Poly[tetra-aqua-μ(3)-benzene-1,2-di-carboxyl-ato-μ(3)-bromido-penta-μ(2)-bromido-octa-μ(3)-isonicotinato-hepta-copper(I)trilanthanum(III)].

A new lanthanum(III)-copper(I) heterometallic coordination polymer, [Cu(7)La(3)Br(6)(C(6)H(4)NO(2))(8)(C(8)H(4)O(4))(H(2)O)(4)](n), has been prepared by a hydro-thermal method. Of the three La atoms in the asymmetric unit, two are eight-coordinate with bicapped trigonal-prismatic configurations; the third is nine-coordinated and has a tricapped trigonal-prismatic coordination geometry. Of the seven Cu atoms, two are two-coordinate with CuBrN and CuN(2) ligand sets, three have trigonal configurations, viz. CuBrN(2), CuBr(2)N and CuBr(3), while the remaining two adopt distorted tetra-hedral CuBr(3)N geometries. In the crystal structure, adjacent La centers are linked by isonicotinate (IN(-)) and benzene-1,2-dicarboxyl-ate ligands to form a two-dimensional La-carboxyl-ate layer in the ab plane. These layers are further inter-connected with each other by bridging [Cu(IN)(2)] motifs, leading to an unusual three-dimensional heterometallic Cu-halide-lanthanide-organic framework, with the inorganic [Cu(6)Br(6)](n) chains located in the resulting channels. Two Cu atoms are disordered over two positions, both with site occupancy factors of 0.80 and 0.20. O-H⋯O hydrogen bonding between water molecules and carboxylate O atoms helps to consolidate the crystal packing.

Related literature

For background on the structures and applications of heterometallic lanthanide–transition metal (Ln–TM) coordination polymers, see: Benelli & Gatteschi (2002 ▶); Shibasaki & Yoshikawa (2002 ▶); Zhao, Cheng et al. (2004 ▶); Zhao, Chen et al. (2004 ▶); Guillou et al. (2006 ▶); Wang et al. (2006 ▶). For some examples of extended heterometallic Ln–TM architectures, see: Ren et al. (2003 ▶); Prasad et al. (2007 ▶); Cheng et al. (2008 ▶); Deng et al. (2008 ▶); Wang, Li et al. (2008 ▶). For the coordination modes of isonicotinate and benzene-1,2-dicarboxyl­ate ligands, see: Gu & Xue (2007 ▶); Wang, Duan et al. (2008 ▶).

Experimental

Crystal data

[Cu7La3Br6(C6H4NO2)8(C8H4O4)(H2O)4]

M = 2553.96

Monoclinic,

a = 10.1071 (5) Å

b = 19.6311 (3) Å

c = 34.4015 (2) Å

β = 92.480 (2)°

V = 6819.3 (4) Å3

Z = 4

Mo Kα radiation

μ = 7.57 mm−1

T = 295 K

0.20 × 0.10 × 0.09 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.313, T max = 0.549 (expected range = 0.288–0.506)

52743 measured reflections

13363 independent reflections

9870 reflections with I > 2σ(I)

R int = 0.071

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.126

S = 1.18

13363 reflections

955 parameters

H-atom parameters constrained

Δρmax = 1.73 e Å−3

Δρmin = −2.22 e Å−3

Data collection: APEX2 (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809014081/sj2614sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809014081/sj2614Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu7La3Br6(C6H4NO2)8(C8H4O4)(H2O)4]	F(000) = 4848
Mr = 2553.96	Dx = 2.488 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 52743 reflections
a = 10.1071 (5) Å	θ = 1.2–26.0°
b = 19.6311 (3) Å	µ = 7.57 mm−1
c = 34.4015 (2) Å	T = 295 K
β = 92.480 (2)°	Prism, brown
V = 6819.3 (4) Å3	0.20 × 0.10 × 0.09 mm
Z = 4

Bruker APEXII area-detector diffractometer	13363 independent reflections
Radiation source: fine-focus sealed tube	9870 reflections with I > 2σ(I)
graphite	Rint = 0.071
φ and ω scans	θmax = 26.0°, θmin = 1.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.313, Tmax = 0.549	k = −23→24
52743 measured reflections	l = −42→42

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126	H-atom parameters constrained
S = 1.18	w = 1/[σ2(Fo2) + (0.0498P)2 + 4.7192P] where P = (Fo2 + 2Fc2)/3
13363 reflections	(Δ/σ)max = 0.001
955 parameters	Δρmax = 1.73 e Å−3
0 restraints	Δρmin = −2.22 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
La1	0.22600 (4)	0.48720 (2)	0.006803 (12)	0.01347 (11)
La2	0.29679 (4)	0.14367 (2)	−0.026957 (12)	0.01318 (11)
La3	−0.24624 (4)	0.16813 (2)	−0.017184 (13)	0.01663 (12)
Cu1	0.38381 (16)	0.52109 (8)	−0.24321 (3)	0.0605 (4)
Cu2	0.1352 (4)	0.2896 (2)	−0.21115 (11)	0.0565 (9)	0.80
Cu2'	0.0878 (17)	0.3052 (9)	−0.2218 (4)	0.074 (5)	0.20
Cu3	0.8350 (3)	0.1565 (2)	−0.26477 (12)	0.0440 (7)	0.80
Cu3'	0.8908 (14)	0.1708 (11)	−0.2644 (5)	0.064 (4)	0.20
Cu4	0.63663 (16)	0.28675 (8)	−0.26968 (5)	0.0653 (4)
Cu5	0.61139 (14)	0.41101 (7)	−0.23317 (4)	0.0530 (4)
Cu6	0.88795 (15)	0.43063 (7)	−0.27424 (3)	0.0514 (4)
Cu7	1.21736 (16)	0.34075 (8)	−0.28116 (4)	0.0576 (4)
Br1	0.21910 (10)	0.22413 (5)	−0.25622 (3)	0.0408 (3)
Br2	0.57870 (12)	0.17237 (6)	−0.26488 (4)	0.0548 (3)
Br3	0.85917 (10)	0.30796 (5)	−0.25766 (3)	0.0443 (3)
Br4	0.47465 (9)	0.36921 (5)	−0.28606 (3)	0.0359 (2)
Br5	0.76335 (9)	0.50127 (5)	−0.23036 (3)	0.0380 (2)
Br6	1.13084 (9)	0.44473 (5)	−0.25274 (3)	0.0362 (2)
O1	0.1380 (6)	0.5739 (3)	−0.04055 (17)	0.0325 (15)
O2	−0.0776 (5)	0.5648 (3)	−0.05687 (16)	0.0269 (14)
O3	0.3829 (5)	0.4716 (3)	−0.04459 (15)	0.0279 (14)
O4	0.5802 (6)	0.5205 (3)	−0.05111 (16)	0.0308 (15)
O5	−0.1574 (6)	0.4261 (3)	−0.05461 (18)	0.0383 (17)
O6	0.0482 (6)	0.4339 (3)	−0.03153 (17)	0.0392 (17)
O7	0.3772 (6)	0.6005 (3)	0.00383 (19)	0.0406 (17)
H7A	0.4177	0.5917	−0.0167	0.080*
H7B	0.4321	0.5951	0.0231	0.080*
O8	0.2809 (6)	0.3656 (3)	0.00780 (17)	0.0325 (15)
O9	0.2517 (7)	0.2573 (3)	−0.00553 (19)	0.0432 (18)
O10	0.6667 (6)	0.2366 (4)	0.0380 (2)	0.050 (2)
O11	0.4973 (6)	0.1853 (3)	0.00866 (16)	0.0275 (14)
O12	0.6320 (6)	0.0893 (4)	−0.06027 (17)	0.0433 (18)
O13	0.4174 (5)	0.0698 (3)	−0.07032 (17)	0.0306 (15)
O14	0.6171 (7)	0.2426 (4)	−0.0589 (2)	0.064 (3)
O15	0.4104 (6)	0.2149 (3)	−0.07631 (18)	0.0381 (16)
O16	0.4042 (5)	0.0575 (3)	0.02259 (16)	0.0295 (14)
H16C	0.3978	0.0251	0.0388	0.080*
H16D	0.4832	0.0734	0.0256	0.080*
O17	0.1231 (5)	0.1276 (3)	0.01773 (16)	0.0285 (14)
O18	−0.0733 (6)	0.1657 (4)	0.03231 (17)	0.0381 (17)
O19	0.1224 (6)	0.1580 (3)	−0.07778 (18)	0.0331 (15)
O20	−0.0813 (6)	0.1887 (4)	−0.06543 (17)	0.0381 (16)
O21	−0.3099 (5)	0.0712 (3)	0.02882 (15)	0.0217 (13)
O22	−0.1878 (5)	−0.0234 (3)	0.03169 (15)	0.0197 (12)
O23	−0.1039 (5)	0.0580 (3)	−0.03168 (17)	0.0321 (15)
H23C	−0.0254	0.0630	−0.0290	0.080*
H23D	−0.1202	0.0204	−0.0159	0.080*
O24	−0.1433 (10)	0.2896 (4)	−0.0098 (3)	0.084 (3)
H24C	−0.1207	0.3284	−0.0007	0.101*
H24D	−0.0999	0.2827	−0.0300	0.101*
C1	0.0388 (8)	0.5791 (4)	−0.0635 (2)	0.0238 (19)
C2	0.0667 (7)	0.6024 (4)	−0.1045 (2)	0.0205 (18)
C3	−0.0229 (8)	0.5899 (5)	−0.1351 (2)	0.030 (2)
H3A	−0.1032	0.5689	−0.1305	0.036*
C4	0.0066 (9)	0.6087 (5)	−0.1727 (3)	0.037 (2)
H4A	−0.0560	0.6005	−0.1928	0.044*
C5	0.2079 (10)	0.6501 (5)	−0.1517 (3)	0.040 (3)
H5A	0.2882	0.6708	−0.1567	0.049*
C6	0.1829 (9)	0.6333 (5)	−0.1140 (3)	0.034 (2)
H6A	0.2463	0.6431	−0.0944	0.040*
C7	0.4703 (8)	0.5001 (4)	−0.0643 (2)	0.0206 (18)
C8	0.4435 (8)	0.5066 (4)	−0.1068 (2)	0.0238 (19)
C9	0.3389 (9)	0.4730 (5)	−0.1256 (2)	0.032 (2)
H9A	0.2799	0.4476	−0.1115	0.038*
C10	0.3229 (10)	0.4776 (5)	−0.1654 (3)	0.044 (3)
H10A	0.2540	0.4534	−0.1777	0.052*
C11	0.5003 (10)	0.5473 (5)	−0.1686 (3)	0.041 (3)
H11A	0.5567	0.5733	−0.1833	0.050*
C12	0.5248 (9)	0.5449 (5)	−0.1292 (2)	0.030 (2)
H12A	0.5955	0.5688	−0.1177	0.035*
C13	−0.0358 (8)	0.4176 (4)	−0.0570 (2)	0.0199 (18)
C14	0.0095 (8)	0.3870 (4)	−0.0943 (2)	0.0205 (18)
C15	−0.0494 (9)	0.4072 (5)	−0.1290 (3)	0.032 (2)
H15A	−0.1170	0.4394	−0.1295	0.038*
C16	−0.0078 (10)	0.3795 (5)	−0.1629 (3)	0.039 (2)
H16A	−0.0463	0.3949	−0.1864	0.047*
C17	0.1388 (9)	0.3108 (5)	−0.1299 (3)	0.039 (3)
H17A	0.2010	0.2759	−0.1301	0.047*
C18	0.1073 (8)	0.3381 (4)	−0.0946 (3)	0.030 (2)
H18A	0.1508	0.3240	−0.0716	0.036*
C19	0.2871 (8)	0.3047 (4)	0.0165 (2)	0.0218 (18)
C20	0.3417 (8)	0.2869 (4)	0.0570 (2)	0.0220 (19)
C21	0.2682 (8)	0.3108 (4)	0.0879 (3)	0.027 (2)
H21A	0.1893	0.3341	0.0827	0.032*
C22	0.3115 (9)	0.3002 (4)	0.1262 (3)	0.032 (2)
H22A	0.2605	0.3151	0.1464	0.038*
C23	0.4283 (9)	0.2680 (5)	0.1342 (3)	0.034 (2)
H23A	0.4574	0.2609	0.1599	0.040*
C24	0.5047 (9)	0.2454 (5)	0.1040 (3)	0.033 (2)
H24A	0.5864	0.2251	0.1098	0.039*
C25	0.4602 (7)	0.2528 (4)	0.0652 (2)	0.0211 (18)
C26	0.5453 (8)	0.2248 (4)	0.0353 (3)	0.0244 (19)
C27	0.5335 (8)	0.0750 (4)	−0.0816 (2)	0.0197 (18)
C28	0.5547 (8)	0.0625 (4)	−0.1237 (2)	0.0201 (18)
C29	0.6764 (8)	0.0441 (5)	−0.1370 (3)	0.032 (2)
H29A	0.7490	0.0395	−0.1196	0.038*
C30	0.6903 (9)	0.0325 (5)	−0.1760 (2)	0.033 (2)
H30A	0.7731	0.0192	−0.1841	0.039*
C31	0.4752 (10)	0.0582 (6)	−0.1901 (3)	0.045 (3)
H31A	0.4060	0.0645	−0.2085	0.054*
C32	0.4512 (9)	0.0690 (5)	−0.1518 (3)	0.038 (2)
H32A	0.3666	0.0805	−0.1444	0.045*
C33	0.5163 (9)	0.2446 (5)	−0.0812 (3)	0.031 (2)
C34	0.5301 (8)	0.2866 (4)	−0.1169 (2)	0.0242 (19)
C35	0.4653 (9)	0.2684 (5)	−0.1515 (3)	0.032 (2)
H35A	0.4074	0.2315	−0.1525	0.038*
C36	0.4877 (9)	0.3059 (5)	−0.1848 (3)	0.037 (2)
H36A	0.4469	0.2921	−0.2083	0.045*
C37	0.6226 (9)	0.3787 (5)	−0.1509 (3)	0.033 (2)
H37A	0.6742	0.4179	−0.1500	0.040*
C38	0.6105 (9)	0.3424 (4)	−0.1166 (3)	0.031 (2)
H38A	0.6563	0.3559	−0.0939	0.038*
C39	0.0442 (8)	0.1505 (4)	0.0412 (2)	0.0208 (18)
C40	0.0887 (7)	0.1565 (4)	0.0830 (2)	0.0195 (18)
C41	0.0109 (8)	0.1899 (4)	0.1090 (2)	0.027 (2)
H41A	−0.0680	0.2106	0.1006	0.032*
C42	0.0531 (9)	0.1919 (5)	0.1480 (3)	0.035 (2)
H42A	0.0019	0.2150	0.1656	0.042*
C43	0.2389 (9)	0.1316 (5)	0.1347 (3)	0.033 (2)
H43A	0.3188	0.1123	0.1434	0.040*
C44	0.2062 (8)	0.1270 (5)	0.0962 (3)	0.030 (2)
H44A	0.2609	0.1048	0.0792	0.036*
C45	0.0064 (8)	0.1715 (4)	−0.0876 (2)	0.0199 (18)
C46	−0.0323 (8)	0.1683 (4)	−0.1304 (2)	0.0214 (18)
C47	−0.1537 (8)	0.1923 (4)	−0.1445 (2)	0.027 (2)
H47A	−0.2133	0.2114	−0.1277	0.033*
C48	−0.1848 (9)	0.1875 (5)	−0.1837 (3)	0.033 (2)
H48A	−0.2639	0.2070	−0.1930	0.040*
C49	0.0058 (9)	0.1337 (5)	−0.1953 (2)	0.032 (2)
H49A	0.0608	0.1126	−0.2126	0.038*
C50	0.0497 (8)	0.1386 (4)	−0.1569 (3)	0.027 (2)
H50A	0.1330	0.1224	−0.1489	0.032*
C51	−0.2364 (7)	0.0287 (4)	0.0465 (2)	0.0179 (17)
C52	−0.2047 (7)	0.0423 (4)	0.0886 (2)	0.0179 (17)
C53	−0.2863 (8)	0.0798 (5)	0.1118 (3)	0.033 (2)
H53A	−0.3620	0.1001	0.1007	0.039*
C54	−0.2575 (10)	0.0875 (5)	0.1509 (3)	0.040 (3)
H54A	−0.3163	0.1113	0.1659	0.048*
C55	−0.0661 (9)	0.0266 (5)	0.1462 (3)	0.035 (2)
H55A	0.0116	0.0091	0.1577	0.042*
C56	−0.0915 (8)	0.0148 (5)	0.1070 (2)	0.029 (2)
H56A	−0.0334	−0.0114	0.0930	0.035*
N1	0.1216 (7)	0.6380 (4)	−0.1813 (2)	0.0334 (19)
N2	0.4013 (8)	0.5150 (4)	−0.1872 (2)	0.040 (2)
N3	0.0842 (9)	0.3320 (4)	−0.1638 (2)	0.043 (2)
N4	0.5940 (8)	0.0390 (4)	−0.2026 (2)	0.0356 (19)
N5	0.5652 (7)	0.3610 (4)	−0.1848 (2)	0.0315 (18)
N6	0.1655 (8)	0.1616 (4)	0.1610 (2)	0.0346 (19)
N7	−0.1092 (8)	0.1570 (4)	−0.2089 (2)	0.0346 (19)
N8	−0.1468 (8)	0.0616 (4)	0.1681 (2)	0.0337 (19)

	U11	U22	U33	U12	U13	U23
La1	0.0140 (2)	0.0170 (2)	0.0094 (2)	0.00099 (17)	0.00035 (17)	0.00074 (18)
La2	0.0137 (2)	0.0148 (2)	0.0109 (2)	0.00006 (18)	−0.00093 (17)	−0.00007 (18)
La3	0.0145 (2)	0.0225 (3)	0.0126 (2)	0.00030 (19)	−0.00268 (17)	0.00349 (19)
Cu1	0.0995 (12)	0.0690 (11)	0.0132 (6)	0.0036 (9)	0.0041 (7)	0.0086 (6)
Cu2	0.075 (2)	0.055 (2)	0.041 (2)	−0.0055 (15)	0.0266 (14)	−0.0164 (14)
Cu2'	0.114 (13)	0.076 (9)	0.037 (8)	0.019 (8)	0.046 (8)	−0.005 (6)
Cu3	0.058 (2)	0.0613 (18)	0.0126 (10)	0.0103 (15)	−0.0006 (14)	−0.0047 (10)
Cu3'	0.093 (12)	0.086 (12)	0.014 (4)	0.031 (9)	−0.001 (8)	−0.006 (6)
Cu4	0.0700 (10)	0.0659 (11)	0.0600 (10)	−0.0001 (8)	0.0015 (8)	0.0028 (8)
Cu5	0.0697 (9)	0.0580 (9)	0.0309 (7)	−0.0293 (8)	−0.0008 (6)	0.0128 (6)
Cu6	0.0762 (10)	0.0571 (9)	0.0201 (7)	0.0036 (7)	−0.0047 (6)	0.0050 (6)
Cu7	0.0823 (11)	0.0660 (10)	0.0236 (7)	−0.0031 (8)	−0.0095 (7)	0.0041 (6)
Br1	0.0451 (6)	0.0387 (6)	0.0395 (6)	−0.0013 (5)	0.0128 (5)	−0.0057 (5)
Br2	0.0543 (7)	0.0558 (8)	0.0539 (7)	−0.0024 (6)	−0.0033 (6)	−0.0041 (6)
Br3	0.0484 (6)	0.0371 (6)	0.0475 (6)	0.0005 (5)	0.0032 (5)	0.0082 (5)
Br4	0.0291 (5)	0.0463 (6)	0.0317 (5)	−0.0051 (4)	−0.0062 (4)	0.0062 (5)
Br5	0.0354 (5)	0.0380 (6)	0.0405 (6)	−0.0063 (4)	0.0006 (4)	−0.0055 (5)
Br6	0.0335 (5)	0.0523 (7)	0.0230 (5)	−0.0105 (4)	0.0018 (4)	−0.0016 (4)
O1	0.029 (3)	0.042 (4)	0.026 (3)	−0.003 (3)	−0.006 (3)	0.020 (3)
O2	0.016 (3)	0.034 (4)	0.030 (3)	0.003 (3)	0.007 (3)	0.016 (3)
O3	0.028 (3)	0.042 (4)	0.014 (3)	−0.007 (3)	0.010 (2)	0.000 (3)
O4	0.028 (3)	0.041 (4)	0.022 (3)	−0.009 (3)	−0.009 (3)	0.003 (3)
O5	0.039 (4)	0.037 (4)	0.039 (4)	−0.002 (3)	0.005 (3)	−0.025 (3)
O6	0.054 (4)	0.039 (4)	0.024 (4)	−0.004 (3)	−0.014 (3)	−0.010 (3)
O7	0.032 (4)	0.044 (4)	0.045 (4)	−0.001 (3)	0.002 (3)	0.003 (3)
O8	0.048 (4)	0.020 (4)	0.028 (4)	0.001 (3)	−0.006 (3)	0.003 (3)
O9	0.063 (5)	0.017 (4)	0.047 (4)	0.015 (3)	−0.025 (4)	−0.012 (3)
O10	0.022 (4)	0.061 (5)	0.066 (5)	−0.005 (3)	0.003 (3)	−0.038 (4)
O11	0.031 (3)	0.027 (4)	0.025 (3)	−0.001 (3)	−0.004 (3)	−0.006 (3)
O12	0.031 (4)	0.079 (6)	0.020 (3)	−0.006 (3)	−0.004 (3)	−0.018 (3)
O13	0.028 (3)	0.033 (4)	0.032 (4)	−0.006 (3)	0.015 (3)	−0.011 (3)
O14	0.034 (4)	0.088 (6)	0.069 (5)	0.000 (4)	−0.009 (4)	0.066 (5)
O15	0.038 (4)	0.046 (4)	0.030 (4)	−0.009 (3)	0.001 (3)	0.017 (3)
O16	0.024 (3)	0.030 (4)	0.034 (4)	0.003 (3)	−0.006 (3)	0.010 (3)
O17	0.024 (3)	0.048 (4)	0.015 (3)	0.007 (3)	0.010 (2)	0.000 (3)
O18	0.021 (3)	0.073 (5)	0.019 (3)	0.016 (3)	−0.012 (3)	−0.012 (3)
O19	0.029 (4)	0.040 (4)	0.029 (4)	0.004 (3)	−0.007 (3)	0.006 (3)
O20	0.033 (4)	0.062 (5)	0.020 (3)	−0.005 (3)	0.004 (3)	0.005 (3)
O21	0.026 (3)	0.023 (3)	0.016 (3)	0.004 (2)	0.001 (2)	0.002 (2)
O22	0.027 (3)	0.013 (3)	0.019 (3)	0.005 (2)	−0.001 (2)	−0.007 (2)
O23	0.023 (3)	0.040 (4)	0.033 (4)	0.005 (3)	0.007 (3)	−0.001 (3)
O24	0.136 (8)	0.038 (5)	0.079 (6)	−0.036 (5)	0.025 (6)	−0.010 (5)
C1	0.030 (5)	0.019 (5)	0.022 (5)	0.009 (4)	0.006 (4)	−0.002 (4)
C2	0.019 (4)	0.017 (4)	0.026 (5)	0.003 (3)	0.004 (3)	0.005 (4)
C3	0.030 (5)	0.033 (6)	0.026 (5)	−0.008 (4)	0.000 (4)	0.004 (4)
C4	0.035 (5)	0.049 (7)	0.026 (5)	−0.009 (5)	−0.001 (4)	−0.001 (5)
C5	0.041 (6)	0.061 (7)	0.020 (5)	−0.024 (5)	0.001 (4)	0.000 (5)
C6	0.027 (5)	0.047 (6)	0.026 (5)	−0.008 (4)	−0.006 (4)	0.003 (4)
C7	0.026 (5)	0.019 (5)	0.017 (4)	0.001 (4)	0.002 (3)	−0.003 (3)
C8	0.033 (5)	0.026 (5)	0.012 (4)	−0.002 (4)	0.000 (3)	0.000 (4)
C9	0.034 (5)	0.048 (6)	0.014 (4)	−0.011 (4)	0.000 (4)	0.001 (4)
C10	0.048 (6)	0.056 (7)	0.027 (5)	−0.020 (5)	−0.007 (5)	0.005 (5)
