A second solvatomorph of poly[[μ4-N,N′-(1,3,5-oxadiazinane-3,5-di­yl)bis­(carbamoyl­methano­ato)]nickel(II)dipotassium]: crystal structure, Hirshfeld surface analysis and semi-empirical geometry optimization

Plutenko, M.O.; Haukka, M.; Husak, A.O.; Golenya, I.A.; Mulloev, N.U.

doi:10.1107/S2056989021011774

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 77| Part 12| December 2021| Pages 1289-1295

https://doi.org/10.1107/S2056989021011774

Open

access

A second solvatomorph of poly[[μ₄-N,N′-(1,3,5-oxadiazinane-3,5-diyl)bis(carbamoylmethanoato)]nickel(II)dipotassium]: crystal structure, Hirshfeld surface analysis and semi-empirical geometry optimization

Maksym O. Plutenko,^a ^* Matti Haukka,^b Alina O. Husak,^a,^c Irina A. Golenya ^a and Nurullo U. Mulloev ^d

^aDepartment of Chemistry, National Taras Shevchenko University, Volodymyrska, Street 64, 01601 Kyiv, Ukraine, ^bDepartment of Chemistry, University of Jyvaskyla, P.O. Box 35, FI-40014 Jyvaskyla, Finland, ^cPBMR Labs Ukraine, Murmanska 1, 02094 Kiev, Ukraine, and ^dThe Faculty of Physics, Tajik National University, Rudaki Avenue 17, 734025 Dushanbe, Tajikistan
^*Correspondence e-mail: plutenkom@gmail.com

Edited by B. Therrien, University of Neuchâtel, Switzerland (Received 13 October 2021; accepted 5 November 2021; online 12 November 2021)

The title compound, poly[triaquabis[μ₄-N,N′-(1,3,5-oxadiazinane-3,5-diyl)bis(carbamoylmethanoato)]dinickel(II)tetrapotassium], [K₄Ni₂(C₇H₆N₄O₇)₂(H₂O)₃]_n, is a second solvatomorph of poly[(μ₄-N,N′-(1,3,5-oxadiazinane-3,5-diyl)bis(carbamoylmethanoato)nickel(II)dipotassium] reported previously [Plutenko et al. (2021 ). Acta Cryst. E77, 298–304]. The asymmetric unit of the title compound includes two structurally independent complex anions [Ni(C₇H₆N₄O₇)]²⁻, which exhibit an L-shaped geometry and consist of two almost flat fragments perpendicular to one another: the 1,3,5-oxadiazinane fragment and the fragment including other atoms of the anion. The central Ni atom is in a square-planar N₂O₂ coordination arrangement formed by two amide N and two carboxylate O atoms. In the crystal, the title compound forms a layered structure in which layers of negatively charged complex anions and positively charged potassium cations are stacked along the a-axis direction. The polymeric framework is stabilized by a system of hydrogen-bonding interactions in which the water molecules act as donors and the carboxylic, amide and water O atoms act as acceptors.

Keywords: nickel(II) complex; template reaction; pseudomacrocyclic ligand; hydrazide-based ligand; SHAPE analysis; Hirshfeld surface analysis; semi-empirical geometry optimization; crystal structure.

CCDC reference: 2120378

1. Chemical context

In 1976, the products of the metal-templated reaction of hydrazide and aldehyde were separated and structurally described (Clark et al., 1976 ). It was further shown that such a synthetic strategy makes it possible to obtain complexes with 3d metals in high oxidation states. In particular, there are several works devoted to copper(III) complexes obtained by this method (Oliver & Waters, 1982 ; Fritsky et al., 1998 , 2006 ). Moreover, the preparation of an unprecedentedly stable iron(IV) clathrochelate complex was reported (Tomyn et al., 2017 ). Some such compounds are promising redox catalysts, as has been shown by Pap et al. (2011 ) and Shylin et al. (2019 ). Thus, the study of the conditions and peculiarities of hydrazide-aldehyde template interactions, as well as the isolation and characterization of their products, is an important task in modern coordination chemistry.

This work is a continuation of our investigation of the interaction of oxalohydrazidehydroxamic acid with formaldehyde and nickel(II) salts. Here we report the crystal structure of the title compound poly[triaquabis[μ₄-N,N′-(1,3,5-oxadiazinane-3,5-diyl)bis(carbamoylmethanoato)]dinickel(II)tetrapotassium] [(2K₂[Ni(L-2H)]·3H₂O)_n, 2], which is the solvatomorph of the earlier published (Plutenko et al., 2021) complex poly[pentaaquabis[μ_n-N,N′-(1,3,5-oxadiazinane-3,5-diyl)bis(carbamoylmethanoato)]nickel(II)tetrapotassium], [(2K₂[Ni(L-2H)]·4.8H₂O)_n, 1, H₂L = N,N′-(1,3,5-oxadiazinane-3,5-diyl)bis(aminooxoacetic acid)]. Both compounds can be obtained in a similar fashion as the result of a one-pot template reaction (see Fig. 1).

Figure 1
A plausible mechanism for the formation of the [Ni(L-2H)]^2– complex anion.

2. Structural commentary

The title compound, 2, (2K₂[Ni(L-2H)]·3H₂O)_n, crystallizes in space group P2₁/c, while the previously reported compound 1, (2K₂[Ni(L-2H)]·4.8H₂O)_n, crystallizes in Pbca. Similarly to 1, the asymmetric unit of 2 (Fig. 2) includes two structurally independent complex anions [Ni(L-2H)]^2– (namely A and B, which contain Ni1 and Ni1B, respectively). In addition, the unit cell of 2 also contains four potassium cations and three solvent water molecules.

Figure 2
The asymmetric unit of 2 with displacement ellipsoids shown at the 50% probability level.

Similarly to 1, the complex anion [Ni(L-2H)]²⁻ has an L-shaped geometry and consists of two almost flat fragments perpendicular to one another: the 1,3,5-oxadiazinane fragment and the fragment including other atoms of the anion. The dihedral angles between the mean planes formed by the non-hydrogen atoms of these fragments are 95.06 (8) and 94.06 (8)° for Ni1 and Ni1B, respectively. The ligand molecule is coordinated in a tetradentate {O_carboxyl,N_amide,N_amide,O_carboxyl}-mode. The central atom of the complex anion exhibits a square-planar coordination arrangement with the N₂O₂ chromophore. The deviation of the Ni^II atom from the mean plane defined by the donor atoms is 0.0073 (13) and 0.0330 (12) Å for Ni1 and Ni1B, respectively.

The Ni—N bond distances are in the range 1.836 (3)–1.849 (3) Å and Ni–O bond lengths are 1.877 (2)–1.897 (2) Å, which is typical for square-planar nickel complexes with similar ligands (Fritsky et al., 1998) and close to the Ni—N and Ni–O bond distances of 1. The O—M—O′, O—M—N and N—M—N′ bond angles have typical values for a square-planar arrangement. The bite angles O1—Ni1—N4, N1—Ni1—O2 and N1—Ni1—N4 deviate from 90°, which is the result of the formation of the five-membered chelate rings. The N—N′, N—C and C—O bond lengths of the ligand have typical values for coordinated deprotonated hydrazide and carboxyl groups.

3. Supramolecular features

In the crystal, the nickel(II) complex anions [Ni(L-2H)]²⁻ form layers parallel to the bc plane (Fig. 3a). Neighbouring complex anion layers are sandwiched by layers of potassium counter-cations (Fig. 4). Thus, negatively charged complex anion layers and positively charged potassium cationic layers are stacked along the a-axis direction. It is useful to note that a similar layered structure motif was observed in the crystal of the previously published compound 1. However, in the crystal of 1 the NiN₂O₂ plane is almost perpendicular to the complex anion layer plane (Fig. 3b): the angle between NiN₂O₂ and the ab plane is 84.43 (4) and 85.03 (5)° for Ni1 and Ni1B, respectively. In contrast, in the crystal of 2 the angle between NiN₂O₂ and the bc plane is 78.30 (8) and 86.29 (7)° for Ni1 and Ni1B, respectively.

Figure 3
Layers formed by the nickel(II) complex anions [Ni(L-2H)]^2– in the crystals of (a) compound 2 and (b) compound 1.

Figure 4
Crystal packing of the title compound in a stick model, showing the coordination polyhedra of the potassium cations. H atoms are omitted for clarity.

The demarcation of bonded and non-bonded K—X interactions (X = N or O) is still an unclear and debatable problem (Alvarez, 2013 ). Therefore, the criteria of such demarcation used in this paper need to be detailed. Based on the aforementioned publication (Alvarez, 2013), we propose 3.7 Å as the maximal distance for K—N bonds. Recently, it was shown (Gagné & Hawthorne, 2016 ) that K—O main and maximal bond distances depend on the coordination number of K. The results of this work permits 3.4, 3.5 and 3.6 Å to be proposed as the maximal distances for K—O bonds in the case of potassium coordination numbers 7, 8 and 9, respectively. In addition, K⋯N_amide interactions were determined as non-bonding because the existence of such bonds would lead to the presence of unstable three-membered KN_amideN_oxadiazinane rings with extremely small N—K—N′ angles.

The potassium cations are bound to the nickel(II) complex anions through the carboxylic O atoms (K4) the carboxylic and the amide O atoms (K1, K2) or through the amide O and the oxadiazinane N atoms (K3). In addition, the potassium cations have contacts with the O atoms of water molecules, with the amide and the carboxylic O atoms, and with the oxadiazinane O and N atoms of neighbouring complex anions. The K1 and K2 cations exhibit an O₆N coordination, while the K3 and K4 cations exhibit O₈N and O₇N coordinations, respectively.

For an evaluation of the coordination geometry of each potassium cation, SHAPE 2.1 software (Llunell et al., 2013 ) was used. A SHAPE analysis of the potassium coordination sphere (Table 1, Fig. 5) yields the lowest continuous shape measure (CShM) value for a distorted pentagonal bipyramid (5.142 for K1 and 3.122 for K2), a distorted muffin (3.691 for K3) and a distorted triangular dodecahedron (5.187 for K4). For K4, comparable CShM values were obtained for a square antiprism (5.463).

Table 1
Values for continuous shapes measures (CShM) of the polyhedra centred by the potassium cations

Shape	CShM
	K1	K2
Heptagon (D7h)	28.515	29.484
Hexagonal pyramid (C6v)	17.225	20.349
Pentagonal bipyramid (D5h)	5.142	3.122
Capped octahedron (C3v)	7.539	7.840
Capped trigonal prism (C2v)	6.374	5.639
Johnson pentagonal bipyramid J13 (D5h)	8.789	6.943
Johnson elongated triangular pyramid J7 (C3v)	16.352	20.453
	K3
Enneagon (D9h)	32.593
Octagonal pyramid (C8v)	23.087
Heptagonal bipyramid (D7h)	14.962
Johnson triangular cupola J3 (C3v)	12.759
Capped cube J8 (C4v)	9.046
Spherical-relaxed capped cube (C4v)	7.600
Capped square antiprism J10 (C4v)	6.360
Spherical capped square antiprism (C4v)	5.020
Tricapped trigonal prism J51 (D3h)	6.694
Spherical tricapped trigonal prism (D3h)	5.698
Tridiminished icosahedron J63 (C3v)	11.379
Hula-hoop (C2v)	6.577
Muffin (Cs)	3.691
	K4
Octagon (D8h)	33.086
Heptagonal pyramid (C7v)	18.988
Hexagonal bipyramid (D6h)	14.426
Cube (Oh)	10.884
Square antiprism (D4d)	5.463
Triangular dodecahedron (D2d)	5.187
Johnson gyrobifastigium J26 (D2d)	11.775
Johnson elongated triangular bipyramid J14 (D3h)	26.080
Biaugmented trigonal prism J50 (C2v)	6.413
Biaugmented trigonal prism (C2v)	6.587
Snub diphenoid J84 (D2d)	7.862
Triakis tetrahedron (Td)	11.175
Elongated trigonal bipyramid (D3h)	20.295

Figure 5
Polyhedral views of the coordination environments for the potassium cations.

The polyhedra around the neighbouring potassium cations are connected with each other through common vertices (K1 with K3, K1 with K4, K2 with K4), edges (K3 with K4) and faces (K1 with K2, K1 with K3, K2 with K3). The K—O bond lengths are in the range 2.628 (2)–3.271 (3) Å, K—N 2.887 (3)–3.025 (3) Å, which is close to those reported for the structures of related carboxylate and amide complexes (Fritsky et al., 1998; Mokhir et al., 2002 ).

The polymeric framework of 2 is stabilized by an extensive system of hydrogen-bonding interactions in which the water molecules act as donors and the carboxylic, the amide and the water O atoms act as acceptors (Table 2). Similarly to 1, the hydrogen bonds are localized mainly at the potassium cation layers (Fig. 6). Moreover, in comparison to 1, the unit cell of 2 contains a smaller number of water molecules, which causes a smaller number of hydrogen-bond interactions in the crystal structure.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H8O⋯O9ⁱ	0.85	2.02	2.869 (4)	173
O8—H8P⋯O4Bⁱⁱ	0.85	2.01	2.858 (3)	166
O9—H9P⋯O4ⁱⁱⁱ	0.86	1.91	2.722 (3)	157
O9—H9O⋯O6B^iv	0.86	2.07	2.864 (3)	153
O10—H10P⋯O4^v	0.88	2.02	2.887 (3)	168
O10—H10O⋯O7B^vi	0.87	2.04	2.882 (3)	164
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) ; (iv) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (v) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) x, y+1, z.

Figure 6
Crystal packing of the title compound. C—H hydrogen atoms are omitted for clarity. Hydrogen bonds are indicated by dashed lines.

4. Hirshfeld analysis

The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) and the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ) were performed with CrystalExplorer17 (Turner et al., 2017 ). The Hirshfeld surfaces of the complex anions are colour-mapped with the normalized contact distance (d_norm) from red (distances shorter than the sum of the van der Waals radii) through white to blue (distances longer than the sum of the van der Waals radii).

The Hirshfeld surface of the title compound is mapped over d_norm, in the colour ranges −0.6388 to 0.9164 a.u. and −0.6768 to 0.7286 a.u. for Ni1 and Ni1B complex anions, respectively (Fig. 7). Similarly to 1, the complex anions of 2 are connected to the other elements of the crystal packing mainly via the amide and the carboxylic O atoms. However, in contrast to 1, one of the oxadiazinane O atoms of 2 is also involved in intermolecular bond formation.

Figure 7
The Hirshfeld surfaces of the Ni1 (A) and Ni1B (B) complex anions mapped over d_norm.

A fingerprint plot delineated into specific interatomic contacts contains information related to specific intermolecular interactions. The blue colour refers to the frequency of occurrence of the (d_i, d_e) pair with the full fingerprint plot outlined in gray. Fig. 8a and 9a show the two-dimensional fingerprint plots of the sum of the contacts contributing to the Hirshfeld surface represented in normal mode for the Ni1 and Ni1B complex anions, respectively.

Figure 8
(a) Full two-dimensional fingerprint plot of the Ni1 complex anion and those delineated into (b) O⋯H/H⋯O (36.9%) (c) O⋯K/K⋯O (20.9%) and (d) H⋯H (10.4%) contacts.

Figure 9
(a) Full two-dimensional fingerprint plot of the Ni1B complex anion and those delineated into (b) O⋯H/H⋯O (38.7%) (c) O⋯K/K⋯O (18.2%) and (d) H⋯H (13.1%) contacts.

The most significant contribution to the Hirshfeld surface is from O⋯H/H⋯O contacts (36.9% and 38.7% for the Ni1 and Ni1B complex anions, respectively; Fig. 8b and 9b). In addition, O⋯K/K⋯O (20.9% and 18.2% for the Ni1 and Ni1B complex anions; Fig. 8c and 9c) and H⋯H (10.4% and 13.1% for the Ni1 and Ni1B complex anions, respectively; Fig. 8d and 9d) make very significant contributions to the total Hirshfeld surface. This indicates that there are more K⋯O contacts and fewer O⋯H contacts compared to the crystal of 1.

5. Geometry optimization

The searching of computationally `cheap' but still sufficiently accurate methods of transition-metal complex geometry optimization is an important task of modern computational chemistry. The geometry optimization calculations were carried out with three semi-empirical methods: PM7, DFTB and GFN2-xTB. The PM7 (Stewart, 2013 ) calculations were performed with MOPAC2016 software (Stewart, 2016 ). The DFTB calculations were carried out with the DFTB+ software package (Hourahine et al., 2020 ) using the `mio-1-1' (Elstner et al., 1998 ) and the `trans3d-0-1' (Zheng et al., 2007 ) Slater–Koster parameterization sets. The GFN2-xTB (Bannwarth et al., 2019 ) calculations were applied with xtb 6.4 package (Grimme, 2019 ). The geometry of the Ni1 complex anion obtained from the crystal structure was used as the starting geometry for the calculations.

In general, for all described semi-empirical methods, the calculated geometric parameters of the oxadiazinane ring are in reasonable agreement with experimental values (see Table 3). On the other hand, the accuracy of the non-oxadiazinane fragment geometry prediction varies greatly depending on the method. The worst agreement with experiments is from the PM7 method, mainly because of the pyramidalization of the amide nitrogen atom (Table 3). Such non-planarity of the amide fragment is a well-known problem of the PMx methods (Feigel & Strassner, 1993 ). In contrast, the DFTB method predicts the amide geometric parameters with high accuracy but demonstrates longer than experimental carboxylate C—O bonds and a slight tetragonal distortion of the nickel(II) coordination polyhedra (Table 3). The best results were obtained with the GFN2-xTB method for which the calculated geometric parameters correlate nicely with experimental values (Table 3). The maximal difference between the calculated and the experimental bond lengths concerns the C—O lengths (shorter than the experimental values within 0.024–0.033 Å). A superimposed analysis of the Ni1 complex anion with its optimized structure gives an RMSD of 0.131 Å (Fig. 10). Thus, the GFN2-xTB method is a promising geometry prediction method for transition-metal complexes based on hydrazide and carboxylate ligands.

Table 3
Comparison of selected geometric data (A,°; mean values) for the Ni1 complex anion from calculated and X-ray data

Geometric parameter	X-ray	PM7	DFTB	GFN2-xTB
Oxadiazinane ring
C—O	1.434	1.413	1.467	1.410
C—N	1.463	1.489	1.463	1.452
Carboxylate moiety
C—O	1.287	1.276	1.451	1.260
C=O	1.233	1.224	1.196	1.208
Hydrazide moiety
C—O	1.249	1.232	1.227	1.216
C—N	1.321	1.357	1.393	1.332
N—N	1.432	1.413	1.413	1.415
C—N_amide—Ni—N_oxadiazine	175.74	133.89	169.00	162.81
Ni coordination arrangement
Ni—O	1.892	1.776	1.780	1.871
Ni—N	1.840	1.955	1.974	1.871
O—Ni—N chelate	85.24	93.35	81.32	82.94
O—Ni—N non-chelate	178.29	173.19	162.52	176.77
N—Ni—N	85.53	88.09	90.73	94.40

Figure 10
Structural overlay between the experimental (blue) and optimized (orange) structures.

6. Database survey

A search in the Cambridge Structural Database (CSD version 5.39, update of May 2018; Groom et al., 2016 ) resulted in 11 hits dealing with 3d-metal complexes with macrocyclic or pseudo-macrocyclic ligands formed by template binding of several hydrazide groups by formaldehyde molecules. These complexes contain the following 3d metals: Ni^II (Fritsky et al., 1998), Cu^II (Clark et al., 1976; Fritsky et al., 2006), Cu^III (Oliver & Waters, 1982; Fritsky et al., 1998, Fritsky et al., 2006) and Fe^IV (Tomyn et al., 2017). Thus, such macrocyclic and pseudo-macrocyclic ligand systems exhibit a tendency to stabilize the high oxidation states of 3d metals.

7. Synthesis and crystallization

A solution of Ni(ClO₄)₂·6H₂O (0.091 g, 0.25 mmol) in 5 ml of water was added to a warm solution of oxalohydrazidehydroxamic acid (0.06 g, 0.5 mmol) in 5 ml of water. The resulting light-green mixture was stirred with heating (320–330 K) for 20 min and then 1 ml of 4M KOH solution was added. As a result, the colour of the solution changed to pink. After 5 min of stirring, 0.03 g of the paraformaldehyde (1 mmol) was added and stirring with heating (323–333 K) was continued for 30 min. The resulting orange solution was left for crystallization by slow evaporation in air. After one week, orange crystals of 2 suitable for X-ray diffraction studies were obtained. The crystals were filtered off, washed with diethyl ether and dried in the air. Yield 0.044 g (42%). Elemental analysis for C₁₄H₁₈N₈O₁₇K₄Ni₂ (mol. mass 844.12), calculated, %: C 19.92; H 2.15; N 13.27; Found, %: C 19.69; H 2.16; N 13.11. UV–vis (H₂O), λ_max (ɛ, mol⁻¹ dm³ cm⁻¹): 520 nm (1380). IR (KBr, cm⁻¹): 3420 br ν(O–H) stretch, 2981, 2910, 2860 ν(C—H) stretch, 1643 (vs) ν(C=O) amide I, 1590 ν_as(COO⁻), 1435 ν_s(COO⁻).

8. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. H atoms were positioned geometrically (O—H = 0.85–0.88, C—H = 0.99 Å) and refined as riding with U_iso(H) = 1.2 U_eq(O, C).

Table 4
Experimental details

Crystal data
Chemical formula	[K₄Ni₂(C₇H₆N₄O₇)₂(H₂O)₃]
M_r	844.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	20.3825 (5), 7.7039 (3), 17.3078 (6)
β (°)	98.240 (2)
V (Å³)	2689.69 (16)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.12
Crystal size (mm)	0.15 × 0.09 × 0.08

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008 )
T_min, T_max	0.746, 0.842
No. of measured, independent and observed [I > 2σ(I)] reflections	25068, 6148, 5118
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.082, 1.14
No. of reflections	6148
No. of parameters	406
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.45
Computer programs: COLLECT (Bruker, 2008 ), DENZO/SCALEPACK (Otwinowski & Minor, 1997 ), SUPERFLIP (Palatinus & Chapuis, 2007 ), SHELXL2018/1 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 2009 ) and SHELXL97 (Sheldrick, 2008).

