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Acta Cryst. (2011). E67, m581-m582    [ doi:10.1107/S1600536811011470 ]

(2-Methyl-4-oxo-4H-pyran-3-olato-[kappa]2O3,O4)bis(triphenylphosphane-[kappa]P)copper(I)-triphenylphosphane-methanol (1/1/1)

F. M. A. Muller, T. J. Muller and G. Steyl

Abstract top

In the title compound, [Cu(C6H5O3)(C18H15P)2]·C18H15P·CH3OH, the pyran-4-one ring is appromimately planar (r.m.s deviation = 0.0138 Å), with the CuI atom 0.451 (5) Å out of the plane. The CuI atom has a distorted tetrahedral coordination. The O-Cu-O angle is 80.07 (8)° and the P-Cu-P angle is 123.49 (3)°. The crystal packing is stablized by intramolecular C-H...O interactions and intermolecular C-H...O and O-H...O interactions.

Comment top

Pyranone ligands have remarkable properties for clinical purposes (Odoko et al. 2003). These ligands are relevant to the control of metal levels in the body and have been tested for administration for the amelioration of anaemia (Hider et al. 1984a,b) and the removal of iron (Kontoghiorghes et al. 1990) and aluminium (Kontoghiorghes, 1995). 3-hydroxy-2-methyl-4H- pyran-4-one is a naturally occurring non-toxic compound typically added as a food flavour enhancer. It has the ability to be deprotonated readily (pKa = 8.38; Hedlund & Öhman, 1988) and can act as an anionic chelating O,O'-bidentate ligand towards a number of biologically active metal ions (Odoko et al. 2002). The efficacy of the CuII and SnII complexes in oral-care formations (Creeth et al. 2000) has also been reported. Only three other examples of copper triphenylphosphine complexes are known to date, which containes a five-membered O,O'-bidentate chelating ring system, i.e., the flavonolato, nitrosophenylhydroxylaminato and tropolonato derivatives (Spier et al., 1990; Charalambous et al. 1984; Steyl, 2009). In this paper, the structure of (2-methyl-4-oxo-4H-pyran-3-olato- κ2O3,O4) Copper(I) complex is reported (Fig. 1). The pyran-4-one ring is essentially planar (r.m.s = 0.0138 fitted atoms C55, C56, C57, C58, C59 and O3). The Cu atom is situated 0.4508 (48) Å above the pyran-4-one ring plane. The Cu—O1 and Cu—O2 bond lengths are 2.046 (2) Å and 2.175 Å, respectively, this correlates well with literature (Steyl, 2009). The bidentate bite angle O1—Cu—O2 is 80.07 (8) ° which correlates with the observed literature values (Odoko et al. 2003). The Cu—P1 and Cu—P2 bond length is 2.2014 (7) and 2.2692 (8) Å, respectively, this is within normal range (Spier et al. 1990; Charalambous et al. 1984). The P1—Cu—P2 bond angle is 123.49 (3) °. O4–H4A···O1 hydrogen interactions between the solvent molecule and the complex and C53—H53···O1 hydrogen interaction between the free phosphie and complex stabilze the crystal packing. The crystal is further stabilized by inter- and intramolecular C—H···O hydrogen interactions (Table 2).

Related literature top

The title compound is structurally related to the flavonolato, nitrosophenylhydroxylaminato and tropolonato derivatives, see: Spier et al. (1990); Charalambous et al. (1984); Steyl (2009). For related diketonato complexes, see: Odoko et al. (2002, 2003). For general background to pyranone ligands, see: Hider et al. (1984a,b); Kontoghiorghes et al. (1990); Kontoghiorghes (1995); Hedlund & Öhman (1988); Creeth et al. (2000)

Experimental top

A solution of [Cu(NO3)(PPh3)2] (0.6502 g, 0.001 mol) in methanol (10 ml) was slowly added to a solution of 3-hydroxy-2-methyl-4H-pyran-4-one (0.1387 g, 0.0011 mol) in methanol (10 ml) and stirred for 30 minutes. Recrystallization from methanol gave X-Ray quality crystals. Yield 78%.

Refinement top

All H atoms were positioned geometrically and allowed to ride on their parent atoms, with Uiso(H) = 1.2Ueq(parent) of the parent atom with a C—H distance of 0.93.The methyl H atoms were placed in geometrically idealized positions and constrained to ride on its parent atoms with Uiso(H) = 1.5Ueq(C) and at a distance of 0.96 Å. The highest peak in the Fourier map (1.51 e.Å–3) is located 0.83Å from Cu1.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2007); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound. Thermal ellipsoids at 50% probability.
(2-Methyl-4-oxo-4H-pyran-3-olato- κ2O3,O4)bis(triphenylphosphane- κP)copper(I)–triphenylphosphane–methanol (1/1/1) top
Crystal data top
[Cu(C6H5O3)(C18H15P)2]·C18H15P·CH4OF(000) = 2104
Mr = 1007.49Dx = 1.355 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ycCell parameters from 8938 reflections
a = 20.5253 (7) Åθ = 2.3–26.4°
b = 13.5716 (4) ŵ = 0.59 mm−1
c = 20.3129 (7) ÅT = 150 K
β = 119.205 (1)°Plate, colourless
V = 4939.1 (3) Å30.19 × 0.19 × 0.06 mm
Z = 4
Data collection top
Bruker X8 APEXII 4K
diffractometer		10787 independent reflections
Radiation source: fine-focus sealed tube8326 reflections with I > 2σ(I)
graphiteRint = 0.058
φ and ω scansθmax = 27°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		h = −26→26
Tmin = 0.894, Tmax = 0.965k = −17→17
58551 measured reflectionsl = −24→25
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)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0475P)2 + 7.9566P]
where P = (Fo2 + 2Fc2)/3
10787 reflections(Δ/σ)max = 0.001
625 parametersΔρmax = 1.51 e Å−3
0 restraintsΔρmin = −0.85 e Å−3
Crystal data top
[Cu(C6H5O3)(C18H15P)2]·C18H15P·CH4OV = 4939.1 (3) Å3
Mr = 1007.49Z = 4
Monoclinic, P21/cMo Kα radiation
a = 20.5253 (7) ŵ = 0.59 mm−1
b = 13.5716 (4) ÅT = 150 K
c = 20.3129 (7) Å0.19 × 0.19 × 0.06 mm
β = 119.205 (1)°
Data collection top
Bruker X8 APEXII 4K
diffractometer		8326 reflections with I > 2σ(I)
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		Rint = 0.058
Tmin = 0.894, Tmax = 0.965θmax = 27°
58551 measured reflectionsStandard reflections: ?
10787 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.127Δρmax = 1.51 e Å−3
S = 1.06Δρmin = −0.85 e Å−3
10787 reflectionsAbsolute structure: ?
625 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Experimental. The intensity data was collected on a Bruker X8 ApexII 4 K Kappa CCD diffractometer using an exposure time of 60 s/frame. A total of 688 frames were collected with a frame width of 0.5° covering up to θ = 28.24° with 99.1% completeness accomplished.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Cu10.214103 (18)0.00326 (2)0.261886 (19)0.01908 (9)
P10.10439 (4)0.06950 (5)0.22835 (4)0.01542 (14)
P20.23466 (4)−0.16169 (5)0.26969 (4)0.01741 (15)
P30.38902 (4)0.48977 (6)0.31013 (4)0.02500 (17)
O10.29079 (11)0.06514 (16)0.23758 (11)0.0265 (5)
O20.29997 (11)0.04399 (15)0.37487 (11)0.0245 (4)
C10.08207 (15)0.08316 (18)0.30441 (15)0.0164 (5)
C20.14009 (15)0.08692 (19)0.37862 (16)0.0199 (6)
H20.19030.08190.38880.024*
C60.00836 (15)0.09007 (18)0.29104 (15)0.0170 (5)
H6−0.03190.08610.24090.02*
C5−0.00614 (15)0.10258 (19)0.35027 (16)0.0186 (5)
H5−0.05620.10910.34050.022*
C30.12498 (16)0.0979 (2)0.43784 (16)0.0217 (6)
H30.16490.10010.48830.026*
C40.05204 (16)0.1056 (2)0.42358 (16)0.0210 (6)
H40.04190.1130.46420.025*
C70.20878 (15)−0.2199 (2)0.33478 (16)0.0202 (6)
C80.18613 (16)−0.3169 (2)0.33070 (17)0.0261 (6)
H80.1824−0.3580.29110.031*
C100.17415 (17)−0.2963 (2)0.44152 (18)0.0298 (7)
H100.1616−0.32190.47740.036*
C90.16883 (16)−0.3550 (2)0.38402 (17)0.0291 (7)
H90.1533−0.42160.38060.035*
C120.21461 (19)−0.1614 (2)0.39378 (19)0.0316 (7)
H120.2302−0.09470.39760.038*
C110.1978 (2)−0.2001 (3)0.4469 (2)0.0361 (8)
H110.2026−0.160.48740.043*
C140.22245 (15)−0.3304 (2)0.18224 (16)0.0206 (6)
H140.2683−0.35190.22340.025*
C130.19240 (15)−0.2392 (2)0.18613 (15)0.0185 (5)
C180.12553 (15)−0.2083 (2)0.12403 (16)0.0193 (6)
H180.1048−0.14620.12540.023*
C170.08922 (15)−0.2673 (2)0.06064 (16)0.0215 (6)
H170.044−0.24550.01870.026*
C150.18590 (16)−0.3892 (2)0.11902 (16)0.0217 (6)
H150.2067−0.4510.11710.026*
C160.11908 (16)−0.3586 (2)0.05846 (16)0.0216 (6)
H160.0937−0.39980.01550.026*
C23−0.05007 (16)−0.1488 (2)0.13305 (17)0.0223 (6)
H23−0.0624−0.20750.150.027*
C190.02499 (14)−0.00172 (19)0.15983 (15)0.0159 (5)
C240.00684 (15)−0.08956 (19)0.18378 (16)0.0196 (6)
H240.034−0.10830.23530.023*
C20−0.01466 (16)0.0231 (2)0.08419 (16)0.0219 (6)
H20−0.00290.0820.0670.026*
C22−0.08934 (17)−0.1231 (2)0.05755 (18)0.0265 (6)
H22−0.1284−0.16430.02260.032*
C21−0.07135 (17)−0.0373 (2)0.03344 (17)0.0262 (6)
H21−0.0981−0.0195−0.01830.031*
C270.37303 (16)−0.2392 (2)0.37962 (17)0.0264 (6)
H270.3475−0.26270.40490.032*
C250.33395 (14)−0.19082 (19)0.31180 (15)0.0183 (5)
C260.37255 (17)−0.1562 (2)0.27614 (19)0.0308 (7)
H260.3466−0.12170.22970.037*
C280.44955 (17)−0.2538 (3)0.41136 (18)0.0333 (7)
H280.4759−0.28750.45810.04*
C290.48730 (17)−0.2200 (2)0.3756 (2)0.0333 (7)
H290.5396−0.230.39740.04*
C300.44870 (18)−0.1718 (3)0.3081 (2)0.0364 (8)
H300.4744−0.14880.28290.044*
C310.08839 (15)0.19196 (18)0.18591 (15)0.0165 (5)
C340.07028 (16)0.3770 (2)0.11999 (15)0.0208 (6)
H340.06450.44040.0980.025*
C350.02073 (15)0.34515 (19)0.14352 (15)0.0187 (5)
H35−0.01920.38650.13740.022*
C360.02951 (15)0.25301 (19)0.17593 (15)0.0181 (5)
H36−0.00480.23110.19150.022*
C320.13759 (15)0.2245 (2)0.16215 (16)0.0211 (6)
H320.1780.18370.16890.025*
C330.12819 (16)0.3166 (2)0.12855 (17)0.0233 (6)
H330.16150.33790.11150.028*
C420.33225 (16)0.4130 (2)0.33699 (16)0.0214 (6)
C410.25678 (17)0.4336 (2)0.30419 (18)0.0285 (7)
H410.23550.48150.26520.034*
C400.21165 (17)0.3860 (2)0.32715 (19)0.0314 (7)
H400.15980.40040.30330.038*
C390.24148 (18)0.3180 (2)0.3842 (2)0.0328 (7)
H390.21070.28570.40040.039*
C380.3168 (2)0.2969 (3)0.4180 (2)0.0418 (9)
H380.33810.25050.4580.05*
C370.36142 (19)0.3430 (3)0.3936 (2)0.0378 (8)
H370.41280.32630.41620.045*
C440.50530 (17)0.3496 (2)0.34617 (19)0.0327 (7)
H440.4720.31550.30140.039*
C430.48189 (16)0.4346 (2)0.36526 (17)0.0263 (6)
C450.57669 (18)0.3128 (3)0.3913 (2)0.0374 (8)
H450.59240.25510.37650.045*
C460.62451 (18)0.3596 (3)0.45730 (19)0.0388 (8)
H460.6730.33370.48880.047*
C470.60193 (19)0.4443 (3)0.4778 (2)0.0451 (9)
H470.63480.47660.52370.054*
C480.53168 (18)0.4823 (3)0.43178 (19)0.0371 (8)
H480.51710.54170.44560.045*
C490.36127 (16)0.4483 (2)0.21457 (17)0.0283 (7)
C540.33106 (17)0.3582 (3)0.18496 (18)0.0318 (7)
H540.32350.31120.21530.038*
C510.35207 (18)0.4942 (3)0.0952 (2)0.0396 (8)
H510.35910.54090.06440.048*
C500.37123 (17)0.5176 (3)0.16850 (19)0.0337 (7)
H500.39130.58070.18810.04*
C520.32287 (18)0.4032 (3)0.06709 (19)0.0362 (8)
H520.31050.3870.01680.043*
C530.31113 (18)0.3348 (3)0.1100 (2)0.0373 (8)
H530.28980.27260.08930.045*
C550.35473 (16)0.0786 (2)0.29884 (17)0.0236 (6)
C590.41971 (16)0.0984 (2)0.29795 (18)0.0282 (7)
C600.42869 (18)0.1052 (3)0.2299 (2)0.0363 (8)
H60A0.43960.03980.21740.054*
H60B0.46990.15010.23990.054*
H60C0.38250.13030.18750.054*
C570.42829 (17)0.0856 (2)0.43665 (19)0.0304 (7)
H570.43270.08330.48540.036*
C580.48828 (18)0.1051 (3)0.42923 (19)0.0348 (7)
H580.53470.11560.47360.042*
C560.35775 (16)0.0683 (2)0.37156 (17)0.0236 (6)
O30.48634 (12)0.11061 (17)0.36300 (13)0.0350 (5)
O40.24131 (15)0.1036 (2)0.09364 (14)0.0463 (6)
H4A0.25820.09560.14020.069*
C610.2624 (3)0.0252 (4)0.0650 (3)0.0755 (16)
H61A0.31640.02740.08430.113*
H61B0.23650.02930.00980.113*
H61C0.2491−0.03670.08040.113*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01644 (17)0.01898 (17)0.02494 (18)0.00279 (13)0.01253 (14)0.00323 (14)
P10.0157 (3)0.0140 (3)0.0198 (3)0.0010 (2)0.0112 (3)0.0015 (3)
P20.0167 (3)0.0182 (3)0.0201 (3)0.0038 (3)0.0112 (3)0.0026 (3)
P30.0204 (4)0.0275 (4)0.0260 (4)0.0003 (3)0.0105 (3)0.0044 (3)
O10.0213 (10)0.0334 (12)0.0270 (11)−0.0004 (9)0.0134 (9)0.0037 (9)
O20.0221 (10)0.0272 (11)0.0258 (11)−0.0037 (8)0.0129 (9)−0.0025 (9)
C10.0201 (13)0.0111 (12)0.0216 (13)0.0005 (10)0.0131 (11)0.0012 (10)
C20.0180 (13)0.0181 (13)0.0265 (15)0.0014 (10)0.0131 (12)0.0004 (11)
C60.0196 (13)0.0133 (12)0.0194 (13)0.0004 (10)0.0105 (11)0.0008 (10)
C50.0191 (13)0.0151 (12)0.0276 (15)0.0004 (10)0.0161 (12)0.0009 (11)
C30.0229 (14)0.0207 (14)0.0206 (14)0.0004 (11)0.0097 (12)−0.0002 (11)
C40.0278 (15)0.0182 (13)0.0218 (14)−0.0001 (11)0.0156 (12)0.0000 (11)
C70.0176 (13)0.0250 (14)0.0218 (14)0.0058 (11)0.0127 (12)0.0042 (11)
C80.0233 (15)0.0327 (16)0.0210 (14)−0.0047 (12)0.0097 (12)0.0004 (12)
C100.0239 (15)0.0439 (19)0.0311 (16)0.0084 (13)0.0209 (14)0.0124 (14)
C90.0211 (15)0.0374 (17)0.0240 (15)−0.0066 (13)0.0073 (13)0.0074 (13)
C120.046 (2)0.0251 (16)0.0373 (18)0.0088 (14)0.0313 (16)0.0043 (13)
C110.053 (2)0.0339 (18)0.0385 (19)0.0141 (16)0.0352 (18)0.0070 (15)
C140.0190 (13)0.0220 (14)0.0227 (14)0.0033 (11)0.0117 (12)0.0042 (11)
C130.0207 (13)0.0191 (13)0.0219 (14)0.0013 (11)0.0152 (12)0.0027 (11)
C180.0209 (14)0.0193 (13)0.0239 (14)0.0045 (11)0.0156 (12)0.0040 (11)
C170.0194 (14)0.0277 (15)0.0202 (14)0.0020 (11)0.0118 (12)0.0076 (12)
C150.0239 (14)0.0205 (14)0.0273 (15)0.0035 (11)0.0176 (13)0.0024 (11)
C160.0247 (14)0.0251 (14)0.0215 (14)−0.0044 (11)0.0164 (12)−0.0002 (11)
C230.0267 (15)0.0149 (13)0.0330 (16)0.0005 (11)0.0206 (13)−0.0002 (11)
C190.0163 (12)0.0144 (12)0.0211 (13)0.0026 (10)0.0122 (11)0.0004 (10)
C240.0189 (13)0.0165 (13)0.0262 (15)0.0038 (10)0.0133 (12)0.0036 (11)
C200.0268 (15)0.0184 (14)0.0265 (15)−0.0004 (11)0.0177 (13)0.0006 (11)
C220.0266 (15)0.0243 (15)0.0323 (16)−0.0077 (12)0.0172 (14)−0.0091 (13)
C210.0278 (16)0.0285 (15)0.0227 (15)−0.0039 (12)0.0125 (13)−0.0027 (12)
C270.0226 (15)0.0313 (16)0.0244 (15)0.0017 (12)0.0108 (13)0.0001 (12)
C250.0151 (13)0.0179 (13)0.0214 (14)0.0022 (10)0.0084 (11)−0.0032 (11)
C260.0248 (16)0.0393 (18)0.0341 (17)0.0093 (13)0.0188 (14)0.0096 (14)
C280.0227 (16)0.0403 (19)0.0270 (17)0.0069 (13)0.0045 (13)0.0024 (14)
C290.0170 (14)0.0339 (17)0.047 (2)−0.0009 (13)0.0140 (15)−0.0096 (15)
C300.0271 (17)0.0401 (19)0.052 (2)0.0040 (14)0.0270 (17)0.0041 (16)
