N-(Cyano­meth­yl)benzamide

Aouine, Y.; Alami, A.; El Hallaoui, A.; Elachqar, A.; Zouihri, H.

doi:10.1107/S1600536810003557

organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o530

doi:10.1107/S1600536810003557

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N-(Cyanomethyl)benzamide

Younas Aouine,^a Anouar Alami,^a ^* Abdelilah El Hallaoui,^a Abdelrhani Elachqar ^a and Hafid Zouihri ^b

^aLaboratoire de Chimie Organique, Faculté des Sciences Dhar el Mahraz, Université Sidi Mohammed Ben Abdellah, Fès, Morocco, and ^bCentre National pour la Recherche Scientifique et Technique, Division UATRS, Rabat, Morocco
^*Correspondence e-mail: alamianouar@yahoo.fr

(Received 21 January 2010; accepted 28 January 2010; online 6 February 2010)

In the structure of the title compound, C₉H₈N₂O, the amide group is twisted by a dihedral angle of 21.86 (7)° with respect to the benzene ring, while the planes of the benzene ring and cyanomethyl group form a dihedral angle of 53.13 (11)°. In the crystal structure, molecules are linked via N—H⋯O hydrogen bonds, forming a chain running parallel to the a axis.

Related literature

For the biological activity and medicinal properties of tetrazole derivatives, see: Smissman et al. (1976 ); McGuire et al. (1990 ); Lunn et al. (1992 ); Itoh et al. (1995 ); Upadhayaya et al. (2004 ); Wu et al. (2008 ); Rostom et al. (2009 ); Burger (1991 ); Singh et al. (1980 ). For the synthetic procedure, see: Adams & Langley (1941a ,b ).

Experimental

Crystal data

C₉H₈N₂O
M_r = 160.17
Orthorhombic, P b c a
a = 9.8623 (5) Å
b = 8.0576 (4) Å
c = 20.9268 (9) Å
V = 1662.98 (14) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.33 × 0.28 × 0.22 mm

Data collection

Bruker X8 APEXII CCD area-detector diffractometer
11132 measured reflections
1920 independent reflections
1433 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.109
S = 1.02
1920 reflections
141 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H6⋯O1ⁱ	0.819 (17)	2.021 (18)	2.8313 (14)	169
Symmetry code: (i) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ) and ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810003557/dn2533sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810003557/dn2533Isup2.hkl

checkCIF report

Comment top

Tetrazoles derivatives are an important class of compounds, which can be used in the fields of bioorganic and medicinal chemistry as antibacterials, anti-cancer, heart disease, neurodegenerative disease, and antifungal activity (Smissman et al.,1976; McGuire et al., 1990; Lunn et al., 1992; Itoh et al., 1995; Upadhayaya et al., 2004; Wu et al., 2008; Rostom et al., 2009.

The tetrazole moiety has long been established as a bioisostere of a carboxyl unit (Burger, 1991). A major advantage of tetrazoles over carboxylic acids is that they are resistant to many biological metabolic degradation pathways (Singh et al., 1980).

With the aim of developing new tetrazolic derived, an analog isosteric of the glycine, we have prepared N-(cyanomethyl)benzamide, a key intermediate, starting from aminoacetonitrile hydrogen sulphate.

In the title compound, the amide group is rotated by 21,86° out of the plane of the benzene ring (Fig. 1). The crystal packing is stabilized by N—H···O hydrogen bonds (Table 1) to form infinite chains parallel to the a axis (Fig. 2).

Related literature top

For the biological activity and medicinal properties of tetrazole derivatives, see: Smissman et al. (1976); McGuire et al. (1990); Lunn et al. (1992); Itoh et al. (1995); Upadhayaya et al. (2004); Wu et al. (2008); Rostom et al. (2009); Burger (1991); Singh et al. (1980). For the synthetic procedure, see: Adams & Langley (1941a,b).

Experimental top

Aminoacetonitrile hydrogen sulphate was prepared in two steps from technical formaldehyde (Adams & Langley, 1941a,b).

To a solution of 10 mmol s of aminoacetonitrile hydrogen sulfate in 10 ml of methylene chloride, triethylamine was added until neutral pH at cold temperature (0 <T< 5°C ), then 11 mmol s of Benzoyl chloride was added at the same temperature. The mixture was stirred at 0°C for 1 hour. The whole is taken to room temperature and left under magnetic agitation during 16 hours. After reaction, the mixture was washed 3 times with a solution of citric acid 15%; then, the organic solution is dried over sodium sulphate and evaporated under reduced pressure. The residue was crystallized from a mixture ether/hexane (1:1) to give white solid in 82% yield. m.p.: 138- 140°C .

