A two-dimensional bilayered Cd^II coordination polymer with a three-dimensional supra­molecular architecture incorporating 1,2-bis­(pyridin-4-yl)ethene and 2,2′-(diazene­diyl)di­benzoic acid

In poly[[μ₂-1,2-bis­(pyridin-4-yl)ethene-κ²N:N′][μ₂-2,2′-(di­az­ene­diyl)dibenzoato-κ³O,O′:O′′]cadmium(II)], [Cd(C₁₄H₈N₂O₄)(C₁₂H₁₀N₂)]_n, the asymmetric unit contains one Cd^II cat­ion, one 2,2′-(diazene­diyl)dibenzoate anion (denoted L²⁻) and one 1,2-bis­(pyridin-4-yl)ethene ligand (denoted bpe). Each Cd^II centre is six-coordinated by four O atoms of bridging/chelating carboxyl­ate groups from three L²⁻ ligands and by two N atoms from two bpe ligands, forming a distorted octa­hedron. The Cd^II cations are bridged by L²⁻ and bpe ligands to give a two-dimensional (4,4) layer. The layers are inter­linked through bridging carboxyl­ate O atoms from L²⁻ ligands, generating a two-dimensional bilayered structure with a 3⁶4¹³6² topology. The bilayered structures are further extended to form a three-dimensional supra­molecular architecture via a combination of hydrogen-bonding and aromatic stacking inter­actions.

S1. Introduction

The synthesis and design of novel coordination polymers currently attract considerable attention, due to their intriguing structural diversity and their potential applications as functional materials (Kong et al., 2013; Schoedel et al., 2013; Tan et al., 2012; Liao et al., 2012; Horcajada et al., 2008). Generally, the organization of such materials is dependent on many factors, such as the metal ion, the nature of the organic ligands, the pH value, solvent, temperature and counterion, and the number of coordination sites provided by the organic ligands (Lee et al., 2010; Han et al., 2010; Horike et al., 2009; Liu et al., 2012). The most important of these factors is the choice of ligand. Ligands containing different functional groups, including pyridine, triazole and carb­oxy­lic acid, are frequently chosen to regulate the structural assembly, thus affording various coordination systems from discrete to infinite one-, two- and three-dimensional polymeric frameworks.

To date, flexible azo­benzene–di­carb­oxy­lic ligands have been employed as bridging ligands for the construction of functional metal–organic frameworks (MOFs) (Cairns et al., 2008; Lee et al., 2008; Bhattacharya et al., 2011; Yang et al., 2011; Liu et al., 2011; Liu et al., 2013 or Liu & Zhao, 2013 ?). For example, Yaghi and co-workers reacted 4,4'-(diazenediyl)di­benzoic acid (H₂L₁) with Tb(NO₃)₃.5H₂O and obtained an inter­penetrating network of {Tb₂(L₁)₃[(CH₃)₂SO]₄.16[(CH₃)₂SO]}_n with a large free volume (Reineke et al., 2000). Recently, our group has synthesized a series of two- and three-dimensional Cd^II coordination polymers based on 3,3'-(diazenediyl)di­benzoic acid through regulating the reaction solvent and temperature (Liu et al., 2013 or Liu & Zhao, 2013 ?). However, to the best of our knowledge, studies of the coordination chemistry of 2,2'-(diazenediyl)di­benzoic acid (H₂L) have attracted little attention. Furthermore, it is known that a mixed-ligand system consisting of two types ligands provides more variability to construct different topologies (Du et al., 2013). One of the most fruitful choices has been the combination of various carb­oxy­lic acids and neutral pyridine-containing auxiliary ligands, where the carb­oxy­lic acid ligands balance the positive charge of the metal centre and develop secondary building units, while the auxiliary ligands increase the dimensionality or supply additional structural versatility. Taking this into account, we reacted Cd(OAc)₂.2H₂O with H₂L and 1,2-bis­(pyridin-4-yl)ethene (bpe), producing the title compound, [CdL(bpe)]_n, (I).

S2. Experimental

S2.1. Synthesis and crystallization

H₂L was prepared according to the literature method of Reid & Pritchett (1953). All other chemicals and reagents were obtained from commercial sources (Alfa Aesar) and used as received. A mixture of Cd(OAc)₂.2H₂O (13 mg, 0.05 mmol), H₂L (7 mg, 0.025 mmol), bpe (5 mg, 0.025 mmol), 0.010 M NaOH (0.3 ml) and H₂O (4 ml) was sealed in a 10 ml Pyrex glass tube and heated at 393 K for 4 d, then cooled to room temperature at a rate of 5 K h^-1. Pink blocks of (I) were collected and washed thoroughly with H₂O and dried in air (yield 7 mg, 50%, based on H₂L). Spectroscopic analysis: IR (KBr disc, ν, cm^-1): 3386 (m), 3300 (m), 3059 (w), 2932 (w), 1607 (s), 1592 (s), 1381 (s), 1254 (w), 1135 (w), 1098 (m), 1014 (w), 965 (m), 826 (m), 778 (m), 770 (m), 661 (m), 586 (m), 479 (w), 416 (w).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were placed in the geometrically idealized positions, with C—H = 0.93 Å for phenyl and pyridine H atoms, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C).

S3. Results and discussion

The title polymer, (I), crystallizes in the monoclinic space group P2₁/n and its asymmetric unit contains one [CdL(bpe)] unit. As shown in Fig. 1, each Cd^II cation is in a six-coordinate geometry formed by four carboxyl­ate O atoms from three L^2- ligands and two N atoms from two bpe ligands to form a distorted o­cta­hedron. There is one weak inter­action [2.7317 (17) Å] between atoms Cd1 and O4ⁱⁱ (see Fig. 1 for symmetry code). See Table 2 for further bond lengths and angles.

In the structure of (I), each L^2- ligand serves as a bridging ligand, linking adjacent Cd^II centres to generate a one-dimensional [CdL]_n chain extending along the a axis (Fig. 2), with a Cd···Cd separation of 11.417 (2) Å. Each chain is connected to adjacent chains via bpe ligands to form a two-dimensional (4,4) layer (extending along the ac plane), with parallelogram-shaped meshes (11.417 × 13.953 Ų) (Fig. 3). The two-dimensional layers are further inter­linked via bridging carboxyl­ate O atoms from L^2- ligands, resulting in a two-dimensional bilayered structure lying parallel to the ac plane (Fig. 4). Topologically (Wells, 1997), if the Cd^II centres are considered as nodes and the L^2- and bpe ligands are considered as linkers, the bilayer structure of (I) can be specified by a Schläfli symbol of 3⁶4¹³6² (Fig. 5).

Atom O4 of the carboxyl­ate group acts as an acceptor and inter­acts with the H atom of benzene atom C11 in an adjacent network, forming an inter­molecular hydrogen bond (C11—H11···O4ⁱ; see Table 3 for symmetry code). These hydrogen-bonding inter­actions join the two-dimensional bilayer structures to generate a three-dimensional hydrogen-bonded motif in the bc plane (Fig. 6). The structure is also stabilized by π–π stacking inter­actions between the pyridine (atoms N3/C15–C19) and benzene (atoms C2–C7) rings, with a centroid-to-centroid distance of 3.7021 (16) Å. The dihedral angle α defined by the stacked rings is 17.11 (12)°, and the slippage angles are β = 27.08° and γ = 10.66° (Fig. 6).

As reported previously (Chen et al., 2007), a Zn^II coordination polymer assembled from 4,4'-(diazenediyl)di­benzoic acid (H₂L₁) and bpe has been investigated, viz. {[Zn(L₁)(bpe)_0.5].2.5DMF.0.5H₂O}_n, (II), and shows a three-dimensional coordination framework. In (I), the L^2- ligands adopt both bridging and chelating coordination modes and link the Cd^II centres in the [100] direction, producing a one-dimensional chain. These chains are further bridged by bpe ligands, resulting in a two-dimensional layer. In (II), the Zn₂ units are bridged by L₁^2- ligands (bridging coordination mode) in two directions to form a two-dimensional (4,4) network and further pillared by bpe to form a three-dimensional triply inter­penetrated structure. Such differences indicate that ligand geometry and choice of metal greatly affect the resulting motifs of coordination polymers.

