Crystal structure of bis(4-benzoyl­pyridine-κN)bis(methanol-κO)bis(thio­cyanato-κN)nickel(II) methanol monosolvate

Wellm, C.; Näther, C.

doi:10.1107/S2056989019001555

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ISSN: 2056-9890

Volume 75| Part 2| February 2019| Pages 299-303

https://doi.org/10.1107/S2056989019001555

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Crystal structure of bis(4-benzoylpyridine-κN)bis(methanol-κO)bis(thiocyanato-κN)nickel(II) methanol monosolvate

Carsten Wellm ^a ^* and Christian Näther ^a

^aInstitut für Anorganische Chemie, Universität Kiel, Max-Eyth. Str. 2, 241128 Kiel
^*Correspondence e-mail: cwellm@ac.uni-kiel.de

Edited by M. Weil, Vienna University of Technology, Austria (Received 18 January 2019; accepted 28 January 2019; online 31 January 2019)

The asymmetric unit of the title compound, [Ni(NCS)₂(C₁₂H₉NO)₂(CH₃OH)₂]·CH₃OH, comprises one Ni^II cation, two thiocyanate anions, two 4-benzoylpyridine coligands, two coordinating, as well as one non-coordinating methanol molecule. The Ni^II cation is coordinated by two terminally N-bonded thiocyanate anions, the N atoms of two 4-benzoylpyridine coligands and the O atoms of two methanol ligands within a slightly distorted octahedron. Individual complexes are linked by intermolecular O—H⋯S hydrogen bonding into chains parallel to [010] that are further connected into layers parallel to (10 $[\overline{1}]$ ) by C—H⋯S hydrogen bonds. Additional C—H⋯O hydrogen-bonding interactions lead to the formation of a three-dimensional network that limits channels extending parallel to [010] in which the non-coordinating methanol molecules are located. They are hydrogen-bonded to the coordinating methanol molecules. X-ray powder diffraction revealed that the compound could not be prepared as a pure phase.

Keywords: crystal structure; nickel(II) thiocyanate; discrete complex; solvate; hydrogen bonding.

CCDC reference: 1894170

1. Chemical context

Thiocyanate anions are versatile ligands that can coordinate to metal cations in different manners, leading to a variety of structural set-ups. The most common coordination modes are the N-terminal and the μ-1,3-bridging coordination, but, as an example, there are also reports of a μ-1,1-coordination (Prananto et al., 2017 ; Buckingham, 1994 ; Palion-Gazda et al., 2017 ; Mautner et al., 2016 , 2017 ; Mahmoudi et al., 2017 ; Hamdani et al., 2018 ; Wöhlert et al., 2014a ,b ). With respect to paramagnetic transition metal cations, the μ-1,3-bridging mode is of special importance because it can mediate the magnetic exchange (Gonzalez et al., 2012 ; Wöhlert et al., 2013a ,b ; Palion-Gazda et al., 2015 ; Guillet et al., 2016 ; Mekuimemba et al., 2018 ). In this context, an increasing number of compounds with different magnetic properties are being reported (Wöhlert et al., 2014a,b; Werner et al., 2015 ; Suckert et al., 2017a ; Mautner et al., 2018 ). In the majority of cases, the metal cations are linked by thiocyanate anions into chains, but there are also examples where layer formation is observed (Suckert et al., 2016 ; Wellm et al., 2018 ; Neumann et al., 2018a ).

Unfortunately, for most paramagnetic transition metal cations, the bridging modes are energetically less favored and thus, compounds with a terminal coordination are usually obtained. Nevertheless, we have found an alternative approach to overcome this problem by transformation of the latter compounds through thermal annealing into the desired compounds that have bridging anions. For the alternative synthesis of such coordination polymers with bridging anionic ligands, a precursor consisting of a discrete complex can be used in which the metal cations are coordinated by two terminal N-bonded thiocyanate anions and four co-ligands that, in our cases, consist of pyridine derivatives. Upon controlled heating, two of the four co-ligands can be removed. Frequently, this treatment yields the desired compounds with bridging coordination as intermediates, which can easily be investigated by thermogravimetry. In some cases, no discrete decomposition steps are observed because all co-ligands are removed in one step. Under these circumstances, alternatives are required that are based on precursor complexes comprising only two of the pyridine derivatives as ligands and two coordinating and volatile molecules such as water or methanol. The ligand molecules are emitted in a discrete step (also observable in a thermogravimetrical measurement), which directly produces the desired compounds in quantitative yield. It is also noted that this approach often leads to the formation of polymorphs or isomers that are different from the compounds obtained from solution (Werner et al., 2015; Jochim et al., 2018 ).

In this context we have reported two isotypic compounds with chain-structures that have the general composition M(NCS)₂(4-benzoylpyridine)₂ where M = Co, Ni (Rams et al., 2017 ; Jochim et al., 2018). Here the metal cations are linked into linear chains with a cis–cis–trans coordination, in contrast to most other compounds with similar linear chains where all ligands are in trans positions. This is somewhat surprising because Cd(NCS)₂(4-benzoylpyridine)₂ also forms linear chains with an all-trans coordination of the cations (Neumann et al., 2018a). Therefore, our intention was to test if a different isomer with, for example, Ni can be prepared by thermal annealing. A complex with composition Ni(NCS)₂(4-benzoylpyridine)₄ has already been reported in the literature. It decomposes in several steps, but only the intermediate after complete removal of 4-benzoylpyridine was examined (Soliman et al., 2014 ). We have synthesized this compound again and investigated its thermal properties. The residue formed after removal of half of the 4-benzoylpyiridine ligands is of poor crystallinity and does not correspond to a pure phase. Therefore, we searched for a more promising precursor; during these investigations, crystals of the title compound were obtained and characterized by single crystal X-ray diffraction. X-ray powder diffraction revealed that the compound directly isolated from the reaction mixture is a nearly pure phase but always contaminated with a very small amount of Ni(NCS)₂(4-benzoylpyridine)₄ (see Fig. S1 in the supporting information). More importantly, if the title compound is filtered off, it decomposes very quickly into an unknown crystalline phase that does not correspond to that of Ni(NCS)₂(4-benzoylpyridine)₄ already reported in the literature. However, this sample is still contaminated with Ni(NCS)₂(4-benzoylpyridine)₄, and any attempt to completely index its powder pattern failed (Fig. S2 in the supporting information).

2. Structural commentary

The crystal structure of the title compound consists of discrete complexes in which the Ni^II cations are sixfold coordinated by two crystallographically independent thiocyanate anions, two methanol molecules and two 4-benzoylpyridine ligands (Fig. 1). The Ni—N bond lengths to the anionic ligands of 2.009 (3) and 2.034 (3) Å are shorter than those to the 4-benzoylpyridine ligands [2.092 (2) and 2.104 (2) Å; the Ni—O distances to the methanol ligands are longer again at 2.108 (2) and 2.154 (2) Å. The coordination sphere around Ni^II can be described as a slightly distorted octahedron. This is also obvious from the angle variance and the quadratic elongation, which were calculated to be 4.7 and 1.022 (Robinson et al., 1971 ). The 4-benzoylpyridine ligand is not planar. The dihedral angle between the pyridine ring (N11, C11–C15) and the carbonyl plane (C13, C16, C17, O11) amounts to 56.86 (16)° and that between the phenyl ring (C17–C22) and the carbonyl group (C13, C16, C17, O11) to 12.49 (17)°. The second ligand has corresponding values of 48.61 (17)° between the pyridine ring (N31, C31–C35) and the carbonyl group (C33, C36, C37, O31) and 16.69 (18)° between the phenyl ring (C37–C42) and the carbonyl group (C33, C36, C37, O31). There is a short intramolecular contact between one of the aromatic hydrogen atoms (H35) and one of the thiocyanate N atoms (N1); however, the corresponding C—H⋯N angle deviates strongly from linearity, indicating only a weak interaction (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C32—H32⋯S2ⁱ	0.95	3.01	3.865 (3)	151
C34—H34⋯O11ⁱⁱ	0.95	2.50	3.406 (4)	160
C35—H35⋯N1	0.95	2.65	3.113 (4)	111
O1—H1⋯O3	0.84	1.83	2.643 (3)	163
O2—H2⋯S1ⁱⁱⁱ	0.84	2.44	3.246 (2)	160
O3—H3⋯O11ⁱⁱⁱ	0.84	1.98	2.808 (3)	166
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x-1, y, z; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The asymmetric unit of the solvated title complex with the atom labelling and displacement ellipsoids drawn at the 50% probability level.

3. Supramolecular features

The crystal structure of the title compound is dominated by extensive intermolecular classical and non-classical hydrogen-bonding interactions of medium-to-weak strengths (Table 1). Discrete complexes are linked by intermolecular O—H⋯S hydrogen bonds into chains extending parallel to [010] (Fig. 2, top). Within such a chain, the complexes are related by the 2₁-screw axis, resulting in a helical arrangement (Fig. 2, bottom). These chains are further linked by pairs of centrosymmetric C—H⋯S hydrogen bonds into layers extending parallel to (10 $[\overline{1}]$ ) (Fig. 3). Adjacent layers are linked into a three-dimensional network by C—H⋯O hydrogen bonding between a hydrogen atom (H34) of one of the phenyl rings and the carbonyl O atom (O11) of a neighboring 4-benzoylpyridine ligand (Fig. 4). Within this network channels are formed in which the non-coordinating methanol molecules are embedded (Fig. 4). The solvent molecules are linked by O—H⋯O hydrogen bonding and act both as a donor (O3) to a neighbouring carbonyl O atom (O11) and as an acceptor for a hydroxyl group (O1) of a methanol ligand (Fig. 4).

Figure 2
Crystal structure of the title compound in a view along (top) and perpendicular (bottom) to the hydrogen-bonded chains. Intermolecular O—H⋯S hydrogen bonding is shown as dashed lines.

Figure 3
Crystal structure of the title compound in a view approximately [110] showing the layers formed by intermolecular O—H⋯S and C—H⋯S hydrogen bonding (shown as dashed lines).

Figure 4
Crystal structure of the title compound in a view along [010] showing the channels that are filled with the non-coordinating methanol molecules. Intermolecular O—H⋯S, C—H⋯S, C—H⋯O and O—H⋯O hydrogen bonding is shown as dashed lines; the oval channels are marked with thick lines.

