Chlorido­((E)-2-{2-[(2-hy­droxy­benzyl­idene)amino]-2-(pyridin-2-yl)-1-[(pyridin-2-ylmeth­yl)amino]eth­yl}phenolato-κ4N,N′,N′′,O)copper(II)

Alkhamis, K.; Gultneh, Y.; Butcher, R.J.

doi:10.1107/S2414314626007169

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 11| Part 7| July 2026| x260716

https://doi.org/10.1107/S2414314626007169

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Chlorido((E)-2-{2-[(2-hydroxybenzylidene)amino]-2-(pyridin-2-yl)-1-[(pyridin-2-ylmethyl)amino]ethyl}phenolato-κ⁴N,N′,N′′,O)copper(II)

Kholood Alkhamis,^a Yilma Gultneh ^b and Ray J. Butcher ^b ^*

^aUniversity City, Duba Road, Tabuk, 71491, Saudi Arabia, and ^bDepartment of Chemistry, Howard University, 525 College St NW, Washington DC 20059, USA
^*Correspondence e-mail: [email protected]

Edited by M. Weil, Vienna University of Technology, Austria (Received 3 July 2026; accepted 13 July 2026; online 16 July 2026)

The title complex, [Cu(C₂₆H₂₃N₄O₂)Cl], has resulted from C—C bond formation during synthesis. The crystal structure comprises a tetradentate ligand, (E)-2-{2-[(2-hydroxybenzylidene)amino]-2-(pyridin-2-yl)-1-[(pyridin-2-ylmethyl)amino]ethyl}phenolato, binding through three N and one O atom, and an additional chlorido ligand. The coordination environment of the central copper(II) atom is slightly distorted square-pyramidal with a geometry index τ₅ of 0.034.

Keywords: crystal structure; C—C bond formation; τ parameter; five-coordinate copper complex; Schiff base ligand.

CCDC reference: 2572974

Structure description

The crystal structure of a copper(II) complex with the ligand (E)-2-{2-[(2-hydroxybenzylidene)amino]-2-(pyridin-2-yl)-1-[(pyridin-2-ylmethyl)amino]ethyl}phenolate (LH; L = C₂₆H₂₃N₄O₂) deprotonated at one of the phenol OH groups is reported. The complex of composition, CuLCl, 1, exhibits a square-pyramidal coordination environment around the Cu^II atom with the Cl atom in the axial position and with a τ₅ parameter of 0.034 (Addison et al., 1984 ). The complex resulted from the reaction of a methanolic solution of CuCl₂ with a methanolic solution of 2-{[(pyridin-2-ylmethyl)imino]methyl}phenol combined with one equivalent of triethylamine; the resulting solution was refluxed for 20 h. The structure of 1 indicates that there has been C—C bond formation between C8 and C14 (Fig. 1).

Figure 1
The molecular structure of 1 with the atom labelling; displacement ellipsoids are shown at the 30% probability level.

As indicated above, 1 has a slightly distorted square-pyramidal coordination environment around the central Cu^II atom (Fig. 1) with the base consisting of donors O1, N1, N2 and N3, and with Cl1 in the axial position. The ON₃ coordination set is almost planar (root-mean-square deviation of 0.025 Å) with Cu deviating from this plane by 0.252 (1) Å. The basal bond lengths range from 1.900 (2) for Cu—O1 to 2.022 (2) for Cu—N2 while the axial Cu—Cl bond length is 2.5516 (9) (Table 1). In an examination of the conformation adopted by the ligand it can be seen that, while O1 and N3 are in the coordination plane of the ON₃ donor atoms, their six-membered rings are not coplanar and make a dihedral angle of 26.2 (2)°.

Table 1
Selected geometric parameters (Å, °)

Cu—O1	1.900 (2)	Cu—N2	2.022 (2)
Cu—N1	1.943 (2)	Cu—Cl1	2.5516 (9)
Cu—N3	2.009 (2)

O1—Cu—N1	95.67 (9)	N3—Cu—N2	81.68 (10)
O1—Cu—N3	95.01 (9)	O1—Cu—Cl1	99.14 (7)
N1—Cu—N3	161.64 (10)	N1—Cu—Cl1	98.61 (7)
O1—Cu—N2	163.69 (10)	N3—Cu—Cl1	94.38 (8)
N1—Cu—N2	83.90 (9)	N2—Cu—Cl1	97.04 (8)

There is a strong hydrogen-bonding interaction between the O—H and Cl moieties of adjoining molecules, leading to the formation of a centrosymmetric dimer (Table 2, Fig. 2). This is also illustrated in the Hirshfeld fingerprint plot as prominent spikes (Fig. 3). There is also an intramolecular N—H⋯O hydrogen bond (Table 2). The packing of the molecules in the unit cell is shown in Fig. 4.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯Cl1ⁱ	0.85 (4)	2.16 (4)	3.005 (3)	177 (4)
N2—H2N⋯O2	0.89 (3)	2.38 (3)	2.898 (3)	117 (2)
C8—H8A⋯O2	0.98	2.46	3.064 (4)	119
C19—H19A⋯Cl1ⁱ	0.93	2.97	3.627 (3)	129
C21—H21B⋯O1ⁱⁱ	0.97	2.45	3.277 (4)	143
Symmetry codes: (i) ; (ii) .

Figure 2
Plot showing the formation of a centrosymmetric dimer by O—H⋯Cl hydrogen bonds (shown as dashed lines). Displacement ellipsoids are shown at the 30% probability level. [Symmetry code: (A) −x, −y + 1, −z + 2].

Figure 3
Hirshfeld fingerprint plot showing the O—H⋯Cl interactions as prominent spikes.

Figure 4
Packing plot of 1 with the molecules linked by various hydrogen-bonding interactions (dashed lines).

A search of the Cambridge Structural Database (CSD version 6.01, update of February 2026; Groom et al., 2016 ) for copper(II) compounds with similar coordination sets resulted in five hits (AHEQUA, Plaul et al., 2009 ; BUQMAD, Keypour et al., 2015 ; HUQHIK, He et al., 2003 ; TIDTAF, Nieger, et al., 2023 ; WECHAN, Li et al., 2000 ) with bond lengths and angles around the central Cu^II atom comparable with the title complex.

Synthesis and crystallization

A solution of 1.66 g (16.37 mmole) of 2-aminomethylpyridine in 10 ml of methanol was added to a solution of 2.00 g (16.37 mmole) of salicylaldehyde in 10 ml of methanol, and a yellow solution was obtained. The solution was stirred and refluxed overnight for 20 h and then the solvent was removed by rotary evaporation.

The ligand (1.914 g. 8.5 mmole) was dissolved in 15 ml methanol and mixed with triethylamine (0.84 ml, 8.5 mmole). To this mixture was added a methanol solution of CuCl₂ (0.578 g, 4.3 mmole). The dark-blue solution was refluxed and stirred overnight for 20 h. The solvent was reduced by rotary evaporation and the blue precipitate formed was filtered, washed with methanol and diethyl ether and dried in a desiccator. Crystals were grown by diffusion of diethyl ether into an acetonitrile solution of the complex.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3.

Table 3
Experimental details

Crystal data
Chemical formula	[CuC₂₆H₂₃N₄O₂)Cl]
M_r	522.47
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	9.8728 (16), 11.525 (3), 11.837 (2)
α, β, γ (°)	85.846 (5), 71.992 (3), 66.799 (3)
V (Å³)	1175.4 (4)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.07
Crystal size (mm)	0.37 × 0.29 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.605, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	11006, 4331, 3578
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.132, 1.05
No. of reflections	4331
No. of parameters	315
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.34, −0.43
Computer programs: APEX2 and SAINT (Bruker, 2005 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), SHELXTL (Sheldrick, 2008 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2572974

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314626007169/wm4253sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314626007169/wm4253Isup2.hkl

checkCIF report

Computing details top

Chlorido((E)-2-{2-[(2-hydroxybenzylidene)amino]-2-(pyridin-2-yl)-1-[(pyridin-2-ylmethyl)amino]ethyl}phenolato-κ⁴N,N',N'',O)copper(II) top

Crystal data top

[CuC₂₆H₂₃N₄O₂)Cl]	Z = 2
M_r = 522.47	F(000) = 538
Triclinic, P1	D_x = 1.476 Mg m⁻³
a = 9.8728 (16) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.525 (3) Å	Cell parameters from 4491 reflections
c = 11.837 (2) Å	θ = 2.4–25.4°
α = 85.846 (5)°	µ = 1.07 mm⁻¹
β = 71.992 (3)°	T = 296 K
γ = 66.799 (3)°	Plate, pale blue
V = 1175.4 (4) Å³	0.37 × 0.29 × 0.08 mm

Data collection top

Bruker APEXII CCD diffractometer	3578 reflections with I > 2σ(I)
ω and φ scans	R_int = 0.038
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 25.5°, θ_min = 1.8°
T_min = 0.605, T_max = 0.745	h = −11→11
11006 measured reflections	k = −13→13
4331 independent reflections	l = −14→14

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: mixed
wR(F²) = 0.132	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0895P)² + 0.0616P] where P = (F_o² + 2F_c²)/3
4331 reflections	(Δ/σ)_max = 0.001
315 parameters	Δρ_max = 1.34 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Special details top

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.

Refinement. Hydrogen atoms attached to O and N atoms involved in hydrogen-bonding were refined freely while the remaining hydrogen atoms were included in their calculated positions as a riding model.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu	0.36805 (4)	0.55198 (3)	0.71051 (3)	0.03228 (15)
Cl1	0.14882 (10)	0.69172 (8)	0.88485 (7)	0.0505 (2)
O1	0.4969 (2)	0.6446 (2)	0.67674 (19)	0.0386 (5)
O2	0.1014 (3)	0.3258 (2)	0.9007 (2)	0.0437 (5)
H2O	0.028 (5)	0.324 (4)	0.961 (4)	0.068 (13)*
N1	0.4844 (3)	0.4256 (2)	0.8001 (2)	0.0308 (5)
N2	0.2754 (3)	0.4254 (2)	0.7035 (2)	0.0312 (5)
H2N	0.182 (4)	0.460 (3)	0.757 (3)	0.032 (8)*
N3	0.2608 (3)	0.6326 (2)	0.5887 (2)	0.0371 (6)
N4	0.6651 (3)	0.1333 (3)	0.7720 (2)	0.0481 (7)
C1	0.6052 (3)	0.6280 (3)	0.7261 (3)	0.0355 (7)
C2	0.6867 (4)	0.7080 (3)	0.6962 (3)	0.0434 (7)
H2A	0.661014	0.771253	0.643881	0.052*
C3	0.8044 (4)	0.6946 (3)	0.7428 (3)	0.0505 (9)
H3A	0.856228	0.748761	0.721114	0.061*
C4	0.8459 (4)	0.6024 (3)	0.8208 (3)	0.0511 (9)
H4A	0.924444	0.594607	0.852068	0.061*
C5	0.7699 (4)	0.5224 (3)	0.8517 (3)	0.0442 (8)
H5A	0.797988	0.460208	0.904372	0.053*
C6	0.6501 (3)	0.5316 (3)	0.8058 (3)	0.0343 (6)
C7	0.5898 (3)	0.4352 (3)	0.8366 (3)	0.0341 (6)
H7A	0.629939	0.374835	0.886977	0.041*
C8	0.4289 (3)	0.3220 (3)	0.8335 (2)	0.0310 (6)
H8A	0.336631	0.351584	0.903442	0.037*
C9	0.5471 (3)	0.2021 (3)	0.8623 (3)	0.0338 (6)
C10	0.5314 (4)	0.1683 (3)	0.9786 (3)	0.0556 (9)
H10A	0.446990	0.217510	1.040642	0.067*
C11	0.6450 (5)	0.0591 (4)	1.0006 (4)	0.0754 (13)
H11A	0.637848	0.034243	1.078080	0.090*
C12	0.7656 (5)	−0.0107 (4)	0.9088 (4)	0.0626 (10)
H12A	0.843208	−0.083875	0.921546	0.075*
C13	0.7708 (4)	0.0290 (4)	0.7969 (4)	0.0577 (9)
H13A	0.853630	−0.019904	0.733782	0.069*
C14	0.3807 (3)	0.2995 (3)	0.7274 (2)	0.0301 (6)
H14A	0.473957	0.271585	0.658173	0.036*
C15	0.3125 (3)	0.2008 (3)	0.7420 (2)	0.0318 (6)
C16	0.3869 (4)	0.0914 (3)	0.6693 (3)	0.0489 (8)
H16A	0.481829	0.077628	0.612432	0.059*
C17	0.3238 (4)	0.0016 (4)	0.6790 (4)	0.0625 (11)
H17A	0.376193	−0.071679	0.629425	0.075*
C18	0.1826 (4)	0.0215 (4)	0.7628 (4)	0.0571 (9)
H18A	0.139959	−0.038619	0.769465	0.069*
C19	0.1042 (4)	0.1301 (3)	0.8369 (3)	0.0423 (7)
H19A	0.008134	0.143975	0.892228	0.051*
C20	0.1706 (3)	0.2192 (3)	0.8280 (2)	0.0332 (6)
C21	0.2459 (4)	0.4299 (3)	0.5877 (3)	0.0393 (7)
H21A	0.161729	0.403345	0.595986	0.047*
