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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 67| Part 10| October 2011| Pages m1417-m1418
https://doi.org/10.1107/S1600536811037809

Bis(1,4,7-tri­thia­cyclo­nona­ne)nickel(II) bis­­(tetra­fluorido­borate) nitro­methane disolvate

John P. Lee,a* Gregory J. Granta and Bruce C. Nollb

aDepartment of Chemistry, The University of Tennessee at Chattanoga, Chattanooga, TN 37403, USA, and bCrystallographic Systems, Bruker AXS Inc., 5465 East Cheryl Parkway, Madison, WI 53711, USA
*Correspondence e-mail: John-Lee@utc.edu

(Received 28 June 2011; accepted 15 September 2011; online 30 September 2011)

The homoleptic thio­ether title complex, [Ni(C6H12S3)2](BF4)2·2CH3NO2, shows the expeced hexa­kis­(thio­ether) octa­hedral environment around the NiII atom. It crystallized as two crystallographically independent complex cations, [Ni(9S3)2]2+ (9S3 = 1,4,7-trithia­cyclo­nona­ne), within the unit cell where each NiII lies on an inversion center. In addition to the complex cations, there are two crystallographically independent BF4− anions present to balance the charge, and each shows disorder along a pseudo-C3 axis with ratios of 0.53 (2):0.47 (2) and 0.55 (2):0.45 (2). Two nitro­methane solvent mol­ecules per complex cation are also present in the unit cell.

Related literature

For other related NiII complexes, see: Setzer et al. (1983[Setzer, W. N., Ogle, C. A., Wilson, G. S. & Glass, R. S. (1983). Inorg. Chem. 22, 266-271.]); Blake et al. (1992[Blake, A. J., Gould, R. O., Halcrow, M. A., Holder, A. J., Hyde, T. I. & Schroder, M. (1992). J. Chem. Soc. Dalton Trans. pp. 3427-3431.], 2001[Blake, A. J., Brooks, N. R., Champness, N. R., Hubberstey, P., Keppie, I. J., Schröder, M. & Marr, A. C. (2001). Acta Cryst. E57, m376-m377.], 2007[Blake, A. J., Li, W.-S., Lippolis, V., Parsons, S. & Schröder, M. (2007). Acta Cryst. B63, 81-92.]); Nishijo et al. (2003[Nishijo, J., Miyazaki, A. & Enoki, T. (2003). Polyhedron, 22, 1755-1758.], 2004[Nishijo, J., Miyazaki, A. & Enoki, T. (2004). Bull. Chem. Soc. Jpn, 77, 715-727.]). For the coordination chemistry of 1,4,7-trithia­cyclo­nonane, see: Blake & Schroder (1990[Blake, A. J. & Schroder, M. (1990). Advances in Inorganic Chemistry, Vol. 35. New York: Academic Press Inc.]); Cooper & Rawle (1990[Cooper, S. R. & Rawle, S. C. (1990). Struct. Bonding (Berlin), 72, 1-72.]); Glass et al. (1980[Glass, R. S., Wilson, G. S. & Setzer, W. N. (1980). J. Am. Chem. Soc. 102, 5068-5069.]); Grant et al. (1991[Grant, G. J., Mauldin, P. M. & Setzer, W. N. (1991). J. Chem. Educ. 68, 605-607.]); Helm et al. (2005[Helm, M. L., Helton, G. P., VanDerveer, D. G. & Grant, G. J. (2005). Inorg. Chem. 44, 5696-5705.]); Setzer et al. (1990[Setzer, W. N., Cacioppo, E. L., Guo, Q., Grant, G. J., Kim, D. D., Hubbard, J. L. & VanDerveer, D. G. (1990). Inorg. Chem. 29, 2672-2681.]). For related complexes that incorporate nitro­methane, see: Grant et al. (2005[Grant, G. J., Lee, J. P., Helm, M. L., VanDerveer, D. G., Pennington, W. T., Harris, J. L., Mehne, L. F. & Klinger, D. W. (2005). J. Organomet. Chem. 690, 629-639.]); Helm et al. (2006[Helm, M. L., Hill, L. L., Lee, J. P., VanDerveer, D. G. & Grant, G. J. (2006). Dalton Trans. pp. 3534-3543.]). 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

  • [Ni(C6H12S3)2](BF4)2·2CH3NO2

  • Mr = 715.09

  • Monoclinic, P 21 /c

  • a = 9.1755 (18) Å

  • b = 19.825 (4) Å

  • c = 15.173 (3) Å

  • β = 90.88 (3)°

  • V = 2759.6 (9) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 1.24 mm−1

  • T = 200 K

  • 0.40 × 0.20 × 0.10 mm
Data collection

  • Bruker SMART X2S benchtop crystallographic system diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2004[Sheldrick, G. M. (2004). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.371, Tmax = 0.941

