Crystal structure of catena-poly[hemi[1,3-bis­(2,6-diisoprop­ylphenyl)imidazolium] [[μ₃-acetato-κ³O:O:O′-tri-μ₂-acetato-κ⁶O:O′-dicopper(II)(Cu—Cu)]-μ-chlorido] di­chloro­methane sesqui­solvate]

The title copper(II) complex, {(C₂₇H₃₇N₂)[Cu₄(CH₃COO)₈Cl]·3CH₂Cl₂}_n, is a one-dimensional coordination polymer. The asymmetric unit is composed of a copper(II) tetra­acetate paddle-wheel complex, a Cl⁻ anion situated on a twofold rotation axis, half a 1,3-bis­(2,6-diisoprop­ylphenyl)imidazolium cation (the whole mol­ecule being generated by twofold rotation symmetry) and one and a half of a di­chloro­methane solvent mol­ecule (one being located about a twofold rotation axis). The central metal-organic framework comprises of a tetra­nuclear copper(II) acetate `paddle-wheel' complex which arises from the dimerization of the copper(II) tetra­acetate core comprising of three μ₂-bidentate acetate and one μ₃-tridentate acetate ligands per binuclear paddle-wheel complex. Both Cu^II atoms of the binuclear component adopt a distorted square-pyramidal coordination geometry (τ = 0.04), with a Cu...Cu separation of 2.6016 (2) Å. The apical coordination site of one Cu^II atom is occupied by an O atom of a neighbouring acetate bridge [Cu—O = 2.200 (2) Å], while that of the second Cu^II atom is occupied by a bridging chloride ligand [Cu...Cl = 2.4364 (4) Å]. The chloride bridge is slightly bent with respect to the Cu...Cu inter­nuclear axis [Cu—Cl—Cu = 167.06 (6)°] and the tetra­nuclear units are located about a twofold rotation axis, forming the one-dimensional polymer that propagates along [101]. Charge neutrality is maintained by the inclusion of the 1,3-bis­(2,6-diisoprop­ylphenyl)imidazolium cation within the crystal lattice. In the crystal, the cation and di­chloro­methane solvent mol­ecules are linked to the coordin­ation polymer by various C—H...O and C—H...Cl hydrogen bonds. There are no other significant inter­molecular inter­actions present.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.054
• wR factor = 0.098
• Data-to-parameter ratio = 20.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of         C23 Check
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      9.037 Check
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.227 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          4 Report

Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          1 Info
PLAT300_ALERT_4_G Atom Site Occupancy of *H24A   is Constrained at      0.500 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *H24B   is Constrained at      0.500 Check
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.12 Ratio
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        323 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

S1. Synthesis and crystallization

To a solution of 1,3-bis­(2,6-di-iso­propyl­phenyl)­imidazol-2-ylidine(0.22 g, 0.55 mmol) in dry toluene, at room temperature under nitro­gen, was added anhydrous copper(II)acetate (0.09g, 0.5 mmol). The reaction mixture was stirred at room temperature for 12 h and the blue coloured precipitate, identified as 1,3-bis­(2,6-di-iso­propyl­phenyl)­imidazolium copper(II) acetate, was removed by filtration. The filtrate was left to stand at 248 K in an enclosed vessel for 1 week and the precipitate was collected at the pump. Recrystallization of this solid (vapour diffusion from CH₂Cl₂/petrol) afforded an admixture of two crystalline products; one colourless (which proved to be 1,3-bis­(2,6-di-iso­propyl­phenyl)­imidazolium chloride) and the other, small blue block-like crystals of the title compound. Physical separation of these two crystalline compounds and further recrystallization of the blue-coloured crystals from CH₂Cl₂/petrol afforded crystals suitable for X-ray diffraction analysis.

S2. Refinement

The H atoms were included in calculated positions and refined as riding atoms: C—H = 0.95 - 98 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for other H atoms.

S3. Structural commentary

N-heterocyclic carbenes (NHCs) have been used as ancillary ligands for the preparation of transition metal based catalysts (Hopkinson et al., 2014), which are very useful in organic transformations (Faulkner et al., 2005; Bull et al., 2008). Binuclear Cu^II carboxyl­ate compounds are inter­esting because of their magnetic properties (Kato et al., 1964, Zhang et al., 2005; Cotton et al., 2000) and electrochemical behaviour (Paschke et al., 2003). Herein, we report on the synthesis and crystal structure of the title copper(II) acetate coordination polymer. Here, acetate acts as a bridging bidentate chelating ligand, giving a typical paddle-wheel structure.

The asymmetric unit of the title compound, Fig. 1, is composed of a copper(II) acetate paddle-wheel complex [Cu1···Cu2 = 2.6016 Å], with atom Cu1 coordinated in the apical position by a Cl^- anion [Cu1—Cl1 = 2.4364 (6) Å] situated on a twofold rotation axis. Both copper(II) atoms have distorted square pyramidal co-ordination geometry with τ values of 0.04 (Addison et al., 1984).

The copper(II) acetate paddle-wheel units are linked by inversion symmetry, with the apical position of the second Cu^II atom, Cu2, being occupied by an acetate O atom; Cu2···Cu2ⁱ = 3.1944 (8) Å and Cu2···O6ⁱ = 2.200 (2) Å [symmetry code: (i) - x + 1/2, - y + 1/2, - z + 1], as shown in Fig. 2. These tetra­nuclear units are bridged by the Cl atom, Cl1, coordinated to atom Cu1 and located on a twofold rotation axis, forming the one-dimensional polymer that propagates along [101]; see Fig. 2.

In the crystal, the cation and di­chloro­methane solvent molecules are linked to the coordination polymer by various C—H···O and C—H···Cl hydrogen bonds (Table 1 and Fig. 3). There are no other significant inter­molecular inter­actions present.

This structure is unique in that it possesses a halide bridge linking tetra­nuclear copper paddle-wheel units (for chloride-bridged binuclear systems, see: Chen et al., 2015) and imidazolium salts inter­spersed within the crystal lattice (for imidazolium-functionalised acetate ligands, see: Suresh et al., 2015).

Related literature

For the use of N-heterocyclic carbenes (NHCs) as ancillary ligands for the preparation of transition-metal-based catalysts, see: Hopkinson et al. (2014). For their use in organic transformations, see: Faulkner et al. (2005); Bull et al. (2008). For details of the magnetic properties of binuclear Cu^II carboxylate compounds, see: Kato et al. (1964); Zhang et al. (2005); Cotton et al. (2000), and for their electrochemical behaviour, see: Paschke et al. (2003). For examples of copper(II) paddle-wheel structures, see: de Meester et al. (1973); Ackermann et al. (2000). For chloride-bridged binuclear systems, see: Chen et al. (2015). For imidazolium-functionalized acetate ligands, see: Suresh et al. (2015). For the description of the fivefold coordination symmetry parameter, τ, see: Addison et al. (1984).

Structure description

N-heterocyclic carbenes (NHCs) have been used as ancillary ligands for the preparation of transition metal based catalysts (Hopkinson et al., 2014), which are very useful in organic transformations (Faulkner et al., 2005; Bull et al., 2008). Binuclear Cu^II carboxyl­ate compounds are inter­esting because of their magnetic properties (Kato et al., 1964, Zhang et al., 2005; Cotton et al., 2000) and electrochemical behaviour (Paschke et al., 2003). Herein, we report on the synthesis and crystal structure of the title copper(II) acetate coordination polymer. Here, acetate acts as a bridging bidentate chelating ligand, giving a typical paddle-wheel structure.

The asymmetric unit of the title compound, Fig. 1, is composed of a copper(II) acetate paddle-wheel complex [Cu1···Cu2 = 2.6016 Å], with atom Cu1 coordinated in the apical position by a Cl^- anion [Cu1—Cl1 = 2.4364 (6) Å] situated on a twofold rotation axis. Both copper(II) atoms have distorted square pyramidal co-ordination geometry with τ values of 0.04 (Addison et al., 1984).

The copper(II) acetate paddle-wheel units are linked by inversion symmetry, with the apical position of the second Cu^II atom, Cu2, being occupied by an acetate O atom; Cu2···Cu2ⁱ = 3.1944 (8) Å and Cu2···O6ⁱ = 2.200 (2) Å [symmetry code: (i) - x + 1/2, - y + 1/2, - z + 1], as shown in Fig. 2. These tetra­nuclear units are bridged by the Cl atom, Cl1, coordinated to atom Cu1 and located on a twofold rotation axis, forming the one-dimensional polymer that propagates along [101]; see Fig. 2.

In the crystal, the cation and di­chloro­methane solvent molecules are linked to the coordination polymer by various C—H···O and C—H···Cl hydrogen bonds (Table 1 and Fig. 3). There are no other significant inter­molecular inter­actions present.

This structure is unique in that it possesses a halide bridge linking tetra­nuclear copper paddle-wheel units (for chloride-bridged binuclear systems, see: Chen et al., 2015) and imidazolium salts inter­spersed within the crystal lattice (for imidazolium-functionalised acetate ligands, see: Suresh et al., 2015).

For the use of N-heterocyclic carbenes (NHCs) as ancillary ligands for the preparation of transition-metal-based catalysts, see: Hopkinson et al. (2014). For their use in organic transformations, see: Faulkner et al. (2005); Bull et al. (2008). For details of the magnetic properties of binuclear Cu^II carboxylate compounds, see: Kato et al. (1964); Zhang et al. (2005); Cotton et al. (2000), and for their electrochemical behaviour, see: Paschke et al. (2003). For examples of copper(II) paddle-wheel structures, see: de Meester et al. (1973); Ackermann et al. (2000). For chloride-bridged binuclear systems, see: Chen et al. (2015). For imidazolium-functionalized acetate ligands, see: Suresh et al. (2015). For the description of the fivefold coordination symmetry parameter, τ, see: Addison et al. (1984).

Synthesis and crystallization

To a solution of 1,3-bis­(2,6-di-iso­propyl­phenyl)­imidazol-2-ylidine(0.22 g, 0.55 mmol) in dry toluene, at room temperature under nitro­gen, was added anhydrous copper(II)acetate (0.09g, 0.5 mmol). The reaction mixture was stirred at room temperature for 12 h and the blue coloured precipitate, identified as 1,3-bis­(2,6-di-iso­propyl­phenyl)­imidazolium copper(II) acetate, was removed by filtration. The filtrate was left to stand at 248 K in an enclosed vessel for 1 week and the precipitate was collected at the pump. Recrystallization of this solid (vapour diffusion from CH₂Cl₂/petrol) afforded an admixture of two crystalline products; one colourless (which proved to be 1,3-bis­(2,6-di-iso­propyl­phenyl)­imidazolium chloride) and the other, small blue block-like crystals of the title compound. Physical separation of these two crystalline compounds and further recrystallization of the blue-coloured crystals from CH₂Cl₂/petrol afforded crystals suitable for X-ray diffraction analysis.

Refinement details

The H atoms were included in calculated positions and refined as riding atoms: C—H = 0.95 - 98 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for other H atoms.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

Figures

	Fig. 1. A view of the molecular structure of the asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view of the tetranuclear paddle-wheel unit of the title polymeric compound [symmetry codes: (a) -x, y, -z + 1/2; (b) -x + 1/2, -y + 1/2, -z + 1; (c) x + 1/2, -y + 1/2, z + 1/2; (d) -x, y, -z + 1/2; (e) -x + 1, y, -z + 1/2].
	Fig. 3. A view along the b axis of the crystal packing of title compound. Colour code: coordination polymer black, organic cation red; CH2Cl2 solvent molecules green and blue.

catena-Poly[hemi(1,3-bis(2,6-diisopropylphenyl)imidazolium) [[µ₃-acetato-κ³O:O:O'- tri-µ₂-acetato-κ⁶O:O'-dicopper(II)(Cu—Cu)]-µ-chlorido] dichloromethane sesquisolvate]

Crystal data

(C27H37N2)[Cu4(C2H3O2)8Cl]·3CH2Cl2	F(000) = 2880
Mr = 1406.32	Dx = 1.530 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 22.097 (2) Å	Cell parameters from 3370 reflections
b = 13.146 (2) Å	θ = 2.3–24.3°
c = 23.607 (3) Å	µ = 1.74 mm^−1
β = 117.122 (4)°	T = 100 K
V = 6103.5 (13) Å^3	Block, blue
Z = 4	0.22 × 0.13 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer	7274 independent reflections
Radiation source: fine-focus sealed tube	5215 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.079
phi and ω scans	θmax = 28.3°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −29→29
Tmin = 0.700, Tmax = 0.918	k = −17→17
26111 measured reflections	l = −31→31

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0252P)^2] where P = (Fo^2 + 2Fc^2)/3
7274 reflections	(Δ/σ)max < 0.001
348 parameters	Δρmax = 0.70 e Å^−3
0 restraints	Δρmin = −0.46 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.11018 (2)	0.34481 (3)	0.34274 (2)	0.01543 (11)
Cu2	0.22901 (2)	0.32446 (3)	0.44052 (2)	0.01720 (12)
Cl1	0.0000	0.36569 (9)	0.2500	0.0197 (3)
O1	0.15907 (12)	0.45167 (19)	0.32111 (12)	0.0215 (6)
O2	0.26294 (13)	0.4197 (2)	0.39901 (12)	0.0276 (7)
O3	0.09345 (12)	0.4383 (2)	0.39834 (12)	0.0257 (6)
O4	0.19967 (13)	0.43484 (19)	0.47704 (12)	0.0242 (6)
O5	0.08495 (12)	0.23045 (19)	0.38354 (12)	0.0244 (6)
O6	0.18267 (11)	0.22502 (18)	0.47165 (11)	0.0170 (6)
O7	0.14402 (13)	0.24162 (19)	0.30413 (12)	0.0233 (6)
O8	0.24153 (12)	0.2136 (2)	0.39190 (12)	0.0243 (6)
C1	0.2223 (2)	0.4655 (3)	0.34956 (18)	0.0206 (8)
C2	0.2526 (2)	0.5414 (3)	0.32215 (19)	0.0287 (10)
H2A	0.2161	0.5773	0.2866	0.043*
H2B	0.2813	0.5059	0.3068	0.043*
H2C	0.2802	0.5905	0.3551	0.043*
C3	0.1390 (2)	0.4647 (3)	0.45198 (18)	0.0214 (9)
C4	0.1181 (2)	0.5375 (3)	0.4893 (2)	0.0336 (11)
H4A	0.0965	0.5974	0.4632	0.050*
H4B	0.1583	0.5586	0.5280	0.050*
H4C	0.0859	0.5037	0.5011	0.050*
C5	0.12274 (18)	0.1946 (3)	0.43727 (17)	0.0182 (8)
C6	0.09553 (18)	0.1106 (3)	0.46205 (17)	0.0231 (9)
H6A	0.0557	0.1351	0.4660	0.035*
H6B	0.1307	0.0889	0.5039	0.035*
H6C	0.0823	0.0530	0.4325	0.035*
C7	0.19844 (19)	0.1934 (3)	0.33588 (18)	0.0204 (8)
C8	0.2120 (2)	0.1034 (3)	0.30460 (19)	0.0309 (10)
H8A	0.2608	0.0884	0.3254	0.046*
H8B	0.1971	0.1183	0.2595	0.046*
H8C	0.1869	0.0444	0.3084	0.046*
N1	0.45188 (14)	0.2152 (2)	0.25127 (13)	0.0154 (6)
C9	0.38905 (18)	0.2530 (3)	0.24934 (18)	0.0181 (8)
C10	0.33835 (18)	0.2839 (3)	0.19043 (18)	0.0202 (8)
C11	0.27799 (19)	0.3182 (3)	0.18894 (18)	0.0239 (9)
H11	0.2417	0.3396	0.1497	0.029*
C12	0.27022 (19)	0.3217 (3)	0.24336 (19)	0.0251 (9)
H12	0.2284	0.3447	0.2412	0.030*
C13	0.32230 (19)	0.2922 (3)	0.30130 (19)	0.0253 (9)
H13	0.3162	0.2966	0.3385	0.030*
C14	0.38368 (18)	0.2560 (3)	0.30584 (18)	0.0204 (8)
C15	0.34523 (19)	0.2799 (3)	0.12880 (18)	0.0261 (9)
H15	0.3923	0.2559	0.1400	0.031*
C16	0.3369 (2)	0.3836 (3)	0.09913 (19)	0.0349 (11)
H16A	0.2901	0.4073	0.0849	0.052*
H16B	0.3466	0.3798	0.0626	0.052*
H16C	0.3685	0.4313	0.1306	0.052*
C17	0.2957 (2)	0.2034 (3)	0.0823 (2)	0.0406 (12)
H17A	0.3010	0.2023	0.0433	0.061*
H17B	0.2491	0.2230	0.0720	0.061*
H17C	0.3052	0.1356	0.1017	0.061*
C18	0.44195 (19)	0.2267 (3)	0.36975 (18)	0.0252 (9)
H18	0.4691	0.1725	0.3621	0.030*
C19	0.4890 (2)	0.3180 (3)	0.4002 (2)	0.0407 (12)
H19A	0.4629	0.3737	0.4060	0.061*
H19B	0.5084	0.3406	0.3724	0.061*
H19C	0.5257	0.2980	0.4416	0.061*
C20	0.4180 (2)	0.1848 (3)	0.41638 (19)	0.0339 (10)
H20A	0.3866	0.1281	0.3965	0.051*
H20B	0.3947	0.2386	0.4277	0.051*
H20C	0.4573	0.1608	0.4549	0.051*
C21	0.46971 (17)	0.1151 (3)	0.25048 (16)	0.0163 (8)
H21	0.4442	0.0570	0.2506	0.020*
C22	0.5000	0.2738 (4)	0.2500	0.0167 (11)
H22	0.5000	0.3460	0.2500	0.020*
Cl2	0.08838 (7)	0.23037 (12)	0.10086 (7)	0.0627 (4)
Cl3	0.09648 (6)	0.43818 (10)	0.14520 (6)	0.0528 (4)
C23	0.0688 (2)	0.3145 (4)	0.1482 (2)	0.0410 (12)
H23A	0.0190	0.3150	0.1332	0.049*
H23B	0.0907	0.2903	0.1929	0.049*
Cl4	0.03361 (6)	0.02638 (9)	0.20944 (6)	0.0455 (3)
C24	0.0000	0.1022 (4)	0.2500	0.0365 (16)
H24A	−0.0363	0.1465	0.2191	0.044*	0.5
H24B	0.0363	0.1465	0.2809	0.044*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0147 (2)	0.0170 (2)	0.0125 (2)	0.00113 (18)	0.00437 (19)	0.00052 (18)
Cu2	0.0138 (2)	0.0222 (3)	0.0141 (2)	0.00123 (19)	0.00498 (19)	0.00456 (19)
Cl1	0.0180 (7)	0.0168 (6)	0.0156 (7)	0.000	0.0001 (5)	0.000
O1	0.0182 (14)	0.0239 (15)	0.0205 (15)	−0.0014 (11)	0.0069 (12)	0.0041 (11)
O2	0.0180 (14)	0.0377 (17)	0.0235 (15)	−0.0006 (12)	0.0064 (12)	0.0130 (13)
O3	0.0171 (14)	0.0358 (17)	0.0235 (15)	0.0020 (12)	0.0085 (12)	−0.0096 (13)
O4	0.0223 (15)	0.0239 (15)	0.0197 (15)	0.0014 (12)	0.0038 (12)	−0.0010 (12)
O5	0.0165 (14)	0.0302 (16)	0.0201 (15)	−0.0023 (12)	0.0027 (12)	0.0105 (12)
O6	0.0098 (12)	0.0241 (14)	0.0154 (13)	0.0002 (10)	0.0041 (11)	0.0042 (11)
O7	0.0235 (15)	0.0236 (15)	0.0196 (15)	0.0048 (12)	0.0070 (12)	−0.0040 (11)
O8	0.0207 (14)	0.0329 (16)	0.0187 (15)	0.0097 (12)	0.0085 (12)	0.0027 (12)
C1	0.026 (2)	0.019 (2)	0.024 (2)	0.0001 (17)	0.0176 (19)	−0.0020 (16)
C2	0.029 (2)	0.028 (2)	0.034 (3)	0.0015 (18)	0.019 (2)	0.0067 (19)
C3	0.030 (2)	0.020 (2)	0.021 (2)	−0.0035 (17)	0.0181 (19)	−0.0010 (16)
C4	0.038 (3)	0.037 (3)	0.033 (3)	−0.003 (2)	0.022 (2)	−0.011 (2)
C5	0.0188 (19)	0.022 (2)	0.016 (2)	0.0017 (16)	0.0097 (17)	−0.0008 (16)
C6	0.021 (2)	0.026 (2)	0.019 (2)	−0.0046 (17)	0.0058 (17)	0.0037 (17)
C7	0.027 (2)	0.020 (2)	0.024 (2)	−0.0019 (17)	0.0195 (19)	0.0021 (17)
C8	0.034 (3)	0.029 (2)	0.037 (3)	0.0050 (19)	0.023 (2)	−0.0033 (19)
N1	0.0135 (15)	0.0192 (16)	0.0143 (16)	0.0014 (12)	0.0072 (13)	−0.0009 (13)
C9	0.0156 (19)	0.0173 (19)	0.024 (2)	−0.0016 (15)	0.0115 (17)	−0.0029 (16)
C10	0.020 (2)	0.0168 (19)	0.023 (2)	0.0001 (16)	0.0092 (17)	0.0008 (16)
C11	0.020 (2)	0.026 (2)	0.024 (2)	−0.0014 (17)	0.0077 (17)	0.0007 (17)
C12	0.017 (2)	0.026 (2)	0.035 (2)	0.0037 (17)	0.0142 (18)	0.0014 (19)
C13	0.025 (2)	0.029 (2)	0.031 (2)	−0.0007 (18)	0.0198 (19)	−0.0046 (18)
C14	0.021 (2)	0.0150 (19)	0.027 (2)	−0.0003 (15)	0.0134 (18)	0.0002 (16)
C15	0.020 (2)	0.038 (3)	0.019 (2)	0.0082 (18)	0.0080 (17)	0.0059 (18)
C16	0.044 (3)	0.039 (3)	0.026 (2)	−0.008 (2)	0.020 (2)	0.001 (2)
C17	0.065 (3)	0.035 (3)	0.026 (2)	−0.005 (2)	0.024 (2)	−0.002 (2)
C18	0.022 (2)	0.039 (2)	0.020 (2)	0.0024 (18)	0.0133 (18)	−0.0001 (18)
C19	0.040 (3)	0.052 (3)	0.028 (3)	−0.008 (2)	0.013 (2)	0.001 (2)
C20	0.037 (3)	0.038 (3)	0.027 (2)	0.001 (2)	0.015 (2)	0.004 (2)
C21	0.020 (2)	0.0148 (18)	0.0162 (19)	−0.0042 (15)	0.0096 (16)	−0.0017 (15)
C22	0.019 (3)	0.016 (3)	0.017 (3)	0.000	0.010 (2)	0.000
Cl2	0.0452 (8)	0.0907 (11)	0.0573 (9)	−0.0103 (7)	0.0279 (7)	−0.0248 (8)
Cl3	0.0508 (8)	0.0583 (9)	0.0599 (9)	0.0080 (6)	0.0344 (7)	0.0196 (7)
C23	0.030 (2)	0.065 (3)	0.030 (3)	−0.007 (2)	0.015 (2)	−0.004 (2)
Cl4	0.0564 (8)	0.0313 (6)	0.0472 (8)	−0.0066 (6)	0.0223 (6)	−0.0007 (5)
C24	0.041 (4)	0.018 (3)	0.036 (4)	0.000	0.006 (3)	0.000

Geometric parameters (Å, º)

Cu1—O3	1.952 (3)	C9—C14	1.393 (5)
Cu1—O7	1.963 (2)	C10—C11	1.394 (5)
Cu1—O1	1.976 (2)	C10—C15	1.531 (5)
Cu1—O5	1.997 (2)	C11—C12	1.372 (5)
Cu1—Cl1	2.4365 (5)	C11—H11	0.9500
Cu1—Cu2	2.6015 (6)	C12—C13	1.382 (5)
Cu2—O2	1.939 (3)	C12—H12	0.9500
Cu2—O4	1.944 (3)	C13—C14	1.394 (5)
Cu2—O8	1.951 (3)	C13—H13	0.9500
Cu2—O6	1.996 (2)	C14—C18	1.520 (5)
Cu2—O6^i	2.200 (2)	C15—C16	1.506 (5)
Cl1—Cu1^ii	2.4365 (5)	C15—C17	1.523 (5)
O1—C1	1.257 (4)	C15—H15	1.0000
O2—C1	1.255 (4)	C16—H16A	0.9800
O3—C3	1.255 (4)	C16—H16B	0.9800
O4—C3	1.257 (4)	C16—H16C	0.9800
O5—C5	1.250 (4)	C17—H17A	0.9800
O6—C5	1.262 (4)	C17—H17B	0.9800
O6—Cu2^i	2.200 (2)	C17—H17C	0.9800
O7—C7	1.260 (4)	C18—C20	1.525 (5)
O8—C7	1.256 (4)	C18—C19	1.535 (5)
C1—C2	1.503 (5)	C18—H18	1.0000
C2—H2A	0.9800	C19—H19A	0.9800
C2—H2B	0.9800	C19—H19B	0.9800
C2—H2C	0.9800	C19—H19C	0.9800
C3—C4	1.509 (5)	C20—H20A	0.9800
C4—H4A	0.9800	C20—H20B	0.9800
C4—H4B	0.9800	C20—H20C	0.9800
C4—H4C	0.9800	C21—C21^iii	1.349 (6)
C5—C6	1.497 (5)	C21—H21	0.9500
C6—H6A	0.9800	C22—N1^iii	1.324 (4)
C6—H6B	0.9800	C22—H22	0.9500
C6—H6C	0.9800	Cl2—C23	1.762 (4)
C7—C8	1.496 (5)	Cl3—C23	1.750 (5)
C8—H8A	0.9800	C23—H23A	0.9900
C8—H8B	0.9800	C23—H23B	0.9900
C8—H8C	0.9800	Cl4—C24	1.764 (3)
N1—C22	1.324 (4)	C24—Cl4^ii	1.764 (3)
N1—C21	1.376 (4)	C24—H24A	0.9900
N1—C9	1.455 (4)	C24—H24B	0.9900
C9—C10	1.390 (5)
O3—Cu1—O7	167.50 (11)	H8B—C8—H8C	109.5
O3—Cu1—O1	91.12 (11)	C22—N1—C21	108.5 (3)
O7—Cu1—O1	90.14 (11)	C22—N1—C9	124.4 (3)
O3—Cu1—O5	88.26 (11)	C21—N1—C9	126.9 (3)
O7—Cu1—O5	87.30 (11)	C10—C9—C14	124.6 (3)
O1—Cu1—O5	164.93 (10)	C10—C9—N1	116.9 (3)
O3—Cu1—Cl1	96.62 (8)	C14—C9—N1	118.5 (3)
O7—Cu1—Cl1	95.55 (8)	C9—C10—C11	116.5 (3)
O1—Cu1—Cl1	97.34 (8)	C9—C10—C15	123.8 (3)
O5—Cu1—Cl1	97.69 (7)	C11—C10—C15	119.7 (3)
O3—Cu1—Cu2	83.81 (8)	C12—C11—C10	120.9 (4)
O7—Cu1—Cu2	84.08 (7)	C12—C11—H11	119.5
O1—Cu1—Cu2	81.54 (7)	C10—C11—H11	119.5
O5—Cu1—Cu2	83.42 (7)	C11—C12—C13	120.9 (4)
Cl1—Cu1—Cu2	178.81 (3)	C11—C12—H12	119.5
O2—Cu2—O4	91.50 (11)	C13—C12—H12	119.5
O2—Cu2—O8	89.64 (11)	C12—C13—C14	120.9 (4)
O4—Cu2—O8	169.67 (11)	C12—C13—H13	119.5
O2—Cu2—O6	172.08 (10)	C14—C13—H13	119.5
O4—Cu2—O6	89.70 (10)	C9—C14—C13	116.2 (4)
O8—Cu2—O6	87.79 (10)	C9—C14—C18	122.7 (3)
O2—Cu2—O6^i	106.62 (10)	C13—C14—C18	121.1 (3)
O4—Cu2—O6^i	97.74 (10)	C16—C15—C17	111.6 (3)
O8—Cu2—O6^i	91.76 (10)	C16—C15—C10	111.5 (3)
O6—Cu2—O6^i	80.96 (10)	C17—C15—C10	111.0 (3)
O2—Cu2—Cu1	87.23 (8)	C16—C15—H15	107.5
O4—Cu2—Cu1	84.89 (7)	C17—C15—H15	107.5
O8—Cu2—Cu1	84.91 (7)	C10—C15—H15	107.5
O6—Cu2—Cu1	85.09 (7)	C15—C16—H16A	109.5
O6^i—Cu2—Cu1	165.77 (6)	C15—C16—H16B	109.5
Cu1—Cl1—Cu1^ii	167.06 (6)	H16A—C16—H16B	109.5
C1—O1—Cu1	124.7 (2)	C15—C16—H16C	109.5
C1—O2—Cu2	120.1 (2)	H16A—C16—H16C	109.5
C3—O3—Cu1	122.8 (2)	H16B—C16—H16C	109.5
C3—O4—Cu2	121.6 (2)	C15—C17—H17A	109.5
C5—O5—Cu1	124.7 (2)	C15—C17—H17B	109.5
C5—O6—Cu2	122.3 (2)	H17A—C17—H17B	109.5
C5—O6—Cu2^i	137.1 (2)	C15—C17—H17C	109.5
Cu2—O6—Cu2^i	99.04 (9)	H17A—C17—H17C	109.5
C7—O7—Cu1	122.3 (2)	H17B—C17—H17C	109.5
C7—O8—Cu2	122.3 (2)	C14—C18—C20	113.1 (3)
O2—C1—O1	125.3 (3)	C14—C18—C19	110.7 (3)
O2—C1—C2	116.6 (3)	C20—C18—C19	109.2 (3)
O1—C1—C2	118.1 (3)	C14—C18—H18	107.9
C1—C2—H2A	109.5	C20—C18—H18	107.9
C1—C2—H2B	109.5	C19—C18—H18	107.9
H2A—C2—H2B	109.5	C18—C19—H19A	109.5
C1—C2—H2C	109.5	C18—C19—H19B	109.5
H2A—C2—H2C	109.5	H19A—C19—H19B	109.5
H2B—C2—H2C	109.5	C18—C19—H19C	109.5
O3—C3—O4	125.5 (4)	H19A—C19—H19C	109.5
O3—C3—C4	116.6 (3)	H19B—C19—H19C	109.5
O4—C3—C4	117.9 (3)	C18—C20—H20A	109.5
C3—C4—H4A	109.5	C18—C20—H20B	109.5
C3—C4—H4B	109.5	H20A—C20—H20B	109.5
H4A—C4—H4B	109.5	C18—C20—H20C	109.5
C3—C4—H4C	109.5	H20A—C20—H20C	109.5
H4A—C4—H4C	109.5	H20B—C20—H20C	109.5
H4B—C4—H4C	109.5	C21^iii—C21—N1	107.02 (18)
O5—C5—O6	123.5 (3)	C21^iii—C21—H21	126.5
O5—C5—C6	118.2 (3)	N1—C21—H21	126.5
O6—C5—C6	118.2 (3)	N1^iii—C22—N1	108.9 (4)
C5—C6—H6A	109.5	N1^iii—C22—H22	125.6
C5—C6—H6B	109.5	N1—C22—H22	125.6
H6A—C6—H6B	109.5	Cl3—C23—Cl2	111.4 (2)
C5—C6—H6C	109.5	Cl3—C23—H23A	109.3
H6A—C6—H6C	109.5	Cl2—C23—H23A	109.3
H6B—C6—H6C	109.5	Cl3—C23—H23B	109.3
O8—C7—O7	125.5 (3)	Cl2—C23—H23B	109.3
O8—C7—C8	117.4 (3)	H23A—C23—H23B	108.0
O7—C7—C8	117.1 (3)	Cl4—C24—Cl4^ii	111.2 (3)
C7—C8—H8A	109.5	Cl4—C24—H24A	109.4
C7—C8—H8B	109.5	Cl4^ii—C24—H24A	109.4
H8A—C8—H8B	109.5	Cl4—C24—H24B	109.4
C7—C8—H8C	109.5	Cl4^ii—C24—H24B	109.4
H8A—C8—H8C	109.5	H24A—C24—H24B	108.0
Cu2—O2—C1—O1	−3.8 (5)	C14—C9—C10—C15	−180.0 (4)
Cu2—O2—C1—C2	177.3 (2)	N1—C9—C10—C15	0.2 (5)
Cu1—O1—C1—O2	−6.5 (5)	C9—C10—C11—C12	0.5 (6)
Cu1—O1—C1—C2	172.4 (2)	C15—C10—C11—C12	179.4 (4)
Cu1—O3—C3—O4	−0.9 (5)	C10—C11—C12—C13	0.7 (6)
Cu1—O3—C3—C4	−180.0 (3)	C11—C12—C13—C14	−1.4 (6)
Cu2—O4—C3—O3	−9.7 (5)	C10—C9—C14—C13	0.5 (6)
Cu2—O4—C3—C4	169.4 (3)	N1—C9—C14—C13	−179.6 (3)
Cu1—O5—C5—O6	−2.0 (5)	C10—C9—C14—C18	−176.6 (3)
Cu1—O5—C5—C6	178.2 (2)	N1—C9—C14—C18	3.3 (5)
Cu2—O6—C5—O5	−7.1 (5)	C12—C13—C14—C9	0.8 (5)
Cu2^i—O6—C5—O5	−169.6 (2)	C12—C13—C14—C18	178.0 (3)
Cu2—O6—C5—C6	172.7 (2)	C9—C10—C15—C16	−120.9 (4)
Cu2^i—O6—C5—C6	10.2 (5)	C11—C10—C15—C16	60.3 (5)
Cu2—O8—C7—O7	1.6 (5)	C9—C10—C15—C17	114.0 (4)
Cu2—O8—C7—C8	−177.0 (2)	C11—C10—C15—C17	−64.7 (5)
Cu1—O7—C7—O8	−10.2 (5)	C9—C14—C18—C20	−151.1 (4)
Cu1—O7—C7—C8	168.4 (2)	C13—C14—C18—C20	31.8 (5)
C22—N1—C9—C10	77.5 (4)	C9—C14—C18—C19	86.0 (4)
C21—N1—C9—C10	−98.0 (4)	C13—C14—C18—C19	−91.0 (4)
C22—N1—C9—C14	−102.4 (4)	C22—N1—C21—C21^iii	0.8 (5)
C21—N1—C9—C14	82.2 (5)	C9—N1—C21—C21^iii	176.8 (4)
C14—C9—C10—C11	−1.2 (6)	C21—N1—C22—N1^iii	−0.29 (17)
N1—C9—C10—C11	178.9 (3)	C9—N1—C22—N1^iii	−176.4 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6B···O2^i	0.98	2.43	3.368 (4)	161
C21—H21···O1^iv	0.95	2.54	3.344 (4)	142
C22—H22···Cl4^v	0.95	2.78	3.626 (5)	149
C22—H22···Cl4^vi	0.95	2.78	3.626 (5)	149
C23—H23A···O5^ii	0.99	2.42	3.316 (5)	151
C23—H23B···O7	0.99	2.42	3.413 (5)	177
C24—H24B···O5	0.99	2.42	3.303 (4)	148
C24—H24B···O7	0.99	2.52	3.378 (4)	145
C24—H24A···O5^ii	0.99	2.42	3.303 (4)	148
C24—H24A···O7^ii	0.99	2.52	3.378 (4)	145

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