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Acta Crystallogr Sect E Struct Rep Online. 2010 June 1; 66(Pt 6): o1362.
Published online 2010 May 15. doi:  10.1107/S1600536810017265
PMCID: PMC2979356

N,N-Bis(cyano­meth­yl)nitrous amide

Abstract

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 R 2 2(12) motifs and the other forms chains of mol­ecules lying along the c axis.

Related literature

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

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Object name is e-66-o1362-scheme1.jpg

Experimental

Crystal data

  • C4H4N4O
  • M r = 124.11
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1362-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.050
  • wR(F 2) = 0.162
  • S = 1.05
  • 1408 reflections
  • 83 parameters
  • H-atom parameters constrained
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810017265/pv2279sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017265/pv2279Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms were positioned geometrically and refined using a riding model, with C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C).

Figures

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.

Crystal data

C4H4N4OF(000) = 256
Mr = 124.11Dx = 1.341 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1409 reflections
a = 6.5622 (13) Åθ = 2.3–27.5°
b = 8.9765 (18) ŵ = 0.10 mm1
c = 11.008 (4) ÅT = 293 K
β = 108.55 (3)°Prism, colorless
V = 614.7 (3) Å30.20 × 0.20 × 0.20 mm
Z = 4

Data collection

Rigaku Mercury2 diffractometer1408 independent reflections
Radiation source: fine-focus sealed tube1094 reflections with I > 2σ(I)
graphiteRint = 0.059
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.0°
CCD_Profile_fitting scansh = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −11→11
Tmin = 0.742, Tmax = 1.000l = −14→14
6154 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.162w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
1408 reflectionsΔρmax = 0.20 e Å3
83 parametersΔρmin = −0.20 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.15 (2)

Special details

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)

xyzUiso*/Ueq
O10.1721 (2)−0.00421 (14)0.24979 (14)0.0738 (5)
N10.1213 (3)0.3227 (2)0.03826 (14)0.0730 (6)
N20.6354 (3)0.36079 (17)0.61699 (14)0.0593 (5)
N30.3553 (2)0.02971 (15)0.31634 (14)0.0537 (5)
N40.38510 (18)0.17474 (12)0.33544 (10)0.0345 (4)
C20.6201 (2)0.29919 (17)0.52436 (14)0.0411 (4)
C10.6039 (2)0.22069 (18)0.40327 (13)0.0419 (4)
H1A0.65430.28600.34870.050*
H1B0.69620.13360.42220.050*
C40.1609 (2)0.30241 (19)0.14509 (15)0.0439 (4)
C30.2111 (2)0.28025 (16)0.28328 (13)0.0405 (4)
H3B0.25040.37520.32640.049*
H3C0.08350.24460.30060.049*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0564 (9)0.0523 (9)0.0991 (11)−0.0192 (6)0.0056 (7)−0.0124 (6)
N10.0569 (11)0.1157 (16)0.0448 (9)0.0196 (9)0.0140 (7)0.0171 (8)
N20.0655 (11)0.0593 (10)0.0484 (8)−0.0107 (8)0.0113 (7)−0.0105 (7)
N30.0509 (9)0.0336 (8)0.0697 (10)−0.0029 (6)0.0094 (7)−0.0008 (6)
N40.0342 (7)0.0298 (7)0.0356 (7)0.0010 (5)0.0056 (5)0.0001 (4)
C20.0369 (8)0.0392 (8)0.0407 (8)−0.0047 (6)0.0032 (6)0.0029 (6)
C10.0357 (9)0.0485 (9)0.0387 (8)−0.0044 (7)0.0076 (6)−0.0030 (6)
C40.0339 (8)0.0545 (9)0.0390 (9)0.0035 (7)0.0058 (6)0.0048 (6)
C30.0449 (9)0.0372 (8)0.0352 (8)0.0099 (6)0.0067 (6)−0.0017 (6)

Geometric parameters (Å, °)

O1—N31.2305 (18)C2—C11.481 (2)
N1—C41.135 (2)C1—H1A0.9700
N2—C21.136 (2)C1—H1B0.9700
N3—N41.3233 (18)C4—C31.464 (2)
N4—C11.4516 (18)C3—H3B0.9700
N4—C31.4539 (17)C3—H3C0.9700
O1—N3—N4113.89 (13)C2—C1—H1B109.2
N3—N4—C1115.67 (12)H1A—C1—H1B107.9
N3—N4—C3121.36 (12)N1—C4—C3178.53 (19)
C1—N4—C3122.83 (12)N4—C3—C4112.80 (12)
N2—C2—C1178.83 (17)N4—C3—H3B109.0
N4—C1—C2111.97 (13)C4—C3—H3B109.0
N4—C1—H1A109.2N4—C3—H3C109.0
C2—C1—H1A109.2C4—C3—H3C109.0
N4—C1—H1B109.2H3B—C3—H3C107.8

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C3—H3B···N2i0.972.503.450 (2)165
C3—H3C···N1ii0.972.623.183 (2)117

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2279).

References

  • Adolf, H., Rheingold, A. L. & Allen, M. B. (1996). Private communication (CCDC deposition number 653284). CCDC, Union Road, Cambridge, England.
  • Bernstein, J., Etter, M. C. & Leiserowitz, L. (1994). Structure Correlation, Vol. 2, edited by H.-B. Bürgi & J. D. Dunitz, pp. 431–507. New York: VCH.
  • Haertling, G. H. (1999). J. Am. Ceram. Soc. A82, 797–810.
  • Homes, C. C., Vogt, T., Shapiro, S. M., Wakimoto, S. & Ramirez, A. P. (2001). Science, 293, 673–676. [PubMed]
  • Kaida, S., Minemoto, H., Shimizu, T., Sonoda, N., Miki, K. & Kasai, N. (1990). Acta Cryst. C46, 2269–2270.
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography