Crystal structure of the coordination polymer catena-poly[[bis­[hy­droxy(phen­yl)acetato-κ2O1,O2]zinc(II)]-μ2-1,2-bis­(pyridin-4-yl)ethane-κ2N:N′]

Fwu Ming, S.; Shie Fu, L.

doi:10.1107/S2056989020014322

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ISSN: 2056-9890

Volume 76| Part 12| December 2020| Pages 1868-1870

https://doi.org/10.1107/S2056989020014322

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Crystal structure of the coordination polymer catena-poly[[bis[hydroxy(phenyl)acetato-κ²O¹,O²]zinc(II)]-μ₂-1,2-bis(pyridin-4-yl)ethane-κ²N:N′]

Shen Fwu Ming ^a and Lush Shie Fu ^b ^*

^aDepartment of Medical Laboratory Science Biotechnology, Yuanpei University, No. 306, Yuanpei Street, Hsinchu, Taiwan 30015, ROC, and ^bDepartment of Biotechnology, Yuanpei University, No. 306, Yuanpei Street, Hsinchu, Taiwan 30015, ROC
^*Correspondence e-mail: lush@mail.ypu.edu.tw

Edited by A. M. Chippindale, University of Reading, England (Received 30 September 2020; accepted 28 October 2020; online 24 November 2020)

In the title polymeric Zn^II compound, [Zn(C₈H₇O₃)₂(C₁₂H₁₂N₂)]_n, the Zn cation is coordinated by two N atoms from 1,2-bis(pyridin-4-yl)ethane unit and four O atoms from two mandelate [or hydroxy(phenyl)acetate] anions in a slightly distorted octahedral coordination geometry. The 1,2-bis(pyridin-4-yl)ethane unit bridges two Zn^II cations, related by an inversion centre, to form a polymeric chain along [110]. The crystal structure features extensive O—H⋯O and weak C—H ⋯O hydrogen bonds, with C—H ⋯ π interactions and π–π interactions also being present. The centroid–centroid distance between the phenyl ring of the mandelate group and the 1,2-bis(pyridine-4-yl)ethane moiety is 4.951 (2) Å. The 1,2-bis(pyridin-4-yl)ethane ligand is disordered over two positions, with a refined occupancy of 0.578 (14) for the major component.

Keywords: crystal structure; coordination polymer; mandelate,1,2-bi(4-pyridyl)ethane; disorder.

CCDC reference: 2040978

1. Chemical context

α-Hydroxycarboxylic acids play an important role in many biological processes and in coordination chemistry (Miyamoto et al., 1989 ). The deprotonated anion of one example, mandelic acid (2-hydroxy-2-phenylacetic acid), can behave as a multifunctional ligand and can act as a bridging ligand in metal complexes by involving the oxygen atoms of the carboxylate and hydroxy groups (Zechel et al., 2019 ; Smatanová et al., 2000 ; Bromant et al., 2005 ). We report the preparation and structural characterization of a new coordination polymer in which the Zn^II cations are coordinated to two mandelate anions, behaving as bidentate ligands, and linked together via 1,2-bis(4-pyridyl)ethane molecules. 1,2-Bis(4-pyridyl)ethane is a versatile building block for the purposes of crystal engineering as the pyridyl N atoms can connect to adjacent metals to form a chain (Lee & Kim, 2015 ).

1.1. Structural commentary

The asymmetric unit of the title compound comprises one Zn^II cation, one mandelate anion and one half of a 1,2-bis(4-pyridin-4-yl)ethane molecule. There is an inversion centre located at the mid-point of the ethane C—C bond in the 1,2-bis(4-pyridin-4-yl)ethane molecule. Each Zn^II cation is coordinated by two N atoms from two 1,2-bis(4-pyridin-4-yl)ethane molecules in a trans arrangement and four O atoms from two mandelate anions in a slightly distorted octahedral coordination geometry, as shown in Table 1 and Fig. 1. The mandelate anions are coordinated to the central Zn²⁺ cation form five-membered chelate rings via an oxygen atom of the OH group [Zn—O3 = 2.1013 (15) Å] and an oxygen atom of the carboxyl group [Zn—O1= 2.0290 (14) Å]. The Zn^II cations are linked together via 1,2-bis(4-pyridin-4-yl)ethane bridges, forming a polymeric chain along [110].

Table 1
Selected geometric parameters (Å, °)

Zn—O1	2.0290 (14)	O2—C1	1.250 (3)
Zn—O3	2.1013 (15)	O3—C2	1.424 (2)
Zn—N	2.2217 (19)	N—C13	1.334 (3)
O1—C1	1.260 (2)	N—C9	1.339 (3)

O1—Zn—O3	80.02 (6)	C9—N—C13	117.3 (2)
O1—Zn—N	90.25 (7)	O2—C1—C2	116.10 (17)
O1—Zn—O3ⁱ	99.98 (6)	O1—C1—O2	124.67 (19)
O1—Zn—Nⁱ	89.75 (7)	O1—C1—C2	119.21 (18)
O3—Zn—N	88.73 (6)	O3—C2—C3	110.90 (18)
O3—Zn—Nⁱ	91.27 (6)	O3—C2—C1	110.17 (16)
Zn—O1—C1	116.96 (13)	N—C9—C10	118.8 (4)
Zn—O3—C2	113.41 (12)	N—C9—C10′	127.1 (6)
Zn—N—C13	120.03 (16)	N—C13—C12′	116.3 (4)
Zn—N—C9	122.45 (16)	N—C13—C12	126.5 (3)
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Figure 1
View of the title compound with the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level [symmetry code: (i) −x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z]. The major disorder component of the pyridine unit is drawn using solid lines and the minor disorder component is drawn using dashed lines.

2. Supramolecular features

The crystal structure features extensive O—H⋯O hydrogen bonding [O3⋯O2ⁱⁱ =2.572 (2) Å] (Fig. 2), establishing a three-dimensional network that is consolidated by further C—H⋯O hydrogen-bonding interactions. The C2—H2A⋯O1ⁱⁱ, C8—H8A⋯O2ⁱⁱⁱ and C13—H13A⋯O2ⁱⁱ distances are 3.193 (2), 3.378 (3), and 3.064 (3) Å, respectively (Table 2). In addition, C—H ⋯π interactions [C9—H9A⋯Cg5^iv = 3.781 (2) Å and C12′–H12B⋯Cg5ⁱⁱ = 3.649 (8) Å, Table 2] and π–π stacking are present in the crystal structure. The distance Cg5⋯Cg3^iv between the centroids of the phenyl ring (C3–C8) of the mandelate group and of the 1,2-bis(pyridine-4-yl)ethane moiety (C9–C13) [symmetry code: (iv) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ ] is 4.951 (2) Å and the dihedral angle between the two rings is 62.6 (2)°.

Table 2
Hydrogen-bond geometry (Å, °)

Cg5 is the centroid of the C3–C8 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O2ⁱⁱ	0.86 (3)	1.72 (3)	2.572 (2)	177.3 (15)
C2—H2A⋯O1ⁱⁱ	1.00	2.46	3.193 (2)	129
C8—H8A⋯O2ⁱⁱⁱ	0.95	2.44	3.378 (3)	168
C13—H13A⋯O2ⁱⁱ	0.96	2.43	3.064 (3)	124
C9—H9A⋯Cg5^iv	0.96	2.88	3.781 (2)	157
C12′—H12B⋯Cg5ⁱⁱ	0.95	2.75	3.649 (8)	159
Symmetry codes: (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+2]$ ; (iv) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
The molecular packing of the title compound. Hydrogen bonds are shown as dashed lines. The minor occupancy components of the disordered pyridine carbon atoms have been omitted for clarity.

3. Database survey

Other examples of complexes containing the mandelate anion and the 1,2-bis(pyridine-4-yl)ethane moiety were found in the Cambridge Structural Database (CSD, version 5.40, update of August 2019; Groom et al., 2016 ). These include catena-[[μ-oxido(phenyl)acetato](μ-4,4′-ethane-1,2-diyldipyridine)zinc(II) perchlorate monohydrate] (CSD refcode QEBFUB; Guo et al., 2015 ), which has a ClO₄⁻ counter-ion. An Ni complex, catena-[bis[(hydroxy)(phenyl)acetato]{μ-4-[2-(pyridin-4-yl)ethyl]pyridine}nickel(II)], isostructural with the title compound, has also been reported (QEBFAH; Guo et al., 2015). A complex with the same molecular formula but different coordination environment of the Zn atom, catena-[[μ₂-1,2-bis(4-pyridyl)ethane]bis(2-hydroxy-2-phenylacetato)zinc(II)] (MUBZEP; Yu et al., 2009 ) has also been characterized. In this case, the 1,2-bis(pyridine-4-yl)ethane and mandelate units are cis to each other.

4. Synthesis and crystallization

Zn(NO₃)₂ (91.4 mg, 0.50 mmol), 1,2-bi(4-pyridyl)ethane (92.1 mg, 0.50 mmol) and mandelic acid (76.0 mg, 0.50 mmol) were mixed in deionized water. The mixture was placed in a 25 mL Teflon linear reactor and heated at 423 K in an autoclave for 24 h. The resulting solution was slowly cooled to room temperature. Yellow transparent single crystals of the title compound were obtained in 75% yield (based on Zn).

5. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3. Atoms C10, C11, C12, C14 of the pyridine ring are disordered over two sets of sites with an occupancy of 0.578 (14) for the major moiety. C-bound H atoms were included in calculated positions and treated as riding: C—H = 0.95 Å with U_iso(H) = 1.5U_eq(C-methyl) and 1.2U_eq(C) for other H atoms·The hydroxy H atoms, which could not be located in a difference-Fourier map, were included in idealized calculated positions that gave the most sensible geometry.

Table 3
Experimental details

Crystal data
Chemical formula	[Zn(C₈H₇O₃)₂(C₁₂H₁₂N₂)]
M_r	551.90
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	25.6754 (19), 9.8838 (5), 10.6208 (7)
β (°)	108.234 (7)
V (Å³)	2559.9 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.01
Crystal size (mm)	0.35 × 0.32 × 0.26

Data collection
Diffractometer	Oxford Diffraction Gemini-S CCD detector
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ )
T_min, T_max	0.936, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5016, 2270, 1970
R_int	0.027

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.082, 1.04
No. of reflections	2270
No. of parameters	210
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.41
Computer programs: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), DIAMOND (Brandenburg & Putz, 1999 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2040978

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989020014322/cq2039sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020014322/cq2039Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 1999); software used to prepare material for publication: PLATON (Spek, 2020).

catena-Poly[[bis[hydroxy(phenyl)acetato-κ²O¹,O²]zinc(II)]-µ₂-1,2-bis(pyridin-4-yl)ethane-κ²N:N'] top

Crystal data top

[Zn(C₈H₇O₃)₂(C₁₂H₁₂N₂)]	F(000) = 1144
M_r = 551.90	D_x = 1.432 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1818 reflections
a = 25.6754 (19) Å	θ = 2.8–29.2°
b = 9.8838 (5) Å	µ = 1.00 mm⁻¹
c = 10.6208 (7) Å	T = 150 K
β = 108.234 (7)°	Parallelepiped, yellow
V = 2559.9 (3) Å³	0.35 × 0.32 × 0.26 mm
Z = 4

Data collection top

Oxford Diffraction Gemini-S CCD detector diffractometer	2270 independent reflections
Radiation source: fine-focus sealed tube	1970 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω scans	θ_max = 25.0°, θ_min = 2.8°
Absorption correction: multi-scan (CrysAlisPro; Oxford Diffraction, 2009)	h = −23→30
T_min = 0.936, T_max = 1.000	k = −7→11
5016 measured reflections	l = −12→11

Refinement top

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.038P)² + 2.1396P] where P = (F_o² + 2F_c²)/3
2270 reflections	(Δ/σ)_max < 0.001
210 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn	0.25000	0.25000	0.50000	0.0138 (1)
O1	0.25093 (6)	0.37191 (14)	0.65439 (14)	0.0171 (5)
O2	0.26248 (7)	0.37664 (14)	0.87065 (15)	0.0229 (5)
O3	0.28062 (6)	0.11415 (15)	0.65814 (14)	0.0151 (5)
N	0.16575 (7)	0.18198 (19)	0.48454 (18)	0.0189 (6)
C1	0.26431 (9)	0.3184 (2)	0.7677 (2)	0.0146 (6)
C2	0.28282 (9)	0.1695 (2)	0.7835 (2)	0.0154 (7)
C3	0.33972 (9)	0.1537 (2)	0.8826 (2)	0.0164 (6)
C4	0.38568 (10)	0.1438 (2)	0.8401 (2)	0.0249 (7)
C5	0.43745 (11)	0.1262 (3)	0.9311 (3)	0.0349 (9)
C6	0.44387 (11)	0.1178 (3)	1.0644 (3)	0.0352 (9)
C7	0.39842 (11)	0.1278 (2)	1.1077 (2)	0.0319 (8)
C8	0.34670 (10)	0.1461 (2)	1.0174 (2)	0.0235 (7)
C9	0.13113 (11)	0.2581 (2)	0.5259 (3)	0.0279 (8)
C10	0.0768 (3)	0.2104 (9)	0.5048 (9)	0.0261 (19)	0.578 (14)
C11	0.0594 (2)	0.0835 (5)	0.4523 (9)	0.026 (2)	0.578 (14)
C12	0.0972 (3)	0.0046 (6)	0.4172 (10)	0.0260 (18)	0.578 (14)
C13	0.14957 (10)	0.0569 (2)	0.4432 (3)	0.0310 (8)
C14	0.0017 (3)	0.0308 (7)	0.4359 (5)	0.0341 (17)	0.578 (14)
C12'	0.1046 (4)	0.0024 (8)	0.4827 (13)	0.025 (3)	0.422 (14)
C14'	0.0228 (4)	0.0209 (9)	0.5626 (7)	0.028 (3)	0.422 (14)
C10'	0.0870 (5)	0.2148 (13)	0.5599 (12)	0.026 (3)	0.422 (14)
C11'	0.0722 (3)	0.0805 (6)	0.5343 (12)	0.021 (2)	0.422 (14)
H4A	0.38160	0.14900	0.74820	0.0300*
H7A	0.40270	0.12210	1.19970	0.0380*
H5A	0.46860	0.12000	0.90120	0.0420*
H6A	0.47930	0.10510	1.12650	0.0420*
H10A	0.05140	0.26770	0.52760	0.0320*	0.578 (14)
H12A	0.08770	−0.08160	0.37700	0.0310*	0.578 (14)
H13A	0.17770	−0.00500	0.43840	0.0370*
H14A	−0.02490	0.10630	0.40920	0.0410*	0.578 (14)
H14B	−0.00830	−0.03820	0.36490	0.0410*	0.578 (14)
H8A	0.31580	0.15360	1.04800	0.0280*
H9A	0.13500	0.35420	0.51880	0.0330*
H2A	0.25660	0.11780	0.81760	0.0180*
H3A	0.2653 (11)	0.036 (3)	0.647 (3)	0.039 (8)*
H10B	0.06730	0.27390	0.59920	0.0310*	0.422 (14)
H12B	0.09720	−0.09190	0.47220	0.0300*	0.422 (14)
H14C	0.00800	0.08830	0.61150	0.0340*	0.422 (14)
H14D	0.03450	−0.05930	0.62030	0.0340*	0.422 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn	0.0156 (2)	0.0132 (2)	0.0143 (2)	−0.0016 (2)	0.0070 (2)	−0.0005 (1)
O1	0.0242 (9)	0.0122 (7)	0.0164 (8)	0.0026 (7)	0.0086 (6)	0.0012 (6)
O2	0.0352 (10)	0.0182 (8)	0.0176 (8)	0.0074 (7)	0.0115 (7)	−0.0001 (6)
O3	0.0222 (9)	0.0085 (7)	0.0157 (8)	−0.0012 (7)	0.0075 (6)	−0.0007 (6)
N	0.0166 (10)	0.0191 (10)	0.0217 (10)	−0.0016 (9)	0.0072 (8)	0.0046 (8)
C1	0.0134 (11)	0.0133 (11)	0.0193 (11)	−0.0012 (9)	0.0084 (9)	−0.0006 (9)
C2	0.0208 (12)	0.0109 (11)	0.0183 (11)	−0.0013 (10)	0.0115 (9)	−0.0014 (8)
C3	0.0214 (12)	0.0088 (10)	0.0196 (11)	0.0000 (9)	0.0074 (9)	0.0015 (8)
C4	0.0221 (13)	0.0303 (13)	0.0227 (12)	0.0043 (11)	0.0075 (10)	0.0005 (10)
C5	0.0222 (14)	0.0431 (16)	0.0388 (16)	0.0047 (13)	0.0089 (12)	0.0005 (12)
C6	0.0274 (15)	0.0358 (15)	0.0324 (15)	0.0032 (12)	−0.0049 (12)	0.0040 (12)
C7	0.0412 (17)	0.0305 (14)	0.0187 (12)	−0.0026 (13)	0.0016 (11)	0.0041 (10)
C8	0.0298 (14)	0.0198 (12)	0.0234 (12)	−0.0020 (11)	0.0118 (10)	0.0015 (10)
C9	0.0229 (14)	0.0229 (13)	0.0414 (15)	0.0022 (11)	0.0151 (12)	0.0065 (11)
C10	0.014 (3)	0.038 (3)	0.028 (4)	−0.001 (3)	0.009 (3)	−0.005 (4)
C11	0.016 (2)	0.032 (3)	0.030 (5)	−0.007 (2)	0.007 (3)	0.005 (2)
C12	0.024 (3)	0.020 (2)	0.034 (4)	−0.003 (2)	0.009 (3)	−0.001 (3)
C13	0.0174 (13)	0.0188 (13)	0.0563 (17)	0.0011 (11)	0.0110 (12)	0.0067 (12)
C14	0.022 (3)	0.042 (3)	0.040 (3)	−0.006 (3)	0.012 (2)	0.007 (3)
C12'	0.024 (4)	0.016 (3)	0.036 (6)	−0.005 (3)	0.011 (4)	−0.002 (4)
C14'	0.026 (5)	0.031 (4)	0.035 (4)	−0.008 (4)	0.020 (3)	0.002 (3)
C10'	0.022 (5)	0.029 (4)	0.025 (6)	−0.004 (3)	0.006 (5)	−0.011 (5)
C11'	0.014 (3)	0.028 (3)	0.021 (6)	−0.005 (3)	0.007 (3)	0.001 (3)

Geometric parameters (Å, º) top

Zn—O1	2.0290 (14)	C11—C12	1.384 (10)
Zn—O3	2.1013 (15)	C11—C14	1.528 (10)
Zn—N	2.2217 (19)	C11'—C14'	1.512 (13)
Zn—O1ⁱ	2.0290 (14)	C11'—C12'	1.369 (14)
Zn—O3ⁱ	2.1013 (15)	C12—C13	1.385 (9)
Zn—Nⁱ	2.2217 (19)	C12'—C13	1.450 (11)
O1—C1	1.260 (2)	C14—C14ⁱⁱ	1.519 (8)
O2—C1	1.250 (3)	C14'—C14'ⁱⁱ	1.528 (12)
O3—C2	1.424 (2)	C2—H2A	1.0000
O3—H3A	0.86 (3)	C4—H4A	0.9500
N—C13	1.334 (3)	C5—H5A	0.9500
N—C9	1.339 (3)	C6—H6A	0.9500
C1—C2	1.540 (3)	C7—H7A	0.9500
C2—C3	1.518 (3)	C8—H8A	0.9500
C3—C8	1.388 (3)	C9—H9A	0.9600
C3—C4	1.393 (4)	C10—H10A	0.9500
C4—C5	1.388 (4)	C10'—H10B	0.9500
C5—C6	1.376 (4)	C12—H12A	0.9500
C6—C7	1.385 (4)	C12'—H12B	0.9500
C7—C8	1.385 (3)	C13—H13A	0.9600
C9—C10	1.422 (9)	C14—H14B	0.9900
C9—C10'	1.361 (14)	C14—H14A	0.9900
C10—C11	1.388 (11)	C14'—H14C	0.9900
C10'—C11'	1.384 (14)	C14'—H14D	0.9900

O1···O3	2.656 (2)	C9···H4Aⁱ	2.9700
O1···N	3.015 (2)	C10···H14Bⁱⁱ	3.0700
O1···C2	2.419 (2)	C10'···H7A^iv	2.9600
O1···C9	3.156 (3)	C12'···H14Cⁱⁱ	2.8900
O1···C13ⁱ	3.123 (3)	C13···H3A	3.09 (3)
O1···C2ⁱⁱⁱ	3.193 (2)	C14'···H12Bⁱⁱ	3.0700
O1···Nⁱ	3.002 (2)	H2A···O1^v	2.4600
O1···O3ⁱ	3.164 (2)	H2A···C1^v	3.0900
O2···C8^iv	3.378 (3)	H2A···H8A	2.4700
O2···O3ⁱⁱⁱ	2.572 (2)	H3A···O1^v	2.79 (3)
O2···C2ⁱⁱⁱ	3.350 (2)	H3A···C13	3.09 (3)
O2···C8	3.192 (3)	H3A···O2^v	1.72 (3)
O2···C13ⁱⁱⁱ	3.064 (3)	H3A···C1^v	2.54 (3)
O3···O1ⁱ	3.164 (2)	H4A···O3	2.4900
O3···N	3.024 (2)	H4A···Nⁱ	2.9200
O3···C1	2.431 (3)	H4A···C9ⁱ	2.9700
O3···O2^v	2.572 (2)	H5A···H10A^vi	2.4000
O3···C1^v	3.326 (3)	H6A···H6A^vii	2.5000
O3···O1	2.656 (2)	H7A···C10'^iv	2.9600
O3···Nⁱ	3.092 (2)	H7A···H10B^iv	2.2800
O1···H13Aⁱ	2.6800	H8A···H2A	2.4700
O1···H3Aⁱⁱⁱ	2.79 (3)	H8A···O2^iv	2.4400
O1···H9A	2.8800	H9A···C8ⁱⁱⁱ	2.9700
O1···H2Aⁱⁱⁱ	2.4600	H9A···C7ⁱⁱⁱ	3.0200
O2···H8A^iv	2.4400	H9A···O1	2.8800
O2···H3Aⁱⁱⁱ	1.72 (3)	H10A···H14A	2.5300
O2···H13Aⁱⁱⁱ	2.4300	H10A···C5^viii	2.9700
O3···H4A	2.4900	H10A···H5A^viii	2.4000
N···O1	3.015 (2)	H10B···H14C	2.4100
N···O3	3.024 (2)	H10B···H7A^iv	2.2800
N···O1ⁱ	3.002 (2)	H12A···H14B	2.4700
N···O3ⁱ	3.092 (2)	H12A···C7^v	2.8900
N···H4Aⁱ	2.9200	H12B···H14D	2.6000
C1···O3ⁱⁱⁱ	3.326 (3)	H12B···C14'ⁱⁱ	3.0700
C2···O2^v	3.350 (2)	H12B···C7^v	2.9100
C2···O1^v	3.193 (2)	H12B···C8^v	2.9500
C8···O2	3.192 (3)	H12B···H14Cⁱⁱ	2.5700
C8···O2^iv	3.378 (3)	H12B···C6^v	3.0400
C13···O2^v	3.064 (3)	H13A···O1ⁱ	2.6800
C1···H3Aⁱⁱⁱ	2.54 (3)	H13A···O2^v	2.4300
C1···H2Aⁱⁱⁱ	3.0900	H14A···C5^viii	2.8500
C5···H10A^vi	2.9700	H14A···H10A	2.5300
C5···H14A^vi	2.8500	H14B···H12A	2.4700
C6···H12Bⁱⁱⁱ	3.0400	H14B···C10ⁱⁱ	3.0700
C7···H12Bⁱⁱⁱ	2.9100	H14C···H10B	2.4100
C7···H12Aⁱⁱⁱ	2.8900	H14C···C12'ⁱⁱ	2.8900
C7···H9A^v	3.0200	H14C···H12Bⁱⁱ	2.5700
C8···H12Bⁱⁱⁱ	2.9500	H14D···H12B	2.6000
C8···H9A^v	2.9700

O1—Zn—O3	80.02 (6)	C10'—C11'—C14'	122.1 (9)
O1—Zn—N	90.25 (7)	C11—C12—C13	117.1 (6)
O1—Zn—O1ⁱ	180.00	C11'—C12'—C13	123.0 (7)
O1—Zn—O3ⁱ	99.98 (6)	N—C13—C12'	116.3 (4)
O1—Zn—Nⁱ	89.75 (7)	N—C13—C12	126.5 (3)
O3—Zn—N	88.73 (6)	C11—C14—C14ⁱⁱ	111.1 (6)
O1ⁱ—Zn—O3	99.98 (6)	C11'—C14'—C14'ⁱⁱ	113.2 (7)
O3—Zn—O3ⁱ	180.00	O3—C2—H2A	108.00
O3—Zn—Nⁱ	91.27 (6)	C1—C2—H2A	108.00
O1ⁱ—Zn—N	89.75 (7)	C3—C2—H2A	108.00
O3ⁱ—Zn—N	91.27 (6)	C3—C4—H4A	120.00
N—Zn—Nⁱ	180.00	C5—C4—H4A	120.00
O1ⁱ—Zn—O3ⁱ	80.02 (6)	C4—C5—H5A	120.00
O1ⁱ—Zn—Nⁱ	90.25 (7)	C6—C5—H5A	120.00
O3ⁱ—Zn—Nⁱ	88.73 (6)	C5—C6—H6A	120.00
Zn—O1—C1	116.96 (13)	C7—C6—H6A	120.00
Zn—O3—C2	113.41 (12)	C6—C7—H7A	120.00
C2—O3—H3A	111 (2)	C8—C7—H7A	120.00
Zn—O3—H3A	115 (2)	C3—C8—H8A	120.00
Zn—N—C13	120.03 (16)	C7—C8—H8A	120.00
Zn—N—C9	122.45 (16)	N—C9—H9A	116.00
C9—N—C13	117.3 (2)	C10—C9—H9A	116.00
O2—C1—C2	116.10 (17)	C10'—C9—H9A	117.00
O1—C1—O2	124.67 (19)	C9—C10—H10A	119.00
O1—C1—C2	119.21 (18)	C11—C10—H10A	119.00
O3—C2—C3	110.90 (18)	C9—C10'—H10B	122.00
O3—C2—C1	110.17 (16)	C11'—C10'—H10B	122.00
C1—C2—C3	111.79 (17)	C11—C12—H12A	122.00
C2—C3—C8	120.4 (2)	C13—C12—H12A	121.00
C2—C3—C4	120.78 (18)	C13—C12'—H12B	119.00
C4—C3—C8	118.8 (2)	C11'—C12'—H12B	118.00
C3—C4—C5	120.5 (2)	N—C13—H13A	116.00
C4—C5—C6	120.3 (3)	C12—C13—H13A	117.00
C5—C6—C7	119.7 (3)	C12'—C13—H13A	117.00
C6—C7—C8	120.3 (2)	C14ⁱⁱ—C14—H14B	109.00
C3—C8—C7	120.5 (2)	H14A—C14—H14B	108.00
N—C9—C10	118.8 (4)	C14ⁱⁱ—C14—H14A	109.00
N—C9—C10'	127.1 (6)	C11—C14—H14A	109.00
C9—C10—C11	122.6 (7)	C11—C14—H14B	109.00
C9—C10'—C11'	116.7 (10)	C11'—C14'—H14C	109.00
C12—C11—C14	120.9 (6)	C11'—C14'—H14D	109.00
C10—C11—C14	122.2 (6)	H14C—C14'—H14D	108.00
C10—C11—C12	116.9 (6)	C14'ⁱⁱ—C14'—H14C	109.00
C12'—C11'—C14'	120.9 (7)	C14'ⁱⁱ—C14'—H14D	109.00
C10'—C11'—C12'	117.1 (9)

O3—Zn—O1—C1	−4.48 (16)	O1—C1—C2—C3	122.9 (2)
N—Zn—O1—C1	84.19 (17)	O2—C1—C2—O3	177.3 (2)
O3ⁱ—Zn—O1—C1	175.52 (16)	O2—C1—C2—C3	−58.9 (3)
Nⁱ—Zn—O1—C1	−95.81 (17)	O3—C2—C3—C4	25.8 (3)
O1—Zn—O3—C2	3.79 (14)	O3—C2—C3—C8	−152.94 (18)
N—Zn—O3—C2	−86.69 (14)	C1—C2—C3—C4	−97.6 (2)
O1ⁱ—Zn—O3—C2	−176.21 (14)	C1—C2—C3—C8	83.7 (2)
Nⁱ—Zn—O3—C2	93.31 (14)	C2—C3—C4—C5	−178.5 (2)
O1—Zn—N—C9	25.77 (19)	C8—C3—C4—C5	0.2 (3)
O1—Zn—N—C13	−148.46 (19)	C2—C3—C8—C7	178.15 (18)
O3—Zn—N—C9	105.78 (19)	C4—C3—C8—C7	−0.6 (3)
O3—Zn—N—C13	−68.45 (19)	C3—C4—C5—C6	0.3 (4)
O1ⁱ—Zn—N—C9	−154.23 (19)	C4—C5—C6—C7	−0.4 (4)
O1ⁱ—Zn—N—C13	31.54 (19)	C5—C6—C7—C8	0.0 (4)
O3ⁱ—Zn—N—C9	−74.22 (19)	C6—C7—C8—C3	0.5 (3)
O3ⁱ—Zn—N—C13	111.55 (19)	N—C9—C10—C11	5.1 (10)
Zn—O1—C1—O2	−173.77 (19)	C9—C10—C11—C12	−1.7 (13)
Zn—O1—C1—C2	4.3 (3)	C9—C10—C11—C14	177.2 (6)
Zn—O3—C2—C1	−2.7 (2)	C10—C11—C12—C13	2.9 (12)
Zn—O3—C2—C3	−127.04 (14)	C14—C11—C12—C13	−176.0 (6)
Zn—N—C9—C10	176.2 (4)	C10—C11—C14—C14ⁱⁱ	−83.6 (9)
C13—N—C9—C10	−9.5 (5)	C12—C11—C14—C14ⁱⁱ	95.2 (9)
Zn—N—C13—C12	−173.7 (5)	C11—C12—C13—N	−8.3 (11)
C9—N—C13—C12	11.8 (6)	C11—C14—C14ⁱⁱ—C11ⁱⁱ	180.0 (5)
O1—C1—C2—O3	−0.9 (3)

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x, −y, −z+1; (iii) −x+1/2, y+1/2, −z+3/2; (iv) −x+1/2, −y+1/2, −z+2; (v) −x+1/2, y−1/2, −z+3/2; (vi) x+1/2, −y+1/2, z+1/2; (vii) −x+1, y, −z+5/2; (viii) x−1/2, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

Cg5 is the centroid of the C3–C8 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2^v	0.86 (3)	1.72 (3)	2.572 (2)	177.3 (15)
C2—H2A···O1^v	1.00	2.46	3.193 (2)	129
C8—H8A···O2^iv	0.95	2.44	3.378 (3)	168
C13—H13A···O2^v	0.96	2.43	3.064 (3)	124
C9—H9A···Cg5ⁱⁱⁱ	0.96	2.88	3.781 (2)	157
C12′—H12B···Cg5^v	0.95	2.75	3.649 (8)	159

Symmetry codes: (iii) −x+1/2, y+1/2, −z+3/2; (iv) −x+1/2, −y+1/2, −z+2; (v) −x+1/2, y−1/2, −z+3/2.

Funding information

This work was supported financially by Yuanpei University, Taiwan.

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