A novel cadmium(II) coordination polymer with a four-connected (4,4)-net based on a trinuclear cadmium(II) node

In the title cadmium(II) coordination polymer, poly[tri-μ₄-adipato-bis­(2-phenyl-1H-1,3,7,8-tetra­azacyclo­penta[l]phen­anthrene-κ²N⁷,N⁸)tricadmium(II)], [Cd₃(C₆H₈O₄)₃(C₁₉H₁₂N₄)₂]_n, one of the Cd atoms is in a distorted pen­ta­gonal bi­py­ramidal coordination environment, surrounded by five O atoms from three adipate (adip) ligands and two N atoms from one 2-phenyl-1H-1,3,7,8-tetra­azacyclo­penta­[l]phenanthrene (L) ligand. A second Cd atom occupies an inversion center and is coordinated by six O atoms from six adip ligands in a distorted octa­hedral geometry. The carboxyl­ate ends of the adip ligands link Cd^II atoms to form unique trinuclear Cd^II clusters, which are further bridged by the adip linkers to produce a two-dimensional layer structure. Topologically, each trinuclear Cd^II cluster is connected to four others through six adip ligands, thus resulting in a unique two-dimensional four-connected framework of (4,4)-topology. This work may help the development of the coordination chemistry of 1,10-phen­an­throline derivatives.

S1. Comment

Metal–organic coordination polymers built up from polynuclear metal clusters and multicarboxylate building blocks have become an attractive area of research in recent years, owing to their interesting molecular topologies and potential applications as functional materials (Eddaoudi et al., 2001; Hagrman et al., 1999; Noveron et al., 2002). Polynuclear metal clusters can be very versatile in terms of coordination properties and rigidity, as well as displaying intriguing physical properties that are not found in mononuclear species. So far, multi-carboxylate building blocks with special configurations have been selected for use in the design of a wide range of polynuclear metal clusters. Following this direction, a variety of coordination polymers based on polynuclear metal clusters have been obtained using multi-carboxylate building blocks. Typically, benzene-1,2-dicarboxylic acid and benzene-1,3-dicarboxylic acid (have been widely used for the design and synthesis of coordination polymers with polynuclear metal clusters (Yang, Li et al. 2007). However, far less effort has been expended on adipatic acid (H₂adip; Yang, Ma et al., 2007). As a dicarboxylate ligand, H₂adip possesses flexibility owing to the presence of –CH₂– spacers between the two carboxylate groups, which is helpful for the formation of coordination polymers with polynuclear metal clusters.

On the other hand, the preparation of ordered functional crystalline solids, which display a variety of well defined supramolecular architectures mediated by supramolecular interactions, is currently of great interest and importance (Lehn, 1988, 2002). In this regard, 1,10-phenanthroline (phen) and 2,2-bipyridyl have been widely used to build supramolecular architectures owing to their excellent coordinating ability and large conjugated system that can easily form π–π interactions (Tong et al., 2000; Zheng et al., 2001). On this basis, a number of coordination polymers have been prepared from one-dimensional covalently bonded chains or layers, yielding extended two- or three-dimensional supramolecular structures through these interactions (Zhang et al., 2005). However, far less attention has been given to their derivatives (Yang, Li et al., 2007; Yang, Ma et al., 2007). For example, the rare phen derivative 2-phenyl-1H-1,3,7,8,-tetraazacyclopenta[l]phenanthrene (L) possesses a fruitful aromatic system and is a good candidate for construction of metal–organic supramolecular architectures (Steck & Day, 1943). In this contribution, we selected H₂adip as a flexible linker and L as a secondary ligand, generating a new trinuclear Cd^II coordination polymer, namely [Cd₃(C₆H₈O₄)₃(C₁₉H₁₂N₄)₂]_n, (I). Compound (I) is a rare example of a two-dimensional structure with four-connected (4,4) topology based on trinuclear Cd^II nodes.

