Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616007798/uk3125sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616007798/uk3125Isup2.hkl | |
MDL mol file https://doi.org/10.1107/S2053229616007798/uk3125Isup4.mol | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616007798/uk3125IIsup3.hkl | |
MDL mol file https://doi.org/10.1107/S2053229616007798/uk3125IIsup5.mol |
CCDC references: 1479262; 1479261
The use of luminescent metal complexes in photooptical devices is an active area of inquiry (Xu et al., 2014). Zinc(II) complexes have received a great deal of attention because of the ability to tune their color, their high thermal stability and their favorable carrier transport character (Xu et al., 2008). In particular, several examples of zinc(II) complexes with aryl diimine and/or heterocyclic ligands have been shown to emit brightly in the blue region of the spectrum (Tan et al., 2012; Liu et al., 2010; Xu et al., 2008; Yue et al., 2006; Singh et al., 2011; Wang et al., 2010). Zinc(II) complexes bearing derivatized imidazoles, especially 2-(2-hydroxyphenyl)imidazole (Xu et al., 2014; Kwon et al., 2012; Eseola et al., 2009) and, to a lesser extent, 2-(pyridin-2-yl)benzimidazole (Liu et al., 2010; Yue et al., 2006), have been explored for possible optoelectronic applications, and the crystallographic characterizations of numerous complexes have been performed. Most of the structurally and spectroscopically characterized compounds contain carboxylate ligands in addition to the benzimidazole ligand in the coordination sphere. Zinc(II) complexes exhibit a wide range of coordination geometries and the effect of changes in the ligand geometry, as well as the ligand donor set, on the optical properties of potential components of optical devices is clearly of significance. The two complexes examined herein provide a comparison of the spectral and structural features of acetate- and chloride-coordinated zinc(II) complexes of 5,6-dimethyl-2-(pyridin-2-yl)-1-[(pyridin-2-yl)methyl]-1H-benzimidazole, namely dichlorido{5,6-dimethyl-2-(pyridin-2-yl-κN)-1-[(pyridin-2-yl)methyl]-1H-benzimidazole-κN3}(dimethylformamide-κO)zinc(II) dimethylformamide monosolvate, (I), and bis(acetato-κ2O,O'){5,6-dimethyl-2-(pyridin-2-yl-κN)-1-[(pyridin-2-yl)methyl]-1H-benzimidazole-κN3}(dimethylformamide-κO)zinc(II) ethanol monosolvate, (II).
Solvents were of commercial analytical grade and were used without further purification. Spectroscopic measurements were performed at ambient temperature. Absorption spectra were recorded on a Varian Cary 50 Bio UV–visible spectrophotometer. Excitation and emission spectra were recorded on a Photon Technology International Inc. QM-40 spectrofluorimeter. NMR spectra were obtained using an Agilent 400-MR spectrometer.
5,6-Dimethyl-2-(pyridin-2-yl)-1-[(pyridin-2-yl)methyl]-1H-benzimidazole, ligand L, was prepared as described previously (Geiger & DeStefano, 2014).
Complex (I) was prepared by stirring zinc(II) chloride tetrahydrate (0.63 mmol) with a stoichiometric amount of L in absolute ethanol (15 ml). After refluxing the mixture for 10 min, the solvent volume was reduced by rotoevaporation, filtered and dried under vacuum. A white microcrystalline material (yield 0.24 g, 84%) was obtained. 1H NMR spectroscopy (400 MHz, DMSO-d6, δ p.p.m.): 2.30 (s, 3H), 2.33 (s, 3H), 6.23 (s, 2H), 7.01 (d, 1H), 7.20 (t, 1H), 7.33 (s, 1H), 7.46 (t, 1H), 7.55 (s, 1H), 7.67 (t, 1H), 7.97 (t, 1H), 8.29 (d, 1H), 8.39 (d, 1H), 8.58 (d, 1H). UV–vis spectroscopy (4.93 × 10-5 M, CHCl3): λmax = 323 nm, ε = 21,500 M-1 cm-1 (approximate oscillator strength f = 2.6). Single crystals of (I) suitable for X-ray diffraction studies were obtained by vapor diffusion of diethyl ether into a dimethylformamide solution of the product at 298 K.
Complex (II) was prepared by stirring zinc(II) acetate dihydrate (0.63 mmol) with a stoichiometric amount of L in absolute ethanol (15 ml). After refluxing the mixture for 10 min, the solvent volume was reduced by rotoevaporation and the reaction mixture was filtered. The resulting white powder was dried under vacuum, leaving 0.26 g (80% yield) of product. 1H NMR spectroscopy: (400 MHz, CDCl3, δ p.p.m.): 2.01 (s, 6H), 2.27 (s, 3H), 2.32 (s, 3H), 5.81 (s, 2H), 6.92 (d, 1H), 7.12 (s, 1H), 7.20 (t, 1H), 7.42 (t, 1H), 7.56 (t, 1H), 7.83 (t, 1H), 7.87 (s, 1H), 8.03 (s, 1H), 8.57 (d, 1H), 8.83 (s, 1H). UV–vis spectroscopy (5.10 × 10-5 M, CHCl3): λmax = 343 nm, ε = 22,000 M-1 cm-1 (approximate oscillator strength f = 2.5). Vapor diffusion of hexanes into an ethanolic solution of the product yielded single crystals of (II).
Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were located in difference Fourier maps, except for those associated with the ethanol solvent molecule of (II). H atoms bonded to C atoms were refined using a riding model, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C). For the ethanol solvent molecule of (II), the hydroxy H atom was refined with the O—H bond restrained to 0.84 Å and with Uiso(H) = 1.2Ueq(O).
In the early stages of the refinement of (II), the ethanol solvent molecule was found to be disordered across the glide plane. The refined occupancies of the two contributors to the disorder model refined to occupancies of 0.503 (14):0.496 (14). The C—C and C—O bond distances were restrained to 1.51 and 1.42 Å, respectively.
All DFT calculations were performed using the Spartan '14 (Wavefunction, 2014) package using the B3LYP functional (Becke, 1993; Stephens et al., 1994) with the 6-31+G(d) basis set. Results refer to systems in the gas phase using atomic coordinates obtained from the crystallographic analysis of benzimidazole L (Geiger & DeStefano, 2014), (I), and (II). Solvent molecules were not included in the calcuations. Because bond distances involving H atoms that are obtained from X-ray analysis are systematically short, calculations employed the crystal coordinates for non-H atoms and optimized [B3LYP/6-31+G(d)] coordinates for H atoms.
The coordination geometry of the ZnII ion in (I) is best described as distorted trigonal bipyramidal, with two chloride ions occupying equatorial sites. The distortion is primarily a result of the restriction placed on the geometry by the bidentate coordination mode of the benzimidazole ligand, which spans an axial and an equatorial site, with a N1—Zn—N2 angle of 75.63 (8)°. An O-bound dimethylformamide (dmf) ligand in the remaining axial site completes the coordination sphere. The axial O1—Zn1—N2 angle is 165.10 (9)° and the equatorial angles range from 116.08 (3)° for Cl1—Zn—Cl2 to 122.26 (6)° for Cl1—Zn—N1. The Zn—N(pyridine) bond length is 2.235 (2) Å, whereas the equatorial Zn—N(imidazole) bond length is 2.067 (2) Å. The average Zn—Cl bond length is 2.2782 (12) Å. A complete listing of bond lengths and angles for the ZnII coordination sphere is given in Table 2. The mean plane of the 2-(pyridin-2-yl) substituent is rotated by 10.89 (10)° from the benzimidazole plane [N1—C7—C8—N2 = 10.0 (3)°]. The orientation of the dmf ligand allows for an intramolecular C19—H19···Cl1 hydrogen-bonding interaction (Table 4).
For (II), the ZnII atom exhibits a distorted trigonal prismatic coordination geometry with the triangular faces of the prism twisted from the ideal eclipsed conformation as a result of the 20.59 (9)° angle between the 2-(pyridin-2-yl) mean plane and the benzimidazole mean plane [N2—C7—C8—N3 = 17.6 (3)°]. Two of the edges are formed by bidentate coordination of the acetate ligands and the third edge by the bidentate coordination of the benzimidazole ligand. The coordination of the acetate ligands is decidedly asymmetric. The two shorter Zn—O distances are 2.008 (2) and 2.079 (2) Å and the two longer ones are 2.292 (2) and 2.362 (2) Å (Table 3). The Zn—N bond lengths are also asymmetric with the Zn—N(imidazole) bond length [2.068 (2) Å] shorter than the Zn—N(pyridine) bond length [2.139 (2) Å].
Asymmetric Zn—N bond lengths are observed in similar Zn 2-(pyridin-2-yl)benzimidazole derivatives (Liu et al., 2010; Yue et al., 2006; Li et al., 2011; Chen et al., 2009; Yang et al., 2005). An examination of the 13 independent Zn—N(imidazole) and Zn—N(pyridine) bond lengths reported for the cited compounds yields average values of 2.031 (15) and 2.239 (17) Å, respectively. The N—C—C—N torsion angles observed for (I) and (II) are on the high end of the range observed in the cited compounds [1.3–13.1°, with an average of 4(2)°].
In (I), pairs of molecules related by inversion centers have an interplanar spacing between the benzimidazole ring systems of 3.386 Å. The closest intermolecular contact is C1···N3i = 3.404 (4) Å (see Fig. 3 for symmetry code). Pairs of molecules are joined by weak C—H···O and C—H···Cl hydrogen bonds to form a double chain structure parallel to [110], as shown in Fig. 3 and detailled in Table 4.
The extended structure of (II) also exhibits a chain structure. Molecules are joined by C—H···O hydrogen bonds involving the acetate O3 atom as acceptor, atoms C9 and C10 as donors, and the ethanol solvent molecule as both a hydrogen-bond donor and acceptor, which results in chains along the [010] direction (see Fig. 4 and Table 5).
Absorption and emission spectra of the free ligand L and compounds (I) and (II) in chloroform solution are shown in Fig. 5. The similarity in the shapes of the absorption and emission bands suggests that the bands result from ligand-centered transitions, although coordination of the ZnII atom shifts the responsible transition to lower energy. Excitation at the absorption maximum results in a featureless emission band in chloroform solution for the free ligand and both of the zinc(II) complexes. Notably, replacement of acetate with chloride results in a pronounced red-shift in the absorption and emission bands.
A red shift in absorption maxima was reported for zinc(II) complexes of 2-(2-hydroxyphenyl)benzimidazole (Xu et al., 2008) and alkylidenebis[2-(pyridin-2-yl)benzimidazole] (Liu et al., 2010) complexes, in which the red shift was attributed to mixed intraligand and ligand-to-ligand charge transfer (LLCT) processes. Metal-to-ligand charge transfer (MLCT) and ligand-to-metal charge transfer (LMCT) in this and similar complexes have been ruled out based on the lack of oxidation–reduction chemistry of d10 metals (Wen et al., 2006, 2007; Zhang et al., 2010).
In an effort to better understand the nature of the electronic transitions exhibited by L, (I), and (II), density functional theory (DFT) calculations were performed at the B3LYP/6-31+G(d) level. The non-H-atom coordinates from the X-ray crystallographic results were employed and the H-atom coordinates were optimized (see Section 2.3). Fig. 6 shows a representation of the frontier orbitals and their calculated energies. HOMO-1 (HOMO is highest occupied molecular orbital) for L is π-bonding and localized on the benzimidazole ring system. The HOMO is also π-bonding and extends throughout the benzimidazole ring and into the 2-(pyridin-2-yl) substituent. The LUMO (LUMO is lowest unoccupied molecular orbital) is best described as π-antibonding and is delocalized throughout the three-ring system. The electron-density distribution for these three orbitals is quite similar to that found for 2-(pyridin-2-yl)benzimidazole (Yue et al., 2006). However, for free L, LUMO+1 is π-antibonding and its primary contribution is from the 1-[(pyridin-2-yl)methyl] substituent.
The HOMO and HOMO-1 of the two zinc(II) complexes show appreciable chloride and dmf [for (I)] or acetate [for (II)] character, whereas the LUMO and LUMO+1 orbitals are strikingly similar to those observed for L (Fig. 6). This result provides support that the absorption and emission bands arise from interligand charge transfer transitions. The HOMO–LUMO gaps obtained from the DFT calculations for L (4.28 eV, 290 nm), (I) (3.66 eV, 338 nm), and (II) (3.62 eV, 342 nm) correspond reasonably well to the wavelength maxima found in the solution absorption spectra (322, 323 and 343 nm, respectively). The HOMO–LUMO gap is significantly smaller for the zinc(II) complexes than for free L, which is consistent with the lower energy transitions observed in their spectra. However, the calculated HOMO–LUMO gap for (I) is slightly greater than that of (II), but the absorption and emission bands of (I) appear at lower energy than those of (II).
The apparent inconsistency may occur because: (i) in the solid state, the 2-(pyridin-2-yl) ring is canted further out of the benzimidazole plane for (II) than for (I) (see above) and (ii) the dmf ligand is not coordinated in solution. Both of these possibilities were explored. A second set of calculations was performed on (II) but with the pyridine coplanar with the benzimidazole. The HOMO–LUMO gap decreased from 3.62 to 3.59 eV, consistent with the lower energy transition observed for the complex with the smaller dihedral angle. To test the effect that coordination of dmf has on (II), a calculation was performed on a structure optimized with the dmf ligand removed, resulting in a distorted tetrahedral coordination geometry. Not surprisingly, removal of the dmf ligand and the accompanying coordination geometry change has a major influence on the character of the frontier orbitals. The resulting HOMO–LUMO gap is reduced to 3.48 eV, consistent with the observed red shift in the solution spectra.
The compounds characterized in this study are two new examples of zinc(II) coordination complexes that photoluminesce in the blue region of the spectrum. Our results show that the electronic transitions that are responsible for the luminescence are ligand centered. The properties of the coordinated counter-ion and/or other ancillary ligands play a role in tuning the frontier orbitals, as they possess an appreciable component from these sources, and the transitions observed for the complexes are best described as interligand charge transfer. Our results also show that small changes in the interplanar angle formed by the benzimidazole ring system and the 2-substituent influences the HOMO–LUMO gap and, hence, the photophysical properties exhibited by the complexes.
The use of luminescent metal complexes in photooptical devices is an active area of inquiry (Xu et al., 2014). Zinc(II) complexes have received a great deal of attention because of the ability to tune their color, their high thermal stability and their favorable carrier transport character (Xu et al., 2008). In particular, several examples of zinc(II) complexes with aryl diimine and/or heterocyclic ligands have been shown to emit brightly in the blue region of the spectrum (Tan et al., 2012; Liu et al., 2010; Xu et al., 2008; Yue et al., 2006; Singh et al., 2011; Wang et al., 2010). Zinc(II) complexes bearing derivatized imidazoles, especially 2-(2-hydroxyphenyl)imidazole (Xu et al., 2014; Kwon et al., 2012; Eseola et al., 2009) and, to a lesser extent, 2-(pyridin-2-yl)benzimidazole (Liu et al., 2010; Yue et al., 2006), have been explored for possible optoelectronic applications, and the crystallographic characterizations of numerous complexes have been performed. Most of the structurally and spectroscopically characterized compounds contain carboxylate ligands in addition to the benzimidazole ligand in the coordination sphere. Zinc(II) complexes exhibit a wide range of coordination geometries and the effect of changes in the ligand geometry, as well as the ligand donor set, on the optical properties of potential components of optical devices is clearly of significance. The two complexes examined herein provide a comparison of the spectral and structural features of acetate- and chloride-coordinated zinc(II) complexes of 5,6-dimethyl-2-(pyridin-2-yl)-1-[(pyridin-2-yl)methyl]-1H-benzimidazole, namely dichlorido{5,6-dimethyl-2-(pyridin-2-yl-κN)-1-[(pyridin-2-yl)methyl]-1H-benzimidazole-κN3}(dimethylformamide-κO)zinc(II) dimethylformamide monosolvate, (I), and bis(acetato-κ2O,O'){5,6-dimethyl-2-(pyridin-2-yl-κN)-1-[(pyridin-2-yl)methyl]-1H-benzimidazole-κN3}(dimethylformamide-κO)zinc(II) ethanol monosolvate, (II).
Solvents were of commercial analytical grade and were used without further purification. Spectroscopic measurements were performed at ambient temperature. Absorption spectra were recorded on a Varian Cary 50 Bio UV–visible spectrophotometer. Excitation and emission spectra were recorded on a Photon Technology International Inc. QM-40 spectrofluorimeter. NMR spectra were obtained using an Agilent 400-MR spectrometer.
Complex (I) was prepared by stirring zinc(II) chloride tetrahydrate (0.63 mmol) with a stoichiometric amount of L in absolute ethanol (15 ml). After refluxing the mixture for 10 min, the solvent volume was reduced by rotoevaporation, filtered and dried under vacuum. A white microcrystalline material (yield 0.24 g, 84%) was obtained. 1H NMR spectroscopy (400 MHz, DMSO-d6, δ p.p.m.): 2.30 (s, 3H), 2.33 (s, 3H), 6.23 (s, 2H), 7.01 (d, 1H), 7.20 (t, 1H), 7.33 (s, 1H), 7.46 (t, 1H), 7.55 (s, 1H), 7.67 (t, 1H), 7.97 (t, 1H), 8.29 (d, 1H), 8.39 (d, 1H), 8.58 (d, 1H). UV–vis spectroscopy (4.93 × 10-5 M, CHCl3): λmax = 323 nm, ε = 21,500 M-1 cm-1 (approximate oscillator strength f = 2.6). Single crystals of (I) suitable for X-ray diffraction studies were obtained by vapor diffusion of diethyl ether into a dimethylformamide solution of the product at 298 K.
Complex (II) was prepared by stirring zinc(II) acetate dihydrate (0.63 mmol) with a stoichiometric amount of L in absolute ethanol (15 ml). After refluxing the mixture for 10 min, the solvent volume was reduced by rotoevaporation and the reaction mixture was filtered. The resulting white powder was dried under vacuum, leaving 0.26 g (80% yield) of product. 1H NMR spectroscopy: (400 MHz, CDCl3, δ p.p.m.): 2.01 (s, 6H), 2.27 (s, 3H), 2.32 (s, 3H), 5.81 (s, 2H), 6.92 (d, 1H), 7.12 (s, 1H), 7.20 (t, 1H), 7.42 (t, 1H), 7.56 (t, 1H), 7.83 (t, 1H), 7.87 (s, 1H), 8.03 (s, 1H), 8.57 (d, 1H), 8.83 (s, 1H). UV–vis spectroscopy (5.10 × 10-5 M, CHCl3): λmax = 343 nm, ε = 22,000 M-1 cm-1 (approximate oscillator strength f = 2.5). Vapor diffusion of hexanes into an ethanolic solution of the product yielded single crystals of (II).
All DFT calculations were performed using the Spartan '14 (Wavefunction, 2014) package using the B3LYP functional (Becke, 1993; Stephens et al., 1994) with the 6-31+G(d) basis set. Results refer to systems in the gas phase using atomic coordinates obtained from the crystallographic analysis of benzimidazole L (Geiger & DeStefano, 2014), (I), and (II). Solvent molecules were not included in the calcuations. Because bond distances involving H atoms that are obtained from X-ray analysis are systematically short, calculations employed the crystal coordinates for non-H atoms and optimized [B3LYP/6-31+G(d)] coordinates for H atoms.
The coordination geometry of the ZnII ion in (I) is best described as distorted trigonal bipyramidal, with two chloride ions occupying equatorial sites. The distortion is primarily a result of the restriction placed on the geometry by the bidentate coordination mode of the benzimidazole ligand, which spans an axial and an equatorial site, with a N1—Zn—N2 angle of 75.63 (8)°. An O-bound dimethylformamide (dmf) ligand in the remaining axial site completes the coordination sphere. The axial O1—Zn1—N2 angle is 165.10 (9)° and the equatorial angles range from 116.08 (3)° for Cl1—Zn—Cl2 to 122.26 (6)° for Cl1—Zn—N1. The Zn—N(pyridine) bond length is 2.235 (2) Å, whereas the equatorial Zn—N(imidazole) bond length is 2.067 (2) Å. The average Zn—Cl bond length is 2.2782 (12) Å. A complete listing of bond lengths and angles for the ZnII coordination sphere is given in Table 2. The mean plane of the 2-(pyridin-2-yl) substituent is rotated by 10.89 (10)° from the benzimidazole plane [N1—C7—C8—N2 = 10.0 (3)°]. The orientation of the dmf ligand allows for an intramolecular C19—H19···Cl1 hydrogen-bonding interaction (Table 4).
For (II), the ZnII atom exhibits a distorted trigonal prismatic coordination geometry with the triangular faces of the prism twisted from the ideal eclipsed conformation as a result of the 20.59 (9)° angle between the 2-(pyridin-2-yl) mean plane and the benzimidazole mean plane [N2—C7—C8—N3 = 17.6 (3)°]. Two of the edges are formed by bidentate coordination of the acetate ligands and the third edge by the bidentate coordination of the benzimidazole ligand. The coordination of the acetate ligands is decidedly asymmetric. The two shorter Zn—O distances are 2.008 (2) and 2.079 (2) Å and the two longer ones are 2.292 (2) and 2.362 (2) Å (Table 3). The Zn—N bond lengths are also asymmetric with the Zn—N(imidazole) bond length [2.068 (2) Å] shorter than the Zn—N(pyridine) bond length [2.139 (2) Å].
Asymmetric Zn—N bond lengths are observed in similar Zn 2-(pyridin-2-yl)benzimidazole derivatives (Liu et al., 2010; Yue et al., 2006; Li et al., 2011; Chen et al., 2009; Yang et al., 2005). An examination of the 13 independent Zn—N(imidazole) and Zn—N(pyridine) bond lengths reported for the cited compounds yields average values of 2.031 (15) and 2.239 (17) Å, respectively. The N—C—C—N torsion angles observed for (I) and (II) are on the high end of the range observed in the cited compounds [1.3–13.1°, with an average of 4(2)°].
In (I), pairs of molecules related by inversion centers have an interplanar spacing between the benzimidazole ring systems of 3.386 Å. The closest intermolecular contact is C1···N3i = 3.404 (4) Å (see Fig. 3 for symmetry code). Pairs of molecules are joined by weak C—H···O and C—H···Cl hydrogen bonds to form a double chain structure parallel to [110], as shown in Fig. 3 and detailled in Table 4.
The extended structure of (II) also exhibits a chain structure. Molecules are joined by C—H···O hydrogen bonds involving the acetate O3 atom as acceptor, atoms C9 and C10 as donors, and the ethanol solvent molecule as both a hydrogen-bond donor and acceptor, which results in chains along the [010] direction (see Fig. 4 and Table 5).
Absorption and emission spectra of the free ligand L and compounds (I) and (II) in chloroform solution are shown in Fig. 5. The similarity in the shapes of the absorption and emission bands suggests that the bands result from ligand-centered transitions, although coordination of the ZnII atom shifts the responsible transition to lower energy. Excitation at the absorption maximum results in a featureless emission band in chloroform solution for the free ligand and both of the zinc(II) complexes. Notably, replacement of acetate with chloride results in a pronounced red-shift in the absorption and emission bands.
A red shift in absorption maxima was reported for zinc(II) complexes of 2-(2-hydroxyphenyl)benzimidazole (Xu et al., 2008) and alkylidenebis[2-(pyridin-2-yl)benzimidazole] (Liu et al., 2010) complexes, in which the red shift was attributed to mixed intraligand and ligand-to-ligand charge transfer (LLCT) processes. Metal-to-ligand charge transfer (MLCT) and ligand-to-metal charge transfer (LMCT) in this and similar complexes have been ruled out based on the lack of oxidation–reduction chemistry of d10 metals (Wen et al., 2006, 2007; Zhang et al., 2010).
In an effort to better understand the nature of the electronic transitions exhibited by L, (I), and (II), density functional theory (DFT) calculations were performed at the B3LYP/6-31+G(d) level. The non-H-atom coordinates from the X-ray crystallographic results were employed and the H-atom coordinates were optimized (see Section 2.3). Fig. 6 shows a representation of the frontier orbitals and their calculated energies. HOMO-1 (HOMO is highest occupied molecular orbital) for L is π-bonding and localized on the benzimidazole ring system. The HOMO is also π-bonding and extends throughout the benzimidazole ring and into the 2-(pyridin-2-yl) substituent. The LUMO (LUMO is lowest unoccupied molecular orbital) is best described as π-antibonding and is delocalized throughout the three-ring system. The electron-density distribution for these three orbitals is quite similar to that found for 2-(pyridin-2-yl)benzimidazole (Yue et al., 2006). However, for free L, LUMO+1 is π-antibonding and its primary contribution is from the 1-[(pyridin-2-yl)methyl] substituent.
The HOMO and HOMO-1 of the two zinc(II) complexes show appreciable chloride and dmf [for (I)] or acetate [for (II)] character, whereas the LUMO and LUMO+1 orbitals are strikingly similar to those observed for L (Fig. 6). This result provides support that the absorption and emission bands arise from interligand charge transfer transitions. The HOMO–LUMO gaps obtained from the DFT calculations for L (4.28 eV, 290 nm), (I) (3.66 eV, 338 nm), and (II) (3.62 eV, 342 nm) correspond reasonably well to the wavelength maxima found in the solution absorption spectra (322, 323 and 343 nm, respectively). The HOMO–LUMO gap is significantly smaller for the zinc(II) complexes than for free L, which is consistent with the lower energy transitions observed in their spectra. However, the calculated HOMO–LUMO gap for (I) is slightly greater than that of (II), but the absorption and emission bands of (I) appear at lower energy than those of (II).
The apparent inconsistency may occur because: (i) in the solid state, the 2-(pyridin-2-yl) ring is canted further out of the benzimidazole plane for (II) than for (I) (see above) and (ii) the dmf ligand is not coordinated in solution. Both of these possibilities were explored. A second set of calculations was performed on (II) but with the pyridine coplanar with the benzimidazole. The HOMO–LUMO gap decreased from 3.62 to 3.59 eV, consistent with the lower energy transition observed for the complex with the smaller dihedral angle. To test the effect that coordination of dmf has on (II), a calculation was performed on a structure optimized with the dmf ligand removed, resulting in a distorted tetrahedral coordination geometry. Not surprisingly, removal of the dmf ligand and the accompanying coordination geometry change has a major influence on the character of the frontier orbitals. The resulting HOMO–LUMO gap is reduced to 3.48 eV, consistent with the observed red shift in the solution spectra.
The compounds characterized in this study are two new examples of zinc(II) coordination complexes that photoluminesce in the blue region of the spectrum. Our results show that the electronic transitions that are responsible for the luminescence are ligand centered. The properties of the coordinated counter-ion and/or other ancillary ligands play a role in tuning the frontier orbitals, as they possess an appreciable component from these sources, and the transitions observed for the complexes are best described as interligand charge transfer. Our results also show that small changes in the interplanar angle formed by the benzimidazole ring system and the 2-substituent influences the HOMO–LUMO gap and, hence, the photophysical properties exhibited by the complexes.
5,6-Dimethyl-2-(pyridin-2-yl)-1-[(pyridin-2-yl)methyl]-1H-benzimidazole, ligand L, was prepared as described previously (Geiger & DeStefano, 2014).
Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were located in difference Fourier maps, except for those associated with the ethanol solvent molecule of (II). H atoms bonded to C atoms were refined using a riding model, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C). For the ethanol solvent molecule of (II), the hydroxy H atom was refined with the O—H bond restrained to 0.84 Å and with Uiso(H) = 1.2Ueq(O).
In the early stages of the refinement of (II), the ethanol solvent molecule was found to be disordered across the glide plane. The refined occupancies of the two contributors to the disorder model refined to occupancies of 0.503 (14):0.496 (14). The C—C and C—O bond distances were restrained to 1.51 and 1.42 Å, respectively.
For both compounds, data collection: APEX2 (Bruker, 2013). Cell refinement: SAINT (Bruker, 2013) for (I); APEX2 (Bruker, 2013) for (II). For both compounds, data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).
[ZnCl2(C20H18N4)(C3H7NO)]·C3H7NO | Z = 2 |
Mr = 596.84 | F(000) = 620 |
Triclinic, P1 | Dx = 1.408 Mg m−3 |
a = 11.2504 (11) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.7298 (11) Å | Cell parameters from 4156 reflections |
c = 12.6588 (13) Å | θ = 2.4–25.2° |
α = 71.518 (4)° | µ = 1.10 mm−1 |
β = 71.087 (3)° | T = 200 K |
γ = 65.760 (3)° | Needle, clear colourless |
V = 1407.9 (2) Å3 | 0.58 × 0.30 × 0.20 mm |
Bruker SMART X2S benchtop diffractometer | 4976 independent reflections |
Radiation source: sealed microfocus tube | 4058 reflections with I > 2σ(I) |
Doubly curved silicon crystal monochromator | Rint = 0.047 |
Detector resolution: 8.3330 pixels mm-1 | θmax = 25.4°, θmin = 2.3° |
/w scans | h = −12→13 |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | k = −13→13 |
Tmin = 0.56, Tmax = 0.81 | l = −15→14 |
12063 measured reflections |
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) = 0.107 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0534P)2] where P = (Fo2 + 2Fc2)/3 |
4976 reflections | (Δ/σ)max = 0.001 |
340 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.64 e Å−3 |
[ZnCl2(C20H18N4)(C3H7NO)]·C3H7NO | γ = 65.760 (3)° |
Mr = 596.84 | V = 1407.9 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.2504 (11) Å | Mo Kα radiation |
b = 11.7298 (11) Å | µ = 1.10 mm−1 |
c = 12.6588 (13) Å | T = 200 K |
α = 71.518 (4)° | 0.58 × 0.30 × 0.20 mm |
β = 71.087 (3)° |
Bruker SMART X2S benchtop diffractometer | 4976 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | 4058 reflections with I > 2σ(I) |
Tmin = 0.56, Tmax = 0.81 | Rint = 0.047 |
12063 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.40 e Å−3 |
4976 reflections | Δρmin = −0.64 e Å−3 |
340 parameters |
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. |
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 > 2sigma(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 | ||
Zn1 | 0.56523 (3) | 0.12184 (3) | 0.66858 (2) | 0.02769 (12) | |
Cl1 | 0.47553 (7) | −0.03597 (7) | 0.75730 (6) | 0.0398 (2) | |
Cl2 | 0.76891 (8) | 0.08344 (8) | 0.69805 (8) | 0.0539 (2) | |
O1 | 0.6512 (2) | 0.0607 (2) | 0.51059 (17) | 0.0518 (6) | |
O2 | 0.0887 (3) | 0.7101 (3) | 0.8691 (2) | 0.0719 (8) | |
N1 | 0.4590 (2) | 0.2990 (2) | 0.58394 (16) | 0.0224 (5) | |
N2 | 0.4455 (2) | 0.2320 (2) | 0.80622 (17) | 0.0273 (5) | |
N3 | 0.31680 (19) | 0.4993 (2) | 0.58193 (16) | 0.0215 (5) | |
N4 | 0.0522 (2) | 0.5219 (2) | 0.6568 (2) | 0.0325 (6) | |
N5 | 0.7837 (2) | −0.0957 (2) | 0.41491 (19) | 0.0343 (6) | |
N6 | −0.0489 (3) | 0.8385 (3) | 0.9914 (2) | 0.0465 (7) | |
C1 | 0.4522 (2) | 0.3607 (3) | 0.4705 (2) | 0.0211 (5) | |
C2 | 0.5174 (2) | 0.3181 (3) | 0.3683 (2) | 0.0238 (6) | |
H2 | 0.579 | 0.2334 | 0.3682 | 0.029* | |
C3 | 0.4897 (3) | 0.4032 (3) | 0.2668 (2) | 0.0268 (6) | |
C4 | 0.3968 (3) | 0.5294 (3) | 0.2673 (2) | 0.0280 (6) | |
C5 | 0.3328 (3) | 0.5717 (3) | 0.3681 (2) | 0.0267 (6) | |
H5 | 0.2708 | 0.6563 | 0.3687 | 0.032* | |
C6 | 0.3625 (2) | 0.4858 (3) | 0.4689 (2) | 0.0220 (6) | |
C7 | 0.3752 (2) | 0.3848 (3) | 0.6468 (2) | 0.0217 (6) | |
C8 | 0.3564 (2) | 0.3466 (3) | 0.7727 (2) | 0.0237 (6) | |
C9 | 0.2576 (3) | 0.4158 (3) | 0.8511 (2) | 0.0328 (7) | |
H9 | 0.1939 | 0.4962 | 0.8265 | 0.039* | |
C10 | 0.2550 (3) | 0.3634 (3) | 0.9669 (2) | 0.0398 (8) | |
H10 | 0.1883 | 0.4081 | 1.0226 | 0.048* | |
C11 | 0.3478 (3) | 0.2481 (3) | 1.0008 (2) | 0.0402 (8) | |
H11 | 0.3481 | 0.2127 | 1.0795 | 0.048* | |
C12 | 0.4417 (3) | 0.1841 (3) | 0.9170 (2) | 0.0351 (7) | |
H12 | 0.5056 | 0.1031 | 0.9398 | 0.042* | |
C13 | 0.2217 (2) | 0.6187 (3) | 0.6145 (2) | 0.0246 (6) | |
H13A | 0.2355 | 0.6912 | 0.5517 | 0.03* | |
H13B | 0.24 | 0.6266 | 0.6828 | 0.03* | |
C14 | 0.0774 (2) | 0.6283 (2) | 0.64060 (19) | 0.0215 (6) | |
C15 | −0.0220 (3) | 0.7448 (3) | 0.6523 (2) | 0.0280 (6) | |
H15 | 0.0004 | 0.819 | 0.6375 | 0.034* | |
C16 | −0.1542 (3) | 0.7525 (3) | 0.6858 (2) | 0.0349 (7) | |
H16 | −0.2241 | 0.8311 | 0.6967 | 0.042* | |
C17 | −0.1819 (3) | 0.6432 (3) | 0.7029 (3) | 0.0395 (8) | |
H17 | −0.2716 | 0.6445 | 0.7262 | 0.047* | |
C18 | −0.0776 (3) | 0.5329 (3) | 0.6855 (3) | 0.0425 (8) | |
H18 | −0.098 | 0.459 | 0.6942 | 0.051* | |
C19 | 0.6822 (3) | −0.0471 (3) | 0.4948 (2) | 0.0365 (7) | |
H19 | 0.63 | −0.0982 | 0.5431 | 0.044* | |
C20 | 0.8633 (4) | −0.0198 (4) | 0.3359 (4) | 0.0749 (14) | |
H20A | 0.9574 | −0.0648 | 0.3398 | 0.112* | |
H20B | 0.8319 | 0.0632 | 0.3565 | 0.112* | |
H20C | 0.8544 | −0.0065 | 0.258 | 0.112* | |
C21 | 0.8162 (4) | −0.2229 (3) | 0.3986 (3) | 0.0524 (9) | |
H21A | 0.9098 | −0.273 | 0.402 | 0.079* | |
H21B | 0.8031 | −0.2166 | 0.3239 | 0.079* | |
H21C | 0.7579 | −0.265 | 0.4589 | 0.079* | |
C22 | −0.0046 (3) | 0.8047 (3) | 0.8915 (3) | 0.0466 (8) | |
H22 | −0.0499 | 0.8593 | 0.8325 | 0.056* | |
C23 | 0.0117 (5) | 0.7549 (5) | 1.0860 (3) | 0.0915 (16) | |
H23A | 0.0968 | 0.6918 | 1.0572 | 0.137* | |
H23B | −0.0485 | 0.7106 | 1.14 | 0.137* | |
H23C | 0.0278 | 0.8057 | 1.1247 | 0.137* | |
C24 | −0.1634 (4) | 0.9519 (4) | 1.0116 (4) | 0.0724 (12) | |
H24A | −0.1972 | 0.9956 | 0.9417 | 0.109* | |
H24B | −0.1369 | 1.0095 | 1.0335 | 0.109* | |
H24C | −0.2337 | 0.9276 | 1.0733 | 0.109* | |
C31 | 0.5605 (3) | 0.3587 (3) | 0.1557 (2) | 0.0371 (7) | |
H31A | 0.6122 | 0.2671 | 0.1718 | 0.056* | |
H31B | 0.6209 | 0.4063 | 0.1097 | 0.056* | |
H31C | 0.4943 | 0.3741 | 0.1134 | 0.056* | |
C41 | 0.3633 (3) | 0.6185 (3) | 0.1564 (2) | 0.0411 (8) | |
H41A | 0.3034 | 0.7032 | 0.1709 | 0.062* | |
H41B | 0.319 | 0.5842 | 0.1251 | 0.062* | |
H41C | 0.4458 | 0.6258 | 0.1015 | 0.062* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.02231 (19) | 0.0221 (2) | 0.03079 (18) | −0.00082 (14) | −0.00302 (13) | −0.00757 (13) |
Cl1 | 0.0373 (4) | 0.0320 (4) | 0.0457 (4) | −0.0127 (4) | 0.0013 (3) | −0.0123 (3) |
Cl2 | 0.0271 (4) | 0.0341 (5) | 0.0989 (7) | 0.0020 (4) | −0.0224 (4) | −0.0204 (4) |
O1 | 0.0677 (16) | 0.0254 (13) | 0.0339 (11) | 0.0049 (12) | 0.0027 (11) | −0.0121 (9) |
O2 | 0.0593 (17) | 0.073 (2) | 0.0688 (17) | 0.0171 (15) | −0.0207 (14) | −0.0431 (15) |
N1 | 0.0169 (11) | 0.0219 (13) | 0.0247 (11) | −0.0033 (10) | −0.0023 (9) | −0.0074 (9) |
N2 | 0.0257 (12) | 0.0276 (14) | 0.0250 (11) | −0.0058 (11) | −0.0033 (9) | −0.0079 (9) |
N3 | 0.0125 (10) | 0.0209 (13) | 0.0265 (11) | −0.0007 (9) | −0.0009 (8) | −0.0093 (9) |
N4 | 0.0200 (12) | 0.0250 (14) | 0.0502 (14) | −0.0050 (11) | −0.0054 (10) | −0.0111 (11) |
N5 | 0.0269 (13) | 0.0342 (16) | 0.0426 (13) | −0.0061 (12) | −0.0008 (11) | −0.0222 (11) |
N6 | 0.0358 (15) | 0.057 (2) | 0.0412 (14) | −0.0067 (14) | −0.0008 (12) | −0.0233 (13) |
C1 | 0.0135 (12) | 0.0231 (15) | 0.0265 (12) | −0.0055 (11) | −0.0014 (10) | −0.0092 (11) |
C2 | 0.0184 (13) | 0.0241 (15) | 0.0306 (13) | −0.0072 (12) | −0.0017 (11) | −0.0118 (11) |
C3 | 0.0262 (14) | 0.0367 (18) | 0.0254 (13) | −0.0184 (14) | −0.0008 (11) | −0.0116 (12) |
C4 | 0.0274 (15) | 0.0344 (18) | 0.0270 (13) | −0.0175 (14) | −0.0059 (11) | −0.0036 (12) |
C5 | 0.0198 (13) | 0.0252 (16) | 0.0338 (14) | −0.0071 (12) | −0.0050 (11) | −0.0064 (12) |
C6 | 0.0179 (13) | 0.0255 (16) | 0.0237 (12) | −0.0107 (12) | −0.0010 (10) | −0.0061 (11) |
C7 | 0.0118 (12) | 0.0272 (16) | 0.0245 (12) | −0.0041 (11) | −0.0011 (10) | −0.0098 (11) |
C8 | 0.0168 (13) | 0.0254 (16) | 0.0285 (13) | −0.0050 (12) | −0.0033 (10) | −0.0102 (11) |
C9 | 0.0277 (15) | 0.0336 (18) | 0.0310 (14) | −0.0030 (14) | −0.0034 (12) | −0.0124 (12) |
C10 | 0.0350 (17) | 0.048 (2) | 0.0283 (14) | −0.0089 (16) | 0.0044 (13) | −0.0168 (14) |
C11 | 0.051 (2) | 0.047 (2) | 0.0236 (14) | −0.0203 (18) | −0.0055 (13) | −0.0061 (13) |
C12 | 0.0367 (17) | 0.0292 (18) | 0.0332 (15) | −0.0088 (14) | −0.0070 (13) | −0.0028 (12) |
C13 | 0.0176 (13) | 0.0195 (15) | 0.0341 (14) | −0.0025 (12) | −0.0009 (11) | −0.0124 (11) |
C14 | 0.0160 (13) | 0.0221 (15) | 0.0244 (12) | −0.0025 (12) | −0.0029 (10) | −0.0095 (11) |
C15 | 0.0242 (14) | 0.0220 (16) | 0.0381 (15) | −0.0041 (13) | −0.0074 (12) | −0.0116 (12) |
C16 | 0.0200 (14) | 0.0322 (18) | 0.0427 (16) | 0.0071 (13) | −0.0084 (12) | −0.0156 (13) |
C17 | 0.0147 (14) | 0.044 (2) | 0.0545 (18) | −0.0073 (14) | −0.0035 (13) | −0.0124 (15) |
C18 | 0.0262 (16) | 0.034 (2) | 0.067 (2) | −0.0116 (15) | −0.0083 (15) | −0.0116 (16) |
C19 | 0.0295 (16) | 0.037 (2) | 0.0297 (14) | 0.0013 (14) | −0.0036 (12) | −0.0099 (13) |
C20 | 0.067 (3) | 0.073 (3) | 0.088 (3) | −0.043 (3) | 0.032 (2) | −0.045 (2) |
C21 | 0.049 (2) | 0.052 (2) | 0.065 (2) | −0.0187 (19) | 0.0049 (17) | −0.0385 (18) |
C22 | 0.043 (2) | 0.055 (2) | 0.0390 (17) | −0.0073 (18) | −0.0086 (15) | −0.0196 (16) |
C23 | 0.095 (4) | 0.108 (4) | 0.050 (2) | −0.001 (3) | −0.027 (2) | −0.024 (2) |
C24 | 0.044 (2) | 0.083 (3) | 0.087 (3) | −0.002 (2) | −0.001 (2) | −0.055 (3) |
C31 | 0.0390 (17) | 0.044 (2) | 0.0281 (14) | −0.0167 (16) | 0.0009 (12) | −0.0128 (13) |
C41 | 0.048 (2) | 0.046 (2) | 0.0307 (15) | −0.0200 (17) | −0.0113 (14) | −0.0022 (14) |
N1—C1 | 1.400 (3) | Zn1—Cl2 | 2.2788 (9) |
C9—C10 | 1.394 (4) | C10—H10 | 0.95 |
C10—C11 | 1.366 (5) | C11—H11 | 0.95 |
C11—C12 | 1.390 (4) | C12—H12 | 0.95 |
N2—C12 | 1.329 (3) | C13—H13A | 0.99 |
N3—C13 | 1.459 (3) | C13—H13B | 0.99 |
C13—C14 | 1.511 (3) | C15—H15 | 0.95 |
N4—C14 | 1.331 (3) | C16—H16 | 0.95 |
C14—C15 | 1.380 (4) | C17—H17 | 0.95 |
C15—C16 | 1.380 (4) | C18—H18 | 0.95 |
C16—C17 | 1.378 (4) | C19—H19 | 0.95 |
C17—C18 | 1.366 (4) | C2—H2 | 0.95 |
N4—C18 | 1.346 (3) | C20—H20A | 0.98 |
N5—C19 | 1.317 (3) | C20—H20B | 0.98 |
O1—C19 | 1.229 (3) | C20—H20C | 0.98 |
C1—C2 | 1.398 (3) | C21—H21A | 0.98 |
N5—C20 | 1.451 (4) | C21—H21B | 0.98 |
N5—C21 | 1.448 (4) | C21—H21C | 0.98 |
N6—C22 | 1.323 (4) | C22—H22 | 0.95 |
O2—C22 | 1.211 (4) | C23—H23A | 0.98 |
N6—C23 | 1.448 (5) | C23—H23B | 0.98 |
N6—C24 | 1.445 (4) | C23—H23C | 0.98 |
C2—C3 | 1.391 (4) | C24—H24A | 0.98 |
C3—C31 | 1.511 (3) | C24—H24B | 0.98 |
C3—C4 | 1.419 (4) | C24—H24C | 0.98 |
C4—C41 | 1.514 (4) | C31—H31A | 0.98 |
C4—C5 | 1.381 (4) | C31—H31B | 0.98 |
C5—C6 | 1.392 (4) | C31—H31C | 0.98 |
C1—C6 | 1.396 (4) | C41—H41A | 0.98 |
N3—C6 | 1.392 (3) | C41—H41B | 0.98 |
N3—C7 | 1.355 (3) | C41—H41C | 0.98 |
N1—C7 | 1.333 (3) | C5—H5 | 0.95 |
C7—C8 | 1.481 (3) | C9—H9 | 0.95 |
N2—C8 | 1.341 (3) | Zn1—N1 | 2.067 (2) |
C8—C9 | 1.391 (3) | Zn1—N2 | 2.235 (2) |
Zn1—Cl1 | 2.2775 (8) | Zn1—O1 | 2.1298 (19) |
N1—Zn1—O1 | 89.50 (8) | N3—C13—C14 | 113.5 (2) |
N1—Zn1—N2 | 75.63 (8) | N3—C13—H13A | 108.9 |
O1—Zn1—N2 | 165.10 (9) | C14—C13—H13A | 108.9 |
N1—Zn1—Cl1 | 122.26 (6) | N3—C13—H13B | 108.9 |
O1—Zn1—Cl1 | 94.81 (6) | C14—C13—H13B | 108.9 |
N2—Zn1—Cl1 | 92.36 (6) | H13A—C13—H13B | 107.7 |
N1—Zn1—Cl2 | 121.19 (6) | N4—C14—C15 | 123.0 (2) |
O1—Zn1—Cl2 | 92.71 (7) | N4—C14—C13 | 118.0 (2) |
N2—Zn1—Cl2 | 95.85 (6) | C15—C14—C13 | 118.9 (2) |
Cl1—Zn1—Cl2 | 116.08 (3) | C16—C15—C14 | 119.5 (2) |
C19—O1—Zn1 | 127.57 (18) | C16—C15—H15 | 120.3 |
C7—N1—C1 | 105.8 (2) | C14—C15—H15 | 120.3 |
C7—N1—Zn1 | 117.44 (16) | C17—C16—C15 | 118.1 (3) |
C1—N1—Zn1 | 136.71 (17) | C17—C16—H16 | 120.9 |
C12—N2—C8 | 119.5 (2) | C15—C16—H16 | 120.9 |
C12—N2—Zn1 | 124.7 (2) | C18—C17—C16 | 118.5 (3) |
C8—N2—Zn1 | 114.86 (16) | C18—C17—H17 | 120.7 |
C7—N3—C6 | 107.0 (2) | C16—C17—H17 | 120.7 |
C7—N3—C13 | 130.6 (2) | N4—C18—C17 | 124.4 (3) |
C6—N3—C13 | 122.4 (2) | N4—C18—H18 | 117.8 |
C14—N4—C18 | 116.3 (2) | C17—C18—H18 | 117.8 |
C19—N5—C21 | 122.0 (2) | O1—C19—N5 | 123.8 (3) |
C19—N5—C20 | 120.3 (3) | O1—C19—H19 | 118.1 |
C21—N5—C20 | 117.6 (2) | N5—C19—H19 | 118.1 |
C22—N6—C24 | 121.8 (3) | N5—C20—H20A | 109.5 |
C22—N6—C23 | 119.4 (3) | N5—C20—H20B | 109.5 |
C24—N6—C23 | 118.7 (3) | H20A—C20—H20B | 109.5 |
C6—C1—C2 | 120.1 (2) | N5—C20—H20C | 109.5 |
C6—C1—N1 | 108.5 (2) | H20A—C20—H20C | 109.5 |
C2—C1—N1 | 131.4 (3) | H20B—C20—H20C | 109.5 |
C3—C2—C1 | 118.2 (3) | N5—C21—H21A | 109.5 |
C3—C2—H2 | 120.9 | N5—C21—H21B | 109.5 |
C1—C2—H2 | 120.9 | H21A—C21—H21B | 109.5 |
C2—C3—C4 | 120.8 (2) | N5—C21—H21C | 109.5 |
C2—C3—C31 | 118.7 (3) | H21A—C21—H21C | 109.5 |
C4—C3—C31 | 120.5 (2) | H21B—C21—H21C | 109.5 |
C5—C4—C3 | 121.0 (2) | O2—C22—N6 | 125.5 (3) |
C5—C4—C41 | 119.0 (3) | O2—C22—H22 | 117.3 |
C3—C4—C41 | 120.0 (2) | N6—C22—H22 | 117.3 |
C4—C5—C6 | 117.4 (3) | N6—C23—H23A | 109.5 |
C4—C5—H5 | 121.3 | N6—C23—H23B | 109.5 |
C6—C5—H5 | 121.3 | H23A—C23—H23B | 109.5 |
N3—C6—C5 | 131.2 (2) | N6—C23—H23C | 109.5 |
N3—C6—C1 | 106.3 (2) | H23A—C23—H23C | 109.5 |
C5—C6—C1 | 122.4 (2) | H23B—C23—H23C | 109.5 |
N1—C7—N3 | 112.3 (2) | N6—C24—H24A | 109.5 |
N1—C7—C8 | 119.0 (2) | N6—C24—H24B | 109.5 |
N3—C7—C8 | 128.7 (2) | H24A—C24—H24B | 109.5 |
N2—C8—C9 | 121.7 (2) | N6—C24—H24C | 109.5 |
N2—C8—C7 | 112.1 (2) | H24A—C24—H24C | 109.5 |
C9—C8—C7 | 126.1 (3) | H24B—C24—H24C | 109.5 |
C8—C9—C10 | 117.8 (3) | C3—C31—H31A | 109.5 |
C8—C9—H9 | 121.1 | C3—C31—H31B | 109.5 |
C10—C9—H9 | 121.1 | H31A—C31—H31B | 109.5 |
C11—C10—C9 | 120.4 (3) | C3—C31—H31C | 109.5 |
C11—C10—H10 | 119.8 | H31A—C31—H31C | 109.5 |
C9—C10—H10 | 119.8 | H31B—C31—H31C | 109.5 |
C10—C11—C12 | 118.1 (3) | C4—C41—H41A | 109.5 |
C10—C11—H11 | 120.9 | C4—C41—H41B | 109.5 |
C12—C11—H11 | 120.9 | H41A—C41—H41B | 109.5 |
N2—C12—C11 | 122.4 (3) | C4—C41—H41C | 109.5 |
N2—C12—H12 | 118.8 | H41A—C41—H41C | 109.5 |
C11—C12—H12 | 118.8 | H41B—C41—H41C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O1 | 0.95 | 2.30 | 3.034 (4) | 134 |
C5—H5···Cl2i | 0.95 | 2.78 | 3.612 (3) | 147 |
C9—H9···O2 | 0.95 | 2.45 | 3.226 (4) | 139 |
C19—H19···Cl1 | 0.95 | 2.84 | 3.389 (2) | 118 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Zn(C2H3O2)2(C20H18N4)]·C2H6O | F(000) = 1136 |
Mr = 543.91 | Dx = 1.378 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 16.0866 (17) Å | Cell parameters from 6456 reflections |
b = 8.7150 (8) Å | θ = 2.2–23.2° |
c = 18.745 (2) Å | µ = 0.98 mm−1 |
β = 94.193 (4)° | T = 200 K |
V = 2620.9 (5) Å3 | Plate, clear pale grey |
Z = 4 | 0.60 × 0.40 × 0.20 mm |
Bruker SMART X2S benchtop diffractometer | 4636 independent reflections |
Radiation source: sealed microfocus tube | 3543 reflections with I > 2σ(I) |
Doubly curved silicon crystal monochromator | Rint = 0.053 |
Detector resolution: 8.3330 pixels mm-1 | θmax = 25.0°, θmin = 2.5° |
ω scans | h = −19→19 |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | k = −10→10 |
Tmin = 0.67, Tmax = 0.83 | l = −21→22 |
23075 measured reflections |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0415P)2 + 0.6452P] where P = (Fo2 + 2Fc2)/3 |
4636 reflections | (Δ/σ)max = 0.002 |
361 parameters | Δρmax = 0.28 e Å−3 |
4 restraints | Δρmin = −0.30 e Å−3 |
Zn(C2H3O2)2(C20H18N4)]·C2H6O | V = 2620.9 (5) Å3 |
Mr = 543.91 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 16.0866 (17) Å | µ = 0.98 mm−1 |
b = 8.7150 (8) Å | T = 200 K |
c = 18.745 (2) Å | 0.60 × 0.40 × 0.20 mm |
β = 94.193 (4)° |
Bruker SMART X2S benchtop diffractometer | 4636 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | 3543 reflections with I > 2σ(I) |
Tmin = 0.67, Tmax = 0.83 | Rint = 0.053 |
23075 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 4 restraints |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.28 e Å−3 |
4636 reflections | Δρmin = −0.30 e Å−3 |
361 parameters |
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. |
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 > 2sigma(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 | Occ. (<1) | |
Zn1 | 1.00931 (2) | 0.64742 (3) | 0.76586 (2) | 0.03809 (11) | |
O1 | 1.11296 (13) | 0.5215 (3) | 0.78573 (12) | 0.0750 (7) | |
O2 | 1.05973 (13) | 0.4878 (3) | 0.67684 (11) | 0.0671 (6) | |
O3 | 0.95559 (14) | 0.8052 (2) | 0.69317 (11) | 0.0620 (6) | |
O4 | 1.06838 (15) | 0.8835 (3) | 0.75097 (13) | 0.0794 (7) | |
N1 | 0.89210 (12) | 0.5955 (2) | 0.95226 (10) | 0.0332 (5) | |
N2 | 0.96702 (12) | 0.6853 (2) | 0.86594 (10) | 0.0333 (5) | |
N3 | 0.89927 (12) | 0.5090 (2) | 0.76307 (10) | 0.0355 (5) | |
N4 | 0.71641 (14) | 0.6761 (2) | 0.96555 (11) | 0.0439 (5) | |
C1 | 1.00139 (14) | 0.7414 (3) | 0.93111 (13) | 0.0354 (6) | |
C2 | 1.06942 (16) | 0.8386 (3) | 0.94653 (14) | 0.0399 (6) | |
H2 | 1.1003 | 0.8785 | 0.9094 | 0.048* | |
C3 | 1.09048 (17) | 0.8751 (3) | 1.01728 (16) | 0.0458 (7) | |
C4 | 1.04362 (18) | 0.8161 (3) | 1.07236 (15) | 0.0458 (7) | |
C5 | 0.97574 (16) | 0.7211 (3) | 1.05715 (13) | 0.0423 (6) | |
H5 | 0.9444 | 0.6815 | 1.0941 | 0.051* | |
C6 | 0.95497 (15) | 0.6855 (2) | 0.98528 (13) | 0.0350 (6) | |
C7 | 0.90267 (15) | 0.6000 (2) | 0.88077 (13) | 0.0319 (5) | |
C8 | 0.85525 (15) | 0.5185 (2) | 0.82155 (12) | 0.0323 (5) | |
C9 | 0.77485 (15) | 0.4623 (3) | 0.82189 (14) | 0.0398 (6) | |
H9 | 0.7435 | 0.4747 | 0.8625 | 0.048* | |
C10 | 0.74102 (17) | 0.3866 (3) | 0.76076 (15) | 0.0451 (7) | |
H10 | 0.6864 | 0.345 | 0.7598 | 0.054* | |
C11 | 0.78682 (17) | 0.3726 (3) | 0.70210 (14) | 0.0453 (7) | |
H11 | 0.7651 | 0.3194 | 0.6606 | 0.054* | |
C12 | 0.86535 (17) | 0.4380 (3) | 0.70506 (13) | 0.0419 (6) | |
H12 | 0.8964 | 0.432 | 0.664 | 0.05* | |
C13 | 0.83317 (15) | 0.5064 (3) | 0.99180 (13) | 0.0386 (6) | |
H12A | 0.8635 | 0.4581 | 1.0338 | 0.046* | |
H13B | 0.8091 | 0.4234 | 0.9607 | 0.046* | |
C14 | 0.76361 (15) | 0.6042 (3) | 1.01669 (13) | 0.0358 (6) | |
C15 | 0.74968 (18) | 0.6147 (3) | 1.08821 (14) | 0.0511 (7) | |
H15 | 0.7841 | 0.5606 | 1.1231 | 0.061* | |
C16 | 0.68468 (19) | 0.7054 (4) | 1.10838 (16) | 0.0644 (9) | |
H16 | 0.6743 | 0.7157 | 1.1574 | 0.077* | |
C17 | 0.63584 (19) | 0.7799 (4) | 1.05690 (16) | 0.0620 (8) | |
H17 | 0.591 | 0.8431 | 1.0692 | 0.074* | |
C18 | 0.65325 (18) | 0.7610 (3) | 0.98690 (15) | 0.0564 (8) | |
H18 | 0.6183 | 0.8114 | 0.9512 | 0.068* | |
C19 | 1.1156 (2) | 0.4625 (4) | 0.72414 (19) | 0.0627 (8) | |
C20 | 1.1889 (2) | 0.3617 (5) | 0.7095 (2) | 0.1041 (15) | |
H20A | 1.183 | 0.3264 | 0.6598 | 0.156* | |
H20B | 1.1905 | 0.2729 | 0.7417 | 0.156* | |
H20C | 1.2406 | 0.4205 | 0.7176 | 0.156* | |
C21 | 1.0095 (2) | 0.9078 (4) | 0.70617 (18) | 0.0612 (8) | |
C22 | 1.0000 (3) | 1.0561 (4) | 0.6651 (2) | 0.0966 (14) | |
H22A | 1.043 | 1.1287 | 0.6833 | 0.145* | |
H22B | 0.9448 | 1.0997 | 0.6711 | 0.145* | |
H22C | 1.0059 | 1.0365 | 0.6143 | 0.145* | |
C31 | 1.16477 (18) | 0.9773 (3) | 1.03577 (18) | 0.0617 (9) | |
H31A | 1.2078 | 0.9191 | 1.0638 | 0.093* | |
H31B | 1.1475 | 1.0651 | 1.0638 | 0.093* | |
H31C | 1.1872 | 1.0142 | 0.9917 | 0.093* | |
C41 | 1.0660 (2) | 0.8603 (3) | 1.14974 (16) | 0.0636 (9) | |
H41A | 1.0295 | 0.8056 | 1.1808 | 0.095* | |
H41B | 1.0588 | 0.9711 | 1.1555 | 0.095* | |
H41C | 1.1241 | 0.8325 | 1.1629 | 0.095* | |
O50 | 0.6649 (10) | 0.2518 (17) | 0.9156 (7) | 0.077 (4) | 0.496 (14) |
H50 | 0.6313 | 0.2702 | 0.8802 | 0.115* | 0.496 (14) |
C51 | 0.6223 (8) | 0.1850 (13) | 0.9699 (5) | 0.094 (4) | 0.496 (14) |
H51A | 0.6623 | 0.1272 | 1.0024 | 0.113* | 0.496 (14) |
H51B | 0.5807 | 0.1114 | 0.9485 | 0.113* | 0.496 (14) |
C52 | 0.5814 (7) | 0.2963 (13) | 1.0097 (7) | 0.099 (4) | 0.496 (14) |
H52A | 0.6226 | 0.368 | 1.0318 | 0.148* | 0.496 (14) |
H52B | 0.552 | 0.2453 | 1.0471 | 0.148* | 0.496 (14) |
H52C | 0.5412 | 0.3528 | 0.9778 | 0.148* | 0.496 (14) |
O60 | 0.6600 (11) | 0.303 (2) | 0.9271 (8) | 0.101 (5) | 0.504 (14) |
H60 | 0.62 | 0.2958 | 0.8958 | 0.151* | 0.504 (14) |
C61 | 0.6301 (12) | 0.292 (2) | 0.9948 (8) | 0.164 (8) | 0.504 (14) |
H61A | 0.5954 | 0.3833 | 1.0028 | 0.197* | 0.504 (14) |
H61B | 0.6781 | 0.2939 | 1.031 | 0.197* | 0.504 (14) |
C62 | 0.5823 (7) | 0.1581 (11) | 1.0052 (7) | 0.102 (4) | 0.504 (14) |
H62A | 0.5439 | 0.1404 | 0.963 | 0.153* | 0.504 (14) |
H62B | 0.5504 | 0.1716 | 1.0474 | 0.153* | 0.504 (14) |
H62C | 0.6196 | 0.0696 | 1.0126 | 0.153* | 0.504 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.03716 (18) | 0.04128 (18) | 0.03629 (19) | 0.00028 (14) | 0.00570 (13) | 0.00074 (13) |
O1 | 0.0623 (14) | 0.0948 (16) | 0.0668 (15) | 0.0325 (13) | −0.0026 (12) | −0.0218 (13) |
O2 | 0.0539 (13) | 0.0952 (16) | 0.0536 (13) | 0.0154 (12) | 0.0137 (11) | 0.0165 (12) |
O3 | 0.0773 (15) | 0.0497 (11) | 0.0604 (13) | 0.0000 (11) | 0.0153 (11) | 0.0111 (10) |
O4 | 0.0693 (16) | 0.1020 (18) | 0.0691 (16) | −0.0058 (14) | 0.0211 (13) | 0.0096 (14) |
N1 | 0.0346 (11) | 0.0346 (10) | 0.0306 (11) | 0.0055 (9) | 0.0031 (9) | −0.0003 (9) |
N2 | 0.0314 (11) | 0.0346 (10) | 0.0338 (11) | 0.0001 (9) | 0.0007 (9) | −0.0025 (9) |
N3 | 0.0426 (12) | 0.0363 (10) | 0.0279 (11) | −0.0011 (10) | 0.0040 (10) | 0.0012 (9) |
N4 | 0.0480 (13) | 0.0487 (12) | 0.0354 (12) | 0.0134 (11) | 0.0050 (10) | 0.0012 (10) |
C1 | 0.0328 (13) | 0.0322 (12) | 0.0408 (15) | 0.0092 (11) | 0.0002 (11) | −0.0053 (11) |
C2 | 0.0358 (14) | 0.0336 (12) | 0.0494 (16) | 0.0054 (11) | −0.0037 (12) | −0.0053 (11) |
C3 | 0.0422 (15) | 0.0328 (13) | 0.0598 (19) | 0.0118 (12) | −0.0133 (14) | −0.0108 (13) |
C4 | 0.0551 (17) | 0.0354 (13) | 0.0443 (16) | 0.0196 (13) | −0.0149 (14) | −0.0097 (12) |
C5 | 0.0505 (16) | 0.0429 (14) | 0.0330 (14) | 0.0176 (13) | −0.0005 (12) | −0.0032 (11) |
C6 | 0.0365 (14) | 0.0315 (12) | 0.0365 (14) | 0.0099 (11) | −0.0022 (11) | −0.0042 (10) |
C7 | 0.0333 (13) | 0.0295 (11) | 0.0329 (14) | 0.0054 (11) | 0.0023 (11) | −0.0002 (10) |
C8 | 0.0352 (13) | 0.0283 (11) | 0.0331 (14) | 0.0022 (10) | 0.0000 (11) | 0.0014 (10) |
C9 | 0.0369 (14) | 0.0403 (13) | 0.0422 (15) | 0.0004 (12) | 0.0029 (12) | −0.0023 (11) |
C10 | 0.0387 (15) | 0.0451 (14) | 0.0504 (18) | −0.0067 (12) | −0.0050 (13) | −0.0027 (13) |
C11 | 0.0535 (17) | 0.0434 (14) | 0.0376 (16) | −0.0061 (13) | −0.0070 (13) | −0.0043 (12) |
C12 | 0.0538 (17) | 0.0427 (14) | 0.0288 (14) | −0.0018 (13) | 0.0009 (12) | −0.0018 (11) |
C13 | 0.0440 (15) | 0.0377 (13) | 0.0342 (14) | 0.0051 (12) | 0.0034 (12) | 0.0043 (11) |
C14 | 0.0370 (14) | 0.0379 (13) | 0.0328 (14) | 0.0000 (11) | 0.0055 (11) | 0.0008 (10) |
C15 | 0.0488 (17) | 0.0722 (18) | 0.0327 (15) | 0.0064 (15) | 0.0059 (13) | 0.0047 (13) |
C16 | 0.0571 (19) | 0.100 (2) | 0.0381 (17) | 0.0096 (19) | 0.0172 (15) | −0.0073 (17) |
C17 | 0.0514 (18) | 0.085 (2) | 0.0517 (19) | 0.0199 (17) | 0.0160 (15) | −0.0101 (17) |
C18 | 0.0574 (18) | 0.0655 (18) | 0.0465 (18) | 0.0231 (16) | 0.0046 (14) | 0.0020 (14) |
C19 | 0.054 (2) | 0.0665 (19) | 0.069 (2) | 0.0159 (16) | 0.0154 (18) | 0.0015 (18) |
C20 | 0.082 (3) | 0.146 (4) | 0.083 (3) | 0.060 (3) | −0.004 (2) | −0.036 (3) |
C21 | 0.069 (2) | 0.0601 (19) | 0.058 (2) | 0.0064 (18) | 0.0320 (18) | 0.0051 (16) |
C22 | 0.156 (4) | 0.0503 (19) | 0.085 (3) | −0.010 (2) | 0.024 (3) | 0.0169 (18) |
C31 | 0.0511 (18) | 0.0468 (15) | 0.084 (2) | 0.0043 (14) | −0.0199 (16) | −0.0171 (15) |
C41 | 0.083 (2) | 0.0528 (16) | 0.0507 (18) | 0.0210 (16) | −0.0249 (17) | −0.0160 (14) |
O50 | 0.079 (6) | 0.099 (7) | 0.055 (5) | 0.023 (5) | 0.020 (4) | 0.021 (5) |
C51 | 0.091 (8) | 0.098 (7) | 0.095 (8) | 0.002 (6) | 0.028 (7) | 0.028 (6) |
C52 | 0.090 (8) | 0.078 (7) | 0.125 (10) | −0.018 (6) | −0.005 (7) | −0.021 (6) |
O60 | 0.095 (8) | 0.137 (12) | 0.074 (7) | −0.041 (8) | 0.038 (5) | −0.003 (6) |
C61 | 0.165 (15) | 0.162 (13) | 0.181 (14) | −0.099 (12) | 0.107 (12) | −0.084 (11) |
C62 | 0.095 (8) | 0.106 (8) | 0.107 (9) | −0.011 (6) | 0.016 (6) | 0.013 (6) |
Zn1—O1 | 2.008 (2) | C13—H12A | 0.99 |
Zn1—N2 | 2.068 (2) | C13—H13B | 0.99 |
Zn1—O3 | 2.079 (2) | C14—C15 | 1.378 (3) |
Zn1—N3 | 2.139 (2) | C15—C16 | 1.386 (4) |
Zn1—O4 | 2.292 (2) | C15—H15 | 0.95 |
Zn1—O2 | 2.362 (2) | C16—C17 | 1.363 (4) |
Zn1—C19 | 2.515 (3) | C16—H16 | 0.95 |
Zn1—C21 | 2.530 (3) | C17—C18 | 1.371 (4) |
O1—C19 | 1.268 (4) | C17—H17 | 0.95 |
O2—C19 | 1.235 (4) | C18—H18 | 0.95 |
O3—C21 | 1.257 (4) | C19—C20 | 1.511 (4) |
O4—C21 | 1.237 (4) | C20—H20A | 0.98 |
N1—C7 | 1.364 (3) | C20—H20B | 0.98 |
N1—C6 | 1.389 (3) | C20—H20C | 0.98 |
N1—C13 | 1.467 (3) | C21—C22 | 1.506 (4) |
N2—C7 | 1.320 (3) | C22—H22A | 0.98 |
N2—C1 | 1.392 (3) | C22—H22B | 0.98 |
N3—C12 | 1.333 (3) | C22—H22C | 0.98 |
N3—C8 | 1.350 (3) | C31—H31A | 0.98 |
N4—C14 | 1.335 (3) | C31—H31B | 0.98 |
N4—C18 | 1.342 (3) | C31—H31C | 0.98 |
C1—C6 | 1.392 (3) | C41—H41A | 0.98 |
C1—C2 | 1.398 (3) | C41—H41B | 0.98 |
C2—C3 | 1.382 (4) | C41—H41C | 0.98 |
C2—H2 | 0.95 | O50—C51 | 1.395 (14) |
C3—C4 | 1.419 (4) | O50—H50 | 0.84 |
C3—C31 | 1.511 (4) | C51—C52 | 1.416 (9) |
C4—C5 | 1.383 (4) | C51—H51A | 0.99 |
C4—C41 | 1.518 (4) | C51—H51B | 0.99 |
C5—C6 | 1.399 (3) | C52—H52A | 0.98 |
C5—H5 | 0.95 | C52—H52B | 0.98 |
C7—C8 | 1.481 (3) | C52—H52C | 0.98 |
C8—C9 | 1.384 (3) | O60—C61 | 1.392 (14) |
C9—C10 | 1.397 (3) | O60—H60 | 0.84 |
C9—H9 | 0.95 | C61—C62 | 1.420 (9) |
C10—C11 | 1.373 (4) | C61—H61A | 0.99 |
C10—H10 | 0.95 | C61—H61B | 0.99 |
C11—C12 | 1.383 (4) | C62—H62A | 0.98 |
C11—H11 | 0.95 | C62—H62B | 0.98 |
C12—H12 | 0.95 | C62—H62C | 0.98 |
C13—C14 | 1.507 (3) | ||
O1—Zn1—N2 | 104.04 (9) | N1—C13—H13B | 109.1 |
O1—Zn1—O3 | 141.51 (9) | C14—C13—H13B | 109.1 |
N2—Zn1—O3 | 109.90 (8) | H12A—C13—H13B | 107.9 |
O1—Zn1—N3 | 111.77 (9) | N4—C14—C15 | 122.9 (2) |
N2—Zn1—N3 | 77.63 (7) | N4—C14—C13 | 116.1 (2) |
O3—Zn1—N3 | 93.07 (8) | C15—C14—C13 | 121.0 (2) |
O1—Zn1—O4 | 99.61 (10) | C14—C15—C16 | 118.9 (3) |
N2—Zn1—O4 | 97.70 (8) | C14—C15—H15 | 120.6 |
O3—Zn1—O4 | 58.83 (9) | C16—C15—H15 | 120.6 |
N3—Zn1—O4 | 148.52 (8) | C17—C16—C15 | 119.1 (3) |
O1—Zn1—O2 | 59.05 (8) | C17—C16—H16 | 120.5 |
N2—Zn1—O2 | 152.59 (7) | C15—C16—H16 | 120.5 |
O3—Zn1—O2 | 94.27 (8) | C16—C17—C18 | 118.2 (3) |
N3—Zn1—O2 | 88.67 (8) | C16—C17—H17 | 120.9 |
O4—Zn1—O2 | 106.02 (8) | C18—C17—H17 | 120.9 |
O1—Zn1—C19 | 29.95 (9) | N4—C18—C17 | 124.3 (3) |
N2—Zn1—C19 | 131.32 (10) | N4—C18—H18 | 117.8 |
O3—Zn1—C19 | 118.65 (10) | C17—C18—H18 | 117.8 |
N3—Zn1—C19 | 102.18 (9) | O2—C19—O1 | 120.7 (3) |
O4—Zn1—C19 | 103.89 (10) | O2—C19—C20 | 120.6 (3) |
O2—Zn1—C19 | 29.12 (8) | O1—C19—C20 | 118.7 (3) |
O1—Zn1—C21 | 122.97 (11) | O2—C19—Zn1 | 68.52 (17) |
N2—Zn1—C21 | 105.61 (9) | O1—C19—Zn1 | 52.27 (14) |
O3—Zn1—C21 | 29.63 (10) | C20—C19—Zn1 | 170.3 (3) |
N3—Zn1—C21 | 121.50 (10) | C19—C20—H20A | 109.5 |
O4—Zn1—C21 | 29.20 (9) | C19—C20—H20B | 109.5 |
O2—Zn1—C21 | 101.80 (9) | H20A—C20—H20B | 109.5 |
C19—Zn1—C21 | 114.48 (10) | C19—C20—H20C | 109.5 |
C19—O1—Zn1 | 97.78 (18) | H20A—C20—H20C | 109.5 |
C19—O2—Zn1 | 82.36 (19) | H20B—C20—H20C | 109.5 |
C21—O3—Zn1 | 95.5 (2) | O4—C21—O3 | 119.5 (3) |
C21—O4—Zn1 | 86.1 (2) | O4—C21—C22 | 122.5 (4) |
C7—N1—C6 | 106.41 (19) | O3—C21—C22 | 117.9 (3) |
C7—N1—C13 | 130.0 (2) | O4—C21—Zn1 | 64.66 (18) |
C6—N1—C13 | 123.4 (2) | O3—C21—Zn1 | 54.87 (15) |
C7—N2—C1 | 106.3 (2) | C22—C21—Zn1 | 172.8 (3) |
C7—N2—Zn1 | 114.58 (15) | C21—C22—H22A | 109.5 |
C1—N2—Zn1 | 135.73 (16) | C21—C22—H22B | 109.5 |
C12—N3—C8 | 118.9 (2) | H22A—C22—H22B | 109.5 |
C12—N3—Zn1 | 124.78 (17) | C21—C22—H22C | 109.5 |
C8—N3—Zn1 | 115.32 (15) | H22A—C22—H22C | 109.5 |
C14—N4—C18 | 116.6 (2) | H22B—C22—H22C | 109.5 |
C6—C1—N2 | 108.5 (2) | C3—C31—H31A | 109.5 |
C6—C1—C2 | 121.0 (2) | C3—C31—H31B | 109.5 |
N2—C1—C2 | 130.5 (2) | H31A—C31—H31B | 109.5 |
C3—C2—C1 | 118.1 (3) | C3—C31—H31C | 109.5 |
C3—C2—H2 | 120.9 | H31A—C31—H31C | 109.5 |
C1—C2—H2 | 120.9 | H31B—C31—H31C | 109.5 |
C2—C3—C4 | 120.6 (2) | C4—C41—H41A | 109.5 |
C2—C3—C31 | 119.4 (3) | C4—C41—H41B | 109.5 |
C4—C3—C31 | 120.0 (3) | H41A—C41—H41B | 109.5 |
C5—C4—C3 | 121.4 (2) | C4—C41—H41C | 109.5 |
C5—C4—C41 | 118.5 (3) | H41A—C41—H41C | 109.5 |
C3—C4—C41 | 120.1 (3) | H41B—C41—H41C | 109.5 |
C4—C5—C6 | 117.4 (3) | C51—O50—H50 | 109.5 |
C4—C5—H5 | 121.3 | O50—C51—C52 | 111.8 (14) |
C6—C5—H5 | 121.3 | O50—C51—H51A | 109.3 |
N1—C6—C1 | 106.5 (2) | C52—C51—H51A | 109.3 |
N1—C6—C5 | 132.0 (2) | O50—C51—H51B | 109.3 |
C1—C6—C5 | 121.5 (2) | C52—C51—H51B | 109.3 |
N2—C7—N1 | 112.3 (2) | H51A—C51—H51B | 107.9 |
N2—C7—C8 | 118.7 (2) | C51—C52—H52A | 109.5 |
N1—C7—C8 | 128.9 (2) | C51—C52—H52B | 109.5 |
N3—C8—C9 | 121.9 (2) | H52A—C52—H52B | 109.5 |
N3—C8—C7 | 111.4 (2) | C51—C52—H52C | 109.5 |
C9—C8—C7 | 126.6 (2) | H52A—C52—H52C | 109.5 |
C8—C9—C10 | 118.1 (2) | H52B—C52—H52C | 109.5 |
C8—C9—H9 | 120.9 | C61—O60—H60 | 109.5 |
C10—C9—H9 | 120.9 | O60—C61—C62 | 114.1 (16) |
C11—C10—C9 | 120.0 (2) | O60—C61—H61A | 108.7 |
C11—C10—H10 | 120.0 | C62—C61—H61A | 108.7 |
C9—C10—H10 | 120.0 | O60—C61—H61B | 108.7 |
C10—C11—C12 | 118.2 (2) | C62—C61—H61B | 108.7 |
C10—C11—H11 | 120.9 | H61A—C61—H61B | 107.6 |
C12—C11—H11 | 120.9 | C61—C62—H62A | 109.5 |
N3—C12—C11 | 122.8 (3) | C61—C62—H62B | 109.5 |
N3—C12—H12 | 118.6 | H62A—C62—H62B | 109.5 |
C11—C12—H12 | 118.6 | C61—C62—H62C | 109.5 |
N1—C13—C14 | 112.28 (18) | H62A—C62—H62C | 109.5 |
N1—C13—H12A | 109.1 | H62B—C62—H62C | 109.5 |
C14—C13—H12A | 109.1 | ||
C7—N2—C1—C6 | 0.2 (2) | C12—N3—C8—C7 | 179.6 (2) |
Zn1—N2—C1—C6 | −156.77 (17) | Zn1—N3—C8—C7 | −11.4 (2) |
C7—N2—C1—C2 | −179.0 (2) | N2—C7—C8—N3 | 17.6 (3) |
Zn1—N2—C1—C2 | 24.0 (4) | N1—C7—C8—N3 | −159.1 (2) |
C6—C1—C2—C3 | 1.4 (3) | N2—C7—C8—C9 | −160.0 (2) |
N2—C1—C2—C3 | −179.5 (2) | N1—C7—C8—C9 | 23.3 (4) |
C1—C2—C3—C4 | −0.5 (3) | N3—C8—C9—C10 | 3.5 (3) |
C1—C2—C3—C31 | 178.8 (2) | C7—C8—C9—C10 | −179.3 (2) |
C2—C3—C4—C5 | −0.1 (4) | C8—C9—C10—C11 | −1.3 (4) |
C31—C3—C4—C5 | −179.4 (2) | C9—C10—C11—C12 | −1.5 (4) |
C2—C3—C4—C41 | −178.4 (2) | C8—N3—C12—C11 | −0.3 (3) |
C31—C3—C4—C41 | 2.3 (3) | Zn1—N3—C12—C11 | −168.15 (18) |
C3—C4—C5—C6 | −0.1 (3) | C10—C11—C12—N3 | 2.3 (4) |
C41—C4—C5—C6 | 178.2 (2) | C7—N1—C13—C14 | −105.8 (3) |
C7—N1—C6—C1 | 0.1 (2) | C6—N1—C13—C14 | 80.1 (3) |
C13—N1—C6—C1 | 175.37 (19) | C18—N4—C14—C15 | −0.1 (4) |
C7—N1—C6—C5 | −179.0 (2) | C18—N4—C14—C13 | 178.7 (2) |
C13—N1—C6—C5 | −3.7 (4) | N1—C13—C14—N4 | 59.4 (3) |
N2—C1—C6—N1 | −0.2 (2) | N1—C13—C14—C15 | −121.8 (3) |
C2—C1—C6—N1 | 179.14 (19) | N4—C14—C15—C16 | −0.9 (4) |
N2—C1—C6—C5 | 179.0 (2) | C13—C14—C15—C16 | −179.7 (3) |
C2—C1—C6—C5 | −1.7 (3) | C14—C15—C16—C17 | 0.9 (5) |
C4—C5—C6—N1 | 179.9 (2) | C15—C16—C17—C18 | 0.2 (5) |
C4—C5—C6—C1 | 0.9 (3) | C14—N4—C18—C17 | 1.2 (4) |
C1—N2—C7—N1 | −0.1 (2) | C16—C17—C18—N4 | −1.3 (5) |
Zn1—N2—C7—N1 | 162.37 (14) | Zn1—O2—C19—O1 | 3.0 (3) |
C1—N2—C7—C8 | −177.37 (19) | Zn1—O2—C19—C20 | −176.5 (3) |
Zn1—N2—C7—C8 | −14.9 (3) | Zn1—O1—C19—O2 | −3.5 (4) |
C6—N1—C7—N2 | 0.1 (2) | Zn1—O1—C19—C20 | 175.9 (3) |
C13—N1—C7—N2 | −174.8 (2) | Zn1—O4—C21—O3 | −0.5 (3) |
C6—N1—C7—C8 | 176.9 (2) | Zn1—O4—C21—C22 | −179.6 (3) |
C13—N1—C7—C8 | 2.0 (4) | Zn1—O3—C21—O4 | 0.6 (3) |
C12—N3—C8—C9 | −2.7 (3) | Zn1—O3—C21—C22 | 179.7 (3) |
Zn1—N3—C8—C9 | 166.30 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9···O50 | 0.95 | 2.56 | 3.167 (15) | 122 |
C9—H9···O60 | 0.95 | 2.40 | 3.125 (14) | 133 |
C15—H15···O1i | 0.95 | 2.40 | 3.333 (3) | 167 |
C17—H17···O2ii | 0.95 | 2.58 | 3.325 (4) | 136 |
O50—H50···O3iii | 0.84 | 1.91 | 2.749 (15) | 173 |
C10—H10···O3iii | 0.95 | 2.53 | 3.414 (4) | 155 |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) x−1/2, −y+3/2, z+1/2; (iii) −x+3/2, y−1/2, −z+3/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [ZnCl2(C20H18N4)(C3H7NO)]·C3H7NO | Zn(C2H3O2)2(C20H18N4)]·C2H6O |
Mr | 596.84 | 543.91 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/n |
Temperature (K) | 200 | 200 |
a, b, c (Å) | 11.2504 (11), 11.7298 (11), 12.6588 (13) | 16.0866 (17), 8.7150 (8), 18.745 (2) |
α, β, γ (°) | 71.518 (4), 71.087 (3), 65.760 (3) | 90, 94.193 (4), 90 |
V (Å3) | 1407.9 (2) | 2620.9 (5) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.10 | 0.98 |
Crystal size (mm) | 0.58 × 0.30 × 0.20 | 0.60 × 0.40 × 0.20 |
Data collection | ||
Diffractometer | Bruker SMART X2S benchtop | Bruker SMART X2S benchtop |
Absorption correction | Multi-scan (SADABS; Bruker, 2013) | Multi-scan (SADABS; Bruker, 2013) |
Tmin, Tmax | 0.56, 0.81 | 0.67, 0.83 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12063, 4976, 4058 | 23075, 4636, 3543 |
Rint | 0.047 | 0.053 |
(sin θ/λ)max (Å−1) | 0.603 | 0.595 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.107, 1.05 | 0.036, 0.090, 1.02 |
No. of reflections | 4976 | 4636 |
No. of parameters | 340 | 361 |
No. of restraints | 0 | 4 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.40, −0.64 | 0.28, −0.30 |
Computer programs: APEX2 (Bruker, 2013), SAINT (Bruker, 2013), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006), publCIF (Westrip, 2010).
Zn1—Cl1 | 2.2775 (8) | Zn1—N2 | 2.235 (2) |
Zn1—Cl2 | 2.2788 (9) | Zn1—O1 | 2.1298 (19) |
Zn1—N1 | 2.067 (2) | ||
N1—Zn1—O1 | 89.50 (8) | N2—Zn1—Cl1 | 92.36 (6) |
N1—Zn1—N2 | 75.63 (8) | N1—Zn1—Cl2 | 121.19 (6) |
O1—Zn1—N2 | 165.10 (9) | O1—Zn1—Cl2 | 92.71 (7) |
N1—Zn1—Cl1 | 122.26 (6) | N2—Zn1—Cl2 | 95.85 (6) |
O1—Zn1—Cl1 | 94.81 (6) | Cl1—Zn1—Cl2 | 116.08 (3) |
Zn1—O1 | 2.008 (2) | Zn1—N3 | 2.139 (2) |
Zn1—N2 | 2.068 (2) | Zn1—O4 | 2.292 (2) |
Zn1—O3 | 2.079 (2) | Zn1—O2 | 2.362 (2) |
O1—Zn1—N2 | 104.04 (9) | N2—Zn1—O4 | 97.70 (8) |
O1—Zn1—O3 | 141.51 (9) | N3—Zn1—O4 | 148.52 (8) |
N2—Zn1—O3 | 109.90 (8) | N2—Zn1—O2 | 152.59 (7) |
O1—Zn1—N3 | 111.77 (9) | O3—Zn1—O2 | 94.27 (8) |
N2—Zn1—N3 | 77.63 (7) | N3—Zn1—O2 | 88.67 (8) |
O3—Zn1—N3 | 93.07 (8) | O4—Zn1—O2 | 106.02 (8) |
O1—Zn1—O4 | 99.61 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O1 | 0.95 | 2.30 | 3.034 (4) | 133.5 |
C5—H5···Cl2i | 0.95 | 2.78 | 3.612 (3) | 146.7 |
C9—H9···O2 | 0.95 | 2.45 | 3.226 (4) | 139.1 |
C19—H19···Cl1 | 0.95 | 2.84 | 3.389 (2) | 117.8 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9···O50 | 0.95 | 2.56 | 3.167 (15) | 122.1 |
C15—H15···O1i | 0.95 | 2.40 | 3.333 (3) | 167.0 |
C17—H17···O2ii | 0.95 | 2.58 | 3.325 (4) | 135.8 |
O50—H50···O3iii | 0.84 | 1.91 | 2.749 (15) | 173.1 |
C10—H10···O3iii | 0.95 | 2.53 | 3.414 (4) | 154.5 |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) x−1/2, −y+3/2, z+1/2; (iii) −x+3/2, y−1/2, −z+3/2. |