Synthesis, structure and characterization of two new metal–organic coordination polymers based on the ligand 5-iodobenzene-1,3-dicarboxyl­ate

Two new coordination polymers (CPs) formed from 5-iodobenzene-1,3-dicarb­oxy­lic acid (H₂iip) in the presence of the flexible 1,4-bis­(1H-imidazol-1-yl)butane (bimb) auxiliary ligand, namely poly[[μ₂-1,4-bis­(1H-imidazol-1-yl)butane-κ²N³:N^3′](μ₃-5-iodobenzene-1,3-dicarboxyl­ato-κ⁴O¹,O^1′:O³:O^3′)cobalt(II)], [Co(C₈H₃IO₄)(C₁₀H₁₄N₄)]_n or [Co(iip)(bimb)]_n, (1), and poly[[[μ₂-1,4-bis­(1H-imidazol-1-yl)butane-κ²N³:N^3′](μ₂-5-iodo­benzene-1,3-dicarboxyl­ato-κ²O¹:O³)zinc(II)] trihydrate], {[Zn(C₈H₃IO₄)(C₁₀H₁₄N₄)]·3H₂O}_n or {[Zn(iip)(bimb)]·3H₂O}_n, (2), were synthesized and characterized by FT–IR spectroscopy, thermogravimetric analysis (TGA), solid-state UV–Vis spectroscopy, single-crystal X-ray diffraction analysis and powder X-ray diffraction analysis (PXRD). The iip²⁻ ligand in (1) adopts the (κ¹,κ¹-μ₂)(κ¹, κ¹-μ₁)-μ₃ coordination mode, linking adjacent secondary building units into a ladder-like chain. These chains are further connected by the flexible bimb ligand in a trans–trans–trans conformation. As a result, a twofold three-dimensional inter­penetrating α-Po network is formed. Complex (2) exhibits a two-dimensional (4,4) topological network architecture in which the iip²⁻ ligand shows the (κ¹)(κ¹)-μ₂ coordination mode. The solid-state UV–Vis spectra of (1) and (2) were investigated, together with the fluorescence properties of (2) in the solid state.

S1. Introduction

In recent years, the rational design and synthesis of coordination polymers (CPs) or metal–organic frameworks (MOFs) have been an inter­esting research field in coordination chemistry, supra­molecular chemistry and materials science, due to their intriguing topological structures and potential applications in gas adsorption, purification, separation, magnetism, luminescence and heterogeneous catalysis (DeCoste & Peterson, 2014; Zhao & Sun, 2014). Nevertheless, it is still a great challenge to construct expected architectures with unique properties. In the past two decades, much effort has been made for the controlled synthesis of MOFs through the deliberate selection of functionalized organic ligands and/or coordination geometries of metal ions. Polycarboxyl­ate ligands are among one of the most important families of organic building blocks and can act as reliable candidates for the assembly of various coordination species with inter­esting topologies and functional properties (Heinze & Reinhart, 2006; Jammi et al., 2008). It should be noted that rigid substituted isophthalic acids, such as 5-R-isophthalic acids (5-R-H₂ip, R is the substituted group), have already been used extensively in the preparation of various novel MOFs with inter­esting architectures and properties (Zhang et al., 2014). The results show that the 5-R-ip^2- ligand in related coordination compounds has flexible conformations, various binding modes and a strong ability to form supra­molecular inter­actions, such as hydrogen bonds and π–π stacking inter­actions (Chang et al., 2012). Furthermore, it has been demonstrated by chemists that coordination-inert substituted groups can influence the structural diversity of the final coordination frameworks (Sotnik et al., 2015; Torres Salgado et al., 2015).

Based upon the above considerations, in the past few years, we have selected 5-iodo­benzene-1,3-di­carb­oxy­lic acid as the main ligand and introduced additional N-donor auxiliary bridging ligands, such as 1,4-bis­(triazol-1-yl­methyl)­benzene (bbtz), 1,4-bis­(1,2,4-triazol-1-yl)ethane (bte) and 1,3-bis­(pyridin-4-yl)propane (bpp), into the assembly system to generate novel Cd^II–MOFs with aesthetically pleasing? [Text incomplete] architectures and inter­esting functional properties (Deng et al., 2013). As a systematic continuation of our previous work, we report herein the syntheses and characterization of two novel Co^II/Zn^II–MOFs with H₂iip in the presence of the flexible 1,4-bis­(1H-imidazol-1-yl)butane (bimb) auxiliary ligand, namely [Co(iip)(bimb)]_n, (1), and {[Zn(iip)(bimb)].3H₂O}_n, (2) (see scheme). Complex (1) shows a twofold three-dimensional inter­penetrating α-polonium framework architecture, while (2) has a two-dimensional (4,4) topological network. The solid-state UV–Vis spectra of (1) and (2) have been recorded, their thermal stabilities have been investigated and the solid-state fluorescence properties of (2) have been studied.

S2. Experimental

H₂iip and bimb were synthesized according to the literature methods (Ma et al., 2003; Zhang et al., 2012). The other reagents were purchased commercially and used without further purification. FT–IR spectra (400–4000 cm^-1) were recorded from KBr pellets in a Magna750 FT–IR spectrophotometer. Powder X-ray diffraction (PXRD) data were collected on a computer-controlled Bruker D8 Advance XRD diffractometer, operating with Cu Kα_1/2 radiation (λ = 1.5418 Å) at a scanning rate of 0.04° s^-1 from 5 to 50° using a Våntec solid-state detector. The solid-state UV–Vis diffuse refle­cta­nce spectra were measured on a Varian Cary 5000. Thermogravimetric analyses (TGA) were carried out on a NETZSCH STA 409 PG/PC instrument under a heating rate of 10 K min^-1 under an N₂ atmosphere (10 ml min^-1). Graphs of relative intensity versus angle (2θ) were plotted from the raw data using Origin 6.1 (www.originlab.com; Clement, 2000).

S2.1. Synthesis and crystallization

S2.1.1. Synthesis of [Co(iip)(bimb)]\~n\~, (1)

A mixture containing CoCl₂.6H₂O (47.6 mg, 0.2 mmol), 5-H₂iip (29.2 mg, 0.1 mmol), bimb (19.0 mg, 0.1 mmol), NaOH (4 mg, 0.1 mmol) and water (6 ml) was sealed in a Teflon reactor, which was heated at 423 K for 3 d and then cooled to room temperature at a rate of 10 K h^-1 over a period of 24 h. Purple block-shaped crystals of (1) were collected in 83% yield (based on 5-H₂iip). Selected IR data (KBr pellet, ν, cm^-1): 3129 (m), 2918 (m), 1630 (vs), 1553 (s), 1505 (s), 1437 (s), 1393 (vs), 1297 (w), 1235 (m), 1094 (s), 1033 (s), 927 (m), 831 (s), 769 (s), 716 (m).

S2.1.2. Synthesis of {[Zn(iip)(bimb)].3H\~2\Õ}\~n\~, (2)

A mixture of ZnCl₂ (27.3 mg, 0.2 mmol), 5-H₂iip (29.2 mg, 0.1 mmol), bimb (19.0 mg, 0.1 mmol) and EtOH/H₂O (8 ml, 1:1 v/v) was placed in a Teflon-lined stainless steel vessel, heated to 423 K for 3 d and then cooled to room temperature at a rate of 10 K h^-1. Colourless block-shaped crystals of (2) were collected in 84% yield (based on 5-H₂iip). Selected IR data (KBr pellet, ν, cm^-1): 3423 (s), 3130 (m), 2945 (m), 1616 (vs), 1554 (s), 1423 (s), 1341 (vs), 1280 (w), 1239 (m), 1094 (s), 1032 (s), 954 (m), 838 (s), 774 (s), 717 (m).

The phase purities of complexes (1) and (2) were verified by PXRD patterns, which are consistent with the corresponding XRD patterns simulated from the single-crystal X-ray diffraction anayses (see Figs. S1 and S2 in the Supporting information).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. C-bound H atoms were positioned geometrically and constrained using the riding-model approximation, with aryl C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). The amino H atoms were also added geometrically, with N—H = 0.86 Å and U_iso(H) = 1.5U_eq(N). The water H atoms of (2) were firstly added through a Fourier map [located in a difference Fourier map?] and then fixed, with O—H = 0.85 Å, H···H = 1.39 Å and U_iso(H) = 1.5U_eq(O).

S3. Results and discussion

S3.1. Structural description of [Co(iip)(bimb)]\~n\~, (1)

Single-crystal X-ray structure analysis shows that the asymmetric unit of (1) consists of one Co^II cation, one iip^2- ligand and one bimb ligand. As shown in Fig. 1, each six-coordinated Co^II cation is bound by two N atoms from two bimb ligands and by four O atoms from three iip^2- ligands, and exhibits a distorted o­cta­hedral coordination geometry with the subtended angles ranging from 60.03 (11) to 171.69 (14)° (Table 2). The O3/C8/O4 carboxyl­ate group in the iip^2- ligand exhibits a bis-monodentate bridging conformation in a syn–anti fashion, resulting in the formation of a centrosymmetric carboxyl­ate-bridged dinuclear secondary building unit (SBU), [Co₂(COO)₂]. The Co1···Co1ⁱ [symmetry code: (i) -x + 1, -y + 2, -z + 2] separation in the SBU is 4.659 (5) Å. The other carboxyl­ate group (O1/C7/O2) of the iip^2- ligand exhibits the chelating coordination mode. Thus, the iip^2- ligand adopts the (κ¹,κ¹-µ₂)(κ¹, κ¹-µ₁)-µ₃ coordination mode, linking adjacent SBUs into a ladder-like double-chain along the [100] direction (Fig. 2). These double chains are further connected by the bimb ligands in three directions with a trans–trans–trans (TTT) conformation (Li et al., 2015), leading to the formation of the three-dimensional architecture (Fig. 3).

If the dimeric [Co₂(COO)₂] SBUs are treated as nodes and both the 5-iip^2- and bimb ligands as linkers, the three-dimensional network of (1) can be viewed as a twofold three-dimensional inter­penetrating α-Po network, in which the networks are further connected to each other through C—I···O [3.076 (3) Å] halogen bonds (Figs. 4 and 5). Compound (1) is isostructural with the 5-Br-ip/Ni^II compound (Ma et al., 2011).

It should be noted that compound (1) is also a new member of the Co/5-iip^2-/bimb family (Zang et al., 2012).

S3.2. Structural description of {[Zn(iip)(bimb)].3H\~2\Õ}\~n\~, (2)

Single-crystal X-ray structure analysis shows that the asymmetric unit of (2) consists of one Zn^II cation, one iip^2- anion, one bimb ligand and three solvent water molecules. As shown in Fig. 6, each Zn^II cation is tetra­coordinated by two N atoms from two bridging bimb ligands and two O atoms from two iip^2- ligands. The Zn—O bond lengths vary from 1.932 (5) to 1.968 (5) Å and the Zn—N bond lengths are in the range 1.988 (6)—2.009 (7) Å (Table 3), comparable with the values reported in the literature (Hua et al., 2015). The bond angles around each Zn^II cation vary from 100.6 (2) to 119.0 (3)°. Therefore, the Zn^II cation shows a slightly distorted tetra­hedral coordination geometry. The auxiliary flexible bimb ligand also adopts a trans–trans–trans (TTT) coordination mode (Li et al., 2015) and links adjacent Zn^II cations into a one-dimensional left-handed helix around the crystallographic 2₁ axis, with a pitch of 13.565 (17) Å along the [010] direction (Fig. 7). The left-handed helices are parallel to one another. Neighbouring bimb-bridged helical chains are further bridged by the iip^2- linkages in a bis-monodentate (κ¹)-(κ¹)-µ₂ coordination mode, leading to the formation of a novel two-dimensional (4,4) topological network (Fig. 8). The structure of compound (2) is similar to a Co^II complex based on the same ligand (Zang et al., 2012) and also to a 5-Me-ip/Co^II/bimb compound (Chang et al., 2013). Compound (2) is also a relative of previous work on similar alkyl bis-imidazole ligands with iip^2- (Sengupta et al., 2013).

Hydrogen bonds exist extensively in the crystal structure of (2). Hydrogen bonds formed through the solvent water molecules O1W and O2W and uncoordinated carboxyl­ate O atoms (O2, O3 and O4) result in a two-dimensional layered structure with two kinds of one-dimensional channel arranged alternately along the [100] direction [O2W—H2WB···O1W, O2W—H2WA···O4ⁱⁱ, O1W—H1WA···O2^v and O1W—H1WB···O3^vi; see Table 4 for hydrogen-bond details and symmetry codes] (see also Fig. S3 in the Supporting information). The O3W solvent water molecule lies in the channel. Hydrogen bonds also exist between the O3W solvent water molecules (O3W—H3WA···O3W^vii; Table 4).

It should be noted that the structure of (2) is quite different from that of (1), although the same N/O-donor ligands were used in both compunds, which further indicates that the central Co^II and Zn^II cations have a great influence on crystalline architecture.

S3.3. Thermal stability

To investigate the thermal stabilities of the compounds, thermogravimetric analyses (TGA) of (1) and (2) were carried out under a nitro­gen atmosphere (Fig. 9). In the case of (1), no obvious weight loss was observed below 617 K, further indicating that the structure contains no water molecules and that the framework has high thermal stability. It should be noted that the framework decomposition temperature of (1) is higher than that of the previously reported Co^II complex {[Co(CH₃-ip)(1,4-bib)]·2H₂O}_n based on the CH₃O-ip anion (Chang et al., 2013). For (2), a weight loss of 8.62% in the temperature range 323–428 K is in agreement with the release of three solvent water molecules (calculated 9.01%). The second step of weight loss from 589 K corresponds to the combustion of the organic groups.

S3.4. UV–Vis spectra

The solid–state UV/vis spectra of H₂iip, (1) and (2) are displayed in Fig. S4 in the Supporting information. H₂iip itself displays two main strong absorption bands in the UV spectroscopic region, at 262 and 312 nm, arising from the π–π* transition of the aromatic ligands.These bands are not strongly perturbed upon the coordination of this ligand to the central Co^II or Zn^II cations, suggesting that coordination of central metal ions hardly alters the intrinsic electronic properties of H₂iip. For (1), two peaks at 546 [⁴T_1g(F)→⁴T_2g(F)] and 1260 nm [⁴T_1g(F)→⁴T_1g(P)] probably originate from the d–d spin-allowed transition of the d⁷ (Co²⁺) cation, which is typical for o­cta­hedrally coordinated Co^II coordination compounds (Guo et al., 2011; Qin et al., 2012). For (2), the two slightly blue-shifted peaks located at 242 and 301 nm compared with those of H₂iip may reult from the coordination effect of the iip^2- ligand to the Zn^II cation.

S3.5. Fluorescence properties

To compare the relative fluorescence intensities of (2), bimb and H₂iip, we measured the emission spectra with the same excitation wavelength (Fig. 10). The free acid H₂iip and ligand bimb exhibit similar fluorescence emissions, with two main peaks located at 417 and 470 nm, respectively, upon excitation at λ_ex = 260 nm. Excitation of the microcrystalline sample of (2), also at 260 nm, leads to the generation of similar fluorescence emissions, with the maximum emission also located at 417 and 470 nm, indicating that the auxiliary bimb ligand has almost no influence on the emission mechanism. Thus, the fluorescence emission of (2) may be assigned to an intra­ligand π–π* transition of the bimb and iip^2- ligands (Ge et al., 2015).

S3.6. Conclusion

In summary, two Co^II/Zn^II MOFs based on the multifunctional ligand H₂iip in the presence of the auxiliary flexible bridging ligand bimb were prepared and characterized. Complex (1) is a twofold three-dimensional inter­penetrating α-polonium network, while complex (2) exhibits a two-dimensional (4,4) topological network architecture. Complex (2) exhibits a similar fluorescence emission to that of the free acid H₂iip, with the maximum emission located at almost the same position as that of H₂iip, indicating that the auxiliary flexible bimb ligand has almost no influence on the emission mechanism of (2). Further work is underway in our laboratory to prepare novel supra­molecular coordination polymers based on the multifunctional ligand H₂iip with inter­esting structures and functional properties.

Computing details

For both compounds, 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: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. A view of the coordination environment of the Co^II cation in (1). [Symmetry codes: (i) -x + 1, -y + 2, -z + 2; (ii) x, -y + 3/2, z + 1/2; (iii) x - 1, y, z.]
	Fig. 2. A view of the one-dimensional carboxylate-bridged double chain in (1), along the [100] direction.
	Fig. 3. The three-dimensional structure of (1).
	Fig. 4. A view of the twofold interpenetrating networks of (1), connected to each other through C—I···O halogen bonds (black dashed lines).
	Fig. 5. A schematic drawing of the twofold interpenetrating three-dimensional network of (1).
	Fig. 6. A view of the coordination environment of the Zn^II cation in (2). [Symmetry codes: (i) -x + 1, y - 1/2, -z + 1/2; (ii) x, -y + 3/2, z + 1/2; (iii) -x + 1, y + 1/2, -z + 1/2.]
	Fig. 7. The one-dimensional left-handed helix of (2), around the crystallographic 21 axis.
	Fig. 8. The two-dimensional (4,4) topological network of (2), showing the coordination modes of the iip^2- and bimb ligands.
	Fig. 9. The TG curves of (1) (black) and (2) (red).
	Fig. 10. The fluorescence intensities for H2iip (black), bimb (red) and (2) (green).

(1) Poly[[µ₂-1,4-bis(1H-imidazol-1-yl)butane-κ²N³:N^3'](µ₃-5-iodobenzene-1,3-dicarboxylato-κ⁴O¹,O^1':O³:O^3')cobalt(II)

Crystal data

[Co(C8H3IO4)(C10H14N4)]	F(000) = 2120
Mr = 539.19	Dx = 1.841 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ac2ab	Cell parameters from 3330 reflections
a = 10.2561 (18) Å	θ = 2.5–24.7°
b = 17.088 (3) Å	µ = 2.50 mm^−1
c = 22.205 (4) Å	T = 296 K
V = 3891.6 (12) Å^3	Block, purple
Z = 8	0.32 × 0.25 × 0.19 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	4459 independent reflections
Radiation source: fine-focus sealed tube	2854 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.071
φ and ω scans	θmax = 27.6°, θmin = 2.4°
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2003)	h = −13→13
Tmin = 0.477, Tmax = 0.622	k = −22→22
32053 measured reflections	l = −28→28

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.090	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0344P)^2 + 0.5923P] where P = (Fo^2 + 2Fc^2)/3
4459 reflections	(Δ/σ)max = 0.004
253 parameters	Δρmax = 0.60 e Å^−3
0 restraints	Δρmin = −1.08 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	0.8506 (3)	0.9166 (2)	1.18175 (15)	0.0307 (8)
C2	0.9742 (3)	0.9168 (2)	1.15662 (15)	0.0317 (9)
H2	1.0477	0.9141	1.1811	0.038*
C3	0.9871 (3)	0.92106 (19)	1.09422 (14)	0.0245 (8)
C4	0.8763 (3)	0.92868 (18)	1.05877 (15)	0.0235 (7)
H4	0.8849	0.9329	1.0172	0.028*
C5	0.7524 (3)	0.93013 (19)	1.08456 (15)	0.0249 (8)
C6	0.7400 (3)	0.9227 (2)	1.14659 (15)	0.0308 (8)
H6	0.6578	0.9218	1.1643	0.037*
C7	1.1214 (3)	0.9201 (2)	1.06742 (15)	0.0259 (8)
C8	0.6334 (3)	0.9411 (2)	1.04572 (16)	0.0249 (8)
C9	0.4666 (4)	0.8926 (2)	0.89721 (16)	0.0333 (9)
H9	0.5134	0.9390	0.9000	0.040*
C10	0.3419 (4)	0.7963 (2)	0.91757 (18)	0.0499 (11)
H10	0.2842	0.7635	0.9377	0.060*
C11	0.3895 (5)	0.7834 (3)	0.86167 (18)	0.0502 (11)
H11	0.3723	0.7407	0.8370	0.060*
C12	0.5522 (4)	0.8536 (3)	0.79539 (16)	0.0519 (12)
H12A	0.6071	0.8076	0.7922	0.062*
H12B	0.6087	0.8986	0.8008	0.062*
C13	0.4762 (4)	0.8635 (3)	0.73711 (16)	0.0462 (11)
H13A	0.4290	0.9126	0.7378	0.055*
H13B	0.4135	0.8213	0.7329	0.055*
C14	0.5704 (4)	0.8625 (3)	0.68407 (16)	0.0493 (11)
H14A	0.6094	0.8108	0.6814	0.059*
H14B	0.6400	0.8995	0.6920	0.059*
C15	0.5090 (5)	0.8824 (2)	0.62333 (17)	0.0507 (12)
H15A	0.4634	0.9319	0.6268	0.061*
H15B	0.5778	0.8889	0.5938	0.061*
C16	0.4461 (4)	0.7479 (2)	0.58625 (17)	0.0393 (10)
H16	0.5279	0.7251	0.5908	0.047*
C17	0.2897 (4)	0.8337 (2)	0.58752 (18)	0.0482 (11)
H17	0.2422	0.8795	0.5927	0.058*
C18	0.2445 (4)	0.7658 (2)	0.56463 (18)	0.0459 (11)
H18	0.1598	0.7571	0.5514	0.055*
Co1	0.34832 (4)	0.90504 (3)	1.02738 (2)	0.02510 (12)
I1	0.83171 (3)	0.90762 (2)	1.276244 (11)	0.06035 (13)
N1	0.3914 (3)	0.86494 (18)	0.94014 (13)	0.0332 (7)
N2	0.4677 (3)	0.84554 (18)	0.84876 (13)	0.0360 (8)
N3	0.4175 (3)	0.82279 (18)	0.60173 (13)	0.0379 (8)
N4	0.3438 (3)	0.71137 (18)	0.56400 (13)	0.0354 (8)
O4	1.2160 (2)	0.94280 (15)	1.09887 (10)	0.0338 (6)
O3	1.1367 (2)	0.89564 (14)	1.01441 (10)	0.0329 (6)
O1	0.5281 (2)	0.91426 (13)	1.06739 (10)	0.0312 (6)
O2	0.6458 (2)	0.97368 (14)	0.99589 (10)	0.0304 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0241 (19)	0.052 (2)	0.0159 (16)	−0.0005 (18)	0.0030 (14)	0.0002 (16)
C2	0.0191 (18)	0.053 (2)	0.0233 (18)	0.0010 (17)	−0.0012 (15)	0.0023 (17)
C3	0.0184 (17)	0.033 (2)	0.0216 (16)	0.0011 (15)	−0.0002 (14)	0.0004 (15)
C4	0.0204 (18)	0.0314 (19)	0.0187 (17)	−0.0023 (15)	0.0031 (14)	0.0009 (15)
C5	0.0174 (17)	0.0302 (19)	0.0269 (18)	−0.0006 (15)	−0.0030 (15)	0.0021 (15)
C6	0.0180 (18)	0.048 (2)	0.0266 (18)	0.0000 (16)	0.0031 (15)	0.0012 (17)
C7	0.0156 (17)	0.038 (2)	0.0243 (19)	0.0047 (15)	0.0011 (14)	0.0063 (15)
C8	0.0161 (18)	0.0261 (18)	0.032 (2)	0.0015 (15)	−0.0018 (15)	−0.0009 (16)
C9	0.032 (2)	0.039 (2)	0.0295 (19)	−0.0010 (18)	0.0017 (17)	−0.0040 (17)
C10	0.057 (3)	0.054 (3)	0.039 (2)	−0.012 (2)	0.004 (2)	−0.002 (2)
C11	0.064 (3)	0.050 (3)	0.037 (2)	−0.006 (2)	−0.001 (2)	−0.013 (2)
C12	0.047 (3)	0.084 (3)	0.025 (2)	0.006 (2)	0.009 (2)	−0.012 (2)
C13	0.045 (3)	0.062 (3)	0.032 (2)	−0.002 (2)	0.0015 (19)	−0.007 (2)
C14	0.054 (3)	0.063 (3)	0.031 (2)	−0.016 (2)	0.011 (2)	−0.016 (2)
C15	0.075 (3)	0.045 (2)	0.033 (2)	−0.020 (2)	0.003 (2)	−0.0069 (19)
C16	0.039 (2)	0.042 (2)	0.037 (2)	0.0048 (19)	−0.0002 (19)	−0.0063 (18)
C17	0.054 (3)	0.048 (3)	0.043 (3)	0.018 (2)	0.010 (2)	−0.007 (2)
C18	0.034 (2)	0.056 (3)	0.048 (3)	0.013 (2)	0.001 (2)	−0.009 (2)
Co1	0.0139 (2)	0.0410 (3)	0.0204 (2)	−0.0009 (2)	0.00073 (18)	0.0010 (2)
I1	0.03528 (18)	0.1246 (3)	0.02114 (15)	−0.00909 (18)	0.00426 (12)	0.00411 (15)
N1	0.0294 (18)	0.0424 (19)	0.0278 (17)	−0.0016 (15)	0.0034 (14)	−0.0037 (15)
N2	0.0372 (19)	0.047 (2)	0.0239 (16)	0.0001 (16)	0.0016 (14)	−0.0050 (15)
N3	0.052 (2)	0.0358 (19)	0.0255 (16)	0.0006 (17)	0.0038 (16)	−0.0005 (14)
N4	0.0287 (18)	0.0438 (19)	0.0337 (17)	0.0058 (16)	0.0004 (14)	−0.0063 (15)
O4	0.0136 (12)	0.0626 (17)	0.0253 (13)	−0.0062 (12)	−0.0016 (10)	−0.0007 (12)
O3	0.0190 (12)	0.0575 (17)	0.0221 (13)	0.0037 (12)	0.0013 (10)	−0.0016 (11)
O1	0.0149 (12)	0.0446 (15)	0.0342 (13)	−0.0039 (12)	−0.0001 (10)	0.0078 (12)
O2	0.0236 (13)	0.0411 (15)	0.0264 (13)	0.0021 (11)	−0.0010 (10)	0.0056 (11)

Geometric parameters (Å, º)

C1—C6	1.381 (5)	C13—C14	1.523 (5)
C1—C2	1.385 (5)	C13—H13A	0.9700
C1—I1	2.113 (3)	C13—H13B	0.9700
C2—C3	1.394 (5)	C14—C15	1.527 (5)
C2—H2	0.9300	C14—H14A	0.9700
C3—C4	1.388 (5)	C14—H14B	0.9700
C3—C7	1.501 (5)	C15—N3	1.466 (5)
C4—C5	1.394 (5)	C15—H15A	0.9700
C4—H4	0.9300	C15—H15B	0.9700
C5—C6	1.389 (5)	C16—N4	1.316 (5)
C5—C8	1.506 (4)	C16—N3	1.358 (4)
C6—H6	0.9300	C16—H16	0.9300
C7—O4	1.257 (4)	C17—C18	1.348 (6)
C7—O3	1.259 (4)	C17—N3	1.362 (5)
C8—O2	1.245 (4)	C17—H17	0.9300
C8—O1	1.268 (4)	C18—N4	1.379 (4)
C9—N1	1.314 (4)	C18—H18	0.9300
C9—N2	1.343 (4)	Co1—O1	2.053 (2)
C9—H9	0.9300	Co1—N1	2.102 (3)
C10—C11	1.352 (5)	Co1—O2^i	2.137 (2)
C10—N1	1.373 (5)	Co1—N4^ii	2.150 (3)
C10—H10	0.9300	Co1—O4^iii	2.186 (2)
C11—N2	1.361 (5)	Co1—O3^iii	2.195 (2)
C11—H11	0.9300	N4—Co1^iv	2.150 (3)
C12—N2	1.474 (5)	O4—Co1^v	2.186 (2)
C12—C13	1.520 (5)	O3—Co1^v	2.195 (2)
C12—H12A	0.9700	O2—Co1^i	2.137 (2)
C12—H12B	0.9700
C6—C1—C2	121.6 (3)	C15—C14—H14B	108.6
C6—C1—I1	119.4 (2)	H14A—C14—H14B	107.6
C2—C1—I1	119.0 (2)	N3—C15—C14	113.4 (3)
C1—C2—C3	119.2 (3)	N3—C15—H15A	108.9
C1—C2—H2	120.4	C14—C15—H15A	108.9
C3—C2—H2	120.4	N3—C15—H15B	108.9
C4—C3—C2	119.4 (3)	C14—C15—H15B	108.9
C4—C3—C7	121.8 (3)	H15A—C15—H15B	107.7
C2—C3—C7	118.7 (3)	N4—C16—N3	111.7 (4)
C3—C4—C5	121.0 (3)	N4—C16—H16	124.2
C3—C4—H4	119.5	N3—C16—H16	124.2
C5—C4—H4	119.5	C18—C17—N3	107.5 (4)
C6—C5—C4	119.3 (3)	C18—C17—H17	126.2
C6—C5—C8	120.3 (3)	N3—C17—H17	126.2
C4—C5—C8	120.4 (3)	C17—C18—N4	109.3 (4)
C1—C6—C5	119.5 (3)	C17—C18—H18	125.4
C1—C6—H6	120.3	N4—C18—H18	125.4
C5—C6—H6	120.3	O1—Co1—N1	103.59 (11)
O4—C7—O3	121.7 (3)	O1—Co1—O2^i	90.27 (9)
O4—C7—C3	119.0 (3)	N1—Co1—O2^i	95.01 (11)
O3—C7—C3	119.3 (3)	O1—Co1—N4^ii	85.79 (10)
O2—C8—O1	125.9 (3)	N1—Co1—N4^ii	92.95 (12)
O2—C8—C5	118.8 (3)	O2^i—Co1—N4^ii	171.75 (10)
O1—C8—C5	115.3 (3)	O1—Co1—O4^iii	102.74 (9)
N1—C9—N2	111.8 (3)	N1—Co1—O4^iii	153.67 (11)
N1—C9—H9	124.1	O2^i—Co1—O4^iii	84.66 (9)
N2—C9—H9	124.1	N4^ii—Co1—O4^iii	89.15 (11)
C11—C10—N1	109.9 (4)	O1—Co1—O3^iii	161.88 (9)
C11—C10—H10	125.1	N1—Co1—O3^iii	93.62 (10)
N1—C10—H10	125.1	O2^i—Co1—O3^iii	93.86 (9)
C10—C11—N2	106.3 (4)	N4^ii—Co1—O3^iii	87.75 (10)
C10—C11—H11	126.9	O4^iii—Co1—O3^iii	60.21 (9)
N2—C11—H11	126.9	C9—N1—C10	105.0 (3)
N2—C12—C13	113.2 (3)	C9—N1—Co1	132.5 (3)
N2—C12—H12A	108.9	C10—N1—Co1	122.5 (3)
C13—C12—H12A	108.9	C9—N2—C11	107.0 (3)
N2—C12—H12B	108.9	C9—N2—C12	126.4 (3)
C13—C12—H12B	108.9	C11—N2—C12	126.1 (3)
H12A—C12—H12B	107.8	C16—N3—C17	106.1 (3)
C12—C13—C14	109.4 (4)	C16—N3—C15	126.9 (4)
C12—C13—H13A	109.8	C17—N3—C15	126.7 (4)
C14—C13—H13A	109.8	C16—N4—C18	105.4 (3)
C12—C13—H13B	109.8	C16—N4—Co1^iv	124.3 (3)
C14—C13—H13B	109.8	C18—N4—Co1^iv	130.1 (3)
H13A—C13—H13B	108.2	C7—O4—Co1^v	89.1 (2)
C13—C14—C15	114.7 (4)	C7—O3—Co1^v	88.6 (2)
C13—C14—H14A	108.6	C8—O1—Co1	128.9 (2)
C15—C14—H14A	108.6	C8—O2—Co1^i	130.6 (2)
C13—C14—H14B	108.6
C6—C1—C2—C3	−1.8 (6)	O2^i—Co1—N1—C10	−146.9 (3)
I1—C1—C2—C3	178.7 (2)	N4^ii—Co1—N1—C10	35.2 (3)
C1—C2—C3—C4	3.0 (5)	O4^iii—Co1—N1—C10	−58.8 (4)
C1—C2—C3—C7	−179.2 (3)	O3^iii—Co1—N1—C10	−52.7 (3)
C2—C3—C4—C5	−1.6 (5)	C7^iii—Co1—N1—C10	−52.7 (3)
C7—C3—C4—C5	−179.5 (3)	N1—C9—N2—C11	−0.7 (4)
C3—C4—C5—C6	−0.9 (5)	N1—C9—N2—C12	−172.6 (3)
C3—C4—C5—C8	178.0 (3)	C10—C11—N2—C9	1.1 (5)
C2—C1—C6—C5	−0.8 (6)	C10—C11—N2—C12	173.1 (4)
I1—C1—C6—C5	178.7 (3)	C13—C12—N2—C9	−120.7 (4)
C4—C5—C6—C1	2.2 (5)	C13—C12—N2—C11	68.9 (5)
C8—C5—C6—C1	−176.7 (3)	N4—C16—N3—C17	−0.7 (4)
C4—C3—C7—O4	153.0 (3)	N4—C16—N3—C15	−174.8 (3)
C2—C3—C7—O4	−24.8 (5)	C18—C17—N3—C16	0.5 (4)
C4—C3—C7—O3	−27.9 (5)	C18—C17—N3—C15	174.7 (3)
C2—C3—C7—O3	154.3 (3)	C14—C15—N3—C16	−64.6 (5)
C6—C5—C8—O2	155.5 (3)	C14—C15—N3—C17	122.5 (4)
C4—C5—C8—O2	−23.4 (5)	N3—C16—N4—C18	0.6 (4)
C6—C5—C8—O1	−25.7 (5)	N3—C16—N4—Co1^iv	175.0 (2)
C4—C5—C8—O1	155.4 (3)	C17—C18—N4—C16	−0.2 (5)
N1—C10—C11—N2	−1.1 (5)	C17—C18—N4—Co1^iv	−174.2 (3)
N2—C12—C13—C14	−173.9 (4)	O3—C7—O4—Co1^v	−5.7 (3)
C12—C13—C14—C15	−172.4 (4)	C3—C7—O4—Co1^v	173.4 (3)
C13—C14—C15—N3	−68.0 (5)	O4—C7—O3—Co1^v	5.7 (3)
N3—C17—C18—N4	−0.2 (5)	C3—C7—O3—Co1^v	−173.4 (3)
N2—C9—N1—C10	0.0 (4)	O2—C8—O1—Co1	6.1 (5)
N2—C9—N1—Co1	178.0 (2)	C5—C8—O1—Co1	−172.6 (2)
C11—C10—N1—C9	0.7 (5)	N1—Co1—O1—C8	42.4 (3)
C11—C10—N1—Co1	−177.6 (3)	O2^i—Co1—O1—C8	−52.8 (3)
O1—Co1—N1—C9	−56.2 (4)	N4^ii—Co1—O1—C8	134.4 (3)
O2^i—Co1—N1—C9	35.3 (3)	O4^iii—Co1—O1—C8	−137.4 (3)
N4^ii—Co1—N1—C9	−142.5 (3)	O3^iii—Co1—O1—C8	−156.2 (3)
O4^iii—Co1—N1—C9	123.4 (3)	O1—C8—O2—Co1^i	98.0 (4)
O3^iii—Co1—N1—C9	129.5 (3)	C5—C8—O2—Co1^i	−83.3 (4)
O1—Co1—N1—C10	121.6 (3)

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

(2) Poly[[[µ₂-1,4-bis(1H-imidazol-1-yl)butane-κ²N³:N^3'](µ₂-5-iodobenzene-1,3-dicarboxylato-κ²O¹:O³)zinc(II)] trihydrate]

Crystal data

[Zn(C8H3IO4)(C10H14N4)]·3H2O	F(000) = 1192
Mr = 599.67	Dx = 1.635 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ybc	Cell parameters from 2506 reflections
a = 7.9910 (9) Å	θ = 2.4–20.9°
b = 17.8363 (19) Å	µ = 2.32 mm^−1
c = 18.2004 (17) Å	T = 293 K
β = 110.080 (4)°	Prism, colourless
V = 2436.4 (4) Å^3	0.26 × 0.23 × 0.22 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	5573 independent reflections
Radiation source: fine-focus sealed tube	2767 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.067
φ and ω scans	θmax = 27.5°, θmin = 2.6°
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2003)	h = −10→10
Tmin = 0.548, Tmax = 0.644	k = −21→23
20965 measured reflections	l = −20→23

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.216	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.117P)^2] where P = (Fo^2 + 2Fc^2)/3
5573 reflections	(Δ/σ)max < 0.001
275 parameters	Δρmax = 0.84 e Å^−3
61 restraints	Δρmin = −0.69 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
N4	−0.0419 (8)	0.4213 (4)	0.2648 (4)	0.0635 (16)
I1	1.81898 (8)	0.92264 (4)	−0.01654 (4)	0.0936 (3)
Zn1	1.11183 (10)	0.81736 (5)	0.21887 (5)	0.0562 (3)
O1	1.2076 (7)	0.8146 (3)	0.1348 (3)	0.0675 (14)
O2	1.4359 (9)	0.8919 (4)	0.1879 (3)	0.0896 (18)
O3	1.2814 (6)	0.7368 (3)	−0.1924 (3)	0.0695 (15)
O4	1.0791 (8)	0.7196 (5)	−0.1352 (4)	0.102 (2)
N1	0.8939 (8)	0.7532 (4)	0.1735 (4)	0.0665 (16)
N2	0.6424 (12)	0.6945 (6)	0.1589 (7)	0.114 (3)
N3	0.1035 (15)	0.5152 (6)	0.2349 (8)	0.152 (5)
C1	1.3446 (10)	0.8526 (5)	0.1332 (4)	0.0599 (18)
C2	1.3889 (9)	0.8452 (4)	0.0598 (4)	0.0560 (17)
C3	1.2855 (9)	0.8015 (4)	−0.0023 (4)	0.0536 (17)
H3	1.1831	0.7783	0.0000	0.064*
C4	1.3348 (9)	0.7923 (4)	−0.0679 (4)	0.0539 (17)
C5	1.4897 (9)	0.8248 (4)	−0.0700 (4)	0.0564 (18)
H5	1.5270	0.8164	−0.1124	0.068*
C6	1.5894 (8)	0.8699 (4)	−0.0086 (4)	0.0560 (17)
C7	1.5401 (9)	0.8805 (5)	0.0555 (4)	0.0584 (18)
H7	1.6077	0.9113	0.0962	0.070*
C8	1.2226 (10)	0.7451 (5)	−0.1357 (4)	0.0644 (19)
C9	0.8425 (13)	0.7175 (5)	0.1036 (5)	0.081 (2)
H9	0.9021	0.7189	0.0677	0.097*
C10	0.6916 (15)	0.6798 (6)	0.0946 (8)	0.106 (3)
H10	0.6307	0.6493	0.0525	0.127*
C11	0.7694 (12)	0.7366 (6)	0.2049 (6)	0.089 (3)
H11	0.7728	0.7532	0.2538	0.107*
C12	0.4850 (15)	0.6658 (7)	0.1773 (10)	0.141 (5)
H12A	0.4578	0.7008	0.2124	0.170*
H12B	0.3828	0.6640	0.1293	0.170*
C13	0.5120 (16)	0.5922 (8)	0.2128 (10)	0.171 (6)
H13A	0.6299	0.5900	0.2522	0.205*
H13B	0.5068	0.5551	0.1731	0.205*
C14	0.3783 (19)	0.5731 (8)	0.2494 (8)	0.147 (5)
H14A	0.4217	0.5317	0.2854	0.176*
H14B	0.3609	0.6158	0.2790	0.176*
C15	0.2100 (18)	0.5528 (11)	0.1905 (9)	0.189 (7)
H15A	0.2287	0.5186	0.1527	0.226*
H15B	0.1485	0.5969	0.1633	0.226*
C16	0.0797 (16)	0.4399 (7)	0.2337 (8)	0.116 (4)
H16	0.1409	0.4058	0.2136	0.139*
C17	−0.0846 (13)	0.4865 (5)	0.2929 (6)	0.083 (3)
H17	−0.1670	0.4915	0.3183	0.100*
C18	0.0110 (16)	0.5425 (6)	0.2781 (8)	0.119 (4)
H18	0.0129	0.5918	0.2949	0.143*
O1W	0.5858 (16)	0.8685 (8)	0.3524 (8)	0.199 (5)
H1WA	0.5630	0.8831	0.3055	0.299*
H1WB	0.5089	0.8356	0.3525	0.299*
O2W	0.916 (2)	0.8651 (9)	0.4505 (9)	0.232 (6)
H2WB	0.8074	0.8686	0.4212	0.348*
H2WA	0.9710	0.8395	0.4266	0.348*
O3W	0.348 (4)	0.957 (3)	0.450 (3)	0.53 (2)*
H3WA	0.4573	0.9573	0.4526	0.802*
H3WB	0.3265	0.9142	0.4662	0.802*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N4	0.074 (4)	0.072 (4)	0.057 (4)	−0.014 (3)	0.037 (3)	−0.007 (3)
I1	0.0713 (4)	0.1330 (7)	0.0837 (5)	−0.0378 (3)	0.0359 (3)	−0.0002 (4)
Zn1	0.0578 (5)	0.0693 (6)	0.0495 (5)	0.0072 (4)	0.0289 (4)	0.0050 (4)
O1	0.068 (3)	0.091 (4)	0.054 (3)	0.001 (3)	0.034 (3)	0.000 (3)
O2	0.095 (4)	0.124 (5)	0.061 (4)	−0.026 (4)	0.041 (3)	−0.028 (4)
O3	0.063 (3)	0.098 (4)	0.053 (3)	−0.013 (3)	0.027 (2)	−0.015 (3)
O4	0.086 (4)	0.160 (6)	0.073 (4)	−0.059 (4)	0.042 (3)	−0.040 (4)
N1	0.062 (4)	0.076 (4)	0.075 (4)	0.003 (3)	0.042 (3)	0.008 (4)
N2	0.092 (6)	0.129 (8)	0.128 (8)	−0.033 (6)	0.047 (6)	0.022 (6)
N3	0.170 (9)	0.090 (7)	0.278 (15)	−0.045 (6)	0.182 (11)	−0.027 (8)
C1	0.059 (4)	0.081 (5)	0.049 (4)	0.002 (4)	0.030 (3)	0.001 (4)
C2	0.061 (4)	0.066 (5)	0.046 (4)	0.007 (3)	0.025 (3)	0.003 (3)
C3	0.045 (3)	0.073 (5)	0.045 (4)	−0.009 (3)	0.020 (3)	0.003 (3)
C4	0.049 (3)	0.073 (5)	0.044 (4)	−0.002 (3)	0.022 (3)	−0.001 (3)
C5	0.059 (4)	0.074 (5)	0.045 (4)	0.001 (4)	0.029 (3)	0.003 (4)
C6	0.047 (4)	0.065 (5)	0.058 (4)	−0.008 (3)	0.022 (3)	0.008 (4)
C7	0.055 (4)	0.078 (5)	0.042 (4)	−0.009 (4)	0.017 (3)	−0.002 (4)
C8	0.061 (4)	0.079 (5)	0.060 (5)	0.000 (4)	0.030 (4)	0.003 (4)
C9	0.100 (7)	0.072 (6)	0.075 (6)	−0.003 (5)	0.038 (5)	0.002 (5)
C10	0.097 (7)	0.091 (7)	0.123 (10)	−0.035 (6)	0.029 (7)	−0.006 (7)
C11	0.081 (6)	0.096 (7)	0.099 (7)	−0.017 (5)	0.040 (5)	0.014 (6)
C12	0.108 (7)	0.153 (9)	0.178 (9)	−0.002 (6)	0.068 (7)	0.001 (7)
C13	0.155 (9)	0.182 (10)	0.186 (10)	−0.009 (8)	0.074 (8)	0.027 (8)
C14	0.146 (9)	0.156 (9)	0.146 (9)	−0.001 (7)	0.058 (7)	−0.009 (7)
C15	0.192 (11)	0.190 (11)	0.194 (11)	0.001 (8)	0.080 (9)	0.009 (8)
C16	0.117 (6)	0.115 (7)	0.153 (8)	−0.020 (6)	0.096 (6)	−0.016 (6)
C17	0.096 (6)	0.066 (6)	0.112 (7)	−0.004 (5)	0.066 (6)	−0.003 (5)
C18	0.125 (9)	0.076 (7)	0.194 (14)	−0.007 (6)	0.103 (10)	0.004 (8)
O1W	0.178 (7)	0.229 (9)	0.195 (8)	−0.069 (7)	0.070 (6)	0.011 (7)
O2W	0.254 (10)	0.245 (10)	0.209 (9)	0.015 (8)	0.094 (8)	−0.010 (8)

Geometric parameters (Å, º)

N4—C16	1.324 (11)	C5—H5	0.9300
N4—C17	1.360 (10)	C6—C7	1.367 (9)
N4—Zn1^i	1.988 (6)	C7—H7	0.9300
I1—C6	2.111 (6)	C9—C10	1.341 (13)
Zn1—O1	1.932 (5)	C9—H9	0.9300
Zn1—O3^ii	1.968 (5)	C10—H10	0.9300
Zn1—N4^iii	1.988 (6)	C11—H11	0.9300
Zn1—N1	2.009 (7)	C12—C13	1.446 (9)
O1—C1	1.297 (9)	C12—H12A	0.9700
O2—C1	1.232 (9)	C12—H12B	0.9700
O3—C8	1.281 (8)	C13—C14	1.479 (9)
O3—Zn1^iv	1.968 (5)	C13—H13A	0.9700
O4—C8	1.236 (8)	C13—H13B	0.9700
N1—C11	1.339 (10)	C14—C15	1.449 (9)
N1—C9	1.355 (10)	C14—H14A	0.9700
N2—C11	1.308 (13)	C14—H14B	0.9700
N2—C10	1.382 (15)	C15—H15A	0.9700
N2—C12	1.498 (8)	C15—H15B	0.9700
N3—C18	1.342 (13)	C16—H16	0.9300
N3—C16	1.355 (14)	C17—C18	1.339 (13)
N3—C15	1.515 (9)	C17—H17	0.9300
C1—C2	1.501 (10)	C18—H18	0.9300
C2—C3	1.388 (10)	O1W—O1W	0.00 (3)
C2—C7	1.389 (10)	O1W—H1WA	0.8500
C3—C4	1.389 (9)	O1W—H1WB	0.8500
C3—H3	0.9300	O2W—H2WB	0.8500
C4—C5	1.378 (9)	O2W—H2WA	0.8501
C4—C8	1.509 (10)	O3W—H3WA	0.8565
C5—C6	1.386 (10)	O3W—H3WB	0.8575
C16—N4—C17	105.2 (8)	N1—C9—H9	125.7
C16—N4—Zn1^i	125.7 (7)	C9—C10—N2	107.9 (10)
C17—N4—Zn1^i	128.4 (5)	C9—C10—H10	126.1
O1—Zn1—O3^ii	106.8 (2)	N2—C10—H10	126.1
O1—Zn1—N4^iii	110.5 (2)	N2—C11—N1	112.4 (10)
O3^ii—Zn1—N4^iii	119.0 (3)	N2—C11—H11	123.8
O1—Zn1—N1	100.6 (2)	N1—C11—H11	123.8
O3^ii—Zn1—N1	108.2 (2)	C13—C12—N2	113.7 (10)
N4^iii—Zn1—N1	110.1 (3)	C13—C12—H12A	108.8
C1—O1—Zn1	124.8 (5)	N2—C12—H12A	108.8
C8—O3—Zn1^iv	112.2 (5)	C13—C12—H12B	108.8
C11—N1—C9	105.5 (8)	N2—C12—H12B	108.8
C11—N1—Zn1	128.1 (7)	H12A—C12—H12B	107.7
C9—N1—Zn1	126.4 (5)	C12—C13—C14	113.0 (9)
C11—N2—C10	105.5 (8)	C12—C13—H13A	109.0
C11—N2—C12	125.4 (12)	C14—C13—H13A	109.0
C10—N2—C12	129.0 (11)	C12—C13—H13B	109.0
C18—N3—C16	105.5 (8)	C14—C13—H13B	109.0
C18—N3—C15	132.5 (12)	H13A—C13—H13B	107.8
C16—N3—C15	122.0 (11)	C15—C14—C13	110.8 (9)
O2—C1—O1	123.4 (6)	C15—C14—H14A	109.5
O2—C1—C2	121.0 (7)	C13—C14—H14A	109.5
O1—C1—C2	115.6 (7)	C15—C14—H14B	109.5
C3—C2—C7	119.7 (6)	C13—C14—H14B	109.5
C3—C2—C1	121.2 (6)	H14A—C14—H14B	108.1
C7—C2—C1	119.1 (7)	C14—C15—N3	105.4 (11)
C2—C3—C4	120.1 (6)	C14—C15—H15A	110.7
C2—C3—H3	120.0	N3—C15—H15A	110.7
C4—C3—H3	120.0	C14—C15—H15B	110.7
C5—C4—C3	119.8 (6)	N3—C15—H15B	110.7
C5—C4—C8	119.9 (6)	H15A—C15—H15B	108.8
C3—C4—C8	120.2 (6)	N4—C16—N3	111.1 (9)
C4—C5—C6	119.6 (6)	N4—C16—H16	124.4
C4—C5—H5	120.2	N3—C16—H16	124.4
C6—C5—H5	120.2	C18—C17—N4	109.2 (8)
C7—C6—C5	121.0 (6)	C18—C17—H17	125.4
C7—C6—I1	120.6 (5)	N4—C17—H17	125.4
C5—C6—I1	118.4 (5)	C17—C18—N3	108.3 (10)
C6—C7—C2	119.8 (7)	C17—C18—H18	125.8
C6—C7—H7	120.1	N3—C18—H18	125.8
C2—C7—H7	120.1	O1W—O1W—H1WA	0.0
O4—C8—O3	124.1 (7)	O1W—O1W—H1WB	0.0
O4—C8—C4	119.5 (6)	H1WA—O1W—H1WB	107.8
O3—C8—C4	116.3 (6)	H2WB—O2W—H2WA	108.2
C10—C9—N1	108.6 (9)	H3WA—O3W—H3WB	108.1
C10—C9—H9	125.7

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2^v	0.85	2.04	2.848 (15)	160
O1W—H1WB···O3^vi	0.85	2.15	2.959 (13)	159
O2W—H2WB···O1W	0.85	1.78	2.63 (2)	174
O2W—H2WA···O4^ii	0.85	1.95	2.796 (16)	175
O3W—H3WA···O3W^vii	0.86	2.45	2.91 (7)	115

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