917 (7)	0.4781 (5)	0.21031 (13)	0.0340 (5)
C3	0.35979 (7)	0.3216 (5)	0.20315 (13)	0.0365 (5)
H3	0.360757	0.268689	0.141167	0.044*
C4	0.40194 (7)	0.2338 (5)	0.28963 (13)	0.0331 (5)
C5	0.40009 (6)	0.3095 (5)	0.38391 (12)	0.0289 (4)
C6	0.44140 (7)	0.2111 (5)	0.47291 (12)	0.0286 (4)
C7	0.35581 (7)	0.4878 (5)	0.38895 (13)	0.0350 (5)
C8	0.44100 (8)	0.2785 (6)	0.57414 (14)	0.0462 (6)
H8A	0.445878	0.071299	0.610416	0.069*
H8B	0.408612	0.375886	0.569385	0.069*
H8C	0.468260	0.431695	0.607768	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0338 (7)	0.0534 (9)	0.0312 (7)	0.0104 (6)	0.0080 (6)	0.0023 (6)
O2	0.0377 (8)	0.0835 (12)	0.0236 (6)	0.0184 (8)	0.0095 (6)	−0.0017 (7)
O3	0.0504 (9)	0.0911 (13)	0.0341 (8)	0.0279 (9)	0.0161 (7)	−0.0045 (8)
N1	0.0281 (8)	0.0433 (10)	0.0218 (7)	0.0037 (6)	0.0061 (6)	0.0014 (6)
C1	0.0391 (11)	0.0533 (14)	0.0381 (11)	0.0050 (10)	0.0015 (9)	0.0075 (10)
C2	0.0328 (10)	0.0379 (11)	0.0279 (9)	−0.0028 (8)	0.0063 (7)	0.0045 (8)
C3	0.0352 (10)	0.0510 (13)	0.0216 (8)	−0.0004 (9)	0.0078 (7)	0.0028 (8)
C4	0.0299 (9)	0.0440 (11)	0.0253 (9)	0.0002 (8)	0.0096 (7)	0.0012 (8)
C5	0.0289 (9)	0.0348 (10)	0.0231 (8)	0.0006 (7)	0.0092 (7)	0.0008 (7)
C6	0.0307 (9)	0.0319 (10)	0.0239 (8)	−0.0024 (7)	0.0105 (7)	0.0006 (7)
C7	0.0314 (9)	0.0432 (11)	0.0294 (9)	0.0046 (8)	0.0095 (7)	0.0027 (8)
C8	0.0489 (12)	0.0662 (15)	0.0236 (9)	0.0188 (11)	0.0130 (8)	0.0027 (9)

Geometric parameters (Å, º) top

O1—C2	1.363 (2)	C2—C3	1.325 (3)
O1—C7	1.392 (2)	C3—C4	1.423 (2)
O2—C4	1.293 (2)	C3—H3	0.9300
O2—H2	0.8200	C4—C5	1.414 (2)
O3—C7	1.206 (2)	C5—C6	1.444 (2)
N1—C6	1.311 (2)	C5—C7	1.444 (3)
N1—N1ⁱ	1.376 (3)	C6—C8	1.492 (2)
C1—C2	1.483 (3)	C8—H8A	0.9600
C1—H1A	0.9600	C8—H8B	0.9600
C1—H1C	0.9600	C8—H8C	0.9600
C1—H1B	0.9600

C2—O1—C7	122.85 (15)	C5—C4—C3	119.73 (17)
C4—O2—H2	109.5	C4—C5—C6	120.89 (16)
C6—N1—N1ⁱ	118.75 (18)	C4—C5—C7	118.31 (16)
C2—C1—H1A	109.5	C6—C5—C7	120.80 (15)
C2—C1—H1C	109.5	N1—C6—C5	115.43 (15)
H1A—C1—H1C	109.5	N1—C6—C8	121.41 (16)
C2—C1—H1B	109.5	C5—C6—C8	123.15 (16)
H1A—C1—H1B	109.5	O3—C7—O1	113.60 (16)
H1C—C1—H1B	109.5	O3—C7—C5	129.10 (17)
C3—C2—O1	121.28 (16)	O1—C7—C5	117.30 (15)
C3—C2—C1	126.66 (18)	C6—C8—H8A	109.5
O1—C2—C1	112.07 (17)	C6—C8—H8B	109.5
C2—C3—C4	120.47 (17)	H8A—C8—H8B	109.5
C2—C3—H3	119.8	C6—C8—H8C	109.5
C4—C3—H3	119.8	H8A—C8—H8C	109.5
O2—C4—C5	122.80 (16)	H8B—C8—H8C	109.5
O2—C4—C3	117.46 (16)

C7—O1—C2—C3	−0.3 (3)	N1ⁱ—N1—C6—C8	−0.2 (3)
C7—O1—C2—C1	179.27 (17)	C4—C5—C6—N1	0.4 (3)
O1—C2—C3—C4	0.5 (3)	C7—C5—C6—N1	−179.64 (17)
C1—C2—C3—C4	−179.1 (2)	C4—C5—C6—C8	−178.80 (18)
C2—C3—C4—O2	−179.86 (19)	C7—C5—C6—C8	1.2 (3)
C2—C3—C4—C5	1.0 (3)	C2—O1—C7—O3	178.35 (18)
O2—C4—C5—C6	−1.6 (3)	C2—O1—C7—C5	−1.2 (3)
C3—C4—C5—C6	177.46 (17)	C4—C5—C7—O3	−176.9 (2)
O2—C4—C5—C7	178.38 (19)	C6—C5—C7—O3	3.1 (3)
C3—C4—C5—C7	−2.5 (3)	C4—C5—C7—O1	2.6 (3)
N1ⁱ—N1—C6—C5	−179.43 (19)	C6—C5—C7—O1	−177.38 (16)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1	0.82	1.73	2.4659 (18)	148
C3—H3···O3ⁱⁱ	0.93	2.57	3.420 (2)	152
C8—H8A···O2ⁱⁱⁱ	0.96	2.55	3.278 (2)	133
C8—H8B···O3	0.96	2.05	2.821 (3)	136

Symmetry codes: (ii) x, −y+1, z−1/2; (iii) x, −y, z+1/2.

Acknowledgements

The authors thank the Faculty of Science, Mohammed V University in Rabat, Morocco for the X-ray measurements and Chouaib Doukkali University (El Jadida Morocco) for support.

References

Bruker (2016). APEX3, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Castillo, S., Ouaddahi, H. & Hérault, V. (1982). Bull. Soc. Chim. Fr. 11, 257–261. Google Scholar
Djerrari, B., Essassi, E. M. & Fifani, J. (1993). Bull. Soc. Chim. Belg. 102, 565–573. CrossRef CAS Google Scholar
Djerrari, B., Essassi, E. M., Fifani, J. & Garrigues, B. (2002). C. R. Chim. 5, 177–183. Web of Science CrossRef CAS Google Scholar
El Abbassi, M., Djerrari, B., Essassi, E. M. & Fifani, J. (1989). Tetrahedron Lett. 30, 7069–7070. CrossRef CAS Web of Science Google Scholar
El Abbassi, M., Essassi, E. M. & Fifani, J. (1997). Bull. Soc. Chim. Belg. 106, 205–210. CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Fettouhi, M., Boukhari, A., El Otmani, B. & Essassi, E. M. (1996). Acta Cryst. C52, 1031–1032. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
El Kihel, A., Benchidmi, M., Essassi, E. M., Bauchat, P. & Danion-Bougot, R. (1999). Synth. Commun. 29, 2435–2445. CAS Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Venkatachalam, G. & Ramesh, R. (2005). Inorg. Chem. Commun. 8, 1009–1013. Web of Science CrossRef CAS Google Scholar
Wang, C. S., Easterly, J. P. & Skelly, N. E. (1971). Tetrahedron, 27, 2581–2589. CrossRef CAS Web of Science Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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