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Bis(μ2-3-isopropyl-7-oxocyclo­hepta-1,3,5-trien-1-olato)bis[(3-isopropyl-7-oxocyclo­hepta-1,3,5-trien-1-olato)copper(II)]–urea–acetone (1/6/2), [Cu2(C10H11O2)4]·6CH4N2O·2C3H6O, where 3-isopropyl-7-oxocyclo­hepta-1,3,5-trien-1-olate is the systematic name for the hinokitiolate anion, contains three novel structural features. First, it contains a bis­(hino­kitiolato)copper(II) dimer, [Cu(hino)2]2, unlike any other, demonstrating that linkage isomerism is another avenue by which Cu(hino)2 can transmute from one form to another. Second, [Cu(hino)2]2 is hydrogen bonded to two urea mol­ecules, indicating that hydrogen bonding cannot yet be discounted from any proposed mechanism of action for the anti­microbial and anti­viral properties of bis­(hino­kitiolato)­copper(II). Finally, corrugated urea layers crosslinked by [Cu(hino)2]2 dimers are observed, suggesting that a new family of host–guest materials, i.e. metallo–urea clathrates, exists to challenge our understanding of crystal engineering and crystal growth and design. Selected details of the structure are that the [Cu(hino)2]2 dimers possess crystallographic inversion symmetry, the Cu atoms have square-pyramidal coordination geometries, the basal Cu—O bonds are in the range 1.916 (2)–1.931 (2) Å, the apical Cu—O bond length is 2.582 (2) Å, the hinokitiolate bite angles are in the range 83.41 (7)–83.96 (8)°, the urea–Cu(hino)2 inter­actions have an R22(8) motif, and the urea layers result from the close packing of R86(28) `butterflies' and R86(24) `strips of tape'.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110035602/eg3059sup1.cif
Contains datablocks global, IV

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110035602/eg3059IVsup2.hkl
Contains datablock IV

CCDC reference: 798585

Comment top

Hinokitiol (β-thujaplicin) is a natural product that was first isolated from Chamaecyparis taiwanensis (Nozoe, 1936) and subsequently found to possess antitumor, antibacterial, antifungal and insecticidal properties (Inamori et al., 1993, 2000; Arima et al., 2003; Morita et al., 2003). Metal complexes of hinokitiol have also been synthesized and found to possess antiviral and antimicrobial properties (Miyamoto et al., 1998; Nomiya et al., 2009). Among the latter metal complexes, bis(hinokitiolato)copper(II) or Cu(hino)2 is unique. In particular, two earlier comments about this bioactive substance have served as the inspiration for the current study, namely `the unusual structural chemistry of CuII hinokitiol' (Barret et al., 2002), and the observation that its `CuO4 core inhibits an interaction of oxygen atoms linked to C1 and C2 atoms with microorganisms/protein' (Nomiya et al., 2004).

Historically, Cu(hino)2 was first synthesized in 1936 (Nozoe, 1936) and large single crystals were clearly available by 1956 (Yamada & Tsuchida, 1956), but only much more recently, in 2002, was it finally subjected to X-ray diffraction by Molloy and co-workers and proclaimed to be somewhat `unusual' (Barret et al., 2002). Cu(hino)2 has since been found to exist in six crystalline forms, i.e. modification (I) with four forms (Barret et al., 2002; Nomiya et al., 2004; Arvanitis et al., 2004; Ho et al., 2009), modification (II) with one form (Barret et al., 2002) and modification (III) with one form (Ho, 2010), and its unusual structural diversity has so far been linked to cis,trans geometric isomerism, syn,anti conformational isomerism, aggregation via weak intermolecular Cu···π interactions, oligomerization via the hinokitiolate O atoms, and cocrystallization with other forms of itself.

A chloroform disolvate of modification (I) has also been structurally characterized and found to contain C—H···O hydrogen bonds (Ho et al., 2009). This latter observation is at odds with the earlier claim that protein–Cu(hino)2 interactions, e.g. via N—H···O hydrogen bonding, are inhibited (Nomiya et al., 2004). As a model for such an N—H···O interaction, a bis(urea) adduct analogous to the chloroform disolvate is both structurally and visually appealing and was pursued. An earlier unsuccessful attempt to isolate a urea adduct (Barret et al., 2002) was re-examined and found to yield [Cu(hino)2]2.6(urea).2(acetone), (IV). An X-ray analysis of (IV), reported herein, has provided the first unequivocal evidence and confirmation of urea adduct formation and N—H···O interactions with Cu(hino)2. A view of the bis(urea) adduct in (IV) is given in Fig. 1, and selected geometric and hydrogen-bonding parameters are summarized in Tables 1 and 2, respectively.

As shown in Fig. 1, the targeted bis(urea) adduct of modification (I) was not obtained. Instead, a [Cu(hino)2]2 dimer was found. However, one quickly comes to appreciate that this unintended cis,cis dimer is unlike any other and is therefore a notable feature in and of itself. The cis,cis dimer has been observed only twice before, in modifications (II) and (III), and in both cases the enoxy O atoms of the hinokitiolate ligands were implicated in the dimerization (Barret et al., 2002; Ho, 2010). This is also true in all known examples of [M(hino)2L]2 dimers (Nomiya et al., 2009). The cis,cis dimer in (IV) is the one exception in which the keto O atoms are implicated instead. That the dimers in (II)–(III) and (IV) are linkage isomers of one another is evident in the reversal of selected distances and angles in Table 1. Hence, Cu1—O1 Cu1—O2 is observed for (II)–(III), but Cu—O1 < Cu1—O2 is observed with (IV). Similarly, O1—Cu1—O2i < O2—Cu1—O2i and O3—Cu1—O2i < O4—Cu1—O2i are observed for (II)–(III), while the opposite is noted for (IV) [symmetry code (i) for (II)–(IV): (-x + 1, -y, -z), (-x, -y, -z + 2), (-x + 1, -y + 1, -z + 1), respectively]. The torsion angles in Table 1 indicate that the full specifications for these dimers are (+ac,+sp),(-ac,-sp)-[cis-Cu(hino)2]2 for (II), (+ap,+sp),(-ap,-sp) for (III), and (+ap,-sp),(-ap,+sp) and (+ac,-sp),(-ac,+sp) for the major and minor conformers of (IV), respectively (Ho et al., 2009). Dimers (II)–(III) have (+,+),(-,-) conformations, versus (+,-),(-,+) for (IV), suggesting that the syn sign reversals may be a characteristic of linkage isomerism in these compounds as well. All three dimers have crystallographic inversion symmetry and bowed Cu(hino)2 moieties, with those in (II)–(III) being more bowed than those in (IV) based on their C4···C14 distances, i.e. 11.176 (5) and 11.166 (6) versus 11.263 (4) Å, respectively.

The hydrogen bonding of a urea molecule to each Cu(hino)2 moiety is the second notable feature of (IV) (Fig. 1). The graph-set motif for these urea–Cu(hino)2 interactions is R22(8) (Etter, 1990; Etter et al., 1990; Bernstein et al., 1995). Surprisingly, while this motif is intuitively obvious, there are no other examples of it among α- or β-hydroxyketone transition metal complexes, and only two examples among unrelated ZnN3O3 and CoN2O4 systems, an aquahydroxyzinc(II) complex (Komen et al., 1999) and a pivalatocobalt(II) dimer (Talismanova et al., 2001). There are also no obvious trends in the O1—Cu1—O3 and O2—Cu1—O4 angles in (II)–(IV) that are attributable to the presence or absence of urea binding. For (IV), the O1—Cu1—O3 and O2—Cu1—O4 angles are 95.58 (8) and 96.20 (8)°, respectively, and the N1···O1 and N2···O3 distances are 2.944 (3) and 2.954 (3) Å, respectively. For comparison, the O—M—O angle and N···O distances are 89.10 (13)° and 2.731 (6)–2.736 (6) Å, respectively, for the urea–Zn adduct, and 96.31 (13)° and 2.875 (4)–3.072 (5) Å, respectively, for the urea–Co adduct.

The third notable feature about (IV) is recognizable at the unit-cell level, in that the crystal structure of (IV) is composed of layers of [Cu(hino)2]2 dimers and acetone solvent molecules (Fig. 2) alternating with layers of fully compacted urea molecules (Fig. 3). Each [Cu(hino)2]2 dimer is weakly associated to two acetone molecules via C5—H5···O8 interactions (graph set D) [C5—H5 = 0.95 Å, H5···O8 = 2.51 Å, C5···O8 = 3.313 (4) Å and C5—H5···O8 = 142°]. The hydrogen bonds within the urea layers are listed in Table 2. Each [Cu(hino)2]2 dimer also serves as a bridge or cross-link between the urea layers, yielding a three-dimensional host lattice with channels running parallel to the crystallographic b axis (Fig. 4). It is believed that (IV) is the only example of a metallo–urea clathrate in the truly classical sense.

The classic structures for urea inclusion compounds have been known since the mid-1900s (Schlenk, 1949; Smith, 1952). As examples, the host lattices for 1,4-dichlorobutane–urea, (V), and tetra-n-propylammonium bromide tris(urea) monohydrate, (VI), are shown in Figs. 5 and 6, respectively (Otto, 1972; Rosenstein et al., 1973; Li & Mak, 1998). All classic urea clathrates contain fully compacted corrugated urea layers, and while other patterns of fully close-packed hydrogen-bonded urea molecules might be imagined, there are only three that have actually been observed (Figs. 5a, 5b and 6a). The pattern of Fig. 5(a) can be described as a close-packing of `bow-ties' and short segmented `strips of tape'. Each bow-tie is composed of two R22(8) and four R32(10) rings. The strips of tape are composed of a central R22(8) ring and two terminal R42(8) rings. For clarity, only the R32(10) rings normal to the viewer are highlighted, to show the motif of corner-sharing bow-ties. The pattern of Fig. 5(b) is just an alternate arrangement of the same R22(8), R32(10) and R42(8) rings, i.e. a close-packing of `double bow-ties' or `butterflies' and longer R86(24) strips of tape. Only the R86(28) rings are highlighted, to show the motif of corner-sharing butterflies. Finally, the pattern of Fig. 6(a) of alternating wide and narrow infinite strips of tape results from each butterfly sharing two wing-tips (rather than one) with each of its neighbors. The urea layer motif in (IV) (Fig. 3) is clearly synonymous with that shown in Fig. 5(b).

The hexagonal channels in a purely urea host lattice are the result of three sets of urea layers being oriented roughly or exactly 120° with respect to each other (Fig. 5c). All three sets may possess the motif depicted in Fig. 5(a) (Schlenk, 1949; Smith, 1952), or the sets may be a mixture of two motifs (Figs. 5a and 5b), as shown for (V) (Otto, 1972). There are no examples with all three sets possessing the motif of Fig. 5(b). The peanut-shaped channels in (VI) are the result of a single set of urea layers being cross-linked by aggregates of two bromide anions and two water molecules (Fig. 6b) (Rosenstein et al., 1973; Li & Mak, 1998). The channels in (IV) (Fig. 4) result from cross-linking with a transition metal complex instead, i.e. [Cu(hino)2]2, and are clearly analogous to those in (VI). The separations between urea layers are 7.08 (3), 14.559 (3) and 15.9471 (2) Å for (V), (VI) and (IV), respectively.

In summary, [Cu(hino)2]2.6(urea).2(acetone), (IV), is a urea adduct of bis(hinokitiolato)copper(II). Urea–Cu(hino)2 N—H···O hydrogen bonding has been confirmed, suggesting that the hinokitiolate O atoms are indeed available for microorganism/protein interactions, e.g. via the N—H group present in all peptide bonds and in arginine, asparagine, glutamine, histidine, lysine and tryptophan residues. Additionally, (IV) is also the only example of a classical metallo–urea clathrate. The clathrate urea layers are cross-linked by [Cu(hino)2]2 dimers, and the dimers themselves are also unique, i.e. no other keto µ2-O-bridged hinokitiolate dimers are known. The 'unusual structural chemistry of CuII hinokitiol' now includes linkage isomerism as yet another pathway for structural diversification.

Experimental top

A small vial was charged with [cis-Cu(hino)2]2.[trans- Cu(hino)2]2.trans-Cu(hino)2, (II) (39 mg, 0.02 mmol), and urea (18 mg, 0.30 mmol). The solids were dissolved in acetone (5 ml), and the vial lightly capped to allow the solution to evaporate slowly at room temperature. Green needles and rectangular prisms of [cis-Cu(hino)2]2.6(urea).2(acetone), (IV), appeared in a few days. Crystals of (IV) desolvate upon standing in air, so the solution should not be allowed to evaporate to dryness. A needle and a prism were both examined and found to have the same unit cell. Both were also dichroic, appearing emerald green when viewed perpendicular to the 100 face and light green when viewed perpendicular to either the 011 or 011 faces. As it was larger, a cut needle was selected for the diffraction experiment.

Refinement top

The positional parameters for the urea H atoms were free to vary. All other H atoms were allowed to ride on their respective C atoms, with C—H = 0.95, 1.00 and 0.98 Å for the cycloheptatriene, methine and methyl H atoms, respectively, and with Uiso(H) = 1.2Ueq(C) for the cycloheptatriene and methine H atoms, 1.5Ueq(C) for the methyl H atoms and 1.5Ueq(N) for the urea H atoms. One of the isopropyl groups was rotationally disordered and was treated with a two-site model, C9–C10/C9*–C10*, with refined site-occupancy factors of 0.66 (2)/0.34 (2), respectively. Atom C8 is common to both components of the disorder. A total of 19 restraints were employed: C8–C9, C8–C10, C8–C9* and C8–C10* DFIX restraints (4), C8–C9*, C8–C10* and C9*–C10* DELU restraints (3), and C8–C9* and C8–C10* SIMU restraints (12) (software commands from SHELXTL; Sheldrick, 2008).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The [cis-Cu(hino)2]2 bis(urea) adduct in (IV). Dashed lines indicate hydrogen bonds, and displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) -x + 1, -y + 1, -z + 1.]
[Figure 2] Fig. 2. A projection diagram, normal to the (h00) family of planes, showing the packing and C5—H5···O8 hydrogen bonding (dashed lines) between the cis,cis dimers and acetone solvent molecules in (IV). Only those molecules intersecting with the h = 2 or (200) plane are shown. All other H atoms and the h = 1 or (100) plane populated solely by urea molecules have been omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 3] Fig. 3. A projection diagram, normal to the bc plane, showing the hydrogen bonding (dashed lines) between urea molecules in (IV). Displacement ellipsoids are drawn at the 50% probability level. Boundary ellipses denote atoms O5, N1, N2 and C21, boundary and principal ellipses denote atoms O6, N3, N4 and C22, and octant-shaded ellipsoids denote atoms O7, N5, N6 and C23.
[Figure 4] Fig. 4. A projection diagram, showing the channels running parallel to [010] formed by cross-linking of the corrugated urea layers by the cis,cis dimers in (IV). The bulk of the hinokitiolate ligands and the acetone solvent molecules have been removed for clarity. Dashed lines indicate hydrogen bonds, and displacement ellipsoids are drawn at the 50% probability level. Boundary ellipses denote atoms O5, N1, N2 and C21, boundary and principal ellipses denote atoms O6, N3, N4 and C22, and octant-shaded ellipsoids denote atoms O7, N5, N6 and C23.
[Figure 5] Fig. 5. Projection diagrams for (V), (a) normal to the (040) plane and (b) normal to the (220) plane, with packing motifs highlighted. In (c), the (040), (220) and (220) planes are viewed on edge and their locations shown by highlighted lines through them. The channels in (V) are completely specified by these three families of planes. The C, H and N atoms for the two unique urea molecules in (V) are indicated by filled and open spheres of arbitrary radii. [C and N only? All H atoms are shown open]
[Figure 6] Fig. 6. Projection diagrams of (a) the urea layers and (b) the channels in (VI). The packing motif in (a) is highlighted for comparison with the motifs in (V). The C, H and N atoms for the three unique urea molecules in (VI) are indicated by filled, shaded and open spheres of arbitrary radii. [C and N only? All H atoms are shown open]
Bis(µ2-3-isopropyl-7-oxocyclohepta-1,3,5-trien-1-olato)- bis[(3-isopropyl-7-oxocyclohepta-1,3,5-trien-1-olato)copper(II)]–urea–acetone (1/6/2) top
Crystal data top
[Cu2(C10H11O2)4]·6CH4N2O·2C3H6OF(000) = 1324
Mr = 1256.36Dx = 1.371 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 41379 reflections
a = 17.0125 (2) Åθ = 2.2–27.5°
b = 11.0470 (2) ŵ = 0.77 mm1
c = 17.2731 (3) ÅT = 200 K
β = 110.385 (1)°Needle, green
V = 3042.95 (8) Å30.30 × 0.10 × 0.04 mm
Z = 2
Data collection top
Nonius KappaCCD area-detector
diffractometer
6996 independent reflections
Radiation source: fine-focus sealed tube4582 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.074
ω scans; 800 0.5° rotationsθmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)
h = 2122
Tmin = 0.801, Tmax = 0.973k = 1414
41379 measured reflectionsl = 2221
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)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.147H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.077P)2 + 0.7191P]
where P = (Fo2 + 2Fc2)/3
6996 reflections(Δ/σ)max = 0.001
433 parametersΔρmax = 0.76 e Å3
19 restraintsΔρmin = 0.63 e Å3
Crystal data top
[Cu2(C10H11O2)4]·6CH4N2O·2C3H6OV = 3042.95 (8) Å3
Mr = 1256.36Z = 2
Monoclinic, P21/cMo Kα radiation
a = 17.0125 (2) ŵ = 0.77 mm1
b = 11.0470 (2) ÅT = 200 K
c = 17.2731 (3) Å0.30 × 0.10 × 0.04 mm
β = 110.385 (1)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
6996 independent reflections
Absorption correction: multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)
4582 reflections with I > 2σ(I)
Tmin = 0.801, Tmax = 0.973Rint = 0.074
41379 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.05319 restraints
wR(F2) = 0.147H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.76 e Å3
6996 reflectionsΔρmin = 0.63 e Å3
433 parameters
Special details top

Experimental. A green needle cut to roughly 0.035 mm × 0.095 mm × 0.300 mm in size was mounted on a glass fiber with silicone grease, and transferred to a Nonius KappaCCD diffractometer equipped with a MSC X-stream cryosystem and Mo Kα radiation (λ = 0.71073 Å). Eight hundred frames were collected at 200 (2) K to θmax = 27.49° with an oscillation range of 0.5°/frame and an exposure time of 320 s/° (Nonius, 1998). A total of 41379 reflections were indexed, integrated and corrected for Lorentz and polarization effects using DENZO, followed by scaling and a multi-scan absorption correction using SCALEPACK to give 6996 unique reflections (Rint = 0.074), of which 4582 had I > 2σ(I) (Otwinowski & Minor, 1997). The minimum and maximum transmission factors were 0.8012 and 0.9734, respectively. Postrefinement of the unit-cell parameters gave a = 17.0125 (2) Å, b = 11.0470 (2) Å, c = 17.2731 (3) Å, α = 90°, β = 110.385 (1)°, γ = 90°, and V = 3042.95 (8) Å3. Axial photographs and systematic absences were consistent with the compound having crystallized in the monoclinic space group P21/c (No. 14). The observed mean |E2-1| value was 1.039 (versus the expectation values of 0.968 and 0.736 for centric and noncentric data, respectively).

________________________________________________________________________

Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.

Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter, Jr. & R. M. Sweet, pp 307-326. New York: Academic Press.

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.

The structure was solved by direct methods and refined by full-matrix least-squares on F2 using SHELXTL (Sheldrick, 2008). The coordinates and anisotropic displacement coefficients for the non-H atoms were free to vary. The coordinates for the urea H atoms were also free to vary. All other H atoms were allowed to ride on their respective carbons. The hydrogen isotropic displacement coefficients were assigned as U(H) = 1.2U(C), 1.5U(Cmethyl) or 1.5U(N). One of the isopropyl groups was found to be rotationally disordered, and was treated with a two-site disorder model consisting of (C9,C10) and (C9*,C10*) with refined site-occupancy factors of 0.66 (2) and 0.34 (2), respectively, and with C8 being a common shared atom to both components of the disorder. Rigid bond, similar Uij and 1,2-distance restraints were employed, and the refinement converged smoothly to R(F) = 0.0529, wR(F2) = 0.1238 and S = 1.057 for 4582 reflections with I > 2σ(I), and R(F) = 0.0943, wR(F2) = 0.1465 and S = 1.057 for 6996 unique reflections, 433 parameters and 19 restraints. The maximum |Δ/σ| in the final cycle of least-squares was 0.001, and the residual peaks on the final difference Fourier map ranged from -0.630 to 0.760 eÅ-3. ________________________________________________________________________

R(F ) = R1 = Σ ||Fo|-|Fc|| / Σ|Fo|, wR(F 2) = wR2 = [ Σ w (Fo2-Fc2)2 / Σ w (Fo2)2 ]1/2, and S = Goodness-of-fit on F 2 = [ Σ w (Fo2-Fc2)2 / (n-p) ]1/2, where n is the number of reflections and p is the number of parameters refined.

________________________________________________________________________

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cu10.414638 (18)0.49976 (3)0.52640 (2)0.02874 (12)
O10.33876 (10)0.45164 (17)0.41958 (12)0.0320 (4)
O20.48030 (11)0.36506 (16)0.51150 (12)0.0308 (4)
C10.36103 (16)0.3518 (2)0.39236 (18)0.0296 (6)
C20.30861 (17)0.3048 (3)0.31692 (19)0.0345 (6)
H20.26020.35260.29070.041*
C30.31366 (17)0.2013 (3)0.27278 (19)0.0375 (7)
C40.37703 (18)0.1141 (3)0.2974 (2)0.0416 (7)
H40.37050.04730.26110.050*
C50.44789 (18)0.1122 (3)0.3676 (2)0.0429 (8)
H50.48320.04400.37210.051*
C60.47587 (16)0.1931 (2)0.43242 (19)0.0357 (7)
H60.52710.17130.47440.043*
C70.44095 (16)0.3015 (2)0.44596 (18)0.0298 (6)
C80.24194 (19)0.1798 (3)0.1913 (2)0.0480 (8)
H80.20190.24910.18210.058*0.66 (2)
H8*0.22000.26210.17060.058*0.34 (2)
C90.2747 (9)0.1768 (13)0.1201 (6)0.073 (3)0.66 (2)
H9A0.22740.17210.06780.109*0.66 (2)
H9B0.31080.10580.12570.109*0.66 (2)
H9C0.30710.25050.12090.109*0.66 (2)
C9*0.2664 (15)0.123 (3)0.1227 (12)0.070 (6)0.34 (2)
H9D0.32340.14790.12840.105*0.34 (2)
H9E0.22720.14920.06900.105*0.34 (2)
H9F0.26430.03440.12660.105*0.34 (2)
C100.1940 (6)0.0629 (8)0.1934 (5)0.060 (3)0.66 (2)
H10A0.17650.06380.24170.090*0.66 (2)
H10B0.23050.00700.19660.090*0.66 (2)
H10C0.14450.05730.14300.090*0.66 (2)
C10*0.1705 (9)0.116 (3)0.2081 (10)0.081 (6)0.34 (2)
H10D0.15040.16690.24380.122*0.34 (2)
H10E0.19040.03860.23560.122*0.34 (2)
H10F0.12460.10160.15580.122*0.34 (2)
O30.34305 (11)0.62228 (17)0.54415 (12)0.0341 (4)
O40.48105 (11)0.53017 (18)0.63954 (12)0.0336 (5)
C110.36761 (16)0.6603 (2)0.62053 (17)0.0307 (6)
C120.31570 (17)0.7375 (3)0.64490 (19)0.0356 (7)
H120.26360.75350.60240.043*
C130.32481 (18)0.7960 (3)0.71920 (19)0.0376 (7)
C140.39466 (18)0.7914 (3)0.79059 (19)0.0403 (7)
H140.39240.84050.83490.048*
C150.46778 (18)0.7242 (3)0.80598 (19)0.0388 (7)
H150.50830.73460.85960.047*
C160.49098 (17)0.6448 (3)0.75587 (18)0.0347 (7)
H160.54410.60730.78110.042*
C170.44818 (15)0.6109 (2)0.67347 (18)0.0298 (6)
C180.24968 (19)0.8705 (3)0.7213 (2)0.0448 (8)
H180.26840.91730.77420.054*
C190.2188 (2)0.9627 (3)0.6505 (2)0.0596 (10)
H19A0.17581.01450.65900.089*
H19B0.19500.91970.59790.089*
H19C0.26611.01270.64950.089*
C200.1785 (2)0.7885 (4)0.7227 (3)0.0620 (10)
H20A0.19900.73220.76930.093*
H20B0.15750.74270.67090.093*
H20C0.13310.83770.72870.093*
O50.04199 (10)0.57382 (16)0.38779 (12)0.0312 (4)
N10.16095 (16)0.4699 (2)0.40302 (18)0.0380 (6)
H1A0.210 (2)0.467 (3)0.410 (2)0.057*
H1B0.134 (2)0.411 (3)0.396 (2)0.057*
N20.16719 (16)0.6690 (2)0.43928 (18)0.0398 (6)
H2A0.219 (2)0.664 (3)0.464 (2)0.060*
H2B0.143 (2)0.733 (3)0.443 (2)0.060*
C210.12109 (16)0.5705 (2)0.40970 (17)0.0286 (6)
O60.06006 (11)0.24689 (16)0.38167 (12)0.0333 (4)
N30.00365 (18)0.3470 (2)0.46461 (19)0.0404 (6)
H3A0.009 (2)0.352 (3)0.513 (2)0.061*
H3B0.010 (2)0.408 (4)0.445 (2)0.061*
N40.03290 (19)0.1440 (2)0.48284 (18)0.0419 (7)
H4A0.004 (2)0.142 (4)0.511 (2)0.063*
H4B0.052 (2)0.081 (3)0.461 (2)0.063*
C220.03297 (16)0.2456 (2)0.44058 (18)0.0314 (6)
O70.06495 (12)0.90506 (16)0.41267 (12)0.0340 (4)
N50.00049 (18)0.8072 (2)0.29272 (18)0.0430 (6)
H5A0.017 (2)0.805 (4)0.241 (2)0.064*
H5B0.005 (2)0.741 (3)0.320 (2)0.064*
N60.03171 (18)1.0088 (2)0.29258 (18)0.0392 (6)
H6A0.010 (2)1.011 (3)0.240 (3)0.059*
H6B0.047 (2)1.078 (3)0.327 (2)0.059*
C230.03337 (16)0.9066 (2)0.33566 (19)0.0306 (6)
O80.62642 (17)0.0364 (3)0.4530 (2)0.0922 (10)
C240.7535 (2)0.1198 (4)0.5434 (3)0.0822 (14)
H24A0.73170.19620.51540.123*
H24B0.76860.13030.60310.123*
H24C0.80320.09560.53090.123*
C250.6880 (2)0.0244 (4)0.5141 (3)0.0622 (11)
C260.7028 (3)0.0878 (4)0.5650 (3)0.0862 (15)
H26A0.68050.07710.60980.129*
H26B0.67440.15610.53030.129*
H26C0.76310.10410.58850.129*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02859 (19)0.0307 (2)0.0267 (2)0.00173 (13)0.00932 (14)0.00243 (14)
O10.0297 (9)0.0329 (10)0.0313 (12)0.0058 (8)0.0079 (8)0.0054 (9)
O20.0316 (9)0.0303 (11)0.0272 (11)0.0013 (8)0.0061 (8)0.0023 (8)
C10.0316 (13)0.0288 (14)0.0312 (17)0.0024 (11)0.0145 (12)0.0006 (12)
C20.0347 (14)0.0291 (15)0.0373 (18)0.0042 (11)0.0097 (13)0.0028 (12)
C30.0402 (15)0.0341 (16)0.0382 (19)0.0012 (12)0.0134 (13)0.0049 (13)
C40.0424 (16)0.0339 (16)0.047 (2)0.0014 (13)0.0143 (15)0.0131 (14)
C50.0394 (16)0.0336 (17)0.055 (2)0.0076 (12)0.0150 (15)0.0049 (15)
C60.0306 (13)0.0303 (15)0.0431 (19)0.0038 (11)0.0087 (13)0.0008 (13)
C70.0301 (13)0.0303 (15)0.0300 (17)0.0005 (11)0.0117 (12)0.0033 (12)
C80.0499 (18)0.0403 (18)0.043 (2)0.0043 (14)0.0025 (15)0.0108 (15)
C90.089 (6)0.078 (7)0.041 (5)0.015 (6)0.009 (4)0.006 (5)
C9*0.056 (8)0.101 (16)0.048 (9)0.000 (11)0.013 (6)0.025 (10)
C100.043 (4)0.075 (5)0.059 (5)0.016 (3)0.012 (3)0.012 (4)
C10*0.031 (6)0.144 (16)0.060 (9)0.004 (8)0.005 (5)0.019 (10)
O30.0349 (10)0.0386 (11)0.0257 (12)0.0054 (8)0.0068 (8)0.0053 (9)
O40.0327 (10)0.0402 (11)0.0269 (12)0.0029 (8)0.0092 (8)0.0016 (9)
C110.0346 (14)0.0288 (14)0.0284 (17)0.0021 (11)0.0107 (12)0.0026 (12)
C120.0359 (14)0.0379 (16)0.0309 (18)0.0031 (12)0.0090 (12)0.0036 (13)
C130.0427 (15)0.0328 (16)0.0383 (19)0.0033 (12)0.0156 (14)0.0063 (13)
C140.0501 (17)0.0394 (17)0.0316 (18)0.0074 (13)0.0145 (14)0.0113 (13)
C150.0402 (15)0.0434 (18)0.0294 (18)0.0089 (13)0.0077 (13)0.0069 (14)
C160.0314 (13)0.0398 (16)0.0313 (17)0.0042 (12)0.0089 (12)0.0012 (13)
C170.0309 (13)0.0283 (14)0.0317 (17)0.0038 (11)0.0127 (12)0.0000 (12)
C180.0530 (18)0.0417 (18)0.040 (2)0.0093 (14)0.0171 (15)0.0080 (15)
C190.072 (2)0.052 (2)0.055 (3)0.0193 (18)0.022 (2)0.0018 (18)
C200.057 (2)0.070 (3)0.069 (3)0.0108 (18)0.035 (2)0.000 (2)
O50.0280 (9)0.0286 (10)0.0360 (12)0.0007 (7)0.0101 (8)0.0015 (8)
N10.0288 (12)0.0319 (14)0.0521 (18)0.0015 (10)0.0124 (12)0.0030 (12)
N20.0336 (13)0.0301 (14)0.0492 (18)0.0021 (10)0.0063 (12)0.0027 (12)
C210.0343 (14)0.0274 (15)0.0237 (15)0.0012 (11)0.0095 (11)0.0037 (11)
O60.0428 (11)0.0290 (10)0.0322 (12)0.0013 (8)0.0180 (9)0.0013 (8)
N30.0565 (16)0.0295 (14)0.0434 (18)0.0012 (12)0.0278 (13)0.0010 (12)
N40.0645 (18)0.0285 (14)0.0452 (18)0.0007 (12)0.0347 (14)0.0022 (12)
C220.0340 (14)0.0280 (15)0.0321 (17)0.0036 (11)0.0115 (12)0.0017 (12)
O70.0447 (11)0.0289 (10)0.0288 (12)0.0002 (8)0.0130 (9)0.0013 (8)
N50.0666 (17)0.0284 (14)0.0306 (16)0.0009 (12)0.0126 (14)0.0010 (12)
N60.0597 (16)0.0310 (14)0.0252 (15)0.0018 (11)0.0128 (13)0.0025 (12)
C230.0348 (14)0.0264 (14)0.0325 (18)0.0037 (11)0.0142 (13)0.0021 (12)
O80.0494 (16)0.139 (3)0.073 (2)0.0058 (17)0.0016 (16)0.001 (2)
C240.066 (3)0.093 (3)0.086 (4)0.016 (2)0.025 (2)0.029 (3)
C250.0372 (18)0.083 (3)0.065 (3)0.0032 (17)0.0158 (19)0.022 (2)
C260.072 (3)0.067 (3)0.104 (4)0.011 (2)0.011 (3)0.021 (3)
Geometric parameters (Å, º) top
Cu1—O31.9157 (18)C14—H140.9500
Cu1—O41.916 (2)C15—C161.383 (4)
Cu1—O11.9219 (19)C15—H150.9500
Cu1—O21.9310 (18)C16—C171.405 (4)
O1—C11.306 (3)C16—H160.9500
O2—C71.302 (3)C18—C201.519 (5)
C1—C21.398 (4)C18—C191.537 (5)
C1—C71.462 (4)C18—H181.0000
C2—C31.393 (4)C19—H19A0.9800
C2—H20.9500C19—H19B0.9800
C3—C41.397 (4)C19—H19C0.9800
C3—C81.526 (4)C20—H20A0.9800
C4—C51.380 (4)C20—H20B0.9800
C4—H40.9500C20—H20C0.9800
C5—C61.381 (4)O5—C211.265 (3)
C5—H50.9500N1—C211.328 (4)
C6—C71.393 (4)N1—H1A0.80 (4)
C6—H60.9500N1—H1B0.78 (4)
C8—H81.0000N2—C211.334 (4)
C8—C91.517 (5)N2—H2A0.84 (4)
C8—C101.534 (4)N2—H2B0.83 (4)
C8—H8*1.0001O6—C221.255 (3)
C8—C9*1.523 (5)N3—C221.349 (4)
C8—C10*1.517 (5)N3—H3A0.94 (4)
C9—H9A0.9800N3—H3B0.78 (4)
C9—H9B0.9800N4—C221.339 (4)
C9—H9C0.9800N4—H4A0.80 (4)
C9*—H9D0.9800N4—H4B0.90 (4)
C9*—H9E0.9800O7—C231.249 (3)
C9*—H9F0.9800N5—C231.338 (4)
C10—H10A0.9800N5—H5A0.84 (4)
C10—H10B0.9800N5—H5B0.86 (4)
C10—H10C0.9800N6—C231.347 (4)
C10*—H10D0.9800N6—H6A0.85 (4)
C10*—H10E0.9800N6—H6B0.94 (4)
C10*—H10F0.9800O8—C251.209 (5)
O3—C111.307 (3)C24—C251.488 (5)
O4—C171.296 (3)C24—H24A0.9800
C11—C121.394 (4)C24—H24B0.9800
C11—C171.463 (4)C24—H24C0.9800
C12—C131.397 (4)C25—C261.490 (6)
C12—H120.9500C26—H26A0.9800
C13—C141.384 (4)C26—H26B0.9800
C13—C181.531 (4)C26—H26C0.9800
C14—C151.392 (4)
O3—Cu1—O483.96 (8)C14—C13—C18117.6 (3)
O3—Cu1—O195.58 (8)C12—C13—C18116.4 (3)
O4—Cu1—O1171.12 (8)C13—C14—C15128.5 (3)
O3—Cu1—O2174.51 (8)C13—C14—H14115.7
O4—Cu1—O296.20 (8)C15—C14—H14115.7
O1—Cu1—O283.41 (7)C16—C15—C14130.5 (3)
C1—O1—Cu1113.40 (16)C16—C15—H15114.7
C7—O2—Cu1112.65 (15)C14—C15—H15114.7
O1—C1—C2118.6 (2)C15—C16—C17130.0 (3)
O1—C1—C7114.5 (2)C15—C16—H16115.0
C2—C1—C7126.8 (2)C17—C16—H16115.0
C3—C2—C1132.4 (3)O4—C17—C16119.2 (2)
C3—C2—H2113.8O4—C17—C11115.6 (2)
C1—C2—H2113.8C16—C17—C11125.2 (2)
C2—C3—C4126.0 (3)C20—C18—C13110.9 (3)
C2—C3—C8116.8 (3)C20—C18—C19110.8 (3)
C4—C3—C8117.2 (3)C13—C18—C19113.1 (3)
C5—C4—C3128.5 (3)C20—C18—H18107.3
C5—C4—H4115.7C13—C18—H18107.3
C3—C4—H4115.7C19—C18—H18107.3
C4—C5—C6130.6 (3)C18—C19—H19A109.5
C4—C5—H5114.7C18—C19—H19B109.5
C6—C5—H5114.7H19A—C19—H19B109.5
C5—C6—C7130.3 (3)C18—C19—H19C109.5
C5—C6—H6114.9H19A—C19—H19C109.5
C7—C6—H6114.9H19B—C19—H19C109.5
O2—C7—C6119.3 (2)C18—C20—H20A109.5
O2—C7—C1115.4 (2)C18—C20—H20B109.5
C6—C7—C1125.3 (3)H20A—C20—H20B109.5
C3—C8—C9110.4 (6)C18—C20—H20C109.5
C3—C8—C10111.8 (4)H20A—C20—H20C109.5
C9—C8—C10110.4 (5)H20B—C20—H20C109.5
C3—C8—H8108.0C21—N1—H1A124 (3)
C9—C8—H8108.0C21—N1—H1B115 (3)
C10—C8—H8108.0H1A—N1—H1B121 (4)
C8—C9—H9A109.5C21—N2—H2A121 (2)
C8—C9—H9B109.5C21—N2—H2B118 (2)
C8—C9—H9C109.5H2A—N2—H2B119 (4)
H9A—C9—H9B109.5O5—C21—N1121.3 (2)
H9A—C9—H9C109.5O5—C21—N2120.9 (2)
H9B—C9—H9C109.5N1—C21—N2117.8 (3)
C8—C10—H10A109.5C22—N3—H3A123 (2)
C8—C10—H10B109.5C22—N3—H3B117 (3)
C8—C10—H10C109.5H3A—N3—H3B117 (4)
H10A—C10—H10B109.5C22—N4—H4A118 (3)
H10A—C10—H10C109.5C22—N4—H4B111 (2)
H10B—C10—H10C109.5H4A—N4—H4B127 (4)
C3—C8—C9*115.8 (10)O6—C22—N4121.5 (3)
C3—C8—C10*109.4 (7)O6—C22—N3121.3 (3)
C9*—C8—C10*114.3 (10)N4—C22—N3117.2 (3)
C3—C8—H8*105.5C23—N5—H5A122 (3)
C9*—C8—H8*105.5C23—N5—H5B117 (3)
C10*—C8—H8*105.5H5A—N5—H5B120 (4)
C8—C9*—H9D109.5C23—N6—H6A122 (2)
C8—C9*—H9E109.5C23—N6—H6B113 (2)
C8—C9*—H9F109.5H6A—N6—H6B124 (3)
H9D—C9*—H9E109.5O7—C23—N5121.4 (3)
H9D—C9*—H9F109.5O7—C23—N6121.2 (3)
H9E—C9*—H9F109.5N5—C23—N6117.4 (3)
C8—C10*—H10D109.5C25—C24—H24A109.5
C8—C10*—H10E109.5C25—C24—H24B109.5
C8—C10*—H10F109.5H24A—C24—H24B109.5
H10D—C10*—H10E109.5C25—C24—H24C109.5
H10D—C10*—H10F109.5H24A—C24—H24C109.5
H10E—C10*—H10F109.5H24B—C24—H24C109.5
C11—O3—Cu1113.04 (16)O8—C25—C24122.5 (5)
C17—O4—Cu1112.82 (17)O8—C25—C26121.6 (4)
O3—C11—C12119.2 (2)C24—C25—C26115.9 (4)
O3—C11—C17114.3 (2)C25—C26—H26A109.5
C12—C11—C17126.4 (3)C25—C26—H26B109.5
C11—C12—C13133.0 (3)H26A—C26—H26B109.5
C11—C12—H12113.5C25—C26—H26C109.5
C13—C12—H12113.5H26A—C26—H26C109.5
C14—C13—C12126.0 (3)H26B—C26—H26C109.5
O3—Cu1—O1—C1168.88 (18)C2—C3—C8—C10117.0 (6)
O2—Cu1—O1—C15.69 (17)C4—C3—C8—C1061.2 (7)
O4—Cu1—O2—C7164.03 (17)O4—Cu1—O3—C114.27 (18)
O1—Cu1—O2—C77.04 (17)O1—Cu1—O3—C11166.81 (18)
Cu1—O1—C1—C2177.1 (2)O3—Cu1—O4—C171.55 (17)
Cu1—O1—C1—C73.4 (3)O2—Cu1—O4—C17172.93 (17)
O1—C1—C2—C3178.7 (3)Cu1—O3—C11—C12171.6 (2)
C7—C1—C2—C31.9 (5)Cu1—O3—C11—C175.9 (3)
C1—C2—C3—C41.3 (5)O3—C11—C12—C13177.3 (3)
C1—C2—C3—C8179.3 (3)C17—C11—C12—C135.5 (5)
C2—C3—C4—C51.9 (5)C11—C12—C13—C141.6 (6)
C8—C3—C4—C5180.0 (3)C11—C12—C13—C18177.5 (3)
C3—C4—C5—C60.5 (6)C12—C13—C14—C153.9 (5)
C4—C5—C6—C70.4 (6)C18—C13—C14—C15175.2 (3)
Cu1—O2—C7—C6172.1 (2)C13—C14—C15—C160.1 (6)
Cu1—O2—C7—C17.1 (3)C14—C15—C16—C171.9 (5)
C5—C6—C7—O2178.2 (3)Cu1—O4—C17—C16178.46 (19)
C5—C6—C7—C12.7 (5)Cu1—O4—C17—C111.2 (3)
O1—C1—C7—O22.5 (3)C15—C16—C17—O4177.3 (3)
C2—C1—C7—O2176.9 (3)C15—C16—C17—C113.1 (5)
O1—C1—C7—C6176.6 (2)O3—C11—C17—O44.8 (3)
C2—C1—C7—C63.9 (4)C12—C11—C17—O4172.5 (3)
C2—C3—C8—C10*84.6 (14)O3—C11—C17—C16174.8 (2)
C4—C3—C8—C10*93.7 (14)C12—C11—C17—C167.9 (4)
C2—C3—C8—C9119.7 (6)C14—C13—C18—C20106.9 (3)
C4—C3—C8—C962.1 (7)C12—C13—C18—C2072.3 (4)
C2—C3—C8—C9*144.6 (14)C14—C13—C18—C19127.9 (3)
C4—C3—C8—C9*37.1 (14)C12—C13—C18—C1952.9 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O10.80 (4)2.15 (4)2.944 (3)175 (4)
N1—H1B···O60.78 (4)2.17 (4)2.951 (3)178 (4)
N2—H2A···O30.84 (4)2.13 (4)2.954 (3)167 (4)
N2—H2B···O70.83 (4)2.27 (4)3.079 (3)164 (4)
N3—H3A···O5i0.94 (4)2.14 (4)3.041 (3)160 (3)
N3—H3B···O50.78 (4)2.24 (4)3.011 (3)174 (4)
N4—H4A···O7i0.80 (4)2.11 (4)2.901 (3)168 (4)
N4—H4B···O7ii0.90 (4)2.16 (4)3.032 (3)163 (3)
N5—H5A···O6iii0.84 (4)2.09 (4)2.901 (4)164 (4)
N5—H5B···O50.86 (4)2.16 (4)3.007 (3)169 (3)
N6—H6A···O5iii0.85 (4)2.19 (4)3.012 (3)163 (3)
N6—H6B···O6iv0.94 (4)2.07 (4)3.000 (3)168 (3)
C5—H5···O80.952.513.313 (4)142
Symmetry codes: (i) x, y+1, z+1; (ii) x, y1, z; (iii) x, y+1/2, z+1/2; (iv) x, y+1, z.

