1-(4-Methyl­phenyl­sulfon­yl)-5,6-di­nitro-1H-indazole

Oulemda, B.; Rakib, E.M.; Abbassi, N.; Saadi, M.; El Ammari, L.

doi:10.1107/S1600536813034326

organic compounds

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ISSN: 2056-9890

Volume 70| Part 1| January 2014| Page o101

https://doi.org/10.1107/S1600536813034326

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1-(4-Methylphenylsulfonyl)-5,6-dinitro-1H-indazole

Bassou Oulemda,^a ^* El Mostapha Rakib,^a Najat Abbassi,^a Mohamed Saadi ^b and Lahcen El Ammari ^b

^aLaboratoire de Chimie Organique et Analytique, Université Sultan Moulay Slimane, Faculté des Sciences et Techniques, Béni-Mellal, BP 523, Morocco, and ^bLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: b_oulemda@yahoo.fr

(Received 19 December 2013; accepted 20 December 2013; online 24 December 2013)

In the title compound, C₁₄H₁₀N₄O₆S, the indazole ring system is almost perpendicular to the tosyl ring, as indicated by the dihedral angle of 89.40 (9)° between their planes. The dihedral angles between the indazole system and the nitro groups are 57.0 (3) and 31.9 (3)°. In the crystal, molecules are linked by C—H⋯O interactions, forming chains running along [100].

CCDC reference: 978262

Related literature

For the biological activity of sulfonamides, see: Schmidt et al. (2008 ); Liu et al. (2004 ); Ali et al. (2008 ); Patel et al. (1999 ); Mosti et al. (2000 ); Bouissane et al. (2006 ); Abbassi et al. (2012 ). For the structures of similar compounds, see: Abbassi et al. (2013 ); Chicha et al. (2013 ).

Experimental

Crystal data

C₁₄H₁₀N₄O₆S
M_r = 362.32
Triclinic, $[P \overline 1]$
a = 7.4125 (3) Å
b = 8.5371 (3) Å
c = 13.0825 (5) Å
α = 90.401 (2)°
β = 95.707 (2)°
γ = 111.302 (2)°
V = 766.66 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 296 K
0.42 × 0.35 × 0.28 mm

Data collection

Bruker X8 APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.693, T_max = 0.747
19101 measured reflections
3383 independent reflections
2984 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.125
S = 1.07
3383 reflections
227 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O5ⁱ	0.93	2.61	3.175 (2)	120
Symmetry code: (i) x-1, y, z.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 978262

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S1600536813034326/bt6953sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813034326/bt6953Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813034326/bt6953Isup3.cml

checkCIF report

Comment top

Indazole derivatives are a versatile class of compounds that have found use in biology, catalysis, and medicinal chemistry (Schmidt et al., 2008). Although rare in nature (Liu et al., 2004; Ali et al., 2008), indazoles exhibit a variety of biological activities such as HIV protease inhibition (Patel et al., 1999), antiarrhythmic and analgesic activities (Mosti et al., 2000), antitumor activity) and antihypertensive properties (Bouissane et al., 2006; Abbassi et al., 2012). The present work is a continuation of the investigation of the sulfonamide derivatives published recently by our team (Abbassi et al., 2013; Chicha et al., 2013).

The molecule of the title compound is built up from an indazole ring system linked to a tosyl ring and to two nitro groups as shown in Fig. 1. The indazole ring system makes dihedral angles of 57.0 (3)° and 31.9 (3)°, with the two plans through the atoms forming the first (N1, O1, O2) and the second (N2, O3, O4) nitro groups, respectively. The plane through the tosyl ring is practically perpendicular to the indazole ring system ring, as indicated by the dihedral angle of 89.40 (9) °. In the crystal, the molecules are linked by a C–H···O interaction to form a one-dimensional chain running along the [100] direction as shown in Fig. 2 and Table 2.

Related literature top

For the biological activity of sulfonamides, see: Schmidt et al. (2008); Liu et al. (2004); Ali et al. (2008); Patel et al. (1999); Mosti et al. (2000); Bouissane et al. (2006); Abbassi et al. (2012). For the structures of similar compounds, see: Abbassi et al. (2013); Chicha et al. (2013).

Experimental top

To a stirred solution of 5,6-dinitroindazole (0.5 g, 2.4 mmol) in pyridine (25 ml) was added crude p-methylbenzenesulfonyl chloride (0.45 g, 2.4 mmol) over 10 min. The reaction mixture was allowed to attain room temperature and was stirred for further 24 h. The mixture was evaporated under reduced pressure and the residue was purified by silica gel flash column chromatography eluting with dichloromethane. The title compound was recrystallized from acetone. Yield: 56%, m.p.: 307–309 K.

