A six-connected [alpha]-polonium net based on tetra­nuclear Cd^II nodes

The cadmium(II) coordination polymer poly[[­(pyrazino[2,3-f][1,10]phenanthroline-[kappa]²N⁸,N⁹)cadmium(II)]-[mu]₃-naphthalene-1,4-­dicarboxylato-[kappa]⁵O¹:O¹,O^1':O⁴,O^4'], [Cd(C₁₂H₆O₄)(C₁₄H₈N₄)]_n, contains two Cd^II cations, two pyrazino[2,3-f][1,10]phenanthroline (L) ligands and two naphthalene-1,4-­dicarboxylate (1,4-ndc) anions in the asymmetric unit. Both Cd^II ions are in a distorted CdO₅N₂ monocapped octa­hedral coordination geometry. Both unique 1,4-ndc ligands are bonded to three Cd^II ions. In these modes, tetra­nuclear clusters are formed in which four Cd^II ions are bridged by the carboxyl­ate groups of the 1,4-ndc ligands to form discrete rods. The tetra­nuclear cadmium carboxyl­ate clusters act as rod-shaped secondary building units (SBUs) within the structure. The SBUs are connected together by the aromatic backbone of the dicarboxyl­ate ligands, connecting the clusters into a three-dimensional [alpha]-polonium net. The title compound represents the first [alpha]-polonium net constructed from rod-like clusters in coordination polymers. The result indicates that an appropriate combination of dicarboxyl­ate and aromatic chelating ligands is critical to the formation of high-dimensional structures based on metal clusters in these systems.

S1. Comment

Recently, coordination polymers constructed of polynuclear metal clusters and polycarboxylates have attracted intense interest due to their interesting molecular topologies and potential applications as functional materials (Eddaoudi et al., 2001). Polynuclear metal clusters can be very versatile in terms of coordination properties and rigidity, as well as displaying intriguing physical properties in comparison with mononuclear species (Hagrman et al., 1999; Noveron et al., 2002). Recent reviews of the framework topologies and other geometric characteristics of network solids reflect that it remains a challenge to achieve a true advance without understanding the structural aspects of such materials at a molecular or an atomic resolution (Eddaoudi et al., 2001). In this regard, the skilful combination of bridging carboxylates, 2,2'-bipyridyl(bpy)-like chelating ligands and metal ions has generated many interesting coordination architectures. Unfortunately, owing to the termination effect of chelating bpy-like ligands, such coordination polymers containing both polycarboxylates and bpy-like ligands are usually only one- or two-dimensional coordination polymers (Hu et al., 2006). As far as we know, high-dimensional complexes based on dicarboxylate and bpy-like ligands have rarely been reported. The utilization of polynuclear metal clusters as building blocks to construct high-dimensional frameworks has proved to be a feasible route (Wang et al., 2005). One common approach to the synthesis of high-nuclearity clusters is to control the hydrolysis of metal salts with the aid of carboxylate ligands, where the carboxylate group may induce core aggregation, and it should be feasible to link discrete clusters into an extended network via the linear bridging ability of the carboxylate. In this work, we chose 1,4-naphthalenedicarboxylic acid (1,4-H₂ndc) as the carboxylate-containing ligand and pyrazino[2,3-f]-1,10-phenanthroline (L) as the chelating ligand, yielding an unusual three-dimensional coordination polymer, [Cd₂(L)₂(1,4-ndc)₂], (I), based on tetranuclear Cd^II clusters.

The asymmetric unit of (I) consists of two crystallographically independent Cd^II atoms, two unique L chelating ligands and two unique bridging 1,4-ndc ligands (Fig. 1). Both Cd^II atoms are in a distorted seven-coordinate [CdO₅N₂] monocapped octahedral coordination geometry. Atom Cd1 bonds to a µ₂-O atom [O4ⁱ; symmetry code: (i) x-1, y, z] from a carboxylate ligand chelated to the adjoining Cd2 atom, four O atoms [O1, O2, O7ⁱⁱⁱ and O8ⁱⁱⁱ; symmetry code: (iii) x-1, 1/2-y, 1/2+z] from three different 1,4-ndc ligands and two N atoms (N1 and N2) from one chelating L ligand. The coordination environment of atom Cd2 is completed by two N atoms (N5 and N6) from a chelating L ligand, four O atoms (O3, O4, O5 and O6) from two different 1,4-ndc ligands and a µ₂-O atom [O6ⁱⁱ; symmetry code: (ii) 1-x, 1-y, -z] from a carboxylate ligand chelated to the adjoining Cd2 [Cd1 ?] atom. Thus, both unique 1,4-ndc ligands are bonded to three Cd^II atoms.

Tetranuclear clusters are formed in which four Cd atoms are bridged by the carboxylate groups of the 1,4-ndc ligands to form discrete rods (Fig. 2). The distance between the Cd atoms at either end of these rods is about 10.92 (2) Å. Each cluster lies across an inversion centre, with the Cd2 atoms in the middle and the Cd1 atoms on the ends of the rod. This rod-like tetranuclear Cd cluster including the bpy-like chelating ligand L has not been reported so far to the best of our knowledge, although other non-coplanar tetranuclear Cd clusters including bpy-like chelating ligands have been reported (Wei et al., 2005).

The tetranuclear cadmium carboxylate clusters act as rod-shaped secondary building units (SBUs) within the structure of (I). The SBUs are connected together by the aromatic backbone of the dicarboxylate ligands, connecting the clusters into a three-dimensional network (Fig. 3). Each SBU has eight 1,4-ndc ligands radiating outwards. However, these only connect to six adjacent clusters (four by single bridges) to give (4,4) sheets parallel to the yz plane, and two by double bridges in the z direction, to give the three-dimensional net. Each SBU therefore acts as a six-connecting node, and the overall network topology is that of α-polonium (Batten & Robson, 1998; Yang et al., 2008). Recently, several 6-connected nets, such as 4⁴.6¹¹, LB-1 (4⁴6¹⁰8), pcu (4¹²6³), roa (4⁴6¹⁰8), and rob (4⁸6⁶8) have been observed in coordination polymers (Zhang et al., 2007). It is noteworthy that the α-polonium net presented here is clearly different from the 6-connected three-dimensional nets mentioned above. To the best of our knowledge, (I) is the first α-polonium net constructed from rod-like clusters in coordination polymers. The result indicates that an appropriate combination of the dicarboxylate and aromatic chelating ligands is critical to the formation of high-dimensional structures based on metal clusters.

Related literature

For related literature, see: Batten & Robson (1998); Eddaoudi et al. (2001); Hagrman et al. (1999); Hu et al. (2006); Noveron et al. (2002); Wang et al. (2005); Wei et al. (2005); Yang et al. (2008); Zhang et al. (2007).

S2. Experimental

A mixture of CdCl₂.2.5H₂O (0.114 g, 0.5 mmol), 1,4-H₂ndc (0.110 g, 0.5 mmol) and L (0.123 g, 0.5 mmol) was dissolved in distilled water (12 ml), followed by addition of triethylamine until the pH of the system was about 5.7. The resulting solution was stirred for about 1 h at room temperature, sealed in a 23 ml Teflon-lined stainless steel autoclave and heated at 458 K for 2 d under autogenous pressure. Afterwards, the reaction system was cooled slowly to room temperature. Pale-yellow block crystals of (I) suitable for single-crystal X-ray diffraction analysis were collected from the final reaction system by filtration, washed several times with distilled water and dried in air at ambient temperature (yield 33% based on Cd^II).

S3. Refinement

All H atoms were positioned geometrically (C—H = 0.93 Å) and refined as riding, with U_iso(H) = 1.2U_eq(carrier).

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. A view of the local coordination of the Cd^II cations in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 20% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry codes: (i) x - 1, y, z; (ii) 1 - x, 1 - y, -z; (iii) x - 1, 1/2 - y, 1/2 + z.]
	Fig. 2. A view of the linkage of the tetranuclear core.
	Fig. 3. A view of the linkage of the tetranuclear core with six adjacent cores (H atoms and part of the aromatic rings have been omitted for clarity).

bis(pyrazino[2,3-f]-1,10-phenanthroline-κ²N,N')- bis(1,4-naphthalenedicarboxylato-κ⁵O,O':O'',O''':O')dicadmium(II)

