N-Phenyl­formamide

Gowda, B.T.; Foro, S.; Fuess, H.

doi:10.1107/S1600536809022776

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1633

doi:10.1107/S1600536809022776

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N-Phenylformamide

B. Thimme Gowda,^a ^* Sabine Foro ^b and Hartmut Fuess ^b

^aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, and ^bInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287 Darmstadt, Germany
^*Correspondence e-mail: gowdabt@yahoo.com

(Received 5 June 2009; accepted 13 June 2009; online 20 June 2009)

There are two independent molecules in the asymmetric unit of the title compound, C₇H₇NO. The conformation of the N—H bond in the structure is syn to the C=O bond in one of the molecules and anti in the other. In the crystal, molecules are packed into chains diagonally in the ac plane via N—H⋯O hydrogen bonds.

Related literature

For related structures, see: Gowda et al. (2006 ); Brown (1966 ). For our study of the effect of ring and side chain substitutions on the crystal structures of aromatic amides, see: Gowda et al. (2000 , 2007 , 2009 ).

Experimental

Crystal data

C₇H₇NO
M_r = 121.14
Monoclinic, C 2/c
a = 30.923 (3) Å
b = 6.1737 (6) Å
c = 14.814 (1) Å
β = 113.14 (1)°
V = 2600.6 (4) Å³
Z = 16
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.48 × 0.44 × 0.40 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.966, T_max = 0.969
8394 measured reflections
2383 independent reflections
1679 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.115
S = 1.12
2383 reflections
170 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.10 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2ⁱ	0.888 (16)	1.936 (16)	2.8239 (17)	178.1 (14)
N2—H2N⋯O1ⁱⁱ	0.857 (16)	2.007 (16)	2.8637 (17)	177.0 (14)
Symmetry codes: (i) $[-x, y, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y, z-{\script{1\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809022776/rk2151sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809022776/rk2151Isup2.hkl

checkCIF report

Comment top

As part of a study of the effect of ring and side chain substitutions on the crystal structures of aromatic amides (Gowda et al., 2000; 2007; 2009), the structure of N–(phenyl)–formamide (I) has been determined. The asymmetric unit contains two independent molecules (Fig. 1). The conformation of the N—H bond is syn to the C═O bond in the side chain, in one of the molecules and is anti in the other, in contrast to the anti conformation observed in N–(2,6–dichlorophenyl)–formamide (Gowda et al., 2000 and N–(phenyl)–acetamide (Brown et al., 1966). The molecules in (I) are linked through intermolecular N—H···O hydrogen bonding (Tab. 1) and the chains formed diagonally as viewed in the ac plane (Fig. 2).

Related literature top

For a related structure, see: Gowda et al. (2006). For background literature, see: Brown (1966); Gowda et al. (2000, 2007, 2009).

Experimental top

The purity of the commmercial sample (Aldrich Chemicals) was checked by determining its melting point and characterized by recording its infrared and NMR spectra (Gowda et al., 2006). The single crystals used in X–ray diffraction studies were grown in ethanol solution by slow evaporation at room temperature.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of (I), showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as a small spheres of arbitrary radii.
	Fig. 2. Molecular packing of (I) with hydrogen bonding shown as dashed lines.

N-Phenylformamide top

Crystal data top

C₇H₇NO	F(000) = 1024
M_r = 121.14	D_x = 1.238 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2475 reflections
a = 30.923 (3) Å	θ = 2.7–28.2°
b = 6.1737 (6) Å	µ = 0.08 mm⁻¹
c = 14.814 (1) Å	T = 298 K
β = 113.14 (1)°	Needle, colourless
V = 2600.6 (4) Å³	0.48 × 0.44 × 0.40 mm
Z = 16

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2383 independent reflections
Radiation source: Fine–focus sealed tube	1679 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ω and ϕ scans	θ_max = 25.4°, θ_min = 2.8°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −37→36
T_min = 0.966, T_max = 0.969	k = −7→7
8394 measured reflections	l = −17→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.115	w = 1/[σ²(F_o²) + (0.0651P)²] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max < 0.001
2383 reflections	Δρ_max = 0.11 e Å⁻³
170 parameters	Δρ_min = −0.10 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0028 (7)

Crystal data top

C₇H₇NO	V = 2600.6 (4) Å³
M_r = 121.14	Z = 16
Monoclinic, C2/c	Mo Kα radiation
a = 30.923 (3) Å	µ = 0.08 mm⁻¹
b = 6.1737 (6) Å	T = 298 K
c = 14.814 (1) Å	0.48 × 0.44 × 0.40 mm
β = 113.14 (1)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2383 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	1679 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.969	R_int = 0.016
8394 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.11 e Å⁻³
2383 reflections	Δρ_min = −0.10 e Å⁻³
170 parameters

