(E)-1-(4-Amino­phen­yl)ethanone oxime

Rafiq, M.; Hanif, M.; Qadeer, G.; Vuoti, S.; Autio, J.

doi:10.1107/S1600536808034120

organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2173

doi:10.1107/S1600536808034120

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(E)-1-(4-Aminophenyl)ethanone oxime

Muhammad Rafiq,^a Muhammad Hanif,^b Ghulam Qadeer,^b Sauli Vuoti ^c and Juho Autio ^c ^*

^aDepartment of Chemistry, BZU, Multan, Pakistan, ^bDepartment of Chemistry, Quaid-i-Azam Univeristy, Islamabad 45320, Pakistan, and ^cDepartment of Chemistry, University of Oulu, PO Box 3000, 90014 Finland
^*Correspondence e-mail: qadeerqau@yahoo.com

(Received 13 October 2008; accepted 18 October 2008; online 22 October 2008)

In the molecule of the title compound, C₈H₁₀N₂O, the oxime group is oriented at a dihedral angle of 5.58 (3)° with respect to the benzene ring. In the crystal structure, intermolecular O—H⋯N and N—H⋯O hydrogen bonds link the molecules, forming a three-dimensional network.

Related literature

For general background, see: Bertolasi et al. (1982 ); Degorre et al. (1998 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₁₀N₂O
M_r = 150.18
Monoclinic, P 2₁ /n
a = 4.8641 (2) Å
b = 9.2016 (3) Å
c = 17.1447 (7) Å
β = 95.535 (2)°
V = 763.78 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 (2) K
0.34 × 0.28 × 0.26 mm

Data collection

Enraf–Nonius KappaCCD diffractometer
Absorption correction: multi-scan (DENZO; Otwinowski & Minor, 1997 ) T_min = 0.972, T_max = 0.979
6132 measured reflections
1761 independent reflections
1483 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.107
S = 1.04
1761 reflections
113 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯N2ⁱ	0.92 (2)	1.88 (2)	2.7919 (14)	169.8 (18)
N2—H2N⋯O1ⁱⁱ	0.916 (18)	2.165 (18)	3.0790 (13)	175.7 (15)
N2—H2M⋯N1ⁱⁱⁱ	0.929 (19)	2.525 (19)	3.3000 (14)	141.0 (14)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: DIAMOND (Brandenburg, 2007 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808034120/hk2552sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808034120/hk2552Isup2.hkl

checkCIF report

Comment top

One of the richest sources of diversity for the medicinal chemist is small heterocyclic rings, which in addition to often exhibiting biological activity, may serve as rigid scaffolds for a further display of functionalities. Oximes are among those, that have been reported to posses a wide range of biological activities including anti-oxidants, anti-inflammatory and as reactivators of organophosphate inhibited acetylcholine esterases (Degorre et al., 1998). The oxime moiety can both donate and accept hydrogen bonds, which makes it a very interesting building block in supramolecular chemistry (Bertolasi et al., 1982). It is also a key intermediate, which undergoes the 1,3-dipolar cycloaddition reaction with mono substituted alkenes to form isoxazolines.Due to importance of these compounds, we decided to synthesize the title compound and report herein its crystal structure.

In the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges . The phenyl ring A (C1-C6) is oriented with respect to the planar (O1/N1/C1/C7/C8) moiety at a dihedral angle of 5.46 (3)°. N2 atom is -0.014 (3) Å away from the phenyl plane.

In the crystal structure, intermolecular O-H···N and N-H···O hydrogen bonds (Table 1) link the molecules to form a supramolecular structure (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For general background, see: Bertolasi et al. (1982); Degorre et al. (1998). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, a solution of 1-(4-aminophenyl)- ethanone (1.35 g, 10 mmol) in methanol (15 ml) was added to a mixture of hydroxylamine sulfate (1.31 g, 10 mmol) and sodium acetate (2.0 g, 25 mmol). The reaction mass was refluxed for 4-5 h, until the reaction completed. The solvent was evaporated under vacuo and demineralized water (40 ml) was added, cooled to 268-265 K and filtered to obtain crystalline solid (yield; 1.11 g, 75%; m.p. 401-402 K).

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2007) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A partial packing diagram. Hydrogen bonds are shown as dashed lines.

(E)-1-(4-Aminophenyl)ethanone oxime top

Crystal data top

C₈H₁₀N₂O	F(000) = 320
M_r = 150.18	D_x = 1.306 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 401(1) K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 4.8641 (2) Å	Cell parameters from 3781 reflections
b = 9.2016 (3) Å	θ = 1.0–30.0°
c = 17.1447 (7) Å	µ = 0.09 mm⁻¹
β = 95.535 (2)°	T = 100 K
V = 763.78 (5) Å³	Block, pale yellow
Z = 4	0.34 × 0.28 × 0.26 mm

Data collection top

Enraf–Nonius KappaCCD diffractometer	1761 independent reflections
Radiation source: fine-focus sealed tube	1483 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	R_int = 0.026
Detector resolution: 9 pixels mm^-1	θ_max = 27.5°, θ_min = 4.2°
ϕ and ω scans	h = −6→6
Absorption correction: multi-scan (DENZO; Otwinowski & Minor, 1997)	k = −11→11
T_min = 0.972, T_max = 0.979	l = −22→22
6132 measured reflections

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)] = 0.040	Hydrogen site location: mixed
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0554P)² + 0.2855P] where P = (F_o² + 2F_c²)/3
1761 reflections	(Δ/σ)_max < 0.001
113 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₈H₁₀N₂O	V = 763.78 (5) Å³
M_r = 150.18	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.8641 (2) Å	µ = 0.09 mm⁻¹
b = 9.2016 (3) Å	T = 100 K
c = 17.1447 (7) Å	0.34 × 0.28 × 0.26 mm
β = 95.535 (2)°

Data collection top

Enraf–Nonius KappaCCD diffractometer	1761 independent reflections
Absorption correction: multi-scan (DENZO; Otwinowski & Minor, 1997)	1483 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.979	R_int = 0.026
6132 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.24 e Å⁻³
1761 reflections	Δρ_min = −0.28 e Å⁻³
113 parameters

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
O1	0.42570 (18)	0.21270 (10)	0.47528 (5)	0.0203 (2)
H1O	0.273 (4)	0.158 (2)	0.4589 (11)	0.049 (5)*
N1	0.38949 (19)	0.23108 (10)	0.55574 (5)	0.0168 (2)
N2	0.4407 (2)	0.42572 (11)	0.91465 (6)	0.0186 (2)
H2N	0.288 (4)	0.3807 (18)	0.9308 (10)	0.035 (4)*
H2M	0.440 (4)	0.525 (2)	0.9257 (10)	0.039 (4)*
C1	0.5281 (2)	0.34967 (12)	0.67458 (6)	0.0147 (2)
C2	0.3462 (2)	0.26638 (12)	0.71490 (7)	0.0179 (3)
H2	0.2421	0.1914	0.6878	0.021*
C3	0.3148 (2)	0.29074 (13)	0.79324 (7)	0.0177 (3)
H3	0.1903	0.2327	0.8192	0.021*
C4	0.4655 (2)	0.40050 (12)	0.83408 (6)	0.0156 (2)
C5	0.6512 (2)	0.48187 (13)	0.79535 (7)	0.0187 (3)
H5	0.7588	0.5550	0.8230	0.022*
C6	0.6810 (2)	0.45726 (13)	0.71660 (7)	0.0178 (3)
H6	0.8075	0.5146	0.6910	0.021*
C7	0.5571 (2)	0.32441 (12)	0.59009 (6)	0.0149 (2)
C8	0.7713 (2)	0.40782 (13)	0.55104 (7)	0.0195 (3)
H8A	0.7606	0.3815	0.4954	0.029*
H8B	0.9553	0.3841	0.5762	0.029*
H8C	0.7377	0.5123	0.5560	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0222 (5)	0.0272 (5)	0.0121 (4)	−0.0020 (4)	0.0043 (3)	−0.0033 (3)
N1	0.0190 (5)	0.0200 (5)	0.0118 (5)	0.0020 (4)	0.0038 (4)	−0.0010 (4)
N2	0.0230 (5)	0.0190 (5)	0.0141 (5)	0.0005 (4)	0.0032 (4)	−0.0012 (4)
C1	0.0144 (5)	0.0144 (5)	0.0156 (5)	0.0029 (4)	0.0024 (4)	0.0005 (4)
C2	0.0191 (6)	0.0168 (5)	0.0178 (5)	−0.0026 (4)	0.0018 (4)	−0.0015 (4)
C3	0.0172 (5)	0.0182 (6)	0.0181 (6)	−0.0017 (4)	0.0042 (4)	0.0018 (4)
C4	0.0168 (5)	0.0160 (5)	0.0138 (5)	0.0042 (4)	0.0012 (4)	0.0003 (4)
C5	0.0200 (6)	0.0173 (6)	0.0187 (6)	−0.0025 (4)	0.0017 (4)	−0.0036 (4)
C6	0.0179 (5)	0.0176 (5)	0.0185 (6)	−0.0017 (4)	0.0041 (4)	0.0006 (4)
C7	0.0139 (5)	0.0158 (5)	0.0153 (5)	0.0039 (4)	0.0027 (4)	0.0019 (4)
C8	0.0177 (5)	0.0231 (6)	0.0182 (5)	−0.0019 (4)	0.0045 (4)	0.0010 (4)