  • 25688 measured reflections

  • 4889 independent reflections

  • 3855 reflections with I > 2σ(I)

  • Rint = 0.054
Refinement

  • R[F2 > 2σ(F2)] = 0.037

  • wR(F2) = 0.090

  • S = 1.05

  • 4889 reflections

  • 395 parameters

  • 258 restraints

  • H-atom parameters constrained

  • Δρmax = 0.56 e Å−3

  • Δρmin = −0.39 e Å−3

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; 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: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL and local programs.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811037809/br2171sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811037809/br2171Isup2.hkl

checkCIF report


Comment top

The coordination chemistry of 1,4,7-trithiacyclononane (9S3) has been well studied both by us as well as other groups (Grant et al., 1991; Helm et al., 2005; Helm et al., 2006; Setzer et al., 1990; Setzer et al., 1983; Cooper et al., 1990; Blake et al., 1990). The three sulfur atoms of the 9S3 ligand have been calculated to be all endodentate in the lowest energy conformation of the free ligand (Glass et al., 1980). The endodentate nature of the sulfur atoms of 9S3 provides facile facial coordination to metal centers, and 9S3 has been complexed, in a bis-homoleptic fashion {i.e., [M(9S3)2]n+}, to 26 transistion metals ions to give a total of 72 different structures in a recent search of the Cambridge Structural Database (Allen, 2002; Release with Feb. and May 2011 updates). The complex, bis(1,4,7-trithiacyclononane)nickel(II) tetrafluoroborate, has been previously synthesized and characterized, which includes a single- crystal X-ray crystal structure where the crystals were obtained from ethanol evaporation with exclusion of any solvent in the structure (Setzer et al., 1983). In addition, the structure of the dication [Ni(9S3)2]2+ has been crystallographically characterized using a number of different anions (Blake et al., 2007; Blake et al., 2001; Nishijo et al., 2003; Nishijo et al., 2004; Blake et al., 1992). Herein, we wish to report the structure of the coordination compound bis(1,4,7-trithiacyclononane)nickel(II)bistetrafluoroborate dinitromethane solvate to include with the previously reported [Ni(9S3)2]2+ complexes.

As can be seen in Figure 1, the title complex displays the expected hexakis (thioether) octahedral geometry around the NiII center where each 9S3 ligand is coordinated to the face of the octahedron. Interestingly, the title complex crystallizes as two crystallographically independent complex cations within the unit cell where each NiII cation lies at the inversion center (Figure 2). In addition, both the tetrafluoroborate anion and nitromethane solvate crystallize as two crystallographically independent anions and solvent molecules, respectively. Out of the seven crystallographically characterized [Ni(9S3)2]2+ complex cations this is the first example where the unit cell contains two crystallographically different complex cations. Packing within the monoclinic crystal lattice shows a face-centered array for the [Ni(9S3)2]2+ dication to give a total of four [Ni(9S3)2]2+ complex cations within the unit cell. Both the BF4- anions and the nitromethane solvate molecules occupy four locations on the face and four locations within the unit cell to give a total of eight BF4- anions and eight nitromethane solvate molecules. Thus, the molecular formula is [Ni(9S3)2][BF4]2.2CH3NO2.

Setzer et al. have published the structure of [Ni(9S3)2][BF4]2 that was crystallized from ethanol, and was solved in the same space group (P21/c) and approximately the same R1 (0.03) as the title compound (Setzer et al., 1983). However, there are several differences between the previously reported structure of the title complex crystallized from ethanol versus that reported herein from nitromethane. Most notably is the presence of two crystallographically different complex cations. This is likely due, at least in part, to differences in crystal packing in the two different solvents. Secondly, the incorporation of solvent in the crystal lattice is unique to this system, but not unprecedented for crystal growth of similar structures from nitromethane (Helm et al., 2006; Grant et al., 2005). Lastly, there is a difference in the tetrafluoroborate anions in the structures. In the original report (Setzer et al., 1983), no disorder was observed in the BF4- anions compared to the compound shown in Figure 2 where disorder in the B-F bonds along a C3 axis is observed. Again, this could be attributed to different crystal packing in the two different solvents; however, temperature effects cannot be discounted as data collection on the Bruker SMART X2S was done at 203 K.

Related literature top

For other related NiII complexes, see: Setzer et al. (1983); Blake et al. (1992, 2001, (2007); Nishijo et al. (2003, 2004). For the coordination chemistry of 1,4,7-trithiacyclononane, see: Blake & Schroder (1990); Cooper & Rawle (1990); Glass et al. (1980); Grant et al. (1991); Helm et al. (2005); Setzer et al. (1990). For related complexes that incorporate nitromethane, see: Grant et al. (2005); Helm et al. (2006). For a description of the Cambridge structural Database, see: Allen (2002).

