Chiral crystallization of a zinc(II) complex

Noor, S.; Suda, S.; Haraguchi, T.; Khatoon, F.; Akitsu, T.

doi:10.1107/S2056989021003650

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 77| Part 5| May 2021| Pages 542-546

https://doi.org/10.1107/S2056989021003650

Open

access

Chiral crystallization of a zinc(II) complex

Shabana Noor,^a Shintaro Suda,^b Tomoyuki Haraguchi,^b Fehmeeda Khatoon ^c and Takashiro Akitsu ^b ^*

^aDepartment of Applied Sciences & Humanities, Faculty of Engineering & Technology, Jamia Millia Islamia, New Delhi-110025, India, ^bDepartment of Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan, and ^cDepartment of Applied, Sciences and Humanities , Faculty of Engineering and Technology, Jamia Millia Islamia, New Delhi - 110025, India
^*Correspondence e-mail: akitsu2@rs.tus.ac.jp

Edited by J. Reibenspies, Texas A & M University, USA (Received 10 March 2021; accepted 5 April 2021; online 23 April 2021)

The compound, {6,6′-dimethoxy-2,2′-[(4-azaheptane-1,7-diyl)bis(nitrilomethanylidyne)]diphenolato}zinc(II) methanol monosolvate, [Zn(C₂₂H₂₇N₃O₄)]·CH₃OH, at 298 K crystallizes in the orthorhombic space group Pna2₁. The Zn atom is coordinated by a pentadentate Schiff base ligand in a distorted trigonal–bipyramidal N₃O₂ geometry. The equatorial plane is formed by the two phenolic O and one amine N atom. The axial positions are occupied by two amine N atoms. The distorted bipyramidal geometry is also supported by the trigonality index (τ), which is found to be 0.85 for the molecule. In the crystal, methanol solvent molecule is connected to the complex molecule by an O—H⋯O hydrogen bond and the complex molecules are connected by weak supramolecular interactions, so achiral molecules generate a chiral crystal. The Hirshfeld surface analysis suggests that H⋯H contacts account for the largest percentage of all interactions.

Keywords: chiral crystallization; zinc(II); Hirshfeld analysis; crystal structure.

CCDC reference: 2075457

1. Chemical context

Schiff bases and their coordination compounds play an important role in metal coordination chemistry owing to their thermal stability, relevant biological properties and high synthesis flexibility (Bartyzel, 2018 ; Siddiqui et al., 2006 ; Sacconi, 1966 ). These ligands are able to coordinate a wide variety of metal ions and to stabilize them in various oxidation states. The coordination geometry of the complexes depends upon the chemical structure of the chosen ligand, the coordination geometry preferred by the metal, the metal-to-ligand ratio, the reaction time and temperature (Thakurta et al., 2010 ; Fleck et al., 2013 ; Sanmartín et al., 2001 ; Khalaji et al., 2011 ). A number of zinc(II) complexes with different Schiff base ligands and their potential applications in sensing and as antibacterial and anticancer agents have been documented in the literature (Lui et al.,2019 ; Niu et al., 2015 ; Tang et al., 2013 ; AlDamen et al., 2016 ; Iksi et al., 2020 ). In addition, lanthanide Schiff base compounds are the subject of immense research interest because of their unique structures and their potential applications in advanced materials such as undoped semiconductors, magnetic, catalytic and florescent and non-linear optical materials (Li et al., 2016 ; Ishikawa et al., 2003 ; Long et al., 2018b ).

In a previous work, we reported the crystal and molecular structure of a Cu^II complex based on Schiff base ligand N1,N3-bis(3-methoxysalicylicylidene)diethylenetriamine where two Schiff base ligands join two Cu^II ions in a chelate–spacer–chelate mode, in which the protonated aliphatic secondary amine moieties represents the spacer to form a double helix (Noor et al., 2018 ). In an another report, we redetermined the crystal structure of an organic–inorganic salt of an Mn^II–Schiff base ligand complex Mn(C₁₈H₁₈N₂O₄)(H₂O)₂]ClO₄ at 100 K. In contrast to crystal-structure determinations at room temperature (Akitsu et al., 2005 , Bermejo et al., 2007 ), positional disorder of the ethylene bridge in the Schiff base and the perchlorate anion was not observed at 100 K (Noor et al. 2016 ). We now report the chiral crystallization on a zinc(II) complex.

2. Structural commentary

In the title compound (Fig. 1), the Zn atom is coordinated by a pentadentate Schiff base ligand in distorted trigonal–bipyramidal [ONNNO] geometry. The equatorial plane is formed by the two phenolic O [Zn—O3 = 2.001 (2) Å; Zn—O2 = 1.975 (2) Å] and one amine N [Zn—N2 = 2.152 (3) Å]. The axial positions are occupied by amine N atoms [Zn—N1 = 2.094 (2) Å, Zn—N3; 2.107 (2) Å]. The trigonality index (τ) for the complex is calculated as τ = (β − α) /60 where α and β are the main opposing angles in the coordination polyhedron (Addison et al., 1984 ). For perfect square-pyramidal and trigonal–bipyramidal coordination geometries, the values of τ are zero and unity, respectively. In the present complex, for Zn, β = O2—Zn—O3 = 122.87 (10)° and α = N1—Zn—N3 = 173.91 (12)° so the trigonality index is 0.85. According to this value, the coordination geometry around the zinc ion is best described as distorted trigonal–bipyramidal. An intramolecular O—H⋯O hydrogen bond is observed between the methoxy function and the oxygen atom in the six-membered ring (Table 1). This molecule has neither an asymmetric carbon nor a helical structure, so it is an achiral compound.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13A⋯O2ⁱ	0.97	2.58	3.549 (6)	172
C10—H10B⋯O5	0.97	2.50	3.340 (7)	144
O5—H5A⋯O3	0.82	2.01	2.722 (5)	144
Symmetry code: (i) $[-x+1, -y+1, z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound, showing the atom-labelling scheme.

3. Supramolecular features

In the crystal, molecules are connected by O—H⋯O hydrogen bonds (Fig. 2, Table 1). In addition, weak supramolecular C—H⋯O interactions are found (Table 1 and Fig. 3).

Figure 2
A view of the O5—H5A⋯O3 and C10—H10B⋯O5 interactions (dashed lines).

Figure 3
A view of the C13—H13A⋯O2 interaction (dashed lines).

4. Hirshfeld Surface analysis

In order to visualize the intermolecular interactions in the crystal of the title compound, a Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) was performed with CrystalExplorer17.5 (Turner et al., 2017 ). The fingerprint plot for this structure shows typical `wings' (Fig. 4i). The percentage contribution to the Hirshfeld surface area by close contacts with H atoms inside the surface and H atoms outside is 57.4% (Fig. 4ii), for O atoms inside the surface and H atoms outside it is 9.1% (Fig. 4iii), for H atoms inside the surface and O atoms outside it is 8.5% (Fig. 4iv), for C atoms inside the surface and H atoms outside it is 14.5% (Fig. 4v), and for H atoms inside the surface and C atoms outside it is 8.2% (Fig. 4vi). Hirshfeld surface analysis of the H⋯O interaction clearly shows the close intermolecular contact near methanol, (d_i is 1.1 Å and d_e is 0.75 Å).

Figure 4
The three-dimensional Hirshfeld surface showing the intermolecular interactions plotted over d_norm and the two-dimensional fingerprint plots of the title compound, showing (i) all interactions, and delineated into (ii) H⋯H, (iii) O⋯H, (iv) H⋯O, (v) C⋯H and (vi) H⋯C interactions.

5. Database survey

A search in the Cambridge Structural Database (CSD, Version 5.41, update November 2019; Groom et al., 2016 ) for similar structures returned three relevant entries: (2,2′-bipyridine-κ²N,N′)[N-(2-oxido-1-naphthylidene)threoninato-κ³O¹,N,O²]copper(II) (BIZGIB; Qiu et al., 2008 ), diaqua(N-salicylidene-L-threoninato)copper(II) (SLCDCU; Korhonen & Hämäläinen, 1981 ) and [N-(3-methoxy-2-oxidobenzylidene-κO²)threoninato-κ²O¹,N](1,10-phenanthroline-κ²N,N′)copper(II) hemihydrate (UQUYUB; Jing et al., 2011 ). The metal atom in BIZGIB is five-coordinated by one N atom and two O atoms, and two N atoms from a distorted square-pyramidal 2,2-bipyridine ligand. In the crystal, a two-dimensional network is formed by a combination of intermolecular O—H⋯O and C—H⋯O hydrogen bonds. In SLCDCU, two molecules form square planes by two intermolecular hydrogen bonds. In UQUYUB, intermolecular O—H⋯O hydrogen bonds form a one-dimensional left-handed helical structure extending parallel to [001].

6. Synthesis and crystallization

The Schiff base ligand H₂L was prepared according to a reported procedure (Matar et al., 2015 ) by a condensation reaction between 3-methoxy-2-hydroxybenzaldehyde (10 mmol, 1.52 mg) and dipropylenetriamine (5.0 mmol, 0.641 mL) in ethanol solution (30 cm³) under reflux conditions. After solvent removal, a yellow oil was obtained in 85% yield. ν(C=N) 1630 cm⁻¹.

The title compound was synthesized by the reaction of H₂L (1 mmol, 0.399 mg) with Zn(OAc)₂·2H₂O (1 mmol, 0.18 mg) in MeOH:H₂O (v/v, 10:1) (50 cm³) with a few drops of LiOH (1%). The reaction mixture was heated to 343 K for 1 h. The yellow solid obtained was filtered off and dried. ν(C=N) 1618 cm⁻¹. Single crystals suitable for X-ray crystallography were obtained several days after dissolving the solid in 40 cm³ of hot methanol.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All C-bound H atoms were placed in geometrically calculated positions and refined using a riding model [C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms, C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms]. The O-bound H atom was located in a difference-Fourier map and refined using a riding model [O—H = 0.82 Å and U_iso(H) = 1.5U_eq(O)].

Table 2
Experimental details

Crystal data
Chemical formula	[Zn(C₂₂H₂₇N₃O₄)]·CH₄O
M_r	494.88
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	293
a, b, c (Å)	14.5937 (6), 11.4425 (5), 13.5794 (5)
V (Å³)	2267.60 (16)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.12
Crystal size (mm)	0.53 × 0.49 × 0.45

Data collection
Diffractometer	Bruker APEXIII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2017 )
T_min, T_max	0.53, 0.63
No. of measured, independent and observed [I > 2σ(I)] reflections	28025, 6099, 4682
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.730

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.087, 1.04
No. of reflections	6099
No. of parameters	294
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.47
Absolute structure	Flack x determined using 1852 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.006 (5)
Computer programs: APEX3 and SAINT (Bruker, 2017), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2016/6 (Sheldrick, 2015b ), shelXle (Hübschle et al., 2011 ) and SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC reference: 2075457

Crystal structure: contains datablocks 1R, I. DOI: https://doi.org/10.1107/S2056989021003650/jy2006sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021003650/jy2006Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2017); cell refinement: APEX3 (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015b); molecular graphics: shelXle (Hübschle et al., 2011); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

{6,6'-Dimethoxy-2,2'-[(4-azaheptane-1,7-diyl)bis(nitrilomethanylidyne)]diphenolato}zinc(II) methanol monosolvate top

Crystal data top

[Zn(C₂₂H₂₇N₃O₄)]·CH₄O	D_x = 1.450 Mg m⁻³
M_r = 494.88	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna2₁	Cell parameters from 3270 reflections
a = 14.5937 (6) Å	θ = 2.2–23.9°
b = 11.4425 (5) Å	µ = 1.12 mm⁻¹
c = 13.5794 (5) Å	T = 293 K
V = 2267.60 (16) Å³	Prism, yellow
Z = 4	0.53 × 0.49 × 0.45 mm
F(000) = 1040

Data collection top

Bruker APEXIII CCD diffractometer	4682 reflections with I > 2σ(I)
Detector resolution: 7.3910 pixels mm^-1	R_int = 0.035
φ and ω scans	θ_max = 31.2°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2017)	h = −21→20
T_min = 0.53, T_max = 0.63	k = −16→16
28025 measured reflections	l = −18→18
6099 independent reflections

Refinement top

Refinement on F²	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0516P)²] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.035	(Δ/σ)_max = 0.001
wR(F²) = 0.087	Δρ_max = 0.56 e Å⁻³
S = 1.04	Δρ_min = −0.47 e Å⁻³
6099 reflections	Extinction correction: SHELXL-2016/6 (Sheldrick 2015b)
294 parameters	Extinction coefficient: 0.0091 (12)
1 restraint	Absolute structure: Flack x determined using 1852 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: dual	Absolute structure parameter: 0.006 (5)
Hydrogen site location: inferred from neighbouring sites

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. Reflections were merged by SHELXL according to the crystal class for the calculation of statistics and refinement.

_reflns_Friedel_fraction is defined as the number of unique Friedel pairs measured divided by the number that would be possible theoretically, ignoring centric projections and systematic absences.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.52170 (2)	0.52816 (3)	0.56294 (4)	0.04284 (12)
O1	0.40493 (18)	0.1936 (2)	0.4333 (2)	0.0724 (8)
N1	0.65984 (15)	0.4787 (2)	0.5612 (3)	0.0493 (5)
C1	0.3627 (3)	0.1110 (5)	0.3702 (4)	0.0857 (13)
H1A	0.396883	0.10538	0.310017	0.129*
H1B	0.301217	0.135516	0.355979	0.129*
H1C	0.361408	0.036045	0.401999	0.129*
O2	0.48708 (13)	0.3687 (2)	0.52144 (19)	0.0520 (5)
N2	0.5413 (2)	0.5782 (3)	0.7143 (2)	0.0650 (8)
H2	0.529572	0.662482	0.715739	0.078*
C2	0.4980 (2)	0.1835 (3)	0.4463 (3)	0.0549 (8)
O3	0.53164 (12)	0.6620 (2)	0.46866 (16)	0.0457 (5)
N3	0.38225 (17)	0.5711 (2)	0.58014 (19)	0.0486 (6)
C3	0.5487 (3)	0.0903 (3)	0.4162 (3)	0.0693 (10)
H3	0.520034	0.028129	0.38465	0.083*
C4	0.6437 (3)	0.0868 (3)	0.4321 (3)	0.0720 (10)
H4	0.677466	0.021275	0.414127	0.086*
O4	0.58178 (14)	0.7754 (2)	0.30994 (16)	0.0545 (5)
C5	0.6856 (2)	0.1802 (3)	0.4741 (3)	0.0610 (8)
H5	0.74875	0.179029	0.483288	0.073*
O5	0.5841 (3)	0.8341 (4)	0.5950 (4)	0.140 (2)
H5A	0.581512	0.801846	0.541104	0.21*
C6	0.5391 (2)	0.2829 (3)	0.4930 (2)	0.0453 (6)
C7	0.6353 (2)	0.2785 (3)	0.5037 (2)	0.0479 (6)
C8	0.68830 (19)	0.3763 (3)	0.54147 (19)	0.0502 (7)
H8	0.750228	0.362278	0.552506	0.06*
C9	0.7273 (3)	0.5641 (4)	0.5954 (3)	0.0735 (11)
H9A	0.731688	0.625957	0.54678	0.088*
H9B	0.786656	0.526017	0.59861	0.088*
C10	0.7079 (3)	0.6176 (5)	0.6924 (4)	0.0995 (17)
H10A	0.763926	0.615887	0.730831	0.119*
H10B	0.692303	0.698978	0.681751	0.119*
C11	0.6358 (4)	0.5649 (5)	0.7506 (3)	0.0890 (14)
H11A	0.638748	0.597758	0.816366	0.107*
H11B	0.648732	0.48201	0.756321	0.107*
C13	0.4737 (4)	0.5284 (4)	0.7786 (4)	0.0809 (15)
H13A	0.488874	0.551024	0.845482	0.097*
H13B	0.47908	0.444052	0.774871	0.097*
C14	0.3754 (4)	0.5598 (5)	0.7606 (3)	0.0848 (14)
H14A	0.369652	0.644202	0.763231	0.102*
H14B	0.338813	0.527906	0.81384	0.102*
C15	0.3349 (3)	0.5172 (4)	0.6626 (3)	0.0708 (11)
H15A	0.340711	0.432901	0.658309	0.085*
H15B	0.270299	0.536678	0.659841	0.085*
C16	0.33585 (19)	0.6329 (3)	0.5196 (2)	0.0491 (7)
H16	0.273212	0.638729	0.531279	0.059*
C17	0.37116 (18)	0.6945 (3)	0.4351 (2)	0.0444 (6)
C18	0.46571 (18)	0.7052 (3)	0.4135 (2)	0.0395 (6)
C19	0.3057 (2)	0.7452 (3)	0.3712 (3)	0.0560 (8)
H19	0.243749	0.739602	0.386674	0.067*
C20	0.3314 (2)	0.8021 (3)	0.2878 (3)	0.0606 (8)
H20	0.287289	0.833751	0.246236	0.073*
C21	0.4235 (2)	0.8127 (3)	0.2647 (2)	0.0536 (8)
H21	0.440955	0.850523	0.207094	0.064*
C22	0.4898 (2)	0.7674 (3)	0.3267 (2)	0.0432 (6)
C23	0.6092 (3)	0.8324 (4)	0.2225 (3)	0.0684 (10)
H23A	0.585095	0.791083	0.166649	0.103*
H23B	0.674874	0.833728	0.218869	0.103*
H23C	0.586221	0.910978	0.222502	0.103*
C24	0.5060 (6)	0.8915 (6)	0.6115 (6)	0.123 (2)
H24A	0.519332	0.971869	0.626096	0.185*
H24B	0.47469	0.856789	0.666377	0.185*
H24C	0.467835	0.887306	0.554073	0.185*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.04857 (18)	0.04890 (19)	0.03106 (16)	0.00482 (12)	−0.00223 (18)	0.00193 (18)
O1	0.0517 (13)	0.0781 (16)	0.0876 (19)	−0.0119 (13)	0.0060 (13)	−0.0318 (16)
N1	0.0489 (10)	0.0563 (13)	0.0427 (11)	−0.0010 (10)	−0.0077 (17)	0.0044 (15)
C1	0.075 (3)	0.101 (3)	0.081 (3)	−0.025 (2)	0.002 (2)	−0.032 (3)
O2	0.0430 (9)	0.0563 (12)	0.0568 (13)	0.0031 (9)	0.0028 (9)	−0.0092 (11)
N2	0.0852 (19)	0.073 (2)	0.0362 (14)	0.0177 (17)	−0.0110 (14)	−0.0066 (15)
C2	0.0546 (15)	0.057 (2)	0.0533 (19)	−0.0019 (15)	0.0102 (15)	−0.0081 (17)
O3	0.0393 (9)	0.0580 (13)	0.0399 (10)	0.0031 (9)	−0.0055 (8)	0.0109 (10)
N3	0.0498 (12)	0.0543 (13)	0.0416 (15)	0.0015 (11)	0.0116 (11)	0.0017 (11)
C3	0.078 (2)	0.056 (2)	0.073 (2)	−0.0023 (18)	0.011 (2)	−0.0154 (19)
C4	0.075 (2)	0.058 (2)	0.083 (3)	0.0167 (18)	0.013 (2)	−0.010 (2)
O4	0.0462 (10)	0.0713 (14)	0.0459 (11)	−0.0025 (10)	−0.0006 (9)	0.0192 (11)
C5	0.0577 (17)	0.065 (2)	0.0597 (19)	0.0159 (16)	0.0042 (15)	0.0035 (17)
O5	0.152 (4)	0.088 (2)	0.181 (5)	0.016 (2)	−0.098 (4)	−0.033 (3)
C6	0.0496 (14)	0.0481 (16)	0.0383 (14)	0.0045 (13)	0.0059 (12)	−0.0011 (13)
C7	0.0490 (14)	0.0536 (16)	0.0411 (15)	0.0061 (14)	0.0025 (13)	0.0063 (13)
C8	0.0425 (12)	0.0681 (18)	0.0399 (18)	0.0039 (13)	−0.0036 (11)	0.0076 (13)
C9	0.068 (2)	0.072 (2)	0.080 (3)	−0.0142 (19)	−0.0219 (19)	0.007 (2)
C10	0.085 (3)	0.116 (4)	0.097 (4)	−0.006 (3)	−0.036 (3)	−0.028 (3)
C11	0.111 (4)	0.109 (3)	0.047 (2)	−0.009 (3)	−0.029 (2)	−0.002 (2)
C13	0.115 (4)	0.088 (4)	0.041 (2)	0.000 (2)	0.009 (2)	0.0057 (19)
C14	0.108 (3)	0.099 (3)	0.047 (2)	0.027 (3)	0.028 (2)	0.010 (2)
C15	0.074 (2)	0.075 (2)	0.063 (2)	−0.0035 (19)	0.026 (2)	0.0137 (19)
C16	0.0394 (12)	0.0556 (16)	0.0522 (15)	0.0033 (13)	0.0045 (13)	−0.0066 (15)
C17	0.0406 (13)	0.0490 (14)	0.0436 (14)	0.0035 (12)	−0.0033 (12)	−0.0017 (13)
C18	0.0405 (12)	0.0432 (14)	0.0347 (13)	0.0033 (11)	−0.0082 (10)	0.0015 (11)
C19	0.0407 (14)	0.0634 (19)	0.064 (2)	0.0070 (14)	−0.0124 (15)	−0.0038 (17)
C20	0.0544 (16)	0.0613 (19)	0.066 (2)	0.0089 (15)	−0.0237 (16)	0.0129 (17)
C21	0.0617 (18)	0.0544 (17)	0.0446 (16)	−0.0014 (15)	−0.0120 (15)	0.0125 (14)
C22	0.0459 (14)	0.0437 (15)	0.0401 (15)	−0.0009 (12)	−0.0065 (12)	0.0036 (13)
C23	0.064 (2)	0.083 (3)	0.058 (2)	−0.002 (2)	0.0065 (18)	0.026 (2)
C24	0.189 (6)	0.083 (4)	0.097 (4)	0.033 (4)	−0.034 (4)	−0.016 (3)

Geometric parameters (Å, º) top

Zn1—O2	1.975 (2)	C9—C10	1.480 (7)
Zn1—O3	2.001 (2)	C9—H9A	0.97
Zn1—N1	2.094 (2)	C9—H9B	0.97
Zn1—N3	2.107 (2)	C10—C11	1.448 (7)
Zn1—N2	2.152 (3)	C10—H10A	0.97
O1—C2	1.375 (4)	C10—H10B	0.97
O1—C1	1.416 (5)	C11—H11A	0.97
N1—C8	1.273 (4)	C11—H11B	0.97
N1—C9	1.462 (5)	C13—C14	1.499 (7)
C1—H1A	0.96	C13—H13A	0.97
C1—H1B	0.96	C13—H13B	0.97
C1—H1C	0.96	C14—C15	1.535 (7)
O2—C6	1.300 (4)	C14—H14A	0.97
N2—C13	1.435 (6)	C14—H14B	0.97
N2—C11	1.473 (6)	C15—H15A	0.97
N2—H2	0.98	C15—H15B	0.97
C2—C3	1.361 (5)	C16—C17	1.443 (4)
C2—C6	1.432 (5)	C16—H16	0.93
O3—C18	1.316 (3)	C17—C19	1.415 (4)
N3—C16	1.278 (4)	C17—C18	1.416 (4)
N3—C15	1.453 (4)	C18—C22	1.421 (4)
C3—C4	1.403 (6)	C19—C20	1.359 (5)
C3—H3	0.93	C19—H19	0.93
C4—C5	1.357 (6)	C20—C21	1.386 (5)
C4—H4	0.93	C20—H20	0.93
O4—C22	1.365 (4)	C21—C22	1.382 (4)
O4—C23	1.413 (4)	C21—H21	0.93
C5—C7	1.402 (4)	C23—H23A	0.96
C5—H5	0.93	C23—H23B	0.96
O5—C24	1.334 (8)	C23—H23C	0.96
O5—H5A	0.82	C24—H24A	0.96
C6—C7	1.413 (4)	C24—H24B	0.96
C7—C8	1.453 (5)	C24—H24C	0.96
C8—H8	0.93

O2—Zn1—O3	122.87 (10)	C9—C10—H10A	108.1
O2—Zn1—N1	89.63 (9)	C11—C10—H10B	108.1
O3—Zn1—N1	97.45 (10)	C9—C10—H10B	108.1
O2—Zn1—N3	90.01 (9)	H10A—C10—H10B	107.3
O3—Zn1—N3	87.84 (9)	C10—C11—N2	117.1 (4)
N1—Zn1—N3	173.91 (12)	C10—C11—H11A	108.0
O2—Zn1—N2	123.50 (13)	N2—C11—H11A	108.0
O3—Zn1—N2	113.44 (12)	C10—C11—H11B	108.0
N1—Zn1—N2	87.40 (13)	N2—C11—H11B	108.0
N3—Zn1—N2	87.73 (11)	H11A—C11—H11B	107.3
C2—O1—C1	116.9 (3)	N2—C13—C14	117.6 (4)
C8—N1—C9	117.5 (3)	N2—C13—H13A	107.9
C8—N1—Zn1	124.4 (2)	C14—C13—H13A	107.9
C9—N1—Zn1	117.7 (2)	N2—C13—H13B	107.9
O1—C1—H1A	109.5	C14—C13—H13B	107.9
O1—C1—H1B	109.5	H13A—C13—H13B	107.2
H1A—C1—H1B	109.5	C13—C14—C15	115.7 (4)
O1—C1—H1C	109.5	C13—C14—H14A	108.4
H1A—C1—H1C	109.5	C15—C14—H14A	108.4
H1B—C1—H1C	109.5	C13—C14—H14B	108.4
C6—O2—Zn1	129.32 (19)	C15—C14—H14B	108.4
C13—N2—C11	113.5 (4)	H14A—C14—H14B	107.4
C13—N2—Zn1	112.6 (3)	N3—C15—C14	110.5 (3)
C11—N2—Zn1	114.6 (3)	N3—C15—H15A	109.5
C13—N2—H2	105.0	C14—C15—H15A	109.5
C11—N2—H2	105.0	N3—C15—H15B	109.5
Zn1—N2—H2	105.0	C14—C15—H15B	109.5
C3—C2—O1	124.3 (4)	H15A—C15—H15B	108.1
C3—C2—C6	121.8 (3)	N3—C16—C17	126.3 (3)
O1—C2—C6	113.8 (3)	N3—C16—H16	116.8
C18—O3—Zn1	126.77 (18)	C17—C16—H16	116.8
C16—N3—C15	118.6 (3)	C19—C17—C18	119.8 (3)
C16—N3—Zn1	124.7 (2)	C19—C17—C16	116.5 (3)
C15—N3—Zn1	116.4 (2)	C18—C17—C16	123.7 (3)
C2—C3—C4	120.9 (4)	O3—C18—C17	124.3 (3)
C2—C3—H3	119.6	O3—C18—C22	118.7 (2)
C4—C3—H3	119.6	C17—C18—C22	117.1 (2)
C5—C4—C3	119.2 (3)	C20—C19—C17	121.3 (3)
C5—C4—H4	120.4	C20—C19—H19	119.3
C3—C4—H4	120.4	C17—C19—H19	119.3
C22—O4—C23	116.7 (2)	C19—C20—C21	119.9 (3)
C4—C5—C7	121.1 (3)	C19—C20—H20	120.0
C4—C5—H5	119.5	C21—C20—H20	120.0
C7—C5—H5	119.5	C22—C21—C20	120.5 (3)
C24—O5—H5A	109.5	C22—C21—H21	119.7
O2—C6—C7	125.2 (3)	C20—C21—H21	119.7
O2—C6—C2	119.2 (3)	O4—C22—C21	124.1 (3)
C7—C6—C2	115.7 (3)	O4—C22—C18	114.5 (2)
C5—C7—C6	121.3 (3)	C21—C22—C18	121.4 (3)
C5—C7—C8	116.1 (3)	O4—C23—H23A	109.5
C6—C7—C8	122.6 (3)	O4—C23—H23B	109.5
N1—C8—C7	127.6 (3)	H23A—C23—H23B	109.5
N1—C8—H8	116.2	O4—C23—H23C	109.5
C7—C8—H8	116.2	H23A—C23—H23C	109.5
N1—C9—C10	115.4 (4)	H23B—C23—H23C	109.5
N1—C9—H9A	108.4	O5—C24—H24A	109.5
C10—C9—H9A	108.4	O5—C24—H24B	109.5
N1—C9—H9B	108.4	H24A—C24—H24B	109.5
C10—C9—H9B	108.4	O5—C24—H24C	109.5
H9A—C9—H9B	107.5	H24A—C24—H24C	109.5
C11—C10—C9	116.9 (4)	H24B—C24—H24C	109.5
C11—C10—H10A	108.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···O2ⁱ	0.97	2.58	3.549 (6)	172
C10—H10B···O5	0.97	2.50	3.340 (7)	144
O5—H5A···O3	0.82	2.01	2.722 (5)	144

Symmetry code: (i) −x+1, −y+1, z+1/2.

Funding information

This work was partly supported by a Grant-in-Aid for Scientific Research (A) KAKENHI (20H00336).

References

Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356. CSD CrossRef Web of Science Google Scholar
Akitsu, T., Takeuchi, Y. & Einaga, Y. (2005). Acta Cryst. C61, m324–m328. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
AlDamen, M. A., Charef, N., Juwhari, H. K., Sweidan, K., Mubarak, M. S. & Peters, D. G. (2016). J. Chem. Crystallogr. 46, 411–420. CSD CrossRef CAS Google Scholar
Bartyzel, A. (2018). J. Therm. Anal. Calorim. 131, 1221–1236. CSD CrossRef CAS Google Scholar
Bermejo, M. R., Fernández, M. I., Gómez-Fórneas, E., González-Noya, A., Maneiro, M., Pedrido, R. & Rodríguez, M. (2007). Eur. J. Inorg. Chem. pp. 3789–3797. Web of Science CSD CrossRef Google Scholar
Bruker (2017). APEX3, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fleck, M., Layek, M., Saha, R. & Bandyopadhyay, D. (2013). Transition Met. Chem. 38, 715–724. CSD CrossRef CAS Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281–1284. Web of Science CrossRef IUCr Journals Google Scholar
Iksi, S., Guemmout, F. E., Reguero, M., Masdeu-Bulto, A. M. & Ghnux, A. (2020). J Chem Crystallogr. https://doi.org/10.1007/s10870-020-00865-y. Google Scholar
Ishikawa, N., Sugita, M., Ishikawa, T., Koshihara, S. Y. & Kaizu, Y. (2003). J. Am. Chem. Soc. 125, 8694–8695. CrossRef PubMed CAS Google Scholar
Jing, B., Li, L., Dong, J. & Li, J. (2011). Acta Cryst. E67, m536. Web of Science CSD CrossRef IUCr Journals Google Scholar
Khalaji, A. D. & Triki, S. (2011). Russ. J. Coord. Chem. 37, 518–522. CrossRef CAS Google Scholar
Korhonen, K. & Hämäläinen, R. (1981). Acta Cryst. B37, 829–834. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Li, B., Wen, H. M., Cui, Y., Zhou, W., Qian, G. & Chen, B. (2016). Adv. Mater. 28, 8819–8860. CrossRef CAS PubMed Google Scholar
Long, J., Guari, Y., Ferreira, R. A. S., Carlos, L. D. & Larionova, J. (2018b). Coord. Chem. Rev. 363, 57–70. CrossRef CAS Google Scholar
Lui, W., Li, G., Zhao, X. & Wang, L. (2019). ChemistrySelect, 4, 29, 9317-9321. Google Scholar
Matar, S. A., Talib, W. H., Mustafa, M. S., Mubarak, M. S. & AlDamen, M. A. (2015). Arab. J. Chem. 8, 850–857. CrossRef CAS Google Scholar
Niu, M. J., Li, Z., Chang, G. L., Kong, X. J., Hong, M. & Zhang, Q. F. (2015). PLOS ONE. https://doi.org/10.1317/journal.pone.0130922. Google Scholar
Noor, S., Goddard, R., Kumar, S., Ahmad, N., Sabir, S., Mitra, P. & Seidel, R. (2018). J. Chem. Crystallogr. 48, 164–169. CSD CrossRef CAS Google Scholar
Noor, S. W., Seidel, R. W., Goddard, R., Kumar, S. & Sabir, S. (2016). IUCrData, 1, x161735. Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Qiu, Z., Li, L., Liu, Y., Xu, T. & Wang, D. (2008). Acta Cryst. E64, m745–m746. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sacconi, L. (1966). Coord. Chem. Rev. 1, 126–132. CrossRef CAS Google Scholar
Sanmartín, J., Bermejo, M. R., García-Deibe, A. M., Nascimento, O. & Costa-Filho, A. J. (2001). Inorg. Chim. Acta, 318, 135–142. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Siddiqui, H. L., Iqbal, A., Ahmad, S. & Weaver, W. (2006). Molecules, 11, 206–211. CrossRef PubMed CAS Google Scholar
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Tang, B., Ma, H., Li, G., Wang, Y., Anwar, G., Shi, R. & Li, H. (2013). CrystEngComm, 15, 8069–8073. CSD CrossRef CAS Google Scholar
Thakurta, S., Rizzoli, C., Butcher, R. J., Gómez-García, C. J., Garribba, E. & Mitra, S. (2010). Inorg. Chim. Acta, 336, 1395–1403. CSD CrossRef Google Scholar
Turner, M. J., Mckinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17. University of Western Australia. Google Scholar