The asymmetric unit of (I) contains of two crystallographically independent Cd^II atoms. As shown in Fig. 1, atom Cd1 is in a distorted pentagonal–bipyramidal coordination environment consisting of five O atoms from three adip ligands and two N atoms from one L ligand. Atoms O2, O3, O4, N1, and N2 atoms form the basal plane, while atoms O1 and O5 occupy the apical positions. Atom Cd2 lies on an inversion center and is coordinated by six O atoms from six adip ligands in a distorted octahedral geometry, where atoms O2, O2ⁱ, O6 and O6ⁱ [symmetry code: (i) -x, -y + 1, -z + 1] form the basal plane, and atoms O4 and O4ⁱ occupy the apical positions. The Cd—N [2.328 (3) and 2.387 (2) Å] and Cd—O distances [2.218 (2)–2.532 (2) Å] in (I) (Table 1) are comparable to those found in another crystallographically characterized Cd^II complex, [Cd₄(OH)₂(H₂O)₂(sip)₂(4,4'-bpy)₄].H₂O (sip is 5-sulfoisophthalate and 4,4'-bpy is 4,4'-bipyridyl; Li et al., 2005). Notably, in (I), two coordination modes for the adip ligands have been found. One type of adip linker coordinates to four Cd^II atoms in a bis-tridentate mode, while the other type of adip connects four Cd^II centers in a bis-bidentate mode. Interestingly, the carboxylate ends of adip ligands link the Cd^II atoms to form a unique trinuclear Cd^II cluster. These clusters are further bridged by the adip linkers to result in a two-dimensional layer structure (Fig. 2). It is noted that the L ligands are extended on both sides of the layers, and the planes of adjacent L ligands are nearly parallel. These parallel L ligands are paired to furnish strong aromatic π–π stacking interactions [with a centroid-to-centroid distance of 3.785 (2) Å, a vertical face-to-face distance of 3.442 (1) Å and a dihedral angle of 0.80 (3)°], which extend the layers into a three-dimensional supramolecular structure in the bc plane (Fig. 3).

A better insight into the structure of (I) can be achieved by the application of the topological approach, that is, reducing multidimensional structures to simple node-and-linker nets. As discussed above, each trinuclear Cd^II cluster is surrounded by eight organic ligands, namely six bridging adip and two chelating L ligands. Therefore, this defines a four-connected node. Each trinuclear Cd^II cluster core is further linked to four nearest neighbors through six adip ligands, thus resulting in a unique four-connected two-dimensional network (Fig. 4). Considering the trinuclear clusters as nodes and keeping the adip ligands as spacers, the overall topology of the two-dimensional framework is best described as a four-connected (4,4)-net (Yang et al., 2008). So far, occurances of the (4,4)-net have been extensively reported; however, a (4,4)-net based on a trinuclear metal node is rarely observed (Batten & Robson, 1998). Therefore, to our knowledge, (I) is the first example of a two-dimensional (4,4)-net based on a trinuclear Cd^II node. The flexibility of the L ligand may play an important role in the formation of the unusual structure.

It is noteworthy that the structure of (I) is entirely different from that of the related compound [Cd₂(Dpq)₂(BPDC)₂].1.5H₂O (Dpq is dipyrido[3,2-d:2',3'-f]quinoxaline and BPDC is biphenyl-4,4'-dicarboxylate; Wang et al., 2007), in which the BPDC ligands are linked the Cd^II centers to give an interesting six-connected twofold interpenetrated three-dimensional α-Po-related architecture.

Finally, an N—H···O hydrogen bond between the N atom of the L ligand and a carboxylate O atom further stabilizes the structure of (I) (Table 2).

Related literature

For related literature, see: Batten & Robson (1998); Eddaoudi et al. (2001); Hagrman et al. (1999); Lehn (2002); Li et al. (2005); Noveron et al. (2002); Steck & Day (1943); Tong et al. (2000); Wang et al. (2007); Yang et al. (2007a, 2007b, 2008); Zhang et al. (2005); Zheng et al. (2001).

S2. Experimental

A mixture of CdCl₂.2.5H₂O (0.114 g, 0.5 mmol), H₂adip (0.073 g, 0.5 mmol) and L (0.148 g, 0.5 mmol) were dissolved in 12 ml of distilled water, followed by addition of triethylamine until the pH value of the system was adjusted to about 5.5. The resulting solution was stirred for about 1 h at room temperature, sealed in a 23 ml Teflon-lined stainless steel autoclave and heated at 185° for 10 days under autogenous pressure. Afterwards, the reaction system was cooled slowly to room temperature. Pale-yellow block crystals of (I) suitable for single-crystal X-ray diffraction analysis were collected from the final reaction system by filtration, washed several times with distilled water and dried in air at ambient temperature (yield 28% based on Cd^II).

S3. Refinement

All H atoms were positioned geometrically (N—H = 0.86 Å, and C—H = 0.93 and 0.97 Å) and refined as riding, with U_iso(H) values of 1.2U_eq(carrier).

Computing details

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

Figures

	Fig. 1. A view of the local coordination of the Cd^II cation in (I), showing the atom-numbering scheme. Displacement ellipsoids are shown at the 30% probability level. [Symmetry operations: (i) -x, -y + 1, -z + 1; (ii) x + 1, y, z; (iii) -x, -y, -z + 1; (iv) -1 + x, y, z.] Don't match Table 2
	Fig. 2. The layer structure of (I) (DIAMOND; Brandenburg, 2006).
	Fig. 3. A view of the three-dimensional supramolecular structure formed through π–π stacking interactions (DIAMOND; Brandenburg, 2006).
	Fig. 4. A schematic representation of the two-dimensional 4-connected (4,4)net.

poly[di-µ₅-adipato-µ₄-adipato-bis(2-phenyl-1H-1,3,7,8- tetraazacyclopenta[l]phenanthrene-κ²N⁷,N⁸)tricadmium(II)]

Crystal data

[Cd3(C6H8O4)3(C19H12N4)2]	Z = 1
Mr = 1362.28	F(000) = 680
Triclinic, P1	Dx = 1.815 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.321 (1) Å	Cell parameters from 9709 reflections
b = 10.977 (2) Å	θ = 3.0–27.5°
c = 15.365 (3) Å	µ = 1.35 mm^−1
α = 71.62 (2)°	T = 293 K
β = 75.16 (3)°	Block, pale yellow
γ = 71.89 (2)°	0.27 × 0.24 × 0.21 mm
V = 1246.3 (4) Å^3

Data collection

Rigaku R-AXIS RAPID diffractometer	5634 independent reflections
Radiation source: rotating anode	4583 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
Detector resolution: 10.0 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ω scans	h = −10→10
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −14→14
Tmin = 0.685, Tmax = 0.751	l = −19→19
12314 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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.069	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0255P)^2 + 1.2155P] where P = (Fo^2 + 2Fc^2)/3
5634 reflections	(Δ/σ)max = 0.001
358 parameters	Δρmax = 0.48 e Å^−3
0 restraints	Δρmin = −0.72 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	−0.1982 (4)	0.6489 (3)	0.3215 (2)	0.0252 (6)
C2	−0.3385 (4)	0.7668 (3)	0.3391 (3)	0.0355 (8)
H2A	−0.3812	0.8159	0.2815	0.043*
H2B	−0.2901	0.8241	0.3560	0.043*
C3	−0.4901 (4)	0.7358 (4)	0.4150 (3)	0.0457 (9)
H3A	−0.4509	0.6995	0.4744	0.055*
H3B	−0.5763	0.8182	0.4179	0.055*
C4	0.2947 (4)	0.5726 (3)	0.2984 (2)	0.0291 (7)
C5	0.3889 (5)	0.6631 (4)	0.3081 (2)	0.0438 (9)
H5A	0.4971	0.6547	0.2648	0.053*
H5B	0.3219	0.7538	0.2895	0.053*
C6	0.4257 (5)	0.6399 (4)	0.4025 (2)	0.0428 (9)
H6A	0.4993	0.5512	0.4192	0.051*
H6B	0.3184	0.6421	0.4464	0.051*
C7	0.1360 (4)	0.2078 (3)	0.4588 (2)	0.0305 (7)
C8	0.1907 (5)	0.0621 (3)	0.5092 (2)	0.0361 (7)
H8A	0.1673	0.0532	0.5758	0.043*
H8B	0.3135	0.0295	0.4907	0.043*
C9	0.0970 (4)	−0.0226 (3)	0.4879 (2)	0.0344 (7)
H9A	0.1290	−0.0198	0.4221	0.041*
H9B	0.1345	−0.1140	0.5226	0.041*
C10	−0.2702 (4)	0.3275 (3)	0.3213 (2)	0.0340 (7)
H10	−0.2870	0.3484	0.3776	0.041*
C11	−0.3885 (4)	0.2714 (4)	0.3075 (2)	0.0383 (8)
H11	−0.4825	0.2558	0.3536	0.046*
C12	−0.3630 (4)	0.2400 (3)	0.2251 (2)	0.0331 (7)
H12	−0.4402	0.2026	0.2147	0.040*
C13	−0.2206 (4)	0.2639 (3)	0.1560 (2)	0.0258 (6)
C14	−0.1081 (4)	0.3216 (3)	0.1757 (2)	0.0244 (6)
C15	0.0451 (4)	0.3468 (3)	0.1072 (2)	0.0233 (6)
C16	0.0806 (4)	0.3174 (3)	0.0210 (2)	0.0249 (6)
C17	0.2297 (4)	0.3412 (3)	−0.0414 (2)	0.0321 (7)
H17	0.2549	0.3237	−0.0995	0.038*
C18	0.3378 (4)	0.3904 (3)	−0.0159 (2)	0.0357 (8)
H18	0.4385	0.4056	−0.0557	0.043*
C19	0.2934 (4)	0.4172 (3)	0.0708 (2)	0.0337 (7)
H19	0.3667	0.4514	0.0876	0.040*
C20	−0.0385 (4)	0.2606 (3)	0.00450 (19)	0.0242 (6)
C21	−0.1795 (4)	0.2316 (3)	0.0686 (2)	0.0264 (6)
C22	−0.1706 (4)	0.1600 (3)	−0.0466 (2)	0.0278 (6)
C23	−0.2030 (4)	0.0944 (3)	−0.1075 (2)	0.0285 (6)
C24	−0.3625 (4)	0.0683 (3)	−0.0922 (2)	0.0342 (7)
H24	−0.4490	0.0972	−0.0458	0.041*
C25	−0.3940 (5)	−0.0005 (3)	−0.1454 (2)	0.0407 (8)
H25	−0.5001	−0.0196	−0.1337	0.049*
C26	−0.2657 (5)	−0.0404 (3)	−0.2161 (2)	0.0405 (8)
H26	−0.2859	−0.0859	−0.2524	0.049*
C27	−0.1094 (5)	−0.0129 (3)	−0.2324 (2)	0.0384 (8)
H27	−0.0244	−0.0390	−0.2803	0.046*
C28	−0.0764 (4)	0.0534 (3)	−0.1783 (2)	0.0347 (7)
H28	0.0308	0.0705	−0.1894	0.042*
N1	−0.1345 (3)	0.3523 (2)	0.25708 (17)	0.0272 (5)
N2	0.1523 (3)	0.3968 (2)	0.13115 (17)	0.0270 (5)
N3	−0.0334 (3)	0.2143 (2)	−0.06913 (17)	0.0278 (6)
H3	0.0413	0.2185	−0.1197	0.033*
N4	−0.2618 (3)	0.1682 (3)	0.03641 (18)	0.0297 (6)
O1	−0.1143 (3)	0.6519 (2)	0.24133 (15)	0.0385 (6)
O2	−0.1656 (3)	0.5454 (2)	0.38768 (15)	0.0332 (5)
O3	0.3030 (3)	0.5584 (3)	0.22032 (17)	0.0460 (6)
O4	0.2067 (3)	0.5132 (2)	0.36927 (17)	0.0402 (6)
O5	0.1721 (3)	0.2371 (2)	0.37212 (17)	0.0423 (6)
O6	0.0577 (4)	0.2854 (2)	0.50925 (19)	0.0483 (7)
Cd1	0.08006 (3)	0.43806 (2)	0.277754 (15)	0.02549 (7)
Cd2	0.0000	0.5000	0.5000	0.02473 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0242 (14)	0.0318 (15)	0.0254 (15)	−0.0114 (13)	−0.0062 (12)	−0.0093 (12)
C2	0.0303 (17)	0.0352 (17)	0.051 (2)	−0.0114 (14)	−0.0079 (15)	−0.0210 (16)
C3	0.0326 (18)	0.065 (2)	0.056 (2)	−0.0151 (18)	0.0003 (17)	−0.042 (2)
C4	0.0272 (15)	0.0284 (15)	0.0331 (17)	−0.0096 (13)	−0.0047 (13)	−0.0080 (13)
C5	0.060 (2)	0.0447 (19)	0.037 (2)	−0.0316 (19)	−0.0161 (17)	−0.0012 (16)
C6	0.0376 (19)	0.067 (2)	0.0337 (19)	−0.0246 (19)	−0.0001 (15)	−0.0208 (18)
C7	0.0329 (16)	0.0264 (15)	0.0387 (18)	−0.0129 (13)	−0.0058 (14)	−0.0122 (13)
C8	0.0436 (19)	0.0305 (16)	0.0386 (19)	−0.0135 (15)	−0.0141 (15)	−0.0051 (14)
C9	0.0421 (19)	0.0246 (15)	0.0391 (19)	−0.0095 (14)	−0.0109 (15)	−0.0077 (13)
C10	0.0400 (18)	0.0396 (17)	0.0269 (16)	−0.0150 (15)	0.0001 (14)	−0.0147 (14)
C11	0.0353 (18)	0.054 (2)	0.0295 (17)	−0.0212 (17)	0.0066 (14)	−0.0154 (15)
C12	0.0314 (17)	0.0448 (18)	0.0312 (17)	−0.0203 (15)	−0.0034 (14)	−0.0118 (14)
C13	0.0282 (15)	0.0270 (14)	0.0245 (15)	−0.0110 (13)	−0.0044 (12)	−0.0057 (12)
C14	0.0292 (15)	0.0244 (14)	0.0230 (15)	−0.0089 (12)	−0.0062 (12)	−0.0071 (11)
C15	0.0275 (15)	0.0222 (13)	0.0222 (14)	−0.0076 (12)	−0.0064 (12)	−0.0055 (11)
C16	0.0277 (15)	0.0265 (14)	0.0214 (14)	−0.0104 (13)	−0.0044 (12)	−0.0038 (11)
C17	0.0348 (17)	0.0378 (17)	0.0266 (16)	−0.0138 (15)	−0.0017 (13)	−0.0107 (13)
C18	0.0333 (17)	0.0484 (19)	0.0301 (17)	−0.0208 (16)	0.0029 (14)	−0.0127 (15)
C19	0.0339 (17)	0.0414 (18)	0.0331 (17)	−0.0208 (15)	−0.0018 (14)	−0.0116 (14)
C20	0.0305 (15)	0.0270 (14)	0.0197 (14)	−0.0109 (13)	−0.0058 (12)	−0.0074 (11)
C21	0.0307 (16)	0.0295 (15)	0.0245 (15)	−0.0142 (13)	−0.0051 (12)	−0.0077 (12)
C22	0.0333 (16)	0.0312 (15)	0.0231 (15)	−0.0135 (14)	−0.0079 (13)	−0.0051 (12)
C23	0.0400 (17)	0.0284 (14)	0.0219 (15)	−0.0139 (14)	−0.0080 (13)	−0.0057 (12)
C24	0.047 (2)	0.0392 (17)	0.0248 (16)	−0.0224 (16)	−0.0056 (14)	−0.0086 (14)
C25	0.057 (2)	0.0428 (19)	0.0341 (18)	−0.0299 (18)	−0.0096 (16)	−0.0071 (15)
C26	0.069 (3)	0.0348 (17)	0.0280 (17)	−0.0196 (18)	−0.0150 (17)	−0.0105 (14)
C27	0.050 (2)	0.0375 (18)	0.0275 (17)	−0.0055 (16)	−0.0067 (15)	−0.0133 (14)
C28	0.0370 (18)	0.0388 (17)	0.0307 (17)	−0.0094 (15)	−0.0067 (14)	−0.0115 (14)
N1	0.0323 (14)	0.0307 (13)	0.0242 (13)	−0.0122 (11)	−0.0036 (11)	−0.0111 (10)
N2	0.0297 (13)	0.0308 (13)	0.0267 (13)	−0.0126 (11)	−0.0045 (11)	−0.0111 (11)
N3	0.0350 (14)	0.0349 (13)	0.0188 (12)	−0.0166 (12)	−0.0017 (11)	−0.0086 (10)
N4	0.0351 (14)	0.0376 (14)	0.0239 (13)	−0.0171 (12)	−0.0049 (11)	−0.0104 (11)
O1	0.0448 (14)	0.0405 (13)	0.0275 (12)	−0.0157 (11)	0.0044 (10)	−0.0087 (10)
O2	0.0374 (12)	0.0351 (12)	0.0300 (12)	−0.0109 (10)	−0.0128 (10)	−0.0047 (10)
O3	0.0597 (16)	0.0601 (16)	0.0329 (13)	−0.0328 (14)	−0.0071 (12)	−0.0151 (12)
O4	0.0407 (13)	0.0473 (14)	0.0390 (14)	−0.0270 (12)	0.0088 (11)	−0.0167 (11)
O5	0.0655 (17)	0.0289 (11)	0.0360 (14)	−0.0147 (12)	−0.0141 (12)	−0.0059 (10)
O6	0.0654 (18)	0.0263 (12)	0.0515 (16)	−0.0162 (12)	0.0018 (13)	−0.0126 (11)
Cd1	0.03053 (12)	0.02833 (11)	0.02298 (12)	−0.01158 (9)	−0.00432 (9)	−0.01008 (9)
Cd2	0.03343 (17)	0.02485 (15)	0.01876 (15)	−0.00966 (13)	−0.00413 (12)	−0.00750 (12)

Geometric parameters (Å, º)

C1—O1	1.246 (4)	C16—C17	1.400 (4)
C1—O2	1.273 (4)	C16—C20	1.431 (4)
C1—C2	1.493 (4)	C17—C18	1.367 (4)
C2—C3	1.527 (5)	C17—H17	0.9300
C2—H2A	0.9700	C18—C19	1.388 (4)
C2—H2B	0.9700	C18—H18	0.9300
C3—C6^i	1.513 (4)	C19—N2	1.328 (4)
C3—H3A	0.9700	C19—H19	0.9300
C3—H3B	0.9700	C20—N3	1.365 (4)
C4—O3	1.239 (4)	C20—C21	1.375 (4)
C4—O4	1.260 (4)	C21—N4	1.373 (4)
C4—C5	1.504 (4)	C22—N4	1.321 (4)
C5—C6	1.487 (5)	C22—N3	1.367 (4)
C5—H5A	0.9700	C22—C23	1.464 (4)
C5—H5B	0.9700	C23—C28	1.387 (4)
C6—C3^ii	1.513 (4)	C23—C24	1.390 (4)
C6—H6A	0.9700	C24—C25	1.388 (4)
C6—H6B	0.9700	C24—H24	0.9300
C7—O5	1.245 (4)	C25—C26	1.389 (5)
C7—O6	1.251 (4)	C25—H25	0.9300
C7—C8	1.520 (4)	C26—C27	1.370 (5)
C8—C9	1.534 (4)	C26—H26	0.9300
C8—H8A	0.9700	C27—C28	1.385 (5)
C8—H8B	0.9700	C27—H27	0.9300
C9—C9^iii	1.517 (7)	C28—H28	0.9300
C9—H9A	0.9700	N3—H3	0.8600
C9—H9B	0.9700	Cd1—N1	2.387 (2)
C10—N1	1.331 (4)	Cd1—N2	2.328 (3)
C10—C11	1.400 (5)	Cd1—O1	2.391 (3)
C10—H10	0.9300	Cd1—O2	2.532 (2)
C11—C12	1.363 (4)	Cd1—O3	2.431 (2)
C11—H11	0.9300	Cd1—O4	2.408 (2)
C12—C13	1.406 (4)	Cd1—O5	2.249 (2)
C12—H12	0.9300	Cd2—O2	2.318 (2)
C13—C14	1.416 (4)	Cd2—O4	2.284 (2)
C13—C21	1.426 (4)	Cd2—O6	2.218 (2)
C14—N1	1.344 (4)	Cd2—O6^iv	2.218 (2)
C14—C15	1.469 (4)	Cd2—O4^iv	2.284 (2)
C15—N2	1.353 (4)	Cd2—O2^iv	2.318 (2)
C15—C16	1.398 (4)
O1—C1—O2	120.1 (3)	N4—C21—C13	128.6 (3)
O1—C1—C2	119.6 (3)	C20—C21—C13	120.7 (2)
O2—C1—C2	120.2 (3)	N4—C22—N3	112.6 (3)
C1—C2—C3	115.3 (3)	N4—C22—C23	125.2 (3)
C1—C2—H2A	108.4	N3—C22—C23	122.2 (3)
C3—C2—H2A	108.4	C28—C23—C24	119.1 (3)
C1—C2—H2B	108.4	C28—C23—C22	121.5 (3)
C3—C2—H2B	108.4	C24—C23—C22	119.4 (3)
H2A—C2—H2B	107.5	C25—C24—C23	120.8 (3)
C6^i—C3—C2	115.4 (3)	C25—C24—H24	119.6
C6^i—C3—H3A	108.4	C23—C24—H24	119.6
C2—C3—H3A	108.4	C26—C25—C24	119.3 (3)
C6^i—C3—H3B	108.4	C26—C25—H25	120.3
C2—C3—H3B	108.4	C24—C25—H25	120.3
H3A—C3—H3B	107.5	C27—C26—C25	120.0 (3)
O3—C4—O4	120.7 (3)	C27—C26—H26	120.0
O3—C4—C5	119.5 (3)	C25—C26—H26	120.0
O4—C4—C5	119.8 (3)	C26—C27—C28	120.8 (3)
C6—C5—C4	116.1 (3)	C26—C27—H27	119.6
C6—C5—H5A	108.3	C28—C27—H27	119.6
C4—C5—H5A	108.3	C27—C28—C23	120.0 (3)
C6—C5—H5B	108.3	C27—C28—H28	120.0
C4—C5—H5B	108.3	C23—C28—H28	120.0
H5A—C5—H5B	107.4	C10—N1—C14	119.1 (2)
C5—C6—C3^ii	116.7 (3)	C10—N1—Cd1	124.8 (2)
