Crystal structure of catena-poly[hemi[1,3-bis-(2,6-diisoprop-ylphenyl)imidazolium] [[μ3-acetato-κ(3) O:O:O'-tri-μ2-acetato-κ(6) O:O'-dicopper(II)(Cu-Cu)]-μ-chlorido] di-chloro-methane sesqui-solvate].

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) tetra-acetate paddle-wheel complex, a Cl(-) anion situated on a twofold rotation axis, half a 1,3-bis-(2,6-diisoprop-ylphenyl)imidazolium cation (the whole mol-ecule being generated by twofold rotation symmetry) and one and a half of a di-chloro-methane solvent mol-ecule (one being located about a twofold rotation axis). The central metal-organic framework comprises of a tetra-nuclear copper(II) acetate 'paddle-wheel' complex which arises from the dimerization of the copper(II) tetra-acetate 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 inter-nuclear axis [Cu-Cl-Cu = 167.06 (6)°] and the tetra-nuclear 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-diisoprop-ylphenyl)imidazolium cation within the crystal lattice. In the crystal, the cation and di-chloro-methane solvent mol-ecules are linked to the coordin-ation polymer by various C-H⋯O and C-H⋯Cl hydrogen bonds. There are no other significant inter-molecular inter-actions present.

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 CuII 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 ▸).

Experimental

Crystal data

(C27H37N2)[Cu4(C2H3O2)8Cl]·3CH2Cl2

M = 1406.32

Monoclinic,

a = 22.097 (2) Å

b = 13.146 (2) Å

c = 23.607 (3) Å

β = 117.122 (4)°

V = 6103.5 (13) Å3

Z = 4

Mo Kα radiation

μ = 1.74 mm−1

T = 100 K

0.22 × 0.13 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▸) T min = 0.700, T max = 0.918

26111 measured reflections

7274 independent reflections

5215 reflections with I > 2σ(I)

R int = 0.079

Refinement

R[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.098

S = 0.98

7274 reflections

348 parameters

H-atom parameters constrained

Δρmax = 0.70 e Å−3

Δρmin = −0.46 e Å−3

Data collection: SMART (Bruker, 2001 ▸); cell refinement: SAINT (Bruker, 2001 ▸); data reduction: SAINT; 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 and PLATON.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015013675/su5152sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015013675/su5152Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S2056989015013675/su5152fig1.tif

A view of the mol­ecular structure of the asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.

x y z x y z x y z x y z x y z . DOI: 10.1107/S2056989015013675/su5152fig2.tif

A view of the tetra­nuclear paddle-wheel unit of the title polymeric compound [symmetry codes: (a) −x, y, −z + ; (b) −x + , −y + , −z + 1; (c) x + , −y + , z + ; (d) −x, y, −z + ; (e) −x + 1, y, −z + ].

Click here for additional data file.

b 2 2 . DOI: 10.1107/S2056989015013675/su5152fig3.tif

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.

CCDC reference: 999046

Additional supporting information: crystallographic information; 3D view; checkCIF report

Enhanced figure: interactive version of Fig. 1d

(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) Å3	Block, blue
Z = 4	0.22 × 0.13 × 0.05 mm

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 on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098	H-atom parameters constrained
S = 0.98	w = 1/[σ2(Fo2) + (0.0252P)2] where P = (Fo2 + 2Fc2)/3
7274 reflections	(Δ/σ)max < 0.001
348 parameters	Δρmax = 0.70 e Å−3
0 restraints	Δρmin = −0.46 e Å−3

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.

	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

	U11	U22	U33	U12	U13	U23
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

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—O6i	2.200 (2)	C15—C16	1.506 (5)
Cl1—Cu1ii	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—Cu2i	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—C21iii	1.349 (6)
C5—C6	1.497 (5)	C21—H21	0.9500
C6—H6A	0.9800	C22—N1iii	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—Cl4ii	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—O6i	106.62 (10)	C13—C14—C18	121.1 (3)
O4—Cu2—O6i	97.74 (10)	C16—C15—C17	111.6 (3)
O8—Cu2—O6i	91.76 (10)	C16—C15—C10	111.5 (3)
O6—Cu2—O6i	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
O6i—Cu2—Cu1	165.77 (6)	C15—C16—H16B	109.5
Cu1—Cl1—Cu1ii	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—Cu2i	137.1 (2)	C15—C17—H17C	109.5
Cu2—O6—Cu2i	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	C21iii—C21—N1	107.02 (18)
O5—C5—O6	123.5 (3)	C21iii—C21—H21	126.5
O5—C5—C6	118.2 (3)	N1—C21—H21	126.5
O6—C5—C6	118.2 (3)	N1iii—C22—N1	108.9 (4)
C5—C6—H6A	109.5	N1iii—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—Cl4ii	111.2 (3)
C7—C8—H8A	109.5	Cl4—C24—H24A	109.4
C7—C8—H8B	109.5	Cl4ii—C24—H24A	109.4
H8A—C8—H8B	109.5	Cl4—C24—H24B	109.4
C7—C8—H8C	109.5	Cl4ii—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)
Cu2i—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)
Cu2i—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—C21iii	0.8 (5)
C21—N1—C9—C14	82.2 (5)	C9—N1—C21—C21iii	176.8 (4)
C14—C9—C10—C11	−1.2 (6)	C21—N1—C22—N1iii	−0.29 (17)
N1—C9—C10—C11	178.9 (3)	C9—N1—C22—N1iii	−176.4 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6B···O2i	0.98	2.43	3.368 (4)	161
C21—H21···O1iv	0.95	2.54	3.344 (4)	142
C22—H22···Cl4v	0.95	2.78	3.626 (5)	149
C22—H22···Cl4vi	0.95	2.78	3.626 (5)	149
C23—H23A···O5ii	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···O5ii	0.99	2.42	3.303 (4)	148
C24—H24A···O7ii	0.99	2.52	3.378 (4)	145

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C6H6BO2i	0.98	2.43	3.368(4)	161
C21H21O1ii	0.95	2.54	3.344(4)	142
C22H22Cl4iii	0.95	2.78	3.626(5)	149
C22H22Cl4iv	0.95	2.78	3.626(5)	149
C23H23AO5v	0.99	2.42	3.316(5)	151
C23H23BO7	0.99	2.42	3.413(5)	177
C24H24BO5	0.99	2.42	3.303(4)	148
C24H24BO7	0.99	2.52	3.378(4)	145
C24H24AO5v	0.99	2.42	3.303(4)	148
C24H24AO7v	0.99	2.52	3.378(4)	145

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .