Poly[aqua­[[mu]₂-1,4-bis­(imidazol-1-yl­meth­yl)benzene-[kappa]²N³:N^3']([mu]₂-5-hy­droxy­benzene-1,3-dicarboxyl­ato-[kappa]⁴O¹,O^1':O³,O^3')cadmium(II)], a twofold inter­penetrated CdSO₄-like metal-organic polymer

In the title cadmium(II) complex, [Cd(C₈H₄O₅)(C₁₄H₁₄N₄)(H₂O)]_n, the 5-hy­droxy­benzene-1,3-dicarboxyl­ate (5-OH-1,3-bdc) and 1,4-bis­(imidazol-1-ylmeth­yl)benzene (1,4,-bix) lig­ands bridge water-coordinated Cd^II atoms to generate a three-dimensional network. Two carboxyl­ate groups from different ligands function as O,O'-chelates, while two imidazole N atoms from different ligands coordinate in a monodentate fashion, and one water mol­ecule completes the seven-coordinate penta­gonal bipyramid around the Cd^II atom, in which the N atoms occupy the axial sites and the O atoms occupy the equatorial sites. The overall architecture is a twofold inter­penetrated CdSO₄-type framework. The two crystallographically equivalent frameworks are linked by O-H...O hydrogen bonds between the water, hy­droxy and carboxyl­ate groups.

S1. Comment

The design and synthesis of metal–organic frameworks (MOFs) have been an area of rapid growth in recent years owing to the potential applications of MOFs in nonlinear optics, luminescence, magnetism, catalysis, gas absorption, ion exchange and as zeolite-like materials for molecular selection (O'Keeffe et al., 2008). Structural diversity in MOFs can occur as a result of various processes, including supramolecular isomerism, interpenetration or interweaving (Batten & Robson, 1998; Batten, 2001). Ideally, the topologies of MOFs can be controlled and modified by the coordination geometry preferred by the metal ion and the chemical structure of the organic ligand chosen (Abrahams et al., 1999; Yang et al., 2008). In this regard, rigid N-donor 4,4'-bipyridine (bipy) and its derivatives have been studied in the construction of MOFs (Qiao et al., 2008). So far, a number of MOFs based on bipy and its derivatives have been reported, including one-dimensional chain, two-dimensional layer and three-dimensional frameworks (Carlucci et al., 2003). However, reports of MOFs constructed by flexible N-donor ligands are relatively rare (Wang et al., 2006). Among such ligands, bis(imidazole) derivatives are a good choice (Yang et al., 2008) leading to some intriguing interpenetrating architectures and topologies (Wang et al., 2006). In this work, we chose 5-hydroxybenzene-1,3-dicarboxylic acid (5-OH-1,3-H₂bdc) as a dicarboxylate ligand and 1,4-bis(imidazol-1-ylmethyl)benzene (1,4-bix) as a flexible N-donor ligand, yielding a new coordination polymer, [Cd(1,4-bix)(5-OH-1,3-bdc)(H₂O)], (I), with a fascinating twofold interpenetrated three-dimensional CdSO₄-like framework.

The asymetric unit of (I) contains one Cd^II atom, one 5-OH-1,3-bdc anion, one 1,4-bix ligand and one coordination water molecule (Fig. 1). Each Cd^II atom is seven-coordinated in a pentagonal bipyramid by four carboxylate oxygen atoms from two different 5-OH-1,3-bdc anions, one water oxygen atom and two nitrogen atoms from two distinct 1,4-bix ligands. The N atoms occupy the apical sites and the O atoms occupy the equatorial sites of the bipyramid. The Cd—O_carboxylate distances (Table 1) are comparable to those observed in [Cd(bpdo)(1,4-bdc)(H₂O)]_n (1,4-bdc = benzene-1,4-dicarboxylate and bpdo = 4,4'-bipyridine N,N'-dioxide) (Xu & Xie, 2010).

Each crystallographically unique Cd^II atom is bridged by the 1,4-bix ligands and 5-OH-1,3-bdc anions to generate a novel three-dimensional framework (Fig. 2). The Cd···Cd distances bridged by 1,4-bix and 5-OH-1,3-bdc are 14.368 (3) and 9.844 (3) Å, respectively. Topologically, the Cd^II centre is defined as a four-connected node, and the 1,4-bix and the 5-OH-1,3-bdc serve as linkers. Therefore, on the basis of the concept of chemical topology, the overall structure of (I) is a four-connected framework with the Schläfli symbol of 6⁵8. Topological analysis reveals that this three-dimensional framework is a typical CdSO₄ net. Interestingly, the large spaces in the single three-dimensional framework allow another identical framework to interpenetrate it, providing a twofold interpenetrating CdSO₄ framework (Fig. 3). Each CdSO₄ net is hydrogen bonded to its neighbour through O—H···O hydrogen bonds among the water molecules, hydroxy group and carboxylate oxygen atoms (Table 2).

So far, some related interpenetrated CdSO₄-like MOFs based on both dicarboxylate and flexible N-donor bridging ligands have been reported. The structure of [Zn₂(1,4-bdc)(bpp)Cl₂]_n (1,4-bdc = 1,4-benzenedicarboxylate and bpp = 1,3-bis(4-pyridyl)propane) (Zhang et al., 2006) also contains two crystallographically equivalent nets, but differs from (I) in that the four-connected nodes are based on Zn^II dimers rather than mononuclear complexes. [Zn(mip)(bpa)]_n [mip = 5-methylisophthalate and bpa = 1,2-bis(4-pyridyl)ethane] (Ma et al., 2009) shows an unusual threefold interpenetrated CdSO₄ topology. [Ni(oba)(bbi)]₂^.H₂O [oba = 4,4'-oxybis(benzoate) and bbi = 1,1'-(1,4-butanediyl)bis(imidazole)] (Yang et al., 2009) also shows twofold interpenetrated nets as in (I); however, the nets are crystallographically distinct. Thus, we believe that (I) represents the first example of this specific type of architecture in a Cd–dicarboxylate–flexible-N-donor system.

Related literature

For related literature, see: Abrahams et al. (1999); Batten (2001); Batten & Robson (1998); Carlucci et al. (2003); Ma et al. (2009); O'Keeffe et al. (2008); Qiao et al. (2008); Wang et al. (2006); Xu & Xie (2010); Yang et al. (2008, 2009); Zhang et al. (2006).

S2. Experimental

A mixture of CdCl₂.2.5H₂O (0.5 mmol), 1,4-bis(imidazol-1-ylmethyl)benzene (0.5 mmol), 5-hydroxybenzene-1,3-dicarboxylic acid (0.5 mmol) and water (12 ml) was sealed in a 23 ml Teflon-lined stainless-steel Parr bomb. The bomb was heated at 413 K for 3 d. It was then cooled to room temperature. Colourless block-shaped crystals were collected and washed with water; the yield based on Cd was about 40%.

S3. Refinement

Carbon-bound H atoms were positioned geometrically [C—H = 0.93 (aromatic) or 0.97 (methylene) Å] and included as riding atoms with U_iso(H) fixed at 1.2U_eq(C). H atoms bonded to water molecules were located in difference Fourier maps and refined isotropically with distance restraints of O—H = 0.85 (1) and H···H = 1.35 (1) with U_iso = 1.5U_eq(O). The hydroxy H atom was located in a difference Fourier map and refined isotropically with a distance restraint of O—H = 0.82 (1) Å and U_iso = 1.5U_eq(O).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. A view of the local coordination of the Cd^II atom in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) x, y - 1, z - 1; (ii) x + 1/2, -y + 1, z - 1/2.]
	Fig. 2. View of a single CdSO4 net of (I), showing bridging by 1,4-bix and 5-OH-1,3-bdc ligands.
	Fig. 3. View of the twofold interpenetrating three-dimensional CdSO4 net of (I).

Poly[aqua[µ₂-1,4-bis(imidazol-1-ylmethyl)benzene- κ²N³:N^3'](µ₂-5-hydroxybenzene-1,3-dicarboxylato- κ⁴O¹,O^1':O³,O^3']cadmium(II)]

Crystal data

[Cd(C8H4O5)(C14H14N4)(H2O)]	F(000) = 552
Mr = 548.82	Dx = 1.749 Mg m^−3
Monoclinic, Pn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yac	Cell parameters from 2693 reflections
a = 11.5800 (9) Å	θ = 2.1–28.3°
b = 8.4221 (6) Å	µ = 1.10 mm^−1
c = 11.6393 (9) Å	T = 293 K
β = 113.354 (1)°	Block, colorless
V = 1042.16 (14) Å^3	0.18 × 0.16 × 0.11 mm
Z = 2

Data collection

Bruker APEX diffractometer	3693 independent reflections
Radiation source: fine-focus sealed tube	3404 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ϕ and ω scans	θmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→15
Tmin = 0.39, Tmax = 0.57	k = −11→8
6155 measured reflections	l = −15→14

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)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.054	w = 1/[σ^2(Fo^2) + (0.0136P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
3693 reflections	Δρmax = 0.38 e Å^−3
307 parameters	Δρmin = −0.39 e Å^−3
6 restraints	Absolute structure: Flack (1983), ???? Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.013 (19)

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	0.74827 (2)	0.59903 (3)	0.92168 (2)	0.02739 (7)
C1	0.8351 (4)	0.2245 (5)	1.0146 (4)	0.0371 (9)
H1	0.9061	0.2274	0.9960	0.044*
C2	0.8004 (5)	0.0995 (5)	1.0672 (5)	0.0371 (11)
H2	0.8416	0.0026	1.0906	0.045*
C3	0.6645 (4)	0.2929 (4)	1.0332 (4)	0.0340 (9)
H3	0.5949	0.3505	1.0302	0.041*
C4	0.6212 (4)	0.0550 (4)	1.1358 (4)	0.0359 (9)
H4A	0.6308	−0.0572	1.1230	0.043*
H4B	0.5327	0.0809	1.0932	0.043*
C5	0.6608 (4)	0.0849 (4)	1.2738 (4)	0.0346 (9)
C6	0.7597 (5)	0.1817 (6)	1.3458 (5)	0.0395 (12)
H6	0.8080	0.2308	1.3085	0.047*
C7	0.5911 (4)	0.0142 (5)	1.3327 (4)	0.0417 (10)
H7	0.5248	−0.0524	1.2868	0.050*
C8	0.6178 (5)	0.0400 (5)	1.4583 (4)	0.0451 (11)
H8	0.5701	−0.0102	1.4957	0.054*
C9	0.7152 (5)	0.1403 (5)	1.5283 (4)	0.0348 (11)
C10	0.7887 (5)	0.2071 (5)	1.4711 (4)	0.0425 (11)
H10	0.8577	0.2694	1.5177	0.051*
C11	0.7392 (5)	0.1826 (5)	1.6620 (4)	0.0429 (11)
H11A	0.8283	0.2030	1.7074	0.052*
H11B	0.6943	0.2797	1.6624	0.052*
C12	0.5960 (4)	0.0628 (5)	1.7552 (4)	0.0405 (10)
H12	0.5370	0.1439	1.7365	0.049*
C13	0.5961 (4)	−0.0752 (4)	1.8158 (4)	0.0373 (9)
H13	0.5365	−0.1041	1.8469	0.045*
C14	0.7585 (4)	−0.0810 (4)	1.7695 (4)	0.0363 (9)
H14	0.8317	−0.1135	1.7614	0.044*
C15	0.4697 (4)	0.4802 (4)	1.3868 (3)	0.0273 (8)
C16	0.5843 (4)	0.5526 (4)	1.3806 (3)	0.0264 (8)
C17	0.5929 (4)	0.5792 (4)	1.2659 (3)	0.0269 (8)
H17	0.5256	0.5546	1.1916	0.032*
C18	0.7039 (4)	0.6434 (4)	1.2634 (4)	0.0274 (8)
C19	0.7169 (4)	0.6621 (4)	1.1412 (4)	0.0300 (9)
C20	0.8022 (4)	0.6847 (5)	1.3746 (4)	0.0282 (8)
H20	0.8751	0.7290	1.3730	0.034*
C21	0.7921 (4)	0.6600 (4)	1.4888 (3)	0.0293 (8)
C22	0.6843 (4)	0.5937 (4)	1.4904 (4)	0.0279 (9)
H22	0.6783	0.5761	1.5667	0.033*
N1	0.7499 (3)	0.3462 (4)	0.9927 (3)	0.0334 (8)
N2	0.6920 (3)	0.1456 (3)	1.0788 (3)	0.0317 (8)
N3	0.7004 (4)	0.0586 (4)	1.7272 (3)	0.0348 (9)
N4	0.6982 (3)	−0.1657 (4)	1.8238 (3)	0.0334 (8)
O1	0.8266 (3)	0.6877 (3)	1.1446 (2)	0.0371 (7)
O2	0.6211 (3)	0.6472 (4)	1.0407 (3)	0.0361 (7)
O3	0.4686 (3)	0.4481 (3)	1.4917 (2)	0.0396 (7)
O4	0.3735 (3)	0.4533 (4)	1.2877 (3)	0.0380 (7)
O5	0.8918 (3)	0.7014 (4)	1.5949 (3)	0.0421 (7)
H5	0.896 (5)	0.670 (6)	1.662 (2)	0.063*
O1W	0.5537 (3)	0.5093 (4)	0.7498 (3)	0.0542 (9)
HW11	0.486 (3)	0.483 (7)	0.756 (4)	0.081*
HW12	0.537 (4)	0.511 (7)	0.6721 (14)	0.081*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.03035 (12)	0.03188 (12)	0.02375 (11)	0.00339 (19)	0.01479 (9)	0.00450 (17)
C1	0.030 (2)	0.038 (2)	0.041 (2)	0.0026 (19)	0.011 (2)	−0.0045 (18)
C2	0.036 (3)	0.034 (3)	0.035 (3)	0.011 (2)	0.007 (2)	−0.0015 (19)
C3	0.038 (2)	0.026 (2)	0.040 (2)	0.0083 (18)	0.017 (2)	0.0066 (16)
C4	0.045 (3)	0.0257 (19)	0.038 (2)	−0.0018 (18)	0.018 (2)	0.0030 (16)
C5	0.039 (2)	0.027 (2)	0.039 (2)	0.0086 (18)	0.016 (2)	0.0055 (17)
C6	0.043 (3)	0.043 (3)	0.037 (3)	−0.006 (3)	0.021 (2)	0.008 (2)
C7	0.044 (3)	0.040 (2)	0.042 (2)	−0.009 (2)	0.018 (2)	−0.0049 (19)
C8	0.054 (3)	0.042 (2)	0.047 (3)	−0.011 (2)	0.029 (3)	0.000 (2)
C9	0.041 (3)	0.030 (2)	0.032 (2)	0.0031 (19)	0.013 (2)	0.0083 (17)
C10	0.047 (3)	0.038 (2)	0.046 (3)	−0.008 (2)	0.022 (2)	0.0024 (18)
C11	0.063 (3)	0.029 (2)	0.037 (2)	−0.004 (2)	0.020 (2)	0.0042 (18)
C12	0.034 (3)	0.041 (2)	0.041 (2)	0.007 (2)	0.010 (2)	0.0008 (18)
C13	0.030 (2)	0.039 (2)	0.044 (2)	0.0001 (18)	0.016 (2)	0.0018 (18)
C14	0.045 (3)	0.033 (2)	0.035 (2)	0.0033 (19)	0.021 (2)	−0.0006 (17)
C15	0.027 (2)	0.031 (2)	0.029 (2)	0.0020 (16)	0.0158 (18)	−0.0016 (15)
C16	0.027 (2)	0.0323 (19)	0.0235 (19)	0.0039 (15)	0.0146 (17)	0.0002 (14)
C17	0.0237 (19)	0.035 (2)	0.0221 (18)	0.0014 (16)	0.0089 (16)	0.0007 (15)
C18	0.035 (2)	0.0288 (19)	0.025 (2)	0.0035 (16)	0.0184 (18)	0.0014 (14)
C19	0.050 (3)	0.0209 (18)	0.029 (2)	0.0050 (18)	0.026 (2)	0.0039 (15)
C20	0.026 (2)	0.032 (2)	0.031 (2)	0.0019 (18)	0.0155 (18)	0.0073 (17)
C21	0.026 (2)	0.033 (2)	0.025 (2)	0.0042 (17)	0.0064 (18)	0.0023 (15)
C22	0.029 (2)	0.034 (2)	0.0222 (19)	0.0005 (18)	0.0125 (17)	0.0026 (16)
N1	0.037 (2)	0.0320 (17)	0.0317 (18)	0.0050 (15)	0.0140 (16)	0.0031 (13)
N2	0.040 (2)	0.0265 (17)	0.0313 (19)	0.0057 (15)	0.0169 (17)	0.0032 (13)
N3	0.048 (3)	0.0309 (18)	0.027 (2)	0.0075 (18)	0.017 (2)	0.0054 (15)
N4	0.039 (2)	0.0335 (17)	0.0289 (18)	0.0012 (15)	0.0146 (16)	0.0032 (13)
O1	0.0397 (17)	0.0464 (17)	0.0346 (16)	−0.0003 (14)	0.0248 (15)	0.0021 (12)
O2	0.045 (2)	0.0384 (16)	0.0290 (17)	0.0068 (16)	0.0191 (16)	0.0056 (13)
O3	0.0350 (17)	0.0622 (19)	0.0284 (15)	−0.0083 (14)	0.0199 (14)	0.0006 (13)
O4	0.0266 (17)	0.0599 (19)	0.0260 (16)	−0.0037 (17)	0.0090 (14)	−0.0046 (15)
O5	0.0351 (17)	0.061 (2)	0.0257 (15)	−0.0080 (15)	0.0070 (14)	0.0037 (14)
O1W	0.047 (2)	0.075 (2)	0.0317 (16)	−0.0192 (18)	0.0054 (15)	0.0046 (16)

Geometric parameters (Å, º)

Cd1—N4^i	2.244 (3)	C11—H11B	0.9700
Cd1—N1	2.282 (3)	C12—C13	1.359 (5)
Cd1—O3^ii	2.384 (3)	C12—N3	1.370 (6)
Cd1—O2	2.423 (3)	C12—H12	0.9300
Cd1—O1W	2.465 (3)	C13—N4	1.378 (5)
Cd1—O1	2.499 (3)	C13—H13	0.9300
Cd1—O4^ii	2.554 (3)	C14—N4	1.322 (5)
C1—C2	1.357 (6)	C14—N3	1.347 (5)
C1—N1	1.375 (5)	C14—H14	0.9300
C1—H1	0.9300	C15—O3	1.256 (4)
C2—N2	1.371 (6)	C15—O4	1.267 (5)
C2—H2	0.9300	C15—C16	1.488 (5)
C3—N1	1.331 (5)	C16—C22	1.386 (5)
C3—N2	1.337 (4)	C16—C17	1.396 (5)
C3—H3	0.9300	C17—C18	1.405 (5)
C4—N2	1.457 (5)	C17—H17	0.9300
C4—C5	1.507 (6)	C18—C20	1.387 (6)
C4—H4A	0.9700	C18—C19	1.496 (5)
C4—H4B	0.9700	C19—O2	1.260 (5)
C5—C7	1.383 (6)	C19—O1	1.274 (5)
C5—C6	1.385 (7)	C20—C21	1.395 (5)
C6—C10	1.377 (7)	C20—H20	0.9300
C6—H6	0.9300	C21—O5	1.359 (5)
C7—C8	1.386 (6)	C21—C22	1.375 (5)
C7—H7	0.9300	C22—H22	0.9300
C8—C9	1.386 (7)	N4—Cd1^iii	2.244 (3)
C8—H8	0.9300	O3—Cd1^iv	2.384 (3)
C9—C10	1.390 (6)	O4—Cd1^iv	2.554 (3)
C9—C11	1.512 (6)	O5—H5	0.814 (10)
C10—H10	0.9300	O1W—HW11	0.846 (10)
C11—N3	1.463 (5)	O1W—HW12	0.847 (10)
C11—H11A	0.9700
N4^i—Cd1—N1	166.24 (13)	N3—C11—H11B	108.9
N4^i—Cd1—O3^ii	110.30 (11)	C9—C11—H11B	108.9
N1—Cd1—O3^ii	82.34 (11)	H11A—C11—H11B	107.7
N4^i—Cd1—O2	92.80 (11)	C13—C12—N3	106.4 (4)
N1—Cd1—O2	82.46 (11)	C13—C12—H12	126.8
O3^ii—Cd1—O2	130.03 (10)	N3—C12—H12	126.8
N4^i—Cd1—O1W	83.67 (12)	C12—C13—N4	109.4 (4)
N1—Cd1—O1W	83.19 (12)	C12—C13—H13	125.3
O3^ii—Cd1—O1W	137.45 (11)	N4—C13—H13	125.3
O2—Cd1—O1W	87.01 (12)	N4—C14—N3	111.3 (4)
N4^i—Cd1—O1	100.22 (10)	N4—C14—H14	124.4
N1—Cd1—O1	87.43 (11)	N3—C14—H14	124.4
O3^ii—Cd1—O1	78.21 (9)	O3—C15—O4	120.2 (4)
O2—Cd1—O1	53.80 (10)	O3—C15—C16	119.2 (4)
O1W—Cd1—O1	140.62 (11)	O4—C15—C16	120.6 (3)
N4^i—Cd1—O4^ii	86.42 (11)	C22—C16—C17	119.4 (3)
N1—Cd1—O4^ii	97.77 (11)	C22—C16—C15	119.5 (3)
O3^ii—Cd1—O4^ii	52.44 (9)	C17—C16—C15	121.0 (3)
O2—Cd1—O4^ii	177.49 (12)	C16—C17—C18	119.7 (4)
O1W—Cd1—O4^ii	90.53 (11)	C16—C17—H17	120.2
O1—Cd1—O4^ii	128.69 (9)	C18—C17—H17	120.2
C2—C1—N1	110.0 (4)	C20—C18—C17	119.7 (3)
C2—C1—H1	125.0	C20—C18—C19	120.4 (4)
N1—C1—H1	125.0	C17—C18—C19	119.9 (4)
C1—C2—N2	105.8 (4)	O2—C19—O1	123.1 (3)
C1—C2—H2	127.1	O2—C19—C18	119.3 (4)
N2—C2—H2	127.1	O1—C19—C18	117.7 (4)
N1—C3—N2	111.2 (3)	C18—C20—C21	120.3 (4)
N1—C3—H3	124.4	C18—C20—H20	119.8
N2—C3—H3	124.4	C21—C20—H20	119.8
N2—C4—C5	114.1 (3)	O5—C21—C22	122.7 (3)
N2—C4—H4A	108.7	O5—C21—C20	117.8 (4)
C5—C4—H4A	108.7	C22—C21—C20	119.5 (4)
N2—C4—H4B	108.7	C21—C22—C16	121.3 (3)
C5—C4—H4B	108.7	C21—C22—H22	119.3
H4A—C4—H4B	107.6	C16—C22—H22	119.3
C7—C5—C6	117.3 (4)	C3—N1—C1	105.2 (3)
C7—C5—C4	117.7 (4)	C3—N1—Cd1	122.9 (3)
C6—C5—C4	125.0 (4)	C1—N1—Cd1	131.7 (3)
C10—C6—C5	121.9 (5)	C3—N2—C2	107.8 (3)
C10—C6—H6	119.1	C3—N2—C4	125.3 (3)
C5—C6—H6	119.1	C2—N2—C4	126.8 (3)
C5—C7—C8	121.7 (4)	C14—N3—C12	107.2 (3)
C5—C7—H7	119.2	C14—N3—C11	126.9 (4)
C8—C7—H7	119.2	C12—N3—C11	125.9 (4)
C7—C8—C9	120.3 (4)	C14—N4—C13	105.7 (3)
C7—C8—H8	119.9	C14—N4—Cd1^iii	129.8 (3)
C9—C8—H8	119.9	C13—N4—Cd1^iii	124.4 (3)
C8—C9—C10	118.4 (4)	C19—O1—Cd1	88.3 (2)
C8—C9—C11	121.5 (4)	C19—O2—Cd1	92.1 (2)
C10—C9—C11	120.0 (5)	C15—O3—Cd1^iv	97.2 (2)
C6—C10—C9	120.4 (5)	C15—O4—Cd1^iv	89.0 (2)
C6—C10—H10	119.8	C21—O5—H5	120 (4)
C9—C10—H10	119.8	Cd1—O1W—HW11	126 (3)
N3—C11—C9	113.4 (4)	Cd1—O1W—HW12	128 (3)
N3—C11—H11A	108.9	HW11—O1W—HW12	106 (4)
C9—C11—H11A	108.9

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O4^v	0.81 (1)	1.89 (2)	2.675 (4)	162 (5)
O1W—HW12···O3^vi	0.85 (1)	2.00 (2)	2.813 (4)	161 (5)
O1W—HW11···O1^vii	0.85 (1)	2.29 (4)	2.935 (4)	133 (4)

Symmetry codes: (v) x+1/2, −y+1, z+1/2; (vi) x, y, z−1; (vii) x−1/2, −y+1, z−1/2.