Bis(methanol-1κO)tetra-μ-pyridazine-1:2κ4N:N′;2:3κ4N:N′-di-μ-thio­cyanato-1:2κ2N:N;2:3κ2N:N-tetrathio­cyanato-1κ2N,3κ2N-trinickel(II) methanol tetra­solvate

Wöhlert, S.; Jess, I.; Näther, C.

doi:10.1107/S1600536812026864

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Pages m940-m941

https://doi.org/10.1107/S1600536812026864

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Bis(methanol-1κO)tetra-μ-pyridazine-1:2κ⁴N:N′;2:3κ⁴N:N′-di-μ-thiocyanato-1:2κ²N:N;2:3κ²N:N-tetrathiocyanato-1κ²N,3κ²N-trinickel(II) methanol tetrasolvate

Susanne Wöhlert,^a ^* Inke Jess ^a and Christian Näther ^a

^aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth-Strasse 2, 24118 Kiel, Germany
^*Correspondence e-mail: swoehlert@ac.uni-kiel.de

(Received 14 May 2012; accepted 13 June 2012; online 16 June 2012)

Reaction of an excess nickel(II) thiocyanate with pyridazine leads to single crystals of the title compound, [Ni₃(NCS)₆(N₂C₄H₄)₄(CH₃OH)₂]·4CH₃OH. The crystal structure consists of trimeric discrete complexes, in which two Ni^II cations are coordinated by two terminal and one μ-1,1 bridging thiocyanato anions, one methanol molecule and two bridging pyridazine ligands, whereas the central Ni^II atom is coordinated by two μ-1,1 bridging anions as well as four bridging pyridazine ligands. The asymmetric unit consists of two crystallographically independent Ni cations, one of which is located on a center of inversion, as well as three crystallographically independent thiocyanato anions, two pyridazine ligands and three independent methanol molecules in general positions. Two of the solvent molecules do not coordinate to the metal atoms and are located in cavities of the structure. The discrete complexes are linked by intermolecular O—H⋯O and O—H⋯S hydrogen bonding into layers parallel to the bc plane.

Related literature

For the background to this work and the synthesis of bridging thiocyanato coordination compounds, see: Boeckmann & Näther (2010 , 2011 ); Wöhlert et al. (2011 ). For structures of related trinuclear complexes, see: Wriedt & Näther (2009 ); Yi et al. (2006 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

[Ni₃(NCS)₆(C₄H₄N₂)₄(CH₄O)₂]·4CH₄O
M_r = 1037.23
Orthorhombic, P b c a
a = 17.6689 (12) Å
b = 15.0760 (7) Å
c = 17.9479 (10) Å
V = 4780.9 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.48 mm⁻¹
T = 200 K
0.13 × 0.09 × 0.07 mm

Data collection

Stoe IPDS-1 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ) T_min = 0.746, T_max = 0.818
31891 measured reflections
4093 independent reflections
3190 reflections with I > 2σ(I)
R_int = 0.065

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.106
S = 1.05
4093 reflections
263 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—N3	2.024 (3)
Ni1—N1	2.031 (3)
Ni1—O1	2.067 (3)
Ni1—N10	2.110 (3)
Ni1—N20	2.128 (3)
Ni1—N2	2.132 (3)
Ni2—N21	2.099 (3)
Ni2—N2	2.114 (3)
Ni2—N11	2.121 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O2ⁱ	0.84	1.84	2.671 (4)	171
O2—H1O2⋯O3	0.84	1.91	2.691 (9)	155
O3—H1O3⋯S1	0.84	2.45	3.285 (6)	178
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: XCIF in SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812026864/hp2040sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812026864/hp2040Isup2.hkl

