Polymeric poly[[decaaquabis(μ6-1,8-disulfonato-9H-carbazole-3,6-dicarboxylato)di-μ3-hydroxy-pentazinc] decahydrate]

Yu, J.; Wang, D.-C.; Wang, B.

doi:10.1107/S2414314619006679

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 5| May 2019| x190667

https://doi.org/10.1107/S2414314619006679

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Polymeric poly[[decaaquabis(μ₆-1,8-disulfonato-9H-carbazole-3,6-dicarboxylato)di-μ₃-hydroxy-pentazinc] decahydrate]

Jiamei Yu,^a De-Chao Wang ^a and Bin Wang ^b ^*

^aCollege of Materials Science and Engineering, Beijing University of Technology, No. 100, Pingleyuan, Chaoyang District, Beijing, People's Republic of China, and ^bBeijing Key Laboratory for Green Catalysis and Separation, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124, People's Republic of China
^*Correspondence e-mail: wangbin10304@gmail.com

Edited by E. R. T. Tiekink, Sunway University, Malaysia (Received 13 March 2019; accepted 9 May 2019; online 14 May 2019)

The asymmetric unit of the title MOF, [Zn₅(C₁₄H₅NO₁₀S₂)₂(OH)₂(H₂O)₁₀]_n comprises three Zn^II atoms, one of which is located on a centre of inversion, a tetra-negative carboxylate ligand, one μ₃-hydroxide and five water molecules, each of which is coordinated. The Zn^II atom, lying on a centre of inversion, is coordinated by trans sulfoxide-O atoms and four water molecules in an octahedral geometry. Another Zn^II atom is coordinated by two carboxylate-O atoms, one hydroxy-O, one sulfoxide-O and a water-O atom to define a distorted trigonal–bipyramidal geometry; a close Zn⋯O(carboxylate) interaction derived from an asymmetrically coordinating ligand (Zn—O = 1.95 and 3.07 Å) suggests a 5 + 1 coordination geometry. The third Zn^II atom is coordinated in an octahedral fashion by two hydroxy-O atoms, one carboxylate-O, one sulfoxide-O and two water-O atoms, the latter being mutually cis. In all, the carboxylate ligand binds six Zn^II ions leading to a three-dimensional architecture. In the crystal, all acidic donors form hydrogen bonds to oxygen acceptors to contribute to the stability of the three-dimensional architecture.

Keywords: crystal structure; metal–organic framework; Zn^II; hydrogen bonding.

CCDC reference: 1915135

Structure description

In recent years, metal–organic frameworks (MOF's) have attracted much attention because of their fascinating architectures as well as their great potential applications in the areas of gas adsorption (Suh et al., 2012 ), gas separation (Li et al., 2012 ), heterogeneous catalysis (Liu et al., 2014 ), sensing (Kreno et al., 2012 ), etc. In this context, the synthesis and structure of a new Zn^II-based MOF, [Zn₅(μ₃-OH)₂(1,8-disulfo-9H-carbazole-3,6-dicarboxylate)₂(H₂O)₁₀]_n, (I), is reported herein. This MOF was constructed by the solvothermal reaction between 1,8-disulfo-9H-carbazole-3,6-dicarboxylic acid and Zn(NO₃)₂ in the presence of HBF₄, as a competing reagent, in dimethylformamide (DMF).

Single-crystal X-ray diffraction reveals that (I) crystallizes in the triclinic space group P $[\overline{1}]$ . The asymmetric unit, Fig. 1, comprises comprises three Zn^II atoms, one of which (Zn3) is located on a centre of inversion, a tetra-negative carboxylate ligand, one μ₃-hydroxide and five water molecules; each water molecule is coordinated. The hydroxide bridges three Zn atoms. A pair of centrosymmetrically related Zn2 atoms is connected by two hydroxide bridges with each hydroxide also bridging a Zn1 atom. Additional links between the Zn1 and Zn2 atoms are provided by bidentate bridging carboxylate ligands and sulfoxide-oxygen atoms. The coordination geometry for the Zn1 atom is completed by oxygen atoms derived from an asymmetrically coordinating (Zn1—O3, O4 = 1.95 and 3.07 Å) carboxylate residue and a water molecule. If the weak interaction were ignored, the Zn1 atom would be considered five-coordinate, distorted trigonal–bipyramidal with the sulfoxide-oxygen and the water-oxygen atoms occupying axial positions. The distorted octahedral coordination geometry for the Zn2 atom is completed by two water molecules which occupy mutually cis positions. A distinct distorted octahedral geometry is found for the Zn3 atom. This atom lies on a centre of inversion and is coordinated by two sulfoxide-oxygen atoms and four water molecules; from symmetry the sulfoxide-oxygen atoms are trans.

Figure 1
A view of the asymmetric unit of (I), showing the atom numbering, with displacement ellipsoids drawn at the 50% probability level.

The carboxylate ligand binds six Zn^II ions with one carboxylate residue (O1, O2) bridging two Zn^II atoms (Zn1 and Zn2) and the other (O15, O16) being connected to a single Zn^II atom (Zn2). One of the sulfoxide-oxygen atoms (O8) connects to a single Zn^II centre (Zn3) while the other (O14) bridges two Zn^II atoms (Zn1 and Zn2). In this way a three-dimensional architecture is generated, Fig. 2.

Figure 2
A view of the three-dimensional structure of (I); H atoms have been omitted for reasons of clarity.

As anticipated from the chemical composition, there are extensive hydrogen-bonding interactions in the crystal, which contribute to the stability of the three-dimensional architecture, Table 1. All acidic donors form hydrogen bonds to oxygen acceptors.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O13ⁱ	1.00	1.83	2.804 (5)	163
O4—H4A⋯O12ⁱ	0.87	1.86	2.632 (4)	147
O4—H4B⋯O16ⁱⁱ	0.87	1.85	2.608 (3)	145
O5—H5A⋯O12ⁱⁱⁱ	0.97	1.81	2.736 (3)	160
O5—H5B⋯O7^iv	0.96	2.09	2.818 (4)	131
O6—H6A⋯O13ⁱ	0.97	2.09	2.976 (5)	151
O6—H6B⋯O7^v	0.97	2.24	3.156 (7)	157
O10—H10A⋯O7^vi	0.96	2.20	2.941 (5)	133
O10—H10B⋯O16ⁱ	0.96	1.72	2.666 (5)	166
O11—H11A⋯O4ⁱ	0.87	1.96	2.837 (3)	179
O11—H11B⋯O9^vi	0.87	1.89	2.757 (5)	171
N1—H1⋯O9	0.88	2.46	2.962 (4)	117
N1—H1⋯O12	0.88	2.40	2.908	117
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y+2, -z+1; (iii) -x+2, -y+1, -z+1; (iv) x, y+1, z; (v) -x+2, -y+1, -z; (vi) x-1, y, z.

Synthesis and crystallization

1,8-Disulfo-9H-carbazole-3,6-dicarboxylic acid (10 mg), Zn(NO₃)₂ (20 mg), and HBF₄ (4 drops) were ultrasonically dissolved in DMF (2 ml) in a 4 ml Pyrex vial and sealed. The reaction system was then heated at 80°C for 24 h in an oven. Colourless crystals of the title complex suitable for single-crystal X-ray analysis were obtained from the reaction vessel.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[Zn₅(C₁₄H₅NO₁₀S₂)₂(OH)₂(H₂O)₁₀]
M_r	1363.64
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	289
a, b, c (Å)	7.3573 (3), 11.2345 (5), 12.9215 (5)
α, β, γ (°)	74.215 (4), 78.085 (4), 85.178 (4)
V (Å³)	1005.17 (8)
Z	1
Radiation type	Cu Kα
μ (mm⁻¹)	6.36
Crystal size (mm)	0.10 × 0.08 × 0.04

Data collection
Diffractometer	Rigaku Oxford Diffraction SuperNova, Dual, Cu at home/near, AtlasS2
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2017 $[Rigaku OD (2017). CrysAlis PRO. Rigaku Oxford Diffraction, Oxford, England.]$ )
T_min, T_max	0.674, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6682, 3966, 3348
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.129, 1.08
No. of reflections	3966
No. of parameters	303
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.73, −0.82
Computer programs: CrysAlis PRO (Rigaku OD, 2017 $[Rigaku OD (2017). CrysAlis PRO. Rigaku Oxford Diffraction, Oxford, England.]$ ), SHELXS2013 (Sheldrick, 2008 ), SHELXL2013 (Gruene et al., 2014 ) and DIAMOND (Brandenburg, 2006 ), publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1915135

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619006679/tk4056sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619006679/tk4056Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314619006679/tk4056Isup3.cdx

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2017); cell refinement: CrysAlis PRO (Rigaku OD, 2017); data reduction: CrysAlis PRO (Rigaku OD, 2017); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Gruene et al., 2014); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Poly[[decaaquabis(µ₆-1,8-disulfonato-9H-carbazole-3,6-dicarboxylato)di-µ₃-hydroxy-pentazinc] decahydrate] top

Crystal data top

[Zn₅(C₁₄H₅NO₁₀S₂)₂(OH)₂(H₂O)₁₀]	Z = 1
M_r = 1363.64	F(000) = 684
Triclinic, P1	D_x = 2.253 Mg m⁻³
a = 7.3573 (3) Å	Cu Kα radiation, λ = 1.54184 Å
b = 11.2345 (5) Å	Cell parameters from 3065 reflections
c = 12.9215 (5) Å	θ = 4.1–74.3°
α = 74.215 (4)°	µ = 6.36 mm⁻¹
β = 78.085 (4)°	T = 289 K
γ = 85.178 (4)°	Prism, colourless
V = 1005.17 (8) Å³	0.10 × 0.08 × 0.04 mm

Data collection top

Rigaku Oxford Diffraction SuperNova, Dual, Cu at home/near, AtlasS2 diffractometer	3966 independent reflections
Radiation source: micro-focus sealed X-ray tube	3348 reflections with I > 2σ(I)
Detector resolution: 10.3376 pixels mm^-1	R_int = 0.037
ω scans	θ_max = 74.6°, θ_min = 3.6°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2017)	h = −9→5
T_min = 0.674, T_max = 1.000	k = −13→13
6682 measured reflections	l = −16→13

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.129	w = 1/[σ²(F_o²) + (0.0715P)² + 0.7146P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
3966 reflections	Δρ_max = 0.73 e Å⁻³
303 parameters	Δρ_min = −0.82 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. The H atoms bound to the O5, O6 and O10 atoms were located from difference Fourier maps and had O—H bond lengths in the vicinity of 0.96 Å, Table 1. The H atoms bound to the O4 and O11 atoms were included in their idealized positions at 0.87 Å; U_iso(water-H) = 1.5U_eq(water-O). The hydroxide-H (1.00 Å) and amine-H (0.88 Å) atoms were included in their idealized positions with U_iso(hydroxide-H) = 1.2U_eq(hydroxide-O) and U_iso(amine-H) = 1.2U_eq(amine-N), respectively.

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

	x	y	z	U_iso*/U_eq
Zn1	1.06687 (8)	0.72625 (5)	0.00084 (4)	0.02631 (17)
Zn2	0.98180 (8)	0.93578 (5)	0.12468 (4)	0.02273 (16)
Zn3	0.5000	0.0000	0.5000	0.0297 (2)
S1	0.88904 (14)	0.18599 (9)	0.43688 (8)	0.0250 (2)
S2	0.56934 (13)	0.19518 (9)	0.89732 (8)	0.0214 (2)
O1	0.9726 (4)	0.6195 (3)	0.1462 (2)	0.0303 (7)
O2	0.8944 (4)	0.7689 (3)	0.2326 (2)	0.0291 (7)
O3	0.9412 (4)	0.8915 (3)	−0.0134 (2)	0.0225 (6)
H3	0.8051	0.8818	−0.0069	0.027*
O4	0.7293 (3)	1.0051 (3)	0.1876 (2)	0.0276 (6)
H4A	0.6418	0.9868	0.1588	0.041*
H4B	0.7277	1.0855	0.1679	0.041*
O5	1.1075 (3)	0.9847 (3)	0.2343 (2)	0.0385 (8)
H5A	1.2378	0.9611	0.2212	0.058*
H5B	1.0955	1.0728	0.2237	0.058*
O6	0.8903 (6)	0.6684 (6)	−0.0892 (4)	0.0745 (16)
H6A	0.7701	0.7101	−0.0773	0.112*
H6B	0.9440	0.6955	−0.1668	0.112*
O7	1.0117 (5)	0.1789 (3)	0.3367 (3)	0.0460 (9)
O8	0.7056 (5)	0.1419 (3)	0.4474 (3)	0.0455 (9)
O9	0.9671 (6)	0.1283 (3)	0.5341 (3)	0.0492 (10)
O10	0.3873 (5)	0.0789 (3)	0.3613 (3)	0.0379 (8)
H10A	0.2901	0.1378	0.3779	0.057*
H10B	0.4828	0.1215	0.3034	0.057*
O11	0.31752 (19)	0.1047 (2)	0.58355 (17)	0.0359 (8)
H11A	0.3019	0.0719	0.6543	0.054*
H11B	0.2063	0.1035	0.5700	0.054*
O12	0.54981 (19)	0.11779 (12)	0.82671 (10)	0.0304 (7)
O13	0.4211 (2)	0.18488 (12)	0.99171 (10)	0.0323 (7)
O14	0.75275 (18)	0.17111 (12)	0.92851 (10)	0.0253 (6)
O15	0.26713 (18)	0.62313 (11)	0.94248 (11)	0.0356 (8)
O16	0.3823 (2)	0.77209 (11)	0.79901 (12)	0.0471 (10)
N1	0.7207 (2)	0.30507 (11)	0.63530 (12)	0.0236 (7)
H1	0.7368	0.2242	0.6561	0.028*
C1	0.9111 (5)	0.6577 (4)	0.2306 (3)	0.0218 (8)
C2	0.8569 (5)	0.5611 (3)	0.3364 (3)	0.0201 (8)
C3	0.8957 (5)	0.4361 (4)	0.3383 (3)	0.0209 (8)
H3A	0.9520	0.4147	0.2724	0.025*
C4	0.8535 (6)	0.3441 (3)	0.4338 (3)	0.0205 (8)
C5	0.7718 (5)	0.3775 (3)	0.5303 (3)	0.0201 (8)
C6	0.7261 (5)	0.5026 (3)	0.5283 (3)	0.0186 (7)
C7	0.7709 (6)	0.5942 (4)	0.4308 (3)	0.0233 (8)
H7	0.7426	0.6787	0.4290	0.028*
C8	0.6395 (6)	0.5024 (4)	0.6396 (3)	0.0210 (8)
C9	0.6405 (5)	0.3788 (4)	0.7030 (3)	0.0197 (8)
C10	0.5641 (5)	0.3480 (3)	0.8149 (3)	0.0194 (7)
C11	0.4823 (6)	0.4419 (4)	0.8617 (3)	0.0232 (8)
H11	0.4295	0.4227	0.9377	0.028*
C12	0.4767 (6)	0.5649 (4)	0.7983 (3)	0.0245 (8)
C13	0.5567 (6)	0.5963 (4)	0.6876 (3)	0.0240 (8)
H13	0.5553	0.6799	0.6453	0.029*
C14	0.3707 (6)	0.6619 (4)	0.8495 (3)	0.0265 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0359 (3)	0.0189 (3)	0.0183 (3)	0.0028 (2)	0.0066 (2)	−0.0050 (2)
Zn2	0.0299 (3)	0.0173 (3)	0.0177 (3)	0.0015 (2)	0.0006 (2)	−0.0036 (2)
Zn3	0.0381 (5)	0.0205 (4)	0.0279 (4)	−0.0003 (3)	0.0019 (3)	−0.0084 (3)
S1	0.0335 (5)	0.0142 (4)	0.0261 (5)	0.0018 (4)	0.0006 (4)	−0.0088 (4)
S2	0.0232 (5)	0.0173 (4)	0.0198 (5)	−0.0003 (3)	−0.0010 (4)	−0.0006 (3)
O1	0.0453 (18)	0.0229 (15)	0.0173 (14)	−0.0038 (13)	0.0070 (12)	−0.0053 (12)
O2	0.0465 (18)	0.0125 (13)	0.0203 (14)	0.0000 (12)	0.0062 (13)	−0.0004 (11)
O3	0.0238 (13)	0.0195 (13)	0.0212 (14)	0.0006 (11)	−0.0008 (11)	−0.0032 (11)
O4	0.0287 (15)	0.0199 (14)	0.0324 (16)	0.0031 (11)	0.0003 (12)	−0.0094 (12)
O5	0.046 (2)	0.0373 (18)	0.0413 (19)	0.0059 (15)	−0.0161 (16)	−0.0212 (16)
O6	0.049 (2)	0.128 (5)	0.068 (3)	−0.002 (3)	−0.006 (2)	−0.067 (3)
O7	0.061 (2)	0.0268 (17)	0.042 (2)	−0.0013 (16)	0.0201 (17)	−0.0166 (15)
O8	0.0417 (19)	0.0243 (17)	0.067 (3)	−0.0139 (14)	0.0021 (18)	−0.0107 (17)
O9	0.073 (3)	0.0278 (18)	0.050 (2)	0.0151 (18)	−0.024 (2)	−0.0111 (16)
O10	0.0384 (18)	0.0402 (19)	0.0323 (18)	0.0020 (15)	−0.0001 (14)	−0.0104 (15)
O11	0.0463 (19)	0.0264 (16)	0.0323 (17)	0.0051 (14)	0.0016 (14)	−0.0117 (14)
O12	0.0344 (17)	0.0204 (15)	0.0368 (17)	−0.0019 (12)	−0.0084 (14)	−0.0066 (13)
O13	0.0268 (15)	0.0342 (17)	0.0261 (16)	−0.0007 (13)	0.0051 (12)	0.0007 (13)
O14	0.0258 (14)	0.0206 (14)	0.0281 (15)	0.0018 (11)	−0.0038 (12)	−0.0056 (12)
O15	0.0427 (18)	0.0313 (17)	0.0282 (16)	0.0121 (14)	0.0052 (14)	−0.0132 (14)
O16	0.076 (3)	0.0220 (16)	0.0325 (18)	0.0126 (16)	0.0118 (17)	−0.0102 (14)
N1	0.0336 (18)	0.0126 (15)	0.0187 (16)	0.0036 (13)	0.0039 (14)	−0.0022 (13)
C1	0.0249 (19)	0.0219 (19)	0.0157 (18)	0.0010 (15)	0.0000 (15)	−0.0034 (15)
C2	0.0243 (18)	0.0138 (17)	0.0172 (18)	−0.0015 (14)	0.0014 (15)	0.0006 (14)
C3	0.0242 (19)	0.0202 (19)	0.0172 (18)	−0.0009 (15)	0.0043 (14)	−0.0091 (15)
C4	0.0269 (19)	0.0153 (18)	0.0210 (19)	0.0017 (14)	−0.0015 (15)	−0.0105 (15)
C5	0.0228 (18)	0.0136 (17)	0.0204 (19)	−0.0001 (14)	0.0018 (15)	−0.0029 (14)
C6	0.0226 (18)	0.0143 (17)	0.0178 (18)	−0.0025 (14)	0.0005 (14)	−0.0051 (14)
C7	0.034 (2)	0.0146 (18)	0.020 (2)	0.0030 (15)	−0.0026 (16)	−0.0063 (15)
C8	0.028 (2)	0.0151 (18)	0.0197 (19)	0.0041 (15)	−0.0037 (15)	−0.0052 (15)
C9	0.0211 (18)	0.0173 (18)	0.0181 (19)	0.0007 (14)	0.0007 (14)	−0.0042 (14)
C10	0.0263 (19)	0.0138 (17)	0.0154 (18)	0.0004 (14)	−0.0013 (14)	−0.0016 (14)
C11	0.030 (2)	0.024 (2)	0.0141 (18)	0.0059 (16)	−0.0011 (15)	−0.0064 (15)
C12	0.030 (2)	0.020 (2)	0.023 (2)	0.0072 (16)	−0.0041 (16)	−0.0087 (16)
C13	0.032 (2)	0.0180 (19)	0.022 (2)	0.0062 (16)	−0.0029 (16)	−0.0100 (16)
C14	0.037 (2)	0.026 (2)	0.0175 (19)	0.0120 (17)	−0.0044 (17)	−0.0115 (16)

Geometric parameters (Å, º) top

Zn1—O15ⁱ	1.9523 (14)	O5—H5B	0.9610
Zn1—O1	1.956 (3)	O6—H6A	0.9687
Zn1—O3	1.983 (3)	O6—H6B	0.9721
Zn1—O6	2.155 (4)	O10—H10A	0.9642
Zn1—O14ⁱⁱ	2.292 (3)	O10—H10B	0.9623
Zn1—Zn2	3.1435 (8)	O11—H11A	0.8742
Zn2—O4	2.048 (2)	O11—H11B	0.8734
Zn2—O5	2.052 (2)	O14—Zn2ⁱⁱ	2.2868 (13)
Zn2—O3	2.061 (3)	O14—Zn1ⁱⁱ	2.2922 (15)
Zn2—O2	2.069 (3)	O15—C14	1.268 (4)
Zn2—O3ⁱⁱⁱ	2.118 (3)	O15—Zn1^v	1.9522 (13)
Zn2—O14ⁱⁱ	2.2868 (15)	O16—C14	1.233 (5)
Zn2—Zn2ⁱⁱⁱ	3.1170 (10)	N1—C5	1.373 (4)
Zn3—O11	2.0438 (12)	N1—C9	1.378 (4)
Zn3—O11^iv	2.0438 (12)	N1—H1	0.8800
Zn3—O10^iv	2.076 (3)	C1—C2	1.499 (5)
Zn3—O10	2.077 (3)	C2—C7	1.384 (5)
Zn3—O8^iv	2.164 (3)	C2—C3	1.404 (5)
Zn3—O8	2.164 (3)	C3—C4	1.375 (5)
S1—O7	1.434 (3)	C3—H3A	0.9500
S1—O8	1.444 (4)	C4—C5	1.401 (5)
S1—O9	1.456 (4)	C5—C6	1.413 (5)
S1—C4	1.764 (4)	C6—C7	1.391 (5)
S2—O13	1.4443 (15)	C6—C8	1.447 (5)
S2—O12	1.4546 (17)	C7—H7	0.9500
S2—O14	1.4698 (16)	C8—C13	1.400 (5)
S2—C10	1.759 (4)	C8—C9	1.407 (5)
O1—C1	1.263 (5)	C9—C10	1.397 (5)
O2—C1	1.252 (5)	C10—C11	1.390 (5)
O3—Zn2ⁱⁱⁱ	2.118 (3)	C11—C12	1.404 (6)
O3—H3	1.0000	C11—H11	0.9500
O4—H4A	0.8700	C12—C13	1.389 (6)
O4—H4B	0.8695	C12—C14	1.507 (5)
O5—H5A	0.9653	C13—H13	0.9500

O15ⁱ—Zn1—O1	102.03 (10)	Zn1—O3—Zn2	102.04 (12)
O15ⁱ—Zn1—O3	148.20 (10)	Zn1—O3—Zn2ⁱⁱⁱ	130.19 (14)
O1—Zn1—O3	109.11 (12)	Zn2—O3—Zn2ⁱⁱⁱ	96.46 (12)
O15ⁱ—Zn1—O6	88.49 (16)	Zn1—O3—H3	108.5
O1—Zn1—O6	98.54 (18)	Zn2—O3—H3	108.5
O3—Zn1—O6	93.05 (18)	Zn2ⁱⁱⁱ—O3—H3	108.5
O15ⁱ—Zn1—O14ⁱⁱ	96.53 (8)	Zn2—O4—H4A	110.9
O1—Zn1—O14ⁱⁱ	91.47 (10)	Zn2—O4—H4B	110.3
O3—Zn1—O14ⁱⁱ	76.75 (9)	H4A—O4—H4B	103.3
O6—Zn1—O14ⁱⁱ	167.65 (17)	Zn2—O5—H5A	109.1
O15ⁱ—Zn1—Zn2	143.08 (10)	Zn2—O5—H5B	109.3
O1—Zn1—Zn2	82.99 (9)	H5A—O5—H5B	108.9
O3—Zn1—Zn2	39.88 (8)	Zn1—O6—H6A	108.4
O6—Zn1—Zn2	127.35 (14)	Zn1—O6—H6B	108.2
O14ⁱⁱ—Zn1—Zn2	46.57 (4)	H6A—O6—H6B	107.8
O4—Zn2—O5	91.79 (9)	S1—O8—Zn3	153.0 (2)
O4—Zn2—O3	104.80 (10)	Zn3—O10—H10A	109.0
O5—Zn2—O3	161.66 (11)	Zn3—O10—H10B	109.1
O4—Zn2—O2	85.16 (12)	H10A—O10—H10B	108.9
O5—Zn2—O2	93.54 (14)	Zn3—O11—H11A	111.1
O3—Zn2—O2	95.59 (12)	Zn3—O11—H11B	110.4
O4—Zn2—O3ⁱⁱⁱ	92.72 (11)	H11A—O11—H11B	103.0
O5—Zn2—O3ⁱⁱⁱ	87.98 (13)	S2—O14—Zn2ⁱⁱ	135.38 (9)
O3—Zn2—O3ⁱⁱⁱ	83.54 (12)	S2—O14—Zn1ⁱⁱ	134.74 (8)
O2—Zn2—O3ⁱⁱⁱ	177.43 (12)	Zn2ⁱⁱ—O14—Zn1ⁱⁱ	86.71 (5)
O4—Zn2—O14ⁱⁱ	170.98 (10)	C14—O15—Zn1^v	121.9 (2)
O5—Zn2—O14ⁱⁱ	89.45 (9)	C5—N1—C9	109.4 (2)
O3—Zn2—O14ⁱⁱ	75.40 (10)	C5—N1—H1	125.3
O2—Zn2—O14ⁱⁱ	85.85 (10)	C9—N1—H1	125.3
O3ⁱⁱⁱ—Zn2—O14ⁱⁱ	96.25 (9)	O2—C1—O1	125.2 (4)
O4—Zn2—Zn2ⁱⁱⁱ	101.60 (8)	O2—C1—C2	118.0 (4)
O5—Zn2—Zn2ⁱⁱⁱ	127.12 (11)	O1—C1—C2	116.8 (4)
O3—Zn2—Zn2ⁱⁱⁱ	42.47 (8)	C7—C2—C3	120.4 (3)
O2—Zn2—Zn2ⁱⁱⁱ	138.00 (9)	C7—C2—C1	120.8 (3)
O3ⁱⁱⁱ—Zn2—Zn2ⁱⁱⁱ	41.07 (8)	C3—C2—C1	118.8 (4)
O14ⁱⁱ—Zn2—Zn2ⁱⁱⁱ	84.68 (4)	C4—C3—C2	121.2 (4)
O4—Zn2—Zn1	128.73 (7)	C4—C3—H3A	119.4
O5—Zn2—Zn1	133.03 (7)	C2—C3—H3A	119.4
O3—Zn2—Zn1	38.08 (8)	C3—C4—C5	118.6 (3)
O2—Zn2—Zn1	70.94 (8)	C3—C4—S1	122.0 (3)
O3ⁱⁱⁱ—Zn2—Zn1	109.46 (8)	C5—C4—S1	119.4 (3)
O14ⁱⁱ—Zn2—Zn1	46.72 (7)	N1—C5—C4	130.1 (3)
Zn2ⁱⁱⁱ—Zn2—Zn1	72.90 (2)	N1—C5—C6	109.3 (3)
O11—Zn3—O11^iv	180.00 (10)	C4—C5—C6	120.6 (3)
O11—Zn3—O10^iv	90.50 (11)	C7—C6—C5	119.7 (4)
O11^iv—Zn3—O10^iv	89.50 (11)	C7—C6—C8	134.6 (4)
O11—Zn3—O10	89.50 (11)	C5—C6—C8	105.7 (3)
O11^iv—Zn3—O10	90.50 (11)	C2—C7—C6	119.5 (4)
O10^iv—Zn3—O10	180.0	C2—C7—H7	120.3
O11—Zn3—O8^iv	88.12 (12)	C6—C7—H7	120.3
O11^iv—Zn3—O8^iv	91.88 (12)	C13—C8—C9	120.2 (4)
O10^iv—Zn3—O8^iv	90.07 (15)	C13—C8—C6	132.6 (4)
O10—Zn3—O8^iv	89.93 (15)	C9—C8—C6	107.2 (3)
O11—Zn3—O8	91.88 (12)	N1—C9—C10	130.6 (3)
O11^iv—Zn3—O8	88.12 (12)	N1—C9—C8	108.4 (3)
O10^iv—Zn3—O8	89.93 (15)	C10—C9—C8	120.9 (4)
O10—Zn3—O8	90.07 (15)	C11—C10—C9	118.4 (3)
O8^iv—Zn3—O8	180.0	C11—C10—S2	119.5 (3)
O7—S1—O8	113.5 (2)	C9—C10—S2	122.1 (3)
O7—S1—O9	113.3 (2)	C10—C11—C12	120.9 (4)
O8—S1—O9	111.2 (3)	C10—C11—H11	119.6
O7—S1—C4	107.3 (2)	C12—C11—H11	119.6
O8—S1—C4	104.8 (2)	C13—C12—C11	120.9 (4)
O9—S1—C4	106.1 (2)	C13—C12—C14	119.8 (4)
O13—S2—O12	114.31 (12)	C11—C12—C14	119.2 (4)
O13—S2—O14	111.87 (10)	C12—C13—C8	118.7 (4)
O12—S2—O14	109.57 (9)	C12—C13—H13	120.7
O13—S2—C10	107.86 (14)	C8—C13—H13	120.7
O12—S2—C10	105.17 (14)	O16—C14—O15	123.6 (3)
O14—S2—C10	107.63 (15)	O16—C14—C12	119.8 (4)
C1—O1—Zn1	124.5 (3)	O15—C14—C12	116.5 (4)
C1—O2—Zn2	135.7 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O13^vi	1.00	1.83	2.804 (5)	163
O4—H4A···O12^vi	0.87	1.86	2.632 (4)	147
O4—H4B···O16^vii	0.87	1.85	2.608 (3)	145
O5—H5A···O12ⁱⁱ	0.97	1.81	2.736 (3)	160
O5—H5B···O7^viii	0.96	2.09	2.818 (4)	131
O6—H6A···O13^vi	0.97	2.09	2.976 (5)	151
O6—H6B···O7^ix	0.97	2.24	3.156 (7)	157
O10—H10A···O7^x	0.96	2.20	2.941 (5)	133
O10—H10B···O16^vi	0.96	1.72	2.666 (5)	166
O11—H11A···O4^vi	0.87	1.96	2.837 (3)	179
O11—H11B···O9^x	0.87	1.89	2.757 (5)	171
N1—H1···O9	0.88	2.46	2.962 (4)	117
N1—H1···O12	0.88	2.40	2.908	117

Symmetry codes: (ii) −x+2, −y+1, −z+1; (vi) −x+1, −y+1, −z+1; (vii) −x+1, −y+2, −z+1; (viii) x, y+1, z; (ix) −x+2, −y+1, −z; (x) x−1, y, z.

Acknowledgements

The authors thank Beijing University of Technology for supporting this work.

Funding information

Funding for this research was provided by: China Postdoctoral Science Foundation (grant No. 2018M642556).

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