Bis(4-ammonio-4-methyl­pentan-2-one-κO)dioxalato-κ4O1,O2-copper(II)

Ji, Z.; Wei, S.; Wu, W.

doi:10.1107/S1600536808042396

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page m182

doi:10.1107/S1600536808042396

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Bis(4-ammonio-4-methylpentan-2-one-κO)dioxalato-κ⁴O¹,O²-copper(II)

Zhiqin Ji,^a Shaopeng Wei ^a and Wenjun Wu ^a ^*

^aInstitute of Pesticide Science, Northwest Agricultural & Forestry University, YangLing, Shaanxi 712100, People's Republic of China
^*Correspondence e-mail: wenjun_wu@263.net

(Received 4 August 2008; accepted 12 December 2008; online 14 January 2009)

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 Cu^II 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.

Related literature

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

Experimental

Crystal data

[Cu(C₂O₄)₂(C₆H₁₄NO)₂]
M_r = 471.94
Monoclinic, C 2/m
a = 13.639 (3) Å
b = 7.9749 (16) Å
c = 10.958 (2) Å
β = 113.27 (3)°
V = 1094.9 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.05 mm⁻¹
T = 113 (2) K
0.16 × 0.14 × 0.14 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.850, T_max = 0.867
4513 measured reflections
1394 independent reflections
1247 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.075
S = 1.11
1394 reflections
83 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—O1	1.9383 (11)
Cu1—O3	2.663 (2)

O1—Cu1—O1ⁱ	179.999 (2)
O1—Cu1—O1ⁱⁱ	94.90 (6)
O1ⁱ—Cu1—O1ⁱⁱ	85.10 (6)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, y, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱⁱⁱ	0.86 (3)	2.23 (2)	2.950 (2)	141.8 (5)
N1—H1A⋯O2^iv	0.86 (3)	2.23 (2)	2.950 (2)	141.8 (5)
N1—H1B⋯O2^v	0.883 (18)	2.014 (19)	2.8651 (14)	161.5 (16)
Symmetry codes: (iii) -x+1, y, -z; (iv) -x+1, -y+1, -z; (v) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ .

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808042396/jh2070sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808042396/jh2070Isup2.hkl

checkCIF report

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

	Fig. 1. Molecular structure of the title compound, showing the coordination geometry. Displacement ellipsoids are drawn at the 50% probability level.
	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
M_r = 471.94	D_x = 1.432 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 13.639 (3) Å	Cell parameters from 2107 reflections
b = 7.9749 (16) Å	θ = 3.3–27.9°
c = 10.958 (2) Å	µ = 1.05 mm⁻¹
β = 113.27 (3)°	T = 113 K
V = 1094.9 (4) Å³	Prism, colorless
Z = 2	0.16 × 0.14 × 0.14 mm

Data collection top

Rigaku Saturn CCD area-detector diffractometer	1394 independent reflections
Radiation source: rotating anode	1247 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.033
Detector resolution: 7.31 pixels mm^-1	θ_max = 27.9°, θ_min = 3.3°
ω and ϕ scans	h = −17→17
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→9
T_min = 0.850, T_max = 0.867	l = −12→14
4513 measured reflections

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.0374P)² + 0.4743P] where P = (F_o² + 2F_c²)/3
1394 reflections	(Δ/σ)_max = 0.001
83 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

[Cu(C₂O₄)₂(C₆H₁₄NO)₂]	V = 1094.9 (4) Å³
M_r = 471.94	Z = 2
Monoclinic, C2/m	Mo Kα radiation
a = 13.639 (3) Å	µ = 1.05 mm⁻¹
b = 7.9749 (16) Å	T = 113 K
c = 10.958 (2) Å	0.16 × 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)
T_min = 0.850, T_max = 0.867	R_int = 0.033
4513 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.31 e Å⁻³
1394 reflections	Δρ_min = −0.45 e Å⁻³
83 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 > 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

