A new one-dimensional NiII coordination polymer with a two-dimensional supra-molecular architecture.

A new one-dimensional NiII coordination polymer of 1,3,5-tris-(imidazol-1-ylmeth-yl)benzene, namely catena-poly[[aqua-(sulfato-κO)hemi(μ-ethane-1,2-diol-κ2O:O')[μ3-1,3,5-tris-(1H-imidazol-1-ylmeth-yl)benzene-κ3N3,N3',N3'']nickel(II)] ethane-1,2-diol monosolvate monohydrate], {[Ni(SO4)(C18H18N6)(C2H6O2)0.5(H2O)]·C2H6O2·H2O} n , was synthesized and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. The NiII cation is coordinated by three N atoms of three different 1,3,5-tris-(imidazol-1-ylmeth-yl)benzene ligands, one O atom of an ethane-1,2-diol mol-ecule, by a sulfate anion and a water mol-ecule, forming a distorted octa-hedral NiN3O3 coordination geometry. The tripodal 1,3,5-tris-(imidazol-1-ylmeth-yl)benzene ligands link the NiII cations, generating metal-organic chains running along the [100] direction. Adjacent chains are further connected by O-H⋯O hydrogen bonds, resulting in a two-dimensional supermolecular architecture running parallel to the (001) plane. Another water mol-ecule and a second ethane-1,2-diol mol-ecule are non-coordinating and are linked to the coordinating sulfate ions via O-H⋯O hydrogen bonds.

Chemical context

In recent years, the self-assembly of coordination pan class="Chemical">polymers and crystal engineering of class="Gene">pan class="Chemical">metal-organic coordination frameworks have attracted great inter­est, owing to their intriguing mol­ecular topologies and the potential applications of these polymers as functional materials (Pan et al., 2004 ▸; Jiang et al., 2011 ▸; Du et al., 2014 ▸). Previously reported studies a major strategy to be the use of multidentate organic ligands and metal ions to construct inorganic–organic hybrid materials through metal–ligand coordination and hydrogen-bonding inter­actions. Imidazole-containing multidentate ligands that contain an aromatic core have received much attention, such as 1,3-bis­(1-imidazol­yl)-5-(imidazol-1-ylmeth­yl)benzene (Fan et al., 2003 ▸), 2,4,6-tris­[4-(imidazol-1-ylmeth­yl)phenyl-1,3,5-triazine (Wan et al., 2004 ▸), 1,3,5-tris­(imidazol-1-ylmeth­yl)-2,4,6-tri­methyl­benzene (Zhao et al., 2004 ▸), 4,4′-bis­(imidazol-1-ylmeth­yl)biphenyl (Carlucci et al., 2008 ▸), 1,3,5-tri(1-imidazol­yl)benzene (Su et al., 2010 ▸), 1,2,4,5-tetra­kis­(imidazol-1-ylmeth­yl)benzene (Hua et al., 2010 ▸) and 1,3,5-tris­(imidazol-1-ylmeth­yl)benzene (Xu et al., 2009 ▸; Zhong, 2014 ▸).

Hydro­thermal (solvothermal) synthesis is an effective method for the construction of new pan class="Chemical">metal–organic coordination class="Gene">pan class="Chemical">polymers because it can provide ideal conditions for crystal growth due to the enhanced transport ability of solvents in superheated systems. In the present work, we carried out the solvothermal reaction between NiSO4·6H2O and imidazole-containing multidentate ligands, 1,3,5-tris(imidazol-1-ylmeth­yl)benzene (timb) and successfully obtained a new NiII one-dimensional coordination polymer, {[Ni(SO4)(C18H18N6)(C2H6O2)0.5(H2O)]·C2H6O2·H2O}, (I). Herein we report its crystal structure and its elemental and IR spectroscopic analysis data.

Structural commentary

The title complex (I) crystallizes in the triclinic space group P and the asymmetric unit of the structure consists of one pan class="Chemical">NiII ion, one class="Gene">pan class="Chemical">sulfate anion, one timb ligand, half a coordinating ethane-1,2-diol mol­ecule, one coordinating water mol­ecules, one additional lattice water mol­ecule and one non-coordinating ethane-1,2-diol solvent mol­ecule. As shown in Fig. 1 ▸, each NiII cation exhibits an irregular octa­hedral NiN3O3 coordination geometry and is coordinated by three N atoms (N1, N5i and N3ii) from three different tripodal timb ligands and three O atoms (O1W, O1 and O5) from a coord­inating water mol­ecule, a sulfate anion and a coordinating ethane-1,2-diol mol­ecule, respectively (see Fig. 1 ▸ and Table 1 ▸ for symmetry codes). The Ni—O [2.0904 (12)–2.1458 (12) Å; Table 1 ▸] and Ni—N bond lengths [2.0597 (15)–2.0777 (15) Å] are in accord with corresponding bond lengths found in previously reported NiII coordination polymers {[Ni(tib)(H2O)2(SO4)]·EtOH·H2O} [tib = 1,3,5-tris­(imidazol-1-ylmeth­yl) benzene; Ni—O = 2.0911 (14)–2.1368 (12) Å and Ni—N = 2.0709 (15)–2.0728 (14) Å; Xu et al., 2009 ▸] and [Ni(timpt)2](ClO4)2 [timpt = 2,4,6-tri[4-(imid­azol-1-ylmeth­yl)phen­yl]-1,3,5-triazine; Ni—N = 2.097 (5)–2.151 (4) Å; Wan et al., 2004 ▸].