The structure of the product was established on the basis of NMR spectroscopy (¹H, ¹³C ), MS data and elemental analysis.

Single crystals of the title compound were obtained from an ethanolic solution and used for X-ray diffraction studies at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. : Molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. : Partial packing view showing the chain generated by N—H···O hydrogen bonds shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.[Symmetry code: (i) x+1/2,y,-z+1/2].

N-(Cyanomethyl)benzamide top

Crystal data top

C₉H₈N₂O	D_x = 1.280 Mg m⁻³
M_r = 160.17	Melting point: 413 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3689 reflections
a = 9.8623 (5) Å	θ = 2.5–27.2°
b = 8.0576 (4) Å	µ = 0.09 mm⁻¹
c = 20.9268 (9) Å	T = 296 K
V = 1662.98 (14) Å³	Block, colourless
Z = 8	0.33 × 0.28 × 0.22 mm
F(000) = 672

Data collection top

Bruker X8 APEXII CCD area-detector diffractometer	1433 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.027
Graphite monochromator	θ_max = 27.6°, θ_min = 2.8°
ϕ and ω scans	h = −12→12
11132 measured reflections	k = −10→10
1920 independent reflections	l = −26→27

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0541P)² + 0.2439P] where P = (F_o² + 2F_c²)/3
1920 reflections	(Δ/σ)_max < 0.001
141 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₉H₈N₂O	V = 1662.98 (14) Å³
M_r = 160.17	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.8623 (5) Å	µ = 0.09 mm⁻¹
b = 8.0576 (4) Å	T = 296 K
c = 20.9268 (9) Å	0.33 × 0.28 × 0.22 mm

Data collection top

Bruker X8 APEXII CCD area-detector diffractometer	1433 reflections with I > 2σ(I)
11132 measured reflections	R_int = 0.027
1920 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.14 e Å⁻³
1920 reflections	Δρ_min = −0.18 e Å⁻³
141 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 > σ(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
C1	0.24170 (14)	0.39220 (16)	0.13675 (7)	0.0488 (3)
C2	0.25299 (17)	0.43033 (18)	0.07283 (7)	0.0591 (4)
C3	0.36704 (17)	0.38418 (18)	0.03941 (7)	0.0592 (4)
C4	0.47054 (16)	0.30131 (19)	0.06980 (7)	0.0552 (4)
C5	0.46079 (13)	0.26308 (16)	0.13418 (6)	0.0448 (3)
C6	0.34534 (11)	0.30793 (14)	0.16810 (6)	0.0387 (3)
C7	0.32434 (11)	0.26377 (15)	0.23629 (6)	0.0415 (3)
C8	0.41628 (14)	0.17663 (17)	0.33761 (6)	0.0498 (3)
C9	0.37055 (14)	0.31427 (19)	0.37822 (6)	0.0529 (3)
O1	0.21031 (8)	0.25889 (15)	0.26031 (5)	0.0645 (3)
N1	0.43271 (11)	0.22652 (14)	0.27184 (5)	0.0456 (3)
N2	0.33580 (17)	0.4211 (2)	0.40988 (7)	0.0792 (4)
H1	0.1646 (16)	0.4224 (18)	0.1609 (7)	0.064 (4)*
H2	0.1826 (17)	0.489 (2)	0.0525 (8)	0.075 (5)*
H3	0.3723 (16)	0.410 (2)	−0.0064 (8)	0.073 (5)*
H4	0.5496 (17)	0.267 (2)	0.0484 (8)	0.067 (5)*
H5	0.5302 (16)	0.2004 (18)	0.1546 (7)	0.054 (4)*
H6	0.5098 (18)	0.2419 (17)	0.2585 (7)	0.053 (4)*
H7	0.5037 (17)	0.1326 (19)	0.3548 (8)	0.065 (4)*
H8	0.3480 (15)	0.0870 (17)	0.3409 (7)	0.057 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0411 (7)	0.0482 (7)	0.0571 (8)	0.0051 (6)	−0.0007 (6)	0.0009 (6)
C2	0.0638 (9)	0.0554 (8)	0.0581 (8)	0.0075 (7)	−0.0087 (7)	0.0066 (7)
C3	0.0733 (11)	0.0587 (8)	0.0457 (7)	−0.0087 (8)	−0.0014 (7)	0.0005 (6)
C4	0.0508 (8)	0.0631 (8)	0.0517 (7)	−0.0064 (7)	0.0110 (6)	−0.0100 (6)
C5	0.0333 (6)	0.0512 (7)	0.0500 (7)	−0.0016 (5)	0.0015 (5)	−0.0043 (5)
C6	0.0290 (5)	0.0400 (5)	0.0470 (6)	−0.0038 (5)	−0.0013 (5)	−0.0023 (5)
C7	0.0240 (5)	0.0503 (6)	0.0502 (7)	−0.0016 (5)	0.0027 (5)	0.0016 (5)
C8	0.0373 (7)	0.0564 (8)	0.0558 (7)	0.0041 (6)	0.0010 (6)	0.0149 (6)
C9	0.0435 (7)	0.0665 (8)	0.0487 (7)	0.0021 (6)	0.0020 (6)	0.0156 (7)
O1	0.0224 (4)	0.1126 (9)	0.0586 (6)	−0.0004 (5)	0.0037 (4)	0.0142 (5)
N1	0.0236 (5)	0.0632 (7)	0.0500 (6)	−0.0002 (5)	0.0027 (4)	0.0093 (5)
N2	0.0867 (11)	0.0836 (9)	0.0675 (8)	0.0108 (8)	0.0100 (8)	−0.0003 (7)

