metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

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 NiII 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 NiII 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[Boeckmann, J. & Näther, C. (2010). Dalton Trans. 39, 11019-11026.], 2011[Boeckmann, J. & Näther, C. (2011). Chem. Commun. 47, 7104-7106.]); Wöhlert et al. (2011[Wöhlert, S., Boeckmann, J., Wriedt, M. & Näther, C. (2011). Angew. Chem. 50, 6920-6923.]). For structures of related trinuclear complexes, see: Wriedt & Näther (2009[Wriedt, M. & Näther, C. (2009). Z. Anorg. Allg. Chem. 635, 2459-2464.]); Yi et al. (2006[Yi, T., Ho-Chol, C., Gao, S. & Kitagawa, S. (2006). Eur. J. Inorg. Chem. 7, 1381-1387.]). For a description of the Cambridge Structural Database, see: Allen (2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]).

[Scheme 1]

Experimental

Crystal data
  • [Ni3(NCS)6(C4H4N2)4(CH4O)2]·4CH4O

  • Mr = 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[Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.]) Tmin = 0.746, Tmax = 0.818

  • 31891 measured reflections

  • 4093 independent reflections

  • 3190 reflections with I > 2σ(I)

  • Rint = 0.065

Refinement
  • R[F2 > 2σ(F2)] = 0.041

  • wR(F2) = 0.106

  • S = 1.05

  • 4093 reflections

  • 263 parameters

  • H-atom parameters constrained

  • Δρmax = 0.34 e Å−3

  • Δρmin = −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 DA 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[Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: XP in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and DIAMOND (Brandenburg, 2011)[Brandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany.]; software used to prepare material for publication: XCIF in SHELXTL.

Supporting information


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.

Refinement top

All H atoms were located in difference map but were positioned with idealized geometry and were refined isotropic with Uiso(H) = 1.2 Ueq(C) (1.5 for methyl H atoms) using a riding model with C—H = 0.95 for aromatic and 0.98 Å for methyl H atoms. The O—H H atoms were located in difference map, their bond lengths set to ideal values of 0.84 Å and afterwards they were refined using a riding model with Uiso(H) = 1.5 Ueq(O).

Structure description 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).

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
[Figure 1] 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.
[Figure 2] 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]·4CH4OF(000) = 2136
Mr = 1037.23Dx = 1.441 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 31891 reflections
a = 17.6689 (12) Åθ = 2.6–25.0°
b = 15.0760 (7) ŵ = 1.48 mm1
c = 17.9479 (10) ÅT = 200 K
V = 4780.9 (5) Å3Block, green
Z = 40.13 × 0.09 × 0.07 mm
Data collection top
Stoe IPDS-1
diffractometer
4093 independent reflections
Radiation source: fine-focus sealed tube3190 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.065
phi scanθmax = 25.0°, θmin = 2.6°
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
h = 2121
Tmin = 0.746, Tmax = 0.818k = 1716
31891 measured reflectionsl = 2121
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.106 w = 1/[σ2(Fo2) + (0.058P)2 + 2.6878P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
4093 reflectionsΔρmax = 0.34 e Å3
263 parametersΔρmin = 0.52 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0022 (4)
Crystal data top
[Ni3(NCS)6(C4H4N2)4(CH4O)2]·4CH4OV = 4780.9 (5) Å3
Mr = 1037.23Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 17.6689 (12) ŵ = 1.48 mm1
b = 15.0760 (7) ÅT = 200 K
c = 17.9479 (10) Å0.13 × 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)
Tmin = 0.746, Tmax = 0.818Rint = 0.065
31891 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.106H-atom parameters constrained
S = 1.05Δρmax = 0.34 e Å3
4093 reflectionsΔρmin = 0.52 e Å3
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
xyzUiso*/Ueq
Ni10.34256 (2)0.62044 (3)0.48362 (3)0.03445 (16)
Ni20.50000.50000.50000.02852 (17)
N10.28878 (17)0.7219 (2)0.5360 (2)0.0472 (8)
C10.2580 (2)0.7648 (3)0.5794 (2)0.0458 (9)
S10.21556 (8)0.82484 (12)0.64235 (8)0.0843 (5)
N20.40392 (14)0.51597 (19)0.43107 (17)0.0323 (6)
C20.38567 (18)0.4742 (3)0.3823 (2)0.0404 (9)
S20.36077 (8)0.41172 (10)0.31352 (7)0.0706 (4)
N30.24364 (17)0.5553 (2)0.46794 (19)0.0472 (8)
C30.1898 (2)0.5208 (3)0.44548 (19)0.0376 (8)
S30.11289 (6)0.47346 (8)0.41480 (6)0.0539 (3)
N100.36318 (14)0.5577 (2)0.58671 (16)0.0340 (7)
N110.42715 (14)0.50917 (19)0.59358 (16)0.0322 (6)
C100.3176 (2)0.5655 (3)0.6453 (2)0.0434 (9)
H100.27210.59820.63970.052*
C110.3333 (2)0.5282 (3)0.7143 (2)0.0500 (10)
H110.30030.53670.75560.060*
C120.3977 (2)0.4789 (3)0.7208 (2)0.0471 (10)
H120.41090.45130.76660.057*
C130.4432 (2)0.4704 (3)0.65802 (19)0.0381 (8)
H130.48780.43540.66140.046*
N200.44811 (15)0.6868 (2)0.49603 (16)0.0351 (6)
N210.51239 (15)0.63848 (19)0.49894 (15)0.0319 (6)
C200.4517 (2)0.7741 (3)0.4989 (2)0.0448 (9)
H200.40590.80700.49780.054*
C210.5200 (2)0.8203 (3)0.5035 (2)0.0516 (10)
H210.52100.88330.50490.062*
C220.5851 (2)0.7719 (3)0.5060 (2)0.0459 (9)
H220.63310.79980.50960.055*
C230.57830 (18)0.6801 (2)0.50301 (19)0.0361 (8)
H230.62320.64540.50390.043*
O10.33376 (15)0.6840 (2)0.38195 (16)0.0551 (8)
H1O10.36910.68850.35090.083*
C300.2715 (3)0.7345 (4)0.3553 (3)0.0757 (16)
H30A0.26120.78330.38990.114*
H30B0.22680.69640.35160.114*
H30C0.28370.75860.30600.114*
O20.4433 (2)0.8203 (3)0.7794 (2)0.0830 (12)
H1O20.41440.83680.74490.125*
C310.4798 (6)0.7414 (7)0.7589 (6)0.175 (5)
H31A0.50990.75150.71390.263*
H31B0.44190.69530.74920.263*
H31C0.51310.72210.79950.263*
O30.3907 (4)0.8965 (6)0.6541 (4)0.155 (3)
H1O30.34610.87790.65010.232*
C320.4027 (5)0.9850 (8)0.6309 (5)0.139 (4)
H32A0.37271.02510.66220.209*
H32B0.38710.99150.57880.209*
H32C0.45640.99980.63580.209*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0228 (2)0.0333 (3)0.0473 (3)0.00354 (17)0.00013 (17)0.00294 (19)
Ni20.0208 (3)0.0264 (3)0.0384 (3)0.0023 (2)0.0014 (2)0.0010 (2)
N10.0294 (15)0.042 (2)0.070 (2)0.0081 (14)0.0004 (15)0.0047 (16)
C10.0334 (18)0.041 (3)0.063 (2)0.0136 (17)0.0067 (17)0.0058 (19)
S10.0679 (8)0.1127 (13)0.0722 (8)0.0446 (8)0.0053 (6)0.0333 (8)
N20.0231 (13)0.0239 (16)0.0501 (18)0.0047 (11)0.0058 (12)0.0018 (13)
C20.0242 (17)0.046 (2)0.050 (2)0.0069 (15)0.0033 (15)0.0134 (19)
S20.0730 (8)0.0795 (10)0.0592 (7)0.0096 (7)0.0096 (6)0.0177 (6)
N30.0301 (16)0.051 (2)0.060 (2)0.0013 (14)0.0017 (14)0.0052 (16)
C30.0341 (18)0.036 (2)0.0425 (19)0.0008 (16)0.0020 (15)0.0024 (15)
S30.0455 (6)0.0616 (8)0.0546 (6)0.0195 (5)0.0071 (4)0.0018 (5)
N100.0232 (13)0.0337 (18)0.0451 (16)0.0009 (11)0.0038 (11)0.0057 (12)
N110.0244 (13)0.0290 (17)0.0430 (15)0.0017 (11)0.0010 (11)0.0024 (12)
C100.0339 (18)0.046 (2)0.051 (2)0.0026 (16)0.0093 (16)0.0062 (17)
C110.047 (2)0.054 (3)0.049 (2)0.0013 (19)0.0137 (17)0.0095 (18)
C120.046 (2)0.057 (3)0.0386 (19)0.0019 (19)0.0024 (16)0.0018 (17)
C130.0321 (17)0.039 (2)0.0428 (19)0.0007 (15)0.0031 (15)0.0005 (15)
N200.0281 (14)0.0290 (18)0.0481 (17)0.0037 (12)0.0010 (12)0.0002 (12)
N210.0214 (13)0.0326 (16)0.0415 (15)0.0031 (11)0.0010 (11)0.0007 (11)
C200.0324 (18)0.030 (2)0.072 (3)0.0039 (14)0.0003 (17)0.0004 (18)
C210.046 (2)0.030 (2)0.079 (3)0.0041 (17)0.003 (2)0.0016 (18)
C220.0332 (18)0.037 (2)0.067 (3)0.0069 (15)0.0010 (17)0.0002 (18)
C230.0241 (16)0.034 (2)0.050 (2)0.0011 (13)0.0007 (14)0.0031 (15)
O10.0385 (15)0.065 (2)0.0616 (17)0.0151 (13)0.0002 (12)0.0150 (14)
C300.052 (3)0.101 (5)0.074 (3)0.032 (3)0.011 (2)0.019 (3)
O20.063 (2)0.092 (3)0.094 (3)0.019 (2)0.0164 (19)0.035 (2)
C310.180 (10)0.115 (8)0.231 (12)0.009 (7)0.093 (9)0.047 (8)
O30.107 (4)0.235 (9)0.122 (5)0.031 (5)0.010 (4)0.054 (5)
C320.080 (5)0.248 (13)0.090 (5)0.007 (7)0.005 (4)0.025 (7)
Geometric parameters (Å, º) top
Ni1—N32.024 (3)C13—H130.9500
Ni1—N12.031 (3)N20—C201.319 (5)
Ni1—O12.067 (3)N20—N211.350 (4)
Ni1—N102.110 (3)N21—C231.325 (4)
Ni1—N202.128 (3)C20—C211.395 (6)
Ni1—N22.132 (3)C20—H200.9500
Ni2—N21i2.099 (3)C21—C221.363 (6)
Ni2—N212.099 (3)C21—H210.9500
Ni2—N22.114 (3)C22—C231.391 (5)
Ni2—N2i2.114 (3)C22—H220.9500
Ni2—N11i2.121 (3)C23—H230.9500
Ni2—N112.121 (3)O1—C301.420 (5)
N1—C11.149 (5)O1—H1O10.8399
C1—S11.631 (4)C30—H30A0.9800
N2—C21.126 (5)C30—H30B0.9800
C2—S21.614 (5)C30—H30C0.9800
N3—C31.156 (5)O2—C311.403 (9)
C3—S31.631 (4)O2—H1O20.8399
N10—C101.329 (5)C31—H31A0.9800
N10—N111.352 (4)C31—H31B0.9800
N11—C131.327 (5)C31—H31C0.9800
C10—C111.388 (6)O3—C321.413 (11)
C10—H100.9500O3—H1O30.8401
C11—C121.364 (6)C32—H32A0.9800
C11—H110.9500C32—H32B0.9800
C12—C131.391 (5)C32—H32C0.9800
C12—H120.9500
N3—Ni1—N191.48 (13)C10—C11—H11121.2
N3—Ni1—O192.14 (13)C11—C12—C13117.6 (4)
N1—Ni1—O191.36 (13)C11—C12—H12121.2
N3—Ni1—N1093.07 (13)C13—C12—H12121.2
N1—Ni1—N1090.74 (13)N11—C13—C12122.8 (3)
O1—Ni1—N10174.33 (10)N11—C13—H13118.6
N3—Ni1—N20177.73 (13)C12—C13—H13118.6
N1—Ni1—N2090.42 (12)C20—N20—N21119.8 (3)
O1—Ni1—N2086.57 (11)C20—N20—Ni1121.1 (2)
N10—Ni1—N2088.15 (11)N21—N20—Ni1119.2 (2)
N3—Ni1—N291.10 (12)C23—N21—N20119.1 (3)
N1—Ni1—N2177.27 (12)C23—N21—Ni2124.2 (2)
O1—Ni1—N289.45 (11)N20—N21—Ni2116.7 (2)
N10—Ni1—N288.22 (11)N20—C20—C21122.9 (3)
N20—Ni1—N287.02 (11)N20—C20—H20118.6
N21i—Ni2—N21180.0C21—C20—H20118.6
N21i—Ni2—N291.99 (11)C22—C21—C20117.6 (4)
N21—Ni2—N288.01 (11)C22—C21—H21121.2
N21i—Ni2—N2i88.01 (11)C20—C21—H21121.2
N21—Ni2—N2i91.99 (11)C21—C22—C23117.3 (3)
N2—Ni2—N2i180.0C21—C22—H22121.3
N21i—Ni2—N11i90.32 (10)C23—C22—H22121.3
N21—Ni2—N11i89.68 (10)N21—C23—C22123.3 (3)
N2—Ni2—N11i91.80 (11)N21—C23—H23118.4
N2i—Ni2—N11i88.20 (11)C22—C23—H23118.4
N21i—Ni2—N1189.68 (10)C30—O1—Ni1127.1 (3)
N21—Ni2—N1190.32 (10)C30—O1—H1O1108.0
N2—Ni2—N1188.20 (11)Ni1—O1—H1O1124.6
N2i—Ni2—N1191.80 (11)O1—C30—H30A109.5
N11i—Ni2—N11180.000 (1)O1—C30—H30B109.5
C1—N1—Ni1163.4 (4)H30A—C30—H30B109.5
N1—C1—S1178.9 (4)O1—C30—H30C109.5
C2—N2—Ni2128.4 (3)H30A—C30—H30C109.5
C2—N2—Ni1127.7 (3)H30B—C30—H30C109.5
Ni2—N2—Ni1103.51 (13)C31—O2—H1O2109.7
N2—C2—S2178.2 (4)O2—C31—H31A109.5
C3—N3—Ni1167.6 (3)O2—C31—H31B109.5
N3—C3—S3178.8 (4)H31A—C31—H31B109.5
C10—N10—N11118.8 (3)O2—C31—H31C109.5
C10—N10—Ni1123.4 (2)H31A—C31—H31C109.5
N11—N10—Ni1117.8 (2)H31B—C31—H31C109.5
C13—N11—N10119.8 (3)C32—O3—H1O3115.6
C13—N11—Ni2122.1 (2)O3—C32—H32A109.5
N10—N11—Ni2118.1 (2)O3—C32—H32B109.5
N10—C10—C11123.4 (4)H32A—C32—H32B109.5
N10—C10—H10118.3O3—C32—H32C109.5
C11—C10—H10118.3H32A—C32—H32C109.5
C12—C11—C10117.6 (3)H32B—C32—H32C109.5
C12—C11—H11121.2
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O1···O2ii0.841.842.671 (4)171
O2—H1O2···O30.841.912.691 (9)155
O3—H1O3···S10.842.453.285 (6)178
Symmetry code: (ii) x, y+3/2, z1/2.

Experimental details

Crystal data
Chemical formula[Ni3(NCS)6(C4H4N2)4(CH4O)2]·4CH4O
Mr1037.23
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)200
a, b, c (Å)17.6689 (12), 15.0760 (7), 17.9479 (10)
V3)4780.9 (5)
Z4
Radiation typeMo Kα
µ (mm1)1.48
Crystal size (mm)0.13 × 0.09 × 0.07
Data collection
DiffractometerStoe IPDS1
Absorption correctionNumerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
Tmin, Tmax0.746, 0.818
No. of measured, independent and
observed [I > 2σ(I)] reflections
31891, 4093, 3190
Rint0.065
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.106, 1.05
No. of reflections4093
No. of parameters263
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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—N32.024 (3)Ni1—N22.132 (3)
Ni1—N12.031 (3)Ni2—N212.099 (3)
Ni1—O12.067 (3)Ni2—N22.114 (3)
Ni1—N102.110 (3)Ni2—N112.121 (3)
Ni1—N202.128 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O1···O2i0.841.842.671 (4)170.9
O2—H1O2···O30.841.912.691 (9)154.5
O3—H1O3···S10.842.453.285 (6)178.3
Symmetry code: (i) x, y+3/2, z1/2.
 

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

First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationBoeckmann, J. & Näther, C. (2010). Dalton Trans. 39, 11019–11026.  Web of Science CSD CrossRef CAS PubMed Google Scholar
First citationBoeckmann, J. & Näther, C. (2011). Chem. Commun. 47, 7104–7106.  Web of Science CSD CrossRef CAS Google Scholar
First citationBrandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationStoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.  Google Scholar
First citationWöhlert, S., Boeckmann, J., Wriedt, M. & Näther, C. (2011). Angew. Chem. 50, 6920–6923.  Google Scholar
First citationWriedt, M. & Näther, C. (2009). Z. Anorg. Allg. Chem. 635, 2459–2464.  Web of Science CSD CrossRef CAS Google Scholar
First citationYi, T., Ho-Chol, C., Gao, S. & Kitagawa, S. (2006). Eur. J. Inorg. Chem. 7, 1381–1387.  Web of Science CSD CrossRef Google Scholar

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