Figure 1

The asymmetric unit of (I), showing the atom-numbering scheme and with displacement ellipsoids drawn at the 25% probability level. All H atoms have been omitted for clarity. [Symmetry codes: (i) −x, 1 − y, 1 − z; (ii) −x, −y, 1 − z.]

Table 1

Selected geometric parameters (Å, °)

Ni1—N5i	2.0597 (15)	Ni1—O5	2.0904 (12)
Ni1—N3ii	2.0735 (15)	Ni1—O1W	2.1048 (12)
Ni1—N1	2.0777 (15)	Ni1—O1	2.1458 (12)
N5i—Ni1—N3ii	89.38 (6)	N1—Ni1—O1W	87.11 (5)
N5i—Ni1—N1	175.70 (6)	O5—Ni1—O1W	89.54 (5)
N3ii—Ni1—N1	92.36 (6)	N5i—Ni1—O1	93.10 (6)
N5i—Ni1—O5	88.70 (6)	N3ii—Ni1—O1	90.67 (5)
N3ii—Ni1—O5	176.18 (5)	N1—Ni1—O1	90.82 (5)
N1—Ni1—O5	89.79 (5)	O5—Ni1—O1	86.13 (5)
N5i—Ni1—O1W	88.85 (6)	O1W—Ni1—O1	175.21 (5)
N3ii—Ni1—O1W	93.73 (6)

Symmetry codes: (i) ; (ii) .

Each pan class="Chemical">NiII atom is coordinated to three individual class="Gene">pan class="Chemical">timb ligands and each timb ligand in turn connects three nickel(II) atoms to generate an infinite laddered chain along the [010] direction (Fig. 2 ▸). Each timb ligand adopts cis, cis, cis substit­uent conformations and coordinates to three NiII atoms (Ni1, Ni1i and Ni1ii), as observed in the Ni compound reported by Xu et al. (2009 ▸). The metal–metal distances (Ni⋯Ni) in the above-mentioned chain are 7.1003 (4) Å (Ni1⋯Ni1i), 8.7577 (4) Å (Ni1⋯Ni1ii) and 11.7296 (6) Å (Ni1i⋯Niii) (see Fig. 2 ▸ for symmetry codes). The three imidazole groups within each timb ligand are inclined to the central benzene ring plane at dihedral angles of 67.60 (6)° (N2/C12/N1/C11/C10), 77.54 (6)° (N4/C15/N3/C14/C13) and 71.75 (6)° (N6/C18/N5/C17/C16), which are different from the values found in a previously reported tib–cadmium compound with the same cis, cis, cis ligand conformations (66.15, 75.58 and 86.33°; Xu et al., 2009 ▸). The three least-square planes of the terminal imidazole rings of the timb ligand are oriented with respect to each other at 56.46 (6)° (N2/C12/N1/C11/C10 and N4/C15/N3/C14/C13), 74.95 (7)° (N2/C12/N1/C11/C10 and N6/C18/N5/C17/C16) and 75.78 (7)° (N4/C15/N3/C14/C13 and N6/C18/N5/C17/C16), respectively.

Figure 2

The one-dimensional polymeric chain along the [010] direction. The 17-membered (A) and 24-membered (B) macrocyclic rings are indicated. [Symmetry codes: (i) −x, 1 − y, 1 − z; (ii) −x, −y, 1 − z.]

It can be seen clearly that one 17-membered pan class="Disease">macrocyclic ring (A) and one 24-membered class="Gene">pan class="Disease">macrocyclic ring (B) exist in the above-mentioned chain (see Fig. 2 ▸), which are evidently different from that observed in the previously noted nickel compound {[Ni(tib)(H2O)2(SO4)]·EtOH·(H2O)} in which A and B are 24-membered macrocyclic rings (Xu et al., 2009 ▸).

Supra­molecular features

In the crystal structure of the title compound, the above-mentioned neighbouring chains are further connected to each other by Opan class="Chemical">water—H⋯Oclass="Gene">pan class="Chemical">sulfate hydrogen bonds (O1W—H1WB⋯O2iii), giving rise to a two-dimensional supermolecular structure running parallel to (001) plane (Fig. 3 ▸). Other O—H⋯O hydrogen-bonding inter­actions involve the coordinating water and ethane-1,2-diol mol­ecules, the lattice water mol­ecule, the solvent ethane-1,2-diol mol­ecule and the sulfate anion, viz. O1W—H1WA⋯O6iii, O2W—H2WA⋯O3iv, O2W—H2WB⋯O3, O5—H1A⋯O3, and O7—H7C⋯O4iv (see Table 2 ▸ for symmetry codes).

Figure 3

Two-dimensional structure of (I), running parallel to (001) plane. Hydrogen bonds are represented by dashed lines. All lattice water and solvent ethane-1,2-diol mol­ecules have been omitted for clarity.

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O6iii	0.82	1.93	2.743 (2)	172
O1W—H1WB⋯O2iii	0.82	1.88	2.6995 (19)	178
O2W—H2WA⋯O3iv	0.83	2.00	2.827 (2)	176
O2W—H2WB⋯O3	0.83	2.13	2.928 (2)	163
O5—H1A⋯O3	0.81	1.81	2.6168 (18)	169
O7—H7C⋯O4iv	0.82	2.07	2.884 (3)	174

Symmetry codes: (iii) ; (iv) .

Synthesis and crystallization

NiSO4·6H2O (0.1 mmol), pan class="Chemical">1,3,5-tris­(imidazol-1-ylmeth­yl)benzene (0.1 mmol), class="Gene">pan class="Chemical">water (6 ml) and ethane-1,2-diol (2 ml) were mixed and placed in a thick Pyrex tube, which was sealed and heated to 413 K for 72 h. After cooling to room temperature, blue block-shaped crystals (45% yield, based on Ni) suitable for X-ray analysis were obtained. Elemental analysis calculated for C21H31N6NiO9S: C 41.86, H 5.15, N 13.95%; found: C 41.90, H 5.12, N 13.86%. IR (KBr disc, ν, cm−1): 3378 (s), 1612 (m), 1521 (s), 1445 (m), 1400 (w), 1283 (w), 1234 (m), 1119 (s), 1055 (s), 963 (w), 830 (m), 750 (s), 661 (s), 637 (m).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. C-bound H atoms were positioned geom­etrically and allowed to ride on their parent atoms, with C—H = 0.93 or 0.97 Å and U iso(H) = 1.2U eq(C). O-bound H atoms of the pan class="Chemical">water and class="Gene">pan class="Chemical">ethane-1,2-diol mol­ecules were either located in difference Fourier maps or placed in calculated positions so as to form a reasonable hydrogen-bonding network, as far as possible. Initially, their positions were refined with tight restraints on the O—H and H⋯H distances [0.82 (1) and 1.35 (1) Å, respectively] in order to ensure a reasonable geometry. They were then constrained to ride on their parent O atoms, with U iso(H) = 1.5U eq(O).

Table 3

Experimental details

Crystal data
Chemical formula	[Ni(SO4)(C18H18N6)(C2H6O2)0.5(H2O)]·C2H6O2·H2O
M r	602.29
Crystal system, space group	Triclinic, P
Temperature (K)	223
a, b, c (Å)	8.6910 (4), 11.7296 (5), 13.1200 (6)
α, β, γ (°)	83.922 (1), 77.829 (1), 74.064 (1)
V (Å3)	1255.53 (10)
Z	2
Radiation type	Mo Kα
μ (mm−1)	0.92
Crystal size (mm)	0.30 × 0.25 × 0.20
Data collection
Diffractometer	Rigaku Mercury CCD
Absorption correction	Multi-scan (REQAB; Jacobson, 1998 ▸)
T min, T max	0.770, 0.837
No. of measured, independent and observed [I > 2σ(I)] reflections	10288, 5701, 5102
R int	0.015
(sin θ/λ)max (Å−1)	0.650
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.031, 0.077, 1.05
No. of reflections	5701
No. of parameters	346
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.64, −0.35

Computer programs: CrystalClear (Rigaku, 2007 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL2014 (Sheldrick, 2015b ▸) and XP in SHELXTL (Sheldrick, 2008 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017000470/zl2688sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017000470/zl2688Isup2.hkl

CCDC reference: 1470095

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Ni(SO4)(C18H18N6)(C2H6O2)0.5(H2O)]·C2H6O2·H2O	Z = 2
Mr = 602.29	F(000) = 630
Triclinic, P1	Dx = 1.593 Mg m−3
a = 8.6910 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.7296 (5) Å	Cell parameters from 5689 reflections
c = 13.1200 (6) Å	θ = 3.6–27.5°
α = 83.922 (1)°	µ = 0.92 mm−1
β = 77.829 (1)°	T = 223 K
γ = 74.064 (1)°	Block, blue
V = 1255.53 (10) Å3	0.30 × 0.25 × 0.20 mm

