Structural, spectroscopic and DFT theoretical studies of phospho­rescent CuIP₂S-containing cuprous com­plexes

Luminescent cuprous com­plexes are important coordination compounds due to their relative abundance, low cost and ability to display excellent luminescence. The structures of two CuIP₂S-type cuprous com­plexes, namely, iodido­(thio­urea-κS)bis­(tri­phenyl­phosphane-κP)copper(I), [CuI(CH₄N₂S)(C₁₈H₁₅P)₂] or [CuI(TU)(TPP)₂] (I), and (2,3-di­hydro­benzimidazole-2-thione-κS)iodido­bis­(tri­phenyl­phosphane-κP)copper(I), [CuI(C₇H₆N₂S)(C₁₈H₁₅P)₂] or [CuI(DHBIT)(TPP)₂] (II), are described. In these two structures, the com­plex mol­ecules of both are constructed by one copper(I) centre, one iodide ion, two TPP ligands and one thione ligand (TU for I and DHBIT for II). The copper(I) centres of I and II are both located in a distorted CuIP₂S tetra­hedron and are coordinated by two P atoms from two TPP ligands, one S atom from the thione ligand and the I atom. The UV–Vis absorption and photoluminescence properties of these CuIP₂S-type cuprous com­plexes have been studied using crystalline powder samples. Detailed time-dependent density functional theory (TD-DFT) calculations and wavefunction analysis reveal that the pale-blue–green phospho­rescence emission should originate from intra-ligand (TPP for I and DHBIT for II) charge transfer, with a small component of the metal-to-ligand charge transfer ³(IL+ML)CT excited state.

Computing details

For both structures, data collection: APEX2 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Iodido(thiourea-κS)bis(triphenylphosphane-κP)copper(I) (I)

Crystal data

[CuI(CH4N2S)(C18H15P)2]	Z = 2
Mr = 791.10	F(000) = 796
Triclinic, P1	Dx = 1.522 Mg m^−3
a = 9.7713 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.8827 (4) Å	Cell parameters from 9881 reflections
c = 16.0872 (6) Å	θ = 3.1–26.4°
α = 85.185 (1)°	µ = 1.71 mm^−1
β = 80.369 (1)°	T = 293 K
γ = 69.634 (1)°	Block, colourless
V = 1725.76 (10) Å^3	0.38 × 0.23 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer	6668 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.020
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 26.4°, θmin = 2.4°
Tmin = 0.613, Tmax = 0.745	h = −11→12
19588 measured reflections	k = −14→14
6979 independent reflections	l = −20→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.075	w = 1/[σ^2(Fo^2) + (0.0259P)^2 + 3.3403P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.002
6979 reflections	Δρmax = 1.38 e Å^−3
401 parameters	Δρmin = −0.70 e Å^−3
1 restraint

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	Occ. (<1)
I1	0.44216 (2)	0.11187 (2)	0.67484 (2)	0.02591 (6)
Cu1	0.16189 (3)	0.11946 (3)	0.69883 (2)	0.01829 (8)
S1A	0.0547 (3)	0.13063 (10)	0.57344 (11)	0.0121 (3)	0.782 (8)
S1B	0.0958 (7)	0.1373 (4)	0.5601 (3)	0.0121 (3)	0.218 (8)
P1	0.04747 (7)	0.30385 (5)	0.75502 (4)	0.01582 (13)
P2	0.18258 (7)	−0.06688 (5)	0.75641 (4)	0.01668 (13)
N1	0.3133 (3)	0.1154 (3)	0.47786 (17)	0.0349 (6)
H1A	0.376883	0.096750	0.432853	0.042*
H1B	0.330436	0.149484	0.518133	0.042*
N2	0.1671 (3)	0.0392 (3)	0.42215 (16)	0.0353 (6)
H2A	0.232266	0.021421	0.377759	0.042*
H2B	0.087265	0.022797	0.425462	0.042*
C1	−0.1544 (3)	0.3586 (2)	0.78235 (17)	0.0198 (5)
C2	−0.2362 (3)	0.3072 (3)	0.7452 (2)	0.0285 (6)
H2	−0.188167	0.246003	0.707154	0.034*
C3	−0.3895 (3)	0.3466 (3)	0.7646 (2)	0.0398 (8)
H3	−0.443570	0.311795	0.739385	0.048*
C4	−0.4613 (3)	0.4375 (3)	0.8213 (2)	0.0431 (8)
H4	−0.563635	0.463783	0.834300	0.052*
C5	−0.3810 (3)	0.4892 (3)	0.8586 (2)	0.0386 (7)
H5	−0.429288	0.549989	0.896914	0.046*
C6	−0.2282 (3)	0.4506 (3)	0.83883 (18)	0.0275 (6)
H6	−0.174765	0.486431	0.863543	0.033*
C7	0.1087 (3)	0.3223 (2)	0.85249 (16)	0.0188 (5)
C8	0.1380 (3)	0.2235 (3)	0.90825 (18)	0.0273 (6)
H8	0.125658	0.153510	0.894410	0.033*
C9	0.1852 (4)	0.2280 (3)	0.9841 (2)	0.0368 (7)
H9	0.203284	0.161693	1.021013	0.044*
C10	0.2055 (3)	0.3311 (3)	1.00495 (19)	0.0336 (7)
H10	0.238592	0.333876	1.055415	0.040*
C11	0.1761 (3)	0.4302 (3)	0.95015 (19)	0.0309 (6)
H11	0.189213	0.499740	0.964135	0.037*
C12	0.1275 (3)	0.4264 (2)	0.87504 (18)	0.0250 (6)
H12	0.107141	0.493791	0.839089	0.030*
C13	0.0804 (3)	0.4224 (2)	0.68374 (16)	0.0187 (5)
C14	−0.0240 (3)	0.4909 (2)	0.63385 (17)	0.0239 (5)
H14	−0.114123	0.478856	0.638590	0.029*
C15	0.0057 (4)	0.5775 (3)	0.57662 (18)	0.0314 (7)
H15	−0.065321	0.623728	0.544101	0.038*
C16	0.1388 (4)	0.5949 (3)	0.56814 (19)	0.0334 (7)
H16	0.157629	0.653215	0.530290	0.040*
C17	0.2453 (4)	0.5258 (3)	0.6159 (2)	0.0313 (6)
H17	0.336184	0.536875	0.609315	0.038*
C18	0.2172 (3)	0.4397 (2)	0.67353 (18)	0.0242 (6)
H18	0.289302	0.393559	0.705423	0.029*
C19	0.2424 (3)	−0.1109 (2)	0.85986 (17)	0.0217 (5)
C20	0.1845 (4)	−0.1815 (3)	0.9184 (2)	0.0406 (8)
H20	0.108603	−0.205164	0.906733	0.049*
C21	0.2393 (5)	−0.2170 (4)	0.9942 (2)	0.0557 (11)
H21	0.198966	−0.263424	1.033198	0.067*
C22	0.3530 (4)	−0.1840 (3)	1.0121 (2)	0.0453 (9)
H22	0.390575	−0.209271	1.062532	0.054*
C23	0.4104 (4)	−0.1134 (3)	0.9549 (2)	0.0367 (7)
H23	0.486939	−0.090704	0.966773	0.044*
C24	0.3546 (3)	−0.0758 (3)	0.87949 (19)	0.0278 (6)
H24	0.392724	−0.026557	0.841755	0.033*
C25	0.0151 (3)	−0.1053 (2)	0.76742 (16)	0.0191 (5)
C26	0.0147 (3)	−0.2175 (3)	0.74930 (19)	0.0278 (6)
H26	0.102883	−0.277156	0.729832	0.033*
C27	−0.1169 (4)	−0.2409 (3)	0.7602 (2)	0.0333 (7)
H27	−0.116470	−0.316137	0.747841	0.040*
C28	−0.2487 (3)	−0.1530 (3)	0.78918 (19)	0.0312 (6)
H28	−0.336774	−0.168598	0.795630	0.037*
C29	−0.2490 (3)	−0.0416 (3)	0.80861 (19)	0.0294 (6)
H29	−0.337171	0.017353	0.829109	0.035*
C30	−0.1180 (3)	−0.0181 (2)	0.79746 (18)	0.0242 (6)
H30	−0.118856	0.057071	0.810235	0.029*
C31	0.3207 (3)	−0.1813 (2)	0.68810 (17)	0.0207 (5)
C32	0.3078 (4)	−0.1776 (2)	0.60318 (18)	0.0290 (6)
H32	0.224442	−0.123196	0.583619	0.035*
C33	0.4179 (4)	−0.2543 (3)	0.5470 (2)	0.0373 (8)
H33	0.408210	−0.250750	0.490223	0.045*
C34	0.5421 (4)	−0.3359 (3)	0.5757 (2)	0.0417 (8)
H34	0.616843	−0.386257	0.538127	0.050*
C35	0.5540 (4)	−0.3418 (3)	0.6593 (3)	0.0442 (9)
H35	0.636649	−0.397698	0.678529	0.053*
C36	0.4446 (3)	−0.2658 (3)	0.7164 (2)	0.0329 (7)
H36	0.454248	−0.271375	0.773281	0.040*
C37	0.1896 (3)	0.0916 (2)	0.48513 (18)	0.0249 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.01923 (9)	0.02945 (10)	0.02953 (11)	−0.00911 (7)	−0.00349 (7)	−0.00007 (7)
Cu1	0.02102 (16)	0.01427 (15)	0.01856 (16)	−0.00515 (12)	−0.00169 (12)	−0.00109 (11)
S1A	0.0063 (8)	0.0188 (3)	0.0113 (5)	−0.0045 (4)	−0.0002 (5)	−0.0025 (3)
S1B	0.0063 (8)	0.0188 (3)	0.0113 (5)	−0.0045 (4)	−0.0002 (5)	−0.0025 (3)
P1	0.0159 (3)	0.0138 (3)	0.0173 (3)	−0.0042 (2)	−0.0026 (2)	−0.0013 (2)
P2	0.0174 (3)	0.0143 (3)	0.0173 (3)	−0.0044 (2)	−0.0022 (2)	0.0004 (2)
N1	0.0378 (14)	0.0490 (16)	0.0259 (13)	−0.0259 (13)	0.0004 (11)	−0.0067 (11)
N2	0.0340 (14)	0.0548 (17)	0.0223 (13)	−0.0214 (13)	−0.0014 (11)	−0.0083 (12)
C1	0.0179 (12)	0.0182 (12)	0.0218 (13)	−0.0057 (10)	−0.0019 (10)	0.0032 (10)
C2	0.0246 (14)	0.0232 (13)	0.0384 (17)	−0.0072 (11)	−0.0082 (12)	−0.0018 (12)
C3	0.0237 (15)	0.0376 (17)	0.063 (2)	−0.0146 (13)	−0.0114 (15)	0.0009 (16)
C4	0.0175 (14)	0.046 (2)	0.060 (2)	−0.0075 (13)	0.0002 (14)	0.0042 (17)
C5	0.0266 (15)	0.0405 (18)	0.0375 (18)	−0.0005 (13)	0.0051 (13)	−0.0071 (14)
C6	0.0228 (13)	0.0308 (15)	0.0259 (14)	−0.0055 (11)	−0.0019 (11)	−0.0040 (11)
C7	0.0161 (11)	0.0197 (12)	0.0190 (12)	−0.0038 (10)	−0.0020 (9)	−0.0034 (10)
C8	0.0353 (15)	0.0221 (13)	0.0247 (14)	−0.0077 (12)	−0.0094 (12)	−0.0008 (11)
C9	0.0473 (19)	0.0333 (16)	0.0264 (16)	−0.0059 (14)	−0.0154 (14)	0.0023 (12)
C10	0.0333 (16)	0.0426 (17)	0.0241 (15)	−0.0073 (14)	−0.0105 (12)	−0.0087 (13)
C11	0.0320 (15)	0.0341 (16)	0.0302 (16)	−0.0138 (13)	−0.0033 (12)	−0.0120 (12)
C12	0.0277 (14)	0.0229 (13)	0.0253 (14)	−0.0090 (11)	−0.0041 (11)	−0.0037 (11)
C13	0.0225 (12)	0.0133 (11)	0.0190 (12)	−0.0050 (10)	−0.0005 (10)	−0.0041 (9)
C14	0.0277 (14)	0.0218 (13)	0.0217 (13)	−0.0073 (11)	−0.0048 (11)	−0.0013 (10)
C15	0.0465 (18)	0.0233 (14)	0.0223 (14)	−0.0081 (13)	−0.0093 (13)	0.0027 (11)
C16	0.055 (2)	0.0234 (14)	0.0229 (14)	−0.0186 (14)	0.0013 (13)	0.0009 (11)
C17	0.0362 (16)	0.0278 (15)	0.0331 (16)	−0.0185 (13)	0.0045 (13)	−0.0041 (12)
C18	0.0242 (13)	0.0197 (12)	0.0281 (14)	−0.0077 (11)	−0.0016 (11)	−0.0017 (11)
C19	0.0214 (12)	0.0201 (12)	0.0199 (13)	−0.0026 (10)	−0.0036 (10)	0.0013 (10)
C20	0.0445 (19)	0.053 (2)	0.0317 (17)	−0.0275 (17)	−0.0132 (14)	0.0186 (15)
C21	0.064 (3)	0.075 (3)	0.0340 (19)	−0.034 (2)	−0.0154 (18)	0.0300 (19)
C22	0.052 (2)	0.055 (2)	0.0245 (16)	−0.0104 (17)	−0.0171 (15)	0.0089 (15)
C23	0.0362 (17)	0.0400 (17)	0.0340 (17)	−0.0081 (14)	−0.0159 (14)	−0.0019 (14)
C24	0.0280 (14)	0.0285 (14)	0.0263 (15)	−0.0084 (12)	−0.0078 (12)	0.0034 (11)
C25	0.0211 (12)	0.0193 (12)	0.0172 (12)	−0.0072 (10)	−0.0033 (10)	0.0004 (9)
C26	0.0277 (14)	0.0232 (13)	0.0317 (15)	−0.0097 (11)	0.0035 (12)	−0.0079 (11)
C27	0.0383 (17)	0.0338 (16)	0.0343 (17)	−0.0220 (14)	0.0024 (13)	−0.0101 (13)
C28	0.0278 (15)	0.0463 (18)	0.0266 (15)	−0.0210 (14)	−0.0053 (12)	−0.0002 (13)
C29	0.0189 (13)	0.0356 (16)	0.0304 (15)	−0.0044 (12)	−0.0046 (11)	−0.0016 (12)
C30	0.0223 (13)	0.0202 (13)	0.0282 (14)	−0.0041 (11)	−0.0050 (11)	−0.0015 (11)
C31	0.0218 (12)	0.0150 (11)	0.0243 (13)	−0.0081 (10)	0.0036 (10)	−0.0012 (10)
C32	0.0394 (16)	0.0190 (13)	0.0250 (14)	−0.0088 (12)	0.0023 (12)	0.0003 (11)
C33	0.058 (2)	0.0281 (15)	0.0262 (16)	−0.0224 (15)	0.0140 (14)	−0.0056 (12)
C34	0.0340 (17)	0.0307 (16)	0.055 (2)	−0.0132 (14)	0.0207 (15)	−0.0178 (15)
C35	0.0241 (15)	0.0354 (18)	0.064 (2)	0.0021 (13)	−0.0007 (15)	−0.0164 (16)
C36	0.0252 (14)	0.0274 (15)	0.0406 (18)	−0.0010 (12)	−0.0039 (13)	−0.0076 (13)
C37	0.0289 (14)	0.0234 (13)	0.0236 (14)	−0.0100 (11)	−0.0078 (11)	0.0044 (11)

Geometric parameters (Å, º)

I1—Cu1	2.6716 (4)	C14—H14	0.9300
Cu1—S1A	2.3978 (11)	C14—C15	1.397 (4)
Cu1—S1B	2.398 (5)	C15—H15	0.9300
Cu1—P1	2.2709 (7)	C15—C16	1.369 (5)
Cu1—P2	2.2822 (7)	C16—H16	0.9300
S1A—C37	1.741 (4)	C16—C17	1.383 (5)
S1B—C37	1.409 (7)	C17—H17	0.9300
P1—C1	1.836 (3)	C17—C18	1.390 (4)
P1—C7	1.824 (3)	C18—H18	0.9300
P1—C13	1.823 (3)	C19—C20	1.389 (4)
P2—C19	1.831 (3)	C19—C24	1.391 (4)
P2—C25	1.824 (3)	C20—H20	0.9300
P2—C31	1.832 (3)	C20—C21	1.387 (5)
N1—H1A	0.8600	C21—H21	0.9300
N1—H1B	0.8600	C21—C22	1.379 (6)
N1—C37	1.319 (4)	C22—H22	0.9300
N2—H2A	0.8600	C22—C23	1.375 (5)
N2—H2B	0.8600	C23—H23	0.9300
N2—C37	1.318 (4)	C23—C24	1.389 (4)
C1—C2	1.389 (4)	C24—H24	0.9300
C1—C6	1.392 (4)	C25—C26	1.391 (4)
C2—H2	0.9300	C25—C30	1.390 (4)
C2—C3	1.394 (4)	C26—H26	0.9300
C3—H3	0.9300	C26—C27	1.388 (4)
C3—C4	1.384 (5)	C27—H27	0.9300
C4—H4	0.9300	C27—C28	1.383 (4)
C4—C5	1.381 (5)	C28—H28	0.9300
C5—H5	0.9300	C28—C29	1.384 (4)
C5—C6	1.389 (4)	C29—H29	0.9300
C6—H6	0.9300	C29—C30	1.383 (4)
C7—C8	1.393 (4)	C30—H30	0.9300
C7—C12	1.397 (4)	C31—C32	1.388 (4)
C8—H8	0.9300	C31—C36	1.394 (4)
C8—C9	1.386 (4)	C32—H32	0.9300
C9—H9	0.9300	C32—C33	1.392 (4)
C9—C10	1.382 (5)	C33—H33	0.9300
C10—H10	0.9300	C33—C34	1.385 (5)
C10—C11	1.386 (5)	C34—H34	0.9300
C11—H11	0.9300	C34—C35	1.363 (6)
C11—C12	1.379 (4)	C35—H35	0.9300
C12—H12	0.9300	C35—C36	1.394 (4)
C13—C14	1.390 (4)	C36—H36	0.9300
C13—C18	1.403 (4)
S1A—Cu1—I1	115.80 (7)	C14—C15—H15	119.8
S1B—Cu1—I1	105.16 (18)	C16—C15—C14	120.4 (3)
P1—Cu1—I1	100.223 (19)	C16—C15—H15	119.8
P1—Cu1—S1A	104.40 (3)	C15—C16—H16	120.0
P1—Cu1—S1B	105.76 (11)	C15—C16—C17	120.0 (3)
P1—Cu1—P2	130.49 (3)	C17—C16—H16	120.0
P2—Cu1—I1	101.78 (2)	C16—C17—H17	119.8
P2—Cu1—S1A	104.85 (5)	C16—C17—C18	120.3 (3)
P2—Cu1—S1B	110.31 (14)	C18—C17—H17	119.8
C37—S1A—Cu1	111.36 (14)	C13—C18—H18	119.9
C37—S1B—Cu1	127.2 (3)	C17—C18—C13	120.2 (3)
C1—P1—Cu1	119.00 (9)	C17—C18—H18	119.9
C7—P1—Cu1	114.27 (8)	C20—C19—P2	123.0 (2)
C7—P1—C1	102.80 (12)	C20—C19—C24	118.5 (3)
C13—P1—Cu1	111.94 (8)	C24—C19—P2	118.5 (2)
C13—P1—C1	102.50 (11)	C19—C20—H20	119.8
C13—P1—C7	104.71 (12)	C21—C20—C19	120.4 (3)
C19—P2—Cu1	120.63 (9)	C21—C20—H20	119.8
C19—P2—C31	102.47 (12)	C20—C21—H21	119.7
C25—P2—Cu1	114.96 (8)	C22—C21—C20	120.6 (3)
C25—P2—C19	102.58 (12)	C22—C21—H21	119.7
C25—P2—C31	104.91 (12)	C21—C22—H22	120.3
C31—P2—Cu1	109.58 (8)	C23—C22—C21	119.5 (3)
H1A—N1—H1B	120.0	C23—C22—H22	120.3
C37—N1—H1A	120.0	C22—C23—H23	119.8
C37—N1—H1B	120.0	C22—C23—C24	120.3 (3)
H2A—N2—H2B	120.0	C24—C23—H23	119.8
C37—N2—H2A	120.0	C19—C24—H24	119.7
C37—N2—H2B	120.0	C23—C24—C19	120.6 (3)
C2—C1—P1	119.0 (2)	C23—C24—H24	119.7
C2—C1—C6	118.9 (3)	C26—C25—P2	123.4 (2)
C6—C1—P1	122.1 (2)	C30—C25—P2	117.8 (2)
C1—C2—H2	119.7	C30—C25—C26	118.8 (2)
C1—C2—C3	120.5 (3)	C25—C26—H26	119.9
C3—C2—H2	119.7	C27—C26—C25	120.2 (3)
C2—C3—H3	120.1	C27—C26—H26	119.9
C4—C3—C2	119.9 (3)	C26—C27—H27	119.8
C4—C3—H3	120.1	C28—C27—C26	120.3 (3)
C3—C4—H4	120.0	C28—C27—H27	119.8
C5—C4—C3	120.0 (3)	C27—C28—H28	120.1
C5—C4—H4	120.0	C27—C28—C29	119.8 (3)
C4—C5—H5	120.0	C29—C28—H28	120.1
C4—C5—C6	120.1 (3)	C28—C29—H29	120.1
C6—C5—H5	120.0	C30—C29—C28	119.8 (3)
C1—C6—H6	119.7	C30—C29—H29	120.1
C5—C6—C1	120.5 (3)	C25—C30—H30	119.5
C5—C6—H6	119.7	C29—C30—C25	120.9 (3)
C8—C7—P1	116.3 (2)	C29—C30—H30	119.5
C8—C7—C12	118.4 (2)	C32—C31—P2	118.6 (2)
C12—C7—P1	125.4 (2)	C32—C31—C36	118.6 (3)
C7—C8—H8	119.6	C36—C31—P2	122.6 (2)
C9—C8—C7	120.9 (3)	C31—C32—H32	119.6
C9—C8—H8	119.6	C31—C32—C33	120.8 (3)
C8—C9—H9	120.0	C33—C32—H32	119.6
C10—C9—C8	120.1 (3)	C32—C33—H33	120.0
C10—C9—H9	120.0	C34—C33—C32	120.0 (3)
C9—C10—H10	120.2	C34—C33—H33	120.0
C9—C10—C11	119.6 (3)	C33—C34—H34	120.2
C11—C10—H10	120.2	C35—C34—C33	119.5 (3)
C10—C11—H11	119.7	C35—C34—H34	120.2
C12—C11—C10	120.5 (3)	C34—C35—H35	119.4
C12—C11—H11	119.7	C34—C35—C36	121.2 (3)
C7—C12—H12	119.7	C36—C35—H35	119.4
C11—C12—C7	120.6 (3)	C31—C36—C35	119.8 (3)
C11—C12—H12	119.7	C31—C36—H36	120.1
C14—C13—P1	121.1 (2)	C35—C36—H36	120.1
C14—C13—C18	118.7 (2)	N1—C37—S1A	122.1 (2)
C18—C13—P1	120.1 (2)	N1—C37—S1B	111.2 (4)
C13—C14—H14	119.8	N2—C37—S1A	119.5 (2)
C13—C14—C15	120.4 (3)	N2—C37—S1B	130.3 (4)
C15—C14—H14	119.8	N2—C37—N1	118.3 (3)
Cu1—S1A—C37—N1	−33.1 (3)	C8—C9—C10—C11	1.0 (5)
Cu1—S1A—C37—N2	148.6 (2)	C9—C10—C11—C12	−0.3 (5)
Cu1—S1B—C37—N1	−46.4 (5)	C10—C11—C12—C7	−0.7 (4)
Cu1—S1B—C37—N2	139.0 (4)	C12—C7—C8—C9	−0.2 (4)
Cu1—P1—C1—C2	−20.2 (3)	C13—P1—C1—C2	103.9 (2)
Cu1—P1—C1—C6	160.1 (2)	C13—P1—C1—C6	−75.8 (2)
Cu1—P1—C7—C8	−38.3 (2)	C13—P1—C7—C8	−161.1 (2)
Cu1—P1—C7—C12	141.9 (2)	C13—P1—C7—C12	19.1 (3)
Cu1—P1—C13—C14	99.3 (2)	C13—C14—C15—C16	0.9 (4)
Cu1—P1—C13—C18	−75.7 (2)	C14—C13—C18—C17	1.4 (4)
Cu1—P2—C19—C20	142.6 (2)	C14—C15—C16—C17	0.5 (5)
Cu1—P2—C19—C24	−39.8 (2)	C15—C16—C17—C18	−1.0 (5)
Cu1—P2—C25—C26	138.3 (2)	C16—C17—C18—C13	0.0 (4)
Cu1—P2—C25—C30	−43.3 (2)	C18—C13—C14—C15	−1.9 (4)
Cu1—P2—C31—C32	−52.2 (2)	C19—P2—C25—C26	−88.8 (2)
Cu1—P2—C31—C36	122.4 (2)	C19—P2—C25—C30	89.6 (2)
P1—C1—C2—C3	180.0 (2)	C19—P2—C31—C32	178.5 (2)
P1—C1—C6—C5	−179.5 (2)	C19—P2—C31—C36	−6.9 (3)
P1—C7—C8—C9	179.9 (2)	C19—C20—C21—C22	−0.8 (7)
P1—C7—C12—C11	−179.3 (2)	C20—C19—C24—C23	1.9 (4)
P1—C13—C14—C15	−177.0 (2)	C20—C21—C22—C23	1.2 (7)
P1—C13—C18—C17	176.5 (2)	C21—C22—C23—C24	−0.2 (6)
P2—C19—C20—C21	176.8 (3)	C22—C23—C24—C19	−1.4 (5)
P2—C19—C24—C23	−175.9 (2)	C24—C19—C20—C21	−0.8 (5)
P2—C25—C26—C27	179.2 (2)	C25—P2—C19—C20	13.2 (3)
P2—C25—C30—C29	−179.0 (2)	C25—P2—C19—C24	−169.2 (2)
P2—C31—C32—C33	173.1 (2)	C25—P2—C31—C32	71.7 (2)
P2—C31—C36—C35	−172.8 (2)	C25—P2—C31—C36	−113.7 (2)
C1—P1—C7—C8	92.1 (2)	C25—C26—C27—C28	−0.1 (5)
C1—P1—C7—C12	−87.7 (2)	C26—C25—C30—C29	−0.5 (4)
C1—P1—C13—C14	−29.4 (2)	C26—C27—C28—C29	−0.9 (5)
C1—P1—C13—C18	155.6 (2)	C27—C28—C29—C30	1.2 (5)
C1—C2—C3—C4	−0.1 (5)	C28—C29—C30—C25	−0.4 (4)
C2—C1—C6—C5	0.8 (4)	C30—C25—C26—C27	0.8 (4)
C2—C3—C4—C5	0.1 (5)	C31—P2—C19—C20	−95.5 (3)
C3—C4—C5—C6	0.4 (5)	C31—P2—C19—C24	82.1 (2)
C4—C5—C6—C1	−0.8 (5)	C31—P2—C25—C26	17.9 (3)
C6—C1—C2—C3	−0.4 (4)	C31—P2—C25—C30	−163.7 (2)
C7—P1—C1—C2	−147.6 (2)	C31—C32—C33—C34	0.2 (4)
C7—P1—C1—C6	32.7 (3)	C32—C31—C36—C35	1.8 (4)
C7—P1—C13—C14	−136.4 (2)	C32—C33—C34—C35	1.2 (5)
C7—P1—C13—C18	48.6 (2)	C33—C34—C35—C36	−1.2 (5)
C7—C8—C9—C10	−0.7 (5)	C34—C35—C36—C31	−0.3 (5)
C8—C7—C12—C11	1.0 (4)	C36—C31—C32—C33	−1.7 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···I1^i	0.86	2.99	3.7004 (1)	142
N1—H1B···I1	0.86	2.85	3.5923 (1)	145
N2—H2A···I1^i^i	0.86	3.03	3.7336 (17)	141
N2—H2B···S1A^ii^ii	0.86	2.64	3.4268 (15)	152
N2—H2B···S1B^ii^iii	0.86	2.72	3.6108 (15)	154

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

(2,3-Dihydrobenzimidazole-2-thione-κS)iodidobis(triphenylphosphane-κP)copper(I) (II)

Crystal data

[CuI(C7H6N2S)(C18H15P)2]	F(000) = 3488
Mr = 865.18	Dx = 1.493 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.9718 (3) Å	Cell parameters from 9613 reflections
b = 15.9975 (4) Å	θ = 2.5–27.1°
c = 44.0539 (12) Å	µ = 1.54 mm^−1
β = 95.2989 (9)°	T = 170 K
V = 7699.4 (4) Å^3	Block, yellow
Z = 8	0.43 × 0.29 × 0.22 mm

Data collection

Bruker APEXII CCD diffractometer	15368 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.022
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 27.1°, θmin = 2.3°
Tmin = 0.632, Tmax = 0.746	h = −14→14
51806 measured reflections	k = −20→18
16944 independent reflections	l = −56→56

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.023	H-atom parameters constrained
wR(F^2) = 0.053	w = 1/[σ^2(Fo^2) + (0.017P)^2 + 4.4532P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.002
16944 reflections	Δρmax = 0.37 e Å^−3
901 parameters	Δρmin = −0.36 e Å^−3
0 restraints

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	0.34895 (2)	0.98672 (2)	0.08933 (2)	0.02459 (3)
Cu1	0.55393 (2)	0.95158 (2)	0.12562 (2)	0.01996 (5)
S1	0.59925 (5)	0.80871 (3)	0.12332 (2)	0.03069 (11)
P1	0.52161 (4)	0.97872 (3)	0.17485 (2)	0.01957 (9)
P2	0.70345 (4)	1.01671 (3)	0.10144 (2)	0.01906 (9)
N1	0.51369 (14)	0.81245 (10)	0.06322 (3)	0.0270 (3)
H1	0.458554	0.851487	0.065292	0.032*
N2	0.65807 (14)	0.72176 (9)	0.07392 (3)	0.0258 (3)
H2	0.713870	0.690866	0.084243	0.031*
C1	0.58995 (16)	0.78121 (11)	0.08622 (4)	0.0245 (4)
C2	0.53435 (16)	0.77433 (11)	0.03572 (4)	0.0254 (4)
C3	0.48212 (19)	0.78526 (13)	0.00619 (4)	0.0332 (4)
H3	0.416996	0.823590	0.001448	0.040*
C4	0.5297 (2)	0.73743 (14)	−0.01611 (5)	0.0365 (5)
H4	0.496924	0.743411	−0.036716	0.044*
C5	0.6243 (2)	0.68082 (14)	−0.00905 (5)	0.0380 (5)
H5	0.655047	0.649639	−0.025036	0.046*
C6	0.67470 (19)	0.66862 (13)	0.02035 (5)	0.0335 (4)
H6	0.738658	0.629408	0.025091	0.040*
C7	0.62741 (16)	0.71648 (11)	0.04274 (4)	0.0249 (4)
C8	0.65215 (16)	0.95588 (11)	0.20270 (4)	0.0227 (4)
C9	0.76805 (17)	0.98269 (14)	0.19635 (4)	0.0333 (4)
H9	0.777025	1.012077	0.177948	0.040*
C10	0.87002 (18)	0.96721 (15)	0.21636 (5)	0.0397 (5)
H10	0.948175	0.986285	0.211726	0.048*
C11	0.85857 (19)	0.92407 (14)	0.24309 (5)	0.0384 (5)
H11	0.928656	0.913396	0.256865	0.046*
C12	0.74468 (19)	0.89652 (13)	0.24970 (5)	0.0353 (5)
H12	0.736625	0.866651	0.268044	0.042*
C13	0.64197 (17)	0.91220 (12)	0.22971 (4)	0.0278 (4)
H13	0.564058	0.892981	0.234477	0.033*
C14	0.39640 (15)	0.92160 (11)	0.19013 (4)	0.0210 (3)
C15	0.36345 (18)	0.84293 (12)	0.17847 (4)	0.0295 (4)
H15	0.404107	0.820062	0.162248	0.035*
C16	0.27105 (19)	0.79804 (13)	0.19062 (5)	0.0354 (5)
H16	0.250781	0.743650	0.183112	0.042*
C17	0.20830 (18)	0.83170 (13)	0.21353 (4)	0.0325 (4)
H17	0.143960	0.801123	0.221389	0.039*
C18	0.23955 (17)	0.90989 (13)	0.22493 (4)	0.0290 (4)
H18	0.196459	0.933349	0.240620	0.035*
C19	0.33383 (16)	0.95431 (12)	0.21350 (4)	0.0259 (4)
H19	0.355920	1.007669	0.221731	0.031*
C20	0.48361 (16)	1.08745 (11)	0.18360 (4)	0.0214 (4)
C21	0.54853 (18)	1.13429 (12)	0.20611 (4)	0.0310 (4)
H21	0.616203	1.109990	0.217942	0.037*
C22	0.5155 (2)	1.21673 (13)	0.21157 (5)	0.0380 (5)
H22	0.560908	1.248398	0.226955	0.046*
C23	0.4169 (2)	1.25230 (12)	0.19464 (5)	0.0360 (5)
H23	0.394092	1.308337	0.198475	0.043*
C24	0.35132 (18)	1.20655 (12)	0.17212 (5)	0.0310 (4)
H24	0.283482	1.231200	0.160464	0.037*
C25	0.38432 (16)	1.12440 (12)	0.16644 (4)	0.0261 (4)
H25	0.339195	1.093291	0.150837	0.031*
C26	0.85588 (15)	1.00359 (11)	0.12155 (4)	0.0225 (4)
C27	0.89947 (17)	0.92262 (12)	0.12809 (4)	0.0294 (4)
H27	0.850059	0.875651	0.122051	0.035*
C28	1.01414 (18)	0.91086 (14)	0.14330 (5)	0.0367 (5)
H28	1.044382	0.855782	0.146950	0.044*
C29	1.08478 (18)	0.97831 (15)	0.15320 (5)	0.0403 (5)
H29	1.164295	0.969789	0.163189	0.048*
C30	1.04005 (18)	1.05827 (15)	0.14861 (5)	0.0398 (5)
H30	1.086978	1.104789	0.156338	0.048*
C31	0.92595 (17)	1.07082 (13)	0.13262 (5)	0.0309 (4)
H31	0.895923	1.126072	0.129277	0.037*
C32	0.68979 (15)	1.12972 (11)	0.09691 (4)	0.0216 (4)
C33	0.60772 (16)	1.17114 (12)	0.11361 (4)	0.0281 (4)
H33	0.557164	1.140153	0.125909	0.034*
C34	0.59870 (19)	1.25774 (13)	0.11253 (5)	0.0379 (5)
H34	0.542240	1.285552	0.124157	0.046*
C35	0.67094 (19)	1.30349 (12)	0.09475 (5)	0.0371 (5)
H35	0.665227	1.362737	0.094293	0.045*
C36	0.75168 (19)	1.26292 (13)	0.07759 (5)	0.0372 (5)
H36	0.800908	1.294216	0.065056	0.045*
C37	0.76113 (18)	1.17661 (12)	0.07860 (5)	0.0332 (5)
H37	0.816830	1.149076	0.066679	0.040*
C38	0.72144 (15)	0.98126 (11)	0.06256 (4)	0.0214 (4)
C39	0.80179 (18)	0.91819 (13)	0.05593 (5)	0.0327 (4)
H39	0.854341	0.894085	0.071927	0.039*
C40	0.80642 (19)	0.88987 (14)	0.02631 (5)	0.0367 (5)
H40	0.860966	0.845934	0.022316	0.044*
C41	0.73315 (18)	0.92458 (13)	0.00270 (4)	0.0325 (4)
H41	0.737772	0.905621	−0.017596	0.039*
C42	0.65270 (18)	0.98731 (13)	0.00877 (4)	0.0313 (4)
H42	0.602382	1.012258	−0.007463	0.038*
C43	0.64486 (17)	1.01426 (12)	0.03856 (4)	0.0281 (4)
H43	0.586477	1.055718	0.042572	0.034*
I2	1.12963 (2)	1.45622 (2)	−0.08931 (2)	0.02757 (3)
Cu2	0.91183 (2)	1.43514 (2)	−0.12231 (2)	0.02151 (5)
S2	0.84665 (5)	1.29642 (3)	−0.11909 (2)	0.03285 (11)
P3	0.94833 (4)	1.45603 (3)	−0.17182 (2)	0.02109 (9)
P4	0.76900 (4)	1.51336 (3)	−0.10031 (2)	0.01850 (9)
N3	0.93057 (15)	1.30857 (10)	−0.05903 (3)	0.0287 (3)
H3A	0.960368	1.359382	−0.060327	0.034*
N4	0.84189 (15)	1.19091 (10)	−0.07140 (4)	0.0314 (4)
H4A	0.803163	1.151129	−0.082199	0.038*
C44	0.87355 (17)	1.26553 (11)	−0.08260 (4)	0.0268 (4)
C45	0.93562 (17)	1.26141 (12)	−0.03243 (4)	0.0289 (4)
C46	0.98490 (19)	1.27701 (14)	−0.00301 (5)	0.0363 (5)
H46	1.023277	1.328735	0.002527	0.044*
C47	0.9756 (2)	1.21336 (16)	0.01812 (5)	0.0432 (5)
H47	1.007626	1.221946	0.038662	0.052*
C48	0.9205 (2)	1.13740 (16)	0.00988 (5)	0.0479 (6)
H48	0.917332	1.094943	0.024862	0.058*
C49	0.8706 (2)	1.12207 (15)	−0.01939 (5)	0.0438 (5)
H49	0.832122	1.070355	−0.024917	0.053*
C50	0.87904 (18)	1.18569 (13)	−0.04042 (5)	0.0314 (4)
C51	1.07424 (16)	1.39658 (11)	−0.18575 (4)	0.0236 (4)
C52	1.13942 (16)	1.42601 (12)	−0.20920 (4)	0.0272 (4)
H52	1.121085	1.479496	−0.217814	0.033*
C53	1.23115 (17)	1.37767 (14)	−0.22009 (5)	0.0343 (5)