Experimental top

Bis(1,4,7-trithiacyclononane)nickel(II) bistetrafluoroborate dinitromethane solvate was synthesized as previously reported (Setzer et al., 1983). Violet needle-like crystals were obtained by slow diffusion of diethyl ether into a concentrated CH3NO2 solution of the title complex.

Refinement top

All hydrogen atoms were set to calculated geometries and allowed to refine on the positions of the parent atoms.

Structure refinement revealed disorder in the BF4 anions. In each case there is rotation about a B—F bond, which creates alternative sites for the remaining F atoms. The B—F distances as well as the F···F distances were restrained to be equal within 0.02 Å. The model contains 174 such restraints. This disorder also manifests itself in the anisotropic thermal parameters of the F atoms. The Uij components were restrained to approximate isotropic behavior. In all, 258 restraints were applied.

Structure description top

The coordination chemistry of 1,4,7-trithiacyclononane (9S3) has been well studied both by us as well as other groups (Grant et al., 1991; Helm et al., 2005; Helm et al., 2006; Setzer et al., 1990; Setzer et al., 1983; Cooper et al., 1990; Blake et al., 1990). The three sulfur atoms of the 9S3 ligand have been calculated to be all endodentate in the lowest energy conformation of the free ligand (Glass et al., 1980). The endodentate nature of the sulfur atoms of 9S3 provides facile facial coordination to metal centers, and 9S3 has been complexed, in a bis-homoleptic fashion {i.e., [M(9S3)2]n+}, to 26 transistion metals ions to give a total of 72 different structures in a recent search of the Cambridge Structural Database (Allen, 2002; Release with Feb. and May 2011 updates). The complex, bis(1,4,7-trithiacyclononane)nickel(II) tetrafluoroborate, has been previously synthesized and characterized, which includes a single- crystal X-ray crystal structure where the crystals were obtained from ethanol evaporation with exclusion of any solvent in the structure (Setzer et al., 1983). In addition, the structure of the dication [Ni(9S3)2]2+ has been crystallographically characterized using a number of different anions (Blake et al., 2007; Blake et al., 2001; Nishijo et al., 2003; Nishijo et al., 2004; Blake et al., 1992). Herein, we wish to report the structure of the coordination compound bis(1,4,7-trithiacyclononane)nickel(II)bistetrafluoroborate dinitromethane solvate to include with the previously reported [Ni(9S3)2]2+ complexes.

As can be seen in Figure 1, the title complex displays the expected hexakis (thioether) octahedral geometry around the NiII center where each 9S3 ligand is coordinated to the face of the octahedron. Interestingly, the title complex crystallizes as two crystallographically independent complex cations within the unit cell where each NiII cation lies at the inversion center (Figure 2). In addition, both the tetrafluoroborate anion and nitromethane solvate crystallize as two crystallographically independent anions and solvent molecules, respectively. Out of the seven crystallographically characterized [Ni(9S3)2]2+ complex cations this is the first example where the unit cell contains two crystallographically different complex cations. Packing within the monoclinic crystal lattice shows a face-centered array for the [Ni(9S3)2]2+ dication to give a total of four [Ni(9S3)2]2+ complex cations within the unit cell. Both the BF4- anions and the nitromethane solvate molecules occupy four locations on the face and four locations within the unit cell to give a total of eight BF4- anions and eight nitromethane solvate molecules. Thus, the molecular formula is [Ni(9S3)2][BF4]2.2CH3NO2.

Setzer et al. have published the structure of [Ni(9S3)2][BF4]2 that was crystallized from ethanol, and was solved in the same space group (P21/c) and approximately the same R1 (0.03) as the title compound (Setzer et al., 1983). However, there are several differences between the previously reported structure of the title complex crystallized from ethanol versus that reported herein from nitromethane. Most notably is the presence of two crystallographically different complex cations. This is likely due, at least in part, to differences in crystal packing in the two different solvents. Secondly, the incorporation of solvent in the crystal lattice is unique to this system, but not unprecedented for crystal growth of similar structures from nitromethane (Helm et al., 2006; Grant et al., 2005). Lastly, there is a difference in the tetrafluoroborate anions in the structures. In the original report (Setzer et al., 1983), no disorder was observed in the BF4- anions compared to the compound shown in Figure 2 where disorder in the B-F bonds along a C3 axis is observed. Again, this could be attributed to different crystal packing in the two different solvents; however, temperature effects cannot be discounted as data collection on the Bruker SMART X2S was done at 203 K.

For other related NiII complexes, see: Setzer et al. (1983); Blake et al. (1992, 2001, (2007); Nishijo et al. (2003, 2004). For the coordination chemistry of 1,4,7-trithiacyclononane, see: Blake & Schroder (1990); Cooper & Rawle (1990); Glass et al. (1980); Grant et al. (1991); Helm et al. (2005); Setzer et al. (1990). For related complexes that incorporate nitromethane, see: Grant et al. (2005); Helm et al. (2006). For a description of the Cambridge structural Database, see: Allen (2002).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid perspective (50% probability) showing one complex cation. Hydrogen atoms have been omitted forclarity.
[Figure 2] Fig. 2. Thermal ellipsoid perspective (50% probability) showing all crystallographically independent complex cations,anions and solvate molecules. Hydrogen atoms have been omitted for clarity.
Bis(1,4,7-trithiacyclononane)nickel(II) bis(tetrafluoridoborate) nitromethane disolvate top
Crystal data top
[Ni(C6H12S3)2](BF4)2·2CH3NO2F(000) = 1464
Mr = 715.09Dx = 1.721 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 241 reflections
a = 9.1755 (18) Åθ = 2.8–26.2°
b = 19.825 (4) ŵ = 1.24 mm−1
c = 15.173 (3) ÅT = 200 K
β = 90.88 (3)°Needle, violet
V = 2759.6 (9) Å30.40 × 0.20 × 0.10 mm
Z = 4
Data collection top
Bruker SMART X2S benchtop crystallographic system
diffractometer		4889 independent reflections
Radiation source: sealed tube3855 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.054
Detector resolution: 8.3330 pixels mm-1θmax = 25.3°, θmin = 1.7°
thin–slice ω scansh = −10→10
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		k = −23→23
Tmin = 0.371, Tmax = 0.941l = −18→18
25688 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0364P)2 + 1.8397P]
where P = (Fo2 + 2Fc2)/3
4889 reflections(Δ/σ)max = 0.001
395 parametersΔρmax = 0.56 e Å−3
258 restraintsΔρmin = −0.39 e Å−3
Crystal data top
[Ni(C6H12S3)2](BF4)2·2CH3NO2V = 2759.6 (9) Å3
Mr = 715.09Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.1755 (18) ŵ = 1.24 mm−1
b = 19.825 (4) ÅT = 200 K
c = 15.173 (3) Å0.40 × 0.20 × 0.10 mm
β = 90.88 (3)°
Data collection top
Bruker SMART X2S benchtop crystallographic system
diffractometer		4889 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		3855 reflections with I > 2σ(I)
Tmin = 0.371, Tmax = 0.941Rint = 0.054
25688 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037258 restraints
wR(F2) = 0.090H-atom parameters constrained
S = 1.05Δρmax = 0.56 e Å−3
4889 reflectionsΔρmin = −0.39 e Å−3
395 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*/UeqOcc. (<1)
Ni11.00000.50000.50000.02711 (14)
S10.74469 (9)0.49669 (4)0.53181 (6)0.0376 (2)
S20.96856 (9)0.61209 (4)0.44732 (5)0.0370 (2)
S31.03907 (9)0.54595 (4)0.64348 (5)0.0355 (2)
C10.6840 (4)0.5643 (2)0.4602 (2)0.0458 (9)
H1A0.68250.54740.39880.055*
H1B0.58260.57600.47540.055*
C20.7751 (3)0.62848 (19)0.4635 (2)0.0448 (8)
H2A0.76230.65060.52130.054*
H2B0.73960.65990.41720.054*
C31.0551 (4)0.65842 (18)0.5360 (2)0.0447 (8)
H3A1.16200.65410.53030.054*
H3B1.03030.70680.52910.054*
C41.0139 (4)0.63624 (18)0.6276 (2)0.0453 (8)
H4A0.91060.64790.63780.054*
H4B1.07440.66100.67140.054*
C50.8694 (4)0.52059 (18)0.6949 (2)0.0421 (8)
H5A0.87420.47170.70760.051*
H5B0.86130.54450.75190.051*
C60.7342 (4)0.5343 (2)0.6409 (2)0.0438 (8)
H6A0.72050.58360.63500.053*
H6B0.64870.51580.67160.053*
Ni20.50000.50001.00000.02718 (14)
S40.46860 (9)0.61205 (4)1.05263 (5)0.0370 (2)
S50.53896 (9)0.54594 (4)0.85648 (5)0.0356 (2)
S60.24477 (9)0.49668 (4)0.96823 (6)0.0376 (2)
C70.5552 (4)0.65834 (18)0.9641 (2)0.0443 (8)
H7A0.53060.70670.97040.053*
H7B0.66220.65400.97160.053*
C80.5141 (4)0.63632 (18)0.8721 (2)0.0443 (8)
H8A0.57460.66100.82940.053*
H8B0.41080.64810.86010.053*
C90.3690 (4)0.52056 (19)0.8050 (2)0.0421 (8)
H9A0.35840.54430.74790.050*
H9B0.37350.47160.79240.050*
C100.2341 (4)0.53443 (19)0.8593 (2)0.0436 (8)
H10A0.14740.51650.82760.052*
H10B0.22150.58380.86550.052*
C110.1840 (4)0.56433 (19)1.0398 (2)0.0456 (9)
H11A0.08210.57581.02350.055*
H11B0.18430.54751.10120.055*
C120.2751 (4)0.62830 (19)1.0366 (2)0.0452 (9)
H12A0.24190.65971.08290.054*
H12B0.25930.65050.97880.054*
B10.5621 (4)0.3228 (2)0.3852 (3)0.0454 (10)
F20.4223 (3)0.31428 (16)0.3592 (2)0.0965 (10)
F10.6404 (15)0.2690 (6)0.3621 (9)0.126 (5)0.47 (2)
F30.5603 (13)0.3216 (7)0.4745 (5)0.098 (4)0.47 (2)
F40.6175 (16)0.3788 (7)0.3580 (12)0.138 (7)0.47 (2)
F1'0.6551 (9)0.2978 (11)0.3282 (12)0.161 (7)0.53 (2)
F3'0.5895 (16)0.3014 (8)0.4656 (8)0.127 (5)0.53 (2)
F4'0.5896 (13)0.3911 (4)0.3868 (9)0.090 (3)0.53 (2)
B20.9384 (4)0.6773 (2)0.8853 (3)0.0466 (10)
F50.9375 (14)0.6777 (8)0.9741 (5)0.102 (5)0.45 (2)
F60.8808 (17)0.6223 (7)0.8555 (13)0.139 (8)0.45 (2)
F70.8620 (15)0.7319 (6)0.8613 (10)0.130 (6)0.45 (2)
F81.0777 (3)0.68555 (16)0.8592 (2)0.0960 (10)
F5'0.9137 (15)0.6977 (8)0.9660 (7)0.135 (6)0.55 (2)
F6'0.9095 (12)0.6092 (4)0.8865 (8)0.086 (3)0.55 (2)
F7'0.8436 (9)0.7031 (10)0.8294 (12)0.163 (7)0.55 (2)
N10.5976 (5)0.3452 (3)0.6971 (3)0.0804 (13)
O10.4758 (5)0.3253 (4)0.6821 (3)0.185 (3)
O20.6242 (8)0.3969 (3)0.7308 (5)0.179 (3)
C130.7127 (5)0.3000 (2)0.6732 (3)0.0674 (12)
H13A0.71330.26100.71300.101*
H13B0.80650.32350.67800.101*
H13C0.69710.28470.61240.101*
N20.9028 (5)0.6549 (3)0.1971 (3)0.0808 (13)
O30.8747 (8)0.6035 (3)0.2312 (5)0.184 (3)
O41.0248 (5)0.6746 (4)0.1823 (3)0.186 (4)
C140.7875 (5)0.7002 (2)0.1735 (3)0.0678 (12)
H14A0.69360.67740.18030.102*
H14B0.79830.71420.11200.102*
H14C0.79180.73990.21180.102*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0251 (3)0.0323 (3)0.0239 (3)0.0019 (2)0.0015 (2)−0.0014 (2)
S10.0277 (4)0.0460 (5)0.0393 (5)−0.0004 (4)0.0041 (3)−0.0042 (4)
S20.0370 (5)0.0401 (5)0.0340 (4)0.0038 (4)0.0024 (3)0.0056 (3)
S30.0386 (5)0.0403 (5)0.0274 (4)0.0029 (3)−0.0026 (3)−0.0032 (3)
C10.0305 (18)0.063 (2)0.044 (2)0.0107 (16)−0.0046 (14)0.0016 (17)
C20.0359 (19)0.050 (2)0.048 (2)0.0160 (16)−0.0016 (15)0.0048 (17)
C30.049 (2)0.0345 (19)0.051 (2)−0.0017 (16)−0.0044 (16)0.0021 (16)
C40.054 (2)0.037 (2)0.045 (2)−0.0006 (16)−0.0049 (16)−0.0117 (15)
C50.053 (2)0.047 (2)0.0269 (17)−0.0001 (16)0.0105 (14)−0.0012 (14)
C60.042 (2)0.052 (2)0.0376 (19)0.0048 (16)0.0141 (15)−0.0005 (16)
Ni20.0252 (3)0.0323 (3)0.0240 (3)0.0022 (2)0.0000 (2)0.0015 (2)
S40.0371 (5)0.0399 (5)0.0339 (4)0.0037 (4)−0.0006 (3)−0.0052 (3)
S50.0391 (5)0.0402 (5)0.0276 (4)0.0022 (3)0.0043 (3)0.0032 (3)
S60.0276 (4)0.0455 (5)0.0396 (5)−0.0010 (4)−0.0022 (3)0.0039 (4)
C70.049 (2)0.0332 (19)0.051 (2)−0.0044 (16)0.0063 (16)−0.0011 (15)
C80.050 (2)0.037 (2)0.046 (2)0.0029 (16)0.0051 (16)0.0096 (15)
C90.049 (2)0.049 (2)0.0281 (17)0.0017 (16)−0.0070 (14)0.0023 (14)
C100.044 (2)0.049 (2)0.0372 (19)0.0046 (17)−0.0131 (14)0.0011 (16)
C110.0302 (18)0.063 (2)0.044 (2)0.0095 (16)0.0066 (14)−0.0004 (17)
C120.038 (2)0.052 (2)0.045 (2)0.0158 (16)0.0034 (15)−0.0059 (17)
B10.040 (2)0.049 (3)0.047 (2)0.0007 (19)−0.0008 (18)0.000 (2)
F20.0520 (16)0.097 (2)0.140 (3)−0.0027 (15)−0.0223 (15)−0.0342 (19)
F10.130 (10)0.091 (7)0.159 (11)0.067 (6)0.022 (7)−0.010 (6)
F30.129 (7)0.122 (9)0.045 (5)0.035 (6)0.016 (4)−0.011 (5)
F40.123 (9)0.145 (12)0.145 (12)−0.047 (9)−0.026 (8)0.123 (11)
F1'0.070 (5)0.256 (16)0.160 (11)−0.004 (7)0.037 (6)−0.144 (11)
F3'0.138 (9)0.120 (8)0.123 (9)−0.064 (7)−0.051 (7)0.083 (7)
F4'0.094 (6)0.061 (4)0.115 (7)−0.025 (4)−0.009 (5)−0.008 (5)
B20.042 (2)0.050 (3)0.047 (2)−0.002 (2)0.0008 (18)−0.002 (2)
F50.123 (8)0.142 (10)0.039 (5)0.034 (7)−0.012 (5)0.018 (5)
F60.125 (10)0.152 (14)0.140 (13)−0.047 (10)0.023 (8)−0.120 (12)
F70.132 (10)0.086 (7)0.171 (12)0.067 (7)−0.030 (7)0.003 (7)
F80.0526 (16)0.098 (2)0.138 (3)−0.0020 (15)0.0230 (16)0.0343 (19)
F5'0.151 (9)0.131 (8)0.123 (9)−0.073 (7)0.059 (7)−0.094 (7)
F6'0.094 (5)0.059 (4)0.104 (7)−0.023 (3)0.011 (4)0.000 (4)
F7'0.067 (5)0.248 (15)0.175 (11)−0.005 (7)−0.035 (5)0.147 (11)
N10.066 (3)0.100 (4)0.077 (3)0.028 (3)0.022 (2)0.043 (3)
O10.054 (3)0.376 (11)0.125 (4)0.029 (4)0.000 (2)0.095 (5)
O20.275 (8)0.060 (3)0.206 (6)0.029 (4)0.132 (6)0.008 (3)
C130.065 (3)0.071 (3)0.066 (3)0.004 (2)0.004 (2)−0.001 (2)
N20.068 (3)0.101 (4)0.073 (3)0.026 (3)−0.023 (2)−0.044 (3)
O30.278 (8)0.060 (3)0.209 (6)0.032 (4)−0.133 (6)−0.008 (4)
O40.052 (3)0.376 (11)0.131 (4)0.028 (4)0.002 (2)−0.097 (5)
C140.067 (3)0.068 (3)0.068 (3)0.004 (2)−0.003 (2)0.000 (2)
Geometric parameters (Å, º) top
Ni1—S2i2.3776 (9)C7—H7A0.9900
Ni1—S22.3776 (9)C7—H7B0.9900
Ni1—S32.3820 (9)C8—H8A0.9900
Ni1—S3i2.3821 (9)C8—H8B0.9900
Ni1—S1i2.3999 (9)C9—C101.522 (5)
Ni1—S12.3999 (9)C9—H9A0.9900
S1—C11.808 (4)C9—H9B0.9900
S1—C61.819 (3)C10—H10A0.9900
S2—C31.803 (4)C10—H10B0.9900
S2—C21.825 (3)C11—C121.520 (5)
S3—C41.820 (4)C11—H11A0.9900
S3—C51.822 (3)C11—H11B0.9900
C1—C21.523 (5)C12—H12A0.9900
C1—H1A0.9900C12—H12B0.9900
C1—H1B0.9900B1—F41.291 (8)
C2—H2A0.9900B1—F3'1.312 (8)
C2—H2B0.9900B1—F1'1.321 (8)
C3—C41.512 (5)B1—F11.336 (8)
C3—H3A0.9900B1—F21.347 (5)
C3—H3B0.9900B1—F31.355 (8)
C4—H4A0.9900B1—F4'1.377 (8)
C4—H4B0.9900B2—F61.289 (9)
C5—C61.500 (5)B2—F7'1.310 (8)
C5—H5A0.9900B2—F5'1.312 (8)
C5—H5B0.9900B2—F71.338 (8)
C6—H6A0.9900B2—F51.348 (8)
C6—H6B0.9900B2—F81.354 (5)
Ni2—S4ii2.3795 (9)B2—F6'1.375 (8)
Ni2—S42.3795 (9)N1—O21.170 (7)
Ni2—S6ii2.3846 (10)N1—O11.204 (7)
Ni2—S62.3846 (10)N1—C131.435 (6)
Ni2—S52.3923 (9)C13—H13A0.9800
Ni2—S5ii2.3923 (9)C13—H13B0.9800
