Solid-state structure and anti­microbial and cytotoxicity studies of a cucurbit[6]uril-like Cu₆L₄ constructed from 3,5-bis­[(1H-tetra­zol-5-yl)meth­yl]-4H-1,2,4-triazol-4-amine

3,5-Bis[(1H-tetra­zol-5-yl)meth­yl]-4H-1,2,4-triazol-4-amine (H₂L) associates under deprotonation with CuSO₄ in aqueous medium to form a new waisted barrel-shaped M₆L₄ cluster, namely hexa­aqua­tetra­kis­{μ₄-3,5-bis­[(1H-tetra­zol-5-yl)meth­yl]-4H-1,2,4-triazol-4-amine}-μ₄-sulfato-hexa­copper(II) sulfate hydrate, [Cu₆(SO₄)(C₆H₆N₁₂)₄(H₂O)₆]SO₄·nH₂O (n = ∼23) (1). Cluster 1 resembles concave cucurbit[6]uril and has one disordered sulfate anion trapped inside the cage, which additionally stabilizes the Cu₆ unit. The Cu^II ions have either a square-pyramidal or a distorted octa­hedral geometry. The equatorial positions are filled by N atoms from the L²⁻ ligand, while the axial positions are occupied by coordinated water mol­ecules and O atoms of the sulfate counter-ion. In the solid state, the Cu₆ clusters are connected through a large number of hydrogen bonds formed by uncoordinated water mol­ecules and an additional sulfate anion. The compound shows good anti­microbial activity against E. coli tested with the Kirby Bauer approach. In addition, the cell viability towards HeLa and L-929 cells was studied.

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009), ORTEPIII (Burnett & Johnson, 1996) and DIAMOND (Brandenburg & Putz, 1999); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Hexaaquatetrakis{µ₄-3,5-bis[(1H-tetrazol-5-yl)methyl]-4H-1,2,4-triazol-4-amine}-µ₄-sulfato-hexacopper(II) sulfate 23-hydrate

Crystal data

[Cu6(SO4)(C6H6N12)4(H2O)6]SO4·10H2O	F(000) = 3736
Mr = 1846.52	Dx = 1.830 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.5813 (13) Å	Cell parameters from 18583 reflections
b = 15.3333 (9) Å	θ = 1.6–25.5°
c = 23.4790 (14) Å	µ = 2.04 mm^−1
β = 115.210 (4)°	T = 200 K
V = 6703.7 (7) Å^3	Prism, dark-blue
Z = 4	0.21 × 0.17 × 0.12 mm

Data collection

Stoe IPDS 2 diffractometer	7035 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	Rint = 0.085
rotation method scans	θmax = 25.2°, θmin = 1.1°
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	h = −24→24
Tmin = 0.692, Tmax = 0.949	k = −18→18
75675 measured reflections	l = −27→27
11937 independent reflections

Refinement

Refinement on F^2	176 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.112	w = 1/[σ^2(Fo^2) + (0.0576P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max = 0.001
11937 reflections	Δρmax = 0.77 e Å^−3
1118 parameters	Δρmin = −0.68 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)
Cu2	0.34169 (2)	0.94511 (3)	0.51407 (2)	0.01911 (13)
Cu3	0.15553 (2)	0.94268 (3)	0.48676 (2)	0.01875 (13)
Cu4	0.03048 (2)	0.75462 (3)	0.46919 (2)	0.02020 (12)
Cu5	0.15603 (2)	0.57343 (3)	0.49131 (2)	0.01914 (13)
Cu6	0.34438 (2)	0.57584 (3)	0.51164 (2)	0.01856 (13)
Cu1	0.46862 (2)	0.75936 (3)	0.52936 (2)	0.01959 (12)
O4	−0.08058 (15)	0.7573 (2)	0.45497 (17)	0.0337 (8)
H4A	−0.1203 (16)	0.739 (3)	0.4301 (19)	0.051*
H4B	−0.087 (2)	0.798 (2)	0.475 (2)	0.051*
O1	0.57991 (15)	0.7524 (2)	0.54217 (15)	0.0304 (7)
H1A	0.606 (2)	0.746 (3)	0.5803 (10)	0.046*
H1B	0.601 (2)	0.785 (3)	0.5284 (17)	0.046*
N45	0.38702 (17)	0.9172 (2)	0.45707 (16)	0.0220 (8)
N46	0.43928 (18)	0.8589 (2)	0.46723 (18)	0.0264 (8)
N47	0.4659 (2)	0.8694 (3)	0.42610 (19)	0.0342 (9)
N48	0.4306 (2)	0.9349 (3)	0.38669 (19)	0.0331 (9)
N42	0.26230 (17)	0.9983 (2)	0.43834 (16)	0.0211 (8)
N41	0.19117 (17)	0.9962 (2)	0.42775 (17)	0.0223 (8)
N43	0.19771 (17)	1.0473 (2)	0.34424 (16)	0.0203 (7)
N44	0.1808 (2)	1.0732 (3)	0.28216 (19)	0.0302 (9)
H44A	0.178 (3)	1.1291 (13)	0.282 (2)	0.036*
H44B	0.1404 (16)	1.051 (3)	0.2567 (19)	0.036*
N37	0.06885 (17)	0.9103 (2)	0.41063 (17)	0.0213 (8)
N38	0.02156 (18)	0.8451 (2)	0.40341 (17)	0.0231 (8)
N39	−0.03218 (18)	0.8484 (2)	0.34789 (18)	0.0270 (8)
N40	−0.02175 (18)	0.9167 (2)	0.31612 (17)	0.0265 (8)
N9	0.10773 (17)	0.9139 (2)	0.54225 (17)	0.0221 (8)
N10	0.05807 (18)	0.8516 (2)	0.53291 (17)	0.0235 (8)
N11	0.0350 (2)	0.8560 (2)	0.57624 (18)	0.0301 (9)
N12	0.0689 (2)	0.9211 (2)	0.61589 (19)	0.0308 (9)
N6	0.23412 (17)	0.9910 (2)	0.56354 (16)	0.0204 (8)
N5	0.30533 (17)	0.9902 (2)	0.57481 (16)	0.0197 (7)
N7	0.29731 (18)	1.0384 (2)	0.65820 (16)	0.0221 (8)
N8	0.3136 (2)	1.0664 (3)	0.72024 (18)	0.0281 (8)
H8A	0.315 (2)	1.1226 (13)	0.721 (2)	0.034*
H8B	0.3533 (16)	1.041 (3)	0.743 (2)	0.034*
N2	0.42977 (17)	0.9116 (2)	0.58985 (16)	0.0206 (8)
N1	0.47696 (18)	0.8469 (2)	0.59544 (17)	0.0248 (8)
N4	0.52881 (19)	0.8480 (2)	0.65210 (18)	0.0313 (9)
N3	0.51719 (18)	0.9126 (2)	0.68520 (17)	0.0279 (9)
N21	0.43624 (17)	0.5997 (2)	0.58547 (17)	0.0224 (8)
N22	0.48594 (18)	0.6596 (2)	0.59016 (17)	0.0233 (8)
N23	0.54339 (18)	0.6490 (2)	0.64263 (17)	0.0269 (8)
N24	0.53270 (18)	0.5813 (2)	0.67414 (17)	0.0250 (8)
N18	0.31056 (17)	0.5301 (2)	0.57414 (16)	0.0191 (7)
N17	0.24085 (17)	0.5347 (2)	0.56794 (16)	0.0204 (7)
N19	0.30881 (17)	0.4814 (2)	0.65999 (16)	0.0210 (7)
N20	0.3279 (2)	0.4506 (3)	0.72113 (19)	0.0304 (9)
H20A	0.3664 (15)	0.4763 (15)	0.7459 (18)	0.037*
H20B	0.331 (2)	0.3945 (11)	0.719 (2)	0.037*
N14	0.11200 (17)	0.6045 (2)	0.54958 (17)	0.0221 (8)
N13	0.06116 (18)	0.6647 (2)	0.53992 (17)	0.0241 (8)
N16	0.0422 (2)	0.6639 (2)	0.58634 (19)	0.0303 (9)
N15	0.0813 (2)	0.6036 (2)	0.62822 (18)	0.0290 (8)
N34	0.01511 (17)	0.6565 (2)	0.40891 (17)	0.0243 (8)
N33	0.06417 (17)	0.5948 (2)	0.41573 (17)	0.0226 (8)
N36	−0.02844 (18)	0.5771 (2)	0.32470 (17)	0.0249 (8)
N35	−0.04036 (18)	0.6464 (2)	0.35451 (18)	0.0284 (9)
N30	0.19161 (17)	0.5241 (2)	0.43079 (16)	0.0212 (8)
N29	0.26087 (17)	0.5296 (2)	0.43695 (16)	0.0204 (7)
N31	0.19542 (18)	0.4691 (2)	0.34746 (16)	0.0227 (8)
N32	0.1766 (2)	0.4314 (3)	0.28794 (19)	0.0341 (10)
H32A	0.183 (2)	0.3717 (17)	0.274 (2)	0.041*
H32B	0.1386 (18)	0.460 (3)	0.264 (2)	0.041*
N26	0.38642 (18)	0.6060 (2)	0.45224 (17)	0.0234 (8)
N25	0.43317 (18)	0.6712 (2)	0.45863 (17)	0.0244 (8)
N28	0.4495 (2)	0.6705 (3)	0.41052 (19)	0.0330 (9)
N27	0.4146 (2)	0.6055 (2)	0.37183 (18)	0.0314 (9)
C24	0.3826 (2)	0.9629 (3)	0.4065 (2)	0.0230 (9)
C23	0.3303 (2)	1.0348 (3)	0.3756 (2)	0.0244 (9)
H23A	0.353866	1.091559	0.391880	0.029*
H23B	0.316309	1.033442	0.329688	0.029*
C22	0.2653 (2)	1.0276 (3)	0.3869 (2)	0.0205 (9)
C21	0.1530 (2)	1.0255 (3)	0.3710 (2)	0.0213 (9)
C20	0.0729 (2)	1.0310 (3)	0.3401 (2)	0.0212 (9)
H20C	0.056082	1.035241	0.293922	0.025*
H20D	0.057201	1.084138	0.354655	0.025*
C19	0.0402 (2)	0.9522 (2)	0.3555 (2)	0.0206 (9)
C6	0.1133 (2)	0.9553 (3)	0.5942 (2)	0.0238 (9)
C5	0.1645 (2)	1.0283 (3)	0.6255 (2)	0.0256 (10)
H5A	0.140940	1.084716	0.608227	0.031*
H5B	0.177426	1.027713	0.671179	0.031*
C4	0.2307 (2)	1.0199 (3)	0.6152 (2)	0.0217 (9)
C3	0.3430 (2)	1.0193 (2)	0.63226 (19)	0.0197 (9)
C2	0.4229 (2)	1.0261 (3)	0.6635 (2)	0.0227 (9)
H2A	0.439561	1.028068	0.709698	0.027*
H2B	0.438103	1.080716	0.650186	0.027*
C1	0.4564 (2)	0.9495 (2)	0.6463 (2)	0.0207 (9)
C13	0.3755 (2)	0.5674 (3)	0.3981 (2)	0.0228 (9)
C14	0.3253 (2)	0.4918 (3)	0.3704 (2)	0.0259 (10)
H14A	0.308442	0.491780	0.324092	0.031*
H14B	0.351433	0.436544	0.386947	0.031*
C15	0.2621 (2)	0.4969 (2)	0.3859 (2)	0.0216 (9)
C16	0.1521 (2)	0.4874 (3)	0.3763 (2)	0.0218 (9)
C17	0.0736 (2)	0.4715 (3)	0.3498 (2)	0.0227 (9)
H17A	0.064271	0.417518	0.368203	0.027*
H17B	0.054608	0.463140	0.303667	0.027*
C18	0.0357 (2)	0.5469 (2)	0.36349 (19)	0.0204 (9)
C7	0.1242 (2)	0.5680 (3)	0.6051 (2)	0.0232 (9)
C8	0.1788 (2)	0.4993 (3)	0.6365 (2)	0.0261 (10)
H8C	0.195692	0.504253	0.682632	0.031*
H8D	0.156250	0.441257	0.623435	0.031*
C9	0.2412 (2)	0.5064 (2)	0.6207 (2)	0.0199 (9)
C10	0.3503 (2)	0.4969 (2)	0.6291 (2)	0.0213 (9)
C11	0.4296 (2)	0.4797 (3)	0.6543 (2)	0.0226 (9)
H11A	0.450069	0.472725	0.700640	0.027*
H11B	0.437771	0.424769	0.636172	0.027*
C12	0.4662 (2)	0.5529 (2)	0.6383 (2)	0.0201 (9)
S1B	0.24045 (8)	0.75503 (10)	0.48194 (10)	0.0284 (3)	0.755 (2)
O1B	0.2185 (2)	0.7452 (3)	0.4133 (2)	0.0401 (9)	0.755 (2)
O2B	0.2466 (2)	0.8474 (2)	0.4973 (2)	0.0273 (4)	0.755 (2)
O3B	0.3099 (2)	0.7129 (2)	0.5156 (2)	0.0343 (10)	0.755 (2)
O4B	0.18460 (19)	0.7154 (2)	0.49574 (19)	0.0291 (5)	0.755 (2)
S1A	0.2517 (3)	0.7609 (3)	0.5162 (3)	0.0275 (4)	0.245 (2)
O1A	0.2778 (6)	0.7650 (7)	0.5824 (6)	0.0282 (14)	0.245 (2)
O2A	0.2964 (6)	0.8106 (7)	0.4925 (6)	0.0281 (5)	0.245 (2)
O3A	0.2457 (7)	0.6704 (7)	0.4947 (6)	0.0287 (5)	0.245 (2)
O4A	0.1782 (6)	0.7983 (7)	0.4889 (6)	0.0284 (5)	0.245 (2)
S2	0.27448 (6)	0.27338 (8)	0.58561 (6)	0.0353 (3)
O7	0.25755 (18)	0.3385 (2)	0.53471 (18)	0.0456 (9)
O8	0.22216 (17)	0.2821 (3)	0.61310 (17)	0.0502 (9)
O9	0.27087 (18)	0.1859 (2)	0.55897 (18)	0.0455 (9)
O10	0.34706 (16)	0.2908 (2)	0.63516 (17)	0.0492 (9)
O3	0.13046 (18)	1.1281 (2)	0.48525 (18)	0.0416 (9)
H3A	0.111 (2)	1.150 (3)	0.4493 (13)	0.062*
H3B	0.1715 (15)	1.149 (3)	0.504 (2)	0.062*
O2	0.37854 (17)	1.1264 (2)	0.52280 (17)	0.0404 (8)
H2C	0.4240 (8)	1.131 (3)	0.5526 (14)	0.061*
H2D	0.3533 (17)	1.151 (3)	0.537 (2)	0.061*
O6	0.37999 (19)	0.4051 (2)	0.51440 (19)	0.0426 (9)
H6A	0.400 (3)	0.366 (3)	0.503 (3)	0.064*
H14C	0.5612 (16)	0.743 (3)	0.873 (2)	0.064*
H14D	0.497 (2)	0.7689 (18)	0.829 (2)	0.064*
H6B	0.349 (2)	0.381 (3)	0.523 (3)	0.064*
O5	0.11926 (17)	0.41395 (19)	0.49395 (17)	0.0346 (8)
H5C	0.0898 (17)	0.375 (2)	0.482 (2)	0.052*
H5D	0.1621 (11)	0.390 (3)	0.511 (2)	0.052*
O12	0.3824 (3)	0.8881 (3)	0.7409 (2)	0.0706 (14)
H12A	0.391 (4)	0.847 (3)	0.722 (3)	0.106*
H12B	0.388 (4)	0.889 (4)	0.7785 (15)	0.106*
O13	0.2943 (2)	0.2544 (4)	0.3536 (2)	0.0862 (17)
H13A	0.277 (4)	0.285 (4)	0.373 (3)	0.129*
H13B	0.285 (4)	0.251 (5)	0.3154 (14)	0.129*
O14	0.5214 (2)	0.7264 (3)	0.8449 (2)	0.0607 (11)
O15	0.4135 (2)	0.6269 (3)	0.7438 (2)	0.0608 (11)
H15A	0.4507 (18)	0.652 (3)	0.771 (2)	0.091*
H15B	0.3761 (19)	0.6193 (15)	0.749 (3)	0.091*
O16	−0.1842 (2)	0.7556 (3)	0.2775 (2)	0.0634 (11)
H16A	−0.199 (3)	0.747 (5)	0.309 (2)	0.095*
H16B	−0.1410 (15)	0.758 (5)	0.284 (3)	0.095*
O17	−0.06364 (18)	0.7556 (2)	0.62144 (18)	0.0423 (8)
H17C	−0.035 (2)	0.755 (4)	0.6609 (10)	0.063*
H17D	−0.040 (3)	0.732 (4)	0.604 (2)	0.063*
O18	0.0991 (2)	0.8891 (2)	0.25728 (19)	0.0497 (10)
H18A	0.076 (3)	0.852 (3)	0.267 (3)	0.075*
H18B	0.100 (3)	0.897 (4)	0.2224 (16)	0.075*
O19	0.6564 (2)	0.7521 (2)	0.75150 (19)	0.0560 (10)
H19A	0.620 (2)	0.742 (3)	0.7141 (11)	0.084*
H19B	0.644 (3)	0.7556 (13)	0.7830 (13)	0.084*
O20	0.3690 (4)	0.7572 (4)	0.6492 (3)	0.0637 (16)	0.755 (2)
H20E	0.398 (5)	0.724 (6)	0.677 (6)	0.095*	0.755 (2)
H20F	0.330 (3)	0.743 (6)	0.619 (3)	0.095*	0.755 (2)
O21	0.4173 (8)	0.7515 (10)	0.6759 (9)	0.046 (4)	0.245 (2)
H21A	0.457 (2)	0.747 (6)	0.706 (3)	0.069*	0.245 (2)
H21B	0.393 (11)	0.709 (15)	0.677 (7)	0.069*	0.245 (2)
O11	0.2062 (3)	0.2837 (4)	0.4078 (2)	0.0775 (14)
H11C	0.221 (4)	0.306 (4)	0.4446 (17)	0.116*
H11D	0.213 (4)	0.2282 (15)	0.417 (3)	0.116*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu2	0.0130 (3)	0.0261 (3)	0.0152 (3)	0.00082 (19)	0.0031 (2)	0.0010 (2)
Cu3	0.0141 (3)	0.0241 (3)	0.0161 (3)	−0.00153 (19)	0.0046 (2)	−0.0004 (2)
Cu4	0.0156 (2)	0.0222 (3)	0.0205 (3)	−0.00101 (19)	0.0055 (2)	−0.0015 (2)
Cu5	0.0132 (3)	0.0254 (3)	0.0157 (3)	0.00111 (19)	0.0031 (2)	−0.0002 (2)
Cu6	0.0130 (3)	0.0248 (3)	0.0156 (3)	−0.00196 (19)	0.0039 (2)	−0.0004 (2)
Cu1	0.0153 (2)	0.0227 (3)	0.0190 (3)	−0.00066 (19)	0.0056 (2)	−0.0009 (2)
O4	0.0165 (14)	0.0371 (19)	0.045 (2)	−0.0034 (13)	0.0104 (15)	−0.0149 (15)
O1	0.0221 (16)	0.0379 (19)	0.0315 (18)	−0.0009 (13)	0.0116 (14)	0.0046 (15)
N45	0.0168 (18)	0.0251 (18)	0.019 (2)	0.0015 (14)	0.0022 (15)	0.0035 (15)
N46	0.0221 (19)	0.032 (2)	0.025 (2)	0.0015 (15)	0.0107 (17)	0.0016 (16)
N47	0.030 (2)	0.040 (2)	0.036 (3)	0.0121 (17)	0.0169 (19)	0.0098 (18)
N48	0.029 (2)	0.043 (2)	0.030 (2)	0.0086 (17)	0.0159 (18)	0.0102 (18)
N42	0.0136 (17)	0.0276 (19)	0.020 (2)	−0.0009 (13)	0.0057 (15)	0.0012 (15)
N41	0.0155 (17)	0.0266 (18)	0.020 (2)	0.0011 (13)	0.0027 (15)	0.0014 (15)
N43	0.0174 (17)	0.0242 (18)	0.0164 (19)	0.0012 (13)	0.0045 (15)	0.0038 (14)
N44	0.024 (2)	0.042 (2)	0.019 (2)	−0.0044 (17)	0.0040 (17)	0.0080 (19)
N37	0.0165 (18)	0.0241 (18)	0.022 (2)	−0.0047 (14)	0.0067 (16)	−0.0003 (15)
N38	0.0178 (18)	0.0275 (19)	0.021 (2)	−0.0042 (14)	0.0057 (16)	−0.0024 (15)
N39	0.0191 (18)	0.0275 (19)	0.028 (2)	−0.0053 (15)	0.0033 (17)	0.0011 (16)
N40	0.0188 (19)	0.0266 (19)	0.028 (2)	−0.0004 (14)	0.0038 (16)	0.0008 (16)
N9	0.0187 (18)	0.0257 (18)	0.023 (2)	−0.0054 (14)	0.0097 (16)	−0.0043 (15)
N10	0.0182 (18)	0.0293 (19)	0.026 (2)	−0.0077 (14)	0.0120 (16)	−0.0034 (16)
N11	0.032 (2)	0.033 (2)	0.031 (2)	−0.0073 (16)	0.0192 (19)	−0.0051 (17)
N12	0.031 (2)	0.034 (2)	0.035 (2)	−0.0089 (16)	0.0205 (19)	−0.0085 (17)
N6	0.0150 (17)	0.0259 (18)	0.020 (2)	0.0027 (13)	0.0069 (15)	0.0018 (15)
N5	0.0110 (16)	0.0264 (18)	0.0174 (19)	−0.0023 (13)	0.0020 (14)	0.0027 (14)
N7	0.0211 (18)	0.0262 (18)	0.018 (2)	0.0001 (14)	0.0077 (15)	−0.0020 (15)
N8	0.026 (2)	0.035 (2)	0.022 (2)	−0.0011 (17)	0.0087 (17)	−0.0087 (18)
N2	0.0180 (18)	0.0248 (18)	0.0159 (19)	−0.0020 (14)	0.0042 (15)	−0.0016 (15)
N1	0.0168 (18)	0.0274 (19)	0.022 (2)	0.0065 (14)	0.0003 (16)	0.0014 (15)
N4	0.026 (2)	0.033 (2)	0.025 (2)	0.0069 (16)	0.0009 (18)	−0.0036 (17)
N3	0.0226 (19)	0.0281 (19)	0.021 (2)	0.0037 (15)	−0.0017 (16)	−0.0051 (16)
N21	0.0174 (18)	0.0244 (18)	0.024 (2)	−0.0016 (14)	0.0076 (16)	−0.0008 (15)
N22	0.0180 (18)	0.0251 (18)	0.022 (2)	−0.0033 (14)	0.0033 (16)	−0.0004 (15)
N23	0.0174 (18)	0.032 (2)	0.026 (2)	−0.0028 (15)	0.0038 (17)	0.0029 (16)
N24	0.0154 (17)	0.0275 (19)	0.024 (2)	−0.0027 (14)	0.0009 (16)	0.0036 (16)
N18	0.0157 (17)	0.0197 (16)	0.0189 (19)	0.0003 (13)	0.0046 (15)	−0.0009 (15)
N17	0.0126 (16)	0.0256 (18)	0.022 (2)	−0.0012 (13)	0.0062 (15)	0.0002 (15)
N19	0.0143 (17)	0.0313 (18)	0.0139 (19)	0.0040 (14)	0.0026 (14)	0.0073 (15)
N20	0.0221 (19)	0.043 (2)	0.023 (2)	0.0044 (16)	0.0067 (17)	0.0138 (18)
N14	0.0160 (18)	0.0277 (18)	0.019 (2)	0.0028 (14)	0.0042 (15)	0.0023 (15)
N13	0.0203 (18)	0.0256 (19)	0.026 (2)	0.0042 (14)	0.0090 (16)	−0.0002 (15)
N16	0.029 (2)	0.032 (2)	0.034 (2)	0.0082 (16)	0.0172 (18)	0.0073 (17)
N15	0.031 (2)	0.032 (2)	0.029 (2)	0.0036 (16)	0.0175 (18)	0.0047 (17)
N34	0.0147 (17)	0.0298 (19)	0.022 (2)	0.0020 (14)	0.0014 (16)	0.0004 (16)
N33	0.0181 (18)	0.0236 (18)	0.023 (2)	0.0025 (14)	0.0052 (16)	−0.0015 (15)
N36	0.0170 (18)	0.0260 (19)	0.022 (2)	−0.0003 (14)	−0.0004 (16)	−0.0049 (16)
N35	0.0201 (19)	0.0260 (19)	0.026 (2)	0.0043 (15)	−0.0027 (17)	−0.0007 (16)
N30	0.0126 (17)	0.0271 (18)	0.022 (2)	−0.0016 (13)	0.0050 (15)	−0.0002 (15)
N29	0.0154 (17)	0.0296 (18)	0.0167 (19)	−0.0014 (14)	0.0073 (15)	−0.0028 (15)
N31	0.0227 (18)	0.0257 (18)	0.0178 (19)	−0.0003 (14)	0.0068 (15)	−0.0062 (15)
N32	0.025 (2)	0.046 (2)	0.024 (2)	0.0069 (17)	0.0038 (17)	−0.0188 (18)
N26	0.0200 (18)	0.0250 (18)	0.023 (2)	−0.0038 (14)	0.0075 (16)	−0.0037 (16)
N25	0.0198 (18)	0.0307 (19)	0.024 (2)	−0.0072 (14)	0.0112 (16)	−0.0038 (16)
N28	0.029 (2)	0.045 (2)	0.031 (2)	−0.0109 (17)	0.0192 (19)	−0.0083 (19)
N27	0.032 (2)	0.038 (2)	0.029 (2)	−0.0143 (17)	0.0181 (18)	−0.0110 (18)
C24	0.015 (2)	0.032 (2)	0.023 (2)	−0.0029 (17)	0.0095 (18)	0.0009 (19)
C23	0.018 (2)	0.033 (2)	0.020 (2)	0.0027 (17)	0.0061 (18)	0.0078 (19)
C22	0.016 (2)	0.021 (2)	0.022 (2)	−0.0020 (15)	0.0056 (18)	0.0011 (18)
C21	0.019 (2)	0.022 (2)	0.022 (2)	−0.0008 (16)	0.0079 (18)	−0.0024 (18)
C20	0.016 (2)	0.023 (2)	0.020 (2)	0.0008 (16)	0.0034 (17)	0.0026 (18)
C19	0.018 (2)	0.021 (2)	0.021 (2)	0.0022 (16)	0.0074 (18)	−0.0014 (17)
C6	0.023 (2)	0.022 (2)	0.028 (3)	0.0002 (16)	0.0119 (19)	−0.0017 (18)
C5	0.023 (2)	0.027 (2)	0.029 (3)	−0.0010 (17)	0.014 (2)	−0.0087 (19)
C4	0.023 (2)	0.022 (2)	0.020 (2)	−0.0039 (16)	0.0096 (19)	−0.0020 (18)
C3	0.017 (2)	0.019 (2)	0.018 (2)	−0.0013 (15)	0.0023 (17)	−0.0001 (17)
C2	0.019 (2)	0.025 (2)	0.021 (2)	−0.0011 (17)	0.0048 (18)	−0.0019 (18)
C1	0.018 (2)	0.021 (2)	0.019 (2)	−0.0034 (16)	0.0039 (18)	−0.0018 (17)
C13	0.018 (2)	0.028 (2)	0.021 (2)	0.0007 (17)	0.0066 (19)	−0.0043 (18)
C14	0.024 (2)	0.031 (2)	0.024 (2)	−0.0019 (17)	0.0112 (19)	−0.0058 (19)
C15	0.020 (2)	0.022 (2)	0.022 (2)	−0.0003 (16)	0.0078 (19)	−0.0035 (17)
C16	0.021 (2)	0.027 (2)	0.018 (2)	−0.0027 (16)	0.0084 (18)	−0.0043 (17)
C17	0.014 (2)	0.024 (2)	0.024 (2)	−0.0013 (16)	0.0030 (17)	−0.0028 (18)
C18	0.016 (2)	0.021 (2)	0.019 (2)	−0.0043 (16)	0.0027 (17)	−0.0015 (17)
C7	0.018 (2)	0.025 (2)	0.024 (3)	−0.0025 (17)	0.0062 (19)	0.0010 (18)
C8	0.022 (2)	0.033 (2)	0.026 (3)	0.0029 (17)	0.013 (2)	0.0080 (19)
C9	0.018 (2)	0.021 (2)	0.021 (2)	0.0014 (15)	0.0092 (18)	0.0027 (17)
C10	0.016 (2)	0.023 (2)	0.023 (2)	0.0015 (15)	0.0059 (18)	0.0018 (17)
C11	0.014 (2)	0.028 (2)	0.021 (2)	0.0021 (16)	0.0031 (17)	0.0059 (18)
C12	0.018 (2)	0.020 (2)	0.020 (2)	0.0046 (16)	0.0057 (18)	0.0008 (17)
S1B	0.0269 (6)	0.0212 (5)	0.0348 (8)	0.0000 (5)	0.0107 (7)	0.0028 (7)
O1B	0.0427 (16)	0.0369 (16)	0.0334 (16)	−0.0018 (14)	0.0094 (14)	0.0001 (15)
O2B	0.0257 (8)	0.0204 (7)	0.0345 (9)	0.0002 (7)	0.0116 (8)	0.0015 (8)
O3B	0.031 (2)	0.022 (2)	0.045 (3)	0.0097 (17)	0.011 (2)	−0.0018 (19)
O4B	0.0273 (8)	0.0217 (7)	0.0356 (9)	−0.0010 (7)	0.0108 (8)	0.0022 (8)
S1A	0.0265 (7)	0.0208 (7)	0.0338 (9)	−0.0002 (6)	0.0115 (8)	0.0018 (9)
O1A	0.029 (2)	0.022 (2)	0.031 (2)	0.001 (2)	0.010 (2)	0.001 (2)
O2A	0.0266 (9)	0.0211 (8)	0.0347 (10)	−0.0003 (8)	0.0112 (9)	0.0019 (9)
O3A	0.0271 (9)	0.0214 (8)	0.0350 (10)	−0.0004 (8)	0.0108 (9)	0.0024 (9)
O4A	0.0268 (8)	0.0213 (8)	0.0350 (9)	−0.0002 (7)	0.0110 (8)	0.0020 (9)
S2	0.0229 (5)	0.0358 (6)	0.0424 (7)	0.0008 (5)	0.0092 (5)	0.0002 (5)
O7	0.042 (2)	0.0314 (17)	0.059 (2)	0.0052 (14)	0.0173 (18)	0.0091 (17)
