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Acta Crystallogr Sect E Struct Rep Online. 2008 May 1; 64(Pt 5): o785.
Published online 2008 April 2. doi:  10.1107/S1600536808005989
PMCID: PMC2961301

Ethyl 4-amino-3-methyl­benzoate

Abstract

The asymmetric unit of the title compound, C10H13NO2, contains two mol­ecules which are linked via an N—H(...)N hydrogen bonds to form a dimer. These dimers are further linked via N—H(...)O inter­molecular hydrogen bonds.

Related literature

For related literature, see: Baraldi et al. (1999 [triangle], 2000 [triangle], 2003 [triangle], 2007 [triangle]); Wang et al. (2003 [triangle]); Zaffaroni et al. (2002 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-64-0o785-scheme1.jpg

Experimental

Crystal data

  • C10H13NO2
  • M r = 179.21
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o785-efi1.jpg
  • a = 8.0110 (16) Å
  • b = 8.7030 (17) Å
  • c = 15.835 (3) Å
  • α = 90.78 (3)°
  • β = 95.13 (3)°
  • γ = 114.34 (3)°
  • V = 1000.3 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 298 (2) K
  • 0.30 × 0.20 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.975, T max = 0.991
  • 3874 measured reflections
  • 3594 independent reflections
  • 2146 reflections with I > 2σ(I)
  • R int = 0.052
  • 3 standard reflections every 200 reflections intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.074
  • wR(F 2) = 0.176
  • S = 1.02
  • 3594 reflections
  • 235 parameters
  • H-atom parameters constrained
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo,1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808005989/er2050sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808005989/er2050Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank Dr Shan Liu for useful discussions.

supplementary crystallographic information

Comment

Ethyl 3-methyl-4-aminobenzoate is a material for preparing the important intermidates of bis-(2-haloethyl)aminophenyl substituted distamycin derivatives(Baraldi et al., 2007), which are used as antitumor alkylating and antiviral agents related to the known antibiotic distamycin A (Baraldi et al., 1999). Distamycin A belongs to the family of the pyrroleamidine antibiotics (Baraldi et al., 2000) and is reported to interact reversibly and selectively with DNA-AT sequences interfering with both replication and transcription (Baraldi et al., 2003). Bis-(2-haloethyl)aminophenyl substituted distamycin derivatives can therefore be used in a treatment to ameliorate a cancer (Wang et al., 2003). They may be administered to improve the condition of a patient having a leukaemia lymphoma, sarcoma, such as myeloblastic leukaemia, neuroblastoma, Wilm's tumor or malignant neoplasm of the bladder, breast, lung or thyroid. (Zaffaroni et al., 2002).

The molecular structure of (I) is shown in Fig. 1. The bond lengths and angles are within normal ranges (Allen et al., 1987).

The asymmetric unit of the title compound, contains two molecules which are linked via N—H···N hydrogen bonds to form dimers. In the crystals, molecules are linked via N—H···O Intermolecular hydrogen bonds (Table 1), which may be effective in the stabilization of the crystals.

Experimental

The title compound was prepared from 3-Methyl-4-aminobenzoic acid (15.2 g, 100 mmole) in ethanol (40.4 ml, 1000 mmole). After the solid has melted, concentrated hydrochloric acid (142 g, 120 ml) was added dropwise from a dropping funnel at 90°C, the the reaction mixture was cooled with ice and water and finaly the product was filtered by suction. Suitable crystals were obtained by evaporation of a methanol solution for about 3 d.

Refinement

All H atoms were placed geometrically at the distances of 0.93–0.97 Å for C—H and 0.86 Å for N—H and included in the refinement in riding motion approximation with Uiso(H) = 1.2 or 1.5Ueq of the carrier atom.

Figures

Fig. 1.
A view of the molecular structure of (I), showing displacement ellipsoids at the 50% probability level. N—H···N hydrogen bonds are shown as dashed lines.