Supporting information

CCDC reference: 2120378

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021011774/tx2044sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021011774/tx2044Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989021011774/tx2044Isup3.cdx

checkCIF report

Computing details top

Data collection: COLLECT (Bruker, 2008); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL2018/1 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Poly[triaquabis[µ₄-N,N'-(1,3,5-oxadiazinane-3,5-diyl)bis(carbamoylmethanoato)]dinickel(II)tetrapotassium] top

Crystal data top

[K₄Ni₂(C₇H₆N₄O₇)₂(H₂O)₃]	F(000) = 1704
M_r = 844.18	D_x = 2.085 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.3825 (5) Å	Cell parameters from 12179 reflections
b = 7.7039 (3) Å	θ = 1.0–30.0°
c = 17.3078 (6) Å	µ = 2.12 mm⁻¹
β = 98.240 (2)°	T = 100 K
V = 2689.69 (16) Å³	Orange, block
Z = 4	0.15 × 0.09 × 0.08 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	6148 independent reflections
Radiation source: fine-focus sealed tube	5118 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	R_int = 0.043
Detector resolution: 16 pixels mm^-1	θ_max = 27.5°, θ_min = 2.5°
φ scans and ω scans with κ offset	h = −26→26
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	k = −10→10
T_min = 0.746, T_max = 0.842	l = −22→22
25068 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.082	w = 1/[σ²(F_o²) + 8.0539P] where P = (F_o² + 2F_c²)/3
S = 1.14	(Δ/σ)_max < 0.001
6148 reflections	Δρ_max = 0.63 e Å⁻³
406 parameters	Δρ_min = −0.45 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
Ni1	0.47434 (2)	0.39867 (5)	0.07544 (2)	0.01087 (9)
K1	0.17619 (4)	0.53183 (9)	0.11705 (4)	0.01892 (16)
K2	0.19572 (3)	0.36084 (9)	−0.07023 (4)	0.01670 (15)
K3	0.27474 (3)	0.87045 (9)	0.01255 (4)	0.01761 (15)
K4	0.37676 (4)	0.05611 (9)	−0.14504 (4)	0.02025 (16)
O1	0.41934 (10)	0.2347 (3)	0.01663 (13)	0.0155 (5)
O2	0.55123 (10)	0.2576 (3)	0.08187 (12)	0.0138 (4)
O3	0.66101 (11)	0.2786 (3)	0.11647 (14)	0.0178 (5)
O4	0.63860 (11)	0.6017 (3)	0.18521 (13)	0.0175 (5)
O5	0.43257 (10)	0.6088 (3)	0.23723 (12)	0.0144 (4)
O6	0.28491 (10)	0.5095 (3)	0.04127 (13)	0.0144 (5)
O7	0.31296 (10)	0.1927 (3)	−0.03135 (13)	0.0145 (4)
O8	0.23728 (13)	0.4224 (4)	0.26454 (15)	0.0296 (6)
H8O	0.234956	0.311841	0.266821	0.044*
H8P	0.220280	0.460928	0.303719	0.044*
O9	0.22781 (12)	0.4456 (3)	−0.21414 (15)	0.0260 (6)
H9P	0.270092	0.459040	−0.210682	0.039*
H9O	0.209842	0.522979	−0.245902	0.039*
O10	0.32908 (13)	1.1134 (4)	0.14694 (15)	0.0306 (6)
H10O	0.287037	1.137097	0.135669	0.046*
H10P	0.338827	1.126557	0.197749	0.046*
N1	0.52942 (12)	0.5586 (3)	0.13120 (14)	0.0113 (5)
N2	0.51068 (13)	0.7242 (3)	0.15852 (15)	0.0124 (5)
N3	0.39268 (13)	0.6979 (3)	0.10530 (15)	0.0131 (5)
N4	0.39871 (13)	0.5297 (3)	0.07165 (15)	0.0122 (5)
C1	0.60452 (15)	0.3371 (4)	0.11225 (18)	0.0137 (6)
C2	0.59253 (16)	0.5163 (4)	0.14705 (18)	0.0146 (6)
C3	0.45459 (15)	0.7945 (4)	0.10429 (19)	0.0140 (6)
H3A	0.447429	0.917052	0.118117	0.017*
H3B	0.466161	0.792495	0.050662	0.017*
C4	0.49161 (15)	0.7092 (4)	0.23624 (18)	0.0140 (6)
H4A	0.528350	0.654533	0.271547	0.017*
H4B	0.484584	0.826836	0.256513	0.017*
C5	0.37883 (16)	0.6825 (4)	0.18499 (18)	0.0155 (6)
H5A	0.368739	0.799144	0.204239	0.019*
H5B	0.338951	0.609318	0.185349	0.019*
C6	0.34231 (15)	0.4539 (4)	0.04236 (17)	0.0117 (6)
C7	0.35790 (15)	0.2774 (4)	0.00678 (17)	0.0122 (6)
Ni1B	0.01223 (2)	0.08795 (5)	0.09162 (2)	0.01243 (9)
O1B	0.08679 (11)	0.2257 (3)	0.07813 (13)	0.0166 (5)
O2B	−0.04769 (11)	0.2677 (3)	0.05952 (13)	0.0156 (5)
O3B	−0.15683 (11)	0.3148 (3)	0.03336 (14)	0.0184 (5)
O4B	−0.17542 (11)	−0.0118 (3)	0.10065 (13)	0.0164 (5)
O5B	0.00334 (11)	−0.1490 (3)	0.25474 (13)	0.0170 (5)
O6B	0.18685 (11)	−0.1330 (3)	0.14427 (14)	0.0185 (5)
O7B	0.19555 (11)	0.1959 (3)	0.07804 (14)	0.0200 (5)
N1B	−0.06184 (13)	−0.0419 (3)	0.10402 (15)	0.0133 (5)
N2B	−0.06258 (13)	−0.2169 (3)	0.13205 (15)	0.0134 (5)
N3B	0.05905 (13)	−0.2534 (3)	0.14984 (15)	0.0135 (5)
N4B	0.07292 (13)	−0.0845 (3)	0.12181 (15)	0.0140 (5)
C1B	−0.10848 (16)	0.2241 (4)	0.05852 (18)	0.0144 (6)
C2B	−0.11930 (16)	0.0406 (4)	0.09058 (17)	0.0137 (6)
C3B	−0.00599 (15)	−0.3127 (4)	0.10940 (19)	0.0146 (6)
H3B1	−0.006462	−0.300402	0.052383	0.017*
H3B2	−0.011318	−0.437434	0.120686	0.017*
C4B	−0.05815 (16)	−0.2189 (4)	0.21681 (18)	0.0152 (6)
H4B1	−0.095254	−0.150425	0.232299	0.018*
H4B2	−0.062785	−0.339827	0.234578	0.018*
C5B	0.05751 (16)	−0.2475 (4)	0.23366 (19)	0.0158 (6)
H5B1	0.054706	−0.367518	0.253325	0.019*
H5B2	0.099552	−0.196407	0.259598	0.019*
C6B	0.13592 (16)	−0.0447 (4)	0.12181 (18)	0.0154 (6)
C7B	0.14124 (15)	0.1389 (4)	0.08983 (18)	0.0143 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0117 (2)	0.00866 (18)	0.01215 (19)	0.00042 (14)	0.00137 (14)	−0.00210 (15)
K1	0.0225 (4)	0.0128 (3)	0.0229 (4)	0.0021 (3)	0.0082 (3)	0.0018 (3)
K2	0.0181 (4)	0.0124 (3)	0.0182 (3)	0.0002 (3)	−0.0022 (3)	−0.0009 (3)
K3	0.0162 (3)	0.0130 (3)	0.0229 (4)	−0.0001 (3)	0.0006 (3)	0.0043 (3)
K4	0.0253 (4)	0.0118 (3)	0.0265 (4)	−0.0019 (3)	0.0134 (3)	−0.0026 (3)
O1	0.0140 (11)	0.0129 (11)	0.0195 (12)	−0.0001 (9)	0.0021 (9)	−0.0028 (9)
O2	0.0149 (11)	0.0116 (10)	0.0149 (11)	0.0018 (8)	0.0020 (8)	−0.0011 (9)
O3	0.0124 (11)	0.0158 (11)	0.0253 (13)	0.0022 (9)	0.0030 (9)	−0.0007 (10)
O4	0.0151 (11)	0.0154 (11)	0.0207 (12)	−0.0003 (9)	−0.0016 (9)	−0.0013 (9)
O5	0.0159 (11)	0.0146 (11)	0.0135 (11)	−0.0009 (9)	0.0044 (8)	0.0014 (9)
O6	0.0135 (11)	0.0127 (11)	0.0168 (11)	0.0013 (9)	0.0016 (9)	−0.0016 (9)
O7	0.0144 (11)	0.0138 (11)	0.0148 (11)	−0.0021 (9)	0.0005 (8)	−0.0015 (9)
O8	0.0368 (16)	0.0286 (14)	0.0253 (14)	0.0059 (12)	0.0103 (11)	0.0025 (11)
O9	0.0159 (13)	0.0345 (15)	0.0268 (14)	−0.0018 (11)	0.0006 (10)	0.0045 (11)
O10	0.0259 (14)	0.0390 (16)	0.0269 (14)	0.0052 (12)	0.0038 (11)	0.0047 (12)
N1	0.0137 (13)	0.0095 (12)	0.0107 (12)	0.0008 (10)	0.0022 (10)	−0.0013 (10)
N2	0.0151 (13)	0.0104 (12)	0.0118 (12)	0.0006 (10)	0.0018 (10)	−0.0017 (10)
N3	0.0177 (14)	0.0090 (12)	0.0125 (13)	0.0001 (10)	0.0021 (10)	−0.0040 (10)
N4	0.0176 (14)	0.0075 (12)	0.0116 (12)	0.0018 (10)	0.0024 (10)	−0.0028 (10)
C1	0.0176 (16)	0.0137 (15)	0.0105 (14)	−0.0010 (12)	0.0042 (12)	0.0031 (12)
C2	0.0179 (17)	0.0124 (15)	0.0141 (15)	−0.0020 (12)	0.0039 (12)	0.0019 (12)
C3	0.0158 (16)	0.0091 (14)	0.0164 (15)	0.0002 (12)	0.0002 (12)	−0.0002 (12)
C4	0.0174 (16)	0.0141 (15)	0.0106 (14)	0.0009 (12)	0.0022 (12)	−0.0019 (12)
C5	0.0177 (16)	0.0152 (15)	0.0139 (15)	−0.0005 (12)	0.0036 (12)	−0.0020 (12)
C6	0.0149 (15)	0.0110 (14)	0.0092 (14)	−0.0001 (12)	0.0023 (11)	0.0008 (11)
C7	0.0165 (16)	0.0098 (14)	0.0105 (14)	−0.0003 (11)	0.0026 (11)	0.0020 (11)
Ni1B	0.0128 (2)	0.00920 (19)	0.0149 (2)	−0.00029 (15)	0.00073 (15)	0.00233 (15)
O1B	0.0159 (12)	0.0116 (11)	0.0224 (12)	−0.0001 (9)	0.0028 (9)	0.0032 (9)
O2B	0.0159 (12)	0.0122 (11)	0.0179 (11)	−0.0007 (9)	−0.0001 (9)	0.0019 (9)
O3B	0.0165 (12)	0.0134 (11)	0.0246 (13)	0.0028 (9)	0.0003 (9)	0.0034 (10)
O4B	0.0149 (12)	0.0140 (11)	0.0203 (12)	0.0005 (9)	0.0021 (9)	0.0004 (9)
O5B	0.0202 (12)	0.0165 (12)	0.0138 (11)	0.0000 (9)	0.0007 (9)	−0.0009 (9)
O6B	0.0139 (11)	0.0157 (11)	0.0251 (12)	0.0009 (9)	0.0004 (9)	−0.0003 (10)
O7B	0.0164 (12)	0.0168 (12)	0.0277 (13)	−0.0025 (9)	0.0067 (10)	0.0025 (10)
N1B	0.0168 (14)	0.0075 (12)	0.0152 (13)	−0.0003 (10)	0.0009 (10)	0.0000 (10)
N2B	0.0158 (13)	0.0095 (12)	0.0149 (13)	0.0000 (10)	0.0021 (10)	0.0021 (10)
N3B	0.0154 (13)	0.0094 (12)	0.0154 (13)	−0.0013 (10)	0.0014 (10)	0.0048 (10)
N4B	0.0146 (13)	0.0101 (12)	0.0170 (13)	−0.0006 (10)	0.0018 (10)	0.0021 (10)
C1B	0.0197 (17)	0.0128 (15)	0.0109 (14)	−0.0019 (12)	0.0023 (12)	−0.0021 (12)
C2B	0.0188 (17)	0.0114 (14)	0.0104 (14)	−0.0001 (12)	0.0004 (12)	−0.0018 (11)
C3B	0.0133 (15)	0.0122 (15)	0.0176 (16)	−0.0013 (12)	0.0002 (12)	−0.0008 (12)
C4B	0.0157 (16)	0.0129 (15)	0.0165 (15)	−0.0008 (12)	0.0009 (12)	0.0037 (12)
C5B	0.0177 (17)	0.0127 (15)	0.0168 (16)	0.0014 (12)	0.0014 (12)	0.0041 (12)
C6B	0.0170 (16)	0.0154 (16)	0.0137 (15)	0.0001 (12)	0.0017 (12)	−0.0035 (12)
C7B	0.0163 (16)	0.0144 (15)	0.0122 (15)	−0.0005 (12)	0.0017 (12)	−0.0007 (12)

Geometric parameters (Å, º) top

Ni1—N4	1.836 (3)	O5—C4	1.433 (4)
Ni1—N1	1.844 (3)	O5—C5	1.434 (4)
Ni1—O1	1.887 (2)	O6—C6	1.244 (4)
Ni1—O2	1.897 (2)	O7—C7	1.236 (4)
K1—O6Bⁱ	2.628 (2)	O8—H8O	0.8546
K1—O7B	2.717 (2)	O8—H8P	0.8575
K1—O6	2.737 (2)	O9—H9P	0.8615
K1—O8	2.805 (3)	O9—H9O	0.8567
K1—O3Bⁱⁱ	2.834 (2)	O10—H10O	0.8704
K1—O1B	2.998 (2)	O10—H10P	0.8792
K1—N3Bⁱ	3.025 (3)	N1—C2	1.317 (4)
K1—C7B	3.130 (3)	N1—N2	1.431 (3)
K1—C6Bⁱ	3.368 (3)	N2—C4	1.457 (4)
K1—K2	3.5736 (10)	N2—C3	1.474 (4)
K1—K3	3.8927 (10)	N3—N4	1.433 (3)
K2—O6	2.708 (2)	N3—C5	1.452 (4)
K2—O7	2.717 (2)	N3—C3	1.467 (4)
K2—O3Bⁱⁱ	2.725 (2)	N4—C6	1.324 (4)
K2—O9	2.743 (3)	C1—C2	1.540 (4)
K2—O4Bⁱⁱⁱ	2.760 (2)	C3—H3A	0.9900
K2—O7B	2.864 (2)	C3—H3B	0.9900
K2—N2Bⁱⁱⁱ	2.984 (3)	C4—H4A	0.9900
K2—C6	3.401 (3)	C4—H4B	0.9900
K2—C7	3.443 (3)	C5—H5A	0.9900
K2—C2Bⁱⁱⁱ	3.458 (3)	C5—H5B	0.9900
K2—K3^iv	4.2728 (10)	C6—C7	1.544 (4)
K3—O7ⁱ	2.742 (2)	Ni1B—N4B	1.839 (3)
K3—O3Bⁱⁱ	2.810 (2)	Ni1B—N1B	1.849 (3)
K3—O4Bⁱⁱ	2.826 (2)	Ni1B—O2B	1.877 (2)
K3—O6	2.827 (2)	Ni1B—O1B	1.895 (2)
K3—O3^v	2.976 (2)	O1B—C7B	1.287 (4)
K3—N3	3.003 (3)	O2B—C1B	1.281 (4)
K3—O10	3.066 (3)	O3B—C1B	1.235 (4)
K3—O6Bⁱ	3.095 (2)	O4B—C2B	1.249 (4)
K3—O7Bⁱ	3.271 (2)	O5B—C5B	1.430 (4)
K3—C2Bⁱⁱ	3.475 (3)	O5B—C4B	1.434 (4)
K3—C6	3.501 (3)	O6B—C6B	1.255 (4)
K3—C1Bⁱⁱ	3.512 (3)	O7B—C7B	1.235 (4)
K3—H10O	2.9446	N1B—C2B	1.323 (4)
K4—O7	2.721 (2)	N1B—N2B	1.434 (3)
K4—O4^v	2.733 (2)	N2B—C4B	1.457 (4)
K4—O3^vi	2.756 (2)	N2B—C3B	1.469 (4)
K4—O5^vii	2.779 (2)	N3B—N4B	1.431 (3)
K4—N2^v	2.887 (3)	N3B—C5B	1.456 (4)
K4—O2^vi	2.955 (2)	N3B—C3B	1.480 (4)
K4—O8^vii	3.047 (3)	N4B—C6B	1.320 (4)
K4—C1^vi	3.095 (3)	C1B—C2B	1.546 (4)
K4—O1	3.127 (2)	C3B—H3B1	0.9900
K4—C7	3.201 (3)	C3B—H3B2	0.9900
K4—C2^v	3.354 (3)	C4B—H4B1	0.9900
K4—C5^vii	3.474 (3)	C4B—H4B2	0.9900
O1—C7	1.282 (4)	C5B—H5B1	0.9900
O2—C1	1.291 (4)	C5B—H5B2	0.9900
O3—C1	1.229 (4)	C6B—C7B	1.528 (4)
O4—C2	1.254 (4)

