Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616000516/wq3106sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616000516/wq3106Isup2.hkl |
CCDC reference: 1446355
Within the developing domain of crystal engineering, building block or modular assembly methodologies have shown great success in the design and construction of metal–organic coordination polymers (Li et al., 2013, 2014; Ma et al., 2012). The critical factor for the construction of coordination polymers is the rational choice of organic building block and metal centre. Accordingly, tectonic ligands with suitable functional groups and molecular backbones are the most pivotal in the structural regulation of coordination polymers (Zhang et al., 2009; Zang et al., 2009; Xu et al., 2014). At the same time, it has been well established by the successful syntheses of this class of materials that the combination of metal ions with N-based neutral ligands and carboxylate groups gives rise to a range of aggregates with interesting extended structures and functional properties (Tang et al., 2008; Liu et al., 2008; Xue et al., 2009). The introduction of a range of organic ligands into a reaction system provides further impetus for research on extended metal–organic coordination polymers. Yet, due to the susceptibility of the assembly process to many subtle factors, the construction of extended solids based on mixed ligands is still at an early stage, despite the fact that many examples have been documented (Tang et al., 2015; Lu et al., 2015; Wu et al., 2012). Thus, it is important to establish appropriate synthetic strategies and rules so that the desired metal–organic coordination polymers may be obtained from mixed ligands and metal ions. In this work, we report the synthesis and structure of [Zn(NBA)2(4,4'-bipy)]n (where 4,4'-bipy is 4,4'-bipyridine and NBA is 3-nitrobenzoate), (1), a one-dimensional zigzag chain linked by 4,4'-bipy ligands, and linked further through aromatic π–π stacking interactions, expanding the structure into a two-dimensional interpenetrating supramolecular architecture. Furthermore, the solid-state fluorescence properties of (1) have also been investigated.
Elemental analyses were performed on a PerkinElmer 2400 element analyzer. IR spectra were recorded on a Shimadzu FT–IR8400 spectrometer using a KBr pellet. A NETZSCH STA 449C thermogravimetric analyzer was used to perform the thermogravimetric analyses. X-ray powder diffraction (XRPD) was carried out on a Shimadzu XRD-7000 analyzer. The photoluminescence spectra were recorded on a Hitachi F-4500 fluorescence spectrophotometer at room temperature.
All reagents and solvents were commercially available and of analytical grade. A mixture of 3-nitrobenzoic acid (0.0344 g, 0.2 mmol), 4,4'-bipyridine (0.0156 g, 0.1 mmol), Zn(OAc)2·2H2O (0.0220 g, 0.1 mmol), CH3CH2OH (2 ml) and H2O (6 ml) was stirred evenly and heated in a 20 ml Teflon-lined autoclave at 433 K for 4 d, followed by slow cooling (5 K h-1) to room temperature. Colourless block-shaped crystals were collected (yield 54%, based on Zn).
Elemental analysis calculated for C24H16N4O8Zn (%): C 52.05, H 2.91, N 10.12; found: C 52.27, H 3.04, N 10.26. IR (KBr, cm-1): 1624 (s), 1531 (m), 1479 (w), 1404 (s), 1359 (m), 1263 (m), 1072 (w), 908 (w), 814 (w), 787 (m), 729 (m), 646 (w), 527 (w).
Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms bonded to C atoms were placed in calculated positions and treated using a riding-model approximation, with C–H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms.
Single-crystal X-ray diffraction analysis shows that complex (1) consists of one ZnII ion, two 3-nitrobenzoate (NBA) ligands and one 4,4'-bipyridine (4,4'-bipy) ligand. Each ZnII centre is six-coordinated by two pyridyl N-atom donors from two different 4,4'-bipy ligands and four O atoms from two different NBA anions [Zn—O = 1.906 (10)–2.597 (11) Å and Zn—N = 2.101 (2) and 2.093 (2) Å; Table 2], with a distorted ZnN2O4 trigonal prismatic geometry (Fig. 1). The O/N—Zn—O/N angles are in the range 56.2 (2)–139.7 (2)°. The Zn—O(carboxylate) and Zn—N(bipy) bond lengths are in agreement with those reported for other carboxylate- and bipy-containing zinc(II) complexes (Lu et al., 2015).
Adjacent ZnII ions are bridged by 4,4'-bipy ligands to form an infinite one-dimensional zigzag chain running along the c-axis direction, with a Zn···Zn separation of 11.241 Å (Fig. 2). Each NBA ligand adopts a bidentate (OCOO-) coordination mode and all the NBA ligands bristle out from the two sides of the one-dimensional zigzag chains; this orientation plays a major role in packing into a higher network. So, through aromatic π–π stacking interactions between the phenyl rings of NBA ligands (the interplanar spacing is 3.376 Å and the centroid-to-centroid distance is 3.967 Å), adjacent chains generate a two-dimensional layer, as shown in Fig. 3. Further, three such two-dimensional layers interpenetrate, resulting in a threefold interpenetrating two-dimensional network. (Fig. 4).
X-ray powder diffraction (PXRD) analysis was used to confirm the phase purity of the bulk materials of (1) at room temperature (Fig. 5). The experimental diffraction pattern of the bulk sample is consistent with the simulated patterns, indicating that the products are a homogeneous pure phases for (1). To examine the thermal stability of complex (1), thermogravimetric (TG) analyses were carried out for (1) between 293 and 973 K (Fig. 6). The samples were heated under a static air atmosphere with a heating rate of 10 K min-1. The TG curve indicates that no weight loss was observed until 493 K, above which temperature, significant weight loss occurred which was complete at about 683 K, indicating complete decomposition of the NBA and 4,4'-bipy ligands. The whole weight loss of (1) was in accordance with the expected value (observed 86.45%, calculated 86.74%). Analysis of the decomposition product of complex (1) indicates that the final residue is likely to be ZnO, which was further confirmed by examination of the PXRD patterns of this residue.
The IR spectra of complex (1) show absorption peaks at 1624 and 1531cm-1 which can be assigned to the asymmetric stretching vibrations of the carboxylate groups, while the absorption peaks at 1479 and 1404 cm-1 correspond to the symmetric stretching vibrations of the carboxylate groups. The separation values between νasym(CO2) and νsym(CO2) are 145 and 127 cm-1, consistent with the carboxylate group coordinating in a chelating bidentate fashion (Wu et al., 2010), which is in agreement with the X-ray analysis.
The luminescence properties of 4,4'-bipyridine and 3-nitrobenzoic acid (HNBA), and of complex (1) were investigated in the solid state at room temperature, as shown in Fig. 7. 4,4'-Bipyridine and HNBA both exhibit a broad emission band; the emission bands are observed at 418 nm (λex =348nm) for 4,4'-bipy and at 451 nm (λex =290nm) for HNBA at room temperature, while complex (1) displays an intense and sharp emission peak at 406 nm upon excitation at 300 nm. Complex (1) has a slight blue-shift compared with that of pure 4,4'-bipyridine and HNBA, but because d10 configurations are not easily susceptible to oxidiization/reduction, this shift is unlikely to be metal-to-ligand charge transfer (MLCT) nor ligand-to-metal charge transfer (LMCT) in nature. Therefore, the blue shift in complex (1) could be attributed to a change in energy levels (HOMO–LUMO; HOMO is the hight occupied molecular orbital and LUMO is the lowest unoccupied molecular orbital) of the carboxylate-based anionic and the neutral 4,4'-bipy ligands (Singh & Bharadwaj, 2013).
Within the developing domain of crystal engineering, building block or modular assembly methodologies have shown great success in the design and construction of metal–organic coordination polymers (Li et al., 2013, 2014; Ma et al., 2012). The critical factor for the construction of coordination polymers is the rational choice of organic building block and metal centre. Accordingly, tectonic ligands with suitable functional groups and molecular backbones are the most pivotal in the structural regulation of coordination polymers (Zhang et al., 2009; Zang et al., 2009; Xu et al., 2014). At the same time, it has been well established by the successful syntheses of this class of materials that the combination of metal ions with N-based neutral ligands and carboxylate groups gives rise to a range of aggregates with interesting extended structures and functional properties (Tang et al., 2008; Liu et al., 2008; Xue et al., 2009). The introduction of a range of organic ligands into a reaction system provides further impetus for research on extended metal–organic coordination polymers. Yet, due to the susceptibility of the assembly process to many subtle factors, the construction of extended solids based on mixed ligands is still at an early stage, despite the fact that many examples have been documented (Tang et al., 2015; Lu et al., 2015; Wu et al., 2012). Thus, it is important to establish appropriate synthetic strategies and rules so that the desired metal–organic coordination polymers may be obtained from mixed ligands and metal ions. In this work, we report the synthesis and structure of [Zn(NBA)2(4,4'-bipy)]n (where 4,4'-bipy is 4,4'-bipyridine and NBA is 3-nitrobenzoate), (1), a one-dimensional zigzag chain linked by 4,4'-bipy ligands, and linked further through aromatic π–π stacking interactions, expanding the structure into a two-dimensional interpenetrating supramolecular architecture. Furthermore, the solid-state fluorescence properties of (1) have also been investigated.
Elemental analyses were performed on a PerkinElmer 2400 element analyzer. IR spectra were recorded on a Shimadzu FT–IR8400 spectrometer using a KBr pellet. A NETZSCH STA 449C thermogravimetric analyzer was used to perform the thermogravimetric analyses. X-ray powder diffraction (XRPD) was carried out on a Shimadzu XRD-7000 analyzer. The photoluminescence spectra were recorded on a Hitachi F-4500 fluorescence spectrophotometer at room temperature.
Elemental analysis calculated for C24H16N4O8Zn (%): C 52.05, H 2.91, N 10.12; found: C 52.27, H 3.04, N 10.26. IR (KBr, cm-1): 1624 (s), 1531 (m), 1479 (w), 1404 (s), 1359 (m), 1263 (m), 1072 (w), 908 (w), 814 (w), 787 (m), 729 (m), 646 (w), 527 (w).
Single-crystal X-ray diffraction analysis shows that complex (1) consists of one ZnII ion, two 3-nitrobenzoate (NBA) ligands and one 4,4'-bipyridine (4,4'-bipy) ligand. Each ZnII centre is six-coordinated by two pyridyl N-atom donors from two different 4,4'-bipy ligands and four O atoms from two different NBA anions [Zn—O = 1.906 (10)–2.597 (11) Å and Zn—N = 2.101 (2) and 2.093 (2) Å; Table 2], with a distorted ZnN2O4 trigonal prismatic geometry (Fig. 1). The O/N—Zn—O/N angles are in the range 56.2 (2)–139.7 (2)°. The Zn—O(carboxylate) and Zn—N(bipy) bond lengths are in agreement with those reported for other carboxylate- and bipy-containing zinc(II) complexes (Lu et al., 2015).
Adjacent ZnII ions are bridged by 4,4'-bipy ligands to form an infinite one-dimensional zigzag chain running along the c-axis direction, with a Zn···Zn separation of 11.241 Å (Fig. 2). Each NBA ligand adopts a bidentate (OCOO-) coordination mode and all the NBA ligands bristle out from the two sides of the one-dimensional zigzag chains; this orientation plays a major role in packing into a higher network. So, through aromatic π–π stacking interactions between the phenyl rings of NBA ligands (the interplanar spacing is 3.376 Å and the centroid-to-centroid distance is 3.967 Å), adjacent chains generate a two-dimensional layer, as shown in Fig. 3. Further, three such two-dimensional layers interpenetrate, resulting in a threefold interpenetrating two-dimensional network. (Fig. 4).
X-ray powder diffraction (PXRD) analysis was used to confirm the phase purity of the bulk materials of (1) at room temperature (Fig. 5). The experimental diffraction pattern of the bulk sample is consistent with the simulated patterns, indicating that the products are a homogeneous pure phases for (1). To examine the thermal stability of complex (1), thermogravimetric (TG) analyses were carried out for (1) between 293 and 973 K (Fig. 6). The samples were heated under a static air atmosphere with a heating rate of 10 K min-1. The TG curve indicates that no weight loss was observed until 493 K, above which temperature, significant weight loss occurred which was complete at about 683 K, indicating complete decomposition of the NBA and 4,4'-bipy ligands. The whole weight loss of (1) was in accordance with the expected value (observed 86.45%, calculated 86.74%). Analysis of the decomposition product of complex (1) indicates that the final residue is likely to be ZnO, which was further confirmed by examination of the PXRD patterns of this residue.
The IR spectra of complex (1) show absorption peaks at 1624 and 1531cm-1 which can be assigned to the asymmetric stretching vibrations of the carboxylate groups, while the absorption peaks at 1479 and 1404 cm-1 correspond to the symmetric stretching vibrations of the carboxylate groups. The separation values between νasym(CO2) and νsym(CO2) are 145 and 127 cm-1, consistent with the carboxylate group coordinating in a chelating bidentate fashion (Wu et al., 2010), which is in agreement with the X-ray analysis.
The luminescence properties of 4,4'-bipyridine and 3-nitrobenzoic acid (HNBA), and of complex (1) were investigated in the solid state at room temperature, as shown in Fig. 7. 4,4'-Bipyridine and HNBA both exhibit a broad emission band; the emission bands are observed at 418 nm (λex =348nm) for 4,4'-bipy and at 451 nm (λex =290nm) for HNBA at room temperature, while complex (1) displays an intense and sharp emission peak at 406 nm upon excitation at 300 nm. Complex (1) has a slight blue-shift compared with that of pure 4,4'-bipyridine and HNBA, but because d10 configurations are not easily susceptible to oxidiization/reduction, this shift is unlikely to be metal-to-ligand charge transfer (MLCT) nor ligand-to-metal charge transfer (LMCT) in nature. Therefore, the blue shift in complex (1) could be attributed to a change in energy levels (HOMO–LUMO; HOMO is the hight occupied molecular orbital and LUMO is the lowest unoccupied molecular orbital) of the carboxylate-based anionic and the neutral 4,4'-bipy ligands (Singh & Bharadwaj, 2013).
All reagents and solvents were commercially available and of analytical grade. A mixture of 3-nitrobenzoic acid (0.0344 g, 0.2 mmol), 4,4'-bipyridine (0.0156 g, 0.1 mmol), Zn(OAc)2·2H2O (0.0220 g, 0.1 mmol), CH3CH2OH (2 ml) and H2O (6 ml) was stirred evenly and heated in a 20 ml Teflon-lined autoclave at 433 K for 4 d, followed by slow cooling (5 K h-1) to room temperature. Colourless block-shaped crystals were collected (yield 54%, based on Zn).
Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms bonded to C atoms were placed in calculated positions and treated using a riding-model approximation, with C–H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms.
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Bruker, 2000).
[Zn(C7H4NO4)2(C10H8N2)] | F(000) = 1128 |
Mr = 553.78 | Dx = 1.585 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 20.526 (3) Å | Cell parameters from 5402 reflections |
b = 7.5873 (10) Å | θ = 2.6–27.9° |
c = 15.473 (2) Å | µ = 1.12 mm−1 |
β = 105.598 (2)° | T = 296 K |
V = 2320.9 (5) Å3 | Block, colorless |
Z = 4 | 0.29 × 0.21 × 0.16 mm |
Bruker SMART diffractometer | 3611 reflections with I > 2σ(I) |
phi and ω scans | Rint = 0.028 |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | θmax = 26.0°, θmin = 2.1° |
Tmin = 0.528, Tmax = 0.746 | h = −24→25 |
12045 measured reflections | k = −9→7 |
4549 independent reflections | l = −15→19 |
Refinement on F2 | 154 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.113 | w = 1/[σ2(Fo2) + (0.0457P)2 + 2.098P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
4549 reflections | Δρmax = 0.62 e Å−3 |
372 parameters | Δρmin = −0.39 e Å−3 |
[Zn(C7H4NO4)2(C10H8N2)] | V = 2320.9 (5) Å3 |
Mr = 553.78 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 20.526 (3) Å | µ = 1.12 mm−1 |
b = 7.5873 (10) Å | T = 296 K |
c = 15.473 (2) Å | 0.29 × 0.21 × 0.16 mm |
β = 105.598 (2)° |
Bruker SMART diffractometer | 4549 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 3611 reflections with I > 2σ(I) |
Tmin = 0.528, Tmax = 0.746 | Rint = 0.028 |
12045 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 154 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.62 e Å−3 |
4549 reflections | Δρmin = −0.39 e Å−3 |
372 parameters |
Experimental. The Zn—O distances are also highly unusual -1.906 Å is a very short bond for six-coordinate Zn, the bond distances is not reliable because of a serious disordered problem. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Zn1 | 0.24452 (2) | 0.71257 (4) | 0.72513 (2) | 0.04473 (13) | |
O3 | 0.0438 (3) | 0.1921 (5) | 0.3920 (2) | 0.1260 (14) | |
O4 | −0.05746 (19) | 0.1171 (4) | 0.3914 (2) | 0.1267 (15) | |
O1 | 0.1784 (5) | 0.530 (2) | 0.6303 (7) | 0.0762 (19) | 0.51 (3) |
O2 | 0.1488 (7) | 0.6105 (19) | 0.7516 (7) | 0.088 (2) | 0.51 (3) |
O1B | 0.1776 (5) | 0.581 (2) | 0.6384 (7) | 0.0611 (19) | 0.49 (3) |
O2B | 0.1421 (7) | 0.563 (2) | 0.7617 (5) | 0.073 (3) | 0.49 (3) |
O5 | 0.3103 (4) | 0.5835 (14) | 0.8126 (6) | 0.0737 (18) | 0.50 (2) |
O6 | 0.3492 (5) | 0.5618 (15) | 0.6932 (5) | 0.0839 (19) | 0.50 (2) |
O5B | 0.3092 (4) | 0.5159 (16) | 0.8240 (5) | 0.0853 (18) | 0.50 (2) |
O6B | 0.3423 (5) | 0.6212 (14) | 0.7098 (7) | 0.089 (2) | 0.50 (2) |
O7 | 0.4474 (2) | 0.2207 (6) | 1.0723 (2) | 0.1182 (12) | |
O8 | 0.54813 (18) | 0.1418 (5) | 1.0759 (2) | 0.1107 (11) | |
N1 | 0.25146 (12) | 0.9071 (3) | 0.63134 (15) | 0.0482 (6) | |
N2 | 0.23881 (12) | 1.5986 (3) | 0.32144 (15) | 0.0490 (6) | |
N3 | −0.0035 (2) | 0.1845 (4) | 0.4256 (3) | 0.0854 (11) | |
N4 | 0.4944 (2) | 0.2113 (5) | 1.0391 (2) | 0.0822 (10) | |
C1 | 0.13685 (17) | 0.5273 (5) | 0.6808 (3) | 0.0675 (10) | |
C2 | 0.07558 (14) | 0.4194 (4) | 0.6372 (2) | 0.0495 (7) | |
C3 | 0.06614 (15) | 0.3481 (4) | 0.5533 (2) | 0.0498 (7) | |
H3A | 0.0988 | 0.3609 | 0.5221 | 0.060* | |
C4 | 0.00732 (17) | 0.2571 (4) | 0.5165 (2) | 0.0560 (8) | |
C5 | −0.04141 (17) | 0.2336 (5) | 0.5612 (3) | 0.0713 (11) | |
H5 | −0.0808 | 0.1716 | 0.5348 | 0.086* | |
C6 | −0.03085 (19) | 0.3032 (5) | 0.6454 (3) | 0.0774 (11) | |
H6 | −0.0629 | 0.2868 | 0.6773 | 0.093* | |
C7 | 0.02663 (17) | 0.3967 (5) | 0.6829 (2) | 0.0642 (9) | |
H7 | 0.0330 | 0.4457 | 0.7396 | 0.077* | |
C8 | 0.35342 (19) | 0.5328 (5) | 0.7774 (4) | 0.0830 (13) | |
C9 | 0.41717 (15) | 0.4368 (4) | 0.8238 (2) | 0.0572 (8) | |
C10 | 0.42580 (15) | 0.3674 (4) | 0.9088 (2) | 0.0590 (8) | |
H10 | 0.3916 | 0.3756 | 0.9376 | 0.071* | |
C11 | 0.48596 (17) | 0.2861 (4) | 0.9498 (2) | 0.0580 (8) | |
C12 | 0.53794 (18) | 0.2731 (5) | 0.9097 (3) | 0.0717 (10) | |
H12 | 0.5784 | 0.2185 | 0.9390 | 0.086* | |
C13 | 0.5289 (2) | 0.3419 (6) | 0.8261 (3) | 0.0809 (11) | |
H13 | 0.5635 | 0.3343 | 0.7980 | 0.097* | |
C14 | 0.46887 (19) | 0.4227 (5) | 0.7828 (3) | 0.0714 (9) | |
H14 | 0.4632 | 0.4682 | 0.7255 | 0.086* | |
C15 | 0.2794 (2) | 1.0640 (5) | 0.6558 (2) | 0.0703 (10) | |
H15 | 0.3005 | 1.0825 | 0.7162 | 0.084* | |
C16 | 0.27879 (19) | 1.2000 (4) | 0.5972 (2) | 0.0660 (9) | |
H16 | 0.2992 | 1.3069 | 0.6180 | 0.079* | |
C17 | 0.24759 (14) | 1.1771 (4) | 0.50683 (19) | 0.0446 (6) | |
C18 | 0.22063 (16) | 1.0125 (4) | 0.48086 (19) | 0.0537 (7) | |
H18 | 0.2005 | 0.9893 | 0.4206 | 0.064* | |
C19 | 0.22347 (16) | 0.8832 (4) | 0.54382 (19) | 0.0522 (7) | |
H19 | 0.2050 | 0.7735 | 0.5245 | 0.063* | |
C20 | 0.24403 (14) | 1.3231 (4) | 0.44273 (19) | 0.0457 (6) | |
C21 | 0.29182 (16) | 1.4553 (4) | 0.4588 (2) | 0.0589 (8) | |
H21 | 0.3269 | 1.4542 | 0.5113 | 0.071* | |
C22 | 0.28780 (16) | 1.5881 (4) | 0.3978 (2) | 0.0578 (8) | |
H22 | 0.3209 | 1.6752 | 0.4102 | 0.069* | |
C23 | 0.19154 (17) | 1.4746 (5) | 0.3072 (2) | 0.0686 (10) | |
H23 | 0.1559 | 1.4818 | 0.2554 | 0.082* | |
C24 | 0.19228 (16) | 1.3359 (5) | 0.3646 (2) | 0.0643 (9) | |
H24 | 0.1582 | 1.2514 | 0.3510 | 0.077* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0492 (2) | 0.0405 (2) | 0.04070 (19) | 0.00133 (14) | 0.00550 (14) | 0.00052 (14) |
O3 | 0.196 (4) | 0.110 (3) | 0.082 (2) | −0.014 (3) | 0.054 (3) | −0.024 (2) |
O4 | 0.133 (3) | 0.073 (2) | 0.123 (3) | 0.017 (2) | −0.056 (2) | −0.0285 (19) |
O1 | 0.059 (3) | 0.029 (4) | 0.124 (4) | −0.010 (3) | −0.004 (3) | 0.017 (3) |
O2 | 0.068 (4) | 0.040 (4) | 0.131 (5) | −0.002 (3) | −0.015 (3) | −0.011 (3) |
O1B | 0.052 (2) | 0.030 (4) | 0.097 (3) | −0.010 (3) | 0.011 (2) | 0.012 (3) |
O2B | 0.087 (5) | 0.053 (6) | 0.064 (4) | −0.011 (4) | −0.007 (3) | −0.022 (3) |
O5 | 0.061 (2) | 0.034 (3) | 0.110 (3) | 0.029 (3) | −0.004 (2) | −0.018 (3) |
O6 | 0.066 (3) | 0.030 (4) | 0.132 (4) | 0.005 (3) | −0.014 (3) | 0.017 (3) |
O5B | 0.063 (3) | 0.045 (4) | 0.127 (3) | 0.035 (3) | −0.010 (3) | −0.018 (3) |
O6B | 0.063 (3) | 0.028 (3) | 0.150 (4) | 0.009 (3) | −0.015 (3) | 0.026 (3) |
O7 | 0.124 (3) | 0.154 (4) | 0.079 (2) | −0.014 (2) | 0.032 (2) | 0.003 (2) |
O8 | 0.111 (2) | 0.099 (2) | 0.094 (2) | 0.003 (2) | −0.0203 (19) | 0.0200 (19) |
N1 | 0.0520 (13) | 0.0429 (13) | 0.0463 (13) | −0.0016 (11) | 0.0071 (11) | 0.0025 (11) |
N2 | 0.0528 (13) | 0.0463 (14) | 0.0422 (12) | −0.0036 (11) | 0.0027 (11) | 0.0037 (11) |
N3 | 0.116 (3) | 0.0484 (18) | 0.072 (2) | 0.0139 (19) | −0.008 (2) | −0.0029 (16) |
N4 | 0.090 (2) | 0.074 (2) | 0.070 (2) | −0.011 (2) | 0.000 (2) | −0.0037 (18) |
C1 | 0.0507 (19) | 0.0465 (19) | 0.094 (3) | 0.0074 (15) | −0.0009 (19) | 0.017 (2) |
C2 | 0.0464 (15) | 0.0412 (15) | 0.0552 (17) | 0.0019 (12) | 0.0040 (13) | 0.0116 (13) |
C3 | 0.0506 (16) | 0.0429 (15) | 0.0572 (17) | 0.0046 (13) | 0.0165 (14) | 0.0123 (14) |
C4 | 0.0615 (19) | 0.0383 (16) | 0.0594 (19) | 0.0050 (13) | 0.0012 (15) | 0.0066 (13) |
C5 | 0.0456 (18) | 0.051 (2) | 0.109 (3) | −0.0057 (15) | 0.0063 (19) | 0.012 (2) |
C6 | 0.065 (2) | 0.077 (3) | 0.102 (3) | −0.003 (2) | 0.043 (2) | 0.017 (2) |
C7 | 0.072 (2) | 0.067 (2) | 0.0575 (19) | 0.0041 (18) | 0.0236 (17) | 0.0097 (16) |
C8 | 0.051 (2) | 0.051 (2) | 0.123 (4) | −0.0019 (17) | −0.017 (2) | −0.031 (2) |
C9 | 0.0492 (17) | 0.0411 (16) | 0.073 (2) | 0.0065 (13) | 0.0012 (15) | −0.0143 (15) |
C10 | 0.0466 (16) | 0.0523 (18) | 0.076 (2) | 0.0005 (14) | 0.0120 (15) | −0.0211 (17) |
C11 | 0.0581 (19) | 0.0478 (17) | 0.0611 (19) | 0.0002 (15) | 0.0037 (15) | −0.0076 (15) |
C12 | 0.0514 (19) | 0.062 (2) | 0.095 (3) | 0.0178 (16) | 0.0086 (19) | 0.000 (2) |
C13 | 0.068 (2) | 0.080 (3) | 0.102 (3) | 0.021 (2) | 0.036 (2) | 0.005 (2) |
C14 | 0.078 (2) | 0.062 (2) | 0.072 (2) | 0.0112 (19) | 0.0151 (19) | 0.0028 (18) |
C15 | 0.096 (3) | 0.057 (2) | 0.0447 (17) | −0.0226 (19) | −0.0053 (17) | 0.0040 (15) |
C16 | 0.091 (3) | 0.0473 (18) | 0.0494 (17) | −0.0218 (18) | 0.0017 (17) | 0.0017 (14) |
C17 | 0.0441 (15) | 0.0430 (15) | 0.0450 (14) | −0.0014 (12) | 0.0090 (12) | −0.0001 (12) |
C18 | 0.0658 (19) | 0.0524 (18) | 0.0410 (15) | −0.0126 (15) | 0.0106 (14) | −0.0031 (13) |
C19 | 0.0644 (18) | 0.0443 (16) | 0.0485 (16) | −0.0098 (14) | 0.0160 (14) | −0.0063 (13) |
C20 | 0.0481 (15) | 0.0434 (16) | 0.0443 (15) | −0.0009 (12) | 0.0104 (12) | 0.0014 (12) |
C21 | 0.0605 (18) | 0.0542 (19) | 0.0488 (16) | −0.0116 (15) | −0.0083 (14) | 0.0077 (14) |
C22 | 0.0627 (19) | 0.0491 (18) | 0.0534 (17) | −0.0136 (15) | 0.0014 (15) | 0.0038 (14) |
C23 | 0.0605 (19) | 0.076 (2) | 0.0542 (18) | −0.0161 (18) | −0.0109 (15) | 0.0174 (17) |
C24 | 0.0571 (19) | 0.066 (2) | 0.0590 (19) | −0.0198 (16) | −0.0029 (15) | 0.0139 (16) |
Zn1—O1 | 2.200 (15) | N3—C4 | 1.471 (5) |
Zn1—O2 | 2.251 (17) | N4—C11 | 1.461 (5) |
Zn1—O5 | 1.906 (10) | C1—C2 | 1.500 (5) |
Zn1—O6 | 2.597 (11) | C2—C3 | 1.370 (4) |
Zn1—N1 | 2.101 (2) | C2—C7 | 1.386 (4) |
Zn1—N2i | 2.093 (2) | C3—C4 | 1.374 (4) |
Zn1—O1B | 1.922 (13) | C4—C5 | 1.373 (5) |
Zn1—O6B | 2.196 (12) | C5—C6 | 1.368 (6) |
Zn1—O5B | 2.288 (11) | C6—C7 | 1.365 (5) |
O3—N3 | 1.219 (5) | C8—C9 | 1.501 (5) |
O4—N3 | 1.206 (5) | C9—C14 | 1.379 (5) |
O1—C1 | 1.302 (7) | C9—C10 | 1.382 (5) |
O2—C1 | 1.231 (7) | C10—C11 | 1.373 (4) |
O1B—C1 | 1.261 (6) | C11—C12 | 1.374 (5) |
O2B—C1 | 1.258 (7) | C12—C13 | 1.360 (6) |
O5—C8 | 1.220 (7) | C13—C14 | 1.378 (5) |
O6—C8 | 1.301 (7) | C15—C16 | 1.372 (4) |
O5B—C8 | 1.308 (8) | C16—C17 | 1.383 (4) |
O6B—C8 | 1.210 (7) | C17—C18 | 1.381 (4) |
O7—N4 | 1.211 (5) | C17—C20 | 1.476 (4) |
O8—N4 | 1.216 (4) | C18—C19 | 1.373 (4) |
N1—C15 | 1.331 (4) | C20—C21 | 1.378 (4) |
N1—C19 | 1.334 (4) | C20—C24 | 1.381 (4) |
N2—C23 | 1.327 (4) | C21—C22 | 1.368 (4) |
N2—C22 | 1.332 (4) | C23—C24 | 1.375 (5) |
N2—Zn1ii | 2.093 (2) | ||
O5—Zn1—N2i | 90.6 (2) | O2—C1—C2 | 128.5 (9) |
O5—Zn1—N1 | 133.2 (3) | O1B—C1—C2 | 122.3 (7) |
N2i—Zn1—N1 | 92.18 (10) | O2B—C1—C2 | 113.7 (8) |
O5—Zn1—O1 | 110.0 (5) | O1—C1—C2 | 110.1 (8) |
N2i—Zn1—O1 | 139.7 (2) | C3—C2—C7 | 119.8 (3) |
N1—Zn1—O1 | 97.2 (3) | C3—C2—C1 | 122.0 (3) |
O5—Zn1—O2 | 100.4 (5) | C7—C2—C1 | 118.2 (3) |
N2i—Zn1—O2 | 83.51 (19) | C2—C3—C4 | 118.4 (3) |
N1—Zn1—O2 | 126.3 (4) | C5—C4—C3 | 122.2 (3) |
O1—Zn1—O2 | 59.5 (2) | C5—C4—N3 | 119.4 (3) |
O5—Zn1—O6 | 56.2 (2) | C3—C4—N3 | 118.4 (3) |
N2i—Zn1—O6 | 130.1 (2) | C6—C5—C4 | 118.7 (3) |
N1—Zn1—O6 | 87.98 (17) | C7—C6—C5 | 120.2 (3) |
O1—Zn1—O6 | 89.4 (3) | C6—C7—C2 | 120.7 (3) |
O2—Zn1—O6 | 133.7 (4) | O5—C8—O6 | 122.3 (5) |
O1B—Zn1—O6B | 105.2 (5) | O6B—C8—O5B | 122.2 (5) |
O1B—Zn1—N2i | 133.4 (4) | O6B—C8—C9 | 128.3 (7) |
O6B—Zn1—N2i | 121.4 (3) | O5—C8—C9 | 125.6 (7) |
O1B—Zn1—N1 | 92.9 (3) | O6—C8—C9 | 112.1 (6) |
O6B—Zn1—N1 | 85.04 (16) | O5B—C8—C9 | 109.4 (6) |
O1B—Zn1—O5B | 107.8 (5) | C14—C9—C10 | 119.3 (3) |
O6B—Zn1—O5B | 58.87 (17) | C14—C9—C8 | 119.8 (4) |
N2i—Zn1—O5B | 96.0 (2) | C10—C9—C8 | 120.8 (4) |
N1—Zn1—O5B | 141.7 (2) | C11—C10—C9 | 118.7 (3) |
C1—O1—Zn1 | 89.8 (7) | C10—C11—C12 | 122.3 (3) |
C1—O2—Zn1 | 89.3 (8) | C10—C11—N4 | 118.3 (3) |
C1—O1B—Zn1 | 104.7 (8) | C12—C11—N4 | 119.4 (3) |
C8—O5—Zn1 | 107.7 (7) | C13—C12—C11 | 118.5 (3) |
C8—O6—Zn1 | 73.7 (5) | C12—C13—C14 | 120.6 (4) |
C8—O5B—Zn1 | 86.1 (6) | C13—C14—C9 | 120.6 (4) |
C8—O6B—Zn1 | 92.7 (7) | N1—C15—C16 | 124.0 (3) |
C15—N1—C19 | 116.4 (3) | C15—C16—C17 | 119.5 (3) |
C15—N1—Zn1 | 122.4 (2) | C18—C17—C16 | 116.6 (3) |
C19—N1—Zn1 | 121.0 (2) | C18—C17—C20 | 122.7 (3) |
C23—N2—C22 | 116.7 (3) | C16—C17—C20 | 120.7 (3) |
C23—N2—Zn1ii | 123.1 (2) | C19—C18—C17 | 120.2 (3) |
C22—N2—Zn1ii | 119.9 (2) | N1—C19—C18 | 123.2 (3) |
O4—N3—O3 | 125.2 (4) | C21—C20—C24 | 116.7 (3) |
O4—N3—C4 | 117.6 (4) | C21—C20—C17 | 121.4 (3) |
O3—N3—C4 | 117.2 (4) | C24—C20—C17 | 121.9 (3) |
O7—N4—O8 | 123.6 (4) | C22—C21—C20 | 120.3 (3) |
O7—N4—C11 | 118.2 (4) | N2—C22—C21 | 123.2 (3) |
O8—N4—C11 | 118.2 (4) | N2—C23—C24 | 123.7 (3) |
O1B—C1—O2B | 123.9 (6) | C23—C24—C20 | 119.4 (3) |
O2—C1—O1 | 121.4 (6) |
Symmetry codes: (i) x, −y+5/2, z+1/2; (ii) x, −y+5/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C7H4NO4)2(C10H8N2)] |
Mr | 553.78 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 20.526 (3), 7.5873 (10), 15.473 (2) |
β (°) | 105.598 (2) |
V (Å3) | 2320.9 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.12 |
Crystal size (mm) | 0.29 × 0.21 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.528, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12045, 4549, 3611 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.113, 1.03 |
No. of reflections | 4549 |
No. of parameters | 372 |
No. of restraints | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.62, −0.39 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), DIAMOND (Brandenburg, 1999), SHELXTL (Bruker, 2000).
Zn1—O1 | 2.200 (15) | Zn1—O6 | 2.597 (11) |
Zn1—O2 | 2.251 (17) | Zn1—N1 | 2.101 (2) |
Zn1—O5 | 1.906 (10) | Zn1—N2i | 2.093 (2) |
O5—Zn1—N2i | 90.6 (2) | N1—Zn1—O2 | 126.3 (4) |
O5—Zn1—N1 | 133.2 (3) | O1—Zn1—O2 | 59.5 (2) |
N2i—Zn1—N1 | 92.18 (10) | O5—Zn1—O6 | 56.2 (2) |
O5—Zn1—O1 | 110.0 (5) | N2i—Zn1—O6 | 130.1 (2) |
N2i—Zn1—O1 | 139.7 (2) | N1—Zn1—O6 | 87.98 (17) |
N1—Zn1—O1 | 97.2 (3) | O1—Zn1—O6 | 89.4 (3) |
O5—Zn1—O2 | 100.4 (5) | O2—Zn1—O6 | 133.7 (4) |
N2i—Zn1—O2 | 83.51 (19) |
Symmetry code: (i) x, −y+5/2, z+1/2. |