Self-assembling of three rare structurally various homomultinuclear Cu^II complexes derived from a bis­(salamo)-based multioxime ligand

A family of rare structurally different homometal multinuclear Cu^II bis­(salamo)-based complexes, [Cu₄(L)₂(MeOH)₂](ClO₄)₂·2MeOH (1), [Cu₄(L)₂(EtOH)₂](NO₃)₂·2EtOH (2) and [Cu₂(HL)(EtOH)Br₂]·CHCl₃ (3), has been successfully synthesized by the reactions of cupric salts with a bis­(salamo)-based multidentate chelate ligand (H₃L). The salamo-based ligand [R-CH=N—O—(CH₂)_n—O—N=CH—R] is a new type of salen-based analog. Complexes (1) and (2) are isostructural structures, and crystallize in monoclinic space group P2₁/n with centrosymmetric spiral structures, where the main structures contain two fully deprotonated ligand (L)³⁻ units, a charged tetranuclear Cu^II folding center and two coordinated solvent molecules. Complex (3) crystallizes in monoclinic space group Cc and consists of two Cu^II cations, one incompletely deprotonated ligand (HL)²⁻ unit and one coordinated ethanol molecule, and forms a novel homo-binuclear Cu^II complex structure due to Br⁻ counter anions. Complexes (1)–(3) have zero-dimensional cluster-based structures and are further assembled into three-dimensional frameworks via intermolecular interactions. Because of the different solvents and counter anions which have a significant influence on the structures of complexes (1)–(3), the interactions were quantitatively evaluated by Hirshfeld surfaces analyses. Complexes (1)–(3) have been characterized by elemental analyses, IR spectra, UV–vis spectra and X-ray crystallography analyses. In addition, fluorescence properties are evaluated and DFT calculations are performed.

Computing details

Cell refinement: SAINT V8.38A (?, 2016) for (3). Data reduction: SAINT V8.38A (?, 2016) for (3). For all structures, program(s) used to solve structure: olex2.solve (Bourhis et al., 2015). Program(s) used to refine structure: olex2.refine (Bourhis et al., 2015) for (1), (2); SHELXL (Sheldrick, 2015) for (3). For all structures, molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

(1)

Crystal data

C56H54Cu4N12O24·2(ClO4)·2(CH4O)	F(000) = 1832
Mr = 1796.25	Dx = 1.744 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 15.2568 (4) Å	Cell parameters from 9913 reflections
b = 14.5155 (4) Å	θ = 2.4–26.7°
c = 15.4550 (4) Å	µ = 1.41 mm^−1
β = 92.086 (1)°	T = 173 K
V = 3420.40 (16) Å^3	BLOCK
Z = 2	0.24 × 0.22 × 0.19 mm

Data collection

Bruker D8 Venture diffractometer	6759 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
phi and ω scans	θmax = 26.7°, θmin = 2.3°
Absorption correction: multi-scan SADABS	h = −19→19
Tmin = 0.659, Tmax = 0.745	k = −18→18
43196 measured reflections	l = −19→17
7259 independent 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)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.089	w = 1/[σ^2(Fo^2) + (0.034P)^2 + 5.5923P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
7259 reflections	Δρmax = 1.76 e Å^−3
530 parameters	Δρmin = −0.84 e Å^−3
24 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.91994 (2)	0.42705 (2)	0.47503 (2)	0.02062 (8)
Cu2	0.81008 (2)	0.54391 (2)	0.32847 (2)	0.02363 (8)
O1	0.99904 (11)	0.50320 (11)	0.40949 (10)	0.0237 (3)
O2	1.1402 (2)	0.4285 (2)	0.04653 (15)	0.0771 (9)
O3	1.16494 (17)	0.2965 (2)	0.10245 (15)	0.0596 (7)
O4	1.01646 (12)	0.26020 (12)	0.53252 (11)	0.0319 (4)
O5	0.84267 (13)	0.27639 (12)	0.58260 (11)	0.0326 (4)
O6	0.82819 (11)	0.51845 (11)	0.45155 (10)	0.0234 (3)
O7	0.82668 (13)	0.75794 (13)	0.31108 (12)	0.0368 (4)
O8	0.76207 (13)	0.64490 (14)	0.17251 (12)	0.0362 (4)
O9	0.84128 (12)	0.41440 (12)	0.31032 (11)	0.0289 (4)
O10	0.98332 (17)	0.2922 (2)	−0.04492 (18)	0.0700 (8)
O11	1.0022 (2)	0.1669 (2)	0.0280 (2)	0.0813 (10)
O12	0.66230 (13)	0.52197 (16)	0.33764 (13)	0.0429 (5)
H12	0.6317 (12)	0.519 (2)	0.2890 (9)	0.064*
N1	1.14247 (17)	0.3761 (2)	0.10805 (15)	0.0464 (7)
N2	1.00387 (13)	0.32580 (14)	0.46466 (12)	0.0241 (4)
N3	0.83437 (13)	0.36773 (13)	0.55317 (13)	0.0239 (4)
N4	0.80778 (14)	0.68020 (14)	0.36246 (13)	0.0266 (4)
N5	0.80502 (15)	0.56364 (16)	0.20435 (13)	0.0308 (5)
N6	0.97630 (18)	0.2464 (2)	0.0207 (2)	0.0582 (8)
C1	1.03816 (15)	0.47239 (17)	0.34105 (14)	0.0225 (4)
C2	1.06584 (15)	0.37967 (17)	0.33332 (15)	0.0238 (5)
C3	1.10456 (16)	0.34945 (19)	0.25788 (16)	0.0295 (5)
H3	1.1249	0.2879	0.2531	0.035*
C4	1.11278 (16)	0.4105 (2)	0.19058 (15)	0.0325 (6)
C5	1.09085 (17)	0.5031 (2)	0.19807 (16)	0.0339 (6)
H5	1.0998	0.5444	0.1515	0.041*
C6	1.05612 (16)	0.53422 (19)	0.27343 (16)	0.0290 (5)
H6	1.0441	0.5980	0.2801	0.035*
C7	1.05748 (15)	0.31437 (17)	0.40359 (15)	0.0255 (5)
H7	1.0933	0.2608	0.4044	0.031*
C8	0.95615 (19)	0.18486 (18)	0.52274 (19)	0.0357 (6)
H8A	0.9628	0.1441	0.5739	0.043*
H8B	0.9712	0.1485	0.4711	0.043*
C9	0.86210 (18)	0.21537 (18)	0.51311 (18)	0.0329 (6)
H9A	0.8522	0.2473	0.4570	0.039*
H9B	0.8229	0.1611	0.5141	0.039*
C10	0.77784 (16)	0.41121 (17)	0.59732 (15)	0.0267 (5)
H10	0.7488	0.3780	0.6408	0.032*
C11	0.75547 (15)	0.50714 (17)	0.58532 (15)	0.0251 (5)
C12	0.78022 (15)	0.55751 (16)	0.51221 (15)	0.0226 (4)
C13	0.75395 (15)	0.65006 (17)	0.50536 (15)	0.0257 (5)
C14	0.70756 (17)	0.69077 (18)	0.57170 (16)	0.0308 (5)
H14	0.6931	0.7543	0.5675	0.037*
C15	0.68193 (18)	0.6416 (2)	0.64357 (17)	0.0337 (6)
C16	0.70581 (17)	0.54948 (19)	0.64842 (16)	0.0312 (5)
H16	0.6878	0.5139	0.6962	0.037*
C17	0.6318 (2)	0.6874 (2)	0.7139 (2)	0.0503 (8)
H17A	0.6730	0.7101	0.7591	0.076*
H17B	0.5917	0.6428	0.7390	0.076*
H17C	0.5979	0.7392	0.6894	0.076*
C18	0.77861 (16)	0.70874 (17)	0.43431 (16)	0.0275 (5)
H18	0.7726	0.7734	0.4417	0.033*
C19	0.88018 (18)	0.7363 (2)	0.24016 (19)	0.0384 (6)
H19A	0.9165	0.6815	0.2547	0.046*
H19B	0.9201	0.7884	0.2294	0.046*
C20	0.8249 (2)	0.7173 (2)	0.15990 (19)	0.0418 (7)
H20A	0.7934	0.7742	0.1422	0.050*
H20B	0.8635	0.6996	0.1125	0.050*
C21	0.83001 (18)	0.5104 (2)	0.14403 (16)	0.0352 (6)
H21	0.8238	0.5319	0.0861	0.042*
C22	0.86678 (17)	0.4204 (2)	0.15805 (17)	0.0328 (6)
C23	0.86576 (16)	0.37506 (18)	0.23964 (16)	0.0288 (5)
C24	0.89341 (18)	0.28137 (19)	0.24222 (19)	0.0356 (6)
H24	0.8877	0.2470	0.2941	0.043*
C25	0.92804 (19)	0.2396 (2)	0.1715 (2)	0.0429 (7)
H25	0.9475	0.1775	0.1750	0.051*
C26	0.93441 (18)	0.2888 (2)	0.0946 (2)	0.0432 (7)
C27	0.90222 (18)	0.3760 (2)	0.08640 (18)	0.0403 (7)
H27	0.9037	0.4068	0.0322	0.048*
C28	0.6151 (2)	0.4694 (2)	0.3978 (2)	0.0492 (8)
H28A	0.5620	0.4443	0.3690	0.074*
H28B	0.5987	0.5089	0.4460	0.074*
H28C	0.6519	0.4187	0.4199	0.074*
Cl1	0.33320 (6)	0.56949 (6)	0.12328 (6)	0.0574 (2)
O13	0.5620 (4)	0.4776 (6)	0.1930 (4)	0.0611 (19)	0.547 (15)
H13	0.5155	0.5084	0.1882	0.092*	0.547 (15)
O13A	0.5677 (6)	0.5340 (13)	0.1909 (6)	0.095 (4)	0.453 (15)
H13A	0.5193	0.5563	0.1739	0.143*	0.453 (15)
O14	0.4164 (6)	0.6041 (7)	0.1665 (8)	0.091 (3)	0.547 (15)
O14A	0.4202 (6)	0.5912 (10)	0.1198 (11)	0.101 (4)	0.453 (15)
O15	0.3299 (8)	0.6125 (6)	0.0459 (4)	0.074 (3)	0.547 (15)
O15A	0.2779 (9)	0.5877 (6)	0.0419 (5)	0.081 (3)	0.453 (15)
O16	0.3268 (2)	0.47310 (17)	0.13361 (18)	0.0745 (9)
O17	0.2807 (3)	0.6142 (2)	0.1861 (2)	0.0921 (11)
C29	0.6033 (3)	0.4814 (3)	0.1205 (3)	0.0741 (12)
H29A	0.5622	0.4680	0.0719	0.111*	0.547 (15)
H29B	0.6507	0.4359	0.1217	0.111*	0.547 (15)
H29C	0.6280	0.5432	0.1134	0.111*	0.547 (15)
H29D	0.5610	0.4808	0.0713	0.111*	0.453 (15)
H29E	0.6149	0.4181	0.1398	0.111*	0.453 (15)
H29F	0.6581	0.5099	0.1029	0.111*	0.453 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02309 (14)	0.02021 (14)	0.01900 (14)	0.00196 (10)	0.00665 (10)	0.00251 (10)
Cu2	0.02706 (15)	0.02623 (15)	0.01779 (14)	0.00225 (11)	0.00347 (11)	0.00262 (11)
O1	0.0279 (8)	0.0235 (8)	0.0201 (7)	−0.0011 (6)	0.0084 (6)	0.0002 (6)
O2	0.102 (2)	0.107 (2)	0.0236 (11)	0.0061 (18)	0.0272 (13)	0.0058 (13)
O3	0.0575 (15)	0.0799 (19)	0.0425 (13)	0.0120 (13)	0.0197 (11)	−0.0205 (12)
O4	0.0345 (9)	0.0309 (9)	0.0304 (9)	0.0043 (7)	0.0020 (7)	0.0136 (7)
O5	0.0458 (11)	0.0240 (9)	0.0291 (9)	0.0049 (8)	0.0159 (8)	0.0082 (7)
O6	0.0264 (8)	0.0260 (8)	0.0181 (7)	0.0047 (7)	0.0059 (6)	0.0024 (6)
O7	0.0501 (12)	0.0258 (9)	0.0348 (10)	−0.0026 (8)	0.0049 (8)	0.0107 (8)
O8	0.0383 (10)	0.0411 (11)	0.0291 (9)	0.0041 (8)	−0.0004 (8)	0.0109 (8)
O9	0.0344 (9)	0.0287 (9)	0.0240 (8)	0.0003 (7)	0.0044 (7)	−0.0019 (7)
O10	0.0537 (15)	0.108 (2)	0.0501 (15)	−0.0144 (15)	0.0230 (12)	−0.0359 (16)
O11	0.0686 (18)	0.079 (2)	0.098 (2)	0.0049 (15)	0.0267 (16)	−0.0525 (18)
O12	0.0349 (11)	0.0584 (13)	0.0353 (11)	0.0004 (9)	0.0018 (8)	0.0060 (10)
N1	0.0354 (13)	0.079 (2)	0.0259 (12)	−0.0005 (13)	0.0115 (10)	−0.0095 (13)
N2	0.0274 (10)	0.0231 (10)	0.0221 (9)	0.0013 (8)	0.0037 (8)	0.0044 (8)
N3	0.0277 (10)	0.0195 (9)	0.0247 (10)	0.0010 (8)	0.0054 (8)	0.0050 (8)
N4	0.0294 (10)	0.0246 (10)	0.0258 (10)	−0.0009 (8)	−0.0002 (8)	0.0078 (8)
N5	0.0328 (11)	0.0367 (12)	0.0231 (10)	0.0028 (9)	0.0039 (8)	0.0060 (9)
N6	0.0394 (15)	0.078 (2)	0.0582 (19)	−0.0093 (15)	0.0135 (13)	−0.0406 (17)
C1	0.0200 (10)	0.0304 (12)	0.0172 (10)	−0.0014 (9)	0.0016 (8)	−0.0006 (9)
C2	0.0208 (11)	0.0296 (12)	0.0212 (11)	−0.0010 (9)	0.0032 (9)	−0.0027 (9)
C3	0.0227 (11)	0.0378 (14)	0.0284 (12)	0.0002 (10)	0.0049 (9)	−0.0074 (10)
C4	0.0244 (12)	0.0555 (17)	0.0182 (11)	−0.0026 (11)	0.0075 (9)	−0.0051 (11)
C5	0.0289 (13)	0.0531 (17)	0.0201 (11)	−0.0028 (12)	0.0053 (10)	0.0089 (11)
C6	0.0260 (12)	0.0355 (13)	0.0259 (12)	0.0005 (10)	0.0038 (9)	0.0065 (10)
C7	0.0238 (11)	0.0252 (11)	0.0276 (12)	0.0019 (9)	0.0026 (9)	−0.0028 (9)
C8	0.0429 (15)	0.0238 (12)	0.0414 (15)	0.0041 (11)	0.0132 (12)	0.0062 (11)
C9	0.0385 (14)	0.0241 (12)	0.0368 (14)	−0.0045 (10)	0.0117 (11)	−0.0004 (10)
C10	0.0281 (12)	0.0300 (12)	0.0225 (11)	−0.0010 (10)	0.0078 (9)	0.0037 (9)
C11	0.0239 (11)	0.0290 (12)	0.0227 (11)	0.0034 (9)	0.0041 (9)	0.0005 (9)
C12	0.0205 (11)	0.0271 (12)	0.0202 (11)	0.0021 (9)	0.0016 (8)	−0.0020 (9)
C13	0.0254 (11)	0.0285 (12)	0.0231 (11)	0.0030 (9)	−0.0010 (9)	−0.0010 (9)
C14	0.0330 (13)	0.0301 (13)	0.0294 (12)	0.0089 (10)	0.0001 (10)	−0.0046 (10)
C15	0.0336 (13)	0.0422 (15)	0.0254 (12)	0.0118 (11)	0.0043 (10)	−0.0053 (11)
C16	0.0322 (13)	0.0400 (14)	0.0218 (11)	0.0064 (11)	0.0070 (10)	0.0015 (10)
C17	0.064 (2)	0.0543 (19)	0.0338 (15)	0.0271 (16)	0.0167 (14)	−0.0030 (14)
C18	0.0283 (12)	0.0235 (11)	0.0306 (12)	0.0032 (9)	−0.0032 (10)	0.0004 (10)
C19	0.0300 (13)	0.0437 (16)	0.0419 (15)	−0.0029 (12)	0.0068 (11)	0.0173 (13)
C20	0.0458 (16)	0.0469 (17)	0.0335 (14)	0.0026 (13)	0.0092 (12)	0.0173 (13)
C21	0.0345 (14)	0.0509 (16)	0.0205 (12)	−0.0029 (12)	0.0058 (10)	0.0022 (11)
C22	0.0287 (13)	0.0438 (15)	0.0262 (12)	−0.0050 (11)	0.0057 (10)	−0.0069 (11)
C23	0.0229 (11)	0.0354 (13)	0.0283 (12)	−0.0039 (10)	0.0030 (9)	−0.0064 (10)
C24	0.0317 (13)	0.0338 (14)	0.0413 (15)	−0.0045 (11)	0.0021 (11)	−0.0099 (12)
C25	0.0321 (14)	0.0410 (16)	0.0557 (18)	−0.0038 (12)	0.0027 (13)	−0.0212 (14)
C26	0.0293 (13)	0.0570 (19)	0.0439 (16)	−0.0078 (13)	0.0088 (12)	−0.0281 (15)
C27	0.0335 (14)	0.0584 (19)	0.0296 (13)	−0.0092 (13)	0.0080 (11)	−0.0135 (13)
C28	0.0446 (17)	0.0513 (19)	0.0523 (19)	−0.0155 (14)	0.0078 (14)	−0.0079 (15)
Cl1	0.0605 (5)	0.0420 (4)	0.0715 (6)	0.0092 (4)	0.0254 (4)	0.0297 (4)
O13	0.056 (3)	0.067 (4)	0.059 (3)	−0.011 (3)	−0.015 (2)	0.017 (3)
O13A	0.065 (5)	0.160 (10)	0.060 (4)	0.001 (6)	−0.013 (3)	0.016 (6)
O14	0.100 (5)	0.069 (4)	0.107 (7)	−0.003 (4)	0.030 (5)	0.025 (5)
O14A	0.060 (4)	0.107 (7)	0.138 (9)	−0.003 (4)	0.050 (6)	0.066 (7)
O15	0.106 (7)	0.062 (4)	0.055 (3)	0.003 (4)	0.010 (4)	0.023 (3)
O15A	0.111 (8)	0.053 (4)	0.077 (5)	−0.014 (4)	−0.032 (5)	0.028 (3)
O16	0.126 (3)	0.0364 (13)	0.0611 (17)	0.0134 (15)	0.0021 (17)	0.0067 (12)
O17	0.123 (3)	0.073 (2)	0.083 (2)	0.034 (2)	0.045 (2)	0.0097 (17)
C29	0.068 (3)	0.063 (3)	0.090 (3)	−0.010 (2)	−0.017 (2)	−0.004 (2)

Geometric parameters (Å, º)

Cu1—O1	1.9477 (16)	C10—C11	1.444 (3)
Cu1—O1^i	2.3618 (17)	C11—C12	1.409 (3)
Cu1—O6	1.9530 (16)	C11—C16	1.399 (3)
Cu1—N2	1.960 (2)	C12—C13	1.405 (3)
Cu1—N3	2.0048 (19)	C13—C14	1.398 (3)
Cu2—O6	1.9476 (16)	C13—C18	1.450 (3)
Cu2—O9	1.9618 (18)	C14—H14	0.9500
Cu2—O12	2.286 (2)	C14—C15	1.388 (4)
Cu2—N4	2.048 (2)	C15—C16	1.388 (4)
Cu2—N5	1.938 (2)	C15—C17	1.507 (4)
O1—Cu1^i	2.3618 (17)	C16—H16	0.9500
O1—C1	1.312 (3)	C17—H17A	0.9800
O2—N1	1.217 (4)	C17—H17B	0.9800
O3—N1	1.209 (4)	C17—H17C	0.9800
O4—N2	1.424 (2)	C18—H18	0.9500
O4—C8	1.434 (3)	C19—H19A	0.9900
O5—N3	1.406 (2)	C19—H19B	0.9900
O5—C9	1.431 (3)	C19—C20	1.500 (4)
O6—C12	1.336 (3)	C20—H20A	0.9900
O7—N4	1.415 (3)	C20—H20B	0.9900
O7—C19	1.425 (3)	C21—H21	0.9500
O8—N5	1.428 (3)	C21—C22	1.435 (4)
O8—C20	1.440 (4)	C22—C23	1.423 (4)
O9—C23	1.299 (3)	C22—C27	1.407 (4)
O10—N6	1.220 (4)	C23—C24	1.424 (4)
O11—N6	1.223 (5)	C24—H24	0.9500
O12—H12	0.872 (9)	C24—C25	1.372 (4)
O12—C28	1.419 (4)	C25—H25	0.9500
N1—C4	1.457 (3)	C25—C26	1.393 (5)
N2—C7	1.282 (3)	C26—C27	1.362 (5)
N3—C10	1.285 (3)	C27—H27	0.9500
N4—C18	1.280 (3)	C28—H28A	0.9800
N5—C21	1.279 (3)	C28—H28B	0.9800
N6—C26	1.465 (4)	C28—H28C	0.9800
C1—C2	1.417 (3)	Cl1—O14	1.500 (9)
C1—C6	1.412 (3)	Cl1—O14A	1.368 (9)
C2—C3	1.397 (3)	Cl1—O15	1.348 (5)
C2—C7	1.451 (3)	Cl1—O15A	1.512 (8)
C3—H3	0.9500	Cl1—O16	1.412 (3)
C3—C4	1.375 (4)	Cl1—O17	1.436 (3)
C4—C5	1.391 (4)	O13—H13	0.8401
C5—H5	0.9500	O13—C29	1.307 (8)
C5—C6	1.373 (4)	O13A—H13A	0.8400
C6—H6	0.9500	O13A—C29	1.451 (11)
C7—H7	0.9500	C29—H29A	0.9800
C8—H8A	0.9900	C29—H29B	0.9800
C8—H8B	0.9900	C29—H29C	0.9800
C8—C9	1.504 (4)	C29—H29D	0.9800
C9—H9A	0.9900	C29—H29E	0.9800
C9—H9B	0.9900	C29—H29F	0.9800
C10—H10	0.9500
O1—Cu1—O1^i	80.36 (6)	C16—C11—C12	119.9 (2)
O1—Cu1—O6	88.36 (7)	O6—C12—C11	120.8 (2)
O1—Cu1—N2	87.94 (7)	O6—C12—C13	121.0 (2)
O1—Cu1—N3	170.57 (7)	C13—C12—C11	118.2 (2)
O6—Cu1—O1^i	101.60 (6)	C12—C13—C18	122.5 (2)
O6—Cu1—N2	163.80 (8)	C14—C13—C12	120.0 (2)
O6—Cu1—N3	85.73 (7)	C14—C13—C18	117.3 (2)
N2—Cu1—O1^i	93.31 (7)	C13—C14—H14	118.8
N2—Cu1—N3	99.73 (8)	C15—C14—C13	122.3 (2)
N3—Cu1—O1^i	93.63 (7)	C15—C14—H14	118.8
O6—Cu2—O9	86.06 (7)	C14—C15—C17	121.1 (3)
O6—Cu2—O12	91.04 (7)	C16—C15—C14	117.2 (2)
O6—Cu2—N4	86.32 (7)	C16—C15—C17	121.7 (3)
O9—Cu2—O12	96.91 (8)	C11—C16—H16	118.9
O9—Cu2—N4	165.70 (8)	C15—C16—C11	122.2 (2)
N4—Cu2—O12	95.31 (8)	C15—C16—H16	118.9
N5—Cu2—O6	173.61 (8)	C15—C17—H17A	109.5
N5—Cu2—O9	90.07 (8)	C15—C17—H17B	109.5
N5—Cu2—O12	94.48 (8)	C15—C17—H17C	109.5
N5—Cu2—N4	96.36 (9)	H17A—C17—H17B	109.5
Cu1—O1—Cu1^i	99.64 (6)	H17A—C17—H17C	109.5
C1—O1—Cu1	122.31 (15)	H17B—C17—H17C	109.5
C1—O1—Cu1^i	120.97 (14)	N4—C18—C13	125.1 (2)
N2—O4—C8	111.31 (19)	N4—C18—H18	117.5
N3—O5—C9	111.07 (17)	C13—C18—H18	117.5
Cu2—O6—Cu1	112.68 (8)	O7—C19—H19A	109.5
C12—O6—Cu1	124.40 (14)	O7—C19—H19B	109.5
C12—O6—Cu2	122.88 (14)	O7—C19—C20	110.8 (2)
N4—O7—C19	112.9 (2)	H19A—C19—H19B	108.1
N5—O8—C20	110.5 (2)	C20—C19—H19A	109.5
C23—O9—Cu2	128.31 (17)	C20—C19—H19B	109.5
Cu2—O12—H12	116.9 (13)	O8—C20—C19	112.3 (2)
C28—O12—Cu2	129.85 (19)	O8—C20—H20A	109.1
C28—O12—H12	105.4 (14)	O8—C20—H20B	109.1
O2—N1—C4	118.0 (3)	C19—C20—H20A	109.1
O3—N1—O2	122.8 (3)	C19—C20—H20B	109.1
O3—N1—C4	119.2 (3)	H20A—C20—H20B	107.9
O4—N2—Cu1	120.80 (14)	N5—C21—H21	117.8
C7—N2—Cu1	126.41 (17)	N5—C21—C22	124.4 (2)
C7—N2—O4	112.52 (19)	C22—C21—H21	117.8
O5—N3—Cu1	123.16 (14)	C23—C22—C21	122.6 (2)
C10—N3—Cu1	124.99 (17)	C27—C22—C21	117.3 (3)
C10—N3—O5	110.23 (18)	C27—C22—C23	120.2 (3)
O7—N4—Cu2	128.35 (15)	O9—C23—C22	123.7 (2)
C18—N4—Cu2	123.03 (17)	O9—C23—C24	119.3 (2)
C18—N4—O7	108.2 (2)	C22—C23—C24	117.0 (2)
O8—N5—Cu2	117.66 (15)	C23—C24—H24	119.3
C21—N5—Cu2	129.0 (2)	C25—C24—C23	121.5 (3)
C21—N5—O8	113.1 (2)	C25—C24—H24	119.3
O10—N6—O11	123.5 (3)	C24—C25—H25	120.2
O10—N6—C26	118.3 (3)	C24—C25—C26	119.5 (3)
O11—N6—C26	118.2 (4)	C26—C25—H25	120.2
O1—C1—C2	122.5 (2)	C25—C26—N6	119.7 (3)
O1—C1—C6	119.1 (2)	C27—C26—N6	118.9 (3)
C6—C1—C2	118.3 (2)	C27—C26—C25	121.4 (3)
C1—C2—C7	121.5 (2)	C22—C27—H27	120.0
C3—C2—C1	120.3 (2)	C26—C27—C22	120.0 (3)
C3—C2—C7	118.1 (2)	C26—C27—H27	120.0
C2—C3—H3	120.6	O12—C28—H28A	109.5
C4—C3—C2	118.8 (2)	O12—C28—H28B	109.5
C4—C3—H3	120.6	O12—C28—H28C	109.5
C3—C4—N1	118.8 (3)	H28A—C28—H28B	109.5
C3—C4—C5	122.0 (2)	H28A—C28—H28C	109.5
C5—C4—N1	119.1 (2)	H28B—C28—H28C	109.5
C4—C5—H5	120.3	O14A—Cl1—O15A	116.1 (6)
C6—C5—C4	119.3 (2)	O14A—Cl1—O16	107.7 (6)
C6—C5—H5	120.3	O14A—Cl1—O17	119.2 (8)
C1—C6—H6	119.7	O15—Cl1—O14	104.0 (5)
C5—C6—C1	120.7 (2)	O15—Cl1—O16	124.0 (4)
C5—C6—H6	119.7	O15—Cl1—O17	112.8 (3)
N2—C7—C2	122.9 (2)	O16—Cl1—O14	110.0 (4)
N2—C7—H7	118.6	O16—Cl1—O15A	103.2 (4)
C2—C7—H7	118.6	O16—Cl1—O17	109.19 (19)
O4—C8—H8A	109.0	O17—Cl1—O14	91.8 (5)
O4—C8—H8B	109.0	O17—Cl1—O15A	100.1 (5)
O4—C8—C9	113.1 (2)	C29—O13—H13	109.5
H8A—C8—H8B	107.8	C29—O13A—H13A	108.4
C9—C8—H8A	109.0	O13—C29—H29A	109.5
C9—C8—H8B	109.0	O13—C29—H29B	109.5
O5—C9—C8	109.3 (2)	O13—C29—H29C	109.5
O5—C9—H9A	109.8	O13A—C29—H29D	109.5
O5—C9—H9B	109.8	O13A—C29—H29E	109.5
C8—C9—H9A	109.8	O13A—C29—H29F	109.5
C8—C9—H9B	109.8	H29A—C29—H29B	109.5
H9A—C9—H9B	108.3	H29A—C29—H29C	109.5
N3—C10—H10	117.8	H29B—C29—H29C	109.5
N3—C10—C11	124.4 (2)	H29D—C29—H29E	109.5
C11—C10—H10	117.8	H29D—C29—H29F	109.5
C12—C11—C10	122.3 (2)	H29E—C29—H29F	109.5
C16—C11—C10	117.7 (2)
Cu1^i—O1—C1—C2	93.6 (2)	C1—C2—C7—N2	20.9 (4)
Cu1—O1—C1—C2	−34.1 (3)	C2—C1—C6—C5	7.0 (4)
Cu1^i—O1—C1—C6	−84.4 (2)	C2—C3—C4—N1	−172.1 (2)
Cu1—O1—C1—C6	148.02 (18)	C2—C3—C4—C5	5.7 (4)
Cu1—O6—C12—C11	−35.1 (3)	C3—C2—C7—N2	−160.9 (2)
Cu1—O6—C12—C13	144.14 (18)	C3—C4—C5—C6	−3.0 (4)
Cu1—N2—C7—C2	2.8 (3)	C4—C5—C6—C1	−3.5 (4)
Cu1—N3—C10—C11	12.4 (4)	C6—C1—C2—C3	−4.2 (3)
Cu2—O6—C12—C11	142.36 (18)	C6—C1—C2—C7	173.9 (2)
Cu2—O6—C12—C13	−38.4 (3)	C7—C2—C3—C4	179.8 (2)
Cu2—O9—C23—C22	−5.8 (4)	C8—O4—N2—Cu1	88.3 (2)
Cu2—O9—C23—C24	174.20 (17)	C8—O4—N2—C7	−97.3 (2)
Cu2—N4—C18—C13	8.2 (3)	C9—O5—N3—Cu1	−46.3 (2)
Cu2—N5—C21—C22	1.4 (4)	C9—O5—N3—C10	147.6 (2)
O1—C1—C2—C3	177.8 (2)	C10—C11—C12—O6	−1.9 (4)
O1—C1—C2—C7	−4.0 (3)	C10—C11—C12—C13	178.8 (2)
O1—C1—C6—C5	−175.0 (2)	C10—C11—C16—C15	179.1 (2)
O2—N1—C4—C3	172.0 (3)	C11—C12—C13—C14	2.5 (3)
O2—N1—C4—C5	−5.8 (4)	C11—C12—C13—C18	177.8 (2)
O3—N1—C4—C3	−5.1 (4)	C12—C11—C16—C15	−2.3 (4)
O3—N1—C4—C5	177.0 (3)	C12—C13—C14—C15	−3.4 (4)
O4—N2—C7—C2	−171.3 (2)	C12—C13—C18—N4	16.9 (4)
O4—C8—C9—O5	−52.3 (3)	C13—C14—C15—C16	1.3 (4)
O5—N3—C10—C11	178.2 (2)	C13—C14—C15—C17	−179.8 (3)
O6—C12—C13—C14	−176.8 (2)	C14—C13—C18—N4	−167.7 (2)
O6—C12—C13—C18	−1.5 (4)	C14—C15—C16—C11	1.5 (4)
O7—N4—C18—C13	−178.3 (2)	C16—C11—C12—O6	179.5 (2)
O7—C19—C20—O8	−56.2 (3)	C16—C11—C12—C13	0.2 (3)
O8—N5—C21—C22	−173.5 (2)	C17—C15—C16—C11	−177.3 (3)
O9—C23—C24—C25	−173.4 (2)	C18—C13—C14—C15	−178.9 (2)
O10—N6—C26—C25	−177.8 (3)	C19—O7—N4—Cu2	−22.4 (3)
O10—N6—C26—C27	2.3 (4)	C19—O7—N4—C18	164.6 (2)
O11—N6—C26—C25	2.3 (4)	C20—O8—N5—Cu2	95.3 (2)
O11—N6—C26—C27	−177.5 (3)	C20—O8—N5—C21	−89.1 (3)
N1—C4—C5—C6	174.8 (2)	C21—C22—C23—O9	−8.3 (4)
N2—O4—C8—C9	−53.1 (3)	C21—C22—C23—C24	171.7 (2)
N3—O5—C9—C8	107.5 (2)	C21—C22—C27—C26	−177.0 (3)
N3—C10—C11—C12	13.4 (4)	C22—C23—C24—C25	6.6 (4)
N3—C10—C11—C16	−168.0 (2)	C23—C22—C27—C26	1.0 (4)
N4—O7—C19—C20	93.9 (3)	C23—C24—C25—C26	−1.7 (4)
N5—O8—C20—C19	−54.5 (3)	C24—C25—C26—N6	176.2 (3)
N5—C21—C22—C23	10.7 (4)	C24—C25—C26—C27	−3.9 (4)
N5—C21—C22—C27	−171.3 (3)	C25—C26—C27—C22	4.2 (4)
N6—C26—C27—C22	−175.9 (2)	C27—C22—C23—O9	173.8 (2)
C1—C2—C3—C4	−2.0 (4)	C27—C22—C23—C24	−6.2 (4)

Symmetry code: (i) −x+2, −y+1, −z+1.

