Synthesis, structure and photophysical properties of two tetra­nuclear copper(I) iodide com­plexes based on acetyl­pyridine and diphosphine mixed ligands

Two copper(I) iodide tetra­mers, namely, [μ₂-1,3-bis­(di­phenyl­phosphan­yl)pro­pane-κ²P:P′]di-μ₃-iodido-di-μ₂-iodido-[1-(pyridin-3-yl)ethan-1-one-κN]tetra­copper(I) di­chloro­methane disolvate, [Cu₄I₄(C₆H₇NO)₂(C₂₇H₂₆P₂)₂]·2CH₂Cl₂ (CuL³), and [μ₂-1,3-bis­(di­phenyl­phosphan­yl)propane-κ²P:P′]di-μ₃-iodido-di-μ₂-iodido-[1-(pyridin-4-yl)ethan-1-one-κN]tetra­copper(I), [Cu₄I₄(C₆H₇NO)₂(C₂₇H₂₆P₂)₂] (CuL⁴), have been synthesized from reactions of CuI, 1,3-bis­(di­phenyl­phosphan­yl)propane (dppp) and 3- or 4-acetyl­pyridine (3/4-acepy). The com­plexes were characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction (XRD), powder XRD and photoluminescence spectroscopy. Both com­plexes possess a stair-step [Cu₄I₄] cluster structure with a crystallographic inversion centre located in the middle of a Cu₂I₂ ring (Z′ = ). The dppp ligands each adopt a bidentate coordination mode that bridges two Cu^I centres on one side of the [Cu₄I₄] cluster and the acepy ligands act as terminal ligands. The solid-state samples of similar com­plexes show highly efficiency thermally activated delayed fluorescence (TADF) at room temperature. At ambient temperature, both CuL³ and CuL⁴ exhibit photoluminescence, with a maximum emission in the region 560–580 nm and with short emissive decay times, but only phospho­rescence was observed at 77 K. The narrow gaps between the higher lying singlet state and the triplet state, ΔE(S₁ − T₁), also confirm the presence of TADF. Structure analysis and consideration of photoluminescence indicates that the position of the acetyl group on the heterocyclic ligand has an obvious influence on the structural arrangement, on inter­molecular inter­actions and on the observed photophysical properties.

Computing details

For both structures, data collection: RAPID AUTO (Rigaku, 1998); cell refinement: RAPID AUTO (Rigaku, 1998); data reduction: RAPID AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: SHELXTL/PC (Sheldrick, 1993); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

[µ₂-1,3-Bis(diphenylphosphanyl)propane-κ²P:P']di-µ₃-iodido-di-µ₂-iodido-[1-(pyridin-3-yl)ethan-1-one-κN]tetracopper(I) dichloromethane disolvate (CuL3)

Crystal data

[Cu4I4(C6H7NO)2(C27H26P2)2]·2CH2Cl2	Z = 1
Mr = 1998.72	F(000) = 976
Triclinic, P1	Dx = 1.733 Mg m^−3
a = 11.950 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.443 (3) Å	Cell parameters from 6740 reflections
c = 13.060 (3) Å	θ = 3.0–25.0°
α = 83.43 (3)°	µ = 2.97 mm^−1
β = 86.30 (3)°	T = 293 K
γ = 83.76 (3)°	Block, yellowish green
V = 1915.0 (7) Å^3	0.38 × 0.20 × 0.15 mm

Data collection

Rigaku R-axis RAPID diffractometer	4522 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.081
Oscillation scans	θmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan (RAPID AUTO; Rigaku, 1998)	h = −14→13
Tmin = 0.363, Tmax = 1.000	k = −14→14
15188 measured reflections	l = −15→15
6740 independent 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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0453P)^2] where P = (Fo^2 + 2Fc^2)/3
6740 reflections	(Δ/σ)max < 0.001
406 parameters	Δρmax = 1.09 e Å^−3
0 restraints	Δρmin = −0.64 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
I1	0.17020 (3)	0.47605 (3)	0.44629 (4)	0.04475 (15)
I2	−0.04015 (3)	0.20019 (3)	0.49130 (4)	0.04860 (16)
Cu1	0.02670 (7)	0.59446 (7)	0.58304 (8)	0.0539 (3)
Cu2	0.16639 (6)	0.25189 (7)	0.48718 (8)	0.0499 (3)
P1	0.06505 (14)	0.55726 (13)	0.75013 (16)	0.0411 (4)
P2	0.25866 (13)	0.22199 (13)	0.63184 (16)	0.0388 (4)
N1	0.2482 (5)	0.1833 (5)	0.3645 (5)	0.0523 (16)
O1	0.2597 (9)	−0.0651 (7)	0.1147 (7)	0.140 (4)
C1	−0.0242 (7)	0.6409 (5)	0.8366 (7)	0.060 (2)
C2	−0.1392 (7)	0.6325 (7)	0.8465 (8)	0.074 (3)
H2A	−0.170857	0.584764	0.809633	0.089*
C3	−0.2062 (9)	0.6950 (9)	0.9110 (9)	0.093 (4)
H3A	−0.282866	0.686929	0.918105	0.112*
C4	−0.1662 (13)	0.7670 (9)	0.9643 (10)	0.110 (5)
H4A	−0.214116	0.808668	1.006859	0.132*
C5	−0.0526 (13)	0.7778 (8)	0.9546 (9)	0.104 (4)
H5A	−0.023231	0.827698	0.990527	0.125*
C6	0.0189 (8)	0.7148 (6)	0.8914 (7)	0.071 (3)
H6A	0.095714	0.722244	0.885862	0.085*
C7	0.2108 (6)	0.5704 (5)	0.7794 (7)	0.0478 (19)
C8	0.2562 (8)	0.5379 (7)	0.8740 (8)	0.073 (3)
H8A	0.210731	0.510965	0.929395	0.088*
C9	0.3668 (10)	0.5451 (7)	0.8865 (10)	0.096 (4)
H9A	0.396042	0.523502	0.950758	0.116*
C10	0.4361 (8)	0.5833 (8)	0.8065 (12)	0.094 (4)
H10A	0.512144	0.586034	0.816280	0.112*
C11	0.3942 (7)	0.6177 (7)	0.7121 (9)	0.078 (3)
H11A	0.440892	0.644190	0.657477	0.094*
C12	0.2804 (6)	0.6123 (6)	0.6992 (7)	0.057 (2)
H12A	0.250625	0.637229	0.635750	0.068*
C13	0.0390 (5)	0.4192 (5)	0.8117 (6)	0.0470 (19)
H13A	0.073913	0.406567	0.877563	0.056*
H13B	−0.041553	0.416933	0.825147	0.056*
C14	0.0837 (5)	0.3276 (5)	0.7470 (7)	0.050 (2)
H14A	0.045668	0.337809	0.682686	0.060*
H14B	0.065566	0.258935	0.783734	0.060*
C15	0.2114 (5)	0.3217 (5)	0.7226 (6)	0.0435 (18)
H15A	0.250212	0.302085	0.786146	0.052*
H15B	0.231231	0.392810	0.693360	0.052*
C16	0.2604 (5)	0.0917 (5)	0.7096 (6)	0.0393 (16)
C17	0.2148 (6)	0.0068 (5)	0.6740 (7)	0.061 (2)
H17A	0.181217	0.017483	0.610832	0.073*
C18	0.2185 (8)	−0.0935 (7)	0.7308 (10)	0.088 (4)
H18A	0.188184	−0.150133	0.705136	0.106*
C19	0.2658 (7)	−0.1113 (6)	0.8241 (9)	0.080 (3)
H19A	0.268379	−0.179851	0.861188	0.095*
C20	0.3095 (7)	−0.0284 (6)	0.8632 (7)	0.066 (2)
H20A	0.340847	−0.039480	0.927408	0.080*
C21	0.3062 (6)	0.0723 (6)	0.8057 (7)	0.056 (2)
H21A	0.335540	0.128806	0.832394	0.068*
C22	0.4103 (5)	0.2382 (6)	0.6101 (6)	0.0481 (19)
C23	0.4474 (6)	0.3423 (6)	0.6006 (7)	0.060 (2)
H23A	0.395653	0.402469	0.608949	0.072*
C24	0.5591 (6)	0.3563 (8)	0.5792 (8)	0.084 (3)
H24A	0.582886	0.425603	0.572534	0.101*
C25	0.6333 (7)	0.2699 (10)	0.5681 (8)	0.087 (3)
H25A	0.709404	0.279467	0.556574	0.104*
C26	0.5995 (7)	0.1653 (9)	0.5732 (9)	0.095 (4)
H26A	0.651838	0.106372	0.561775	0.114*
C27	0.4852 (6)	0.1506 (7)	0.5959 (8)	0.069 (3)
H27A	0.461203	0.081415	0.601171	0.082*
C28	0.2029 (6)	0.1121 (6)	0.3151 (7)	0.054 (2)
H28A	0.128068	0.100349	0.331962	0.065*
C29	0.2607 (7)	0.0547 (6)	0.2405 (7)	0.062 (2)
C30	0.3714 (8)	0.0717 (8)	0.2161 (9)	0.087 (3)
H30A	0.412570	0.034146	0.166104	0.104*
C31	0.4212 (8)	0.1442 (9)	0.2658 (10)	0.091 (3)
H31A	0.496073	0.156569	0.250136	0.110*
C32	0.3572 (6)	0.1981 (7)	0.3394 (8)	0.071 (3)
H32A	0.390728	0.247071	0.373310	0.086*
C33	0.2057 (10)	−0.0206 (7)	0.1837 (9)	0.084 (3)
C34	0.0910 (11)	−0.0454 (8)	0.2156 (10)	0.116 (4)
H34A	0.062181	−0.002980	0.270322	0.174*
H34B	0.043764	−0.028029	0.158022	0.174*
H34C	0.091588	−0.121296	0.239507	0.174*
C41	0.4199 (12)	0.7138 (11)	0.1522 (12)	0.139 (5)
H41A	0.393662	0.779514	0.183621	0.166*
H41B	0.470928	0.669689	0.198667	0.166*
Cl1	0.4928 (3)	0.7487 (3)	0.0406 (4)	0.1445 (14)
Cl2	0.3071 (4)	0.6443 (4)	0.1413 (5)	0.197 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0350 (2)	0.0434 (2)	0.0553 (4)	−0.00649 (19)	−0.0002 (2)	−0.0020 (2)
I2	0.0338 (2)	0.0445 (3)	0.0661 (4)	−0.00487 (19)	−0.0020 (2)	0.0007 (2)
Cu1	0.0487 (5)	0.0606 (5)	0.0512 (7)	−0.0090 (4)	−0.0085 (4)	0.0063 (5)
Cu2	0.0386 (4)	0.0590 (5)	0.0522 (7)	−0.0033 (4)	−0.0032 (4)	−0.0083 (5)
P1	0.0429 (9)	0.0343 (8)	0.0433 (13)	−0.0005 (7)	0.0036 (8)	0.0007 (8)
P2	0.0314 (8)	0.0359 (8)	0.0489 (13)	−0.0013 (7)	−0.0039 (8)	−0.0050 (8)
N1	0.046 (3)	0.059 (4)	0.052 (5)	−0.001 (3)	0.007 (3)	−0.014 (3)
O1	0.212 (10)	0.122 (7)	0.092 (8)	−0.009 (6)	0.032 (7)	−0.061 (6)
C1	0.089 (6)	0.034 (4)	0.050 (6)	0.007 (4)	0.009 (4)	0.001 (4)
C2	0.061 (5)	0.070 (5)	0.077 (8)	0.021 (4)	0.015 (5)	0.018 (5)
C3	0.096 (7)	0.079 (7)	0.080 (9)	0.042 (6)	0.038 (6)	0.022 (6)
C4	0.182 (14)	0.069 (7)	0.056 (8)	0.041 (8)	0.036 (9)	0.014 (6)
C5	0.191 (13)	0.049 (5)	0.065 (9)	0.007 (7)	0.016 (9)	−0.010 (5)
C6	0.106 (7)	0.043 (4)	0.060 (7)	0.001 (4)	0.013 (5)	−0.008 (4)
C7	0.054 (4)	0.039 (3)	0.054 (6)	−0.014 (3)	−0.008 (4)	−0.009 (4)
C8	0.091 (6)	0.076 (6)	0.055 (7)	−0.018 (5)	−0.030 (5)	0.006 (5)
C9	0.114 (8)	0.066 (6)	0.114 (12)	−0.006 (6)	−0.067 (8)	0.000 (6)
C10	0.067 (6)	0.084 (7)	0.139 (13)	−0.018 (5)	−0.051 (7)	−0.014 (7)
C11	0.055 (5)	0.082 (6)	0.104 (9)	−0.032 (5)	−0.015 (5)	−0.010 (6)
C12	0.056 (4)	0.050 (4)	0.068 (7)	−0.011 (4)	−0.016 (4)	−0.005 (4)
C13	0.042 (3)	0.039 (3)	0.057 (6)	−0.005 (3)	0.016 (3)	−0.002 (4)
C14	0.041 (3)	0.041 (4)	0.071 (6)	−0.007 (3)	0.011 (4)	−0.017 (4)
C15	0.034 (3)	0.036 (3)	0.061 (6)	−0.004 (3)	0.000 (3)	−0.012 (3)
C16	0.035 (3)	0.034 (3)	0.047 (5)	0.004 (3)	−0.003 (3)	−0.001 (3)
C17	0.061 (4)	0.045 (4)	0.079 (7)	−0.005 (4)	−0.027 (5)	−0.004 (4)
C18	0.088 (6)	0.050 (5)	0.130 (11)	−0.015 (5)	−0.042 (7)	0.010 (6)
C19	0.070 (5)	0.046 (5)	0.114 (10)	0.004 (4)	−0.016 (6)	0.026 (5)
C20	0.074 (5)	0.057 (5)	0.058 (7)	0.015 (4)	−0.003 (5)	0.011 (4)
C21	0.060 (4)	0.043 (4)	0.065 (7)	0.003 (3)	0.003 (4)	−0.013 (4)
C22	0.031 (3)	0.068 (5)	0.043 (5)	0.002 (3)	−0.008 (3)	−0.003 (4)
C23	0.042 (4)	0.061 (5)	0.077 (7)	−0.013 (4)	0.001 (4)	−0.003 (5)
C24	0.030 (4)	0.108 (7)	0.106 (10)	−0.008 (5)	0.003 (5)	0.016 (7)
C25	0.040 (4)	0.137 (9)	0.072 (8)	−0.014 (6)	0.008 (4)	0.040 (7)
C26	0.057 (5)	0.114 (8)	0.091 (9)	0.037 (6)	0.016 (5)	0.029 (7)
C27	0.043 (4)	0.065 (5)	0.090 (8)	0.009 (4)	0.010 (4)	0.004 (5)
C28	0.053 (4)	0.052 (4)	0.052 (6)	0.008 (4)	0.004 (4)	−0.003 (4)
C29	0.077 (5)	0.049 (4)	0.053 (6)	0.008 (4)	0.004 (5)	0.001 (4)
C30	0.084 (7)	0.090 (7)	0.072 (8)	0.037 (6)	0.019 (6)	0.001 (6)
C31	0.057 (5)	0.115 (8)	0.095 (10)	0.008 (6)	0.019 (6)	−0.006 (7)
C32	0.050 (4)	0.084 (6)	0.078 (8)	−0.001 (4)	0.008 (5)	−0.009 (6)
C33	0.135 (9)	0.057 (5)	0.060 (8)	−0.016 (6)	0.011 (7)	−0.009 (5)
C34	0.184 (12)	0.094 (7)	0.087 (10)	−0.072 (8)	0.014 (9)	−0.032 (7)
C41	0.162 (12)	0.138 (11)	0.105 (13)	−0.008 (10)	0.024 (10)	0.006 (9)
Cl1	0.118 (2)	0.163 (3)	0.150 (4)	−0.006 (2)	0.002 (2)	−0.018 (3)
Cl2	0.164 (4)	0.198 (4)	0.233 (7)	−0.057 (4)	0.040 (4)	−0.028 (4)

Geometric parameters (Å, º)

I1—Cu1^i	2.6636 (11)	C14—H14A	0.9700
I1—Cu2	2.7840 (11)	C14—H14B	0.9700
I1—Cu1	2.8212 (15)	C15—H15A	0.9700
I2—Cu2	2.6132 (10)	C15—H15B	0.9700
I2—Cu1^i	2.6455 (12)	C16—C17	1.378 (9)
Cu1—P1	2.245 (2)	C16—C21	1.387 (11)
Cu1—Cu2^i	2.9552 (16)	C17—C18	1.376 (11)
Cu2—N1	2.044 (6)	C17—H17A	0.9300
Cu2—P2	2.223 (2)	C18—C19	1.360 (13)
P1—C1	1.835 (8)	C18—H18A	0.9300
P1—C7	1.835 (7)	C19—C20	1.368 (11)
P1—C13	1.861 (6)	C19—H19A	0.9300
P2—C16	1.811 (7)	C20—C21	1.382 (10)
P2—C15	1.834 (7)	C20—H20A	0.9300
P2—C22	1.846 (6)	C21—H21A	0.9300
N1—C28	1.332 (9)	C22—C27	1.354 (10)
N1—C32	1.350 (9)	C22—C23	1.404 (10)
O1—C33	1.223 (12)	C23—C24	1.372 (9)
C1—C6	1.387 (11)	C23—H23A	0.9300
C1—C2	1.386 (11)	C24—C25	1.332 (13)
C2—C3	1.372 (13)	C24—H24A	0.9300
C2—H2A	0.9300	C25—C26	1.397 (13)
C3—C4	1.340 (16)	C25—H25A	0.9300
C3—H3A	0.9300	C26—C27	1.407 (11)
C4—C5	1.375 (16)	C26—H26A	0.9300
C4—H4A	0.9300	C27—H27A	0.9300
C5—C6	1.392 (14)	C28—C29	1.380 (11)
C5—H5A	0.9300	C28—H28A	0.9300
C6—H6A	0.9300	C29—C30	1.373 (12)
C7—C8	1.382 (11)	C29—C33	1.489 (12)
C7—C12	1.385 (11)	C30—C31	1.375 (13)
C8—C9	1.356 (12)	C30—H30A	0.9300
C8—H8A	0.9300	C31—C32	1.379 (13)
C9—C10	1.366 (16)	C31—H31A	0.9300
C9—H9A	0.9300	C32—H32A	0.9300
C10—C11	1.366 (15)	C33—C34	1.462 (14)
C10—H10A	0.9300	C34—H34A	0.9600
C11—C12	1.390 (10)	C34—H34B	0.9600
C11—H11A	0.9300	C34—H34C	0.9600
C12—H12A	0.9300	C41—Cl1	1.687 (14)
C13—C14	1.525 (9)	C41—Cl2	1.700 (13)
C13—H13A	0.9700	C41—H41A	0.9700
C13—H13B	0.9700	C41—H41B	0.9700
C14—C15	1.535 (8)
Cu1^i—I1—Cu2	65.66 (4)	H13A—C13—H13B	107.6
Cu1^i—I1—Cu1	79.47 (4)	C13—C14—C15	113.4 (5)
Cu2—I1—Cu1	113.32 (4)	C13—C14—H14A	108.9
Cu2—I2—Cu1^i	68.38 (4)	C15—C14—H14A	108.9
P1—Cu1—I2^i	114.11 (6)	C13—C14—H14B	108.9
P1—Cu1—I1^i	109.28 (6)	C15—C14—H14B	108.9
I2^i—Cu1—I1^i	113.31 (4)	H14A—C14—H14B	107.7
P1—Cu1—I1	114.97 (6)	C14—C15—P2	111.8 (4)
I2^i—Cu1—I1	103.87 (4)	C14—C15—H15A	109.2
I1^i—Cu1—I1	100.53 (4)	P2—C15—H15A	109.2
P1—Cu1—Cu2^i	122.44 (7)	C14—C15—H15B	109.2
I2^i—Cu1—Cu2^i	55.29 (3)	P2—C15—H15B	109.2
I1^i—Cu1—Cu2^i	59.13 (3)	H15A—C15—H15B	107.9
I1—Cu1—Cu2^i	122.52 (5)	C17—C16—C21	117.2 (6)
N1—Cu2—P2	114.48 (18)	C17—C16—P2	120.1 (6)
N1—Cu2—I2	105.40 (16)	C21—C16—P2	122.7 (5)
P2—Cu2—I2	118.77 (7)	C18—C17—C16	120.7 (8)
N1—Cu2—I1	107.22 (18)	C18—C17—H17A	119.7
P2—Cu2—I1	99.97 (6)	C16—C17—H17A	119.7
I2—Cu2—I1	110.48 (4)	C19—C18—C17	121.0 (8)
N1—Cu2—Cu1^i	110.15 (19)	C19—C18—H18A	119.5
P2—Cu2—Cu1^i	133.95 (7)	C17—C18—H18A	119.5
I2—Cu2—Cu1^i	56.33 (3)	C18—C19—C20	120.0 (8)
I1—Cu2—Cu1^i	55.21 (3)	C18—C19—H19A	120.0
C1—P1—C7	105.7 (4)	C20—C19—H19A	120.0
C1—P1—C13	99.9 (3)	C19—C20—C21	118.8 (8)
C7—P1—C13	104.0 (3)	C19—C20—H20A	120.6
C1—P1—Cu1	114.1 (3)	C21—C20—H20A	120.6
C7—P1—Cu1	115.2 (3)	C20—C21—C16	122.2 (7)
C13—P1—Cu1	116.2 (3)	C20—C21—H21A	118.9
C16—P2—C15	104.5 (3)	C16—C21—H21A	118.9
C16—P2—C22	102.1 (3)	C27—C22—C23	119.8 (6)
C15—P2—C22	102.7 (3)	C27—C22—P2	120.0 (5)
C16—P2—Cu2	120.3 (2)	C23—C22—P2	120.0 (5)
C15—P2—Cu2	112.5 (2)	C24—C23—C22	120.8 (8)
C22—P2—Cu2	112.9 (3)	C24—C23—H23A	119.6
C28—N1—C32	117.0 (7)	C22—C23—H23A	119.6
C28—N1—Cu2	122.3 (5)	C25—C24—C23	119.5 (9)
C32—N1—Cu2	120.1 (6)	C25—C24—H24A	120.2
C6—C1—C2	118.2 (8)	C23—C24—H24A	120.2
C6—C1—P1	122.3 (7)	C24—C25—C26	121.5 (8)
C2—C1—P1	119.5 (7)	C24—C25—H25A	119.2
C3—C2—C1	119.6 (10)	C26—C25—H25A	119.2
C3—C2—H2A	120.2	C25—C26—C27	119.0 (9)
C1—C2—H2A	120.2	C25—C26—H26A	120.5
C4—C3—C2	123.0 (11)	C27—C26—H26A	120.5
C4—C3—H3A	118.5	C22—C27—C26	119.3 (8)
C2—C3—H3A	118.5	C22—C27—H27A	120.4
C3—C4—C5	118.3 (12)	C26—C27—H27A	120.4
C3—C4—H4A	120.9	N1—C28—C29	123.7 (7)
C5—C4—H4A	120.8	N1—C28—H28A	118.2
C4—C5—C6	120.7 (11)	C29—C28—H28A	118.2
C4—C5—H5A	119.7	C30—C29—C28	118.1 (8)
C6—C5—H5A	119.7	C30—C29—C33	119.8 (9)
C1—C6—C5	120.1 (10)	C28—C29—C33	122.1 (8)
C1—C6—H6A	119.9	C29—C30—C31	119.9 (9)
C5—C6—H6A	119.9	C29—C30—H30A	120.1
C8—C7—C12	118.3 (7)	C31—C30—H30A	120.1
C8—C7—P1	124.7 (7)	C30—C31—C32	118.2 (9)
C12—C7—P1	117.0 (6)	C30—C31—H31A	120.9
C9—C8—C7	120.3 (10)	C32—C31—H31A	120.9
C9—C8—H8A	119.8	N1—C32—C31	123.1 (9)
C7—C8—H8A	119.8	N1—C32—H32A	118.4
C8—C9—C10	121.3 (10)	C31—C32—H32A	118.4
C8—C9—H9A	119.4	O1—C33—C34	121.2 (10)
C10—C9—H9A	119.4	O1—C33—C29	119.2 (11)
C9—C10—C11	120.2 (9)	C34—C33—C29	119.5 (9)
C9—C10—H10A	119.9	C33—C34—H34A	109.5
C11—C10—H10A	119.9	C33—C34—H34B	109.5
C10—C11—C12	118.9 (10)	H34A—C34—H34B	109.5
C10—C11—H11A	120.6	C33—C34—H34C	109.5
C12—C11—H11A	120.6	H34A—C34—H34C	109.5
C7—C12—C11	121.0 (9)	H34B—C34—H34C	109.5
C7—C12—H12A	119.5	Cl1—C41—Cl2	115.5 (9)
C11—C12—H12A	119.5	Cl1—C41—H41A	108.4
C14—C13—P1	114.1 (5)	Cl2—C41—H41A	108.4
C14—C13—H13A	108.7	Cl1—C41—H41B	108.4
P1—C13—H13A	108.7	Cl2—C41—H41B	108.4
C14—C13—H13B	108.7	H41A—C41—H41B	107.5
P1—C13—H13B	108.7
C7—P1—C1—C6	13.1 (8)	C15—P2—C16—C21	−45.4 (6)
C13—P1—C1—C6	120.8 (7)	C22—P2—C16—C21	61.3 (7)
Cu1—P1—C1—C6	−114.5 (7)	Cu2—P2—C16—C21	−172.9 (5)
C7—P1—C1—C2	−168.4 (7)	C21—C16—C17—C18	−2.1 (12)
C13—P1—C1—C2	−60.7 (7)	P2—C16—C17—C18	178.1 (7)
Cu1—P1—C1—C2	64.0 (7)	C16—C17—C18—C19	0.9 (15)
C6—C1—C2—C3	−1.4 (13)	C17—C18—C19—C20	0.8 (16)
P1—C1—C2—C3	−179.9 (7)	C18—C19—C20—C21	−1.0 (14)
C1—C2—C3—C4	1.6 (15)	C19—C20—C21—C16	−0.3 (12)
C2—C3—C4—C5	−0.7 (17)	C17—C16—C21—C20	1.8 (11)
C3—C4—C5—C6	−0.4 (17)	P2—C16—C21—C20	−178.4 (6)
C2—C1—C6—C5	0.3 (13)	C16—P2—C22—C27	36.8 (8)
P1—C1—C6—C5	178.8 (8)	C15—P2—C22—C27	144.9 (7)
C4—C5—C6—C1	0.6 (16)	Cu2—P2—C22—C27	−93.8 (7)
C1—P1—C7—C8	62.0 (7)	C16—P2—C22—C23	−147.9 (7)
C13—P1—C7—C8	−42.7 (8)	C15—P2—C22—C23	−39.8 (8)
Cu1—P1—C7—C8	−171.1 (6)	Cu2—P2—C22—C23	81.5 (7)
C1—P1—C7—C12	−120.5 (6)	C27—C22—C23—C24	−1.3 (13)
C13—P1—C7—C12	134.8 (6)	P2—C22—C23—C24	−176.7 (7)
Cu1—P1—C7—C12	6.5 (6)	C22—C23—C24—C25	−0.5 (15)
C12—C7—C8—C9	−1.4 (12)	C23—C24—C25—C26	2.8 (16)
P1—C7—C8—C9	176.1 (7)	C24—C25—C26—C27	−3.3 (17)
C7—C8—C9—C10	−0.6 (15)	C23—C22—C27—C26	0.8 (14)
C8—C9—C10—C11	1.5 (16)	P2—C22—C27—C26	176.1 (8)
C9—C10—C11—C12	−0.4 (15)	C25—C26—C27—C22	1.4 (15)
C8—C7—C12—C11	2.5 (11)	C32—N1—C28—C29	−0.6 (12)
P1—C7—C12—C11	−175.2 (6)	Cu2—N1—C28—C29	−172.0 (7)
C10—C11—C12—C7	−1.7 (13)	N1—C28—C29—C30	0.3 (13)
C1—P1—C13—C14	168.9 (6)	N1—C28—C29—C33	−177.2 (8)
C7—P1—C13—C14	−82.0 (6)	C28—C29—C30—C31	0.0 (14)
Cu1—P1—C13—C14	45.7 (6)	C33—C29—C30—C31	177.6 (9)
P1—C13—C14—C15	59.7 (8)	C29—C30—C31—C32	0.0 (16)
C13—C14—C15—P2	−172.9 (5)	C28—N1—C32—C31	0.5 (14)
C16—P2—C15—C14	−77.3 (6)	Cu2—N1—C32—C31	172.1 (8)
C22—P2—C15—C14	176.4 (5)	C30—C31—C32—N1	−0.2 (16)
Cu2—P2—C15—C14	54.8 (6)	C30—C29—C33—O1	−1.2 (15)
C15—P2—C16—C17	134.4 (6)	C28—C29—C33—O1	176.4 (10)
C22—P2—C16—C17	−119.0 (6)	C30—C29—C33—C34	174.9 (9)
Cu2—P2—C16—C17	6.9 (7)	C28—C29—C33—C34	−7.5 (14)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C28—H28A···I2	0.93	3.07	3.735 (8)	130
C41—H41A···O1^ii	0.97	2.50	3.185 (17)	128

Symmetry code: (ii) x, y+1, z.

[µ₂-1,3-Bis(diphenylphosphanyl)propane-κ²P:P']di-µ₃-iodido-di-µ₂-iodido-[1-(pyridin-4-yl)ethan-1-one-κN]tetracopper(I) (CuL4)

Crystal data

[Cu4I4(C6H7NO)2(C27H26P2)2]	Z = 1
Mr = 1828.86	F(000) = 892
Triclinic, P1	Dx = 1.794 Mg m^−3
a = 11.981 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.996 (3) Å	Cell parameters from 5949 reflections
c = 13.230 (3) Å	θ = 3.0–25.0°
α = 62.49 (3)°	µ = 3.20 mm^−1
β = 68.32 (3)°	T = 293 K
γ = 83.71 (3)°	Block, yellow
V = 1693.2 (8) Å^3	0.26 × 0.25 × 0.18 mm

Data collection

Rigaku R-axis RAPID diffractometer	3380 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.112
Oscillation scans	θmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan (RAPID AUTO; Rigaku, 1998)	h = −14→13
Tmin = 0.410, Tmax = 1.000	k = −15→15
13417 measured reflections	l = −15→15
5949 independent 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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.154	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.027P)^2] where P = (Fo^2 + 2Fc^2)/3
5949 reflections	(Δ/σ)max < 0.001
379 parameters	Δρmax = 1.05 e Å^−3
0 restraints	Δρmin = −1.31 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
I1	0.84534 (6)	0.40748 (6)	0.04377 (6)	0.0454 (2)
I2	0.83888 (7)	0.57809 (6)	0.26992 (6)	0.0516 (2)
Cu1	1.09434 (13)	0.39277 (12)	−0.04689 (12)	0.0591 (4)
Cu2	0.74647 (11)	0.40079 (11)	0.26659 (11)	0.0480 (4)
P1	1.1371 (2)	0.2260 (2)	0.0895 (2)	0.0413 (7)
P2	0.7798 (2)	0.2409 (2)	0.4168 (2)	0.0402 (6)
N1	0.5717 (8)	0.4382 (8)	0.2837 (8)	0.052 (2)
C1	1.2893 (9)	0.2244 (8)	0.0921 (8)	0.037 (2)
C2	1.3668 (10)	0.3214 (10)	0.0162 (10)	0.060 (3)
H2A	1.341316	0.389392	−0.034145	0.072*
C3	1.4817 (11)	0.3188 (11)	0.0142 (10)	0.068 (4)
H3A	1.533874	0.385333	−0.039362	0.082*
C4	1.5223 (11)	0.2233 (12)	0.0869 (12)	0.070 (4)
H4A	1.600688	0.223603	0.084963	0.084*
C5	1.4458 (15)	0.1272 (12)	0.1628 (15)	0.098 (5)
H5A	1.472488	0.059774	0.212553	0.118*
C6	1.3271 (12)	0.1270 (11)	0.1680 (12)	0.087 (5)
H6A	1.274463	0.060973	0.222734	0.104*
C7	1.1240 (9)	0.0931 (9)	0.0794 (9)	0.044 (3)
C8	1.1918 (12)	0.0883 (10)	−0.0269 (10)	0.063 (3)
H8A	1.241000	0.153271	−0.092066	0.076*
C9	1.1889 (13)	−0.0102 (13)	−0.0399 (12)	0.084 (4)
H9A	1.238394	−0.011780	−0.112275	0.101*
C10	1.1132 (14)	−0.1074 (12)	0.0534 (14)	0.079 (4)
H10A	1.108179	−0.172510	0.042846	0.094*
C11	1.0481 (13)	−0.1051 (11)	0.1582 (12)	0.078 (4)
H11A	0.999612	−0.170454	0.223444	0.093*
C12	1.0526 (12)	−0.0029 (10)	0.1707 (11)	0.067 (3)
H12A	1.004881	−0.002103	0.243910	0.080*
C13	1.0366 (10)	0.1873 (9)	0.2450 (9)	0.053 (3)
H13A	0.956337	0.169134	0.253179	0.063*
H13B	1.062212	0.117121	0.299562	0.063*
C14	1.0297 (9)	0.2789 (8)	0.2861 (8)	0.042 (2)
H14A	1.012456	0.351706	0.227213	0.051*
H14B	1.107409	0.290651	0.287873	0.051*
C15	0.9337 (10)	0.2470 (9)	0.4120 (9)	0.051 (3)
H15A	0.941161	0.303859	0.437886	0.061*
H15B	0.948274	0.171858	0.469806	0.061*
C16	0.7524 (8)	0.0986 (8)	0.4300 (8)	0.039 (2)
C17	0.7994 (12)	−0.0014 (9)	0.4917 (11)	0.069 (4)
H17A	0.849100	0.001006	0.530573	0.083*
C18	0.7754 (14)	−0.1036 (11)	0.4974 (13)	0.086 (5)
H18A	0.806441	−0.170907	0.541931	0.104*
C19	0.7052 (13)	−0.1083 (11)	0.4377 (12)	0.076 (4)
H19A	0.691618	−0.178094	0.439148	0.092*
C20	0.6551 (13)	−0.0108 (10)	0.3761 (11)	0.074 (4)
H20A	0.604960	−0.013915	0.338065	0.089*
C21	0.6809 (11)	0.0915 (9)	0.3720 (10)	0.061 (3)
H21A	0.648890	0.158660	0.328499	0.073*
C22	0.6836 (9)	0.2185 (8)	0.5715 (8)	0.038 (2)
C23	0.7248 (11)	0.1871 (9)	0.6658 (9)	0.059 (3)
H23A	0.806462	0.178594	0.651742	0.071*
C24	0.6458 (12)	0.1682 (10)	0.7810 (10)	0.065 (3)
H24A	0.674328	0.148542	0.843764	0.079*
C25	0.5257 (12)	0.1787 (11)	0.8016 (11)	0.067 (3)
H25A	0.472593	0.163210	0.879777	0.081*
C26	0.4810 (10)	0.2117 (10)	0.7095 (10)	0.057 (3)
H26A	0.399431	0.221198	0.723675	0.068*
C27	0.5611 (9)	0.2299 (9)	0.5964 (9)	0.051 (3)
H27A	0.532147	0.250777	0.533724	0.061*
C28	0.5062 (11)	0.3863 (9)	0.2575 (10)	0.059 (3)
H28A	0.545805	0.341120	0.219148	0.070*
C29	0.3850 (10)	0.3927 (9)	0.2815 (10)	0.057 (3)
H29A	0.344730	0.355154	0.258231	0.068*
C30	0.3252 (10)	0.4567 (9)	0.3412 (9)	0.048 (3)
C31	0.3895 (10)	0.5117 (11)	0.3704 (11)	0.072 (4)
H31A	0.352262	0.557765	0.408470	0.087*
C32	0.5120 (10)	0.4975 (9)	0.3422 (9)	0.052 (3)
H32A	0.554468	0.532259	0.366131	0.062*
C33	0.1870 (12)	0.4610 (11)	0.3796 (12)	0.068 (3)
C34	0.1407 (13)	0.5749 (12)	0.3487 (17)	0.138 (8)
H34A	0.206577	0.633003	0.307392	0.208*
H34B	0.096937	0.589140	0.296225	0.208*
H34C	0.088070	0.578119	0.422102	0.208*
O1	0.1274 (9)	0.3734 (8)	0.4305 (11)	0.110 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0362 (4)	0.0478 (4)	0.0510 (4)	0.0082 (3)	−0.0109 (3)	−0.0264 (3)
I2	0.0500 (5)	0.0536 (5)	0.0541 (5)	0.0027 (4)	−0.0155 (4)	−0.0290 (4)
Cu1	0.0610 (10)	0.0557 (9)	0.0550 (8)	0.0216 (7)	−0.0237 (7)	−0.0224 (7)
Cu2	0.0399 (8)	0.0461 (8)	0.0538 (8)	0.0116 (6)	−0.0169 (6)	−0.0213 (6)
P1	0.0362 (16)	0.0418 (15)	0.0413 (15)	0.0142 (12)	−0.0112 (12)	−0.0197 (12)
P2	0.0348 (16)	0.0448 (15)	0.0425 (15)	0.0088 (12)	−0.0120 (12)	−0.0238 (12)
N1	0.044 (6)	0.054 (6)	0.060 (6)	0.016 (5)	−0.018 (5)	−0.030 (5)
C1	0.038 (6)	0.042 (6)	0.033 (5)	0.006 (5)	−0.013 (4)	−0.021 (4)
C2	0.037 (7)	0.054 (7)	0.066 (7)	0.010 (6)	−0.010 (6)	−0.017 (6)
C3	0.040 (8)	0.080 (9)	0.063 (8)	−0.006 (7)	−0.007 (6)	−0.022 (6)
C4	0.039 (8)	0.089 (10)	0.109 (10)	0.029 (7)	−0.037 (7)	−0.064 (8)
C5	0.098 (13)	0.052 (8)	0.160 (14)	0.023 (8)	−0.091 (12)	−0.030 (9)
C6	0.058 (9)	0.067 (9)	0.106 (11)	0.006 (7)	−0.046 (8)	−0.004 (8)
C7	0.036 (6)	0.046 (6)	0.056 (7)	0.019 (5)	−0.020 (5)	−0.030 (5)
C8	0.082 (10)	0.060 (8)	0.050 (7)	0.014 (7)	−0.020 (6)	−0.032 (6)
C9	0.081 (11)	0.102 (11)	0.084 (10)	0.022 (9)	−0.013 (8)	−0.068 (9)
C10	0.089 (12)	0.078 (10)	0.118 (13)	0.028 (9)	−0.060 (10)	−0.071 (10)
C11	0.093 (12)	0.058 (8)	0.085 (10)	−0.003 (8)	−0.034 (9)	−0.031 (7)
C12	0.067 (9)	0.060 (8)	0.076 (8)	0.010 (7)	−0.026 (7)	−0.034 (7)
C13	0.046 (7)	0.046 (6)	0.052 (6)	0.020 (5)	−0.016 (5)	−0.016 (5)
C14	0.029 (6)	0.047 (6)	0.051 (6)	0.009 (5)	−0.014 (5)	−0.024 (5)
C15	0.056 (8)	0.050 (6)	0.050 (6)	0.001 (6)	−0.015 (5)	−0.029 (5)
C16	0.027 (6)	0.042 (6)	0.047 (6)	0.000 (5)	−0.011 (5)	−0.021 (5)
C17	0.087 (10)	0.044 (7)	0.081 (9)	0.004 (7)	−0.045 (8)	−0.021 (6)
C18	0.107 (13)	0.049 (8)	0.105 (11)	0.006 (8)	−0.058 (10)	−0.021 (7)
C19	0.095 (12)	0.051 (8)	0.085 (9)	−0.002 (7)	−0.028 (8)	−0.035 (7)
C20	0.111 (12)	0.056 (8)	0.080 (9)	0.013 (8)	−0.059 (9)	−0.035 (7)
C21	0.082 (10)	0.040 (6)	0.066 (8)	0.002 (6)	−0.041 (7)	−0.017 (6)
C22	0.039 (6)	0.039 (5)	0.043 (6)	0.013 (5)	−0.009 (5)	−0.030 (5)
C23	0.057 (8)	0.074 (8)	0.045 (7)	0.019 (6)	−0.024 (6)	−0.025 (6)
C24	0.067 (9)	0.077 (9)	0.057 (8)	0.015 (7)	−0.025 (7)	−0.035 (6)
C25	0.058 (9)	0.082 (9)	0.057 (8)	0.002 (7)	−0.006 (6)	−0.039 (6)
C26	0.033 (7)	0.075 (8)	0.061 (7)	−0.005 (6)	0.002 (6)	−0.042 (6)
C27	0.031 (6)	0.067 (7)	0.047 (6)	0.003 (5)	−0.004 (5)	−0.027 (5)
C28	0.048 (8)	0.051 (7)	0.060 (7)	0.011 (6)	−0.007 (6)	−0.023 (6)
C29	0.047 (8)	0.054 (7)	0.088 (8)	0.005 (6)	−0.019 (6)	−0.051 (6)
C30	0.042 (7)	0.042 (6)	0.067 (7)	0.015 (5)	−0.021 (6)	−0.032 (5)
C31	0.038 (8)	0.099 (10)	0.117 (10)	0.021 (7)	−0.025 (7)	−0.084 (9)
C32	0.047 (7)	0.062 (7)	0.067 (7)	0.009 (6)	−0.022 (6)	−0.046 (6)
C33	0.044 (8)	0.061 (8)	0.117 (10)	0.027 (7)	−0.029 (7)	−0.059 (8)
C34	0.052 (10)	0.080 (11)	0.25 (2)	0.025 (9)	−0.051 (12)	−0.060 (12)
O1	0.053 (6)	0.067 (6)	0.213 (12)	−0.009 (5)	−0.039 (7)	−0.071 (7)

Geometric parameters (Å, º)

I1—Cu2	2.7032 (17)	C14—C15	1.523 (13)
I1—Cu1^i	2.7920 (18)	C14—H14A	0.9700
I1—Cu1	2.7962 (18)	C14—H14B	0.9700
I2—Cu1^i	2.6039 (17)	C15—H15A	0.9700
I2—Cu2	2.6881 (17)	C15—H15B	0.9700
Cu1—P1	2.246 (3)	C16—C17	1.368 (13)
Cu1—Cu2^i	3.017 (3)	C16—C21	1.379 (13)
Cu2—N1	2.050 (9)	C17—C18	1.353 (17)
Cu2—P2	2.240 (3)	C17—H17A	0.9300
P1—C13	1.811 (10)	C18—C19	1.371 (17)
P1—C7	1.820 (11)	C18—H18A	0.9300
P1—C1	1.835 (10)	C19—C20	1.367 (15)
P2—C16	1.830 (10)	C19—H19A	0.9300
P2—C15	1.831 (11)	C20—C21	1.370 (15)
P2—C22	1.839 (9)	C20—H20A	0.9300
N1—C32	1.313 (13)	C21—H21A	0.9300
N1—C28	1.313 (14)	C22—C23	1.382 (13)
C1—C6	1.360 (13)	C22—C27	1.387 (13)
C1—C2	1.363 (13)	C23—C24	1.385 (15)
C2—C3	1.364 (15)	C23—H23A	0.9300
C2—H2A	0.9300	C24—C25	1.366 (16)
C3—C4	1.347 (15)	C24—H24A	0.9300
C3—H3A	0.9300	C25—C26	1.380 (15)
C4—C5	1.350 (17)	C25—H25A	0.9300
C4—H4A	0.9300	C26—C27	1.370 (14)
C5—C6	1.399 (18)	C26—H26A	0.9300
C5—H5A	0.9300	C27—H27A	0.9300
C6—H6A	0.9300	C28—C29	1.369 (15)
C7—C12	1.351 (15)	C28—H28A	0.9300
C7—C8	1.367 (14)	C29—C30	1.375 (14)
C8—C9	1.373 (16)	C29—H29A	0.9300
C8—H8A	0.9300	C30—C31	1.360 (15)
C9—C10	1.387 (18)	C30—C33	1.546 (16)
C9—H9A	0.9300	C31—C32	1.388 (15)
C10—C11	1.329 (18)	C31—H31A	0.9300
C10—H10A	0.9300	C32—H32A	0.9300
C11—C12	1.420 (17)	C33—O1	1.172 (14)
C11—H11A	0.9300	C33—C34	1.447 (17)
C12—H12A	0.9300	C34—H34A	0.9600
C13—C14	1.505 (14)	C34—H34B	0.9600
C13—H13A	0.9700	C34—H34C	0.9600
C13—H13B	0.9700
Cu2—I1—Cu1^i	66.59 (6)	P1—C13—H13A	108.4
Cu2—I1—Cu1	117.54 (5)	C14—C13—H13B	108.4
Cu1^i—I1—Cu1	84.66 (6)	P1—C13—H13B	108.4
Cu1^i—I2—Cu2	69.51 (6)	H13A—C13—H13B	107.5
P1—Cu1—I2^i	117.05 (10)	C13—C14—C15	112.9 (8)
P1—Cu1—I1^i	114.46 (10)	C13—C14—H14A	109.0
I2^i—Cu1—I1^i	111.04 (6)	C15—C14—H14A	109.0
P1—Cu1—I1	107.26 (10)	C13—C14—H14B	109.0
I2^i—Cu1—I1	109.28 (6)	C15—C14—H14B	109.0
I1^i—Cu1—I1	95.34 (6)	H14A—C14—H14B	107.8
P1—Cu1—Cu2^i	131.81 (10)	C14—C15—P2	113.6 (7)
I2^i—Cu1—Cu2^i	56.56 (5)	C14—C15—H15A	108.8
I1^i—Cu1—Cu2^i	55.30 (5)	P2—C15—H15A	108.8
I1—Cu1—Cu2^i	120.02 (6)	C14—C15—H15B	108.8
N1—Cu2—P2	118.3 (3)	P2—C15—H15B	108.8
N1—Cu2—I2	104.2 (3)	H15A—C15—H15B	107.7
P2—Cu2—I2	104.59 (9)	C17—C16—C21	117.3 (10)
N1—Cu2—I1	104.0 (3)	C17—C16—P2	124.8 (8)
P2—Cu2—I1	114.27 (9)	C21—C16—P2	117.9 (7)
I2—Cu2—I1	111.23 (6)	C18—C17—C16	121.5 (12)
N1—Cu2—Cu1^i	107.2 (2)	C18—C17—H17A	119.2
P2—Cu2—Cu1^i	133.85 (9)	C16—C17—H17A	119.2
I2—Cu2—Cu1^i	53.93 (5)	C17—C18—C19	120.1 (12)
I1—Cu2—Cu1^i	58.12 (5)	C17—C18—H18A	120.0
C13—P1—C7	101.4 (5)	C19—C18—H18A	120.0
C13—P1—C1	105.2 (5)	C20—C19—C18	120.4 (12)
C7—P1—C1	102.4 (4)	C20—C19—H19A	119.8
C13—P1—Cu1	112.4 (3)	C18—C19—H19A	119.8
C7—P1—Cu1	118.1 (3)	C19—C20—C21	118.2 (12)
C1—P1—Cu1	115.6 (3)	C19—C20—H20A	120.9
C16—P2—C15	106.5 (5)	C21—C20—H20A	120.9
C16—P2—C22	99.8 (4)	C20—C21—C16	122.4 (10)
C15—P2—C22	104.5 (5)	C20—C21—H21A	118.8
C16—P2—Cu2	118.7 (3)	C16—C21—H21A	118.8
C15—P2—Cu2	111.6 (3)	C23—C22—C27	117.8 (9)
C22—P2—Cu2	114.2 (3)	C23—C22—P2	124.2 (8)
C32—N1—C28	115.3 (10)	C27—C22—P2	118.0 (7)
C32—N1—Cu2	122.1 (8)	C22—C23—C24	120.7 (11)
C28—N1—Cu2	121.4 (8)	C22—C23—H23A	119.6
C6—C1—C2	119.1 (10)	C24—C23—H23A	119.6
C6—C1—P1	120.9 (8)	C25—C24—C23	119.3 (11)
C2—C1—P1	119.9 (7)	C25—C24—H24A	120.3
C3—C2—C1	120.0 (10)	C23—C24—H24A	120.3
C3—C2—H2A	120.0	C24—C25—C26	121.8 (11)
C1—C2—H2A	120.0	C24—C25—H25A	119.1
C4—C3—C2	122.3 (11)	C26—C25—H25A	119.1
C4—C3—H3A	118.8	C27—C26—C25	117.6 (11)
C2—C3—H3A	118.8	C27—C26—H26A	121.2
C3—C4—C5	118.0 (11)	C25—C26—H26A	121.2
C3—C4—H4A	121.0	C26—C27—C22	122.7 (10)
C5—C4—H4A	121.0	C26—C27—H27A	118.6
C4—C5—C6	121.3 (11)	C22—C27—H27A	118.6
C4—C5—H5A	119.4	N1—C28—C29	126.0 (11)
C6—C5—H5A	119.4	N1—C28—H28A	117.0
C1—C6—C5	119.3 (12)	C29—C28—H28A	117.0
C1—C6—H6A	120.4	C28—C29—C30	117.3 (11)
C5—C6—H6A	120.4	C28—C29—H29A	121.3
C12—C7—C8	117.0 (11)	C30—C29—H29A	121.3
C12—C7—P1	124.6 (9)	C31—C30—C29	118.6 (11)
C8—C7—P1	118.4 (9)	C31—C30—C33	120.9 (10)
C7—C8—C9	121.6 (11)	C29—C30—C33	120.4 (10)
C7—C8—H8A	119.2	C30—C31—C32	118.5 (11)
C9—C8—H8A	119.2	C30—C31—H31A	120.7
C8—C9—C10	121.0 (12)	C32—C31—H31A	120.7
C8—C9—H9A	119.5	N1—C32—C31	124.1 (11)
C10—C9—H9A	119.5	N1—C32—H32A	117.9
C11—C10—C9	118.3 (13)	C31—C32—H32A	117.9
C11—C10—H10A	120.9	O1—C33—C34	124.8 (13)
C9—C10—H10A	120.9	O1—C33—C30	118.6 (11)
C10—C11—C12	120.1 (13)	C34—C33—C30	116.6 (12)
C10—C11—H11A	119.9	C33—C34—H34A	109.5
C12—C11—H11A	119.9	C33—C34—H34B	109.5
C7—C12—C11	122.0 (12)	H34A—C34—H34B	109.5
C7—C12—H12A	119.0	C33—C34—H34C	109.5
C11—C12—H12A	119.0	H34A—C34—H34C	109.5
C14—C13—P1	115.4 (7)	H34B—C34—H34C	109.5
C14—C13—H13A	108.4
C13—P1—C1—C6	57.6 (11)	C15—P2—C16—C21	−145.3 (9)
C7—P1—C1—C6	−48.0 (11)	C22—P2—C16—C21	106.3 (9)
Cu1—P1—C1—C6	−177.8 (9)	Cu2—P2—C16—C21	−18.4 (10)
C13—P1—C1—C2	−123.1 (9)	C21—C16—C17—C18	−1.0 (18)
C7—P1—C1—C2	131.2 (9)	P2—C16—C17—C18	−179.9 (11)
Cu1—P1—C1—C2	1.4 (10)	C16—C17—C18—C19	2 (2)
C6—C1—C2—C3	2.1 (18)	C17—C18—C19—C20	−3 (2)
P1—C1—C2—C3	−177.1 (10)	C18—C19—C20—C21	2 (2)
C1—C2—C3—C4	−1 (2)	C19—C20—C21—C16	−2 (2)
C2—C3—C4—C5	1 (2)	C17—C16—C21—C20	0.9 (18)
C3—C4—C5—C6	−1 (2)	P2—C16—C21—C20	179.9 (10)
C2—C1—C6—C5	−3 (2)	C16—P2—C22—C23	97.0 (9)
P1—C1—C6—C5	176.6 (12)	C15—P2—C22—C23	−13.0 (10)
C4—C5—C6—C1	2 (3)	Cu2—P2—C22—C23	−135.2 (8)
C13—P1—C7—C12	1.0 (10)	C16—P2—C22—C27	−80.7 (9)
C1—P1—C7—C12	109.5 (10)	C15—P2—C22—C27	169.2 (8)
Cu1—P1—C7—C12	−122.2 (9)	Cu2—P2—C22—C27	47.0 (9)
C13—P1—C7—C8	−178.1 (9)	C27—C22—C23—C24	−0.2 (16)
C1—P1—C7—C8	−69.6 (9)	P2—C22—C23—C24	−177.9 (9)
Cu1—P1—C7—C8	58.6 (9)	C22—C23—C24—C25	1.2 (18)
C12—C7—C8—C9	−1.0 (18)	C23—C24—C25—C26	−2 (2)
P1—C7—C8—C9	178.2 (10)	C24—C25—C26—C27	2.2 (19)
C7—C8—C9—C10	2 (2)	C25—C26—C27—C22	−1.2 (18)
C8—C9—C10—C11	−3 (2)	C23—C22—C27—C26	0.2 (17)
C9—C10—C11—C12	3 (2)	P2—C22—C27—C26	178.0 (9)
C8—C7—C12—C11	0.5 (17)	C32—N1—C28—C29	2.6 (16)
P1—C7—C12—C11	−178.6 (10)	Cu2—N1—C28—C29	170.4 (8)
C10—C11—C12—C7	−2 (2)	N1—C28—C29—C30	−1.8 (17)
C7—P1—C13—C14	177.7 (7)	C28—C29—C30—C31	1.5 (16)
C1—P1—C13—C14	71.3 (8)	C28—C29—C30—C33	−175.7 (10)
Cu1—P1—C13—C14	−55.2 (8)	C29—C30—C31—C32	−2.1 (17)
P1—C13—C14—C15	173.5 (7)	C33—C30—C31—C32	175.0 (10)
C13—C14—C15—P2	−66.3 (10)	C28—N1—C32—C31	−3.3 (16)
C16—P2—C15—C14	81.4 (8)	Cu2—N1—C32—C31	−171.0 (9)
C22—P2—C15—C14	−173.5 (7)	C30—C31—C32—N1	3.2 (18)
Cu2—P2—C15—C14	−49.7 (8)	C31—C30—C33—O1	−128.9 (15)
C15—P2—C16—C17	33.5 (11)	C29—C30—C33—O1	48.2 (18)
C22—P2—C16—C17	−74.9 (10)	C31—C30—C33—C34	51.3 (18)
Cu2—P2—C16—C17	160.4 (9)	C29—C30—C33—C34	−131.6 (14)

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···I1^i	0.93	3.25	4.056 (11)	146
C14—H14B···O1^ii	0.97	2.65	3.265 (15)	121
C15—H15A···O1^ii	0.97	2.45	3.125 (14)	126
C32—H32A···I2	0.93	3.18	3.815 (11)	127
C34—H34B···I2^iii	0.96	3.26	4.109 (16)	148

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