Poly[bis­[μ2-4,4′-bis­(imidazol-1-ylmeth­yl)biphenyl-κ2N:N′]di­chlorido­nickel(II)]

Deng, M.; Yin, Y.; Wang, S.-S.; Qi, X.-Y.; Zhu, A.-X.

doi:10.1107/S2414314622003777

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 7| Part 4| April 2022| x220377

https://doi.org/10.1107/S2414314622003777

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Poly[bis[μ₂-4,4′-bis(imidazol-1-ylmethyl)biphenyl-κ²N:N′]dichloridonickel(II)]

Min Deng,^a Yue Yin,^a Shan-Shan Wang,^a Xin-Yi Qi ^a and Ai-Xin Zhu ^a ^*

^aFaculty of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650050, People's Republic of China
^*Correspondence e-mail: zaxchem@126.com

Edited by M. Zeller, Purdue University, USA (Received 1 April 2022; accepted 6 April 2022; online 12 April 2022)

In the title compound, [NiCl₂(C₂₀H₁₈N₄)₂]_n, the Ni²⁺ cation is situated on an inversion center and is coordinated by two chloride ions and four imidazole N atoms of four different 4,4′-bis[(1H-imidazol-1-yl)methyl]-1,1′-biphenyl (BIMB), forming a slightly distorted octahedral geometry. Each BIMB ligand adopts a linear linker to connect Ni²⁺ ions, forming a two-dimensional layer with an sql network. In the crystal, neighboring layers repeat in an ABAB stacking mode, and weak intermolecular C—H⋯Cl hydrogen bonds between alternate layers lead to a three-dimensional, twofold interpenetrated, supramolecular framework with a pcu topology net.

Keywords: crystal structure; coordination polymer; imidazole; nickel.

CCDC reference: 2164744

Structure description

Over the last two decades, imidazole and its derivatives have attracted a lot of attention as N-heterocyclic aromatic ligands, since they can easily form metal–imidazole frameworks with special luminescent, magnetic and favorable gas-adsorption abilities (Banerjee et al. 2008 ; Zhang et al. 2012 ; Zhu et al. 2012 ; Chen et al. 2014 ). As an extended imidazole-type linker, the flexible ligand 4,4′-bis[(1H-imidazol-1-yl)methyl]-1,1′-biphenyl (BIMB) exhibits a geometrical diversity with cis or trans conformations, leading to diverse structures of coordination compounds. Until now, most reported metal–organic compounds based on BIMB ligands have employed organic multicarboxylates as co-ligands because BIMB is a neutral ligand and another anion is needed to balance the charge requirement to form a neutral framework. Common inorganic anions such as Cl⁻, Br⁻, I⁻, NO₃⁻, SO₄²⁻, N₃⁻, etc. can also be used as co-ligands to balance the charge requirement. However, only ten examples of neutral, BIMB-based metal–organic compounds have been reported [according to the Cambridge Structural Database (CSD, Version 5.43 with update of March, 2022; Groom et al., 2016 ) with inorganic anions as co-ligands.

The asymmetric unit of the title compound, [NiCl₂(C₂₀H₁₈N₄)₂]_n, contains one half nickel(II) ion, two half BIMB ligands and one chloride ion (Fig. 1). The nickel(II) ion sits on an inversion center and is coordinated by four imidazole nitrogen atoms from four different BIMB ligands [Ni—N = 2.100 (3)–2.108 (3) Å] and two chloride ions [Ni—Cl = 2.4793 (11) Å], forming a slightly distorted octahedral geometry. In the crystal, the BIMB ligands have twofold rotational symmetry, being bisected by rotation axes, and the biphenyl groups are not coplanar, with dihedral angles of 33.21 (10) and 35.4 (10)° between the ring planes. The dihedral angles between the imidazole ring plane and the average plane of the biphenyl group are 87.71 (14) and 81.93 (14)°. Each BIMB ligand exhibits a cis-conformation relative to the average plane of the biphenyl group, and acts as a linear linker between Ni²⁺ ions, which gives a corrugated two-dimensional layer structure with an sql (square lattice) network as illustrated in Fig. 2. The layers stack in an –ABAB– mode, and the Ni²⁺ ion in one layer is located at the center of the grid of adjacent layers. Thus, there are no residual solvent-accessible voids in this compound. Alternate layers between A—A or B—B layers are further linked by C—H⋯Cl hydrogen bonds (Table 1, Figs. 3 and 4) to form a three-dimensional, twofold interpenetrated, supramolecular framework with a pcu (primitive cubic) topology network (Fig. 5).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯Cl1ⁱ	0.93	2.79	3.605 (4)	147
C14—H14B⋯Cl1ⁱ	0.97	2.80	3.686 (5)	153
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Figure 1
The coordination environment of the zinc ions and the BIMB ligands in the title compound, with displacement ellipsoids drawn at the 30% probability level. H atoms are omitted for clarity. [Symmetry codes: (A) $[{1\over 2}]$ − x, $[{1\over 2}]$ − y, 1 − z; (B) −x, y, $[{1\over 2}]$ − z; (C) 1 − x, y, $[{1\over 2}]$ − z; (D) $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z; (E) x − $[{1\over 2}]$ , $[{1\over 2}]$ − y, $[{1\over 2}]$ + z.]

Figure 2
The two-dimensional structure of the title compound with sql network viewed along the b axis.

Figure 3
The packing of the title compound viewed along the b axis. H atoms are omitted for clarity.

Figure 4
View of the C—H⋯Cl hydrogen bonds (dashed lines) between alternate layers along the c axis. H atoms not involved in hydrogen bonding are omitted.

Figure 5
The twofold interpenetrated supramolecular framework with a pcu topology network connected by C—H⋯Cl hydrogen bonds (shown as dashed lines).

The structure of the title compound is isomorphous to that of the cadmium(II) compound, whose structure has been studied at 200 K (Zhao et al. 2003 ). This structural similarity of the Cd^II and Ni^II compounds is somewhat unexpected in view of the different effective radii of these ions (Shannon & Prewitt, 1969 , 1970 ), which causes the differences between M—N distances [Cd—-N = 2.339 (2)–2.364 (2) Å in the cadmium(II) compound]. It should also be noted that the title compound was easily obtained within one day using solvothermal conditions, whereas the cadmium(II) compound was obtained after several weeks using a slow-diffusion method.

Synthesis and crystallization

A mixture of NiCl₂·H₂O (24 mg, 0.1 mmol), BIMB (62 mg, 0.2 mmol) and DMF (6 ml) was added to a 20 ml glass vial and then ultrasonicated for 1 minute. The vial was capped tightly and placed in an oven at 120°C. After 12 h, the vial was removed from the oven and allowed to cool to room temperature. The light-green transparent needle-like crystals were collected by filtration, washed with DMF and dried under ambient conditions. About 34 mg of product was obtained (44% yield based on BIMB ligand). The phase purity of the bulk sample was verified by powder X-ray diffraction (PXRD). The experimental and simulated powder XRD patterns of the title compound are displayed in Fig. S1 of the supporting information. Their peak positions are in good agreement with each other, indicating the phase purity of the title compound (slight intensity mismatches due to preferred orientation are observed).

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	[NiCl₂(C₂₀H₁₈N₄)₂]
M_r	758.38
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	26.453 (3), 7.3571 (7), 18.099 (2)
β (°)	93.223 (11)
V (Å³)	3516.8 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.75
Crystal size (mm)	0.30 × 0.22 × 0.16

Data collection
Diffractometer	Oxford Diffraction, Xcalibur, Eos, Gemini
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.856, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	16025, 4343, 2543
R_int	0.078
(sin θ/λ)_max (Å⁻¹)	0.692

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.072, 0.161, 1.06
No. of reflections	4343
No. of parameters	232
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.27
Computer programs: CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and DIAMOND (Brandenburg, 1999 ).

Structural data

CCDC reference: 2164744

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314622003777/zl4050sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314622003777/zl4050Isup3.hkl

The experimental and simulated powder XRD patterns of the title compound. DOI: https://doi.org/10.1107/S2414314622003777/zl4050sup4.docx

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: DIAMOND (Brandenburg, 1999).

Poly[bis[µ₂-4,4'-bis(imidazol-1-ylmethyl)biphenyl-κ²N:N']dichloridonickel(II)] top

Crystal data top

[NiCl₂(C₂₀H₁₈N₄)₂]	F(000) = 1576
M_r = 758.38	D_x = 1.432 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 26.453 (3) Å	Cell parameters from 3041 reflections
b = 7.3571 (7) Å	θ = 2.7–22.6°
c = 18.099 (2) Å	µ = 0.75 mm⁻¹
β = 93.223 (11)°	T = 296 K
V = 3516.8 (7) Å³	Needle, green
Z = 4	0.30 × 0.22 × 0.16 mm

Data collection top

Oxford Diffraction, Xcalibur, Eos, Gemini diffractometer	2543 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	R_int = 0.078
ω scans	θ_max = 29.5°, θ_min = 2.3°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2015)	h = −35→35
T_min = 0.856, T_max = 1.000	k = −9→10
16025 measured reflections	l = −24→19
4343 independent reflections

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)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.161	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0438P)² + 5.351P] where P = (F_o² + 2F_c²)/3
4343 reflections	(Δ/σ)_max < 0.001
232 parameters	Δρ_max = 0.61 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. All H atoms were placed in idealized positions (C—H = 0.93 Å for aromatic H; C—H = 0.97 Å for methylene H) and refined as riding atoms with U_iso(H) = 1.2U_eq(C).

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

	x	y	z	U_iso*/U_eq
Ni1	0.250000	0.250000	0.500000	0.0419 (2)
Cl1	0.21866 (4)	0.51154 (14)	0.57071 (6)	0.0488 (3)
N1	0.22244 (12)	0.3739 (5)	0.40075 (19)	0.0423 (8)
N2	0.20188 (12)	0.5693 (5)	0.31205 (19)	0.0454 (9)
N3	0.32078 (12)	0.3777 (5)	0.49579 (19)	0.0451 (9)
N4	0.38019 (12)	0.5864 (5)	0.4895 (2)	0.0454 (9)
C1	0.21920 (15)	0.5462 (6)	0.3818 (2)	0.0480 (11)
H1	0.228055	0.641502	0.413725	0.058*
C2	0.19229 (17)	0.4035 (7)	0.2839 (3)	0.0605 (13)
H2	0.179357	0.375818	0.236414	0.073*
C3	0.20524 (17)	0.2848 (7)	0.3387 (3)	0.0594 (13)
H3	0.202711	0.159098	0.334459	0.071*
C4	0.19061 (16)	0.7409 (7)	0.2746 (3)	0.0598 (13)
H4A	0.205060	0.740434	0.226555	0.072*
H4B	0.205927	0.839897	0.303368	0.072*
C5	0.13415 (16)	0.7708 (6)	0.2650 (3)	0.0485 (11)
C6	0.10774 (17)	0.7322 (6)	0.1991 (3)	0.0555 (12)
H6	0.125207	0.697958	0.158149	0.067*
C7	0.05550 (17)	0.7438 (6)	0.1933 (3)	0.0511 (11)
H7	0.038471	0.716996	0.148230	0.061*
C8	0.02803 (15)	0.7940 (5)	0.2523 (2)	0.0443 (11)
C9	0.05500 (17)	0.8394 (7)	0.3182 (3)	0.0568 (12)
H9	0.037767	0.877617	0.358795	0.068*
C10	0.10719 (17)	0.8279 (7)	0.3234 (3)	0.0601 (13)
H10	0.124556	0.859617	0.367591	0.072*
C11	0.33046 (15)	0.5513 (6)	0.4876 (2)	0.0460 (11)
H11	0.305554	0.639986	0.481224	0.055*
C12	0.36761 (17)	0.2989 (6)	0.5055 (3)	0.0573 (13)
H12	0.373160	0.175661	0.513987	0.069*
C13	0.40491 (18)	0.4252 (6)	0.5009 (3)	0.0580 (13)
H13	0.439701	0.405819	0.504830	0.070*
C14	0.40289 (17)	0.7651 (6)	0.4815 (3)	0.0523 (12)
H14A	0.425099	0.790809	0.524742	0.063*
H14B	0.376426	0.856560	0.478823	0.063*
C15	0.43247 (16)	0.7761 (6)	0.4137 (3)	0.0474 (11)
C16	0.48277 (16)	0.8245 (6)	0.4154 (3)	0.0558 (12)
H16	0.499348	0.852339	0.460692	0.067*
C17	0.50950 (17)	0.8329 (7)	0.3518 (3)	0.0588 (13)
H17	0.543335	0.867828	0.354691	0.071*
C18	0.48594 (16)	0.7894 (5)	0.2841 (2)	0.0468 (11)
C19	0.43553 (17)	0.7414 (6)	0.2819 (3)	0.0544 (12)
H19	0.418879	0.713521	0.236701	0.065*
C20	0.40927 (17)	0.7340 (6)	0.3457 (3)	0.0556 (12)
H20	0.375352	0.700011	0.342800	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0420 (4)	0.0360 (4)	0.0478 (5)	0.0039 (3)	0.0020 (3)	0.0062 (4)
Cl1	0.0494 (6)	0.0406 (6)	0.0563 (7)	0.0077 (5)	0.0024 (5)	0.0018 (5)
N1	0.0364 (19)	0.042 (2)	0.048 (2)	−0.0009 (16)	−0.0007 (16)	0.0031 (17)
N2	0.0367 (19)	0.050 (2)	0.049 (2)	0.0005 (17)	−0.0055 (16)	0.0120 (18)
N3	0.0380 (19)	0.039 (2)	0.059 (2)	0.0035 (16)	0.0041 (17)	0.0061 (18)
N4	0.040 (2)	0.036 (2)	0.060 (2)	−0.0003 (16)	0.0051 (17)	0.0076 (17)
C1	0.046 (3)	0.047 (3)	0.050 (3)	−0.002 (2)	−0.007 (2)	0.000 (2)
C2	0.060 (3)	0.060 (3)	0.059 (3)	0.014 (3)	−0.016 (2)	−0.005 (3)
C3	0.055 (3)	0.046 (3)	0.075 (4)	0.009 (2)	−0.013 (3)	−0.005 (3)
C4	0.044 (3)	0.065 (3)	0.069 (3)	−0.003 (2)	−0.004 (2)	0.027 (3)
C5	0.045 (2)	0.045 (3)	0.055 (3)	0.000 (2)	−0.005 (2)	0.015 (2)
C6	0.052 (3)	0.056 (3)	0.058 (3)	0.005 (2)	−0.004 (2)	0.002 (2)
C7	0.053 (3)	0.051 (3)	0.048 (3)	−0.001 (2)	−0.013 (2)	−0.002 (2)
C8	0.048 (2)	0.037 (2)	0.046 (3)	−0.0001 (18)	−0.009 (2)	0.004 (2)
C9	0.053 (3)	0.068 (3)	0.048 (3)	0.002 (2)	−0.006 (2)	−0.001 (3)
C10	0.052 (3)	0.072 (3)	0.055 (3)	−0.002 (3)	−0.018 (2)	0.001 (3)
C11	0.037 (2)	0.045 (3)	0.056 (3)	0.0067 (19)	0.001 (2)	0.006 (2)
C12	0.055 (3)	0.040 (3)	0.077 (4)	0.008 (2)	0.007 (3)	0.012 (2)
C13	0.049 (3)	0.046 (3)	0.079 (4)	0.008 (2)	0.002 (2)	0.004 (3)
C14	0.051 (3)	0.046 (3)	0.060 (3)	−0.003 (2)	0.005 (2)	−0.001 (2)
C15	0.045 (2)	0.040 (3)	0.057 (3)	0.001 (2)	0.003 (2)	0.001 (2)
C16	0.044 (3)	0.062 (3)	0.061 (3)	−0.004 (2)	0.000 (2)	0.000 (3)
C17	0.039 (2)	0.060 (3)	0.078 (4)	−0.006 (2)	0.005 (2)	−0.002 (3)
C18	0.046 (3)	0.032 (2)	0.062 (3)	0.0030 (18)	0.005 (2)	0.000 (2)
C19	0.048 (3)	0.058 (3)	0.057 (3)	−0.002 (2)	−0.001 (2)	−0.002 (2)
C20	0.043 (3)	0.058 (3)	0.066 (3)	−0.004 (2)	0.003 (2)	−0.001 (3)

Geometric parameters (Å, º) top

Ni1—N3ⁱ	2.100 (3)	C6—H6	0.9300
Ni1—N3	2.100 (3)	C7—C8	1.377 (6)
Ni1—N1	2.108 (3)	C7—H7	0.9300
Ni1—N1ⁱ	2.108 (3)	C8—C9	1.395 (6)
Ni1—Cl1	2.4793 (11)	C8—C8ⁱⁱ	1.480 (8)
Ni1—Cl1ⁱ	2.4793 (11)	C9—C10	1.381 (6)
N1—C1	1.315 (5)	C9—H9	0.9300
N1—C3	1.357 (5)	C10—H10	0.9300
N2—C1	1.330 (5)	C11—H11	0.9300
N2—C2	1.341 (6)	C12—C13	1.361 (6)
N2—C4	1.456 (5)	C12—H12	0.9300
N3—C11	1.312 (5)	C13—H13	0.9300
N3—C12	1.370 (5)	C14—C15	1.495 (6)
N4—C11	1.339 (5)	C14—H14A	0.9700
N4—C13	1.365 (5)	C14—H14B	0.9700
N4—C14	1.456 (5)	C15—C16	1.376 (6)
C1—H1	0.9300	C15—C20	1.378 (6)
C2—C3	1.351 (6)	C16—C17	1.386 (6)
C2—H2	0.9300	C16—H16	0.9300
C3—H3	0.9300	C17—C18	1.380 (6)
C4—C5	1.510 (6)	C17—H17	0.9300
C4—H4A	0.9700	C18—C19	1.378 (6)
C4—H4B	0.9700	C18—C18ⁱⁱⁱ	1.476 (9)
C5—C10	1.374 (6)	C19—C20	1.382 (6)
C5—C6	1.377 (6)	C19—H19	0.9300
C6—C7	1.383 (6)	C20—H20	0.9300

N3ⁱ—Ni1—N3	180.0	C7—C6—H6	119.7
N3ⁱ—Ni1—N1	87.59 (13)	C8—C7—C6	121.8 (4)
N3—Ni1—N1	92.41 (13)	C8—C7—H7	119.1
N3ⁱ—Ni1—N1ⁱ	92.41 (13)	C6—C7—H7	119.1
N3—Ni1—N1ⁱ	87.59 (13)	C7—C8—C9	117.4 (4)
N1—Ni1—N1ⁱ	180.00 (17)	C7—C8—C8ⁱⁱ	121.8 (4)
N3ⁱ—Ni1—Cl1	90.22 (10)	C9—C8—C8ⁱⁱ	120.8 (5)
N3—Ni1—Cl1	89.78 (10)	C10—C9—C8	120.3 (5)
N1—Ni1—Cl1	89.69 (10)	C10—C9—H9	119.8
N1ⁱ—Ni1—Cl1	90.31 (10)	C8—C9—H9	119.8
N3ⁱ—Ni1—Cl1ⁱ	89.78 (10)	C5—C10—C9	121.8 (4)
N3—Ni1—Cl1ⁱ	90.22 (10)	C5—C10—H10	119.1
N1—Ni1—Cl1ⁱ	90.31 (10)	C9—C10—H10	119.1
N1ⁱ—Ni1—Cl1ⁱ	89.69 (10)	N3—C11—N4	112.5 (4)
Cl1—Ni1—Cl1ⁱ	180.0	N3—C11—H11	123.8
C1—N1—C3	103.7 (4)	N4—C11—H11	123.8
C1—N1—Ni1	130.8 (3)	C13—C12—N3	110.9 (4)
C3—N1—Ni1	125.5 (3)	C13—C12—H12	124.6
C1—N2—C2	107.0 (4)	N3—C12—H12	124.6
C1—N2—C4	127.1 (4)	C12—C13—N4	105.0 (4)
C2—N2—C4	125.7 (4)	C12—C13—H13	127.5
C11—N3—C12	104.2 (4)	N4—C13—H13	127.5
C11—N3—Ni1	128.3 (3)	N4—C14—C15	111.6 (4)
C12—N3—Ni1	127.4 (3)	N4—C14—H14A	109.3
C11—N4—C13	107.3 (4)	C15—C14—H14A	109.3
C11—N4—C14	125.6 (4)	N4—C14—H14B	109.3
C13—N4—C14	127.1 (4)	C15—C14—H14B	109.3
N1—C1—N2	112.6 (4)	H14A—C14—H14B	108.0
N1—C1—H1	123.7	C16—C15—C20	117.4 (4)
N2—C1—H1	123.7	C16—C15—C14	123.0 (4)
N2—C2—C3	106.0 (4)	C20—C15—C14	119.6 (4)
N2—C2—H2	127.0	C15—C16—C17	122.0 (4)
C3—C2—H2	127.0	C15—C16—H16	119.0
C2—C3—N1	110.8 (4)	C17—C16—H16	119.0
C2—C3—H3	124.6	C18—C17—C16	120.1 (4)
N1—C3—H3	124.6	C18—C17—H17	120.0
N2—C4—C5	110.8 (3)	C16—C17—H17	120.0
N2—C4—H4A	109.5	C19—C18—C17	118.2 (4)
C5—C4—H4A	109.5	C19—C18—C18ⁱⁱⁱ	120.6 (5)
N2—C4—H4B	109.5	C17—C18—C18ⁱⁱⁱ	121.2 (5)
C5—C4—H4B	109.5	C18—C19—C20	121.1 (4)
H4A—C4—H4B	108.1	C18—C19—H19	119.4
C10—C5—C6	118.0 (4)	C20—C19—H19	119.4
C10—C5—C4	120.5 (4)	C15—C20—C19	121.1 (4)
C6—C5—C4	121.4 (5)	C15—C20—H20	119.4
C5—C6—C7	120.6 (5)	C19—C20—H20	119.4
C5—C6—H6	119.7

C3—N1—C1—N2	−0.9 (5)	C12—N3—C11—N4	1.7 (5)
Ni1—N1—C1—N2	176.6 (3)	Ni1—N3—C11—N4	178.2 (3)
C2—N2—C1—N1	1.2 (5)	C13—N4—C11—N3	−1.1 (5)
C4—N2—C1—N1	175.8 (4)	C14—N4—C11—N3	179.6 (4)
C1—N2—C2—C3	−0.9 (5)	C11—N3—C12—C13	−1.7 (5)
C4—N2—C2—C3	−175.6 (4)	Ni1—N3—C12—C13	−178.2 (3)
N2—C2—C3—N1	0.4 (6)	N3—C12—C13—N4	1.1 (6)
C1—N1—C3—C2	0.3 (5)	C11—N4—C13—C12	0.0 (5)
Ni1—N1—C3—C2	−177.4 (3)	C14—N4—C13—C12	179.3 (4)
C1—N2—C4—C5	−105.6 (5)	C11—N4—C14—C15	−116.3 (5)
C2—N2—C4—C5	68.0 (6)	C13—N4—C14—C15	64.6 (6)
N2—C4—C5—C10	77.7 (6)	N4—C14—C15—C16	−123.9 (5)
N2—C4—C5—C6	−98.6 (5)	N4—C14—C15—C20	55.2 (5)
C10—C5—C6—C7	−2.6 (7)	C20—C15—C16—C17	0.6 (7)
C4—C5—C6—C7	173.8 (4)	C14—C15—C16—C17	179.7 (4)
C5—C6—C7—C8	0.0 (7)	C15—C16—C17—C18	−1.0 (7)
C6—C7—C8—C9	2.2 (7)	C16—C17—C18—C19	1.2 (7)
C6—C7—C8—C8ⁱⁱ	−175.6 (3)	C16—C17—C18—C18ⁱⁱⁱ	−177.3 (3)
C7—C8—C9—C10	−2.0 (7)	C17—C18—C19—C20	−1.0 (7)
C8ⁱⁱ—C8—C9—C10	175.9 (4)	C18ⁱⁱⁱ—C18—C19—C20	177.5 (3)
C6—C5—C10—C9	2.8 (7)	C16—C15—C20—C19	−0.4 (7)
C4—C5—C10—C9	−173.6 (4)	C14—C15—C20—C19	−179.5 (4)
C8—C9—C10—C5	−0.5 (8)	C18—C19—C20—C15	0.7 (7)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···Cl1^iv	0.93	2.79	3.605 (4)	147
C14—H14B···Cl1^iv	0.97	2.80	3.686 (5)	153

Symmetry code: (iv) −x+1/2, −y+3/2, −z+1.

Funding information

Funding for this research was provided by: the Research Training Program (KX2021018) for College Students of Yunnan Normal University.

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