Biphase synthesis of a one-dimensional coordination polymer based on a dinuclear Cd^II secondary building unit and a novel semi-rigid dicarboxyl­ate

A one-dimensional coordination polymer, namely catena-poly[[aqua­pyridine­cadmium(II)]-μ₃-{4,4′-[(2,4,6-trimethyl-1,3-phenyl­ene)bis­(methyl­ene)]dibenzoato}], [Cd(C₂₅H₂₂O₄)(C₅H₅N)(H₂O)]_n, has been synthesized by a biphasic solvo­thermal reaction. The Cd^II cation is located in a CdO₅N six-coordinated environment. The trans 4,4′-[(2,4,6-trimethyl-1,3-phenyl­ene)bis­(methyl­ene)]dibenzoate ligand connects the Cd^II cations to form a one-dimensional ribbon incorporating centrosymmetric [Cd₂(COO)₂] secondary building units. Inter-­ribbon O—H...O hydrogen bonds extend the one-dimensional ribbons into a two-dimensional sheet. No π–π inter­actions are observed. Comparing products synthesized using a different method, it was found that biphasic solvothermal conditions play a crucial role in obtaining large well-shaped single crystals; only intractable precipitates were obtained by the traditional single-phase solvothermal method.

S1. Comment

The search for new coordination polymers (CPs) remains at the forefront of synthetic materials science, as their networks continue to be of interest for many potential applications such as luminescence, gas adsorption, catalysis, magnetism, molecular recognition etc. (Chen et al., 2010; Liu et al., 2010; Kong et al., 2008; Tao et al., 2012; Li et al., 2010; Sun, Liu et al., 2011). One of the main synthetic strategies for CPs is based on the diversity of polynuclear metallic units known as secondary building units (SBUs), as well as predesigned organic spacers (Zhao et al., 2011). Current studies of CPs have suggested that choosing a suitable ligand is very important for the achievement of CPs possessing the required properties, not only because the structure of the ligands has a significant influence on the topology, but also because the functionality of the ligand can be embedded into the whole framework (Blatov, 2007; Sun, Luo et al., 2011; Sun, Wang et al., 2011; Sun et al., 2010). The widely used carboxylic acids, such as aromatic carboxylic acids, often participate in coordination with transition metals, rare earth metal ions or mixed metal ions, exhibiting diverse coordination modes such as monodentate bridging, bidentate chelating or bridging (Wang et al., 2011; Ma et al., 2011; Zheng et al., 2011; Yin et al., 2012; Zhang et al., 2011; Li et al., 2011). Despite CPs constructed from a range of carboxylates having been widely reported, to the best of our knowledge CPs based on H₂TMBDC {4,4'-[(2,4,6-trimethyl-1,3-phenylene)bis(methylene)]dibenzoic acid} have not yet been reported. The presence of methyl groups on the central phenyl ring and methylene groups as connectors between the central phenyl ring and the benzoic acid units could give both steric hindance and flexiblility, giving the H₂TMBDC ligand very interesting structural and functional features. Based on all these points, we have here chosen the semirigid H₂TMBDC ligand and pyridine (py) as mixed ligands and Cd^II as the metal centre to build an infinite one-dimensional ribbon incorporating [Cd₂(COO)₄] SBUs, namely catena-poly[[aquapyridinecadmium(II)]µ₃-{4,4'-[(2,4,6-trimethyl- 1,3-phenylene)bis(methylene)]dibenzoato}], (I).

The asymmetric unit of (I) contains one crystallographically independent Cd^II centre, one TMBDC ligand, one py ligand and one coordinated water ligand. As shown in Fig. 1, atom Cd1 is six-coordinated by the py N atom, four carboxylate O atoms from three different TMBDC ligands and a water molecule, giving a distorted octahedral coordination geometry. The Cd—N and Cd—O distances, in the range 2.2431 (19)–2.3846 (18) Å (Table 1), are comparable with those reported for Cd-based CPs (He et al., 2010; Dai et al., 2010). Interestingly, the terminal coordinated water and pyridine molecules form the shortest and the second longest bond distances to Cd^II, respectively. One carboxylate group of the TMBDC ligand adopts the syn–anti bridging mode and the other adopts a chelating mode.

Two inversion-related Cd^II cations are bridged by four carboxylate groups to form a dinuclear [Cd₂(COO)₄] SBU with a Cd···Cd distance of 5.4568 (5) Å. The two benzoate units are not coplanar with the central benzene ring but distributed on either side of the central benzene ring, generating an anti conformation.

The [Cd₂(COO)₄] SBUs are joined by TMBDC ligands to form an infinite one-dimensional ribbon (Fig. 2). The py ligand acts as a terminal group occupying the remaining coordination site, which prevents the structure from attaining a higher dimensionality. Adjacent one-dimensional ribbons are extended into a two-dimensional supramolecular sheet by interribbon water–TMBDC O—H···O hydrogen bonds (Fig. 3 and Table 2). No π–π interactions are observed in the crystal structure.

The effect of the synthetic method on the structure of this system was investigated by running the reaction in biphasic solvothermal (cyclohexanol–toluene = 1:1) and traditional single-phase solvothermal methods (N,N'-dimethylformamide). Under biphasic solvothermal conditions, we obtained large well shaped single crystals, but only intractable precipitates were obtained by the traditional single-phase solvothermal method. The difference between the two methods confirms that biphasic solvothermal conditions could reduce reaction times and avoid the formation of precipitates (Forster & Cheetham, 2002), thus favouring the growth of single crystals at the interface of the two immiscible solvents.

Related literature

For related literature, see: Blatov (2007); Chen et al. (2010); Dai et al. (2010); Forster & Cheetham (2002); He et al. (2010); Kong et al. (2008); Li et al. (2010, 2011); Liu et al. (2010); Ma et al. (2011); Sun et al. (2010); Sun, Liu, Huang & Zheng (2011); Sun, Luo, Zhang, Huang & Zheng (2011); Sun, Wang, Han, Zhang, Huang & Zheng (2011); Tao et al. (2012); Wang et al. (2011); Yin et al. (2012); Zhang et al. (2011); Zhao et al. (2011); Zheng et al. (2011).

S2. Experimental

A solution of H₂TMBDC (4 mg, 0.010 mmol) in cyclohexanol and toluene (0.5 ml, 1:1 v:v) was layered onto an aqueous solution (0.5 ml) of Cd(NO₃)₂.4H₂O (6 mg, 0.020 mmol) and 18-crown-6 (1 mg, 0.004 mmol), and 2 drops of pyridine were added. The solution was sealed in a glass tube and heated to 403 K for 5 h, kept at 403 K for 72 h, then slowly cooled to 303 K over 10 h. Colourless block-shaped crystals of (I) were collected (yield 48%).

S3. Refinement

C-bound H atoms were placed geometrically and treated as riding on their parent atoms, with C—H = 0.96 (methyl), 0.97 (methenyl) or 0.93 Å (aromatic), and with U_iso(H) = 1.2U_eq(C). The H atoms of the water molecule were located in a difference map and then included in the model as riding, with O—H = 0.85 Å and U_iso(H) = 1.2U_eq(O).

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The structure of (I), showing the atom-numbering scheme and the coordination environment around the Cd^II centre. Displacement ellipsoids are drawn at 30% probability level. [Symmetry codes: (i) -x + 3/2, -y + 1/2, -z + 2; (ii) -x + 1, y, -z + 3/2.]
	Fig. 2. A ball-and-stick perspective view of the one-dimensional ribbon of (I). H atoms have been omitted for clarity.
	Fig. 3. A perspective view of the two-dimensional supramolecular sheet of (I) constructed from one-dimensional ribbons (highlighted by different colours in the electronic version of the journal). H atoms, except for those of the water molecules, have been omitted for clarity. Hydrogen bonds are shown as dashed lines.

catena-poly[[aquapyridinecadmium(II)]µ₃-{4,4'-[(2,4,6-trimethyl- 1,3-phenylene)bis(methylene)]dibenzoato}]

Crystal data

[Cd(C25H22O4)(C5H5N)(H2O)]	F(000) = 2432
Mr = 595.94	Dx = 1.491 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 40.058 (4) Å	Cell parameters from 4106 reflections
b = 5.9102 (5) Å	θ = 4.5–53.6°
c = 24.142 (2) Å	µ = 0.86 mm^−1
β = 111.723 (1)°	T = 298 K
V = 5309.8 (8) Å^3	Block, colourless
Z = 8	0.10 × 0.10 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	6029 independent reflections
Radiation source: fine-focus sealed tube	4415 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ω and ϕ scans	θmax = 27.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −50→51
Tmin = 0.919, Tmax = 0.934	k = −7→7
14990 measured reflections	l = −31→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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.071	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0287P)^2 + 1.6485P] where P = (Fo^2 + 2Fc^2)/3
6029 reflections	(Δ/σ)max = 0.003
337 parameters	Δρmax = 0.48 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.712203 (5)	0.41631 (3)	1.028794 (8)	0.03501 (7)
C1	0.71592 (6)	0.2840 (5)	0.90723 (11)	0.0394 (6)
C2	0.68222 (6)	0.3377 (4)	0.85560 (10)	0.0350 (6)
C3	0.66517 (7)	0.5452 (5)	0.85087 (11)	0.0433 (7)
H3	0.6738	0.6502	0.8816	0.052*
C4	0.63537 (7)	0.5963 (5)	0.80056 (12)	0.0462 (7)
H4	0.6239	0.7350	0.7981	0.055*
C5	0.62239 (7)	0.4438 (5)	0.75390 (11)	0.0407 (6)
C6	0.63862 (7)	0.2353 (5)	0.76003 (12)	0.0490 (7)
H6	0.6295	0.1279	0.7300	0.059*
C7	0.66839 (7)	0.1832 (5)	0.81039 (12)	0.0463 (7)
H7	0.6791	0.0417	0.8136	0.056*
C8	0.59218 (8)	0.5106 (5)	0.69607 (13)	0.0549 (8)
H8A	0.5749	0.6018	0.7056	0.066*
H8B	0.6021	0.6037	0.6728	0.066*
C9	0.57273 (7)	0.3103 (5)	0.65829 (11)	0.0445 (7)
C10	0.58113 (7)	0.2381 (6)	0.61010 (12)	0.0499 (7)
C11	0.56298 (8)	0.0547 (6)	0.57769 (12)	0.0576 (8)
H11	0.5688	0.0053	0.5458	0.069*
C12	0.53656 (8)	−0.0595 (5)	0.59015 (12)	0.0512 (7)
C13	0.52838 (7)	0.0098 (5)	0.63866 (12)	0.0467 (7)
C14	0.54686 (7)	0.1937 (5)	0.67331 (12)	0.0453 (7)
C15	0.53877 (8)	0.2679 (6)	0.72702 (13)	0.0680 (9)
H15A	0.5414	0.1413	0.7532	0.102*
H15B	0.5146	0.3241	0.7142	0.102*
H15C	0.5552	0.3853	0.7478	0.102*