O8	0.0274 (17)	0.073 (2)	0.046 (2)	−0.0038 (17)	0.0120 (16)	−0.0084 (19)
O9	0.0369 (19)	0.0260 (16)	0.071 (3)	0.0011 (14)	0.0202 (18)	0.0023 (16)
O10	0.0243 (17)	0.060 (2)	0.053 (2)	−0.0029 (15)	0.0066 (16)	−0.0056 (19)
O3	0.0292 (19)	0.049 (2)	0.040 (2)	0.0107 (16)	0.0077 (16)	−0.0038 (17)
O2	0.0249 (17)	0.057 (2)	0.039 (2)	−0.0054 (16)	0.0137 (15)	0.0009 (17)
O6	0.038 (2)	0.041 (2)	0.049 (2)	0.0051 (16)	0.0197 (18)	−0.0030 (17)
O5	0.0250 (17)	0.0311 (17)	0.041 (2)	−0.0032 (13)	0.0080 (16)	0.0051 (15)
O12	0.135 (4)	0.040 (2)	0.040 (3)	0.013 (2)	0.040 (3)	0.0083 (19)
O13	0.044 (2)	0.168 (5)	0.040 (3)	0.018 (3)	0.012 (2)	−0.009 (3)
O14	0.058 (3)	0.053 (2)	0.088 (3)	−0.015 (2)	0.047 (2)	−0.024 (2)
O15	0.046 (2)	0.063 (3)	0.062 (3)	0.0017 (19)	0.011 (2)	−0.018 (2)
O16	0.047 (2)	0.068 (3)	0.056 (3)	−0.001 (2)	0.004 (2)	0.008 (2)
O17	0.0356 (19)	0.043 (2)	0.053 (2)	−0.0005 (15)	0.0238 (17)	−0.0047 (18)
O18	0.073 (3)	0.044 (2)	0.047 (3)	−0.0085 (18)	0.039 (2)	−0.0054 (18)
O19	0.045 (2)	0.055 (2)	0.044 (2)	0.0016 (17)	−0.0039 (18)	−0.0049 (18)
O20	0.076 (5)	0.069 (4)	0.045 (4)	−0.005 (4)	0.025 (3)	−0.003 (3)
O21	0.023 (8)	0.048 (9)	0.057 (11)	0.004 (7)	0.008 (8)	0.001 (8)
O11	0.066 (3)	0.120 (4)	0.056 (3)	−0.026 (3)	0.035 (3)	−0.014 (3)

Geometric parameters (Å, º)

Cu1—N1	2.003 (4)	N34—N33	1.342 (4)
Cu1—N22	2.017 (3)	N34—N35	1.310 (5)
Cu1—N25	2.022 (4)	N33—C18	1.332 (5)
Cu1—N46	2.018 (4)	N36—N35	1.350 (5)
Cu1—O1	2.182 (3)	N36—C18	1.327 (5)
Cu2—N2	1.992 (3)	N30—N29	1.373 (4)
Cu2—N5	1.995 (3)	N30—C16	1.314 (5)
Cu2—N42	2.006 (3)	N29—C15	1.310 (5)
Cu2—N45	1.977 (4)	N31—N32	1.406 (5)
Cu2—O2A	2.231 (11)	N31—C15	1.350 (5)
Cu2—O2B	2.360 (4)	N31—C16	1.360 (5)
Cu3—N6	1.983 (3)	N32—H32A	0.995 (15)
Cu3—N9	1.988 (3)	N32—H32B	0.86 (2)
Cu3—N37	1.977 (3)	N26—N25	1.350 (5)
Cu3—N41	1.999 (4)	N26—C13	1.331 (5)
Cu3—O2B	2.305 (4)	N25—N28	1.309 (5)
Cu3—O4A	2.258 (11)	N28—N27	1.334 (5)
Cu4—N10	2.013 (3)	N27—C13	1.340 (5)
Cu4—N13	2.040 (4)	C24—C23	1.495 (6)
Cu4—N34	1.997 (4)	C23—H23A	0.9900
Cu4—N38	2.025 (3)	C23—H23B	0.9900
Cu4—O4	2.165 (3)	C23—C22	1.476 (6)
Cu5—N14	1.994 (4)	C21—C20	1.494 (5)
Cu5—N17	1.990 (3)	C20—H20C	0.9900
Cu5—N30	2.003 (3)	C20—H20D	0.9900
Cu5—N33	1.993 (3)	C20—C19	1.500 (5)
Cu5—O3A	2.346 (12)	C6—C5	1.497 (6)
Cu5—O4B	2.246 (4)	C5—H5A	0.9900
Cu6—N18	2.000 (3)	C5—H5B	0.9900
Cu6—N21	1.980 (3)	C5—C4	1.487 (6)
Cu6—N26	1.984 (4)	C3—C2	1.493 (5)
Cu6—N29	1.991 (3)	C2—H2A	0.9900
Cu6—O3A	2.386 (12)	C2—H2B	0.9900
Cu6—O3B	2.233 (4)	C2—C1	1.502 (6)
O4—H4A	0.823 (19)	C13—C14	1.503 (6)
O4—H4B	0.826 (19)	C14—H14A	0.9900
O1—H1A	0.829 (19)	C14—H14B	0.9900
O1—H1B	0.811 (19)	C14—C15	1.495 (6)
N45—N46	1.340 (5)	C16—C17	1.483 (5)
N45—C24	1.347 (5)	C17—H17A	0.9900
N46—N47	1.307 (5)	C17—H17B	0.9900
N47—N48	1.349 (5)	C17—C18	1.505 (5)
N48—C24	1.331 (5)	C7—C8	1.485 (6)
N42—N41	1.377 (4)	C8—H8C	0.9900
N42—C22	1.314 (5)	C8—H8D	0.9900
N41—C21	1.306 (5)	C8—C9	1.485 (6)
N43—N44	1.404 (5)	C10—C11	1.503 (5)
N43—C22	1.357 (5)	C11—H11A	0.9900
N43—C21	1.357 (5)	C11—H11B	0.9900
N44—H44A	0.859 (19)	C11—C12	1.489 (6)
N44—H44B	0.86 (2)	S1B—O1B	1.484 (5)
N37—N38	1.355 (4)	S1B—O2B	1.454 (4)
N37—C19	1.337 (5)	S1B—O3B	1.457 (4)
N38—N39	1.303 (5)	S1B—O4B	1.454 (4)
N39—N40	1.354 (5)	S1A—O1A	1.414 (14)
N40—C19	1.331 (5)	S1A—O2A	1.475 (13)
N9—N10	1.346 (4)	S1A—O3A	1.463 (12)
N9—C6	1.337 (5)	S1A—O4A	1.483 (12)
N10—N11	1.295 (5)	S2—O7	1.480 (4)
N11—N12	1.340 (5)	S2—O8	1.479 (4)
N12—C6	1.330 (5)	S2—O9	1.469 (3)
N6—N5	1.374 (4)	S2—O10	1.475 (3)
N6—C4	1.322 (5)	O3—H3A	0.835 (19)
N5—C3	1.315 (5)	O3—H3B	0.835 (19)
N7—N8	1.415 (5)	O2—H2C	0.902 (18)
N7—C4	1.341 (5)	O2—H2D	0.819 (19)
N7—C3	1.352 (5)	O6—H6A	0.829 (19)
N8—H8A	0.863 (19)	O6—H6B	0.842 (19)
N8—H8B	0.86 (2)	O5—H5C	0.808 (19)
N2—N1	1.355 (5)	O5—H5D	0.876 (15)
N2—C1	1.332 (5)	O12—H12A	0.828 (19)
N1—N4	1.304 (5)	O12—H12B	0.840 (19)
N4—N3	1.342 (5)	O13—H13A	0.83 (2)
N3—C1	1.321 (5)	O13—H13B	0.83 (2)
N21—N22	1.344 (4)	O14—H14C	0.837 (19)
N21—C12	1.334 (5)	O14—H14D	0.814 (19)
N22—N23	1.304 (5)	O15—H15A	0.855 (19)
N23—N24	1.345 (5)	O15—H15B	0.836 (19)
N24—C12	1.337 (5)	O16—H16A	0.912 (12)
N18—N17	1.381 (4)	O16—H16B	0.835 (19)
N18—C10	1.301 (5)	O17—H17C	0.861 (19)
N17—C9	1.310 (5)	O17—H17D	0.840 (19)
N19—N20	1.399 (5)	O18—H18A	0.835 (19)
N19—C9	1.357 (5)	O18—H18B	0.832 (19)
N19—C10	1.357 (5)	O19—H19A	0.895 (17)
N20—H20A	0.853 (19)	O19—H19B	0.883 (17)
N20—H20B	0.865 (16)	O20—H20E	0.84 (2)
N14—N13	1.341 (4)	O20—H20F	0.85 (2)
N14—C7	1.339 (5)	O21—H21A	0.83 (2)
N13—N16	1.305 (5)	O21—H21B	0.831 (15)
N16—N15	1.340 (5)	O11—H11C	0.86 (2)
N15—C7	1.337 (5)	O11—H11D	0.87 (2)
N45—Cu2—N42	85.92 (14)	N35—N34—Cu4	126.1 (3)
N45—Cu2—N5	171.00 (13)	N35—N34—N33	109.4 (3)
N45—Cu2—N2	92.10 (14)	N34—N33—Cu5	127.0 (3)
N45—Cu2—O2B	110.28 (14)	C18—N33—Cu5	127.5 (3)
N45—Cu2—O2A	85.3 (3)	C18—N33—N34	105.4 (3)
N42—Cu2—O2B	78.81 (13)	C18—N36—N35	105.4 (3)
N42—Cu2—O2A	94.1 (3)	N34—N35—N36	108.8 (3)
N5—Cu2—N42	94.64 (14)	N29—N30—Cu5	125.4 (3)
N5—Cu2—O2B	78.60 (14)	C16—N30—Cu5	126.2 (3)
N5—Cu2—O2A	103.6 (3)	C16—N30—N29	108.2 (3)
N2—Cu2—N42	169.92 (13)	N30—N29—Cu6	125.6 (3)
N2—Cu2—N5	85.79 (14)	C15—N29—Cu6	126.6 (3)
N2—Cu2—O2B	111.08 (14)	C15—N29—N30	107.7 (3)
N2—Cu2—O2A	95.6 (3)	C15—N31—N32	124.4 (4)
N41—Cu3—O2B	79.21 (14)	C15—N31—C16	107.3 (3)
N41—Cu3—O4A	106.5 (3)	C16—N31—N32	128.3 (3)
N37—Cu3—N41	86.13 (14)	N31—N32—H32A	133 (3)
N37—Cu3—N9	91.66 (14)	N31—N32—H32B	103 (3)
N37—Cu3—N6	171.29 (14)	H32A—N32—H32B	117 (4)
N37—Cu3—O2B	108.53 (14)	N25—N26—Cu6	126.7 (3)
N37—Cu3—O4A	82.7 (3)	C13—N26—Cu6	128.4 (3)
N9—Cu3—N41	167.29 (14)	C13—N26—N25	104.9 (3)
N9—Cu3—O2B	113.29 (14)	N26—N25—Cu1	125.2 (3)
N9—Cu3—O4A	85.6 (3)	N28—N25—Cu1	125.4 (3)
N6—Cu3—N41	94.51 (14)	N28—N25—N26	109.3 (3)
N6—Cu3—N9	85.81 (14)	N25—N28—N27	109.4 (3)
N6—Cu3—O2B	80.09 (14)	N28—N27—C13	105.5 (4)
N6—Cu3—O4A	105.4 (3)	N45—C24—C23	125.2 (4)
N38—Cu4—O4	97.03 (13)	N48—C24—N45	111.0 (4)
N38—Cu4—N13	168.37 (14)	N48—C24—C23	123.8 (4)
N10—Cu4—O4	92.61 (13)	C24—C23—H23A	109.2
N10—Cu4—N38	88.05 (14)	C24—C23—H23B	109.2
N10—Cu4—N13	90.17 (14)	H23A—C23—H23B	107.9
N13—Cu4—O4	94.53 (14)	C22—C23—C24	112.1 (3)
N34—Cu4—O4	93.84 (13)	C22—C23—H23A	109.2
N34—Cu4—N38	92.29 (14)	C22—C23—H23B	109.2
N34—Cu4—N10	173.45 (13)	N42—C22—N43	108.6 (3)
N34—Cu4—N13	88.18 (14)	N42—C22—C23	126.3 (4)
N17—Cu5—N14	86.03 (14)	N43—C22—C23	125.0 (4)
N17—Cu5—N33	171.09 (14)	N41—C21—N43	109.0 (3)
N17—Cu5—N30	94.81 (14)	N41—C21—C20	125.0 (4)
N17—Cu5—O4B	97.79 (14)	N43—C21—C20	126.0 (4)
N17—Cu5—O3A	77.5 (3)	C21—C20—H20C	109.5
N14—Cu5—N30	170.75 (14)	C21—C20—H20D	109.5
N14—Cu5—O4B	85.61 (14)	C21—C20—C19	110.8 (3)
N14—Cu5—O3A	114.0 (3)	H20C—C20—H20D	108.1
N33—Cu5—N14	92.05 (14)	C19—C20—H20C	109.5
N33—Cu5—N30	85.71 (14)	C19—C20—H20D	109.5
N33—Cu5—O4B	90.72 (14)	N37—C19—C20	124.2 (4)
N33—Cu5—O3A	111.1 (3)	N40—C19—N37	111.9 (4)
N30—Cu5—O4B	103.36 (14)	N40—C19—C20	123.9 (4)
N30—Cu5—O3A	75.1 (3)	N9—C6—C5	124.9 (4)
N21—Cu6—N18	85.60 (14)	N12—C6—N9	110.8 (4)
N21—Cu6—N29	168.77 (14)	N12—C6—C5	124.3 (4)
N21—Cu6—N26	91.87 (14)	C6—C5—H5A	109.4
N21—Cu6—O3B	89.51 (14)	C6—C5—H5B	109.4
N21—Cu6—O3A	117.5 (3)	H5A—C5—H5B	108.0
N18—Cu6—O3B	94.78 (14)	C4—C5—C6	111.0 (3)
N18—Cu6—O3A	78.4 (3)	C4—C5—H5A	109.4
N29—Cu6—N18	94.69 (14)	C4—C5—H5B	109.4
N29—Cu6—O3B	101.64 (14)	N6—C4—N7	109.0 (4)
N29—Cu6—O3A	73.5 (3)	N6—C4—C5	126.0 (4)
N26—Cu6—N18	171.84 (13)	N7—C4—C5	125.0 (4)
N26—Cu6—N29	86.29 (14)	N5—C3—N7	108.5 (3)
N26—Cu6—O3B	92.95 (15)	N5—C3—C2	124.9 (4)
N26—Cu6—O3A	109.6 (3)	N7—C3—C2	126.6 (4)
N46—Cu1—O1	96.32 (13)	C3—C2—H2A	109.6
N46—Cu1—N25	91.14 (14)	C3—C2—H2B	109.6
N1—Cu1—O1	100.80 (13)	C3—C2—C1	110.5 (3)
N1—Cu1—N46	87.33 (14)	H2A—C2—H2B	108.1
N1—Cu1—N22	91.68 (14)	C1—C2—H2A	109.6
N1—Cu1—N25	165.14 (14)	C1—C2—H2B	109.6
N22—Cu1—O1	90.37 (13)	N2—C1—C2	124.5 (4)
N22—Cu1—N46	173.30 (14)	N3—C1—N2	111.7 (4)
N22—Cu1—N25	88.13 (14)	N3—C1—C2	123.8 (4)
N25—Cu1—O1	94.06 (13)	N26—C13—N27	110.8 (4)
Cu4—O4—H4A	140 (3)	N26—C13—C14	124.2 (4)
Cu4—O4—H4B	109 (3)	N27—C13—C14	125.0 (4)
H4A—O4—H4B	108 (3)	C13—C14—H14A	109.4
Cu1—O1—H1A	108 (3)	C13—C14—H14B	109.4
Cu1—O1—H1B	128 (3)	H14A—C14—H14B	108.0
H1A—O1—H1B	107 (3)	C15—C14—C13	111.3 (3)
N46—N45—Cu2	126.7 (3)	C15—C14—H14A	109.4
N46—N45—C24	104.6 (3)	C15—C14—H14B	109.4
C24—N45—Cu2	127.6 (3)	N29—C15—N31	108.8 (3)
N45—N46—Cu1	127.2 (3)	N29—C15—C14	126.9 (4)
N47—N46—Cu1	122.4 (3)	N31—C15—C14	124.3 (4)
N47—N46—N45	110.1 (3)	N30—C16—N31	107.9 (3)
N46—N47—N48	109.0 (3)	N30—C16—C17	126.3 (4)
C24—N48—N47	105.3 (4)	N31—C16—C17	125.8 (4)
N41—N42—Cu2	123.5 (3)	C16—C17—H17A	109.5
C22—N42—Cu2	127.9 (3)	C16—C17—H17B	109.5
C22—N42—N41	107.7 (3)	C16—C17—C18	110.7 (3)
N42—N41—Cu3	124.1 (3)	H17A—C17—H17B	108.1
C21—N41—Cu3	127.6 (3)	C18—C17—H17A	109.5
C21—N41—N42	107.9 (3)	C18—C17—H17B	109.5
C22—N43—N44	123.5 (3)	N33—C18—C17	123.8 (3)
C21—N43—N44	129.2 (3)	N36—C18—N33	111.0 (4)
C21—N43—C22	106.7 (3)	N36—C18—C17	125.2 (4)
N43—N44—H44A	106 (3)	N14—C7—C8	124.6 (4)
N43—N44—H44B	110 (3)	N15—C7—N14	110.0 (4)
H44A—N44—H44B	111 (5)	N15—C7—C8	125.4 (4)
N38—N37—Cu3	128.4 (3)	C7—C8—H8C	109.2
C19—N37—Cu3	127.7 (3)	C7—C8—H8D	109.2
C19—N37—N38	103.7 (3)	H8C—C8—H8D	107.9
N37—N38—Cu4	125.7 (3)	C9—C8—C7	112.1 (4)
N39—N38—Cu4	123.6 (3)	C9—C8—H8C	109.2
N39—N38—N37	110.7 (3)	C9—C8—H8D	109.2
N38—N39—N40	108.4 (3)	N17—C9—N19	109.1 (3)
C19—N40—N39	105.3 (3)	N17—C9—C8	127.1 (4)
N10—N9—Cu3	127.2 (3)	N19—C9—C8	123.8 (4)
C6—N9—Cu3	128.2 (3)	N18—C10—N19	109.0 (3)
C6—N9—N10	104.5 (3)	N18—C10—C11	125.4 (4)
N9—N10—Cu4	126.8 (3)	N19—C10—C11	125.7 (4)
N11—N10—Cu4	122.7 (3)	C10—C11—H11A	109.6
N11—N10—N9	110.1 (3)	C10—C11—H11B	109.6
N10—N11—N12	109.1 (3)	H11A—C11—H11B	108.1
C6—N12—N11	105.5 (4)	C12—C11—C10	110.4 (3)
N5—N6—Cu3	124.2 (3)	C12—C11—H11A	109.6
C4—N6—Cu3	128.2 (3)	C12—C11—H11B	109.6
C4—N6—N5	107.2 (3)	N21—C12—N24	110.8 (4)
N6—N5—Cu2	124.0 (3)	N21—C12—C11	123.9 (4)
C3—N5—Cu2	127.9 (3)	N24—C12—C11	125.3 (4)
C3—N5—N6	108.0 (3)	O2B—S1B—O1B	108.8 (3)
C4—N7—N8	123.8 (3)	O2B—S1B—O3B	109.6 (3)
C4—N7—C3	107.4 (3)	O3B—S1B—O1B	108.6 (3)
C3—N7—N8	128.6 (3)	O4B—S1B—O1B	107.2 (3)
N7—N8—H8A	108 (3)	O4B—S1B—O2B	110.2 (2)
N7—N8—H8B	105 (3)	O4B—S1B—O3B	112.3 (2)
H8A—N8—H8B	115 (5)	Cu3—O2B—Cu2	101.20 (12)
N1—N2—Cu2	128.1 (3)	S1B—O2B—Cu2	129.7 (2)
C1—N2—Cu2	127.5 (3)	S1B—O2B—Cu3	127.5 (2)
C1—N2—N1	104.4 (3)	S1B—O3B—Cu6	130.5 (2)
N2—N1—Cu1	126.5 (3)	S1B—O4B—Cu5	127.7 (2)
N4—N1—Cu1	124.1 (3)	O1A—S1A—O2A	112.7 (7)
N4—N1—N2	109.4 (3)	O1A—S1A—O3A	111.0 (8)
N1—N4—N3	109.2 (3)	O1A—S1A—O4A	107.3 (8)
C1—N3—N4	105.4 (3)	O2A—S1A—O4A	108.8 (7)
N22—N21—Cu6	127.4 (3)	O3A—S1A—O2A	109.5 (8)
C12—N21—Cu6	127.3 (3)	O3A—S1A—O4A	107.3 (7)
C12—N21—N22	104.8 (3)	S1A—O2A—Cu2	131.2 (7)
N21—N22—Cu1	124.1 (3)	Cu5—O3A—Cu6	102.8 (4)
N23—N22—Cu1	125.4 (3)	S1A—O3A—Cu5	124.1 (8)
N23—N22—N21	110.1 (3)	S1A—O3A—Cu6	125.4 (7)
N22—N23—N24	108.7 (3)	S1A—O4A—Cu3	123.5 (7)
C12—N24—N23	105.5 (3)	O8—S2—O7	109.1 (2)
N17—N18—Cu6	125.1 (3)	O9—S2—O7	108.7 (2)
C10—N18—Cu6	126.6 (3)	O9—S2—O8	110.7 (2)
C10—N18—N17	108.1 (3)	O9—S2—O10	110.6 (2)
N18—N17—Cu5	125.6 (3)	O10—S2—O7	109.0 (2)
C9—N17—Cu5	127.1 (3)	O10—S2—O8	108.7 (2)
C9—N17—N18	107.2 (3)	H3A—O3—H3B	108 (3)
C9—N19—N20	123.5 (3)	H2C—O2—H2D	106 (3)
C9—N19—C10	106.5 (3)	H6A—O6—H6B	107 (3)
C10—N19—N20	129.9 (3)	H5C—O5—H5D	109 (3)
N19—N20—H20A	108 (3)	H12A—O12—H12B	127 (4)
N19—N20—H20B	106 (3)	H13A—O13—H13B	131 (5)
H20A—N20—H20B	116 (4)	H14C—O14—H14D	110 (3)
N13—N14—Cu5	126.7 (3)	H15A—O15—H15B	123 (4)
C7—N14—Cu5	128.0 (3)	H16A—O16—H16B	123 (4)
C7—N14—N13	105.2 (3)	H17C—O17—H17D	104 (3)
N14—N13—Cu4	123.5 (3)	H18A—O18—H18B	128 (4)
N16—N13—Cu4	126.0 (3)	H19A—O19—H19B	114 (3)
N16—N13—N14	110.0 (3)	H20E—O20—H20F	128 (5)
N13—N16—N15	108.7 (3)	H21A—O21—H21B	108 (3)
C7—N15—N16	106.1 (4)	H11C—O11—H11D	101 (3)
N33—N34—Cu4	124.2 (3)
Cu2—N45—N46—Cu1	18.6 (5)	N18—C10—C11—C12	41.1 (6)
Cu2—N45—N46—N47	−167.6 (3)	N17—N18—C10—N19	−1.4 (4)
Cu2—N45—C24—N48	167.7 (3)	N17—N18—C10—C11	179.2 (4)
Cu2—N45—C24—C23	−13.0 (6)	N19—C10—C11—C12	−138.1 (4)
Cu2—N42—N41—Cu3	1.6 (4)	N20—N19—C9—N17	177.8 (4)
Cu2—N42—N41—C21	−171.5 (3)	N20—N19—C9—C8	−3.6 (6)
Cu2—N42—C22—N43	171.9 (3)	N20—N19—C10—N18	−176.3 (4)
Cu2—N42—C22—C23	−5.7 (6)	N20—N19—C10—C11	3.0 (7)
Cu2—N5—C3—N7	−176.3 (3)	N14—N13—N16—N15	0.9 (5)
Cu2—N5—C3—C2	1.5 (6)	N14—C7—C8—C9	29.7 (6)
Cu2—N2—N1—Cu1	−4.2 (5)	N13—N14—C7—N15	1.1 (4)
Cu2—N2—N1—N4	177.9 (3)	N13—N14—C7—C8	−177.7 (4)
Cu2—N2—C1—N3	−177.7 (3)	N13—N16—N15—C7	−0.2 (5)
Cu2—N2—C1—C2	0.9 (6)	N16—N15—C7—N14	−0.6 (5)
Cu3—N41—C21—N43	−173.0 (3)	N16—N15—C7—C8	178.2 (4)
Cu3—N41—C21—C20	4.9 (6)	N15—C7—C8—C9	−148.9 (4)
Cu3—N37—N38—Cu4	−4.4 (5)	N34—N33—C18—N36	0.5 (5)
Cu3—N37—N38—N39	174.7 (3)	N34—N33—C18—C17	177.8 (4)
Cu3—N37—C19—N40	−174.6 (3)	N33—N34—N35—N36	0.2 (5)
Cu3—N37—C19—C20	4.2 (6)	N35—N34—N33—Cu5	−175.6 (3)
Cu3—N9—N10—Cu4	12.4 (5)	N35—N34—N33—C18	−0.4 (4)
Cu3—N9—N10—N11	−175.1 (3)	N35—N36—C18—N33	−0.4 (5)
Cu3—N9—C6—N12	175.0 (3)	N35—N36—C18—C17	−177.7 (4)
Cu3—N9—C6—C5	−7.2 (6)	N30—N29—C15—N31	−1.1 (4)
Cu3—N6—N5—Cu2	3.0 (4)	N30—N29—C15—C14	177.7 (4)
Cu3—N6—N5—C3	−173.8 (3)	N30—C16—C17—C18	39.2 (6)
Cu3—N6—C4—N7	173.6 (3)	N29—N30—C16—N31	0.1 (5)
Cu3—N6—C4—C5	−4.6 (6)	N29—N30—C16—C17	−177.9 (4)
Cu4—N38—N39—N40	179.5 (3)	N31—C16—C17—C18	−138.5 (4)
Cu4—N10—N11—N12	172.6 (3)	N32—N31—C15—N29	179.1 (4)
Cu4—N13—N16—N15	−170.6 (3)	N32—N31—C15—C14	0.3 (6)
Cu4—N34—N33—Cu5	10.2 (5)	N32—N31—C16—N30	−178.6 (4)
Cu4—N34—N33—C18	−174.6 (3)	N32—N31—C16—C17	−0.6 (7)
Cu4—N34—N35—N36	174.2 (3)	N26—N25—N28—N27	−0.3 (5)
Cu5—N17—C9—N19	176.3 (3)	N26—C13—C14—C15	32.6 (6)
Cu5—N17—C9—C8	−2.3 (6)	N25—N26—C13—N27	1.0 (5)
Cu5—N14—N13—Cu4	−11.8 (5)	N25—N26—C13—C14	−178.4 (4)
Cu5—N14—N13—N16	176.4 (3)	N25—N28—N27—C13	0.9 (5)
Cu5—N14—C7—N15	−176.5 (3)	N28—N27—C13—N26	−1.1 (5)
Cu5—N14—C7—C8	4.7 (6)	N28—N27—C13—C14	178.2 (4)
Cu5—N33—C18—N36	175.7 (3)	N27—C13—C14—C15	−146.6 (4)
Cu5—N33—C18—C17	−7.0 (6)	C24—N45—N46—Cu1	−172.7 (3)
Cu5—N30—N29—Cu6	7.2 (5)	C24—N45—N46—N47	1.1 (4)
Cu5—N30—N29—C15	−174.5 (3)	C24—C23—C22—N42	34.4 (6)
Cu5—N30—C16—N31	175.1 (3)	C24—C23—C22—N43	−142.9 (4)
Cu5—N30—C16—C17	−2.9 (6)	C22—N42—N41—Cu3	171.9 (3)
Cu6—N21—N22—Cu1	14.9 (5)	C22—N42—N41—C21	−1.2 (4)
Cu6—N21—N22—N23	−171.7 (3)	C22—N43—C21—N41	1.6 (4)
Cu6—N21—C12—N24	171.4 (3)	C22—N43—C21—C20	−176.4 (4)
Cu6—N21—C12—C11	−8.9 (6)	C21—N43—C22—N42	−2.3 (4)
Cu6—N18—N17—Cu5	8.5 (4)	C21—N43—C22—C23	175.3 (4)
Cu6—N18—N17—C9	−173.6 (3)	C21—C20—C19—N37	34.6 (6)
Cu6—N18—C10—N19	174.0 (3)	C21—C20—C19—N40	−146.7 (4)
Cu6—N18—C10—C11	−5.3 (6)	C19—N37—N38—Cu4	−179.8 (3)
Cu6—N29—C15—N31	177.2 (3)	C19—N37—N38—N39	−0.7 (4)
Cu6—N29—C15—C14	−4.0 (6)	C6—N9—N10—Cu4	−172.1 (3)
Cu6—N26—N25—Cu1	−3.3 (5)	C6—N9—N10—N11	0.4 (4)
Cu6—N26—N25—N28	179.4 (3)	C6—C5—C4—N6	36.1 (6)
Cu6—N26—C13—N27	−178.8 (3)	C6—C5—C4—N7	−141.8 (4)
Cu6—N26—C13—C14	1.9 (6)	C4—N6—N5—Cu2	176.1 (3)
Cu1—N46—N47—N48	173.1 (3)	C4—N6—N5—C3	−0.7 (4)
Cu1—N1—N4—N3	−177.7 (3)	C4—N7—C3—N5	0.3 (4)
Cu1—N22—N23—N24	173.1 (3)	C4—N7—C3—C2	−177.5 (4)
Cu1—N25—N28—N27	−177.6 (3)	C3—N7—C4—N6	−0.7 (4)
N45—N46—N47—N48	−1.0 (5)	C3—N7—C4—C5	177.5 (4)
N45—C24—C23—C22	−24.6 (6)	C3—C2—C1—N2	36.9 (6)
N46—N45—C24—N48	−0.8 (5)	C3—C2—C1—N3	−144.8 (4)
N46—N45—C24—C23	178.4 (4)	C1—N2—N1—Cu1	177.2 (3)
N46—N47—N48—C24	0.4 (5)	C1—N2—N1—N4	−0.7 (4)
N47—N48—C24—N45	0.3 (5)	C13—N26—N25—Cu1	176.9 (3)
N47—N48—C24—C23	−179.0 (4)	C13—N26—N25—N28	−0.4 (4)
N48—C24—C23—C22	154.6 (4)	C13—C14—C15—N29	−31.9 (6)
N42—N41—C21—N43	−0.3 (4)	C13—C14—C15—N31	146.7 (4)
N42—N41—C21—C20	177.7 (4)	C15—N31—C16—N30	−0.7 (5)
N41—N42—C22—N43	2.1 (4)	C15—N31—C16—C17	177.3 (4)
N41—N42—C22—C23	−175.5 (4)	C16—N30—N29—Cu6	−177.7 (3)
N41—C21—C20—C19	−39.6 (6)	C16—N30—N29—C15	0.6 (4)
N43—C21—C20—C19	138.1 (4)	C16—N31—C15—N29	1.1 (5)
N44—N43—C22—N42	−174.3 (4)	C16—N31—C15—C14	−177.7 (4)
N44—N43—C22—C23	3.3 (6)	C16—C17—C18—N33	−33.5 (6)
N44—N43—C21—N41	173.0 (4)	C16—C17—C18—N36	143.4 (4)
N44—N43—C21—C20	−5.0 (7)	C18—N36—N35—N34	0.1 (5)
N37—N38—N39—N40	0.3 (5)	C7—N14—N13—Cu4	170.6 (3)
N38—N37—C19—N40	0.8 (4)	C7—N14—N13—N16	−1.2 (4)
N38—N37—C19—C20	179.7 (4)	C7—C8—C9—N17	−31.5 (6)
N38—N39—N40—C19	0.2 (4)	C7—C8—C9—N19	150.1 (4)
N39—N40—C19—N37	−0.6 (5)	C9—N19—C10—N18	0.4 (5)
N39—N40—C19—C20	−179.5 (4)	C9—N19—C10—C11	179.8 (4)
N9—N10—N11—N12	−0.3 (5)	C10—N18—N17—Cu5	−176.0 (3)
N9—C6—C5—C4	−29.7 (6)	C10—N18—N17—C9	1.9 (4)
N10—N9—C6—N12	−0.4 (5)	C10—N19—C9—N17	0.8 (5)
N10—N9—C6—C5	177.4 (4)	C10—N19—C9—C8	179.4 (4)
N10—N11—N12—C6	0.0 (5)	C10—C11—C12—N21	−33.3 (6)
N11—N12—C6—N9	0.3 (5)	C10—C11—C12—N24	146.4 (4)
N11—N12—C6—C5	−177.5 (4)	C12—N21—N22—Cu1	−172.6 (3)
N12—C6—C5—C4	147.8 (4)	C12—N21—N22—N23	0.8 (4)
N6—N5—C3—N7	0.3 (4)	O1B—S1B—O2B—Cu2	−81.0 (4)
N6—N5—C3—C2	178.1 (4)	O1B—S1B—O2B—Cu3	81.9 (4)
N5—N6—C4—N7	0.9 (4)	O1B—S1B—O3B—Cu6	−56.9 (4)
N5—N6—C4—C5	−177.4 (4)	O1B—S1B—O4B—Cu5	68.1 (3)
N5—C3—C2—C1	−38.2 (6)	O2B—S1B—O3B—Cu6	−175.7 (3)
N7—C3—C2—C1	139.2 (4)	O2B—S1B—O4B—Cu5	−173.6 (3)
N8—N7—C4—N6	−176.5 (3)	O3B—S1B—O2B—Cu2	37.5 (4)
N8—N7—C4—C5	1.8 (6)	O3B—S1B—O2B—Cu3	−159.6 (3)
N8—N7—C3—N5	175.8 (4)	O3B—S1B—O4B—Cu5	−51.1 (4)
N8—N7—C3—C2	−2.0 (7)	O4B—S1B—O2B—Cu2	161.6 (3)
N2—N1—N4—N3	0.2 (5)	O4B—S1B—O2B—Cu3	−35.4 (4)
N1—N2—C1—N3	0.9 (5)	O4B—S1B—O3B—Cu6	61.5 (4)
N1—N2—C1—C2	179.5 (4)	O1A—S1A—O2A—Cu2	−47.2 (11)
N1—N4—N3—C1	0.4 (5)	O1A—S1A—O3A—Cu5	74.2 (10)
N4—N3—C1—N2	−0.8 (5)	O1A—S1A—O3A—Cu6	−69.9 (11)
N4—N3—C1—C2	−179.4 (4)	O1A—S1A—O4A—Cu3	75.1 (9)
N21—N22—N23—N24	−0.2 (4)	O2A—S1A—O3A—Cu5	−160.8 (8)
N22—N21—C12—N24	−1.2 (4)	O2A—S1A—O3A—Cu6	55.2 (11)
N22—N21—C12—C11	178.5 (4)	O2A—S1A—O4A—Cu3	−47.2 (11)
N22—N23—N24—C12	−0.5 (4)	O3A—S1A—O2A—Cu2	−171.2 (8)
N23—N24—C12—N21	1.1 (5)	O3A—S1A—O4A—Cu3	−165.6 (8)
N23—N24—C12—C11	−178.6 (4)	O4A—S1A—O2A—Cu2	71.8 (11)
N18—N17—C9—N19	−1.6 (4)	O4A—S1A—O3A—Cu5	−42.8 (11)
N18—N17—C9—C8	179.8 (4)	O4A—S1A—O3A—Cu6	173.1 (8)