C11	0.063 (7)	0.038 (6)	0.024 (5)	−0.008 (5)	0.010 (5)	0.005 (5)
C12	0.039 (5)	0.031 (5)	0.018 (5)	−0.011 (4)	0.003 (4)	0.009 (4)
C13	0.022 (4)	0.018 (5)	0.021 (4)	−0.005 (3)	0.005 (4)	−0.002 (3)
C14	0.021 (4)	0.016 (4)	0.025 (5)	−0.006 (3)	0.006 (3)	0.001 (4)
C15	0.036 (5)	0.033 (6)	0.026 (5)	0.008 (4)	−0.003 (4)	−0.005 (4)
C16	0.051 (6)	0.043 (7)	0.025 (5)	0.003 (5)	−0.001 (5)	−0.001 (5)
C17	0.030 (5)	0.030 (6)	0.059 (7)	0.004 (4)	0.020 (5)	0.003 (5)
C18	0.023 (5)	0.029 (5)	0.037 (6)	0.004 (4)	0.005 (4)	0.004 (4)
C19	0.024 (4)	0.021 (5)	0.021 (4)	0.003 (4)	0.001 (3)	−0.004 (4)
C20	0.028 (5)	0.011 (4)	0.026 (5)	0.001 (3)	−0.003 (4)	−0.004 (4)
C21	0.024 (5)	0.020 (5)	0.037 (5)	0.002 (4)	0.003 (4)	0.000 (4)
C22	0.046 (6)	0.022 (5)	0.027 (5)	0.004 (4)	0.009 (4)	0.004 (4)
C23	0.050 (6)	0.028 (5)	0.022 (5)	−0.001 (5)	−0.005 (4)	−0.006 (4)
C24	0.035 (5)	0.031 (6)	0.031 (5)	0.004 (4)	−0.014 (4)	−0.002 (4)
C25	0.017 (4)	0.024 (5)	0.022 (4)	−0.005 (3)	0.000 (3)	−0.003 (4)
C26	0.016 (4)	0.023 (5)	0.035 (5)	0.005 (3)	0.004 (4)	0.005 (4)
C27	0.025 (5)	0.021 (5)	0.014 (4)	0.002 (3)	0.001 (3)	−0.006 (3)
C28	0.025 (4)	0.025 (5)	0.010 (4)	0.002 (4)	0.000 (3)	−0.002 (3)
C29	0.024 (5)	0.044 (6)	0.027 (5)	0.003 (4)	0.000 (4)	−0.001 (4)
C30	0.035 (5)	0.047 (6)	0.017 (5)	0.007 (5)	0.012 (4)	−0.008 (4)
C31	0.050 (7)	0.069 (8)	0.013 (5)	0.004 (6)	−0.018 (4)	−0.010 (5)
C32	0.031 (5)	0.062 (7)	0.021 (5)	0.002 (5)	0.002 (4)	−0.007 (5)
C33	0.030 (5)	0.038 (6)	0.024 (5)	0.011 (4)	−0.002 (4)	0.014 (4)
C34	0.015 (4)	0.027 (5)	0.031 (5)	0.002 (3)	0.003 (4)	0.009 (4)
C35	0.031 (5)	0.033 (6)	0.031 (5)	−0.004 (4)	0.005 (4)	0.004 (4)
C36	0.046 (6)	0.037 (6)	0.029 (5)	−0.015 (5)	−0.007 (4)	0.000 (5)
C37	0.043 (6)	0.025 (5)	0.031 (5)	−0.011 (4)	−0.010 (4)	0.005 (4)
C38	0.031 (5)	0.022 (5)	0.041 (6)	−0.004 (4)	−0.002 (4)	0.006 (4)
C39	0.021 (4)	0.025 (5)	0.017 (4)	−0.005 (4)	0.005 (3)	0.000 (4)
C40	0.015 (4)	0.024 (5)	0.020 (4)	0.000 (3)	−0.003 (3)	0.001 (4)
C41	0.030 (5)	0.028 (5)	0.022 (5)	0.000 (4)	0.002 (4)	0.001 (4)
C42	0.041 (6)	0.041 (6)	0.024 (5)	−0.003 (5)	0.007 (4)	−0.006 (4)
C43	0.035 (5)	0.031 (6)	0.034 (6)	0.004 (4)	−0.008 (4)	−0.001 (4)
C44	0.019 (4)	0.041 (6)	0.029 (5)	−0.006 (4)	−0.003 (4)	−0.005 (4)
C45	0.019 (4)	0.018 (4)	0.023 (5)	−0.007 (3)	−0.002 (4)	0.010 (4)
C46	0.025 (4)	0.018 (4)	0.022 (5)	0.000 (3)	0.000 (3)	0.007 (4)
C47	0.026 (5)	0.034 (5)	0.022 (5)	0.006 (4)	−0.002 (4)	−0.002 (4)
C48	0.031 (5)	0.045 (6)	0.023 (5)	0.013 (4)	−0.007 (4)	0.005 (4)
C49	0.041 (6)	0.036 (6)	0.020 (5)	0.011 (4)	0.010 (4)	0.003 (4)
C50	0.019 (4)	0.031 (5)	0.031 (5)	0.008 (4)	0.001 (4)	0.000 (4)
C51	0.013 (4)	0.026 (5)	0.015 (4)	−0.009 (3)	0.001 (3)	0.008 (4)
C52	0.020 (4)	0.016 (4)	0.018 (4)	−0.002 (3)	−0.001 (3)	−0.003 (3)
C53	0.024 (5)	0.045 (6)	0.029 (5)	0.009 (4)	−0.004 (4)	−0.003 (4)
C54	0.045 (6)	0.051 (7)	0.025 (5)	0.006 (5)	0.006 (5)	−0.017 (5)
C55	0.043 (6)	0.034 (6)	0.026 (5)	−0.007 (5)	−0.007 (4)	−0.007 (4)
C56	0.030 (5)	0.038 (6)	0.020 (5)	0.005 (4)	−0.003 (4)	−0.004 (4)
N1	0.035 (4)	0.043 (5)	0.022 (4)	−0.013 (4)	−0.001 (3)	0.000 (4)
N2	0.051 (5)	0.049 (5)	0.018 (4)	−0.016 (4)	−0.001 (4)	−0.005 (4)
N3	0.055 (6)	0.044 (6)	0.033 (5)	−0.012 (4)	0.020 (4)	−0.006 (4)
N4	0.057 (5)	0.038 (5)	0.012 (4)	0.007 (4)	0.001 (4)	−0.007 (3)
N5	0.028 (4)	0.036 (5)	0.030 (4)	−0.014 (3)	−0.002 (3)	0.006 (4)
N6	0.048 (5)	0.036 (5)	0.019 (4)	−0.005 (4)	−0.004 (4)	0.001 (3)
N7	0.042 (5)	0.045 (5)	0.017 (4)	0.011 (4)	−0.004 (3)	−0.002 (4)
N8	0.048 (5)	0.035 (5)	0.018 (4)	−0.007 (4)	0.002 (4)	−0.008 (4)

La1—O6	2.420 (6)	C4—N1	1.342 (11)
La1—O4i	2.434 (5)	C4—H4A	0.9300
La1—O3	2.445 (5)	C5—N1	1.334 (11)
La1—O8	2.451 (6)	C5—C6	1.370 (12)
La1—O5ii	2.486 (6)	C5—H5A	0.9300
La1—O1	2.494 (5)	C6—H6A	0.9300
La1—O2ii	2.545 (5)	C7—C8	1.480 (11)
La1—O7	2.703 (6)	C8—C12	1.374 (11)
La2—O9	2.399 (6)	C8—C9	1.383 (11)
La2—O17	2.404 (5)	C9—C10	1.373 (12)
La2—O13	2.443 (6)	C9—H9A	0.9300
La2—O19	2.444 (6)	C10—N2	1.336 (12)
La2—O11	2.462 (5)	C10—H10A	0.9300
La2—O15	2.515 (6)	C11—N2	1.326 (12)
La2—O16	2.606 (5)	C11—C12	1.369 (12)
La2—O22iii	2.607 (5)	C11—H11A	0.9300
La3—O18	2.387 (5)	C12—H12A	0.9300
La3—O14iv	2.436 (6)	C13—C14	1.505 (11)
La3—O20	2.436 (6)	C14—C15	1.369 (11)
La3—O12iv	2.439 (6)	C14—C18	1.378 (11)
La3—O10iv	2.515 (6)	C15—C16	1.371 (12)
La3—O21	2.574 (5)	C15—H15A	0.9300
La3—O24	2.610 (7)	C16—N3	1.319 (12)
La3—O23	2.657 (6)	C16—H16A	0.9300
La3—O11iv	2.797 (6)	C17—N3	1.338 (13)
La3—C26iv	3.043 (8)	C17—C18	1.377 (13)
Cu1—N4v	1.920 (7)	C17—H17A	0.9300
Cu1—N2	1.931 (7)	C18—H18A	0.9300
Cu2—Cu2'	0.666 (13)	C19—C20	1.516 (11)
Cu2—N3	1.917 (9)	C20—C25	1.390 (11)
Cu2—Br1	2.212 (4)	C20—C21	1.405 (11)
Cu2—Cu7iv	2.770 (4)	C21—C22	1.384 (12)
Cu2'—N3	2.064 (18)	C21—H21A	0.9300
Cu2'—Br1	2.415 (16)	C22—C23	1.357 (12)
Cu2'—Cu7iv	2.569 (17)	C22—H22A	0.9300
Cu2'—Br3iv	2.572 (16)	C23—C24	1.393 (12)
Cu3—Cu3'	0.629 (14)	C23—H23A	0.9300
Cu3—N1vi	1.959 (8)	C24—C25	1.400 (11)
Cu3—N7vii	1.980 (8)	C24—H24A	0.9300
Cu3—Br2	2.609 (4)	C25—C26	1.476 (11)
Cu3'—N7vii	1.927 (19)	C26—La3vii	3.043 (8)
Cu3'—N1vi	1.976 (19)	C27—C28	1.493 (10)
Cu3'—Br3	2.72 (2)	C28—C29	1.380 (11)
Cu4—Br3	2.3071 (19)	C28—C32	1.399 (11)
Cu4—Br2	2.328 (2)	C29—C30	1.376 (11)
Cu4—Br4	2.3533 (19)	C29—H29A	0.9300
Cu4—Cu5	2.761 (2)	C30—N4	1.311 (11)
Cu5—N5	2.005 (7)	C30—H30A	0.9300
Cu5—Br5	2.3441 (16)	C31—N4	1.347 (12)
Cu5—Br4	2.3827 (16)	C31—C32	1.369 (12)
Cu6—N8viii	2.004 (7)	C31—H31A	0.9300
Cu6—Br5	2.4397 (17)	C32—H32A	0.9300
Cu6—Br3	2.4946 (18)	C33—C34	1.490 (11)
Cu6—Br6	2.5481 (17)	C34—C38	1.364 (11)
Cu7—N6viii	2.037 (7)	C34—C35	1.381 (12)
Cu7—Br6	2.4415 (18)	C35—C36	1.389 (12)
Cu7—Br1vii	2.4447 (18)	C35—H35A	0.9300
Cu7—Cu2'vii	2.569 (17)	C36—N5	1.335 (11)
Cu7—Br4vii	2.6722 (19)	C36—H36A	0.9300
Cu7—Cu2vii	2.770 (4)	C37—N5	1.326 (11)
Br1—Cu7iv	2.4447 (18)	C37—C38	1.386 (12)
Br3—Cu2'vii	2.572 (17)	C37—H37A	0.9300
Br4—Cu7iv	2.6722 (19)	C38—H38A	0.9300
O1—C1	1.253 (9)	C39—C40	1.491 (11)
O2—C1	1.240 (9)	C40—C44	1.380 (11)
O2—La1ii	2.545 (5)	C40—C41	1.382 (11)
O3—C7	1.268 (9)	C41—C42	1.389 (12)
O4—C7	1.247 (9)	C41—H41A	0.9300
O4—La1i	2.434 (5)	C42—N6	1.342 (12)
O5—C13	1.247 (9)	C42—H42A	0.9300
O5—La1ii	2.486 (6)	C43—N6	1.332 (12)
O6—C13	1.236 (9)	C43—C44	1.354 (12)
O7—H7A	0.8505	C43—H43A	0.9300
O7—H7B	0.8512	C44—H44A	0.9300
O8—C19	1.232 (10)	C45—C46	1.507 (11)
O9—C19	1.244 (10)	C46—C47	1.383 (11)
O10—C26	1.247 (9)	C46—C50	1.388 (11)
O10—La3vii	2.515 (6)	C47—C48	1.374 (11)
O11—C26	1.279 (10)	C47—H47A	0.9300
O11—La3vii	2.797 (6)	C48—N7	1.324 (11)
O12—C27	1.243 (9)	C48—H48A	0.9300
O12—La3vii	2.439 (6)	C49—N7	1.317 (11)
O13—C27	1.256 (9)	C49—C50	1.377 (12)
O14—C33	1.250 (10)	C49—H49A	0.9300
O14—La3vii	2.436 (6)	C50—H50A	0.9300
O15—C33	1.237 (10)	C51—C52	1.493 (10)
O16—H16C	0.8495	C52—C53	1.384 (11)
O16—H16D	0.8589	C52—C56	1.393 (11)
O17—C39	1.243 (9)	C53—C54	1.371 (12)
O18—C39	1.250 (9)	C53—H53A	0.9300
O19—C45	1.235 (9)	C54—N8	1.343 (12)
O20—C45	1.241 (10)	C54—H54A	0.9300
O21—C51	1.258 (9)	C55—N8	1.328 (11)
O22—C51	1.252 (9)	C55—C56	1.379 (12)
O22—La2iii	2.607 (5)	C55—H55A	0.9300
O23—H23C	0.8013	C56—H56A	0.9300
O23—H23D	0.9328	N1—Cu3v	1.959 (8)
O24—H24C	0.8501	N1—Cu3'v	1.976 (19)
O24—H24D	0.8498	N4—Cu1vi	1.920 (7)
C1—C2	1.521 (11)	N6—Cu7ix	2.037 (7)
C2—C6	1.375 (11)	N7—Cu3'iv	1.927 (19)
C2—C3	1.380 (11)	N7—Cu3iv	1.980 (8)
C3—C4	1.390 (12)	N8—Cu6ix	2.004 (7)
C3—H3A	0.9300
O6—La1—O4i	150.8 (2)	H23C—O23—H23D	103.4
O6—La1—O3	92.4 (2)	La3—O24—H24C	162.5
O4i—La1—O3	85.15 (19)	La3—O24—H24D	89.5
O6—La1—O8	75.4 (2)	H24C—O24—H24D	107.7
O4i—La1—O8	75.8 (2)	O2—C1—O1	127.2 (8)
O3—La1—O8	74.6 (2)	O2—C1—C2	117.0 (7)
O6—La1—O5ii	115.8 (2)	O1—C1—C2	115.7 (7)
O4i—La1—O5ii	82.4 (2)	C6—C2—C3	115.9 (8)
O3—La1—O5ii	140.6 (2)	C6—C2—C1	123.3 (8)
O8—La1—O5ii	136.6 (2)	C3—C2—C1	120.8 (7)
O6—La1—O1	72.8 (2)	C2—C3—C4	120.1 (8)
O4i—La1—O1	134.92 (19)	C2—C3—H3A	119.9
O3—La1—O1	80.7 (2)	C4—C3—H3A	119.9
O8—La1—O1	138.4 (2)	N1—C4—C3	122.8 (8)
O5ii—La1—O1	82.1 (2)	N1—C4—H4A	118.6
O6—La1—O2ii	75.5 (2)	C3—C4—H4A	118.6
O4i—La1—O2ii	91.89 (18)	N1—C5—C6	122.6 (9)
O3—La1—O2ii	149.2 (2)	N1—C5—H5A	118.7
O8—La1—O2ii	74.9 (2)	C6—C5—H5A	118.7
O5ii—La1—O2ii	68.7 (2)	C5—C6—C2	121.7 (8)
O1—La1—O2ii	120.78 (18)	C5—C6—H6A	119.1
O6—La1—O7	138.0 (2)	C2—C6—H6A	119.1
O4i—La1—O7	68.51 (19)	O4—C7—O3	125.2 (7)
O3—La1—O7	71.97 (19)	O4—C7—C8	117.0 (7)
O8—La1—O7	132.38 (19)	O3—C7—C8	117.7 (7)
O5ii—La1—O7	68.7 (2)	C12—C8—C9	117.5 (8)
O1—La1—O7	66.41 (19)	C12—C8—C7	120.8 (8)
O2ii—La1—O7	134.9 (2)	C9—C8—C7	121.7 (8)
O9—La2—O17	76.8 (2)	C10—C9—C8	119.3 (8)
O9—La2—O13	147.7 (2)	C10—C9—H9A	120.3
O17—La2—O13	135.3 (2)	C8—C9—H9A	120.3
O9—La2—O19	88.4 (2)	N2—C10—C9	123.3 (9)
O17—La2—O19	87.0 (2)	N2—C10—H10A	118.3
O13—La2—O19	89.7 (2)	C9—C10—H10A	118.3
O9—La2—O11	72.6 (2)	N2—C11—C12	124.1 (9)
O17—La2—O11	109.47 (19)	N2—C11—H11A	117.9
O13—La2—O11	94.55 (19)	C12—C11—H11A	117.9
O19—La2—O11	150.5 (2)	C11—C12—C8	119.2 (9)
O9—La2—O15	77.8 (2)	C11—C12—H12A	120.4
O17—La2—O15	150.7 (2)	C8—C12—H12A	120.4
O13—La2—O15	70.3 (2)	O6—C13—O5	124.6 (8)
O19—La2—O15	77.8 (2)	O6—C13—C14	118.9 (7)
O11—La2—O15	76.2 (2)	O5—C13—C14	116.6 (7)
O9—La2—O16	118.8 (2)	C15—C14—C18	118.7 (8)
O17—La2—O16	77.99 (19)	C15—C14—C13	119.3 (8)
O13—La2—O16	79.00 (19)	C18—C14—C13	122.0 (8)
O19—La2—O16	144.06 (19)	C14—C15—C16	119.3 (9)
O11—La2—O16	65.12 (18)	C14—C15—H15A	120.3
O15—La2—O16	127.83 (19)	C16—C15—H15A	120.3
O9—La2—O22iii	140.9 (2)	N3—C16—C15	122.9 (9)
O17—La2—O22iii	66.62 (19)	N3—C16—H16A	118.5
O13—La2—O22iii	69.22 (17)	C15—C16—H16A	118.5
O19—La2—O22iii	76.68 (18)	N3—C17—C18	123.1 (9)
O11—La2—O22iii	131.93 (18)	N3—C17—H17A	118.5
O15—La2—O22iii	131.72 (19)	C18—C17—H17A	118.5
O16—La2—O22iii	67.40 (17)	C17—C18—C14	118.2 (9)
O18—La3—O14iv	144.2 (3)	C17—C18—H18A	120.9
O18—La3—O20	89.3 (2)	C14—C18—H18A	120.9
O14iv—La3—O20	83.5 (2)	O8—C19—O9	124.5 (8)
O18—La3—O12iv	139.1 (2)	O8—C19—C20	117.4 (7)
O14iv—La3—O12iv	76.4 (3)	O9—C19—C20	118.1 (8)
O20—La3—O12iv	91.9 (2)	C25—C20—C21	119.1 (8)
O18—La3—O10iv	75.0 (2)	C25—C20—C19	124.9 (7)
O14iv—La3—O10iv	85.1 (3)	C21—C20—C19	115.8 (7)
O20—La3—O10iv	134.2 (2)	C22—C21—C20	120.9 (8)
O12iv—La3—O10iv	127.9 (2)	C22—C21—H21A	119.5
O18—La3—O21	75.0 (2)	C20—C21—H21A	119.5
O14iv—La3—O21	131.0 (2)	C23—C22—C21	120.1 (9)
O20—La3—O21	137.6 (2)	C23—C22—H22A	120.0
O12iv—La3—O21	76.8 (2)	C21—C22—H22A	120.0
O10iv—La3—O21	80.0 (2)	C22—C23—C24	120.1 (9)
O18—La3—O24	70.9 (3)	C22—C23—H23A	120.0
O14iv—La3—O24	73.9 (3)	C24—C23—H23A	120.0
O20—La3—O24	68.5 (3)	C23—C24—C25	120.9 (8)
O12iv—La3—O24	145.8 (3)	C23—C24—H24A	119.5
O10iv—La3—O24	65.7 (3)	C25—C24—H24A	119.5
O21—La3—O24	136.4 (2)	C20—C25—C24	118.8 (8)
O18—La3—O23	74.5 (2)	C20—C25—C26	124.2 (7)
O14iv—La3—O23	132.5 (3)	C24—C25—C26	117.0 (7)
O20—La3—O23	67.4 (2)	O10—C26—O11	120.5 (8)
O12iv—La3—O23	68.4 (2)	O10—C26—C25	118.7 (8)
O10iv—La3—O23	141.9 (2)	O11—C26—C25	120.6 (7)
O21—La3—O23	70.47 (17)	O10—C26—La3vii	53.7 (4)
O24—La3—O23	123.1 (3)	O11—C26—La3vii	66.8 (4)
O18—La3—O11iv	115.82 (19)	C25—C26—La3vii	171.5 (6)
O14iv—La3—O11iv	66.7 (2)	O12—C27—O13	124.9 (7)
O20—La3—O11iv	150.15 (19)	O12—C27—C28	117.7 (7)
O12iv—La3—O11iv	79.61 (18)	O13—C27—C28	117.4 (7)
O10iv—La3—O11iv	48.42 (18)	C29—C28—C32	116.4 (8)
O21—La3—O11iv	68.52 (17)	C29—C28—C27	122.2 (7)
O24—La3—O11iv	103.3 (2)	C32—C28—C27	121.4 (7)
O23—La3—O11iv	132.43 (17)	C30—C29—C28	119.9 (8)
O18—La3—C26iv	95.1 (2)	C30—C29—H29A	120.1
O14iv—La3—C26iv	74.9 (3)	C28—C29—H29A	120.1
O20—La3—C26iv	148.7 (2)	N4—C30—C29	124.0 (8)
O12iv—La3—C26iv	104.4 (2)	N4—C30—H30A	118.0
O10iv—La3—C26iv	23.6 (2)	C29—C30—H30A	118.0
O21—La3—C26iv	73.01 (19)	N4—C31—C32	123.2 (8)
O24—La3—C26iv	83.7 (3)	N4—C31—H31A	118.4
O23—La3—C26iv	143.5 (2)	C32—C31—H31A	118.4
O11iv—La3—C26iv	24.84 (19)	C31—C32—C28	119.6 (9)
N4v—Cu1—N2	166.2 (3)	C31—C32—H32A	120.2
Cu2'—Cu2—N3	93.2 (18)	C28—C32—H32A	120.2
Cu2'—Cu2—Br1	99.8 (18)	O15—C33—O14	126.0 (8)
N3—Cu2—Br1	166.5 (3)	O15—C33—C34	119.1 (7)
Cu2'—Cu2—Cu7iv	65.7 (18)	O14—C33—C34	114.9 (8)
N3—Cu2—Cu7iv	133.0 (3)	C38—C34—C35	118.3 (8)
Br1—Cu2—Cu7iv	57.48 (10)	C38—C34—C33	121.0 (8)
Cu2—Cu2'—N3	68.0 (16)	C35—C34—C33	120.6 (8)
Cu2—Cu2'—Br1	64.5 (16)	C34—C35—C36	119.0 (8)
N3—Cu2'—Br1	132.4 (7)	C34—C35—H35A	120.5
Cu2—Cu2'—Cu7iv	101 (2)	C36—C35—H35A	120.5
N3—Cu2'—Cu7iv	136.8 (10)	N5—C36—C35	123.1 (9)
Br1—Cu2'—Cu7iv	58.6 (4)	N5—C36—H36A	118.5
Cu2—Cu2'—Br3iv	152 (3)	C35—C36—H36A	118.5
N3—Cu2'—Br3iv	113.9 (7)	N5—C37—C38	124.2 (8)
Br1—Cu2'—Br3iv	106.3 (7)	N5—C37—H37A	117.9
Cu7iv—Cu2'—Br3iv	95.3 (5)	C38—C37—H37A	117.9
Cu3'—Cu3—N1vi	82.3 (19)	C34—C38—C37	118.7 (9)
Cu3'—Cu3—N7vii	76.0 (19)	C34—C38—H38A	120.6
N1vi—Cu3—N7vii	148.7 (4)	C37—C38—H38A	120.6
Cu3'—Cu3—Br2	147 (2)	O17—C39—O18	123.8 (7)
N1vi—Cu3—Br2	106.5 (3)	O17—C39—C40	118.7 (7)
N7vii—Cu3—Br2	104.0 (3)	O18—C39—C40	117.5 (7)
Cu3—Cu3'—N7vii	86 (2)	C44—C40—C41	119.4 (8)
Cu3—Cu3'—N1vi	79.3 (19)	C44—C40—C39	120.2 (7)
N7vii—Cu3'—N1vi	152.7 (12)	C41—C40—C39	120.4 (7)
Cu3—Cu3'—Br3	109 (2)	C40—C41—C42	118.7 (8)
N7vii—Cu3'—Br3	92.9 (7)	C40—C41—H41A	120.7
N1vi—Cu3'—Br3	113.5 (9)	C42—C41—H41A	120.7
Br3—Cu4—Br2	114.05 (8)	N6—C42—C41	121.9 (9)
Br3—Cu4—Br4	125.56 (8)	N6—C42—H42A	119.0
Br2—Cu4—Br4	120.39 (8)	C41—C42—H42A	119.0
Br3—Cu4—Cu5	82.39 (6)	N6—C43—C44	125.1 (9)
Br2—Cu4—Cu5	142.32 (8)	N6—C43—H43A	117.5
Br4—Cu4—Cu5	54.84 (5)	C44—C43—H43A	117.5
N5—Cu5—Br5	120.8 (2)	C43—C44—C40	117.7 (9)
N5—Cu5—Br4	108.5 (2)	C43—C44—H44A	121.2
Br5—Cu5—Br4	130.48 (6)	C40—C44—H44A	121.2
N5—Cu5—Cu4	88.5 (2)	O19—C45—O20	125.8 (8)
Br5—Cu5—Cu4	127.83 (7)	O19—C45—C46	117.5 (8)
Br4—Cu5—Cu4	53.85 (5)	O20—C45—C46	116.7 (7)
N8viii—Cu6—Br5	119.7 (2)	C47—C46—C50	117.3 (8)
N8viii—Cu6—Br3	106.4 (2)	C47—C46—C45	121.1 (8)
Br5—Cu6—Br3	109.80 (6)	C50—C46—C45	121.5 (7)
N8viii—Cu6—Br6	113.8 (2)	C48—C47—C46	118.9 (8)
Br5—Cu6—Br6	105.98 (6)	C48—C47—H47A	120.6
Br3—Cu6—Br6	99.15 (6)	C46—C47—H47A	120.6
N6viii—Cu7—Br6	109.2 (2)	N7—C48—C47	124.0 (8)
N6viii—Cu7—Br1vii	108.6 (2)	N7—C48—H48A	118.0
Br6—Cu7—Br1vii	129.77 (7)	C47—C48—H48A	118.0
N6viii—Cu7—Cu2'vii	130.7 (5)	N7—C49—C50	124.0 (8)
Br6—Cu7—Cu2'vii	72.8 (4)	N7—C49—H49A	118.0
Br1vii—Cu7—Cu2'vii	57.5 (4)	C50—C49—H49A	118.0
N6viii—Cu7—Br4vii	98.8 (2)	C49—C50—C46	118.9 (8)
Br6—Cu7—Br4vii	102.53 (6)	C49—C50—H50A	120.5
Br1vii—Cu7—Br4vii	103.04 (6)	C46—C50—H50A	120.5
Cu2'vii—Cu7—Br4vii	129.6 (4)	O22—C51—O21	125.4 (7)
N6viii—Cu7—Cu2vii	140.1 (3)	O22—C51—C52	118.1 (7)
Br6—Cu7—Cu2vii	80.14 (9)	O21—C51—C52	116.6 (7)
Br1vii—Cu7—Cu2vii	49.72 (9)	C53—C52—C56	116.2 (7)
Cu2'vii—Cu7—Cu2vii	13.7 (3)	C53—C52—C51	123.1 (7)
Br4vii—Cu7—Cu2vii	117.39 (9)	C56—C52—C51	120.6 (7)
Cu2—Br1—Cu2'	15.8 (3)	C54—C53—C52	121.2 (8)
Cu2—Br1—Cu7iv	72.81 (11)	C54—C53—H53A	119.4
Cu2'—Br1—Cu7iv	63.8 (4)	C52—C53—H53A	119.4
Cu4—Br2—Cu3	82.10 (12)	N8—C54—C53	121.9 (9)
Cu4—Br3—Cu6	104.81 (7)	N8—C54—H54A	119.0
Cu4—Br3—Cu2'vii	158.6 (4)	C53—C54—H54A	119.0
Cu6—Br3—Cu2'vii	91.1 (4)	N8—C55—C56	123.3 (9)
Cu4—Br3—Cu3'	85.6 (3)	N8—C55—H55A	118.3
Cu6—Br3—Cu3'	156.9 (4)	C56—C55—H55A	118.3
Cu2'vii—Br3—Cu3'	85.1 (5)	C55—C56—C52	119.6 (8)
Cu4—Br4—Cu5	71.31 (6)	C55—C56—H56A	120.2
Cu4—Br4—Cu7iv	120.66 (6)	C52—C56—H56A	120.2
Cu5—Br4—Cu7iv	123.90 (6)	C5—N1—C4	116.9 (8)
Cu5—Br5—Cu6	84.24 (6)	C5—N1—Cu3v	121.7 (6)
Cu7—Br6—Cu6	98.64 (6)	C4—N1—Cu3v	121.3 (6)
C1—O1—La1	136.1 (6)	C5—N1—Cu3'v	132.7 (8)
C1—O2—La1ii	143.8 (5)	C4—N1—Cu3'v	109.2 (8)
C7—O3—La1	145.1 (5)	Cu3v—N1—Cu3'v	18.4 (4)
C7—O4—La1i	152.6 (6)	C11—N2—C10	116.4 (8)
C13—O5—La1ii	116.1 (5)	C11—N2—Cu1	119.1 (6)
C13—O6—La1	165.8 (6)	C10—N2—Cu1	124.4 (6)
La1—O7—H7A	99.1	C16—N3—C17	117.6 (8)
La1—O7—H7B	102.7	C16—N3—Cu2	122.9 (7)
H7A—O7—H7B	107.5	C17—N3—Cu2	119.4 (7)
C19—O8—La1	163.1 (6)	C16—N3—Cu2'	104.2 (8)
C19—O9—La2	146.1 (6)	C17—N3—Cu2'	137.9 (8)
C26—O10—La3vii	102.7 (5)	Cu2—N3—Cu2'	18.8 (4)
C26—O11—La2	146.8 (5)	C30—N4—C31	116.8 (7)
C26—O11—La3vii	88.4 (5)	C30—N4—Cu1vi	123.0 (6)
La2—O11—La3vii	123.8 (2)	C31—N4—Cu1vi	120.2 (6)
C27—O12—La3vii	150.7 (6)	C37—N5—C36	116.5 (8)
C27—O13—La2	129.7 (5)	C37—N5—Cu5	119.6 (6)
C33—O14—La3vii	143.8 (7)	C36—N5—Cu5	123.6 (6)
C33—O15—La2	141.0 (6)	C43—N6—C42	117.2 (8)
La2—O16—H16C	150.9	C43—N6—Cu7ix	121.8 (6)
La2—O16—H16D	101.5	C42—N6—Cu7ix	121.0 (6)
H16C—O16—H16D	107.0	C49—N7—C48	116.8 (7)
C39—O17—La2	151.1 (6)	C49—N7—Cu3'iv	111.3 (8)
C39—O18—La3	147.0 (5)	C48—N7—Cu3'iv	127.6 (9)
C45—O19—La2	150.1 (6)	C49—N7—Cu3iv	123.6 (6)
C45—O20—La3	154.4 (6)	C48—N7—Cu3iv	119.4 (6)
C51—O21—La3	129.1 (5)	Cu3'iv—N7—Cu3iv	18.5 (4)
C51—O22—La2iii	126.3 (5)	C55—N8—C54	117.7 (8)
La3—O23—H23C	114.8	C55—N8—Cu6ix	121.1 (6)
La3—O23—H23D	115.0	C54—N8—Cu6ix	121.0 (6)

D—H···A	D—H	H···A	D···A	D—H···A
O16—H16D···O21vii	0.86	2.09	2.901 (7)	157
O23—H23D···O22	0.93	2.00	2.861 (8)	153
O24—H24D···O20	0.85	2.22	2.844 (11)	130

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O16—H16D⋯O21i	0.86	2.09	2.901 (7)	157
O23—H23D⋯O22	0.93	2.00	2.861 (8)	153
O24—H24D⋯O20	0.85	2.22	2.844 (11)	130

Symmetry code: (i) .