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Acta Crystallogr Sect E Struct Rep Online. 2012 October 1; 68(Pt 10): o3029.
Published online 2012 September 29. doi:  10.1107/S1600536812038196
PMCID: PMC3470383

4-(Cyclo­propane­carboxamido)­benzoic acid

Abstract

In the title compound, C11H11NO3, the dihedral angle between the benzene ring and the cyclo­propane ring is 63.2 (1)°. In the crystal, mol­ecules are linked through classical cyclic carb­oxy­lic acid O—H(...)O hydrogen-bond inter­actions [graph set R 2 2(8)] giving centrosymmetric dimers which are extended along the b-axis direction through amide N—H(...)O hydrogen-bond inter­actions, giving one-dimensional ribbon structures. Weak C—H(...)O inter­actions are also present in the structure.

Related literature  

For general background to the biological activity of similar substituted benzoic acids, see: Gediya et al. (2008 [triangle]). For applications of analogs of the title compound, see: Sobotka et al. (1991 [triangle]); Chernoivanov et al. (1993 [triangle], 1997 [triangle]). For graph-set analysis, see: Etter et al. (1990 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-68-o3029-scheme1.jpg

Experimental  

Crystal data  

  • C11H11NO3
  • M r = 205.21
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-68-o3029-efi1.jpg
  • a = 13.2429 (14) Å
  • b = 4.7704 (5) Å
  • c = 16.7983 (18) Å
  • β = 111.227 (2)°
  • V = 989.21 (18) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 293 K
  • 0.31 × 0.21 × 0.17 mm

Data collection  

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2003 [triangle]) T min = 0.789, T max = 1.000
  • 5558 measured reflections
  • 1934 independent reflections
  • 1682 reflections with I > 2σ(I)
  • R int = 0.022

Refinement  

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.119
  • S = 1.05
  • 1934 reflections
  • 145 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.15 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: SMART (Bruker, 2003 [triangle]); cell refinement: sAINT (Bruker, 2003 [triangle]); data reduction: SAINT; 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: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812038196/zs2222sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812038196/zs2222Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812038196/zs2222Isup3.cml

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

Acknowledgments

This work was supported by the Fundamental Research Funds for the Central Universities.

supplementary crystallographic information

Comment

The title compound, C11H11NO3, has been of great interest for many years because it has different biological activities and been used as a ligand in the synthesis of various Cathepsin-S reversible inhibitor compounds (Gediya et al., 2008). In order to obtain a new potentially active histone deacetylase inhibitor, the title compound was synthesized and its crystal structure is reported here. In this molecule (Fig. 1), the dihedral angle between the benzene ring and the cyclopropane ring is 63.2 (1)°. In the crystal, molecules are linked through classic cyclic carboxylic acid O—H···O hydrogen-bonding interactions [graph set R22(8) (Etter et al., 1990)] giving centrosymmetric dimers which are extended along b through amide N—H···O hydrogen-bonding interactions (Table 1), giving one-dimensional ribbon structures (Fig. 2). Present also in the structure are weak C—H···O interactions to both amide and carboxyl O-acceptors.

Experimental

Cyclopropanecarboxylic acid (500mg, 5.8 mmol) and N, N'- carbonyldiimidazole (1.035 g, 6.38 mmol) were dissolved in acetonitrile (5ml) and the solotion was stirred for 0.5h, then added dropwise into 5 ml of an acetonitrile solution of 4-aminobenzoic acid (1.59 g, 11.6 mmol). This solution was then added dropwise to 5 ml of a trifluoroacetic acid solution in acetonitrile (727 mg, 6.38 mmol) which was stirred for 1h. The resulting mixture was dried, then diluted with ethyl acetate, washed with water, then dried in vacuo. The residue was purified by colunm chromatography (CH3OH/CH2Cl2, 5/95). Crystals suitable for X-ray diffraction were grown in a dilute CH3OH/CH2Cl2 solution at room temperature by slow evaporation.

Refinement

Hydrogen atoms on O and N were located in a difference-Fourier map and both coordinates and isotropic displacement parameters were refined. Other H-atoms were placed in idealized positions and allowed to ride on their respective parent atoms, with C—H = 0.93 Å (aromatic) or 0.97 or 0.98 Å (aliphatic) and Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
A view of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level.
Fig. 2.
The structure of the infinite one-dimensional ribbon structures, with hydrogen bonds shown as dashed lines.

Crystal data

C11H11NO3F(000) = 432
Mr = 205.21Dx = 1.378 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2486 reflections
a = 13.2429 (14) Åθ = 4.9–56.1°
b = 4.7704 (5) ŵ = 0.10 mm1
c = 16.7983 (18) ÅT = 293 K
β = 111.227 (2)°Prismatic, colorless
V = 989.21 (18) Å30.31 × 0.21 × 0.17 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer1934 independent reflections
Radiation source: fine-focus sealed tube1682 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
[var phi] and ω scansθmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2003)h = −16→16
Tmin = 0.789, Tmax = 1.000k = −5→5
5558 measured reflectionsl = −20→15

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.119w = 1/[σ2(Fo2) + (0.0639P)2 + 0.2147P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
1934 reflectionsΔρmax = 0.15 e Å3
145 parametersΔρmin = −0.20 e Å3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.022 (4)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
N10.56625 (9)0.5748 (2)0.15289 (8)0.0404 (3)
O10.49517 (9)0.1514 (2)0.16147 (9)0.0605 (4)
O20.87070 (9)−0.0148 (3)−0.01839 (8)0.0707 (4)
O30.98671 (9)0.2842 (3)0.06937 (8)0.0647 (4)
C10.49424 (11)0.4057 (3)0.16928 (9)0.0394 (3)
C20.41426 (12)0.5484 (3)0.19760 (11)0.0498 (4)
H20.42170.75200.20530.060*
C30.30111 (13)0.4331 (4)0.16602 (12)0.0649 (5)
H3A0.24180.56560.15330.078*
H3B0.28620.27070.12880.078*
C40.36945 (14)0.3933 (4)0.25499 (11)0.0591 (5)
H4A0.39690.20610.27300.071*
H4B0.35240.50100.29750.071*
C50.64690 (10)0.4785 (3)0.12217 (8)0.0361 (3)
C60.75069 (11)0.5867 (3)0.15619 (10)0.0466 (4)
H60.76710.72350.19840.056*
C70.83018 (11)0.4915 (3)0.12747 (9)0.0479 (4)
H70.89980.56490.15050.058*
C80.80668 (10)0.2874 (3)0.06466 (9)0.0407 (3)
C90.70189 (11)0.1846 (3)0.02946 (9)0.0471 (4)
H90.68500.0505−0.01360.057*
C100.62238 (11)0.2803 (3)0.05789 (9)0.0449 (4)
H100.55220.21110.03370.054*
C110.89105 (11)0.1726 (3)0.03496 (9)0.0447 (4)
H10.5640 (13)0.744 (4)0.1630 (10)0.049 (5)*
H31.0297 (19)0.200 (5)0.0483 (16)0.110 (9)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0449 (6)0.0271 (6)0.0596 (7)0.0002 (5)0.0314 (6)−0.0046 (5)
O10.0739 (8)0.0284 (5)0.1042 (9)0.0011 (5)0.0621 (7)−0.0012 (5)
O20.0470 (6)0.0924 (10)0.0813 (8)−0.0001 (6)0.0334 (6)−0.0349 (7)
O30.0408 (6)0.0872 (9)0.0737 (8)−0.0002 (6)0.0300 (6)−0.0204 (7)
C10.0437 (7)0.0293 (7)0.0531 (8)0.0010 (5)0.0270 (6)−0.0004 (5)
C20.0569 (9)0.0321 (7)0.0781 (11)−0.0027 (6)0.0457 (8)−0.0058 (7)
C30.0451 (8)0.0789 (12)0.0805 (12)0.0013 (8)0.0345 (8)−0.0126 (10)
C40.0635 (10)0.0607 (10)0.0722 (11)−0.0040 (8)0.0474 (9)−0.0034 (8)
C50.0384 (7)0.0319 (6)0.0445 (7)0.0036 (5)0.0226 (6)0.0031 (5)
C60.0456 (8)0.0478 (8)0.0527 (8)−0.0067 (6)0.0252 (6)−0.0136 (6)
C70.0357 (7)0.0583 (9)0.0534 (8)−0.0053 (6)0.0204 (6)−0.0091 (7)
C80.0385 (7)0.0473 (8)0.0413 (7)0.0064 (6)0.0206 (6)0.0030 (6)
C90.0435 (7)0.0532 (9)0.0499 (8)−0.0001 (6)0.0231 (6)−0.0135 (7)
C100.0349 (7)0.0503 (8)0.0524 (8)−0.0026 (6)0.0193 (6)−0.0098 (6)
C110.0391 (7)0.0559 (9)0.0434 (7)0.0063 (6)0.0199 (6)0.0008 (7)

Geometric parameters (Å, º)

N1—C11.3515 (17)C4—H4A0.9700
N1—C51.4202 (16)C4—H4B0.9700
N1—H10.827 (18)C5—C101.3827 (19)
O1—C11.2208 (17)C5—C61.3832 (19)
O2—C111.2249 (19)C6—C71.3839 (19)
O3—C111.3007 (18)C6—H60.9300
O3—H30.870 (17)C7—C81.386 (2)
C1—C21.4753 (18)C7—H70.9300
C2—C41.498 (2)C8—C91.386 (2)
C2—C31.501 (2)C8—C111.4834 (18)
C2—H20.9800C9—C101.3817 (19)
C3—C41.452 (3)C9—H90.9300
C3—H3A0.9700C10—H100.9300
C3—H3B0.9700
C1—N1—C5124.04 (11)C2—C4—H4B117.7
C1—N1—H1117.4 (11)H4A—C4—H4B114.8
C5—N1—H1118.6 (11)C10—C5—C6119.67 (12)
C11—O3—H3107.8 (18)C10—C5—N1120.68 (12)
O1—C1—N1122.42 (12)C6—C5—N1119.65 (12)
O1—C1—C2121.98 (12)C5—C6—C7120.07 (13)
N1—C1—C2115.59 (12)C5—C6—H6120.0
C1—C2—C4118.53 (13)C7—C6—H6120.0
C1—C2—C3117.27 (13)C6—C7—C8120.44 (13)
C4—C2—C357.93 (11)C6—C7—H7119.8
C1—C2—H2116.7C8—C7—H7119.8
C4—C2—H2116.7C7—C8—C9119.16 (12)
C3—C2—H2116.7C7—C8—C11121.77 (13)
C4—C3—C260.91 (11)C9—C8—C11119.06 (13)
C4—C3—H3A117.7C10—C9—C8120.42 (13)
C2—C3—H3A117.7C10—C9—H9119.8
C4—C3—H3B117.7C8—C9—H9119.8
C2—C3—H3B117.7C9—C10—C5120.19 (13)
H3A—C3—H3B114.8C9—C10—H10119.9
C3—C4—C261.15 (11)C5—C10—H10119.9
C3—C4—H4A117.7O2—C11—O3123.00 (13)
C2—C4—H4A117.7O2—C11—C8121.50 (13)
C3—C4—H4B117.7O3—C11—C8115.50 (13)
C5—N1—C1—O12.5 (2)C5—C6—C7—C8−0.1 (2)
C5—N1—C1—C2−177.69 (12)C6—C7—C8—C91.6 (2)
O1—C1—C2—C428.8 (2)C6—C7—C8—C11−177.50 (14)
N1—C1—C2—C4−150.99 (15)C7—C8—C9—C10−1.3 (2)
O1—C1—C2—C3−37.6 (2)C11—C8—C9—C10177.75 (13)
N1—C1—C2—C3142.56 (15)C8—C9—C10—C5−0.4 (2)
C1—C2—C3—C4108.12 (16)C6—C5—C10—C91.9 (2)
C1—C2—C4—C3−105.96 (17)N1—C5—C10—C9−178.93 (14)
C1—N1—C5—C1043.3 (2)C7—C8—C11—O2177.35 (16)
C1—N1—C5—C6−137.46 (15)C9—C8—C11—O2−1.7 (2)
C10—C5—C6—C7−1.6 (2)C7—C8—C11—O3−2.6 (2)
N1—C5—C6—C7179.14 (13)C9—C8—C11—O3178.37 (13)

Hydrogen-bond geometry (Å, º)

D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.827 (18)2.144 (19)2.9273 (16)158.2 (16)
O3—H3···O2ii0.87 (2)1.80 (2)2.6685 (15)173 (3)
C2—H2···O1i0.982.373.2034 (18)142
C3—H3B···O2iii0.972.543.350 (2)141

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZS2222).

References

  • Bruker (2003). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chernoivanov, V. A. (1993). Zh. Org. Khim. II, 29, 2148-2152.
  • Chernoivanov, V. A. (1997). Mol. Cryst. Liq. Cryst. A, 297, 239-245.
  • Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. [PubMed]
  • Gediya, L. K., Belosay, A., Khandelwal, A. & Purushottamachar, P. (2008). Bioorg. Med. Chem. 16, 3352–3360. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Sobotka, W., Nawrot, J. & Konopinska, D. (1991). Mater. Sesji Naukowej Instytutu Ochrony Roslin, 30, 11–14.

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