(Pyridine-2,6-di­carboxyl­ato-κ3O,N,O′)(2,2′:6′,2′′- terpyridine-κ3N,N′,N′′)nickel(II) di­methyl­formamide monosolvate monohydrate

Ha, K.

doi:10.1107/S2414314619010356

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 7| July 2019| x191035

https://doi.org/10.1107/S2414314619010356

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(Pyridine-2,6-dicarboxylato-κ³O,N,O′)(2,2′:6′,2′′- terpyridine-κ³N,N′,N′′)nickel(II) dimethylformamide monosolvate monohydrate

Kwang Ha ^a ^*

^aChonnam National University, School of Chemical Engineering, Research Institute of Catalysis, Gwangju, Republic of Korea
^*Correspondence e-mail: hakwang@chonnam.ac.kr

Edited by E. R. T. Tiekink, Sunway University, Malaysia (Received 17 July 2019; accepted 20 July 2019; online 26 July 2019)

In the title complex, [Ni(C₇H₃NO₄)(C₁₅H₁₁N₃)]·C₃H₇NO·H₂O, the Ni^II ion is six-coordinated within an octahedral geometry defined by three N atoms of the 2,2′:6′,2′′-terpyridine ligand, and two O atoms and the N atom of the pyridine-2,6-dicarboxylate di-anion. In the crystal, the complex molecules are stacked in columns parallel to the a axis being connected by π–π stacking [closest inter-centroid separation between pyridyl rings = 3.669 (3) Å]. The connections between columns and solvent molecules to sustain a three-dimensional architecture are of the type water-O—H⋯O(carbonyl) and pyridyl-, methyl-C—H⋯O(carbonyl).

Keywords: crystal structure; nickel(II) complex; terpyridine; pyridine-2,6-dicarboxylic acid.

CCDC reference: 1941852

Structure description

With reference to the title complex, [Ni(dipic)(terpy)]·C₃H₇NO·H₂O (dipic = pyridine-2,6-dicarboxylate; terpy = 2,2′:6′,2"-terpyridine), the crystal structures of related Ni^II complexes [Ni(dipic)(H₂O)₂] (Liu et al., 2006 ), [Ni(dipic)(1,10-phenanthroline)(H₂O)]·H₂O (Ramadevi et al., 2006 ) and [NiCl(terpy)(H₂O)₂]Cl·H₂O (Cortés et al., 1985 ) have been determined previously.

In the title complex, the central Ni^II ion is six-coordinated in a distorted octahedral coordination geometry defined by three N atoms from the tridentate terpy ligand, and two O atoms and the N atom from the dipic di-anion (Fig. 1). The tight O—Ni—N and N—Ni—N chelating angles of O—Ni1—N1 = 78.07 (10) and 78.18 (11)°, and N—Ni1—N = 78.25 (11) and 78.67 (11)° contribute to the distortion of the octahedron. The apical N1—Ni1—N3, N2—Ni1—N4 and O1—Ni1—O3 bond angles are 177.95 (12), 156.92 (10) and 156.26 (9)°, respectively. The Ni—N bonds [1.963 (2)-2.091 (3) Å] are slightly shorter than the Ni—O bonds [2.126 (2) and 2.131 (2) Å]. The two outer pyridyl rings of the terpy ligand are located approximately parallel to the central pyridyl ring, making dihedral angles of 4.7 (3) and 2.3 (3)°. The dihedral angle between the least-squares planes of dipic and terpy ligands is 83.23 (3)°.

Figure 1
The molecular structure of the title compound showing the atom labelling and displacement ellipsoids drawn at the 50% probability level for non-H atoms.

In the crystal, the complex molecules are stacked in columns parallel to the a axis. Within the columns, numerous intermolecular π–π interactions between adjacent six-membered rings are present. For Cg1 (the centroid of ring N2/C8–C12) and Cg2ⁱ [the centroid of ring N3/C13–C17; symmetry code: (i) x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z], the centroid-centroid distance is 3.669 (3) Å and the dihedral angle between the ring planes is 9.6 (2)° (Spek, 2009 ). The complex and solvent molecules display intermolecular O—H⋯O and C—H⋯O hydrogen bonds (Table 1) to stabilize the three-dimensional packing.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6A⋯O2ⁱ	0.71 (5)	2.21 (5)	2.907 (5)	172 (5)
O6—H6B⋯O4	0.74 (6)	2.14 (6)	2.881 (5)	175 (7)
C2—H2⋯O2ⁱⁱ	0.94	2.49	3.254 (4)	138
C8—H8⋯O5ⁱⁱⁱ	0.94	2.47	3.133 (5)	128
C9—H9⋯O2^iv	0.94	2.55	3.465 (5)	163
C25—H25C⋯O4^v	0.97	2.45	3.361 (6)	157
Symmetry codes: (i) x+1, y, z+1; (ii) -x, -y, -z; (iii) x, y, z-1; (iv) x+1, y, z; (v) x-1, y, z.

Synthesis and crystallization

To a solution of Ni(CH₃CO₂)₂·4H₂O (0.2605 g, 1.047 mmol) in MeOH (20 ml) were added pyridine-2,6-dicarboxylic acid (0.1750 g, 1.047 mmol) and 2,2′:6′,2"-terpyridine (0.2444 g, 1.048 mmol), followed by stirring for 1 h at room temperature. The formed precipitate was separated by filtration, washed with MeOH and acetone, and dried at 323 K, to give a pale-green powder (0.3580 g). Green crystals suitable for X-ray analysis were obtained by the slow evaporation of its N,N-dimethylformamide solution at 333 K.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The highest peak (0.42 e Å⁻³) and the deepest hole (−0.39 e Å⁻³) in the final difference Fourier map are located 0.88 Å and 0.29 Å, respectively, from the C20 atom.

Table 2
Experimental details

Crystal data
Chemical formula	[Ni(C₇H₃NO₄)(C₁₅H₁₁N₃)]·C₃H₇NO·H2O
M_r	548.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	223
a, b, c (Å)	8.6188 (4), 27.5899 (13), 10.7559 (5)
β (°)	111.3813 (11)
V (Å³)	2381.62 (19)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.87
Crystal size (mm)	0.16 × 0.13 × 0.09

Data collection
Diffractometer	PHOTON 100 CMOS detector
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.683, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	66113, 4729, 3085
R_int	0.176

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.105, 1.04
No. of reflections	4729
No. of parameters	344
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.39
Computer programs: APEX2 and SAINT (Bruker, 2016), SHELXL2014 (Sheldrick, 2015 ) and ORTEP-3 for Windows (Farrugia, 1997 ).

Structural data

CCDC reference: 1941852

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619010356/tk4060sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619010356/tk4060Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXL2014 (Sheldrick, 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

(Pyridine-2,6-dicarboxylato-κ³O,N,O')(2,2':6',2''-terpyridine-κ³N,N',N'')nickel(II) dimethylformamide monosolvate monohydrate top

Crystal data top

[Ni(C₇H₃NO₄)(C₁₅H₁₁N₃)]·C₃H₇NO·H2O	F(000) = 1136
M_r = 548.19	D_x = 1.529 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.6188 (4) Å	Cell parameters from 7834 reflections
b = 27.5899 (13) Å	θ = 2.5–25.4°
c = 10.7559 (5) Å	µ = 0.87 mm⁻¹
β = 111.3813 (11)°	T = 223 K
V = 2381.62 (19) Å³	Block, green
Z = 4	0.16 × 0.13 × 0.09 mm

Data collection top

PHOTON 100 CMOS detector diffractometer	3085 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.176
φ and ω scans	θ_max = 26.1°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −10→10
T_min = 0.683, T_max = 0.745	k = −34→34
66113 measured reflections	l = −13→13
4729 independent reflections

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)] = 0.051	Hydrogen site location: mixed
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0327P)² + 2.9447P] where P = (F_o² + 2F_c²)/3
4729 reflections	(Δ/σ)_max < 0.001
344 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.39 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.

Refinement. Hydrogen atoms were positioned geometrically and allowed to ride on their respective parent atoms: C—H = 0.94 Å (CH) or 0.97 Å (CH₃), and U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C). The H atoms of the solvent water molecule were localized from Fourier difference maps and refined with isotropic thermal parameters.