Crystal data

[Cd2(C14H8N4)2(C12H6O4)2]	F(000) = 2224
Mr = 1117.62	Dx = 1.678 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 32808 reflections
a = 10.162 (2) Å	θ = 3.0–27.5°
b = 18.040 (4) Å	µ = 1.03 mm^−1
c = 24.160 (5) Å	T = 293 K
β = 92.78 (3)°	Block, pale yellow
V = 4423.9 (15) Å^3	0.31 × 0.29 × 0.24 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	10059 independent reflections
Radiation source: rotating anode	7470 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
Detector resolution: 10.0 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ω scans	h = −13→13
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −23→23
Tmin = 0.721, Tmax = 0.784	l = −31→28
41917 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.086	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0387P)^2 + 1.5094P] where P = (Fo^2 + 2Fc^2)/3
10059 reflections	(Δ/σ)max = 0.001
631 parameters	Δρmax = 0.55 e Å^−3
42 restraints	Δρmin = −0.42 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
C1	−0.1817 (3)	0.2785 (2)	0.10967 (12)	0.0445 (8)
C2	−0.0414 (3)	0.30369 (17)	0.10833 (12)	0.0398 (7)
C3	0.0363 (3)	0.27313 (19)	0.06958 (14)	0.0484 (8)
H3	0.0018	0.2366	0.0459	0.058*
C4	0.1674 (3)	0.2963 (2)	0.06519 (13)	0.0471 (8)
H4	0.2192	0.2742	0.0391	0.057*
C5	0.2201 (3)	0.35097 (18)	0.09874 (12)	0.0414 (7)
C6	0.3547 (3)	0.3810 (2)	0.08698 (12)	0.0460 (8)
C7	0.1453 (3)	0.38070 (18)	0.14205 (12)	0.0410 (7)
C8	0.1990 (3)	0.4308 (2)	0.18224 (15)	0.0547 (9)
H8	0.2838	0.4490	0.1788	0.066*
C9	0.1284 (4)	0.4527 (2)	0.22584 (16)	0.0656 (11)
H9	0.1665	0.4845	0.2523	0.079*
C10	−0.0011 (4)	0.4278 (2)	0.23128 (16)	0.0601 (10)
H10	−0.0481	0.4428	0.2614	0.072*
C11	−0.0577 (3)	0.38162 (19)	0.19249 (13)	0.0479 (8)
H11	−0.1443	0.3663	0.1961	0.058*
C12	0.0123 (3)	0.35635 (17)	0.14671 (12)	0.0391 (7)
C13	−0.3092 (4)	0.2129 (3)	−0.01395 (16)	0.0700 (11)
H13	−0.2517	0.2490	0.0002	0.084*
C14	−0.2883 (6)	0.1845 (3)	−0.06573 (19)	0.0922 (16)
H14	−0.2183	0.2013	−0.0857	0.111*
C15	−0.3710 (6)	0.1317 (3)	−0.08722 (19)	0.0941 (17)
H15	−0.3579	0.1118	−0.1221	0.113*
C16	−0.4757 (5)	0.1074 (2)	−0.05670 (17)	0.0745 (13)
C17	−0.4900 (4)	0.1399 (2)	−0.00375 (15)	0.0576 (9)
C18	−0.6015 (4)	0.1187 (2)	0.02941 (16)	0.0594 (9)
C19	−0.7109 (4)	0.1349 (3)	0.11008 (18)	0.0728 (12)
H19	−0.7177	0.1574	0.1444	0.087*
C20	−0.8077 (5)	0.0843 (3)	0.0918 (2)	0.0939 (16)
H20	−0.8771	0.0730	0.1140	0.113*
C21	−0.8000 (6)	0.0519 (3)	0.0412 (2)	0.0998 (18)
H21	−0.8649	0.0187	0.0287	0.120*
C22	−0.6958 (5)	0.0681 (2)	0.0083 (2)	0.0756 (13)
C23	−0.6763 (6)	0.0345 (2)	−0.0464 (2)	0.0881 (16)
C24	−0.5695 (6)	0.0536 (3)	−0.0767 (2)	0.0886 (16)
C25	−0.6398 (9)	−0.0267 (4)	−0.1436 (3)	0.136 (3)
H25	−0.6293	−0.0496	−0.1776	0.163*
C37	0.5715 (3)	0.39238 (19)	−0.05089 (12)	0.0446 (8)
C27	0.5540 (3)	0.35972 (18)	−0.10812 (12)	0.0410 (7)
C28	0.6395 (3)	0.3818 (2)	−0.14703 (13)	0.0499 (8)
H28	0.7086	0.4138	−0.1372	0.060*
C29	0.6224 (3)	0.3559 (2)	−0.20185 (13)	0.0517 (9)
H29	0.6786	0.3733	−0.2282	0.062*
C30	0.5264 (3)	0.30628 (19)	−0.21783 (12)	0.0442 (7)
C31	0.4382 (3)	0.27968 (18)	−0.17752 (13)	0.0445 (7)
C32	0.4512 (3)	0.30909 (17)	−0.12241 (12)	0.0397 (7)
C33	0.3619 (3)	0.28391 (19)	−0.08297 (14)	0.0494 (8)
H33	0.3691	0.3024	−0.0470	0.059*
C34	0.2665 (4)	0.2336 (2)	−0.09643 (16)	0.0592 (9)
H34	0.2092	0.2181	−0.0699	0.071*
C35	0.2542 (4)	0.2049 (2)	−0.15068 (17)	0.0674 (11)
H35	0.1888	0.1703	−0.1597	0.081*
C36	0.3372 (4)	0.2273 (2)	−0.19022 (15)	0.0580 (9)
H36	0.3273	0.2081	−0.2259	0.070*
C51	0.8524 (3)	0.5368 (2)	0.02255 (17)	0.0620 (10)
H51	0.8307	0.5181	−0.0126	0.074*
C52	0.9583 (4)	0.5867 (3)	0.0293 (2)	0.0751 (12)
H52	1.0071	0.5997	−0.0008	0.090*
C39	0.9884 (4)	0.6155 (2)	0.0800 (2)	0.0741 (12)
H39	1.0591	0.6480	0.0851	0.089*
C40	0.9125 (3)	0.5962 (2)	0.12481 (18)	0.0603 (10)
C41	0.8104 (3)	0.54562 (18)	0.11505 (15)	0.0487 (8)
C42	0.7306 (3)	0.52209 (18)	0.16042 (13)	0.0460 (8)
C43	0.5710 (4)	0.4436 (2)	0.19117 (14)	0.0560 (9)
H43	0.5094	0.4063	0.1837	0.067*
C44	0.5895 (4)	0.4687 (3)	0.24498 (15)	0.0713 (12)
H44	0.5412	0.4486	0.2731	0.086*
C45	0.6790 (5)	0.5229 (3)	0.25628 (16)	0.0748 (12)
H45	0.6903	0.5417	0.2920	0.090*
C46	0.7542 (4)	0.5505 (2)	0.21401 (16)	0.0606 (10)
C47	0.8596 (4)	0.6035 (2)	0.22339 (19)	0.0721 (12)
C48	0.9361 (4)	0.6261 (2)	0.1809 (2)	0.0717 (12)
C49	1.0560 (6)	0.6983 (4)	0.2412 (3)	0.133 (3)
H49	1.1250	0.7307	0.2502	0.159*
C50	0.9796 (7)	0.6756 (4)	0.2822 (3)	0.139 (3)
H50	0.9973	0.6949	0.3175	0.166*
C26	−0.7458 (9)	−0.0447 (3)	−0.1141 (3)	0.135 (3)
H26	−0.8039	−0.0799	−0.1292	0.162*
C38	0.5209 (4)	0.2833 (2)	−0.27837 (14)	0.0550 (9)
N1	−0.4071 (3)	0.19142 (18)	0.01702 (11)	0.0566 (8)
N2	−0.6093 (3)	0.15162 (17)	0.07961 (12)	0.0572 (8)
N3	−0.5537 (6)	0.0211 (3)	−0.12589 (18)	0.1127 (16)
N4	−0.7733 (6)	−0.0151 (3)	−0.0640 (2)	0.1245 (18)
N5	0.7827 (3)	0.51551 (16)	0.06439 (11)	0.0493 (7)
N6	0.6371 (3)	0.47031 (16)	0.14962 (11)	0.0475 (6)
N7	1.0374 (4)	0.6763 (2)	0.1874 (2)	0.1060 (15)
N8	0.8831 (4)	0.6286 (3)	0.27568 (18)	0.1051 (15)
O1	−0.2026 (2)	0.21104 (15)	0.11367 (13)	0.0757 (8)
O2	−0.2733 (2)	0.32490 (14)	0.10492 (10)	0.0542 (6)
O3	0.3700 (2)	0.44930 (15)	0.08679 (10)	0.0592 (7)
O4	0.4440 (2)	0.33603 (14)	0.07412 (9)	0.0541 (6)
O5	0.6779 (2)	0.38371 (15)	−0.02369 (9)	0.0590 (6)
O6	0.4775 (2)	0.42831 (13)	−0.03190 (9)	0.0499 (6)
O7	0.4653 (4)	0.2287 (2)	−0.29578 (13)	0.1165 (14)
O8	0.5719 (4)	0.3244 (2)	−0.31033 (11)	0.1151 (14)
Cd1	−0.44274 (2)	0.236071 (14)	0.109183 (9)	0.04296 (8)
Cd2	0.59398 (2)	0.441582 (15)	0.056187 (9)	0.04714 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0371 (17)	0.059 (2)	0.0370 (16)	−0.0046 (15)	−0.0003 (13)	0.0083 (15)
C2	0.0334 (15)	0.0430 (18)	0.0428 (16)	−0.0021 (13)	0.0007 (13)	0.0079 (14)
C3	0.0432 (18)	0.054 (2)	0.0477 (18)	−0.0060 (15)	0.0002 (15)	−0.0037 (16)
C4	0.0385 (17)	0.061 (2)	0.0426 (17)	−0.0009 (15)	0.0093 (14)	−0.0037 (16)
C5	0.0312 (15)	0.054 (2)	0.0390 (16)	−0.0021 (13)	0.0022 (13)	0.0073 (14)
C6	0.0321 (16)	0.075 (3)	0.0304 (15)	−0.0060 (16)	−0.0003 (12)	0.0044 (15)
C7	0.0333 (15)	0.0464 (18)	0.0431 (16)	−0.0006 (13)	0.0018 (13)	0.0045 (14)
C8	0.0412 (18)	0.064 (2)	0.058 (2)	−0.0062 (16)	0.0019 (16)	−0.0098 (18)
C9	0.058 (2)	0.077 (3)	0.062 (2)	−0.001 (2)	0.0012 (19)	−0.021 (2)
C10	0.052 (2)	0.074 (3)	0.055 (2)	0.0129 (19)	0.0085 (18)	−0.0076 (19)
C11	0.0372 (16)	0.058 (2)	0.0486 (18)	0.0056 (15)	0.0031 (14)	0.0030 (16)
C12	0.0355 (15)	0.0424 (18)	0.0392 (15)	0.0026 (13)	0.0011 (13)	0.0076 (13)
C13	0.065 (3)	0.091 (3)	0.054 (2)	0.008 (2)	0.007 (2)	0.003 (2)
C14	0.096 (4)	0.121 (5)	0.060 (3)	0.015 (3)	0.015 (3)	−0.009 (3)
C15	0.117 (4)	0.114 (4)	0.052 (2)	0.042 (4)	0.011 (3)	−0.007 (3)
C16	0.099 (3)	0.065 (3)	0.057 (2)	0.029 (2)	−0.025 (2)	−0.011 (2)
C17	0.068 (2)	0.055 (2)	0.0483 (19)	0.0132 (19)	−0.0153 (18)	0.0039 (17)
C18	0.068 (2)	0.050 (2)	0.057 (2)	0.0029 (18)	−0.0254 (19)	0.0090 (17)
C19	0.061 (2)	0.086 (3)	0.071 (3)	−0.020 (2)	−0.005 (2)	0.020 (2)
C20	0.072 (3)	0.107 (4)	0.102 (4)	−0.037 (3)	−0.009 (3)	0.037 (3)
C21	0.112 (4)	0.080 (4)	0.102 (4)	−0.042 (3)	−0.052 (3)	0.022 (3)
C22	0.085 (3)	0.055 (3)	0.083 (3)	−0.012 (2)	−0.032 (3)	0.020 (2)
C23	0.129 (4)	0.044 (2)	0.085 (3)	0.000 (3)	−0.058 (3)	−0.001 (2)
C24	0.132 (5)	0.062 (3)	0.068 (3)	0.026 (3)	−0.033 (3)	−0.009 (2)
C25	0.192 (7)	0.092 (5)	0.117 (5)	0.024 (5)	−0.055 (5)	−0.026 (4)
C37	0.054 (2)	0.049 (2)	0.0310 (15)	−0.0104 (15)	0.0018 (15)	−0.0018 (14)
C27	0.0449 (17)	0.0470 (19)	0.0311 (14)	0.0069 (14)	0.0013 (13)	−0.0033 (13)
C28	0.0512 (19)	0.057 (2)	0.0414 (17)	−0.0062 (16)	0.0026 (15)	−0.0079 (15)
C29	0.055 (2)	0.066 (2)	0.0353 (16)	0.0031 (18)	0.0117 (15)	−0.0066 (16)
C30	0.0530 (19)	0.048 (2)	0.0310 (15)	0.0097 (15)	0.0005 (14)	−0.0055 (14)
C31	0.0486 (18)	0.0437 (19)	0.0407 (16)	0.0088 (14)	−0.0034 (14)	−0.0048 (14)
C32	0.0433 (17)	0.0411 (18)	0.0344 (15)	0.0066 (13)	−0.0002 (13)	−0.0031 (13)
C33	0.054 (2)	0.051 (2)	0.0428 (17)	−0.0013 (16)	0.0047 (16)	−0.0018 (15)
C34	0.061 (2)	0.061 (2)	0.057 (2)	−0.0100 (19)	0.0071 (18)	0.0013 (18)
C35	0.067 (3)	0.059 (2)	0.075 (3)	−0.015 (2)	−0.006 (2)	−0.007 (2)
C36	0.065 (2)	0.057 (2)	0.051 (2)	−0.0052 (18)	−0.0059 (18)	−0.0150 (17)
C51	0.0455 (19)	0.078 (3)	0.062 (2)	−0.0051 (18)	−0.0009 (17)	0.010 (2)
C52	0.052 (2)	0.078 (3)	0.095 (3)	−0.006 (2)	0.001 (2)	0.022 (3)
C39	0.047 (2)	0.055 (3)	0.119 (4)	−0.0069 (18)	−0.012 (2)	0.002 (2)
C40	0.0409 (19)	0.050 (2)	0.088 (3)	0.0020 (16)	−0.0132 (19)	−0.007 (2)
C41	0.0400 (17)	0.0422 (19)	0.062 (2)	0.0024 (14)	−0.0117 (16)	−0.0065 (16)
C42	0.0435 (17)	0.0437 (19)	0.0492 (18)	0.0118 (15)	−0.0135 (15)	−0.0100 (15)
C43	0.055 (2)	0.069 (2)	0.0431 (18)	0.0020 (18)	−0.0015 (16)	−0.0034 (17)
C44	0.075 (3)	0.098 (3)	0.0413 (19)	0.004 (3)	0.0014 (19)	−0.005 (2)
C45	0.085 (3)	0.097 (3)	0.041 (2)	0.014 (3)	−0.010 (2)	−0.022 (2)
C46	0.060 (2)	0.058 (2)	0.062 (2)	0.0125 (18)	−0.0204 (19)	−0.0219 (19)
C47	0.063 (2)	0.064 (3)	0.087 (3)	0.010 (2)	−0.019 (2)	−0.038 (2)
C48	0.049 (2)	0.052 (2)	0.111 (3)	0.0065 (18)	−0.026 (2)	−0.033 (2)
C49	0.072 (4)	0.121 (5)	0.201 (8)	−0.008 (3)	−0.032 (4)	−0.106 (6)
C50	0.105 (5)	0.149 (6)	0.159 (6)	−0.014 (5)	−0.021 (4)	−0.102 (5)
C26	0.228 (9)	0.046 (3)	0.121 (5)	−0.009 (4)	−0.088 (6)	−0.021 (3)
C38	0.063 (2)	0.066 (3)	0.0362 (17)	0.0125 (19)	0.0031 (17)	−0.0149 (17)
N1	0.0557 (18)	0.070 (2)	0.0437 (15)	0.0025 (16)	−0.0037 (14)	0.0003 (15)
N2	0.0562 (18)	0.060 (2)	0.0542 (17)	−0.0088 (15)	−0.0060 (14)	0.0111 (15)
N3	0.167 (4)	0.084 (3)	0.082 (3)	0.036 (3)	−0.045 (3)	−0.033 (2)
N4	0.170 (5)	0.070 (3)	0.127 (4)	−0.018 (3)	−0.069 (3)	0.004 (3)
N5	0.0393 (14)	0.0575 (18)	0.0503 (16)	−0.0036 (13)	−0.0046 (12)	0.0021 (14)
N6	0.0469 (15)	0.0522 (17)	0.0426 (14)	0.0013 (13)	−0.0047 (12)	−0.0086 (13)
N7	0.060 (2)	0.087 (3)	0.169 (4)	−0.008 (2)	−0.020 (2)	−0.062 (3)
N8	0.094 (3)	0.113 (3)	0.106 (3)	0.000 (3)	−0.026 (2)	−0.067 (3)
O1	0.0499 (15)	0.0560 (17)	0.119 (2)	−0.0124 (13)	−0.0162 (15)	0.0243 (16)
O2	0.0339 (12)	0.0611 (16)	0.0675 (15)	0.0025 (11)	0.0015 (11)	0.0031 (12)
O3	0.0568 (15)	0.0641 (17)	0.0574 (15)	−0.0205 (12)	0.0101 (12)	−0.0056 (12)
O4	0.0349 (12)	0.0788 (17)	0.0488 (13)	0.0077 (11)	0.0056 (10)	0.0202 (12)
O5	0.0551 (15)	0.0814 (19)	0.0398 (12)	−0.0068 (13)	−0.0068 (11)	−0.0041 (12)
O6	0.0620 (14)	0.0525 (14)	0.0362 (11)	−0.0039 (11)	0.0131 (11)	−0.0078 (10)
O7	0.175 (4)	0.116 (3)	0.0603 (19)	−0.043 (3)	0.021 (2)	−0.0422 (19)
O8	0.188 (4)	0.121 (3)	0.0386 (15)	−0.047 (3)	0.025 (2)	−0.0161 (17)
Cd1	0.03732 (12)	0.05805 (16)	0.03338 (12)	−0.00738 (10)	0.00029 (9)	0.00770 (10)
Cd2	0.03955 (13)	0.06988 (18)	0.03222 (12)	−0.01781 (11)	0.00419 (9)	−0.01023 (11)

Geometric parameters (Å, º)

C1—O1	1.239 (4)	C30—C31	1.437 (4)
C1—O2	1.253 (4)	C30—C38	1.519 (4)
C1—C2	1.499 (4)	C31—C36	1.418 (5)
C2—C3	1.369 (4)	C31—C32	1.433 (4)
C2—C12	1.418 (4)	C32—C33	1.422 (4)
C3—C4	1.406 (4)	C33—C34	1.356 (5)
C3—H3	0.9300	C33—H33	0.9300
C4—C5	1.369 (4)	C34—C35	1.409 (5)
C4—H4	0.9300	C34—H34	0.9300
C5—C7	1.428 (4)	C35—C36	1.366 (5)
C5—C6	1.510 (4)	C35—H35	0.9300
C6—O3	1.241 (4)	C36—H36	0.9300
C6—O4	1.268 (4)	C51—N5	1.319 (4)
C7—C8	1.416 (5)	C51—C52	1.407 (5)
C7—C12	1.431 (4)	C51—H51	0.9300
C8—C9	1.361 (5)	C52—C39	1.352 (6)
C8—H8	0.9300	C52—H52	0.9300
C9—C10	1.403 (5)	C39—C40	1.404 (6)
C9—H9	0.9300	C39—H39	0.9300
C10—C11	1.361 (5)	C40—C41	1.393 (5)
C10—H10	0.9300	C40—C48	1.468 (6)
C11—C12	1.419 (4)	C41—N5	1.356 (4)
C11—H11	0.9300	C41—C42	1.458 (5)
C13—N1	1.331 (5)	C42—N6	1.349 (4)
C13—C14	1.378 (6)	C42—C46	1.402 (5)
C13—H13	0.9300	C43—N6	1.326 (4)
C14—C15	1.357 (7)	C43—C44	1.381 (5)
C14—H14	0.9300	C43—H43	0.9300
C15—C16	1.394 (7)	C44—C45	1.355 (6)
C15—H15	0.9300	C44—H44	0.9300
C16—C17	1.421 (5)	C45—C46	1.396 (6)
C16—C24	1.429 (7)	C45—H45	0.9300
C17—N1	1.336 (5)	C46—C47	1.446 (6)
C17—C18	1.469 (5)	C47—N8	1.352 (5)
C18—N2	1.356 (5)	C47—C48	1.379 (6)
C18—C22	1.402 (5)	C48—N7	1.374 (5)
C19—N2	1.332 (5)	C49—C50	1.352 (9)
C19—C20	1.397 (6)	C49—N7	1.365 (7)
C19—H19	0.9300	C49—H49	0.9300
C20—C21	1.360 (7)	C50—N8	1.300 (7)
C20—H20	0.9300	C50—H50	0.9300
C21—C22	1.387 (7)	C26—N4	1.365 (8)
C21—H21	0.9300	C26—H26	0.9300
C22—C23	1.475 (7)	C38—O7	1.200 (5)
C23—N4	1.383 (6)	C38—O8	1.206 (5)
C23—C24	1.383 (8)	Cd1—N1	2.412 (3)
C24—N3	1.341 (6)	Cd1—N2	2.362 (3)
C25—N3	1.287 (9)	Cd2—N5	2.336 (3)
C25—C26	1.359 (10)	Cd2—N6	2.337 (3)
C25—H25	0.9300	Cd1—O1	2.479 (3)
C37—O5	1.248 (4)	Cd1—O2	2.358 (2)
C37—O6	1.259 (4)	Cd2—O3	2.431 (2)
C37—C27	1.506 (4)	Cd2—O4	2.490 (2)
C37—Cd2	2.734 (3)	Cd2—O5	2.388 (2)
C27—C28	1.370 (4)	Cd2—O6	2.396 (2)
C27—C32	1.418 (4)	Cd1—O8^i	2.228 (3)
C28—C29	1.407 (4)	Cd1—O4^ii	2.280 (2)
C28—H28	0.9300	Cd1—O7^i	2.599 (3)
C29—C30	1.366 (5)	Cd2—O6^iii	2.518 (2)
C29—H29	0.9300
O1—C1—O2	122.3 (3)	C52—C51—H51	118.9
O1—C1—C2	117.8 (3)	C39—C52—C51	119.3 (4)
O2—C1—C2	119.9 (3)	C39—C52—H52	120.3
O1—C1—Cd1	63.94 (18)	C51—C52—H52	120.3
O2—C1—Cd1	58.38 (16)	C52—C39—C40	119.6 (4)
C2—C1—Cd1	177.8 (2)	C52—C39—H39	120.2
C3—C2—C12	120.1 (3)	C40—C39—H39	120.2
C3—C2—C1	118.2 (3)	C41—C40—C39	117.7 (4)
C12—C2—C1	121.7 (3)	C41—C40—C48	119.0 (4)
C2—C3—C4	120.8 (3)	C39—C40—C48	123.3 (4)
C2—C3—H3	119.6	N5—C41—C40	122.4 (3)
C4—C3—H3	119.6	N5—C41—C42	117.6 (3)
C5—C4—C3	121.0 (3)	C40—C41—C42	120.0 (3)
C5—C4—H4	119.5	N6—C42—C46	121.2 (3)
C3—C4—H4	119.5	N6—C42—C41	117.9 (3)
C4—C5—C7	119.8 (3)	C46—C42—C41	120.8 (3)
C4—C5—C6	118.6 (3)	N6—C43—C44	122.9 (4)
C7—C5—C6	121.5 (3)	N6—C43—H43	118.6
O3—C6—O4	122.8 (3)	C44—C43—H43	118.6
O3—C6—C5	118.2 (3)	C45—C44—C43	119.1 (4)
O4—C6—C5	118.8 (3)	C45—C44—H44	120.5
C8—C7—C5	122.7 (3)	C43—C44—H44	120.5
C8—C7—C12	118.4 (3)	C44—C45—C46	119.7 (3)
C5—C7—C12	118.8 (3)	C44—C45—H45	120.1
C9—C8—C7	121.0 (3)	C46—C45—H45	120.1
C9—C8—H8	119.5	C45—C46—C42	118.1 (4)
C7—C8—H8	119.5	C45—C46—C47	123.3 (4)
C8—C9—C10	120.8 (4)	C42—C46—C47	118.6 (4)
C8—C9—H9	119.6	N8—C47—C48	121.1 (4)
C10—C9—H9	119.6	N8—C47—C46	117.6 (5)
C11—C10—C9	119.9 (3)	C48—C47—C46	121.3 (4)
C11—C10—H10	120.0	N7—C48—C47	123.8 (4)
C9—C10—H10	120.0	N7—C48—C40	115.8 (5)
C10—C11—C12	121.5 (3)	C47—C48—C40	120.4 (4)
C10—C11—H11	119.3	C50—C49—N7	123.5 (5)
C12—C11—H11	119.3	C50—C49—H49	118.2