H53	1.276344	1.398610	−0.235827	0.041*
C54	1.25668 (19)	1.29934 (14)	−0.20808 (5)	0.0401 (5)
H54	1.319114	1.266204	−0.215615	0.048*
C55	1.1915 (2)	1.26910 (14)	−0.18509 (5)	0.0429 (5)
H55	1.208215	1.214748	−0.177082	0.051*
C56	1.10139 (19)	1.31788 (13)	−0.17362 (5)	0.0340 (5)
H56	1.058281	1.297318	−0.157433	0.041*
C57	0.82130 (16)	1.42955 (11)	−0.20024 (4)	0.0227 (4)
C58	0.83703 (16)	1.39025 (11)	−0.22779 (4)	0.0243 (4)
H58	0.917260	1.377258	−0.232793	0.029*
C59	0.73709 (18)	1.36979 (12)	−0.24802 (4)	0.0293 (4)
H59	0.749153	1.342720	−0.266705	0.035*
C60	0.62029 (18)	1.38868 (14)	−0.24107 (5)	0.0356 (5)
H60	0.551832	1.374668	−0.254930	0.043*
C61	0.60316 (19)	1.42782 (16)	−0.21403 (5)	0.0443 (6)
H61	0.522781	1.441342	−0.209281	0.053*
C62	0.70277 (18)	1.44760 (15)	−0.19370 (5)	0.0392 (5)
H62	0.689788	1.473965	−0.174941	0.047*
C63	0.98772 (16)	1.56362 (11)	−0.18128 (4)	0.0238 (4)
C64	1.09042 (17)	1.60002 (12)	−0.16533 (4)	0.0285 (4)
H64	1.138599	1.568376	−0.150433	0.034*
C65	1.12246 (19)	1.68199 (13)	−0.17111 (5)	0.0354 (5)
H65	1.192129	1.706299	−0.160092	0.043*
C66	1.0534 (2)	1.72831 (13)	−0.19282 (5)	0.0431 (5)
H66	1.075685	1.784353	−0.196803	0.052*
C67	0.9522 (2)	1.69324 (14)	−0.20870 (6)	0.0496 (6)
H67	0.904591	1.725138	−0.223642	0.059*
C68	0.9193 (2)	1.61107 (13)	−0.20290 (5)	0.0370 (5)
H68	0.849169	1.587345	−0.213904	0.044*
C69	0.74368 (16)	1.48940 (11)	−0.06062 (4)	0.0222 (4)
C70	0.6357 (2)	1.45773 (15)	−0.05108 (5)	0.0425 (5)
H70	0.567337	1.448453	−0.065538	0.051*
C71	0.6271 (2)	1.43950 (17)	−0.02048 (5)	0.0543 (7)
H71	0.553037	1.417339	−0.014270	0.065*
C72	0.7241 (2)	1.45311 (14)	0.00081 (5)	0.0422 (5)
H72	0.718031	1.439616	0.021611	0.051*
C73	0.83075 (19)	1.48658 (14)	−0.00825 (5)	0.0361 (5)
H73	0.897543	1.497765	0.006481	0.043*
C74	0.84109 (17)	1.50401 (13)	−0.03874 (4)	0.0296 (4)
H74	0.915501	1.526170	−0.044760	0.036*
C75	0.61795 (15)	1.50287 (11)	−0.12109 (4)	0.0211 (4)
C76	0.56018 (17)	1.42462 (12)	−0.12281 (4)	0.0302 (4)
H76	0.598194	1.378216	−0.112331	0.036*
C77	0.44851 (18)	1.41436 (14)	−0.13960 (5)	0.0362 (5)
H77	0.409423	1.361321	−0.140284	0.043*
C78	0.39367 (18)	1.48081 (15)	−0.15536 (5)	0.0382 (5)
H78	0.315738	1.473930	−0.166387	0.046*
C79	0.45156 (18)	1.55721 (13)	−0.15517 (5)	0.0349 (5)
H79	0.415122	1.602298	−0.166744	0.042*
C80	0.56323 (16)	1.56840 (12)	−0.13806 (4)	0.0253 (4)
H80	0.602595	1.621312	−0.137948	0.030*
C81	0.79318 (15)	1.62603 (11)	−0.09808 (4)	0.0199 (3)
C82	0.89883 (16)	1.65871 (12)	−0.10858 (4)	0.0261 (4)
H82	0.956568	1.622533	−0.116604	0.031*
C83	0.92007 (18)	1.74454 (12)	−0.10735 (5)	0.0327 (4)
H83	0.992233	1.766679	−0.114647	0.039*
C84	0.83732 (18)	1.79754 (12)	−0.09566 (5)	0.0309 (4)
H84	0.852335	1.856023	−0.094923	0.037*
C85	0.73211 (18)	1.76542 (12)	−0.08495 (4)	0.0288 (4)
H85	0.674906	1.801895	−0.076870	0.035*
C86	0.71035 (16)	1.68031 (11)	−0.08603 (4)	0.0242 (4)
H86	0.638407	1.658541	−0.078506	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.02180 (6)	0.02259 (6)	0.02857 (6)	0.00195 (5)	−0.00206 (4)	−0.00436 (5)
Cu1	0.02350 (10)	0.01882 (11)	0.01774 (10)	−0.00087 (8)	0.00282 (8)	−0.00191 (8)
S1	0.0502 (3)	0.0203 (2)	0.0213 (2)	0.0066 (2)	0.0017 (2)	−0.00142 (18)
P1	0.0228 (2)	0.0190 (2)	0.0168 (2)	−0.00105 (18)	0.00155 (17)	−0.00199 (17)
P2	0.0183 (2)	0.0182 (2)	0.0208 (2)	0.00264 (17)	0.00282 (17)	0.00128 (17)
N1	0.0333 (8)	0.0222 (8)	0.0255 (8)	0.0084 (7)	0.0026 (7)	−0.0030 (6)
N2	0.0322 (8)	0.0217 (8)	0.0234 (8)	0.0082 (7)	0.0020 (6)	−0.0020 (6)
C1	0.0306 (9)	0.0169 (9)	0.0261 (9)	0.0011 (7)	0.0038 (7)	−0.0008 (7)
C2	0.0292 (9)	0.0214 (9)	0.0257 (9)	0.0004 (8)	0.0033 (7)	−0.0026 (7)
C3	0.0400 (11)	0.0297 (11)	0.0288 (11)	0.0032 (9)	−0.0023 (9)	0.0032 (8)
C4	0.0488 (12)	0.0383 (12)	0.0218 (10)	−0.0030 (10)	0.0001 (9)	0.0007 (8)
C5	0.0483 (12)	0.0400 (12)	0.0272 (11)	0.0010 (10)	0.0118 (9)	−0.0069 (9)
C6	0.0373 (11)	0.0344 (11)	0.0297 (11)	0.0063 (9)	0.0078 (9)	−0.0050 (8)
C7	0.0287 (9)	0.0220 (9)	0.0242 (9)	−0.0002 (8)	0.0037 (7)	−0.0006 (7)
C8	0.0250 (8)	0.0225 (9)	0.0204 (9)	0.0022 (7)	−0.0003 (7)	−0.0046 (7)
C9	0.0301 (10)	0.0452 (12)	0.0248 (10)	−0.0042 (9)	0.0036 (8)	−0.0030 (9)
C10	0.0242 (10)	0.0542 (14)	0.0403 (12)	−0.0024 (10)	0.0010 (9)	−0.0081 (10)
C11	0.0339 (11)	0.0401 (12)	0.0385 (12)	0.0085 (10)	−0.0104 (9)	−0.0061 (10)
C12	0.0409 (11)	0.0327 (11)	0.0307 (11)	0.0078 (9)	−0.0057 (9)	0.0048 (9)
C13	0.0303 (9)	0.0256 (10)	0.0273 (10)	0.0031 (8)	0.0009 (8)	0.0026 (8)
C14	0.0229 (8)	0.0212 (9)	0.0185 (8)	−0.0002 (7)	−0.0007 (7)	0.0010 (7)
C15	0.0382 (10)	0.0246 (10)	0.0261 (10)	−0.0042 (8)	0.0054 (8)	−0.0032 (8)
C16	0.0469 (12)	0.0252 (10)	0.0338 (11)	−0.0111 (9)	0.0030 (9)	−0.0008 (8)
C17	0.0312 (10)	0.0370 (11)	0.0293 (10)	−0.0080 (9)	0.0023 (8)	0.0095 (9)
C18	0.0277 (9)	0.0358 (11)	0.0241 (9)	0.0008 (8)	0.0052 (8)	0.0029 (8)
C19	0.0280 (9)	0.0262 (10)	0.0233 (9)	−0.0029 (8)	0.0020 (7)	−0.0033 (7)
C20	0.0260 (8)	0.0187 (8)	0.0201 (8)	−0.0015 (7)	0.0055 (7)	−0.0003 (7)
C21	0.0378 (10)	0.0255 (10)	0.0285 (10)	−0.0005 (9)	−0.0042 (8)	−0.0023 (8)
C22	0.0503 (13)	0.0250 (10)	0.0372 (12)	−0.0062 (10)	−0.0037 (10)	−0.0092 (9)
C23	0.0514 (12)	0.0199 (10)	0.0375 (12)	0.0023 (9)	0.0087 (10)	−0.0022 (8)
C24	0.0345 (10)	0.0274 (10)	0.0315 (11)	0.0062 (8)	0.0045 (8)	0.0032 (8)
C25	0.0284 (9)	0.0254 (9)	0.0246 (9)	0.0000 (8)	0.0024 (7)	−0.0041 (7)
C26	0.0189 (8)	0.0266 (9)	0.0223 (9)	0.0019 (7)	0.0032 (7)	0.0033 (7)
C27	0.0316 (10)	0.0273 (10)	0.0284 (10)	0.0062 (8)	−0.0018 (8)	−0.0005 (8)
C28	0.0353 (11)	0.0404 (12)	0.0334 (11)	0.0160 (10)	−0.0021 (9)	0.0052 (9)
C29	0.0221 (9)	0.0590 (15)	0.0387 (12)	0.0035 (10)	−0.0036 (8)	0.0153 (11)
C30	0.0279 (10)	0.0429 (13)	0.0464 (13)	−0.0122 (9)	−0.0079 (9)	0.0130 (10)
C31	0.0255 (9)	0.0278 (10)	0.0387 (11)	−0.0036 (8)	−0.0008 (8)	0.0090 (8)
C32	0.0199 (8)	0.0199 (9)	0.0247 (9)	0.0021 (7)	0.0000 (7)	0.0004 (7)
C33	0.0260 (9)	0.0261 (10)	0.0330 (10)	0.0020 (8)	0.0060 (8)	−0.0016 (8)
C34	0.0352 (11)	0.0270 (11)	0.0520 (14)	0.0085 (9)	0.0061 (10)	−0.0085 (9)
C35	0.0398 (11)	0.0171 (9)	0.0518 (14)	0.0032 (9)	−0.0099 (10)	−0.0007 (9)
C36	0.0391 (11)	0.0254 (10)	0.0473 (13)	−0.0019 (9)	0.0046 (10)	0.0118 (9)
C37	0.0342 (10)	0.0270 (10)	0.0401 (12)	0.0041 (9)	0.0133 (9)	0.0064 (9)
C38	0.0216 (8)	0.0207 (9)	0.0224 (9)	−0.0008 (7)	0.0043 (7)	0.0012 (7)
C39	0.0332 (10)	0.0367 (11)	0.0284 (10)	0.0115 (9)	0.0043 (8)	0.0008 (8)
C40	0.0397 (11)	0.0390 (12)	0.0326 (11)	0.0114 (10)	0.0090 (9)	−0.0069 (9)
C41	0.0388 (11)	0.0352 (11)	0.0244 (10)	−0.0061 (9)	0.0081 (8)	−0.0039 (8)
C42	0.0299 (9)	0.0384 (11)	0.0249 (10)	−0.0031 (9)	−0.0007 (8)	0.0033 (8)
C43	0.0258 (9)	0.0300 (10)	0.0284 (10)	0.0033 (8)	0.0025 (8)	0.0008 (8)
I2	0.02336 (6)	0.03192 (7)	0.02653 (6)	0.00317 (5)	−0.00262 (5)	0.00392 (5)
Cu2	0.02659 (11)	0.01950 (11)	0.01800 (10)	0.00410 (9)	−0.00018 (8)	0.00078 (8)
S2	0.0510 (3)	0.0200 (2)	0.0257 (2)	−0.0012 (2)	−0.0064 (2)	0.00009 (18)
P3	0.0259 (2)	0.0204 (2)	0.0165 (2)	0.00431 (18)	−0.00098 (17)	0.00023 (17)
P4	0.0196 (2)	0.0161 (2)	0.0195 (2)	−0.00075 (17)	0.00086 (17)	−0.00018 (16)
N3	0.0401 (9)	0.0192 (8)	0.0260 (8)	−0.0018 (7)	−0.0004 (7)	0.0003 (6)
N4	0.0373 (9)	0.0256 (9)	0.0304 (9)	−0.0113 (7)	−0.0008 (7)	0.0026 (7)
C44	0.0300 (9)	0.0199 (9)	0.0302 (10)	0.0005 (8)	0.0016 (8)	−0.0006 (7)
C45	0.0312 (10)	0.0290 (10)	0.0272 (10)	0.0038 (8)	0.0070 (8)	0.0017 (8)
C46	0.0426 (12)	0.0376 (12)	0.0290 (11)	0.0050 (10)	0.0047 (9)	−0.0039 (9)
C47	0.0507 (13)	0.0589 (15)	0.0208 (10)	0.0075 (12)	0.0078 (9)	0.0028 (10)
C48	0.0594 (15)	0.0536 (15)	0.0334 (12)	−0.0007 (12)	0.0180 (11)	0.0162 (11)
C49	0.0511 (13)	0.0417 (13)	0.0398 (13)	−0.0114 (11)	0.0110 (10)	0.0118 (10)
C50	0.0308 (10)	0.0348 (11)	0.0295 (10)	−0.0037 (9)	0.0065 (8)	0.0044 (8)
C51	0.0257 (9)	0.0235 (9)	0.0204 (9)	0.0034 (7)	−0.0040 (7)	−0.0042 (7)
C52	0.0259 (9)	0.0294 (10)	0.0255 (10)	0.0018 (8)	−0.0015 (7)	−0.0025 (8)
C53	0.0284 (10)	0.0448 (13)	0.0293 (11)	0.0018 (9)	0.0011 (8)	−0.0112 (9)
C54	0.0337 (11)	0.0458 (13)	0.0396 (12)	0.0159 (10)	−0.0032 (9)	−0.0162 (10)
C55	0.0530 (13)	0.0330 (12)	0.0408 (13)	0.0201 (11)	−0.0049 (10)	−0.0028 (10)
C56	0.0427 (11)	0.0305 (11)	0.0284 (10)	0.0104 (9)	0.0009 (9)	0.0034 (8)
C57	0.0280 (9)	0.0208 (9)	0.0188 (8)	0.0019 (7)	−0.0008 (7)	0.0020 (7)
C58	0.0278 (9)	0.0234 (9)	0.0218 (9)	−0.0023 (8)	0.0026 (7)	−0.0005 (7)
C59	0.0374 (10)	0.0272 (10)	0.0229 (9)	−0.0067 (9)	0.0002 (8)	−0.0033 (8)
C60	0.0310 (10)	0.0408 (12)	0.0331 (11)	−0.0035 (9)	−0.0074 (8)	−0.0021 (9)
C61	0.0272 (10)	0.0684 (17)	0.0368 (12)	0.0104 (11)	0.0005 (9)	−0.0091 (11)
C62	0.0331 (10)	0.0559 (14)	0.0279 (11)	0.0100 (10)	−0.0005 (8)	−0.0114 (10)
C63	0.0305 (9)	0.0211 (9)	0.0198 (9)	0.0056 (8)	0.0028 (7)	−0.0009 (7)
C64	0.0321 (10)	0.0292 (10)	0.0237 (9)	0.0021 (8)	0.0006 (8)	0.0026 (8)
C65	0.0386 (11)	0.0314 (11)	0.0363 (12)	−0.0057 (9)	0.0032 (9)	−0.0040 (9)
C66	0.0574 (14)	0.0209 (10)	0.0505 (14)	−0.0013 (10)	0.0024 (11)	0.0039 (9)
C67	0.0608 (15)	0.0276 (12)	0.0568 (16)	0.0072 (11)	−0.0131 (12)	0.0125 (11)
C68	0.0449 (12)	0.0257 (10)	0.0372 (12)	0.0029 (9)	−0.0126 (9)	0.0037 (9)
C69	0.0279 (9)	0.0167 (8)	0.0224 (9)	0.0002 (7)	0.0041 (7)	0.0004 (7)
C70	0.0423 (12)	0.0557 (15)	0.0293 (11)	−0.0228 (11)	0.0030 (9)	−0.0007 (10)
C71	0.0644 (16)	0.0669 (17)	0.0335 (13)	−0.0348 (14)	0.0144 (11)	0.0026 (11)
C72	0.0660 (15)	0.0382 (12)	0.0235 (10)	−0.0031 (11)	0.0096 (10)	0.0053 (9)
C73	0.0399 (11)	0.0439 (12)	0.0237 (10)	0.0120 (10)	−0.0012 (8)	−0.0012 (9)
C74	0.0272 (9)	0.0356 (11)	0.0261 (10)	0.0046 (8)	0.0032 (8)	−0.0025 (8)
C75	0.0203 (8)	0.0216 (9)	0.0214 (9)	−0.0007 (7)	0.0020 (7)	−0.0033 (7)
C76	0.0330 (10)	0.0257 (10)	0.0312 (10)	−0.0057 (8)	−0.0011 (8)	−0.0002 (8)
C77	0.0333 (10)	0.0336 (11)	0.0413 (12)	−0.0130 (9)	0.0004 (9)	−0.0067 (9)
C78	0.0217 (9)	0.0490 (13)	0.0420 (12)	0.0002 (9)	−0.0071 (8)	−0.0175 (10)
C79	0.0308 (10)	0.0345 (11)	0.0373 (11)	0.0131 (9)	−0.0086 (8)	−0.0084 (9)
C80	0.0259 (9)	0.0208 (9)	0.0284 (10)	0.0037 (7)	−0.0011 (7)	−0.0058 (7)
C81	0.0224 (8)	0.0178 (8)	0.0190 (8)	−0.0003 (7)	−0.0011 (6)	−0.0013 (6)
C82	0.0238 (9)	0.0225 (9)	0.0323 (10)	0.0002 (7)	0.0041 (7)	0.0006 (8)
C83	0.0291 (10)	0.0257 (10)	0.0433 (12)	−0.0081 (8)	0.0037 (9)	0.0031 (9)
C84	0.0393 (11)	0.0165 (9)	0.0357 (11)	−0.0043 (8)	−0.0027 (9)	0.0000 (8)
C85	0.0359 (10)	0.0228 (9)	0.0278 (10)	0.0037 (8)	0.0034 (8)	−0.0044 (8)
C86	0.0270 (9)	0.0227 (9)	0.0235 (9)	−0.0012 (7)	0.0047 (7)	−0.0020 (7)

Geometric parameters (Å, º)

I1—Cu1	2.6956 (2)	I2—Cu2	2.7011 (3)
Cu1—S1	2.3432 (5)	Cu2—S2	2.3399 (5)
Cu1—P1	2.2715 (5)	Cu2—P3	2.2781 (5)
Cu1—P2	2.2879 (5)	Cu2—P4	2.2895 (5)
S1—C1	1.6863 (18)	S2—C44	1.682 (2)
P1—C8	1.8345 (18)	P3—C51	1.8293 (18)
P1—C14	1.8292 (17)	P3—C57	1.8351 (18)
P1—C20	1.8378 (18)	P3—C63	1.8321 (19)
P2—C26	1.8308 (18)	P4—C69	1.8362 (18)
P2—C32	1.8234 (18)	P4—C75	1.8255 (18)
P2—C38	1.8325 (18)	P4—C81	1.8232 (17)
N1—H1	0.8800	N3—H3A	0.8800
N1—C1	1.349 (2)	N3—C44	1.350 (2)
N1—C2	1.393 (2)	N3—C45	1.390 (2)
N2—H2	0.8800	N4—H4A	0.8800
N2—C1	1.353 (2)	N4—C44	1.349 (2)
N2—C7	1.386 (2)	N4—C50	1.391 (2)
C2—C3	1.384 (3)	C45—C46	1.380 (3)
C2—C7	1.392 (3)	C45—C50	1.391 (3)
C3—H3	0.9500	C46—H46	0.9500
C3—C4	1.385 (3)	C46—C47	1.390 (3)
C4—H4	0.9500	C47—H47	0.9500
C4—C5	1.391 (3)	C47—C48	1.390 (3)
C5—H5	0.9500	C48—H48	0.9500
C5—C6	1.374 (3)	C48—C49	1.376 (3)
C6—H6	0.9500	C49—H49	0.9500
C6—C7	1.387 (2)	C49—C50	1.385 (3)
C8—C9	1.395 (3)	C51—C52	1.392 (2)
C8—C13	1.393 (2)	C51—C56	1.389 (3)
C9—H9	0.9500	C52—H52	0.9500
C9—C10	1.381 (3)	C52—C53	1.389 (3)
C10—H10	0.9500	C53—H53	0.9500
C10—C11	1.380 (3)	C53—C54	1.379 (3)
C11—H11	0.9500	C54—H54	0.9500
C11—C12	1.381 (3)	C54—C55	1.380 (3)
C12—H12	0.9500	C55—H55	0.9500
C12—C13	1.387 (3)	C55—C56	1.391 (3)
C13—H13	0.9500	C56—H56	0.9500
C14—C15	1.394 (2)	C57—C58	1.391 (2)
C14—C19	1.391 (2)	C57—C62	1.388 (3)
C15—H15	0.9500	C58—H58	0.9500
C15—C16	1.389 (3)	C58—C59	1.387 (3)
C16—H16	0.9500	C59—H59	0.9500
C16—C17	1.382 (3)	C59—C60	1.378 (3)
C17—H17	0.9500	C60—H60	0.9500
C17—C18	1.379 (3)	C60—C61	1.374 (3)
C18—H18	0.9500	C61—H61	0.9500
C18—C19	1.387 (2)	C61—C62	1.384 (3)
C19—H19	0.9500	C62—H62	0.9500
C20—C21	1.386 (3)	C63—C64	1.399 (3)
C20—C25	1.398 (3)	C63—C68	1.384 (3)
C21—H21	0.9500	C64—H64	0.9500
C21—C22	1.394 (3)	C64—C65	1.387 (3)
C22—H22	0.9500	C65—H65	0.9500
C22—C23	1.379 (3)	C65—C66	1.380 (3)
C23—H23	0.9500	C66—H66	0.9500
C23—C24	1.381 (3)	C66—C67	1.376 (3)
C24—H24	0.9500	C67—H67	0.9500
C24—C25	1.392 (3)	C67—C68	1.393 (3)
C25—H25	0.9500	C68—H68	0.9500
C26—C27	1.401 (3)	C69—C70	1.389 (3)
C26—C31	1.384 (3)	C69—C74	1.391 (3)
C27—H27	0.9500	C70—H70	0.9500
C27—C28	1.383 (3)	C70—C71	1.391 (3)
C28—H28	0.9500	C71—H71	0.9500
C28—C29	1.376 (3)	C71—C72	1.369 (3)
C29—H29	0.9500	C72—H72	0.9500
C29—C30	1.378 (3)	C72—C73	1.379 (3)
C30—H30	0.9500	C73—H73	0.9500
C30—C31	1.393 (3)	C73—C74	1.387 (3)
C31—H31	0.9500	C74—H74	0.9500
C32—C33	1.383 (2)	C75—C76	1.402 (2)
C32—C37	1.394 (2)	C75—C80	1.391 (3)
C33—H33	0.9500	C76—H76	0.9500
C33—C34	1.389 (3)	C76—C77	1.381 (3)
C34—H34	0.9500	C77—H77	0.9500
C34—C35	1.376 (3)	C77—C78	1.377 (3)
C35—H35	0.9500	C78—H78	0.9500
C35—C36	1.379 (3)	C78—C79	1.377 (3)
C36—H36	0.9500	C79—H79	0.9500
C36—C37	1.385 (3)	C79—C80	1.390 (3)
C37—H37	0.9500	C80—H80	0.9500
C38—C39	1.388 (2)	C81—C82	1.389 (2)
C38—C43	1.392 (3)	C81—C86	1.397 (2)
C39—H39	0.9500	C82—H82	0.9500
C39—C40	1.387 (3)	C82—C83	1.393 (3)
C40—H40	0.9500	C83—H83	0.9500
C40—C41	1.372 (3)	C83—C84	1.377 (3)
C41—H41	0.9500	C84—H84	0.9500
C41—C42	1.379 (3)	C84—C85	1.385 (3)
C42—H42	0.9500	C85—H85	0.9500
C42—C43	1.391 (3)	C85—C86	1.382 (3)
C43—H43	0.9500	C86—H86	0.9500
S1—Cu1—I1	110.271 (15)	S2—Cu2—I2	110.242 (15)
P1—Cu1—I1	109.340 (14)	P3—Cu2—I2	105.783 (14)
P1—Cu1—S1	106.277 (18)	P3—Cu2—S2	106.190 (19)
P1—Cu1—P2	122.642 (19)	P3—Cu2—P4	120.848 (18)
P2—Cu1—I1	102.925 (14)	P4—Cu2—I2	108.061 (14)
P2—Cu1—S1	105.064 (18)	P4—Cu2—S2	105.532 (19)
C1—S1—Cu1	107.60 (6)	C44—S2—Cu2	107.99 (7)
C8—P1—Cu1	114.79 (6)	C51—P3—Cu2	116.74 (6)
C8—P1—C20	103.08 (8)	C51—P3—C57	101.57 (8)
C14—P1—Cu1	116.40 (6)	C51—P3—C63	102.16 (8)
C14—P1—C8	102.76 (8)	C57—P3—Cu2	115.46 (6)
C14—P1—C20	101.71 (8)	C63—P3—Cu2	114.94 (6)
C20—P1—Cu1	116.08 (6)	C63—P3—C57	103.99 (8)
C26—P2—Cu1	112.63 (6)	C69—P4—Cu2	117.30 (6)
C26—P2—C38	104.14 (8)	C75—P4—Cu2	111.27 (6)
C32—P2—Cu1	116.57 (6)	C75—P4—C69	104.37 (8)
C32—P2—C26	103.23 (8)	C81—P4—Cu2	117.47 (6)
C32—P2—C38	102.67 (8)	C81—P4—C69	100.90 (8)
C38—P2—Cu1	115.98 (6)	C81—P4—C75	103.82 (8)
C1—N1—H1	124.7	C44—N3—H3A	124.7
C1—N1—C2	110.58 (15)	C44—N3—C45	110.54 (16)
C2—N1—H1	124.7	C45—N3—H3A	124.7
C1—N2—H2	124.8	C44—N4—H4A	124.8
C1—N2—C7	110.31 (15)	C44—N4—C50	110.48 (16)
C7—N2—H2	124.8	C50—N4—H4A	124.8
N1—C1—S1	127.53 (14)	N3—C44—S2	127.82 (14)
N1—C1—N2	106.66 (15)	N4—C44—S2	125.51 (15)
N2—C1—S1	125.81 (14)	N4—C44—N3	106.67 (16)
C3—C2—N1	132.52 (17)	N3—C45—C50	106.10 (17)
C3—C2—C7	121.65 (17)	C46—C45—N3	132.45 (19)
C7—C2—N1	105.84 (16)	C46—C45—C50	121.45 (19)
C2—C3—H3	121.7	C45—C46—H46	121.6
C2—C3—C4	116.53 (19)	C45—C46—C47	116.7 (2)
C4—C3—H3	121.7	C47—C46—H46	121.6
C3—C4—H4	119.2	C46—C47—H47	119.2
C3—C4—C5	121.58 (19)	C46—C47—C48	121.5 (2)
C5—C4—H4	119.2	C48—C47—H47	119.2
C4—C5—H5	119.0	C47—C48—H48	119.1
C6—C5—C4	122.01 (18)	C49—C48—C47	121.8 (2)
C6—C5—H5	119.0	C49—C48—H48	119.1
C5—C6—H6	121.7	C48—C49—H49	121.6
C5—C6—C7	116.59 (19)	C48—C49—C50	116.8 (2)
C7—C6—H6	121.7	C50—C49—H49	121.6
N2—C7—C2	106.59 (15)	N4—C50—C45	106.22 (16)
N2—C7—C6	131.75 (18)	C49—C50—N4	132.0 (2)
C6—C7—C2	121.62 (18)	C49—C50—C45	121.8 (2)
C9—C8—P1	118.33 (14)	C52—C51—P3	121.94 (14)
C13—C8—P1	123.49 (14)	C56—C51—P3	118.93 (14)
C13—C8—C9	118.17 (17)	C56—C51—C52	119.05 (17)
C8—C9—H9	119.5	C51—C52—H52	119.8
C10—C9—C8	121.10 (19)	C53—C52—C51	120.41 (18)
C10—C9—H9	119.5	C53—C52—H52	119.8
C9—C10—H10	119.9	C52—C53—H53	120.0
C11—C10—C9	120.13 (19)	C54—C53—C52	120.1 (2)
C11—C10—H10	119.9	C54—C53—H53	120.0
C10—C11—H11	120.2	C53—C54—H54	120.0
C10—C11—C12	119.65 (19)	C53—C54—C55	119.95 (19)
C12—C11—H11	120.2	C55—C54—H54	120.0
C11—C12—H12	119.8	C54—C55—H55	119.9
C11—C12—C13	120.41 (19)	C54—C55—C56	120.3 (2)
C13—C12—H12	119.8	C56—C55—H55	119.9
C8—C13—H13	119.7	C51—C56—C55	120.19 (19)
C12—C13—C8	120.55 (18)	C51—C56—H56	119.9
C12—C13—H13	119.7	C55—C56—H56	119.9
C15—C14—P1	119.56 (13)	C58—C57—P3	123.49 (14)
C19—C14—P1	121.54 (13)	C62—C57—P3	118.51 (14)
C19—C14—C15	118.89 (16)	C62—C57—C58	117.98 (17)
C14—C15—H15	120.1	C57—C58—H58	119.6
C16—C15—C14	119.88 (17)	C59—C58—C57	120.85 (17)
C16—C15—H15	120.1	C59—C58—H58	119.6
C15—C16—H16	119.7	C58—C59—H59	120.0
C17—C16—C15	120.69 (18)	C60—C59—C58	120.10 (18)
C17—C16—H16	119.7	C60—C59—H59	120.0
C16—C17—H17	120.2	C59—C60—H60	120.1
C18—C17—C16	119.68 (17)	C61—C60—C59	119.80 (19)
C18—C17—H17	120.2	C61—C60—H60	120.1
C17—C18—H18	120.0	C60—C61—H61	119.9
C17—C18—C19	120.07 (17)	C60—C61—C62	120.15 (19)
C19—C18—H18	120.0	C62—C61—H61	119.9
C14—C19—H19	119.6	C57—C62—H62	119.4
C18—C19—C14	120.75 (17)	C61—C62—C57	121.11 (18)
C18—C19—H19	119.6	C61—C62—H62	119.4
C21—C20—P1	123.38 (14)	C64—C63—P3	118.22 (14)
C21—C20—C25	118.77 (17)	C68—C63—P3	123.21 (15)
C25—C20—P1	117.85 (13)	C68—C63—C64	118.55 (18)
C20—C21—H21	119.7	C63—C64—H64	119.8
C20—C21—C22	120.65 (19)	C65—C64—C63	120.50 (18)
C22—C21—H21	119.7	C65—C64—H64	119.8
C21—C22—H22	120.0	C64—C65—H65	119.9
C23—C22—C21	120.06 (19)	C66—C65—C64	120.2 (2)
C23—C22—H22	120.0	C66—C65—H65	119.9
C22—C23—H23	120.0	C65—C66—H66	120.0
C22—C23—C24	120.04 (19)	C67—C66—C65	120.0 (2)
C24—C23—H23	120.0	C67—C66—H66	120.0
C23—C24—H24	119.9	C66—C67—H67	119.9
C23—C24—C25	120.18 (19)	C66—C67—C68	120.1 (2)
C25—C24—H24	119.9	C68—C67—H67	119.9
C20—C25—H25	119.8	C63—C68—C67	120.7 (2)
C24—C25—C20	120.30 (18)	C63—C68—H68	119.6
C24—C25—H25	119.8	C67—C68—H68	119.6
C27—C26—P2	118.99 (14)	C70—C69—P4	124.94 (15)
C31—C26—P2	122.28 (14)	C70—C69—C74	118.29 (17)
C31—C26—C27	118.54 (17)	C74—C69—P4	116.77 (13)
C26—C27—H27	119.9	C69—C70—H70	119.8
C28—C27—C26	120.22 (19)	C69—C70—C71	120.4 (2)
C28—C27—H27	119.9	C71—C70—H70	119.8
C27—C28—H28	119.7	C70—C71—H71	119.6
C29—C28—C27	120.5 (2)	C72—C71—C70	120.8 (2)
C29—C28—H28	119.7	C72—C71—H71	119.6
C28—C29—H29	120.0	C71—C72—H72	120.3
C28—C29—C30	119.92 (19)	C71—C72—C73	119.35 (19)
C30—C29—H29	120.0	C73—C72—H72	120.3
C29—C30—H30	120.0	C72—C73—H73	119.8
C29—C30—C31	119.9 (2)	C72—C73—C74	120.4 (2)
C31—C30—H30	120.0	C74—C73—H73	119.8
C26—C31—C30	120.67 (19)	C69—C74—H74	119.6
C26—C31—H31	119.7	C73—C74—C69	120.72 (18)
C30—C31—H31	119.7	C73—C74—H74	119.6
C33—C32—P2	117.88 (13)	C76—C75—P4	119.61 (14)
C33—C32—C37	118.54 (17)	C80—C75—P4	121.79 (13)
C37—C32—P2	123.51 (13)	C80—C75—C76	118.25 (17)
C32—C33—H33	119.8	C75—C76—H76	119.7
C32—C33—C34	120.48 (18)	C77—C76—C75	120.61 (19)
C34—C33—H33	119.8	C77—C76—H76	119.7
C33—C34—H34	119.8	C76—C77—H77	119.9
C35—C34—C33	120.46 (18)	C78—C77—C76	120.19 (19)
C35—C34—H34	119.8	C78—C77—H77	119.9
C34—C35—H35	120.2	C77—C78—H78	119.9
C34—C35—C36	119.67 (18)	C79—C78—C77	120.14 (18)
C36—C35—H35	120.2	C79—C78—H78	119.9
C35—C36—H36	119.9	C78—C79—H79	120.0
C35—C36—C37	120.11 (19)	C78—C79—C80	120.1 (2)
C37—C36—H36	119.9	C80—C79—H79	120.0
C32—C37—H37	119.6	C75—C80—H80	119.7
C36—C37—C32	120.71 (18)	C79—C80—C75	120.63 (18)
C36—C37—H37	119.6	C79—C80—H80	119.7
C39—C38—P2	123.14 (14)	C82—C81—P4	118.41 (13)
C39—C38—C43	117.80 (17)	C82—C81—C86	119.00 (16)
C43—C38—P2	118.88 (13)	C86—C81—P4	122.59 (13)
C38—C39—H39	119.5	C81—C82—H82	120.0
C40—C39—C38	120.95 (19)	C81—C82—C83	119.98 (17)
C40—C39—H39	119.5	C83—C82—H82	120.0
C39—C40—H40	119.6	C82—C83—H83	119.7
C41—C40—C39	120.75 (19)	C84—C83—C82	120.52 (17)
C41—C40—H40	119.6	C84—C83—H83	119.7
C40—C41—H41	120.4	C83—C84—H84	120.1
C40—C41—C42	119.24 (18)	C83—C84—C85	119.87 (17)
C42—C41—H41	120.4	C85—C84—H84	120.1
C41—C42—H42	119.8	C84—C85—H85	120.0
C41—C42—C43	120.32 (19)	C86—C85—C84	120.02 (17)
C43—C42—H42	119.8	C86—C85—H85	120.0
C38—C43—H43	119.6	C81—C86—H86	119.7
C42—C43—C38	120.88 (18)	C85—C86—C81	120.60 (16)
C42—C43—H43	119.6	C85—C86—H86	119.7
Cu1—S1—C1—N1	−33.23 (18)	Cu2—S2—C44—N3	−4.59 (19)
Cu1—S1—C1—N2	147.66 (15)	Cu2—S2—C44—N4	175.97 (15)
Cu1—P1—C8—C9	45.75 (16)	Cu2—P3—C51—C52	−152.14 (13)
Cu1—P1—C8—C13	−133.37 (14)	Cu2—P3—C51—C56	31.20 (17)
Cu1—P1—C14—C15	28.37 (17)	Cu2—P3—C57—C58	−140.17 (14)
Cu1—P1—C14—C19	−152.49 (13)	Cu2—P3—C57—C62	38.09 (18)
Cu1—P1—C20—C21	−124.91 (14)	Cu2—P3—C63—C64	58.74 (15)
Cu1—P1—C20—C25	54.76 (15)	Cu2—P3—C63—C68	−119.73 (16)
Cu1—P2—C26—C27	55.50 (15)	Cu2—P4—C69—C70	−114.52 (17)
Cu1—P2—C26—C31	−119.40 (14)	Cu2—P4—C69—C74	65.13 (15)
Cu1—P2—C32—C33	13.55 (17)	Cu2—P4—C75—C76	63.10 (15)
Cu1—P2—C32—C37	−169.30 (15)	Cu2—P4—C75—C80	−110.06 (14)
Cu1—P2—C38—C39	−91.81 (16)	Cu2—P4—C81—C82	−2.60 (16)
Cu1—P2—C38—C43	83.16 (15)	Cu2—P4—C81—C86	177.94 (13)
P1—C8—C9—C10	−179.81 (16)	P3—C51—C52—C53	−177.29 (14)
P1—C8—C13—C12	179.53 (15)	P3—C51—C56—C55	175.97 (16)
P1—C14—C15—C16	177.96 (15)	P3—C57—C58—C59	178.25 (14)
P1—C14—C19—C18	−179.63 (14)	P3—C57—C62—C61	−178.92 (19)
P1—C20—C21—C22	179.69 (15)	P3—C63—C64—C65	−178.43 (15)
P1—C20—C25—C24	179.90 (14)	P3—C63—C68—C67	178.61 (18)
P2—C26—C27—C28	−179.87 (15)	P4—C69—C70—C71	178.20 (19)
P2—C26—C31—C30	178.07 (15)	P4—C69—C74—C73	−179.07 (15)
P2—C32—C33—C34	176.06 (16)	P4—C75—C76—C77	−176.93 (15)
P2—C32—C37—C36	−175.94 (16)	P4—C75—C80—C79	176.03 (14)
P2—C38—C39—C40	175.81 (16)	P4—C81—C82—C83	179.72 (15)
P2—C38—C43—C42	−178.02 (15)	P4—C81—C86—C85	−179.62 (14)
N1—C2—C3—C4	177.7 (2)	N3—C45—C46—C47	−178.4 (2)
N1—C2—C7—N2	0.38 (19)	N3—C45—C50—N4	−0.3 (2)
N1—C2—C7—C6	−177.77 (17)	N3—C45—C50—C49	178.23 (19)
C1—N1—C2—C3	−179.0 (2)	C44—N3—C45—C46	179.1 (2)
C1—N1—C2—C7	0.6 (2)	C44—N3—C45—C50	0.3 (2)
C1—N2—C7—C2	−1.2 (2)	C44—N4—C50—C45	0.3 (2)
C1—N2—C7—C6	176.7 (2)	C44—N4—C50—C49	−178.0 (2)
C2—N1—C1—S1	179.44 (14)	C45—N3—C44—S2	−179.58 (14)
C2—N1—C1—N2	−1.3 (2)	C45—N3—C44—N4	−0.1 (2)
C2—C3—C4—C5	0.6 (3)	C45—C46—C47—C48	0.7 (3)
C3—C2—C7—N2	179.98 (17)	C46—C45—C50—N4	−179.30 (17)
C3—C2—C7—C6	1.8 (3)	C46—C45—C50—C49	−0.7 (3)
C3—C4—C5—C6	0.7 (3)	C46—C47—C48—C49	−1.2 (4)
C4—C5—C6—C7	−0.8 (3)	C47—C48—C49—C50	0.8 (3)
C5—C6—C7—N2	−178.10 (19)	C48—C49—C50—N4	178.4 (2)
C5—C6—C7—C2	−0.5 (3)	C48—C49—C50—C45	0.2 (3)
C7—N2—C1—S1	−179.18 (14)	C50—N4—C44—S2	179.38 (14)
C7—N2—C1—N1	1.6 (2)	C50—N4—C44—N3	−0.2 (2)
C7—C2—C3—C4	−1.8 (3)	C50—C45—C46—C47	0.3 (3)
C8—P1—C14—C15	−97.96 (16)	C51—P3—C57—C58	−12.86 (17)
C8—P1—C14—C19	81.18 (16)	C51—P3—C57—C62	165.40 (16)
C8—P1—C20—C21	1.47 (17)	C51—P3—C63—C64	−68.70 (15)
C8—P1—C20—C25	−178.86 (13)	C51—P3—C63—C68	112.83 (17)
C8—C9—C10—C11	0.5 (3)	C51—C52—C53—C54	1.2 (3)
C9—C8—C13—C12	0.4 (3)	C52—C51—C56—C55	−0.8 (3)
C9—C10—C11—C12	0.0 (3)	C52—C53—C54—C55	−0.4 (3)
C10—C11—C12—C13	−0.2 (3)	C53—C54—C55—C56	−1.1 (3)
C11—C12—C13—C8	0.0 (3)	C54—C55—C56—C51	1.6 (3)
C13—C8—C9—C10	−0.6 (3)	C56—C51—C52—C53	−0.6 (3)
C14—P1—C8—C9	173.11 (15)	C57—P3—C51—C52	81.39 (16)
C14—P1—C8—C13	−6.01 (17)	C57—P3—C51—C56	−95.27 (16)
C14—P1—C20—C21	107.72 (16)	C57—P3—C63—C64	−174.07 (14)
C14—P1—C20—C25	−72.62 (15)	C57—P3—C63—C68	7.46 (18)
C14—C15—C16—C17	2.2 (3)	C57—C58—C59—C60	0.3 (3)
C15—C14—C19—C18	−0.5 (3)	C58—C57—C62—C61	−0.6 (3)
C15—C16—C17—C18	−1.5 (3)	C58—C59—C60—C61	0.0 (3)
C16—C17—C18—C19	−0.2 (3)	C59—C60—C61—C62	−0.6 (4)
C17—C18—C19—C14	1.2 (3)	C60—C61—C62—C57	0.9 (4)
C19—C14—C15—C16	−1.2 (3)	C62—C57—C58—C59	0.0 (3)
C20—P1—C8—C9	−81.44 (16)	C63—P3—C51—C52	−25.87 (17)
C20—P1—C8—C13	99.43 (16)	C63—P3—C51—C56	157.48 (15)
C20—P1—C14—C15	155.54 (15)	C63—P3—C57—C58	92.96 (16)
C20—P1—C14—C19	−25.32 (17)	C63—P3—C57—C62	−88.78 (17)
C20—C21—C22—C23	0.4 (3)	C63—C64—C65—C66	−0.3 (3)
C21—C20—C25—C24	−0.4 (3)	C64—C63—C68—C67	0.1 (3)
C21—C22—C23—C24	−0.5 (3)	C64—C65—C66—C67	0.3 (3)
C22—C23—C24—C25	0.1 (3)	C65—C66—C67—C68	0.0 (4)
C23—C24—C25—C20	0.4 (3)	C66—C67—C68—C63	−0.2 (4)
C25—C20—C21—C22	0.0 (3)	C68—C63—C64—C65	0.1 (3)
C26—P2—C32—C33	−110.47 (15)	C69—P4—C75—C76	−64.32 (16)
C26—P2—C32—C37	66.68 (18)	C69—P4—C75—C80	122.52 (15)
C26—P2—C38—C39	32.53 (18)	C69—P4—C81—C82	126.20 (15)
C26—P2—C38—C43	−152.50 (14)	C69—P4—C81—C86	−53.26 (16)
C26—C27—C28—C29	2.5 (3)	C69—C70—C71—C72	0.6 (4)
C27—C26—C31—C30	3.1 (3)	C70—C69—C74—C73	0.6 (3)
C27—C28—C29—C30	1.6 (3)	C70—C71—C72—C73	1.1 (4)
C28—C29—C30—C31	−3.2 (3)	C71—C72—C73—C74	−1.9 (3)
C29—C30—C31—C26	0.8 (3)	C72—C73—C74—C69	1.1 (3)
C31—C26—C27—C28	−4.8 (3)	C74—C69—C70—C71	−1.4 (3)
C32—P2—C26—C27	−177.93 (14)	C75—P4—C69—C70	9.1 (2)
C32—P2—C26—C31	7.17 (17)	C75—P4—C69—C74	−171.26 (14)
C32—P2—C38—C39	139.90 (16)	C75—P4—C81—C82	−125.89 (15)
C32—P2—C38—C43	−45.13 (16)	C75—P4—C81—C86	54.65 (16)
C32—C33—C34—C35	0.2 (3)	C75—C76—C77—C78	1.2 (3)
C33—C32—C37—C36	1.2 (3)	C76—C75—C80—C79	2.8 (3)
C33—C34—C35—C36	0.8 (3)	C76—C77—C78—C79	1.9 (3)
C34—C35—C36—C37	−0.9 (3)	C77—C78—C79—C80	−2.6 (3)
C35—C36—C37—C32	−0.1 (3)	C78—C79—C80—C75	0.3 (3)
C37—C32—C33—C34	−1.2 (3)	C80—C75—C76—C77	−3.5 (3)
C38—P2—C26—C27	−70.98 (15)	C81—P4—C69—C70	116.57 (18)
C38—P2—C26—C31	114.12 (16)	C81—P4—C69—C74	−63.78 (15)
C38—P2—C32—C33	141.46 (15)	C81—P4—C75—C76	−169.63 (14)
C38—P2—C32—C37	−41.39 (18)	C81—P4—C75—C80	17.21 (16)
C38—C39—C40—C41	1.2 (3)	C81—C82—C83—C84	0.3 (3)
C39—C38—C43—C42	−2.8 (3)	C82—C81—C86—C85	0.9 (3)
C39—C40—C41—C42	−1.1 (3)	C82—C83—C84—C85	0.1 (3)
C40—C41—C42—C43	−0.9 (3)	C83—C84—C85—C86	0.0 (3)
C41—C42—C43—C38	2.9 (3)	C84—C85—C86—C81	−0.5 (3)
C43—C38—C39—C40	0.8 (3)	C86—C81—C82—C83	−0.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···I1	0.86	2.74	3.5702 (12)	159
N2—H2···I2^i	0.86	2.91	3.7014 (13)	151
N3—H3A···I2	0.86	2.81	3.5590 (17)	143
N4—H4A···I1	0.86	2.77	3.5746 (15)	153

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