(2)

Crystal data

C58H58Cu4N12O24·2(NO3)·2(C2H6O)	F(000) = 1824
Mr = 1777.48	Dx = 1.690 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 15.1553 (6) Å	Cell parameters from 3115 reflections
b = 15.2135 (6) Å	θ = 2.1–25.2°
c = 15.1959 (6) Å	µ = 1.31 mm^−1
β = 94.292 (1)°	T = 173 K
V = 3493.8 (2) Å^3	Block
Z = 2	0.17 × 0.14 × 0.13 mm

Data collection

Bruker D8 Venture diffractometer	Rint = 0.044
Absorption correction: multi-scan	θmax = 26.8°, θmin = 2.3°
Tmin = 0.81, Tmax = 0.85	h = −19→19
35111 measured reflections	k = −19→19
7413 independent reflections	l = −19→19
5276 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.052	H-atom parameters constrained
wR(F^2) = 0.101	w = 1/[σ^2(Fo^2) + (0.05P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
7413 reflections	Δρmax = 0.23 e Å^−3
509 parameters	Δρmin = −0.24 e Å^−3
2 restraints

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
C1	0.33791 (18)	0.5227 (2)	1.03790 (19)	0.0335 (7)
C2	0.32845 (19)	0.6117 (2)	1.06068 (19)	0.0340 (7)
C3	0.25315 (19)	0.6403 (2)	1.10234 (18)	0.0380 (7)
H3	0.245337	0.700376	1.116829	0.046*
C4	0.19249 (19)	0.5787 (2)	1.12082 (19)	0.0371 (7)
C5	0.20186 (18)	0.4897 (2)	1.10392 (18)	0.0342 (7)
H5	0.159270	0.448467	1.120978	0.041*
C6	0.2745 (2)	0.4627 (2)	1.0618 (2)	0.0377 (7)
H6	0.281483	0.402159	1.048774	0.045*
C7	0.3959 (2)	0.6771 (2)	1.0472 (2)	0.0400 (8)
H7	0.393123	0.731693	1.077210	0.048*
C8	0.5085 (2)	0.8015 (2)	0.9450 (2)	0.0379 (7)
H8A	0.558021	0.843999	0.951181	0.045*
H8B	0.453831	0.832676	0.958862	0.045*
C9	0.49813 (19)	0.76860 (19)	0.8513 (2)	0.0380 (7)
H9A	0.442366	0.734871	0.841837	0.046*
H9B	0.495073	0.819118	0.810094	0.046*
C10	0.58975 (19)	0.5846 (2)	0.7724 (2)	0.0358 (7)
H10	0.630050	0.618199	0.741227	0.043*
C11	0.58350 (19)	0.4919 (2)	0.75353 (19)	0.0360 (7)
C12	0.51482 (19)	0.43971 (19)	0.78010 (19)	0.0328 (6)
C13	0.51294 (19)	0.3513 (2)	0.75695 (19)	0.0379 (8)
C14	0.5808 (2)	0.3159 (2)	0.7100 (2)	0.0396 (8)
H14	0.579497	0.255125	0.695550	0.048*
C15	0.65043 (19)	0.3682 (2)	0.68396 (19)	0.0375 (7)
C16	0.64744 (19)	0.4567 (2)	0.7040 (2)	0.0355 (7)
H16	0.690970	0.494591	0.682874	0.043*
C17	0.7222 (2)	0.3281 (2)	0.6334 (2)	0.0455 (8)
H17A	0.764695	0.373769	0.619599	0.068*
H17B	0.695945	0.302279	0.578506	0.068*
H17C	0.752772	0.282289	0.669329	0.068*
C18	0.44666 (19)	0.2905 (2)	0.78443 (19)	0.0356 (7)
H18	0.457987	0.229494	0.778524	0.043*
C19	0.26186 (19)	0.2536 (2)	0.89600 (19)	0.0379 (7)
H19A	0.276646	0.307907	0.929811	0.045*
H19B	0.258949	0.204507	0.938472	0.045*
C20	0.17413 (19)	0.2642 (2)	0.8456 (2)	0.0415 (8)
H20A	0.157010	0.207652	0.816884	0.050*
H20B	0.129096	0.278748	0.887246	0.050*
C21	0.1416 (2)	0.4602 (2)	0.8401 (2)	0.0380 (8)
H21	0.084054	0.435174	0.838443	0.046*
C22	0.15151 (19)	0.5496 (2)	0.86787 (19)	0.0366 (7)
C23	0.2306 (2)	0.5988 (2)	0.85973 (19)	0.0361 (7)
C24	0.22802 (19)	0.6905 (2)	0.8787 (2)	0.0374 (7)
H24	0.277182	0.726519	0.867730	0.045*
C25	0.15494 (19)	0.7272 (2)	0.91294 (19)	0.0381 (7)
H25	0.154435	0.788197	0.926490	0.046*
C26	0.0827 (2)	0.6761 (2)	0.9275 (2)	0.0419 (8)
C27	0.0784 (2)	0.5907 (2)	0.9026 (2)	0.0390 (8)
H27	0.025617	0.558220	0.908558	0.047*
C28	0.3976 (3)	0.5074 (2)	0.5471 (2)	0.0626 (11)
H28A	0.442454	0.461224	0.556456	0.094*
H28B	0.425323	0.560899	0.526152	0.094*
H28C	0.351376	0.487710	0.502934	0.094*
C29	0.3589 (2)	0.5255 (2)	0.6292 (2)	0.0469 (9)
H29A	0.308877	0.566953	0.618388	0.056*
H29B	0.403559	0.553564	0.671006	0.056*
C30	0.0982 (2)	0.5265 (2)	0.6231 (2)	0.0500 (9)
H30A	0.064378	0.478950	0.648242	0.075*
H30B	0.059851	0.577828	0.612250	0.075*
H30C	0.148265	0.542343	0.664643	0.075*
C31	0.1323 (2)	0.4961 (2)	0.5370 (2)	0.0482 (9)
H31A	0.082069	0.483734	0.493280	0.058*
H31B	0.169357	0.542525	0.512808	0.058*
Cu1	0.47140 (2)	0.56651 (2)	0.91649 (2)	0.03352 (11)
Cu2	0.32899 (2)	0.43912 (2)	0.81502 (2)	0.03459 (11)
N1	0.11334 (17)	0.6093 (2)	1.16244 (17)	0.0427 (7)
N2	0.45940 (15)	0.66496 (15)	0.99640 (16)	0.0343 (6)
N3	0.54430 (15)	0.62579 (15)	0.82910 (16)	0.0341 (6)
N4	0.37470 (16)	0.31276 (15)	0.81575 (16)	0.0352 (6)
N5	0.20406 (16)	0.41196 (16)	0.81750 (16)	0.0382 (6)
N6	0.00632 (17)	0.71417 (19)	0.96823 (17)	0.0423 (7)
N7	0.1785 (2)	0.36510 (18)	0.3330 (2)	0.0481 (7)
O1	0.40638 (12)	0.49447 (12)	0.99615 (12)	0.0341 (5)
O2	0.06763 (15)	0.55226 (16)	1.19597 (16)	0.0539 (6)
O3	0.09506 (15)	0.68610 (16)	1.16139 (15)	0.0521 (6)
O4	0.52541 (13)	0.73042 (13)	1.00717 (13)	0.0389 (5)
O5	0.57089 (13)	0.71405 (13)	0.83391 (13)	0.0387 (5)
O6	0.45305 (12)	0.47279 (13)	0.82991 (13)	0.0360 (5)
O7	0.32853 (13)	0.23625 (13)	0.83797 (14)	0.0403 (5)
O8	0.17448 (13)	0.33125 (13)	0.77977 (14)	0.0399 (5)
O9	0.30322 (13)	0.56362 (12)	0.83457 (13)	0.0350 (5)
O10	−0.05610 (15)	0.66677 (15)	0.98053 (15)	0.0505 (6)
O11	0.00997 (14)	0.79181 (15)	0.98864 (14)	0.0492 (6)
O12	0.32757 (13)	0.44537 (13)	0.66761 (13)	0.0392 (5)
H12B	0.265983	0.435494	0.643134	0.047*
O13	0.18392 (14)	0.41751 (14)	0.55423 (14)	0.0448 (6)
H13	0.199378	0.397015	0.506407	0.067*
O14	0.23843 (15)	0.37232 (16)	0.39305 (15)	0.0544 (6)
O15	0.19887 (15)	0.35885 (16)	0.25515 (16)	0.0574 (6)
O16	0.09853 (15)	0.36182 (14)	0.34977 (14)	0.0484 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0226 (15)	0.047 (2)	0.0299 (17)	0.0073 (14)	−0.0047 (14)	−0.0050 (14)
C2	0.0302 (16)	0.044 (2)	0.0276 (16)	0.0030 (14)	−0.0025 (13)	0.0045 (14)
C3	0.0373 (17)	0.049 (2)	0.0279 (17)	0.0046 (15)	0.0048 (14)	−0.0052 (14)
C4	0.0294 (16)	0.0549 (15)	0.0280 (16)	0.0111 (15)	0.0081 (14)	−0.0057 (14)
C5	0.0265 (15)	0.0457 (14)	0.0311 (16)	−0.0080 (13)	0.0071 (14)	0.0083 (13)
C6	0.0375 (18)	0.0415 (19)	0.0346 (18)	−0.0036 (14)	0.0053 (15)	−0.0081 (14)
C7	0.0369 (18)	0.043 (2)	0.0395 (19)	0.0030 (14)	0.0017 (16)	0.0010 (14)
C8	0.0378 (17)	0.0352 (18)	0.0412 (18)	−0.0070 (14)	0.0059 (15)	−0.0007 (14)
C9	0.0376 (17)	0.0370 (18)	0.0394 (18)	0.0044 (14)	0.0033 (15)	0.0099 (14)
C10	0.0271 (15)	0.043 (2)	0.0372 (18)	0.0059 (13)	0.0029 (14)	0.0097 (14)
C11	0.0336 (16)	0.045 (2)	0.0295 (17)	0.0058 (12)	0.0054 (14)	−0.0052 (14)
C12	0.0306 (15)	0.0400 (18)	0.0268 (15)	0.0039 (12)	−0.0057 (13)	−0.0068 (13)
C13	0.0294 (16)	0.049 (2)	0.0334 (17)	−0.0023 (14)	−0.0108 (14)	−0.0084 (15)
C14	0.0363 (17)	0.0437 (19)	0.0367 (18)	0.0131 (15)	−0.0120 (15)	−0.0093 (14)
C15	0.0316 (16)	0.051 (2)	0.0306 (17)	0.0103 (14)	0.0095 (14)	−0.0095 (14)
C16	0.0295 (16)	0.043 (2)	0.0358 (17)	−0.0027 (13)	0.0117 (14)	0.0035 (14)
C17	0.0403 (18)	0.052 (2)	0.046 (2)	0.0071 (15)	0.0139 (16)	−0.0120 (16)
C18	0.0309 (16)	0.0388 (18)	0.0354 (17)	0.0062 (14)	−0.0084 (14)	−0.0106 (14)
C19	0.0397 (18)	0.0437 (19)	0.0312 (17)	−0.0146 (14)	0.0098 (15)	0.0102 (14)
C20	0.0349 (17)	0.0394 (19)	0.052 (2)	−0.0105 (14)	0.0163 (16)	−0.0082 (16)
C21	0.0309 (17)	0.045 (2)	0.0385 (18)	−0.0079 (14)	0.0074 (15)	−0.0074 (14)
C22	0.0348 (17)	0.044 (2)	0.0323 (17)	0.0086 (14)	0.0068 (14)	0.0060 (14)
C23	0.0341 (17)	0.0450 (19)	0.0290 (17)	0.0025 (15)	0.0018 (14)	0.0084 (14)
C24	0.0321 (17)	0.0408 (19)	0.0375 (18)	−0.0058 (14)	−0.0086 (15)	0.0083 (14)
C25	0.0386 (17)	0.0407 (19)	0.0331 (18)	0.0121 (15)	−0.0096 (15)	0.0085 (14)
C26	0.0404 (19)	0.047 (2)	0.0393 (19)	0.0120 (15)	0.0087 (16)	0.0082 (15)
C27	0.0357 (17)	0.045 (2)	0.0374 (18)	−0.0094 (14)	0.0099 (15)	0.0073 (15)
C28	0.073 (3)	0.054 (2)	0.064 (3)	−0.018 (2)	0.028 (2)	0.0161 (19)
C29	0.053 (2)	0.046 (2)	0.039 (2)	−0.0086 (17)	−0.0106 (17)	0.0102 (16)
C30	0.049 (2)	0.052 (2)	0.048 (2)	0.0097 (17)	−0.0065 (18)	−0.0083 (17)
C31	0.046 (2)	0.046 (2)	0.050 (2)	0.0148 (16)	−0.0121 (17)	0.0067 (16)
Cu1	0.0306 (2)	0.0389 (2)	0.0319 (2)	−0.00670 (16)	0.00786 (17)	0.00623 (16)
Cu2	0.0294 (2)	0.0392 (2)	0.0357 (2)	−0.00614 (16)	0.00610 (17)	−0.00706 (17)
N1	0.0350 (15)	0.056 (2)	0.0389 (16)	0.0030 (15)	0.0138 (13)	−0.0124 (14)
N2	0.0294 (13)	0.0387 (15)	0.0337 (14)	−0.0065 (11)	−0.0047 (12)	0.0060 (11)
N3	0.0333 (14)	0.0336 (15)	0.0357 (14)	−0.0082 (11)	0.0055 (12)	0.0080 (11)
N4	0.0363 (14)	0.0335 (15)	0.0369 (15)	−0.0047 (11)	0.0089 (12)	0.0077 (11)
N5	0.0377 (15)	0.0382 (16)	0.0396 (15)	−0.0064 (12)	0.0085 (13)	−0.0101 (12)
N6	0.0390 (16)	0.0447 (18)	0.0441 (17)	0.0095 (14)	0.0097 (13)	−0.0116 (13)
N7	0.0527 (19)	0.0490 (18)	0.0412 (18)	−0.0131 (14)	−0.0059 (17)	0.0157 (13)
O1	0.0314 (11)	0.0410 (13)	0.0313 (11)	0.0037 (9)	0.0112 (9)	0.0085 (9)
O2	0.0411 (13)	0.0646 (17)	0.0581 (16)	−0.0069 (12)	0.0175 (12)	−0.0152 (12)
O3	0.0499 (14)	0.0556 (16)	0.0528 (15)	0.0184 (12)	0.0165 (12)	−0.0113 (12)
O4	0.0368 (11)	0.0434 (13)	0.0353 (12)	−0.0079 (10)	−0.0057 (10)	0.0047 (10)
O5	0.0363 (11)	0.0360 (13)	0.0454 (13)	−0.0038 (10)	0.0134 (10)	0.0061 (10)
O6	0.0293 (11)	0.0421 (12)	0.0372 (12)	−0.0073 (9)	0.0062 (10)	−0.0017 (10)
O7	0.0360 (12)	0.0408 (13)	0.0446 (13)	−0.0108 (10)	0.0076 (10)	−0.0067 (10)
O8	0.0343 (12)	0.0401 (13)	0.0456 (13)	−0.0076 (9)	0.0055 (10)	−0.0092 (10)
O9	0.0277 (10)	0.0387 (12)	0.0375 (12)	−0.0047 (9)	−0.0038 (9)	0.0065 (9)
O10	0.0416 (13)	0.0560 (15)	0.0557 (15)	−0.0037 (12)	0.0152 (12)	−0.0170 (12)
O11	0.0517 (14)	0.0473 (15)	0.0501 (14)	0.0166 (11)	0.0135 (12)	−0.0091 (12)
O12	0.0371 (12)	0.0471 (14)	0.0319 (11)	−0.0077 (10)	−0.0077 (10)	0.0071 (9)
O13	0.0411 (13)	0.0475 (14)	0.0440 (13)	−0.0099 (10)	−0.0079 (11)	−0.0084 (11)
O14	0.0463 (14)	0.0674 (17)	0.0476 (14)	−0.0090 (12)	−0.0095 (13)	0.0089 (12)
O15	0.0554 (15)	0.0668 (17)	0.0512 (16)	−0.0173 (12)	0.0122 (13)	0.0104 (13)
O16	0.0432 (14)	0.0529 (15)	0.0508 (14)	−0.0095 (11)	0.0143 (12)	0.0097 (11)

