1-(2-Amino-4, 5-dimethylphenyl) ethanone

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Feb 22, 2018 - Eric Bosch* and Laura Jeffries. Department of Chemistrry, Missouri State University, 901 South National Avenue, Springfield, MO 65804, USA.
data reports 1-(2-Amino-4,5-dimethylphenyl)ethanone Eric Bosch* and Laura Jeffries ISSN 2414-3146 Department of Chemistrry, Missouri State University, 901 South National Avenue, Springfield, MO 65804, USA. *Correspondence e-mail: [email protected]

Received 21 February 2018 Accepted 22 February 2018

Edited by J. Simpson, University of Otago, New Zealand

The molecule of the title compound, C10H13NO, also referred to as 2-amino-4,5dimethylacetophenone, lies on a crystallographic mirror plane with four molecules in the orthorhombic unit cell and features an intramolecular N— H  O hydrogen bond. In the crystal, the molecules are linked by N—H  O hydrogen bonds, forming ribbons along the a axis that pack to form sheets lying in the (010) plane.

Keywords: crystal structure; 2-aminoacetophenone; hydrogen bonding. CCDC reference: 1825318 Structural data: full structural data are available from iucrdata.iucr.org

Structure description The synthesis of 2-aminoacetophenone was accomplished in a one-pot reduction and hydration of 2-nitrophenacetylene with a variety of reagents generally used for the reduction of nitrobenzenes (Bosch & Jeffries, 2001). The asymmetric unit of the title compound comprises a single molecule that lies on a mirror plane with hydrogen atoms of the three methyl groups disordered over two positions. An intramolecular N1— H1N  O1 hydrogen bond (Fig. 1 and Table 1) supports the planar structure. A search of the Cambridge Structural Database (CSD, Version 5.39, November 2017, Groom et al., 2016) using Conquest (Bruno et al., 2002) for neutral uncomplexed molecules, including the 2-aminoacetophenone framework, yielded 99 hits. CSD entries not including atomic coordinates for H atoms were excluded. In 96 of these structures, an intramolecular N— H  O hydrogen bond was observed. In the crystal, ribbons form along the a-axis direction through N1—H2N  O1 hydrogen bonds. Adjacent ribbons pack to form sheets lying in the (010) plane (Fig. 2). These sheets stack parallel to (101). There are possible extremely weak offset – stacking interactions (Fig. 3), with a centroid-to-centroid distance between the stacked ˚ and with a slippage of 3.768 A ˚ . In addition, the closest benzene rings of 5.1075 (8) A contact between stacked molecules is between the acetophenone methyl group and the ˚ , suggesting that centroid of the benzene ring, with a C8  Cg1 distance of 3.4531 (3) A

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data reports Table 1

Table 2

˚ ,  ). Hydrogen-bond geometry (A

Experimental details.

D—H  A

D—H

H  A

D  A

D—H  A

N1—H1N  O1 N1—H2N  O1i

0.89 (2) 0.86 (2)

1.96 (2) 2.09 (2)

2.6603 (19) 2.9478 (18)

135 (2) 170 (2)

Symmetry code: (i) x þ 12; y; z þ 12.

Crystal data Chemical formula Mr Crystal system, space group Temperature (K) ˚) a, b, c (A ˚ 3) V (A Z Radiation type  (mm1) Crystal size (mm) Data collection Diffractometer Absorption correction Tmin, Tmax No. of measured, independent and observed [I > 2(I)] reflections Rint ˚ 1) (sin /)max (A

Figure 1 The asymmetric unit of the title compound, showing the atom-numbering scheme. Displacement ellipsoids of non-H atoms are drawn at the 50% probability level and H atoms are shown as circles of arbitrary size. An intramolecular hydrogen bond is shown as a dashed line.

C8—H8  Cg1 contacts may also consolidate the stacking interaction, Cg1 is the centroid of the C1–C6 benzene ring.

Synthesis and crystallization The title compound was synthesized by a one-pot hydration and reduction of 1-ethynyl-4,5-dimethyl-2-nitrobenzene with

Refinement R[F 2 > 2(F 2)], wR(F 2), S No. of reflections No. of parameters No. of restraints H-atom treatment ˚ 3) max, min (e A

C10H13NO 163.21 Orthorhombic, Pnma 173 10.4838 (7), 6.8965 (5), 12.8538 (9) 929.35 (11) 4 Mo K 0.08 0.33  0.32  0.21

Bruker APEXII CCD Multi-scan (SADABS; Bruker, 2014) 0.954, 1.000 11353, 1115, 883 0.028 0.641

0.040, 0.116, 1.09 1115 80 2 H atoms treated by a mixture of independent and constrained refinement 0.25, 0.19

Computer programs: SMART and SAINT (Bruker 2014), SHELXT2014 (Sheldrick, 2015a), SHELXL2017 (Sheldrick, 2015b) and X-SEED (Barbour, 2001).

Fe/HCl, SnCl2 or nickel boride and the isolation and characterization have been reported previously (Bosch & Jeffries, 2001). Crystals suitable for X-ray data collection were obtained by slow evaporation of a dichloromethane solution.

Refinement Crystal data, data collection and structure refinement details are summarized in Table 2.

Figure 2 A view of a sheet comprising side-by-side packing of one-dimensional hydrogen-bonded ribbons of the title compound. Hydrogen bonds are shown as a dashed lines.

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Figure 3 View along the a axis of the offset -stacked planes shown in Fig. 2. IUCrData (2018). 3, x180313

data reports Acknowledgements We thank the Missouri State University Provost Incentive Fund that funded the purchase of the X-ray diffractometer.

References Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. Bosch, E. & Jeffries, L. (2001). Tetrahedron Lett. 42, 8141–8142.

IUCrData (2018). 3, x180313

Bruker (2014). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389– 397. Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8.

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full crystallographic data IUCrData (2018). 3, x180313

[https://doi.org/10.1107/S2414314618003139]

1-(2-Amino-4,5-dimethylphenyl)ethanone Eric Bosch and Laura Jeffries 1-(2-Amino-4,5-dimethylphenyl)ethanone Crystal data C10H13NO Mr = 163.21 Orthorhombic, Pnma a = 10.4838 (7) Å b = 6.8965 (5) Å c = 12.8538 (9) Å V = 929.35 (11) Å3 Z=4 F(000) = 352

Dx = 1.167 Mg m−3 Mo Kα radiation, λ = 0.71073 Å Cell parameters from 2665 reflections θ = 2.5–26.4° µ = 0.08 mm−1 T = 173 K Cut block, yellow 0.33 × 0.32 × 0.21 mm

Data collection Bruker APEXII CCD diffractometer Radiation source: fine-focus sealed tube Graphite monochromator Detector resolution: 8.3660 pixels mm-1 phi and ω scans Absorption correction: multi-scan (SADABS; Bruker, 2014) Tmin = 0.954, Tmax = 1.000

11353 measured reflections 1115 independent reflections 883 reflections with I > 2σ(I) Rint = 0.028 θmax = 27.1°, θmin = 2.5° h = −13→13 k = −8→8 l = −16→16

Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.040 wR(F2) = 0.116 S = 1.09 1115 reflections 80 parameters 2 restraints

Hydrogen site location: mixed H atoms treated by a mixture of independent and constrained refinement w = 1/[σ2(Fo2) + (0.0555P)2 + 0.1911P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001 Δρmax = 0.25 e Å−3 Δρmin = −0.19 e Å−3

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.

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data-1

data reports Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

O1 N1 H1N H2N C1 C2 C7 C6 H6 C5 C8 H8A H8B H8C C3 H3 C4 C10 H10A H10B H10C C9 H9A H9B H9C

x

y

z

Uiso*/Ueq

Occ. (