Crystal structure of poly[di­chlorido­(μ-2,5-di­carb­oxy­benzene-1,4-di­carboxyl­ato-κ2O1:O4)bis­[μ-4′-(pyridin-3-yl)-4,2′:6′,4′′-terpyridine-κ2N1:N4′]dizinc]

Tian, Y.; Xu, S.-S.; Su, J.; Zhang, Y.; Zhao, S.-S.; Tian, Y.-P.

doi:10.1107/S2056989016016285

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ISSN: 2056-9890

Volume 72| Part 11| November 2016| Pages 1663-1665

https://doi.org/10.1107/S2056989016016285

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Crystal structure of poly[dichlorido(μ-2,5-dicarboxybenzene-1,4-dicarboxylato-κ²O¹:O⁴)bis[μ-4′-(pyridin-3-yl)-4,2′:6′,4′′-terpyridine-κ²N¹:N^4′]dizinc]

Yue Tian,^a Sha-Sha Xu,^a Jian Su,^a Yang Zhang,^a Shao-Shuai Zhao ^a and Yu-Peng Tian ^a ^*

^aDepartment of Chemistry, Key Laboratory of Functional Inorganic Materials Chemistry of Anhui Province, Anhui University, Hefei 230601, People's Republic of China
^*Correspondence e-mail: yptian@ahu.edu.cn

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 23 August 2016; accepted 13 October 2016; online 28 October 2016)

In the title polymeric Zn^II complex, [Zn₂(C₁₀H₄O₈)Cl₂(C₂₀H₁₄N₄)₂]_n, the Zn^II cations are bridged by both 2,5-dicarboxybenzene-1,4-dicarboxylate dianions and 4′-(pyridin-3-yl)-4,2′:6′,4′′-terpyridine ligands, forming ladder-like polymeric chains propagating along [1-10]. The Cl⁻ anion further coordinates the Zn^II cation to complete a distorted tetrahedral environment. In the 4′-(pyridin-3-yl)-4,2′:6′,4′′-terpyridine ligand, the three sideward pyridine rings are twisted with respect to the central pyridine ring by 39.27 (12), 14.89 (13) and 3.36 (13)°, respectively. In the crystal, classical O—H⋯N hydrogen bonds and weak C—H⋯O and C—H⋯Cl hydrogen bonds link the chains into a three-dimensional supramolecular architecture. π–π stacking is observed between the pyridine and benzene rings of neighbouring polymeric chains, with a centroid-to-centroid distance of 3.7280 (14) Å.

Keywords: crystal structure; 4′-(pyridin-3-yl)-4,2′:6′,4′′-terpyridine; zinc(II) complex; coordination polymer.

CCDC reference: 1509671

1. Chemical context

Coordination polymers (CPs) represent a class of crystalline materials which consist of different ligands interconnected by metallic nodes (Yaghi & Li; 1995 ; Hinterholzinger et al., 2012 ). Compared to traditional inorganic materials, CPs have fascinating structures with regular pore shape and size obtained by rational design (Kepert, 2006 ; Brammer, 2004 ). In addition, studies over several decades have revealed that CPs have multi-functional applications such as gas storage and separation (Rosi et al., 2003 ; Jiang et al., 2013 ), chemical purification (Li et al., 2012 ), catalysis (Seo et al., 2000 ), and sensors (Kreno et al., 2012 ), etc.

Pyridine-containing compounds, such as 4,2′:6′,4′′-terpyridine derivatives, are of great importance in the design of organic ligands, because conjugated polypyridyl ligands can form a better rigid plane and improve the stability of the network (Hancock, 2013 ; Li et al., 2011 ; Bhaumik et al., 2011 ). As a rigid planar and triangular ligand, 4′-(3-pyridyl)-4,2′:6′,4′′-terpyridine (344-pytpy; Housecroft, 2014 ) is different from commonly employed polypyridyl ligands such as 1,3,5-tri(4-pyridyl)-2,4,6-triazine (Ma & Coppens, 2003 ; Kumazawa et al., 2003 ), which have been widely studied in the field of coordination chemistry. Its rigidity and trigonal geometry may lead to the formation of nanosized cages and porous frameworks enclosing cavities and channels (Li et al., 2008 ; Yoshizawa et al., 2004 ; Dai et al., 2008 ). 1,2,4,5-Benzenetetracarbonic acid (H₄bta) is frequently employed due to the rich coordination binding sites of the carboxylate groups (Hou et al., 2011 ). We selected 344-pytpy and 1,2,4,5-benzenetetracarbonic acid as the organic linkers which, when assembled with Zn cations, resulted in the title coordination polymer [Zn₂(344-pytpy)₂(H₂bta)Cl₂]_n.

2. Structural commentary

As shown in Fig. 1, the asymmetric unit of the title compound contains one Zn^II cation, one 344-pytpy ligand, a half of an H₂bta²⁻ anion and one coordinating Cl⁻ anion. The Zn^II atom is four-coordinated by two nitrogen atoms (N1, N3) from two different 344-pytpy ligands [Zn1—N1 = 2.070 (2) and Zn1—N3 = 2.0217 (18) Å], one oxygen atom (O2) from an H₂bta²⁻ anion [Zn1—O2 = 1.9171 (16) Å] and one Cl atom [Zn1—Cl1 = 2.2278 (7) Å] in a distorted tetrahedral coordination geometry. The bond lengths around Zn1 are similar to those reported by Wang et al. (2009 ). The X—Zn—X (X = N, O or Cl atom) angles range from 97.21 (8) to 115.73 (8)° and the tetrahedron edge lengths range from 2.992 (3) to 3.591 (2) Å. Each 344-pytpy ligand act as 2-connecting node, linking two Zn atoms by the outer N-terminal atoms (N1, N3), the central and another outer pyridine N atom (N2, N4) are free. The H₂bta²⁻ anion is located on an inversion center, and bridges two Zn^II atoms through the two carboxylate groups. In this way, chains propagating along [1 $[\overline1]$ 0] are formed (Fig. 2).

Figure 1
Part of the polymeric structure of the title complex [symmetry codes: (i) −x, −y + 1, −z + 2; (ii) x + 1, y − 1, z]. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
Part of the polymeric chain.

3. Supramolecular features

In the crystal, classical O—H⋯N hydrogen bonds, weak C—H⋯O and C—H⋯Cl hydrogen bonds (Table 1) link the chains into a three-dimensional supramolecular architecture. π–π stacking is observed between the N3-pyridine ring and benzene ring of the neighboring chain, with a centroid-to-centroid distance of 3.7280 (14) Å.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯N4ⁱⁱ	0.82	1.83	2.633 (3)	167
C15—H15⋯O1ⁱⁱⁱ	0.93	2.46	3.383 (3)	172
C17—H17⋯Cl1^iv	0.93	2.75	3.678 (3)	173
C22—H22⋯O4^v	0.93	2.59	3.305 (4)	134
C25—H25⋯O1ⁱⁱⁱ	0.93	2.34	3.267 (3)	175
Symmetry codes: (ii) -x, -y+1, -z+3; (iii) -x+1, -y+1, -z+2; (iv) -x+1, -y+2, -z+1; (v) x, y+1, z.

3.1. Synthesis and crystallization

4′-(3-Pyridyl)-4,2′:6′,4′′-terpyridine was synthesized according to a literature method (Yang et al., 2014 ). 344-pytpy (0.0310 g, 0.1 mmol), ZnCl₂ (0.0136 g, 0.1 mmol) and 1,2,4,5-benzenetetracarbonic acid (0.0254 g, 0.1 mmol) were adequately dispersed in 10 mL of distilled water, and then the mixture was sealed and heated to 453 K for three days under hydrothermal conditions. The vial was then allowed to cool to room temperature. Colorless block-shaped crystals were collected (0.010 g, yield 38.9%, based on Zn).

3.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were placed in geometrically idealized positions and treated as riding, with C—H = 0.93 and O—H = 0.82 Å, and with U_iso(H) = 1.2U_eq(C) and 1.5U_eq(O).

Table 2
Experimental details

Crystal data
Chemical formula	[Zn₂(C₁₀H₄O₈)Cl₂(C₂₀H₁₄N₄)₂]
M_r	537.24
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	8.6557 (6), 12.1432 (8), 12.5842 (9)
α, β, γ (°)	61.396 (1), 74.216 (1), 75.411 (1)
V (Å³)	1105.83 (13)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.27
Crystal size (mm)	0.23 × 0.22 × 0.17

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2000 )
T_min, T_max	0.758, 0.813
No. of measured, independent and observed [I > 2σ(I)] reflections	7896, 3840, 3435
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.080, 1.07
No. of reflections	3840
No. of parameters	317
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.27
Computer programs: SMART and SAINT (Bruker, 2000), SHELXS97 and SHELXTL (Sheldrick, 2008 ) and SHELXL2013 (Sheldrick, 2015 ).

Supporting information

CCDC reference: 1509671

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989016016285/xu5893sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016016285/xu5893Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989016016285/xu5893Isup3.cdx

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Poly[dichlorido(µ-2,5-dicarboxybenzene-1,4-dicarboxylato-κ²O¹:O⁴)bis[µ-4'-(pyridin-3-yl)-4,2':6',4''-terpyridine-κ²N¹:N^4']dizinc] top

Crystal data top

[Zn₂(C₁₀H₄O₈)Cl₂(C₂₀H₁₄N₄)₂]	Z = 2
M_r = 537.24	F(000) = 546
Triclinic, P1	D_x = 1.613 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6557 (6) Å	Cell parameters from 4113 reflections
b = 12.1432 (8) Å	θ = 2.5–26.8°
c = 12.5842 (9) Å	µ = 1.27 mm⁻¹
α = 61.396 (1)°	T = 296 K
β = 74.216 (1)°	Block, colorless
γ = 75.411 (1)°	0.23 × 0.22 × 0.17 mm
V = 1105.83 (13) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	3840 independent reflections
Radiation source: fine-focus sealed tube	3435 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
phi and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
T_min = 0.758, T_max = 0.813	k = −14→12
7896 measured reflections	l = −14→14

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.043P)² + 0.4805P] where P = (F_o² + 2F_c²)/3
3840 reflections	(Δ/σ)_max = 0.001
317 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

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

	x	y	z	U_iso*/U_eq
C1	0.3397 (3)	0.4695 (2)	0.8900 (2)	0.0279 (5)
C2	0.1613 (3)	0.4839 (2)	0.9422 (2)	0.0218 (5)
C3	0.1062 (3)	0.3951 (2)	1.0600 (2)	0.0239 (5)
H3	0.1774	0.3240	1.1002	0.029*
C4	−0.0533 (3)	0.4105 (2)	1.11919 (19)	0.0219 (5)
C5	−0.0971 (3)	0.3173 (2)	1.2513 (2)	0.0306 (6)
C6	0.6841 (3)	0.8624 (2)	0.5920 (2)	0.0297 (5)
H6	0.7535	0.8319	0.5380	0.036*
C7	0.6660 (3)	0.9894 (2)	0.5599 (2)	0.0317 (6)
H7	0.7220	1.0438	0.4860	0.038*
C8	0.5628 (3)	1.0346 (2)	0.6398 (2)	0.0280 (5)
H8	0.5457	1.1208	0.6186	0.034*
C9	0.4845 (3)	0.9514 (2)	0.7519 (2)	0.0228 (5)
C10	0.5101 (3)	0.8245 (2)	0.7761 (2)	0.0269 (5)
H10	0.4580	0.7676	0.8505	0.032*
C11	0.3721 (3)	0.9962 (2)	0.8406 (2)	0.0234 (5)
C12	0.2691 (3)	1.1105 (2)	0.7983 (2)	0.0259 (5)
H12	0.2725	1.1608	0.7143	0.031*
C13	0.1608 (3)	1.1490 (2)	0.8828 (2)	0.0236 (5)
C14	0.2517 (3)	0.9694 (2)	1.0459 (2)	0.0230 (5)
C15	0.3640 (3)	0.9256 (2)	0.9672 (2)	0.0254 (5)
H15	0.4331	0.8497	0.9987	0.030*
C16	0.0390 (3)	1.2655 (2)	0.8443 (2)	0.0237 (5)
C17	0.0453 (3)	1.3573 (2)	0.7232 (2)	0.0303 (6)
H17	0.1331	1.3513	0.6632	0.036*
C18	−0.0777 (3)	1.4565 (2)	0.6922 (2)	0.0299 (6)
H18	−0.0715	1.5165	0.6104	0.036*
C19	−0.2098 (3)	1.3857 (2)	0.8926 (2)	0.0251 (5)
H19	−0.2965	1.3958	0.9514	0.030*
C20	−0.0910 (3)	1.2841 (2)	0.9303 (2)	0.0254 (5)
H20	−0.0971	1.2276	1.0133	0.030*
C21	0.2301 (3)	0.8971 (2)	1.1827 (2)	0.0239 (5)
C22	0.1156 (3)	0.9462 (3)	1.2565 (2)	0.0334 (6)
H22	0.0533	1.0248	1.2213	0.040*
C23	0.0956 (3)	0.8769 (3)	1.3826 (2)	0.0374 (6)
H23	0.0199	0.9115	1.4309	0.045*
C24	0.2886 (3)	0.7152 (2)	1.3680 (2)	0.0331 (6)
H24	0.3473	0.6355	1.4060	0.040*
C25	0.3188 (3)	0.7786 (2)	1.2413 (2)	0.0283 (5)
H25	0.3975	0.7426	1.1955	0.034*
Cl1	0.60963 (8)	0.63418 (6)	0.52615 (5)	0.03639 (17)
N1	0.6063 (2)	0.78037 (18)	0.69741 (18)	0.0272 (4)
N2	0.1514 (2)	1.07932 (18)	1.00421 (17)	0.0252 (4)
N3	−0.2072 (2)	1.47156 (17)	0.77436 (17)	0.0234 (4)
N4	0.1792 (3)	0.7629 (2)	1.43877 (18)	0.0352 (5)
O1	0.4167 (2)	0.36497 (18)	0.9094 (2)	0.0572 (6)
O2	0.3980 (2)	0.57395 (16)	0.83257 (16)	0.0351 (4)
O3	−0.1565 (3)	0.37407 (17)	1.32170 (15)	0.0459 (5)
H3A	−0.1605	0.3216	1.3939	0.069*
O4	−0.0721 (4)	0.20509 (19)	1.2873 (2)	0.0792 (9)
Zn1	0.59827 (3)	0.60234 (2)	0.71763 (2)	0.02356 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0224 (12)	0.0315 (14)	0.0246 (12)	−0.0014 (11)	0.0023 (10)	−0.0128 (11)
C2	0.0208 (11)	0.0233 (12)	0.0210 (11)	−0.0041 (9)	0.0016 (9)	−0.0117 (10)
C3	0.0225 (12)	0.0239 (12)	0.0212 (11)	−0.0017 (9)	−0.0032 (9)	−0.0078 (10)
C4	0.0236 (12)	0.0216 (12)	0.0177 (11)	−0.0052 (9)	0.0018 (9)	−0.0085 (9)
C5	0.0269 (13)	0.0289 (14)	0.0248 (12)	−0.0014 (10)	0.0015 (10)	−0.0074 (11)
C6	0.0296 (13)	0.0293 (13)	0.0285 (12)	−0.0070 (10)	0.0075 (10)	−0.0167 (11)
C7	0.0355 (14)	0.0297 (14)	0.0254 (12)	−0.0126 (11)	0.0064 (10)	−0.0110 (11)
C8	0.0319 (13)	0.0198 (12)	0.0285 (12)	−0.0032 (10)	−0.0028 (10)	−0.0094 (10)
C9	0.0232 (12)	0.0207 (12)	0.0222 (11)	0.0001 (9)	−0.0041 (9)	−0.0092 (10)
C10	0.0277 (13)	0.0223 (12)	0.0221 (11)	−0.0024 (10)	0.0034 (10)	−0.0077 (10)
C11	0.0247 (12)	0.0220 (12)	0.0228 (11)	−0.0017 (9)	−0.0027 (9)	−0.0109 (10)
C12	0.0284 (13)	0.0235 (12)	0.0185 (11)	0.0001 (10)	−0.0017 (9)	−0.0065 (10)
C13	0.0244 (12)	0.0206 (12)	0.0217 (11)	0.0007 (9)	−0.0044 (9)	−0.0078 (9)
C14	0.0242 (12)	0.0199 (12)	0.0228 (11)	0.0002 (9)	−0.0046 (9)	−0.0093 (10)
C15	0.0259 (12)	0.0197 (12)	0.0243 (12)	0.0030 (9)	−0.0051 (10)	−0.0075 (10)
C16	0.0240 (12)	0.0212 (12)	0.0244 (11)	−0.0009 (9)	−0.0039 (9)	−0.0102 (10)
C17	0.0240 (12)	0.0294 (13)	0.0234 (12)	0.0045 (10)	0.0034 (10)	−0.0085 (10)
C18	0.0290 (13)	0.0254 (13)	0.0229 (12)	0.0027 (10)	−0.0004 (10)	−0.0063 (10)
C19	0.0228 (12)	0.0279 (13)	0.0235 (11)	−0.0026 (10)	0.0026 (9)	−0.0145 (10)
C20	0.0301 (13)	0.0227 (12)	0.0207 (11)	−0.0015 (10)	−0.0042 (10)	−0.0088 (10)
C21	0.0255 (12)	0.0231 (12)	0.0216 (11)	−0.0030 (9)	−0.0043 (9)	−0.0089 (10)
C22	0.0314 (14)	0.0353 (15)	0.0274 (13)	0.0053 (11)	−0.0047 (11)	−0.0142 (11)
C23	0.0309 (14)	0.0513 (17)	0.0277 (13)	−0.0027 (12)	0.0020 (11)	−0.0207 (13)
C24	0.0459 (16)	0.0254 (13)	0.0254 (12)	−0.0056 (11)	−0.0115 (11)	−0.0062 (11)
C25	0.0338 (13)	0.0264 (13)	0.0236 (12)	0.0003 (10)	−0.0055 (10)	−0.0122 (10)
Cl1	0.0431 (4)	0.0347 (4)	0.0254 (3)	0.0005 (3)	−0.0060 (3)	−0.0116 (3)
N1	0.0283 (11)	0.0197 (10)	0.0263 (10)	−0.0008 (8)	0.0023 (8)	−0.0094 (8)
N2	0.0246 (10)	0.0228 (10)	0.0229 (10)	0.0026 (8)	−0.0027 (8)	−0.0096 (8)
N3	0.0216 (10)	0.0211 (10)	0.0236 (10)	0.0011 (8)	−0.0020 (8)	−0.0098 (8)
N4	0.0430 (13)	0.0395 (13)	0.0204 (10)	−0.0138 (11)	−0.0020 (9)	−0.0092 (10)
O1	0.0329 (11)	0.0332 (11)	0.0777 (15)	0.0026 (9)	0.0135 (10)	−0.0184 (11)
O2	0.0243 (9)	0.0326 (10)	0.0384 (10)	−0.0087 (8)	0.0103 (8)	−0.0140 (8)
O3	0.0776 (15)	0.0351 (11)	0.0173 (8)	−0.0151 (10)	0.0021 (9)	−0.0076 (8)
O4	0.125 (2)	0.0231 (12)	0.0391 (12)	0.0033 (12)	0.0276 (13)	−0.0023 (9)
Zn1	0.02041 (16)	0.01912 (16)	0.02327 (15)	0.00026 (10)	0.00197 (11)	−0.00766 (11)

Geometric parameters (Å, º) top

C1—O1	1.217 (3)	C14—C15	1.389 (3)
C1—O2	1.277 (3)	C14—C21	1.493 (3)
C1—C2	1.507 (3)	C15—H15	0.9300
C2—C3	1.389 (3)	C16—C20	1.390 (3)
C2—C4ⁱ	1.399 (3)	C16—C17	1.389 (3)
C3—C4	1.393 (3)	C17—C18	1.366 (3)
C3—H3	0.9300	C17—H17	0.9300
C4—C2ⁱ	1.399 (3)	C18—N3	1.344 (3)
C4—C5	1.503 (3)	C18—H18	0.9300
C5—O4	1.192 (3)	C19—N3	1.345 (3)
C5—O3	1.298 (3)	C19—C20	1.368 (3)
C6—N1	1.339 (3)	C19—H19	0.9300
C6—C7	1.372 (3)	C20—H20	0.9300
C6—H6	0.9300	C21—C22	1.390 (3)
C7—C8	1.379 (3)	C21—C25	1.392 (3)
C7—H7	0.9300	C22—C23	1.379 (3)
C8—C9	1.390 (3)	C22—H22	0.9300
C8—H8	0.9300	C23—N4	1.333 (3)
C9—C10	1.389 (3)	C23—H23	0.9300
C9—C11	1.488 (3)	C24—N4	1.336 (3)
C10—N1	1.341 (3)	C24—C25	1.379 (3)
C10—H10	0.9300	C24—H24	0.9300
C11—C12	1.390 (3)	C25—H25	0.9300
C11—C15	1.392 (3)	Zn1—Cl1	2.2278 (7)
C12—C13	1.393 (3)	Zn1—N1	2.070 (2)
C12—H12	0.9300	Zn1—O2	1.9171 (16)
C13—N2	1.336 (3)	Zn1—N3ⁱⁱ	2.0217 (18)
C13—C16	1.490 (3)	O3—H3A	0.8200
C14—N2	1.343 (3)

O1—C1—O2	125.8 (2)	C20—C16—C13	120.1 (2)
O1—C1—C2	120.4 (2)	C17—C16—C13	122.8 (2)
O2—C1—C2	113.6 (2)	C18—C17—C16	119.9 (2)
C3—C2—C4ⁱ	119.3 (2)	C18—C17—H17	120.1
C3—C2—C1	118.5 (2)	C16—C17—H17	120.1
C4ⁱ—C2—C1	122.0 (2)	N3—C18—C17	123.1 (2)
C2—C3—C4	121.4 (2)	N3—C18—H18	118.4
C2—C3—H3	119.3	C17—C18—H18	118.4
C4—C3—H3	119.3	N3—C19—C20	123.1 (2)
C3—C4—C2ⁱ	119.3 (2)	N3—C19—H19	118.5
C3—C4—C5	117.6 (2)	C20—C19—H19	118.5
C2ⁱ—C4—C5	122.9 (2)	C19—C20—C16	119.8 (2)
O4—C5—O3	124.4 (2)	C19—C20—H20	120.1
O4—C5—C4	124.0 (2)	C16—C20—H20	120.1
O3—C5—C4	111.4 (2)	C22—C21—C25	117.5 (2)
N1—C6—C7	122.9 (2)	C22—C21—C14	120.1 (2)
N1—C6—H6	118.5	C25—C21—C14	122.4 (2)
C7—C6—H6	118.5	C23—C22—C21	119.2 (2)
C6—C7—C8	118.5 (2)	C23—C22—H22	120.4
C6—C7—H7	120.7	C21—C22—H22	120.4
C8—C7—H7	120.7	N4—C23—C22	123.4 (2)
C7—C8—C9	120.0 (2)	N4—C23—H23	118.3
C7—C8—H8	120.0	C22—C23—H23	118.3
C9—C8—H8	120.0	N4—C24—C25	123.1 (2)
C8—C9—C10	117.3 (2)	N4—C24—H24	118.4
C8—C9—C11	121.7 (2)	C25—C24—H24	118.4
C10—C9—C11	121.0 (2)	C24—C25—C21	119.3 (2)
N1—C10—C9	123.1 (2)	C24—C25—H25	120.4
N1—C10—H10	118.5	C21—C25—H25	120.4
C9—C10—H10	118.5	C6—N1—C10	118.1 (2)
C12—C11—C15	118.0 (2)	C6—N1—Zn1	119.29 (16)
C12—C11—C9	120.2 (2)	C10—N1—Zn1	121.30 (16)
C15—C11—C9	121.8 (2)	C13—N2—C14	118.72 (19)
C11—C12—C13	119.4 (2)	C18—N3—C19	116.97 (19)
C11—C12—H12	120.3	C18—N3—Zn1ⁱⁱⁱ	120.55 (15)
C13—C12—H12	120.3	C19—N3—Zn1ⁱⁱⁱ	121.90 (15)
N2—C13—C12	122.3 (2)	C23—N4—C24	117.5 (2)
N2—C13—C16	115.34 (19)	C1—O2—Zn1	125.37 (16)
C12—C13—C16	122.25 (19)	C5—O3—H3A	109.5
N2—C14—C15	122.2 (2)	O2—Zn1—N3ⁱⁱ	115.73 (8)
N2—C14—C21	114.85 (19)	O2—Zn1—N1	97.21 (8)
C15—C14—C21	122.9 (2)	N3ⁱⁱ—Zn1—N1	115.16 (8)
C11—C15—C14	119.4 (2)	O2—Zn1—Cl1	119.86 (6)
C11—C15—H15	120.3	N3ⁱⁱ—Zn1—Cl1	104.98 (6)
C14—C15—H15	120.3	N1—Zn1—Cl1	103.51 (6)
C20—C16—C17	117.0 (2)

O1—C1—C2—C3	38.5 (3)	C17—C16—C20—C19	3.6 (3)
O2—C1—C2—C3	−137.7 (2)	C13—C16—C20—C19	−174.3 (2)
O1—C1—C2—C4ⁱ	−147.7 (3)	N2—C14—C21—C22	−1.5 (3)
O2—C1—C2—C4ⁱ	36.1 (3)	C15—C14—C21—C22	180.0 (2)
C4ⁱ—C2—C3—C4	−1.3 (4)	N2—C14—C21—C25	177.0 (2)
C1—C2—C3—C4	172.7 (2)	C15—C14—C21—C25	−1.6 (4)
C2—C3—C4—C2ⁱ	1.3 (4)	C25—C21—C22—C23	0.3 (4)
C2—C3—C4—C5	−173.6 (2)	C14—C21—C22—C23	178.9 (2)
C3—C4—C5—O4	−53.0 (4)	C21—C22—C23—N4	−1.1 (4)
C2ⁱ—C4—C5—O4	132.3 (3)	N4—C24—C25—C21	−1.2 (4)
C3—C4—C5—O3	123.2 (2)	C22—C21—C25—C24	0.7 (4)
C2ⁱ—C4—C5—O3	−51.5 (3)	C14—C21—C25—C24	−177.8 (2)
N1—C6—C7—C8	−0.1 (4)	C7—C6—N1—C10	−1.8 (4)
C6—C7—C8—C9	2.3 (4)	C7—C6—N1—Zn1	165.3 (2)
C7—C8—C9—C10	−2.5 (3)	C9—C10—N1—C6	1.6 (4)
C7—C8—C9—C11	−179.9 (2)	C9—C10—N1—Zn1	−165.17 (18)
C8—C9—C10—N1	0.5 (4)	C12—C13—N2—C14	1.0 (4)
C11—C9—C10—N1	177.9 (2)	C16—C13—N2—C14	176.5 (2)
C8—C9—C11—C12	38.0 (3)	C15—C14—N2—C13	−0.4 (3)
C10—C9—C11—C12	−139.3 (2)	C21—C14—N2—C13	−178.9 (2)
C8—C9—C11—C15	−143.1 (2)	C17—C18—N3—C19	2.2 (4)
C10—C9—C11—C15	39.5 (3)	C17—C18—N3—Zn1ⁱⁱⁱ	−169.2 (2)
C15—C11—C12—C13	−1.1 (3)	C20—C19—N3—C18	−2.1 (3)
C9—C11—C12—C13	177.8 (2)	C20—C19—N3—Zn1ⁱⁱⁱ	169.18 (18)
C11—C12—C13—N2	−0.3 (4)	C22—C23—N4—C24	0.7 (4)
C11—C12—C13—C16	−175.5 (2)	C25—C24—N4—C23	0.4 (4)
C12—C11—C15—C14	1.7 (3)	O1—C1—O2—Zn1	22.1 (4)
C9—C11—C15—C14	−177.2 (2)	C2—C1—O2—Zn1	−161.85 (15)
N2—C14—C15—C11	−1.0 (4)	C1—O2—Zn1—N3ⁱⁱ	−49.0 (2)
C21—C14—C15—C11	177.4 (2)	C1—O2—Zn1—N1	−171.5 (2)
N2—C13—C16—C20	−11.3 (3)	C1—O2—Zn1—Cl1	78.4 (2)
C12—C13—C16—C20	164.2 (2)	C6—N1—Zn1—O2	−152.28 (19)
N2—C13—C16—C17	170.8 (2)	C10—N1—Zn1—O2	14.38 (19)
C12—C13—C16—C17	−13.7 (4)	C6—N1—Zn1—N3ⁱⁱ	84.84 (19)
C20—C16—C17—C18	−3.6 (4)	C10—N1—Zn1—N3ⁱⁱ	−108.50 (18)
C13—C16—C17—C18	174.4 (2)	C6—N1—Zn1—Cl1	−29.16 (19)
C16—C17—C18—N3	0.7 (4)	C10—N1—Zn1—Cl1	137.50 (17)
N3—C19—C20—C16	−0.8 (4)

Symmetry codes: (i) −x, −y+1, −z+2; (ii) x+1, y−1, z; (iii) x−1, y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···N4^iv	0.82	1.83	2.633 (3)	167
C15—H15···O1^v	0.93	2.46	3.383 (3)	172
C17—H17···Cl1^vi	0.93	2.75	3.678 (3)	173
C22—H22···O4^vii	0.93	2.59	3.305 (4)	134
C25—H25···O1^v	0.93	2.34	3.267 (3)	175

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

Acknowledgements

This work was supported by the National Natural Science Foundation of China (21271004, 21271003, 51372003, 51432001, 51472002), Focus on returned overseas scholars of the Ministry of Education of China, the Program for New Century Excellent Talents in Universities (China) and the Higher Education Revitalization Plan Talent Project (2013).

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