Syntheses and structures of two coordination polymers formed by Ni(cyclam)2+ cations and sulfate anions

Tsymbal, L.V.; Andriichuk, I.L.; Bahrin, L.G.; Lampeka, Y.D.

doi:10.1107/S2056989024012337

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Volume 81| Part 2| February 2025|

https://doi.org/10.1107/S2056989024012337

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Syntheses and structures of two coordination polymers formed by Ni(cyclam)²⁺ cations and sulfate anions

Liudmyla V. Tsymbal,^a Irina L. Andriichuk,^a Lucian G. Bahrin ^b and Yaroslaw D. Lampeka ^a ^*

^aL. V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of Ukraine, Prospekt Nauki 31, 03028, Kyiv, Ukraine, and ^b"Petru Poni" Institute of Macromolecular Chemistry, Aleea Gr. Ghica Voda 41A, RO 700487 Iasi, Romania
^*Correspondence e-mail: lampeka@adamant.net

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 17 December 2024; accepted 20 December 2024; online 3 January 2025)

The asymmetric units of catena-poly[[(1,4,8,11-tetraazacyclotetradecane-κ⁴N¹,N⁴,N⁸,N¹¹)nickel(II)]-μ₂-sulfato-κ²O³:O⁴], [Ni(SO₄)(C₁₀H₂₄N₄)]_n (I), and catena-poly[[(1,4,8,11-tetraazacyclotetradecane-κ⁴N¹,N⁴,N⁸,N¹¹)nickel(II)]-μ₂-sulfato-κ²O³:O⁴] hemi[4,4′,4′′,4′′′-(2,2′,4,4′,6,6′-hexamethyl-[1,1′-biphenyl]-3,3′,5,5′-tetrayl)tetrabenzoic acid] nonahydrate], {[Ni(SO₄)(C₁₀H₂₄N₄)]₂·C₄₆H₃₈O₈·18H₂O}_n (II), consist of two crystallographically unique centrosymmetric macrocyclic dications and a sulfate dianion. In II it includes additionally a molecule of the undissociated acid (2,2′,4,4′,6,6′-hexamethyl[1,1′-biphenyl]-3,3′,5,5′-tetrayl)tetra(benzoic acid) located on a crystallographic twofold axis and nine highly disordered water molecules of crystallization. In both compounds, the metal ions are coordinated in the equatorial plane by the four secondary N atoms of the macrocyclic ligand, which adopts the most energetically stable trans-III conformation. Two O atoms of the sulfate anions occupy the trans-axial positions resulting in a slightly tetragonally distorted trans-NiN₄O₂ octahedral coordination geometry. The crystals of both compounds are composed of parallel coordination polymeric chains running along the [101] and [100] directions in I and II, respectively. The distances between the neighboring metal ions in the chains are significantly different [6.5121 (6) Å in I and 6.0649 (3) Å in II] and this peculiarity is explained by the different spatial directivity of the Ni—O coordination bonds (different S—O—Ni angles). As a result of the C—H⋯O hydrogen bonds between the methylene groups of the macrocyclic ligands and the non-coordinated O atoms of the sulfate anion, the coordination-polymeric chains in I are arranged in the two-dimensional layers oriented parallel to the (010) and (101) planes, the intersection of which provides the three-dimensional coherence of the crystals. The three-dimensional supramolecular structure of the crystals II is determined by the network of strong hydrogen bonds formed by the carboxylic acid and the non-coordinated O atoms of the sulfate anions.

Keywords: crystal structure; coordination polymer; cyclam; nickel; sulfate; hydrogen bonds.

CCDC references: 2373135; 2373134

1. Chemical context

Nickel(II) complexes of 14-membered tetradentate azamacrocyclic ligands, in particular, cyclam and its analogues (cyclam = 1,4,8,11-tetraazacyclotetradecane, C₁₀H₂₄N₄, L), are widely used in the formation of coordination polymers and metal–organic frameworks based on oligocarboxylate linkers, which possess many promising applications (Lampeka & Tsymbal, 2004 ; Suh & Moon, 2007 ; Stackhouse & Ma, 2018 ). At the same time, examples of coordination polymers formed by these Ni^II-containing nodes and simple inorganic oxoanions are rare and are limited mainly to compounds containing bridging chromate ligands (see Database survey). Surprisingly, no polymers formed by the sulfate dianion and tetraazamacrocyclic Ni^II cations have been described to date. At the same time, it can be expected that the formation of structures containing two different types of bridging ligand (i.e., organic carboxylates and inorganic oxoanions) will enrich the topological variability of the coordination polymers and their functional characteristics. To check such a possibility, we conducted the reaction between an excess (8:1) of [Ni(L)](ClO₄)₂ and (2,2′,4,4′,6,6′-hexamethyl[1,1′-biphenyl]-3,3′,5,5′-tetrayl)tetra(benzoic acid) (H₄A) in the presence of Na₂SO₄.

The present work describes the preparation and structural characterization of the products of this reaction which are the first representatives of polymeric complexes formed by the [Ni(L)]²⁺ cation and SO₄^2– anions, namely, catena-poly[[(1,4,8,11-tetraazacyclotetradecane-κ⁴N¹,N⁴,N⁸,N¹¹)nickel(II)]-μ₂-sulfato-κ²O³:O⁴], [Ni(SO₄)(C₁₀H₂₄N₄)]_n (I), and catena-poly[[(1,4,8,11-tetraazacyclotetradecane-κ⁴N¹,N⁴,N⁸,N¹¹)nickel(II)]-μ₂-sulfato-κ²O³:O⁴] hemi[4,4′,4′′,4′′′-(2,2′,4,4′,6,6′-hexamethyl-[1,1′-biphenyl]-3,3′,5,5′-tetrayl)tetrabenzoic acid] nonahydrate], {[Ni(SO₄)(C₁₀H₂₄N₄)]₂·C₄₆H₃₈O₈·18H₂O}_n (II).

2. Structural commentary

The asymmetric units of both compounds contain two crystallographically unique centrosymmetric macrocyclic cations [Ni(L)]²⁺ and one sulfate anion (Fig. 1). In II it includes additionally the molecule of the acid H₄A and, according to SQUEEZE calculations, nine highly disordered water molecules of crystallization.

Figure 1
The extended asymmetric units involving complex cations in (a) I and (b) II showing the atom-labeling scheme (displacement ellipsoids are drawn at the 30% probability level, C-bound H atoms are omitted for clarity, intramolecular hydrogen bonds are shown as dotted lines). The relative orientations of the coordination links Ni1—O1—SO₂—O2—Ni2 in each compound are shown on the right. Symmetry codes: (i) −x, −y + 1, −z + 1; (ii) −x + 1, −y + 1, −z + 2; (iii) −x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z + $[{3\over 2}]$ ; (iv) −x + $[{3\over 2}]$ , −y + $[{3\over 2}]$ , −z + $[{3\over 2}]$ .

The coordination environments of the metal ions in I and II are very similar. The Ni^II ions are equatorially coordinated to the four secondary N atoms of the macrocycle L, while the axial positions in the coordination spheres are occupied by the O atoms of the sulfate anions. Since the Ni—N bond lengths, which are typical of high-spin Ni^II 3d⁸ electronic configuration, are slightly shorter than the Ni—O ones (Table 1), the coordination polyhedra in both compounds can be described as tetragonally elongated trans-NiN₄O₂ octahedra. Interestingly, the Ni—O distances are nearly equal in I, while they differ significantly in II (Table 1).

Table 1
Selected geometric parameters (Å, °)

	I	II
Ni1—N1	2.064 (2)	2.061 (4)
Ni1—N2	2.072 (2)	2.065 (4)
Ni2—N3	2.063 (2)	2.073 (4)
Ni2—N4	2.072 (2)	2.062 (4)
Ni1—O1	2.1625 (16)	2.191 (2)
Ni2—O2	2.1696 (16)	2.107 (3)

N1—Ni1—N2ⁱ	85.51 (9)	85.28 (19)
N1—Ni1—N2	94.49 (9)	94.72 (19)
N3—Ni2—N4ⁱⁱ	85.41 (9)	85.84 (19)
N3—Ni2—N4	94.59 (9)	94.16 (19)
Symmetry codes: (i) −x, −y + 1, −z + 1 in I and −x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z + $[{3\over 2}]$ in II; (ii) −x + 1, −y + 1, −z + 2 in I and −x + $[{3\over 2}]$ , −y + $[{3\over 2}]$ , −z + $[{3\over 2}]$ in II.

The macrocyclic ligands L adopt the most energetically stable trans-III (R,R,S,S) conformation (Barefield et al., 1986 ) with the five-membered (N—Ni—N bite angles ca 85°) and six-membered (N—Ni—N bite angles ca 95°) chelate rings being in gauche and chair conformations, respectively (Table 1).

The NiN₄ coordination moieties in I and II are strictly planar because of the location of the metal ions on crystallographic inversion centers. The axial Ni—O bonds are nearly orthogonal to the NiN₄ planes (deviations of the angles N—Ni—O from 90° do not exceed 4°). Analogously to other complexes of the Ni^II macrocyclic cations and carboxylate ligands (Tsymbal et al., 2021 ) the Ni—O coordination interactions in I and II are reinforced by intramolecular hydrogen bonds between the secondary NH atoms of the amine groups and the non-coordinated O atoms of the sulfate anions (Fig. 1, Tables 2 and 3).

Table 2
Hydrogen-bond geometry (Å, °) for I

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3	0.98	2.02	2.916 (3)	151
N2—H2⋯O4	0.98	2.05	2.960 (3)	154
N3—H3⋯O4	0.98	2.01	2.938 (3)	157
N4—H4⋯O3	0.98	2.04	2.946 (3)	153
C5—H5A⋯O3ⁱ	0.97	2.52	3.336 (4)	141
C6—H6B⋯O4ⁱⁱ	0.97	2.51	3.245 (3)	133
Symmetry codes: (i) ; (ii) .

Table 3
Hydrogen-bond geometry (Å, °) for II

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4	0.98	2.32	3.113 (5)	138
N2—H2⋯O3	0.98	2.42	3.267 (4)	144
N4—H4⋯O3ⁱ	0.98	2.10	3.012 (5)	154
O5—H5⋯O4	0.82	1.79	2.597 (5)	169
O7—H7⋯O3ⁱⁱ	0.82	1.85	2.654 (5)	166
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

In both complexes, the sulfate ligands display a μ₂-bis-monodentate bridging mode resulting in the formation of linear (i.e., an angle Ni⋯Ni⋯Ni of 180°), parallel, coordination-polymeric chains running along the [101] and [100] directions in I and II, respectively. Despite close similarities in coordination bond lengths in both compounds, there are several differences in the structures of the polymeric chains connected with the mutual orientation of the constituents. In particular, the angle between the mean NiN₄ planes of the structurally non-equivalent macrocyclic cations in I is 31.44 (9)°, while in II it is 41.6 (2)°. Additionally, the angles between the long axes of these macrocyclic cations passing through the symmetry-related central C atoms of the trimethylene fragments (C2 or C7) and the Ni^II ion are 7.51 (9) and 56.2 (2)° in I and II, respectively. Besides, the distances between the neighboring metal ions in the chains are significantly different [6.5121 (6) Å in I and 6.0649 (3) Å in II]. Obviously, this feature is explained by different mutual spatial directivity of the Ni—O coordination bonds. That is to say, though the angles S1—O1—Ni1 are nearly equal in I and II [126.17 (11) and 127.61 (19)°, respectively], the angles S1—O2—Ni2 differ significantly [126.36 (11) and 135.8 (2)°] (Fig. 1).

The clathrated molecule of the acid H₄A in the crystal of II is localized on a crystallographic twofold axis passing through the C20/C29 carbon atoms (Fig. 2) and is characterized by the non-planar structure manifesting itself in substantial mutual tilting of the aromatic rings. This is caused by repulsive interactions of the hydrogen atoms of the methyl substituents between themselves [the angle between the mean planes of the central trimethylbenzene fragments is 75.3 (2)°] or with the hydrogen atoms of the pendant aromatic rings [the angles between the mean planes of trimethylbenzene rings and the lateral carboxyl-substituted ones are 71.4 (2) and 77.8 (2)°]. The latter values are close to those observed in the complex of a structurally related triphenylphosphonic acid built on a trimethylbenzene core (Tsymbal et al., 2022 ). The angles C11—Cg—C11(−x + $[{3\over 2}]$ , y, −z + 1) and C36—Cg—C36(−x + $[{3\over 2}]$ , y, −z + 1) are 131.2 (1) and 114.8 (1)° (Cg represents the centroid of the corresponding trimethylbenzene ring) and, because of the tilting of these rings, the molecule H₄A as a whole possesses a tetrahedron-like shape. The carboxylic acid groups in H₄A are close to coplanar with their corresponding benzene rings (the angles between their mean planes are smaller than 8°) and are non-delocalized as indicated by the large differences in the lengths of the C—OH (ca 1.30 Å) and C=O (ca 1.20 Å) bonds.

Figure 2
The conformation of the acid H₄A in II with the hydrogen bonds (dotted lines) it forms with the sulfate anions (displacement ellipsoids are drawn at the 30% probability level, C-bound H atoms are omitted for clarity). Symmetry codes: (i) −x + $[{3\over 2}]$ , y, −z + 1; (ii) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (iii) −x + $[{3\over 2}]$ , −y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ .

3. Supramolecular features

The three-dimensional coherence of the crystal of I is supported by weak C—H⋯O hydrogen bonds between the C5 and C6 methylene groups belonging to the structurally non-equivalent macrocyclic cations and the non-coordinated O3 and O4 atoms of the sulfate anion (Table 2). In particular, the polymeric chains in I are arranged in pseudo layers oriented parallel to the (010) plane due to C5—H5A⋯O3 contacts (Fig. 3a). Simultaneously, similar layers, though oriented parallel to the (10 $[\overline{1}]$ ) plane (Fig. 3b), are formed as a result of the C6—H6B⋯O4 interactions. The intersection of these layers results in the formation of a three-dimensional system of hydrogen bonds in the crystal. The shortest distance between the Ni^II ions in neighboring chains is ca 8.0 and 8.3 Å in the former and the latter cases, respectively. It is noteworthy that both the non-coordinated O atoms of the sulfate anion in I are saturated by hydrogen bonds, acting as triple proton acceptors. According to PLATON calculations (Spek, 2020 ), the crystals of I are non-porous.

Figure 3
The hydrogen-bonded (dashed lines) sheets in I parallel to the (a) (010) and (b) (10 $[\overline{1}]$ ) planes (only atoms H5A and H6B participating in interchain hydrogen bonding are shown). Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) −x + 1, −y + 2, −z + 2.

A pivotal role in the formation of the extended structure of the crystals of II is played by the carboxylic acid H₄A. Acting as the proton donor, it forms strong hydrogen bonds with the non-coordinated O3 and O4 atoms of the sulfate anion (Table 3), which belong to four different polymeric chains. These chains act as pillars and, in turn, the anions of each asymmetric units interact with four molecules of the acid (Fig. 4). At the same time, the tetrahedral shape of this molecule prevents the formation of any two-dimensional aggregates, thus resulting in a three-dimensional system of hydrogen bonds in the crystals II. As estimated by PLATON (Spek, 2020), the volume of the solvent-accessible void in II in the form of isolated cavities equals 1667 Å³ (20.9% of the unit-cell volume) which, according to SQUEEZE calculations, are filled with eighteen highly disordered water molecules of crystallization.

Figure 4
Fragment of the crystal structure of II showing the hydrogen bonds (dashed lines) between carboxylate groups of the acid H₄L and the non-coordinated oxygen atoms of the sulfate anions. H atoms at C atoms and methylene groups in benzene rings are not shown. The coordination environment of the Ni^II ions is shown in polyhedral presentation. Symmetry code: (i) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ .

4. Database survey

Data concerning the crystal structure of sulfate complexes of the Ni(L) cation(s) are very limited. In particular, the Cambridge Structural Database (CSD, Version 5.45, last update September 2024; Groom et al., 2016 ) contains characterization of the only one non-polymeric Ni^II complex anion trans-[Ni^II(L)(SO₄)₂]²⁻ (refcode FAFLUV; Churchard et al., 2010 ) and two compounds of the Ni^III complex cation trans-[Ni^III(L)(HSO₄)₂]⁺ (RIGFUM and RIGGIB; Morrison et al., 2023 ). Additionally, the one-dimensional coordination polymer based on the trans-[Ni^III(L)(SO₄)₂]⁻ unit has also been described (RIGGEX; Morrison et al., 2023). It is noteworthy that, despite the different chemical nature of FAFLUV and I and II (i.e. non-polymeric and polymeric, respectively), the coordination bond lengths in all complexes are very similar (cf. average Ni—N and Ni—O distances in FAFLUV of 2.07 and 2.15 Å, respectively, with the corresponding parameters presented in Table 1).

Despite the lack of structurally characterized polymeric Ni^II(L)–sulfate compounds, there is one example of a polymeric complex of this cation with the chromate anion – a ligand that is closely related to sulfate (NAYWUF; Oshio et al., 1997 ). In addition, a number of polymeric complexes of the [Ni(diazacyclam)]²⁺ macrocyclic cation [diazacyclam = (3,10)-R₂-1,3,5,8,10,12-hexaazacyclotetradecane] with the CrO₄^2– anion have been described [GUJNUU; Kim et al., 2000 , and GUJNUU01, Gu et al., 2008 (R = 2-hydroxyethyl); RAHZAD; Ou et al., 2011 (R = propyl); VEWWEB and VEWWIF; Shin et al., 2013 (R = S,S- or R,R-1-phenylethyl)], as well as the coordination polymer with the molybdate anion [GUJPAC; Kim et al., 2000 (R = 2-hydroxyethyl)].

In general, the crystal structures of all of the above-mentioned polymeric complexes of the Ni^II ion are rather similar and related to I and II. Their crystals are also built from parallel polymeric chains and the lengths of the Ni^II—O axial coordination bonds (2.06–2.10 Å) are only slightly shorter than those observed in I and II. This feature, together with strictly linear (NAYWUF and RAHZAD) or close to linear (other complexes) arrangement of the Ni²⁺ ions in the chains and a similar mode of coordination of the MO₄^2– anions to that observed in I, results in a narrow spread of the intrachain metal–metal distances (6.6–6.8 Å). Interestingly, though the average Ni^III—O bond length in RIGGEX (2.11 Å) does not differs significantly from that observed in I or II, a shorter Ni⋯Ni intrachain distance (6.28 Å) in the former polymer is explained by the essential non-linearity of the chains (the angle Ni⋯Ni⋯Ni is ca 164°).

The acid H₄A has been used for the preparation of several polymeric compounds, including complexes of Zr^IV and Hf^IV (Yan et al., 2018 ; Lv et al., 2019 ; Zhang et al., 2020 ), Eu^III (Lv et al., 2021 ), Cd^II (Wang et al., 2019 ) and alkali- and alkaline-earth metal ions (Bahrin et al., 2019 ; Li et al., 2022 ). Additionally, the structures of the uncoordinated acid in solvated (RAXXIY; Moorthy et al., 2005 ) and unsolvated (HEGCEF; Wang et al., 2021 ) states as well as in mono- and dianionic forms (BOVNEI; Bahrin et al., 2019) have been reported. The comparison of structural data available in the literature for uncoordinated H_nA^(4–n)– with those of H₄A in II demonstrates rather minor differences in interatomic distances and angles and in general shapes of the ions and molecules, which obviously is connected with their low conformational flexibility caused by strong intramolecular interatomic repulsions.

5. Synthesis and crystallization

All chemicals and solvents used in this work were purchased from Sigma–Aldrich and used without further purification. The acid H₄A was synthesized according to a procedure described previously (Bahrin et al., 2019). The complex [Ni(L)](ClO₄)₂ was prepared from ethanol solutions as described in the literature (Bosnich et al., 1965 ).

The coordination polymers I and II were prepared as by-products of the reaction between the excess of the perchlorate salt of [Ni(L)]²⁺ cation and the acid H₄A (8:1) in the presence of Na₂SO₄ as follows.

A solution of H₄A (35 mg, 0.050 mmol) in 5 ml of DMF was mixed with a solution of [Ni(L)](ClO₄)₂ (183 mg, 0.40 mmol) dissolved in 5 ml of a DMF/H₂O mixture (1:1 by volume). Na₂SO₄ (100 mg, 0.70 mmol) was then added and a solution was heated at 353 K for 30 min and left to stand at ambient conditions. Light-violet prisms of I, which formed in a week, were filtered off, washed with small amounts of methanol and diethyl ether, and dried in air. Yield: 14 mg (10% based on nickel complex). Analysis calculated for C₁₀H₂₄N₄NiO₄S: C 33.83, H 6.81, N 15.58%. Found: C 33.71, H 6.92, N 15.39%.

Refrigerating the mother liquor obtained after filtering off complex I resulted in the formation of II after one day in the form of nearly colorless light-pink plates. These were filtered off, washed with small amounts of methanol and diethyl ether, and dried in air. Yield: 22 mg (7% based on nickel complex). Analysis calculated for C₆₆H₁₂₂N₈Ni₂O₃₄S₂: C 45.22, H 7.01, N 6.39%. Found: C 45.41, H 7.47, N 6.59%. Single crystals of I and II suitable for X-ray diffraction analysis were selected from the samples resulting from the synthesis.

Caution! Perchlorate salts of metal complexes are potentially explosive and should be handled with care.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. The H atoms in I and II were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.93, 0.96 and 0.97 Å (ring, methyl and methylene H atoms, respectively), N—H distances of 0.98 Å, O—H distances of 0.82 Å (protonated carboxylic group) with U_iso(H) values of 1.2U_eq or 1.5U_eq times those of the corresponding parent atoms. SQUEEZE calculations indicate the presence of nine water molecules of crystallization per asymmetric unit of II.

Table 4
Experimental details

	I	II
Crystal data
Chemical formula	[Ni(SO₄)(C₁₀H₂₄N₄)]	[Ni(SO₄)(C₁₀H₂₄N₄)]₂·C₄₆H₃₈O₈·18H₂O
M_r	355.10	1428.96
Crystal system, space group	Triclinic, P $[\overline{1}]$	Monoclinic, I2/a
Temperature (K)	293	293
a, b, c (Å)	7.9935 (6), 8.3181 (6), 12.1998 (9)	12.1299 (5), 18.5163 (11), 35.621 (2)
α, β, γ (°)	108.308 (7), 102.767 (7), 99.145 (6)	90, 94.777 (4), 90
V (Å³)	727.88 (10)	7972.7 (8)
Z	2	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	1.50	0.59
Crystal size (mm)	0.10 × 0.05 × 0.04	0.10 × 0.04 × 0.01

Data collection
Diffractometer	Xcalibur, Eos	Xcalibur, Eos
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )	Multi-scan (CrysAlis PRO; Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.986, 1.000	0.920, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7381, 2965, 2356	20054, 8085, 3223
R_int	0.036	0.086
(sin θ/λ)_max (Å⁻¹)	0.625	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.080, 1.02	0.077, 0.123, 0.99
No. of reflections	2965	8085
No. of parameters	184	432
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.41	0.25, −0.35
Computer programs: CrysAlis PRO (Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 2373135; 2373134

Crystal structure: contains datablocks I, II. DOI: https://doi.org/10.1107/S2056989024012337/hb8118sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024012337/hb8118Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989024012337/hb8118IIsup3.hkl

checkCIF report

Computing details top

catena-Poly[[(1,4,8,11-tetraazacyclotetradecane-κ⁴N¹,N⁴,N⁸,N¹¹)nickel(II)]-µ₂-sulfato-κ²O³:O⁴] (I) top

Crystal data top

[Ni(SO₄)(C₁₀H₂₄N₄)]	Z = 2
M_r = 355.10	F(000) = 376
Triclinic, P1	D_x = 1.620 Mg m⁻³
a = 7.9935 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.3181 (6) Å	Cell parameters from 2779 reflections
c = 12.1998 (9) Å	θ = 2.6–27.9°
α = 108.308 (7)°	µ = 1.50 mm⁻¹
β = 102.767 (7)°	T = 293 K
γ = 99.145 (6)°	Prism, clear light violet
V = 727.88 (10) Å³	0.10 × 0.05 × 0.04 mm

Data collection top

Xcalibur, Eos diffractometer	2965 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2356 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 16.1593 pixels mm^-1	θ_max = 26.4°, θ_min = 1.8°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2022)	k = −10→10
T_min = 0.986, T_max = 1.000	l = −15→15
7381 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.080	w = 1/[σ²(F_o²) + (0.0285P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
2965 reflections	Δρ_max = 0.41 e Å⁻³
184 parameters	Δρ_min = −0.41 e Å⁻³
0 restraints

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
Ni1	0.000000	0.500000	0.500000	0.01844 (14)
Ni2	0.500000	0.500000	1.000000	0.01761 (14)
S1	0.25415 (9)	0.52446 (9)	0.75638 (5)	0.02297 (18)
O2	0.2854 (2)	0.4234 (2)	0.83542 (14)	0.0247 (4)
O3	0.4087 (3)	0.5606 (4)	0.71535 (19)	0.0627 (8)
O1	0.0987 (2)	0.4245 (2)	0.65152 (14)	0.0255 (5)
O4	0.2186 (3)	0.6902 (3)	0.82444 (17)	0.0520 (7)
N4	0.6885 (3)	0.5545 (3)	0.91572 (18)	0.0234 (5)
H4	0.625381	0.552117	0.836403	0.028*
N1	0.2431 (3)	0.5189 (3)	0.46653 (18)	0.0257 (5)
H1	0.326732	0.513375	0.536522	0.031*
N2	0.0549 (3)	0.7614 (3)	0.60765 (18)	0.0241 (5)
H2	0.126128	0.775590	0.688102	0.029*
N3	0.4696 (3)	0.7518 (3)	1.05788 (18)	0.0227 (5)
H3	0.389541	0.764987	0.989536	0.027*
C4	−0.1178 (4)	0.7948 (4)	0.6181 (3)	0.0375 (8)
H4A	−0.181748	0.808385	0.545437	0.045*
H4B	−0.100321	0.901524	0.685933	0.045*
C5	0.2222 (4)	0.3575 (4)	0.3638 (2)	0.0342 (8)
H5A	0.337616	0.339375	0.358732	0.041*
H5B	0.160841	0.367627	0.289181	0.041*
C10	0.3754 (4)	0.7608 (4)	1.1497 (2)	0.0316 (7)
H10A	0.325008	0.861514	1.163556	0.038*
H10B	0.456846	0.772294	1.225193	0.038*
C7	0.7280 (4)	0.8752 (4)	1.0018 (3)	0.0354 (8)
H7A	0.816441	0.983602	1.025167	0.043*
H7B	0.642961	0.860916	0.926965	0.043*
C6	0.6331 (4)	0.8916 (3)	1.0980 (3)	0.0322 (7)
H6A	0.711889	0.887524	1.169491	0.039*
H6B	0.603806	1.004011	1.119676	0.039*
C3	0.1549 (4)	0.8829 (4)	0.5660 (2)	0.0330 (7)
H3A	0.176117	1.001434	0.622139	0.040*
H3B	0.084841	0.875543	0.487966	0.040*
C2	0.3306 (4)	0.8428 (4)	0.5557 (3)	0.0377 (8)
H2A	0.390275	0.829608	0.629642	0.045*
H2B	0.403653	0.942128	0.549018	0.045*
C9	0.7699 (4)	0.4053 (4)	0.8955 (2)	0.0301 (7)
H9A	0.852602	0.415529	0.970157	0.036*
H9B	0.834192	0.403040	0.836469	0.036*
C8	0.8185 (4)	0.7247 (4)	0.9782 (2)	0.0314 (7)
H8A	0.896344	0.739395	0.929486	0.038*
H8B	0.890260	0.727149	1.054362	0.038*
C1	0.3180 (4)	0.6798 (4)	0.4498 (3)	0.0360 (8)
H1A	0.244293	0.684103	0.376506	0.043*
H1B	0.435079	0.677907	0.440370	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0161 (3)	0.0253 (3)	0.0139 (2)	0.0052 (2)	0.00150 (19)	0.0091 (2)
Ni2	0.0177 (3)	0.0196 (3)	0.0146 (2)	0.0044 (2)	0.00097 (19)	0.0076 (2)
S1	0.0191 (4)	0.0317 (4)	0.0166 (3)	0.0020 (3)	−0.0022 (3)	0.0138 (3)
O2	0.0273 (11)	0.0258 (10)	0.0180 (9)	0.0037 (9)	−0.0044 (8)	0.0129 (8)
O3	0.0203 (12)	0.136 (2)	0.0444 (14)	0.0038 (13)	0.0024 (10)	0.0619 (15)
O1	0.0251 (11)	0.0296 (11)	0.0165 (9)	0.0023 (9)	−0.0044 (8)	0.0104 (8)
O4	0.0816 (18)	0.0276 (12)	0.0285 (12)	0.0197 (12)	−0.0156 (12)	0.0046 (10)
N4	0.0214 (13)	0.0282 (13)	0.0193 (11)	0.0051 (10)	0.0006 (10)	0.0111 (10)
N1	0.0221 (13)	0.0386 (14)	0.0181 (12)	0.0080 (11)	0.0036 (10)	0.0138 (11)
N2	0.0276 (14)	0.0272 (13)	0.0167 (11)	0.0078 (11)	0.0007 (10)	0.0106 (10)
N3	0.0233 (13)	0.0203 (12)	0.0197 (11)	0.0052 (10)	−0.0020 (10)	0.0065 (10)
C4	0.040 (2)	0.0401 (19)	0.0343 (17)	0.0225 (16)	0.0109 (15)	0.0104 (15)
C5	0.0279 (18)	0.050 (2)	0.0317 (17)	0.0179 (16)	0.0165 (14)	0.0151 (15)
C10	0.0370 (19)	0.0306 (17)	0.0246 (15)	0.0150 (14)	0.0076 (13)	0.0039 (13)
C7	0.0340 (19)	0.0276 (16)	0.0391 (18)	−0.0032 (13)	−0.0011 (14)	0.0179 (14)
C6	0.0355 (19)	0.0190 (15)	0.0340 (17)	0.0024 (13)	−0.0006 (14)	0.0085 (13)
C3	0.043 (2)	0.0235 (16)	0.0248 (16)	0.0008 (14)	0.0003 (14)	0.0089 (13)
C2	0.0333 (19)	0.0409 (19)	0.0334 (17)	−0.0101 (15)	0.0016 (14)	0.0213 (15)
C9	0.0266 (17)	0.0396 (18)	0.0251 (15)	0.0134 (14)	0.0077 (13)	0.0104 (14)
C8	0.0240 (17)	0.0365 (18)	0.0302 (16)	−0.0023 (13)	0.0021 (13)	0.0160 (14)
C1	0.0240 (17)	0.058 (2)	0.0313 (16)	0.0046 (15)	0.0089 (13)	0.0247 (16)

Geometric parameters (Å, º) top

Ni1—O1ⁱ	2.1625 (16)	N3—C6	1.475 (4)
Ni1—O1	2.1625 (16)	C4—H4A	0.9700
Ni1—N1	2.064 (2)	C4—H4B	0.9700
Ni1—N1ⁱ	2.064 (2)	C4—C5ⁱ	1.507 (4)
Ni1—N2	2.072 (2)	C5—H5A	0.9700
Ni1—N2ⁱ	2.072 (2)	C5—H5B	0.9700
Ni2—O2ⁱⁱ	2.1696 (16)	C10—H10A	0.9700
Ni2—O2	2.1696 (16)	C10—H10B	0.9700
Ni2—N4ⁱⁱ	2.072 (2)	C10—C9ⁱⁱ	1.514 (4)
Ni2—N4	2.072 (2)	C7—H7A	0.9700
Ni2—N3ⁱⁱ	2.063 (2)	C7—H7B	0.9700
Ni2—N3	2.063 (2)	C7—C6	1.516 (4)
S1—O2	1.4722 (17)	C7—C8	1.526 (4)
S1—O3	1.455 (2)	C6—H6A	0.9700
S1—O1	1.4742 (17)	C6—H6B	0.9700
S1—O4	1.477 (2)	C3—H3A	0.9700
N4—H4	0.9800	C3—H3B	0.9700
N4—C9	1.470 (3)	C3—C2	1.517 (4)
N4—C8	1.473 (3)	C2—H2A	0.9700
N1—H1	0.9800	C2—H2B	0.9700
N1—C5	1.476 (3)	C2—C1	1.522 (4)
N1—C1	1.471 (4)	C9—H9A	0.9700
N2—H2	0.9800	C9—H9B	0.9700
N2—C4	1.475 (3)	C8—H8A	0.9700
N2—C3	1.470 (3)	C8—H8B	0.9700
N3—H3	0.9800	C1—H1A	0.9700
N3—C10	1.471 (3)	C1—H1B	0.9700

O1ⁱ—Ni1—O1	180.0	C6—N3—H3	107.1
N1—Ni1—O1	90.53 (7)	N2—C4—H4A	110.0
N1ⁱ—Ni1—O1	89.47 (7)	N2—C4—H4B	110.0
N1ⁱ—Ni1—O1ⁱ	90.53 (7)	N2—C4—C5ⁱ	108.6 (2)
N1—Ni1—O1ⁱ	89.47 (7)	H4A—C4—H4B	108.3
N1ⁱ—Ni1—N1	180.0	C5ⁱ—C4—H4A	110.0
N1—Ni1—N2	94.49 (9)	C5ⁱ—C4—H4B	110.0
N1—Ni1—N2ⁱ	85.51 (9)	N1—C5—C4ⁱ	108.9 (2)
N1ⁱ—Ni1—N2	85.51 (9)	N1—C5—H5A	109.9
N1ⁱ—Ni1—N2ⁱ	94.49 (9)	N1—C5—H5B	109.9
N2ⁱ—Ni1—O1	87.02 (7)	C4ⁱ—C5—H5A	109.9
N2—Ni1—O1	92.98 (7)	C4ⁱ—C5—H5B	109.9
N2ⁱ—Ni1—O1ⁱ	92.98 (7)	H5A—C5—H5B	108.3
N2—Ni1—O1ⁱ	87.02 (7)	N3—C10—H10A	110.1
N2—Ni1—N2ⁱ	180.00 (7)	N3—C10—H10B	110.1
O2—Ni2—O2ⁱⁱ	180.0	N3—C10—C9ⁱⁱ	108.2 (2)
N4ⁱⁱ—Ni2—O2ⁱⁱ	92.22 (7)	H10A—C10—H10B	108.4
N4—Ni2—O2ⁱⁱ	87.78 (7)	C9ⁱⁱ—C10—H10A	110.1
N4ⁱⁱ—Ni2—O2	87.78 (7)	C9ⁱⁱ—C10—H10B	110.1
N4—Ni2—O2	92.22 (7)	H7A—C7—H7B	107.5
N4—Ni2—N4ⁱⁱ	180.0	C6—C7—H7A	108.5
N3ⁱⁱ—Ni2—O2	87.88 (7)	C6—C7—H7B	108.5
N3—Ni2—O2ⁱⁱ	87.87 (7)	C6—C7—C8	115.2 (2)
N3ⁱⁱ—Ni2—O2ⁱⁱ	92.12 (7)	C8—C7—H7A	108.5
N3—Ni2—O2	92.13 (7)	C8—C7—H7B	108.5
N3ⁱⁱ—Ni2—N4	85.41 (9)	N3—C6—C7	112.4 (2)
N3—Ni2—N4	94.59 (9)	N3—C6—H6A	109.1
N3—Ni2—N4ⁱⁱ	85.41 (9)	N3—C6—H6B	109.1
N3ⁱⁱ—Ni2—N4ⁱⁱ	94.58 (9)	C7—C6—H6A	109.1
N3—Ni2—N3ⁱⁱ	180.00 (11)	C7—C6—H6B	109.1
O2—S1—O1	109.61 (11)	H6A—C6—H6B	107.8
O2—S1—O4	108.92 (11)	N2—C3—H3A	109.2
O3—S1—O2	109.99 (12)	N2—C3—H3B	109.2
O3—S1—O1	109.64 (12)	N2—C3—C2	111.9 (2)
O3—S1—O4	109.85 (16)	H3A—C3—H3B	107.9
O1—S1—O4	108.81 (11)	C2—C3—H3A	109.2
S1—O2—Ni2	126.36 (11)	C2—C3—H3B	109.2
S1—O1—Ni1	126.17 (11)	C3—C2—H2A	108.5
Ni2—N4—H4	107.4	C3—C2—H2B	108.5
C9—N4—Ni2	104.98 (17)	C3—C2—C1	115.1 (2)
C9—N4—H4	107.4	H2A—C2—H2B	107.5
C9—N4—C8	113.3 (2)	C1—C2—H2A	108.5
C8—N4—Ni2	116.05 (17)	C1—C2—H2B	108.5
C8—N4—H4	107.4	N4—C9—C10ⁱⁱ	108.4 (2)
Ni1—N1—H1	106.9	N4—C9—H9A	110.0
C5—N1—Ni1	105.39 (17)	N4—C9—H9B	110.0
C5—N1—H1	106.9	C10ⁱⁱ—C9—H9A	110.0
C1—N1—Ni1	116.45 (17)	C10ⁱⁱ—C9—H9B	110.0
C1—N1—H1	106.9	H9A—C9—H9B	108.4
C1—N1—C5	113.8 (2)	N4—C8—C7	111.5 (2)
Ni1—N2—H2	107.5	N4—C8—H8A	109.3
C4—N2—Ni1	105.35 (17)	N4—C8—H8B	109.3
C4—N2—H2	107.5	C7—C8—H8A	109.3
C3—N2—Ni1	114.87 (16)	C7—C8—H8B	109.3
C3—N2—H2	107.5	H8A—C8—H8B	108.0
C3—N2—C4	113.8 (2)	N1—C1—C2	112.0 (2)
Ni2—N3—H3	107.1	N1—C1—H1A	109.2
C10—N3—Ni2	105.45 (16)	N1—C1—H1B	109.2
C10—N3—H3	107.1	C2—C1—H1A	109.2
C10—N3—C6	114.1 (2)	C2—C1—H1B	109.2
C6—N3—Ni2	115.61 (16)	H1A—C1—H1B	107.9

Ni1—N1—C5—C4ⁱ	−41.9 (2)	O4—S1—O1—Ni1	65.05 (16)
Ni1—N1—C1—C2	54.9 (3)	N2—C3—C2—C1	73.0 (3)
Ni1—N2—C4—C5ⁱ	41.8 (2)	C4—N2—C3—C2	−179.6 (2)
Ni1—N2—C3—C2	−58.0 (2)	C5—N1—C1—C2	177.9 (2)
Ni2—N4—C9—C10ⁱⁱ	43.1 (2)	C10—N3—C6—C7	178.8 (2)
Ni2—N4—C8—C7	−56.2 (3)	C6—N3—C10—C9ⁱⁱ	−170.5 (2)
Ni2—N3—C10—C9ⁱⁱ	−42.5 (2)	C6—C7—C8—N4	71.5 (3)
Ni2—N3—C6—C7	56.2 (3)	C3—N2—C4—C5ⁱ	168.5 (2)
O2—S1—O1—Ni1	−175.93 (11)	C3—C2—C1—N1	−70.7 (3)
O3—S1—O2—Ni2	57.29 (17)	C9—N4—C8—C7	−177.7 (2)
O3—S1—O1—Ni1	−55.11 (17)	C8—N4—C9—C10ⁱⁱ	170.7 (2)
O1—S1—O2—Ni2	177.90 (11)	C8—C7—C6—N3	−71.8 (3)
O4—S1—O2—Ni2	−63.16 (16)	C1—N1—C5—C4ⁱ	−170.7 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3	0.98	2.02	2.916 (3)	151
N2—H2···O4	0.98	2.05	2.960 (3)	154
N3—H3···O4	0.98	2.01	2.938 (3)	157
N4—H4···O3	0.98	2.04	2.946 (3)	153
C5—H5A···O3ⁱⁱⁱ	0.97	2.52	3.336 (4)	141
C6—H6B···O4^iv	0.97	2.51	3.245 (3)	133

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

catena-Poly[[[(1,4,8,11-tetraazacyclotetradecane-κ⁴N¹,N⁴,N⁸,N¹¹)nickel(II)]-µ₂-sulfato-κ²O³:O⁴] hemi[4,4',4'',4'''-(2,2',4,4',6,6'-hexamethyl-[1,1'-biphenyl]-3,3',5,5'-tetrayl)tetrabenzoic acid] nonahydrate] (II) top

Crystal data top

[Ni(SO₄)(C₁₀H₂₄N₄)]₂·C₄₆H₃₈O₈·18H₂O	F(000) = 3016
M_r = 1428.96	D_x = 1.190 Mg m⁻³
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
a = 12.1299 (5) Å	Cell parameters from 2340 reflections
b = 18.5163 (11) Å	θ = 2.0–21.1°
c = 35.621 (2) Å	µ = 0.59 mm⁻¹
β = 94.777 (4)°	T = 293 K
V = 7972.7 (8) Å³	Plate, clear light colourless
Z = 4	0.10 × 0.04 × 0.01 mm

Data collection top

Xcalibur, Eos diffractometer	8085 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	3223 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.086
Detector resolution: 16.1593 pixels mm^-1	θ_max = 26.4°, θ_min = 2.0°
ω scans	h = −15→15
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2022)	k = −15→23
T_min = 0.920, T_max = 1.000	l = −23→44
20054 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.077	H-atom parameters constrained
wR(F²) = 0.123	w = 1/[σ²(F_o²) + (0.0206P)²] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max < 0.001
8085 reflections	Δρ_max = 0.25 e Å⁻³
432 parameters	Δρ_min = −0.35 e Å⁻³
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni1	0.250000	0.750000	0.750000	0.0562 (3)
Ni2	0.750000	0.750000	0.750000	0.0628 (3)
S1	0.50054 (10)	0.67856 (9)	0.75649 (4)	0.0648 (5)
O3	0.5194 (2)	0.6766 (2)	0.79768 (10)	0.0784 (12)
O2	0.60695 (19)	0.68618 (17)	0.73957 (8)	0.0637 (10)
N3	0.8460 (3)	0.6578 (3)	0.74746 (15)	0.0723 (14)
H3	0.923074	0.673461	0.747240	0.087*
O1	0.4286 (2)	0.74068 (18)	0.74571 (9)	0.0633 (10)
O4	0.4467 (2)	0.6099 (2)	0.74284 (10)	0.0839 (13)
N1	0.2244 (3)	0.6743 (3)	0.70776 (12)	0.0646 (13)
H1	0.296188	0.651709	0.704761	0.078*
N2	0.2493 (3)	0.6758 (3)	0.79323 (12)	0.0724 (15)
H2	0.322725	0.653431	0.796249	0.087*
N4	0.7455 (3)	0.7698 (3)	0.69294 (12)	0.0752 (15)
H4	0.815571	0.792987	0.688167	0.090*
C30	0.6311 (4)	0.1028 (2)	0.43972 (16)	0.0549 (15)
O6	0.3958 (3)	0.6092 (2)	0.64754 (11)	0.1048 (15)
C11	0.4785 (4)	0.5740 (3)	0.6510 (2)	0.0739 (19)
O8	0.3879 (3)	−0.0478 (2)	0.34768 (11)	0.0993 (15)
C18	0.6922 (3)	0.4520 (2)	0.52586 (16)	0.0565 (15)
C15	0.6387 (4)	0.4891 (3)	0.55700 (18)	0.0578 (16)
O5	0.5273 (3)	0.5560 (3)	0.68365 (12)	0.1085 (17)
H5	0.494848	0.574604	0.700454	0.163*
C35	0.6920 (4)	0.0749 (3)	0.41216 (17)	0.0641 (17)
H35	0.767412	0.084687	0.413391	0.077*
O7	0.5501 (4)	−0.0438 (2)	0.32448 (15)	0.141 (2)
H7	0.544646	−0.087006	0.319664	0.212*
C24	0.750000	0.2565 (4)	0.500000	0.061 (2)
C10	0.8358 (4)	0.6201 (4)	0.7837 (2)	0.099 (2)
H10A	0.894279	0.584556	0.787911	0.118*
H10B	0.765234	0.595217	0.783070	0.118*
C12	0.5369 (4)	0.5458 (3)	0.61875 (18)	0.0632 (17)
C33	0.5339 (4)	0.0202 (2)	0.37979 (15)	0.0549 (15)
C32	0.4706 (4)	0.0485 (3)	0.40693 (17)	0.0667 (17)
H32	0.394832	0.040027	0.405222	0.080*
C29	0.750000	0.0240 (3)	0.500000	0.081 (3)
H29A	0.682200	0.006673	0.508860	0.122*	0.5
H29B	0.811420	0.006673	0.516270	0.122*	0.5
H29C	0.756370	0.006673	0.474860	0.122*	0.5
C25	0.6867 (4)	0.2198 (3)	0.47185 (17)	0.0632 (16)
C31	0.5178 (4)	0.0887 (3)	0.43612 (17)	0.0724 (18)
H31	0.473456	0.107060	0.453963	0.087*
C21	0.6887 (4)	0.3754 (2)	0.52488 (16)	0.0598 (16)
C2	0.1792 (4)	0.5761 (3)	0.7521 (2)	0.102 (3)
H2A	0.134603	0.532745	0.752629	0.123*
H2B	0.255789	0.561034	0.751981	0.123*
C14	0.5408 (4)	0.5268 (3)	0.55178 (17)	0.0761 (18)
H14	0.507398	0.533655	0.527591	0.091*
C19	0.750000	0.4897 (4)	0.500000	0.059 (2)
C7	0.8269 (4)	0.6526 (4)	0.67781 (18)	0.100 (2)
H7A	0.827753	0.618110	0.657331	0.120*
H7B	0.896294	0.678843	0.679027	0.120*
C1	0.1470 (4)	0.6156 (3)	0.71504 (19)	0.091 (2)
H1A	0.145034	0.581271	0.694445	0.109*
H1B	0.073304	0.635565	0.715824	0.109*
C34	0.6463 (4)	0.0332 (3)	0.38290 (16)	0.0628 (16)
H34	0.690847	0.014029	0.365352	0.075*
C26	0.6144 (4)	0.2602 (3)	0.44165 (17)	0.093 (2)
H26A	0.628524	0.311130	0.443719	0.140*
H26B	0.537924	0.251010	0.444999	0.140*
H26C	0.630924	0.243690	0.417199	0.140*
C28	0.750000	0.1063 (3)	0.500000	0.053 (2)
C36	0.4816 (5)	−0.0268 (3)	0.34931 (17)	0.0710 (18)
C6	0.8214 (4)	0.6113 (3)	0.7142 (2)	0.093 (2)
H6A	0.748034	0.590791	0.714947	0.112*
H6B	0.874045	0.571789	0.714897	0.112*
C27	0.6889 (4)	0.1440 (3)	0.47161 (16)	0.0581 (15)
C23	0.750000	0.3381 (3)	0.500000	0.059 (2)
C4	0.2352 (4)	0.7191 (4)	0.82776 (17)	0.092 (2)
H4A	0.257107	0.690753	0.850039	0.111*
H4B	0.158213	0.732707	0.828578	0.111*
C13	0.4922 (4)	0.5543 (3)	0.5823 (2)	0.077 (2)
H13	0.426278	0.579840	0.578109	0.092*
C17	0.6369 (4)	0.5105 (3)	0.62374 (17)	0.087 (2)
H17	0.671219	0.504953	0.647893	0.105*
C16	0.6867 (4)	0.4833 (3)	0.5933 (2)	0.099 (2)
H16	0.754840	0.460414	0.597436	0.118*
C5	0.1940 (4)	0.7144 (4)	0.67308 (16)	0.089 (2)
H5A	0.116564	0.728053	0.672049	0.106*
H5B	0.204755	0.684329	0.651400	0.106*
C3	0.1672 (4)	0.6173 (4)	0.7876 (2)	0.099 (2)
H3A	0.093417	0.637773	0.786818	0.119*
H3B	0.175758	0.584418	0.808869	0.119*
C9	0.6560 (4)	0.8245 (4)	0.68479 (18)	0.100 (2)
H9A	0.584152	0.801136	0.683389	0.120*
H9B	0.664611	0.847849	0.660847	0.120*
C22	0.6150 (4)	0.3346 (3)	0.55038 (16)	0.096 (2)
H22A	0.652519	0.330370	0.575101	0.144*
H22B	0.598969	0.287350	0.540311	0.144*
H22C	0.547179	0.360810	0.551891	0.144*
C8	0.7330 (4)	0.7059 (4)	0.66839 (17)	0.099 (2)
H8A	0.733069	0.720682	0.642270	0.119*
H8B	0.662777	0.682610	0.671625	0.119*
C20	0.750000	0.5710 (3)	0.500000	0.086 (3)
H20A	0.675440	0.588307	0.500220	0.129*	0.5
H20B	0.781320	0.588307	0.477810	0.129*	0.5
H20C	0.793240	0.588307	0.521970	0.129*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0282 (5)	0.1032 (8)	0.0381 (6)	0.0154 (5)	0.0081 (4)	0.0213 (6)
Ni2	0.0268 (5)	0.1156 (8)	0.0474 (7)	0.0160 (5)	0.0113 (4)	0.0303 (7)
S1	0.0272 (6)	0.1131 (13)	0.0562 (11)	0.0168 (8)	0.0155 (6)	0.0301 (11)
O3	0.047 (2)	0.140 (3)	0.049 (3)	0.029 (2)	0.0138 (17)	0.044 (3)
O2	0.0217 (16)	0.117 (3)	0.055 (3)	0.0142 (16)	0.0150 (15)	0.018 (2)
N3	0.030 (2)	0.122 (4)	0.066 (4)	0.014 (2)	0.010 (2)	0.023 (4)
O1	0.0313 (16)	0.104 (3)	0.055 (2)	0.0224 (17)	0.0082 (15)	0.026 (2)
O4	0.040 (2)	0.105 (3)	0.110 (4)	0.005 (2)	0.028 (2)	0.009 (3)
N1	0.032 (2)	0.117 (4)	0.046 (3)	0.022 (2)	0.010 (2)	−0.001 (3)
N2	0.030 (2)	0.132 (4)	0.057 (4)	0.025 (3)	0.015 (2)	0.042 (3)
N4	0.037 (2)	0.139 (5)	0.051 (4)	0.010 (3)	0.014 (2)	0.029 (3)
C30	0.068 (4)	0.033 (3)	0.066 (5)	0.004 (3)	0.020 (3)	0.004 (3)
O6	0.065 (3)	0.143 (4)	0.108 (4)	0.053 (2)	0.011 (2)	−0.008 (3)
C11	0.047 (4)	0.084 (5)	0.092 (6)	0.012 (3)	0.015 (4)	−0.009 (4)
O8	0.051 (2)	0.133 (3)	0.116 (4)	−0.020 (2)	0.025 (2)	−0.044 (3)
C18	0.041 (3)	0.044 (3)	0.085 (5)	0.009 (2)	0.010 (3)	−0.007 (3)
C15	0.045 (3)	0.048 (3)	0.082 (5)	−0.002 (3)	0.011 (3)	0.004 (4)
O5	0.075 (3)	0.167 (4)	0.084 (4)	0.057 (3)	0.010 (3)	−0.005 (4)
C35	0.056 (3)	0.059 (4)	0.079 (5)	−0.010 (3)	0.015 (3)	0.000 (4)
O7	0.103 (3)	0.163 (4)	0.172 (5)	−0.076 (3)	0.096 (3)	−0.115 (4)
C24	0.069 (5)	0.032 (5)	0.086 (8)	0.000	0.026 (5)	0.000
C10	0.047 (4)	0.144 (7)	0.105 (7)	0.021 (4)	0.008 (4)	0.048 (6)
C12	0.042 (3)	0.068 (4)	0.081 (5)	0.012 (3)	0.009 (3)	0.004 (4)
C33	0.049 (3)	0.052 (3)	0.067 (5)	−0.001 (2)	0.021 (3)	−0.003 (3)
C32	0.043 (3)	0.072 (4)	0.087 (5)	−0.004 (3)	0.018 (3)	−0.019 (4)
C29	0.116 (6)	0.044 (5)	0.081 (7)	0.000	−0.010 (5)	0.000
C25	0.072 (4)	0.037 (4)	0.082 (5)	0.002 (3)	0.012 (3)	0.010 (3)
C31	0.062 (4)	0.073 (4)	0.086 (5)	0.003 (3)	0.032 (3)	−0.015 (4)
C21	0.055 (3)	0.042 (3)	0.086 (5)	−0.006 (3)	0.024 (3)	0.004 (3)
C2	0.042 (4)	0.105 (6)	0.161 (9)	0.005 (3)	0.019 (4)	0.025 (6)
C14	0.052 (3)	0.097 (4)	0.079 (5)	0.020 (3)	0.003 (3)	−0.020 (4)
C19	0.041 (4)	0.041 (5)	0.095 (7)	0.000	0.013 (4)	0.000
C7	0.071 (4)	0.156 (6)	0.077 (6)	−0.007 (4)	0.027 (4)	−0.004 (5)
C1	0.043 (3)	0.121 (6)	0.111 (7)	−0.003 (4)	0.011 (4)	−0.022 (5)
C34	0.054 (3)	0.057 (4)	0.082 (5)	−0.006 (3)	0.030 (3)	0.007 (3)
C26	0.105 (5)	0.053 (4)	0.121 (6)	0.009 (3)	0.000 (4)	0.005 (4)
C28	0.083 (5)	0.010 (4)	0.068 (7)	0.000	0.013 (4)	0.000
C36	0.066 (4)	0.077 (4)	0.074 (5)	−0.014 (3)	0.029 (4)	−0.022 (4)
C6	0.040 (3)	0.134 (6)	0.107 (7)	0.011 (3)	0.018 (4)	0.011 (6)
C27	0.055 (3)	0.045 (4)	0.074 (5)	0.000 (3)	0.008 (3)	−0.001 (3)
C23	0.050 (4)	0.028 (5)	0.099 (8)	0.000	0.014 (4)	0.000
C4	0.059 (4)	0.168 (7)	0.054 (5)	0.046 (4)	0.027 (3)	0.041 (5)
C13	0.049 (4)	0.081 (4)	0.100 (6)	0.027 (3)	0.008 (4)	0.004 (4)
C17	0.058 (3)	0.121 (5)	0.082 (5)	0.040 (3)	0.004 (3)	−0.005 (4)
C16	0.055 (4)	0.139 (6)	0.103 (6)	0.046 (4)	0.016 (4)	−0.015 (5)
C5	0.064 (4)	0.159 (7)	0.043 (4)	0.039 (4)	0.008 (3)	0.002 (5)
C3	0.050 (4)	0.129 (6)	0.123 (7)	0.015 (4)	0.032 (4)	0.057 (5)
C9	0.053 (4)	0.178 (7)	0.067 (5)	0.018 (4)	0.002 (3)	0.064 (5)
C22	0.103 (5)	0.064 (4)	0.129 (6)	−0.008 (3)	0.051 (4)	0.017 (4)
C8	0.057 (4)	0.181 (7)	0.062 (5)	0.000 (4)	0.013 (3)	0.021 (5)
C20	0.111 (6)	0.019 (4)	0.135 (9)	0.000	0.055 (5)	0.000

Geometric parameters (Å, º) top

Ni1—O1	2.191 (2)	C33—C36	1.491 (6)
Ni1—O1ⁱ	2.191 (2)	C32—H32	0.9300
Ni1—N1	2.061 (4)	C32—C31	1.365 (6)
Ni1—N1ⁱ	2.061 (4)	C29—H29A	0.9600
Ni1—N2	2.065 (4)	C29—H29B	0.9600
Ni1—N2ⁱ	2.065 (4)	C29—H29C	0.9602
Ni2—O2	2.107 (3)	C29—C28	1.524 (8)
Ni2—O2ⁱⁱ	2.107 (3)	C25—C26	1.526 (6)
Ni2—N3ⁱⁱ	2.073 (4)	C25—C27	1.403 (6)
Ni2—N3	2.073 (4)	C31—H31	0.9300
Ni2—N4	2.062 (4)	C21—C23	1.388 (5)
Ni2—N4ⁱⁱ	2.062 (4)	C21—C22	1.526 (6)
S1—O3	1.466 (3)	C2—H2A	0.9700
S1—O2	1.476 (3)	C2—H2B	0.9700
S1—O1	1.476 (3)	C2—C1	1.530 (7)
S1—O4	1.491 (4)	C2—C3	1.496 (7)
N3—H3	0.9800	C14—H14	0.9300
N3—C10	1.481 (6)	C14—C13	1.378 (7)
N3—C6	1.476 (6)	C19—C20	1.506 (8)
N1—H1	0.9800	C7—H7A	0.9700
N1—C1	1.473 (6)	C7—H7B	0.9700
N1—C5	1.462 (6)	C7—C6	1.510 (7)
N2—H2	0.9800	C7—C8	1.523 (7)
N2—C4	1.490 (6)	C1—H1A	0.9700
N2—C3	1.473 (6)	C1—H1B	0.9700
N4—H4	0.9800	C34—H34	0.9300
N4—C9	1.495 (6)	C26—H26A	0.9599
N4—C8	1.472 (6)	C26—H26B	0.9601
C30—C35	1.377 (6)	C26—H26C	0.9600
C30—C31	1.395 (6)	C28—C27ⁱⁱⁱ	1.391 (5)
C30—C27	1.494 (7)	C28—C27	1.391 (5)
O6—C11	1.194 (5)	C6—H6A	0.9700
C11—O5	1.305 (6)	C6—H6B	0.9700
C11—C12	1.492 (7)	C4—H4A	0.9700
O8—C36	1.198 (5)	C4—H4B	0.9700
C18—C15	1.498 (6)	C4—C5ⁱ	1.503 (7)
C18—C21	1.419 (6)	C13—H13	0.9300
C18—C19	1.391 (5)	C17—H17	0.9300
C15—C14	1.377 (6)	C17—C16	1.380 (7)
C15—C16	1.377 (7)	C16—H16	0.9300
O5—H5	0.8200	C5—H5A	0.9700
C35—H35	0.9300	C5—H5B	0.9700
C35—C34	1.376 (6)	C3—H3A	0.9700
O7—H7	0.8200	C3—H3B	0.9700
O7—C36	1.302 (5)	C9—H9A	0.9700
C24—C25ⁱⁱⁱ	1.389 (6)	C9—H9B	0.9700
C24—C25	1.389 (6)	C22—H22A	0.9602
C24—C23	1.510 (9)	C22—H22B	0.9600
C10—H10A	0.9700	C22—H22C	0.9601
C10—H10B	0.9700	C8—H8A	0.9700
C10—C9ⁱⁱ	1.519 (7)	C8—H8B	0.9700
C12—C13	1.372 (7)	C20—H20A	0.9600
C12—C17	1.376 (6)	C20—H20B	0.9599
C33—C32	1.386 (6)	C20—H20C	0.9600
C33—C34	1.381 (5)

O1—Ni1—O1ⁱ	180.0	C32—C31—C30	121.3 (5)
N1ⁱ—Ni1—O1	90.85 (13)	C32—C31—H31	119.4
N1—Ni1—O1ⁱ	90.85 (13)	C18—C21—C22	119.8 (4)
N1—Ni1—O1	89.15 (13)	C23—C21—C18	119.8 (5)
N1ⁱ—Ni1—O1ⁱ	89.15 (13)	C23—C21—C22	120.3 (4)
N1—Ni1—N1ⁱ	180.0	H2A—C2—H2B	107.3
N1ⁱ—Ni1—N2ⁱ	94.72 (19)	C1—C2—H2A	108.1
N1ⁱ—Ni1—N2	85.28 (19)	C1—C2—H2B	108.1
N1—Ni1—N2ⁱ	85.28 (19)	C3—C2—H2A	108.1
N1—Ni1—N2	94.72 (19)	C3—C2—H2B	108.1
N2—Ni1—O1ⁱ	86.26 (12)	C3—C2—C1	116.8 (6)
N2—Ni1—O1	93.74 (12)	C15—C14—H14	119.9
N2ⁱ—Ni1—O1ⁱ	93.74 (12)	C15—C14—C13	120.1 (6)
N2ⁱ—Ni1—O1	86.26 (12)	C13—C14—H14	119.9
N2—Ni1—N2ⁱ	180.0	C18—C19—C18ⁱⁱⁱ	119.8 (6)
O2ⁱⁱ—Ni2—O2	180.0	C18ⁱⁱⁱ—C19—C20	120.1 (3)
N3ⁱⁱ—Ni2—O2ⁱⁱ	89.28 (14)	C18—C19—C20	120.1 (3)
N3—Ni2—O2	89.28 (14)	H7A—C7—H7B	107.5
N3ⁱⁱ—Ni2—O2	90.72 (14)	C6—C7—H7A	108.4
N3—Ni2—O2ⁱⁱ	90.72 (14)	C6—C7—H7B	108.4
N3ⁱⁱ—Ni2—N3	180.0	C6—C7—C8	115.6 (5)
N4—Ni2—O2ⁱⁱ	91.61 (15)	C8—C7—H7A	108.4
N4ⁱⁱ—Ni2—O2	91.61 (15)	C8—C7—H7B	108.4
N4ⁱⁱ—Ni2—O2ⁱⁱ	88.39 (15)	N1—C1—C2	112.6 (5)
N4—Ni2—O2	88.39 (15)	N1—C1—H1A	109.1
N4—Ni2—N3ⁱⁱ	85.84 (19)	N1—C1—H1B	109.1
N4ⁱⁱ—Ni2—N3ⁱⁱ	94.16 (19)	C2—C1—H1A	109.1
N4ⁱⁱ—Ni2—N3	85.84 (19)	C2—C1—H1B	109.1
N4—Ni2—N3	94.16 (19)	H1A—C1—H1B	107.8
N4ⁱⁱ—Ni2—N4	180.00 (4)	C35—C34—C33	119.5 (5)
O3—S1—O2	110.02 (18)	C35—C34—H34	120.3
O3—S1—O1	108.6 (2)	C33—C34—H34	120.3
O3—S1—O4	109.5 (2)	C25—C26—H26A	109.8
O2—S1—O4	108.8 (2)	C25—C26—H26B	109.3
O1—S1—O2	109.74 (19)	C25—C26—H26C	109.4
O1—S1—O4	110.2 (2)	H26A—C26—H26B	109.5
S1—O2—Ni2	135.8 (2)	H26A—C26—H26C	109.5
Ni2—N3—H3	107.2	H26B—C26—H26C	109.5
C10—N3—Ni2	105.2 (3)	C27ⁱⁱⁱ—C28—C29	120.2 (3)
C10—N3—H3	107.2	C27—C28—C29	120.2 (3)
C6—N3—Ni2	116.0 (3)	C27ⁱⁱⁱ—C28—C27	119.7 (7)
C6—N3—H3	107.2	O8—C36—O7	123.0 (6)
C6—N3—C10	113.6 (5)	O8—C36—C33	124.7 (5)
S1—O1—Ni1	127.61 (19)	O7—C36—C33	112.3 (5)
Ni1—N1—H1	106.8	N3—C6—C7	111.9 (6)
C1—N1—Ni1	115.6 (3)	N3—C6—H6A	109.2
C1—N1—H1	106.8	N3—C6—H6B	109.2
C5—N1—Ni1	106.5 (4)	C7—C6—H6A	109.2
C5—N1—H1	106.8	C7—C6—H6B	109.2
C5—N1—C1	113.8 (5)	H6A—C6—H6B	107.9
Ni1—N2—H2	107.6	C25—C27—C30	120.5 (5)
C4—N2—Ni1	105.4 (4)	C28—C27—C30	118.9 (5)
C4—N2—H2	107.6	C28—C27—C25	120.5 (6)
C3—N2—Ni1	115.7 (3)	C21—C23—C24	119.9 (3)
C3—N2—H2	107.6	C21ⁱⁱⁱ—C23—C24	119.9 (3)
C3—N2—C4	112.6 (4)	C21—C23—C21ⁱⁱⁱ	120.2 (6)
Ni2—N4—H4	107.3	N2—C4—H4A	110.0
C9—N4—Ni2	105.7 (3)	N2—C4—H4B	110.0
C9—N4—H4	107.3	N2—C4—C5ⁱ	108.6 (4)
C8—N4—Ni2	115.8 (4)	H4A—C4—H4B	108.3
C8—N4—H4	107.3	C5ⁱ—C4—H4A	110.0
C8—N4—C9	113.1 (5)	C5ⁱ—C4—H4B	110.0
C35—C30—C31	116.6 (5)	C12—C13—C14	122.8 (5)
C35—C30—C27	119.2 (5)	C12—C13—H13	118.6
C31—C30—C27	124.2 (5)	C14—C13—H13	118.6
O6—C11—O5	123.1 (6)	C12—C17—H17	119.6
O6—C11—C12	124.2 (6)	C12—C17—C16	120.7 (6)
O5—C11—C12	112.8 (5)	C16—C17—H17	119.6
C21—C18—C15	117.5 (5)	C15—C16—C17	122.1 (5)
C19—C18—C15	122.3 (4)	C15—C16—H16	119.0
C19—C18—C21	120.1 (5)	C17—C16—H16	119.0
C14—C15—C18	123.7 (6)	N1—C5—C4ⁱ	109.2 (5)
C16—C15—C18	119.0 (5)	N1—C5—H5A	109.8
C16—C15—C14	117.3 (5)	N1—C5—H5B	109.8
C11—O5—H5	109.5	C4ⁱ—C5—H5A	109.8
C30—C35—H35	118.5	C4ⁱ—C5—H5B	109.8
C30—C35—C34	123.0 (5)	H5A—C5—H5B	108.3
C34—C35—H35	118.5	N2—C3—C2	112.1 (5)
C36—O7—H7	109.5	N2—C3—H3A	109.2
C25—C24—C25ⁱⁱⁱ	121.4 (7)	N2—C3—H3B	109.2
C25ⁱⁱⁱ—C24—C23	119.3 (4)	C2—C3—H3A	109.2
C25—C24—C23	119.3 (4)	C2—C3—H3B	109.2
N3—C10—H10A	110.0	H3A—C3—H3B	107.9
N3—C10—H10B	110.0	N4—C9—C10ⁱⁱ	108.2 (5)
N3—C10—C9ⁱⁱ	108.7 (5)	N4—C9—H9A	110.1
H10A—C10—H10B	108.3	N4—C9—H9B	110.1
C9ⁱⁱ—C10—H10A	110.0	C10ⁱⁱ—C9—H9A	110.1
C9ⁱⁱ—C10—H10B	110.0	C10ⁱⁱ—C9—H9B	110.1
C13—C12—C11	120.7 (5)	H9A—C9—H9B	108.4
C13—C12—C17	116.8 (5)	C21—C22—H22A	109.3
C17—C12—C11	122.5 (6)	C21—C22—H22B	109.8
C32—C33—C36	120.2 (5)	C21—C22—H22C	109.3
C34—C33—C32	118.5 (5)	H22A—C22—H22B	109.5
C34—C33—C36	121.2 (5)	H22A—C22—H22C	109.5
C33—C32—H32	119.4	H22B—C22—H22C	109.5
C31—C32—C33	121.1 (5)	N4—C8—C7	110.6 (5)
C31—C32—H32	119.4	N4—C8—H8A	109.5
H29A—C29—H29B	109.5	N4—C8—H8B	109.5
H29A—C29—H29C	109.5	C7—C8—H8A	109.5
H29B—C29—H29C	109.5	C7—C8—H8B	109.5
C28—C29—H29A	109.5	H8A—C8—H8B	108.1
C28—C29—H29B	109.5	C19—C20—H20A	109.5
C28—C29—H29C	109.5	C19—C20—H20B	109.5
C24—C25—C26	121.3 (5)	C19—C20—H20C	109.5
C24—C25—C27	118.9 (6)	H20A—C20—H20B	109.5
C27—C25—C26	119.7 (5)	H20A—C20—H20C	109.5
C30—C31—H31	119.4	H20B—C20—H20C	109.5

Ni1—N1—C1—C2	−54.6 (6)	C25ⁱⁱⁱ—C24—C23—C21ⁱⁱⁱ	102.8 (3)
Ni1—N1—C5—C4ⁱ	40.7 (4)	C25—C24—C23—C21	102.8 (3)
Ni1—N2—C4—C5ⁱ	−41.7 (5)	C25—C24—C23—C21ⁱⁱⁱ	−77.2 (3)
Ni1—N2—C3—C2	56.4 (6)	C25ⁱⁱⁱ—C24—C23—C21	−77.2 (3)
Ni2—N3—C10—C9ⁱⁱ	−42.8 (5)	C31—C30—C35—C34	−2.0 (8)
Ni2—N3—C6—C7	55.0 (5)	C31—C30—C27—C25	−80.6 (7)
Ni2—N4—C9—C10ⁱⁱ	41.2 (5)	C31—C30—C27—C28	103.0 (5)
Ni2—N4—C8—C7	−58.2 (5)	C21—C18—C15—C14	−107.6 (6)
O3—S1—O2—Ni2	−44.7 (3)	C21—C18—C15—C16	69.7 (7)
O3—S1—O1—Ni1	−75.3 (3)	C21—C18—C19—C18ⁱⁱⁱ	−2.5 (3)
O2—S1—O1—Ni1	164.4 (2)	C21—C18—C19—C20	177.5 (3)
O1—S1—O2—Ni2	74.7 (3)	C14—C15—C16—C17	3.4 (9)
O4—S1—O2—Ni2	−164.6 (2)	C19—C18—C15—C14	76.6 (6)
O4—S1—O1—Ni1	44.6 (3)	C19—C18—C15—C16	−106.1 (6)
C30—C35—C34—C33	2.3 (8)	C19—C18—C21—C23	5.0 (7)
O6—C11—C12—C13	−5.3 (9)	C19—C18—C21—C22	−173.3 (4)
O6—C11—C12—C17	174.5 (6)	C1—N1—C5—C4ⁱ	169.2 (4)
C11—C12—C13—C14	−177.4 (5)	C1—C2—C3—N2	−70.0 (6)
C11—C12—C17—C16	178.1 (6)	C34—C33—C32—C31	0.2 (8)
C18—C15—C14—C13	174.6 (5)	C34—C33—C36—O8	170.1 (5)
C18—C15—C16—C17	−174.1 (5)	C34—C33—C36—O7	−9.0 (8)
C18—C21—C23—C24	177.6 (3)	C26—C25—C27—C30	6.9 (8)
C18—C21—C23—C21ⁱⁱⁱ	−2.4 (3)	C26—C25—C27—C28	−176.8 (4)
C15—C18—C21—C23	−171.0 (4)	C36—C33—C32—C31	176.7 (5)
C15—C18—C21—C22	10.8 (7)	C36—C33—C34—C35	−177.8 (5)
C15—C18—C19—C18ⁱⁱⁱ	173.3 (5)	C6—N3—C10—C9ⁱⁱ	−170.7 (4)
C15—C18—C19—C20	−6.7 (5)	C6—C7—C8—N4	73.2 (7)
C15—C14—C13—C12	−0.3 (9)	C27—C30—C35—C34	176.6 (5)
O5—C11—C12—C13	174.5 (6)	C27—C30—C31—C32	−177.7 (5)
O5—C11—C12—C17	−5.7 (8)	C27ⁱⁱⁱ—C28—C27—C30	175.1 (5)
C35—C30—C31—C32	0.8 (8)	C27ⁱⁱⁱ—C28—C27—C25	−1.3 (3)
C35—C30—C27—C25	101.0 (6)	C23—C24—C25—C26	−2.0 (5)
C35—C30—C27—C28	−75.5 (6)	C23—C24—C25—C27	178.7 (3)
C24—C25—C27—C30	−173.8 (4)	C4—N2—C3—C2	177.7 (5)
C24—C25—C27—C28	2.6 (7)	C13—C12—C17—C16	−2.1 (9)
C10—N3—C6—C7	177.0 (4)	C17—C12—C13—C14	2.8 (9)
C12—C17—C16—C15	−1.0 (10)	C16—C15—C14—C13	−2.8 (8)
C33—C32—C31—C30	0.1 (9)	C5—N1—C1—C2	−178.3 (5)
C32—C33—C34—C35	−1.3 (7)	C3—N2—C4—C5ⁱ	−168.6 (4)
C32—C33—C36—O8	−6.3 (9)	C3—C2—C1—N1	69.3 (6)
C32—C33—C36—O7	174.6 (5)	C9—N4—C8—C7	179.5 (4)
C29—C28—C27—C30	−4.9 (5)	C22—C21—C23—C24	−4.2 (5)
C29—C28—C27—C25	178.7 (3)	C22—C21—C23—C21ⁱⁱⁱ	175.7 (5)
C25ⁱⁱⁱ—C24—C25—C26	178.0 (5)	C8—N4—C9—C10ⁱⁱ	169.0 (5)
C25ⁱⁱⁱ—C24—C25—C27	−1.3 (3)	C8—C7—C6—N3	−71.6 (7)

Symmetry codes: (i) −x+1/2, −y+3/2, −z+3/2; (ii) −x+3/2, −y+3/2, −z+3/2; (iii) −x+3/2, y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4	0.98	2.32	3.113 (5)	138
N2—H2···O3	0.98	2.42	3.267 (4)	144
N4—H4···O3ⁱⁱ	0.98	2.10	3.012 (5)	154
O5—H5···O4	0.82	1.79	2.597 (5)	169
O7—H7···O3^iv	0.82	1.85	2.654 (5)	166

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

Selected geometric parameters (Å, °) top

	I	II
Ni1—N1	2.064 (2)	2.061 (4)
Ni1—N2	2.072 (2)	2.065 (4)
Ni2—N3	2.063 (2)	2.073 (4)
Ni2—N4	2.072 (2)	2.062 (4)
Ni1—O1	2.1625 (16)	2.191 (2)
Ni2—O2	2.1696 (16)	2.107 (3)

N1—Ni1—N2ⁱ	85.51 (9)	85.28 (19)
N1—Ni1—N2	94.49 (9)	94.72 (19)
N3—Ni2—N4ⁱⁱ	85.41 (9)	85.84 (19)
N3—Ni2—N4	94.59 (9)	94.16 (19)

Symmetry codes: (i) -x, -y + 1, -z + 1 in (I) and -x + 1/2, -y + 3/2, -z + 3/2 in (II); (ii) -x + 1, -y + 1, -z + 2 in (I) and -x + 3/2, -y + 3/2, -z + 3/2 in (II).

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