Hirshfeld surface analysis and crystal structure of N-(2-meth­oxy­phen­yl)acetamide

Yaman, M.; Dege, N.; Ayoob, M.M.; Hussein, A.J.; Samad, M.K.; Fritsky, I.O.

doi:10.1107/S2056989019006972

research communications

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Volume 75| Part 6| June 2019| Pages 830-833

https://doi.org/10.1107/S2056989019006972

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Hirshfeld surface analysis and crystal structure of N-(2-methoxyphenyl)acetamide

Mavise Yaman,^a ^* Necmi Dege,^a ^* Mzgin M. Ayoob,^b Awaz J. Hussein,^b Mohammed K. Samad ^c and Igor O. Fritsky ^d ^*

^aOndokuz Mayıs University, Faculty of Arts and Sciences, Department of Physics, 55139, Samsun, Turkey, ^bDepartment of Chemistry, College of Education, Salahaddin University-Erbil, Erbil-Kurdistan, Iraq, 44002, ^cDepartment of Chemistry, College of Education, Salahaddin University – Hawler, Erbil-Kurdistan, Iraq, and ^dTaras Shevchenko National University of Kyiv, Department of Chemistry, 64, Vladimirska Str., Kiev 01601, Ukraine
^*Correspondence e-mail: maviseseker@hotmail.com, necmid@omu.edu.tr, ifritsky@univ.kiev.ua

Edited by J. T. Mague, Tulane University, USA (Received 16 April 2019; accepted 14 May 2019; online 21 May 2019)

The title compound, C₉H₁₁NO₂, was obtained as unexpected product from the reaction of (4-{2-benzyloxy-5-[(E)-(3-chloro-4-methylphenyl)diazenyl]benzylidene}-2-phenyloxazol-5(4H)-one) with 2-methoxyaniline in the presence of acetic acid as solvent. The amide group is not coplanar with the benzene ring, as shown by the C—N—C—O and C—N—C—C torsion angles of −2.5 (3) and 176.54 (19)°, respectively. Hirshfeld surface analysis and two-dimensional fingerprint plots indicate that the most important contributions to the crystal packing are from H⋯H (53.9%), C⋯H/H⋯C (21.4%), O⋯H/H⋯O (21.4%) and N⋯H/H⋯N (1.7%) interactions.

Keywords: crystal structure; hydrogen bonding; amide; methoxyphenyl; Hirshfeld surface analysis.

CCDC reference: 1899995

1. Chemical context

The amide function is one of the most important linkages in natural chemistry. It is the key linker in peptides and a number of polymers, and is additionally found in numerous pharmaceuticals and other items (Dam et al., 2010 ) with natural activity, including about 25% of commercially available drugs. Consequentially, the amide bond is a standout amongst the most vital changes in a current natural blend (Ojeda-Porras & Gamba-Sánchez, 2016 ). In the light of such discoveries, we report the crystal structure of the title compound.

2. Structural commentary

The molecular structure of the asymmetric unit of the C₉H₁₁NO₂ compound is shown in Fig. 1. The N1—C2, C2—O2 and C2—C1 bond lengths are 1.347 (2), 1.2285 (19) and 1.480 (3) Å, respectively. The C2—O2 bond in the amide group shows partial double-bond character and is similar in length to those found in amide compounds in the literature [1.215 (2) Å (Kansiz et al., 2018 ), 1.240 (2) Å (Aydemir et al., 2018 ) and 1.2205 (10) Å (Chkirate et al., 2019 )]. The C3—C8 benzene ring is planar with an r.m.s. deviation of 0.0019. The amide group is not coplanar with the benzene ring, as shown by the C3—N1—C2—O2 and C3—N1—C2—C1 torsion angles of −2.5 (3) and 176.54 (19)°, respectively.

Figure 1
The asymmetric unit of the title compound with displacement ellipsoids drawn at the 50% probability level.

3. Supramolecular features

In the crystal, adjacent molecules are linked by weak C—H⋯O hydrogen bonds, forming supramolecular chains propagating along the a-axis direction (Table 1 and Fig. 2). The chains are further connected by weak C—H⋯π interactions.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C3–C8 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.86	2.10	2.9486 (17)	168
C1—H1B⋯O2ⁱ	0.96	2.56	3.378 (2)	143
C1—H9B⋯Cg1ⁱⁱ	0.96	2.61	3.387	139
Symmetry codes: (i) $[x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (ii) $[-x-1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
A partial view of the crystal packing. Dashed lines denote the intermolecular C—H⋯O and N—H⋯O hydrogen bonds (Table 1

4. Hirshfeld surface analysis

Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) and the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ) were generated using CrystalExplorer17 (Turner et al., 2017 ). Plots of the Hirshfeld surface mapped over d_norm, d_i and d_e using a fixed colour scale of −0.5051 (red) to 1.2978 (blue) a.u. are shown in Fig. 3.. The red spots in the d_norm plot indicate the intermolecular contacts associated with the strong hydrogen bonds and interatomic contacts such as N—H⋯O. Fig. 4 shows the d_norm mapped on the Hirshfeld surface to visualize the intermolecular interactions of the title compound. The fingerprint plots complement the Hirshfeld surface, quantitatively summarizing the nature and type of the intermolecular contacts by illustrating atom_inside/atom_outside interactions (Fig. 5). The contribution from the H⋯H contacts is observed to be highest towards the Hirshfeld surface with a 53.9% contribution. The contribution from the C—H⋯O hydrogen bond (21.4% contribution) appears as a pair of sharp spikes at d_e + d_i =1.9 Å. A view of the three-dimensional Hirshfeld surface plotted over electrostatic potentials in the range −0.1028 to 0.1158 a.u. is shown in Fig. 6. The hydrogen-bond donors and acceptors are showed as blue and red regions around the atoms corresponding to positive and negative potentials, respectively.

Figure 3
The Hirshfeld surface of the title compound mapped over d_norm, d_i and d_e.

Figure 4
d_norm mapped on the Hirshfeld surface for visualizing the intermolecular interactions of the title compound.

Figure 5
Two-dimensional fingerprint plots with a d_norm view of the H⋯H/H⋯H (53.9%), C⋯H/H⋯C (21.4%), O⋯H/H⋯O (21.4%) and N⋯H/ H⋯N (1.7%) contacts in the title compound.

Figure 6
The view of the three-dimensional Hirshfeld surface of the title compound plotted over the electrostatic potentials.

5. Database survey

A search in the Cambridge Structural Database (CSD version 5.39, update of August 2018; Groom et al., 2016 ) for N-(2-methoxyphenyl)acetamide derivatives found several similar structures: 3-hydroxy-7,8-dimethoxyquinolin-2(1H)-one (BIZGAT; Song et al., 2008 ), 1-(2-methoxyphenyl)-1H-pyrrole-2,5-dione (XEBZIP; Sirajuddin et al., 2012 ) and cis-cyclohexane-1,2-carboxylic anhydride with o- and p-anisidine and m- and p-aminobenzoic acids (BECVAI; Smith et al., 2012 ). In the structure of BIZGAT, the molecules are linked into chains by N—H⋯O hydrogen bonds as in the title structure.

6. Synthesis and crystallization

This compound was formed as by-product in the synthesis of a benzamide derivative from the reaction between an oxazolone with o- methoxyaniline (Samad & Hawaiz, 2019 ) in the presence of acetic acid as solvent. The reaction mixture was refluxed for 2 h, cooled, poured into water, filtered and dried. The remaining filtrate was left for seven days to obtain good-quality crystals.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The H atoms were positioned geometrically and refined using a riding model with C—H = 0.93 Å for aromatic H atoms, C—H = 0.96 Å for methyl H atoms, and with U_iso(H) = 1.2–1.5 U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	C₉H₁₁NO₂
M_r	165.19
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	9.5115 (7), 18.7385 (19), 10.0216 (8)
V (Å³)	1786.2 (3)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.43 × 0.39 × 0.37

Data collection
Diffractometer	Stoe IPDS 2
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002 )
T_min, T_max	0.946, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	14575, 1748, 1168
R_int	0.090
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.148, 1.05
No. of reflections	1748
No. of parameters	111
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.12
Computer programs: X-AREA and X-RED32 (Stoe & Cie, 2002), SHELXT2018 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ), Mercury (Macrae et al., 2006 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1899995

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019006972/mw2145sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019006972/mw2145Isup2.hkl

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b), WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

N-(2-Methoxyphenyl)acetamide top

Crystal data top

C₉H₁₁NO₂	D_x = 1.229 Mg m⁻³
M_r = 165.19	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 26458 reflections
a = 9.5115 (7) Å	θ = 2.0–28.3°
b = 18.7385 (19) Å	µ = 0.09 mm⁻¹
c = 10.0216 (8) Å	T = 296 K
V = 1786.2 (3) Å³	Prism, yellow
Z = 8	0.43 × 0.39 × 0.37 mm
F(000) = 704

Data collection top

Stoe IPDS 2 diffractometer	1748 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	1168 reflections with I > 2σ(I)
Plane graphite monochromator	R_int = 0.090
Detector resolution: 6.67 pixels mm^-1	θ_max = 26.0°, θ_min = 2.2°
rotation method scans	h = −11→10
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −22→22
T_min = 0.946, T_max = 0.978	l = −12→12
14575 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.050	H-atom parameters constrained
wR(F²) = 0.148	w = 1/[σ²(F_o²) + (0.0718P)²] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1748 reflections	Δρ_max = 0.13 e Å⁻³
111 parameters	Δρ_min = −0.12 e Å⁻³

Special details top

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.

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

	x	y	z	U_iso*/U_eq
O1	0.64879 (13)	0.70439 (8)	0.55583 (15)	0.0835 (5)
O2	0.25840 (10)	0.58665 (10)	0.69551 (15)	0.0943 (6)
N1	0.49079 (12)	0.60150 (8)	0.65857 (16)	0.0654 (5)
H1	0.572027	0.603270	0.696112	0.078*
C3	0.48608 (15)	0.61300 (10)	0.5196 (2)	0.0622 (5)
C8	0.57097 (16)	0.66649 (11)	0.4655 (2)	0.0678 (5)
C2	0.37959 (16)	0.58800 (10)	0.7378 (2)	0.0702 (5)
C4	0.40284 (18)	0.57277 (11)	0.4362 (2)	0.0739 (6)
H4	0.346101	0.537006	0.471444	0.089*
C7	0.5712 (2)	0.67836 (14)	0.3299 (2)	0.0872 (7)
H7	0.627687	0.713842	0.293428	0.105*
C1	0.4131 (2)	0.57364 (14)	0.8795 (2)	0.0937 (8)
H1A	0.349072	0.599462	0.935617	0.141*
H1B	0.507637	0.588706	0.897970	0.141*
H1C	0.404506	0.523450	0.896863	0.141*
C5	0.4032 (2)	0.58533 (13)	0.3000 (3)	0.0917 (7)
H5	0.346474	0.558364	0.243764	0.110*
C6	0.4874 (2)	0.63744 (16)	0.2492 (3)	0.0996 (8)
H6	0.487972	0.645447	0.157579	0.119*
C9	0.7372 (2)	0.75987 (14)	0.5065 (3)	0.1092 (9)
H9A	0.802856	0.740327	0.443554	0.164*
H9B	0.787667	0.781102	0.579383	0.164*
H9C	0.680779	0.795524	0.463403	0.164*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0703 (8)	0.0959 (10)	0.0843 (11)	−0.0264 (7)	0.0062 (7)	−0.0008 (8)
O2	0.0401 (6)	0.1531 (15)	0.0896 (11)	−0.0056 (7)	0.0017 (6)	0.0087 (10)
N1	0.0397 (6)	0.0882 (11)	0.0682 (11)	−0.0052 (6)	−0.0012 (6)	0.0051 (8)
C3	0.0445 (7)	0.0737 (11)	0.0683 (13)	0.0031 (7)	0.0007 (7)	−0.0008 (9)
C8	0.0530 (8)	0.0804 (12)	0.0699 (14)	0.0004 (9)	0.0043 (8)	0.0014 (10)
C2	0.0459 (8)	0.0903 (14)	0.0744 (14)	−0.0029 (9)	0.0031 (8)	0.0061 (11)
C4	0.0579 (9)	0.0824 (13)	0.0813 (16)	−0.0002 (9)	−0.0059 (9)	−0.0065 (11)
C7	0.0767 (13)	0.1117 (18)	0.0732 (17)	0.0005 (12)	0.0110 (11)	0.0104 (13)
C1	0.0611 (11)	0.142 (2)	0.0778 (16)	−0.0005 (12)	0.0054 (10)	0.0168 (14)
C5	0.0773 (12)	0.1154 (19)	0.0823 (17)	0.0060 (13)	−0.0135 (12)	−0.0179 (14)
C6	0.0955 (16)	0.134 (2)	0.0697 (16)	0.0068 (15)	0.0001 (12)	0.0016 (16)
C9	0.0960 (15)	0.1067 (18)	0.125 (2)	−0.0392 (14)	0.0343 (15)	−0.0085 (17)

Geometric parameters (Å, º) top

O1—C8	1.368 (2)	C7—C6	1.370 (3)
O1—C9	1.426 (2)	C7—H7	0.9300
O2—C2	1.2285 (19)	C1—H1A	0.9600
N1—C2	1.347 (2)	C1—H1B	0.9600
N1—C3	1.410 (2)	C1—H1C	0.9600
N1—H1	0.8600	C5—C6	1.362 (3)
C3—C4	1.376 (3)	C5—H5	0.9300
C3—C8	1.397 (3)	C6—H6	0.9300
C8—C7	1.377 (3)	C9—H9A	0.9600
C2—C1	1.480 (3)	C9—H9B	0.9600
C4—C5	1.385 (3)	C9—H9C	0.9600
C4—H4	0.9300

C8—O1—C9	117.93 (18)	C2—C1—H1A	109.5
C2—N1—C3	125.90 (14)	C2—C1—H1B	109.5
C2—N1—H1	117.1	H1A—C1—H1B	109.5
C3—N1—H1	117.1	C2—C1—H1C	109.5
C4—C3—C8	119.4 (2)	H1A—C1—H1C	109.5
C4—C3—N1	122.29 (17)	H1B—C1—H1C	109.5
C8—C3—N1	118.33 (16)	C6—C5—C4	119.5 (2)
O1—C8—C7	124.65 (18)	C6—C5—H5	120.2
O1—C8—C3	115.38 (18)	C4—C5—H5	120.2
C7—C8—C3	119.97 (19)	C5—C6—C7	121.5 (2)
O2—C2—N1	122.48 (19)	C5—C6—H6	119.3
O2—C2—C1	122.00 (16)	C7—C6—H6	119.3
N1—C2—C1	115.51 (15)	O1—C9—H9A	109.5
C3—C4—C5	120.2 (2)	O1—C9—H9B	109.5
C3—C4—H4	119.9	H9A—C9—H9B	109.5
C5—C4—H4	119.9	O1—C9—H9C	109.5
C6—C7—C8	119.5 (2)	H9A—C9—H9C	109.5
C6—C7—H7	120.3	H9B—C9—H9C	109.5
C8—C7—H7	120.3

C2—N1—C3—C4	−41.9 (3)	C3—N1—C2—C1	176.54 (19)
C2—N1—C3—C8	139.18 (19)	C8—C3—C4—C5	−0.1 (3)
C9—O1—C8—C7	−0.4 (3)	N1—C3—C4—C5	−179.04 (17)
C9—O1—C8—C3	−179.83 (17)	O1—C8—C7—C6	−179.23 (19)
C4—C3—C8—O1	179.21 (15)	C3—C8—C7—C6	0.2 (3)
N1—C3—C8—O1	−1.8 (2)	C3—C4—C5—C6	0.5 (3)
C4—C3—C8—C7	−0.2 (3)	C4—C5—C6—C7	−0.6 (3)
N1—C3—C8—C7	178.77 (17)	C8—C7—C6—C5	0.2 (4)
C3—N1—C2—O2	−2.5 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C3–C8 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.86	2.10	2.9486 (17)	168
C1—H1B···O2ⁱ	0.96	2.56	3.378 (2)	143
C1—H9B···Cg1ⁱⁱ	0.96	2.61	3.387	139

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

Funding information

This study was supported by Ondokuz Mayıs University under project No. PYO·FEN.1906.19.001.

References

Aydemir, E., Kansiz, S., Dege, N., Genc, H. & Gaidai, S. V. (2018). Acta Cryst. E74, 1674–1677. CSD CrossRef IUCr Journals Google Scholar
Chkirate, K., Kansiz, S., Karrouchi, K., Mague, J. T., Dege, N. & Essassi, E. M. (2019). Acta Cryst. E75, 154–158. CSD CrossRef IUCr Journals Google Scholar
Dam, J. H., Osztrovszky, G., Nordstrøm, L. U. & Madsen, R. (2010). Chem. Eur. J. 16, 6820–6827. CrossRef CAS PubMed Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Kansiz, S., Çakmak, Ş., Dege, N., Meral, G. & KÜtÜk, H. (2018). X-ray Struct. Anal. Online, 34, 17–18. CSD CrossRef CAS Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814-3816. Web of Science CrossRef Google Scholar
Ojeda-Porras, A. & Gamba-Sánchez, D. (2016). J. Org. Chem. 81, 11548–11555. CAS PubMed Google Scholar
Samad, M. K. & Hawaiz, F. E. (2019). Bioorg. Chem. 85, 431–444. CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sirajuddin, M., Ali, S. & Tahir, M. N. (2012). Acta Cryst. E68, o2282. CSD CrossRef IUCr Journals Google Scholar
Smith, G. & Wermuth, U. D. (2012). Acta Cryst. C68, o253–o256. Web of Science CSD CrossRef IUCr Journals Google Scholar
Song, J., Lin, Y. & Chan, W. L. (2008). Acta Cryst. E64, o934. Web of Science CSD CrossRef IUCr Journals Google Scholar
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2002). X-AREA and X-RED32. Stoe & Cie GmbH, Darmstadt, Germany. Google Scholar
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17. University of Western Australia. https://hirshfeldsurface.net. Google Scholar

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Hirshfeld surface analysis and crystal structure of N-(2-meth­­oxy­phen­yl)acetamide

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Hirshfeld surface analysis

5. Database survey

6. Synthesis and crystallization

7. Refinement

Supporting information

Funding information

References

research communications

Hirshfeld surface analysis and crystal structure of N-(2-methoxyphenyl)acetamide

3. Supramolecular features