Bis[μ-1-(1,10-phenanthrolin-2-yl)-2-pyridone]bis­{aqua­[1-(1,10-phenanthrolin-2-yl)-2-pyridone]cadmium(II)} tetra­kis(perchlorate)

In the title centrosymmetric binuclear complex, [Cd₂(C₁₇H₁₁N₃O)₄(H₂O)₂](ClO₄)₄, the Cd^II ion assumes a distorted octa­hedral geometry. There are π–π stacking inter­actions between the pyridine and 1,10-phenanthroline ring systems of adjacent ligands at the same Cd^II centre. Inter­molecular hydrogen bonds between the coordinated aqua ligand and the O atom of a keto group connect adjacent complex cations into extended chains. Hydrogen bonds also exist between the complex cations and the perchlorate anions. Compared with the fluorescence spectrum of the organic ligand, the complex displays strong fluorescent emission and an ipsochromic shift of the emission peaks, which may be attributed to the structural character.

S1. Comment

Derivatives of 1,10-phenanthroline play a pivotal role in modern coordination chemistry and a number of complexes with these ligands have been synthesized. Some of them exhibit interesting properties as molecular electrical conductors (Zheng et al. 2003), as photolumisescent materials (Zhang et al., 2006) and for cancer therapy (Liu et al., 2004). Complexes with 2-(2-keto-pyridin-1-yl)-1,10-phenanthroline (PP) as a ligand have not been reported to our knowledge to date. Our interest in synthesizing new complexes with derivatives of 1,10-phenanthroline as ligand resulted in the title binuclear complex, (I). We report here the structure and fluorescence properties of (I).

Fig. 1 shows the dinuclear cation, which sits about a crystallographic centre of inversion. The Cd^II ion assumes a distorted octahdral CdN₄O₂ coordination geometry (Table 1). Each Cd^II ion is coordinated in a bidentate fashion by the N atoms of two PP ligands. One of the PP ligands also bridges via keto atom O3 to the other Cd^II ion in the cation. The two Cd^II ions are separated by 5.8159 (11) Å. The other PP ligand only functions as a terminal bidentate ligand, but its keto atom O2 is a hydrogen-bond acceptor (Table 2). This interaction is with a water ligand of an adjacent cation and leads to the formation of a supramolecular one-dimensional chain which runs parallel to the [100] direction (Fig. 2). Table 2 and Fig. 2 also depict the hydrogen bonds and weaker C—H···O interactions between the complex cations and surrounding perchlorate anions.

The dihedral angles between the pyridine and 1,10-phenanthroline ring system planes are 64.44 (18)° for PP as a terminal ligand and 80.15 (15)° for PP as a bridging ligand. These differences can be expected in terms of steric relief. There are π–π stacking interactions between the pyridine and 1,10-phenanthroline ring systems of adjacent ligands at the same Cd^II center [Cg1···Cg2 = 3.439 (2) Å, Cg1···Cg2_perp = 3.333 Å, α = 8.05° and Cg3···Cg4 = 3.426 (3) Å, Cg3···Cg4_perp = 3.238°, α = 9.23°; Cg1, Cg2, Cg3 and Cg4 are the centroids of the Cd1/N1/C10/C11/N2, N5/C31–C34, Cd1/N3/C26/C22N/4 and N6/C1–C5 rings, respectively; CgI···J_perp is the perpendicular distance from CgI to the plane containing ring J; α is the dihedral angle between planes I and J].

The fluorescence spectra for complex (I) and native PP were measured at room temperature in the solid state, and the excitation wavelengths are at 395 nm for the complex and 467 nm for PP. The emission peak positions are at 444 and 473 nm for the complex and at 529 nm for PP. The appearance of the two emission peaks for the complex implys that there may be two different structures for the PP ligand in complex (I), which is consistent with the crystal structure. The peak at 444 nm may be attributed to the PP bridging ligand because of the larger dihedral angle between the pyridine and 1,10-phenanthroline ring planes and, consequently, the lower degree of conjugation. Compared with the fluorescence spectrum of the complex, the bathochromic shift of the maximum emission peak of uncoordinated PP may imply that there should be a larger degree of conjugation and a smaller dihedral angle between the pyridine and 1,10-phenanthroline ring planes, although the crystal data for the PP ligand are not available as yet. At the same time, the emission intensity of complex (I) is stronger than that of the PP ligand, which may imply the existance of a strong π–π stacking interaction between PP molecules (Mizobe et al., 2006).

Related literature

For related literature, see: Liu et al. (2004); Mizobe et al. (2006); Zhang et al. (2006); Zheng et al. (2003).

S2. Experimental

Cd(ClO₄)₂·6H₂O (0.2727 g, 0.65 mmol) was dissolved in 10 ml of methanol and then mixed with 10 ml of a methanol solution of PP (0.1774 g, 0.65 mmol), and the mixed solution was stirred for a few minutes. Yellow single crystals were obtained after allowing the mixed solution to stand at room temperature for two weeks (m.p. 367 K). The IR spectrum displays a strong and sharp peak at 1661 cm^-1 corresponding to the vibration of the C═O group, and strong peaks at 1145, 1115 and 1085 cm^-1 can be attributed to vibrations of the perchlorate ion.

S3. Refinement

The H atoms of the water ligand were located in a difference map and the other H atoms were placed in calculated positions. All H atoms were refined using a riding model [O—H = 0.897–0.898 Å, C—H = 0.93 Å, and U_iso(H) = 1.5U_eq(O) and 1.2U_eq(C)].

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL (Bruker, 2001); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures

	Fig. 1. The binuclear complex cation of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme for the asymmetric unit; perchlorate anions have been omitted for clarity.
	Fig. 2. The packing and intermolecular interactions (dashed lines) of (I), viewed along the c axis.

Bis[µ-1-(1,10-phenanthrolin-2-yl)-2-pyridone]bis{aqua[1-(1,10-phenanthrolin-2- yl)-2-pyridone]cadmium(II)} tetrakis(perchlorate)

Crystal data

[Cd2(C17H11N3O)4(H2O)2](ClO4)4	Z = 1
Mr = 1751.78	F(000) = 880
Triclinic, P1	Dx = 1.734 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.681 (2) Å	Cell parameters from 2995 reflections
b = 12.437 (2) Å	θ = 2.0–24.0°
c = 12.709 (2) Å	µ = 0.88 mm^−1
α = 107.317 (2)°	T = 298 K
β = 106.340 (2)°	Block, pale yellow
γ = 91.838 (2)°	0.24 × 0.16 × 0.10 mm
V = 1677.9 (5) Å^3