H21B	0.337575	0.372490	0.529480	0.047*
C22	0.2046 (3)	0.5626 (3)	0.5460 (2)	0.0354 (7)
C23	0.1198 (4)	0.6093 (3)	0.4679 (3)	0.0461 (8)
H23A	0.083269	0.558695	0.438360	0.055*
C24	0.0894 (4)	0.7322 (4)	0.4339 (3)	0.0570 (9)
H24A	0.033653	0.765234	0.380354	0.068*
C25	0.1441 (4)	0.8046 (4)	0.4813 (3)	0.0581 (10)
H25A	0.122561	0.888307	0.461969	0.070*
C26	0.2292 (4)	0.7527 (3)	0.5563 (3)	0.0498 (8)
H26A	0.267070	0.801782	0.586498	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.0387 (2)	0.0327 (2)	0.0312 (2)	−0.01685 (17)	−0.01561 (16)	0.00614 (15)
Cl1	0.0474 (5)	0.0503 (5)	0.0419 (5)	−0.0184 (4)	0.0031 (4)	−0.0044 (4)
O1	0.0445 (12)	0.0400 (12)	0.0404 (11)	−0.0237 (10)	−0.0174 (10)	0.0100 (9)
O2	0.0409 (12)	0.0413 (13)	0.0435 (13)	−0.0186 (10)	−0.0011 (10)	−0.0033 (10)
N1	0.0323 (12)	0.0324 (13)	0.0295 (12)	−0.0134 (10)	−0.0115 (10)	0.0031 (10)
N2	0.0319 (13)	0.0331 (13)	0.0272 (12)	−0.0118 (11)	−0.0089 (10)	0.0034 (10)
N3	0.0442 (15)	0.0352 (14)	0.0345 (13)	−0.0173 (11)	−0.0145 (11)	0.0079 (11)
N4	0.0446 (16)	0.0409 (16)	0.0431 (16)	−0.0052 (13)	−0.0082 (13)	0.0046 (12)
C1	0.0329 (15)	0.0379 (16)	0.0326 (15)	−0.0145 (13)	−0.0037 (12)	−0.0051 (12)
C2	0.0469 (18)	0.0448 (18)	0.0409 (17)	−0.0245 (15)	−0.0068 (14)	−0.0030 (14)
C3	0.0452 (19)	0.052 (2)	0.057 (2)	−0.0278 (17)	−0.0044 (16)	−0.0133 (17)
C4	0.0388 (18)	0.061 (2)	0.060 (2)	−0.0215 (17)	−0.0174 (16)	−0.0110 (18)
C5	0.0402 (17)	0.0447 (19)	0.0506 (19)	−0.0149 (15)	−0.0182 (15)	−0.0051 (15)
C6	0.0304 (15)	0.0365 (16)	0.0343 (15)	−0.0115 (12)	−0.0086 (12)	−0.0039 (12)
C7	0.0353 (15)	0.0346 (16)	0.0316 (14)	−0.0117 (13)	−0.0121 (12)	0.0021 (12)
C8	0.0346 (15)	0.0320 (15)	0.0283 (14)	−0.0150 (12)	−0.0098 (12)	0.0034 (11)
C9	0.0341 (15)	0.0339 (16)	0.0363 (15)	−0.0157 (13)	−0.0120 (13)	0.0046 (12)
C10	0.058 (2)	0.054 (2)	0.0387 (18)	−0.0063 (18)	−0.0152 (17)	0.0085 (16)
C11	0.085 (3)	0.071 (3)	0.052 (2)	−0.009 (2)	−0.031 (2)	0.024 (2)
C12	0.060 (2)	0.048 (2)	0.072 (3)	−0.0067 (18)	−0.031 (2)	0.0167 (19)
C13	0.047 (2)	0.047 (2)	0.061 (2)	−0.0027 (16)	−0.0128 (17)	0.0026 (17)
C14	0.0316 (14)	0.0317 (15)	0.0246 (13)	−0.0124 (12)	−0.0049 (11)	−0.0009 (11)
C15	0.0348 (15)	0.0337 (15)	0.0287 (14)	−0.0140 (12)	−0.0112 (12)	0.0017 (12)
C16	0.0477 (19)	0.050 (2)	0.0457 (19)	−0.0239 (16)	−0.0012 (15)	−0.0110 (16)
C17	0.067 (2)	0.055 (2)	0.067 (2)	−0.031 (2)	−0.007 (2)	−0.0203 (19)
C18	0.068 (2)	0.053 (2)	0.065 (2)	−0.039 (2)	−0.019 (2)	−0.0038 (18)
C19	0.0424 (17)	0.0469 (19)	0.0435 (18)	−0.0265 (15)	−0.0098 (14)	0.0051 (14)
C20	0.0366 (16)	0.0328 (16)	0.0296 (14)	−0.0125 (13)	−0.0113 (12)	0.0038 (12)
C21	0.0472 (18)	0.0456 (18)	0.0357 (16)	−0.0237 (15)	−0.0204 (14)	0.0061 (13)
C22	0.0352 (15)	0.0443 (18)	0.0266 (14)	−0.0161 (13)	−0.0091 (12)	0.0037 (12)
C23	0.0480 (19)	0.057 (2)	0.0371 (17)	−0.0205 (16)	−0.0195 (15)	0.0089 (15)
C24	0.061 (2)	0.065 (2)	0.0415 (19)	−0.0164 (19)	−0.0260 (18)	0.0176 (17)
C25	0.073 (3)	0.042 (2)	0.049 (2)	−0.0139 (18)	−0.0199 (19)	0.0167 (16)
C26	0.068 (2)	0.0424 (19)	0.0410 (18)	−0.0229 (17)	−0.0187 (17)	0.0081 (15)

Geometric parameters (Å, º) top

Cu—O1	1.900 (2)	C9—C10	1.382 (4)
Cu—N1	1.943 (2)	C10—C11	1.390 (5)
Cu—N3	2.009 (2)	C10—H10A	0.9300
Cu—N2	2.022 (2)	C11—C12	1.348 (6)
Cu—Cl1	2.5516 (9)	C11—H11A	0.9300
O1—C1	1.315 (3)	C12—C13	1.363 (5)
O2—C20	1.359 (4)	C12—H12A	0.9300
O2—H2O	0.85 (4)	C13—H13A	0.9300
N1—C7	1.288 (4)	C14—C15	1.510 (4)
N1—C8	1.482 (3)	C14—H14A	0.9800
N2—C21	1.480 (4)	C15—C16	1.381 (4)
N2—C14	1.483 (4)	C15—C20	1.400 (4)
N2—H2N	0.89 (3)	C16—C17	1.386 (5)
N3—C22	1.341 (4)	C16—H16A	0.9300
N3—C26	1.349 (4)	C17—C18	1.380 (5)
N4—C9	1.324 (4)	C17—H17A	0.9300
N4—C13	1.331 (4)	C18—C19	1.383 (5)
C1—C2	1.409 (4)	C18—H18A	0.9300
C1—C6	1.429 (4)	C19—C20	1.402 (4)
C2—C3	1.386 (5)	C19—H19A	0.9300
C2—H2A	0.9300	C21—C22	1.508 (4)
C3—C4	1.378 (5)	C21—H21A	0.9700
C3—H3A	0.9300	C21—H21B	0.9700
C4—C5	1.368 (5)	C22—C23	1.377 (4)
C4—H4A	0.9300	C23—C24	1.384 (5)
C5—C6	1.412 (4)	C23—H23A	0.9300
C5—H5A	0.9300	C24—C25	1.384 (6)
C6—C7	1.431 (4)	C24—H24A	0.9300
C7—H7A	0.9300	C25—C26	1.357 (5)
C8—C9	1.515 (4)	C25—H25A	0.9300
C8—C14	1.545 (4)	C26—H26A	0.9300
C8—H8A	0.9800

O1—Cu—N1	95.67 (9)	C9—C10—H10A	120.8
O1—Cu—N3	95.01 (9)	C11—C10—H10A	120.8
N1—Cu—N3	161.64 (10)	C12—C11—C10	119.5 (4)
O1—Cu—N2	163.69 (10)	C12—C11—H11A	120.3
N1—Cu—N2	83.90 (9)	C10—C11—H11A	120.3
N3—Cu—N2	81.68 (10)	C11—C12—C13	118.2 (3)
O1—Cu—Cl1	99.14 (7)	C11—C12—H12A	120.9
N1—Cu—Cl1	98.61 (7)	C13—C12—H12A	120.9
N3—Cu—Cl1	94.38 (8)	N4—C13—C12	124.3 (4)
N2—Cu—Cl1	97.04 (8)	N4—C13—H13A	117.9
C1—O1—Cu	124.75 (19)	C12—C13—H13A	117.9
C20—O2—H2O	113 (3)	N2—C14—C15	112.9 (2)
C7—N1—C8	122.5 (2)	N2—C14—C8	105.9 (2)
C7—N1—Cu	124.1 (2)	C15—C14—C8	115.8 (2)
C8—N1—Cu	113.12 (16)	N2—C14—H14A	107.3
C21—N2—C14	114.2 (2)	C15—C14—H14A	107.3
C21—N2—Cu	109.34 (17)	C8—C14—H14A	107.3
C14—N2—Cu	108.23 (16)	C16—C15—C20	118.3 (3)
C21—N2—H2N	105.2 (19)	C16—C15—C14	120.8 (3)
C14—N2—H2N	117.2 (19)	C20—C15—C14	120.8 (2)
Cu—N2—H2N	101.9 (19)	C15—C16—C17	121.7 (3)
C22—N3—C26	118.7 (3)	C15—C16—H16A	119.2
C22—N3—Cu	115.58 (19)	C17—C16—H16A	119.2
C26—N3—Cu	125.4 (2)	C18—C17—C16	119.6 (3)
C9—N4—C13	117.5 (3)	C18—C17—H17A	120.2
O1—C1—C2	118.3 (3)	C16—C17—H17A	120.2
O1—C1—C6	124.7 (3)	C17—C18—C19	120.5 (3)
C2—C1—C6	117.0 (3)	C17—C18—H18A	119.7
C3—C2—C1	121.5 (3)	C19—C18—H18A	119.7
C3—C2—H2A	119.2	C18—C19—C20	119.4 (3)
C1—C2—H2A	119.2	C18—C19—H19A	120.3
C4—C3—C2	121.1 (3)	C20—C19—H19A	120.3
C4—C3—H3A	119.4	O2—C20—C15	117.3 (3)
C2—C3—H3A	119.4	O2—C20—C19	122.2 (3)
C5—C4—C3	119.1 (3)	C15—C20—C19	120.5 (3)
C5—C4—H4A	120.4	N2—C21—C22	109.8 (2)
C3—C4—H4A	120.4	N2—C21—H21A	109.7
C4—C5—C6	121.9 (3)	C22—C21—H21A	109.7
C4—C5—H5A	119.1	N2—C21—H21B	109.7
C6—C5—H5A	119.1	C22—C21—H21B	109.7
C5—C6—C1	119.3 (3)	H21A—C21—H21B	108.2
C5—C6—C7	116.2 (3)	N3—C22—C23	121.7 (3)
C1—C6—C7	124.3 (3)	N3—C22—C21	114.6 (2)
N1—C7—C6	125.1 (3)	C23—C22—C21	123.7 (3)
N1—C7—H7A	117.4	C22—C23—C24	119.3 (3)
C6—C7—H7A	117.4	C22—C23—H23A	120.3
N1—C8—C9	113.9 (2)	C24—C23—H23A	120.3
N1—C8—C14	105.4 (2)	C25—C24—C23	118.4 (3)
C9—C8—C14	111.8 (2)	C25—C24—H24A	120.8
N1—C8—H8A	108.5	C23—C24—H24A	120.8
C9—C8—H8A	108.5	C26—C25—C24	119.6 (3)
C14—C8—H8A	108.5	C26—C25—H25A	120.2
N4—C9—C10	122.3 (3)	C24—C25—H25A	120.2
N4—C9—C8	117.2 (3)	N3—C26—C25	122.3 (3)
C10—C9—C8	120.6 (3)	N3—C26—H26A	118.8
C9—C10—C11	118.4 (3)	C25—C26—H26A	118.8

