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Acta Cryst. (2007). E63, m2741
https://doi.org/10.1107/S1600536807049070
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2,3-Diethyl­thia­zolium bis­(2-thioxo-1,3-dithiole-4,5-dithiol­ato)nickelate(III)

E. Tomiyama, K. Tomono and K. Miyamura
In the title complex, (C7H12NS)[Ni(C3S5)2], the dihedral angle between the thia­zole ring of the cation and the plane of the anion is 8.0 (2)°. In the crystal structure, S...S inter­molecular inter­actions between the anions form a distorted honeycomb structure parallel to the (002) plane, with cavities ∼12.34 Å in diameter. The cavities are filled with cations. The cations and anions are linked via S...S [3.6657 (15) and 3.6240 (15) Å] and C—H...S inter­actions.
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Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049070/ci2476sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049070/ci2476Isup2.hkl
Contains datablock I

CCDC reference: 667169

checkCIF report

Key indicators

  • Single-crystal X-ray study
  • T = 300 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.052
  • wR factor = 0.099
  • Data-to-parameter ratio = 20.9

checkCIF/PLATON results

No syntax errors found




Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   S2      ..       5.10 su


Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1         (3)       2.86


   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check
Comment top

The control of molecular organization in the solid state is an important theme of coordination chemistry. Self-assembled metal complexes with specific network topologies attract great attention due to their potential applications as functional solid materials, as well as their fascinating framework structures, especially the 'honeycomb' structure (Gardner et al., 1995). In the construction of diverse networks, there is preference for the use of directional intermolecular interactions such as hydrogen bonds (Frankenbach & Etter 1992), metal–ligand coordination bonds (Abrahams et al., 1994), and donor–acceptor interactions (Russell et al., 1994). This approach is based on the premise that if these interactions dominate the crystal field, then the solid-state structure should follow from the directional preferences associated with these interactions. Metal complexes with 2-thioxo-1,3-dithiole-4,5-dithiolate (dmit) ligand have drawn our attention to the role of S···S interaction between anions and cations, because conduction pathways between cation and anion may be constructed by S···S interactions. In order to explore new crystal structures of dmit complexes and to gain more insight into the structure-regulating ability of S···S interactions between anion and cation, the title complex salt (I) has been synthesized and analysed by X-ray crystallography.

The asymmetric unit of (I) is shown in Fig. 1. The Ni—S distances range from 2.1551 (11) to 2.1703 (10) Å, with an average of 2.163 (6) Å, and the cis-S—Ni—S angles range from 85.02 (4) to 93.13 (4)° (Table 1). Therefore, the NiS4 geometry is slightly distorted square-planar. The whole [Ni(dmit)2]- anion is essentially planar, although the planes of the two coordinated C3S52- ligands make a dihedral angle of 2.83 (6)°. In the crystal structure (Fig. 2), the anions and cations are almost parallel. The dihedral angle and distance between the thiazole ring of the cation and plane of the anion are 8.0 (2)° and 3.633 Å, respectively. The C13—C12—N1—C9 [92.3 (5)°] and S11—C9—C10—C11 [-8.3 (5)°] torsion angles indicate that one of the ethyl groups is almost coplanar with the thiazolium ring and in the other group, the C(sp3)—C(sp3) bond is oriented perpendicular to the thiazolium ring. The anions are arranged in a zigzag manner along the c axis (Fig. 2).

In the crystal structure of (I), four S···S contacts shorter than 3.70 Å, the sum of van der Waals radii, are observed and are shown in Fig. 3 by dotted lines. Of the four contacts, two are between anions [S5···S10i and S7···S9iii] and the other two are between anion and cation [S5···S11ii and S9···S11iii] (see Table 1 for distances and symmetry codes); two [Ni(dmit)2]- anions form a quasi-dimeric structure. Inversion related anions at (x, y, z) and (1 - x, 2 - y, -z) are stacked along the a axis, without any significant S···S contacts; the shortest contact of 3.7490 (15) Å is observed between S3 and S7.

In the crystal structure, the anions form a distorted honeycomb structure parallel to the (002) plane. The cavity size is 12.34 Å in diameter as measured by the average of three Ni···Ni distances. The cavities are filled with cations. The cations and anions are linked through the S···S interactions, as mentioned above, and via the C12–H12A···S6(-x,2 - y,-z) interactions [H···S = 2.86 Å].

The electrical conductivity of crystal measured by the two-probe alternating current method was 10-7 S cm-1 at room temperature, which is not very high among the (cation):[Ni(dmit)2] type of 1:1 complexes.

Related literature top

For related literature, see: Abrahams et al. (1994); Frankenbach & Etter (1992); Gardner et al. (1995); Russell et al. (1994); Steimecke et al. (1979).

Experimental top

All starting materials were of reagent grade and used as purchased. 2,3-Diethylthiazolium bromide was synthesized as follows: Ethyl bromide (10 mmol) was mixed with 2-methylthiazole (1 mmol) and the resultant solid was filtered and washed several times by diethyl ether to give 2,3-diethylthiazolium bromide. (Bu4N)[Ni(dmit)2] was synthesized according to the literature method (Steimecke et al., 1979). Compound (I) was prepared by the cation-exchange method by slow interdiffusion of an acetone solution (25 ml) of (Bu4N)[Ni(dmit)2] (0.05 mol) and a chloroform–methanol solution (50 ml; 4:1) of 2,3-diethylthiazolium bromide (0.10 mol) at room temperature. Black plate crystals of suitable size for X-ray diffraction and conductivity measurement were obtained.

Refinement top

All H atoms were positioned geometrically and allowed to ride on their attached atoms, with C—H distances in the range 0.93–0.97 Å and Uiso = 1.2Ueq(C) [or 1.5Ueq(C) for methyl groups].

Structure description top

The control of molecular organization in the solid state is an important theme of coordination chemistry. Self-assembled metal complexes with specific network topologies attract great attention due to their potential applications as functional solid materials, as well as their fascinating framework structures, especially the 'honeycomb' structure (Gardner et al., 1995). In the construction of diverse networks, there is preference for the use of directional intermolecular interactions such as hydrogen bonds (Frankenbach & Etter 1992), metal–ligand coordination bonds (Abrahams et al., 1994), and donor–acceptor interactions (Russell et al., 1994). This approach is based on the premise that if these interactions dominate the crystal field, then the solid-state structure should follow from the directional preferences associated with these interactions. Metal complexes with 2-thioxo-1,3-dithiole-4,5-dithiolate (dmit) ligand have drawn our attention to the role of S···S interaction between anions and cations, because conduction pathways between cation and anion may be constructed by S···S interactions. In order to explore new crystal structures of dmit complexes and to gain more insight into the structure-regulating ability of S···S interactions between anion and cation, the title complex salt (I) has been synthesized and analysed by X-ray crystallography.

The asymmetric unit of (I) is shown in Fig. 1. The Ni—S distances range from 2.1551 (11) to 2.1703 (10) Å, with an average of 2.163 (6) Å, and the cis-S—Ni—S angles range from 85.02 (4) to 93.13 (4)° (Table 1). Therefore, the NiS4 geometry is slightly distorted square-planar. The whole [Ni(dmit)2]- anion is essentially planar, although the planes of the two coordinated C3S52- ligands make a dihedral angle of 2.83 (6)°. In the crystal structure (Fig. 2), the anions and cations are almost parallel. The dihedral angle and distance between the thiazole ring of the cation and plane of the anion are 8.0 (2)° and 3.633 Å, respectively. The C13—C12—N1—C9 [92.3 (5)°] and S11—C9—C10—C11 [-8.3 (5)°] torsion angles indicate that one of the ethyl groups is almost coplanar with the thiazolium ring and in the other group, the C(sp3)—C(sp3) bond is oriented perpendicular to the thiazolium ring. The anions are arranged in a zigzag manner along the c axis (Fig. 2).