Data collection

Bruker SMART APEX CCD diffractometer	6304 independent reflections
Radiation source: fine-focus sealed tube	5004 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ϕ and ω scans	θmax = 25.8°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→12
Tmin = 0.816, Tmax = 0.917	k = −12→15
9002 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.103	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0572P)^2] where P = (Fo^2 + 2Fc^2)/3
6304 reflections	(Δ/σ)max = 0.001
488 parameters	Δρmax = 0.81 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
C1	0.8506 (4)	0.8888 (3)	0.5029 (4)	0.0530 (11)
H1	0.7921	0.8944	0.4385	0.064*
C2	0.8858 (5)	0.9779 (4)	0.5998 (5)	0.0644 (13)
H2	0.8497	1.0440	0.6042	0.077*
C3	0.9768 (5)	0.9703 (4)	0.6936 (4)	0.0639 (13)
H3	1.0032	1.0325	0.7607	0.077*
C4	1.0272 (4)	0.8747 (4)	0.6889 (4)	0.0586 (11)
H4	1.0880	0.8721	0.7533	0.070*
C5	0.9912 (4)	0.7767 (3)	0.5887 (3)	0.0463 (10)
C6	0.8662 (3)	0.7014 (3)	0.3873 (3)	0.0397 (9)
C7	0.8905 (4)	0.7242 (3)	0.2956 (4)	0.0494 (10)
H7	0.9267	0.7955	0.3047	0.059*
C8	0.8606 (4)	0.6405 (4)	0.1914 (4)	0.0547 (11)
H8	0.8752	0.6543	0.1280	0.066*
C9	0.8080 (4)	0.5342 (3)	0.1803 (3)	0.0432 (9)
C10	0.7843 (3)	0.5188 (3)	0.2779 (3)	0.0351 (8)
C11	0.7265 (3)	0.4107 (3)	0.2678 (3)	0.0356 (8)
C12	0.6981 (4)	0.3224 (3)	0.1624 (3)	0.0436 (9)
C13	0.7223 (4)	0.3414 (4)	0.0657 (3)	0.0538 (11)
H13	0.7013	0.2828	−0.0044	0.065*
C14	0.7745 (4)	0.4417 (4)	0.0732 (3)	0.0520 (11)
H14	0.7893	0.4518	0.0084	0.062*
C15	0.6471 (4)	0.2182 (4)	0.1583 (4)	0.0602 (12)
H15	0.6272	0.1573	0.0901	0.072*
C16	0.6265 (5)	0.2054 (3)	0.2532 (4)	0.0680 (14)
H16	0.5942	0.1353	0.2514	0.082*
C17	0.6540 (4)	0.2978 (3)	0.3538 (4)	0.0593 (12)
H17	0.6388	0.2883	0.4188	0.071*
C18	0.9210 (4)	0.6649 (4)	0.7921 (4)	0.0576 (12)
H18	0.9608	0.6017	0.7735	0.069*
C19	0.9582 (5)	0.7387 (5)	0.9046 (4)	0.0739 (15)
H19	1.0202	0.7237	0.9608	0.089*
C20	0.9037 (5)	0.8323 (4)	0.9318 (4)	0.0714 (14)
H20	0.9283	0.8824	1.0071	0.086*
C21	0.8103 (4)	0.8546 (3)	0.8475 (3)	0.0490 (10)
C22	0.7752 (3)	0.7741 (3)	0.7361 (3)	0.0372 (8)
C23	0.7503 (5)	0.9532 (4)	0.8696 (4)	0.0648 (13)
H23	0.7736	1.0059	0.9435	0.078*
C24	0.6615 (4)	0.9714 (3)	0.7865 (4)	0.0581 (12)
H24	0.6253	1.0374	0.8030	0.070*
C25	0.6212 (4)	0.8905 (3)	0.6723 (3)	0.0429 (9)
C26	0.6765 (3)	0.7912 (3)	0.6476 (3)	0.0343 (8)
C27	0.5267 (4)	0.9037 (3)	0.5840 (4)	0.0499 (10)
H27	0.4895	0.9692	0.5970	0.060*
C28	0.4880 (4)	0.8217 (3)	0.4786 (3)	0.0451 (9)
H28	0.4248	0.8297	0.4189	0.054*
C29	0.5470 (3)	0.7250 (3)	0.4640 (3)	0.0344 (8)
C30	0.4280 (3)	0.5434 (3)	0.3450 (3)	0.0371 (8)
C31	0.3986 (4)	0.4551 (3)	0.2356 (3)	0.0466 (10)
H31	0.3527	0.3881	0.2252	0.056*
C32	0.4347 (4)	0.4660 (4)	0.1483 (3)	0.0494 (10)
H32	0.4138	0.4069	0.0785	0.059*
C33	0.5039 (4)	0.5654 (3)	0.1608 (3)	0.0455 (10)
H33	0.5259	0.5739	0.0986	0.055*
C34	0.5382 (3)	0.6478 (3)	0.2622 (3)	0.0407 (9)
H34	0.5838	0.7143	0.2708	0.049*
Cd1	0.75342 (2)	0.55115 (2)	0.52738 (2)	0.03562 (11)
Cl1	0.81961 (10)	0.28114 (9)	0.77260 (8)	0.0493 (3)
Cl2	0.64738 (10)	0.87777 (8)	0.14325 (9)	0.0550 (3)
N1	0.8136 (3)	0.6030 (2)	0.3815 (2)	0.0334 (7)
N2	0.7009 (3)	0.3984 (2)	0.3606 (3)	0.0411 (8)
N3	0.6377 (3)	0.7092 (2)	0.5427 (2)	0.0313 (6)
N4	0.8310 (3)	0.6810 (3)	0.7099 (3)	0.0393 (7)
N5	0.8994 (3)	0.7893 (2)	0.4972 (3)	0.0421 (7)
N6	0.5061 (3)	0.6348 (2)	0.3543 (2)	0.0328 (6)
O1	0.8961 (3)	0.4436 (2)	0.5954 (2)	0.0522 (7)
H10	0.8597	0.3878	0.6106	0.078*
H9	0.9262	0.4042	0.5401	0.078*
O2	1.0333 (3)	0.6864 (2)	0.5789 (2)	0.0625 (8)
O3	0.3926 (2)	0.5445 (2)	0.4279 (2)	0.0456 (7)
O4	0.6224 (5)	0.7621 (3)	0.0875 (4)	0.1285 (18)
O5	0.7559 (5)	0.9176 (5)	0.1408 (5)	0.163 (2)
O6	0.6520 (5)	0.9025 (3)	0.2605 (3)	0.1084 (15)
O7	0.5617 (5)	0.9343 (4)	0.0901 (4)	0.137 (2)
O8	0.8088 (3)	0.2512 (3)	0.6516 (2)	0.0645 (8)
O9	0.7059 (3)	0.2557 (3)	0.7859 (3)	0.0801 (10)
O10	0.9035 (3)	0.2190 (3)	0.8237 (3)	0.0699 (9)
O11	0.8608 (4)	0.3994 (3)	0.8252 (4)	0.0981 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.054 (3)	0.037 (2)	0.067 (3)	0.0078 (19)	0.019 (2)	0.015 (2)
C2	0.074 (3)	0.036 (2)	0.079 (4)	0.008 (2)	0.029 (3)	0.006 (2)
C3	0.078 (4)	0.043 (2)	0.059 (3)	−0.005 (2)	0.025 (3)	−0.004 (2)
C4	0.065 (3)	0.057 (3)	0.041 (2)	0.002 (2)	0.010 (2)	0.004 (2)
C5	0.051 (3)	0.047 (2)	0.039 (2)	0.007 (2)	0.017 (2)	0.0093 (18)
C6	0.039 (2)	0.039 (2)	0.043 (2)	0.0108 (17)	0.0151 (18)	0.0124 (17)
C7	0.058 (3)	0.043 (2)	0.054 (3)	0.005 (2)	0.023 (2)	0.021 (2)
C8	0.066 (3)	0.068 (3)	0.046 (3)	0.016 (2)	0.028 (2)	0.029 (2)
C9	0.045 (2)	0.055 (2)	0.034 (2)	0.0170 (19)	0.0157 (18)	0.0161 (18)
C10	0.036 (2)	0.041 (2)	0.0272 (18)	0.0125 (16)	0.0096 (16)	0.0085 (15)
C11	0.037 (2)	0.0379 (19)	0.0294 (19)	0.0110 (16)	0.0109 (16)	0.0058 (15)
C12	0.047 (2)	0.043 (2)	0.034 (2)	0.0077 (18)	0.0137 (18)	0.0006 (16)
C13	0.062 (3)	0.060 (3)	0.027 (2)	0.011 (2)	0.012 (2)	−0.0028 (18)
C14	0.059 (3)	0.070 (3)	0.027 (2)	0.020 (2)	0.017 (2)	0.0121 (19)
C15	0.068 (3)	0.045 (2)	0.049 (3)	−0.001 (2)	0.018 (2)	−0.012 (2)
C16	0.096 (4)	0.035 (2)	0.069 (3)	−0.010 (2)	0.044 (3)	−0.005 (2)
C17	0.089 (4)	0.036 (2)	0.055 (3)	0.000 (2)	0.044 (3)	−0.0010 (19)
C18	0.060 (3)	0.067 (3)	0.039 (2)	0.022 (2)	0.009 (2)	0.012 (2)
C19	0.075 (3)	0.095 (4)	0.031 (2)	0.023 (3)	−0.003 (2)	0.007 (2)
C20	0.077 (3)	0.085 (4)	0.028 (2)	0.011 (3)	0.004 (2)	−0.006 (2)
C21	0.057 (3)	0.051 (2)	0.029 (2)	0.004 (2)	0.0118 (19)	−0.0013 (17)
C22	0.046 (2)	0.0371 (19)	0.0246 (18)	0.0031 (17)	0.0117 (17)	0.0033 (15)
C23	0.077 (3)	0.054 (3)	0.040 (3)	0.007 (2)	0.016 (2)	−0.018 (2)
C24	0.075 (3)	0.036 (2)	0.053 (3)	0.010 (2)	0.025 (3)	−0.0065 (19)
C25	0.053 (3)	0.0312 (19)	0.042 (2)	0.0036 (17)	0.016 (2)	0.0063 (16)
C26	0.044 (2)	0.0277 (17)	0.0317 (19)	0.0026 (15)	0.0178 (17)	0.0053 (14)
C27	0.061 (3)	0.031 (2)	0.058 (3)	0.0138 (19)	0.022 (2)	0.0102 (18)
C28	0.053 (3)	0.039 (2)	0.044 (2)	0.0145 (18)	0.012 (2)	0.0144 (17)
C29	0.042 (2)	0.0306 (18)	0.0306 (19)	0.0030 (16)	0.0123 (17)	0.0084 (15)
C30	0.046 (2)	0.0323 (19)	0.033 (2)	0.0074 (17)	0.0136 (18)	0.0098 (15)
C31	0.060 (3)	0.037 (2)	0.036 (2)	−0.0012 (19)	0.016 (2)	0.0017 (16)
C32	0.054 (3)	0.055 (2)	0.033 (2)	0.006 (2)	0.017 (2)	0.0007 (18)
C33	0.047 (2)	0.062 (3)	0.031 (2)	0.010 (2)	0.0160 (18)	0.0157 (18)
C34	0.042 (2)	0.049 (2)	0.037 (2)	0.0086 (18)	0.0151 (18)	0.0183 (18)
Cd1	0.05008 (19)	0.02992 (15)	0.02490 (15)	0.00881 (11)	0.01215 (12)	0.00486 (10)
Cl1	0.0582 (7)	0.0550 (6)	0.0368 (5)	0.0177 (5)	0.0169 (5)	0.0142 (4)
Cl2	0.0636 (7)	0.0419 (5)	0.0497 (6)	0.0063 (5)	0.0076 (5)	0.0094 (5)
N1	0.0366 (17)	0.0345 (16)	0.0281 (16)	0.0076 (13)	0.0111 (13)	0.0072 (12)
N2	0.055 (2)	0.0335 (16)	0.0340 (17)	0.0042 (15)	0.0203 (16)	0.0027 (13)
N3	0.0415 (17)	0.0271 (14)	0.0266 (15)	0.0061 (13)	0.0149 (14)	0.0060 (12)
N4	0.0449 (19)	0.0428 (18)	0.0278 (16)	0.0090 (15)	0.0094 (14)	0.0088 (13)
N5	0.0460 (19)	0.0307 (16)	0.047 (2)	0.0048 (14)	0.0155 (16)	0.0074 (14)
N6	0.0383 (17)	0.0327 (15)	0.0264 (15)	0.0068 (13)	0.0089 (13)	0.0085 (12)
O1	0.068 (2)	0.0493 (16)	0.0460 (17)	0.0224 (14)	0.0218 (15)	0.0200 (13)
O2	0.081 (2)	0.0566 (19)	0.0446 (18)	0.0319 (17)	0.0157 (16)	0.0101 (14)
O3	0.0583 (18)	0.0405 (14)	0.0376 (15)	−0.0028 (13)	0.0221 (14)	0.0058 (12)
O4	0.227 (6)	0.044 (2)	0.093 (3)	0.006 (3)	0.041 (4)	0.001 (2)
O5	0.113 (4)	0.211 (6)	0.155 (5)	−0.050 (4)	0.061 (4)	0.033 (4)
O6	0.175 (5)	0.086 (3)	0.054 (2)	0.017 (3)	0.025 (3)	0.016 (2)
O7	0.161 (5)	0.113 (4)	0.092 (3)	0.068 (3)	−0.017 (3)	0.016 (3)
O8	0.081 (2)	0.079 (2)	0.0379 (17)	0.0209 (18)	0.0220 (16)	0.0211 (15)
O9	0.057 (2)	0.130 (3)	0.061 (2)	0.015 (2)	0.0264 (18)	0.034 (2)
O10	0.068 (2)	0.086 (2)	0.057 (2)	0.0250 (18)	0.0089 (17)	0.0318 (18)
O11	0.144 (4)	0.050 (2)	0.096 (3)	0.011 (2)	0.052 (3)	0.0015 (19)

