An Ni-based coordination polymer with a bamboo-like crystal structure

Li, Y.; Xie, W.; Lin, C.

doi:10.1107/S2056989025002993

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Volume 81| Part 5| May 2025|

https://doi.org/10.1107/S2056989025002993

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An Ni-based coordination polymer with a bamboo-like crystal structure

Yi Li,^a Wang Xie ^b and Chen Lin ^b ^*

^aNanjing Petmedicine Technology Co., Ltd, Nanjing, People's Republic of China, and ^bSchool of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, People's Republic of China
^*Correspondence e-mail: linchen@nju.edu.cn

Edited by X. Hao, Institute of Chemistry, Chinese Academy of Sciences (Received 24 March 2025; accepted 3 April 2025; online 8 April 2025)

An Ni-based coordination polymer, namely, poly[tetraaquabis[4,7-bis(1H-pyrazol-4-yl)benzo[c][1,2,5]thiadiazole][μ₄-5,5′-(1,3,6,8-tetraoxo-1,3,6,8-tetrahydrobenzo[lmn][3,8]phenanthroline-2,7-diyl)diisophthalato]dinickel(II)], {[Ni₂(C₃₀H₁₀N₂O₁₂)(C₁₂H₈N₆S)₂(H₂O)₄]·2C₃H₇NO·H₂O}_n or Ni-BIBT-BINDI, with a crystal structure reminiscent of bamboo has been synthesized, the Ni²⁺ ions exhibiting a slightly distorted octahedral coordination geometry with N atoms and O atoms. The bond lengths of the Ni—O bonds range from 2.032 to 2.121 Å, and those of the Ni—N bonds are approximately 2.080 Å. The BINDI ligands are connected to each other by the Ni—O bonds, which form the backbone of the bamboo, while the BIBT ligands are connected to the backbone of the bamboo through Ni—N bonds and grows on both sides of the bamboo, constituting the bamboo leaves.

Keywords: crystal structure; Ni-based coordination polymer; sing-crystal; chain structure.

CCDC reference: 2364669

1. Chemical context

Coordination polymers are defined as polymers formed by the association of inorganic metal ions and organic ligands with coordination bonds (Xia et al., 2022 ). Currently, coordination polymers are being widely used in the fields of catalysis (Li et al., 2024 ), sensing (Tian et al., 2023 ) and gas storage (Dong et al., 2023 ). In particular, Ni-based coordination polymers have received much attention from researchers in recent years because of their excellent catalytic properties (Shah et al., 2019 ) and electrical conductivity (Khokhar et al., 2022 ).

In this context, a novel one-dimensional Ni-based coordination polymer with the formula {[Ni (BINDI)_0.5(BIBT)(H₂O)₂]·DMF·0.5H₂O]}_n [DMF = N,N-dimethylformamide, BIBT = 4,7-di(1H-pyrazol-4-yl)benzo[c][1,2,5]thiadiazole and H₄BINDI = 5,5′-(1,3,6,8-tetraoxo-1,3,6,8-tetrahydrobenzo[lmn][3,8]phenanthroline-2,7-diyl)diisophthalic acid], namely Ni-BIBT-BINDI, was synthesized. The crystal structure of Ni-BIBT-BINDI exhibits a bamboo-like morphology, with BINDI⁴⁻ ions and Ni²⁺ ions connected to form the bamboo trunk, and BIBT ligands and Ni²⁺ ions coordinated to form the bamboo leaves.

2. Structural commentary

Ni-BIBT-BINDI crystallizes in the triclinic crystal system, space group P $[\overline{1}]$ . The asymmetric unit contains one Ni^II ion, one BIBT ligand and half a BINDI⁴⁻ ion, one DMF molecule, as well as two coordinated H₂O molecules and half of a free H₂O molecule (Fig. 1). The Ni^II ion is surrounded by one nitrogen atom (N1) from one BIBT molecule, two oxygen atoms (O3, O4) from two different H₂O molecules, and three oxygen (O1, O5, O6) atoms from two different BINDI⁴⁻ ions (Fig. 1), resulting in a distorted octahedral coordination geometry (Fig. 1). The Ni—O bond lengths range from 2.032 (3) to 2.122 (3) Å, while the Ni—N bond length is 2.079 (4) Å (Table 1), which is consistent with previously reported Ni-based coordination complexes (Wang et al., 2020 ). The BINDI⁴⁻ ions are linked by the Ni²⁺ ions, extending along the b-axis direction (Fig. 2a), forming a structure comparable to that of bamboo, while the naphthalene diimide functional group is almost perpendicular to the b-axis, resembling a bamboo joint (Fig. 2b). The distance between adjacent naphthalene diimide functional groups is 10.15 Å (Fig. 2b). The N atom at the terminal end of the BIBT ligand on the bamboo coordinates with the Ni²⁺ ion and grows in a manner analogous to a bamboo leaf (Fig. 2b). It has been established that only one end of the N atom of the BIBT ligand is coordinated to the Ni²⁺ ion, thus resulting in the formation of a mono-periodic chain.

Table 1
Selected geometric parameters (Å, °)

Ni1—O1	2.042 (3)	Ni1—O5ⁱ	2.115 (3)
Ni1—O3	2.101 (3)	Ni1—O6ⁱ	2.122 (3)
Ni1—O4	2.032 (3)	Ni1—N1	2.079 (4)

O1—Ni1—O3	89.17 (14)	O4—Ni1—O5ⁱ	103.05 (13)
O1—Ni1—O5ⁱ	160.93 (13)	O4—Ni1—O6ⁱ	164.09 (13)
O1—Ni1—O6ⁱ	98.70 (12)	O4—Ni1—N1	96.72 (15)
O1—Ni1—N1	89.40 (15)	O5ⁱ—Ni1—O6ⁱ	62.43 (12)
O3—Ni1—O5ⁱ	87.54 (13)	N1—Ni1—O3	178.02 (14)
O3—Ni1—O6ⁱ	87.96 (13)	N1—Ni1—O5ⁱ	93.37 (15)
O4—Ni1—O1	95.34 (13)	N1—Ni1—O6ⁱ	90.90 (15)
O4—Ni1—O3	84.78 (14)
Symmetry code: (i) .

Figure 1
[The coordination environment of Ni-BIBT-BINDI, Symmetry codes: (i) x, y − 1,z?(ii) x, y + 1, z; (iii) −x, −y + 2, −z]

Figure 2
[(a)The Ni—BT-BINDI chain was observed from the b axis direction. (b) The Ni—BT-BINDI chain exhibits a structural similarity to bamboo, with nodes positioned at intervals of 10.15 Å]

3. Supramolecular features

In the crystal structure of Ni-BIBT-BINDI, the coordination polymer chains are oriented along the b-axis direction. The chains are linked by face-to-face π–π stacking interactions [centroid–centroid distance = 3.515 (3) Å] between the BIBT ligand and BINDI ion, as shown in Fig. 3a. Within an Ni-BIBT-BINDI chain, the pore between two neighbouring ligand BINDIs contains two ligand BIBTs, which are from different Ni-BIBT-BINDI chains. The distance between the BIBT ligand and the neighbouring BINDI ligand is 3.5 Å, as shown in Fig. 3b. In addition to these π–π stacking interactions, there is also evidence of hydrogen-bonding interactions between a DMF molecule and two distinct Ni-BIBT-BINDI chains (C28—H28C⋯O8, 2.26 Å; O4—H4B⋯O9ⁱⁱ, 1.83 Å; N2—H2⋯O9ⁱⁱ, 1.92 Å; Table 2). Hydrogen bonding is also present between two different Ni-BIBT-BINDI chains (O3—H3A⋯O2ⁱⁱ; Fig. 3b, Table 2). These weak interactions connect Ni-BIBT-BINDI chains and build the 3D framework structure of Ni-BIBT-BINDI.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O2ⁱⁱ	0.87	1.92	2.758 (5)	162
O3—H3B⋯N6ⁱⁱⁱ	0.87	2.18	2.986 (5)	154
O4—H4A⋯O2	0.87	1.86	2.640 (4)	148
O4—H4B⋯O9ⁱⁱ	0.87	1.83	2.695 (5)	173
N2—H2⋯O9ⁱⁱ	0.88	1.92	2.779 (5)	166
N5—H5⋯N6^iv	0.88	2.20	2.956 (6)	144
C1—H1⋯O10ⁱⁱⁱ	0.95	2.57	3.46 (3)	155
C11—H11⋯O1ⁱⁱⁱ	0.95	2.54	3.210 (6)	127
C11—H11⋯O6^v	0.95	2.49	3.279 (6)	141
C12—H12⋯O2^vi	0.95	2.46	3.168 (6)	131
C28—H28A⋯N5ⁱⁱⁱ	0.98	2.65	3.426 (8)	136
C28—H28B⋯O4ⁱⁱ	0.98	2.72	3.414 (6)	128
C28—H28C⋯O8	0.98	2.26	3.157 (7)	151
O10—H10A⋯O7	0.87	2.08	2.95 (3)	180
O10—H10B⋯O6^v	0.87	2.20	3.01 (3)	155
Symmetry codes: (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Figure 3
[(a) The π-π stacking interactions between the ligand BIBT and BINDI, (b) The H-bond interactions between a DMF molecule and two distinct Ni—BT-BINDI chains.]

4. Database survey

A search in CSD (version 5.46, last update November 2024; Groom et al., 2016 ) using CONQUEST (Bruno et al., 2002 ) for compounds based on BIBT and BINDI ligands revealed that no identical compounds have been reported. However, there are two metal–organic frameworks assembled from ligand BT [4,7-di(1H-benzoimidazol-1-yl)benzo[c][1,2,5]thiadiazole, structurally analogous to BIBT] in combination with BINDI ligands. The structural unit of the first compound includes Ni²⁺ ions, BINDI and BT ligands (BODCOQ; Xiong et al., 2024 ),while that of the second compound includes Cu²⁺ ions, BINDI and BT ligands (TILTHU; Huang et al., 2023 ).

5. Synthesis and crystallization

The crystal of Ni-BIBT-BINDI was synthesized by the solvothermal method. 2.7 mg of BIBT, 6 mg of BINDI, 58 mg of Ni(NO₃)₂·6H₂O, 3.5 mL of DMF and 2.5 mL of deionized water were added in a 10 mL glass tube. After sonication for about 10 min, the glass tube was sealed and heated at 368 K for 24 h. After cooling to room temperature, green crystals were collected.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms were positioned geometrically and refined using a riding model.

Table 3
Experimental details

Crystal data
Chemical formula	[Ni₂(C₃₀H₁₀N₂O₁₂)(C₁₂H₈N₆S)₂(H₂O)₄]·2(C₃H₇NO)·H₂O
M_r	1480.70
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	193
a, b, c (Å)	9.5384 (4), 10.1543 (4), 16.2521 (8)
α, β, γ (°)	81.511 (3), 75.790 (3), 75.920 (3)
V (Å³)	1473.62 (12)
Z	1
Radiation type	Cu Kα
μ (mm⁻¹)	2.27
Crystal size (mm)	0.16 × 0.12 × 0.11

Data collection
Diffractometer	Bruker PHOTON-II area detector
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.544, 0.753
No. of measured, independent and observed [I > 2σ(I)] reflections	24224, 5414, 4005
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.076, 0.247, 1.06
No. of reflections	5414
No. of parameters	455
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.46, −1.04
Computer programs: APEX2 and SAINT (Bruker, 2016 ), OLEX2.solve (Bourhis et al., 2015 ), SHELXL2018/3 (Sheldrick, 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2364669

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025002993/nx2022sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025002993/nx2022Isup3.hkl

checkCIF report

Computing details top

Poly[tetraaquabis[4,7-bis(1H-pyrazol-4-yl)benzo[c][1,2,5]thiadiazole][µ₄-5,5'-(1,3,6,8-tetraoxo-1,3,6,8-tetrahydrobenzo[lmn][3,8]phenanthroline-2,7-diyl)diisophthalato]dinickel(II)] top

Crystal data top

[Ni₂(C₃₀H₁₀N₂O₁₂)(C₁₂H₈N₆S)₂(H₂O)₄]·2(C₃H₇NO)·H₂O	Z = 1
M_r = 1480.70	F(000) = 762
Triclinic, P1	D_x = 1.669 Mg m⁻³
a = 9.5384 (4) Å	Cu Kα radiation, λ = 1.54178 Å
b = 10.1543 (4) Å	Cell parameters from 7699 reflections
c = 16.2521 (8) Å	θ = 4.5–68.1°
α = 81.511 (3)°	µ = 2.27 mm⁻¹
β = 75.790 (3)°	T = 193 K
γ = 75.920 (3)°	Block, dull greenish green
V = 1473.62 (12) Å³	0.16 × 0.12 × 0.11 mm

Data collection top

Bruker PHOTON-II area detector diffractometer	4005 reflections with I > 2σ(I)
Detector resolution: 7.4 pixels mm^-1	R_int = 0.068
phi and ω scans	θ_max = 68.6°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −11→11
T_min = 0.544, T_max = 0.753	k = −12→12
24224 measured reflections	l = −19→19
5414 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.076	H-atom parameters constrained
wR(F²) = 0.247	w = 1/[σ²(F_o²) + (0.1781P)² + 0.7895P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
5414 reflections	Δρ_max = 1.46 e Å⁻³
455 parameters	Δρ_min = −1.04 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)
Ni1	0.57153 (8)	0.31000 (7)	0.84217 (5)	0.0304 (3)
S1	1.29018 (14)	0.30007 (14)	0.39030 (9)	0.0450 (4)
O1	0.4971 (4)	0.5137 (3)	0.8127 (2)	0.0341 (7)
O2	0.5865 (3)	0.6001 (3)	0.9027 (2)	0.0335 (7)
O3	0.3923 (4)	0.3157 (3)	0.9478 (2)	0.0378 (8)
H3A	0.418410	0.332432	0.992361	0.057*
H3B	0.321320	0.385253	0.939452	0.057*
O4	0.6859 (4)	0.3342 (3)	0.9272 (2)	0.0359 (7)
H4A	0.680119	0.420791	0.928462	0.054*
H4B	0.779938	0.300760	0.908602	0.054*
O5	0.5926 (4)	1.0963 (3)	0.8525 (2)	0.0349 (7)
O6	0.4480 (4)	1.2335 (3)	0.7751 (2)	0.0337 (7)
O7	0.4323 (4)	0.8766 (4)	0.5411 (2)	0.0492 (9)
O8	0.0255 (4)	0.9415 (4)	0.7567 (2)	0.0496 (10)
N1	0.7439 (4)	0.3085 (4)	0.7351 (3)	0.0359 (9)
N2	0.8912 (5)	0.2834 (4)	0.7296 (3)	0.0393 (9)
H2	0.933374	0.260189	0.773567	0.047*
N3	1.1602 (5)	0.3014 (4)	0.4758 (3)	0.0423 (10)
N4	1.1933 (5)	0.3483 (4)	0.3182 (3)	0.0408 (10)
N5	1.0322 (5)	0.4553 (5)	0.0894 (3)	0.0454 (10)
H5	1.094565	0.446406	0.039685	0.055*
N6	0.8855 (5)	0.5163 (5)	0.0989 (3)	0.0416 (10)
N7	0.2282 (4)	0.9214 (4)	0.6484 (2)	0.0311 (8)
C1	0.7268 (6)	0.3386 (5)	0.6562 (3)	0.0396 (11)
H1	0.633402	0.359982	0.640809	0.048*
C2	0.8620 (5)	0.3357 (5)	0.5972 (3)	0.0358 (10)
C3	0.9646 (6)	0.2981 (5)	0.6490 (3)	0.0372 (10)
H3	1.069080	0.285286	0.630045	0.045*
C4	0.8869 (5)	0.3612 (5)	0.5052 (3)	0.0363 (10)
C5	0.7710 (6)	0.4059 (5)	0.4641 (3)	0.0410 (11)
H5A	0.672881	0.419811	0.497727	0.049*
C6	0.7905 (6)	0.4322 (6)	0.3745 (3)	0.0434 (12)
H6	0.704894	0.463219	0.351132	0.052*
C7	0.9277 (5)	0.4149 (5)	0.3194 (3)	0.0346 (10)
C8	1.0512 (6)	0.3685 (5)	0.3594 (3)	0.0356 (10)
C9	1.0309 (6)	0.3426 (5)	0.4498 (3)	0.0361 (10)
C10	0.9456 (5)	0.4426 (5)	0.2269 (3)	0.0368 (10)
C11	0.8347 (6)	0.5097 (5)	0.1819 (3)	0.0393 (11)
H11	0.734986	0.545945	0.208585	0.047*
C12	1.0702 (6)	0.4106 (6)	0.1641 (3)	0.0434 (12)
H12	1.166018	0.364911	0.172088	0.052*
C13	0.5182 (5)	0.6112 (4)	0.8442 (3)	0.0292 (9)
C14	0.4599 (5)	0.7526 (4)	0.8049 (3)	0.0293 (9)
C15	0.3696 (5)	0.7719 (4)	0.7469 (3)	0.0313 (9)
H15	0.340778	0.696185	0.732957	0.038*
C16	0.3218 (5)	0.9009 (5)	0.7094 (3)	0.0320 (10)
C17	0.3612 (5)	1.0118 (4)	0.7286 (3)	0.0323 (10)
H17	0.326368	1.100122	0.702890	0.039*
C18	0.4529 (5)	0.9944 (4)	0.7863 (3)	0.0295 (9)
C19	0.5010 (5)	0.8645 (4)	0.8249 (3)	0.0306 (9)
H19	0.561972	0.852347	0.864919	0.037*
C20	0.5006 (5)	1.1154 (4)	0.8060 (3)	0.0309 (9)
C21	0.2983 (5)	0.9141 (5)	0.5622 (3)	0.0344 (10)
C22	0.0752 (5)	0.9435 (5)	0.6811 (3)	0.0323 (10)
C23	−0.0198 (5)	0.9732 (4)	0.6173 (3)	0.0314 (10)
C24	0.0452 (5)	0.9811 (4)	0.5302 (3)	0.0298 (9)
C25	−0.1718 (5)	0.9988 (5)	0.6451 (3)	0.0358 (10)
H25	−0.214907	0.991401	0.704439	0.043*
C26	−0.2624 (6)	1.0358 (5)	0.5860 (3)	0.0381 (11)
H26	−0.367033	1.053781	0.605420	0.046*
C27	−0.2012 (5)	1.0462 (4)	0.5001 (3)	0.0309 (9)
O9	0.0216 (4)	0.7746 (4)	1.1156 (2)	0.0448 (9)
N8	−0.0606 (5)	0.8531 (5)	0.9943 (3)	0.0427 (10)
C28	0.0864 (7)	0.8243 (7)	0.9386 (4)	0.0523 (14)
H28A	0.112379	0.728549	0.926460	0.078*
H28B	0.159091	0.841639	0.966780	0.078*
H28C	0.086624	0.883241	0.885104	0.078*
C29	−0.1853 (7)	0.9179 (6)	0.9545 (4)	0.0526 (14)
H29A	−0.168246	1.004746	0.923080	0.079*
H29B	−0.276681	0.934675	0.998658	0.079*
H29C	−0.194565	0.857833	0.915068	0.079*
C30	−0.0785 (6)	0.8241 (5)	1.0773 (3)	0.0415 (11)
H30	−0.176878	0.842806	1.110522	0.050*
O10	0.584 (3)	0.692 (2)	0.4066 (17)	0.217 (12)	0.5
H10A	0.539592	0.746254	0.446417	0.326*	0.5
H10B	0.557502	0.736204	0.360787	0.326*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0285 (5)	0.0232 (4)	0.0429 (5)	−0.0058 (3)	−0.0149 (3)	−0.0012 (3)
S1	0.0326 (7)	0.0497 (8)	0.0521 (8)	−0.0048 (5)	−0.0156 (5)	0.0007 (6)
O1	0.0359 (18)	0.0220 (15)	0.0500 (19)	−0.0064 (13)	−0.0215 (14)	−0.0001 (13)
O2	0.0311 (17)	0.0249 (15)	0.0477 (18)	−0.0025 (13)	−0.0198 (14)	−0.0004 (13)
O3	0.0331 (17)	0.0382 (18)	0.0457 (19)	−0.0060 (14)	−0.0160 (14)	−0.0057 (14)
O4	0.0321 (17)	0.0288 (16)	0.0497 (19)	−0.0045 (13)	−0.0172 (14)	−0.0027 (13)
O5	0.0336 (17)	0.0254 (16)	0.0515 (19)	−0.0069 (13)	−0.0217 (14)	−0.0001 (13)
O6	0.0335 (17)	0.0216 (15)	0.0504 (19)	−0.0044 (12)	−0.0202 (14)	−0.0015 (13)
O7	0.0244 (18)	0.069 (3)	0.054 (2)	−0.0009 (17)	−0.0190 (15)	−0.0023 (18)
O8	0.0354 (19)	0.071 (3)	0.042 (2)	−0.0040 (18)	−0.0182 (15)	0.0006 (17)
N1	0.032 (2)	0.033 (2)	0.045 (2)	−0.0080 (16)	−0.0119 (17)	−0.0034 (16)
N2	0.037 (2)	0.036 (2)	0.047 (2)	−0.0058 (18)	−0.0170 (18)	−0.0021 (17)
N3	0.042 (2)	0.036 (2)	0.052 (2)	−0.0081 (18)	−0.0181 (19)	0.0003 (18)
N4	0.032 (2)	0.038 (2)	0.054 (3)	−0.0078 (17)	−0.0136 (18)	−0.0016 (18)
N5	0.036 (2)	0.057 (3)	0.042 (2)	−0.010 (2)	−0.0089 (18)	−0.0025 (19)
N6	0.035 (2)	0.046 (2)	0.045 (2)	−0.0084 (19)	−0.0124 (18)	−0.0032 (18)
N7	0.0269 (19)	0.0271 (18)	0.043 (2)	−0.0060 (15)	−0.0174 (15)	0.0019 (15)
C1	0.040 (3)	0.034 (2)	0.048 (3)	−0.007 (2)	−0.017 (2)	−0.003 (2)
C2	0.035 (3)	0.028 (2)	0.047 (3)	−0.0097 (19)	−0.014 (2)	−0.0032 (19)
C3	0.035 (3)	0.034 (2)	0.045 (3)	−0.009 (2)	−0.014 (2)	−0.0008 (19)
C4	0.035 (3)	0.030 (2)	0.049 (3)	−0.0120 (19)	−0.013 (2)	−0.0020 (19)
C5	0.031 (3)	0.047 (3)	0.047 (3)	−0.011 (2)	−0.008 (2)	−0.004 (2)
C6	0.033 (3)	0.049 (3)	0.053 (3)	−0.008 (2)	−0.018 (2)	−0.006 (2)
C7	0.030 (2)	0.031 (2)	0.045 (3)	−0.0070 (19)	−0.0131 (19)	−0.0036 (19)
C8	0.034 (2)	0.028 (2)	0.046 (3)	−0.0090 (19)	−0.012 (2)	−0.0013 (19)
C9	0.037 (3)	0.028 (2)	0.048 (3)	−0.0105 (19)	−0.015 (2)	−0.0026 (19)
C10	0.030 (2)	0.033 (2)	0.049 (3)	−0.0072 (19)	−0.014 (2)	−0.002 (2)
C11	0.032 (2)	0.037 (3)	0.051 (3)	−0.005 (2)	−0.014 (2)	−0.005 (2)
C12	0.033 (3)	0.052 (3)	0.047 (3)	−0.008 (2)	−0.014 (2)	−0.003 (2)
C13	0.026 (2)	0.024 (2)	0.041 (2)	−0.0089 (17)	−0.0120 (17)	0.0002 (17)
C14	0.023 (2)	0.024 (2)	0.041 (2)	−0.0011 (17)	−0.0110 (17)	−0.0022 (17)
C15	0.026 (2)	0.025 (2)	0.046 (3)	−0.0068 (17)	−0.0114 (18)	−0.0031 (18)
C16	0.029 (2)	0.031 (2)	0.040 (2)	−0.0063 (18)	−0.0171 (18)	−0.0003 (18)
C17	0.028 (2)	0.023 (2)	0.044 (3)	−0.0019 (17)	−0.0125 (18)	0.0003 (17)
C18	0.022 (2)	0.023 (2)	0.046 (2)	−0.0056 (16)	−0.0113 (17)	−0.0028 (17)
C19	0.026 (2)	0.029 (2)	0.039 (2)	−0.0058 (17)	−0.0133 (18)	−0.0024 (18)
C20	0.026 (2)	0.026 (2)	0.041 (2)	−0.0044 (17)	−0.0091 (18)	−0.0024 (17)
C21	0.032 (2)	0.030 (2)	0.046 (3)	−0.0068 (19)	−0.0196 (19)	−0.0001 (18)
C22	0.029 (2)	0.029 (2)	0.043 (3)	−0.0054 (18)	−0.0180 (19)	0.0018 (18)
C23	0.028 (2)	0.025 (2)	0.044 (2)	−0.0060 (18)	−0.0168 (19)	−0.0001 (17)
C24	0.028 (2)	0.021 (2)	0.044 (2)	−0.0057 (17)	−0.0159 (19)	0.0002 (17)
C25	0.031 (2)	0.034 (2)	0.043 (3)	−0.0076 (19)	−0.0123 (19)	0.0021 (19)
C26	0.029 (2)	0.038 (3)	0.047 (3)	−0.005 (2)	−0.012 (2)	−0.001 (2)
C27	0.025 (2)	0.028 (2)	0.043 (2)	−0.0047 (17)	−0.0150 (18)	−0.0008 (17)
O9	0.0387 (19)	0.050 (2)	0.047 (2)	−0.0044 (16)	−0.0193 (16)	0.0019 (15)
N8	0.038 (2)	0.044 (2)	0.048 (2)	−0.0057 (19)	−0.0194 (19)	0.0007 (18)
C28	0.043 (3)	0.062 (4)	0.049 (3)	−0.007 (3)	−0.014 (2)	0.001 (3)
C29	0.046 (3)	0.050 (3)	0.065 (4)	−0.005 (3)	−0.029 (3)	0.006 (3)
C30	0.032 (3)	0.038 (3)	0.056 (3)	−0.008 (2)	−0.013 (2)	−0.001 (2)
O10	0.29 (3)	0.16 (2)	0.22 (2)	−0.02 (2)	−0.11 (2)	−0.028 (17)

Geometric parameters (Å, º) top

Ni1—O1	2.042 (3)	C6—C7	1.380 (7)
Ni1—O3	2.101 (3)	C7—C8	1.432 (7)
Ni1—O4	2.032 (3)	C7—C10	1.462 (7)
Ni1—O5ⁱ	2.115 (3)	C8—C9	1.428 (7)
Ni1—O6ⁱ	2.122 (3)	C10—C11	1.415 (7)
Ni1—N1	2.079 (4)	C10—C12	1.370 (7)
Ni1—C20ⁱ	2.428 (5)	C11—H11	0.9500
S1—N3	1.618 (5)	C12—H12	0.9500
S1—N4	1.615 (4)	C13—C14	1.515 (6)
O1—C13	1.257 (5)	C14—C15	1.390 (6)
O2—C13	1.257 (5)	C14—C19	1.393 (6)
O3—H3A	0.8717	C15—H15	0.9500
O3—H3B	0.8720	C15—C16	1.380 (6)
O4—H4A	0.8703	C16—C17	1.368 (7)
O4—H4B	0.8715	C17—H17	0.9500
O5—C20	1.256 (6)	C17—C18	1.398 (6)
O6—C20	1.263 (5)	C18—C19	1.395 (6)
O7—C21	1.217 (6)	C18—C20	1.510 (6)
O8—C22	1.202 (6)	C19—H19	0.9500
N1—N2	1.348 (6)	C21—C27ⁱⁱ	1.484 (6)
N1—C1	1.314 (6)	C22—C23	1.491 (6)
N2—H2	0.8800	C23—C24	1.398 (7)
N2—C3	1.330 (7)	C23—C25	1.380 (7)
N3—C9	1.351 (6)	C24—C24ⁱⁱ	1.413 (8)
N4—C8	1.336 (6)	C24—C27ⁱⁱ	1.419 (6)
N5—H5	0.8800	C25—H25	0.9500
N5—N6	1.366 (6)	C25—C26	1.397 (7)
N5—C12	1.335 (7)	C26—H26	0.9500
N6—C11	1.314 (7)	C26—C27	1.375 (7)
N7—C16	1.452 (5)	O9—C30	1.232 (6)
N7—C21	1.401 (6)	N8—C28	1.459 (7)
N7—C22	1.399 (6)	N8—C29	1.462 (6)
C1—H1	0.9500	N8—C30	1.315 (7)
C1—C2	1.401 (7)	C28—H28A	0.9800
C2—C3	1.393 (7)	C28—H28B	0.9800
C2—C4	1.450 (7)	C28—H28C	0.9800
C3—H3	0.9500	C29—H29A	0.9800
C4—C5	1.380 (7)	C29—H29B	0.9800
C4—C9	1.431 (7)	C29—H29C	0.9800
C5—H5A	0.9500	C30—H30	0.9500
C5—C6	1.415 (7)	O10—H10A	0.8701
C6—H6	0.9500	O10—H10B	0.8699

O1—Ni1—O3	89.17 (14)	C12—C10—C11	103.9 (4)
O1—Ni1—O5ⁱ	160.93 (13)	N6—C11—C10	112.2 (5)
O1—Ni1—O6ⁱ	98.70 (12)	N6—C11—H11	123.9
O1—Ni1—N1	89.40 (15)	C10—C11—H11	123.9
O1—Ni1—C20ⁱ	129.91 (14)	N5—C12—C10	107.5 (5)
O3—Ni1—O5ⁱ	87.54 (13)	N5—C12—H12	126.3
O3—Ni1—O6ⁱ	87.96 (13)	C10—C12—H12	126.3
O3—Ni1—C20ⁱ	86.63 (14)	O1—C13—O2	125.5 (4)
O4—Ni1—O1	95.34 (13)	O1—C13—C14	116.0 (4)
O4—Ni1—O3	84.78 (14)	O2—C13—C14	118.5 (4)
O4—Ni1—O5ⁱ	103.05 (13)	C15—C14—C13	120.9 (4)
O4—Ni1—O6ⁱ	164.09 (13)	C15—C14—C19	119.4 (4)
O4—Ni1—N1	96.72 (15)	C19—C14—C13	119.7 (4)
O4—Ni1—C20ⁱ	133.75 (14)	C14—C15—H15	120.0
O5ⁱ—Ni1—O6ⁱ	62.43 (12)	C16—C15—C14	120.1 (4)
O5ⁱ—Ni1—C20ⁱ	31.13 (13)	C16—C15—H15	120.0
O6ⁱ—Ni1—C20ⁱ	31.31 (14)	C15—C16—N7	120.3 (4)
N1—Ni1—O3	178.02 (14)	C17—C16—N7	118.6 (4)
N1—Ni1—O5ⁱ	93.37 (15)	C17—C16—C15	121.1 (4)
N1—Ni1—O6ⁱ	90.90 (15)	C16—C17—H17	120.2
N1—Ni1—C20ⁱ	93.24 (16)	C16—C17—C18	119.7 (4)
N4—S1—N3	100.7 (2)	C18—C17—H17	120.2
C13—O1—Ni1	127.5 (3)	C17—C18—C20	120.1 (4)
Ni1—O3—H3A	109.5	C19—C18—C17	119.6 (4)
Ni1—O3—H3B	109.5	C19—C18—C20	120.3 (4)
H3A—O3—H3B	104.4	C14—C19—C18	120.1 (4)
Ni1—O4—H4A	109.2	C14—C19—H19	119.9
Ni1—O4—H4B	109.3	C18—C19—H19	119.9
H4A—O4—H4B	104.5	O5—C20—Ni1ⁱⁱⁱ	60.6 (2)
C20—O5—Ni1ⁱⁱⁱ	88.3 (3)	O5—C20—O6	121.4 (4)
C20—O6—Ni1ⁱⁱⁱ	87.8 (3)	O5—C20—C18	119.1 (4)
N2—N1—Ni1	129.7 (3)	O6—C20—Ni1ⁱⁱⁱ	60.9 (2)
C1—N1—Ni1	124.8 (4)	O6—C20—C18	119.5 (4)
C1—N1—N2	105.4 (4)	C18—C20—Ni1ⁱⁱⁱ	178.1 (3)
N1—N2—H2	124.3	O7—C21—N7	120.4 (4)
C3—N2—N1	111.3 (4)	O7—C21—C27ⁱⁱ	123.0 (5)
C3—N2—H2	124.3	N7—C21—C27ⁱⁱ	116.6 (4)
C9—N3—S1	106.3 (4)	O8—C22—N7	120.7 (4)
C8—N4—S1	106.5 (4)	O8—C22—C23	123.0 (4)
N6—N5—H5	123.8	N7—C22—C23	116.3 (4)
C12—N5—H5	123.8	C24—C23—C22	119.9 (4)
C12—N5—N6	112.4 (4)	C25—C23—C22	119.3 (4)
C11—N6—N5	104.0 (4)	C25—C23—C24	120.7 (4)
C21—N7—C16	117.5 (4)	C23—C24—C24ⁱⁱ	119.9 (5)
C22—N7—C16	117.0 (4)	C23—C24—C27ⁱⁱ	121.8 (4)
C22—N7—C21	125.5 (4)	C24ⁱⁱ—C24—C27ⁱⁱ	118.3 (5)
N1—C1—H1	123.8	C23—C25—H25	120.0
N1—C1—C2	112.4 (5)	C23—C25—C26	120.0 (5)
C2—C1—H1	123.8	C26—C25—H25	120.0
C1—C2—C4	128.0 (4)	C25—C26—H26	119.8
C3—C2—C1	102.7 (4)	C27—C26—C25	120.5 (5)
C3—C2—C4	129.3 (5)	C27—C26—H26	119.8
N2—C3—C2	108.2 (5)	C24ⁱⁱ—C27—C21ⁱⁱ	119.3 (4)
N2—C3—H3	125.9	C26—C27—C21ⁱⁱ	120.1 (4)
C2—C3—H3	125.9	C26—C27—C24ⁱⁱ	120.6 (4)
C5—C4—C2	121.7 (5)	C28—N8—C29	117.5 (5)
C5—C4—C9	114.7 (5)	C30—N8—C28	120.7 (4)
C9—C4—C2	123.6 (4)	C30—N8—C29	121.8 (5)
C4—C5—H5A	118.2	N8—C28—H28A	109.5
C4—C5—C6	123.5 (5)	N8—C28—H28B	109.5
C6—C5—H5A	118.2	N8—C28—H28C	109.5
C5—C6—H6	118.3	H28A—C28—H28B	109.5
C7—C6—C5	123.3 (5)	H28A—C28—H28C	109.5
C7—C6—H6	118.3	H28B—C28—H28C	109.5
C6—C7—C8	115.0 (4)	N8—C29—H29A	109.5
C6—C7—C10	122.5 (4)	N8—C29—H29B	109.5
C8—C7—C10	122.4 (4)	N8—C29—H29C	109.5
N4—C8—C7	124.9 (5)	H29A—C29—H29B	109.5
N4—C8—C9	113.7 (4)	H29A—C29—H29C	109.5
C9—C8—C7	121.4 (4)	H29B—C29—H29C	109.5
N3—C9—C4	125.1 (5)	O9—C30—N8	125.4 (5)
N3—C9—C8	112.8 (4)	O9—C30—H30	117.3
C8—C9—C4	122.1 (4)	N8—C30—H30	117.3
C11—C10—C7	127.0 (5)	H10A—O10—H10B	104.5
C12—C10—C7	129.1 (4)

Ni1—O1—C13—O2	−2.5 (7)	C7—C8—C9—N3	−179.1 (4)
Ni1—O1—C13—C14	175.2 (3)	C7—C8—C9—C4	0.1 (7)
Ni1ⁱⁱⁱ—O5—C20—O6	2.5 (4)	C7—C10—C11—N6	−178.7 (5)
Ni1ⁱⁱⁱ—O5—C20—C18	−177.8 (4)	C7—C10—C12—N5	179.4 (5)
Ni1ⁱⁱⁱ—O6—C20—O5	−2.5 (4)	C8—C7—C10—C11	−168.5 (5)
Ni1ⁱⁱⁱ—O6—C20—C18	177.8 (4)	C8—C7—C10—C12	11.8 (8)
Ni1—N1—N2—C3	−177.3 (3)	C9—C4—C5—C6	−0.1 (7)
Ni1—N1—C1—C2	177.0 (3)	C10—C7—C8—N4	1.4 (8)
S1—N3—C9—C4	−178.5 (4)	C10—C7—C8—C9	179.8 (4)
S1—N3—C9—C8	0.7 (5)	C11—C10—C12—N5	−0.4 (6)
S1—N4—C8—C7	178.6 (4)	C12—N5—N6—C11	1.0 (6)
S1—N4—C8—C9	0.1 (5)	C12—C10—C11—N6	1.1 (6)
O1—C13—C14—C15	9.4 (6)	C13—C14—C15—C16	−177.7 (4)
O1—C13—C14—C19	−168.5 (4)	C13—C14—C19—C18	177.3 (4)
O2—C13—C14—C15	−172.8 (4)	C14—C15—C16—N7	179.7 (4)
O2—C13—C14—C19	9.4 (7)	C14—C15—C16—C17	−0.3 (7)
O8—C22—C23—C24	176.5 (5)	C15—C14—C19—C18	−0.6 (7)
O8—C22—C23—C25	−0.5 (7)	C15—C16—C17—C18	0.8 (7)
N1—N2—C3—C2	0.2 (5)	C16—N7—C21—O7	8.2 (7)
N1—C1—C2—C3	0.9 (6)	C16—N7—C21—C27ⁱⁱ	−171.9 (4)
N1—C1—C2—C4	179.0 (4)	C16—N7—C22—O8	−1.9 (6)
N2—N1—C1—C2	−0.8 (5)	C16—N7—C22—C23	176.2 (4)
N3—S1—N4—C8	0.2 (4)	C16—C17—C18—C19	−1.2 (7)
N4—S1—N3—C9	−0.5 (4)	C16—C17—C18—C20	178.2 (4)
N4—C8—C9—N3	−0.6 (6)	C17—C18—C19—C14	1.1 (7)
N4—C8—C9—C4	178.7 (4)	C17—C18—C20—O5	−174.2 (4)
N5—N6—C11—C10	−1.2 (6)	C17—C18—C20—O6	5.5 (7)
N6—N5—C12—C10	−0.3 (6)	C19—C14—C15—C16	0.2 (7)
N7—C16—C17—C18	−179.2 (4)	C19—C18—C20—O5	5.2 (7)
N7—C22—C23—C24	−1.6 (6)	C19—C18—C20—O6	−175.1 (4)
N7—C22—C23—C25	−178.6 (4)	C20—C18—C19—C14	−178.3 (4)
C1—N1—N2—C3	0.3 (5)	C21—N7—C16—C15	−90.6 (5)
C1—C2—C3—N2	−0.6 (5)	C21—N7—C16—C17	89.4 (5)
C1—C2—C4—C5	6.4 (8)	C21—N7—C22—O8	176.4 (4)
C1—C2—C4—C9	−173.6 (5)	C21—N7—C22—C23	−5.5 (6)
C2—C4—C5—C6	179.9 (5)	C22—N7—C16—C15	87.8 (5)
C2—C4—C9—N3	−1.0 (8)	C22—N7—C16—C17	−92.2 (5)
C2—C4—C9—C8	179.9 (4)	C22—N7—C21—O7	−170.1 (5)
C3—C2—C4—C5	−176.0 (5)	C22—N7—C21—C27ⁱⁱ	9.8 (6)
C3—C2—C4—C9	4.0 (8)	C22—C23—C24—C24ⁱⁱ	−175.5 (5)
C4—C2—C3—N2	−178.7 (5)	C22—C23—C24—C27ⁱⁱ	3.7 (6)
C4—C5—C6—C7	0.3 (9)	C22—C23—C25—C26	175.8 (4)
C5—C4—C9—N3	179.1 (5)	C23—C25—C26—C27	0.3 (7)
C5—C4—C9—C8	−0.1 (7)	C24—C23—C25—C26	−1.3 (7)
C5—C6—C7—C8	−0.3 (8)	C25—C23—C24—C24ⁱⁱ	1.5 (8)
C5—C6—C7—C10	180.0 (5)	C25—C23—C24—C27ⁱⁱ	−179.3 (4)
C6—C7—C8—N4	−178.3 (5)	C25—C26—C27—C21ⁱⁱ	−179.8 (5)
C6—C7—C8—C9	0.1 (7)	C25—C26—C27—C24ⁱⁱ	0.4 (7)
C6—C7—C10—C11	11.2 (8)	C28—N8—C30—O9	1.6 (9)
C6—C7—C10—C12	−168.5 (5)	C29—N8—C30—O9	−177.0 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2^iv	0.87	1.92	2.758 (5)	162
O3—H3B···N6^v	0.87	2.18	2.986 (5)	154
O4—H4A···O2	0.87	1.86	2.640 (4)	148
O4—H4B···O9^iv	0.87	1.83	2.695 (5)	173
N2—H2···O9^iv	0.88	1.92	2.779 (5)	166
N5—H5···N6^vi	0.88	2.20	2.956 (6)	144
C1—H1···O10^v	0.95	2.57	3.46 (3)	155
C11—H11···O1^v	0.95	2.54	3.210 (6)	127
C11—H11···O6^vii	0.95	2.49	3.279 (6)	141
C12—H12···O2^viii	0.95	2.46	3.168 (6)	131
C28—H28A···N5^v	0.98	2.65	3.426 (8)	136
C28—H28B···O4^iv	0.98	2.72	3.414 (6)	128
C28—H28C···O8	0.98	2.26	3.157 (7)	151
O10—H10A···O7	0.87	2.08	2.95 (3)	180
O10—H10B···O6^vii	0.87	2.20	3.01 (3)	155

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

Acknowledgements

We appreciate the College of Chemistry and Chemical Engineering of Nanjing University for providing the experimental platforms.

Funding information

Funding for this research was provided by: National Natural Science Foundation of China (award No. 22071104).

References

Bourhis, L. J., Dolomanov, O. V., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2015). Acta Cryst. A71, 59–75. Web of Science CrossRef IUCr Journals Google Scholar
Bruker (2016). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389–397. Web of Science CrossRef CAS IUCr Journals Google Scholar
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 Google Scholar
Dong, Q., Huang, Y., Wan, J., Lu, Z., Wang, Z., Gu, C., Duan, J. & Bai, J. (2023). J. Am. Chem. Soc. 145, 8043–8051. CSD CrossRef CAS PubMed 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
Huang, K. (2023). CCDC 2270656: Experimental Crystal Structure Determination. https://dx.doi.org/10.5517/ccdc.csd.cc2g6szg. Google Scholar
Khokhar, S., Anand, H. & Chand, P. (2022). J. Energy Storage, 56, 124045. CrossRef Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Li, X.-S., Zhao, J., Hou, S.-L., Xu, H., Liang, Z.-L., Shi, Y. & Zhao, B. (2024). CCS Chem. 6, 2982–2995. CrossRef CAS Google Scholar
Shah, J., Wu, T., Lucero, J., Carreon, M. A. & Carreon, M. L. (2019). ACS Sustainable Chem. Eng. 7, 377–383. CrossRef CAS Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Tian, Y., Li, J., Chen, Y.-Q., Wu, H.-P., Yang, G.-L., Li, M. & Liu, S.-J. (2023). J. Solid State Chem. 323, 124045. CSD CrossRef Google Scholar
Wang, X., Li, B., Wu, Y.-P., Tsamis, A., Yu, H.-G., Liu, S., Zhao, J., Li, Y.-S. & Li, D.-S. (2020). Inorg. Chem. 59, 4764–4771. CSD CrossRef CAS PubMed Google Scholar
Xia, L., Wang, Q. & Hu, M. (2022). Beilstein J. Nanotechnol. 13, 763–777. CrossRef CAS PubMed Google Scholar
Xiong, G., Xu, W., Liang, L., Huang, K., Zhang, X. & Qin, D. (2024). J. Mol. Struct. 1303, 137538. CSD CrossRef Google Scholar