Rigaku Mercury CCD diffractometer	5701 independent reflections
Radiation source: fine-focus sealed tube	5102 reflections with I > 2σ(I)
Detector resolution: 28.5714 pixels mm-1	Rint = 0.015
ω scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	h = −11→3
Tmin = 0.770, Tmax = 0.837	k = −15→14
10288 measured reflections	l = −17→16

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031	H-atom parameters constrained
wR(F2) = 0.077	w = 1/[σ2(Fo2) + (0.0339P)2 + 0.5937P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
5701 reflections	Δρmax = 0.64 e Å−3
346 parameters	Δρmin = −0.35 e Å−3

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.

	x	y	z	Uiso*/Ueq
Ni1	0.04969 (2)	0.26468 (2)	0.69398 (2)	0.02264 (7)
S1	0.39700 (5)	0.31684 (4)	0.73486 (3)	0.02532 (10)
N1	0.17497 (17)	0.15324 (13)	0.57365 (11)	0.0264 (3)
N2	0.35427 (17)	0.07352 (13)	0.43798 (11)	0.0272 (3)
N3	−0.00592 (17)	−0.12373 (13)	0.20513 (11)	0.0275 (3)
N4	0.12631 (18)	−0.00981 (14)	0.09797 (11)	0.0288 (3)
N5	0.08774 (18)	0.61960 (13)	0.19341 (11)	0.0280 (3)
N6	0.28790 (17)	0.48786 (13)	0.10352 (11)	0.0271 (3)
O1	0.27204 (14)	0.25000 (12)	0.74691 (10)	0.0332 (3)
O1W	−0.16019 (15)	0.28607 (13)	0.63045 (10)	0.0375 (3)
H1WA	−0.1485	0.2805	0.5674	0.045*
H1WB	−0.2450	0.2694	0.6602	0.045*
O2	0.55747 (16)	0.23427 (14)	0.72399 (15)	0.0551 (5)
O2W	0.4836 (2)	0.61941 (19)	0.57640 (16)	0.0644 (5)
H2WA	0.5186	0.6125	0.5127	0.091 (12)*
H2WB	0.4695	0.5551	0.6032	0.19 (2)*
O4	0.3645 (2)	0.39103 (17)	0.82364 (12)	0.0585 (5)
O3	0.38778 (17)	0.39792 (13)	0.63970 (11)	0.0405 (3)
O5	0.10109 (15)	0.40988 (11)	0.59967 (10)	0.0309 (3)
H1A	0.1896	0.4142	0.6075	0.066 (8)*
O7	0.7848 (2)	0.36115 (16)	0.21737 (13)	0.0581 (4)
H7C	0.7487	0.4328	0.2068	0.087*
O6	0.8462 (2)	0.27266 (19)	0.42207 (12)	0.0641 (5)
H6B	0.7551	0.3036	0.4092	0.096*
C1	0.44203 (19)	0.11243 (16)	0.24838 (13)	0.0270 (4)
C2	0.3776 (2)	0.05094 (16)	0.19147 (13)	0.0281 (4)
H2A	0.3650	−0.0240	0.2159	0.034*
C3	0.3312 (2)	0.10036 (16)	0.09739 (13)	0.0267 (3)
C4	0.3538 (2)	0.21075 (16)	0.06059 (13)	0.0272 (3)
H4A	0.3251	0.2435	−0.0026	0.033*
C5	0.4194 (2)	0.27334 (15)	0.11748 (14)	0.0264 (3)
C6	0.4632 (2)	0.22389 (16)	0.21129 (14)	0.0290 (4)
H6A	0.5068	0.2653	0.2496	0.035*
C7	0.4926 (2)	0.05685 (18)	0.34988 (13)	0.0321 (4)
H7A	0.5418	−0.0274	0.3423	0.039*
H7B	0.5740	0.0920	0.3645	0.039*
C8	0.2624 (2)	0.03201 (19)	0.03467 (14)	0.0349 (4)
H8A	0.2253	0.0826	−0.0235	0.042*
H8B	0.3478	−0.0356	0.0064	0.042*
C9	0.4402 (2)	0.39447 (16)	0.07772 (15)	0.0306 (4)
H9A	0.5237	0.4113	0.1080	0.037*
H9B	0.4765	0.3949	0.0025	0.037*
C10	0.2496 (2)	0.00224 (17)	0.46746 (14)	0.0323 (4)
H10A	0.2531	−0.0665	0.4367	0.039*
C11	0.1396 (2)	0.05254 (17)	0.55086 (14)	0.0307 (4)
H11A	0.0532	0.0232	0.5872	0.037*
C12	0.3053 (2)	0.16280 (16)	0.50339 (13)	0.0270 (3)
H12A	0.3563	0.2236	0.4998	0.032*
C13	−0.0332 (2)	0.05429 (17)	0.12110 (15)	0.0337 (4)
H13A	−0.0776	0.1313	0.0968	0.040*
C14	−0.1129 (2)	−0.01670 (17)	0.18614 (14)	0.0329 (4)
H14A	−0.2239	0.0037	0.2141	0.040*
C15	0.1375 (2)	−0.11575 (16)	0.15006 (14)	0.0299 (4)
H15A	0.2336	−0.1758	0.1478	0.036*
C16	0.1711 (2)	0.52835 (18)	0.04308 (15)	0.0362 (4)
H16A	0.1747	0.5047	−0.0230	0.043*
C17	0.0496 (2)	0.60986 (18)	0.09903 (15)	0.0356 (4)
H17A	−0.0456	0.6528	0.0767	0.043*
C18	0.2324 (2)	0.54442 (16)	0.19310 (14)	0.0298 (4)
H18A	0.2886	0.5322	0.2480	0.036*
C20	0.0760 (2)	0.45061 (18)	0.49659 (15)	0.0349 (4)
H20A	0.0660	0.3861	0.4600	0.042*
H20B	0.1682	0.4783	0.4581	0.042*
C21	0.9401 (3)	0.3387 (2)	0.24521 (18)	0.0498 (5)
H21A	0.9519	0.4103	0.2700	0.060*
H21B	1.0250	0.3158	0.1844	0.060*
C22	0.9574 (3)	0.2421 (2)	0.32855 (19)	0.0533 (6)
H22A	0.9415	0.1718	0.3039	0.064*
H22B	1.0673	0.2225	0.3422	0.064*

	U11	U22	U33	U12	U13	U23
Ni1	0.02106 (11)	0.02523 (12)	0.02195 (11)	−0.00719 (8)	−0.00350 (8)	−0.00055 (8)
S1	0.02180 (18)	0.0309 (2)	0.0249 (2)	−0.00984 (16)	−0.00678 (15)	0.00368 (16)
N1	0.0254 (7)	0.0282 (8)	0.0252 (7)	−0.0072 (6)	−0.0043 (6)	−0.0008 (6)
N2	0.0267 (7)	0.0305 (8)	0.0220 (7)	−0.0043 (6)	−0.0040 (5)	0.0001 (6)
N3	0.0269 (7)	0.0299 (8)	0.0263 (7)	−0.0102 (6)	−0.0022 (6)	−0.0016 (6)
N4	0.0317 (7)	0.0313 (8)	0.0263 (7)	−0.0151 (6)	−0.0040 (6)	0.0008 (6)
N5	0.0293 (7)	0.0287 (8)	0.0261 (7)	−0.0077 (6)	−0.0049 (6)	−0.0026 (6)
N6	0.0296 (7)	0.0239 (7)	0.0265 (7)	−0.0075 (6)	−0.0019 (6)	−0.0011 (6)
O1	0.0261 (6)	0.0392 (8)	0.0386 (7)	−0.0155 (5)	−0.0128 (5)	0.0111 (6)
O1W	0.0257 (6)	0.0619 (9)	0.0279 (7)	−0.0159 (6)	−0.0043 (5)	−0.0058 (6)
O2	0.0231 (6)	0.0416 (9)	0.0939 (13)	−0.0063 (6)	−0.0090 (7)	0.0162 (9)
O2W	0.0637 (11)	0.0762 (14)	0.0583 (12)	−0.0359 (10)	0.0060 (9)	−0.0144 (10)
O4	0.0787 (12)	0.0705 (12)	0.0375 (8)	−0.0353 (10)	−0.0087 (8)	−0.0141 (8)
O3	0.0393 (7)	0.0474 (9)	0.0394 (8)	−0.0212 (6)	−0.0143 (6)	0.0181 (6)
O5	0.0320 (6)	0.0338 (7)	0.0301 (6)	−0.0112 (5)	−0.0153 (5)	0.0098 (5)
O7	0.0763 (12)	0.0541 (10)	0.0512 (10)	−0.0234 (9)	−0.0231 (9)	0.0046 (8)
O6	0.0594 (10)	0.1007 (15)	0.0345 (8)	−0.0213 (10)	−0.0141 (7)	−0.0020 (9)
C1	0.0224 (7)	0.0313 (9)	0.0232 (8)	−0.0035 (7)	−0.0013 (6)	0.0014 (7)
C2	0.0307 (8)	0.0271 (9)	0.0251 (8)	−0.0096 (7)	−0.0017 (7)	0.0035 (7)
C3	0.0269 (8)	0.0295 (9)	0.0235 (8)	−0.0107 (7)	−0.0004 (6)	−0.0004 (7)
C4	0.0273 (8)	0.0291 (9)	0.0240 (8)	−0.0074 (7)	−0.0044 (6)	0.0036 (7)
C5	0.0238 (7)	0.0234 (8)	0.0297 (9)	−0.0061 (6)	−0.0010 (6)	0.0005 (7)
C6	0.0278 (8)	0.0313 (9)	0.0291 (9)	−0.0088 (7)	−0.0048 (7)	−0.0043 (7)
C7	0.0254 (8)	0.0403 (11)	0.0236 (8)	0.0001 (7)	−0.0024 (7)	0.0019 (7)
C8	0.0425 (10)	0.0416 (11)	0.0259 (9)	−0.0241 (9)	−0.0008 (8)	−0.0013 (8)
C9	0.0279 (8)	0.0256 (9)	0.0351 (10)	−0.0081 (7)	0.0020 (7)	−0.0005 (7)
C10	0.0376 (9)	0.0329 (10)	0.0296 (9)	−0.0125 (8)	−0.0077 (7)	−0.0037 (7)
C11	0.0309 (8)	0.0357 (10)	0.0290 (9)	−0.0155 (8)	−0.0047 (7)	−0.0012 (7)
C12	0.0273 (8)	0.0270 (9)	0.0264 (8)	−0.0075 (7)	−0.0049 (7)	0.0010 (7)
C13	0.0361 (9)	0.0311 (10)	0.0319 (9)	−0.0042 (8)	−0.0092 (8)	0.0007 (8)
C14	0.0273 (8)	0.0389 (11)	0.0297 (9)	−0.0056 (8)	−0.0030 (7)	−0.0019 (8)
C15	0.0279 (8)	0.0290 (9)	0.0330 (9)	−0.0106 (7)	−0.0028 (7)	−0.0006 (7)
C16	0.0407 (10)	0.0413 (11)	0.0262 (9)	−0.0067 (9)	−0.0087 (8)	−0.0063 (8)
C17	0.0344 (9)	0.0411 (11)	0.0307 (9)	−0.0032 (8)	−0.0120 (8)	−0.0047 (8)
C18	0.0325 (9)	0.0299 (9)	0.0273 (9)	−0.0069 (7)	−0.0071 (7)	−0.0030 (7)
C20	0.0366 (10)	0.0364 (10)	0.0298 (9)	−0.0055 (8)	−0.0102 (8)	0.0031 (8)
C21	0.0546 (13)	0.0468 (13)	0.0463 (13)	−0.0177 (11)	0.0023 (10)	−0.0065 (10)
C22	0.0651 (15)	0.0489 (14)	0.0455 (13)	−0.0091 (12)	−0.0142 (11)	−0.0077 (11)

Ni1—N5i	2.0597 (15)	C1—C6	1.393 (3)
Ni1—N3ii	2.0735 (15)	C1—C7	1.516 (2)
Ni1—N1	2.0777 (15)	C2—C3	1.397 (2)
Ni1—O5	2.0904 (12)	C2—H2A	0.9300
Ni1—O1W	2.1048 (12)	C3—C4	1.384 (2)
Ni1—O1	2.1458 (12)	C3—C8	1.513 (2)
S1—O2	1.4516 (14)	C4—C5	1.395 (2)
S1—O4	1.4611 (16)	C4—H4A	0.9300
S1—O1	1.4792 (12)	C5—C6	1.386 (2)
S1—O3	1.4895 (13)	C5—C9	1.506 (2)
N1—C12	1.324 (2)	C6—H6A	0.9300
N1—C11	1.375 (2)	C7—H7A	0.9700
N2—C12	1.344 (2)	C7—H7B	0.9700
N2—C10	1.370 (2)	C8—H8A	0.9700
N2—C7	1.467 (2)	C8—H8B	0.9700
N3—C15	1.325 (2)	C9—H9A	0.9700
N3—C14	1.376 (2)	C9—H9B	0.9700
N3—Ni1ii	2.0736 (15)	C10—C11	1.358 (3)
N4—C15	1.343 (2)	C10—H10A	0.9300
N4—C13	1.371 (2)	C11—H11A	0.9300
N4—C8	1.465 (2)	C12—H12A	0.9300
N5—C18	1.322 (2)	C13—C14	1.348 (3)
N5—C17	1.371 (2)	C13—H13A	0.9300
N5—Ni1i	2.0597 (15)	C14—H14A	0.9300
N6—C18	1.343 (2)	C15—H15A	0.9300
N6—C16	1.371 (2)	C16—C17	1.355 (3)
N6—C9	1.469 (2)	C16—H16A	0.9300
O1W—H1WA	0.8187	C17—H17A	0.9300
O1W—H1WB	0.8219	C18—H18A	0.9300
O2W—H2WA	0.8318	C20—C20i	1.492 (4)
O2W—H2WB	0.8269	C20—H20A	0.9700
O5—C20	1.427 (2)	C20—H20B	0.9700
O5—H1A	0.8129	C21—C22	1.489 (3)
O7—C21	1.420 (3)	C21—H21A	0.9700
O7—H7C	0.8200	C21—H21B	0.9700
O6—C22	1.404 (3)	C22—H22A	0.9700
O6—H6B	0.8200	C22—H22B	0.9700
C1—C2	1.379 (3)
N5i—Ni1—N3ii	89.38 (6)	C5—C6—H6A	119.9
N5i—Ni1—N1	175.70 (6)	C1—C6—H6A	119.9
N3ii—Ni1—N1	92.36 (6)	N2—C7—C1	112.19 (14)
N5i—Ni1—O5	88.70 (6)	N2—C7—H7A	109.2
N3ii—Ni1—O5	176.18 (5)	C1—C7—H7A	109.2
N1—Ni1—O5	89.79 (5)	N2—C7—H7B	109.2
N5i—Ni1—O1W	88.85 (6)	C1—C7—H7B	109.2
N3ii—Ni1—O1W	93.73 (6)	H7A—C7—H7B	107.9
N1—Ni1—O1W	87.11 (5)	N4—C8—C3	112.00 (15)
O5—Ni1—O1W	89.54 (5)	N4—C8—H8A	109.2
N5i—Ni1—O1	93.10 (6)	C3—C8—H8A	109.2
N3ii—Ni1—O1	90.67 (5)	N4—C8—H8B	109.2
N1—Ni1—O1	90.82 (5)	C3—C8—H8B	109.2
O5—Ni1—O1	86.13 (5)	H8A—C8—H8B	107.9
O1W—Ni1—O1	175.21 (5)	N6—C9—C5	111.96 (14)
O2—S1—O4	111.46 (11)	N6—C9—H9A	109.2
O2—S1—O1	109.44 (9)	C5—C9—H9A	109.2
O4—S1—O1	110.26 (9)	N6—C9—H9B	109.2
O2—S1—O3	109.46 (9)	C5—C9—H9B	109.2
O4—S1—O3	107.10 (10)	H9A—C9—H9B	107.9
O1—S1—O3	109.06 (7)	C11—C10—N2	105.93 (16)
C12—N1—C11	105.32 (15)	C11—C10—H10A	127.0
C12—N1—Ni1	127.89 (12)	N2—C10—H10A	127.0
C11—N1—Ni1	126.79 (12)	C10—C11—N1	109.93 (16)
C12—N2—C10	107.46 (14)	C10—C11—H11A	125.0
C12—N2—C7	126.22 (16)	N1—C11—H11A	125.0
C10—N2—C7	126.31 (16)	N1—C12—N2	111.36 (15)
C15—N3—C14	105.22 (15)	N1—C12—H12A	124.3
C15—N3—Ni1ii	126.02 (12)	N2—C12—H12A	124.3
C14—N3—Ni1ii	128.61 (12)	C14—C13—N4	106.18 (16)
C15—N4—C13	107.33 (15)	C14—C13—H13A	126.9
C15—N4—C8	125.92 (16)	N4—C13—H13A	126.9
C13—N4—C8	126.61 (16)	C13—C14—N3	110.02 (16)
C18—N5—C17	105.44 (15)	C13—C14—H14A	125.0
C18—N5—Ni1i	128.44 (12)	N3—C14—H14A	125.0
C17—N5—Ni1i	126.04 (12)	N3—C15—N4	111.25 (16)
C18—N6—C16	107.12 (15)	N3—C15—H15A	124.4
C18—N6—C9	126.52 (15)	N4—C15—H15A	124.4
C16—N6—C9	126.24 (15)	C17—C16—N6	106.14 (16)
S1—O1—Ni1	138.40 (8)	C17—C16—H16A	126.9
Ni1—O1W—H1WA	118.1	N6—C16—H16A	126.9
Ni1—O1W—H1WB	126.3	C16—C17—N5	109.86 (16)
H1WA—O1W—H1WB	109.6	C16—C17—H17A	125.1
H2WA—O2W—H2WB	108.8	N5—C17—H17A	125.1
C20—O5—Ni1	131.31 (12)	N5—C18—N6	111.43 (15)
C20—O5—H1A	110.7	N5—C18—H18A	124.3
Ni1—O5—H1A	106.8	N6—C18—H18A	124.3
C21—O7—H7C	109.5	O5—C20—C20i	108.89 (19)
C22—O6—H6B	109.5	O5—C20—H20A	109.9
C2—C1—C6	119.90 (16)	C20i—C20—H20A	109.9
C2—C1—C7	119.62 (16)	O5—C20—H20B	109.9
C6—C1—C7	120.47 (16)	C20i—C20—H20B	109.9
C1—C2—C3	120.49 (16)	H20A—C20—H20B	108.3
C1—C2—H2A	119.8	O7—C21—C22	109.84 (19)
C3—C2—H2A	119.8	O7—C21—H21A	109.7
C4—C3—C2	119.28 (16)	C22—C21—H21A	109.7
C4—C3—C8	120.40 (16)	O7—C21—H21B	109.7
C2—C3—C8	120.29 (16)	C22—C21—H21B	109.7
C3—C4—C5	120.59 (16)	H21A—C21—H21B	108.2
C3—C4—H4A	119.7	O6—C22—C21	113.0 (2)
C5—C4—H4A	119.7	O6—C22—H22A	109.0
C6—C5—C4	119.54 (16)	C21—C22—H22A	109.0
C6—C5—C9	120.37 (16)	O6—C22—H22B	109.0
C4—C5—C9	120.09 (16)	C21—C22—H22B	109.0
C5—C6—C1	120.19 (16)	H22A—C22—H22B	107.8
O2—S1—O1—Ni1	−139.62 (13)	C7—N2—C10—C11	−178.79 (16)
O4—S1—O1—Ni1	97.44 (15)	N2—C10—C11—N1	−0.3 (2)
O3—S1—O1—Ni1	−19.90 (16)	C12—N1—C11—C10	0.3 (2)
C6—C1—C2—C3	−0.9 (3)	Ni1—N1—C11—C10	−179.26 (12)
C7—C1—C2—C3	−179.63 (15)	C11—N1—C12—N2	−0.27 (19)
C1—C2—C3—C4	1.4 (3)	Ni1—N1—C12—N2	179.31 (11)
C1—C2—C3—C8	179.31 (16)	C10—N2—C12—N1	0.12 (19)
C2—C3—C4—C5	−1.2 (3)	C7—N2—C12—N1	179.00 (15)
C8—C3—C4—C5	−179.09 (16)	C15—N4—C13—C14	−0.6 (2)
C3—C4—C5—C6	0.5 (3)	C8—N4—C13—C14	−176.31 (17)
C3—C4—C5—C9	−178.73 (15)	N4—C13—C14—N3	0.7 (2)
C4—C5—C6—C1	0.1 (3)	C15—N3—C14—C13	−0.5 (2)
C9—C5—C6—C1	179.27 (15)	Ni1ii—N3—C14—C13	175.22 (13)
C2—C1—C6—C5	0.2 (3)	C14—N3—C15—N4	0.1 (2)
C7—C1—C6—C5	178.86 (15)	Ni1ii—N3—C15—N4	−175.73 (11)
C12—N2—C7—C1	−92.6 (2)	C13—N4—C15—N3	0.3 (2)
C10—N2—C7—C1	86.1 (2)	C8—N4—C15—N3	176.05 (16)
C2—C1—C7—N2	−82.8 (2)	C18—N6—C16—C17	0.8 (2)
C6—C1—C7—N2	98.5 (2)	C9—N6—C16—C17	177.19 (17)
C15—N4—C8—C3	−92.2 (2)	N6—C16—C17—N5	−0.7 (2)
C13—N4—C8—C3	82.8 (2)	C18—N5—C17—C16	0.4 (2)
C4—C3—C8—N4	−129.77 (17)	Ni1i—N5—C17—C16	177.31 (13)
C2—C3—C8—N4	52.4 (2)	C17—N5—C18—N6	0.1 (2)
C18—N6—C9—C5	85.2 (2)	Ni1i—N5—C18—N6	−176.68 (12)
C16—N6—C9—C5	−90.5 (2)	C16—N6—C18—N5	−0.6 (2)
C6—C5—C9—N6	−97.28 (19)	C9—N6—C18—N5	−176.97 (15)
C4—C5—C9—N6	81.9 (2)	Ni1—O5—C20—C20i	99.0 (2)
C12—N2—C10—C11	0.09 (19)	O7—C21—C22—O6	−64.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O6iii	0.82	1.93	2.743 (2)	172
O1W—H1WB···O2iii	0.82	1.88	2.6995 (19)	178
O2W—H2WA···O3iv	0.83	2.00	2.827 (2)	176
O2W—H2WB···O3	0.83	2.13	2.928 (2)	163
O5—H1A···O3	0.81	1.81	2.6168 (18)	169
O7—H7C···O4iv	0.82	2.07	2.884 (3)	174