2-Hydr­oxy-3,3-dimethyl-7-nitro-3,4-dihydro­isoquinolin-1(2H)-one

Ben Salah, H.; Kammoun, M.; Hamdi, B.; Bohé, L.; Damak, M.

doi:10.1107/S1600536808013457

organic compounds

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doi:10.1107/S1600536808013457

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2-Hydroxy-3,3-dimethyl-7-nitro-3,4-dihydroisoquinolin-1(2H)-one

Hassen Ben Salah,^a Majed Kammoun,^a Besma Hamdi,^b Luis Bohé ^c and Mohamed Damak ^a ^*

^aLaboratoire de Chimie des Substances Naturelles, Faculté des Sciences de Sfax, BP 1171, 3000 Sfax, Tunisia, ^bLaboratoire de Sciences de Matériaux et d'Environnement, Faculté des Sciences de Sfax, BP 1171, 3000 Sfax, Tunisia, and ^cICSN–CNRS, 1 avenue de la Terrasse, 91198 Gif sur Yvette, France
^*Correspondence e-mail: mohamed.damak@fss.rnu.tn

(Received 27 March 2008; accepted 6 May 2008; online 10 May 2008)

In the title compound, C₁₁H₁₂N₂O₄, a new hydroxamic acid which belonging to the isoquinole family, the heterocyclic ring adopts a half-chair conformation. The nitro group is essentially coplanar with the aromatic ring. Intermolecular O—H⋯O hydrogen bonds assemble the molecules around inversion centres to form pseudo-dimers.

Related literature

For related literature, see: Bohé & Kammoun (2004 ); Kurzak et al. (1992 ); Porcheddu & Giacomelli (2006 ); Weber (1983 ); Miller (1989 ); Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₁H₁₂N₂O₄
M_r = 236.23
Monoclinic, P 2₁ /n
a = 5.8805 (9) Å
b = 18.605 (4) Å
c = 10.1588 (17) Å
β = 103.056 (12)°
V = 1082.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.60 × 0.51 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (Coppens et al., 1965 ) T_min = 0.938, T_max = 0.975
7659 measured reflections
3286 independent reflections
2051 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.150
S = 1.11
3286 reflections
157 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O12—H12⋯O11ⁱ	0.82	1.99	2.7013 (14)	144
O12—H12⋯O11	0.82	2.20	2.6305 (15)	113
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ), ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808013457/dn2332sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808013457/dn2332Isup2.hkl

checkCIF report

Comment top

Hydroxamic acids are strong metal ion chelators (Kurzak et al., 1992), they posses a wide spectrum of biological activities, such as antibacterial, antifungal, anti-inflammatory, and anti-asthmatic properties, etc. (Weber, 1983; Miller 1989).

The growing number of published synthetic methods further points to the biological significance of hydroxamic acids (Porcheddu & Giacomelli, 2006). Among this family of hydroxamic acids is the title compound (1). We report herein its synthesis and its crystal structure determination. Synthesis of the title compound has been prepared from the corresponding dihydroisoquinoleine (2) by metachloroperbenzoic acid oxidation (Fig. 1). Imine (2) was described by Bohé and Kammoun (2004), in three steps from the commercially available tertiary alcohol (3).

In the title compound, the heterocyclic ring adopts a half-chair conformation as indicated by the puckering parameters: Q = 0.4224 (14)Å, θ = 57.87 (18)°, ϕ = 281.2 (2)° (Cremer & Pople, 1975). The nitro group attached on C7 is essentially coplanar with the aromatic nucleus (Fig. 2). The methyl substituent in position 3 of the heterocyclic ring is pseudo-axial, the second methyl in position 3 is pseudo-equatorial.

The conformation of (1) is stabilized by an intramolecular hydrogen bond between the hydroxyl O12—H12 group and atom O11 (Table 1).The molecules are assembled by intermolecualr O-H···O hydrogen bonds to form pseudo dimer arranged around inversion centre (Table 1, Fig. 3)

Related literature top

For related literature, see: Bohé & Kammoun (2004); Kurzak et al. (1992); Porcheddu & Giacomelli (2006); Weber (1983); Miller (1989); Cremer & Pople (1975).

