2-[(Dimethyl­amino)­methyl­idene]propane­dinitrile

Kant, R.; Gupta, V.K.; Kapoor, K.; Patil, D.R.; Deshmukh, M.B.

doi:10.1107/S1600536813004960

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 3| March 2013| Page o433

doi:10.1107/S1600536813004960

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2-[(Dimethylamino)methylidene]propanedinitrile

Rajni Kant,^a ^* Vivek K. Gupta,^a Kamini Kapoor,^a D. R. Patil ^b and Madhukar B. Deshmukh ^b

^aX-ray Crystallography Laboratory, Post-Graduate Department of Physics & Electronics, University of Jammu, Jammu Tawi 180 006, India, and ^bDepartment of Chemistry, Shivaji University, Kolhapur 416 004, India
^*Correspondence e-mail: rkvk.paper11@gmail.com

(Received 14 February 2013; accepted 20 February 2013; online 23 February 2013)

In the title moleclue, C₆H₇N₃, the mean plane of the dimethylamino group [maximum deviation = 0.006 (2) Å] forms a dihedral angle of 7.95 (18)° with the mean plane of the propanedinitrile fragment [maximum deviation = 0.008 (2) Å]. In the crystal, weak C—H⋯N hydrogen bonds link the molecules into a three-dimensional network.

Related literature

For applications of enamines, see: Omran et al. (1997 ); Saleh et al. (1999 ). For related structures, see: Kant et al. (2012 ); Karlsen et al. (2002 ).

Experimental

Crystal data

C₆H₇N₃
M_r = 121.15
Monoclinic, P 2₁ /c
a = 4.0368 (3) Å
b = 15.5642 (10) Å
c = 10.8500 (7) Å
β = 97.488 (6)°
V = 675.89 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.637, T_max = 1.000
15029 measured reflections
1320 independent reflections
875 reflections with I > 2σ(I)
R_int = 0.067

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.206
S = 1.05
1320 reflections
84 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯N8ⁱ	0.93	2.51	3.399 (4)	161
C4—H4B⋯N9ⁱⁱ	0.96	2.62	3.569 (4)	170
Symmetry codes: (i) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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: PLATON.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813004960/lh5587sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813004960/lh5587Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813004960/lh5587Isup3.cml

checkCIF report

Comment top

[(Dimethylamino)methylidene]propanedinitrile (I) is a potentially versatile substance which can be used for the synthesis of number of heterocyclic compounds and drug intermediates (Omran et al., 1997; Saleh et al., 1999).

In (I)(Fig.1), all bond lengths and angles are normal and correspond to those observed in related structures (Kant et al., 2012; Karlsen et al., 2002). The dihedral angle between dimethylamino group (N3/C2/C4/C5 with a maximum deviation of 0.006 (2)Å for N3) and propanedinitrile fragment (C1/C6/C7/N8/N9 with a maximum deviation of 0.008 (2)Å for C6) is 7.95 (18)°. In the crystal, weak C2—H2···N8ⁱ and C4—H4B···N9ⁱⁱ hydrogen bonds link molecules to form a three-dimensional supramolecular structure (Fig. 2, Table 1.).

Related literature top

For applications of enamines, see: Omran et al. (1997); Saleh et al. (1999). For related structures, see: Kant et al. (2012); Karlsen et al. (2002).

Experimental top

In a 50 ml round bottomed flask charged with 3 mmol of malononitrile and 3 mmol of dimethyl formamide dimethylacetal was stirred for 2 - 3hrs at room temp. The reaction was monitored by TLC. After completion of the reaction, a precipitate was formed. Finally, the product was filtered and washed with pet ether. Yield: 75%, m.p. 361–363 K. Diffraction quality single crystals were grown by slow evaporation of an ethanol solution of the title compound at room temperature

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); 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: PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at the 40% probability level. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Part of the crystal structure with dashed lines showing weak intermolecular C—H···N hydrogen bonds.

2-[(Dimethylamino)methylidene]propanedinitrile top

Crystal data top

C₆H₇N₃	F(000) = 256
M_r = 121.15	D_x = 1.191 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3950 reflections
a = 4.0368 (3) Å	θ = 3.8–29.2°
b = 15.5642 (10) Å	µ = 0.08 mm⁻¹
c = 10.8500 (7) Å	T = 293 K
β = 97.488 (6)°	Block, colourless
V = 675.89 (8) Å³	0.3 × 0.2 × 0.2 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	1320 independent reflections
Radiation source: fine-focus sealed tube	875 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.067
Detector resolution: 16.1049 pixels mm^-1	θ_max = 26.0°, θ_min = 3.8°
ω scans	h = −4→4
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −19→19
T_min = 0.637, T_max = 1.000	l = −13→13
15029 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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.206	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.1075P)² + 0.0919P] where P = (F_o² + 2F_c²)/3
1320 reflections	(Δ/σ)_max = 0.001
84 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₆H₇N₃	V = 675.89 (8) Å³
M_r = 121.15	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.0368 (3) Å	µ = 0.08 mm⁻¹
b = 15.5642 (10) Å	T = 293 K
c = 10.8500 (7) Å	0.3 × 0.2 × 0.2 mm
β = 97.488 (6)°

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	1320 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	875 reflections with I > 2σ(I)
T_min = 0.637, T_max = 1.000	R_int = 0.067
15029 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.206	H-atom parameters constrained
S = 1.05	Δρ_max = 0.23 e Å⁻³
1320 reflections	Δρ_min = −0.16 e Å⁻³
84 parameters

