{Δ-1,4,7,10-Tetrakis[(S)-2-hydroxy­propyl-κO]-1,4,7,10-tetra­aza­cyclo­do­dec­ane-κ⁴N}cad­mium(II) 4-nitrophenolate per­chlor­ate hydrate

Crystallization of [Cd(S-thpc12)](ClO₄)₂·H₂O {S-thpc12 is 1,4,7,10-tetra­kis[(S)-2-hy­drox­y­propyl]-1,4,7,10-tetra­aza­cy­clo-do­dec­ane} in the presence of sodium p-nitrophenolate forms the title complex, [Cd(C₂₀H₄₄N₄O₄)](C₆H₄NO₃)(ClO₄)·H₂O, in which p-nitrophenolate and water separately hydrogen bond to a different pair of cis-related pendant hydroxyl groups which, together with the four N atoms, are themselves bound to Cd^II in an approximately square antiprismatic arrangement. The diastereoselectivity of the complex-forming process is apparent from the fact that both different disymmetric cations in the asymmetric unit have the same Δ helicity.

S1. Comment

The ability of optically active pendant hydroxyl donor macrocyclic ligands based on cyclen (cyclen is 1,4,7,10-tetraazacyclododecane) to coordinate in a diastereoselective manner has been noted previously (Dhillon et al., 1997, 1998). The structures of such complexes generally approximate to that of a square antiprism (Buøen et al., 1982; Chin et al., 1994; Hancock et al., 1988; Luckay et al., 1997) and as such have an inherent helicity which may be described as Λ or Δ according to whether the four hydroxyl donors are displaced anticlockwise or clockwise, with respect to the nitrogen atom to which each is attached, when the molecule is viewed from the plane of the hydroxyl groups towards the plane of the four nitrogen atoms along the C₄ axis (Dhillon et al., 1995). Recent research has been directed towards attaching aromatic groups to each of the pendant arms in such a way that they will juxtapose to form a cavity suitable for the inclusion of smaller guest molecules (Smith et al., 1999). In the present work the attached group is the smaller methyl group and it was of interest to determine whether association with potential guest molecules for the larger complexes would occur in the absence of aromatic attachments.

There are two formula units of Δ[Cd(S-thpc12)] p-nitrophenolate perchlorate hydrate, (I), in the asymmetric unit which, apart from their orientation in the crystal, are very nearly identical, so they will be discussed as one (Fig. 1). There is a high degree of pseudosymmetry in the structure with average weak intensity data indicating approximate glide planes and a space group that tends towards Pcab. This space group is precluded because of the presence of enantiomerically pure chiral cations. Fig. 2 shows the relationship between the crystallographically independent species and illustrates one of the approximate glide planes.

The structures of the two cations (A and B) show the expected, approximately square antiprismatic, geometry with Cd—O (hydroxyl) bond lengths in the range 2.349 (5)–2.626 (5) Å and Cd—N bond lengths in the range 2.435 (7)–2.492 (7) Å. The twist angles for the cations are ca +12.5° giving both complexes the Δ helicity. This is similar to the configuration for [K(S-thpc12)]⁺ predicted by molecular orbital calculations (Dhillon et al., 1997). The p-nitrophenolate is associated with two adjacent pendant hydroxyl donors via hydrogen bonds (Fig. 1 & Table 1). The Cd^II-phenolate O distances are 4.005 (6) and 3.993 (6) Å for A & B, respectively, eliminating the possibility of significant ionic interaction between these two charged centres. The displacement ellipsoids of the nitro groups indicate that there is considerable positional freedom for the p-nitrophenolate anions (Fig. 1). There are no base-stacking interactions between the p-nitrophenolates. The other pair of adjacent hydroxyl groups is hydrogen bonded to the water molecule (Fig. 1 & Table 1). The water molecule also acts as the donor in hydrogen bonds to the phenolate O and to perchlorate.

The results of the crystal structure of (I) described here, show that p-nitrophenolate and water can both associate with the complex in the solid state. The electrical conductivity of the complex in DMF solution (92 Ω⁻¹ cm² mol⁻¹), however, is above the range normally shown by 1:1 electrolytes in this solvent (65–90 and 130–170 Ω⁻¹cm²mol⁻¹) for 1:1 and 1:2 electrolytes, respectively (Geary, 1971), showing that the p-nitrophenolate, at least, is partially dissociated in DMF, and probably more so in solvents of higher dielectric constant.

S2. Experimental

[Cd(S-thpc12)](ClO₄)₂·H₂O:- A solution of cadmium perchlorate hexahydrate (356 mg, 0.84 mmol) in dry ethanol (4 cm³) was added over several minutes to a refluxing solution of S-thpc12 (229 mg, 0.56 mmol) in dry ethanol (10 cm³). The solution was heated under reflux for 1 h, then allowed to cool slowly overnight. Very large white needles formed that were filtered off and washed with cold ethanol (2 cm³). Yield 328 mg, 81%. ¹³C NMR (DMSO-d₆) δ 62.01 (4 C), 59.42 (4 C), 49.99 (4 C), 48.03 (4 C), 20.96 (4 C). Analysis calculated for C₂₀H₄₆CdCl₂N₄O₁₃: C 32.73, H 6.32, N 7.63%. Found C 32.88, H 5.98, N 7.64%. Conductivity 153 Ω⁻¹ cm² mol⁻¹ (0.001 M, DMF) (1:2).

The title compound was prepared by adding sodium p-nitrophenolate (46 mg, 0.28 mmol) to a solution of [Cd(S-thpc12)](ClO₄)₂·H₂O (205 mg, 0.28 mmol) in dry acetonitrile (15 cm³). The yellow solution was then heated under reflux for 2 h, cooled and the solvent removed in vacuo. The yellow solid residue that remained was dissolved in boiling ethanol (10 cm³) and allowed to cool slowly. Fine pale yellow needles formed that were collected by filtration and dried under vacuum. Yield: 131 mg, 60%. ¹³C NMR (DMSO-d₆) δ 177.16 (1 C), 131.77 (1 C), 127.19 (2 C), 118.94 (2 C), 61.79 (4 C), 59.77 (4 C), 50.06 (4 C), 48.09 (4 C), 20.98 (4 C). Analysis calculated for C₂₆H₅₀CdClN₅O₁₂: C 40.42, H 6.52, N 9.07%. Found C 40.67, H 6.40, N 9.10%. Crystals suitable for X-ray analysis were grown by diffusion of ether into a solution of the complex in acetonitrile.

S3. Refinement

Attempts to collect the data at 150 K failed because the crystal appeared to undergo a phase change. At 200 K there was a high degree of streaking in parts of reciprocal space leading to large background imbalances for some reflections. 363 measured reflections where the background ratios were greater than 2:1 were removed from the data set. All reflections (6622) with F² > 0.0 were used in the refinement. Bondlength restraints for the bonds of the macrocycle and the phenyl C—C bonds were used in the refinement. The chirality followed from the synthesis. The absolute configuration was checked by refining a Flack parameter in early refinement cycles. No additional rotational symmetry was found by BUNYIP (Hester & Hall, 1995).

Computing details

Data reduction: DIFDAT, SORTRF and ADDREF in Xtal (Hall et al., 1995); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYLSQ in Xtal; molecular graphics: Xtal; software used to prepare material for publication: BONDLA and CIFIO in Xtal.

Figures

	Fig. 1. A perspective view of one of the crystallographically independent units in the structure. Hydrogen bonds are shown as dashed lines. Displacement ellipsoids are at the 50% probability level.
	Fig. 2. A view of one layer of the structure looking down c. (A), (D) and (F) are related to (B), (C) and (E) by the pseudo a glide plane perpendicular to b. Cations labeled A & B have the same chirality. Letters correspond to atom labels in the coordinate table.

