organic compounds
4-(Cyclopropanecarboxamido)benzoic acid
aCollege of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620, People's Republic of China
*Correspondence e-mail: zyshao@dhu.edu.cn
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 R22(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). For applications of analogs of the title compound, see: Sobotka et al. (1991); Chernoivanov et al. (1993, 1997). For graph-set analysis, see: Etter et al. (1990).
Experimental
Crystal data
|
Refinement
|
Data collection: SMART (Bruker, 2003); cell sAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536812038196/zs2222sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812038196/zs2222Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812038196/zs2222Isup3.cml
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
(CH3OH/CH2Cl2, 5/95). Crystals suitable for X-ray diffraction were grown in a dilute CH3OH/CH2Cl2 solution at room temperature by slow evaporation.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).
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
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.For general background to the biological activity of similar substituted benzoic acids, see: Gediya et al. (2008). For applications of analogs of the title compound, see: Sobotka et al. (1991); Chernoivanov et al. (1993, 1997). For graph-set analysis, see: Etter et al. (1990).
Data collection: SMART (Bruker, 2003); cell
sAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C11H11NO3 | F(000) = 432 |
Mr = 205.21 | Dx = 1.378 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2486 reflections |
a = 13.2429 (14) Å | θ = 4.9–56.1° |
b = 4.7704 (5) Å | µ = 0.10 mm−1 |
c = 16.7983 (18) Å | T = 293 K |
β = 111.227 (2)° | Prismatic, colorless |
V = 989.21 (18) Å3 | 0.31 × 0.21 × 0.17 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 1934 independent reflections |
Radiation source: fine-focus sealed tube | 1682 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
φ and ω scans | θmax = 26.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −16→16 |
Tmin = 0.789, Tmax = 1.000 | k = −5→5 |
5558 measured reflections | l = −20→15 |
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)] = 0.041 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.119 | w = 1/[σ2(Fo2) + (0.0639P)2 + 0.2147P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
1934 reflections | Δρmax = 0.15 e Å−3 |
145 parameters | Δρmin = −0.20 e Å−3 |
1 restraint | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.022 (4) |
C11H11NO3 | V = 989.21 (18) Å3 |
Mr = 205.21 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.2429 (14) Å | µ = 0.10 mm−1 |
b = 4.7704 (5) Å | T = 293 K |
c = 16.7983 (18) Å | 0.31 × 0.21 × 0.17 mm |
β = 111.227 (2)° |
Bruker SMART CCD area-detector diffractometer | 1934 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 1682 reflections with I > 2σ(I) |
Tmin = 0.789, Tmax = 1.000 | Rint = 0.022 |
5558 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 1 restraint |
wR(F2) = 0.119 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.15 e Å−3 |
1934 reflections | Δρmin = −0.20 e Å−3 |
145 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.56625 (9) | 0.5748 (2) | 0.15289 (8) | 0.0404 (3) | |
O1 | 0.49517 (9) | 0.1514 (2) | 0.16147 (9) | 0.0605 (4) | |
O2 | 0.87070 (9) | −0.0148 (3) | −0.01839 (8) | 0.0707 (4) | |
O3 | 0.98671 (9) | 0.2842 (3) | 0.06937 (8) | 0.0647 (4) | |
C1 | 0.49424 (11) | 0.4057 (3) | 0.16928 (9) | 0.0394 (3) | |
C2 | 0.41426 (12) | 0.5484 (3) | 0.19760 (11) | 0.0498 (4) | |
H2 | 0.4217 | 0.7520 | 0.2053 | 0.060* | |
C3 | 0.30111 (13) | 0.4331 (4) | 0.16602 (12) | 0.0649 (5) | |
H3A | 0.2418 | 0.5656 | 0.1533 | 0.078* | |
H3B | 0.2862 | 0.2707 | 0.1288 | 0.078* | |
C4 | 0.36945 (14) | 0.3933 (4) | 0.25499 (11) | 0.0591 (5) | |
H4A | 0.3969 | 0.2061 | 0.2730 | 0.071* | |
H4B | 0.3524 | 0.5010 | 0.2975 | 0.071* | |
C5 | 0.64690 (10) | 0.4785 (3) | 0.12217 (8) | 0.0361 (3) | |
C6 | 0.75069 (11) | 0.5867 (3) | 0.15619 (10) | 0.0466 (4) | |
H6 | 0.7671 | 0.7235 | 0.1984 | 0.056* | |
C7 | 0.83018 (11) | 0.4915 (3) | 0.12747 (9) | 0.0479 (4) | |
H7 | 0.8998 | 0.5649 | 0.1505 | 0.058* | |
C8 | 0.80668 (10) | 0.2874 (3) | 0.06466 (9) | 0.0407 (3) | |
C9 | 0.70189 (11) | 0.1846 (3) | 0.02946 (9) | 0.0471 (4) | |
H9 | 0.6850 | 0.0505 | −0.0136 | 0.057* | |
C10 | 0.62238 (11) | 0.2803 (3) | 0.05789 (9) | 0.0449 (4) | |
H10 | 0.5522 | 0.2111 | 0.0337 | 0.054* | |
C11 | 0.89105 (11) | 0.1726 (3) | 0.03496 (9) | 0.0447 (4) | |
H1 | 0.5640 (13) | 0.744 (4) | 0.1630 (10) | 0.049 (5)* | |
H3 | 1.0297 (19) | 0.200 (5) | 0.0483 (16) | 0.110 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0449 (6) | 0.0271 (6) | 0.0596 (7) | 0.0002 (5) | 0.0314 (6) | −0.0046 (5) |
O1 | 0.0739 (8) | 0.0284 (5) | 0.1042 (9) | 0.0011 (5) | 0.0621 (7) | −0.0012 (5) |
O2 | 0.0470 (6) | 0.0924 (10) | 0.0813 (8) | −0.0001 (6) | 0.0334 (6) | −0.0349 (7) |
O3 | 0.0408 (6) | 0.0872 (9) | 0.0737 (8) | −0.0002 (6) | 0.0300 (6) | −0.0204 (7) |
C1 | 0.0437 (7) | 0.0293 (7) | 0.0531 (8) | 0.0010 (5) | 0.0270 (6) | −0.0004 (5) |
C2 | 0.0569 (9) | 0.0321 (7) | 0.0781 (11) | −0.0027 (6) | 0.0457 (8) | −0.0058 (7) |
C3 | 0.0451 (8) | 0.0789 (12) | 0.0805 (12) | 0.0013 (8) | 0.0345 (8) | −0.0126 (10) |
C4 | 0.0635 (10) | 0.0607 (10) | 0.0722 (11) | −0.0040 (8) | 0.0474 (9) | −0.0034 (8) |
C5 | 0.0384 (7) | 0.0319 (6) | 0.0445 (7) | 0.0036 (5) | 0.0226 (6) | 0.0031 (5) |
C6 | 0.0456 (8) | 0.0478 (8) | 0.0527 (8) | −0.0067 (6) | 0.0252 (6) | −0.0136 (6) |
C7 | 0.0357 (7) | 0.0583 (9) | 0.0534 (8) | −0.0053 (6) | 0.0204 (6) | −0.0091 (7) |
C8 | 0.0385 (7) | 0.0473 (8) | 0.0413 (7) | 0.0064 (6) | 0.0206 (6) | 0.0030 (6) |
C9 | 0.0435 (7) | 0.0532 (9) | 0.0499 (8) | −0.0001 (6) | 0.0231 (6) | −0.0135 (7) |
C10 | 0.0349 (7) | 0.0503 (8) | 0.0524 (8) | −0.0026 (6) | 0.0193 (6) | −0.0098 (6) |
C11 | 0.0391 (7) | 0.0559 (9) | 0.0434 (7) | 0.0063 (6) | 0.0199 (6) | 0.0008 (7) |
N1—C1 | 1.3515 (17) | C4—H4A | 0.9700 |
N1—C5 | 1.4202 (16) | C4—H4B | 0.9700 |
N1—H1 | 0.827 (18) | C5—C10 | 1.3827 (19) |
O1—C1 | 1.2208 (17) | C5—C6 | 1.3832 (19) |
O2—C11 | 1.2249 (19) | C6—C7 | 1.3839 (19) |
O3—C11 | 1.3007 (18) | C6—H6 | 0.9300 |
O3—H3 | 0.870 (17) | C7—C8 | 1.386 (2) |
C1—C2 | 1.4753 (18) | C7—H7 | 0.9300 |
C2—C4 | 1.498 (2) | C8—C9 | 1.386 (2) |
C2—C3 | 1.501 (2) | C8—C11 | 1.4834 (18) |
C2—H2 | 0.9800 | C9—C10 | 1.3817 (19) |
C3—C4 | 1.452 (3) | C9—H9 | 0.9300 |
C3—H3A | 0.9700 | C10—H10 | 0.9300 |
C3—H3B | 0.9700 | ||
C1—N1—C5 | 124.04 (11) | C2—C4—H4B | 117.7 |
C1—N1—H1 | 117.4 (11) | H4A—C4—H4B | 114.8 |
C5—N1—H1 | 118.6 (11) | C10—C5—C6 | 119.67 (12) |
C11—O3—H3 | 107.8 (18) | C10—C5—N1 | 120.68 (12) |
O1—C1—N1 | 122.42 (12) | C6—C5—N1 | 119.65 (12) |
O1—C1—C2 | 121.98 (12) | C5—C6—C7 | 120.07 (13) |
N1—C1—C2 | 115.59 (12) | C5—C6—H6 | 120.0 |
C1—C2—C4 | 118.53 (13) | C7—C6—H6 | 120.0 |
C1—C2—C3 | 117.27 (13) | C6—C7—C8 | 120.44 (13) |
C4—C2—C3 | 57.93 (11) | C6—C7—H7 | 119.8 |
C1—C2—H2 | 116.7 | C8—C7—H7 | 119.8 |
C4—C2—H2 | 116.7 | C7—C8—C9 | 119.16 (12) |
C3—C2—H2 | 116.7 | C7—C8—C11 | 121.77 (13) |
C4—C3—C2 | 60.91 (11) | C9—C8—C11 | 119.06 (13) |
C4—C3—H3A | 117.7 | C10—C9—C8 | 120.42 (13) |
C2—C3—H3A | 117.7 | C10—C9—H9 | 119.8 |
C4—C3—H3B | 117.7 | C8—C9—H9 | 119.8 |
C2—C3—H3B | 117.7 | C9—C10—C5 | 120.19 (13) |
H3A—C3—H3B | 114.8 | C9—C10—H10 | 119.9 |
C3—C4—C2 | 61.15 (11) | C5—C10—H10 | 119.9 |
C3—C4—H4A | 117.7 | O2—C11—O3 | 123.00 (13) |
C2—C4—H4A | 117.7 | O2—C11—C8 | 121.50 (13) |
C3—C4—H4B | 117.7 | O3—C11—C8 | 115.50 (13) |
C5—N1—C1—O1 | 2.5 (2) | C5—C6—C7—C8 | −0.1 (2) |
C5—N1—C1—C2 | −177.69 (12) | C6—C7—C8—C9 | 1.6 (2) |
O1—C1—C2—C4 | 28.8 (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—C10 | 177.75 (13) |
N1—C1—C2—C3 | 142.56 (15) | C8—C9—C10—C5 | −0.4 (2) |
C1—C2—C3—C4 | 108.12 (16) | C6—C5—C10—C9 | 1.9 (2) |
C1—C2—C4—C3 | −105.96 (17) | N1—C5—C10—C9 | −178.93 (14) |
C1—N1—C5—C10 | 43.3 (2) | C7—C8—C11—O2 | 177.35 (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—C7 | 179.14 (13) | C9—C8—C11—O3 | 178.37 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.827 (18) | 2.144 (19) | 2.9273 (16) | 158.2 (16) |
O3—H3···O2ii | 0.87 (2) | 1.80 (2) | 2.6685 (15) | 173 (3) |
C2—H2···O1i | 0.98 | 2.37 | 3.2034 (18) | 142 |
C3—H3B···O2iii | 0.97 | 2.54 | 3.350 (2) | 141 |
Symmetry codes: (i) x, y+1, z; (ii) −x+2, −y, −z; (iii) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C11H11NO3 |
Mr | 205.21 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 13.2429 (14), 4.7704 (5), 16.7983 (18) |
β (°) | 111.227 (2) |
V (Å3) | 989.21 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.31 × 0.21 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.789, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5558, 1934, 1682 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.119, 1.05 |
No. of reflections | 1934 |
No. of parameters | 145 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.15, −0.20 |
Computer programs: SMART (Bruker, 2003), sAINT (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.827 (18) | 2.144 (19) | 2.9273 (16) | 158.2 (16) |
O3—H3···O2ii | 0.870 (17) | 1.803 (17) | 2.6685 (15) | 173 (3) |
C2—H2···O1i | 0.98 | 2.37 | 3.2034 (18) | 142 |
C3—H3B···O2iii | 0.97 | 2.54 | 3.350 (2) | 141 |
Symmetry codes: (i) x, y+1, z; (ii) −x+2, −y, −z; (iii) −x+1, −y, −z. |
Acknowledgements
This work was supported by the Fundamental Research Funds for the Central Universities.
References
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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.