3,8-Dimethyl-4,7-diaza­deca-3,7-diene-2,9-dione dioxime

Achiwawanich, S.; Duangtongyou, T.; Pakawatchai, C.; Siripaisarnpipat, S.

doi:10.1107/S1600536810051603

organic compounds

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ISSN: 2056-9890

Volume 67| Part 1| January 2011| Page o135

https://doi.org/10.1107/S1600536810051603

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3,8-Dimethyl-4,7-diazadeca-3,7-diene-2,9-dione dioxime

Supakit Achiwawanich,^a Tanwawan Duangtongyou,^a Chaveng Pakawatchai ^b and Sutatip Siripaisarnpipat ^a ^*

^aCenter of Excellence in Functional Materials, Department of Chemistry, Faculty of Science, Kasetsart University, Bangkok 10903, Thailand, and ^bDepartment of Chemistry, Faculty of Science, Prince Songkla University, Hatyai, Songkla, Thailand
^*Correspondence e-mail: fscists@ku.ac.th

(Received 16 November 2010; accepted 9 December 2010; online 15 December 2010)

The complete molecule of the title compound, C₁₀H₁₈N₄O₂, is generated by a crystallographic inversion centre at the mid-point of the central C—C bond. The two oxime groups have an E configuration. In the crystal, molecules are linked through intermolecular O—H⋯N hydrogen bonds.

Related literature

For a related synthesis and the application of the title compound as a ligand, see: Uhlig et al. (1966 ); Kitiphaisalnont et al. (2006 ).

Experimental

Crystal data

C₁₀H₁₈N₄O₂
M_r = 226.28
Monoclinic, P 2₁ /n
a = 4.4128 (3) Å
b = 12.8534 (8) Å
c = 10.4860 (7) Å
β = 90.762 (2)°
V = 594.71 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.16 × 0.13 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
3578 measured reflections
1293 independent reflections
939 reflections with I > 2σ(I)
R_int = 0.032
3 standard reflections every 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.132
S = 1.05
1293 reflections
75 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2ⁱ	0.82	2.12	2.8384 (19)	146
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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/S1600536810051603/lx2184sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810051603/lx2184Isup2.hkl

checkCIF report

Comment top

The diiminedioxime have been used as ligand for the complexation of transition metal ions (Uhlig et al., 1966). The title molecule, C₁₀H₁₈N₄O₂,is a diiminedioxime which contains shortest methylene backbone. The hydrogen bonds are formed between two oxime groups (Kitiphaisalnont et al., 2006). Herein, we report on the crystal structue of the title compound.

The centrosymmetric unit of the title compound (Fig. 1) is generated by a crystallographic inversion centre (symmetry code: -x,-y,-z) at the mid-point of the the central C—C bond and there is a crystallographic twofold screw axis (symmetry code: -x + 1/2,y + 1/2,-z + 1/2). The two oxime groups have a E configuration. The crystal packing (Fig. 2) is stabilized by weak intermolecular O—H···N hydrogen bonds (Table 1; O1—H1···N2ⁱⁱ).

Related literature top

For a related synthesis and the application of the title compound as a ligand, see: Uhlig et al. (1966); Kitiphaisalnont et al. (2006).

Experimental top

The title compound was prepared from the simple reaction between diacetylmonoxime 20.2 g (0.200 mole)and ethylenediamine 6.7 ml (0.100 mole)in 50 ml me thanol. After the mixture was stirred at room temperature for 30 min, white solid precipitated (yield 75%).After recrystalization,the colorless crystals were obtained.

Structure description top

For a related synthesis and the application of the title compound as a ligand, see: Uhlig et al. (1966); Kitiphaisalnont et al. (2006).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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 compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as a small spheres of arbitrary radius.[Symmetry codes:(i) -x, 1 - y, -z.]
	Fig. 2. A view of O—H···N interactions (dotted lines) in the crystal structure of the title compound. [Symmetry codes: (i) 1/2 + x, 0.5 - y, 1/2 + z; (ii) -1/2 + x, 0.5 - y, -1/2 + z; (iii) -x, 1 - y, -z; (iv) -0.5 - x, 1/2 + y, -0.5 - z.]

3,8-Dimethyl-4,7-diazadeca-3,7-diene-2,9-dione dioxime top

Crystal data top

C₁₀H₁₈N₄O₂	F(000) = 244
M_r = 226.28	D_x = 1.264 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 4.4128 (3) Å	θ = 25–35°
b = 12.8534 (8) Å	µ = 0.09 mm⁻¹
c = 10.4860 (7) Å	T = 293 K
β = 90.762 (2)°	Needle, colorless
V = 594.71 (7) Å³	0.16 × 0.13 × 0.12 mm
Z = 2

Data collection top

Bruker SMART CCD area detector diffractometer	939 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.032
Graphite monochromator	θ_max = 27.0°, θ_min = 2.5°
multi–scan	h = −5→5
3578 measured reflections	k = −16→16
1293 independent reflections	l = −13→7

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)] = 0.049	Hydrogen site location: difference Fourier map
wR(F²) = 0.132	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0571P)² + 0.1569P] where P = (F_o² + 2F_c²)/3
1293 reflections	(Δ/σ)_max < 0.001
75 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₀H₁₈N₄O₂	V = 594.71 (7) Å³
M_r = 226.28	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.4128 (3) Å	µ = 0.09 mm⁻¹
b = 12.8534 (8) Å	T = 293 K
c = 10.4860 (7) Å	0.16 × 0.13 × 0.12 mm
β = 90.762 (2)°

Data collection top

Bruker SMART CCD area detector diffractometer	939 reflections with I > 2σ(I)
3578 measured reflections	R_int = 0.032
1293 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.132	H-atom parameters constrained
S = 1.05	Δρ_max = 0.16 e Å⁻³
1293 reflections	Δρ_min = −0.22 e Å⁻³
75 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	0.8167 (3)	0.17534 (10)	0.32669 (12)	0.0477 (4)
H1	0.8704	0.1661	0.4010	0.072*
N1	0.6414 (3)	0.26556 (11)	0.31833 (13)	0.0378 (4)
N2	0.2568 (3)	0.40201 (11)	0.07864 (13)	0.0351 (4)
C1	0.5506 (4)	0.28417 (13)	0.20383 (15)	0.0345 (4)
C2	0.3631 (4)	0.37999 (13)	0.19019 (15)	0.0335 (4)
C3	0.0664 (4)	0.49535 (14)	0.06676 (16)	0.0378 (4)
H3A	0.1871	0.5566	0.0861	0.045*
H3B	−0.0964	0.4918	0.1279	0.045*
C4	0.6133 (5)	0.21689 (16)	0.09136 (17)	0.0521 (6)
H4A	0.7442	0.2532	0.0340	0.078*
H4B	0.4262	0.2003	0.0483	0.078*
H4C	0.7100	0.1539	0.1194	0.078*
C5	0.3088 (5)	0.44515 (16)	0.30710 (17)	0.0478 (5)
H5A	0.3519	0.5167	0.2885	0.072*
H5B	0.4387	0.4218	0.3754	0.072*
H5C	0.1010	0.4385	0.3319	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0611 (9)	0.0471 (8)	0.0345 (7)	0.0125 (7)	−0.0118 (6)	0.0046 (6)
N1	0.0454 (9)	0.0382 (8)	0.0297 (8)	0.0030 (7)	−0.0085 (6)	0.0034 (6)
N2	0.0385 (8)	0.0369 (8)	0.0296 (7)	−0.0036 (6)	−0.0083 (6)	0.0039 (6)
C1	0.0380 (9)	0.0379 (9)	0.0274 (9)	−0.0049 (7)	−0.0057 (7)	0.0034 (7)
C2	0.0367 (9)	0.0367 (9)	0.0271 (8)	−0.0049 (7)	−0.0057 (7)	0.0022 (7)
C3	0.0404 (9)	0.0386 (10)	0.0343 (9)	−0.0016 (8)	−0.0083 (7)	0.0042 (7)
C4	0.0754 (15)	0.0487 (12)	0.0319 (10)	0.0139 (10)	−0.0097 (9)	−0.0010 (8)
C5	0.0622 (13)	0.0491 (11)	0.0319 (9)	0.0079 (9)	−0.0082 (8)	−0.0005 (8)

Geometric parameters (Å, º) top

O1—N1	1.3959 (19)	C3—H3A	0.9700
O1—H1	0.8200	C3—H3B	0.9700
N1—C1	1.283 (2)	C4—H4A	0.9600
N2—C2	1.286 (2)	C4—H4B	0.9600
N2—C3	1.469 (2)	C4—H4C	0.9600
C1—C2	1.490 (2)	C5—H5A	0.9600
C1—C4	1.491 (2)	C5—H5B	0.9600
C2—C5	1.507 (2)	C5—H5C	0.9600
C3—C3ⁱ	1.515 (3)

N1—O1—H1	109.5	H3A—C3—H3B	108.1
C1—N1—O1	112.30 (14)	C1—C4—H4A	109.5
C2—N2—C3	117.27 (15)	C1—C4—H4B	109.5
N1—C1—C2	114.21 (15)	H4A—C4—H4B	109.5
N1—C1—C4	124.96 (16)	C1—C4—H4C	109.5
C2—C1—C4	120.81 (14)	H4A—C4—H4C	109.5
N2—C2—C1	117.70 (15)	H4B—C4—H4C	109.5
N2—C2—C5	123.89 (16)	C2—C5—H5A	109.5
C1—C2—C5	118.41 (14)	C2—C5—H5B	109.5
N2—C3—C3ⁱ	110.88 (19)	H5A—C5—H5B	109.5
N2—C3—H3A	109.5	C2—C5—H5C	109.5
C3ⁱ—C3—H3A	109.5	H5A—C5—H5C	109.5
N2—C3—H3B	109.5	H5B—C5—H5C	109.5
C3ⁱ—C3—H3B	109.5

O1—N1—C1—C2	−179.86 (14)	C4—C1—C2—N2	0.4 (3)
O1—N1—C1—C4	1.8 (3)	N1—C1—C2—C5	1.9 (2)
C3—N2—C2—C1	178.63 (15)	C4—C1—C2—C5	−179.72 (18)
C3—N2—C2—C5	−1.3 (2)	C2—N2—C3—C3ⁱ	−174.31 (18)
N1—C1—C2—N2	−178.05 (16)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2ⁱⁱ	0.82	2.12	2.8384 (19)	146

Symmetry code: (ii) x+1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₈N₄O₂
M_r	226.28
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	4.4128 (3), 12.8534 (8), 10.4860 (7)
β (°)	90.762 (2)
V (Å³)	594.71 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.16 × 0.13 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3578, 1293, 939
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.132, 1.05
No. of reflections	1293
No. of parameters	75
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.22

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), 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
O1—H1···N2ⁱ	0.82	2.12	2.8384 (19)	146

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

Acknowledgements

The authors thank Kasetsart University Research and Development Institute and the Department of Chemistry, Faculty of Science, Kasetsart University, for financial support.

References

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