(+ac,−ac)-trans-Bis(hinokitiolato)copper(II) and its chloro­form disolvate

The complex trans-bis­(hinokitiolato)copper(II) [systematic name: trans-bis­(3-isopropyl-7-oxo­cyclo­hepta-1,3,5-trienolato)copper(II); abbreviated name: trans-Cu(hino)₂], [Cu(C₁₀H₁₁O₂)₂], is a biologically active compound. Three poly­morphs of this square-planar monomer, all with (+sp,−sp) isopropyl substituents, have been reported previously. A fourth polymorph containing (+ac,−ac) isopropyl groups and its chloro­form disolvate, [Cu(C₁₀H₁₁O₂)₂]·2CHCl₃, both exhibiting nonmerohedral twinning and with all Cu atoms on centers of crystallographic inversion symmetry, are reported here. One of the differences between all of these polymorphs is the relative conformation of the isopropyl groups with respect to the plane of the mol­ecule. Stacking and Cu...olefin π distances ranging from 3.214 (4) to 3.311 (2) Å are observed, and the chloro­form solvent mol­ecules participate in bifurcated C—H...O hydrogen bonds [H...O = 2.26–2.40 Å, C...O = 3.123 (5)–3.214 (5) Å, C—H...O = 127–151° and O...H...O = 74°].

S1. Comment

Hinokitiol (β-thujaplicin), a natural product first isolated from Chamaecyparis taiwanensis (Nozoe, 1936), is a tropolone possessing antimicrobial activity. Its antibacterial and antifungal properties have contributed to its widespread utilization in agricultural and personal care products. Not surprisingly, it is also an excellent ligand for the chelation of metal ions. Hence metal hinokitiolate complexes, M(hino)_x, have also come under renewed interest and scrutiny. For example, Cu, Zn and Sn hinokitiolate complexes have been examined for their suitability in oral care products (Creeth et al., 2000), one polymorph of trans-Cu(hino)₂ has been shown to possess antibacterial properties (Nomiya, Yoshizawa, Tsukagoshi et al., 2004; Nomiya, Yoshizawa, Kasuga et al., 2004), and Cu(hino)₂ has been reported to inhibit the replication of human influenza viruses (Miyamoto et al., 1998). In the last example, our use of Cu(hino)₂ without qualifications is to specify that, to our knowledge, the identity of the compound in that study is not known with certainty.

Antibacterial studies involving Cu indicate a growing need for more precise language and nomenclature in the discussion of these compounds. Readers are cautioned that Cu(hino)₂ as written does not imply a single compound. Rather, Cu(hino)₂ is shorthand for a family of compounds. The members of that family include cis-Cu(hino)₂, trans-Cu(hino)₂, and any combination of monomers, dimers and/or oligomers with the empirical formulation Cu(hino)₂. Molloy and co-workers were the first to `report on the unusual structural chemistry' of Cu(hino)₂ (Barret et al., 2002). The cis monomer has yet to be isolated in pure form, the trans monomer is polymorphic, and a third family member, i.e. [cis-Cu(hino)₂]₂.[trans-Cu(hino)₂]₂.trans- Cu(hino)₂, has been confirmed. The last was used as the starting material for this study.

It is also important to clarify that the 1:1:1 combination of cis-dimer:trans-dimer:trans-monomer has never been shown to pack in any arrangement other than that reported in 2002, and hence cannot be said to be polymorphic. Further, it is not a polymorph of the cis- or trans-monomeric members of the family. To transform one family member into another requires geometric isomerization and/or covalent bond breaking and bond making, and as such they are not polymorphs of each other by the most widely accepted definition of polymorphism (McCrone, 1965). These polymers (dimers, oligomers, etc.) and dynamic isomers (as stated by McCrone) `cannot be called polymorphs although they may behave in a confusingly similar manner'. Currently, only one member within the Cu(hino)₂ family of compounds, i.e. trans-Cu(hino)₂, has been established with certainty to be polymorphic.

Three polymorphs of trans-Cu(hino)₂ have been previously described in the literature, and we report here on a fourth polymorph and its chloroform disolvate. Polymorphs (I) (Barret et al., 2002), (II) (Nomiya, Yoshizawa, Kasuga et al., 2004; Arvanitis et al., 2004) and (III) (Arvanitis et al., 2004) contain (+sp,-sp)-trans-Cu(hino)₂, while the new polymorph, (IV), and its chloroform disolvate, (V), contain (+ac,-ac)-trans-Cu(hino)₂. The synperiplanar (sp) and anticlinal (ac) designators specify the average methyl orientation of each isopropyl group relative to the tropolone ring to which it is attached (see Fig. 1). The + and - signs with the sp designators are not standard nomenclature (Moss, 1996); they are used here to clarify that sp substituents can indeed possess positive and negative values, and to help specify whether the average methyl vectors are rotated slightly to one side or to opposite sides of the best plane through the molecule. Also, our convention is that a syn isopropyl substituent will have its average methyl vector oriented inwards or towards the half of the tropolone molecule containing the metal atom, and conversely, an anti isopropyl group will have its methyl vector directed outwards or away from the metal. Views of (IV) and (V) are given in Fig. 2, and comparative geometric parameters for (I)–(V) are summarized in Table 1.