S4—C121.817 (3)C13—H13C0.9800
S4—C71.819 (4)N2—O31.174 (7)
S5—C91.805 (3)N2—O41.210 (6)
S5—C81.822 (4)N2—C141.428 (6)
S6—C101.815 (3)C14—H14A0.9800
S6—C111.819 (4)C14—H14B0.9800
C7—C81.505 (5)C14—H14C0.9800
S2i—Ni1—S2180.000 (1)S4ii—Ni2—S4180.00 (4)
S2i—Ni1—S391.97 (3)S4ii—Ni2—S6ii88.28 (3)
S2—Ni1—S388.03 (3)S4—Ni2—S6ii91.72 (3)
S2i—Ni1—S3i88.03 (3)S4ii—Ni2—S691.72 (3)
S2—Ni1—S3i91.97 (3)S4—Ni2—S688.28 (3)
S3—Ni1—S3i180.0S6ii—Ni2—S6180.00 (4)
S2i—Ni1—S1i88.82 (3)S4ii—Ni2—S591.68 (3)
S2—Ni1—S1i91.18 (3)S4—Ni2—S588.32 (3)
S3—Ni1—S1i92.27 (4)S6ii—Ni2—S590.78 (4)
S3i—Ni1—S1i87.73 (4)S6—Ni2—S589.22 (4)
S2i—Ni1—S191.18 (3)S4ii—Ni2—S5ii88.32 (3)
S2—Ni1—S188.82 (3)S4—Ni2—S5ii91.68 (3)
S3—Ni1—S187.73 (4)S6ii—Ni2—S5ii89.22 (4)
S3i—Ni1—S192.27 (4)S6—Ni2—S5ii90.78 (4)
S1i—Ni1—S1180.0S5—Ni2—S5ii180.00 (4)
C1—S1—C6102.91 (17)C12—S4—C7104.40 (17)
C1—S1—Ni198.70 (12)C12—S4—Ni2104.10 (12)
C6—S1—Ni1103.71 (12)C7—S4—Ni299.60 (12)
C3—S2—C2103.14 (17)C9—S5—C8102.78 (17)
C3—S2—Ni1100.11 (12)C9—S5—Ni298.47 (11)
C2—S2—Ni1103.56 (12)C8—S5—Ni2103.58 (11)
C4—S3—C5102.74 (17)C10—S6—C11103.12 (17)
C4—S3—Ni1103.76 (11)C10—S6—Ni2102.22 (12)
C5—S3—Ni199.66 (11)C11—S6—Ni299.66 (12)
C2—C1—S1115.8 (2)C8—C7—S4115.6 (2)
C2—C1—H1A108.3C8—C7—H7A108.4
S1—C1—H1A108.3S4—C7—H7A108.4
C2—C1—H1B108.3C8—C7—H7B108.4
S1—C1—H1B108.3S4—C7—H7B108.4
H1A—C1—H1B107.4H7A—C7—H7B107.4
C1—C2—S2112.4 (2)C7—C8—S5112.1 (2)
C1—C2—H2A109.1C7—C8—H8A109.2
S2—C2—H2A109.1S5—C8—H8A109.2
C1—C2—H2B109.1C7—C8—H8B109.2
S2—C2—H2B109.1S5—C8—H8B109.2
H2A—C2—H2B107.9H8A—C8—H8B107.9
C4—C3—S2115.1 (3)C10—C9—S5114.8 (2)
C4—C3—H3A108.5C10—C9—H9A108.6
S2—C3—H3A108.5S5—C9—H9A108.6
C4—C3—H3B108.5C10—C9—H9B108.6
S2—C3—H3B108.5S5—C9—H9B108.6
H3A—C3—H3B107.5H9A—C9—H9B107.5
C3—C4—S3112.0 (2)C9—C10—S6112.7 (2)
C3—C4—H4A109.2C9—C10—H10A109.1
S3—C4—H4A109.2S6—C10—H10A109.1
C3—C4—H4B109.2C9—C10—H10B109.1
S3—C4—H4B109.2S6—C10—H10B109.1
H4A—C4—H4B107.9H10A—C10—H10B107.8
C6—C5—S3114.9 (2)C12—C11—S6115.0 (2)
C6—C5—H5A108.5C12—C11—H11A108.5
S3—C5—H5A108.5S6—C11—H11A108.5
C6—C5—H5B108.5C12—C11—H11B108.5
S3—C5—H5B108.5S6—C11—H11B108.5
H5A—C5—H5B107.5H11A—C11—H11B107.5
C5—C6—S1111.6 (2)C11—C12—S4112.6 (2)
C5—C6—H6A109.3C11—C12—H12A109.1
S1—C6—H6A109.3S4—C12—H12A109.1
C5—C6—H6B109.3C11—C12—H12B109.1
S1—C6—H6B109.3S4—C12—H12B109.1
H6A—C6—H6B108.0H12A—C12—H12B107.8
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula[Ni(C6H12S3)2](BF4)2·2CH3NO2
Mr715.09
Crystal system, space groupMonoclinic, P21/c
Temperature (K)200
a, b, c (Å)9.1755 (18), 19.825 (4), 15.173 (3)
β (°) 90.88 (3)
V (Å3)2759.6 (9)
Z4
Radiation typeMo Kα
µ (mm−1)1.24
Crystal size (mm)0.40 × 0.20 × 0.10
Data collection
DiffractometerBruker SMART X2S benchtop crystallographic system
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2004)
Tmin, Tmax0.371, 0.941
No. of measured, independent and
observed [I > 2σ(I)] reflections		25688, 4889, 3855
Rint0.054
(sin θ/λ)max (Å−1)0.602
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.090, 1.05
No. of reflections4889
No. of parameters395
No. of restraints258
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.56, −0.39

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and local programs.

 

Acknowledgements

Acknowledgements are made to the following for their generous support of this research: the National Science Foundation RUI Program (CHE-0841659), the National Science Foundation MRI Program (CHE-0951711), the Grote Chemistry Fund at the University of Tennessee at Chattanooga. Professor Daron E. Janzen is also thanked for useful discussions.

References

First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
 First citationBlake, A. J., Brooks, N. R., Champness, N. R., Hubberstey, P., Keppie, I. J., Schröder, M. & Marr, A. C. (2001). Acta Cryst. E57, m376–m377.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationBlake, A. J., Gould, R. O., Halcrow, M. A., Holder, A. J., Hyde, T. I. & Schroder, M. (1992). J. Chem. Soc. Dalton Trans. pp. 3427–3431.  CSD CrossRef Web of Science Google Scholar
 First citationBlake, A. J., Li, W.-S., Lippolis, V., Parsons, S. & Schröder, M. (2007). Acta Cryst. B63, 81–92.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationBlake, A. J. & Schroder, M. (1990). Advances in Inorganic Chemistry, Vol. 35. New York: Academic Press Inc.  Google Scholar
 First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationCooper, S. R. & Rawle, S. C. (1990). Struct. Bonding (Berlin), 72, 1–72.  CrossRef CAS Google Scholar
 First citationGlass, R. S., Wilson, G. S. & Setzer, W. N. (1980). J. Am. Chem. Soc. 102, 5068–5069.  CSD CrossRef CAS Web of Science Google Scholar
 First citationGrant, G. J., Lee, J. P., Helm, M. L., VanDerveer, D. G., Pennington, W. T., Harris, J. L., Mehne, L. F. & Klinger, D. W. (2005). J. Organomet. Chem. 690, 629–639.  Web of Science CSD CrossRef CAS Google Scholar
 First citationGrant, G. J., Mauldin, P. M. & Setzer, W. N. (1991). J. Chem. Educ. 68, 605–607.  CrossRef CAS Google Scholar
 First citationHelm, M. L., Helton, G. P., VanDerveer, D. G. & Grant, G. J. (2005). Inorg. Chem. 44, 5696–5705.  Web of Science CSD CrossRef PubMed CAS Google Scholar
 First citationHelm, M. L., Hill, L. L., Lee, J. P., VanDerveer, D. G. & Grant, G. J. (2006). Dalton Trans. pp. 3534–3543.  Web of Science CSD CrossRef Google Scholar
 First citationNishijo, J., Miyazaki, A. & Enoki, T. (2003). Polyhedron, 22, 1755–1758.  CrossRef CAS Google Scholar
 First citationNishijo, J., Miyazaki, A. & Enoki, T. (2004). Bull. Chem. Soc. Jpn, 77, 715–727.  Web of Science CSD CrossRef CAS Google Scholar
 First citationSetzer, W. N., Cacioppo, E. L., Guo, Q., Grant, G. J., Kim, D. D., Hubbard, J. L. & VanDerveer, D. G. (1990). Inorg. Chem. 29, 2672–2681.  CSD CrossRef CAS Web of Science Google Scholar
 First citationSetzer, W. N., Ogle, C. A., Wilson, G. S. & Glass, R. S. (1983). Inorg. Chem. 22, 266–271.  CSD CrossRef CAS Web of Science Google Scholar
 First citationSheldrick, G. M. (2004). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
Volume 67| Part 10| October 2011| Pages m1417-m1418
https://doi.org/10.1107/S1600536811037809
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