Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615014655/ly3018sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615014655/ly30181sup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615014655/ly30182sup3.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2053229615014655/ly3018sup4.pdf |
CCDC references: 832842; 832839
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 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 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.
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).
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).
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).
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).
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,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-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).
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.
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.
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 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 d–d 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.
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 π–π* transition of the bimb and iip2- ligands (Ge et al., 2015).
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.
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).
[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) Å3 | Block, purple |
Z = 8 | 0.32 × 0.25 × 0.19 mm |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.090 | H-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 parameters | Δρmax = 0.60 e Å−3 |
0 restraints | Δρmin = −1.08 e Å−3 |
[Co(C8H3IO4)(C10H14N4)] | V = 3891.6 (12) Å3 |
Mr = 539.19 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 10.2561 (18) Å | µ = 2.50 mm−1 |
b = 17.088 (3) Å | T = 296 K |
c = 22.205 (4) Å | 0.32 × 0.25 × 0.19 mm |
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 = 0.622 | Rint = 0.071 |
32053 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.60 e Å−3 |
4459 reflections | Δρmin = −1.08 e Å−3 |
253 parameters |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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—O2i | 2.137 (2) |
C10—N1 | 1.373 (5) | Co1—N4ii | 2.150 (3) |
C10—H10 | 0.9300 | Co1—O4iii | 2.186 (2) |
C11—N2 | 1.361 (5) | Co1—O3iii | 2.195 (2) |
C11—H11 | 0.9300 | N4—Co1iv | 2.150 (3) |
C12—N2 | 1.474 (5) | O4—Co1v | 2.186 (2) |
C12—C13 | 1.520 (5) | O3—Co1v | 2.195 (2) |
C12—H12A | 0.9700 | O2—Co1i | 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—O2i | 90.27 (9) |
O4—C7—C3 | 119.0 (3) | N1—Co1—O2i | 95.01 (11) |
O3—C7—C3 | 119.3 (3) | O1—Co1—N4ii | 85.79 (10) |
O2—C8—O1 | 125.9 (3) | N1—Co1—N4ii | 92.95 (12) |
O2—C8—C5 | 118.8 (3) | O2i—Co1—N4ii | 171.75 (10) |
O1—C8—C5 | 115.3 (3) | O1—Co1—O4iii | 102.74 (9) |
N1—C9—N2 | 111.8 (3) | N1—Co1—O4iii | 153.67 (11) |
N1—C9—H9 | 124.1 | O2i—Co1—O4iii | 84.66 (9) |
N2—C9—H9 | 124.1 | N4ii—Co1—O4iii | 89.15 (11) |
C11—C10—N1 | 109.9 (4) | O1—Co1—O3iii | 161.88 (9) |
C11—C10—H10 | 125.1 | N1—Co1—O3iii | 93.62 (10) |
N1—C10—H10 | 125.1 | O2i—Co1—O3iii | 93.86 (9) |
C10—C11—N2 | 106.3 (4) | N4ii—Co1—O3iii | 87.75 (10) |
C10—C11—H11 | 126.9 | O4iii—Co1—O3iii | 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—Co1iv | 124.3 (3) |
C14—C13—H13B | 109.8 | C18—N4—Co1iv | 130.1 (3) |
H13A—C13—H13B | 108.2 | C7—O4—Co1v | 89.1 (2) |
C13—C14—C15 | 114.7 (4) | C7—O3—Co1v | 88.6 (2) |
C13—C14—H14A | 108.6 | C8—O1—Co1 | 128.9 (2) |
C15—C14—H14A | 108.6 | C8—O2—Co1i | 130.6 (2) |
C13—C14—H14B | 108.6 | ||
C6—C1—C2—C3 | −1.8 (6) | O2i—Co1—N1—C10 | −146.9 (3) |
I1—C1—C2—C3 | 178.7 (2) | N4ii—Co1—N1—C10 | 35.2 (3) |
C1—C2—C3—C4 | 3.0 (5) | O4iii—Co1—N1—C10 | −58.8 (4) |
C1—C2—C3—C7 | −179.2 (3) | O3iii—Co1—N1—C10 | −52.7 (3) |
C2—C3—C4—C5 | −1.6 (5) | C7iii—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—Co1iv | 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—Co1iv | −174.2 (3) |
N2—C12—C13—C14 | −173.9 (4) | O3—C7—O4—Co1v | −5.7 (3) |
C12—C13—C14—C15 | −172.4 (4) | C3—C7—O4—Co1v | 173.4 (3) |
C13—C14—C15—N3 | −68.0 (5) | O4—C7—O3—Co1v | 5.7 (3) |
N3—C17—C18—N4 | −0.2 (5) | C3—C7—O3—Co1v | −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) | O2i—Co1—O1—C8 | −52.8 (3) |
O1—Co1—N1—C9 | −56.2 (4) | N4ii—Co1—O1—C8 | 134.4 (3) |
O2i—Co1—N1—C9 | 35.3 (3) | O4iii—Co1—O1—C8 | −137.4 (3) |
N4ii—Co1—N1—C9 | −142.5 (3) | O3iii—Co1—O1—C8 | −156.2 (3) |
O4iii—Co1—N1—C9 | 123.4 (3) | O1—C8—O2—Co1i | 98.0 (4) |
O3iii—Co1—N1—C9 | 129.5 (3) | C5—C8—O2—Co1i | −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. |
[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) Å3 | 0.26 × 0.23 × 0.22 mm |
Z = 4 |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.216 | H-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 parameters | Δρmax = 0.84 e Å−3 |
61 restraints | Δρmin = −0.69 e Å−3 |
[Zn(C8H3IO4)(C10H14N4)]·3H2O | V = 2436.4 (4) Å3 |
Mr = 599.67 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.9910 (9) Å | µ = 2.32 mm−1 |
b = 17.8363 (19) Å | T = 293 K |
c = 18.2004 (17) Å | 0.26 × 0.23 × 0.22 mm |
β = 110.080 (4)° |
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 = 0.644 | Rint = 0.067 |
20965 measured reflections |
R[F2 > 2σ(F2)] = 0.065 | 61 restraints |
wR(F2) = 0.216 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.84 e Å−3 |
5573 reflections | Δρmin = −0.69 e Å−3 |
275 parameters |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
N4—C16 | 1.324 (11) | C5—H5 | 0.9300 |
N4—C17 | 1.360 (10) | C6—C7 | 1.367 (9) |
N4—Zn1i | 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—O3ii | 1.968 (5) | C10—H10 | 0.9300 |
Zn1—N4iii | 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—Zn1iv | 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—Zn1i | 125.7 (7) | C9—C10—N2 | 107.9 (10) |
C17—N4—Zn1i | 128.4 (5) | C9—C10—H10 | 126.1 |
O1—Zn1—O3ii | 106.8 (2) | N2—C10—H10 | 126.1 |
O1—Zn1—N4iii | 110.5 (2) | N2—C11—N1 | 112.4 (10) |
O3ii—Zn1—N4iii | 119.0 (3) | N2—C11—H11 | 123.8 |
O1—Zn1—N1 | 100.6 (2) | N1—C11—H11 | 123.8 |
O3ii—Zn1—N1 | 108.2 (2) | C13—C12—N2 | 113.7 (10) |
N4iii—Zn1—N1 | 110.1 (3) | C13—C12—H12A | 108.8 |
C1—O1—Zn1 | 124.8 (5) | N2—C12—H12A | 108.8 |
C8—O3—Zn1iv | 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. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O2v | 0.85 | 2.04 | 2.848 (15) | 160 |
O1W—H1WB···O3vi | 0.85 | 2.15 | 2.959 (13) | 159 |
O2W—H2WB···O1W | 0.85 | 1.78 | 2.63 (2) | 174 |
O2W—H2WA···O4ii | 0.85 | 1.95 | 2.796 (16) | 175 |
O3W—H3WA···O3Wvii | 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. |
Experimental details
(1) | (2) | |
Crystal data | ||
Chemical formula | [Co(C8H3IO4)(C10H14N4)] | [Zn(C8H3IO4)(C10H14N4)]·3H2O |
Mr | 539.19 | 599.67 |
Crystal system, space group | Orthorhombic, Pbca | Monoclinic, P21/c |
Temperature (K) | 296 | 293 |
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, 90 | 90, 110.080 (4), 90 |
V (Å3) | 3891.6 (12) | 2436.4 (4) |
Z | 8 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 2.50 | 2.32 |
Crystal size (mm) | 0.32 × 0.25 × 0.19 | 0.26 × 0.23 × 0.22 |
Data collection | ||
Diffractometer | Bruker APEXII CCD area-detector diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Bruker, 2003) | Empirical (using intensity measurements) (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.477, 0.622 | 0.548, 0.644 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32053, 4459, 2854 | 20965, 5573, 2767 |
Rint | 0.071 | 0.067 |
(sin θ/λ)max (Å−1) | 0.651 | 0.651 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.090, 1.03 | 0.065, 0.216, 0.97 |
No. of reflections | 4459 | 5573 |
No. of parameters | 253 | 275 |
No. of restraints | 0 | 61 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.60, −1.08 | 0.84, −0.69 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), publCIF (Westrip, 2010).
Co1—O1 | 2.053 (2) | Co1—O3iii | 2.195 (2) |
Co1—N1 | 2.102 (3) | N4—Co1iv | 2.150 (3) |
Co1—O2i | 2.137 (2) | O4—Co1v | 2.186 (2) |
Co1—N4ii | 2.150 (3) | O3—Co1v | 2.195 (2) |
Co1—O4iii | 2.186 (2) | O2—Co1i | 2.137 (2) |
O1—Co1—O2i | 90.27 (9) | O2i—Co1—O4iii | 84.66 (9) |
N1—Co1—O2i | 95.01 (11) | N4ii—Co1—O4iii | 89.15 (11) |
O1—Co1—N4ii | 85.79 (10) | O1—Co1—O3iii | 161.88 (9) |
N1—Co1—N4ii | 92.95 (12) | N1—Co1—O3iii | 93.62 (10) |
O2i—Co1—N4ii | 171.75 (10) | O2i—Co1—O3iii | 93.86 (9) |
O1—Co1—O4iii | 102.74 (9) | N4ii—Co1—O3iii | 87.75 (10) |
N1—Co1—O4iii | 153.67 (11) | O4iii—Co1—O3iii | 60.21 (9) |
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. |
N4—Zn1i | 1.988 (6) | Zn1—N4iii | 1.988 (6) |
Zn1—O1 | 1.932 (5) | Zn1—N1 | 2.009 (7) |
Zn1—O3ii | 1.968 (5) | O3—Zn1iv | 1.968 (5) |
O1—Zn1—O3ii | 106.8 (2) | O1—Zn1—N1 | 100.6 (2) |
O1—Zn1—N4iii | 110.5 (2) | O3ii—Zn1—N1 | 108.2 (2) |
O3ii—Zn1—N4iii | 119.0 (3) | N4iii—Zn1—N1 | 110.1 (3) |
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. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O2v | 0.85 | 2.04 | 2.848 (15) | 159.6 |
O1W—H1WB···O3vi | 0.85 | 2.15 | 2.959 (13) | 158.7 |
O2W—H2WB···O1W | 0.85 | 1.78 | 2.63 (2) | 173.6 |
O2W—H2WA···O4ii | 0.85 | 1.95 | 2.796 (16) | 175.3 |
O3W—H3WA···O3Wvii | 0.86 | 2.45 | 2.91 (7) | 114.9 |
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. |
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