C5—C6—H6A	108.1	C14—N1—Cd1	115.96 (18)
C3^ii—C6—H6A	108.1	C19—N2—C15	118.4 (3)
C5—C6—H6B	108.1	C19—N2—Cd1	123.8 (2)
C3^ii—C6—H6B	108.1	C15—N2—Cd1	117.73 (18)
H6A—C6—H6B	107.3	C20—N3—C22	106.4 (2)
O5—C7—O6	127.0 (3)	C20—N3—H3	126.8
O5—C7—C8	117.0 (3)	C22—N3—H3	126.8
O6—C7—C8	116.1 (3)	C22—N4—C21	104.4 (2)
C7—C8—C9	112.1 (3)	C1—O1—Cd1	97.3 (2)
C7—C8—H8A	109.2	C1—O2—Cd2	129.29 (18)
C9—C8—H8A	109.2	C1—O2—Cd1	89.94 (18)
C7—C8—H8B	109.2	Cd2—O2—Cd1	93.91 (8)
C9—C8—H8B	109.2	C4—O3—Cd1	92.36 (18)
H8A—C8—H8B	107.9	C4—O4—Cd2	154.8 (2)
C9^iii—C9—C8	113.4 (3)	C4—O4—Cd1	92.9 (2)
C9^iii—C9—H9A	108.9	Cd2—O4—Cd1	98.20 (8)
C8—C9—H9A	108.9	C7—O5—Cd1	125.2 (2)
C9^iii—C9—H9B	108.9	C7—O6—Cd2	138.3 (2)
C8—C9—H9B	108.9	O5—Cd1—N2	103.07 (9)
H9A—C9—H9B	107.7	O5—Cd1—N1	86.65 (9)
N1—C10—C11	122.8 (3)	N2—Cd1—N1	70.66 (8)
N1—C10—H10	118.6	O5—Cd1—O1	153.45 (9)
C11—C10—H10	118.6	N2—Cd1—O1	98.78 (9)
C12—C11—C10	118.6 (3)	N1—Cd1—O1	86.53 (9)
C12—C11—H11	120.7	O5—Cd1—O4	84.01 (9)
C10—C11—H11	120.7	N2—Cd1—O4	136.70 (8)
C11—C12—C13	120.2 (3)	N1—Cd1—O4	152.51 (8)
C11—C12—H12	119.9	O1—Cd1—O4	90.38 (9)
C13—C12—H12	119.9	O5—Cd1—O3	111.41 (10)
C12—C13—C14	117.4 (3)	N2—Cd1—O3	85.23 (8)
C12—C13—C21	124.7 (3)	N1—Cd1—O3	152.91 (8)
C14—C13—C21	117.9 (3)	O1—Cd1—O3	85.10 (9)
N1—C14—C13	121.9 (3)	O4—Cd1—O3	53.32 (8)
N1—C14—C15	117.9 (2)	O5—Cd1—O2	101.13 (9)
C13—C14—C15	120.1 (3)	N2—Cd1—O2	142.84 (8)
N2—C15—C16	121.3 (3)	N1—Cd1—O2	83.13 (8)
N2—C15—C14	117.7 (2)	O1—Cd1—O2	52.56 (7)
C16—C15—C14	121.0 (2)	O4—Cd1—O2	73.45 (8)
C15—C16—C17	118.9 (3)	O3—Cd1—O2	111.39 (8)
C15—C16—C20	116.4 (2)	O6—Cd2—O6^iv	180.00 (14)
C17—C16—C20	124.7 (3)	O6—Cd2—O4	86.90 (9)
C18—C17—C16	119.3 (3)	O6^iv—Cd2—O4	93.10 (9)
C18—C17—H17	120.4	O6—Cd2—O4^iv	93.10 (9)
C16—C17—H17	120.4	O6^iv—Cd2—O4^iv	86.90 (9)
C17—C18—C19	118.4 (3)	O4—Cd2—O4^iv	180.0
C17—C18—H18	120.8	O6—Cd2—O2	89.51 (10)
C19—C18—H18	120.8	O6^iv—Cd2—O2	90.49 (10)
N2—C19—C18	123.8 (3)	O4—Cd2—O2	79.91 (9)
N2—C19—H19	118.1	O4^iv—Cd2—O2	100.09 (9)
C18—C19—H19	118.1	O6—Cd2—O2^iv	90.49 (10)
N3—C20—C21	105.9 (2)	O6^iv—Cd2—O2^iv	89.51 (10)
N3—C20—C16	130.1 (3)	O4—Cd2—O2^iv	100.09 (9)
C21—C20—C16	123.8 (3)	O4^iv—Cd2—O2^iv	79.91 (9)
N4—C21—C20	110.7 (3)	O2—Cd2—O2^iv	180.0

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1^v	0.86	2.04	2.770 (3)	142

Symmetry code: (v) −x, −y+1, −z.