Poly[[bis­(μ4-acetato-κ4O:O:O′:O′)tetra­kis­(μ3-acetato-κ3O:O:O′)bis­(μ2-acetato-κ2O:O′)bis­(μ3-hydroxido)penta­nickel(II)] 2.60-hydrate]

Pfeiffer, M.; Stöger, B.; Weil, M.

doi:10.1107/S2414314625000823

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 10| Part 2| February 2025| x250082

https://doi.org/10.1107/S2414314625000823

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Poly[[bis(μ₄-acetato-κ⁴O:O:O′:O′)tetrakis(μ₃-acetato-κ³O:O:O′)bis(μ₂-acetato-κ²O:O′)bis(μ₃-hydroxido)pentanickel(II)] 2.60-hydrate]

Maximilian Pfeiffer,^a Berthold Stöger ^a and Matthias Weil ^b ^*

^aTU Wien, X-Ray Centre, Getreidemarkt 9/E057, 1060 Vienna, Austria, and ^bTU Wien, Institute for Chemical Technologies and Analytics, Division of Structural Chemistry, Getreidemarkt 9/E164-05-1, 1060 Vienna, Austria
^*Correspondence e-mail: matthias.weil@tuwien.ac.at

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 22 January 2025; accepted 29 January 2025; online 7 February 2025)

The title compound, {[Ni₅(C₂H₃O₂)₈(OH)₂]·2.60H₂O}_n or [Ni₅(OAc)₈(OH)₂]·2.60H₂O (OAc is the acetate anion, C₂H₃O₂), represents a hydrated basic acetate. Its asymmetric unit comprises half of the formula unit, with one of the three unique Ni^II cations situated at an inversion centre. The Ni^II atoms are in octahedral coordination environments by O atoms of the acetato ligands and by the basic OH group. The different kinds of bridging modes (μ₂, 2×μ₃, and μ₄ for the acetato ligands; μ₃ for the OH group) lead to the formation of a framework structure with hydrophobic channels extending parallel to the main crystallographic axes. Disordered water molecules are situated in pockets close to the OH groups and are held in place by hydrogen-bonding interactions.

Keywords: crystal structure; nickel; basic acetate; disorder; hydrogen-bonding.

CCDC reference: 2420345

Structure description

Nickel acetate, Ni(OAc)₂, is a common precursor for the synthesis of oxygen-containing nickel compounds and is usually employed in form of its tetrahydrate. As it decomposes easily when the temperature is increased, it is used for typical solid-state reactions. As a result of its good solubility in water, nickel acetate can also be used for syntheses in aqueous media or under hydrothermal conditions. Precisely for this purpose, Ni(OAc)₂ was employed as a precursor intended for phase-formation studies of nickel arsenates under hydrothermal conditions. However, a basic nickel acetate of composition [Ni₅(OAc)₈(OH)₂]·2.60H₂O had formed serendipitously instead, and its crystal structure is reported here.

In general, basic acetates comprise metal cations bound to a collection of acetate anions and to an O^2– ion or an OH⁻ group. The latter bridge several metal atoms (M) and thus form oxido-centred coordination polyhedra, usually with {OM₃}-/{(HO)M₂}-trigonal–planar or {OM₄}-/{(HO)M₃}-tetrahedral shapes. These kinds of structural features are observed, for example, in the acetate compounds Be₄O(OAc)₆ (Pauling & Sherman, 1934 ), Mg₃O(OAc)₄ (Scheurell et al., 2015 ), [Cr₈(OH)₈(OAc)₁₆]·30H₂O (Eshel & Bino, 2001 ), Fe₃O(OAc)₇(HOAc) (Abrahams et al., 2024 ), Cu₂(OH)₃(OAc)·H₂O (Švarcová et al., 2011 ), Pb₃O₂(OAc)₂·0.5H₂O (Mauck et al., 2010 ), Pb₄O(OAc)₆ or Pb₂O(OAc)₂ (Martínez Casado et al., 2016 ). In the title compound, an {(HO)Ni₃} unit with tetrahedral shape is present, as discussed in more detail below.

[Ni₅(OAc)₈(OH)₂]·2.60H₂O is isostructural with the magnesium analogue, [Mg₅(OAc)₈(OH)₂]·1.19H₂O (Scheurell et al., 2015). The asymmetric unit of [Ni₅(OAc)₈(OH)₂]·2.60H₂O comprises of half of the formula unit, with Ni1 situated at a special position (multiplicity 8, Wyckoff letter d, site symmetry $[\overline{1}]$ ) of space group I4₁/a. The three Ni^II cations are octahedrally surrounded by O atoms, with Ni1 only by carboxylate O atoms, Ni2 by five carboxylate O atoms and one O atom (O9) of the OH group, and Ni3 by four carboxylate O atoms and two OH groups (Fig. 1Table 1). The Ni—O distances range from 1.993 (2) to 2.1259 (18) Å, with a mean of 2.063 (55) Å, which is close to the literature value of 2.070 (54) calculated for 242 [NiO₆] polyhedra (Gagné & Hawthorne, 2020 ).

Table 1
Selected bond lengths (Å)

Ni1—O2	1.993 (2)	Ni2—O6ⁱⁱ	2.1140 (18)
Ni1—O3	2.1037 (18)	Ni3—O9	1.9747 (18)
Ni1—O5	2.1257 (19)	Ni3—O9ⁱ	1.9902 (17)
Ni2—O1	1.993 (2)	Ni3—O7	2.0474 (19)
Ni2—O9	1.9962 (18)	Ni3—O4ⁱ	2.0750 (19)
Ni2—O3	2.0698 (18)	Ni3—O8ⁱ	2.1023 (19)
Ni2—O5	2.0937 (19)	Ni3—O6	2.1259 (18)
Ni2—O8ⁱ	2.1016 (18)
Symmetry codes: (i) $[y+{\script{1\over 4}}, -x+{\script{5\over 4}}, z+{\script{1\over 4}}]$ ; (ii) $[-y+{\script{5\over 4}}, x-{\script{1\over 4}}, z-{\script{1\over 4}}]$ .

Figure 1
The coordination of the Ni^II atoms in the crystal structure of [Ni₅(OAc)₈(OH)₂]·2.6H₂O. Displacement ellipsoids are drawn at the 40% probability level; for clarity, methyl H atoms and the O atoms of disordered water molecules are not shown. [Symmetry codes: (i) −y + $[{5\over 4}]$ , x − $[{1\over 4}]$ , z − $[{1\over 4}]$ ; (ii) y + $[{1\over 4}]$ , −x + $[{5\over 4}]$ , z + $[{1\over 4}]$ ; (iii) −x + 2, −y + 1, −z + 1.]

From the seven different possible coordination modes of acetato ligands to central M^II cations shown in Fig. 2, the acetate groups in the structure of the title compound feature only three. Coordination mode (a) is bridging two Ni^II cations in a bis-monodentate manner, μ₂-(-κ¹O,κ¹O′), and realized for carboxylate group C2(O1)O2; mode (b) is bridging three Ni^II cations in a monodentate-bis-monodentate manner, μ₃-(-κ¹Oκ²O′), and realized for carboxylate groups C4(O3)O4 and C7(O8)O7; mode (c) is bridging four Ni^II cations in a bis(bis-monodentate) manner, μ₄-(-κ²Oκ²O′, and realized for carboxylate group C5(O5)O6. Monodentate coordination mode (d), or any of the chelating coordination modes (e–g) detailed in Fig. 2 are not realized, but are known for other divalent first-row transition metals M, e.g. for anhydrous iron(II) acetate (Weber et al., 2011 ). The oxygen atom of the hydroxy group, O9H9, bridges three Ni^II cations (Ni2, Ni3, Ni3′). Together with the attached H9 atom, the environment of O9 is distorted tetrahedral, with Ni—O—Ni angles ranging from 97.13 (8) to 121.18 (9)°.

Figure 2
Possible coordination modes of the acetato ligand to metal cations M.

The μ₂- μ₃-, μ₄- and μ₃-bridging modes of the acetato ligands and the μ₃-mode of the OH group, respectively, lead to the formation of a framework structure, whereby the arrangement of the acetato ligands with the methyl groups pointing away from the Ni^II cations creates hydrophobic channels extending parallel to the main crystallographic axes (Figs. 3, 4). The disordered water molecules of crystallization are situated in pockets near to the hydroxy group to which they are hydrogen-bonded (Table 2, Fig. 4). In addition, typical donor⋯acceptor distances suitable for hydrogen bonds of moderate strength are present between O7⋯OW2 and O2W⋯O3W (Table 2). These interactions might further consolidate the crystal structure.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9⋯OW1	1.00	2.06	2.957 (4)	147
O9—H9⋯OW3	1.00	1.85	2.827 (8)	166
O7⋯OW2ⁱⁱ			2.87
OW2⋯OW3			2.85
Symmetry code: (ii) $[-y+{\script{5\over 4}}, x-{\script{1\over 4}}, z-{\script{1\over 4}}]$ .

Figure 3
Packing plot of [Ni₅(OAc)₈(OH)₂]·2.60H₂O along [100].

Figure 4
Packing plot of [Ni₅(OAc)₈(OH)₂]·2.60H₂O along [001] with hydrogen-bonding interactions between the hydroxy group and the O atoms of disordered water molecules (shown as blue dotted lines).

Synthesis and crystallization

Single crystals of [Ni₅(OAc)₈(OH)₂]·2.60H₂O were inadvertently obtained by reacting Ni(OAc)₂·4H₂O, KOH (>85%_wt) and ∼80%_wt H₃AsO₄ under hydrothermal conditions in an approximate 3:2:3 molar ratio. The reactants were introduced in a Teflon lined steal autoclave and heated at 493 K for 3 d. After cooling to room temperature, large faint greenish plates of [Ni₅(OAc)₈(OH)₂]·2.60H₂O were directly isolated from the mother liquor under a polarizing microscope.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The H atom of the hydroxide group was located in a difference-Fourier map and was refined as riding on the parent O atom with U_iso(H) = 1.5U_eq(O). Free refinement of the occupation factors of the three crystal water O-atom positions indicated underoccupation for all of them. For the final structure model, the two least occupied positions (OW2, OW3) were paired and coupled with the occupation factor of the most occupied site (OW1) so that the sum of site occupation factors equals 1. The water H atoms could not be located and were excluded from the structural model, but are included for calculation of crystal data.

Table 3
Experimental details

Crystal data
Chemical formula	[Ni₅(C₂H₃O₂)₈(OH)₂]·2.60H2O
M_r	846.80
Crystal system, space group	Tetragonal, I4₁/a
Temperature (K)	100
a, c (Å)	23.3025 (11), 11.2648 (5)
V (Å³)	6116.9 (6)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	3.10
Crystal size (mm)	0.20 × 0.12 × 0.05 × 0.04 (radius)

Data collection
Diffractometer	Stoe Stadivari
Absorption correction	Multi-scan (LANA; Koziskova et al., 2016 )
T_min, T_max	0.581, 0.710
No. of measured, independent and observed [I > 2σ(I)] reflections	20999, 5145, 2744
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.756

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.069, 0.83
No. of reflections	5145
No. of parameters	210
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.91
Computer programs: X-AREA (Stoe & Cie, 2024 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2420345

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314625000823/bt4163sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314625000823/bt4163Isup2.hkl

checkCIF report

Computing details top

Poly[[bis(µ₄-acetato-κ⁴O:O:O':O')tetrakis(µ₃-acetato-κ³O:O:O')bis(µ₂-acetato-κ²O:O')bis(µ₃-hydroxido)pentanickel(II)] 2.60-hydrate] top

Crystal data top

[Ni₅(C₂H₃O₂)₈(OH)₂]·2.60H2O	D_x = 1.839 Mg m⁻³
M_r = 846.80	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4₁/a	Cell parameters from 9821 reflections
a = 23.3025 (11) Å	θ = 1.8–30.9°
c = 11.2648 (5) Å	µ = 3.10 mm⁻¹
V = 6116.9 (6) Å³	T = 100 K
Z = 8	Plate, light green
F(000) = 3456	0.20 × 0.12 × 0.05 × 0.04 (radius) mm

Data collection top

Stoe Stadivari diffractometer	5145 independent reflections
Radiation source: Axo_Mo	2744 reflections with I > 2σ(I)
Graded multilayer mirror monochromator	R_int = 0.069
Detector resolution: 13.33 pixels mm^-1	θ_max = 32.5°, θ_min = 2.0°
rotation method, ω scans	h = −31→35
Absorption correction: multi-scan (LANA; Koziskova et al., 2016)	k = −34→33
T_min = 0.581, T_max = 0.710	l = −16→7
20999 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.069	w = 1/[σ²(F_o²) + (0.026P)²] where P = (F_o² + 2F_c²)/3
S = 0.83	(Δ/σ)_max = 0.002
5145 reflections	Δρ_max = 0.53 e Å⁻³
210 parameters	Δρ_min = −0.91 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	1.000000	0.500000	0.500000	0.01941 (13)
Ni2	0.87305 (2)	0.53890 (2)	0.49712 (3)	0.01354 (8)
Ni3	0.77923 (2)	0.44682 (2)	0.52555 (3)	0.01217 (8)
O1	0.90748 (9)	0.59881 (9)	0.60134 (16)	0.0211 (5)
O2	1.00011 (9)	0.57249 (10)	0.59387 (17)	0.0284 (5)
O3	0.94065 (8)	0.53418 (9)	0.37833 (14)	0.0183 (5)
O4	0.88695 (8)	0.53130 (9)	0.21325 (15)	0.0214 (5)
O5	0.92122 (8)	0.47408 (9)	0.57859 (15)	0.0191 (5)
O6	0.84795 (8)	0.42100 (8)	0.63759 (14)	0.0134 (4)
O7	0.70649 (8)	0.46180 (8)	0.42844 (15)	0.0178 (4)
O8	0.72147 (8)	0.54712 (8)	0.34548 (14)	0.0136 (4)
O9	0.83183 (8)	0.47852 (8)	0.40476 (14)	0.0122 (4)
H9	0.858792	0.448659	0.373873	0.018*
OW1	0.8698 (2)	0.37614 (17)	0.2711 (4)	0.0573 (14)	0.699 (5)
OW2	0.8781 (4)	0.3908 (4)	0.0907 (8)	0.070 (4)	0.301 (5)
OW3	0.8977 (4)	0.3816 (4)	0.3396 (8)	0.041 (3)	0.301 (5)
C1	0.97488 (17)	0.65457 (18)	0.7052 (4)	0.0710 (15)
H1A	0.965806	0.690456	0.663914	0.106*
H1B	1.015970	0.653458	0.723552	0.106*
H1C	0.952762	0.652406	0.779061	0.106*
C2	0.95967 (16)	0.60452 (16)	0.6271 (3)	0.0316 (8)
C3	0.98514 (14)	0.51384 (18)	0.1903 (3)	0.0435 (11)
H3A	0.994597	0.547377	0.141613	0.065*
H3B	0.976865	0.481045	0.138644	0.065*
H3C	1.017715	0.504596	0.241930	0.065*
C4	0.93369 (12)	0.52682 (13)	0.2648 (2)	0.0205 (6)
C5	0.94067 (13)	0.37866 (14)	0.6475 (3)	0.0338 (9)
H5A	0.938084	0.369374	0.732144	0.051*
H5B	0.980102	0.389891	0.628096	0.051*
H5C	0.929924	0.344947	0.600447	0.051*
C6	0.90074 (13)	0.42727 (13)	0.6195 (2)	0.0183 (7)
C7	0.62615 (14)	0.52147 (16)	0.4064 (3)	0.0487 (11)
H7A	0.618561	0.561801	0.387364	0.073*
H7B	0.614544	0.513707	0.488435	0.073*
H7C	0.604258	0.496792	0.352400	0.073*
C8	0.68878 (12)	0.50943 (13)	0.3925 (2)	0.0167 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0095 (3)	0.0283 (3)	0.0204 (3)	−0.0013 (2)	−0.0010 (2)	0.0099 (2)
Ni2	0.01025 (19)	0.0152 (2)	0.01523 (16)	−0.00078 (14)	−0.00080 (15)	0.00298 (15)
Ni3	0.0127 (2)	0.01059 (19)	0.01326 (15)	−0.00031 (14)	0.00098 (14)	0.00057 (14)
O1	0.0166 (12)	0.0224 (13)	0.0244 (10)	−0.0019 (9)	−0.0067 (9)	−0.0002 (9)
O2	0.0157 (13)	0.0348 (15)	0.0348 (12)	−0.0056 (10)	−0.0080 (10)	0.0042 (11)
O3	0.0107 (11)	0.0305 (13)	0.0138 (9)	−0.0011 (9)	−0.0005 (8)	0.0093 (9)
O4	0.0134 (11)	0.0343 (14)	0.0165 (9)	0.0008 (9)	−0.0017 (8)	0.0020 (9)
O5	0.0110 (11)	0.0244 (13)	0.0219 (10)	−0.0022 (9)	−0.0023 (8)	0.0117 (9)
O6	0.0107 (11)	0.0138 (11)	0.0157 (9)	−0.0002 (8)	0.0016 (8)	0.0037 (8)
O7	0.0201 (12)	0.0142 (11)	0.0192 (9)	−0.0033 (9)	−0.0056 (9)	0.0021 (9)
O8	0.0114 (11)	0.0141 (11)	0.0154 (8)	−0.0020 (8)	0.0005 (8)	0.0001 (8)
O9	0.0125 (11)	0.0103 (10)	0.0138 (8)	0.0021 (8)	0.0014 (8)	0.0005 (8)
OW1	0.062 (3)	0.050 (3)	0.060 (3)	0.013 (2)	0.009 (3)	0.001 (2)
OW2	0.057 (8)	0.087 (9)	0.065 (6)	0.037 (6)	−0.022 (5)	−0.016 (6)
OW3	0.044 (6)	0.033 (5)	0.047 (5)	0.016 (4)	−0.029 (4)	−0.020 (4)
C1	0.049 (3)	0.060 (3)	0.104 (3)	0.001 (2)	−0.044 (3)	−0.038 (3)
C2	0.034 (2)	0.031 (2)	0.0298 (18)	−0.0104 (17)	−0.0141 (16)	0.0046 (15)
C3	0.019 (2)	0.087 (3)	0.0240 (16)	0.0062 (19)	0.0037 (15)	0.0094 (19)
C4	0.0133 (15)	0.0274 (18)	0.0208 (14)	0.0023 (12)	0.0019 (13)	0.0057 (13)
C5	0.0184 (19)	0.036 (2)	0.0472 (19)	0.0124 (15)	0.0106 (16)	0.0220 (17)
C6	0.0160 (17)	0.0234 (18)	0.0154 (13)	0.0011 (13)	0.0001 (12)	0.0036 (12)
C7	0.015 (2)	0.056 (3)	0.075 (3)	0.0044 (18)	0.0072 (19)	0.044 (2)
C8	0.0114 (15)	0.0257 (18)	0.0129 (12)	0.0006 (13)	−0.0030 (11)	0.0013 (12)

Geometric parameters (Å, º) top

Ni1—O2ⁱ	1.993 (2)	O5—C6	1.277 (3)
Ni1—O2	1.993 (2)	O6—C6	1.255 (3)
Ni1—O3ⁱ	2.1037 (18)	O7—C8	1.251 (3)
Ni1—O3	2.1037 (18)	O8—C8	1.278 (3)
Ni1—O5	2.1257 (19)	O9—H9	1.0000
Ni1—O5ⁱ	2.1257 (19)	C1—H1A	0.9800
Ni2—O1	1.993 (2)	C1—H1B	0.9800
Ni2—O9	1.9962 (18)	C1—H1C	0.9800
Ni2—O3	2.0698 (18)	C1—C2	1.503 (5)
Ni2—O5	2.0937 (19)	C3—H3A	0.9800
Ni2—O8ⁱⁱ	2.1016 (18)	C3—H3B	0.9800
Ni2—O6ⁱⁱⁱ	2.1140 (18)	C3—H3C	0.9800
Ni3—O9	1.9747 (18)	C3—C4	1.494 (4)
Ni3—O9ⁱⁱ	1.9902 (17)	C5—H5A	0.9800
Ni3—O7	2.0474 (19)	C5—H5B	0.9800
Ni3—O4ⁱⁱ	2.0750 (19)	C5—H5C	0.9800
Ni3—O8ⁱⁱ	2.1023 (19)	C5—C6	1.499 (4)
Ni3—O6	2.1259 (18)	C7—H7A	0.9800
O1—C2	1.257 (4)	C7—H7B	0.9800
O2—C2	1.259 (4)	C7—H7C	0.9800
O3—C4	1.301 (3)	C7—C8	1.495 (4)
O4—C4	1.238 (3)

O2ⁱ—Ni1—O2	180.0	C6—O5—Ni1	135.72 (19)
O2—Ni1—O3	91.47 (8)	C6—O5—Ni2	125.03 (18)
O2—Ni1—O3ⁱ	88.53 (8)	Ni2ⁱⁱ—O6—Ni3	89.64 (7)
O2ⁱ—Ni1—O3	88.53 (8)	C6—O6—Ni2ⁱⁱ	142.11 (18)
O2ⁱ—Ni1—O3ⁱ	91.47 (8)	C6—O6—Ni3	127.48 (17)
O2—Ni1—O5	91.20 (8)	C8—O7—Ni3	126.65 (19)
O2—Ni1—O5ⁱ	88.80 (8)	Ni2ⁱⁱⁱ—O8—Ni3ⁱⁱⁱ	94.22 (7)
O2ⁱ—Ni1—O5ⁱ	91.20 (8)	C8—O8—Ni2ⁱⁱⁱ	136.79 (19)
O2ⁱ—Ni1—O5	88.80 (8)	C8—O8—Ni3ⁱⁱⁱ	123.99 (18)
O3—Ni1—O3ⁱ	180.0	Ni2—O9—H9	111.7
O3ⁱ—Ni1—O5	100.88 (7)	Ni3—O9—Ni2	101.72 (7)
O3—Ni1—O5	79.12 (7)	Ni3ⁱⁱⁱ—O9—Ni2	97.13 (8)
O3ⁱ—Ni1—O5ⁱ	79.12 (7)	Ni3—O9—Ni3ⁱⁱⁱ	121.18 (9)
O3—Ni1—O5ⁱ	100.89 (7)	Ni3—O9—H9	111.7
O5—Ni1—O5ⁱ	180.0	Ni3ⁱⁱⁱ—O9—H9	111.7
O1—Ni2—O3	96.42 (8)	H1A—C1—H1B	109.5
O1—Ni2—O5	91.80 (8)	H1A—C1—H1C	109.5
O1—Ni2—O6ⁱⁱⁱ	94.78 (7)	H1B—C1—H1C	109.5
O1—Ni2—O8ⁱⁱ	96.25 (8)	C2—C1—H1A	109.5
O1—Ni2—O9	174.04 (8)	C2—C1—H1B	109.5
O3—Ni2—O5	80.62 (7)	C2—C1—H1C	109.5
O3—Ni2—O6ⁱⁱⁱ	91.54 (7)	O1—C2—O2	126.4 (3)
O3—Ni2—O8ⁱⁱ	167.29 (7)	O1—C2—C1	116.4 (3)
O5—Ni2—O6ⁱⁱⁱ	170.29 (7)	O2—C2—C1	117.2 (3)
O5—Ni2—O8ⁱⁱ	97.89 (7)	H3A—C3—H3B	109.5
O8ⁱⁱ—Ni2—O6ⁱⁱⁱ	88.49 (7)	H3A—C3—H3C	109.5
O9—Ni2—O3	89.53 (7)	H3B—C3—H3C	109.5
O9—Ni2—O5	88.74 (7)	C4—C3—H3A	109.5
O9—Ni2—O6ⁱⁱⁱ	85.46 (7)	C4—C3—H3B	109.5
O9—Ni2—O8ⁱⁱ	77.80 (7)	C4—C3—H3C	109.5
O4ⁱⁱ—Ni3—O6	85.24 (7)	O3—C4—C3	118.6 (3)
O4ⁱⁱ—Ni3—O8ⁱⁱ	166.95 (8)	O4—C4—O3	124.0 (3)
O7—Ni3—O4ⁱⁱ	89.94 (8)	O4—C4—C3	117.4 (2)
O7—Ni3—O6	171.54 (7)	H5A—C5—H5B	109.5
O7—Ni3—O8ⁱⁱ	102.12 (7)	H5A—C5—H5C	109.5
O8ⁱⁱ—Ni3—O6	83.37 (7)	H5B—C5—H5C	109.5
O9ⁱⁱ—Ni3—O4ⁱⁱ	86.88 (7)	C6—C5—H5A	109.5
O9—Ni3—O4ⁱⁱ	95.99 (7)	C6—C5—H5B	109.5
O9—Ni3—O6	92.72 (7)	C6—C5—H5C	109.5
O9ⁱⁱ—Ni3—O6	85.30 (7)	O5—C6—C5	119.3 (3)
O9—Ni3—O7	94.70 (7)	O6—C6—O5	121.6 (3)
O9ⁱⁱ—Ni3—O7	87.50 (7)	O6—C6—C5	119.1 (3)
O9—Ni3—O8ⁱⁱ	78.25 (7)	H7A—C7—H7B	109.5
O9ⁱⁱ—Ni3—O8ⁱⁱ	98.49 (7)	H7A—C7—H7C	109.5
O9—Ni3—O9ⁱⁱ	176.38 (9)	H7B—C7—H7C	109.5
C2—O1—Ni2	126.8 (2)	C8—C7—H7A	109.5
C2—O2—Ni1	131.2 (2)	C8—C7—H7B	109.5
Ni2—O3—Ni1	95.69 (7)	C8—C7—H7C	109.5
C4—O3—Ni1	132.29 (19)	O7—C8—O8	123.2 (3)
C4—O3—Ni2	123.22 (18)	O7—C8—C7	117.0 (3)
C4—O4—Ni3ⁱⁱⁱ	131.83 (17)	O8—C8—C7	119.8 (3)
Ni2—O5—Ni1	94.33 (7)

Ni1—O2—C2—O1	−4.1 (5)	Ni2ⁱⁱ—O6—C6—O5	−150.4 (2)
Ni1—O2—C2—C1	175.8 (2)	Ni2ⁱⁱ—O6—C6—C5	29.1 (5)
Ni1—O3—C4—O4	151.5 (2)	Ni2ⁱⁱⁱ—O8—C8—O7	166.11 (17)
Ni1—O3—C4—C3	−30.4 (4)	Ni2ⁱⁱⁱ—O8—C8—C7	−13.8 (4)
Ni1—O5—C6—O6	−164.02 (18)	Ni3ⁱⁱⁱ—O4—C4—O3	−18.6 (5)
Ni1—O5—C6—C5	16.4 (4)	Ni3ⁱⁱⁱ—O4—C4—C3	163.2 (2)
Ni2—O1—C2—O2	−1.8 (5)	Ni3—O6—C6—O5	43.1 (4)
Ni2—O1—C2—C1	178.3 (2)	Ni3—O6—C6—C5	−137.4 (2)
Ni2—O3—C4—O4	12.4 (4)	Ni3—O7—C8—O8	44.2 (3)
Ni2—O3—C4—C3	−169.5 (2)	Ni3—O7—C8—C7	−135.9 (2)
Ni2—O5—C6—O6	−15.7 (4)	Ni3ⁱⁱⁱ—O8—C8—O7	18.2 (4)
Ni2—O5—C6—C5	164.8 (2)	Ni3ⁱⁱⁱ—O8—C8—C7	−161.7 (2)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) y+1/4, −x+5/4, z+1/4; (iii) −y+5/4, x−1/4, z−1/4.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9···OW1	1.00	2.06	2.957 (4)	147
O9—H9···OW3	1.00	1.85	2.827 (8)	166
O7···OW2ⁱⁱⁱ			2.87
OW2···OW3			2.85

Symmetry code: (iii) −y+5/4, x−1/4, z−1/4.

Acknowledgements

We acknowledge TU Wien Bibliothek for financial support through its Open Access Funding Programme.

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