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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2359.
Published online 2008 November 13. doi:  10.1107/S1600536808035277
PMCID: PMC2959954

3-(2-Acetyl­anilino)propanoic acid

Abstract

The title mol­ecule, C11H13NO3, has its propanoic acid group in an extended conformation, such that the mol­ecule is nearly planar, with a mean deviation of 0.036 Å [the maxima being 0.106 (1) and 0.110 (1) Å for the two methyl­ene C atoms]. The NH group forms an intra­molecular hydrogen bond with the acetyl group; in the crystal COOH group forms a centrosymmetric hydrogen-bonded dimer.

Related literature

For general background, see: Crosby et al. (1961 [triangle], 1962 [triangle]); Foley et al. (2003 [triangle]); Walker Jr et al. (2004 [triangle]); Yoshihara et al. (2001 [triangle]). For related structures, see: Slater et al. (2006 [triangle]). For hydrogen-bonding patterns, see: Etter (1990 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o2359-scheme1.jpg

Experimental

Crystal data

  • C11H13NO3
  • M r = 207.22
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2359-efi1.jpg
  • a = 5.1935 (10) Å
  • b = 9.8342 (16) Å
  • c = 9.920 (2) Å
  • α = 77.084 (12)°
  • β = 85.174 (11)°
  • γ = 83.019 (12)°
  • V = 489.32 (16) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 90.0 (5) K
  • 0.30 × 0.20 × 0.10 mm

Data collection

  • Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler
  • Absorption correction: none
  • 11014 measured reflections
  • 3012 independent reflections
  • 2467 reflections with I > 2s(I)
  • R int = 0.021

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.113
  • S = 1.04
  • 3012 reflections
  • 143 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.39 e Å−3
  • Δρmin = −0.29 e Å−3

Data collection: COLLECT (Nonius, 2000 [triangle]); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 [triangle]); data reduction: DENZO (Otwinowski & Minor, 1997 [triangle]) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808035277/pv2116sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808035277/pv2116Isup2.hkl

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

Acknowledgments

This research was made possible by a grant supplied by the National Science Foundation’s Early CAREER program (Cooperative Agreement DMR-0449886) at Southern University, and by a grant supplied by the US Deptartment of Education Title III Part B HBGI program (grant No. P031B040030) at Southern University. The purchase of the NMR was made possible by the National Science Foundation’s Major Research Instrument Program (Cooperative Agreement CHE-0321591) at Southern University. The purchase of the FTIR was made possible by grant No. LEQSF(2005–2007)-ENH-TR-65, and the purchase of the diffractometer was made possible by grant No. LEQSF (1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents.

supplementary crystallographic information

Comment

Since the discovery that energy transfer from the triplet state of an organic ligand can efficiently sensitize the emissive states of metal ions (Crosby et al., 1961; 1962) there has been considerable effort devoted to designing ligands that optimize this energy transfer and thus give efficient metal luminescence (Foley et al., 2003). The radiationless energy transfer photoluminescence and/or electro-luminescence properties of aromatic carbonyl compounds are strongly affected by the presence of a substituent on the aromatic ring. In general, the π, π* state is stabilized by introducing an electron-donating substituent on the aromatic ring, while the location of the n, π* state is only slightly modified by the electron-donating substituent. Thus, the fluorescence properties of the compounds with close-lying 1(n, π*) and 1(π, π*) states are expected to depend markedly on the nature of the solvent, such as its polarity and hydrogen-bonding ability. In 2'-aminoacetophenone, the 1(n, π*) and 1(π, π*) states are closely located in the lowest excited singlet state because of the presence of a strong electron-donating substituent. Owing to the proximity of two electronic levels, the photophysical properties of 2'-aminoacetophenone is very sensitive to environment, such as solvent polarity and temperature (Yoshihara et al., 2001). Therefore, the addition of a strong electron-donating substituent such as acrylic acid, which has the ability to form a solventless gel via hydrogen bonding, has been synthesized. The structure of the title compound, also known as 3-[(N-acetyl-phenyl)-azanediyl]-propionic acid, is herein described. Its synthesis takes advantage of the self-initiating condensation of 2'-aminoacetophenone with the vinyl group of the ab unsaturated acrylic acid via anti-Markovnikov addition, which is similar to chemistry involved in the synthesis of the novel 3,3',3"-nitrilotripropionic acid precursor gel that we have developed (Walker, et al., 2004).

The structure of the molecule is shown in Figure 1. The acetyl group is nearly coplanar with the phenyl group, the C2—C1—C7—O2 torsion angle being -1.64 (15)°. The NH(CH2)2COOH substituent is extended, with torsion angles C1—C2—N1—C9 - 176.52 (9), C2—N1—C9—C10 - 172.10 (9), N1—C9—C10—C11 179.81 (8), and C9—C10—C11—O2 173.73 (8)°. Thus, the molecule does not differ greatly from planarity, with mean and maximum deviations given in the abstract. The geometry of the intramolecular hydrogen bond, graph set S(6), (Etter, 1990) is given in Table 1, and is quite similar to that found in N-(2-acetylphenyl)acetamide (Slater et al., 2006). The COOH group forms a typical hydrogen bonded dimer of graph set R22(8) about an inversion center, thus there are no extended networks of traditional hydrogen bonds.

Experimental

A round bottom flask containing acrylic acid (1.051 g, 14.58 mmol) was stoppered and placed into the refrigerator overnight. In a similar round bottom flask, 2'-aminoacetophenoneHCl (1.0056 g, 0.79199 g of liberated 2-aminoacetophenone 5.861 mmol) was dissolved in 10 ml of deionized water and chilled overnight. The round bottom flask containing the cold acrylic acid was then placed into to an ice bath to maintain a temperature of approximately 273 K. The ice bath was used because the reaction of acrylic acid and 2'-aminoacetophenone was thought to be exothermic. The cold 2'-aminoacetophenone solution was slowly added with stirring to the cold acrylic acid. The mixture was allowed to sit in the ice bath for 30 minutes and then gradually warmed to room temperature, then kept at room temperature with continuous stirring overnight. A yellow precipitate was isolated by gravimetric filtration and washed with deionized water. The yellow solid material resulted in a yield of 0.8963 g (79.991%).

Refinement

H atoms on C were placed in idealized positions with C—H distances 0.95 - 0.99 Å and thereafter treated as riding. Coordinates for the H atoms on N and O were refined. Uiso for H was assigned as 1.2 times Ueq of the attached atoms (1.5 for methyl and OH). A torsional parameter was refined for the methyl group.

Figures

Fig. 1.
A view of the title compound; ellipsoids have been plotted at the 50% level and H atoms have been assigned arbitrary radii.

Crystal data

C11H13NO3Z = 2
Mr = 207.22F000 = 220
Triclinic, P1Dx = 1.406 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 5.1935 (10) ÅCell parameters from 2652 reflections
b = 9.8342 (16) Åθ = 2.5–30.8º
c = 9.920 (2) ŵ = 0.10 mm1
α = 77.084 (12)ºT = 90.0 (5) K
β = 85.174 (11)ºFragment, colorless
γ = 83.019 (12)º0.30 × 0.20 × 0.10 mm
V = 489.32 (16) Å3

Data collection

Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler2467 reflections with I > 2s(I)
Radiation source: fine-focus sealed tubeRint = 0.021
Monochromator: graphiteθmax = 30.8º
T = 90.0(5) Kθmin = 2.6º
ω scans with κ offsetsh = −7→7
Absorption correction: nonek = −13→13
11014 measured reflectionsl = −14→14
3012 independent reflections

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) = 0.113  w = 1/[σ2(Fo2) + (0.0573P)2 + 0.1339P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
3012 reflectionsΔρmax = 0.39 e Å3
143 parametersΔρmin = −0.29 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

Experimental. 1H (CDCl3): δ(p.p.m.) 9.02 (s, 1H), 7.78 (d, J = 8.0 Hz, 1H), 7.38 (t, J = 8.0 Hz, 1H), 6.74 (d, J = 8.0 Hz, 1H), 6.62 (t, J = 8.0 Hz, 1H), 3.58 (t, J = 7.0 Hz, 2H), 2.73 (t, J = 7.0 Hz, 2H), and 2.60 (s, 3H). 13C (CDCl3): δ (p.p.m.) 201.1, 176.7, 150.5, 135.2, 132.9, 117.9, 114.5, 111.3, 37.9, 33.8, and 27.9. IR (thin film, KBr plates, cm-1): 3297 (m), 2925 (w, br), 2881 (sh, w), 2635 (w), 2373 (w), 1698 (s), 1634 (s), 1569 (m), 1517 (m), 1430 (m), 1366 (sh), 1326(m), 1240 (s), 1156 (w), 1092(w), 1031(w), 943 (m), 825(w), 742 (m), 675(w), and 624 (w). Crystals were grown by evaporation from CDCl3.
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
O10.96261 (15)0.13504 (8)0.35274 (7)0.01656 (17)
O20.30686 (15)−0.07587 (8)0.93327 (7)0.01593 (17)
H2O0.183 (3)−0.0849 (15)1.0039 (16)0.024*
O30.04143 (14)0.11745 (8)0.85415 (7)0.01599 (17)
N10.53905 (17)0.21868 (9)0.49711 (8)0.01437 (18)
H1N0.673 (3)0.1541 (14)0.4924 (13)0.017*
C10.70722 (18)0.35189 (10)0.27655 (10)0.01194 (19)
C20.51897 (19)0.33391 (10)0.39115 (10)0.01242 (19)
C30.3083 (2)0.43948 (11)0.39170 (10)0.0161 (2)
H30.17870.42820.46570.019*
C40.2866 (2)0.55873 (11)0.28701 (11)0.0168 (2)
H40.14380.62830.29060.020*
C50.4725 (2)0.57819 (11)0.17590 (11)0.0165 (2)
H50.45810.66050.10430.020*
C60.6778 (2)0.47510 (10)0.17238 (10)0.0145 (2)
H60.80380.48790.09670.017*
C70.92650 (19)0.24478 (10)0.26361 (10)0.01281 (19)
C81.1133 (2)0.26868 (11)0.13707 (10)0.0157 (2)
H8A1.21160.34720.13860.024*
H8B1.01550.29050.05320.024*
H8C1.23370.18380.13740.024*
C90.34277 (19)0.19459 (11)0.61054 (10)0.0142 (2)
H9A0.17980.17670.57570.017*
H9B0.30600.27890.65080.017*
C100.43852 (19)0.06928 (10)0.72115 (10)0.01378 (19)
H10A0.4756−0.01450.68010.017*
H10B0.60250.08750.75480.017*
C110.24229 (19)0.04048 (10)0.84099 (10)0.01244 (19)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0166 (4)0.0146 (3)0.0149 (3)0.0019 (3)0.0026 (3)0.0012 (3)
O20.0148 (4)0.0162 (4)0.0127 (3)0.0014 (3)0.0038 (3)0.0020 (3)
O30.0152 (4)0.0162 (4)0.0132 (3)0.0019 (3)0.0041 (3)0.0003 (3)
N10.0136 (4)0.0144 (4)0.0111 (4)0.0025 (3)0.0048 (3)0.0014 (3)
C10.0110 (4)0.0123 (4)0.0114 (4)−0.0009 (3)0.0016 (3)−0.0012 (3)
C20.0127 (4)0.0134 (4)0.0104 (4)−0.0015 (3)0.0016 (3)−0.0018 (3)
C30.0145 (5)0.0179 (5)0.0141 (4)0.0014 (4)0.0030 (3)−0.0027 (4)
C40.0160 (5)0.0150 (5)0.0177 (5)0.0030 (4)0.0004 (4)−0.0030 (4)
C50.0174 (5)0.0135 (4)0.0162 (5)0.0002 (4)0.0000 (4)0.0005 (3)
C60.0152 (4)0.0145 (4)0.0125 (4)−0.0021 (4)0.0021 (3)−0.0006 (3)
C70.0115 (4)0.0146 (4)0.0118 (4)−0.0016 (3)0.0015 (3)−0.0024 (3)
C80.0146 (4)0.0162 (5)0.0136 (4)0.0001 (4)0.0045 (3)−0.0005 (3)
C90.0126 (4)0.0169 (5)0.0109 (4)−0.0001 (3)0.0033 (3)−0.0008 (3)
C100.0126 (4)0.0155 (4)0.0113 (4)−0.0007 (3)0.0028 (3)−0.0005 (3)
C110.0132 (4)0.0130 (4)0.0107 (4)−0.0022 (3)0.0015 (3)−0.0020 (3)

Geometric parameters (Å, °)

O1—C71.2384 (12)C4—H40.9500
O2—C111.3228 (12)C5—C61.3829 (14)
O2—H2O0.909 (16)C5—H50.9500
O3—C111.2278 (12)C6—H60.9500
N1—C21.3628 (12)C7—C81.5135 (13)
N1—C91.4519 (12)C8—H8A0.9800
N1—H1N0.887 (14)C8—H8B0.9800
C1—C61.4075 (13)C8—H8C0.9800
C1—C21.4299 (13)C9—C101.5193 (14)
C1—C71.4722 (14)C9—H9A0.9900
C2—C31.4145 (14)C9—H9B0.9900
C3—C41.3819 (14)C10—C111.4993 (13)
C3—H30.9500C10—H10A0.9900
C4—C51.3983 (15)C10—H10B0.9900
C11—O2—H2O108.7 (9)O1—C7—C8118.76 (9)
C2—N1—C9122.44 (8)C1—C7—C8119.13 (8)
C2—N1—H1N117.8 (9)C7—C8—H8A109.5
C9—N1—H1N119.7 (9)C7—C8—H8B109.5
C6—C1—C2118.53 (9)H8A—C8—H8B109.5
C6—C1—C7119.47 (9)C7—C8—H8C109.5
C2—C1—C7122.00 (8)H8A—C8—H8C109.5
N1—C2—C3120.39 (9)H8B—C8—H8C109.5
N1—C2—C1121.56 (9)N1—C9—C10109.68 (8)
C3—C2—C1118.05 (9)N1—C9—H9A109.7
C4—C3—C2121.48 (9)C10—C9—H9A109.7
C4—C3—H3119.3N1—C9—H9B109.7
C2—C3—H3119.3C10—C9—H9B109.7
C3—C4—C5120.76 (9)H9A—C9—H9B108.2
C3—C4—H4119.6C11—C10—C9111.66 (8)
C5—C4—H4119.6C11—C10—H10A109.3
C6—C5—C4118.62 (9)C9—C10—H10A109.3
C6—C5—H5120.7C11—C10—H10B109.3
C4—C5—H5120.7C9—C10—H10B109.3
C5—C6—C1122.54 (9)H10A—C10—H10B107.9
C5—C6—H6118.7O3—C11—O2122.63 (9)
C1—C6—H6118.7O3—C11—C10123.78 (9)
O1—C7—C1122.11 (9)O2—C11—C10113.59 (8)
C9—N1—C2—C33.20 (15)C2—C1—C6—C5−0.84 (15)
C9—N1—C2—C1−176.52 (9)C7—C1—C6—C5178.13 (10)
C6—C1—C2—N1−178.48 (9)C6—C1—C7—O1179.42 (9)
C7—C1—C2—N12.57 (15)C2—C1—C7—O1−1.64 (15)
C6—C1—C2—C31.80 (14)C6—C1—C7—C8−0.98 (14)
C7—C1—C2—C3−177.15 (9)C2—C1—C7—C8177.96 (9)
N1—C2—C3—C4178.57 (10)C2—N1—C9—C10−172.10 (9)
C1—C2—C3—C4−1.71 (15)N1—C9—C10—C11179.81 (8)
C2—C3—C4—C50.58 (16)C9—C10—C11—O3−6.99 (14)
C3—C4—C5—C60.45 (16)C9—C10—C11—O2173.73 (8)
C4—C5—C6—C1−0.30 (16)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2O···O3i0.909 (16)1.747 (16)2.6531 (11)174.7 (14)
N1—H1N···O10.887 (14)1.980 (14)2.6690 (12)133.4 (11)

Symmetry codes: (i) −x, −y, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2116).

References

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