organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

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 ππ stacking [centroid–centroid separation = 3.604 (3) Å] is also observed.

Related literature

For related structures, see: Chen et al. (2011[Chen, G., Gao, H., Tang, J., Huang, Y., Chen, Y., Wang, Y., Zhao, H., Lin, H., Xie, Q., Hong, K., Li, J. & Yao, X. (2011). Chem. Pharm. Bull. 59, 447-451.]); Naz et al. (2013[Naz, S. S., Islam, N. U., Tahir, M. N. & Shah, M. R. (2013). Acta Cryst. E69, o207.]).

[Scheme 1]

Experimental

Crystal data
  • C12H15NO5

  • Mr = 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[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.981, Tmax = 0.985

  • 8480 measured reflections

  • 2218 independent reflections

  • 950 reflections with I > 2σ(I)

  • Rint = 0.090

Refinement
  • R[F2 > 2σ(F2)] = 0.065

  • wR(F2) = 0.168

  • S = 0.96

  • 2218 reflections

  • 169 parameters

  • H-atom parameters constrained

  • Δρmax = 0.25 e Å−3

  • Δρmin = −0.19 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and PLATON.

Supporting information


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 ππ 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.

Refinement top

The H-atoms were positioned geometrically (C–H = 0.93–0.98, N—H = 0.86 and O—H = 0.82 Å) and refined as riding with Uiso(H) = xUeq (C, N, O), where x = 1.5 for hydroxy & methyl groups and x = 1.2 for all other H-atoms.

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
[Figure 1] Fig. 1. View of the title compound with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] 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
C12H15NO5F(000) = 1072
Mr = 253.25Dx = 1.330 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 950 reflections
a = 22.732 (4) Åθ = 2.0–25.0°
b = 8.2338 (16) ŵ = 0.10 mm1
c = 14.743 (3) ÅT = 296 K
β = 113.506 (9)°Needle, brown
V = 2530.4 (9) Å30.26 × 0.16 × 0.14 mm
Z = 8
Data collection top
Bruker Kappa APEXII CCD
diffractometer
2218 independent reflections
Radiation source: fine-focus sealed tube950 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.090
Detector resolution: 8.10 pixels mm-1θmax = 25.0°, θmin = 2.0°
ω scansh = 2626
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
k = 99
Tmin = 0.981, Tmax = 0.985l = 1217
8480 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.065H-atom parameters constrained
wR(F2) = 0.168 w = 1/[σ2(Fo2) + (0.067P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.96(Δ/σ)max < 0.001
2218 reflectionsΔρmax = 0.25 e Å3
169 parametersΔρmin = 0.19 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0032 (7)
Crystal data top
C12H15NO5V = 2530.4 (9) Å3
Mr = 253.25Z = 8
Monoclinic, C2/cMo Kα radiation
a = 22.732 (4) ŵ = 0.10 mm1
b = 8.2338 (16) ÅT = 296 K
c = 14.743 (3) Å0.26 × 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)
Tmin = 0.981, Tmax = 0.985Rint = 0.090
8480 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0650 restraints
wR(F2) = 0.168H-atom parameters constrained
S = 0.96Δρmax = 0.25 e Å3
2218 reflectionsΔρmin = 0.19 e Å3
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
xyzUiso*/Ueq
O10.03069 (13)0.6890 (3)0.1237 (2)0.0561 (11)
O20.07828 (14)0.6152 (4)0.0343 (2)0.0674 (14)
O30.02971 (14)0.7095 (4)0.1577 (2)0.0664 (13)
O40.15588 (13)1.0422 (4)0.02943 (18)0.0528 (10)
O50.15037 (13)0.9581 (4)0.28873 (18)0.0574 (11)
N10.15743 (14)1.0418 (4)0.1481 (2)0.0418 (11)
C10.0795 (2)0.6008 (6)0.1437 (3)0.0673 (19)
C20.0344 (2)0.6874 (5)0.0313 (3)0.0473 (17)
C30.01556 (18)0.7776 (5)0.0160 (3)0.0393 (16)
C40.01545 (19)0.7844 (5)0.0792 (3)0.0427 (17)
C50.06228 (18)0.8703 (5)0.0956 (3)0.0461 (16)
C60.10844 (18)0.9523 (5)0.0193 (3)0.0394 (14)
C70.10893 (18)0.9489 (5)0.0764 (3)0.0347 (14)
C80.06285 (18)0.8611 (5)0.0931 (3)0.0401 (16)
C90.17569 (18)1.0465 (5)0.2465 (3)0.0405 (16)
C100.22833 (19)1.1646 (5)0.3026 (3)0.0488 (16)
C110.2012 (2)1.3027 (6)0.3419 (3)0.071 (2)
C120.2825 (2)1.0777 (6)0.3844 (3)0.081 (2)
H10.178461.104890.125240.0500*
H1A0.080750.490150.122480.1011*
H1B0.120550.650590.108540.1011*
H1C0.069540.603250.213430.1011*
H30.055050.662310.139880.0994*
H40.153181.034930.086430.0791*
H50.062610.872590.158480.0552*
H80.063170.857320.156330.0484*
H100.245341.209930.256530.0581*
H11A0.169851.360480.287490.1067*
H11B0.235201.375300.379630.1067*
H11C0.181391.259790.383350.1067*
H12A0.300850.997820.356060.1215*
H12B0.266051.025290.427660.1215*
H12C0.314771.154960.421340.1215*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.064 (2)0.065 (2)0.0401 (19)0.0134 (17)0.0215 (15)0.0018 (17)
O20.059 (2)0.084 (3)0.050 (2)0.0224 (18)0.0122 (16)0.0199 (18)
O30.057 (2)0.100 (3)0.0340 (18)0.0108 (19)0.0094 (15)0.0240 (19)
O40.0585 (18)0.080 (2)0.0239 (15)0.0023 (17)0.0207 (14)0.0022 (17)
O50.071 (2)0.082 (2)0.0214 (15)0.0249 (18)0.0209 (14)0.0079 (16)
N10.048 (2)0.056 (2)0.0250 (19)0.0101 (18)0.0185 (16)0.0026 (18)
C10.064 (3)0.072 (4)0.070 (3)0.017 (3)0.031 (3)0.005 (3)
C20.055 (3)0.045 (3)0.040 (3)0.007 (2)0.017 (2)0.001 (2)
C30.044 (3)0.041 (3)0.031 (2)0.002 (2)0.013 (2)0.001 (2)
C40.040 (3)0.053 (3)0.031 (3)0.004 (2)0.010 (2)0.010 (2)
C50.045 (3)0.062 (3)0.027 (2)0.009 (2)0.010 (2)0.006 (2)
C60.042 (2)0.054 (3)0.024 (2)0.009 (2)0.015 (2)0.005 (2)
C70.041 (2)0.041 (3)0.020 (2)0.005 (2)0.0100 (18)0.002 (2)
C80.049 (3)0.049 (3)0.023 (2)0.005 (2)0.015 (2)0.001 (2)
C90.046 (3)0.056 (3)0.021 (2)0.001 (2)0.015 (2)0.010 (2)
C100.053 (3)0.067 (3)0.028 (2)0.013 (3)0.018 (2)0.009 (2)
C110.081 (4)0.073 (4)0.064 (3)0.018 (3)0.034 (3)0.022 (3)
C120.057 (3)0.103 (5)0.068 (4)0.010 (3)0.009 (3)0.009 (3)
Geometric parameters (Å, º) top
O1—C11.451 (6)C7—C81.373 (6)
O1—C21.331 (5)C9—C101.507 (6)
O2—C21.231 (5)C10—C111.515 (6)
O3—C41.351 (5)C10—C121.516 (6)
O4—C61.364 (5)C1—H1A0.9600
O5—C91.239 (5)C1—H1B0.9600
O3—H30.8200C1—H1C0.9600
O4—H40.8200C5—H50.9300
N1—C91.341 (5)C8—H80.9300
N1—C71.410 (5)C10—H100.9800
N1—H10.8600C11—H11A0.9600
C2—C31.448 (6)C11—H11B0.9600
C3—C41.404 (6)C11—H11C0.9600
C3—C81.395 (6)C12—H12A0.9600
C4—C51.377 (6)C12—H12B0.9600
C5—C61.371 (6)C12—H12C0.9600
C6—C71.407 (6)
C1—O1—C2117.5 (3)C11—C10—C12112.1 (3)
C4—O3—H3109.00C9—C10—C11109.8 (4)
C6—O4—H4109.00O1—C1—H1A110.00
C7—N1—C9129.7 (4)O1—C1—H1B110.00
C7—N1—H1115.00O1—C1—H1C110.00
C9—N1—H1115.00H1A—C1—H1B109.00
O1—C2—O2120.7 (4)H1A—C1—H1C109.00
O1—C2—C3114.9 (4)H1B—C1—H1C109.00
O2—C2—C3124.5 (4)C4—C5—H5120.00
C2—C3—C4119.2 (4)C6—C5—H5120.00
C4—C3—C8119.3 (4)C3—C8—H8120.00
C2—C3—C8121.6 (4)C7—C8—H8120.00
O3—C4—C3122.4 (4)C9—C10—H10108.00
O3—C4—C5117.4 (4)C11—C10—H10108.00
C3—C4—C5120.2 (4)C12—C10—H10108.00
C4—C5—C6120.1 (4)C10—C11—H11A109.00
C5—C6—C7120.7 (4)C10—C11—H11B109.00
O4—C6—C5123.8 (4)C10—C11—H11C109.00
O4—C6—C7115.5 (4)H11A—C11—H11B109.00
N1—C7—C8125.1 (4)H11A—C11—H11C110.00
C6—C7—C8119.3 (4)H11B—C11—H11C110.00
N1—C7—C6115.6 (4)C10—C12—H12A109.00
C3—C8—C7120.6 (4)C10—C12—H12B109.00
O5—C9—N1121.4 (4)C10—C12—H12C109.00
O5—C9—C10122.0 (4)H12A—C12—H12B109.00
N1—C9—C10116.6 (4)H12A—C12—H12C110.00
C9—C10—C12110.3 (4)H12B—C12—H12C109.00
C1—O1—C2—O20.9 (6)C4—C3—C8—C70.1 (6)
C1—O1—C2—C3179.9 (4)O3—C4—C5—C6178.3 (4)
C9—N1—C7—C6170.2 (4)C3—C4—C5—C61.4 (6)
C9—N1—C7—C811.3 (7)C4—C5—C6—O4179.0 (4)
C7—N1—C9—O52.0 (7)C4—C5—C6—C70.5 (6)
C7—N1—C9—C10177.9 (4)O4—C6—C7—N11.4 (5)
O1—C2—C3—C4179.4 (4)O4—C6—C7—C8179.9 (4)
O1—C2—C3—C81.0 (6)C5—C6—C7—N1178.1 (4)
O2—C2—C3—C40.5 (7)C5—C6—C7—C80.6 (6)
O2—C2—C3—C8178.0 (4)N1—C7—C8—C3177.8 (4)
C2—C3—C4—O30.1 (6)C6—C7—C8—C30.7 (6)
C2—C3—C4—C5179.6 (4)O5—C9—C10—C1170.1 (5)
C8—C3—C4—O3178.5 (4)O5—C9—C10—C1253.9 (6)
C8—C3—C4—C51.2 (6)N1—C9—C10—C11109.9 (4)
C2—C3—C8—C7178.5 (4)N1—C9—C10—C12126.1 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O40.862.192.604 (4)109
O3—H3···O20.821.872.595 (4)146
O4—H4···O5i0.821.8202.633 (4)174
Symmetry code: (i) x, y+2, z1/2.

Experimental details

Crystal data
Chemical formulaC12H15NO5
Mr253.25
Crystal system, space groupMonoclinic, C2/c
Temperature (K)296
a, b, c (Å)22.732 (4), 8.2338 (16), 14.743 (3)
β (°) 113.506 (9)
V3)2530.4 (9)
Z8
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.26 × 0.16 × 0.14
Data collection
DiffractometerBruker Kappa APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2009)
Tmin, Tmax0.981, 0.985
No. of measured, independent and
observed [I > 2σ(I)] reflections
8480, 2218, 950
Rint0.090
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.065, 0.168, 0.96
No. of reflections2218
No. of parameters169
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N1—H1···O40.862.192.604 (4)109
O3—H3···O20.821.872.595 (4)146
O4—H4···O5i0.821.8202.633 (4)174
Symmetry code: (i) x, y+2, z1/2.
 

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

First citationBruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationChen, G., Gao, H., Tang, J., Huang, Y., Chen, Y., Wang, Y., Zhao, H., Lin, H., Xie, Q., Hong, K., Li, J. & Yao, X. (2011). Chem. Pharm. Bull. 59, 447–451.  CSD CrossRef CAS PubMed
First citationFarrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.  Web of Science CrossRef CAS IUCr Journals
First citationNaz, S. S., Islam, N. U., Tahir, M. N. & Shah, M. R. (2013). Acta Cryst. E69, o207.  CSD CrossRef IUCr Journals
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals

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