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

Tian-Xiang Lei

doi:10.1107/S160053681202627X

. 2012 Jun 16;68(Pt 7):o2110. doi: 10.1107/S160053681202627X

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

Tian-Xiang Lei ^a,^*

PMCID: PMC3393922 PMID: 22798787

Abstract

In the title compound, C₂₅H₂₂ClN₃O₅S, the two N atoms in the pyrazole ring have a pyramidal environment, with the sums of the valence angles around them being 349.3 (2) and 357.5 (2)°. The phenyl ring is twisted by 50.97 (12)° from the pyrazole mean plane. In the crystal, pairs of weak C—H⋯O hydrogen bonds link the molecules into inversion 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 related structures, see: Zhang et al. (2006 ▶); Han et al. (2008 ▶); Guo et al. (2010 ▶). For reference bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₂₅H₂₂ClN₃O₅S
M _r = 511.98
Monoclinic,
a = 11.063 (2) Å
b = 10.153 (2) Å
c = 22.159 (4) Å
β = 98.73 (3)°
V = 2460.1 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 294 K
0.30 × 0.26 × 0.18 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.907, T _max = 0.951
19683 measured reflections
4315 independent reflections
3016 reflections with I > 2σ(I)
R _int = 0.052

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.154
S = 1.00
4315 reflections
319 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.45 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/S160053681202627X/cv5310sup1.cif

e-68-o2110-sup1.cif^{(28.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681202627X/cv5310Isup2.hkl

e-68-o2110-Isup2.hkl^{(211.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681202627X/cv5310Isup3.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
C11—H11⋯O5ⁱ	0.93	2.43	3.199 (3)	140

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

Schiff bases have extensively been studied because of 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-ylimino)methyl) -2-methoxyphenyl 4-bromobenzenesulfonate (Guo et al., 2010), (E)-4-((1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-ylimino)methyl) phenyl 4-bromobenzenesulfonate (Han et al., 2008) and (E)-4-(2-(4-Chlorobenzyloxy)benzylideneamino) -2,3-dimethyl-1-phenyl-1,2-dihydropyrazol-5-one (Zhang et al., 2006) have been reported. Herewith we report the synthesis and crystal structure of the title Schiff base compound.

In the title molecule (Fig. 1), bond lengths and angles are within normal ranges (Allen et al., 1987). Two N atoms in the pyrazole ring have a pyramidal environment with the sums of the valence angles around them of 349.3 (2) and 357.5 (2)°, respectively. The phenyl ring is twisted at 50.97 (12)° from the pyrazole mean plane. The central benzene ring (C7—C12) with three attached atoms (C14/O3/O4) is nearly planar, with an r.m.s. deviation for fitted atoms of 0.0392 Å. The mean plane of this fragment formss dihedral angles of 32.89 (8)°, 38.18 (10)° and 82.42 (7)°, respectively, with the the pyrazolone ring (C15—C17/N1—N3/O5), the chlorobenzene ring (C1—C6) and the terminal phenyl ring (C20—C25). Similar values of 32.02 (14)°, 37.49 (18)° and 80.52 (13)°, respectively, were observed in isostructural (E)-5-((1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol -4-ylimino)methyl)-2-methoxyphenyl 4-bromobenzenesulfonate (Guo et al., 2010).

In the crystal, non-classical intermolecular C11—H11···O5═ C16 hydrogen bonds (Table 1) form inversion-related dimers (Fig. 2).

Experimental

An anhydrous ethanol solution (100 ml) of 5-formyl-2-methoxyphenyl 4-chlorobenzenesulfonate (3.27 g, 10 mmol) was added to an anhydrous ethanol solution (100 ml) of 4-amino-1,5-dimethyl-2-phenylpyrazol-3-one (2.03 g, 10 mmol) and the mixture refluxed 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 76% yield. Yellow single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an acetonitrile solution.