(Methanol-κO)bis­(thio­cyanato-κN)[2,4,6-tris(pyridin-2-yl)-1,3,5-triazine-κ3N2,N1,N6]nickel(II) methanol monosolvate

Ha, K.

doi:10.1107/S241431461900169X

metal-organic compounds

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ISSN: 2414-3146

Volume 4| Part 2| February 2019| x190169

https://doi.org/10.1107/S241431461900169X

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(Methanol-κO)bis(thiocyanato-κN)[2,4,6-tris(pyridin-2-yl)-1,3,5-triazine-κ³N²,N¹,N⁶]nickel(II) methanol monosolvate

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 M. Weil, Vienna University of Technology, Austria (Received 28 January 2019; accepted 30 January 2019; online 5 February 2019)

In the structure of the title compound, [Ni(NCS)₂(C₁₈H₁₂N₆)(CH₃OH)]·CH₃OH, the Ni^II ion is six-coordinated in an octahedral coordination environment defined by three N atoms from a 2,4,6-tris(pyridin-2-yl)-1,3,5-triazine ligand, two N atoms from two mutually cis-positioned SCN⁻ anions and one O atom from a methanol ligand. The complex and methanol solvent molecules are linked by intermolecular hydrogen bonds. In the crystal, the complex molecules are stacked in columns parallel to the b axis.

Keywords: crystal structure; nickel(II) complex; 2,4,6-tris(pyridin-2-yl)-1,3,5-triazine; thiocyanate.

CCDC reference: 1894495

Structure description

With reference to the title compound, [Ni(NCS)₂(tptz)(CH₃OH)]·CH₃OH, the crystal structures of related tptz-Ni^II [tptz = 2,4,6-tris(pyridin-2-yl)-1,3,5-triazine] complexes [NiCl₂(tptz)(CH₃OH)] (Hadadzadeh et al., 2012 ), [NiBr(μ-Br)(tptz)]₂ and [Ni(tptz)₂](I₃)₂ (Aragoni et al., 2007 ) have previously been determined.

In the structure of the title complex, the central Ni^II ion is six-coordinated in a distorted octahedral coordination environment defined by three N atoms from a tridentate tptz ligand, two N atoms derived from two mutually cis-positioned SCN⁻ anions and one O atom from a methanol ligand (Fig. 1). The acute N—Ni—N chelating angles of N1—Ni1—N4 = 76.33 (7)° and N1—Ni1—N6 = 76.39 (7)° contribute to the distortion of the octahedron. The axial O1—Ni1—N7, N1—Ni1—N8, and N4—Ni1—N6 bond angles are 175.85 (8), 174.35 (8) and 152.19 (7)°, respectively. The Ni—N(pyridyl) bonds [2.1623 (18) and 2.165 (2) Å] are considerably longer than the Ni—N(triazine, NCS) bonds [1.9943 (18)-2.049 (2) Å].

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

The two pyridyl rings coordinating to the Ni^II atom are positioned approximately parallel to their carrier triazine ring, making dihedral angles of 3.9 (1) and 8.2 (1)°. The dihedral angle between the non-coordinating pyridyl and triazine rings is 10.5 (1)°. The thiocyanato ligands are almost linear, displaying N—C—S bond angles of 178.3 (2) and 179.6 (2)°; the Ni—N—C(NCS) bond angles are slightly bent with 170.6 (2) and 166.7 (2)°, characteristic of an N-bonded conformation (Ha, 2017 ). The complex and additional methanol solvent molecules display intermolecular O—H⋯N and O—H⋯S hydrogen bonds (Table 1, Fig. 2). In the crystal structure, the complex molecules are stacked in columns parallel to the b axis. In the columns, numerous intermolecular π–π interactions between adjacent six-membered rings are present. For Cg1 (the centroid of ring N1–N3/C1/C7/C13) and Cg2ⁱ [the centroid of ring N4/C2–C6; symmetry code: (i) 2 − x, y, 1 − z], the centroid-to-centroid distance is 3.658 (1) Å, and the dihedral angle between the ring planes is 3.7 (1)°.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2ⁱ	0.83	2.61	3.154 (2)	124
O1—H1⋯N5ⁱ	0.83	1.97	2.784 (2)	165
O2—H2⋯S1ⁱⁱ	0.83	2.63	3.403 (2)	156
Symmetry codes: (i) -x+2, -y, -z+1; (ii) -x+1, -y+1, -z+1.

