Chloro(2,9-dimethyl-1,10-phenanthroline-N,N')(isoquinoline-1-carboxylato-O,N)copper(II)

The asymmetric unit of the title compound, [CuCl(C₁₀H₆NO₂)(C₁₄H₁₂N₂)], contains two monomeric copper mol­ecules, A and B. Each Cu atom is coordinated to one 2,9-di­methyl-1,10-phenanthroline (neocuproine) ligand via both N atoms, to one iso­quinoline-1-carboxyl­ate anion (IQC^-) via the N and one O atom, and to one Cl^- anion. The environment of the Cu atom is approximately square pyramidal, with the apical position occupied by an N atom of neocuproine. In mol­ecule A, the Cu atom is 0.301 (1) Å above the basal plane; this distance is 0.316 (1) Å in mol­ecule B. The crystal packing is characterized by several hydrogen bonds.

S1. Comment

Copper(II) complexes with nonsteroidal antiinflammatory drugs (NSAIDs) have been extensively studied since Sorenson (1976) demonstrated that they are more active than their parent drugs and exhibit antiulcer activity. He also showed that 3,5-diisopropylsalicylic acid, which is an inactive agent, becomes a potent antiinflammatory compound when it chelates to Cu^II. Moreover, binary complexes of Cu^II with 3,5-disubstituted salicylates, and ternary complexes with added phenanthrolines, have been prepared and characterized by Randford et al. (1993). These complexes have been tested for antiviral and cytotoxic activities; ternary complexes were ten times as cytotoxic as their binary analogues.

Among the molecules investigated by Sorenson, the group of heterocyclic carboxylic acid chelates has not been adequately evaluated to enable the separation of members of this class of coordination compounds based upon their antiinflammatory activity. Therefore, in the course of our investigations, we have previously examined the synthesis and crystal structures of two binary complexes formed by Cu^II salts with N,O-1-isoquinolinecarboxylic acid (HIQC; (Pardo et al., 1999, 2000). Following Randford's work, we decided to synthesize and characterize ternary complexes of Cu^II with HIQC and the heteroaromatic N base 2,9-dimethyl-1,10-phenanthroline, before testing their biological activities. To this end, the title compound, (I), has been prepared and its crystal structure is presented here. \sch

Compound (I) consists of two crystallographically independant and monomeric molecules, A and B. Each Cu^II cation is surrounded by one 2,9-dimethyl-1,10-phenanthroline (neocuproine) ligand via both N atoms, one isoquinoline-1-carboxylate anion (IQC^-) and one Cl^- anion. The IQC^- anion is bidentate via the carboxylate and the N atom. The Cu^II cation shows a distorted square pyramidal coordination. Each pseudo basal plane, P1 or P2 for molecules A or B, respectively, is formed by atom N20 (or N70) from the neocuproine, O1 (or O51) and N1 (or N51) from IQC^-, and Cl1 (or Cl51) [maximum deviations: 0.056 (1) Å for O1 out of P1 and 0.080 (1) Å for O51 out of P2]. The apical position is occupied by atom N11 of the neocuproine in molecule A, at 2.424 (2) Å from P1; in molecule B, N61 is 2.439 (2) Å from P2. Atom Cu1 lies 0.301 (1) Å out of P1 in molecule A, and atom Cu51 is 0.316 (1) Å out of P2 in molecule B. The copper-to-carboxylate oxygen distances Cu1—O1 and Cu51—O51 [1.950 (2) and 1.948 (2) Å, respectively] are to be compared with the corresponding values in bis[N,O-1-isoquinolinecarboxylato]copper(II) [1.928 (3) Å; Pardo et al., 1999].

The distances between Cu and the N atoms belonging to the basal planes are similar [average 2.024 (2) Å]. The observed Cu—N_apical bond lengths [2.231 (2) in A and 2.228 (2) Å in B] agree fairly well with the corresponding value of 2.290 (3) Å de scribed by Li et al. (1999) in µ-[1,1'-(1,2-ethanediyl)bis(1H-1,2,4-triazole)]-N⁴:N⁴'- bis{bis[1,1,1-trifluoro-3-(2-thenoyl)acetonato-O,O']copper(II)}. In the basal planes, the values of the bond angles at the Cu atoms are in the range 80.99 (9)–94.83 (7)° for molecule A and 80.77 (9)–94.72 (7)° for molecule B.

The distances and angles within the IQC^- ligand are analogous to those observed in bis[N,O-1-isoquinolinecarboxylato]copper(II) (Pardo et al., 1999). The isoquinoline mean plane P3 in molecule A makes a dihedral angle of 8.9 (2)° with the O1/O2/C1/C2 mean plane; the equivalent plane P4 in molecule B makes a dihedral angle of 6.8 (2)° with O51/O52/C51/C52.

The distances and angles within the neocuproine ligands do not differ from those found in the literature. The neocuproine mean plane in molecule A makes a dihedral angle of 71.26 (3)° with P3; in molecule B, the neocuproine mean plane makes a dihedral angle of 69.07 (3)° with P4.

The packing in (I) is characterized by interactions that can be considered as hydrogen bonds, since they correspond to H···A contacts significantly shorter than the sum of van der Waals radii (Table 2). The first two are responsible for the orientation of the isoquinoline plane in both molecules; the third and fourth are related to the orientation of the isoquinoline with respect to the chlorine ligand. The last two interactions are the ones mainly responsible for the crystal packing. The crystalline cohesion is likewise ensured by several van der Waals contacts, the shortest being 3.198 (4) Å.

Related literature

For related literature, see: Li et al. (1999); Pardo et al. (1999, 2000); Randford et al. (1993); Sorenson (1976).

S2. Experimental

The copper(II) coordination compound of 1-carboxyisoquinoline was synthesized using the procedure of Sorenson (1976). The title complex was prepared by the reaction of neocuproine (NC) with isoquinolinecarboxylatocopper(II) (NC:Cu 2:1) in methanol. After addition of HCl (H⁺:Cu 1:1) and stirring for about 1 hr, a precipitate was formed and collected by filtration. This blue precipitate was washed with methanol, dried overnight at 333 K and 15 mm H g (1 mm H g = 133.322 Pa) and dissolved in N,N-dimethylacetamide. Single crystals of (I) were obtained by slow evaporation of this solution under ambient air pressure. The crystal density was measured by flotation in?

S3. Refinement

All H atoms were refined in idealized positions using a riding model (C—H = 0.95 and 0.98 Å) with a collective isotropic displacement parameter U_iso(H) = 0.049 (2) Ų.

Computing details

Data collection: KappaCCD Server Software (Nonius, 1998); cell refinement: SCALEPACK in HKL (Otwinowski & Minor, 1997); data reduction: SCALEPACK in HKL; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. A perspective view of the asymetric unit of (I) showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

Chloro(isoquinoline-1-carboxylato-O,N)(2,9-dimethyl-1,10-phenanthroline- N,N')copper(II)

Crystal data

[CuCl(C12H6NO2)(C14H12N2)]	F(000) = 1960
Mr = 479.41	Dx = 1.548 Mg m^−3 Dm = 1.54 Mg m^−3 Dm measured by flotation
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.855 (1) Å	Cell parameters from 72742 reflections
b = 15.955 (1) Å	θ = 1.0–27.5°
c = 22.391 (1) Å	µ = 1.22 mm^−1
β = 103.77 (1)°	T = 180 K
V = 4113.5 (5) Å^3	Parallelepiped, blue
Z = 8	0.25 × 0.23 × 0.20 mm

Data collection

Nonius KappaCCD diffractometer	5404 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.040
Horizonally mounted graphite crystal monochromator	θmax = 26.0°, θmin = 1.8°
Detector resolution: 9 pixels mm^-1	h = −14→9
CCD scans	k = −13→19
14915 measured reflections	l = −20→27
7291 independent reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.118	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
7291 reflections	(Δ/σ)max = 0.001
564 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.63 e Å^−3

Special details

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

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 > σ(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.

Refinement on F² for all reflections except for 16 flagged for potential systematic errors.

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

	x	y	z	Uiso*/Ueq
Cu1	0.85423 (3)	0.11159 (2)	0.34493 (2)	0.02421 (12)
Cl1	0.71937 (7)	0.10748 (5)	0.25373 (4)	0.0349 (2)
O1	0.99955 (17)	0.09785 (12)	0.40693 (10)	0.0326 (5)
N1	0.8409 (2)	−0.01078 (15)	0.36344 (11)	0.0252 (5)
C1	1.0267 (3)	0.02433 (19)	0.42741 (14)	0.0297 (7)
O2	1.11572 (19)	0.00542 (14)	0.46510 (11)	0.0450 (6)
C2	0.9363 (2)	−0.04292 (18)	0.39963 (13)	0.0247 (6)
C3	0.9516 (2)	−0.13104 (18)	0.40889 (13)	0.0258 (6)
C4	1.0538 (3)	−0.1691 (2)	0.44372 (15)	0.0346 (7)
H4	1.1163	−0.1353	0.4654	0.0486 (18)*
C5	1.0627 (3)	−0.2544 (2)	0.44624 (16)	0.0421 (8)
H5	1.1323	−0.2794	0.4692	0.0486 (18)*
C6	0.9713 (3)	−0.3056 (2)	0.41558 (16)	0.0401 (8)
H6	0.9799	−0.3648	0.4176	0.0486 (18)*
C7	0.8707 (3)	−0.27168 (19)	0.38309 (15)	0.0363 (8)
H7	0.8083	−0.3070	0.3636	0.0486 (18)*
C8	0.8584 (2)	−0.18360 (17)	0.37813 (14)	0.0265 (6)
C9	0.7569 (3)	−0.14592 (19)	0.34269 (14)	0.0318 (7)
H9	0.6924	−0.1797	0.3236	0.0486 (18)*
C10	0.7512 (2)	−0.06150 (18)	0.33576 (14)	0.0288 (7)
H10	0.6829	−0.0371	0.3110	0.0486 (18)*
N11	0.75995 (19)	0.19653 (14)	0.39560 (11)	0.0237 (5)
C12	0.6827 (2)	0.18092 (18)	0.42886 (13)	0.0250 (6)
C13	0.6277 (2)	0.24658 (19)	0.45341 (14)	0.0302 (7)
H13	0.5726	0.2339	0.4768	0.0486 (18)*
C14	0.6531 (2)	0.3278 (2)	0.44384 (14)	0.0312 (7)
H14	0.6160	0.3719	0.4603	0.0486 (18)*
C15	0.7674 (3)	0.42978 (19)	0.39651 (15)	0.0337 (7)
H15	0.7344	0.4761	0.4129	0.0486 (18)*
C16	0.8438 (3)	0.44360 (19)	0.36155 (15)	0.0327 (7)
H16	0.8638	0.4995	0.3538	0.0486 (18)*
C17	0.9761 (2)	0.38612 (19)	0.29971 (14)	0.0313 (7)
H17	0.9995	0.4409	0.2912	0.0486 (18)*
C18	1.0211 (2)	0.3177 (2)	0.27671 (14)	0.0324 (7)
H18	1.0753	0.3250	0.2520	0.0486 (18)*
C19	0.9872 (2)	0.23660 (19)	0.28960 (14)	0.0289 (7)
N20	0.91137 (19)	0.22526 (14)	0.32417 (11)	0.0245 (5)
C21	0.8660 (2)	0.29268 (18)	0.34796 (13)	0.0253 (6)
C22	0.8953 (2)	0.37560 (18)	0.33591 (14)	0.0278 (7)
C23	0.7350 (2)	0.34595 (18)	0.40933 (13)	0.0276 (7)
C24	0.7856 (2)	0.27772 (17)	0.38563 (13)	0.0238 (6)
C25	0.6542 (3)	0.09135 (19)	0.43782 (15)	0.0333 (7)
H251	0.6254	0.0647	0.3977	0.0486 (18)*
H252	0.5943	0.0884	0.4613	0.0486 (18)*
H253	0.7242	0.0622	0.4604	0.0486 (18)*
C26	1.0316 (3)	0.1602 (2)	0.26391 (15)	0.0370 (8)
H261	1.0533	0.1178	0.2963	0.0486 (18)*
H262	1.0998	0.1750	0.2485	0.0486 (18)*
H263	0.9708	0.1377	0.2301	0.0486 (18)*
Cu51	1.14745 (3)	−0.02256 (2)	0.15969 (2)	0.02570 (12)
Cl51	1.28626 (7)	−0.01808 (5)	0.24910 (4)	0.0350 (2)
O51	0.99770 (18)	−0.00803 (13)	0.10166 (10)	0.0373 (5)
N51	1.1584 (2)	0.10103 (15)	0.14109 (11)	0.0266 (6)
C51	0.9683 (3)	0.0657 (2)	0.08261 (15)	0.0362 (8)
O52	0.8765 (2)	0.08489 (16)	0.04750 (14)	0.0666 (9)
C52	1.0596 (2)	0.13272 (19)	0.10763 (13)	0.0260 (6)
C53	1.0443 (3)	0.22087 (18)	0.09725 (13)	0.0280 (7)
C54	0.9391 (3)	0.2582 (2)	0.06507 (15)	0.0357 (7)
H54	0.8733	0.2242	0.0486	0.0486 (18)*
C55	0.9322 (3)	0.3437 (2)	0.05771 (16)	0.0459 (9)
H55	0.8611	0.3686	0.0365	0.0486 (18)*
C56	1.0286 (4)	0.3943 (2)	0.08106 (17)	0.0493 (10)
H56	1.0224	0.4532	0.0750	0.0486 (18)*
C57	1.1308 (3)	0.3611 (2)	0.11219 (16)	0.0450 (9)
H57	1.1955	0.3965	0.1277	0.0486 (18)*
C58	1.1411 (3)	0.27309 (19)	0.12161 (14)	0.0329 (7)
C59	1.2441 (3)	0.2362 (2)	0.15572 (15)	0.0360 (8)
H59	1.3100	0.2703	0.1720	0.0486 (18)*
C60	1.2501 (3)	0.15181 (19)	0.16549 (14)	0.0316 (7)
H60	1.3194	0.1280	0.1897	0.0486 (18)*
N61	1.2382 (2)	−0.10542 (14)	0.10602 (11)	0.0251 (5)
C62	1.3122 (2)	−0.08861 (19)	0.07141 (14)	0.0291 (7)
C63	1.3661 (3)	−0.1533 (2)	0.04530 (14)	0.0351 (8)
H63	1.4202	−0.1397	0.0216	0.0486 (18)*
C64	1.3410 (3)	−0.2347 (2)	0.05384 (15)	0.0359 (8)
H64	1.3765	−0.2779	0.0356	0.0486 (18)*
C65	1.2312 (3)	−0.3389 (2)	0.10153 (15)	0.0365 (8)
H65	1.2633	−0.3846	0.0840	0.0486 (18)*
C66	1.1565 (3)	−0.3540 (2)	0.13721 (15)	0.0348 (8)
H66	1.1370	−0.4102	0.1443	0.0486 (18)*
C67	1.0264 (3)	−0.2993 (2)	0.20116 (15)	0.0347 (7)
H67	1.0030	−0.3544	0.2089	0.0486 (18)*
C68	0.9822 (3)	−0.2319 (2)	0.22565 (15)	0.0345 (7)
H68	0.9277	−0.2401	0.2501	0.0486 (18)*
C69	1.0176 (2)	−0.15030 (19)	0.21473 (14)	0.0306 (7)
N70	1.0925 (2)	−0.13730 (15)	0.17985 (11)	0.0263 (5)
C71	1.1362 (2)	−0.20369 (17)	0.15426 (12)	0.0214 (6)
C72	1.1062 (3)	−0.28731 (19)	0.16460 (14)	0.0299 (7)
C73	1.2627 (2)	−0.25504 (19)	0.08964 (14)	0.0302 (7)
C74	1.2141 (2)	−0.18735 (17)	0.11542 (13)	0.0253 (6)
C75	1.3372 (3)	0.0013 (2)	0.06167 (16)	0.0388 (8)
H751	1.2646	0.0302	0.0425	0.0486 (18)*
H752	1.3911	0.0052	0.0347	0.0486 (18)*
H753	1.3721	0.0275	0.1013	0.0486 (18)*
C76	0.9733 (3)	−0.0753 (2)	0.24195 (16)	0.0405 (8)
H761	1.0365	−0.0504	0.2733	0.0486 (18)*
H762	0.9104	−0.0922	0.2609	0.0486 (18)*
H763	0.9440	−0.0340	0.2096	0.0486 (18)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0241 (2)	0.0232 (2)	0.0256 (2)	0.00144 (13)	0.00654 (16)	0.00088 (14)
Cl1	0.0393 (5)	0.0338 (4)	0.0276 (4)	0.0049 (3)	−0.0001 (3)	0.0000 (3)
O1	0.0293 (12)	0.0249 (11)	0.0400 (13)	−0.0037 (8)	0.0008 (10)	0.0020 (9)
N1	0.0253 (13)	0.0267 (14)	0.0244 (13)	0.0018 (10)	0.0075 (11)	0.0011 (10)
C1	0.0245 (16)	0.0347 (18)	0.0293 (17)	−0.0021 (13)	0.0051 (13)	0.0041 (14)
O2	0.0338 (13)	0.0380 (13)	0.0516 (15)	−0.0042 (10)	−0.0130 (11)	0.0104 (11)
C2	0.0245 (15)	0.0270 (16)	0.0240 (15)	−0.0004 (12)	0.0087 (12)	0.0016 (12)
C3	0.0282 (16)	0.0285 (16)	0.0214 (15)	0.0017 (12)	0.0074 (12)	0.0032 (13)
C4	0.0336 (17)	0.0326 (18)	0.0347 (19)	0.0035 (13)	0.0022 (14)	0.0026 (14)
C5	0.042 (2)	0.038 (2)	0.044 (2)	0.0115 (15)	0.0062 (16)	0.0088 (16)
C6	0.058 (2)	0.0269 (18)	0.037 (2)	0.0100 (15)	0.0161 (17)	0.0032 (15)
C7	0.050 (2)	0.0265 (17)	0.0337 (19)	−0.0016 (14)	0.0117 (16)	0.0032 (14)
C8	0.0327 (16)	0.0230 (16)	0.0247 (16)	0.0002 (12)	0.0086 (13)	0.0016 (12)
C9	0.0308 (16)	0.0320 (18)	0.0313 (18)	−0.0067 (13)	0.0050 (14)	−0.0003 (14)
C10	0.0235 (15)	0.0296 (17)	0.0307 (17)	−0.0010 (12)	0.0013 (13)	−0.0002 (13)
N11	0.0234 (12)	0.0243 (13)	0.0235 (13)	0.0010 (9)	0.0058 (10)	0.0001 (10)
C12	0.0209 (14)	0.0322 (17)	0.0212 (15)	−0.0015 (12)	0.0035 (12)	−0.0014 (12)
C13	0.0274 (16)	0.0362 (18)	0.0283 (17)	0.0029 (13)	0.0090 (13)	0.0004 (14)
C14	0.0278 (16)	0.0389 (19)	0.0258 (17)	0.0086 (13)	0.0044 (13)	−0.0066 (14)
C15	0.0345 (17)	0.0263 (17)	0.0367 (19)	0.0068 (13)	0.0018 (14)	−0.0027 (14)
C16	0.0345 (18)	0.0227 (16)	0.0369 (19)	−0.0021 (12)	0.0006 (15)	0.0015 (14)
C17	0.0264 (16)	0.0315 (18)	0.0337 (18)	−0.0061 (12)	0.0028 (14)	0.0077 (14)
C18	0.0250 (15)	0.0431 (19)	0.0299 (18)	−0.0051 (13)	0.0082 (13)	0.0049 (14)
C19	0.0226 (15)	0.0404 (18)	0.0239 (16)	0.0005 (12)	0.0062 (12)	0.0024 (13)
N20	0.0226 (12)	0.0281 (14)	0.0232 (13)	−0.0004 (10)	0.0061 (10)	0.0009 (10)
C21	0.0216 (14)	0.0265 (16)	0.0269 (16)	0.0013 (11)	0.0040 (12)	0.0021 (12)
C22	0.0229 (15)	0.0279 (16)	0.0298 (17)	0.0000 (12)	0.0005 (12)	0.0043 (13)
C23	0.0269 (15)	0.0270 (16)	0.0265 (17)	0.0059 (12)	0.0016 (13)	−0.0013 (13)
C24	0.0220 (14)	0.0241 (15)	0.0232 (15)	0.0007 (11)	0.0012 (12)	−0.0007 (12)
C25	0.0318 (17)	0.0352 (18)	0.0361 (19)	−0.0049 (13)	0.0144 (14)	−0.0001 (14)
C26	0.0357 (18)	0.045 (2)	0.0353 (19)	0.0041 (14)	0.0189 (15)	−0.0023 (15)
Cu51	0.0245 (2)	0.0253 (2)	0.0275 (2)	−0.00001 (14)	0.00657 (16)	0.00057 (15)
Cl51	0.0376 (4)	0.0345 (4)	0.0297 (4)	0.0040 (3)	0.0015 (3)	−0.0019 (3)
O51	0.0307 (12)	0.0320 (13)	0.0448 (14)	−0.0045 (9)	0.0004 (10)	0.0048 (10)
N51	0.0246 (13)	0.0303 (14)	0.0253 (14)	−0.0016 (10)	0.0071 (11)	−0.0004 (11)
C51	0.0293 (18)	0.042 (2)	0.0361 (19)	−0.0072 (14)	0.0054 (15)	0.0086 (16)
O52	0.0434 (16)	0.0527 (17)	0.083 (2)	−0.0141 (12)	−0.0265 (15)	0.0276 (15)
C52	0.0246 (15)	0.0331 (17)	0.0215 (15)	−0.0002 (12)	0.0082 (12)	0.0017 (13)
C53	0.0335 (17)	0.0321 (17)	0.0216 (15)	0.0032 (13)	0.0128 (13)	0.0024 (13)
C54	0.0381 (18)	0.040 (2)	0.0306 (18)	0.0083 (14)	0.0118 (15)	0.0036 (15)
C55	0.053 (2)	0.048 (2)	0.038 (2)	0.0229 (18)	0.0140 (17)	0.0008 (17)
C56	0.073 (3)	0.031 (2)	0.044 (2)	0.0135 (18)	0.015 (2)	−0.0014 (16)
C57	0.065 (2)	0.0304 (19)	0.038 (2)	−0.0043 (16)	0.0106 (18)	−0.0046 (15)
C58	0.0412 (18)	0.0305 (18)	0.0287 (17)	0.0019 (14)	0.0118 (14)	−0.0026 (13)
C59	0.0398 (19)	0.0328 (19)	0.0337 (18)	−0.0088 (14)	0.0051 (15)	−0.0023 (14)
C60	0.0264 (16)	0.0355 (19)	0.0310 (18)	−0.0027 (13)	0.0030 (13)	0.0003 (14)
N61	0.0230 (12)	0.0293 (14)	0.0236 (13)	−0.0004 (10)	0.0068 (10)	−0.0013 (10)
C62	0.0260 (16)	0.0373 (18)	0.0236 (16)	−0.0025 (13)	0.0049 (13)	−0.0007 (13)
C63	0.0307 (17)	0.047 (2)	0.0296 (18)	0.0000 (14)	0.0112 (14)	−0.0055 (15)
C64	0.0299 (17)	0.045 (2)	0.0321 (18)	0.0073 (14)	0.0053 (14)	−0.0069 (15)
C65	0.0358 (18)	0.0279 (18)	0.041 (2)	0.0081 (14)	0.0003 (15)	−0.0030 (15)
C66	0.0340 (18)	0.0253 (17)	0.0394 (19)	−0.0004 (13)	−0.0028 (15)	0.0016 (14)
C67	0.0335 (17)	0.0337 (18)	0.0325 (18)	−0.0066 (14)	−0.0008 (14)	0.0074 (14)
C68	0.0285 (16)	0.045 (2)	0.0306 (18)	−0.0066 (14)	0.0086 (14)	0.0060 (15)
C69	0.0268 (16)	0.0386 (19)	0.0273 (17)	−0.0017 (13)	0.0085 (13)	0.0033 (14)
N70	0.0241 (12)	0.0303 (14)	0.0247 (13)	−0.0011 (10)	0.0063 (10)	0.0013 (11)
C71	0.0206 (14)	0.0247 (15)	0.0156 (14)	0.0024 (11)	−0.0022 (11)	0.0015 (11)
C72	0.0251 (15)	0.0301 (17)	0.0306 (17)	−0.0016 (12)	−0.0010 (13)	0.0041 (13)
C73	0.0251 (16)	0.0342 (18)	0.0283 (17)	0.0058 (12)	0.0007 (13)	−0.0016 (14)
C74	0.0222 (14)	0.0288 (16)	0.0227 (15)	0.0014 (11)	0.0009 (12)	−0.0005 (12)
C75	0.0413 (19)	0.0397 (19)	0.040 (2)	−0.0068 (15)	0.0198 (16)	0.0004 (16)
C76	0.0411 (19)	0.044 (2)	0.042 (2)	0.0002 (15)	0.0219 (16)	0.0005 (16)

Geometric parameters (Å, º)

Cu1—O1	1.950 (2)	Cu51—O51	1.948 (2)
Cu1—N1	2.010 (2)	Cu51—N51	2.026 (2)
Cu1—N20	2.028 (2)	Cu51—N70	2.030 (2)
Cu1—N11	2.231 (2)	Cu51—N61	2.228 (2)
Cu1—Cl1	2.2752 (9)	Cu51—Cl51	2.2701 (9)
O1—C1	1.273 (3)	O51—C51	1.271 (4)
N1—C2	1.327 (4)	N51—C52	1.330 (4)
N1—C10	1.363 (4)	N51—C60	1.362 (4)
C1—O2	1.222 (3)	C51—O52	1.220 (4)
C1—C2	1.539 (4)	C51—C52	1.530 (4)
C2—C3	1.427 (4)	C52—C53	1.430 (4)
C3—C4	1.412 (4)	C53—C54	1.415 (4)
C3—C8	1.427 (4)	C53—C58	1.418 (4)
C4—C5	1.365 (4)	C54—C55	1.374 (5)
C5—C6	1.400 (5)	C55—C56	1.395 (5)
C6—C7	1.353 (4)	C56—C57	1.354 (5)
C7—C8	1.415 (4)	C57—C58	1.420 (4)
C8—C9	1.409 (4)	C58—C59	1.406 (4)
C9—C10	1.356 (4)	C59—C60	1.363 (4)
N11—C12	1.334 (4)	N61—C62	1.329 (4)
N11—C24	1.361 (3)	N61—C74	1.365 (3)
C12—C13	1.413 (4)	C62—C63	1.411 (4)
C12—C25	1.493 (4)	C62—C75	1.491 (4)
C13—C14	1.359 (4)	C63—C64	1.356 (5)
C14—C23	1.407 (4)	C64—C73	1.402 (4)
C15—C16	1.349 (4)	C65—C66	1.347 (5)
C15—C23	1.439 (4)	C65—C73	1.431 (4)
C16—C22	1.430 (4)	C66—C72	1.428 (4)
C17—C18	1.369 (4)	C67—C68	1.367 (4)
C17—C22	1.404 (4)	C67—C72	1.404 (4)
C18—C19	1.405 (4)	C68—C69	1.406 (4)
C19—N20	1.331 (4)	C69—N70	1.331 (4)
C19—C26	1.496 (4)	C69—C76	1.494 (4)
N20—C21	1.366 (4)	N70—C71	1.364 (4)
C21—C22	1.410 (4)	C71—C72	1.414 (4)
C21—C24	1.435 (4)	C71—C74	1.435 (4)
C23—C24	1.406 (4)	C73—C74	1.411 (4)
O1—Cu1—N1	80.99 (9)	O51—Cu51—N51	80.77 (9)
O1—Cu1—N20	88.68 (9)	O51—Cu51—N70	88.05 (9)
N1—Cu1—N20	164.30 (9)	N51—Cu51—N70	164.41 (9)
O1—Cu1—N11	99.84 (9)	O51—Cu51—N61	101.03 (9)
N1—Cu1—N11	114.33 (9)	N51—Cu51—N61	113.83 (9)
N20—Cu1—N11	78.95 (9)	N70—Cu51—N61	78.85 (9)
O1—Cu1—Cl1	161.53 (7)	O51—Cu51—Cl51	159.83 (7)
N1—Cu1—Cl1	94.83 (7)	N51—Cu51—Cl51	94.72 (7)
N20—Cu1—Cl1	91.24 (7)	N70—Cu51—Cl51	92.06 (7)
N11—Cu1—Cl1	98.27 (6)	N61—Cu51—Cl51	98.78 (6)
C1—O1—Cu1	117.69 (18)	C51—O51—Cu51	117.88 (19)
C2—N1—C10	120.5 (3)	C52—N51—C60	120.8 (3)
C2—N1—Cu1	113.83 (19)	C52—N51—Cu51	113.27 (19)
C10—N1—Cu1	125.0 (2)	C60—N51—Cu51	125.5 (2)
O2—C1—O1	125.4 (3)	O52—C51—O51	125.5 (3)
O2—C1—C2	120.7 (3)	O52—C51—C52	120.3 (3)
O1—C1—C2	113.9 (2)	O51—C51—C52	114.2 (3)
N1—C2—C3	122.0 (3)	N51—C52—C53	121.7 (3)
N1—C2—C1	112.8 (2)	N51—C52—C51	113.0 (3)
C3—C2—C1	125.2 (3)	C53—C52—C51	125.2 (3)
C4—C3—C2	124.5 (3)	C54—C53—C58	118.9 (3)
C4—C3—C8	118.6 (3)	C54—C53—C52	124.0 (3)
C2—C3—C8	116.9 (3)	C58—C53—C52	117.1 (3)
C5—C4—C3	119.9 (3)	C55—C54—C53	119.9 (3)
C4—C5—C6	121.2 (3)	C54—C55—C56	120.6 (3)
C7—C6—C5	120.7 (3)	C57—C56—C55	121.2 (3)
C6—C7—C8	120.1 (3)	C56—C57—C58	119.9 (3)
C9—C8—C7	121.8 (3)	C59—C58—C53	118.8 (3)
C9—C8—C3	118.7 (3)	C59—C58—C57	121.8 (3)
C7—C8—C3	119.5 (3)	C53—C58—C57	119.4 (3)
C10—C9—C8	120.1 (3)	C60—C59—C58	120.4 (3)
C9—C10—N1	121.7 (3)	N51—C60—C59	121.2 (3)
C12—N11—C24	118.6 (2)	C62—N61—C74	118.3 (2)
C12—N11—Cu1	131.60 (19)	C62—N61—Cu51	131.70 (19)
C24—N11—Cu1	109.65 (17)	C74—N61—Cu51	109.84 (18)
N11—C12—C13	121.4 (3)	N61—C62—C63	121.4 (3)
N11—C12—C25	117.4 (2)	N61—C62—C75	117.5 (3)
C13—C12—C25	121.2 (3)	C63—C62—C75	121.2 (3)
C14—C13—C12	120.4 (3)	C64—C63—C62	120.4 (3)
C13—C14—C23	119.4 (3)	C63—C64—C73	120.0 (3)
C16—C15—C23	121.0 (3)	C66—C65—C73	121.0 (3)
C15—C16—C22	121.2 (3)	C65—C66—C72	121.5 (3)
C18—C17—C22	120.2 (3)	C68—C67—C72	120.1 (3)
C17—C18—C19	120.1 (3)	C67—C68—C69	120.0 (3)
N20—C19—C18	120.7 (3)	N70—C69—C68	120.9 (3)
N20—C19—C26	117.4 (3)	N70—C69—C76	117.6 (3)
C18—C19—C26	121.8 (3)	C68—C69—C76	121.5 (3)
C19—N20—C21	120.2 (2)	C69—N70—C71	119.9 (2)
C19—N20—Cu1	124.3 (2)	C69—N70—Cu51	124.4 (2)
C21—N20—Cu1	115.52 (18)	C71—N70—Cu51	115.66 (18)
N20—C21—C22	121.8 (3)	N70—C71—C72	121.9 (3)
N20—C21—C24	118.4 (2)	N70—C71—C74	118.5 (2)
C22—C21—C24	119.8 (3)	C72—C71—C74	119.6 (3)
C17—C22—C21	117.1 (3)	C67—C72—C71	117.1 (3)
C17—C22—C16	123.8 (3)	C67—C72—C66	123.9 (3)
C21—C22—C16	119.1 (3)	C71—C72—C66	119.0 (3)
C24—C23—C14	117.4 (3)	C64—C73—C74	116.6 (3)
C24—C23—C15	119.1 (3)	C64—C73—C65	124.1 (3)
C14—C23—C15	123.5 (3)	C74—C73—C65	119.3 (3)
N11—C24—C23	122.9 (3)	N61—C74—C73	123.3 (3)
N11—C24—C21	117.4 (2)	N61—C74—C71	117.1 (2)
C23—C24—C21	119.7 (3)	C73—C74—C71	119.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O2	0.95	2.24	2.890 (4)	124
C54—H54···O52	0.95	2.22	2.866 (4)	124
C10—H10···Cl1	0.95	2.72	3.233 (3)	114
C60—H60···Cl51	0.95	2.76	3.264 (3)	114
C25—H253···O2^i	0.98	2.46	3.424 (4)	169
C15—H15···O52^ii	0.95	2.47	3.409 (4)	172

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