A new two-dimensional cadmium metal–organic framework: poly[bis­(4,7-di­phenyl-1,10-phen­an­thro­line)(μ₃-5-nitro­isophthalato)cadmium(II)]

In the title cadmium metal–organic framework complex, [Cd(C₈H₃NO₆)(C₂₄H₁₆N₂)]_n or [Cd(NIPH)(dpphen)] (NIPH is nitro­isophthalate and dpphen is 4,7-diphenyl-1,10-phenanthroline), the unique Cd^II cation in a general position is coordinated by four carb­oxy O atoms from three symmetry-related NIPH anions and two N atoms from a dpphen ligand. The Cd^II cations are bridged by pairs of NIPH anions to generate a dinuclear mol­ecular building block, [Cd₂N₄(CO₂R)₄], with a Cd...Cd separation of 4.0936 (10) Å. Each such building block is connected to four adjacent dinuclear building blocks by NIPH anions, resulting in a two-dimensional layer framework in the bc plane. The dpphen ligands occupy the space between these layers and are linked by π–π inter­actions, with a separation of 3.4541 (6) Å between the central aromatic rings of inversion-related dpphen ligands. The thermogravimetric and photoluminescent properties of the complex have also been investigated.

S1. Comment

The design and construction of metal–organic frameworks (MOFs) have attracted considerable attention due to their diverse structures and potential applications in many fields, such as gas adsorption, ion exchange, magnetism and as photoluminescence materials (Kim et al., 2011; Uemura et al., 2009). To date, numerous one-, two- and three-dimensional MOFs have been synthesized by a molecular self-assembly method using appropriate metal ions or metal clusters and versatile bridging organic ligands (Chen et al., 2010). Among the most commonly reported d¹⁰ metal complexes, cadmium metal–organic frameworks (Cd-MOFs) have undergone tremendous development because of their interesting structural topologies and excellent photoluminescent properties [(Seo et al., 2009; Zheng et al., 2012). For example, Deng and co-workers reported a luminescent microporous Cd-MOF that exhibits a high-sensitivity sensing function with respect to nitrite in both dimethylformamide and water (Qiu et al., 2009), and more recently Dincä and co-workers have shown turn-on fluorescence phenomena in a tetraphenylethylene-based Cd-MOF that exhibits guest-dependent emission maxima (Shustova et al., 2011). Many multidentate ligands containing N-, O- or S-donors have been used in the synthesis of MOFs. In particular, polybenzenecarboxylate ligands are frequently employed to form fascinating topologies. Recently, we have focused our attention on a systematic study of MOFs constructed from 5-nitroisophthalic acid (H₂NIPH) and auxiliary ligands, and have obtained various organic–inorganic hybrids with interesting structures and properties (Lu et al., 2012; Ye et al., 2008). H₂NIPH is a versatile ligand for the construction of MOFs, not only due to the rich coordination modes of its two carboxylate groups, but also because its nitro group can act as a hydrogen-bond acceptor to form hydrogen bonds, which is often useful for the formation of high-dimensional networks. In this work, we used H₂NIPH as the bridging ligand and 4,7-diphenyl-1,10-phenanthroline (dpphen) as the ancillary ligand to construct the title two-dimensional coordination framework, [Cd(NIPH)(dpphen)]_n, (I), under hydrothermal conditions. The crystal structure and thermal and photoluminescent properties of (I) are reported here.

The asymmetric unit of (I) contains one Cd^II cation, one NIPH anion and one dpphen ligand, all in general positions. Atom Cd1 (see Fig. 1) is coordinated by four carboxyl O atoms (O1, O2, O3A and O4B) from three NIPH anions and two N atoms (N2 and N3) from one dpphen ligand, to yield a distorted octahedral geometry (Fig. 1). The Cd—O bond lengths are in the range 2.204 (2)–2.703 (2) Å, and Cd—N = 2.332 (2) and 2.333 (2)Å; these dimensions are in good agreement with those found in other extended Cd-MOFs (Zhang et al., 2009). In the structure, Cd^II cations are bridged by two carboxylate groups in bis-monodentate fashion about an inversion centre to form a dinuclear molecular building block, [Cd₂N₄(CO₂R)₄], with a Cd···Cd separation of 4.0936 (10) Å (Fig. 2). Each such building block is connected to four adjacent dinuclear building blocks by NIPH anions, resulting in a two-dimensional framework (Fig. 3). The dpphen ligands occupy the space between these layers and are linked by π–π interactions, with a separation of 3.4541 (6) Å between the central aromatic rings of inversion-related dpphen ligands, giving rise to a three-dimensional supramolecular network (Fig. 4).

The framework of (I) is stable in air at ambient temperature and almost insoluble in common solvents, such as water, chloroform, carbon tetrachloride, alcohol, acetone and acetonitrile. The thermal behaviour of (I) was examined by thermogravimetric analysis (TGA) under [What sort of?] atmosphere. The TGA results indicate that (I) is stable up to 644 K, and then the framework starts to collapse as the organic ligands decompose. A study of the fluorescent properties of (I) in the solid state at room temperature was also carried out. Fig. 5 shows the intense fluorescence emission bands with a maximum at 448 nm when excited at 341 nm. The blue light emission of (I) may be attributed to ligand-to-metal charge transfer (LMCT) (Feng et al., 2009). It may thus be possible to develop highly stable luminescent materials based on (I).

In summary, we have successfully assembled Cd^II cations, 5-nitroisophthalic acid (H₂NIPH) and 4,7-diphenyl-1,10-phenanthroline (dpphen) into a cadmium metal–organic framework, [Cd(NIPH)(dpphen)]_n, (I), under hydrothermal conditions. Single-crystal X-ray diffraction analysis revealed that (I) is a two-dimensional framework based on a dinuclear cadmium cluster. In addition, a three-dimensional supramolecular network is formed in (I) by π–π interactions. Compound (I) exhibits an intense blue emission and it may be possible to develop highly stable luminescent materials. [Can this repetition be omitted?]

Related literature

For related literature, see: Chen et al. (2010); Feng et al. (2009); Kim et al. (2011); Lu et al. (2012); Qiu et al. (2009); Seo et al. (2009); Shustova et al. (2011); Uemura et al. (2009); Ye et al. (2008); Zhang et al. (2009); Zheng et al. (2012).

S2. Experimental

The title compound was prepared by a hydrothermal method. A mixture of Cd(NO₃)₂.4H₂O (0.118 g, 0.5 mmol), H₂NIPH (0.105 g, 0.5 mmol) and dpphen (0.166 g, 0.5 mmol) in H₂O (12 ml) was stirred for 30 min and then heated at 433 K for 72 h in a Teflon-lined stainless steel autoclave (25 ml) under autogenous pressure. After cooling to room temperature, colourless block-shaped crystals of (I) were obtained; they were washed with water and dried in air.

S3. Refinement

H atoms were placed in calculated positions, with C—H = 0.93 Å (aromatic) or 0.98 Å (methine), and refined in the riding-model approximation, with U_iso(H) = 1.2U_eq(C).

Computing details

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

Figures

	Fig. 1. A perspective view of the coordination environment around the Cd^II cation of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at 30% probability level. [Symmetry codes: (A) x, 1/2 - y, 1/2 + z; (B) -x, -1/2 + y, -1/2 - z.]
	Fig. 2. A view of the dinuclear molecular building block of (I), with displacement ellipsoids drawn at the 30% probability level. For simplicity, the C and H atoms of the dpphen ligands have been omitted. [Symmetry codes: (a) -x, -y, -z; (b) x, 1/2 - y, 1/2 + z; (c) -x, -1/2 + y, -1/2 - z.]
	Fig. 3. A view of the two-dimensional framework in (I). The dpphen ligands have been omitted for clarity.
	Fig. 4. A view of the three-dimensional supramolecular network of (I).
	Fig. 5. The emission spectrum of (I) at room temperature on excitation at 341 nm.

poly[bis(4,7-diphenyl-1,10-phenanthroline)(µ₃-5- nitroisophthalato)cadmium(II)]

Crystal data

[Cd(C8H3NO6)(C24H16N2)]	F(000) = 1312
Mr = 653.91	Dx = 1.664 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5857 reflections
a = 11.649 (2) Å	θ = 3.0–27.5°
b = 12.702 (3) Å	µ = 0.89 mm^−1
c = 17.720 (3) Å	T = 293 K
β = 95.41 (3)°	Block, colourless
V = 2610.3 (9) Å^3	0.19 × 0.19 × 0.17 mm
Z = 4

Data collection

Rigaku RAXIS-RAPID diffractometer	5857 independent reflections
Radiation source: fine-focus sealed tube	4838 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
Detector resolution: 10.0 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ω scans	h = −15→14
Absorption correction: empirical (using intensity measurements) (ABSCOR; Higashi, 1995)	k = −16→16
Tmin = 0.848, Tmax = 0.866	l = −22→22
24740 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.080	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0381P)^2 + 2.2863P] where P = (Fo^2 + 2Fc^2)/3
5857 reflections	(Δ/σ)max < 0.001
379 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.45 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.148651 (15)	0.084141 (15)	−0.006270 (10)	0.02249 (7)
O1	0.0432 (2)	0.2159 (2)	−0.05515 (12)	0.0457 (6)
O2	0.16365 (19)	0.18151 (19)	−0.14065 (13)	0.0419 (5)
O3	0.1001 (2)	0.3884 (2)	−0.38791 (12)	0.0488 (6)
O4	−0.0744 (2)	0.4553 (2)	−0.41600 (12)	0.0518 (7)
O5	−0.2578 (4)	0.5788 (4)	−0.1894 (2)	0.129 (2)
O6	−0.2340 (3)	0.4936 (2)	−0.08812 (16)	0.0699 (9)
N1	−0.2109 (2)	0.5114 (2)	−0.15181 (16)	0.0438 (7)
N2	0.32942 (18)	0.15943 (18)	0.02530 (12)	0.0239 (5)
N3	0.27478 (18)	−0.04421 (18)	0.04684 (12)	0.0240 (5)
C1	0.0202 (2)	0.3138 (2)	−0.16833 (15)	0.0247 (5)
C2	0.0421 (2)	0.3283 (2)	−0.24369 (15)	0.0260 (6)
H2A	0.0996	0.2891	−0.2635	0.031*
C3	−0.0208 (2)	0.4005 (2)	−0.28966 (14)	0.0247 (6)
C4	−0.1051 (2)	0.4607 (2)	−0.26012 (15)	0.0286 (6)
H4A	−0.1481	0.5094	−0.2901	0.034*
C5	−0.1237 (2)	0.4466 (2)	−0.18479 (16)	0.0285 (6)
C6	−0.0634 (2)	0.3743 (2)	−0.13866 (15)	0.0274 (6)
H6A	−0.0787	0.3662	−0.0884	0.033*
C7	0.0820 (2)	0.2307 (2)	−0.11895 (15)	0.0285 (6)
C8	0.0039 (3)	0.4166 (2)	−0.37151 (15)	0.0313 (6)
C9	0.3531 (2)	0.2607 (2)	0.01753 (16)	0.0314 (6)
H9A	0.2969	0.3039	−0.0070	0.038*
C10	0.4586 (3)	0.3053 (2)	0.04457 (17)	0.0333 (6)
H10A	0.4707	0.3771	0.0388	0.040*
C11	0.5444 (2)	0.2439 (2)	0.07952 (14)	0.0256 (5)
C12	0.5229 (2)	0.1341 (2)	0.08641 (14)	0.0229 (5)
