N-(4-Methyl­phen­yl)formamide

Zhao, M.-M.

doi:10.1107/S1600536812024300

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1961

doi:10.1107/S1600536812024300

Open

access

N-(4-Methylphenyl)formamide

Min-Min Zhao ^a ^*

^aCollege of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: chenxinyuanseu@yahoo.com.cn

(Received 21 May 2012; accepted 28 May 2012; online 31 May 2012)

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

C₈H₉NO
M_r = 135.16
Triclinic, $[P \overline 1]$
a = 6.5511 (11) Å
b = 6.9192 (12) Å
c = 8.0265 (17) Å
α = 93.730 (1)°
β = 102.780 (1)°
γ = 91.769 (1)°
V = 353.68 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 153 K
0.10 × 0.05 × 0.05 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.910, T_max = 1.000
2597 measured reflections
1570 independent reflections
943 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.127
S = 0.90
1570 reflections
92 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812024300/pv2549sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812024300/pv2549Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812024300/pv2549Isup3.cml

checkCIF report

Comment top

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)

Related literature top

For the structures and properties of related compounds, see: Tam et al. (2003); Omondi et al. (2005).

Experimental top

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.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: 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).

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 and C—-H···O hydrogen bonds (dotted lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen-bonding were omitted for clarity.

N-(4-Methylphenyl)formamide top

Crystal data top

C₈H₉NO	Z = 2
M_r = 135.16	F(000) = 144
Triclinic, P1	D_x = 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

Data collection top

Rigaku Mercury2 diffractometer	1570 independent reflections
Radiation source: fine-focus sealed tube	943 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.6°
CCD profile fitting scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −7→8
T_min = 0.910, T_max = 1.000	l = −10→10
2597 measured reflections

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H-atom parameters constrained
S = 0.90	w = 1/[σ²(F_o²) + (0.0693P)²] where P = (F_o² + 2F_c²)/3
1570 reflections	(Δ/σ)_max < 0.001
92 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₈H₉NO	γ = 91.769 (1)°
M_r = 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)°

Data collection top

Rigaku Mercury2 diffractometer	1570 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	943 reflections with I > 2σ(I)
T_min = 0.910, T_max = 1.000	R_int = 0.030
2597 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 0.90	Δρ_max = 0.24 e Å⁻³
1570 reflections	Δρ_min = −0.21 e Å⁻³
92 parameters

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.

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.

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.910, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	2597, 1570, 943
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.21

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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