2-[2-(4-Nitro­phen­yl)hydrazinyl­idene]-1,3-diphenyl­propane-1,3-dione

Carlos Bustos; Luis Alvarez-Thon; Daniela Barría; Maria Teresa Garland; Christian Sánchez

doi:10.1107/S1600536811021143

. 2011 Jun 4;67(Pt 7):o1587. doi: 10.1107/S1600536811021143

2-[2-(4-Nitrophenyl)hydrazinylidene]-1,3-diphenylpropane-1,3-dione

Carlos Bustos ^a, Luis Alvarez-Thon ^b,^*, Daniela Barría ^a, Maria Teresa Garland ^c, Christian Sánchez ^a

PMCID: PMC3151834 PMID: 21836996

Abstract

In the molecular structure of the title compound, C₂₁H₁₅N₃O₄, the interplanar angle between the benzoyl units is 89.7 (1)°. The corresponding angles between the phenylhydrazono and the benzoyl groups are 31.4 (3) and 60.8 (2)°, respectively. In the crystal, a strong resonance-assisted intramolecular hydrogen bond (N—H⋯O) and a weak intramolecular hydrogen bond (C—H⋯N) strongly affect the observed conformation of the molecule. The crystal packing is determined by a strong intermolecular hydrogen bond (N—H⋯O), giving rise to a helical chain along the a axis. In addition, two weak intermolecular contacts (C—H⋯O) are observed.

Related literature

For details of the synthesis, see: Bustos et al. (2007 ▶, 2009 ▶); Yao (1964 ▶). For resonance-assisted hydrogen bonds and related structures, see: Bertolasi et al. (1993 ▶, 1994 ▶); Bustos et al. (2011 ▶).

Experimental

Crystal data

C₂₁H₁₅N₃O₄
M _r = 373.36
Orthorhombic,
a = 8.2994 (7) Å
b = 8.6250 (7) Å
c = 25.018 (2) Å
V = 1790.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 150 K
0.30 × 0.28 × 0.12 mm

Data collection

Bruker D8 Discover with SMART CCD area-detector diffractometer
13939 measured reflections
2114 independent reflections
1826 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.084
S = 1.00
2114 reflections
257 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: 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: XP in SHELXTL/PC (Sheldrick, 2008 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2006 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811021143/im2291sup1.cif

e-67-o1587-sup1.cif^{(24KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811021143/im2291Isup2.hkl

e-67-o1587-Isup2.hkl^{(104KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811021143/im2291Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯O2	0.96 (3)	2.25 (3)	2.793 (2)	115.3 (19)
N2—H1⋯O1ⁱ	0.96 (3)	2.15 (2)	2.956 (2)	142 (2)
C5—H5⋯O3ⁱⁱ	0.95	2.60	3.419 (3)	145
C15—H15⋯N1	0.95	2.42	2.849 (3)	107
C20—H20⋯O2ⁱⁱⁱ	0.95	2.44	3.352 (2)	161

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors thank the Fondo Nacional de Desarrollo Científico y Tecnológico (FONDECYT; grant Nos. 11100446 and 1080269) and the Universidad Andrés Bello (grant No. DI-06-10-R) for financial assistance.

supplementary crystallographic information

Comment

The crystal structure of 2-[(4-nitro-phenyl)-hydrazono]-1,3-diphenyl-propane-1,3-dione is reported. This compound belongs to a family that contain a six-membered π–conjugated ring closed via strong intramolecular resonance assisted hydrogen bonds, N–H···O, RAHB (Resonance Assisted Hydrogen Bond) which, inter alia, could have remarkable importance as bistate in molecular switches (Bertolasi et al., 1993; Bertolasi et al., 1994; Bustos et al., 2011). On the other hand, it is well known that the phenyl diazonium salts are capable of coupling with a series of β-diketonate anions to give β-diketohydrazones containing N–H···O moieties (Yao, 1964; Bustos et al., 2007; Bustos et al., 2009). Using this reaction (Yao, 1964) we have prepared the title compound.

The molecular structure of the title compound, C₂₁H₁₅N₃O₄, exhibits a strong intramolecular hydrogen bond (N2–H1···O2) and a weak intramolecular hydrogen bond (C15–H15···N1) (Fig. 1 and Tab. 1). In the crystal structure, strong intermolecular hydrogen bonds (N2–H1···O1ⁱ) link the molecules into helical chains along the a axis, which may be the reason why the title compound crystallizes in the chiral space group P2₁2₁2₁ (see Fig. 2 and Tab. 1), [symmetry code: (i) x + 1/2, -y + 3/2, -z]. On the other hand, weak intermolecular contacts of the type C5–H5···O3ⁱⁱ and C20–H20···O2ⁱⁱⁱ, further stabilize the crystal packing to construct the entire three-dimensional network, see Fig. 3 and Tab. 1, [symmetry codes: (ii) -x + 3/2, -y + 1, -1/2 + z; (iii) x + 1/2, -y + 1/2, -z]. The interplanar angle between the benzoyl moieties is 89.7 (1)°. The corresponding angles between the phenyl-hydrazono and the benzoyl groups, are 31.4 (3)° and 60.8 (2)°, respectively.

Experimental

In a 500 ml flask, 2.24 g (0.01 mole) of 1,3-diphenylpropane-1,3-dione were dissolved in 100 ml of a ethanolic solution that contained 0.4 g (0.01 mole) of sodium hydroxide and 3.65 g (0.045 mole) of sodium acetate. The resulting β-diketonate solution was diluted with water to a final volume of about 220 ml, stirred and cooled at 268 K. In another 50 ml beaker a diazonium ion solution was prepared adding 1.39 g (0.01 mole) of 4-nitroaniline (99%) in 8 ml of hydrochloric acid (5 mol/L), cooling at 268 K, and adding a saturated aqueous solution containing 0.69 g (0.01 mole) of sodium nitrite. The diazonium salt solution was then added dropwise with vigorous stirring at 268 K into the β-diketonate solution. During the addition a yellow solid precipitate of the title compound was formed which was filtered by suction, washed with an abundant quantity of water and dried in the vacuum at 313 K (Yield: 91% of crude product). Single crystals suitable for X-ray studies were obtained by recrystallization from ethanol.