N4—Ni1—N1	95.53 (11)	N2^v—K4—O1	72.10 (7)
N4—Ni1—O1	85.30 (10)	O2^vi—K4—O1	88.24 (6)
N1—Ni1—O1	178.66 (11)	O8^vii—K4—O1	123.68 (7)
N4—Ni1—O2	177.92 (11)	C1^vi—K4—O1	104.79 (7)
N1—Ni1—O2	85.18 (10)	O7—K4—C7	22.25 (7)
O1—Ni1—O2	94.02 (9)	O4^v—K4—C7	70.87 (7)
O6Bⁱ—K1—O7B	165.68 (7)	O3^vi—K4—C7	106.35 (7)
O6Bⁱ—K1—O6	95.50 (7)	O5^vii—K4—C7	162.77 (8)
O7B—K1—O6	70.41 (7)	N2^v—K4—C7	86.82 (8)
O6Bⁱ—K1—O8	96.75 (8)	O2^vi—K4—C7	104.10 (7)
O7B—K1—O8	83.03 (8)	O8^vii—K4—C7	100.36 (8)
O6—K1—O8	97.64 (7)	C1^vi—K4—C7	113.38 (8)
O6Bⁱ—K1—O3Bⁱⁱ	75.65 (7)	O1—K4—C7	23.34 (7)
O7B—K1—O3Bⁱⁱ	100.07 (7)	O7—K4—C2^v	74.75 (7)
O6—K1—O3Bⁱⁱ	66.54 (7)	O4^v—K4—C2^v	20.73 (7)
O8—K1—O3Bⁱⁱ	161.16 (8)	O3^vi—K4—C2^v	167.98 (8)
O6Bⁱ—K1—O1B	147.71 (7)	O5^vii—K4—C2^v	110.16 (7)
O7B—K1—O1B	45.58 (6)	N2^v—K4—C2^v	43.27 (7)
O6—K1—O1B	110.52 (7)	O2^vi—K4—C2^v	136.36 (7)
O8—K1—O1B	98.30 (7)	O8^vii—K4—C2^v	95.92 (8)
O3Bⁱⁱ—K1—O1B	96.98 (7)	C1^vi—K4—C2^v	160.86 (8)
O6Bⁱ—K1—N3Bⁱ	58.41 (7)	O1—K4—C2^v	63.19 (7)
O7B—K1—N3Bⁱ	135.57 (7)	C7—K4—C2^v	61.97 (8)
O6—K1—N3Bⁱ	147.07 (7)	O7—K4—C5^vii	151.88 (7)
O8—K1—N3Bⁱ	104.66 (8)	O4^v—K4—C5^vii	108.05 (7)
O3Bⁱⁱ—K1—N3Bⁱ	86.25 (7)	O3^vi—K4—C5^vii	72.21 (7)
O1B—K1—N3Bⁱ	90.10 (7)	O5^vii—K4—C5^vii	23.29 (7)
O6Bⁱ—K1—C7B	171.25 (8)	N2^v—K4—C5^vii	97.79 (7)
O7B—K1—C7B	23.02 (7)	O2^vi—K4—C5^vii	79.33 (7)
O6—K1—C7B	92.84 (8)	O8^vii—K4—C5^vii	73.58 (7)
O8—K1—C7B	84.73 (8)	C1^vi—K4—C5^vii	67.75 (8)
O3Bⁱⁱ—K1—C7B	105.44 (8)	O1—K4—C5^vii	162.73 (7)
O1B—K1—C7B	24.11 (7)	C7—K4—C5^vii	173.84 (8)
N3Bⁱ—K1—C7B	112.86 (8)	C2^v—K4—C5^vii	119.08 (8)
O6Bⁱ—K1—C6Bⁱ	19.63 (7)	C7—O1—Ni1	113.14 (19)
O7B—K1—C6Bⁱ	166.68 (8)	C7—O1—K4	81.58 (17)
O6—K1—C6Bⁱ	106.83 (7)	Ni1—O1—K4	147.60 (10)
O8—K1—C6Bⁱ	110.29 (8)	C1—O2—Ni1	113.09 (19)
O3Bⁱⁱ—K1—C6Bⁱ	67.44 (7)	C1—O2—K4^vi	83.85 (17)
O1B—K1—C6Bⁱ	128.70 (7)	Ni1—O2—K4^vi	148.49 (10)
N3Bⁱ—K1—C6Bⁱ	42.60 (7)	C1—O3—K4^vi	94.03 (19)
C7B—K1—C6Bⁱ	152.81 (8)	C1—O3—K3^v	127.3 (2)
O6Bⁱ—K1—K2	120.51 (6)	K4^vi—O3—K3^v	86.44 (6)
O7B—K1—K2	52.02 (5)	C2—O4—K4^v	108.80 (19)
O6—K1—K2	48.63 (5)	C4—O5—C5	110.2 (2)
O8—K1—K2	128.47 (6)	C4—O5—K4^viii	133.50 (17)
O3Bⁱⁱ—K1—K2	48.67 (5)	C5—O5—K4^viii	106.70 (16)
O1B—K1—K2	69.47 (5)	C6—O6—K2	113.52 (19)
N3Bⁱ—K1—K2	124.43 (6)	C6—O6—K1	147.0 (2)
C7B—K1—K2	63.86 (6)	K2—O6—K1	82.02 (6)
C6Bⁱ—K1—K2	116.01 (6)	C6—O6—K3	112.75 (18)
O6Bⁱ—K1—K3	52.41 (5)	K2—O6—K3	105.41 (7)
O7B—K1—K3	114.82 (5)	K1—O6—K3	88.76 (6)
O6—K1—K3	46.56 (5)	C7—O7—K2	116.01 (19)
O8—K1—K3	115.66 (6)	C7—O7—K4	101.30 (18)
O3Bⁱⁱ—K1—K3	46.14 (5)	K2—O7—K4	119.99 (8)
O1B—K1—K3	139.50 (5)	C7—O7—K3^iv	123.27 (19)
N3Bⁱ—K1—K3	101.21 (5)	K2—O7—K3^iv	103.04 (7)
C7B—K1—K3	134.40 (6)	K4—O7—K3^iv	91.98 (7)
C6Bⁱ—K1—K3	60.40 (6)	K1—O8—K4^viii	135.32 (10)
K2—K1—K3	72.16 (2)	K1—O8—H8O	108.7
O6—K2—O7	63.15 (6)	K4^viii—O8—H8O	94.8
O6—K2—O3Bⁱⁱ	68.50 (7)	K1—O8—H8P	116.0
O7—K2—O3Bⁱⁱ	130.88 (7)	K4^viii—O8—H8P	91.6
O6—K2—O9	108.86 (7)	H8O—O8—H8P	106.1
O7—K2—O9	91.30 (7)	K2—O9—H9P	109.4
O3Bⁱⁱ—K2—O9	96.29 (8)	K2—O9—H9O	127.8
O6—K2—O4Bⁱⁱⁱ	127.95 (7)	H9P—O9—H9O	107.0
O7—K2—O4Bⁱⁱⁱ	71.65 (7)	K3—O10—H10O	73.8
O3Bⁱⁱ—K2—O4Bⁱⁱⁱ	153.83 (7)	K3—O10—H10P	146.5
O9—K2—O4Bⁱⁱⁱ	96.17 (8)	H10O—O10—H10P	105.9
O6—K2—O7B	68.65 (7)	C2—N1—N2	116.8 (3)
O7—K2—O7B	71.37 (7)	C2—N1—Ni1	116.5 (2)
O3Bⁱⁱ—K2—O7B	99.16 (7)	N2—N1—Ni1	126.66 (19)
O9—K2—O7B	161.85 (8)	N1—N2—C4	110.7 (2)
O4Bⁱⁱⁱ—K2—O7B	73.70 (7)	N1—N2—C3	109.7 (2)
O6—K2—N2Bⁱⁱⁱ	153.59 (7)	C4—N2—C3	109.4 (2)
O7—K2—N2Bⁱⁱⁱ	129.35 (7)	N1—N2—K4^v	104.06 (16)
O3Bⁱⁱ—K2—N2Bⁱⁱⁱ	98.31 (7)	C4—N2—K4^v	116.19 (18)
O9—K2—N2Bⁱⁱⁱ	94.92 (7)	C3—N2—K4^v	106.62 (17)
O4Bⁱⁱⁱ—K2—N2Bⁱⁱⁱ	57.71 (7)	N4—N3—C5	110.6 (2)
O7B—K2—N2Bⁱⁱⁱ	92.22 (7)	N4—N3—C3	109.3 (2)
O6—K2—C6	19.59 (7)	C5—N3—C3	109.7 (2)
O7—K2—C6	44.71 (7)	N4—N3—K3	106.96 (16)
O3Bⁱⁱ—K2—C6	86.20 (7)	C5—N3—K3	107.10 (18)
O9—K2—C6	99.55 (7)	C3—N3—K3	113.13 (18)
O4Bⁱⁱⁱ—K2—C6	114.21 (7)	C6—N4—N3	115.7 (2)
O7B—K2—C6	72.17 (7)	C6—N4—Ni1	116.7 (2)
N2Bⁱⁱⁱ—K2—C6	164.29 (7)	N3—N4—Ni1	127.1 (2)
O6—K2—C7	45.08 (7)	O3—C1—O2	125.2 (3)
O7—K2—C7	18.82 (7)	O3—C1—C2	120.4 (3)
O3Bⁱⁱ—K2—C7	112.08 (7)	O2—C1—C2	114.4 (3)
O9—K2—C7	93.17 (7)	O3—C1—K4^vi	62.64 (17)
O4Bⁱⁱⁱ—K2—C7	90.08 (7)	O2—C1—K4^vi	71.65 (16)
O7B—K2—C7	72.22 (7)	C2—C1—K4^vi	145.90 (19)
N2Bⁱⁱⁱ—K2—C7	147.43 (7)	O4—C2—N1	127.9 (3)
C6—K2—C7	26.07 (7)	O4—C2—C1	121.8 (3)
O6—K2—C2Bⁱⁱⁱ	134.22 (7)	N1—C2—C1	110.2 (3)
O7—K2—C2Bⁱⁱⁱ	88.06 (7)	O4—C2—K4^v	50.47 (16)
O3Bⁱⁱ—K2—C2Bⁱⁱⁱ	134.59 (7)	N1—C2—K4^v	86.15 (18)
O9—K2—C2Bⁱⁱⁱ	106.44 (8)	C1—C2—K4^v	146.74 (19)
O4Bⁱⁱⁱ—K2—C2Bⁱⁱⁱ	19.29 (7)	N3—C3—N2	113.3 (2)
O7B—K2—C2Bⁱⁱⁱ	68.67 (7)	N3—C3—H3A	108.9
N2Bⁱⁱⁱ—K2—C2Bⁱⁱⁱ	42.10 (7)	N2—C3—H3A	108.9
C6—K2—C2Bⁱⁱⁱ	126.35 (7)	N3—C3—H3B	108.9
C7—K2—C2Bⁱⁱⁱ	105.43 (7)	N2—C3—H3B	108.9
O6—K2—K1	49.34 (5)	H3A—C3—H3B	107.7
O7—K2—K1	99.18 (5)	O5—C4—N2	112.9 (2)
O3Bⁱⁱ—K2—K1	51.36 (5)	O5—C4—H4A	109.0
O9—K2—K1	143.89 (6)	N2—C4—H4A	109.0
O4Bⁱⁱⁱ—K2—K1	119.94 (5)	O5—C4—H4B	109.0
O7B—K2—K1	48.41 (5)	N2—C4—H4B	109.0
N2Bⁱⁱⁱ—K2—K1	104.38 (6)	H4A—C4—H4B	107.8
C6—K2—K1	66.77 (5)	O5—C5—N3	113.3 (2)
C7—K2—K1	86.75 (5)	O5—C5—K4^viii	50.01 (13)
C2Bⁱⁱⁱ—K2—K1	108.36 (5)	N3—C5—K4^viii	151.1 (2)
O6—K2—K3^iv	87.29 (5)	O5—C5—H5A	108.9
O7—K2—K3^iv	38.69 (5)	N3—C5—H5A	108.9
O3Bⁱⁱ—K2—K3^iv	147.21 (6)	K4^viii—C5—H5A	99.6
O9—K2—K3^iv	112.80 (6)	O5—C5—H5B	108.9
O4Bⁱⁱⁱ—K2—K3^iv	40.67 (5)	N3—C5—H5B	108.9
O7B—K2—K3^iv	49.92 (5)	K4^viii—C5—H5B	65.4
N2Bⁱⁱⁱ—K2—K3^iv	94.10 (5)	H5A—C5—H5B	107.7
C6—K2—K3^iv	74.71 (5)	O6—C6—N4	128.1 (3)
C7—K2—K3^iv	53.87 (5)	O6—C6—C7	123.0 (3)
C2Bⁱⁱⁱ—K2—K3^iv	52.13 (5)	N4—C6—C7	108.9 (3)
K1—K2—K3^iv	96.17 (2)	O6—C6—K2	46.89 (15)
O7ⁱ—K3—O3Bⁱⁱ	130.32 (7)	N4—C6—K2	162.9 (2)
O7ⁱ—K3—O4Bⁱⁱ	70.29 (6)	C7—C6—K2	78.47 (16)
O3Bⁱⁱ—K3—O4Bⁱⁱ	60.07 (7)	O6—C6—K3	48.13 (15)
O7ⁱ—K3—O6	157.32 (7)	N4—C6—K3	87.33 (18)
O3Bⁱⁱ—K3—O6	65.69 (6)	C7—C6—K3	147.92 (19)
O4Bⁱⁱ—K3—O6	121.88 (7)	K2—C6—K3	79.28 (7)
O7ⁱ—K3—O3^v	88.18 (7)	O7—C7—O1	124.8 (3)
O3Bⁱⁱ—K3—O3^v	92.43 (7)	O7—C7—C6	119.9 (3)
O4Bⁱⁱ—K3—O3^v	88.69 (7)	O1—C7—C6	115.2 (3)
O6—K3—O3^v	73.94 (6)	O7—C7—K4	56.45 (16)
O7ⁱ—K3—N3	108.15 (7)	O1—C7—K4	75.08 (16)
O3Bⁱⁱ—K3—N3	120.86 (7)	C6—C7—K4	148.43 (19)
O4Bⁱⁱ—K3—N3	168.61 (7)	O7—C7—K2	45.16 (15)
O6—K3—N3	55.78 (7)	O1—C7—K2	164.7 (2)
O3^v—K3—N3	79.96 (7)	C6—C7—K2	75.46 (16)
O7ⁱ—K3—O10	64.62 (7)	K4—C7—K2	90.18 (8)
O3Bⁱⁱ—K3—O10	136.54 (7)	N4B—Ni1B—N1B	95.93 (11)
O4Bⁱⁱ—K3—O10	115.82 (7)	N4B—Ni1B—O2B	178.25 (11)
O6—K3—O10	117.23 (7)	N1B—Ni1B—O2B	85.75 (10)
O3^v—K3—O10	130.90 (7)	N4B—Ni1B—O1B	85.46 (10)
N3—K3—O10	71.96 (7)	N1B—Ni1B—O1B	178.61 (11)
O7ⁱ—K3—O6Bⁱ	115.43 (7)	O2B—Ni1B—O1B	92.86 (9)
O3Bⁱⁱ—K3—O6Bⁱ	69.03 (7)	C7B—O1B—Ni1B	112.2 (2)
O4Bⁱⁱ—K3—O6Bⁱ	94.66 (6)	C7B—O1B—K1	83.73 (17)
O6—K3—O6Bⁱ	84.13 (6)	Ni1B—O1B—K1	152.27 (11)
O3^v—K3—O6Bⁱ	155.90 (7)	C1B—O2B—Ni1B	113.4 (2)
N3—K3—O6Bⁱ	96.08 (7)	C1B—O3B—K2ⁱⁱ	132.9 (2)
O10—K3—O6Bⁱ	68.32 (7)	C1B—O3B—K3ⁱⁱ	114.8 (2)
O7ⁱ—K3—O7Bⁱ	64.91 (6)	K2ⁱⁱ—O3B—K3ⁱⁱ	105.44 (8)
O3Bⁱⁱ—K3—O7Bⁱ	92.46 (6)	C1B—O3B—K1ⁱⁱ	124.0 (2)
O4Bⁱⁱ—K3—O7Bⁱ	66.72 (6)	K2ⁱⁱ—O3B—K1ⁱⁱ	79.97 (6)
O6—K3—O7Bⁱ	136.08 (6)	K3ⁱⁱ—O3B—K1ⁱⁱ	87.20 (7)
O3^v—K3—O7Bⁱ	147.96 (7)	C2B—O4B—K2ⁱⁱⁱ	113.82 (19)
N3—K3—O7Bⁱ	123.44 (7)	C2B—O4B—K3ⁱⁱ	110.98 (19)
O10—K3—O7Bⁱ	53.97 (6)	K2ⁱⁱⁱ—O4B—K3ⁱⁱ	99.81 (7)
O6Bⁱ—K3—O7Bⁱ	52.04 (6)	C5B—O5B—C4B	109.9 (2)
O7ⁱ—K3—C2Bⁱⁱ	87.34 (7)	C6B—O6B—K1^iv	115.7 (2)
O3Bⁱⁱ—K3—C2Bⁱⁱ	43.53 (7)	C6B—O6B—K3^iv	107.9 (2)
O4Bⁱⁱ—K3—C2Bⁱⁱ	19.60 (7)	K1^iv—O6B—K3^iv	85.30 (7)
O6—K3—C2Bⁱⁱ	108.83 (7)	C7B—O7B—K1	97.60 (19)
O3^v—K3—C2Bⁱⁱ	99.07 (7)	C7B—O7B—K2	115.0 (2)
N3—K3—C2Bⁱⁱ	164.39 (7)	K1—O7B—K2	79.58 (6)
O10—K3—C2Bⁱⁱ	118.22 (7)	C7B—O7B—K3^iv	106.4 (2)
O6Bⁱ—K3—C2Bⁱⁱ	78.38 (7)	K1—O7B—K3^iv	155.85 (9)
O7Bⁱ—K3—C2Bⁱⁱ	64.41 (7)	K2—O7B—K3^iv	88.02 (6)
O7ⁱ—K3—C6	138.54 (7)	C2B—N1B—N2B	117.3 (3)
O3Bⁱⁱ—K3—C6	83.02 (7)	C2B—N1B—Ni1B	115.9 (2)
O4Bⁱⁱ—K3—C6	133.08 (7)	N2B—N1B—Ni1B	126.6 (2)
O6—K3—C6	19.12 (6)	N1B—N2B—C4B	110.4 (2)
O3^v—K3—C6	63.31 (7)	N1B—N2B—C3B	109.6 (2)
N3—K3—C6	41.19 (7)	C4B—N2B—C3B	109.0 (2)
O10—K3—C6	110.86 (7)	N1B—N2B—K2ⁱⁱⁱ	106.33 (17)
O6Bⁱ—K3—C6	98.09 (7)	C4B—N2B—K2ⁱⁱⁱ	106.21 (18)
O7Bⁱ—K3—C6	148.73 (7)	C3B—N2B—K2ⁱⁱⁱ	115.23 (18)
C2Bⁱⁱ—K3—C6	124.54 (7)	N4B—N3B—C5B	110.0 (2)
O7ⁱ—K3—C1Bⁱⁱ	112.89 (7)	N4B—N3B—C3B	109.1 (2)
O3Bⁱⁱ—K3—C1Bⁱⁱ	18.63 (7)	C5B—N3B—C3B	109.6 (2)
O4Bⁱⁱ—K3—C1Bⁱⁱ	43.75 (7)	N4B—N3B—K1^iv	103.54 (16)
O6—K3—C1Bⁱⁱ	84.28 (7)	C5B—N3B—K1^iv	109.54 (18)
O3^v—K3—C1Bⁱⁱ	99.41 (7)	C3B—N3B—K1^iv	114.86 (18)
N3—K3—C1Bⁱⁱ	138.92 (7)	C6B—N4B—N3B	116.8 (3)
O10—K3—C1Bⁱⁱ	128.16 (7)	C6B—N4B—Ni1B	116.5 (2)
O6Bⁱ—K3—C1Bⁱⁱ	67.97 (7)	N3B—N4B—Ni1B	126.6 (2)
O7Bⁱ—K3—C1Bⁱⁱ	77.36 (7)	O3B—C1B—O2B	125.3 (3)
C2Bⁱⁱ—K3—C1Bⁱⁱ	25.56 (7)	O3B—C1B—C2B	119.7 (3)
C6—K3—C1Bⁱⁱ	101.59 (7)	O2B—C1B—C2B	115.0 (3)
O7ⁱ—K3—H10O	64.6	O3B—C1B—K3ⁱⁱ	46.60 (16)
O3Bⁱⁱ—K3—H10O	122.7	O2B—C1B—K3ⁱⁱ	160.3 (2)
O4Bⁱⁱ—K3—H10O	102.2	C2B—C1B—K3ⁱⁱ	75.88 (17)
O6—K3—H10O	124.2	O4B—C2B—N1B	128.7 (3)
O3^v—K3—H10O	144.2	O4B—C2B—C1B	121.8 (3)
N3—K3—H10O	86.8	N1B—C2B—C1B	109.5 (3)
O10—K3—H10O	16.5	O4B—C2B—K2ⁱⁱⁱ	46.89 (15)
O6Bⁱ—K3—H10O	58.1	N1B—C2B—K2ⁱⁱⁱ	87.87 (18)
O7Bⁱ—K3—H10O	37.8	C1B—C2B—K2ⁱⁱⁱ	150.1 (2)
C2Bⁱⁱ—K3—H10O	102.2	O4B—C2B—K3ⁱⁱ	49.41 (15)
C6—K3—H10O	122.8	N1B—C2B—K3ⁱⁱ	154.7 (2)
C1Bⁱⁱ—K3—H10O	112.1	C1B—C2B—K3ⁱⁱ	78.56 (17)
O7—K4—O4^v	76.22 (7)	K2ⁱⁱⁱ—C2B—K3ⁱⁱ	76.10 (7)
O7—K4—O3^vi	93.28 (7)	N2B—C3B—N3B	113.8 (3)
O4^v—K4—O3^vi	157.43 (7)	N2B—C3B—H3B1	108.8
O7—K4—O5^vii	174.39 (7)	N3B—C3B—H3B1	108.8
O4^v—K4—O5^vii	107.36 (7)	N2B—C3B—H3B2	108.8
O3^vi—K4—O5^vii	81.84 (7)	N3B—C3B—H3B2	108.8
O7—K4—N2^v	107.43 (7)	H3B1—C3B—H3B2	107.7
O4^v—K4—N2^v	58.50 (7)	O5B—C4B—N2B	112.4 (3)
O3^vi—K4—N2^v	143.96 (7)	O5B—C4B—H4B1	109.1
O5^vii—K4—N2^v	78.18 (7)	N2B—C4B—H4B1	109.1
O7—K4—O2^vi	108.20 (7)	O5B—C4B—H4B2	109.1
O4^v—K4—O2^vi	156.33 (7)	N2B—C4B—H4B2	109.1
O3^vi—K4—O2^vi	45.97 (6)	H4B1—C4B—H4B2	107.9
O5^vii—K4—O2^vi	70.34 (6)	O5B—C5B—N3B	113.5 (2)
N2^v—K4—O2^vi	98.69 (7)	O5B—C5B—H5B1	108.9
O7—K4—O8^vii	80.97 (7)	N3B—C5B—H5B1	108.9
O4^v—K4—O8^vii	75.67 (7)	O5B—C5B—H5B2	108.9
O3^vi—K4—O8^vii	83.04 (7)	N3B—C5B—H5B2	108.9
O5^vii—K4—O8^vii	95.62 (7)	H5B1—C5B—H5B2	107.7
N2^v—K4—O8^vii	128.35 (8)	O6B—C6B—N4B	129.5 (3)
O2^vi—K4—O8^vii	127.72 (7)	O6B—C6B—C7B	121.0 (3)
O7—K4—C1^vi	107.76 (8)	N4B—C6B—C7B	109.5 (3)
O4^v—K4—C1^vi	175.75 (8)	O6B—C6B—K1^iv	44.70 (15)
O3^vi—K4—C1^vi	23.33 (7)	N4B—C6B—K1^iv	90.89 (19)
O5^vii—K4—C1^vi	68.56 (7)	C7B—C6B—K1^iv	149.0 (2)
N2^v—K4—C1^vi	120.66 (8)	O7B—C7B—O1B	124.2 (3)
O2^vi—K4—C1^vi	24.50 (7)	O7B—C7B—C6B	120.1 (3)
O8^vii—K4—C1^vi	103.22 (8)	O1B—C7B—C6B	115.7 (3)
O7—K4—O1	44.19 (6)	O7B—C7B—K1	59.38 (17)
O4^v—K4—O1	79.06 (6)	O1B—C7B—K1	72.16 (17)
O3^vi—K4—O1	107.45 (7)	C6B—C7B—K1	150.1 (2)
O5^vii—K4—O1	140.07 (6)