C13	0.6076 (2)	0.0599 (2)	0.11655 (15)	0.0251 (6)
H13A	0.6829	0.0825	0.1290	0.030*
C14	0.5806 (2)	−0.0422 (2)	0.12734 (15)	0.0244 (5)
H14A	0.6379	−0.0883	0.1468	0.029*
C15	0.4653 (2)	−0.0809 (2)	0.10943 (14)	0.0223 (5)
C16	0.4296 (2)	−0.1856 (2)	0.12536 (14)	0.0239 (5)
C17	0.3185 (2)	−0.2136 (2)	0.09956 (17)	0.0306 (6)
H17A	0.2924	−0.2811	0.1089	0.037*
C18	0.2445 (2)	−0.1424 (2)	0.05964 (16)	0.0299 (6)
H18A	0.1712	−0.1648	0.0413	0.036*
C19	0.4126 (2)	0.0970 (2)	0.06035 (13)	0.0206 (5)
C20	0.3833 (2)	−0.0128 (2)	0.07203 (13)	0.0210 (5)
C21	0.6550 (2)	0.2933 (2)	0.11046 (16)	0.0276 (6)
C22	0.7119 (3)	0.3626 (3)	0.06649 (18)	0.0406 (8)
H22A	0.6827	0.3762	0.0168	0.049*
C23	0.8125 (3)	0.4117 (3)	0.0964 (2)	0.0553 (10)
H23A	0.8513	0.4570	0.0664	0.066*
C24	0.8551 (3)	0.3935 (3)	0.1704 (2)	0.0545 (10)
H24A	0.9228	0.4263	0.1901	0.065*
C25	0.7978 (3)	0.3272 (3)	0.21499 (19)	0.0416 (8)
H25A	0.8258	0.3164	0.2653	0.050*
C26	0.6989 (2)	0.2764 (2)	0.18587 (16)	0.0313 (6)
H26A	0.6612	0.2308	0.2163	0.038*
C27	0.5054 (2)	−0.2633 (2)	0.16826 (15)	0.0262 (6)
C28	0.5751 (2)	−0.2342 (2)	0.23317 (15)	0.0298 (6)
H28A	0.5741	−0.1651	0.2506	0.036*
C29	0.6459 (3)	−0.3080 (3)	0.27183 (17)	0.0366 (7)
H29A	0.6930	−0.2877	0.3147	0.044*
C30	0.6474 (3)	−0.4103 (3)	0.24785 (19)	0.0432 (8)
H30A	0.6964	−0.4588	0.2736	0.052*
C31	0.5760 (3)	−0.4410 (3)	0.1854 (2)	0.0472 (9)
H31A	0.5752	−0.5109	0.1699	0.057*
C32	0.5054 (3)	−0.3684 (2)	0.14545 (17)	0.0365 (7)
H32A	0.4578	−0.3898	0.1032	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02041 (10)	0.02646 (11)	0.01964 (10)	0.00215 (8)	−0.00320 (7)	0.00055 (8)
O1	0.0523 (14)	0.0556 (16)	0.0298 (11)	0.0203 (11)	0.0076 (10)	0.0220 (10)
O2	0.0390 (12)	0.0437 (14)	0.0425 (12)	0.0169 (10)	0.0018 (10)	0.0094 (10)
O3	0.0396 (13)	0.084 (2)	0.0231 (10)	−0.0069 (12)	0.0054 (10)	0.0031 (11)
O4	0.0832 (19)	0.0458 (14)	0.0232 (10)	0.0148 (13)	−0.0124 (12)	0.0064 (10)
O5	0.157 (4)	0.159 (4)	0.078 (2)	0.131 (3)	0.048 (2)	0.057 (2)
O6	0.086 (2)	0.071 (2)	0.0585 (17)	0.0377 (17)	0.0398 (16)	0.0197 (15)
N1	0.0429 (15)	0.0458 (18)	0.0438 (15)	0.0179 (13)	0.0097 (13)	0.0123 (13)
N2	0.0226 (11)	0.0256 (12)	0.0232 (10)	0.0018 (9)	−0.0002 (9)	0.0024 (9)
N3	0.0209 (10)	0.0256 (12)	0.0250 (11)	0.0002 (9)	−0.0001 (9)	−0.0011 (9)
C1	0.0231 (12)	0.0250 (14)	0.0249 (13)	−0.0007 (10)	−0.0037 (11)	0.0057 (10)
