Tetra­aqua­[3-oxo-1,3-bis­(pyridinium-2-yl)propan-1-olato]nickel(II) tribromide dihydrate

Westcott, B.L.; Crundwell, G.; Alicea-Velázquez, N.L.

doi:10.1107/S205698902000081X

research communications

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ISSN: 2056-9890

Volume 76| Part 2| February 2020| Pages 270-272

https://doi.org/10.1107/S205698902000081X

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Tetraaqua[3-oxo-1,3-bis(pyridinium-2-yl)propan-1-olato]nickel(II) tribromide dihydrate

Barry L. Westcott,^a Guy Crundwell ^a ^* and Nilda L. Alicea-Velázquez ^a

^aDepartment of Chemistry & Biochemistry, Central Connecticut State University, 1619 Stanley Street, New Britain, CT 06053, USA
^*Correspondence e-mail: crundwellg@ccsu.edu

Edited by M. Zeller, Purdue University, USA (Received 14 January 2020; accepted 22 January 2020; online 31 January 2020)

The crystal structure of the title compound, [Ni(C₁₃H₁₁N₂O₂)(H₂O)₄]Br₃·2H₂O, contains an octahedral Ni^II atom coordinated to the enol form of 1,3-dipyridylpropane-1,3-dione (dppo) and four water molecules. Both pyridyl rings on the ligand are protonated, forming pyridinium rings and creating an overall ligand charge of +1. The protonated nitrogen-containing rings are involved in hydrogen-bonding interactions with neighoring bromide anions. There are many additional hydrogen-bonding interactions involving coordinated water molecules on the Ni^II atom, bromide anions and hydration water molecules.

Keywords: crystal structure; dipyridylpropanedione; pyridinium; nickel.

CCDC reference: 1979583

1. Chemical context

We chose to study 1,3-dipyridylpropane-1,3-dione (dppo) in our ongoing investigations of bridged dipyridyl compounds as ligands for transition metals and rare earths. Previous studies of the di-2-pyridyl ketone (dpk) ligand illustrated that it can undergo a Lewis acid assisted hydration reaction at the ketone to form a diol (Sommerer & Abboud, 1993 ). This hydration can also occur with Arrhenius acids; however, in the absence of a metal for coordination, the pyridyl N atoms of the resulting diol are protonated (Sommerer et al., 1994 ). For the dppo in this study, the coordination to the metal center required the presence of an Arrhenius acid (HBr). No hydration of the dione occurred, the ligand adopted the enol form where O atoms behaved as a bidentate ligand, and protonation of the pyridyl rings was observed.

2. Structural commentary

Since the synthesis of the complex was in hydrobromic acid in methanol, the existence of three bromide anions required a trivalent cation. Planar dppo is in its enol form allowing the O atoms to behave as Lewis bases to the nickel center; however, the pyridine rings are both protonated. The H atoms were readily found in difference maps and refined as unconstrained atoms. The organic ligand therefore has an overall +1 charge. There are also four water molecules coordinated to the Ni^II atom, thereby completing the octahedral geometry of the [Ni(C₁₃H₁₁N₂O₂)(H₂O)₄]⁺³ cation (Fig. 1). During refinement, two additional waters of hydration were located. There is an angle of 19.48 (7)° between the mean plane of the dipyridinium ligand and the plane defined by the Ni^II atom and its four equatorial O atoms. Selected geometric parameters are listed in Table 1.

Table 1
Selected geometric parameters (Å, °)

Ni1—O1	2.003 (2)	Ni1—O6	2.080 (3)
Ni1—O2	2.006 (2)	Ni1—O5	2.088 (3)
Ni1—O3	2.031 (2)	Ni1—O4	2.088 (2)

O1—Ni1—O2	88.75 (9)	O3—Ni1—O5	93.21 (12)
O1—Ni1—O3	176.19 (9)	O6—Ni1—O5	176.52 (11)
O2—Ni1—O3	87.65 (9)	O1—Ni1—O4	90.82 (9)
O1—Ni1—O6	91.18 (10)	O2—Ni1—O4	177.08 (11)
O2—Ni1—O6	89.88 (10)	O3—Ni1—O4	92.72 (10)
O3—Ni1—O6	87.57 (12)	O6—Ni1—O4	87.24 (11)
O1—Ni1—O5	88.26 (11)	O5—Ni1—O4	89.34 (12)
O2—Ni1—O5	93.54 (11)

Figure 1
A view of the the title compound, with displacement ellipsoids drawn at the 50% probability level.

3. Supramolecular features

A packing diagram of the compound as viewed down (100) is shown in Fig. 2. There are many hydrogen-bonding interactions. The pyridinium H atoms are involved in hydrogen bonding with one of the bromide anions. Bromide anions are also engaged in hydrogen bonding with the waters of hydration and the water molecules coordinated to the Ni^II atom. The waters of hydration extend the hydrogen-bonding network by also interacting with the water molecules coordinated to the Ni^II center. A summary of the hydrogen-bonding interactions is listed in Table 2.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Br1	0.86	2.94	3.774 (4)	165
N2—H2⋯Br1	0.86	3.02	3.852 (3)	165
C1—H1A⋯Br2	0.93	2.75	3.567 (3)	147
C4—H4⋯Br3ⁱ	0.93	2.47	3.330 (3)	154
C10—H10⋯Br2ⁱⁱ	0.93	2.48	3.305 (3)	149
O3—H3A⋯Br2ⁱⁱ	0.84 (2)	2.48 (4)	3.285 (3)	161 (9)
O3—H3B⋯Br3ⁱⁱⁱ	0.83 (2)	2.40 (3)	3.212 (2)	165 (8)
O4—H4A⋯O7^iv	0.84 (2)	2.16 (5)	2.917 (4)	150 (9)
O4—H4B⋯Br3ⁱ	0.82 (2)	2.48 (3)	3.284 (3)	167 (9)
O5—H5A⋯O7	0.84 (2)	1.99 (3)	2.808 (5)	163 (10)
O5—H5B⋯O8	0.84 (2)	2.29 (6)	3.002 (6)	142 (9)
O6—H6A⋯Br1^v	0.84 (2)	2.51 (2)	3.342 (3)	175 (9)
O6—H6B⋯Br2^v	0.83 (2)	2.45 (3)	3.266 (3)	165 (9)
O7—H7A⋯Br1ⁱ	0.84 (2)	2.59 (6)	3.335 (4)	149 (9)
O7—H7B⋯Br3ⁱ	0.85 (2)	2.54 (2)	3.386 (3)	173 (9)
O8—H8A⋯Br3^vi	0.85 (2)	3.06 (3)	3.880 (7)	165 (9)
O8—H8B⋯Br1ⁱⁱⁱ	0.84 (2)	2.65 (6)	3.393 (5)	149 (9)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x, y, z+1; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) x-1, y, z; (v) -x, -y+1, -z+1; (vi) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
A view of the unit cell along (100). Bromines and free water molecules are shown as balls and sticks and hydrogen bonds as black dashed lines (Macrae et al., 2020

4. Database survey

The enol form of dppo has been used to make extended structures with cadmium (Tan et al., 2012 ), as well as with manganese (Langley et al., 2010 ). The cadmium structure is a two-dimensional chain of cadmium, chlorides, and ligands. The ligand uses both of its O atoms and pyridyl N atoms to bond to multiple Cd atoms. In Langley, several manganese clusters (with six, seven, and ten manganese atoms) were studied, all having the enol form of the ligand. The ligands vary their coordination, sometimes bonding in a bidentate fashion via the two oxygens, sometimes bidentate with a pyridine nitrogen and enol oxygen, and sometimes even monodentate via the pyridine nitrogen. Through its multiple modes of bonding in these clusters, the ligand can bond from two to four metal centers.

The ligand has also been shown to use its O atoms and one pyridyl N atom to form a bridging dilanthium complex (Brück et al., 2000 ) and a bridging triholmium species (Andrews et al., 2009 ). Finally, the ligand has formed a simpler tris[1,3-bis(pyridin-2-yl)propane-1,3-dionato]iron(III) compound where the ligand simply bonds to the iron via its O atoms (Lee et al., 2017 ). Whereas protonation of pyridyl rings on ligands are common in the literature, this structure is the first to display pyridyl protonation for this particular ligand.

5. Synthesis and crystallization

All chemicals were used as received. To 0.1458 g (0.5 mmol) of nickel bromide hydrate (Aldrich) in 35 ml of water was added 0.2424 g (1.0 mmol) of 1,3-di(2-pyridyl)-1,3-propanedione (TCI) under stirring. To this mixture, concentrated HBr (Fisher) was added dropwise until all the ligand had dissolved (pH ∼ 1). This solution was stirred at room temperature for 30 min and filtered to afford an olive-colored solution. Slow evaporation for 28 d yielded pale-red–orange crystals of the title compound. The yield of the product was 64%. The crystals decomposed when a melting-point determination was attempted. FT–IR data for the free ligand and the title compound are included as supporting information and the appearance of a broad band at 3300 cm⁻¹ and a broad band with fine structure at 3000 cm⁻¹ confirms the presence of water molecules and pyridinium rings.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms on sp²-hybridized C and N atoms were included in calculated positions, with C—H distances of 0.93 Å and U_iso(H) = 1.2U_eq(C). Water H atoms were refined applying a distance restraint of 0.84 (2) Å.

Table 3
Experimental details

Crystal data
Chemical formula	[Ni(C₁₃H₁₁N₂O₂)(H₂O)₄]Br₃·2H₂O
M_r	633.77
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.8071 (6), 23.8031 (16), 13.6302 (10)
β (°)	97.476 (9)
V (Å³)	2189.7 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	6.40
Crystal size (mm)	0.32 × 0.28 × 0.19

Data collection
Diffractometer	Agilent Xcalibur Sapphire3
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ )
T_min, T_max	0.504, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	26929, 7970, 5803
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.781

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.125, 1.05
No. of reflections	7970
No. of parameters	280
No. of restraints	12
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.10, −1.39
Computer programs: CrysAlis CCD and CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ), SHELXS2014 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2020 ) and OLEX2 (Bourhis et al., 2015 ).

Supporting information

CCDC reference: 1979583

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S205698902000081X/zl2768sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902000081X/zl2768Isup2.hkl

IR spectrum of NI(dppo). DOI: https://doi.org/10.1107/S205698902000081X/zl2768sup3.pdf

checkCIF report

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2020); software used to prepare material for publication: OLEX2 (Bourhis et al., 2015).

Tetraaqua[3-oxo-1,3-bis(pyridinium-2-yl)propan-1-olato]nickel(II) tribromide dihydrate top

Crystal data top

[Ni(C₁₃H₁₁N₂O₂)(H₂O)₄]3Br·2H₂O	F(000) = 1248
M_r = 633.77	D_x = 1.922 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.8071 (6) Å	Cell parameters from 4741 reflections
b = 23.8031 (16) Å	θ = 4.6–32.1°
c = 13.6302 (10) Å	µ = 6.40 mm⁻¹
β = 97.476 (9)°	T = 293 K
V = 2189.7 (3) Å³	Block, orange
Z = 4	0.32 × 0.28 × 0.19 mm

Data collection top

Agilent Xcalibur Sapphire3 diffractometer	7970 independent reflections
Radiation source: Enhance (Mo) X-ray Source	5803 reflections with I > 2σ(I)
Detector resolution: 16.1790 pixels mm^-1	R_int = 0.034
ω scans	θ_max = 33.7°, θ_min = 4.3°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −10→10
T_min = 0.503, T_max = 1.000	k = −36→36
26929 measured reflections	l = −20→21

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: mixed
wR(F²) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0561P)² + 2.3402P] where P = (F_o² + 2F_c²)/3
7970 reflections	(Δ/σ)_max = 0.001
280 parameters	Δρ_max = 1.10 e Å⁻³
12 restraints	Δρ_min = −1.39 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
Br1	0.28363 (5)	0.60904 (2)	0.46388 (3)	0.04291 (10)
Br2	0.22784 (5)	0.48206 (2)	0.10507 (2)	0.03503 (9)
Br3	0.80885 (8)	0.76767 (2)	0.39510 (3)	0.05624 (13)
Ni1	0.15038 (6)	0.37164 (2)	0.81987 (3)	0.02833 (10)
O1	0.2089 (4)	0.37484 (8)	0.67975 (15)	0.0311 (4)
O2	0.2542 (4)	0.45031 (9)	0.83901 (15)	0.0318 (5)
O3	0.0917 (5)	0.37407 (10)	0.96216 (18)	0.0439 (6)
O4	0.0286 (4)	0.29148 (10)	0.79662 (19)	0.0417 (6)
O5	0.4287 (5)	0.33525 (12)	0.8585 (2)	0.0489 (6)
O6	−0.1333 (4)	0.40312 (11)	0.77851 (19)	0.0414 (5)
N1	0.2313 (5)	0.45128 (15)	0.4508 (2)	0.0488 (8)
H1	0.2437	0.4862	0.4669	0.059*
N2	0.3028 (5)	0.59168 (13)	0.7459 (2)	0.0473 (7)
H2	0.3017	0.5882	0.6831	0.057*
C1	0.2240 (6)	0.43458 (18)	0.3530 (2)	0.0464 (9)
H1A	0.2312	0.4615	0.3041	0.056*
C2	0.2062 (7)	0.37877 (18)	0.3273 (2)	0.0480 (9)
H2A	0.2029	0.3677	0.2617	0.058*
C3	0.1935 (6)	0.33996 (17)	0.3999 (2)	0.0432 (8)
H3	0.1814	0.3020	0.3841	0.052*
C4	0.1984 (4)	0.35680 (12)	0.49387 (18)	0.0241 (5)
H4	0.1874	0.3297	0.5420	0.029*
C5	0.2182 (4)	0.41042 (12)	0.52228 (19)	0.0267 (5)
C6	0.2239 (5)	0.41925 (12)	0.6312 (2)	0.0267 (5)
C7	0.2441 (5)	0.47393 (12)	0.6692 (2)	0.0300 (6)
H7	0.2477	0.5037	0.6254	0.036*
C8	0.2593 (4)	0.48545 (11)	0.7704 (2)	0.0264 (5)
C9	0.2832 (4)	0.54534 (11)	0.8042 (2)	0.0246 (5)
C10	0.2865 (4)	0.55252 (11)	0.90202 (18)	0.0216 (5)
H10	0.2701	0.5211	0.9408	0.026*
C11	0.3121 (6)	0.60228 (14)	0.9464 (3)	0.0387 (7)
H11	0.3170	0.6051	1.0148	0.046*
C12	0.3313 (6)	0.64942 (15)	0.8900 (3)	0.0469 (9)
H12	0.3490	0.6845	0.9198	0.056*
C13	0.3243 (6)	0.64421 (14)	0.7904 (3)	0.0450 (8)
H13	0.3339	0.6760	0.7517	0.054*
O7	0.6193 (5)	0.29510 (15)	0.7017 (3)	0.0586 (8)
O8	0.6929 (11)	0.2404 (2)	0.9388 (4)	0.1057 (17)
H3A	0.120 (13)	0.4061 (18)	0.986 (6)	0.159*
H3B	0.140 (12)	0.349 (3)	1.000 (5)	0.159*
H4A	−0.095 (3)	0.289 (4)	0.791 (7)	0.159*
H4B	0.061 (14)	0.272 (3)	0.752 (5)	0.159*
H5A	0.489 (13)	0.317 (4)	0.818 (6)	0.159*
H5B	0.448 (15)	0.304 (2)	0.886 (7)	0.159*
H6A	−0.169 (13)	0.402 (4)	0.7173 (18)	0.159*
H6B	−0.178 (13)	0.432 (2)	0.802 (7)	0.159*
H7A	0.592 (15)	0.319 (3)	0.656 (5)	0.159*
H7B	0.513 (8)	0.281 (4)	0.673 (7)	0.159*
H8A	0.789 (10)	0.252 (4)	0.980 (6)	0.159*
H8B	0.658 (15)	0.2068 (16)	0.945 (8)	0.159*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.03826 (18)	0.0478 (2)	0.04137 (18)	−0.00130 (14)	0.00006 (14)	0.00498 (15)
Br2	0.04109 (18)	0.04094 (18)	0.02300 (13)	0.00484 (13)	0.00390 (12)	−0.00060 (11)
Br3	0.0857 (3)	0.02834 (17)	0.0548 (2)	−0.00371 (17)	0.0097 (2)	−0.01026 (15)
Ni1	0.0437 (2)	0.02121 (17)	0.02022 (16)	−0.00070 (14)	0.00474 (15)	0.00139 (12)
O1	0.0497 (13)	0.0228 (9)	0.0210 (9)	0.0008 (9)	0.0051 (9)	0.0011 (7)
O2	0.0510 (13)	0.0230 (9)	0.0213 (9)	−0.0049 (9)	0.0038 (9)	0.0000 (7)
O3	0.0761 (19)	0.0318 (12)	0.0258 (10)	−0.0031 (12)	0.0139 (12)	0.0026 (9)
O4	0.0597 (16)	0.0247 (10)	0.0418 (13)	−0.0045 (11)	0.0105 (12)	−0.0001 (9)
O5	0.0583 (17)	0.0447 (15)	0.0407 (13)	0.0133 (13)	−0.0053 (12)	0.0019 (11)
O6	0.0482 (14)	0.0358 (12)	0.0392 (12)	0.0026 (11)	0.0021 (11)	−0.0038 (10)
N1	0.064 (2)	0.0480 (18)	0.0351 (15)	0.0050 (16)	0.0085 (15)	0.0064 (13)
N2	0.064 (2)	0.0373 (15)	0.0405 (15)	−0.0065 (15)	0.0061 (15)	−0.0003 (13)
C1	0.061 (2)	0.055 (2)	0.0230 (13)	0.0033 (18)	0.0076 (15)	0.0093 (14)
C2	0.058 (2)	0.066 (3)	0.0200 (13)	0.0027 (19)	0.0057 (15)	−0.0077 (14)
C3	0.054 (2)	0.0456 (19)	0.0301 (15)	−0.0022 (16)	0.0045 (15)	−0.0164 (14)
C4	0.0314 (13)	0.0240 (11)	0.0170 (10)	−0.0010 (10)	0.0033 (10)	−0.0048 (9)
C5	0.0314 (14)	0.0292 (13)	0.0193 (10)	0.0021 (11)	0.0029 (10)	−0.0013 (10)
C6	0.0349 (14)	0.0250 (12)	0.0201 (10)	0.0019 (11)	0.0038 (10)	0.0000 (9)
C7	0.0476 (17)	0.0219 (12)	0.0204 (11)	−0.0025 (11)	0.0040 (12)	0.0018 (9)
C8	0.0341 (14)	0.0219 (11)	0.0227 (11)	−0.0020 (10)	0.0021 (11)	−0.0011 (9)
C9	0.0275 (12)	0.0226 (12)	0.0232 (11)	−0.0021 (10)	0.0022 (10)	−0.0023 (9)
C10	0.0260 (12)	0.0190 (11)	0.0202 (10)	−0.0032 (9)	0.0052 (9)	−0.0035 (8)
C11	0.0496 (19)	0.0339 (16)	0.0346 (15)	−0.0085 (14)	0.0135 (15)	−0.0141 (13)
C12	0.062 (2)	0.0276 (16)	0.053 (2)	−0.0092 (15)	0.0142 (18)	−0.0108 (14)
C13	0.065 (2)	0.0242 (14)	0.0465 (19)	−0.0097 (15)	0.0092 (18)	0.0011 (14)
O7	0.0591 (18)	0.0536 (18)	0.0612 (19)	0.0006 (14)	0.0002 (15)	0.0041 (14)
O8	0.161 (5)	0.071 (3)	0.086 (3)	0.024 (3)	0.020 (3)	0.020 (3)

Geometric parameters (Å, º) top

Ni1—O1	2.003 (2)	C2—C3	1.365 (6)
Ni1—O2	2.006 (2)	C2—H2A	0.9300
Ni1—O3	2.031 (2)	C3—C4	1.339 (4)
Ni1—O6	2.080 (3)	C3—H3	0.9300
Ni1—O5	2.088 (3)	C4—C5	1.336 (4)
Ni1—O4	2.088 (2)	C4—H4	0.9300
O1—C6	1.258 (3)	C5—C6	1.495 (4)
O2—C8	1.259 (3)	C6—C7	1.401 (4)
O3—H3A	0.84 (2)	C7—C8	1.396 (4)
O3—H3B	0.83 (2)	C7—H7	0.9300
O4—H4A	0.84 (2)	C8—C9	1.501 (4)
O4—H4B	0.82 (2)	C9—C10	1.341 (3)
O5—H5A	0.84 (2)	C10—C11	1.331 (4)
O5—H5B	0.84 (2)	C10—H10	0.9300
O6—H6A	0.84 (2)	C11—C12	1.376 (5)
O6—H6B	0.83 (2)	C11—H11	0.9300
N1—C1	1.386 (5)	C12—C13	1.358 (5)
N1—C5	1.387 (4)	C12—H12	0.9300
N1—H1	0.8600	C13—H13	0.9300
N2—C9	1.376 (4)	O7—H7A	0.84 (2)
N2—C13	1.389 (5)	O7—H7B	0.85 (2)
N2—H2	0.8600	O8—H8A	0.85 (2)
C1—C2	1.375 (6)	O8—H8B	0.84 (2)
C1—H1A	0.9300

O1—Ni1—O2	88.75 (9)	C3—C2—C1	118.7 (3)
O1—Ni1—O3	176.19 (9)	C3—C2—H2A	120.6
O2—Ni1—O3	87.65 (9)	C1—C2—H2A	120.6
O1—Ni1—O6	91.18 (10)	C4—C3—C2	119.7 (3)
O2—Ni1—O6	89.88 (10)	C4—C3—H3	120.2
O3—Ni1—O6	87.57 (12)	C2—C3—H3	120.2
O1—Ni1—O5	88.26 (11)	C5—C4—C3	123.5 (3)
O2—Ni1—O5	93.54 (11)	C5—C4—H4	118.2
O3—Ni1—O5	93.21 (12)	C3—C4—H4	118.2
O6—Ni1—O5	176.52 (11)	C4—C5—N1	118.7 (3)
O1—Ni1—O4	90.82 (9)	C4—C5—C6	114.3 (2)
O2—Ni1—O4	177.08 (11)	N1—C5—C6	127.1 (3)
O3—Ni1—O4	92.72 (10)	O1—C6—C7	126.6 (3)
O6—Ni1—O4	87.24 (11)	O1—C6—C5	114.3 (2)
O5—Ni1—O4	89.34 (12)	C7—C6—C5	119.1 (2)
C6—O1—Ni1	124.99 (19)	C8—C7—C6	122.6 (3)
C8—O2—Ni1	124.54 (18)	C8—C7—H7	118.7
Ni1—O3—H3A	109 (6)	C6—C7—H7	118.7
Ni1—O3—H3B	117 (6)	O2—C8—C7	126.7 (3)
H3A—O3—H3B	112 (9)	O2—C8—C9	114.5 (2)
Ni1—O4—H4A	118 (7)	C7—C8—C9	118.8 (2)
Ni1—O4—H4B	120 (7)	C10—C9—N2	118.8 (3)
H4A—O4—H4B	104 (8)	C10—C9—C8	114.5 (2)
Ni1—O5—H5A	123 (7)	N2—C9—C8	126.8 (3)
Ni1—O5—H5B	124 (7)	C11—C10—C9	123.3 (3)
H5A—O5—H5B	77 (8)	C11—C10—H10	118.3
Ni1—O6—H6A	114 (6)	C9—C10—H10	118.3
Ni1—O6—H6B	125 (7)	C10—C11—C12	119.2 (3)
H6A—O6—H6B	109 (8)	C10—C11—H11	120.4
C1—N1—C5	118.5 (3)	C12—C11—H11	120.4
C1—N1—H1	120.8	C13—C12—C11	119.4 (3)
C5—N1—H1	120.8	C13—C12—H12	120.3
C9—N2—C13	118.8 (3)	C11—C12—H12	120.3
C9—N2—H2	120.6	C12—C13—N2	120.4 (3)
C13—N2—H2	120.6	C12—C13—H13	119.8
C2—C1—N1	120.9 (3)	N2—C13—H13	119.8
C2—C1—H1A	119.5	H7A—O7—H7B	80 (8)
N1—C1—H1A	119.5	H8A—O8—H8B	116 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br1	0.86	2.94	3.774 (4)	165
N2—H2···Br1	0.86	3.02	3.852 (3)	165
C1—H1A···Br2	0.93	2.75	3.567 (3)	147
C4—H4···Br3ⁱ	0.93	2.47	3.330 (3)	154
C10—H10···Br2ⁱⁱ	0.93	2.48	3.305 (3)	149
O3—H3A···Br2ⁱⁱ	0.84 (2)	2.48 (4)	3.285 (3)	161 (9)
O3—H3B···Br3ⁱⁱⁱ	0.83 (2)	2.40 (3)	3.212 (2)	165 (8)
O4—H4A···O7^iv	0.84 (2)	2.16 (5)	2.917 (4)	150 (9)
O4—H4B···Br3ⁱ	0.82 (2)	2.48 (3)	3.284 (3)	167 (9)
O5—H5A···O7	0.84 (2)	1.99 (3)	2.808 (5)	163 (10)
O5—H5B···O8	0.84 (2)	2.29 (6)	3.002 (6)	142 (9)
O6—H6A···Br1^v	0.84 (2)	2.51 (2)	3.342 (3)	175 (9)
O6—H6B···Br2^v	0.83 (2)	2.45 (3)	3.266 (3)	165 (9)
O7—H7A···Br1ⁱ	0.84 (2)	2.59 (6)	3.335 (4)	149 (9)
O7—H7B···Br3ⁱ	0.85 (2)	2.54 (2)	3.386 (3)	173 (9)
O8—H8A···Br3^vi	0.85 (2)	3.06 (3)	3.880 (7)	165 (9)
O8—H8B···Br1ⁱⁱⁱ	0.84 (2)	2.65 (6)	3.393 (5)	149 (9)

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

Acknowledgements

The authors thank CSU–AAUP for research funds.

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