Poly[di-μ-aqua-μ-1,2-bis(pyridin-4-yl)ethene-κ²N:N′-tetrakis(4-iodobenzo­ato-κ²O,O′)dicadmium]

Colourless crystals of the title compound, [Cd₂(C₇H₄IO₂)₄(C₁₂H₁₀N₂)(H₂O)₂]_n, were obtained by the self-assembly of Cd(NO₃)₂·4H₂O, 1,2-bis­(pyridin-4-yl)ethene (bpe) and 4-iodo­benzoic acid (4-IBA). Each Cd^II atom is seven-coordinated in a penta­gonal–bipyramidal coordination environment by four carboxyl­ate O atoms from two different 4-IBA ligands, two O atoms from two water mol­ecules and one N atom from a bpe ligand. The Cd^II centres are bridged by the aqua mol­ecules and bpe ligands, which lie across centres of inversion, to give a two-dimensional net. Topologically, taking the Cd^II atoms as nodes and the μ-aqua and μ-bpe ligands as linkers, the two-dimensional structure can be simplified as a (6,3) network.

S1. Comment

In recent years, coordination polymers have attracted much attention owing to their enormous variety of interesting framework topologies and wide range of potential applications in adsorption, separation, catalysis, magnetism and luminescence (Chen et al., 2006; Fang et al., 2007; Yuan et al., 2010; Zhao et al., 2009). A comprehensive review of coordination polymers with O- or N-containing ligands showed that this field of research has witnessed tremendous growth (Batten & Robson, 1998). Previously, coordination polymers were usually constructed by metal ions and one type of ligand. However, the number of such coordination polymers is limited since the types of ligands are limited. Compared with complexes assembled by one type of ligand, the co-ligand assembly system, consisting of more linkers which are capable of providing more variability to build complicated and interesting structures, has been widely adopted for the generation of new compounds (Kitagawa et al., 2004). As a result, a large number of co-ligand achitectures have been reported, most of which use multi-pyridinyl ligands in metal-carboxylate systems. The application of bis(pyridin-4-yl)-like ligands is an effective method of forming meaningful coordination networks because they can satisfy and even mediate the coordination needs of the metal centres.

To date, a large number of coordination polymers assembled from carboxylates and bis(pyridin-4-yl)-like ligands, as well as their derivatives, have been extensively investigated. These complexes exhibit extraordinary structure diversity and facile accessibility of functionalized new materials. If water is employed as the solvent to synthesize the aforementioned complexes, the water molecules usually function as bridges to link the metal centres to form new subunits (Liu et al., 2010). Herein, we report the synthesis and structure of the title complex, (I), which was constructed from the mixed ligands of 4-iodobenzoate (IBA), 1,2-bis(pyridin-4-yl)ethene (bpe) and H₂O.

A segment of the polymeric structure of (I) lies acoss an inversion centre located at the centre of the bridging bpe ligand [symmetry code: (i) -x + 1, -y + 2, -z + 1], so that the asymmetric unit is composed of one Cd^II atom, one µ-aqua ligand, two 4-IBA ligands and half of a bpe ligand. As shown in Fig. 1, the symmetry-unique Cd^II atom is located in a pentagonal–bipyramidal environment, coordinated by four carboxylate O atoms from two different 4-IBA ligands, two O atoms from two water molecules and one N atom from a bpe ligand. Overall, each Cd^II atom is completely coordinated by one N atom and six O atoms. Such a coordination mode is different from those of the Cd atoms in [Cd(CBA)₂(bpe)]_n (CBA is 4-chlorobenzoate; Liu et al., 2011) and [Cd(bpe)(CH₃COO)₂(H₂O)]_n (Nagarathinam & Vittal, 2008), which are coordinated by two N and five O atoms. The average Cd—O distance [2.374 (3) Å] is shorter than those in [Cd(CBA)₂(bpe)]_n [2.410 (19) Å; Liu et al., 2011] and [Cd(CH₃COO)₂(bpe)(H₂O)]_n [2.423 (4) Å; Nagarathinam & Vittal, 2008]. The Cd—N distance [2.320 (3) Å] is also somewhat shorter than those in [Cd(CBA)₂(bpe)]_n [2.321 (19) Å; Liu et al., 2011] and [Cd(CH₃COO)₂(bpe)(H₂O)]_n [2.397 (4) Å; Nagarathinam & Vittal, 2008]. The N1—Cd1—O5 angle [174.63 (10)°] is close to 180°, and the other N—Cd—O and O—Cd—O angles are in the range of 55.87 (9)–160.55 (11)°, consistent with a pentagonal–bipyramidal coordination environment about the Cd^II centre.

In (I), each Cd^II atom is interlinked by µ-aqua molecules to form a one-dimensional [Cd(µ-aqua)]_n chain extending along the b axis (Fig. 2). Each Cd^II atom is then chelated by two ligands in the one-dimensional chain (Fig. 3). The chain is stabilized by intermolecular hydrogen bonding interactions (O5—H1W···O4 and O5—H2W···O1) between H₂O and carboxylate groups (Table 1). The unsaturated coordinated Cd^II atoms are further linked to neighbouring ones by bridging bpe ligands to produce a two-dimensional net (Fig. 4). From a topological point of view, this two-dimensional net can be simplified as a (6,3) network by treating the Cd^II centres as nodes and the H₂O and bpe ligands as linkers (Fig. 5).

Some Cd^II coordination polymers with bpe and monocarboxylate ligands have been reported in recent years. For example, the Cd complex [Cd(CBA)₂(bpe)]_n was isolated from the reaction between Cd(NO₃)₂, bpe and 4-chlorobenzoic acid under hydrothermal conditions. In [Cd(CBA)₂(bpe)]_n, the carboxylate groups of the CBA ligands adopt both chelating and tridentate modes, coordinating the Cd atoms to form dinuclear [Cd₂(CBA)₄] units. The dinuclear [Cd₂(CBA)₄] units are then linked by pairs of bpe ligands to form a one-dimensional ladder-like structure (Liu et al., 2011). In (I), the carboxylate groups of the IBA ligands adopt only chelating coordination modes. As a result, each pair of IBA ligands can supply only four coordination sites for each Cd^II centre. In order to complete its coordination environment, the Cd^II atom must be coordinated by more atoms. Thus, the H₂O molecules could work as bridges to connect the Cd^II atoms to form a polymeric structure.

If Cd(CH₃COO)₂ and bpe are employed as the starting materials, the complex [Cd(CH₃COO)₂(bpe)(H₂O)]_n is obtained through the slow evaporation of a solution containing the starting materials in an ethanol and water mixture (Nagarathinam & Vittal, 2008). It is noted that the solvent water molecules function as ligands in the product. The main structure of [Cd(CH₃COO)₂(bpe)(H₂O)]_n is still a one-dimensional chain, since the water molecules are only terminal ligands. The H atoms of the coordinated water molecules in one chain form complementary hydrogen bonds to the O atoms of the chelating acetate ions in an adjacent chain. As a result, these one-dimensional chains are interconnected to form a two-dimensional supramolecular sheet via hydrogen-bonding interactions. However, In (I), the H₂O molecules function as linkers, so they can only connect adjacent Cd^II atoms into a one-dimensional polymeric chain. These one-dimensional chains are further linked by bpe ligands to form a two-dimensional coordination network which is completely different from those of the two previously reported complexes.

In summary, we have demonstrated the formation of a coordination polymer, (I), from the hydrothermal reaction of Cd(NO₃)₂ with 4-IBA, bpe and H₂O. The results indicate that the bridging H₂O molecules can increase the dimensionality of the final structure. It is expected that other systems containing carboxylate, dipyridinyl and H₂O ligands can produce other multi-dimensional coordination polymers with new topological structures.

Related literature

For related literature, see: Batten & Robson (1998); Chen et al. (2006); Fang et al. (2007); Kitagawa et al. (2004); Liu et al. (2010, 2011); Nagarathinam & Vittal (2008); Yuan et al. (2010); Zhao et al. (2009).

S2. Experimental

Into a 25 ml Teflon-lined stainless steel autoclave were loaded Cd(NO₃)₂.4H₂O (154 mg, 0.5 mmol), 1,2-bis(pyridin-4-yl)ethene (91 mg, 0.5 mmol) and 4-iodobenzoic acid (248 mg, 1 mmol). The tube was sealed and heated in an oven to 443 K for 3 d, and then cooled to ambient temperature at a rate of 5 K h^-1 to form colourless crystals of (I), which were washed with water/ethanol and dried in air (yield 297 mg, 83% yield based on Cd). Analysis, calculated for C₂₀H₁₅CdI₂NO₅: C 33.57, H 2.11, N 1.96%; found: C 33.82, H 2.01, N 1.63%. Spectroscopic analysis: IR (KBr, ν, cm^-1): 3440 (m), 3029 (m), 1616 (s), 1560 (s), 1431 (m), 1385 (s), 1224 (w), 1204 (m), 1086 (m), 1028 (m), 959 (m), 833 (s), 757 (s), 716 (s), 618 (m), 555 (s), 436 (m).

S3. Refinement

The H atoms of the coordinated water molecules were located in a Fourier map. All other H atoms were placed in geometrically idealized positions, with C—H = 0.95 Å for phenyl, pyridinyl and vinyl groups, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C). The minimum and maximum residual electron densities are located 0.30 and 0.80 Å, respectively, from atom I2. The location of the maximum residual electron-density peak does not fit the geometry of any expected disorder or impurity.

Computing details

Data collection: CrystalClear (Rigaku, 2001); cell refinement: CrystalClear (Rigaku, 2001); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: 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), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) -x + 1, -y + 2, -z + 1; (ii) -x + 3/2, y + 1/2, -z + 3/2.]
	Fig. 2. A view of the one-dimensional [Cd(µ-aqua)]n chain extending along the b axis.
	Fig. 3. A view of the one-dimensional [Cd(µ-aqua)(4-IBA)2]n chain extending along the b axis.
	Fig. 4. A view of the two-dimensional network of (I).
	Fig. 5. A view of the topological net of (I).

Poly[di-µ-aqua-µ-1,2-bis(pyridin-4-yl)ethene-κ²N:N'- tetrakis(4-iodobenzoato-κ²O,O')dicadmium]

Crystal data

[Cd2(C7H4IO2)4(C12H10N2)(H2O)2]	F(000) = 2688
Mr = 715.54	Dx = 2.167 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8841 reflections
a = 29.236 (6) Å	θ = 3.0–27.5°
b = 5.7289 (11) Å	µ = 3.84 mm^−1
c = 28.417 (6) Å	T = 223 K
β = 112.82 (3)°	Block, colourless
V = 4387.0 (18) Å^3	0.45 × 0.30 × 0.30 mm
Z = 8

Data collection

Rigaku MercuryCCD area-detector diffractometer	5018 independent reflections
Radiation source: fine-focus sealed tube	3615 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	h = −37→35
Tmin = 0.277, Tmax = 0.392	k = −7→7
20159 measured reflections	l = −28→36

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.089	w = 1/[σ^2(Fo^2) + (0.0407P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.91	(Δ/σ)max = 0.001
5018 reflections	Δρmax = 1.16 e Å^−3
265 parameters	Δρmin = −1.76 e Å^−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00100 (4)