Structure description top

For the biological activity of sulfonamides, see: Schmidt et al. (2008); Liu et al. (2004); Ali et al. (2008); Patel et al. (1999); Mosti et al. (2000); Bouissane et al. (2006); Abbassi et al. (2012). For the structures of similar compounds, see: Abbassi et al. (2013); Chicha et al. (2013).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. Plot of the molecule of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small circles.
	Fig. 2. : Partial crystal packing for the title compound showing hydrogen bonds as dashed lines.

1-(4-Methylphenylsulfonyl)-5,6-dinitro-1H-indazole top

Crystal data top

C₁₄H₁₀N₄O₆S	Z = 2
M_r = 362.32	F(000) = 372
Triclinic, P1	D_x = 1.570 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4125 (3) Å	Cell parameters from 3383 reflections
b = 8.5371 (3) Å	θ = 2.6–27.1°
c = 13.0825 (5) Å	µ = 0.25 mm⁻¹
α = 90.401 (2)°	T = 296 K
β = 95.707 (2)°	Block, colourless
γ = 111.302 (2)°	0.42 × 0.35 × 0.28 mm
V = 766.66 (5) Å³

Data collection top

Bruker X8 APEX diffractometer	3383 independent reflections
Radiation source: fine-focus sealed tube	2984 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
φ and ω scans	θ_max = 27.1°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→9
T_min = 0.693, T_max = 0.747	k = −10→10
19101 measured reflections	l = −16→16

Refinement top

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)] = 0.042	H-atom parameters constrained
wR(F²) = 0.125	w = 1/[σ²(F_o²) + (0.0641P)² + 0.3549P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
3383 reflections	Δρ_max = 0.46 e Å⁻³
227 parameters	Δρ_min = −0.32 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: 0.023 (4)

Crystal data top

C₁₄H₁₀N₄O₆S	γ = 111.302 (2)°
M_r = 362.32	V = 766.66 (5) Å³
Triclinic, P1	Z = 2
a = 7.4125 (3) Å	Mo Kα radiation
b = 8.5371 (3) Å	µ = 0.25 mm⁻¹
c = 13.0825 (5) Å	T = 296 K
α = 90.401 (2)°	0.42 × 0.35 × 0.28 mm
β = 95.707 (2)°

Data collection top

Bruker X8 APEX diffractometer	3383 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2984 reflections with I > 2σ(I)
T_min = 0.693, T_max = 0.747	R_int = 0.031
19101 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.125	H-atom parameters constrained
S = 1.07	Δρ_max = 0.46 e Å⁻³
3383 reflections	Δρ_min = −0.32 e Å⁻³
227 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
C1	0.0249 (2)	0.1414 (2)	0.35023 (12)	0.0319 (3)
C2	0.1588 (3)	0.2338 (2)	0.43202 (13)	0.0365 (4)
H2	0.2924	0.2632	0.4312	0.044*
C3	0.0814 (3)	0.2782 (2)	0.51328 (13)	0.0370 (4)
C4	−0.1209 (3)	0.2326 (2)	0.51564 (13)	0.0389 (4)
C5	−0.2510 (3)	0.1422 (2)	0.43547 (14)	0.0395 (4)
H5	−0.3845	0.1121	0.4373	0.047*
C6	−0.1768 (2)	0.0965 (2)	0.35082 (13)	0.0340 (4)
C7	−0.2599 (3)	0.0120 (2)	0.25344 (14)	0.0401 (4)
H7	−0.3929	−0.0317	0.2322	0.048*
C8	0.2592 (2)	0.2835 (2)	0.12063 (13)	0.0341 (4)
C9	0.3100 (3)	0.4449 (2)	0.16444 (15)	0.0459 (4)
H9	0.3465	0.4669	0.2347	0.055*
C10	0.3047 (3)	0.5715 (3)	0.10045 (19)	0.0540 (5)
H10	0.3356	0.6796	0.1286	0.065*
C11	0.2545 (3)	0.5414 (3)	−0.00455 (17)	0.0494 (5)
C12	0.2060 (3)	0.3792 (3)	−0.04551 (16)	0.0523 (5)
H12	0.1725	0.3578	−0.1160	0.063*
C13	0.2064 (3)	0.2490 (3)	0.01622 (14)	0.0434 (4)
H13	0.1718	0.1404	−0.0118	0.052*
C14	0.2506 (4)	0.6822 (4)	−0.0728 (2)	0.0757 (8)
H14A	0.3662	0.7798	−0.0550	0.114*
H14B	0.1380	0.7089	−0.0635	0.114*
H14C	0.2451	0.6474	−0.1434	0.114*
N1	0.2229 (3)	0.3722 (2)	0.59984 (13)	0.0499 (4)
N2	−0.1975 (3)	0.2944 (2)	0.60016 (14)	0.0537 (5)
N3	−0.1278 (2)	0.00328 (19)	0.19798 (11)	0.0396 (3)
N4	0.0489 (2)	0.07838 (19)	0.25754 (11)	0.0361 (3)
O1	0.3506 (3)	0.5014 (3)	0.58078 (16)	0.0959 (8)
O2	0.2091 (4)	0.3122 (3)	0.68252 (13)	0.0874 (7)
O3	−0.0949 (3)	0.4309 (2)	0.64245 (15)	0.0780 (6)
O4	−0.3607 (3)	0.2146 (3)	0.61839 (17)	0.0944 (7)
O5	0.4057 (2)	0.1788 (2)	0.28403 (11)	0.0491 (4)
O6	0.2305 (2)	−0.02753 (18)	0.14045 (12)	0.0538 (4)
S1	0.25624 (6)	0.11985 (6)	0.20019 (3)	0.03714 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0385 (8)	0.0306 (8)	0.0282 (8)	0.0145 (7)	0.0030 (6)	0.0020 (6)
C2	0.0380 (9)	0.0381 (9)	0.0325 (8)	0.0140 (7)	−0.0008 (7)	−0.0007 (7)
C3	0.0487 (10)	0.0311 (8)	0.0301 (8)	0.0145 (7)	0.0004 (7)	0.0002 (6)
C4	0.0540 (11)	0.0348 (9)	0.0329 (9)	0.0200 (8)	0.0128 (8)	0.0052 (7)
C5	0.0400 (9)	0.0410 (9)	0.0396 (9)	0.0160 (8)	0.0096 (7)	0.0059 (7)
C6	0.0357 (8)	0.0326 (8)	0.0337 (8)	0.0126 (7)	0.0028 (7)	0.0038 (6)
C7	0.0359 (9)	0.0423 (9)	0.0384 (9)	0.0112 (7)	−0.0012 (7)	−0.0009 (7)
C8	0.0316 (8)	0.0409 (9)	0.0322 (8)	0.0157 (7)	0.0053 (6)	−0.0024 (7)
C9	0.0515 (11)	0.0454 (10)	0.0396 (10)	0.0172 (9)	0.0019 (8)	−0.0073 (8)
C10	0.0575 (13)	0.0419 (11)	0.0643 (14)	0.0192 (9)	0.0102 (11)	0.0015 (10)
C11	0.0371 (10)	0.0604 (12)	0.0581 (12)	0.0230 (9)	0.0183 (9)	0.0208 (10)
C12	0.0515 (11)	0.0751 (14)	0.0351 (10)	0.0277 (11)	0.0092 (8)	0.0092 (9)
C13	0.0475 (10)	0.0515 (11)	0.0322 (9)	0.0193 (9)	0.0057 (8)	−0.0061 (8)
C14	0.0625 (15)	0.0889 (19)	0.094 (2)	0.0421 (14)	0.0337 (14)	0.0504 (16)
N1	0.0650 (11)	0.0446 (9)	0.0355 (9)	0.0168 (8)	−0.0028 (8)	−0.0076 (7)
N2	0.0717 (12)	0.0547 (10)	0.0418 (9)	0.0282 (9)	0.0205 (9)	0.0028 (8)
N3	0.0415 (8)	0.0407 (8)	0.0332 (8)	0.0129 (7)	−0.0027 (6)	−0.0040 (6)
N4	0.0360 (7)	0.0409 (8)	0.0298 (7)	0.0127 (6)	0.0015 (6)	−0.0040 (6)
O1	0.0898 (15)	0.0859 (14)	0.0680 (12)	−0.0171 (12)	−0.0005 (11)	−0.0216 (11)
O2	0.1383 (19)	0.0776 (12)	0.0387 (9)	0.0375 (13)	−0.0184 (10)	0.0019 (8)
O3	0.1032 (15)	0.0646 (11)	0.0696 (11)	0.0315 (10)	0.0245 (11)	−0.0176 (9)
O4	0.0930 (15)	0.0952 (15)	0.0867 (14)	0.0130 (12)	0.0569 (13)	−0.0114 (12)
O5	0.0403 (7)	0.0691 (9)	0.0438 (7)	0.0289 (7)	−0.0017 (6)	0.0018 (7)
O6	0.0701 (10)	0.0486 (8)	0.0543 (9)	0.0339 (7)	0.0137 (7)	−0.0048 (7)
S1	0.0394 (3)	0.0435 (3)	0.0349 (2)	0.0227 (2)	0.00423 (18)	−0.00191 (18)

