Crystal structure of the [(1,3-dimesityl-1H-imidazol-3-ium-2-yl)methano-lato]copper(II) chloride dimer: insertion of formaldehyde into a copper-carbene bond.

The crystal structure of bis-[μ-(1,3-dimesityl-1H-imidazol-3-ium-2-yl)methano-lato-κ2O:O]bis-[di-chlorido-copper(II)], [Cu2Cl4(C22H26N2O)2], is reported. The complex is assumed to have formed via the insertion of formaldehyde into the copper-carbon bond in an N-heterocyclic carbene complex of copper(I) chloride. The structure of the binuclear mol-ecule possesses a crystallographic-ally centrosymmetric Cu2O2 central core with the O atoms bridging between the CuII atoms and thus Z' = 0.5. The copper centres are further ligated by two chloride ligands, resulting in the CuII atoms residing in a distorted square-planar environment. The Cu-O bond lengths are shorter than those previously reported in structures with the same central Cu2O2 motif. The complex displays C-H⋯Cl inter-actions involving the H atoms of the heterocycle backbone and the chloride ligands of a neighbouring mol-ecule.

Chemical context

The chemistry of N-heterocyclic carbene (NHC) ligands is prominent within the landscape of inorganic and organometallic chemistry and now, more than 25 years on from Arduengo’s land-mark paper (Arduengo et al., 1991 ▸), this prominence looks set to continue. One area that has proven fruitful is the chemistry of NHCs with the group 11 transition metal elements. In particular, the chemistry with copper has resulted in an abundance of complexes that have proven to be effective catalysts for a range of organic transformations, including conjugate addition and carboxyl­ation (Egbert et al., 2013 ▸). The preparation of neutral mono-NHC complexes with the general formulae [Cu(NHC)Cl] is routine and straightforward with a variety of synthetic routes to such species available (McLean et al., 2010 ▸; Santoro et al., 2013 ▸; Gibard et al., 2013 ▸; Lake et al., 2012 ▸). One of the simplest routes is the reaction of imidazol(in)ium chloride with Cu2O under reflux conditions with no requirement for the exclusion of air and water. The species formed are stable when they are isolated in the solid state but solutions show signs of oxidation upon standing for prolonged periods, especially when they are prepared in coordinating solvents such as THF or aceto­nitrile. The tell-tale green colour, which indicates the formation of copper(II) species, is surely a common observation for chemists who work with copper(I)–NHC species, but surprisingly the literature offers little on the identification of these species and corresponding reaction pathways. This is most likely a consequence of the inherent difficulty in characterizing the paramagnetic copper(II) species formed. Our inter­est in this area has previously revolved around the modification of [Cu(NHC)Cl] complexes through the replacement of the chloride ligand with the thio­cyanate ligand (Dodds & Kennedy, 2014 ▸). Herein we report the formation of the unusual (1,3-dimesityl-1H-imidazol-3-ium-2-yl) copper(II) chloride dimer, formed presumably from the insertion of formaldehyde into the Cu—NHC bond, upon prolonged standing of a THF solution containing [Cu(IMes)Cl] [IMes = 1,3-bis­(2,4,6-tri­methyl­phen­yl)imidazol-2-yl­idene] and trace amounts of formaldehyde at 255 K. The presence of formaldehyde was a result of the preparation of the imidazolium chloride precursor, which utilises paraformaldehyde. Evidently trace amounts of paraformaldehyde have been present during the reflux of Cu2O with imidazolium chloride, with the resulting solution generating the reported complex upon prolonged standing. This is the first structurally characterized example of a species formed through the insertion of a small mol­ecule into a copper—NHC bond. To date, all attempts to prepare the complex rationally have proven unsuccessful.

Structural commentary

The structure of the binuclear mol­ecule (I) consists of a Cu2O2Cl4 central core, possessing a Cu2O2 four-membered ring with each copper centre further coordinated by two chloride ligands. Each dimer is sited around a crystallographic centre of symmetry and thus Z′ = 0.5. The structure of the asymmetric unit, with atom labels, is given in Fig. 1 ▸ and the dimeric unit is shown in Fig. 2 ▸. The copper centres reside in a distorted square-planar environment, as can be evidenced by the O—Cu—O and Cl—Cu—Cl bond angles [74.10 (11) and 97.58 (5)° respectively], which both deviate markedly from 90°. This distortion from ideal square planar geometry is further illustrated by the trans O—Cu—Cl bond angles [162.46 (10) and 162.36 (9)°], which also deviate noticeably from the expected 180 °. Similar Cu2O2Cl4 central cores have been observed previously by a number of groups (Schäfer et al., 1965 ▸; Sager et al., 1967 ▸; Watson & Johnson, 1971 ▸; Ivashevskaja et al., 2002 ▸) with a similar distortion around the CuII atom observed. The Cu—O and Cu—Cl bond lengths are 1.934 (3) and 1.944 (3) Å and 2.2326 (13) and 2.2395 (12) Å, respectively. The Cu—O bond lengths are shorter than those observed in these previous reports [1.979–2.106 Å] while the Cu—Cl bond distances compare well to the previously reported examples [2.205–2.243 Å]. Finally, with regards to the central core, the Cu⋯Cu and O⋯O inter­nuclear distances are 3.0950 (12) and 2.337 (5) Å, respectively. The O⋯O distance is comparable to previous reports [2.366-2.591 Å] while the Cu⋯Cu distance is appreciably shorter when the comparison is made [3.190–3.245 Å]. The C—O bond length is 1.398 (4) Å, which is comparable with a structure previously reported by Hevia and co-workers (Uzelac et al., 2016 ▸) in which the zwitterion [ItBuCH2OGaR 3] [where ItBu = 1,3-bis­(tert-but­yl)imidazol-2-yl­idene; R = tri­methyl­silylmeth­yl] displays a C—O bond length of 1.384 (3) Å. The new C—C bond formed has a bond length of 1.497 (6) Å, which again compares well with the equivalent bond in the aforementioned zwitterion [1.505 (3) Å]. The imidazolium ring is positioned such that it forms a dihedral angle of 90° with the plane of the Cu2O2 ring, torsion angle O1—C1—C2—N1 = 0.2 (7)°. This syn arrangement results in the C5–C10 mesityl rings lying above and below the Cu2O2 ring, as shown in Fig. 2 ▸. The distance between the centroids of the Cu2O2 ring and the mesityl ring is 3.390 (2) Å.

Figure 1

View of the contents of the asymmetric unit of (I). Non-H atoms are drawn as 50% probability ellipsoids and H atoms as small spheres of arbitrary size.

Figure 2

Mol­ecular structure of dimeric (I). The two halves of the dimer are related by −x, −y + 1, −z + 2. H atoms are omitted for clarity.

Supra­molecular features

The complex exhibits inter­molecular C—H⋯Cl inter­actions, specifically two short inter­actions between the H atoms on the unsaturated backbone of the heterocycle and the chloride ligands of a neighbouring mol­ecule at position −x − , y + , −z + . The inter­molecular H⋯Cl distances measure 2.51 and 2.76 Å. These inter­actions combine to give a two-dimensional supra­molecular motif than propagates parallel to the (01) plane. Fig. 3 ▸ illustrates the C—H⋯Cl inter­molecular inter­actions and numerical details are given in Table 1 ▸.

Figure 3

View highlighting the close Cl⋯H contacts between neighbouring mol­ecules of (I). See text for details.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯Cl1i	0.99	2.59	3.216 (5)	121
C1—H1B⋯Cl2	0.99	2.54	3.215 (5)	126
C3—H3⋯Cl2ii	0.95	2.51	3.458 (6)	173
C4—H4⋯Cl1ii	0.95	2.76	3.385 (5)	124
C13—H13A⋯Cl2	0.98	2.79	3.684 (6)	152

Symmetry codes: (i) ; (ii) .

Database survey

Outside the complex reported herein, there are eight structures reported in the Cambridge Structural Database (CSD, Version 5.39, update No. 2, February 2018; Groom et al., 2016 ▸) that contain a Cu2O2Cl4 core and in which there is no additional coordination to the CuII atoms. The majority of structures reported contain pyridine N-oxide ligands (Schäfer et al., 1965 ▸: refcodes CUCPYO, CUCPYO11 and CUCPYO13; Sager et al., 1967 ▸: refcodes QQQBWD, QQQBWG and QQQBWJ; Watson & Johnson, 1971 ▸: refcode PHPYOC). The lone example that does not include a pyridine N-oxide ligand instead contains the related quinoline N-oxide ligand (Ivashevskaja et al., 2002 ▸; refcode HULZOD). We are aware of no previous examples of ligands formed from NHC by an insertion reaction similar to the one reported herein.