Triclinic green–yellow plates of (IV) and grey–green plates of (V) were obtained by recrystallization of [cis-Cu(hino)₂]₂.[trans-Cu(hino)₂]₂.trans- Cu(hino)₂ from ethylene glycol–water and chloroform, respectively. The Cu atoms in all forms of monomeric trans-Cu(hino)₂, i.e. (I)–(V), reside on centers of crystallographic inversion symmetry and have square-planar coordination geometries. The five atoms of the CuO₄ cores in these monomers are required by symmetry to be coplanar. All core bond distances and angles in (I)–(V), with the possible exception of (II), are statistically equivalent (see Table 1). Subtle structural variations do of course exist as one moves outwards away from the CuO₄ core. In (I) and (II), the Cu(tropolone)₂ moieties, i.e. excluding the isopropyl substituents, are best described as planar. In (III), a 7.1 (1)° folding along the O1···O2 vector is observed. In (IV) and (V), each half-moiety exhibits a 4.5 (2)° torsional twist (see Fig. 3). Clearly, any computational study regarding polymorph prediction for trans-Cu(hino)₂ would need to consider the conformational flexibility of the Cu(tropolone)₂ moiety, in addition to the rotational degrees of freedom of the isopropyl substituents and intermolecular packing interactions.

As shown in Table 1, the geometry at atom C3 is the most meaningful, and it should come as no surprise that the positioning and orientation of the isopropyl substituents should vary from one polymorph to another. In (I)–(III), the C2—C3—C8 angles are slightly smaller than the C4—C3—C8 angles, but all are near 117°. In (IV) and (V), C2—C3—C8 and C4—C3—C8 are significantly different, with the latter approaching 120°. The C2—C3—C8—X torsion angles in (I)–(III) are also noticably different than those in (IV) and (V). These are the hallmarks for (+sp,-sp) isopropyl substituents in (I)–(III) and for (+ac,-ac) isopropyl substituents in (IV) and (V). These angular and torsional differences are also observed in hinokitiol itself (Derry & Hamor, 1972; Ohishi et al., 1994; Tanaka et al., 2001), and are generally applicable to other metal hinokitiolate complexes as well (Nomiya et al., 2009). Exceptions will inevitably occur with changes in coordination geometries.

The crystal structures of (II)–(V) are consistent with the presence of weak Cu—olefin π interactions. With the exception of (I), the trans-Cu(hino)₂ molecules in these polymorphs pack into extended columns or stacks, such that the π-systems of neighboring molecules are positioned above and below each formally four-coordinate Cu atom. Segments of that stacking for (IV) and (V) are shown in Fig. 3. The Cu atom is 3.336 (1) Å from the centroid defined by atoms C1/C4–C7 in (II), and 3.226 (2), 3.290 (4) and 3.290 (4) Å from the centroid of the C4—C5 bond in (III)–(V), respectively. For (IV) and (V), the closest contacts are actually shifted towards atom C5 and are 3.258 (4) and 3.214 (4) Å, respectively. These distances may be compared with values of 3.25–3.55 Å reported for longer-range noncovalent Cu···arene contacts (Mascal et al., 2000). The distances between the least-squares planes through adjacent molecules, or stacking distances, are 3.336 (1), 3.235 (2), 3.311 (2) and 3.257 (2) Å for (II)–(V), respectively. The Cu···Cu distances between neighboring molecules within a stack are 5.1549 (3), 6.7470 (1), 6.3371 (2) and 6.1893 (2) Å for (II)–(V), respectively, and correspond to a unit translation in the crystallographic a direction for (II), (IV) and (V), and in the b direction for (III). The slippages (see Fig. 3) of one molecule from orthogonal coincidence with a neighboring molecule within a stack are 3.930 (1), 5.921 (2), 5.403 (2) and 5.263 (2) Å for (II)–(V), respectively. It is remarkable that, in spite of the presence of solvent molecules in (V), its trans-Cu(hino)₂ stacks are strikingly similar to those in (IV). The only visual difference in the segments shown in Fig. 3 would appear to be the orientations of the isopropyl groups. Clearly, the reader is encouraged to examine the data above and not just illustrations when comparing such closely related structures.

Finally, each trans-monomer in (V) is also hydrogen-bonded to two chloroform molecules, and so, not surprisingly, the chloroform molecules are also organized into columns running parallel to the crystallographic a axis. The bifurcated hydrogen bonding is shown in Fig. 2. The distances and angles are C21—H21 = 1.00 Å, H21···O1 = 2.26 Å, H21···O2ⁱⁱ = 2.43 Å, C21···O1 = 3.167 (5) Å, C21···O2ⁱⁱ = 3.138 (6) Å, C21—H21···O1 = 151°, C21—H21···O2ⁱⁱ = 127° and O1···H21···O2ⁱⁱ = 74° for one of the crystallographically independent chloroform molecules in the asymmetric unit, and C22—H22 = 1.00 Å, H22···O3ⁱⁱⁱ = 2.31 Å, H22···O4 = 2.40 Å, C22···O3ⁱⁱⁱ = 3.214 (5) Å, C22···O4 = 3.123 (5) Å, C22—H22···O3ⁱⁱⁱ = 149°, C22—H22···O4 = 129° and O3ⁱⁱⁱ···H22···O4 = 74° for the other [symmetry codes: (ii) 1 - x, 1 - y, 2 - z, (iii) 1 - x, -y, 1 - z]. We are not aware of any published examples of bifurcated chloroform hydrogen bonds with metal tropolone complexes. However, there is a plethora of bifurcated chloroform hydrogen bonds with other complexes, among which are two examples containing square-planar CuO₄ cores (Maverick et al., 1986; Pariya et al., 2007). The distances and angles in those examples are C—H = 1.00 Å, H···O = 2.32–2.42 Å, C···O = 3.101–3.281 Å, C—H···O = 132–146° and O···H···O = 66–67°, similar enough to say that the hydrogen bonding in (V) is normal.

