A potential Cu/V-organophosphonate platform for tailored void spaces via terpyridine mold casting

The reaction of appropriate copper and vanadium salts with tetratopic methane tetra-p-phenylphosphonic acid (MTPPA) in the presence of 2,2′:6′:2′′-terpyridine (terpy) yielded the three-dimensional bimetallic copper vanadium phosphonate framework [{Cu(terpy)}₄Cu(VO₂)₄(MTPPA-H)₂]·4H₂O (1). Terpy has no net contribution to the three-dimensional structure providing a potential platform for void space formation via mold-casting. The structure was characterized by single-crystal X-ray diffraction and thermogravimetric analysis (TGA). Magnetic measurements were performed using a SQUID magnetometer. The crystal structure of the methanol solvate of the free ligand, MTPPA·MeOH, was analysed using Hirshfeld surfaces and fingerprint plots.

Computing details

Data collection: SMART v5.630 (Bruker, 2003) for p_1_new; Bruker Instrument Service v2013.12.0.0 (Bruker AXS) for (I). Cell refinement: SAINT v8.34A (Bruker, 2013) for p_1_new; APEX2 v2014.11-0 (Bruker AXS) for (I). Data reduction: SAINT v8.34A (Bruker, 2013) for p_1_new; SAINT V8.34A (Bruker AXS) for (I). Program(s) used to solve structure: XS (Sheldrick, 2008) for p_1_new; SHELXTL V6.14 (Bruker AXS) for (I). Program(s) used to refine structure: XL (Sheldrick, 2008) for p_1_new; SHELXTL V6.14 (Bruker AXS) for (I). Molecular graphics: Olex2 (Dolomanov et al., 2009) for p_1_new; Mercury (Macrae et al., 2006) for (I). Software used to prepare material for publication: Olex2 (Dolomanov et al., 2009) for p_1_new; PLATON V1.16 (Spek, 2009), SHELXTL V6.14 (Bruker AXS) for (I).

(p_1_new)

Crystal data

C55H38.47Cu2.24N6O15.88P4V1.94·2(H2O)	Z = 2
Mr = 1438.47	F(000) = 1454
Triclinic, P1	Dx = 1.734 Mg m^−3
a = 13.6173 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 14.3205 (9) Å	Cell parameters from 9857 reflections
c = 15.4896 (9) Å	θ = 2.4–31.5°
α = 77.4902 (10)°	µ = 1.37 mm^−1
β = 71.7418 (10)°	T = 100 K
γ = 76.5041 (11)°	Plate, green
V = 2755.4 (3) Å^3	0.33 × 0.16 × 0.06 mm

Data collection

Bruker SMART Platform with a Apex I-detector diffractometer	15399 independent reflections
Radiation source: sealed X-ray tube	13434 reflections with I > 2σ(I)
Parallel,graphite monochromator	Rint = 0.018
Detector resolution: 7.9 pixels mm^-1	θmax = 31.5°, θmin = 1.6°
ω scans	h = −19→17
Absorption correction: multi-scan SADABS-2014/4 (Bruker,2014/4) was used for absorption correction. wR2(int) was 0.0409 before and 0.0281 after correction. The Ratio of minimum to maximum transmission is 0.8998. The λ/2 correction factor is 0.00150.	k = −20→20
Tmin = 0.672, Tmax = 0.746	l = −22→17
22427 measured reflections

Refinement

Refinement on F^2	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.119	w = 1/[σ^2(Fo^2) + (0.0495P)^2 + 4.888P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
15399 reflections	Δρmax = 1.34 e Å^−3
922 parameters	Δρmin = −0.80 e Å^−3
181 restraints

Special details

Experimental. The data collection nominally covered a full sphere of reciprocal space by a combination of 4 sets of ω scans each set at different φ and/or 2θ angles and each scan (10 s exposure) covering -0.300° degrees in ω. The crystal to detector distance was 4.956 cm.

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. Several parts of the network exhibits strong positional and occupational disorder. The disorder prevented for some split atom positions the free refinement of the anisotropic displacement parameters, as for the terpyridin ligand coordinating Cu2. For some other disordered atom positions, as for the oxygen atoms of the phosphonate group of P1, P1A and P1B, isotropic displacement parameters were used. Here as well some distance restraints were used. If a full occupancy of the major component is assumed, the ideal overall composition of 1 would be [{Cu(C15H11N3)}4 Cu(VO2)4 (C25H16P4O12H)2].4H2O. The disorder seems to be triggered by the mixed occupancy of the Cu3/V3-site, where about 50 percent of the Cu atoms is substituted by a VO-unit in two different orientations. This disorder causes an underoccupancy of the neighboring distorted VO4-tetrahedra. As a result, the tetrahedra have an occupancy of about 75 percent only. Additional electron density in the vicinty of the tetrahedral centers found in the difference Fourier map accounts for an additional occupancy of about 9.7 percent of a V-atom close to the position of V1 and in total about 11.3 percent of a V-atom close to the position of V2. Unfortunately, due to the low occupancies, we were not able to determine the respective coordination polyhedra around the residual V-centers (V1A, V2A and V2B). Regarding the charges, the Cu2±ions on the Cu3 positions are formally replaced by a VO3±unit, which in turn requires an abstraction of the last acidic proton H9 a the MTPPA-unit too, forming an anion with an 8-fold charge to maintain electroneutrality. The Cu/V mass percent ration of an assumed non-disordered structure is 1.559/1. By laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) on three single crystals a mass percent ratio of Cu/V of 1.50 (4)/1 has been determined, which is fairly close to the value of 1.43/1 we find from the structure analysis. The agreement is be even better if we assume that the atom-sites V1A, V2A and V2B contain an certain amount of Cu, too. Since we were not able to completely resolve the residual density in the disordered areas, a further detailed analysis of charges and building units present is not possible here. Initially, we assumed, that a certain amount of fluoride and sodium-cations (origination from the sodium vanadate and HF used for thr the synthesis) may have be incorporated into the framework. However, element analyses on single crystals of 1 by LA-ICP-MS and by EDX reavealed, that only traces of sodium (Na/V mass percent ratio of about 0.0007 (5)/1) are present and no significant amounts of F or any other element other than C,O,P,Cu and V can be detected.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.88522 (2)	0.39613 (2)	0.03713 (2)	0.01715 (7)
P2	0.64228 (5)	0.85506 (4)	0.62773 (4)	0.01508 (12)
P3	0.47136 (5)	1.14709 (4)	0.64840 (4)	0.01501 (12)
P4	0.89663 (5)	0.58920 (4)	0.11186 (4)	0.01557 (12)
O4	0.54465 (14)	0.90682 (12)	0.60015 (12)	0.0170 (3)
O7	0.53277 (16)	1.07809 (13)	0.70883 (14)	0.0250 (4)
O8	0.46272 (16)	1.10730 (13)	0.56965 (13)	0.0225 (4)
O9	0.36262 (15)	1.18878 (15)	0.70933 (15)	0.0276 (4)
H9	0.3198	1.2079	0.6775	0.041*	0.4709
O11	0.83162 (14)	0.55040 (14)	0.06986 (12)	0.0195 (3)
O12	0.98525 (14)	0.44096 (14)	−0.07351 (12)	0.0199 (3)
O19	0.62899 (19)	0.60927 (19)	0.0556 (2)	0.0458 (6)
H19A	0.6888	0.5888	0.0687	0.069*
H19B	0.6369	0.6528	0.0063	0.069*
N1	0.97006 (16)	0.33017 (15)	0.13226 (14)	0.0177 (4)
N2	0.78157 (16)	0.32914 (15)	0.13278 (14)	0.0178 (4)
N3	0.76884 (16)	0.41879 (15)	−0.02596 (14)	0.0178 (4)
C1	0.76649 (18)	1.44288 (16)	0.52695 (15)	0.0144 (4)
C2	0.85575 (18)	1.37687 (16)	0.56436 (17)	0.0158 (4)
C3	0.9518 (2)	1.33771 (19)	0.50776 (19)	0.0237 (5)
H3	0.9649	1.3532	0.4428	0.028*
C4	1.0281 (2)	1.2766 (2)	0.5450 (2)	0.0276 (6)
H4	1.0929	1.2508	0.5052	0.033*
C5	1.0116 (2)	1.25246 (19)	0.6394 (2)	0.0240 (5)
C6	0.9136 (2)	1.28762 (18)	0.69748 (19)	0.0212 (5)
H6	0.8998	1.2701	0.7624	0.025*
C7	0.83728 (19)	1.34811 (17)	0.65943 (17)	0.0176 (4)
H7	0.7707	1.3706	0.6990	0.021*
C8	0.72919 (18)	1.54004 (15)	0.56470 (15)	0.0131 (4)
C9	0.78516 (18)	1.57253 (16)	0.61043 (16)	0.0141 (4)
H9A	0.8436	1.5302	0.6271	0.017*
C10	0.75595 (19)	1.66675 (16)	0.63195 (16)	0.0151 (4)
H10	0.7944	1.6874	0.6638	0.018*
C11	0.67173 (18)	1.73085 (16)	0.60770 (15)	0.0141 (4)
C12	0.61464 (19)	1.69810 (16)	0.56296 (16)	0.0162 (4)
H12	0.5559	1.7403	0.5468	0.019*
C13	0.64308 (19)	1.60445 (16)	0.54206 (16)	0.0161 (4)
H13	0.6033	1.5835	0.5117	0.019*
C14	0.68132 (18)	1.37921 (16)	0.55418 (16)	0.0150 (4)
C15	0.58471 (19)	1.39689 (16)	0.61795 (16)	0.0161 (4)
H15	0.5649	1.4547	0.6445	0.019*
C16	0.51579 (18)	1.33078 (17)	0.64383 (17)	0.0168 (4)
H16	0.4498	1.3439	0.6880	0.020*
C17	0.54312 (19)	1.24592 (16)	0.60533 (16)	0.0157 (4)
C18	0.6390 (2)	1.22942 (18)	0.53924 (18)	0.0226 (5)
H18	0.6577	1.1730	0.5106	0.027*
C19	0.7072 (2)	1.29427 (18)	0.51492 (18)	0.0210 (5)
H19	0.7731	1.2811	0.4707	0.025*
C20	0.80107 (19)	1.47513 (17)	0.42197 (16)	0.0156 (4)
C21	0.74162 (19)	1.46983 (19)	0.36539 (17)	0.0191 (5)
H21	0.6798	1.4421	0.3912	0.023*
C22	0.77129 (19)	1.50446 (19)	0.27176 (17)	0.0188 (5)
H22	0.7292	1.5009	0.2343	0.023*
C23	0.86215 (18)	1.54442 (17)	0.23226 (16)	0.0156 (4)
C24	0.92071 (19)	1.55242 (18)	0.28931 (17)	0.0178 (4)
H24	0.9823	1.5806	0.2635	0.021*
C25	0.8898 (2)	1.51981 (18)	0.38270 (17)	0.0180 (4)
H25	0.9291	1.5277	0.4209	0.022*
C26	1.0702 (2)	0.33100 (19)	0.12576 (17)	0.0198 (5)
H26	1.1098	0.3674	0.0730	0.024*
C27	1.1183 (2)	0.2805 (2)	0.19349 (18)	0.0227 (5)
H27	1.1899	0.2819	0.1862	0.027*
C28	1.0615 (2)	0.22806 (19)	0.27148 (18)	0.0227 (5)
H28	1.0932	0.1931	0.3183	0.027*
C29	0.9569 (2)	0.22773 (19)	0.27974 (17)	0.0211 (5)
H29	0.9156	0.1930	0.3327	0.025*
C30	0.9140 (2)	0.27890 (18)	0.20933 (17)	0.0182 (4)
C31	0.8050 (2)	0.28036 (18)	0.20968 (17)	0.0189 (5)
C32	0.7315 (2)	0.2342 (2)	0.28001 (18)	0.0232 (5)
H32	0.7481	0.1997	0.3348	0.028*
C33	0.6334 (2)	0.2400 (2)	0.26789 (19)	0.0264 (6)
H33	0.5816	0.2096	0.3151	0.032*
C34	0.6107 (2)	0.2898 (2)	0.18715 (19)	0.0244 (5)
H34	0.5436	0.2942	0.1785	0.029*
C35	0.68834 (19)	0.33345 (18)	0.11883 (17)	0.0187 (5)
C36	0.68175 (19)	0.38282 (17)	0.02589 (17)	0.0169 (4)
C37	0.5971 (2)	0.38953 (18)	−0.00736 (18)	0.0202 (5)
H37	0.5369	0.3632	0.0303	0.024*
C38	0.6014 (2)	0.43543 (19)	−0.09681 (19)	0.0212 (5)
H38	0.5441	0.4411	−0.1214	0.025*
C39	0.6901 (2)	0.47282 (19)	−0.14959 (18)	0.0210 (5)
H39	0.6944	0.5049	−0.2108	0.025*
C40	0.7731 (2)	0.46294 (19)	−0.11218 (17)	0.0200 (5)
H40	0.8343	0.4882	−0.1487	0.024*
Cu2	0.56018 (6)	0.97573 (6)	0.79726 (6)	0.01538 (12)	0.7352 (14)
Cu3	0.5000	1.0000	0.5000	0.01047 (13)*	0.4709
V1	0.95076 (9)	0.79335 (5)	0.10550 (6)	0.01270 (15)	0.7352 (14)
V2	0.77601 (4)	0.97960 (4)	0.44990 (4)	0.01551 (14)	0.7352 (14)
P1	0.88092 (7)	0.81892 (8)	0.32345 (8)	0.01655 (19)	0.7352 (14)
O1	0.8668 (2)	0.91785 (19)	0.35435 (18)	0.0244 (5)	0.7352 (14)
O2	0.7864 (2)	0.7721 (2)	0.3632 (2)	0.0299 (6)	0.7352 (14)
O3	0.9169 (2)	0.8363 (2)	0.2171 (2)	0.0224 (6)	0.7352 (14)
O5	0.64045 (18)	0.85336 (19)	0.72429 (18)	0.0148 (4)*	0.7352 (14)
O6	0.7417 (2)	0.8989 (2)	0.55903 (18)	0.0176 (5)*	0.7352 (14)
O10	0.87623 (18)	0.7029 (3)	0.1010 (3)	0.0172 (6)	0.7352 (14)
O13	0.9359 (3)	0.8868 (3)	0.0278 (3)	0.0278 (8)	0.7352 (14)
O14	1.07312 (19)	0.74676 (17)	0.07921 (18)	0.0212 (5)	0.7352 (14)
O15	0.8349 (3)	1.0643 (2)	0.4592 (2)	0.0271 (6)	0.7352 (14)
O16	0.6712 (2)	1.0386 (2)	0.4240 (2)	0.0225 (6)	0.7352 (14)
N4	0.7041 (3)	1.0021 (2)	0.7853 (2)	0.0191 (6)	0.7352 (14)
N5	0.5752 (3)	0.9153 (2)	0.9179 (2)	0.0221 (6)	0.7352 (14)
N6	0.4157 (3)	0.9410 (5)	0.8554 (5)	0.0274 (11)	0.7352 (14)
C41	0.7653 (3)	1.0467 (3)	0.7096 (3)	0.0257 (7)	0.7352 (14)
H41	0.7378	1.0755	0.6588	0.031*	0.7352 (14)
C42	0.8686 (3)	1.0524 (3)	0.7031 (3)	0.0321 (8)	0.7352 (14)
H42	0.9115	1.0830	0.6482	0.038*	0.7352 (14)
C43	0.9067 (4)	1.0124 (3)	0.7780 (4)	0.0371 (9)	0.7352 (14)
H43	0.9758	1.0172	0.7761	0.045*	0.7352 (14)
C44	0.8433 (4)	0.9648 (4)	0.8572 (5)	0.0344 (11)	0.7352 (14)
H44	0.8688	0.9360	0.9092	0.041*	0.7352 (14)
C45	0.7423 (3)	0.9607 (3)	0.8577 (3)	0.0235 (7)	0.7352 (14)
C46	0.6679 (4)	0.9127 (3)	0.9346 (3)	0.0232 (7)	0.7352 (14)
C47	0.6826 (5)	0.8680 (3)	1.0205 (3)	0.0372 (10)	0.7352 (14)
H47	0.7470	0.8639	1.0341	0.045*	0.7352 (14)
C48	0.5986 (5)	0.8295 (4)	1.0858 (3)	0.0403 (11)	0.7352 (14)
H48	0.6065	0.7988	1.1447	0.048*	0.7352 (14)
C49	0.5065 (4)	0.8346 (3)	1.0673 (3)	0.0373 (10)	0.7352 (14)
H49	0.4503	0.8085	1.1127	0.045*	0.7352 (14)
C50	0.4952 (4)	0.8795 (3)	0.9795 (3)	0.0263 (8)	0.7352 (14)
C51	0.4021 (4)	0.8945 (3)	0.9440 (3)	0.0298 (9)	0.7352 (14)
C52	0.3055 (5)	0.8683 (3)	0.9952 (4)	0.0442 (13)	0.7352 (14)
H52	0.2967	0.8336	1.0560	0.053*	0.7352 (14)
C53	0.2241 (5)	0.8931 (5)	0.9565 (6)	0.0539 (18)	0.7352 (14)
H53	0.1573	0.8778	0.9918	0.065*	0.7352 (14)
C54	0.2371 (5)	0.9412 (4)	0.8649 (5)	0.0510 (17)	0.7352 (14)
H54	0.1806	0.9573	0.8376	0.061*	0.7352 (14)
C55	0.3364 (8)	0.9643 (8)	0.8155 (8)	0.0366 (16)	0.7352 (14)
H55	0.3478	0.9965	0.7537	0.044*	0.7352 (14)
Cu2A	0.5369 (2)	0.9667 (2)	0.81309 (19)	0.01538 (12)	0.2648 (14)
V1A	0.9234 (8)	0.7958 (8)	0.1146 (8)	0.036 (4)*	0.097 (3)
V2A	0.8391 (5)	0.9555 (5)	0.4768 (5)	0.0265 (19)*	0.074 (2)
V3	0.48270 (12)	0.99669 (12)	0.50607 (12)	0.01047 (13)*	0.2645
P1A	0.8992 (4)	0.8347 (4)	0.2758 (6)	0.0236 (9)*	0.1658 (19)
O1A	0.8196 (13)	0.8947 (11)	0.3518 (11)	0.037 (3)*	0.1658 (19)
O2A	0.8349 (10)	0.7741 (9)	0.2551 (9)	0.029 (3)*	0.1658 (19)
O3A	0.9567 (13)	0.8886 (12)	0.1947 (11)	0.042 (3)*	0.1658 (19)
O5A	0.6121 (6)	0.8495 (5)	0.7371 (5)	0.0148 (4)*	0.2648 (14)
O6A	0.7401 (7)	0.8995 (6)	0.5816 (6)	0.0176 (5)*	0.2648 (14)
O13A	0.996 (3)	0.916 (2)	0.530 (2)	0.086 (11)*	0.140 (10)
O16A	0.6372 (7)	1.0326 (8)	0.4453 (8)	0.0225 (6)	0.2648 (14)
N4A	0.6779 (8)	0.9815 (6)	0.8250 (7)	0.0191 (6)	0.2648 (14)
N5A	0.5303 (10)	0.8997 (7)	0.9378 (8)	0.0221 (6)	0.2648 (14)
N6A	0.3893 (14)	0.9393 (17)	0.8521 (17)	0.0274 (11)	0.2648 (14)
C41A	0.7503 (11)	1.0250 (9)	0.7575 (10)	0.0257 (7)	0.2648 (14)
H41A	0.7334	1.0577	0.7024	0.031*	0.2648 (14)
C42A	0.8523 (10)	1.0233 (9)	0.7666 (10)	0.0321 (8)	0.2648 (14)