	x	y	z	U_iso*/U_eq
Cu1	0.5000	0.5000	0.5000	0.01576 (13)
O1	0.44732 (8)	0.33564 (13)	0.35854 (10)	0.0177 (2)
O2	0.36121 (9)	0.32743 (14)	0.13800 (10)	0.0200 (2)
N1	0.76865 (14)	0.5000	0.11200 (17)	0.0153 (4)
H1A	0.727 (2)	0.5000	0.029 (3)	0.023*
H1B	0.8108 (14)	0.412 (2)	0.1262 (17)	0.023*
O3	0.67707 (15)	0.5000	0.45267 (19)	0.0361 (4)
C1	0.40342 (10)	0.40251 (18)	0.24483 (13)	0.0142 (3)
C2	0.8619 (2)	0.5000	0.5942 (2)	0.0320 (6)
H2A	0.8364	0.5000	0.6642	0.048*
H2B	0.9045	0.4017	0.6013	0.048*
C3	0.76883 (19)	0.5000	0.4625 (2)	0.0216 (5)
C4	0.80035 (16)	0.5000	0.3451 (2)	0.0170 (4)
H4A	0.8441	0.4031	0.3524	0.020*
C5	0.71136 (16)	0.5000	0.2061 (2)	0.0168 (4)
C6	0.64379 (13)	0.6585 (2)	0.17734 (17)	0.0274 (4)
H6A	0.5934	0.6585	0.0841	0.041*
H6B	0.6903	0.7570	0.1944	0.041*
H6C	0.6042	0.6620	0.2349	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0216 (2)	0.00972 (19)	0.01316 (19)	0.000	0.00386 (14)	0.000
O1	0.0239 (6)	0.0113 (5)	0.0155 (5)	−0.0008 (4)	0.0053 (4)	0.0002 (4)
O2	0.0245 (6)	0.0152 (6)	0.0166 (5)	−0.0027 (4)	0.0042 (4)	−0.0028 (4)
N1	0.0160 (9)	0.0143 (9)	0.0147 (8)	0.000	0.0052 (7)	0.000
O3	0.0348 (10)	0.0458 (12)	0.0400 (10)	0.000	0.0280 (9)	0.000
C1	0.0133 (7)	0.0114 (7)	0.0189 (7)	−0.0013 (5)	0.0074 (6)	−0.0009 (5)
C2	0.0452 (15)	0.0325 (14)	0.0208 (11)	0.000	0.0156 (11)	0.000
C3	0.0303 (12)	0.0149 (10)	0.0248 (11)	0.000	0.0165 (9)	0.000
C4	0.0168 (10)	0.0172 (10)	0.0189 (10)	0.000	0.0089 (8)	0.000
C5	0.0152 (10)	0.0172 (11)	0.0200 (10)	0.000	0.0092 (8)	0.000
C6	0.0222 (8)	0.0298 (10)	0.0326 (9)	0.0100 (7)	0.0133 (7)	0.0059 (7)

Geometric parameters (Å, º) top

Cu1—O1ⁱ	1.9383 (11)	C1—C1ⁱ	1.555 (3)
Cu1—O1	1.9383 (11)	C2—C3	1.499 (3)
Cu1—O1ⁱⁱ	1.9383 (11)	C2—H2A	0.9601
Cu1—O1ⁱⁱⁱ	1.9383 (11)	C2—H2B	0.9600
Cu1—O3	2.663 (2)	C3—C4	1.508 (3)
Cu1—O3	2.663 (2)	C4—C5	1.528 (3)
O1—C1	1.2672 (17)	C4—H4A	0.9601
O2—C1	1.2361 (17)	C5—C6	1.522 (2)
N1—C5	1.520 (3)	C5—C6ⁱ	1.522 (2)
N1—H1A	0.86 (3)	C6—H6A	0.9800
N1—H1B	0.883 (18)	C6—H6B	0.9800
O3—C3	1.213 (3)	C6—H6C	0.9800

O1ⁱ—Cu1—O1	85.10 (6)	O3—C3—C4	123.8 (2)
O1ⁱ—Cu1—O1ⁱⁱ	94.90 (6)	C2—C3—C4	113.71 (19)
O1—Cu1—O1ⁱⁱ	179.999 (2)	C3—C4—C5	117.95 (18)
O1ⁱ—Cu1—O1ⁱⁱⁱ	180	C3—C4—H4A	107.8
O1—Cu1—O1ⁱⁱⁱ	94.90 (6)	C5—C4—H4A	107.8
O1ⁱⁱ—Cu1—O1ⁱⁱⁱ	85.10 (6)	N1—C5—C6	106.94 (11)
C1—O1—Cu1	112.56 (10)	N1—C5—C6ⁱ	106.94 (11)
C5—N1—H1A	114.0 (17)	C6—C5—C6ⁱ	112.28 (19)
C5—N1—H1B	110.8 (11)	N1—C5—C4	104.95 (16)
H1A—N1—H1B	107.6 (14)	C6—C5—C4	112.57 (11)
O2—C1—O1	126.13 (14)	C6ⁱ—C5—C4	112.57 (11)
O2—C1—C1ⁱ	118.98 (8)	C5—C6—H6A	109.5
O1—C1—C1ⁱ	114.89 (8)	C5—C6—H6B	109.5
C3—C2—H2A	109.5	H6A—C6—H6B	109.5
C3—C2—H2B	109.5	C5—C6—H6C	109.5
H2A—C2—H2B	109.5	H6A—C6—H6C	109.5
O3—C3—C2	122.5 (2)	H6B—C6—H6C	109.5

O1ⁱ—Cu1—O1—C1	−1.03 (11)	O3—C3—C4—C5	0.0
O1ⁱⁱ—Cu1—O1—C1	−71 (11)	C2—C3—C4—C5	180.0
O1ⁱⁱⁱ—Cu1—O1—C1	178.97 (11)	C3—C4—C5—N1	180.0
Cu1—O1—C1—O2	−178.41 (11)	C3—C4—C5—C6	64.06 (12)
Cu1—O1—C1—C1ⁱ	0.84 (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, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2^iv	0.86 (3)	2.23 (2)	2.950 (2)	142 (1)
N1—H1A···O2^v	0.86 (3)	2.23 (2)	2.950 (2)	142 (1)
N1—H1B···O2^vi	0.883 (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.

Experimental details

Crystal data
Chemical formula	[Cu(C₂O₄)₂(C₆H₁₄NO)₂]
M_r	471.94
Crystal system, space group	Monoclinic, C2/m
Temperature (K)	113
a, b, c (Å)	13.639 (3), 7.9749 (16), 10.958 (2)
β (°)	113.27 (3)
V (Å³)	1094.9 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.05
Crystal size (mm)	0.16 × 0.14 × 0.14

Data collection
Diffractometer	Rigaku Saturn CCD area-detector diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.850, 0.867
No. of measured, independent and observed [I > 2σ(I)] reflections	4513, 1394, 1247
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.657

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.075, 1.11
No. of reflections	1394
No. of parameters	83
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.45

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), CrystalStructure (Rigaku, 2005).

Selected geometric parameters (Å, º) top

Cu1—O1	1.9383 (11)

O1—Cu1—O1ⁱ	179.999 (2)	O1ⁱ—Cu1—O1ⁱⁱ	85.10 (6)
O1—Cu1—O1ⁱⁱ	94.90 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱⁱⁱ	0.86 (3)	2.23 (2)	2.950 (2)	141.8 (5)
N1—H1A···O2^iv	0.86 (3)	2.23 (2)	2.950 (2)	141.8 (5)
N1—H1B···O2^v	0.883 (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

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

References

Haeseler (1925). J. Am. Chem. Soc. 47, 1195y. Google Scholar
Rigaku (2005). CrystalStructure and CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar