(E)-5-[(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)imino­meth­yl]-2-methoxy­phenyl 4-bromo­benzene­sulfonate

Min-Jie Guo; Xin Chen; Jing-Xia Yao

doi:10.1107/S1600536810017198

. 2010 May 15;66(Pt 6):o1360. doi: 10.1107/S1600536810017198

(E)-5-[(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)iminomethyl]-2-methoxyphenyl 4-bromobenzenesulfonate

Min-Jie Guo ^a, Xin Chen ^a, Jing-Xia Yao ^a,^*

PMCID: PMC2979573 PMID: 21579444

Abstract

In the title compound, C₂₅H₂₂BrN₃O₅S, the central benzene ring makes dihedral angles of 32.02 (14), 37.49 (18) and 80.52 (13)°, respectively, with the pyrazolone ring, the bromobenzene ring and the terminal phenyl ring. This conformation features a short intramolecular C—H⋯O contact that generates an S(6) ring. In the crystal, inversion dimers linked by pairs of C—H⋯O=C hydrogen bonds occur.

Related literature

For general background to Schiff bases, see: Santos et al. (2001 ▶). For related structures, see: Chen & Yu (2006 ▶); Zhang et al. (2006 ▶). For reference structural data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₂₅H₂₂BrN₃O₅S
M _r = 556.43
Monoclinic,
a = 11.102 (2) Å
b = 10.336 (2) Å
c = 22.160 (4) Å
β = 98.81 (3)°
V = 2512.9 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.76 mm⁻¹
T = 294 K
0.24 × 0.20 × 0.12 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.628, T _max = 0.810
12656 measured reflections
4431 independent reflections
2007 reflections with I > 2σ(I)
R _int = 0.080

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.163
S = 1.00
4431 reflections
320 parameters
H-atom parameters constrained
Δρ_max = 0.98 e Å⁻³
Δρ_min = −0.82 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 datablocks I, global. DOI: 10.1107/S1600536810017198/hb5442sup1.cif

e-66-o1360-sup1.cif^{(23.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017198/hb5442Isup2.hkl

e-66-o1360-Isup2.hkl^{(217.1KB, hkl)}

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	2.36	3.046 (7)	130
C9—H9⋯O5ⁱ	0.93	2.45	3.238 (6)	143

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Symmetry code: (i) Inline graphic .

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-(2-(4-Chlorobenzyloxy)benzylideneamino) -2,3-dimethyl-1-phenyl-1,2-dihydropyrazol-5-one (Zhang et al., 2006) 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 and angles are within normal ranges (Allen et al., 1987). The pyrazolone ring (C15—C17/N1—N3/O5) is almost planar, with an r.m.s. deviation for fitted atoms of 0.0331 Å. It makes a dihedral angle of 51.63 (17)° with the attached phenyl ring (C20—C25). The central benzene ring (C7—C12/C14/O3/O4) is nearly planar, with an r.m.s. deviation for fitted atoms of 0.0371 Å. This group makes dihedral angles of 32.02 (14)°, 37.49 (18)° and 80.52 (13)°, respectively, with the the pyrazolone ring (C15—C17/N1—N3/O5), the bromobenzene ring (C1—C6) and the terminal phenyl ring (C20—C25).

An intramolecular C14—H14···O5═C16 hydrogen bond is found in (I) (Table 1), which helps to stabilize the conformation of the molecule. Packing is stabilised by weak, non-classical intermolecular C9—H9···O5═C16 hydrogen bonds that form inversion related dimers (Table 1, Fig. 2).

Experimental

An anhydrous ethanol solution (50 ml) of 5-formyl-2-methoxyphenyl 4-bromobenzenesulfonate (3.71 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 83% yield. Yellow blocks of (I) were obtained by slow evaporation of an acetonitrile solution.