(E)-5-[(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)imino-meth-yl]-2-meth-oxy-phenyl 4-chloro-benzene-sulfonate.

Abstract

In the title compound, C(25)H(22)ClN(3)O(5)S, 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 mol-ecules into inversion dimers.

Full text

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(E)-5-[(1,5-Dimethyl-3-oxo-2-phenyl-2,3-
dihydro-1H-pyrazol-4-yl)iminomethyl]-2-
methoxyphenyl 4-chlorobenzene-
sulfonate
Tian-Xiang Lei
Department Of Electrical Engineering, North China Electric Power University,
Baoding City, Hebei Province 071003, People’s Republic of China
Correspondence e-mail: lei_tianxiang@163.com
Received 6 June 2012; accepted 10 June 2012
Key indicators: single-crystal X-ray study; T = 294 K; mean ?(C–C) = 0.004 A ˚;
R factor = 0.056; wR factor = 0.154; data-to-parameter ratio = 13.5.
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
C25H22ClN3O5SMr= 511.98
Monoclinic, P21=c
a = 11.063 (2) A˚
b = 10.153 (2) A˚
c = 22.159 (4) A˚
? = 98.73 (3)?
V = 2460.1 (8) A˚3
Z = 4
Mo K? radiation
? = 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)
Tmin= 0.907, Tmax= 0.951
19683 measured reflections
4315 independent reflections
3016 reflections with I > 2?(I)
Rint= 0.052
Refinement
R[F2> 2?(F2)] = 0.056
wR(F2) = 0.154
S = 1.00
4315 reflections
319 parameters
H-atom parameters constrained
??max= 0.34 e A˚?3
??min= ?0.45 e A˚?3
Table 1
Hydrogen-bond geometry (A˚,?).
D—H???A
C11—H11???O5i
Symmetry code: (i) ?x þ 2;?y þ 1;?z.
D—HH???AD???AD—H???A
0.932.43 3.199 (3) 140
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,
SHELXTL (Sheldrick, 2008); software used to prepare material for
publication: SHELXTL.
2008);molecular graphics:
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: CV5310).
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor,
R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Bruker (1999). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin,
USA.
Guo, M.-J., Chen, X. & Yao, J.-X. (2010). Acta Cryst. E66, o1360.
Han, J.-R., Tian, X., Zhen, X.-L., Li, Z.-C. & Liu, S.-X. (2008). Acta Cryst. E64,
o2244.
Santos, M. L. P., Bagatin, I. A., Pereira, E. M. & Ferreira, A. M. D. C. (2001). J.
Chem. Soc. Dalton Trans. pp. 838–844.
Sheldrick, G. M. (1996). SADABS. University of Go ¨ttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Zhang, Q.-Z., Zhao, Y.-L., Chen, X. & Yu, M. (2006). Acta Cryst. E62, o5252–
o5254.
organic compounds
o2110
Tian-Xiang Leidoi:10.1107/S160053681202627X
Acta Cryst. (2012). E68, o2110
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

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Acta Cryst. (2012). E68, o2110
supplementary materials
Acta Cryst. (2012). E68, o2110 [doi:10.1107/S160053681202627X]
(E)-5-[(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)imino-
methyl]-2-methoxyphenyl 4-chlorobenzenesulfonate
Tian-Xiang Lei
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-bromobenzene-
sulfonate (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-Di-
methyl-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 aceto-
nitrile, 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.
Refinement
The H atoms were included in calculated positions and refined using a riding model approximation. Constrained C—H
bond lengths and isotropic U parameters: 0.93 Å and Uiso(H) = 1.2Ueq(C) for Csp2—H; 0.96 Å and Uiso(H) = 1.5Ueq(C) for
methyl C—H.

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Acta Cryst. (2012). E68, o2110
Computing details
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999);
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 (Sheldrick, 2008).
Figure 1
The structure of the title molecule, with displacement ellipsoids for non-H atoms drawn at the 50% probability level.