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

	x	y	z	U_iso*/U_eq
Ni1	0.36206 (5)	0.16002 (2)	0.23583 (4)	0.02137 (13)
O1	0.1553 (3)	0.14429 (8)	0.0586 (2)	0.0267 (6)
O2	−0.0024 (3)	0.08186 (9)	−0.0495 (2)	0.0378 (6)
O3	0.5679 (3)	0.14403 (9)	0.4142 (2)	0.0309 (6)
O4	0.7196 (3)	0.08116 (10)	0.5247 (3)	0.0467 (7)
N1	0.3587 (3)	0.08889 (9)	0.2374 (3)	0.0203 (6)
N2	0.5267 (3)	0.17374 (10)	0.1390 (3)	0.0260 (7)
N3	0.3713 (3)	0.23164 (9)	0.2408 (3)	0.0233 (6)
N4	0.2007 (3)	0.17652 (10)	0.3353 (3)	0.0259 (7)
C1	0.2379 (4)	0.06562 (12)	0.1423 (3)	0.0224 (8)
C2	0.2282 (5)	0.01548 (13)	0.1436 (4)	0.0304 (9)
H2	0.1413	−0.0011	0.0780	0.037*
C3	0.3494 (5)	−0.00932 (12)	0.2437 (4)	0.0347 (9)
H3	0.3457	−0.0433	0.2467	0.042*
C4	0.4770 (5)	0.01570 (13)	0.3402 (4)	0.0313 (9)
H4	0.5614	−0.0011	0.4076	0.038*
C5	0.4770 (4)	0.06553 (12)	0.3350 (3)	0.0239 (8)
C6	0.1188 (4)	0.09963 (13)	0.0402 (3)	0.0262 (8)
C7	0.6005 (4)	0.09928 (14)	0.4347 (4)	0.0295 (8)
C8	0.6049 (5)	0.14092 (14)	0.0920 (4)	0.0349 (9)
H8	0.5753	0.1081	0.0923	0.042*
C9	0.7263 (6)	0.15281 (16)	0.0435 (5)	0.0611 (14)
H9	0.7804	0.1288	0.0121	0.073*
C10	0.7662 (7)	0.20063 (18)	0.0422 (7)	0.099 (2)
H10	0.8502	0.2099	0.0106	0.119*
C11	0.6846 (6)	0.23548 (16)	0.0869 (6)	0.0767 (18)
H11	0.7097	0.2685	0.0837	0.092*
C12	0.5658 (4)	0.22089 (13)	0.1361 (4)	0.0328 (9)
C13	0.4719 (4)	0.25468 (12)	0.1902 (4)	0.0303 (9)
C14	0.4840 (5)	0.30440 (14)	0.1940 (4)	0.0451 (11)
H14	0.5530	0.3206	0.1571	0.054*
C15	0.3911 (5)	0.33003 (13)	0.2541 (5)	0.0506 (12)
H15	0.3992	0.3640	0.2599	0.061*
C16	0.2876 (5)	0.30606 (14)	0.3051 (4)	0.0423 (10)
H16	0.2230	0.3233	0.3441	0.051*
C17	0.2804 (4)	0.25613 (12)	0.2978 (3)	0.0273 (8)
C18	0.1788 (5)	0.22411 (13)	0.3493 (4)	0.0311 (9)
C19	0.0730 (7)	0.24084 (16)	0.4088 (6)	0.0727 (17)
H19	0.0593	0.2742	0.4188	0.087*
C20	−0.0130 (8)	0.20715 (19)	0.4536 (7)	0.100 (2)
H20	−0.0847	0.2177	0.4962	0.120*
C21	0.0047 (6)	0.15893 (17)	0.4370 (5)	0.0616 (14)
H21	−0.0564	0.1359	0.4647	0.074*
C22	0.1139 (5)	0.14506 (14)	0.3787 (4)	0.0364 (10)
H22	0.1290	0.1118	0.3685	0.044*
O5	0.4038 (4)	0.05868 (11)	0.8998 (3)	0.0635 (9)
N5	0.1913 (4)	0.01358 (12)	0.7603 (3)	0.0400 (8)
C23	0.3260 (6)	0.02115 (17)	0.8683 (4)	0.0503 (11)
H23	0.3651	−0.0053	0.9265	0.060*
C24	0.1119 (6)	−0.03242 (17)	0.7291 (5)	0.0701 (15)
H24A	−0.0072	−0.0284	0.7054	0.105*
H24B	0.1553	−0.0536	0.8060	0.105*
H24C	0.1336	−0.0466	0.6544	0.105*
C25	0.1256 (7)	0.05288 (19)	0.6690 (6)	0.0858 (18)
H25A	0.1672	0.0507	0.5967	0.129*
H25B	0.1602	0.0834	0.7156	0.129*
H25C	0.0049	0.0511	0.6331	0.129*
O6	0.8679 (5)	0.15110 (13)	0.7334 (5)	0.0590 (10)
H6A	0.896 (6)	0.1358 (18)	0.790 (5)	0.052 (19)*
