N,N-Bis(cyano­meth­yl)nitrous amide

Zhang, Y.; Han, M.T.

doi:10.1107/S1600536810017265

organic compounds

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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1362

https://doi.org/10.1107/S1600536810017265

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N,N-Bis(cyanomethyl)nitrous amide

Yuan Zhang ^a ^* and Meng Ting Han ^a

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: zhangshelley86@hotmail.com

(Received 6 May 2010; accepted 11 May 2010; online 15 May 2010)

In the title compound, C₄H₄N₄O, both H atoms bonded to one methylene C atom are involved in C—H⋯N hydrogen-bonding interactions; one of the interactions results in dimers of the title molecule lying about inversion centers in R₂²(12) motifs and the other forms chains of molecules lying along the c axis.

Related literature

For background to ferroelectric compounds, see: Haertling (1999 ); Homes et al. (2001 ). For related structures, see: Adolf et al. (1996 ); Kaida et al. (1990 ). For graph-set notation, see: Bernstein et al. (1994 ).

Experimental

Crystal data

C₄H₄N₄O
M_r = 124.11
Monoclinic, P 2₁ /c
a = 6.5622 (13) Å
b = 8.9765 (18) Å
c = 11.008 (4) Å
β = 108.55 (3)°
V = 614.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.742, T_max = 1.000
6154 measured reflections
1408 independent reflections
1094 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.162
S = 1.05
1408 reflections
83 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3B⋯N2ⁱ	0.97	2.50	3.450 (2)	165
C3—H3C⋯N1ⁱⁱ	0.97	2.62	3.183 (2)	117
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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: https://doi.org/10.1107/S1600536810017265/pv2279sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810017265/pv2279Isup2.hkl

checkCIF report

Comment top

At present, much attention in the field of ferroelectric materials is focused on developing ferroelectric organic or inorganic compounds (Haertling et al., 1999; Homes et al., 2001). It has been reported that N,N-bis(cyanomethyl)nitramide crystallizes in space group (C 2) at room temperature (Adolf et al., 1996), a noncentrosymmetric space group is required for ferroelectric behavior. Its ferroelectric property still needs to be further confirmed by many experiments, such as dielectric measurements and DSC to varify the permittivity anomaly, phase transition, etc. For this reason, we have synthesized the title compound to investigate its physical properties. The dielectric constant of the title compound as a function of temperature indicates that the permittivity is basically temperature-independent (dielectric constant = 3.2 to 5.6), suggesting that this compound should not be a real ferroelectric or there may be no distinct phase transition within the measured temperature range. Similarly, below the melting point (308 K) of the compound, the dielectric constant as a function of temperature also goes smoothly, and there is no dielectric anomaly observed. Herein, we report the synthesis and crystal structure of the title compound.

The bond distances and bond angles in the title compound agree very well with the corresponding distances and angles reported for a closely related compound (Kaida et al., 1990); both cyanic groups are linear (Fig. 1). It is interesting to note that both H-atoms bonded to only one methylene carbon (C3) are involved in hydrogen bonding interactions of the type C—H···N, C3—H3B···N2 hydrogen bonds result in dimers of the title molecule lying about inversion centers in R₂²(12) motifs in graph set notation (Bernstein et al., 1994) while C3—H3C···N1 interactions result in chains of molecules lying along the c-axis (Tab. 1, Fig. 2). Dipole–dipole and van der Waals interactions are effective in the molecular packing.

Related literature top

For background to ferroelectric compounds, see: Haertling et al. (1999); Homes et al. (2001). For related structures, see: Adolf et al. (1996); Kaida et al. (1990). For graph-set notation, see: Bernstein et al. (1994).

Experimental top

A solution of sodium nitrite (2.3 g, 33 mmoles) in water (10 ml) was added at 291–293 K to a solution of 2,2'-azanediyldiacetonitrile hydrochloride (1.7 g, 28 mmoles) in water (30 ml). The mixture was heated for 1.5 h at 313–323 K and allowed to stand for 12 h at 293 K. The title compound as nitroso derivative, was extracted with ether, the ether solution was evaporated. Single crystals suitable for X-ray diffraction analysis were obtained from slow evaporation of an ethyl acetate solution of the title compound.

Structure description top

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. Perspective drawing of the title compound with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed along the a-axis showing H-bondings interactions; the H atoms not involved in H-bonds have been ommitted for clarity.

N,N-Bis(cyanomethyl)nitrous amide top

Crystal data top

C₄H₄N₄O	F(000) = 256
M_r = 124.11	D_x = 1.341 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1409 reflections
a = 6.5622 (13) Å	θ = 2.3–27.5°
b = 8.9765 (18) Å	µ = 0.10 mm⁻¹
c = 11.008 (4) Å	T = 293 K
β = 108.55 (3)°	Prism, colorless
V = 614.7 (3) Å³	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	1408 independent reflections
Radiation source: fine-focus sealed tube	1094 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
CCD_Profile_fitting scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −11→11
T_min = 0.742, T_max = 1.000	l = −14→14
6154 measured reflections

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-atom parameters constrained
wR(F²) = 0.162	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1408 reflections	Δρ_max = 0.20 e Å⁻³
83 parameters	Δρ_min = −0.20 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: 0.15 (2)

