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

Carlos Bustos; Luis Alvarez-Thon; Juan-Guillermo Cárcamo; Andrés Ibañez; Christian Sánchez

doi:10.1107/S1600536811017909

. 2011 May 20;67(Pt 6):o1450–o1451. doi: 10.1107/S1600536811017909

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

Carlos Bustos ^a, Luis Alvarez-Thon ^b,^*, Juan-Guillermo Cárcamo ^c, Andrés Ibañez ^d, Christian Sánchez ^a

PMCID: PMC3120543 PMID: 21754825

Abstract

The molecular structure of the title compound, C₂₁H₁₅ClN₂O₂, features one strong intramolecular N—H⋯O resonance-assisted hydrogen bond (RAHB). In the crystal, molecules form inversion-related dimers via pairs of weak intermolecular N—H⋯O contacts. These dimers are further stabilized via three weak C—H⋯O contacts, developing the three-dimensional structure.

Related literature

For resonance-assisted hydrogen bonds, see: Bertolasi et al. (1993 ▶, 1994a ▶,b ▶); Inabe (1991 ▶); Krygowski et al. (1997 ▶); Olivieri et al. (1989 ▶). For details of the synthesis, see: Bustos et al. (2007 ▶, 2009 ▶); Yao (1964 ▶).

Experimental

Crystal data

C₂₁H₁₅ClN₂O₂
M _r = 362.80
Monoclinic,
a = 10.2970 (9) Å
b = 10.3526 (9) Å
c = 16.8926 (15) Å
β = 102.131 (1)°
V = 1760.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 297 K
0.60 × 0.31 × 0.23 mm

Data collection

Bruker D8 Discover with SMART CCD area-detector diffractometer
11123 measured reflections
3573 independent reflections
2657 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.119
S = 0.98
3573 reflections
239 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 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 datablocks global, I. DOI: 10.1107/S1600536811017909/pk2324sup1.cif

e-67-o1450-sup1.cif^{(22.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811017909/pk2324Isup2.hkl

e-67-o1450-Isup2.hkl^{(175.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811017909/pk2324Isup3.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
N1—H1⋯O2	0.922 (17)	1.930 (18)	2.6205 (18)	130.1 (14)
C12—H12⋯N2	0.93	2.55	3.016 (2)	111
N1—H1⋯O1ⁱ	0.922 (17)	2.628 (17)	3.344 (3)	135.0 (13)
C6—H6⋯O1ⁱ	0.93	2.63	3.390 (2)	140

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the FONDECYT (grant Nos. 11100446 and 1080269) and Universidad Andrés Bello (grant No. DI-06–10-R).

supplementary crystallographic information

Comment

In recent years, much attention has been devoted to structural studies on heterodienic systems forming strong intramolecular hydrogen bonds, N—H···O, assisted by resonance (RAHB) which, inter alia, could have potential technological applications as bistate molecular switches (Olivieri et al., 1989; Inabe, 1991; Bertolasi et al., 1993; Bertolasi et al., 1994a; Bertolasi et al., 1994b; Krygowski et al., 1997; Bustos et al., 2007). On the other hand, it is well known that the phenyl diazonium salts are capable of coupling with a series of β-diketones that may yield the N—H···O moiety (Yao, 1964; Bustos et al., 2007; Bustos et al., 2009). In this report we present the crystal and molecular structure of the title compound 2-(2-(3-chlorophenyl)hydrazono)-1,3-diphenylpropane-1,3-dione, of formula 3-Cl—C₆H₄—NHN=C(COC₆H₅)₂.

The molecular structure of the title compound exhibits one weak intramolecular hydrogen bond (C12–H12···N2) and one strong intramolecular hydrogen bond (N1–H1···O2) assisted by resonance (RAHB), see Fig. 1 and Table 2. The molecules form an inversion dimer via a pair of weak intermolecular contacts N1–H1···O1^# and C6–H6···O1^# hydrogen bonds [Symmetry code: (#) -x, -y, 2 - z], (see Fig. 2). These dimers are further stabilized via three weak contacts of the type shown in Fig. 3, to develop the three-dimensional structure.

Experimental

Chemicals: 1,3-diphenylpropane-1,3-dione, 3-chloroaniline and sodium nitrite were procured from Sigma-Aldrich, and sodium hydroxide, sodium acetate, solvents and hydrochloric acid from Merck. Chemicals were used without further purification.

Procedure: In a 500 ml beaker were dissolved 2.24 g (0.01 mole) of 1,3-diphenylpropane-1,3-dione in 100 ml of an ethanol solution containing 0.4 g (0.01 mole) of sodium hydroxide and 3.65 g of sodium acetate. The resulting β-diketonate solution was kept at -5°C and diluted with water to around 220 mL with vigorous stirring. In another beaker, a diazonium ion solution was prepared adding 1.06 ml (0.01 mole) of 3-chloroaniline (99%, density 1.215 g/ml) in 8 ml of hydrochloric acid (5 mol/L), cooling at -5 °C, and adding a saturated aqueous solution containing 0.69 g (0.01 mole) of sodium nitrite. This solution was then added dropwise, with vigorous stirring, into the β-diketonate solution. During the addition, a yellow solid precipitate was observed. This precipitate was filtered by suction and washed with an abundant quantity of water. Single crystals suitable for X-ray studies were obtained by recrystallization from a saturated solution of the compound in a 3:1 ethanol/acetone mixture.