4-(4-Bromo­phen­yl)-3-methyl-1-phenyl-6,7-dihydro-1H-pyrazolo­[3,4-b]thieno[2,3-e]pyridine 5,5-dioxide

Li, T.; Zhang, H.

doi:10.1107/S1600536811045697

organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3166

https://doi.org/10.1107/S1600536811045697

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4-(4-Bromophenyl)-3-methyl-1-phenyl-6,7-dihydro-1H-pyrazolo[3,4-b]thieno[2,3-e]pyridine 5,5-dioxide

Tuanjie Li ^a ^* and Honghong Zhang ^a

^aSchool of Chemistry and Engineering, Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, Xuzhou Normal University, Xuzhou, Jiangsu 221116, People's Republic of China
^*Correspondence e-mail: ltj2008@xznu.edu.cn

(Received 27 October 2011; accepted 31 October 2011; online 5 November 2011)

In the title compound, C₂₁H₁₆BrN₃O₂S, the pyrazole and pyridine rings are nearly coplanar, the dihedral angle between their planes being 3.17 (14)°. The 2,3-dihydrothiophene ring adopts an envelope conformation. The 4-bromophenyl/pyridine ring and phenyl/pyrazole rings form dihedral angles of 60.06 (9) and 33.49 (11)°, respectively. There is an intramolecular C—H⋯N hydrogen bond. The crystal packing is stabilized by intermolecular C—H⋯O hydrogen bonding and C—H⋯π interactions.

Related literature

For the bioactivity of thienopyridine derivatives, see: Goerlitzer et al. (2004 , 2000 ); Kamel et al. (2003 ). For the preparation of the title compound, see: Shi & Yang (2011 ).

Experimental

Crystal data

C₂₁H₁₆BrN₃O₂S
M_r = 454.34
Triclinic, $[P \overline 1]$
a = 9.881 (3) Å
b = 9.904 (3) Å
c = 11.333 (4) Å
α = 108.642 (1)°
β = 102.000 (4)°
γ = 107.346 (3)°
V = 945.1 (5) Å³
Z = 2
Mo Kα radiation
μ = 2.31 mm⁻¹
T = 113 K
0.24 × 0.22 × 0.16 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002) T_min = 0.607, T_max = 0.709
10810 measured reflections
4429 independent reflections
2695 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.096
S = 0.98
4429 reflections
254 parameters
H-atom parameters constrained
Δρ_max = 1.14 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cgⁱ	0.95	2.84	3.235 (3)	106
C5—H5⋯O1ⁱⁱ	0.95	2.48	3.239 (3)	136
C19—H19⋯O1ⁱⁱⁱ	0.95	2.57	3.514 (4)	174
C21—H21⋯N1	0.95	2.56	3.065 (3)	114
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y+1, -z+2; (iii) x-1, y, z-1.

Data collection: CrystalClear (Rigaku/MSC, 2002); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811045697/hg5128sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811045697/hg5128Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811045697/hg5128Isup3.cml

checkCIF report

Comment top

Some synthetic thienopyridine compounds exhibit antimalarial activities (Goerlitzer et al. 2004) and act as gyrase inhibitors (Goerlitzer et al. 2000). Recently, A-312110, a thienopyridine derivative was also reported as a potent KATP channel opener (Kamel et al. 2003). These reports inspired us to study the relationship between their structures and activities. During the synthesis of thienopyridine derivatives, the title compound, (I) was isolated and its structure was determined by X-ray diffraction. In the molecular structure (Fig. 1), the pyrazole and pyridine rings adopt planar conformations, with RMS of 0.0035 Å and 0.0170 Å, respectively. The largest deviation of the two rings are 0.005 (1) Å(N2) and 0.0325 (2) Å(C7), respectively. They are nearly coplanar, since the dihedral angle between them is 3.17 (14) °. The 2,3-dihydrothiophene ring adopts an envelope conformation. The distance between atom C9 and the plane of C10/C11/C8/S1 is 0.322 (4) Å. Besides, the 4-bromophenyl and pyridine ring, phenyl and pyrazole ring forms dihedral angles of 60.06 (9)° and 33.49 (11)° respectively. There is an intramolecular C—H···O hydrogen bond. In addition, the crystal packing is stabilized by intermolecular C—H···O hydrogen bond and C—H··· π interactions (Fig. 2).

