The crystal and mol­ecular structures of three copper-containing complexes and their activities in mimicking galactose oxidase

The structures of three copper-containing complexes, namely (benzoato-κ²O,O′)[(E)-2-({[2-(di­ethyl­amino)­eth­yl]imino}­meth­yl)phenolato-κ³N,N′,O]cop­per(II) dihydrate, [Cu(C₇H₅O₂)(C₁₃H₁₉N₂O)]·2H₂O, 1, [(E)-2-({[2-(di­ethyl­amino)­eth­yl]imino}­meth­yl)phenolato-κ³N,N′,O](2-phenyl­acetato-κ²O,O′)copper(II), [Cu(C₈H₇O₂)(C₁₃H₁₉N₂O)], 2, and bis­[μ-(E)-2-({[3-(di­ethyl­amino)­prop­yl]imino}­meth­yl)phenolato]-κ⁴N,N′,O:O;κ⁴O:N,N′,O-(μ-2-methyl­benzoato-κ²O:O′)cop­per(II) perchlorate, [Cu₂(C₈H₇O₂)(C₁₂H₁₇N₂O)₂]ClO₄, 3, have been reported and all have been tested for their activity in the oxidation of D-galactose. The results suggest that, unlike the enzyme galactose oxidase, due to the pre­cipitation of Cu₂O, this reaction is not catalytic as would have been expected. The structures of 1 and 2 are monomeric, while 3 consists of a dimeric cation and a perchlorate anion [which is disordered over two orientations, with occupancies of 0.64 (4) and 0.36 (4)]. In all three structures, the central Cu atom is five-coordinated in a distorted square-pyramidal arrangment (τ parameter of 0.0932 for 1, 0.0888 for 2, and 0.142 and 0.248 for the two Cu centers in 3). In each species, the environment about the Cu atom is such that the vacant sixth position is open, with very little steric crowding.

Computing details

For all structures, data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(Benzoato-κ²O,O')[(E)-2-({[2-(diethylamino)ethyl]imino}methyl)phenolato-κ³N,N',O]copper(II) dihydrate (1)

Crystal data

[Cu(C7H5O2)(C13H19N2O)]·2H2O	F(000) = 924
Mr = 439.98	Dx = 1.446 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.2427 (3) Å	Cell parameters from 20474 reflections
b = 10.1287 (2) Å	θ = 3.8–40.9°
c = 17.7683 (3) Å	µ = 1.11 mm^−1
β = 92.501 (2)°	T = 100 K
V = 2021.42 (8) Å^3	Multi-faceted prism, blue
Z = 4	0.35 × 0.23 × 0.18 mm

Data collection

Rigaku OD SuperNova Dual source diffractometer with an Atlas detector	13125 independent reflections
Radiation source: micro-focus sealed X-ray tube	10770 reflections with I > 2σ(I)
Detector resolution: 10.6501 pixels mm^-1	Rint = 0.030
ω scans	θmax = 41.3°, θmin = 3.5°
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2018)	h = −20→20
Tmin = 0.474, Tmax = 1.000	k = −18→18
51132 measured reflections	l = −25→32

Refinement

Refinement on F^2	6 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.076	w = 1/[σ^2(Fo^2) + (0.0327P)^2 + 0.3747P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.002
13125 reflections	Δρmax = 0.57 e Å^−3
270 parameters	Δρmin = −0.60 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
Cu	0.23818 (2)	0.69525 (2)	0.47778 (2)	0.01137 (2)
O1	0.27766 (5)	0.54601 (5)	0.41727 (3)	0.01650 (9)
O2	0.15402 (5)	0.78344 (6)	0.39331 (3)	0.01670 (9)
O3	0.33453 (5)	0.86472 (6)	0.37715 (3)	0.01897 (10)
O1W	0.52308 (7)	0.83109 (7)	0.28425 (4)	0.02636 (13)
H1W1	0.4716 (12)	0.8598 (15)	0.3113 (8)	0.034 (4)*
H1W2	0.5502 (16)	0.8967 (16)	0.2641 (10)	0.060 (5)*
O2W	0.39643 (9)	0.57738 (7)	0.27758 (4)	0.03167 (16)
H2W1	0.3575 (13)	0.5822 (15)	0.3162 (8)	0.037 (4)*
H2W2	0.4310 (14)	0.6492 (14)	0.2765 (9)	0.042 (4)*
N1	0.33000 (6)	0.63419 (6)	0.56489 (3)	0.01338 (9)
N2	0.16538 (6)	0.82506 (6)	0.55446 (3)	0.01380 (9)
C1	0.32672 (6)	0.43555 (7)	0.44259 (4)	0.01414 (10)
C2	0.32873 (8)	0.32474 (8)	0.39411 (5)	0.02019 (13)
H2A	0.294165	0.331522	0.344513	0.024*
C3	0.38021 (8)	0.20647 (8)	0.41763 (6)	0.02339 (15)
H3A	0.378582	0.133178	0.384235	0.028*
C4	0.43441 (8)	0.19302 (7)	0.48948 (6)	0.02259 (15)
H4A	0.471294	0.112327	0.504607	0.027*
C5	0.43329 (8)	0.29896 (7)	0.53786 (5)	0.01865 (12)
H5A	0.469865	0.290767	0.586855	0.022*
C6	0.37906 (6)	0.41938 (7)	0.51635 (4)	0.01382 (10)
C7	0.38029 (6)	0.52083 (7)	0.57282 (4)	0.01411 (10)
H7A	0.421362	0.502782	0.619548	0.017*
C8	0.32821 (7)	0.72459 (8)	0.62904 (4)	0.01648 (11)
H8A	0.383817	0.799046	0.622365	0.020*
H8B	0.351197	0.678039	0.676465	0.020*
C9	0.20140 (7)	0.77360 (8)	0.63053 (4)	0.01702 (12)
H9A	0.147997	0.700558	0.644253	0.020*
H9B	0.195502	0.844521	0.668525	0.020*
C10	0.21916 (7)	0.95742 (7)	0.54046 (4)	0.01689 (12)
H10A	0.188508	0.989212	0.490618	0.020*
H10B	0.306310	0.946107	0.537607	0.020*
C11	0.19639 (9)	1.06407 (8)	0.59850 (5)	0.02305 (15)
H11A	0.226691	1.148804	0.580836	0.035*
H11B	0.237177	1.040824	0.646542	0.035*
H11C	0.110635	1.071227	0.605459	0.035*
C12	0.03368 (7)	0.82973 (8)	0.54397 (5)	0.01943 (13)
H12A	0.012276	0.883028	0.498678	0.023*
H12B	0.000355	0.874369	0.587918	0.023*
C13	−0.02251 (8)	0.69370 (9)	0.53516 (6)	0.02444 (15)
H13A	−0.109103	0.702796	0.528447	0.037*
H13B	0.008651	0.649662	0.491031	0.037*
H13C	−0.003276	0.640999	0.580316	0.037*
C14	0.22685 (7)	0.85663 (7)	0.35854 (4)	0.01419 (10)
C15	0.17491 (7)	0.93920 (7)	0.29497 (4)	0.01484 (11)
C16	0.24644 (8)	1.02998 (8)	0.25883 (4)	0.01974 (13)
H16A	0.328766	1.035916	0.272873	0.024*
C17	0.19839 (10)	1.11179 (9)	0.20249 (5)	0.02590 (17)
H17A	0.247678	1.173462	0.178319	0.031*
C18	0.07821 (10)	1.10309 (9)	0.18165 (5)	0.02722 (18)
H18A	0.045041	1.159443	0.143495	0.033*
C19	0.00625 (9)	1.01191 (10)	0.21660 (5)	0.02489 (16)
H19A	−0.075915	1.005821	0.202140	0.030*
C20	0.05468 (8)	0.92951 (8)	0.27283 (4)	0.01896 (12)
H20A	0.005618	0.866548	0.296135	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.01340 (4)	0.01114 (3)	0.00955 (3)	0.00143 (3)	0.00042 (2)	0.00089 (2)
O1	0.0219 (2)	0.0150 (2)	0.01244 (19)	0.00371 (18)	−0.00101 (17)	−0.00138 (16)
O2	0.0184 (2)	0.0180 (2)	0.0136 (2)	0.00053 (18)	−0.00005 (17)	0.00472 (16)
O3	0.0171 (2)	0.0228 (2)	0.0169 (2)	0.0019 (2)	−0.00086 (18)	0.00397 (19)
O1W	0.0273 (3)	0.0280 (3)	0.0243 (3)	0.0005 (3)	0.0065 (2)	0.0045 (2)
O2W	0.0522 (5)	0.0228 (3)	0.0208 (3)	0.0024 (3)	0.0110 (3)	−0.0015 (2)
N1	0.0154 (2)	0.0137 (2)	0.01093 (19)	0.00220 (18)	−0.00039 (17)	−0.00069 (16)
N2	0.0142 (2)	0.0133 (2)	0.0142 (2)	0.00149 (18)	0.00314 (18)	0.00104 (17)
C1	0.0148 (3)	0.0126 (2)	0.0152 (2)	−0.0006 (2)	0.0022 (2)	−0.00182 (19)
C2	0.0212 (3)	0.0175 (3)	0.0219 (3)	−0.0010 (2)	0.0017 (3)	−0.0070 (2)
C3	0.0236 (4)	0.0142 (3)	0.0329 (4)	−0.0017 (3)	0.0062 (3)	−0.0075 (3)
C4	0.0245 (4)	0.0112 (2)	0.0327 (4)	0.0017 (2)	0.0079 (3)	0.0017 (3)
C5	0.0209 (3)	0.0128 (2)	0.0225 (3)	0.0027 (2)	0.0043 (3)	0.0042 (2)
C6	0.0150 (3)	0.0113 (2)	0.0153 (2)	0.0008 (2)	0.0027 (2)	0.00123 (19)
C7	0.0149 (3)	0.0148 (2)	0.0126 (2)	0.0018 (2)	0.0004 (2)	0.00160 (19)
C8	0.0193 (3)	0.0177 (3)	0.0123 (2)	0.0021 (2)	−0.0010 (2)	−0.0027 (2)
C9	0.0204 (3)	0.0184 (3)	0.0126 (2)	0.0026 (2)	0.0042 (2)	0.0003 (2)
C10	0.0183 (3)	0.0130 (2)	0.0198 (3)	0.0000 (2)	0.0056 (2)	−0.0008 (2)
C11	0.0270 (4)	0.0181 (3)	0.0243 (3)	−0.0015 (3)	0.0043 (3)	−0.0066 (3)
C12	0.0139 (3)	0.0198 (3)	0.0248 (3)	0.0024 (2)	0.0038 (2)	0.0009 (2)
C13	0.0206 (3)	0.0264 (4)	0.0263 (4)	−0.0059 (3)	0.0004 (3)	0.0052 (3)
C14	0.0186 (3)	0.0139 (2)	0.0101 (2)	0.0031 (2)	0.0004 (2)	0.00105 (18)
C15	0.0200 (3)	0.0148 (2)	0.0097 (2)	0.0042 (2)	0.0003 (2)	0.00078 (19)
C16	0.0270 (4)	0.0176 (3)	0.0146 (3)	0.0018 (3)	0.0011 (3)	0.0038 (2)
C17	0.0419 (5)	0.0192 (3)	0.0168 (3)	0.0050 (3)	0.0027 (3)	0.0063 (2)
C18	0.0429 (5)	0.0236 (4)	0.0148 (3)	0.0152 (4)	−0.0030 (3)	0.0031 (3)
C19	0.0284 (4)	0.0287 (4)	0.0171 (3)	0.0129 (3)	−0.0048 (3)	−0.0009 (3)
C20	0.0205 (3)	0.0219 (3)	0.0144 (3)	0.0065 (3)	−0.0005 (2)	0.0002 (2)

Geometric parameters (Å, º)

Cu—O1	1.9183 (5)	C8—C9	1.5110 (11)
Cu—N1	1.9246 (6)	C8—H8A	0.9900
Cu—O2	1.9550 (6)	C8—H8B	0.9900
Cu—N2	2.0863 (6)	C9—H9A	0.9900
Cu—O3	2.7360 (6)	C9—H9B	0.9900
O1—C1	1.3178 (9)	C10—C11	1.5228 (11)
O2—C14	1.2828 (9)	C10—H10A	0.9900
O3—C14	1.2437 (10)	C10—H10B	0.9900
O1W—H1W1	0.821 (12)	C11—H11A	0.9800
O1W—H1W2	0.820 (14)	C11—H11B	0.9800
O2W—H2W1	0.831 (12)	C11—H11C	0.9800
O2W—H2W2	0.825 (13)	C12—C13	1.5210 (12)
N1—C7	1.2849 (9)	C12—H12A	0.9900
N1—C8	1.4630 (9)	C12—H12B	0.9900
N2—C12	1.4850 (10)	C13—H13A	0.9800
N2—C9	1.4881 (10)	C13—H13B	0.9800
N2—C10	1.4960 (9)	C13—H13C	0.9800
C1—C2	1.4156 (10)	C14—C15	1.5029 (9)
C1—C6	1.4225 (10)	C15—C20	1.3947 (11)
C2—C3	1.3870 (12)	C15—C16	1.3963 (11)
C2—H2A	0.9500	C16—C17	1.3904 (12)
C3—C4	1.3970 (15)	C16—H16A	0.9500
C3—H3A	0.9500	C17—C18	1.3881 (16)
C4—C5	1.3754 (12)	C17—H17A	0.9500
C4—H4A	0.9500	C18—C19	1.3917 (15)
C5—C6	1.4089 (10)	C18—H18A	0.9500
C5—H5A	0.9500	C19—C20	1.3941 (11)
C6—C7	1.4359 (10)	C19—H19A	0.9500
C7—H7A	0.9500	C20—H20A	0.9500
O1—Cu—N1	93.92 (2)	N2—C9—C8	108.59 (6)
O1—Cu—O2	92.62 (2)	N2—C9—H9A	110.0
N1—Cu—O2	171.44 (3)	C8—C9—H9A	110.0
O1—Cu—N2	165.85 (2)	N2—C9—H9B	110.0
N1—Cu—N2	83.64 (2)	C8—C9—H9B	110.0
O2—Cu—N2	91.31 (2)	H9A—C9—H9B	108.4
O1—Cu—O3	91.16 (2)	N2—C10—C11	116.23 (6)
N1—Cu—O3	120.89 (2)	N2—C10—H10A	108.2
O2—Cu—O3	53.40 (2)	C11—C10—H10A	108.2
N2—Cu—O3	102.08 (2)	N2—C10—H10B	108.2
C1—O1—Cu	125.54 (5)	C11—C10—H10B	108.2
C14—O2—Cu	109.64 (5)	H10A—C10—H10B	107.4
C14—O3—Cu	73.97 (4)	C10—C11—H11A	109.5
H1W1—O1W—H1W2	104.6 (15)	C10—C11—H11B	109.5
H2W1—O2W—H2W2	103.5 (14)	H11A—C11—H11B	109.5
C7—N1—C8	119.66 (6)	C10—C11—H11C	109.5
C7—N1—Cu	126.40 (5)	H11A—C11—H11C	109.5
C8—N1—Cu	113.60 (5)	H11B—C11—H11C	109.5
C12—N2—C9	110.82 (6)	N2—C12—C13	113.04 (7)
C12—N2—C10	111.01 (6)	N2—C12—H12A	109.0
C9—N2—C10	111.65 (6)	C13—C12—H12A	109.0
C12—N2—Cu	110.82 (5)	N2—C12—H12B	109.0
C9—N2—Cu	105.87 (4)	C13—C12—H12B	109.0
C10—N2—Cu	106.45 (4)	H12A—C12—H12B	107.8
O1—C1—C2	118.88 (7)	C12—C13—H13A	109.5
O1—C1—C6	124.23 (6)	C12—C13—H13B	109.5
C2—C1—C6	116.89 (7)	H13A—C13—H13B	109.5
C3—C2—C1	121.27 (8)	C12—C13—H13C	109.5
C3—C2—H2A	119.4	H13A—C13—H13C	109.5
C1—C2—H2A	119.4	H13B—C13—H13C	109.5
C2—C3—C4	121.28 (7)	O3—C14—O2	122.98 (6)
C2—C3—H3A	119.4	O3—C14—C15	120.33 (7)
C4—C3—H3A	119.4	O2—C14—C15	116.63 (7)
C5—C4—C3	118.66 (8)	C20—C15—C16	119.15 (7)
C5—C4—H4A	120.7	C20—C15—C14	120.86 (7)
C3—C4—H4A	120.7	C16—C15—C14	119.96 (7)
C4—C5—C6	121.43 (8)	C17—C16—C15	120.67 (9)
C4—C5—H5A	119.3	C17—C16—H16A	119.7
C6—C5—H5A	119.3	C15—C16—H16A	119.7
C5—C6—C1	120.43 (7)	C18—C17—C16	119.82 (9)
C5—C6—C7	116.04 (7)	C18—C17—H17A	120.1
C1—C6—C7	123.53 (6)	C16—C17—H17A	120.1
N1—C7—C6	124.89 (6)	C17—C18—C19	120.08 (8)
N1—C7—H7A	117.6	C17—C18—H18A	120.0
C6—C7—H7A	117.6	C19—C18—H18A	120.0
N1—C8—C9	105.33 (6)	C18—C19—C20	120.04 (9)
N1—C8—H8A	110.7	C18—C19—H19A	120.0
C9—C8—H8A	110.7	C20—C19—H19A	120.0
N1—C8—H8B	110.7	C19—C20—C15	120.23 (8)
C9—C8—H8B	110.7	C19—C20—H20A	119.9
H8A—C8—H8B	108.8	C15—C20—H20A	119.9
Cu—O1—C1—C2	167.40 (5)	C12—N2—C10—C11	69.58 (9)
Cu—O1—C1—C6	−12.80 (10)	C9—N2—C10—C11	−54.64 (9)
O1—C1—C2—C3	179.39 (8)	Cu—N2—C10—C11	−169.73 (6)
C6—C1—C2—C3	−0.42 (11)	C9—N2—C12—C13	−71.87 (8)
C1—C2—C3—C4	−1.45 (13)	C10—N2—C12—C13	163.45 (7)
C2—C3—C4—C5	1.69 (13)	Cu—N2—C12—C13	45.36 (8)
C3—C4—C5—C6	−0.04 (12)	Cu—O3—C14—O2	−0.92 (6)
C4—C5—C6—C1	−1.84 (11)	Cu—O3—C14—C15	176.22 (6)
C4—C5—C6—C7	177.93 (7)	Cu—O2—C14—O3	1.32 (9)
O1—C1—C6—C5	−177.78 (7)	Cu—O2—C14—C15	−175.93 (5)
C2—C1—C6—C5	2.02 (10)	O3—C14—C15—C20	179.00 (7)
O1—C1—C6—C7	2.47 (11)	O2—C14—C15—C20	−3.67 (10)
C2—C1—C6—C7	−177.73 (7)	O3—C14—C15—C16	−3.00 (10)
C8—N1—C7—C6	174.37 (7)	O2—C14—C15—C16	174.33 (7)
Cu—N1—C7—C6	1.60 (11)	C20—C15—C16—C17	1.29 (11)
C5—C6—C7—N1	−176.20 (7)	C14—C15—C16—C17	−176.75 (7)
C1—C6—C7—N1	3.56 (11)	C15—C16—C17—C18	−0.21 (13)
C7—N1—C8—C9	−133.03 (7)	C16—C17—C18—C19	−0.57 (13)
Cu—N1—C8—C9	40.63 (7)	C17—C18—C19—C20	0.26 (13)
C12—N2—C9—C8	159.78 (6)	C18—C19—C20—C15	0.83 (12)
C10—N2—C9—C8	−75.90 (7)	C16—C15—C20—C19	−1.60 (11)
Cu—N2—C9—C8	39.55 (7)	C14—C15—C20—C19	176.42 (7)
N1—C8—C9—N2	−52.20 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O3	0.82 (1)	1.98 (1)	2.7641 (9)	161 (2)
O1W—H1W2···O2W^i	0.82 (1)	2.07 (1)	2.8871 (10)	172 (2)
O2W—H2W1···O1	0.83 (1)	2.08 (1)	2.8868 (9)	165 (2)
O2W—H2W2···O1W	0.83 (1)	2.12 (1)	2.9378 (11)	175 (2)

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

[(E)-2-({[2-(Diethylamino)ethyl]imino}methyl)phenolato-κ³N,N',O](2-phenylacetato-κ²O,O')copper(II) (2)

Crystal data

[Cu(C8H7O2)(C13H19N2O)]	Dx = 1.418 Mg m^−3
Mr = 417.98	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca21	Cell parameters from 6436 reflections
a = 23.1862 (10) Å	θ = 3.9–33.6°
b = 6.4178 (3) Å	µ = 1.14 mm^−1
c = 13.1598 (6) Å	T = 100 K
V = 1958.22 (15) Å^3	Plate, blue
Z = 4	0.20 × 0.11 × 0.03 mm
F(000) = 876

Data collection

Rigaku OD SuperNova Dual source diffractometer with an Atlas detector	11501 independent reflections
Radiation source: micro-focus sealed X-ray tube	7093 reflections with I > 2σ(I)
Detector resolution: 10.6501 pixels mm^-1	Rint = 0.089
ω scans	θmax = 41.3°, θmin = 3.5°
Absorption correction: gaussian CrysAlis PRO (Rigaku OD, 2018) Numerical absorption correction based on gaussian integration over a multifaceted crystal model. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −37→42
Tmin = 0.684, Tmax = 1.000	k = −11→11
46196 measured reflections	l = −23→22

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.056	w = 1/[σ^2(Fo^2) + (0.0359P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.121	(Δ/σ)max = 0.002
S = 1.04	Δρmax = 1.20 e Å^−3
11501 reflections	Δρmin = −1.04 e Å^−3
245 parameters	Absolute structure: Flack x determined using 1976 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: −0.035 (10)

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
Cu	0.50251 (2)	0.67151 (4)	0.58234 (5)	0.01478 (6)
O1	0.55832 (9)	0.8376 (3)	0.51299 (18)	0.0204 (4)
O2	0.44362 (8)	0.8849 (3)	0.55955 (16)	0.0185 (4)
O3	0.43374 (10)	0.6755 (3)	0.42593 (18)	0.0219 (5)
N1	0.55334 (9)	0.4358 (3)	0.5937 (2)	0.0180 (5)
N2	0.45221 (10)	0.5167 (4)	0.68793 (19)	0.0176 (4)
C1	0.61121 (12)	0.7875 (4)	0.4914 (2)	0.0167 (5)
C2	0.64665 (13)	0.9369 (5)	0.4416 (2)	0.0186 (5)
H2A	0.630815	1.069146	0.425069	0.022*
C3	0.70285 (13)	0.8961 (5)	0.4169 (2)	0.0201 (5)
H3A	0.725123	1.000151	0.383750	0.024*
C4	0.72806 (13)	0.7032 (5)	0.4396 (2)	0.0215 (6)
H4A	0.767133	0.675768	0.422466	0.026*
C5	0.69497 (12)	0.5539 (5)	0.4874 (2)	0.0200 (5)
H5A	0.711564	0.422133	0.502459	0.024*
C6	0.63715 (12)	0.5921 (5)	0.5145 (2)	0.0176 (5)
C7	0.60647 (11)	0.4276 (4)	0.5657 (2)	0.0181 (6)
H7A	0.627107	0.303159	0.580009	0.022*
C8	0.52631 (13)	0.2571 (5)	0.6443 (3)	0.0224 (6)
H8A	0.556181	0.164060	0.673164	0.027*
H8B	0.502894	0.176370	0.595273	0.027*
C9	0.48849 (14)	0.3425 (5)	0.7279 (3)	0.0226 (6)
H9A	0.463338	0.230491	0.754515	0.027*
H9B	0.512849	0.393847	0.784358	0.027*
C10	0.43476 (15)	0.6603 (5)	0.7715 (3)	0.0222 (6)
H10A	0.415201	0.578917	0.825322	0.027*
H10B	0.406761	0.762946	0.744670	0.027*
C11	0.48557 (16)	0.7759 (6)	0.8177 (3)	0.0283 (7)
H11A	0.471804	0.867734	0.872038	0.043*
H11B	0.513054	0.675182	0.845802	0.043*
H11C	0.504613	0.859261	0.765128	0.043*
C12	0.40028 (13)	0.4385 (5)	0.6321 (2)	0.0222 (6)
H12A	0.413673	0.356314	0.572965	0.027*
H12B	0.378887	0.560191	0.605402	0.027*
C13	0.35861 (15)	0.3051 (6)	0.6926 (3)	0.0319 (8)
H13A	0.324823	0.272829	0.650745	0.048*
H13B	0.346350	0.381139	0.753507	0.048*
H13C	0.377714	0.175336	0.712744	0.048*
C14	0.42161 (12)	0.8351 (5)	0.4727 (2)	0.0170 (5)
C15	0.37829 (13)	0.9942 (5)	0.4325 (2)	0.0215 (6)
H15A	0.351429	1.028904	0.488492	0.026*
H15B	0.399690	1.123004	0.415505	0.026*
C16	0.34295 (12)	0.9344 (5)	0.3416 (2)	0.0192 (5)
C17	0.33190 (13)	1.0802 (5)	0.2656 (2)	0.0212 (6)
H17A	0.350911	1.211234	0.267692	0.025*
C18	0.29376 (14)	1.0383 (6)	0.1867 (3)	0.0258 (6)
H18A	0.286285	1.140770	0.136301	0.031*
C19	0.26675 (14)	0.8464 (6)	0.1823 (3)	0.0278 (7)
H19A	0.240039	0.817626	0.129361	0.033*
C20	0.27865 (15)	0.6955 (6)	0.2551 (3)	0.0275 (7)
H20A	0.260772	0.562618	0.250909	0.033*
C21	0.31655 (13)	0.7385 (5)	0.3340 (3)	0.0226 (6)
H21A	0.324698	0.634210	0.383164	0.027*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.01389 (12)	0.01448 (11)	0.01595 (12)	0.00064 (11)	0.00013 (14)	0.00139 (17)
O1	0.0152 (9)	0.0202 (10)	0.0257 (11)	0.0031 (7)	0.0032 (8)	0.0053 (8)
O2	0.0156 (8)	0.0208 (10)	0.0191 (11)	0.0012 (7)	−0.0011 (7)	0.0018 (7)
O3	0.0217 (10)	0.0242 (11)	0.0197 (11)	0.0051 (8)	0.0012 (8)	−0.0013 (8)
N1	0.0176 (9)	0.0150 (9)	0.0214 (14)	−0.0002 (7)	0.0000 (9)	0.0003 (9)
N2	0.0165 (10)	0.0200 (11)	0.0165 (11)	−0.0005 (8)	0.0008 (8)	0.0026 (9)
C1	0.0169 (12)	0.0184 (12)	0.0148 (12)	0.0005 (9)	−0.0008 (9)	0.0001 (9)
C2	0.0173 (12)	0.0192 (13)	0.0192 (13)	0.0007 (10)	0.0010 (9)	0.0000 (10)
C3	0.0175 (13)	0.0249 (14)	0.0178 (14)	−0.0032 (10)	0.0012 (10)	−0.0004 (11)
C4	0.0161 (13)	0.0275 (16)	0.0210 (14)	0.0014 (10)	0.0037 (10)	−0.0019 (11)
C5	0.0174 (13)	0.0202 (14)	0.0226 (14)	0.0035 (10)	0.0011 (10)	−0.0011 (11)
C6	0.0162 (12)	0.0182 (13)	0.0186 (13)	0.0005 (9)	−0.0015 (9)	−0.0016 (10)
C7	0.0171 (11)	0.0148 (11)	0.0225 (16)	0.0022 (8)	−0.0020 (9)	−0.0017 (10)
C8	0.0204 (14)	0.0187 (14)	0.0281 (16)	−0.0010 (11)	0.0003 (11)	0.0025 (12)
C9	0.0237 (14)	0.0216 (15)	0.0227 (15)	0.0014 (11)	0.0015 (11)	0.0057 (11)
C10	0.0245 (15)	0.0240 (16)	0.0180 (14)	0.0005 (12)	0.0042 (11)	0.0002 (11)
C11	0.0327 (17)	0.0254 (16)	0.0269 (18)	−0.0012 (13)	0.0006 (13)	−0.0014 (13)
C12	0.0192 (13)	0.0270 (15)	0.0205 (15)	−0.0046 (11)	−0.0002 (10)	0.0010 (12)
C13	0.0255 (17)	0.038 (2)	0.0323 (19)	−0.0116 (14)	0.0027 (14)	0.0040 (15)
C14	0.0127 (11)	0.0224 (13)	0.0160 (12)	0.0005 (9)	0.0020 (8)	0.0042 (10)
C15	0.0208 (14)	0.0203 (14)	0.0234 (15)	0.0027 (10)	−0.0039 (11)	0.0018 (11)
C16	0.0154 (12)	0.0226 (14)	0.0196 (14)	0.0018 (10)	−0.0002 (10)	0.0026 (10)
C17	0.0164 (13)	0.0243 (15)	0.0228 (15)	0.0026 (11)	0.0031 (10)	0.0049 (11)
C18	0.0254 (15)	0.0350 (18)	0.0170 (14)	0.0087 (13)	0.0026 (11)	0.0055 (12)
C19	0.0232 (15)	0.041 (2)	0.0193 (15)	0.0076 (13)	−0.0038 (11)	−0.0079 (13)
C20	0.0245 (16)	0.0287 (18)	0.0294 (18)	0.0011 (12)	−0.0019 (13)	−0.0047 (13)
C21	0.0214 (13)	0.0220 (14)	0.0244 (15)	0.0003 (11)	−0.0015 (12)	0.0021 (12)

Geometric parameters (Å, º)

Cu—O1	1.909 (2)	C9—H9B	0.9900
Cu—N1	1.923 (2)	C10—C11	1.519 (5)
Cu—O2	1.957 (2)	C10—H10A	0.9900
Cu—N2	2.068 (2)	C10—H10B	0.9900
Cu—O3	2.604 (2)	C11—H11A	0.9800
O1—C1	1.299 (3)	C11—H11B	0.9800
O2—C14	1.292 (4)	C11—H11C	0.9800
O3—C14	1.228 (4)	C12—C13	1.517 (4)
N1—C7	1.287 (3)	C12—H12A	0.9900
N1—C8	1.467 (4)	C12—H12B	0.9900
N2—C10	1.490 (4)	C13—H13A	0.9800
N2—C9	1.495 (4)	C13—H13B	0.9800
N2—C12	1.497 (4)	C13—H13C	0.9800
C1—C2	1.423 (4)	C14—C15	1.526 (4)
C1—C6	1.424 (4)	C15—C16	1.500 (4)
C2—C3	1.368 (4)	C15—H15A	0.9900
C2—H2A	0.9500	C15—H15B	0.9900
C3—C4	1.402 (4)	C16—C17	1.394 (4)
C3—H3A	0.9500	C16—C21	1.402 (4)
C4—C5	1.379 (4)	C17—C18	1.390 (5)
C4—H4A	0.9500	C17—H17A	0.9500
C5—C6	1.408 (4)	C18—C19	1.383 (5)
C5—H5A	0.9500	C18—H18A	0.9500
C6—C7	1.441 (4)	C19—C20	1.390 (5)
C7—H7A	0.9500	C19—H19A	0.9500
C8—C9	1.509 (5)	C20—C21	1.387 (5)
C8—H8A	0.9900	C20—H20A	0.9500
C8—H8B	0.9900	C21—H21A	0.9500
C9—H9A	0.9900
O1—Cu—N1	93.49 (9)	C8—C9—H9B	109.7
O1—Cu—O2	90.51 (9)	H9A—C9—H9B	108.2
N1—Cu—O2	171.79 (10)	N2—C10—C11	112.8 (3)
O1—Cu—N2	166.33 (11)	N2—C10—H10A	109.0
N1—Cu—N2	85.17 (10)	C11—C10—H10A	109.0
O2—Cu—N2	92.61 (9)	N2—C10—H10B	109.0
O1—Cu—O3	91.81 (9)	C11—C10—H10B	109.0
N1—Cu—O3	116.37 (10)	H10A—C10—H10B	107.8
O2—Cu—O3	56.27 (8)	C10—C11—H11A	109.5
N2—Cu—O3	100.98 (9)	C10—C11—H11B	109.5
C1—O1—Cu	127.30 (19)	H11A—C11—H11B	109.5
C14—O2—Cu	103.79 (18)	C10—C11—H11C	109.5
C14—O3—Cu	75.67 (17)	H11A—C11—H11C	109.5
C7—N1—C8	120.5 (2)	H11B—C11—H11C	109.5
C7—N1—Cu	126.6 (2)	N2—C12—C13	116.4 (3)
C8—N1—Cu	112.84 (18)	N2—C12—H12A	108.2
C10—N2—C9	110.8 (3)	C13—C12—H12A	108.2
C10—N2—C12	110.6 (2)	N2—C12—H12B	108.2
C9—N2—C12	112.0 (2)	C13—C12—H12B	108.2
C10—N2—Cu	110.60 (19)	H12A—C12—H12B	107.4
C9—N2—Cu	106.15 (18)	C12—C13—H13A	109.5
C12—N2—Cu	106.56 (18)	C12—C13—H13B	109.5
O1—C1—C2	118.6 (3)	H13A—C13—H13B	109.5
O1—C1—C6	124.8 (3)	C12—C13—H13C	109.5
C2—C1—C6	116.6 (3)	H13A—C13—H13C	109.5
C3—C2—C1	122.1 (3)	H13B—C13—H13C	109.5
C3—C2—H2A	119.0	O3—C14—O2	124.0 (3)
C1—C2—H2A	119.0	O3—C14—C15	122.4 (3)
C2—C3—C4	121.0 (3)	O2—C14—C15	113.6 (3)
C2—C3—H3A	119.5	C16—C15—C14	117.7 (3)
C4—C3—H3A	119.5	C16—C15—H15A	107.9
C5—C4—C3	118.6 (3)	C14—C15—H15A	107.9
C5—C4—H4A	120.7	C16—C15—H15B	107.9
C3—C4—H4A	120.7	C14—C15—H15B	107.9
C4—C5—C6	121.6 (3)	H15A—C15—H15B	107.2
C4—C5—H5A	119.2	C17—C16—C21	118.0 (3)
C6—C5—H5A	119.2	C17—C16—C15	120.1 (3)
C5—C6—C1	120.1 (3)	C21—C16—C15	121.7 (3)
C5—C6—C7	117.4 (3)	C18—C17—C16	121.6 (3)
C1—C6—C7	122.4 (3)	C18—C17—H17A	119.2
N1—C7—C6	125.2 (3)	C16—C17—H17A	119.2
N1—C7—H7A	117.4	C19—C18—C17	119.5 (3)
C6—C7—H7A	117.4	C19—C18—H18A	120.3
N1—C8—C9	107.2 (3)	C17—C18—H18A	120.3
N1—C8—H8A	110.3	C18—C19—C20	120.1 (3)
C9—C8—H8A	110.3	C18—C19—H19A	120.0
N1—C8—H8B	110.3	C20—C19—H19A	120.0
C9—C8—H8B	110.3	C21—C20—C19	120.2 (3)
H8A—C8—H8B	108.5	C21—C20—H20A	119.9
N2—C9—C8	110.0 (3)	C19—C20—H20A	119.9
N2—C9—H9A	109.7	C20—C21—C16	120.6 (3)
C8—C9—H9A	109.7	C20—C21—H21A	119.7
N2—C9—H9B	109.7	C16—C21—H21A	119.7
Cu—O1—C1—C2	−178.1 (2)	C9—N2—C10—C11	66.1 (3)
Cu—O1—C1—C6	1.5 (4)	C12—N2—C10—C11	−169.2 (3)
O1—C1—C2—C3	179.7 (3)	Cu—N2—C10—C11	−51.4 (3)
C6—C1—C2—C3	0.0 (4)	C10—N2—C12—C13	−64.0 (4)
C1—C2—C3—C4	0.1 (5)	C9—N2—C12—C13	60.1 (4)
C2—C3—C4—C5	0.2 (5)	Cu—N2—C12—C13	175.8 (3)
C3—C4—C5—C6	−0.7 (5)	Cu—O3—C14—O2	−4.8 (2)
C4—C5—C6—C1	0.8 (5)	Cu—O3—C14—C15	175.4 (3)
C4—C5—C6—C7	−179.0 (3)	Cu—O2—C14—O3	6.4 (3)
O1—C1—C6—C5	179.9 (3)	Cu—O2—C14—C15	−173.84 (19)
C2—C1—C6—C5	−0.5 (4)	O3—C14—C15—C16	10.0 (4)
O1—C1—C6—C7	−0.4 (5)	O2—C14—C15—C16	−169.8 (3)
C2—C1—C6—C7	179.3 (3)	C14—C15—C16—C17	−139.8 (3)
C8—N1—C7—C6	179.2 (3)	C14—C15—C16—C21	45.1 (4)
Cu—N1—C7—C6	−4.0 (4)	C21—C16—C17—C18	3.1 (5)
C5—C6—C7—N1	−178.5 (3)	C15—C16—C17—C18	−172.1 (3)
C1—C6—C7—N1	1.7 (5)	C16—C17—C18—C19	−1.2 (5)
C7—N1—C8—C9	139.9 (3)	C17—C18—C19—C20	−1.2 (5)
Cu—N1—C8—C9	−37.3 (3)	C18—C19—C20—C21	1.6 (5)
C10—N2—C9—C8	−155.3 (3)	C19—C20—C21—C16	0.5 (5)
C12—N2—C9—C8	80.7 (3)	C17—C16—C21—C20	−2.8 (5)
Cu—N2—C9—C8	−35.2 (3)	C15—C16—C21—C20	172.4 (3)
N1—C8—C9—N2	47.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O2^i	0.99	2.37	3.260 (4)	149
C9—H9B···O3^ii	0.99	2.28	3.172 (4)	149
C12—H12B···O2	0.99	2.64	3.183 (4)	115

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

Bis[µ-(E)-2-({[3-(diethylamino)propyl]imino}methyl)phenolato]-κ⁴N,N',O:O;κ⁴O:N,N',O-(µ-2-methylbenzoato-κ²O:O')copper(II) perchlorate (3)

Crystal data

[Cu2(C8H7O2)(C12H17N2O)2]ClO4	Dx = 1.521 Mg m^−3
Mr = 772.22	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 21097 reflections
a = 10.51085 (16) Å	θ = 3.7–36.4°
b = 22.2419 (5) Å	µ = 1.40 mm^−1
c = 28.8403 (5) Å	T = 100 K
V = 6742.3 (2) Å^3	Plate, green-blue
Z = 8	0.26 × 0.21 × 0.03 mm
F(000) = 3200

Data collection

Rigaku OD SuperNova Dual source diffractometer with an Atlas detector	22070 independent reflections
Radiation source: micro-focus sealed X-ray tube	12413 reflections with I > 2σ(I)
Detector resolution: 10.6501 pixels mm^-1	Rint = 0.090
ω scans	θmax = 41.6°, θmin = 3.4°
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2018)	h = −18→19
Tmin = 0.614, Tmax = 1.000	k = −33→40
154652 measured reflections	l = −35→52

Refinement

Refinement on F^2	44 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.053	H-atom parameters constrained
wR(F^2) = 0.135	w = 1/[σ^2(Fo^2) + (0.039P)^2 + 5.3824P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
22070 reflections	Δρmax = 1.13 e Å^−3
467 parameters	Δρmin = −1.10 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	0.28173 (2)	1.08502 (2)	0.16413 (2)	0.01838 (4)
Cu2	0.32761 (2)	0.99599 (2)	0.08706 (2)	0.01958 (4)
O1	0.18853 (12)	1.01143 (6)	0.14771 (5)	0.0219 (2)
O2	0.44003 (11)	1.05731 (6)	0.11374 (5)	0.0215 (2)
O3	0.18608 (13)	1.12125 (6)	0.11331 (5)	0.0241 (3)
O4	0.24510 (13)	1.06268 (6)	0.05351 (5)	0.0255 (3)
N1	0.32825 (14)	1.17468 (7)	0.18137 (6)	0.0223 (3)
N2	0.35486 (14)	1.04593 (7)	0.21946 (5)	0.0229 (3)
N3	0.42640 (14)	0.93093 (7)	0.11619 (6)	0.0232 (3)
N4	0.24861 (19)	0.93856 (9)	0.03741 (7)	0.0353 (4)
C1	0.15786 (15)	0.96685 (8)	0.17591 (6)	0.0204 (3)
C2	0.06056 (16)	0.92586 (8)	0.16282 (8)	0.0259 (3)
H2A	0.018193	0.931168	0.134018	0.031*
C3	0.02630 (19)	0.87838 (9)	0.19118 (9)	0.0326 (4)
H3A	−0.040146	0.852123	0.181767	0.039*
C4	0.0877 (2)	0.86842 (10)	0.23339 (9)	0.0377 (5)
H4A	0.063932	0.835617	0.252624	0.045*
C5	0.1835 (2)	0.90699 (10)	0.24663 (8)	0.0340 (4)
H5A	0.226834	0.900052	0.275026	0.041*
C6	0.21861 (18)	0.95663 (8)	0.21897 (7)	0.0238 (3)
C7	0.31918 (17)	0.99510 (8)	0.23622 (7)	0.0235 (3)
H7A	0.363661	0.981258	0.262830	0.028*
C8	0.45833 (19)	1.07664 (10)	0.24478 (7)	0.0305 (4)
H8A	0.535325	1.078379	0.225058	0.037*
H8B	0.479509	1.053689	0.273162	0.037*
C9	0.4179 (2)	1.13985 (10)	0.25785 (7)	0.0310 (4)
H9A	0.328741	1.138993	0.268907	0.037*
H9B	0.471883	1.154315	0.283668	0.037*
C10	0.42827 (18)	1.18331 (10)	0.21765 (7)	0.0297 (4)
H10A	0.422390	1.224879	0.229733	0.036*
H10B	0.512998	1.178625	0.203100	0.036*
C11	0.20745 (19)	1.20172 (11)	0.19811 (8)	0.0338 (5)
H11A	0.220059	1.244773	0.203678	0.051*
H11B	0.181586	1.182086	0.227028	0.051*
H11C	0.141026	1.196136	0.174653	0.051*
C12	0.3685 (2)	1.21036 (10)	0.14034 (8)	0.0314 (4)
H12A	0.390609	1.251243	0.150133	0.047*
H12B	0.298717	1.212011	0.117853	0.047*
H12C	0.442856	1.191360	0.125973	0.047*
C13	0.56329 (16)	1.04925 (8)	0.12129 (6)	0.0195 (3)
C14	0.64547 (17)	1.09933 (8)	0.12300 (7)	0.0232 (3)
H14A	0.611230	1.138621	0.119659	0.028*
C15	0.77541 (17)	1.09226 (9)	0.12948 (7)	0.0243 (3)
H15A	0.828659	1.126763	0.130131	0.029*
C16	0.82929 (17)	1.03539 (9)	0.13505 (8)	0.0273 (4)
H16A	0.918577	1.030819	0.138755	0.033*
C17	0.75007 (18)	0.98594 (9)	0.13505 (8)	0.0276 (4)
H17A	0.785487	0.947130	0.139803	0.033*
C18	0.61758 (16)	0.99162 (8)	0.12815 (6)	0.0216 (3)
C19	0.54316 (17)	0.93722 (8)	0.12929 (7)	0.0247 (3)
H19A	0.584320	0.902305	0.140915	0.030*
C20	0.37186 (19)	0.87002 (9)	0.12140 (8)	0.0295 (4)
H20A	0.294207	0.872019	0.140770	0.035*
H20B	0.433996	0.843546	0.137170	0.035*
C21	0.3391 (2)	0.84414 (11)	0.07424 (11)	0.0425 (6)
H21A	0.414251	0.847807	0.053734	0.051*
H21B	0.319906	0.800810	0.077773	0.051*
C22	0.2275 (3)	0.87454 (11)	0.05142 (10)	0.0431 (6)
H22A	0.203933	0.851222	0.023480	0.052*
H22B	0.154364	0.873092	0.073008	0.052*
C23	0.3397 (3)	0.94346 (15)	−0.00141 (10)	0.0532 (7)
H23A	0.309784	0.919079	−0.027527	0.080*
H23B	0.423371	0.928975	0.008627	0.080*
H23C	0.346501	0.985575	−0.011092	0.080*
C24	0.1215 (3)	0.95918 (14)	0.02074 (11)	0.0534 (7)
H24A	0.089533	0.931073	−0.002688	0.080*
H24B	0.129479	0.999341	0.007071	0.080*
H24C	0.062063	0.960663	0.046891	0.080*
C25	0.19144 (16)	1.10812 (8)	0.07068 (6)	0.0209 (3)
C26	0.12577 (17)	1.15150 (8)	0.03844 (6)	0.0220 (3)
C27	0.02568 (18)	1.18557 (9)	0.05705 (7)	0.0259 (3)
H27A	0.003035	1.180622	0.088715	0.031*
C28	−0.0408 (2)	1.22642 (10)	0.02983 (8)	0.0333 (4)
H28A	−0.110083	1.248384	0.042477	0.040*
C29	−0.0050 (2)	1.23482 (10)	−0.01588 (9)	0.0388 (5)
H29A	−0.048923	1.263227	−0.034560	0.047*
C30	0.0943 (2)	1.20205 (11)	−0.03445 (8)	0.0358 (5)
H30A	0.117859	1.208614	−0.065840	0.043*
C31	0.16139 (19)	1.15931 (9)	−0.00827 (7)	0.0277 (4)
C32	0.2693 (2)	1.12608 (12)	−0.03120 (8)	0.0384 (5)
H32A	0.290621	1.145716	−0.060613	0.058*
H32B	0.243726	1.084418	−0.037115	0.058*
H32C	0.343858	1.126512	−0.010781	0.058*
Cl1	0.71528 (4)	0.76845 (2)	0.15982 (2)	0.02309 (8)
O11A	0.7359 (13)	0.8310 (3)	0.1481 (5)	0.0305 (14)	0.64 (4)
O12A	0.5835 (7)	0.7574 (6)	0.1677 (4)	0.0448 (17)	0.64 (4)
O13A	0.7872 (10)	0.7544 (7)	0.2006 (4)	0.054 (2)	0.64 (4)
O14A	0.7590 (13)	0.7325 (4)	0.1220 (4)	0.059 (2)	0.64 (4)
O11B	0.752 (2)	0.8298 (6)	0.1535 (9)	0.030 (2)	0.36 (4)
O12B	0.5852 (13)	0.7673 (13)	0.1760 (10)	0.058 (5)	0.36 (4)
O13B	0.7955 (17)	0.7392 (9)	0.1922 (7)	0.053 (3)	0.36 (4)
O14B	0.722 (3)	0.7377 (9)	0.1163 (5)	0.068 (4)	0.36 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02042 (9)	0.01657 (9)	0.01815 (8)	−0.00045 (7)	−0.00320 (7)	−0.00008 (7)
Cu2	0.01951 (9)	0.01557 (9)	0.02365 (10)	0.00206 (7)	−0.00306 (7)	−0.00206 (7)
O1	0.0221 (5)	0.0193 (6)	0.0244 (6)	−0.0017 (4)	−0.0033 (4)	−0.0001 (5)
O2	0.0177 (5)	0.0171 (6)	0.0296 (6)	0.0018 (4)	−0.0019 (4)	−0.0030 (5)
O3	0.0316 (6)	0.0205 (6)	0.0203 (6)	0.0060 (5)	−0.0060 (5)	−0.0016 (5)
O4	0.0320 (6)	0.0224 (6)	0.0221 (6)	0.0068 (5)	−0.0036 (5)	−0.0010 (5)
N1	0.0204 (6)	0.0199 (7)	0.0266 (7)	−0.0024 (5)	0.0026 (5)	−0.0039 (5)
N2	0.0220 (6)	0.0246 (8)	0.0221 (7)	−0.0023 (5)	−0.0050 (5)	0.0014 (5)
N3	0.0204 (6)	0.0166 (6)	0.0326 (8)	0.0014 (5)	−0.0028 (5)	−0.0002 (6)
N4	0.0414 (10)	0.0278 (9)	0.0367 (10)	−0.0033 (7)	−0.0122 (8)	−0.0086 (8)
C1	0.0184 (7)	0.0159 (7)	0.0269 (8)	0.0019 (5)	0.0015 (6)	−0.0010 (6)
C2	0.0187 (7)	0.0201 (8)	0.0388 (10)	0.0010 (6)	−0.0001 (7)	−0.0048 (7)
C3	0.0257 (8)	0.0181 (9)	0.0539 (13)	−0.0036 (6)	0.0070 (8)	−0.0052 (8)
C4	0.0469 (12)	0.0214 (10)	0.0449 (13)	−0.0063 (8)	0.0116 (10)	0.0046 (9)
C5	0.0463 (12)	0.0223 (9)	0.0333 (10)	−0.0012 (8)	0.0021 (9)	0.0057 (8)
C6	0.0266 (8)	0.0182 (8)	0.0266 (8)	0.0004 (6)	0.0000 (6)	0.0029 (6)
C7	0.0263 (8)	0.0209 (8)	0.0234 (7)	0.0009 (6)	−0.0046 (6)	0.0031 (6)
C8	0.0257 (8)	0.0383 (12)	0.0273 (9)	−0.0082 (7)	−0.0091 (7)	0.0042 (8)
C9	0.0307 (9)	0.0371 (11)	0.0253 (9)	−0.0117 (8)	−0.0039 (7)	−0.0058 (8)
C10	0.0251 (8)	0.0297 (10)	0.0343 (10)	−0.0091 (7)	−0.0013 (7)	−0.0045 (8)
C11	0.0246 (8)	0.0384 (12)	0.0383 (11)	0.0001 (8)	0.0053 (8)	−0.0165 (9)
C12	0.0315 (9)	0.0228 (9)	0.0399 (11)	0.0001 (7)	0.0057 (8)	0.0068 (8)
C13	0.0198 (6)	0.0180 (7)	0.0207 (7)	0.0006 (5)	−0.0001 (5)	−0.0011 (5)
C14	0.0215 (7)	0.0190 (8)	0.0291 (8)	−0.0001 (6)	0.0005 (6)	−0.0031 (6)
C15	0.0208 (7)	0.0238 (9)	0.0282 (8)	−0.0026 (6)	0.0001 (6)	−0.0037 (7)
C16	0.0192 (7)	0.0260 (9)	0.0367 (10)	−0.0003 (6)	−0.0047 (7)	−0.0010 (7)
C17	0.0221 (7)	0.0228 (9)	0.0380 (10)	0.0017 (6)	−0.0064 (7)	0.0031 (7)
C18	0.0199 (7)	0.0188 (8)	0.0261 (8)	0.0016 (5)	−0.0033 (6)	0.0013 (6)
C19	0.0231 (7)	0.0173 (8)	0.0336 (9)	0.0034 (6)	−0.0028 (6)	0.0025 (7)
C20	0.0240 (8)	0.0161 (8)	0.0484 (12)	0.0015 (6)	−0.0005 (8)	0.0024 (8)
C21	0.0417 (12)	0.0216 (10)	0.0643 (17)	−0.0029 (8)	0.0073 (11)	−0.0096 (10)
C22	0.0471 (13)	0.0308 (12)	0.0514 (15)	−0.0087 (10)	−0.0051 (11)	−0.0138 (11)
C23	0.0700 (19)	0.0531 (18)	0.0365 (13)	−0.0012 (14)	0.0041 (13)	−0.0218 (12)
C24	0.0475 (14)	0.0573 (18)	0.0553 (16)	−0.0143 (13)	−0.0279 (13)	0.0002 (14)
C25	0.0232 (7)	0.0175 (7)	0.0221 (7)	0.0004 (5)	−0.0037 (6)	0.0010 (6)
C26	0.0249 (7)	0.0184 (8)	0.0227 (7)	−0.0014 (6)	−0.0050 (6)	0.0029 (6)
C27	0.0275 (8)	0.0199 (8)	0.0303 (9)	0.0012 (6)	−0.0056 (7)	0.0012 (7)
C28	0.0336 (10)	0.0224 (9)	0.0440 (12)	0.0036 (7)	−0.0117 (9)	0.0037 (8)
C29	0.0462 (12)	0.0262 (11)	0.0439 (12)	0.0001 (9)	−0.0183 (10)	0.0131 (9)
C30	0.0474 (12)	0.0314 (11)	0.0287 (10)	−0.0057 (9)	−0.0092 (9)	0.0105 (8)
C31	0.0333 (9)	0.0251 (9)	0.0249 (8)	−0.0049 (7)	−0.0045 (7)	0.0045 (7)
C32	0.0481 (13)	0.0394 (13)	0.0277 (10)	0.0012 (10)	0.0058 (9)	0.0043 (9)
Cl1	0.02552 (18)	0.01891 (18)	0.02484 (18)	0.00209 (14)	−0.00050 (14)	0.00546 (14)
O11A	0.040 (4)	0.0144 (16)	0.037 (3)	0.0024 (15)	−0.008 (3)	0.0036 (14)
O12A	0.026 (2)	0.051 (4)	0.057 (3)	−0.010 (2)	−0.0030 (17)	0.013 (2)
O13A	0.040 (3)	0.069 (5)	0.052 (3)	−0.001 (3)	−0.013 (2)	0.037 (3)
O14A	0.092 (5)	0.0242 (19)	0.060 (4)	0.003 (3)	0.038 (3)	−0.010 (3)
O11B	0.031 (4)	0.018 (3)	0.041 (6)	0.001 (3)	−0.015 (3)	0.000 (3)
O12B	0.026 (4)	0.056 (8)	0.092 (11)	0.007 (4)	0.008 (5)	0.019 (7)
O13B	0.042 (4)	0.050 (6)	0.066 (7)	0.020 (4)	−0.016 (4)	0.025 (5)
O14B	0.135 (12)	0.036 (6)	0.033 (4)	−0.032 (7)	−0.001 (6)	−0.010 (3)

