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Acta Crystallogr Sect E Struct Rep Online. 2012 March 1; 68(Pt 3): o842.
Published online 2012 February 24. doi:  10.1107/S1600536812007398
PMCID: PMC3297900

Diethyl 2,2′-bis­(hy­droxy­imino)-3,3′-(hydrazinediyl­idene)dibutano­ate

Abstract

Each mol­ecule of the title compound, C12H18N4O6, is located on an inversion centre at the mid-point of the central N—N bond. The azo groups C=N of the Schiff base group have an E conformation and the azo groups in the oxime C=N—O groups have a Z conformation. O–H(...)O hydrogen bonds link neighbouring mol­ecules into infinite monolayers perpendicular to the a axis.

Related literature  

For background to strobilurin A and strobilurin analogs, see: Zhao et al. (2007 [triangle]); Balbaa (2007 [triangle]); Li et al. (2010 [triangle]); Zakharychev et al. (1999 [triangle], 2001 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-68-0o842-scheme1.jpg

Experimental  

Crystal data  

  • C12H18N4O6
  • M r = 314.30
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-68-0o842-efi1.jpg
  • a = 10.8587 (11) Å
  • b = 8.3068 (9) Å
  • c = 8.8465 (9) Å
  • β = 99.782 (2)°
  • V = 786.36 (14) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 296 K
  • 0.18 × 0.18 × 0.10 mm

Data collection  

  • Bruker APEXII CCD diffractometer
  • 3779 measured reflections
  • 1385 independent reflections
  • 1235 reflections with I > 2σ(I)
  • R int = 0.015

Refinement  

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.110
  • S = 1.09
  • 1385 reflections
  • 103 parameters
  • H-atom parameters constrained
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.24 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; 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 datablock(s) global, I. DOI: 10.1107/S1600536812007398/zl2446sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812007398/zl2446Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812007398/zl2446Isup3.cml

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

Acknowledgments

The authors acknowledge support by the Foundation of the Defense Industrial Technology Development Program of China (grant No. B09201100051).

supplementary crystallographic information

Comment

The strobilurins (Balbaa, 2007; Li et al., 2010; Zhao et al., 2007) are one of the most important classes of agricultural fungicides, with Strobilurin A as the lead compound, which inhibit electron transfer in mitochondria, disrupt metabolism and prevent growth of the target fungi. Reaction of 2-hydroxyimino-3-oxobutanoic acid esters with hydrazine hydrate can afford a product with a structure close to that of Strobilurin A (Zakharychev et al., 1999; Zakharychev et al., 2001). Herein, we report the synthesis and crystal structure of this compound, diethyl-2,2'-(hydroxyimino)-3,3'-azino-di-butanoate.

A perspective view of the title compound, showing the atomic numbering scheme, is given in Fig. 1. The complete molecule of the title compound is located on an inversion centre at the mid-point of the the central N—N bond. The azo groups in Schiff base C═N group are in E configuration and the azo groups in the oxime C═N—O groups are in Z configuration. The bond lengths (Allen et al., 1987) and angles in the molecule are within normal ranges. In each molecule, twelve atoms including C4, C4i, C5, C5i, C6, C6i, N1, N1i, N2, N2i, O3, O3i (symmetry code: i = -x, -y, -z) are coplanar with little deviation from their mean plane of 0.090 (3), 0.039 (4), 0.026 (3), 0.030 (1), 0.088 (5), and 0.007 (1) Å, respectively, and the deviation from the mean plane of other atoms C1, C1i, C2, C2i, C3, C3i, O1, O1i, and O2, O2i are 0.778 (2), 0.545 (4), 0.396 (5), 0.691 (1) and 1.523 (7) Å, respectively. Meanwhile, the dihedral angle between the plane defined by C2, C3, C4, O1 and O2 and the main plane is 87.87 (2) °.

In the crystal environment of each molecule of the title compound, there exist four symmetry equivalent intermolecular O3—H3···O2 hydrogen bonds (Table 1, Fig. 2), two of which originate from the each molecule and two for which the molecule acts as the H bonding acceptor unit. Each molecule links neighbouring molecules into an infinite monolayer perpendicular to the a axis (Fig. 3).

Experimental

To an acetic acid (32 ml) solution of ethyl acetoacetate (15 g) was added a solution of sodium nitrite in water (25 ml) at 263 K, and the reaction mixture was poured to ice-water (100 ml), then the mixture was extracted three times with ether (50 ml). The extracts were washed with water, after which the solvent was distilled off to give a light yellow residue. This residue was dissolved in methanol (20 ml) and the solution was added dropwise to a mixture of hydrazine hydrate (2.9 g, 85%), methanol (50 ml) and water (37 ml) at 273 K, and the resulting mixture was stirred for six hours at the same temperature. The reaction mixture was extracted two times with ethyl acetate (50 ml), then the extracts were washed with water and dried over magnesium sulfate, filtered and the solvent was removed to give the crude product. The title compound was purified by column chromatography on silica gel using a mixture of dichloromethane and methanol (Rf = 0.35, 20:1, V/V) as the eluent, affording the title compound 4.71 g. Yield, 26.1%. m. p. 473–475 K. 1H NMR (d6-DMSO): 1.24 (t, 6H, 3J = 7.10 Hz), 1.96 (s, 6H), 4.25 (q, 4H, 3J = 7.08 Hz), 12.54 (s, 2H).

Pale yellow block-like single crystals of the title compound suitable for X-ray diffraction studies were obtained after three weeks by slow evaporation from a mixture of dichloromethane and methanol at room temperature.

Refinement

The carbon-bound H-atoms were positioned geometrically and included in the refinement using a riding model with distances C—H = 0.96 Å (CH3) and 0.97 Å (CH2). And the oxygen-bound H-atoms were located in difference Fourier maps and refined with an O—H distance constrained to 0.85 Å. The isotropic displacement parameters for all H atoms were set equal to 1.2 Ueq (for CH2) or 1.5 Ueq (for CH3 and OH) of the carrier atom.

Figures

Fig. 1.
The molecular structure of the title compound with the atom numbering scheme [symmetry code: i) -x, -y, -z]. Displacement ellipsoids for non-hydrogen atoms are drawn at the 30% probability level.
Fig. 2.
Intermolecular hydrogen bonding of the title compound viewed along the a axis. Hydrogen atoms not involved in hydrogen bonding have been omitted for clarity.
Fig. 3.
View of intermolecular hydrogen bonding, showing sections of two infinite two-dimensional monolayers viewed along the b axis. H atoms not involved in hydrogen bonding have been omitted for clarity.

Crystal data

C12H18N4O6F(000) = 332
Mr = 314.30Dx = 1.327 Mg m3
Monoclinic, P21/cMelting point = 473–475 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 10.8587 (11) ÅCell parameters from 2318 reflections
b = 8.3068 (9) Åθ = 3.1–28.2°
c = 8.8465 (9) ŵ = 0.11 mm1
β = 99.782 (2)°T = 296 K
V = 786.36 (14) Å3Block-like, yellow
Z = 20.18 × 0.18 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer1235 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.015
Graphite monochromatorθmax = 25.0°, θmin = 1.9°
[var phi] and ω scansh = −6→12
3779 measured reflectionsk = −9→9
1385 independent reflectionsl = −10→10

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110H-atom parameters constrained
S = 1.09w = 1/[σ2(Fo2) + (0.0587P)2 + 0.202P] where P = (Fo2 + 2Fc2)/3
1385 reflections(Δ/σ)max = 0.001
103 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = −0.24 e Å3

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 (Å2)

xyzUiso*/Ueq
C10.3173 (2)−0.3855 (3)0.1974 (3)0.0815 (7)
H1A0.2823−0.34860.09640.122*
H1B0.2514−0.42290.24850.122*
H1C0.3745−0.47200.18990.122*
C20.38401 (17)−0.2522 (2)0.2854 (2)0.0543 (5)
H2A0.4193−0.28900.38770.065*
H2B0.4520−0.21590.23550.065*
C30.29765 (13)0.00236 (17)0.20059 (16)0.0335 (3)
C40.20477 (13)0.12983 (16)0.22471 (16)0.0350 (4)
C50.08145 (13)0.12936 (17)0.12596 (17)0.0364 (4)
C6−0.00087 (18)0.2722 (2)0.1254 (3)0.0702 (6)
H6A−0.07990.25110.06150.105*
H6B0.03770.36360.08620.105*
H6C−0.01370.29430.22810.105*
O10.29746 (10)−0.11865 (13)0.29545 (13)0.0455 (3)
O20.36466 (10)0.01499 (13)0.10565 (12)0.0442 (3)
O30.34902 (10)0.22632 (15)0.40794 (13)0.0518 (4)
H30.36260.29980.47040.078*
N20.22952 (12)0.24201 (15)0.32449 (15)0.0431 (4)
N10.05904 (11)0.00033 (14)0.04649 (14)0.0372 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0890 (16)0.0520 (12)0.0992 (17)0.0159 (11)0.0036 (13)−0.0098 (11)
C20.0521 (10)0.0444 (10)0.0662 (11)0.0153 (7)0.0097 (9)0.0135 (8)
C30.0317 (7)0.0335 (8)0.0333 (7)−0.0029 (6)−0.0005 (6)−0.0018 (5)
C40.0343 (8)0.0335 (8)0.0370 (7)−0.0025 (6)0.0056 (6)−0.0020 (6)
C50.0333 (8)0.0356 (8)0.0399 (8)0.0008 (6)0.0051 (6)−0.0025 (6)
C60.0517 (11)0.0600 (12)0.0899 (15)0.0196 (9)−0.0140 (10)−0.0303 (11)
O10.0461 (7)0.0393 (6)0.0530 (7)0.0064 (5)0.0133 (5)0.0100 (5)
O20.0430 (6)0.0473 (7)0.0441 (6)0.0072 (5)0.0123 (5)0.0068 (5)
O30.0424 (6)0.0549 (7)0.0529 (7)−0.0011 (5)−0.0065 (5)−0.0187 (5)
N20.0381 (7)0.0438 (8)0.0458 (7)−0.0014 (5)0.0026 (6)−0.0101 (6)
N10.0318 (6)0.0352 (7)0.0420 (7)−0.0003 (5)−0.0012 (5)−0.0008 (5)

Geometric parameters (Å, º)

C1—C21.472 (3)C4—N21.2803 (19)
C1—H1A0.9600C4—C51.469 (2)
C1—H1B0.9600C5—N11.2822 (19)
C1—H1C0.9600C5—C61.485 (2)
C2—O11.4663 (19)C6—H6A0.9600
C2—H2A0.9700C6—H6B0.9600
C2—H2B0.9700C6—H6C0.9600
C3—O21.2056 (17)O3—N21.3857 (17)
C3—O11.3097 (18)O3—H30.8200
C3—C41.5024 (19)N1—N1i1.401 (2)
C2—C1—H1A109.5N2—C4—C3122.92 (13)
C2—C1—H1B109.5C5—C4—C3118.66 (12)
H1A—C1—H1B109.5N1—C5—C4113.40 (12)
C2—C1—H1C109.5N1—C5—C6127.44 (14)
H1A—C1—H1C109.5C4—C5—C6119.15 (13)
H1B—C1—H1C109.5C5—C6—H6A109.5
O1—C2—C1109.77 (16)C5—C6—H6B109.5
O1—C2—H2A109.7H6A—C6—H6B109.5
C1—C2—H2A109.7C5—C6—H6C109.5
O1—C2—H2B109.7H6A—C6—H6C109.5
C1—C2—H2B109.7H6B—C6—H6C109.5
H2A—C2—H2B108.2C3—O1—C2118.11 (12)
O2—C3—O1125.45 (13)N2—O3—H3109.5
O2—C3—C4122.47 (13)C4—N2—O3111.52 (12)
O1—C3—C4112.07 (12)C5—N1—N1i113.25 (14)
N2—C4—C5118.38 (13)
O2—C3—C4—N2−93.59 (18)O2—C3—O1—C2−1.0 (2)
O1—C3—C4—N285.26 (17)C4—C3—O1—C2−179.80 (13)
O2—C3—C4—C584.22 (17)C1—C2—O1—C3−99.25 (19)
O1—C3—C4—C5−96.93 (15)C5—C4—N2—O3−179.79 (12)
N2—C4—C5—N1−170.22 (14)C3—C4—N2—O3−2.0 (2)
C3—C4—C5—N111.88 (19)C4—C5—N1—N1i179.46 (13)
N2—C4—C5—C610.7 (2)C6—C5—N1—N1i−1.6 (3)
C3—C4—C5—C6−167.18 (16)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···AD—HH···AD···AD—H···A
O3—H3···O2ii0.821.952.7577 (15)170

Symmetry code: (ii) x, −y+1/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2446).

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.
  • Balbaa, H. (2007). J. Environ. Sci. Health Part B, 4, 441–451.
  • Bruker (2007). APEX2 and SAINTBruker AXS Inc., Madison, Wisconsin, USA.
  • Li, M., Liu, C.-L., Yang, J.-C., Zhang, G.-B., Li, Z.-N., Zhang, H. & Li, Z.-M. (2010). J. Agric. Food Chem. 5, 2664–2667. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zakharychev, V. V., Golubtsova, M. D. & Kovalenko, L. V. (1999). Russ. Chem. Bull. 3, 495–500.
  • Zakharychev, V. V., Golubtsova, M. D. & Kovalenko, L. V. (2001). Russ. J. Org. Chem. 8, 1184–1185.
  • Zhao, P.-L., Liu, C.-L., Huang, W., Wang, Y.-Z. & Yang, G.-F. (2007). J. Agric. Food Chem. 14, 5697–5700. [PubMed]

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