[N-(2-Aminoethyl)-N-(2-{(E)-[9-(di­ethoxy­methyl)-1,10-phenanthrolin-2-yl]­methyl­ideneamino}eth­yl)ethane-1,2-diamine]­copper(II) bis(perchlorate)

In the title compound, [Cu(C₂₄H₃₄N₆O₂)](ClO₄)₂, the copper(II) coordination geometry is intermediate between square-based-pyramidal and trigonal-bipyramidal. The H atoms of the sixth non-metal-coordinating nitro­gen donor engage in intra­molecular hydrogen bonding with the eth­oxy O atom and the uncoordinated phenanthroline N atom. Hydrogen bonding is also observed between the NH₂ H atoms and two of the phenanthroline H atoms with the perchlorate anions.

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](C-C) = 0.011 Å
• R factor = 0.074
• wR factor = 0.255
• Data-to-parameter ratio = 13.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT222_ALERT_3_B Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.53 Ratio

Alert level C
RFACR01_ALERT_3_C  The value of the weighted R factor is > 0.25
            Weighted R factor given   0.255
PLAT084_ALERT_2_C High R2 Value ..................................       0.26
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       3.06
PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct...          2
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.18 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C17    -   C18     ..       5.65 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        O10
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl1
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl2
PLAT245_ALERT_2_C U(iso) H2      Smaller than U(eq) C2      by ...       0.02 AngSq
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         11
PLAT360_ALERT_2_C Short  C(sp3)-C(sp3) Bond  C13    -   C14    ...       1.36 Ang.

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (1)       1.19

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

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

---

S1. Comment

We have been interested for some time in the design and synthesis of novel macrocyclic and macroacyclic Schiff base compounds (Keypour et al., 2000), The title compound was obtained by the templated condensation of tris(2-aminoethyl)amine (tren) with 2,9-dicarboxaldehyde-1,10-phenathroline in the presence of copper(II) perchlorate. Assignment of the complex as an acyclic Schiff base was based on the observation of a single sharp imine band at 1644 cm^-1 in the infrared spectrum, indicating that the imine macroacycle had been formed. The solid-state structure involves a five-coordinate CuN5 chromophore constituted by one imine (N2), one phenanthroline (N1) and three amine (N3, N4, N5) N atoms of the pentadentate ligand. Additionally, the non-coordinating end of the ligand has undergone reaction with the ethanol solvent to yield the observed product. The angles of the coordination polyhedron surrounding the copper(II) centre suggest that the coordination geometry lies between square-based-pyramidal and trigonal-bipyramidal extremes. In this case, the structural index parameter (τ) can be used to identify the coordination geometry of the complex (Addison et al., 1984). τ is expressed as (β - α) /60°, where β and α correspond to two angles showing tendency to linearity and the τ values of square-based-pyramidal and trigonal-bipyramidal extremes are 0 and 1, respectively. For this complex, the N1—Cu—N3 and N2—Cu—N5 angles are 160.3 (2)° and 131.1 (2)°, respectively (table 1), giving a τ value of 0.498. This value is very close to τ = 1/2, which means approximately 50% contribution of each pyramidal form, with a slightly greater tendency toward square-based-pyramidal geometry (τ < 1/2). Consequently, the N1, N2, N3 and N5 atoms form the equatorial plane of the square-pyramid, while the N4 atom occupies the axial position (Yilmaz et al., 2003).

One of the H atoms of each of the amine groups not bonded to the copper forms intramolecular hydrogen bonds to the oxygen and the uncoordinated phenanthralene N atoms (N6), (Table 2). Hydrogen bonding is also observed between the oxygen atoms of the perchlorate anions and H(4 A), H(5 A), H(23) and H(24). In this way a network is formed.

Related literature

For related literature, see: Addison et al. (1984); Chandler et al. (1981); Keypour et al. (2000, 2007); Yilmaz et al. (2003).

S2. Experimental

Safety note: Perchlorate complexes are potentially explosive. While we have not experienced any problems with the compounds described, they should be treated with caution and handled in small quantities. All of the reagents and solvents used were of analytical grade and purchased commercially. 2,9-dicarboxyaldehyde-1,10-phenanthroline was prepared by reaction of neocuproine with selenium dioxide (Chandler et al., 1981).

The title compound was prepared based on a previous method (Keypour et al., 2007). The chloride salt of the amine(0.5 mmol) was added to a solution of 2,9-dicarboxyaldehyde-1,10-phenanthroline (0.118 g, 0.5 mmol) and CuCl₂ (0.5 mmol) in 200 ml EtOH/H₂O (3/1 ratio). A NaOH solution was added dropwise over 2–3 hr to the above solution to give a pH of 7–7.5.The resulting solution was heated for 18–24 h. The solution was reduced in volume to ca 20–30 ml, then sodium perchlorate (1 mmol) was added and precipitate was filtered. Suitable crystals were obtained by slow diffusion of diethylether vapour into the MeOH/MeCN solution of the above solid.

[CuL](ClO₄)₂.MeCN.H₂O Yield: 0.13 g (34%). analysis, calculated for C₂₉H₃₉N₇Cl₂O₁₁Cu: C 41.1, H 5.2, N 12.9%; found: C 40.8, H 5.4, N 13.3%.IR (Nujol mull, ν cm^-1): 3607, 3350, 3292, 1644 (ν_C═N imine), 1600, 1506, 1314, 1272, 1250, 1236, 1086, 934, 900, 885, 868, 721, 624, 568, 556.

S3. Refinement

All H atoms were initially located in a difference Fourier map. The methyl H atoms were then constrained to an ideal geometry with C—H distances of 0.98 Å and U_iso(H) = 1.5U_eq(C), but each group was allowed to rotate freely about its C—C bond. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances in the range 0.95–1.00 Å and U_iso(H) = 1.2U_eq(C). The R factor is slightly high because of the high vibrational amplitude associated with the perchlorate anions.

Computing details

Data collection: Collect (Nonius, 2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary size.
	Fig. 2. A representation of the intra- and intermolecular hydrogen bonding interactions present in I.

[<it>N</it>-(2-Aminoethyl)-<it>N</it>-(2-{(<it>E</it>)-[9-(diethoxymethyl)-\1,10-phenanthrolin-2-yl]methylideneamino}ethyl)ethane-1,2-diamine]copper(II) bis(perchlorate)

Crystal data

[Cu(C24H34N6O2)](ClO4)2	F(000) = 2904
Mr = 701.01	Dx = 1.531 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 11162 reflections
a = 14.1439 (3) Å	θ = 1.0–25.4°
b = 16.6060 (3) Å	µ = 0.96 mm^−1
c = 25.8952 (6) Å	T = 200 K
V = 6082.1 (2) Å^3	Prism, green
Z = 8	0.25 × 0.2 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer	5524 independent reflections
Radiation source: Enraf Nonius FR590	2925 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.076
Detector resolution: 9 pixels mm^-1	θmax = 25.3°, θmin = 3.0°
CCD rotation images, thick slices scans	h = −17→17
Absorption correction: multi-scan Blessing (1995)	k = −19→19
Tmin = 0.796, Tmax = 0.870	l = −31→31
19358 measured 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)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.256	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.153P)^2 + 0.4527P] where P = (Fo^2 + 2Fc^2)/3
5524 reflections	(Δ/σ)max = 0.003
396 parameters	Δρmax = 1.25 e Å^−3
0 restraints	Δρmin = −0.41 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.

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

	x	y	z	Uiso*/Ueq
C1	0.6258 (4)	0.4963 (4)	0.6678 (3)	0.0773 (18)
C2	0.6055 (6)	0.5122 (6)	0.7212 (3)	0.089 (2)
C3	0.5350 (6)	0.6030 (5)	0.7832 (3)	0.090 (2)
H3A	0.5824	0.5854	0.8089	0.109*
H3B	0.4722	0.5824	0.7936	0.109*
C4	0.5336 (5)	0.6947 (5)	0.7789 (3)	0.088 (2)
H4A	0.5026	0.7183	0.8096	0.106*
H4B	0.599	0.7157	0.7769	0.106*
C5	0.3769 (4)	0.7059 (5)	0.7378 (2)	0.0756 (18)
H5A	0.3498	0.7533	0.7556	0.091*
H5B	0.3653	0.6578	0.7595	0.091*
C6	0.3301 (5)	0.6952 (5)	0.6867 (3)	0.0782 (18)
H6A	0.2626	0.6815	0.6918	0.094*
H6B	0.3337	0.746	0.6668	0.094*
C7	0.5050 (5)	0.8008 (5)	0.7152 (3)	0.085 (2)
H7A	0.514	0.8343	0.7465	0.102*
H7B	0.4525	0.8243	0.6949	0.102*
C8	0.5945 (5)	0.8017 (4)	0.6833 (3)	0.084 (2)
H8A	0.6052	0.8561	0.6687	0.101*
H8B	0.6495	0.7873	0.705	0.101*
C9	0.4628 (4)	0.6876 (4)	0.5202 (3)	0.0733 (17)
C10	0.3885 (5)	0.7492 (5)	0.5363 (3)	0.081 (2)
C11	0.2258 (5)	0.7414 (5)	0.5623 (3)	0.100 (2)
H11A	0.2072	0.7625	0.528	0.121*
H11B	0.228	0.7869	0.587	0.121*
C12	0.1561 (5)	0.6799 (6)	0.5801 (4)	0.107 (3)
H12A	0.0932	0.7045	0.5824	0.161*
H12B	0.1748	0.6598	0.6142	0.161*
H12C	0.1544	0.6352	0.5555	0.161*
C13	0.4060 (10)	0.8864 (6)	0.5616 (5)	0.145 (4)
H13A	0.405	0.8946	0.5237	0.175*
H13B	0.3416	0.8979	0.5747	0.175*
C14	0.4668 (11)	0.9410 (8)	0.5827 (8)	0.211 (8)
H14A	0.4468	0.9956	0.5733	0.317*
H14B	0.5308	0.9313	0.5696	0.317*
H14C	0.4664	0.9354	0.6204	0.317*
C15	0.6083 (4)	0.5367 (4)	0.5825 (3)	0.0667 (16)
C16	0.5673 (4)	0.5878 (4)	0.5432 (2)	0.0663 (16)
C17	0.6808 (6)	0.4294 (5)	0.6533 (4)	0.096 (2)
H17	0.7009	0.3912	0.6783	0.115*
C18	0.7038 (5)	0.4207 (4)	0.6045 (4)	0.099 (3)
H18	0.744	0.3774	0.5948	0.119*
C19	0.6708 (5)	0.4735 (4)	0.5662 (3)	0.083 (2)
C20	0.6942 (5)	0.4650 (5)	0.5126 (4)	0.097 (2)
H20	0.7365	0.4235	0.5023	0.116*
C21	0.6587 (5)	0.5133 (5)	0.4773 (3)	0.091 (2)
H21	0.6777	0.5076	0.4423	0.109*
C22	0.5912 (5)	0.5748 (4)	0.4909 (3)	0.0793 (19)
C23	0.5473 (5)	0.6220 (5)	0.4538 (3)	0.087 (2)
H23	0.5624	0.6143	0.4184	0.105*
C24	0.4832 (5)	0.6790 (5)	0.4672 (3)	0.083 (2)
H24	0.4533	0.7118	0.442	0.099*
O1	0.2518 (6)	0.3662 (4)	0.7218 (3)	0.132 (2)
O2	0.3490 (6)	0.4692 (4)	0.7325 (3)	0.155 (3)
O3	0.3851 (9)	0.3810 (8)	0.6723 (3)	0.229 (6)
O4	0.2604 (6)	0.4672 (5)	0.6607 (3)	0.155 (3)
O5	0.7883 (6)	0.6157 (6)	0.6525 (3)	0.185 (4)
O6	0.7609 (5)	0.6826 (6)	0.5753 (3)	0.176 (4)
O7	0.8571 (11)	0.7340 (5)	0.6342 (3)	0.239 (7)
O8	0.9110 (8)	0.6377 (7)	0.5957 (5)	0.235 (6)
O9	0.3156 (3)	0.7038 (3)	0.55923 (17)	0.0819 (13)
O10	0.4268 (4)	0.8049 (3)	0.5714 (2)	0.0931 (14)
Cl1	0.30966 (14)	0.42004 (11)	0.69472 (7)	0.0820 (5)
Cl2	0.82578 (12)	0.66199 (12)	0.61327 (7)	0.0840 (6)
Cu1	0.52275 (5)	0.64203 (5)	0.67161 (3)	0.0631 (3)
N1	0.5886 (3)	0.5476 (3)	0.6334 (2)	0.0653 (12)
N2	0.5600 (4)	0.5739 (4)	0.7319 (2)	0.0773 (15)
N3	0.4799 (4)	0.7174 (4)	0.7308 (2)	0.0739 (14)
N4	0.3779 (3)	0.6302 (3)	0.6584 (2)	0.0654 (13)
H4C	0.3653	0.6342	0.6236	0.078*
H4D	0.3571	0.5808	0.6698	0.078*
N5	0.5829 (4)	0.7423 (3)	0.6412 (2)	0.0721 (14)
H5C	0.6408	0.7299	0.6271	0.087*
H5D	0.545	0.7631	0.6157	0.087*
N6	0.5035 (4)	0.6447 (3)	0.5569 (2)	0.0648 (13)
H2	0.628 (4)	0.476 (4)	0.743 (3)	0.07 (2)*
H10	0.363 (5)	0.777 (4)	0.511 (3)	0.08 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.063 (4)	0.063 (4)	0.105 (6)	0.005 (3)	−0.001 (4)	0.011 (4)
C2	0.084 (5)	0.085 (6)	0.097 (6)	−0.004 (4)	−0.004 (4)	0.024 (5)
C3	0.095 (5)	0.106 (6)	0.070 (4)	0.016 (4)	−0.006 (4)	0.016 (4)
C4	0.085 (5)	0.108 (6)	0.071 (4)	0.017 (4)	−0.010 (4)	−0.007 (4)
C5	0.066 (4)	0.095 (5)	0.067 (4)	0.011 (3)	0.009 (3)	−0.006 (3)
C6	0.066 (4)	0.089 (5)	0.080 (4)	0.006 (4)	0.003 (3)	0.001 (4)
C7	0.095 (5)	0.077 (5)	0.083 (5)	0.010 (4)	−0.011 (4)	−0.018 (4)
C8	0.079 (4)	0.075 (5)	0.098 (5)	−0.007 (4)	−0.009 (4)	−0.009 (4)
C9	0.070 (4)	0.077 (4)	0.073 (4)	−0.008 (3)	0.006 (3)	0.003 (4)
C10	0.076 (4)	0.085 (5)	0.083 (5)	0.013 (4)	−0.003 (4)	0.013 (4)
C11	0.076 (5)	0.107 (6)	0.118 (6)	0.025 (4)	0.007 (4)	0.021 (5)
C12	0.069 (4)	0.122 (7)	0.132 (7)	0.005 (5)	0.003 (5)	−0.006 (6)
C13	0.189 (12)	0.069 (6)	0.179 (10)	0.018 (7)	−0.042 (9)	0.015 (7)
C14	0.192 (13)	0.109 (10)	0.33 (2)	−0.023 (9)	−0.066 (14)	0.049 (12)
C15	0.051 (3)	0.054 (4)	0.096 (5)	−0.003 (3)	0.006 (3)	−0.008 (3)
C16	0.059 (3)	0.065 (4)	0.075 (4)	−0.006 (3)	0.005 (3)	−0.013 (3)
C17	0.105 (6)	0.071 (5)	0.112 (6)	0.018 (4)	0.009 (5)	−0.001 (5)
C18	0.078 (5)	0.060 (5)	0.160 (9)	0.021 (4)	−0.007 (5)	−0.011 (5)
C19	0.066 (4)	0.069 (4)	0.113 (6)	−0.003 (3)	0.003 (4)	−0.020 (4)
C20	0.087 (5)	0.078 (5)	0.126 (7)	0.006 (4)	0.022 (5)	−0.041 (5)
C21	0.076 (4)	0.104 (6)	0.093 (5)	−0.016 (4)	0.018 (4)	−0.028 (5)
C22	0.065 (4)	0.094 (5)	0.080 (5)	−0.012 (4)	0.012 (4)	−0.019 (4)
C23	0.075 (4)	0.112 (6)	0.075 (5)	−0.033 (4)	0.021 (4)	−0.018 (5)
C24	0.076 (4)	0.103 (5)	0.070 (4)	−0.013 (4)	0.004 (4)	0.009 (4)
O1	0.169 (6)	0.092 (4)	0.134 (5)	−0.038 (4)	0.036 (4)	0.016 (4)
O2	0.192 (7)	0.113 (5)	0.161 (6)	−0.054 (5)	−0.059 (5)	0.012 (5)
O3	0.230 (11)	0.331 (14)	0.126 (6)	0.134 (10)	0.080 (6)	0.052 (7)
O4	0.161 (6)	0.137 (6)	0.166 (6)	−0.010 (5)	−0.072 (5)	0.056 (5)
O5	0.178 (7)	0.261 (9)	0.116 (5)	−0.134 (7)	−0.059 (5)	0.088 (6)
O6	0.101 (4)	0.321 (11)	0.107 (4)	−0.030 (6)	−0.015 (4)	0.085 (6)
O7	0.446 (19)	0.138 (7)	0.132 (6)	−0.105 (9)	−0.090 (9)	0.024 (6)
O8	0.195 (9)	0.278 (13)	0.232 (10)	0.127 (9)	0.085 (9)	0.083 (10)
O9	0.070 (3)	0.092 (3)	0.084 (3)	0.012 (2)	0.009 (2)	0.013 (3)
O10	0.104 (3)	0.069 (3)	0.106 (4)	0.007 (3)	−0.023 (3)	−0.002 (3)
Cl1	0.1012 (13)	0.0670 (11)	0.0779 (11)	−0.0026 (9)	0.0058 (10)	0.0090 (9)
Cl2	0.0669 (10)	0.0998 (14)	0.0853 (12)	−0.0182 (9)	−0.0058 (9)	0.0140 (10)
Cu1	0.0602 (5)	0.0609 (5)	0.0682 (5)	0.0034 (3)	0.0013 (3)	0.0005 (3)
N1	0.055 (3)	0.058 (3)	0.083 (3)	−0.002 (2)	0.004 (3)	0.005 (3)
N2	0.075 (3)	0.077 (4)	0.081 (4)	0.006 (3)	0.005 (3)	0.013 (3)
N3	0.071 (3)	0.082 (4)	0.069 (3)	0.009 (3)	−0.004 (3)	−0.005 (3)
N4	0.068 (3)	0.056 (3)	0.072 (3)	0.003 (2)	0.010 (2)	0.002 (2)
N5	0.065 (3)	0.066 (3)	0.085 (4)	−0.003 (3)	0.002 (3)	−0.005 (3)
N6	0.065 (3)	0.063 (3)	0.065 (3)	−0.004 (2)	0.005 (2)	−0.001 (3)

Geometric parameters (Å, º)

C1—N1	1.340 (8)	C13—H13A	0.99
C1—C17	1.408 (10)	C13—H13B	0.99
C1—C2	1.438 (10)	C14—H14A	0.98
C2—N2	1.240 (10)	C14—H14B	0.98
C2—H2	0.89 (7)	C14—H14C	0.98
C3—N2	1.457 (9)	C15—N1	1.360 (8)
C3—C4	1.528 (12)	C15—C19	1.437 (9)
C3—H3A	0.99	C15—C16	1.445 (9)
C3—H3B	0.99	C16—N6	1.356 (8)
C4—N3	1.506 (8)	C16—C22	1.411 (9)
C4—H4A	0.99	C17—C18	1.311 (11)
C4—H4B	0.99	C17—H17	0.95
C5—N3	1.480 (8)	C18—C19	1.404 (11)
C5—C6	1.489 (9)	C18—H18	0.95
C5—H5A	0.99	C19—C20	1.434 (11)
C5—H5B	0.99	C20—C21	1.316 (11)
C6—N4	1.471 (8)	C20—H20	0.95
C6—H6A	0.99	C21—C22	1.442 (10)
C6—H6B	0.99	C21—H21	0.95
C7—N3	1.486 (10)	C22—C23	1.387 (11)
C7—C8	1.512 (10)	C23—C24	1.355 (11)
C7—H7A	0.99	C23—H23	0.95
C7—H7B	0.99	C24—H24	0.95
C8—N5	1.479 (9)	O1—Cl1	1.401 (6)
C8—H8A	0.99	O2—Cl1	1.390 (7)
C8—H8B	0.99	O3—Cl1	1.376 (9)
C9—N6	1.320 (8)	O4—Cl1	1.369 (6)
C9—C24	1.409 (10)	O5—Cl2	1.379 (6)
C9—C10	1.525 (10)	O6—Cl2	1.388 (7)
C10—O10	1.407 (9)	O7—Cl2	1.386 (8)
C10—O9	1.408 (9)	O8—Cl2	1.350 (9)
C10—H10	0.89 (7)	Cu1—N2	1.999 (6)
C11—O9	1.418 (8)	Cu1—N5	2.028 (5)
C11—C12	1.492 (12)	Cu1—N3	2.069 (5)
C11—H11A	0.99	Cu1—N1	2.074 (5)
C11—H11B	0.99	Cu1—N4	2.086 (5)
C12—H12A	0.98	N4—H4C	0.92
C12—H12B	0.98	N4—H4D	0.92
C12—H12C	0.98	N5—H5C	0.92
C13—C14	1.364 (16)	N5—H5D	0.92
C13—O10	1.408 (10)
N1—C1—C17	122.8 (8)	C19—C15—C16	118.0 (6)
N1—C1—C2	116.4 (7)	N6—C16—C22	121.1 (6)
C17—C1—C2	120.8 (8)	N6—C16—C15	119.5 (6)
N2—C2—C1	117.9 (8)	C22—C16—C15	119.3 (6)
N2—C2—H2	127 (4)	C18—C17—C1	118.8 (8)
C1—C2—H2	115 (4)	C18—C17—H17	120.6
N2—C3—C4	105.5 (6)	C1—C17—H17	120.6
N2—C3—H3A	110.6	C17—C18—C19	121.9 (7)
C4—C3—H3A	110.6	C17—C18—H18	119
N2—C3—H3B	110.6	C19—C18—H18	119
C4—C3—H3B	110.6	C18—C19—C20	123.1 (8)
H3A—C3—H3B	108.8	C18—C19—C15	117.0 (7)
N3—C4—C3	108.4 (6)	C20—C19—C15	119.9 (7)
N3—C4—H4A	110	C21—C20—C19	121.6 (7)
C3—C4—H4A	110	C21—C20—H20	119.2
N3—C4—H4B	110	C19—C20—H20	119.2
C3—C4—H4B	110	C20—C21—C22	121.0 (7)
H4A—C4—H4B	108.4	C20—C21—H21	119.5
N3—C5—C6	110.2 (5)	C22—C21—H21	119.5
N3—C5—H5A	109.6	C23—C22—C16	118.1 (6)
C6—C5—H5A	109.6	C23—C22—C21	121.8 (7)
N3—C5—H5B	109.6	C16—C22—C21	120.1 (7)
C6—C5—H5B	109.6	C24—C23—C22	121.2 (7)
H5A—C5—H5B	108.1	C24—C23—H23	119.4
N4—C6—C5	109.0 (5)	C22—C23—H23	119.4
N4—C6—H6A	109.9	C23—C24—C9	117.1 (7)
C5—C6—H6A	109.9	C23—C24—H24	121.4
N4—C6—H6B	109.9	C9—C24—H24	121.4
C5—C6—H6B	109.9	C10—O9—C11	116.4 (6)
H6A—C6—H6B	108.3	C10—O10—C13	115.7 (7)
N3—C7—C8	110.9 (6)	O4—Cl1—O3	113.1 (5)
N3—C7—H7A	109.5	O4—Cl1—O2	108.7 (5)
C8—C7—H7A	109.5	O3—Cl1—O2	105.2 (8)
N3—C7—H7B	109.5	O4—Cl1—O1	113.0 (5)
C8—C7—H7B	109.5	O3—Cl1—O1	111.3 (7)
H7A—C7—H7B	108.1	O2—Cl1—O1	104.8 (4)
N5—C8—C7	107.7 (6)	O8—Cl2—O5	115.2 (7)
N5—C8—H8A	110.2	O8—Cl2—O7	95.9 (9)
C7—C8—H8A	110.2	O5—Cl2—O7	108.4 (6)
N5—C8—H8B	110.2	O8—Cl2—O6	115.1 (6)
C7—C8—H8B	110.2	O5—Cl2—O6	113.9 (4)
H8A—C8—H8B	108.5	O7—Cl2—O6	106.0 (7)
N6—C9—C24	123.9 (7)	N2—Cu1—N5	131.1 (2)
N6—C9—C10	117.8 (6)	N2—Cu1—N3	80.9 (2)
C24—C9—C10	118.3 (7)	N5—Cu1—N3	85.0 (2)
O10—C10—O9	111.1 (6)	N2—Cu1—N1	80.0 (2)
O10—C10—C9	110.6 (6)	N5—Cu1—N1	104.3 (2)
O9—C10—C9	105.1 (6)	N3—Cu1—N1	160.3 (2)
O10—C10—H10	107 (4)	N2—Cu1—N4	109.5 (2)
O9—C10—H10	107 (4)	N5—Cu1—N4	115.2 (2)
C9—C10—H10	116 (4)	N3—Cu1—N4	83.8 (2)
O9—C11—C12	108.0 (6)	N1—Cu1—N4	106.90 (19)
O9—C11—H11A	110.1	C1—N1—C15	118.7 (5)
C12—C11—H11A	110.1	C1—N1—Cu1	109.9 (4)
O9—C11—H11B	110.1	C15—N1—Cu1	130.9 (4)
C12—C11—H11B	110.1	C2—N2—C3	127.0 (7)
H11A—C11—H11B	108.4	C2—N2—Cu1	115.5 (6)
C11—C12—H12A	109.5	C3—N2—Cu1	117.4 (5)
C11—C12—H12B	109.5	C5—N3—C7	112.8 (5)
H12A—C12—H12B	109.5	C5—N3—C4	111.3 (5)
C11—C12—H12C	109.5	C7—N3—C4	109.7 (6)
H12A—C12—H12C	109.5	C5—N3—Cu1	107.5 (4)
H12B—C12—H12C	109.5	C7—N3—Cu1	107.1 (4)
C14—C13—O10	115.8 (10)	C4—N3—Cu1	108.3 (4)
C14—C13—H13A	108.3	C6—N4—Cu1	107.5 (4)
O10—C13—H13A	108.3	C6—N4—H4C	110.2
C14—C13—H13B	108.3	Cu1—N4—H4C	110.2
O10—C13—H13B	108.3	C6—N4—H4D	110.2
H13A—C13—H13B	107.4	Cu1—N4—H4D	110.2
C13—C14—H14A	109.5	H4C—N4—H4D	108.5
C13—C14—H14B	109.5	C8—N5—Cu1	108.0 (4)
H14A—C14—H14B	109.5	C8—N5—H5C	110.1
C13—C14—H14C	109.5	Cu1—N5—H5C	110.1
H14A—C14—H14C	109.5	C8—N5—H5D	110.1
H14B—C14—H14C	109.5	Cu1—N5—H5D	110.1
N1—C15—C19	120.5 (6)	H5C—N5—H5D	108.4
N1—C15—C16	121.5 (5)	C9—N6—C16	118.6 (6)
N1—C1—C2—N2	−3.9 (10)	N4—Cu1—N1—C1	−112.0 (4)
C17—C1—C2—N2	177.0 (7)	N2—Cu1—N1—C15	−175.4 (5)
N2—C3—C4—N3	46.2 (7)	N5—Cu1—N1—C15	−45.3 (6)
N3—C5—C6—N4	53.2 (8)	N3—Cu1—N1—C15	−162.0 (6)
N3—C7—C8—N5	51.2 (8)	N4—Cu1—N1—C15	77.1 (5)
N6—C9—C10—O10	57.6 (8)	C1—C2—N2—C3	−177.4 (7)
C24—C9—C10—O10	−123.2 (7)	C1—C2—N2—Cu1	−0.3 (9)
N6—C9—C10—O9	−62.4 (8)	C4—C3—N2—C2	148.1 (7)
C24—C9—C10—O9	116.8 (7)	C4—C3—N2—Cu1	−29.0 (7)
N1—C15—C16—N6	−4.0 (8)	N5—Cu1—N2—C2	−97.7 (6)
C19—C15—C16—N6	175.8 (5)	N3—Cu1—N2—C2	−172.9 (6)
N1—C15—C16—C22	179.0 (5)	N1—Cu1—N2—C2	2.6 (5)
C19—C15—C16—C22	−1.1 (8)	N4—Cu1—N2—C2	107.1 (6)
N1—C1—C17—C18	6.3 (12)	N5—Cu1—N2—C3	79.8 (6)
C2—C1—C17—C18	−174.7 (7)	N3—Cu1—N2—C3	4.6 (5)
C1—C17—C18—C19	−3.7 (13)	N1—Cu1—N2—C3	−179.9 (5)
C17—C18—C19—C20	−179.5 (8)	N4—Cu1—N2—C3	−75.4 (6)
C17—C18—C19—C15	−1.6 (11)	C6—C5—N3—C7	79.5 (7)
N1—C15—C19—C18	4.8 (9)	C6—C5—N3—C4	−156.7 (6)
C16—C15—C19—C18	−175.1 (6)	C6—C5—N3—Cu1	−38.3 (7)
N1—C15—C19—C20	−177.2 (6)	C8—C7—N3—C5	−151.0 (6)
C16—C15—C19—C20	2.9 (9)	C8—C7—N3—C4	84.3 (7)
C18—C19—C20—C21	176.8 (7)	C8—C7—N3—Cu1	−33.0 (7)
C15—C19—C20—C21	−1.0 (11)	C3—C4—N3—C5	74.3 (7)
C19—C20—C21—C22	−2.7 (12)	C3—C4—N3—C7	−160.2 (6)
N6—C16—C22—C23	0.0 (9)	C3—C4—N3—Cu1	−43.6 (6)
C15—C16—C22—C23	176.9 (6)	N2—Cu1—N3—C5	−98.5 (5)
N6—C16—C22—C21	−179.4 (6)	N5—Cu1—N3—C5	128.5 (5)
C15—C16—C22—C21	−2.5 (9)	N1—Cu1—N3—C5	−111.8 (6)
C20—C21—C22—C23	−174.8 (7)	N4—Cu1—N3—C5	12.5 (4)
C20—C21—C22—C16	4.5 (10)	N2—Cu1—N3—C7	140.0 (4)
C16—C22—C23—C24	−0.1 (10)	N5—Cu1—N3—C7	7.1 (5)
C21—C22—C23—C24	179.3 (7)	N1—Cu1—N3—C7	126.7 (6)
C22—C23—C24—C9	−0.4 (11)	N4—Cu1—N3—C7	−109.0 (4)
N6—C9—C24—C23	1.2 (11)	N2—Cu1—N3—C4	21.9 (5)
C10—C9—C24—C23	−177.9 (6)	N5—Cu1—N3—C4	−111.1 (5)
O10—C10—O9—C11	80.3 (8)	N1—Cu1—N3—C4	8.6 (9)
C9—C10—O9—C11	−160.0 (6)	N4—Cu1—N3—C4	132.8 (5)
C12—C11—O9—C10	171.5 (7)	C5—C6—N4—Cu1	−39.9 (6)
O9—C10—O10—C13	−109.5 (9)	N2—Cu1—N4—C6	93.0 (4)
C9—C10—O10—C13	134.1 (8)	N5—Cu1—N4—C6	−66.5 (4)
C14—C13—O10—C10	−157.8 (13)	N3—Cu1—N4—C6	15.0 (4)
C17—C1—N1—C15	−3.1 (9)	N1—Cu1—N4—C6	178.1 (4)
C2—C1—N1—C15	177.9 (6)	C7—C8—N5—Cu1	−42.9 (6)
C17—C1—N1—Cu1	−175.3 (6)	N2—Cu1—N5—C8	−53.3 (5)
C2—C1—N1—Cu1	5.7 (7)	N3—Cu1—N5—C8	20.1 (4)
C19—C15—N1—C1	−2.5 (8)	N1—Cu1—N5—C8	−142.3 (4)
C16—C15—N1—C1	177.4 (5)	N4—Cu1—N5—C8	100.8 (4)
C19—C15—N1—Cu1	167.8 (4)	C24—C9—N6—C16	−1.3 (10)
C16—C15—N1—Cu1	−12.3 (8)	C10—C9—N6—C16	177.8 (6)
N2—Cu1—N1—C1	−4.4 (4)	C22—C16—N6—C9	0.7 (9)
N5—Cu1—N1—C1	125.6 (4)	C15—C16—N6—C9	−176.2 (5)
N3—Cu1—N1—C1	8.9 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4C···O9	0.92	2.15	2.977 (7)	150
N4—H4C···N6	0.92	2.61	3.182 (7)	120
N5—H5D···O10	0.92	2.14	3.037 (8)	164
N5—H5D···N6	0.92	2.56	2.942 (7)	106
C4—H4A···O7^i	0.99	2.53	3.424 (15)	150
C5—H5A···O1^ii	0.99	2.52	3.251 (10)	131
C23—H23···O3^iii	0.95	2.46	3.403 (11)	169
C24—H24···O7^iv	0.95	2.56	3.488 (13)	166

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