N4—Ni1—O1—C7	−5.2 (2)	K3—C6—C7—O1	121.4 (3)
O2—Ni1—O1—C7	172.8 (2)	O6—C6—C7—K4	80.9 (5)
N4—Ni1—O1—K4	106.9 (2)	N4—C6—C7—K4	−98.5 (4)
O2—Ni1—O1—K4	−75.08 (19)	K2—C6—C7—K4	65.4 (3)
N1—Ni1—O2—C1	−6.6 (2)	K3—C6—C7—K4	18.5 (7)
O1—Ni1—O2—C1	172.3 (2)	O6—C6—C7—K2	15.5 (3)
N1—Ni1—O2—K4^vi	111.6 (2)	N4—C6—C7—K2	−163.9 (2)
O1—Ni1—O2—K4^vi	−69.5 (2)	K3—C6—C7—K2	−46.9 (3)
N4—Ni1—N1—C2	−179.1 (2)	N4B—Ni1B—O1B—C7B	4.4 (2)
O2—Ni1—N1—C2	2.9 (2)	O2B—Ni1B—O1B—C7B	−175.1 (2)
N4—Ni1—N1—N2	0.5 (2)	N4B—Ni1B—O1B—K1	−117.2 (2)
O2—Ni1—N1—N2	−177.6 (2)	O2B—Ni1B—O1B—K1	63.2 (2)
C2—N1—N2—C4	−90.7 (3)	N1B—Ni1B—O2B—C1B	−1.5 (2)
Ni1—N1—N2—C4	89.7 (3)	O1B—Ni1B—O2B—C1B	178.5 (2)
C2—N1—N2—C3	148.5 (3)	N4B—Ni1B—N1B—C2B	177.3 (2)
Ni1—N1—N2—C3	−31.1 (3)	O2B—Ni1B—N1B—C2B	−3.2 (2)
C2—N1—N2—K4^v	34.8 (3)	N4B—Ni1B—N1B—N2B	2.3 (3)
Ni1—N1—N2—K4^v	−144.78 (16)	O2B—Ni1B—N1B—N2B	−178.2 (2)
C5—N3—N4—C6	83.1 (3)	C2B—N1B—N2B—C4B	−86.4 (3)
C3—N3—N4—C6	−156.0 (3)	Ni1B—N1B—N2B—C4B	88.5 (3)
K3—N3—N4—C6	−33.3 (3)	C2B—N1B—N2B—C3B	153.5 (3)
C5—N3—N4—Ni1	−88.9 (3)	Ni1B—N1B—N2B—C3B	−31.5 (3)
C3—N3—N4—Ni1	32.0 (3)	C2B—N1B—N2B—K2ⁱⁱⁱ	28.4 (3)
K3—N3—N4—Ni1	154.80 (16)	Ni1B—N1B—N2B—K2ⁱⁱⁱ	−156.67 (16)
N1—Ni1—N4—C6	−172.8 (2)	C5B—N3B—N4B—C6B	89.9 (3)
O1—Ni1—N4—C6	8.2 (2)	C3B—N3B—N4B—C6B	−149.9 (3)
N1—Ni1—N4—N3	−1.0 (2)	K1^iv—N3B—N4B—C6B	−27.1 (3)
O1—Ni1—N4—N3	−179.9 (2)	C5B—N3B—N4B—Ni1B	−85.9 (3)
K4^vi—O3—C1—O2	−36.9 (3)	C3B—N3B—N4B—Ni1B	34.3 (3)
K3^v—O3—C1—O2	51.7 (4)	K1^iv—N3B—N4B—Ni1B	157.07 (16)
K4^vi—O3—C1—C2	141.0 (2)	N1B—Ni1B—N4B—C6B	−179.7 (2)
K3^v—O3—C1—C2	−130.4 (2)	O1B—Ni1B—N4B—C6B	0.3 (2)
K3^v—O3—C1—K4^vi	88.59 (18)	N1B—Ni1B—N4B—N3B	−3.9 (3)
Ni1—O2—C1—O3	−173.4 (2)	O1B—Ni1B—N4B—N3B	176.1 (2)
K4^vi—O2—C1—O3	34.2 (3)	K2ⁱⁱ—O3B—C1B—O2B	−57.3 (4)
Ni1—O2—C1—C2	8.5 (3)	K3ⁱⁱ—O3B—C1B—O2B	156.7 (2)
K4^vi—O2—C1—C2	−143.9 (2)	K1ⁱⁱ—O3B—C1B—O2B	52.5 (4)
Ni1—O2—C1—K4^vi	152.39 (15)	K2ⁱⁱ—O3B—C1B—C2B	124.0 (3)
K4^v—O4—C2—N1	−41.1 (4)	K3ⁱⁱ—O3B—C1B—C2B	−22.0 (3)
K4^v—O4—C2—C1	139.8 (2)	K1ⁱⁱ—O3B—C1B—C2B	−126.2 (2)
N2—N1—C2—O4	2.0 (5)	K2ⁱⁱ—O3B—C1B—K3ⁱⁱ	146.0 (3)
Ni1—N1—C2—O4	−178.4 (3)	K1ⁱⁱ—O3B—C1B—K3ⁱⁱ	−104.2 (2)
N2—N1—C2—C1	−178.8 (2)	Ni1B—O2B—C1B—O3B	−173.6 (3)
Ni1—N1—C2—C1	0.8 (3)	Ni1B—O2B—C1B—C2B	5.2 (3)
N2—N1—C2—K4^v	−28.5 (2)	Ni1B—O2B—C1B—K3ⁱⁱ	−115.0 (6)
Ni1—N1—C2—K4^v	151.09 (15)	K2ⁱⁱⁱ—O4B—C2B—N1B	−35.3 (4)
O3—C1—C2—O4	−5.2 (5)	K3ⁱⁱ—O4B—C2B—N1B	−147.0 (3)
O2—C1—C2—O4	173.0 (3)	K2ⁱⁱⁱ—O4B—C2B—C1B	144.7 (2)
K4^vi—C1—C2—O4	79.9 (4)	K3ⁱⁱ—O4B—C2B—C1B	33.1 (3)
O3—C1—C2—N1	175.5 (3)	K3ⁱⁱ—O4B—C2B—K2ⁱⁱⁱ	−111.64 (18)
O2—C1—C2—N1	−6.3 (4)	K2ⁱⁱⁱ—O4B—C2B—K3ⁱⁱ	111.64 (18)
K4^vi—C1—C2—N1	−99.3 (4)	N2B—N1B—C2B—O4B	1.8 (5)
O3—C1—C2—K4^v	60.0 (5)	Ni1B—N1B—C2B—O4B	−173.7 (3)
O2—C1—C2—K4^v	−121.8 (3)	N2B—N1B—C2B—C1B	−178.3 (2)
K4^vi—C1—C2—K4^v	145.1 (2)	Ni1B—N1B—C2B—C1B	6.2 (3)
N4—N3—C3—N2	−69.2 (3)	N2B—N1B—C2B—K2ⁱⁱⁱ	−23.2 (2)
C5—N3—C3—N2	52.2 (3)	Ni1B—N1B—C2B—K2ⁱⁱⁱ	161.31 (15)
K3—N3—C3—N2	171.75 (18)	N2B—N1B—C2B—K3ⁱⁱ	−73.4 (6)
N1—N2—C3—N3	69.0 (3)	Ni1B—N1B—C2B—K3ⁱⁱ	111.1 (5)
C4—N2—C3—N3	−52.6 (3)	O3B—C1B—C2B—O4B	−8.7 (4)
K4^v—N2—C3—N3	−178.98 (19)	O2B—C1B—C2B—O4B	172.4 (3)
C5—O5—C4—N2	−57.2 (3)	K3ⁱⁱ—C1B—C2B—O4B	−25.0 (3)
K4^viii—O5—C4—N2	162.24 (18)	O3B—C1B—C2B—N1B	171.3 (3)
N1—N2—C4—O5	−66.0 (3)	O2B—C1B—C2B—N1B	−7.5 (4)
C3—N2—C4—O5	54.9 (3)	K3ⁱⁱ—C1B—C2B—N1B	155.0 (2)
K4^v—N2—C4—O5	175.62 (17)	O3B—C1B—C2B—K2ⁱⁱⁱ	48.9 (5)
C4—O5—C5—N3	56.9 (3)	O2B—C1B—C2B—K2ⁱⁱⁱ	−129.9 (3)
K4^viii—O5—C5—N3	−151.9 (2)	K3ⁱⁱ—C1B—C2B—K2ⁱⁱⁱ	32.6 (4)
C4—O5—C5—K4^viii	−151.2 (2)	O3B—C1B—C2B—K3ⁱⁱ	16.3 (3)
N4—N3—C5—O5	66.4 (3)	O2B—C1B—C2B—K3ⁱⁱ	−162.6 (3)
C3—N3—C5—O5	−54.2 (3)	N1B—N2B—C3B—N3B	68.4 (3)
K3—N3—C5—O5	−177.35 (19)	C4B—N2B—C3B—N3B	−52.5 (3)
N4—N3—C5—K4^viii	18.2 (5)	K2ⁱⁱⁱ—N2B—C3B—N3B	−171.76 (18)
C3—N3—C5—K4^viii	−102.4 (4)	N4B—N3B—C3B—N2B	−69.9 (3)
K3—N3—C5—K4^viii	134.4 (3)	C5B—N3B—C3B—N2B	50.6 (3)
K2—O6—C6—N4	158.3 (3)	K1^iv—N3B—C3B—N2B	174.42 (18)
K1—O6—C6—N4	−88.6 (5)	C5B—O5B—C4B—N2B	−59.4 (3)
K3—O6—C6—N4	38.5 (4)	N1B—N2B—C4B—O5B	−63.8 (3)
K2—O6—C6—C7	−21.0 (3)	C3B—N2B—C4B—O5B	56.6 (3)
K1—O6—C6—C7	92.1 (4)	K2ⁱⁱⁱ—N2B—C4B—O5B	−178.71 (19)
K3—O6—C6—C7	−140.8 (2)	C4B—O5B—C5B—N3B	57.7 (3)
K1—O6—C6—K2	113.1 (4)	N4B—N3B—C5B—O5B	67.1 (3)
K3—O6—C6—K2	−119.79 (19)	C3B—N3B—C5B—O5B	−52.9 (3)
K2—O6—C6—K3	119.79 (19)	K1^iv—N3B—C5B—O5B	−179.72 (19)
K1—O6—C6—K3	−127.1 (4)	K1^iv—O6B—C6B—N4B	36.6 (4)
N3—N4—C6—O6	−0.9 (5)	K3^iv—O6B—C6B—N4B	130.0 (3)
Ni1—N4—C6—O6	171.9 (2)	K1^iv—O6B—C6B—C7B	−144.6 (2)
N3—N4—C6—C7	178.5 (2)	K3^iv—O6B—C6B—C7B	−51.1 (3)
Ni1—N4—C6—C7	−8.7 (3)	K3^iv—O6B—C6B—K1^iv	93.42 (17)
N3—N4—C6—K2	65.3 (8)	N3B—N4B—C6B—O6B	−1.3 (5)
Ni1—N4—C6—K2	−121.9 (6)	Ni1B—N4B—C6B—O6B	174.9 (3)
N3—N4—C6—K3	26.8 (2)	N3B—N4B—C6B—C7B	179.7 (2)
Ni1—N4—C6—K3	−160.42 (15)	Ni1B—N4B—C6B—C7B	−4.0 (3)
K2—O7—C7—O1	−164.9 (2)	N3B—N4B—C6B—K1^iv	23.5 (2)
K4—O7—C7—O1	−33.2 (3)	Ni1B—N4B—C6B—K1^iv	−160.30 (15)
K3^iv—O7—C7—O1	66.7 (4)	K1—O7B—C7B—O1B	33.6 (3)
K2—O7—C7—C6	11.3 (3)	K2—O7B—C7B—O1B	−48.4 (4)
K4—O7—C7—C6	142.9 (2)	K3^iv—O7B—C7B—O1B	−144.0 (3)
K3^iv—O7—C7—C6	−117.1 (2)	K1—O7B—C7B—C6B	−145.2 (2)
K2—O7—C7—K4	−131.67 (18)	K2—O7B—C7B—C6B	132.8 (2)
K3^iv—O7—C7—K4	99.98 (18)	K3^iv—O7B—C7B—C6B	37.2 (3)
K4—O7—C7—K2	131.67 (18)	K2—O7B—C7B—K1	−82.00 (13)
K3^iv—O7—C7—K2	−128.3 (2)	K3^iv—O7B—C7B—K1	−177.60 (16)
Ni1—O1—C7—O7	178.1 (2)	Ni1B—O1B—C7B—O7B	173.5 (3)
K4—O1—C7—O7	28.2 (3)	K1—O1B—C7B—O7B	−30.0 (3)
Ni1—O1—C7—C6	1.8 (3)	Ni1B—O1B—C7B—C6B	−7.7 (3)
K4—O1—C7—C6	−148.1 (2)	K1—O1B—C7B—C6B	148.9 (2)
Ni1—O1—C7—K4	149.87 (15)	Ni1B—O1B—C7B—K1	−156.51 (16)
Ni1—O1—C7—K2	133.7 (7)	O6B—C6B—C7B—O7B	7.6 (5)
K4—O1—C7—K2	−16.1 (8)	N4B—C6B—C7B—O7B	−173.3 (3)
O6—C6—C7—O7	7.3 (4)	K1^iv—C6B—C7B—O7B	−44.8 (5)
N4—C6—C7—O7	−172.2 (3)	O6B—C6B—C7B—O1B	−171.3 (3)
K2—C6—C7—O7	−8.2 (2)	N4B—C6B—C7B—O1B	7.8 (4)
K3—C6—C7—O7	−55.2 (5)	K1^iv—C6B—C7B—O1B	136.3 (3)
O6—C6—C7—O1	−176.2 (3)	O6B—C6B—C7B—K1	−72.3 (5)
N4—C6—C7—O1	4.4 (4)	N4B—C6B—C7B—K1	106.7 (4)
K2—C6—C7—O1	168.3 (2)	K1^iv—C6B—C7B—K1	−124.7 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8O···O9^viii	0.85	2.02	2.869 (4)	173
O8—H8P···O4B^ix	0.85	2.01	2.858 (3)	166
O9—H9P···O4^v	0.86	1.91	2.722 (3)	157
O9—H9O···O6B^vii	0.86	2.07	2.864 (3)	153
O10—H10P···O4^x	0.88	2.02	2.887 (3)	168
O10—H10O···O7Bⁱ	0.87	2.04	2.882 (3)	164

Symmetry codes: (i) x, y+1, z; (v) −x+1, −y+1, −z; (vii) x, −y+1/2, z−1/2; (viii) x, −y+1/2, z+1/2; (ix) −x, y+1/2, −z+1/2; (x) −x+1, y+1/2, −z+1/2.

Values for continuous shapes measures (CShM) of the polyhedra centred by the potassium cations top

Shape	CShM
	K1	K2
Heptagon (D7h)	28.515	29.484
Hexagonal pyramid (C6v)	17.225	20.349
Pentagonal bipyramid (D5h)	5.142	3.122
Capped octahedron (C3v)	7.539	7.840
Capped trigonal prism (C2v)	6.374	5.639
Johnson pentagonal bipyramid J13 (D5h)	8.789	6.943
Johnson elongated triangular pyramid J7 (C3v)	16.352	20.453
	K3
Enneagon (D9h)	32.593
Octagonal pyramid (C8v)	23.087
Heptagonal bipyramid (D7h)	14.962
Johnson triangular cupola J3 (C3v)	12.759
Capped cube J8 (C4v)	9.046
Spherical-relaxed capped cube (C4v)	7.600
Capped square antiprism J10 (C4v)	6.360
Spherical capped square antiprism (C4v)	5.020
Tricapped trigonal prism J51 (D3h)	6.694
Spherical tricapped trigonal prism (D3h)	5.698
Tridiminished icosahedron J63 (C3v)	11.379
Hula-hoop (C2v)	6.577
Muffin (Cs)	3.691
	K4
Octagon (D8h)	33.086
Heptagonal pyramid (C7v)	18.988
Hexagonal bipyramid (D6h)	14.426
Cube (Oh)	10.884
Square antiprism (D4d)	5.463
Triangular dodecahedron (D2d)	5.187
Johnson gyrobifastigium J26 (D2d)	11.775
Johnson elongated triangular bipyramid J14 (D3h)	26.080
Biaugmented trigonal prism J50 (C2v)	6.413
Biaugmented trigonal prism (C2v)	6.587
Snub diphenoid J84 (D2d)	7.862
Triakis tetrahedron (Td)	11.175
Elongated trigonal bipyramid (D3h)	20.295

Comparison of selected geometric data (A,°; mean values) for the Ni1 complex anion from calculated and X-ray data top

Geometric parameter	X-ray	PM7	DFTB	GFN2-xTB
Oxadiazinane ring
C—O	1.434	1.413	1.467	1.410
C—N	1.463	1.489	1.463	1.452
Carboxylate moiety
C—O	1.287	1.276	1.451	1.260
C═O	1.233	1.224	1.196	1.208
Hydrazide moiety
C—O	1.249	1.232	1.227	1.216
C—N	1.321	1.357	1.393	1.332
N—N	1.432	1.413	1.413	1.415
C—N_amide—Ni—N_oxadiazine	175.74	133.89	169.00	162.81
Ni coordination arrangement
Ni—O	1.892	1.776	1.780	1.871
Ni—N	1.840	1.955	1.974	1.871
O—Ni—N chelate	85.24	93.35	81.32	82.94
O—Ni—N non-chelate	178.29	173.19	162.52	176.77
N—Ni—N	85.53	88.09	90.73	94.40

Funding information

This work was supported by the Ministry of Education and Science of Ukraine: Grant of the Ministry of Education and Science of Ukraine for perspective development of a scientific direction `Mathematical sciences and natural sciences' at Taras Shevchenko National University of Kyiv.

References

Alvarez, S. (2013). Dalton Trans. 42, 8617–8636. Web of Science CrossRef CAS PubMed Google Scholar
Bannwarth, C., Ehlert, S. & Grimme, S. (2019). J. Chem. Theory Comput. 15, 1652–1671. Web of Science CrossRef CAS PubMed Google Scholar
Brandenburg, K. (2009). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2008). COLLECT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Clark, G. R., Skelton, B. W. & Waters, T. N. (1976). J. Chem. Soc. Dalton Trans. pp. 1528–1536. CSD CrossRef Web of Science Google Scholar
Elstner, M., Porezag, D., Jungnickel, G., Elsner, J., Haugk, M., Frauenheim, Th., Suhai, S. & Seifert, G. (1998). Phys. Rev. B, 58, 7260–7268. Web of Science CrossRef CAS Google Scholar
Feigel, M. & Strassner, T. (1993). J. Mol. Struct. Theochem, 283, 33–48. CrossRef Google Scholar
Fritsky, I. O., Kozłowski, H., Kanderal, O. M., Haukka, M., Świątek-Kozłowska, J., Gumienna-Kontecka, E. & Meyer, F. (2006). Chem. Commun. pp. 4125–4127. Web of Science CSD CrossRef Google Scholar
Fritsky, I. O., Kozłowski, H., Sadler, P. J., Yefetova, O. P., Śwątek-Kozłowska, J., Kalibabchuk, V. A. & Głowiak, T. (1998). J. Chem. Soc. Dalton Trans. pp. 3269–3274. Web of Science CSD CrossRef Google Scholar
Gagné, O. C. & Hawthorne, F. C. (2016). Acta Cryst. B72, 602–625. Web of Science CrossRef IUCr Journals Google Scholar
Grimme, S. (2019). xtb 6.4. Mulliken Center for Theoretical Chemistry, University of Bonn, Bonn, Germany. 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
Hourahine, B., Aradi, B., Blum, V., Bonafé, F., Buccheri, A., Camacho, C., Cevallos, C., Deshaye, M. Y., Dumitrică, T., Dominguez, A., Ehlert, S., Elstner, M., van der Heide, T., Hermann, J., Irle, S., Kranz, J. J., Köhler, C., Kowalczyk, T., Kubař, T., Lee, I. S., Lutsker, V., Maurer, R. J., Min, S. K., Mitchell, I., Negre, C., Niehaus, T. A., Niklasson, A. M. N., Page, A. J., Pecchia, A., Penazzi, G., Persson, M. P., Řezáč, J., Sánchez, C. G., Sternberg, M., Stöhr, M., Stuckenberg, F., Tkatchenko, A., Yu, V. W. & Frauenheim, T. (2020). J. Chem. Phys. 152, 124101. Web of Science CrossRef PubMed Google Scholar
Llunell, M., Casanova, D., Cirera, J., Alemany, P. & Alvarez, S. (2013). SHAPE. Barcelona, Spain. Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814–3816. Web of Science CrossRef Google Scholar
Mokhir, A. A., Gumienna-Kontecka, E., Świątek-Kozłowska, J. J., Petkova, E. G., Fritsky, I. O., Jerzykiewicz, L., Kapshuk, A. A. & Sliva, T. Yu. (2002). Inorg. Chim. Acta, 329, 113–121. Web of Science CSD CrossRef CAS Google Scholar
Oliver, K. J. & Waters, T. N. (1982). J. Chem. Soc. Chem. Commun. pp. 1111–1112. CSD CrossRef Web of Science Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods Enzymol. 276, 307–326. CrossRef CAS PubMed Web of Science Google Scholar
Palatinus, L. & Chapuis, G. (2007). J. Appl. Cryst. 40, 786–790. Web of Science CrossRef CAS IUCr Journals Google Scholar
Pap, J. S., Szywriel, Ł., Rowińska-Żyrek, M., Nikitin, K., Fritsky, I. O. & Kozłowski, H. J. (2011). J. Mol. Catal. A Chem. 334, 77–82. Web of Science CrossRef CAS Google Scholar
Plutenko, M. O., Haukka, M., Husak, A. O., Iskenderov, T. S. & Mulloev, N. U. (2021). Acta Cryst. E77, 298–304. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shylin, S. I., Pavliuk, M. V., D'Amario, L., Mamedov, F., Sá, J., Berggren, G. & Fritsky, I. O. (2019). Chem. Commun. 55, 3335–3338. Web of Science CrossRef CAS Google Scholar
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Stewart, J. J. P. (2013). J. Mol. Model. 19, 1–32. Web of Science CrossRef CAS PubMed Google Scholar
Stewart, J. J. P. (2016). MOPAC2016. Stewart Computational Chemistry, Colorado Springs, CO, USA. Google Scholar
Tomyn, S., Shylin, S. I., Bykov, D., Ksenofontov, V., Gumienna-Kontecka, E., Bon, V. & Fritsky, I. O. (2017). Nat. Commun. 8, 14099. Web of Science CSD CrossRef PubMed Google Scholar
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17. University of Western Australia. Google Scholar
Zheng, G., Witek, H. A., Bobadova-Parvanova, P., Irle, S., Musaev, D. G., Prabhakar, R., Morokuma, K., Lundberg, M., Elstner, M., Köhler, C. & Frauenheim, T. (2007). J. Chem. Theory Comput. 3, 1349–1367. Web of Science CrossRef PubMed Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.