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

Abstract

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,

• a = 4.4128 (3) Å

• b = 12.8534 (8) Å

• c = 10.4860 (7) Å

• β = 90.762 (2)°

• V = 594.71 (7) ų

• 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[F ² > 2σ(F ²)] = 0.049

• wR(F ²) = 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

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.

Supplementary Material

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

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) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

All H atoms were geometrically positioned (C—H 0.93–0.97 A^o) and refined as riding, with U_iso(H)= 1.2–1.5 U_eq of the parent atom.

Figures

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.]

Crystal data

C10H18N4O2	F(000) = 244
Mr = 226.28	Dx = 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

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

Refinement

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(Fo2) + (0.0571P)2 + 0.1569P] where P = (Fo2 + 2Fc2)/3
1293 reflections	(Δ/σ)max < 0.001
75 parameters	Δρmax = 0.16 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, °)

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

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