organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

N-(2-Eth­­oxy­phen­yl)formamide

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[Melardi, M. R., Ghannadan, A., Peyman, M., Bruno, G. & Amiri Rudbari, H. (2011). Acta Cryst. E67, o3485.]). For similar crystal structures, see: Landman et al. (2011[Landman, M., Westhuizen, B. van der, Bezuidenhout, D. I. & Liles, D. C. (2011). Acta Cryst. E67, o120.]); Chitanda et al. (2008[Chitanda, J. M., Quail, J. W. & Foley, S. R. (2008). Acta Cryst. E64, o1728.]); Hu et al. (2010[Hu, H.-L., Wu, C.-J., Cheng, P.-C. & Chen, J.-D. (2010). Acta Cryst. E66, o180.]).

[Scheme 1]

Experimental

Crystal data
  • C9H11NO2

  • Mr = 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)[Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA] Tmin = 0.671, Tmax = 0.746

  • 8725 measured reflections

  • 1961 independent reflections

  • 1248 reflections with I > 2σ(I)

  • Rint = 0.024

Refinement
  • R[F2 > 2σ(F2)] = 0.043

  • wR(F2) = 0.120

  • S = 1.03

  • 1961 reflections

  • 110 parameters

  • H-atom parameters constrained

  • Δρmax = 0.12 e Å−3

  • Δρmin = −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 DA D—H⋯A
N1—H1⋯O2i 0.86 2.24 2.9741 (18) 144
C2—H2ACgii 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[Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: XPW in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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.

Refinement top

The H atoms were placed in calculated positions and refined as riding, with N—H = 0.86 Å and C—H = 0.93, 0.96 and 0.97 Å for aryl, methy and methylene type H-atoms, respectively, with Uiso(H) = 1.2–1.5 Ueq(C/N).

