Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615021221/yf3096sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615021221/yf3096Isup2.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2053229615021221/yf3096sup3.pdf |
CCDC reference: 1057977
In recent decades, increasing attention has been paid to the design and preparation of crystalline polymeric materials not only due to their aesthetic structural beauty but also in view of their diverse applications as functional materials in gas storage, separation, catalysis, sensing and photoluminescence (Perman et al., 2011; Long & Yaghi, 2009; Agarwal et al., 2014; Eddaoudi et al., 2015; Weng et al., 2011). Compared to conventional inorganic materials, the functionality of coordination polymers can be tuned through variation of the organic linkers, reaction conditions etc. For example, tunable photoluminescence via charge transfer between the ligands and metal atoms can be achieved by incorporating ancillary organic bridges into the coordination frameworks (Aakeroy et al., 2007; Zhang et al., 2008; Calderone et al., 2013). In this sense, the judicious selection of organic linkers is critical for varying the coordination behaviour of the metal ions and determining the overall characteristics of the networks. Among the diverse types of ligands adopted to construct metal–organic frameworks (MOFs), rigid polycarboxylate ligands are particularly well placed due to their robustness and the affinity for transition metal ions (Cong et al., 2011; Zhao et al., 2009; Rancan & Armelao, 2015; Luebke et al., 2012). Along this line, numerous MOFs with desired size of pores, enhanced luminescences and various architectures have been successfully constructed from aromatic (Abu-Youssef et al., 2008; Fabelo et al., 2008) or pyridine-based polycarboxylates (Li et al., 2009; Bo et al., 2009; Banerjee et al., 2011; Cepeda et al., 2011). Thiophene-2,5-dicarboxylic acid (H2tdc) may be considered as a rational candidate for the construction of functional materials, because it can serve as a sensitizing chromophore and as a multicarboxylate linker to impact the luminescence behaviour of the final product through ligand–metal charge transfer (LMCT) or π*→ n transition (Song et al., 2015; Erer et al., 2015; Chen et al., 2008; Xu et al., 2011; Tan et al., 2014). The strong coordination tendency of H2tdc towards transition metals and its diverse bridging abilities allow chemists to develop advanced functional materials with potential application for magnetism or luminescence.
With regard to the synthetic strategy, increasing attention is being paid to the grafting of nitrogen-containing organic linkers into carboxylate-bridged transition–metal networks. The structural diversity and property applications of multicarboxylate MOFs have been expanded by the incorporation of neutral tethering organodiimines or multitopic N-donor ligands like 4,4'-bipyridine (Montney et al., 2007; Kathalikkattil et al., 2011) and 5-aminotetrazolate (Panda et al., 2011; Liu et al., 2015; Seco et al., 2015; Liu et al., 2012). Likewise, adenine, an important nucleobase for biosystems, shows extremely versatile coordination modes and a broad variety of adenine complexes with different metal-ion binding patterns have been reported (Yang et al., 2009; González-Pérez et al., 2005; Mishra et al., 2010; Paul et al., 2010; El Bakkali et al., 2014). Recently, Rosseinsky and co-workers have been assembled a robust porous network with pyrazole-3,5-dicarboxylic acid and adenine ligands as coligands under hydrothermal conditions (Stylianou et al., 2011). Along this line, a ZnII compound, [Zn(tdc)(ade)], (1), based has been synthesized under hydrothermal conditions. The material shows a two-dimensional network topology with thiophene-2,5-dicarboxylate and adenine as structure-directing agents. The synthesis, structure, thermogravimetric and photoluminescence studies are discussed in detail below.
All chemicals were used as purchased without further purification. Elemental analysis (EA) for C, H and N was performed on a PerkinElmer 240 analyzer. Thermogaravimeric analyses were performed with a Shimadzu TGA-50H TG analyzer in the range of 303–1073 K under a nitrogen flow at a heating rate of 5 K min-1 for all measurements. FT–IR spectra were recorded on a PerkinElmer Spectrum 2000 spectrometer using KBr pellets in the range 4000–400 cm-1. The fluorescence measurement is conducted on a Shimadzu RF-5301PC Fluorescence spectrophotometer.
A mixture of Zn(NO3)2.6H2O (0.3 mmol, 0.0891 g), H2tdc (0.3 mmol, 0.0516 g), adenine (0.3 mmol, 0.0405 g) and H2O (8 ml) was sealed in a 23 ml Teflon-lined stainless steel vessel and heated to 423 K for 15 h, and then cooled to room temperature. Colourless crystals (63% yield, based on Zn) were obtained in pure phase, washed with ethanol and dried at room temperature. Elemental analysis calculated: C 35.71, H 1.63, N 18.94%; found: C 35.63, H 1.52, N 19.07%.
Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were positioned geometrically and constrained using the riding-model approximation, with C—H = 0.93 Å (aromatic) and N—H = 0.86 Å. All H atoms were refined with Uiso(H) = 1.2Ueq(C,N).
As shown in Fig. 1, the asymmetric unit of complex (1) consists of one ZnII ion, one thiophene-2,5-dicarboxylate (tdc2-) ligand and one adenine (ade) molecule. The central ZnII ions have a slightly distorted tetrahedral geometry formed by two tdc2- carboxylate O atoms (O2 and O4) and two ade N atoms (N1 and N7). The Zn—O and Zn—N bond lengths are in agreement with those previously reported for other H2tdc- or ade-containing ZnII complexes (Sapchenko et al., 2013). The O/N—Zn—O/N angles are in the range 98.76 (19)–129.3 (2)°. The neutral adenine is bound to the central ZnII atom through the N1 and N7 sites, which is quite unique. A search of the Cambridge Structural Database (CSD, Version 5.34, Groom & Allen, 2014) shows that only one case has such a µ-N1,N7-coordination mode among all known adenine-based coordination polymers. The tdc2- ligand adopts a single bis-monodentate mode connecting two Zn2+ ions. Thus, the ZnII ions are linked alternatively via the bidentate ade and bis-monodentate tdc2- ligands along both the a and b axes, giving rise to a two-dimensional (4,4) grid sheet parallel to the ab plane, featuring two distinct square cavities delimited by two ligands and the ZnII ions with dimensions of about 6.6 × 6.6 and 10.2 × 10.2 Å2 (based on the Zn···Zn distances), respectively (Fig. 2).
As depicted in Fig. 3, the neighbouring two-dimensional planes are stacked together in such a way that the adenine molecules are protruding into the interior void space of the cavity enclosed by the tdc2- ligands and central ZnII ions within adjacent layers, giving rise to π–π stacking interactions between thiophene rings and imidazole/pyrimidine rings, with centroid–centroid distances of 3.908(?) and 3.723(?) Å. In addition, the architecture is reinforced by the extensive hydrogen-bonding interactions between the uncoordinated N atoms and the carboxylate O atoms. The N3 atom acts as an acceptor of hydrogen-bond interactions established with the N9 atom of the other nucleobase molecule. And the N6-amine site of the Watson–Crick face completes its hydrogen-bonding interaction with two carboxylate O atoms (O1 and O4) of the tdc2- ligands by an intramolecular linkage. The hydrogen-bonding parameters are tabulated in Table 2.
The thermogravimetric analysis (TGA) measurements were carried out in the range 303–973 K in order to estimate the thermal stabilities of the complex. As depicted in Fig. 4, the frameworks of complex (1) is thermally robust and persistent to at least 663 K; after that, (1) starts to decompose.
The emission spectra of complex (1) in the solid state at room temperature are depicted in Fig. 5. Complex (1) displays fluorescent emission bands at ca 388 and 405 nm upon excitation at ca 378 nm. According to the literature, free H2tdc displays emission peaks at 369 and 477 nm (Gong et al., 2007), while the strongest emission peak of adenine is at 420 nm (Chen et al., 2008). Since ZnII is difficult to oxidize or reduce due to the d10 configuration, these peaks can probably be assigned to the intraligand fluorescent emission (Wen et al., 2007). Compared with the emission behaviour of free H2tdc and adenine, the enhancement of fluorescence in (1) may be attributed to the coordination of H2tdc or ade to the metal centre, which effectively increases the rigidity of the ligands and reduce energy loss by radiation decay of intraligand excited states.
In conclusion, a new extended nucleobase ZnII coordination polymer was synthesized using thiophene-2,5-dicarboxylate and adenine as coligands. The title compound exhibits the packing of two-dimensional (4,4) grid sheets parallel to the ab plane, featuring two distinct square cavities delimited by two ligands and the ZnII ions. The photoluminescence measurement reveals that the fluorescence intensities of complexes (1) are enhanced compared to free H2tdc and adenine, suggesting that the increases in the rigidity of the ligands reduce energy loss by radiation decay of intraligand excited states.
Data collection: SMART (Bruker, 2012); cell refinement: SMART (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
[Zn(C6H2O4S)(C5H5N5)] | Melting point: 663 K |
Mr = 370.65 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P421c | Cell parameters from 9871 reflections |
a = 16.7143 (4) Å | θ = 3.3–27.5° |
c = 9.4518 (5) Å | µ = 2.05 mm−1 |
V = 2640.53 (17) Å3 | T = 296 K |
Z = 8 | Block, colorless |
F(000) = 1488 | 0.20 × 0.20 × 0.20 mm |
Dx = 1.865 Mg m−3 |
Bruker SMART CCD area-detector diffractometer | 3035 independent reflections |
Radiation source: fine-focus sealed tube | 2618 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
phi and ω scans | θmax = 27.6°, θmin = 3.3° |
Absorption correction: multi-scan | h = −21→21 |
Tmin = 0.685, Tmax = 0.685 | k = −21→21 |
38166 measured reflections | l = −11→12 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.064 | w = 1/[σ2(Fo2) + (0.1323P)2 + 1.1847P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.186 | (Δ/σ)max < 0.001 |
S = 1.14 | Δρmax = 1.70 e Å−3 |
3035 reflections | Δρmin = −1.00 e Å−3 |
200 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0031 (12) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 1322 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.05 (2) |
[Zn(C6H2O4S)(C5H5N5)] | Z = 8 |
Mr = 370.65 | Mo Kα radiation |
Tetragonal, P421c | µ = 2.05 mm−1 |
a = 16.7143 (4) Å | T = 296 K |
c = 9.4518 (5) Å | 0.20 × 0.20 × 0.20 mm |
V = 2640.53 (17) Å3 |
Bruker SMART CCD area-detector diffractometer | 3035 independent reflections |
Absorption correction: multi-scan | 2618 reflections with I > 2σ(I) |
Tmin = 0.685, Tmax = 0.685 | Rint = 0.039 |
38166 measured reflections |
R[F2 > 2σ(F2)] = 0.064 | H-atom parameters constrained |
wR(F2) = 0.186 | Δρmax = 1.70 e Å−3 |
S = 1.14 | Δρmin = −1.00 e Å−3 |
3035 reflections | Absolute structure: Flack (1983), 1322 Friedel pairs |
200 parameters | Absolute structure parameter: 0.05 (2) |
0 restraints |
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 | ||
N3 | 0.9483 (3) | 0.8798 (3) | 0.3437 (5) | 0.0506 (12) | |
C2 | 0.8976 (4) | 0.8528 (4) | 0.2483 (6) | 0.0489 (13) | |
H2 | 0.8435 | 0.8569 | 0.2698 | 0.059* | |
C4 | 1.0257 (3) | 0.8717 (3) | 0.3028 (6) | 0.0435 (12) | |
C5 | 1.0522 (3) | 0.8396 (3) | 0.1756 (6) | 0.0428 (11) | |
C6 | 0.9955 (4) | 0.8104 (3) | 0.0811 (6) | 0.0443 (12) | |
C8 | 1.1564 (4) | 0.8705 (4) | 0.2971 (7) | 0.0487 (13) | |
H8 | 1.2092 | 0.8772 | 0.3258 | 0.058* | |
C10 | 0.8618 (5) | 0.6398 (4) | −0.1096 (8) | 0.0620 (17) | |
C11 | 0.8578 (4) | 0.5521 (4) | −0.1281 (8) | 0.0538 (14) | |
C12 | 0.8917 (5) | 0.5063 (4) | −0.2308 (9) | 0.069 (2) | |
H12 | 0.9209 | 0.5270 | −0.3061 | 0.083* | |
C13 | 0.8775 (5) | 0.4241 (4) | −0.2108 (8) | 0.0666 (19) | |
H13 | 0.8972 | 0.3844 | −0.2703 | 0.080* | |
C14 | 0.8313 (4) | 0.4089 (3) | −0.0939 (7) | 0.0498 (13) | |
C15 | 0.6674 (3) | 0.8045 (3) | 0.0350 (6) | 0.0444 (11) | |
N1 | 0.9166 (3) | 0.8196 (3) | 0.1218 (5) | 0.0456 (10) | |
N6 | 1.0117 (3) | 0.7750 (4) | −0.0411 (5) | 0.0537 (12) | |
H6A | 0.9734 | 0.7581 | −0.0939 | 0.080* | |
H6B | 1.0606 | 0.7690 | −0.0675 | 0.080* | |
N7 | 1.1353 (3) | 0.8406 (3) | 0.1742 (6) | 0.0452 (11) | |
N9 | 1.0915 (3) | 0.8907 (3) | 0.3779 (6) | 0.0520 (11) | |
H9 | 1.0925 | 0.9117 | 0.4610 | 0.062* | |
O1 | 0.9052 (5) | 0.6800 (3) | −0.1897 (7) | 0.0798 (16) | |
O2 | 0.8192 (3) | 0.6689 (3) | −0.0130 (6) | 0.0662 (12) | |
O3 | 0.6681 (3) | 0.7615 (4) | −0.0685 (6) | 0.0710 (14) | |
O4 | 0.7313 (2) | 0.8286 (3) | 0.0970 (5) | 0.0488 (9) | |
S1 | 0.80772 (9) | 0.49544 (8) | −0.00596 (19) | 0.0515 (3) | |
Zn1 | 0.82162 (3) | 0.78509 (3) | −0.00973 (8) | 0.0420 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N3 | 0.043 (2) | 0.062 (3) | 0.047 (3) | −0.001 (2) | 0.008 (2) | −0.001 (2) |
C2 | 0.047 (3) | 0.055 (3) | 0.044 (3) | 0.001 (3) | −0.001 (2) | −0.003 (2) |
C4 | 0.047 (3) | 0.046 (3) | 0.038 (3) | −0.001 (2) | 0.003 (2) | −0.002 (2) |
C5 | 0.040 (3) | 0.044 (3) | 0.045 (3) | 0.001 (2) | 0.001 (2) | −0.001 (2) |
C6 | 0.044 (3) | 0.046 (3) | 0.043 (3) | −0.004 (2) | −0.005 (2) | −0.004 (2) |
C8 | 0.046 (3) | 0.054 (3) | 0.047 (3) | −0.004 (3) | 0.003 (2) | −0.008 (2) |
C10 | 0.067 (4) | 0.043 (3) | 0.076 (4) | 0.000 (3) | −0.018 (4) | 0.006 (3) |
C11 | 0.058 (3) | 0.042 (3) | 0.062 (4) | 0.004 (3) | −0.004 (3) | 0.006 (3) |
C12 | 0.087 (5) | 0.048 (3) | 0.074 (5) | 0.002 (4) | 0.022 (4) | 0.007 (3) |
C13 | 0.088 (5) | 0.043 (3) | 0.068 (4) | 0.002 (3) | 0.020 (4) | −0.007 (3) |
C14 | 0.055 (3) | 0.038 (3) | 0.056 (3) | −0.003 (2) | 0.003 (3) | 0.000 (2) |
C15 | 0.043 (3) | 0.045 (3) | 0.044 (3) | 0.000 (2) | 0.001 (2) | −0.003 (2) |
N1 | 0.039 (2) | 0.060 (3) | 0.038 (2) | −0.003 (2) | 0.0025 (17) | −0.004 (2) |
N6 | 0.043 (3) | 0.069 (3) | 0.049 (2) | −0.004 (2) | 0.002 (2) | −0.013 (2) |
N7 | 0.033 (2) | 0.047 (2) | 0.055 (3) | −0.0016 (18) | 0.0054 (19) | −0.001 (2) |
N9 | 0.044 (2) | 0.060 (3) | 0.051 (3) | 0.002 (2) | 0.004 (2) | −0.002 (2) |
O1 | 0.109 (5) | 0.048 (3) | 0.082 (4) | −0.015 (3) | −0.006 (3) | 0.010 (2) |
O2 | 0.071 (3) | 0.0369 (19) | 0.091 (4) | 0.0049 (17) | 0.005 (3) | 0.000 (3) |
O3 | 0.064 (3) | 0.079 (3) | 0.070 (3) | 0.013 (3) | −0.004 (2) | −0.023 (3) |
O4 | 0.0337 (18) | 0.054 (2) | 0.059 (2) | −0.0004 (16) | 0.0040 (17) | −0.0027 (19) |
S1 | 0.0552 (7) | 0.0382 (6) | 0.0611 (8) | 0.0037 (5) | 0.0033 (7) | −0.0041 (7) |
Zn1 | 0.0386 (3) | 0.0366 (3) | 0.0508 (4) | 0.00110 (19) | 0.0034 (3) | −0.0003 (3) |
N3—C2 | 1.317 (8) | C12—C13 | 1.407 (10) |
N3—C4 | 1.357 (8) | C12—H12 | 0.9300 |
C2—N1 | 1.355 (7) | C13—C14 | 1.372 (10) |
C2—H2 | 0.9300 | C13—H13 | 0.9300 |
C4—N9 | 1.346 (8) | C14—C15i | 1.461 (8) |
C4—C5 | 1.389 (8) | C14—S1 | 1.715 (6) |
C5—N7 | 1.389 (7) | C15—O3 | 1.213 (8) |
C5—C6 | 1.391 (8) | C15—O4 | 1.283 (7) |
C6—N6 | 1.325 (7) | C15—C14ii | 1.461 (8) |
C6—N1 | 1.382 (7) | N1—Zn1 | 2.098 (5) |
C8—N7 | 1.313 (8) | N6—H6A | 0.8600 |
C8—N9 | 1.370 (8) | N6—H6B | 0.8600 |
C8—H8 | 0.9300 | N7—Zn1iii | 2.071 (5) |
C10—O1 | 1.245 (10) | N9—H9 | 0.8600 |
C10—O2 | 1.256 (9) | O2—Zn1 | 1.942 (4) |
C10—C11 | 1.477 (9) | O4—Zn1 | 1.957 (4) |
C11—C12 | 1.360 (10) | Zn1—N7iv | 2.071 (5) |
C11—S1 | 1.712 (7) | ||
C2—N3—C4 | 112.6 (5) | C13—C14—C15i | 129.9 (6) |
N3—C2—N1 | 126.4 (6) | C13—C14—S1 | 111.3 (4) |
N3—C2—H2 | 116.8 | C15i—C14—S1 | 118.8 (5) |
N1—C2—H2 | 116.8 | O3—C15—O4 | 123.1 (6) |
N9—C4—N3 | 127.2 (5) | O3—C15—C14ii | 119.8 (6) |
N9—C4—C5 | 106.7 (5) | O4—C15—C14ii | 117.1 (5) |
N3—C4—C5 | 126.1 (5) | C2—N1—C6 | 121.0 (5) |
N7—C5—C4 | 108.8 (5) | C2—N1—Zn1 | 117.3 (4) |
N7—C5—C6 | 132.8 (6) | C6—N1—Zn1 | 121.7 (4) |
C4—C5—C6 | 118.3 (5) | C6—N6—H6A | 120.0 |
N6—C6—N1 | 119.2 (5) | C6—N6—H6B | 120.0 |
N6—C6—C5 | 125.2 (6) | H6A—N6—H6B | 120.0 |
N1—C6—C5 | 115.6 (5) | C8—N7—C5 | 105.4 (5) |
N7—C8—N9 | 112.0 (6) | C8—N7—Zn1iii | 123.3 (4) |
N7—C8—H8 | 124.0 | C5—N7—Zn1iii | 130.4 (4) |
N9—C8—H8 | 124.0 | C4—N9—C8 | 107.1 (5) |
O1—C10—O2 | 124.3 (6) | C4—N9—H9 | 126.4 |
O1—C10—C11 | 119.3 (7) | C8—N9—H9 | 126.4 |
O2—C10—C11 | 116.4 (7) | C10—O2—Zn1 | 112.8 (5) |
C12—C11—C10 | 128.7 (7) | C15—O4—Zn1 | 106.8 (4) |
C12—C11—S1 | 111.9 (5) | C11—S1—C14 | 91.6 (3) |
C10—C11—S1 | 119.4 (6) | O2—Zn1—O4 | 111.4 (2) |
C11—C12—C13 | 112.6 (7) | O2—Zn1—N7iv | 129.3 (2) |
C11—C12—H12 | 123.7 | O4—Zn1—N7iv | 105.42 (19) |
C13—C12—H12 | 123.7 | O2—Zn1—N1 | 107.5 (2) |
C14—C13—C12 | 112.6 (6) | O4—Zn1—N1 | 100.16 (18) |
C14—C13—H13 | 123.7 | N7iv—Zn1—N1 | 98.76 (19) |
C12—C13—H13 | 123.7 | ||
C4—N3—C2—N1 | 0.3 (9) | C4—C5—N7—C8 | 1.3 (7) |
C2—N3—C4—N9 | −177.5 (6) | C6—C5—N7—C8 | −175.2 (6) |
C2—N3—C4—C5 | 0.5 (9) | C4—C5—N7—Zn1iii | −167.8 (4) |
N9—C4—C5—N7 | −0.8 (7) | C6—C5—N7—Zn1iii | 15.7 (10) |
N3—C4—C5—N7 | −179.1 (6) | N3—C4—N9—C8 | 178.3 (6) |
N9—C4—C5—C6 | 176.3 (5) | C5—C4—N9—C8 | 0.0 (7) |
N3—C4—C5—C6 | −2.0 (9) | N7—C8—N9—C4 | 0.8 (8) |
N7—C5—C6—N6 | −0.6 (11) | O1—C10—O2—Zn1 | 4.3 (9) |
C4—C5—C6—N6 | −176.9 (6) | C11—C10—O2—Zn1 | −174.7 (5) |
N7—C5—C6—N1 | 178.9 (6) | O3—C15—O4—Zn1 | 1.1 (8) |
C4—C5—C6—N1 | 2.6 (8) | C14ii—C15—O4—Zn1 | −178.5 (5) |
O1—C10—C11—C12 | −5.4 (13) | C12—C11—S1—C14 | −0.5 (6) |
O2—C10—C11—C12 | 173.7 (8) | C10—C11—S1—C14 | −178.7 (6) |
O1—C10—C11—S1 | 172.4 (6) | C13—C14—S1—C11 | 1.3 (6) |
O2—C10—C11—S1 | −8.5 (9) | C15i—C14—S1—C11 | 178.7 (6) |
C10—C11—C12—C13 | 177.6 (8) | C10—O2—Zn1—O4 | 161.7 (5) |
S1—C11—C12—C13 | −0.3 (10) | C10—O2—Zn1—N7iv | 28.1 (6) |
C11—C12—C13—C14 | 1.3 (12) | C10—O2—Zn1—N1 | −89.5 (5) |
C12—C13—C14—C15i | −178.7 (7) | C15—O4—Zn1—O2 | −60.0 (4) |
C12—C13—C14—S1 | −1.7 (10) | C15—O4—Zn1—N7iv | 84.4 (4) |
N3—C2—N1—C6 | 0.5 (10) | C15—O4—Zn1—N1 | −173.5 (4) |
N3—C2—N1—Zn1 | −178.4 (5) | C2—N1—Zn1—O2 | −109.4 (5) |
N6—C6—N1—C2 | 177.5 (6) | C6—N1—Zn1—O2 | 71.8 (5) |
C5—C6—N1—C2 | −2.0 (8) | C2—N1—Zn1—O4 | 7.0 (5) |
N6—C6—N1—Zn1 | −3.6 (8) | C6—N1—Zn1—O4 | −171.8 (4) |
C5—C6—N1—Zn1 | 176.8 (4) | C2—N1—Zn1—N7iv | 114.5 (5) |
N9—C8—N7—C5 | −1.3 (7) | C6—N1—Zn1—N7iv | −64.3 (5) |
N9—C8—N7—Zn1iii | 168.8 (4) |
Symmetry codes: (i) y, −x+1, −z; (ii) −y+1, x, −z; (iii) −y+2, x, −z; (iv) y, −x+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6A···O1 | 0.86 | 1.96 | 2.770 (8) | 157 |
N6—H6B···O4iii | 0.86 | 1.98 | 2.816 (7) | 166 |
N9—H9···N3v | 0.86 | 2.00 | 2.843 (8) | 167 |
Symmetry codes: (iii) −y+2, x, −z; (v) −y+2, x, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C6H2O4S)(C5H5N5)] |
Mr | 370.65 |
Crystal system, space group | Tetragonal, P421c |
Temperature (K) | 296 |
a, c (Å) | 16.7143 (4), 9.4518 (5) |
V (Å3) | 2640.53 (17) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 2.05 |
Crystal size (mm) | 0.20 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan |
Tmin, Tmax | 0.685, 0.685 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 38166, 3035, 2618 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.064, 0.186, 1.14 |
No. of reflections | 3035 |
No. of parameters | 200 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.70, −1.00 |
Absolute structure | Flack (1983), 1322 Friedel pairs |
Absolute structure parameter | 0.05 (2) |
Computer programs: SMART (Bruker, 2012), SAINT (Bruker, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6A···O1 | 0.86 | 1.96 | 2.770 (8) | 157.3 |
N6—H6B···O4i | 0.86 | 1.98 | 2.816 (7) | 165.6 |
N9—H9···N3ii | 0.86 | 2.00 | 2.843 (8) | 166.5 |
Symmetry codes: (i) −y+2, x, −z; (ii) −y+2, x, −z+1. |