Geometric parameters (Å, º)

Cu1—O3	1.9514 (13)	C12—H12C	0.9800
Cu1—O1	1.9654 (13)	C13—C14	1.410 (2)
Cu1—N2	1.9731 (15)	C13—C18	1.417 (2)
Cu1—N1	2.1126 (16)	C14—C15	1.387 (2)
Cu1—O2	2.2935 (13)	C14—H14A	0.9500
Cu1—Cu2	3.0155 (3)	C15—C16	1.395 (3)
Cu2—O2	1.9615 (13)	C15—H15A	0.9500
Cu2—N3	1.9693 (15)	C16—C17	1.379 (3)
Cu2—O4	1.9719 (14)	C16—H16A	0.9500
Cu2—N4	2.0909 (18)	C17—C18	1.412 (3)
Cu2—O1	2.3053 (14)	C17—H17A	0.9500
O1—C1	1.322 (2)	C18—C19	1.441 (3)
O2—C13	1.326 (2)	C19—H19A	0.9500
O3—C25	1.265 (2)	C20—C21	1.517 (4)
O4—C25	1.259 (2)	C20—H20A	0.9900
N1—C11	1.485 (2)	C20—H20B	0.9900
N1—C12	1.486 (3)	C21—C22	1.505 (4)
N1—C10	1.496 (3)	C21—H21A	0.9900
N2—C7	1.285 (2)	C21—H21B	0.9900
N2—C8	1.477 (2)	C22—H22A	0.9900
N3—C19	1.292 (2)	C22—H22B	0.9900
N3—C20	1.479 (2)	C23—H23A	0.9800
N4—C23	1.478 (4)	C23—H23B	0.9800
N4—C24	1.492 (3)	C23—H23C	0.9800
N4—C22	1.497 (3)	C24—H24A	0.9800
C1—C6	1.415 (3)	C24—H24B	0.9800
C1—C2	1.421 (2)	C24—H24C	0.9800
C2—C3	1.383 (3)	C25—C26	1.507 (2)
C2—H2A	0.9500	C26—C27	1.403 (3)
C3—C4	1.396 (4)	C26—C31	1.409 (3)
C3—H3A	0.9500	C27—C28	1.389 (3)
C4—C5	1.376 (3)	C27—H27A	0.9500
C4—H4A	0.9500	C28—C29	1.383 (4)
C5—C6	1.411 (3)	C28—H28A	0.9500
C5—H5A	0.9500	C29—C30	1.381 (4)
C6—C7	1.448 (3)	C29—H29A	0.9500
C7—H7A	0.9500	C30—C31	1.404 (3)
C8—C9	1.516 (3)	C30—H30A	0.9500
C8—H8A	0.9900	C31—C32	1.507 (3)
C8—H8B	0.9900	C32—H32A	0.9800
C9—C10	1.513 (3)	C32—H32B	0.9800
C9—H9A	0.9900	C32—H32C	0.9800
C9—H9B	0.9900	Cl1—O13B	1.417 (11)
C10—H10A	0.9900	Cl1—O12A	1.425 (7)
C10—H10B	0.9900	Cl1—O11B	1.428 (12)
C11—H11A	0.9800	Cl1—O14A	1.430 (6)
C11—H11B	0.9800	Cl1—O14B	1.433 (11)
C11—H11C	0.9800	Cl1—O13A	1.433 (7)
C12—H12A	0.9800	Cl1—O12B	1.445 (12)
C12—H12B	0.9800	Cl1—O11A	1.448 (7)
O3—Cu1—O1	84.62 (6)	H11A—C11—H11C	109.5
O3—Cu1—N2	171.91 (6)	H11B—C11—H11C	109.5
O1—Cu1—N2	91.26 (6)	N1—C12—H12A	109.5
O3—Cu1—N1	84.62 (6)	N1—C12—H12B	109.5
O1—Cu1—N1	163.37 (6)	H12A—C12—H12B	109.5
N2—Cu1—N1	97.79 (7)	N1—C12—H12C	109.5
O3—Cu1—O2	90.51 (5)	H12A—C12—H12C	109.5
O1—Cu1—O2	89.15 (5)	H12B—C12—H12C	109.5
N2—Cu1—O2	96.40 (6)	O2—C13—C14	119.83 (16)
N1—Cu1—O2	103.59 (5)	O2—C13—C18	122.59 (15)
O3—Cu1—Cu2	78.46 (4)	C14—C13—C18	117.58 (15)
O1—Cu1—Cu2	49.86 (4)	C15—C14—C13	121.20 (17)
N2—Cu1—Cu2	104.15 (5)	C15—C14—H14A	119.4
N1—Cu1—Cu2	139.14 (4)	C13—C14—H14A	119.4
O2—Cu1—Cu2	40.58 (3)	C14—C15—C16	121.19 (17)
O2—Cu2—N3	91.49 (6)	C14—C15—H15A	119.4
O2—Cu2—O4	86.24 (6)	C16—C15—H15A	119.4
N3—Cu2—O4	173.70 (6)	C17—C16—C15	118.55 (17)
O2—Cu2—N4	158.84 (7)	C17—C16—H16A	120.7
N3—Cu2—N4	93.01 (7)	C15—C16—H16A	120.7
O4—Cu2—N4	87.06 (7)	C16—C17—C18	121.59 (18)
O2—Cu2—O1	88.90 (5)	C16—C17—H17A	119.2
N3—Cu2—O1	96.90 (6)	C18—C17—H17A	119.2
O4—Cu2—O1	88.94 (5)	C17—C18—C13	119.84 (16)
N4—Cu2—O1	111.03 (7)	C17—C18—C19	117.18 (16)
O2—Cu2—Cu1	49.52 (4)	C13—C18—C19	122.97 (15)
N3—Cu2—Cu1	104.63 (5)	N3—C19—C18	126.86 (17)
O4—Cu2—Cu1	78.32 (4)	N3—C19—H19A	116.6
N4—Cu2—Cu1	147.40 (6)	C18—C19—H19A	116.6
O1—Cu2—Cu1	40.67 (3)	N3—C20—C21	110.15 (19)
C1—O1—Cu1	126.72 (12)	N3—C20—H20A	109.6
C1—O1—Cu2	120.64 (11)	C21—C20—H20A	109.6
Cu1—O1—Cu2	89.47 (5)	N3—C20—H20B	109.6
C13—O2—Cu2	123.99 (11)	C21—C20—H20B	109.6
C13—O2—Cu1	129.87 (11)	H20A—C20—H20B	108.1
Cu2—O2—Cu1	89.91 (5)	C22—C21—C20	113.5 (2)
C25—O3—Cu1	127.72 (12)	C22—C21—H21A	108.9
C25—O4—Cu2	127.43 (12)	C20—C21—H21A	108.9
C11—N1—C12	106.62 (17)	C22—C21—H21B	108.9
C11—N1—C10	108.75 (15)	C20—C21—H21B	108.9
C12—N1—C10	106.75 (15)	H21A—C21—H21B	107.7
C11—N1—Cu1	105.12 (12)	N4—C22—C21	115.5 (2)
C12—N1—Cu1	112.50 (13)	N4—C22—H22A	108.4
C10—N1—Cu1	116.64 (13)	C21—C22—H22A	108.4
C7—N2—C8	115.82 (16)	N4—C22—H22B	108.4
C7—N2—Cu1	125.31 (13)	C21—C22—H22B	108.4
C8—N2—Cu1	118.87 (13)	H22A—C22—H22B	107.5
C19—N3—C20	115.97 (16)	N4—C23—H23A	109.5
C19—N3—Cu2	123.10 (13)	N4—C23—H23B	109.5
C20—N3—Cu2	120.81 (12)	H23A—C23—H23B	109.5
C23—N4—C24	108.3 (2)	N4—C23—H23C	109.5
C23—N4—C22	111.8 (2)	H23A—C23—H23C	109.5
C24—N4—C22	104.3 (2)	H23B—C23—H23C	109.5
C23—N4—Cu2	102.51 (15)	N4—C24—H24A	109.5
C24—N4—Cu2	112.86 (16)	N4—C24—H24B	109.5
C22—N4—Cu2	117.07 (15)	H24A—C24—H24B	109.5
O1—C1—C6	123.39 (16)	N4—C24—H24C	109.5
O1—C1—C2	119.55 (17)	H24A—C24—H24C	109.5
C6—C1—C2	117.05 (17)	H24B—C24—H24C	109.5
C3—C2—C1	121.3 (2)	O4—C25—O3	125.98 (16)
C3—C2—H2A	119.3	O4—C25—C26	118.45 (16)
C1—C2—H2A	119.3	O3—C25—C26	115.56 (16)
C2—C3—C4	121.09 (19)	C27—C26—C31	119.90 (17)
C2—C3—H3A	119.5	C27—C26—C25	116.94 (16)
C4—C3—H3A	119.5	C31—C26—C25	123.16 (17)
C5—C4—C3	118.8 (2)	C28—C27—C26	120.9 (2)
C5—C4—H4A	120.6	C28—C27—H27A	119.5
C3—C4—H4A	120.6	C26—C27—H27A	119.5
C4—C5—C6	121.5 (2)	C29—C28—C27	119.4 (2)
C4—C5—H5A	119.3	C29—C28—H28A	120.3
C6—C5—H5A	119.3	C27—C28—H28A	120.3
C5—C6—C1	120.24 (18)	C30—C29—C28	120.2 (2)
C5—C6—C7	117.34 (18)	C30—C29—H29A	119.9
C1—C6—C7	122.41 (16)	C28—C29—H29A	119.9
N2—C7—C6	127.13 (17)	C29—C30—C31	121.9 (2)
N2—C7—H7A	116.4	C29—C30—H30A	119.0
C6—C7—H7A	116.4	C31—C30—H30A	119.0
N2—C8—C9	110.19 (16)	C30—C31—C26	117.7 (2)
N2—C8—H8A	109.6	C30—C31—C32	118.3 (2)
C9—C8—H8A	109.6	C26—C31—C32	124.01 (18)
N2—C8—H8B	109.6	C31—C32—H32A	109.5
C9—C8—H8B	109.6	C31—C32—H32B	109.5
H8A—C8—H8B	108.1	H32A—C32—H32B	109.5
C10—C9—C8	112.43 (17)	C31—C32—H32C	109.5
C10—C9—H9A	109.1	H32A—C32—H32C	109.5
C8—C9—H9A	109.1	H32B—C32—H32C	109.5
C10—C9—H9B	109.1	O13B—Cl1—O11B	111.3 (10)
C8—C9—H9B	109.1	O12A—Cl1—O14A	109.8 (5)
H9A—C9—H9B	107.8	O13B—Cl1—O14B	109.3 (9)
N1—C10—C9	113.79 (16)	O11B—Cl1—O14B	109.4 (11)
N1—C10—H10A	108.8	O12A—Cl1—O13A	110.1 (5)
C9—C10—H10A	108.8	O14A—Cl1—O13A	109.6 (5)
N1—C10—H10B	108.8	O13B—Cl1—O12B	110.0 (11)
C9—C10—H10B	108.8	O11B—Cl1—O12B	108.2 (11)
H10A—C10—H10B	107.7	O14B—Cl1—O12B	108.6 (9)
N1—C11—H11A	109.5	O12A—Cl1—O11A	110.4 (6)
N1—C11—H11B	109.5	O14A—Cl1—O11A	108.1 (6)
H11A—C11—H11B	109.5	O13A—Cl1—O11A	108.8 (5)
N1—C11—H11C	109.5
Cu1—O1—C1—C6	−19.3 (2)	C16—C17—C18—C19	−179.3 (2)
Cu2—O1—C1—C6	96.02 (18)	O2—C13—C18—C17	178.64 (18)
Cu1—O1—C1—C2	161.71 (13)	C14—C13—C18—C17	−1.7 (3)
Cu2—O1—C1—C2	−82.93 (17)	O2—C13—C18—C19	−2.5 (3)
O1—C1—C2—C3	179.52 (17)	C14—C13—C18—C19	177.14 (18)
C6—C1—C2—C3	0.5 (3)	C20—N3—C19—C18	−179.53 (19)
C1—C2—C3—C4	−1.1 (3)	Cu2—N3—C19—C18	4.4 (3)
C2—C3—C4—C5	0.3 (3)	C17—C18—C19—N3	−167.3 (2)
C3—C4—C5—C6	1.2 (4)	C13—C18—C19—N3	13.8 (3)
C4—C5—C6—C1	−1.8 (3)	C19—N3—C20—C21	−115.9 (2)
C4—C5—C6—C7	179.1 (2)	Cu2—N3—C20—C21	60.3 (2)
O1—C1—C6—C5	−178.04 (18)	N3—C20—C21—C22	−70.2 (2)
C2—C1—C6—C5	0.9 (3)	C23—N4—C22—C21	69.0 (3)
O1—C1—C6—C7	1.0 (3)	C24—N4—C22—C21	−174.2 (2)
C2—C1—C6—C7	179.95 (17)	Cu2—N4—C22—C21	−48.7 (3)
C8—N2—C7—C6	178.45 (19)	C20—C21—C22—N4	67.0 (3)
Cu1—N2—C7—C6	−0.9 (3)	Cu2—O4—C25—O3	4.0 (3)
C5—C6—C7—N2	−171.1 (2)	Cu2—O4—C25—C26	−175.52 (12)
C1—C6—C7—N2	9.9 (3)	Cu1—O3—C25—O4	11.9 (3)
C7—N2—C8—C9	−125.45 (19)	Cu1—O3—C25—C26	−168.62 (12)
Cu1—N2—C8—C9	54.0 (2)	O4—C25—C26—C27	153.93 (18)
N2—C8—C9—C10	−79.2 (2)	O3—C25—C26—C27	−25.6 (2)
C11—N1—C10—C9	77.9 (2)	O4—C25—C26—C31	−26.8 (3)
C12—N1—C10—C9	−167.42 (18)	O3—C25—C26—C31	153.65 (18)
Cu1—N1—C10—C9	−40.7 (2)	C31—C26—C27—C28	1.1 (3)
C8—C9—C10—N1	72.8 (2)	C25—C26—C27—C28	−179.63 (18)
Cu2—O2—C13—C14	155.33 (13)	C26—C27—C28—C29	−1.9 (3)
Cu1—O2—C13—C14	−80.6 (2)	C27—C28—C29—C30	1.2 (3)
Cu2—O2—C13—C18	−25.1 (2)	C28—C29—C30—C31	0.4 (4)
Cu1—O2—C13—C18	99.03 (18)	C29—C30—C31—C26	−1.2 (3)
O2—C13—C14—C15	−178.08 (17)	C29—C30—C31—C32	−179.4 (2)
C18—C13—C14—C15	2.3 (3)	C27—C26—C31—C30	0.5 (3)
C13—C14—C15—C16	−0.7 (3)	C25—C26—C31—C30	−178.74 (18)
C14—C15—C16—C17	−1.5 (3)	C27—C26—C31—C32	178.5 (2)
C15—C16—C17—C18	2.0 (3)	C25—C26—C31—C32	−0.7 (3)
C16—C17—C18—C13	−0.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10B···O13A^a^i	0.99	2.69	3.418 (12)	130
C10—H10B···O13B^b^i	0.99	2.44	3.242 (14)	138
C11—H11B···O13A^a^ii	0.98	2.65	3.148 (8)	111
C11—H11C···O3	0.98	2.48	3.039 (2)	116
C12—H12B···O3	0.98	2.34	2.866 (3)	113
C14—H14A···O14A^a^i	0.95	2.49	3.127 (10)	124
C19—H19A···O11A^a	0.95	2.26	3.159 (12)	158
C20—H20B···O12A^a	0.99	2.63	3.606 (13)	169
C24—H24B···O4	0.98	2.29	2.807 (3)	112

Symmetry codes: (i) −x+3/2, y+1/2, z; (ii) −x+1, y+1/2, −z+1/2.