(Methyl­enedinitrilo)tetra­acetonitrile

Song, X.-H.; Feng, M.-L.; Wang, K.; Li, Y.-F.; Zhu, H.-J.

doi:10.1107/S160053681000824X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o785

doi:10.1107/S160053681000824X

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(Methylenedinitrilo)tetraacetonitrile

Xiang-Hua Song,^a Mei-Li Feng,^a Kai Wang,^a Yu-Feng Li ^a and Hong-Jun Zhu ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: zhuhj@njut.edu.cn

(Received 20 January 2010; accepted 3 March 2010; online 10 March 2010)

The molecular structure of the title compound, C₉H₁₀N₆, exhibits four cyanomethyl groups around a central N—CH₂—N unit. In the crystal structure, molecules are connected via intermolecular C—H⋯N hydrogen bonds, forming a three-dimensional network.

Related literature

For bond-length data, see: Allen et al. (1987 ). For the synthetic procedure, see: W. R. Grace & Co. (1969 ). For the use of the title compound in the synthesis of N-(phosphonomethyl) iminodiacetic acid, see: Obeso Caceres & Urcelay del Pozo (1991 ).

Experimental

Crystal data

C₉H₁₀N₆
M_r = 202.23
Monoclinic, P 2₁ /n
a = 6.743 (1) Å
b = 15.984 (3) Å
c = 10.610 (2) Å
β = 105.88 (3)°
V = 1099.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.976, T_max = 0.992
2167 measured reflections
1991 independent reflections
1396 reflections with I > 2σ(I)
R_int = 0.016
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.143
S = 1.00
1991 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2B⋯N4ⁱ	0.97	2.56	3.409 (3)	146
C4—H4B⋯N3ⁱⁱ	0.97	2.58	3.432 (3)	147
Symmetry codes: (i) -x, -y+2, -z+1; (ii) $[-x-{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; 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/S160053681000824X/im2179sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681000824X/im2179Isup2.hkl

checkCIF report

Comment top

The tittle compound, {[(Bis-cyanomethyl-amino)-methyl]cyanomethyl-amino}-acetonitrile is an important intermediate for the synthesis of N-(Phosphonomethyl) iminodiacetic acid (Obeso Caceres & Urcelay del Pozo, 1991), which can be used to synthesize glyphosphates. Herein we report the crystal structure of the title compound, (I).

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

In the crystal of the title compound molecules are connected via intermolecular C—H···N hydrogen bonds to form a three dimensional network.

Related literature top

For bond-length data, see: Allen et al. (1987). For the synthetic procedure, see: W.R. Grace & Co. (1969). For the use of the title compound in the synthesis of N-(Phosphonomethyl) iminodiacetic acid, see: Obeso Caceres & Urcelay del Pozo (1991).

Experimental top

The title compound, (I) was synthesized according to a literature method (W.R. Grace &Co., 1969). Crystals were obtained by dissolving compound (I) (1.5 g) in methanol (25 ml) and evaporating the solvent slowly at room temperature for about 8 d.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); 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. Molecular structure of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Packing diagram for (I). C—H···N hydrogen bonds are shown as dashed lines.

(Methylenedinitrilo)tetraacetonitrile top

Crystal data top

C₉H₁₀N₆	F(000) = 424
M_r = 202.23	D_x = 1.221 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 6.743 (1) Å	θ = 10–13°
b = 15.984 (3) Å	µ = 0.08 mm⁻¹
c = 10.610 (2) Å	T = 293 K
β = 105.88 (3)°	Block, colorless
V = 1099.9 (4) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1396 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.016
Graphite monochromator	θ_max = 25.3°, θ_min = 2.4°
ω/2θ scans	h = 0→8
Absorption correction: ψ scan (North et al., 1968)	k = 0→19
T_min = 0.976, T_max = 0.992	l = −12→12
2167 measured reflections	3 standard reflections every 200 reflections
1991 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)] = 0.047	H-atom parameters constrained
wR(F²) = 0.143	w = 1/[σ²(F_o²) + (0.085P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1991 reflections	Δρ_max = 0.13 e Å⁻³
137 parameters	Δρ_min = −0.14 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: 0.112 (10)

Crystal data top

C₉H₁₀N₆	V = 1099.9 (4) Å³
M_r = 202.23	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.743 (1) Å	µ = 0.08 mm⁻¹
b = 15.984 (3) Å	T = 293 K
c = 10.610 (2) Å	0.30 × 0.20 × 0.10 mm
β = 105.88 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1396 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.016
T_min = 0.976, T_max = 0.992	3 standard reflections every 200 reflections
2167 measured reflections	intensity decay: 1%
1991 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 1.00	Δρ_max = 0.13 e Å⁻³
1991 reflections	Δρ_min = −0.14 e Å⁻³
137 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	−0.0963 (3)	0.70909 (15)	0.4827 (2)	0.0615 (6)
N1	−0.0281 (3)	0.67348 (19)	0.5772 (2)	0.1033 (9)
C2	−0.1891 (3)	0.75550 (13)	0.3610 (2)	0.0500 (5)
H2A	−0.2811	0.7179	0.3005	0.060*
H2B	−0.2727	0.8002	0.3813	0.060*
N2	0.3724 (3)	0.66055 (14)	0.3957 (2)	0.0783 (7)
C3	0.2363 (3)	0.69176 (13)	0.3233 (2)	0.0528 (6)
N3	−0.2530 (3)	1.06022 (13)	0.3005 (2)	0.0812 (7)
C4	0.0600 (3)	0.73457 (12)	0.23192 (19)	0.0472 (5)
H4A	0.1101	0.7652	0.1679	0.057*
H4B	−0.0362	0.6926	0.1851	0.057*
N4	0.3020 (3)	1.08661 (11)	0.45391 (19)	0.0650 (6)
N5	−0.0489 (2)	0.79180 (9)	0.29447 (15)	0.0444 (4)
C5	−0.1757 (3)	1.01621 (13)	0.2444 (2)	0.0563 (6)
N6	0.1060 (2)	0.91629 (9)	0.25246 (15)	0.0451 (4)
C6	−0.0768 (3)	0.95691 (13)	0.1736 (2)	0.0560 (6)
H6A	−0.1765	0.9142	0.1338	0.067*
H6B	−0.0411	0.9868	0.1032	0.067*
C7	0.2980 (3)	1.03432 (12)	0.3814 (2)	0.0480 (5)
C8	0.2920 (3)	0.96600 (12)	0.2853 (2)	0.0555 (6)
H8A	0.3094	0.9905	0.2053	0.067*
H8B	0.4083	0.9292	0.3202	0.067*
C9	0.0716 (3)	0.86329 (11)	0.35568 (18)	0.0457 (5)
H9A	0.2025	0.8449	0.4129	0.055*
H9B	−0.0018	0.8941	0.4076	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0474 (12)	0.0761 (15)	0.0674 (15)	0.0003 (11)	0.0266 (11)	0.0082 (13)
N1	0.0719 (15)	0.150 (2)	0.0938 (17)	0.0147 (15)	0.0319 (13)	0.0500 (17)
C2	0.0450 (11)	0.0465 (11)	0.0627 (12)	0.0006 (9)	0.0219 (10)	0.0000 (9)
N2	0.0670 (13)	0.0839 (15)	0.0872 (15)	0.0192 (12)	0.0263 (12)	0.0043 (12)
C3	0.0534 (13)	0.0451 (11)	0.0675 (13)	0.0022 (10)	0.0292 (11)	−0.0072 (10)
N3	0.0713 (14)	0.0637 (13)	0.1181 (18)	0.0208 (11)	0.0419 (13)	0.0157 (12)
C4	0.0527 (11)	0.0397 (10)	0.0530 (11)	−0.0015 (9)	0.0210 (10)	−0.0084 (9)
N4	0.0758 (13)	0.0522 (11)	0.0720 (12)	−0.0069 (10)	0.0287 (10)	−0.0107 (10)
N5	0.0462 (9)	0.0358 (8)	0.0559 (9)	−0.0021 (7)	0.0218 (8)	−0.0058 (7)
C5	0.0470 (12)	0.0459 (12)	0.0764 (15)	0.0039 (10)	0.0176 (11)	0.0155 (11)
N6	0.0438 (9)	0.0388 (8)	0.0552 (9)	−0.0052 (7)	0.0176 (7)	−0.0047 (7)
C6	0.0596 (13)	0.0518 (12)	0.0559 (12)	−0.0032 (10)	0.0148 (10)	0.0026 (10)
C7	0.0479 (12)	0.0408 (11)	0.0590 (12)	−0.0067 (9)	0.0210 (10)	−0.0010 (9)
C8	0.0529 (13)	0.0479 (11)	0.0733 (14)	−0.0092 (10)	0.0303 (11)	−0.0149 (10)
C9	0.0514 (11)	0.0352 (10)	0.0510 (11)	0.0026 (9)	0.0151 (9)	−0.0056 (8)

Geometric parameters (Å, º) top

C1—N1	1.135 (3)	N5—C9	1.449 (2)
C1—C2	1.472 (3)	C5—C6	1.478 (3)
C2—N5	1.447 (2)	N6—C6	1.441 (2)
C2—H2A	0.9700	N6—C8	1.445 (2)
C2—H2B	0.9700	N6—C9	1.452 (2)
N2—C3	1.138 (3)	C6—H6A	0.9700
C3—C4	1.480 (3)	C6—H6B	0.9700
N3—C5	1.136 (3)	C7—C8	1.487 (3)
C4—N5	1.443 (2)	C8—H8A	0.9700
C4—H4A	0.9700	C8—H8B	0.9700
C4—H4B	0.9700	C9—H9A	0.9700
N4—C7	1.132 (2)	C9—H9B	0.9700

N1—C1—C2	178.7 (2)	C8—N6—C9	116.50 (16)
N5—C2—C1	116.91 (16)	N6—C6—C5	115.26 (17)
N5—C2—H2A	108.1	N6—C6—H6A	108.5
C1—C2—H2A	108.1	C5—C6—H6A	108.5
N5—C2—H2B	108.1	N6—C6—H6B	108.5
C1—C2—H2B	108.1	C5—C6—H6B	108.5
H2A—C2—H2B	107.3	H6A—C6—H6B	107.5
N2—C3—C4	178.2 (2)	N4—C7—C8	179.6 (2)
N5—C4—C3	114.24 (16)	N6—C8—C7	115.34 (16)
N5—C4—H4A	108.7	N6—C8—H8A	108.4
C3—C4—H4A	108.7	C7—C8—H8A	108.4
N5—C4—H4B	108.7	N6—C8—H8B	108.4
C3—C4—H4B	108.7	C7—C8—H8B	108.4
H4A—C4—H4B	107.6	H8A—C8—H8B	107.5
C4—N5—C2	116.91 (15)	N5—C9—N6	107.91 (14)
C4—N5—C9	114.36 (14)	N5—C9—H9A	110.1
C2—N5—C9	117.30 (15)	N6—C9—H9A	110.1
N3—C5—C6	178.4 (2)	N5—C9—H9B	110.1
C6—N6—C8	116.11 (16)	N6—C9—H9B	110.1
C6—N6—C9	114.43 (15)	H9A—C9—H9B	108.4

N1—C1—C2—N5	160 (12)	N3—C5—C6—N6	−68 (9)
N2—C3—C4—N5	−26 (7)	C6—N6—C8—C7	71.1 (2)
C3—C4—N5—C2	−77.5 (2)	C9—N6—C8—C7	−68.2 (2)
C3—C4—N5—C9	65.1 (2)	N4—C7—C8—N6	−92 (32)
C1—C2—N5—C4	70.3 (2)	C4—N5—C9—N6	69.05 (19)
C1—C2—N5—C9	−71.2 (2)	C2—N5—C9—N6	−148.50 (16)
C8—N6—C6—C5	−77.2 (2)	C6—N6—C9—N5	68.47 (19)
C9—N6—C6—C5	63.0 (2)	C8—N6—C9—N5	−151.47 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···N4ⁱ	0.97	2.56	3.409 (3)	146
C4—H4B···N3ⁱⁱ	0.97	2.58	3.432 (3)	147

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

Experimental details

Crystal data
Chemical formula	C₉H₁₀N₆
M_r	202.23
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.743 (1), 15.984 (3), 10.610 (2)
β (°)	105.88 (3)
V (Å³)	1099.9 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.976, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	2167, 1991, 1396
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.143, 1.00
No. of reflections	1991
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.14

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), 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
C2—H2B···N4ⁱ	0.9700	2.5600	3.409 (3)	146.00
C4—H4B···N3ⁱⁱ	0.9700	2.5800	3.432 (3)	147.00

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

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for 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. CrossRef Web of Science Google Scholar
Enraf–Nonius (1994). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
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Obeso Caceres, R. M. & Urcelay del Pozo, M. I. (1991). ES Patent No. 2018746. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
W. R. Grace & Co. (1969). GB Patent No. 1167693. Google Scholar