A three-dimensional Cd^II coordination framework: poly[di-[mu]₂-aqua-{[mu]₂-1,4-bis[(1H-1,2,4-triazol-1-yl)methyl]benzene-[kappa]²N⁴:N^4'}di-[mu]₃-terephthalato-[kappa]³O:O':O''-dicadmium(II)]

The title Cd^II coordination polymer, [Cd(C₁₀H₈O₄)(C₁₂H₁₂N₆)_0.5(H₂O)]_n, has been obtained by the hydro­thermal method and studied by single-crystal X-ray diffraction, elemental analysis, thermo­gravimetric analysis, IR spectroscopy and fluorescence spectroscopy. The compound forms a novel three-dimensional framework with 3,8-connected three-dimensional binodal {4.5²}₂{4².5¹⁰.6¹².7.8³} topology. An investigation of its photo­luminescence properties shows that the compound exhibits a strong fluorescence emission in the solid state at room temperature.

S1. Introduction

Metal–organic frameworks (MOFs) have enjoyed tremendous popularity in recent years, not only owing to their intriguing variety of topologies but also because of their potential applications in many fields, such as ion-exchange materials, heterogeneous catalysts, optical devices, magnets and gas-storage media (Krishna, 2012; Laguna et al., 2010; Liu et al., 2012; Lu et al., 2011; Sumida et al., 2012; Train et al., 2009). Generally, the structure of a MOF depends greatly on factors such as the temperature, the neutral ligands, the organic anions, the metal atoms and so on (Cook et al., 2013; Liu et al., 2013; Paz et al., 2012). Among these factors, the choice of the organic ligand is the key factor that influences the construction of MOFs with distinctive structures. Polycarboxyl­ate ligands are frequently used for MOFs since carboxyl­ate groups have an excellent coordination capability and flexible coordination patterns. Terephthalic acid (H₂PBEA), a symmetrical V-shaped aromatic polycarb­oxy­lic derivative, has been used as a bridging ligand in the synthesis of novel MOFs (Blake et al., 2010; Sengupta et al., 2012; Wang et al., 2012; Yang et al., 2010). Polytriazole derivatives are also good ligands for the construction of MOFs. The ligand 1,4-bis­(1,2,4-triazol-1-yl­methyl)-benzene (BTX), a flexible derivative of triazole, have been shown to be a good bridging ligand to construct novel MOFs (Meng et al., 2004; Peng et al., 2006; Wang et al., 2013; Yu et al., 2011).

Taking inspiration from the points mentioned above, we explored the self-assembly of Cd^II, H₂PBEA and BTX under hydro­thermal conditions, and obtained a novel three-dimensional coordination polymer, the title compound, (I). Herein, we report its synthesis, crystal structure and physical properties.

S2. Experimental

The 1,4-bis­(1,2,4-triazol-1-yl­methyl)-benzene (BTX) ligand was prepared according to a previously reported procedure (Peng et al., 2004). All other reagents and solvents used in the experiment were purchased from commercial sources and used without further purification. The FT–IR spectrum was recorded from a KBr pellet in the range 4000–400 cm^-1 on a VECTOR 22 spectrometer. The CHN elemental analysis was performed on a Perkin–Elmer 240C elemental analyser. The fluorescence spectrum was recorded on a Fluoro Max-P spectrophotometer. The thermogravimetric analysis (TGA) was performed on a Perkin–Elmer Pyris 1 TGA analyser from 298 to 1073 K with a heating rate of 20 K min^-1 under nitro­gen.