Related literature top

For the bioactivity of thienopyridine derivatives, see: Goerlitzer et al. (2004, 2000); Kamel et al. (2003). For the preparation of the title compound, see: Shi & Yang (2011).

Experimental top

The title compound was synthesized according to the procedure (Shi et al. 2011). A dry 50 ml flask was charged with 4-bromobenzaldehyde (1 mmol), dihydrothiophen-3(2H)-one 1,1-dioxide (1 mmol), 5-amino-3-methyl-1-phenyl-pyrazole (1 mmol), and ionic liquid [bmim]Br (2 ml). The mixture was stirred at 363 K for 1.5 h to complete the reaction (monitored by TLC), then 5 ml water was added. The solid was filtered off and washed with water. The crude product was purified by recrystallization from the mixture of DMF and ethanol to give pure product.The recrystallization gave single-crystals suitable for X-ray diffraction.

Structure description top

For the bioactivity of thienopyridine derivatives, see: Goerlitzer et al. (2004, 2000); Kamel et al. (2003). For the preparation of the title compound, see: Shi & Yang (2011).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2002); cell refinement: CrystalClear (Rigaku/MSC, 2002); data reduction: CrystalClear (Rigaku/MSC, 2002); 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).

Figures top

	Fig. 1. The structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme, hydrogen bond represented by the dashed line. Cg is the centroid of the ring of C16/C17/C18/C19/C20/C21.
	Fig. 2. The packing diagram of (I), hydrogen bond represented by the dashed line.

4-(4-Bromophenyl)-3-methyl-1-phenyl-6,7-dihydro-1H- pyrazolo[3,4-b]thieno[2,3-e]pyridine 5,5-dioxide top

Crystal data top

C₂₁H₁₆BrN₃O₂S	Z = 2
M_r = 454.34	F(000) = 460
Triclinic, P1	D_x = 1.597 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.881 (3) Å	Cell parameters from 3340 reflections
b = 9.904 (3) Å	θ = 2.0–27.9°
c = 11.333 (4) Å	µ = 2.31 mm⁻¹
α = 108.642 (1)°	T = 113 K
β = 102.000 (4)°	Prism, colorless
γ = 107.346 (3)°	0.24 × 0.22 × 0.16 mm
V = 945.1 (5) Å³

Data collection top

Rigaku Saturn CCD area-detector diffractometer	4429 independent reflections
Radiation source: rotating anode	2695 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.041
Detector resolution: 14.63 pixels mm^-1	θ_max = 27.9°, θ_min = 2.0°
ω and φ scans	h = −11→12
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002)	k = −13→13
T_min = 0.607, T_max = 0.709	l = −14→14
10810 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0437P)²] where P = (F_o² + 2F_c²)/3
4429 reflections	(Δ/σ)_max = 0.001
254 parameters	Δρ_max = 1.14 e Å⁻³
0 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

C₂₁H₁₆BrN₃O₂S	γ = 107.346 (3)°
M_r = 454.34	V = 945.1 (5) Å³
Triclinic, P1	Z = 2
a = 9.881 (3) Å	Mo Kα radiation
b = 9.904 (3) Å	µ = 2.31 mm⁻¹
c = 11.333 (4) Å	T = 113 K
α = 108.642 (1)°	0.24 × 0.22 × 0.16 mm
β = 102.000 (4)°

Data collection top

Rigaku Saturn CCD area-detector diffractometer	4429 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002)	2695 reflections with I > 2σ(I)
T_min = 0.607, T_max = 0.709	R_int = 0.041
10810 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 0.98	Δρ_max = 1.14 e Å⁻³
4429 reflections	Δρ_min = −0.58 e Å⁻³
254 parameters

Special details top

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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	1.02598 (4)	0.80211 (4)	1.16776 (3)	0.04812 (13)
S1	0.45768 (7)	0.09317 (7)	0.71274 (6)	0.02120 (15)
O1	0.4863 (2)	0.1482 (2)	0.85218 (18)	0.0380 (5)
O2	0.5755 (2)	0.0686 (2)	0.6663 (2)	0.0372 (5)
N1	0.1738 (2)	0.1677 (2)	0.4704 (2)	0.0220 (5)
N2	0.1926 (2)	0.4054 (2)	0.4460 (2)	0.0233 (5)
N3	0.2917 (2)	0.5588 (2)	0.5057 (2)	0.0240 (5)
C1	0.5936 (3)	0.4707 (3)	0.8034 (2)	0.0190 (5)
C2	0.7289 (3)	0.4526 (3)	0.8108 (2)	0.0204 (5)
H2	0.7331	0.3712	0.7411	0.025*
C3	0.8563 (3)	0.5509 (3)	0.9177 (2)	0.0243 (6)
H3	0.9490	0.5395	0.9206	0.029*
C4	0.8497 (3)	0.6665 (3)	1.0212 (2)	0.0273 (6)
C5	0.7152 (3)	0.6852 (3)	1.0175 (3)	0.0318 (7)
H5	0.7111	0.7644	1.0892	0.038*
C6	0.5877 (3)	0.5877 (3)	0.9089 (3)	0.0270 (6)
H6	0.4954	0.6001	0.9057	0.032*
C7	0.4559 (3)	0.3682 (3)	0.6872 (2)	0.0193 (5)
C8	0.3902 (3)	0.2086 (3)	0.6455 (2)	0.0183 (5)
C9	0.2875 (3)	−0.0719 (3)	0.6279 (3)	0.0416 (8)
H9A	0.3088	−0.1659	0.5938	0.050*
H9B	0.2307	−0.0839	0.6888	0.050*
C10	0.1963 (3)	−0.0532 (3)	0.5156 (3)	0.0291 (6)
H10A	0.2062	−0.1134	0.4316	0.035*
H10B	0.0887	−0.0919	0.5076	0.035*
C11	0.2532 (3)	0.1152 (3)	0.5425 (2)	0.0210 (5)
C12	0.2421 (3)	0.3213 (3)	0.5059 (2)	0.0205 (5)
C13	0.3777 (3)	0.4255 (3)	0.6098 (2)	0.0206 (5)
C14	0.4020 (3)	0.5728 (3)	0.6035 (2)	0.0214 (5)
C15	0.5315 (3)	0.7246 (3)	0.6841 (3)	0.0267 (6)
H15A	0.5434	0.7867	0.6320	0.040*
H15B	0.6236	0.7069	0.7099	0.040*
H15C	0.5127	0.7800	0.7636	0.040*
C16	0.0596 (3)	0.3565 (3)	0.3378 (3)	0.0260 (6)
C17	−0.0100 (3)	0.4602 (4)	0.3356 (3)	0.0310 (7)
H17	0.0300	0.5609	0.4049	0.037*
C18	−0.1381 (3)	0.4129 (4)	0.2301 (3)	0.0393 (8)
H18	−0.1857	0.4828	0.2273	0.047*
C19	−0.1981 (3)	0.2683 (4)	0.1296 (3)	0.0446 (8)
H19	−0.2872	0.2380	0.0589	0.054*
C20	−0.1277 (3)	0.1653 (4)	0.1315 (3)	0.0433 (8)
H20	−0.1680	0.0651	0.0616	0.052*