(I)

Crystal data

[Cd(C20H44N4O4)](C6H4NO3)(ClO4)·H2O	F(000) = 3216
Mr = 772.57	Dx = 1.498 Mg m^−3
Orthorhombic, P212121	Mo_ Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 13.9929 (11) Å	θ = 15.2–19.4°
b = 19.6661 (11) Å	µ = 0.78 mm^−1
c = 24.890 (3) Å	T = 200 K
V = 6849.3 (11) Å^3	Tabular, pale yellow
Z = 8	0.40 × 0.24 × 0.20 mm

Data collection

CAD4/PC diffractometer	5325 reflections with I > 2σ(I)
Radiation source: xray tube	Rint = 0.025
Graphite monochromator	θmax = 26.0°, θmin = 2.1°
ω/2θ scans	h = −16→17
Absorption correction: gaussian (ABSORB; Hall et al., 1995)	k = 0→24
Tmin = 0.831, Tmax = 0.864	l = 0→30
13751 measured reflections	3 standard reflections every 120 min
7229 independent reflections	intensity decay: 2%

Refinement

Refinement on F^2	0 constraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: geometrical
wR(F^2) = 0.070	H-atom parameters not refined
S = 1.47	Weighting scheme based on measured s.u.'s
6622 reflections	(Δ/σ)max = 0.003
811 parameters	Δρmax = 0.58 e Å^−3
36 restraints	Δρmin = −0.82 e Å^−3

Special details

Refinement. Sfls F² σ weight full_matrix

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

	x	y	z	Uiso*/Ueq
Cd1a	0.95302 (4)	0.17800 (3)	0.11266 (2)	0.0247 (3)
C11a	1.0232 (7)	0.3112 (5)	0.0384 (4)	0.039 (5)
C12a	0.9143 (6)	0.3072 (5)	0.0344 (3)	0.035 (5)
C13a	0.8731 (7)	0.3784 (5)	0.0240 (4)	0.048 (6)
C1a	1.0885 (6)	0.2039 (4)	0.0075 (3)	0.044 (5)
C21a	0.9459 (8)	0.0834 (4)	0.0003 (3)	0.039 (5)
C22a	0.8427 (6)	0.0835 (4)	0.0189 (4)	0.032 (5)
C23a	0.7773 (8)	0.0654 (5)	−0.0276 (4)	0.058 (7)
C2a	1.1025 (5)	0.1296 (4)	0.0213 (3)	0.039 (5)
C31a	0.9472 (7)	0.0353 (4)	0.1860 (3)	0.035 (4)
C32a	0.8556 (7)	0.0723 (5)	0.1969 (3)	0.038 (5)
C33a	0.7777 (7)	0.0243 (6)	0.2153 (4)	0.049 (6)
C3a	1.0387 (5)	0.0336 (3)	0.0726 (3)	0.034 (4)
C41a	1.0188 (7)	0.2620 (4)	0.2215 (4)	0.039 (5)
C42a	0.9232 (6)	0.2930 (4)	0.2063 (3)	0.035 (5)
C43a	0.8754 (8)	0.3271 (6)	0.2535 (4)	0.057 (6)
C4a	1.0860 (5)	0.0441 (4)	0.1272 (3)	0.031 (4)
C5a	1.0744 (5)	0.1120 (4)	0.2110 (3)	0.041 (5)
C6a	1.1312 (5)	0.1747 (3)	0.1953 (3)	0.038 (4)
C7a	1.1246 (5)	0.2809 (4)	0.1453 (3)	0.040 (5)
C8a	1.1520 (5)	0.2582 (4)	0.0895 (3)	0.042 (5)
N1a	1.0658 (5)	0.2450 (4)	0.0561 (3)	0.033 (4)
N2a	1.0147 (5)	0.0985 (4)	0.0448 (3)	0.032 (4)
N3a	1.0210 (5)	0.0816 (4)	0.1643 (3)	0.034 (5)
N4a	1.0675 (5)	0.2295 (3)	0.1753 (3)	0.030 (4)
O12a	0.8839 (3)	0.2808 (2)	0.0844 (2)	0.034 (3)
O22a	0.8256 (3)	0.1505 (3)	0.0383 (2)	0.043 (3)
O32a	0.8292 (3)	0.1014 (3)	0.1456 (2)	0.037 (3)
O42a	0.8638 (4)	0.2357 (2)	0.1886 (2)	0.035 (3)
Cd1b	0.54836 (5)	0.32404 (3)	0.38430 (2)	0.0259 (3)
C11b	0.4846 (7)	0.2184 (5)	0.2849 (4)	0.037 (5)
C12b	0.5917 (6)	0.2312 (4)	0.2795 (3)	0.035 (5)
C13b	0.6405 (8)	0.1722 (5)	0.2516 (4)	0.053 (6)
C1b	0.4114 (5)	0.3304 (4)	0.2785 (2)	0.036 (4)
C21b	0.5496 (7)	0.4509 (4)	0.2976 (4)	0.043 (5)
C22b	0.6524 (7)	0.4484 (4)	0.3165 (4)	0.041 (5)
C23b	0.7180 (7)	0.4816 (5)	0.2756 (5)	0.050 (6)
C2b	0.3951 (5)	0.3972 (4)	0.3068 (3)	0.039 (5)
C31b	0.5473 (8)	0.4367 (5)	0.4859 (3)	0.042 (5)
C32b	0.6415 (7)	0.3988 (5)	0.4890 (4)	0.042 (5)
C33b	0.7166 (7)	0.4400 (6)	0.5188 (4)	0.052 (6)
C3b	0.4545 (5)	0.4732 (4)	0.3766 (3)	0.043 (5)
C41b	0.4900 (7)	0.2043 (5)	0.4702 (4)	0.046 (6)
C42b	0.5809 (6)	0.1813 (5)	0.4461 (3)	0.039 (4)
C43b	0.6312 (9)	0.1273 (6)	0.4793 (5)	0.063 (8)
C4b	0.4100 (5)	0.4440 (4)	0.4267 (3)	0.047 (5)
C5b	0.4229 (6)	0.3513 (4)	0.4931 (3)	0.051 (6)
C6b	0.3692 (5)	0.2952 (4)	0.4650 (3)	0.050 (5)
C7b	0.3810 (5)	0.2104 (4)	0.3950 (3)	0.045 (5)
C8b	0.3537 (5)	0.2494 (4)	0.3449 (3)	0.038 (5)
N1b	0.4381 (5)	0.2753 (3)	0.3160 (3)	0.034 (4)
N2b	0.4814 (5)	0.4205 (4)	0.3359 (3)	0.028 (4)
N3b	0.4756 (5)	0.3969 (4)	0.4556 (3)	0.035 (4)
N4b	0.4367 (5)	0.2508 (4)	0.4343 (3)	0.036 (4)
O12b	0.6242 (4)	0.2387 (3)	0.3331 (2)	0.040 (3)
O22b	0.6717 (3)	0.3780 (3)	0.3225 (2)	0.042 (3)
O32b	0.6686 (3)	0.3887 (3)	0.4342 (2)	0.036 (3)
O42b	0.6403 (3)	0.2413 (3)	0.4435 (2)	0.037 (3)
N1c	1.0383 (14)	0.0027 (7)	0.3480 (5)	0.093 (10)
C1c	0.8509 (6)	0.1697 (4)	0.3686 (4)	0.036 (5)
C2c	0.9506 (5)	0.1793 (4)	0.3652 (3)	0.037 (5)
C3c	1.0129 (7)	0.1250 (5)	0.3580 (4)	0.050 (7)
C4c	0.9741 (8)	0.0610 (6)	0.3548 (4)	0.054 (7)
C5c	0.8763 (8)	0.0486 (5)	0.3561 (4)	0.059 (7)
C6c	0.8171 (7)	0.1031 (4)	0.3642 (5)	0.059 (7)
O1c	1.0048 (9)	−0.0544 (6)	0.3463 (5)	0.130 (10)
O2c	1.1233 (9)	0.0135 (6)	0.3444 (5)	0.117 (10)
O3c	0.7935 (4)	0.2206 (3)	0.3764 (3)	0.043 (4)
N1d	0.4546 (12)	0.4982 (6)	0.1474 (4)	0.070 (8)
C1d	0.6527 (5)	0.3365 (4)	0.1324 (3)	0.034 (5)
C2d	0.5541 (6)	0.3233 (4)	0.1383 (3)	0.037 (5)
C3d	0.4892 (6)	0.3765 (4)	0.1432 (3)	0.035 (6)
C4d	0.5215 (8)	0.4429 (5)	0.1423 (4)	0.043 (6)
C5d	0.6180 (7)	0.4573 (5)	0.1359 (4)	0.056 (7)
C6d	0.6829 (7)	0.4046 (4)	0.1328 (4)	0.041 (6)
O1d	0.4833 (9)	0.5564 (6)	0.1432 (4)	0.117 (9)
O2d	0.3694 (9)	0.4835 (6)	0.1586 (5)	0.111 (9)
O3d	0.7124 (4)	0.2866 (3)	0.1274 (3)	0.043 (4)
Cl1e	1.1205 (2)	0.35364 (14)	0.36630 (14)	0.0559 (17)
O1e	1.0271 (4)	0.3782 (4)	0.3755 (4)	0.114 (6)
O2e	1.1308 (6)	0.2878 (4)	0.3909 (4)	0.093 (6)
O3e	1.1850 (5)	0.4003 (4)	0.3902 (3)	0.057 (4)
O4e	1.1413 (7)	0.3506 (5)	0.3103 (3)	0.123 (8)
Cl1f	0.39051 (18)	0.14944 (15)	0.13008 (12)	0.0477 (15)
O1f	0.4708 (5)	0.1443 (4)	0.0940 (3)	0.092 (5)
O2f	0.3141 (4)	0.1103 (4)	0.1085 (3)	0.055 (4)
O3f	0.3633 (5)	0.2165 (4)	0.1377 (5)	0.126 (7)
O4f	0.4193 (6)	0.1221 (4)	0.1804 (3)	0.102 (6)
O5e	0.8348 (4)	0.3481 (3)	0.3951 (3)	0.048 (4)
O5f	0.6691 (4)	0.1599 (3)	0.1045 (3)	0.046 (4)
H1a	0.81763	0.26789	0.08554	0.08000*
H2a	0.76585	0.15492	0.05870	0.08000*
H3a	0.77386	0.12939	0.14660	0.08000*
H4a	0.80939	0.24828	0.16768	0.08000*
H1b	0.68680	0.22275	0.33958	0.08000*
H2b	0.73656	0.36771	0.33147	0.08000*
H3b	0.72938	0.36772	0.42937	0.08000*
H4b	0.69421	0.23713	0.42047	0.08000*
H11a	1.03710	0.20778	−0.01747	0.07000*
H12a	1.14528	0.22071	−0.00847	0.07000*
H21a	1.11849	0.10543	−0.01050	0.07000*
H22a	1.15287	0.12577	0.04653	0.07000*
H31a	0.98134	0.00843	0.07755	0.07000*
H32a	1.08104	0.00846	0.05029	0.07000*
H41a	1.10090	0.00103	0.14230	0.07000*
H42a	1.14295	0.06963	0.12259	0.07000*
H51a	1.03000	0.12404	0.23803	0.07000*
H52a	1.11759	0.07878	0.22460	0.07000*
H61a	1.16475	0.19082	0.22604	0.07000*
H62a	1.17559	0.16294	0.16805	0.07000*
H71a	1.08800	0.32145	0.14264	0.07000*
H72a	1.18145	0.28977	0.16494	0.07000*
H81a	1.18854	0.29348	0.07289	0.07000*
H82a	1.18908	0.21829	0.09169	0.07000*
H111a	1.03992	0.34532	0.06353	0.07000*
H112a	1.04841	0.32261	0.00405	0.07000*
H211a	0.95311	0.11676	−0.02691	0.07000*
H212a	0.96013	0.03974	−0.01406	0.07000*
H311a	0.93529	0.00019	0.16056	0.07000*
H312a	0.96985	0.01567	0.21851	0.07000*
H411a	1.00896	0.22879	0.24865	0.07000*
H412a	1.05898	0.29711	0.23525	0.07000*
H121a	0.89321	0.27958	0.00543	0.07000*
H221a	0.83018	0.05101	0.04627	0.07000*
H321a	0.86407	0.10524	0.22454	0.07000*
H421a	0.93177	0.32621	0.17916	0.07000*
H131a	0.89050	0.40766	0.05262	0.07000*
H132a	0.89848	0.39559	−0.00880	0.07000*
H133a	0.80563	0.37593	0.02140	0.07000*
H231a	0.78576	0.09787	−0.05581	0.07000*
H232a	0.79395	0.02147	−0.04095	0.07000*
H233a	0.71316	0.06553	−0.01625	0.07000*
H331a	0.76684	−0.00853	0.18872	0.07000*
H332a	0.79839	0.00267	0.24781	0.07000*
H333a	0.72006	0.04817	0.22279	0.07000*
H431a	0.86636	0.29519	0.28128	0.07000*
H432a	0.91679	0.36276	0.26611	0.07000*
H433a	0.81607	0.34680	0.24392	0.07000*
H11b	0.46122	0.33630	0.25294	0.07000*
H12b	0.35421	0.31791	0.26030	0.07000*
H21b	0.37763	0.43056	0.28114	0.07000*
H22b	0.34431	0.39156	0.33198	0.07000*
H31b	0.51031	0.49760	0.38645	0.07000*
H32b	0.40982	0.50343	0.36053	0.07000*
H41b	0.39395	0.48060	0.45019	0.07000*
H42b	0.35381	0.42010	0.41717	0.07000*
H51b	0.46752	0.33134	0.51725	0.07000*
H52b	0.37836	0.37788	0.51291	0.07000*
H61b	0.33657	0.26852	0.49092	0.07000*
H62b	0.32455	0.31466	0.44082	0.07000*
H71b	0.41803	0.17216	0.38459	0.07000*
H72b	0.32397	0.19532	0.41205	0.07000*
H81b	0.31882	0.22009	0.32170	0.07000*
H82b	0.31446	0.28680	0.35487	0.07000*
H111b	0.47461	0.17688	0.30329	0.07000*
H112b	0.45691	0.21609	0.25013	0.07000*
H211b	0.54531	0.42670	0.26477	0.07000*
H212b	0.53249	0.49689	0.29229	0.07000*
H311b	0.55669	0.47901	0.46821	0.07000*
H312b	0.52396	0.44454	0.52116	0.07000*
H411b	0.50338	0.22709	0.50300	0.07000*
H412b	0.45126	0.16543	0.47746	0.07000*
H121b	0.60579	0.26989	0.25807	0.07000*
H221b	0.66277	0.47279	0.34886	0.07000*
H321b	0.63479	0.35761	0.50824	0.07000*
H421b	0.56864	0.16124	0.41205	0.07000*
H131b	0.63037	0.13238	0.27209	0.07000*
H132b	0.61340	0.16707	0.21693	0.07000*
H133b	0.70702	0.18039	0.24827	0.07000*
H231b	0.71283	0.45876	0.24247	0.07000*
H232b	0.69926	0.52807	0.27123	0.07000*
H233b	0.78258	0.48061	0.28752	0.07000*
H331b	0.72667	0.48179	0.50024	0.07000*
H332b	0.69509	0.44889	0.55404	0.07000*
H333b	0.77611	0.41637	0.52054	0.07000*
H431b	0.64450	0.14549	0.51378	0.07000*
H432b	0.59026	0.08912	0.48262	0.07000*
H433b	0.68985	0.11262	0.46362	0.07000*
H2c	0.97556	0.22406	0.36790	0.08000*
H3c	1.08020	0.13227	0.35539	0.08000*
H5c	0.85176	0.00399	0.35248	0.08000*
H6c	0.75018	0.09534	0.36576	0.08000*
H2d	0.53197	0.27767	0.13910	0.08000*
H3d	0.42312	0.36724	0.14708	0.08000*
H5d	0.63959	0.50340	0.13453	0.08000*
H6d	0.74880	0.41462	0.13012	0.08000*
H51e	0.82830	0.31400	0.37941	0.08000*
H52e	0.88089	0.37200	0.38460	0.08000*
H51f	0.67160	0.20089	0.11250	0.08000*
H52f	0.62100	0.14000	0.10600	0.08000*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1a	0.0188 (3)	0.0284 (4)	0.0268 (3)	0.0008 (3)	0.0012 (3)	0.0003 (3)
C11a	0.029 (4)	0.044 (5)	0.045 (5)	−0.005 (4)	−0.001 (4)	0.014 (4)
C12a	0.031 (4)	0.039 (5)	0.034 (4)	−0.001 (4)	−0.004 (4)	−0.000 (4)
C13a	0.042 (6)	0.047 (6)	0.056 (6)	0.015 (5)	−0.009 (5)	0.013 (5)
C1a	0.033 (4)	0.049 (5)	0.048 (5)	−0.001 (4)	0.020 (4)	0.003 (4)
C21a	0.042 (5)	0.041 (5)	0.035 (4)	0.013 (4)	−0.002 (4)	0.000 (4)
C22a	0.019 (4)	0.036 (5)	0.042 (5)	0.008 (4)	−0.001 (4)	−0.006 (4)
C23a	0.067 (8)	0.047 (6)	0.060 (6)	0.009 (5)	−0.030 (6)	−0.004 (5)
C2a	0.033 (5)	0.047 (5)	0.035 (5)	−0.001 (4)	0.014 (4)	0.003 (4)
C31a	0.036 (4)	0.036 (4)	0.033 (4)	−0.001 (4)	0.005 (4)	0.006 (3)
C32a	0.031 (5)	0.046 (5)	0.037 (5)	−0.007 (4)	0.007 (4)	−0.004 (4)
C33a	0.043 (6)	0.054 (6)	0.050 (6)	−0.007 (5)	0.017 (5)	−0.008 (5)
C3a	0.034 (4)	0.034 (4)	0.035 (4)	0.005 (4)	0.001 (4)	−0.003 (3)
C41a	0.042 (5)	0.036 (5)	0.038 (5)	−0.001 (4)	−0.009 (4)	−0.006 (4)
C42a	0.036 (5)	0.034 (4)	0.036 (5)	−0.004 (4)	−0.001 (4)	−0.010 (4)
C43a	0.050 (6)	0.062 (7)	0.060 (6)	0.013 (6)	0.009 (5)	−0.020 (6)
C4a	0.024 (4)	0.034 (4)	0.036 (4)	0.005 (3)	−0.001 (3)	0.008 (3)
C5a	0.029 (5)	0.054 (6)	0.041 (5)	0.004 (4)	−0.005 (4)	0.004 (4)
C6a	0.026 (4)	0.039 (4)	0.048 (4)	0.010 (4)	−0.011 (3)	0.001 (4)
C7a	0.029 (4)	0.036 (5)	0.055 (6)	−0.005 (4)	−0.007 (4)	−0.006 (4)
C8a	0.027 (4)	0.049 (5)	0.051 (5)	−0.001 (4)	0.006 (4)	0.004 (4)
N1a	0.024 (4)	0.038 (4)	0.037 (4)	0.001 (4)	0.010 (3)	0.005 (3)
N2a	0.028 (4)	0.044 (5)	0.024 (4)	−0.002 (4)	0.003 (3)	0.004 (4)
N3a	0.020 (4)	0.034 (5)	0.049 (5)	0.002 (4)	0.001 (4)	0.002 (4)
N4a	0.021 (4)	0.035 (4)	0.033 (4)	−0.002 (3)	−0.007 (3)	−0.003 (3)
O12a	0.027 (3)	0.035 (3)	0.040 (3)	0.000 (2)	−0.001 (2)	0.010 (2)
O22a	0.032 (3)	0.042 (3)	0.056 (4)	0.001 (2)	0.006 (3)	−0.010 (3)
O32a	0.019 (3)	0.042 (3)	0.048 (3)	−0.001 (2)	−0.002 (2)	0.004 (3)
O42a	0.031 (3)	0.033 (3)	0.041 (3)	0.003 (2)	−0.002 (3)	−0.001 (2)
Cd1b	0.0200 (3)	0.0305 (4)	0.0271 (3)	0.0015 (3)	0.0015 (3)	−0.0035 (3)
C11b	0.033 (5)	0.039 (5)	0.039 (5)	0.003 (4)	0.003 (4)	−0.007 (4)
C12b	0.038 (5)	0.035 (5)	0.032 (4)	0.005 (4)	0.007 (4)	−0.001 (4)
C13b	0.058 (6)	0.053 (6)	0.048 (5)	0.005 (6)	0.015 (5)	−0.011 (5)
C1b	0.038 (4)	0.043 (5)	0.027 (4)	−0.000 (4)	0.000 (3)	0.001 (4)
C21b	0.036 (5)	0.040 (5)	0.054 (5)	−0.000 (5)	−0.004 (5)	−0.002 (4)
C22b	0.036 (5)	0.038 (5)	0.048 (5)	−0.004 (4)	−0.005 (4)	0.003 (4)
C23b	0.040 (6)	0.046 (6)	0.065 (7)	−0.019 (5)	0.008 (5)	−0.003 (5)
C2b	0.028 (5)	0.038 (5)	0.051 (5)	0.003 (4)	−0.011 (4)	−0.002 (4)
C31b	0.030 (5)	0.061 (6)	0.035 (4)	0.008 (5)	0.000 (4)	−0.026 (4)
C32b	0.034 (5)	0.060 (6)	0.033 (5)	−0.008 (5)	0.002 (4)	−0.010 (4)
C33b	0.031 (5)	0.071 (7)	0.055 (6)	0.007 (5)	−0.005 (5)	−0.013 (5)
C3b	0.029 (4)	0.043 (4)	0.056 (5)	0.009 (4)	−0.005 (4)	−0.006 (4)
C41b	0.045 (6)	0.061 (7)	0.031 (5)	−0.008 (5)	0.005 (4)	0.012 (4)
C42b	0.033 (4)	0.035 (4)	0.049 (5)	−0.007 (4)	−0.006 (4)	0.005 (5)
C43b	0.063 (8)	0.060 (7)	0.064 (8)	−0.013 (7)	0.003 (7)	0.017 (6)
C4b	0.036 (5)	0.050 (5)	0.053 (5)	0.008 (4)	−0.000 (4)	−0.026 (4)
C5b	0.042 (5)	0.071 (7)	0.038 (5)	0.005 (5)	0.010 (4)	−0.016 (5)
C6b	0.030 (4)	0.076 (6)	0.043 (5)	−0.003 (4)	0.017 (4)	−0.002 (4)
C7b	0.036 (5)	0.058 (5)	0.042 (5)	−0.020 (4)	0.004 (4)	0.010 (4)
C8b	0.023 (4)	0.046 (5)	0.044 (5)	−0.008 (4)	−0.008 (3)	−0.003 (4)
N1b	0.033 (4)	0.032 (4)	0.038 (4)	0.004 (4)	−0.000 (3)	−0.003 (3)
N2b	0.026 (4)	0.034 (5)	0.024 (4)	−0.000 (4)	0.004 (4)	−0.008 (3)
N3b	0.024 (4)	0.042 (5)	0.037 (4)	0.004 (4)	0.003 (3)	−0.011 (4)
N4b	0.027 (4)	0.050 (4)	0.032 (4)	0.006 (4)	0.003 (3)	−0.007 (3)
O12b	0.028 (3)	0.049 (4)	0.041 (3)	0.009 (3)	−0.001 (3)	−0.005 (3)
O22b	0.025 (3)	0.043 (3)	0.056 (4)	0.002 (3)	0.004 (3)	−0.005 (3)
O32b	0.025 (3)	0.044 (3)	0.039 (3)	0.004 (2)	0.005 (2)	−0.011 (3)
O42b	0.027 (3)	0.043 (3)	0.041 (3)	−0.001 (3)	0.004 (2)	0.003 (3)
N1c	0.134 (12)	0.080 (10)	0.065 (7)	0.059 (11)	−0.019 (9)	−0.006 (7)
C1c	0.038 (5)	0.030 (5)	0.040 (5)	−0.001 (5)	−0.005 (4)	0.003 (5)
C2c	0.022 (5)	0.048 (6)	0.042 (5)	−0.001 (5)	0.009 (4)	0.009 (5)
C3c	0.048 (8)	0.073 (9)	0.029 (6)	0.020 (7)	0.005 (5)	0.012 (6)
C4c	0.064 (8)	0.058 (8)	0.041 (6)	0.042 (7)	−0.009 (6)	0.005 (6)
C5c	0.098 (10)	0.035 (6)	0.045 (6)	−0.013 (7)	−0.014 (6)	0.003 (5)
C6c	0.047 (7)	0.043 (6)	0.086 (9)	−0.012 (5)	−0.015 (6)	0.002 (6)
O1c	0.192 (15)	0.045 (6)	0.153 (10)	0.047 (7)	−0.002 (8)	−0.021 (6)
O2c	0.103 (9)	0.127 (10)	0.121 (10)	0.084 (8)	−0.003 (8)	−0.002 (7)
O3c	0.024 (3)	0.037 (3)	0.068 (4)	−0.001 (3)	0.008 (3)	−0.011 (4)
N1d	0.102 (9)	0.054 (8)	0.055 (6)	0.045 (8)	−0.016 (7)	−0.006 (5)
C1d	0.022 (5)	0.044 (6)	0.036 (5)	0.000 (4)	0.001 (4)	−0.007 (5)
C2d	0.036 (5)	0.036 (5)	0.040 (5)	0.013 (5)	−0.009 (5)	−0.002 (5)
C3d	0.030 (6)	0.046 (7)	0.027 (5)	0.013 (5)	0.001 (4)	−0.000 (4)
C4d	0.072 (8)	0.035 (6)	0.023 (5)	0.012 (6)	0.003 (5)	−0.005 (4)
C5d	0.091 (10)	0.036 (6)	0.040 (6)	0.001 (6)	−0.002 (6)	0.004 (5)
C6d	0.044 (6)	0.036 (5)	0.041 (5)	−0.010 (5)	0.010 (5)	−0.010 (4)
O1d	0.165 (12)	0.061 (7)	0.126 (8)	0.060 (7)	−0.010 (7)	0.009 (6)
O2d	0.083 (8)	0.117 (9)	0.132 (10)	0.064 (7)	−0.008 (8)	−0.019 (7)
O3d	0.029 (4)	0.045 (4)	0.055 (4)	0.004 (3)	−0.005 (3)	−0.002 (3)
Cl1e	0.0293 (14)	0.0484 (16)	0.090 (2)	−0.0029 (12)	−0.0114 (14)	−0.0022 (15)
O1e	0.021 (3)	0.071 (4)	0.251 (12)	0.000 (3)	0.017 (6)	0.029 (6)
O2e	0.057 (5)	0.051 (4)	0.170 (8)	−0.002 (4)	−0.010 (5)	0.009 (5)
O3e	0.045 (4)	0.073 (4)	0.053 (4)	−0.029 (4)	0.009 (4)	−0.002 (4)
O4e	0.145 (8)	0.153 (9)	0.070 (5)	−0.033 (7)	−0.041 (6)	−0.032 (5)
Cl1f	0.0283 (13)	0.0532 (16)	0.0616 (17)	−0.0069 (11)	−0.0007 (11)	−0.0029 (13)
O1f	0.031 (3)	0.169 (8)	0.077 (5)	−0.035 (5)	0.001 (3)	−0.013 (5)
O2f	0.024 (3)	0.070 (4)	0.072 (5)	−0.012 (3)	−0.007 (4)	−0.013 (4)
O3f	0.038 (4)	0.047 (5)	0.293 (13)	−0.005 (4)	−0.019 (6)	−0.015 (6)
O4f	0.128 (8)	0.107 (6)	0.072 (5)	−0.026 (6)	−0.035 (5)	0.012 (5)
O5e	0.024 (4)	0.045 (4)	0.075 (5)	−0.002 (3)	0.015 (3)	−0.009 (4)
O5f	0.022 (3)	0.049 (4)	0.066 (4)	−0.000 (3)	−0.002 (3)	−0.014 (4)

Geometric parameters (Å, º)

Cd1a—N1a	2.492 (7)	C12b—C13b	1.515 (13)
Cd1a—N2a	2.458 (7)	C13b—H131b	0.945
Cd1a—N3a	2.480 (7)	C13b—H133b	0.948
Cd1a—N4a	2.454 (7)	C13b—H132b	0.949
Cd1a—O12a	2.349 (5)	C1b—H11b	0.951 (7)
Cd1a—O22a	2.626 (5)	C1b—H12b	0.952 (7)
Cd1a—O32a	2.438 (5)	C1b—N1b	1.478 (9)
Cd1a—O42a	2.534 (5)	C1b—C2b	1.508 (10)
O12a—O3d	2.630 (8)	C21b—H212b	0.946
O22a—O5f	2.746 (8)	C21b—H211b	0.946
O32a—O5f	2.720 (8)	C21b—N2b	1.476 (12)
O42a—O3d	2.797 (8)	C21b—C22b	1.514 (14)
O5f—O3d	2.627 (9)	C22b—H221b	0.949
O5f—O1f	2.803 (9)	C22b—O22b	1.418 (10)
Cd1b—N1b	2.488 (7)	C22b—C23b	1.519 (14)
Cd1b—N2b	2.435 (7)	C23b—H231b	0.942
Cd1b—N3b	2.498 (7)	C23b—H233b	0.951
Cd1b—N4b	2.463 (7)	C23b—H232b	0.957
Cd1b—O12b	2.359 (5)	C2b—H21b	0.947
Cd1b—O22b	2.544 (5)	C2b—H22b	0.955
Cd1b—O32b	2.448 (5)	C2b—N2b	1.481 (10)
Cd1b—O42b	2.543 (5)	C31b—H311b	0.950
O12b—O3c	2.627 (8)	C31b—H312b	0.950
O22b—O5e	2.970 (8)	C31b—N3b	1.479 (12)
O32b—O5e	2.645 (8)	C31b—C32b	1.516 (14)
O42b—O3c	2.749 (8)	C32b—H321b	0.946
O5e—O3c	2.615 (8)	C32b—O32b	1.428 (10)
O5e—O1e	2.798 (9)	C32b—C33b	1.521 (14)
C11a—H111a	0.947	C33b—H332b	0.944
C11a—H112a	0.950	C33b—H331b	0.952
C11a—N1a	1.499 (12)	C33b—H333b	0.956
C11a—C12a	1.529 (12)	C3b—H31b	0.948 (7)
C12a—H121a	0.950	C3b—H32b	0.951 (7)
C12a—O12a	1.413 (9)	C3b—N2b	1.497 (10)
C12a—C13a	1.536 (13)	C3b—C4b	1.507 (10)
C13a—H133a	0.948	C41b—H411b	0.949
C13a—H131a	0.949	C41b—H412b	0.955
C13a—H132a	0.952	C41b—C42b	1.477 (13)
C1a—H12a	0.948	C41b—N4b	1.479 (12)
C1a—H11a	0.954	C42b—H421b	0.949
C1a—N1a	1.489 (10)	C42b—O42b	1.446 (10)
C1a—C2a	1.515 (10)	C42b—C43b	1.519 (15)
C21a—H211a	0.948	C43b—H431b	0.947 (12)
C21a—H212a	0.950	C43b—H432b	0.948 (12)
C21a—N2a	1.499 (12)	C43b—H433b	0.954 (12)
C21a—C22a	1.516 (14)	C4b—H42b	0.946 (7)
C22a—H221a	0.950	C4b—H41b	0.954 (7)
C22a—O22a	1.425 (10)	C4b—N3b	1.491 (10)
C22a—C23a	1.517 (14)	C5b—H51b	0.951
C23a—H233a	0.941	C5b—H52b	0.951
C23a—H232a	0.955	C5b—N3b	1.489 (11)
C23a—H231a	0.957	C5b—C6b	1.507 (11)
C2a—H22a	0.947	C6b—H62b	0.948 (7)
C2a—H21a	0.950	C6b—H61b	0.948
C2a—N2a	1.491 (10)	C6b—N4b	1.497 (10)
C31a—H312a	0.951	C7b—H71b	0.949
C31a—H311a	0.952	C7b—H72b	0.951 (7)
C31a—N3a	1.478 (11)	C7b—N4b	1.482 (10)
C31a—C32a	1.499 (13)	C7b—C8b	1.515 (10)
C32a—H321a	0.952	C8b—H81b	0.950 (7)
C32a—O32a	1.447 (10)	C8b—H82b	0.952 (7)
C32a—C33a	1.513 (14)	C8b—N1b	1.474 (10)
C33a—H331a	0.937	O12b—H1b	0.945 (5)
C33a—H333a	0.952	O22b—H2b	0.956 (5)
C33a—H332a	0.959	O32b—H3b	0.952 (5)
C3a—H31a	0.951	O42b—H4b	0.951 (5)
C3a—H32a	0.951	N1c—O2c	1.21 (2)
C3a—N2a	1.488 (10)	N1c—O1c	1.22 (2)
C3a—C4a	1.525 (9)	N1c—C4c	1.47 (2)
C41a—H411a	0.949	C1c—O3c	1.297 (10)
C41a—H412a	0.954	C1c—C6c	1.397 (12)
C41a—N4a	1.483 (11)	C1c—C2c	1.410 (11)
C41a—C42a	1.517 (12)	C2c—H2c	0.950
C42a—H421a	0.947	C2c—C3c	1.389 (13)
C42a—O42a	1.468 (9)	C3c—H3c	0.955
C42a—C43a	1.508 (13)	C3c—C4c	1.373 (15)
C43a—H431a	0.942	C4c—C5c	1.392 (16)
C43a—H433a	0.947	C5c—H5c	0.947
C43a—H432a	0.961	C5c—C6c	1.369 (14)
C4a—H42a	0.948	C6c—H6c	0.950
C4a—H41a	0.951	N1d—O1d	1.219 (17)
C4a—N3a	1.491 (10)	N1d—O2d	1.26 (2)
C5a—H51a	0.945	N1d—C4d	1.439 (17)
C5a—H52a	0.952	C1d—O3d	1.293 (10)
C5a—N3a	1.506 (10)	C1d—C6d	1.405 (11)
C5a—C6a	1.518 (10)	C1d—C2d	1.412 (11)
C6a—H62a	0.948	C2d—H2d	0.950
C6a—H61a	0.952	C2d—C3d	1.390 (11)
C6a—N4a	1.485 (9)	C3d—H3d	0.947
C7a—H72a	0.950	C3d—C4d	1.383 (12)
C7a—H71a	0.951	C4d—C5d	1.389 (15)
C7a—N4a	1.488 (10)	C5d—H5d	0.956
C7a—C8a	1.508 (10)	C5d—C6d	1.380 (13)
C8a—H82a	0.942	C6d—H6d	0.945
C8a—H81a	0.956	Cl1e—O1e	1.413 (7)
C8a—N1a	1.488 (10)	Cl1e—O3e	1.417 (7)
O12a—H1a	0.961	Cl1e—O4e	1.425 (9)
O22a—H2a	0.982	Cl1e—O2e	1.440 (8)
O32a—H3a	0.951	Cl1f—O3f	1.385 (8)
O42a—H4a	0.956	Cl1f—O4f	1.421 (8)
C11b—H111b	0.948	Cl1f—O2f	1.423 (7)
C11b—H112b	0.948	Cl1f—O1f	1.442 (7)
C11b—N1b	1.508 (11)	O5e—H51e	0.781
C11b—C12b	1.526 (13)	O5e—H52e	0.840
C12b—H121b	0.950	O5f—H52f	0.780
C12b—O12b	1.417 (9)	O5f—H51f	0.831
O12a—Cd1a—O32a	109.87 (16)	H111b—C11b—H112b	109.8 (9)
O12a—Cd1a—N4a	95.99 (19)	H111b—C11b—N1b	109.1
O12a—Cd1a—N2a	119.1 (2)	H111b—C11b—C12b	109.2
O12a—Cd1a—N3a	166.2 (2)	H112b—C11b—N1b	109.2
O12a—Cd1a—N1a	68.7 (2)	H112b—C11b—C12b	109.3
O12a—Cd1a—O42a	68.62 (16)	N1b—C11b—C12b	110.2 (7)
O12a—Cd1a—O22a	71.68 (16)	H121b—C12b—O12b	112.3 (7)
O32a—Cd1a—N4a	120.4 (2)	H121b—C12b—C13b	105.2 (7)
O32a—Cd1a—N2a	95.0 (2)	H121b—C12b—C11b	112.6
O32a—Cd1a—N3a	68.0 (2)	O12b—C12b—C13b	111.5 (7)
O32a—Cd1a—N1a	165.2 (2)	O12b—C12b—C11b	104.5 (6)
O32a—Cd1a—O42a	71.10 (16)	C13b—C12b—C11b	110.9 (7)
O32a—Cd1a—O22a	68.15 (16)	H131b—C13b—H133b	109.6
N4a—Cd1a—N2a	118.0 (2)	H131b—C13b—H132b	110.0
N4a—Cd1a—N3a	74.7 (2)	H131b—C13b—C12b	108.7 (9)
N4a—Cd1a—N1a	74.2 (2)	H133b—C13b—H132b	109.3
N4a—Cd1a—O42a	70.3 (2)	H133b—C13b—C12b	110.7 (9)
N4a—Cd1a—O22a	167.36 (19)	H132b—C13b—C12b	108.6 (9)
N2a—Cd1a—N3a	74.6 (2)	H11b—C1b—H12b	109.3 (6)
N2a—Cd1a—N1a	74.1 (2)	H11b—C1b—N1b	109.0 (6)
N2a—Cd1a—O42a	166.1 (2)	H11b—C1b—C2b	108.5 (6)
N2a—Cd1a—O22a	67.9 (2)	H12b—C1b—N1b	108.9 (6)
N3a—Cd1a—N1a	117.0 (2)	H12b—C1b—C2b	108.7 (6)
N3a—Cd1a—O42a	98.3 (2)	N1b—C1b—C2b	112.5 (6)
N3a—Cd1a—O22a	117.9 (2)	H212b—C21b—H211b	110.2 (9)
N1a—Cd1a—O42a	119.8 (2)	H212b—C21b—N2b	108.2
N1a—Cd1a—O22a	98.07 (19)	H212b—C21b—C22b	108.4
O42a—Cd1a—O22a	106.49 (16)	H211b—C21b—N2b	108.3
H111a—C11a—H112a	109.7	H211b—C21b—C22b	108.2 (9)
H111a—C11a—N1a	108.8	N2b—C21b—C22b	113.6 (7)
H111a—C11a—C12a	109.0	H221b—C22b—O22b	112.1
H112a—C11a—N1a	108.8	H221b—C22b—C21b	113.2
H112a—C11a—C12a	108.9	H221b—C22b—C23b	104.9
N1a—C11a—C12a	111.7 (7)	O22b—C22b—C21b	104.2 (7)
H121a—C12a—O12a	111.4	O22b—C22b—C23b	112.1 (7)
H121a—C12a—C11a	112.9	C21b—C22b—C23b	110.6 (8)
H121a—C12a—C13a	106.0 (7)	H231b—C23b—H233b	109.6
O12a—C12a—C11a	105.3 (6)	H231b—C23b—H232b	109.6
O12a—C12a—C13a	111.8 (7)	H231b—C23b—C22b	109.5 (9)
C11a—C12a—C13a	109.7 (7)	H233b—C23b—H232b	108.4
H133a—C13a—H131a	109.7	H233b—C23b—C22b	110.9
H133a—C13a—H132a	109.4	H232b—C23b—C22b	108.8 (9)
H133a—C13a—C12a	109.8	H21b—C2b—H22b	109.3 (7)
H131a—C13a—H132a	109.4	H21b—C2b—N2b	109.1 (7)
H131a—C13a—C12a	109.3	H21b—C2b—C1b	109.1 (7)
H132a—C13a—C12a	109.3	H22b—C2b—N2b	108.8 (7)
H12a—C1a—H11a	109.3 (7)	H22b—C2b—C1b	108.5 (6)
H12a—C1a—N1a	109.3 (6)	N2b—C2b—C1b	112.0 (6)
H12a—C1a—C2a	108.9 (7)	H311b—C31b—H312b	109.5 (9)
H11a—C1a—N1a	109.0 (7)	H311b—C31b—N3b	108.8
H11a—C1a—C2a	108.8 (7)	H311b—C31b—C32b	109.5 (9)
N1a—C1a—C2a	111.5 (6)	H312b—C31b—N3b	108.9 (9)
H211a—C21a—H212a	109.6	H312b—C31b—C32b	109.4
H211a—C21a—N2a	108.8	N3b—C31b—C32b	110.8 (7)
H211a—C21a—C22a	108.6	H321b—C32b—O32b	113.0
H212a—C21a—N2a	108.8	H321b—C32b—C31b	111.2 (9)
H212a—C21a—C22a	108.4	H321b—C32b—C33b	106.1
N2a—C21a—C22a	112.6 (7)	O32b—C32b—C31b	104.6 (7)
H221a—C22a—O22a	110.4	O32b—C32b—C33b	110.9 (7)
H221a—C22a—C21a	113.3	C31b—C32b—C33b	111.3 (8)
H221a—C22a—C23a	106.1	H332b—C33b—H331b	109.8
O22a—C22a—C21a	105.4 (6)	H332b—C33b—H333b	109.0
O22a—C22a—C23a	111.9 (7)	H332b—C33b—C32b	109.4 (9)
C21a—C22a—C23a	109.9 (8)	H331b—C33b—H333b	108.2
H233a—C23a—H232a	109.9	H331b—C33b—C32b	109.0 (9)
H233a—C23a—H231a	109.6	H333b—C33b—C32b	111.4
H233a—C23a—C22a	110.3	H31b—C3b—H32b	109.5 (7)
H232a—C23a—H231a	108.5	H31b—C3b—N2b	108.6 (7)
H232a—C23a—C22a	109.3	H31b—C3b—C4b	108.7 (6)
H231a—C23a—C22a	109.2	H32b—C3b—N2b	108.2 (6)
H22a—C2a—H21a	109.7	H32b—C3b—C4b	108.3 (7)
H22a—C2a—N2a	108.7 (7)	N2b—C3b—C4b	113.6 (6)
H22a—C2a—C1a	108.8 (7)	H411b—C41b—H412b	109.1 (9)
H21a—C2a—N2a	108.5 (7)	H411b—C41b—C42b	109.0 (9)
H21a—C2a—C1a	108.9 (7)	H411b—C41b—N4b	109.1 (9)
N2a—C2a—C1a	112.3 (6)	H412b—C41b—C42b	108.6 (9)
H312a—C31a—H311a	109.2	H412b—C41b—N4b	108.8
H312a—C31a—N3a	109.2	C42b—C41b—N4b	112.2 (7)
H312a—C31a—C32a	109.1 (7)	H421b—C42b—O42b	113.7 (7)
H311a—C31a—N3a	109.0 (7)	H421b—C42b—C41b	109.6
H311a—C31a—C32a	108.8	H421b—C42b—C43b	106.2
N3a—C31a—C32a	111.4 (7)	O42b—C42b—C41b	105.2 (7)
H321a—C32a—O32a	113.6	O42b—C42b—C43b	109.2 (7)
H321a—C32a—C31a	110.8	C41b—C42b—C43b	113.1 (8)
H321a—C32a—C33a	107.2	H431b—C43b—H432b	109.9 (12)
O32a—C32a—C31a	104.5 (6)	H431b—C43b—H433b	108.4 (12)
O32a—C32a—C33a	109.3 (7)	H431b—C43b—C42b	108.7
C31a—C32a—C33a	111.6 (8)	H432b—C43b—H433b	108.4
H331a—C33a—H333a	109.9	H432b—C43b—C42b	108.7
H331a—C33a—H332a	109.9	H433b—C43b—C42b	112.7
H331a—C33a—C32a	109.5	H42b—C4b—H41b	109.5 (7)
H333a—C33a—H332a	108.0	H42b—C4b—N3b	108.8 (7)
H333a—C33a—C32a	111.2	H42b—C4b—C3b	109.1 (7)
H332a—C33a—C32a	108.4	H41b—C4b—N3b	108.5 (6)
H31a—C3a—H32a	109.3	H41b—C4b—C3b	108.5 (7)
H31a—C3a—N2a	108.5	N3b—C4b—C3b	112.4 (6)
H31a—C3a—C4a	108.7	H51b—C5b—H52b	109.3
H32a—C3a—N2a	108.4	H51b—C5b—N3b	108.7 (7)
H32a—C3a—C4a	108.6	H51b—C5b—C6b	108.6
N2a—C3a—C4a	113.3 (6)	H52b—C5b—N3b	108.6
H411a—C41a—H412a	109.2	H52b—C5b—C6b	108.4 (7)
H411a—C41a—N4a	108.8	N3b—C5b—C6b	113.3 (6)
H411a—C41a—C42a	109.1	H62b—C6b—H61b	109.8 (7)
H412a—C41a—N4a	108.5	H62b—C6b—N4b	109.1 (7)
H412a—C41a—C42a	108.5	H62b—C6b—C5b	109.2 (7)
N4a—C41a—C42a	112.7 (7)	H61b—C6b—N4b	109.1 (7)
H421a—C42a—O42a	112.7	H61b—C6b—C5b	109.2 (7)
H421a—C42a—C43a	107.8	N4b—C6b—C5b	110.4 (6)
H421a—C42a—C41a	110.1	H71b—C7b—H72b	109.5
O42a—C42a—C43a	108.9 (7)	H71b—C7b—N4b	108.5 (7)
O42a—C42a—C41a	105.4 (6)	H71b—C7b—C8b	108.3 (6)
C43a—C42a—C41a	112.0 (7)	H72b—C7b—N4b	108.3 (6)
H431a—C43a—H433a	109.8	H72b—C7b—C8b	108.3 (6)
H431a—C43a—H432a	109.2	N4b—C7b—C8b	113.9 (6)
H431a—C43a—C42a	109.6	H81b—C8b—H82b	109.3 (7)
H433a—C43a—H432a	108.2	H81b—C8b—N1b	109.0 (6)
H433a—C43a—C42a	112.0	H81b—C8b—C7b	108.8 (7)
H432a—C43a—C42a	108.1	H82b—C8b—N1b	108.9 (7)
H42a—C4a—H41a	109.5	H82b—C8b—C7b	108.7 (6)
H42a—C4a—N3a	109.0	N1b—C8b—C7b	112.1 (6)
H42a—C4a—C3a	109.3	C8b—N1b—C1b	111.0 (6)
H41a—C4a—N3a	109.2	C8b—N1b—C11b	109.8 (6)
H41a—C4a—C3a	109.1	C8b—N1b—Cd1b	107.3 (4)
N3a—C4a—C3a	110.7 (6)	C1b—N1b—C11b	109.2 (6)
H51a—C5a—H52a	109.7	C1b—N1b—Cd1b	107.8 (4)
H51a—C5a—N3a	108.9	C11b—N1b—Cd1b	111.7 (5)
H51a—C5a—C6a	108.9	C21b—N2b—C2b	109.6 (6)
H52a—C5a—N3a	108.4	C21b—N2b—C3b	108.7 (6)
H52a—C5a—C6a	108.4	C21b—N2b—Cd1b	112.7 (5)
N3a—C5a—C6a	112.5 (6)	C2b—N2b—C3b	109.9 (6)
H62a—C6a—H61a	109.5	C2b—N2b—Cd1b	108.3 (5)
H62a—C6a—N4a	109.3	C3b—N2b—Cd1b	107.6 (4)
H62a—C6a—C5a	109.3	C31b—N3b—C5b	109.6 (6)
H61a—C6a—N4a	108.8	C31b—N3b—C4b	109.5 (6)
H61a—C6a—C5a	108.8	C31b—N3b—Cd1b	112.9 (5)
N4a—C6a—C5a	111.2 (5)	C5b—N3b—C4b	111.9 (6)
H72a—C7a—H71a	109.4	C5b—N3b—Cd1b	107.6 (5)
H72a—C7a—N4a	108.4	C4b—N3b—Cd1b	105.4 (4)
H72a—C7a—C8a	108.4	C41b—N4b—C7b	109.5 (7)
H71a—C7a—N4a	108.4	C41b—N4b—C6b	111.8 (6)
H71a—C7a—C8a	108.8	C41b—N4b—Cd1b	110.3 (5)
N4a—C7a—C8a	113.4 (6)	C7b—N4b—C6b	108.5 (6)
H82a—C8a—H81a	109.6	C7b—N4b—Cd1b	108.3 (4)
H82a—C8a—N1a	109.5	C6b—N4b—Cd1b	108.5 (5)
H82a—C8a—C7a	109.4	H1b—O12b—C12b	115.0 (6)
H81a—C8a—N1a	108.6	H1b—O12b—Cd1b	124.2 (4)
H81a—C8a—C7a	108.6	C12b—O12b—Cd1b	116.0 (4)
N1a—C8a—C7a	111.1 (6)	H2b—O22b—C22b	114.3 (6)
C8a—N1a—C1a	112.0 (6)	H2b—O22b—Cd1b	114.5 (4)
C8a—N1a—C11a	109.6 (6)	C22b—O22b—Cd1b	109.9 (5)
C8a—N1a—Cd1a	106.9 (4)	H3b—O32b—C32b	114.8 (6)
C1a—N1a—C11a	108.5 (6)	H3b—O32b—Cd1b	109.0 (4)
C1a—N1a—Cd1a	107.9 (5)	C32b—O32b—Cd1b	111.9 (5)
C11a—N1a—Cd1a	112.0 (5)	H4b—O42b—C42b	114.4 (5)
C3a—N2a—C2a	110.4 (6)	H4b—O42b—Cd1b	96.2 (3)
C3a—N2a—C21a	108.6 (6)	C42b—O42b—Cd1b	104.9 (4)
C3a—N2a—Cd1a	107.8 (4)	O2c—N1c—O1c	122.5 (16)
C2a—N2a—C21a	108.7 (6)	O2c—N1c—C4c	118.2 (13)
C2a—N2a—Cd1a	107.3 (5)	O1c—N1c—C4c	119.3 (17)
C21a—N2a—Cd1a	114.1 (5)	O3c—C1c—C6c	121.7 (8)
C31a—N3a—C4a	110.4 (6)	O3c—C1c—C2c	121.2 (7)
C31a—N3a—C5a	108.0 (6)	C6c—C1c—C2c	117.0 (8)
C31a—N3a—Cd1a	113.1 (5)	H2c—C2c—C3c	119.3 (8)
C4a—N3a—C5a	111.9 (6)	H2c—C2c—C1c	118.9 (8)
C4a—N3a—Cd1a	106.9 (4)	C3c—C2c—C1c	121.8 (8)
C5a—N3a—Cd1a	106.6 (5)	H3c—C3c—C4c	121.5 (10)
C41a—N4a—C6a	109.2 (6)	H3c—C3c—C2c	120.9 (10)
C41a—N4a—C7a	110.1 (6)	C4c—C3c—C2c	117.6 (9)
C41a—N4a—Cd1a	111.7 (5)	C3c—C4c—C5c	123.2 (10)
C6a—N4a—C7a	109.8 (6)	C3c—C4c—N1c	118.8 (11)
C6a—N4a—Cd1a	107.8 (4)	C5c—C4c—N1c	118.0 (11)
C7a—N4a—Cd1a	108.2 (4)	H5c—C5c—C6c	121.4 (11)
H1a—O12a—C12a	114.5 (5)	H5c—C5c—C4c	121.1 (11)
H1a—O12a—Cd1a	99.3 (3)	C6c—C5c—C4c	117.5 (10)
C12a—O12a—Cd1a	117.1 (4)	H6c—C6c—C5c	118.4 (9)
H2a—O22a—C22a	113.5 (5)	H6c—C6c—C1c	118.8 (9)
H2a—O22a—Cd1a	101.3 (3)	C5c—C6c—C1c	122.8 (9)
C22a—O22a—Cd1a	108.3 (4)	O1d—N1d—O2d	123.1 (14)
H3a—O32a—C32a	114.5 (6)	O1d—N1d—C4d	119.2 (14)
H3a—O32a—Cd1a	103.3 (4)	O2d—N1d—C4d	117.5 (11)
C32a—O32a—Cd1a	111.1 (4)	O3d—C1d—C6d	122.0 (7)
H4a—O42a—C42a	114.7 (5)	O3d—C1d—C2d	120.2 (7)
H4a—O42a—Cd1a	95.8 (3)	C6d—C1d—C2d	117.8 (8)
C42a—O42a—Cd1a	106.8 (4)	H2d—C2d—C3d	119.8 (8)
O12b—Cd1b—N2b	117.4 (2)	H2d—C2d—C1d	119.5 (8)
O12b—Cd1b—O32b	109.54 (17)	C3d—C2d—C1d	120.7 (8)
O12b—Cd1b—N4b	98.2 (2)	H3d—C3d—C4d	120.1 (8)
O12b—Cd1b—N1b	68.6 (2)	H3d—C3d—C2d	120.2 (8)
O12b—Cd1b—N3b	167.2 (2)	C4d—C3d—C2d	119.7 (8)
O12b—Cd1b—O42b	68.29 (17)	C3d—C4d—C5d	120.8 (9)
O12b—Cd1b—O22b	70.43 (17)	C3d—C4d—N1d	120.0 (10)
N2b—Cd1b—O32b	96.4 (2)	C5d—C4d—N1d	119.2 (10)
N2b—Cd1b—N4b	117.5 (2)	H5d—C5d—C6d	120.1 (10)
N2b—Cd1b—N1b	73.9 (2)	H5d—C5d—C4d	120.3 (10)
N2b—Cd1b—N3b	75.4 (2)	C6d—C5d—C4d	119.6 (9)
N2b—Cd1b—O42b	168.3 (2)	H6d—C6d—C5d	119.3 (8)
N2b—Cd1b—O22b	68.7 (2)	H6d—C6d—C1d	119.4 (8)
O32b—Cd1b—N4b	118.9 (2)	C5d—C6d—C1d	121.3 (9)
O32b—Cd1b—N1b	166.72 (19)	O1e—Cl1e—O3e	107.4 (5)
O32b—Cd1b—N3b	67.8 (2)	O1e—Cl1e—O4e	111.1 (6)
O32b—Cd1b—O42b	71.97 (16)	O1e—Cl1e—O2e	109.4 (5)
O32b—Cd1b—O22b	67.91 (17)	O3e—Cl1e—O4e	107.9 (5)
N4b—Cd1b—N1b	74.2 (2)	O3e—Cl1e—O2e	110.0 (5)
N4b—Cd1b—N3b	73.6 (2)	O4e—Cl1e—O2e	111.0 (6)
N4b—Cd1b—O42b	69.7 (2)	O3f—Cl1f—O4f	108.5 (6)
N4b—Cd1b—O22b	168.5 (2)	O3f—Cl1f—O2f	111.1 (5)
N1b—Cd1b—N3b	117.0 (2)	O3f—Cl1f—O1f	111.5 (6)
N1b—Cd1b—O42b	117.58 (19)	O4f—Cl1f—O2f	109.9 (5)
N1b—Cd1b—O22b	99.7 (2)	O4f—Cl1f—O1f	107.5 (5)
N3b—Cd1b—O42b	99.3 (2)	O2f—Cl1f—O1f	108.2 (4)
N3b—Cd1b—O22b	117.9 (2)	H51e—O5e—H52e	114.5 (8)
O42b—Cd1b—O22b	105.88 (16)	H52f—O5f—H51f	120.8 (7)