H6B	0.825 (8)	0.133 (2)	0.681 (6)	0.10 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0231 (2)	0.0176 (2)	0.0246 (2)	−0.0026 (2)	0.01005 (17)	−0.0023 (2)
O1	0.0277 (13)	0.0196 (13)	0.0297 (14)	−0.0020 (10)	0.0067 (11)	−0.0014 (10)
O2	0.0318 (15)	0.0330 (16)	0.0351 (15)	−0.0064 (12)	−0.0038 (13)	−0.0066 (12)
O3	0.0301 (14)	0.0295 (15)	0.0282 (14)	−0.0047 (11)	0.0048 (12)	−0.0050 (11)
O4	0.0410 (17)	0.0473 (18)	0.0350 (16)	0.0014 (14)	−0.0061 (14)	0.0063 (14)
N1	0.0212 (14)	0.0200 (14)	0.0211 (14)	0.0003 (13)	0.0096 (12)	0.0015 (13)
N2	0.0278 (16)	0.0220 (17)	0.0313 (17)	−0.0016 (12)	0.0145 (14)	−0.0019 (13)
N3	0.0244 (15)	0.0189 (14)	0.0280 (15)	−0.0009 (13)	0.0112 (13)	−0.0031 (13)
N4	0.0280 (16)	0.0218 (16)	0.0306 (17)	−0.0042 (13)	0.0141 (14)	−0.0042 (13)
C1	0.0236 (18)	0.0212 (19)	0.0246 (19)	−0.0027 (15)	0.0113 (16)	−0.0056 (15)
C2	0.033 (2)	0.024 (2)	0.035 (2)	−0.0027 (17)	0.0129 (18)	−0.0049 (17)
C3	0.047 (2)	0.0163 (18)	0.046 (2)	0.0005 (19)	0.023 (2)	0.0017 (19)
C4	0.034 (2)	0.028 (2)	0.032 (2)	0.0094 (17)	0.0125 (18)	0.0100 (17)
C5	0.0254 (19)	0.027 (2)	0.0228 (19)	0.0034 (15)	0.0130 (16)	0.0051 (15)
C6	0.027 (2)	0.026 (2)	0.028 (2)	−0.0055 (16)	0.0120 (17)	−0.0041 (16)
C7	0.029 (2)	0.034 (2)	0.026 (2)	−0.0038 (18)	0.0104 (18)	0.0014 (18)
C8	0.039 (2)	0.028 (2)	0.045 (2)	0.0015 (18)	0.024 (2)	−0.0037 (18)
C9	0.074 (3)	0.039 (3)	0.104 (4)	0.003 (2)	0.072 (3)	−0.006 (3)
C10	0.120 (5)	0.043 (3)	0.205 (7)	−0.008 (3)	0.143 (5)	−0.007 (4)
C11	0.095 (4)	0.028 (3)	0.157 (5)	−0.010 (3)	0.106 (4)	−0.006 (3)
C12	0.034 (2)	0.024 (2)	0.048 (2)	−0.0033 (17)	0.026 (2)	−0.0026 (18)
C13	0.031 (2)	0.0197 (19)	0.043 (2)	−0.0033 (16)	0.0162 (19)	0.0010 (17)
C14	0.050 (3)	0.026 (2)	0.073 (3)	−0.0043 (19)	0.039 (3)	0.005 (2)
C15	0.062 (3)	0.018 (2)	0.084 (4)	−0.005 (2)	0.041 (3)	−0.003 (2)
C16	0.050 (3)	0.024 (2)	0.064 (3)	0.0024 (19)	0.033 (2)	−0.008 (2)
C17	0.027 (2)	0.023 (2)	0.032 (2)	0.0006 (15)	0.0116 (17)	−0.0040 (16)
C18	0.040 (2)	0.025 (2)	0.036 (2)	−0.0011 (17)	0.0229 (19)	−0.0053 (17)
C19	0.103 (4)	0.031 (3)	0.132 (5)	0.002 (3)	0.100 (4)	−0.005 (3)
C20	0.141 (5)	0.049 (3)	0.184 (7)	0.005 (3)	0.146 (6)	−0.002 (4)
C21	0.081 (3)	0.038 (3)	0.101 (4)	−0.007 (3)	0.075 (3)	−0.003 (3)
C22	0.047 (2)	0.025 (2)	0.048 (3)	−0.0044 (18)	0.030 (2)	−0.0031 (17)
O5	0.068 (2)	0.046 (2)	0.068 (2)	−0.0134 (17)	0.0142 (18)	−0.0164 (17)
N5	0.041 (2)	0.0323 (19)	0.045 (2)	0.0012 (16)	0.0135 (18)	−0.0004 (16)
C23	0.061 (3)	0.052 (3)	0.041 (3)	0.003 (2)	0.022 (2)	−0.003 (2)
C24	0.071 (4)	0.057 (3)	0.090 (4)	−0.021 (3)	0.039 (3)	−0.014 (3)
C25	0.067 (4)	0.065 (4)	0.099 (5)	0.012 (3)	0.000 (3)	0.017 (3)
O6	0.063 (2)	0.046 (2)	0.053 (2)	0.009 (2)	0.0028 (18)	0.003 (2)

Geometric parameters (Å, º) top

Ni1—N1	1.963 (2)	C11—C12	1.373 (5)
Ni1—N3	1.978 (3)	C11—H11	0.9400
Ni1—N2	2.078 (3)	C12—C13	1.486 (5)
Ni1—N4	2.091 (3)	C13—C14	1.375 (5)
Ni1—O1	2.126 (2)	C14—C15	1.391 (5)
Ni1—O3	2.131 (2)	C14—H14	0.9400
O1—C6	1.269 (4)	C15—C16	1.375 (5)
O2—C6	1.236 (4)	C15—H15	0.9400
O3—C7	1.268 (4)	C16—C17	1.380 (5)
O4—C7	1.232 (4)	C16—H16	0.9400
N1—C1	1.329 (4)	C17—C18	1.485 (5)
N1—C5	1.333 (4)	C18—C19	1.372 (5)
N2—C8	1.333 (4)	C19—C20	1.380 (6)
N2—C12	1.347 (4)	C19—H19	0.9400
N3—C17	1.340 (4)	C20—C21	1.358 (6)
N3—C13	1.340 (4)	C20—H20	0.9400
N4—C22	1.336 (4)	C21—C22	1.362 (5)
N4—C18	1.343 (4)	C21—H21	0.9400
C1—C2	1.386 (5)	C22—H22	0.9400
C1—C6	1.523 (5)	O5—C23	1.213 (5)
C2—C3	1.377 (5)	N5—C23	1.326 (5)
C2—H2	0.9400	N5—C24	1.423 (5)
C3—C4	1.390 (5)	N5—C25	1.433 (6)
C3—H3	0.9400	C23—H23	0.9400
C4—C5	1.376 (5)	C24—H24A	0.9700
C4—H4	0.9400	C24—H24B	0.9700
C5—C7	1.523 (5)	C24—H24C	0.9700
C8—C9	1.369 (5)	C25—H25A	0.9700
C8—H8	0.9400	C25—H25B	0.9700
C9—C10	1.365 (6)	C25—H25C	0.9700
C9—H9	0.9400	O6—H6A	0.71 (5)
C10—C11	1.377 (6)	O6—H6B	0.74 (6)
C10—H10	0.9400

N1—Ni1—N3	177.95 (12)	C9—C10—H10	119.7
N1—Ni1—N2	101.62 (11)	C11—C10—H10	119.7
N3—Ni1—N2	78.67 (11)	C12—C11—C10	118.5 (4)
N1—Ni1—N4	101.44 (11)	C12—C11—H11	120.7
N3—Ni1—N4	78.25 (11)	C10—C11—H11	120.7
N2—Ni1—N4	156.92 (10)	N2—C12—C11	121.4 (3)
N1—Ni1—O1	78.07 (10)	N2—C12—C13	114.8 (3)
N3—Ni1—O1	103.93 (10)	C11—C12—C13	123.8 (3)
N2—Ni1—O1	95.16 (10)	N3—C13—C14	120.9 (3)
N4—Ni1—O1	90.40 (10)	N3—C13—C12	112.8 (3)
N1—Ni1—O3	78.18 (11)	C14—C13—C12	126.3 (3)
N3—Ni1—O3	99.81 (11)	C13—C14—C15	118.1 (3)
N2—Ni1—O3	89.59 (10)	C13—C14—H14	121.0
N4—Ni1—O3	94.29 (10)	C15—C14—H14	121.0
O1—Ni1—O3	156.26 (9)	C16—C15—C14	120.5 (3)
C6—O1—Ni1	114.7 (2)	C16—C15—H15	119.7
C7—O3—Ni1	114.7 (2)	C14—C15—H15	119.7
C1—N1—C5	122.2 (3)	C15—C16—C17	118.7 (3)
C1—N1—Ni1	119.1 (2)	C15—C16—H16	120.7
C5—N1—Ni1	118.7 (2)	C17—C16—H16	120.7
C8—N2—C12	118.8 (3)	N3—C17—C16	120.5 (3)
C8—N2—Ni1	126.7 (2)	N3—C17—C18	113.1 (3)
C12—N2—Ni1	114.2 (2)	C16—C17—C18	126.4 (3)
C17—N3—C13	121.3 (3)	N4—C18—C19	121.7 (3)
C17—N3—Ni1	119.4 (2)	N4—C18—C17	114.4 (3)
C13—N3—Ni1	119.2 (2)	C19—C18—C17	123.8 (3)
C22—N4—C18	118.5 (3)	C18—C19—C20	118.0 (4)
C22—N4—Ni1	126.8 (2)	C18—C19—H19	121.0
C18—N4—Ni1	114.6 (2)	C20—C19—H19	121.0
N1—C1—C2	120.5 (3)	C21—C20—C19	120.9 (4)
N1—C1—C6	113.0 (3)	C21—C20—H20	119.5
C2—C1—C6	126.5 (3)	C19—C20—H20	119.5
C3—C2—C1	118.2 (3)	C20—C21—C22	117.7 (4)
C3—C2—H2	120.9	C20—C21—H21	121.1
C1—C2—H2	120.9	C22—C21—H21	121.1
C2—C3—C4	120.3 (3)	N4—C22—C21	123.2 (4)
C2—C3—H3	119.8	N4—C22—H22	118.4
C4—C3—H3	119.8	C21—C22—H22	118.4
C5—C4—C3	118.5 (3)	C23—N5—C24	122.6 (4)
C5—C4—H4	120.7	C23—N5—C25	118.8 (4)
C3—C4—H4	120.7	C24—N5—C25	118.5 (4)
N1—C5—C4	120.3 (3)	O5—C23—N5	126.7 (5)
N1—C5—C7	113.4 (3)	O5—C23—H23	116.7
C4—C5—C7	126.4 (3)	N5—C23—H23	116.7
O2—C6—O1	126.7 (3)	N5—C24—H24A	109.5
O2—C6—C1	118.3 (3)	N5—C24—H24B	109.5
O1—C6—C1	115.0 (3)	H24A—C24—H24B	109.5
O4—C7—O3	126.9 (3)	N5—C24—H24C	109.5
O4—C7—C5	118.3 (3)	H24A—C24—H24C	109.5
O3—C7—C5	114.8 (3)	H24B—C24—H24C	109.5
N2—C8—C9	122.9 (4)	N5—C25—H25A	109.5
N2—C8—H8	118.5	N5—C25—H25B	109.5
C9—C8—H8	118.5	H25A—C25—H25B	109.5
C10—C9—C8	117.8 (4)	N5—C25—H25C	109.5
C10—C9—H9	121.1	H25A—C25—H25C	109.5
C8—C9—H9	121.1	H25B—C25—H25C	109.5
C9—C10—C11	120.6 (4)	H6A—O6—H6B	100 (6)

C5—N1—C1—C2	1.9 (5)	C10—C11—C12—C13	178.5 (5)
Ni1—N1—C1—C2	−177.4 (2)	C17—N3—C13—C14	−0.6 (6)
C5—N1—C1—C6	−179.0 (3)	Ni1—N3—C13—C14	−178.8 (3)
Ni1—N1—C1—C6	1.7 (3)	C17—N3—C13—C12	178.0 (3)
N1—C1—C2—C3	−1.8 (5)	Ni1—N3—C13—C12	−0.3 (4)
C6—C1—C2—C3	179.2 (3)	N2—C12—C13—N3	4.1 (5)
C1—C2—C3—C4	0.1 (5)	C11—C12—C13—N3	−175.6 (4)
C2—C3—C4—C5	1.5 (5)	N2—C12—C13—C14	−177.4 (4)
C1—N1—C5—C4	−0.2 (5)	C11—C12—C13—C14	2.9 (7)
Ni1—N1—C5—C4	179.1 (2)	N3—C13—C14—C15	1.1 (6)
C1—N1—C5—C7	−178.8 (3)	C12—C13—C14—C15	−177.2 (4)
Ni1—N1—C5—C7	0.5 (3)	C13—C14—C15—C16	−1.5 (7)
C3—C4—C5—N1	−1.5 (5)	C14—C15—C16—C17	1.3 (7)
C3—C4—C5—C7	176.9 (3)	C13—N3—C17—C16	0.4 (5)
Ni1—O1—C6—O2	174.4 (3)	Ni1—N3—C17—C16	178.6 (3)
Ni1—O1—C6—C1	−4.7 (3)	C13—N3—C17—C18	−179.3 (3)
N1—C1—C6—O2	−177.0 (3)	Ni1—N3—C17—C18	−1.0 (4)
C2—C1—C6—O2	2.1 (5)	C15—C16—C17—N3	−0.7 (6)
N1—C1—C6—O1	2.2 (4)	C15—C16—C17—C18	178.9 (4)
C2—C1—C6—O1	−178.7 (3)	C22—N4—C18—C19	1.3 (6)
Ni1—O3—C7—O4	174.3 (3)	Ni1—N4—C18—C19	178.0 (4)
Ni1—O3—C7—C5	−5.4 (3)	C22—N4—C18—C17	−179.9 (3)
N1—C5—C7—O4	−176.2 (3)	Ni1—N4—C18—C17	−3.1 (4)
C4—C5—C7—O4	5.3 (5)	N3—C17—C18—N4	2.7 (5)
N1—C5—C7—O3	3.4 (4)	C16—C17—C18—N4	−176.9 (4)
C4—C5—C7—O3	−175.0 (3)	N3—C17—C18—C19	−178.4 (4)
C12—N2—C8—C9	1.5 (6)	C16—C17—C18—C19	2.0 (7)
Ni1—N2—C8—C9	−172.1 (3)	N4—C18—C19—C20	−0.6 (8)
N2—C8—C9—C10	−0.8 (8)	C17—C18—C19—C20	−179.3 (5)
C8—C9—C10—C11	−0.9 (9)	C18—C19—C20—C21	−1.2 (10)
C9—C10—C11—C12	1.8 (10)	C19—C20—C21—C22	2.1 (10)
C8—N2—C12—C11	−0.4 (6)	C18—N4—C22—C21	−0.3 (6)
Ni1—N2—C12—C11	173.9 (4)	Ni1—N4—C22—C21	−176.6 (3)
C8—N2—C12—C13	179.8 (3)	C20—C21—C22—N4	−1.4 (8)
Ni1—N2—C12—C13	−5.8 (4)	C24—N5—C23—O5	177.5 (4)
C10—C11—C12—N2	−1.2 (8)	C25—N5—C23—O5	−0.7 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6A···O2ⁱ	0.71 (5)	2.21 (5)	2.907 (5)	172 (5)
O6—H6B···O4	0.74 (6)	2.14 (6)	2.881 (5)	175 (7)
C2—H2···O2ⁱⁱ	0.94	2.49	3.254 (4)	138
C8—H8···O5ⁱⁱⁱ	0.94	2.47	3.133 (5)	128
C9—H9···O2^iv	0.94	2.55	3.465 (5)	163
C25—H25C···O4^v	0.97	2.45	3.361 (6)	157

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

Acknowledgements

The author thanks the KBSI, Seoul Center, for the X-ray data collection.

Funding information

This study was supported financially by Chonnam National University (grant No. 2018–3317).

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