(E)-2-Bromo-4-[(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)imino­meth­yl]-6-meth­oxy­phenyl 4-methyl­benzene­sulfonate

Zhong-Yu Duan; Lin Yang; Li-Ping Yang; Xiu-Wu Liu

doi:10.1107/S160053681201447X

. 2012 Apr 6;68(Pt 5):o1335. doi: 10.1107/S160053681201447X

(E)-2-Bromo-4-[(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)iminomethyl]-6-methoxyphenyl 4-methylbenzenesulfonate

Zhong-Yu Duan ^a,^*, Lin Yang ^a, Li-Ping Yang ^a, Xiu-Wu Liu ^a

PMCID: PMC3344472 PMID: 22590234

Abstract

In the title compound, C₂₆H₂₄BrN₃O₅S, the central benzene ring makes dihedral angles of 6.27 (6), 33.63 (6) and 69.31 (5)°, respectively, with the pyrazolone ring, the bromobenzene ring and the terminal phenyl ring. An intramolecular C—H⋯O hydrogen bond occurs. The crystal packing features weak non-classical C—Br⋯O interactions [Br⋯O = 3.222 (2) Å] that form inversion-related dimers.

Related literature

For general background to the use of Schiff base derivatives in the development of protein and enzyme mimics, see: Santos et al. (2001 ▶). For closely related crystal structures, see: Chen & Yu (2006 ▶); Han et al. (2008 ▶). For reference bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₂₆H₂₄BrN₃O₅S
M _r = 570.45
Monoclinic,
a = 10.210 (2) Å
b = 20.364 (5) Å
c = 12.171 (3) Å
β = 90.906 (4)°
V = 2530.2 (10) Å³
Z = 4
Mo Kα radiation
μ = 1.75 mm⁻¹
T = 294 K
0.25 × 0.20 × 0.13 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.653, T _max = 0.797
21416 measured reflections
4462 independent reflections
3998 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.071
S = 1.02
4462 reflections
329 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; 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.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681201447X/ds2184sup1.cif

e-68-o1335-sup1.cif^{(21.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681201447X/ds2184Isup2.hkl

e-68-o1335-Isup2.hkl^{(218.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681201447X/ds2184Isup3.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
C14—H14⋯O5	0.93	2.30	2.991 (2)	131

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Acknowledgments

The project was supported by Hebei Provincial Natural Science Foundation of China (project grant Nos. B2010000039 and B2008000023).

supplementary crystallographic information

Comment

There has been steady growth of interest in the synthesis, structure, and reactivity of Schiff bases due to their potentially biological activities such as protein and enzyme mimics (Santos et al., 2001). Among the large number of compounds, 4-amino-1,5-dimethyl-2-phenylpyrazol-3-one forms a variety of Schiff bases with aldehydes, and the synthesis and crystal structures of some of them, such as (E)-5-(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro- 1H-pyrazol-4-yliminomethyl)-2-methoxyphenyl benzenesulfonate (Chen & Yu, 2006) and (E)-4-((1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-ylimino) methyl)phenyl 4-bromobenzenesulfonate (Han et al., 2008) have been reported.

Structural information is useful when investigating the coordination properties of Schiff bases functioning as ligands. We report here the synthesis and molecular structure of the title Schiff base compound, (I), (Fig. 1)

In the title molecule (Fig. 1), bond lengths are within normal ranges (Allen et al., 1987). The pyrazolone ring (C16—C18/N1—N3/O5) is almost planar, with an r.m.s. deviation for fitted atoms of 0.0426 Å. It makes a dihedral angle of 63.05 (6)° with the attached phenyl ring (C21—C26). The central benzene ring (C8—C14/O3/O4) is nearly planar, with an r.m.s. deviation for fitted atoms of 0.0559 Å. This group makes dihedral angles of 6.27 (6)°, 33.63 (6)° and 69.31 (5)°, respectively, with the the pyrazolone ring (C16—C18/N1—N3/O5), the bromobenzene ring (C1—C6) and the terminal phenyl ring (C21—C26).

An intramolecular C14—H14···O5═C17 hydrogen bond is found in (I) (Table 1, Fig. 2), which helps to stabilize the conformation of the molecule. The crystal packing is stabilized by weak, non-classical intermolecular C9—Br1···O1═S1 interactions (the Br···O distance and the C—Br···O angle, 3.222 Å and 147.62 °) that form inversion related dimers.

Experimental

An anhydrous ethanol solution (50 ml) of 2-bromo-4-formyl-6-methoxyphenyl 4-methylbenzenesulfonate (3.85 g, 10 mmol) was added to an anhydrous ethanol solution (50 ml) of 4-amino-1,5-dimethyl-2-phenylpyrazol-3-one (2.03 g, 10 mmol) and the mixture stirred at 350 K for 3 h under N₂, giving a yellow precipitate. The product was isolated, recrystallized from acetonitrile, and then dried in a vacuum to give pure compound (I) in 85% yield. Yellow single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an acetonitrile solution.