C2—C12—C11	122.3 (3)	N7—C49—H49	118.2
C2—C12—C7	119.3 (3)	N8—C50—C49	124.4 (6)
C11—C12—C7	118.3 (3)	N8—C50—H50	117.8
N1—C13—C14	123.7 (5)	C49—C50—H50	117.8
N1—C13—H13	118.1	C25—C26—N4	125.0 (7)
C14—C13—H13	118.1	C25—C26—H26	117.5
C15—C14—C13	119.2 (5)	N4—C26—H26	117.5
C15—C14—H14	120.4	O7—C38—O8	119.3 (4)
C13—C14—H14	120.4	O7—C38—C30	123.8 (4)
C14—C15—C16	119.5 (4)	O8—C38—C30	116.8 (4)
C14—C15—H15	120.2	C13—N1—C17	117.8 (3)
C16—C15—H15	120.2	C13—N1—Cd1	124.9 (3)
C15—C16—C17	117.4 (4)	C17—N1—Cd1	117.3 (2)
C15—C16—C24	123.2 (5)	C19—N2—C18	118.4 (3)
C17—C16—C24	119.3 (5)	C19—N2—Cd1	122.9 (3)
N1—C17—C16	122.3 (4)	C18—N2—Cd1	118.7 (2)
N1—C17—C18	117.7 (3)	C25—N3—C24	118.6 (7)
C16—C17—C18	119.9 (4)	C26—N4—C23	110.7 (6)
N2—C18—C22	122.9 (4)	C51—N5—C41	118.7 (3)
N2—C18—C17	117.0 (3)	C51—N5—Cd2	124.7 (2)
C22—C18—C17	120.1 (4)	C41—N5—Cd2	116.0 (2)
N2—C19—C20	121.7 (4)	C43—N6—C42	118.9 (3)
N2—C19—H19	119.1	C43—N6—Cd2	124.9 (2)
C20—C19—H19	119.1	C42—N6—Cd2	116.0 (2)
C21—C20—C19	119.7 (5)	C49—N7—C48	111.6 (5)
C21—C20—H20	120.2	C50—N8—C47	115.5 (6)
C19—C20—H20	120.2	C1—O1—Cd1	89.4 (2)
C20—C21—C22	120.2 (4)	C1—O2—Cd1	94.7 (2)
C20—C21—H21	119.9	C6—O3—Cd2	93.7 (2)
C22—C21—H21	119.9	C6—O4—Cd1^iv	140.3 (2)
C21—C22—C18	117.1 (4)	C6—O4—Cd2	90.3 (2)
C21—C22—C23	124.5 (5)	Cd1^iv—O4—Cd2	111.56 (9)
C18—C22—C23	118.4 (5)	C37—O5—Cd2	92.09 (19)
N4—C23—C24	124.3 (5)	C37—O6—Cd2	91.39 (19)
N4—C23—C22	114.6 (6)	C37—O6—Cd2^iii	127.61 (19)
C24—C23—C22	121.0 (4)	Cd2—O6—Cd2^iii	103.78 (8)
N3—C24—C23	119.4 (6)	C38—O7—Cd1^v	85.8 (2)
N3—C24—C16	119.4 (6)	C38—O8—Cd1^v	104.2 (3)
C23—C24—C16	121.2 (4)	O8^i—Cd1—O4^ii	136.26 (11)
N3—C25—C26	121.9 (7)	O8^i—Cd1—O2	110.67 (14)
N3—C25—H25	119.1	O4^ii—Cd1—O2	78.62 (8)
C26—C25—H25	119.1	O8^i—Cd1—N2	87.97 (14)
O5—C37—O6	121.7 (3)	O4^ii—Cd1—N2	93.24 (10)
O5—C37—C27	119.7 (3)	O2—Cd1—N2	159.91 (9)
O6—C37—C27	118.6 (3)	O8^i—Cd1—N1	129.46 (12)
O5—C37—Cd2	60.77 (16)	O4^ii—Cd1—N1	90.96 (9)
O6—C37—Cd2	61.20 (16)	O2—Cd1—N1	92.53 (10)
C27—C37—Cd2	175.4 (2)	N2—Cd1—N1	69.07 (11)
C28—C27—C32	120.3 (3)	O8^i—Cd1—O1	81.31 (13)
C28—C27—C37	117.8 (3)	O4^ii—Cd1—O1	129.66 (8)
C32—C27—C37	121.9 (3)	O2—Cd1—O1	53.58 (8)
C27—C28—C29	119.7 (3)	N2—Cd1—O1	125.82 (10)
C27—C28—H28	120.1	N1—Cd1—O1	77.76 (11)
C29—C28—H28	120.1	O8^i—Cd1—O7^i	50.23 (11)
C30—C29—C28	122.5 (3)	O4^ii—Cd1—O7^i	86.47 (10)
C30—C29—H29	118.7	O2—Cd1—O7^i	99.61 (12)
C28—C29—H29	118.7	N2—Cd1—O7^i	98.16 (13)
C29—C30—C31	119.2 (3)	N1—Cd1—O7^i	166.83 (13)
C29—C30—C38	116.4 (3)	O1—Cd1—O7^i	113.64 (13)
C31—C30—C38	124.5 (3)	N5—Cd2—N6	71.14 (10)
C36—C31—C32	118.7 (3)	N5—Cd2—O5	89.68 (9)
C36—C31—C30	123.0 (3)	N6—Cd2—O5	145.10 (9)
C32—C31—C30	118.3 (3)	N5—Cd2—O6	120.03 (9)
C27—C32—C33	122.0 (3)	N6—Cd2—O6	160.30 (9)
C27—C32—C31	119.9 (3)	O5—Cd2—O6	54.47 (8)
C33—C32—C31	118.1 (3)	N5—Cd2—O3	135.91 (9)
C34—C33—C32	121.7 (3)	N6—Cd2—O3	80.09 (9)
C34—C33—H33	119.2	O5—Cd2—O3	130.33 (9)
C32—C33—H33	119.2	O6—Cd2—O3	81.17 (8)
C33—C34—C35	120.0 (3)	N5—Cd2—O4	158.20 (9)
C33—C34—H34	120.0	N6—Cd2—O4	95.11 (9)
C35—C34—H34	120.0	O5—Cd2—O4	92.97 (8)
C36—C35—C34	120.8 (4)	O6—Cd2—O4	78.35 (8)
C36—C35—H35	119.6	O3—Cd2—O4	53.20 (8)
C34—C35—H35	119.6	N5—Cd2—O6^iii	73.38 (9)
C35—C36—C31	120.8 (3)	N6—Cd2—O6^iii	93.26 (9)
C35—C36—H36	119.6	O5—Cd2—O6^iii	109.24 (8)
C31—C36—H36	119.6	O6—Cd2—O6^iii	76.22 (8)
N5—C51—C52	122.2 (4)	O3—Cd2—O6^iii	75.75 (8)
N5—C51—H51	118.9	O4—Cd2—O6^iii	125.55 (8)

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