In summary, reaction of Cd(OAc)₂.2H₂O with 2,2'-(diazenediyl)di­benzoic acid and 1,2-bis­(pyridin-4-yl)ethene in H₂O affords the title complex under hydro­thermal conditions. The compound displays a rare two-dimensional bilayered structure with a 3⁶4¹³6² topology. The three-dimensional supra­molecular architecture is produced via hydrogen-bonding and aromatic stacking inter­actions.

Related literature

For related literature, see: Bhattacharya et al. (2011); Cairns et al. (2008); Chen et al. (2007); Du et al. (2013); Han et al. (2010); Horcajada et al. (2008); Horike et al. (2009); Kong et al. (2013); Lee et al. (2008, 2010); Liao et al. (2012); Liu & Zhao (2013); Liu et al. (2011, 2012); Reid & Pritchett (1953); Reineke et al. (2000); Schoedel et al. (2013); Tan et al. (2012); Wells (1997); Yang et al. (2011).

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXL2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

Fig. 1. The coordination environment of the Cd atom in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The dashed line represents the weak interaction between atoms Cd1 and O4ⁱⁱ. [Symmetry codes: (ii) x + 1, y, z; (iii) x, y, z - 1; (iv) -x + 1, -y + 1, -z + 1.]

Fig. 2. A view of the one-dimensional coordination chain of (I), linked via bridging L^2- ligands.

Fig. 3. A view of the two-dimensional (4,4) layer of (I), extending along the ac plane. All H atoms have been omitted for clarity.

Fig. 4. A view of the two-dimensional bi-layered structure of (I), extending along the ac plane. All H atoms have been omitted for clarity.

Fig. 5. A view of the topological structure of (I). Turquoise balls represent 7-connected nodes and purple lines represent linkers of L^2- and bpe ligands.

Fig. 6. A view of the three-dimensional supramolecular structure of (I), formed via hydrogen bonding and aromatic stacking interactions. Adjacent layers are shown in different colours. Red dashed lines represent hydrogen bonds and blue dashed lines indicate aromatic stacking interactions. All H atoms except those related to hydrogen-bonding interactions have been omitted for clarity.

Poly[[µ₂-1,2-bis(pyridin-4-yl)ethene-κ²N:N'][µ₂-2,2'-(diazenediyl)dibenzoato-κ³O,O':O'']cadmium(II)]

Crystal data

[Cd(C14H8N2O4)(C12H10N2)]	F(000) = 1128
Mr = 562.84	Dx = 1.692 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.417 (2) Å	Cell parameters from 9920 reflections
b = 15.127 (3) Å	θ = 2.4–28.4°
c = 13.953 (3) Å	µ = 1.03 mm^−1
β = 113.56 (3)°	T = 296 K
V = 2208.8 (9) Å^3	Block, pink
Z = 4	0.20 × 0.15 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	4476 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.032
φ and ω scans	θmax = 28.4°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −15→15
Tmin = 0.830, Tmax = 0.857	k = −19→20
29346 measured reflections	l = −18→18
5546 independent 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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.065	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0267P)^2 + 1.2884P] where P = (Fo^2 + 2Fc^2)/3
5531 reflections	(Δ/σ)max = 0.001
316 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.54 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.

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

	x	y	z	Uiso*/Ueq
Cd1	0.85744 (2)	0.57934 (2)	0.46226 (2)	0.03224 (6)
C1	0.6081 (2)	0.63127 (17)	0.37153 (16)	0.0338 (5)
C2	0.47303 (19)	0.65276 (15)	0.29705 (17)	0.0332 (5)
C3	0.4481 (2)	0.66125 (17)	0.19126 (18)	0.0409 (5)
H3	0.5139	0.6529	0.1688	0.049*
C4	0.3272 (2)	0.68185 (18)	0.11938 (19)	0.0452 (6)
H4	0.3117	0.6874	0.0489	0.054*
C5	0.2291 (2)	0.69416 (18)	0.1525 (2)	0.0466 (6)
H5	0.1476	0.7084	0.1042	0.056*
C6	0.2518 (2)	0.68542 (17)	0.2569 (2)	0.0434 (6)
H6	0.1853	0.6934	0.2785	0.052*
C7	0.37338 (19)	0.66482 (15)	0.32993 (17)	0.0324 (5)
C8	0.3502 (2)	0.66117 (15)	0.57681 (17)	0.0333 (5)
C9	0.4762 (2)	0.66090 (18)	0.6494 (2)	0.0448 (6)
H9	0.5421	0.6536	0.6270	0.054*
C10	0.5041 (2)	0.67139 (19)	0.7546 (2)	0.0501 (6)
H10	0.5883	0.6680	0.8031	0.060*
C11	0.4072 (3)	0.68693 (19)	0.78789 (19)	0.0514 (7)
H11	0.4263	0.6976	0.8582	0.062*
C12	0.2816 (2)	0.68655 (19)	0.71616 (18)	0.0460 (6)
H12	0.2165	0.6977	0.7387	0.055*
C13	0.2509 (2)	0.66967 (15)	0.61075 (17)	0.0337 (5)
C14	0.11219 (19)	0.65396 (16)	0.54090 (15)	0.0321 (5)
C15	0.9595 (2)	0.61844 (18)	0.70803 (17)	0.0401 (5)
H15	1.0255	0.6439	0.6946	0.048*
C16	0.9660 (2)	0.62197 (17)	0.80875 (16)	0.0385 (5)
H16	1.0345	0.6497	0.8613	0.046*
C17	0.8691 (2)	0.58364 (15)	0.83072 (16)	0.0330 (5)
C18	0.7690 (2)	0.54389 (17)	0.74839 (17)	0.0376 (5)
H18	0.7023	0.5173	0.7599	0.045*
C19	0.7694 (2)	0.54426 (16)	0.64984 (16)	0.0365 (5)
H19	0.7013	0.5182	0.5954	0.044*
C20	0.8766 (2)	0.58749 (17)	0.93792 (17)	0.0401 (5)
H20	0.9460	0.6180	0.9859	0.048*
C21	0.7968 (2)	0.55290 (17)	0.97436 (17)	0.0403 (5)
H21	0.7260	0.5229	0.9275	0.048*
C22	0.8115 (2)	0.55828 (16)	1.08339 (16)	0.0351 (5)
C23	0.9183 (2)	0.59518 (17)	1.16178 (17)	0.0410 (6)
H23	0.9834	0.6189	1.1456	0.049*
C24	0.9281 (2)	0.59679 (17)	1.26284 (17)	0.0393 (5)
H24	1.0012	0.6211	1.3140	0.047*
C25	0.7350 (2)	0.52888 (18)	1.21695 (17)	0.0413 (6)
H25	0.6714	0.5060	1.2355	0.050*
C26	0.7187 (2)	0.52370 (19)	1.11355 (17)	0.0451 (6)
H26	0.6460	0.4972	1.0644	0.054*
N1	0.40723 (17)	0.66223 (13)	0.44004 (15)	0.0359 (4)
N2	0.31425 (17)	0.65714 (13)	0.46625 (14)	0.0355 (4)
N3	0.86399 (17)	0.58059 (13)	0.62892 (13)	0.0334 (4)
N4	0.83739 (17)	0.56498 (13)	1.29135 (13)	0.0335 (4)
O1	0.63330 (15)	0.55260 (12)	0.39939 (13)	0.0421 (4)
O2	0.68988 (15)	0.69148 (12)	0.39413 (13)	0.0461 (4)
O3	0.08109 (15)	0.57455 (11)	0.51322 (12)	0.0399 (4)
O4	0.03255 (16)	0.71318 (13)	0.52188 (14)	0.0538 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02453 (8)	0.05550 (12)	0.01840 (7)	0.00586 (7)	0.01038 (6)	0.00213 (7)
C1	0.0274 (10)	0.0530 (15)	0.0245 (9)	0.0047 (10)	0.0142 (8)	−0.0003 (10)
C2	0.0254 (10)	0.0402 (13)	0.0334 (11)	0.0033 (9)	0.0113 (9)	0.0034 (10)
C3	0.0346 (11)	0.0562 (16)	0.0336 (11)	0.0055 (11)	0.0152 (10)	0.0056 (11)
C4	0.0431 (13)	0.0550 (16)	0.0319 (11)	0.0013 (12)	0.0090 (10)	0.0062 (11)
C5	0.0296 (11)	0.0567 (17)	0.0444 (13)	0.0040 (11)	0.0050 (10)	0.0071 (12)
C6	0.0262 (10)	0.0544 (16)	0.0490 (14)	0.0046 (10)	0.0145 (10)	0.0067 (12)
C7	0.0267 (10)	0.0360 (12)	0.0362 (11)	0.0003 (9)	0.0144 (9)	0.0014 (9)
C8	0.0279 (10)	0.0385 (13)	0.0341 (11)	−0.0045 (9)	0.0129 (9)	−0.0051 (10)
C9	0.0290 (11)	0.0543 (16)	0.0477 (14)	−0.0033 (11)	0.0117 (10)	−0.0007 (12)
C10	0.0353 (13)	0.0589 (17)	0.0430 (14)	−0.0103 (12)	0.0019 (11)	−0.0002 (13)
C11	0.0512 (15)	0.0651 (19)	0.0315 (12)	−0.0181 (13)	0.0099 (11)	−0.0083 (12)
C12	0.0418 (13)	0.0668 (18)	0.0320 (11)	−0.0125 (12)	0.0174 (10)	−0.0106 (12)
C13	0.0303 (10)	0.0414 (13)	0.0304 (10)	−0.0056 (9)	0.0131 (9)	−0.0035 (10)
C14	0.0267 (10)	0.0533 (15)	0.0196 (9)	−0.0037 (10)	0.0128 (8)	0.0019 (9)
C15	0.0363 (12)	0.0596 (16)	0.0279 (10)	−0.0056 (11)	0.0166 (9)	0.0006 (11)
C16	0.0378 (12)	0.0541 (15)	0.0234 (10)	−0.0065 (11)	0.0121 (9)	−0.0029 (10)
C17	0.0406 (11)	0.0390 (12)	0.0223 (9)	0.0020 (10)	0.0156 (9)	0.0016 (9)
C18	0.0431 (13)	0.0462 (14)	0.0293 (10)	−0.0050 (10)	0.0206 (10)	−0.0008 (10)
C19	0.0409 (12)	0.0459 (13)	0.0239 (10)	−0.0034 (10)	0.0142 (9)	−0.0032 (10)
C20	0.0464 (13)	0.0535 (15)	0.0218 (9)	−0.0059 (11)	0.0151 (9)	−0.0035 (10)
C21	0.0455 (13)	0.0551 (15)	0.0226 (10)	−0.0044 (11)	0.0161 (9)	−0.0028 (10)
C22	0.0405 (12)	0.0467 (14)	0.0210 (9)	0.0007 (10)	0.0154 (9)	0.0002 (9)
C23	0.0424 (13)	0.0591 (16)	0.0260 (10)	−0.0111 (11)	0.0184 (10)	−0.0024 (10)
C24	0.0393 (12)	0.0559 (16)	0.0244 (10)	−0.0074 (11)	0.0147 (9)	−0.0020 (10)
C25	0.0391 (12)	0.0614 (17)	0.0291 (11)	−0.0042 (11)	0.0195 (10)	−0.0017 (11)
C26	0.0394 (12)	0.0711 (18)	0.0254 (10)	−0.0107 (12)	0.0135 (10)	−0.0068 (11)
N1	0.0291 (9)	0.0448 (11)	0.0377 (10)	0.0021 (8)	0.0176 (8)	0.0015 (9)
N2	0.0285 (9)	0.0452 (12)	0.0367 (10)	−0.0020 (8)	0.0170 (8)	−0.0037 (9)
N3	0.0361 (9)	0.0443 (11)	0.0239 (8)	0.0015 (8)	0.0163 (7)	0.0002 (8)
N4	0.0339 (9)	0.0475 (12)	0.0216 (8)	0.0031 (8)	0.0137 (7)	0.0007 (8)
O1	0.0346 (8)	0.0515 (11)	0.0398 (9)	0.0082 (7)	0.0144 (7)	0.0103 (8)
O2	0.0302 (8)	0.0556 (11)	0.0469 (10)	−0.0031 (8)	0.0094 (7)	−0.0017 (8)
O3	0.0299 (8)	0.0465 (10)	0.0365 (8)	−0.0064 (7)	0.0060 (7)	−0.0014 (8)
O4	0.0424 (10)	0.0663 (13)	0.0472 (10)	0.0167 (9)	0.0120 (8)	−0.0011 (9)

Geometric parameters (Å, º)

Cd1—N3	2.2966 (17)	C13—C14	1.510 (3)
Cd1—N4^i	2.3130 (17)	C14—O4	1.227 (3)
Cd1—O3^ii	2.3621 (17)	C14—O3	1.268 (3)
Cd1—O1	2.3848 (18)	C15—N3	1.331 (3)
Cd1—O3^iii	2.4158 (18)	C15—C16	1.378 (3)
Cd1—O2	2.4469 (18)	C15—H15	0.9300
Cd1—C1	2.728 (2)	C16—C17	1.388 (3)
C1—O1	1.249 (3)	C16—H16	0.9300
C1—O2	1.251 (3)	C17—C18	1.392 (3)
C1—C2	1.511 (3)	C17—C20	1.465 (3)
C2—C3	1.393 (3)	C18—C19	1.377 (3)
C2—C7	1.398 (3)	C18—H18	0.9300
C3—C4	1.379 (3)	C19—N3	1.343 (3)
C3—H3	0.9300	C19—H19	0.9300
C4—C5	1.384 (3)	C20—C21	1.316 (3)
C4—H4	0.9300	C20—H20	0.9300
C5—C6	1.381 (3)	C21—C22	1.464 (3)
C5—H5	0.9300	C21—H21	0.9300
C6—C7	1.390 (3)	C22—C23	1.389 (3)
C6—H6	0.9300	C22—C26	1.390 (3)
C7—N1	1.427 (3)	C23—C24	1.369 (3)
C8—C9	1.390 (3)	C23—H23	0.9300
C8—C13	1.398 (3)	C24—N4	1.339 (3)
C8—N2	1.430 (3)	C24—H24	0.9300
C9—C10	1.381 (4)	C25—N4	1.331 (3)
C9—H9	0.9300	C25—C26	1.381 (3)
C10—C11	1.381 (4)	C25—H25	0.9300
C10—H10	0.9300	C26—H26	0.9300
C11—C12	1.382 (3)	N1—N2	1.256 (2)
C11—H11	0.9300	N4—Cd1^iv	2.3130 (17)
C12—C13	1.393 (3)	O3—Cd1^v	2.3621 (17)
C12—H12	0.9300	O3—Cd1^iii	2.4158 (18)
N3—Cd1—N4^i	173.96 (7)	C11—C12—H12	119.5
N3—Cd1—O3^ii	95.83 (7)	C13—C12—H12	119.5
N4^i—Cd1—O3^ii	87.54 (7)	C12—C13—C8	118.6 (2)
N3—Cd1—O1	88.27 (7)	C12—C13—C14	117.82 (19)
N4^i—Cd1—O1	87.44 (7)	C8—C13—C14	123.36 (19)
O3^ii—Cd1—O1	167.82 (6)	O4—C14—O3	122.2 (2)
N3—Cd1—O3^iii	88.54 (6)	O4—C14—C13	121.3 (2)
N4^i—Cd1—O3^iii	87.65 (6)	O3—C14—C13	116.1 (2)
O3^ii—Cd1—O3^iii	73.14 (6)	N3—C15—C16	123.7 (2)
O1—Cd1—O3^iii	95.56 (6)	N3—C15—H15	118.1
N3—Cd1—O2	95.26 (7)	C16—C15—H15	118.1
N4^i—Cd1—O2	85.68 (7)	C15—C16—C17	119.1 (2)
O3^ii—Cd1—O2	136.17 (6)	C15—C16—H16	120.5
O1—Cd1—O2	54.36 (6)	C17—C16—H16	120.5
O3^iii—Cd1—O2	149.40 (6)	C16—C17—C18	117.53 (19)
N3—Cd1—C1	94.19 (7)	C16—C17—C20	118.9 (2)
N4^i—Cd1—C1	83.90 (7)	C18—C17—C20	123.6 (2)
O3^ii—Cd1—C1	161.89 (7)	C19—C18—C17	119.5 (2)
O1—Cd1—C1	27.24 (6)	C19—C18—H18	120.2
O3^iii—Cd1—C1	122.23 (7)	C17—C18—H18	120.2
O2—Cd1—C1	27.29 (6)	N3—C19—C18	122.8 (2)
O1—C1—O2	124.0 (2)	N3—C19—H19	118.6
O1—C1—C2	117.6 (2)	C18—C19—H19	118.6
O2—C1—C2	118.1 (2)	C21—C20—C17	127.7 (2)
O1—C1—Cd1	60.88 (11)	C21—C20—H20	116.1
O2—C1—Cd1	63.73 (12)	C17—C20—H20	116.1
C2—C1—Cd1	165.93 (14)	C20—C21—C22	124.7 (2)
C3—C2—C7	119.2 (2)	C20—C21—H21	117.6
C3—C2—C1	117.94 (18)	C22—C21—H21	117.6
C7—C2—C1	122.89 (19)	C23—C22—C26	116.65 (19)
C4—C3—C2	120.8 (2)	C23—C22—C21	122.7 (2)
C4—C3—H3	119.6	C26—C22—C21	120.6 (2)
C2—C3—H3	119.6	C24—C23—C22	120.2 (2)
C3—C4—C5	119.7 (2)	C24—C23—H23	119.9
C3—C4—H4	120.1	C22—C23—H23	119.9
C5—C4—H4	120.1	N4—C24—C23	123.0 (2)
C6—C5—C4	120.3 (2)	N4—C24—H24	118.5
C6—C5—H5	119.9	C23—C24—H24	118.5
C4—C5—H5	119.9	N4—C25—C26	123.2 (2)
C5—C6—C7	120.4 (2)	N4—C25—H25	118.4
C5—C6—H6	119.8	C26—C25—H25	118.4
C7—C6—H6	119.8	C25—C26—C22	119.6 (2)
C6—C7—C2	119.6 (2)	C25—C26—H26	120.2
C6—C7—N1	123.82 (19)	C22—C26—H26	120.2
C2—C7—N1	116.35 (19)	N2—N1—C7	114.74 (19)
C9—C8—C13	119.8 (2)	N1—N2—C8	113.60 (18)
C9—C8—N2	123.58 (19)	C15—N3—C19	117.29 (18)
C13—C8—N2	116.59 (19)	C15—N3—Cd1	121.84 (14)
C10—C9—C8	120.4 (2)	C19—N3—Cd1	120.85 (14)
C10—C9—H9	119.8	C25—N4—C24	117.26 (18)
C8—C9—H9	119.8	C25—N4—Cd1^iv	122.47 (14)
C9—C10—C11	120.1 (2)	C24—N4—Cd1^iv	120.21 (15)
C9—C10—H10	120.0	C1—O1—Cd1	91.88 (13)
C11—C10—H10	120.0	C1—O2—Cd1	88.97 (14)
C10—C11—C12	119.7 (2)	C14—O3—Cd1^v	101.53 (13)
C10—C11—H11	120.2	C14—O3—Cd1^iii	147.07 (14)
C12—C11—H11	120.2	Cd1^v—O3—Cd1^iii	106.86 (6)
C11—C12—C13	121.0 (2)
O1—C1—C2—C3	−99.1 (3)	C16—C17—C18—C19	−0.2 (4)
O2—C1—C2—C3	74.8 (3)	C20—C17—C18—C19	179.3 (2)
Cd1—C1—C2—C3	−18.9 (8)	C17—C18—C19—N3	1.0 (4)
O1—C1—C2—C7	81.2 (3)	C16—C17—C20—C21	−177.7 (3)
O2—C1—C2—C7	−104.9 (3)	C18—C17—C20—C21	2.7 (4)
Cd1—C1—C2—C7	161.5 (6)	C17—C20—C21—C22	179.0 (2)
C7—C2—C3—C4	0.4 (4)	C20—C21—C22—C23	−5.2 (4)
C1—C2—C3—C4	−179.2 (2)	C20—C21—C22—C26	176.6 (3)
C2—C3—C4—C5	−0.1 (4)	C26—C22—C23—C24	−0.4 (4)
C3—C4—C5—C6	−0.4 (4)	C21—C22—C23—C24	−178.7 (2)
C4—C5—C6—C7	0.5 (4)	C22—C23—C24—N4	−0.9 (4)
C5—C6—C7—C2	−0.1 (4)	N4—C25—C26—C22	−0.8 (4)
C5—C6—C7—N1	174.3 (2)	C23—C22—C26—C25	1.2 (4)
C3—C2—C7—C6	−0.3 (4)	C21—C22—C26—C25	179.5 (2)
C1—C2—C7—C6	179.3 (2)	C6—C7—N1—N2	17.7 (3)
C3—C2—C7—N1	−175.2 (2)	C2—C7—N1—N2	−167.7 (2)
C1—C2—C7—N1	4.5 (3)	C7—N1—N2—C8	−175.67 (19)
C13—C8—C9—C10	−1.8 (4)	C9—C8—N2—N1	−6.7 (3)
N2—C8—C9—C10	175.3 (2)	C13—C8—N2—N1	170.4 (2)
C8—C9—C10—C11	−3.4 (4)	C16—C15—N3—C19	0.1 (4)
C9—C10—C11—C12	3.9 (4)	C16—C15—N3—Cd1	178.9 (2)
C10—C11—C12—C13	0.8 (4)	C18—C19—N3—C15	−0.9 (4)
C11—C12—C13—C8	−5.9 (4)	C18—C19—N3—Cd1	−179.65 (18)
C11—C12—C13—C14	169.1 (3)	C26—C25—N4—C24	−0.5 (4)
C9—C8—C13—C12	6.3 (4)	C26—C25—N4—Cd1^iv	176.7 (2)
N2—C8—C13—C12	−170.9 (2)	C23—C24—N4—C25	1.4 (4)
C9—C8—C13—C14	−168.3 (2)	C23—C24—N4—Cd1^iv	−175.93 (19)
N2—C8—C13—C14	14.4 (3)	O2—C1—O1—Cd1	−9.4 (2)
C12—C13—C14—O4	66.9 (3)	C2—C1—O1—Cd1	164.09 (15)
C8—C13—C14—O4	−118.4 (3)	O1—C1—O2—Cd1	9.2 (2)
C12—C13—C14—O3	−105.5 (3)	C2—C1—O2—Cd1	−164.30 (16)
C8—C13—C14—O3	69.3 (3)	O4—C14—O3—Cd1^v	−11.7 (2)
N3—C15—C16—C17	0.6 (4)	C13—C14—O3—Cd1^v	160.59 (14)
C15—C16—C17—C18	−0.5 (4)	O4—C14—O3—Cd1^iii	−161.02 (19)
C15—C16—C17—C20	179.9 (2)	C13—C14—O3—Cd1^iii	11.3 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O4^vi	0.93	2.51	3.355 (3)	151

Symmetry code: (vi) x+1/2, −y+3/2, z+1/2.