C21	0.0016 (3)	0.2105 (3)	0.2362 (3)	0.0337 (7)
H21	0.0502	0.1412	0.2379	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0535 (2)	0.02996 (18)	0.02916 (18)	0.00753 (16)	−0.01463 (14)	−0.00030 (13)
S1	0.0202 (3)	0.0170 (3)	0.0251 (3)	0.0074 (3)	0.0038 (3)	0.0093 (3)
O1	0.0592 (14)	0.0385 (12)	0.0241 (10)	0.0289 (11)	0.0091 (10)	0.0163 (9)
O2	0.0347 (12)	0.0336 (12)	0.0642 (15)	0.0229 (10)	0.0272 (11)	0.0300 (11)
N1	0.0198 (12)	0.0196 (11)	0.0260 (12)	0.0070 (9)	0.0047 (9)	0.0112 (9)
N2	0.0201 (12)	0.0233 (12)	0.0277 (12)	0.0089 (10)	0.0036 (9)	0.0141 (10)
N3	0.0222 (12)	0.0209 (12)	0.0294 (12)	0.0080 (10)	0.0067 (10)	0.0124 (10)
C1	0.0213 (14)	0.0160 (12)	0.0218 (13)	0.0071 (11)	0.0065 (10)	0.0109 (10)
C2	0.0237 (14)	0.0172 (13)	0.0193 (13)	0.0087 (11)	0.0046 (10)	0.0072 (10)
C3	0.0228 (14)	0.0219 (14)	0.0245 (14)	0.0077 (12)	0.0018 (11)	0.0097 (11)
C4	0.0302 (16)	0.0198 (14)	0.0196 (13)	0.0047 (12)	−0.0028 (11)	0.0048 (11)
C5	0.0472 (19)	0.0215 (14)	0.0224 (14)	0.0138 (14)	0.0121 (13)	0.0032 (11)
C6	0.0306 (16)	0.0253 (14)	0.0293 (15)	0.0153 (13)	0.0128 (12)	0.0107 (12)
C7	0.0173 (13)	0.0190 (13)	0.0225 (13)	0.0085 (11)	0.0061 (10)	0.0086 (11)
C8	0.0186 (13)	0.0196 (13)	0.0192 (12)	0.0092 (11)	0.0063 (10)	0.0095 (10)
C9	0.0330 (18)	0.0248 (16)	0.053 (2)	0.0000 (14)	−0.0055 (14)	0.0215 (15)
C10	0.0248 (15)	0.0203 (14)	0.0343 (16)	0.0050 (12)	0.0011 (12)	0.0109 (12)
C11	0.0201 (14)	0.0207 (13)	0.0234 (13)	0.0081 (11)	0.0084 (11)	0.0096 (11)
C12	0.0168 (13)	0.0219 (13)	0.0272 (14)	0.0092 (11)	0.0075 (11)	0.0136 (11)
C13	0.0204 (14)	0.0187 (13)	0.0228 (13)	0.0078 (11)	0.0060 (11)	0.0094 (11)
C14	0.0221 (14)	0.0201 (13)	0.0257 (14)	0.0103 (12)	0.0097 (11)	0.0108 (11)
C15	0.0272 (15)	0.0189 (13)	0.0321 (15)	0.0081 (12)	0.0050 (12)	0.0122 (12)
C16	0.0170 (14)	0.0354 (16)	0.0294 (15)	0.0070 (12)	0.0064 (11)	0.0218 (13)
C17	0.0300 (17)	0.0483 (19)	0.0311 (15)	0.0235 (15)	0.0155 (13)	0.0253 (14)
C18	0.0275 (17)	0.069 (2)	0.0427 (19)	0.0285 (18)	0.0170 (15)	0.0368 (18)
C19	0.0242 (17)	0.067 (2)	0.0415 (19)	0.0077 (16)	−0.0007 (13)	0.0368 (18)
C20	0.0358 (18)	0.046 (2)	0.0355 (17)	0.0008 (16)	−0.0005 (14)	0.0236 (16)
C21	0.0294 (16)	0.0334 (17)	0.0348 (16)	0.0070 (14)	0.0014 (13)	0.0205 (14)