C16	0.60921 (9)	0.3562 (7)	0.59200 (16)	0.0812 (12)
H16A	0.6011	0.5060	0.5781	0.122*
H16B	0.6128	0.2721	0.5607	0.122*
H16C	0.6314	0.3650	0.6257	0.122*
C17	0.51738 (9)	−0.2554 (6)	0.55088 (15)	0.0763 (11)
H17A	0.5230	−0.3930	0.5736	0.114*
H17B	0.5251	−0.2673	0.5177	0.114*
H17C	0.4919	−0.2300	0.5364	0.114*
C18	0.49866 (7)	−0.1080 (5)	0.65219 (14)	0.0576 (8)
H18A	0.5044	−0.1028	0.6949	0.069*
H18B	0.4981	−0.2658	0.6409	0.069*
C19	0.46135 (7)	−0.0082 (5)	0.62091 (12)	0.0439 (7)
C20	0.43140 (7)	−0.1317 (5)	0.61823 (14)	0.0527 (8)
H20	0.4344	−0.2732	0.6363	0.063*
C21	0.39694 (7)	−0.0480 (5)	0.58901 (13)	0.0512 (7)
H21	0.3772	−0.1354	0.5867	0.061*
C22	0.39184 (6)	0.1647 (4)	0.56331 (11)	0.0372 (6)
C23	0.42143 (7)	0.2881 (5)	0.56611 (12)	0.0470 (7)
H23	0.4184	0.4312	0.5489	0.056*
C24	0.45580 (7)	0.2023 (5)	0.59427 (13)	0.0520 (8)
H24	0.4755	0.2881	0.5952	0.062*
C25	0.35503 (7)	0.2602 (5)	0.53201 (11)	0.0388 (6)
C26	0.71673 (10)	0.5108 (7)	1.16252 (15)	0.0721 (10)
H26	0.7287	0.6354	1.1552	0.087*
C27	0.71442 (11)	0.4934 (8)	1.21776 (17)	0.0815 (11)
H27	0.7241	0.6047	1.2465	0.098*
C28	0.69805 (13)	0.3143 (9)	1.22914 (19)	0.0921 (13)
H28	0.6968	0.2951	1.2666	0.111*
C29	0.68310 (14)	0.1588 (8)	1.1853 (2)	0.1049 (15)
H29	0.6709	0.0343	1.1920	0.126*
C30	0.68627 (11)	0.1886 (6)	1.13040 (17)	0.0766 (11)
H30	0.6761	0.0818	1.1006	0.092*
N1	0.70310 (7)	0.3622 (4)	1.11923 (11)	0.0536 (6)
O1	0.72884 (5)	0.4313 (3)	0.94771 (8)	0.0491 (5)
O1W	0.71470 (5)	0.7930 (3)	1.04106 (8)	0.0523 (5)
H1WA	0.7335	0.8425	1.0367	0.063*
H1WB	0.6962	0.8524	1.0150	0.063*
O2	0.73032 (5)	0.0959 (4)	0.90692 (8)	0.0566 (6)
O3	0.35118 (5)	0.4644 (3)	0.51865 (9)	0.0511 (5)
O4	0.32799 (5)	0.1295 (3)	0.51925 (9)	0.0490 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02656 (10)	0.03547 (11)	0.03684 (11)	−0.00178 (9)	0.00455 (7)	0.00330 (9)
C1	0.0254 (13)	0.0599 (19)	0.0297 (13)	−0.0040 (13)	0.0064 (10)	0.0067 (13)
C2	0.0256 (12)	0.0459 (15)	0.0294 (13)	−0.0022 (11)	0.0054 (10)	0.0020 (11)
C3	0.0432 (16)	0.0453 (17)	0.0357 (14)	0.0006 (13)	0.0078 (12)	−0.0033 (12)
C4	0.0421 (15)	0.0416 (16)	0.0482 (16)	0.0109 (13)	0.0090 (13)	0.0025 (13)
C5	0.0295 (13)	0.0468 (17)	0.0372 (14)	0.0018 (12)	0.0025 (11)	0.0064 (12)
C6	0.0425 (16)	0.0475 (17)	0.0402 (15)	0.0059 (14)	−0.0042 (12)	−0.0071 (13)
C7	0.0397 (15)	0.0411 (16)	0.0446 (16)	0.0116 (13)	−0.0003 (12)	−0.0027 (13)
C8	0.0418 (17)	0.0608 (19)	0.0476 (17)	0.0080 (14)	−0.0005 (14)	0.0133 (15)
C9	0.0249 (13)	0.0616 (18)	0.0338 (14)	0.0071 (13)	−0.0047 (11)	0.0083 (13)
C10	0.0273 (14)	0.077 (2)	0.0372 (15)	0.0051 (15)	0.0024 (12)	0.0143 (15)
C11	0.0432 (17)	0.089 (3)	0.0342 (15)	0.0190 (18)	0.0069 (13)	0.0062 (16)
C12	0.0372 (15)	0.0577 (19)	0.0437 (16)	0.0123 (15)	−0.0025 (12)	0.0052 (14)
C13	0.0243 (13)	0.0602 (18)	0.0453 (16)	0.0127 (12)	0.0007 (12)	0.0163 (14)
C14	0.0274 (14)	0.0647 (19)	0.0369 (15)	0.0114 (13)	0.0038 (11)	0.0077 (14)
C15	0.0530 (19)	0.097 (3)	0.058 (2)	0.003 (2)	0.0242 (16)	−0.002 (2)
C16	0.059 (2)	0.121 (3)	0.066 (2)	−0.003 (2)	0.0268 (18)	0.022 (2)
C17	0.069 (2)	0.069 (2)	0.065 (2)	0.009 (2)	−0.0048 (18)	−0.0049 (19)
C18	0.0349 (15)	0.061 (2)	0.067 (2)	0.0097 (14)	0.0069 (14)	0.0207 (16)
C19	0.0279 (14)	0.0470 (16)	0.0505 (17)	0.0028 (12)	0.0069 (12)	0.0056 (13)
C20	0.0361 (15)	0.0425 (17)	0.070 (2)	0.0010 (13)	0.0087 (14)	0.0143 (14)
C21	0.0294 (14)	0.0479 (18)	0.071 (2)	−0.0051 (13)	0.0120 (13)	0.0076 (15)
C22	0.0250 (13)	0.0388 (14)	0.0416 (15)	0.0006 (11)	0.0050 (11)	−0.0036 (11)
C23	0.0313 (14)	0.0430 (17)	0.0590 (18)	0.0007 (13)	0.0077 (13)	0.0099 (14)
C24	0.0256 (14)	0.0537 (19)	0.068 (2)	−0.0054 (13)	0.0080 (13)	0.0127 (15)
C25	0.0296 (13)	0.0435 (16)	0.0395 (14)	0.0002 (12)	0.0083 (11)	−0.0063 (12)
C26	0.078 (3)	0.082 (3)	0.061 (2)	−0.012 (2)	0.031 (2)	0.001 (2)
C27	0.088 (3)	0.102 (3)	0.061 (2)	0.001 (2)	0.035 (2)	−0.005 (2)
C28	0.111 (3)	0.112 (4)	0.079 (3)	0.017 (3)	0.065 (3)	0.013 (3)
C29	0.141 (4)	0.100 (3)	0.110 (4)	−0.016 (3)	0.088 (3)	0.018 (3)
C30	0.098 (3)	0.068 (2)	0.084 (3)	−0.012 (2)	0.057 (2)	0.003 (2)
N1	0.0551 (16)	0.0588 (17)	0.0503 (15)	−0.0023 (13)	0.0236 (12)	0.0066 (12)
O1	0.0406 (11)	0.0654 (13)	0.0322 (10)	−0.0227 (10)	0.0029 (8)	0.0012 (9)
O1W	0.0306 (10)	0.0381 (11)	0.0775 (14)	−0.0007 (9)	0.0076 (9)	0.0106 (10)
O2	0.0352 (10)	0.0798 (16)	0.0429 (11)	0.0201 (11)	0.0007 (8)	0.0016 (10)
O3	0.0306 (10)	0.0409 (12)	0.0698 (13)	0.0028 (8)	0.0047 (9)	0.0016 (10)
O4	0.0260 (9)	0.0425 (11)	0.0675 (13)	−0.0023 (8)	0.0044 (9)	−0.0065 (9)

Geometric parameters (Å, º)

Cd1—O1W	2.2431 (19)	C16—H16B	0.9600
Cd1—O2^i	2.2516 (18)	C16—H16C	0.9600
Cd1—O1	2.2913 (18)	C17—H17A	0.9600
Cd1—O4^ii	2.3302 (18)	C17—H17B	0.9600
Cd1—N1	2.365 (2)	C17—H17C	0.9600
Cd1—O3^ii	2.3846 (18)	C18—C19	1.522 (4)
C1—O2	1.254 (3)	C18—H18A	0.9700
C1—O1	1.267 (3)	C18—H18B	0.9700
C1—C2	1.494 (3)	C19—C24	1.380 (4)
C2—C7	1.373 (3)	C19—C20	1.385 (4)
C2—C3	1.387 (4)	C20—C21	1.388 (4)
C3—C4	1.385 (4)	C20—H20	0.9300
C3—H3	0.9300	C21—C22	1.383 (4)
C4—C5	1.385 (4)	C21—H21	0.9300
C4—H4	0.9300	C22—C23	1.372 (3)
C5—C6	1.376 (4)	C22—C25	1.496 (3)
C5—C8	1.523 (3)	C23—C24	1.386 (4)
C6—C7	1.386 (3)	C23—H23	0.9300
C6—H6	0.9300	C24—H24	0.9300
C7—H7	0.9300	C25—O3	1.244 (3)
C8—C9	1.521 (4)	C25—O4	1.272 (3)
C8—H8A	0.9700	C25—Cd1^ii	2.708 (3)
C8—H8B	0.9700	C26—N1	1.319 (4)
C9—C10	1.393 (4)	C26—C27	1.375 (5)
C9—C14	1.400 (4)	C26—H26	0.9300
C10—C11	1.377 (4)	C27—C28	1.326 (6)
C10—C16	1.519 (4)	C27—H27	0.9300
C11—C12	1.379 (4)	C28—C29	1.362 (6)
C11—H11	0.9300	C28—H28	0.9300
C12—C13	1.390 (4)	C29—C30	1.388 (5)
C12—C17	1.513 (4)	C29—H29	0.9300
C13—C14	1.403 (4)	C30—N1	1.309 (4)
C13—C18	1.516 (4)	C30—H30	0.9300
C14—C15	1.513 (4)	O1W—H1WA	0.8501
C15—H15A	0.9600	O1W—H1WB	0.8498
C15—H15B	0.9600	O2—Cd1^i	2.2516 (18)
C15—H15C	0.9600	O3—Cd1^ii	2.3846 (18)
C16—H16A	0.9600	O4—Cd1^ii	2.3302 (17)
O1W—Cd1—O2^i	87.51 (7)	H15B—C15—H15C	109.5
O1W—Cd1—O1	93.53 (7)	C10—C16—H16A	109.5
O2^i—Cd1—O1	92.50 (7)	C10—C16—H16B	109.5
O1W—Cd1—O4^ii	140.95 (6)	H16A—C16—H16B	109.5
O2^i—Cd1—O4^ii	131.43 (7)	C10—C16—H16C	109.5
O1—Cd1—O4^ii	88.21 (7)	H16A—C16—H16C	109.5
O1W—Cd1—N1	91.54 (8)	H16B—C16—H16C	109.5
O2^i—Cd1—N1	80.04 (8)	C12—C17—H17A	109.5
O1—Cd1—N1	170.79 (8)	C12—C17—H17B	109.5
O4^ii—Cd1—N1	92.69 (8)	H17A—C17—H17B	109.5
O1W—Cd1—O3^ii	86.14 (6)	C12—C17—H17C	109.5
O2^i—Cd1—O3^ii	165.98 (7)	H17A—C17—H17C	109.5
O1—Cd1—O3^ii	100.35 (7)	H17B—C17—H17C	109.5
O4^ii—Cd1—O3^ii	55.31 (6)	C13—C18—C19	114.9 (2)
N1—Cd1—O3^ii	87.65 (8)	C13—C18—H18A	108.5
O2—C1—O1	123.8 (2)	C19—C18—H18A	108.5
O2—C1—C2	117.3 (2)	C13—C18—H18B	108.5
O1—C1—C2	118.9 (3)	C19—C18—H18B	108.5
C7—C2—C3	118.7 (2)	H18A—C18—H18B	107.5
C7—C2—C1	119.8 (2)	C24—C19—C20	117.8 (2)
C3—C2—C1	121.4 (2)	C24—C19—C18	122.6 (2)
C4—C3—C2	120.2 (3)	C20—C19—C18	119.6 (2)
C4—C3—H3	119.9	C19—C20—C21	121.1 (3)
C2—C3—H3	119.9	C19—C20—H20	119.4
C3—C4—C5	120.9 (3)	C21—C20—H20	119.4
C3—C4—H4	119.6	C22—C21—C20	120.4 (3)
C5—C4—H4	119.6	C22—C21—H21	119.8
C6—C5—C4	118.4 (2)	C20—C21—H21	119.8
C6—C5—C8	121.0 (3)	C23—C22—C21	118.7 (2)
C4—C5—C8	120.6 (2)	C23—C22—C25	119.8 (2)
C5—C6—C7	120.8 (3)	C21—C22—C25	121.6 (2)
C5—C6—H6	119.6	C22—C23—C24	120.8 (3)
C7—C6—H6	119.6	C22—C23—H23	119.6
C2—C7—C6	120.8 (3)	C24—C23—H23	119.6
C2—C7—H7	119.6	C19—C24—C23	121.2 (3)
C6—C7—H7	119.6	C19—C24—H24	119.4
C9—C8—C5	113.9 (2)	C23—C24—H24	119.4
C9—C8—H8A	108.8	O3—C25—O4	120.9 (2)
C5—C8—H8A	108.8	O3—C25—C22	120.1 (2)
C9—C8—H8B	108.8	O4—C25—C22	119.0 (2)
C5—C8—H8B	108.8	O3—C25—Cd1^ii	61.70 (13)
H8A—C8—H8B	107.7	O4—C25—Cd1^ii	59.26 (13)
C10—C9—C14	119.8 (3)	C22—C25—Cd1^ii	177.11 (18)
C10—C9—C8	120.7 (3)	N1—C26—C27	124.2 (4)
C14—C9—C8	119.5 (3)	N1—C26—H26	117.9
C11—C10—C9	118.4 (3)	C27—C26—H26	117.9
C11—C10—C16	119.3 (3)	C28—C27—C26	118.5 (4)
C9—C10—C16	122.2 (3)	C28—C27—H27	120.8
C10—C11—C12	123.2 (3)	C26—C27—H27	120.8
C10—C11—H11	118.4	C27—C28—C29	119.1 (4)
C12—C11—H11	118.4	C27—C28—H28	120.5
C11—C12—C13	118.6 (3)	C29—C28—H28	120.5
C11—C12—C17	119.4 (3)	C28—C29—C30	119.2 (4)
C13—C12—C17	122.0 (3)	C28—C29—H29	120.4
C12—C13—C14	119.6 (3)	C30—C29—H29	120.4
C12—C13—C18	119.7 (3)	N1—C30—C29	122.1 (4)
C14—C13—C18	120.7 (3)	N1—C30—H30	118.9
C9—C14—C13	120.3 (3)	C29—C30—H30	118.9
C9—C14—C15	119.6 (3)	C30—N1—C26	116.9 (3)
C13—C14—C15	120.1 (3)	C30—N1—Cd1	124.3 (2)
C14—C15—H15A	109.5	C26—N1—Cd1	118.8 (2)
C14—C15—H15B	109.5	C1—O1—Cd1	117.87 (16)
H15A—C15—H15B	109.5	Cd1—O1W—H1WA	108.9
C14—C15—H15C	109.5	Cd1—O1W—H1WB	109.2
H15A—C15—H15C	109.5	H1WA—O1W—H1WB	109.5

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O1^iii	0.85	1.95	2.719 (2)	151
O1W—H1WB···O4^iv	0.85	1.93	2.675 (2)	146

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