4. Database survey

In the Cambridge Structure Database (Version 5.39, last update Aug 2018; Groom et al., 2016 ) several structures of transition-metal thiocyanate coordination compounds with 4-benzoylpyridine as ligand have been deposited. They include three compounds with the composition [M(NCS)₂(4-benzoylpyridine)₂]_n (M = Cd, Co, Ni), in which the metal cations are octahedrally coordinated and linked into chains by pairs of μ-1,3 bridging thiocyanate anions (Neumann et al., 2018a; Rams et al., 2017; Jochim et al., 2018). Discrete complexes with general composition M(NCS)₂(4-benzoylpyridine)₄ (M = Co, Ni, Mn, Cd and Zn) are also reported in which the metal cations are octahedrally coordinated by two terminal N-bonded thiocyanate anions and four 4-benzoylpyridine co-ligands (Drew et al., 1985 ; Soliman et al., 2014; Wellm & Näther, 2018 ; Neumann et al., 2018b ). There are also compounds where the metal cations are fourfold coordinated by the two N-bonded terminal thiocyanate anions and two 4-benzoylpyridine co-ligands, forming either a tetrahedral (Zn^II complex) or a square-planar (Cu^II complex) coordination sphere (Neumann et al., 2018a; Bai et al., 2011 ). The last group consists of octahedrally coordinated Co^II cations that either contain two acetonitrile (Suckert et al., 2017b ) or two methanol molecules (Suckert et al., 2017c ) as coordinating solvent molecules.

5. Synthesis and crystallization

Ba(SCN)₂·3H₂O and 4-benzoylpyridine were purchased from Alfa Aesar. NiSO₄·6H₂O was purchased from Merck. All solvents and reactants were used without further purification. Ni(NCS)₂ was prepared by the reaction of equimolar amounts of NiSO₄·6H₂O and Ba(NCS)₂·3H₂O in water. The resulting white precipitate of BaSO₄ was filtered off, and the solvent was evaporated from the filtrate. The product was dried at room temperature. Crystals of the title compound suitable for single-crystal X-ray diffraction were obtained within a few days by the reaction of 52.5 mg Ni(NCS)₂ (0.30 mmol) with 27.5 mg 4-benzoylpyridine (0.15 mmol) in methanol (1.5 ml) at 354 K using culture tubes.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The hydrogen atoms were positioned with idealized geometry (C–H = 0.95–0.98 Å; methyl H atoms in part were allowed to rotate but not to tip) and were refined with U_iso(H) = 1.2U_eq(C) (1.5 for methyl H atoms) using a riding model. The OH hydrogen atoms were located in a difference-Fourier map; their bond lengths were set to ideal values and finally they were refined with U_iso(H) = 1.5U_eq(O) using a riding model.

Table 2
Experimental details

Crystal data
Chemical formula	[Ni(NCS)₂(C₁₂H₉NO)₂(CH₄O)₂]·CH₄O
M_r	637.40
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	200
a, b, c (Å)	12.0588 (6), 7.5515 (3), 33.0408 (16)
β (°)	94.021 (4)
V (Å³)	3001.4 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.83
Crystal size (mm)	0.25 × 0.15 × 0.08

Data collection
Diffractometer	Stoe IPDS2
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe, 2008 )
T_min, T_max	0.638, 0.875
No. of measured, independent and observed [I > 2σ(I)] reflections	17675, 4726, 4004
R_int	0.036
θ_max (°)	24.1
(sin θ/λ)_max (Å⁻¹)	0.574

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.105, 1.10
No. of reflections	4726
No. of parameters	371
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.26
Computer programs: X-AREA (Stoe, 2008), XP in SHELXTL and SHELXS97 (Sheldrick, 2008 ), SHELXL2014/7 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 1999 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1894170

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019001555/wm5485sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019001555/wm5485Isup2.hkl

Figure S1. Calculated X-ray powder pattern of the title compound (A) and of [Ni(NCS)2(4-benzoylpyridine)4] (B) as well as the experimental X-ray powder pattern (C) of the freshly prepared title compound isolated before filtration. DOI: https://doi.org/10.1107/S2056989019001555/wm5485sup3.tif

Figure S2. Calculated X-ray powder pattern of the title compound (A), of [Ni(NCS)2(4-benzoylpyridine)4] (B) and [Ni(NCS)2(4-benzoylpyridine)2] (C) as well as the experimental X-ray powder pattern (D) of the title compound isolated after filtration with a Buchner funnel. DOI: https://doi.org/10.1107/S2056989019001555/wm5485sup4.tif

checkCIF report

Computing details top

Data collection: X-AREA (Stoe, 2008); cell refinement: X-AREA (Stoe, 2008); data reduction: X-AREA (Stoe, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis(4-benzoylpyridine-κN)bis(methanol-κO)bis(thiocyanato-κN)nickel(II) methanol monosolvate top

Crystal data top

[Ni(NCS)₂(C₁₂H₉NO)₂(CH₄O)₂]·CH₄O	F(000) = 1328
M_r = 637.40	D_x = 1.411 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.0588 (6) Å	Cell parameters from 17675 reflections
b = 7.5515 (3) Å	θ = 1.2–24.1°
c = 33.0408 (16) Å	µ = 0.83 mm⁻¹
β = 94.021 (4)°	T = 200 K
V = 3001.4 (2) Å³	Block, green
Z = 4	0.25 × 0.15 × 0.08 mm

Data collection top

Stoe IPDS-2 diffractometer	4004 reflections with I > 2σ(I)
ω scans	R_int = 0.036
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2008)	θ_max = 24.1°, θ_min = 1.2°
T_min = 0.638, T_max = 0.875	h = −13→13
17675 measured reflections	k = −8→8
4726 independent reflections	l = −37→37

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) = 0.105	w = 1/[σ²(F_o²) + (0.0571P)² + 0.7722P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
4726 reflections	Δρ_max = 0.46 e Å⁻³
371 parameters	Δρ_min = −0.26 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	0.58556 (3)	0.48583 (5)	0.16271 (2)	0.04735 (13)
N1	0.5502 (2)	0.3421 (3)	0.21226 (7)	0.0550 (6)
C1	0.5445 (2)	0.2585 (4)	0.24141 (9)	0.0488 (7)
S1	0.53684 (8)	0.13868 (12)	0.28229 (2)	0.0659 (2)
N2	0.6201 (2)	0.6432 (3)	0.11620 (8)	0.0584 (6)
C2	0.6290 (2)	0.7419 (4)	0.08932 (8)	0.0488 (6)
S2	0.64295 (7)	0.87918 (12)	0.05253 (2)	0.0638 (2)
N11	0.7197 (2)	0.3188 (3)	0.15150 (7)	0.0487 (5)
C11	0.7138 (3)	0.1421 (4)	0.15605 (9)	0.0528 (7)
H11	0.6443	0.0913	0.1614	0.063*
C12	0.8037 (3)	0.0310 (4)	0.15339 (9)	0.0545 (7)
H12	0.7950	−0.0936	0.1556	0.065*
C13	0.9062 (2)	0.1032 (4)	0.14754 (8)	0.0516 (7)
C14	0.9127 (3)	0.2864 (4)	0.14232 (9)	0.0534 (7)
H14	0.9819	0.3406	0.1378	0.064*
C15	0.8191 (3)	0.3869 (4)	0.14378 (8)	0.0524 (7)
H15	0.8244	0.5107	0.1391	0.063*
C16	1.0109 (3)	−0.0051 (4)	0.14785 (9)	0.0543 (7)
C17	1.0192 (3)	−0.1532 (4)	0.11893 (9)	0.0538 (7)
C18	1.1107 (3)	−0.2650 (5)	0.12354 (11)	0.0645 (8)
H18	1.1639	−0.2506	0.1459	0.077*
C19	1.1240 (3)	−0.3976 (5)	0.09531 (12)	0.0723 (10)
H19	1.1861	−0.4751	0.0985	0.087*
C20	1.0476 (3)	−0.4176 (4)	0.06269 (11)	0.0689 (9)
H20	1.0577	−0.5080	0.0433	0.083*
C21	0.9566 (3)	−0.3071 (4)	0.05800 (10)	0.0638 (8)
H21	0.9038	−0.3216	0.0355	0.077*
C22	0.9424 (3)	−0.1748 (4)	0.08619 (9)	0.0555 (7)
H22	0.8797	−0.0986	0.0830	0.067*
O11	1.08903 (18)	0.0371 (3)	0.17175 (7)	0.0681 (6)
N31	0.4723 (2)	0.3367 (3)	0.12595 (7)	0.0496 (6)
C31	0.4886 (3)	0.2922 (4)	0.08771 (9)	0.0536 (7)
H31	0.5575	0.3230	0.0773	0.064*
C32	0.4118 (3)	0.2047 (4)	0.06254 (9)	0.0553 (7)
H32	0.4283	0.1743	0.0357	0.066*
C33	0.3094 (2)	0.1610 (4)	0.07678 (9)	0.0510 (7)
C34	0.2925 (3)	0.2062 (4)	0.11660 (9)	0.0541 (7)
H34	0.2241	0.1780	0.1277	0.065*
C35	0.3740 (3)	0.2911 (4)	0.13971 (9)	0.0534 (7)
H35	0.3608	0.3194	0.1670	0.064*
C36	0.2167 (3)	0.0776 (4)	0.05069 (9)	0.0556 (7)
C37	0.2378 (3)	−0.0814 (4)	0.02630 (9)	0.0529 (7)
C38	0.1594 (3)	−0.1303 (5)	−0.00466 (9)	0.0626 (8)
H38	0.0944	−0.0608	−0.0100	0.075*
C39	0.1759 (4)	−0.2788 (5)	−0.02748 (11)	0.0747 (10)
H39	0.1228	−0.3105	−0.0488	0.090*
C40	0.2696 (4)	−0.3824 (5)	−0.01951 (12)	0.0828 (12)
H40	0.2800	−0.4858	−0.0352	0.099*
C41	0.3480 (3)	−0.3361 (5)	0.01117 (12)	0.0758 (10)
H41	0.4120	−0.4077	0.0167	0.091*
C42	0.3325 (3)	−0.1839 (4)	0.03387 (10)	0.0596 (8)
H42	0.3869	−0.1501	0.0546	0.071*
O31	0.1247 (2)	0.1446 (3)	0.05102 (8)	0.0762 (7)
O1	0.45471 (18)	0.6547 (3)	0.17699 (6)	0.0590 (5)
H1	0.4265	0.6291	0.1988	0.089*
C3	0.4305 (3)	0.8282 (5)	0.16255 (13)	0.0801 (11)
H3A	0.3642	0.8727	0.1747	0.120*
H3B	0.4937	0.9062	0.1700	0.120*
H3C	0.4171	0.8256	0.1330	0.120*
O2	0.69448 (18)	0.6461 (3)	0.20203 (6)	0.0604 (5)
H2	0.7622	0.6195	0.2026	0.091*
C4	0.6653 (3)	0.7267 (6)	0.23878 (12)	0.0854 (12)
H4A	0.7293	0.7924	0.2510	0.128*
H4B	0.6030	0.8082	0.2330	0.128*
H4C	0.6437	0.6349	0.2577	0.128*
O3	0.3644 (2)	0.6458 (4)	0.24757 (8)	0.0844 (8)
H3	0.3838	0.5988	0.2700	0.127*
C5	0.2807 (4)	0.7704 (7)	0.25548 (14)	0.1051 (15)
H5A	0.2179	0.7090	0.2666	0.158*
H5B	0.2553	0.8303	0.2302	0.158*
H5C	0.3109	0.8580	0.2752	0.158*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0524 (2)	0.0467 (2)	0.0431 (2)	−0.00002 (16)	0.00477 (15)	0.00073 (15)
N1	0.0544 (15)	0.0607 (15)	0.0499 (13)	0.0041 (12)	0.0036 (11)	0.0030 (12)
C1	0.0465 (16)	0.0523 (16)	0.0477 (15)	0.0025 (13)	0.0045 (12)	−0.0028 (13)
S1	0.0660 (5)	0.0740 (5)	0.0582 (4)	0.0013 (4)	0.0086 (4)	0.0192 (4)
N2	0.0653 (17)	0.0552 (15)	0.0551 (14)	−0.0033 (12)	0.0074 (12)	−0.0009 (12)
C2	0.0482 (16)	0.0511 (16)	0.0471 (15)	−0.0007 (13)	0.0036 (13)	−0.0006 (13)
S2	0.0660 (5)	0.0682 (5)	0.0574 (4)	−0.0027 (4)	0.0056 (4)	0.0168 (4)
N11	0.0527 (14)	0.0484 (13)	0.0454 (12)	−0.0049 (11)	0.0066 (11)	−0.0028 (10)
C11	0.0473 (16)	0.0508 (17)	0.0609 (17)	−0.0061 (13)	0.0089 (14)	−0.0011 (13)
C12	0.0552 (18)	0.0482 (16)	0.0607 (17)	−0.0008 (14)	0.0076 (14)	−0.0016 (13)
C13	0.0521 (17)	0.0562 (17)	0.0468 (14)	−0.0021 (14)	0.0064 (13)	−0.0059 (13)
C14	0.0509 (17)	0.0540 (17)	0.0566 (16)	−0.0069 (14)	0.0129 (14)	−0.0041 (13)
C15	0.0595 (18)	0.0475 (15)	0.0508 (15)	−0.0096 (14)	0.0091 (14)	−0.0030 (12)
C16	0.0503 (17)	0.0591 (18)	0.0542 (16)	−0.0020 (14)	0.0084 (14)	0.0003 (14)
C17	0.0517 (17)	0.0541 (17)	0.0568 (17)	−0.0014 (14)	0.0114 (14)	0.0025 (13)
C18	0.0559 (19)	0.065 (2)	0.074 (2)	0.0064 (16)	0.0109 (16)	0.0085 (16)
C19	0.074 (2)	0.0584 (19)	0.087 (2)	0.0152 (17)	0.029 (2)	0.0090 (18)
C20	0.082 (2)	0.0527 (18)	0.075 (2)	0.0000 (17)	0.028 (2)	−0.0030 (16)
C21	0.072 (2)	0.0563 (18)	0.0642 (19)	−0.0028 (17)	0.0143 (16)	−0.0047 (15)
C22	0.0573 (18)	0.0527 (17)	0.0571 (16)	0.0004 (14)	0.0092 (14)	−0.0001 (13)
O11	0.0538 (13)	0.0825 (16)	0.0674 (13)	−0.0034 (11)	0.0007 (12)	−0.0082 (12)
N31	0.0513 (14)	0.0516 (13)	0.0464 (12)	0.0024 (11)	0.0056 (11)	0.0013 (10)
C31	0.0535 (17)	0.0590 (17)	0.0492 (15)	−0.0048 (14)	0.0096 (13)	−0.0017 (13)
C32	0.0594 (19)	0.0586 (17)	0.0481 (15)	−0.0037 (15)	0.0053 (14)	−0.0052 (13)
C33	0.0511 (17)	0.0450 (15)	0.0566 (16)	0.0026 (13)	0.0021 (14)	0.0010 (13)
C34	0.0506 (17)	0.0531 (17)	0.0591 (17)	0.0005 (14)	0.0084 (14)	0.0016 (14)
C35	0.0545 (18)	0.0576 (17)	0.0486 (15)	0.0014 (14)	0.0070 (14)	0.0013 (13)
C36	0.0528 (19)	0.0538 (17)	0.0594 (17)	−0.0007 (14)	−0.0019 (14)	0.0020 (14)
C37	0.0575 (18)	0.0497 (16)	0.0520 (16)	−0.0070 (14)	0.0083 (14)	0.0016 (13)
C38	0.067 (2)	0.068 (2)	0.0534 (17)	−0.0148 (17)	0.0042 (15)	0.0026 (15)
C39	0.085 (3)	0.080 (2)	0.0602 (19)	−0.029 (2)	0.0132 (18)	−0.0120 (18)
C40	0.096 (3)	0.073 (2)	0.084 (3)	−0.027 (2)	0.037 (2)	−0.025 (2)
C41	0.076 (2)	0.062 (2)	0.092 (3)	−0.0005 (18)	0.025 (2)	−0.0069 (19)
C42	0.0594 (19)	0.0527 (17)	0.0674 (19)	−0.0043 (15)	0.0101 (15)	−0.0008 (15)
O31	0.0551 (14)	0.0694 (15)	0.1020 (18)	0.0078 (12)	−0.0103 (13)	−0.0142 (13)
O1	0.0676 (14)	0.0550 (12)	0.0551 (11)	0.0074 (10)	0.0087 (10)	0.0036 (9)
C3	0.080 (3)	0.063 (2)	0.099 (3)	0.0178 (19)	0.021 (2)	0.023 (2)
O2	0.0602 (13)	0.0646 (13)	0.0567 (11)	−0.0027 (10)	0.0057 (10)	−0.0121 (10)
C4	0.069 (2)	0.111 (3)	0.076 (2)	0.004 (2)	0.0030 (19)	−0.042 (2)
O3	0.0767 (17)	0.108 (2)	0.0711 (15)	0.0280 (15)	0.0213 (13)	0.0161 (14)
C5	0.095 (3)	0.129 (4)	0.092 (3)	0.033 (3)	0.018 (3)	−0.002 (3)