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
Cd1	0.702659 (10)	0.51512 (4)	0.699916 (11)	0.02118 (10)
I1	0.859079 (16)	0.01161 (6)	0.499087 (16)	0.05781 (14)
I2	0.512605 (15)	0.02582 (7)	0.867649 (18)	0.06487 (15)
N1	0.63233 (12)	0.6432 (5)	0.63249 (13)	0.0260 (7)
O1	0.72282 (10)	0.2206 (4)	0.65260 (11)	0.0295 (7)
O2	0.75698 (11)	0.5688 (5)	0.65800 (12)	0.0337 (7)
O3	0.66681 (11)	0.5545 (5)	0.75996 (13)	0.0354 (7)
O4	0.65569 (10)	0.2162 (4)	0.71995 (11)	0.0299 (7)
O5	0.77403 (9)	0.4079 (4)	0.77508 (10)	0.0236 (6)
H1W	0.7967	0.4972	0.7737	0.049 (16)*
H2W	0.7672	0.4911	0.7962	0.045 (15)*
C1	0.63383 (15)	0.8378 (7)	0.60699 (17)	0.0298 (9)
H1	0.6642	0.9173	0.6163	0.036*
C2	0.59296 (16)	0.9271 (7)	0.56765 (17)	0.0310 (10)
H2	0.5958	1.0643	0.5508	0.037*
C3	0.54744 (14)	0.8134 (7)	0.55295 (16)	0.0273 (9)
C4	0.54645 (15)	0.6101 (7)	0.57942 (17)	0.0316 (10)
H4	0.5167	0.5257	0.5707	0.038*
C5	0.58901 (15)	0.5322 (6)	0.61836 (17)	0.0290 (9)
H5	0.5874	0.3948	0.6357	0.035*
C6	0.50194 (14)	0.9012 (7)	0.51309 (17)	0.0296 (9)
H6	0.4730	0.8112	0.5053	0.036*
C7	0.75131 (14)	0.3619 (7)	0.64207 (16)	0.0265 (9)
C8	0.77652 (14)	0.2800 (7)	0.60864 (16)	0.0261 (9)
C9	0.76555 (17)	0.0635 (7)	0.58451 (19)	0.0357 (11)
H9	0.7423	−0.0346	0.5899	0.043*
C10	0.78837 (19)	−0.0075 (7)	0.55304 (19)	0.0378 (11)
H10	0.7803	−0.1527	0.5364	0.045*
C11	0.82314 (16)	0.1337 (7)	0.54571 (17)	0.0335 (10)
C12	0.83515 (17)	0.3486 (7)	0.56929 (19)	0.0386 (11)
H12	0.8590	0.4441	0.5642	0.046*
C13	0.81162 (16)	0.4211 (7)	0.60046 (17)	0.0310 (10)
H13	0.8194	0.5678	0.6164	0.037*
C14	0.64925 (14)	0.3523 (7)	0.75235 (17)	0.0276 (9)
C15	0.61771 (15)	0.2728 (7)	0.78011 (17)	0.0292 (9)
C16	0.61094 (16)	0.4180 (7)	0.81593 (18)	0.0338 (10)
H16	0.6271	0.5633	0.8235	0.041*
C17	0.58060 (17)	0.3503 (8)	0.84062 (19)	0.0423 (12)
H17	0.5759	0.4486	0.8648	0.051*
C18	0.55729 (16)	0.1350 (8)	0.8290 (2)	0.0399 (11)
C19	0.56438 (18)	−0.0121 (7)	0.7940 (2)	0.0411 (12)
H19	0.5486	−0.1583	0.7867	0.049*
C20	0.59473 (16)	0.0570 (7)	0.76967 (19)	0.0350 (10)
H20	0.5999	−0.0428	0.7459	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02199 (17)	0.02064 (15)	0.02179 (17)	0.00074 (11)	0.00946 (13)	0.00158 (11)
I1	0.0791 (3)	0.0610 (2)	0.0577 (3)	0.00261 (18)	0.0532 (2)	−0.00859 (18)
I2	0.0592 (3)	0.0836 (3)	0.0752 (3)	0.00361 (19)	0.0517 (3)	0.0227 (2)
N1	0.0254 (18)	0.0274 (17)	0.0241 (19)	−0.0011 (14)	0.0084 (15)	0.0014 (14)
O1	0.0343 (16)	0.0257 (14)	0.0359 (19)	−0.0031 (12)	0.0218 (15)	−0.0003 (13)
O2	0.0426 (18)	0.0251 (14)	0.045 (2)	−0.0062 (13)	0.0291 (16)	−0.0085 (13)
O3	0.0412 (18)	0.0314 (15)	0.042 (2)	−0.0053 (13)	0.0250 (16)	0.0008 (14)
O4	0.0317 (16)	0.0302 (15)	0.0327 (18)	0.0027 (12)	0.0176 (14)	0.0028 (13)
O5	0.0277 (15)	0.0187 (12)	0.0270 (16)	0.0005 (11)	0.0135 (13)	−0.0006 (12)
C1	0.025 (2)	0.032 (2)	0.030 (2)	−0.0052 (17)	0.0076 (19)	0.0004 (18)
C2	0.031 (2)	0.032 (2)	0.026 (2)	−0.0007 (18)	0.008 (2)	0.0103 (18)
C3	0.025 (2)	0.031 (2)	0.026 (2)	0.0014 (17)	0.0093 (19)	−0.0009 (18)
C4	0.025 (2)	0.030 (2)	0.038 (3)	−0.0027 (18)	0.009 (2)	0.003 (2)
C5	0.028 (2)	0.026 (2)	0.030 (2)	−0.0020 (17)	0.008 (2)	0.0062 (17)
C6	0.023 (2)	0.031 (2)	0.032 (3)	0.0005 (17)	0.007 (2)	0.0033 (18)
C7	0.026 (2)	0.027 (2)	0.028 (2)	0.0035 (17)	0.0124 (19)	0.0059 (17)
C8	0.030 (2)	0.027 (2)	0.023 (2)	0.0014 (17)	0.0133 (19)	0.0009 (17)
C9	0.044 (3)	0.028 (2)	0.044 (3)	−0.0106 (19)	0.027 (2)	−0.006 (2)
C10	0.049 (3)	0.032 (2)	0.039 (3)	−0.005 (2)	0.024 (2)	−0.008 (2)
C11	0.041 (3)	0.038 (2)	0.031 (3)	0.002 (2)	0.024 (2)	−0.001 (2)
C12	0.048 (3)	0.036 (2)	0.044 (3)	−0.008 (2)	0.030 (3)	−0.004 (2)
C13	0.038 (2)	0.0267 (19)	0.033 (3)	−0.0083 (18)	0.019 (2)	−0.0033 (18)
C14	0.024 (2)	0.031 (2)	0.029 (2)	0.0064 (17)	0.0117 (19)	0.0071 (18)
C15	0.030 (2)	0.028 (2)	0.034 (3)	0.0059 (17)	0.016 (2)	0.0079 (18)
C16	0.035 (2)	0.034 (2)	0.038 (3)	0.0004 (19)	0.020 (2)	0.001 (2)
C17	0.046 (3)	0.050 (3)	0.040 (3)	0.008 (2)	0.026 (3)	0.001 (2)
C18	0.035 (3)	0.050 (3)	0.047 (3)	0.006 (2)	0.029 (2)	0.014 (2)
C19	0.039 (3)	0.036 (2)	0.056 (3)	−0.003 (2)	0.028 (3)	0.007 (2)
C20	0.035 (2)	0.035 (2)	0.043 (3)	0.0012 (19)	0.024 (2)	−0.002 (2)