checkCIF report

Comment top

The structure determination of the title compound was performed within a project on the synthesis of transition metal coordination compounds in which the metal centers are linked by bridging anionic ligands (Boeckmann & Näther (2010, 2011); Wöhlert et al. (2011)). Within this project we reported on two modification of a trinuclear complex based on nickel(II) thiocyanate and pyridazine (Wriedt & Näther (2009)). In further investigations we have reacted nickel(II) thiocyanate with pyridazine in methanol which results in the formation of single-crystals of the title compound, which were characterized by single-crystal X-ray diffraction. The asymmetric unit of the title compound consists of two nickel(II) cations, one of them is located on a center of inversion, three thiocyanato anions, two pyridazine ligands and three methanol molecules all of them located in general position (Fig. 1). In the crystal structure two crystallographic independent nickel(II) cations are present. Ni1 is coordinated by two terminal N-bonded and one µ-1,1 bridging thiocyanato anions, one methanol molecule and two bridging pyridazine ligands in a slightly distorted octahedral geometry (Tab. 1). Ni2 is coordinated by two µ-1,1 bridging thiocyanato anions and four pyridazine ligands and the coordination environment can also be described as a sligthly distorted octahedron (Tab. 1). The nickel(II) cations are connected through µ-1,1 bridging thiocyanato anions and the two µ₂-N,N pyridazine ligands into trimeric units. The Ni—N distances are in range of 2.025 (3) Å to 2.133 (3) Å with angles between 86.53 (12) ° to 180 ° (Tab. 1). The intramolecular Ni···Ni distances amount to 3.3349 (4) Å. The crystal structure contains additional methanol molecules located in cavities of the structure which are not coordinated to the metal cations. These methanol molecules are linked by intermolecular O—H···O and O—H···S hydrogen bonding to the metal complexes forming layers which are parallel to the b-c plane (Fig. 2 and Tab. 2). It must be noted that according to a search in the CCDC database (CONQUEST Ver. 1 12.2010) (Allen, 2002) a trinuclear complex with cobalt(II) thiocyanate and pyridazine was reported by Yi et al. (2006).

Related literature top

For the background to this work and the synthesis of bridging thiocyanato coordination compounds, see: Boeckmann & Näther (2010, 2011); Wöhlert et al. (2011). For structures of related trinuclear complexes, see: Wriedt & Näther (2009); Yi et al. (2006). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

Nickel(II) thiocyanate (Ni(NCS)₂) and pyridazine were obtained from Alfa Aesar. All chemicals were used without further purification. 0.5 mmol (87.0 mg) and 0.125 mmol (9.1 µL) pyridazine were reacted in 0.5 ml methanol. Green single crystals of the title compound were obtained after two days.

Structure description top

For the background to this work and the synthesis of bridging thiocyanato coordination compounds, see: Boeckmann & Näther (2010, 2011); Wöhlert et al. (2011). For structures of related trinuclear complexes, see: Wriedt & Näther (2009); Yi et al. (2006). For a description of the Cambridge Structural Database, see: Allen (2002).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: XCIF in SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. : Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 30% probability level. Symmetry code: i = -x + 1, -y + 1, -z + 1.
	Fig. 2. : Crystal structure of the title compound with view along the a-axis. Intermolecular O—H···O and O—H···S hydrogen bonding is shown as dashed lines.

Bis(methanol-1κO)tetra-µ-pyridazine- 1:2κ⁴N:N';2:3κ⁴N:N'-di-µ-thiocyanato- 1:2κ²N:N;2:3κ²N:N-tetrathiocyanato- 1κ²N,3κ²N-trinickel(II) methanol tetrasolvate top

Crystal data top

[Ni₃(NCS)₆(C₄H₄N₂)₄(CH₄O)₂]·4CH₄O	F(000) = 2136
M_r = 1037.23	D_x = 1.441 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 31891 reflections
a = 17.6689 (12) Å	θ = 2.6–25.0°
b = 15.0760 (7) Å	µ = 1.48 mm⁻¹
c = 17.9479 (10) Å	T = 200 K
V = 4780.9 (5) Å³	Block, green
Z = 4	0.13 × 0.09 × 0.07 mm

Data collection top

Stoe IPDS-1 diffractometer	4093 independent reflections
Radiation source: fine-focus sealed tube	3190 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
phi scan	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −21→21
T_min = 0.746, T_max = 0.818	k = −17→16
31891 measured reflections	l = −21→21

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.106	w = 1/[σ²(F_o²) + (0.058P)² + 2.6878P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
4093 reflections	Δρ_max = 0.34 e Å⁻³
263 parameters	Δρ_min = −0.52 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0022 (4)

Crystal data top

[Ni₃(NCS)₆(C₄H₄N₂)₄(CH₄O)₂]·4CH₄O	V = 4780.9 (5) Å³
M_r = 1037.23	Z = 4
Orthorhombic, Pbca	Mo Kα radiation
a = 17.6689 (12) Å	µ = 1.48 mm⁻¹
b = 15.0760 (7) Å	T = 200 K
c = 17.9479 (10) Å	0.13 × 0.09 × 0.07 mm

Data collection top

Stoe IPDS-1 diffractometer	4093 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	3190 reflections with I > 2σ(I)
T_min = 0.746, T_max = 0.818	R_int = 0.065
31891 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.05	Δρ_max = 0.34 e Å⁻³
4093 reflections	Δρ_min = −0.52 e Å⁻³
263 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Ni1	0.34256 (2)	0.62044 (3)	0.48362 (3)	0.03445 (16)
Ni2	0.5000	0.5000	0.5000	0.02852 (17)
N1	0.28878 (17)	0.7219 (2)	0.5360 (2)	0.0472 (8)
C1	0.2580 (2)	0.7648 (3)	0.5794 (2)	0.0458 (9)
S1	0.21556 (8)	0.82484 (12)	0.64235 (8)	0.0843 (5)
N2	0.40392 (14)	0.51597 (19)	0.43107 (17)	0.0323 (6)
C2	0.38567 (18)	0.4742 (3)	0.3823 (2)	0.0404 (9)
S2	0.36077 (8)	0.41172 (10)	0.31352 (7)	0.0706 (4)
N3	0.24364 (17)	0.5553 (2)	0.46794 (19)	0.0472 (8)
C3	0.1898 (2)	0.5208 (3)	0.44548 (19)	0.0376 (8)
S3	0.11289 (6)	0.47346 (8)	0.41480 (6)	0.0539 (3)
N10	0.36318 (14)	0.5577 (2)	0.58671 (16)	0.0340 (7)
N11	0.42715 (14)	0.50917 (19)	0.59358 (16)	0.0322 (6)
C10	0.3176 (2)	0.5655 (3)	0.6453 (2)	0.0434 (9)
H10	0.2721	0.5982	0.6397	0.052*
C11	0.3333 (2)	0.5282 (3)	0.7143 (2)	0.0500 (10)
H11	0.3003	0.5367	0.7556	0.060*
C12	0.3977 (2)	0.4789 (3)	0.7208 (2)	0.0471 (10)
H12	0.4109	0.4513	0.7666	0.057*
C13	0.4432 (2)	0.4704 (3)	0.65802 (19)	0.0381 (8)
H13	0.4878	0.4354	0.6614	0.046*
N20	0.44811 (15)	0.6868 (2)	0.49603 (16)	0.0351 (6)
N21	0.51239 (15)	0.63848 (19)	0.49894 (15)	0.0319 (6)
C20	0.4517 (2)	0.7741 (3)	0.4989 (2)	0.0448 (9)
H20	0.4059	0.8070	0.4978	0.054*
C21	0.5200 (2)	0.8203 (3)	0.5035 (2)	0.0516 (10)
H21	0.5210	0.8833	0.5049	0.062*
C22	0.5851 (2)	0.7719 (3)	0.5060 (2)	0.0459 (9)
H22	0.6331	0.7998	0.5096	0.055*
C23	0.57830 (18)	0.6801 (2)	0.50301 (19)	0.0361 (8)
H23	0.6232	0.6454	0.5039	0.043*
O1	0.33376 (15)	0.6840 (2)	0.38195 (16)	0.0551 (8)
H1O1	0.3691	0.6885	0.3509	0.083*
C30	0.2715 (3)	0.7345 (4)	0.3553 (3)	0.0757 (16)
H30A	0.2612	0.7833	0.3899	0.114*
H30B	0.2268	0.6964	0.3516	0.114*
H30C	0.2837	0.7586	0.3060	0.114*
O2	0.4433 (2)	0.8203 (3)	0.7794 (2)	0.0830 (12)
H1O2	0.4144	0.8368	0.7449	0.125*
C31	0.4798 (6)	0.7414 (7)	0.7589 (6)	0.175 (5)
H31A	0.5099	0.7515	0.7139	0.263*
H31B	0.4419	0.6953	0.7492	0.263*
H31C	0.5131	0.7221	0.7995	0.263*
O3	0.3907 (4)	0.8965 (6)	0.6541 (4)	0.155 (3)
H1O3	0.3461	0.8779	0.6501	0.232*
C32	0.4027 (5)	0.9850 (8)	0.6309 (5)	0.139 (4)
H32A	0.3727	1.0251	0.6622	0.209*
H32B	0.3871	0.9915	0.5788	0.209*
H32C	0.4564	0.9998	0.6358	0.209*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0228 (2)	0.0333 (3)	0.0473 (3)	0.00354 (17)	−0.00013 (17)	−0.00294 (19)
Ni2	0.0208 (3)	0.0264 (3)	0.0384 (3)	0.0023 (2)	0.0014 (2)	−0.0010 (2)
N1	0.0294 (15)	0.042 (2)	0.070 (2)	0.0081 (14)	−0.0004 (15)	−0.0047 (16)
C1	0.0334 (18)	0.041 (3)	0.063 (2)	0.0136 (17)	−0.0067 (17)	−0.0058 (19)
S1	0.0679 (8)	0.1127 (13)	0.0722 (8)	0.0446 (8)	−0.0053 (6)	−0.0333 (8)
N2	0.0231 (13)	0.0239 (16)	0.0501 (18)	0.0047 (11)	0.0058 (12)	0.0018 (13)
C2	0.0242 (17)	0.046 (2)	0.050 (2)	0.0069 (15)	0.0033 (15)	0.0134 (19)
S2	0.0730 (8)	0.0795 (10)	0.0592 (7)	−0.0096 (7)	−0.0096 (6)	−0.0177 (6)
N3	0.0301 (16)	0.051 (2)	0.060 (2)	−0.0013 (14)	−0.0017 (14)	−0.0052 (16)
C3	0.0341 (18)	0.036 (2)	0.0425 (19)	0.0008 (16)	0.0020 (15)	0.0024 (15)
S3	0.0455 (6)	0.0616 (8)	0.0546 (6)	−0.0195 (5)	−0.0071 (4)	0.0018 (5)
N10	0.0232 (13)	0.0337 (18)	0.0451 (16)	0.0009 (11)	0.0038 (11)	−0.0057 (12)
N11	0.0244 (13)	0.0290 (17)	0.0430 (15)	0.0017 (11)	0.0010 (11)	−0.0024 (12)
C10	0.0339 (18)	0.046 (2)	0.051 (2)	0.0026 (16)	0.0093 (16)	−0.0062 (17)
C11	0.047 (2)	0.054 (3)	0.049 (2)	−0.0013 (19)	0.0137 (17)	−0.0095 (18)
C12	0.046 (2)	0.057 (3)	0.0386 (19)	−0.0019 (19)	0.0024 (16)	−0.0018 (17)
C13	0.0321 (17)	0.039 (2)	0.0428 (19)	0.0007 (15)	0.0031 (15)	0.0005 (15)
N20	0.0281 (14)	0.0290 (18)	0.0481 (17)	0.0037 (12)	−0.0010 (12)	−0.0002 (12)
N21	0.0214 (13)	0.0326 (16)	0.0415 (15)	0.0031 (11)	0.0010 (11)	0.0007 (11)
C20	0.0324 (18)	0.030 (2)	0.072 (3)	0.0039 (14)	0.0003 (17)	0.0004 (18)
C21	0.046 (2)	0.030 (2)	0.079 (3)	−0.0041 (17)	−0.003 (2)	0.0016 (18)
C22	0.0332 (18)	0.037 (2)	0.067 (3)	−0.0069 (15)	−0.0010 (17)	0.0002 (18)
C23	0.0241 (16)	0.034 (2)	0.050 (2)	−0.0011 (13)	0.0007 (14)	0.0031 (15)
O1	0.0385 (15)	0.065 (2)	0.0616 (17)	0.0151 (13)	0.0002 (12)	0.0150 (14)
C30	0.052 (3)	0.101 (5)	0.074 (3)	0.032 (3)	−0.011 (2)	0.019 (3)
O2	0.063 (2)	0.092 (3)	0.094 (3)	−0.019 (2)	0.0164 (19)	−0.035 (2)
C31	0.180 (10)	0.115 (8)	0.231 (12)	0.009 (7)	0.093 (9)	−0.047 (8)
O3	0.107 (4)	0.235 (9)	0.122 (5)	−0.031 (5)	−0.010 (4)	−0.054 (5)
C32	0.080 (5)	0.248 (13)	0.090 (5)	−0.007 (7)	0.005 (4)	−0.025 (7)

Geometric parameters (Å, º) top

Ni1—N3	2.024 (3)	C13—H13	0.9500
Ni1—N1	2.031 (3)	N20—C20	1.319 (5)
Ni1—O1	2.067 (3)	N20—N21	1.350 (4)
Ni1—N10	2.110 (3)	N21—C23	1.325 (4)
Ni1—N20	2.128 (3)	C20—C21	1.395 (6)
Ni1—N2	2.132 (3)	C20—H20	0.9500
Ni2—N21ⁱ	2.099 (3)	C21—C22	1.363 (6)
Ni2—N21	2.099 (3)	C21—H21	0.9500
Ni2—N2	2.114 (3)	C22—C23	1.391 (5)
Ni2—N2ⁱ	2.114 (3)	C22—H22	0.9500
Ni2—N11ⁱ	2.121 (3)	C23—H23	0.9500
Ni2—N11	2.121 (3)	O1—C30	1.420 (5)
N1—C1	1.149 (5)	O1—H1O1	0.8399
C1—S1	1.631 (4)	C30—H30A	0.9800
N2—C2	1.126 (5)	C30—H30B	0.9800
C2—S2	1.614 (5)	C30—H30C	0.9800
N3—C3	1.156 (5)	O2—C31	1.403 (9)
C3—S3	1.631 (4)	O2—H1O2	0.8399
N10—C10	1.329 (5)	C31—H31A	0.9800
N10—N11	1.352 (4)	C31—H31B	0.9800
N11—C13	1.327 (5)	C31—H31C	0.9800
C10—C11	1.388 (6)	O3—C32	1.413 (11)
C10—H10	0.9500	O3—H1O3	0.8401
C11—C12	1.364 (6)	C32—H32A	0.9800
C11—H11	0.9500	C32—H32B	0.9800
C12—C13	1.391 (5)	C32—H32C	0.9800
C12—H12	0.9500

N3—Ni1—N1	91.48 (13)	C10—C11—H11	121.2
N3—Ni1—O1	92.14 (13)	C11—C12—C13	117.6 (4)
N1—Ni1—O1	91.36 (13)	C11—C12—H12	121.2
N3—Ni1—N10	93.07 (13)	C13—C12—H12	121.2
N1—Ni1—N10	90.74 (13)	N11—C13—C12	122.8 (3)
O1—Ni1—N10	174.33 (10)	N11—C13—H13	118.6
N3—Ni1—N20	177.73 (13)	C12—C13—H13	118.6
N1—Ni1—N20	90.42 (12)	C20—N20—N21	119.8 (3)
O1—Ni1—N20	86.57 (11)	C20—N20—Ni1	121.1 (2)
N10—Ni1—N20	88.15 (11)	N21—N20—Ni1	119.2 (2)
N3—Ni1—N2	91.10 (12)	C23—N21—N20	119.1 (3)
N1—Ni1—N2	177.27 (12)	C23—N21—Ni2	124.2 (2)
O1—Ni1—N2	89.45 (11)	N20—N21—Ni2	116.7 (2)
N10—Ni1—N2	88.22 (11)	N20—C20—C21	122.9 (3)
N20—Ni1—N2	87.02 (11)	N20—C20—H20	118.6
N21ⁱ—Ni2—N21	180.0	C21—C20—H20	118.6
N21ⁱ—Ni2—N2	91.99 (11)	C22—C21—C20	117.6 (4)
N21—Ni2—N2	88.01 (11)	C22—C21—H21	121.2
N21ⁱ—Ni2—N2ⁱ	88.01 (11)	C20—C21—H21	121.2
N21—Ni2—N2ⁱ	91.99 (11)	C21—C22—C23	117.3 (3)
N2—Ni2—N2ⁱ	180.0	C21—C22—H22	121.3
N21ⁱ—Ni2—N11ⁱ	90.32 (10)	C23—C22—H22	121.3
N21—Ni2—N11ⁱ	89.68 (10)	N21—C23—C22	123.3 (3)
N2—Ni2—N11ⁱ	91.80 (11)	N21—C23—H23	118.4
N2ⁱ—Ni2—N11ⁱ	88.20 (11)	C22—C23—H23	118.4
N21ⁱ—Ni2—N11	89.68 (10)	C30—O1—Ni1	127.1 (3)
N21—Ni2—N11	90.32 (10)	C30—O1—H1O1	108.0
N2—Ni2—N11	88.20 (11)	Ni1—O1—H1O1	124.6
N2ⁱ—Ni2—N11	91.80 (11)	O1—C30—H30A	109.5
N11ⁱ—Ni2—N11	180.000 (1)	O1—C30—H30B	109.5
C1—N1—Ni1	163.4 (4)	H30A—C30—H30B	109.5
N1—C1—S1	178.9 (4)	O1—C30—H30C	109.5
C2—N2—Ni2	128.4 (3)	H30A—C30—H30C	109.5
C2—N2—Ni1	127.7 (3)	H30B—C30—H30C	109.5
Ni2—N2—Ni1	103.51 (13)	C31—O2—H1O2	109.7
N2—C2—S2	178.2 (4)	O2—C31—H31A	109.5
C3—N3—Ni1	167.6 (3)	O2—C31—H31B	109.5
N3—C3—S3	178.8 (4)	H31A—C31—H31B	109.5
C10—N10—N11	118.8 (3)	O2—C31—H31C	109.5
C10—N10—Ni1	123.4 (2)	H31A—C31—H31C	109.5
N11—N10—Ni1	117.8 (2)	H31B—C31—H31C	109.5
C13—N11—N10	119.8 (3)	C32—O3—H1O3	115.6
C13—N11—Ni2	122.1 (2)	O3—C32—H32A	109.5
N10—N11—Ni2	118.1 (2)	O3—C32—H32B	109.5
N10—C10—C11	123.4 (4)	H32A—C32—H32B	109.5
N10—C10—H10	118.3	O3—C32—H32C	109.5
C11—C10—H10	118.3	H32A—C32—H32C	109.5
C12—C11—C10	117.6 (3)	H32B—C32—H32C	109.5
C12—C11—H11	121.2

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O2ⁱⁱ	0.84	1.84	2.671 (4)	171
O2—H1O2···O3	0.84	1.91	2.691 (9)	155
O3—H1O3···S1	0.84	2.45	3.285 (6)	178

Symmetry code: (ii) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[Ni₃(NCS)₆(C₄H₄N₂)₄(CH₄O)₂]·4CH₄O
M_r	1037.23
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	200
a, b, c (Å)	17.6689 (12), 15.0760 (7), 17.9479 (10)
V (Å³)	4780.9 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.48
Crystal size (mm)	0.13 × 0.09 × 0.07

Data collection
Diffractometer	Stoe IPDS1
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)
T_min, T_max	0.746, 0.818
No. of measured, independent and observed [I > 2σ(I)] reflections	31891, 4093, 3190
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.106, 1.05
No. of reflections	4093
No. of parameters	263
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.52

Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011), XCIF in SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Ni1—N3	2.024 (3)	Ni1—N2	2.132 (3)
Ni1—N1	2.031 (3)	Ni2—N21	2.099 (3)
Ni1—O1	2.067 (3)	Ni2—N2	2.114 (3)
Ni1—N10	2.110 (3)	Ni2—N11	2.121 (3)
Ni1—N20	2.128 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O2ⁱ	0.84	1.84	2.671 (4)	170.9
O2—H1O2···O3	0.84	1.91	2.691 (9)	154.5
O3—H1O3···S1	0.84	2.45	3.285 (6)	178.3

Symmetry code: (i) x, −y+3/2, z−1/2.

Acknowledgements

We gratefully acknowledge financial support by the DFG (project No. NA 720/3–1) and the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facility.

References

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