Synthesis and crystallization

[Cu(IMes)Cl] was prepared according to literature procedures outlined by Abernethy and co-workers (McLean et al., 2010 ▸). After isolation of an initial crop of [Cu(IMes)Cl], the filtrate was placed in the freezer (255 K) and left standing for ∼6 months. After this time the pale-orange THF solution had changed to a deep green and a small amount of green crystalline solid had precipitated alongside some green powder. This solid was isolated by filtration, yielding 34 mg of solid. The crystalline material isolated was suitable for single crystal X-ray diffraction. Additionally the isolated product was characterized by elemental analysis and ATR FT–IR.

Analysis calculated for C44H52N4O2Cl4Cu2: C, 56.38; H, 5.55; N, 5.98%. Found: C, 57.26; H, 5.64; N, 5.13%. ATR FT–IR: ν = 1502 (CO) cm−1.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. All H atoms were placed in calculated positions and refined in riding modes. C—H distances were 0.95, 0.99 and 0.98 Å for CH, CH2 and CH3 groups, respectively. For CH3 groups U iso(H) = 1.5U eq(C) and for all other types, U iso(H)i = 1.2U eq(C).

Table 2

Experimental details

Crystal data
Chemical formula	[Cu2Cl4(C22H26N2O)2]
M r	937.77
Crystal system, space group	Monoclinic, P21/n
Temperature (K)	123
a, b, c (Å)	11.1962 (8), 13.5321 (10), 15.5615 (8)
β (°)	107.705 (6)
V (Å3)	2246.0 (3)
Z	2
Radiation type	Mo Kα
μ (mm−1)	1.23
Crystal size (mm)	0.10 × 0.08 × 0.05
Data collection
Diffractometer	Oxford Diffraction Xcalibur E
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014 ▸)
T min, T max	0.993, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10241, 4960, 2814
R int	0.049
(sin θ/λ)max (Å−1)	0.676
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.062, 0.144, 1.05
No. of reflections	4960
No. of parameters	259
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.43, −0.32

Computer programs: CrysAlis PRO (Agilent, 2014 ▸), SIR92 (Altomare et al., 1994 ▸), SHELXL2014 (Sheldrick, 2015 ▸) and Mercury (Macrae et al., 2008 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S205698901801201X/pj2057sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901801201X/pj2057Isup2.hkl

CCDC reference: 1863799

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Cu2Cl4(C22H26N2O)2]	F(000) = 972
Mr = 937.77	Dx = 1.387 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.1962 (8) Å	Cell parameters from 2164 reflections
b = 13.5321 (10) Å	θ = 3.0–28.7°
c = 15.5615 (8) Å	µ = 1.23 mm−1
β = 107.705 (6)°	T = 123 K
V = 2246.0 (3) Å3	Prism, green
Z = 2	0.10 × 0.08 × 0.05 mm

Oxford Diffraction Xcalibur E diffractometer	2814 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.049
ω scans	θmax = 28.7°, θmin = 3.0°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −14→14
Tmin = 0.993, Tmax = 1.000	k = −18→16
10241 measured reflections	l = −19→19
4960 independent reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.062	H-atom parameters constrained
wR(F2) = 0.144	w = 1/[σ2(Fo2) + (0.0526P)2 + 0.3159P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
4960 reflections	Δρmax = 0.43 e Å−3
259 parameters	Δρmin = −0.32 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cu1	−0.06291 (5)	0.59936 (4)	0.96249 (3)	0.03601 (19)
Cl1	−0.20608 (13)	0.68984 (10)	1.00019 (8)	0.0548 (4)
Cl2	−0.03916 (12)	0.69819 (10)	0.85340 (7)	0.0489 (4)
O1	0.0280 (3)	0.4888 (2)	0.93419 (16)	0.0318 (7)
N1	−0.1319 (3)	0.3733 (3)	0.7821 (2)	0.0399 (10)
N2	−0.0002 (4)	0.3953 (3)	0.7078 (2)	0.0398 (10)
C1	0.0662 (4)	0.4767 (4)	0.8572 (2)	0.0333 (11)
H1A	0.1493	0.4442	0.8747	0.040*
H1B	0.0754	0.5426	0.8324	0.040*
C2	−0.0235 (4)	0.4165 (3)	0.7853 (3)	0.0321 (11)
C3	−0.1780 (5)	0.3228 (4)	0.7013 (3)	0.0551 (15)
H3	−0.2531	0.2852	0.6824	0.066*
C4	−0.0958 (5)	0.3371 (4)	0.6549 (3)	0.0585 (16)
H4	−0.1024	0.3119	0.5967	0.070*
C5	−0.1998 (4)	0.3750 (4)	0.8489 (3)	0.0350 (11)
C6	−0.1849 (4)	0.2964 (4)	0.9081 (3)	0.0396 (12)
C7	−0.2554 (5)	0.2987 (4)	0.9679 (3)	0.0476 (13)
H7	−0.2456	0.2469	1.0108	0.057*
C8	−0.3382 (5)	0.3731 (5)	0.9669 (3)	0.0604 (16)
C9	−0.3530 (5)	0.4476 (4)	0.9046 (3)	0.0582 (15)
H9	−0.4104	0.4996	0.9038	0.070*
C10	−0.2855 (5)	0.4490 (4)	0.8423 (3)	0.0470 (13)
C11	−0.1024 (5)	0.2100 (4)	0.9088 (3)	0.0574 (15)
H11A	−0.0598	0.1905	0.9712	0.086*
H11B	−0.0399	0.2280	0.8790	0.086*
H11C	−0.1532	0.1548	0.8765	0.086*
C12	−0.4118 (6)	0.3732 (6)	1.0350 (4)	0.104 (3)
H12A	−0.3942	0.3123	1.0706	0.156*
H12B	−0.5018	0.3771	1.0028	0.156*
H12C	−0.3868	0.4303	1.0751	0.156*
C13	−0.3075 (5)	0.5289 (4)	0.7712 (3)	0.0633 (16)
H13A	−0.2279	0.5618	0.7755	0.095*
H13B	−0.3672	0.5773	0.7808	0.095*
H13C	−0.3415	0.4992	0.7113	0.095*
C14	0.1027 (4)	0.4299 (4)	0.6795 (3)	0.0385 (12)
C15	0.2083 (5)	0.3714 (4)	0.6951 (3)	0.0460 (13)
C16	0.3012 (5)	0.4043 (4)	0.6583 (3)	0.0532 (14)
H16	0.3751	0.3659	0.6670	0.064*
C17	0.2875 (5)	0.4917 (4)	0.6093 (3)	0.0492 (14)
C18	0.1831 (5)	0.5488 (4)	0.5989 (3)	0.0433 (13)
H18	0.1762	0.6097	0.5674	0.052*
C19	0.0875 (4)	0.5205 (4)	0.6326 (3)	0.0376 (12)
C20	0.2251 (6)	0.2775 (4)	0.7500 (4)	0.0688 (18)
H20A	0.2424	0.2941	0.8140	0.103*
H20B	0.2955	0.2396	0.7419	0.103*
H20C	0.1484	0.2378	0.7299	0.103*
C21	0.3850 (5)	0.5198 (5)	0.5650 (4)	0.076 (2)
H21A	0.3568	0.4996	0.5015	0.115*
H21B	0.4643	0.4867	0.5959	0.115*
H21C	0.3975	0.5916	0.5687	0.115*
C22	−0.0275 (5)	0.5833 (4)	0.6182 (3)	0.0524 (15)
H22A	−0.0312	0.6085	0.6764	0.079*
H22B	−0.1023	0.5435	0.5900	0.079*
H22C	−0.0240	0.6390	0.5787	0.079*

	U11	U22	U33	U12	U13	U23
Cu1	0.0437 (4)	0.0389 (4)	0.0313 (3)	0.0073 (3)	0.0201 (2)	0.0036 (3)
Cl1	0.0691 (9)	0.0562 (9)	0.0510 (7)	0.0252 (8)	0.0361 (7)	0.0140 (7)
Cl2	0.0570 (8)	0.0511 (8)	0.0478 (7)	0.0139 (7)	0.0297 (6)	0.0161 (6)
O1	0.0394 (18)	0.0363 (18)	0.0253 (14)	0.0041 (15)	0.0180 (13)	−0.0012 (14)
N1	0.042 (2)	0.053 (3)	0.0291 (19)	−0.008 (2)	0.0179 (17)	−0.0087 (19)
N2	0.048 (2)	0.047 (3)	0.0303 (19)	−0.012 (2)	0.0217 (17)	−0.0134 (19)
C1	0.037 (3)	0.041 (3)	0.026 (2)	0.004 (2)	0.0169 (19)	−0.001 (2)
C2	0.040 (3)	0.032 (3)	0.029 (2)	−0.002 (2)	0.0169 (19)	−0.001 (2)
C3	0.060 (4)	0.070 (4)	0.039 (3)	−0.030 (3)	0.021 (2)	−0.018 (3)
C4	0.073 (4)	0.074 (4)	0.037 (3)	−0.029 (3)	0.029 (3)	−0.023 (3)
C5	0.027 (2)	0.044 (3)	0.036 (2)	−0.004 (2)	0.0137 (19)	−0.001 (2)
C6	0.036 (3)	0.045 (3)	0.040 (3)	−0.007 (2)	0.015 (2)	−0.005 (2)
C7	0.050 (3)	0.054 (4)	0.046 (3)	0.001 (3)	0.025 (2)	0.012 (3)
C8	0.054 (4)	0.081 (5)	0.062 (3)	0.009 (3)	0.041 (3)	0.013 (3)
C9	0.050 (3)	0.064 (4)	0.072 (4)	0.023 (3)	0.035 (3)	0.016 (3)
C10	0.043 (3)	0.059 (4)	0.040 (3)	0.001 (3)	0.014 (2)	0.011 (3)
C11	0.061 (4)	0.054 (4)	0.064 (3)	0.001 (3)	0.028 (3)	−0.009 (3)
C12	0.100 (5)	0.136 (7)	0.114 (5)	0.040 (5)	0.089 (5)	0.037 (5)
C13	0.070 (4)	0.062 (4)	0.057 (3)	0.010 (3)	0.018 (3)	0.017 (3)
C14	0.041 (3)	0.053 (3)	0.028 (2)	−0.012 (3)	0.021 (2)	−0.012 (2)
C15	0.061 (4)	0.041 (3)	0.042 (3)	0.000 (3)	0.026 (2)	−0.006 (2)
C16	0.051 (3)	0.063 (4)	0.054 (3)	0.011 (3)	0.027 (3)	−0.014 (3)
C17	0.052 (3)	0.061 (4)	0.043 (3)	−0.021 (3)	0.027 (2)	−0.015 (3)
C18	0.058 (3)	0.046 (3)	0.032 (2)	−0.011 (3)	0.023 (2)	−0.010 (2)
C19	0.045 (3)	0.047 (3)	0.024 (2)	−0.002 (3)	0.014 (2)	−0.008 (2)
C20	0.096 (5)	0.054 (4)	0.064 (3)	0.028 (4)	0.036 (3)	0.004 (3)
C21	0.072 (4)	0.082 (5)	0.097 (4)	−0.031 (4)	0.058 (4)	−0.029 (4)
C22	0.061 (4)	0.062 (4)	0.034 (3)	0.003 (3)	0.016 (2)	−0.006 (3)

Cu1—O1	1.934 (3)	C11—H11A	0.9800
Cu1—O1i	1.944 (3)	C11—H11B	0.9800
Cu1—Cl1	2.2326 (13)	C11—H11C	0.9800
Cu1—Cl2	2.2395 (12)	C12—H12A	0.9800
O1—C1	1.398 (4)	C12—H12B	0.9800
O1—Cu1i	1.944 (3)	C12—H12C	0.9800
N1—C2	1.334 (5)	C13—H13A	0.9800
N1—C3	1.386 (6)	C13—H13B	0.9800
N1—C5	1.463 (5)	C13—H13C	0.9800
N2—C2	1.341 (5)	C14—C15	1.381 (7)
N2—C4	1.381 (6)	C14—C19	1.410 (7)
N2—C14	1.432 (5)	C15—C16	1.404 (7)
C1—C2	1.497 (6)	C15—C20	1.511 (7)
C1—H1A	0.9900	C16—C17	1.390 (7)
C1—H1B	0.9900	C16—H16	0.9500
C3—C4	1.345 (6)	C17—C18	1.369 (7)
C3—H3	0.9500	C17—C21	1.507 (6)
C4—H4	0.9500	C18—C19	1.383 (6)
C5—C10	1.368 (6)	C18—H18	0.9500
C5—C6	1.383 (6)	C19—C22	1.502 (6)
C6—C7	1.392 (6)	C20—H20A	0.9800
C6—C11	1.488 (7)	C20—H20B	0.9800
C7—C8	1.365 (7)	C20—H20C	0.9800
C7—H7	0.9500	C21—H21A	0.9800
C8—C9	1.374 (7)	C21—H21B	0.9800
C8—C12	1.528 (6)	C21—H21C	0.9800
C9—C10	1.398 (6)	C22—H22A	0.9800
C9—H9	0.9500	C22—H22B	0.9800
C10—C13	1.513 (7)	C22—H22C	0.9800
O1—Cu1—O1i	74.10 (11)	C6—C11—H11C	109.5
O1—Cu1—Cl1	162.46 (10)	H11A—C11—H11C	109.5
O1i—Cu1—Cl1	95.69 (9)	H11B—C11—H11C	109.5
O1—Cu1—Cl2	95.60 (8)	C8—C12—H12A	109.5
O1i—Cu1—Cl2	162.36 (9)	C8—C12—H12B	109.5
Cl1—Cu1—Cl2	97.58 (5)	H12A—C12—H12B	109.5
C1—O1—Cu1	127.2 (3)	C8—C12—H12C	109.5
C1—O1—Cu1i	126.8 (3)	H12A—C12—H12C	109.5
Cu1—O1—Cu1i	105.90 (11)	H12B—C12—H12C	109.5
C2—N1—C3	109.5 (4)	C10—C13—H13A	109.5
C2—N1—C5	129.0 (4)	C10—C13—H13B	109.5
C3—N1—C5	121.5 (4)	H13A—C13—H13B	109.5
C2—N2—C4	109.3 (4)	C10—C13—H13C	109.5
C2—N2—C14	127.0 (4)	H13A—C13—H13C	109.5
C4—N2—C14	123.6 (3)	H13B—C13—H13C	109.5
O1—C1—C2	113.2 (3)	C15—C14—C19	123.5 (4)
O1—C1—H1A	108.9	C15—C14—N2	119.0 (5)
C2—C1—H1A	108.9	C19—C14—N2	117.5 (4)
O1—C1—H1B	108.9	C14—C15—C16	116.6 (5)
C2—C1—H1B	108.9	C14—C15—C20	122.3 (5)
H1A—C1—H1B	107.8	C16—C15—C20	121.1 (5)
N1—C2—N2	107.2 (4)	C17—C16—C15	121.4 (5)
N1—C2—C1	131.5 (3)	C17—C16—H16	119.3
N2—C2—C1	121.3 (4)	C15—C16—H16	119.3
C4—C3—N1	106.8 (4)	C18—C17—C16	119.6 (5)
C4—C3—H3	126.6	C18—C17—C21	120.9 (5)
N1—C3—H3	126.6	C16—C17—C21	119.4 (5)
C3—C4—N2	107.2 (4)	C17—C18—C19	122.0 (5)
C3—C4—H4	126.4	C17—C18—H18	119.0
N2—C4—H4	126.4	C19—C18—H18	119.0
C10—C5—C6	123.5 (4)	C18—C19—C14	116.9 (5)
C10—C5—N1	117.6 (4)	C18—C19—C22	120.9 (5)
C6—C5—N1	118.5 (4)	C14—C19—C22	122.2 (4)
C5—C6—C7	116.8 (5)	C15—C20—H20A	109.5
C5—C6—C11	123.9 (4)	C15—C20—H20B	109.5
C7—C6—C11	119.3 (5)	H20A—C20—H20B	109.5
C8—C7—C6	121.9 (5)	C15—C20—H20C	109.5
C8—C7—H7	119.0	H20A—C20—H20C	109.5
C6—C7—H7	119.0	H20B—C20—H20C	109.5
C7—C8—C9	119.1 (4)	C17—C21—H21A	109.5
C7—C8—C12	120.0 (5)	C17—C21—H21B	109.5
C9—C8—C12	120.9 (6)	H21A—C21—H21B	109.5
C8—C9—C10	121.6 (5)	C17—C21—H21C	109.5
C8—C9—H9	119.2	H21A—C21—H21C	109.5
C10—C9—H9	119.2	H21B—C21—H21C	109.5
C5—C10—C9	117.0 (5)	C19—C22—H22A	109.5
C5—C10—C13	122.1 (4)	C19—C22—H22B	109.5
C9—C10—C13	120.9 (5)	H22A—C22—H22B	109.5
C6—C11—H11A	109.5	C19—C22—H22C	109.5
C6—C11—H11B	109.5	H22A—C22—H22C	109.5
H11A—C11—H11B	109.5	H22B—C22—H22C	109.5
Cu1—O1—C1—C2	−95.8 (4)	C7—C8—C9—C10	0.1 (9)
Cu1i—O1—C1—C2	87.6 (4)	C12—C8—C9—C10	179.5 (6)
C3—N1—C2—N2	0.6 (5)	C6—C5—C10—C9	5.5 (7)
C5—N1—C2—N2	−178.9 (4)	N1—C5—C10—C9	177.7 (5)
C3—N1—C2—C1	−178.0 (5)	C6—C5—C10—C13	−174.4 (5)
C5—N1—C2—C1	2.5 (8)	N1—C5—C10—C13	−2.1 (7)
C4—N2—C2—N1	−0.3 (6)	C8—C9—C10—C5	−2.9 (8)
C14—N2—C2—N1	176.7 (5)	C8—C9—C10—C13	177.0 (5)
C4—N2—C2—C1	178.5 (4)	C2—N2—C14—C15	95.2 (6)
C14—N2—C2—C1	−4.5 (7)	C4—N2—C14—C15	−88.2 (6)
O1—C1—C2—N1	0.2 (7)	C2—N2—C14—C19	−88.1 (5)
O1—C1—C2—N2	−178.3 (4)	C4—N2—C14—C19	88.6 (6)
C2—N1—C3—C4	−0.7 (6)	C19—C14—C15—C16	−2.6 (7)
C5—N1—C3—C4	178.9 (5)	N2—C14—C15—C16	173.9 (4)
N1—C3—C4—N2	0.5 (7)	C19—C14—C15—C20	176.5 (4)
C2—N2—C4—C3	−0.1 (7)	N2—C14—C15—C20	−7.0 (7)
C14—N2—C4—C3	−177.3 (5)	C14—C15—C16—C17	0.5 (7)
C2—N1—C5—C10	90.0 (6)	C20—C15—C16—C17	−178.6 (5)
C3—N1—C5—C10	−89.4 (6)	C15—C16—C17—C18	2.0 (7)
C2—N1—C5—C6	−97.3 (6)	C15—C16—C17—C21	−175.3 (4)
C3—N1—C5—C6	83.2 (6)	C16—C17—C18—C19	−2.6 (7)
C10—C5—C6—C7	−5.0 (7)	C21—C17—C18—C19	174.7 (4)
N1—C5—C6—C7	−177.2 (4)	C17—C18—C19—C14	0.6 (6)
C10—C5—C6—C11	172.9 (5)	C17—C18—C19—C22	−178.4 (4)
N1—C5—C6—C11	0.7 (7)	C15—C14—C19—C18	2.1 (6)
C5—C6—C7—C8	1.9 (8)	N2—C14—C19—C18	−174.5 (4)
C11—C6—C7—C8	−176.1 (5)	C15—C14—C19—C22	−178.9 (4)
C6—C7—C8—C9	0.4 (9)	N2—C14—C19—C22	4.5 (6)
C6—C7—C8—C12	−179.0 (6)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···Cl1i	0.99	2.59	3.216 (5)	121
C1—H1B···Cl2	0.99	2.54	3.215 (5)	126
C3—H3···Cl2ii	0.95	2.51	3.458 (6)	173
C4—H4···Cl1ii	0.95	2.76	3.385 (5)	124
C13—H13A···Cl2	0.98	2.79	3.684 (6)	152