Methyl 2,4-dihy­droxy-5-(2-methyl­propanamido)­benzoate

Naz, S.S.; Islam, N.U.; Tahir, M.N.; Shah, M.R.

doi:10.1107/S1600536813000457

organic compounds

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ISSN: 2056-9890

Volume 69| Part 2| February 2013| Page o221

doi:10.1107/S1600536813000457

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Methyl 2,4-dihydroxy-5-(2-methylpropanamido)benzoate

Syeda Sohaila Naz,^a Nazar Ul Islam,^a M. Nawaz Tahir ^b ^* and Muhammad Raza Shah ^c

^aUniversity of Peshawar, Institute of Chemical Sciences, Peshawar, Pakistan, ^bUniversity of Sargodha, Department of Physics, Sargodha, Pakistan, and ^cH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 5 January 2013; accepted 5 January 2013; online 12 January 2013)

In the title compound, C₁₂H₁₅NO₅, the dihedral angle between the benzene ring and the C atoms of the terminal isopropyl group is 83.48 (16)°. Intramolecular N—H⋯O and O—H⋯O hydrogen bonds generate S(5) and S(6) rings, respectively. In the crystal, molecules are linked by O—H⋯O hydrogen bonds, generating C(7) chains propagating in [001]. Weak aromatic π–π stacking [centroid–centroid separation = 3.604 (3) Å] is also observed.

Related literature

For related structures, see: Chen et al. (2011 ); Naz et al. (2013 ).

Experimental

Crystal data

C₁₂H₁₅NO₅
M_r = 253.25
Monoclinic, C 2/c
a = 22.732 (4) Å
b = 8.2338 (16) Å
c = 14.743 (3) Å
β = 113.506 (9)°
V = 2530.4 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.26 × 0.16 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.981, T_max = 0.985
8480 measured reflections
2218 independent reflections
950 reflections with I > 2σ(I)
R_int = 0.090

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.168
S = 0.96
2218 reflections
169 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4	0.86	2.19	2.604 (4)	109
O3—H3⋯O2	0.82	1.87	2.595 (4)	146
O4—H4⋯O5ⁱ	0.82	1.820	2.633 (4)	174
Symmetry code: (i) $[x, -y+2, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); 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, 2012 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813000457/hb7024sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813000457/hb7024Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813000457/hb7024Isup3.cml

checkCIF report

Comment top

The title compound (I, Fig. 1) has been prepared for derivatization and for the biological studies in continuation to form different derivatives of methyl 5-amino-2,4-dihydroxybenzoate (Naz et al., 2013). The crystal structure of 3-hydroxy-2-(isobutyrylamino)benzamide (Chen et al., 2011) has been published which is related to the title compound.

In (I), the groups A (C1—C8/O1—O4/N1) of methyl 5-amino-2,4-dihydroxybenzoate is almost planar with r. m. s. deviation of 0.0190 Å. The C9 and O5 atoms are at a distance of -0.1205 (50) and -0.3867 (44) Å from the mean square plane of the group A. The isopropyl group B (C10—C12) is of course planar. The dihedral angle between A/B is 83.24 (15)°. There exist strong intramolecular H-bondings of N—H···O and O—H···O types (Table 1, Fig. 2) completing S(5) and S(6) ring motifs. There also exist strong intermolecular H-bondings of O—H···O type due to which C(7) chains are formed (Table 1, Fig. 2) resulting in the formation of one dimensional polymeric network along the c-axis. There also exist π–π interactions between the centroids of benzene rings at a distance of 3.604 (3) Å.

Related literature top

For related structures, see: Chen et al. (2011); Naz et al. (2013).

Experimental top

Equivalent amounts of methyl 5-amino-2,4-dihydroxybenzoate (0.2 g, 1.1 mmol) and Isobutyric anhydride (0.2 ml, 1.1 mmol) were heated at 333 K for 3 h in dimethylformamide (DMF). The reaction mixture was kept for 48 h to afford brown needles of the title compound.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The partial packing of (I), which shows that molecules form S(5) & S(6) loops and one dimensional polymeric chains are formed due to O—H···O H-bonds along the [001] direction.

