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organic compounds
N-(4-Methylphenyl)formamide
aCollege of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
*Correspondence e-mail: chenxinyuanseu@yahoo.com.cn
In the title compound, C8H9NO, the amide group makes a dihedral of 32.35 (1)° with the benzene ring. In the crystal, pairs of strong N—H⋯O hydrogen bonds link the molecules into inversion dimers. Weak C—H⋯O interactions further connect the molecules into chains along the a axis.
Related literature
For the structures and properties of related compounds, see: Tam et al. (2003); Omondi et al. (2005
).
Experimental
Crystal data
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Refinement
|
|
Data collection: CrystalClear (Rigaku, 2005); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: SHELXTL (Sheldrick, 2008
); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536812024300/pv2549sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812024300/pv2549Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812024300/pv2549Isup3.cml
A mixture of formic acid (30 mmol), 4-toluidine (10 mmol), H2SO4 (0.5 ml, molar concentration 98%) and ethanol (50 mL) in a 100 ml flask was stirred at 333 K for 10 h. Colourless crystals suitable for X-ray diffraction were obtained by slow evaporation of the solution.
All H atoms were positioned geometrically and refined using a riding model, with distances N—H = 0.86 Å and C—H = 0.93 and 0.96 Å, for aryl and methyl H-atoms, respectively. The Uiso(H) were allowed at 1.5Ueq(C methyl) or 1.2Ueq(N/C non-methyl).
Data collection: CrystalClear (Rigaku, 2005); cell
CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C8H9NO | Z = 2 |
Mr = 135.16 | F(000) = 144 |
Triclinic, P1 | Dx = 1.269 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.5511 (11) Å | Cell parameters from 1570 reflections |
b = 6.9192 (12) Å | θ = 3.6–27.5° |
c = 8.0265 (17) Å | µ = 0.09 mm−1 |
α = 93.730 (1)° | T = 153 K |
β = 102.780 (1)° | Block, colorless |
γ = 91.769 (1)° | 0.10 × 0.05 × 0.05 mm |
V = 353.68 (11) Å3 |
Rigaku Mercury2 diffractometer | 1570 independent reflections |
Radiation source: fine-focus sealed tube | 943 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 3.6° |
CCD profile fitting scans | h = −8→8 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −7→8 |
Tmin = 0.910, Tmax = 1.000 | l = −10→10 |
2597 measured reflections |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 0.90 | w = 1/[σ2(Fo2) + (0.0693P)2] where P = (Fo2 + 2Fc2)/3 |
1570 reflections | (Δ/σ)max < 0.001 |
92 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C8H9NO | γ = 91.769 (1)° |
Mr = 135.16 | V = 353.68 (11) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.5511 (11) Å | Mo Kα radiation |
b = 6.9192 (12) Å | µ = 0.09 mm−1 |
c = 8.0265 (17) Å | T = 153 K |
α = 93.730 (1)° | 0.10 × 0.05 × 0.05 mm |
β = 102.780 (1)° |
Rigaku Mercury2 diffractometer | 1570 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 943 reflections with I > 2σ(I) |
Tmin = 0.910, Tmax = 1.000 | Rint = 0.030 |
2597 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 0.90 | Δρmax = 0.24 e Å−3 |
1570 reflections | Δρmin = −0.21 e Å−3 |
92 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.23436 (18) | 1.02875 (15) | 0.39355 (14) | 0.0308 (3) | |
N1 | 0.3558 (2) | 0.80633 (18) | 0.58427 (17) | 0.0232 (3) | |
H1B | 0.4814 | 0.8558 | 0.6014 | 0.028* | |
C7 | 0.1344 (3) | 0.6126 (2) | 0.7268 (2) | 0.0247 (4) | |
H7A | 0.0295 | 0.7011 | 0.7049 | 0.030* | |
C3 | 0.4782 (2) | 0.5127 (2) | 0.7131 (2) | 0.0238 (4) | |
H3A | 0.6044 | 0.5333 | 0.6805 | 0.029* | |
C2 | 0.3215 (2) | 0.6435 (2) | 0.67500 (19) | 0.0210 (4) | |
C4 | 0.4474 (3) | 0.3510 (2) | 0.7997 (2) | 0.0249 (4) | |
H4A | 0.5542 | 0.2648 | 0.8251 | 0.030* | |
C1 | 0.2053 (3) | 0.8876 (2) | 0.4739 (2) | 0.0251 (4) | |
H1A | 0.0695 | 0.8344 | 0.4562 | 0.030* | |
C6 | 0.1060 (3) | 0.4493 (2) | 0.8112 (2) | 0.0261 (4) | |
H6A | −0.0204 | 0.4285 | 0.8434 | 0.031* | |
C5 | 0.2602 (3) | 0.3151 (2) | 0.8494 (2) | 0.0251 (4) | |
C8 | 0.2248 (3) | 0.1390 (2) | 0.9420 (2) | 0.0359 (5) | |
H8A | 0.0850 | 0.0854 | 0.8973 | 0.054* | |
H8B | 0.2434 | 0.1753 | 1.0620 | 0.054* | |
H8C | 0.3236 | 0.0439 | 0.9255 | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0283 (7) | 0.0289 (7) | 0.0364 (7) | 0.0013 (5) | 0.0065 (5) | 0.0132 (6) |
N1 | 0.0220 (7) | 0.0227 (7) | 0.0251 (7) | −0.0013 (5) | 0.0053 (6) | 0.0054 (6) |
C7 | 0.0244 (9) | 0.0237 (8) | 0.0267 (9) | 0.0018 (7) | 0.0075 (7) | 0.0018 (7) |
C3 | 0.0231 (8) | 0.0263 (9) | 0.0226 (8) | −0.0012 (7) | 0.0066 (7) | 0.0017 (7) |
C2 | 0.0258 (9) | 0.0177 (8) | 0.0189 (8) | −0.0014 (6) | 0.0043 (6) | 0.0011 (6) |
C4 | 0.0268 (9) | 0.0234 (9) | 0.0238 (9) | 0.0030 (7) | 0.0039 (7) | 0.0027 (7) |
C1 | 0.0226 (9) | 0.0255 (9) | 0.0279 (9) | 0.0018 (7) | 0.0066 (7) | 0.0029 (7) |
C6 | 0.0251 (9) | 0.0295 (9) | 0.0248 (9) | −0.0042 (7) | 0.0087 (7) | 0.0013 (7) |
C5 | 0.0322 (10) | 0.0215 (8) | 0.0202 (8) | −0.0045 (7) | 0.0041 (7) | 0.0015 (7) |
C8 | 0.0412 (12) | 0.0317 (10) | 0.0355 (11) | −0.0041 (8) | 0.0087 (9) | 0.0111 (8) |
O1—C1 | 1.2369 (18) | C4—C5 | 1.391 (2) |
N1—C1 | 1.3364 (19) | C4—H4A | 0.9300 |
N1—C2 | 1.4189 (19) | C1—H1A | 0.9300 |
N1—H1B | 0.8600 | C6—C5 | 1.391 (2) |
C7—C6 | 1.383 (2) | C6—H6A | 0.9300 |
C7—C2 | 1.393 (2) | C5—C8 | 1.506 (2) |
C7—H7A | 0.9300 | C8—H8A | 0.9600 |
C3—C2 | 1.387 (2) | C8—H8B | 0.9600 |
C3—C4 | 1.387 (2) | C8—H8C | 0.9600 |
C3—H3A | 0.9300 | ||
C1—N1—C2 | 124.15 (14) | O1—C1—N1 | 124.50 (15) |
C1—N1—H1B | 117.9 | O1—C1—H1A | 117.8 |
C2—N1—H1B | 117.9 | N1—C1—H1A | 117.8 |
C6—C7—C2 | 119.50 (15) | C7—C6—C5 | 122.15 (15) |
C6—C7—H7A | 120.3 | C7—C6—H6A | 118.9 |
C2—C7—H7A | 120.3 | C5—C6—H6A | 118.9 |
C2—C3—C4 | 120.16 (15) | C6—C5—C4 | 117.38 (14) |
C2—C3—H3A | 119.9 | C6—C5—C8 | 120.91 (15) |
C4—C3—H3A | 119.9 | C4—C5—C8 | 121.71 (15) |
C3—C2—C7 | 119.37 (14) | C5—C8—H8A | 109.5 |
C3—C2—N1 | 119.07 (14) | C5—C8—H8B | 109.5 |
C7—C2—N1 | 121.56 (14) | H8A—C8—H8B | 109.5 |
C3—C4—C5 | 121.42 (15) | C5—C8—H8C | 109.5 |
C3—C4—H4A | 119.3 | H8A—C8—H8C | 109.5 |
C5—C4—H4A | 119.3 | H8B—C8—H8C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O1i | 0.86 | 1.99 | 2.849 (2) | 172 |
C7—H7A···O1ii | 0.93 | 2.63 | 3.546 (2) | 171 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C8H9NO |
Mr | 135.16 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 153 |
a, b, c (Å) | 6.5511 (11), 6.9192 (12), 8.0265 (17) |
α, β, γ (°) | 93.730 (1), 102.780 (1), 91.769 (1) |
V (Å3) | 353.68 (11) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.10 × 0.05 × 0.05 |
Data collection | |
Diffractometer | Rigaku Mercury2 diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) |
Tmin, Tmax | 0.910, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2597, 1570, 943 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.127, 0.90 |
No. of reflections | 1570 |
No. of parameters | 92 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.21 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O1i | 0.86 | 1.99 | 2.849 (2) | 172.2 |
C7—H7A···O1ii | 0.93 | 2.626 | 3.546 (2) | 170.7 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x, −y+2, −z+1. |
Acknowledgements
This work was supported by a start-up grant from Southeast University, China.
References
Omondi, B., Fernandes, M. A., Layh, M., Levendis, D. C., Look, J. L. & Mkwizu, T. S. P. (2005). CrystEngComm, 7, 690–700. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tam, C. N., Cowan, J. A., Schultz, A. J., Young, V. G., Trouw, F. R. & Sykes, A. G. (2003). J. Phys. Chem. B, 107, 7601–7606. Web of Science CSD CrossRef CAS 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.
N-(4-Chlorophenyl)formamide and N-(2,6-dichlorophenyl)formamide exhibit phase transitions under different thermal conditions from disordered model to ordered model (Tam et al., 2003; Omondi et al., 2005). Therefore, with the purpose of obtaining phase transition crystals of organic compounds, various similar organic molecules have been studied. The title compound has been synthesized to determine its crystal structure and dielectric properties. In this article, the synthesis and crystal structure of the title compound are reported.
In the title compound (Fig. 1), the amide group (O1/N1/C1) makes a dihedral of 32.35 (1)° with the benzene ring (C2–C7). In the crystal structure, the H atom bonded to the N atom is involved in a strong intermolecular N1—H1B···O1 hydrogen bond. In addition, weak C7—H7A···O1 further stabilize the crystal structure. These H-bonding interactions connect the molecules into a 1D chain along the a-axis (Fig. 2 and Table 1). The bond lengths and bond angles in the title molecule agree very well with the corresponding bond distances and bond angles reported in closely related compounds (Tam et al., 2003; Omondi et al., 2005)