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Acta Crystallogr Sect E Struct Rep Online. 2011 October 1; 67(Pt 10): o2606.
Published online 2011 September 14. doi:  10.1107/S1600536811036300
PMCID: PMC3201243

Ethyl 4-[3-(1H-imidazol-1-yl)propyl­amino]-3-nitro­benzoate

Abstract

In the title compound, C15H18N4O4, the 1H-imidazole ring forms a dihedral angle of 67.12 (8)° with the benzene ring. An S(6) ring motif is formed via an intra­molecular N—H(...)O hydrogen bond. In the crystal, neighbouring mol­ecules are linked by a pair of inter­molecular N—H(...)N hydrogen bonds, forming an inversion dimer. The dimers are further linked by a pair of C—H(...)O hydrogen bonds, leading to the formation of chain along [021]. A C—H(...)π inter­action involving the centroid of the benzene ring is also observed between the chains.

Related literature

For applications of phenyl­enediamines, see: Sabelle (2006 [triangle]); Glebowska et al. (2009 [triangle]); Remusat et al. (2004 [triangle]). For hydrogen-bond motifs, see: Bernstein et al. (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-67-o2606-scheme1.jpg

Experimental

Crystal data

  • C15H18N4O4
  • M r = 318.33
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-67-o2606-efi1.jpg
  • a = 8.4860 (4) Å
  • b = 8.6175 (4) Å
  • c = 11.7507 (6) Å
  • α = 77.489 (1)°
  • β = 81.732 (1)°
  • γ = 67.977 (1)°
  • V = 775.83 (7) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 297 K
  • 0.43 × 0.37 × 0.23 mm

Data collection

  • Bruker SMART APEXII DUO CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.958, T max = 0.978
  • 15358 measured reflections
  • 4470 independent reflections
  • 3627 reflections with I > 2σ(I)
  • R int = 0.021

Refinement

  • R[F 2 > 2σ(F 2)] = 0.049
  • wR(F 2) = 0.173
  • S = 1.05
  • 4470 reflections
  • 213 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811036300/is2771sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036300/is2771Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811036300/is2771Isup3.cml

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

Acknowledgments

The authors wish to express their thanks to Universiti Sains Malaysia (USM), Penang, Malaysia, for providing research facilities. HKF and WSL thank USM for the Research University Grant (1001/PFIZIK/811160). WSL also thanks the Malaysian Government and USM for the award of a research fellowship.

supplementary crystallographic information

Comment

Nitrophenyleneamine is an important class of compounds in organic synthetic chemistry. They are most of the time used to synthesize phenylenediamines by reducing the nitro (NO2) group to amine (NH2). Phenylenediamines themselves are then used as composition in making dyes (Sabelle, 2006), metallomesogens (Glebowska et al., 2009) as well as ligand precursors. Condensation of substituted o-phenylenediamine with various diketones is then used in the preparation of a variety of pharmaceuticals (Remusat et al., 2004).

In the title compound (Fig. 1), the 1H-imidazole (C1/C2/N3/C3/N2) is almost planar with a maximum deviation of 0.003 (2) Å at atom C3 and it forms a dihedral angle of 67.12 (8)° with the benzene ring (C7–C12). An S(6) ring motif (Bernstein et al., 1995) is formed via an intramolecular N1—H1N1···O2 hydrogen bond (Table 1).

In the crystal packing (Fig. 2), pairs of intermolecular N1—H1N1···N3 and C15—H15A···O1 hydrogen bonds (Table 1) link the neighbouring molecules to form dimers, leading to the formation of chains along the [021]. The crystal packing is further stabilized by a C—H···π interaction (Table 1), involving the centroid of the benzene ring (Cg1).

Experimental

Ethyl-4-fluro-3-nitro benzoate (4.6 mmol) in dichloromethane (20 mL) was added into the solution of 3-(1H-imidazole-1yl)propane-1-amine (7.0 mmol) and N, N-diisopropylethylamine (5.6 mmol) in dichloromethane (20 mL). The reaction mixture was stirred overnight at room temperature. After completion of the reaction, evidenced by TLC analysis. The reaction mixture was washed with water (10 mL × 2) and 10% Na2CO3 (10 ml × 2). The dichloromethane layer was collected and dried over Na2SO4. The organic layer was concentrated under reduced pressure to afford white-colored crystals.

Refinement

Atom H1N1 was located in a difference Fourier map and was refined freely. The remaining H atoms were positioned geometrically and refined using a riding model, with Uiso(H) = 1.2 or 1.5Ueq(C) (C—H = 0.93–0.97 Å). A rotating group model was applied to the methyl group. Three outliners were omitted for the final refinement, 0 -1 4, -5 0 4 and -4 0 5.

Figures

Fig. 1.
The molecular structure of the title compound, showing 30% probability displacement ellipsoids. The dashed line indicates the intramolecular hydrogen bond.
Fig. 2.
The crystal packing of the title compound, viewed along the a axis. H atoms not involved in the intermolecular interactions (dashed lines) have been omitted for clarity.

Crystal data

C15H18N4O4Z = 2
Mr = 318.33F(000) = 336
Triclinic, P1Dx = 1.363 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.4860 (4) ÅCell parameters from 6626 reflections
b = 8.6175 (4) Åθ = 2.6–32.5°
c = 11.7507 (6) ŵ = 0.10 mm1
α = 77.489 (1)°T = 297 K
β = 81.732 (1)°Block, yellow
γ = 67.977 (1)°0.43 × 0.37 × 0.23 mm
V = 775.83 (7) Å3

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer4470 independent reflections
Radiation source: fine-focus sealed tube3627 reflections with I > 2σ(I)
graphiteRint = 0.021
[var phi] and ω scansθmax = 30.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)h = −11→11
Tmin = 0.958, Tmax = 0.978k = −11→12
15358 measured reflectionsl = −16→16

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.173H atoms treated by a mixture of independent and constrained refinement
S = 1.05w = 1/[σ2(Fo2) + (0.1056P)2 + 0.1039P] where P = (Fo2 + 2Fc2)/3
4470 reflections(Δ/σ)max = 0.001
213 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = −0.23 e Å3

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
O10.70039 (15)1.08819 (19)0.76638 (14)0.0819 (4)
O20.66111 (13)0.92725 (15)0.66648 (11)0.0630 (3)
O30.28465 (12)1.36380 (12)1.04716 (9)0.0495 (2)
O40.04276 (15)1.30975 (15)1.09224 (9)0.0602 (3)
N10.39536 (14)0.82823 (14)0.71627 (10)0.0439 (3)
N20.16593 (13)0.56169 (13)0.55424 (9)0.0411 (2)
N30.32584 (19)0.38579 (17)0.43667 (11)0.0598 (3)
N40.61326 (13)1.01531 (14)0.74276 (10)0.0457 (3)
C10.1987 (2)0.4015 (2)0.61436 (12)0.0579 (4)
H1A0.16130.37020.69120.069*
C20.2965 (2)0.29595 (19)0.54111 (13)0.0586 (4)
H2A0.33760.17790.56010.070*
C30.2444 (2)0.5452 (2)0.44782 (13)0.0605 (4)
H3A0.24150.63680.38830.073*
C40.06090 (17)0.72024 (18)0.59566 (13)0.0511 (3)
H4A0.00240.69340.67020.061*
H4B−0.02490.78780.54060.061*
C50.16440 (18)0.82458 (16)0.60979 (12)0.0487 (3)
H5A0.08790.93130.63180.058*
H5B0.22400.85050.53550.058*
C60.29333 (16)0.73156 (15)0.70181 (11)0.0423 (3)
H6A0.23320.70640.77600.051*
