Crystal structure of (aceto­nitrile-κN)iodido­(2-(naphthalen-1-yl)-6-{1-[(2,4,6-tri­methyl­phen­yl)imino]ethyl}­pyridine-κ2N,N′)copper(I)

Al-Najjar, N.; Solan, G.A.; Singh, K.

doi:10.1107/S2056989016018685

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Volume 72| Part 12| December 2016| Pages 1845-1847

https://doi.org/10.1107/S2056989016018685

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Crystal structure of (acetonitrile-κN)iodido(2-(naphthalen-1-yl)-6-{1-[(2,4,6-trimethylphenyl)imino]ethyl}pyridine-κ²N,N′)copper(I)

Nada Al-Najjar,^a ^*‡ Gregory A. Solan ^b ^* and Kuldip Singh ^b

^aDepartment of Chemistry, College of Science for Women, University of Baghdad, Iraq, and ^bDepartment of Chemistry, University of Leicester, University Road, Leicester LE1 7RH, England
^*Correspondence e-mail: nadaaj_chem@csw.uobaghdad.edu.iq, gas8@leicester.ac.uk

Edited by M. Weil, Vienna University of Technology, Austria (Received 11 November 2016; accepted 22 November 2016; online 29 November 2016)

In the mononuclear title complex, [CuI(C₂H₃N)(C₂₆H₂₄N₂)], the Cu^I ion has a distorted tetrahedral coordination environment, defined by two N atoms of the chelating 2-(naphthalen-1-yl)-6-[(2,4,6-trimethylphenyl)imino]pyridine ligand, one N atom of an acetonitrile ligand and one iodide ligand. Within the complex, there are weak intramolecular C—H⋯N hydrogen bonds, while weak intermolecular C—H⋯I interactions between complex molecules, help to facilitate a three-dimensional network.

Keywords: crystal structure; copper(I) complex; 2-imino-6-(naphthalen-1-yl)pyridine; Schiff base; iodide; bidentate ligand.

CCDC reference: 1518571

1. Chemical context

Coordination complexes of copper(I) halides bearing a variety of co-ligands have been of interest in coordination chemistry (Karahan et al., 2015 ; Dennehy et al., 2011 ; Oshio et al., 1996 ; Seward et al., 2003 ) due, in some measure, to their preparative accessibility, structural variability, magnetic properties (Oshio et al., 1996) and their relevance to biological or medicinal applications (Corey et al., 1987 ; Dias et al., 2006 ). The role of copper(I) is evident in several biologically important reactions, such as a dioxygen carrier and models for several enzymes (Krupanidhi et al., 2008 ). Elsewhere, these compounds have been reported to be luminescent (Aslanidis et al., 2010 ; Gallego et al., 2012 ) and exhibit corrosion inhibiting properties (Tian et al., 2004 ). The structures of metal complexes bearing naphthyl-substituted N,N-pyridine-alkylamides were reported by Armitage et al. (2015 ) and related structures were presented by Wattanakanjana et al. (2014 ). Cotton et al. (1999 ) highlighted details of the affinity of nitrile ligands for Cu^I ions. Within this context, we report herein the crystal structure of the title complex, [CuI(C₂H₃N)(C₂₆H₂₄N₂)].

2. Structural commentary

The molecular structure of the title complex is shown in Fig. 1. The Cu^I ion is coordinated by atoms N1 and N2 of the 2-(naphthalen-1-yl)-6-[(2,4,6-trimethylphenyl)imino]pyridine ligand, by atom N3 of an acetonitrile ligand and by an iodide anion (I1), leading to a distorted tetrahedral coordination environment. The two N atoms of the bidentate ligand chelate to Cu^I with similar Cu—N bond lengths [Cu1—N1 = 2.091 (4), Cu1—N2 = 2.085 (4) Å]. A comparable N,N′-binding has been observed in related structures with bis[2-(2-pyridyl)ethyl]amine ligands (Osako et al., 2001 ). At 1.960 (5) Å, the Cu1—N3 distance is significantly shorter than the Cu—N_pyridine and Cu—N_imine distances. The Cu1—I distance amounts to 2.5479 (9) Å. The N2—Cu1—N1 bite angle of the chelating ligand is 78.86 (18)°, while the N3—Cu—I angle between the monodentate acetonitrile and iodide ligands is closer to tetrahedral, 112.74 (15)°. The naphthyl ring system is inclined by 58.20 (17)° to the central N=C(CH₃)—pyridine moiety, whereas the trimethylphenyl ring is almost perpendicular to the latter, at 84.8 (3)°. Within the complex, an intramolecular C—H⋯N hydrogen-bonding interaction is present, stabilizing the molecular conformation (Table 1, Fig. 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C26—H26B⋯N1	0.98	2.52	2.891 (8)	102

Figure 1
The molecular structure of the title complex, with displacement ellipsoids drawn at the 50% probability level. The C—H⋯N hydrogen bond is shown as a dashed line.

3. Supramolecular features

In the crystal, weak C—H⋯I contacts involving a phenyl H atom [C16—H16B⋯Iⁱ, 3.958 (6) Å, 152°; symmetry code: (i) x, y − 1, z] and a H atom of the acetonitrile methyl group [[C28—H28B⋯Iⁱ, 4.010 (6) Å, 109°] link the complex molecules, forming a three-dimensional network (Fig. 2).

Figure 2
Part of the crystal structure, showing intermolecular C—H⋯I interactions (dashed lines).

4. Synthesis and crystallization

All synthetic manipulations were performed under a nitrogen atmosphere, using standard Schlenk techniques. Solvents were distilled under nitrogen from appropriate drying agents and degassed prior to use (Armarego et al., 1996 ). The 2-(naphthalen-1-yl)-6-[(2,4,6-trimethylphenyl)imino]pyridine ligand (L_mes) was synthesized according to a modified literature procedure (Armitage et al., 2015).

A solution of 0.0262 g of CuI (0.137 mmol) in 5 ml of acetonitrile was mixed with a solution of 0.05 g of L_mes (0.134 mmol) in 5 ml of acetonitrile. The mixture was stirred at room temperature for 24 h before evaporating the volatiles. The residue was extracted with n-hexane (5 × 3 ml). The extracts were combined and the solvent removed under reduced pressure to give a red solid which was recrystallized from acetonitrile solution. Yield: 54%. M.p. >253 K (decomp). ¹H NMR (400 MHz, CD₂Cl₂): δ 1.88 [s, 6H, ortho- (CH₃)₂], 1.97 (s, 3H, N≡CCH₃), 2.16 (s, 3H, N=CCH₃), 2.20 [s, 3H, para-(CH₃)₂], 6.84 (s, 2H, Mes-H), 7.39 (s, 1H, Nap-H), 7.45 (t, J 7.8, 2H, Nap-H/Py–H), 7.51 (s, 1H, Py–H), 7.73 (s, 1H, Py-H), 7.81 (s, 2H, Nap-H), 7.87 (d, J 3.7, 2H, Nap-H), 8.04 (s, 1H, Nap-H). IR ν_max (solid)/cm⁻¹ 1620 (C=N_imine), 1555 (C=N_py). ESI MS: m/z 428 [M–I–MeCN]⁺.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms were positioned geometrically, with C—H = 0.95 Å and with U_iso(H) = 1.2U_eq(C) for H atoms on Csp² and 0.98 Å with U_iso(H) = 1.5U_eq(C) for H atoms on Csp³.

Table 2
Experimental details

Crystal data
Chemical formula	[CuI(C₂H₃N)(C₂₆H₂₄N₂)]
M_r	595.97
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	14.689 (3), 8.0775 (15), 21.861 (4)
β (°)	103.942 (3)
V (Å³)	2517.4 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.11
Crystal size (mm)	0.25 × 0.07 × 0.03

Data collection
Diffractometer	Bruker APEX 2000 CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2001 )
T_min, T_max	0.679, 0.862
No. of measured, independent and observed [I > 2σ(I)] reflections	19143, 4936, 2757
R_int	0.125
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.085, 0.77
No. of reflections	4936
No. of parameters	303
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.13, −0.81
Computer programs: SMART and SAINT (Bruker, 2001), SHELXS97, SHELXL97 and SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC reference: 1518571

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989016018685/wm5341sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016018685/wm5341Isup2.hkl

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(Acetonitrile-κN)iodido(2-(naphthalen-1-yl)-6-{1-[(2,4,6-trimethylphenyl)imino]ethyl}pyridine-κ²N,N')copper(I) top

Crystal data top

[CuI(C₂H₃N)(C₂₆H₂₄N₂)]	F(000) = 1192
M_r = 595.97	D_x = 1.572 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 639 reflections
a = 14.689 (3) Å	θ = 2.9–23.2°
b = 8.0775 (15) Å	µ = 2.11 mm⁻¹
c = 21.861 (4) Å	T = 150 K
β = 103.942 (3)°	Needle, orange
V = 2517.4 (8) Å³	0.25 × 0.07 × 0.03 mm
Z = 4

Data collection top

Bruker APEX 2000 CCD area detector diffractometer	4936 independent reflections
Radiation source: fine-focus sealed tube	2757 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.125
phi and ω scans	θ_max = 26.0°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −18→17
T_min = 0.679, T_max = 0.862	k = −9→9
19143 measured reflections	l = −26→26

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H-atom parameters constrained
S = 0.77	w = 1/[σ²(F_o²) + (0.0178P)²] where P = (F_o² + 2F_c²)/3
4936 reflections	(Δ/σ)_max = 0.002
303 parameters	Δρ_max = 1.13 e Å⁻³
0 restraints	Δρ_min = −0.81 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. 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 > 2sigma(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 (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.27041 (5)	0.46133 (9)	0.24724 (3)	0.0280 (2)
I1	0.27321 (3)	0.69329 (5)	0.16873 (2)	0.03325 (13)
N1	0.2948 (3)	0.5389 (6)	0.3410 (2)	0.0241 (12)
N2	0.1440 (3)	0.3972 (5)	0.2685 (2)	0.0196 (11)
N3	0.3532 (3)	0.2768 (6)	0.2390 (2)	0.0307 (13)
C1	0.3799 (4)	0.6189 (7)	0.3735 (3)	0.0241 (14)
C2	0.3847 (4)	0.7897 (8)	0.3723 (3)	0.0277 (15)
C3	0.4709 (4)	0.8651 (7)	0.3999 (3)	0.0309 (16)
H3	0.4755	0.9824	0.3996	0.037*
C4	0.5483 (4)	0.7737 (8)	0.4270 (3)	0.0322 (16)
C5	0.5416 (4)	0.6047 (8)	0.4277 (3)	0.0335 (16)
H5	0.5956	0.5412	0.4463	0.040*
C6	0.4569 (4)	0.5231 (7)	0.4015 (3)	0.0293 (15)
C7	0.2277 (4)	0.5153 (7)	0.3683 (3)	0.0245 (14)
C8	0.2289 (4)	0.5595 (7)	0.4358 (2)	0.0293 (15)
H8A	0.2892	0.6104	0.4560	0.044*
H8B	0.2200	0.4590	0.4588	0.044*
H8C	0.1781	0.6378	0.4363	0.044*
C9	0.1407 (4)	0.4362 (7)	0.3290 (3)	0.0237 (14)
C10	0.0617 (4)	0.4098 (7)	0.3511 (3)	0.0246 (14)
H10	0.0612	0.4389	0.3931	0.030*
C11	−0.0174 (4)	0.3404 (7)	0.3115 (3)	0.0260 (15)
H11	−0.0723	0.3197	0.3260	0.031*
C12	−0.0143 (4)	0.3028 (7)	0.2511 (3)	0.0249 (14)
H12	−0.0679	0.2569	0.2230	0.030*
C13	0.0668 (4)	0.3312 (7)	0.2308 (3)	0.0224 (14)
C14	0.0726 (4)	0.2803 (7)	0.1655 (3)	0.0193 (13)
C15	0.1401 (4)	0.1717 (7)	0.1593 (3)	0.0281 (15)
H15	0.1865	0.1391	0.1956	0.034*
C16	0.1429 (4)	0.1057 (7)	0.0993 (3)	0.0282 (15)
H16	0.1905	0.0295	0.0955	0.034*
C17	0.0766 (4)	0.1533 (7)	0.0478 (3)	0.0303 (16)
H17	0.0781	0.1087	0.0079	0.036*
C18	0.0056 (4)	0.2669 (7)	0.0517 (3)	0.0244 (15)
C19	0.0043 (4)	0.3361 (7)	0.1116 (3)	0.0224 (14)
C20	−0.0648 (4)	0.4581 (7)	0.1131 (3)	0.0266 (15)
H20	−0.0671	0.5070	0.1522	0.032*
C21	−0.1273 (4)	0.5060 (7)	0.0600 (3)	0.0305 (16)
H21	−0.1712	0.5906	0.0626	0.037*
C22	−0.1293 (4)	0.4334 (8)	0.0006 (3)	0.0337 (16)
H22	−0.1754	0.4644	−0.0361	0.040*
C23	−0.0625 (4)	0.3175 (7)	−0.0021 (3)	0.0294 (15)
H23	−0.0620	0.2693	−0.0417	0.035*
C24	0.3003 (4)	0.8937 (7)	0.3427 (3)	0.0347 (17)
H24A	0.2747	0.8572	0.2992	0.052*
H24B	0.3189	1.0102	0.3428	0.052*
H24C	0.2524	0.8811	0.3668	0.052*
C25	0.6418 (4)	0.8592 (8)	0.4547 (3)	0.051 (2)
H25A	0.6356	0.9314	0.4895	0.076*
H25B	0.6598	0.9255	0.4220	0.076*
H25C	0.6901	0.7755	0.4704	0.076*
C26	0.4524 (4)	0.3376 (7)	0.4039 (3)	0.0379 (17)
H26A	0.5139	0.2910	0.4037	0.057*
H26B	0.4055	0.2970	0.3672	0.057*
H26C	0.4347	0.3036	0.4426	0.057*
C27	0.4029 (4)	0.1710 (8)	0.2387 (3)	0.0284 (15)
C28	0.4682 (4)	0.0349 (7)	0.2396 (3)	0.0367 (17)
H28A	0.5068	0.0200	0.2825	0.055*
H28B	0.5088	0.0601	0.2112	0.055*
H28C	0.4330	−0.0670	0.2257	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0280 (4)	0.0304 (5)	0.0269 (4)	−0.0010 (4)	0.0089 (4)	−0.0029 (4)
I1	0.0350 (2)	0.0339 (3)	0.0303 (2)	0.0026 (2)	0.00674 (18)	0.0044 (2)
N1	0.024 (3)	0.027 (3)	0.021 (3)	−0.003 (2)	0.002 (2)	−0.003 (2)
N2	0.018 (3)	0.021 (3)	0.018 (3)	0.001 (2)	0.000 (2)	0.003 (2)
N3	0.025 (3)	0.033 (3)	0.037 (3)	0.004 (3)	0.012 (3)	−0.002 (3)
C1	0.022 (4)	0.032 (4)	0.017 (3)	−0.005 (3)	0.002 (3)	−0.002 (3)
C2	0.038 (4)	0.029 (4)	0.017 (3)	−0.007 (3)	0.009 (3)	−0.006 (3)
C3	0.040 (4)	0.025 (4)	0.028 (4)	−0.013 (3)	0.008 (3)	−0.006 (3)
C4	0.024 (4)	0.042 (5)	0.028 (4)	−0.008 (3)	0.001 (3)	0.007 (3)
C5	0.033 (4)	0.033 (4)	0.028 (4)	−0.004 (3)	−0.004 (3)	−0.001 (3)
C6	0.036 (4)	0.028 (4)	0.022 (4)	−0.009 (3)	0.003 (3)	0.002 (3)
C7	0.029 (4)	0.018 (3)	0.025 (4)	−0.003 (3)	0.005 (3)	−0.003 (3)
C8	0.018 (3)	0.039 (4)	0.030 (4)	−0.008 (3)	0.005 (3)	0.002 (3)
C9	0.027 (4)	0.015 (3)	0.027 (4)	−0.001 (3)	0.003 (3)	0.007 (3)
C10	0.029 (4)	0.024 (4)	0.024 (4)	0.004 (3)	0.012 (3)	0.002 (3)
C11	0.021 (3)	0.024 (4)	0.037 (4)	−0.001 (3)	0.016 (3)	0.002 (3)
C12	0.018 (3)	0.028 (4)	0.029 (4)	−0.001 (3)	0.006 (3)	0.001 (3)
C13	0.021 (3)	0.014 (3)	0.030 (4)	0.002 (3)	0.002 (3)	−0.002 (3)
C14	0.014 (3)	0.021 (3)	0.023 (3)	−0.005 (3)	0.004 (3)	0.003 (3)
C15	0.022 (3)	0.027 (4)	0.033 (4)	0.000 (3)	0.001 (3)	0.003 (3)
C16	0.026 (4)	0.029 (4)	0.034 (4)	0.005 (3)	0.014 (3)	0.000 (3)
C17	0.034 (4)	0.028 (4)	0.031 (4)	−0.006 (3)	0.011 (3)	−0.005 (3)
C18	0.021 (3)	0.025 (4)	0.026 (4)	−0.006 (3)	0.002 (3)	0.003 (3)
C19	0.024 (3)	0.018 (4)	0.025 (3)	−0.004 (3)	0.006 (3)	−0.001 (3)
C20	0.027 (4)	0.024 (4)	0.026 (4)	−0.007 (3)	0.003 (3)	−0.002 (3)
C21	0.023 (4)	0.029 (4)	0.038 (4)	0.007 (3)	0.004 (3)	0.004 (3)
C22	0.031 (4)	0.036 (4)	0.029 (4)	−0.001 (3)	−0.001 (3)	0.008 (3)
C23	0.034 (4)	0.034 (4)	0.020 (3)	−0.008 (3)	0.007 (3)	−0.001 (3)
C24	0.038 (4)	0.032 (4)	0.037 (4)	−0.004 (3)	0.014 (3)	−0.008 (3)
C25	0.041 (4)	0.047 (5)	0.054 (5)	−0.024 (4)	−0.008 (4)	0.001 (4)
C26	0.042 (4)	0.032 (4)	0.034 (4)	0.001 (3)	−0.002 (3)	0.007 (3)
C27	0.024 (4)	0.040 (4)	0.022 (3)	−0.006 (3)	0.006 (3)	0.000 (3)
C28	0.035 (4)	0.031 (4)	0.046 (4)	0.006 (3)	0.014 (3)	0.000 (3)

Geometric parameters (Å, º) top

Cu1—N3	1.960 (5)	C13—C14	1.507 (7)
Cu1—N2	2.085 (4)	C14—C15	1.355 (7)
Cu1—N1	2.091 (4)	C14—C19	1.426 (7)
Cu1—I1	2.5479 (9)	C15—C16	1.427 (7)
N1—C7	1.282 (7)	C15—H15	0.9500
N1—C1	1.434 (6)	C16—C17	1.354 (7)
N2—C13	1.342 (6)	C16—H16	0.9500
N2—C9	1.372 (6)	C17—C18	1.408 (7)
N3—C27	1.125 (7)	C17—H17	0.9500
C1—C2	1.382 (7)	C18—C23	1.409 (7)
C1—C6	1.386 (7)	C18—C19	1.427 (7)
C2—C3	1.403 (7)	C19—C20	1.420 (7)
C2—C24	1.508 (7)	C20—C21	1.351 (7)
C3—C4	1.366 (8)	C20—H20	0.9500
C3—H3	0.9500	C21—C22	1.420 (8)
C4—C5	1.369 (8)	C21—H21	0.9500
C4—C25	1.527 (7)	C22—C23	1.368 (7)
C5—C6	1.402 (7)	C22—H22	0.9500
C5—H5	0.9500	C23—H23	0.9500
C6—C26	1.501 (7)	C24—H24A	0.9800
C7—C9	1.500 (7)	C24—H24B	0.9800
C7—C8	1.515 (7)	C24—H24C	0.9800
C8—H8A	0.9800	C25—H25A	0.9800
C8—H8B	0.9800	C25—H25B	0.9800
C8—H8C	0.9800	C25—H25C	0.9800
C9—C10	1.377 (7)	C26—H26A	0.9800
C10—C11	1.389 (7)	C26—H26B	0.9800
C10—H10	0.9500	C26—H26C	0.9800
C11—C12	1.364 (7)	C27—C28	1.456 (8)
C11—H11	0.9500	C28—H28A	0.9800
C12—C13	1.387 (7)	C28—H28B	0.9800
C12—H12	0.9500	C28—H28C	0.9800

N3—Cu1—N2	115.94 (19)	C15—C14—C19	120.5 (5)
N3—Cu1—N1	110.75 (19)	C15—C14—C13	118.8 (5)
N2—Cu1—N1	78.86 (18)	C19—C14—C13	120.5 (5)
N3—Cu1—I1	112.74 (15)	C14—C15—C16	121.2 (5)
N2—Cu1—I1	119.51 (12)	C14—C15—H15	119.4
N1—Cu1—I1	114.43 (13)	C16—C15—H15	119.4
C7—N1—C1	120.8 (5)	C17—C16—C15	118.9 (6)
C7—N1—Cu1	116.2 (4)	C17—C16—H16	120.5
C1—N1—Cu1	122.9 (4)	C15—C16—H16	120.5
C13—N2—C9	117.5 (5)	C16—C17—C18	122.0 (6)
C13—N2—Cu1	128.9 (4)	C16—C17—H17	119.0
C9—N2—Cu1	113.5 (4)	C18—C17—H17	119.0
C27—N3—Cu1	175.3 (5)	C17—C18—C23	121.7 (6)
C2—C1—C6	121.7 (6)	C17—C18—C19	119.0 (5)
C2—C1—N1	118.9 (5)	C23—C18—C19	119.2 (5)
C6—C1—N1	119.2 (5)	C20—C19—C14	124.3 (5)
C1—C2—C3	118.0 (6)	C20—C19—C18	117.5 (5)
C1—C2—C24	121.6 (5)	C14—C19—C18	118.2 (5)
C3—C2—C24	120.4 (6)	C21—C20—C19	121.4 (6)
C4—C3—C2	121.5 (6)	C21—C20—H20	119.3
C4—C3—H3	119.2	C19—C20—H20	119.3
C2—C3—H3	119.2	C20—C21—C22	121.8 (6)
C3—C4—C5	119.3 (6)	C20—C21—H21	119.1
C3—C4—C25	120.2 (6)	C22—C21—H21	119.1
C5—C4—C25	120.5 (6)	C23—C22—C21	117.8 (6)
C4—C5—C6	121.6 (6)	C23—C22—H22	121.1
C4—C5—H5	119.2	C21—C22—H22	121.1
C6—C5—H5	119.2	C22—C23—C18	122.3 (6)
C1—C6—C5	117.9 (6)	C22—C23—H23	118.8
C1—C6—C26	122.3 (6)	C18—C23—H23	118.8
C5—C6—C26	119.8 (6)	C2—C24—H24A	109.5
N1—C7—C9	116.2 (5)	C2—C24—H24B	109.5
N1—C7—C8	126.0 (5)	H24A—C24—H24B	109.5
C9—C7—C8	117.8 (5)	C2—C24—H24C	109.5
C7—C8—H8A	109.5	H24A—C24—H24C	109.5
C7—C8—H8B	109.5	H24B—C24—H24C	109.5
H8A—C8—H8B	109.5	C4—C25—H25A	109.5
C7—C8—H8C	109.5	C4—C25—H25B	109.5
H8A—C8—H8C	109.5	H25A—C25—H25B	109.5
H8B—C8—H8C	109.5	C4—C25—H25C	109.5
N2—C9—C10	122.0 (5)	H25A—C25—H25C	109.5
N2—C9—C7	115.2 (5)	H25B—C25—H25C	109.5
C10—C9—C7	122.7 (5)	C6—C26—H26A	109.5
C9—C10—C11	119.6 (5)	C6—C26—H26B	109.5
C9—C10—H10	120.2	H26A—C26—H26B	109.5
C11—C10—H10	120.2	C6—C26—H26C	109.5
C12—C11—C10	118.3 (5)	H26A—C26—H26C	109.5
C12—C11—H11	120.8	H26B—C26—H26C	109.5
C10—C11—H11	120.8	N3—C27—C28	178.7 (7)
C11—C12—C13	120.2 (5)	C27—C28—H28A	109.5
C11—C12—H12	119.9	C27—C28—H28B	109.5
C13—C12—H12	119.9	H28A—C28—H28B	109.5
N2—C13—C12	122.2 (5)	C27—C28—H28C	109.5
N2—C13—C14	117.2 (5)	H28A—C28—H28C	109.5
C12—C13—C14	120.5 (5)	H28B—C28—H28C	109.5

N3—Cu1—N1—C7	−113.7 (4)	N1—C7—C9—N2	0.5 (7)
N2—Cu1—N1—C7	0.1 (4)	C8—C7—C9—N2	−179.3 (5)
I1—Cu1—N1—C7	117.6 (4)	N1—C7—C9—C10	−177.1 (5)
N3—Cu1—N1—C1	68.3 (5)	C8—C7—C9—C10	3.0 (8)
N2—Cu1—N1—C1	−178.0 (5)	N2—C9—C10—C11	0.6 (8)
I1—Cu1—N1—C1	−60.5 (4)	C7—C9—C10—C11	178.1 (5)
N3—Cu1—N2—C13	−74.9 (5)	C9—C10—C11—C12	−1.0 (8)
N1—Cu1—N2—C13	177.3 (5)	C10—C11—C12—C13	1.0 (9)
I1—Cu1—N2—C13	65.3 (5)	C9—N2—C13—C12	0.2 (8)
N3—Cu1—N2—C9	108.0 (4)	Cu1—N2—C13—C12	−176.7 (4)
N1—Cu1—N2—C9	0.2 (4)	C9—N2—C13—C14	−176.8 (5)
I1—Cu1—N2—C9	−111.7 (3)	Cu1—N2—C13—C14	6.3 (7)
C7—N1—C1—C2	−86.8 (7)	C11—C12—C13—N2	−0.7 (9)
Cu1—N1—C1—C2	91.2 (6)	C11—C12—C13—C14	176.2 (5)
C7—N1—C1—C6	97.6 (7)	N2—C13—C14—C15	56.3 (7)
Cu1—N1—C1—C6	−84.4 (6)	C12—C13—C14—C15	−120.8 (6)
C6—C1—C2—C3	0.7 (9)	N2—C13—C14—C19	−128.1 (5)
N1—C1—C2—C3	−174.8 (5)	C12—C13—C14—C19	54.8 (8)
C6—C1—C2—C24	−179.1 (5)	C19—C14—C15—C16	−2.4 (8)
N1—C1—C2—C24	5.4 (8)	C13—C14—C15—C16	173.3 (5)
C1—C2—C3—C4	0.2 (9)	C14—C15—C16—C17	0.1 (9)
C24—C2—C3—C4	180.0 (5)	C15—C16—C17—C18	0.5 (9)
C2—C3—C4—C5	−0.3 (9)	C16—C17—C18—C23	179.2 (6)
C2—C3—C4—C25	178.0 (5)	C16—C17—C18—C19	1.1 (8)
C3—C4—C5—C6	−0.5 (10)	C15—C14—C19—C20	−175.4 (5)
C25—C4—C5—C6	−178.8 (5)	C13—C14—C19—C20	9.0 (8)
C2—C1—C6—C5	−1.4 (9)	C15—C14—C19—C18	3.9 (8)
N1—C1—C6—C5	174.1 (5)	C13—C14—C19—C18	−171.7 (5)
C2—C1—C6—C26	179.1 (5)	C17—C18—C19—C20	176.1 (5)
N1—C1—C6—C26	−5.4 (9)	C23—C18—C19—C20	−2.1 (8)
C4—C5—C6—C1	1.3 (9)	C17—C18—C19—C14	−3.2 (8)
C4—C5—C6—C26	−179.2 (6)	C23—C18—C19—C14	178.6 (5)
C1—N1—C7—C9	177.8 (5)	C14—C19—C20—C21	179.7 (5)
Cu1—N1—C7—C9	−0.3 (7)	C18—C19—C20—C21	0.5 (8)
C1—N1—C7—C8	−2.4 (9)	C19—C20—C21—C22	2.1 (9)
Cu1—N1—C7—C8	179.5 (4)	C20—C21—C22—C23	−3.0 (9)
C13—N2—C9—C10	−0.2 (8)	C21—C22—C23—C18	1.3 (9)
Cu1—N2—C9—C10	177.2 (4)	C17—C18—C23—C22	−176.9 (5)
C13—N2—C9—C7	−177.8 (5)	C19—C18—C23—C22	1.2 (9)
Cu1—N2—C9—C7	−0.5 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C26—H26B···N1	0.98	2.52	2.891 (8)	102

Footnotes

‡Research Visitor at University of Leicester, UK.

Acknowledgements

The authors acknowledge the technical support given by the staff of the Department of Chemistry, University of Leicester. Special thanks to the postgraduate students Mona H. Alhalafi and Amina Isbilir for their constant support throughout the period of research.

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