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Acta Cryst. (2009). E65, m182    [ doi:10.1107/S1600536808042396 ]

Bis(4-ammonio-4-methylpentan-2-one-[kappa]O)dioxalato-[kappa]4O1,O2-copper(II)

Z. Ji, S. Wei and W. Wu

Abstract top

The title compound, [Cu(C2O4)2(C6H14NO)2], was synthesized by mixing diacetonamine hydrogen oxalate and copper sulfate in ethanol/water. The molecule is centrosymmetric, so two pairs of equivalent ligands lie trans to each other. The CuII center, located on a position with 2/m site symmetry, is six-coordinated by four O atoms from two oxalate ligands at short distances and the carbonyl O atoms from the 4-amino-4-methylpentan-2-one ligands at longer distances. Molecules are linked through intermolecular N-H...O hydrogen bonds between the amino groups and carbonyl O atoms; no intramolecular hydrogen bonds are formed.

Comment top

In the screening of novel antibiotics, diacetonamine was obtained in the procedure of isolating active ingredients by the silica gel chromatography. Diacetonamine exhibites moderatly antimicrobial activities against many species of plant-pathogenic fungus. To enhance the bio-activity, a complex was designed and prepared by the mixture of diacetonamine hydrogen oxalate and copper sulfate. Compared with diacetonamine, the antimicrobial activities of copper complex was increased dramaticaly. Diacetonamine could be prepared from a mixture of mesityl oxide with aqueous ammonia or liquid ammonia(Haeseler, 1925). In this paper, [Cu(C6H13NO)2 (C2H2O4)2] was synthesized by the reaction of CuSO4.5H2O and diacetonamine hydrogen oxalate in ethanol/water and the structure of the resulting complex is presented herein.

Related literature top

For the preparation of diacetonamine, see: Haeseler (1925).

Experimental top

Diacetonamine hydrogen oxalate(0.6 mmol 123 mg) was dissolved in ethnaol/water (2/1,volume ratio, 10 ml) and the solution was heated to boiling. Copper sulfate(0.3 mmol 75 mg) was dissolved in deionized water(10 ml), and was added dropwise to the solution and stirred for 10 minutes. The mother liquid was placed at room temperature, and single crystals were obtained on standing.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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: CrystalStructure (Rigaku, 2005).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound, showing the coordination geometry. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Packing diagram viewed down the c-axis,showing hydrogen bonds.
Bis(4-ammonio-4-methylpentan-2-one-κO)dioxalato- κ4O1,O2)copper(II) top
Crystal data top
[Cu(C2O4)2(C6H14NO)2]F(000) = 494
Mr = 471.94Dx = 1.432 Mg m−3
Monoclinic, C2/mMo Kα radiation, λ = 0.71073 Å
a = 13.639 (3) ÅCell parameters from 2107 reflections
b = 7.9749 (16) Åθ = 3.3–27.9°
c = 10.958 (2) ŵ = 1.05 mm−1
β = 113.27 (3)°T = 113 K
V = 1094.9 (4) Å3Prism, colorless
Z = 20.16 × 0.14 × 0.14 mm
Data collection top
Rigaku Saturn CCD area-detector
diffractometer		1394 independent reflections
Radiation source: rotating anode1247 reflections with I > 2σ(I)
confocalRint = 0.033
Detector resolution: 7.31 pixels mm-1θmax = 27.9°, θmin = 3.3°
ω and φ scansh = −17→17
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		k = −10→9
Tmin = 0.850, Tmax = 0.867l = −12→14
4513 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075H atoms treated by a mixture of independent and constrained refinement
S = 1.11 w = 1/[σ2(Fo2) + (0.0374P)2 + 0.4743P]
where P = (Fo2 + 2Fc2)/3
1394 reflections(Δ/σ)max = 0.001
83 parametersΔρmax = 0.31 e Å−3
0 restraintsΔρmin = −0.45 e Å−3
Crystal data top
[Cu(C2O4)2(C6H14NO)2]V = 1094.9 (4) Å3
Mr = 471.94Z = 2
Monoclinic, C2/mMo Kα radiation
a = 13.639 (3) ŵ = 1.05 mm−1
b = 7.9749 (16) ÅT = 113 K
c = 10.958 (2) Å0.16 × 0.14 × 0.14 mm
β = 113.27 (3)°
Data collection top
Rigaku Saturn CCD area-detector
diffractometer		1394 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		1247 reflections with I > 2σ(I)
Tmin = 0.850, Tmax = 0.867Rint = 0.033
4513 measured reflectionsθmax = 27.9°
Refinement top
R[F2 > 2σ(F2)] = 0.026H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.075Δρmax = 0.31 e Å−3
S = 1.11Δρmin = −0.45 e Å−3
1394 reflectionsAbsolute structure: ?
83 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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 > 2sigma(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
xyzUiso*/Ueq
Cu10.50000.50000.50000.01576 (13)
O10.44732 (8)0.33564 (13)0.35854 (10)0.0177 (2)
O20.36121 (9)0.32743 (14)0.13800 (10)0.0200 (2)
N10.76865 (14)0.50000.11200 (17)0.0153 (4)
H1A0.727 (2)0.50000.029 (3)0.023*
H1B0.8108 (14)0.412 (2)0.1262 (17)0.023*
O30.67707 (15)0.50000.45267 (19)0.0361 (4)
C10.40342 (10)0.40251 (18)0.24483 (13)0.0142 (3)
C20.8619 (2)0.50000.5942 (2)0.0320 (6)
H2A0.83640.50000.66420.048*
H2B0.90450.40170.60130.048*
C30.76883 (19)0.50000.4625 (2)0.0216 (5)
C40.80035 (16)0.50000.3451 (2)0.0170 (4)
H4A0.84410.40310.35240.020*
C50.71136 (16)0.50000.2061 (2)0.0168 (4)
C60.64379 (13)0.6585 (2)0.17734 (17)0.0274 (4)
H6A0.59340.65850.08410.041*
H6B0.69030.75700.19440.041*
H6C0.60420.66200.23490.041*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0216 (2)0.00972 (19)0.01316 (19)0.0000.00386 (14)0.000
O10.0239 (6)0.0113 (5)0.0155 (5)−0.0008 (4)0.0053 (4)0.0002 (4)
O20.0245 (6)0.0152 (6)0.0166 (5)−0.0027 (4)0.0042 (4)−0.0028 (4)
N10.0160 (9)0.0143 (9)0.0147 (8)0.0000.0052 (7)0.000
O30.0348 (10)0.0458 (12)0.0400 (10)0.0000.0280 (9)0.000
C10.0133 (7)0.0114 (7)0.0189 (7)−0.0013 (5)0.0074 (6)−0.0009 (5)
C20.0452 (15)0.0325 (14)0.0208 (11)0.0000.0156 (11)0.000
C30.0303 (12)0.0149 (10)0.0248 (11)0.0000.0165 (9)0.000
C40.0168 (10)0.0172 (10)0.0189 (10)0.0000.0089 (8)0.000
C50.0152 (10)0.0172 (11)0.0200 (10)0.0000.0092 (8)0.000
C60.0222 (8)0.0298 (10)0.0326 (9)0.0100 (7)0.0133 (7)0.0059 (7)
Geometric parameters (Å, °) top
Cu1—O1i1.9383 (11)C1—C1i1.555 (3)
Cu1—O11.9383 (11)C2—C31.499 (3)
Cu1—O1ii1.9383 (11)C2—H2A0.9601
Cu1—O1iii1.9383 (11)C2—H2B0.9600
Cu1—O32.663 (2)C3—C41.508 (3)
Cu1—O32.663 (2)C4—C51.528 (3)
O1—C11.2672 (17)C4—H4A0.9601
O2—C11.2361 (17)C5—C61.522 (2)
N1—C51.520 (3)C5—C6i1.522 (2)
N1—H1A0.86 (3)C6—H6A0.9800
N1—H1B0.883 (18)C6—H6B0.9800
O3—C31.213 (3)C6—H6C0.9800
O1i—Cu1—O185.10 (6)O3—C3—C4123.8 (2)
O1i—Cu1—O1ii94.90 (6)C2—C3—C4113.71 (19)
O1—Cu1—O1ii179.999 (2)C3—C4—C5117.95 (18)
O1i—Cu1—O1iii180C3—C4—H4A107.8
O1—Cu1—O1iii94.90 (6)C5—C4—H4A107.8
O1ii—Cu1—O1iii85.10 (6)N1—C5—C6106.94 (11)
C1—O1—Cu1112.56 (10)N1—C5—C6i106.94 (11)
C5—N1—H1A114.0 (17)C6—C5—C6i112.28 (19)
C5—N1—H1B110.8 (11)N1—C5—C4104.95 (16)
H1A—N1—H1B107.6 (14)C6—C5—C4112.57 (11)
O2—C1—O1126.13 (14)C6i—C5—C4112.57 (11)
O2—C1—C1i118.98 (8)C5—C6—H6A109.5
O1—C1—C1i114.89 (8)C5—C6—H6B109.5
C3—C2—H2A109.5H6A—C6—H6B109.5
C3—C2—H2B109.5C5—C6—H6C109.5
H2A—C2—H2B109.5H6A—C6—H6C109.5
O3—C3—C2122.5 (2)H6B—C6—H6C109.5
O1i—Cu1—O1—C1−1.03 (11)O3—C3—C4—C50.0
O1ii—Cu1—O1—C1−71 (11)C2—C3—C4—C5180.0
O1iii—Cu1—O1—C1178.97 (11)C3—C4—C5—N1180.0
Cu1—O1—C1—O2−178.41 (11)C3—C4—C5—C664.06 (12)
Cu1—O1—C1—C1i0.84 (9)C3—C4—C5—C6i−64.06 (12)
Symmetry codes: (i) x, −y+1, z; (ii) −x+1, −y+1, −z+1; (iii) −x+1, y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2iv0.86 (3)2.23 (2)2.950 (2)142 (1)
N1—H1A···O2v0.86 (3)2.23 (2)2.950 (2)142 (1)
N1—H1B···O2vi0.883 (18)2.014 (19)2.8651 (14)161.5 (16)
Symmetry codes: (iv) −x+1, y, −z; (v) −x+1, −y+1, −z; (vi) x+1/2, −y+1/2, z.
Table 1
Selected geometric parameters (Å, °) top
Cu1—O11.9383 (11)
O1—Cu1—O1i179.999 (2)O1i—Cu1—O1ii85.10 (6)
O1—Cu1—O1ii94.90 (6)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2iii0.86 (3)2.23 (2)2.950 (2)142 (1)
N1—H1A···O2iv0.86 (3)2.23 (2)2.950 (2)142 (1)
N1—H1B···O2v0.883 (18)2.014 (19)2.8651 (14)161.5 (16)
Symmetry codes: (iii) −x+1, y, −z; (iv) −x+1, −y+1, −z; (v) x+1/2, −y+1/2, z.
Acknowledgements top

The authors thank Dr Qingmin Wang for assistance with the X-ray structure determination.

references
References top

Haeseler (1925). J. Am. Chem. Soc. 47, 1195y

Rigaku (2005). CrystalStructure and CrystalClear. Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.