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
[Figure 1] 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.
[Figure 2] 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
C9H11NO2F(000) = 704
Mr = 165.19Dx = 1.231 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 2150 reflections
a = 7.9079 (4) Åθ = 2.6–23.1°
b = 14.1253 (6) ŵ = 0.09 mm1
c = 15.9555 (7) ÅT = 296 K
V = 1782.25 (14) Å3Cubic, colourless
Z = 80.45 × 0.23 × 0.18 mm
Data collection top
Bruker APEXII CCD
diffractometer
1961 independent reflections
Radiation source: fine-focus sealed tube1248 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
ϕ and ω scansθmax = 27.1°, θmin = 3.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
h = 1010
Tmin = 0.671, Tmax = 0.746k = 1817
8725 measured reflectionsl = 2015
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0514P)2 + 0.278P]
where P = (Fo2 + 2Fc2)/3
1961 reflections(Δ/σ)max < 0.001
110 parametersΔρmax = 0.12 e Å3
0 restraintsΔρmin = 0.14 e Å3
Crystal data top
C9H11NO2V = 1782.25 (14) Å3
Mr = 165.19Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 7.9079 (4) ŵ = 0.09 mm1
b = 14.1253 (6) ÅT = 296 K
c = 15.9555 (7) Å0.45 × 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)
Tmin = 0.671, Tmax = 0.746Rint = 0.024
8725 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.120H-atom parameters constrained
S = 1.03Δρmax = 0.12 e Å3
1961 reflectionsΔρmin = 0.14 e Å3
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
xyzUiso*/Ueq
O10.14029 (12)0.40133 (8)0.12756 (7)0.0571 (3)
N10.12270 (15)0.33831 (10)0.04588 (8)0.0525 (4)
H10.03000.30860.05610.063*
O20.37570 (15)0.31796 (10)0.02102 (9)0.0808 (4)
C10.3874 (2)0.33886 (16)0.18902 (13)0.0842 (7)
H1A0.31830.28750.20850.126*
H1B0.47590.35070.22880.126*
H1C0.43610.32260.13580.126*
C20.2815 (2)0.42535 (14)0.17963 (11)0.0653 (5)
H2A0.24250.44680.23400.078*
H2B0.34690.47580.15400.078*
C30.00875 (19)0.46374 (11)0.12280 (10)0.0489 (4)
C40.13409 (18)0.43045 (11)0.07964 (9)0.0466 (4)
C50.23581 (19)0.29108 (14)0.00042 (10)0.0597 (5)
H50.20450.23070.01700.072*
C60.2759 (2)0.48701 (12)0.07355 (11)0.0585 (5)
H60.37040.46560.04460.070*
C70.2773 (2)0.57530 (14)0.11042 (14)0.0732 (6)
H70.37400.61260.10750.088*
C80.1370 (3)0.60824 (13)0.15134 (14)0.0784 (6)
H80.13840.66830.17510.094*
C90.0067 (2)0.55295 (13)0.15765 (12)0.0661 (5)
H90.10170.57590.18530.079*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0371 (6)0.0752 (8)0.0591 (7)0.0031 (5)0.0080 (5)0.0113 (5)
N10.0351 (6)0.0705 (9)0.0520 (8)0.0038 (6)0.0041 (6)0.0075 (7)
O20.0456 (7)0.0982 (10)0.0987 (10)0.0009 (7)0.0234 (6)0.0143 (8)
C10.0558 (11)0.1186 (17)0.0781 (13)0.0172 (11)0.0227 (10)0.0244 (12)
C20.0391 (8)0.0894 (13)0.0675 (11)0.0060 (9)0.0073 (8)0.0142 (10)
C30.0410 (8)0.0582 (9)0.0476 (9)0.0031 (7)0.0054 (7)0.0057 (7)
C40.0390 (7)0.0587 (10)0.0421 (8)0.0028 (7)0.0041 (6)0.0076 (7)
C50.0450 (9)0.0784 (12)0.0556 (10)0.0038 (9)0.0016 (8)0.0094 (8)
C60.0457 (9)0.0660 (11)0.0638 (10)0.0035 (8)0.0006 (8)0.0135 (9)
C70.0614 (12)0.0597 (11)0.0984 (15)0.0127 (10)0.0058 (11)0.0182 (10)
C80.0793 (14)0.0480 (11)0.1079 (17)0.0010 (10)0.0074 (12)0.0047 (10)
C90.0584 (11)0.0632 (11)0.0768 (13)0.0131 (9)0.0000 (9)0.0013 (9)
Geometric parameters (Å, º) top
O1—C31.3656 (18)C3—C91.377 (2)
O1—C21.4328 (18)C3—C41.404 (2)
N1—C51.331 (2)C4—C61.380 (2)
N1—C41.411 (2)C5—H50.9300
N1—H10.8600C6—C71.379 (3)
O2—C51.2185 (19)C6—H60.9300
C1—C21.488 (3)C7—C81.369 (3)
C1—H1A0.9600C7—H70.9300
C1—H1B0.9600C8—C91.383 (3)
C1—H1C0.9600C8—H80.9300
C2—H2A0.9700C9—H90.9300
C2—H2B0.9700
C3—O1—C2118.24 (12)C6—C4—C3119.61 (15)
C5—N1—C4128.85 (14)C6—C4—N1123.97 (14)
C5—N1—H1115.6C3—C4—N1116.40 (13)
C4—N1—H1115.6O2—C5—N1127.37 (18)
C2—C1—H1A109.5O2—C5—H5116.3
C2—C1—H1B109.5N1—C5—H5116.3
H1A—C1—H1B109.5C7—C6—C4120.02 (17)
C2—C1—H1C109.5C7—C6—H6120.0
H1A—C1—H1C109.5C4—C6—H6120.0
H1B—C1—H1C109.5C8—C7—C6120.28 (18)
O1—C2—C1107.60 (14)C8—C7—H7119.9
O1—C2—H2A110.2C6—C7—H7119.9
C1—C2—H2A110.2C7—C8—C9120.60 (18)
O1—C2—H2B110.2C7—C8—H8119.7
C1—C2—H2B110.2C9—C8—H8119.7
H2A—C2—H2B108.5C3—C9—C8119.78 (17)
O1—C3—C9125.23 (15)C3—C9—H9120.1
O1—C3—C4115.08 (14)C8—C9—H9120.1
C9—C3—C4119.68 (15)
C3—O1—C2—C1167.77 (15)C4—N1—C5—O20.8 (3)
C2—O1—C3—C96.7 (2)C3—C4—C6—C70.6 (2)
C2—O1—C3—C4172.08 (14)N1—C4—C6—C7178.25 (15)
O1—C3—C4—C6178.00 (13)C4—C6—C7—C81.7 (3)
C9—C3—C4—C60.8 (2)C6—C7—C8—C91.2 (3)
O1—C3—C4—N10.97 (19)O1—C3—C9—C8177.42 (16)
C9—C3—C4—N1179.82 (14)C4—C3—C9—C81.3 (3)
C5—N1—C4—C63.4 (3)C7—C8—C9—C30.3 (3)
C5—N1—C4—C3177.67 (15)
Hydrogen-bond geometry (Å, º) top
Cg is the centroid of the C3–C9 ring.
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.862.202.6108 (16)109
N1—H1···O2i0.862.242.9741 (18)144
C2—H2A···Cgii0.972.783.5853 (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 formulaC9H11NO2
Mr165.19
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)296
a, b, c (Å)7.9079 (4), 14.1253 (6), 15.9555 (7)
V3)1782.25 (14)
Z8
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.45 × 0.23 × 0.18
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2007)
Tmin, Tmax0.671, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections
8725, 1961, 1248
Rint0.024
(sin θ/λ)max1)0.641
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.120, 1.03
No. of reflections1961
No. of parameters110
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N1—H1···O10.862.202.6108 (16)109.3
N1—H1···O2i0.862.242.9741 (18)143.9
C2—H2A···Cgii0.972.783.5853 (19)141
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x+1/2, y, z+1/2.
 

References

First citationBruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA  Google Scholar
First citationChitanda, J. M., Quail, J. W. & Foley, S. R. (2008). Acta Cryst. E64, o1728.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationHu, 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
First citationLandman, M., Westhuizen, B. van der, Bezuidenhout, D. I. & Liles, D. C. (2011). Acta Cryst. E67, o120.  Web of Science CrossRef IUCr Journals Google Scholar
First citationMelardi, 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
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds