1,2,3,4-Tetra­hydro­isoquinoline-2-sulfonamide

Bouasla, R.; Berredjem, M.; Aouf, N.-E.; Barbey, C.

doi:10.1107/S1600536807068158

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o432

doi:10.1107/S1600536807068158

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1,2,3,4-Tetrahydroisoquinoline-2-sulfonamide

Radia Bouasla,^a Malika Berredjem,^a Nour-Eddine Aouf ^a and Carole Barbey ^b ^*

^aLaboratoire de Chimie Organique Appliquée, LCOA, Groupe de Chimie Bioorganique, Faculté des Sciences, Département de Chimie, Université d'Annaba, Algeria, and ^bLaboratoire de Biophysique Moléculaire Cellulaire et Tissulaire (UMR 7033 CNRS), UFR-SMBH Université Paris-Nord, 74 rue M. Cachin, 93017 Bobigny Cedex, France
^*Correspondence e-mail: carole.barbey@smbh.univ-paris13.fr

(Received 18 December 2007; accepted 21 December 2007; online 11 January 2008)

The title compound, C₉H₁₂N₂O₂S, is a useful precursor of a variety of modified sulfonamide molecules. Due to the importance of these molecules in biological systems (antibacterials, antidepressants and many other applications), there is a growing interest in the discovery of new biologically active compounds. In the title compound, the molecules are linked by N—H⋯O intermolecular hydrogen bonds involving the sulfonamide function to form an infinite two-dimensional network parallel to the (001) plane.

Related literature

For related literature, see: Berredjem et al. (2000 ); Lee & Lee (2002 ); Martinez et al. (2000 ); Xiao & Timberlake (2000 ); Esteve & Bidal (2002 ); Soledade et al. (2006 ).

Experimental

Crystal data

C₉H₁₂N₂O₂S
M_r = 212.27
Monoclinic, P 2₁
a = 5.275 (1) Å
b = 9.541 (1) Å
c = 10.229 (1) Å
β = 101.80 (5)°
V = 503.93 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 293 (2) K
0.10 × 0.10 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
8285 measured reflections
2210 independent reflections
2106 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.087
S = 1.13
2210 reflections
127 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.30 e Å⁻³
Absolute structure: Flack (1983 ), 979 Friedel pairs
Flack parameter: −0.01 (6)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O1ⁱ	0.91	2.03	2.928 (2)	173
N2—H22⋯O2ⁱⁱ	0.92	2.10	2.971 (2)	159
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+1]$ ; (ii) x-1, y, z.

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and CrystalBuilder (DECOMET Laboratory, 2007 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807068158/dn2304sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807068158/dn2304Isup2.hkl

checkCIF report

Comment top

The sulfamide unit is an ubiquitous structural entity in many naturally occurring compounds and medicinal agents (i.e. anticonvulsant, antihypertensive, hypoglycemic agents, histamine H2-receptor antagonist, herbicide, human cytomegalovirus inibitors···) (Soledade et al., 2006; Esteve & Bidal, 2002; Xiao & Timberlake, 2000; Martinez et al., 2000; Berredjem et al., 2000; Lee et al., 2002) We report herein the synthesis and the crystal structure determination of the title compound (Fig. 1).

The crystal structure consists of layers of hydrophobic regions that enclose the bicyclic moiety and polar regions where the sulfamide atoms are involved in hydrogen bond network. Namely, the sulfamide group is involved in four hydrogen bonds (2 with sulfamide O atoms, 2 with nitrogen atom) with four different symmetry-related molecules, building a two dimensional network parallel to the (0 0 1) plane (Table 1, Fig. 2).

Related literature top

For related literature, see: Berredjem et al. (2000); Lee & Lee (2002); Martinez et al. (2000); Xiao & Timberlake (2000); Esteve & Bidal(2002); Soledade et al. (2006).

Experimental top

A solution of dimethyl malate (2,27 g, 14.1 mmol) in anhydrous CH₂Cl₂ (10 ml) was added to a stirring solution of chlorosulfonyl isocyanate (1.23 ml, 14.1 mmol) in CH₂Cl₂ (10 ml) at 0°C dropwise over period of 10 min. The resulting solution was transferred to a mixture of 1, 2, 3, 4 tetrahydroquinoleine (1,87 g, 14,1 mmol) in CH₂Cl₂ (20 ml) in the presence of triethylamine (1.1 equiv.). The solution was stirred at 0°C for less than 1.5 h. The reaction mixture was washed with HCl 0.1 N and water, and the organic layer was dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. Two compounds were obtained after purification by silica gel chromatography (Fig. 3). Slow evaporation at room temperature of a concentrated dichloromethane / methanol (9/1) solution of the most polar product (sulfamide I) afforded yellow crystals suitable for diffraction.

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: COLLECT (Hooft, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and CrystalBuilder (DECOMET Laboratory, 2007).

Figures top

	Fig. 1. Molecular View of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Partial packing view showing the formation of the two dimensional network. H bonds are represented as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (i) x - 1, y, z; (ii) -x + 1, y + 1/2, -z + 1]
	Fig. 3. Chemical pathway of the formation of (I)

1,2,3,4-Tetrahydroisoquinoline-2-sulfonamide top

Crystal data top

C₉H₁₂N₂O₂S	F(000) = 224
M_r = 212.27	D_x = 1.399 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: P 2yb	Cell parameters from 6025 reflections
a = 5.275 (1) Å	θ = 2.0–27.5°
b = 9.541 (1) Å	µ = 0.30 mm⁻¹
c = 10.229 (1) Å	T = 293 K
β = 101.80 (5)°	Parallelepipedic, yellow
V = 503.93 (15) Å³	0.10 × 0.10 × 0.10 mm
Z = 2

Data collection top

Nonius KappaCCD diffractometer	2106 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.032
Graphite monochromator	θ_max = 27.5°, θ_min = 2.0°
Detector resolution: 9 pixels mm^-1	h = −6→6
ϕ and ω scans	k = −12→11
8285 measured reflections	l = −13→13
2210 independent 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)] = 0.030	H-atom parameters constrained
wR(F²) = 0.087	w = 1/[σ²(F_o²) + (0.0575P)² + 0.0148P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max < 0.001
2210 reflections	Δρ_max = 0.25 e Å⁻³
127 parameters	Δρ_min = −0.30 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 979 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (6)

Crystal data top

C₉H₁₂N₂O₂S	V = 503.93 (15) Å³
M_r = 212.27	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 5.275 (1) Å	µ = 0.30 mm⁻¹
b = 9.541 (1) Å	T = 293 K
c = 10.229 (1) Å	0.10 × 0.10 × 0.10 mm
β = 101.80 (5)°

Data collection top

Nonius KappaCCD diffractometer	2106 reflections with I > 2σ(I)
8285 measured reflections	R_int = 0.032
2210 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.087	Δρ_max = 0.25 e Å⁻³
S = 1.13	Δρ_min = −0.30 e Å⁻³
2210 reflections	Absolute structure: Flack (1983), 979 Friedel pairs
127 parameters	Absolute structure parameter: −0.01 (6)
1 restraint

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
S1	0.56649 (7)	0.52966 (4)	0.42439 (3)	0.03710 (13)
N1	0.4887 (3)	0.60389 (14)	0.27757 (14)	0.0369 (3)
C3	0.5408 (4)	0.7557 (2)	0.2719 (2)	0.0475 (5)
H3A	0.6993	0.7792	0.3345	0.057*
H3B	0.3998	0.8087	0.2956	0.057*
O2	0.8298 (3)	0.5665 (2)	0.47635 (14)	0.0624 (5)
C6	0.1947 (4)	0.6250 (2)	0.06005 (17)	0.0415 (4)
C7	0.2282 (4)	0.5698 (2)	0.20079 (17)	0.0451 (4)
H7A	0.0985	0.6112	0.2439	0.054*
H7B	0.2038	0.4690	0.1987	0.054*
C8	0.3113 (5)	0.7727 (3)	−0.1068 (2)	0.0608 (6)
H8	0.4195	0.8406	−0.1311	0.073*
C9	0.3522 (4)	0.7280 (2)	0.02630 (18)	0.0442 (4)
C10	0.1146 (5)	0.7182 (3)	−0.2021 (2)	0.0631 (6)
H10	0.0888	0.7499	−0.2898	0.076*
C11	−0.0028 (5)	0.5703 (3)	−0.0374 (2)	0.0611 (6)
H11	−0.1098	0.5009	−0.0146	0.073*
C12	−0.0432 (5)	0.6172 (3)	−0.1677 (2)	0.0669 (7)
H12	−0.1773	0.5802	−0.2317	0.080*
C13	0.5667 (4)	0.7918 (2)	0.1305 (2)	0.0538 (5)
H13A	0.5636	0.8929	0.1200	0.065*
H13B	0.7325	0.7582	0.1162	0.065*
O1	0.4929 (3)	0.38595 (15)	0.40334 (14)	0.0580 (4)
N2	0.4032 (3)	0.59065 (17)	0.52808 (16)	0.0426 (3)
H21	0.4478	0.6796	0.5540	0.051*
H22	0.2355	0.5596	0.5109	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0370 (2)	0.0412 (2)	0.03170 (18)	0.00882 (17)	0.00373 (13)	0.00083 (17)
N1	0.0378 (8)	0.0365 (8)	0.0340 (6)	0.0022 (6)	0.0012 (5)	0.0019 (6)
C3	0.0564 (12)	0.0391 (10)	0.0451 (10)	−0.0060 (8)	0.0055 (9)	0.0004 (8)
O2	0.0313 (7)	0.1054 (14)	0.0475 (7)	0.0094 (7)	0.0011 (5)	0.0075 (8)
C6	0.0424 (10)	0.0444 (9)	0.0356 (8)	0.0066 (8)	0.0029 (7)	0.0031 (7)
C7	0.0430 (9)	0.0500 (11)	0.0385 (8)	−0.0071 (8)	−0.0008 (7)	0.0080 (7)
C8	0.0667 (15)	0.0737 (15)	0.0458 (11)	0.0099 (12)	0.0204 (11)	0.0167 (11)
C9	0.0457 (9)	0.0485 (10)	0.0399 (8)	0.0096 (8)	0.0122 (8)	0.0069 (8)
C10	0.0767 (15)	0.0790 (15)	0.0340 (9)	0.0256 (13)	0.0121 (10)	0.0077 (10)
C11	0.0631 (13)	0.0690 (14)	0.0434 (10)	−0.0081 (11)	−0.0069 (9)	0.0031 (9)
C12	0.0745 (15)	0.0789 (17)	0.0395 (10)	0.0129 (13)	−0.0066 (10)	−0.0040 (10)
C13	0.0525 (12)	0.0564 (13)	0.0514 (11)	−0.0089 (10)	0.0080 (9)	0.0130 (10)
O1	0.0933 (12)	0.0335 (7)	0.0448 (7)	0.0131 (7)	0.0087 (7)	0.0030 (6)
N2	0.0424 (8)	0.0439 (8)	0.0431 (8)	−0.0024 (6)	0.0122 (6)	−0.0091 (7)

Geometric parameters (Å, º) top

S1—O2	1.4261 (16)	C8—C10	1.373 (4)
S1—O1	1.4293 (16)	C8—C9	1.401 (3)
S1—N2	1.6060 (16)	C8—H8	0.9300
S1—N1	1.6350 (14)	C9—C13	1.515 (3)
N1—C7	1.473 (2)	C10—C12	1.366 (4)
N1—C3	1.478 (2)	C10—H10	0.9300
C3—C13	1.520 (3)	C11—C12	1.380 (3)
C3—H3A	0.9700	C11—H11	0.9300
C3—H3B	0.9700	C12—H12	0.9300
C6—C9	1.376 (3)	C13—H13A	0.9700
C6—C11	1.388 (3)	C13—H13B	0.9700
C6—C7	1.509 (2)	N2—H21	0.9059
C7—H7A	0.9700	N2—H22	0.9154
C7—H7B	0.9700

O2—S1—O1	120.43 (11)	C10—C8—C9	121.3 (2)
O2—S1—N2	106.12 (10)	C10—C8—H8	119.4
O1—S1—N2	106.34 (10)	C9—C8—H8	119.4
O2—S1—N1	106.13 (10)	C6—C9—C8	118.7 (2)
O1—S1—N1	105.53 (8)	C6—C9—C13	120.86 (17)
N2—S1—N1	112.45 (9)	C8—C9—C13	120.4 (2)
C7—N1—C3	110.85 (15)	C12—C10—C8	119.7 (2)
C7—N1—S1	115.19 (12)	C12—C10—H10	120.1
C3—N1—S1	116.54 (12)	C8—C10—H10	120.1
N1—C3—C13	108.23 (16)	C12—C11—C6	121.1 (2)
N1—C3—H3A	110.1	C12—C11—H11	119.5
C13—C3—H3A	110.1	C6—C11—H11	119.5
N1—C3—H3B	110.1	C10—C12—C11	119.7 (2)
C13—C3—H3B	110.1	C10—C12—H12	120.1
H3A—C3—H3B	108.4	C11—C12—H12	120.1
C9—C6—C11	119.43 (18)	C9—C13—C3	112.27 (17)
C9—C6—C7	122.01 (17)	C9—C13—H13A	109.1
C11—C6—C7	118.57 (18)	C3—C13—H13A	109.1
N1—C7—C6	110.24 (15)	C9—C13—H13B	109.1
N1—C7—H7A	109.6	C3—C13—H13B	109.1
C6—C7—H7A	109.6	H13A—C13—H13B	107.9
N1—C7—H7B	109.6	S1—N2—H21	113.0
C6—C7—H7B	109.6	S1—N2—H22	112.6
H7A—C7—H7B	108.1	H21—N2—H22	122.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O1ⁱ	0.91	2.03	2.928 (2)	173
N2—H22···O2ⁱⁱ	0.92	2.10	2.971 (2)	159

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

Experimental details

Crystal data
Chemical formula	C₉H₁₂N₂O₂S
M_r	212.27
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	5.275 (1), 9.541 (1), 10.229 (1)
β (°)	101.80 (5)
V (Å³)	503.93 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.10 × 0.10 × 0.10

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8285, 2210, 2106
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.087, 1.13
No. of reflections	2210
No. of parameters	127
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.30
Absolute structure	Flack (1983), 979 Friedel pairs
Absolute structure parameter	−0.01 (6)

Computer programs: COLLECT (Hooft, 1998), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), SHELXL97 (Sheldrick, 1997) and CrystalBuilder (DECOMET Laboratory, 2007).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O1ⁱ	0.91	2.03	2.928 (2)	173.0
N2—H22···O2ⁱⁱ	0.92	2.10	2.971 (2)	159.2

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

Acknowledgements

The authors thank Dr Pascal Retailleau from the Service de Cristallochimie of the Institut de Chimie des Substances Naturelles, CNRS, for help with data collection and processing. The authors acknowledge Professor Marc Lecouvey for his advice. This study was supported by the University Paris-Nord and the University of Annaba.

References

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