Figure 2
The packing in the crystal structure of the title compound, viewed approximately along the b axis. Hydrogen-bonding interactions are drawn as dashed lines.

Synthesis and crystallization

To a solution of Ni(NCS)₂·4H₂O (0.1829 g, 0.741 mmol) in acetone (20 ml) was added 2,4,6-tris(pyridin-2-yl)-1,3,5-triazine (0.2332 g, 0.747 mmol) and stirred for 3 h at room temperature. The formed precipitate was separated by filtration, washed with acetone, and dried at 323 K, to give a green–yellow powder (0.2501 g). Green crystals suitable for X-ray analysis were obtained by slow evaporation from a methanol solution at room temperature.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[Ni(NCS)₂(C₁₈H₁₂N₆)(CH₄O)]·CH₄O
M_r	551.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	223
a, b, c (Å)	10.5022 (3), 11.1772 (4), 20.8084 (7)
β (°)	95.1737 (12)
V (Å³)	2432.65 (14)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.01
Crystal size (mm)	0.25 × 0.14 × 0.09

Data collection
Diffractometer	PHOTON 100 CMOS detector
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.677, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	66153, 4809, 3788
R_int	0.075
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.083, 1.06
No. of reflections	4809
No. of parameters	320
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.27
Computer programs: APEX2 and SAINT (Bruker, 2016), SHELXT2014/7 (Sheldrick, 2015a ), SHELXL2014/7 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1894495

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S241431461900169X/wm4098sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461900169X/wm4098Isup2.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: SHELXT2014/7 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014/7 (Sheldrick, 2015b).

(Methanol-κO)bis(thiocyanato-κN)[2,4,6-tris(pyridin-2-yl)-1,3,5-triazine-κ³N²,N¹,N⁶]nickel(II) methanol monosolvate top

Crystal data top

[Ni(NCS)₂(C₁₈H₁₂N₆)(CH₄O)]·CH₄O	F(000) = 1136
M_r = 551.29	D_x = 1.505 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.5022 (3) Å	Cell parameters from 9985 reflections
b = 11.1772 (4) Å	θ = 2.6–25.9°
c = 20.8084 (7) Å	µ = 1.01 mm⁻¹
β = 95.1737 (12)°	T = 223 K
V = 2432.65 (14) Å³	Block, green
Z = 4	0.25 × 0.14 × 0.09 mm

Data collection top

PHOTON 100 CMOS detector diffractometer	3788 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.075
φ and ω scans	θ_max = 26.1°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −12→12
T_min = 0.677, T_max = 0.745	k = −13→13
66153 measured reflections	l = −25→25
4809 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.083	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0342P)² + 1.4276P] where P = (F_o² + 2F_c²)/3
4809 reflections	(Δ/σ)_max = 0.001
320 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.27 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), O—H = 0.83 Å and U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C, O). The remaining maximum electron density (0.31 e^- Å^-3) and the minimum electron density (-0.27 e^- Å^-3) in the difference Fourier map are located 0.64 Å and 0.71 Å, respectively, from the atoms N1 and Ni1.

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

	x	y	z	U_iso*/U_eq
Ni1	0.76420 (3)	0.04297 (3)	0.35072 (2)	0.03224 (10)
S1	0.47633 (7)	0.37353 (7)	0.37185 (4)	0.0615 (2)
S2	0.85612 (7)	0.08721 (7)	0.13357 (3)	0.05033 (19)
N1	0.76531 (16)	0.02980 (16)	0.44635 (9)	0.0298 (4)
N2	0.85785 (17)	0.08124 (16)	0.54915 (9)	0.0289 (4)
N3	0.67864 (17)	−0.05148 (17)	0.53620 (9)	0.0332 (4)
N4	0.92575 (17)	0.15144 (16)	0.38653 (9)	0.0297 (4)
N5	0.86950 (18)	0.04978 (17)	0.67830 (9)	0.0348 (4)
N6	0.61519 (17)	−0.08624 (18)	0.36378 (10)	0.0360 (5)
N7	0.6425 (2)	0.1862 (2)	0.35067 (10)	0.0450 (5)
N8	0.7806 (2)	0.0500 (2)	0.25666 (10)	0.0471 (5)
C1	0.85167 (19)	0.08808 (19)	0.48540 (10)	0.0268 (5)
C2	0.9443 (2)	0.15844 (19)	0.45141 (10)	0.0279 (5)
C3	1.0426 (2)	0.2232 (2)	0.48358 (11)	0.0329 (5)
H3	1.0519	0.2269	0.5289	0.039*
C4	1.1265 (2)	0.2823 (2)	0.44732 (12)	0.0388 (6)
H4	1.1949	0.3266	0.4675	0.047*
C5	1.1085 (2)	0.2755 (2)	0.38089 (12)	0.0390 (6)
H5	1.1647	0.3149	0.3553	0.047*
C6	1.0073 (2)	0.2101 (2)	0.35257 (11)	0.0352 (5)
H6	0.9953	0.2067	0.3073	0.042*
C7	0.7682 (2)	0.01166 (19)	0.57226 (11)	0.0288 (5)
C8	0.7681 (2)	0.0024 (2)	0.64301 (11)	0.0299 (5)
C9	0.6692 (2)	−0.0542 (2)	0.67030 (12)	0.0417 (6)
H9	0.6021	−0.0900	0.6442	0.050*
C10	0.6708 (3)	−0.0572 (3)	0.73660 (14)	0.0530 (7)
H10	0.6032	−0.0925	0.7564	0.064*
C11	0.7721 (3)	−0.0080 (3)	0.77305 (13)	0.0506 (7)
H11	0.7753	−0.0086	0.8183	0.061*
C12	0.8699 (3)	0.0428 (2)	0.74214 (12)	0.0443 (6)
H12	0.9406	0.0740	0.7676	0.053*
C13	0.6837 (2)	−0.0412 (2)	0.47331 (11)	0.0304 (5)
C14	0.6000 (2)	−0.1117 (2)	0.42620 (12)	0.0346 (5)
C15	0.5189 (2)	−0.1993 (2)	0.44523 (14)	0.0452 (6)
H15	0.5120	−0.2152	0.4891	0.054*
C16	0.4479 (2)	−0.2632 (3)	0.39732 (16)	0.0560 (8)
H16	0.3919	−0.3240	0.4083	0.067*
C17	0.4602 (2)	−0.2369 (3)	0.33408 (15)	0.0533 (8)
H17	0.4117	−0.2786	0.3012	0.064*
C18	0.5446 (2)	−0.1484 (2)	0.31875 (13)	0.0455 (7)
H18	0.5525	−0.1315	0.2750	0.055*
C19	0.5753 (2)	0.2647 (2)	0.35972 (12)	0.0396 (6)
C20	0.8120 (2)	0.0659 (2)	0.20530 (12)	0.0366 (6)
O1	0.88931 (14)	−0.10777 (14)	0.35803 (8)	0.0349 (4)
H1	0.9647	−0.0883	0.3545	0.052*
C21	0.8602 (2)	−0.2147 (2)	0.32201 (13)	0.0466 (6)
H21A	0.8044	−0.2648	0.3452	0.070*
H21B	0.9387	−0.2575	0.3163	0.070*
H21C	0.8177	−0.1942	0.2801	0.070*
O2	0.2762 (2)	0.45232 (19)	0.56669 (11)	0.0695 (6)
H2	0.3492	0.4799	0.5749	0.104*
C22	0.1909 (4)	0.5459 (3)	0.54825 (16)	0.0794 (11)
H22A	0.1064	0.5132	0.5366	0.119*
H22B	0.2203	0.5877	0.5115	0.119*
H22C	0.1872	0.6012	0.5839	0.119*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.03140 (17)	0.03424 (17)	0.03000 (16)	0.00026 (13)	−0.00313 (11)	−0.00294 (13)
S1	0.0502 (4)	0.0488 (4)	0.0865 (6)	0.0127 (3)	0.0110 (4)	−0.0049 (4)
S2	0.0542 (4)	0.0564 (4)	0.0406 (4)	0.0048 (3)	0.0055 (3)	0.0057 (3)
N1	0.0258 (9)	0.0306 (10)	0.0323 (10)	−0.0014 (8)	−0.0009 (8)	−0.0033 (8)
N2	0.0263 (9)	0.0298 (10)	0.0305 (10)	−0.0006 (8)	0.0022 (8)	−0.0013 (8)
N3	0.0256 (10)	0.0332 (11)	0.0406 (11)	−0.0018 (8)	0.0030 (8)	−0.0022 (9)
N4	0.0312 (10)	0.0269 (10)	0.0309 (10)	0.0009 (8)	0.0024 (8)	0.0005 (8)
N5	0.0399 (11)	0.0347 (11)	0.0298 (10)	0.0004 (9)	0.0040 (8)	−0.0023 (9)
N6	0.0258 (10)	0.0393 (11)	0.0414 (12)	0.0016 (8)	−0.0048 (8)	−0.0111 (9)
N7	0.0395 (12)	0.0422 (13)	0.0516 (14)	0.0048 (10)	−0.0047 (10)	−0.0033 (10)
N8	0.0516 (13)	0.0529 (14)	0.0355 (12)	0.0061 (11)	−0.0044 (10)	0.0001 (11)
C1	0.0252 (11)	0.0248 (11)	0.0302 (12)	0.0015 (9)	0.0010 (9)	−0.0031 (9)
C2	0.0278 (11)	0.0223 (11)	0.0332 (12)	0.0022 (9)	0.0006 (9)	0.0004 (9)
C3	0.0322 (12)	0.0304 (12)	0.0352 (13)	−0.0030 (10)	−0.0014 (10)	−0.0020 (10)
C4	0.0346 (13)	0.0298 (13)	0.0518 (15)	−0.0055 (10)	0.0033 (11)	−0.0029 (11)
C5	0.0408 (14)	0.0298 (13)	0.0481 (15)	−0.0036 (11)	0.0140 (11)	0.0036 (11)
C6	0.0443 (14)	0.0275 (12)	0.0343 (13)	0.0027 (11)	0.0060 (10)	0.0024 (10)
C7	0.0258 (11)	0.0263 (12)	0.0343 (12)	0.0040 (9)	0.0036 (9)	−0.0007 (9)
C8	0.0282 (12)	0.0271 (11)	0.0348 (12)	0.0058 (9)	0.0048 (10)	0.0003 (9)
C9	0.0345 (13)	0.0441 (15)	0.0469 (15)	0.0014 (11)	0.0064 (11)	0.0077 (12)
C10	0.0545 (17)	0.0574 (18)	0.0502 (17)	0.0020 (14)	0.0215 (14)	0.0175 (14)
C11	0.0686 (19)	0.0524 (17)	0.0329 (14)	0.0106 (15)	0.0156 (13)	0.0072 (12)
C12	0.0554 (16)	0.0422 (15)	0.0344 (13)	0.0025 (13)	−0.0001 (11)	−0.0044 (12)
C13	0.0236 (11)	0.0292 (12)	0.0381 (13)	0.0005 (10)	0.0012 (9)	−0.0019 (10)
C14	0.0229 (11)	0.0341 (13)	0.0462 (14)	−0.0001 (10)	−0.0005 (10)	−0.0078 (11)
C15	0.0334 (13)	0.0432 (15)	0.0589 (17)	−0.0075 (11)	0.0033 (12)	−0.0070 (13)
C16	0.0361 (15)	0.0472 (17)	0.084 (2)	−0.0138 (13)	0.0011 (14)	−0.0133 (16)
C17	0.0324 (14)	0.0535 (18)	0.071 (2)	−0.0040 (13)	−0.0091 (13)	−0.0270 (16)
C18	0.0347 (14)	0.0499 (16)	0.0497 (16)	0.0032 (12)	−0.0076 (11)	−0.0175 (13)
C19	0.0377 (14)	0.0399 (15)	0.0401 (14)	−0.0040 (12)	−0.0021 (11)	0.0017 (11)
C20	0.0375 (13)	0.0325 (13)	0.0375 (14)	0.0044 (10)	−0.0085 (11)	−0.0018 (10)
O1	0.0303 (8)	0.0350 (9)	0.0388 (9)	−0.0011 (7)	−0.0008 (7)	−0.0054 (7)
C21	0.0422 (15)	0.0376 (15)	0.0590 (17)	0.0015 (12)	0.0001 (12)	−0.0123 (13)
O2	0.0694 (14)	0.0655 (14)	0.0724 (15)	0.0098 (12)	0.0000 (12)	−0.0137 (12)
C22	0.095 (3)	0.078 (2)	0.060 (2)	0.025 (2)	−0.0200 (19)	−0.0141 (18)

Geometric parameters (Å, º) top

Ni1—N8	1.982 (2)	C6—H6	0.9400
Ni1—N1	1.9943 (18)	C7—C8	1.476 (3)
Ni1—N7	2.049 (2)	C8—C9	1.381 (3)
Ni1—O1	2.1336 (16)	C9—C10	1.379 (4)
Ni1—N4	2.1623 (18)	C9—H9	0.9400
Ni1—N6	2.165 (2)	C10—C11	1.365 (4)
S1—C19	1.634 (3)	C10—H10	0.9400
S2—C20	1.620 (3)	C11—C12	1.381 (4)
N1—C13	1.329 (3)	C11—H11	0.9400
N1—C1	1.332 (3)	C12—H12	0.9400
N2—C1	1.324 (3)	C13—C14	1.483 (3)
N2—C7	1.343 (3)	C14—C15	1.379 (3)
N3—C13	1.320 (3)	C15—C16	1.388 (4)
N3—C7	1.348 (3)	C15—H15	0.9400
N4—C6	1.331 (3)	C16—C17	1.366 (4)
N4—C2	1.349 (3)	C16—H16	0.9400
N5—C12	1.330 (3)	C17—C18	1.384 (4)
N5—C8	1.346 (3)	C17—H17	0.9400
N6—C18	1.336 (3)	C18—H18	0.9400
N6—C14	1.353 (3)	O1—C21	1.429 (3)
N7—C19	1.152 (3)	O1—H1	0.8300
N8—C20	1.160 (3)	C21—H21A	0.9700
C1—C2	1.479 (3)	C21—H21B	0.9700
C2—C3	1.383 (3)	C21—H21C	0.9700
C3—C4	1.379 (3)	O2—C22	1.407 (4)
C3—H3	0.9400	O2—H2	0.8300
C4—C5	1.380 (3)	C22—H22A	0.9700
C4—H4	0.9400	C22—H22B	0.9700
C5—C6	1.378 (3)	C22—H22C	0.9700
C5—H5	0.9400

N8—Ni1—N1	174.35 (8)	N5—C8—C7	116.4 (2)
N8—Ni1—N7	94.50 (9)	C9—C8—C7	120.7 (2)
N1—Ni1—N7	90.32 (8)	C10—C9—C8	118.7 (2)
N8—Ni1—O1	89.64 (8)	C10—C9—H9	120.6
N1—Ni1—O1	85.55 (7)	C8—C9—H9	120.6
N7—Ni1—O1	175.85 (8)	C11—C10—C9	119.0 (3)
N8—Ni1—N4	100.53 (8)	C11—C10—H10	120.5
N1—Ni1—N4	76.33 (7)	C9—C10—H10	120.5
N7—Ni1—N4	91.83 (8)	C10—C11—C12	118.8 (2)
O1—Ni1—N4	87.66 (6)	C10—C11—H11	120.6
N8—Ni1—N6	106.18 (8)	C12—C11—H11	120.6
N1—Ni1—N6	76.39 (7)	N5—C12—C11	123.6 (3)
N7—Ni1—N6	93.64 (8)	N5—C12—H12	118.2
O1—Ni1—N6	84.94 (7)	C11—C12—H12	118.2
N4—Ni1—N6	152.19 (7)	N3—C13—N1	123.8 (2)
C13—N1—C1	117.65 (19)	N3—C13—C14	122.3 (2)
C13—N1—Ni1	121.29 (14)	N1—C13—C14	113.9 (2)
C1—N1—Ni1	121.00 (15)	N6—C14—C15	123.6 (2)
C1—N2—C7	114.80 (18)	N6—C14—C13	114.1 (2)
C13—N3—C7	114.70 (19)	C15—C14—C13	122.2 (2)
C6—N4—C2	117.47 (19)	C14—C15—C16	117.7 (3)
C6—N4—Ni1	128.00 (16)	C14—C15—H15	121.1
C2—N4—Ni1	114.53 (14)	C16—C15—H15	121.1
C12—N5—C8	116.9 (2)	C17—C16—C15	119.3 (3)
C18—N6—C14	117.2 (2)	C17—C16—H16	120.4
C18—N6—Ni1	128.38 (19)	C15—C16—H16	120.4
C14—N6—Ni1	114.20 (14)	C16—C17—C18	119.6 (2)
C19—N7—Ni1	170.6 (2)	C16—C17—H17	120.2
C20—N8—Ni1	166.7 (2)	C18—C17—H17	120.2
N2—C1—N1	123.5 (2)	N6—C18—C17	122.4 (3)
N2—C1—C2	122.32 (19)	N6—C18—H18	118.8
N1—C1—C2	114.14 (19)	C17—C18—H18	118.8
N4—C2—C3	123.3 (2)	N7—C19—S1	178.3 (2)
N4—C2—C1	113.97 (18)	N8—C20—S2	179.6 (2)
C3—C2—C1	122.7 (2)	C21—O1—Ni1	121.43 (14)
C4—C3—C2	118.1 (2)	C21—O1—H1	109.5
C4—C3—H3	120.9	Ni1—O1—H1	111.9
C2—C3—H3	120.9	O1—C21—H21A	109.5
C3—C4—C5	119.0 (2)	O1—C21—H21B	109.5
C3—C4—H4	120.5	H21A—C21—H21B	109.5
C5—C4—H4	120.5	O1—C21—H21C	109.5
C6—C5—C4	119.2 (2)	H21A—C21—H21C	109.5
C6—C5—H5	120.4	H21B—C21—H21C	109.5
C4—C5—H5	120.4	C22—O2—H2	109.5
N4—C6—C5	122.9 (2)	O2—C22—H22A	109.5
N4—C6—H6	118.6	O2—C22—H22B	109.5
C5—C6—H6	118.6	H22A—C22—H22B	109.5
N2—C7—N3	125.5 (2)	O2—C22—H22C	109.5
N2—C7—C8	117.47 (19)	H22A—C22—H22C	109.5
N3—C7—C8	117.1 (2)	H22B—C22—H22C	109.5
N5—C8—C9	122.9 (2)

C7—N2—C1—N1	−1.0 (3)	N2—C7—C8—C9	171.4 (2)
C7—N2—C1—C2	−178.66 (19)	N3—C7—C8—C9	−9.2 (3)
C13—N1—C1—N2	−1.8 (3)	N5—C8—C9—C10	3.4 (4)
Ni1—N1—C1—N2	−179.04 (16)	C7—C8—C9—C10	−177.8 (2)
C13—N1—C1—C2	176.00 (18)	C8—C9—C10—C11	−2.3 (4)
Ni1—N1—C1—C2	−1.2 (2)	C9—C10—C11—C12	−0.3 (4)
C6—N4—C2—C3	0.2 (3)	C8—N5—C12—C11	−1.1 (4)
Ni1—N4—C2—C3	179.87 (17)	C10—C11—C12—N5	2.1 (4)
C6—N4—C2—C1	−178.40 (18)	C7—N3—C13—N1	−3.3 (3)
Ni1—N4—C2—C1	1.3 (2)	C7—N3—C13—C14	174.84 (19)
N2—C1—C2—N4	177.72 (19)	C1—N1—C13—N3	4.2 (3)
N1—C1—C2—N4	−0.2 (3)	Ni1—N1—C13—N3	−178.65 (16)
N2—C1—C2—C3	−0.9 (3)	C1—N1—C13—C14	−174.09 (18)
N1—C1—C2—C3	−178.8 (2)	Ni1—N1—C13—C14	3.1 (3)
N4—C2—C3—C4	−0.8 (3)	C18—N6—C14—C15	1.7 (3)
C1—C2—C3—C4	177.7 (2)	Ni1—N6—C14—C15	−173.79 (19)
C2—C3—C4—C5	0.6 (3)	C18—N6—C14—C13	178.6 (2)
C3—C4—C5—C6	0.1 (4)	Ni1—N6—C14—C13	3.1 (2)
C2—N4—C6—C5	0.6 (3)	N3—C13—C14—N6	177.7 (2)
Ni1—N4—C6—C5	−179.05 (17)	N1—C13—C14—N6	−4.0 (3)
C4—C5—C6—N4	−0.7 (4)	N3—C13—C14—C15	−5.3 (3)
C1—N2—C7—N3	1.9 (3)	N1—C13—C14—C15	172.9 (2)
C1—N2—C7—C8	−178.67 (18)	N6—C14—C15—C16	−1.1 (4)
C13—N3—C7—N2	0.1 (3)	C13—C14—C15—C16	−177.7 (2)
C13—N3—C7—C8	−179.32 (19)	C14—C15—C16—C17	−0.3 (4)
C12—N5—C8—C9	−1.7 (3)	C15—C16—C17—C18	1.0 (4)
C12—N5—C8—C7	179.5 (2)	C14—N6—C18—C17	−1.0 (3)
N2—C7—C8—N5	−9.8 (3)	Ni1—N6—C18—C17	173.78 (18)
N3—C7—C8—N5	169.66 (19)	C16—C17—C18—N6	−0.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2ⁱ	0.83	2.61	3.154 (2)	124
O1—H1···N5ⁱ	0.83	1.97	2.784 (2)	165
O2—H2···S1ⁱⁱ	0.83	2.63	3.403 (2)	156

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

Acknowledgements

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

Funding information

This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (grant No. 2018R1D1A1B07050550).

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