Geometric parameters (Å, º)

C1—C2	1.406 (4)	C21—N5	1.265 (4)
C1—C6	1.393 (4)	C22—C23	1.427 (4)
C1—O1	1.328 (3)	C22—C27	1.409 (4)
C2—C3	1.415 (4)	C23—C24	1.425 (4)
C2—C7	1.453 (4)	C23—O9	1.307 (3)
C3—H3	0.9500	C24—H24	0.9500
C3—C4	1.357 (4)	C24—C25	1.377 (4)
C4—C5	1.387 (4)	C25—H25	0.9500
C4—N1	1.473 (4)	C25—C26	1.374 (4)
C5—H5	0.9500	C26—C27	1.354 (4)
C5—C6	1.377 (4)	C26—N6	1.472 (4)
C6—H6	0.9500	C27—H27	0.9500
C7—H7	0.9500	C28—H28A	0.9800
C7—N2	1.291 (4)	C28—H28B	0.9800
C8—H8A	0.9900	C28—H28C	0.9800
C8—H8B	0.9900	C28—C29	1.445 (5)
C8—C9	1.507 (4)	C29—H29A	0.9900
C8—O4	1.446 (3)	C29—H29B	0.9900
C9—H9A	0.9900	C29—O12	1.447 (4)
C9—H9B	0.9900	C30—H30A	0.9800
C9—O5	1.421 (3)	C30—H30B	0.9800
C10—H10	0.9500	C30—H30C	0.9800
C10—C11	1.440 (4)	C30—C31	1.515 (4)
C10—N3	1.303 (4)	C31—H31A	0.9900
C11—C12	1.393 (4)	C31—H31B	0.9900
C11—C16	1.379 (4)	C31—O13	1.443 (4)
C12—C13	1.390 (4)	Cu1—N2	1.945 (2)
C12—O6	1.345 (3)	Cu1—N3	2.004 (2)
C13—C14	1.402 (4)	Cu1—O1^i	2.3845 (19)
C13—C18	1.450 (4)	Cu1—O1	1.9535 (18)
C14—H14	0.9500	Cu1—O6	1.946 (2)
C14—C15	1.403 (4)	Cu2—N4	2.043 (2)
C15—C16	1.381 (4)	Cu2—N5	1.941 (2)
C15—C17	1.507 (4)	Cu2—O6	1.9455 (19)
C16—H16	0.9500	Cu2—O9	1.961 (2)
C17—H17A	0.9800	Cu2—O12	2.240 (2)
C17—H17B	0.9800	N1—O2	1.244 (3)
C17—H17C	0.9800	N1—O3	1.200 (3)
C18—H18	0.9500	N2—O4	1.412 (3)
C18—N4	1.268 (3)	N3—O5	1.402 (3)
C19—H19A	0.9900	N4—O7	1.412 (3)
C19—H19B	0.9900	N5—O8	1.414 (3)
C19—C20	1.493 (4)	N6—O10	1.215 (3)
C19—O7	1.415 (3)	N6—O11	1.222 (3)
C20—H20A	0.9900	N7—O14	1.244 (3)
C20—H20B	0.9900	N7—O15	1.249 (3)
C20—O8	1.429 (4)	N7—O16	1.257 (3)
C21—H21	0.9500	O12—H12B	0.9900
C21—C22	1.428 (4)	O13—H13	0.8400
C6—C1—C2	118.8 (3)	C26—C25—C24	120.2 (3)
O1—C1—C2	121.8 (3)	C26—C25—H25	119.9
O1—C1—C6	119.4 (3)	C25—C26—N6	120.4 (3)
C1—C2—C3	120.4 (3)	C27—C26—C25	121.4 (3)
C1—C2—C7	122.6 (3)	C27—C26—N6	118.1 (3)
C3—C2—C7	116.9 (3)	C22—C27—H27	119.7
C2—C3—H3	121.2	C26—C27—C22	120.5 (3)
C4—C3—C2	117.5 (3)	C26—C27—H27	119.7
C4—C3—H3	121.2	H28A—C28—H28B	109.5
C3—C4—C5	123.7 (3)	H28A—C28—H28C	109.5
C3—C4—N1	117.1 (3)	H28B—C28—H28C	109.5
C5—C4—N1	119.1 (3)	C29—C28—H28A	109.5
C4—C5—H5	120.9	C29—C28—H28B	109.5
C6—C5—C4	118.3 (3)	C29—C28—H28C	109.5
C6—C5—H5	120.9	C28—C29—H29A	109.5
C1—C6—H6	119.4	C28—C29—H29B	109.5
C5—C6—C1	121.1 (3)	C28—C29—O12	110.8 (3)
C5—C6—H6	119.4	H29A—C29—H29B	108.1
C2—C7—H7	118.3	O12—C29—H29A	109.5
N2—C7—C2	123.4 (3)	O12—C29—H29B	109.5
N2—C7—H7	118.3	H30A—C30—H30B	109.5
H8A—C8—H8B	107.9	H30A—C30—H30C	109.5
C9—C8—H8A	109.3	H30B—C30—H30C	109.5
C9—C8—H8B	109.3	C31—C30—H30A	109.5
O4—C8—H8A	109.3	C31—C30—H30B	109.5
O4—C8—H8B	109.3	C31—C30—H30C	109.5
O4—C8—C9	111.7 (2)	C30—C31—H31A	110.1
C8—C9—H9A	109.7	C30—C31—H31B	110.1
C8—C9—H9B	109.7	H31A—C31—H31B	108.4
H9A—C9—H9B	108.2	O13—C31—C30	108.1 (3)
O5—C9—C8	110.0 (2)	O13—C31—H31A	110.1
O5—C9—H9A	109.7	O13—C31—H31B	110.1
O5—C9—H9B	109.7	N2—Cu1—N3	98.58 (10)
C11—C10—H10	117.5	N2—Cu1—O1^i	93.27 (8)
N3—C10—H10	117.5	N2—Cu1—O1	88.29 (9)
N3—C10—C11	124.9 (3)	N2—Cu1—O6	166.15 (9)
C12—C11—C10	122.7 (3)	N3—Cu1—O1^i	95.75 (8)
C16—C11—C10	116.8 (3)	O1—Cu1—N3	172.59 (9)
C16—C11—C12	120.5 (3)	O1—Cu1—O1^i	81.00 (8)
C13—C12—C11	118.7 (3)	O6—Cu1—N3	86.54 (9)
O6—C12—C11	121.1 (3)	O6—Cu1—O1	87.40 (8)
O6—C12—C13	120.2 (3)	O6—Cu1—O1^i	99.04 (8)
C12—C13—C14	119.9 (3)	N4—Cu2—O12	91.33 (9)
C12—C13—C18	123.1 (3)	N5—Cu2—N4	97.49 (10)
C14—C13—C18	116.8 (3)	N5—Cu2—O6	171.65 (9)
C13—C14—H14	119.3	N5—Cu2—O9	89.83 (9)
C13—C14—C15	121.4 (3)	N5—Cu2—O12	95.28 (9)
C15—C14—H14	119.3	O6—Cu2—N4	85.57 (9)
C14—C15—C17	120.1 (3)	O6—Cu2—O9	85.97 (8)
C16—C15—C14	116.9 (3)	O6—Cu2—O12	92.41 (8)
C16—C15—C17	122.9 (3)	O9—Cu2—N4	168.30 (9)
C11—C16—H16	118.8	O9—Cu2—O12	97.09 (8)
C15—C16—C11	122.4 (3)	O2—N1—C4	116.8 (3)
C15—C16—H16	118.8	O3—N1—C4	119.8 (3)
C15—C17—H17A	109.5	O3—N1—O2	123.4 (3)
C15—C17—H17B	109.5	C7—N2—Cu1	126.3 (2)
C15—C17—H17C	109.5	C7—N2—O4	112.5 (2)
H17A—C17—H17B	109.5	O4—N2—Cu1	121.11 (17)
H17A—C17—H17C	109.5	C10—N3—Cu1	124.5 (2)
H17B—C17—H17C	109.5	C10—N3—O5	109.3 (2)
C13—C18—H18	117.6	O5—N3—Cu1	124.53 (17)
N4—C18—C13	124.9 (3)	C18—N4—Cu2	123.3 (2)
N4—C18—H18	117.6	C18—N4—O7	109.0 (2)
H19A—C19—H19B	108.1	O7—N4—Cu2	127.09 (17)
C20—C19—H19A	109.5	C21—N5—Cu2	129.2 (2)
C20—C19—H19B	109.5	C21—N5—O8	113.1 (2)
O7—C19—H19A	109.5	O8—N5—Cu2	117.21 (17)
O7—C19—H19B	109.5	O10—N6—C26	118.5 (3)
O7—C19—C20	110.5 (2)	O10—N6—O11	123.8 (3)
C19—C20—H20A	109.0	O11—N6—C26	117.7 (3)
C19—C20—H20B	109.0	O14—N7—O15	118.8 (3)
H20A—C20—H20B	107.8	O14—N7—O16	121.1 (3)
O8—C20—C19	112.7 (2)	O15—N7—O16	120.0 (3)
O8—C20—H20A	109.0	C1—O1—Cu1^i	117.54 (16)
O8—C20—H20B	109.0	C1—O1—Cu1	124.26 (18)
C22—C21—H21	117.7	Cu1—O1—Cu1^i	99.00 (8)
N5—C21—H21	117.7	N2—O4—C8	111.2 (2)
N5—C21—C22	124.6 (3)	N3—O5—C9	110.2 (2)
C23—C22—C21	123.0 (3)	C12—O6—Cu1	125.76 (17)
C27—C22—C21	117.7 (3)	C12—O6—Cu2	122.92 (17)
C27—C22—C23	119.2 (3)	Cu1—O6—Cu2	111.07 (9)
C24—C23—C22	117.5 (3)	N4—O7—C19	112.7 (2)
O9—C23—C22	122.8 (3)	N5—O8—C20	110.7 (2)
O9—C23—C24	119.8 (3)	C23—O9—Cu2	128.45 (19)
C23—C24—H24	119.7	C29—O12—Cu2	117.40 (17)
C25—C24—C23	120.6 (3)	C29—O12—H12B	107.7
C25—C24—H24	119.7	Cu2—O12—H12B	107.9
C24—C25—H25	119.9	C31—O13—H13	109.5

Symmetry code: (i) −x+1, −y+1, −z+2.

(3)

Crystal data

C29H30Br2Cu2N6O12·CHCl3	F(000) = 2112
Mr = 1060.86	Dx = 1.796 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 14.3330 (4) Å	Cell parameters from 9688 reflections
b = 17.1049 (4) Å	θ = 2.4–26.7°
c = 16.3502 (5) Å	µ = 3.39 mm^−1
β = 101.859 (2)°	T = 173 K
V = 3922.93 (19) Å^3	Block
Z = 4	0.26 × 0.24 × 0.23 mm

Data collection

Bruker D8 Venture diffractometer	7711 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.048
Absorption correction: multi-scan SADABS	θmax = 26.8°, θmin = 2.4°
Tmin = 0.607, Tmax = 0.745	h = −18→18
35876 measured reflections	k = −21→21
8303 independent reflections	l = −20→20

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.026	w = 1/[σ^2(Fo^2) + (0.0373P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.068	(Δ/σ)max = 0.001
S = 1.06	Δρmax = 0.55 e Å^−3
8303 reflections	Δρmin = −0.56 e Å^−3
540 parameters	Absolute structure: Refined as an inversion twin.
119 restraints	Absolute structure parameter: 0.023 (8)
Primary atom site location: iterative

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. Refined as a 2-component inversion twin.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br1	0.51014 (3)	0.58335 (3)	0.61276 (3)	0.03264 (11)
Br2	0.19557 (4)	0.61898 (3)	0.46705 (3)	0.03903 (13)
C1	0.2776 (3)	0.5489 (2)	0.6849 (3)	0.0211 (8)
C2	0.2944 (3)	0.6299 (3)	0.6963 (3)	0.0265 (9)
H2	0.324182	0.657931	0.658518	0.032*
C3	0.2678 (3)	0.6688 (3)	0.7620 (3)	0.0295 (9)
H3	0.279561	0.723227	0.769475	0.035*
C4	0.2238 (3)	0.6279 (3)	0.8172 (3)	0.0285 (9)
C5	0.2077 (3)	0.5493 (3)	0.8094 (3)	0.0263 (9)
H5	0.178553	0.522418	0.848477	0.032*
C6	0.2344 (3)	0.5082 (3)	0.7432 (3)	0.0241 (8)
C7	0.2082 (3)	0.4266 (3)	0.7363 (3)	0.0259 (9)
H7	0.173834	0.406737	0.775713	0.031*
C8	0.1670 (4)	0.2608 (3)	0.6147 (3)	0.0351 (10)
H8A	0.166724	0.295939	0.566477	0.042*
H8B	0.103544	0.235786	0.607299	0.042*
C9	0.2414 (5)	0.2001 (3)	0.6178 (4)	0.0437 (13)
H9A	0.234210	0.160437	0.660145	0.052*
H9B	0.232049	0.173629	0.562885	0.052*
C10	0.3989 (4)	0.2706 (3)	0.5298 (3)	0.0294 (10)
H10	0.416165	0.216975	0.530681	0.035*
C11	0.4321 (3)	0.3206 (2)	0.4706 (3)	0.0257 (9)
C12	0.4114 (3)	0.4013 (2)	0.4620 (3)	0.0209 (8)
C13	0.4465 (3)	0.4427 (3)	0.3995 (3)	0.0225 (8)
C14	0.4989 (3)	0.4030 (3)	0.3492 (3)	0.0293 (10)
H14	0.520864	0.431438	0.306902	0.035*
C15	0.5204 (4)	0.3233 (3)	0.3581 (3)	0.0329 (10)
C16	0.4870 (3)	0.2839 (3)	0.4193 (3)	0.0317 (10)
H16	0.501282	0.229838	0.427321	0.038*
C17	0.5778 (5)	0.2837 (4)	0.3036 (4)	0.0501 (15)
H17A	0.542290	0.284222	0.245630	0.075*
H17B	0.590292	0.229500	0.322152	0.075*
H17C	0.638402	0.311330	0.307408	0.075*
C18	0.4301 (3)	0.5248 (3)	0.3803 (3)	0.0246 (9)
H18	0.447120	0.542908	0.330447	0.030*
C19	0.4090 (5)	0.7128 (3)	0.4357 (3)	0.0423 (13)
H19A	0.478362	0.711790	0.459489	0.051*
H19B	0.374469	0.710039	0.482139	0.051*
C20	0.3831 (4)	0.7857 (3)	0.3864 (3)	0.0400 (12)
H20A	0.318135	0.780975	0.351561	0.048*
H20B	0.384117	0.830837	0.424473	0.048*
C21	0.4823 (4)	0.8735 (3)	0.2372 (3)	0.0354 (11)
H21	0.517868	0.829135	0.226500	0.042*
C22	0.4829 (4)	0.9450 (3)	0.1864 (3)	0.0350 (11)
C23	0.5251 (4)	0.9412 (3)	0.1161 (4)	0.0369 (11)
C24	0.5307 (4)	1.0068 (3)	0.0679 (4)	0.0447 (13)
H24	0.561494	1.003804	0.021801	0.054*
C25	0.4915 (4)	1.0767 (3)	0.0866 (4)	0.0452 (13)
H25	0.494775	1.122039	0.053667	0.054*
C26	0.4479 (4)	1.0792 (3)	0.1536 (4)	0.0476 (14)
C27	0.4433 (4)	1.0149 (3)	0.2061 (4)	0.0432 (12)
H27	0.414291	1.019102	0.253136	0.052*
C28	0.6058 (7)	0.3466 (8)	0.6739 (7)	0.106 (4)
H28A	0.573877	0.323387	0.620719	0.159*
H28B	0.655963	0.311182	0.702274	0.159*
H28C	0.634246	0.396730	0.663385	0.159*
C29	0.5371 (5)	0.3590 (4)	0.7262 (5)	0.0617 (17)
H29A	0.571934	0.375740	0.782163	0.074*
H29B	0.506292	0.308335	0.733174	0.074*
Cu1	0.31508 (4)	0.39953 (3)	0.60575 (3)	0.02174 (11)
Cu2	0.34921 (3)	0.55862 (3)	0.52622 (3)	0.02157 (12)
N1	0.1933 (3)	0.6696 (3)	0.8857 (3)	0.0370 (10)
N2	0.2271 (3)	0.3789 (2)	0.6818 (2)	0.0254 (8)
N3	0.3480 (3)	0.2930 (2)	0.5814 (2)	0.0290 (8)
N4	0.3954 (3)	0.5754 (2)	0.4226 (2)	0.0237 (7)
N5	0.4353 (3)	0.8702 (2)	0.2947 (3)	0.0360 (9)
N6	0.4047 (5)	1.1524 (3)	0.1733 (4)	0.0648 (16)
O1	0.2997 (2)	0.51216 (17)	0.62030 (18)	0.0234 (6)
O2	0.2051 (3)	0.7402 (2)	0.8909 (3)	0.0527 (11)
O3	0.1578 (3)	0.6307 (2)	0.9351 (2)	0.0466 (9)
O4	0.1857 (3)	0.30552 (19)	0.6911 (2)	0.0371 (8)
O5	0.3381 (3)	0.23237 (19)	0.6384 (2)	0.0387 (8)
O6	0.3608 (2)	0.43761 (16)	0.50914 (18)	0.0217 (6)
O7	0.3831 (2)	0.64799 (17)	0.38000 (19)	0.0294 (7)
O8	0.4513 (3)	0.7971 (2)	0.3342 (2)	0.0400 (8)
O9	0.5600 (3)	0.8715 (2)	0.0983 (3)	0.0432 (9)
H9	0.601264	0.878456	0.069221	0.065*
O10	0.3725 (5)	1.1552 (3)	0.2370 (5)	0.0880 (19)
O11	0.4049 (5)	1.2086 (3)	0.1261 (4)	0.0887 (19)
O12	0.4629 (3)	0.4161 (2)	0.6960 (2)	0.0373 (8)
H12	0.4972 (19)	0.4563 (19)	0.681 (3)	0.056*
C30	0.7369 (11)	0.4317 (14)	0.8697 (15)	0.100 (7)	0.492 (7)
H30	0.725321	0.384382	0.833161	0.120*	0.492 (7)
C30A	0.7911 (14)	0.5079 (9)	0.8951 (12)	0.087 (5)	0.508 (7)
H30A	0.852597	0.536130	0.897341	0.104*	0.508 (7)
Cl0A	0.8598 (5)	0.4390 (7)	0.9319 (6)	0.140 (3)	0.492 (7)
Cl1	0.7239 (12)	0.5184 (11)	0.8160 (12)	0.207 (5)	0.492 (7)
Cl1A	0.7173 (3)	0.5183 (3)	0.7967 (3)	0.0605 (11)	0.508 (7)
Cl2	0.6614 (4)	0.4379 (4)	0.9445 (4)	0.115 (2)	0.492 (7)
Cl2A	0.7357 (5)	0.5416 (6)	0.9723 (5)	0.149 (3)	0.508 (7)
Cl3	0.8109 (9)	0.4065 (4)	0.9040 (6)	0.139 (3)	0.508 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0400 (2)	0.0315 (2)	0.0275 (2)	−0.0132 (2)	0.00937 (18)	0.00038 (18)
Br2	0.0448 (3)	0.0460 (3)	0.0307 (2)	0.0171 (2)	0.0180 (2)	0.0093 (2)
C1	0.0231 (19)	0.025 (2)	0.0170 (19)	0.0012 (16)	0.0078 (15)	−0.0019 (16)
C2	0.035 (2)	0.023 (2)	0.024 (2)	0.0019 (17)	0.0113 (17)	0.0014 (16)
C3	0.036 (2)	0.022 (2)	0.030 (2)	0.0010 (18)	0.0085 (18)	−0.0070 (17)
C4	0.029 (2)	0.036 (2)	0.021 (2)	0.0055 (19)	0.0078 (17)	−0.0076 (18)
C5	0.029 (2)	0.036 (2)	0.018 (2)	0.0010 (18)	0.0121 (16)	0.0009 (17)
C6	0.029 (2)	0.026 (2)	0.0196 (19)	0.0000 (17)	0.0088 (16)	0.0004 (16)
C7	0.032 (2)	0.031 (2)	0.018 (2)	−0.0031 (18)	0.0125 (17)	0.0061 (16)
C8	0.051 (3)	0.028 (2)	0.031 (2)	−0.018 (2)	0.020 (2)	−0.0027 (18)
C9	0.075 (4)	0.021 (2)	0.044 (3)	−0.013 (2)	0.033 (3)	0.000 (2)
C10	0.047 (3)	0.019 (2)	0.025 (2)	0.0086 (19)	0.0136 (19)	0.0021 (16)
C11	0.037 (2)	0.0214 (19)	0.020 (2)	0.0062 (17)	0.0098 (17)	0.0007 (16)
C12	0.024 (2)	0.022 (2)	0.0174 (19)	0.0006 (16)	0.0057 (16)	−0.0027 (15)
C13	0.0250 (19)	0.028 (2)	0.0162 (19)	0.0001 (16)	0.0086 (15)	−0.0026 (15)
C14	0.035 (2)	0.035 (2)	0.021 (2)	0.0061 (19)	0.0149 (19)	0.0024 (18)
C15	0.042 (3)	0.035 (2)	0.026 (2)	0.016 (2)	0.0160 (19)	0.0017 (19)
C16	0.041 (3)	0.029 (2)	0.027 (2)	0.016 (2)	0.0119 (19)	0.0014 (18)
C17	0.067 (4)	0.054 (3)	0.038 (3)	0.031 (3)	0.031 (3)	0.009 (3)
C18	0.031 (2)	0.028 (2)	0.018 (2)	−0.0017 (17)	0.0110 (17)	0.0015 (16)
C19	0.080 (4)	0.022 (2)	0.028 (2)	−0.011 (2)	0.020 (2)	−0.0001 (19)
C20	0.065 (4)	0.022 (2)	0.041 (3)	−0.002 (2)	0.029 (3)	0.0022 (19)
C21	0.036 (3)	0.029 (2)	0.044 (3)	−0.001 (2)	0.014 (2)	0.000 (2)
C22	0.035 (2)	0.029 (2)	0.043 (3)	−0.006 (2)	0.013 (2)	0.004 (2)
C23	0.033 (2)	0.036 (2)	0.042 (3)	−0.002 (2)	0.009 (2)	0.003 (2)
C24	0.045 (3)	0.047 (3)	0.044 (3)	−0.007 (2)	0.017 (2)	0.012 (2)
C25	0.051 (3)	0.032 (3)	0.052 (3)	−0.003 (2)	0.007 (3)	0.015 (2)
C26	0.050 (3)	0.030 (3)	0.063 (4)	0.000 (2)	0.013 (3)	0.008 (2)
C27	0.047 (3)	0.036 (3)	0.050 (3)	−0.001 (2)	0.019 (3)	0.006 (2)
C28	0.073 (6)	0.145 (10)	0.100 (7)	0.019 (6)	0.018 (5)	−0.027 (7)
C29	0.067 (4)	0.047 (3)	0.068 (5)	0.007 (3)	0.008 (3)	0.003 (3)
Cu1	0.0332 (3)	0.0155 (2)	0.0206 (2)	−0.0021 (2)	0.0150 (2)	0.00117 (19)
Cu2	0.0332 (3)	0.0172 (2)	0.0180 (2)	−0.0013 (2)	0.01399 (19)	0.00117 (19)
N1	0.039 (2)	0.044 (3)	0.029 (2)	0.0091 (19)	0.0110 (17)	−0.0119 (18)
N2	0.038 (2)	0.0190 (17)	0.0236 (18)	−0.0072 (15)	0.0156 (15)	0.0024 (14)
N3	0.044 (2)	0.0194 (17)	0.0266 (19)	0.0019 (16)	0.0149 (16)	0.0079 (14)
N4	0.0357 (19)	0.0175 (16)	0.0209 (18)	−0.0006 (14)	0.0129 (15)	0.0042 (13)
N5	0.046 (2)	0.0224 (18)	0.041 (2)	−0.0027 (17)	0.0115 (19)	0.0050 (16)
N6	0.080 (4)	0.030 (2)	0.089 (5)	0.008 (3)	0.030 (4)	0.008 (3)
O1	0.0337 (16)	0.0200 (14)	0.0202 (14)	−0.0023 (12)	0.0144 (12)	−0.0003 (11)
O2	0.070 (3)	0.040 (2)	0.053 (2)	0.008 (2)	0.026 (2)	−0.0211 (19)
O3	0.056 (2)	0.059 (2)	0.0305 (19)	0.0118 (19)	0.0217 (17)	−0.0060 (17)
O4	0.064 (2)	0.0249 (16)	0.0310 (18)	−0.0197 (16)	0.0291 (16)	−0.0034 (13)
O5	0.058 (2)	0.0237 (16)	0.0396 (19)	0.0035 (15)	0.0225 (17)	0.0181 (14)
O6	0.0315 (15)	0.0167 (13)	0.0206 (15)	−0.0011 (12)	0.0140 (12)	0.0001 (11)
O7	0.053 (2)	0.0182 (14)	0.0205 (15)	−0.0011 (13)	0.0167 (14)	0.0050 (11)
O8	0.051 (2)	0.0258 (17)	0.048 (2)	0.0005 (15)	0.0194 (17)	0.0135 (15)
O9	0.051 (2)	0.0347 (19)	0.052 (2)	−0.0019 (16)	0.0289 (19)	0.0009 (16)
O10	0.120 (5)	0.043 (3)	0.115 (5)	0.025 (3)	0.056 (4)	0.004 (3)
O11	0.124 (5)	0.035 (2)	0.109 (5)	0.016 (3)	0.027 (4)	0.025 (3)
O12	0.044 (2)	0.0334 (18)	0.0342 (19)	−0.0009 (15)	0.0078 (16)	−0.0008 (15)
C30	0.074 (11)	0.118 (17)	0.104 (16)	0.044 (12)	0.006 (11)	0.043 (14)
C30A	0.090 (12)	0.069 (10)	0.092 (13)	−0.006 (9)	−0.002 (10)	−0.008 (9)
Cl0A	0.078 (3)	0.174 (7)	0.148 (6)	0.002 (4)	−0.024 (4)	0.021 (6)
Cl1	0.183 (9)	0.228 (10)	0.204 (10)	0.036 (8)	0.026 (8)	0.041 (9)
Cl1A	0.0417 (17)	0.081 (3)	0.060 (2)	−0.0033 (17)	0.0151 (15)	0.0030 (17)
Cl2	0.099 (4)	0.135 (5)	0.121 (5)	0.052 (3)	0.042 (3)	0.057 (4)
Cl2A	0.101 (4)	0.226 (8)	0.115 (5)	0.019 (5)	0.011 (4)	−0.035 (5)
Cl3	0.193 (8)	0.089 (4)	0.127 (6)	0.003 (5)	0.017 (6)	0.024 (4)