Geometric parameters (Å, º) top

C1—C2	1.377 (2)	C5—H5	0.952 (16)
C1—C6	1.3915 (17)	C6—C7	1.4852 (17)
C1—H1	0.945 (16)	C7—O1	1.2324 (13)
C2—C3	1.376 (2)	C7—N1	1.3364 (15)
C2—H2	0.940 (18)	C8—N1	1.4430 (17)
C3—H3	0.984 (16)	C8—C9	1.468 (2)
C4—C3	1.376 (2)	C8—H8	0.990 (15)
C4—H4	0.940 (17)	C8—H7	0.999 (17)
C5—C4	1.3854 (19)	C9—N2	1.1389 (19)
C5—C6	1.3896 (17)	N1—H6	0.820 (17)

C5—C6—C1	119.21 (12)	N1—C8—H8	110.2 (8)
C5—C6—C7	122.87 (11)	C9—C8—H8	107.6 (8)
C1—C6—C7	117.86 (11)	N1—C8—H7	110.2 (9)
O1—C7—N1	119.70 (11)	C9—C8—H7	109.0 (9)
O1—C7—C6	121.79 (11)	H8—C8—H7	107.6 (12)
N1—C7—C6	118.50 (10)	N2—C9—C8	179.61 (18)
C4—C5—C6	119.72 (13)	C3—C2—C1	119.98 (14)
C4—C5—H5	120.3 (9)	C3—C2—H2	120.6 (10)
C6—C5—H5	119.9 (9)	C1—C2—H2	119.4 (10)
C3—C4—C5	120.40 (14)	C4—C3—C2	120.20 (14)
C3—C4—H4	122.4 (10)	C4—C3—H3	121.1 (10)
C5—C4—H4	117.2 (10)	C2—C3—H3	118.7 (9)
C2—C1—C6	120.49 (13)	C7—N1—C8	120.25 (11)
C2—C1—H1	121.8 (9)	C7—N1—H6	121.2 (11)
C6—C1—H1	117.7 (9)	C8—N1—H6	118.2 (11)
N1—C8—C9	112.10 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H6···O1ⁱ	0.819 (17)	2.021 (18)	2.8313 (14)	169

Symmetry code: (i) x+1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₉H₈N₂O
M_r	160.17
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	9.8623 (5), 8.0576 (4), 20.9268 (9)
V (Å³)	1662.98 (14)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.33 × 0.28 × 0.22

Data collection
Diffractometer	Bruker X8 APEXII CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11132, 1920, 1433
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.652

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.109, 1.02
No. of reflections	1920
No. of parameters	141
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.18

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and ORTEP-3 for Windows (Farrugia, 1997), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H6···O1ⁱ	0.819 (17)	2.021 (18)	2.8313 (14)	169

Symmetry code: (i) x+1/2, y, −z+1/2.

Acknowledgements

The authors thank the CNRST Morocco for financial support (Programs PROTAS D13/03).

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