Crystal data top

C₄H₄N₄O	V = 614.7 (3) Å³
M_r = 124.11	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.5622 (13) Å	µ = 0.10 mm⁻¹
b = 8.9765 (18) Å	T = 293 K
c = 11.008 (4) Å	0.20 × 0.20 × 0.20 mm
β = 108.55 (3)°

Data collection top

Rigaku Mercury2 diffractometer	1408 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1094 reflections with I > 2σ(I)
T_min = 0.742, T_max = 1.000	R_int = 0.059
6154 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.162	H-atom parameters constrained
S = 1.05	Δρ_max = 0.20 e Å⁻³
1408 reflections	Δρ_min = −0.20 e Å⁻³
83 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
O1	0.1721 (2)	−0.00421 (14)	0.24979 (14)	0.0738 (5)
N1	0.1213 (3)	0.3227 (2)	0.03826 (14)	0.0730 (6)
N2	0.6354 (3)	0.36079 (17)	0.61699 (14)	0.0593 (5)
N3	0.3553 (2)	0.02971 (15)	0.31634 (14)	0.0537 (5)
N4	0.38510 (18)	0.17474 (12)	0.33544 (10)	0.0345 (4)
C2	0.6201 (2)	0.29919 (17)	0.52436 (14)	0.0411 (4)
C1	0.6039 (2)	0.22069 (18)	0.40327 (13)	0.0419 (4)
H1A	0.6543	0.2860	0.3487	0.050*
H1B	0.6962	0.1336	0.4222	0.050*
C4	0.1609 (2)	0.30241 (19)	0.14509 (15)	0.0439 (4)
C3	0.2111 (2)	0.28025 (16)	0.28328 (13)	0.0405 (4)
H3B	0.2504	0.3752	0.3264	0.049*
H3C	0.0835	0.2446	0.3006	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0564 (9)	0.0523 (9)	0.0991 (11)	−0.0192 (6)	0.0056 (7)	−0.0124 (6)
N1	0.0569 (11)	0.1157 (16)	0.0448 (9)	0.0196 (9)	0.0140 (7)	0.0171 (8)
N2	0.0655 (11)	0.0593 (10)	0.0484 (8)	−0.0107 (8)	0.0113 (7)	−0.0105 (7)
N3	0.0509 (9)	0.0336 (8)	0.0697 (10)	−0.0029 (6)	0.0094 (7)	−0.0008 (6)
N4	0.0342 (7)	0.0298 (7)	0.0356 (7)	0.0010 (5)	0.0056 (5)	0.0001 (4)
C2	0.0369 (8)	0.0392 (8)	0.0407 (8)	−0.0047 (6)	0.0032 (6)	0.0029 (6)
C1	0.0357 (9)	0.0485 (9)	0.0387 (8)	−0.0044 (7)	0.0076 (6)	−0.0030 (6)
C4	0.0339 (8)	0.0545 (9)	0.0390 (9)	0.0035 (7)	0.0058 (6)	0.0048 (6)
C3	0.0449 (9)	0.0372 (8)	0.0352 (8)	0.0099 (6)	0.0067 (6)	−0.0017 (6)

Geometric parameters (Å, º) top

O1—N3	1.2305 (18)	C2—C1	1.481 (2)
N1—C4	1.135 (2)	C1—H1A	0.9700
N2—C2	1.136 (2)	C1—H1B	0.9700
N3—N4	1.3233 (18)	C4—C3	1.464 (2)
N4—C1	1.4516 (18)	C3—H3B	0.9700
N4—C3	1.4539 (17)	C3—H3C	0.9700

O1—N3—N4	113.89 (13)	C2—C1—H1B	109.2
N3—N4—C1	115.67 (12)	H1A—C1—H1B	107.9
N3—N4—C3	121.36 (12)	N1—C4—C3	178.53 (19)
C1—N4—C3	122.83 (12)	N4—C3—C4	112.80 (12)
N2—C2—C1	178.83 (17)	N4—C3—H3B	109.0
N4—C1—C2	111.97 (13)	C4—C3—H3B	109.0
N4—C1—H1A	109.2	N4—C3—H3C	109.0
C2—C1—H1A	109.2	C4—C3—H3C	109.0
N4—C1—H1B	109.2	H3B—C3—H3C	107.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···N2ⁱ	0.97	2.50	3.450 (2)	165
C3—H3C···N1ⁱⁱ	0.97	2.62	3.183 (2)	117

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

Experimental details

Crystal data
Chemical formula	C₄H₄N₄O
M_r	124.11
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.5622 (13), 8.9765 (18), 11.008 (4)
β (°)	108.55 (3)
V (Å³)	614.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku Mercury2
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.742, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6154, 1408, 1094
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.162, 1.05
No. of reflections	1408
No. of parameters	83
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.20

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
C3—H3B···N2ⁱ	0.97	2.50	3.450 (2)	165
C3—H3C···N1ⁱⁱ	0.97	2.62	3.183 (2)	117

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

Acknowledgements

The authors are grateful to the starter fund of Southeast University for financial support to buy the X-ray diffractometer.

References

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