H6B0.36860.62420.68010.051*
C70.34741 (14)0.94586 (14)0.78555 (10)0.0364 (2)
C80.18281 (16)0.98950 (16)0.84576 (11)0.0432 (3)
H8A0.10760.94080.83270.052*
C90.13241 (16)1.10113 (16)0.92231 (11)0.0435 (3)
H9A0.02381.12610.95980.052*
C100.23935 (15)1.17874 (14)0.94578 (10)0.0383 (2)
C110.39749 (15)1.14588 (14)0.88549 (10)0.0379 (2)
H11A0.46951.19850.89820.045*
C120.44984 (14)1.03452 (14)0.80583 (10)0.0361 (2)
C130.17697 (17)1.28977 (15)1.03544 (10)0.0417 (3)
C140.22780 (19)1.47706 (18)1.13211 (12)0.0512 (3)
H14A0.24021.41151.21070.061*
H14B0.10871.54751.12450.061*
C150.3332 (3)1.5847 (2)1.10987 (17)0.0705 (5)
H15A0.29721.66121.16480.106*
H15B0.32031.64881.03190.106*
H15C0.45061.51401.11850.106*
H1N10.495 (2)0.808 (2)0.6809 (15)0.058 (5)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0597 (7)0.1035 (10)0.1167 (11)−0.0523 (7)0.0326 (7)−0.0724 (9)
O20.0512 (5)0.0719 (7)0.0792 (7)−0.0281 (5)0.0258 (5)−0.0497 (6)
O30.0513 (5)0.0525 (5)0.0546 (5)−0.0209 (4)0.0062 (4)−0.0319 (4)
O40.0660 (6)0.0713 (7)0.0563 (6)−0.0357 (5)0.0245 (5)−0.0365 (5)
N10.0431 (5)0.0441 (5)0.0525 (6)−0.0187 (4)0.0085 (4)−0.0272 (4)
N20.0406 (5)0.0477 (5)0.0404 (5)−0.0169 (4)0.0025 (4)−0.0202 (4)
N30.0698 (8)0.0594 (7)0.0533 (7)−0.0226 (6)0.0142 (6)−0.0296 (6)
N40.0406 (5)0.0446 (5)0.0577 (6)−0.0183 (4)0.0090 (4)−0.0235 (5)
C10.0748 (9)0.0574 (8)0.0400 (6)−0.0233 (7)0.0052 (6)−0.0120 (6)
C20.0720 (9)0.0480 (7)0.0528 (8)−0.0128 (6)−0.0063 (7)−0.0170 (6)
C30.0832 (10)0.0545 (8)0.0434 (7)−0.0261 (7)0.0163 (7)−0.0186 (6)
C40.0396 (6)0.0556 (7)0.0600 (8)−0.0093 (5)−0.0002 (5)−0.0302 (6)
C50.0544 (7)0.0413 (6)0.0514 (7)−0.0126 (5)−0.0025 (5)−0.0194 (5)
C60.0470 (6)0.0380 (5)0.0482 (6)−0.0172 (5)0.0019 (5)−0.0203 (5)
C70.0416 (5)0.0336 (5)0.0368 (5)−0.0146 (4)0.0032 (4)−0.0133 (4)
C80.0458 (6)0.0454 (6)0.0478 (6)−0.0245 (5)0.0110 (5)−0.0215 (5)
C90.0470 (6)0.0436 (6)0.0454 (6)−0.0221 (5)0.0132 (5)−0.0193 (5)
C100.0463 (6)0.0359 (5)0.0357 (5)−0.0165 (4)0.0053 (4)−0.0144 (4)
C110.0416 (5)0.0356 (5)0.0407 (5)−0.0157 (4)0.0012 (4)−0.0143 (4)
C120.0373 (5)0.0344 (5)0.0386 (5)−0.0136 (4)0.0043 (4)−0.0136 (4)
C130.0500 (6)0.0406 (6)0.0379 (5)−0.0179 (5)0.0047 (4)−0.0159 (4)
C140.0616 (8)0.0506 (7)0.0481 (7)−0.0195 (6)0.0019 (6)−0.0275 (5)
C150.0860 (12)0.0714 (10)0.0742 (10)−0.0428 (9)0.0087 (9)−0.0364 (8)

Geometric parameters (Å, °)

O1—N41.2251 (15)C5—C61.5217 (19)
O2—N41.2261 (14)C5—H5A0.9700
O3—C131.3313 (15)C5—H5B0.9700
O3—C141.4533 (14)C6—H6A0.9700
O4—C131.2067 (16)C6—H6B0.9700
N1—C71.3449 (13)C7—C81.4249 (16)
N1—C61.4551 (15)C7—C121.4257 (15)
N1—H1N10.856 (19)C8—C91.3686 (15)
N2—C31.3395 (16)C8—H8A0.9300
N2—C11.3518 (19)C9—C101.3978 (17)
N2—C41.4657 (15)C9—H9A0.9300
N3—C31.3120 (19)C10—C111.3826 (16)
N3—C21.346 (2)C10—C131.4840 (15)
N4—C121.4440 (15)C11—C121.3944 (14)
C1—C21.351 (2)C11—H11A0.9300
C1—H1A0.9300C14—C151.476 (2)
C2—H2A0.9300C14—H14A0.9700
C3—H3A0.9300C14—H14B0.9700
C4—C51.5186 (19)C15—H15A0.9600
C4—H4A0.9700C15—H15B0.9600
C4—H4B0.9700C15—H15C0.9600
C13—O3—C14115.30 (10)C5—C6—H6B108.9
C7—N1—C6124.49 (10)H6A—C6—H6B107.8
C7—N1—H1N1116.5 (12)N1—C7—C8119.86 (10)
C6—N1—H1N1119.0 (12)N1—C7—C12125.14 (10)
C3—N2—C1105.75 (12)C8—C7—C12115.00 (9)
C3—N2—C4127.17 (12)C9—C8—C7121.81 (11)
C1—N2—C4127.05 (11)C9—C8—H8A119.1
C3—N3—C2104.48 (12)C7—C8—H8A119.1
O1—N4—O2121.58 (11)C8—C9—C10121.93 (11)
O1—N4—C12119.17 (10)C8—C9—H9A119.0
O2—N4—C12119.25 (10)C10—C9—H9A119.0
C2—C1—N2106.62 (13)C11—C10—C9118.24 (10)
C2—C1—H1A126.7C11—C10—C13123.90 (11)
N2—C1—H1A126.7C9—C10—C13117.86 (10)
N3—C2—C1110.43 (13)C10—C11—C12120.55 (11)
N3—C2—H2A124.8C10—C11—H11A119.7
C1—C2—H2A124.8C12—C11—H11A119.7
N3—C3—N2112.72 (13)C11—C12—C7122.29 (10)
N3—C3—H3A123.6C11—C12—N4116.41 (10)
N2—C3—H3A123.6C7—C12—N4121.29 (9)
N2—C4—C5112.73 (10)O4—C13—O3123.64 (11)
N2—C4—H4A109.0O4—C13—C10123.26 (11)
C5—C4—H4A109.0O3—C13—C10113.10 (10)
N2—C4—H4B109.0O3—C14—C15108.04 (12)
C5—C4—H4B109.0O3—C14—H14A110.1
H4A—C4—H4B107.8C15—C14—H14A110.1
C4—C5—C6112.09 (11)O3—C14—H14B110.1
C4—C5—H5A109.2C15—C14—H14B110.1
C6—C5—H5A109.2H14A—C14—H14B108.4
C4—C5—H5B109.2C14—C15—H15A109.5
C6—C5—H5B109.2C14—C15—H15B109.5
H5A—C5—H5B107.9H15A—C15—H15B109.5
N1—C6—C5113.19 (11)C14—C15—H15C109.5
N1—C6—H6A108.9H15A—C15—H15C109.5
C5—C6—H6A108.9H15B—C15—H15C109.5
N1—C6—H6B108.9
C3—N2—C1—C20.29 (18)C9—C10—C11—C12−1.70 (18)
C4—N2—C1—C2178.23 (13)C13—C10—C11—C12177.37 (10)
C3—N3—C2—C1−0.4 (2)C10—C11—C12—C7−2.12 (18)
N2—C1—C2—N30.0 (2)C10—C11—C12—N4176.86 (11)
C2—N3—C3—N20.6 (2)N1—C7—C12—C11−175.11 (11)
C1—N2—C3—N3−0.5 (2)C8—C7—C12—C114.66 (17)
C4—N2—C3—N3−178.48 (13)N1—C7—C12—N45.96 (19)
C3—N2—C4—C5−70.00 (19)C8—C7—C12—N4−174.27 (11)
C1—N2—C4—C5112.49 (16)O1—N4—C12—C114.07 (19)
N2—C4—C5—C6−62.97 (15)O2—N4—C12—C11−175.55 (12)
C7—N1—C6—C585.02 (15)O1—N4—C12—C7−176.93 (13)
C4—C5—C6—N1179.45 (10)O2—N4—C12—C73.44 (19)
C6—N1—C7—C8−3.56 (19)C14—O3—C13—O4−1.8 (2)
C6—N1—C7—C12176.19 (11)C14—O3—C13—C10178.66 (10)
N1—C7—C8—C9176.17 (12)C11—C10—C13—O4−175.61 (13)
C12—C7—C8—C9−3.61 (18)C9—C10—C13—O43.5 (2)
C7—C8—C9—C100.0 (2)C11—C10—C13—O33.97 (18)
C8—C9—C10—C112.76 (19)C9—C10—C13—O3−176.96 (11)
C8—C9—C10—C13−176.37 (12)C13—O3—C14—C15−163.51 (13)

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C7–C12 benzene ring.
D—H···AD—HH···AD···AD—H···A
N1—H1N1···O20.859 (18)2.004 (18)2.6464 (18)130.9 (15)
N1—H1N1···N3i0.859 (18)2.345 (17)3.0281 (18)136.7 (15)
C15—H15A···O1ii0.962.473.346 (2)151
C1—H1A···Cg1iii0.932.903.5962 (16)132

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+3, −z+2; (iii) x, y−1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS2771).

References

  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.
  • Bruker (2009). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Glebowska, A., Przybylski, P., Winek, M., Krzyczkowska, P., Krówczyński, A., Szydłowska, J., Pociecha, D. & Górecka, E. (2009). J. Mater. Chem. 19, 1395–1398.
  • Remusat, V., Terme, T., Gellis, A., Rathelot, P. & Vanelle, P. (2004). J. Heterocycl. Chem. 41, 221–225.
  • Sabelle, S. (2006). US Patent 20060005323.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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