In summary, (+ac,-ac)-trans-Cu(hino)₂, (IV), and its chloroform disolvate, (V), have been crystallographically characterized. The hinokitiolate O atoms in (V) participate in hydrogen bonding. Hydrogen bonding was also previously observed in (III) (Arvanitis et al., 2004). These observations are at odds with the suggestion that the formation of the CuO₄ core inhibits an interaction of the O atoms with microorganisms/proteins (Nomiya , Yoshizawa, Tsukagoshi et al., 2004). If C—H···O(hino) hydrogen bonding is possible, surely the stronger N—H···O(hino) and O—H···O(hino) interactions are possible as well.

S2. Experimental

[cis-Cu(hino)₂]₂.[trans-Cu(hino)₂]₂.trans- Cu(hino)₂ was prepared by the literature procedure (Barret et al., 2002). Room-temperature recrystallization from ethylene glycol–water [Solvent ratio?] yielded green–yellow plates of (IV). Recrystallization from chloroform yielded grey–green plates of (V). The crystallographic quality of the latter degrades rapidly via solvent loss. Retaining a small amount of mother liquor, a blanket of chloroform vapor over the solids and/or speed in handling (V) are recommended.

S3. Refinement

The structures of (IV) and (V) were determined from nonmerohedrally twinned data sets. The twin law for (IV) was [-1 0 0, -0.338 1 - 0.379, 0 0 - 1] and corresponds to twinning by two-fold rotation about the a* axis. The contributions from the major and minor components of the twinning were 0.741 (6) and 0.259 (6), respectively. The twin law for (V) was [-1 0 0, 0 - 1 0, 0.447 0.671 1] and corresponds to twinning by two-fold rotation about the c* axis. The twinning was minor but still significant, with contributions of 0.961 (2) and 0.039 (2) from the major and minor components, respectively. The derivation of the twin laws and the subsequent generation of HKLF 5 data sets for refinements were achieved using PLATON (Spek, 2009).

All H atoms were allowed to ride on their respective C atoms, with C—H distances constrained to the SHELXTL (Sheldrick, 2008) default values for the specified functional groups at 200 K, i.e. 0.95, 1.00 and 0.98 Å for the tropolone, methine and methyl H atoms, respectively. The U_iso(H) values were set at 1.2U_eq(C) for the tropolone and methine H atoms, and 1.5U_eq(C) for the methyl H atoms.

Computing details

For both compounds, data collection: COLLECT (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. Projection diagrams of the isopropyl substituents in (IV), showing that the average methyl vector (arrow) for one of the isopropyl groups resides in the -anticlinal region of torsional space (left), while the other isopropyl group resides in the +anticlinal region (right). Hence the use here of the designation (+ac,-ac), where the + and - signs indicate positive and negative torsion angle values.
	Fig. 2. The molecular structures of (IV) (top) and (V) (bottom). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The second crystallographically independent chloroform disolvate is statistically identical and therefore not shown. [Two CHCl3 molecules are shown - please clarify] [Symmetry codes: (i) 2 - x, 2 - y, -z, (ii) 1 - x, 1 - y, 2 - z.]
	Fig. 3. Stacking and π–π interactions in (IV) (top) and (V) (bottom). Displacement ellipsoids are drawn at the 50% probability level. The chloroform moleculess in (V) have been omitted for clarity. The stacking involving the second independent disolvate is also equivalent and therefore not shown.

(IV) (+ac,-ac)-trans-bis(3-isopropyl-7-oxocyclohepta- 1,3,5-trienolato)copper(II)

Crystal data

[Cu(C10H11O2)2]	Z = 1
Mr = 389.92	F(000) = 203
Triclinic, P1	Dx = 1.468 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.3371 (2) Å	Cell parameters from 8954 reflections
b = 8.4915 (5) Å	θ = 2.5–27.5°
c = 8.7216 (5) Å	µ = 1.26 mm^−1
α = 77.037 (2)°	T = 200 K
β = 76.362 (3)°	Plate, green-yellow
γ = 80.093 (3)°	0.20 × 0.10 × 0.02 mm
V = 440.93 (4) Å^3

Data collection

Nonius KappaCCD area-detector diffractometer	2006 independent reflections
Radiation source: fine-focus sealed tube	1461 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.084
ω scans; 600 1.0° rotations	θmax = 27.5°, θmin = 2.5°
Absorption correction: ψ scan (SHELXTL; Sheldrick, 2008)	h = −8→8
Tmin = 0.787, Tmax = 0.975	k = −10→10
8954 measured reflections	l = −9→11

Refinement

Refinement on F^2	Primary atom site location: isomorphous structure methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.204	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.1341P)^2] where P = (Fo^2 + 2Fc^2)/3
2006 reflections	(Δ/σ)max < 0.001
118 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.83 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	1.0000	1.0000	0.0000	0.0392 (3)
O1	0.7824 (5)	0.9796 (4)	0.1949 (4)	0.0373 (7)
O2	0.8394 (5)	0.8586 (4)	−0.0569 (4)	0.0402 (8)
C1	0.6366 (6)	0.8883 (5)	0.1962 (5)	0.0321 (9)
C2	0.4724 (7)	0.8603 (5)	0.3351 (5)	0.0337 (9)
H2	0.4867	0.9096	0.4191	0.040*
C3	0.2916 (7)	0.7740 (5)	0.3742 (5)	0.0327 (9)
C4	0.2286 (7)	0.6954 (5)	0.2706 (5)	0.0356 (10)
H4	0.0971	0.6472	0.3126	0.043*
C5	0.3307 (7)	0.6778 (5)	0.1152 (5)	0.0364 (10)
H5	0.2577	0.6197	0.0665	0.044*
C6	0.5220 (7)	0.7314 (5)	0.0198 (5)	0.0375 (10)
H6	0.5618	0.7018	−0.0829	0.045*
C7	0.6662 (6)	0.8227 (5)	0.0510 (5)	0.0331 (9)
C8	0.1586 (7)	0.7671 (6)	0.5446 (5)	0.0372 (10)
H8	0.1701	0.8699	0.5782	0.045*
C9	−0.0839 (7)	0.7566 (6)	0.5636 (6)	0.0435 (11)
H9A	−0.1402	0.8338	0.4763	0.065*
H9B	−0.1638	0.7833	0.6672	0.065*
H9C	−0.1039	0.6458	0.5594	0.065*
C10	0.2610 (8)	0.6252 (7)	0.6584 (6)	0.0545 (14)
H10A	0.4092	0.6438	0.6590	0.082*
H10B	0.2679	0.5232	0.6215	0.082*
H10C	0.1714	0.6179	0.7674	0.082*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0369 (5)	0.0472 (6)	0.0350 (5)	−0.0120 (3)	−0.0044 (3)	−0.0092 (4)
O1	0.0378 (16)	0.0438 (18)	0.0337 (16)	−0.0140 (13)	−0.0066 (12)	−0.0089 (13)
O2	0.0380 (17)	0.051 (2)	0.0307 (16)	−0.0134 (14)	0.0028 (12)	−0.0112 (14)
C1	0.034 (2)	0.033 (2)	0.032 (2)	−0.0034 (17)	−0.0104 (17)	−0.0071 (17)
C2	0.036 (2)	0.038 (2)	0.031 (2)	−0.0041 (17)	−0.0077 (17)	−0.0133 (18)
C3	0.033 (2)	0.036 (2)	0.029 (2)	−0.0035 (17)	−0.0052 (16)	−0.0086 (17)
C4	0.033 (2)	0.036 (2)	0.038 (2)	−0.0074 (17)	−0.0054 (17)	−0.0060 (18)
C5	0.039 (2)	0.039 (2)	0.034 (2)	−0.0090 (18)	−0.0069 (18)	−0.0108 (18)
C6	0.040 (2)	0.040 (3)	0.032 (2)	−0.0051 (19)	−0.0048 (18)	−0.0092 (19)
C7	0.034 (2)	0.037 (2)	0.028 (2)	−0.0023 (17)	−0.0082 (17)	−0.0046 (17)
C8	0.043 (2)	0.039 (3)	0.032 (2)	−0.0071 (18)	−0.0072 (18)	−0.0088 (18)
C9	0.038 (2)	0.051 (3)	0.038 (2)	−0.007 (2)	−0.0007 (19)	−0.009 (2)
C10	0.045 (3)	0.073 (4)	0.037 (3)	−0.002 (2)	−0.008 (2)	0.000 (2)

Geometric parameters (Å, º)

Cu1—O2^i	1.911 (3)	C5—C6	1.383 (6)
Cu1—O2	1.911 (3)	C5—H5	0.9500
Cu1—O1	1.915 (3)	C6—C7	1.402 (6)
Cu1—O1^i	1.915 (3)	C6—H6	0.9500
O1—C1	1.301 (5)	C8—C9	1.523 (6)
O2—C7	1.297 (5)	C8—C10	1.535 (6)
C1—C2	1.403 (6)	C8—H8	1.0000
C1—C7	1.455 (6)	C9—H9A	0.9800
C2—C3	1.399 (6)	C9—H9B	0.9800
C2—H2	0.9500	C9—H9C	0.9800
C3—C4	1.398 (6)	C10—H10A	0.9800
C3—C8	1.521 (6)	C10—H10B	0.9800
C4—C5	1.386 (6)	C10—H10C	0.9800
C4—H4	0.9500
O2^i—Cu1—O2	180.000 (1)	C5—C6—H6	114.9
O2^i—Cu1—O1	96.24 (12)	C7—C6—H6	114.9
O2—Cu1—O1	83.76 (12)	O2—C7—C6	119.7 (4)
O2^i—Cu1—O1^i	83.76 (12)	O2—C7—C1	114.9 (3)
O2—Cu1—O1^i	96.24 (12)	C6—C7—C1	125.4 (4)
O1—Cu1—O1^i	180.0 (2)	C3—C8—C9	114.8 (4)
C1—O1—Cu1	112.9 (3)	C3—C8—C10	109.6 (4)
C7—O2—Cu1	113.3 (3)	C9—C8—C10	110.4 (4)
O1—C1—C2	118.1 (4)	C3—C8—H8	107.2
O1—C1—C7	115.1 (3)	C9—C8—H8	107.2
C2—C1—C7	126.8 (4)	C10—C8—H8	107.2
C3—C2—C1	132.6 (4)	C8—C9—H9A	109.5
C3—C2—H2	113.7	C8—C9—H9B	109.5
C1—C2—H2	113.7	H9A—C9—H9B	109.5
C4—C3—C2	125.3 (4)	C8—C9—H9C	109.5
C4—C3—C8	119.2 (4)	H9A—C9—H9C	109.5
C2—C3—C8	115.5 (4)	H9B—C9—H9C	109.5
C5—C4—C3	129.2 (4)	C8—C10—H10A	109.5
C5—C4—H4	115.4	C8—C10—H10B	109.5
C3—C4—H4	115.4	H10A—C10—H10B	109.5
C6—C5—C4	130.2 (4)	C8—C10—H10C	109.5
C6—C5—H5	114.9	H10A—C10—H10C	109.5
C4—C5—H5	114.9	H10B—C10—H10C	109.5
C5—C6—C7	130.1 (4)
O2^i—Cu1—O1—C1	179.0 (3)	C4—C5—C6—C7	−1.7 (8)
O2—Cu1—O1—C1	−1.0 (3)	Cu1—O2—C7—C6	174.5 (3)
O1—Cu1—O2—C7	2.6 (3)	Cu1—O2—C7—C1	−3.5 (5)
O1^i—Cu1—O2—C7	−177.4 (3)	C5—C6—C7—O2	179.4 (4)
Cu1—O1—C1—C2	178.1 (3)	C5—C6—C7—C1	−2.8 (7)
Cu1—O1—C1—C7	−0.7 (4)	O1—C1—C7—O2	2.8 (6)
O1—C1—C2—C3	178.0 (4)	C2—C1—C7—O2	−175.8 (4)
C7—C1—C2—C3	−3.4 (8)	O1—C1—C7—C6	−175.1 (4)
C1—C2—C3—C4	−2.5 (8)	C2—C1—C7—C6	6.3 (7)
C1—C2—C3—C8	177.0 (4)	C4—C3—C8—C9	−30.8 (6)
C2—C3—C4—C5	3.5 (8)	C2—C3—C8—C9	149.7 (4)
C8—C3—C4—C5	−176.0 (4)	C4—C3—C8—C10	94.2 (5)
C3—C4—C5—C6	0.4 (8)	C2—C3—C8—C10	−85.4 (5)

Symmetry code: (i) −x+2, −y+2, −z.

(V) (+ac,-ac)-trans-bis(3-isopropyl-7-oxocyclohepta- 1,3,5-trienolato)copper(II) chloroform disolvate

Crystal data

[Cu(C10H11O2)2]·2CHCl3	Z = 2
Mr = 628.65	F(000) = 638
Triclinic, P1	Dx = 1.584 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.1893 (2) Å	Cell parameters from 21329 reflections
b = 8.4581 (3) Å	θ = 1.6–24.9°
c = 25.7989 (10) Å	µ = 1.46 mm^−1
α = 95.730 (2)°	T = 200 K
β = 91.884 (2)°	Plate, grey-green
γ = 100.878 (3)°	0.23 × 0.13 × 0.03 mm
V = 1317.82 (8) Å^3

Data collection

Nonius KappaCCD area-detector diffractometer	4574 independent reflections
Radiation source: fine-focus sealed tube	3392 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.078
ω scans; 1200 0.5° rotations	θmax = 24.9°, θmin = 1.6°
Absorption correction: ψ scan (SHELXTL; Sheldrick, 2008)	h = −7→7
Tmin = 0.734, Tmax = 0.964	k = −10→9
21329 measured reflections	l = −5→30

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.050	H-atom parameters constrained
wR(F^2) = 0.136	w = 1/[σ^2(Fo^2) + (0.0574P)^2 + 1.8234P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
4574 reflections	Δρmax = 0.55 e Å^−3
307 parameters	Δρmin = −0.62 e Å^−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0050 (12)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.5000	0.5000	1.0000	0.0366 (2)
O1	0.6415 (5)	0.4882 (3)	0.93554 (11)	0.0380 (7)
O2	0.6893 (5)	0.3606 (4)	1.02021 (11)	0.0402 (7)
C1	0.7920 (7)	0.3990 (5)	0.93523 (16)	0.0324 (9)
C2	0.9035 (7)	0.3768 (5)	0.88963 (16)	0.0354 (10)
H2	0.8585	0.4313	0.8619	0.042*
C3	1.0678 (7)	0.2900 (5)	0.87710 (17)	0.0355 (10)
C4	1.1711 (7)	0.2048 (5)	0.91088 (18)	0.0405 (10)
H4	1.2839	0.1543	0.8967	0.049*
C5	1.1301 (7)	0.1845 (5)	0.96221 (17)	0.0394 (10)
H5	1.2236	0.1244	0.9783	0.047*
C6	0.9775 (7)	0.2360 (5)	0.99456 (17)	0.0369 (10)
H6	0.9799	0.2041	1.0288	0.044*
C7	0.8200 (7)	0.3285 (5)	0.98366 (16)	0.0344 (10)
C8	1.1288 (7)	0.2866 (6)	0.82041 (18)	0.0439 (11)
H8	1.1269	0.3963	0.8094	0.053*
C9	1.3540 (8)	0.2478 (7)	0.8096 (2)	0.0594 (14)
H9A	1.4669	0.3229	0.8321	0.089*
H9B	1.3841	0.2592	0.7729	0.089*
H9C	1.3562	0.1365	0.8167	0.089*
C10	0.9511 (8)	0.1653 (7)	0.78681 (19)	0.0605 (15)
H10A	0.8084	0.1983	0.7906	0.091*
H10B	0.9427	0.0573	0.7982	0.091*
H10C	0.9884	0.1629	0.7502	0.091*
Cu2	0.5000	0.0000	0.5000	0.0359 (2)
O3	0.3278 (5)	−0.0286 (3)	0.43581 (11)	0.0366 (7)
O4	0.3209 (5)	0.1517 (3)	0.52118 (11)	0.0386 (7)
C11	0.1800 (7)	0.0614 (5)	0.43630 (16)	0.0322 (9)
C12	0.0447 (6)	0.0544 (5)	0.39081 (16)	0.0330 (9)
H12	0.0738	−0.0200	0.3630	0.040*
C13	−0.1226 (7)	0.1348 (5)	0.37877 (16)	0.0325 (9)
C14	−0.2106 (7)	0.2418 (5)	0.41280 (17)	0.0370 (10)
H14	−0.3288	0.2839	0.3986	0.044*
C15	−0.1475 (7)	0.2947 (5)	0.46472 (17)	0.0372 (10)
H15	−0.2339	0.3646	0.4813	0.045*
C16	0.0214 (7)	0.2624 (5)	0.49662 (16)	0.0343 (9)
H16	0.0353	0.3160	0.5311	0.041*
C17	0.1731 (7)	0.1626 (5)	0.48525 (16)	0.0326 (9)
C18	−0.2114 (7)	0.1031 (5)	0.32202 (16)	0.0386 (10)
H18	−0.1984	−0.0098	0.3089	0.046*
C19	−0.4502 (8)	0.1179 (6)	0.31303 (19)	0.0509 (12)
H19A	−0.5421	0.0530	0.3364	0.076*
H19B	−0.4994	0.0786	0.2767	0.076*
H19C	−0.4633	0.2316	0.3201	0.076*
C20	−0.0622 (8)	0.2197 (7)	0.28999 (19)	0.0553 (13)
H20A	−0.1045	0.1915	0.2528	0.083*
H20B	0.0918	0.2106	0.2963	0.083*
H20C	−0.0791	0.3311	0.3005	0.083*
C21	0.4770 (8)	0.7511 (6)	0.87323 (19)	0.0459 (11)
H21	0.4722	0.6606	0.8956	0.055*
Cl1	0.6028 (3)	0.7017 (2)	0.81496 (6)	0.0792 (5)
Cl2	0.2062 (2)	0.77513 (16)	0.85920 (5)	0.0561 (4)
Cl3	0.6298 (3)	0.92920 (18)	0.90753 (7)	0.0751 (5)
C22	0.5322 (7)	0.3384 (5)	0.62680 (18)	0.0401 (10)
H22	0.5147	0.2326	0.6045	0.048*
Cl4	0.7011 (2)	0.33140 (18)	0.68236 (5)	0.0642 (4)
Cl5	0.6540 (2)	0.49373 (15)	0.59055 (5)	0.0574 (4)
Cl6	0.2701 (2)	0.36734 (16)	0.64548 (5)	0.0563 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0396 (4)	0.0388 (5)	0.0347 (4)	0.0139 (3)	0.0049 (3)	0.0075 (3)
O1	0.0419 (17)	0.0397 (17)	0.0371 (17)	0.0184 (14)	0.0040 (13)	0.0070 (13)
O2	0.0443 (18)	0.0466 (18)	0.0342 (17)	0.0166 (14)	0.0077 (13)	0.0100 (14)
C1	0.034 (2)	0.029 (2)	0.034 (2)	0.0066 (18)	0.0018 (18)	0.0038 (17)
C2	0.034 (2)	0.037 (2)	0.035 (2)	0.0077 (18)	−0.0004 (18)	0.0055 (19)
C3	0.032 (2)	0.035 (2)	0.038 (2)	0.0037 (18)	0.0010 (18)	0.0014 (18)
C4	0.040 (2)	0.035 (2)	0.048 (3)	0.0107 (19)	0.002 (2)	0.002 (2)
C5	0.040 (2)	0.038 (3)	0.043 (3)	0.014 (2)	0.001 (2)	0.006 (2)
C6	0.041 (2)	0.036 (2)	0.035 (2)	0.0101 (19)	0.0013 (19)	0.0047 (19)
C7	0.033 (2)	0.032 (2)	0.038 (2)	0.0037 (18)	0.0031 (18)	0.0028 (18)
C8	0.043 (3)	0.047 (3)	0.045 (3)	0.014 (2)	0.005 (2)	0.006 (2)
C9	0.040 (3)	0.085 (4)	0.054 (3)	0.016 (3)	0.013 (2)	0.004 (3)
C10	0.049 (3)	0.094 (4)	0.039 (3)	0.024 (3)	0.003 (2)	−0.009 (3)
Cu2	0.0371 (4)	0.0369 (4)	0.0353 (4)	0.0121 (3)	−0.0016 (3)	0.0037 (3)
O3	0.0364 (16)	0.0379 (17)	0.0385 (17)	0.0146 (13)	0.0010 (13)	0.0053 (13)
O4	0.0408 (17)	0.0399 (17)	0.0370 (17)	0.0146 (13)	−0.0038 (13)	0.0026 (13)
C11	0.035 (2)	0.026 (2)	0.035 (2)	0.0049 (18)	0.0024 (18)	0.0067 (17)
C12	0.033 (2)	0.031 (2)	0.035 (2)	0.0049 (17)	0.0047 (17)	0.0039 (18)
C13	0.031 (2)	0.030 (2)	0.037 (2)	0.0039 (17)	0.0017 (17)	0.0053 (18)
C14	0.038 (2)	0.033 (2)	0.043 (3)	0.0122 (19)	0.0024 (19)	0.0081 (19)
C15	0.039 (2)	0.030 (2)	0.045 (3)	0.0125 (18)	0.0043 (19)	0.0040 (19)
C16	0.037 (2)	0.035 (2)	0.032 (2)	0.0095 (18)	0.0041 (18)	0.0054 (18)
C17	0.031 (2)	0.029 (2)	0.038 (2)	0.0029 (17)	0.0028 (18)	0.0069 (18)
C18	0.043 (3)	0.041 (3)	0.033 (2)	0.014 (2)	−0.0054 (19)	0.0017 (19)
C19	0.043 (3)	0.067 (3)	0.043 (3)	0.014 (2)	−0.006 (2)	0.004 (2)
C20	0.053 (3)	0.076 (4)	0.039 (3)	0.014 (3)	0.002 (2)	0.013 (3)
C21	0.051 (3)	0.044 (3)	0.047 (3)	0.016 (2)	0.000 (2)	0.013 (2)
Cl1	0.0895 (11)	0.0970 (12)	0.0644 (10)	0.0391 (9)	0.0246 (8)	0.0255 (8)
Cl2	0.0541 (8)	0.0607 (8)	0.0546 (8)	0.0121 (6)	−0.0062 (6)	0.0125 (6)
Cl3	0.0709 (10)	0.0596 (9)	0.0882 (11)	−0.0025 (7)	−0.0239 (8)	0.0141 (8)
C22	0.042 (3)	0.036 (2)	0.043 (3)	0.011 (2)	0.006 (2)	0.005 (2)
Cl4	0.0601 (8)	0.0795 (10)	0.0547 (8)	0.0179 (7)	−0.0052 (6)	0.0098 (7)
Cl5	0.0643 (8)	0.0496 (7)	0.0604 (8)	0.0086 (6)	0.0200 (6)	0.0142 (6)
Cl6	0.0477 (7)	0.0561 (8)	0.0673 (9)	0.0133 (6)	0.0135 (6)	0.0081 (6)

Geometric parameters (Å, º)

Cu1—O2^i	1.907 (3)	O3—C11	1.296 (5)
Cu1—O2	1.907 (3)	O4—C17	1.303 (5)
Cu1—O1	1.908 (3)	C11—C12	1.409 (6)
Cu1—O1^i	1.908 (3)	C11—C17	1.460 (6)
O1—C1	1.304 (5)	C12—C13	1.385 (6)
O2—C7	1.304 (5)	C12—H12	0.9500
C1—C2	1.398 (6)	C13—C14	1.394 (6)
C1—C7	1.456 (6)	C13—C18	1.526 (6)
C2—C3	1.390 (6)	C14—C15	1.388 (6)
C2—H2	0.9500	C14—H14	0.9500
C3—C4	1.397 (6)	C15—C16	1.393 (6)
C3—C8	1.521 (6)	C15—H15	0.9500
C4—C5	1.378 (6)	C16—C17	1.395 (6)
C4—H4	0.9500	C16—H16	0.9500
C5—C6	1.383 (6)	C18—C19	1.519 (6)
C5—H5	0.9500	C18—C20	1.542 (7)
C6—C7	1.398 (6)	C18—H18	1.0000
C6—H6	0.9500	C19—H19A	0.9800
C8—C9	1.519 (6)	C19—H19B	0.9800
C8—C10	1.532 (7)	C19—H19C	0.9800
C8—H8	1.0000	C20—H20A	0.9800
C9—H9A	0.9800	C20—H20B	0.9800
C9—H9B	0.9800	C20—H20C	0.9800
C9—H9C	0.9800	C21—Cl2	1.757 (5)
C10—H10A	0.9800	C21—Cl3	1.757 (5)
C10—H10B	0.9800	C21—Cl1	1.765 (5)
C10—H10C	0.9800	C21—H21	1.0000
Cu2—O4^ii	1.900 (3)	C22—Cl5	1.757 (5)
Cu2—O4	1.900 (3)	C22—Cl4	1.759 (5)
Cu2—O3	1.909 (3)	C22—Cl6	1.761 (4)
Cu2—O3^ii	1.909 (3)	C22—H22	1.0000
O2^i—Cu1—O2	180.00 (16)	C11—O3—Cu2	112.8 (2)
O2^i—Cu1—O1	95.56 (12)	C17—O4—Cu2	112.9 (3)
O2—Cu1—O1	84.44 (12)	O3—C11—C12	118.5 (4)
O2^i—Cu1—O1^i	84.44 (12)	O3—C11—C17	115.1 (3)
O2—Cu1—O1^i	95.56 (12)	C12—C11—C17	126.5 (4)
O1—Cu1—O1^i	180.000 (2)	C13—C12—C11	132.4 (4)
C1—O1—Cu1	113.0 (2)	C13—C12—H12	113.8
C7—O2—Cu1	112.3 (3)	C11—C12—H12	113.8
O1—C1—C2	118.6 (4)	C12—C13—C14	126.4 (4)
O1—C1—C7	114.5 (4)	C12—C13—C18	115.0 (4)
C2—C1—C7	126.9 (4)	C14—C13—C18	118.6 (4)
C3—C2—C1	132.3 (4)	C15—C14—C13	128.3 (4)
C3—C2—H2	113.9	C15—C14—H14	115.8
C1—C2—H2	113.9	C13—C14—H14	115.8
C2—C3—C4	126.0 (4)	C14—C15—C16	130.8 (4)
C2—C3—C8	114.6 (4)	C14—C15—H15	114.6
C4—C3—C8	119.3 (4)	C16—C15—H15	114.6
C5—C4—C3	128.3 (4)	C15—C16—C17	129.3 (4)
C5—C4—H4	115.9	C15—C16—H16	115.4
C3—C4—H4	115.9	C17—C16—H16	115.4
C4—C5—C6	131.6 (4)	O4—C17—C16	119.0 (4)
C4—C5—H5	114.2	O4—C17—C11	114.9 (4)
C6—C5—H5	114.2	C16—C17—C11	126.1 (4)
C5—C6—C7	128.8 (4)	C19—C18—C13	115.3 (4)
C5—C6—H6	115.6	C19—C18—C20	109.9 (4)
C7—C6—H6	115.6	C13—C18—C20	108.3 (4)
O2—C7—C6	118.2 (4)	C19—C18—H18	107.7
O2—C7—C1	115.8 (4)	C13—C18—H18	107.7
C6—C7—C1	126.0 (4)	C20—C18—H18	107.7
C9—C8—C3	115.6 (4)	C18—C19—H19A	109.5
C9—C8—C10	109.6 (4)	C18—C19—H19B	109.5
C3—C8—C10	108.9 (4)	H19A—C19—H19B	109.5
C9—C8—H8	107.5	C18—C19—H19C	109.5
C3—C8—H8	107.5	H19A—C19—H19C	109.5
C10—C8—H8	107.5	H19B—C19—H19C	109.5
C8—C9—H9A	109.5	C18—C20—H20A	109.5
C8—C9—H9B	109.5	C18—C20—H20B	109.5
H9A—C9—H9B	109.5	H20A—C20—H20B	109.5
C8—C9—H9C	109.5	C18—C20—H20C	109.5
H9A—C9—H9C	109.5	H20A—C20—H20C	109.5
H9B—C9—H9C	109.5	H20B—C20—H20C	109.5
C8—C10—H10A	109.5	Cl2—C21—Cl3	110.1 (3)
C8—C10—H10B	109.5	Cl2—C21—Cl1	110.1 (3)
H10A—C10—H10B	109.5	Cl3—C21—Cl1	110.4 (3)
C8—C10—H10C	109.5	Cl2—C21—H21	108.7
H10A—C10—H10C	109.5	Cl3—C21—H21	108.7
H10B—C10—H10C	109.5	Cl1—C21—H21	108.7
O4^ii—Cu2—O4	180.00 (17)	Cl5—C22—Cl4	110.4 (3)
O4^ii—Cu2—O3	95.64 (12)	Cl5—C22—Cl6	110.6 (2)
O4—Cu2—O3	84.36 (12)	Cl4—C22—Cl6	110.0 (2)
O4^ii—Cu2—O3^ii	84.36 (12)	Cl5—C22—H22	108.6
O4—Cu2—O3^ii	95.64 (12)	Cl4—C22—H22	108.6
O3—Cu2—O3^ii	180.000 (1)	Cl6—C22—H22	108.6
O2^i—Cu1—O1—C1	179.3 (3)	O4^ii—Cu2—O3—C11	180.0 (3)
O2—Cu1—O1—C1	−0.7 (3)	O4—Cu2—O3—C11	0.0 (3)
O1—Cu1—O2—C7	1.4 (3)	O3—Cu2—O4—C17	1.1 (3)
O1^i—Cu1—O2—C7	−178.6 (3)	O3^ii—Cu2—O4—C17	−178.9 (3)
Cu1—O1—C1—C2	178.2 (3)	Cu2—O3—C11—C12	178.7 (3)
Cu1—O1—C1—C7	−0.1 (4)	Cu2—O3—C11—C17	−0.9 (4)
O1—C1—C2—C3	−179.6 (4)	O3—C11—C12—C13	−179.0 (4)
C7—C1—C2—C3	−1.6 (8)	C17—C11—C12—C13	0.5 (7)
C1—C2—C3—C4	−3.0 (8)	C11—C12—C13—C14	−4.7 (7)
C1—C2—C3—C8	174.8 (4)	C11—C12—C13—C18	173.8 (4)
C2—C3—C4—C5	1.9 (8)	C12—C13—C14—C15	2.2 (7)
C8—C3—C4—C5	−175.7 (4)	C18—C13—C14—C15	−176.3 (4)
C3—C4—C5—C6	1.9 (8)	C13—C14—C15—C16	2.5 (8)
C4—C5—C6—C7	−1.3 (8)	C14—C15—C16—C17	−1.9 (8)
Cu1—O2—C7—C6	175.9 (3)	Cu2—O4—C17—C16	176.2 (3)
Cu1—O2—C7—C1	−1.9 (4)	Cu2—O4—C17—C11	−1.8 (4)
C5—C6—C7—O2	178.8 (4)	C15—C16—C17—O4	179.1 (4)
C5—C6—C7—C1	−3.6 (7)	C15—C16—C17—C11	−3.2 (7)
O1—C1—C7—O2	1.4 (5)	O3—C11—C17—O4	1.9 (5)
C2—C1—C7—O2	−176.7 (4)	C12—C11—C17—O4	−177.7 (4)
O1—C1—C7—C6	−176.3 (4)	O3—C11—C17—C16	−176.0 (4)
C2—C1—C7—C6	5.6 (7)	C12—C11—C17—C16	4.5 (7)
C2—C3—C8—C9	159.0 (4)	C12—C13—C18—C19	151.7 (4)
C4—C3—C8—C9	−23.1 (6)	C14—C13—C18—C19	−29.6 (6)
C2—C3—C8—C10	−77.1 (5)	C12—C13—C18—C20	−84.7 (5)
C4—C3—C8—C10	100.8 (5)	C14—C13—C18—C20	93.9 (5)

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21···O1	1.00	2.26	3.167 (5)	151
C21—H21···O2^i	1.00	2.43	3.138 (6)	127
C22—H22···O3^ii	1.00	2.31	3.214 (5)	149
C22—H22···O4	1.00	2.40	3.123 (5)	129

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y, −z+1.