Geometric parameters (Å, º) top

Ni1—N2	2.009 (3)	C31—H31	0.9500
Ni1—N1	2.034 (3)	C32—C33	1.392 (4)
Ni1—N31	2.092 (2)	C32—H32	0.9500
Ni1—N11	2.104 (2)	C33—C34	1.388 (4)
Ni1—O1	2.108 (2)	C33—C36	1.501 (4)
Ni1—O2	2.154 (2)	C34—C35	1.362 (4)
N1—C1	1.158 (4)	C34—H34	0.9500
C1—S1	1.634 (3)	C35—H35	0.9500
N2—C2	1.170 (4)	C36—O31	1.220 (4)
C2—S2	1.615 (3)	C36—C37	1.478 (4)
N11—C11	1.345 (4)	C37—C42	1.387 (5)
N11—C15	1.345 (4)	C37—C38	1.394 (4)
C11—C12	1.378 (4)	C38—C39	1.373 (5)
C11—H11	0.9500	C38—H38	0.9500
C12—C13	1.378 (4)	C39—C40	1.384 (6)
C12—H12	0.9500	C39—H39	0.9500
C13—C14	1.397 (4)	C40—C41	1.382 (6)
C13—C16	1.503 (4)	C40—H40	0.9500
C14—C15	1.364 (4)	C41—C42	1.393 (5)
C14—H14	0.9500	C41—H41	0.9500
C15—H15	0.9500	C42—H42	0.9500
C16—O11	1.228 (4)	O1—C3	1.417 (4)
C16—C17	1.479 (4)	O1—H1	0.8401
C17—C22	1.383 (4)	C3—H3A	0.9800
C17—C18	1.389 (5)	C3—H3B	0.9800
C18—C19	1.386 (5)	C3—H3C	0.9800
C18—H18	0.9500	O2—C4	1.424 (4)
C19—C20	1.376 (5)	O2—H2	0.8400
C19—H19	0.9500	C4—H4A	0.9800
C20—C21	1.380 (5)	C4—H4B	0.9800
C20—H20	0.9500	C4—H4C	0.9800
C21—C22	1.384 (4)	O3—C5	1.418 (5)
C21—H21	0.9500	O3—H3	0.8402
C22—H22	0.9500	C5—H5A	0.9800
N31—C31	1.335 (4)	C5—H5B	0.9800
N31—C35	1.343 (4)	C5—H5C	0.9800
C31—C32	1.369 (4)

N2—Ni1—N1	175.96 (10)	N31—C31—C32	123.9 (3)
N2—Ni1—N31	92.09 (10)	N31—C31—H31	118.0
N1—Ni1—N31	90.85 (10)	C32—C31—H31	118.0
N2—Ni1—N11	90.95 (10)	C31—C32—C33	119.1 (3)
N1—Ni1—N11	91.66 (9)	C31—C32—H32	120.4
N31—Ni1—N11	93.10 (9)	C33—C32—H32	120.4
N2—Ni1—O1	90.70 (10)	C34—C33—C32	117.1 (3)
N1—Ni1—O1	86.56 (9)	C34—C33—C36	119.6 (3)
N31—Ni1—O1	89.25 (9)	C32—C33—C36	123.2 (3)
N11—Ni1—O1	177.08 (8)	C35—C34—C33	119.9 (3)
N2—Ni1—O2	88.77 (10)	C35—C34—H34	120.0
N1—Ni1—O2	88.15 (9)	C33—C34—H34	120.0
N31—Ni1—O2	176.81 (9)	N31—C35—C34	123.4 (3)
N11—Ni1—O2	89.96 (9)	N31—C35—H35	118.3
O1—Ni1—O2	87.67 (8)	C34—C35—H35	118.3
C1—N1—Ni1	171.3 (2)	O31—C36—C37	122.2 (3)
N1—C1—S1	179.4 (3)	O31—C36—C33	117.5 (3)
C2—N2—Ni1	172.8 (3)	C37—C36—C33	120.2 (3)
N2—C2—S2	179.2 (3)	C42—C37—C38	119.5 (3)
C11—N11—C15	117.0 (3)	C42—C37—C36	121.7 (3)
C11—N11—Ni1	121.87 (19)	C38—C37—C36	118.8 (3)
C15—N11—Ni1	120.7 (2)	C39—C38—C37	120.2 (4)
N11—C11—C12	123.3 (3)	C39—C38—H38	119.9
N11—C11—H11	118.3	C37—C38—H38	119.9
C12—C11—H11	118.3	C38—C39—C40	120.3 (4)
C13—C12—C11	119.1 (3)	C38—C39—H39	119.8
C13—C12—H12	120.5	C40—C39—H39	119.8
C11—C12—H12	120.5	C41—C40—C39	120.3 (4)
C12—C13—C14	117.9 (3)	C41—C40—H40	119.9
C12—C13—C16	123.0 (3)	C39—C40—H40	119.9
C14—C13—C16	119.0 (3)	C40—C41—C42	119.5 (4)
C15—C14—C13	119.5 (3)	C40—C41—H41	120.2
C15—C14—H14	120.2	C42—C41—H41	120.2
C13—C14—H14	120.2	C37—C42—C41	120.2 (3)
N11—C15—C14	123.0 (3)	C37—C42—H42	119.9
N11—C15—H15	118.5	C41—C42—H42	119.9
C14—C15—H15	118.5	C3—O1—Ni1	128.6 (2)
O11—C16—C17	121.9 (3)	C3—O1—H1	114.5
O11—C16—C13	118.0 (3)	Ni1—O1—H1	114.0
C17—C16—C13	120.1 (3)	O1—C3—H3A	109.5
C22—C17—C18	119.8 (3)	O1—C3—H3B	109.5
C22—C17—C16	121.5 (3)	H3A—C3—H3B	109.5
C18—C17—C16	118.6 (3)	O1—C3—H3C	109.5
C19—C18—C17	119.6 (3)	H3A—C3—H3C	109.5
C19—C18—H18	120.2	H3B—C3—H3C	109.5
C17—C18—H18	120.2	C4—O2—Ni1	125.3 (2)
C20—C19—C18	120.3 (3)	C4—O2—H2	112.4
C20—C19—H19	119.9	Ni1—O2—H2	115.5
C18—C19—H19	119.9	O2—C4—H4A	109.5
C19—C20—C21	120.3 (3)	O2—C4—H4B	109.5
C19—C20—H20	119.8	H4A—C4—H4B	109.5
C21—C20—H20	119.8	O2—C4—H4C	109.5
C20—C21—C22	119.7 (3)	H4A—C4—H4C	109.5
C20—C21—H21	120.1	H4B—C4—H4C	109.5
C22—C21—H21	120.1	C5—O3—H3	106.0
C17—C22—C21	120.2 (3)	O3—C5—H5A	109.5
C17—C22—H22	119.9	O3—C5—H5B	109.5
C21—C22—H22	119.9	H5A—C5—H5B	109.5
C31—N31—C35	116.6 (3)	O3—C5—H5C	109.5
C31—N31—Ni1	123.5 (2)	H5A—C5—H5C	109.5
C35—N31—Ni1	119.82 (19)	H5B—C5—H5C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C32—H32···S2ⁱ	0.95	3.01	3.865 (3)	151
C34—H34···O11ⁱⁱ	0.95	2.50	3.406 (4)	160
C35—H35···N1	0.95	2.65	3.113 (4)	111
O1—H1···O3	0.84	1.83	2.643 (3)	163
O2—H2···S1ⁱⁱⁱ	0.84	2.44	3.246 (2)	160
O3—H3···O11ⁱⁱⁱ	0.84	1.98	2.808 (3)	166

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

Acknowledgements

We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

Funding information

This project was supported by the Deutsche Forschungsgemeinschaft (Project No. NA 720/6–1) and the State of Schleswig-Holstein.

References

Bai, Y., Zheng, G.-S., Dang, D.-B., Zheng, Y.-N. & Ma, P.-T. (2011). Spectrochim. Acta A, 79, 1338–1344. CrossRef CAS Google Scholar
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Buckingham, D. A. (1994). Coord. Chem. Rev. 135–136, 587–621. CrossRef Web of Science Google Scholar
Drew, M. G. B., Gray, N. I., Cabral, M. F. & Cabral, J. deO. (1985). Acta Cryst. C41, 1434–1437. CrossRef CAS Web of Science IUCr Journals Google Scholar
EL Hamdani, H., EL Amane, M. & Duhayon, C. (2018). J. Mol. Struct. 1157, 1–7. CrossRef CAS Google Scholar
González, R., Acosta, A., Chiozzone, R., Kremer, C., Armentano, D., De Munno, G., Julve, M., Lloret, F. & Faus, J. C. (2012). Inorg. Chem. 51, 5737–5747. 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
Guillet, J. L., Bhowmick, I., Shores, M. P., Daley, C. J. A., Gembicky, M., Golen, J. A., Rheingold, A. L. & Doerrer, L. H. (2016). Inorg. Chem. 55, 8099–8109. Web of Science CrossRef CAS PubMed Google Scholar
Jochim, A., Rams, M., Neumann, T., Wellm, C., Reinsch, H., Wójtowicz, G. M. & Näther, C. (2018). Eur. J. Inorg. Chem. pp. 4779–4789. CrossRef Google Scholar
Mahmoudi, G., Zangrando, E., Kaminsky, W., Garczarek, P. & Frontera, A. (2017). Inorg. Chim. Acta, 455, 204–212. CrossRef CAS Google Scholar
Mautner, F. A., Berger, C., Fischer, R. & Massoud, S. (2016). Inorg. Chim. Acta, 448, 34–41. CrossRef CAS Google Scholar
Mautner, F. A., Fischer, R. C., Rashmawi, L. G., Louka, F. R. & Massoud, S. (2017). Polyhedron, 124, 237–242. CrossRef CAS Google Scholar
Mautner, F. A., Traber, M., Fischer, R. C., Torvisco, A., Reichmann, K., Speed, S., Vicente, R. & Massoud, S. S. (2018). Polyhedron, 154, 436–442. CrossRef CAS Google Scholar
Mekuimemba, C. D., Conan, F., Mota, A. J., Palacios, M. A., Colacio, E. & Triki, S. (2018). Inorg. Chem. 57, 2184–2192. CrossRef CAS Google Scholar
Neumann, T., Ceglarska, M., Germann, L. S., Rams, M., Dinnebier, R. E., Suckert, S., Jess, I. & Näther, C. (2018a). Inorg. Chem. 57, 3305–3314. CrossRef CAS Google Scholar
Neumann, T., Jess, I., dos Santos Cunha, C., Terraschke, H. & Näther, C. (2018b). Inorg. Chim. Acta, 478, 15–24. CrossRef CAS Google Scholar
Palion-Gazda, J., Gryca, I., Maroń, A., Machura, B. & Kruszynski, R. (2017). Polyhedron, 135, 109–120. CAS Google Scholar
Palion-Gazda, J., Machura, B., Lloret, F. & Julve, M. (2015). Cryst. Growth Des. 15, 2380–2388. CAS Google Scholar
Prananto, Y. B., Urbatsch, A., Moubaraki, B., Murray, K. S., Turner, D. R., Deacon, G. B. & Batten, S. R. (2017). Aust. J. Chem. 70, 516–528. CrossRef CAS Google Scholar
Rams, M., Tomkowicz, Z., Böhme, M., Plass, W., Suckert, S., Werner, J., Jess, I. & Näther, C. (2017). Phys. Chem. Chem. Phys. 19, 3232–3243. CrossRef CAS PubMed Google Scholar
Robinson, K., Gibbs, G. V. & Ribbe, P. H. (1971). Science, 172, 567–570. CrossRef PubMed CAS Web of Science 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
Soliman, S. M., Elzawy, Z. B., Abu-Youssef, M. A. M., Albering, J., Gatterer, K., Öhrström, L. & Kettle, S. F. A. (2014). Acta Cryst. B70, 115–125. Web of Science CrossRef IUCr Journals Google Scholar
Stoe (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Suckert, S., Rams, M., Böhme, M., Germann, L. S., Dinnebier, R. E., Plass, W., Werner, J. & Näther, C. (2016). Dalton Trans. 45, 18190–18201. Web of Science CrossRef CAS PubMed Google Scholar
Suckert, S., Rams, M., Rams, M. R. & Näther, C. (2017a). Inorg. Chem. 56, 8007–8017. CrossRef CAS Google Scholar
Suckert, S., Werner, J., Jess, I. & Näther, C. (2017b). Acta Cryst. E73, 365–368. CrossRef IUCr Journals Google Scholar
Suckert, S., Werner, J., Jess, I. & Näther, C. (2017c). Acta Cryst. E73, 616–619. CrossRef IUCr Journals Google Scholar
Wellm, C. & Näther, C. (2018). Acta Cryst. E74, 1899–1902. CrossRef IUCr Journals Google Scholar
Wellm, C., Rams, M., Neumann, T., Ceglarska, M. & Näther, C. (2018). Cryst. Growth Des. 18, 3117–3123. CrossRef CAS Google Scholar
Werner, J., Rams, M., Tomkowicz, Z., Runčevski, T., Dinnebier, R. E., Suckert, S. & Näther, C. (2015). Inorg. Chem. 54, 2893–2901. Web of Science CrossRef CAS PubMed Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wöhlert, S., Fic, T., Tomkowicz, Z., Ebbinghaus, S. G., Rams, M., Haase, W. & Näther, C. (2013b). Inorg. Chem. 52, 12947–12957. Google Scholar
Wöhlert, S., Runčevski, T., Dinnebier, R., Ebbinghaus, S. & Näther, C. (2014a). Cryst. Growth Des. 14, 1902–1913. Google Scholar
Wöhlert, S., Tomkowicz, Z., Rams, M., Ebbinghaus, S. G., Fink, L., Schmidt, M. U. & Näther, C. (2014b). Inorg. Chem. 53, 8298–8310. Google Scholar
Wöhlert, S., Wriedt, M., Fic, T., Tomkowicz, Z., Haase, W. & Näther, C. (2013a). Inorg. Chem. 52, 1061–1068. Google Scholar

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