Crystal data

C10H13NO2Z = 4
Mr = 179.21F000 = 384
Triclinic, P1Dx = 1.190 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 8.0110 (16) ÅCell parameters from 25 reflections
b = 8.7030 (17) Åθ = 10–14º
c = 15.835 (3) ŵ = 0.08 mm1
α = 90.78 (3)ºT = 298 (2) K
β = 95.13 (3)ºBlock, colorless
γ = 114.34 (3)º0.30 × 0.20 × 0.10 mm
V = 1000.3 (3) Å3

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.052
Radiation source: fine-focus sealed tubeθmax = 25.2º
Monochromator: graphiteθmin = 1.3º
T = 298(2) Kh = −9→9
ω/2θ scansk = −10→10
Absorption correction: ψ scan(North et al., 1968)l = 0→18
Tmin = 0.975, Tmax = 0.9913 standard reflections
3874 measured reflections every 200 reflections
3594 independent reflections intensity decay: none
2146 reflections with I > 2σ(I)

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.075H-atom parameters constrained
wR(F2) = 0.177  w = 1/[σ2(Fo2) + (0.04P)2 + 1.2P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
3594 reflectionsΔρmax = 0.23 e Å3
235 parametersΔρmin = −0.22 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
O11.2476 (4)0.4839 (3)1.01662 (15)0.0684 (7)
O21.2577 (4)0.5912 (3)0.88836 (15)0.0742 (8)
N10.5942 (5)−0.1423 (4)0.8227 (2)0.0872 (11)
H1A0.5484−0.21920.85800.105*
H1B0.5509−0.16040.77010.105*
C11.4390 (7)0.6205 (6)1.1432 (2)0.0884 (13)
H1C1.53890.72201.16740.133*
H1D1.47180.52671.15050.133*
H1E1.33110.60121.17120.133*
C21.3999 (6)0.6384 (5)1.0501 (2)0.0695 (10)
H2A1.36810.73381.04200.083*
H2B1.50770.65711.02110.083*
C31.1842 (5)0.4730 (4)0.9338 (2)0.0549 (8)
C41.0343 (5)0.3145 (4)0.9073 (2)0.0514 (8)
C50.9506 (5)0.1886 (4)0.9638 (2)0.0620 (10)
H5A0.99320.20721.02120.074*
C60.8093 (5)0.0413 (4)0.9358 (2)0.0629 (10)
H6A0.7590−0.04100.97430.075*
C70.7362 (5)0.0087 (4)0.8503 (2)0.0607 (9)
C80.8176 (5)0.1308 (4)0.7910 (2)0.0579 (9)
C90.9597 (5)0.2792 (4)0.8216 (2)0.0537 (8)
H9A1.01030.36200.78340.064*
C100.7439 (6)0.0996 (5)0.6984 (2)0.0790 (12)
H10A0.81840.19260.66720.119*
H10B0.61920.08890.69240.119*
H10C0.7471−0.00260.67670.119*
O30.2589 (4)0.2954 (3)0.47872 (15)0.0695 (7)
O40.1772 (4)0.3743 (3)0.59841 (17)0.0836 (9)
N20.2153 (5)−0.3189 (4)0.69728 (19)0.0828 (11)
H2C0.1979−0.33800.74960.099*
H2D0.2337−0.39030.66560.099*
C110.3055 (7)0.4392 (6)0.3509 (3)0.0990 (15)
H11A0.30720.53700.32290.149*
H11B0.21520.33910.32040.149*
H11C0.42480.43750.35230.149*
C120.2570 (6)0.4456 (5)0.4406 (2)0.0764 (11)
H12A0.34650.54660.47220.092*
H12B0.13600.44610.44030.092*
C130.2119 (5)0.2726 (5)0.5596 (2)0.0608 (9)
C140.2194 (5)0.1199 (4)0.59291 (19)0.0543 (8)
C150.1854 (5)0.0871 (4)0.6782 (2)0.0545 (8)
H15A0.16320.16490.71080.065*
C160.1840 (5)−0.0559 (4)0.7146 (2)0.0549 (8)
C170.2137 (5)−0.1753 (4)0.6644 (2)0.0597 (9)
C180.2476 (6)−0.1425 (5)0.5793 (2)0.0682 (11)
H18A0.2686−0.22000.54580.082*
C190.2499 (5)0.0029 (5)0.5451 (2)0.0660 (10)
H19A0.27240.02210.48870.079*
C200.1455 (6)−0.0876 (5)0.8067 (2)0.0768 (12)
H20A0.12790.00550.83120.115*
H20B0.2479−0.09860.83790.115*
H20C0.0363−0.18970.80890.115*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0901 (18)0.0660 (16)0.0515 (14)0.0347 (14)0.0056 (13)0.0157 (12)
O20.100 (2)0.0594 (15)0.0596 (16)0.0282 (14)0.0118 (14)0.0263 (13)
N10.099 (3)0.072 (2)0.078 (2)0.021 (2)0.013 (2)0.0202 (18)
C10.114 (4)0.099 (3)0.063 (3)0.059 (3)−0.010 (2)−0.008 (2)
C20.090 (3)0.060 (2)0.067 (2)0.040 (2)0.000 (2)0.0075 (19)
C30.068 (2)0.055 (2)0.051 (2)0.0334 (18)0.0094 (17)0.0118 (16)
C40.068 (2)0.0485 (19)0.0467 (18)0.0319 (17)0.0108 (16)0.0142 (15)
C50.087 (3)0.060 (2)0.048 (2)0.037 (2)0.0177 (18)0.0259 (17)
C60.078 (3)0.057 (2)0.057 (2)0.030 (2)0.0191 (19)0.0255 (18)
C70.072 (2)0.049 (2)0.067 (2)0.0285 (18)0.0145 (19)0.0180 (17)
C80.073 (2)0.062 (2)0.049 (2)0.0373 (19)0.0100 (17)0.0149 (17)
C90.073 (2)0.0505 (19)0.0439 (18)0.0305 (18)0.0133 (16)0.0173 (15)
C100.096 (3)0.076 (3)0.056 (2)0.026 (2)0.006 (2)0.012 (2)
O30.0994 (19)0.0705 (16)0.0524 (15)0.0462 (15)0.0200 (13)0.0246 (12)
O40.140 (3)0.0684 (17)0.0626 (17)0.0603 (18)0.0224 (16)0.0110 (14)
N20.148 (3)0.070 (2)0.0511 (18)0.065 (2)0.0102 (19)0.0136 (16)
C110.135 (4)0.104 (4)0.066 (3)0.053 (3)0.022 (3)0.038 (3)
C120.102 (3)0.068 (2)0.066 (3)0.041 (2)0.012 (2)0.027 (2)
C130.077 (2)0.064 (2)0.047 (2)0.034 (2)0.0102 (17)0.0113 (17)
C140.072 (2)0.055 (2)0.0380 (17)0.0288 (17)0.0062 (15)0.0088 (15)
C150.079 (2)0.056 (2)0.0427 (18)0.0406 (18)0.0107 (16)0.0082 (15)
C160.076 (2)0.061 (2)0.0390 (17)0.0380 (18)0.0113 (16)0.0099 (15)
C170.094 (3)0.055 (2)0.0438 (19)0.045 (2)0.0064 (17)0.0099 (15)
C180.117 (3)0.064 (2)0.0439 (19)0.057 (2)0.011 (2)0.0021 (17)
C190.099 (3)0.069 (2)0.0382 (18)0.041 (2)0.0134 (18)0.0084 (17)
C200.120 (3)0.095 (3)0.042 (2)0.068 (3)0.022 (2)0.0199 (19)

