Bis[4,5-dimethyl-2-(2-pyrid­yl)-1H-imidazole-κ²N²,N³](1H-imidazole-κN³)copper(II) bis­(perchlorate)

In the title complex, [Cu(C₃H₄N₂)(C₁₀H₁₁N₃)₂](ClO₄)₂, the Cu^II cation has a distorted trigonal-bipyramidal geometry defined by a CuN₂N′₂N′′ donor set. The imidazole ligand is disordered over two orientations of equal occupancy. Two of the perchlorate ion sites are located on a twofold rotation axis, and one of is disordered over two sites of equal occupancy. In the crystal structure there is a two-dimensional infinite network of hydrogen-bonded mol­ecules parallel to the ab plane.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• Disorder in main residue
• R factor = 0.049
• wR factor = 0.117
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT301_ALERT_3_C Main Residue  Disorder .........................      14.00 Perc.
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C9
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C10
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C19
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C20
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Labels ..........          1

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.99
           From the CIF: _reflns_number_total               5775
           Count of symmetry unique reflns         3342
           Completeness (_total/calc)            172.80%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      2433
           Fraction of Friedel pairs measured     0.728
           Are heavy atom types Z>Si present        yes
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT302_ALERT_4_G Anion/Solvent Disorder .........................      21.00 Perc.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   1 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
   1 ALERT type 3 Indicator that the structure quality may be low
   7 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Imidazole is ubiquitous in biology and chemistry. It is therefore of interest to synthesize ligands containing imidazole and related heterocyclic system (Tan et al., 1997; Kapinos et al., 1998; Matthews et al., 1998). Imidazole and its derivatives are an important class of heterocycle with N-donor atoms, therefore the investigation of mixed-ligand complexes of a variety of transitional metal ions with imidazole and its derivatives has attracted considerable interest in recent years. The copper-imidazole systems have demonstrated capacities for construction of inorganic-organic hybrid supramolecular isomers (Huang et al., 2004; Huang et al., 2005), and also have profound effects on functions in biological systems (Holm et al., 1996). We report here the crystal structure of the title compound, a mixed-ligand Cu^II complex.

The crystal structure of the title compound contains distorted Cu^II complexes in which individual Cu centres exist in a CuN₂N'₂N'' donor set that defines a distorted trigonal bipyramid geometry. The two N atoms of pyridyl rings and the N atom of imidazole coordinate in a plane around the Cu atom. The N atoms of the two imidazole rings distribute in the axial positions; the Cu1—N2 distance is 1.990 (3) Å. The imidazole ligand is not a ordered system, and the imidazole ring is disordered over two orientations. Two of the perchlorate ion sites (containing Cl1 and Cl2) are located on a twofold rotation axis, and one of these (containing Cl1) displays disorder.

The N3 atom of 4,5-dimethyl-2-(2-pyridyl)imidazole form two hydrogen bonds with the O atom of perchlorate. The N6 atom and N8 atom also each form a hydrogen bond with the O atom of perchlorate; details are presented in Table 2. A two-dimensional infinite network of hydrogen-bonded molecules is present in the structure, running parallel to the ab-plane.

Related literature

For related literature, see: Holm et al. (1996); Huang et al. (2004); Huang et al. (2005); Kapinos et al. (1998); Matthews et al. (1998); Tan et al. (1997).

S2. Experimental

The title complex was synthesized by the reaction of 4,5-dimethyl-2- (2-pyridyl)imidazole (0.52 g, 3.0 mmol) and imidazole (0.10 g, 1.5 mmol) with copper(II) perchlorate (0.50 g, 1.5 mmol) dissolved in the methanol (20 ml). Single crystals of (I) suitable for X-ray diffraction were obtained by evaporation of the methanol solution at room temperature.

S3. Refinement

All H atoms were allowed to ride on their parent atoms at distances of 0.96Å (methyl H), 0.93Å (pyridyl H), 0.93Å (imidazole H) and 0.86Å (N—H imidazole), and with U_iso(H) values of 1.2–1.5 times U_eq of the parent atom.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: CrystalClear (Rigaku, 2005); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The molecular structure of the complex in (I), showing the atomic labelling. Displacement ellipsoids are shown at the 50% probability level. H atoms, counter ions and one disorder component have been omitted for clarity.

Bis[4,5-dimethyl-2-(2-pyridyl)-1H-imidazole-κ²N²,N³](1H- imidazole-κN³)copper(II) bis(perchlorate)

Crystal data

[Cu(C3H4N2)(C10H11N3)2](ClO4)2	Dx = 1.532 Mg m^−3
Mr = 676.96	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P41212	Cell parameters from 8320 reflections
Hall symbol: P 4abw 2nw	θ = 2.5–23.8°
a = 14.6374 (5) Å	µ = 0.99 mm^−1
c = 27.3945 (14) Å	T = 293 K
V = 5869.4 (4) Å^3	Bipyramid, green
Z = 8	0.32 × 0.26 × 0.24 mm
F(000) = 2776

Data collection

Bruker SMART APEX CCD area-detector diffractometer	5775 independent reflections
Radiation source: sealed tube	5315 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
ϕ and ω scans	θmax = 26.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −18→14
Tmin = 0.74, Tmax = 0.79	k = −18→18
32170 measured reflections	l = −33→27

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.048	H-atom parameters constrained
wR(F^2) = 0.117	w = 1/[σ^2(Fo^2) + (0.049P)^2 + 5.1204P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
5775 reflections	Δρmax = 0.54 e Å^−3
410 parameters	Δρmin = −0.64 e Å^−3
0 restraints	Absolute structure: Flack (1983), 2433 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.013 (17)

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.49074 (3)	0.81891 (3)	0.002420 (17)	0.04289 (13)
C1	0.5381 (3)	0.7035 (3)	−0.09104 (15)	0.0491 (10)
H1A	0.5698	0.7544	−0.1023	0.059*
C2	0.5351 (3)	0.6266 (3)	−0.12011 (16)	0.0560 (11)
H2A	0.5649	0.6258	−0.1501	0.067*
C3	0.4875 (3)	0.5508 (3)	−0.10421 (17)	0.0590 (12)
H3B	0.4848	0.4985	−0.1234	0.071*
C4	0.4438 (3)	0.5534 (3)	−0.05947 (17)	0.0547 (10)
H4A	0.4104	0.5037	−0.0482	0.066*
C5	0.4516 (3)	0.6338 (3)	−0.03163 (14)	0.0406 (8)
C6	0.4098 (3)	0.6474 (3)	0.01525 (14)	0.0434 (9)
C7	0.3344 (3)	0.6321 (3)	0.08455 (16)	0.0555 (11)
C8	0.3702 (3)	0.7184 (3)	0.08219 (16)	0.0531 (11)
C9	0.2772 (4)	0.5869 (4)	0.1227 (2)	0.0822 (17)
H9A	0.2638	0.5254	0.1128	0.123*
H9B	0.2213	0.6202	0.1267	0.123*
H9C	0.3099	0.5859	0.1531	0.123*
C10	0.3611 (5)	0.7958 (5)	0.1173 (2)	0.0863 (19)
H10A	0.3258	0.7764	0.1450	0.129*
H10B	0.3309	0.8460	0.1016	0.129*
H10C	0.4206	0.8147	0.1280	0.129*
C11	0.6139 (3)	0.7685 (3)	0.09316 (16)	0.0532 (11)
H11A	0.5641	0.7359	0.1051	0.064*
C12	0.6937 (3)	0.7703 (3)	0.12029 (17)	0.0557 (11)
H12A	0.6976	0.7394	0.1499	0.067*
C13	0.7668 (3)	0.8185 (3)	0.10272 (17)	0.0579 (12)
H13A	0.8209	0.8210	0.1205	0.070*
C14	0.7602 (3)	0.8632 (3)	0.05894 (17)	0.0551 (11)
H14A	0.8098	0.8950	0.0462	0.066*
C15	0.6777 (3)	0.8597 (2)	0.03390 (15)	0.0412 (8)
C16	0.6608 (2)	0.9028 (2)	−0.01296 (14)	0.0383 (8)
C17	0.6694 (3)	0.9807 (3)	−0.08144 (15)	0.0502 (9)
C18	0.5849 (3)	0.9440 (3)	−0.07755 (15)	0.0479 (10)
C19	0.7111 (4)	1.0404 (4)	−0.1201 (2)	0.0766 (16)
H19A	0.6671	1.0515	−0.1454	0.115*
H19B	0.7636	1.0104	−0.1338	0.115*
H19C	0.7294	1.0975	−0.1059	0.115*
C20	0.5027 (4)	0.9551 (4)	−0.1099 (2)	0.0757 (16)
H20A	0.5189	0.9907	−0.1380	0.114*
H20B	0.4550	0.9856	−0.0921	0.114*
H20C	0.4815	0.8961	−0.1201	0.114*
C21	0.4109 (4)	1.0078 (3)	0.0069 (2)	0.0658 (13)	0.50
H21A	0.4679	1.0357	0.0090	0.079*	0.50
C22	0.2631 (3)	0.9850 (4)	0.0016 (2)	0.075 (5)	0.50
H22A	0.2004	0.9950	−0.0001	0.090*	0.50
N8	0.3313 (4)	1.0509 (4)	0.00487 (19)	0.069 (3)	0.50
H8A	0.3233	1.1091	0.0055	0.083*	0.50
C23	0.3044 (3)	0.9069 (5)	0.0015 (2)	0.0707 (14)	0.50
H23A	0.2751	0.8507	−0.0010	0.085*	0.50
N7	0.3958 (2)	0.9177 (2)	0.00537 (13)	0.0492 (8)	0.50
C23'	0.4109 (4)	1.0078 (3)	0.0069 (2)	0.0658 (13)	0.50
H21B	0.4679	1.0357	0.0090	0.079*	0.50
N8'	0.2631 (3)	0.9850 (4)	0.0016 (2)	0.075 (3)	0.50
H8'A	0.2051	0.9942	0.0000	0.090*	0.50
N7'	0.3958 (2)	0.9177 (2)	0.00537 (13)	0.0492 (8)	0.50
C21'	0.3044 (3)	0.9069 (5)	0.0015 (2)	0.0707 (14)	0.50
H23B	0.2751	0.8507	−0.0010	0.085*	0.50
C22'	0.3313 (4)	1.0509 (4)	0.00487 (19)	0.069 (3)	0.50
H22B	0.3226	1.1138	0.0055	0.083*	0.50
N1	0.4977 (2)	0.7080 (2)	−0.04776 (12)	0.0412 (7)
N2	0.4179 (2)	0.7263 (2)	0.03865 (12)	0.0463 (8)
N3	0.3601 (2)	0.5891 (2)	0.04254 (14)	0.0514 (9)
H3A	0.3468	0.5338	0.0347	0.062*
N4	0.6058 (2)	0.8120 (2)	0.05027 (12)	0.0420 (7)
N5	0.5794 (2)	0.8946 (2)	−0.03395 (12)	0.0419 (7)
N6	0.7161 (2)	0.9535 (2)	−0.04085 (13)	0.0481 (8)
H6	0.7720	0.9668	−0.0343	0.058*
Cl1	0.32257 (8)	0.32257 (8)	0.0000	0.0702 (5)
O11	0.2532 (6)	0.2691 (6)	−0.0184 (2)	0.081 (3)	0.50
O12	0.2849 (7)	0.4105 (5)	0.0068 (4)	0.084 (2)	0.50
O13	0.3603 (6)	0.2882 (6)	0.0403 (3)	0.089 (3)	0.50
O14	0.3877 (6)	0.3325 (6)	−0.0371 (3)	0.080 (2)	0.50
Cl2	0.99578 (7)	0.99578 (7)	0.0000	0.0583 (4)
O21	0.9987 (3)	0.9145 (2)	0.02515 (14)	0.0775 (11)
O22	1.0050 (3)	1.0666 (3)	0.03420 (14)	0.0815 (12)
Cl3	0.66607 (8)	0.15608 (7)	0.02360 (4)	0.0550 (3)
O31	0.7316 (3)	0.1668 (3)	−0.01093 (13)	0.0798 (12)
O32	0.6524 (3)	0.2387 (3)	0.04837 (15)	0.0804 (12)
O33	0.6871 (3)	0.0867 (3)	0.05352 (15)	0.0864 (13)
O34	0.5931 (3)	0.1353 (3)	−0.00339 (17)	0.0867 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0378 (2)	0.0426 (3)	0.0483 (2)	−0.00376 (19)	0.0047 (2)	0.0029 (2)
C1	0.043 (2)	0.059 (3)	0.046 (2)	−0.0063 (19)	0.0089 (18)	0.0013 (19)
C2	0.050 (3)	0.074 (3)	0.044 (2)	0.003 (2)	0.0059 (19)	−0.011 (2)
C3	0.069 (3)	0.054 (3)	0.054 (3)	0.003 (2)	−0.006 (2)	−0.015 (2)
C4	0.056 (3)	0.045 (2)	0.063 (3)	−0.0016 (19)	0.001 (2)	−0.010 (2)
C5	0.0354 (19)	0.046 (2)	0.041 (2)	−0.0006 (16)	−0.0021 (16)	−0.0004 (17)
C6	0.041 (2)	0.046 (2)	0.043 (2)	−0.0021 (17)	0.0036 (17)	0.0039 (17)
C7	0.049 (2)	0.063 (3)	0.055 (2)	−0.003 (2)	0.005 (2)	0.011 (2)
C8	0.048 (2)	0.066 (3)	0.046 (2)	−0.006 (2)	0.0104 (19)	0.002 (2)
C9	0.084 (4)	0.086 (4)	0.077 (4)	−0.002 (3)	0.033 (3)	0.025 (3)
C10	0.099 (5)	0.092 (4)	0.068 (3)	−0.016 (4)	0.025 (3)	−0.022 (3)
C11	0.059 (3)	0.047 (2)	0.054 (3)	−0.007 (2)	−0.007 (2)	0.014 (2)
C12	0.061 (3)	0.049 (2)	0.057 (3)	−0.001 (2)	−0.015 (2)	0.006 (2)
C13	0.061 (3)	0.054 (3)	0.059 (3)	0.007 (2)	−0.023 (2)	−0.004 (2)
C14	0.043 (2)	0.057 (3)	0.066 (3)	−0.0044 (19)	−0.005 (2)	−0.006 (2)
C15	0.040 (2)	0.0344 (18)	0.049 (2)	−0.0007 (16)	−0.0077 (17)	−0.0044 (16)
C16	0.0306 (18)	0.0389 (19)	0.045 (2)	−0.0029 (15)	0.0010 (15)	0.0024 (16)
C17	0.055 (2)	0.046 (2)	0.050 (2)	0.0019 (19)	0.0063 (19)	0.0026 (18)
C18	0.047 (2)	0.049 (2)	0.048 (2)	0.0022 (18)	0.0001 (18)	0.0077 (18)
C19	0.065 (3)	0.079 (4)	0.086 (4)	−0.009 (3)	0.021 (3)	0.025 (3)
C20	0.072 (3)	0.095 (4)	0.060 (3)	0.003 (3)	−0.010 (3)	0.025 (3)
C21	0.083 (4)	0.044 (2)	0.071 (3)	−0.003 (2)	0.005 (3)	0.005 (2)
C22	0.055 (9)	0.089 (11)	0.081 (8)	0.02 (11)	0.01 (11)	0.02 (13)
N8	0.070 (7)	0.068 (7)	0.070 (6)	0.02 (10)	0.01 (9)	0.02 (9)
C23	0.046 (3)	0.095 (4)	0.071 (3)	−0.006 (3)	0.008 (3)	−0.011 (3)
N7	0.0397 (18)	0.0479 (19)	0.060 (2)	0.0012 (14)	−0.0002 (17)	−0.0015 (17)
C23'	0.083 (4)	0.044 (2)	0.071 (3)	−0.003 (2)	0.005 (3)	0.005 (2)
N8'	0.055 (6)	0.089 (6)	0.081 (3)	0.02 (10)	0.01 (9)	0.02 (11)
N7'	0.0397 (18)	0.0479 (19)	0.060 (2)	0.0012 (14)	−0.0002 (17)	−0.0015 (17)
C21'	0.046 (3)	0.095 (4)	0.071 (3)	−0.006 (3)	0.008 (3)	−0.011 (3)
C22'	0.070 (6)	0.068 (6)	0.070 (3)	0.02 (11)	0.01 (11)	0.02 (10)
N1	0.0327 (16)	0.0462 (18)	0.0449 (17)	−0.0019 (14)	0.0006 (14)	−0.0035 (14)
N2	0.0441 (19)	0.051 (2)	0.0436 (17)	−0.0092 (15)	0.0047 (15)	−0.0012 (16)
N3	0.050 (2)	0.0419 (18)	0.062 (2)	−0.0091 (15)	0.0039 (17)	0.0088 (17)
N4	0.0422 (17)	0.0372 (17)	0.0465 (18)	−0.0048 (14)	−0.0034 (14)	0.0044 (14)
N5	0.0346 (16)	0.0450 (18)	0.0460 (17)	−0.0004 (13)	0.0029 (14)	0.0051 (14)
N6	0.0363 (17)	0.049 (2)	0.059 (2)	−0.0059 (14)	−0.0003 (16)	0.0036 (16)
Cl1	0.0593 (6)	0.0593 (6)	0.0920 (13)	−0.0108 (8)	−0.0109 (8)	0.0109 (8)
O11	0.078 (6)	0.075 (5)	0.090 (6)	−0.035 (4)	0.034 (5)	−0.009 (5)
O12	0.102 (6)	0.052 (4)	0.098 (6)	−0.019 (4)	0.015 (6)	−0.027 (5)
O13	0.099 (6)	0.096 (6)	0.072 (5)	−0.050 (5)	−0.016 (5)	0.027 (4)
O14	0.095 (6)	0.074 (5)	0.072 (5)	−0.019 (5)	0.031 (5)	−0.014 (4)
Cl2	0.0531 (5)	0.0531 (5)	0.0686 (9)	−0.0092 (6)	0.0084 (6)	−0.0084 (6)
O21	0.094 (3)	0.0521 (19)	0.087 (2)	−0.0083 (19)	−0.043 (2)	0.0116 (18)
O22	0.093 (3)	0.074 (2)	0.078 (2)	−0.033 (2)	0.039 (2)	−0.0269 (19)
Cl3	0.0676 (7)	0.0422 (5)	0.0552 (6)	−0.0112 (5)	−0.0081 (5)	−0.0014 (4)
O31	0.072 (2)	0.097 (3)	0.070 (2)	−0.031 (2)	0.0292 (18)	−0.037 (2)
O32	0.078 (2)	0.064 (2)	0.099 (3)	0.0249 (19)	−0.039 (2)	−0.028 (2)
O33	0.085 (3)	0.083 (3)	0.092 (3)	0.039 (2)	−0.035 (2)	0.013 (2)
O34	0.095 (3)	0.065 (2)	0.101 (3)	−0.016 (2)	−0.024 (2)	−0.024 (2)

Geometric parameters (Å, º)

Cu1—N5	1.977 (3)	C18—N5	1.398 (5)
Cu1—N2	1.990 (3)	C18—C20	1.503 (7)
Cu1—N7	2.007 (3)	C19—H19A	0.9600
Cu1—N1	2.129 (3)	C19—H19B	0.9600
Cu1—N4	2.137 (3)	C19—H19C	0.9600
C1—N1	1.327 (5)	C20—H20A	0.9600
C1—C2	1.380 (6)	C20—H20B	0.9600
C1—H1A	0.9300	C20—H20C	0.9600
C2—C3	1.380 (7)	C21—N8	1.326 (7)
C2—H2A	0.9300	C21—N7	1.338 (6)
C3—C4	1.383 (7)	C21—H21A	0.9300
C3—H3B	0.9300	C22—C23	1.293 (8)
C4—C5	1.407 (6)	C22—N8	1.392 (8)
C4—H4A	0.9300	C22—H22A	0.9300
C5—N1	1.352 (5)	N8—H8A	0.8600
C5—C6	1.437 (5)	C23—N7	1.352 (6)
C6—N2	1.326 (5)	C23—H23A	0.9300
C6—N3	1.347 (5)	N3—H3A	0.8600
C7—N3	1.364 (6)	N6—H6	0.8600
C7—C8	1.369 (6)	Cl1—O13	1.334 (8)
C7—C9	1.493 (6)	Cl1—O13^i	1.334 (8)
C8—N2	1.386 (5)	Cl1—O11^i	1.378 (7)
C8—C10	1.492 (7)	Cl1—O11	1.378 (7)
C9—H9A	0.9600	Cl1—O14^i	1.401 (8)
C9—H9B	0.9600	Cl1—O14	1.401 (8)
C9—H9C	0.9600	Cl1—O12	1.413 (8)
C10—H10A	0.9600	Cl1—O12^i	1.413 (8)
C10—H10B	0.9600	O11—O11^i	1.060 (15)
C10—H10C	0.9600	O11—O13^i	1.551 (10)
C11—N4	1.342 (5)	O12—O14^i	1.135 (11)
C11—C12	1.385 (6)	O12—O13^i	1.486 (11)
C11—H11A	0.9300	O13—O12^i	1.486 (11)
C12—C13	1.369 (7)	O13—O14^i	1.515 (13)
C12—H12A	0.9300	O13—O11^i	1.551 (10)
C13—C14	1.369 (6)	O14—O12^i	1.135 (11)
C13—H13A	0.9300	O14—O13^i	1.515 (13)
C14—C15	1.391 (6)	Cl2—O21^i	1.375 (3)
C14—H14A	0.9300	Cl2—O21	1.375 (3)
C15—N4	1.340 (5)	Cl2—O22	1.403 (3)
C15—C16	1.452 (5)	Cl2—O22^i	1.403 (3)
C16—N5	1.327 (5)	Cl3—O34	1.334 (4)
C16—N6	1.338 (5)	Cl3—O33	1.341 (4)
C17—C18	1.353 (6)	Cl3—O31	1.356 (3)
C17—N6	1.365 (5)	Cl3—O32	1.402 (4)
C17—C19	1.504 (6)
N5—Cu1—N2	170.20 (15)	C23—C22—N8	106.1 (4)
N5—Cu1—N7	94.06 (14)	C23—C22—H22A	127.0
N2—Cu1—N7	95.74 (15)	N8—C22—H22A	127.0
N5—Cu1—N1	94.06 (13)	C21—N8—C22	107.7 (5)
N2—Cu1—N1	80.10 (13)	C21—N8—H8A	126.2
N7—Cu1—N1	127.46 (14)	C22—N8—H8A	126.2
N5—Cu1—N4	79.52 (13)	C22—C23—N7	111.1 (5)
N2—Cu1—N4	94.82 (13)	C22—C23—H23A	124.4
N7—Cu1—N4	123.73 (14)	N7—C23—H23A	124.4
N1—Cu1—N4	108.79 (13)	C21—N7—C23	106.3 (4)
N1—C1—C2	122.9 (4)	C21—N7—Cu1	126.7 (3)
N1—C1—H1A	118.6	C23—N7—Cu1	126.7 (4)
C2—C1—H1A	118.6	C1—N1—C5	118.3 (3)
C1—C2—C3	119.3 (4)	C1—N1—Cu1	129.5 (3)
C1—C2—H2A	120.4	C5—N1—Cu1	112.2 (2)
C3—C2—H2A	120.4	C6—N2—C8	107.4 (3)
C2—C3—C4	119.4 (4)	C6—N2—Cu1	113.6 (3)
C2—C3—H3B	120.3	C8—N2—Cu1	139.0 (3)
C4—C3—H3B	120.3	C6—N3—C7	109.0 (4)
C3—C4—C5	117.8 (4)	C6—N3—H3A	125.5
C3—C4—H4A	121.1	C7—N3—H3A	125.5
C5—C4—H4A	121.1	C15—N4—C11	118.1 (4)
N1—C5—C4	122.4 (4)	C15—N4—Cu1	112.9 (3)
N1—C5—C6	113.2 (3)	C11—N4—Cu1	129.0 (3)
C4—C5—C6	124.4 (4)	C16—N5—C18	105.8 (3)
N2—C6—N3	109.3 (4)	C16—N5—Cu1	114.9 (3)
N2—C6—C5	120.9 (4)	C18—N5—Cu1	139.2 (3)
N3—C6—C5	129.7 (4)	C16—N6—C17	108.8 (3)
N3—C7—C8	106.2 (4)	C16—N6—H6	125.6
N3—C7—C9	122.7 (4)	C17—N6—H6	125.6
C8—C7—C9	131.0 (5)	O13—Cl1—O13^i	177.0 (6)
C7—C8—N2	108.1 (4)	O13—Cl1—O11^i	69.8 (5)
C7—C8—C10	129.4 (4)	O13^i—Cl1—O11^i	113.2 (5)
N2—C8—C10	122.5 (4)	O13—Cl1—O11	113.2 (5)
C7—C9—H9A	109.5	O13^i—Cl1—O11	69.8 (5)
C7—C9—H9B	109.5	O11^i—Cl1—O11	45.3 (6)
H9A—C9—H9B	109.5	O13—Cl1—O14^i	67.2 (6)
C7—C9—H9C	109.5	O13^i—Cl1—O14^i	111.0 (6)
H9A—C9—H9C	109.5	O11^i—Cl1—O14^i	107.1 (5)
H9B—C9—H9C	109.5	O11—Cl1—O14^i	136.7 (5)
C8—C10—H10A	109.5	O13—Cl1—O14	111.0 (6)
C8—C10—H10B	109.5	O13^i—Cl1—O14	67.2 (6)
H10A—C10—H10B	109.5	O11^i—Cl1—O14	136.7 (5)
C8—C10—H10C	109.5	O11—Cl1—O14	107.1 (5)
H10A—C10—H10C	109.5	O14^i—Cl1—O14	112.7 (7)
H10B—C10—H10C	109.5	O13—Cl1—O12	113.4 (6)
N4—C11—C12	122.3 (4)	O13^i—Cl1—O12	65.4 (6)
N4—C11—H11A	118.8	O11^i—Cl1—O12	113.7 (6)
C12—C11—H11A	118.8	O11—Cl1—O12	106.2 (6)
C13—C12—C11	118.7 (4)	O14^i—Cl1—O12	47.6 (5)
C13—C12—H12A	120.6	O14—Cl1—O12	105.5 (5)
C11—C12—H12A	120.6	O13—Cl1—O12^i	65.4 (6)
C12—C13—C14	119.9 (4)	O13^i—Cl1—O12^i	113.4 (6)
C12—C13—H13A	120.0	O11^i—Cl1—O12^i	106.2 (6)
C14—C13—H13A	120.0	O11—Cl1—O12^i	113.7 (6)
C13—C14—C15	118.4 (4)	O14^i—Cl1—O12^i	105.5 (5)
C13—C14—H14A	120.8	O14—Cl1—O12^i	47.6 (5)
C15—C14—H14A	120.8	O12—Cl1—O12^i	136.7 (7)
N4—C15—C14	122.4 (4)	O11^i—O11—Cl1	67.4 (3)
N4—C15—C16	112.9 (3)	O11^i—O11—O13^i	119.0 (5)
C14—C15—C16	124.6 (4)	Cl1—O11—O13^i	53.8 (4)
N5—C16—N6	110.2 (3)	O14^i—O12—Cl1	65.7 (6)
N5—C16—C15	119.8 (3)	O14^i—O12—O13^i	118.1 (9)
N6—C16—C15	130.0 (4)	Cl1—O12—O13^i	54.7 (4)
C18—C17—N6	106.2 (4)	Cl1—O13—O12^i	59.8 (5)
C18—C17—C19	131.2 (4)	Cl1—O13—O14^i	58.5 (5)
N6—C17—C19	122.6 (4)	O12^i—O13—O14^i	96.5 (6)
C17—C18—N5	108.9 (4)	Cl1—O13—O11^i	56.4 (4)
C17—C18—C20	130.0 (4)	O12^i—O13—O11^i	94.5 (6)
N5—C18—C20	120.9 (4)	O14^i—O13—O11^i	93.6 (7)
C17—C19—H19A	109.5	O12^i—O14—Cl1	66.7 (6)
C17—C19—H19B	109.5	O12^i—O14—O13^i	119.4 (8)
H19A—C19—H19B	109.5	Cl1—O14—O13^i	54.3 (4)
C17—C19—H19C	109.5	O21^i—Cl2—O21	107.7 (3)
H19A—C19—H19C	109.5	O21^i—Cl2—O22	113.3 (3)
H19B—C19—H19C	109.5	O21—Cl2—O22	107.5 (2)
C18—C20—H20A	109.5	O21^i—Cl2—O22^i	107.5 (2)
C18—C20—H20B	109.5	O21—Cl2—O22^i	113.3 (3)
H20A—C20—H20B	109.5	O22—Cl2—O22^i	107.7 (3)
C18—C20—H20C	109.5	O34—Cl3—O33	110.5 (3)
H20A—C20—H20C	109.5	O34—Cl3—O31	101.9 (3)
H20B—C20—H20C	109.5	O33—Cl3—O31	110.6 (3)
N8—C21—N7	108.8 (5)	O34—Cl3—O32	110.5 (2)
N8—C21—H21A	125.6	O33—Cl3—O32	113.0 (3)
N7—C21—H21A	125.6	O31—Cl3—O32	109.8 (3)

Symmetry code: (i) y, x, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O12	0.86	2.16	3.001 (8)	166
N3—H3A···O14^i	0.86	2.15	2.980 (10)	162
N6—H6···O21^i	0.86	2.15	3.009 (5)	175

Symmetry code: (i) y, x, −z.