Special details top

Experimental. Absorption correction: CrysAlis RED (Oxford Diffraction, 2009); empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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	0.09999 (4)	0.21410 (18)	0.62537 (8)	0.0921 (4)
N1	0.04841 (4)	0.34831 (19)	0.47961 (9)	0.0694 (4)
H1N	0.0202 (6)	0.322 (2)	0.4332 (11)	0.083*
C1	0.07229 (4)	0.5289 (2)	0.46365 (9)	0.0561 (3)
C2	0.04734 (5)	0.6657 (3)	0.38753 (10)	0.0727 (4)
H2	0.0159	0.6367	0.3491	0.087*
C3	0.06857 (6)	0.8441 (3)	0.36825 (12)	0.0893 (5)
H3	0.0515	0.9351	0.3164	0.107*
C4	0.11462 (6)	0.8895 (3)	0.42461 (12)	0.0890 (5)
H4	0.1289	1.0119	0.4119	0.107*
C5	0.13948 (6)	0.7535 (3)	0.49972 (12)	0.0828 (5)
H5	0.1709	0.7834	0.5378	0.099*
C6	0.11890 (5)	0.5734 (2)	0.51989 (11)	0.0687 (4)
H6	0.1363	0.4818	0.5712	0.082*
C7	0.06296 (6)	0.2094 (2)	0.55435 (12)	0.0792 (5)
H7	0.0426	0.0966	0.5518	0.095*
O2	0.04140 (4)	0.2563 (2)	0.16582 (9)	0.0996 (4)
N2	0.11861 (4)	0.1904 (2)	0.22825 (8)	0.0628 (3)
H2N	0.1131 (5)	0.067 (3)	0.1994 (10)	0.075*
C8	0.16640 (5)	0.2389 (2)	0.28235 (9)	0.0565 (3)
C9	0.18179 (6)	0.4299 (3)	0.33258 (13)	0.0862 (5)
H9	0.1603	0.5369	0.3309	0.103*
C10	0.22921 (7)	0.4618 (3)	0.38543 (14)	0.1024 (6)
H10	0.2394	0.5901	0.4202	0.123*
C11	0.26131 (6)	0.3093 (3)	0.38760 (14)	0.0963 (6)
H11	0.2932	0.3324	0.4235	0.116*
C12	0.24605 (6)	0.1230 (3)	0.33668 (13)	0.0919 (5)
H12	0.2678	0.0184	0.3371	0.110*
C13	0.19895 (5)	0.0867 (2)	0.28451 (11)	0.0750 (4)
H13	0.1891	−0.0425	0.2503	0.090*
C14	0.08175 (6)	0.3109 (3)	0.21441 (12)	0.0771 (4)
H14	0.0867	0.4471	0.2436	0.093*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0813 (8)	0.0791 (7)	0.0881 (8)	−0.0120 (6)	0.0032 (6)	0.0215 (5)
N1	0.0527 (7)	0.0658 (8)	0.0743 (8)	−0.0096 (6)	0.0082 (6)	0.0067 (6)
C1	0.0522 (8)	0.0564 (8)	0.0570 (7)	−0.0001 (6)	0.0186 (6)	−0.0032 (6)
C2	0.0644 (9)	0.0780 (10)	0.0644 (9)	−0.0023 (7)	0.0131 (7)	0.0049 (7)
C3	0.1006 (14)	0.0823 (11)	0.0750 (10)	−0.0058 (10)	0.0236 (9)	0.0207 (9)
C4	0.0993 (14)	0.0849 (12)	0.0826 (11)	−0.0263 (10)	0.0355 (10)	0.0063 (9)
C5	0.0682 (10)	0.0902 (12)	0.0847 (11)	−0.0210 (9)	0.0242 (8)	0.0026 (9)
C6	0.0555 (8)	0.0699 (9)	0.0742 (9)	−0.0033 (7)	0.0184 (7)	0.0063 (7)
C7	0.0714 (10)	0.0648 (9)	0.0897 (11)	−0.0116 (8)	0.0189 (9)	0.0098 (8)
O2	0.0556 (7)	0.1164 (10)	0.1092 (9)	0.0152 (6)	0.0132 (6)	0.0123 (7)
N2	0.0567 (7)	0.0615 (7)	0.0645 (7)	0.0048 (6)	0.0175 (6)	−0.0040 (5)
C8	0.0557 (8)	0.0602 (8)	0.0522 (7)	−0.0013 (6)	0.0197 (6)	0.0026 (6)
C9	0.0790 (12)	0.0746 (10)	0.1005 (12)	−0.0037 (8)	0.0303 (9)	−0.0202 (9)
C10	0.0939 (14)	0.0939 (13)	0.1047 (13)	−0.0311 (11)	0.0233 (11)	−0.0271 (10)
C11	0.0647 (11)	0.1055 (15)	0.0999 (13)	−0.0158 (11)	0.0122 (9)	0.0068 (11)
C12	0.0601 (10)	0.0924 (12)	0.1119 (13)	0.0070 (9)	0.0218 (9)	0.0067 (10)
C13	0.0618 (9)	0.0680 (9)	0.0873 (10)	0.0029 (7)	0.0209 (8)	−0.0064 (7)
C14	0.0667 (11)	0.0739 (10)	0.0865 (11)	0.0132 (8)	0.0256 (9)	0.0104 (8)