Geometric parameters (Å, º) top

Br1—C4	1.890 (3)	C8—C11	1.399 (3)
S1—O2	1.4261 (19)	C9—C10	1.497 (4)
S1—O1	1.4304 (19)	C9—H9A	0.9900
S1—C9	1.763 (3)	C9—H9B	0.9900
S1—C8	1.770 (2)	C10—C11	1.495 (4)
N1—C11	1.342 (3)	C10—H10A	0.9900
N1—C12	1.347 (3)	C10—H10B	0.9900
N2—C12	1.364 (3)	C12—C13	1.411 (3)
N2—N3	1.381 (3)	C13—C14	1.434 (3)
N2—C16	1.427 (3)	C14—C15	1.490 (3)
N3—C14	1.322 (3)	C15—H15A	0.9800
C1—C2	1.390 (3)	C15—H15B	0.9800
C1—C6	1.400 (3)	C15—H15C	0.9800
C1—C7	1.481 (3)	C16—C21	1.383 (4)
C2—C3	1.372 (3)	C16—C17	1.400 (4)
C2—H2	0.9500	C17—C18	1.382 (4)
C3—C4	1.381 (4)	C17—H17	0.9500
C3—H3	0.9500	C18—C19	1.367 (5)
C4—C5	1.389 (4)	C18—H18	0.9500
C5—C6	1.380 (4)	C19—C20	1.399 (4)
C5—H5	0.9500	C19—H19	0.9500
C6—H6	0.9500	C20—C21	1.389 (4)
C7—C8	1.388 (3)	C20—H20	0.9500
C7—C13	1.409 (3)	C21—H21	0.9500

O2—S1—O1	117.48 (13)	C11—C10—H10A	110.1
O2—S1—C9	111.19 (15)	C9—C10—H10A	110.1
O1—S1—C9	110.26 (14)	C11—C10—H10B	110.1
O2—S1—C8	109.80 (11)	C9—C10—H10B	110.1
O1—S1—C8	111.74 (11)	H10A—C10—H10B	108.4
C9—S1—C8	93.92 (13)	N1—C11—C8	124.4 (2)
C11—N1—C12	112.6 (2)	N1—C11—C10	120.2 (2)
C12—N2—N3	110.6 (2)	C8—C11—C10	115.4 (2)
C12—N2—C16	129.5 (2)	N1—C12—N2	125.9 (2)
N3—N2—C16	119.9 (2)	N1—C12—C13	127.2 (2)
C14—N3—N2	107.4 (2)	N2—C12—C13	106.9 (2)
C2—C1—C6	119.0 (2)	C7—C13—C12	119.0 (2)
C2—C1—C7	121.4 (2)	C7—C13—C14	136.0 (2)
C6—C1—C7	119.5 (2)	C12—C13—C14	104.9 (2)
C3—C2—C1	120.7 (2)	N3—C14—C13	110.2 (2)
C3—C2—H2	119.6	N3—C14—C15	120.5 (2)
C1—C2—H2	119.6	C13—C14—C15	129.3 (2)
C2—C3—C4	119.8 (2)	C14—C15—H15A	109.5
C2—C3—H3	120.1	C14—C15—H15B	109.5
C4—C3—H3	120.1	H15A—C15—H15B	109.5
C3—C4—C5	120.6 (2)	C14—C15—H15C	109.5
C3—C4—Br1	119.6 (2)	H15A—C15—H15C	109.5
C5—C4—Br1	119.8 (2)	H15B—C15—H15C	109.5
C6—C5—C4	119.5 (2)	C21—C16—C17	120.6 (3)
C6—C5—H5	120.3	C21—C16—N2	120.8 (2)
C4—C5—H5	120.3	C17—C16—N2	118.6 (3)
C5—C6—C1	120.3 (2)	C18—C17—C16	118.5 (3)
C5—C6—H6	119.9	C18—C17—H17	120.8
C1—C6—H6	119.9	C16—C17—H17	120.8
C8—C7—C13	113.7 (2)	C19—C18—C17	121.8 (3)
C8—C7—C1	123.8 (2)	C19—C18—H18	119.1
C13—C7—C1	122.5 (2)	C17—C18—H18	119.1
C7—C8—C11	122.9 (2)	C18—C19—C20	119.7 (3)
C7—C8—S1	127.27 (19)	C18—C19—H19	120.2
C11—C8—S1	109.75 (18)	C20—C19—H19	120.2
C10—C9—S1	108.94 (19)	C21—C20—C19	119.6 (3)
C10—C9—H9A	109.9	C21—C20—H20	120.2
S1—C9—H9A	109.9	C19—C20—H20	120.2
C10—C9—H9B	109.9	C16—C21—C20	119.9 (3)
S1—C9—H9B	109.9	C16—C21—H21	120.1
H9A—C9—H9B	108.3	C20—C21—H21	120.1
C11—C10—C9	108.2 (2)

C12—N2—N3—C14	−0.8 (3)	S1—C8—C11—C10	1.0 (3)
C16—N2—N3—C14	178.7 (2)	C9—C10—C11—N1	−167.5 (2)
C6—C1—C2—C3	−2.2 (4)	C9—C10—C11—C8	12.2 (3)
C7—C1—C2—C3	178.4 (2)	C11—N1—C12—N2	176.3 (2)
C1—C2—C3—C4	1.9 (4)	C11—N1—C12—C13	−3.1 (3)
C2—C3—C4—C5	−0.6 (4)	N3—N2—C12—N1	−178.5 (2)
C2—C3—C4—Br1	−179.70 (18)	C16—N2—C12—N1	2.0 (4)
C3—C4—C5—C6	−0.4 (4)	N3—N2—C12—C13	0.9 (3)
Br1—C4—C5—C6	178.66 (19)	C16—N2—C12—C13	−178.5 (2)
C4—C5—C6—C1	0.1 (4)	C8—C7—C13—C12	3.0 (3)
C2—C1—C6—C5	1.1 (4)	C1—C7—C13—C12	−176.0 (2)
C7—C1—C6—C5	−179.5 (2)	C8—C7—C13—C14	−174.1 (3)
C2—C1—C7—C8	59.7 (3)	C1—C7—C13—C14	7.0 (4)
C6—C1—C7—C8	−119.7 (3)	N1—C12—C13—C7	0.9 (4)
C2—C1—C7—C13	−121.5 (3)	N2—C12—C13—C7	−178.6 (2)
C6—C1—C7—C13	59.2 (3)	N1—C12—C13—C14	178.8 (2)
C13—C7—C8—C11	−4.6 (3)	N2—C12—C13—C14	−0.7 (3)
C1—C7—C8—C11	174.4 (2)	N2—N3—C14—C13	0.3 (3)
C13—C7—C8—S1	177.58 (18)	N2—N3—C14—C15	177.3 (2)
C1—C7—C8—S1	−3.5 (3)	C7—C13—C14—N3	177.6 (3)
O2—S1—C8—C7	−78.9 (2)	C12—C13—C14—N3	0.2 (3)
O1—S1—C8—C7	53.3 (2)	C7—C13—C14—C15	0.9 (5)
C9—S1—C8—C7	166.9 (2)	C12—C13—C14—C15	−176.5 (2)
O2—S1—C8—C11	103.01 (19)	C12—N2—C16—C21	−34.4 (4)
O1—S1—C8—C11	−124.82 (18)	N3—N2—C16—C21	146.2 (2)
C9—S1—C8—C11	−11.2 (2)	C12—N2—C16—C17	146.6 (2)
O2—S1—C9—C10	−95.0 (2)	N3—N2—C16—C17	−32.9 (3)
O1—S1—C9—C10	132.9 (2)	C21—C16—C17—C18	0.4 (4)
C8—S1—C9—C10	18.0 (2)	N2—C16—C17—C18	179.5 (2)
S1—C9—C10—C11	−19.6 (3)	C16—C17—C18—C19	0.5 (4)
C12—N1—C11—C8	1.4 (3)	C17—C18—C19—C20	−1.0 (5)
C12—N1—C11—C10	−178.9 (2)	C18—C19—C20—C21	0.7 (4)
C7—C8—C11—N1	2.5 (4)	C17—C16—C21—C20	−0.8 (4)
S1—C8—C11—N1	−179.29 (19)	N2—C16—C21—C20	−179.8 (2)
C7—C8—C11—C10	−177.2 (2)	C19—C20—C21—C16	0.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cgⁱ	0.95	2.84	3.235 (3)	106
C5—H5···O1ⁱⁱ	0.95	2.48	3.239 (3)	136
C19—H19···O1ⁱⁱⁱ	0.95	2.57	3.514 (4)	174
C21—H21···N1	0.95	2.56	3.065 (3)	114

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z+2; (iii) x−1, y, z−1.

Experimental details

Crystal data
Chemical formula	C₂₁H₁₆BrN₃O₂S
M_r	454.34
Crystal system, space group	Triclinic, P1
Temperature (K)	113
a, b, c (Å)	9.881 (3), 9.904 (3), 11.333 (4)
α, β, γ (°)	108.642 (1), 102.000 (4), 107.346 (3)
V (Å³)	945.1 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.31
Crystal size (mm)	0.24 × 0.22 × 0.16

Data collection
Diffractometer	Rigaku Saturn CCD area-detector
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2002)
T_min, T_max	0.607, 0.709
No. of measured, independent and observed [I > 2σ(I)] reflections	10810, 4429, 2695
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.096, 0.98
No. of reflections	4429
No. of parameters	254
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.14, −0.58

Computer programs: CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cgⁱ	0.95	2.84	3.235 (3)	106.0
C5—H5···O1ⁱⁱ	0.95	2.48	3.239 (3)	136.4
C19—H19···O1ⁱⁱⁱ	0.95	2.57	3.514 (4)	174.3
C21—H21···N1	0.95	2.56	3.065 (3)	113.8

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z+2; (iii) x−1, y, z−1.

Acknowledgements

We are thankful to Dr Youquan Zhu (zyq8165@nankai.edu.cn) of Nankai University for the data collection and the Natural Science Foundation of Xuzhou Normal University for financial support (08XRL05).

References

Goerlitzer, K., Kramer, C. & Boyle, C. (2000). Pharmazie, 55, 595–600. Web of Science PubMed Google Scholar
Goerlitzer, K., Meyer, H., Walter, R. D., Jomaa, H. & Wiesner, J. (2004). Pharmazie, 59, 506–512. Web of Science PubMed CAS Google Scholar
Kamel, M. M., El-Deen, E. M. M. & Abdou, W. A. M. (2003). Bull. Fac. Pharm. 41, 197–206. CAS Google Scholar
Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shi, D.-Q. & Yang, F. (2011). J. Heterocycl. Chem. 48, 308–311. Web of Science CrossRef CAS Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

4-(4-Bromo­phen­yl)-3-methyl-1-phenyl-6,7-di­hydro-1H-pyrazolo­[3,4-b]thieno[2,3-e]pyridine 5,5-dioxide

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4-(4-Bromophenyl)-3-methyl-1-phenyl-6,7-dihydro-1H-pyrazolo[3,4-b]thieno[2,3-e]pyridine 5,5-dioxide