2-Hy­droxy-N-(2-hy­droxy­eth­yl)benzamide

Betz, R.; Gerber, T.; Hosten, E.; Schalekamp, H.

doi:10.1107/S1600536811029175

organic compounds

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Volume 67| Part 8| August 2011| Page o2117

doi:10.1107/S1600536811029175

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2-Hydroxy-N-(2-hydroxyethyl)benzamide

Richard Betz,^a ^* Thomas Gerber,^a Eric Hosten ^a and Henk Schalekamp ^a

^aNelson Mandela Metropolitan University, Summerstrand Campus, Department of Chemistry, University Way, Summerstrand, PO Box 77000, Port Elizabeth 6031, South Africa
^*Correspondence e-mail: richard.betz@webmail.co.za

(Received 12 July 2011; accepted 19 July 2011; online 23 July 2011)

In the title compound, C₉H₁₁NO₃, a derivative of salicylamide, the intracyclic C—C—C angles span the range 117.96 (13)–121.56 (14)°. An intramolecular O—H⋯O hydrogen bond occurs. In the crystal, intermolecular O—H⋯O and N—H⋯O hydrogen bonds occur and C—H⋯O contacts connect the molecules into a three-dimensional network. The closest intercentroid distance between two π-systems is 3.8809 (10) Å.

Related literature

For the crystal structure of N-acetylsalicylamide, see: Vyas et al. (1987 ). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ); Bernstein et al. (1995 ). Structures containing similar dihedral angles were retrieved from the Cambridge Structural Database (Allen, 2002 ). For the use of chelating ligands in coordination chemistry, see: Gade (1998 ).

Experimental

Crystal data

C₉H₁₁NO₃
M_r = 181.19
Monoclinic, P 2₁ /c
a = 8.5852 (5) Å
b = 12.1716 (7) Å
c = 9.1113 (4) Å
β = 115.682 (2)°
V = 858.04 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 200 K
0.39 × 0.14 × 0.13 mm

Data collection

Bruker APEXII CCD diffractometer
7333 measured reflections
2063 independent reflections
1561 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.113
S = 1.04
2063 reflections
130 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H82⋯O1	0.90 (2)	1.73 (2)	2.5570 (15)	150 (2)
O3—H83⋯O1ⁱ	0.90 (2)	1.93 (2)	2.8197 (15)	168.3 (19)
N1—H71⋯O3ⁱⁱ	0.874 (18)	2.113 (19)	2.9697 (16)	166.6 (17)
C4—H4⋯O2ⁱⁱⁱ	0.95	2.54	3.4864 (19)	173
C7—H7⋯O3ⁱⁱ	0.95	2.57	3.4496 (19)	155
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x, -y, -z; (iii) -x+1, -y, -z+2.

Data collection: APEX2 (Bruker, 2010 ); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811029175/qm2017sup1.cif

Supporting information file. DOI: 10.1107/S1600536811029175/qm2017Isup2.cdx

Structure factors: contains datablock I. DOI: 10.1107/S1600536811029175/qm2017Isup3.hkl

Supporting information file. DOI: 10.1107/S1600536811029175/qm2017Isup4.cml

checkCIF report

Comment top

Chelate ligands have found widespread use in coordination chemistry due to the enhanced thermodynamic stability of resultant coordination compounds in relation to coordination compounds exclusively applying comparable monodentate ligands (Gade, 1998). Combining different donor atoms, a molecular set-up to accomodate a large variety of metal centers of variable Lewis acidity is at hand. In this aspect, N-(2-hydroxyethyl)-salicylamide seemed of interest due to its possible use as a strictly neutral or, depending on the pH value, as an anionic or cationic ligand. In addition, due to the set-up of its functional groups, it may act as mono-, bi-, tri- or even tetradentate ligand offering the possibility to create chelate rings of various size. The intriguing combination of a secondary amino group, a keto group as well as an aliphatic and an aromatic hydroxyl group classifies the title compound as a highly versatile ligand. To enable comparative studies in terms of bond lengths and angles in envisioned coordination compounds, we determined the molecular and crystal structure of the title compound. Information about the crystal structure of N-acetylsalicylamide (Vyas et al., 1987) is available in the literature.

Due to the possible resonance between the amide group and the aromatic system, a projection of the molecule shows nearly all atoms to reside in the same plane. The only marked exception from this finding is the aliphatic hydroxyl group which adopts a staggered conformation with respect to the plane of the phenyl moiety. Intracyclic C–C–C angles span a range from 117.96 (13)–121.56 (14) °. The least-squares planes defined by the carbon atoms of the aromatic system on the one hand and the CON-motif of the amide group on the other hand intersect at an angle of 11.71 (20) ° (Fig. 1). This finding is in good agreement with values reported for other salicylic acid-derived amides whose crystal structural data have been deposited with the Cambridge Structural Database (Allen, 2002; Fig. 2).

In the crystal structure, intra- as well as intermolecular hydrogen bonds are obvious. The intramolecular hydrogen bond is formed between the hydrogen atom of the hydroxyl group bonded to the aromatic system and the oxygen atom of the keto group, with the latter one also serving as acceptor for one intermolecular hydrogen bond stemming from the aliphatic hydroxyl group. The amino group acts as donor in a hydrogen bond applying the aliphatic hydroxyl group's oxygen atom as acceptor. Apart from these classical hydrogen bonds, C–H···O contacts are observed whose range falls by more than 0.1 below the sum of van-der-Waals radii of the atoms participating. These contacts are manifest between the CH group in ortho position to the hydroxyl group on the aromatic system and the O atom of this hydroxyl group in the neighbouring molecule thus connecting the molecules to centrosymmetric dimers. A second C–H···O contact can be observed between one of the aromatic CH groups and the O atom of the aliphatic hydroxyl group (Fig. 2). In terms of graph-set analysis (Etter et al., 1990; Bernstein et al., 1995), the descriptor for the classical hydrogen bonds is S(6)C¹₁(7)R²₂(10) on the unitary level while a description of the C–H···O contatcs necessitates a C¹₁(8)R²₂(8) descriptor on the same level. In total, the molecules are connected to a three-dimensional network. The closest intercentroid distance between two π-systems was found at 3.8809 (10) Å.

The packing of the title compound is shown in Figure 4.

Related literature top

For the crystal structure of N-acetylsalicylamide, see: Vyas et al. (1987). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990); Bernstein et al. (1995). Structures containing similar dihedral angles were retrieved from the Cambridge Structural Database (Allen, 2002). For the use of chelate ligands in coordination chemistry, see: Gade (1998).

Experimental top

The compound was obtained commercially (Aldrich). Crystals suitable for the X-ray diffraction study were taken directly from the provided compound.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level).
	Fig. 2. Statistical distribution of C_ar–C_ar–C=O dihedral angles in salicylic acid-derived amides (data based on CSD search including all structures up to November 2010).
	Fig. 3. Intermolecular contacts, viewed along [-1 - 1 0] (green dashed lines: C–H···O contacts, yellow dashed lines: intramolecular hydrogen bonds, blue dashed lines: intermolecular hydrogen bonds). Symmetry operators: ⁱ -x + 1, -y, -z + 2; ⁱⁱ x, -y + 1/2, z + 1/2; ⁱⁱⁱ -x, -y, -z.
	Fig. 4. Molecular packing of the title compound, viewed along [0 1 0] (anisotropic displacement ellipsoids drawn at 50% probability level).

2-Hydroxy-N-(2-hydroxyethyl)benzamide top

Crystal data top

C₉H₁₁NO₃	F(000) = 384
M_r = 181.19	D_x = 1.403 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3230 reflections
a = 8.5852 (5) Å	θ = 2.6–28.2°
b = 12.1716 (7) Å	µ = 0.11 mm⁻¹
c = 9.1113 (4) Å	T = 200 K
β = 115.682 (2)°	Rod, colourless
V = 858.04 (8) Å³	0.39 × 0.14 × 0.13 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1561 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.061
Graphite monochromator	θ_max = 28.0°, θ_min = 2.6°
ϕ and ω scans	h = −7→11
7333 measured reflections	k = −15→16
2063 independent reflections	l = −11→11

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0456P)² + 0.2715P] where P = (F_o² + 2F_c²)/3
2063 reflections	(Δ/σ)_max < 0.001
130 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₉H₁₁NO₃	V = 858.04 (8) Å³
M_r = 181.19	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.5852 (5) Å	µ = 0.11 mm⁻¹
b = 12.1716 (7) Å	T = 200 K
c = 9.1113 (4) Å	0.39 × 0.14 × 0.13 mm
β = 115.682 (2)°

Data collection top

Bruker APEXII CCD diffractometer	1561 reflections with I > 2σ(I)
7333 measured reflections	R_int = 0.061
2063 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.26 e Å⁻³
2063 reflections	Δρ_min = −0.21 e Å⁻³
130 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.12173 (15)	0.16491 (9)	0.50668 (12)	0.0345 (3)
O2	0.30777 (16)	0.07953 (10)	0.78461 (13)	0.0385 (3)
H82	0.234 (3)	0.1262 (18)	0.709 (3)	0.059 (6)*
O3	−0.01603 (15)	0.12074 (9)	−0.05944 (13)	0.0320 (3)
H83	0.031 (3)	0.188 (2)	−0.050 (3)	0.064 (7)*
N1	0.05024 (16)	0.06865 (10)	0.27683 (15)	0.0265 (3)
H71	0.055 (2)	0.0087 (15)	0.226 (2)	0.040 (5)*
C1	0.14136 (19)	0.08091 (11)	0.43613 (17)	0.0245 (3)
C2	0.26991 (18)	−0.00403 (11)	0.53026 (17)	0.0240 (3)
C3	0.35056 (19)	0.00197 (12)	0.70163 (17)	0.0272 (3)
C4	0.4777 (2)	−0.07369 (13)	0.79138 (19)	0.0325 (4)
H4	0.5303	−0.0700	0.9069	0.039*
C5	0.5277 (2)	−0.15370 (13)	0.7143 (2)	0.0341 (4)
H5	0.6155	−0.2045	0.7768	0.041*
C6	0.4508 (2)	−0.16085 (12)	0.54536 (19)	0.0317 (4)
H6	0.4856	−0.2162	0.4923	0.038*
C7	0.3235 (2)	−0.08696 (12)	0.45544 (18)	0.0283 (3)
H7	0.2708	−0.0923	0.3400	0.034*
C8	−0.0703 (2)	0.15326 (12)	0.17864 (18)	0.0280 (3)
H8A	−0.0098	0.2248	0.1976	0.034*
H8B	−0.1655	0.1603	0.2118	0.034*
C9	−0.1441 (2)	0.12462 (13)	−0.00029 (18)	0.0310 (3)
H9A	−0.2021	0.0523	−0.0179	0.037*
H9B	−0.2324	0.1799	−0.0633	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0439 (7)	0.0284 (5)	0.0239 (6)	0.0066 (5)	0.0079 (5)	−0.0031 (4)
O2	0.0498 (8)	0.0381 (6)	0.0212 (6)	0.0072 (6)	0.0093 (5)	−0.0028 (5)
O3	0.0442 (7)	0.0261 (5)	0.0238 (5)	−0.0026 (5)	0.0131 (5)	−0.0015 (4)
N1	0.0295 (7)	0.0247 (6)	0.0211 (6)	0.0024 (5)	0.0068 (5)	−0.0005 (5)
C1	0.0269 (8)	0.0251 (7)	0.0214 (7)	−0.0029 (6)	0.0103 (6)	−0.0004 (6)
C2	0.0243 (7)	0.0233 (7)	0.0221 (7)	−0.0043 (6)	0.0078 (6)	−0.0001 (5)
C3	0.0297 (8)	0.0274 (7)	0.0222 (7)	−0.0051 (6)	0.0092 (6)	−0.0009 (6)
C4	0.0325 (9)	0.0352 (8)	0.0224 (7)	−0.0026 (7)	0.0049 (6)	0.0048 (6)
C5	0.0284 (8)	0.0325 (8)	0.0341 (9)	0.0014 (6)	0.0067 (7)	0.0075 (7)
C6	0.0320 (9)	0.0275 (7)	0.0335 (8)	0.0018 (6)	0.0122 (7)	−0.0013 (6)
C7	0.0303 (8)	0.0278 (7)	0.0233 (7)	−0.0021 (6)	0.0082 (6)	−0.0016 (6)
C8	0.0299 (8)	0.0271 (7)	0.0240 (7)	0.0047 (6)	0.0089 (6)	0.0026 (6)
C9	0.0293 (8)	0.0315 (8)	0.0231 (7)	0.0030 (6)	0.0029 (6)	0.0005 (6)

Geometric parameters (Å, º) top

O1—C1	1.2573 (17)	C4—C5	1.374 (2)
O2—C3	1.3559 (18)	C4—H4	0.9500
O2—H82	0.90 (2)	C5—C6	1.390 (2)
O3—C9	1.4193 (19)	C5—H5	0.9500
O3—H83	0.90 (2)	C6—C7	1.378 (2)
N1—C1	1.3255 (18)	C6—H6	0.9500
N1—C8	1.4594 (18)	C7—H7	0.9500
N1—H71	0.874 (18)	C8—C9	1.512 (2)
C1—C2	1.484 (2)	C8—H8A	0.9900
C2—C7	1.402 (2)	C8—H8B	0.9900
C2—C3	1.4092 (19)	C9—H9A	0.9900
C3—C4	1.391 (2)	C9—H9B	0.9900

C3—O2—H82	106.2 (13)	C6—C5—H5	119.8
C9—O3—H83	109.0 (13)	C7—C6—C5	119.45 (14)
C1—N1—C8	121.13 (12)	C7—C6—H6	120.3
C1—N1—H71	122.0 (12)	C5—C6—H6	120.3
C8—N1—H71	116.8 (12)	C6—C7—C2	121.56 (14)
O1—C1—N1	120.34 (13)	C6—C7—H7	119.2
O1—C1—C2	120.13 (13)	C2—C7—H7	119.2
N1—C1—C2	119.51 (12)	N1—C8—C9	110.64 (12)
C7—C2—C3	117.96 (13)	N1—C8—H8A	109.5
C7—C2—C1	122.61 (13)	C9—C8—H8A	109.5
C3—C2—C1	119.30 (12)	N1—C8—H8B	109.5
O2—C3—C4	117.80 (13)	C9—C8—H8B	109.5
O2—C3—C2	122.16 (13)	H8A—C8—H8B	108.1
C4—C3—C2	120.04 (13)	O3—C9—C8	112.70 (13)
C5—C4—C3	120.54 (14)	O3—C9—H9A	109.1
C5—C4—H4	119.7	C8—C9—H9A	109.1
C3—C4—H4	119.7	O3—C9—H9B	109.1
C4—C5—C6	120.44 (14)	C8—C9—H9B	109.1
C4—C5—H5	119.8	H9A—C9—H9B	107.8

C8—N1—C1—O1	2.0 (2)	O2—C3—C4—C5	−179.44 (14)
C8—N1—C1—C2	−176.53 (12)	C2—C3—C4—C5	1.0 (2)
O1—C1—C2—C7	−166.39 (14)	C3—C4—C5—C6	−0.7 (2)
N1—C1—C2—C7	12.2 (2)	C4—C5—C6—C7	0.0 (2)
O1—C1—C2—C3	9.4 (2)	C5—C6—C7—C2	0.3 (2)
N1—C1—C2—C3	−172.01 (13)	C3—C2—C7—C6	0.1 (2)
C7—C2—C3—O2	179.76 (13)	C1—C2—C7—C6	175.95 (13)
C1—C2—C3—O2	3.8 (2)	C1—N1—C8—C9	174.38 (13)
C7—C2—C3—C4	−0.7 (2)	N1—C8—C9—O3	−63.35 (16)
C1—C2—C3—C4	−176.74 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H82···O1	0.90 (2)	1.73 (2)	2.5570 (15)	150 (2)
O3—H83···O1ⁱ	0.90 (2)	1.93 (2)	2.8197 (15)	168.3 (19)
N1—H71···O3ⁱⁱ	0.874 (18)	2.113 (19)	2.9697 (16)	166.6 (17)
C4—H4···O2ⁱⁱⁱ	0.95	2.54	3.4864 (19)	173
C7—H7···O3ⁱⁱ	0.95	2.57	3.4496 (19)	155

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

Experimental details

Crystal data
Chemical formula	C₉H₁₁NO₃
M_r	181.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	8.5852 (5), 12.1716 (7), 9.1113 (4)
β (°)	115.682 (2)
V (Å³)	858.04 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.39 × 0.14 × 0.13

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7333, 2063, 1561
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.113, 1.04
No. of reflections	2063
No. of parameters	130
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.21

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H82···O1	0.90 (2)	1.73 (2)	2.5570 (15)	150 (2)
O3—H83···O1ⁱ	0.90 (2)	1.93 (2)	2.8197 (15)	168.3 (19)
N1—H71···O3ⁱⁱ	0.874 (18)	2.113 (19)	2.9697 (16)	166.6 (17)
C4—H4···O2ⁱⁱⁱ	0.95	2.54	3.4864 (19)	173.3
C7—H7···O3ⁱⁱ	0.95	2.57	3.4496 (19)	154.6

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

Acknowledgements

The authors thank Ms Brogan Neale-Shutte for helpful discussions.

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