Geometric parameters (Å, º)

C2—C1	1.337 (6)	C21—C23	1.425 (6)
C2—C3	1.387 (7)	C22—N4	1.348 (4)
C2—H2	0.9300	C22—C26	1.438 (5)
C1—N5	1.370 (5)	C23—C24	1.336 (7)
C1—H1	0.9300	C23—H23	0.9300
C3—C4	1.336 (6)	C24—C25	1.435 (5)
C3—H3	0.9300	C24—H24	0.9300
C4—C5	1.423 (6)	C25—C27	1.389 (6)
C4—H4	0.9300	C25—C26	1.405 (5)
C5—O2	1.228 (5)	C26—N3	1.357 (4)
C5—N5	1.394 (5)	C27—C28	1.362 (5)
C7—C8	1.363 (6)	C27—H27	0.9300
C7—C6	1.377 (5)	C28—C29	1.396 (5)
C7—H7	0.9300	C28—H28	0.9300
C6—N1	1.323 (4)	C29—N3	1.302 (4)
C6—N5	1.434 (5)	C29—N6	1.446 (4)
C8—C9	1.390 (6)	C30—O3	1.233 (4)
C8—H8	0.9300	C30—N6	1.389 (4)
C9—C10	1.408 (5)	C30—C31	1.433 (5)
C9—C14	1.439 (5)	C31—C32	1.333 (5)
C10—N1	1.360 (4)	C31—H31	0.9300
C10—C11	1.439 (5)	C32—C33	1.398 (6)
C11—N2	1.344 (4)	C32—H32	0.9300
C11—C12	1.400 (5)	C33—C34	1.330 (5)
C12—C15	1.390 (6)	C33—H33	0.9300
C12—C13	1.418 (5)	C34—N6	1.376 (4)
C13—C14	1.335 (6)	C34—H34	0.9300
C13—H13	0.9300	Cd1—N2	2.296 (3)
C14—H14	0.9300	Cd1—N4	2.303 (3)
C15—C16	1.346 (6)	Cd1—O1	2.309 (3)
C15—H15	0.9300	Cd1—O3^i	2.337 (2)
C16—C17	1.389 (6)	Cd1—N1	2.402 (3)
C16—H16	0.9300	Cd1—N3	2.412 (3)
C17—N2	1.319 (5)	Cl1—O10	1.403 (3)
C17—H17	0.9300	Cl1—O9	1.423 (3)
C18—N4	1.325 (5)	Cl1—O11	1.424 (4)
C18—C19	1.386 (6)	Cl1—O8	1.437 (3)
C18—H18	0.9300	Cl2—O5	1.358 (5)
C19—C20	1.347 (6)	Cl2—O7	1.379 (4)
C19—H19	0.9300	Cl2—O4	1.381 (4)
C20—C21	1.398 (6)	Cl2—O6	1.414 (4)
C20—H20	0.9300	O1—H10	0.8983
C21—C22	1.407 (5)	O1—H9	0.8965
C1—C2—C3	119.0 (4)	N3—C26—C22	118.7 (3)
C1—C2—H2	120.5	C25—C26—C22	119.5 (3)
C3—C2—H2	120.5	C28—C27—C25	120.8 (4)
C2—C1—N5	121.0 (4)	C28—C27—H27	119.6
C2—C1—H1	119.5	C25—C27—H27	119.6
N5—C1—H1	119.5	C27—C28—C29	117.2 (4)
C4—C3—C2	120.9 (4)	C27—C28—H28	121.4
C4—C3—H3	119.6	C29—C28—H28	121.4
C2—C3—H3	119.6	N3—C29—C28	124.7 (3)
C3—C4—C5	122.2 (4)	N3—C29—N6	116.6 (3)
C3—C4—H4	118.9	C28—C29—N6	118.7 (3)
C5—C4—H4	118.9	O3—C30—N6	119.3 (3)
O2—C5—N5	120.2 (4)	O3—C30—C31	126.9 (3)
O2—C5—C4	125.5 (4)	N6—C30—C31	113.8 (3)
N5—C5—C4	114.4 (4)	C32—C31—C30	122.1 (4)
C8—C7—C6	118.7 (4)	C32—C31—H31	118.9
C8—C7—H7	120.6	C30—C31—H31	118.9
C6—C7—H7	120.6	C31—C32—C33	120.6 (4)
N1—C6—C7	124.5 (4)	C31—C32—H32	119.7
N1—C6—N5	117.0 (3)	C33—C32—H32	119.7
C7—C6—N5	118.5 (3)	C34—C33—C32	119.6 (4)
C7—C8—C9	119.6 (4)	C34—C33—H33	120.2
C7—C8—H8	120.2	C32—C33—H33	120.2
C9—C8—H8	120.2	C33—C34—N6	120.0 (4)
C8—C9—C10	117.9 (4)	C33—C34—H34	120.0
C8—C9—C14	122.6 (4)	N6—C34—H34	120.0
C10—C9—C14	119.4 (4)	N2—Cd1—N4	168.48 (11)
N1—C10—C9	122.2 (3)	N2—Cd1—O1	84.05 (11)
N1—C10—C11	118.8 (3)	N4—Cd1—O1	84.52 (10)
C9—C10—C11	119.1 (3)	N2—Cd1—O3^i	83.31 (10)
N2—C11—C12	122.2 (3)	N4—Cd1—O3^i	95.45 (10)
N2—C11—C10	118.3 (3)	O1—Cd1—O3^i	90.95 (10)
C12—C11—C10	119.4 (3)	N2—Cd1—N1	71.08 (10)
C15—C12—C11	117.3 (4)	N4—Cd1—N1	113.63 (10)
C15—C12—C13	122.8 (4)	O1—Cd1—N1	105.73 (9)
C11—C12—C13	119.9 (4)	O3^i—Cd1—N1	147.35 (10)
C14—C13—C12	121.4 (4)	N2—Cd1—N3	120.17 (11)
C14—C13—H13	119.3	N4—Cd1—N3	71.13 (10)
C12—C13—H13	119.3	O1—Cd1—N3	155.43 (10)
C13—C14—C9	120.8 (4)	O3^i—Cd1—N3	88.18 (9)
C13—C14—H14	119.6	N1—Cd1—N3	87.58 (9)
C9—C14—H14	119.6	O10—Cl1—O9	109.8 (2)
C16—C15—C12	120.0 (4)	O10—Cl1—O11	109.5 (3)
C16—C15—H15	120.0	O9—Cl1—O11	110.4 (2)
C12—C15—H15	120.0	O10—Cl1—O8	109.11 (19)
C15—C16—C17	119.4 (4)	O9—Cl1—O8	109.6 (2)
C15—C16—H16	120.3	O11—Cl1—O8	108.4 (2)
C17—C16—H16	120.3	O5—Cl2—O7	107.8 (4)
N2—C17—C16	122.4 (4)	O5—Cl2—O4	110.5 (4)
N2—C17—H17	118.8	O7—Cl2—O4	110.8 (3)
C16—C17—H17	118.8	O5—Cl2—O6	107.8 (3)
N4—C18—C19	122.6 (4)	O7—Cl2—O6	109.7 (3)
N4—C18—H18	118.7	O4—Cl2—O6	110.1 (3)
C19—C18—H18	118.7	C6—N1—C10	117.1 (3)
C20—C19—C18	119.3 (4)	C6—N1—Cd1	129.2 (2)
C20—C19—H19	120.4	C10—N1—Cd1	113.7 (2)
C18—C19—H19	120.4	C17—N2—C11	118.6 (3)
C19—C20—C21	120.3 (4)	C17—N2—Cd1	123.2 (3)
C19—C20—H20	119.8	C11—N2—Cd1	118.1 (2)
C21—C20—H20	119.8	C29—N3—C26	118.0 (3)
C20—C21—C22	117.1 (4)	C29—N3—Cd1	128.4 (2)
C20—C21—C23	123.4 (4)	C26—N3—Cd1	113.6 (2)
C22—C21—C23	119.6 (4)	C18—N4—C22	118.8 (3)
N4—C22—C21	122.0 (3)	C18—N4—Cd1	123.6 (3)
N4—C22—C26	118.9 (3)	C22—N4—Cd1	117.5 (2)
C21—C22—C26	119.1 (3)	C34—N6—C30	123.2 (3)
C24—C23—C21	121.5 (4)	C34—N6—C29	118.6 (3)
C24—C23—H23	119.2	C30—N6—C29	118.0 (3)
C21—C23—H23	119.2	C1—N5—C5	122.5 (3)
C23—C24—C25	120.7 (4)	C1—N5—C6	117.8 (3)
C23—C24—H24	119.6	C5—N5—C6	119.1 (3)
C25—C24—H24	119.6	Cd1—O1—H10	108.9
C27—C25—C26	117.5 (3)	Cd1—O1—H9	111.8
C27—C25—C24	123.0 (4)	H10—O1—H9	101.8
C26—C25—C24	119.5 (4)	C30—O3—Cd1^i	140.3 (2)
N3—C26—C25	121.8 (3)
C3—C2—C1—N5	2.8 (7)	N4—Cd1—N1—C10	170.0 (2)
C1—C2—C3—C4	−1.5 (7)	O1—Cd1—N1—C10	79.2 (2)
C2—C3—C4—C5	0.2 (7)	O3^i—Cd1—N1—C10	−39.0 (3)
C3—C4—C5—O2	−179.7 (4)	N3—Cd1—N1—C10	−121.8 (2)
C3—C4—C5—N5	−0.2 (6)	C16—C17—N2—C11	−2.2 (7)
C8—C7—C6—N1	−0.9 (6)	C16—C17—N2—Cd1	−177.8 (4)
C8—C7—C6—N5	179.2 (4)	C12—C11—N2—C17	4.2 (6)
C6—C7—C8—C9	−0.9 (6)	C10—C11—N2—C17	−176.3 (4)
C7—C8—C9—C10	2.0 (6)	C12—C11—N2—Cd1	180.0 (3)
C7—C8—C9—C14	−179.7 (4)	C10—C11—N2—Cd1	−0.5 (4)
C8—C9—C10—N1	−1.6 (5)	N4—Cd1—N2—C17	59.1 (7)
C14—C9—C10—N1	−179.9 (3)	O1—Cd1—N2—C17	66.3 (4)
C8—C9—C10—C11	178.1 (4)	O3^i—Cd1—N2—C17	−25.4 (3)
C14—C9—C10—C11	−0.2 (5)	N1—Cd1—N2—C17	175.2 (4)
N1—C10—C11—N2	1.8 (5)	N3—Cd1—N2—C17	−109.3 (3)
C9—C10—C11—N2	−177.9 (3)	N4—Cd1—N2—C11	−116.5 (5)
N1—C10—C11—C12	−178.6 (3)	O1—Cd1—N2—C11	−109.3 (3)
C9—C10—C11—C12	1.6 (5)	O3^i—Cd1—N2—C11	159.0 (3)
N2—C11—C12—C15	−3.2 (6)	N1—Cd1—N2—C11	−0.4 (3)
C10—C11—C12—C15	177.3 (4)	N3—Cd1—N2—C11	75.1 (3)
N2—C11—C12—C13	177.2 (4)	C28—C29—N3—C26	1.5 (5)
C10—C11—C12—C13	−2.3 (6)	N6—C29—N3—C26	−178.5 (3)
C15—C12—C13—C14	−178.1 (4)	C28—C29—N3—Cd1	−177.2 (3)
C11—C12—C13—C14	1.5 (6)	N6—C29—N3—Cd1	2.8 (4)
C12—C13—C14—C9	0.0 (7)	C25—C26—N3—C29	0.3 (5)
C8—C9—C14—C13	−178.8 (4)	C22—C26—N3—C29	178.9 (3)
C10—C9—C14—C13	−0.6 (6)	C25—C26—N3—Cd1	179.2 (3)
C11—C12—C15—C16	0.3 (7)	C22—C26—N3—Cd1	−2.3 (4)
C13—C12—C15—C16	179.9 (4)	N2—Cd1—N3—C29	−3.6 (3)
C12—C15—C16—C17	1.5 (8)	N4—Cd1—N3—C29	178.9 (3)
C15—C16—C17—N2	−0.6 (8)	O1—Cd1—N3—C29	−173.1 (3)
N4—C18—C19—C20	−1.9 (8)	O3^i—Cd1—N3—C29	−84.8 (3)
C18—C19—C20—C21	0.2 (8)	N1—Cd1—N3—C29	62.9 (3)
C19—C20—C21—C22	1.6 (7)	N2—Cd1—N3—C26	177.7 (2)
C19—C20—C21—C23	−178.6 (5)	N4—Cd1—N3—C26	0.1 (2)
C20—C21—C22—N4	−2.0 (6)	O1—Cd1—N3—C26	8.2 (4)
C23—C21—C22—N4	178.2 (4)	O3^i—Cd1—N3—C26	96.5 (2)
C20—C21—C22—C26	177.7 (4)	N1—Cd1—N3—C26	−115.9 (2)
C23—C21—C22—C26	−2.1 (6)	C19—C18—N4—C22	1.5 (7)
C20—C21—C23—C24	179.9 (5)	C19—C18—N4—Cd1	−173.2 (4)
C22—C21—C23—C24	−0.3 (7)	C21—C22—N4—C18	0.5 (6)
C21—C23—C24—C25	1.5 (8)	C26—C22—N4—C18	−179.2 (4)
C23—C24—C25—C27	177.9 (4)	C21—C22—N4—Cd1	175.6 (3)
C23—C24—C25—C26	−0.4 (7)	C26—C22—N4—Cd1	−4.2 (4)
C27—C25—C26—N3	−1.8 (5)	N2—Cd1—N4—C18	7.5 (7)
C24—C25—C26—N3	176.5 (4)	O1—Cd1—N4—C18	0.3 (3)
C27—C25—C26—C22	179.7 (3)	O3^i—Cd1—N4—C18	90.7 (3)
C24—C25—C26—C22	−2.0 (5)	N1—Cd1—N4—C18	−104.5 (3)
N4—C22—C26—N3	4.4 (5)	N3—Cd1—N4—C18	176.9 (3)
C21—C22—C26—N3	−175.4 (3)	N2—Cd1—N4—C22	−167.3 (5)
N4—C22—C26—C25	−177.0 (3)	O1—Cd1—N4—C22	−174.5 (3)
C21—C22—C26—C25	3.2 (5)	O3^i—Cd1—N4—C22	−84.1 (3)
C26—C25—C27—C28	1.5 (6)	N1—Cd1—N4—C22	80.7 (3)
C24—C25—C27—C28	−176.7 (4)	N3—Cd1—N4—C22	2.1 (2)
C25—C27—C28—C29	0.1 (6)	C33—C34—N6—C30	−6.9 (5)
C27—C28—C29—N3	−1.7 (6)	C33—C34—N6—C29	178.6 (3)
C27—C28—C29—N6	178.3 (3)	O3—C30—N6—C34	−171.5 (3)
O3—C30—C31—C32	175.0 (4)	C31—C30—N6—C34	9.2 (5)
N6—C30—C31—C32	−5.8 (6)	O3—C30—N6—C29	3.0 (5)
C30—C31—C32—C33	0.1 (7)	C31—C30—N6—C29	−176.2 (3)
C31—C32—C33—C34	2.8 (6)	N3—C29—N6—C34	−102.2 (4)
C32—C33—C34—N6	0.4 (6)	C28—C29—N6—C34	77.8 (4)
C7—C6—N1—C10	1.3 (5)	N3—C29—N6—C30	83.0 (4)
N5—C6—N1—C10	−178.7 (3)	C28—C29—N6—C30	−97.0 (4)
C7—C6—N1—Cd1	−175.9 (3)	C2—C1—N5—C5	−2.9 (6)
N5—C6—N1—Cd1	4.1 (5)	C2—C1—N5—C6	−173.9 (4)
C9—C10—N1—C6	0.0 (5)	O2—C5—N5—C1	−179.0 (4)
C11—C10—N1—C6	−179.8 (3)	C4—C5—N5—C1	1.5 (6)
C9—C10—N1—Cd1	177.6 (3)	O2—C5—N5—C6	−8.1 (6)
C11—C10—N1—Cd1	−2.1 (4)	C4—C5—N5—C6	172.4 (3)
N2—Cd1—N1—C6	178.6 (3)	N1—C6—N5—C1	−120.6 (4)
N4—Cd1—N1—C6	−12.7 (3)	C7—C6—N5—C1	59.3 (5)
O1—Cd1—N1—C6	−103.5 (3)	N1—C6—N5—C5	68.1 (5)
O3^i—Cd1—N1—C6	138.3 (3)	C7—C6—N5—C5	−112.0 (4)
N3—Cd1—N1—C6	55.5 (3)	N6—C30—O3—Cd1^i	166.7 (2)
N2—Cd1—N1—C10	1.3 (2)	C31—C30—O3—Cd1^i	−14.1 (7)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H9···O2^ii	0.90	1.79	2.680 (4)	172
O1—H10···O8	0.90	2.04	2.924 (5)	169
C2—H2···O8^iii	0.93	2.56	3.463 (5)	164
C17—H17···O3^i	0.93	2.51	3.085 (5)	120
C19—H19···O10^iv	0.93	2.50	3.246 (5)	138
C28—H28···O9^i	0.93	2.50	3.318 (5)	147
C32—H32···O4^v	0.93	2.42	3.342 (5)	172

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