A novel two-dimensional layered Cu²⁺ complex based on Dawson-like [H₃BiW₁₈O₆₀]⁶⁻: synthesis, structure and magnetic properties

A novel complex based on the Dawson-like [H₃BiW₁₈O₆₀]⁶⁻, i.e. (C₂H₉N₂)₂[{Cu(C₁₀H₈N₂)(C₂H₈N₂)}₂(H₃BiW₁₈O₆₀)]·5.5H₂O or (enH)₂[{Cu(2,2′-bipy)(en)}₂(μ₄-H₃BiW₁₈O₆₀)]·5.5H₂O, (1), where enH is protonated ethane-1,2-di­amine, 2,2′-bipy is 2,2′-bi­pyridine and en is ethane-1,2-di­amine, has been synthesized hydro­thermally and characterized by elemental analysis, single-crystal X-ray diffraction analysis, IR spectroscopy, powder XRD, and thermogravimetry and differential thermal analysis (TG–DTA). For (1), each [H₃BiW₁₈O₆₀]⁶⁻ anion acts as a tetra­dentate ligand connecting [Cu(2,2′-bipy)(en)]²⁺ fragments via two terminal and two bridging O atoms, forming a two-dimensional network structure. Along the a and c axes, polyoxometalate units are arranged in an AB…AB manner. The electrochemical behaviour of (1)–CPE (CPE is a carbon paste electrode) was investigated in 2 M H₂SO₄ solution by cyclic voltammetry (CV). The redox process of W^VI/V takes place at E_1/2 = −0.58 (I–I′) and −0.37 V (II–II′), and at −0.04 V (III–III′) for Cu^II/0. The magnetic properties of (1) were investigated in the range 2–300 K and indicated the existence of strong anti­ferromagnetic exchange inter­actions between the Cu²⁺ centres.

Computing details

Data collection: SMART (Bruker, 2005); cell refinement: SMART (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(enH)₂[{Cu(2,2'-bipy)(en)}₂(µ₄-H₃BiW₁₈O₆₀)], 5.5H₂O

Crystal data

(C2H9N2)2[{Cu(C10H8N2)(C2H8N2)}2(H3BiW18O60)]·5.5H2O	F(000) = 4626
Mr = 5262.27	Dx = 4.465 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 16.0955 (10) Å	Cell parameters from 14338 reflections
b = 12.9013 (8) Å	θ = 1.0–26.7°
c = 19.2456 (12) Å	µ = 29.21 mm^−1
β = 101.664 (1)°	T = 296 K
V = 3913.9 (4) Å^3	Block, dark_green
Z = 2	0.20 × 0.05 × 0.04 mm

Data collection

Bruker SMART CCD area detector diffractometer	5288 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.052
Absorption correction: multi-scan (SADABS; Bruker, 2005)	θmax = 25.0°, θmin = 1.8°
Tmin = 0.068, Tmax = 0.323	h = −19→19
19789 measured reflections	k = −15→11
6892 independent reflections	l = −22→21

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.074	w = 1/[σ^2(Fo^2) + (0.0262P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
6892 reflections	Δρmax = 2.34 e Å^−3
570 parameters	Δρmin = −1.77 e Å^−3
370 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.000057 (6)

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

During the refinement, the command 'omit-3 50' was used to omit the weak reflections above 50 degree.

The restraint command 'ISOR' and was used to restrain some non-H atoms with ADP and NPD problems. These atoms are as follows:

isor 0.01 o2 o25 o29 isor 0.01 c8

The restraint command 'SIMU' was also used to restrain the atoms on organic ligands possess the similar thermal parameters. The refinement commands are as follows:

simu 0.01 0.01 3.8 c1 c2 c3 c4 c5 c6 c7 c8 c9 c10 n1 n2 simu 0.01 0.01 3.8 c11 c12 n3 n4 simu 0.01 0.01 3.8 c13 c14 n5 n6

The distances of some C-C,C-O,C-N and C-H bonds of the organic ligands were fixed with the restraint command 'DFIX'

dfix 1.50 0.01 c11 c12 c13 c14 dfix 1.34 0.02 c1 c2 c2 c3 c3 c4 c7 c8 c8 c9 c9 c10 dfix 1.40 0.02 c1 c6

The distances of O-H bonds of the water molecules were fixed with the restraint command 'DFIX'

dfix 0.85 0.01 o1w h1wa o1w h1wb

dfix 0.85 0.01 o2w h2wa o2w h2wb

The distances of W2a-O18 and O20 bonds were fixed with the restraint command 'DFIX'

dfix 2.3 0.02 w2a o18 w2a o20

Because [H₃BiW₁₈O₆₀]^6- was a large cluster and a high symmetry, about 3% of [H₃BiW₁₈O₆₀]^6- ions in crystal are rotated 60 ^o along the C₃ axis, making W2, W5 and W7 atoms in the cap disodered with the occupancy of 97% and the occupancy of corresponding W2a, W5a and W7a was 3%. However, the O atoms linked with W2a, W5a and W7a could not be observed in the electron density map. 3H atoms of [H3BiW18O60]6- and 3.5 water molecules could not be observed in the electron density map because there were too much heavy W atoms in crystal. Therefore, 5.5 water molecules in chemical fomula were added based on the TG analysis.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
W1	1.05928 (3)	0.57971 (4)	0.20004 (3)	0.01960 (13)
W2	0.71733 (3)	0.41674 (4)	0.05137 (3)	0.02047 (14)	0.97
W3	0.82244 (4)	0.70558 (4)	−0.06738 (3)	0.02231 (14)
W4	0.95891 (4)	0.78191 (4)	0.07122 (3)	0.02222 (14)
W5	0.77285 (4)	0.69187 (4)	0.08808 (3)	0.02000 (14)	0.97
W6	1.01406 (3)	0.33152 (4)	0.16929 (3)	0.01761 (13)
W7	0.87179 (3)	0.48791 (4)	0.21308 (3)	0.01715 (13)	0.97
W8	0.85466 (4)	0.24988 (4)	0.01001 (3)	0.02056 (13)
W9	0.77073 (4)	0.42843 (4)	−0.10350 (3)	0.02311 (14)
Bi1	0.95546 (6)	0.50679 (7)	0.02229 (4)	0.0111 (2)	0.5
O1	1.0897 (5)	0.4324 (6)	0.2232 (4)	0.0157 (19)
O2	0.8279 (6)	0.6151 (7)	0.1708 (4)	0.020 (2)
O3	0.7717 (5)	0.5759 (7)	−0.0943 (4)	0.022 (2)
O4	0.9246 (5)	0.6545 (6)	−0.0947 (4)	0.0166 (19)
O5	0.9578 (5)	0.4851 (6)	0.1316 (4)	0.0174 (19)
O6	0.8393 (5)	0.4210 (6)	0.0077 (4)	0.0158 (19)
O7	1.0066 (5)	0.6976 (7)	0.1532 (4)	0.021 (2)
O8	0.7824 (6)	0.7784 (7)	−0.1405 (4)	0.026 (2)
O9	1.1374 (5)	0.6335 (7)	0.2626 (4)	0.024 (2)
O10	1.1186 (5)	0.5605 (6)	0.1234 (4)	0.020 (2)
O11	0.7434 (5)	0.7397 (7)	−0.0090 (4)	0.023 (2)
O12	0.6199 (6)	0.3999 (8)	0.0712 (5)	0.035 (3)
O13	0.9228 (5)	0.2703 (6)	0.1021 (4)	0.018 (2)
O14	0.9742 (5)	0.5639 (7)	0.2545 (4)	0.022 (2)
O15	0.8498 (6)	0.1180 (7)	0.0041 (4)	0.025 (2)
O16	0.8833 (5)	0.6440 (6)	0.0348 (4)	0.0174 (19)
O17	1.0442 (5)	0.7261 (6)	0.0279 (4)	0.019 (2)
O18	0.7540 (5)	0.2731 (6)	0.0465 (4)	0.019 (2)
O19	1.0612 (6)	0.2244 (7)	0.2117 (4)	0.023 (2)
O20	0.9335 (5)	0.3604 (6)	0.2296 (4)	0.020 (2)
O21	0.8948 (5)	0.8197 (7)	−0.0197 (4)	0.023 (2)
O22	0.7110 (6)	0.4145 (7)	−0.1871 (4)	0.029 (2)
O23	0.8268 (6)	0.4881 (7)	0.2864 (4)	0.028 (2)
O24	0.6825 (5)	0.4208 (7)	−0.0507 (4)	0.022 (2)
O25	0.7899 (6)	0.4182 (8)	0.1478 (5)	0.026 (2)
O26	0.7899 (5)	0.2809 (6)	−0.0855 (4)	0.021 (2)
O27	0.6944 (6)	0.7500 (8)	0.1204 (5)	0.037 (3)
O28	1.0010 (6)	0.8999 (7)	0.0989 (5)	0.035 (3)
O29	0.7213 (7)	0.5605 (10)	0.0528 (6)	0.024 (3)
O30	0.8579 (6)	0.7980 (6)	0.1109 (4)	0.022 (2)
N1	0.6418 (9)	0.0712 (11)	0.0398 (7)	0.050 (2)
N2	0.6048 (9)	0.1984 (11)	0.1351 (7)	0.047 (2)
N3	0.7878 (8)	0.1795 (10)	0.2155 (6)	0.043 (3)
H3B	0.8108	0.2363	0.2010	0.051*
H3C	0.7584	0.1984	0.2478	0.051*
N4	0.8096 (8)	0.0211 (10)	0.1331 (6)	0.041 (3)
H4B	0.7955	−0.0438	0.1414	0.049*
H4C	0.8234	0.0229	0.0906	0.049*
N5	0.7607 (7)	0.6876 (9)	−0.2799 (6)	0.037 (3)
H5B	0.7543	0.7395	−0.2509	0.055*	0.8333
H5C	0.8082	0.6532	−0.2621	0.055*	0.8333
H5D	0.7639	0.7130	−0.3223	0.055*	0.8333
N6	0.6243 (8)	0.4597 (9)	−0.3469 (7)	0.041 (3)
H6A	0.6321	0.4086	−0.3760	0.062*	0.8333
H6B	0.6183	0.4333	−0.3055	0.062*	0.8333
H6C	0.5778	0.4951	−0.3661	0.062*	0.8333
C1	0.5449 (10)	0.1933 (13)	0.0728 (8)	0.050 (2)
C2	0.4714 (10)	0.2481 (13)	0.0676 (9)	0.053 (2)
H2A	0.4327	0.2494	0.0246	0.063*
C3	0.4536 (11)	0.3004 (13)	0.1234 (7)	0.051 (3)
H3A	0.4015	0.3331	0.1198	0.061*
C4	0.5115 (10)	0.3050 (14)	0.1845 (8)	0.048 (3)
H4A	0.5003	0.3415	0.2232	0.058*
C5	0.5865 (11)	0.2555 (14)	0.1883 (9)	0.047 (2)
H5A	0.6274	0.2613	0.2298	0.057*
C6	0.5689 (11)	0.1305 (14)	0.0186 (8)	0.052 (2)
C7	0.5270 (11)	0.1237 (14)	−0.0499 (9)	0.056 (2)
H7A	0.4805	0.1665	−0.0654	0.068*
C8	0.5509 (11)	0.0556 (13)	−0.0973 (9)	0.058 (3)
H8A	0.5198	0.0515	−0.1436	0.069*
C9	0.6195 (10)	−0.0049 (14)	−0.0763 (8)	0.057 (3)
H9A	0.6363	−0.0522	−0.1072	0.069*
C10	0.6636 (11)	0.0052 (15)	−0.0080 (8)	0.054 (3)
H10A	0.7116	−0.0358	0.0063	0.065*
C11	0.8545 (11)	0.1092 (13)	0.2473 (8)	0.048 (3)
H11A	0.8336	0.0601	0.2779	0.058*
H11B	0.9015	0.1472	0.2755	0.058*
C12	0.8828 (10)	0.0535 (12)	0.1877 (7)	0.045 (3)
H12A	0.9190	0.0988	0.1665	0.054*
H12B	0.9158	−0.0071	0.2062	0.054*
C13	0.6970 (9)	0.5283 (10)	−0.3360 (7)	0.032 (3)
H13A	0.7039	0.5560	−0.3813	0.039*
H13B	0.7476	0.4893	−0.3159	0.039*
C14	0.6871 (9)	0.6163 (10)	−0.2872 (7)	0.034 (3)
H14A	0.6353	0.6539	−0.3060	0.041*
H14B	0.6832	0.5893	−0.2410	0.041*
Cu1	0.70985 (12)	0.11541 (14)	0.13345 (9)	0.0335 (4)
W7A	0.8621 (14)	0.6541 (19)	0.1867 (11)	0.027 (5)*	0.03
W2A	0.8118 (17)	0.3874 (13)	0.1415 (10)	0.073 (11)*	0.03
W5A	0.708 (3)	0.569 (3)	0.0280 (18)	0.046 (10)*	0.03
O1W	1.047 (4)	0.038 (4)	0.309 (3)	0.110 (19)*	0.3
H1WA	1.0925	0.0027	0.3149	0.132*	0.3
H1WB	1.0393	0.0595	0.3489	0.132*	0.3
O2W	0.992 (2)	0.091 (3)	0.4053 (15)	0.166 (12)*	0.7
H2WA	0.9981	0.0278	0.4170	0.200*	0.7
H2WB	1.0397	0.1164	0.4014	0.200*	0.7

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
W1	0.0240 (3)	0.0172 (3)	0.0156 (3)	−0.0046 (2)	−0.0007 (2)	−0.0029 (2)
W2	0.0200 (3)	0.0192 (3)	0.0224 (3)	−0.0059 (2)	0.0046 (2)	−0.0004 (3)
W3	0.0255 (3)	0.0209 (3)	0.0194 (3)	0.0019 (2)	0.0018 (2)	0.0042 (3)
W4	0.0272 (3)	0.0114 (3)	0.0273 (3)	−0.0036 (2)	0.0035 (2)	−0.0051 (2)
W5	0.0263 (3)	0.0137 (3)	0.0212 (3)	0.0041 (2)	0.0079 (2)	0.0027 (2)
W6	0.0242 (3)	0.0119 (3)	0.0158 (3)	0.0020 (2)	0.0019 (2)	0.0032 (2)
W7	0.0244 (3)	0.0145 (3)	0.0135 (3)	0.0002 (2)	0.0061 (2)	−0.0001 (2)
W8	0.0286 (3)	0.0115 (3)	0.0214 (3)	−0.0049 (2)	0.0046 (2)	0.0012 (2)
W9	0.0275 (3)	0.0224 (3)	0.0176 (3)	−0.0055 (3)	0.0002 (2)	0.0029 (3)
Bi1	0.0155 (5)	0.0069 (5)	0.0100 (4)	−0.0010 (4)	0.0001 (4)	0.0007 (4)
O1	0.024 (5)	0.007 (4)	0.015 (4)	−0.001 (4)	0.002 (4)	0.003 (4)
O2	0.028 (5)	0.013 (5)	0.021 (4)	−0.007 (4)	0.009 (4)	−0.004 (4)
O3	0.024 (5)	0.015 (5)	0.024 (5)	−0.005 (4)	−0.004 (4)	−0.004 (4)
O4	0.024 (5)	0.014 (5)	0.013 (4)	0.000 (4)	0.005 (4)	−0.002 (4)
O5	0.023 (5)	0.022 (5)	0.009 (4)	0.000 (4)	0.007 (4)	0.001 (4)
O6	0.023 (5)	0.006 (4)	0.016 (4)	−0.001 (4)	0.000 (4)	0.004 (4)
O7	0.025 (5)	0.019 (5)	0.019 (4)	−0.006 (4)	0.003 (4)	−0.006 (4)
O8	0.032 (6)	0.021 (5)	0.026 (5)	0.002 (4)	0.005 (4)	0.001 (4)
O9	0.027 (5)	0.021 (5)	0.020 (5)	−0.002 (4)	−0.004 (4)	−0.003 (4)
O10	0.017 (5)	0.011 (5)	0.028 (5)	0.005 (4)	−0.003 (4)	−0.004 (4)
O11	0.023 (5)	0.019 (5)	0.026 (5)	0.006 (4)	0.004 (4)	0.003 (4)
O12	0.030 (6)	0.038 (6)	0.041 (6)	−0.002 (5)	0.013 (5)	0.005 (5)
O13	0.027 (5)	0.016 (5)	0.015 (4)	−0.009 (4)	0.010 (4)	0.000 (4)
O14	0.027 (5)	0.017 (5)	0.019 (4)	0.006 (4)	0.002 (4)	−0.001 (4)
O15	0.039 (6)	0.011 (5)	0.024 (5)	−0.006 (4)	0.000 (4)	0.000 (4)
O16	0.016 (5)	0.010 (5)	0.025 (5)	−0.002 (4)	0.003 (4)	−0.001 (4)
O17	0.021 (5)	0.017 (5)	0.016 (4)	0.003 (4)	−0.001 (4)	−0.002 (4)
O18	0.031 (5)	0.006 (4)	0.019 (4)	−0.005 (4)	0.001 (4)	0.002 (4)
O19	0.040 (6)	0.016 (5)	0.012 (4)	0.009 (4)	0.004 (4)	0.005 (4)
O20	0.029 (5)	0.014 (5)	0.015 (4)	−0.002 (4)	0.002 (4)	0.001 (4)
O21	0.027 (5)	0.018 (5)	0.023 (5)	−0.001 (4)	0.004 (4)	0.006 (4)
O22	0.036 (6)	0.024 (6)	0.025 (5)	−0.008 (5)	−0.002 (4)	0.005 (4)
O23	0.038 (6)	0.025 (6)	0.025 (5)	0.003 (5)	0.014 (4)	0.001 (4)
O24	0.017 (5)	0.023 (5)	0.021 (4)	−0.001 (4)	−0.008 (4)	−0.001 (4)
O25	0.026 (3)	0.027 (3)	0.026 (3)	−0.0006 (10)	0.0063 (11)	−0.0011 (10)
O26	0.029 (5)	0.012 (5)	0.018 (4)	0.002 (4)	−0.003 (4)	−0.001 (4)
O27	0.036 (6)	0.037 (6)	0.044 (6)	0.018 (5)	0.023 (5)	0.013 (5)
O28	0.055 (7)	0.017 (6)	0.031 (5)	0.001 (5)	0.000 (5)	−0.011 (5)
O29	0.017 (5)	0.028 (6)	0.028 (6)	0.004 (4)	0.005 (5)	−0.002 (5)
O30	0.030 (5)	0.012 (5)	0.027 (5)	0.005 (4)	0.015 (4)	0.002 (4)
N1	0.051 (4)	0.054 (5)	0.047 (4)	−0.015 (4)	0.015 (4)	−0.008 (4)
N2	0.049 (4)	0.048 (5)	0.045 (4)	−0.010 (4)	0.015 (4)	−0.004 (4)
N3	0.053 (6)	0.032 (6)	0.045 (6)	0.004 (5)	0.013 (5)	0.008 (5)
N4	0.053 (6)	0.032 (6)	0.041 (6)	0.005 (5)	0.019 (5)	0.004 (5)
N5	0.039 (5)	0.029 (5)	0.038 (5)	0.000 (5)	−0.005 (5)	0.005 (5)
N6	0.037 (5)	0.025 (5)	0.059 (6)	0.004 (5)	0.003 (5)	0.004 (5)
C1	0.049 (4)	0.052 (4)	0.049 (4)	−0.013 (4)	0.013 (4)	−0.004 (4)
C2	0.051 (4)	0.054 (5)	0.052 (4)	−0.010 (4)	0.009 (4)	−0.006 (4)
C3	0.048 (5)	0.052 (5)	0.053 (5)	−0.008 (4)	0.014 (4)	−0.002 (5)
C4	0.049 (5)	0.048 (5)	0.050 (5)	−0.007 (5)	0.016 (5)	−0.002 (5)
C5	0.048 (5)	0.051 (5)	0.046 (5)	−0.010 (4)	0.015 (4)	−0.003 (4)
C6	0.051 (4)	0.054 (4)	0.049 (4)	−0.013 (4)	0.010 (4)	−0.006 (4)
C7	0.056 (4)	0.060 (5)	0.053 (4)	−0.012 (4)	0.009 (4)	−0.009 (4)
C8	0.060 (5)	0.060 (5)	0.052 (4)	−0.016 (4)	0.009 (4)	−0.009 (4)
C9	0.060 (5)	0.062 (5)	0.051 (5)	−0.017 (5)	0.014 (5)	−0.012 (5)
C10	0.055 (5)	0.058 (5)	0.050 (5)	−0.016 (5)	0.013 (4)	−0.012 (5)
C11	0.056 (7)	0.038 (6)	0.050 (6)	0.005 (6)	0.011 (6)	0.005 (6)
C12	0.053 (7)	0.037 (6)	0.049 (6)	0.007 (5)	0.017 (5)	0.007 (6)
C13	0.027 (6)	0.024 (6)	0.042 (6)	0.003 (5)	−0.001 (5)	0.008 (5)
C14	0.030 (6)	0.028 (6)	0.042 (6)	0.003 (5)	0.002 (5)	0.006 (5)
Cu1	0.0441 (12)	0.0280 (10)	0.0297 (9)	−0.0005 (9)	0.0108 (9)	−0.0047 (9)

Geometric parameters (Å, º)

W1—O9	1.703 (8)	O14—W7A	2.32 (2)
W1—O7	1.880 (9)	O17—W8^i	1.939 (9)
W1—O14	1.897 (9)	O18—W2A	2.388 (18)
W1—O10	1.928 (9)	O20—W2A	2.343 (17)
W1—O1	1.990 (8)	O23—Cu1^ii	2.407 (9)
W1—O5	2.242 (8)	O24—W5A	2.42 (4)
W2—O12	1.701 (9)	O25—W2A	0.56 (3)
W2—O29	1.856 (13)	O30—W7A	2.35 (2)
W2—O24	1.932 (8)	N1—C10	1.35 (2)
W2—O18	1.953 (8)	N1—C6	1.39 (2)
W2—O25	1.983 (9)	N1—Cu1	1.993 (13)
W2—O6	2.287 (8)	N2—C5	1.341 (19)
W3—O8	1.707 (8)	N2—C1	1.379 (19)
W3—O3	1.888 (8)	N2—Cu1	2.007 (14)
W3—O11	1.911 (9)	N3—C11	1.445 (18)
W3—O4	1.940 (8)	N3—Cu1	1.987 (12)
W3—O21	1.983 (9)	N3—H3B	0.8900
W3—O16	2.164 (8)	N3—H3C	0.8900
W4—O28	1.707 (9)	N4—C12	1.473 (18)
W4—O17	1.886 (8)	N4—Cu1	2.015 (12)
W4—O21	1.906 (8)	N4—H4B	0.8900
W4—O30	1.941 (9)	N4—H4C	0.8900
W4—O7	1.942 (8)	N5—C14	1.484 (18)
W4—O16	2.190 (8)	N5—H5B	0.8900
W5—O27	1.691 (9)	N5—H5C	0.8900
W5—O30	1.924 (9)	N5—H5D	0.8900
W5—O2	1.932 (8)	N6—C13	1.448 (17)
W5—O11	1.934 (8)	N6—H6A	0.8900
W5—O29	1.948 (12)	N6—H6B	0.8900
W5—O16	2.308 (8)	N6—H6C	0.8900
W6—O19	1.703 (8)	C1—C2	1.365 (15)
W6—O4^i	1.908 (8)	C1—C6	1.434 (15)
W6—O13	1.920 (8)	C2—C3	1.346 (15)
W6—O1	1.934 (8)	C2—H2A	0.9300
W6—O20	1.943 (9)	C3—C4	1.345 (15)
W6—O5	2.237 (8)	C3—H3A	0.9300
W7—O23	1.712 (8)	C4—C5	1.36 (2)
W7—O25	1.859 (9)	C4—H4A	0.9300
W7—O2	1.903 (9)	C5—H5A	0.9300
W7—O20	1.915 (8)	C6—C7	1.36 (2)
W7—O14	1.944 (9)	C7—C8	1.375 (16)
W7—O5	2.292 (8)	C7—H7A	0.9300
W8—O15	1.706 (9)	C8—C9	1.347 (16)
W8—O13	1.904 (8)	C8—H8A	0.9300
W8—O18	1.915 (9)	C9—C10	1.367 (15)
W8—O17^i	1.939 (9)	C9—H9A	0.9300
W8—O26	1.962 (8)	C10—H10A	0.9300
W8—O6	2.221 (8)	C11—C12	1.501 (9)
W9—O22	1.709 (8)	C11—H11A	0.9700
W9—O10^i	1.902 (9)	C11—H11B	0.9700
W9—O24	1.908 (9)	C12—H12A	0.9700
W9—O3	1.911 (8)	C12—H12B	0.9700
W9—O26	1.948 (8)	C13—C14	1.501 (9)
W9—O6	2.203 (7)	C13—H13A	0.9700
Bi1—Bi1^i	1.8218 (18)	C13—H13B	0.9700
Bi1—O5	2.115 (7)	C14—H14A	0.9700
Bi1—O6	2.142 (8)	C14—H14B	0.9700
Bi1—O16	2.158 (8)	Cu1—O23^iii	2.407 (9)
O2—W7A	0.76 (2)	O1W—H1WA	0.8500
O4—W6^i	1.908 (8)	O1W—H1WB	0.8501
O10—W9^i	1.902 (9)	O2W—H2WA	0.8501
O11—W5A	2.41 (4)	O2W—H2WB	0.8500
O9—W1—O7	101.9 (4)	W6^i—O4—W3	140.1 (4)
O9—W1—O14	99.5 (4)	Bi1—O5—W6	111.4 (3)
O7—W1—O14	92.7 (4)	Bi1—O5—W1	112.1 (4)
O9—W1—O10	100.6 (4)	W6—O5—W1	95.3 (3)
O7—W1—O10	89.0 (3)	Bi1—O5—W7	141.9 (4)
O14—W1—O10	159.0 (3)	W6—O5—W7	93.0 (3)
O9—W1—O1	96.8 (4)	W1—O5—W7	93.3 (3)
O7—W1—O1	161.1 (3)	Bi1—O6—W9	110.9 (3)
O14—W1—O1	86.9 (3)	Bi1—O6—W8	114.9 (4)
O10—W1—O1	84.9 (3)	W9—O6—W8	95.4 (3)
O9—W1—O5	169.6 (4)	Bi1—O6—W2	139.1 (4)
O7—W1—O5	87.4 (3)	W9—O6—W2	93.4 (3)
O14—W1—O5	75.2 (3)	W8—O6—W2	94.0 (3)
O10—W1—O5	84.0 (3)	W1—O7—W4	155.3 (5)
O1—W1—O5	74.2 (3)	W9^i—O10—W1	140.6 (4)
O12—W2—O29	99.0 (5)	W3—O11—W5	115.6 (4)
O12—W2—O24	98.1 (4)	W3—O11—W5A	100.8 (11)
O29—W2—O24	89.4 (5)	W8—O13—W6	154.5 (5)
O12—W2—O18	101.0 (4)	W1—O14—W7	118.3 (4)
O29—W2—O18	159.9 (4)	W1—O14—W7A	101.6 (7)
O24—W2—O18	90.3 (3)	Bi1—O16—W3	110.8 (4)
O12—W2—O25	100.7 (4)	Bi1—O16—W4	115.2 (4)
O29—W2—O25	88.0 (5)	W3—O16—W4	96.4 (3)
O24—W2—O25	161.2 (4)	Bi1—O16—W5	138.6 (4)
O18—W2—O25	85.8 (4)	W3—O16—W5	93.3 (3)
O12—W2—O6	169.8 (4)	W4—O16—W5	93.9 (3)
O29—W2—O6	87.2 (4)	W4—O17—W8^i	147.9 (5)
O24—W2—O6	73.7 (3)	W8—O18—W2	116.9 (4)
O18—W2—O6	73.4 (3)	W8—O18—W2A	98.6 (8)
O25—W2—O6	87.5 (3)	W7—O20—W6	116.9 (4)
O8—W3—O3	101.0 (4)	W6—O20—W2A	99.1 (8)
O8—W3—O11	99.9 (4)	W4—O21—W3	113.2 (4)
O3—W3—O11	93.6 (4)	W7—O23—Cu1^ii	136.8 (5)
O8—W3—O4	99.4 (4)	W9—O24—W2	116.7 (4)
O3—W3—O4	88.2 (4)	W9—O24—W5A	103.9 (10)
O11—W3—O4	159.9 (3)	W7—O25—W2	147.1 (6)
O8—W3—O21	93.6 (4)	W9—O26—W8	113.6 (4)
O3—W3—O21	165.0 (3)	W2—O29—W5	152.4 (7)
O11—W3—O21	87.5 (4)	W5—O30—W4	116.6 (4)
O4—W3—O21	85.8 (3)	W4—O30—W7A	103.7 (6)
O8—W3—O16	168.0 (4)	C10—N1—C6	117.8 (14)
O3—W3—O16	90.9 (3)	C10—N1—Cu1	128.7 (12)
O11—W3—O16	77.5 (3)	C6—N1—Cu1	112.6 (11)
O4—W3—O16	82.5 (3)	C5—N2—C1	117.8 (15)
O21—W3—O16	74.7 (3)	C5—N2—Cu1	128.3 (12)
O28—W4—O17	101.5 (4)	C1—N2—Cu1	113.9 (10)
O28—W4—O21	99.5 (4)	C11—N3—Cu1	111.8 (10)
O17—W4—O21	90.0 (3)	C11—N3—H3B	109.3
O28—W4—O30	95.3 (4)	Cu1—N3—H3B	109.3
O17—W4—O30	163.0 (4)	C11—N3—H3C	109.3
O21—W4—O30	89.6 (4)	Cu1—N3—H3C	109.3
O28—W4—O7	100.4 (4)	H3B—N3—H3C	107.9
O17—W4—O7	86.7 (3)	C12—N4—Cu1	110.5 (9)
O21—W4—O7	160.1 (4)	C12—N4—H4B	109.6
O30—W4—O7	88.0 (3)	Cu1—N4—H4B	109.6
O28—W4—O16	169.8 (4)	C12—N4—H4C	109.6
O17—W4—O16	87.5 (3)	Cu1—N4—H4C	109.6
O21—W4—O16	75.6 (3)	H4B—N4—H4C	108.1
O30—W4—O16	75.9 (3)	C14—N5—H5B	109.5
O7—W4—O16	84.7 (3)	C14—N5—H5C	109.5
O27—W5—O30	98.6 (4)	H5B—N5—H5C	109.5
O27—W5—O2	100.1 (4)	C14—N5—H5D	109.5
O30—W5—O2	89.5 (4)	H5B—N5—H5D	109.5
O27—W5—O11	99.1 (4)	H5C—N5—H5D	109.5
O30—W5—O11	91.0 (4)	C13—N6—H6A	109.5
O2—W5—O11	160.5 (4)	C13—N6—H6B	109.5
O27—W5—O29	102.6 (5)	H6A—N6—H6B	109.5
O30—W5—O29	158.8 (4)	C13—N6—H6C	109.5
O2—W5—O29	86.2 (5)	H6A—N6—H6C	109.5
O11—W5—O29	86.4 (4)	H6B—N6—H6C	109.5
O27—W5—O16	168.8 (4)	C2—C1—N2	118.8 (15)
O30—W5—O16	73.5 (3)	C2—C1—C6	126.7 (16)
O2—W5—O16	87.9 (3)	N2—C1—C6	114.5 (14)
O11—W5—O16	73.6 (3)	C3—C2—C1	121.4 (16)
O29—W5—O16	85.6 (4)	C3—C2—H2A	119.3
O19—W6—O4^i	100.9 (4)	C1—C2—H2A	119.3
O19—W6—O13	101.3 (4)	C4—C3—C2	119.9 (17)
O4^i—W6—O13	88.5 (3)	C4—C3—H3A	120.1
O19—W6—O1	96.8 (4)	C2—C3—H3A	120.1
O4^i—W6—O1	88.6 (3)	C3—C4—C5	118.6 (17)
O13—W6—O1	162.0 (3)	C3—C4—H4A	120.7
O19—W6—O20	99.0 (4)	C5—C4—H4A	120.7
O4^i—W6—O20	160.1 (3)	N2—C5—C4	123.3 (16)
O13—W6—O20	88.2 (3)	N2—C5—H5A	118.4
O1—W6—O20	88.5 (3)	C4—C5—H5A	118.4
O19—W6—O5	170.3 (3)	C7—C6—N1	118.3 (15)
O4^i—W6—O5	84.8 (3)	C7—C6—C1	126.0 (17)
O13—W6—O5	86.6 (3)	N1—C6—C1	115.7 (14)
O1—W6—O5	75.4 (3)	C6—C7—C8	122.3 (18)
O20—W6—O5	75.5 (3)	C6—C7—H7A	118.8
O23—W7—O25	101.4 (4)	C8—C7—H7A	118.8
O23—W7—O2	99.7 (4)	C9—C8—C7	119.5 (17)
O25—W7—O2	88.7 (4)	C9—C8—H8A	120.2
O23—W7—O20	99.0 (4)	C7—C8—H8A	120.2
O25—W7—O20	88.2 (4)	C8—C9—C10	118.0 (18)
O2—W7—O20	161.3 (4)	C8—C9—H9A	121.0
O23—W7—O14	97.2 (4)	C10—C9—H9A	121.0
O25—W7—O14	161.4 (4)	N1—C10—C9	124.0 (18)
O2—W7—O14	87.2 (4)	N1—C10—H10A	118.0
O20—W7—O14	89.8 (3)	C9—C10—H10A	118.0
O23—W7—O5	168.2 (4)	N3—C11—C12	106.9 (12)
O25—W7—O5	88.5 (4)	N3—C11—H11A	110.3
O2—W7—O5	86.9 (3)	C12—C11—H11A	110.3
O20—W7—O5	74.6 (3)	N3—C11—H11B	110.3
O14—W7—O5	73.1 (3)	C12—C11—H11B	110.3
O15—W8—O13	102.1 (4)	H11A—C11—H11B	108.6
O15—W8—O18	98.6 (4)	N4—C12—C11	111.0 (13)
O13—W8—O18	90.5 (3)	N4—C12—H12A	109.4
O15—W8—O17^i	99.5 (4)	C11—C12—H12A	109.4
O13—W8—O17^i	87.6 (3)	N4—C12—H12B	109.4
O18—W8—O17^i	161.8 (3)	C11—C12—H12B	109.4
O15—W8—O26	97.6 (4)	H12A—C12—H12B	108.0
O13—W8—O26	160.1 (3)	N6—C13—C14	111.7 (12)
O18—W8—O26	89.0 (3)	N6—C13—H13A	109.3
O17^i—W8—O26	86.7 (3)	C14—C13—H13A	109.3
O15—W8—O6	170.6 (4)	N6—C13—H13B	109.3
O13—W8—O6	85.5 (3)	C14—C13—H13B	109.3
O18—W8—O6	75.7 (3)	H13A—C13—H13B	107.9
O17^i—W8—O6	86.1 (3)	N5—C14—C13	110.2 (12)
O26—W8—O6	75.1 (3)	N5—C14—H14A	109.6
O22—W9—O10^i	100.9 (4)	C13—C14—H14A	109.6
O22—W9—O24	99.1 (4)	N5—C14—H14B	109.6
O10^i—W9—O24	159.9 (3)	C13—C14—H14B	109.6
O22—W9—O3	100.6 (4)	H14A—C14—H14B	108.1
O10^i—W9—O3	87.3 (4)	N3—Cu1—N1	168.6 (5)
O24—W9—O3	89.7 (4)	N3—Cu1—N2	99.5 (5)
O22—W9—O26	95.9 (4)	N1—Cu1—N2	81.7 (6)
O10^i—W9—O26	89.3 (4)	N3—Cu1—N4	83.0 (5)
O24—W9—O26	87.9 (4)	N1—Cu1—N4	96.7 (6)
O3—W9—O26	163.4 (3)	N2—Cu1—N4	175.0 (5)
O22—W9—O6	170.5 (4)	N3—Cu1—O23^iii	88.4 (4)
O10^i—W9—O6	83.9 (3)	N1—Cu1—O23^iii	102.9 (5)
O24—W9—O6	76.2 (3)	N2—Cu1—O23^iii	92.2 (4)
O3—W9—O6	87.7 (3)	N4—Cu1—O23^iii	83.6 (4)
O26—W9—O6	75.8 (3)	O2—W7A—O14	108 (2)
Bi1^i—Bi1—O5	126.7 (2)	O2—W7A—O30	110 (2)
Bi1^i—Bi1—O6	129.6 (2)	O14—W7A—O30	131.9 (11)
O5—Bi1—O6	84.3 (3)	O25—W2A—O20	115 (2)
Bi1^i—Bi1—O16	128.7 (2)	O25—W2A—O18	116 (2)
O5—Bi1—O16	84.2 (3)	O20—W2A—O18	127.0 (11)
O6—Bi1—O16	87.9 (3)	O11—W5A—O24	123.7 (15)
W6—O1—W1	115.0 (4)	H1WA—O1W—H1WB	109.5
W7—O2—W5	149.7 (5)	H2WA—O2W—H2WB	109.5
W3—O3—W9	154.5 (5)
O8—W3—O3—W9	136.1 (12)	O12—W2—O29—W5	121.9 (14)
O11—W3—O3—W9	−123.0 (12)	O24—W2—O29—W5	−140.0 (15)
O4—W3—O3—W9	36.9 (12)	O18—W2—O29—W5	−51 (2)
O21—W3—O3—W9	−30 (2)	O25—W2—O29—W5	21.3 (15)
O16—W3—O3—W9	−45.5 (12)	O6—W2—O29—W5	−66.3 (14)
O9—W1—O7—W4	131.9 (12)	C5—N2—C1—C2	2 (2)
O14—W1—O7—W4	−127.8 (12)	Cu1—N2—C1—C2	−179.0 (13)
O10—W1—O7—W4	31.2 (12)	C5—N2—C1—C6	−179.7 (15)
O1—W1—O7—W4	−40 (2)	Cu1—N2—C1—C6	−0.3 (19)
O5—W1—O7—W4	−52.8 (12)	N2—C1—C2—C3	−5 (3)
O9—W1—O14—W7	−172.3 (5)	C6—C1—C2—C3	176.5 (17)
O7—W1—O14—W7	85.2 (5)	C1—C2—C3—C4	5 (3)
O10—W1—O14—W7	−8.9 (12)	C2—C3—C4—C5	−1 (3)
O1—W1—O14—W7	−75.9 (5)	C1—N2—C5—C4	2 (2)
O5—W1—O14—W7	−1.4 (4)	Cu1—N2—C5—C4	−177.0 (13)
O9—W1—O14—W7A	124.0 (7)	C3—C4—C5—N2	−3 (3)
O7—W1—O14—W7A	21.4 (7)	C10—N1—C6—C7	−4 (2)
O10—W1—O14—W7A	−72.7 (12)	Cu1—N1—C6—C7	166.0 (13)
O1—W1—O14—W7A	−139.7 (7)	C10—N1—C6—C1	175.4 (15)
O5—W1—O14—W7A	−65.2 (7)	Cu1—N1—C6—C1	−14.4 (19)
O28—W4—O17—W8^i	−14.6 (9)	C2—C1—C6—C7	8 (3)
O21—W4—O17—W8^i	85.0 (8)	N2—C1—C6—C7	−170.7 (17)
O30—W4—O17—W8^i	173.5 (8)	C2—C1—C6—N1	−171.6 (17)
O7—W4—O17—W8^i	−114.5 (8)	N2—C1—C6—N1	10 (2)
O16—W4—O17—W8^i	160.6 (8)	N1—C6—C7—C8	4 (3)
O25—W7—O23—Cu1^ii	−125.2 (7)	C1—C6—C7—C8	−175.1 (18)
O2—W7—O23—Cu1^ii	−34.6 (7)	C6—C7—C8—C9	−2 (3)
O20—W7—O23—Cu1^ii	144.8 (7)	C7—C8—C9—C10	−1 (3)
O14—W7—O23—Cu1^ii	53.8 (7)	C6—N1—C10—C9	2 (3)
O5—W7—O23—Cu1^ii	88.5 (19)	Cu1—N1—C10—C9	−166.8 (13)
O23—W7—O25—W2	129.6 (11)	C8—C9—C10—N1	1 (3)
O2—W7—O25—W2	29.9 (11)	Cu1—N3—C11—C12	40.6 (16)
O20—W7—O25—W2	−131.6 (12)	Cu1—N4—C12—C11	26.6 (15)
O14—W7—O25—W2	−47 (2)	N3—C11—C12—N4	−43.5 (18)
O5—W7—O25—W2	−57.0 (11)	N6—C13—C14—N5	−177.3 (11)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O20	0.89	2.52	3.280 (15)	144
N3—H3B···O25	0.89	2.55	3.345 (17)	148
N3—H3C···O2^iii	0.89	2.53	3.255 (15)	139
N3—H3C···O27^iii	0.89	2.58	3.243 (15)	132
N4—H4B···O30^iv	0.89	2.40	3.033 (15)	128
N4—H4C···O15	0.89	2.18	2.965 (15)	147
N5—H5B···O8	0.89	2.14	2.883 (15)	140
N5—H5B···O9^v	0.89	2.55	3.255 (15)	137
N5—H5C···O1^i	0.89	2.00	2.885 (14)	176
N5—H5C···O19^i	0.89	2.65	3.115 (15)	114
N5—H5D···O26^vi	0.89	2.01	2.822 (13)	151
N6—H6A···O8^vii	0.89	2.15	2.817 (15)	131
N6—H6A···O21^vii	0.89	2.28	3.103 (15)	154
N6—H6B···O19^viii	0.89	2.28	2.899 (15)	126
N6—H6B···O22	0.89	2.47	3.164 (14)	135
N6—H6C···O28^v	0.89	1.87	2.733 (15)	164
O1W—H1WA···O22^ix	0.85	2.19	2.70 (6)	118
O2W—H2WA···O12^iii	0.85	2.56	3.14 (3)	127
O2W—H2WB···O24^ix	0.85	2.35	3.02 (3)	136

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