S2.1. Synthesis and crystallization

A mixture of Cd(NO₃)₂·6H₂O (0.0346 g, 0.100 mmol), H₂PBEA (0.0194 g, 0.100 mmol), BTX (0.0240 g, 0.100 mmol) and NaOH (0.00600 g, 0.150 mmol) in H₂O (10 ml) was sealed in a 16 ml Teflon-lined stainless steel container and heated at 423 K for 72 h. After cooling to room temperature, colourless block crystals of (I) were collected by filtration and washed with water and ethanol several times (yield 26.4%, based on BTX). Elemental analysis for C₁₆H₁₆CdN₃O₅ (M_r = 442.72): C 43.41, H 3.64, N 9.49%; found: C 41.50, H 3.65, N 9.52%. IR (KBr, ν, cm^-1) : 3619 (m), 3421 (m), 3100 (m), 1635 (m), 1611 (s), 1583 (s), 1561 (w), 1362 (s), 1259 (s), 1123 (m), 981 (s), 917 (s), 832 (s), 763 (s), 721 (s), 652 (s).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. C-bound H atoms were placed in calculated positions and refined using a riding-model approximation, with C—H = 0.93 (triazole and benzene) or 0.97 Å (methyl­ene), and with U_iso(H) = 1.2U_eq(C). Water H atoms were located in a difference Fourier synthesis. The positional parameters of the water H atoms were refined with a restraint of O—H = 0.85 (2) Å, with U_iso(H) = 1.2U_eq(O).

S3. Results and discussion

X-ray crystallography reveals that the asymmetric unit of (I) consists of a divalent cadmium cation, one fully deprotonated PBEA ligand, one half of a BTX ligand that is located over a crystallographic inversion centre and one aqua ligand. As shown in Fig. 1, atom Cd1 is six-coordinated by three donor O atoms from three individual PBEA anions [Cd1—O2 = 2.294 (3), Cd1—O3ⁱⁱ = 2.242 (3) and Cd1—O4ⁱⁱⁱ = 2.277 (3) Å], two coordinated water molecules [Cd1—O5 = 2.382 (3) and Cd1—O5^iv = 2.359 (3) Å] and a triazole donor N atom from one BTX ligand [Cd1—N1 = 2.311 (4) Å] in an o­cta­hedral coordination environment [symmetry codes: (ii) x + 1, -y + 1/2, z + 1/2; (iii) x, -y + 1/2, z + 1/2; (iv) -x + 2, -y + 1, -z + 2].

In (I), two crystallographically equivalent Cd atoms are bridged by two coordinated water molecules to form a binuclear Cd₂O₂ cluster. The Cd···Cd and O···O through-space distances across the dinuclear clusters measure 3.690 (3) and 2.984 (4) Å, respectively. These binuclear Cd₂O₂ clusters are noticeably pinched, with Cd—O—Cd and O—Cd—O angles of 102.08 (10) and 77.91 (9)°, respectively. Each PBEA anion in (I) links three Cd^II cations in a µ₂-η¹:η⁰, µ₂-η¹:η¹ coordination fashion through its two carboxyl­ate groups. In this way the binuclear Cd₂O₂ clusters are further connected by O atoms of two carboxyl­ate groups from two different PBEA^2- ligands to form an infinite rod-shaped secondary building unit (SBU) along the a axis (Fig. 2). The PBEA^2- ligands link these rod-shaped SBUs to give rise to a complicated three-dimensional [Cd(PBEA)]_n framework. The topology of the neutral [Cd(PBEA)]_n three-dimensional framework can be simplified by regarding the Cd₂O₂ atoms and PBEA^2- ligands as 6- and 3-connected nodes, respectively. The resulting network has a 3,6-connected binodal net topology of point symbol {4.6²}₂{4².6¹⁰.8³} (Fig. 3).

The BTX ligand exhibits a trans conformation and the two triazole rings are parallel to each other. The Cd···Cd contact distance through the BTX ligand is 15.088 (11) Å. In this manner, the three-dimensional network made up of only PBEA^2- ligands is further connected by the BTX ligands to result in the final three-dimensional framework of (I) (Fig. 4). Topologically, if the Cd₂O₂ clusters and PBEA^2- ligands are considered as 8- and 3-connected nodes, respectively, and the BTX ligands are simplified as linkers, the structure of (I) can be described as a 3,8-connected net with the point symbol {4.5²}₂{4².5¹⁰.6¹².7.8³}, as shown in Fig. 5. In addition, there are inter­molecular hydrogen bonds between the water molecules and PBEA anions which further stabilize the three-dimensional architecture of (I) (Table 2).

Thermogravimetric analysis (TGA) was conducted to test the thermal stability of (I). As shown in Fig. 6, the weight loss corresponding to the release of one bound water molecule is observed between 371 and 400 K (observed 4.12%, calculated 4.07%). After removal of the solvent molecules, the remaining solid is stable up to 431 K. The decomposition of the organic ligand is observed from 431 to 1028 K and the remaining weight corresponds to the formation of CdO (observed 29.2%, calculated 29.00%).

Investigations into the photoluminescent properties of coordination polymers with d¹⁰ metal atoms remain intensely active owing to their potential applications in chemical sensors, photochemistry and so on (Allendorf et al., 2009; Gomes et al., 2009). The solid-state photoluminescence of (I) has been investigated at room temperature. The main emission peaks of the BTX and H₂PBEA ligands are located at 462 (λ_ex = 395 nm) and 454 nm (λ_ex = 365 nm), respectively, which are probably attributed to the π^*–n or π^*–π transitions as previously reported (Huang et al., 2010; Luo et al., 2012). Irradiation of (I) with UV light (λ_ex = 360 nm) in the solid state resulted in a relatively [Strong? Weak? Text missing] emission band centred on ~424 nm (Fig. 7). According to a recent review of d¹⁰ metal coordination polymer luminescence, the Cd^II cation is difficult to oxidize or reduce. As a result, the emissive behaviour of (I) can be attributed to ligand-centred electronic transitions (Guo et al., 2011; Wen et al., 2007).

Related literature

For related literature, see: Allendorf et al. (2009); Blake et al. (2010); Cook et al. (2013); Gomes et al. (2009); Guo et al. (2011); Huang et al. (2010); Krishna (2012); Laguna et al. (2010); Liu et al. (2012, 2013); Lu et al. (2011); Luo et al. (2012); Meng et al. (2004); Paz et al. (2012); Peng et al. (2004, 2006); Sengupta et al. (2012); Sumida et al. (2012); Train et al. (2009); Wang et al. (2012, 2013); Wen et al. (2007); Yang et al. (2010); Yu et al. (2011).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (ii) x + 1, -y + 1/2, z + 1/2; (iii) x, -y + 1/2, z + 1/2; (iv) -x + 2, -y + 1, -z + 2.]
	Fig. 2. A view of the infinite rod-shaped secondary building unit in (I).
	Fig. 3. A network perspective of the 3,6-connected binodal {4.6^2}2{4^2.6^10.8^3} network in (I). The red and bright-green spheres represent the Cd2O2 clusters and PBEA^2- ligands, respectively.
	Fig. 4. A view of the three-dimensional structure of (I).
	Fig. 5. A network perspective of the 3,8-connected three-dimensional {4.5^2}2{4^2.5^10.6^12.7.8^3} network in (I). The red and bright-green spheres represent the Cd2O2 clusters and PBEA^2- ligands, respectively.
	Fig. 6. The thermogravimetric curve of (I).
	Fig. 7. The solid-state emission spectrum of (I), recorded at room temperature.

poly[di-µ₂-aqua-{µ₂-1,4-bis[(1H-1,2,4-triazol-1-yl)methyl]benzene-κ²N⁴:N^4'}di-µ₃-terephthalato-κ³O:O':O''-dicadmium(II)]

Crystal data

[Cd(C10H8O4)(C12H12N6)0.5(H2O)]	F(000) = 884
Mr = 442.72	Dx = 1.815 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1819 reflections
a = 5.335 (4) Å	θ = 2.5–21.1°
b = 18.437 (14) Å	µ = 1.38 mm^−1
c = 16.471 (12) Å	T = 296 K
β = 90.488 (10)°	Block, colourless
V = 1620 (2) Å^3	0.25 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker SMART ? CCD area-detector diffractometer	3005 independent reflections
Radiation source: fine-focus sealed tube	2264 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
ϕ and ω scans	θmax = 25.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −6→6
Tmin = 0.724, Tmax = 0.789	k = −22→21
8822 measured reflections	l = −18→19

