The crystal structure and photocatalytic properties of a three-dimensional cadmium(II) metal-organic framework: poly[bis­([mu]₃-benzene-1,2-di­carboxyl­ato)[[mu]₂-1,4-bis­(pyridin-3-ylmeth­oxy)benzene]­dicadmium(II)]

Photocatalysis is a green technology for the treatment of all kinds of con­tami­nants and has advantages over other treatment methods. Recently, much effort has been devoted to developing new photocatalytic materials based on metal-organic frameworks for use in the degradation of many kinds of organic contaminants. With the aim of searching for more effective photocatalysts, the title three-dimensional coordination polymer, [Cd₂(C₈H₄O₄)₂(C₁₈H₁₆N₂O₂)]_n, was pre­pared. The asymmetric unit contains one Cd^II cation, one benzene-1,2-di­­car­boxyl­ate anion (denoted L^2-) and half of a centrosymmetric 1,4-bis­(pyridin-3-yl­meth­oxy)benzene ligand (denoted bpmb). Each Cd^II centre is five-coordinated by four carboxyl­ate O atoms from two L^2- ligands and by one N atom from a bpmb ligand, forming a disordered penta­gonal pyramidal coordination geometry. The Cd^II centres are inter­linked by L^2- ligands to form a one-dimensional [Cd₂L₂]_n chain. Adjacent chains are further connected by bpmb linkers, giving rise to a two-dimensional network, and these networks are pillared by bpmb to afford a three-dimensional framework with a 3³.4².6³.7¹.8¹ topology. Each grid in the framework has large channels which are filled mainly by the two other equivalent frameworks to form a threefold inter­penetrating net. The com­pound exhibits relatively good photocatalytic activity towards the degradation of methyl­ene blue in aqueous solution under UV irradiation.

S1. Introduction

Photocatalysis is a green technology for the treatment of all kinds of contaminants, which has many advantages over other treatment methods, for instance, the use of the environmentally friendly oxidant (O₂ or H₂O₂), the ambient temperature reaction condition, and the oxidation of the organic compounds, even at low concentrations (Ma et al., 2003; Liu et al., 2010). Recently, considering the novelty of this field in metal–organic frameworks (MOFs), much effort has been devoted to developing new photocatalytic materials based on MOFs in the degradation of many kinds of organic contaminants with up to 90% efficiency (Liu, Ding, Li et al., 2014; Liu, Ding, Huang et al., 2014; Wu et al., 2015). Compared to the traditional semiconductor metal oxide, the advantages of MOFs as photocatalyst lie in the fact that their combination of inorganic and organic moieties can result in different metal–ligand charge-transfer-related tunable photocatalysts (Wen et al., 2012).

Thus, the examination of the photocatalytic properties of MOFs have been productive (Wang et al., 2011, 2015; Dai et al., 2014). In particular, Cd-based MOFs have exhibited efficient photocatalytic activities for the organic dyes (Wen et al., 2012; Liu, Ding, Huang et al., 2014; Dai et al., 2014; Liu, Yu, Ma et al., 2015). For example, Hou and co-workers reported that four polynuclear Cd^II polymers showed high photocatalytic activity towards the degradation of methyl­ene blue (MB) (Liu, Ding, Huang et al., 2014). Lang et al. utilized tetra­kis(pyridin-4-yl)cyclo­butane to synthesize a series of Cd^II coordination polymers, and the results revealed that some coordination polymers may be active photocatalytic materials due to their high catalytic activities for the degradation of methyl orange, methyl blue or rhodamine B in aqueous solution (Li et al., 2014). Aiming to search for more effective photocatalysts, we combined Cd(OAc)₂·2H₂O with benzene-1,2-di­carb­oxy­lic acid (H₂L) and 1,4-bis­(pyridin-3-yl­meth­oxy)­benzene (bpmb) to produce the title compound, [Cd₂(L)₂(bpmb)]_n, (I), and report the characterization of the material and photocatalytic activity herein.

S2. Experimental

S2.1. Synthesis and crystallization

1,4-Bis(pyridin-3-yl­meth­oxy)­benzene (bpmb) was prepared according to the literature method of Liu, Yu, Li et al. (2015). All other chemicals and reagents were obtained from commercial sources (Sigma–Aldrich) and used as received. A mixture of Cd(OAc)₂·2H₂O (11 mg, 0.04 mmol; OAc is acetate), benzene-1,2-di­carb­oxy­lic acid (3 mg, 0.02 mmol), bpmb (6 mg, 0.02 mmol) and MeOH–H₂O (1:1 v/v, 4 ml) was sealed in a 10 ml Pyrex glass tube and heated at 438 K for 4 d, and then cooled to room temperature at a rate of 5 K h⁻¹. Colourless blocks of (I) were collected and dried in air (yield 7 mg, 41%, based on bpmb). Analysis calculated for C₃₄H₂₄Cd₂N₂O₁₀ (%): H 2.86, C 48.31, N 3.31; found: H 2.59, C 48.14, N 3.60.

S2.2. Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 1. A l l H atoms are placed in geometrically idealized positions, with C—H = 0.93 Å for aromatic and 0.97 Å for methyl­ene H atoms, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C,O).

S3. Results and discussion

The title compound, (I), crystallizes in the monoclinic space group C2/c, and its asymmetric unit contains half of a [Cd₂(L)₂(bpmb)] unit. As shown in Fig. 1, each Cd^II centre is five-coordinated by four carboxyl­ate O atoms [O2, O3, O4ⁱ and O1ⁱⁱ; symmetry codes: (i) −x + 1, y, −z + 3/2; (ii) −x + 1, −y + 1, −z + 1] from two L²⁻ ligands and one N atom (N1) from a bpmb ligand, forming a disordered penta­gonal pyramidal coordination geometry. Selected bond lengths and angles for (I) are listed in Table 2.

In the structure of (I), each adjoining pair of Cd^II atoms is connected by two carboxyl­ate groups (µ²-η¹:η¹) from two L²⁻ ligands to generate a [Cd₂(CO₂)₂] subunit with a Cd···Cd distance of 4.037 (3) Å (Fig. 2). Such subunits are bridged by L²⁻ ligands to form an infinite [Cd₂(L)₂]_n chain extending along the c axis (Fig. 2). Each chain is inter­linked to adjacent chains through bpmb linkers, producing a two-dimensional network with parallelogrammic meshes (15.54 × 16.62 Ų) extending along the bc plane (Fig. 3). Furthermore, additional bpmb ligands are employed as pillars to link the two-dimensional networks to afford a three-dimensional framework with one-dimensional rhombic channels along the [001] direction (Fig. 4). These channels are filled by mutual inter­penetration of three independent equivalent frameworks, generating a threefold inter­penetrating three-dimensional architecture (Fig. 5). Topologically (Wells, 1997), if the Cd^II centres are regarded as 5-connected nodes, and the L²⁻ and bpmb ligands are considered as linkers, the overall structure of (I) can be specified by a Schläfli symbol of 3³4²6³7¹8¹ (Fig. 5). Geometric details of the hydrogen-bond inter­actions are given in Table 3.

Compound (I) was also characterized by powder X-ray diffraction (PXRD) at room temperature. The PXRD pattern of (I) is coincident with the simulated pattern derived from the single-crystal X-ray data (see Fig. S1 in the Supporting information), which implies that the structure of the bulk sample is the same as that of the single-crystal.

The photocatalytic activity of compound (I) was evaluated by the degradation of MB under irradiation of a 350 W Xe lamp. In a catalytic process, 20 mg of compound (I) as photocatalyst was added into 50 ml of MB solution (4 × 10 ⁻⁵ mol l⁻¹). The solution was stirred for 30 min in the dark before irradiation to reach adsorption equilibrium between the catalyst and solution and was then exposed to UV irradiation. About 4 ml of the suspension was continually taken from the reaction cell and collected by centrifugation at 30 min inter­vals during the irradiation. The resulting solution was analyzed on a Varian 50 UV/Vis spectrophotometer.

To evaluate the band gaps, the UV–vis absorption spectrum of (I) was measured at room temperature (see Fig. S2 in the Supporting information). The result gives E_g (band-gap energy) value of 3.43 eV for (I) (see Fig. S3 in the Supporting information). As illustrated in Fig. 6, the absorption of MB notably decreased in the presence of (I). The degradation efficiency is defined as C/C₀, where C and C₀ represent the resultant and initial concentration of MB, respectively. By contrast, the simple photolysis experiment was also completed under the same conditions without any catalyst (Fig. 7). The organic dye concentrations were estimated by the absorbance at 665 nm (MB). Compound (I) shows a relatively good photocatalytic activity towards the degradation ratio of MB reached 96.8% exposed to UV light for 120 min (Fig. 7). Compared with other Cd-based coordination polymer (CP) materials, e.g. {[Cd(tpcb)_0.75(OH)(H₂O)₂]NO₃}_n [tpcp is tetra­kis(pyridin-4-yl)cyclo­butane; Li et al., 2014], {[Cd(btbb)_0.5(btec)_0.5(H₂O)]·2H₂O}_n {btbb is 1,4-bis­[2-(thia­zol-2-yl)benzimidazole-1-yl­methyl]­benzene and H₄btec is benzene-1,2,4,5-tetra­carboxyl­ate; Liu, Ding, Li et al., 2014} and {[Cd₃(bcb)₂(H₂O)₅]·H₂O}_n [H₃bcb is 3,4-bis­(4-carb­oxy­phenyl)­benzoic acid; Liu, Ding, Huang et al., 2014], as catalysts, ca 82.0, 92.7 and 88.7% of MB was degraded in 120, 140 and 180 min, respectively. These results suggest that compound (I) may be of use as a potential photoactive material.

Structure description

Photocatalysis is a green technology for the treatment of all kinds of contaminants, which has many advantages over other treatment methods, for instance, the use of the environmentally friendly oxidant (O₂ or H₂O₂), the ambient temperature reaction condition, and the oxidation of the organic compounds, even at low concentrations (Ma et al., 2003; Liu et al., 2010). Recently, considering the novelty of this field in metal–organic frameworks (MOFs), much effort has been devoted to developing new photocatalytic materials based on MOFs in the degradation of many kinds of organic contaminants with up to 90% efficiency (Liu, Ding, Li et al., 2014; Liu, Ding, Huang et al., 2014; Wu et al., 2015). Compared to the traditional semiconductor metal oxide, the advantages of MOFs as photocatalyst lie in the fact that their combination of inorganic and organic moieties can result in different metal–ligand charge-transfer-related tunable photocatalysts (Wen et al., 2012).

Thus, the examination of the photocatalytic properties of MOFs have been productive (Wang et al., 2011, 2015; Dai et al., 2014). In particular, Cd-based MOFs have exhibited efficient photocatalytic activities for the organic dyes (Wen et al., 2012; Liu, Ding, Huang et al., 2014; Dai et al., 2014; Liu, Yu, Ma et al., 2015). For example, Hou and co-workers reported that four polynuclear Cd^II polymers showed high photocatalytic activity towards the degradation of methyl­ene blue (MB) (Liu, Ding, Huang et al., 2014). Lang et al. utilized tetra­kis(pyridin-4-yl)cyclo­butane to synthesize a series of Cd^II coordination polymers, and the results revealed that some coordination polymers may be active photocatalytic materials due to their high catalytic activities for the degradation of methyl orange, methyl blue or rhodamine B in aqueous solution (Li et al., 2014). Aiming to search for more effective photocatalysts, we combined Cd(OAc)₂·2H₂O with benzene-1,2-di­carb­oxy­lic acid (H₂L) and 1,4-bis­(pyridin-3-yl­meth­oxy)­benzene (bpmb) to produce the title compound, [Cd₂(L)₂(bpmb)]_n, (I), and report the characterization of the material and photocatalytic activity herein.

The title compound, (I), crystallizes in the monoclinic space group C2/c, and its asymmetric unit contains half of a [Cd₂(L)₂(bpmb)] unit. As shown in Fig. 1, each Cd^II centre is five-coordinated by four carboxyl­ate O atoms [O2, O3, O4ⁱ and O1ⁱⁱ; symmetry codes: (i) −x + 1, y, −z + 3/2; (ii) −x + 1, −y + 1, −z + 1] from two L²⁻ ligands and one N atom (N1) from a bpmb ligand, forming a disordered penta­gonal pyramidal coordination geometry. Selected bond lengths and angles for (I) are listed in Table 2.

In the structure of (I), each adjoining pair of Cd^II atoms is connected by two carboxyl­ate groups (µ²-η¹:η¹) from two L²⁻ ligands to generate a [Cd₂(CO₂)₂] subunit with a Cd···Cd distance of 4.037 (3) Å (Fig. 2). Such subunits are bridged by L²⁻ ligands to form an infinite [Cd₂(L)₂]_n chain extending along the c axis (Fig. 2). Each chain is inter­linked to adjacent chains through bpmb linkers, producing a two-dimensional network with parallelogrammic meshes (15.54 × 16.62 Ų) extending along the bc plane (Fig. 3). Furthermore, additional bpmb ligands are employed as pillars to link the two-dimensional networks to afford a three-dimensional framework with one-dimensional rhombic channels along the [001] direction (Fig. 4). These channels are filled by mutual inter­penetration of three independent equivalent frameworks, generating a threefold inter­penetrating three-dimensional architecture (Fig. 5). Topologically (Wells, 1997), if the Cd^II centres are regarded as 5-connected nodes, and the L²⁻ and bpmb ligands are considered as linkers, the overall structure of (I) can be specified by a Schläfli symbol of 3³4²6³7¹8¹ (Fig. 5). Geometric details of the hydrogen-bond inter­actions are given in Table 3.

Compound (I) was also characterized by powder X-ray diffraction (PXRD) at room temperature. The PXRD pattern of (I) is coincident with the simulated pattern derived from the single-crystal X-ray data (see Fig. S1 in the Supporting information), which implies that the structure of the bulk sample is the same as that of the single-crystal.

The photocatalytic activity of compound (I) was evaluated by the degradation of MB under irradiation of a 350 W Xe lamp. In a catalytic process, 20 mg of compound (I) as photocatalyst was added into 50 ml of MB solution (4 × 10 ⁻⁵ mol l⁻¹). The solution was stirred for 30 min in the dark before irradiation to reach adsorption equilibrium between the catalyst and solution and was then exposed to UV irradiation. About 4 ml of the suspension was continually taken from the reaction cell and collected by centrifugation at 30 min inter­vals during the irradiation. The resulting solution was analyzed on a Varian 50 UV/Vis spectrophotometer.

To evaluate the band gaps, the UV–vis absorption spectrum of (I) was measured at room temperature (see Fig. S2 in the Supporting information). The result gives E_g (band-gap energy) value of 3.43 eV for (I) (see Fig. S3 in the Supporting information). As illustrated in Fig. 6, the absorption of MB notably decreased in the presence of (I). The degradation efficiency is defined as C/C₀, where C and C₀ represent the resultant and initial concentration of MB, respectively. By contrast, the simple photolysis experiment was also completed under the same conditions without any catalyst (Fig. 7). The organic dye concentrations were estimated by the absorbance at 665 nm (MB). Compound (I) shows a relatively good photocatalytic activity towards the degradation ratio of MB reached 96.8% exposed to UV light for 120 min (Fig. 7). Compared with other Cd-based coordination polymer (CP) materials, e.g. {[Cd(tpcb)_0.75(OH)(H₂O)₂]NO₃}_n [tpcp is tetra­kis(pyridin-4-yl)cyclo­butane; Li et al., 2014], {[Cd(btbb)_0.5(btec)_0.5(H₂O)]·2H₂O}_n {btbb is 1,4-bis­[2-(thia­zol-2-yl)benzimidazole-1-yl­methyl]­benzene and H₄btec is benzene-1,2,4,5-tetra­carboxyl­ate; Liu, Ding, Li et al., 2014} and {[Cd₃(bcb)₂(H₂O)₅]·H₂O}_n [H₃bcb is 3,4-bis­(4-carb­oxy­phenyl)­benzoic acid; Liu, Ding, Huang et al., 2014], as catalysts, ca 82.0, 92.7 and 88.7% of MB was degraded in 120, 140 and 180 min, respectively. These results suggest that compound (I) may be of use as a potential photoactive material.

Synthesis and crystallization

1,4-Bis(pyridin-3-yl­meth­oxy)­benzene (bpmb) was prepared according to the literature method of Liu, Yu, Li et al. (2015). All other chemicals and reagents were obtained from commercial sources (Sigma–Aldrich) and used as received. A mixture of Cd(OAc)₂·2H₂O (11 mg, 0.04 mmol; OAc is acetate), benzene-1,2-di­carb­oxy­lic acid (3 mg, 0.02 mmol), bpmb (6 mg, 0.02 mmol) and MeOH–H₂O (1:1 v/v, 4 ml) was sealed in a 10 ml Pyrex glass tube and heated at 438 K for 4 d, and then cooled to room temperature at a rate of 5 K h⁻¹. Colourless blocks of (I) were collected and dried in air (yield 7 mg, 41%, based on bpmb). Analysis calculated for C₃₄H₂₄Cd₂N₂O₁₀ (%): H 2.86, C 48.31, N 3.31; found: H 2.59, C 48.14, N 3.60.

Refinement details

Crystal data, data collection, and structure refinement details are summarized in Table 1. A l l H atoms are placed in geometrically idealized positions, with C—H = 0.93 Å for aromatic and 0.97 Å for methyl­ene H atoms, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C,O).

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (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. [Symmetry codes: (i) −x + 1, y, −z + 3/2; (ii) −x + 1, −y + 1, −z + 1; (iv) −x + 1/2, −y + 5/2, −z + 1.]
	Fig. 2. A view of the one-dimensional [Cd2(L)2]n chain of (I), linked via bridging L^2− ligands. All H atoms have been omitted for clarity.
	Fig. 3. A view of the two-dimensional network of (I), extending in the bc plane. All H atoms have been omitted for clarity.
	Fig. 4. A view of the three-dimensional framework of (I). All H atoms have been omitted for clarity.
	Fig. 5. A view of the threefold interpenetration model in (I). Each single net represents a topological structure with a Schläfli symbol 3^34^26^37^18^1. Crossing points represent five-connected nodes and lines represent L^2− and bpmb linkers.
	Fig. 6. A view of the absorption spectra of the MB solution (4 × 10 ^−5 mol l^−1, 50 ml) during the decomposition reaction under UV light irradiation with the presence of compound (I) (20 mg).
	Fig. 7. A view of the concentration changes of MB at different time intervals under Xe lamp irradiation with (I) as catalyst and without catalyst.

Poly[bis(µ₃-benzene-1,2-dicarboxylato)[µ₂-1,4-bis(pyridin-3-ylmethoxy)benzene]dicadmium(II)]

Crystal data

[Cd2(C8H4O4)2(C18H16N2O2)]	F(000) = 1672
Mr = 422.68	Dx = 1.868 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.490 (4) Å	Cell parameters from 8901 reflections
b = 9.985 (2) Å	θ = 2.6–28.4°
c = 15.540 (3) Å	µ = 1.48 mm^−1
β = 96.25 (3)°	T = 296 K
V = 3006.4 (11) Å^3	Block, colourless
Z = 8	0.40 × 0.35 × 0.30 mm

Data collection

Bruker APEXII CCD diffractometer	2575 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
φ and ω scans	θmax = 25.3°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −23→23
Tmin = 0.559, Tmax = 0.641	k = −11→11
10582 measured reflections	l = −17→18
2726 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.019	H-atom parameters constrained
wR(F^2) = 0.050	w = 1/[σ^2(Fo^2) + (0.0244P)^2 + 2.9124P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.002
2726 reflections	Δρmax = 0.49 e Å^−3
218 parameters	Δρmin = −0.50 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00155 (9)

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	0.47738 (2)	0.55800 (2)	0.62009 (2)	0.02664 (8)
C1	0.59402 (10)	0.37244 (19)	0.54707 (12)	0.0275 (4)
C2	0.64743 (9)	0.31891 (19)	0.61587 (12)	0.0268 (4)
C3	0.69675 (10)	0.2327 (2)	0.58786 (14)	0.0370 (5)
H3	0.6962	0.2155	0.5290	0.044*
C4	0.74634 (12)	0.1724 (3)	0.64544 (16)	0.0467 (6)
H4	0.7785	0.1148	0.6254	0.056*
C5	0.74781 (11)	0.1981 (3)	0.73249 (16)	0.0462 (6)
H5	0.7814	0.1586	0.7715	0.055*
C6	0.69917 (11)	0.2828 (2)	0.76203 (14)	0.0367 (5)
H6	0.7004	0.2994	0.8211	0.044*
C7	0.64867 (9)	0.3434 (2)	0.70502 (13)	0.0274 (4)
C8	0.59964 (10)	0.43616 (19)	0.74401 (14)	0.0302 (5)
C9	0.56250 (11)	0.8258 (2)	0.66987 (16)	0.0420 (5)
H9	0.5949	0.7621	0.6910	0.050*
C10	0.57996 (14)	0.9592 (2)	0.6773 (2)	0.0533 (7)
H10	0.6231	0.9848	0.7036	0.064*
C11	0.53318 (13)	1.0533 (2)	0.64563 (18)	0.0467 (6)
H11	0.5440	1.1439	0.6506	0.056*
C12	0.46960 (11)	1.0133 (2)	0.60610 (15)	0.0352 (5)
C13	0.45515 (11)	0.8783 (2)	0.60228 (14)	0.0328 (4)
H13	0.4120	0.8508	0.5770	0.039*
C14	0.42123 (11)	1.1201 (2)	0.56917 (17)	0.0439 (6)
H14A	0.4204	1.1925	0.6106	0.053*
H14B	0.4376	1.1559	0.5171	0.053*
C15	0.30410 (11)	1.1629 (2)	0.52356 (14)	0.0339 (5)
C16	0.23693 (11)	1.1207 (2)	0.52420 (15)	0.0385 (5)
H16	0.2280	1.0333	0.5404	0.046*
C17	0.31735 (11)	1.2929 (2)	0.49896 (15)	0.0379 (5)
H17	0.3626	1.3220	0.4981	0.045*
N1	0.50085 (9)	0.78433 (17)	0.63354 (11)	0.0303 (4)
O1	0.61458 (7)	0.39855 (16)	0.47526 (9)	0.0363 (3)
O2	0.53142 (7)	0.38073 (15)	0.56053 (10)	0.0349 (3)
O3	0.58020 (8)	0.54186 (14)	0.70469 (12)	0.0421 (4)
O4	0.58290 (9)	0.40550 (18)	0.81667 (10)	0.0457 (4)
O5	0.35474 (9)	1.06960 (14)	0.54953 (13)	0.0479 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02504 (10)	0.02343 (11)	0.03080 (11)	−0.00069 (5)	0.00017 (6)	0.00245 (5)
C1	0.0297 (10)	0.0219 (10)	0.0298 (11)	−0.0043 (7)	−0.0018 (8)	−0.0003 (8)
C2	0.0223 (9)	0.0277 (10)	0.0304 (10)	−0.0025 (7)	0.0024 (7)	0.0035 (8)
C3	0.0306 (10)	0.0498 (13)	0.0318 (11)	0.0065 (9)	0.0086 (8)	0.0004 (10)
C4	0.0359 (12)	0.0602 (16)	0.0452 (14)	0.0200 (11)	0.0095 (10)	0.0016 (12)
C5	0.0353 (12)	0.0605 (17)	0.0418 (13)	0.0211 (11)	0.0000 (9)	0.0098 (11)
C6	0.0349 (11)	0.0446 (13)	0.0300 (11)	0.0087 (9)	0.0007 (8)	0.0035 (9)
C7	0.0250 (9)	0.0257 (10)	0.0311 (10)	0.0004 (7)	0.0007 (7)	0.0035 (8)
C8	0.0268 (10)	0.0280 (11)	0.0334 (12)	0.0016 (8)	−0.0075 (8)	−0.0061 (8)
C9	0.0339 (11)	0.0343 (12)	0.0550 (14)	−0.0031 (9)	−0.0082 (10)	0.0113 (10)
C10	0.0412 (14)	0.0389 (14)	0.075 (2)	−0.0137 (10)	−0.0139 (13)	0.0098 (12)
C11	0.0450 (14)	0.0288 (13)	0.0641 (17)	−0.0112 (9)	−0.0038 (12)	0.0056 (10)
C12	0.0376 (12)	0.0266 (11)	0.0414 (12)	0.0020 (9)	0.0042 (9)	0.0015 (9)
C13	0.0298 (10)	0.0279 (11)	0.0395 (12)	−0.0004 (8)	−0.0011 (8)	−0.0016 (9)
C14	0.0372 (12)	0.0289 (12)	0.0652 (16)	0.0010 (9)	0.0042 (11)	0.0042 (11)
C15	0.0368 (11)	0.0242 (10)	0.0396 (12)	0.0013 (8)	−0.0010 (9)	−0.0005 (9)
C16	0.0419 (12)	0.0234 (11)	0.0493 (14)	−0.0025 (9)	0.0001 (10)	0.0052 (9)
C17	0.0333 (11)	0.0311 (12)	0.0488 (13)	−0.0036 (9)	0.0019 (9)	0.0018 (10)
N1	0.0303 (8)	0.0245 (9)	0.0352 (9)	−0.0016 (7)	−0.0008 (7)	0.0028 (7)
O1	0.0343 (8)	0.0445 (9)	0.0288 (8)	−0.0061 (7)	−0.0017 (6)	0.0078 (7)
O2	0.0242 (7)	0.0363 (8)	0.0430 (9)	0.0037 (6)	−0.0018 (6)	−0.0026 (7)
O3	0.0370 (8)	0.0245 (8)	0.0606 (11)	0.0043 (6)	−0.0138 (7)	0.0014 (7)
O4	0.0544 (10)	0.0515 (10)	0.0320 (9)	0.0226 (8)	0.0082 (7)	−0.0047 (7)
O5	0.0364 (9)	0.0246 (8)	0.0796 (13)	0.0002 (6)	−0.0079 (8)	0.0046 (7)

Geometric parameters (Å, º)

Cd1—O4^i	2.2173 (16)	C9—C10	1.376 (3)
Cd1—O1^ii	2.2399 (16)	C9—H9	0.9300
Cd1—O3	2.2796 (17)	C10—C11	1.364 (4)
Cd1—O2	2.3047 (15)	C10—H10	0.9300
Cd1—N1	2.3108 (17)	C11—C12	1.381 (3)
C1—O1	1.254 (2)	C11—H11	0.9300
C1—O2	1.263 (2)	C12—C13	1.377 (3)
C1—C2	1.507 (3)	C12—C14	1.496 (3)
C2—C3	1.395 (3)	C13—N1	1.347 (3)
C2—C7	1.404 (3)	C13—H13	0.9300
C3—C4	1.382 (3)	C14—O5	1.393 (3)
C3—H3	0.9300	C14—H14A	0.9700
C4—C5	1.374 (3)	C14—H14B	0.9700
C4—H4	0.9300	C15—C16	1.376 (3)
C5—C6	1.386 (3)	C15—O5	1.385 (3)
C5—H5	0.9300	C15—C17	1.386 (3)
C6—C7	1.389 (3)	C16—C17^iii	1.382 (3)
C6—H6	0.9300	C16—H16	0.9300
C7—C8	1.505 (3)	C17—C16^iii	1.382 (3)
C8—O4	1.247 (3)	C17—H17	0.9300
C8—O3	1.257 (2)	O1—Cd1^ii	2.2400 (16)
C9—N1	1.337 (3)	O4—Cd1^i	2.2172 (16)
O4^i—Cd1—O1^ii	90.11 (6)	C10—C9—H9	118.7
O4^i—Cd1—O3	99.84 (6)	C11—C10—C9	119.2 (2)
O1^ii—Cd1—O3	170.06 (6)	C11—C10—H10	120.4
O4^i—Cd1—O2	86.44 (7)	C9—C10—H10	120.4
O1^ii—Cd1—O2	104.53 (6)	C10—C11—C12	119.6 (2)
O3—Cd1—O2	76.45 (5)	C10—C11—H11	120.2
O4^i—Cd1—N1	137.80 (6)	C12—C11—H11	120.2
O1^ii—Cd1—N1	90.38 (6)	C13—C12—C11	118.2 (2)
O3—Cd1—N1	82.19 (6)	C13—C12—C14	124.3 (2)
O2—Cd1—N1	133.86 (6)	C11—C12—C14	117.5 (2)
O1—C1—O2	122.83 (18)	N1—C13—C12	122.83 (19)
O1—C1—C2	116.26 (17)	N1—C13—H13	118.6
O2—C1—C2	120.73 (17)	C12—C13—H13	118.6
C3—C2—C7	118.50 (18)	O5—C14—C12	111.02 (18)
C3—C2—C1	116.34 (18)	O5—C14—H14A	109.4
C7—C2—C1	125.07 (17)	C12—C14—H14A	109.4
C4—C3—C2	121.6 (2)	O5—C14—H14B	109.4
C4—C3—H3	119.2	C12—C14—H14B	109.4
C2—C3—H3	119.2	H14A—C14—H14B	108.0
C5—C4—C3	119.6 (2)	C16—C15—O5	116.13 (19)
C5—C4—H4	120.2	C16—C15—C17	119.6 (2)
C3—C4—H4	120.2	O5—C15—C17	124.21 (19)
C4—C5—C6	119.9 (2)	C15—C16—C17^iii	120.6 (2)
C4—C5—H5	120.1	C15—C16—H16	119.7
C6—C5—H5	120.1	C17^iii—C16—H16	119.7
C5—C6—C7	121.2 (2)	C16^iii—C17—C15	119.8 (2)
C5—C6—H6	119.4	C16^iii—C17—H17	120.1
C7—C6—H6	119.4	C15—C17—H17	120.1
C6—C7—C2	119.20 (18)	C9—N1—C13	117.70 (19)
C6—C7—C8	116.64 (18)	C9—N1—Cd1	120.10 (14)
C2—C7—C8	124.13 (17)	C13—N1—Cd1	122.14 (14)
O4—C8—O3	123.5 (2)	C1—O1—Cd1^ii	108.59 (12)
O4—C8—C7	116.99 (17)	C1—O2—Cd1	127.52 (13)
O3—C8—C7	119.5 (2)	C8—O3—Cd1	122.62 (13)
N1—C9—C10	122.6 (2)	C8—O4—Cd1^i	115.86 (14)
N1—C9—H9	118.7	C15—O5—C14	115.92 (16)
O1—C1—C2—C3	−36.7 (3)	C11—C12—C13—N1	−1.6 (3)
O2—C1—C2—C3	138.5 (2)	C14—C12—C13—N1	177.6 (2)
O1—C1—C2—C7	146.91 (19)	C13—C12—C14—O5	14.3 (3)
O2—C1—C2—C7	−37.9 (3)	C11—C12—C14—O5	−166.5 (2)
C7—C2—C3—C4	−0.3 (3)	O5—C15—C16—C17^iii	178.7 (2)
C1—C2—C3—C4	−176.9 (2)	C17—C15—C16—C17^iii	−0.4 (4)
C2—C3—C4—C5	−0.5 (4)	C16—C15—C17—C16^iii	0.4 (4)
C3—C4—C5—C6	0.8 (4)	O5—C15—C17—C16^iii	−178.7 (2)
C4—C5—C6—C7	−0.3 (4)	C10—C9—N1—C13	1.0 (4)
C5—C6—C7—C2	−0.5 (3)	C10—C9—N1—Cd1	178.1 (2)
C5—C6—C7—C8	−178.5 (2)	C12—C13—N1—C9	0.3 (3)
C3—C2—C7—C6	0.8 (3)	C12—C13—N1—Cd1	−176.80 (16)
C1—C2—C7—C6	177.07 (19)	O2—C1—O1—Cd1^ii	−4.6 (2)
C3—C2—C7—C8	178.66 (19)	C2—C1—O1—Cd1^ii	170.47 (13)
C1—C2—C7—C8	−5.1 (3)	O1—C1—O2—Cd1	−96.2 (2)
C6—C7—C8—O4	−35.2 (3)	C2—C1—O2—Cd1	88.9 (2)
C2—C7—C8—O4	146.9 (2)	O4—C8—O3—Cd1	−85.3 (2)
C6—C7—C8—O3	141.6 (2)	C7—C8—O3—Cd1	98.1 (2)
C2—C7—C8—O3	−36.3 (3)	O3—C8—O4—Cd1^i	−5.0 (3)
N1—C9—C10—C11	−0.8 (5)	C7—C8—O4—Cd1^i	171.77 (13)
C9—C10—C11—C12	−0.6 (5)	C16—C15—O5—C14	−164.9 (2)
C10—C11—C12—C13	1.7 (4)	C17—C15—O5—C14	14.2 (3)
C10—C11—C12—C14	−177.5 (3)	C12—C14—O5—C15	173.4 (2)

Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1, −y+1, −z+1; (iii) −x+1/2, −y+5/2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O3	0.93	2.23	2.900 (3)	128
C14—H14A···O4^iv	0.97	2.41	3.363 (3)	166

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