Geometric parameters (Å, º)

Cd1—N1	2.320 (3)	C4—H4	0.9400
Cd1—O3	2.334 (3)	C5—H5	0.9400
Cd1—O2	2.346 (3)	C6—C6^iii	1.335 (8)
Cd1—O1	2.370 (3)	C6—H6	0.9400
Cd1—O5^i	2.378 (2)	C7—C8	1.486 (5)
Cd1—O4	2.398 (3)	C8—C9	1.393 (5)
Cd1—O5	2.416 (3)	C8—C13	1.395 (5)
Cd1—C7	2.704 (4)	C9—C10	1.369 (6)
Cd1—C14	2.708 (4)	C9—H9	0.9400
I1—C11	2.104 (4)	C10—C11	1.377 (6)
I2—C18	2.101 (4)	C10—H10	0.9400
N1—C5	1.332 (5)	C11—C12	1.380 (6)
N1—C1	1.340 (5)	C12—C13	1.379 (6)
O1—C7	1.277 (5)	C12—H12	0.9400
O2—C7	1.257 (5)	C13—H13	0.9400
O3—C14	1.251 (5)	C14—C15	1.498 (6)
O4—C14	1.275 (5)	C15—C20	1.383 (6)
O5—Cd1^ii	2.378 (2)	C15—C16	1.387 (6)
O5—H1W	0.8504	C16—C17	1.383 (6)
O5—H2W	0.8498	C16—H16	0.9400
C1—C2	1.379 (6)	C17—C18	1.386 (7)
C1—H1	0.9400	C17—H17	0.9400
C2—C3	1.393 (6)	C18—C19	1.380 (7)
C2—H2	0.9400	C19—C20	1.376 (6)
C3—C4	1.393 (6)	C19—H19	0.9400
C3—C6	1.462 (5)	C20—H20	0.9400
C4—C5	1.380 (6)
N1—Cd1—O3	93.89 (12)	C5—C4—C3	120.2 (4)
N1—Cd1—O2	95.56 (12)	C5—C4—H4	119.9
O3—Cd1—O2	160.55 (11)	C3—C4—H4	119.9
N1—Cd1—O1	95.31 (11)	N1—C5—C4	122.9 (4)
O3—Cd1—O1	139.86 (9)	N1—C5—H5	118.5
O2—Cd1—O1	55.87 (9)	C4—C5—H5	118.5
N1—Cd1—O5^i	90.40 (10)	C6^iii—C6—C3	125.4 (5)
O3—Cd1—O5^i	81.26 (9)	C6^iii—C6—H6	117.3
O2—Cd1—O5^i	81.71 (9)	C3—C6—H6	117.3
O1—Cd1—O5^i	137.52 (9)	O2—C7—O1	121.4 (4)
N1—Cd1—O4	90.93 (11)	O2—C7—C8	119.9 (3)
O3—Cd1—O4	55.56 (9)	O1—C7—C8	118.7 (4)
O2—Cd1—O4	140.99 (9)	O2—C7—Cd1	60.1 (2)
O1—Cd1—O4	85.27 (9)	O1—C7—Cd1	61.2 (2)
O5^i—Cd1—O4	136.80 (9)	C8—C7—Cd1	178.0 (3)
N1—Cd1—O5	174.63 (10)	C9—C8—C13	118.5 (4)
O3—Cd1—O5	81.78 (10)	C9—C8—C7	121.3 (4)
O2—Cd1—O5	87.69 (10)	C13—C8—C7	120.2 (4)
O1—Cd1—O5	90.05 (9)	C10—C9—C8	120.6 (4)
O5^i—Cd1—O5	85.83 (6)	C10—C9—H9	119.7
O4—Cd1—O5	89.21 (9)	C8—C9—H9	119.7
N1—Cd1—C7	96.16 (12)	C9—C10—C11	120.0 (4)
O3—Cd1—C7	165.26 (11)	C9—C10—H10	120.0
O2—Cd1—C7	27.67 (10)	C11—C10—H10	120.0
O1—Cd1—C7	28.19 (10)	C10—C11—C12	121.0 (4)
O5^i—Cd1—C7	109.36 (11)	C10—C11—I1	118.6 (3)
O4—Cd1—C7	113.40 (11)	C12—C11—I1	120.5 (3)
O5—Cd1—C7	88.70 (11)	C13—C12—C11	118.9 (4)
N1—Cd1—C14	92.75 (12)	C13—C12—H12	120.5
O3—Cd1—C14	27.48 (11)	C11—C12—H12	120.5
O2—Cd1—C14	166.63 (11)	C12—C13—C8	121.0 (4)
O1—Cd1—C14	112.97 (11)	C12—C13—H13	119.5
O5^i—Cd1—C14	108.73 (11)	C8—C13—H13	119.5
O4—Cd1—C14	28.08 (11)	O3—C14—O4	121.7 (4)
O5—Cd1—C14	84.86 (11)	O3—C14—C15	119.0 (4)
C7—Cd1—C14	140.73 (12)	O4—C14—C15	119.2 (4)
C5—N1—C1	117.4 (4)	O3—C14—Cd1	59.4 (2)
C5—N1—Cd1	122.2 (3)	O4—C14—Cd1	62.3 (2)
C1—N1—Cd1	120.4 (3)	C15—C14—Cd1	176.9 (3)
C7—O1—Cd1	90.6 (2)	C20—C15—C16	119.8 (4)
C7—O2—Cd1	92.2 (2)	C20—C15—C14	120.4 (4)
C14—O3—Cd1	93.1 (2)	C16—C15—C14	119.8 (4)
C14—O4—Cd1	89.6 (2)	C17—C16—C15	120.4 (4)
Cd1^ii—O5—Cd1	123.64 (11)	C17—C16—H16	119.8
Cd1^ii—O5—H1W	116.4	C15—C16—H16	119.8
Cd1—O5—H1W	103.1	C16—C17—C18	118.8 (4)
Cd1^ii—O5—H2W	116.0	C16—C17—H17	120.6
Cd1—O5—H2W	97.0	C18—C17—H17	120.6
H1W—O5—H2W	95.6	C19—C18—C17	121.2 (4)
N1—C1—C2	123.2 (4)	C19—C18—I2	119.6 (3)
N1—C1—H1	118.4	C17—C18—I2	119.2 (3)
C2—C1—H1	118.4	C20—C19—C18	119.5 (4)
C1—C2—C3	119.7 (4)	C20—C19—H19	120.2
C1—C2—H2	120.1	C18—C19—H19	120.2
C3—C2—H2	120.1	C19—C20—C15	120.2 (4)
C2—C3—C4	116.5 (4)	C19—C20—H20	119.9
C2—C3—C6	123.2 (4)	C15—C20—H20	119.9
C4—C3—C6	120.2 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1W···O4^i	0.85	1.83	2.672 (4)	170
O5—H2W···O1^i	0.85	1.90	2.701 (4)	157

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