A tetra­nuclear cadmium(II) complex based on the 2-(quinolin-8-yl­oxy)acetonitrile ligand

The hydro­thermal reaction of 2-(quinolin-8-yl­oxy)acetonitrile and Cd(ClO₄)₂ yielded the noncentrosymmetric coordination complex tetra­kis­[[mu]-2-(quinolin-8-yl­oxy)acetato]­tetra­kis­[[mu]-2-(quinolin-8-yl­oxy)acetonitrile]­tetra­cadmium tetra­kis­(perchlorate) dihydrate, [Cd₄(C₁₁H₈NO₃)₄(C₁₁H₈N₂O)₄](ClO₄)₄·2H₂O. The local coordination environment around the Cd^II cation can be best described as a capped octa­hedron defined by two N atoms and five O atoms from three ligands. The Cd^II cations are linked by the ligands with Cd-O-Cd and Cd-O-C-C-O-Cd bridges, forming tetra­nuclear units, there being two independent tertranuclear units in the structure. The fourfold rotoinversion centre sits at the centre of each Cd₄ core. The two perchlorate anions in the asymmetric unit are linked by the water mol­ecule through O-H...O hydrogen bonds.

S1. Comment

The rational design and construction of novel functional metal complexes have attracted much attention, owing to their intriguing architectures and topologies (Ye & Tong et al., 2005; Hill et al., 2005; Hong, 2007) and their potential application in many fields, including ferroelectricity, magnetism, electrical conductivity, molecular adsorption, heterogeneous catalysis and fluorescence (Zhang et al., 2009; Zhang & Xiong, 2012; Nouar et al., 2008; Li et al., 2009; Yao et al., 2008). In particular, noncentrosymmetric bulk materials or polar crystals possess technologically useful properties, such as ferroelectricity, pyroelectricity, piezoelectricity, triboluminescence and nonlinear optical (NLO) function (especially second harmonic generation, SHG) (Marks & Ratner, 1995; Desiraju, 1989; Xiong & You, 2002), and SHG, piezoelectric and ferroelectric properties are of particular importance in areas such as telecommunications, optical storage, information processing and mechanical energy transfer. However, the rational design and synthesis of metal complexes crystallizing as acentric and homochiral solids still remain long-term challenges. Recent progress in the synthesis (or self-assembly) and design of novel materials based on metal–organic coordination compounds has shown that acentric and homochiral metal–organic solids can be achieved through the following protocols: (i) using asymmetric, flexible or racemic organic ligands to self-assemble with metal ions; (ii) using racemic organic ligands coordinating to metal ions to result in self-resolution to obtain chiral compounds; (iii) obtaining asymmetric coordination compounds through self-assembly of metal and homochiral organic ligands (Ye & Wu et al., 2005; Xiong et al., 2000; Ye et al., 2008; Zhao et al., 2004). We are interested in hydrothermal or solvothermal reactions because they allow in situ reactions to occur without exerting synthetic control, and we have obtained a fascinating variety of acentric and novel metal–organic coordination compounds through these processes (Ye, Wu et al., 2005; Ye et al., 2008; Ye & Wang et al., 2005).

A series of cadmium coordination polymers containing carboxylate ligands have been reported (Yang et al., 2009; Zhang et al., 2012; Zhou et al., 2011; Nie & Wang, 2011; Han et al., 2012; Wang et al., 2012) and, compared with the above-mentioned cases, seven-coordinated complexes crystallizing in noncentrosymmetric space groups are rare. We report here the synthesis and crystal structure of an acentric seven-coordinated tetranuclear cadmium coordination compound, tetrakis[µ-2-(quinolin-8-yloxy)acetato]tetrakis[µ-2-(quinolin-8-yloxy)acetonitrile]tetracadmium tetrakis(perchlorate) dihydrate, (I).

Compound (I) has an asymmetric unit containing two crystallographically unique Cd^II cations, two 2-(quinolin-8-yloxy)acetate anions, two 2-(quinolin-8-yloxy)acetonitrile molecules, two perchlorate anions and a water molecule (Fig. 1). X-ray analysis of (I) reveals that half of the cyano groups of 2-(quinolin-8-yloxy)acetonitrile were hydrolyzed in situ, leading to the formation of carboxylate groups. Three O atoms (O14, O15 and O16) in one of the perchlorate anions are disordered. The local coordination environments around the two Cd^II cations are similar and are best described as capped octahedra, with coordination from two N atoms and five O atoms from one 2-(quinolin-8-yloxy)acetonitrile and two 2-(quinolin-8-yloxy)acetate ligands. The 2-(quinolin-8-yloxy)acetonitrile ligand coordinates to one Cd^II atom through the O and ring N atom to form a stable five-membered chelate ring (N2/Cd1/O4/C27/C28 and N2/Cd2/O15/C17/C16), while the cyano group of the 2-(quinolin-8-yloxy)acetonitrile ligand is not coordinated.

The coordination mode of the 2-(quinolin-8-yloxy)acetate ligand is more complex than that of the 2-(quinolin-8-yloxy)acetonitrile ligand. In addition to the O and N atoms chelating the Cd^II centre, two carboxylate O atoms are also coordinated to the Cd^II centre to form two five-membered chelate rings (O6/Cd1/O77/C43/C44 and O77/Cd1/N5/C38/C39, and O1/Cd2/O2/C11/C10 and O1/Cd2/N1/C5/C6) and one four-membered chelate ring (O5A/Cd1/O6A/C44 and O2C/Cd2/O3C/C11). Thus, the seven-coordinated Cd^II coordination environment is fulfilled by one O atom and one N atom from one 2-(quinolin-8-yloxy)acetonitrile ligand, two O atoms of the carboxylate group of one 2-(quinolin-8-yloxy)acetate ligand, and two O atoms and one N atom from another 2-(quinolin-8-yloxy)acetate ligand, as shown in Fig. 1.

Although the two unique Cd^II centres show similar coordination environments, the coordination bond lengths and angles are significantly different. Atoms N1, O1, O2 and O3A around Cd1 are nearly coplanar, with a mean deviation from the plane of 0.3503 Å, while atoms N5, O5, O6 and O7A around Cd2 are also nearly coplanar, with a mean deviation from the plane of 0.3041 Å. The Cd1—O and Cd1—N bond lengths are in the ranges 2.190 (4)–2.631 (4) and 2.254 (5)-2.270 (4) Å, respectively, while the Cd2—O and Cd2—N bond lengths are in the ranges 2.219 (4)–2.573 (4) and 2.269 (4)–2.283 (4) Å, respectively. The Cd—O bond lengths are comparable with those found in [KCd₂(edta)I]_n (H₄edta = ethylenediaminetetraacetic acid; Wang et al., 2012), which range from 2.208 (3) to 2.518 (3) Å, but the Cd—N distances are shorter than those found in [KCd₂(edta)I]_n [2.382 (3)–2.416 (3) Å]. Both bond lengths and angles observed in the ordered ClO₄^- anion are in agreement with standard values [Standard reference?], with Cl—O = 1.366 (6)–1.447 (7) Å.