Geometric parameters (Å, º) top

O1—C7	1.2132 (17)	O2—C14	1.2178 (18)
N1—C7	1.3314 (19)	N2—C14	1.3082 (19)
N1—C1	1.4076 (17)	N2—C8	1.4089 (17)
N1—H1N	0.888 (16)	N2—H2N	0.857 (16)
C1—C2	1.3771 (19)	C8—C13	1.3684 (19)
C1—C6	1.3797 (18)	C8—C9	1.375 (2)
C2—C3	1.369 (2)	C9—C10	1.378 (2)
C2—H2	0.9300	C9—H9	0.9300
C3—C4	1.367 (2)	C10—C11	1.359 (3)
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.365 (2)	C11—C12	1.354 (3)
C4—H4	0.9300	C11—H11	0.9300
C5—C6	1.371 (2)	C12—C13	1.373 (2)
C5—H5	0.9300	C12—H12	0.9300
C6—H6	0.9300	C13—H13	0.9300
C7—H7	0.9300	C14—H14	0.9300

C7—N1—C1	128.45 (13)	C14—N2—C8	128.51 (14)
C7—N1—H1N	115.8 (10)	C14—N2—H2N	115.9 (10)
C1—N1—H1N	115.7 (10)	C8—N2—H2N	115.6 (10)
C2—C1—C6	119.24 (13)	C13—C8—C9	118.76 (14)
C2—C1—N1	117.46 (12)	C13—C8—N2	117.69 (12)
C6—C1—N1	123.29 (12)	C9—C8—N2	123.55 (13)
C3—C2—C1	120.27 (14)	C8—C9—C10	119.64 (16)
C3—C2—H2	119.9	C8—C9—H9	120.2
C1—C2—H2	119.9	C10—C9—H9	120.2
C4—C3—C2	120.51 (15)	C11—C10—C9	121.22 (17)
C4—C3—H3	119.7	C11—C10—H10	119.4
C2—C3—H3	119.7	C9—C10—H10	119.4
C5—C4—C3	119.30 (15)	C12—C11—C10	118.93 (17)
C5—C4—H4	120.4	C12—C11—H11	120.5
C3—C4—H4	120.4	C10—C11—H11	120.5
C4—C5—C6	121.06 (15)	C11—C12—C13	120.85 (17)
C4—C5—H5	119.5	C11—C12—H12	119.6
C6—C5—H5	119.5	C13—C12—H12	119.6
C5—C6—C1	119.62 (14)	C8—C13—C12	120.59 (15)
C5—C6—H6	120.2	C8—C13—H13	119.7
C1—C6—H6	120.2	C12—C13—H13	119.7
O1—C7—N1	126.94 (14)	O2—C14—N2	124.22 (16)
O1—C7—H7	116.5	O2—C14—H14	117.9
N1—C7—H7	116.5	N2—C14—H14	117.9

C7—N1—C1—C2	−171.26 (15)	C14—N2—C8—C13	−178.73 (14)
C7—N1—C1—C6	9.0 (2)	C14—N2—C8—C9	1.3 (2)
C6—C1—C2—C3	−0.2 (2)	C13—C8—C9—C10	−1.4 (2)
N1—C1—C2—C3	180.00 (14)	N2—C8—C9—C10	178.58 (15)
C1—C2—C3—C4	−0.5 (3)	C8—C9—C10—C11	1.1 (3)
C2—C3—C4—C5	0.8 (3)	C9—C10—C11—C12	0.0 (3)
C3—C4—C5—C6	−0.5 (3)	C10—C11—C12—C13	−0.8 (3)
C4—C5—C6—C1	−0.2 (2)	C9—C8—C13—C12	0.7 (2)
C2—C1—C6—C5	0.5 (2)	N2—C8—C13—C12	−179.34 (13)
N1—C1—C6—C5	−179.70 (14)	C11—C12—C13—C8	0.4 (3)
C1—N1—C7—O1	1.5 (3)	C8—N2—C14—O2	179.62 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2ⁱ	0.888 (16)	1.936 (16)	2.8239 (17)	178.1 (14)
N2—H2N···O1ⁱⁱ	0.857 (16)	2.007 (16)	2.8637 (17)	177.0 (14)

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

Experimental details

Crystal data
Chemical formula	C₇H₇NO
M_r	121.14
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	30.923 (3), 6.1737 (6), 14.814 (1)
β (°)	113.14 (1)
V (Å³)	2600.6 (4)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.48 × 0.44 × 0.40

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009)
T_min, T_max	0.966, 0.969
No. of measured, independent and observed [I > 2σ(I)] reflections	8394, 2383, 1679
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.115, 1.12
No. of reflections	2383
No. of parameters	170
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.10

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2ⁱ	0.888 (16)	1.936 (16)	2.8239 (17)	178.1 (14)
N2—H2N···O1ⁱⁱ	0.857 (16)	2.007 (16)	2.8637 (17)	177.0 (14)

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

Acknowledgements

BTG thanks the Alexander von Humboldt Foundation, Bonn, Germany for the resumption of his research fellowship.

References

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