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In the structure of the mononuclear title complex, [Cu(C8H7O4)2(C2H6OS)2], the CuII atom lies on an inversion centre and has an octahedral coordination geometry of type MO6. The bidentate dehydroacetic acid (DHA) ligands occupy the equatorial plane of the complex in a trans configuration, and the dimethylsulfoxide (DMSO) ligands are weakly coordinated through their O atoms.
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.003 Å
- R factor = 0.035
- wR factor = 0.093
- Data-to-parameter ratio = 22.6
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - O5 .. 6.75 su
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
1 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
A solution of copper acetate monohydrate was added, with stirring, to a solution of dehydroacetic acid in absolute ethanol in a 1:2 stoichiometric ratio. The title complex precipitated after 1 h. The resulting precipitate of (I) was filtered off and recrystallized by slow evaporation of a dimethylsulfoxide solution.
All H atoms were located in difference Fourier maps but introduced in calculated positions and treated as riding on their parent C atoms, with C—H distances of 0.96 Å (CH3) and 0.93 Å (Caromatic) and with Uiso(H) = 1.2Ueq(Caromatic) or 1.5Ueq(CH3).
Data collection: KappaCCD (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia,
1997)
and
PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).
Crystal data top
[Cu(C8H7O4)2(C2H6OS)2] | F(000) = 574 |
Mr = 554.07 | Dx = 1.532 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 11050 reflections |
a = 11.580 (5) Å | θ = 2.1–30.1° |
b = 6.320 (5) Å | µ = 1.14 mm−1 |
c = 16.424 (5) Å | T = 294 K |
β = 92.27 (5)° | Prism, blue |
V = 1201.1 (11) Å3 | 0.1 × 0.1 × 0.1 mm |
Z = 2 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 2651 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.040 |
Graphite monochromator | θmax = 30.1°, θmin = 2.1° |
ϕ scans, and ω scans with κ offsets | h = −13→16 |
11050 measured reflections | k = −6→8 |
3506 independent reflections | l = −22→23 |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0438P)2 + 0.1877P] where P = (Fo2 + 2Fc2)/3 |
3506 reflections | (Δ/σ)max < 0.001 |
155 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
Crystal data top
[Cu(C8H7O4)2(C2H6OS)2] | V = 1201.1 (11) Å3 |
Mr = 554.07 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.580 (5) Å | µ = 1.14 mm−1 |
b = 6.320 (5) Å | T = 294 K |
c = 16.424 (5) Å | 0.1 × 0.1 × 0.1 mm |
β = 92.27 (5)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 2651 reflections with I > 2σ(I) |
11050 measured reflections | Rint = 0.040 |
3506 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.37 e Å−3 |
3506 reflections | Δρmin = −0.39 e Å−3 |
155 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 | Uiso*/Ueq | |
Cu1 | 0.5000 | 0.5000 | 0.5000 | 0.03410 (10) | |
S1 | 0.73751 (4) | 0.21537 (7) | 0.47488 (3) | 0.04139 (13) | |
O1 | 0.45594 (10) | 0.26689 (17) | 0.43168 (7) | 0.0370 (3) | |
O2 | 0.45847 (12) | 0.1864 (2) | 0.18715 (7) | 0.0440 (3) | |
O3 | 0.55902 (15) | 0.4706 (2) | 0.16465 (9) | 0.0545 (4) | |
O4 | 0.58586 (10) | 0.62317 (18) | 0.41185 (7) | 0.0380 (3) | |
O5 | 0.67750 (12) | 0.3121 (2) | 0.54540 (8) | 0.0490 (3) | |
C1 | 0.46505 (13) | 0.2507 (2) | 0.35549 (10) | 0.0300 (3) | |
C2 | 0.41204 (15) | 0.0666 (3) | 0.31725 (11) | 0.0352 (4) | |
H2 | 0.3803 | −0.0375 | 0.3496 | 0.042* | |
C3 | 0.40800 (15) | 0.0437 (3) | 0.23720 (12) | 0.0376 (4) | |
C4 | 0.51841 (15) | 0.3628 (3) | 0.21731 (11) | 0.0372 (4) | |
C5 | 0.52246 (13) | 0.3973 (2) | 0.30415 (10) | 0.0303 (3) | |
C6 | 0.58663 (14) | 0.5735 (3) | 0.33815 (10) | 0.0315 (3) | |
C7 | 0.66346 (17) | 0.7094 (3) | 0.28811 (12) | 0.0462 (4) | |
H7A | 0.6168 | 0.7918 | 0.2503 | 0.069* | |
H7B | 0.7147 | 0.6209 | 0.2586 | 0.069* | |
H7C | 0.7079 | 0.8023 | 0.3234 | 0.069* | |
C8 | 0.35032 (19) | −0.1283 (3) | 0.18953 (13) | 0.0540 (5) | |
H8A | 0.3185 | −0.2294 | 0.2261 | 0.081* | |
H8B | 0.4057 | −0.1971 | 0.1565 | 0.081* | |
H8C | 0.2894 | −0.0698 | 0.1551 | 0.081* | |
C9 | 0.8695 (2) | 0.3578 (3) | 0.46739 (15) | 0.0630 (6) | |
H9A | 0.8531 | 0.4998 | 0.4497 | 0.095* | |
H9B | 0.9170 | 0.2892 | 0.4287 | 0.095* | |
H9C | 0.9095 | 0.3611 | 0.5197 | 0.095* | |
C10 | 0.7993 (2) | −0.0257 (3) | 0.51126 (15) | 0.0553 (5) | |
H10A | 0.8419 | −0.0004 | 0.5616 | 0.083* | |
H10B | 0.8503 | −0.0806 | 0.4717 | 0.083* | |
H10C | 0.7389 | −0.1264 | 0.5201 | 0.083* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.04192 (18) | 0.03601 (16) | 0.02500 (16) | −0.00903 (12) | 0.00933 (12) | −0.00397 (11) |
S1 | 0.0423 (3) | 0.0479 (3) | 0.0340 (2) | 0.00514 (19) | 0.00183 (19) | −0.00032 (19) |
O1 | 0.0475 (7) | 0.0372 (6) | 0.0270 (6) | −0.0099 (5) | 0.0111 (5) | −0.0032 (5) |
O2 | 0.0546 (8) | 0.0496 (7) | 0.0277 (6) | −0.0116 (6) | 0.0014 (6) | −0.0035 (5) |
O3 | 0.0750 (10) | 0.0616 (9) | 0.0275 (7) | −0.0181 (7) | 0.0111 (7) | 0.0047 (6) |
O4 | 0.0453 (7) | 0.0405 (7) | 0.0288 (6) | −0.0106 (5) | 0.0089 (5) | −0.0028 (5) |
O5 | 0.0473 (7) | 0.0564 (8) | 0.0440 (8) | 0.0105 (6) | 0.0104 (6) | −0.0034 (6) |
C1 | 0.0293 (8) | 0.0321 (8) | 0.0289 (8) | 0.0022 (6) | 0.0052 (6) | −0.0010 (6) |
C2 | 0.0368 (9) | 0.0338 (8) | 0.0356 (9) | −0.0034 (7) | 0.0084 (7) | −0.0030 (7) |
C3 | 0.0345 (9) | 0.0401 (9) | 0.0383 (10) | −0.0012 (7) | 0.0014 (7) | −0.0054 (7) |
C4 | 0.0396 (9) | 0.0418 (9) | 0.0303 (9) | −0.0017 (7) | 0.0037 (7) | 0.0000 (7) |
C5 | 0.0301 (8) | 0.0334 (8) | 0.0278 (8) | 0.0000 (6) | 0.0055 (6) | 0.0006 (6) |
C6 | 0.0304 (8) | 0.0339 (7) | 0.0305 (9) | −0.0002 (6) | 0.0061 (6) | 0.0015 (7) |
C7 | 0.0516 (11) | 0.0503 (10) | 0.0378 (10) | −0.0153 (8) | 0.0151 (9) | 0.0003 (8) |
C8 | 0.0582 (12) | 0.0557 (12) | 0.0479 (12) | −0.0142 (10) | −0.0014 (10) | −0.0142 (10) |
C9 | 0.0680 (14) | 0.0525 (12) | 0.0708 (16) | −0.0139 (10) | 0.0307 (12) | −0.0054 (11) |
C10 | 0.0646 (14) | 0.0468 (11) | 0.0557 (14) | 0.0076 (9) | 0.0167 (11) | 0.0052 (9) |
Geometric parameters (Å, º) top
Cu1—O1 | 1.9091 (15) | C3—C8 | 1.483 (3) |
Cu1—O1i | 1.9091 (15) | C4—C5 | 1.442 (2) |
Cu1—O4i | 1.9506 (14) | C5—C6 | 1.439 (3) |
Cu1—O4 | 1.9506 (14) | C6—C7 | 1.504 (2) |
S1—O5 | 1.5040 (15) | C7—H7A | 0.9600 |
S1—C10 | 1.776 (2) | C7—H7B | 0.9600 |
S1—C9 | 1.782 (2) | C7—H7C | 0.9600 |
O1—C1 | 1.264 (2) | C8—H8A | 0.9600 |
O2—C3 | 1.367 (2) | C8—H8B | 0.9600 |
O2—C4 | 1.394 (2) | C8—H8C | 0.9600 |
O3—C4 | 1.210 (2) | C9—H9A | 0.9600 |
O4—C6 | 1.2508 (19) | C9—H9B | 0.9600 |
C1—C5 | 1.434 (2) | C9—H9C | 0.9600 |
C1—C2 | 1.447 (2) | C10—H10A | 0.9600 |
C2—C3 | 1.322 (3) | C10—H10B | 0.9600 |
C2—H2 | 0.9300 | C10—H10C | 0.9600 |
| | | |
O1—Cu1—O1i | 180.0 | O4—C6—C5 | 123.12 (15) |
O1—Cu1—O4i | 89.78 (6) | O4—C6—C7 | 114.35 (15) |
O1i—Cu1—O4i | 90.22 (6) | C5—C6—C7 | 122.50 (15) |
O1—Cu1—O4 | 90.22 (6) | C6—C7—H7A | 109.5 |
O1i—Cu1—O4 | 89.78 (6) | C6—C7—H7B | 109.5 |
O4i—Cu1—O4 | 180.0 | H7A—C7—H7B | 109.5 |
O5—S1—C10 | 106.36 (10) | C6—C7—H7C | 109.5 |
O5—S1—C9 | 105.76 (10) | H7A—C7—H7C | 109.5 |
C10—S1—C9 | 96.98 (13) | H7B—C7—H7C | 109.5 |
C1—O1—Cu1 | 127.85 (10) | C3—C8—H8A | 109.5 |
C3—O2—C4 | 122.20 (14) | C3—C8—H8B | 109.5 |
C6—O4—Cu1 | 129.90 (11) | H8A—C8—H8B | 109.5 |
O1—C1—C5 | 126.05 (15) | C3—C8—H8C | 109.5 |
O1—C1—C2 | 116.37 (15) | H8A—C8—H8C | 109.5 |
C5—C1—C2 | 117.58 (15) | H8B—C8—H8C | 109.5 |
C3—C2—C1 | 121.14 (16) | S1—C9—H9A | 109.5 |
C3—C2—H2 | 119.4 | S1—C9—H9B | 109.5 |
C1—C2—H2 | 119.4 | H9A—C9—H9B | 109.5 |
C2—C3—O2 | 121.79 (16) | S1—C9—H9C | 109.5 |
C2—C3—C8 | 127.07 (18) | H9A—C9—H9C | 109.5 |
O2—C3—C8 | 111.14 (17) | H9B—C9—H9C | 109.5 |
O3—C4—O2 | 113.46 (16) | S1—C10—H10A | 109.5 |
O3—C4—C5 | 128.58 (17) | S1—C10—H10B | 109.5 |
O2—C4—C5 | 117.94 (15) | H10A—C10—H10B | 109.5 |
C1—C5—C6 | 121.08 (15) | S1—C10—H10C | 109.5 |
C1—C5—C4 | 119.11 (15) | H10A—C10—H10C | 109.5 |
C6—C5—C4 | 119.79 (14) | H10B—C10—H10C | 109.5 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O5ii | 0.93 | 2.55 | 3.475 (3) | 170 |
C9—H9B···O3iii | 0.96 | 2.55 | 3.394 (3) | 146 |
C10—H10B···O3iii | 0.96 | 2.53 | 3.379 (3) | 147 |
C10—H10C···O1ii | 0.96 | 2.58 | 3.486 (3) | 158 |
Symmetry codes: (ii) −x+1, −y, −z+1; (iii) −x+3/2, y−1/2, −z+1/2. |
Experimental details
Crystal data |
Chemical formula | [Cu(C8H7O4)2(C2H6OS)2] |
Mr | 554.07 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 294 |
a, b, c (Å) | 11.580 (5), 6.320 (5), 16.424 (5) |
β (°) | 92.27 (5) |
V (Å3) | 1201.1 (11) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.14 |
Crystal size (mm) | 0.1 × 0.1 × 0.1 |
|
Data collection |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11050, 3506, 2651 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.705 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.093, 1.05 |
No. of reflections | 3506 |
No. of parameters | 155 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.39 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O5i | 0.93 | 2.55 | 3.475 (3) | 170 |
C9—H9B···O3ii | 0.96 | 2.55 | 3.394 (3) | 146 |
C10—H10B···O3ii | 0.96 | 2.53 | 3.379 (3) | 147 |
C10—H10C···O1i | 0.96 | 2.58 | 3.486 (3) | 158 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+3/2, y−1/2, −z+1/2. |
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Mixed d-transition metal–β-diketone compounds were used extensively as starting materials in the early days of metallocene chemistry (Smith & Andersen, 1996). Dehydroacetic acid [DHA, 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione], a commercially available compound usually obtained through the auto-condensation of ethyl acetoacetate (Arndt et al., 1936), has been shown to possess modest antifungal properties (Rao et al., 1978). The importance of similar pyrones as potential fungicides is reinforced by the existence of several natural fungicides possessing structures analogous to 5,6-dihydrodehydroacetic acid, such as alternaric acid (Bartels-Keith, 1960), the podoblastins (Miyakado et al., 1982) and lachnelluloic acid (Ayer et al., 1988). Also, it has been shown that the complexes of DHA with zinc and with several other transition metal cations are fungistatic (Rao et al., 1978). This has motivated our study of the structural characterization of complexes of dehydroacetic acid. The complex of DHA with Cu was previously reported by Casabò et al. (1987), but their characterization of the compound was based only on thermal and elemental analysis, and on IR and NMR spectroscopy. We present here the crystal structure determination of the title complex, [Cu(DHA)2(DMSO)2], (I) (DMSO is dimethylsulfoxide).
The CuII atom of (I), located on an inversion centre, is surrounded by two DHA ligands occupying the equatorial plane. The two apical positions are occupied by O atoms of two dimethylsulfoxyde molecules (Fig. 1). Complexes with related structures have been already reported with thiosemicarbazone 2-pyridineformamide (Castiñeiras et al., 2000), and thiosemicarbazone of acenaphthenequinone (Rodriguez-Argüelles et al., 1997).
The structure of (I) is isostructural with the two complexes [Zn(DHA)2(DMSO)2] and [Cd(DHA)2(DMSO)2] (Zucolotto Chalaça et al., 2002). The O5···Cu bond length for the DMSO in the copper complex, (I) (2.463 Å) is significantly longer than the Zn···O and Cd···O distances of 2.185 and 2.316 Å, respectively, found in the above complexes. This difference may be related to the tendancy of Cu to prefer a square-planar geometry.
The packing of (I) is stabilized by weak intermolecular C—H···O hydrogen bonds (Table 1) which form a three-dimensional network (Fig. 2).