The 2-(quinolin-8-yloxy)acetate anion acts as a tetradentate linker, connecting two Cd^II centres through the ring N atom and three O atoms of the oxyacetate group. Thus, the Cd^II cations at (x, y, z), (y, -x + 1, z), (-x + 1, -y + 1, z) and (-y + 1, x, -z + 2) are linked by the 2-(quinolin-8-yloxy)acetate ligand to form a tetranuclear unit (Fig. 2), which is like a disthe [Text missing?] Cd₄ core. The oxyacetate group bridges the two nearest Cd^II cations: one of the O atoms from the oxyacetate group links the Cd^II cations via an O—Cd bond, and two linked Cd^II cations are strengthened by the oxyacetate group with a Cd—O—C—C—O—Cd bridge.

In the structure of (I), numerous intermolecular hydrogen bonds (O1W—H1W···O9, O1W—H2W···O15 and O1W—H2W···O15B; Table 1) play an important role in stabilizing the structure, linking the ions of the asymmetric unit, the water molecules and perchlorate anions. In addition, there are numerous nonclassical C—H···O hydrogen bonds (Table 1) in the structure, with C—H···O angles in the range 106–170°, and C···O and H···O distances in the ranges 2.982 (8)–3.495 (10) and 2.29–2.58 Å, respectively. The weak C23—H23···O12 and C43—H43B···O11 intramolecular hygrogen bonds link one of the perchlorate anions and part of the tetranuclear unit in the asymmetric unit. All the tetranuclear units are linked by the perchlorate anions and water molecules via weak C2—H2···O11ⁱ, C8—H8···O13ⁱⁱ, C10—H10A···O3ⁱⁱⁱ, C12—H12···O16B^iv, C13—H13···O1W^iv, C21—H21B···O3^v, C32—H32A···O7^vi, C41—H41···O9^vii and C43—H43A···O7^viii intermolecular hydrogen bonds, forming the three-dimensional structure (Fig. 3; see Table 1 for symmetry codes).

In summary, (I) crystallizes fortuitously in an acentric space group stabilised by hydrogen-bonding interactions. The hydrothermal reaction leads to in situ ligand synthesis and the formation of this novel tetranuclear Cd^II coordination compound. In addition, the Cd^II cation has a capped octahedral geometry, and coordination compounds with such a geometry for a Cd^II centre are extremely rare in the Cambridge Structural Database (Version?; Allen 2002).

Related literature

For related literature, see: Allen (2002); Desiraju (1989); Han et al. (2012); Hill et al. (2005); Hong (2007); Li et al. (2009); Marks & Ratner (1995); Nie & Wang (2011); Nouar et al. (2008); Wang et al. (2012); Xiong & You (2002); Xiong et al. (2000); Yang et al. (2009); Yao et al. (2008); Ye et al. (2008); Ye, Tong & Chen (2005); Ye, Wang, Zhao & Xiong (2005); Ye, Wu, Song, Wang, Xiong & Xue (2005); Zhang & Xiong (2012); Zhang et al. (2009); Zhang, Wu, Zheng & Liu (2012); Zhao et al. (2004); Zhou et al. (2011).

S2. Experimental

The hydrothermal reaction of 2-(quinolin-8-yloxy)acetonitrile (1 mmol) and Cd(ClO₄) (1 mmol) in the presence of water (1.5 ml) in a sealed Pyrex tube at 383 K for several days gave colourless block-shaped crystals of (I). Crystals were isolated from the solution and then washed and dried.

S3. Refinement

Three O atoms of the perchlorate anion were modelled as disordered over two sites. The site-occupancy factor of the major component refined to 0.55 (4). All atom lengths in the anions were restrained to reasonable distances, and restraints were also applied to the three disordered O atoms to ensure that reasonable displacement parameters were obtained. Constraints were added to give equivalent displacement parameters for the corresponding atoms of the minor and major disorder components.

H atoms were refined isotropically. H atoms on C atoms were included in calculated positions and were refined using a riding model, with C—H = 0.93 or 0.97 Å for aromatic or methylene C atoms, respectively, and with U_iso(H) = 1.2U_eq(C). The H atoms bonded to O1W were discernible in difference electron-density maps. These atoms were placed as found and allowed to refine, with the O—H distances restrained to 0.85 (1) Å and H···H distances restrained to 1.39 (1) Å. For water H atoms, U_iso(H) = 1.5U_eq(O). In total, the structure had 111 restraints imposed.

Computing details

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. All H atoms have been omitted for clarity.

Fig. 2. A view of the tetranuclear unit of (I).

Fig. 3. The crystal structure of (I), viewed along the c axis. All H atoms have been omitted, except for those on atom O1W. Dashed lines indicate intermolecular O1W—H···O hydrogen bonds. [Image very grainy - can a sharper plot be provided?]

Tetrakis[µ-2-(quinolin-8-yloxy)acetato]tetrakis[µ-2-(quinolin-8- yloxy)acetonitrile]tetracadmium tetrakis(perchlorate) dihydrate

Crystal data

[Cd4(C11H8NO3)4(C11H8N2O)4](ClO4)4·2H2O	Dx = 1.767 Mg m^−3
Mr = 2428.94	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4	Cell parameters from 10477 reflections
Hall symbol: I -4	θ = 3.1–27.5°
a = 27.838 (4) Å	µ = 1.13 mm^−1
c = 11.779 (2) Å	T = 293 K
V = 9128 (2) Å^3	Block, colourless
Z = 4	0.2 × 0.2 × 0.2 mm
F(000) = 4848

Data collection

Rigaku Mercury2 diffractometer	8258 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.075
Graphite monochromator	θmax = 27.5°, θmin = 3.1°
ω scans	h = −36→35
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −36→36
Tmin = 0.795, Tmax = 0.810	l = −15→15
47881 measured reflections	180 standard reflections every 3 reflections
10477 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.048	H-atom parameters constrained
wR(F^2) = 0.103	w = 1/[σ^2(Fo^2) + (0.0495P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.002
10477 reflections	Δρmax = 0.56 e Å^−3
668 parameters	Δρmin = −0.34 e Å^−3
111 restraints	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (2)