Methyl 2,4-dihydroxy-5-(2-methylpropanamido)benzoate top

Crystal data top

C₁₂H₁₅NO₅	F(000) = 1072
M_r = 253.25	D_x = 1.330 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 950 reflections
a = 22.732 (4) Å	θ = 2.0–25.0°
b = 8.2338 (16) Å	µ = 0.10 mm⁻¹
c = 14.743 (3) Å	T = 296 K
β = 113.506 (9)°	Needle, brown
V = 2530.4 (9) Å³	0.26 × 0.16 × 0.14 mm
Z = 8

Data collection top

Bruker Kappa APEXII CCD diffractometer	2218 independent reflections
Radiation source: fine-focus sealed tube	950 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.090
Detector resolution: 8.10 pixels mm^-1	θ_max = 25.0°, θ_min = 2.0°
ω scans	h = −26→26
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −9→9
T_min = 0.981, T_max = 0.985	l = −12→17
8480 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.065	H-atom parameters constrained
wR(F²) = 0.168	w = 1/[σ²(F_o²) + (0.067P)²] where P = (F_o² + 2F_c²)/3
S = 0.96	(Δ/σ)_max < 0.001
2218 reflections	Δρ_max = 0.25 e Å⁻³
169 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0032 (7)

Crystal data top

C₁₂H₁₅NO₅	V = 2530.4 (9) Å³
M_r = 253.25	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 22.732 (4) Å	µ = 0.10 mm⁻¹
b = 8.2338 (16) Å	T = 296 K
c = 14.743 (3) Å	0.26 × 0.16 × 0.14 mm
β = 113.506 (9)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2218 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	950 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.985	R_int = 0.090
8480 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.168	H-atom parameters constrained
S = 0.96	Δρ_max = 0.25 e Å⁻³
2218 reflections	Δρ_min = −0.19 e Å⁻³
169 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	−0.03069 (13)	0.6890 (3)	0.1237 (2)	0.0561 (11)
O2	−0.07828 (14)	0.6152 (4)	−0.0343 (2)	0.0674 (14)
O3	−0.02971 (14)	0.7095 (4)	−0.1577 (2)	0.0664 (13)
O4	0.15588 (13)	1.0422 (4)	−0.02943 (18)	0.0528 (10)
O5	0.15037 (13)	0.9581 (4)	0.28873 (18)	0.0574 (11)
N1	0.15743 (14)	1.0418 (4)	0.1481 (2)	0.0418 (11)
C1	−0.0795 (2)	0.6008 (6)	0.1437 (3)	0.0673 (19)
C2	−0.0344 (2)	0.6874 (5)	0.0313 (3)	0.0473 (17)
C3	0.01556 (18)	0.7776 (5)	0.0160 (3)	0.0393 (16)
C4	0.01545 (19)	0.7844 (5)	−0.0792 (3)	0.0427 (17)
C5	0.06228 (18)	0.8703 (5)	−0.0956 (3)	0.0461 (16)
C6	0.10844 (18)	0.9523 (5)	−0.0193 (3)	0.0394 (14)
C7	0.10893 (18)	0.9489 (5)	0.0764 (3)	0.0347 (14)
C8	0.06285 (18)	0.8611 (5)	0.0931 (3)	0.0401 (16)
C9	0.17569 (18)	1.0465 (5)	0.2465 (3)	0.0405 (16)
C10	0.22833 (19)	1.1646 (5)	0.3026 (3)	0.0488 (16)
C11	0.2012 (2)	1.3027 (6)	0.3419 (3)	0.071 (2)
C12	0.2825 (2)	1.0777 (6)	0.3844 (3)	0.081 (2)
H1	0.17846	1.10489	0.12524	0.0500*
H1A	−0.08075	0.49015	0.12248	0.1011*
H1B	−0.12055	0.65059	0.10854	0.1011*
H1C	−0.06954	0.60325	0.21343	0.1011*
H3	−0.05505	0.66231	−0.13988	0.0994*
H4	0.15318	1.03493	−0.08643	0.0791*
H5	0.06261	0.87259	−0.15848	0.0552*
H8	0.06317	0.85732	0.15633	0.0484*
H10	0.24534	1.20993	0.25653	0.0581*
H11A	0.16985	1.36048	0.28749	0.1067*
H11B	0.23520	1.37530	0.37963	0.1067*
H11C	0.18139	1.25979	0.38335	0.1067*
H12A	0.30085	0.99782	0.35606	0.1215*
H12B	0.26605	1.02529	0.42766	0.1215*
H12C	0.31477	1.15496	0.42134	0.1215*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.064 (2)	0.065 (2)	0.0401 (19)	−0.0134 (17)	0.0215 (15)	0.0018 (17)
O2	0.059 (2)	0.084 (3)	0.050 (2)	−0.0224 (18)	0.0122 (16)	−0.0199 (18)
O3	0.057 (2)	0.100 (3)	0.0340 (18)	−0.0108 (19)	0.0094 (15)	−0.0240 (19)
O4	0.0585 (18)	0.080 (2)	0.0239 (15)	−0.0023 (17)	0.0207 (14)	−0.0022 (17)
O5	0.071 (2)	0.082 (2)	0.0214 (15)	−0.0249 (18)	0.0209 (14)	−0.0079 (16)
N1	0.048 (2)	0.056 (2)	0.0250 (19)	−0.0101 (18)	0.0185 (16)	−0.0026 (18)
C1	0.064 (3)	0.072 (4)	0.070 (3)	−0.017 (3)	0.031 (3)	0.005 (3)
C2	0.055 (3)	0.045 (3)	0.040 (3)	0.007 (2)	0.017 (2)	0.001 (2)
C3	0.044 (3)	0.041 (3)	0.031 (2)	0.002 (2)	0.013 (2)	−0.001 (2)
C4	0.040 (3)	0.053 (3)	0.031 (3)	0.004 (2)	0.010 (2)	−0.010 (2)
C5	0.045 (3)	0.062 (3)	0.027 (2)	0.009 (2)	0.010 (2)	−0.006 (2)
C6	0.042 (2)	0.054 (3)	0.024 (2)	0.009 (2)	0.015 (2)	0.005 (2)
C7	0.041 (2)	0.041 (3)	0.020 (2)	0.005 (2)	0.0100 (18)	0.002 (2)
C8	0.049 (3)	0.049 (3)	0.023 (2)	0.005 (2)	0.015 (2)	−0.001 (2)
C9	0.046 (3)	0.056 (3)	0.021 (2)	−0.001 (2)	0.015 (2)	−0.010 (2)
C10	0.053 (3)	0.067 (3)	0.028 (2)	−0.013 (3)	0.018 (2)	−0.009 (2)
C11	0.081 (4)	0.073 (4)	0.064 (3)	−0.018 (3)	0.034 (3)	−0.022 (3)
C12	0.057 (3)	0.103 (5)	0.068 (4)	−0.010 (3)	0.009 (3)	−0.009 (3)

Geometric parameters (Å, º) top

O1—C1	1.451 (6)	C7—C8	1.373 (6)
O1—C2	1.331 (5)	C9—C10	1.507 (6)
O2—C2	1.231 (5)	C10—C11	1.515 (6)
O3—C4	1.351 (5)	C10—C12	1.516 (6)
O4—C6	1.364 (5)	C1—H1A	0.9600
O5—C9	1.239 (5)	C1—H1B	0.9600
O3—H3	0.8200	C1—H1C	0.9600
O4—H4	0.8200	C5—H5	0.9300
N1—C9	1.341 (5)	C8—H8	0.9300
N1—C7	1.410 (5)	C10—H10	0.9800
N1—H1	0.8600	C11—H11A	0.9600
C2—C3	1.448 (6)	C11—H11B	0.9600
C3—C4	1.404 (6)	C11—H11C	0.9600
C3—C8	1.395 (6)	C12—H12A	0.9600
C4—C5	1.377 (6)	C12—H12B	0.9600
C5—C6	1.371 (6)	C12—H12C	0.9600
C6—C7	1.407 (6)

C1—O1—C2	117.5 (3)	C11—C10—C12	112.1 (3)
C4—O3—H3	109.00	C9—C10—C11	109.8 (4)
C6—O4—H4	109.00	O1—C1—H1A	110.00
C7—N1—C9	129.7 (4)	O1—C1—H1B	110.00
C7—N1—H1	115.00	O1—C1—H1C	110.00
C9—N1—H1	115.00	H1A—C1—H1B	109.00
O1—C2—O2	120.7 (4)	H1A—C1—H1C	109.00
O1—C2—C3	114.9 (4)	H1B—C1—H1C	109.00
O2—C2—C3	124.5 (4)	C4—C5—H5	120.00
C2—C3—C4	119.2 (4)	C6—C5—H5	120.00
C4—C3—C8	119.3 (4)	C3—C8—H8	120.00
C2—C3—C8	121.6 (4)	C7—C8—H8	120.00
O3—C4—C3	122.4 (4)	C9—C10—H10	108.00
O3—C4—C5	117.4 (4)	C11—C10—H10	108.00
C3—C4—C5	120.2 (4)	C12—C10—H10	108.00
C4—C5—C6	120.1 (4)	C10—C11—H11A	109.00
C5—C6—C7	120.7 (4)	C10—C11—H11B	109.00
O4—C6—C5	123.8 (4)	C10—C11—H11C	109.00
O4—C6—C7	115.5 (4)	H11A—C11—H11B	109.00
N1—C7—C8	125.1 (4)	H11A—C11—H11C	110.00
C6—C7—C8	119.3 (4)	H11B—C11—H11C	110.00
N1—C7—C6	115.6 (4)	C10—C12—H12A	109.00
C3—C8—C7	120.6 (4)	C10—C12—H12B	109.00
O5—C9—N1	121.4 (4)	C10—C12—H12C	109.00
O5—C9—C10	122.0 (4)	H12A—C12—H12B	109.00
N1—C9—C10	116.6 (4)	H12A—C12—H12C	110.00
C9—C10—C12	110.3 (4)	H12B—C12—H12C	109.00

C1—O1—C2—O2	0.9 (6)	C4—C3—C8—C7	−0.1 (6)
C1—O1—C2—C3	179.9 (4)	O3—C4—C5—C6	178.3 (4)
C9—N1—C7—C6	−170.2 (4)	C3—C4—C5—C6	−1.4 (6)
C9—N1—C7—C8	11.3 (7)	C4—C5—C6—O4	−179.0 (4)
C7—N1—C9—O5	2.0 (7)	C4—C5—C6—C7	0.5 (6)
C7—N1—C9—C10	−177.9 (4)	O4—C6—C7—N1	1.4 (5)
O1—C2—C3—C4	−179.4 (4)	O4—C6—C7—C8	−179.9 (4)
O1—C2—C3—C8	−1.0 (6)	C5—C6—C7—N1	−178.1 (4)
O2—C2—C3—C4	−0.5 (7)	C5—C6—C7—C8	0.6 (6)
O2—C2—C3—C8	178.0 (4)	N1—C7—C8—C3	177.8 (4)
C2—C3—C4—O3	−0.1 (6)	C6—C7—C8—C3	−0.7 (6)
C2—C3—C4—C5	179.6 (4)	O5—C9—C10—C11	−70.1 (5)
C8—C3—C4—O3	−178.5 (4)	O5—C9—C10—C12	53.9 (6)
C8—C3—C4—C5	1.2 (6)	N1—C9—C10—C11	109.9 (4)
C2—C3—C8—C7	−178.5 (4)	N1—C9—C10—C12	−126.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4	0.86	2.19	2.604 (4)	109
O3—H3···O2	0.82	1.87	2.595 (4)	146
O4—H4···O5ⁱ	0.82	1.820	2.633 (4)	174

Symmetry code: (i) x, −y+2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₅NO₅
M_r	253.25
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	22.732 (4), 8.2338 (16), 14.743 (3)
β (°)	113.506 (9)
V (Å³)	2530.4 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.26 × 0.16 × 0.14

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.981, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	8480, 2218, 950
R_int	0.090
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.168, 0.96
No. of reflections	2218
No. of parameters	169
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.19

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012) and PLATON (Spek, 2009), WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4	0.86	2.19	2.604 (4)	109
O3—H3···O2	0.82	1.87	2.595 (4)	146
O4—H4···O5ⁱ	0.82	1.820	2.633 (4)	174

Symmetry code: (i) x, −y+2, z−1/2.

Acknowledgements

The authors acknowledge the provision of funds for the purchase of a diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha. Pakistan.

References

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