Hexa­aqua­nickel(II) bis­[tri­aqua-μ3-oxalato-di-μ-oxalato-bariumchromate(III)] tetra­hydrate

Mbiangué, Y.A.; Ndinga, M.L.; Nduga, J.P.; Wenger, E.; Lecomte, C.

doi:10.1107/S2056989020009536

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ISSN: 2056-9890

Volume 76| Part 8| August 2020| Pages 1316-1319

https://doi.org/10.1107/S2056989020009536

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Hexaaquanickel(II) bis[triaqua-μ₃-oxalato-di-μ-oxalato-bariumchromate(III)] tetrahydrate

Yves Alain Mbiangué,^a ^* Manelsa Lande Ndinga,^a Jean Pierre Nduga,^a Emmanuel Wenger ^b and Claude Lecomte ^b

^aChemistry Department, Higher Teachers' Training College, University of Maroua, PO Box 55, Maroua, Cameroon, and ^bUniversité de Lorraine, CNRS, CRM², F54000, Nancy, France
^*Correspondence e-mail: mbiangueya@yahoo.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 22 June 2020; accepted 13 July 2020; online 17 July 2020)

The title compound, [Ni(H₂O)₆][BaCr(C₂O₄)₃(H₂O)₃]₂·4H₂O, was obtained in the form of single crystals from the slow evaporation of an aqueous mixture of {Ba₆(H₂O)₁₇[Cr(C₂O₄)₃]₄}·7H₂O and NiSO₄·6H₂O in the molar ratio 1:4. Its structure is made up of corrugated anionic (101) layers of formula [BaCr(C₂O₄)₃(H₂O)₃]_nⁿ⁻ that leave voids accommodating the charge-compensating cations, [Ni(H₂O)₆]²⁺ (point group symmetry $[\overline{1}]$ ), as well as the water molecules of crystallization. The anionic layers are built from the connection of barium and chromium atoms through bridging oxalate ligands. The Cr^III atom is hexacoordinated by O atoms of three oxalate ligands while the Ba^II atom is tenfold coordinated by three O atoms of water molecules and seven O atoms of four oxalate ligands. Each Ni^II atom sits on an inversion center and is coordinated by six water molecules. One of the uncoordinated water molecules is disordered over two sites, with a refined occupancy ratio of 0.51 (5):0.49 (5). In the crystal, extensive O—H⋯O hydrogen-bonding interactions link the anionic layers, the charge-balancing cations as well as the water molecules of crystallization into a three-dimensional supramolecular network.

Keywords: crystal structure; tris(oxalato)chromate(III); barium complexes; nickel complexes; corrugated layers.

CCDC reference: 1953456

1. Chemical context

Over the past three decades, tris(oxalato)metalate(III) complex anions, [M(C₂O₄)₃]^3–, have been extensively used for the design of many compounds with fascinating physical properties (Zhong et al., 1990 ; Bénard et al., 2001 ; Coronado et al., 2008 ; Pardo et al., 2011 ; Martin et al., 2017 ; Tsobnang et al., 2019 ; Ōkawa et al., 2020 ). One of the main reasons for that is the ability of these anions to act like ligands towards a variety of metallic cations and to build a diversity of extended structures in which neighboring metallic ions are linked through bridging oxalate ligands. From the synthetic point of view, the tris(oxalato)chromate(III) anion, [Cr(C₂O₄)₃]^3– or [Cr(ox)₃]^3–, is most attractive because of its stability and inertness toward ligand substitution. As a source of this anion, the polymeric complex salt {Ba₆(H₂O)₁₇[Cr(C₂O₄)₃]₄}·7H₂O (Bélombé et al., 2003 ) offers the possibility of easily replacing, in the reaction medium and under daylight, the Ba²⁺ ions by other cations, provided the latter are brought into that medium as their sulfates. Since Ba²⁺ has a flexible coordination sphere with coordination numbers ranging from three to twelve (Hancock et al., 2004 ), this inspired us to start a research program aimed at exploring the various structures that might arise from different combinations of [Cr(ox)₃]^3–, Ba²⁺ and other cations, and possibly studying the physical properties of the corresponding compounds. From an aqueous suspension of {Ba₆(H₂O)₁₇[Cr(C₂O₄)₃]₄}·7H₂O, a partial replacement of Ba²⁺ by Ni²⁺ led to [Ni(H₂O)₆][BaCr(C₂O₄)₃(H₂O)₃]₂·4H₂O (I), the structure of which is described herein.

2. Structural commentary

The asymmetric unit of (I) is depicted in Fig. 1. It contains one half of an [Ni(H₂O)₆]²⁺ cation situated on an inversion center, one [BaCr(C₂O₄)₃(H₂O)₃]⁻ anion and two water molecules of crystallization, one of which being equally disordered over two positions (O20A and O20B). The Ba²⁺ ion is linked to ten O atoms from three water molecules and four oxalate ligands (three chelating, one monodentately binding), with Ba—O bond lengths in the range 2.784 (3)–2.933 (3) Å (Table 1). These values are typical for ten-coordinate barium complexes with oxalate and water ligands (Alabada et al., 2015 ). One of the oxalate ligands (bearing O18) bridges three cations (two Ba and one Cr) while the two others are bis-chelating (one Ba and one Cr). In the crystal, neighboring [Cr(C₂O₄)₃]^3– units are linked through barium ions into a ladder-like chain running parallel to [010] (Fig. 2). Adjacent ladders are then connected, through Ba—O18 coordination bonds, into a corrugated layer extending parallel to (101) (Fig. 3). The packing of the layers delineates voids that accommodate the cationic complex, [Ni(H₂O)₆]²⁺, as well as the water molecules of crystallization (Fig. 4).

Table 1
Selected bond lengths (Å)

Ba1—O2	2.784 (3)	Ba1—O18ⁱ	2.873 (2)
Ba1—O17ⁱ	2.802 (2)	Ba1—O13ⁱⁱⁱ	2.874 (2)
Ba1—O15ⁱⁱ	2.855 (2)	Ba1—O3	2.880 (3)
Ba1—O18	2.856 (2)	Ba1—O14ⁱⁱⁱ	2.912 (2)
Ba1—O16ⁱⁱ	2.859 (2)	Ba1—O1	2.933 (2)
Symmetry codes: (i) -x, -y+2, -z+2; (ii) -x, -y+1, -z+2; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Figure 1
The components of the asymmetric unit of (I)

, showing the atom-numbering scheme and displacement ellipsoids at the 50% probability level.

Figure 2
Connection of [Cr(C₂O₄)₃]^3– units with Ba²⁺ cations into a ladder-like chain. Barium-coordinating water molecules have been omitted for clarity.

Figure 3
Three adjacent ladder-like chains connected through Ba₂O₂ units into a corrugated layer, viewed in the (101) plane (a) and along [010] (b). Barium-coordinating water molecules have been omitted for clarity.

Figure 4
Packing of the crystal structure of (I)

in a view along [010], showing corrugated layers interleaved by [Ni(H₂O)₆]²⁺ complex cations and water molecules of crystallization. Barium-coordinating water molecules have been omitted for clarity.

3. Supramolecular features

In the crystal, extensive O—H⋯O hydrogen-bonding interactions of medium-to-weak strength are observed (Table 2), with all the water molecules acting as hydrogen-bond donors. The water molecules of crystallization also act as hydrogen-bond acceptors, as well as all of the oxalate O atoms except O12, O14 and O18. Two barium-coordinating water molecules (O1 and O3) behave as hydrogen-bond donors toward both components of the disordered lattice water molecule (O20A and O20B) via three-center bonds, O1—H1B⋯(O20A,O20B) and O3—H3B⋯(O20A,O20B). The cationic complex, [Ni(H₂O)₆]²⁺, functions as a hydrogen-bond donor group towards one barium-coordinating water molecule (O3), one water molecule of crystallization (O19) and four oxalate O atoms, viz. O9^vi, O13^vi, O11^iv and O17^iv [symmetry codes refer to Table 2]. Together, these interactions lead to a three-dimensional supramolecular network structure.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O16^iv	0.88 (1)	2.20 (2)	3.038 (4)	160 (3)
O1—H1B⋯O20A	0.88 (1)	1.80 (2)	2.660 (18)	165 (4)
O1—H1B⋯O20B	0.88 (1)	2.25 (3)	3.08 (2)	156 (3)
O2—H2A⋯O10^iv	0.88 (1)	1.98 (1)	2.851 (3)	175 (4)
O2—H2B⋯O19^v	0.88 (1)	1.96 (1)	2.835 (4)	175 (4)
O3—H3A⋯O7	0.89 (1)	2.32 (3)	2.993 (3)	132 (3)
O3—H3B⋯O20A	0.89 (1)	2.00 (2)	2.893 (16)	176 (3)
O3—H3B⋯O20B	0.89 (1)	1.86 (2)	2.722 (11)	163 (3)
O4—H4A⋯O3	0.88 (1)	1.96 (1)	2.819 (4)	166 (4)
O4—H4B⋯O17^iv	0.87 (1)	1.92 (1)	2.791 (3)	179 (4)
O5—H5A⋯O11^iv	0.87 (1)	1.96 (1)	2.811 (3)	165 (4)
O5—H5B⋯O9^vi	0.88 (1)	1.84 (1)	2.703 (3)	167 (4)
O6—H6A⋯O13^vi	0.87 (1)	1.91 (1)	2.761 (3)	165 (4)
O6—H6B⋯O19	0.87 (1)	1.83 (1)	2.693 (3)	172 (3)
O19—H19A⋯O1^vii	0.87 (1)	1.94 (2)	2.759 (4)	157 (4)
O19—H19B⋯O15	0.87 (1)	1.93 (1)	2.789 (3)	172 (4)
O20A—H20A⋯O8^iv	0.88 (1)	2.01 (3)	2.855 (10)	161 (8)
O20A—H20B⋯O20A^viii	0.88 (1)	1.74 (3)	2.60 (2)	168 (9)
O20B—H20C⋯O8^iv	0.88 (1)	2.11 (4)	2.893 (11)	149 (7)
O20B—H20D⋯O6^vi	0.88 (1)	2.07 (4)	2.90 (3)	159 (8)
Symmetry codes: (iv) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (v) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{5\over 2}}]$ ; (vi) -x+1, -y+1, -z+2; (vii) x, y-1, z; (viii) -x+1, -y+2, -z+2.

4. Database survey

A search of the Cambridge Structural Database (CSD version 5.41, May 2020; Groom et al., 2016 ) for [M(C₂O₄)₃]ⁿ⁻ complexes with each oxalate ligand bis-chelating M and another metal M′ gave 316 hits. Of these hits, 86 contain M = Cr and only one, the parent complex of (I), contains M = Cr and M′ = Ba.

5. Synthesis and crystallization

The parent complex of (I), {Ba₆(H₂O)₁₇[Cr(C₂O₄)₃]₄}·7H₂O, was prepared as previously described (Bélombé et al., 2003). The title compound was synthesized as follows: NiSO₄·6H₂O (0.21 g, 0.8 mmol) was dissolved in water (20 ml) and the resulting green solution added dropwise, under stirring and at 313 K, to a violet suspension of {Ba₆(H₂O)₁₇[Cr(C₂O₄)₃]₄}·7H₂O (0.50 g, 0.2 mmol) in water (25 ml). After one h, the colorless precipitate of BaSO₄ was filtered off, and the filtrate was left to evaporate at room temperature. Two days later, crystals suitable for X-ray analysis were harvested.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All hydrogen atoms were located in difference-Fourier maps and refined with O—H and H⋯H distance restraints of 0.88 (1) and 1.37 (2) Å, respectively, and with U_iso(H) = 1.5U_eq(O). One lattice water molecule was refined as being disordered over two positions (O20A and O20B), with the occupancy ratio refined to 0.51 (5):0.49 (5). The distances Ba1—H3A and Ba1—H3B were restrained to be equal using a SADI instruction.

Table 3
Experimental details

Crystal data
Chemical formula	[Ni(H₂O)₆][BaCr(C₂O₄)₃(H₂O)₃]₂·4H₂O
M_r	1253.76
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	11.5556 (11), 11.0774 (13), 14.6105 (17)
β (°)	93.794 (4)
V (Å³)	1866.1 (4)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	3.27
Crystal size (mm)	0.14 × 0.09 × 0.06

Data collection
Diffractometer	Bruker D8 Venture
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.564, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	53111, 4278, 3539
R_int	0.102
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.058, 1.03
No. of reflections	4278
No. of parameters	324
No. of restraints	28
H-atom treatment	Only H-atom coordinates refined
Δρ_max, Δρ_min (e Å⁻³)	0.91, −0.85
Computer programs: APEX2 and SAINT (Bruker, 2012 ), SHELXS (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ), DIAMOND (Brandenburg & Putz, 2018 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1953456

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989020009536/wm5572sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020009536/wm5572Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Putz, 2018); software used to prepare material for publication: WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).

Hexaaquanickel(II) bis[triaqua-µ₃-oxalato-di-µ-oxalato-bariumchromate(III)] tetrahydrate top

Crystal data top

[Ni(H₂O)₆][BaCr(C₂O₄)₃(H₂O)₃]₂·4H₂O	F(000) = 1224
M_r = 1253.76	D_x = 2.231 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.5556 (11) Å	Cell parameters from 53111 reflections
b = 11.0774 (13) Å	θ = 2.2–27.5°
c = 14.6105 (17) Å	µ = 3.27 mm⁻¹
β = 93.794 (4)°	T = 100 K
V = 1866.1 (4) Å³	Block, metallic dark red
Z = 2	0.14 × 0.09 × 0.06 mm

Data collection top

Bruker D8 Venture diffractometer	3539 reflections with I > 2σ(I)
ω scans	R_int = 0.102
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 27.5°, θ_min = 2.2°
T_min = 0.564, T_max = 0.746	h = −15→14
53111 measured reflections	k = −14→14
4278 independent reflections	l = −18→18

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.026	Only H-atom coordinates refined
wR(F²) = 0.058	w = 1/[σ²(F_o²) + (0.0172P)² + 3.0153P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
4278 reflections	Δρ_max = 0.91 e Å⁻³
324 parameters	Δρ_min = −0.85 e Å⁻³
28 restraints	Extinction correction: SHELXL-2018/3 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00113 (15)

