N′-(5-Fluoro-2-oxo-2,3-dihydro-1H-indol-3-yl­idene)benzene­sulfono­hydrazide

Ali, H.M.; Laila, M.; Rizal, M.R.; Ng, S.W.

doi:10.1107/S1600536808011136

organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o921

doi:10.1107/S1600536808011136

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N′-(5-Fluoro-2-oxo-2,3-dihydro-1H-indol-3-ylidene)benzenesulfonohydrazide

Hapipah M. Ali,^a Musalem Laila,^a Mohd. Razali Rizal ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 29 January 2008; accepted 20 April 2008; online 26 April 2008)

The molecule of the title compound, C₁₄H₁₀FN₃O₃S, consists of an indole unit and a phenylsulfonyl unit that are disposed in an approximately trans orientation relative to the N—N single bond. Two molecules are arranged about a center of inversion, forming a hydrazide–carbonyl N—H⋯O hydrogen-bonded dimer; the dimers are linked by an indole–sulfonyl N—H⋯O hydrogen bond into a ribbon.

Related literature

For the crystal structures of related 3-indole benzenesulfonylhydrazones, see: Ali et al. (2007a ,b ,c ). For the crystal structure of 5-fluoro-1H-indole-2,3-dione, see: Naumov et al. (2000 ).

Experimental

Crystal data

C₁₄H₁₀FN₃O₃S
M_r = 319.31
Monoclinic, P 2₁ /c
a = 8.2218 (2) Å
b = 16.4933 (3) Å
c = 10.8585 (2) Å
β = 110.249 (1)°
V = 1381.46 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 123 (2) K
0.50 × 0.20 × 0.15 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.816, T_max = 0.962
10513 measured reflections
3166 independent reflections
2741 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.145
S = 1.20
3166 reflections
207 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1n⋯O3ⁱ	0.88 (1)	2.10 (2)	2.896 (2)	151 (2)
N3—H3n⋯O1ⁱⁱ	0.88 (1)	2.22 (2)	2.986 (2)	145 (2)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808011136/sg2224sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808011136/sg2224Isup2.hkl

checkCIF report

Comment top

We have reported the crystal structures of 3-indole benzenesulfonohydrazides (Ali et al., 2007a, 2007b, 2007c). The studies continue with the benzenesulfonohydrazide that is obtained by condensing benzenesulfonohydrazine with a substituted 1H-indol-2,3-dione, 5-fluroisatin. This compound exists as a hydrogen-bonded dimer (Naumov et al., 2000). The title compound (Scheme I) has the indolyl fused-ring portion and the phenylsulfonyl portion disposed in an approximately trans-alignment relative to the N–N single-bond (Fig. 1). Two molecules are arranged about a center-of-inversion to form an N–H_hydrazide···O_carbonyl hydrogen-bonded dimer; the dimers are linked by another N–H_indole···O_sulfonyl hydrogen bond into a ribbon structure (Fig. 2).

Related literature top

For the crystal structures of related 3-indole benzenesulfonylhydrazones, see: Ali et al. (2007a,b,c). For the crystal structure of 5-fluro-1H-indole-2,3-dione, see: Naumov et al. (2000).

Experimental top

Benzenesulfonyl hydrazide (0. 69 g, 4 mmol) and 5-fluoroisatin (0.66 g, 4 mmol) were heated in ethanol (50 ml) for an hour. The solution when cooled afforded yellow crystals.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

	Fig. 1. Thermal ellipsoid plot of C₁₄H₁₀FN₃O₃S. Displacement ellipsoids are drawn at the 70% probability level, and H atoms are shown as spheres of arbitrary radii.
	Fig. 2. Ribbon structure of C₁₀H₁₀FN₃O₃S.

N'-(5-Fluoro-2-oxo-2,3-dihydro-1H-indol-3-ylidene)benzenesulfonohydrazide top

Crystal data top

C₁₄H₁₀FN₃O₃S	F(000) = 656
M_r = 319.31	D_x = 1.535 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6063 reflections
a = 8.2218 (2) Å	θ = 3.0–31.3°
b = 16.4933 (3) Å	µ = 0.26 mm⁻¹
c = 10.8585 (2) Å	T = 123 K
β = 110.249 (1)°	Irregular block, yellow
V = 1381.46 (5) Å³	0.50 × 0.20 × 0.15 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	3166 independent reflections
Radiation source: medium-focus sealed tube	2741 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.816, T_max = 0.962	k = −21→21
10513 measured reflections	l = −13→14

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) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	w = 1/[σ²(F_o²) + (0.0922P)² + 0.2432P] where P = (F_o² + 2F_c²)/3
3166 reflections	(Δ/σ)_max = 0.001
207 parameters	Δρ_max = 0.54 e Å⁻³
2 restraints	Δρ_min = −0.60 e Å⁻³

Crystal data top

C₁₄H₁₀FN₃O₃S	V = 1381.46 (5) Å³
M_r = 319.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.2218 (2) Å	µ = 0.26 mm⁻¹
b = 16.4933 (3) Å	T = 123 K
c = 10.8585 (2) Å	0.50 × 0.20 × 0.15 mm
β = 110.249 (1)°

Data collection top

Bruker SMART APEX diffractometer	3166 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2741 reflections with I > 2σ(I)
T_min = 0.816, T_max = 0.962	R_int = 0.024
10513 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	2 restraints
wR(F²) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	Δρ_max = 0.54 e Å⁻³
3166 reflections	Δρ_min = −0.60 e Å⁻³
207 parameters

Special details top

Experimental. A medium-focus collimator of 0.8 mm diameter was used on the diffractometer to measure the somewhat large crystal.

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.

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

	x	y	z	U_iso*/U_eq
S1	0.65386 (5)	0.28692 (2)	0.54366 (4)	0.01609 (16)
O1	0.61921 (18)	0.21966 (7)	0.61409 (14)	0.0248 (3)
O2	0.56524 (17)	0.29375 (8)	0.40497 (13)	0.0255 (3)
O3	0.42474 (17)	0.51614 (8)	0.60498 (13)	0.0240 (3)
N1	0.59808 (19)	0.37034 (9)	0.60384 (14)	0.0183 (3)
H1N	0.557 (3)	0.4089 (11)	0.546 (2)	0.036 (7)*
N2	0.67998 (18)	0.38149 (8)	0.73560 (14)	0.0172 (3)
N3	0.5337 (2)	0.57008 (9)	0.81558 (16)	0.0232 (3)
H3N	0.478 (3)	0.6168 (9)	0.799 (2)	0.038 (7)*
C1	0.8794 (2)	0.29132 (9)	0.58025 (17)	0.0165 (3)
C2	0.9467 (3)	0.33843 (13)	0.50285 (19)	0.0277 (4)
H2	0.8730	0.3696	0.4318	0.033*
C3	1.1256 (3)	0.33841 (16)	0.5329 (2)	0.0368 (5)
H3	1.1754	0.3703	0.4823	0.044*
C4	1.2315 (3)	0.29211 (13)	0.6361 (2)	0.0349 (5)
H4	1.3530	0.2914	0.6541	0.042*
C5	1.1624 (2)	0.24721 (12)	0.7127 (2)	0.0300 (4)
H5	1.2364	0.2164	0.7841	0.036*
C6	0.9846 (2)	0.24692 (10)	0.68578 (19)	0.0227 (4)
H6	0.9360	0.2167	0.7390	0.027*
C7	0.6472 (2)	0.44753 (10)	0.78623 (17)	0.0174 (3)
C8	0.7275 (2)	0.47125 (10)	0.92317 (17)	0.0182 (4)
C9	0.8561 (2)	0.43576 (10)	1.02774 (17)	0.0219 (4)
H9	0.9069	0.3853	1.0192	0.026*
C10	0.9065 (3)	0.47769 (11)	1.14518 (18)	0.0252 (4)
C11	0.8372 (3)	0.55171 (11)	1.16168 (19)	0.0285 (4)
H11	0.8765	0.5779	1.2447	0.034*
C12	0.7090 (3)	0.58763 (11)	1.05538 (19)	0.0276 (4)
H12	0.6597	0.6385	1.0641	0.033*
C13	0.6564 (2)	0.54660 (10)	0.93715 (18)	0.0204 (4)
C14	0.5206 (2)	0.51454 (10)	0.72023 (17)	0.0187 (4)
F1	1.03509 (17)	0.44573 (7)	1.25055 (11)	0.0374 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0133 (2)	0.0151 (2)	0.0192 (3)	−0.00149 (13)	0.00483 (17)	−0.00402 (14)
O1	0.0232 (7)	0.0164 (6)	0.0388 (8)	−0.0042 (5)	0.0157 (6)	−0.0018 (5)
O2	0.0199 (7)	0.0309 (7)	0.0207 (7)	−0.0001 (5)	0.0006 (5)	−0.0086 (5)
O3	0.0257 (7)	0.0238 (6)	0.0195 (6)	0.0050 (5)	0.0039 (5)	−0.0003 (5)
N1	0.0202 (7)	0.0158 (7)	0.0180 (7)	0.0032 (5)	0.0053 (6)	−0.0009 (5)
N2	0.0179 (7)	0.0163 (7)	0.0179 (7)	−0.0007 (5)	0.0069 (6)	−0.0010 (5)
N3	0.0250 (8)	0.0194 (7)	0.0219 (8)	0.0074 (6)	0.0039 (6)	−0.0024 (6)
C1	0.0132 (8)	0.0191 (8)	0.0172 (8)	−0.0017 (6)	0.0053 (6)	−0.0053 (6)
C2	0.0251 (9)	0.0409 (11)	0.0185 (9)	−0.0057 (8)	0.0093 (7)	0.0000 (8)
C3	0.0284 (10)	0.0596 (14)	0.0287 (11)	−0.0140 (10)	0.0178 (9)	−0.0058 (10)
C4	0.0153 (9)	0.0477 (13)	0.0424 (12)	−0.0030 (8)	0.0108 (9)	−0.0180 (10)
C5	0.0196 (9)	0.0262 (10)	0.0370 (11)	0.0035 (7)	0.0005 (8)	−0.0062 (8)
C6	0.0202 (8)	0.0180 (8)	0.0269 (9)	0.0000 (6)	0.0042 (7)	0.0001 (7)
C7	0.0182 (8)	0.0154 (7)	0.0191 (8)	0.0007 (6)	0.0072 (7)	0.0000 (6)
C8	0.0223 (8)	0.0144 (7)	0.0183 (8)	−0.0007 (6)	0.0076 (7)	−0.0013 (6)
C9	0.0266 (9)	0.0166 (8)	0.0207 (9)	0.0012 (6)	0.0059 (7)	0.0019 (6)
C10	0.0287 (9)	0.0225 (9)	0.0197 (9)	−0.0010 (7)	0.0023 (7)	0.0037 (7)
C11	0.0364 (11)	0.0251 (9)	0.0202 (9)	−0.0022 (8)	0.0052 (8)	−0.0058 (7)
C12	0.0327 (10)	0.0217 (9)	0.0251 (10)	0.0039 (8)	0.0059 (8)	−0.0073 (7)
C13	0.0216 (8)	0.0180 (8)	0.0206 (9)	0.0019 (6)	0.0060 (7)	−0.0008 (6)
C14	0.0184 (8)	0.0172 (8)	0.0206 (9)	0.0016 (6)	0.0069 (7)	0.0005 (6)
F1	0.0471 (8)	0.0298 (6)	0.0211 (6)	0.0055 (5)	−0.0061 (5)	0.0026 (5)

Geometric parameters (Å, º) top

S1—O1	1.4309 (13)	C4—C5	1.375 (3)
S1—O2	1.4325 (14)	C4—H4	0.9500
S1—N1	1.6545 (14)	C5—C6	1.388 (3)
S1—C1	1.7582 (17)	C5—H5	0.9500
O3—C14	1.227 (2)	C6—H6	0.9500
N1—N2	1.367 (2)	C7—C8	1.456 (2)
N1—H1N	0.876 (10)	C7—C14	1.518 (2)
N2—C7	1.290 (2)	C8—C9	1.385 (2)
N3—C14	1.358 (2)	C8—C13	1.404 (2)
N3—C13	1.410 (2)	C9—C10	1.382 (3)
N3—H3N	0.884 (10)	C9—H9	0.9500
C1—C6	1.383 (2)	C10—F1	1.366 (2)
C1—C2	1.392 (3)	C10—C11	1.385 (3)
C2—C3	1.392 (3)	C11—C12	1.397 (3)
C2—H2	0.9500	C11—H11	0.9500
C3—C4	1.386 (3)	C12—C13	1.382 (3)
C3—H3	0.9500	C12—H12	0.9500

O1—S1—O2	119.99 (8)	C1—C6—C5	118.97 (18)
O1—S1—N1	107.46 (8)	C1—C6—H6	120.5
O2—S1—N1	103.90 (8)	C5—C6—H6	120.5
O1—S1—C1	107.50 (8)	N2—C7—C8	125.06 (15)
O2—S1—C1	110.32 (8)	N2—C7—C14	128.61 (16)
N1—S1—C1	106.93 (7)	C8—C7—C14	106.32 (14)
N2—N1—S1	114.96 (11)	C9—C8—C13	120.91 (16)
N2—N1—H1N	125.5 (17)	C9—C8—C7	132.16 (16)
S1—N1—H1N	114.2 (17)	C13—C8—C7	106.84 (15)
C7—N2—N1	117.39 (14)	C10—C9—C8	116.43 (16)
C14—N3—C13	111.76 (15)	C10—C9—H9	121.8
C14—N3—H3N	122.4 (17)	C8—C9—H9	121.8
C13—N3—H3N	125.6 (17)	F1—C10—C9	118.54 (17)
C6—C1—C2	122.02 (17)	F1—C10—C11	117.74 (17)
C6—C1—S1	118.29 (14)	C9—C10—C11	123.70 (17)
C2—C1—S1	119.69 (14)	C10—C11—C12	119.57 (17)
C1—C2—C3	117.85 (19)	C10—C11—H11	120.2
C1—C2—H2	121.1	C12—C11—H11	120.2
C3—C2—H2	121.1	C13—C12—C11	117.64 (17)
C4—C3—C2	120.4 (2)	C13—C12—H12	121.2
C4—C3—H3	119.8	C11—C12—H12	121.2
C2—C3—H3	119.8	C12—C13—C8	121.74 (17)
C5—C4—C3	120.72 (19)	C12—C13—N3	128.89 (16)
C5—C4—H4	119.6	C8—C13—N3	109.37 (15)
C3—C4—H4	119.6	O3—C14—N3	128.06 (16)
C4—C5—C6	119.97 (19)	O3—C14—C7	126.22 (15)
C4—C5—H5	120.0	N3—C14—C7	105.70 (15)
C6—C5—H5	120.0

O1—S1—N1—N2	57.51 (14)	C14—C7—C8—C13	−0.74 (19)
O2—S1—N1—N2	−174.35 (12)	C13—C8—C9—C10	1.2 (3)
C1—S1—N1—N2	−57.66 (14)	C7—C8—C9—C10	177.29 (18)
S1—N1—N2—C7	176.78 (12)	C8—C9—C10—F1	−178.89 (16)
O1—S1—C1—C6	−14.56 (16)	C8—C9—C10—C11	−0.6 (3)
O2—S1—C1—C6	−147.07 (13)	F1—C10—C11—C12	178.16 (18)
N1—S1—C1—C6	100.57 (14)	C9—C10—C11—C12	−0.1 (3)
O1—S1—C1—C2	165.08 (14)	C10—C11—C12—C13	0.3 (3)
O2—S1—C1—C2	32.58 (16)	C11—C12—C13—C8	0.3 (3)
N1—S1—C1—C2	−79.78 (16)	C11—C12—C13—N3	−178.45 (19)
C6—C1—C2—C3	1.4 (3)	C9—C8—C13—C12	−1.1 (3)
S1—C1—C2—C3	−178.20 (16)	C7—C8—C13—C12	−178.09 (17)
C1—C2—C3—C4	0.5 (3)	C9—C8—C13—N3	177.87 (16)
C2—C3—C4—C5	−1.8 (3)	C7—C8—C13—N3	0.9 (2)
C3—C4—C5—C6	1.0 (3)	C14—N3—C13—C12	178.14 (19)
C2—C1—C6—C5	−2.2 (3)	C14—N3—C13—C8	−0.8 (2)
S1—C1—C6—C5	177.47 (14)	C13—N3—C14—O3	178.88 (18)
C4—C5—C6—C1	0.9 (3)	C13—N3—C14—C7	0.3 (2)
N1—N2—C7—C8	−177.31 (15)	N2—C7—C14—O3	0.9 (3)
N1—N2—C7—C14	3.5 (3)	C8—C7—C14—O3	−178.35 (17)
N2—C7—C8—C9	3.5 (3)	N2—C7—C14—N3	179.59 (17)
C14—C7—C8—C9	−177.21 (18)	C8—C7—C14—N3	0.29 (19)
N2—C7—C8—C13	179.93 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···O3ⁱ	0.88 (1)	2.10 (2)	2.896 (2)	151 (2)
N3—H3n···O1ⁱⁱ	0.88 (1)	2.22 (2)	2.986 (2)	145 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₀FN₃O₃S
M_r	319.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	123
a, b, c (Å)	8.2218 (2), 16.4933 (3), 10.8585 (2)
β (°)	110.249 (1)
V (Å³)	1381.46 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.50 × 0.20 × 0.15

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.816, 0.962
No. of measured, independent and observed [I > 2σ(I)] reflections	10513, 3166, 2741
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.145, 1.20
No. of reflections	3166
No. of parameters	207
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.60

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···O3ⁱ	0.88 (1)	2.10 (2)	2.896 (2)	151 (2)
N3—H3n···O1ⁱⁱ	0.88 (1)	2.22 (2)	2.986 (2)	145 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y+1/2, −z+3/2.

Acknowledgements

The authors thank the University of Canterbury, New Zealand, for the diffraction measurements, and the Science Fund (12–02-03–2031) for supporting this study.

References

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