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	w = 1/[σ^2(Fo^2) + (0.0379P)^2] where P = (Fo^2 + 2Fc^2)/3
3005 reflections	(Δ/σ)max = 0.002
232 parameters	Δρmax = 0.59 e Å^−3
2 restraints	Δρmin = −0.79 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	0.7221 (8)	0.4614 (2)	0.8070 (3)	0.0256 (10)
C2	0.5387 (8)	0.4522 (2)	0.7364 (2)	0.0295 (11)
H2A	0.3756	0.4709	0.7514	0.035*
H2B	0.5972	0.4794	0.6898	0.035*
C3	0.5170 (8)	0.3726 (2)	0.7145 (2)	0.0254 (10)
C4	0.3242 (8)	0.3298 (3)	0.7424 (3)	0.0319 (11)
H4	0.1969	0.3509	0.7726	0.038*
C5	0.3160 (8)	0.2560 (3)	0.7265 (3)	0.0318 (11)
H5	0.1816	0.2287	0.7451	0.038*
C6	0.5044 (8)	0.2223 (2)	0.6834 (3)	0.0269 (10)
C7	0.6951 (8)	0.2653 (3)	0.6536 (3)	0.0386 (13)
H7	0.8217	0.2442	0.6231	0.046*
C8	0.7004 (9)	0.3396 (3)	0.6686 (3)	0.0360 (12)
H8	0.8294	0.3675	0.6474	0.043*
C9	0.4973 (8)	0.1417 (2)	0.6677 (3)	0.0323 (11)
H9A	0.4140	0.1172	0.7121	0.039*
H9B	0.6666	0.1229	0.6641	0.039*
C10	0.3563 (8)	0.1277 (2)	0.5887 (3)	0.0239 (10)
C11	0.7911 (9)	0.2559 (3)	0.8834 (3)	0.0388 (13)
H11	0.6457	0.2754	0.8608	0.047*
C12	1.1225 (9)	0.2471 (3)	0.9490 (3)	0.0367 (12)
H12	1.2617	0.2568	0.9816	0.044*
C13	1.2333 (10)	0.1183 (3)	0.9115 (3)	0.0517 (15)
H13A	1.3964	0.1285	0.9354	0.062*
H13B	1.2586	0.1037	0.8556	0.062*
C14	1.1121 (9)	0.0566 (2)	0.9575 (3)	0.0337 (11)
C15	1.1714 (10)	0.0439 (3)	1.0372 (3)	0.0500 (15)
H15	1.2887	0.0734	1.0631	0.060*
C16	0.9402 (10)	0.0122 (3)	0.9197 (3)	0.0511 (15)
H16	0.8984	0.0196	0.8654	0.061*
Cd1	0.87305 (6)	0.407414 (17)	0.988934 (19)	0.02522 (12)
N1	0.9426 (7)	0.2942 (2)	0.9332 (2)	0.0341 (10)
N2	0.8628 (8)	0.1894 (2)	0.8691 (3)	0.0450 (11)
N3	1.0803 (7)	0.1848 (2)	0.9129 (2)	0.0356 (10)
O1	0.9359 (5)	0.48341 (19)	0.79251 (17)	0.0393 (9)
O2	0.6464 (5)	0.44314 (18)	0.87691 (17)	0.0331 (8)
O3	0.1204 (5)	0.12561 (17)	0.59325 (17)	0.0323 (8)
O4	0.4741 (5)	0.12244 (17)	0.52390 (18)	0.0317 (8)
O5	0.8284 (5)	0.51414 (17)	1.06899 (18)	0.0275 (7)
H5A	0.685 (5)	0.531 (2)	1.076 (3)	0.033*
H5B	0.893 (7)	0.505 (2)	1.1141 (16)	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.029 (3)	0.017 (2)	0.031 (3)	0.005 (2)	−0.004 (2)	−0.003 (2)
C2	0.034 (3)	0.029 (3)	0.025 (3)	−0.001 (2)	−0.004 (2)	0.004 (2)
C3	0.022 (2)	0.030 (3)	0.023 (2)	0.000 (2)	−0.0040 (19)	0.002 (2)
C4	0.026 (3)	0.037 (3)	0.032 (3)	0.001 (2)	0.004 (2)	0.000 (2)
C5	0.022 (3)	0.039 (3)	0.035 (3)	−0.009 (2)	0.002 (2)	0.000 (2)
C6	0.025 (2)	0.030 (3)	0.026 (2)	−0.002 (2)	−0.0085 (19)	−0.005 (2)
C7	0.026 (3)	0.046 (3)	0.044 (3)	−0.002 (2)	0.009 (2)	−0.015 (3)
C8	0.029 (3)	0.038 (3)	0.041 (3)	−0.012 (2)	0.007 (2)	−0.007 (2)
C9	0.031 (3)	0.030 (3)	0.036 (3)	−0.003 (2)	−0.005 (2)	−0.004 (2)
C10	0.031 (3)	0.016 (2)	0.025 (3)	0.000 (2)	−0.007 (2)	−0.0040 (19)
C11	0.037 (3)	0.030 (3)	0.049 (3)	0.000 (2)	−0.006 (2)	0.000 (2)
C12	0.034 (3)	0.035 (3)	0.041 (3)	−0.003 (2)	0.001 (2)	0.001 (2)
C13	0.054 (4)	0.031 (3)	0.071 (4)	0.011 (3)	0.025 (3)	0.008 (3)
C14	0.039 (3)	0.023 (3)	0.039 (3)	0.007 (2)	0.009 (2)	−0.004 (2)
C15	0.054 (4)	0.037 (3)	0.058 (4)	−0.011 (3)	−0.017 (3)	−0.006 (3)
C16	0.073 (4)	0.050 (4)	0.031 (3)	−0.007 (3)	−0.014 (3)	0.006 (3)
Cd1	0.02350 (19)	0.0222 (2)	0.0299 (2)	0.00082 (15)	−0.00296 (13)	0.00154 (15)
N1	0.036 (2)	0.026 (2)	0.040 (2)	0.0055 (19)	−0.0008 (19)	−0.0074 (19)
N2	0.052 (3)	0.028 (3)	0.055 (3)	−0.008 (2)	−0.002 (2)	−0.003 (2)
N3	0.035 (2)	0.023 (2)	0.049 (3)	−0.0007 (19)	0.011 (2)	0.006 (2)
O1	0.0256 (18)	0.062 (2)	0.0304 (19)	−0.0102 (17)	−0.0003 (14)	−0.0018 (16)
O2	0.0252 (17)	0.045 (2)	0.0286 (18)	−0.0064 (15)	−0.0019 (14)	0.0078 (16)
O3	0.0227 (17)	0.039 (2)	0.0355 (19)	−0.0030 (15)	0.0005 (14)	−0.0068 (15)
O4	0.0237 (17)	0.044 (2)	0.0273 (18)	0.0058 (15)	−0.0006 (14)	−0.0048 (15)
O5	0.0223 (17)	0.0300 (19)	0.0301 (18)	0.0064 (15)	−0.0047 (14)	0.0017 (15)

Geometric parameters (Å, º)

C1—O1	1.236 (5)	C12—N3	1.311 (6)
C1—O2	1.268 (5)	C12—N1	1.319 (6)
C1—C2	1.524 (5)	C12—H12	0.9300
C2—C3	1.516 (6)	C13—N3	1.473 (6)
C2—H2A	0.9700	C13—C14	1.515 (7)
C2—H2B	0.9700	C13—H13A	0.9700
C3—C4	1.378 (6)	C13—H13B	0.9700
C3—C8	1.382 (6)	C14—C15	1.368 (7)
C4—C5	1.387 (6)	C14—C16	1.374 (6)
C4—H4	0.9300	C15—C16^i	1.392 (7)
C5—C6	1.382 (6)	C15—H15	0.9300
C5—H5	0.9300	C16—C15^i	1.392 (7)
C6—C7	1.383 (6)	C16—H16	0.9300
C6—C9	1.510 (6)	Cd1—O3^ii	2.242 (3)
C7—C8	1.393 (6)	Cd1—O4^iii	2.277 (3)
C7—H7	0.9300	Cd1—O2	2.294 (3)
C8—H8	0.9300	Cd1—N1	2.311 (4)
C9—C10	1.520 (5)	Cd1—O5^iv	2.359 (3)
C9—H9A	0.9700	Cd1—O5	2.382 (3)
C9—H9B	0.9700	N2—N3	1.364 (5)
C10—O4	1.247 (5)	O3—Cd1^v	2.242 (3)
C10—O3	1.262 (5)	O4—Cd1^vi	2.277 (3)
C11—N2	1.308 (6)	O5—Cd1^iv	2.359 (3)
C11—N1	1.346 (5)	O5—H5A	0.833 (19)
C11—H11	0.9300	O5—H5B	0.831 (19)
O1—C1—O2	124.3 (4)	C14—C13—H13A	109.2
O1—C1—C2	118.4 (4)	N3—C13—H13B	109.2
O2—C1—C2	117.2 (4)	C14—C13—H13B	109.2
C3—C2—C1	109.6 (3)	H13A—C13—H13B	107.9
C3—C2—H2A	109.7	C15—C14—C16	118.7 (5)
C1—C2—H2A	109.7	C15—C14—C13	120.7 (5)
C3—C2—H2B	109.7	C16—C14—C13	120.5 (5)
C1—C2—H2B	109.7	C14—C15—C16^i	121.3 (5)
H2A—C2—H2B	108.2	C14—C15—H15	119.3
C4—C3—C8	117.7 (4)	C16^i—C15—H15	119.3
C4—C3—C2	122.0 (4)	C14—C16—C15^i	119.9 (5)
C8—C3—C2	120.2 (4)	C14—C16—H16	120.0
C3—C4—C5	121.3 (4)	C15^i—C16—H16	120.0
C3—C4—H4	119.3	O3^ii—Cd1—O4^iii	106.61 (12)
C5—C4—H4	119.3	O3^ii—Cd1—O2	175.75 (11)
C6—C5—C4	121.1 (4)	O4^iii—Cd1—O2	77.61 (11)
C6—C5—H5	119.5	O3^ii—Cd1—N1	87.94 (13)
C4—C5—H5	119.5	O4^iii—Cd1—N1	92.05 (13)
C5—C6—C7	117.8 (4)	O2—Cd1—N1	91.43 (13)
C5—C6—C9	120.9 (4)	O3^ii—Cd1—O5^iv	94.68 (11)
C7—C6—C9	121.3 (4)	O4^iii—Cd1—O5^iv	152.40 (11)
C6—C7—C8	120.9 (4)	O2—Cd1—O5^iv	81.47 (11)
C6—C7—H7	119.5	N1—Cd1—O5^iv	106.35 (13)
C8—C7—H7	119.5	O3^ii—Cd1—O5	82.01 (11)
C3—C8—C7	121.1 (4)	O4^iii—Cd1—O5	87.80 (11)
C3—C8—H8	119.4	O2—Cd1—O5	98.83 (11)
C7—C8—H8	119.4	N1—Cd1—O5	169.46 (12)
C6—C9—C10	108.9 (4)	O5^iv—Cd1—O5	77.79 (12)
C6—C9—H9A	109.9	C12—N1—C11	101.9 (4)
C10—C9—H9A	109.9	C12—N1—Cd1	129.4 (3)
C6—C9—H9B	109.9	C11—N1—Cd1	128.2 (3)
C10—C9—H9B	109.9	C11—N2—N3	102.2 (4)
H9A—C9—H9B	108.3	C12—N3—N2	109.2 (4)
O4—C10—O3	124.0 (4)	C12—N3—C13	130.0 (5)
O4—C10—C9	119.8 (4)	N2—N3—C13	120.8 (4)
O3—C10—C9	116.1 (4)	C1—O2—Cd1	129.5 (3)
N2—C11—N1	115.3 (4)	C10—O3—Cd1^v	122.9 (3)
N2—C11—H11	122.4	C10—O4—Cd1^vi	135.6 (3)
N1—C11—H11	122.4	Cd1^iv—O5—Cd1	102.21 (12)
N3—C12—N1	111.4 (4)	Cd1^iv—O5—H5A	117 (3)
N3—C12—H12	124.3	Cd1—O5—H5A	119 (3)
N1—C12—H12	124.3	Cd1^iv—O5—H5B	102 (3)
N3—C13—C14	112.3 (4)	Cd1—O5—H5B	107 (3)
N3—C13—H13A	109.2	H5A—O5—H5B	108 (4)
O1—C1—C2—C3	102.6 (5)	O2—Cd1—N1—C12	156.9 (4)
O2—C1—C2—C3	−74.9 (5)	O5^iv—Cd1—N1—C12	75.4 (4)
C1—C2—C3—C4	97.7 (5)	O5—Cd1—N1—C12	−36.4 (9)
C1—C2—C3—C8	−79.0 (5)	O3^ii—Cd1—N1—C11	151.9 (4)
C8—C3—C4—C5	1.2 (6)	O4^iii—Cd1—N1—C11	45.3 (4)
C2—C3—C4—C5	−175.5 (4)	O2—Cd1—N1—C11	−32.3 (4)
C3—C4—C5—C6	1.4 (7)	O5^iv—Cd1—N1—C11	−113.9 (4)
C4—C5—C6—C7	−2.9 (6)	O5—Cd1—N1—C11	134.3 (6)
C4—C5—C6—C9	178.7 (4)	N1—C11—N2—N3	−0.5 (6)
C5—C6—C7—C8	1.9 (6)	N1—C12—N3—N2	0.9 (6)
C9—C6—C7—C8	−179.8 (4)	N1—C12—N3—C13	177.8 (4)
C4—C3—C8—C7	−2.3 (7)	C11—N2—N3—C12	−0.2 (5)
C2—C3—C8—C7	174.5 (4)	C11—N2—N3—C13	−177.4 (4)
C6—C7—C8—C3	0.7 (7)	C14—C13—N3—C12	111.6 (6)
C5—C6—C9—C10	89.5 (5)	C14—C13—N3—N2	−71.8 (6)
C7—C6—C9—C10	−88.8 (5)	O1—C1—O2—Cd1	−22.2 (6)
C6—C9—C10—O4	93.5 (5)	C2—C1—O2—Cd1	155.1 (3)
C6—C9—C10—O3	−83.3 (5)	O4^iii—Cd1—O2—C1	−167.5 (4)
N3—C13—C14—C15	−94.1 (6)	N1—Cd1—O2—C1	−75.7 (4)
N3—C13—C14—C16	85.8 (6)	O5^iv—Cd1—O2—C1	30.6 (4)
C16—C14—C15—C16^i	−0.6 (9)	O5—Cd1—O2—C1	106.8 (4)
C13—C14—C15—C16^i	179.4 (5)	O4—C10—O3—Cd1^v	11.0 (6)
C15—C14—C16—C15^i	0.5 (9)	C9—C10—O3—Cd1^v	−172.3 (3)
C13—C14—C16—C15^i	−179.4 (5)	O3—C10—O4—Cd1^vi	−159.3 (3)
N3—C12—N1—C11	−1.2 (5)	C9—C10—O4—Cd1^vi	24.1 (6)
N3—C12—N1—Cd1	171.4 (3)	O3^ii—Cd1—O5—Cd1^iv	96.58 (12)
N2—C11—N1—C12	1.1 (6)	O4^iii—Cd1—O5—Cd1^iv	−156.31 (11)
N2—C11—N1—Cd1	−171.7 (3)	O2—Cd1—O5—Cd1^iv	−79.21 (12)
O3^ii—Cd1—N1—C12	−18.9 (4)	N1—Cd1—O5—Cd1^iv	114.3 (6)
O4^iii—Cd1—N1—C12	−125.5 (4)	O5^iv—Cd1—O5—Cd1^iv	0.0

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O4^ii	0.93	2.59	3.284 (6)	132
C2—H2A···O1^vii	0.97	2.46	3.403 (6)	165
O5—H5B···O1^iv	0.83 (2)	1.80 (2)	2.596 (4)	161 (4)
O5—H5A···O2^viii	0.83 (2)	1.99 (2)	2.805 (5)	164 (4)
O5—H5A···O4^ix	0.83 (2)	2.51 (4)	2.982 (4)	117 (3)

Symmetry codes: (ii) x+1, −y+1/2, z+1/2; (iv) −x+2, −y+1, −z+2; (vii) x−1, y, z; (viii) −x+1, −y+1, −z+2; (ix) −x+1, y+1/2, −z+3/2.