N-Hydr­oxy-N-o-tolyl­acetamide

Li, Y.-H.; Liu, R.; Zhang, X.-N.; Zhu, H.-J.

doi:10.1107/S1600536808002468

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o533

doi:10.1107/S1600536808002468

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N-Hydroxy-N-o-tolylacetamide

Yu-Hao Li,^a Rui Liu,^a Xiang-Ning Zhang ^b and Hong-Jun Zhu ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China, and ^bJiangsu Pesticide Research Institute Co. Ltd., Nanjing 210019, People's Republic of China
^*Correspondence e-mail: zhuhj@njut.edu.cn

(Received 19 January 2008; accepted 23 January 2008; online 30 January 2008)

In the molecule of the title compound, C₉H₁₁NO₂, the methyl C atom bonded to the ring and the N atom lie in the benzene ring plane. An intramolecular O—H⋯O hydrogen bond results in the formation of a five-membered planar ring, which is oriented at a dihedral angle of 81.37 (3)° with respect to the benzene ring. In the crystal structure, intermolecular O—H⋯O hydrogen bonds link the molecules stacked along the b axis. There are also π–π interactions between benzene rings with a face-to-face stacking distance of 3.434 Å.

Related literature

For related literature, see: Fu et al. (2000 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₉H₁₁NO₂
M_r = 165.19
Monoclinic, P 2₁ /c
a = 7.7890 (16) Å
b = 7.1570 (14) Å
c = 15.613 (3) Å
β = 96.86 (3)°
V = 864.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 294 (2) K
0.40 × 0.30 × 0.30 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.965, T_max = 0.973
1821 measured reflections
1695 independent reflections
1187 reflections with I > 2σ(I)
R_int = 0.054
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.182
S = 1.05
1695 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O2	0.82	2.19	2.608 (3)	112
O1—H1A⋯O2ⁱ	0.82	1.97	2.719 (3)	152
Symmetry code: (i) -x+2, -y, -z.

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808002468/hk2420sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808002468/hk2420Isup2.hkl

checkCIF report

Comment top

The title compound, (I), contains hydroxy and formyl groups, which can react with different groups to prepare various function organic compounds. It is a kind of aromatic organic intermediate that can be used for many fields such as pesticide, paper making etc. (Fu et al., 2000). We report herein its crystal structure.

In the molecule of (I), (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. The atoms N and C1 lie in the benzene ring plane. The intramolecular O—H···O hydrogen bond (Table 1) results in the formation of a five-membered planar ring A (O1/H1A/O2/N/C8). The dihedral angle between five- and six-membered rings is 81.37 (3)°.

In the crystal structure, intermolecular O—H···O hydrogen bonds (Table 1) link the molecules stacked along the b axis (Fig. 2), in which they may be effective in the stabilization of the structure.

There are also the π-π interactions of benzene rings with a face-to-face stacking distance of 3.434 Å.

Related literature top

For related literature, see: Fu et al. (2000). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I), was prepared by the literature method (Fu et al., 2000). Crystals suitable for X-ray analysis were obtained by dissolving (I) (0.5 g) in petroleum ether (20 ml) and evaporating the solvent slowly at room temperature for about 7 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (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 packing diagram of (I). Hydrogen bonds are shown as dashed lines.

N-Hydroxy-N-o-tolylacetamide top

Crystal data top

C₉H₁₁NO₂	F(000) = 352
M_r = 165.19	D_x = 1.270 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 350 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.7890 (16) Å	Cell parameters from 25 reflections
b = 7.1570 (14) Å	θ = 10–13°
c = 15.613 (3) Å	µ = 0.09 mm⁻¹
β = 96.86 (3)°	T = 294 K
V = 864.1 (3) Å³	Block, colorless
Z = 4	0.40 × 0.30 × 0.30 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1187 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.054
Graphite monochromator	θ_max = 26.0°, θ_min = 2.6°
ω/2θ scans	h = −9→9
Absorption correction: ψ scan (North et al., 1968)	k = 0→8
T_min = 0.965, T_max = 0.973	l = 0→19
1821 measured reflections	3 standard reflections every 120 min
1695 independent reflections	intensity decay: none

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.182	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.05P)² + 1.5P] where P = (F_o² + 2F_c²)/3
1695 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₉H₁₁NO₂	V = 864.1 (3) Å³
M_r = 165.19	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.7890 (16) Å	µ = 0.09 mm⁻¹
b = 7.1570 (14) Å	T = 294 K
c = 15.613 (3) Å	0.40 × 0.30 × 0.30 mm
β = 96.86 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1187 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.054
T_min = 0.965, T_max = 0.973	3 standard reflections every 120 min
1821 measured reflections	intensity decay: none
1695 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	0 restraints
wR(F²) = 0.182	H-atom parameters constrained
S = 1.05	Δρ_max = 0.31 e Å⁻³
1695 reflections	Δρ_min = −0.36 e Å⁻³
109 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
N	0.7518 (4)	0.1297 (4)	0.08788 (17)	0.0451 (7)
O1	0.8117 (3)	−0.0536 (3)	0.08895 (15)	0.0554 (7)
H1A	0.8888	−0.0624	0.0577	0.083*
O2	0.9365 (3)	0.2046 (3)	−0.00399 (16)	0.0573 (7)
C1	0.8476 (4)	0.1834 (6)	0.2703 (2)	0.0593 (10)
H1B	0.8527	0.2003	0.3316	0.089*
H1C	0.9065	0.2848	0.2461	0.089*
H1D	0.9022	0.0675	0.2585	0.089*
C2	0.6626 (4)	0.1799 (4)	0.23108 (19)	0.0406 (7)
C3	0.5278 (5)	0.2025 (5)	0.2806 (2)	0.0508 (9)
H3A	0.5533	0.2200	0.3398	0.061*
C4	0.3579 (5)	0.1999 (5)	0.2453 (2)	0.0536 (9)
H4A	0.2706	0.2150	0.2805	0.064*
C5	0.3164 (4)	0.1750 (5)	0.1577 (2)	0.0572 (9)
H5A	0.2013	0.1721	0.1337	0.069*
C6	0.4465 (4)	0.1545 (5)	0.1062 (2)	0.0454 (8)
H6A	0.4194	0.1392	0.0470	0.054*
C7	0.6189 (4)	0.1567 (4)	0.14250 (18)	0.0370 (7)
C8	0.8214 (4)	0.2543 (5)	0.03929 (18)	0.0411 (7)
C9	0.7578 (5)	0.4524 (5)	0.0400 (3)	0.0586 (10)
H9A	0.8186	0.5270	0.0023	0.088*
H9B	0.7779	0.5013	0.0975	0.088*
H9C	0.6362	0.4555	0.0205	0.088*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N	0.0584 (17)	0.0377 (14)	0.0420 (14)	0.0072 (12)	0.0179 (12)	0.0028 (12)
O1	0.0735 (16)	0.0420 (13)	0.0570 (15)	0.0174 (11)	0.0338 (12)	0.0085 (11)
O2	0.0654 (15)	0.0530 (15)	0.0599 (15)	0.0118 (12)	0.0343 (13)	0.0102 (12)
C1	0.054 (2)	0.066 (2)	0.057 (2)	−0.0089 (18)	0.0002 (16)	−0.0039 (18)
C2	0.0504 (18)	0.0360 (16)	0.0352 (16)	0.0026 (14)	0.0045 (13)	−0.0034 (12)
C3	0.073 (2)	0.0481 (19)	0.0339 (16)	0.0030 (17)	0.0155 (15)	−0.0029 (14)
C4	0.057 (2)	0.050 (2)	0.059 (2)	0.0045 (16)	0.0285 (17)	0.0015 (17)
C5	0.0411 (18)	0.064 (2)	0.066 (2)	0.0057 (17)	0.0044 (16)	−0.0010 (19)
C6	0.0486 (18)	0.0471 (19)	0.0401 (17)	0.0052 (15)	0.0043 (14)	0.0001 (14)
C7	0.0423 (16)	0.0363 (16)	0.0349 (15)	0.0036 (13)	0.0150 (12)	0.0012 (12)
C8	0.0440 (16)	0.0482 (18)	0.0318 (15)	0.0009 (14)	0.0076 (12)	0.0017 (13)
C9	0.069 (2)	0.044 (2)	0.066 (2)	0.0046 (17)	0.0243 (19)	0.0052 (17)

Geometric parameters (Å, º) top

N—C8	1.328 (4)	C3—H3A	0.9300
N—O1	1.392 (3)	C4—C5	1.378 (5)
N—C7	1.431 (4)	C4—H4A	0.9300
O1—H1A	0.8200	C5—C6	1.375 (5)
C1—C2	1.497 (5)	C5—H5A	0.9300
C1—H1B	0.9600	C6—C7	1.394 (4)
C1—H1C	0.9600	C6—H6A	0.9300
C1—H1D	0.9600	C8—C9	1.502 (5)
O2—C8	1.238 (3)	C9—H9A	0.9600
C2—C3	1.386 (4)	C9—H9B	0.9600
C2—C7	1.394 (4)	C9—H9C	0.9600
C3—C4	1.371 (5)

C8—N—O1	118.8 (2)	C6—C5—C4	119.5 (3)
C8—N—C7	128.6 (3)	C6—C5—H5A	120.3
O1—N—C7	112.7 (2)	C4—C5—H5A	120.3
N—O1—H1A	109.5	C5—C6—C7	120.2 (3)
C2—C1—H1B	109.5	C5—C6—H6A	119.9
C2—C1—H1C	109.5	C7—C6—H6A	119.9
H1B—C1—H1C	109.5	C6—C7—C2	120.9 (3)
C2—C1—H1D	109.5	C6—C7—N	119.1 (3)
H1B—C1—H1D	109.5	C2—C7—N	119.9 (3)
H1C—C1—H1D	109.5	O2—C8—N	119.4 (3)
C3—C2—C7	117.1 (3)	O2—C8—C9	122.4 (3)
C3—C2—C1	121.7 (3)	N—C8—C9	118.2 (3)
C7—C2—C1	121.1 (3)	C8—C9—H9A	109.5
C4—C3—C2	122.2 (3)	C8—C9—H9B	109.5
C4—C3—H3A	118.9	H9A—C9—H9B	109.5
C2—C3—H3A	118.9	C8—C9—H9C	109.5
C3—C4—C5	120.1 (3)	H9A—C9—H9C	109.5
C3—C4—H4A	119.9	H9B—C9—H9C	109.5
C5—C4—H4A	119.9

C7—C2—C3—C4	0.9 (5)	C1—C2—C7—N	2.0 (4)
C1—C2—C3—C4	179.9 (3)	C8—N—C7—C6	82.5 (4)
C2—C3—C4—C5	−0.3 (5)	O1—N—C7—C6	−98.0 (3)
C3—C4—C5—C6	−0.6 (6)	C8—N—C7—C2	−99.2 (4)
C4—C5—C6—C7	0.8 (5)	O1—N—C7—C2	80.4 (3)
C5—C6—C7—C2	−0.1 (5)	O1—N—C8—O2	0.4 (5)
C5—C6—C7—N	178.2 (3)	C7—N—C8—O2	179.9 (3)
C3—C2—C7—C6	−0.7 (4)	O1—N—C8—C9	−178.9 (3)
C1—C2—C7—C6	−179.7 (3)	C7—N—C8—C9	0.6 (5)
C3—C2—C7—N	−179.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2	0.82	2.19	2.608 (3)	112
O1—H1A···O2ⁱ	0.82	1.97	2.719 (3)	152

Symmetry code: (i) −x+2, −y, −z.

Experimental details

Crystal data
Chemical formula	C₉H₁₁NO₂
M_r	165.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	7.7890 (16), 7.1570 (14), 15.613 (3)
β (°)	96.86 (3)
V (Å³)	864.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.40 × 0.30 × 0.30

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.965, 0.973
No. of measured, independent and observed [I > 2σ(I)] reflections	1821, 1695, 1187
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.182, 1.05
No. of reflections	1695
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.36

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2	0.82	2.19	2.608 (3)	112.00
O1—H1A···O2ⁱ	0.82	1.97	2.719 (3)	152.00

Symmetry code: (i) −x+2, −y, −z.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

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