Special details top

Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
C1	0.3330 (6)	0.77364 (16)	0.7562 (2)	0.0501 (7)
C2	0.2937 (6)	0.69295 (15)	0.7036 (2)	0.0510 (7)
H2	0.1698	0.6914	0.6251	0.061*
N3	0.4033 (5)	0.61815 (13)	0.74689 (19)	0.0565 (6)
C4	0.3449 (7)	0.54179 (18)	0.6690 (3)	0.0752 (9)
H4A	0.2019	0.5562	0.5941	0.113*
H4B	0.2401	0.4983	0.7132	0.113*
H4C	0.5542	0.5206	0.6483	0.113*
C5	0.5891 (7)	0.6056 (2)	0.8695 (3)	0.0726 (9)
H5A	0.7939	0.6377	0.8759	0.109*
H5B	0.6386	0.5457	0.8821	0.109*
H5C	0.4577	0.6253	0.9316	0.109*
C6	0.5281 (6)	0.79802 (16)	0.8689 (2)	0.0568 (7)
C7	0.1665 (6)	0.84244 (17)	0.6873 (2)	0.0578 (7)
N8	0.6838 (6)	0.82284 (18)	0.9572 (2)	0.0805 (8)
N9	0.0355 (6)	0.89864 (16)	0.6341 (2)	0.0789 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0514 (13)	0.0581 (15)	0.0392 (13)	−0.0003 (11)	0.0003 (10)	0.0009 (11)
C2	0.0508 (13)	0.0622 (17)	0.0391 (13)	−0.0035 (11)	0.0017 (10)	0.0040 (11)
N3	0.0647 (13)	0.0565 (13)	0.0466 (13)	0.0020 (10)	0.0009 (10)	0.0064 (10)
C4	0.090 (2)	0.0557 (17)	0.077 (2)	−0.0048 (14)	0.0003 (16)	−0.0040 (15)
C5	0.0853 (19)	0.0757 (19)	0.0537 (18)	0.0151 (15)	−0.0032 (14)	0.0126 (15)
C6	0.0573 (15)	0.0640 (17)	0.0477 (15)	0.0020 (12)	0.0016 (12)	−0.0023 (13)
C7	0.0643 (16)	0.0599 (16)	0.0469 (16)	−0.0022 (13)	−0.0018 (12)	−0.0053 (13)
N8	0.0883 (17)	0.0896 (19)	0.0576 (16)	−0.0012 (14)	−0.0125 (13)	−0.0126 (14)
N9	0.0944 (18)	0.0635 (15)	0.0717 (18)	0.0074 (13)	−0.0155 (14)	0.0030 (14)

Geometric parameters (Å, º) top

C1—C2	1.380 (3)	C4—H4B	0.9600
C1—C6	1.417 (3)	C4—H4C	0.9600
C1—C7	1.424 (3)	C5—H5A	0.9600
C2—N3	1.311 (3)	C5—H5B	0.9600
C2—H2	0.9300	C5—H5C	0.9600
N3—C5	1.453 (3)	C6—N8	1.143 (3)
N3—C4	1.460 (3)	C7—N9	1.139 (3)
C4—H4A	0.9600

C2—C1—C6	128.4 (2)	N3—C4—H4C	109.5
C2—C1—C7	116.5 (2)	H4A—C4—H4C	109.5
C6—C1—C7	115.0 (2)	H4B—C4—H4C	109.5
N3—C2—C1	130.2 (2)	N3—C5—H5A	109.5
N3—C2—H2	114.9	N3—C5—H5B	109.5
C1—C2—H2	114.9	H5A—C5—H5B	109.5
C2—N3—C5	123.9 (2)	N3—C5—H5C	109.5
C2—N3—C4	119.6 (2)	H5A—C5—H5C	109.5
C5—N3—C4	116.5 (2)	H5B—C5—H5C	109.5
N3—C4—H4A	109.5	N8—C6—C1	175.8 (3)
N3—C4—H4B	109.5	N9—C7—C1	178.6 (3)
H4A—C4—H4B	109.5

C6—C1—C2—N3	5.6 (4)	C1—C2—N3—C5	2.7 (4)
C7—C1—C2—N3	−176.8 (2)	C1—C2—N3—C4	−176.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N8ⁱ	0.93	2.51	3.399 (4)	161
C4—H4B···N9ⁱⁱ	0.96	2.62	3.569 (4)	170

Symmetry codes: (i) x−1, −y+3/2, z−1/2; (ii) −x, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₆H₇N₃
M_r	121.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	4.0368 (3), 15.5642 (10), 10.8500 (7)
β (°)	97.488 (6)
V (Å³)	675.89 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.637, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15029, 1320, 875
R_int	0.067
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.206, 1.05
No. of reflections	1320
No. of parameters	84
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.16

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), 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
C2—H2···N8ⁱ	0.93	2.51	3.399 (4)	161
C4—H4B···N9ⁱⁱ	0.96	2.62	3.569 (4)	170

Symmetry codes: (i) x−1, −y+3/2, z−1/2; (ii) −x, y−1/2, −z+3/2.

Acknowledgements

RK acknowledges the Department of Science & Technology for access to the single-crystal X-ray diffractometer sanctioned as a National Facility under Project No. SR/S2/CMP-47/2003.

References

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