H42A	0.9032	1.0553	0.7200	0.038*	0.2648 (14)
C43A	0.8712 (14)	0.9729 (16)	0.8463 (17)	0.0371 (9)	0.2648 (14)
H43A	0.9380	0.9698	0.8550	0.045*	0.2648 (14)
C44A	0.7998 (10)	0.9262 (9)	0.9147 (10)	0.0344 (11)	0.2648 (14)
H44A	0.8158	0.8911	0.9695	0.041*	0.2648 (14)
C45A	0.7017 (11)	0.9327 (9)	0.8999 (11)	0.0235 (7)	0.2648 (14)
C46A	0.6137 (10)	0.8909 (7)	0.9677 (7)	0.0232 (7)	0.2648 (14)
C47A	0.6103 (17)	0.8462 (11)	1.0570 (11)	0.0372 (10)	0.2648 (14)
H47A	0.6688	0.8381	1.0806	0.045*	0.2648 (14)
C48A	0.5160 (13)	0.8129 (9)	1.1124 (9)	0.0403 (11)	0.2648 (14)
H48A	0.5112	0.7821	1.1740	0.048*	0.2648 (14)
C49A	0.4307 (13)	0.8251 (8)	1.0771 (8)	0.0373 (10)	0.2648 (14)
H49A	0.3680	0.8025	1.1139	0.045*	0.2648 (14)
C50A	0.4395 (12)	0.8714 (8)	0.9862 (8)	0.0263 (8)	0.2648 (14)
C51A	0.3577 (11)	0.8923 (9)	0.9383 (10)	0.0298 (9)	0.2648 (14)
C52A	0.2560 (18)	0.8691 (12)	0.9739 (14)	0.0442 (13)	0.2648 (14)
H52A	0.2353	0.8323	1.0333	0.053*	0.2648 (14)
C53A	0.1885 (14)	0.9007 (12)	0.9208 (15)	0.0539 (18)	0.2648 (14)
H53A	0.1173	0.8929	0.9473	0.065*	0.2648 (14)
C54A	0.2192 (15)	0.9440 (15)	0.8293 (17)	0.0510 (17)	0.2648 (14)
H54A	0.1740	0.9620	0.7902	0.061*	0.2648 (14)
C55A	0.323 (3)	0.958 (3)	0.801 (3)	0.0366 (16)	0.2648 (14)
H55A	0.3496	0.9841	0.7381	0.044*	0.2648 (14)
V2B	0.7880 (10)	0.9234 (11)	0.4634 (9)	0.027 (2)*	0.0389 (18)
P1B	0.8900 (7)	0.8553 (7)	0.3137 (6)	0.0236 (9)*	0.099 (2)
O1B	0.7876 (15)	0.8436 (15)	0.3824 (13)	0.031 (3)*	0.099 (2)
O2B	0.894 (2)	0.817 (2)	0.2312 (16)	0.031 (3)*	0.099 (2)
O3B	0.9123 (16)	0.9505 (13)	0.2961 (14)	0.031 (3)*	0.099 (2)
O10A	0.8449 (7)	0.7026 (10)	0.1083 (10)	0.0172 (6)	0.2648 (14)
O17	0.8559 (11)	1.0364 (10)	0.4352 (11)	0.0271 (6)	0.180 (7)
O18	0.7490 (14)	0.7712 (12)	0.1997 (12)	0.023 (5)*	0.109 (8)
O21	0.8987 (18)	0.8852 (18)	0.0435 (17)	0.0278 (8)	0.131 (8)
O24	0.38317 (18)	0.29779 (16)	0.13384 (16)	0.0353 (5)
H24A	0.3547	0.3508	0.1577	0.053*
H24B	0.3783	0.2478	0.1774	0.053*
O12A	0.951 (4)	0.913 (3)	0.509 (3)	0.086 (10)*	0.115 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01616 (14)	0.02409 (15)	0.01259 (14)	−0.01198 (11)	−0.00153 (10)	−0.00032 (11)
P2	0.0173 (3)	0.0110 (2)	0.0185 (3)	−0.0038 (2)	−0.0058 (2)	−0.0029 (2)
P3	0.0165 (3)	0.0132 (2)	0.0161 (3)	−0.0059 (2)	−0.0032 (2)	−0.0022 (2)
P4	0.0174 (3)	0.0183 (3)	0.0118 (3)	−0.0072 (2)	−0.0020 (2)	−0.0027 (2)
O4	0.0208 (8)	0.0144 (7)	0.0164 (8)	−0.0037 (6)	−0.0067 (6)	−0.0007 (6)
O7	0.0328 (10)	0.0187 (8)	0.0281 (10)	−0.0079 (7)	−0.0171 (8)	0.0032 (7)
O8	0.0352 (10)	0.0144 (8)	0.0229 (9)	−0.0059 (7)	−0.0138 (8)	−0.0030 (6)
O9	0.0179 (9)	0.0259 (9)	0.0343 (11)	−0.0071 (7)	0.0042 (8)	−0.0081 (8)
O11	0.0169 (8)	0.0305 (9)	0.0135 (8)	−0.0104 (7)	−0.0029 (6)	−0.0033 (7)
O12	0.0158 (8)	0.0307 (9)	0.0147 (8)	−0.0118 (7)	−0.0014 (6)	−0.0025 (7)
O19	0.0323 (12)	0.0388 (13)	0.077 (2)	0.0021 (10)	−0.0276 (13)	−0.0212 (13)
N1	0.0184 (9)	0.0226 (10)	0.0125 (9)	−0.0101 (8)	−0.0007 (7)	−0.0020 (7)
N2	0.0174 (9)	0.0219 (9)	0.0153 (9)	−0.0104 (8)	−0.0013 (7)	−0.0024 (7)
N3	0.0169 (9)	0.0223 (10)	0.0152 (10)	−0.0084 (8)	−0.0010 (7)	−0.0049 (7)
C1	0.0180 (10)	0.0138 (9)	0.0120 (10)	−0.0066 (8)	−0.0007 (8)	−0.0044 (7)
C2	0.0158 (10)	0.0123 (9)	0.0196 (11)	−0.0060 (8)	−0.0010 (8)	−0.0053 (8)
C3	0.0218 (12)	0.0202 (11)	0.0237 (13)	−0.0038 (9)	0.0024 (10)	−0.0053 (9)
C4	0.0176 (12)	0.0241 (12)	0.0348 (15)	−0.0014 (9)	0.0023 (10)	−0.0079 (11)
C5	0.0154 (11)	0.0207 (11)	0.0383 (15)	−0.0024 (9)	−0.0083 (10)	−0.0092 (10)
C6	0.0200 (11)	0.0211 (11)	0.0245 (13)	−0.0030 (9)	−0.0077 (10)	−0.0062 (9)
C7	0.0142 (10)	0.0179 (10)	0.0210 (12)	−0.0041 (8)	−0.0018 (8)	−0.0069 (8)
C8	0.0183 (10)	0.0118 (9)	0.0093 (9)	−0.0065 (8)	−0.0012 (8)	−0.0013 (7)
C9	0.0139 (10)	0.0138 (9)	0.0150 (10)	−0.0046 (7)	−0.0026 (8)	−0.0028 (8)
C10	0.0189 (11)	0.0145 (9)	0.0150 (10)	−0.0054 (8)	−0.0062 (8)	−0.0038 (8)
C11	0.0176 (10)	0.0123 (9)	0.0127 (10)	−0.0050 (8)	−0.0029 (8)	−0.0020 (7)
C12	0.0192 (11)	0.0137 (9)	0.0172 (11)	−0.0052 (8)	−0.0070 (9)	0.0002 (8)
C13	0.0217 (11)	0.0149 (10)	0.0140 (10)	−0.0073 (8)	−0.0066 (8)	−0.0003 (8)
C14	0.0182 (10)	0.0144 (9)	0.0132 (10)	−0.0083 (8)	−0.0009 (8)	−0.0030 (8)
C15	0.0187 (11)	0.0130 (9)	0.0159 (11)	−0.0047 (8)	−0.0013 (8)	−0.0043 (8)
C16	0.0150 (10)	0.0161 (10)	0.0180 (11)	−0.0051 (8)	−0.0010 (8)	−0.0025 (8)
C17	0.0191 (11)	0.0144 (9)	0.0157 (11)	−0.0081 (8)	−0.0034 (8)	−0.0031 (8)
C18	0.0273 (13)	0.0186 (11)	0.0221 (12)	−0.0110 (9)	0.0030 (10)	−0.0107 (9)
C19	0.0208 (11)	0.0204 (11)	0.0203 (12)	−0.0097 (9)	0.0056 (9)	−0.0103 (9)
C20	0.0187 (11)	0.0169 (10)	0.0116 (10)	−0.0076 (8)	0.0002 (8)	−0.0048 (8)
C21	0.0179 (11)	0.0261 (12)	0.0150 (11)	−0.0115 (9)	0.0003 (8)	−0.0059 (9)
C22	0.0170 (11)	0.0265 (12)	0.0150 (11)	−0.0103 (9)	−0.0012 (8)	−0.0053 (9)
C23	0.0164 (10)	0.0180 (10)	0.0127 (10)	−0.0056 (8)	−0.0007 (8)	−0.0050 (8)
C24	0.0187 (11)	0.0205 (11)	0.0157 (11)	−0.0107 (9)	−0.0020 (8)	−0.0026 (8)
C25	0.0201 (11)	0.0219 (11)	0.0157 (11)	−0.0115 (9)	−0.0040 (9)	−0.0035 (9)
C26	0.0195 (11)	0.0255 (12)	0.0157 (11)	−0.0105 (9)	−0.0026 (9)	−0.0022 (9)
C27	0.0204 (12)	0.0295 (13)	0.0213 (12)	−0.0098 (10)	−0.0064 (10)	−0.0036 (10)
C28	0.0267 (13)	0.0251 (12)	0.0191 (12)	−0.0084 (10)	−0.0084 (10)	−0.0018 (9)
C29	0.0255 (12)	0.0228 (11)	0.0158 (11)	−0.0097 (9)	−0.0039 (9)	−0.0019 (9)
C30	0.0193 (11)	0.0212 (11)	0.0158 (11)	−0.0095 (9)	−0.0018 (9)	−0.0045 (8)
C31	0.0207 (11)	0.0219 (11)	0.0152 (11)	−0.0090 (9)	−0.0025 (9)	−0.0032 (9)
C32	0.0249 (13)	0.0274 (12)	0.0174 (12)	−0.0119 (10)	−0.0027 (10)	−0.0005 (9)
C33	0.0231 (13)	0.0328 (14)	0.0211 (13)	−0.0142 (11)	0.0001 (10)	0.0014 (10)
C34	0.0186 (12)	0.0287 (13)	0.0248 (13)	−0.0112 (10)	−0.0013 (10)	−0.0011 (10)
C35	0.0170 (11)	0.0214 (11)	0.0182 (11)	−0.0077 (9)	−0.0021 (9)	−0.0036 (9)
C36	0.0161 (10)	0.0180 (10)	0.0172 (11)	−0.0073 (8)	−0.0020 (8)	−0.0037 (8)
C37	0.0167 (11)	0.0210 (11)	0.0227 (12)	−0.0069 (9)	−0.0024 (9)	−0.0038 (9)
C38	0.0185 (11)	0.0227 (11)	0.0253 (13)	−0.0045 (9)	−0.0074 (9)	−0.0067 (9)
C39	0.0226 (12)	0.0233 (11)	0.0168 (11)	−0.0042 (9)	−0.0039 (9)	−0.0047 (9)
C40	0.0192 (11)	0.0252 (12)	0.0155 (11)	−0.0089 (9)	−0.0003 (9)	−0.0045 (9)
Cu2	0.0193 (4)	0.0151 (2)	0.0114 (3)	−0.0060 (2)	−0.0037 (2)	0.0009 (2)
V1	0.0148 (4)	0.0114 (3)	0.0115 (3)	−0.0032 (3)	−0.0039 (3)	0.00046 (19)
V2	0.0142 (3)	0.0124 (3)	0.0159 (3)	−0.00148 (18)	−0.00193 (19)	0.00172 (19)
P1	0.0127 (4)	0.0184 (4)	0.0177 (6)	0.0002 (3)	−0.0054 (3)	−0.0025 (4)
O1	0.0279 (14)	0.0180 (11)	0.0224 (13)	0.0030 (10)	−0.0041 (11)	−0.0046 (9)
O2	0.0173 (12)	0.0357 (15)	0.0339 (15)	−0.0098 (11)	−0.0090 (11)	0.0087 (12)
O3	0.0230 (16)	0.0275 (16)	0.0149 (14)	−0.0019 (11)	−0.0060 (10)	−0.0010 (11)
O10	0.0085 (16)	0.0206 (9)	0.0228 (12)	−0.0046 (15)	−0.0038 (16)	−0.0028 (8)
O13	0.041 (2)	0.0238 (13)	0.0194 (17)	−0.0121 (17)	−0.0105 (16)	0.0052 (11)
O14	0.0161 (11)	0.0155 (10)	0.0298 (13)	−0.0059 (8)	0.0014 (9)	−0.0072 (9)
O15	0.0268 (15)	0.0197 (15)	0.0343 (18)	−0.0082 (12)	−0.0032 (13)	−0.0067 (11)
O16	0.0164 (17)	0.0226 (11)	0.0255 (19)	−0.0005 (13)	−0.0045 (13)	−0.0028 (12)
N4	0.0256 (16)	0.0162 (13)	0.0176 (17)	−0.0048 (11)	−0.0077 (13)	−0.0031 (12)
N5	0.0386 (19)	0.0122 (12)	0.0099 (14)	−0.0008 (12)	−0.0025 (13)	−0.0007 (10)
N6	0.025 (3)	0.0151 (10)	0.0331 (14)	−0.006 (2)	0.003 (2)	0.0019 (10)
C41	0.0295 (18)	0.0234 (17)	0.026 (2)	−0.0114 (13)	−0.0082 (16)	−0.0011 (15)
C42	0.0288 (18)	0.0303 (18)	0.042 (2)	−0.0113 (14)	−0.0097 (17)	−0.0088 (16)
C43	0.028 (2)	0.038 (2)	0.054 (3)	−0.0043 (16)	−0.0189 (19)	−0.0155 (18)
C44	0.036 (3)	0.031 (2)	0.044 (3)	−0.0013 (19)	−0.020 (2)	−0.0135 (17)
C45	0.0326 (18)	0.0186 (15)	0.0224 (18)	0.0008 (13)	−0.0136 (14)	−0.0067 (13)
C46	0.040 (2)	0.0156 (15)	0.0142 (16)	0.0024 (13)	−0.0114 (14)	−0.0048 (12)
C47	0.069 (3)	0.0250 (18)	0.0205 (18)	0.0004 (18)	−0.0245 (19)	−0.0015 (14)
C48	0.076 (3)	0.025 (2)	0.0149 (19)	−0.001 (2)	−0.014 (2)	−0.0001 (15)
C49	0.067 (3)	0.0187 (15)	0.0148 (16)	−0.0050 (18)	0.0006 (18)	0.0003 (12)
C50	0.041 (2)	0.0129 (13)	0.0144 (15)	−0.0017 (16)	0.0050 (17)	−0.0035 (11)
C51	0.033 (2)	0.0128 (12)	0.0315 (17)	−0.0058 (17)	0.0102 (19)	−0.0040 (12)
C52	0.043 (3)	0.0212 (17)	0.051 (3)	−0.0155 (19)	0.021 (2)	−0.0095 (17)
C53	0.038 (3)	0.027 (2)	0.081 (4)	−0.017 (2)	0.023 (2)	−0.022 (3)
C54	0.027 (2)	0.0220 (16)	0.096 (5)	−0.0112 (17)	0.002 (2)	−0.015 (3)
C55	0.027 (3)	0.017 (2)	0.063 (4)	−0.0120 (17)	−0.008 (2)	0.000 (2)
Cu2A	0.0193 (4)	0.0151 (2)	0.0114 (3)	−0.0060 (2)	−0.0037 (2)	0.0009 (2)
O16A	0.0164 (17)	0.0226 (11)	0.0255 (19)	−0.0005 (13)	−0.0045 (13)	−0.0028 (12)
N4A	0.0256 (16)	0.0162 (13)	0.0176 (17)	−0.0048 (11)	−0.0077 (13)	−0.0031 (12)
N5A	0.0386 (19)	0.0122 (12)	0.0099 (14)	−0.0008 (12)	−0.0025 (13)	−0.0007 (10)
N6A	0.025 (3)	0.0151 (10)	0.0331 (14)	−0.006 (2)	0.003 (2)	0.0019 (10)
C41A	0.0295 (18)	0.0234 (17)	0.026 (2)	−0.0114 (13)	−0.0082 (16)	−0.0011 (15)
C42A	0.0288 (18)	0.0303 (18)	0.042 (2)	−0.0113 (14)	−0.0097 (17)	−0.0088 (16)
C43A	0.028 (2)	0.038 (2)	0.054 (3)	−0.0043 (16)	−0.0189 (19)	−0.0155 (18)
C44A	0.036 (3)	0.031 (2)	0.044 (3)	−0.0013 (19)	−0.020 (2)	−0.0135 (17)
C45A	0.0326 (18)	0.0186 (15)	0.0224 (18)	0.0008 (13)	−0.0136 (14)	−0.0067 (13)
C46A	0.040 (2)	0.0156 (15)	0.0142 (16)	0.0024 (13)	−0.0114 (14)	−0.0048 (12)
C47A	0.069 (3)	0.0250 (18)	0.0205 (18)	0.0004 (18)	−0.0245 (19)	−0.0015 (14)
C48A	0.076 (3)	0.025 (2)	0.0149 (19)	−0.001 (2)	−0.014 (2)	−0.0001 (15)
C49A	0.067 (3)	0.0187 (15)	0.0148 (16)	−0.0050 (18)	0.0006 (18)	0.0003 (12)
C50A	0.041 (2)	0.0129 (13)	0.0144 (15)	−0.0017 (16)	0.0050 (17)	−0.0035 (11)
C51A	0.033 (2)	0.0128 (12)	0.0315 (17)	−0.0058 (17)	0.0102 (19)	−0.0040 (12)
C52A	0.043 (3)	0.0212 (17)	0.051 (3)	−0.0155 (19)	0.021 (2)	−0.0095 (17)
C53A	0.038 (3)	0.027 (2)	0.081 (4)	−0.017 (2)	0.023 (2)	−0.022 (3)
C54A	0.027 (2)	0.0220 (16)	0.096 (5)	−0.0112 (17)	0.002 (2)	−0.015 (3)
C55A	0.027 (3)	0.017 (2)	0.063 (4)	−0.0120 (17)	−0.008 (2)	0.000 (2)
O10A	0.0085 (16)	0.0206 (9)	0.0228 (12)	−0.0046 (15)	−0.0038 (16)	−0.0028 (8)
O17	0.0268 (15)	0.0197 (15)	0.0343 (18)	−0.0082 (12)	−0.0032 (13)	−0.0067 (11)
O21	0.041 (2)	0.0238 (13)	0.0194 (17)	−0.0121 (17)	−0.0105 (16)	0.0052 (11)
O24	0.0320 (11)	0.0278 (10)	0.0393 (13)	−0.0053 (9)	−0.0055 (10)	0.0020 (9)

Geometric parameters (Å, º)

Cu1—O11	2.2740 (19)	C40—H40	0.9500
Cu1—O12	1.9166 (17)	Cu2—O5	2.176 (3)
Cu1—N1	2.086 (2)	Cu2—N4	2.027 (4)
Cu1—N2	1.953 (2)	Cu2—N5	1.933 (3)
Cu1—N3	2.041 (2)	Cu2—N6	2.021 (4)
P2—O4	1.5027 (18)	Cu3—O4^iii	1.9679 (17)
P2—C11^i	1.803 (2)	Cu3—O8^iii	1.9478 (18)
P2—O5	1.483 (3)	Cu3—O16	2.393 (3)
P2—O6	1.601 (3)	Cu3—O16^iii	2.393 (3)
P2—O5A	1.602 (8)	V1—O3	1.847 (3)
P2—O6A	1.514 (9)	V1—O10	1.846 (4)
P2—V2B	2.835 (14)	V1—O13	1.615 (4)
P3—O7	1.5019 (19)	V1—O14	1.600 (3)
P3—O8	1.4995 (19)	V2—O1	1.847 (3)
P3—O9	1.548 (2)	V2—O6	1.823 (3)
P3—C17	1.798 (2)	V2—O15	1.654 (3)
P4—O11	1.5041 (19)	V2—O16	1.600 (3)
P4—O12^ii	1.5214 (19)	P1—C5^iv	1.758 (3)
P4—C23^i	1.784 (2)	P1—O1	1.543 (3)
P4—O10	1.568 (4)	P1—O2	1.487 (3)
P4—O10A	1.609 (14)	P1—O3	1.545 (3)
O4—Cu3	1.9679 (17)	N4—C41	1.338 (5)
O4—V3^iii	1.978 (2)	N4—C45	1.346 (5)
O4—V3	1.986 (2)	N5—C46	1.357 (6)
O7—Cu2	1.833 (2)	N5—C50	1.326 (5)
O7—Cu2A	2.013 (3)	N6—C51	1.365 (9)
O8—Cu3	1.9478 (18)	N6—C55	1.348 (9)
O8—V3^iii	1.959 (2)	C41—H41	0.9500
O8—V3	1.965 (2)	C41—C42	1.399 (6)
O9—H9	0.8400	C42—H42	0.9500
O9—O18^iii	1.796 (18)	C42—C43	1.377 (7)
O12—P4^ii	1.5215 (19)	C43—H43	0.9500
O19—H19A	0.8706	C43—C44	1.401 (8)
O19—H19B	0.8702	C44—H44	0.9500
N1—C26	1.338 (3)	C44—C45	1.389 (6)
N1—C30	1.363 (3)	C45—C46	1.460 (6)
N2—C31	1.335 (3)	C46—C47	1.400 (5)
N2—C35	1.339 (3)	C47—H47	0.9500
N3—C36	1.351 (3)	C47—C48	1.401 (8)
N3—C40	1.338 (3)	C48—H48	0.9500
C1—C2	1.541 (3)	C48—C49	1.354 (9)
C1—C8	1.540 (3)	C49—H49	0.9500
C1—C14	1.541 (3)	C49—C50	1.411 (6)
C1—C20	1.541 (3)	C50—C51	1.489 (7)
C2—C3	1.395 (3)	C51—C52	1.396 (6)
C2—C7	1.398 (3)	C52—H52	0.9500
C3—H3	0.9500	C52—C53	1.361 (11)
C3—C4	1.382 (4)	C53—H53	0.9500
C4—H4	0.9500	C53—C54	1.413 (11)
C4—C5	1.386 (4)	C54—H54	0.9500
C5—C6	1.405 (4)	C54—C55	1.406 (12)
C5—P1^iv	1.758 (3)	C55—H55	0.9500
C5—P1A^iv	2.084 (7)	Cu2A—O5A	2.133 (8)
C5—P1B^iv	1.965 (10)	Cu2A—N4A	2.046 (10)
C6—H6	0.9500	Cu2A—N5A	1.946 (12)
C6—C7	1.386 (3)	Cu2A—N6A	2.016 (17)
C7—H7	0.9500	V1A—O18	2.39 (2)
C8—C9	1.395 (3)	V1A—O21	1.54 (3)
C8—C13	1.401 (3)	V2A—O13A	2.42 (4)
C9—H9A	0.9500	V2A—V2B	1.010 (15)
C9—C10	1.397 (3)	V2A—O17	1.231 (15)
C10—H10	0.9500	V2A—O12A	1.68 (5)
C10—C11	1.388 (3)	V3—O4^iii	1.978 (2)
C11—P2^v	1.803 (2)	V3—O8^iii	1.959 (2)
C11—C12	1.398 (3)	V3—V3^iii	0.473 (3)
C12—H12	0.9500	V3—O16A	2.151 (9)
C12—C13	1.386 (3)	V3—O16A^iii	1.679 (9)
C13—H13	0.9500	P1A—C5^iv	2.084 (7)
C14—C15	1.382 (3)	P1A—O1A	1.582 (16)
C14—C19	1.400 (3)	P1A—O2A	1.507 (14)
C15—H15	0.9500	P1A—O3A	1.425 (18)
C15—C16	1.397 (3)	O13A—O12A	0.79 (4)
C16—H16	0.9500	O16A—V3^iii	1.679 (9)
C16—C17	1.391 (3)	N4A—C41A	1.346 (16)
C17—C18	1.390 (3)	N4A—C45A	1.312 (16)
C18—H18	0.9500	N5A—C46A	1.326 (16)
C18—C19	1.378 (3)	N5A—C50A	1.333 (17)
C19—H19	0.9500	N6A—C51A	1.34 (3)
C20—C21	1.390 (3)	N6A—C55A	1.32 (3)
C20—C25	1.404 (3)	C41A—H41A	0.9500
C21—H21	0.9500	C41A—C42A	1.434 (18)
C21—C22	1.388 (3)	C42A—H42A	0.9500
C22—H22	0.9500	C42A—C43A	1.35 (3)
C22—C23	1.392 (3)	C43A—H43A	0.9500
C23—P4^v	1.784 (2)	C43A—C44A	1.37 (2)
C23—C24	1.399 (3)	C44A—H44A	0.9500
C24—H24	0.9500	C44A—C45A	1.403 (17)
C24—C25	1.380 (3)	C45A—C46A	1.473 (19)
C25—H25	0.9500	C46A—C47A	1.384 (17)
C26—H26	0.9500	C47A—H47A	0.9500
C26—C27	1.391 (4)	C47A—C48A	1.43 (3)
C27—H27	0.9500	C48A—H48A	0.9500
C27—C28	1.383 (4)	C48A—C49A	1.39 (2)
C28—H28	0.9500	C49A—H49A	0.9500
C28—C29	1.390 (4)	C49A—C50A	1.401 (16)
C29—H29	0.9500	C50A—C51A	1.46 (2)
C29—C30	1.386 (4)	C51A—C52A	1.41 (3)
C30—C31	1.479 (3)	C52A—H52A	0.9500
C31—C32	1.392 (3)	C52A—C53A	1.36 (3)
C32—H32	0.9500	C53A—H53A	0.9500
C32—C33	1.388 (4)	C53A—C54A	1.39 (3)
C33—H33	0.9500	C54A—H54A	0.9500
C33—C34	1.386 (4)	C54A—C55A	1.40 (4)
C34—H34	0.9500	C55A—H55A	0.9500
C34—C35	1.396 (3)	V2B—O17	1.95 (2)
C35—C36	1.480 (3)	P1B—C5^iv	1.965 (10)
C36—C37	1.380 (4)	P1B—O1B	1.486 (18)
C37—H37	0.9500	P1B—O2B	1.47 (2)
C37—C38	1.388 (4)	P1B—O3B	1.416 (17)
C38—H38	0.9500	O18—O9^iii	1.796 (17)
C38—C39	1.381 (4)	O24—H24A	0.8704
C39—H39	0.9500	O24—H24B	0.8704
C39—C40	1.390 (4)
O12—Cu1—O11	89.91 (7)	O4^iii—Cu3—O16	85.63 (10)
O12—Cu1—N1	106.28 (8)	O8—Cu3—O4	92.18 (7)
O12—Cu1—N2	166.66 (8)	O8^iii—Cu3—O4^iii	92.18 (7)
O12—Cu1—N3	93.41 (8)	O8—Cu3—O4^iii	87.82 (7)
N1—Cu1—O11	101.90 (7)	O8^iii—Cu3—O4	87.82 (7)
N2—Cu1—O11	101.18 (8)	O8^iii—Cu3—O8	180.0
N2—Cu1—N1	78.87 (8)	O8^iii—Cu3—O16	88.49 (11)
N2—Cu1—N3	79.45 (9)	O8^iii—Cu3—O16^iii	91.51 (11)
N3—Cu1—O11	89.44 (7)	O8—Cu3—O16^iii	88.49 (11)
N3—Cu1—N1	157.11 (8)	O8—Cu3—O16	91.51 (11)
O4—P2—C11^i	109.57 (10)	O16—Cu3—O16^iii	180.0
O4—P2—O6	109.62 (13)	O10—V1—O3	115.92 (16)
O4—P2—O5A	105.8 (3)	O13—V1—O3	108.17 (18)
O4—P2—O6A	116.5 (3)	O13—V1—O10	109.53 (19)
O4—P2—V2B	96.6 (3)	O14—V1—O3	108.03 (15)
C11^i—P2—V2B	95.5 (3)	O14—V1—O10	108.29 (14)
O5—P2—O4	116.60 (12)	O14—V1—O13	106.50 (18)
O5—P2—C11^i	107.57 (13)	O6—V2—O1	114.12 (12)
O5—P2—O6	109.70 (14)	O15—V2—O1	106.01 (16)
O6—P2—C11^i	102.88 (13)	O15—V2—O6	110.77 (15)
O5A—P2—C11^i	105.7 (3)	O16—V2—O1	111.13 (16)
O6A—P2—C11^i	108.3 (3)	O16—V2—O6	109.70 (15)
O6A—P2—O5A	110.5 (4)	O16—V2—O15	104.63 (17)
O7—P3—O9	108.95 (12)	O1—P1—C5^iv	104.28 (15)
O7—P3—C17	103.13 (11)	O1—P1—O3	106.69 (17)
O8—P3—O7	115.51 (11)	O2—P1—C5^iv	110.96 (15)
O8—P3—O9	112.28 (12)	O2—P1—O1	113.47 (18)
O8—P3—C17	109.89 (11)	O2—P1—O3	113.92 (18)
O9—P3—C17	106.34 (11)	O3—P1—C5^iv	106.86 (16)
O11—P4—O12^ii	114.46 (10)	P1—O1—V2	135.17 (19)
O11—P4—C23^i	107.42 (11)	P1—O3—V1	151.1 (2)
O11—P4—O10	113.93 (15)	P2—O5—Cu2	122.04 (15)
O11—P4—O10A	103.2 (5)	P2—O6—V2	139.55 (18)
O12^ii—P4—C23^i	108.12 (11)	P4—O10—V1	134.68 (18)
O12^ii—P4—O10	105.51 (12)	V2—O16—Cu3	124.02 (18)
O12^ii—P4—O10A	119.9 (3)	C41—N4—Cu2	125.3 (3)
O10—P4—C23^i	107.05 (17)	C41—N4—C45	119.7 (4)
O10A—P4—C23^i	102.6 (5)	C45—N4—Cu2	114.6 (3)
P2—O4—Cu3	140.93 (11)	C46—N5—Cu2	117.5 (3)
P2—O4—V3^iii	134.19 (12)	C50—N5—Cu2	118.9 (3)
P2—O4—V3	147.61 (12)	C50—N5—C46	123.6 (4)
V3^iii—O4—V3	13.71 (9)	C51—N6—Cu2	113.1 (4)
P3—O7—Cu2	157.78 (14)	C55—N6—Cu2	125.5 (6)
P3—O7—Cu2A	148.60 (15)	C55—N6—C51	121.4 (6)
P3—O8—Cu3	148.54 (12)	N4—C41—H41	119.0
P3—O8—V3^iii	145.83 (13)	N4—C41—C42	121.9 (4)
P3—O8—V3	150.00 (13)	C42—C41—H41	119.0
V3^iii—O8—V3	13.85 (9)	C41—C42—H42	120.8
P3—O9—H9	109.5	C43—C42—C41	118.4 (4)
P3—O9—O18^iii	167.0 (6)	C43—C42—H42	120.8
P4—O11—Cu1	118.60 (10)	C42—C43—H43	120.1
P4^ii—O12—Cu1	133.19 (12)	C42—C43—C44	119.9 (5)
H19A—O19—H19B	109.5	C44—C43—H43	120.1
C26—N1—Cu1	128.45 (17)	C43—C44—H44	120.9
C26—N1—C30	117.9 (2)	C45—C44—C43	118.2 (6)
C30—N1—Cu1	113.69 (16)	C45—C44—H44	120.9
C31—N2—Cu1	119.75 (17)	N4—C45—C44	121.8 (5)
C31—N2—C35	121.8 (2)	N4—C45—C46	113.8 (4)
C35—N2—Cu1	118.50 (17)	C44—C45—C46	124.4 (4)
C36—N3—Cu1	114.83 (16)	N5—C46—C45	113.7 (3)
C40—N3—Cu1	126.06 (17)	N5—C46—C47	119.3 (5)
C40—N3—C36	119.1 (2)	C47—C46—C45	127.1 (4)
C2—C1—C14	103.56 (18)	C46—C47—H47	121.3
C2—C1—C20	112.85 (19)	C46—C47—C48	117.3 (5)
C8—C1—C2	112.32 (19)	C48—C47—H47	121.3
C8—C1—C14	114.11 (19)	C47—C48—H48	119.0
C8—C1—C20	103.05 (17)	C49—C48—C47	121.9 (4)
C14—C1—C20	111.28 (19)	C49—C48—H48	119.0
C3—C2—C1	123.2 (2)	C48—C49—H49	120.5
C3—C2—C7	117.8 (2)	C48—C49—C50	118.9 (5)
C7—C2—C1	118.8 (2)	C50—C49—H49	120.5
C2—C3—H3	119.6	N5—C50—C49	118.9 (5)
C4—C3—C2	120.8 (3)	N5—C50—C51	112.5 (4)
C4—C3—H3	119.6	C49—C50—C51	128.6 (5)
C3—C4—H4	119.4	N6—C51—C50	114.7 (4)
C3—C4—C5	121.2 (2)	N6—C51—C52	120.4 (5)
C5—C4—H4	119.4	C52—C51—C50	124.9 (5)
C4—C5—C6	118.8 (2)	C51—C52—H52	120.5
C4—C5—P1^iv	115.9 (2)	C53—C52—C51	119.0 (5)
C4—C5—P1A^iv	134.4 (3)	C53—C52—H52	120.5
C4—C5—P1B^iv	118.2 (3)	C52—C53—H53	119.4
C6—C5—P1^iv	125.2 (2)	C52—C53—C54	121.2 (5)
C6—C5—P1A^iv	106.8 (3)	C54—C53—H53	119.4
C6—C5—P1B^iv	121.0 (3)	C53—C54—H54	121.1
C5—C6—H6	120.2	C55—C54—C53	117.7 (7)
C7—C6—C5	119.5 (2)	C55—C54—H54	121.1
C7—C6—H6	120.2	N6—C55—C54	120.4 (9)
C2—C7—H7	119.1	N6—C55—H55	119.8
C6—C7—C2	121.7 (2)	C54—C55—H55	119.8
C6—C7—H7	119.1	O7—Cu2A—O5A	100.0 (2)
C9—C8—C1	122.9 (2)	O7—Cu2A—N4A	94.8 (3)
C9—C8—C13	117.9 (2)	O7—Cu2A—N6A	102.5 (7)
C13—C8—C1	118.7 (2)	N4A—Cu2A—O5A	91.0 (3)
C8—C9—H9A	119.7	N5A—Cu2A—O7	158.7 (3)
C8—C9—C10	120.5 (2)	N5A—Cu2A—O5A	100.5 (4)
C10—C9—H9A	119.7	N5A—Cu2A—N4A	79.1 (5)
C9—C10—H10	119.4	N5A—Cu2A—N6A	80.3 (8)
C11—C10—C9	121.3 (2)	N6A—Cu2A—O5A	98.0 (7)
C11—C10—H10	119.4	N6A—Cu2A—N4A	158.7 (8)
C10—C11—P2^v	120.40 (18)	O21—V1A—O18	100.2 (10)
C10—C11—C12	118.3 (2)	V2B—V2A—O13A	141.1 (13)
C12—C11—P2^v	121.15 (17)	V2B—V2A—O17	120.6 (13)
C11—C12—H12	119.8	V2B—V2A—O12A	133.5 (17)
C13—C12—C11	120.5 (2)	O17—V2A—O13A	94.6 (11)
C13—C12—H12	119.8	O17—V2A—O12A	100.3 (16)
C8—C13—H13	119.3	O12A—V2A—O13A	8.0 (17)
C12—C13—C8	121.5 (2)	O4^iii—V3—O4	166.29 (9)
C12—C13—H13	119.3	O4—V3—O16A	85.4 (3)
C15—C14—C1	124.9 (2)	O4^iii—V3—O16A	80.9 (3)
C15—C14—C19	118.1 (2)	O8—V3—O4	91.14 (10)
C19—C14—C1	116.8 (2)	O8^iii—V3—O4	86.99 (10)
C14—C15—H15	119.6	O8—V3—O4^iii	87.05 (10)
C14—C15—C16	120.8 (2)	O8^iii—V3—O4^iii	91.51 (10)
C16—C15—H15	119.6	O8^iii—V3—O8	166.15 (9)
C15—C16—H16	119.8	O8^iii—V3—O16A	84.0 (3)
C17—C16—C15	120.5 (2)	O8—V3—O16A	82.2 (3)
C17—C16—H16	119.8	V3^iii—V3—O4^iii	84.0 (4)
C16—C17—P3	123.51 (18)	V3^iii—V3—O4	82.3 (4)
C18—C17—P3	117.03 (17)	V3^iii—V3—O8	82.4 (4)
C18—C17—C16	118.7 (2)	V3^iii—V3—O8^iii	83.7 (4)
C17—C18—H18	119.8	V3^iii—V3—O16A	3.1 (5)
C19—C18—C17	120.5 (2)	V3^iii—V3—O16A^iii	176.0 (6)
C19—C18—H18	119.8	O16A^iii—V3—O4^iii	99.9 (4)
C14—C19—H19	119.4	O16A^iii—V3—O4	93.8 (4)
C18—C19—C14	121.3 (2)	O16A^iii—V3—O8	97.9 (4)
C18—C19—H19	119.4	O16A^iii—V3—O8^iii	95.9 (4)
C21—C20—C1	122.0 (2)	O16A^iii—V3—O16A	179.13 (15)
C21—C20—C25	118.3 (2)	O1A—P1A—C5^iv	96.2 (7)
C25—C20—C1	119.4 (2)	O2A—P1A—C5^iv	109.2 (6)
C20—C21—H21	119.5	O2A—P1A—O1A	105.2 (9)
C22—C21—C20	120.9 (2)	O3A—P1A—C5^iv	115.2 (7)
C22—C21—H21	119.5	O3A—P1A—O1A	117.0 (9)
C21—C22—H22	119.7	O3A—P1A—O2A	112.5 (10)
C21—C22—C23	120.6 (2)	P2—O5A—Cu2A	126.7 (4)
C23—C22—H22	119.7	O12A—O13A—V2A	17 (4)
C22—C23—P4^v	119.10 (19)	V3^iii—O16A—V3	0.87 (14)
C22—C23—C24	118.7 (2)	C41A—N4A—Cu2A	124.6 (8)
C24—C23—P4^v	122.13 (18)	C45A—N4A—Cu2A	115.0 (9)
C23—C24—H24	119.7	C45A—N4A—C41A	119.7 (12)
C25—C24—C23	120.6 (2)	C46A—N5A—Cu2A	117.3 (10)
C25—C24—H24	119.7	C46A—N5A—C50A	126.5 (12)
C20—C25—H25	119.6	C50A—N5A—Cu2A	116.1 (9)
C24—C25—C20	120.8 (2)	C51A—N6A—Cu2A	115.5 (15)
C24—C25—H25	119.6	C55A—N6A—Cu2A	127 (2)
N1—C26—H26	118.8	C55A—N6A—C51A	117 (2)
N1—C26—C27	122.4 (2)	N4A—C41A—H41A	119.1
C27—C26—H26	118.8	N4A—C41A—C42A	121.8 (12)
C26—C27—H27	120.2	C42A—C41A—H41A	119.1
C28—C27—C26	119.7 (2)	C41A—C42A—H42A	122.3
C28—C27—H27	120.2	C43A—C42A—C41A	115.4 (13)
C27—C28—H28	120.7	C43A—C42A—H42A	122.3
C27—C28—C29	118.5 (2)	C42A—C43A—H43A	118.1
C29—C28—H28	120.7	C42A—C43A—C44A	123.8 (15)
C28—C29—H29	120.6	C44A—C43A—H43A	118.1
C30—C29—C28	118.9 (2)	C43A—C44A—H44A	121.6
C30—C29—H29	120.6	C43A—C44A—C45A	116.7 (15)
N1—C30—C29	122.7 (2)	C45A—C44A—H44A	121.6
N1—C30—C31	114.1 (2)	N4A—C45A—C44A	122.6 (15)
C29—C30—C31	123.2 (2)	N4A—C45A—C46A	113.1 (11)
N2—C31—C30	113.5 (2)	C44A—C45A—C46A	124.3 (13)
N2—C31—C32	120.9 (2)	N5A—C46A—C45A	114.6 (10)
C32—C31—C30	125.6 (2)	N5A—C46A—C47A	118.8 (15)
C31—C32—H32	120.9	C47A—C46A—C45A	126.6 (14)
C33—C32—C31	118.2 (2)	C46A—C47A—H47A	121.1
C33—C32—H32	120.9	C46A—C47A—C48A	117.7 (15)
C32—C33—H33	119.9	C48A—C47A—H47A	121.1
C34—C33—C32	120.2 (2)	C47A—C48A—H48A	119.6
C34—C33—H33	119.9	C49A—C48A—C47A	120.7 (12)
C33—C34—H34	120.7	C49A—C48A—H48A	119.6
C33—C34—C35	118.7 (2)	C48A—C49A—H49A	120.7
C35—C34—H34	120.7	C48A—C49A—C50A	118.5 (14)
N2—C35—C34	120.2 (2)	C50A—C49A—H49A	120.7
N2—C35—C36	113.3 (2)	N5A—C50A—C49A	117.7 (14)
C34—C35—C36	126.5 (2)	N5A—C50A—C51A	116.0 (10)
N3—C36—C35	113.7 (2)	C49A—C50A—C51A	126.2 (13)
N3—C36—C37	122.1 (2)	N6A—C51A—C50A	112.1 (13)
C37—C36—C35	124.2 (2)	N6A—C51A—C52A	121.0 (17)
C36—C37—H37	120.6	C52A—C51A—C50A	127.0 (14)
C36—C37—C38	118.8 (2)	C51A—C52A—H52A	120.9
C38—C37—H37	120.6	C53A—C52A—C51A	118.3 (16)
C37—C38—H38	120.5	C53A—C52A—H52A	120.9
C39—C38—C37	119.1 (2)	C52A—C53A—H53A	118.6
C39—C38—H38	120.5	C52A—C53A—C54A	122.8 (17)
C38—C39—H39	120.4	C54A—C53A—H53A	118.6
C38—C39—C40	119.3 (2)	C53A—C54A—H54A	123.6
C40—C39—H39	120.4	C53A—C54A—C55A	113 (2)
N3—C40—C39	121.6 (2)	C55A—C54A—H54A	123.6
N3—C40—H40	119.2	N6A—C55A—C54A	127 (3)
C39—C40—H40	119.2	N6A—C55A—H55A	116.4
O7—Cu2—O5	105.68 (10)	C54A—C55A—H55A	116.4
O7—Cu2—N4	94.28 (12)	V2A—V2B—P2	111.3 (10)
O7—Cu2—N5	155.14 (12)	V2A—V2B—O17	32.9 (8)
O7—Cu2—N6	100.7 (2)	O17—V2B—P2	129.2 (7)
N4—Cu2—O5	87.34 (11)	O1B—P1B—C5^iv	102.7 (10)
N5—Cu2—O5	98.28 (12)	O2B—P1B—C5^iv	97.6 (15)
N5—Cu2—N4	80.10 (16)	O2B—P1B—O1B	108.0 (10)
N5—Cu2—N6	80.9 (2)	O3B—P1B—C5^iv	118.3 (10)
N6—Cu2—O5	100.9 (2)	O3B—P1B—O1B	113.9 (10)
N6—Cu2—N4	160.2 (2)	O3B—P1B—O2B	114.5 (11)
O4^iii—Cu3—O4	180.0	V2A—O17—V2B	26.5 (6)
O4—Cu3—O16^iii	85.63 (10)	O9^iii—O18—V1A	143.4 (10)
O4^iii—Cu3—O16^iii	94.38 (10)	H24A—O24—H24B	109.4
O4—Cu3—O16	94.37 (10)	O13A—O12A—V2A	155 (5)
Cu1—N1—C26—C27	−177.51 (19)	C34—C35—C36—N3	179.8 (2)
Cu1—N1—C30—C29	178.33 (19)	C34—C35—C36—C37	−2.3 (4)
Cu1—N1—C30—C31	0.1 (3)	C35—N2—C31—C30	176.2 (2)
Cu1—N2—C31—C30	−3.6 (3)	C35—N2—C31—C32	−2.0 (4)
Cu1—N2—C31—C32	178.22 (19)	C35—C36—C37—C38	−178.2 (2)
Cu1—N2—C35—C34	−177.41 (19)	C36—N3—C40—C39	0.1 (4)
Cu1—N2—C35—C36	5.4 (3)	C36—C37—C38—C39	0.0 (4)
Cu1—N3—C36—C35	−0.2 (3)	C37—C38—C39—C40	0.5 (4)
Cu1—N3—C36—C37	−178.12 (19)	C38—C39—C40—N3	−0.6 (4)
Cu1—N3—C40—C39	178.48 (18)	C40—N3—C36—C35	178.4 (2)
P2^v—C11—C12—C13	175.26 (18)	C40—N3—C36—C37	0.4 (4)
P3—O7—Cu2—O5	94.2 (4)	Cu2—N4—C41—C42	−172.4 (3)
P3—O7—Cu2—N4	−177.4 (4)	Cu2—N4—C45—C44	174.5 (4)
P3—O7—Cu2—N5	−101.8 (5)	Cu2—N4—C45—C46	−5.8 (4)
P3—O7—Cu2—N6	−10.5 (5)	Cu2—N5—C46—C45	2.2 (4)
P3—C17—C18—C19	−168.3 (2)	Cu2—N5—C46—C47	−178.8 (3)
P4^v—C23—C24—C25	177.89 (19)	Cu2—N5—C50—C49	179.5 (3)
O4—P2—O5—Cu2	−35.9 (2)	Cu2—N5—C50—C51	−1.2 (4)
O4—P2—O6—V2	−11.0 (3)	Cu2—N6—C51—C50	0.2 (6)
O4—P2—O5A—Cu2A	−49.6 (5)	Cu2—N6—C51—C52	177.9 (4)
O7—P3—O8—Cu3	−3.1 (3)	Cu2—N6—C55—C54	−176.1 (6)
O7—P3—O8—V3^iii	−14.9 (3)	P1^iv—C5—C6—C7	176.2 (2)
O7—P3—O8—V3	10.1 (3)	O1—V2—O6—P2	−111.4 (3)
O7—P3—O9—O18^iii	20 (3)	O1—V2—O16—Cu3	114.8 (2)
O7—P3—C17—C16	−96.9 (2)	O1—P1—O3—V1	−174.8 (4)
O7—P3—C17—C18	73.3 (2)	O2—P1—O1—V2	18.9 (3)
O8—P3—O7—Cu2	−75.7 (4)	O2—P1—O3—V1	−48.8 (5)
O8—P3—O7—Cu2A	−81.1 (3)	O3—V1—O10—P4	−96.1 (3)
O8—P3—O9—O18^iii	150 (3)	O3—P1—O1—V2	145.2 (2)
O8—P3—C17—C16	139.4 (2)	O5—P2—O4—Cu3	134.84 (18)
O8—P3—C17—C18	−50.4 (2)	O5—P2—O6—V2	−140.2 (2)
O9—P3—O7—Cu2	51.7 (4)	O6—P2—O4—Cu3	9.5 (2)
O9—P3—O7—Cu2A	46.3 (3)	O6—P2—O5—Cu2	89.45 (18)
O9—P3—O8—Cu3	−128.9 (2)	O6—V2—O1—P1	37.8 (3)
O9—P3—O8—V3^iii	−140.7 (2)	O6—V2—O16—Cu3	−12.3 (3)
O9—P3—O8—V3	−115.6 (3)	O10—P4—O11—Cu1	160.43 (15)
O9—P3—C17—C16	17.7 (2)	O10—V1—O3—P1	33.4 (5)
O9—P3—C17—C18	−172.2 (2)	O13—V1—O3—P1	156.9 (4)
O11—P4—O10—V1	−159.2 (3)	O13—V1—O10—P4	141.2 (3)
O12^ii—P4—O11—Cu1	38.88 (14)	O14—V1—O3—P1	−88.2 (5)
O12^ii—P4—O10—V1	−32.8 (4)	O14—V1—O10—P4	25.4 (4)
N1—C26—C27—C28	−0.9 (4)	O15—V2—O1—P1	160.0 (3)
N1—C30—C31—N2	2.1 (3)	O15—V2—O6—P2	129.1 (3)
N1—C30—C31—C32	−179.8 (2)	O15—V2—O16—Cu3	−131.2 (2)
N2—C31—C32—C33	0.2 (4)	O16—V2—O1—P1	−86.9 (3)
N2—C35—C36—N3	−3.2 (3)	O16—V2—O6—P2	14.0 (3)
N2—C35—C36—C37	174.7 (2)	N4—C41—C42—C43	−1.5 (6)
N3—C36—C37—C38	−0.5 (4)	N4—C45—C46—N5	2.5 (4)
C1—C2—C3—C4	−178.1 (2)	N4—C45—C46—C47	−176.4 (4)
C1—C2—C7—C6	179.0 (2)	N5—C46—C47—C48	−1.2 (5)
C1—C8—C9—C10	171.0 (2)	N5—C50—C51—N6	0.6 (6)
C1—C8—C13—C12	−171.0 (2)	N5—C50—C51—C52	−177.0 (4)
C1—C14—C15—C16	−174.7 (2)	N6—C51—C52—C53	−2.6 (8)
C1—C14—C19—C18	175.9 (2)	C41—N4—C45—C44	1.6 (6)
C1—C20—C21—C22	176.3 (2)	C41—N4—C45—C46	−178.7 (3)
C1—C20—C25—C24	−177.8 (2)	C41—C42—C43—C44	2.1 (7)
C2—C1—C8—C9	13.2 (3)	C42—C43—C44—C45	−0.9 (7)
C2—C1—C8—C13	−175.3 (2)	C43—C44—C45—N4	−1.0 (7)
C2—C1—C14—C15	112.6 (3)	C43—C44—C45—C46	179.3 (4)
C2—C1—C14—C19	−63.5 (3)	C44—C45—C46—N5	−177.8 (4)
C2—C1—C20—C21	132.6 (2)	C44—C45—C46—C47	3.3 (6)
C2—C1—C20—C25	−53.6 (3)	C45—N4—C41—C42	−0.4 (6)
C2—C3—C4—C5	0.0 (4)	C45—C46—C47—C48	177.6 (4)
C3—C2—C7—C6	4.1 (4)	C46—N5—C50—C49	−1.0 (5)
C3—C4—C5—C6	2.9 (4)	C46—N5—C50—C51	178.3 (3)
C3—C4—C5—P1^iv	−175.7 (2)	C46—C47—C48—C49	0.1 (6)
C3—C4—C5—P1A^iv	179.6 (3)	C47—C48—C49—C50	0.5 (7)
C3—C4—C5—P1B^iv	167.1 (4)	C48—C49—C50—N5	−0.1 (6)
C4—C5—C6—C7	−2.2 (4)	C48—C49—C50—C51	−179.3 (4)
C5—C6—C7—C2	−1.2 (4)	C49—C50—C51—N6	179.8 (5)
C5^iv—P1—O1—V2	−101.9 (3)	C49—C50—C51—C52	2.3 (6)
C5^iv—P1—O3—V1	74.1 (5)	C50—N5—C46—C45	−177.3 (3)
C7—C2—C3—C4	−3.4 (4)	C50—N5—C46—C47	1.6 (5)
C8—C1—C2—C3	−125.9 (2)	C50—C51—C52—C53	174.9 (4)
C8—C1—C2—C7	59.4 (3)	C51—N6—C55—C54	0.1 (12)
C8—C1—C14—C15	−9.8 (3)	C51—C52—C53—C54	2.6 (8)
C8—C1—C14—C19	174.1 (2)	C52—C53—C54—C55	−1.3 (10)
C8—C1—C20—C21	−106.0 (2)	C53—C54—C55—N6	−0.1 (12)
C8—C1—C20—C25	67.8 (3)	C55—N6—C51—C50	−176.4 (7)
C8—C9—C10—C11	−0.8 (3)	C55—N6—C51—C52	1.3 (10)
C9—C8—C13—C12	0.9 (3)	Cu2A—N4A—C41A—C42A	−172.8 (8)
C9—C10—C11—P2^v	−174.87 (18)	Cu2A—N4A—C45A—C44A	173.1 (9)
C9—C10—C11—C12	1.6 (3)	Cu2A—N4A—C45A—C46A	−10.0 (12)
C10—C11—C12—C13	−1.2 (3)	Cu2A—N5A—C46A—C45A	−0.9 (12)
C11^i—P2—O4—Cu3	−102.72 (17)	Cu2A—N5A—C46A—C47A	178.0 (9)
C11^i—P2—O4—V3^iii	−104.66 (17)	Cu2A—N5A—C50A—C49A	−178.4 (8)
C11^i—P2—O4—V3	−100.1 (2)	Cu2A—N5A—C50A—C51A	1.5 (13)
C11^i—P2—O5—Cu2	−159.34 (13)	Cu2A—N6A—C51A—C50A	0 (2)
C11^i—P2—O6—V2	105.5 (3)	Cu2A—N6A—C51A—C52A	179.9 (12)
C11^i—P2—O5A—Cu2A	−165.8 (4)	Cu2A—N6A—C55A—C54A	−176 (2)
C11—C12—C13—C8	−0.1 (4)	P1A^iv—C5—C6—C7	−179.8 (2)
C13—C8—C9—C10	−0.5 (3)	O5A—P2—O4—V3^iii	141.9 (3)
C14—C1—C2—C3	110.5 (2)	O5A—P2—O4—V3	146.4 (3)
C14—C1—C2—C7	−64.2 (2)	O6A—P2—O4—V3	23.2 (4)
C14—C1—C8—C9	130.7 (2)	O6A—P2—O4—V3^iii	18.7 (4)
C14—C1—C8—C13	−57.8 (3)	O6A—P2—O5A—Cu2A	77.3 (6)
C14—C1—C20—C21	16.7 (3)	O13A—V2A—V2B—P2	78.1 (19)
C14—C1—C20—C25	−169.5 (2)	O13A—V2A—V2B—O17	−152 (2)
C14—C15—C16—C17	−0.3 (4)	O13A—V2A—O17—V2B	162.5 (15)
C15—C14—C19—C18	−0.4 (4)	N4A—C41A—C42A—C43A	1.8 (19)
C15—C16—C17—P3	168.50 (19)	N4A—C45A—C46A—N5A	7.3 (14)
C15—C16—C17—C18	−1.5 (4)	N4A—C45A—C46A—C47A	−171.5 (11)
C16—C17—C18—C19	2.4 (4)	N5A—C46A—C47A—C48A	−0.6 (18)
C17—P3—O7—Cu2	164.4 (4)	N5A—C50A—C51A—N6A	−1.1 (18)
C17—P3—O7—Cu2A	159.0 (3)	N5A—C50A—C51A—C52A	179.3 (13)
C17—P3—O8—Cu3	113.0 (2)	N6A—C51A—C52A—C53A	−4 (3)
C17—P3—O8—V3	126.2 (3)	C41A—N4A—C45A—C44A	2.2 (17)
C17—P3—O8—V3^iii	101.2 (2)	C41A—N4A—C45A—C46A	179.1 (10)
C17—P3—O9—O18^iii	−90 (3)	C41A—C42A—C43A—C44A	0 (3)
C17—C18—C19—C14	−1.4 (4)	C42A—C43A—C44A—C45A	0 (3)
C19—C14—C15—C16	1.3 (4)	C43A—C44A—C45A—N4A	−0.6 (19)
C20—C1—C2—C3	−10.0 (3)	C43A—C44A—C45A—C46A	−177.1 (14)
C20—C1—C2—C7	175.4 (2)	C44A—C45A—C46A—N5A	−175.8 (10)
C20—C1—C8—C9	−108.5 (2)	C44A—C45A—C46A—C47A	5.3 (19)
C20—C1—C8—C13	63.0 (3)	C45A—N4A—C41A—C42A	−2.8 (17)
C20—C1—C14—C15	−125.9 (2)	C45A—C46A—C47A—C48A	178.2 (11)
C20—C1—C14—C19	58.0 (3)	C46A—N5A—C50A—C49A	−1.9 (16)
C20—C21—C22—C23	0.7 (4)	C46A—N5A—C50A—C51A	178.0 (10)
C21—C20—C25—C24	−3.8 (4)	C46A—C47A—C48A—C49A	0 (2)
C21—C22—C23—P4^v	−179.36 (19)	C47A—C48A—C49A—C50A	−0.4 (18)
C21—C22—C23—C24	−2.4 (4)	C48A—C49A—C50A—N5A	1.2 (16)
C22—C23—C24—C25	1.1 (4)	C48A—C49A—C50A—C51A	−178.6 (11)
C23^i—P4—O11—Cu1	−81.17 (12)	C49A—C50A—C51A—N6A	178.7 (15)
C23^i—P4—O10—V1	82.2 (3)	C49A—C50A—C51A—C52A	−1 (2)
C23—C24—C25—C20	2.1 (4)	C50A—N5A—C46A—C45A	−177.4 (10)
C25—C20—C21—C22	2.4 (4)	C50A—N5A—C46A—C47A	1.5 (17)
C26—N1—C30—C29	−0.5 (4)	C50A—C51A—C52A—C53A	175.5 (14)
C26—N1—C30—C31	−178.8 (2)	C51A—N6A—C55A—C54A	7 (4)
C26—C27—C28—C29	−0.1 (4)	C51A—C52A—C53A—C54A	8 (3)
C27—C28—C29—C30	0.7 (4)	C52A—C53A—C54A—C55A	−5 (3)
C28—C29—C30—N1	−0.4 (4)	C53A—C54A—C55A—N6A	−3 (4)
C28—C29—C30—C31	177.7 (2)	C55A—N6A—C51A—C50A	177 (2)
C29—C30—C31—N2	−176.1 (2)	C55A—N6A—C51A—C52A	−3 (3)
C29—C30—C31—C32	2.0 (4)	V2B—V2A—O12A—O13A	−162 (12)
C30—N1—C26—C27	1.2 (4)	P1B^iv—C5—C6—C7	−166.0 (4)
C30—C31—C32—C33	−177.7 (3)	O10A—P4—O11—Cu1	170.9 (5)
C31—N2—C35—C34	2.8 (4)	O17—V2A—V2B—P2	−130.3 (11)
C31—N2—C35—C36	−174.4 (2)	O17—V2A—O12A—O13A	46 (13)
C31—C32—C33—C34	0.6 (4)	O12A—V2A—V2B—P2	82 (2)
C32—C33—C34—C35	0.2 (4)	O12A—V2A—V2B—O17	−148 (3)
C33—C34—C35—N2	−1.9 (4)	O12A—V2A—O17—V2B	157 (2)
C33—C34—C35—C36	174.9 (3)

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

(I)

Crystal data

C25H24O12P4·2(CH4O)	Z = 4
Mr = 704.40	F(000) = 1464
Monoclinic, C2/c	Dx = 1.492 Mg m^−3
a = 29.093 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.2893 (8) Å	µ = 0.31 mm^−1
c = 18.672 (2) Å	T = 296 K
β = 127.610 (5)°	Block, colorless
V = 3136.8 (6) Å^3	0.11 × 0.10 × 0.06 mm

Data collection

Bruker APEX II QUAZAR three-circle diffractometer	2772 independent reflections
Radiation source: microfocus sealed tube, ImuS	2215 reflections with I > 2σ(I)
Multilayer QUAZAR mirrors monochromator	Rint = 0.053
Detector resolution: 8.3333 pixels mm^-1	θmax = 25.1°, θmin = 2.2°
φ and ω scans	h = −34→34
Absorption correction: multi-scan SADABS V2014/5 (Bruker AXS)	k = −8→8
Tmin = 0.97, Tmax = 0.98	l = −22→22
14601 measured reflections

Refinement

Refinement on F^2	102 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.054	H-atom parameters constrained
wR(F^2) = 0.141	w = 1/[σ^2(Fo^2) + (0.0601P)^2 + 9.8652P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
2772 reflections	Δρmax = 0.49 e Å^−3
262 parameters	Δρmin = −0.47 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)
C1	0.5	0.7543 (6)	0.75	0.0201 (9)
C2	0.45843 (13)	0.6248 (4)	0.67007 (19)	0.0215 (6)
C3	0.48080 (14)	0.5023 (4)	0.6411 (2)	0.0294 (7)
H3	0.5205	0.5005	0.6702	0.035*
C4	0.44510 (14)	0.3832 (5)	0.5700 (2)	0.0331 (8)
H4	0.461	0.3044	0.5512	0.04*
C5	0.38592 (14)	0.3801 (4)	0.5265 (2)	0.0275 (7)
C6	0.36439 (14)	0.4946 (5)	0.5582 (2)	0.0361 (8)
H6	0.325	0.4908	0.5316	0.043*
C7	0.39999 (14)	0.6155 (5)	0.6287 (2)	0.0340 (8)
H7	0.3841	0.6916	0.6484	0.041*
C8	0.46641 (13)	0.8852 (4)	0.7691 (2)	0.0223 (7)
C9	0.47309 (14)	0.8897 (5)	0.8493 (2)	0.0303 (8)
H9	0.4991	0.8099	0.8959	0.036*
C10	0.44141 (14)	1.0117 (5)	0.8608 (2)	0.0319 (8)
H10	0.4462	1.0115	0.9148	0.038*
C11	0.40288 (13)	1.1335 (4)	0.7932 (2)	0.0262 (7)
C12	0.39721 (15)	1.1327 (5)	0.7139 (2)	0.0332 (8)
H12	0.3719	1.2147	0.6679	0.04*
C13	0.42871 (15)	1.0111 (5)	0.7024 (2)	0.0319 (8)
H13	0.4246	1.0136	0.6489	0.038*
C14	0.2250 (2)	0.2780 (7)	0.8758 (4)	0.0695 (14)
H14A	0.2607	0.261	0.9354	0.104*
H14B	0.2049	0.163	0.8533	0.104*
H14C	0.2011	0.365	0.8781	0.104*
O7	0.23750 (14)	0.3461 (5)	0.8163 (2)	0.0682 (9)
H7A	0.2123	0.3109	0.7646	0.102*
P1	0.33894 (4)	0.23837 (12)	0.42935 (6)	0.0332 (3)
P2	0.36115 (4)	1.29093 (13)	0.80635 (6)	0.0308 (3)
O1	0.3493 (2)	0.0381 (5)	0.4614 (3)	0.0378 (9)	0.766 (9)
H1	0.3283	−0.0295	0.4178	0.057*	0.766 (9)
O2	0.27663 (14)	0.2975 (7)	0.3880 (3)	0.0420 (9)	0.766 (9)
H2	0.2725	0.4064	0.3743	0.063*	0.766 (9)
O3	0.35320 (19)	0.2664 (7)	0.3648 (3)	0.0363 (9)	0.766 (9)
O2A	0.2824 (5)	0.224 (2)	0.4158 (9)	0.0384 (17)	0.234 (9)
H2A	0.2627	0.1416	0.3801	0.058*	0.234 (9)
O1A	0.3729 (6)	0.0457 (15)	0.4733 (9)	0.0370 (18)	0.234 (9)
H1A	0.3569	−0.0351	0.4348	0.055*	0.234 (9)
O3A	0.3369 (7)	0.280 (3)	0.3496 (9)	0.0349 (18)	0.234 (9)
O4	0.33591 (14)	1.2024 (4)	0.8455 (2)	0.0384 (7)	0.868 (3)
O5	0.31416 (11)	1.3798 (4)	0.71242 (18)	0.0354 (7)	0.868 (3)
H5	0.2916	1.3004	0.6771	0.053*	0.868 (3)
O6	0.40348 (12)	1.4518 (4)	0.8630 (2)	0.0374 (7)	0.868 (3)
H6A	0.3862	1.532	0.8689	0.056*	0.868 (3)
O4A	0.3663 (9)	1.230 (2)	0.8915 (11)	0.0302 (18)	0.132 (3)
O6A	0.3825 (8)	1.4765 (18)	0.8126 (14)	0.0311 (19)	0.132 (3)
H6A1	0.3641	1.5502	0.8193	0.047*	0.132 (3)
O5A	0.2990 (5)	1.226 (2)	0.7360 (11)	0.0364 (19)	0.132 (3)
H5A	0.2984	1.1462	0.7044	0.055*	0.132 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.019 (2)	0.021 (2)	0.021 (2)	0	0.0131 (18)	0
C2	0.0232 (15)	0.0202 (16)	0.0200 (14)	0.0003 (12)	0.0127 (13)	0.0015 (12)
C3	0.0210 (15)	0.0303 (18)	0.0316 (17)	0.0007 (13)	0.0134 (14)	−0.0049 (14)
C4	0.0308 (18)	0.0309 (19)	0.0381 (19)	0.0005 (14)	0.0213 (16)	−0.0095 (15)
C5	0.0290 (17)	0.0253 (17)	0.0243 (16)	−0.0042 (13)	0.0143 (14)	−0.0017 (13)
C6	0.0200 (16)	0.045 (2)	0.0356 (18)	−0.0035 (15)	0.0131 (15)	−0.0099 (16)
C7	0.0239 (17)	0.040 (2)	0.0369 (18)	−0.0012 (14)	0.0179 (15)	−0.0109 (15)
C8	0.0229 (15)	0.0217 (16)	0.0247 (15)	−0.0011 (12)	0.0158 (13)	−0.0022 (12)
C9	0.0318 (18)	0.0362 (19)	0.0233 (16)	0.0117 (15)	0.0170 (15)	0.0070 (14)
C10	0.0330 (18)	0.042 (2)	0.0240 (16)	0.0069 (15)	0.0190 (15)	−0.0001 (14)
C11	0.0239 (16)	0.0253 (17)	0.0315 (17)	−0.0013 (13)	0.0180 (14)	−0.0051 (13)
C12	0.0385 (19)	0.0287 (19)	0.0358 (19)	0.0128 (15)	0.0243 (17)	0.0095 (14)
C13	0.0426 (19)	0.0320 (19)	0.0286 (16)	0.0092 (15)	0.0256 (16)	0.0074 (14)
C14	0.088 (4)	0.066 (3)	0.081 (3)	−0.021 (3)	0.065 (3)	−0.018 (3)
O7	0.061 (2)	0.091 (3)	0.0553 (19)	−0.0035 (18)	0.0368 (18)	−0.0123 (18)
P1	0.0354 (5)	0.0318 (5)	0.0269 (4)	−0.0112 (4)	0.0162 (4)	−0.0081 (3)
P2	0.0274 (4)	0.0322 (5)	0.0367 (5)	0.0040 (3)	0.0216 (4)	−0.0018 (4)
O1	0.0440 (16)	0.0300 (14)	0.0301 (13)	−0.0136 (13)	0.0179 (13)	−0.0038 (11)
O2	0.0341 (14)	0.0328 (16)	0.0366 (15)	−0.0065 (12)	0.0100 (11)	−0.0035 (13)
O3	0.0408 (17)	0.0319 (15)	0.0241 (14)	−0.0105 (15)	0.0136 (12)	−0.0033 (12)
O2A	0.037 (2)	0.037 (2)	0.031 (2)	−0.0132 (19)	0.0154 (18)	−0.0069 (19)
O1A	0.036 (2)	0.032 (2)	0.029 (2)	−0.015 (2)	0.0130 (19)	−0.0066 (19)
O3A	0.036 (2)	0.033 (2)	0.027 (2)	−0.012 (2)	0.0145 (18)	−0.0056 (19)
O4	0.0349 (12)	0.0390 (13)	0.0471 (13)	0.0083 (11)	0.0279 (11)	0.0085 (11)
O5	0.0314 (12)	0.0301 (13)	0.0372 (12)	0.0024 (10)	0.0171 (10)	0.0026 (10)
O6	0.0295 (12)	0.0356 (13)	0.0412 (13)	0.0040 (10)	0.0186 (10)	−0.0079 (11)
O4A	0.027 (2)	0.031 (2)	0.037 (2)	0.004 (2)	0.0222 (19)	−0.003 (2)
O6A	0.029 (2)	0.032 (2)	0.037 (2)	0.004 (2)	0.0222 (19)	0.001 (2)
O5A	0.029 (2)	0.035 (2)	0.040 (2)	0.004 (2)	0.0190 (19)	−0.003 (2)

Geometric parameters (Å, º)

C1—C2^i	1.542 (4)	C14—O7	1.451 (5)
C1—C2	1.542 (4)	C14—H14A	0.96
C1—C8^i	1.555 (4)	C14—H14B	0.96
C1—C8	1.555 (4)	C14—H14C	0.96
C2—C7	1.374 (4)	O7—H7A	0.82
C2—C3	1.394 (4)	P1—O3A	1.484 (12)
C3—C4	1.383 (5)	P1—O3	1.508 (4)
C3—H3	0.93	P1—O2A	1.509 (10)
C4—C5	1.385 (5)	P1—O2	1.536 (4)
C4—H4	0.93	P1—O1	1.536 (4)
C5—C6	1.374 (5)	P1—O1A	1.622 (11)
C5—P1	1.789 (3)	P2—O6A	1.463 (13)
C6—C7	1.385 (5)	P2—O4	1.465 (3)
C6—H6	0.93	P2—O5A	1.524 (12)
C7—H7	0.93	P2—O6	1.556 (3)
C8—C9	1.388 (4)	P2—O5	1.561 (3)
C8—C13	1.389 (4)	P2—O4A	1.568 (12)
C9—C10	1.389 (4)	O1—H1	0.82
C9—H9	0.93	O2—H2	0.82
C10—C11	1.382 (4)	O2A—H2A	0.82
C10—H10	0.93	O1A—H1A	0.82
C11—C12	1.388 (4)	O5—H5	0.82
C11—P2	1.792 (3)	O6—H6A	0.82
C12—C13	1.383 (5)	O6A—H6A1	0.82
C12—H12	0.93	O5A—H5A	0.82
C13—H13	0.93
C2^i—C1—C2	104.5 (3)	C8—C13—H13	119.3
C2^i—C1—C8^i	111.49 (15)	O7—C14—H14A	109.5
C2—C1—C8^i	112.66 (15)	O7—C14—H14B	109.5
C2^i—C1—C8	112.66 (15)	H14A—C14—H14B	109.5
C2—C1—C8	111.49 (15)	O7—C14—H14C	109.5
C8^i—C1—C8	104.2 (3)	H14A—C14—H14C	109.5
C7—C2—C3	117.4 (3)	H14B—C14—H14C	109.5
C7—C2—C1	123.0 (3)	C14—O7—H7A	109.5
C3—C2—C1	119.4 (2)	O3A—P1—O2A	118.3 (7)
C4—C3—C2	121.3 (3)	O3—P1—O2	112.1 (2)
C4—C3—H3	119.3	O3—P1—O1	110.9 (3)
C2—C3—H3	119.3	O2—P1—O1	110.6 (2)
C3—C4—C5	120.6 (3)	O3A—P1—O1A	108.9 (9)
C3—C4—H4	119.7	O2A—P1—O1A	106.9 (7)
C5—C4—H4	119.7	O3A—P1—C5	116.0 (7)
C6—C5—C4	117.9 (3)	O3—P1—C5	108.6 (2)
C6—C5—P1	121.3 (2)	O2A—P1—C5	106.8 (5)
C4—C5—P1	120.7 (2)	O2—P1—C5	106.52 (17)
C5—C6—C7	121.5 (3)	O1—P1—C5	107.85 (19)
C5—C6—H6	119.2	O1A—P1—C5	97.7 (5)
C7—C6—H6	119.2	O6A—P2—O5A	125.4 (10)
C2—C7—C6	121.1 (3)	O4—P2—O6	114.97 (18)
C2—C7—H7	119.5	O4—P2—O5	112.42 (17)
C6—C7—H7	119.5	O6—P2—O5	103.79 (17)
C9—C8—C13	117.8 (3)	O6A—P2—O4A	114.1 (10)
C9—C8—C1	124.6 (3)	O5A—P2—O4A	96.6 (10)
C13—C8—C1	117.6 (2)	O6A—P2—C11	108.2 (7)
C8—C9—C10	120.8 (3)	O4—P2—C11	111.96 (16)
C8—C9—H9	119.6	O5A—P2—C11	103.2 (7)
C10—C9—H9	119.6	O6—P2—C11	104.74 (15)
C11—C10—C9	121.1 (3)	O5—P2—C11	108.29 (15)
C11—C10—H10	119.5	O4A—P2—C11	107.6 (6)
C9—C10—H10	119.5	P1—O1—H1	109.5
C10—C11—C12	118.2 (3)	P1—O2—H2	109.5
C10—C11—P2	121.8 (2)	P1—O2A—H2A	109.5
C12—C11—P2	120.0 (2)	P1—O1A—H1A	109.5
C13—C12—C11	120.7 (3)	P2—O5—H5	109.5
C13—C12—H12	119.6	P2—O6—H6A	109.5
C11—C12—H12	119.6	P2—O6A—H6A1	109.5
C12—C13—C8	121.3 (3)	P2—O5A—H5A	109.5
C12—C13—H13	119.3
C2^i—C1—C2—C7	115.3 (3)	P2—C11—C12—C13	−179.5 (3)
C8^i—C1—C2—C7	−123.4 (3)	C11—C12—C13—C8	0.7 (5)
C8—C1—C2—C7	−6.6 (4)	C9—C8—C13—C12	−2.3 (5)
C2^i—C1—C2—C3	−60.4 (2)	C1—C8—C13—C12	−179.9 (3)
C8^i—C1—C2—C3	60.8 (4)	C6—C5—P1—O3A	115.4 (8)
C8—C1—C2—C3	177.6 (3)	C4—C5—P1—O3A	−61.8 (8)
C7—C2—C3—C4	3.7 (5)	C6—C5—P1—O3	129.4 (3)
C1—C2—C3—C4	179.7 (3)	C4—C5—P1—O3	−47.8 (4)
C2—C3—C4—C5	−1.3 (5)	C6—C5—P1—O2A	−18.8 (8)
C3—C4—C5—C6	−2.0 (5)	C4—C5—P1—O2A	163.9 (8)
C3—C4—C5—P1	175.4 (3)	C6—C5—P1—O2	8.5 (4)
C4—C5—C6—C7	2.8 (5)	C4—C5—P1—O2	−168.8 (3)
P1—C5—C6—C7	−174.6 (3)	C6—C5—P1—O1	−110.3 (3)
C3—C2—C7—C6	−2.9 (5)	C4—C5—P1—O1	72.5 (4)
C1—C2—C7—C6	−178.8 (3)	C6—C5—P1—O1A	−129.2 (6)
C5—C6—C7—C2	−0.3 (6)	C4—C5—P1—O1A	53.6 (6)
C2^i—C1—C8—C9	1.0 (4)	C10—C11—P2—O6A	110.9 (9)
C2—C1—C8—C9	118.1 (3)	C12—C11—P2—O6A	−68.7 (9)
C8^i—C1—C8—C9	−120.0 (3)	C10—C11—P2—O4	−44.7 (3)
C2^i—C1—C8—C13	178.5 (3)	C12—C11—P2—O4	135.7 (3)
C2—C1—C8—C13	−64.4 (4)	C10—C11—P2—O5A	−114.3 (8)
C8^i—C1—C8—C13	57.5 (2)	C12—C11—P2—O5A	66.1 (8)
C13—C8—C9—C10	2.3 (5)	C10—C11—P2—O6	80.6 (3)
C1—C8—C9—C10	179.8 (3)	C12—C11—P2—O6	−99.0 (3)
C8—C9—C10—C11	−0.7 (5)	C10—C11—P2—O5	−169.2 (3)
C9—C10—C11—C12	−0.9 (5)	C12—C11—P2—O5	11.2 (3)
C9—C10—C11—P2	179.5 (3)	C10—C11—P2—O4A	−12.9 (9)
C10—C11—C12—C13	0.9 (5)	C12—C11—P2—O4A	167.5 (8)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14B···O5^ii	0.96	2.29	3.185 (6)	155
O7—H7A···O3^iii	0.82	2.04	2.861 (5)	177
O7—H7A···O3A^iii	0.82	1.82	2.635 (15)	173
O2—H2···O7^iv	0.82	2.03	2.824 (7)	163
O5A—H5A···O7^v	0.82	2.35	2.910 (17)	126

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