Acetonyltri-phenyl-phospho-nium 2,3,5-tri-phenyl-tetra-zolium tetra-chlorido-cuprate(II).

The title compound, (C21H20OP)(C19H15N4)[CuCl4], was obtained by reacting CuCl2·2H2O with a mixture of one equivalent of acetonyltri-phenyl-phospho-nium chloride and one equivalent of 2,3,5-tri-phenyl-tetra-zolium chloride in aceto-nitrile. In the structure, the Cu centre in the dianion is bonded to four chloride ligands and adopts a distorted tetra-hedral geometry. The phospho-nium cation likewise adopts the expected tetra-hedral geometry. The tetra-zolium ring forms dihedral angles of 77.68 (10), 26.85 (11) and 66.48 (10)° with the planes of the benzene rings of the substituent groups. In the crystal, weak C-H⋯Cl hydrogen-bonding inter-actions involving both cations and the anion give rise to a three-dimensional supra-molecular structure.

Chemical context

Compounds containing the [CuCl4]2− tetra­hedral dianion with various cations have been widely studied (Wei & Willett, 2002 ▸; Elangovan et al., 2007 ▸; Haddad & Al-Far, 2008 ▸; Al-Ktaifani & Rukiah, 2012 ▸; Wikaira et al., 2013 ▸; Laus et al., 2015 ▸). Likewise, a few compounds with an acetonyl tri­phenyl­phospho­nium or 2,3,5-tri­phenyl­tetra­zolium cation have also been reported (Diop et al., 2013 ▸, 2015 ▸; Zhang et al., 2007 ▸). To expand on the available data on both the [CuCl4]2− anion as well as that on acetonyltri­phenyl­phospho­nium and 2,3,5-tri­phenyl­tetra­zolium cations, we have initiated in this work the study of the inter­actions between CuCl2·2H2O, acetonyl tri­phenyl­phospho­nium chloride and 2,3,5-tri­phenyl­tetra­zolium chloride, expecting the presence of both cations in the resulting compound. This has yielded the title complex salt, (C21H20OP)+·(C19H15N4)+·[CuCl4]2− whose crystal structure is reported herein.

Structural commentary

The asymmetric unit of the title complex comprises an acetonyl tri­phenyl­phospho­nium cation, a 2,3,5-tri­phenyl­tetra­zolium cation and a tetra­chlorido­cuprate dianion (Fig. 1 ▸). The environment around the CuII atom is distorted tetra­hedral with distances and angles [Cu—Cl = 2.2327 (6)–2.2540 (5) Å and Cl—Cu—Cl = 97.67 (2)–135.49 (2)°] in normal ranges for the [CuCl4]2− complex anion (Clay et al., 1975 ▸; Laus et al., 2015 ▸). The P—C distances within the acetonyl tri­phenyl­phospho­nium cation are similar to those reported for the same cation (Diop et al., 2013 ▸, 2015 ▸). The range for the C—P—C angles [107.07 (9)–113.36 (10)°] indicate a small variation of the geometry for this cation. Present in the cation is a C21—H⋯O1 inter­action [3.147 (3) Å with C—H⋯O angle = 115°]. The N—C and N—N distances within the 2,3,5-triphenyl tetra­zolium cation are consistent with a π delocalization in the tetra­zolium ring, which forms dihedral angles of 77.68 (10), 26.85 (11) and 66.48 (10)° with the planes of the benzene rings of the substituent groups.

Figure 1

The mol­ecular components of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

Supra­molecular features

In the crystal, inter-species C—H⋯Cl hydrogen bonds between aromatic, methyl­ene and methyl H atoms of the acetonyl tri­phenyl­phospho­nium cation and the [CuCl4]2− anions are present (Table 1 ▸) together with weak C—H⋯Cl hydrogen-bonding inter­actions involving phenyl H atoms of the 2,3,5-triphenyl tetra­zolium cations. A three-dimensional supra­molecular structure is formed (Fig. 2 ▸).

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯Cl2i	0.99	2.54	3.363 (2)	141
C1—H1B⋯Cl2ii	0.99	2.69	3.662 (2)	168
C3—H3B⋯Cl3ii	0.98	2.74	3.714 (2)	171
C3—H3C⋯Cl2i	0.98	2.90	3.630 (2)	132
C9—H9⋯Cl2ii	0.95	2.97	3.917 (2)	172
C24—H24⋯Cl3ii	0.95	2.99	3.783 (2)	142
C28—H28⋯Cl1	0.95	2.72	3.605 (2)	156
C30—H30⋯Cl3ii	0.95	2.87	3.683 (2)	144
C30—H30⋯Cl4ii	0.95	2.85	3.630 (2)	140

Symmetry codes: (i) ; (ii) .

