Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
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:N3′](μ3-5-iodobenzene-1,3-dicarboxyl­ato-κ4O1,O1′:O3:O3′)cobalt(II)], [Co(C8H3IO4)(C10H14N4)]n or [Co(iip)(bimb)]n, (1), and poly[[[μ2-1,4-bis­(1H-imidazol-1-yl)butane-κ2N3:N3′](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 (κ112)(κ1, κ11)-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 transtranstrans 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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615014655/ly3018sup1.cif
Contains datablocks 1, 2, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615014655/ly30181sup2.hkl
Contains datablock 1

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615014655/ly30182sup3.hkl
Contains datablock 2

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2053229615014655/ly3018sup4.pdf
PXRD patterns, packing diagram and FT-IR spectra

CCDC references: 832842; 832839

Introduction top

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-ip2- ligand in related coordination compounds has flexible conformations, various binding modes and a strong ability to form supra­molecular inter­actions, such as hydrogen bonds and ππ 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 CdII–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 CoII/ZnII–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.

Experimental top

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 Kα1/2 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).

Synthesis and crystallization top

Synthesis of [Co(iip)(bimb)]\~n\~, (1) top

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).

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

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).

Refinement top

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 Uiso(H) = 1.2Ueq(C). The amino H atoms were also added geometrically, with N—H = 0.86 Å and Uiso(H) = 1.5Ueq(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 Uiso(H) = 1.5Ueq(O).

Results and discussion top

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

Single-crystal X-ray structure analysis shows that the asymmetric unit of (1) consists of one CoII cation, one iip2- ligand and one bimb ligand. As shown in Fig. 1, each six-coordinated CoII cation is bound by two N atoms from two bimb ligands and by four O atoms from three iip2- 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 iip2- 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 iip2- ligand exhibits the chelating coordination mode. Thus, the iip2- ligand adopts the (κ1,κ12)(κ1, κ11)-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 transtranstrans (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-iip2- 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/NiII compound (Ma et al., 2011).

It should be noted that compound (1) is also a new member of the Co/5-iip2-/bimb family (Zang et al., 2012).

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

Single-crystal X-ray structure analysis shows that the asymmetric unit of (2) consists of one ZnII cation, one iip2- anion, one bimb ligand and three solvent water molecules. As shown in Fig. 6, each ZnII cation is tetra­coordinated by two N atoms from two bridging bimb ligands and two O atoms from two iip2- 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 ZnII cation vary from 100.6 (2) to 119.0 (3)°. Therefore, the ZnII 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 ZnII 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 iip2- 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 CoII complex based on the same ligand (Zang et al., 2012) and also to a 5-Me-ip/CoII/bimb compound (Chang et al., 2013). Compound (2) is also a relative of previous work on similar alkyl bis-imidazole ligands with iip2- (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···O2v and O1W—H1WB···O3vi; 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···O3Wvii; 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 CoII and ZnII cations have a great influence on crystalline architecture.

Thermal stability top

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 CoII 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.

UV–Vis spectra top

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 ππ* transition of the aromatic ligands.These bands are not strongly perturbed upon the coordination of this ligand to the central CoII or ZnII cations, suggesting that coordination of central metal ions hardly alters the intrinsic electronic properties of H2iip. For (1), two peaks at 546 [4T1g(F)4T2g(F)] and 1260 nm [4T1g(F)4T1g(P)] probably originate from the dd spin-allowed transition of the d7 (Co2+) cation, which is typical for o­cta­hedrally coordinated CoII 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 iip2- ligand to the ZnII cation.

Fluorescence properties top

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 λex = 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 ππ* transition of the bimb and iip2- ligands (Ge et al., 2015).

Conclusion top

In summary, two CoII/ZnII 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 top

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 top
[Figure 1] Fig. 1. A view of the coordination environment of the CoII 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.]
[Figure 2] Fig. 2. A view of the one-dimensional carboxylate-bridged double chain in (1), along the [100] direction.
[Figure 3] Fig. 3. The three-dimensional structure of (1).
[Figure 4] Fig. 4. A view of the twofold interpenetrating networks of (1), connected to each other through C—I···O halogen bonds (black dashed lines).
[Figure 5] Fig. 5. A schematic drawing of the twofold interpenetrating three-dimensional network of (1).
[Figure 6] Fig. 6. A view of the coordination environment of the ZnII 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.]
[Figure 7] Fig. 7. The one-dimensional left-handed helix of (2), around the crystallographic 21 axis.
[Figure 8] Fig. 8. The two-dimensional (4,4) topological network of (2), showing the coordination modes of the iip2- and bimb ligands.
[Figure 9] Fig. 9. The TG curves of (1) (black) and (2) (red).
[Figure 10] 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:N3'](µ3-5-iodobenzene-1,3-dicarboxylato-κ4O1,O1':O3:O3')cobalt(II) top
Crystal data top
[Co(C8H3IO4)(C10H14N4)]F(000) = 2120
Mr = 539.19Dx = 1.841 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ac2abCell parameters from 3330 reflections
a = 10.2561 (18) Åθ = 2.5–24.7°
b = 17.088 (3) ŵ = 2.50 mm1
c = 22.205 (4) ÅT = 296 K
V = 3891.6 (12) Å3Block, purple
Z = 80.32 × 0.25 × 0.19 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
4459 independent reflections
Radiation source: fine-focus sealed tube2854 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.071
φ and ω scansθmax = 27.6°, θmin = 2.4°
Absorption correction: empirical (using intensity measurements)
(SADABS; Bruker, 2003)
h = 1313
Tmin = 0.477, Tmax = 0.622k = 2222
32053 measured reflectionsl = 2828
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0344P)2 + 0.5923P]
where P = (Fo2 + 2Fc2)/3
4459 reflections(Δ/σ)max = 0.004
253 parametersΔρmax = 0.60 e Å3
0 restraintsΔρmin = 1.08 e Å3
Crystal data top
[Co(C8H3IO4)(C10H14N4)]V = 3891.6 (12) Å3
Mr = 539.19Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 10.2561 (18) ŵ = 2.50 mm1
b = 17.088 (3) ÅT = 296 K
c = 22.205 (4) Å0.32 × 0.25 × 0.19 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
4459 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Bruker, 2003)
2854 reflections with I > 2σ(I)
Tmin = 0.477, Tmax = 0.622Rint = 0.071
32053 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.090H-atom parameters constrained
S = 1.03Δρmax = 0.60 e Å3
4459 reflectionsΔρmin = 1.08 e Å3
253 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
C10.8506 (3)0.9166 (2)1.18175 (15)0.0307 (8)
C20.9742 (3)0.9168 (2)1.15662 (15)0.0317 (9)
H21.04770.91411.18110.038*
C30.9871 (3)0.92106 (19)1.09422 (14)0.0245 (8)
C40.8763 (3)0.92868 (18)1.05877 (15)0.0235 (7)
H40.88490.93291.01720.028*
C50.7524 (3)0.93013 (19)1.08456 (15)0.0249 (8)
C60.7400 (3)0.9227 (2)1.14659 (15)0.0308 (8)
H60.65780.92181.16430.037*
C71.1214 (3)0.9201 (2)1.06742 (15)0.0259 (8)
C80.6334 (3)0.9411 (2)1.04572 (16)0.0249 (8)
C90.4666 (4)0.8926 (2)0.89721 (16)0.0333 (9)
H90.51340.93900.90000.040*
C100.3419 (4)0.7963 (2)0.91757 (18)0.0499 (11)
H100.28420.76350.93770.060*
C110.3895 (5)0.7834 (3)0.86167 (18)0.0502 (11)
H110.37230.74070.83700.060*
C120.5522 (4)0.8536 (3)0.79539 (16)0.0519 (12)
H12A0.60710.80760.79220.062*
H12B0.60870.89860.80080.062*
C130.4762 (4)0.8635 (3)0.73711 (16)0.0462 (11)
H13A0.42900.91260.73780.055*
H13B0.41350.82130.73290.055*
C140.5704 (4)0.8625 (3)0.68407 (16)0.0493 (11)
H14A0.60940.81080.68140.059*
H14B0.64000.89950.69200.059*
C150.5090 (5)0.8824 (2)0.62333 (17)0.0507 (12)
H15A0.46340.93190.62680.061*
H15B0.57780.88890.59380.061*
C160.4461 (4)0.7479 (2)0.58625 (17)0.0393 (10)
H160.52790.72510.59080.047*
C170.2897 (4)0.8337 (2)0.58752 (18)0.0482 (11)
H170.24220.87950.59270.058*
C180.2445 (4)0.7658 (2)0.56463 (18)0.0459 (11)
H180.15980.75710.55140.055*
Co10.34832 (4)0.90504 (3)1.02738 (2)0.02510 (12)
I10.83171 (3)0.90762 (2)1.276244 (11)0.06035 (13)
N10.3914 (3)0.86494 (18)0.94014 (13)0.0332 (7)
N20.4677 (3)0.84554 (18)0.84876 (13)0.0360 (8)
N30.4175 (3)0.82279 (18)0.60173 (13)0.0379 (8)
N40.3438 (3)0.71137 (18)0.56400 (13)0.0354 (8)
O41.2160 (2)0.94280 (15)1.09887 (10)0.0338 (6)
O31.1367 (2)0.89564 (14)1.01441 (10)0.0329 (6)
O10.5281 (2)0.91426 (13)1.06739 (10)0.0312 (6)
O20.6458 (2)0.97368 (14)0.99589 (10)0.0304 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0241 (19)0.052 (2)0.0159 (16)0.0005 (18)0.0030 (14)0.0002 (16)
C20.0191 (18)0.053 (2)0.0233 (18)0.0010 (17)0.0012 (15)0.0023 (17)
C30.0184 (17)0.033 (2)0.0216 (16)0.0011 (15)0.0002 (14)0.0004 (15)
C40.0204 (18)0.0314 (19)0.0187 (17)0.0023 (15)0.0031 (14)0.0009 (15)
C50.0174 (17)0.0302 (19)0.0269 (18)0.0006 (15)0.0030 (15)0.0021 (15)
C60.0180 (18)0.048 (2)0.0266 (18)0.0000 (16)0.0031 (15)0.0012 (17)
C70.0156 (17)0.038 (2)0.0243 (19)0.0047 (15)0.0011 (14)0.0063 (15)
C80.0161 (18)0.0261 (18)0.032 (2)0.0015 (15)0.0018 (15)0.0009 (16)
C90.032 (2)0.039 (2)0.0295 (19)0.0010 (18)0.0017 (17)0.0040 (17)
C100.057 (3)0.054 (3)0.039 (2)0.012 (2)0.004 (2)0.002 (2)
C110.064 (3)0.050 (3)0.037 (2)0.006 (2)0.001 (2)0.013 (2)
C120.047 (3)0.084 (3)0.025 (2)0.006 (2)0.009 (2)0.012 (2)
C130.045 (3)0.062 (3)0.032 (2)0.002 (2)0.0015 (19)0.007 (2)
C140.054 (3)0.063 (3)0.031 (2)0.016 (2)0.011 (2)0.016 (2)
C150.075 (3)0.045 (2)0.033 (2)0.020 (2)0.003 (2)0.0069 (19)
C160.039 (2)0.042 (2)0.037 (2)0.0048 (19)0.0002 (19)0.0063 (18)
C170.054 (3)0.048 (3)0.043 (3)0.018 (2)0.010 (2)0.007 (2)
C180.034 (2)0.056 (3)0.048 (3)0.013 (2)0.001 (2)0.009 (2)
Co10.0139 (2)0.0410 (3)0.0204 (2)0.0009 (2)0.00073 (18)0.0010 (2)
I10.03528 (18)0.1246 (3)0.02114 (15)0.00909 (18)0.00426 (12)0.00411 (15)
N10.0294 (18)0.0424 (19)0.0278 (17)0.0016 (15)0.0034 (14)0.0037 (15)
N20.0372 (19)0.047 (2)0.0239 (16)0.0001 (16)0.0016 (14)0.0050 (15)
N30.052 (2)0.0358 (19)0.0255 (16)0.0006 (17)0.0038 (16)0.0005 (14)
N40.0287 (18)0.0438 (19)0.0337 (17)0.0058 (16)0.0004 (14)0.0063 (15)
O40.0136 (12)0.0626 (17)0.0253 (13)0.0062 (12)0.0016 (10)0.0007 (12)
O30.0190 (12)0.0575 (17)0.0221 (13)0.0037 (12)0.0013 (10)0.0016 (11)
O10.0149 (12)0.0446 (15)0.0342 (13)0.0039 (12)0.0001 (10)0.0078 (12)
O20.0236 (13)0.0411 (15)0.0264 (13)0.0021 (11)0.0010 (10)0.0056 (11)
Geometric parameters (Å, º) top
C1—C61.381 (5)C13—C141.523 (5)
C1—C21.385 (5)C13—H13A0.9700
C1—I12.113 (3)C13—H13B0.9700
C2—C31.394 (5)C14—C151.527 (5)
C2—H20.9300C14—H14A0.9700
C3—C41.388 (5)C14—H14B0.9700
C3—C71.501 (5)C15—N31.466 (5)
C4—C51.394 (5)C15—H15A0.9700
C4—H40.9300C15—H15B0.9700
C5—C61.389 (5)C16—N41.316 (5)
C5—C81.506 (4)C16—N31.358 (4)
C6—H60.9300C16—H160.9300
C7—O41.257 (4)C17—C181.348 (6)
C7—O31.259 (4)C17—N31.362 (5)
C8—O21.245 (4)C17—H170.9300
C8—O11.268 (4)C18—N41.379 (4)
C9—N11.314 (4)C18—H180.9300
C9—N21.343 (4)Co1—O12.053 (2)
C9—H90.9300Co1—N12.102 (3)
C10—C111.352 (5)Co1—O2i2.137 (2)
C10—N11.373 (5)Co1—N4ii2.150 (3)
C10—H100.9300Co1—O4iii2.186 (2)
C11—N21.361 (5)Co1—O3iii2.195 (2)
C11—H110.9300N4—Co1iv2.150 (3)
C12—N21.474 (5)O4—Co1v2.186 (2)
C12—C131.520 (5)O3—Co1v2.195 (2)
C12—H12A0.9700O2—Co1i2.137 (2)
C12—H12B0.9700
C6—C1—C2121.6 (3)C15—C14—H14B108.6
C6—C1—I1119.4 (2)H14A—C14—H14B107.6
C2—C1—I1119.0 (2)N3—C15—C14113.4 (3)
C1—C2—C3119.2 (3)N3—C15—H15A108.9
C1—C2—H2120.4C14—C15—H15A108.9
C3—C2—H2120.4N3—C15—H15B108.9
C4—C3—C2119.4 (3)C14—C15—H15B108.9
C4—C3—C7121.8 (3)H15A—C15—H15B107.7
C2—C3—C7118.7 (3)N4—C16—N3111.7 (4)
C3—C4—C5121.0 (3)N4—C16—H16124.2
C3—C4—H4119.5N3—C16—H16124.2
C5—C4—H4119.5C18—C17—N3107.5 (4)
C6—C5—C4119.3 (3)C18—C17—H17126.2
C6—C5—C8120.3 (3)N3—C17—H17126.2
C4—C5—C8120.4 (3)C17—C18—N4109.3 (4)
C1—C6—C5119.5 (3)C17—C18—H18125.4
C1—C6—H6120.3N4—C18—H18125.4
C5—C6—H6120.3O1—Co1—N1103.59 (11)
O4—C7—O3121.7 (3)O1—Co1—O2i90.27 (9)
O4—C7—C3119.0 (3)N1—Co1—O2i95.01 (11)
O3—C7—C3119.3 (3)O1—Co1—N4ii85.79 (10)
O2—C8—O1125.9 (3)N1—Co1—N4ii92.95 (12)
O2—C8—C5118.8 (3)O2i—Co1—N4ii171.75 (10)
O1—C8—C5115.3 (3)O1—Co1—O4iii102.74 (9)
N1—C9—N2111.8 (3)N1—Co1—O4iii153.67 (11)
N1—C9—H9124.1O2i—Co1—O4iii84.66 (9)
N2—C9—H9124.1N4ii—Co1—O4iii89.15 (11)
C11—C10—N1109.9 (4)O1—Co1—O3iii161.88 (9)
C11—C10—H10125.1N1—Co1—O3iii93.62 (10)
N1—C10—H10125.1O2i—Co1—O3iii93.86 (9)
C10—C11—N2106.3 (4)N4ii—Co1—O3iii87.75 (10)
C10—C11—H11126.9O4iii—Co1—O3iii60.21 (9)
N2—C11—H11126.9C9—N1—C10105.0 (3)
N2—C12—C13113.2 (3)C9—N1—Co1132.5 (3)
N2—C12—H12A108.9C10—N1—Co1122.5 (3)
C13—C12—H12A108.9C9—N2—C11107.0 (3)
N2—C12—H12B108.9C9—N2—C12126.4 (3)
C13—C12—H12B108.9C11—N2—C12126.1 (3)
H12A—C12—H12B107.8C16—N3—C17106.1 (3)
C12—C13—C14109.4 (4)C16—N3—C15126.9 (4)
C12—C13—H13A109.8C17—N3—C15126.7 (4)
C14—C13—H13A109.8C16—N4—C18105.4 (3)
C12—C13—H13B109.8C16—N4—Co1iv124.3 (3)
C14—C13—H13B109.8C18—N4—Co1iv130.1 (3)
H13A—C13—H13B108.2C7—O4—Co1v89.1 (2)
C13—C14—C15114.7 (4)C7—O3—Co1v88.6 (2)
C13—C14—H14A108.6C8—O1—Co1128.9 (2)
C15—C14—H14A108.6C8—O2—Co1i130.6 (2)
C13—C14—H14B108.6
C6—C1—C2—C31.8 (6)O2i—Co1—N1—C10146.9 (3)
I1—C1—C2—C3178.7 (2)N4ii—Co1—N1—C1035.2 (3)
C1—C2—C3—C43.0 (5)O4iii—Co1—N1—C1058.8 (4)
C1—C2—C3—C7179.2 (3)O3iii—Co1—N1—C1052.7 (3)
C2—C3—C4—C51.6 (5)C7iii—Co1—N1—C1052.7 (3)
C7—C3—C4—C5179.5 (3)N1—C9—N2—C110.7 (4)
C3—C4—C5—C60.9 (5)N1—C9—N2—C12172.6 (3)
C3—C4—C5—C8178.0 (3)C10—C11—N2—C91.1 (5)
C2—C1—C6—C50.8 (6)C10—C11—N2—C12173.1 (4)
I1—C1—C6—C5178.7 (3)C13—C12—N2—C9120.7 (4)
C4—C5—C6—C12.2 (5)C13—C12—N2—C1168.9 (5)
C8—C5—C6—C1176.7 (3)N4—C16—N3—C170.7 (4)
C4—C3—C7—O4153.0 (3)N4—C16—N3—C15174.8 (3)
C2—C3—C7—O424.8 (5)C18—C17—N3—C160.5 (4)
C4—C3—C7—O327.9 (5)C18—C17—N3—C15174.7 (3)
C2—C3—C7—O3154.3 (3)C14—C15—N3—C1664.6 (5)
C6—C5—C8—O2155.5 (3)C14—C15—N3—C17122.5 (4)
C4—C5—C8—O223.4 (5)N3—C16—N4—C180.6 (4)
C6—C5—C8—O125.7 (5)N3—C16—N4—Co1iv175.0 (2)
C4—C5—C8—O1155.4 (3)C17—C18—N4—C160.2 (5)
N1—C10—C11—N21.1 (5)C17—C18—N4—Co1iv174.2 (3)
N2—C12—C13—C14173.9 (4)O3—C7—O4—Co1v5.7 (3)
C12—C13—C14—C15172.4 (4)C3—C7—O4—Co1v173.4 (3)
C13—C14—C15—N368.0 (5)O4—C7—O3—Co1v5.7 (3)
N3—C17—C18—N40.2 (5)C3—C7—O3—Co1v173.4 (3)
N2—C9—N1—C100.0 (4)O2—C8—O1—Co16.1 (5)
N2—C9—N1—Co1178.0 (2)C5—C8—O1—Co1172.6 (2)
C11—C10—N1—C90.7 (5)N1—Co1—O1—C842.4 (3)
C11—C10—N1—Co1177.6 (3)O2i—Co1—O1—C852.8 (3)
O1—Co1—N1—C956.2 (4)N4ii—Co1—O1—C8134.4 (3)
O2i—Co1—N1—C935.3 (3)O4iii—Co1—O1—C8137.4 (3)
N4ii—Co1—N1—C9142.5 (3)O3iii—Co1—O1—C8156.2 (3)
O4iii—Co1—N1—C9123.4 (3)O1—C8—O2—Co1i98.0 (4)
O3iii—Co1—N1—C9129.5 (3)C5—C8—O2—Co1i83.3 (4)
O1—Co1—N1—C10121.6 (3)
Symmetry codes: (i) x+1, y+2, z+2; (ii) x, y+3/2, z+1/2; (iii) x1, y, z; (iv) x, y+3/2, z1/2; (v) x+1, y, z.
(2) Poly[[[µ2-1,4-bis(1H-imidazol-1-yl)butane-κ2N3:N3'](µ2-5-iodobenzene-1,3-dicarboxylato-κ2O1:O3)zinc(II)] trihydrate] top
Crystal data top
[Zn(C8H3IO4)(C10H14N4)]·3H2OF(000) = 1192
Mr = 599.67Dx = 1.635 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ybcCell parameters from 2506 reflections
a = 7.9910 (9) Åθ = 2.4–20.9°
b = 17.8363 (19) ŵ = 2.32 mm1
c = 18.2004 (17) ÅT = 293 K
β = 110.080 (4)°Prism, colourless
V = 2436.4 (4) Å30.26 × 0.23 × 0.22 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer
5573 independent reflections
Radiation source: fine-focus sealed tube2767 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.067
φ and ω scansθmax = 27.5°, θmin = 2.6°
Absorption correction: empirical (using intensity measurements)
(SADABS; Bruker, 2003)
h = 1010
Tmin = 0.548, Tmax = 0.644k = 2123
20965 measured reflectionsl = 2023
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.065Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.216H-atom parameters constrained
S = 0.97 w = 1/[σ2(Fo2) + (0.117P)2]
where P = (Fo2 + 2Fc2)/3
5573 reflections(Δ/σ)max < 0.001
275 parametersΔρmax = 0.84 e Å3
61 restraintsΔρmin = 0.69 e Å3
Crystal data top
[Zn(C8H3IO4)(C10H14N4)]·3H2OV = 2436.4 (4) Å3
Mr = 599.67Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.9910 (9) ŵ = 2.32 mm1
b = 17.8363 (19) ÅT = 293 K
c = 18.2004 (17) Å0.26 × 0.23 × 0.22 mm
β = 110.080 (4)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
5573 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Bruker, 2003)
2767 reflections with I > 2σ(I)
Tmin = 0.548, Tmax = 0.644Rint = 0.067
20965 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.06561 restraints
wR(F2) = 0.216H-atom parameters constrained
S = 0.97Δρmax = 0.84 e Å3
5573 reflectionsΔρmin = 0.69 e Å3
275 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
N40.0419 (8)0.4213 (4)0.2648 (4)0.0635 (16)
I11.81898 (8)0.92264 (4)0.01654 (4)0.0936 (3)
Zn11.11183 (10)0.81736 (5)0.21887 (5)0.0562 (3)
O11.2076 (7)0.8146 (3)0.1348 (3)0.0675 (14)
O21.4359 (9)0.8919 (4)0.1879 (3)0.0896 (18)
O31.2814 (6)0.7368 (3)0.1924 (3)0.0695 (15)
O41.0791 (8)0.7196 (5)0.1352 (4)0.102 (2)
N10.8939 (8)0.7532 (4)0.1735 (4)0.0665 (16)
N20.6424 (12)0.6945 (6)0.1589 (7)0.114 (3)
N30.1035 (15)0.5152 (6)0.2349 (8)0.152 (5)
C11.3446 (10)0.8526 (5)0.1332 (4)0.0599 (18)
C21.3889 (9)0.8452 (4)0.0598 (4)0.0560 (17)
C31.2855 (9)0.8015 (4)0.0023 (4)0.0536 (17)
H31.18310.77830.00000.064*
C41.3348 (9)0.7923 (4)0.0679 (4)0.0539 (17)
C51.4897 (9)0.8248 (4)0.0700 (4)0.0564 (18)
H51.52700.81640.11240.068*
C61.5894 (8)0.8699 (4)0.0086 (4)0.0560 (17)
C71.5401 (9)0.8805 (5)0.0555 (4)0.0584 (18)
H71.60770.91130.09620.070*
C81.2226 (10)0.7451 (5)0.1357 (4)0.0644 (19)
C90.8425 (13)0.7175 (5)0.1036 (5)0.081 (2)
H90.90210.71890.06770.097*
C100.6916 (15)0.6798 (6)0.0946 (8)0.106 (3)
H100.63070.64930.05250.127*
C110.7694 (12)0.7366 (6)0.2049 (6)0.089 (3)
H110.77280.75320.25380.107*
C120.4850 (15)0.6658 (7)0.1773 (10)0.141 (5)
H12A0.45780.70080.21240.170*
H12B0.38280.66400.12930.170*
C130.5120 (16)0.5922 (8)0.2128 (10)0.171 (6)
H13A0.62990.59000.25220.205*
H13B0.50680.55510.17310.205*
C140.3783 (19)0.5731 (8)0.2494 (8)0.147 (5)
H14A0.42170.53170.28540.176*
H14B0.36090.61580.27900.176*
C150.2100 (18)0.5528 (11)0.1905 (9)0.189 (7)
H15A0.22870.51860.15270.226*
H15B0.14850.59690.16330.226*
C160.0797 (16)0.4399 (7)0.2337 (8)0.116 (4)
H160.14090.40580.21360.139*
C170.0846 (13)0.4865 (5)0.2929 (6)0.083 (3)
H170.16700.49150.31830.100*
C180.0110 (16)0.5425 (6)0.2781 (8)0.119 (4)
H180.01290.59180.29490.143*
O1W0.5858 (16)0.8685 (8)0.3524 (8)0.199 (5)
H1WA0.56300.88310.30550.299*
H1WB0.50890.83560.35250.299*
O2W0.916 (2)0.8651 (9)0.4505 (9)0.232 (6)
H2WB0.80740.86860.42120.348*
H2WA0.97100.83950.42660.348*
O3W0.348 (4)0.957 (3)0.450 (3)0.53 (2)*
H3WA0.45730.95730.45260.802*
H3WB0.32650.91420.46620.802*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N40.074 (4)0.072 (4)0.057 (4)0.014 (3)0.037 (3)0.007 (3)
I10.0713 (4)0.1330 (7)0.0837 (5)0.0378 (3)0.0359 (3)0.0002 (4)
Zn10.0578 (5)0.0693 (6)0.0495 (5)0.0072 (4)0.0289 (4)0.0050 (4)
O10.068 (3)0.091 (4)0.054 (3)0.001 (3)0.034 (3)0.000 (3)
O20.095 (4)0.124 (5)0.061 (4)0.026 (4)0.041 (3)0.028 (4)
O30.063 (3)0.098 (4)0.053 (3)0.013 (3)0.027 (2)0.015 (3)
O40.086 (4)0.160 (6)0.073 (4)0.059 (4)0.042 (3)0.040 (4)
N10.062 (4)0.076 (4)0.075 (4)0.003 (3)0.042 (3)0.008 (4)
N20.092 (6)0.129 (8)0.128 (8)0.033 (6)0.047 (6)0.022 (6)
N30.170 (9)0.090 (7)0.278 (15)0.045 (6)0.182 (11)0.027 (8)
C10.059 (4)0.081 (5)0.049 (4)0.002 (4)0.030 (3)0.001 (4)
C20.061 (4)0.066 (5)0.046 (4)0.007 (3)0.025 (3)0.003 (3)
C30.045 (3)0.073 (5)0.045 (4)0.009 (3)0.020 (3)0.003 (3)
C40.049 (3)0.073 (5)0.044 (4)0.002 (3)0.022 (3)0.001 (3)
C50.059 (4)0.074 (5)0.045 (4)0.001 (4)0.029 (3)0.003 (4)
C60.047 (4)0.065 (5)0.058 (4)0.008 (3)0.022 (3)0.008 (4)
C70.055 (4)0.078 (5)0.042 (4)0.009 (4)0.017 (3)0.002 (4)
C80.061 (4)0.079 (5)0.060 (5)0.000 (4)0.030 (4)0.003 (4)
C90.100 (7)0.072 (6)0.075 (6)0.003 (5)0.038 (5)0.002 (5)
C100.097 (7)0.091 (7)0.123 (10)0.035 (6)0.029 (7)0.006 (7)
C110.081 (6)0.096 (7)0.099 (7)0.017 (5)0.040 (5)0.014 (6)
C120.108 (7)0.153 (9)0.178 (9)0.002 (6)0.068 (7)0.001 (7)
C130.155 (9)0.182 (10)0.186 (10)0.009 (8)0.074 (8)0.027 (8)
C140.146 (9)0.156 (9)0.146 (9)0.001 (7)0.058 (7)0.009 (7)
C150.192 (11)0.190 (11)0.194 (11)0.001 (8)0.080 (9)0.009 (8)
C160.117 (6)0.115 (7)0.153 (8)0.020 (6)0.096 (6)0.016 (6)
C170.096 (6)0.066 (6)0.112 (7)0.004 (5)0.066 (6)0.003 (5)
C180.125 (9)0.076 (7)0.194 (14)0.007 (6)0.103 (10)0.004 (8)
O1W0.178 (7)0.229 (9)0.195 (8)0.069 (7)0.070 (6)0.011 (7)
O2W0.254 (10)0.245 (10)0.209 (9)0.015 (8)0.094 (8)0.010 (8)
Geometric parameters (Å, º) top
N4—C161.324 (11)C5—H50.9300
N4—C171.360 (10)C6—C71.367 (9)
N4—Zn1i1.988 (6)C7—H70.9300
I1—C62.111 (6)C9—C101.341 (13)
Zn1—O11.932 (5)C9—H90.9300
Zn1—O3ii1.968 (5)C10—H100.9300
Zn1—N4iii1.988 (6)C11—H110.9300
Zn1—N12.009 (7)C12—C131.446 (9)
O1—C11.297 (9)C12—H12A0.9700
O2—C11.232 (9)C12—H12B0.9700
O3—C81.281 (8)C13—C141.479 (9)
O3—Zn1iv1.968 (5)C13—H13A0.9700
O4—C81.236 (8)C13—H13B0.9700
N1—C111.339 (10)C14—C151.449 (9)
N1—C91.355 (10)C14—H14A0.9700
N2—C111.308 (13)C14—H14B0.9700
N2—C101.382 (15)C15—H15A0.9700
N2—C121.498 (8)C15—H15B0.9700
N3—C181.342 (13)C16—H160.9300
N3—C161.355 (14)C17—C181.339 (13)
N3—C151.515 (9)C17—H170.9300
C1—C21.501 (10)C18—H180.9300
C2—C31.388 (10)O1W—O1W0.00 (3)
C2—C71.389 (10)O1W—H1WA0.8500
C3—C41.389 (9)O1W—H1WB0.8500
C3—H30.9300O2W—H2WB0.8500
C4—C51.378 (9)O2W—H2WA0.8501
C4—C81.509 (10)O3W—H3WA0.8565
C5—C61.386 (10)O3W—H3WB0.8575
C16—N4—C17105.2 (8)N1—C9—H9125.7
C16—N4—Zn1i125.7 (7)C9—C10—N2107.9 (10)
C17—N4—Zn1i128.4 (5)C9—C10—H10126.1
O1—Zn1—O3ii106.8 (2)N2—C10—H10126.1
O1—Zn1—N4iii110.5 (2)N2—C11—N1112.4 (10)
O3ii—Zn1—N4iii119.0 (3)N2—C11—H11123.8
O1—Zn1—N1100.6 (2)N1—C11—H11123.8
O3ii—Zn1—N1108.2 (2)C13—C12—N2113.7 (10)
N4iii—Zn1—N1110.1 (3)C13—C12—H12A108.8
C1—O1—Zn1124.8 (5)N2—C12—H12A108.8
C8—O3—Zn1iv112.2 (5)C13—C12—H12B108.8
C11—N1—C9105.5 (8)N2—C12—H12B108.8
C11—N1—Zn1128.1 (7)H12A—C12—H12B107.7
C9—N1—Zn1126.4 (5)C12—C13—C14113.0 (9)
C11—N2—C10105.5 (8)C12—C13—H13A109.0
C11—N2—C12125.4 (12)C14—C13—H13A109.0
C10—N2—C12129.0 (11)C12—C13—H13B109.0
C18—N3—C16105.5 (8)C14—C13—H13B109.0
C18—N3—C15132.5 (12)H13A—C13—H13B107.8
C16—N3—C15122.0 (11)C15—C14—C13110.8 (9)
O2—C1—O1123.4 (6)C15—C14—H14A109.5
O2—C1—C2121.0 (7)C13—C14—H14A109.5
O1—C1—C2115.6 (7)C15—C14—H14B109.5
C3—C2—C7119.7 (6)C13—C14—H14B109.5
C3—C2—C1121.2 (6)H14A—C14—H14B108.1
C7—C2—C1119.1 (7)C14—C15—N3105.4 (11)
C2—C3—C4120.1 (6)C14—C15—H15A110.7
C2—C3—H3120.0N3—C15—H15A110.7
C4—C3—H3120.0C14—C15—H15B110.7
C5—C4—C3119.8 (6)N3—C15—H15B110.7
C5—C4—C8119.9 (6)H15A—C15—H15B108.8
C3—C4—C8120.2 (6)N4—C16—N3111.1 (9)
C4—C5—C6119.6 (6)N4—C16—H16124.4
C4—C5—H5120.2N3—C16—H16124.4
C6—C5—H5120.2C18—C17—N4109.2 (8)
C7—C6—C5121.0 (6)C18—C17—H17125.4
C7—C6—I1120.6 (5)N4—C17—H17125.4
C5—C6—I1118.4 (5)C17—C18—N3108.3 (10)
C6—C7—C2119.8 (7)C17—C18—H18125.8
C6—C7—H7120.1N3—C18—H18125.8
C2—C7—H7120.1O1W—O1W—H1WA0.0
O4—C8—O3124.1 (7)O1W—O1W—H1WB0.0
O4—C8—C4119.5 (6)H1WA—O1W—H1WB107.8
O3—C8—C4116.3 (6)H2WB—O2W—H2WA108.2
C10—C9—N1108.6 (9)H3WA—O3W—H3WB108.1
C10—C9—H9125.7
Symmetry codes: (i) x+1, y1/2, 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, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O2v0.852.042.848 (15)160
O1W—H1WB···O3vi0.852.152.959 (13)159
O2W—H2WB···O1W0.851.782.63 (2)174
O2W—H2WA···O4ii0.851.952.796 (16)175
O3W—H3WA···O3Wvii0.862.452.91 (7)115
Symmetry codes: (ii) x, y+3/2, z+1/2; (v) x1, y, z; (vi) x1, y+3/2, z+1/2; (vii) x+1, y+2, z+1.

Experimental details

(1)(2)
Crystal data
Chemical formula[Co(C8H3IO4)(C10H14N4)][Zn(C8H3IO4)(C10H14N4)]·3H2O
Mr539.19599.67
Crystal system, space groupOrthorhombic, PbcaMonoclinic, P21/c
Temperature (K)296293
a, b, c (Å)10.2561 (18), 17.088 (3), 22.205 (4)7.9910 (9), 17.8363 (19), 18.2004 (17)
α, β, γ (°)90, 90, 9090, 110.080 (4), 90
V3)3891.6 (12)2436.4 (4)
Z84
Radiation typeMo KαMo Kα
µ (mm1)2.502.32
Crystal size (mm)0.32 × 0.25 × 0.190.26 × 0.23 × 0.22
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Bruker APEXII CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Bruker, 2003)
Empirical (using intensity measurements)
(SADABS; Bruker, 2003)
Tmin, Tmax0.477, 0.6220.548, 0.644
No. of measured, independent and
observed [I > 2σ(I)] reflections
32053, 4459, 2854 20965, 5573, 2767
Rint0.0710.067
(sin θ/λ)max1)0.6510.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.090, 1.03 0.065, 0.216, 0.97
No. of reflections44595573
No. of parameters253275
No. of restraints061
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.60, 1.080.84, 0.69

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), publCIF (Westrip, 2010).

Selected geometric parameters (Å, º) for (1) top
Co1—O12.053 (2)Co1—O3iii2.195 (2)
Co1—N12.102 (3)N4—Co1iv2.150 (3)
Co1—O2i2.137 (2)O4—Co1v2.186 (2)
Co1—N4ii2.150 (3)O3—Co1v2.195 (2)
Co1—O4iii2.186 (2)O2—Co1i2.137 (2)
O1—Co1—O2i90.27 (9)O2i—Co1—O4iii84.66 (9)
N1—Co1—O2i95.01 (11)N4ii—Co1—O4iii89.15 (11)
O1—Co1—N4ii85.79 (10)O1—Co1—O3iii161.88 (9)
N1—Co1—N4ii92.95 (12)N1—Co1—O3iii93.62 (10)
O2i—Co1—N4ii171.75 (10)O2i—Co1—O3iii93.86 (9)
O1—Co1—O4iii102.74 (9)N4ii—Co1—O3iii87.75 (10)
N1—Co1—O4iii153.67 (11)O4iii—Co1—O3iii60.21 (9)
Symmetry codes: (i) x+1, y+2, z+2; (ii) x, y+3/2, z+1/2; (iii) x1, y, z; (iv) x, y+3/2, z1/2; (v) x+1, y, z.
Selected geometric parameters (Å, º) for (2) top
N4—Zn1i1.988 (6)Zn1—N4iii1.988 (6)
Zn1—O11.932 (5)Zn1—N12.009 (7)
Zn1—O3ii1.968 (5)O3—Zn1iv1.968 (5)
O1—Zn1—O3ii106.8 (2)O1—Zn1—N1100.6 (2)
O1—Zn1—N4iii110.5 (2)O3ii—Zn1—N1108.2 (2)
O3ii—Zn1—N4iii119.0 (3)N4iii—Zn1—N1110.1 (3)
Symmetry codes: (i) x+1, y1/2, 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, z1/2.
Hydrogen-bond geometry (Å, º) for (2) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O2v0.852.042.848 (15)159.6
O1W—H1WB···O3vi0.852.152.959 (13)158.7
O2W—H2WB···O1W0.851.782.63 (2)173.6
O2W—H2WA···O4ii0.851.952.796 (16)175.3
O3W—H3WA···O3Wvii0.862.452.91 (7)114.9
Symmetry codes: (ii) x, y+3/2, z+1/2; (v) x1, y, z; (vi) x1, y+3/2, z+1/2; (vii) x+1, y+2, z+1.
 

Subscribe to Acta Crystallographica Section C: Structural Chemistry

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds