2-Cyano-2-methyl­propanamide

Xu, J.-Y.; Cheng, W.-H.

doi:10.1107/S1600536812013360

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1250

doi:10.1107/S1600536812013360

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2-Cyano-2-methylpropanamide

Jia-Ying Xu ^a ^* and Wei-Hua Cheng ^b

^aCollege of Chemical and Biological Engineering, Yancheng Institute of Technology, Yinbing Road No. 9 Yancheng, Yancheng 224051, People's Republic of China, and ^bDepartment of Chemical Engineering, Yancheng College of Textile Technology, People's Republic of China
^*Correspondence e-mail: xujiaying-1984@163.com

(Received 21 March 2012; accepted 27 March 2012; online 31 March 2012)

In the crystal structure of the title compound, C₅H₈N₂O, molecules are linked via pairs of N—H⋯O hydrogen bonds, forming inversion dimers. These dimers are linked via pairs of N—H⋯H hydrogen bonds into zigzag chains propagating along [101].

Related literature

For the synthesis of the title compound, see: Zhang et al. (2011 ). For standard bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₅H₈N₂O
M_r = 112.13
Triclinic, $[P \overline 1]$
a = 5.8916 (12) Å
b = 6.4349 (14) Å
c = 9.1263 (19) Å
α = 95.659 (4)°
β = 102.379 (4)°
γ = 109.859 (4)°
V = 312.27 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.20 × 0.18 × 0.15 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.983, T_max = 0.987
1699 measured reflections
1077 independent reflections
1000 reflections with I > 2σ(I)
R_int = 0.021
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.143
S = 1.05
1077 reflections
84 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.92 (2)	2.07 (2)	2.9714 (18)	168.2 (18)
N1—H1B⋯N2ⁱⁱ	0.874 (18)	2.328 (18)	3.166 (2)	160.8 (19)
Symmetry codes: (i) -x, -y+1, -z; (ii) -x+1, -y+1, -z+1.

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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/S1600536812013360/su2395sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812013360/su2395Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812013360/su2395Isup3.cml

checkCIF report

Comment top

The title compound has attracted considerable attention in drug research because of its outstanding biological activity. In recent years it has been used as an imtermediate in the synthesis of the high blood pressure rennin inhibitor, Aliskiren (Zhang et al., 2011).

The molecular structure of the title compound is shown in Fig. 1. The bond lengths (Allen et al., 1987) and angles are within normal ranges.

In the crystal, molecules are connected via pairs of N—H···O hydrogen bonds to form inversion dimers (Table 1 and Fig. 2). These dimers are connected via pairs of N—H···N hydrogen bonds resulting in the formation of zigzag chains (Table 1 and Fig. 2), propagating along direction [101].

Related literature top

For the synthesis of the title compound, see: Zhang et al. (2011). For standard bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was prepared by the literature procedure (Zhang et al., 2011). To a solution of methyl 2-cyano-2-methylpropanoate (5 g, 39.3 mmol) in methanol (20 ml), ammonia was added slowly at room temperature. After being stirred for 18 h at the room tempreature, a yellow solid was obtained. It was dissolved in ethanol and colourless block-like crystals of the title compound, suitable for X-ray diffraction analysis, were obtained by slow evaporation of the solvent over 7 days.

Structure description top

The molecular structure of the title compound is shown in Fig. 1. The bond lengths (Allen et al., 1987) and angles are within normal ranges.

For the synthesis of the title compound, see: Zhang et al. (2011). For standard bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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 molecule, with atom-numbering. Displacement ellipsoids are drawn at the 35% probability level.
	Fig. 2. A view along the b axis of the crystal packing of the title compound. The N—H···O and N—H···N hydrogen bonds are shown as dashed lines (see Table 1 for details).

2-Cyano-2-methylpropanamide top

Crystal data top

C₅H₈N₂O	Z = 2
M_r = 112.13	F(000) = 120
Triclinic, P1	D_x = 1.193 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.8916 (12) Å	Cell parameters from 1603 reflections
b = 6.4349 (14) Å	θ = 2.3–30.1°
c = 9.1263 (19) Å	µ = 0.09 mm⁻¹
α = 95.659 (4)°	T = 293 K
β = 102.379 (4)°	Block, colourless
γ = 109.859 (4)°	0.20 × 0.18 × 0.15 mm
V = 312.27 (11) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	1000 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.021
Graphite monochromator	θ_max = 25.0°, θ_min = 2.3°
ω/2θ scans	h = −6→6
Absorption correction: ψ scan (North et al., 1968)	k = −6→7
T_min = 0.983, T_max = 0.987	l = −10→7
1699 measured reflections	3 standard reflections every 200 reflections
1077 independent reflections	intensity decay: 1%

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)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.143	w = 1/[σ²(F_o²) + (0.1061P)² + 0.0265P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1077 reflections	Δρ_max = 0.26 e Å⁻³
84 parameters	Δρ_min = −0.26 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: 2.05 (18)

Crystal data top

C₅H₈N₂O	γ = 109.859 (4)°
M_r = 112.13	V = 312.27 (11) Å³
Triclinic, P1	Z = 2
a = 5.8916 (12) Å	Mo Kα radiation
b = 6.4349 (14) Å	µ = 0.09 mm⁻¹
c = 9.1263 (19) Å	T = 293 K
α = 95.659 (4)°	0.20 × 0.18 × 0.15 mm
β = 102.379 (4)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1000 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.021
T_min = 0.983, T_max = 0.987	3 standard reflections every 200 reflections
1699 measured reflections	intensity decay: 1%
1077 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.26 e Å⁻³
1077 reflections	Δρ_min = −0.26 e Å⁻³
84 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > 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
O1	0.29396 (18)	0.69885 (17)	0.01288 (11)	0.0555 (4)
N1	0.2126 (2)	0.51350 (19)	0.20281 (15)	0.0495 (5)
N2	0.7598 (2)	0.6725 (2)	0.48798 (16)	0.0644 (5)
C1	0.6955 (2)	0.7399 (2)	0.38232 (15)	0.0448 (5)
C2	0.6156 (2)	0.83173 (18)	0.24687 (13)	0.0364 (4)
C3	0.8132 (2)	0.8719 (2)	0.15614 (16)	0.0479 (5)
H3A	0.9726	0.9721	0.2208	0.072*
H3B	0.7658	0.9376	0.0703	0.072*
H3C	0.8246	0.7312	0.1206	0.072*
C4	0.5862 (3)	1.0547 (2)	0.29886 (16)	0.0494 (5)
H4A	0.4580	1.0266	0.3521	0.074*
H4B	0.5407	1.1176	0.2112	0.074*
H4C	0.7418	1.1586	0.3656	0.074*
C5	0.3573 (2)	0.66995 (19)	0.14359 (14)	0.0381 (4)
H1A	0.059 (4)	0.429 (3)	0.138 (2)	0.069 (5)*
H1B	0.254 (4)	0.491 (3)	0.296 (2)	0.064 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0468 (7)	0.0567 (7)	0.0374 (6)	−0.0025 (5)	−0.0094 (4)	0.0185 (5)
N1	0.0391 (7)	0.0511 (8)	0.0394 (7)	0.0004 (5)	−0.0051 (5)	0.0174 (5)
N2	0.0506 (8)	0.0740 (9)	0.0501 (8)	0.0094 (6)	−0.0086 (6)	0.0274 (7)
C1	0.0344 (7)	0.0472 (7)	0.0392 (8)	0.0058 (5)	−0.0033 (5)	0.0101 (6)
C2	0.0332 (7)	0.0376 (7)	0.0308 (7)	0.0087 (5)	−0.0002 (5)	0.0073 (5)
C3	0.0390 (7)	0.0570 (8)	0.0438 (8)	0.0150 (6)	0.0075 (6)	0.0102 (6)
C4	0.0487 (8)	0.0470 (8)	0.0447 (8)	0.0170 (6)	0.0013 (6)	0.0001 (6)
C5	0.0360 (7)	0.0366 (7)	0.0328 (7)	0.0086 (5)	−0.0018 (5)	0.0087 (5)

Geometric parameters (Å, º) top

O1—C5	1.2234 (16)	C2—C5	1.5504 (15)
N1—C5	1.3243 (17)	C3—H3A	0.9600
N1—H1A	0.92 (2)	C3—H3B	0.9600
N1—H1B	0.88 (2)	C3—H3C	0.9600
N2—C1	1.1395 (18)	C4—H4A	0.9600
C1—C2	1.4774 (17)	C4—H4B	0.9600
C2—C3	1.5356 (18)	C4—H4C	0.9600
C2—C4	1.5438 (18)

C5—N1—H1A	114.6 (12)	C2—C3—H3C	109.5
C5—N1—H1B	124.9 (12)	H3A—C3—H3C	109.5
H1A—N1—H1B	120.5 (18)	H3B—C3—H3C	109.5
N2—C1—C2	178.86 (14)	C2—C4—H4A	109.5
C1—C2—C3	109.07 (10)	C2—C4—H4B	109.5
C1—C2—C4	109.37 (10)	H4A—C4—H4B	109.5
C3—C2—C4	110.22 (10)	C2—C4—H4C	109.5
C1—C2—C5	111.37 (9)	H4A—C4—H4C	109.5
C3—C2—C5	109.91 (10)	H4B—C4—H4C	109.5
C4—C2—C5	106.88 (10)	O1—C5—N1	123.35 (11)
C2—C3—H3A	109.5	O1—C5—C2	118.09 (10)
C2—C3—H3B	109.5	N1—C5—C2	118.50 (10)
H3A—C3—H3B	109.5

N2—C1—C2—C3	78 (8)	C4—C2—C5—O1	76.58 (15)
N2—C1—C2—C4	−42 (8)	C1—C2—C5—N1	18.55 (16)
N2—C1—C2—C5	−160 (8)	C3—C2—C5—N1	139.54 (12)
C1—C2—C5—O1	−164.02 (12)	C4—C2—C5—N1	−100.85 (14)
C3—C2—C5—O1	−43.03 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.92 (2)	2.07 (2)	2.9714 (18)	168.2 (18)
N1—H1B···N2ⁱⁱ	0.874 (18)	2.328 (18)	3.166 (2)	160.8 (19)

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

Experimental details

Crystal data
Chemical formula	C₅H₈N₂O
M_r	112.13
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.8916 (12), 6.4349 (14), 9.1263 (19)
α, β, γ (°)	95.659 (4), 102.379 (4), 109.859 (4)
V (Å³)	312.27 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.18 × 0.15

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.983, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	1699, 1077, 1000
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.143, 1.05
No. of reflections	1077
No. of parameters	84
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.26

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), 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—H1A···O1ⁱ	0.92 (2)	2.07 (2)	2.9714 (18)	168.2 (18)
N1—H1B···N2ⁱⁱ	0.874 (18)	2.328 (18)	3.166 (2)	160.8 (19)

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

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for the data collection. They also thank the Foundation of Yancheng Institute of Technology (XKR2010055) and the National Natural Science Foundation of China (No. 31000142) for financial support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Enraf–Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, W. L., Wang, P. & Gan, L. X. (2011). Patent Pub. No. WO/2011/091677; Int. Appl. No. PCT/CN2010/078549. Google Scholar