Geometric parameters (Å, º)

Br1—Cu2	2.4819 (7)	C20—O8	1.437 (6)
Br2—Cu2	2.4445 (7)	C21—H21	0.9500
C1—C2	1.412 (6)	C21—C22	1.480 (7)
C1—C6	1.422 (6)	C21—N5	1.264 (7)
C1—O1	1.322 (5)	C22—C23	1.405 (8)
C2—H2	0.9500	C22—C27	1.390 (8)
C2—C3	1.382 (6)	C23—C24	1.384 (7)
C3—H3	0.9500	C23—O9	1.348 (6)
C3—C4	1.390 (7)	C24—H24	0.9500
C4—C5	1.367 (7)	C24—C25	1.381 (8)
C4—N1	1.469 (5)	C25—H25	0.9500
C5—H5	0.9500	C25—C26	1.370 (9)
C5—C6	1.408 (6)	C26—C27	1.404 (8)
C6—C7	1.443 (6)	C26—N6	1.461 (8)
C7—H7	0.9500	C27—H27	0.9500
C7—N2	1.279 (6)	C28—H28A	0.9800
C8—H8A	0.9900	C28—H28B	0.9800
C8—H8B	0.9900	C28—H28C	0.9800
C8—C9	1.482 (8)	C28—C29	1.446 (12)
C8—O4	1.442 (6)	C29—H29A	0.9900
C9—H9A	0.9900	C29—H29B	0.9900
C9—H9B	0.9900	C29—O12	1.454 (8)
C9—O5	1.465 (7)	Cu1—N2	1.976 (4)
C10—H10	0.9500	Cu1—N3	1.943 (4)
C10—C11	1.443 (6)	Cu1—O1	1.959 (3)
C10—N3	1.282 (6)	Cu1—O6	1.943 (3)
C11—C12	1.413 (6)	Cu1—O12	2.337 (4)
C11—C16	1.410 (6)	Cu2—N4	1.962 (4)
C12—C13	1.418 (6)	Cu2—O1	1.987 (3)
C12—O6	1.317 (5)	Cu2—O6	2.100 (3)
C13—C14	1.400 (6)	N1—O2	1.220 (6)
C13—C18	1.447 (6)	N1—O3	1.233 (6)
C14—H14	0.9500	N2—O4	1.410 (4)
C14—C15	1.398 (7)	N3—O5	1.421 (4)
C15—C16	1.371 (7)	N4—O7	1.417 (4)
C15—C17	1.494 (6)	N5—O8	1.404 (5)
C16—H16	0.9500	N6—O10	1.225 (8)
C17—H17A	0.9800	N6—O11	1.233 (7)
C17—H17B	0.9800	O9—H9	0.8400
C17—H17C	0.9800	O12—H12	0.906 (14)
C18—H18	0.9500	C30—H30	1.0000
C18—N4	1.272 (6)	C30—Cl0A	1.848 (19)
C19—H19A	0.9900	C30—Cl1	1.71 (3)
C19—H19B	0.9900	C30—Cl2	1.79 (2)
C19—C20	1.490 (7)	C30A—H30A	1.0000
C19—O7	1.433 (6)	C30A—Cl1A	1.74 (2)
C20—H20A	0.9900	C30A—Cl2A	1.722 (18)
C20—H20B	0.9900	C30A—Cl3	1.758 (16)
C2—C1—C6	118.5 (4)	C25—C24—C23	120.2 (5)
O1—C1—C2	120.7 (4)	C25—C24—H24	119.9
O1—C1—C6	120.8 (4)	C24—C25—H25	120.8
C1—C2—H2	119.7	C26—C25—C24	118.5 (5)
C3—C2—C1	120.6 (4)	C26—C25—H25	120.8
C3—C2—H2	119.7	C25—C26—C27	123.4 (5)
C2—C3—H3	120.1	C25—C26—N6	119.1 (5)
C2—C3—C4	119.8 (4)	C27—C26—N6	117.5 (6)
C4—C3—H3	120.1	C22—C27—C26	117.4 (5)
C3—C4—N1	119.8 (4)	C22—C27—H27	121.3
C5—C4—C3	121.7 (4)	C26—C27—H27	121.3
C5—C4—N1	118.5 (4)	H28A—C28—H28B	109.5
C4—C5—H5	120.2	H28A—C28—H28C	109.5
C4—C5—C6	119.6 (4)	H28B—C28—H28C	109.5
C6—C5—H5	120.2	C29—C28—H28A	109.5
C1—C6—C7	124.3 (4)	C29—C28—H28B	109.5
C5—C6—C1	119.8 (4)	C29—C28—H28C	109.5
C5—C6—C7	115.7 (4)	C28—C29—H29A	108.3
C6—C7—H7	117.2	C28—C29—H29B	108.3
N2—C7—C6	125.6 (4)	C28—C29—O12	116.0 (7)
N2—C7—H7	117.2	H29A—C29—H29B	107.4
H8A—C8—H8B	108.2	O12—C29—H29A	108.3
C9—C8—H8A	109.7	O12—C29—H29B	108.3
C9—C8—H8B	109.7	N2—Cu1—O12	103.70 (15)
O4—C8—H8A	109.7	N3—Cu1—N2	100.05 (15)
O4—C8—H8B	109.7	N3—Cu1—O1	169.97 (14)
O4—C8—C9	109.7 (5)	N3—Cu1—O12	90.91 (16)
C8—C9—H9A	109.1	O1—Cu1—N2	89.85 (13)
C8—C9—H9B	109.1	O1—Cu1—O12	85.06 (13)
H9A—C9—H9B	107.8	O6—Cu1—N2	159.56 (14)
O5—C9—C8	112.6 (4)	O6—Cu1—N3	90.64 (14)
O5—C9—H9A	109.1	O6—Cu1—O1	80.45 (11)
O5—C9—H9B	109.1	O6—Cu1—O12	93.41 (13)
C11—C10—H10	117.4	Br2—Cu2—Br1	144.07 (3)
N3—C10—H10	117.4	N4—Cu2—Br1	91.63 (11)
N3—C10—C11	125.1 (4)	N4—Cu2—Br2	91.86 (11)
C12—C11—C10	123.6 (4)	N4—Cu2—O1	164.60 (13)
C16—C11—C10	115.9 (4)	N4—Cu2—O6	88.83 (13)
C16—C11—C12	120.5 (4)	O1—Cu2—Br1	93.70 (9)
C11—C12—C13	117.5 (4)	O1—Cu2—Br2	92.27 (9)
O6—C12—C11	122.2 (4)	O1—Cu2—O6	76.08 (11)
O6—C12—C13	120.3 (4)	O6—Cu2—Br1	98.87 (9)
C12—C13—C18	125.1 (4)	O6—Cu2—Br2	116.95 (9)
C14—C13—C12	119.6 (4)	O2—N1—C4	118.3 (4)
C14—C13—C18	115.3 (4)	O2—N1—O3	124.0 (4)
C13—C14—H14	118.5	O3—N1—C4	117.8 (4)
C15—C14—C13	123.0 (4)	C7—N2—Cu1	125.4 (3)
C15—C14—H14	118.5	C7—N2—O4	109.8 (3)
C14—C15—C17	121.1 (4)	O4—N2—Cu1	124.3 (3)
C16—C15—C14	117.0 (4)	C10—N3—Cu1	127.6 (3)
C16—C15—C17	122.0 (4)	C10—N3—O5	111.1 (3)
C11—C16—H16	118.8	O5—N3—Cu1	119.3 (3)
C15—C16—C11	122.4 (4)	C18—N4—Cu2	127.5 (3)
C15—C16—H16	118.8	C18—N4—O7	110.6 (3)
C15—C17—H17A	109.5	O7—N4—Cu2	121.6 (3)
C15—C17—H17B	109.5	C21—N5—O8	108.7 (4)
C15—C17—H17C	109.5	O10—N6—C26	118.2 (5)
H17A—C17—H17B	109.5	O10—N6—O11	123.4 (6)
H17A—C17—H17C	109.5	O11—N6—C26	118.4 (6)
H17B—C17—H17C	109.5	C1—O1—Cu1	128.0 (3)
C13—C18—H18	116.3	C1—O1—Cu2	127.6 (3)
N4—C18—C13	127.4 (4)	Cu1—O1—Cu2	103.44 (13)
N4—C18—H18	116.3	N2—O4—C8	112.7 (3)
H19A—C19—H19B	108.5	N3—O5—C9	110.0 (4)
C20—C19—H19A	110.2	C12—O6—Cu1	129.5 (3)
C20—C19—H19B	110.2	C12—O6—Cu2	127.7 (2)
O7—C19—H19A	110.2	Cu1—O6—Cu2	99.97 (12)
O7—C19—H19B	110.2	N4—O7—C19	112.0 (3)
O7—C19—C20	107.5 (4)	N5—O8—C20	109.1 (4)
C19—C20—H20A	110.1	C23—O9—H9	109.5
C19—C20—H20B	110.1	C29—O12—Cu1	129.7 (4)
H20A—C20—H20B	108.4	C29—O12—H12	102 (2)
O8—C20—C19	108.1 (4)	Cu1—O12—H12	113 (2)
O8—C20—H20A	110.1	Cl0A—C30—H30	114.0
O8—C20—H20B	110.1	Cl1—C30—H30	114.0
C22—C21—H21	119.3	Cl1—C30—Cl0A	102.4 (13)
N5—C21—H21	119.3	Cl1—C30—Cl2	106.3 (13)
N5—C21—C22	121.3 (5)	Cl2—C30—H30	114.0
C23—C22—C21	118.3 (5)	Cl2—C30—Cl0A	105.1 (13)
C27—C22—C21	122.1 (5)	Cl1A—C30A—H30A	110.3
C27—C22—C23	119.6 (5)	Cl1A—C30A—Cl3	103.5 (9)
C24—C23—C22	120.9 (5)	Cl2A—C30A—H30A	110.3
O9—C23—C22	117.3 (5)	Cl2A—C30A—Cl1A	111.0 (10)
O9—C23—C24	121.8 (5)	Cl2A—C30A—Cl3	111.2 (13)
C23—C24—H24	119.9	Cl3—C30A—H30A	110.3