A two-dimensional Zn coordination polymer with a three-dimensional supra­molecular architecture

Liu, F.; Ding, Y.; Li, Q.; Zhang, L.

doi:10.1107/S2056989017012452

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Volume 73| Part 10| October 2017| Pages 1402-1404

https://doi.org/10.1107/S2056989017012452

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A two-dimensional Zn coordination polymer with a three-dimensional supramolecular architecture

Fuhong Liu,^a ^* Yan Ding,^a Qiuyu Li ^a and Liping Zhang ^a

^aBasis Department, Jilin Business and Technology College, Changchun, Jilin, People's Republic of China
^*Correspondence e-mail: liufh563@nenu.edu.cn

Edited by A. Van der Lee, Université de Montpellier II, France (Received 27 July 2017; accepted 29 August 2017; online 5 September 2017)

The title compound, poly[bis{μ₂-4,4′-bis[(1,2,4-triazol-1-yl)methyl]biphenyl-κ²N⁴:N^4′}bis(nitrato-κO)zinc(II)], [Zn(NO₃)₂(C₁₈H₁₆N₆)₂]_n, is a two-dimensional zinc coordination polymer constructed from 4,4′-bis[(1H-1,2,4-triazol-1-yl)methyl]-1,1′-biphenyl units. It was synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Zn^II cation is located on an inversion centre and is coordinated by two O atoms from two symmetry-related nitrate groups and four N atoms from four symmetry-related 4,4′-bis[(1H-1,2,4-triazol-1-yl)methyl]-1,1′-biphenyl ligands, forming a distorted octahedral {ZnN₄O₂} coordination geometry. The linear 4,4′-bis[(1H-1,2,4-triazol-1-yl)methyl]-1,1′-biphenyl ligand links two Zn^II cations, generating two-dimensional layers parallel to the crystallographic (132) plane. The parallel layers are connected by C—H⋯O, C—H⋯N, C—H⋯π and π–π stacking interactions, resulting in a three-dimensional supramolecular architecture.

Keywords: crystal structure; coordination polymer; zinc complex; two-dimensional layer.

CCDC reference: 1564369

1. Chemical context

Over the past few decades, the self-assembly of coordination polymers (CPs) or metal–organic frameworks (MOFs) based on metal ions or clusters and organic ligands has attracted much attention, owing to their intriguing molecular topologies and potential applications. Multidentate ligands derived from 1,2,4-triazole that contain an aromatic core have been used for this purpose, examples being 1,4-bis(1H-1,2,4-triazol-1-ylmethyl)benzene (Wang et al., 2007 ; Ding & Zou, 2010 ; Zhu et al., 2010 ), 1,3-bis(1H-1,2,4-triazol-1-ylmethyl)benzene (Zhang et al., 2012 ; Ge et al., 2008 ; Zhu et al., 2015 ), 1,2-bis(1H-1,2,4-triazol-1-ylmethyl)benzene (Yang et al., 2009 ; Zhao et al., 2017 ; Zhang et al., 2013 ), 1,3,5-tris(1H-1,2,4-triazol-1-ylmethyl)benzene (Li et al., 2012 ; Yin et al., 2009 ; Shi et al., 2011 ), 4,4′-bis[(1H-1,2,4-triazol-1-yl)methyl]-1,1′-biphenyl (Mu et al., 2011 ; Ren et al., 2010 ; Ni et al., 2010 ). Hydrothermal synthesis has been proved to be an effective method for the construction of these new coordination polymers. In this study, a new two-dimensional CP, viz. poly[bis{μ₂-4,4′-bis[(1,2,4-triazol-1-yl)methyl]biphenyl-κ²N⁴:N^4′}bis(nitrato-κO)zinc], [Zn(NO₃)₂(C₁₈H₁₆N₆)₂]_n, was synthesized under hydrothermal conditions by the reaction of Zn(NO₃)₂·6H₂O and 4,4′-bis[(1H-1,2,4-triazol-1-yl)methyl]-1,1′-biphenyl at 313 K for 48 h. We report here its crystal structure and its elemental analysis.

2. Structural commentary

The title complex crystallizes in the triclinic space group P $[\overline{1}]$ ; the asymmetric unit of the structure consists of one Zn^II cation (site symmetry $[\overline 1]$ ), one nitrate anion and one 4,4′-bis[(1H-1,2,4-triazol-1-yl)methyl]-1,1′-biphenyl ligand.

As shown in Fig. 1, each Zn^II cation exhibits a slightly distorted octahedral {ZnN₄O₂} coordination geometry and is coordinated by four N atoms (N1, N4, N1ⁱ and N4ⁱ) from four symmetry-related organic ligands and two O atoms (O3 and O3ⁱ) from two symmetry-related nitrate groups (see Fig. 1 for symmetry code). The Zn—O [2.191 (2) Å] and Zn—N bond lengths [2.124 (3)–2.168 (2) Å] are in agreement with corresponding bond lengths found in previously reported Zn^II coordination polymers. For the title coordination polymer, the Zn^II cation is coordinated by four 4,4′-bis[(1H-1,2,4-triazol-1-yl)methyl]-1,1′-biphenyl ligands and two nitrate anions, and each organic ligand in turn connects two Zn^II cations to generate a two-dimensional layer parallel to the crystallographic (132) plane. The organic ligand adopts a cis,cis substituent conformation. The two distinct Zn⋯Zn distances are 18.397 (3) and 18.964 (3) Å (see Fig. 2). The two benzene rings of the 4,4′-bis[(1H-1,2,4-triazol-1-yl)methyl]-1,1′-biphenyl ligand lie nearly in one plane [dihedral angle = 0.00 (2)°]. The two triazole groups of the 4,4′-bis[(1H-1,2,4-triazol-1-yl)methyl]-1,1′-biphenyl ligand are inclined to the plane of the central biphenyl groups, with dihedral angles of 80.050 (2) (C1/C2/N1/N2/N3) and 85.511 (2)° (C10/C11/N4/N5/N6). Four adjacent Zn^II cations are connected by four linear organic ligands and form a 72-membered macrocyclic ring in the above-mentioned two-dimensional layer (see Fig. 2).

Figure 1
The asymmetric unit of (I)

, showing the atom-numbering scheme. Displacement ellipsoids drawn at the 25% probability level. [Symmetry code: (i) −x, 2 − y, −z.]

Figure 2
The two-dimensional layer parallel to the crystallographic (132) plane.

3. Supramolecular features

Neighbouring layers are linked to each other by by weak interactions (Table 1), including C—H⋯O, C—H⋯N, C—H⋯π [C11—H11⋯Cg1ⁱⁱ = 3.6756 (8) Å and C12—H12⋯Cg2ⁱⁱⁱ = 3.5252 (7) Å; Cg1 and Cg2 are the centroids of the triazole (C1/C2/N1/N2/N3) and phenyl (C4–C9) rings, respectively; symmetry codes: (ii) 2 − x, −y, −z; (iii) 1 − x, 1 − y, −z] contacts and π–π stacking interactions [Cg1⋯Cg1ⁱⁱ = 3.6296 (10) Å]. These interactions, together with the covalent interactions in the infinite two-dimensional polymeric-like layer, make up a three-dimensional supramolecular structure.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3B⋯O1ⁱ	0.97	2.31	3.2728 (7)	170
C3—H3B⋯O1Aⁱ	0.97	2.33	3.2765 (7)	165
C10—H10⋯O2Aⁱⁱ	0.93	2.53	3.0888 (6)	115
C14—H14⋯O2ⁱⁱ	0.93	2.46	3.5454 (7)	158
C15—H15⋯N6ⁱⁱⁱ	0.93	2.58	3.482 (16)	162
Symmetry codes: (i) x-1, y+1, z; (ii) -x+1, -y, -z; (iii) x-1, y, z.

4. Database survey

A search in the Cambridge Structural Database (Groom et al., 2016 ) for zinc and the 4,4′-bis[(1H-1,2,4-triazol-1-yl)methyl]-1,1′-biphenyl moiety gave eight hits. Seven of them are constructed by 4,4′-bis[(1H-1,2,4-triazol-1-yl)methyl]-1,1′-biphenyl units and different carboxylate ligands. One example is a chain structure based on Zn and 4,4′-bis[(1H-1,2,4-triazol-1-yl)methyl]-1,1′-biphenyl (PUQWAA; Ni et al., 2010).

5. Synthesis and crystallization

Zn(NO₃)₂·6H₂O (0.1 mmol), 4,4′-bis[(1H-1,2,4-triazol-1-yl)methyl]-1,1′-biphenyl (0.1 mmol) and water (6 ml) were mixed and placed in a thick Pyrex tube, which was sealed and heated to 413 K for 72 h. After cooling to room temperature, colourless block-shaped crystals (53% yield, based on Zn) suitable for X-ray analysis were obtained. Elemental analysis calculated for C₃₆H₃₂N₁₄O₆Zn: C 52.59, H 3.92, N 23.85%; found: C 52.23, H 3.74, N 23.49%.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms bonded to C atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å with U_iso(H) = 1.2U_eq(C) for other H atoms. Atoms O1 and O2 of the nitrate group are disordered over two orientations, with occupancies of 0.511 (11) and 0.489 (11), and were refined through the use of SADI, RIGU and SIMU commands.

Table 2
Experimental details

Crystal data
Chemical formula	[Zn(NO₃)₂(C₁₈H₁₆N₆)₂]
M_r	822.12
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	7.3257 (15), 9.0188 (18), 15.578 (3)
α, β, γ (°)	81.70 (3), 77.64 (3), 68.90 (3)
V (Å³)	935.4 (4)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.72
Crystal size (mm)	0.24 × 0.22 × 0.20

Data collection
Diffractometer	Bruker APEXII Quazar
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.84, 0.86
No. of measured, independent and observed [I > 2σ(I)] reflections	7292, 3271, 2589
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.143, 1.05
No. of reflections	3271
No. of parameters	278
No. of restraints	85
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.54
Computer programs: APEX3 (Bruker, 2016 ), SAINT-Plus (Bruker, 2016), SHELXT (Sheldrick, 2008 ), SHELXTL-Plus (Sheldrick, 2008) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1564369

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989017012452/vn2130sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017012452/vn2130Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989017012452/vn2130Isup3.mol

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT-Plus (Bruker, 2016); data reduction: SAINT-Plus (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2008); program(s) used to refine structure: SHELXTL-Plus (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Poly[bis{µ₂-4,4'-bis[(1,2,4-triazol-1-yl)methyl]biphenyl-κ²N⁴:N^4'}bis(nitrato-κO)zinc(II)] top

Crystal data top

[Zn(NO₃)₂(C₁₈H₁₆N₆)₂]	Z = 1
M_r = 822.12	F(000) = 424
Triclinic, P1	D_x = 1.459 Mg m⁻³
a = 7.3257 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.0188 (18) Å	Cell parameters from 7292 reflections
c = 15.578 (3) Å	θ = 1.6–25.1°
α = 81.70 (3)°	µ = 0.72 mm⁻¹
β = 77.64 (3)°	T = 293 K
γ = 68.90 (3)°	Block, colorless
V = 935.4 (4) Å³	0.24 × 0.22 × 0.2 mm

Data collection top

Bruker APEXII Quazar diffractometer	3271 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	2589 reflections with I > 2σ(I)
Mirror optics monochromator	R_int = 0.042
Detector resolution: 7.9 pixels mm^-1	θ_max = 25.0°, θ_min = 3.0°
0.5° ω and 0.5° φ scans	h = −8→8
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −10→9
T_min = 0.84, T_max = 0.86	l = −18→18
7292 measured reflections

Refinement top

Refinement on F²	85 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.143	w = 1/[σ²(F_o²) + (0.079P)² + 0.2956P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3271 reflections	Δρ_max = 0.34 e Å⁻³
278 parameters	Δρ_min = −0.54 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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.000000	1.000000	0.000000	0.0406 (2)
O3	0.1631 (4)	1.1607 (3)	0.00189 (17)	0.0574 (7)
N1	0.2322 (4)	0.8123 (3)	0.05733 (18)	0.0441 (7)
N2	0.4790 (5)	0.6937 (4)	0.1274 (2)	0.0482 (7)
N3	0.4061 (6)	0.5766 (4)	0.1198 (2)	0.0602 (9)
N4	0.1701 (4)	0.9540 (4)	−0.12813 (18)	0.0457 (7)
N5	0.3961 (5)	0.8456 (4)	−0.23645 (19)	0.0466 (7)
N6	0.2787 (6)	0.9865 (5)	−0.2713 (2)	0.0729 (11)
N7	0.1398 (5)	1.2530 (4)	0.0601 (2)	0.0570 (8)
C1	0.2590 (6)	0.6550 (5)	0.0771 (3)	0.0554 (10)
H1	0.179295	0.606514	0.061538	0.066*
C2	0.3743 (6)	0.8301 (4)	0.0904 (2)	0.0474 (8)
H2	0.397217	0.925660	0.087958	0.057*
C3	0.6466 (6)	0.6585 (5)	0.1731 (3)	0.0601 (10)
H3A	0.687840	0.751186	0.165279	0.072*
H3B	0.757323	0.571442	0.146296	0.072*
C4	0.5997 (6)	0.6146 (4)	0.2700 (3)	0.0513 (9)
C5	0.7455 (7)	0.5120 (7)	0.3132 (4)	0.0902 (17)
H5	0.873179	0.468413	0.281685	0.108*
C6	0.7082 (8)	0.4711 (8)	0.4028 (4)	0.0927 (17)
H6	0.812884	0.404978	0.430318	0.111*
C7	0.5224 (6)	0.5251 (4)	0.4518 (3)	0.0532 (9)
C8	0.3756 (8)	0.6273 (6)	0.4079 (3)	0.0813 (16)
H8	0.246945	0.667746	0.439147	0.098*
C9	0.4126 (8)	0.6717 (6)	0.3195 (3)	0.0823 (16)
H9	0.309014	0.741721	0.292602	0.099*
C10	0.3284 (6)	0.8298 (5)	−0.1520 (2)	0.0515 (9)
H10	0.384162	0.743198	−0.114162	0.062*
C11	0.1465 (6)	1.0486 (5)	−0.2035 (2)	0.0588 (10)
H11	0.046686	1.147437	−0.206804	0.071*
C12	0.5625 (7)	0.7311 (5)	−0.2909 (3)	0.0658 (13)
H12A	0.509806	0.678916	−0.324861	0.079*
H12B	0.641231	0.649898	−0.252615	0.079*
C13	0.6941 (6)	0.8103 (4)	−0.3527 (3)	0.0530 (10)
C14	0.8175 (7)	0.8650 (6)	−0.3228 (3)	0.0722 (13)
H14	0.821652	0.853057	−0.262825	0.087*
C15	0.9375 (7)	0.9384 (6)	−0.3803 (3)	0.0684 (13)
H15	1.021917	0.973475	−0.358088	0.082*
C16	0.9348 (5)	0.9608 (4)	−0.4696 (2)	0.0431 (8)
C17	0.8101 (7)	0.9040 (6)	−0.4990 (3)	0.0738 (14)
H17	0.804965	0.915631	−0.558860	0.089*
C18	0.6915 (8)	0.8296 (6)	−0.4409 (3)	0.0750 (14)
H18	0.608813	0.792084	−0.462688	0.090*
O1	−0.0075 (14)	1.3759 (11)	0.0613 (8)	0.0890 (19)	0.500 (12)
O2	0.2754 (14)	1.2075 (12)	0.1048 (6)	0.0792 (17)	0.500 (12)
O1A	−0.0249 (12)	1.3242 (11)	0.1028 (7)	0.0807 (18)	0.500 (12)
O2A	0.2775 (13)	1.2743 (14)	0.0828 (7)	0.0812 (17)	0.500 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0365 (3)	0.0492 (4)	0.0287 (3)	−0.0098 (2)	−0.0025 (2)	0.0033 (2)
O3	0.0658 (17)	0.0635 (16)	0.0492 (15)	−0.0325 (14)	−0.0020 (13)	−0.0084 (13)
N1	0.0444 (16)	0.0499 (17)	0.0331 (15)	−0.0123 (13)	−0.0074 (13)	0.0027 (13)
N2	0.0514 (18)	0.0509 (17)	0.0384 (16)	−0.0136 (14)	−0.0123 (14)	0.0052 (13)
N3	0.077 (2)	0.0481 (18)	0.060 (2)	−0.0216 (17)	−0.0251 (19)	0.0036 (16)
N4	0.0463 (17)	0.0559 (18)	0.0310 (15)	−0.0158 (14)	−0.0048 (13)	0.0013 (13)
N5	0.0506 (17)	0.0545 (17)	0.0347 (16)	−0.0245 (15)	0.0054 (14)	−0.0049 (14)
N6	0.072 (3)	0.088 (3)	0.042 (2)	−0.019 (2)	0.0022 (19)	0.0074 (19)
N7	0.0616 (17)	0.0610 (18)	0.0580 (19)	−0.0299 (14)	−0.0085 (15)	−0.0136 (15)
C1	0.065 (3)	0.052 (2)	0.052 (2)	−0.0185 (19)	−0.022 (2)	−0.0003 (18)
C2	0.052 (2)	0.0469 (19)	0.0385 (19)	−0.0165 (17)	−0.0040 (17)	0.0047 (15)
C3	0.052 (2)	0.071 (3)	0.057 (3)	−0.020 (2)	−0.020 (2)	0.009 (2)
C4	0.059 (2)	0.048 (2)	0.046 (2)	−0.0146 (17)	−0.0201 (18)	0.0056 (17)
C5	0.044 (3)	0.133 (5)	0.070 (3)	−0.017 (3)	−0.018 (2)	0.044 (3)
C6	0.057 (3)	0.133 (5)	0.070 (3)	−0.021 (3)	−0.028 (3)	0.047 (3)
C7	0.071 (3)	0.043 (2)	0.047 (2)	−0.0121 (18)	−0.027 (2)	0.0009 (16)
C8	0.083 (3)	0.077 (3)	0.041 (2)	0.025 (2)	−0.010 (2)	−0.006 (2)
C9	0.091 (4)	0.075 (3)	0.045 (2)	0.021 (3)	−0.027 (2)	0.002 (2)
C10	0.052 (2)	0.055 (2)	0.0356 (19)	−0.0112 (17)	0.0015 (17)	0.0035 (16)
C11	0.049 (2)	0.068 (2)	0.036 (2)	−0.0013 (19)	0.0002 (17)	0.0047 (18)
C12	0.079 (3)	0.055 (2)	0.057 (3)	−0.033 (2)	0.028 (2)	−0.017 (2)
C13	0.058 (2)	0.047 (2)	0.045 (2)	−0.0194 (18)	0.0153 (18)	−0.0088 (17)
C14	0.087 (3)	0.100 (3)	0.034 (2)	−0.048 (3)	0.002 (2)	0.000 (2)
C15	0.075 (3)	0.108 (4)	0.039 (2)	−0.054 (3)	−0.004 (2)	−0.002 (2)
C16	0.0386 (18)	0.0427 (18)	0.0388 (18)	−0.0073 (14)	0.0024 (15)	−0.0055 (15)
C17	0.087 (3)	0.114 (4)	0.038 (2)	−0.060 (3)	−0.007 (2)	0.003 (2)
C18	0.085 (3)	0.111 (4)	0.051 (3)	−0.066 (3)	−0.002 (2)	−0.005 (2)
O1	0.091 (3)	0.077 (3)	0.080 (4)	−0.006 (3)	−0.008 (3)	−0.016 (3)
O2	0.094 (3)	0.080 (4)	0.075 (3)	−0.035 (3)	−0.032 (3)	−0.003 (3)
O1A	0.080 (3)	0.075 (3)	0.074 (4)	−0.020 (3)	0.009 (3)	−0.016 (3)
O2A	0.085 (3)	0.088 (4)	0.087 (4)	−0.041 (3)	−0.030 (3)	−0.008 (3)

Geometric parameters (Å, º) top

Zn1—O3	2.191 (2)	C4—C5	1.367 (6)
Zn1—O3ⁱ	2.191 (2)	C4—C9	1.376 (6)
Zn1—N1ⁱ	2.167 (3)	C5—H5	0.9300
Zn1—N1	2.167 (3)	C5—C6	1.385 (7)
Zn1—N4ⁱ	2.124 (3)	C6—H6	0.9300
Zn1—N4	2.124 (3)	C6—C7	1.363 (7)
O3—N7	1.263 (4)	C7—C7ⁱⁱ	1.505 (8)
N1—C1	1.359 (5)	C7—C8	1.376 (6)
N1—C2	1.322 (5)	C8—H8	0.9300
N2—N3	1.372 (4)	C8—C9	1.375 (7)
N2—C2	1.318 (5)	C9—H9	0.9300
N2—C3	1.465 (5)	C10—H10	0.9300
N3—C1	1.314 (5)	C11—H11	0.9300
N4—C10	1.318 (5)	C12—H12A	0.9700
N4—C11	1.353 (5)	C12—H12B	0.9700
N5—N6	1.365 (5)	C12—C13	1.506 (5)
N5—C10	1.310 (5)	C13—C14	1.359 (6)
N5—C12	1.475 (5)	C13—C18	1.364 (6)
N6—C11	1.307 (5)	C14—H14	0.9300
N7—O1	1.237 (8)	C14—C15	1.387 (6)
N7—O2	1.249 (8)	C15—H15	0.9300
N7—O1A	1.237 (7)	C15—C16	1.381 (5)
N7—O2A	1.221 (8)	C16—C16ⁱⁱⁱ	1.487 (7)
C1—H1	0.9300	C16—C17	1.375 (5)
C2—H2	0.9300	C17—H17	0.9300
C3—H3A	0.9700	C17—C18	1.390 (6)
C3—H3B	0.9700	C18—H18	0.9300
C3—C4	1.501 (6)

O3—Zn1—O3ⁱ	180.0	C5—C4—C3	120.3 (4)
N1—Zn1—O3ⁱ	92.22 (11)	C5—C4—C9	116.5 (4)
N1ⁱ—Zn1—O3	92.22 (11)	C9—C4—C3	123.2 (4)
N1ⁱ—Zn1—O3ⁱ	87.78 (11)	C4—C5—H5	119.1
N1—Zn1—O3	87.78 (11)	C4—C5—C6	121.8 (5)
N1ⁱ—Zn1—N1	180.0	C6—C5—H5	119.1
N4—Zn1—O3ⁱ	94.65 (10)	C5—C6—H6	119.1
N4ⁱ—Zn1—O3	94.65 (10)	C7—C6—C5	121.9 (5)
N4—Zn1—O3	85.35 (10)	C7—C6—H6	119.1
N4ⁱ—Zn1—O3ⁱ	85.35 (10)	C6—C7—C7ⁱⁱ	122.4 (5)
N4ⁱ—Zn1—N1ⁱ	90.36 (12)	C6—C7—C8	116.2 (4)
N4ⁱ—Zn1—N1	89.64 (12)	C8—C7—C7ⁱⁱ	121.4 (5)
N4—Zn1—N1	90.36 (12)	C7—C8—H8	118.9
N4—Zn1—N1ⁱ	89.64 (12)	C9—C8—C7	122.2 (4)
N4ⁱ—Zn1—N4	180.0	C9—C8—H8	118.9
N7—O3—Zn1	128.5 (2)	C4—C9—H9	119.3
C1—N1—Zn1	130.5 (3)	C8—C9—C4	121.4 (4)
C2—N1—Zn1	126.5 (2)	C8—C9—H9	119.3
C2—N1—C1	102.7 (3)	N4—C10—H10	124.8
N3—N2—C3	120.7 (3)	N5—C10—N4	110.5 (4)
C2—N2—N3	109.9 (3)	N5—C10—H10	124.8
C2—N2—C3	129.4 (3)	N4—C11—H11	123.6
C1—N3—N2	102.0 (3)	N6—C11—N4	112.9 (4)
C10—N4—Zn1	128.1 (3)	N6—C11—H11	123.6
C10—N4—C11	103.9 (3)	N5—C12—H12A	109.2
C11—N4—Zn1	128.0 (3)	N5—C12—H12B	109.2
N6—N5—C12	122.6 (3)	N5—C12—C13	112.2 (3)
C10—N5—N6	109.0 (3)	H12A—C12—H12B	107.9
C10—N5—C12	128.3 (4)	C13—C12—H12A	109.2
C11—N6—N5	103.8 (3)	C13—C12—H12B	109.2
O1—N7—O3	115.4 (6)	C14—C13—C12	121.5 (4)
O1—N7—O2	130.6 (7)	C14—C13—C18	118.1 (4)
O2—N7—O3	114.0 (5)	C18—C13—C12	120.4 (4)
O1A—N7—O3	122.8 (5)	C13—C14—H14	119.5
O2A—N7—O3	123.5 (6)	C13—C14—C15	121.0 (4)
O2A—N7—O1A	113.6 (7)	C15—C14—H14	119.5
N1—C1—H1	122.6	C14—C15—H15	119.2
N3—C1—N1	114.8 (3)	C16—C15—C14	121.7 (4)
N3—C1—H1	122.6	C16—C15—H15	119.2
N1—C2—H2	124.7	C15—C16—C16ⁱⁱⁱ	120.9 (4)
N2—C2—N1	110.7 (3)	C17—C16—C15	116.7 (3)
N2—C2—H2	124.7	C17—C16—C16ⁱⁱⁱ	122.4 (4)
N2—C3—H3A	108.9	C16—C17—H17	119.4
N2—C3—H3B	108.9	C16—C17—C18	121.2 (4)
N2—C3—C4	113.5 (3)	C18—C17—H17	119.4
H3A—C3—H3B	107.7	C13—C18—C17	121.4 (4)
C4—C3—H3A	108.9	C13—C18—H18	119.3
C4—C3—H3B	108.9	C17—C18—H18	119.3

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···O1^iv	0.97	2.31	3.2728 (7)	170
C3—H3B···O1A^iv	0.97	2.33	3.2765 (7)	165
C10—H10···O2A^v	0.93	2.53	3.0888 (6)	115
C14—H14···O2^v	0.93	2.46	3.5454 (7)	158
C15—H15···N6^vi	0.93	2.58	3.482 (16)	162

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

Funding information

Funding for this research was provided by: Science and Technology Research Projects of Jilin Province Department of Education (JJKH20170186KJ) .

References

Bruker (2016). APEX3. Bruker AXS Inc., Madison, Wisconsin, USA.
Ding, B. & Zou, H.-A. (2010). Acta Cryst. E66, m932. Web of Science CSD CrossRef IUCr Journals
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals
Ge, H., Liu, K., Yang, Y., Li, B. & Zhang, Y. (2008). Inorg. Chem. Commun. 11, 260–264. Web of Science CSD CrossRef CAS
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef CAS IUCr Journals
Li, Q.-X., Shi, X.-J. & Chen, L.-C. (2012). Acta Cryst. E68, m1299. CSD CrossRef IUCr Journals
Mu, Y., Song, Y., Wang, C., Hou, H. & Fan, Y. (2011). Inorg. Chim. Acta, 365, 167–176. Web of Science CSD CrossRef CAS
Ni, T., Shao, M., Zhu, S., Zhao, Y., Xing, F. & Li, M. (2010). Cryst. Growth Des. 10, 943–951. Web of Science CSD CrossRef CAS
Ren, C., Liu, P., Wang, Y.-Y., Huang, W.-H. & Shi, Q.-Z. (2010). Eur. J. Inorg. Chem. pp. 5545–5555. Web of Science CSD CrossRef
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals
Shi, X., Li, Q., Zhang, Y., Chang, X. & Hou, H. (2011). J. Coord. Chem. 64, 3918–3927. Web of Science CSD CrossRef CAS
Wang, W.-B., Wang, L.-Y., Li, B.-L. & Zhang, Y. (2007). Acta Cryst. E63, m2416–m2417. Web of Science CSD CrossRef IUCr Journals
Yang, Y., Feng, Y.-F., Liang, N., Li, B.-L. & Zhang, Y. (2009). J. Coord. Chem. 62, 3819–3827. Web of Science CSD CrossRef CAS
Yin, X.-J., Zhou, X.-H., Gu, Z.-G., Zuo, J.-L. & You, X.-Z. (2009). Inorg. Chem. Commun. 12, 548–551. Web of Science CSD CrossRef CAS
Zhang, Z., Ma, J.-F., Liu, Y.-Y., Kan, W.-Q. & Yang, J. (2013). CrystEngComm, 15, 2009–2018. Web of Science CSD CrossRef CAS
Zhang, H.-K., Wang, X., Wang, S. & Wang, X.-D. (2012). Acta Cryst. E68, m856. CSD CrossRef IUCr Journals
Zhao, S., Zheng, T.-R., Zhang, Y.-Q., Lv, X.-X., Li, B.-L. & Zhang, Y. (2017). Polyhedron, 121, 61–69. Web of Science CSD CrossRef CAS
Zhu, X., Guo, Y. & Zou, Y.-L. (2010). Acta Cryst. E66, m85. Web of Science CSD CrossRef IUCr Journals
Zhu, X., Yang, Y., Jiang, N., Li, B., Zhou, D., Fu, H. & Wang, N. (2015). Z. Anorg. Allg. Chem. 641, 699–703. Web of Science CSD CrossRef CAS

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