Structure and photophysical and electrochemical properties of a copper porphyrin com­plex with a three-dimensional framework

Porphyrins and metalloporphyrins can generally show attractive structural motifs and inter­esting properties. A new copper porphyrin, namely poly[[μ-chlorido-[μ₅-5,10,15,20-tetra­kis­(pyridin-4-yl)-21H,23H-porphine]tricopper(I)] [aqua­dichlorido­copper(II)]], {[Cu₃(C₄₀H₂₄N₈)Cl][CuCl₂(H₂O)]}_n (1), was syn­thesized by the self-assembly of copper chloride with 5,10,15,20-tetra­kis­(pyridin-4-yl)-21H,23H-porphine under solvothermal conditions. The structure of this copper porphyrin was characterized by single-crystal X-ray crystallography and elemental analysis. The porphyrin macrocycle shows a distorted saddle geometry, with the four pyrrole rings slightly distorted in an alternating mode either upwards or downwards. The copper ions show three-coordinated triangular and four-coordinated square-planar geometries. Every copper–porphyrin unit connects to 12 others via four μ₄-bridging Cu₂Cl moieties to com­plete the three-dimensional framework of com­pound 1, with isolated CuCl₂(H₂O) units located in the voids. This copper porphyrin displays a red photoluminescence. Electrochemical measurements showed that com­pound 1 has two redox waves (E_1/2 = −160 and 91 mV).

Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b) and publCIF (Westrip, 2010).

Poly[[µ-chlorido-[µ₅-5,10,15,20-tetrakis(pyridin-4-yl)-21H,23H-porphine]tricopper(I)] [aquadichloridocopper(II)]]

Crystal data

[Cu3(C40H24N8)Cl][CuCl2(H2O)]	F(000) = 1988
Mr = 995.20	Dx = 1.833 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.2443 (5) Å	Cell parameters from 4525 reflections
b = 20.2354 (12) Å	θ = 3.6–28.5°
c = 21.618 (1) Å	µ = 2.60 mm^−1
β = 91.389 (4)°	T = 293 K
V = 3605.4 (3) Å^3	Needle-like, purple
Z = 4	0.11 × 0.02 × 0.02 mm

Data collection

Rigaku SuperNova (Mo) X-ray Source diffractometer	6685 independent reflections
Radiation source: micro-focus sealed X-ray tube	4170 reflections with I > 2σ(I)
Detector resolution: 16.1787 pixels mm^-1	Rint = 0.050
ω scans	θmax = 25.5°, θmin = 3.3°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −9→9
Tmin = 0.951, Tmax = 0.959	k = −24→15
21307 measured reflections	l = −26→26

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.078	H-atom parameters constrained
wR(F^2) = 0.231	w = 1/[σ^2(Fo^2) + (0.0999P)^2 + 15.3236P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
6685 reflections	Δρmax = 1.18 e Å^−3
509 parameters	Δρmin = −1.63 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	Occ. (<1)
Cu1	0.76892 (10)	0.49705 (4)	0.56839 (4)	0.0327 (3)
Cu2	1.12265 (14)	0.94928 (6)	0.62290 (5)	0.0508 (3)
Cu3	0.40410 (17)	0.04858 (7)	0.51300 (5)	0.0700 (4)
Cu4	−0.0071 (5)	0.2191 (2)	0.7407 (2)	0.1053 (10)	0.515 (3)
Cu4B	0.0519 (5)	0.2392 (2)	0.7759 (3)	0.1053 (10)	0.485 (3)
Cl1	1.1677 (3)	1.03123 (15)	0.56000 (13)	0.0763 (8)
Cl2	−0.0585 (5)	0.2674 (2)	0.8402 (2)	0.1323 (17)
Cl3	0.0136 (12)	0.1815 (5)	0.6528 (6)	0.335 (7)
N1	0.7360 (7)	0.4246 (3)	0.6294 (2)	0.0324 (14)
N2	0.8264 (7)	0.5588 (3)	0.6379 (3)	0.0356 (15)
N3	0.8191 (7)	0.5673 (3)	0.5069 (3)	0.0354 (14)
N4	0.6941 (7)	0.4378 (3)	0.4999 (3)	0.0346 (14)
N5	0.4979 (9)	0.1341 (3)	0.5416 (3)	0.0431 (16)
N6	0.8867 (8)	0.4723 (3)	0.9224 (3)	0.0444 (17)
N7	1.0606 (9)	0.8572 (4)	0.5999 (3)	0.0475 (17)
N8	0.6627 (8)	0.5338 (3)	0.2139 (3)	0.0391 (15)
C1	0.6404 (9)	0.3372 (4)	0.5594 (3)	0.0370 (18)
C2	0.6960 (9)	0.3592 (4)	0.6166 (3)	0.0369 (18)
C3	0.7077 (9)	0.3206 (4)	0.6715 (3)	0.0400 (18)
H3A	0.688652	0.275421	0.674572	0.048*
C4	0.7516 (10)	0.3614 (4)	0.7182 (3)	0.0421 (19)
H4A	0.768449	0.349569	0.759375	0.051*
C5	0.7675 (9)	0.4263 (4)	0.6928 (3)	0.0356 (17)
C6	0.7989 (9)	0.4841 (4)	0.7266 (3)	0.0339 (17)
C7	0.8188 (9)	0.5464 (4)	0.7007 (3)	0.0350 (17)
C8	0.8495 (10)	0.6061 (4)	0.7340 (4)	0.045 (2)
H8A	0.849145	0.611096	0.776738	0.054*
C9	0.8787 (10)	0.6534 (4)	0.6931 (3)	0.045 (2)
H9A	0.902110	0.697389	0.701987	0.054*
C10	0.8677 (9)	0.6243 (4)	0.6328 (3)	0.0343 (17)
C11	0.9013 (9)	0.6568 (4)	0.5779 (3)	0.0346 (17)
C12	0.8840 (9)	0.6289 (4)	0.5192 (3)	0.0364 (17)
C13	0.9284 (9)	0.6601 (4)	0.4624 (4)	0.044 (2)
H13A	0.977213	0.701252	0.458504	0.053*
C14	0.8863 (10)	0.6187 (4)	0.4158 (3)	0.0414 (19)
H14A	0.902630	0.625620	0.373874	0.050*
C15	0.8109 (9)	0.5614 (4)	0.4433 (3)	0.0331 (16)
C16	0.7355 (9)	0.5107 (4)	0.4100 (3)	0.0361 (17)
C17	0.6744 (9)	0.4542 (4)	0.4378 (3)	0.0351 (17)
C18	0.5861 (9)	0.4019 (4)	0.4068 (3)	0.042 (2)
H18A	0.552109	0.401870	0.365487	0.051*
C19	0.5614 (10)	0.3532 (4)	0.4478 (4)	0.044 (2)
H19A	0.508799	0.313285	0.440106	0.052*
C20	0.6320 (9)	0.3748 (4)	0.5060 (3)	0.0359 (17)
C21	0.6333 (11)	0.1569 (5)	0.5170 (4)	0.051 (2)
H21A	0.696696	0.128006	0.494526	0.061*
C22	0.6830 (10)	0.2206 (4)	0.5234 (4)	0.048 (2)
H22A	0.780812	0.233751	0.506665	0.058*
C23	0.5895 (10)	0.2663 (4)	0.5544 (3)	0.0410 (19)
C24	0.4509 (10)	0.2414 (4)	0.5822 (4)	0.047 (2)
H24A	0.386756	0.268780	0.605983	0.056*
C25	0.4102 (11)	0.1764 (5)	0.5740 (4)	0.048 (2)
H25A	0.316235	0.160961	0.592022	0.058*
C26	0.9739 (10)	0.4376 (4)	0.8832 (3)	0.044 (2)
H26A	1.057005	0.410967	0.898943	0.053*
C27	0.9463 (9)	0.4395 (4)	0.8193 (3)	0.0392 (18)
H27A	1.010850	0.414929	0.793210	0.047*
C28	0.8216 (9)	0.4784 (4)	0.7951 (3)	0.0346 (17)
C29	0.7263 (9)	0.5121 (4)	0.8376 (3)	0.0417 (19)
H29A	0.638385	0.537241	0.823714	0.050*
C30	0.7627 (10)	0.5079 (4)	0.8996 (4)	0.0424 (19)
H30A	0.698234	0.530834	0.927045	0.051*
C31	1.1435 (10)	0.8069 (4)	0.6248 (3)	0.044 (2)
H31A	1.236726	0.816038	0.648300	0.052*
C32	1.0978 (9)	0.7423 (4)	0.6174 (3)	0.0424 (19)
H32A	1.160637	0.709048	0.635436	0.051*
C33	0.9594 (9)	0.7259 (4)	0.5834 (3)	0.0397 (19)
C34	0.8755 (11)	0.7793 (4)	0.5558 (4)	0.050 (2)
H34A	0.783328	0.771626	0.531151	0.059*
C35	0.9303 (11)	0.8427 (4)	0.5652 (4)	0.049 (2)
H35A	0.873258	0.877192	0.546364	0.059*
C36	0.6198 (9)	0.5809 (4)	0.2541 (3)	0.044 (2)
H36A	0.572829	0.619447	0.238615	0.053*
C37	0.6423 (9)	0.5745 (4)	0.3174 (3)	0.0394 (18)
H37A	0.608687	0.608091	0.343525	0.047*
C38	0.7155 (9)	0.5177 (4)	0.3421 (3)	0.0360 (17)
C39	0.7622 (10)	0.4691 (4)	0.2997 (3)	0.0427 (19)
H39A	0.813245	0.430585	0.313187	0.051*
C40	0.7307 (10)	0.4798 (4)	0.2378 (3)	0.043 (2)
H40A	0.759326	0.446586	0.210418	0.052*
O1W	0.2319 (19)	0.2180 (10)	0.7127 (6)	0.206 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0469 (5)	0.0240 (6)	0.0271 (4)	−0.0040 (4)	−0.0038 (3)	−0.0003 (4)
Cu2	0.0735 (8)	0.0379 (7)	0.0411 (6)	−0.0070 (5)	0.0007 (5)	−0.0008 (5)
Cu3	0.0962 (10)	0.0641 (10)	0.0500 (7)	−0.0271 (7)	0.0052 (6)	−0.0105 (6)
Cu4	0.076 (2)	0.089 (2)	0.150 (4)	0.0068 (15)	−0.0046 (16)	0.017 (2)
Cu4B	0.076 (2)	0.089 (2)	0.150 (4)	0.0068 (15)	−0.0046 (16)	0.017 (2)
Cl1	0.0709 (16)	0.078 (2)	0.0802 (17)	−0.0114 (14)	0.0092 (13)	0.0376 (15)
Cl2	0.140 (3)	0.105 (3)	0.149 (4)	−0.023 (2)	−0.065 (3)	0.059 (3)
Cl3	0.280 (10)	0.223 (9)	0.513 (18)	0.099 (8)	0.243 (12)	0.115 (10)
N1	0.044 (4)	0.027 (4)	0.026 (3)	−0.006 (3)	−0.001 (2)	0.000 (3)
N2	0.045 (4)	0.028 (4)	0.034 (3)	−0.005 (3)	−0.005 (3)	0.001 (3)
N3	0.043 (4)	0.030 (4)	0.032 (3)	−0.003 (3)	−0.003 (3)	0.002 (3)
N4	0.047 (4)	0.028 (4)	0.028 (3)	−0.007 (3)	−0.003 (3)	0.000 (3)
N5	0.063 (4)	0.025 (4)	0.041 (4)	−0.009 (3)	−0.006 (3)	−0.008 (3)
N6	0.069 (5)	0.034 (4)	0.030 (3)	0.007 (3)	−0.009 (3)	0.002 (3)
N7	0.066 (5)	0.038 (5)	0.038 (4)	−0.004 (3)	−0.003 (3)	0.003 (3)
N8	0.052 (4)	0.038 (4)	0.027 (3)	0.007 (3)	0.000 (3)	0.002 (3)
C1	0.051 (5)	0.026 (5)	0.034 (4)	−0.001 (3)	−0.002 (3)	−0.003 (3)
C2	0.042 (4)	0.028 (5)	0.041 (4)	−0.007 (3)	−0.001 (3)	−0.002 (3)
C3	0.054 (5)	0.031 (5)	0.035 (4)	−0.002 (4)	−0.002 (3)	0.002 (3)
C4	0.058 (5)	0.033 (5)	0.034 (4)	−0.001 (4)	−0.008 (3)	0.009 (4)
C5	0.042 (4)	0.033 (5)	0.032 (4)	−0.005 (3)	−0.004 (3)	0.002 (3)
C6	0.051 (4)	0.026 (5)	0.024 (3)	−0.004 (3)	−0.005 (3)	−0.003 (3)
C7	0.038 (4)	0.033 (5)	0.034 (4)	−0.003 (3)	−0.003 (3)	−0.003 (3)
C8	0.068 (5)	0.035 (5)	0.032 (4)	−0.002 (4)	−0.002 (4)	−0.010 (4)
C9	0.076 (6)	0.022 (5)	0.038 (4)	−0.005 (4)	−0.004 (4)	0.000 (3)
C10	0.048 (4)	0.019 (4)	0.035 (4)	−0.003 (3)	−0.006 (3)	0.000 (3)
C11	0.046 (4)	0.023 (4)	0.034 (4)	−0.002 (3)	−0.006 (3)	0.003 (3)
C12	0.043 (4)	0.033 (5)	0.034 (4)	−0.004 (3)	0.000 (3)	0.001 (3)
C13	0.050 (5)	0.042 (6)	0.041 (4)	−0.011 (4)	−0.003 (3)	0.005 (4)
C14	0.055 (5)	0.038 (5)	0.031 (4)	−0.003 (4)	0.004 (3)	−0.001 (3)
C15	0.044 (4)	0.022 (4)	0.033 (4)	−0.001 (3)	−0.002 (3)	0.001 (3)
C16	0.045 (4)	0.030 (5)	0.033 (4)	0.004 (3)	0.000 (3)	0.000 (3)
C17	0.045 (4)	0.028 (5)	0.032 (4)	0.000 (3)	0.000 (3)	−0.001 (3)
C18	0.053 (5)	0.047 (6)	0.027 (4)	−0.006 (4)	−0.008 (3)	−0.004 (4)
C19	0.054 (5)	0.032 (5)	0.045 (5)	−0.008 (4)	−0.008 (4)	−0.003 (4)
C20	0.050 (5)	0.028 (5)	0.030 (4)	−0.004 (3)	−0.001 (3)	−0.009 (3)
C21	0.068 (6)	0.036 (6)	0.050 (5)	0.000 (4)	0.010 (4)	−0.010 (4)
C22	0.056 (5)	0.041 (6)	0.049 (5)	−0.008 (4)	0.012 (4)	−0.002 (4)
C23	0.057 (5)	0.033 (5)	0.033 (4)	−0.008 (4)	−0.003 (3)	−0.002 (3)
C24	0.064 (6)	0.032 (5)	0.044 (5)	−0.002 (4)	0.006 (4)	−0.010 (4)
C25	0.057 (5)	0.038 (6)	0.049 (5)	−0.010 (4)	0.000 (4)	0.004 (4)
C26	0.057 (5)	0.041 (6)	0.035 (4)	0.014 (4)	−0.006 (3)	0.001 (4)
C27	0.046 (4)	0.036 (5)	0.035 (4)	0.000 (3)	−0.004 (3)	−0.006 (3)
C28	0.043 (4)	0.029 (5)	0.032 (4)	−0.005 (3)	−0.006 (3)	0.003 (3)
C29	0.048 (5)	0.038 (5)	0.038 (4)	−0.001 (4)	−0.007 (3)	0.000 (4)
C30	0.056 (5)	0.034 (5)	0.037 (4)	0.000 (4)	−0.001 (3)	−0.004 (4)
C31	0.051 (5)	0.040 (6)	0.040 (4)	−0.010 (4)	0.000 (3)	−0.001 (4)
C32	0.050 (5)	0.036 (5)	0.040 (4)	0.000 (4)	−0.008 (3)	0.002 (4)
C33	0.054 (5)	0.037 (5)	0.028 (4)	−0.008 (4)	0.000 (3)	−0.002 (3)
C34	0.062 (5)	0.037 (6)	0.049 (5)	−0.002 (4)	−0.015 (4)	0.002 (4)
C35	0.073 (6)	0.025 (5)	0.048 (5)	0.007 (4)	−0.015 (4)	0.002 (4)
C36	0.051 (5)	0.045 (6)	0.037 (4)	0.006 (4)	−0.005 (3)	0.007 (4)
C37	0.051 (5)	0.033 (5)	0.034 (4)	0.002 (4)	0.001 (3)	−0.003 (3)
C38	0.043 (4)	0.035 (5)	0.029 (4)	−0.004 (3)	0.002 (3)	0.002 (3)
C39	0.055 (5)	0.033 (5)	0.041 (4)	0.008 (4)	0.000 (3)	0.000 (4)
C40	0.063 (5)	0.033 (5)	0.034 (4)	0.002 (4)	0.003 (4)	−0.008 (4)
O1W	0.184 (14)	0.31 (2)	0.128 (10)	0.036 (13)	0.045 (9)	−0.001 (12)

Geometric parameters (Å, º)

Cu1—N1	1.994 (6)	C10—C11	1.391 (10)
Cu1—N2	2.003 (6)	C11—C12	1.395 (10)
Cu1—N3	1.997 (6)	C11—C33	1.481 (11)
Cu1—N4	1.992 (6)	C12—C13	1.435 (10)
Cu2—N7	1.991 (7)	C13—C14	1.349 (11)
Cu2—N8^i	2.017 (6)	C13—H13A	0.9300
Cu2—Cl1	2.182 (3)	C14—C15	1.450 (10)
Cu3—N5	1.988 (6)	C14—H14A	0.9300
Cu3—N6^ii	2.005 (6)	C15—C16	1.392 (10)
Cu3—Cl1^iii	2.247 (3)	C16—C17	1.392 (11)
Cu3—Cu3^iv	2.593 (3)	C16—C38	1.480 (10)
Cu4—Cl2	2.408 (8)	C17—C18	1.440 (11)
Cu4—Cu4B	0.982 (5)	C18—C19	1.344 (11)
Cu4—Cl3	2.058 (14)	C18—H18A	0.9300
Cu4—O1W	2.076 (15)	C19—C20	1.441 (10)
Cu4B—Cl2	1.772 (7)	C19—H19A	0.9300
Cu4B—O1W	2.087 (14)	C21—C22	1.358 (12)
N1—C5	1.388 (9)	C21—H21A	0.9300
N1—C2	1.391 (9)	C22—C23	1.388 (11)
N2—C10	1.373 (9)	C22—H22A	0.9300
N2—C7	1.383 (9)	C23—C24	1.398 (11)
N3—C12	1.379 (10)	C24—C25	1.368 (12)
N3—C15	1.380 (9)	C24—H24A	0.9300
N4—C20	1.382 (9)	C25—H25A	0.9300
N4—C17	1.387 (9)	C26—C27	1.394 (10)
N5—C25	1.330 (11)	C26—H26A	0.9300
N5—C21	1.331 (11)	C27—C28	1.387 (10)
N6—C26	1.326 (10)	C27—H27A	0.9300
N6—C30	1.334 (10)	C28—C29	1.399 (11)
N7—C35	1.328 (10)	C29—C30	1.369 (11)
N7—C31	1.333 (11)	C29—H29A	0.9300
N8—C40	1.326 (10)	C30—H30A	0.9300
N8—C36	1.341 (10)	C31—C32	1.367 (11)
C1—C20	1.382 (10)	C31—H31A	0.9300
C1—C2	1.383 (10)	C32—C33	1.382 (10)
C1—C23	1.498 (11)	C32—H32A	0.9300
C2—C3	1.421 (10)	C33—C34	1.408 (12)
C3—C4	1.347 (11)	C34—C35	1.374 (12)
C3—H3A	0.9300	C34—H34A	0.9300
C4—C5	1.431 (11)	C35—H35A	0.9300
C4—H4A	0.9300	C36—C37	1.382 (10)
C5—C6	1.400 (10)	C36—H36A	0.9300
C6—C7	1.390 (11)	C37—C38	1.399 (11)
C6—C28	1.493 (9)	C37—H37A	0.9300
C7—C8	1.427 (11)	C38—C39	1.404 (11)
C8—C9	1.329 (11)	C39—C40	1.374 (11)
C8—H8A	0.9300	C39—H39A	0.9300
C9—C10	1.431 (10)	C40—H40A	0.9300
C9—H9A	0.9300
N4—Cu1—N1	90.3 (2)	C14—C13—C12	107.4 (7)
N4—Cu1—N3	89.9 (2)	C14—C13—H13A	126.3
N1—Cu1—N3	175.7 (2)	C12—C13—H13A	126.3
N4—Cu1—N2	175.6 (2)	C13—C14—C15	107.2 (7)
N1—Cu1—N2	89.7 (2)	C13—C14—H14A	126.4
N3—Cu1—N2	90.4 (2)	C15—C14—H14A	126.4
N7—Cu2—N8^i	115.9 (3)	N3—C15—C16	126.1 (7)
N7—Cu2—Cl1	127.0 (2)	N3—C15—C14	109.1 (6)
N8^i—Cu2—Cl1	116.9 (2)	C16—C15—C14	124.7 (7)
N5—Cu3—N6^ii	120.4 (3)	C17—C16—C15	123.0 (7)
N5—Cu3—Cl1^iii	109.3 (2)	C17—C16—C38	118.4 (7)
N6^ii—Cu3—Cl1^iii	111.5 (2)	C15—C16—C38	118.6 (7)
N5—Cu3—Cu3^iv	119.5 (2)	N4—C17—C16	125.4 (7)
N6^ii—Cu3—Cu3^iv	70.0 (2)	N4—C17—C18	108.7 (7)
Cl1^iii—Cu3—Cu3^iv	121.31 (11)	C16—C17—C18	125.9 (7)
Cu4B—Cu4—Cl3	144.9 (6)	C19—C18—C17	108.3 (7)
Cu4B—Cu4—O1W	77.0 (6)	C19—C18—H18A	125.8
Cl3—Cu4—O1W	68.0 (5)	C17—C18—H18A	125.8
Cu4B—Cu4—Cl2	40.0 (4)	C18—C19—C20	106.8 (7)
Cl3—Cu4—Cl2	174.1 (4)	C18—C19—H19A	126.6
O1W—Cu4—Cl2	117.0 (5)	C20—C19—H19A	126.6
Cu4—Cu4B—Cl2	119.1 (5)	C1—C20—N4	125.2 (6)
Cu4—Cu4B—O1W	75.8 (7)	C1—C20—C19	125.0 (7)
Cl2—Cu4B—O1W	165.1 (6)	N4—C20—C19	109.8 (6)
Cu2—Cl1—Cu3^v	124.26 (14)	N5—C21—C22	122.9 (8)
Cu4B—Cl2—Cu4	20.87 (16)	N5—C21—H21A	118.5
C5—N1—C2	104.9 (6)	C22—C21—H21A	118.5
C5—N1—Cu1	127.5 (5)	C21—C22—C23	120.7 (8)
C2—N1—Cu1	127.1 (5)	C21—C22—H22A	119.6
C10—N2—C7	105.8 (6)	C23—C22—H22A	119.6
C10—N2—Cu1	126.6 (5)	C22—C23—C24	115.9 (8)
C7—N2—Cu1	127.4 (5)	C22—C23—C1	121.0 (7)
C12—N3—C15	106.2 (6)	C24—C23—C1	123.1 (7)
C12—N3—Cu1	126.9 (5)	C25—C24—C23	119.5 (8)