C2	0.0225 (12)	0.0304 (15)	0.0249 (13)	−0.0013 (11)	0.0004 (11)	0.0028 (11)
C3	0.0234 (12)	0.0289 (15)	0.0206 (12)	−0.0066 (11)	−0.0044 (10)	0.0034 (10)
C4	0.0253 (13)	0.0296 (15)	0.0289 (14)	−0.0026 (11)	−0.0071 (12)	0.0092 (11)
C5	0.0236 (13)	0.0284 (15)	0.0337 (14)	0.0031 (11)	0.0039 (12)	0.0055 (11)
C6	0.0290 (14)	0.0291 (15)	0.0242 (13)	0.0008 (11)	0.0026 (11)	0.0075 (11)
C7	0.0280 (14)	0.0280 (15)	0.0280 (13)	0.0012 (11)	−0.0053 (12)	0.0068 (11)
C8	0.0402 (16)	0.0302 (15)	0.0222 (13)	−0.0106 (13)	−0.0046 (12)	0.0031 (11)
C9	0.0292 (14)	0.0288 (15)	0.0347 (15)	0.0047 (12)	−0.0053 (12)	0.0084 (12)
C10	0.0373 (15)	0.0231 (15)	0.0384 (16)	−0.0031 (12)	−0.0022 (13)	0.0051 (12)
C11	0.0270 (13)	0.0260 (14)	0.0237 (12)	−0.0046 (11)	0.0014 (11)	0.0006 (11)
C12	0.0209 (12)	0.0265 (14)	0.0214 (12)	−0.0012 (10)	0.0034 (10)	0.0000 (10)
C13	0.0191 (12)	0.0296 (15)	0.0262 (13)	−0.0020 (10)	−0.0005 (11)	−0.0008 (10)
C14	0.0188 (12)	0.0275 (14)	0.0265 (13)	0.0038 (10)	0.0004 (11)	0.0010 (11)
C15	0.0221 (12)	0.0240 (13)	0.0212 (12)	0.0017 (10)	0.0040 (10)	0.0004 (10)
C16	0.0261 (13)	0.0215 (13)	0.0237 (12)	0.0005 (10)	0.0010 (11)	−0.0015 (10)
C17	0.0283 (14)	0.0225 (14)	0.0401 (16)	−0.0041 (11)	−0.0011 (13)	0.0024 (12)
C18	0.0219 (13)	0.0300 (16)	0.0365 (15)	−0.0056 (11)	−0.0043 (12)	−0.0009 (12)
C19	0.0217 (12)	0.0224 (14)	0.0178 (11)	0.0006 (10)	0.0024 (10)	−0.0008 (9)
C20	0.0202 (12)	0.0243 (13)	0.0184 (11)	−0.0006 (10)	0.0016 (10)	−0.0023 (9)
C21	0.0289 (14)	0.0225 (14)	0.0311 (14)	−0.0032 (11)	0.0012 (12)	−0.0049 (11)
C22	0.0481 (18)	0.0412 (19)	0.0323 (15)	−0.0193 (15)	0.0021 (14)	0.0000 (13)
C23	0.058 (2)	0.057 (2)	0.053 (2)	−0.0325 (19)	0.0117 (19)	−0.0040 (18)
C24	0.0380 (18)	0.062 (3)	0.061 (2)	−0.0233 (17)	−0.0035 (18)	−0.0137 (19)
C25	0.0339 (16)	0.048 (2)	0.0404 (17)	−0.0013 (14)	−0.0080 (14)	−0.0054 (15)
C26	0.0290 (14)	0.0322 (16)	0.0322 (14)	0.0001 (12)	0.0004 (12)	0.0010 (12)
C27	0.0247 (13)	0.0271 (15)	0.0268 (13)	−0.0004 (11)	0.0029 (11)	0.0028 (11)
C28	0.0314 (14)	0.0288 (15)	0.0288 (13)	−0.0031 (12)	0.0008 (12)	0.0026 (11)
C29	0.0322 (15)	0.048 (2)	0.0291 (14)	0.0001 (14)	0.0005 (13)	0.0115 (13)
C30	0.0460 (18)	0.045 (2)	0.0387 (17)	0.0161 (16)	0.0038 (15)	0.0164 (15)
C31	0.066 (2)	0.0270 (18)	0.0491 (19)	0.0144 (15)	0.0056 (18)	0.0036 (14)
C32	0.0463 (18)	0.0274 (16)	0.0344 (15)	0.0010 (13)	−0.0030 (14)	0.0002 (12)

Geometric parameters (Å, º)

Cd1—O1	2.204 (2)	C12—C19	1.406 (4)
Cd1—O3^i	2.250 (2)	C12—C13	1.430 (4)
Cd1—O4^ii	2.258 (2)	C13—C14	1.352 (4)
Cd1—N2	2.332 (2)	C13—H13A	0.9300
Cd1—N3	2.333 (2)	C14—C15	1.437 (4)
Cd1—O2	2.703 (2)	C14—H14A	0.9300
Cd1—C7	2.786 (3)	C15—C20	1.408 (4)
O1—C7	1.271 (3)	C15—C16	1.428 (4)
O2—C7	1.230 (3)	C16—C17	1.379 (4)
O3—C8	1.236 (4)	C16—C27	1.485 (4)
O3—Cd1^iii	2.250 (2)	C17—C18	1.395 (4)
O4—C8	1.249 (4)	C17—H17A	0.9300
O4—Cd1^iv	2.258 (2)	C18—H18A	0.9300
O5—N1	1.186 (4)	C19—C20	1.455 (4)
O6—N1	1.206 (3)	C21—C22	1.385 (4)
N1—C5	1.471 (4)	C21—C26	1.402 (4)
N2—C9	1.325 (4)	C22—C23	1.388 (5)
N2—C19	1.356 (3)	C22—H22A	0.9300
N3—C18	1.321 (4)	C23—C24	1.376 (5)
N3—C20	1.360 (3)	C23—H23A	0.9300
C1—C6	1.383 (4)	C24—C25	1.371 (5)
C1—C2	1.395 (4)	C24—H24A	0.9300
C1—C7	1.509 (4)	C25—C26	1.377 (4)
C2—C3	1.389 (4)	C25—H25A	0.9300
C2—H2A	0.9300	C26—H26A	0.9300
C3—C4	1.386 (4)	C27—C32	1.395 (4)
C3—C8	1.519 (4)	C27—C28	1.394 (4)
C4—C5	1.384 (4)	C28—C29	1.386 (4)
C4—H4A	0.9300	C28—H28A	0.9300
C5—C6	1.377 (4)	C29—C30	1.368 (5)
C6—H6A	0.9300	C29—H29A	0.9300
C9—C10	1.397 (4)	C30—C31	1.377 (5)
C9—H9A	0.9300	C30—H30A	0.9300
C10—C11	1.370 (4)	C31—C32	1.385 (5)
C10—H10A	0.9300	C31—H31A	0.9300
C11—C12	1.424 (4)	C32—H32A	0.9300
C11—C21	1.490 (4)
O1—Cd1—O3^i	93.94 (9)	C10—C11—C12	118.0 (2)
O1—Cd1—O4^ii	98.23 (10)	C10—C11—C21	119.7 (3)
O3^i—Cd1—O4^ii	124.43 (9)	C12—C11—C21	122.3 (2)
O1—Cd1—N2	103.89 (9)	C19—C12—C11	117.6 (2)
O3^i—Cd1—N2	90.77 (9)	C19—C12—C13	118.6 (2)
O4^ii—Cd1—N2	136.79 (9)	C11—C12—C13	123.8 (2)
O1—Cd1—N3	174.60 (9)	C14—C13—C12	121.5 (2)
O3^i—Cd1—N3	86.36 (8)	C14—C13—H13A	119.2
O4^ii—Cd1—N3	86.00 (9)	C12—C13—H13A	119.2
N2—Cd1—N3	70.71 (8)	C13—C14—C15	121.5 (2)
O1—Cd1—O2	52.15 (7)	C13—C14—H14A	119.3
O3^i—Cd1—O2	142.44 (9)	C15—C14—H14A	119.3
O4^ii—Cd1—O2	81.20 (8)	C20—C15—C16	117.9 (2)
N2—Cd1—O2	83.79 (8)	C20—C15—C14	118.1 (2)
N3—Cd1—O2	125.77 (7)	C16—C15—C14	124.0 (2)
O1—Cd1—C7	26.34 (8)	C17—C16—C15	117.2 (2)
O3^i—Cd1—C7	119.12 (9)	C17—C16—C27	119.5 (2)
O4^ii—Cd1—C7	88.98 (9)	C15—C16—C27	123.3 (2)
N2—Cd1—C7	94.71 (8)	C16—C17—C18	121.1 (3)
N3—Cd1—C7	151.45 (8)	C16—C17—H17A	119.5
O2—Cd1—C7	25.83 (7)	C18—C17—H17A	119.5
C7—O1—Cd1	103.33 (18)	N3—C18—C17	122.5 (2)
C7—O2—Cd1	80.86 (16)	N3—C18—H18A	118.7
C8—O3—Cd1^iii	119.1 (2)	C17—C18—H18A	118.7
C8—O4—Cd1^iv	152.3 (2)	N2—C19—C12	123.1 (2)
O5—N1—O6	121.9 (3)	N2—C19—C20	117.3 (2)
O5—N1—C5	118.7 (3)	C12—C19—C20	119.6 (2)
O6—N1—C5	119.4 (3)	N3—C20—C15	122.8 (2)
C9—N2—C19	117.9 (2)	N3—C20—C19	117.2 (2)
C9—N2—Cd1	124.39 (18)	C15—C20—C19	119.9 (2)
C19—N2—Cd1	117.37 (17)	C22—C21—C26	118.8 (3)
C18—N3—C20	118.4 (2)	C22—C21—C11	120.2 (3)
C18—N3—Cd1	124.11 (17)	C26—C21—C11	120.8 (2)
C20—N3—Cd1	117.24 (18)	C21—C22—C23	120.2 (3)
C6—C1—C2	119.2 (2)	C21—C22—H22A	119.9
C6—C1—C7	118.8 (2)	C23—C22—H22A	119.9
C2—C1—C7	121.9 (2)	C24—C23—C22	120.3 (3)
C3—C2—C1	121.0 (3)	C24—C23—H23A	119.9
C3—C2—H2A	119.5	C22—C23—H23A	119.9
C1—C2—H2A	119.5	C25—C24—C23	120.0 (3)
C4—C3—C2	119.8 (2)	C25—C24—H24A	120.0
C4—C3—C8	119.4 (2)	C23—C24—H24A	120.0
C2—C3—C8	120.8 (3)	C24—C25—C26	120.5 (3)
C3—C4—C5	118.2 (3)	C24—C25—H25A	119.8
C3—C4—H4A	120.9	C26—C25—H25A	119.8
C5—C4—H4A	120.9	C25—C26—C21	120.2 (3)
C6—C5—C4	122.8 (3)	C25—C26—H26A	119.9
C6—C5—N1	118.0 (2)	C21—C26—H26A	119.9
C4—C5—N1	119.2 (3)	C32—C27—C28	118.5 (3)
C5—C6—C1	118.9 (2)	C32—C27—C16	120.3 (2)
C5—C6—H6A	120.6	C28—C27—C16	121.2 (3)
C1—C6—H6A	120.6	C29—C28—C27	120.1 (3)
O2—C7—O1	123.6 (3)	C29—C28—H28A	120.0
O2—C7—C1	121.0 (2)	C27—C28—H28A	120.0
O1—C7—C1	115.4 (2)	C30—C29—C28	120.9 (3)
O2—C7—Cd1	73.32 (16)	C30—C29—H29A	119.5
O1—C7—Cd1	50.33 (14)	C28—C29—H29A	119.5
C1—C7—Cd1	165.46 (19)	C31—C30—C29	119.6 (3)
O3—C8—O4	126.1 (3)	C31—C30—H30A	120.2
O3—C8—C3	116.3 (3)	C29—C30—H30A	120.2
O4—C8—C3	117.5 (3)	C30—C31—C32	120.4 (3)
N2—C9—C10	122.9 (3)	C30—C31—H31A	119.8
N2—C9—H9A	118.6	C32—C31—H31A	119.8
C10—C9—H9A	118.6	C31—C32—C27	120.4 (3)
C11—C10—C9	120.3 (3)	C31—C32—H32A	119.8
C11—C10—H10A	119.8	C27—C32—H32A	119.8
C9—C10—H10A	119.8

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