N-[3-(Prop-1-yn-1-yl)phen­yl]benzene­sulfonamide

Pineda, L.W.; Cabezas, J.A.

doi:10.1107/S2414314619011763

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 9| September 2019| x191176

https://doi.org/10.1107/S2414314619011763

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N-[3-(Prop-1-yn-1-yl)phenyl]benzenesulfonamide

Leslie W. Pineda ^a,^b and Jorge A. Cabezas ^a ^*

^aEscuela de Química, Universidad de Costa Rica, 11501-2060, San José, Costa Rica, and ^bCentro de Electroquímica y Energía Química (CELEQ), Universidad de Costa Rica, 11501-2060, San José, Costa Rica
^*Correspondence e-mail: jorge.cabezas@ucr.ac.cr

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 30 July 2019; accepted 26 August 2019; online 3 September 2019)

In the title sulfanilamide derivative, C₁₅H₁₃NO₂S, which shows significant activity against Staphylococcus aureus and Escherichia coli, the dihedral angle between the planes of the aromatic rings is 62.15 (19)° and the four-coordinate S atom adopts an almost ideal tetrahedral geometry. In the crystal, N—H⋯O and C—H⋯O hydrogen bonds link the molecules into a three-dimensional network.

Keywords: crystal structure; antibacterial activity; N—H⋯O hydrogen bonding; propyne substituent; sulfonamide.

CCDC reference: 1887179

Structure description

In 1932, a drug called Prontosil was discovered by the pharmaceutical division of IG Farbenindustrie, an industrial conglomerate of German companies, including Bayer Company. It was found to be very successful treating several diseases in humans, provoked by Staphylococcus and Streptococcus. Prontosil was the first antibacterial drug, with life-saving capability, to be used systematically for the treatment of bacterial infections in the body. It belongs to a family of compounds called sulfa drugs or sulfonamides. In the 1940s and 1950s, most of the sulfa drugs were replaced by penicillin and other drugs, which proved to be more effective against more types of bacteria. However, nowadays, some sulfa drugs such as sulfamethoxazole, in combination with trimethoprim (co-trimoxazole), are still used extensively to inhibit the growth of bacteria that produce opportunistic infections in patients with AIDS, and bacterial infections such as pneumonia, bronchitis and infections of the urinary tract, ears and intestines (Brumfitt & Hamilton-Miller, 1993 ).

As part of our studies in this area we now report the synthesis of of the title sulfanilamide derivative, 1, and its crystal structure. This compound, has been found to be very effective against Staphylococcus aureus and Escherichia coli, and minimal inhibitory concentrations (MIC) of 12.5 µg ml⁻¹ and 25.0 µg ml⁻¹ have been obtained respectively (Cabezas & Arias, 2019 ).

The crystal structure of 1 has monoclinic symmetry with one molecule in the asymmetric unit: the molecular structure consists of a benzenesulfonamide fragment bound to a benzene ring bearing in its 3-position a propyne substituent (Fig. 1): the dihedral angle between the C1–C6 and C10–C15 benzene rings is 62.15 (19)°. The length of the carbon–carbon triple bond (C7≡C8) is 1.181 (5) Å, with the C7—C8—C9 and C8—C7—C1 angles being 178.8 (4) and 178.1 (4)°, respectively, which are slightly distorted from the expected linear geometry. The calculation of the angular structural index (τ₄ = 0.94; and τ₄' = 0.90) for the four-coordinate S1 atom, which binds to O1, O2, N1 and C10 from the benzene ring (Yang et al., 2007 ; Okuniewski et al., 2015 ; Rosiak et al., 2018 ) indicates that it adopts an almost ideal tetrahedral geometry (τ₄ = 0 for an ideal square and 1 for an ideal tetrahedron). In the extended structure of 1, weak N1—H1⋯O2, C4—H4⋯O1 and C6—H6⋯O1 hydrogen bonds are observed (Table 1, Fig. 2), leading to the formation of a three-dimensional network.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.88	2.55	2.984 (4)	111
C4—H4⋯O1ⁱⁱ	0.95	2.45	3.256 (4)	143
C6—H6⋯O1	0.95	2.39	2.955 (4)	118
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) x, y, z+1.

Figure 1
The title molecule with 50% probability ellipsoids.

Figure 2
Part of an [001] hydrogen-bonded chain with N—H⋯O2, C—H⋯O1 hydrogen bonds shown as green lines.