Figure 2

A view of the packing of the title compound viewed along [100], with hydrogen-bonding inter­actions shown as dashed lines. Displacement ellipsoids are drawn at the 50% probability level. The acetonyltriphenylphosphonium cations form supramolecular dimers through pairs of centrosymmetric C—H⋯O interactions.

Database survey

A search of the Cambridge Structural Database (CSD version 5.39; Groom et al., 2016 ▸) returned hundreds and hundreds of different structures containing the [CuCl4]2− dianion. To date, only nine structures of acetonyl tri­phenyl­phospho­nium and seventeen structures of 2,3,5-tri­phenyl­tetra­zolium have been deposited in the CSD. No structure including both acetonyltri­phenyl­phospho­nium and 2,3,5-tri­phenyl­tetra­zolium species was found.

Synthesis and crystallization

All chemicals were purchased from Aldrich Company, Germany and used as received. Acetonyl tri­phenyl­phospho­nium chloride and 2,3,5-triphenyl tetra­zolium chloride were mixed in aceto­nitrile with CuCl2·2H2O in a 1:1:1 ratio: a yellow–orange solution was obtained. Orange crystals suitable for a single-crystal X-ray diffraction study were obtained after a slow solvent evaporation at room temperature (300 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. All H atoms were placed at calculated positions and refined as riding atoms, with C—H = 0.95 Å (aromatic), 0.99 Å (methyl­ene) or 0.98 Å (meth­yl), and with U iso(H) = 1.2U eq(aromatic or methyl­ene) or 1.5U eq(meth­yl).

Table 2

Experimental details

Crystal data
Chemical formula	(C21H20OP)(C19H15N4)[CuCl4]
M r	824.03
Crystal system, space group	Monoclinic, P21/n
Temperature (K)	120
a, b, c (Å)	10.6868 (12), 26.421 (3), 13.5628 (15)
β (°)	90.709 (1)
V (Å3)	3829.2 (7)
Z	4
Radiation type	Mo Kα
μ (mm−1)	0.93
Crystal size (mm)	0.29 × 0.20 × 0.16
Data collection
Diffractometer	Bruker APEXII
Absorption correction	Numerical (SADABS; Krause et al., 2015 ▸)
T min, T max	0.850, 0.939
No. of measured, independent and observed [I > 2σ(I)] reflections	86744, 9517, 7659
R int	0.046
(sin θ/λ)max (Å−1)	0.668
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.037, 0.096, 1.04
No. of reflections	9517
No. of parameters	461
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.59, −0.31

Computer programs: APEX2 , SAINT and XP (Bruker, 2015 ▸), SHELXS2014 (Sheldrick, 2015a ▸), SHELXL2014 (Sheldrick, 2015b ▸) and CIFTAB (Sheldrick, 2015b ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S205698901701800X/zs2394sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901701800X/zs2394Isup2.hkl

CCDC reference: 1811873

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

(C21H20OP)(C19H15N4)[CuCl4]	F(000) = 1692
Mr = 824.03	Dx = 1.429 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.6868 (12) Å	Cell parameters from 9465 reflections
b = 26.421 (3) Å	θ = 2.4–28.1°
c = 13.5628 (15) Å	µ = 0.93 mm−1
β = 90.709 (1)°	T = 120 K
V = 3829.2 (7) Å3	Irregular fragment, orange
Z = 4	0.29 × 0.20 × 0.16 mm

Bruker APEXII diffractometer	9517 independent reflections
Radiation source: fine-focus sealed tube	7659 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
Detector resolution: 8.33 pixels mm-1	θmax = 28.3°, θmin = 1.5°
combination of ω and φ–scans	h = −14→14
Absorption correction: numerical (SADABS; Krause et al., 2015)	k = −35→35
Tmin = 0.850, Tmax = 0.939	l = −18→18
86744 measured reflections

Refinement on F2	Primary atom site location: real-space vector search
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0444P)2 + 2.8241P] where P = (Fo2 + 2Fc2)/3
9517 reflections	(Δ/σ)max = 0.003
461 parameters	Δρmax = 0.59 e Å−3
0 restraints	Δρmin = −0.31 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	0.18416 (2)	0.83950 (2)	0.46171 (2)	0.01990 (7)
Cl1	0.37755 (5)	0.83273 (2)	0.40187 (4)	0.03219 (12)
Cl2	0.18895 (5)	0.92209 (2)	0.50256 (4)	0.03061 (12)
Cl3	−0.00778 (4)	0.83854 (2)	0.39095 (4)	0.02588 (11)
Cl4	0.17809 (5)	0.76656 (2)	0.54465 (4)	0.03418 (13)
P1	0.62501 (5)	0.46610 (2)	0.76661 (4)	0.02193 (11)
O1	0.35961 (15)	0.49029 (6)	0.72476 (11)	0.0365 (4)
C1	0.51075 (18)	0.48642 (8)	0.85438 (14)	0.0242 (4)
H1A	0.4910	0.4578	0.8987	0.029*
H1B	0.5471	0.5139	0.8953	0.029*
C2	0.38982 (18)	0.50531 (8)	0.80594 (15)	0.0258 (4)
C3	0.3142 (2)	0.54137 (8)	0.86465 (16)	0.0299 (4)
H3A	0.2388	0.5508	0.8271	0.045*
H3B	0.3639	0.5718	0.8788	0.045*
H3C	0.2902	0.5253	0.9267	0.045*
C4	0.64250 (18)	0.51654 (8)	0.67895 (15)	0.0242 (4)
C5	0.6371 (2)	0.50811 (8)	0.57820 (15)	0.0286 (4)
H5	0.6253	0.4748	0.5534	0.034*
C6	0.6490 (2)	0.54866 (9)	0.51329 (16)	0.0344 (5)
H6	0.6462	0.5430	0.4441	0.041*
C7	0.6650 (2)	0.59706 (9)	0.54977 (18)	0.0363 (5)
H7	0.6730	0.6248	0.5056	0.044*
C8	0.6693 (2)	0.60526 (9)	0.65035 (18)	0.0372 (5)
H8	0.6805	0.6386	0.6749	0.045*
C9	0.6576 (2)	0.56546 (8)	0.71550 (17)	0.0333 (5)
H9	0.6599	0.5714	0.7846	0.040*
C10	0.76907 (18)	0.45595 (8)	0.83306 (15)	0.0262 (4)
C11	0.8699 (2)	0.48849 (10)	0.82425 (19)	0.0408 (6)
H11	0.8650	0.5172	0.7822	0.049*
C12	0.9787 (2)	0.47832 (13)	0.8783 (2)	0.0576 (8)
H12	1.0487	0.5002	0.8725	0.069*
C13	0.9863 (2)	0.43719 (12)	0.9400 (2)	0.0528 (7)
H13	1.0613	0.4307	0.9760	0.063*
C14	0.8858 (2)	0.40559 (10)	0.9494 (2)	0.0450 (6)
H14	0.8908	0.3775	0.9930	0.054*
C15	0.7763 (2)	0.41431 (9)	0.89564 (18)	0.0361 (5)
H15	0.7070	0.3920	0.9016	0.043*
C16	0.5878 (2)	0.40659 (8)	0.71009 (15)	0.0268 (4)
C17	0.6791 (2)	0.38438 (9)	0.65135 (16)	0.0355 (5)
H17	0.7554	0.4017	0.6396	0.043*
C18	0.6582 (3)	0.33723 (9)	0.61035 (18)	0.0441 (6)
H18	0.7192	0.3223	0.5691	0.053*
C19	0.5484 (3)	0.31196 (9)	0.6296 (2)	0.0500 (7)
H19	0.5346	0.2793	0.6022	0.060*
C20	0.4587 (3)	0.33336 (9)	0.6881 (2)	0.0486 (7)
H20	0.3836	0.3154	0.7008	0.058*
C21	0.4772 (2)	0.38109 (8)	0.72871 (18)	0.0355 (5)
H21	0.4148	0.3961	0.7687	0.043*
N1	0.41588 (15)	0.68767 (6)	0.64421 (12)	0.0231 (3)
N2	0.46486 (15)	0.72999 (6)	0.67689 (12)	0.0218 (3)
N3	0.38773 (14)	0.75180 (6)	0.74104 (12)	0.0219 (3)
N4	0.28719 (15)	0.72419 (6)	0.75175 (12)	0.0225 (3)
C22	0.30628 (17)	0.68472 (7)	0.69106 (14)	0.0217 (4)
C23	0.58844 (18)	0.74780 (7)	0.65044 (15)	0.0237 (4)
C24	0.68680 (19)	0.73834 (8)	0.71430 (16)	0.0280 (4)
H24	0.6733	0.7241	0.7776	0.034*
C25	0.80653 (19)	0.75032 (8)	0.68297 (17)	0.0318 (5)
H25	0.8765	0.7440	0.7251	0.038*
C26	0.8245 (2)	0.77132 (9)	0.59150 (18)	0.0349 (5)
H26	0.9067	0.7793	0.5707	0.042*
C27	0.7234 (2)	0.78090 (10)	0.52971 (17)	0.0389 (5)
H27	0.7367	0.7956	0.4668	0.047*
C28	0.6029 (2)	0.76927 (9)	0.55851 (16)	0.0315 (5)
H28	0.5329	0.7758	0.5166	0.038*
C29	0.40967 (18)	0.80011 (8)	0.78841 (15)	0.0243 (4)
C30	0.4634 (2)	0.80027 (8)	0.88116 (16)	0.0315 (5)
H30	0.4889	0.7697	0.9122	0.038*
C31	0.4789 (2)	0.84658 (9)	0.92767 (18)	0.0392 (5)
H31	0.5162	0.8481	0.9915	0.047*
C32	0.4403 (2)	0.89058 (9)	0.88143 (19)	0.0376 (5)
H32	0.4505	0.9221	0.9141	0.045*
C33	0.3869 (3)	0.88917 (9)	0.7881 (2)	0.0442 (6)
H33	0.3608	0.9197	0.7570	0.053*
C34	0.3714 (2)	0.84312 (8)	0.73976 (18)	0.0373 (5)
H34	0.3356	0.8415	0.6754	0.045*
C35	0.21638 (18)	0.64331 (7)	0.67518 (14)	0.0225 (4)
C36	0.0992 (2)	0.64553 (9)	0.71863 (17)	0.0314 (5)
H36	0.0781	0.6733	0.7596	0.038*
C37	0.0135 (2)	0.60693 (9)	0.70173 (18)	0.0371 (5)
H37	−0.0665	0.6081	0.7314	0.045*
C38	0.0449 (2)	0.56676 (9)	0.64165 (17)	0.0344 (5)
H38	−0.0146	0.5408	0.6287	0.041*
C39	0.1622 (2)	0.56409 (8)	0.60035 (16)	0.0322 (5)
H39	0.1837	0.5359	0.5605	0.039*
C40	0.24869 (19)	0.60236 (8)	0.61681 (15)	0.0276 (4)
H40	0.3294	0.6005	0.5884	0.033*

	U11	U22	U33	U12	U13	U23
Cu1	0.01889 (12)	0.01888 (12)	0.02188 (12)	0.00136 (8)	−0.00154 (8)	−0.00022 (9)
Cl1	0.0206 (2)	0.0399 (3)	0.0361 (3)	0.0023 (2)	0.00368 (19)	−0.0073 (2)
Cl2	0.0262 (2)	0.0225 (2)	0.0430 (3)	0.00192 (19)	−0.0028 (2)	−0.0096 (2)
Cl3	0.0214 (2)	0.0246 (2)	0.0315 (2)	−0.00047 (17)	−0.00662 (18)	0.00112 (19)
Cl4	0.0374 (3)	0.0270 (3)	0.0379 (3)	−0.0007 (2)	−0.0100 (2)	0.0112 (2)
P1	0.0215 (2)	0.0225 (2)	0.0219 (2)	−0.00009 (19)	0.00078 (18)	−0.00152 (19)
O1	0.0346 (8)	0.0422 (9)	0.0324 (8)	0.0075 (7)	−0.0091 (7)	−0.0084 (7)
C1	0.0229 (9)	0.0283 (10)	0.0214 (9)	0.0004 (8)	0.0029 (7)	−0.0025 (8)
C2	0.0239 (9)	0.0245 (10)	0.0290 (10)	−0.0021 (8)	0.0016 (8)	0.0005 (8)
C3	0.0303 (11)	0.0227 (10)	0.0366 (11)	0.0029 (8)	0.0051 (9)	0.0017 (9)
C4	0.0238 (9)	0.0230 (10)	0.0260 (10)	0.0013 (7)	0.0034 (7)	−0.0004 (8)
C5	0.0312 (11)	0.0266 (11)	0.0279 (10)	−0.0002 (8)	0.0005 (8)	−0.0029 (8)
C6	0.0367 (12)	0.0402 (13)	0.0263 (11)	−0.0003 (10)	0.0013 (9)	0.0045 (9)
C7	0.0385 (12)	0.0321 (12)	0.0385 (12)	0.0040 (10)	0.0016 (10)	0.0100 (10)
C8	0.0474 (14)	0.0222 (11)	0.0422 (13)	0.0008 (10)	0.0035 (10)	0.0010 (9)
C9	0.0450 (13)	0.0259 (11)	0.0293 (11)	0.0020 (9)	0.0020 (9)	−0.0029 (9)
C10	0.0230 (9)	0.0288 (11)	0.0268 (10)	0.0033 (8)	0.0011 (7)	−0.0032 (8)
C11	0.0267 (11)	0.0484 (15)	0.0471 (14)	−0.0069 (10)	−0.0003 (10)	0.0021 (11)
C12	0.0228 (12)	0.078 (2)	0.072 (2)	−0.0072 (13)	−0.0036 (12)	−0.0031 (17)
C13	0.0309 (13)	0.0672 (19)	0.0598 (17)	0.0169 (13)	−0.0146 (12)	−0.0122 (15)
C14	0.0468 (15)	0.0390 (14)	0.0488 (15)	0.0165 (11)	−0.0157 (12)	−0.0051 (11)
C15	0.0357 (12)	0.0309 (12)	0.0414 (13)	0.0038 (9)	−0.0095 (10)	−0.0019 (10)
C16	0.0335 (11)	0.0218 (10)	0.0249 (10)	−0.0004 (8)	−0.0032 (8)	0.0005 (8)
C17	0.0474 (13)	0.0300 (12)	0.0292 (11)	0.0033 (10)	0.0042 (10)	−0.0011 (9)
C18	0.0739 (19)	0.0283 (12)	0.0300 (12)	0.0084 (12)	0.0016 (12)	−0.0045 (9)
C19	0.078 (2)	0.0225 (12)	0.0493 (16)	−0.0013 (12)	−0.0186 (14)	−0.0061 (11)
C20	0.0479 (15)	0.0266 (12)	0.0709 (19)	−0.0099 (11)	−0.0150 (14)	−0.0003 (12)
C21	0.0342 (12)	0.0270 (11)	0.0452 (13)	−0.0009 (9)	−0.0055 (10)	0.0008 (10)
N1	0.0213 (8)	0.0232 (8)	0.0247 (8)	0.0005 (6)	−0.0019 (6)	0.0004 (6)
N2	0.0208 (8)	0.0220 (8)	0.0225 (8)	0.0013 (6)	0.0011 (6)	−0.0002 (6)
N3	0.0190 (7)	0.0237 (8)	0.0228 (8)	0.0030 (6)	−0.0006 (6)	0.0000 (6)
N4	0.0199 (8)	0.0236 (8)	0.0240 (8)	−0.0001 (6)	−0.0017 (6)	0.0026 (6)
C22	0.0205 (9)	0.0227 (9)	0.0219 (9)	0.0018 (7)	−0.0015 (7)	0.0039 (7)
C23	0.0207 (9)	0.0227 (10)	0.0277 (10)	−0.0007 (7)	0.0031 (7)	−0.0026 (8)
C24	0.0261 (10)	0.0290 (11)	0.0288 (10)	−0.0021 (8)	−0.0004 (8)	0.0015 (8)
C25	0.0226 (10)	0.0316 (11)	0.0411 (12)	−0.0017 (8)	−0.0005 (8)	−0.0031 (9)
C26	0.0296 (11)	0.0316 (12)	0.0438 (13)	−0.0066 (9)	0.0111 (9)	−0.0080 (10)
C27	0.0420 (13)	0.0451 (14)	0.0300 (11)	−0.0077 (11)	0.0124 (10)	0.0028 (10)
C28	0.0318 (11)	0.0367 (12)	0.0260 (10)	−0.0025 (9)	−0.0008 (8)	0.0019 (9)
C29	0.0227 (9)	0.0232 (10)	0.0270 (10)	0.0004 (7)	0.0027 (7)	−0.0026 (8)
C30	0.0374 (12)	0.0273 (11)	0.0298 (11)	0.0035 (9)	−0.0021 (9)	−0.0011 (9)
C31	0.0462 (14)	0.0373 (13)	0.0339 (12)	−0.0017 (11)	−0.0022 (10)	−0.0083 (10)
C32	0.0379 (12)	0.0277 (11)	0.0472 (14)	−0.0023 (9)	0.0065 (10)	−0.0092 (10)
C33	0.0549 (16)	0.0244 (12)	0.0531 (15)	0.0043 (11)	−0.0057 (12)	0.0016 (11)
C34	0.0471 (14)	0.0284 (12)	0.0361 (12)	0.0035 (10)	−0.0086 (10)	0.0017 (9)
C35	0.0215 (9)	0.0220 (9)	0.0239 (9)	−0.0004 (7)	−0.0022 (7)	0.0033 (7)
C36	0.0251 (10)	0.0324 (11)	0.0368 (12)	−0.0023 (9)	0.0049 (8)	−0.0037 (9)
C37	0.0284 (11)	0.0386 (13)	0.0446 (13)	−0.0076 (9)	0.0072 (9)	−0.0040 (10)
C38	0.0356 (12)	0.0298 (11)	0.0379 (12)	−0.0109 (9)	0.0009 (9)	0.0005 (9)
C39	0.0391 (12)	0.0257 (11)	0.0320 (11)	−0.0035 (9)	0.0021 (9)	−0.0016 (9)
C40	0.0275 (10)	0.0256 (10)	0.0299 (10)	0.0009 (8)	0.0047 (8)	0.0013 (8)

Cu1—Cl4	2.2327 (6)	C19—H19	0.9500
Cu1—Cl1	2.2368 (6)	C20—C21	1.389 (3)
Cu1—Cl2	2.2518 (6)	C20—H20	0.9500
Cu1—Cl3	2.2540 (5)	C21—H21	0.9500
P1—C16	1.792 (2)	N1—N2	1.310 (2)
P1—C10	1.794 (2)	N1—C22	1.342 (2)
P1—C4	1.797 (2)	N2—N3	1.336 (2)
P1—C1	1.7979 (19)	N2—C23	1.451 (2)
O1—C2	1.210 (3)	N3—N4	1.308 (2)
C1—C2	1.526 (3)	N3—C29	1.447 (3)
C1—H1A	0.9900	N4—C22	1.346 (3)
C1—H1B	0.9900	C22—C35	1.470 (3)
C2—C3	1.487 (3)	C23—C24	1.377 (3)
C3—H3A	0.9800	C23—C28	1.380 (3)
C3—H3B	0.9800	C24—C25	1.390 (3)
C3—H3C	0.9800	C24—H24	0.9500
C4—C5	1.385 (3)	C25—C26	1.375 (3)
C4—C9	1.393 (3)	C25—H25	0.9500
C5—C6	1.393 (3)	C26—C27	1.383 (3)
C5—H5	0.9500	C26—H26	0.9500
C6—C7	1.381 (3)	C27—C28	1.384 (3)
C6—H6	0.9500	C27—H27	0.9500
C7—C8	1.381 (3)	C28—H28	0.9500
C7—H7	0.9500	C29—C34	1.374 (3)
C8—C9	1.380 (3)	C29—C30	1.376 (3)
C8—H8	0.9500	C30—C31	1.385 (3)
C9—H9	0.9500	C30—H30	0.9500
C10—C11	1.385 (3)	C31—C32	1.382 (3)
C10—C15	1.391 (3)	C31—H31	0.9500
C11—C12	1.393 (4)	C32—C33	1.383 (4)
C11—H11	0.9500	C32—H32	0.9500
C12—C13	1.373 (4)	C33—C34	1.391 (3)
C12—H12	0.9500	C33—H33	0.9500
C13—C14	1.368 (4)	C34—H34	0.9500
C13—H13	0.9500	C35—C40	1.387 (3)
C14—C15	1.390 (3)	C35—C36	1.391 (3)
C14—H14	0.9500	C36—C37	1.388 (3)
C15—H15	0.9500	C36—H36	0.9500
C16—C21	1.387 (3)	C37—C38	1.382 (3)
C16—C17	1.396 (3)	C37—H37	0.9500
C17—C18	1.381 (3)	C38—C39	1.381 (3)
C17—H17	0.9500	C38—H38	0.9500
C18—C19	1.378 (4)	C39—C40	1.386 (3)
C18—H18	0.9500	C39—H39	0.9500
C19—C20	1.373 (4)	C40—H40	0.9500
Cl4—Cu1—Cl1	98.43 (2)	C20—C19—H19	119.6
Cl4—Cu1—Cl2	135.49 (2)	C18—C19—H19	119.6
Cl1—Cu1—Cl2	98.54 (2)	C19—C20—C21	120.4 (3)
Cl4—Cu1—Cl3	99.95 (2)	C19—C20—H20	119.8
Cl1—Cu1—Cl3	133.21 (2)	C21—C20—H20	119.8
Cl2—Cu1—Cl3	97.67 (2)	C16—C21—C20	119.0 (2)
C16—P1—C10	105.55 (10)	C16—C21—H21	120.5
C16—P1—C4	113.08 (9)	C20—C21—H21	120.5
C10—P1—C4	110.33 (10)	N2—N1—C22	103.71 (16)
C16—P1—C1	113.36 (10)	N1—N2—N3	109.96 (15)
C10—P1—C1	107.31 (9)	N1—N2—C23	123.66 (16)
C4—P1—C1	107.07 (9)	N3—N2—C23	126.28 (16)
C2—C1—P1	113.02 (14)	N4—N3—N2	110.24 (15)
C2—C1—H1A	109.0	N4—N3—C29	124.84 (16)
P1—C1—H1A	109.0	N2—N3—C29	124.86 (16)
C2—C1—H1B	109.0	N3—N4—C22	103.49 (15)
P1—C1—H1B	109.0	N1—C22—N4	112.61 (17)
H1A—C1—H1B	107.8	N1—C22—C35	123.14 (18)
O1—C2—C3	123.83 (19)	N4—C22—C35	124.23 (17)
O1—C2—C1	119.95 (18)	C24—C23—C28	123.34 (19)
C3—C2—C1	116.22 (17)	C24—C23—N2	118.41 (18)
C2—C3—H3A	109.5	C28—C23—N2	117.98 (18)
C2—C3—H3B	109.5	C23—C24—C25	117.7 (2)
H3A—C3—H3B	109.5	C23—C24—H24	121.1
C2—C3—H3C	109.5	C25—C24—H24	121.1
H3A—C3—H3C	109.5	C26—C25—C24	120.5 (2)
H3B—C3—H3C	109.5	C26—C25—H25	119.8
C5—C4—C9	120.24 (19)	C24—C25—H25	119.8
C5—C4—P1	122.00 (16)	C25—C26—C27	120.3 (2)
C9—C4—P1	117.72 (15)	C25—C26—H26	119.9
C4—C5—C6	119.8 (2)	C27—C26—H26	119.9
C4—C5—H5	120.1	C26—C27—C28	120.7 (2)
C6—C5—H5	120.1	C26—C27—H27	119.6
C7—C6—C5	119.8 (2)	C28—C27—H27	119.6
C7—C6—H6	120.1	C23—C28—C27	117.5 (2)
C5—C6—H6	120.1	C23—C28—H28	121.3
C6—C7—C8	120.1 (2)	C27—C28—H28	121.3
C6—C7—H7	120.0	C34—C29—C30	123.7 (2)
C8—C7—H7	120.0	C34—C29—N3	118.08 (18)
C9—C8—C7	120.7 (2)	C30—C29—N3	118.17 (18)
C9—C8—H8	119.6	C29—C30—C31	117.7 (2)
C7—C8—H8	119.6	C29—C30—H30	121.1
C8—C9—C4	119.3 (2)	C31—C30—H30	121.1
C8—C9—H9	120.3	C32—C31—C30	120.2 (2)
C4—C9—H9	120.3	C32—C31—H31	119.9
C11—C10—C15	120.4 (2)	C30—C31—H31	119.9
C11—C10—P1	121.84 (17)	C31—C32—C33	120.7 (2)
C15—C10—P1	117.74 (16)	C31—C32—H32	119.7
C10—C11—C12	118.7 (3)	C33—C32—H32	119.7
C10—C11—H11	120.7	C32—C33—C34	120.0 (2)
C12—C11—H11	120.7	C32—C33—H33	120.0
C13—C12—C11	121.1 (3)	C34—C33—H33	120.0
C13—C12—H12	119.5	C29—C34—C33	117.6 (2)
C11—C12—H12	119.5	C29—C34—H34	121.2
C14—C13—C12	120.0 (2)	C33—C34—H34	121.2
C14—C13—H13	120.0	C40—C35—C36	120.41 (19)
C12—C13—H13	120.0	C40—C35—C22	119.82 (18)
C13—C14—C15	120.4 (3)	C36—C35—C22	119.77 (18)
C13—C14—H14	119.8	C37—C36—C35	119.6 (2)
C15—C14—H14	119.8	C37—C36—H36	120.2
C14—C15—C10	119.4 (2)	C35—C36—H36	120.2
C14—C15—H15	120.3	C38—C37—C36	119.8 (2)
C10—C15—H15	120.3	C38—C37—H37	120.1
C21—C16—C17	120.2 (2)	C36—C37—H37	120.1
C21—C16—P1	122.23 (17)	C39—C38—C37	120.4 (2)
C17—C16—P1	117.39 (17)	C39—C38—H38	119.8
C18—C17—C16	119.9 (2)	C37—C38—H38	119.8
C18—C17—H17	120.1	C38—C39—C40	120.3 (2)
C16—C17—H17	120.1	C38—C39—H39	119.9
C19—C18—C17	119.6 (3)	C40—C39—H39	119.9
C19—C18—H18	120.2	C39—C40—C35	119.39 (19)
C17—C18—H18	120.2	C39—C40—H40	120.3
C20—C19—C18	120.8 (2)	C35—C40—H40	120.3
C16—P1—C1—C2	−73.90 (17)	C22—N1—N2—C23	176.44 (17)
C10—P1—C1—C2	169.96 (14)	N1—N2—N3—N4	0.2 (2)
C4—P1—C1—C2	51.51 (17)	C23—N2—N3—N4	−176.19 (17)
P1—C1—C2—O1	25.5 (3)	N1—N2—N3—C29	−177.26 (16)
P1—C1—C2—C3	−155.48 (15)	C23—N2—N3—C29	6.4 (3)
C16—P1—C4—C5	−4.8 (2)	N2—N3—N4—C22	−0.21 (19)
C10—P1—C4—C5	113.14 (18)	C29—N3—N4—C22	177.20 (17)
C1—P1—C4—C5	−130.39 (17)	N2—N1—C22—N4	−0.1 (2)
C16—P1—C4—C9	173.01 (17)	N2—N1—C22—C35	178.44 (17)
C10—P1—C4—C9	−69.04 (19)	N3—N4—C22—N1	0.2 (2)
C1—P1—C4—C9	47.43 (19)	N3—N4—C22—C35	−178.33 (17)
C9—C4—C5—C6	1.1 (3)	N1—N2—C23—C24	−97.3 (2)
P1—C4—C5—C6	178.89 (16)	N3—N2—C23—C24	78.6 (3)
C4—C5—C6—C7	−0.6 (3)	N1—N2—C23—C28	77.0 (2)
C5—C6—C7—C8	0.1 (4)	N3—N2—C23—C28	−107.2 (2)
C6—C7—C8—C9	−0.1 (4)	C28—C23—C24—C25	−1.2 (3)
C7—C8—C9—C4	0.6 (4)	N2—C23—C24—C25	172.68 (18)
C5—C4—C9—C8	−1.1 (3)	C23—C24—C25—C26	0.6 (3)
P1—C4—C9—C8	−178.98 (18)	C24—C25—C26—C27	0.2 (3)
C16—P1—C10—C11	130.83 (19)	C25—C26—C27—C28	−0.4 (4)
C4—P1—C10—C11	8.3 (2)	C24—C23—C28—C27	1.0 (3)
C1—P1—C10—C11	−108.0 (2)	N2—C23—C28—C27	−172.92 (19)
C16—P1—C10—C15	−50.06 (19)	C26—C27—C28—C23	−0.2 (4)
C4—P1—C10—C15	−172.54 (17)	N4—N3—C29—C34	−90.4 (2)
C1—P1—C10—C15	71.13 (19)	N2—N3—C29—C34	86.6 (2)
C15—C10—C11—C12	0.7 (4)	N4—N3—C29—C30	87.2 (2)
P1—C10—C11—C12	179.8 (2)	N2—N3—C29—C30	−95.8 (2)
C10—C11—C12—C13	−0.5 (4)	C34—C29—C30—C31	0.2 (3)
C11—C12—C13—C14	−0.4 (5)	N3—C29—C30—C31	−177.20 (19)
C12—C13—C14—C15	1.1 (4)	C29—C30—C31—C32	0.5 (4)
C13—C14—C15—C10	−1.0 (4)	C30—C31—C32—C33	−0.6 (4)
C11—C10—C15—C14	0.0 (3)	C31—C32—C33—C34	0.1 (4)
P1—C10—C15—C14	−179.11 (18)	C30—C29—C34—C33	−0.8 (4)
C10—P1—C16—C21	121.13 (19)	N3—C29—C34—C33	176.7 (2)
C4—P1—C16—C21	−118.17 (18)	C32—C33—C34—C29	0.6 (4)
C1—P1—C16—C21	4.0 (2)	N1—C22—C35—C40	6.5 (3)
C10—P1—C16—C17	−54.18 (19)	N4—C22—C35—C40	−175.14 (18)
C4—P1—C16—C17	66.53 (19)	N1—C22—C35—C36	−173.36 (19)
C1—P1—C16—C17	−171.35 (16)	N4—C22—C35—C36	5.0 (3)
C21—C16—C17—C18	1.1 (3)	C40—C35—C36—C37	−1.3 (3)
P1—C16—C17—C18	176.46 (18)	C22—C35—C36—C37	178.6 (2)
C16—C17—C18—C19	−1.5 (4)	C35—C36—C37—C38	−0.3 (4)
C17—C18—C19—C20	0.9 (4)	C36—C37—C38—C39	1.7 (4)
C18—C19—C20—C21	0.1 (4)	C37—C38—C39—C40	−1.6 (4)
C17—C16—C21—C20	−0.1 (3)	C38—C39—C40—C35	0.0 (3)
P1—C16—C21—C20	−175.23 (19)	C36—C35—C40—C39	1.4 (3)
C19—C20—C21—C16	−0.5 (4)	C22—C35—C40—C39	−178.46 (19)
C22—N1—N2—N3	−0.02 (19)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···Cl2i	0.99	2.54	3.363 (2)	141
C1—H1B···Cl2ii	0.99	2.69	3.662 (2)	168
C3—H3B···Cl3ii	0.98	2.74	3.714 (2)	171
C3—H3C···Cl2i	0.98	2.90	3.630 (2)	132
C9—H9···Cl2ii	0.95	2.97	3.917 (2)	172
C24—H24···Cl3ii	0.95	2.99	3.783 (2)	142
C28—H28···Cl1	0.95	2.72	3.605 (2)	156
C30—H30···Cl3ii	0.95	2.87	3.683 (2)	144
C30—H30···Cl4ii	0.95	2.85	3.630 (2)	140