Cu—O1—C1—C2	−177.1 (2)	Cu—N2—C14—C8	44.0 (2)
Cu—O1—C1—C6	4.9 (4)	N1—C8—C14—N2	−51.4 (3)
O1—C1—C2—C3	−178.7 (3)	C9—C8—C14—N2	−175.7 (2)
C6—C1—C2—C3	−0.6 (4)	N1—C8—C14—C15	−177.4 (2)
C1—C2—C3—C4	−0.2 (5)	C9—C8—C14—C15	58.3 (3)
C2—C3—C4—C5	0.5 (5)	N2—C14—C15—C16	122.0 (3)
C3—C4—C5—C6	0.0 (5)	C8—C14—C15—C16	−115.7 (3)
C4—C5—C6—C1	−0.8 (5)	N2—C14—C15—C20	−56.7 (3)
C4—C5—C6—C7	174.5 (3)	C8—C14—C15—C20	65.6 (3)
O1—C1—C6—C5	179.1 (3)	C20—C15—C16—C17	0.7 (5)
C2—C1—C6—C5	1.1 (4)	C14—C15—C16—C17	−178.0 (3)
O1—C1—C6—C7	4.1 (5)	C15—C16—C17—C18	0.3 (6)
C2—C1—C6—C7	−173.9 (3)	C16—C17—C18—C19	−0.1 (6)
C8—N1—C7—C6	178.8 (3)	C17—C18—C19—C20	−1.2 (6)
Cu—N1—C7—C6	−7.6 (4)	C16—C15—C20—O2	178.2 (3)
C5—C6—C7—N1	−177.6 (3)	C14—C15—C20—O2	−3.1 (4)
C1—C6—C7—N1	−2.5 (5)	C16—C15—C20—C19	−2.0 (4)
C7—N1—C8—C9	−26.7 (4)	C14—C15—C20—C19	176.7 (3)
Cu—N1—C8—C9	159.09 (19)	C18—C19—C20—O2	−178.0 (3)
C7—N1—C8—C14	−149.6 (3)	C18—C19—C20—C15	2.3 (5)
Cu—N1—C8—C14	36.2 (2)	C14—N2—C21—C22	−153.9 (2)
C13—N4—C9—C10	−0.4 (5)	Cu—N2—C21—C22	−32.5 (3)
C13—N4—C9—C8	178.8 (3)	C26—N3—C22—C23	1.8 (4)
N1—C8—C9—N4	−73.2 (3)	Cu—N3—C22—C23	175.7 (2)
C14—C8—C9—N4	46.2 (3)	C26—N3—C22—C21	−179.8 (3)
N1—C8—C9—C10	106.1 (3)	Cu—N3—C22—C21	−5.9 (3)
C14—C8—C9—C10	−134.6 (3)	N2—C21—C22—N3	25.6 (4)
N4—C9—C10—C11	0.8 (5)	N2—C21—C22—C23	−156.0 (3)
C8—C9—C10—C11	−178.4 (3)	N3—C22—C23—C24	−1.0 (5)
C9—C10—C11—C12	−0.4 (6)	C21—C22—C23—C24	−179.2 (3)
C10—C11—C12—C13	−0.3 (7)	C22—C23—C24—C25	−0.9 (5)
C9—N4—C13—C12	−0.3 (6)	C23—C24—C25—C26	2.0 (6)
C11—C12—C13—N4	0.7 (7)	C22—N3—C26—C25	−0.7 (5)
C21—N2—C14—C15	−66.3 (3)	Cu—N3—C26—C25	−173.9 (3)
Cu—N2—C14—C15	171.70 (17)	C24—C25—C26—N3	−1.3 (6)
C21—N2—C14—C8	166.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···Cl1ⁱ	0.85 (4)	2.16 (4)	3.005 (3)	177 (4)
N2—H2N···O2	0.89 (3)	2.38 (3)	2.898 (3)	117 (2)
C8—H8A···O2	0.98	2.46	3.064 (4)	119
C19—H19A···Cl1ⁱ	0.93	2.97	3.627 (3)	129
C21—H21B···O1ⁱⁱ	0.97	2.45	3.277 (4)	143

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

Acknowledgements

RJB wishes to acknowledge both the Howard University Nanoscience Center for access to liquid nitrogen and the NSF–MRI program (grant CHE-0619278) for funds to purchase the diffractometer.

Funding information

Funding for this research was provided by: National Science Foundation (grant No. CHE-0619278).

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