Synthesis and crystallization

The title compound, 1, was synthesized by treatment of 3-iodoaniline, 2, with benzenesulfonyl chloride, 3, in the presence of pyridine, at room temperature to obtain, after purification by column chromatography (ether:hexane, 40:60), iodosulfonamide, 4, in 75% yield. This aromatic iodide 4, was treated with propyne, under Sonogashira's reaction conditions (Sonogashira et al., 1975 ), using CuI and (Ph₃P)₂PdCl₂ as catalysts, (Fig. 3). After purification by column chromatography, using a solvent mixture of hexane:ethyl acetate (75:25), compound 1 was isolated in 70% yield, and with an overall yield of 53%. The product was recrystallized from ethyl acetate solution at room temperature to result in light-yellow blocks of the title compound.

Figure 3
A synthetic scheme for the preparation of the title compound.

Refinement

Crystal data, data collection and structure refinement are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₃NO₂S
M_r	271.32
Crystal system, space group	Monoclinic, Cc
Temperature (K)	100
a, b, c (Å)	8.4596 (4), 24.9769 (13), 7.1310 (4)
β (°)	117.557 (2)
V (Å³)	1335.80 (12)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.24
Crystal size (mm)	0.35 × 0.20 × 0.15

Data collection
Diffractometer	Bruker D8 Venture CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2015 )
T_min, T_max	0.704, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	9630, 3028, 2716
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.089, 1.03
No. of reflections	3028
No. of parameters	173
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.47
Absolute structure	Flack x determined using 1163 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013)
Absolute structure parameter	0.02 (3)
Computer programs: APEX3 and SAINT (Bruker, 2015), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), Mercury (Macrae et al., 2006 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1887179

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314619011763/hb4312sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619011763/hb4312Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314619011763/hb4312Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

N-[3-(Prop-1-yn-1-yl)phenyl]benzenesulfonamide top

Crystal data top

C₁₅H₁₃NO₂S	F(000) = 568
M_r = 271.32	D_x = 1.349 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 8.4596 (4) Å	Cell parameters from 4995 reflections
b = 24.9769 (13) Å	θ = 2.8–27.5°
c = 7.1310 (4) Å	µ = 0.24 mm⁻¹
β = 117.557 (2)°	T = 100 K
V = 1335.80 (12) Å³	Block, clear light yellow
Z = 4	0.35 × 0.20 × 0.15 mm

Data collection top

Bruker D8 Venture CCD diffractometer	3028 independent reflections
Radiation source: Incoatec Microsource	2716 reflections with I > 2σ(I)
Mirrors monochromator	R_int = 0.037
Detector resolution: 10.4167 pixels mm^-1	θ_max = 27.5°, θ_min = 2.8°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = −32→32
T_min = 0.704, T_max = 0.746	l = −9→9
9630 measured reflections

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) = 0.089	w = 1/[σ²(F_o²) + (0.0401P)² + 1.2876P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3028 reflections	Δρ_max = 0.39 e Å⁻³
173 parameters	Δρ_min = −0.47 e Å⁻³
2 restraints	Absolute structure: Flack x determined using 1163 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (3)

Special details top

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. All hydrogen atoms were placed geometrically and refined using a riding-atom model approximation, with C—H = 0.95–1.00 Å, with U_iso(H) = 1.2U_eq(C). A rotating group model was used for the methyl groups.

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

	x	y	z	U_iso*/U_eq
S1	0.73168 (11)	0.55417 (3)	0.33500 (12)	0.01205 (19)
O1	0.7499 (3)	0.58926 (10)	0.1883 (4)	0.0159 (5)
O2	0.7908 (3)	0.49971 (10)	0.3513 (4)	0.0171 (6)
N1	0.8464 (4)	0.57903 (11)	0.5727 (4)	0.0138 (6)
H1	0.9279	0.5593	0.6732	0.017*
C1	0.7946 (5)	0.72772 (15)	0.5484 (6)	0.0188 (8)
C2	0.7594 (6)	0.73618 (15)	0.7189 (6)	0.0243 (9)
H2	0.7403	0.7715	0.7534	0.029*
C3	0.7522 (6)	0.69340 (15)	0.8383 (8)	0.0267 (9)
H3	0.7297	0.6994	0.9553	0.032*
C4	0.7781 (5)	0.64153 (15)	0.7865 (6)	0.0176 (8)
H4	0.7705	0.612	0.8661	0.021*
C5	0.8149 (4)	0.63297 (13)	0.6184 (5)	0.0134 (7)
C6	0.8256 (5)	0.67587 (14)	0.5006 (5)	0.0156 (7)
H6	0.8538	0.6699	0.388	0.019*
C7	0.7989 (5)	0.77163 (15)	0.4189 (6)	0.0216 (9)
C8	0.7988 (5)	0.80679 (16)	0.3081 (6)	0.0232 (9)
C9	0.7969 (7)	0.85150 (17)	0.1717 (8)	0.0345 (11)
H9A	0.8463	0.8393	0.0788	0.052*
H9B	0.8692	0.8811	0.26	0.052*
H9C	0.6741	0.8637	0.0855	0.052*
C10	0.5068 (4)	0.55427 (14)	0.2802 (5)	0.0138 (7)
C11	0.4331 (5)	0.50847 (14)	0.3182 (5)	0.0159 (7)
H11	0.5029	0.477	0.3718	0.019*
C12	0.2569 (5)	0.50936 (17)	0.2771 (6)	0.0207 (8)
H12	0.205	0.4782	0.3023	0.025*
C13	0.1549 (5)	0.55524 (16)	0.1993 (6)	0.0202 (8)
H13	0.0343	0.5557	0.1737	0.024*
C14	0.2302 (5)	0.60067 (15)	0.1587 (6)	0.0215 (8)
H14	0.1597	0.6319	0.1025	0.026*
C15	0.4069 (5)	0.60055 (14)	0.1997 (6)	0.0168 (7)
H15	0.4588	0.6315	0.1733	0.02*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0130 (4)	0.0114 (4)	0.0127 (4)	0.0013 (4)	0.0067 (3)	−0.0001 (4)
O1	0.0207 (14)	0.0150 (12)	0.0146 (12)	0.0001 (10)	0.0103 (11)	0.0000 (10)
O2	0.0190 (13)	0.0147 (12)	0.0183 (13)	0.0030 (10)	0.0094 (11)	−0.0010 (10)
N1	0.0139 (15)	0.0131 (14)	0.0117 (14)	0.0025 (12)	0.0035 (12)	0.0011 (11)
C1	0.0196 (19)	0.0142 (17)	0.0189 (19)	−0.0017 (15)	0.0057 (15)	0.0006 (15)
C2	0.037 (2)	0.0141 (19)	0.022 (2)	0.0016 (17)	0.0139 (19)	−0.0035 (16)
C3	0.040 (3)	0.0230 (19)	0.0225 (19)	0.001 (2)	0.0188 (19)	−0.002 (2)
C4	0.0222 (19)	0.0162 (18)	0.0174 (18)	−0.0003 (15)	0.0119 (16)	0.0039 (15)
C5	0.0119 (17)	0.0106 (17)	0.0132 (17)	−0.0002 (13)	0.0019 (14)	−0.0016 (13)
C6	0.0148 (17)	0.0169 (18)	0.0140 (17)	−0.0019 (14)	0.0058 (14)	−0.0005 (14)
C7	0.026 (2)	0.0125 (19)	0.025 (2)	−0.0011 (16)	0.0105 (17)	−0.0060 (16)
C8	0.028 (2)	0.017 (2)	0.025 (2)	−0.0021 (17)	0.0128 (19)	−0.0025 (18)
C9	0.043 (3)	0.024 (2)	0.039 (3)	0.001 (2)	0.021 (2)	0.011 (2)
C10	0.0132 (15)	0.0171 (17)	0.0110 (16)	0.0015 (15)	0.0054 (14)	−0.0030 (14)
C11	0.0180 (18)	0.0158 (18)	0.0129 (16)	−0.0009 (15)	0.0062 (14)	0.0010 (14)
C12	0.0190 (19)	0.028 (2)	0.0158 (18)	−0.0072 (16)	0.0088 (15)	0.0017 (16)
C13	0.0142 (18)	0.030 (2)	0.0172 (18)	−0.0017 (17)	0.0078 (15)	−0.0075 (17)
C14	0.0182 (19)	0.019 (2)	0.022 (2)	0.0015 (16)	0.0046 (16)	−0.0051 (16)
C15	0.0194 (19)	0.0125 (17)	0.0168 (17)	−0.0014 (14)	0.0069 (15)	−0.0034 (14)

Geometric parameters (Å, º) top

S1—O1	1.427 (3)	C7—C8	1.181 (5)
S1—O2	1.435 (3)	C8—C9	1.477 (5)
S1—N1	1.636 (3)	C9—H9A	0.98
S1—C10	1.756 (3)	C9—H9B	0.98
N1—C5	1.440 (4)	C9—H9C	0.98
N1—H1	0.88	C10—C11	1.388 (5)
C1—C6	1.394 (5)	C10—C15	1.390 (5)
C1—C2	1.396 (6)	C11—C12	1.380 (5)
C1—C7	1.445 (5)	C11—H11	0.95
C2—C3	1.385 (6)	C12—C13	1.387 (6)
C2—H2	0.95	C12—H12	0.95
C3—C4	1.392 (5)	C13—C14	1.395 (5)
C3—H3	0.95	C13—H13	0.95
C4—C5	1.387 (5)	C14—C15	1.384 (5)
C4—H4	0.95	C14—H14	0.95
C5—C6	1.390 (5)	C15—H15	0.95
C6—H6	0.95

O1—S1—O2	119.34 (15)	C8—C7—C1	178.1 (4)
O1—S1—N1	108.24 (15)	C7—C8—C9	178.8 (4)
O2—S1—N1	104.96 (15)	C8—C9—H9A	109.5
O1—S1—C10	108.01 (16)	C8—C9—H9B	109.5
O2—S1—C10	108.67 (16)	H9A—C9—H9B	109.5
N1—S1—C10	107.00 (15)	C8—C9—H9C	109.5
C5—N1—S1	120.4 (2)	H9A—C9—H9C	109.5
C5—N1—H1	119.8	H9B—C9—H9C	109.5
S1—N1—H1	119.8	C11—C10—C15	121.6 (3)
C6—C1—C2	119.5 (3)	C11—C10—S1	119.6 (3)
C6—C1—C7	119.1 (3)	C15—C10—S1	118.8 (3)
C2—C1—C7	121.4 (3)	C12—C11—C10	118.9 (3)
C3—C2—C1	120.4 (4)	C12—C11—H11	120.5
C3—C2—H2	119.8	C10—C11—H11	120.5
C1—C2—H2	119.8	C11—C12—C13	120.6 (4)
C2—C3—C4	119.9 (4)	C11—C12—H12	119.7
C2—C3—H3	120.1	C13—C12—H12	119.7
C4—C3—H3	120.1	C12—C13—C14	119.7 (3)
C5—C4—C3	119.9 (4)	C12—C13—H13	120.1
C5—C4—H4	120.1	C14—C13—H13	120.1
C3—C4—H4	120.1	C15—C14—C13	120.4 (4)
C4—C5—C6	120.4 (3)	C15—C14—H14	119.8
C4—C5—N1	118.6 (3)	C13—C14—H14	119.8
C6—C5—N1	120.9 (3)	C14—C15—C10	118.7 (3)
C5—C6—C1	119.8 (3)	C14—C15—H15	120.7
C5—C6—H6	120.1	C10—C15—H15	120.7
C1—C6—H6	120.1

O1—S1—N1—C5	54.7 (3)	O1—S1—C10—C11	148.8 (3)
O2—S1—N1—C5	−176.8 (3)	O2—S1—C10—C11	18.0 (3)
C10—S1—N1—C5	−61.5 (3)	N1—S1—C10—C11	−94.9 (3)
C6—C1—C2—C3	−1.1 (6)	O1—S1—C10—C15	−31.3 (3)
C7—C1—C2—C3	178.6 (4)	O2—S1—C10—C15	−162.1 (3)
C1—C2—C3—C4	−0.8 (6)	N1—S1—C10—C15	85.0 (3)
C2—C3—C4—C5	1.4 (6)	C15—C10—C11—C12	−0.7 (5)
C3—C4—C5—C6	−0.2 (5)	S1—C10—C11—C12	179.1 (3)
C3—C4—C5—N1	178.1 (4)	C10—C11—C12—C13	−0.1 (5)
S1—N1—C5—C4	126.3 (3)	C11—C12—C13—C14	1.1 (6)
S1—N1—C5—C6	−55.4 (4)	C12—C13—C14—C15	−1.3 (6)
C4—C5—C6—C1	−1.6 (5)	C13—C14—C15—C10	0.5 (5)
N1—C5—C6—C1	−179.9 (3)	C11—C10—C15—C14	0.5 (5)
C2—C1—C6—C5	2.3 (5)	S1—C10—C15—C14	−179.3 (3)
C7—C1—C6—C5	−177.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.88	2.55	2.984 (4)	111
C4—H4···O1ⁱⁱ	0.95	2.45	3.256 (4)	143
C6—H6···O1	0.95	2.39	2.955 (4)	118

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

Acknowledgements

CELEQ is thanked for supplying liquid nitrogen for the X-ray measurements.

Funding information

Funding for this research was provided by: Vicerrectoría de Investigación, Universidad de Costa Rica (UCR); Escuela de Química (UCR).

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