Bis{tris­[(1H-benzimidazol-3-ium-2-yl)methyl]amine} tetra­aqua­octa-[mu]₂-chlorido-octa­chloridopenta­cadmate(II) monohydrate

The title compound, (C₂₄H₂₄N₇)₂[Cd₅Cl₁₆(H₂O)₄]·H₂O, con­tains a [Cd₅Cl₁₆(H₂O)₄]^6- anion, two triply protonated tris­[(1H-benzimidazol-3-ium-2-yl)methyl]amine cations and one solvent water mol­ecule. The structure of the anion is a novel chloride-bridged penta­nuclear cluster. The five unique Cd^II centres have quite different coordination environments. Two of the central hexa­coordinated Cd^II cations have a CdOCl₅ chromophore, in which each Cd^II cation is ligated by four bridging chloride ligands, one terminal chloride ligand and one water mol­ecule, adopting a distorted octa­hedral environment. The third central Cd^II cation is octa­hedrally coordinated by four bridging chloride ligands and two water mol­ecules. Finally, the two terminal Cd^II cations are penta­coordinated by two bridging and three terminal chloride ligands and adopt a trigonal-bipyramidal geometry. A three-dimensional supra­molecular network is formed through intra- and inter­molecular O-H...O, O-H...Cl, N-H...Cl and N-H...O hydrogen bonds and [pi]-[pi] inter­actions between the cations and anions.

S1. Comment

In recent years, growing attention has been paid to the rational design and construction of novel functional metal–organic compounds, owing not only to their intriguing structural diversities and topologies (Ye et al., 2005; Hill et al., 2005; Hong, 2007), but also to their potential applications in many fields, such as ferroelectricity, electrical conductivity, magnetism, molecular adsorption, fluorescence and heterogeneous catalysis (Zhang et al., 2009, 2010; Zhang & Xiong, 2012; Yao et al., 2008; Nouar et al., 2008; Li et al., 2009). Numerous zero-, one-, two- and three-dimensional cadmium complexes, in which the metal centres are connected by small anionic bridging ligands such as Cl^- (Willett, 1977; Charles et al., 1984; Puget et al., 1991; Jin & Wu, 2013), have been synthesized and characterized with the aim of designing new materials with inter­esting physical properties. The diverse structures of these Cd^II complexes are based on the variable coordination geometry of the metal ion, because of the wide range of different atom contacts. To the best of our knowledge, zero-dimensional [Title compound is linear, i.e. one-dimensional, not zero-dimensional. What is the connection?] cadmium complexes containing five differently coordinated Cd atoms have not been reported so far and thus structural information on such compounds is scarce. We report here the synthesis and structure determination of the title compound, (I), containing a chloride-bridged penta­nuclear cluster.

In the crystal structure of (I), the asymmetric unit consists of a [Cd₅Cl₁₆(H₂O)₄]^6- anion, two triply protonated tris­[(1H-benzimidazol-3-ium-2-yl)methyl]­amine cations and one solvent water molecule (Fig. 1). The complex anionic group is a linear [Cd₅Cl₁₆(H₂O)₄]^6- penta­mer inter­connected by bridging (edge-sharing) chloride ligands. Five crystallographically independent Cd^II cations are present, linked by double chloride anion bridges to form a finite —Cd—Cl₂—Cd— ribbon. In this way, the Cd1 and Cd5 centres are five-coordinated by three terminal and two bridging Cl^- anions, showing a distorted trigonal–bipyramidal geometry. The Cd2 and Cd3 centres are coordinated by one water and five chloride ligands (four bridging and one terminal), leading to a distorted o­cta­hedral coordination environment in which the water ligand occupies an axial position. The Cd2—O4 bond is shorter than Cd3—O3 [2.382 (3) and 2.530 (3) Å, respectively]. The Cd4 cation is surrounded by four chloride ligands and two water molecules, giving rise to a slightly distorted o­cta­hedral geometry. The Cl—Cd—Cl angles are in the ranges 84.75 (4)–96.12 (4)° and 174.21 (4)–177.46 (4)°, and the O—Cd—O angle is 171.23 (10)°, deviating slightly from ideal o­cta­hedral angle values (90 and 180°). The Cd4—Cl bond lengths are in the range 2.5273 (12)–2.6713 (12) Å, the Cd4—O1 and Cd4—O2 bond lengths are 2.366 (3) and 2.453 (3) Å, respectively, and the Cd3···Cd2 and Cd3···Cd4 distances are 3.736 (1) and 3.719 (1) Å, respectively, both of which are less than the distances to the terminal cadmium ions, viz. Cd1···Cd2 and Cd5···Cd4 of 3.894 (1) and 3.812 (1) Å, respectively. The Cd—Cl bond lengths range from 2.4393 (12) to 2.6927 (12) Å, which appear to be shorter than those observed in the CdCl₂ crystal structure (2.74 Å; Pauling & Hoard, 1930). The terminal Cd^II cations (Cd1 and Cd5) adopt trigonal–bipyrimadal geometries with the chloride ligands; Cl1/Cl2/Cl4 and Cl13/Cl14/Cl16 fill the basal locations for Cd1 and Cd5, respectively, while Cl2/Cl5 and Cl12/Cl15 take up the apical positions. The apical Cd—Cl bonds on the terminal Cd^II cations have bond lengths in the range 2.6347 (11)–2.6856 (12) Å, while the basal Cd—Cl bond lengths are in the range 2.4393 (12)–2.5843 (11) Å.

There are abundant intra- and inter­molecular O—H···O, O—H···Cl, N—H···Cl and N—H···O hydrogen bonds in (I). Intra­molecular O—H···Cl hydrogen bonds (O1—H1C···Cl14, O2—H2C···Cl9, O3—H3D···Cl6, O4—H4D···Cl7 and O4—H4D···Cl9; see Table 2) are generated by the water ligands and the Cl^- anions in the penta­mer. Three hydrogen bonds [O1—H1B···Cl1ⁱ, O3—H3C···Cl1ⁱ and O4—H4C···Cl14ⁱⁱ; symmetry codes: (i) x + 1, y, z; (ii) x - 1, y, z] extend the anionic groups along the a-axis direction in a zigzag chain. The solvent water molecule forms further hydrogen bonds [O2—H2D···O5ⁱⁱ, O5—H5C···Cl3^vii and O5—H5D···Cl6^vii; symmetry codes: (ii) x - 1, y, z; (vii) x + 1, y + 1, z] as a bridge to connect two [Cd₅Cl₁₆(H₂O)₄]^6- anions oriented parallel and end-to-end to each other. Thus, these zigzag chains are linked together into two-dimensional step-like layers (Fig. 2).

The presence of the organic cations as spacers between the inorganic anions gives rise to distinctive hydrogen-bonding features which influence the structural packing. In (I), the anionic layers are well separated by the triply protonated cations. There is a network of inter­molecular hydrogen-bonding inter­actions between the organic cations and inorganic layers (Table 2). Two kinds of inter­molecular N—H···Cl and N—H···O hydrogen bonds contribute to the formation of a three-dimensional supra­molecular framework (Fig. 3).

It is notable that the cation has a tweezer-like conformation, which is stabilized not only by the hydrogen bonds (Table 2) between the N atoms on the imidazole rings and the O and Cl atoms of the water molecules and the anionic clusters, respectively, but also by π–π inter­actions among the organic cations. Such a conformation for free tris­[(benzimidazol-2-yl)methyl]­amine or its protonated form has been only rarely reported so far, though it is often used as a symmetric tripodal ligand to coordinate to metal ions (Zhou et al., 2000; Miao et al., 1999). The N—H···Cl hydrogen-bond distances are in the range 3.100 (3)–3.432 (3) Å, while the N—H···O distances [N5—H5B···O3^iv and N10—H10B···O2^vi; symmetry code: (iv) -x + 1, -y, -z + 1; (vi) x + 1, y - 1, z] are 2.942 (4) and 2.815 (4) Å, respectively, both of which are less than the N—H···Cl distances.

The structure of (I) is further stabilised by π–π inter­actions between the benzene and imidazole rings of the organic cations (Fig. 4). Except for the intra­molecular π–π inter­actions that exist in each cation with a face-to-face (FF) motif, each cation has π–π inter­actions with three adjacent cations with offset face-to-face (OFF) motifs (Russell et al., 2001). The smallest centroid-to-centroid distance is a Cg2···Cg3 separation of 3.305 (2) Å, while the longest one is a Cg3···Cg5 distance of 3.933 (3) Å [Cg2, Cg3 and Cg5 are the centroids of the N3/C9/C14/N4/C15, N5/C17/C22/N6/C23 and C9–C14 rings, respectively]. The dihedral angle between the N3/C9–C14/N4/C15 and N5/C17–C22/N6/C23 rings is 15.61 (8)°, and that between the N10/C33–C38/N11/C39 and N12/C41–C46/N13/C47 rings is 14.63 (9)°.

S2. Synthesis and crystallization

Tris[(benzimidazol-2-yl)methyl]­amine was prepared by the conventional condensation of 1,2-phenyl­enedi­amine with nitrilo­tri­acetic acid (Thompson et al., 1977). Cadmium chloride hydrate (3.0 g, 15 mmol) was dissolved in concentrated hydro­chloric acid (10 ml) and tris­[(benzimidazol-2-yl)methyl]­amine (2.0 g, 5 mmol) was added. After stirring the mixture for several minutes, the liquid was filtered to give a clear solution. Single crystals of (I) suitable for X-ray structure analysis were obtained by slow evaporation of the solution for several days at ambient temperature.

S3. Refinement

H atoms bonded to C and N atoms were placed in calculated positions, with C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C) for methyl­ene H atoms, C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms, and N—H = 0.86 Å and U_iso(H) = 1.2U_eq(N). Water H atoms were located in a difference Fourier synthesis and refined with an O—H distance restraint of 0.85 Å and with U_iso(H) = 1.2U_eq(O), except for atom O1, for which O—H = 0.96 Å and U_iso(H) = 1.5U_eq(O).

Related literature

For related literature, see: Charles et al. (1984); Hill et al. (2005); Hong (2007); Jin & Wu (2013); Li et al. (2009); Miao et al. (1999); Nouar et al. (2008); Pauling & Hoard (1930); Puget et al. (1991); Russell et al. (2001); Thompson et al. (1977); Willett (1977); Yao et al. (2008); Ye et al. (2005); Zhang & Xiong (2012); Zhang et al. (2009, 2010); Zhou et al. (2000).

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: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. A view of the local coordination of the Cd^II cations in (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Dashed lines indicate intramolecular hydrogen bonds.
	Fig. 2. A view of the anions and free water molecules in (I), showing how the zigzag chains are linked together into two-dimensional step-like layers by hydrogen bonding. Dashed lines indicate intermolecular hydrogen bonds.
	Fig. 3. A perspective view of the three-dimensional supramolecular structure of (I), viewed along the c axis. All H atoms have been omitted for clarity.
	Fig. 4. A view of the cations in (I). Dashed lines indicate π–π interactions. All H atoms have been omitted for clarity. FF and OFF denote face-to-face and offset face-to-face motifs, respectively (see text).

Bis{tris[(1H-benzimidazol-3-ium-2-yl)methyl]amime} tetraaquaocta-µ₂-chlorido-octachloridopentacadmate(II) monohydrate

Crystal data

(C24H24N7)2[Cd5Cl16(H2O)4]·H2O	Z = 2
Mr = 2040.33	F(000) = 1992
Triclinic, P1	Dx = 1.989 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 12.879 (3) Å	Cell parameters from 15625 reflections
b = 13.485 (3) Å	θ = 3.0–27.5°
c = 21.364 (4) Å	µ = 2.22 mm^−1
α = 79.74 (3)°	T = 293 K
β = 86.82 (3)°	Block, colourless
γ = 68.92 (3)°	0.24 × 0.22 × 0.20 mm
V = 3406.6 (15) Å^3

Data collection

Rigaku SCXmini diffractometer	13233 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.038
Graphite monochromator	θmax = 27.5°, θmin = 3.0°
ω scans	h = −16→16
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −17→17
Tmin = 0.593, Tmax = 0.642	l = −27→27
35082 measured reflections	3 standard reflections every 180 reflections
15625 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)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.076	w = 1/[σ^2(Fo^2) + (0.0133P)^2 + 3.8476P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
15625 reflections	Δρmax = 0.62 e Å^−3
794 parameters	Δρmin = −0.80 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00280 (5)

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
Cd1	−0.37003 (2)	0.17841 (2)	0.313961 (12)	0.02621 (7)
Cd2	−0.14830 (2)	0.31472 (2)	0.277289 (12)	0.02745 (7)
Cd3	0.02066 (2)	0.49276 (2)	0.251793 (12)	0.03022 (7)
Cd4	0.19210 (2)	0.66662 (2)	0.218705 (13)	0.02983 (7)
Cd5	0.35526 (2)	0.85597 (2)	0.180495 (12)	0.02644 (7)
Cl1	−0.56061 (8)	0.29319 (8)	0.27231 (5)	0.0420 (2)
Cl2	−0.43106 (7)	0.09588 (7)	0.42763 (4)	0.03199 (19)
Cl3	−0.30419 (9)	−0.00264 (7)	0.28580 (4)	0.0419 (2)
Cl4	−0.25114 (8)	0.23990 (7)	0.37772 (4)	0.0331 (2)
Cl5	−0.27911 (8)	0.26390 (9)	0.21232 (4)	0.0419 (2)
Cl6	0.02777 (8)	0.14529 (7)	0.28607 (4)	0.0361 (2)
Cl7	−0.04940 (8)	0.39343 (7)	0.35053 (4)	0.0329 (2)
Cl8	−0.06865 (9)	0.40761 (8)	0.18101 (4)	0.0386 (2)
Cl9	−0.15346 (8)	0.66576 (7)	0.24593 (4)	0.0347 (2)
Cl10	0.13908 (10)	0.55746 (9)	0.31780 (5)	0.0513 (3)
Cl11	0.12564 (9)	0.55784 (8)	0.15529 (4)	0.0404 (2)
Cl12	0.24173 (10)	0.79124 (10)	0.27696 (5)	0.0581 (3)
Cl13	0.25533 (8)	0.77274 (7)	0.11491 (4)	0.0368 (2)
Cl14	0.53089 (8)	0.70960 (8)	0.22220 (5)	0.0492 (3)
Cl15	0.42895 (7)	0.92269 (7)	0.06946 (4)	0.03008 (18)
Cl16	0.32389 (10)	1.02939 (8)	0.21230 (5)	0.0488 (3)
O1	0.3799 (3)	0.5487 (2)	0.22152 (16)	0.0635 (9)
H1B	0.3914	0.4919	0.2576	0.095*
H1C	0.4274	0.5883	0.2253	0.095*
O2	0.0018 (2)	0.79626 (18)	0.19833 (11)	0.0339 (6)
H2D	−0.0064	0.8457	0.2199	0.041*
H2C	−0.0415	0.7636	0.2142	0.041*
O3	0.1765 (2)	0.3107 (2)	0.26600 (12)	0.0422 (7)
H3C	0.2329	0.3141	0.2443	0.051*
H3D	0.1553	0.2640	0.2542	0.051*
O4	−0.2878 (2)	0.4871 (2)	0.28028 (16)	0.0610 (9)
H4C	−0.3207	0.5239	0.2458	0.073*
H4D	−0.2487	0.5125	0.2988	0.073*
C1	0.4447 (3)	0.3444 (3)	0.51401 (17)	0.0313 (8)
C2	0.4138 (3)	0.4037 (3)	0.45295 (19)	0.0400 (9)
H2A	0.4304	0.3720	0.4166	0.048*
C3	0.3569 (3)	0.5126 (3)	0.4507 (2)	0.0496 (11)
H3A	0.3334	0.5561	0.4114	0.060*
C4	0.3335 (3)	0.5597 (3)	0.5049 (2)	0.0505 (12)
H4A	0.2963	0.6338	0.5005	0.061*
C5	0.3630 (3)	0.5013 (3)	0.5646 (2)	0.0463 (11)
H5A	0.3456	0.5334	0.6008	0.056*
C6	0.4203 (3)	0.3916 (3)	0.56808 (18)	0.0346 (8)
C7	0.5128 (3)	0.2161 (3)	0.59702 (17)	0.0299 (8)
C8	0.5631 (3)	0.1091 (3)	0.63752 (16)	0.0320 (8)
H8A	0.5945	0.1174	0.6756	0.038*
H8B	0.5058	0.0788	0.6503	0.038*
C9	0.9624 (3)	−0.1278 (3)	0.51431 (15)	0.0228 (7)
C10	1.0445 (3)	−0.2230 (3)	0.50286 (17)	0.0309 (8)
H10A	1.0826	−0.2771	0.5357	0.037*
C11	1.0657 (3)	−0.2324 (3)	0.44001 (18)	0.0363 (9)
H11A	1.1194	−0.2952	0.4302	0.044*
C12	1.0100 (3)	−0.1514 (3)	0.39048 (17)	0.0378 (9)
H12A	1.0278	−0.1616	0.3487	0.045*
C13	0.9292 (3)	−0.0568 (3)	0.40155 (17)	0.0361 (9)
H13A	0.8924	−0.0021	0.3686	0.043*
C14	0.9059 (3)	−0.0478 (3)	0.46493 (16)	0.0249 (7)
C15	0.8334 (3)	0.0024 (3)	0.55593 (16)	0.0255 (7)
C16	0.7535 (3)	0.0597 (3)	0.60236 (16)	0.0291 (8)
H16A	0.7872	0.0370	0.6445	0.035*
H16B	0.7361	0.1368	0.5905	0.035*
C17	0.7938 (3)	−0.2966 (3)	0.54095 (15)	0.0253 (7)
C18	0.8533 (3)	−0.3994 (3)	0.52849 (18)	0.0350 (8)
H18A	0.8857	−0.4572	0.5608	0.042*
C19	0.8613 (3)	−0.4105 (3)	0.46538 (19)	0.0396 (9)
H19A	0.8996	−0.4782	0.4548	0.048*
C20	0.8143 (3)	−0.3242 (3)	0.41698 (18)	0.0385 (9)
H20A	0.8228	−0.3358	0.3751	0.046*
C21	0.7555 (3)	−0.2220 (3)	0.42906 (16)	0.0319 (8)
H21A	0.7245	−0.1639	0.3966	0.038*
C22	0.7453 (3)	−0.2110 (3)	0.49273 (15)	0.0243 (7)
C23	0.7105 (3)	−0.1507 (3)	0.58409 (15)	0.0243 (7)
C24	0.6695 (3)	−0.0771 (3)	0.63187 (16)	0.0295 (8)
H24A	0.6006	−0.0827	0.6499	0.035*
H24B	0.7238	−0.0995	0.6661	0.035*
C25	0.4528 (3)	0.3365 (3)	0.00832 (17)	0.0303 (8)
C26	0.4226 (3)	0.3917 (3)	−0.05355 (19)	0.0401 (9)
H26A	0.4390	0.3572	−0.0888	0.048*
C27	0.3668 (3)	0.5011 (4)	−0.0584 (2)	0.0524 (12)
H27A	0.3446	0.5419	−0.0985	0.063*
C28	0.3424 (3)	0.5532 (3)	−0.0062 (3)	0.0519 (12)
H28A	0.3051	0.6275	−0.0126	0.062*
C29	0.3714 (3)	0.4989 (3)	0.0546 (2)	0.0445 (10)
H29A	0.3549	0.5339	0.0897	0.053*
C30	0.4269 (3)	0.3885 (3)	0.06057 (18)	0.0321 (8)
C31	0.5175 (3)	0.2141 (3)	0.09436 (16)	0.0280 (7)
C32	0.5659 (3)	0.1091 (3)	0.13786 (16)	0.0316 (8)
H32A	0.5949	0.1206	0.1758	0.038*
H32B	0.5079	0.0797	0.1507	0.038*
C33	0.9669 (3)	−0.1367 (3)	0.01930 (15)	0.0231 (7)
C34	1.0464 (3)	−0.2331 (3)	0.00810 (17)	0.0308 (8)
H34A	1.0837	−0.2873	0.0411	0.037*
C35	1.0669 (3)	−0.2437 (3)	−0.05451 (19)	0.0378 (9)
H35A	1.1186	−0.3077	−0.0641	0.045*
C36	1.0132 (3)	−0.1622 (3)	−0.10411 (18)	0.0379 (9)
H36A	1.0309	−0.1731	−0.1457	0.046*
C37	0.9351 (3)	−0.0664 (3)	−0.09379 (16)	0.0327 (8)
H37A	0.8998	−0.0115	−0.1270	0.039*
C38	0.9121 (3)	−0.0564 (3)	−0.03030 (16)	0.0240 (7)
C39	0.8397 (3)	−0.0048 (3)	0.06091 (16)	0.0238 (7)
C40	0.7595 (3)	0.0538 (3)	0.10614 (16)	0.0283 (7)
H40A	0.7922	0.0318	0.1485	0.034*
H40B	0.7433	0.1307	0.0938	0.034*
C41	0.7942 (3)	−0.3016 (3)	0.04773 (15)	0.0242 (7)
C42	0.8533 (3)	−0.4046 (3)	0.03544 (18)	0.0358 (9)
H42A	0.8857	−0.4624	0.0677	0.043*
C43	0.8607 (3)	−0.4155 (3)	−0.02730 (19)	0.0395 (9)
H43A	0.8982	−0.4835	−0.0377	0.047*
C44	0.8146 (3)	−0.3294 (3)	−0.07612 (18)	0.0361 (9)
H44A	0.8234	−0.3413	−0.1180	0.043*
C45	0.7563 (3)	−0.2270 (3)	−0.06434 (16)	0.0284 (7)
H45A	0.7254	−0.1691	−0.0968	0.034*
C46	0.7467 (3)	−0.2158 (2)	−0.00092 (15)	0.0218 (7)
C47	0.7113 (3)	−0.1549 (3)	0.09066 (15)	0.0248 (7)
C48	0.6705 (3)	−0.0794 (3)	0.13700 (15)	0.0293 (8)
H48A	0.6001	−0.0821	0.1543	0.035*
H48B	0.7234	−0.1017	0.1719	0.035*
N1	0.5026 (2)	0.2359 (2)	0.53440 (14)	0.0304 (7)
H1A	0.5281	0.1884	0.5100	0.036*
N2	0.4643 (2)	0.3084 (2)	0.61898 (14)	0.0338 (7)
H2B	0.4607	0.3155	0.6583	0.041*
N3	0.9150 (2)	−0.0916 (2)	0.56992 (13)	0.0268 (6)
H3B	0.9359	−0.1254	0.6078	0.032*
N4	0.8273 (2)	0.0318 (2)	0.49290 (13)	0.0267 (6)
H4B	0.7816	0.0911	0.4727	0.032*
N5	0.7699 (2)	−0.2547 (2)	0.59717 (13)	0.0267 (6)
H5B	0.7905	−0.2908	0.6346	0.032*
N6	0.6935 (2)	−0.1217 (2)	0.52177 (12)	0.0232 (6)
H6A	0.6563	−0.0579	0.5025	0.028*
N7	0.6504 (2)	0.0355 (2)	0.60341 (13)	0.0248 (6)
N8	0.5094 (2)	0.2290 (2)	0.03123 (13)	0.0288 (6)
H8C	0.5355	0.1792	0.0083	0.035*
N9	0.4691 (2)	0.3092 (2)	0.11295 (14)	0.0324 (7)
H9A	0.4648	0.3198	0.1517	0.039*
N10	0.9204 (2)	−0.1004 (2)	0.07506 (13)	0.0245 (6)
H10B	0.9407	−0.1346	0.1129	0.029*
N11	0.8347 (2)	0.0244 (2)	−0.00246 (13)	0.0250 (6)
H11B	0.7902	0.0843	−0.0228	0.030*
N12	0.7697 (2)	−0.2593 (2)	0.10416 (13)	0.0278 (6)
H12B	0.7894	−0.2955	0.1417	0.033*
N13	0.6955 (2)	−0.1262 (2)	0.02822 (12)	0.0235 (6)
H13B	0.6592	−0.0622	0.0088	0.028*
N14	0.6556 (2)	0.0314 (2)	0.10697 (12)	0.0237 (6)
O5	0.9397 (3)	0.9824 (2)	0.23642 (14)	0.0548 (8)
H5C	0.8751	0.9886	0.2505	0.066*
H5D	0.9608	1.0271	0.2507	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02552 (13)	0.02860 (14)	0.02501 (13)	−0.00950 (10)	−0.00175 (10)	−0.00545 (10)
Cd2	0.02845 (14)	0.02631 (13)	0.02904 (14)	−0.01285 (11)	−0.00095 (10)	−0.00138 (10)
Cd3	0.03672 (15)	0.03111 (14)	0.02671 (14)	−0.01949 (12)	−0.00244 (11)	0.00189 (10)
Cd4	0.03477 (15)	0.02896 (14)	0.03084 (14)	−0.01747 (11)	0.00041 (11)	−0.00492 (10)
Cd5	0.02703 (14)	0.02876 (14)	0.02387 (13)	−0.01015 (11)	−0.00147 (10)	−0.00439 (10)
Cl1	0.0282 (5)	0.0428 (5)	0.0455 (6)	−0.0046 (4)	−0.0033 (4)	0.0005 (4)
Cl2	0.0336 (5)	0.0395 (5)	0.0203 (4)	−0.0114 (4)	0.0032 (3)	−0.0030 (3)
Cl3	0.0657 (7)	0.0297 (5)	0.0275 (5)	−0.0121 (4)	−0.0023 (4)	−0.0076 (4)
Cl4	0.0442 (5)	0.0358 (5)	0.0265 (5)	−0.0238 (4)	−0.0033 (4)	−0.0023 (4)
Cl5	0.0476 (6)	0.0633 (7)	0.0270 (5)	−0.0363 (5)	−0.0015 (4)	−0.0025 (4)
Cl6	0.0391 (5)	0.0332 (5)	0.0286 (5)	−0.0030 (4)	−0.0050 (4)	−0.0060 (4)
Cl7	0.0466 (5)	0.0372 (5)	0.0214 (4)	−0.0242 (4)	−0.0005 (4)	−0.0018 (3)
Cl8	0.0595 (6)	0.0452 (5)	0.0220 (4)	−0.0334 (5)	−0.0012 (4)	−0.0012 (4)
Cl9	0.0398 (5)	0.0355 (5)	0.0253 (4)	−0.0102 (4)	−0.0015 (4)	−0.0025 (4)
Cl10	0.0732 (8)	0.0736 (7)	0.0257 (5)	−0.0538 (6)	−0.0112 (5)	0.0066 (5)
Cl11	0.0654 (7)	0.0435 (5)	0.0288 (5)	−0.0369 (5)	0.0140 (4)	−0.0149 (4)
Cl12	0.0739 (8)	0.0869 (9)	0.0505 (7)	−0.0621 (7)	0.0334 (6)	−0.0442 (6)
Cl13	0.0539 (6)	0.0363 (5)	0.0282 (5)	−0.0276 (4)	−0.0094 (4)	0.0022 (4)
Cl14	0.0374 (6)	0.0495 (6)	0.0425 (6)	0.0045 (5)	−0.0084 (4)	−0.0012 (5)
Cl15	0.0345 (5)	0.0354 (5)	0.0183 (4)	−0.0114 (4)	0.0023 (3)	−0.0023 (3)
Cl16	0.0832 (8)	0.0350 (5)	0.0277 (5)	−0.0192 (5)	0.0031 (5)	−0.0085 (4)
O1	0.0503 (19)	0.0406 (17)	0.091 (3)	−0.0129 (15)	−0.0065 (18)	0.0071 (16)
O2	0.0404 (15)	0.0302 (13)	0.0348 (15)	−0.0165 (11)	0.0005 (12)	−0.0065 (11)
O3	0.0393 (16)	0.0452 (16)	0.0411 (16)	−0.0175 (13)	0.0005 (13)	0.0003 (12)
O4	0.0441 (18)	0.0439 (18)	0.076 (2)	−0.0014 (14)	−0.0028 (16)	0.0093 (16)
C1	0.0268 (19)	0.0311 (19)	0.034 (2)	−0.0078 (15)	−0.0020 (15)	−0.0043 (15)
C2	0.032 (2)	0.045 (2)	0.040 (2)	−0.0124 (18)	−0.0022 (17)	−0.0030 (18)
C3	0.034 (2)	0.044 (3)	0.063 (3)	−0.0121 (19)	−0.011 (2)	0.011 (2)
C4	0.038 (2)	0.031 (2)	0.078 (4)	−0.0073 (18)	−0.007 (2)	−0.003 (2)
C5	0.038 (2)	0.033 (2)	0.066 (3)	−0.0054 (18)	0.001 (2)	−0.021 (2)