Experimental top

The title compound was prepared by reaction of imine (2) (100 mg, 0.49 mmol), and methachloroperbenzoique acid 86% (197 mg, 0.98 mmol) in dichloromethane (15 ml). The mixture was stirred at room temperature for 24 h. Then, the mixture was diluted with CH₂Cl₂ and washed with a solution of saturated NaHCO₃. The organic phase was dried over sodium sulfate, filtered and concentrated under reduced pressure. The concentrate was chromatographed on silica gel, with (ether) as eluent (yield 40%). m.p.418 K. Spectroscopic analysis, 1H NMR (300 MHz; DMSO-d₆, p.p.m): 1.26 (s, 6H, 2Me 3); 3.23 (s, 2H); 7.59 (d, J = 8.4, 1H, aromatic H); 8.33 (dd, J = 8.4, J= 2.4, 1H, aromatic H); 8.56 (d, J = 2.4, 1H aromatic H); 9.8 (s wide, 1H, OH). 13 C NMR (75 MHz; DMSO-d₆, p.p.m): 25.24; 41.80; 60.66; 122.02; 126.87; 129.91;130.41; 144.05; 147.21; 160.08. M.S (EI, 70 ev): m/z: 236 (M+.); 221 [(M–15)+., base peak]. MS (HR): Found: 236,0844 calcd mass for C₁₁H₁₂N₂O₄: 236,0875. Recrystallizations from dichloromethane afford yellow crystals suitable for diffraction.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Chemical pathway of the formation of hydroxamic acid.
	Fig. 2. Molecular view of the title compound with the atom-labelling scheme. Ellispsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 3. Partial packing view showing the formation of pseudo dimer through O-H···O hydrogen bonds. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bondings have been omitted for clarity. [Symmetry code: (i) 1-x, 1-y, 1-z]

2-Hydroxy-3,3-dimethyl-7-nitro-3,4-dihydroisoquinolin-1(2H)-one top

Crystal data top

C₁₁H₁₂N₂O₄	F(000) = 496
M_r = 236.23	D_x = 1.449 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 418 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 5.8805 (9) Å	Cell parameters from 2421 reflections
b = 18.605 (4) Å	θ = 2.5–23.2°
c = 10.1588 (17) Å	µ = 0.11 mm⁻¹
β = 103.056 (12)°	T = 296 K
V = 1082.7 (3) Å³	Prism, colourless
Z = 4	0.60 × 0.51 × 0.22 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3286 independent reflections
Radiation source: sealed tube	2051 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 30.4°, θ_min = 2.2°
Absorption correction: multi-scan (Coppens et al., 1965)	h = −8→8
T_min = 0.938, T_max = 0.975	k = 0→26
7659 measured reflections	l = 0→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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.151	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0543P)² + 0.0949P] where P = (F_o² + 2F_c²)/3
3286 reflections	(Δ/σ)_max = 0.001
157 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₁H₁₂N₂O₄	V = 1082.7 (3) Å³
M_r = 236.23	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.8805 (9) Å	µ = 0.11 mm⁻¹
b = 18.605 (4) Å	T = 296 K
c = 10.1588 (17) Å	0.60 × 0.51 × 0.22 mm
β = 103.056 (12)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3286 independent reflections
Absorption correction: multi-scan (Coppens et al., 1965)	2051 reflections with I > 2σ(I)
T_min = 0.938, T_max = 0.975	R_int = 0.021
7659 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.151	H-atom parameters constrained
S = 1.11	Δρ_max = 0.26 e Å⁻³
3286 reflections	Δρ_min = −0.27 e Å⁻³
157 parameters

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. 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	0.7652 (2)	0.53911 (7)	0.36105 (13)	0.0323 (3)
C3	0.7990 (2)	0.67410 (7)	0.36068 (15)	0.0380 (3)
C4	0.8660 (3)	0.66689 (8)	0.22427 (15)	0.0426 (3)
H4A	0.7256	0.6692	0.1527	0.051*
H4B	0.9645	0.7072	0.2127	0.051*
C5	1.1554 (3)	0.59404 (8)	0.13045 (14)	0.0393 (3)
H5	1.1903	0.6347	0.0857	0.047*
C6	1.2662 (3)	0.52948 (8)	0.11699 (14)	0.0410 (3)
H6	1.3779	0.5268	0.0653	0.049*
C7	1.2075 (2)	0.46956 (7)	0.18163 (13)	0.0339 (3)
C8	1.0435 (2)	0.47108 (7)	0.25982 (13)	0.0330 (3)
H8	1.0052	0.4297	0.3015	0.040*
C9	0.9371 (2)	0.53674 (7)	0.27418 (12)	0.0296 (2)
C10	0.9923 (2)	0.59838 (7)	0.21048 (13)	0.0338 (3)
C13	1.0066 (3)	0.68808 (8)	0.47591 (16)	0.0471 (3)
H13A	0.9566	0.6890	0.5596	0.071*
H13B	1.0752	0.7335	0.4625	0.071*
H13C	1.1200	0.6506	0.4789	0.071*
C14	0.6172 (3)	0.73411 (8)	0.35087 (19)	0.0538 (4)
H14A	0.4823	0.7226	0.2813	0.081*
H14B	0.6829	0.7787	0.3294	0.081*
H14C	0.5727	0.7386	0.4358	0.081*
N2	0.6880 (2)	0.60494 (6)	0.38233 (13)	0.0402 (3)
N15	1.3238 (2)	0.40117 (7)	0.16643 (13)	0.0438 (3)
O11	0.69294 (19)	0.48475 (5)	0.40857 (11)	0.0437 (3)
O12	0.5448 (2)	0.61049 (6)	0.47313 (13)	0.0542 (3)
H12	0.5129	0.5702	0.4961	0.081*
O16	1.4723 (3)	0.40057 (7)	0.09958 (16)	0.0701 (4)
O17	1.2691 (3)	0.34788 (6)	0.22078 (16)	0.0724 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0312 (5)	0.0344 (6)	0.0338 (6)	−0.0011 (5)	0.0129 (4)	−0.0013 (5)
C3	0.0393 (7)	0.0316 (6)	0.0463 (8)	0.0024 (5)	0.0163 (5)	0.0012 (5)
C4	0.0514 (8)	0.0382 (7)	0.0403 (7)	0.0039 (6)	0.0146 (6)	0.0078 (5)
C5	0.0468 (8)	0.0409 (7)	0.0340 (7)	−0.0071 (5)	0.0172 (5)	0.0027 (5)
C6	0.0422 (7)	0.0506 (8)	0.0357 (7)	−0.0047 (6)	0.0203 (5)	−0.0025 (6)
C7	0.0331 (6)	0.0385 (7)	0.0323 (6)	−0.0022 (5)	0.0118 (4)	−0.0066 (5)
C8	0.0341 (6)	0.0356 (6)	0.0316 (6)	−0.0023 (4)	0.0125 (4)	−0.0028 (5)
C9	0.0251 (5)	0.0356 (6)	0.0300 (5)	−0.0015 (4)	0.0102 (4)	−0.0009 (4)
C10	0.0369 (6)	0.0378 (7)	0.0283 (6)	−0.0015 (5)	0.0104 (4)	0.0001 (5)
C13	0.0491 (8)	0.0449 (8)	0.0478 (8)	−0.0067 (6)	0.0120 (6)	−0.0062 (6)
C14	0.0549 (10)	0.0395 (8)	0.0710 (11)	0.0094 (7)	0.0224 (8)	0.0025 (7)
N2	0.0398 (6)	0.0384 (6)	0.0484 (7)	0.0012 (5)	0.0225 (5)	−0.0004 (5)
N15	0.0435 (7)	0.0449 (7)	0.0484 (7)	−0.0015 (5)	0.0216 (5)	−0.0107 (5)
O11	0.0474 (6)	0.0392 (5)	0.0530 (6)	−0.0016 (4)	0.0290 (5)	0.0036 (4)
O12	0.0577 (7)	0.0439 (6)	0.0759 (8)	0.0026 (5)	0.0466 (6)	−0.0024 (5)
O16	0.0803 (10)	0.0621 (8)	0.0872 (10)	0.0148 (7)	0.0593 (9)	0.0031 (7)
O17	0.0887 (11)	0.0377 (6)	0.1104 (12)	−0.0020 (6)	0.0633 (10)	−0.0055 (7)

Geometric parameters (Å, º) top

C1—O11	1.2366 (15)	C7—C8	1.3816 (17)
C1—N2	1.3407 (16)	C7—N15	1.4690 (18)
C1—C9	1.4851 (16)	C8—C9	1.3950 (17)
C3—N2	1.4818 (18)	C8—H8	0.9300
C3—C13	1.511 (2)	C9—C10	1.3905 (17)
C3—C4	1.530 (2)	C13—H13A	0.9600
C3—C14	1.533 (2)	C13—H13B	0.9600
C4—C10	1.497 (2)	C13—H13C	0.9600
C4—H4A	0.9700	C14—H14A	0.9600
C4—H4B	0.9700	C14—H14B	0.9600
C5—C6	1.388 (2)	C14—H14C	0.9600
C5—C10	1.3927 (18)	N2—O12	1.3862 (14)
C5—H5	0.9300	N15—O17	1.2130 (17)
C6—C7	1.3768 (19)	N15—O16	1.2215 (16)
C6—H6	0.9300	O12—H12	0.8200

O11—C1—N2	121.69 (11)	C9—C8—H8	121.1
O11—C1—C9	123.22 (11)	C10—C9—C8	121.09 (11)
N2—C1—C9	115.07 (11)	C10—C9—C1	120.91 (11)
N2—C3—C13	109.91 (12)	C8—C9—C1	118.00 (11)
N2—C3—C4	105.70 (11)	C9—C10—C5	119.18 (12)
C13—C3—C4	112.86 (12)	C9—C10—C4	119.07 (12)
N2—C3—C14	108.53 (12)	C5—C10—C4	121.68 (12)
C13—C3—C14	110.76 (13)	C3—C13—H13A	109.5
C4—C3—C14	108.88 (12)	C3—C13—H13B	109.5
C10—C4—C3	113.20 (11)	H13A—C13—H13B	109.5
C10—C4—H4A	108.9	C3—C13—H13C	109.5
C3—C4—H4A	108.9	H13A—C13—H13C	109.5
C10—C4—H4B	108.9	H13B—C13—H13C	109.5
C3—C4—H4B	108.9	C3—C14—H14A	109.5
H4A—C4—H4B	107.8	C3—C14—H14B	109.5
C6—C5—C10	120.56 (12)	H14A—C14—H14B	109.5
C6—C5—H5	119.7	C3—C14—H14C	109.5
C10—C5—H5	119.7	H14A—C14—H14C	109.5
C7—C6—C5	118.67 (12)	H14B—C14—H14C	109.5
C7—C6—H6	120.7	C1—N2—O12	117.02 (11)
C5—C6—H6	120.7	C1—N2—C3	126.35 (11)
C6—C7—C8	122.71 (12)	O12—N2—C3	112.85 (10)
C6—C7—N15	118.59 (11)	O17—N15—O16	122.81 (13)
C8—C7—N15	118.70 (12)	O17—N15—C7	118.86 (12)
C7—C8—C9	117.77 (11)	O16—N15—C7	118.34 (12)
C7—C8—H8	121.1	N2—O12—H12	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12···O11ⁱ	0.82	1.99	2.7013 (14)	144
O12—H12···O11	0.82	2.20	2.6305 (15)	113

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂N₂O₄
M_r	236.23
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	5.8805 (9), 18.605 (4), 10.1588 (17)
β (°)	103.056 (12)
V (Å³)	1082.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.60 × 0.51 × 0.22

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (Coppens et al., 1965)
T_min, T_max	0.938, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	7659, 3286, 2051
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.712

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.151, 1.11
No. of reflections	3286
No. of parameters	157
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.27

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12···O11ⁱ	0.82	1.99	2.7013 (14)	144.1
O12—H12···O11	0.82	2.20	2.6305 (15)	112.5

Symmetry code: (i) −x+1, −y+1, −z+1.

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