Geometric parameters (Å, º) top

O1—N1	1.4175 (11)	C3—C4	1.3961 (16)
O1—H1O	0.92 (2)	C3—H3	0.9500
N1—C7	1.2869 (15)	C4—C5	1.3905 (16)
N2—C4	1.4173 (14)	C5—C6	1.3903 (15)
N2—H2N	0.916 (18)	C5—H5	0.9500
N2—H2M	0.929 (19)	C6—H6	0.9500
C1—C6	1.3961 (16)	C7—C8	1.5026 (15)
C1—C2	1.4020 (16)	C8—H8A	0.9800
C1—C7	1.4872 (14)	C8—H8B	0.9800
C2—C3	1.3846 (15)	C8—H8C	0.9800
C2—H2	0.9500

N1—O1—H1O	100.9 (11)	C3—C4—N2	121.15 (10)
C7—N1—O1	113.10 (9)	C6—C5—C4	120.63 (10)
C4—N2—H2N	111.6 (10)	C6—C5—H5	119.7
C4—N2—H2M	111.1 (11)	C4—C5—H5	119.7
H2N—N2—H2M	111.2 (15)	C5—C6—C1	121.09 (10)
C6—C1—C2	117.60 (10)	C5—C6—H6	119.5
C6—C1—C7	121.17 (10)	C1—C6—H6	119.5
C2—C1—C7	121.23 (10)	N1—C7—C1	115.76 (9)
C3—C2—C1	121.59 (11)	N1—C7—C8	124.95 (10)
C3—C2—H2	119.2	C1—C7—C8	119.29 (10)
C1—C2—H2	119.2	C7—C8—H8A	109.5
C2—C3—C4	120.12 (10)	C7—C8—H8B	109.5
C2—C3—H3	119.9	H8A—C8—H8B	109.5
C4—C3—H3	119.9	C7—C8—H8C	109.5
C5—C4—C3	118.94 (10)	H8A—C8—H8C	109.5
C5—C4—N2	119.85 (10)	H8B—C8—H8C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N2ⁱ	0.92 (2)	1.88 (2)	2.7919 (14)	169.8 (18)
N2—H2N···O1ⁱⁱ	0.916 (18)	2.165 (18)	3.0790 (13)	175.7 (15)
N2—H2M···N1ⁱⁱⁱ	0.929 (19)	2.525 (19)	3.3000 (14)	141.0 (14)

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

Experimental details

Crystal data
Chemical formula	C₈H₁₀N₂O
M_r	150.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	4.8641 (2), 9.2016 (3), 17.1447 (7)
β (°)	95.535 (2)
V (Å³)	763.78 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.34 × 0.28 × 0.26

Data collection
Diffractometer	Enraf–Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (DENZO; Otwinowski & Minor, 1997)
T_min, T_max	0.972, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	6132, 1761, 1483
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.108, 1.04
No. of reflections	1761
No. of parameters	113
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.28

Computer programs: , DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2007) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N2ⁱ	0.92 (2)	1.88 (2)	2.7919 (14)	169.8 (18)
N2—H2N···O1ⁱⁱ	0.916 (18)	2.165 (18)	3.0790 (13)	175.7 (15)
N2—H2M···N1ⁱⁱⁱ	0.929 (19)	2.525 (19)	3.3000 (14)	141.0 (14)

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

Acknowledgements

The authors gratefully acknowledge funds from the Higher Education Commission, Islamabad, Pakistan.

References

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