Geometric parameters (Å, º) top

C1—N4	1.377 (2)	C10—C11	1.384 (3)
C1—C2	1.400 (2)	C10—H10	0.9300
C1—C6	1.403 (2)	C11—C12	1.387 (3)
C2—C3	1.370 (2)	C11—C14	1.509 (3)
C2—H2	0.9300	C12—C13	1.379 (3)
C3—C4	1.409 (3)	C12—H12	0.9300
C3—N1	1.472 (2)	C13—H13	0.9300
C4—C5	1.368 (3)	C14—H14A	0.9600
C4—N2	1.469 (2)	C14—H14B	0.9600
C5—C6	1.397 (2)	C14—H14C	0.9600
C5—H5	0.9300	N1—O2	1.198 (2)
C6—C7	1.425 (2)	N1—O1	1.211 (3)
C7—N3	1.298 (2)	N2—O4	1.202 (3)
C7—H7	0.9300	N2—O3	1.227 (3)
C8—C13	1.382 (2)	N3—N4	1.383 (2)
C8—C9	1.392 (3)	N4—S1	1.6992 (15)
C8—S1	1.7429 (18)	O5—S1	1.4245 (14)
C9—C10	1.381 (3)	O6—S1	1.4186 (14)
C9—H9	0.9300

N4—C1—C2	132.03 (16)	C10—C11—C14	120.6 (2)
N4—C1—C6	105.65 (15)	C12—C11—C14	120.8 (2)
C2—C1—C6	122.32 (16)	C13—C12—C11	121.32 (19)
C3—C2—C1	116.04 (16)	C13—C12—H12	119.3
C3—C2—H2	122.0	C11—C12—H12	119.3
C1—C2—H2	122.0	C12—C13—C8	118.61 (19)
C2—C3—C4	122.37 (16)	C12—C13—H13	120.7
C2—C3—N1	115.68 (17)	C8—C13—H13	120.7
C4—C3—N1	121.92 (16)	C11—C14—H14A	109.5
C5—C4—C3	121.29 (16)	C11—C14—H14B	109.5
C5—C4—N2	117.78 (18)	H14A—C14—H14B	109.5
C3—C4—N2	120.69 (17)	C11—C14—H14C	109.5
C4—C5—C6	117.80 (17)	H14A—C14—H14C	109.5
C4—C5—H5	121.1	H14B—C14—H14C	109.5
C6—C5—H5	121.1	O2—N1—O1	124.8 (2)
C5—C6—C1	120.16 (16)	O2—N1—C3	118.03 (18)
C5—C6—C7	134.80 (17)	O1—N1—C3	117.08 (18)
C1—C6—C7	105.00 (15)	O4—N2—O3	124.3 (2)
N3—C7—C6	111.90 (16)	O4—N2—C4	118.2 (2)
N3—C7—H7	124.1	O3—N2—C4	117.26 (19)
C6—C7—H7	124.1	C7—N3—N4	106.16 (14)
C13—C8—C9	121.71 (18)	C1—N4—N3	111.21 (14)
C13—C8—S1	119.26 (14)	C1—N4—S1	128.92 (12)
C9—C8—S1	119.01 (14)	N3—N4—S1	118.15 (11)
C10—C9—C8	118.03 (18)	O6—S1—O5	121.02 (9)
C10—C9—H9	121.0	O6—S1—N4	106.26 (8)
C8—C9—H9	121.0	O5—S1—N4	103.11 (8)
C9—C10—C11	121.7 (2)	O6—S1—C8	110.38 (9)
C9—C10—H10	119.2	O5—S1—C8	110.65 (9)
C11—C10—H10	119.2	N4—S1—C8	103.62 (8)
C10—C11—C12	118.67 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O5ⁱ	0.93	2.61	3.175 (2)	120

Symmetry code: (i) x−1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O5ⁱ	0.93	2.61	3.175 (2)	119.9

Symmetry code: (i) x−1, y, z.

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.

References

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