Geometric parameters (Å, °)

O1—C31.351 (4)O3—C131.362 (4)
O1—C21.446 (4)O3—C121.452 (4)
O2—C31.232 (4)O4—C131.207 (4)
N1—C71.369 (5)N2—C171.365 (4)
N1—H1A0.8600N2—H2C0.8600
N1—H1B0.8600N2—H2D0.8600
C1—C21.503 (5)C11—C121.513 (5)
C1—H1C0.9600C11—H11A0.9600
C1—H1D0.9600C11—H11B0.9600
C1—H1E0.9600C11—H11C0.9600
C2—H2A0.9700C12—H12A0.9700
C2—H2B0.9700C12—H12B0.9700
C3—C41.432 (5)C13—C141.458 (5)
C4—C51.407 (4)C14—C191.374 (5)
C4—C91.409 (4)C14—C151.411 (4)
C5—C61.349 (5)C15—C161.375 (4)
C5—H5A0.9300C15—H15A0.9300
C6—C71.404 (5)C16—C171.409 (4)
C6—H6A0.9300C16—C201.522 (4)
C7—C81.414 (5)C17—C181.409 (4)
C8—C91.367 (5)C18—C191.376 (5)
C8—C101.509 (5)C18—H18A0.9300
C9—H9A0.9300C19—H19A0.9300
C10—H10A0.9600C20—H20A0.9600
C10—H10B0.9600C20—H20B0.9600
C10—H10C0.9600C20—H20C0.9600
C3—O1—C2118.2 (3)C13—O3—C12116.0 (3)
C7—N1—H1A120.0C17—N2—H2C120.0
C7—N1—H1B120.0C17—N2—H2D120.0
H1A—N1—H1B120.0H2C—N2—H2D120.0
C2—C1—H1C109.5C12—C11—H11A109.5
C2—C1—H1D109.5C12—C11—H11B109.5
H1C—C1—H1D109.5H11A—C11—H11B109.5
C2—C1—H1E109.5C12—C11—H11C109.5
H1C—C1—H1E109.5H11A—C11—H11C109.5
H1D—C1—H1E109.5H11B—C11—H11C109.5
O1—C2—C1107.6 (3)O3—C12—C11106.2 (3)
O1—C2—H2A110.2O3—C12—H12A110.5
C1—C2—H2A110.2C11—C12—H12A110.5
O1—C2—H2B110.2O3—C12—H12B110.5
C1—C2—H2B110.2C11—C12—H12B110.5
H2A—C2—H2B108.5H12A—C12—H12B108.7
O2—C3—O1120.3 (3)O4—C13—O3121.9 (3)
O2—C3—C4126.2 (3)O4—C13—C14125.8 (3)
O1—C3—C4113.5 (3)O3—C13—C14112.2 (3)
C5—C4—C9116.4 (3)C19—C14—C15118.2 (3)
C5—C4—C3123.1 (3)C19—C14—C13123.8 (3)
C9—C4—C3120.5 (3)C15—C14—C13118.0 (3)
C6—C5—C4121.0 (3)C16—C15—C14122.3 (3)
C6—C5—H5A119.5C16—C15—H15A118.8
C4—C5—H5A119.5C14—C15—H15A118.8
C5—C6—C7121.8 (3)C15—C16—C17118.7 (3)
C5—C6—H6A119.1C15—C16—C20120.9 (3)
C7—C6—H6A119.1C17—C16—C20120.4 (3)
N1—C7—C6121.1 (3)N2—C17—C16121.3 (3)
N1—C7—C8119.7 (3)N2—C17—C18119.7 (3)
C6—C7—C8119.1 (3)C16—C17—C18119.0 (3)
C9—C8—C7117.5 (3)C19—C18—C17120.8 (3)
C9—C8—C10121.9 (3)C19—C18—H18A119.6
C7—C8—C10120.6 (3)C17—C18—H18A119.6
C8—C9—C4124.2 (3)C14—C19—C18121.0 (3)
C8—C9—H9A117.9C14—C19—H19A119.5
C4—C9—H9A117.9C18—C19—H19A119.5
C8—C10—H10A109.5C16—C20—H20A109.5
C8—C10—H10B109.5C16—C20—H20B109.5
H10A—C10—H10B109.5H20A—C20—H20B109.5
C8—C10—H10C109.5C16—C20—H20C109.5
H10A—C10—H10C109.5H20A—C20—H20C109.5
H10B—C10—H10C109.5H20B—C20—H20C109.5
C3—O1—C2—C1178.1 (3)C13—O3—C12—C11−177.7 (3)
C2—O1—C3—O21.4 (5)C12—O3—C13—O4−2.5 (5)
C2—O1—C3—C4179.7 (3)C12—O3—C13—C14−179.4 (3)
O2—C3—C4—C5−176.4 (3)O4—C13—C14—C19176.4 (4)
O1—C3—C4—C55.4 (5)O3—C13—C14—C19−6.9 (5)
O2—C3—C4—C92.0 (5)O4—C13—C14—C15−0.8 (6)
O1—C3—C4—C9−176.2 (3)O3—C13—C14—C15176.0 (3)
C9—C4—C5—C61.4 (5)C19—C14—C15—C160.8 (5)
C3—C4—C5—C6179.9 (3)C13—C14—C15—C16178.1 (3)
C4—C5—C6—C7−1.9 (6)C14—C15—C16—C17−1.4 (5)
C5—C6—C7—N1179.2 (4)C14—C15—C16—C20−179.6 (3)
C5—C6—C7—C82.7 (6)C15—C16—C17—N2179.5 (4)
N1—C7—C8—C9−179.6 (3)C20—C16—C17—N2−2.3 (6)
C6—C7—C8—C9−3.0 (5)C15—C16—C17—C181.3 (5)
N1—C7—C8—C102.9 (5)C20—C16—C17—C18179.5 (4)
C6—C7—C8—C10179.4 (3)N2—C17—C18—C19−178.9 (4)
C7—C8—C9—C42.8 (5)C16—C17—C18—C19−0.7 (6)
C10—C8—C9—C4−179.7 (3)C15—C14—C19—C18−0.1 (6)
C5—C4—C9—C8−2.0 (5)C13—C14—C19—C18−177.2 (4)
C3—C4—C9—C8179.6 (3)C17—C18—C19—C140.0 (6)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.862.333.023 (5)138
N1—H1B···N20.862.613.242 (5)131
N2—H2C···O2i0.862.353.160 (4)157
N2—H2D···O4ii0.862.152.967 (4)158

Symmetry codes: (i) x−1, y−1, z; (ii) x, y−1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ER2050).

References

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Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography