N-(2-Eth­oxy­phen­yl)formamide

Rofouei, M.K.; Attar Gharamaleki, J.; Younesian, F.; Bruno, G.; Rudbari, H.A.

doi:10.1107/S160053681200205X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o505

doi:10.1107/S160053681200205X

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N-(2-Ethoxyphenyl)formamide

Mohammad Kazem Rofouei,^a Jafar Attar Gharamaleki,^a ^* Fereshteh Younesian,^b Giuseppe Bruno ^c and Hadi Amiri Rudbari ^c

^aFaculty of Chemistry, Tarbiat Moallem University, Tehran, Iran, ^bDepartment of Chemistry, Islamic Azad University, Tehran Central Branch, Tehran, Iran, and ^cDipartimento di Chimica Inorganica, Universita di Messina, Messina, Italy
^*Correspondence e-mail: attar_jafar@yahoo.com

(Received 4 January 2012; accepted 17 January 2012; online 21 January 2012)

The title compound, C₉H₁₁NO₂, was obtained as an unexpected product in an attempt to synthesize a triazene ligand. The title molecule is almost planar, with the formamide and ethoxy groups oriented at 2.7 (3) and 12.9 (2)°, respectively, with respect to the mean plane of the benzene ring. In the crystal, molecules are linked by intermolecular N—H⋯O hydrogen bonds, forming a chain along the a axis. Weak C—H⋯π interactions with an H⋯π distance of 2.78 Å reinforce the crystal packing, resulting in a three-dimensional network.

Related literature

For preparation of several trizene compounds in our laboratory, see: Melardi et al. (2011 ). For similar crystal structures, see: Landman et al. (2011 ); Chitanda et al. (2008 ); Hu et al. (2010 ).

Experimental

Crystal data

C₉H₁₁NO₂
M_r = 165.19
Orthorhombic, P b c a
a = 7.9079 (4) Å
b = 14.1253 (6) Å
c = 15.9555 (7) Å
V = 1782.25 (14) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.45 × 0.23 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007) T_min = 0.671, T_max = 0.746
8725 measured reflections
1961 independent reflections
1248 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.120
S = 1.03
1961 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C3–C9 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.86	2.24	2.9741 (18)	144
C2—H2A⋯Cgⁱⁱ	0.97	2.78	3.5853 (19)	141
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (ii) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XPW in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681200205X/pv2505sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681200205X/pv2505Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681200205X/pv2505Isup3.cml

checkCIF report

Comment top

The preparation of several trizene compounds as ligands in our laboratory has already been reported (Melardi et al., 2011). However, the title compound was formed as an unexpected product in an attempt for the synthesis of a triazene ligand, 1-(2-methylphenyl)-3(2-ethoxyphenyl)triazene). In this article, we report the synthesis and crystal structure of the title compound.

The title molecule (Fig. 1) is almost planar with formamide and ethoxy groups oriented at 2.7 (3) and 12.9 (2)°, respectively, with respect to the mean-plane of the benzene ring. The bond lengths and angles in the title molecule are in accord with the corresponding bond lengths and angles reported in a few similar structures (Landman et al., 2011; Chitanda et al., 2008; Hu et al., 2010).

In the crystal structure molecules are linked by intermolecular N—H···O hydrogen bonds (Table 1) to form a chain along the a-axis. Weak edge-to-face C—H···Cg1 stacking interaction between an ethoxy hydrogen and a benzene ring with H···π distance of 2.78 Å, (Cg1 is the center of benzene ring atoms C3/C4/C6—C9) reinforce the crystal packing resulting in a three-dimensional network (Fig. 2).

Related literature top

For preparation of several trizene compounds in our laboratory, see: Melardi et al. (2011). For similar crystal structures, see: Landman et al. (2011); Chitanda et al. (2008); Hu et al. (2010).

Experimental top

The title compound was obtained as an unexpected product in an attempt for the synthesis of a triazene ligand, 1-(2-methylphenyl)-3(2-ethoxyphenyl)triazene). A 100 ml flask was charged with 10 g of ice and 15 ml of water and then cooled to 273 K in an ice-bath. To this were added 2-methylaniline (0.215 g, 2 mmol), hydrochloric acid (36.5%, 2 mmol) and 2 ml water. To this solution was then added a solution containing NaNO₂ (0.16 g, 2 mmol) in 2 ml water during a 15 min period. After mixing for 15 min, the obtained solution was added to a solution of o-phenetidin (0.261 ml, 2 mmol), 2 ml methanol and 2 ml water. After that a solution containing sodium acetate (2.95 g, 36 mmol) in 10 ml water was added. After mixing for 24 h the colorless material was filtered off and dissolved in DMSO. By recrystallization from DMSO, the crystals of the title compound were obtained instead of the expected triazene.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XPW in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. A view of the N—-H···O hydrogen bonds and and C—H···π interactions (dotted lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen-bonding were omitted for clarity.

N-(2-Ethoxyphenyl)formamide top

Crystal data top

C₉H₁₁NO₂	F(000) = 704
M_r = 165.19	D_x = 1.231 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2150 reflections
a = 7.9079 (4) Å	θ = 2.6–23.1°
b = 14.1253 (6) Å	µ = 0.09 mm⁻¹
c = 15.9555 (7) Å	T = 296 K
V = 1782.25 (14) Å³	Cubic, colourless
Z = 8	0.45 × 0.23 × 0.18 mm

Data collection top

Bruker APEXII CCD diffractometer	1961 independent reflections
Radiation source: fine-focus sealed tube	1248 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 27.1°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −10→10
T_min = 0.671, T_max = 0.746	k = −18→17
8725 measured reflections	l = −20→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0514P)² + 0.278P] where P = (F_o² + 2F_c²)/3
1961 reflections	(Δ/σ)_max < 0.001
110 parameters	Δρ_max = 0.12 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₉H₁₁NO₂	V = 1782.25 (14) Å³
M_r = 165.19	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 7.9079 (4) Å	µ = 0.09 mm⁻¹
b = 14.1253 (6) Å	T = 296 K
c = 15.9555 (7) Å	0.45 × 0.23 × 0.18 mm

Data collection top

Bruker APEXII CCD diffractometer	1961 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1248 reflections with I > 2σ(I)
T_min = 0.671, T_max = 0.746	R_int = 0.024
8725 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.03	Δρ_max = 0.12 e Å⁻³
1961 reflections	Δρ_min = −0.14 e Å⁻³
110 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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) top

	x	y	z	U_iso*/U_eq
O1	0.14029 (12)	0.40133 (8)	0.12756 (7)	0.0571 (3)
N1	−0.12270 (15)	0.33831 (10)	0.04588 (8)	0.0525 (4)
H1	−0.0300	0.3086	0.0561	0.063*
O2	−0.37570 (15)	0.31796 (10)	−0.02102 (9)	0.0808 (4)
C1	0.3874 (2)	0.33886 (16)	0.18902 (13)	0.0842 (7)
H1A	0.3183	0.2875	0.2085	0.126*
H1B	0.4759	0.3507	0.2288	0.126*
H1C	0.4361	0.3226	0.1358	0.126*
C2	0.2815 (2)	0.42535 (14)	0.17963 (11)	0.0653 (5)
H2A	0.2425	0.4468	0.2340	0.078*
H2B	0.3469	0.4758	0.1540	0.078*
C3	0.00875 (19)	0.46374 (11)	0.12280 (10)	0.0489 (4)
C4	−0.13409 (18)	0.43045 (11)	0.07964 (9)	0.0466 (4)
C5	−0.23581 (19)	0.29108 (14)	0.00042 (10)	0.0597 (5)
H5	−0.2045	0.2307	−0.0170	0.072*
C6	−0.2759 (2)	0.48701 (12)	0.07355 (11)	0.0585 (5)
H6	−0.3704	0.4656	0.0446	0.070*
C7	−0.2773 (2)	0.57530 (14)	0.11042 (14)	0.0732 (6)
H7	−0.3740	0.6126	0.1075	0.088*
C8	−0.1370 (3)	0.60824 (13)	0.15134 (14)	0.0784 (6)
H8	−0.1384	0.6683	0.1751	0.094*
C9	0.0067 (2)	0.55295 (13)	0.15765 (12)	0.0661 (5)
H9	0.1017	0.5759	0.1853	0.079*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0371 (6)	0.0752 (8)	0.0591 (7)	0.0031 (5)	−0.0080 (5)	−0.0113 (5)
N1	0.0351 (6)	0.0705 (9)	0.0520 (8)	0.0038 (6)	−0.0041 (6)	−0.0075 (7)
O2	0.0456 (7)	0.0982 (10)	0.0987 (10)	0.0009 (7)	−0.0234 (6)	−0.0143 (8)
C1	0.0558 (11)	0.1186 (17)	0.0781 (13)	0.0172 (11)	−0.0227 (10)	−0.0244 (12)
C2	0.0391 (8)	0.0894 (13)	0.0675 (11)	−0.0060 (9)	−0.0073 (8)	−0.0142 (10)
C3	0.0410 (8)	0.0582 (9)	0.0476 (9)	−0.0031 (7)	0.0054 (7)	0.0057 (7)
C4	0.0390 (7)	0.0587 (10)	0.0421 (8)	−0.0028 (7)	0.0041 (6)	0.0076 (7)
C5	0.0450 (9)	0.0784 (12)	0.0556 (10)	−0.0038 (9)	−0.0016 (8)	−0.0094 (8)
C6	0.0457 (9)	0.0660 (11)	0.0638 (10)	0.0035 (8)	−0.0006 (8)	0.0135 (9)
C7	0.0614 (12)	0.0597 (11)	0.0984 (15)	0.0127 (10)	0.0058 (11)	0.0182 (10)
C8	0.0793 (14)	0.0480 (11)	0.1079 (17)	−0.0010 (10)	0.0074 (12)	0.0047 (10)
C9	0.0584 (11)	0.0632 (11)	0.0768 (13)	−0.0131 (9)	0.0000 (9)	0.0013 (9)

Geometric parameters (Å, º) top

O1—C3	1.3656 (18)	C3—C9	1.377 (2)
O1—C2	1.4328 (18)	C3—C4	1.404 (2)
N1—C5	1.331 (2)	C4—C6	1.380 (2)
N1—C4	1.411 (2)	C5—H5	0.9300
N1—H1	0.8600	C6—C7	1.379 (3)
O2—C5	1.2185 (19)	C6—H6	0.9300
C1—C2	1.488 (3)	C7—C8	1.369 (3)
C1—H1A	0.9600	C7—H7	0.9300
C1—H1B	0.9600	C8—C9	1.383 (3)
C1—H1C	0.9600	C8—H8	0.9300
C2—H2A	0.9700	C9—H9	0.9300
C2—H2B	0.9700

C3—O1—C2	118.24 (12)	C6—C4—C3	119.61 (15)
C5—N1—C4	128.85 (14)	C6—C4—N1	123.97 (14)
C5—N1—H1	115.6	C3—C4—N1	116.40 (13)
C4—N1—H1	115.6	O2—C5—N1	127.37 (18)
C2—C1—H1A	109.5	O2—C5—H5	116.3
C2—C1—H1B	109.5	N1—C5—H5	116.3
H1A—C1—H1B	109.5	C7—C6—C4	120.02 (17)
C2—C1—H1C	109.5	C7—C6—H6	120.0
H1A—C1—H1C	109.5	C4—C6—H6	120.0
H1B—C1—H1C	109.5	C8—C7—C6	120.28 (18)
O1—C2—C1	107.60 (14)	C8—C7—H7	119.9
O1—C2—H2A	110.2	C6—C7—H7	119.9
C1—C2—H2A	110.2	C7—C8—C9	120.60 (18)
O1—C2—H2B	110.2	C7—C8—H8	119.7
C1—C2—H2B	110.2	C9—C8—H8	119.7
H2A—C2—H2B	108.5	C3—C9—C8	119.78 (17)
O1—C3—C9	125.23 (15)	C3—C9—H9	120.1
O1—C3—C4	115.08 (14)	C8—C9—H9	120.1
C9—C3—C4	119.68 (15)

C3—O1—C2—C1	167.77 (15)	C4—N1—C5—O2	−0.8 (3)
C2—O1—C3—C9	6.7 (2)	C3—C4—C6—C7	−0.6 (2)
C2—O1—C3—C4	−172.08 (14)	N1—C4—C6—C7	178.25 (15)
O1—C3—C4—C6	178.00 (13)	C4—C6—C7—C8	1.7 (3)
C9—C3—C4—C6	−0.8 (2)	C6—C7—C8—C9	−1.2 (3)
O1—C3—C4—N1	−0.97 (19)	O1—C3—C9—C8	−177.42 (16)
C9—C3—C4—N1	−179.82 (14)	C4—C3—C9—C8	1.3 (3)
C5—N1—C4—C6	3.4 (3)	C7—C8—C9—C3	−0.3 (3)
C5—N1—C4—C3	−177.67 (15)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C3–C9 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	2.20	2.6108 (16)	109
N1—H1···O2ⁱ	0.86	2.24	2.9741 (18)	144
C2—H2A···Cgⁱⁱ	0.97	2.78	3.5853 (19)	141

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

Experimental details

Crystal data
Chemical formula	C₉H₁₁NO₂
M_r	165.19
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	7.9079 (4), 14.1253 (6), 15.9555 (7)
V (Å³)	1782.25 (14)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.45 × 0.23 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.671, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	8725, 1961, 1248
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.120, 1.03
No. of reflections	1961
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.14

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XPW in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C3–C9 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	2.20	2.6108 (16)	109.3
N1—H1···O2ⁱ	0.86	2.24	2.9741 (18)	143.9
C2—H2A···Cgⁱⁱ	0.97	2.78	3.5853 (19)	141

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

References

Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA Google Scholar
Chitanda, J. M., Quail, J. W. & Foley, S. R. (2008). Acta Cryst. E64, o1728. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hu, H.-L., Wu, C.-J., Cheng, P.-C. & Chen, J.-D. (2010). Acta Cryst. E66, o180. Web of Science CSD CrossRef IUCr Journals Google Scholar
Landman, M., Westhuizen, B. van der, Bezuidenhout, D. I. & Liles, D. C. (2011). Acta Cryst. E67, o120. Web of Science CrossRef IUCr Journals Google Scholar
Melardi, M. R., Ghannadan, A., Peyman, M., Bruno, G. & Amiri Rudbari, H. (2011). Acta Cryst. E67, o3485. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o505

doi:10.1107/S160053681200205X

Open

access