3-Phenyl­isoxazolin-5-one: a redetermination

Essaghouani, A.; Boulhaoua, M.; El Ouasif, L.; Sebbar, N.K.; Essassi, E.M.; Mague, J.T.

doi:10.1107/S2414314617000323

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 1| January 2017| x170032

https://doi.org/10.1107/S2414314617000323

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3-Phenylisoxazolin-5-one: a redetermination

Abdelhanine Essaghouani,^a ^* Mohammed Boulhaoua,^a Latifa El Ouasif,^a Nada Kheira Sebbar,^a El Mokhtar Essassi ^a and Joel T. Mague ^b

^aLaboratoire de Chimie Organique Hétérocyclique, URAC 21, Pôle de Compétence Pharmacochimie, Av Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V, Rabat, Morocco, and ^bDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
^*Correspondence e-mail: essaghouani.hanine@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 4 January 2017; accepted 8 January 2017; online 13 January 2017)

The structure of the title molecule, C₉H₇NO₂, has been redetermined to improved precision and the H atoms located [Cannas et al. (1969 ). Acta Cryst. B25, 1050]. The five-membered ring is almost planar (r.m.s. deviation = 0.006 Å) and subtends a dihedral angle of 2.45 (6)° with the benzene ring. In the crystal, molecules form ribbons running parallel to the a-axis direction through a combination of C—H⋯N and C—H⋯O hydrogen bonds. `Stair-step' offset π–π stacking interactions are also observed.

Keywords: crystal structure; isoxazolinone; hydrogen bonds; π–π stacking.

CCDC reference: 1526138

Structure description

Isoxazole derivatives are employed in different areas of pharmaceuticals such as antifungal (Mares, et al., 2002 ), antibacterial (Kwon, et al., 1995 ), and anti-inflammatory agents (Panda, et al., 2009 ).

In an attempt to prepare a different compound (shown in Fig. 1), the title molecule (Fig. 2) was obtained instead. Noting that the original structure determination (Cannas et al., 1969) cited in the Cambridge Crystallographic Database was performed at room temperature with film data (R₁ = 0.108), we felt that a detailed report of the low temperature structure (R₁ = 0.0338) of the title molecule was warranted. The present determination decreases the s.u.s on the bond distances and bond angles to about one fourth to one sixth of those in the original determination as well as unambiguously locating and refining the hydrogen atoms. The molecule is twisted about the C1⋯C4 axis by 2.45 (6)°, which is almost identical to the degree of twist found previously (2.45°).

Figure 1
The intended compound.

Figure 2
The title molecule with 50% probability displacement ellipsoids.

In the crystal, a combination of pairwise C5—H5⋯N1ⁱⁱ [symmetry code: (ii) 1 − x, −y, 1 − z] and single C8—H8⋯O2ⁱⁱⁱ [symmetry code: (iii) −1 + x, y, z] hydrogen bonds (Table 1 and Fig. 3) form ribbons running parallel to the a direction and alternately inclined at 32.7 (1) and −32.7 (1)° to (001). This motif was noted in the earlier report but we find, in addition, that the ribbons are formed into `stair-step' stacks through complementary, offset π–π-stacking interactions between centrosymmetrically related six-membered and five-membered rings [centroid–centroid separation = 3.812 (1) Å, dihedral angle = 2.45 (6)°] (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯N1ⁱ	0.995 (16)	2.602 (16)	3.5525 (17)	160.0 (12)
C5—H5⋯N1ⁱⁱ	0.991 (17)	2.55 (2)	3.438 (2)	149 (1)
C8—H8⋯O2ⁱⁱⁱ	0.972 (18)	2.57 (2)	3.306 (2)	133 (1)
Symmetry codes: (i) x, y+1, z; (ii) -x+1, -y, -z+1; (iii) x-1, y, z.

Figure 3
The packing viewed along the a axis with C—H⋯N and C—H⋯O hydrogen bonds and π–π stacking interactions shown, respectively, as black, purple and orange dotted lines.

Synthesis and crystallization

A mixture of 4-phenyl-1,5-benzodiazepin-2-one (1.18 g, 5.0 mmol) and hydroxylamine hydrochloride (0.86 g, 12.5 mmol) in anhydrous ethanol (40 ml) was stirred at room temperature for 24 h. The solvent was evaporated under reduced pressure. The resulted solid residue was recrystallized from ethanol solution to afford the title compound as orange crystals (yield: 65%).