Experimental details

Crystal data
Chemical formula[Cu2(C10H11O2)4]·6CH4N2O·2C3H6O
Mr1256.36
Crystal system, space groupMonoclinic, P21/c
Temperature (K)200
a, b, c (Å)17.0125 (2), 11.0470 (2), 17.2731 (3)
β (°) 110.385 (1)
V3)3042.95 (8)
Z2
Radiation typeMo Kα
µ (mm1)0.77
Crystal size (mm)0.30 × 0.10 × 0.04
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SCALEPACK; Otwinowski & Minor, 1997)
Tmin, Tmax0.801, 0.973
No. of measured, independent and
observed [I > 2σ(I)] reflections
41379, 6996, 4582
Rint0.074
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.147, 1.06
No. of reflections6996
No. of parameters433
No. of restraints19
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.76, 0.63

Computer programs: COLLECT (Nonius, 1998), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SHELXTL (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O10.80 (4)2.15 (4)2.944 (3)175 (4)
N1—H1B···O60.78 (4)2.17 (4)2.951 (3)178 (4)
N2—H2A···O30.84 (4)2.13 (4)2.954 (3)167 (4)
N2—H2B···O70.83 (4)2.27 (4)3.079 (3)164 (4)
N3—H3A···O5i0.94 (4)2.14 (4)3.041 (3)160 (3)
N3—H3B···O50.78 (4)2.24 (4)3.011 (3)174 (4)
N4—H4A···O7i0.80 (4)2.11 (4)2.901 (3)168 (4)
N4—H4B···O7ii0.90 (4)2.16 (4)3.032 (3)163 (3)
N5—H5A···O6iii0.84 (4)2.09 (4)2.901 (4)164 (4)
N5—H5B···O50.86 (4)2.16 (4)3.007 (3)169 (3)
N6—H6A···O5iii0.85 (4)2.19 (4)3.012 (3)163 (3)
N6—H6B···O6iv0.94 (4)2.07 (4)3.000 (3)168 (3)
Symmetry codes: (i) x, y+1, z+1; (ii) x, y1, z; (iii) x, y+1/2, z+1/2; (iv) x, y+1, z.
Selected geometric parameters (Å, °) top
(II)a(III)b(IV)c
Cu1–O11.933 (2)1.931 (3)1.922 (2)
Cu1–O21.932 (2)1.921 (3)1.931 (2)
Cu1–O31.920 (2)1.915 (2)1.916 (2)
Cu1–O41.919 (2)1.915 (3)1.916 (2)
Cu1–O2i2.476 (2)2.658 (3)2.582 (2)
C4···C1411.176 (5)11.166 (6)11.263 (4)
O1–Cu1–O283.26 (7)83.49 (11)83.41 (7)
O3–Cu1–O483.86 (7)83.64 (10)83.96 (8)
O1–Cu1–O2i86.92 (6)86.26 (10)102.09 (7)
O2–Cu1–O2i103.62 (7)100.17 (9)85.89 (7)
O3–Cu1–O2i90.79 (7)85.62 (9)99.60 (7)
O4–Cu1–O2i93.42 (7)100.44 (10)86.72 (7)
Cu1–O2–Cu1i93.09 (6)93.74 (10)94.11 (7)
C2–C3–C8–X,X*145.4 (7)171.6 (5)-178.6 (6), -147 (1)
C12–C13–C18–X4.6 (4)5.8 (4)10.1 (4)
Notes: (a) The cis,cis dimer in Barret et al. (2002); (b) Ho (2010); (c) this work. For each isopropyl substituent, X corresponds to the centroid for each pair of methyl C atoms, i.e. C9–C10, C9*–C10* and C19–C20, respectively; Ho et al. (2009). Symmetry codes for (II)–(IV): (i) -x + 1, -y, -z; -x, -y, -z + 2; -x + 1, -y + 1, -z + 1.
 

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