C15—N3—Cu1	126.5 (5)	C25—C24—H24A	120.3
C20—N4—C17	106.2 (6)	C23—C24—H24A	120.3
C20—N4—Cu1	126.3 (5)	N5—C25—C24	123.6 (8)
C17—N4—Cu1	127.0 (5)	N5—C25—H25A	118.2
C25—N5—C21	117.3 (7)	C24—C25—H25A	118.2
C25—N5—Cu3	120.8 (6)	N6—C26—C27	122.7 (7)
C21—N5—Cu3	120.1 (6)	N6—C26—H26A	118.7
C26—N6—C30	118.2 (7)	C27—C26—H26A	118.7
C26—N6—Cu3^vi	119.0 (5)	C28—C27—C26	119.4 (7)
C30—N6—Cu3^vi	120.7 (5)	C28—C27—H27A	120.3
C35—N7—C31	117.3 (7)	C26—C27—H27A	120.3
C35—N7—Cu2	123.2 (6)	C27—C28—C29	116.8 (7)
C31—N7—Cu2	119.3 (6)	C27—C28—C6	119.5 (7)
C40—N8—C36	116.7 (6)	C29—C28—C6	123.7 (7)
C40—N8—Cu2^vii	125.2 (5)	C30—C29—C28	120.0 (7)
C36—N8—Cu2^vii	118.1 (5)	C30—C29—H29A	120.0
C20—C1—C2	125.4 (7)	C28—C29—H29A	120.0
C20—C1—C23	117.3 (6)	N6—C30—C29	122.8 (8)
C2—C1—C23	117.3 (7)	N6—C30—H30A	118.6
C1—C2—N1	123.7 (7)	C29—C30—H30A	118.6
C1—C2—C3	125.8 (7)	N7—C31—C32	123.1 (8)
N1—C2—C3	110.3 (6)	N7—C31—H31A	118.5
C4—C3—C2	107.4 (7)	C32—C31—H31A	118.5
C4—C3—H3A	126.3	C31—C32—C33	120.9 (8)
C2—C3—H3A	126.3	C31—C32—H32A	119.6
C3—C4—C5	107.5 (7)	C33—C32—H32A	119.6
C3—C4—H4A	126.2	C32—C33—C34	115.6 (8)
C5—C4—H4A	126.2	C32—C33—C11	122.0 (7)
N1—C5—C6	124.3 (7)	C34—C33—C11	122.3 (7)
N1—C5—C4	109.8 (7)	C35—C34—C33	119.8 (8)
C6—C5—C4	125.7 (7)	C35—C34—H34A	120.1
C7—C6—C5	124.6 (7)	C33—C34—H34A	120.1
C7—C6—C28	117.2 (7)	N7—C35—C34	123.3 (8)
C5—C6—C28	118.1 (7)	N7—C35—H35A	118.3
N2—C7—C6	124.7 (7)	C34—C35—H35A	118.3
N2—C7—C8	109.2 (7)	N8—C36—C37	122.9 (8)
C6—C7—C8	125.9 (7)	N8—C36—H36A	118.5
C9—C8—C7	107.9 (7)	C37—C36—H36A	118.5
C9—C8—H8A	126.0	C36—C37—C38	120.1 (8)
C7—C8—H8A	126.0	C36—C37—H37A	120.0
C8—C9—C10	107.5 (7)	C38—C37—H37A	120.0
C8—C9—H9A	126.2	C37—C38—C39	116.6 (7)
C10—C9—H9A	126.2	C37—C38—C16	119.7 (7)
N2—C10—C11	125.5 (7)	C39—C38—C16	123.7 (7)
N2—C10—C9	109.5 (6)	C40—C39—C38	118.5 (8)
C11—C10—C9	124.9 (7)	C40—C39—H39A	120.7
C10—C11—C12	124.5 (7)	C38—C39—H39A	120.7
C10—C11—C33	116.7 (6)	N8—C40—C39	125.2 (8)
C12—C11—C33	118.8 (6)	N8—C40—H40A	117.4
N3—C12—C11	124.9 (7)	C39—C40—H40A	117.4
N3—C12—C13	109.8 (6)	Cu4—O1W—Cu4B	27.3 (2)
C11—C12—C13	125.3 (7)

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) x−1, y−1, z; (iv) −x+1, −y, −z+1; (v) x+1, y+1, z; (vi) x+1/2, −y+1/2, z+1/2; (vii) x−1/2, −y+3/2, z−1/2.