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

Carlos Bustos; Luis Alvarez-Thon; Juan-Guillermo Cárcamo; Maria Teresa Garland; Christian Sánchez

doi:10.1107/S1600536811017557

. 2011 May 14;67(Pt 6):o1426. doi: 10.1107/S1600536811017557

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

Carlos Bustos ^a, Luis Alvarez-Thon ^b,^*, Juan-Guillermo Cárcamo ^c, Maria Teresa Garland ^d, Christian Sánchez ^a

PMCID: PMC3120580 PMID: 21754806

Abstract

The conformation of the title molecule, C₂₁H₁₅BrN₂O₂, is stabilized by a weak intramolecular C—H⋯N hydrogen bond and a strong resonance-assisted N—H⋯O intramolecular hydrogen bond. In the crystal, the molecules are linked by weak intermolecular C—H⋯O interactions, forming zigzag chains along the b axis.

Related literature

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

Experimental

Crystal data

C₂₁H₁₅BrN₂O₂
M _r = 407.25
Monoclinic,
a = 12.0273 (9) Å
b = 10.2977 (8) Å
c = 14.2626 (11) Å
β = 96.452 (1)°
V = 1755.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 2.36 mm⁻¹
T = 150 K
0.44 × 0.41 × 0.12 mm

Data collection

Bruker D8 Discover diffractometer with SMART CCD area detector
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.368, T _max = 0.753
13742 measured reflections
3575 independent reflections
3107 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.079
S = 1.06
3575 reflections
235 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.17 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/S1600536811017557/pv2416sup1.cif

e-67-o1426-sup1.cif^{(23.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811017557/pv2416Isup2.hkl

e-67-o1426-Isup2.hkl^{(175.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811017557/pv2416Isup3.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—H21⋯O2	0.88	1.90	2.592 (2)	135
C8—H8⋯N1	0.95	2.60	3.060 (3)	110
C17—H17⋯O2ⁱ	0.95	2.46	3.382 (3)	162

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Symmetry code: (i) Inline graphic .

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

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, Resonance Assisted Hydrogen Bond) which, inter alia, could have potential technological applications as bistate molecular switches (Bertolasi et al., 1994; 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-diketonate anions to give β-diketohidrazones that contain the N—H···O core (Yao, 1964; Bustos et al., 2007; Bustos et al., 2009). Using this reaction (Yao, 1964) we have prepared the title compound and, in this report, we present its crystal and molecular structure determined by X-ray diffraction method.

The molecular structure of the title compound exhibits a strong intramolecular hydrogen bond (N2–H21···O2) and a weak intramolecular hydrogen bond (C8–H8···N1) (Fig. 1 and Tab. 1). The molecules are linked by weak intermolecular C17–H17···O2ⁱ interactions forming zigzag chains along the b axis (Fig. 2).

Experimental

In a 500 ml flask, 1,3-diphenylpropane-1,3-dione (2.24 g, 0.01 mole) was dissolved in an ethanol solution (100 ml) containing of sodium hydroxide (0.4 g, 0.01 mole) and of sodium acetate (3.65 g, 0.045 mole). 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 by adding 4-bromoaniline (97%) (1.77 g, 0.01 mole) in 8 ml of hydrochloric acid (5 mol/L), cooling at 268 K, and adding a saturated aqueous solution containing sodium nitrite (0.69 g, 0.01 mole). The diazonium salt solution was then added dropwise, with vigorous stirring, into the β-diketonate solution. During the addition a yellow solid precipitate of the title compound was formed which was filtered by suction and washed with an abundant quantity of water (Yield: 96% of crude product). Single crystals suitable for X-ray studies were obtained by recrystallization from a concentrated solution of the compound in ethanol.