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Luminescent metal complexes are used in photooptical devices. Zinc(II) com­plexes are of interest because of the ability to tune their color, their high thermal stability and their favorable carrier transport character. In particular, some zinc(II) com­plexes with aryl di­imine and/or heterocyclic ligands have been shown to emit brightly in the blue region of the spectrum. Zinc(II) complexes bearing derivatized imidazoles have been explored for possible optoelectronic applications. The structures of two zinc(II) complexes of 5,6-dimethyl-2-(pyri­din-2-yl)-1-[(pyridin-2-yl)meth­yl]-1H-benzimidazole (L), namely di­chlorido(di­methyl­formamide-[kappa]O)­{5,6-di­methyl-2-(pyridin-2-yl-[kappa]N)-1-[(pyridin-2-yl)meth­yl]-1H-benzimidazole-[kappa]N3}zinc(II) di­methyl­formamide monosolvate, [ZnCl2(C20H18N4)(C3H7NO)]·C3H7NO, (I), and bis­(acetato-[kappa]2O,O'){5,6-dimethyl-2-(pyridin-2-yl-[kappa]N)-1-[(pyridin-2-yl)meth­yl]-1H-benzimidazole-[kappa]N3}zinc(II) ethanol monosolvate, [Zn(C2H3O2)2(C20H18N4)]·C2H5OH, (II), are reported. Complex (I) crystallized as a di­methyl­formamide solvate and exhibits a distorted trigonal bipyramidal coordination geometry. The coordination sphere consists of a bidentate L ligand spanning axial to equatorial sites, two chloride ligands in equatorial sites, and an O-bound di­methyl­formamide ligand in the remaining axial site. The other complex, (II), crystallized as an ethanol solvate. The ZnII atom has a distorted trigonal prismatic coordination geometry, with two bidentate acetate ligands occupying two edges and a bidentate L ligand occupying the third edge of the prism. Complexes (I) and (II) emit in the blue region of the spectrum. The results of density functional theory (DFT) calculations suggest that the luminescence of L results from [pi]*[leftwards arrow][pi] transitions and that the luminescence of the complexes results from inter­ligand charge-transfer transitions. The orientation of the 2-(pyridin-2-yl) substituent with respect to the benzimidazole system was found to have an impact on the calculated HOMO-LUMO gap (HOMO is highest occupied mol­ecular orbital and LUMO is lowest unoccupied mol­ecular orbital).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616007798/uk3125sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229616007798/uk3125Isup2.hkl
Contains datablock I

mol

MDL mol file https://doi.org/10.1107/S2053229616007798/uk3125Isup4.mol
Supplementary material

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229616007798/uk3125IIsup3.hkl
Contains datablock II

mol

MDL mol file https://doi.org/10.1107/S2053229616007798/uk3125IIsup5.mol
Supplementary material

CCDC references: 1479262; 1479261

Introduction top

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).

Experimental top

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.

Synthesis and crystallization top

5,6-Di­methyl-2-(pyridin-2-yl)-1-[(pyridin-2-yl)methyl]-1H-benzimidazole, ligand L, was prepared as described previously (Geiger & DeStefano, 2014).

Preparation of complex (I) top

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.

Preparation of complex (II) top

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).

Refinement top

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.

Computations top

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.

Results and discussion top

Description of structures top

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).

Spectroscopy top

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.

Conclusions top

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.

Structure description top

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.

Synthesis and crystallization top

5,6-Di­methyl-2-(pyridin-2-yl)-1-[(pyridin-2-yl)methyl]-1H-benzimidazole, ligand L, was prepared as described previously (Geiger & DeStefano, 2014).

Refinement details top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. A perspective view of (I), showing the atom-labeling scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
[Figure 2] Fig. 2. A perspective view of (II), showing the atom-labeling scheme. Displacemenet ellipsoids for non-H atoms are drawn at the 30% probability level. Only one contributor to the ethanol disorder model is shown.
[Figure 3] Fig. 3. A partial packing diagram of (I), showing the double chain along [110] formed by weak hydrogen-bonding interactions. Only H atoms involved in the interactions are shown. [Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) x + 1, y + 1, z; (iii) -x + 1, y + 1, z; (iv) -x + 2, -y, -z + 1.]
[Figure 4] Fig. 4. A partial packing diagram of (II), showing hydrogen-bonding interactions leading to chains along [010]. Only H atoms involved in the interactions are shown and only one contributor to the disordered ethanol molecule is shown. [Symmetry codes: (i) -x + 3/2, y - 1/2, -z + 3/2; (ii) -x + 3/2, y + 1/2, -z + 3/2; (iii) x, y - 1, z.]
[Figure 5] Fig. 5. Absorbance and emission spectra of 5 × 10-5 M solutions in CHCl3 for L (full black lines), (I) (dotted lines), and (II) (dashed lines).
[Figure 6] Fig. 6. Frontier molecular orbitals and their energies for L, (I), and (II).
(I) Dichlorido(dimethylformamide-κO){5,6-dimethyl-2-(pyridin-2-yl-κN)-1-[(pyridin-2-yl)methyl]-1H-benzimidazole-κN3}zinc(II) dimethylformamide monosolvate top
Crystal data top
[ZnCl2(C20H18N4)(C3H7NO)]·C3H7NOZ = 2
Mr = 596.84F(000) = 620
Triclinic, P1Dx = 1.408 Mg m3
a = 11.2504 (11) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.7298 (11) ÅCell parameters from 4156 reflections
c = 12.6588 (13) Åθ = 2.4–25.2°
α = 71.518 (4)°µ = 1.10 mm1
β = 71.087 (3)°T = 200 K
γ = 65.760 (3)°Needle, clear colourless
V = 1407.9 (2) Å30.58 × 0.30 × 0.20 mm
Data collection top
Bruker SMART X2S benchtop
diffractometer
4976 independent reflections
Radiation source: sealed microfocus tube4058 reflections with I > 2σ(I)
Doubly curved silicon crystal monochromatorRint = 0.047
Detector resolution: 8.3330 pixels mm-1θmax = 25.4°, θmin = 2.3°
/w scansh = 1213
Absorption correction: multi-scan
(SADABS; Bruker, 2013)
k = 1313
Tmin = 0.56, Tmax = 0.81l = 1514
12063 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107H-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 parametersΔρmax = 0.40 e Å3
0 restraintsΔρmin = 0.64 e Å3
Crystal data top
[ZnCl2(C20H18N4)(C3H7NO)]·C3H7NOγ = 65.760 (3)°
Mr = 596.84V = 1407.9 (2) Å3
Triclinic, P1Z = 2
a = 11.2504 (11) ÅMo Kα radiation
b = 11.7298 (11) ŵ = 1.10 mm1
c = 12.6588 (13) ÅT = 200 K
α = 71.518 (4)°0.58 × 0.30 × 0.20 mm
β = 71.087 (3)°
Data collection top
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 = 0.81Rint = 0.047
12063 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.107H-atom parameters constrained
S = 1.05Δρmax = 0.40 e Å3
4976 reflectionsΔρmin = 0.64 e Å3
340 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.56523 (3)0.12184 (3)0.66858 (2)0.02769 (12)
Cl10.47553 (7)0.03597 (7)0.75730 (6)0.0398 (2)
Cl20.76891 (8)0.08344 (8)0.69805 (8)0.0539 (2)
O10.6512 (2)0.0607 (2)0.51059 (17)0.0518 (6)
O20.0887 (3)0.7101 (3)0.8691 (2)0.0719 (8)
N10.4590 (2)0.2990 (2)0.58394 (16)0.0224 (5)
N20.4455 (2)0.2320 (2)0.80622 (17)0.0273 (5)
N30.31680 (19)0.4993 (2)0.58193 (16)0.0215 (5)
N40.0522 (2)0.5219 (2)0.6568 (2)0.0325 (6)
N50.7837 (2)0.0957 (2)0.41491 (19)0.0343 (6)
N60.0489 (3)0.8385 (3)0.9914 (2)0.0465 (7)
C10.4522 (2)0.3607 (3)0.4705 (2)0.0211 (5)
C20.5174 (2)0.3181 (3)0.3683 (2)0.0238 (6)
H20.5790.23340.36820.029*
C30.4897 (3)0.4032 (3)0.2668 (2)0.0268 (6)
C40.3968 (3)0.5294 (3)0.2673 (2)0.0280 (6)
C50.3328 (3)0.5717 (3)0.3681 (2)0.0267 (6)
H50.27080.65630.36870.032*
C60.3625 (2)0.4858 (3)0.4689 (2)0.0220 (6)
C70.3752 (2)0.3848 (3)0.6468 (2)0.0217 (6)
C80.3564 (2)0.3466 (3)0.7727 (2)0.0237 (6)
C90.2576 (3)0.4158 (3)0.8511 (2)0.0328 (7)
H90.19390.49620.82650.039*
C100.2550 (3)0.3634 (3)0.9669 (2)0.0398 (8)
H100.18830.40811.02260.048*
C110.3478 (3)0.2481 (3)1.0008 (2)0.0402 (8)
H110.34810.21271.07950.048*
C120.4417 (3)0.1841 (3)0.9170 (2)0.0351 (7)
H120.50560.10310.93980.042*
C130.2217 (2)0.6187 (3)0.6145 (2)0.0246 (6)
H13A0.23550.69120.55170.03*
H13B0.240.62660.68280.03*
C140.0774 (2)0.6283 (2)0.64060 (19)0.0215 (6)
C150.0220 (3)0.7448 (3)0.6523 (2)0.0280 (6)
H150.00040.8190.63750.034*
C160.1542 (3)0.7525 (3)0.6858 (2)0.0349 (7)
H160.22410.83110.69670.042*
C170.1819 (3)0.6432 (3)0.7029 (3)0.0395 (8)
H170.27160.64450.72620.047*
C180.0776 (3)0.5329 (3)0.6855 (3)0.0425 (8)
H180.0980.4590.69420.051*
C190.6822 (3)0.0471 (3)0.4948 (2)0.0365 (7)
H190.630.09820.54310.044*
C200.8633 (4)0.0198 (4)0.3359 (4)0.0749 (14)
H20A0.95740.06480.33980.112*
H20B0.83190.06320.35650.112*
H20C0.85440.00650.2580.112*
C210.8162 (4)0.2229 (3)0.3986 (3)0.0524 (9)
H21A0.90980.2730.4020.079*
H21B0.80310.21660.32390.079*
H21C0.75790.2650.45890.079*
C220.0046 (3)0.8047 (3)0.8915 (3)0.0466 (8)
H220.04990.85930.83250.056*
C230.0117 (5)0.7549 (5)1.0860 (3)0.0915 (16)
H23A0.09680.69181.05720.137*
H23B0.04850.71061.140.137*
H23C0.02780.80571.12470.137*
C240.1634 (4)0.9519 (4)1.0116 (4)0.0724 (12)
H24A0.19720.99560.94170.109*
H24B0.13691.00951.03350.109*
H24C0.23370.92761.07330.109*
C310.5605 (3)0.3587 (3)0.1557 (2)0.0371 (7)
H31A0.61220.26710.17180.056*
H31B0.62090.40630.10970.056*
H31C0.49430.37410.11340.056*
C410.3633 (3)0.6185 (3)0.1564 (2)0.0411 (8)
H41A0.30340.70320.17090.062*
H41B0.3190.58420.12510.062*
H41C0.44580.62580.10150.062*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.02231 (19)0.0221 (2)0.03079 (18)0.00082 (14)0.00302 (13)0.00757 (13)
Cl10.0373 (4)0.0320 (4)0.0457 (4)0.0127 (4)0.0013 (3)0.0123 (3)
Cl20.0271 (4)0.0341 (5)0.0989 (7)0.0020 (4)0.0224 (4)0.0204 (4)
O10.0677 (16)0.0254 (13)0.0339 (11)0.0049 (12)0.0027 (11)0.0121 (9)
O20.0593 (17)0.073 (2)0.0688 (17)0.0171 (15)0.0207 (14)0.0431 (15)
N10.0169 (11)0.0219 (13)0.0247 (11)0.0033 (10)0.0023 (9)0.0074 (9)
N20.0257 (12)0.0276 (14)0.0250 (11)0.0058 (11)0.0033 (9)0.0079 (9)
N30.0125 (10)0.0209 (13)0.0265 (11)0.0007 (9)0.0009 (8)0.0093 (9)
N40.0200 (12)0.0250 (14)0.0502 (14)0.0050 (11)0.0054 (10)0.0111 (11)
N50.0269 (13)0.0342 (16)0.0426 (13)0.0061 (12)0.0008 (11)0.0222 (11)
N60.0358 (15)0.057 (2)0.0412 (14)0.0067 (14)0.0008 (12)0.0233 (13)
C10.0135 (12)0.0231 (15)0.0265 (12)0.0055 (11)0.0014 (10)0.0092 (11)
C20.0184 (13)0.0241 (15)0.0306 (13)0.0072 (12)0.0017 (11)0.0118 (11)
C30.0262 (14)0.0367 (18)0.0254 (13)0.0184 (14)0.0008 (11)0.0116 (12)
C40.0274 (15)0.0344 (18)0.0270 (13)0.0175 (14)0.0059 (11)0.0036 (12)
C50.0198 (13)0.0252 (16)0.0338 (14)0.0071 (12)0.0050 (11)0.0064 (12)
C60.0179 (13)0.0255 (16)0.0237 (12)0.0107 (12)0.0010 (10)0.0061 (11)
C70.0118 (12)0.0272 (16)0.0245 (12)0.0041 (11)0.0011 (10)0.0098 (11)
C80.0168 (13)0.0254 (16)0.0285 (13)0.0050 (12)0.0033 (10)0.0102 (11)
C90.0277 (15)0.0336 (18)0.0310 (14)0.0030 (14)0.0034 (12)0.0124 (12)
C100.0350 (17)0.048 (2)0.0283 (14)0.0089 (16)0.0044 (13)0.0168 (14)
C110.051 (2)0.047 (2)0.0236 (14)0.0203 (18)0.0055 (13)0.0061 (13)
C120.0367 (17)0.0292 (18)0.0332 (15)0.0088 (14)0.0070 (13)0.0028 (12)
C130.0176 (13)0.0195 (15)0.0341 (14)0.0025 (12)0.0009 (11)0.0124 (11)
C140.0160 (13)0.0221 (15)0.0244 (12)0.0025 (12)0.0029 (10)0.0095 (11)
C150.0242 (14)0.0220 (16)0.0381 (15)0.0041 (13)0.0074 (12)0.0116 (12)
C160.0200 (14)0.0322 (18)0.0427 (16)0.0071 (13)0.0084 (12)0.0156 (13)
C170.0147 (14)0.044 (2)0.0545 (18)0.0073 (14)0.0035 (13)0.0124 (15)
C180.0262 (16)0.034 (2)0.067 (2)0.0116 (15)0.0083 (15)0.0116 (16)
C190.0295 (16)0.037 (2)0.0297 (14)0.0013 (14)0.0036 (12)0.0099 (13)
C200.067 (3)0.073 (3)0.088 (3)0.043 (3)0.032 (2)0.045 (2)
C210.049 (2)0.052 (2)0.065 (2)0.0187 (19)0.0049 (17)0.0385 (18)
C220.043 (2)0.055 (2)0.0390 (17)0.0073 (18)0.0086 (15)0.0196 (16)
C230.095 (4)0.108 (4)0.050 (2)0.001 (3)0.027 (2)0.024 (2)
C240.044 (2)0.083 (3)0.087 (3)0.002 (2)0.001 (2)0.055 (3)
C310.0390 (17)0.044 (2)0.0281 (14)0.0167 (16)0.0009 (12)0.0128 (13)
C410.048 (2)0.046 (2)0.0307 (15)0.0200 (17)0.0113 (14)0.0022 (14)
Geometric parameters (Å, º) top
N1—C11.400 (3)Zn1—Cl22.2788 (9)
C9—C101.394 (4)C10—H100.95
C10—C111.366 (5)C11—H110.95
C11—C121.390 (4)C12—H120.95
N2—C121.329 (3)C13—H13A0.99
N3—C131.459 (3)C13—H13B0.99
C13—C141.511 (3)C15—H150.95
N4—C141.331 (3)C16—H160.95
C14—C151.380 (4)C17—H170.95
C15—C161.380 (4)C18—H180.95
C16—C171.378 (4)C19—H190.95
C17—C181.366 (4)C2—H20.95
N4—C181.346 (3)C20—H20A0.98
N5—C191.317 (3)C20—H20B0.98
O1—C191.229 (3)C20—H20C0.98
C1—C21.398 (3)C21—H21A0.98
N5—C201.451 (4)C21—H21B0.98
N5—C211.448 (4)C21—H21C0.98
N6—C221.323 (4)C22—H220.95
O2—C221.211 (4)C23—H23A0.98
N6—C231.448 (5)C23—H23B0.98
N6—C241.445 (4)C23—H23C0.98
C2—C31.391 (4)C24—H24A0.98
C3—C311.511 (3)C24—H24B0.98
C3—C41.419 (4)C24—H24C0.98
C4—C411.514 (4)C31—H31A0.98
C4—C51.381 (4)C31—H31B0.98
C5—C61.392 (4)C31—H31C0.98
C1—C61.396 (4)C41—H41A0.98
N3—C61.392 (3)C41—H41B0.98
N3—C71.355 (3)C41—H41C0.98
N1—C71.333 (3)C5—H50.95
C7—C81.481 (3)C9—H90.95
N2—C81.341 (3)Zn1—N12.067 (2)
C8—C91.391 (3)Zn1—N22.235 (2)
Zn1—Cl12.2775 (8)Zn1—O12.1298 (19)
N1—Zn1—O189.50 (8)N3—C13—C14113.5 (2)
N1—Zn1—N275.63 (8)N3—C13—H13A108.9
O1—Zn1—N2165.10 (9)C14—C13—H13A108.9
N1—Zn1—Cl1122.26 (6)N3—C13—H13B108.9
O1—Zn1—Cl194.81 (6)C14—C13—H13B108.9
N2—Zn1—Cl192.36 (6)H13A—C13—H13B107.7
N1—Zn1—Cl2121.19 (6)N4—C14—C15123.0 (2)
O1—Zn1—Cl292.71 (7)N4—C14—C13118.0 (2)
N2—Zn1—Cl295.85 (6)C15—C14—C13118.9 (2)
Cl1—Zn1—Cl2116.08 (3)C16—C15—C14119.5 (2)
C19—O1—Zn1127.57 (18)C16—C15—H15120.3
C7—N1—C1105.8 (2)C14—C15—H15120.3
C7—N1—Zn1117.44 (16)C17—C16—C15118.1 (3)
C1—N1—Zn1136.71 (17)C17—C16—H16120.9
C12—N2—C8119.5 (2)C15—C16—H16120.9
C12—N2—Zn1124.7 (2)C18—C17—C16118.5 (3)
C8—N2—Zn1114.86 (16)C18—C17—H17120.7
C7—N3—C6107.0 (2)C16—C17—H17120.7
C7—N3—C13130.6 (2)N4—C18—C17124.4 (3)
C6—N3—C13122.4 (2)N4—C18—H18117.8
C14—N4—C18116.3 (2)C17—C18—H18117.8
C19—N5—C21122.0 (2)O1—C19—N5123.8 (3)
C19—N5—C20120.3 (3)O1—C19—H19118.1
C21—N5—C20117.6 (2)N5—C19—H19118.1
C22—N6—C24121.8 (3)N5—C20—H20A109.5
C22—N6—C23119.4 (3)N5—C20—H20B109.5
C24—N6—C23118.7 (3)H20A—C20—H20B109.5
C6—C1—C2120.1 (2)N5—C20—H20C109.5
C6—C1—N1108.5 (2)H20A—C20—H20C109.5
C2—C1—N1131.4 (3)H20B—C20—H20C109.5
C3—C2—C1118.2 (3)N5—C21—H21A109.5
C3—C2—H2120.9N5—C21—H21B109.5
C1—C2—H2120.9H21A—C21—H21B109.5
C2—C3—C4120.8 (2)N5—C21—H21C109.5
C2—C3—C31118.7 (3)H21A—C21—H21C109.5
C4—C3—C31120.5 (2)H21B—C21—H21C109.5
C5—C4—C3121.0 (2)O2—C22—N6125.5 (3)
C5—C4—C41119.0 (3)O2—C22—H22117.3
C3—C4—C41120.0 (2)N6—C22—H22117.3
C4—C5—C6117.4 (3)N6—C23—H23A109.5
C4—C5—H5121.3N6—C23—H23B109.5
C6—C5—H5121.3H23A—C23—H23B109.5
N3—C6—C5131.2 (2)N6—C23—H23C109.5
N3—C6—C1106.3 (2)H23A—C23—H23C109.5
C5—C6—C1122.4 (2)H23B—C23—H23C109.5
N1—C7—N3112.3 (2)N6—C24—H24A109.5
N1—C7—C8119.0 (2)N6—C24—H24B109.5
N3—C7—C8128.7 (2)H24A—C24—H24B109.5
N2—C8—C9121.7 (2)N6—C24—H24C109.5
N2—C8—C7112.1 (2)H24A—C24—H24C109.5
C9—C8—C7126.1 (3)H24B—C24—H24C109.5
C8—C9—C10117.8 (3)C3—C31—H31A109.5
C8—C9—H9121.1C3—C31—H31B109.5
C10—C9—H9121.1H31A—C31—H31B109.5
C11—C10—C9120.4 (3)C3—C31—H31C109.5
C11—C10—H10119.8H31A—C31—H31C109.5
C9—C10—H10119.8H31B—C31—H31C109.5
C10—C11—C12118.1 (3)C4—C41—H41A109.5
C10—C11—H11120.9C4—C41—H41B109.5
C12—C11—H11120.9H41A—C41—H41B109.5
N2—C12—C11122.4 (3)C4—C41—H41C109.5
N2—C12—H12118.8H41A—C41—H41C109.5
C11—C12—H12118.8H41B—C41—H41C109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O10.952.303.034 (4)134
C5—H5···Cl2i0.952.783.612 (3)147
C9—H9···O20.952.453.226 (4)139
C19—H19···Cl10.952.843.389 (2)118
Symmetry code: (i) x+1, y+1, z+1.
(II) Bis(acetato-κ2O,O'){5,6-dimethyl-2-(pyridin-2-yl-κN)-1-[(pyridin-2-yl)methyl]-1H-benzimidazole-κN3}zinc(II) ethanol monosolvate top
Crystal data top
Zn(C2H3O2)2(C20H18N4)]·C2H6OF(000) = 1136
Mr = 543.91Dx = 1.378 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 16.0866 (17) ÅCell parameters from 6456 reflections
b = 8.7150 (8) Åθ = 2.2–23.2°
c = 18.745 (2) ŵ = 0.98 mm1
β = 94.193 (4)°T = 200 K
V = 2620.9 (5) Å3Plate, clear pale grey
Z = 40.60 × 0.40 × 0.20 mm
Data collection top
Bruker SMART X2S benchtop
diffractometer
4636 independent reflections
Radiation source: sealed microfocus tube3543 reflections with I > 2σ(I)
Doubly curved silicon crystal monochromatorRint = 0.053
Detector resolution: 8.3330 pixels mm-1θmax = 25.0°, θmin = 2.5°
ω scansh = 1919
Absorption correction: multi-scan
(SADABS; Bruker, 2013)
k = 1010
Tmin = 0.67, Tmax = 0.83l = 2122
23075 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H-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 parametersΔρmax = 0.28 e Å3
4 restraintsΔρmin = 0.30 e Å3
Crystal data top
Zn(C2H3O2)2(C20H18N4)]·C2H6OV = 2620.9 (5) Å3
Mr = 543.91Z = 4
Monoclinic, P21/nMo Kα radiation
a = 16.0866 (17) ŵ = 0.98 mm1
b = 8.7150 (8) ÅT = 200 K
c = 18.745 (2) Å0.60 × 0.40 × 0.20 mm
β = 94.193 (4)°
Data collection top
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 = 0.83Rint = 0.053
23075 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0364 restraints
wR(F2) = 0.090H-atom parameters constrained
S = 1.02Δρmax = 0.28 e Å3
4636 reflectionsΔρmin = 0.30 e Å3
361 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Zn11.00931 (2)0.64742 (3)0.76586 (2)0.03809 (11)
O11.11296 (13)0.5215 (3)0.78573 (12)0.0750 (7)
O21.05973 (13)0.4878 (3)0.67684 (11)0.0671 (6)
O30.95559 (14)0.8052 (2)0.69317 (11)0.0620 (6)
O41.06838 (15)0.8835 (3)0.75097 (13)0.0794 (7)
N10.89210 (12)0.5955 (2)0.95226 (10)0.0332 (5)
N20.96702 (12)0.6853 (2)0.86594 (10)0.0333 (5)
N30.89927 (12)0.5090 (2)0.76307 (10)0.0355 (5)
N40.71641 (14)0.6761 (2)0.96555 (11)0.0439 (5)
C11.00139 (14)0.7414 (3)0.93111 (13)0.0354 (6)
C21.06942 (16)0.8386 (3)0.94653 (14)0.0399 (6)
H21.10030.87850.90940.048*
C31.09048 (17)0.8751 (3)1.01728 (16)0.0458 (7)
C41.04362 (18)0.8161 (3)1.07236 (15)0.0458 (7)
C50.97574 (16)0.7211 (3)1.05715 (13)0.0423 (6)
H50.94440.68151.09410.051*
C60.95497 (15)0.6855 (2)0.98528 (13)0.0350 (6)
C70.90267 (15)0.6000 (2)0.88077 (13)0.0319 (5)
C80.85525 (15)0.5185 (2)0.82155 (12)0.0323 (5)
C90.77485 (15)0.4623 (3)0.82189 (14)0.0398 (6)
H90.74350.47470.86250.048*
C100.74102 (17)0.3866 (3)0.76076 (15)0.0451 (7)
H100.68640.3450.75980.054*
C110.78682 (17)0.3726 (3)0.70210 (14)0.0453 (7)
H110.76510.31940.66060.054*
C120.86535 (17)0.4380 (3)0.70506 (13)0.0419 (6)
H120.89640.4320.6640.05*
C130.83317 (15)0.5064 (3)0.99180 (13)0.0386 (6)
H12A0.86350.45811.03380.046*
H13B0.80910.42340.96070.046*
C140.76361 (15)0.6042 (3)1.01669 (13)0.0358 (6)
C150.74968 (18)0.6147 (3)1.08821 (14)0.0511 (7)
H150.78410.56061.12310.061*
C160.68468 (19)0.7054 (4)1.10838 (16)0.0644 (9)
H160.67430.71571.15740.077*
C170.63584 (19)0.7799 (4)1.05690 (16)0.0620 (8)
H170.5910.84311.06920.074*
C180.65325 (18)0.7610 (3)0.98690 (15)0.0564 (8)
H180.61830.81140.95120.068*
C191.1156 (2)0.4625 (4)0.72414 (19)0.0627 (8)
C201.1889 (2)0.3617 (5)0.7095 (2)0.1041 (15)
H20A1.1830.32640.65980.156*
H20B1.19050.27290.74170.156*
H20C1.24060.42050.71760.156*
C211.0095 (2)0.9078 (4)0.70617 (18)0.0612 (8)
C221.0000 (3)1.0561 (4)0.6651 (2)0.0966 (14)
H22A1.0431.12870.68330.145*
H22B0.94481.09970.67110.145*
H22C1.00591.03650.61430.145*
C311.16477 (18)0.9773 (3)1.03577 (18)0.0617 (9)
H31A1.20780.91911.06380.093*
H31B1.14751.06511.06380.093*
H31C1.18721.01420.99170.093*
C411.0660 (2)0.8603 (3)1.14974 (16)0.0636 (9)
H41A1.02950.80561.18080.095*
H41B1.05880.97111.15550.095*
H41C1.12410.83251.16290.095*
O500.6649 (10)0.2518 (17)0.9156 (7)0.077 (4)0.496 (14)
H500.63130.27020.88020.115*0.496 (14)
C510.6223 (8)0.1850 (13)0.9699 (5)0.094 (4)0.496 (14)
H51A0.66230.12721.00240.113*0.496 (14)
H51B0.58070.11140.94850.113*0.496 (14)
C520.5814 (7)0.2963 (13)1.0097 (7)0.099 (4)0.496 (14)
H52A0.62260.3681.03180.148*0.496 (14)
H52B0.5520.24531.04710.148*0.496 (14)
H52C0.54120.35280.97780.148*0.496 (14)
O600.6600 (11)0.303 (2)0.9271 (8)0.101 (5)0.504 (14)
H600.620.29580.89580.151*0.504 (14)
C610.6301 (12)0.292 (2)0.9948 (8)0.164 (8)0.504 (14)
H61A0.59540.38331.00280.197*0.504 (14)
H61B0.67810.29391.0310.197*0.504 (14)
C620.5823 (7)0.1581 (11)1.0052 (7)0.102 (4)0.504 (14)
H62A0.54390.14040.9630.153*0.504 (14)
H62B0.55040.17161.04740.153*0.504 (14)
H62C0.61960.06961.01260.153*0.504 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.03716 (18)0.04128 (18)0.03629 (19)0.00028 (14)0.00570 (13)0.00074 (13)
O10.0623 (14)0.0948 (16)0.0668 (15)0.0325 (13)0.0026 (12)0.0218 (13)
O20.0539 (13)0.0952 (16)0.0536 (13)0.0154 (12)0.0137 (11)0.0165 (12)
O30.0773 (15)0.0497 (11)0.0604 (13)0.0000 (11)0.0153 (11)0.0111 (10)
O40.0693 (16)0.1020 (18)0.0691 (16)0.0058 (14)0.0211 (13)0.0096 (14)
N10.0346 (11)0.0346 (10)0.0306 (11)0.0055 (9)0.0031 (9)0.0003 (9)
N20.0314 (11)0.0346 (10)0.0338 (11)0.0001 (9)0.0007 (9)0.0025 (9)
N30.0426 (12)0.0363 (10)0.0279 (11)0.0011 (10)0.0040 (10)0.0012 (9)
N40.0480 (13)0.0487 (12)0.0354 (12)0.0134 (11)0.0050 (10)0.0012 (10)
C10.0328 (13)0.0322 (12)0.0408 (15)0.0092 (11)0.0002 (11)0.0053 (11)
C20.0358 (14)0.0336 (12)0.0494 (16)0.0054 (11)0.0037 (12)0.0053 (11)
C30.0422 (15)0.0328 (13)0.0598 (19)0.0118 (12)0.0133 (14)0.0108 (13)
C40.0551 (17)0.0354 (13)0.0443 (16)0.0196 (13)0.0149 (14)0.0097 (12)
C50.0505 (16)0.0429 (14)0.0330 (14)0.0176 (13)0.0005 (12)0.0032 (11)
C60.0365 (14)0.0315 (12)0.0365 (14)0.0099 (11)0.0022 (11)0.0042 (10)
C70.0333 (13)0.0295 (11)0.0329 (14)0.0054 (11)0.0023 (11)0.0002 (10)
C80.0352 (13)0.0283 (11)0.0331 (14)0.0022 (10)0.0000 (11)0.0014 (10)
C90.0369 (14)0.0403 (13)0.0422 (15)0.0004 (12)0.0029 (12)0.0023 (11)
C100.0387 (15)0.0451 (14)0.0504 (18)0.0067 (12)0.0050 (13)0.0027 (13)
C110.0535 (17)0.0434 (14)0.0376 (16)0.0061 (13)0.0070 (13)0.0043 (12)
C120.0538 (17)0.0427 (14)0.0288 (14)0.0018 (13)0.0009 (12)0.0018 (11)
C130.0440 (15)0.0377 (13)0.0342 (14)0.0051 (12)0.0034 (12)0.0043 (11)
C140.0370 (14)0.0379 (13)0.0328 (14)0.0000 (11)0.0055 (11)0.0008 (10)
C150.0488 (17)0.0722 (18)0.0327 (15)0.0064 (15)0.0059 (13)0.0047 (13)
C160.0571 (19)0.100 (2)0.0381 (17)0.0096 (19)0.0172 (15)0.0073 (17)
C170.0514 (18)0.085 (2)0.0517 (19)0.0199 (17)0.0160 (15)0.0101 (17)
C180.0574 (18)0.0655 (18)0.0465 (18)0.0231 (16)0.0046 (14)0.0020 (14)
C190.054 (2)0.0665 (19)0.069 (2)0.0159 (16)0.0154 (18)0.0015 (18)
C200.082 (3)0.146 (4)0.083 (3)0.060 (3)0.004 (2)0.036 (3)
C210.069 (2)0.0601 (19)0.058 (2)0.0064 (18)0.0320 (18)0.0051 (16)
C220.156 (4)0.0503 (19)0.085 (3)0.010 (2)0.024 (3)0.0169 (18)
C310.0511 (18)0.0468 (15)0.084 (2)0.0043 (14)0.0199 (16)0.0171 (15)
C410.083 (2)0.0528 (16)0.0507 (18)0.0210 (16)0.0249 (17)0.0160 (14)
O500.079 (6)0.099 (7)0.055 (5)0.023 (5)0.020 (4)0.021 (5)
C510.091 (8)0.098 (7)0.095 (8)0.002 (6)0.028 (7)0.028 (6)
C520.090 (8)0.078 (7)0.125 (10)0.018 (6)0.005 (7)0.021 (6)
O600.095 (8)0.137 (12)0.074 (7)0.041 (8)0.038 (5)0.003 (6)
C610.165 (15)0.162 (13)0.181 (14)0.099 (12)0.107 (12)0.084 (11)
C620.095 (8)0.106 (8)0.107 (9)0.011 (6)0.016 (6)0.013 (6)
Geometric parameters (Å, º) top
Zn1—O12.008 (2)C13—H12A0.99
Zn1—N22.068 (2)C13—H13B0.99
Zn1—O32.079 (2)C14—C151.378 (3)
Zn1—N32.139 (2)C15—C161.386 (4)
Zn1—O42.292 (2)C15—H150.95
Zn1—O22.362 (2)C16—C171.363 (4)
Zn1—C192.515 (3)C16—H160.95
Zn1—C212.530 (3)C17—C181.371 (4)
O1—C191.268 (4)C17—H170.95
O2—C191.235 (4)C18—H180.95
O3—C211.257 (4)C19—C201.511 (4)
O4—C211.237 (4)C20—H20A0.98
N1—C71.364 (3)C20—H20B0.98
N1—C61.389 (3)C20—H20C0.98
N1—C131.467 (3)C21—C221.506 (4)
N2—C71.320 (3)C22—H22A0.98
N2—C11.392 (3)C22—H22B0.98
N3—C121.333 (3)C22—H22C0.98
N3—C81.350 (3)C31—H31A0.98
N4—C141.335 (3)C31—H31B0.98
N4—C181.342 (3)C31—H31C0.98
C1—C61.392 (3)C41—H41A0.98
C1—C21.398 (3)C41—H41B0.98
C2—C31.382 (4)C41—H41C0.98
C2—H20.95O50—C511.395 (14)
C3—C41.419 (4)O50—H500.84
C3—C311.511 (4)C51—C521.416 (9)
C4—C51.383 (4)C51—H51A0.99
C4—C411.518 (4)C51—H51B0.99
C5—C61.399 (3)C52—H52A0.98
C5—H50.95C52—H52B0.98
C7—C81.481 (3)C52—H52C0.98
C8—C91.384 (3)O60—C611.392 (14)
C9—C101.397 (3)O60—H600.84
C9—H90.95C61—C621.420 (9)
C10—C111.373 (4)C61—H61A0.99
C10—H100.95C61—H61B0.99
C11—C121.383 (4)C62—H62A0.98
C11—H110.95C62—H62B0.98
C12—H120.95C62—H62C0.98
C13—C141.507 (3)
O1—Zn1—N2104.04 (9)N1—C13—H13B109.1
O1—Zn1—O3141.51 (9)C14—C13—H13B109.1
N2—Zn1—O3109.90 (8)H12A—C13—H13B107.9
O1—Zn1—N3111.77 (9)N4—C14—C15122.9 (2)
N2—Zn1—N377.63 (7)N4—C14—C13116.1 (2)
O3—Zn1—N393.07 (8)C15—C14—C13121.0 (2)
O1—Zn1—O499.61 (10)C14—C15—C16118.9 (3)
N2—Zn1—O497.70 (8)C14—C15—H15120.6
O3—Zn1—O458.83 (9)C16—C15—H15120.6
N3—Zn1—O4148.52 (8)C17—C16—C15119.1 (3)
O1—Zn1—O259.05 (8)C17—C16—H16120.5
N2—Zn1—O2152.59 (7)C15—C16—H16120.5
O3—Zn1—O294.27 (8)C16—C17—C18118.2 (3)
N3—Zn1—O288.67 (8)C16—C17—H17120.9
O4—Zn1—O2106.02 (8)C18—C17—H17120.9
O1—Zn1—C1929.95 (9)N4—C18—C17124.3 (3)
N2—Zn1—C19131.32 (10)N4—C18—H18117.8
O3—Zn1—C19118.65 (10)C17—C18—H18117.8
N3—Zn1—C19102.18 (9)O2—C19—O1120.7 (3)
O4—Zn1—C19103.89 (10)O2—C19—C20120.6 (3)
O2—Zn1—C1929.12 (8)O1—C19—C20118.7 (3)
O1—Zn1—C21122.97 (11)O2—C19—Zn168.52 (17)
N2—Zn1—C21105.61 (9)O1—C19—Zn152.27 (14)
O3—Zn1—C2129.63 (10)C20—C19—Zn1170.3 (3)
N3—Zn1—C21121.50 (10)C19—C20—H20A109.5
O4—Zn1—C2129.20 (9)C19—C20—H20B109.5
O2—Zn1—C21101.80 (9)H20A—C20—H20B109.5
C19—Zn1—C21114.48 (10)C19—C20—H20C109.5
C19—O1—Zn197.78 (18)H20A—C20—H20C109.5
C19—O2—Zn182.36 (19)H20B—C20—H20C109.5
C21—O3—Zn195.5 (2)O4—C21—O3119.5 (3)
C21—O4—Zn186.1 (2)O4—C21—C22122.5 (4)
C7—N1—C6106.41 (19)O3—C21—C22117.9 (3)
C7—N1—C13130.0 (2)O4—C21—Zn164.66 (18)
C6—N1—C13123.4 (2)O3—C21—Zn154.87 (15)
C7—N2—C1106.3 (2)C22—C21—Zn1172.8 (3)
C7—N2—Zn1114.58 (15)C21—C22—H22A109.5
C1—N2—Zn1135.73 (16)C21—C22—H22B109.5
C12—N3—C8118.9 (2)H22A—C22—H22B109.5
C12—N3—Zn1124.78 (17)C21—C22—H22C109.5
C8—N3—Zn1115.32 (15)H22A—C22—H22C109.5
C14—N4—C18116.6 (2)H22B—C22—H22C109.5
C6—C1—N2108.5 (2)C3—C31—H31A109.5
C6—C1—C2121.0 (2)C3—C31—H31B109.5
N2—C1—C2130.5 (2)H31A—C31—H31B109.5
C3—C2—C1118.1 (3)C3—C31—H31C109.5
C3—C2—H2120.9H31A—C31—H31C109.5
C1—C2—H2120.9H31B—C31—H31C109.5
C2—C3—C4120.6 (2)C4—C41—H41A109.5
C2—C3—C31119.4 (3)C4—C41—H41B109.5
C4—C3—C31120.0 (3)H41A—C41—H41B109.5
C5—C4—C3121.4 (2)C4—C41—H41C109.5
C5—C4—C41118.5 (3)H41A—C41—H41C109.5
C3—C4—C41120.1 (3)H41B—C41—H41C109.5
C4—C5—C6117.4 (3)C51—O50—H50109.5
C4—C5—H5121.3O50—C51—C52111.8 (14)
C6—C5—H5121.3O50—C51—H51A109.3
N1—C6—C1106.5 (2)C52—C51—H51A109.3
N1—C6—C5132.0 (2)O50—C51—H51B109.3
C1—C6—C5121.5 (2)C52—C51—H51B109.3
N2—C7—N1112.3 (2)H51A—C51—H51B107.9
N2—C7—C8118.7 (2)C51—C52—H52A109.5
N1—C7—C8128.9 (2)C51—C52—H52B109.5
N3—C8—C9121.9 (2)H52A—C52—H52B109.5
N3—C8—C7111.4 (2)C51—C52—H52C109.5
C9—C8—C7126.6 (2)H52A—C52—H52C109.5
C8—C9—C10118.1 (2)H52B—C52—H52C109.5
C8—C9—H9120.9C61—O60—H60109.5
C10—C9—H9120.9O60—C61—C62114.1 (16)
C11—C10—C9120.0 (2)O60—C61—H61A108.7
C11—C10—H10120.0C62—C61—H61A108.7
C9—C10—H10120.0O60—C61—H61B108.7
C10—C11—C12118.2 (2)C62—C61—H61B108.7
C10—C11—H11120.9H61A—C61—H61B107.6
C12—C11—H11120.9C61—C62—H62A109.5
N3—C12—C11122.8 (3)C61—C62—H62B109.5
N3—C12—H12118.6H62A—C62—H62B109.5
C11—C12—H12118.6C61—C62—H62C109.5
N1—C13—C14112.28 (18)H62A—C62—H62C109.5
N1—C13—H12A109.1H62B—C62—H62C109.5
C14—C13—H12A109.1
C7—N2—C1—C60.2 (2)C12—N3—C8—C7179.6 (2)
Zn1—N2—C1—C6156.77 (17)Zn1—N3—C8—C711.4 (2)
C7—N2—C1—C2179.0 (2)N2—C7—C8—N317.6 (3)
Zn1—N2—C1—C224.0 (4)N1—C7—C8—N3159.1 (2)
C6—C1—C2—C31.4 (3)N2—C7—C8—C9160.0 (2)
N2—C1—C2—C3179.5 (2)N1—C7—C8—C923.3 (4)
C1—C2—C3—C40.5 (3)N3—C8—C9—C103.5 (3)
C1—C2—C3—C31178.8 (2)C7—C8—C9—C10179.3 (2)
C2—C3—C4—C50.1 (4)C8—C9—C10—C111.3 (4)
C31—C3—C4—C5179.4 (2)C9—C10—C11—C121.5 (4)
C2—C3—C4—C41178.4 (2)C8—N3—C12—C110.3 (3)
C31—C3—C4—C412.3 (3)Zn1—N3—C12—C11168.15 (18)
C3—C4—C5—C60.1 (3)C10—C11—C12—N32.3 (4)
C41—C4—C5—C6178.2 (2)C7—N1—C13—C14105.8 (3)
C7—N1—C6—C10.1 (2)C6—N1—C13—C1480.1 (3)
C13—N1—C6—C1175.37 (19)C18—N4—C14—C150.1 (4)
C7—N1—C6—C5179.0 (2)C18—N4—C14—C13178.7 (2)
C13—N1—C6—C53.7 (4)N1—C13—C14—N459.4 (3)
N2—C1—C6—N10.2 (2)N1—C13—C14—C15121.8 (3)
C2—C1—C6—N1179.14 (19)N4—C14—C15—C160.9 (4)
N2—C1—C6—C5179.0 (2)C13—C14—C15—C16179.7 (3)
C2—C1—C6—C51.7 (3)C14—C15—C16—C170.9 (5)
C4—C5—C6—N1179.9 (2)C15—C16—C17—C180.2 (5)
C4—C5—C6—C10.9 (3)C14—N4—C18—C171.2 (4)
C1—N2—C7—N10.1 (2)C16—C17—C18—N41.3 (5)
Zn1—N2—C7—N1162.37 (14)Zn1—O2—C19—O13.0 (3)
C1—N2—C7—C8177.37 (19)Zn1—O2—C19—C20176.5 (3)
Zn1—N2—C7—C814.9 (3)Zn1—O1—C19—O23.5 (4)
C6—N1—C7—N20.1 (2)Zn1—O1—C19—C20175.9 (3)
C13—N1—C7—N2174.8 (2)Zn1—O4—C21—O30.5 (3)
C6—N1—C7—C8176.9 (2)Zn1—O4—C21—C22179.6 (3)
C13—N1—C7—C82.0 (4)Zn1—O3—C21—O40.6 (3)
C12—N3—C8—C92.7 (3)Zn1—O3—C21—C22179.7 (3)
Zn1—N3—C8—C9166.30 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9···O500.952.563.167 (15)122
C9—H9···O600.952.403.125 (14)133
C15—H15···O1i0.952.403.333 (3)167
C17—H17···O2ii0.952.583.325 (4)136
O50—H50···O3iii0.841.912.749 (15)173
C10—H10···O3iii0.952.533.414 (4)155
Symmetry codes: (i) x+2, y+1, z+2; (ii) x1/2, y+3/2, z+1/2; (iii) x+3/2, y1/2, z+3/2.

Experimental details

(I)(II)
Crystal data
Chemical formula[ZnCl2(C20H18N4)(C3H7NO)]·C3H7NOZn(C2H3O2)2(C20H18N4)]·C2H6O
Mr596.84543.91
Crystal system, space groupTriclinic, P1Monoclinic, P21/n
Temperature (K)200200
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
V3)1407.9 (2)2620.9 (5)
Z24
Radiation typeMo KαMo Kα
µ (mm1)1.100.98
Crystal size (mm)0.58 × 0.30 × 0.200.60 × 0.40 × 0.20
Data collection
DiffractometerBruker SMART X2S benchtopBruker SMART X2S benchtop
Absorption correctionMulti-scan
(SADABS; Bruker, 2013)
Multi-scan
(SADABS; Bruker, 2013)
Tmin, Tmax0.56, 0.810.67, 0.83
No. of measured, independent and
observed [I > 2σ(I)] reflections
12063, 4976, 4058 23075, 4636, 3543
Rint0.0470.053
(sin θ/λ)max1)0.6030.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.107, 1.05 0.036, 0.090, 1.02
No. of reflections49764636
No. of parameters340361
No. of restraints04
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.40, 0.640.28, 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).

Selected geometric parameters (Å, º) for (I) top
Zn1—Cl12.2775 (8)Zn1—N22.235 (2)
Zn1—Cl22.2788 (9)Zn1—O12.1298 (19)
Zn1—N12.067 (2)
N1—Zn1—O189.50 (8)N2—Zn1—Cl192.36 (6)
N1—Zn1—N275.63 (8)N1—Zn1—Cl2121.19 (6)
O1—Zn1—N2165.10 (9)O1—Zn1—Cl292.71 (7)
N1—Zn1—Cl1122.26 (6)N2—Zn1—Cl295.85 (6)
O1—Zn1—Cl194.81 (6)Cl1—Zn1—Cl2116.08 (3)
Selected geometric parameters (Å, º) for (II) top
Zn1—O12.008 (2)Zn1—N32.139 (2)
Zn1—N22.068 (2)Zn1—O42.292 (2)
Zn1—O32.079 (2)Zn1—O22.362 (2)
O1—Zn1—N2104.04 (9)N2—Zn1—O497.70 (8)
O1—Zn1—O3141.51 (9)N3—Zn1—O4148.52 (8)
N2—Zn1—O3109.90 (8)N2—Zn1—O2152.59 (7)
O1—Zn1—N3111.77 (9)O3—Zn1—O294.27 (8)
N2—Zn1—N377.63 (7)N3—Zn1—O288.67 (8)
O3—Zn1—N393.07 (8)O4—Zn1—O2106.02 (8)
O1—Zn1—O499.61 (10)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O10.952.303.034 (4)133.5
C5—H5···Cl2i0.952.783.612 (3)146.7
C9—H9···O20.952.453.226 (4)139.1
C19—H19···Cl10.952.843.389 (2)117.8
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
C9—H9···O500.952.563.167 (15)122.1
C15—H15···O1i0.952.403.333 (3)167.0
C17—H17···O2ii0.952.583.325 (4)135.8
O50—H50···O3iii0.841.912.749 (15)173.1
C10—H10···O3iii0.952.533.414 (4)154.5
Symmetry codes: (i) x+2, y+1, z+2; (ii) x1/2, y+3/2, z+1/2; (iii) x+3/2, y1/2, z+3/2.
 

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