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₉H₇NO₂
M_r	161.16
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	9.9869 (6), 5.3008 (3), 13.9874 (9)
β (°)	93.106 (2)
V (Å³)	739.39 (8)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.86
Crystal size (mm)	0.19 × 0.12 × 0.06

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.83, 0.95
No. of measured, independent and observed [I > 2σ(I)] reflections	5465, 1433, 1282
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.089, 1.10
No. of reflections	1433
No. of parameters	138
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.14
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1526138

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617000323/hb4110sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617000323/hb4110Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617000323/hb4110Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314617000323/hb4110Isup4.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314617000323/hb4110Isup5.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314617000323/hb4110Isup6.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

3-Phenylisoxazolin-5-one top

Crystal data top

C₉H₇NO₂	F(000) = 336
M_r = 161.16	D_x = 1.448 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54178 Å
a = 9.9869 (6) Å	Cell parameters from 4379 reflections
b = 5.3008 (3) Å	θ = 5.6–72.1°
c = 13.9874 (9) Å	µ = 0.86 mm⁻¹
β = 93.106 (2)°	T = 150 K
V = 739.39 (8) Å³	Plate, orange
Z = 4	0.19 × 0.12 × 0.06 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	1433 independent reflections
Radiation source: INCOATEC IµS micro-focus source	1282 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.029
Detector resolution: 10.4167 pixels mm^-1	θ_max = 72.1°, θ_min = 5.3°
ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −6→5
T_min = 0.83, T_max = 0.95	l = −17→17
5465 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	All H-atom parameters refined
wR(F²) = 0.089	w = 1/[σ²(F_o²) + (0.0441P)² + 0.1913P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
1433 reflections	Δρ_max = 0.26 e Å⁻³
138 parameters	Δρ_min = −0.14 e Å⁻³
0 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0097 (11)

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 > 2sigma(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
O1	0.72988 (8)	0.35740 (17)	0.61102 (6)	0.0291 (3)
O2	0.83139 (9)	0.67872 (19)	0.68908 (7)	0.0345 (3)
N1	0.59421 (10)	0.2725 (2)	0.59036 (8)	0.0276 (3)
C1	0.51416 (12)	0.4307 (2)	0.62725 (8)	0.0219 (3)
C2	0.58547 (12)	0.6434 (2)	0.67731 (9)	0.0254 (3)
H2A	0.5637 (15)	0.811 (3)	0.6485 (11)	0.033 (4)*
H2B	0.5708 (16)	0.650 (3)	0.7461 (12)	0.036 (4)*
C3	0.72877 (12)	0.5762 (2)	0.66339 (9)	0.0260 (3)
C4	0.36809 (12)	0.3949 (2)	0.61691 (8)	0.0223 (3)
C5	0.31305 (13)	0.1913 (2)	0.56468 (9)	0.0270 (3)
H5	0.3730 (16)	0.070 (3)	0.5343 (11)	0.037 (4)*
C6	0.17523 (13)	0.1648 (3)	0.55302 (9)	0.0308 (3)
H6	0.1396 (18)	0.020 (4)	0.5152 (13)	0.050 (5)*
C7	0.09063 (13)	0.3393 (3)	0.59296 (9)	0.0297 (3)
H7	−0.0084 (17)	0.321 (3)	0.5830 (11)	0.035 (4)*
C8	0.14499 (13)	0.5399 (3)	0.64548 (9)	0.0293 (3)
H8	0.0864 (18)	0.661 (3)	0.6743 (12)	0.043 (4)*
C9	0.28324 (12)	0.5680 (2)	0.65752 (9)	0.0258 (3)
H9	0.3184 (16)	0.708 (3)	0.6934 (11)	0.037 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0220 (4)	0.0294 (5)	0.0360 (5)	0.0020 (3)	0.0029 (4)	−0.0048 (4)
O2	0.0227 (5)	0.0418 (6)	0.0390 (5)	−0.0033 (4)	0.0001 (4)	−0.0054 (4)
N1	0.0234 (5)	0.0263 (6)	0.0329 (6)	0.0000 (4)	0.0018 (4)	−0.0038 (4)
C1	0.0237 (6)	0.0192 (6)	0.0228 (5)	0.0013 (4)	0.0010 (4)	0.0023 (5)
C2	0.0218 (6)	0.0232 (6)	0.0311 (6)	0.0008 (5)	0.0001 (5)	−0.0028 (5)
C3	0.0240 (6)	0.0280 (6)	0.0259 (6)	0.0007 (5)	0.0014 (5)	0.0009 (5)
C4	0.0242 (6)	0.0204 (6)	0.0221 (6)	−0.0006 (4)	0.0001 (4)	0.0028 (5)
C5	0.0294 (6)	0.0230 (6)	0.0285 (6)	−0.0005 (5)	0.0004 (5)	−0.0008 (5)
C6	0.0315 (7)	0.0289 (7)	0.0313 (7)	−0.0070 (5)	−0.0036 (5)	−0.0008 (5)
C7	0.0247 (6)	0.0337 (7)	0.0305 (6)	−0.0036 (5)	−0.0014 (5)	0.0060 (5)
C8	0.0248 (6)	0.0306 (7)	0.0328 (7)	0.0023 (5)	0.0033 (5)	0.0018 (6)
C9	0.0252 (6)	0.0238 (6)	0.0284 (6)	0.0003 (5)	0.0011 (5)	−0.0012 (5)

Geometric parameters (Å, º) top

O1—C3	1.3720 (16)	C4—C5	1.3990 (17)
O1—N1	1.4420 (13)	C5—C6	1.3843 (18)
O2—C3	1.1980 (16)	C5—H5	0.991 (17)
N1—C1	1.2857 (16)	C6—C7	1.390 (2)
C1—C4	1.4704 (16)	C6—H6	0.988 (19)
C1—C2	1.4881 (17)	C7—C8	1.386 (2)
C2—C3	1.4977 (16)	C7—H7	0.995 (16)
C2—H2A	0.995 (16)	C8—C9	1.3899 (17)
C2—H2B	0.981 (16)	C8—H8	0.972 (18)
C4—C9	1.3913 (17)	C9—H9	0.952 (17)

C3—O1—N1	109.63 (8)	C5—C4—C1	120.71 (11)
C1—N1—O1	108.30 (10)	C6—C5—C4	119.98 (12)
N1—C1—C4	120.76 (11)	C6—C5—H5	120.2 (9)
N1—C1—C2	113.00 (10)	C4—C5—H5	119.8 (9)
C4—C1—C2	126.23 (10)	C5—C6—C7	120.49 (12)
C1—C2—C3	101.24 (10)	C5—C6—H6	118.0 (11)
C1—C2—H2A	113.4 (9)	C7—C6—H6	121.5 (11)
C3—C2—H2A	110.5 (9)	C8—C7—C6	119.61 (12)
C1—C2—H2B	113.2 (9)	C8—C7—H7	120.3 (9)
C3—C2—H2B	109.3 (9)	C6—C7—H7	120.1 (9)
H2A—C2—H2B	109.0 (13)	C7—C8—C9	120.30 (12)
O2—C3—O1	120.81 (11)	C7—C8—H8	120.1 (10)
O2—C3—C2	131.38 (12)	C9—C8—H8	119.6 (10)
O1—C3—C2	107.81 (10)	C8—C9—C4	120.18 (12)
C9—C4—C5	119.43 (11)	C8—C9—H9	118.9 (9)
C9—C4—C1	119.84 (11)	C4—C9—H9	120.9 (10)

C3—O1—N1—C1	0.43 (13)	N1—C1—C4—C5	−1.60 (17)
O1—N1—C1—C4	179.36 (9)	C2—C1—C4—C5	177.44 (11)
O1—N1—C1—C2	0.20 (14)	C9—C4—C5—C6	0.62 (18)
N1—C1—C2—C3	−0.68 (14)	C1—C4—C5—C6	−177.90 (11)
C4—C1—C2—C3	−179.79 (11)	C4—C5—C6—C7	−0.07 (19)
N1—O1—C3—O2	179.42 (11)	C5—C6—C7—C8	−0.5 (2)
N1—O1—C3—C2	−0.86 (13)	C6—C7—C8—C9	0.56 (19)
C1—C2—C3—O2	−179.41 (14)	C7—C8—C9—C4	−0.01 (19)
C1—C2—C3—O1	0.91 (12)	C5—C4—C9—C8	−0.58 (18)
N1—C1—C4—C9	179.89 (11)	C1—C4—C9—C8	177.95 (11)
C2—C1—C4—C9	−1.07 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···N1ⁱ	0.995 (16)	2.602 (16)	3.5525 (17)	160.0 (12)
C5—H5···N1ⁱⁱ	0.991 (17)	2.55 (2)	3.438 (2)	149 (1)
C8—H8···O2ⁱⁱⁱ	0.972 (18)	2.57 (2)	3.306 (2)	133 (1)

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

Acknowledgements

The support of NSF–MRI Grant No. 1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.

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