An unexpected mononuclear nickel thiolate, bis(perthioacetato-
S,S′)nickel(II), [Ni(C
2H
3S
3)
2], has been obtained by the reaction of Ni
II ions with thiolacetic acid. It consists of a planar rectangular NiS
4 unit. Weak hydrogen bonds of the type C—H
Ni form molecular ribbons along the
a axis. Among the products, γ-sulfur is also detected.
Supporting information
CCDC reference: 159824
Key indicators
- Single-crystal X-ray study
- T = 297 K
- Mean (C-C) = 0.005 Å
- R factor = 0.034
- wR factor = 0.087
- Data-to-parameter ratio = 18.7
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
ABSTM_02 Alert C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
Tmin and Tmax reported: 0.467 0.890
Tmin and Tmax expected: 0.418 0.887
RR = 1.113
Please check that your absorption correction is appropriate.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
Complex (I) has been obtained by a microscale reaction of NiCl2.H2O
(Aldrich) and thiolacetic acid (Aldrich) in the presence of KOH in ethanol as
solvent according to the method reported elsewhere (Mahmoudkhani & Langer,
1999a,b). Solvents were removed by vacuum distillation·The
products were then isolated by microextraction with benzene and subsequent
crystallization from benzene–acetone solution. Crystals of (I) suitable for
X-ray diffraction analysis were obtained after few days by slow evaporation of
the solution in acetone when allowed to stand over silica gel in a desiccator.
H atoms were constrained to the ideal geometry using an appropriate riding
model. The C—H distances (0.96 Å) and C—C—H angles (109.5°) were kept
fixed, while the torsion angles were allowed to refine with the starting
position based on threefold averaged circular Fourier synthesis.
Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT and SADABS (Sheldrick, 2001); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Crystal data top
[Ni(C2H3S3)2] | F(000) = 308 |
Mr = 305.16 | Dx = 1.942 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 5.3169 (3) Å | Cell parameters from 3360 reflections |
b = 6.1524 (3) Å | θ = 1–25° |
c = 15.9722 (8) Å | µ = 2.99 mm−1 |
β = 92.50 (1)° | T = 297 K |
V = 521.98 (5) Å3 | Parallepide, dark red |
Z = 2 | 0.30 × 0.25 × 0.04 mm |
Data collection top
Siemens SMART CCD diffractometer | 992 independent reflections |
Radiation source: fine-focus sealed tube | 848 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
Detector resolution: no pixels mm-1 | θmax = 25.7°, θmin = 2.6° |
ω scans | h = −6→6 |
Absorption correction: multi-scan Blessing (1995) | k = −7→7 |
Tmin = 0.467, Tmax = 0.890 | l = −19→19 |
4984 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0565P)2] where P = (Fo2 + 2Fc2)/3 |
992 reflections | (Δ/σ)max = 0.001 |
53 parameters | Δρmax = 0.56 e Å−3 |
0 restraints | Δρmin = −0.46 e Å−3 |
Crystal data top
[Ni(C2H3S3)2] | V = 521.98 (5) Å3 |
Mr = 305.16 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.3169 (3) Å | µ = 2.99 mm−1 |
b = 6.1524 (3) Å | T = 297 K |
c = 15.9722 (8) Å | 0.30 × 0.25 × 0.04 mm |
β = 92.50 (1)° | |
Data collection top
Siemens SMART CCD diffractometer | 992 independent reflections |
Absorption correction: multi-scan Blessing (1995) | 848 reflections with I > 2σ(I) |
Tmin = 0.467, Tmax = 0.890 | Rint = 0.047 |
4984 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.56 e Å−3 |
992 reflections | Δρmin = −0.46 e Å−3 |
53 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 | Uiso*/Ueq | |
Ni1 | 0.0000 | 0.0000 | 0.0000 | 0.0387 (2) | |
S3 | 0.07836 (17) | −0.17320 (15) | 0.11602 (5) | 0.0607 (3) | |
S2 | 0.35389 (19) | −0.00717 (14) | 0.18086 (6) | 0.0579 (3) | |
S1 | 0.27462 (17) | 0.25107 (13) | 0.02763 (5) | 0.0542 (3) | |
C2 | 0.6249 (6) | 0.3537 (6) | 0.1523 (2) | 0.0622 (9) | |
H2A | 0.6870 | 0.3053 | 0.2065 | 0.093* | |
H2B | 0.5583 | 0.4981 | 0.1568 | 0.093* | |
H2C | 0.7600 | 0.3541 | 0.1143 | 0.093* | |
C1 | 0.4217 (6) | 0.2036 (5) | 0.12013 (18) | 0.0464 (7) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.0409 (3) | 0.0398 (3) | 0.0349 (3) | −0.0043 (2) | −0.0047 (2) | −0.00078 (19) |
S3 | 0.0718 (6) | 0.0588 (5) | 0.0495 (5) | −0.0227 (4) | −0.0204 (4) | 0.0135 (4) |
S2 | 0.0594 (6) | 0.0647 (6) | 0.0477 (5) | −0.0121 (4) | −0.0191 (4) | 0.0079 (3) |
S1 | 0.0613 (5) | 0.0536 (5) | 0.0466 (5) | −0.0189 (4) | −0.0124 (4) | 0.0057 (3) |
C2 | 0.0541 (19) | 0.074 (2) | 0.057 (2) | −0.0187 (17) | −0.0132 (16) | −0.0069 (17) |
C1 | 0.0419 (15) | 0.0531 (18) | 0.0436 (16) | −0.0037 (13) | −0.0034 (12) | −0.0053 (13) |
Geometric parameters (Å, º) top
Ni1—S1 | 2.1579 (8) | S1—C1 | 1.667 (3) |
Ni1—S1i | 2.1579 (8) | C2—C1 | 1.496 (4) |
Ni1—S3i | 2.1623 (8) | C2—H2A | 0.96 |
Ni1—S3 | 2.1623 (8) | C2—H2B | 0.96 |
S3—S2 | 2.0322 (12) | C2—H2C | 0.96 |
S2—C1 | 1.668 (3) | | |
| | | |
S1—Ni1—S1i | 180.00 (5) | C1—C2—H2A | 109.5 |
S1—Ni1—S3i | 85.75 (3) | C1—C2—H2B | 109.5 |
S1i—Ni1—S3i | 94.25 (3) | H2A—C2—H2B | 109.5 |
S1—Ni1—S3 | 94.25 (3) | C1—C2—H2C | 109.5 |
S1i—Ni1—S3 | 85.75 (3) | H2A—C2—H2C | 109.5 |
S3i—Ni1—S3 | 180.00 (5) | H2B—C2—H2C | 109.5 |
S2—S3—Ni1 | 107.26 (4) | C2—C1—S1 | 120.0 (2) |
C1—S2—S3 | 105.29 (11) | C2—C1—S2 | 116.8 (2) |
C1—S1—Ni1 | 110.05 (11) | S1—C1—S2 | 123.14 (18) |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2C···Ni1ii | 0.96 | 3.15 | 3.880 (4) | 134 |
Symmetry code: (ii) x+1, y, z. |
Experimental details
Crystal data |
Chemical formula | [Ni(C2H3S3)2] |
Mr | 305.16 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 297 |
a, b, c (Å) | 5.3169 (3), 6.1524 (3), 15.9722 (8) |
β (°) | 92.50 (1) |
V (Å3) | 521.98 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.99 |
Crystal size (mm) | 0.30 × 0.25 × 0.04 |
|
Data collection |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Multi-scan Blessing (1995) |
Tmin, Tmax | 0.467, 0.890 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4984, 992, 848 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.610 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.087, 1.02 |
No. of reflections | 992 |
No. of parameters | 53 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.56, −0.46 |
Selected geometric parameters (Å, º) topNi1—S1 | 2.1579 (8) | S2—C1 | 1.668 (3) |
Ni1—S3 | 2.1623 (8) | S1—C1 | 1.667 (3) |
S3—S2 | 2.0322 (12) | C2—C1 | 1.496 (4) |
| | | |
S1—Ni1—S1i | 180.00 (5) | C1—S2—S3 | 105.29 (11) |
S1—Ni1—S3i | 85.75 (3) | C1—S1—Ni1 | 110.05 (11) |
S1—Ni1—S3 | 94.25 (3) | C2—C1—S1 | 120.0 (2) |
S3i—Ni1—S3 | 180.00 (5) | C2—C1—S2 | 116.8 (2) |
S2—S3—Ni1 | 107.26 (4) | S1—C1—S2 | 123.14 (18) |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2C···Ni1ii | 0.96 | 3.15 | 3.880 (4) | 134.3 |
Symmetry code: (ii) x+1, y, z. |
Metal thiolates, including nickel thiolates, are a rich class of compounds and they are relevant to the coordination of metal ions by sulfur-containing amino acids in biological systems. They are also of interest as synthetic models related to metal sulfide catalysis (Krebs & Henkel, 1991). The reaction of NiII ions with thiolate ligands, provides a large variety of structural possibilities ranging from mononuclear to polynuclear complexes including cyclic clusters and chain fragments. So far, several cyclic nickel thiolates have been synthesized and characterized by diffraction techniques, nevertheless, the governing factors of the degree of oligomerization of cyclic or chain nickel thiolates are still unknown. We believe that the study of structural systematics and relationships may lead to an understanding of the architecture of these compounds in order to design new cyclic clusters. Recently, we have reported the synthesis and structures of a pentanuclear and a hexanuclear cyclic nickel thiolates where the thiolate ligands were only different by the substituents on the β-C atom (Mahmoudkhani & Langer, 1999a,b). In order to understand the effect of electronic modulations on α-C atom of thiolate ligand, we have undertaken the reaction of NiII ions with thiolacetic acid. To our surprise, instead of a cyclic cluster, we obtained a mononuclear nickel thiolate, (I), in which the primary thiolcarboxylate ligand was transformed to a perthiocarboxylate ligand. This is to our best knowledge, the first example of an alkylperthiocarboxylato–metal complex, although there are some reports on the structure of arylperthiocarboxylate-metal complexes (Coucouvanis et al., 1985; Coucouvanis & Fackler, 1967; Fackler et al., 1968; Lanferdi et al., 1988).
These complexes are in general prepared by an oxidative addition of sulfur to the corresponding dithiocarboxylate–metal complex. But formation of this mononuclear nickel thiolate from the reaction of NiII ions with thiolacetic acid, seems to be rather unusual and unique. Furthermore, we have also detected the formation of γ-sulfur by this reaction which makes the interpretation much more complicated. Complex (I) crystallizes in the monoclinic system with space group P21/n. The structure is centrosymmetric and the asymmetric unit contains only a half of the molecule. The complex consists of a planar rectangular NiS4 unit with no trace of bridging by thiolate-S atom. The atomic numbering for the complex (I) is presented in Fig. 1. The bond distances and angles are about the same order as for other sulfur-rich nickel thiolates with a similar skeleton. The structure exhibits a hydrogen mediated interaction in the form of a weak hydrogen bonds of the type C—H···M forming molecular ribbons along a axis (see Fig. 2). The ability of metal centers to be involved in hydrogen bonds and hydrogen mediated interactions has been recently reviewed by Desiraju & Steiner (1999). For complex (I), the interaction C—H···Ni with an H···Ni distance of 3.15 Å and an angle of 134.3°, lies just in the range 2.5–3.2 Å to be regarded as a weak C—H···M hydrogen bond, and is shorter than the sum of van der Waals radii of 3.5 Å.