C310.0200 (13)0.0132 (12)0.0176 (13)−0.0001 (10)0.0102 (11)−0.0004 (10)
C340.0287 (15)0.0138 (13)0.0209 (14)−0.0004 (11)0.0129 (12)0.0026 (11)
C350.0228 (14)0.0158 (13)0.0195 (13)0.0020 (10)0.0119 (12)−0.0012 (10)
C360.0171 (13)0.0188 (13)0.0200 (13)−0.0031 (10)0.0104 (11)−0.0008 (10)
C320.0213 (14)0.0207 (14)0.0258 (15)0.0030 (11)0.0149 (12)0.0023 (11)
C330.0256 (15)0.0234 (14)0.0279 (15)0.0000 (11)0.0187 (13)0.0041 (12)
C420.0208 (14)0.0193 (13)0.0249 (15)0.0013 (11)0.0118 (12)−0.0015 (11)
C410.0269 (16)0.0296 (16)0.0320 (17)0.0054 (12)0.0168 (14)0.0059 (13)
C400.0204 (15)0.0381 (18)0.0352 (18)0.0008 (13)0.0132 (14)0.0007 (14)
C390.0324 (17)0.0281 (16)0.047 (2)−0.0045 (13)0.0262 (16)0.0013 (14)
C380.039 (2)0.041 (2)0.052 (2)0.0076 (16)0.0277 (18)0.0205 (17)
C370.0256 (17)0.0418 (19)0.046 (2)0.0063 (14)0.0171 (16)0.0167 (16)
C440.0226 (15)0.0343 (17)0.0345 (18)−0.0013 (13)0.0087 (14)0.0051 (14)
C430.0192 (14)0.0346 (17)0.0265 (15)−0.0016 (12)0.0123 (13)0.0073 (13)
C450.0253 (17)0.0384 (19)0.048 (2)0.0052 (14)0.0170 (16)0.0120 (16)
C460.0211 (16)0.063 (2)0.0319 (18)0.0039 (15)0.0125 (14)0.0146 (17)
C470.0267 (18)0.077 (3)0.0277 (18)−0.0047 (18)0.0105 (15)−0.0073 (18)
C480.0290 (17)0.055 (2)0.0305 (17)−0.0007 (15)0.0173 (15)−0.0044 (16)
C490.0170 (14)0.0427 (18)0.0238 (15)0.0050 (13)0.0089 (12)0.0031 (13)
C540.0213 (15)0.0408 (19)0.0314 (17)0.0077 (13)0.0112 (14)0.0040 (14)
C510.0275 (17)0.059 (2)0.0343 (18)0.0030 (16)0.0166 (15)0.0109 (17)
C500.0218 (15)0.045 (2)0.0343 (18)0.0018 (14)0.0134 (14)0.0056 (15)
C520.0234 (16)0.059 (2)0.0291 (17)0.0069 (15)0.0150 (14)−0.0015 (16)
C530.0230 (16)0.043 (2)0.0386 (19)0.0034 (14)0.0091 (15)−0.0041 (16)
C550.0186 (14)0.0236 (14)0.0289 (16)0.0030 (11)0.0119 (13)0.0042 (12)
C590.0202 (15)0.0299 (16)0.0331 (17)0.0007 (12)0.0118 (13)0.0032 (13)
C600.0259 (16)0.045 (2)0.046 (2)0.0012 (14)0.0237 (16)0.0066 (16)
C570.0250 (16)0.0336 (17)0.0290 (17)0.0007 (13)0.0103 (14)−0.0004 (13)
C580.0262 (16)0.0382 (18)0.0331 (18)−0.0009 (14)0.0090 (14)−0.0012 (15)
C560.0227 (15)0.0191 (14)0.0294 (16)0.0008 (11)0.0130 (13)0.0001 (12)
O30.0185 (11)0.0428 (13)0.0398 (13)−0.0019 (9)0.0111 (10)0.0018 (11)
O40.0463 (16)0.0579 (17)0.0320 (13)0.0056 (13)0.0170 (13)−0.0006 (12)
C610.064 (3)0.093 (4)0.052 (3)0.024 (3)0.015 (2)−0.028 (3)
Geometric parameters (Å, °) top
Cu1—O12.046 (2)C28—H280.95
Cu1—O22.175 (2)C29—C301.370 (5)
Cu1—P12.2014 (7)C29—H290.95
Cu1—P22.2692 (8)C30—H300.95
P1—C191.820 (3)C31—C321.387 (4)
P1—C11.823 (3)C31—C361.396 (4)
P1—C311.827 (3)C34—C331.384 (4)
P2—C131.817 (3)C34—C351.387 (4)
P2—C71.827 (3)C34—H340.95
P2—C251.828 (3)C35—C361.383 (4)
P3—C491.825 (3)C35—H350.95
P3—C421.833 (3)C36—H360.95
P3—C431.834 (3)C32—C331.391 (4)
O1—C551.308 (4)C32—H320.95
O2—C561.264 (3)C33—H330.95
C1—C21.393 (4)C42—C371.383 (4)
C1—C61.404 (4)C42—C411.384 (4)
C2—C31.389 (4)C41—C401.384 (4)
C2—H20.95C41—H410.95
C6—C51.384 (4)C40—C391.370 (5)
C6—H60.95C40—H400.95
C5—C41.382 (4)C39—C381.382 (5)
C5—H50.95C39—H390.95
C3—C41.383 (4)C38—C371.384 (5)
C3—H30.95C38—H380.95
C4—H40.95C37—H370.95
C7—C81.386 (4)C44—C431.377 (5)
C7—C121.393 (4)C44—C451.388 (4)
C8—C91.393 (4)C44—H440.95
C8—H80.95C43—C481.393 (5)
C10—C91.373 (5)C45—C461.372 (5)
C10—C111.379 (5)C45—H450.95
C10—H100.95C46—C471.378 (5)
C9—H90.95C46—H460.95
C12—C111.387 (4)C47—C481.379 (5)
C12—H120.95C47—H470.95
C11—H110.95C48—H480.95
C14—C151.382 (4)C49—C541.370 (5)
C14—C131.402 (4)C49—C501.410 (5)
C14—H140.95C54—C531.407 (5)
C13—C181.400 (4)C54—H540.95
C18—C171.385 (4)C51—C521.371 (5)
C18—H180.95C51—C501.379 (5)
C17—C161.392 (4)C51—H510.95
C17—H170.95C50—H500.95
C15—C161.386 (4)C52—C531.372 (5)
C15—H150.95C52—H520.95
C16—H160.95C53—H530.95
C23—C241.378 (4)C55—C591.369 (4)
C23—C221.384 (4)C55—C561.455 (4)
C23—H230.95C59—O31.371 (4)
C19—C201.384 (4)C59—C601.483 (5)
C19—C241.405 (4)C60—H60A0.98
C24—H240.95C60—H60B0.98
C20—C211.384 (4)C60—H60C0.98
C20—H200.95C57—C581.338 (5)
C22—C211.383 (4)C57—C561.425 (4)
C22—H220.95C57—H570.95
C21—H210.95C58—O31.328 (4)
C27—C251.376 (4)C58—H580.95
C27—C281.391 (4)O4—C611.379 (5)
C27—H270.95O4—H4A0.84
C25—C261.390 (4)C61—H61A0.98
C26—C301.386 (4)C61—H61B0.98
C26—H260.95C61—H61C0.98
C28—C291.374 (5)
O1—Cu1—O280.07 (8)C30—C29—C28119.3 (3)
O1—Cu1—P1123.30 (6)C30—C29—H29120.4
O2—Cu1—P1113.74 (6)C28—C29—H29120.4
O1—Cu1—P2106.44 (6)C29—C30—C26120.7 (3)
O2—Cu1—P298.61 (6)C29—C30—H30119.6
P1—Cu1—P2123.49 (3)C26—C30—H30119.6
C19—P1—C1101.57 (12)C32—C31—C36119.1 (2)
C19—P1—C31103.56 (12)C32—C31—P1117.4 (2)
C1—P1—C31104.23 (12)C36—C31—P1123.5 (2)
C19—P1—Cu1114.75 (8)C33—C34—C35120.1 (2)
C1—P1—Cu1114.93 (9)C33—C34—H34120
C31—P1—Cu1116.03 (9)C35—C34—H34120
C13—P2—C7104.53 (13)C36—C35—C34119.9 (3)
C13—P2—C25103.13 (12)C36—C35—H35120
C7—P2—C25102.67 (12)C34—C35—H35120
C13—P2—Cu1121.19 (9)C35—C36—C31120.5 (2)
C7—P2—Cu1111.53 (9)C35—C36—H36119.7
C25—P2—Cu1111.90 (9)C31—C36—H36119.7
C49—P3—C42103.15 (14)C31—C32—C33120.4 (3)
C49—P3—C43102.45 (14)C31—C32—H32119.8
C42—P3—C43102.04 (13)C33—C32—H32119.8
C55—O1—Cu1111.17 (18)C34—C33—C32120.0 (3)
C56—O2—Cu1107.97 (18)C34—C33—H33120
C2—C1—C6118.6 (2)C32—C33—H33120
C2—C1—P1119.0 (2)C37—C42—C41117.9 (3)
C6—C1—P1122.4 (2)C37—C42—P3123.9 (2)
C3—C2—C1120.4 (3)C41—C42—P3117.8 (2)
C3—C2—H2119.8C42—C41—C40121.3 (3)
C1—C2—H2119.8C42—C41—H41119.4
C5—C6—C1120.6 (3)C40—C41—H41119.4
C5—C6—H6119.7C39—C40—C41120.2 (3)
C1—C6—H6119.7C39—C40—H40119.9
C4—C5—C6120.1 (3)C41—C40—H40119.9
C4—C5—H5120C40—C39—C38119.3 (3)
C6—C5—H5120C40—C39—H39120.3
C4—C3—C2120.2 (3)C38—C39—H39120.3
C4—C3—H3119.9C39—C38—C37120.3 (3)
C2—C3—H3119.9C39—C38—H38119.9
C5—C4—C3120.1 (3)C37—C38—H38119.9
C5—C4—H4120C42—C37—C38121.0 (3)
C3—C4—H4120C42—C37—H37119.5
C8—C7—C12118.6 (3)C38—C37—H37119.5
C8—C7—P2125.1 (2)C43—C44—C45121.1 (3)
C12—C7—P2116.3 (2)C43—C44—H44119.4
C7—C8—C9120.7 (3)C45—C44—H44119.4
C7—C8—H8119.6C44—C43—C48118.1 (3)
C9—C8—H8119.6C44—C43—P3124.9 (2)
C9—C10—C11119.7 (3)C48—C43—P3117.1 (2)
C9—C10—H10120.1C46—C45—C44120.0 (3)
C11—C10—H10120.1C46—C45—H45120
C10—C9—C8120.1 (3)C44—C45—H45120
C10—C9—H9119.9C45—C46—C47119.8 (3)
C8—C9—H9119.9C45—C46—H46120.1
C11—C12—C7120.3 (3)C47—C46—H46120.1
C11—C12—H12119.9C46—C47—C48120.0 (3)
C7—C12—H12119.9C46—C47—H47120
C10—C11—C12120.6 (3)C48—C47—H47120
C10—C11—H11119.7C47—C48—C43120.9 (3)
C12—C11—H11119.7C47—C48—H48119.5
C15—C14—C13120.5 (3)C43—C48—H48119.5
C15—C14—H14119.7C54—C49—C50119.0 (3)
C13—C14—H14119.7C54—C49—P3125.6 (3)
C18—C13—C14118.5 (3)C50—C49—P3115.4 (3)
C18—C13—P2118.7 (2)C49—C54—C53120.4 (3)
C14—C13—P2122.7 (2)C49—C54—H54119.8
C17—C18—C13120.7 (3)C53—C54—H54119.8
C17—C18—H18119.6C52—C51—C50119.5 (3)
C13—C18—H18119.6C52—C51—H51120.2
C18—C17—C16119.9 (3)C50—C51—H51120.2
C18—C17—H17120.1C51—C50—C49120.4 (3)
C16—C17—H17120.1C51—C50—H50119.8
C14—C15—C16120.3 (3)C49—C50—H50119.8
C14—C15—H15119.8C51—C52—C53121.4 (3)
C16—C15—H15119.8C51—C52—H52119.3
C15—C16—C17119.9 (3)C53—C52—H52119.3
C15—C16—H16120C52—C53—C54119.1 (3)
C17—C16—H16120C52—C53—H53120.4
C24—C23—C22120.3 (3)C54—C53—H53120.4
C24—C23—H23119.8O1—C55—C59123.1 (3)
C22—C23—H23119.8O1—C55—C56118.6 (2)
C20—C19—C24118.6 (3)C59—C55—C56118.2 (3)
C20—C19—P1122.8 (2)C55—C59—O3122.1 (3)
C24—C19—P1118.4 (2)C55—C59—C60126.1 (3)
C23—C24—C19120.5 (3)O3—C59—C60111.8 (3)
C23—C24—H24119.8C59—C60—H60A109.5
C19—C24—H24119.8C59—C60—H60B109.5
C19—C20—C21120.5 (3)H60A—C60—H60B109.5
C19—C20—H20119.7C59—C60—H60C109.5
C21—C20—H20119.7H60A—C60—H60C109.5
C21—C22—C23119.5 (3)H60B—C60—H60C109.5
C21—C22—H22120.2C58—C57—C56120.2 (3)
C23—C22—H22120.2C58—C57—H57119.9
C22—C21—C20120.5 (3)C56—C57—H57119.9
C22—C21—H21119.7O3—C58—C57123.4 (3)
C20—C21—H21119.7O3—C58—H58118.3
C25—C27—C28120.5 (3)C57—C58—H58118.3
C25—C27—H27119.8O2—C56—C57123.3 (3)
C28—C27—H27119.8O2—C56—C55120.2 (3)
C27—C25—C26118.7 (3)C57—C56—C55116.5 (3)
C27—C25—P2123.0 (2)C58—O3—C59119.5 (3)
C26—C25—P2118.2 (2)C61—O4—H4A109.5
C30—C26—C25120.3 (3)O4—C61—H61A109.5
C30—C26—H26119.9O4—C61—H61B109.5
C25—C26—H26119.9H61A—C61—H61B109.5
C29—C28—C27120.5 (3)O4—C61—H61C109.5
C29—C28—H28119.7H61A—C61—H61C109.5
C27—C28—H28119.7H61B—C61—H61C109.5
O1—Cu1—P1—C19114.17 (12)C28—C27—C25—P2−175.9 (2)
O2—Cu1—P1—C19−152.19 (11)C13—P2—C25—C27−112.7 (3)
P2—Cu1—P1—C19−33.04 (10)C7—P2—C25—C27−4.2 (3)
O1—Cu1—P1—C1−128.58 (12)Cu1—P2—C25—C27115.5 (2)
O2—Cu1—P1—C1−34.94 (11)C13—P2—C25—C2672.0 (3)
P2—Cu1—P1—C184.21 (10)C7—P2—C25—C26−179.5 (2)
O1—Cu1—P1—C31−6.66 (13)Cu1—P2—C25—C26−59.8 (2)
O2—Cu1—P1—C3186.98 (11)C27—C25—C26—C301.0 (5)
P2—Cu1—P1—C31−153.88 (10)P2—C25—C26—C30176.5 (3)
O1—Cu1—P2—C13−85.70 (12)C25—C27—C28—C290.2 (5)
O2—Cu1—P2—C13−167.81 (11)C27—C28—C29—C30−0.2 (5)
P1—Cu1—P2—C1366.15 (11)C28—C29—C30—C260.6 (5)
O1—Cu1—P2—C7150.65 (11)C25—C26—C30—C29−1.0 (5)
O2—Cu1—P2—C768.54 (11)C19—P1—C31—C32−112.3 (2)
P1—Cu1—P2—C7−57.51 (10)C1—P1—C31—C32141.8 (2)
O1—Cu1—P2—C2536.28 (12)Cu1—P1—C31—C3214.4 (2)
O2—Cu1—P2—C25−45.84 (11)C19—P1—C31—C3667.2 (2)
P1—Cu1—P2—C25−171.88 (10)C1—P1—C31—C36−38.7 (3)
O2—Cu1—O1—C5512.32 (19)Cu1—P1—C31—C36−166.1 (2)
P1—Cu1—O1—C55124.29 (17)C33—C34—C35—C360.3 (4)
P2—Cu1—O1—C55−83.80 (19)C34—C35—C36—C310.6 (4)
O1—Cu1—O2—C56−11.20 (18)C32—C31—C36—C35−0.7 (4)
P1—Cu1—O2—C56−133.33 (17)P1—C31—C36—C35179.8 (2)
P2—Cu1—O2—C5694.12 (18)C36—C31—C32—C33−0.3 (4)
C19—P1—C1—C2147.6 (2)P1—C31—C32—C33179.2 (2)
C31—P1—C1—C2−105.0 (2)C35—C34—C33—C32−1.3 (4)
Cu1—P1—C1—C223.1 (2)C31—C32—C33—C341.3 (4)
C19—P1—C1—C6−32.4 (2)C49—P3—C42—C37114.1 (3)
C31—P1—C1—C675.0 (2)C43—P3—C42—C378.1 (3)
Cu1—P1—C1—C6−156.94 (18)C49—P3—C42—C41−73.1 (3)
C6—C1—C2—C3−0.4 (4)C43—P3—C42—C41−179.1 (2)
P1—C1—C2—C3179.6 (2)C37—C42—C41—C400.0 (5)
C2—C1—C6—C51.4 (4)P3—C42—C41—C40−173.2 (3)
P1—C1—C6—C5−178.6 (2)C42—C41—C40—C391.1 (5)
C1—C6—C5—C4−1.8 (4)C41—C40—C39—C38−0.6 (5)
C1—C2—C3—C4−0.3 (4)C40—C39—C38—C37−0.9 (6)
C6—C5—C4—C31.1 (4)C41—C42—C37—C38−1.5 (5)
C2—C3—C4—C5−0.1 (4)P3—C42—C37—C38171.3 (3)
C13—P2—C7—C820.2 (3)C39—C38—C37—C422.0 (6)
C25—P2—C7—C8−87.2 (3)C45—C44—C43—C48−0.8 (5)
Cu1—P2—C7—C8152.8 (2)C45—C44—C43—P3−179.9 (2)
C13—P2—C7—C12−161.6 (2)C49—P3—C43—C44−27.5 (3)
C25—P2—C7—C1291.0 (2)C42—P3—C43—C4479.1 (3)
Cu1—P2—C7—C12−29.0 (2)C49—P3—C43—C48153.4 (3)
C12—C7—C8—C90.6 (4)C42—P3—C43—C48−100.1 (3)
P2—C7—C8—C9178.8 (2)C43—C44—C45—C462.0 (5)
C11—C10—C9—C8−1.0 (5)C44—C45—C46—C47−1.3 (5)
C7—C8—C9—C10−0.1 (4)C45—C46—C47—C48−0.5 (5)
C8—C7—C12—C11−0.2 (5)C46—C47—C48—C431.8 (6)
P2—C7—C12—C11−178.5 (3)C44—C43—C48—C47−1.1 (5)
C9—C10—C11—C121.5 (5)P3—C43—C48—C47178.1 (3)
C7—C12—C11—C10−0.9 (5)C42—P3—C49—C54−23.6 (3)
C15—C14—C13—C18−1.3 (4)C43—P3—C49—C5482.1 (3)
C15—C14—C13—P2176.2 (2)C42—P3—C49—C50155.1 (2)
C7—P2—C13—C18100.7 (2)C43—P3—C49—C50−99.2 (2)
C25—P2—C13—C18−152.3 (2)C50—C49—C54—C530.8 (4)
Cu1—P2—C13—C18−26.2 (2)P3—C49—C54—C53179.4 (2)
C7—P2—C13—C14−76.8 (2)C52—C51—C50—C490.3 (5)
C25—P2—C13—C1430.2 (3)C54—C49—C50—C51−1.2 (5)
Cu1—P2—C13—C14156.28 (19)P3—C49—C50—C51−179.9 (2)
C14—C13—C18—C171.0 (4)C50—C51—C52—C531.0 (5)
P2—C13—C18—C17−176.6 (2)C51—C52—C53—C54−1.4 (5)
C13—C18—C17—C160.3 (4)C49—C54—C53—C520.5 (5)
C13—C14—C15—C160.2 (4)Cu1—O1—C55—C59165.3 (2)
C14—C15—C16—C171.2 (4)Cu1—O1—C55—C56−12.1 (3)
C18—C17—C16—C15−1.4 (4)O1—C55—C59—O3−178.9 (3)
C1—P1—C19—C20132.2 (2)C56—C55—C59—O3−1.4 (4)
C31—P1—C19—C2024.3 (3)O1—C55—C59—C60−1.5 (5)
Cu1—P1—C19—C20−103.2 (2)C56—C55—C59—C60175.9 (3)
C1—P1—C19—C24−52.8 (2)C56—C57—C58—O30.7 (5)
C31—P1—C19—C24−160.7 (2)Cu1—O2—C56—C57−170.7 (2)
Cu1—P1—C19—C2471.9 (2)Cu1—O2—C56—C558.5 (3)
C22—C23—C24—C191.0 (4)C58—C57—C56—O2175.8 (3)
C20—C19—C24—C23−1.0 (4)C58—C57—C56—C55−3.4 (4)
P1—C19—C24—C23−176.3 (2)O1—C55—C56—O22.0 (4)
C24—C19—C20—C210.5 (4)C59—C55—C56—O2−175.6 (3)
P1—C19—C20—C21175.5 (2)O1—C55—C56—C57−178.8 (3)
C24—C23—C22—C21−0.4 (4)C59—C55—C56—C573.7 (4)
C23—C22—C21—C20−0.2 (4)C57—C58—O3—C591.8 (5)
C19—C20—C21—C220.1 (4)C55—C59—O3—C58−1.3 (4)
C28—C27—C25—C26−0.6 (4)C60—C59—O3—C58−179.0 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H4A···O10.841.82.637 (3)174
C2—H2···O20.952.463.370 (3)162
C12—H12···O20.952.543.412 (4)153
C22—H22···O4i0.952.513.144 (4)125
C32—H32···O10.952.63.495 (3)158
C53—H53···O40.952.523.398 (5)154
Symmetry codes: (i) −x, −y, −z.
Table 1
Selected geometric parameters (Å) top
Cu1—O12.046 (2)Cu1—P22.2692 (8)
Cu1—O22.175 (2)O1—C551.308 (4)
Cu1—P12.2014 (7)O2—C561.264 (3)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H4A···O10.841.82.637 (3)174
C2—H2···O20.952.463.370 (3)162
C12—H12···O20.952.543.412 (4)153
C22—H22···O4i0.952.513.144 (4)125
C32—H32···O10.952.63.495 (3)158
C53—H53···O40.952.523.398 (5)154
Symmetry codes: (i) −x, −y, −z.
Acknowledgements top

The University of the Free State is gratefully acknowledged for financial support and Leo Kirsten for the data collection.

references
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