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)
Ba1	0.08524 (2)	0.86116 (2)	1.12114 (2)	0.00717 (7)
Ni1	0.500000	0.500000	1.000000	0.00719 (12)
Cr1	0.11343 (4)	0.64371 (4)	0.80510 (3)	0.00671 (11)
O1	0.2825 (2)	1.0283 (2)	1.13529 (18)	0.0194 (5)
H1A	0.295 (3)	1.065 (4)	1.1884 (15)	0.029*
H1B	0.3528 (16)	1.008 (4)	1.120 (3)	0.029*
O2	0.2458 (2)	0.8272 (2)	1.2695 (2)	0.0254 (6)
H2A	0.311 (2)	0.867 (4)	1.273 (3)	0.038*
H2B	0.242 (3)	0.798 (4)	1.3252 (14)	0.038*
O3	0.2799 (2)	0.7817 (2)	1.02345 (18)	0.0239 (6)
H3A	0.268 (3)	0.809 (4)	0.9661 (11)	0.036*
H3B	0.340 (2)	0.829 (3)	1.041 (2)	0.036*
O4	0.36196 (19)	0.5495 (2)	1.07281 (16)	0.0128 (5)
H4A	0.327 (3)	0.6188 (19)	1.064 (2)	0.019*
H4B	0.384 (3)	0.551 (3)	1.1313 (9)	0.019*
O5	0.61283 (18)	0.5438 (2)	1.10821 (15)	0.0111 (5)
H5A	0.597 (3)	0.606 (2)	1.141 (2)	0.017*
H5B	0.6886 (9)	0.541 (3)	1.109 (3)	0.017*
O6	0.4836 (2)	0.3258 (2)	1.04722 (16)	0.0117 (5)
H6A	0.508 (3)	0.304 (3)	1.1027 (12)	0.018*
H6B	0.4116 (13)	0.301 (3)	1.041 (2)	0.018*
O7	0.27008 (18)	0.71183 (19)	0.82518 (14)	0.0088 (4)
O8	0.17713 (18)	0.57697 (19)	0.69450 (15)	0.0098 (4)
O9	0.15646 (18)	0.49939 (19)	0.87894 (15)	0.0095 (4)
O10	−0.03403 (18)	0.55595 (19)	0.78547 (15)	0.0105 (5)
O11	0.04723 (18)	0.78461 (19)	0.73672 (14)	0.0090 (4)
O12	0.06071 (18)	0.73167 (19)	0.91145 (15)	0.0099 (4)
O13	0.44555 (18)	0.7013 (2)	0.76971 (15)	0.0109 (5)
O14	0.34645 (19)	0.5579 (2)	0.62938 (16)	0.0125 (5)
O15	0.08516 (19)	0.32087 (19)	0.92016 (15)	0.0117 (5)
O16	−0.12046 (19)	0.3838 (2)	0.82179 (17)	0.0158 (5)
O17	−0.06735 (19)	0.94310 (19)	0.75914 (15)	0.0103 (4)
O18	−0.03303 (18)	0.89973 (19)	0.94573 (15)	0.0088 (4)
O19	0.2628 (2)	0.2480 (2)	1.04657 (19)	0.0244 (6)
H19A	0.256 (4)	0.1727 (15)	1.062 (3)	0.037*
H19B	0.206 (3)	0.263 (3)	1.007 (2)	0.037*
O20A	0.4749 (9)	0.938 (2)	1.0718 (8)	0.015 (3)	0.51 (5)
H20A	0.543 (3)	0.923 (8)	1.099 (5)	0.023*	0.51 (5)
H20B	0.493 (6)	0.970 (8)	1.020 (3)	0.023*	0.51 (5)
O20B	0.4877 (12)	0.895 (2)	1.0565 (11)	0.018 (2)	0.49 (5)
H20C	0.536 (6)	0.875 (7)	1.103 (4)	0.027*	0.49 (5)
H20D	0.477 (7)	0.825 (4)	1.028 (5)	0.027*	0.49 (5)
C1	0.3415 (3)	0.6770 (3)	0.7665 (2)	0.0085 (6)
C2	0.2869 (3)	0.5965 (3)	0.6882 (2)	0.0087 (6)
C3	0.0763 (3)	0.4184 (3)	0.8807 (2)	0.0081 (6)
C4	−0.0373 (3)	0.4528 (3)	0.8258 (2)	0.0092 (6)
C5	−0.0088 (3)	0.8571 (3)	0.7871 (2)	0.0073 (6)
C6	0.0054 (3)	0.8296 (3)	0.8905 (2)	0.0078 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ba1	0.00780 (10)	0.00561 (9)	0.00811 (10)	0.00062 (7)	0.00049 (6)	0.00064 (7)
Ni1	0.0055 (3)	0.0091 (3)	0.0068 (3)	0.0002 (2)	−0.0008 (2)	−0.0013 (2)
Cr1	0.0055 (2)	0.0055 (2)	0.0092 (2)	0.00058 (18)	0.00116 (18)	0.00096 (19)
O1	0.0149 (12)	0.0216 (13)	0.0213 (14)	−0.0025 (10)	−0.0011 (10)	0.0013 (11)
O2	0.0171 (13)	0.0242 (14)	0.0329 (16)	−0.0095 (11)	−0.0126 (12)	0.0088 (12)
O3	0.0239 (14)	0.0266 (15)	0.0211 (14)	0.0006 (11)	0.0012 (11)	−0.0033 (11)
O4	0.0101 (11)	0.0168 (12)	0.0113 (11)	0.0026 (9)	0.0003 (9)	−0.0013 (9)
O5	0.0063 (10)	0.0142 (11)	0.0127 (12)	0.0021 (9)	−0.0008 (9)	−0.0051 (9)
O6	0.0103 (11)	0.0144 (11)	0.0100 (11)	0.0000 (9)	−0.0020 (9)	0.0033 (9)
O7	0.0073 (10)	0.0086 (10)	0.0105 (11)	−0.0005 (8)	0.0015 (8)	−0.0015 (9)
O8	0.0063 (10)	0.0120 (11)	0.0111 (11)	0.0000 (8)	0.0010 (8)	−0.0022 (9)
O9	0.0063 (10)	0.0064 (10)	0.0155 (12)	0.0000 (8)	−0.0014 (9)	0.0020 (9)
O10	0.0066 (10)	0.0087 (10)	0.0162 (12)	0.0000 (8)	−0.0004 (9)	0.0035 (9)
O11	0.0101 (10)	0.0086 (10)	0.0084 (11)	0.0011 (8)	0.0024 (8)	0.0010 (9)
O12	0.0114 (11)	0.0095 (11)	0.0088 (11)	0.0028 (9)	0.0017 (8)	0.0033 (9)
O13	0.0061 (10)	0.0157 (12)	0.0108 (11)	−0.0021 (8)	0.0002 (8)	0.0009 (9)
O14	0.0097 (11)	0.0139 (11)	0.0142 (12)	−0.0003 (9)	0.0042 (9)	−0.0018 (9)
O15	0.0144 (11)	0.0076 (10)	0.0126 (12)	−0.0002 (9)	−0.0019 (9)	0.0036 (9)
O16	0.0075 (11)	0.0110 (12)	0.0282 (14)	−0.0014 (9)	−0.0034 (10)	0.0037 (10)
O17	0.0138 (11)	0.0086 (11)	0.0081 (11)	0.0038 (9)	−0.0018 (9)	0.0014 (9)
O18	0.0117 (11)	0.0070 (10)	0.0078 (11)	−0.0003 (8)	0.0017 (9)	0.0000 (8)
O19	0.0201 (13)	0.0203 (14)	0.0307 (15)	−0.0076 (11)	−0.0138 (11)	0.0119 (12)
O20A	0.015 (3)	0.021 (7)	0.009 (4)	−0.003 (4)	0.000 (2)	−0.004 (4)
O20B	0.021 (4)	0.020 (6)	0.012 (4)	−0.003 (4)	−0.002 (3)	−0.001 (4)
C1	0.0100 (15)	0.0081 (13)	0.0075 (15)	0.0006 (11)	0.0005 (12)	0.0030 (11)
C2	0.0106 (15)	0.0068 (13)	0.0089 (15)	−0.0004 (11)	0.0010 (12)	0.0019 (12)
C3	0.0093 (14)	0.0079 (15)	0.0074 (15)	0.0000 (12)	0.0021 (12)	−0.0029 (12)
C4	0.0066 (14)	0.0085 (14)	0.0124 (16)	0.0011 (11)	0.0010 (12)	−0.0007 (12)
C5	0.0071 (14)	0.0067 (13)	0.0081 (14)	−0.0027 (12)	0.0014 (11)	−0.0009 (12)
C6	0.0048 (14)	0.0070 (14)	0.0115 (15)	−0.0035 (11)	−0.0005 (12)	0.0026 (12)

Geometric parameters (Å, º) top

Ba1—O2	2.784 (3)	O4—H4A	0.875 (10)
Ba1—O17ⁱ	2.802 (2)	O4—H4B	0.874 (10)
Ba1—O15ⁱⁱ	2.855 (2)	O5—H5A	0.870 (10)
Ba1—O18	2.856 (2)	O5—H5B	0.875 (10)
Ba1—O16ⁱⁱ	2.859 (2)	O6—H6A	0.873 (10)
Ba1—O18ⁱ	2.873 (2)	O6—H6B	0.874 (10)
Ba1—O13ⁱⁱⁱ	2.874 (2)	O7—C1	1.288 (4)
Ba1—O3	2.880 (3)	O8—C2	1.297 (4)
Ba1—O14ⁱⁱⁱ	2.912 (2)	O9—C3	1.291 (4)
Ba1—O1	2.933 (2)	O10—C4	1.287 (4)
Ni1—O5^iv	2.040 (2)	O11—C5	1.292 (4)
Ni1—O5	2.040 (2)	O12—C6	1.285 (4)
Ni1—O4^iv	2.050 (2)	O13—C1	1.230 (4)
Ni1—O4	2.050 (2)	O14—C2	1.213 (4)
Ni1—O6^iv	2.062 (2)	O15—C3	1.225 (4)
Ni1—O6	2.062 (2)	O16—C4	1.226 (4)
Cr1—O8	1.964 (2)	O17—C5	1.223 (4)
Cr1—O12	1.965 (2)	O18—C6	1.225 (4)
Cr1—O7	1.965 (2)	O19—H19A	0.870 (10)
Cr1—O10	1.966 (2)	O19—H19B	0.870 (10)
Cr1—O9	1.974 (2)	O20A—H20A	0.878 (10)
Cr1—O11	1.979 (2)	O20A—H20B	0.878 (10)
O1—H1A	0.879 (10)	O20B—H20C	0.878 (10)
O1—H1B	0.884 (10)	O20B—H20D	0.879 (10)
O2—H2A	0.875 (10)	C1—C2	1.550 (4)
O2—H2B	0.878 (10)	C3—C4	1.542 (4)
O3—H3A	0.893 (10)	C5—C6	1.540 (4)
O3—H3B	0.891 (10)

O2—Ba1—O17ⁱ	72.03 (7)	O12—Cr1—O10	92.84 (9)
O2—Ba1—O15ⁱⁱ	118.93 (7)	O7—Cr1—O10	172.94 (9)
O17ⁱ—Ba1—O15ⁱⁱ	126.88 (6)	O8—Cr1—O9	92.88 (9)
O2—Ba1—O18	166.84 (7)	O12—Cr1—O9	92.84 (9)
O17ⁱ—Ba1—O18	113.19 (6)	O7—Cr1—O9	91.90 (9)
O15ⁱⁱ—Ba1—O18	68.50 (6)	O10—Cr1—O9	82.17 (9)
O2—Ba1—O16ⁱⁱ	64.53 (7)	O8—Cr1—O11	92.00 (9)
O17ⁱ—Ba1—O16ⁱⁱ	124.55 (7)	O12—Cr1—O11	83.02 (9)
O15ⁱⁱ—Ba1—O16ⁱⁱ	58.29 (6)	O7—Cr1—O11	95.39 (9)
O18—Ba1—O16ⁱⁱ	117.00 (7)	O10—Cr1—O11	90.80 (9)
O2—Ba1—O18ⁱ	120.24 (7)	O9—Cr1—O11	171.68 (9)
O17ⁱ—Ba1—O18ⁱ	58.43 (6)	Ba1—O1—H1A	116 (3)
O15ⁱⁱ—Ba1—O18ⁱ	116.93 (6)	Ba1—O1—H1B	123 (3)
O18—Ba1—O18ⁱ	58.65 (7)	H1A—O1—H1B	104 (2)
O16ⁱⁱ—Ba1—O18ⁱ	175.13 (6)	Ba1—O2—H2A	121 (3)
O2—Ba1—O13ⁱⁱⁱ	76.00 (7)	Ba1—O2—H2B	134 (3)
O17ⁱ—Ba1—O13ⁱⁱⁱ	69.29 (6)	H2A—O2—H2B	103 (2)
O15ⁱⁱ—Ba1—O13ⁱⁱⁱ	64.89 (6)	Ba1—O3—H3A	106 (2)
O18—Ba1—O13ⁱⁱⁱ	117.03 (6)	Ba1—O3—H3B	107 (2)
O16ⁱⁱ—Ba1—O13ⁱⁱⁱ	68.14 (7)	H3A—O3—H3B	99 (2)
O18ⁱ—Ba1—O13ⁱⁱⁱ	111.27 (6)	Ni1—O4—H4A	122 (3)
O2—Ba1—O3	80.94 (8)	Ni1—O4—H4B	109 (2)
O17ⁱ—Ba1—O3	129.65 (7)	H4A—O4—H4B	103 (2)
O15ⁱⁱ—Ba1—O3	103.29 (7)	Ni1—O5—H5A	118 (2)
O18—Ba1—O3	86.79 (7)	Ni1—O5—H5B	126 (2)
O16ⁱⁱ—Ba1—O3	75.75 (7)	H5A—O5—H5B	105 (2)
O18ⁱ—Ba1—O3	105.45 (7)	Ni1—O6—H6A	123 (2)
O13ⁱⁱⁱ—Ba1—O3	142.83 (7)	Ni1—O6—H6B	111 (2)
O2—Ba1—O14ⁱⁱⁱ	126.45 (8)	H6A—O6—H6B	104 (2)
O17ⁱ—Ba1—O14ⁱⁱⁱ	68.07 (6)	C1—O7—Cr1	114.17 (19)
O15ⁱⁱ—Ba1—O14ⁱⁱⁱ	65.42 (6)	C2—O8—Cr1	114.68 (19)
O18—Ba1—O14ⁱⁱⁱ	65.95 (6)	C3—O9—Cr1	114.79 (19)
O16ⁱⁱ—Ba1—O14ⁱⁱⁱ	113.40 (6)	C4—O10—Cr1	115.08 (19)
O18ⁱ—Ba1—O14ⁱⁱⁱ	63.38 (6)	C5—O11—Cr1	113.24 (19)
O13ⁱⁱⁱ—Ba1—O14ⁱⁱⁱ	57.43 (6)	C6—O12—Cr1	113.91 (19)
O3—Ba1—O14ⁱⁱⁱ	152.62 (7)	C1—O13—Ba1^v	120.99 (19)
O2—Ba1—O1	63.63 (7)	C2—O14—Ba1^v	120.2 (2)
O17ⁱ—Ba1—O1	63.68 (7)	C3—O15—Ba1ⁱⁱ	119.24 (19)
O15ⁱⁱ—Ba1—O1	169.31 (7)	C4—O16—Ba1ⁱⁱ	118.81 (19)
O18—Ba1—O1	107.00 (7)	C5—O17—Ba1ⁱ	117.15 (19)
O16ⁱⁱ—Ba1—O1	118.91 (7)	C6—O18—Ba1	108.89 (19)
O18ⁱ—Ba1—O1	65.59 (7)	C6—O18—Ba1ⁱ	115.98 (19)
O13ⁱⁱⁱ—Ba1—O1	124.84 (7)	Ba1—O18—Ba1ⁱ	121.35 (7)
O3—Ba1—O1	66.37 (8)	H19A—O19—H19B	106 (2)
O14ⁱⁱⁱ—Ba1—O1	122.46 (7)	H20A—O20A—H20B	102 (2)
O5^iv—Ni1—O5	180.00 (8)	H20C—O20B—H20D	103 (2)
O5^iv—Ni1—O4^iv	90.78 (9)	O13—C1—O7	125.2 (3)
O5—Ni1—O4^iv	89.22 (9)	O13—C1—C2	120.2 (3)
O5^iv—Ni1—O4	89.22 (9)	O7—C1—C2	114.6 (3)
O5—Ni1—O4	90.78 (9)	O14—C2—O8	126.5 (3)
O4^iv—Ni1—O4	180.0	O14—C2—C1	120.2 (3)
O5^iv—Ni1—O6^iv	91.79 (9)	O8—C2—C1	113.3 (3)
O5—Ni1—O6^iv	88.21 (9)	O15—C3—O9	125.8 (3)
O4^iv—Ni1—O6^iv	89.13 (9)	O15—C3—C4	120.3 (3)
O4—Ni1—O6^iv	90.87 (9)	O9—C3—C4	113.9 (3)
O5^iv—Ni1—O6	88.21 (9)	O16—C4—O10	125.4 (3)
O5—Ni1—O6	91.79 (9)	O16—C4—C3	120.6 (3)
O4^iv—Ni1—O6	90.87 (9)	O10—C4—C3	114.1 (3)
O4—Ni1—O6	89.13 (9)	O17—C5—O11	125.6 (3)
O6^iv—Ni1—O6	180.00 (4)	O17—C5—C6	120.2 (3)
O8—Cr1—O12	171.94 (9)	O11—C5—C6	114.3 (3)
O8—Cr1—O7	82.86 (9)	O18—C6—O12	125.1 (3)
O12—Cr1—O7	91.28 (9)	O18—C6—C5	120.1 (3)
O8—Cr1—O10	93.57 (9)	O12—C6—C5	114.8 (3)

Ba1^v—O13—C1—O7	−172.7 (2)	Cr1—O10—C4—C3	−0.6 (3)
Ba1^v—O13—C1—C2	8.4 (4)	O15—C3—C4—O16	0.9 (4)
Cr1—O7—C1—O13	−174.5 (2)	O9—C3—C4—O16	180.0 (3)
Cr1—O7—C1—C2	4.4 (3)	O15—C3—C4—O10	−178.0 (3)
Ba1^v—O14—C2—O8	173.1 (2)	O9—C3—C4—O10	1.1 (4)
Ba1^v—O14—C2—C1	−7.5 (4)	Ba1ⁱ—O17—C5—O11	−150.8 (2)
Cr1—O8—C2—O14	175.1 (3)	Ba1ⁱ—O17—C5—C6	27.7 (3)
Cr1—O8—C2—C1	−4.3 (3)	Cr1—O11—C5—O17	−171.9 (2)
O13—C1—C2—O14	−0.5 (5)	Cr1—O11—C5—C6	9.5 (3)
O7—C1—C2—O14	−179.5 (3)	Ba1—O18—C6—O12	20.2 (4)
O13—C1—C2—O8	178.9 (3)	Ba1ⁱ—O18—C6—O12	161.3 (2)
O7—C1—C2—O8	−0.1 (4)	Ba1—O18—C6—C5	−158.5 (2)
Ba1ⁱⁱ—O15—C3—O9	−166.0 (2)	Ba1ⁱ—O18—C6—C5	−17.4 (3)
Ba1ⁱⁱ—O15—C3—C4	13.0 (3)	Cr1—O12—C6—O18	−178.3 (2)
Cr1—O9—C3—O15	178.1 (2)	Cr1—O12—C6—C5	0.4 (3)
Cr1—O9—C3—C4	−1.0 (3)	O17—C5—C6—O18	−6.7 (4)
Ba1ⁱⁱ—O16—C4—O10	164.6 (2)	O11—C5—C6—O18	172.0 (3)
Ba1ⁱⁱ—O16—C4—C3	−14.2 (4)	O17—C5—C6—O12	174.6 (3)
Cr1—O10—C4—O16	−179.4 (3)	O11—C5—C6—O12	−6.8 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O16^vi	0.88 (1)	2.20 (2)	3.038 (4)	160 (3)
O1—H1B···O20A	0.88 (1)	1.80 (2)	2.660 (18)	165 (4)
O1—H1B···O20B	0.88 (1)	2.25 (3)	3.08 (2)	156 (3)
O2—H2A···O10^vi	0.88 (1)	1.98 (1)	2.851 (3)	175 (4)
O2—H2B···O19^vii	0.88 (1)	1.96 (1)	2.835 (4)	175 (4)
O3—H3A···O7	0.89 (1)	2.32 (3)	2.993 (3)	132 (3)
O3—H3B···O20A	0.89 (1)	2.00 (2)	2.893 (16)	176 (3)
O3—H3B···O20B	0.89 (1)	1.86 (2)	2.722 (11)	163 (3)
O4—H4A···O3	0.88 (1)	1.96 (1)	2.819 (4)	166 (4)
O4—H4B···O17^vi	0.87 (1)	1.92 (1)	2.791 (3)	179 (4)
O5—H5A···O11^vi	0.87 (1)	1.96 (1)	2.811 (3)	165 (4)
O5—H5B···O9^iv	0.88 (1)	1.84 (1)	2.703 (3)	167 (4)
O6—H6A···O13^iv	0.87 (1)	1.91 (1)	2.761 (3)	165 (4)
O6—H6B···O19	0.87 (1)	1.83 (1)	2.693 (3)	172 (3)
O19—H19A···O1^viii	0.87 (1)	1.94 (2)	2.759 (4)	157 (4)
O19—H19B···O15	0.87 (1)	1.93 (1)	2.789 (3)	172 (4)
O20A—H20A···O8^vi	0.88 (1)	2.01 (3)	2.855 (10)	161 (8)
O20A—H20B···O20A^ix	0.88 (1)	1.74 (3)	2.60 (2)	168 (9)
O20B—H20C···O8^vi	0.88 (1)	2.11 (4)	2.893 (11)	149 (7)
O20B—H20D···O6^iv	0.88 (1)	2.07 (4)	2.90 (3)	159 (8)

Symmetry codes: (iv) −x+1, −y+1, −z+2; (vi) x+1/2, −y+3/2, z+1/2; (vii) −x+1/2, y+1/2, −z+5/2; (viii) x, y−1, z; (ix) −x+1, −y+2, −z+2.

Acknowledgements

YAM thanks the PMD²X X-ray diffraction facility (https://crm2.univ-lorraine.fr/lab/fr/services/pmd2x) of the Institut Jean Barriol, Université de Lorraine, for the X-ray diffraction measurements, data processing and analysis, and providing reports for publication. YAM thanks also the CCDC for providing access to the Cambridge Structural Database through the FAIRE programme.

References

Alabada, R., Kovalchukova, O., Polyakova, I., Strashnova, S. & Sergienko, V. (2015). Acta Cryst. E71, 459–462. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bélombé, M. M., Nenwa, J., Mbiangué, Y. A., Nnanga, G. E., Mbomekallé, I.-M., Hey-Hawkins, E., Lönnecke, P. & Majoumo, F. (2003). Dalton Trans. pp. 2117–2118. Google Scholar
Bénard, S., Rivière, E., Yu, P., Nakatani, K. & Delouis, J. F. (2001). Chem. Mater. 13, 159–162. Google Scholar
Brandenburg, K. & Putz, H. (2018). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2012). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Coronado, E., Galán-Mascarós, J. R., Martí-Gastaldo, C., Waerenborgh, J. C. & Gaczyński, P. (2008). Inorg. Chem. 47, 6829–6839. Web of Science CSD CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals 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
Hancock, R. D., Siddons, C. J., Oscarson, K. A. & Reibenspies, J. M. (2004). Inorg. Chim. Acta, 357, 723–727. Web of Science CSD CrossRef CAS 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
Martin, L., Lopez, J. R., Akutsu, H., Nakazawa, Y. & Imajo, S. (2017). Inorg. Chem. 56, 14045–14052. Web of Science CSD CrossRef CAS PubMed Google Scholar
Ōkawa, H., Yoshida, Y., Otsubo, K. & Kitagawa, H. (2020). Inorg. Chem. 59, 623–628. Web of Science PubMed Google Scholar
Pardo, E., Train, C., Gontard, G., Boubekeur, K., Fabelo, O., Liu, H., Dkhil, B., Lloret, F., Nakagawa, K., Tokoro, H., Ohkoshi, S. & Verdaguer, M. (2011). J. Am. Chem. Soc. 133, 15328–15331. Web of Science CSD CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Tsobnang, P. K., Hastürk, E., Fröhlich, D., Wenger, E., Durand, P., Ngolui, L. J., Lecomte, C. & Janiak, C. (2019). Cryst. Growth Des. 19, 2869–2880. Web of Science CSD CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhong, Z. J., Matsumoto, N., Okawa, H. & Kida, S. (1990). Chem. Lett. 19, 87–90. CrossRef Web of Science Google Scholar

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