In the crystal structure of (I), four S···S contacts shorter than 3.70 Å, the sum of van der Waals radii, are observed and are shown in Fig. 3 by dotted lines. Of the four contacts, two are between anions [S5···S10i and S7···S9iii] and the other two are between anion and cation [S5···S11ii and S9···S11iii] (see Table 1 for distances and symmetry codes); two [Ni(dmit)2]- anions form a quasi-dimeric structure. Inversion related anions at (x, y, z) and (1 - x, 2 - y, -z) are stacked along the a axis, without any significant S···S contacts; the shortest contact of 3.7490 (15) Å is observed between S3 and S7.

In the crystal structure, the anions form a distorted honeycomb structure parallel to the (002) plane. The cavity size is 12.34 Å in diameter as measured by the average of three Ni···Ni distances. The cavities are filled with cations. The cations and anions are linked through the S···S interactions, as mentioned above, and via the C12–H12A···S6(-x,2 - y,-z) interactions [H···S = 2.86 Å].

The electrical conductivity of crystal measured by the two-probe alternating current method was 10-7 S cm-1 at room temperature, which is not very high among the (cation):[Ni(dmit)2] type of 1:1 complexes.

For related literature, see: Abrahams et al. (1994); Frankenbach & Etter (1992); Gardner et al. (1995); Russell et al. (1994); Steimecke et al. (1979).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and KENX (Sakai, 2002).

Figures top
[Figure 1] Fig. 1. An ORTEPIII (Burnett & Johnson, 1996) view of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. The crystal packing of (I), viewed along the a axis.
[Figure 3] Fig. 3. Packing of the [Ni(dmit)2] anions of (I), viewed from their molecular axes. Dashed lines indicate short S···S contacts; red dashed lines are S···S contacts between anion and cation, and light blue dashed lines are S···S contacts between anions. Green lines and circles show one hexagon of the honeycomb structure.
2,3-Diethylthiazolium bis(2-thioxo-1,3-dithiole-4,5-dithiolato)nickelate(III) top
Crystal data top
(C7H12NS)[Ni(C3S5)2]F(000) = 1204
Mr = 593.61Dx = 1.809 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4004 reflections
a = 8.2465 (9) Åθ = 2.5–27.4°
b = 10.4325 (12) ŵ = 1.95 mm−1
c = 25.382 (3) ÅT = 300 K
β = 93.344 (2)°Plate, black
V = 2179.9 (4) Å30.29 × 0.08 × 0.04 mm
Z = 4
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		4945 independent reflections
Radiation source: fine-focus sealed tube3804 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
Detector resolution: 8.366 pixels mm-1θmax = 27.5°, θmin = 2.5°
ω scansh = −10→10
Absorption correction: analytical
(XPREP; Bruker, 2002)		k = −10→13
Tmin = 0.719, Tmax = 0.933l = −30→32
13052 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)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0377P)2]
where P = (Fo2 + 2Fc2)/3
4945 reflections(Δ/σ)max = 0.001
237 parametersΔρmax = 0.66 e Å−3
0 restraintsΔρmin = −0.33 e Å−3
Crystal data top
(C7H12NS)[Ni(C3S5)2]V = 2179.9 (4) Å3
Mr = 593.61Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.2465 (9) ŵ = 1.95 mm−1
b = 10.4325 (12) ÅT = 300 K
c = 25.382 (3) Å0.29 × 0.08 × 0.04 mm
β = 93.344 (2)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		4945 independent reflections
Absorption correction: analytical
(XPREP; Bruker, 2002)		3804 reflections with I > 2σ(I)
Tmin = 0.719, Tmax = 0.933Rint = 0.042
13052 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.099H-atom parameters constrained
S = 1.04Δρmax = 0.66 e Å−3
4945 reflectionsΔρmin = −0.33 e Å−3
237 parameters
Special details top

Experimental. The first 50 frames were rescanned at the end of data collection to evaluate any possible decay phenomenon. Since it was judged to be negligible, no decay correction was applied to the data.

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.

Mean-plane data from final SHELXL refinement run:-

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

6.1704 (0.0020) x + 4.8344 (0.0022) y - 13.1376 (0.0048) z = 6.1128 (0.0016)

* -0.0383 (0.0007) Ni1 * -0.0106 (0.0011) S1 * -0.0476 (0.0011) S2 * 0.0304 (0.0011) S3 * -0.0189 (0.0012) S4 * 0.0678 (0.0013) S5 * -0.0729 (0.0012) S6 * -0.0221 (0.0011) S7 * -0.0154 (0.0012) S8 * 0.0405 (0.0012) S9 * 0.0746 (0.0014) S10 * 0.0095 (0.0031) C1 * -0.0134 (0.0031) C2 * 0.0276 (0.0029) C3 * -0.0376 (0.0031) C4 * -0.0171 (0.0030) C5 * 0.0434 (0.0030) C6

Rms deviation of fitted atoms = 0.0403

5.9897 (0.0105) x + 3.8809 (0.0123) y - 15.7207 (0.0340) z = 1.3365 (0.0105)

Angle to previous plane (with approximate e.s.d.) = 8.00 (0.17)

* -0.0036 (0.0025) C7 * 0.0044 (0.0023) C8 * 0.0022 (0.0020) C9 * 0.0003 (0.0022) N1 * -0.0034 (0.0018) S11

Rms deviation of fitted atoms = 0.0031

6.2436 (0.0026) x + 4.6387 (0.0036) y - 13.2480 (0.0082) z = 5.9160 (0.0038)

Angle to previous plane (with approximate e.s.d.) = 7.28 (0.18)

* 0.0074 (0.0028) C1 * 0.0043 (0.0028) C2 * -0.0037 (0.0026) C3 * -0.0031 (0.0012) S1 * 0.0054 (0.0012) S2 * -0.0068 (0.0012) S3 * -0.0147 (0.0012) S4 * 0.0112 (0.0013) S5

Rms deviation of fitted atoms = 0.0080

6.0849 (0.0027) x + 5.0943 (0.0037) y - 12.8985 (0.0079) z = 6.2220 (0.0020)

Angle to previous plane (with approximate e.s.d.) = 2.83 (0.06)

* -0.0058 (0.0028) C4 * -0.0089 (0.0028) C5 * 0.0072 (0.0028) C6 * 0.0073 (0.0012) S6 * 0.0037 (0.0012) S7 * -0.0051 (0.0012) S8 * 0.0004 (0.0012) S9 * 0.0013 (0.0014) S10

Rms deviation of fitted atoms = 0.0057

6.1704 (0.0020) x + 4.8344 (0.0022) y - 13.1376 (0.0048) z = 6.1128 (0.0016)

Angle to previous plane (with approximate e.s.d.) = 1.63 (0.05)

* -0.0383 (0.0007) Ni1 * -0.0106 (0.0011) S1 * -0.0476 (0.0011) S2 * 0.0304 (0.0011) S3 * -0.0189 (0.0012) S4 * 0.0678 (0.0013) S5 * -0.0729 (0.0012) S6 * -0.0221 (0.0011) S7 * -0.0154 (0.0012) S8 * 0.0405 (0.0012) S9 * 0.0746 (0.0014) S10 * 0.0095 (0.0031) C1 * -0.0134 (0.0031) C2 * 0.0276 (0.0029) C3 * -0.0376 (0.0031) C4 * -0.0171 (0.0030) C5 * 0.0434 (0.0030) C6

Rms deviation of fitted atoms = 0.0403

4.6551 (0.0255) x + 2.6266 (0.0523) y + 19.0832 (0.0922) z = 5.8094 (0.0341)

Angle to previous plane (with approximate e.s.d.) = 80.45 (0.22)

* 0.0000 (0.0000) C12 * 0.0000 (0.0000) C13 * 0.0000 (0.0000) N1

Rms deviation of fitted atoms = 0.0000

6.1704 (0.0020) x + 4.8344 (0.0022) y - 13.1376 (0.0048) z = 6.1128 (0.0016)

Angle to previous plane (with approximate e.s.d.) = 80.45 (0.22)

* -0.0383 (0.0007) Ni1 * 0.0095 (0.0030) C1 * -0.0134 (0.0031) C2 * 0.0276 (0.0029) C3 * -0.0376 (0.0031) C4 * -0.0171 (0.0030) C5 * 0.0434 (0.0030) C6 * -0.0106 (0.0011) S1 * -0.0476 (0.0011) S2 * 0.0304 (0.0012) S3 * -0.0189 (0.0012) S4 * 0.0678 (0.0013) S5 * -0.0729 (0.0012) S6 * -0.0221 (0.0011) S7 * -0.0154 (0.0012) S8 * 0.0405 (0.0012) S9 * 0.0746 (0.0014) S10 - 3.5538 (0.0031) N1 - 3.4707 (0.0039) C7 - 3.5866 (0.0044) C8 - 3.7369 (0.0036) C9 - 3.8162 (0.0016) S11

Rms deviation of fitted atoms = 0.0403

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
C10.3050 (4)1.0872 (3)0.07732 (13)0.0325 (8)
C20.4172 (4)1.0131 (3)0.10446 (13)0.0332 (8)
C30.3853 (4)1.2187 (3)0.16206 (13)0.0338 (8)
C40.2354 (4)0.7049 (3)−0.09246 (13)0.0327 (8)
C50.3496 (4)0.6291 (3)−0.06828 (13)0.0319 (8)
C60.2647 (5)0.5114 (3)−0.15609 (13)0.0378 (9)
C70.2390 (5)0.7855 (4)0.20018 (15)0.0435 (10)
H70.27590.83850.22780.052*
C80.2956 (5)0.6670 (4)0.19200 (16)0.0515 (11)
H80.37750.62800.21300.062*
C90.0838 (5)0.7288 (4)0.12669 (14)0.0376 (9)
C10−0.0389 (5)0.7418 (4)0.08211 (16)0.0555 (12)
H10A−0.02040.82200.06410.067*
H10B−0.14580.74630.09610.067*
C11−0.0377 (6)0.6340 (5)0.04253 (16)0.0686 (14)
H11A0.06410.63370.02600.103*
H11B−0.12470.64590.01620.103*
H11C−0.05160.55370.06020.103*
C120.0392 (5)0.9453 (4)0.16475 (16)0.0515 (11)
H12A0.00160.97060.12940.062*
H12B0.11771.00850.17800.062*
C13−0.1011 (6)0.9437 (5)0.19919 (19)0.0725 (15)
H13A−0.18390.88780.18420.109*
H13B−0.14401.02890.20180.109*
H13C−0.06570.91350.23370.109*
N10.1194 (4)0.8188 (3)0.16260 (12)0.0395 (8)
Ni10.32928 (6)0.85483 (4)0.006835 (16)0.03197 (13)
S10.21514 (13)1.03771 (10)0.01842 (4)0.0438 (3)
S20.47494 (12)0.86763 (9)0.08067 (4)0.0407 (2)
S30.25571 (12)1.23261 (9)0.10606 (4)0.0405 (2)
S40.49365 (12)1.07699 (10)0.16431 (4)0.0424 (3)
S50.40348 (14)1.32933 (10)0.20821 (4)0.0463 (3)
S60.17662 (13)0.84662 (10)−0.06525 (4)0.0442 (3)
S70.44327 (12)0.67219 (9)−0.00807 (4)0.0408 (2)
S80.15232 (13)0.65050 (10)−0.15321 (4)0.0437 (3)
S90.39739 (12)0.48947 (9)−0.10162 (4)0.0403 (2)
S100.24644 (15)0.40762 (11)−0.20523 (4)0.0520 (3)
S110.19918 (14)0.59741 (11)0.13857 (4)0.0535 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.035 (2)0.031 (2)0.0315 (18)−0.0003 (16)0.0030 (15)−0.0022 (16)
C20.035 (2)0.031 (2)0.0331 (18)−0.0029 (16)0.0014 (16)−0.0028 (15)
C30.036 (2)0.032 (2)0.0334 (18)−0.0034 (16)0.0042 (16)0.0007 (16)
C40.037 (2)0.032 (2)0.0291 (18)0.0011 (16)0.0033 (15)−0.0049 (15)
C50.034 (2)0.029 (2)0.0329 (18)0.0021 (16)0.0076 (15)−0.0013 (15)
C60.043 (2)0.037 (2)0.0344 (19)−0.0029 (17)0.0071 (17)−0.0014 (16)
C70.044 (2)0.046 (3)0.039 (2)−0.0008 (19)−0.0076 (18)0.0038 (19)
C80.047 (3)0.053 (3)0.053 (2)0.009 (2)−0.009 (2)0.005 (2)
C90.036 (2)0.039 (2)0.038 (2)0.0004 (17)0.0033 (17)0.0067 (18)
C100.054 (3)0.061 (3)0.050 (2)−0.004 (2)−0.008 (2)0.009 (2)
C110.064 (3)0.090 (4)0.051 (3)−0.020 (3)0.001 (2)0.000 (3)
C120.058 (3)0.038 (2)0.058 (3)0.011 (2)0.001 (2)0.009 (2)
C130.050 (3)0.070 (3)0.098 (4)0.019 (3)0.018 (3)−0.004 (3)
N10.0415 (19)0.0363 (19)0.0412 (18)0.0051 (15)0.0081 (15)0.0076 (15)
Ni10.0340 (3)0.0310 (3)0.0310 (2)0.0024 (2)0.00217 (19)−0.0012 (2)
S10.0507 (6)0.0384 (6)0.0405 (5)0.0122 (5)−0.0129 (5)−0.0072 (4)
S20.0422 (6)0.0379 (6)0.0411 (5)0.0113 (4)−0.0052 (4)−0.0053 (4)
S30.0471 (6)0.0326 (5)0.0409 (5)0.0068 (4)−0.0058 (4)−0.0041 (4)
S40.0434 (6)0.0430 (6)0.0395 (5)0.0076 (5)−0.0082 (4)−0.0057 (4)
S50.0612 (7)0.0387 (6)0.0386 (5)−0.0020 (5)0.0001 (5)−0.0068 (4)
S60.0548 (7)0.0389 (6)0.0376 (5)0.0161 (5)−0.0089 (5)−0.0063 (4)
S70.0455 (6)0.0402 (6)0.0357 (5)0.0125 (5)−0.0052 (4)−0.0050 (4)
S80.0519 (6)0.0426 (6)0.0355 (5)0.0090 (5)−0.0066 (4)−0.0060 (4)
S90.0472 (6)0.0369 (6)0.0367 (5)0.0092 (4)0.0027 (4)−0.0044 (4)
S100.0685 (8)0.0462 (7)0.0410 (6)0.0027 (6)0.0007 (5)−0.0130 (5)
S110.0514 (7)0.0457 (7)0.0629 (7)0.0097 (5)−0.0004 (5)−0.0047 (5)
Geometric parameters (Å, º) top
C1—C21.361 (5)C9—N11.329 (5)
C1—S11.709 (3)C9—C101.480 (5)
C1—S31.742 (4)C9—S111.686 (4)
C2—S21.711 (4)C10—C111.509 (6)
C2—S41.743 (3)C10—H10A0.97
C3—S51.645 (3)C10—H10B0.97
C3—S41.727 (4)C11—H11A0.96
C3—S31.734 (4)C11—H11B0.96
C4—C51.349 (5)C11—H11C0.96
C4—S61.714 (4)C12—N11.478 (5)
C4—S81.745 (3)C12—C131.490 (5)
C5—S71.731 (4)C12—H12A0.97
C5—S91.742 (3)C12—H12B0.97
C6—S101.652 (4)C13—H13A0.96
C6—S81.726 (4)C13—H13B0.96
C6—S91.728 (4)C13—H13C0.96
C7—C81.342 (5)Ni1—S12.1551 (11)
C7—N11.376 (5)Ni1—S62.1613 (10)
C7—H70.93Ni1—S72.1677 (11)
C8—S111.695 (4)Ni1—S22.1703 (10)
C8—H80.93
S5···S10i3.5981 (15)S7···S9iii3.4489 (13)
S5···S11ii3.6657 (15)S9···S11iii3.6240 (15)
C2—C1—S1121.2 (3)H11A—C11—H11B109.5
C2—C1—S3116.8 (3)C10—C11—H11C109.5
S1—C1—S3122.0 (2)H11A—C11—H11C109.5
C1—C2—S2121.3 (3)H11B—C11—H11C109.5
C1—C2—S4115.1 (3)N1—C12—C13112.1 (3)
S2—C2—S4123.6 (2)N1—C12—H12A109.2
S5—C3—S4123.5 (2)C13—C12—H12A109.2
S5—C3—S3123.5 (2)N1—C12—H12B109.2
S4—C3—S3113.07 (19)C13—C12—H12B109.2
C5—C4—S6121.9 (3)H12A—C12—H12B107.9
C5—C4—S8116.0 (3)C12—C13—H13A109.5
S6—C4—S8122.1 (2)C12—C13—H13B109.5
C4—C5—S7120.9 (3)H13A—C13—H13B109.5
C4—C5—S9116.2 (3)C12—C13—H13C109.5
S7—C5—S9123.0 (2)H13A—C13—H13C109.5
S10—C6—S8123.9 (2)H13B—C13—H13C109.5
S10—C6—S9122.9 (2)C9—N1—C7114.7 (3)
S8—C6—S9113.2 (2)C9—N1—C12125.0 (3)
C8—C7—N1111.5 (4)C7—N1—C12120.2 (3)
C8—C7—H7124.2S1—Ni1—S685.02 (4)
N1—C7—H7124.2S1—Ni1—S7177.79 (4)
C7—C8—S11111.5 (3)S6—Ni1—S793.13 (4)
C7—C8—H8124.2S1—Ni1—S292.97 (4)
S11—C8—H8124.2S6—Ni1—S2177.66 (4)
N1—C9—C10125.0 (3)S7—Ni1—S288.91 (4)
N1—C9—S11110.6 (3)C1—S1—Ni1102.48 (13)
C10—C9—S11124.4 (3)C2—S2—Ni1101.99 (12)
C9—C10—C11114.2 (4)C3—S3—C197.05 (16)
C9—C10—H10A108.7C3—S4—C297.96 (17)
C11—C10—H10A108.7C4—S6—Ni1102.17 (12)
C9—C10—H10B108.7C5—S7—Ni1101.91 (12)
C11—C10—H10B108.7C6—S8—C497.29 (17)
H10A—C10—H10B107.6C6—S9—C597.32 (17)
C10—C11—H11A109.5C9—S11—C891.6 (2)
C10—C11—H11B109.5
S1—C1—C2—S20.6 (5)S5—C3—S3—C1179.0 (2)
S3—C1—C2—S2179.53 (19)S4—C3—S3—C1−0.9 (2)
S1—C1—C2—S4−178.88 (19)C2—C1—S3—C30.5 (3)
S3—C1—C2—S40.0 (4)S1—C1—S3—C3179.5 (2)
S6—C4—C5—S7−0.1 (5)S5—C3—S4—C2−178.9 (2)
S8—C4—C5—S7179.48 (19)S3—C3—S4—C21.0 (2)
S6—C4—C5—S9−179.16 (19)C1—C2—S4—C3−0.6 (3)
S8—C4—C5—S90.4 (4)S2—C2—S4—C3179.9 (2)
N1—C7—C8—S11−0.7 (4)C5—C4—S6—Ni10.9 (3)
N1—C9—C10—C11171.1 (4)S8—C4—S6—Ni1−178.68 (19)
S11—C9—C10—C11−8.3 (5)S1—Ni1—S6—C4177.78 (13)
C10—C9—N1—C7−179.4 (4)S7—Ni1—S6—C4−1.03 (13)
S11—C9—N1—C70.1 (4)C4—C5—S7—Ni1−0.7 (3)
C10—C9—N1—C121.7 (6)S9—C5—S7—Ni1178.25 (18)
S11—C9—N1—C12−178.7 (3)S6—Ni1—S7—C50.97 (13)
C8—C7—N1—C90.4 (5)S2—Ni1—S7—C5179.83 (12)
C8—C7—N1—C12179.3 (3)S10—C6—S8—C4179.5 (2)
C13—C12—N1—C992.3 (5)S9—C6—S8—C40.5 (2)
C13—C12—N1—C7−86.5 (5)C5—C4—S8—C6−0.5 (3)
C2—C1—S1—Ni1−0.9 (3)S6—C4—S8—C6179.1 (2)
S3—C1—S1—Ni1−179.79 (18)S10—C6—S9—C5−179.3 (2)
S6—Ni1—S1—C1179.54 (13)S8—C6—S9—C5−0.3 (2)
S2—Ni1—S1—C10.74 (13)C4—C5—S9—C6−0.1 (3)
C1—C2—S2—Ni10.1 (3)S7—C5—S9—C6−179.1 (2)
S4—C2—S2—Ni1179.52 (19)N1—C9—S11—C8−0.4 (3)
S1—Ni1—S2—C2−0.50 (13)C10—C9—S11—C8179.1 (4)
S7—Ni1—S2—C2178.34 (13)C7—C8—S11—C90.7 (3)
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, y+1, z; (iii) −x+1, −y+1, −z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12A···S6iv0.972.863.706 (4)147
Symmetry code: (iv) −x, −y+2, −z.

Experimental details

Crystal data
Chemical formula(C7H12NS)[Ni(C3S5)2]
Mr593.61
Crystal system, space groupMonoclinic, P21/c
Temperature (K)300
a, b, c (Å)8.2465 (9), 10.4325 (12), 25.382 (3)
β (°) 93.344 (2)
V (Å3)2179.9 (4)
Z4
Radiation typeMo Kα
µ (mm−1)1.95
Crystal size (mm)0.29 × 0.08 × 0.04
Data collection
DiffractometerBruker SMART APEX CCD area-detector
Absorption correctionAnalytical
(XPREP; Bruker, 2002)
Tmin, Tmax0.719, 0.933
No. of measured, independent and
observed [I > 2σ(I)] reflections		13052, 4945, 3804
Rint0.042
(sin θ/λ)max (Å−1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.099, 1.04
No. of reflections4945
No. of parameters237
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.66, −0.33

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996) and Mercury (Bruno et al., 2002), SHELXL97 (Sheldrick, 1997) and KENX (Sakai, 2002).

Selected geometric parameters (Å, º) top
C1—S11.709 (3)C5—S71.731 (4)
C1—S31.742 (4)C5—S91.742 (3)
C2—S21.711 (4)C6—S101.652 (4)
C2—S41.743 (3)C6—S81.726 (4)
C3—S51.645 (3)C6—S91.728 (4)
C3—S41.727 (4)Ni1—S12.1551 (11)
C3—S31.734 (4)Ni1—S62.1613 (10)
C4—S61.714 (4)Ni1—S72.1677 (11)
C4—S81.745 (3)Ni1—S22.1703 (10)
S5···S10i3.5981 (15)S7···S9iii3.4489 (13)
S5···S11ii3.6657 (15)S9···S11iii3.6240 (15)
S1—Ni1—S685.02 (4)S1—Ni1—S292.97 (4)
S1—Ni1—S7177.79 (4)S6—Ni1—S2177.66 (4)
S6—Ni1—S793.13 (4)S7—Ni1—S288.91 (4)
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, y+1, z; (iii) −x+1, −y+1, −z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12A···S6iv0.972.863.706 (4)147
Symmetry code: (iv) −x, −y+2, −z.
 

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