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	Occ. (<1)
Cd1	0.523032 (15)	0.616086 (14)	0.93900 (4)	0.04217 (11)
O1	0.50675 (15)	0.61697 (14)	1.1405 (3)	0.0494 (10)
O2	0.56113 (14)	0.55616 (13)	1.0376 (3)	0.0472 (10)
O3	0.56552 (14)	0.50741 (13)	1.1839 (4)	0.0492 (9)
O4	0.53631 (15)	0.64955 (17)	0.7325 (3)	0.0609 (12)
N1	0.48034 (16)	0.68182 (16)	0.9920 (4)	0.0403 (11)
N2	0.59576 (17)	0.64940 (16)	0.9094 (4)	0.0437 (11)
N3	0.5496 (5)	0.5753 (5)	0.5093 (8)	0.164 (5)
C1	0.4699 (2)	0.7164 (2)	0.9196 (6)	0.0535 (15)
H1	0.4825	0.7145	0.8466	0.064*
C2	0.4410 (2)	0.7557 (2)	0.9465 (7)	0.0570 (16)
H2	0.4347	0.7794	0.8928	0.068*
C3	0.4225 (2)	0.7587 (2)	1.0502 (7)	0.0591 (17)
H3	0.4025	0.7843	1.0684	0.071*
C4	0.4327 (2)	0.7240 (2)	1.1326 (6)	0.0476 (15)
C5	0.46257 (18)	0.68543 (19)	1.1002 (4)	0.0350 (12)
C6	0.47488 (18)	0.64998 (18)	1.1788 (5)	0.0385 (12)
C7	0.4551 (2)	0.6511 (2)	1.2859 (5)	0.0496 (15)
H7	0.4621	0.6266	1.3369	0.059*
C8	0.4249 (2)	0.6885 (2)	1.3194 (6)	0.0629 (18)
H8	0.4120	0.6890	1.3922	0.076*
C9	0.4145 (2)	0.7237 (2)	1.2450 (6)	0.0568 (17)
H9	0.3947	0.7488	1.2682	0.068*
C10	0.5181 (2)	0.57645 (19)	1.2070 (5)	0.0425 (13)
H10A	0.4890	0.5592	1.2271	0.051*
H10B	0.5340	0.5863	1.2765	0.051*
C11	0.5506 (2)	0.5449 (2)	1.1381 (5)	0.0433 (13)
C12	0.6250 (2)	0.6495 (2)	0.9972 (6)	0.0560 (17)
H12	0.6147	0.6355	1.0647	0.067*
C13	0.6710 (3)	0.6697 (3)	0.9928 (8)	0.072 (2)
H13	0.6910	0.6687	1.0560	0.086*
C14	0.6858 (3)	0.6906 (3)	0.8973 (8)	0.072 (2)
H14	0.7160	0.7049	0.8944	0.087*
C15	0.6563 (2)	0.6911 (2)	0.8016 (7)	0.0594 (17)
C16	0.6109 (2)	0.67023 (18)	0.8110 (5)	0.0462 (14)
C17	0.5799 (2)	0.6695 (2)	0.7156 (5)	0.0532 (15)
C18	0.5959 (3)	0.6881 (3)	0.6152 (6)	0.079 (2)
H18	0.5764	0.6875	0.5510	0.095*
C19	0.6432 (4)	0.7088 (3)	0.6100 (8)	0.095 (3)
H19	0.6539	0.7216	0.5416	0.114*
C20	0.6720 (3)	0.7102 (3)	0.6988 (8)	0.079 (2)
H20	0.7024	0.7238	0.6929	0.095*
C21	0.5075 (3)	0.6393 (3)	0.6360 (6)	0.082 (2)
H21A	0.5029	0.6685	0.5922	0.099*
H21B	0.4761	0.6282	0.6607	0.099*
C22	0.5294 (4)	0.6032 (5)	0.5652 (8)	0.112 (4)
Cd2	0.612382 (14)	0.961270 (14)	0.19432 (3)	0.04009 (10)
O5	0.61361 (14)	0.98048 (13)	0.3937 (3)	0.0434 (10)
O6	0.54604 (13)	0.93311 (13)	0.2875 (3)	0.0458 (9)
O7	0.49790 (13)	0.93213 (14)	0.4358 (4)	0.0496 (9)
O8	0.64871 (16)	0.93304 (14)	0.0049 (3)	0.0514 (10)
N4	0.64092 (15)	0.88495 (15)	0.1991 (4)	0.0423 (10)
N5	0.67877 (15)	1.00501 (16)	0.2419 (4)	0.0378 (10)
N6	0.7314 (3)	0.9896 (3)	−0.1571 (7)	0.115 (3)
C23	0.6376 (2)	0.8614 (2)	0.2966 (6)	0.0556 (15)
H23	0.6212	0.8760	0.3561	0.067*
C24	0.6571 (2)	0.8165 (2)	0.3154 (7)	0.0660 (18)
H24	0.6530	0.8011	0.3849	0.079*
C25	0.6818 (2)	0.7954 (2)	0.2318 (7)	0.065 (2)
H25	0.6958	0.7655	0.2435	0.078*
C26	0.6867 (2)	0.8188 (2)	0.1248 (6)	0.0494 (15)
C27	0.66579 (19)	0.8643 (2)	0.1130 (5)	0.0423 (13)
C28	0.6702 (2)	0.8879 (2)	0.0084 (5)	0.0478 (15)
C29	0.6945 (3)	0.8682 (2)	−0.0798 (6)	0.070 (2)
H29	0.6973	0.8845	−0.1483	0.084*
C30	0.7155 (3)	0.8223 (3)	−0.0660 (9)	0.083 (2)
H30	0.7321	0.8081	−0.1258	0.100*
C31	0.7113 (3)	0.7989 (2)	0.0353 (7)	0.070 (2)
H31	0.7255	0.7688	0.0440	0.084*
C32	0.6457 (3)	0.9567 (2)	−0.1010 (6)	0.0632 (18)
H32A	0.6227	0.9828	−0.0963	0.076*
H32B	0.6348	0.9343	−0.1586	0.076*
C33	0.6951 (3)	0.9765 (3)	−0.1339 (7)	0.076 (2)
C34	0.7131 (2)	1.0162 (2)	0.1669 (5)	0.0513 (15)
H34	0.7109	1.0034	0.0942	0.062*
C35	0.7509 (2)	1.0453 (2)	0.1910 (6)	0.0537 (15)
H35	0.7741	1.0515	0.1361	0.064*
C36	0.75459 (19)	1.0654 (2)	0.2963 (6)	0.0513 (15)
H36	0.7803	1.0855	0.3130	0.062*
C37	0.71982 (18)	1.05583 (19)	0.3795 (5)	0.0390 (13)
C38	0.68234 (18)	1.02470 (18)	0.3473 (5)	0.0368 (12)
C39	0.64666 (18)	1.01325 (18)	0.4313 (5)	0.0401 (12)
C40	0.6480 (2)	1.0331 (2)	0.5347 (5)	0.0489 (14)
H40	0.6243	1.0259	0.5878	0.059*
C41	0.6855 (2)	1.0648 (2)	0.5624 (6)	0.0549 (15)
H41	0.6861	1.0786	0.6343	0.066*
C42	0.7205 (2)	1.0759 (2)	0.4884 (6)	0.0541 (16)
H42	0.7450	1.0968	0.5093	0.065*
C43	0.57017 (18)	0.9741 (2)	0.4575 (5)	0.0420 (13)
H43A	0.5558	1.0051	0.4741	0.050*
H43B	0.5770	0.9580	0.5287	0.050*
C44	0.53637 (19)	0.94426 (19)	0.3874 (5)	0.0401 (13)
Cl1	0.60467 (7)	0.86489 (7)	0.62933 (16)	0.0695 (5)
O9	0.6258 (3)	0.8249 (2)	0.6794 (7)	0.133 (3)
O10	0.5717 (3)	0.8859 (2)	0.7072 (6)	0.120 (2)
O11	0.6394 (2)	0.8977 (3)	0.6031 (8)	0.149 (3)
O12	0.5784 (2)	0.8534 (3)	0.5320 (5)	0.117 (2)
Cl2	0.84046 (8)	0.86683 (7)	0.81348 (17)	0.0806 (5)
O13	0.8297 (3)	0.8870 (2)	0.9199 (5)	0.122 (2)
O14	0.8882 (4)	0.8483 (7)	0.8260 (17)	0.135 (6)	0.435 (12)
O15	0.8161 (8)	0.8266 (7)	0.7711 (18)	0.136 (7)	0.435 (12)
O16	0.8503 (8)	0.9054 (6)	0.7378 (17)	0.106 (6)	0.435 (12)
O14B	0.8430 (6)	0.8164 (3)	0.8210 (15)	0.125 (5)	0.565 (12)
O15B	0.7955 (3)	0.8758 (5)	0.7556 (10)	0.123 (5)	0.565 (12)
O16B	0.8747 (6)	0.8910 (6)	0.7473 (13)	0.128 (6)	0.565 (12)
O1W	0.7277 (3)	0.8093 (3)	0.6219 (9)	0.172 (4)
H1W	0.7002	0.8193	0.6299	0.258*
H2W	0.7404	0.8353	0.6336	0.258*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.0478 (2)	0.0402 (2)	0.0385 (2)	0.0055 (2)	0.0074 (2)	0.00281 (19)
O1	0.063 (3)	0.046 (2)	0.039 (2)	0.016 (2)	0.0066 (18)	0.0036 (19)
O2	0.050 (2)	0.042 (2)	0.050 (3)	0.0109 (18)	0.0050 (19)	0.0074 (19)
O3	0.061 (2)	0.043 (2)	0.044 (2)	0.0084 (18)	−0.002 (2)	0.010 (2)
O4	0.058 (3)	0.080 (3)	0.044 (2)	−0.014 (2)	−0.001 (2)	0.019 (2)
N1	0.037 (2)	0.036 (2)	0.048 (3)	0.001 (2)	0.001 (2)	0.004 (2)
N2	0.048 (3)	0.040 (3)	0.043 (3)	0.003 (2)	0.003 (2)	−0.003 (2)
N3	0.181 (11)	0.205 (13)	0.106 (8)	−0.067 (10)	−0.006 (8)	−0.039 (8)
C1	0.058 (4)	0.047 (3)	0.056 (4)	0.006 (3)	−0.003 (3)	0.009 (3)
C2	0.066 (4)	0.042 (3)	0.063 (4)	0.009 (3)	−0.015 (4)	0.003 (3)
C3	0.052 (4)	0.042 (3)	0.084 (5)	0.009 (3)	−0.010 (4)	−0.011 (4)
C4	0.037 (3)	0.045 (3)	0.061 (4)	−0.001 (3)	−0.006 (3)	−0.013 (3)
C5	0.032 (3)	0.035 (3)	0.039 (3)	−0.004 (2)	−0.004 (2)	−0.004 (2)
C6	0.039 (3)	0.036 (3)	0.040 (3)	−0.003 (2)	−0.006 (2)	−0.002 (2)
C7	0.060 (4)	0.048 (3)	0.042 (4)	−0.003 (3)	0.004 (3)	−0.007 (3)
C8	0.064 (4)	0.065 (4)	0.060 (4)	−0.003 (3)	0.024 (4)	−0.016 (4)
C9	0.049 (4)	0.051 (4)	0.071 (4)	0.002 (3)	0.012 (3)	−0.019 (3)
C10	0.051 (3)	0.041 (3)	0.035 (3)	0.000 (3)	0.003 (3)	−0.001 (3)
C11	0.038 (3)	0.042 (3)	0.050 (4)	−0.006 (2)	−0.002 (3)	0.002 (3)
C12	0.065 (4)	0.046 (4)	0.057 (4)	0.004 (3)	−0.001 (3)	−0.005 (3)
C13	0.063 (5)	0.061 (5)	0.092 (6)	−0.001 (4)	−0.020 (4)	−0.006 (4)
C14	0.064 (5)	0.061 (5)	0.092 (6)	−0.016 (4)	0.010 (4)	−0.024 (4)
C15	0.059 (4)	0.050 (4)	0.069 (5)	−0.006 (3)	0.014 (4)	−0.015 (4)
C16	0.055 (3)	0.034 (3)	0.049 (3)	0.003 (2)	0.015 (3)	0.001 (3)
C17	0.063 (4)	0.051 (3)	0.046 (4)	−0.004 (3)	0.003 (3)	0.005 (3)
C18	0.093 (6)	0.086 (6)	0.059 (4)	−0.014 (5)	0.005 (4)	0.022 (4)
C19	0.119 (8)	0.083 (6)	0.084 (6)	−0.024 (5)	0.042 (6)	0.026 (5)
C20	0.087 (6)	0.073 (5)	0.077 (6)	−0.021 (4)	0.026 (5)	0.000 (5)
C21	0.073 (5)	0.110 (7)	0.064 (5)	−0.007 (5)	−0.019 (4)	0.037 (5)
C22	0.132 (9)	0.152 (10)	0.052 (5)	−0.028 (8)	0.000 (6)	−0.018 (6)
Cd2	0.0405 (2)	0.0410 (2)	0.0388 (2)	−0.00297 (19)	0.00407 (18)	−0.00562 (19)
O5	0.038 (2)	0.051 (2)	0.041 (2)	−0.0068 (17)	0.0113 (18)	−0.0053 (17)
O6	0.046 (2)	0.049 (2)	0.042 (2)	−0.0065 (18)	0.0043 (18)	−0.0077 (18)
O7	0.038 (2)	0.059 (2)	0.052 (2)	−0.0059 (18)	0.006 (2)	0.007 (2)
O8	0.073 (3)	0.043 (2)	0.038 (2)	0.009 (2)	0.016 (2)	0.0021 (18)
N4	0.041 (2)	0.043 (2)	0.044 (3)	−0.004 (2)	0.002 (2)	0.001 (2)
N5	0.038 (2)	0.039 (2)	0.037 (3)	−0.003 (2)	0.003 (2)	−0.004 (2)
N6	0.131 (7)	0.093 (6)	0.121 (7)	−0.011 (5)	0.067 (6)	0.007 (5)
C23	0.053 (4)	0.055 (4)	0.058 (4)	−0.003 (3)	−0.003 (3)	0.008 (3)
C24	0.065 (4)	0.055 (4)	0.078 (5)	−0.004 (3)	−0.017 (4)	0.009 (4)
C25	0.054 (4)	0.041 (3)	0.100 (6)	0.003 (3)	−0.021 (4)	0.002 (4)
C26	0.042 (3)	0.033 (3)	0.073 (5)	0.001 (3)	−0.007 (3)	−0.012 (3)
C27	0.036 (3)	0.040 (3)	0.050 (3)	−0.005 (2)	0.000 (3)	−0.008 (3)
C28	0.048 (3)	0.036 (3)	0.059 (4)	−0.004 (3)	0.007 (3)	−0.011 (3)
C29	0.086 (5)	0.050 (4)	0.073 (5)	0.010 (4)	0.033 (4)	−0.006 (4)
C30	0.081 (5)	0.067 (5)	0.101 (7)	0.008 (4)	0.033 (5)	−0.034 (5)
C31	0.066 (4)	0.046 (4)	0.099 (6)	0.006 (3)	−0.007 (4)	−0.022 (4)
C32	0.081 (5)	0.061 (4)	0.048 (4)	0.014 (4)	0.011 (3)	0.002 (3)
C33	0.104 (6)	0.056 (4)	0.069 (5)	0.012 (4)	0.031 (5)	0.000 (4)
C34	0.051 (3)	0.064 (4)	0.039 (3)	−0.003 (3)	0.008 (3)	−0.005 (3)
C35	0.046 (3)	0.060 (4)	0.055 (4)	−0.010 (3)	0.013 (3)	0.009 (4)
C36	0.034 (3)	0.050 (3)	0.070 (4)	−0.012 (3)	0.003 (3)	0.009 (3)
C37	0.030 (3)	0.035 (3)	0.053 (3)	0.001 (2)	−0.005 (3)	0.006 (3)
C38	0.031 (3)	0.033 (3)	0.047 (3)	0.007 (2)	0.000 (2)	0.001 (2)
C39	0.033 (3)	0.036 (3)	0.051 (3)	0.000 (2)	0.001 (3)	0.003 (3)
C40	0.050 (3)	0.059 (4)	0.038 (3)	−0.004 (3)	0.006 (3)	−0.006 (3)
C41	0.057 (4)	0.061 (4)	0.046 (4)	−0.007 (3)	−0.004 (3)	−0.020 (3)
C42	0.048 (3)	0.052 (4)	0.063 (4)	−0.005 (3)	−0.009 (3)	−0.011 (3)
C43	0.034 (3)	0.049 (3)	0.043 (3)	0.002 (2)	0.001 (2)	−0.001 (3)
C44	0.036 (3)	0.039 (3)	0.045 (3)	−0.002 (2)	−0.002 (3)	0.010 (3)
Cl1	0.0681 (11)	0.0801 (12)	0.0604 (11)	−0.0011 (10)	0.0022 (9)	0.0197 (9)
O9	0.146 (6)	0.120 (5)	0.133 (6)	0.060 (5)	0.010 (5)	0.042 (5)
O10	0.127 (5)	0.133 (5)	0.101 (5)	0.038 (4)	0.031 (4)	−0.010 (4)
O11	0.060 (4)	0.181 (7)	0.208 (9)	−0.046 (4)	0.000 (5)	0.074 (7)
O12	0.118 (5)	0.173 (7)	0.060 (4)	−0.031 (5)	−0.005 (3)	−0.007 (4)
Cl2	0.1076 (16)	0.0773 (13)	0.0570 (11)	0.0033 (12)	0.0203 (12)	−0.0115 (10)
O13	0.162 (6)	0.129 (5)	0.075 (4)	−0.007 (4)	0.054 (4)	−0.029 (4)
O14	0.140 (12)	0.121 (12)	0.142 (13)	0.045 (10)	0.009 (11)	−0.032 (10)
O15	0.155 (15)	0.118 (12)	0.135 (13)	−0.062 (11)	0.031 (11)	−0.046 (10)
O16	0.134 (14)	0.098 (10)	0.086 (9)	0.024 (10)	0.030 (11)	0.015 (8)
O14B	0.152 (12)	0.075 (7)	0.148 (12)	0.024 (7)	−0.007 (10)	−0.011 (8)
O15B	0.122 (10)	0.155 (11)	0.093 (8)	0.031 (8)	−0.010 (7)	0.010 (8)
O16B	0.114 (11)	0.173 (13)	0.098 (9)	−0.073 (9)	0.065 (9)	−0.045 (9)
O1W	0.129 (6)	0.131 (6)	0.257 (11)	−0.005 (5)	0.074 (7)	0.006 (7)

Geometric parameters (Å, º)

Cd1—O3^i	2.190 (4)	O5—C43	1.434 (6)
Cd1—N2	2.254 (5)	O6—C44	1.245 (7)
Cd1—N1	2.270 (4)	O7—C44	1.259 (6)
Cd1—O2	2.293 (4)	O7—Cd2^iv	2.219 (4)
Cd1—O1	2.416 (4)	O8—C28	1.391 (7)
Cd1—O4	2.631 (4)	O8—C32	1.413 (7)
O1—C6	1.355 (6)	N4—C23	1.326 (8)
O1—C10	1.410 (6)	N4—C27	1.356 (7)
O2—C11	1.258 (7)	N5—C34	1.338 (7)
O3—C11	1.245 (6)	N5—C38	1.361 (7)
O3—Cd1^ii	2.190 (4)	N6—C33	1.106 (10)
O4—C17	1.349 (7)	C23—C24	1.380 (9)
O4—C21	1.420 (8)	C23—H23	0.9300
N1—C1	1.319 (7)	C24—C25	1.338 (10)
N1—C5	1.372 (7)	C24—H24	0.9300
N2—C12	1.316 (8)	C25—C26	1.424 (10)
N2—C16	1.362 (7)	C25—H25	0.9300
N3—C22	1.163 (14)	C26—C31	1.374 (10)
C1—C2	1.394 (8)	C26—C27	1.402 (8)
C1—H1	0.9300	C27—C28	1.402 (8)
C2—C3	1.328 (10)	C28—C29	1.356 (8)
C2—H2	0.9300	C29—C30	1.414 (10)
C3—C4	1.398 (9)	C29—H29	0.9300
C3—H3	0.9300	C30—C31	1.365 (12)
C4—C5	1.410 (8)	C30—H30	0.9300
C4—C9	1.417 (9)	C31—H31	0.9300
C5—C6	1.395 (7)	C32—C33	1.531 (11)
C6—C7	1.377 (8)	C32—H32A	0.9700
C7—C8	1.395 (8)	C32—H32B	0.9700
C7—H7	0.9300	C34—C35	1.357 (8)
C8—C9	1.346 (10)	C34—H34	0.9300
C8—H8	0.9300	C35—C36	1.364 (9)
C9—H9	0.9300	C35—H35	0.9300
C10—C11	1.502 (8)	C36—C37	1.403 (8)
C10—H10A	0.9700	C36—H36	0.9300
C10—H10B	0.9700	C37—C42	1.399 (8)
C12—C13	1.400 (10)	C37—C38	1.408 (7)
C12—H12	0.9300	C38—C39	1.438 (8)
C13—C14	1.331 (10)	C39—C40	1.338 (8)
C13—H13	0.9300	C40—C41	1.407 (8)
C14—C15	1.394 (10)	C40—H40	0.9300
C14—H14	0.9300	C41—C42	1.343 (9)
C15—C20	1.394 (11)	C41—H41	0.9300
C15—C16	1.396 (8)	C42—H42	0.9300
C16—C17	1.416 (8)	C43—C44	1.503 (7)
C17—C18	1.366 (9)	C43—H43A	0.9700
C18—C19	1.440 (11)	C43—H43B	0.9700
C18—H18	0.9300	Cl1—O11	1.366 (6)
C19—C20	1.317 (12)	Cl1—O9	1.389 (6)
C19—H19	0.9300	Cl1—O12	1.396 (6)
C20—H20	0.9300	Cl1—O10	1.424 (6)
C21—C22	1.442 (13)	Cl2—O15	1.403 (8)
C21—H21A	0.9700	Cl2—O16B	1.403 (7)
C21—H21B	0.9700	Cl2—O13	1.407 (5)
Cd2—O7^iii	2.219 (4)	Cl2—O14B	1.408 (7)
Cd2—N4	2.269 (4)	Cl2—O16	1.421 (8)
Cd2—N5	2.283 (4)	Cl2—O14	1.433 (8)
Cd2—O6	2.287 (4)	Cl2—O15B	1.447 (7)
Cd2—O5	2.409 (4)	O1W—H1W	0.8201
Cd2—O8	2.573 (4)	O1W—H2W	0.8200
O5—C39	1.369 (6)
O3^i—Cd1—N2	120.65 (15)	O5—Cd2—O8	155.20 (14)
O3^i—Cd1—N1	119.83 (15)	C39—O5—C43	118.7 (4)
N2—Cd1—N1	100.44 (15)	C39—O5—Cd2	118.2 (3)
O3^i—Cd1—O2	92.65 (15)	C43—O5—Cd2	118.1 (3)
N2—Cd1—O2	87.84 (15)	C44—O6—Cd2	122.8 (3)
N1—Cd1—O2	133.59 (15)	C44—O7—Cd2^iv	103.2 (4)
O3^i—Cd1—O1	125.68 (14)	C28—O8—C32	118.1 (5)
N2—Cd1—O1	108.44 (16)	C28—O8—Cd2	114.8 (3)
N1—Cd1—O1	67.87 (15)	C32—O8—Cd2	126.9 (3)
O2—Cd1—O1	66.20 (13)	C23—N4—C27	118.3 (5)
O3^i—Cd1—O4	70.78 (14)	C23—N4—Cd2	117.4 (4)
N2—Cd1—O4	65.48 (15)	C27—N4—Cd2	123.9 (4)
N1—Cd1—O4	92.43 (16)	C34—N5—C38	117.1 (5)
O2—Cd1—O4	131.39 (15)	C34—N5—Cd2	122.7 (4)
O1—Cd1—O4	158.57 (14)	C38—N5—Cd2	119.9 (3)
C6—O1—C10	120.3 (4)	N4—C23—C24	124.1 (7)
C6—O1—Cd1	117.2 (3)	N4—C23—H23	118.0
C10—O1—Cd1	119.8 (3)	C24—C23—H23	118.0
C11—O2—Cd1	123.4 (4)	C25—C24—C23	118.7 (7)
C11—O3—Cd1^ii	104.6 (4)	C25—C24—H24	120.6
C17—O4—C21	118.2 (5)	C23—C24—H24	120.6
C17—O4—Cd1	114.1 (3)	C24—C25—C26	120.0 (6)
C21—O4—Cd1	126.1 (4)	C24—C25—H25	120.0
C1—N1—C5	117.9 (5)	C26—C25—H25	120.0
C1—N1—Cd1	121.8 (4)	C31—C26—C27	119.7 (7)
C5—N1—Cd1	120.2 (4)	C31—C26—C25	122.9 (6)
C12—N2—C16	118.5 (5)	C27—C26—C25	117.5 (6)
C12—N2—Cd1	115.7 (4)	N4—C27—C28	120.2 (5)
C16—N2—Cd1	125.7 (4)	N4—C27—C26	121.4 (6)
N1—C1—C2	123.6 (6)	C28—C27—C26	118.4 (6)
N1—C1—H1	118.2	C29—C28—O8	123.9 (6)
C2—C1—H1	118.2	C29—C28—C27	121.7 (6)
C3—C2—C1	118.8 (6)	O8—C28—C27	114.3 (5)
C3—C2—H2	120.6	C28—C29—C30	119.0 (7)
C1—C2—H2	120.6	C28—C29—H29	120.5
C2—C3—C4	121.1 (6)	C30—C29—H29	120.5
C2—C3—H3	119.4	C31—C30—C29	119.8 (7)
C4—C3—H3	119.4	C31—C30—H30	120.1
C3—C4—C5	117.2 (6)	C29—C30—H30	120.1
C3—C4—C9	125.4 (6)	C30—C31—C26	121.4 (7)
C5—C4—C9	117.3 (6)	C30—C31—H31	119.3
N1—C5—C6	118.4 (5)	C26—C31—H31	119.3
N1—C5—C4	121.3 (5)	O8—C32—C33	109.8 (6)
C6—C5—C4	120.2 (5)	O8—C32—H32A	109.7
O1—C6—C7	125.6 (5)	C33—C32—H32A	109.7
O1—C6—C5	114.8 (5)	O8—C32—H32B	109.7
C7—C6—C5	119.5 (5)	C33—C32—H32B	109.7
C6—C7—C8	121.2 (6)	H32A—C32—H32B	108.2
C6—C7—H7	119.4	N6—C33—C32	178.0 (9)
C8—C7—H7	119.4	N5—C34—C35	123.7 (6)
C9—C8—C7	119.2 (6)	N5—C34—H34	118.1
C9—C8—H8	120.4	C35—C34—H34	118.1
C7—C8—H8	120.4	C34—C35—C36	119.5 (6)
C8—C9—C4	122.4 (6)	C34—C35—H35	120.2
C8—C9—H9	118.8	C36—C35—H35	120.2
C4—C9—H9	118.8	C35—C36—C37	120.4 (5)
O1—C10—C11	107.6 (5)	C35—C36—H36	119.8
O1—C10—H10A	110.2	C37—C36—H36	119.8
C11—C10—H10A	110.2	C42—C37—C36	123.8 (6)
O1—C10—H10B	110.2	C42—C37—C38	120.2 (5)
C11—C10—H10B	110.2	C36—C37—C38	116.1 (5)
H10A—C10—H10B	108.5	N5—C38—C37	123.2 (5)
O3—C11—O2	122.7 (5)	N5—C38—C39	119.2 (5)
O3—C11—C10	117.2 (5)	C37—C38—C39	117.6 (5)
O2—C11—C10	120.2 (5)	C40—C39—O5	126.0 (5)
N2—C12—C13	122.5 (7)	C40—C39—C38	121.1 (5)
N2—C12—H12	118.8	O5—C39—C38	112.9 (5)
C13—C12—H12	118.8	C39—C40—C41	119.4 (6)
C14—C13—C12	119.3 (7)	C39—C40—H40	120.3
C14—C13—H13	120.3	C41—C40—H40	120.3
C12—C13—H13	120.3	C42—C41—C40	122.2 (6)
C13—C14—C15	120.3 (7)	C42—C41—H41	118.9
C13—C14—H14	119.8	C40—C41—H41	118.9
C15—C14—H14	119.8	C41—C42—C37	119.6 (6)
C20—C15—C14	121.4 (7)	C41—C42—H42	120.2
C20—C15—C16	120.8 (7)	C37—C42—H42	120.2
C14—C15—C16	117.8 (7)	O5—C43—C44	108.0 (4)
N2—C16—C15	121.6 (6)	O5—C43—H43A	110.1
N2—C16—C17	118.8 (5)	C44—C43—H43A	110.1
C15—C16—C17	119.6 (6)	O5—C43—H43B	110.1
O4—C17—C18	125.2 (6)	C44—C43—H43B	110.1
O4—C17—C16	115.9 (5)	H43A—C43—H43B	108.4
C18—C17—C16	118.9 (6)	O6—C44—O7	123.0 (5)
C17—C18—C19	119.1 (8)	O6—C44—C43	121.4 (5)
C17—C18—H18	120.4	O7—C44—C43	115.6 (5)
C19—C18—H18	120.4	O11—Cl1—O9	109.4 (5)
C20—C19—C18	122.4 (8)	O11—Cl1—O12	109.8 (5)
C20—C19—H19	118.8	O9—Cl1—O12	112.7 (5)
C18—C19—H19	118.8	O11—Cl1—O10	109.2 (5)
C19—C20—C15	119.2 (7)	O9—Cl1—O10	109.2 (4)
C19—C20—H20	120.4	O12—Cl1—O10	106.5 (4)
C15—C20—H20	120.4	O15—Cl2—O16B	121.0 (11)
O4—C21—C22	111.3 (7)	O15—Cl2—O13	122.3 (9)
O4—C21—H21A	109.4	O16B—Cl2—O13	116.6 (7)
C22—C21—H21A	109.4	O15—Cl2—O14B	41.4 (10)
O4—C21—H21B	109.4	O16B—Cl2—O14B	118.6 (10)
C22—C21—H21B	109.4	O13—Cl2—O14B	110.7 (8)
H21A—C21—H21B	108.0	O15—Cl2—O16	118.3 (15)
N3—C22—C21	176.0 (13)	O16B—Cl2—O16	32.7 (9)
O7^iii—Cd2—N4	130.02 (16)	O13—Cl2—O16	107.3 (10)
O7^iii—Cd2—N5	112.12 (15)	O14B—Cl2—O16	141.4 (11)
N4—Cd2—N5	102.11 (15)	O15—Cl2—O14	101.3 (13)
O7^iii—Cd2—O6	92.18 (14)	O16B—Cl2—O14	66.5 (10)
N4—Cd2—O6	87.13 (15)	O13—Cl2—O14	104.5 (8)
N5—Cd2—O6	135.95 (14)	O14B—Cl2—O14	65.6 (9)
O7^iii—Cd2—O5	125.40 (14)	O16—Cl2—O14	99.1 (11)
N4—Cd2—O5	100.29 (15)	O15—Cl2—O15B	63.3 (12)
N5—Cd2—O5	68.34 (14)	O16B—Cl2—O15B	104.1 (10)
O6—Cd2—O5	67.63 (13)	O13—Cl2—O15B	99.6 (6)
O7^iii—Cd2—O8	76.17 (14)	O14B—Cl2—O15B	104.2 (9)
N4—Cd2—O8	66.29 (15)	O16—Cl2—O15B	75.0 (11)
N5—Cd2—O8	93.30 (15)	O14—Cl2—O15B	155.8 (9)
O6—Cd2—O8	128.98 (13)	H1W—O1W—H2W	94.8
O3^i—Cd1—O1—C6	−100.9 (4)	O7^iii—Cd2—O5—C39	−91.5 (4)
N2—Cd1—O1—C6	104.9 (4)	N4—Cd2—O5—C39	110.0 (4)
N1—Cd1—O1—C6	10.8 (3)	N5—Cd2—O5—C39	10.9 (3)
O2—Cd1—O1—C6	−176.1 (4)	O6—Cd2—O5—C39	−167.5 (4)
O4—Cd1—O1—C6	35.2 (6)	O8—Cd2—O5—C39	55.5 (5)
O3^i—Cd1—O1—C10	60.3 (4)	O7^iii—Cd2—O5—C43	63.1 (4)
N2—Cd1—O1—C10	−94.0 (4)	N4—Cd2—O5—C43	−95.4 (4)
N1—Cd1—O1—C10	171.9 (4)	N5—Cd2—O5—C43	165.5 (4)
O2—Cd1—O1—C10	−15.0 (4)	O6—Cd2—O5—C43	−12.9 (3)
O4—Cd1—O1—C10	−163.7 (4)	O8—Cd2—O5—C43	−149.9 (3)
O3^i—Cd1—O2—C11	−114.5 (4)	O7^iii—Cd2—O6—C44	−118.2 (4)
N2—Cd1—O2—C11	124.9 (4)	N4—Cd2—O6—C44	111.9 (4)
N1—Cd1—O2—C11	22.5 (5)	N5—Cd2—O6—C44	7.4 (5)
O1—Cd1—O2—C11	13.7 (4)	O5—Cd2—O6—C44	9.5 (4)
O4—Cd1—O2—C11	179.0 (4)	O8—Cd2—O6—C44	167.9 (4)
O3^i—Cd1—O4—C17	−138.9 (4)	O7^iii—Cd2—O8—C28	−151.5 (4)
N2—Cd1—O4—C17	−0.1 (4)	N4—Cd2—O8—C28	−5.3 (4)
N1—Cd1—O4—C17	100.2 (4)	N5—Cd2—O8—C28	96.5 (4)
O2—Cd1—O4—C17	−62.9 (5)	O6—Cd2—O8—C28	−70.1 (4)
O1—Cd1—O4—C17	77.7 (6)	O5—Cd2—O8—C28	55.7 (5)
O3^i—Cd1—O4—C21	26.5 (6)	O7^iii—Cd2—O8—C32	23.3 (5)
N2—Cd1—O4—C21	165.3 (6)	N4—Cd2—O8—C32	169.6 (5)
N1—Cd1—O4—C21	−94.3 (6)	N5—Cd2—O8—C32	−88.6 (5)
O2—Cd1—O4—C21	102.5 (6)	O6—Cd2—O8—C32	104.8 (5)
O1—Cd1—O4—C21	−116.8 (6)	O5—Cd2—O8—C32	−129.5 (5)
O3^i—Cd1—N1—C1	−65.6 (5)	O7^iii—Cd2—N4—C23	−136.2 (4)
N2—Cd1—N1—C1	69.1 (5)	N5—Cd2—N4—C23	90.7 (4)
O2—Cd1—N1—C1	166.2 (4)	O6—Cd2—N4—C23	−45.8 (4)
O1—Cd1—N1—C1	174.9 (5)	O5—Cd2—N4—C23	20.9 (4)
O4—Cd1—N1—C1	3.6 (5)	O8—Cd2—N4—C23	179.0 (4)
O3^i—Cd1—N1—C5	111.2 (4)	O7^iii—Cd2—N4—C27	51.6 (5)
N2—Cd1—N1—C5	−114.1 (4)	N5—Cd2—N4—C27	−81.5 (4)
O2—Cd1—N1—C5	−17.0 (5)	O6—Cd2—N4—C27	142.1 (4)
O1—Cd1—N1—C5	−8.3 (4)	O5—Cd2—N4—C27	−151.3 (4)
O4—Cd1—N1—C5	−179.6 (4)	O8—Cd2—N4—C27	6.8 (4)
O3^i—Cd1—N2—C12	−134.0 (4)	O7^iii—Cd2—N5—C34	−61.8 (5)
N1—Cd1—N2—C12	91.8 (4)	N4—Cd2—N5—C34	81.0 (5)
O2—Cd1—N2—C12	−42.2 (4)	O6—Cd2—N5—C34	179.5 (4)
O1—Cd1—N2—C12	21.8 (4)	O5—Cd2—N5—C34	177.4 (5)
O4—Cd1—N2—C12	179.7 (5)	O8—Cd2—N5—C34	14.6 (5)
O3^i—Cd1—N2—C16	48.1 (5)	O7^iii—Cd2—N5—C38	111.8 (4)
N1—Cd1—N2—C16	−86.1 (4)	N4—Cd2—N5—C38	−105.3 (4)
O2—Cd1—N2—C16	139.9 (4)	O6—Cd2—N5—C38	−6.8 (5)
O1—Cd1—N2—C16	−156.1 (4)	O5—Cd2—N5—C38	−8.9 (4)
O4—Cd1—N2—C16	1.8 (4)	O8—Cd2—N5—C38	−171.8 (4)
C5—N1—C1—C2	−1.5 (9)	C27—N4—C23—C24	−1.6 (9)
Cd1—N1—C1—C2	175.3 (5)	Cd2—N4—C23—C24	−174.2 (5)
N1—C1—C2—C3	−0.4 (10)	N4—C23—C24—C25	1.7 (10)
C1—C2—C3—C4	1.7 (10)	C23—C24—C25—C26	−1.6 (10)
C2—C3—C4—C5	−1.0 (9)	C24—C25—C26—C31	−179.5 (6)
C2—C3—C4—C9	−179.4 (6)	C24—C25—C26—C27	1.5 (9)
C1—N1—C5—C6	−177.6 (5)	C23—N4—C27—C28	180.0 (5)
Cd1—N1—C5—C6	5.5 (6)	Cd2—N4—C27—C28	−7.9 (7)
C1—N1—C5—C4	2.2 (8)	C23—N4—C27—C26	1.4 (8)
Cd1—N1—C5—C4	−174.8 (4)	Cd2—N4—C27—C26	173.5 (4)
C3—C4—C5—N1	−0.9 (8)	C31—C26—C27—N4	179.5 (6)
C9—C4—C5—N1	177.6 (5)	C25—C26—C27—N4	−1.4 (8)
C3—C4—C5—C6	178.8 (5)	C31—C26—C27—C28	1.0 (9)
C9—C4—C5—C6	−2.6 (8)	C25—C26—C27—C28	−180.0 (5)
C10—O1—C6—C7	7.8 (8)	C32—O8—C28—C29	9.9 (9)
Cd1—O1—C6—C7	168.8 (4)	Cd2—O8—C28—C29	−174.8 (5)
C10—O1—C6—C5	−173.1 (5)	C32—O8—C28—C27	−171.7 (5)
Cd1—O1—C6—C5	−12.0 (6)	Cd2—O8—C28—C27	3.6 (6)
N1—C5—C6—O1	4.8 (7)	N4—C27—C28—C29	−179.5 (6)
C4—C5—C6—O1	−175.0 (5)	C26—C27—C28—C29	−1.0 (9)
N1—C5—C6—C7	−176.0 (5)	N4—C27—C28—O8	2.0 (8)
C4—C5—C6—C7	4.2 (8)	C26—C27—C28—O8	−179.4 (5)
O1—C6—C7—C8	175.9 (5)	O8—C28—C29—C30	179.0 (6)
C5—C6—C7—C8	−3.2 (8)	C27—C28—C29—C30	0.7 (10)
C6—C7—C8—C9	0.6 (10)	C28—C29—C30—C31	−0.4 (12)
C7—C8—C9—C4	1.0 (10)	C29—C30—C31—C26	0.5 (12)
C3—C4—C9—C8	178.4 (6)	C27—C26—C31—C30	−0.8 (10)
C5—C4—C9—C8	0.0 (9)	C25—C26—C31—C30	−179.8 (7)
C6—O1—C10—C11	175.1 (5)	C28—O8—C32—C33	−75.2 (7)
Cd1—O1—C10—C11	14.6 (6)	Cd2—O8—C32—C33	110.1 (5)
Cd1^ii—O3—C11—O2	6.6 (6)	O8—C32—C33—N6	50 (28)
Cd1^ii—O3—C11—C10	−174.8 (4)	C38—N5—C34—C35	0.8 (9)
Cd1—O2—C11—O3	167.4 (4)	Cd2—N5—C34—C35	174.6 (5)
Cd1—O2—C11—C10	−11.3 (7)	N5—C34—C35—C36	−1.1 (10)
O1—C10—C11—O3	178.5 (5)	C34—C35—C36—C37	0.4 (9)
O1—C10—C11—O2	−2.8 (7)	C35—C36—C37—C42	−178.4 (6)
C16—N2—C12—C13	−0.5 (9)	C35—C36—C37—C38	0.6 (8)
Cd1—N2—C12—C13	−178.6 (5)	C34—N5—C38—C37	0.2 (8)
N2—C12—C13—C14	1.2 (11)	Cd2—N5—C38—C37	−173.8 (4)
C12—C13—C14—C15	−1.7 (11)	C34—N5—C38—C39	−179.2 (5)
C13—C14—C15—C20	−176.3 (7)	Cd2—N5—C38—C39	6.8 (6)
C13—C14—C15—C16	1.7 (10)	C42—C37—C38—N5	178.1 (5)
C12—N2—C16—C15	0.5 (8)	C36—C37—C38—N5	−0.9 (8)
Cd1—N2—C16—C15	178.4 (4)	C42—C37—C38—C39	−2.4 (8)
C12—N2—C16—C17	178.9 (5)	C36—C37—C38—C39	178.6 (5)
Cd1—N2—C16—C17	−3.2 (7)	C43—O5—C39—C40	15.4 (8)
C20—C15—C16—N2	177.0 (6)	Cd2—O5—C39—C40	169.8 (5)
C14—C15—C16—N2	−1.0 (9)	C43—O5—C39—C38	−165.7 (4)
C20—C15—C16—C17	−1.4 (9)	Cd2—O5—C39—C38	−11.3 (5)
C14—C15—C16—C17	−179.4 (6)	N5—C38—C39—C40	−177.7 (5)
C21—O4—C17—C18	11.5 (10)	C37—C38—C39—C40	2.8 (8)
Cd1—O4—C17—C18	178.1 (6)	N5—C38—C39—O5	3.3 (7)
C21—O4—C17—C16	−168.0 (6)	C37—C38—C39—O5	−176.2 (4)
Cd1—O4—C17—C16	−1.3 (7)	O5—C39—C40—C41	177.4 (5)
N2—C16—C17—O4	2.8 (8)	C38—C39—C40—C41	−1.4 (9)
C15—C16—C17—O4	−178.8 (5)	C39—C40—C41—C42	−0.3 (10)
N2—C16—C17—C18	−176.7 (6)	C40—C41—C42—C37	0.6 (10)
C15—C16—C17—C18	1.8 (9)	C36—C37—C42—C41	179.7 (6)
O4—C17—C18—C19	179.4 (7)	C38—C37—C42—C41	0.8 (9)
C16—C17—C18—C19	−1.2 (11)	C39—O5—C43—C44	168.9 (4)
C17—C18—C19—C20	0.4 (13)	Cd2—O5—C43—C44	14.4 (5)
C18—C19—C20—C15	0.0 (14)	Cd2—O6—C44—O7	173.8 (4)
C14—C15—C20—C19	178.4 (8)	Cd2—O6—C44—C43	−5.2 (7)
C16—C15—C20—C19	0.5 (12)	Cd2^iv—O7—C44—O6	2.8 (6)
C17—O4—C21—C22	64.7 (9)	Cd2^iv—O7—C44—C43	−178.2 (4)
Cd1—O4—C21—C22	−100.2 (7)	O5—C43—C44—O6	−6.6 (7)
O4—C21—C22—N3	−40 (19)	O5—C43—C44—O7	174.4 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W···O15B	0.82	2.38	3.078 (15)	143
O1W—H2W···O15	0.82	2.67	3.06 (2)	111
O1W—H1W···O9	0.82	2.16	2.948 (10)	162
C2—H2···O11^v	0.93	2.49	3.212 (8)	135
C8—H8···O13^vi	0.93	2.38	3.285 (9)	165
C10—H10A···O3^vii	0.97	2.45	3.308 (7)	147
C12—H12···O16B^viii	0.93	2.29	3.155 (17)	154
C13—H13···O1W^viii	0.93	2.47	3.258 (10)	142
C21—H21B···O3^i	0.97	2.57	2.982 (8)	106
C23—H23···O12	0.93	2.47	3.233 (9)	139
C32—H32A···O7^iii	0.97	2.47	3.131 (8)	126
C41—H41···O9^ix	0.93	2.58	3.495 (10)	170
C43—H43A···O7^x	0.97	2.34	3.236 (7)	153
C43—H43B···O11	0.97	2.57	3.344 (9)	137

Symmetry codes: (i) −y+1, x, −z+2; (iii) −y+3/2, x+1/2, −z+1/2; (v) y−1/2, −x+3/2, −z+3/2; (vi) y−1/2, −x+3/2, −z+5/2; (vii) −x+1, −y+1, z; (viii) −x+3/2, −y+3/2, z+1/2; (ix) −y+3/2, x+1/2, −z+3/2; (x) −x+1, −y+2, z.