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

In the title compound, C(25)H(22)BrN(3)O(5)S, the central benzene ring makes dihedral angles of 32.02 (14), 37.49 (18) and 80.52 (13)°, respectively, with the pyrazolone ring, the bromo-benzene 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 = 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

Δρmax = 0.98 e Å−3

Δρmin = −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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810017198/hb5442sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C25H22BrN3O5S	F(000) = 1136
Mr = 556.43	Dx = 1.471 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1629 reflections
a = 11.102 (2) Å	θ = 2.2–19.4°
b = 10.336 (2) Å	µ = 1.76 mm−1
c = 22.160 (4) Å	T = 294 K
β = 98.81 (3)°	Block, yellow
V = 2512.9 (8) Å3	0.24 × 0.20 × 0.12 mm
Z = 4

Bruker SMART APEX CCD diffractometer	4431 independent reflections
Radiation source: fine-focus sealed tube	2007 reflections with I > 2σ(I)
graphite	Rint = 0.080
φ and ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→13
Tmin = 0.628, Tmax = 0.810	k = −12→11
12656 measured reflections	l = −26→25

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.057	H-atom parameters constrained
wR(F2) = 0.163	w = 1/[σ2(Fo2) + (0.0562P)2 + 2.7821P] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
4431 reflections	Δρmax = 0.98 e Å−3
320 parameters	Δρmin = −0.82 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0027 (4)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > σ(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.

	x	y	z	Uiso*/Ueq
Br1	−0.02396 (8)	−0.56145 (7)	0.12388 (5)	0.1174 (5)
S1	−0.05698 (13)	0.05809 (14)	0.13190 (8)	0.0487 (4)
N1	0.3100 (4)	0.3198 (4)	0.0051 (2)	0.0395 (11)
N2	0.4162 (4)	0.4909 (4)	−0.1195 (2)	0.0452 (12)
N3	0.3891 (4)	0.5927 (4)	−0.0811 (2)	0.0417 (12)
O1	−0.1268 (4)	0.1008 (4)	0.1771 (2)	0.0718 (13)
O2	−0.0793 (3)	0.1107 (4)	0.07154 (18)	0.0615 (12)
O3	0.0813 (3)	0.0930 (3)	0.16212 (16)	0.0422 (9)
O4	0.2066 (3)	−0.1252 (3)	0.19075 (17)	0.0508 (10)
O5	0.4261 (3)	0.2660 (3)	−0.11424 (18)	0.0584 (11)
C1	−0.0754 (5)	−0.1852 (6)	0.1783 (3)	0.0611 (18)
H1	−0.0927	−0.1440	0.2133	0.073*
C2	−0.0685 (6)	−0.3191 (7)	0.1770 (4)	0.070 (2)
H2	−0.0824	−0.3682	0.2104	0.084*
C3	−0.0402 (6)	−0.3780 (7)	0.1246 (4)	0.071 (2)
C4	−0.0228 (6)	−0.3070 (7)	0.0741 (4)	0.069 (2)
H4	−0.0055	−0.3483	0.0392	0.083*
C5	−0.0314 (5)	−0.1730 (6)	0.0759 (3)	0.0566 (17)
H5	−0.0200	−0.1240	0.0420	0.068*
C6	−0.0571 (5)	−0.1124 (5)	0.1284 (3)	0.0449 (15)
C7	0.1760 (4)	0.0594 (5)	0.1284 (2)	0.0356 (13)
C8	0.2399 (4)	−0.0569 (5)	0.1435 (2)	0.0370 (13)
C9	0.3316 (5)	−0.0897 (5)	0.1096 (3)	0.0421 (14)
H9	0.3750	−0.1663	0.1178	0.050*
C10	0.3579 (5)	−0.0081 (5)	0.0636 (3)	0.0449 (15)
H10	0.4177	−0.0331	0.0408	0.054*
C11	0.2986 (4)	0.1100 (5)	0.0501 (2)	0.0379 (13)
C12	0.2050 (5)	0.1420 (5)	0.0842 (2)	0.0388 (14)
H12	0.1628	0.2195	0.0767	0.047*
C13	0.2697 (5)	−0.2459 (5)	0.2063 (3)	0.0636 (18)
H13A	0.2586	−0.3022	0.1714	0.095*
H13B	0.2374	−0.2863	0.2394	0.095*
H13C	0.3551	−0.2292	0.2184	0.095*
C14	0.3353 (5)	0.1982 (5)	0.0048 (3)	0.0429 (14)
H14	0.3779	0.1660	−0.0250	0.052*
C15	0.3472 (4)	0.4037 (5)	−0.0382 (2)	0.0361 (13)
C16	0.3973 (5)	0.3721 (5)	−0.0931 (3)	0.0403 (14)
C17	0.3399 (5)	0.5359 (5)	−0.0341 (2)	0.0406 (14)
C18	0.2903 (5)	0.6155 (5)	0.0127 (3)	0.0573 (17)
H18A	0.2546	0.5597	0.0397	0.086*
H18B	0.2293	0.6736	−0.0072	0.086*
H18C	0.3550	0.6645	0.0357	0.086*
C19	0.3517 (6)	0.7179 (5)	−0.1087 (3)	0.0663 (19)
H19A	0.2817	0.7063	−0.1394	0.099*
H19B	0.4173	0.7539	−0.1269	0.099*
H19C	0.3317	0.7757	−0.0778	0.099*
C20	0.4861 (5)	0.5129 (5)	−0.1677 (3)	0.0415 (14)
C21	0.4518 (5)	0.4494 (5)	−0.2229 (3)	0.0518 (16)
H21	0.3847	0.3944	−0.2280	0.062*
C22	0.5180 (6)	0.4683 (6)	−0.2703 (3)	0.0634 (19)
H22	0.4958	0.4249	−0.3071	0.076*
C23	0.6173 (7)	0.5514 (7)	−0.2633 (3)	0.074 (2)
H23	0.6601	0.5658	−0.2957	0.089*
C24	0.6519 (6)	0.6123 (6)	−0.2083 (3)	0.0669 (19)
H24	0.7196	0.6664	−0.2034	0.080*
C25	0.5879 (5)	0.5945 (5)	−0.1599 (3)	0.0543 (16)
H25	0.6121	0.6362	−0.1229	0.065*

	U11	U22	U33	U12	U13	U23
Br1	0.1074 (7)	0.0431 (5)	0.1895 (12)	0.0027 (4)	−0.0163 (6)	−0.0076 (5)
S1	0.0404 (9)	0.0425 (8)	0.0666 (12)	0.0128 (7)	0.0188 (8)	0.0081 (8)
N1	0.038 (3)	0.042 (3)	0.040 (3)	−0.002 (2)	0.007 (2)	0.008 (2)
N2	0.054 (3)	0.035 (3)	0.053 (3)	0.006 (2)	0.027 (3)	0.001 (2)
N3	0.050 (3)	0.031 (3)	0.046 (3)	0.008 (2)	0.013 (2)	0.005 (2)
O1	0.063 (3)	0.065 (3)	0.099 (4)	0.025 (2)	0.048 (3)	0.002 (3)
O2	0.057 (3)	0.067 (3)	0.060 (3)	0.015 (2)	0.006 (2)	0.032 (2)
O3	0.041 (2)	0.037 (2)	0.052 (3)	0.0062 (16)	0.0158 (18)	−0.0046 (18)
O4	0.051 (2)	0.047 (2)	0.054 (3)	0.0093 (18)	0.010 (2)	0.016 (2)
O5	0.074 (3)	0.039 (2)	0.068 (3)	0.006 (2)	0.031 (2)	−0.004 (2)
C1	0.058 (4)	0.056 (4)	0.073 (5)	0.000 (3)	0.020 (4)	0.008 (4)
C2	0.062 (5)	0.053 (5)	0.093 (6)	−0.006 (3)	0.005 (4)	0.027 (4)
C3	0.049 (4)	0.049 (4)	0.107 (7)	0.000 (3)	−0.012 (4)	−0.004 (5)
C4	0.060 (5)	0.061 (5)	0.081 (6)	0.007 (3)	−0.007 (4)	−0.021 (4)
C5	0.046 (4)	0.064 (5)	0.055 (5)	0.001 (3)	−0.008 (3)	−0.001 (4)
C6	0.039 (3)	0.038 (3)	0.057 (4)	0.001 (3)	0.006 (3)	0.007 (3)
C7	0.039 (3)	0.029 (3)	0.039 (3)	0.006 (2)	0.005 (3)	−0.001 (3)
C8	0.036 (3)	0.031 (3)	0.043 (4)	−0.001 (2)	0.003 (3)	0.005 (3)
C9	0.039 (3)	0.029 (3)	0.057 (4)	0.009 (2)	0.003 (3)	−0.004 (3)
C10	0.041 (3)	0.042 (3)	0.056 (4)	0.007 (3)	0.019 (3)	−0.001 (3)
C11	0.034 (3)	0.037 (3)	0.044 (4)	−0.001 (2)	0.009 (3)	0.001 (3)
C12	0.040 (3)	0.028 (3)	0.047 (4)	0.003 (2)	0.004 (3)	0.000 (3)
C13	0.069 (4)	0.045 (4)	0.076 (5)	0.014 (3)	0.009 (3)	0.020 (4)
C14	0.040 (4)	0.044 (3)	0.048 (4)	0.003 (3)	0.017 (3)	0.002 (3)
C15	0.030 (3)	0.035 (3)	0.044 (4)	0.005 (2)	0.007 (3)	−0.001 (3)
C16	0.039 (3)	0.034 (3)	0.049 (4)	0.002 (3)	0.010 (3)	0.003 (3)
C17	0.041 (3)	0.040 (3)	0.040 (4)	0.004 (3)	0.003 (3)	0.001 (3)
C18	0.066 (4)	0.048 (4)	0.061 (4)	0.008 (3)	0.016 (3)	−0.001 (3)
C19	0.085 (5)	0.041 (4)	0.078 (5)	0.018 (3)	0.029 (4)	0.016 (3)
C20	0.043 (4)	0.042 (3)	0.040 (4)	0.008 (3)	0.009 (3)	0.007 (3)
C21	0.052 (4)	0.056 (4)	0.048 (4)	0.011 (3)	0.009 (3)	0.004 (3)
C22	0.074 (5)	0.077 (5)	0.040 (4)	0.028 (4)	0.010 (4)	0.004 (4)
C23	0.082 (5)	0.089 (5)	0.061 (5)	0.024 (5)	0.040 (4)	0.031 (5)
C24	0.060 (4)	0.074 (5)	0.071 (5)	−0.003 (3)	0.023 (4)	0.012 (4)
C25	0.057 (4)	0.054 (4)	0.054 (4)	−0.003 (3)	0.016 (3)	0.004 (3)

Br1—C3	1.905 (7)	C9—H9	0.9300
S1—O1	1.427 (4)	C10—C11	1.398 (7)
S1—O2	1.430 (4)	C10—H10	0.9300
S1—O3	1.619 (4)	C11—C12	1.415 (7)
S1—C6	1.764 (6)	C11—C14	1.461 (7)
N1—C14	1.287 (6)	C12—H12	0.9300
N1—C15	1.403 (6)	C13—H13A	0.9600
N2—C16	1.390 (6)	C13—H13B	0.9600
N2—N3	1.414 (6)	C13—H13C	0.9600
N2—C20	1.433 (7)	C14—H14	0.9300
N3—C17	1.378 (6)	C15—C17	1.373 (7)
N3—C19	1.464 (6)	C15—C16	1.449 (7)
O3—C7	1.423 (6)	C17—C18	1.495 (7)
O4—C8	1.359 (6)	C18—H18A	0.9600
O4—C13	1.446 (6)	C18—H18B	0.9600
O5—C16	1.253 (6)	C18—H18C	0.9600
C1—C6	1.378 (8)	C19—H19A	0.9600
C1—C2	1.386 (8)	C19—H19B	0.9600
C1—H1	0.9300	C19—H19C	0.9600
C2—C3	1.389 (9)	C20—C21	1.388 (7)
C2—H2	0.9300	C20—C25	1.399 (7)
C3—C4	1.375 (9)	C21—C22	1.386 (8)
C4—C5	1.389 (8)	C21—H21	0.9300
C4—H4	0.9300	C22—C23	1.387 (9)
C5—C6	1.388 (8)	C22—H22	0.9300
C5—H5	0.9300	C23—C24	1.374 (9)
C7—C12	1.374 (7)	C23—H23	0.9300
C7—C8	1.410 (6)	C24—C25	1.386 (8)
C8—C9	1.397 (7)	C24—H24	0.9300
C9—C10	1.388 (7)	C25—H25	0.9300
O1—S1—O2	120.2 (3)	C11—C12—H12	119.8
O1—S1—O3	102.9 (2)	O4—C13—H13A	109.5
O2—S1—O3	108.7 (2)	O4—C13—H13B	109.5
O1—S1—C6	110.1 (3)	H13A—C13—H13B	109.5
O2—S1—C6	109.9 (3)	O4—C13—H13C	109.5
O3—S1—C6	103.6 (2)	H13A—C13—H13C	109.5
C14—N1—C15	120.8 (5)	H13B—C13—H13C	109.5
C16—N2—N3	110.2 (4)	N1—C14—C11	121.4 (5)
C16—N2—C20	126.0 (4)	N1—C14—H14	119.3
N3—N2—C20	121.4 (4)	C11—C14—H14	119.3
C17—N3—N2	106.4 (4)	C17—C15—N1	122.9 (5)
C17—N3—C19	124.9 (4)	C17—C15—C16	108.3 (5)
N2—N3—C19	118.6 (4)	N1—C15—C16	128.7 (4)
C7—O3—S1	117.3 (3)	O5—C16—N2	123.5 (5)
C8—O4—C13	116.9 (4)	O5—C16—C15	131.6 (5)
C6—C1—C2	120.9 (7)	N2—C16—C15	104.8 (4)
C6—C1—H1	119.6	C15—C17—N3	109.9 (5)
C2—C1—H1	119.6	C15—C17—C18	128.7 (5)
C1—C2—C3	118.4 (7)	N3—C17—C18	121.4 (5)
C1—C2—H2	120.8	C17—C18—H18A	109.5
C3—C2—H2	120.8	C17—C18—H18B	109.5
C4—C3—C2	121.5 (7)	H18A—C18—H18B	109.5
C4—C3—Br1	119.9 (6)	C17—C18—H18C	109.5
C2—C3—Br1	118.5 (6)	H18A—C18—H18C	109.5
C3—C4—C5	119.3 (7)	H18B—C18—H18C	109.5
C3—C4—H4	120.3	N3—C19—H19A	109.5
C5—C4—H4	120.3	N3—C19—H19B	109.5
C6—C5—C4	119.8 (6)	H19A—C19—H19B	109.5
C6—C5—H5	120.1	N3—C19—H19C	109.5
C4—C5—H5	120.1	H19A—C19—H19C	109.5
C1—C6—C5	120.0 (6)	H19B—C19—H19C	109.5
C1—C6—S1	120.6 (5)	C21—C20—C25	120.1 (5)
C5—C6—S1	119.3 (5)	C21—C20—N2	118.4 (5)
C12—C7—C8	122.4 (5)	C25—C20—N2	121.5 (5)
C12—C7—O3	119.6 (4)	C22—C21—C20	119.7 (6)
C8—C7—O3	117.9 (4)	C22—C21—H21	120.2
O4—C8—C9	126.5 (5)	C20—C21—H21	120.2
O4—C8—C7	116.1 (5)	C21—C22—C23	120.5 (6)
C9—C8—C7	117.4 (5)	C21—C22—H22	119.7
C10—C9—C8	120.0 (5)	C23—C22—H22	119.7
C10—C9—H9	120.0	C24—C23—C22	119.4 (6)
C8—C9—H9	120.0	C24—C23—H23	120.3
C9—C10—C11	122.9 (5)	C22—C23—H23	120.3
C9—C10—H10	118.6	C23—C24—C25	121.3 (6)
C11—C10—H10	118.6	C23—C24—H24	119.4
C10—C11—C12	116.8 (5)	C25—C24—H24	119.4
C10—C11—C14	121.4 (5)	C24—C25—C20	119.0 (6)
C12—C11—C14	121.8 (5)	C24—C25—H25	120.5
C7—C12—C11	120.4 (5)	C20—C25—H25	120.5
C7—C12—H12	119.8
C16—N2—N3—C17	−6.8 (5)	O3—C7—C12—C11	−179.8 (4)
C20—N2—N3—C17	−170.1 (5)	C10—C11—C12—C7	0.3 (7)
C16—N2—N3—C19	−154.0 (5)	C14—C11—C12—C7	−177.2 (5)
C20—N2—N3—C19	42.7 (7)	C15—N1—C14—C11	179.2 (4)
O1—S1—O3—C7	178.7 (3)	C10—C11—C14—N1	−158.1 (5)
O2—S1—O3—C7	−52.8 (4)	C12—C11—C14—N1	19.3 (8)
C6—S1—O3—C7	64.0 (4)	C14—N1—C15—C17	−169.3 (5)
C6—C1—C2—C3	1.2 (10)	C14—N1—C15—C16	11.0 (8)
C1—C2—C3—C4	−1.9 (10)	N3—N2—C16—O5	−172.4 (5)
C1—C2—C3—Br1	177.4 (5)	C20—N2—C16—O5	−10.1 (9)
C2—C3—C4—C5	1.2 (10)	N3—N2—C16—C15	4.5 (5)
Br1—C3—C4—C5	−178.1 (4)	C20—N2—C16—C15	166.9 (5)
C3—C4—C5—C6	0.2 (9)	C17—C15—C16—O5	175.9 (6)
C2—C1—C6—C5	0.1 (9)	N1—C15—C16—O5	−4.3 (9)
C2—C1—C6—S1	−176.2 (5)	C17—C15—C16—N2	−0.6 (6)
C4—C5—C6—C1	−0.8 (8)	N1—C15—C16—N2	179.1 (5)
C4—C5—C6—S1	175.5 (4)	N1—C15—C17—N3	176.6 (4)
O1—S1—C6—C1	−25.1 (6)	C16—C15—C17—N3	−3.6 (6)
O2—S1—C6—C1	−159.7 (4)	N1—C15—C17—C18	−2.3 (9)
O3—S1—C6—C1	84.3 (5)	C16—C15—C17—C18	177.5 (5)
O1—S1—C6—C5	158.6 (4)	N2—N3—C17—C15	6.3 (6)
O2—S1—C6—C5	24.0 (5)	C19—N3—C17—C15	150.8 (5)
O3—S1—C6—C5	−91.9 (5)	N2—N3—C17—C18	−174.7 (5)
S1—O3—C7—C12	84.6 (5)	C19—N3—C17—C18	−30.1 (8)
S1—O3—C7—C8	−97.6 (5)	C16—N2—C20—C21	59.0 (7)
C13—O4—C8—C9	−2.1 (7)	N3—N2—C20—C21	−140.4 (5)
C13—O4—C8—C7	179.0 (4)	C16—N2—C20—C25	−120.0 (6)
C12—C7—C8—O4	175.9 (5)	N3—N2—C20—C25	40.6 (7)
O3—C7—C8—O4	−1.8 (7)	C25—C20—C21—C22	−0.7 (8)
C12—C7—C8—C9	−3.1 (7)	N2—C20—C21—C22	−179.7 (5)
O3—C7—C8—C9	179.2 (4)	C20—C21—C22—C23	−0.8 (9)
O4—C8—C9—C10	−178.0 (5)	C21—C22—C23—C24	1.9 (9)
C7—C8—C9—C10	0.9 (7)	C22—C23—C24—C25	−1.5 (10)
C8—C9—C10—C11	1.9 (8)	C23—C24—C25—C20	0.0 (9)
C9—C10—C11—C12	−2.5 (8)	C21—C20—C25—C24	1.1 (8)
C9—C10—C11—C14	175.0 (5)	N2—C20—C25—C24	−179.9 (5)
C8—C7—C12—C11	2.5 (8)

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

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

Symmetry code: (i) .