C6	0.0281 (19)	0.030 (2)	0.042 (2)	−0.0055 (16)	−0.0032 (17)	−0.0072 (16)
C7	0.0243 (18)	0.0308 (19)	0.030 (2)	−0.0027 (15)	−0.0007 (15)	−0.0096 (15)
C8	0.0298 (19)	0.035 (2)	0.0238 (18)	−0.0007 (15)	0.0024 (15)	−0.0088 (15)
C9	0.0188 (16)	0.0301 (18)	0.0201 (17)	−0.0106 (14)	−0.0003 (13)	−0.0015 (13)
C10	0.0243 (18)	0.0323 (19)	0.0290 (19)	−0.0037 (15)	−0.0023 (15)	−0.0001 (15)
C11	0.031 (2)	0.038 (2)	0.035 (2)	−0.0060 (17)	0.0047 (16)	−0.0119 (17)
C12	0.040 (2)	0.051 (2)	0.0202 (19)	−0.0130 (19)	0.0024 (16)	−0.0066 (16)
C13	0.036 (2)	0.045 (2)	0.0218 (19)	−0.0118 (18)	−0.0031 (16)	0.0027 (16)
C14	0.0259 (17)	0.0284 (18)	0.0215 (17)	−0.0118 (14)	−0.0006 (14)	−0.0023 (13)
C15	0.0232 (17)	0.0305 (18)	0.0265 (18)	−0.0135 (14)	−0.0031 (14)	−0.0046 (14)
C16	0.0295 (19)	0.0318 (19)	0.0281 (19)	−0.0110 (15)	−0.0017 (15)	−0.0097 (14)
C17	0.0298 (18)	0.0277 (18)	0.0212 (17)	−0.0129 (15)	0.0014 (14)	−0.0059 (13)
C18	0.037 (2)	0.0291 (19)	0.037 (2)	−0.0095 (16)	−0.0007 (17)	−0.0042 (16)
C19	0.041 (2)	0.038 (2)	0.041 (2)	−0.0103 (18)	0.0088 (18)	−0.0209 (18)
C20	0.046 (2)	0.052 (2)	0.023 (2)	−0.020 (2)	0.0073 (17)	−0.0163 (17)
C21	0.037 (2)	0.039 (2)	0.0213 (18)	−0.0168 (17)	−0.0004 (15)	−0.0037 (15)
C22	0.0275 (18)	0.0275 (17)	0.0212 (17)	−0.0139 (14)	0.0005 (14)	−0.0045 (13)
C23	0.0224 (17)	0.0298 (18)	0.0230 (17)	−0.0114 (14)	0.0014 (13)	−0.0064 (13)
C24	0.038 (2)	0.0304 (19)	0.0222 (18)	−0.0133 (16)	0.0030 (15)	−0.0080 (14)
C25	0.0246 (18)	0.0323 (19)	0.036 (2)	−0.0113 (15)	0.0016 (15)	−0.0084 (15)
C26	0.039 (2)	0.042 (2)	0.036 (2)	−0.0135 (18)	−0.0066 (18)	0.0005 (17)
C27	0.036 (2)	0.048 (3)	0.063 (3)	−0.014 (2)	−0.009 (2)	0.016 (2)
C28	0.032 (2)	0.032 (2)	0.085 (4)	−0.0063 (18)	0.002 (2)	−0.006 (2)
C29	0.030 (2)	0.033 (2)	0.070 (3)	−0.0068 (17)	0.007 (2)	−0.018 (2)
C30	0.0247 (18)	0.033 (2)	0.039 (2)	−0.0094 (15)	0.0028 (16)	−0.0097 (16)
C31	0.0213 (17)	0.0345 (19)	0.0286 (19)	−0.0078 (15)	0.0014 (14)	−0.0118 (15)
C32	0.0260 (18)	0.036 (2)	0.0247 (19)	−0.0014 (15)	0.0032 (15)	−0.0067 (15)
C33	0.0206 (16)	0.0252 (17)	0.0247 (18)	−0.0101 (13)	0.0006 (13)	−0.0030 (13)
C34	0.0261 (18)	0.0267 (18)	0.035 (2)	−0.0039 (15)	−0.0075 (15)	−0.0040 (15)
C35	0.035 (2)	0.034 (2)	0.043 (2)	−0.0055 (17)	0.0030 (18)	−0.0175 (17)
C36	0.040 (2)	0.046 (2)	0.028 (2)	−0.0127 (18)	0.0030 (17)	−0.0124 (17)
C37	0.034 (2)	0.042 (2)	0.0207 (18)	−0.0135 (17)	0.0017 (15)	−0.0034 (15)
C38	0.0214 (16)	0.0259 (17)	0.0251 (18)	−0.0097 (14)	−0.0004 (13)	−0.0029 (13)
C39	0.0217 (17)	0.0282 (18)	0.0249 (18)	−0.0123 (14)	0.0012 (13)	−0.0057 (13)
C40	0.0289 (19)	0.0310 (19)	0.0273 (19)	−0.0109 (15)	−0.0003 (15)	−0.0100 (14)
C41	0.0302 (18)	0.0246 (17)	0.0205 (17)	−0.0129 (14)	−0.0012 (14)	−0.0034 (13)
C42	0.045 (2)	0.0231 (18)	0.034 (2)	−0.0073 (16)	−0.0046 (17)	−0.0013 (15)
C43	0.044 (2)	0.029 (2)	0.044 (2)	−0.0070 (17)	0.0003 (19)	−0.0144 (17)
C44	0.042 (2)	0.041 (2)	0.027 (2)	−0.0142 (18)	0.0042 (17)	−0.0140 (16)
C45	0.035 (2)	0.0310 (19)	0.0204 (17)	−0.0126 (15)	−0.0031 (14)	−0.0033 (14)
C46	0.0237 (17)	0.0226 (16)	0.0209 (17)	−0.0112 (13)	−0.0018 (13)	−0.0012 (12)
C47	0.0264 (17)	0.0285 (18)	0.0238 (17)	−0.0144 (14)	−0.0017 (14)	−0.0049 (13)
C48	0.037 (2)	0.0330 (19)	0.0192 (17)	−0.0135 (16)	0.0024 (15)	−0.0058 (14)
N1	0.0308 (16)	0.0283 (16)	0.0281 (16)	−0.0031 (13)	0.0002 (13)	−0.0104 (12)
N2	0.0345 (17)	0.0334 (17)	0.0300 (17)	−0.0041 (14)	0.0003 (13)	−0.0139 (13)
N3	0.0250 (15)	0.0333 (16)	0.0202 (15)	−0.0088 (12)	−0.0034 (12)	−0.0018 (12)
N4	0.0262 (15)	0.0253 (15)	0.0252 (15)	−0.0073 (12)	−0.0020 (12)	0.0008 (11)
N5	0.0339 (16)	0.0268 (15)	0.0176 (14)	−0.0093 (13)	−0.0023 (12)	−0.0012 (11)
N6	0.0248 (14)	0.0215 (14)	0.0221 (14)	−0.0078 (11)	−0.0031 (11)	−0.0011 (11)
N7	0.0227 (14)	0.0255 (15)	0.0255 (15)	−0.0058 (12)	0.0008 (12)	−0.0087 (11)
N8	0.0310 (16)	0.0286 (16)	0.0256 (16)	−0.0065 (13)	0.0008 (12)	−0.0100 (12)
N9	0.0319 (17)	0.0352 (17)	0.0289 (17)	−0.0066 (13)	0.0031 (13)	−0.0145 (13)
N10	0.0253 (15)	0.0285 (15)	0.0201 (14)	−0.0105 (12)	−0.0018 (11)	−0.0027 (11)
N11	0.0245 (15)	0.0245 (14)	0.0220 (15)	−0.0054 (12)	−0.0002 (11)	−0.0010 (11)
N12	0.0389 (17)	0.0271 (15)	0.0177 (14)	−0.0135 (13)	−0.0054 (12)	0.0010 (11)
N13	0.0268 (15)	0.0206 (14)	0.0229 (15)	−0.0085 (11)	−0.0024 (12)	−0.0020 (11)
N14	0.0225 (14)	0.0279 (15)	0.0206 (14)	−0.0083 (12)	0.0018 (11)	−0.0062 (11)
O5	0.069 (2)	0.0440 (17)	0.0528 (19)	−0.0148 (15)	−0.0005 (16)	−0.0217 (14)

Geometric parameters (Å, º)

Cd1—Cl3	2.4533 (12)	C20—C21	1.376 (5)
Cd1—Cl1	2.4962 (14)	C20—H20A	0.9300
Cd1—Cl4	2.5368 (11)	C21—C22	1.389 (4)
Cd1—Cl2	2.6847 (11)	C21—H21A	0.9300
Cd1—Cl5	2.6856 (12)	C22—N6	1.386 (4)
Cd2—O4	2.382 (3)	C23—N5	1.319 (4)
Cd2—Cl6	2.5622 (14)	C23—N6	1.326 (4)
Cd2—Cl8	2.5738 (12)	C23—C24	1.493 (4)
Cd2—Cl5	2.5814 (11)	C24—N7	1.469 (4)
Cd2—Cl7	2.6424 (11)	C24—H24A	0.9700
Cd2—Cl4	2.6927 (12)	C24—H24B	0.9700
Cd3—O3	2.530 (3)	C25—N8	1.378 (4)
Cd3—Cl9	2.5789 (14)	C25—C30	1.386 (5)
Cd3—Cl8	2.5863 (11)	C25—C26	1.397 (5)
Cd3—Cl7	2.5902 (12)	C26—C27	1.377 (6)
Cd3—Cl10	2.5904 (12)	C26—H26A	0.9300
Cd3—Cl11	2.5978 (12)	C27—C28	1.383 (6)
Cd4—O1	2.366 (3)	C27—H27A	0.9300
Cd4—O2	2.453 (3)	C28—C29	1.373 (6)
Cd4—Cl12	2.5273 (12)	C28—H28A	0.9300
Cd4—Cl11	2.5417 (11)	C29—C30	1.385 (5)
Cd4—Cl10	2.5628 (13)	C29—H29A	0.9300
Cd4—Cl13	2.6713 (12)	C30—N9	1.384 (5)
Cd5—Cl16	2.4393 (12)	C31—N8	1.332 (4)
Cd5—Cl14	2.4883 (15)	C31—N9	1.330 (4)
Cd5—Cl13	2.5843 (11)	C31—C32	1.489 (5)
Cd5—Cl15	2.6347 (11)	C32—N14	1.469 (4)
Cd5—Cl12	2.6628 (13)	C32—H32A	0.9700
O1—H1B	0.9601	C32—H32B	0.9700
O1—H1C	0.9599	C33—C34	1.386 (5)
O2—H2D	0.8501	C33—C38	1.385 (4)
O2—H2C	0.8499	C33—N10	1.391 (4)
O3—H3C	0.8500	C34—C35	1.372 (5)
O3—H3D	0.8500	C34—H34A	0.9300
O4—H4C	0.8500	C35—C36	1.389 (5)
O4—H4D	0.8498	C35—H35A	0.9300
C1—N1	1.383 (4)	C36—C37	1.368 (5)
C1—C6	1.384 (5)	C36—H36A	0.9300
C1—C2	1.398 (5)	C37—C38	1.392 (5)
C2—C3	1.379 (6)	C37—H37A	0.9300
C2—H2A	0.9300	C38—N11	1.385 (4)
C3—C4	1.385 (6)	C39—N10	1.328 (4)
C3—H3A	0.9300	C39—N11	1.339 (4)
C4—C5	1.370 (6)	C39—C40	1.483 (4)
C4—H4A	0.9300	C40—N14	1.473 (4)
C5—C6	1.386 (5)	C40—H40A	0.9700
C5—H5A	0.9300	C40—H40B	0.9700
C6—N2	1.392 (5)	C41—C42	1.387 (5)
C7—N1	1.321 (4)	C41—C46	1.388 (4)
C7—N2	1.333 (4)	C41—N12	1.397 (4)
C7—C8	1.481 (5)	C42—C43	1.369 (5)
C8—N7	1.464 (4)	C42—H42A	0.9300
C8—H8A	0.9700	C43—C44	1.390 (5)
C8—H8B	0.9700	C43—H43A	0.9300
C9—C14	1.386 (4)	C44—C45	1.375 (5)
C9—C10	1.390 (5)	C44—H44A	0.9300
C9—N3	1.391 (4)	C45—C46	1.383 (4)
C10—C11	1.374 (5)	C45—H45A	0.9300
C10—H10A	0.9300	C46—N13	1.390 (4)
C11—C12	1.391 (5)	C47—N12	1.322 (4)
C11—H11A	0.9300	C47—N13	1.327 (4)
C12—C13	1.376 (5)	C47—C48	1.487 (4)
C12—H12A	0.9300	C48—N14	1.465 (4)
C13—C14	1.387 (5)	C48—H48A	0.9700
C13—H13A	0.9300	C48—H48B	0.9700
C14—N4	1.384 (4)	N1—H1A	0.8600
C15—N3	1.320 (4)	N2—H2B	0.8600
C15—N4	1.332 (4)	N3—H3B	0.8600
C15—C16	1.493 (5)	N4—H4B	0.8600
C16—N7	1.475 (4)	N5—H5B	0.8600
C16—H16A	0.9700	N6—H6A	0.8600
C16—H16B	0.9700	N8—H8C	0.8600
C17—C22	1.383 (5)	N9—H9A	0.8600
C17—C18	1.387 (5)	N10—H10B	0.8600
C17—N5	1.390 (4)	N11—H11B	0.8600
C18—C19	1.377 (5)	N12—H12B	0.8600
C18—H18A	0.9300	N13—H13B	0.8600
C19—C20	1.387 (5)	O5—H5C	0.8501
C19—H19A	0.9300	O5—H5D	0.8500
Cl3—Cd1—Cl1	113.44 (4)	C18—C19—C20	122.3 (3)
Cl3—Cd1—Cl4	122.08 (4)	C18—C19—H19A	118.8
Cl1—Cd1—Cl4	124.47 (4)	C20—C19—H19A	118.8
Cl3—Cd1—Cl2	88.75 (4)	C21—C20—C19	122.0 (3)
Cl1—Cd1—Cl2	97.33 (4)	C21—C20—H20A	119.0
Cl4—Cd1—Cl2	85.20 (3)	C19—C20—H20A	119.0
Cl3—Cd1—Cl5	94.46 (4)	C20—C21—C22	115.8 (3)
Cl1—Cd1—Cl5	90.57 (4)	C20—C21—H21A	122.1
Cl4—Cd1—Cl5	84.63 (3)	C22—C21—H21A	122.1
Cl2—Cd1—Cl5	169.50 (3)	C17—C22—N6	106.5 (3)
O4—Cd2—Cl6	167.60 (9)	C17—C22—C21	122.2 (3)
O4—Cd2—Cl8	86.65 (8)	N6—C22—C21	131.3 (3)
Cl6—Cd2—Cl8	90.97 (5)	N5—C23—N6	109.3 (3)
O4—Cd2—Cl5	90.67 (9)	N5—C23—C24	125.4 (3)
Cl6—Cd2—Cl5	101.68 (4)	N6—C23—C24	125.3 (3)
Cl8—Cd2—Cl5	95.95 (4)	N7—C24—C23	111.8 (3)
O4—Cd2—Cl7	79.30 (9)	N7—C24—H24A	109.3
Cl6—Cd2—Cl7	88.44 (4)	C23—C24—H24A	109.3
Cl8—Cd2—Cl7	87.58 (3)	N7—C24—H24B	109.3
Cl5—Cd2—Cl7	169.19 (3)	C23—C24—H24B	109.3
O4—Cd2—Cl4	86.66 (8)	H24A—C24—H24B	107.9
Cl6—Cd2—Cl4	95.66 (4)	N8—C25—C30	106.7 (3)
Cl8—Cd2—Cl4	173.30 (3)	N8—C25—C26	131.3 (3)
Cl5—Cd2—Cl4	83.63 (3)	C30—C25—C26	122.1 (3)
Cl7—Cd2—Cl4	91.67 (3)	C27—C26—C25	114.9 (4)
O3—Cd3—Cl9	172.63 (6)	C27—C26—H26A	122.6
O3—Cd3—Cl8	84.31 (7)	C25—C26—H26A	122.6
Cl9—Cd3—Cl8	93.06 (4)	C26—C27—C28	123.0 (4)
O3—Cd3—Cl7	79.70 (7)	C26—C27—H27A	118.5
Cl9—Cd3—Cl7	93.37 (4)	C28—C27—H27A	118.5
Cl8—Cd3—Cl7	88.43 (3)	C29—C28—C27	122.2 (4)
O3—Cd3—Cl10	87.86 (7)	C29—C28—H28A	118.9
Cl9—Cd3—Cl10	95.19 (4)	C27—C28—H28A	118.9
Cl8—Cd3—Cl10	171.18 (4)	C28—C29—C30	115.8 (4)
Cl7—Cd3—Cl10	94.18 (4)	C28—C29—H29A	122.1
O3—Cd3—Cl11	88.99 (7)	C30—C29—H29A	122.1
Cl9—Cd3—Cl11	97.97 (5)	C29—C30—C25	122.1 (4)
Cl8—Cd3—Cl11	91.39 (3)	C29—C30—N9	132.1 (4)
Cl7—Cd3—Cl11	168.65 (3)	C25—C30—N9	105.8 (3)
Cl10—Cd3—Cl11	84.39 (4)	N8—C31—N9	108.3 (3)
O1—Cd4—O2	171.23 (10)	N8—C31—C32	126.6 (3)
O1—Cd4—Cl12	91.16 (9)	N9—C31—C32	125.0 (3)
O2—Cd4—Cl12	91.64 (7)	N14—C32—C31	111.3 (3)
O1—Cd4—Cl11	94.02 (9)	N14—C32—H32A	109.4
O2—Cd4—Cl11	82.87 (7)	C31—C32—H32A	109.4
Cl12—Cd4—Cl11	174.21 (4)	N14—C32—H32B	109.4
O1—Cd4—Cl10	93.85 (9)	C31—C32—H32B	109.4
O2—Cd4—Cl10	94.12 (7)	H32A—C32—H32B	108.0
Cl12—Cd4—Cl10	96.12 (4)	C34—C33—C38	121.4 (3)
Cl11—Cd4—Cl10	86.11 (4)	C34—C33—N10	132.2 (3)
O1—Cd4—Cl13	83.75 (9)	C38—C33—N10	106.3 (3)
O2—Cd4—Cl13	88.23 (7)	C35—C34—C33	116.1 (3)
Cl12—Cd4—Cl13	84.75 (4)	C35—C34—H34A	121.9
Cl11—Cd4—Cl13	93.24 (3)	C33—C34—H34A	121.9
Cl10—Cd4—Cl13	177.46 (4)	C34—C35—C36	122.3 (3)
Cl16—Cd5—Cl14	114.71 (5)	C34—C35—H35A	118.8
Cl16—Cd5—Cl13	138.39 (4)	C36—C35—H35A	118.8
Cl14—Cd5—Cl13	106.89 (4)	C37—C36—C35	122.2 (4)
Cl16—Cd5—Cl15	90.12 (4)	C37—C36—H36A	118.9
Cl14—Cd5—Cl15	98.41 (5)	C35—C36—H36A	118.9
Cl13—Cd5—Cl15	84.62 (3)	C36—C37—C38	115.6 (3)
Cl16—Cd5—Cl12	94.43 (4)	C36—C37—H37A	122.2
Cl14—Cd5—Cl12	90.84 (5)	C38—C37—H37A	122.2
Cl13—Cd5—Cl12	83.83 (4)	C33—C38—N11	106.1 (3)
Cl15—Cd5—Cl12	166.90 (3)	C33—C38—C37	122.3 (3)
Cd1—Cl4—Cd2	96.20 (3)	N11—C38—C37	131.5 (3)
Cd2—Cl5—Cd1	95.32 (4)	N10—C39—N11	108.2 (3)
Cd3—Cl7—Cd2	91.11 (3)	N10—C39—C40	126.3 (3)
Cd2—Cl8—Cd3	92.77 (3)	N11—C39—C40	125.1 (3)
Cd4—Cl10—Cd3	92.39 (4)	N14—C40—C39	110.6 (3)
Cd4—Cl11—Cd3	92.71 (4)	N14—C40—H40A	109.5
Cd4—Cl12—Cd5	94.47 (4)	C39—C40—H40A	109.5
Cd5—Cl13—Cd4	92.96 (3)	N14—C40—H40B	109.5
Cd4—O1—H1B	109.2	C39—C40—H40B	109.5
Cd4—O1—H1C	109.2	H40A—C40—H40B	108.1
H1B—O1—H1C	109.5	C42—C41—C46	121.6 (3)
Cd4—O2—H2D	106.8	C42—C41—N12	132.3 (3)
Cd4—O2—H2C	106.6	C46—C41—N12	106.1 (3)
H2D—O2—H2C	106.6	C43—C42—C41	115.7 (3)
Cd3—O3—H3C	110.8	C43—C42—H42A	122.2
Cd3—O3—H3D	110.4	C41—C42—H42A	122.2
H3C—O3—H3D	108.8	C42—C43—C44	122.8 (3)
Cd2—O4—H4C	118.4	C42—C43—H43A	118.6
Cd2—O4—H4D	97.0	C44—C43—H43A	118.6
H4C—O4—H4D	118.0	C45—C44—C43	121.9 (3)
N1—C1—C6	106.3 (3)	C45—C44—H44A	119.0
N1—C1—C2	131.1 (3)	C43—C44—H44A	119.0
C6—C1—C2	122.5 (3)	C44—C45—C46	115.6 (3)
C3—C2—C1	114.9 (4)	C44—C45—H45A	122.2
C3—C2—H2A	122.5	C46—C45—H45A	122.2
C1—C2—H2A	122.5	C45—C46—N13	131.4 (3)
C2—C3—C4	122.4 (4)	C45—C46—C41	122.5 (3)
C2—C3—H3A	118.8	N13—C46—C41	106.1 (3)
C4—C3—H3A	118.8	N12—C47—N13	109.3 (3)
C5—C4—C3	122.5 (4)	N12—C47—C48	126.4 (3)
C5—C4—H4A	118.7	N13—C47—C48	124.3 (3)
C3—C4—H4A	118.7	N14—C48—C47	111.3 (3)
C4—C5—C6	116.1 (4)	N14—C48—H48A	109.4
C4—C5—H5A	121.9	C47—C48—H48A	109.4
C6—C5—H5A	121.9	N14—C48—H48B	109.4
C1—C6—C5	121.5 (4)	C47—C48—H48B	109.4
C1—C6—N2	106.0 (3)	H48A—C48—H48B	108.0
C5—C6—N2	132.5 (4)	C7—N1—C1	109.9 (3)
N1—C7—N2	108.6 (3)	C7—N1—H1A	125.1
N1—C7—C8	126.6 (3)	C1—N1—H1A	125.1
N2—C7—C8	124.6 (3)	C7—N2—C6	109.2 (3)
N7—C8—C7	111.0 (3)	C7—N2—H2B	125.4
N7—C8—H8A	109.4	C6—N2—H2B	125.4
C7—C8—H8A	109.4	C15—N3—C9	109.9 (3)
N7—C8—H8B	109.4	C15—N3—H3B	125.0
C7—C8—H8B	109.4	C9—N3—H3B	125.0
H8A—C8—H8B	108.0	C15—N4—C14	109.5 (3)
C14—C9—C10	121.5 (3)	C15—N4—H4B	125.2
C14—C9—N3	105.8 (3)	C14—N4—H4B	125.2
C10—C9—N3	132.7 (3)	C23—N5—C17	109.3 (3)
C11—C10—C9	116.0 (3)	C23—N5—H5B	125.3
C11—C10—H10A	122.0	C17—N5—H5B	125.3
C9—C10—H10A	122.0	C23—N6—C22	109.0 (3)
C10—C11—C12	122.5 (3)	C23—N6—H6A	125.5
C10—C11—H11A	118.8	C22—N6—H6A	125.5
C12—C11—H11A	118.8	C8—N7—C24	110.6 (3)
C13—C12—C11	121.8 (3)	C8—N7—C16	110.3 (3)
C13—C12—H12A	119.1	C24—N7—C16	111.4 (3)
C11—C12—H12A	119.1	C31—N8—C25	109.5 (3)
C12—C13—C14	115.9 (3)	C31—N8—H8C	125.2
C12—C13—H13A	122.0	C25—N8—H8C	125.2
C14—C13—H13A	122.0	C31—N9—C30	109.8 (3)
N4—C14—C13	131.4 (3)	C31—N9—H9A	125.1
N4—C14—C9	106.3 (3)	C30—N9—H9A	125.1
C13—C14—C9	122.3 (3)	C39—N10—C33	109.6 (3)
N3—C15—N4	108.4 (3)	C39—N10—H10B	125.2
N3—C15—C16	125.6 (3)	C33—N10—H10B	125.2
N4—C15—C16	125.7 (3)	C39—N11—C38	109.7 (3)
N7—C16—C15	110.2 (3)	C39—N11—H11B	125.1
N7—C16—H16A	109.6	C38—N11—H11B	125.1
C15—C16—H16A	109.6	C47—N12—C41	109.1 (3)
N7—C16—H16B	109.6	C47—N12—H12B	125.4
C15—C16—H16B	109.6	C41—N12—H12B	125.4
H16A—C16—H16B	108.1	C47—N13—C46	109.3 (3)
C22—C17—C18	121.8 (3)	C47—N13—H13B	125.3
C22—C17—N5	105.9 (3)	C46—N13—H13B	125.3
C18—C17—N5	132.3 (3)	C48—N14—C32	110.7 (3)
C19—C18—C17	115.9 (3)	C48—N14—C40	112.3 (3)
C19—C18—H18A	122.1	C32—N14—C40	111.2 (3)
C17—C18—H18A	122.1	H5C—O5—H5D	108.5
Cl3—Cd1—Cl4—Cd2	88.41 (5)	C18—C17—C22—N6	−179.9 (3)
Cl1—Cd1—Cl4—Cd2	−90.49 (5)	N5—C17—C22—N6	−0.6 (4)
Cl2—Cd1—Cl4—Cd2	173.91 (3)	C18—C17—C22—C21	−1.6 (5)
Cl5—Cd1—Cl4—Cd2	−3.49 (3)	N5—C17—C22—C21	177.7 (3)
O4—Cd2—Cl4—Cd1	94.70 (9)	C20—C21—C22—C17	1.7 (5)
Cl6—Cd2—Cl4—Cd1	−97.53 (4)	C20—C21—C22—N6	179.6 (3)
Cl8—Cd2—Cl4—Cd1	90.4 (2)	N5—C23—C24—N7	155.2 (3)
Cl5—Cd2—Cl4—Cd1	3.64 (3)	N6—C23—C24—N7	−24.3 (5)
Cl7—Cd2—Cl4—Cd1	173.88 (3)	N8—C25—C26—C27	−179.2 (4)
O4—Cd2—Cl5—Cd1	−90.00 (9)	C30—C25—C26—C27	0.7 (5)
Cl6—Cd2—Cl5—Cd1	91.06 (5)	C25—C26—C27—C28	0.2 (6)
Cl8—Cd2—Cl5—Cd1	−176.70 (3)	C26—C27—C28—C29	−0.6 (7)
Cl7—Cd2—Cl5—Cd1	−68.07 (16)	C27—C28—C29—C30	0.1 (6)
Cl4—Cd2—Cl5—Cd1	−3.43 (3)	C28—C29—C30—C25	0.8 (6)
Cl3—Cd1—Cl5—Cd2	−118.22 (5)	C28—C29—C30—N9	179.4 (4)
Cl1—Cd1—Cl5—Cd2	128.22 (4)	N8—C25—C30—C29	178.6 (3)
Cl4—Cd1—Cl5—Cd2	3.64 (3)	C26—C25—C30—C29	−1.3 (6)
Cl2—Cd1—Cl5—Cd2	−10.72 (19)	N8—C25—C30—N9	−0.3 (4)
O3—Cd3—Cl7—Cd2	−87.04 (7)	C26—C25—C30—N9	179.8 (3)
Cl9—Cd3—Cl7—Cd2	90.44 (4)	N8—C31—C32—N14	31.1 (5)
Cl8—Cd3—Cl7—Cd2	−2.54 (3)	N9—C31—C32—N14	−152.8 (3)
Cl10—Cd3—Cl7—Cd2	−174.10 (3)	C38—C33—C34—C35	−0.1 (5)
Cl11—Cd3—Cl7—Cd2	−91.80 (15)	N10—C33—C34—C35	175.6 (3)
O4—Cd2—Cl7—Cd3	−84.50 (8)	C33—C34—C35—C36	1.3 (6)
Cl6—Cd2—Cl7—Cd3	93.59 (5)	C34—C35—C36—C37	−0.9 (6)
Cl8—Cd2—Cl7—Cd3	2.55 (3)	C35—C36—C37—C38	−0.7 (6)
Cl5—Cd2—Cl7—Cd3	−106.83 (15)	C34—C33—C38—N11	176.4 (3)
Cl4—Cd2—Cl7—Cd3	−170.78 (3)	N10—C33—C38—N11	−0.3 (3)
O4—Cd2—Cl8—Cd3	76.86 (9)	C34—C33—C38—C37	−1.5 (5)
Cl6—Cd2—Cl8—Cd3	−90.95 (4)	N10—C33—C38—C37	−178.2 (3)
Cl5—Cd2—Cl8—Cd3	167.19 (3)	C36—C37—C38—C33	1.9 (5)
Cl7—Cd2—Cl8—Cd3	−2.56 (3)	C36—C37—C38—N11	−175.4 (3)
Cl4—Cd2—Cl8—Cd3	81.1 (2)	N10—C39—C40—N14	−94.7 (4)
O3—Cd3—Cl8—Cd2	82.41 (7)	N11—C39—C40—N14	77.2 (4)
Cl9—Cd3—Cl8—Cd2	−90.68 (5)	C46—C41—C42—C43	−0.3 (5)
Cl7—Cd3—Cl8—Cd2	2.61 (3)	N12—C41—C42—C43	−179.6 (4)
Cl10—Cd3—Cl8—Cd2	109.99 (19)	C41—C42—C43—C44	1.3 (6)
Cl11—Cd3—Cl8—Cd2	171.26 (3)	C42—C43—C44—C45	−1.2 (6)
O1—Cd4—Cl10—Cd3	−109.70 (9)	C43—C44—C45—C46	−0.1 (5)
O2—Cd4—Cl10—Cd3	66.62 (7)	C44—C45—C46—N13	179.5 (3)
Cl12—Cd4—Cl10—Cd3	158.71 (4)	C44—C45—C46—C41	1.1 (5)
Cl11—Cd4—Cl10—Cd3	−15.93 (4)	C42—C41—C46—C45	−0.9 (5)
Cl13—Cd4—Cl10—Cd3	−91.1 (7)	N12—C41—C46—C45	178.5 (3)
O3—Cd3—Cl10—Cd4	104.81 (7)	C42—C41—C46—N13	−179.6 (3)
Cl9—Cd3—Cl10—Cd4	−81.92 (5)	N12—C41—C46—N13	−0.2 (3)
Cl8—Cd3—Cl10—Cd4	77.3 (2)	N12—C47—C48—N14	154.0 (3)
Cl7—Cd3—Cl10—Cd4	−175.69 (3)	N13—C47—C48—N14	−24.9 (5)
Cl11—Cd3—Cl10—Cd4	15.61 (4)	N2—C7—N1—C1	−0.5 (4)
O1—Cd4—Cl11—Cd3	109.47 (9)	C8—C7—N1—C1	175.9 (3)
O2—Cd4—Cl11—Cd3	−78.77 (7)	C6—C1—N1—C7	0.6 (4)
Cl12—Cd4—Cl11—Cd3	−97.0 (3)	C2—C1—N1—C7	179.7 (4)
Cl10—Cd4—Cl11—Cd3	15.88 (4)	N1—C7—N2—C6	0.2 (4)
Cl13—Cd4—Cl11—Cd3	−166.57 (3)	C8—C7—N2—C6	−176.3 (3)
O3—Cd3—Cl11—Cd4	−103.70 (7)	C1—C6—N2—C7	0.1 (4)
Cl9—Cd3—Cl11—Cd4	78.73 (4)	C5—C6—N2—C7	−179.7 (4)
Cl8—Cd3—Cl11—Cd4	172.02 (3)	N4—C15—N3—C9	−2.2 (4)
Cl7—Cd3—Cl11—Cd4	−99.02 (14)	C16—C15—N3—C9	171.6 (3)
Cl10—Cd3—Cl11—Cd4	−15.75 (4)	C14—C9—N3—C15	1.6 (4)
O1—Cd4—Cl12—Cd5	68.72 (9)	C10—C9—N3—C15	−175.3 (4)
O2—Cd4—Cl12—Cd5	−102.96 (7)	N3—C15—N4—C14	1.9 (4)
Cl11—Cd4—Cl12—Cd5	−84.8 (3)	C16—C15—N4—C14	−171.9 (3)
Cl10—Cd4—Cl12—Cd5	162.72 (4)	C13—C14—N4—C15	177.2 (4)
Cl13—Cd4—Cl12—Cd5	−14.89 (4)	C9—C14—N4—C15	−0.9 (4)
Cl16—Cd5—Cl12—Cd4	153.66 (5)	N6—C23—N5—C17	0.2 (4)
Cl14—Cd5—Cl12—Cd4	−91.47 (5)	C24—C23—N5—C17	−179.3 (3)
Cl13—Cd5—Cl12—Cd4	15.43 (4)	C22—C17—N5—C23	0.2 (4)
Cl15—Cd5—Cl12—Cd4	43.63 (17)	C18—C17—N5—C23	179.5 (4)
Cl16—Cd5—Cl13—Cd4	−104.28 (6)	N5—C23—N6—C22	−0.6 (4)
Cl14—Cd5—Cl13—Cd4	74.45 (5)	C24—C23—N6—C22	179.0 (3)
Cl15—Cd5—Cl13—Cd4	171.62 (3)	C17—C22—N6—C23	0.7 (4)
Cl12—Cd5—Cl13—Cd4	−14.55 (4)	C21—C22—N6—C23	−177.3 (4)
O1—Cd4—Cl13—Cd5	−76.42 (9)	C7—C8—N7—C24	−158.2 (3)
O2—Cd4—Cl13—Cd5	107.13 (7)	C7—C8—N7—C16	78.1 (4)
Cl12—Cd4—Cl13—Cd5	15.33 (4)	C23—C24—N7—C8	151.6 (3)
Cl11—Cd4—Cl13—Cd5	−170.12 (3)	C23—C24—N7—C16	−85.3 (3)
Cl10—Cd4—Cl13—Cd5	−95.1 (7)	C15—C16—N7—C8	−167.4 (3)
N1—C1—C2—C3	−179.2 (4)	C15—C16—N7—C24	69.3 (3)
C6—C1—C2—C3	−0.2 (5)	N9—C31—N8—C25	−0.9 (4)
C1—C2—C3—C4	0.7 (6)	C32—C31—N8—C25	175.7 (3)
C2—C3—C4—C5	−1.4 (7)	C30—C25—N8—C31	0.7 (4)
C3—C4—C5—C6	1.3 (6)	C26—C25—N8—C31	−179.4 (4)
N1—C1—C6—C5	179.4 (3)	N8—C31—N9—C30	0.8 (4)
C2—C1—C6—C5	0.2 (6)	C32—C31—N9—C30	−175.9 (3)
N1—C1—C6—N2	−0.4 (4)	C29—C30—N9—C31	−179.0 (4)
C2—C1—C6—N2	−179.6 (3)	C25—C30—N9—C31	−0.3 (4)
C4—C5—C6—C1	−0.8 (6)	N11—C39—N10—C33	−2.2 (4)
C4—C5—C6—N2	179.1 (4)	C40—C39—N10—C33	170.8 (3)
N1—C7—C8—N7	30.2 (5)	C34—C33—N10—C39	−174.6 (4)
N2—C7—C8—N7	−153.9 (3)	C38—C33—N10—C39	1.6 (3)
C14—C9—C10—C11	0.1 (5)	N10—C39—N11—C38	2.1 (4)
N3—C9—C10—C11	176.6 (3)	C40—C39—N11—C38	−171.1 (3)
C9—C10—C11—C12	0.7 (6)	C33—C38—N11—C39	−1.1 (4)
C10—C11—C12—C13	−0.4 (6)	C37—C38—N11—C39	176.6 (3)
C11—C12—C13—C14	−0.8 (6)	N13—C47—N12—C41	0.4 (4)
C12—C13—C14—N4	−176.1 (4)	C48—C47—N12—C41	−178.6 (3)
C12—C13—C14—C9	1.7 (5)	C42—C41—N12—C47	179.2 (4)
C10—C9—C14—N4	176.9 (3)	C46—C41—N12—C47	−0.1 (4)
N3—C9—C14—N4	−0.4 (3)	N12—C47—N13—C46	−0.5 (4)
C10—C9—C14—C13	−1.4 (5)	C48—C47—N13—C46	178.5 (3)
N3—C9—C14—C13	−178.7 (3)	C45—C46—N13—C47	−178.1 (3)
N3—C15—C16—N7	−95.7 (4)	C41—C46—N13—C47	0.5 (4)
N4—C15—C16—N7	77.0 (4)	C47—C48—N14—C32	149.9 (3)
C22—C17—C18—C19	0.3 (5)	C47—C48—N14—C40	−85.2 (3)
N5—C17—C18—C19	−178.9 (4)	C31—C32—N14—C48	−156.3 (3)
C17—C18—C19—C20	0.9 (6)	C31—C32—N14—C40	78.2 (3)
C18—C19—C20—C21	−0.7 (6)	C39—C40—N14—C48	70.3 (3)
C19—C20—C21—C22	−0.6 (6)	C39—C40—N14—C32	−165.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···Cl1^i	0.96	2.49	3.240 (3)	135
O1—H1C···Cl14	0.96	2.44	3.397 (3)	171
O2—H2D···O5^ii	0.85	1.81	2.610 (4)	156
O2—H2C···Cl9	0.85	2.29	3.130 (3)	173
O3—H3C···Cl1^i	0.85	2.66	3.317 (3)	135
O3—H3D···Cl6	0.85	2.67	3.387 (3)	144
O4—H4C···Cl14^ii	0.85	2.53	3.154 (3)	131
O4—H4D···Cl7	0.85	2.67	3.212 (3)	123
O4—H4D···Cl9	0.85	2.81	3.400 (3)	128
N1—H1A···Cl2^i	0.86	2.27	3.108 (3)	166
N2—H2B···Cl14^iii	0.86	2.52	3.361 (3)	167
N3—H3B···Cl6^iv	0.86	2.29	3.100 (3)	157
N4—H4B···Cl4^i	0.86	2.52	3.275 (3)	147
N4—H4B···Cl2^i	0.86	2.93	3.432 (3)	119
N5—H5B···O3^iv	0.86	2.14	2.942 (4)	155
N6—H6A···Cl2^i	0.86	2.34	3.178 (3)	166
N8—H8C···Cl15^v	0.86	2.27	3.107 (3)	166
N9—H9A···Cl1^i	0.86	2.56	3.382 (3)	161
N10—H10B···O2^vi	0.86	1.96	2.815 (4)	173
N11—H11B···Cl13^v	0.86	2.43	3.207 (3)	151
N12—H12B···Cl9^vi	0.86	2.29	3.114 (3)	159
N13—H13B···Cl15^v	0.86	2.28	3.102 (3)	161
O5—H5C···Cl3^vii	0.85	2.36	3.205 (4)	176
O5—H5D···Cl6^vii	0.85	2.31	3.161 (3)	177

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