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Acta Cryst. (2012). E68, o2110
Figure 2
A portion of the crystal packing showing weak C—H···O interactions as dashed lines.
(E)-5-[(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4- yl)iminomethyl]-2-methoxyphenyl 4-
chlorobenzenesulfonate
Crystal data
C25H22ClN3O5S
Mr = 511.98
Monoclinic, P21/c
Hall symbol: -P 2ybc
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
F(000) = 1064
Dx = 1.382 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 5316 reflections
θ = 2.7–27.9°
µ = 0.28 mm−1
T = 294 K
Block, yellow
0.30 × 0.26 × 0.18 mm
Data collection
Bruker SMART APEX CCD area-detector
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
φ and ω scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.907, Tmax = 0.951
19683 measured reflections
4315 independent reflections
3016 reflections with I > 2σ(I)
Rint = 0.052
θmax = 25.0°, θmin = 2.4°
h = −11→13
k = −12→11
l = −26→26
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.056
wR(F2) = 0.154
S = 1.00
4315 reflections
319 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0919P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.34 e Å−3
Δρmin = −0.45 e Å−3
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full
covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and
torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry.
An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is
used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based
on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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Acta Cryst. (2012). E68, o2110
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
xyzUiso*/Ueq
Cl1
S1
N1
N2
N3
O1
O2
O3
O4
O5
C1
C2
H2
C3
H3
C4
C5
H5
C6
H6
C7
C8
H8
C9
C10
H10
C11
H11
C12
C13
H13A
H13B
H13C
C14
H14
C15
C16
C17
C18
H18A
H18B
H18C
C19
H19A
H19B
H19C
C20
0.47353 (11)
0.44039 (6)
0.80799 (17)
0.91575 (19)
0.88868 (18)
0.36954 (18)
0.41778 (17)
0.57713 (14)
0.70559 (15)
0.92591 (17)
0.4426 (2)
0.4230 (3)
0.4046
0.4310 (3)
0.4171
0.4600 (3)
0.4784 (3)
0.4966
0.4693 (2)
0.4812
0.67271 (19)
0.7020 (2)
0.6593
0.7967 (2)
0.8574 (2)
0.9176
0.8311 (2)
0.8754
0.7384 (2)
0.7683 (3)
0.8534
0.7334
0.7602
0.8334 (2)
0.8762
0.8452 (2)
0.8973 (2)
0.8386 (2)
0.7882 (3)
0.7636
0.8497
0.7188
0.8505 (3)
0.8321
0.9152
0.7790
0.9860 (2)
1.05947 (9)
0.44761 (7)
0.1811 (2)
0.0090 (2)
−0.09430 (19)
0.4061 (2)
0.3950 (2)
0.40946 (15)
0.62701 (17)
0.23713 (16)
0.6207 (3)
0.6931 (3)
0.6510
0.8292 (3)
0.8797
0.8884 (3)
0.8173 (4)
0.8596
0.6812 (3)
0.6311
0.4424 (2)
0.3589 (2)
0.2804
0.3923 (2)
0.5106 (2)
0.5362
0.5919 (2)
0.6690
0.5579 (2)
0.7483 (3)
0.7307
0.7898
0.8058
0.3028 (3)
0.3361
0.0964 (2)
0.1298 (2)
−0.0375 (2)
−0.1191 (3)
−0.0631
−0.1794
−0.1676
−0.2198 (3)
−0.2801
−0.2551
−0.2070
−0.0126 (2)
0.12284 (7)
0.13133 (3)
0.00538 (9)
−0.11867 (10)
−0.08078 (9)
0.17629 (10)
0.07100 (9)
0.16147 (7)
0.19204 (8)
−0.11241 (9)
0.12761 (12)
0.17786 (15)
0.2126
0.17608 (19)
0.2094
0.1241 (2)
0.07370 (18)
0.0389
0.07553 (14)
0.0418
0.12844 (10)
0.08434 (11)
0.0761
0.05159 (11)
0.06549 (11)
0.0428
0.11203 (11)
0.1213
0.14468 (11)
0.20859 (15)
0.2222
0.2409
0.1738
0.00548 (11)
−0.0242
−0.03798 (11)
−0.09185 (11)
−0.03448 (11)
0.01137 (13)
0.0422
0.0299
−0.0083
−0.10901 (15)
−0.0783
−0.1285
−0.1389
−0.16676 (11)
0.1381 (5)
0.0563 (3)
0.0454 (5)
0.0515 (6)
0.0477 (5)
0.0786 (7)
0.0729 (6)
0.0497 (5)
0.0548 (5)
0.0617 (5)
0.0516 (7)
0.0699 (8)
0.084*
0.0835 (10)
0.100*
0.0829 (10)
0.0809 (10)
0.097*
0.0651 (8)
0.078*
0.0406 (6)
0.0440 (6)
0.053*
0.0426 (6)
0.0480 (6)
0.058*
0.0462 (6)
0.055*
0.0425 (6)
0.0705 (9)
0.106*
0.106*
0.106*
0.0479 (6)
0.057*
0.0426 (6)
0.0464 (6)
0.0454 (6)
0.0641 (8)
0.096*
0.096*
0.096*
0.0740 (9)
0.111*
0.111*
0.111*
0.0464 (6)