Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807037725/zl2056sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807037725/zl2056Isup2.hkl |
CCDC reference: 660059
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.002 Å
- R factor = 0.020
- wR factor = 0.063
- Data-to-parameter ratio = 21.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.96 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 1.01 PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni1 - S1 .. 5.86 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni1 - S2 .. 5.70 su PLAT411_ALERT_2_C Short Inter H...H Contact H4A .. H4A .. 2.11 Ang.
Alert level G PLAT793_ALERT_1_G Check the Absolute Configuration of N1 = ... R PLAT793_ALERT_1_G Check the Absolute Configuration of N2 = ... R PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1 (2) 2.02
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For related literature, see: Golden et al. (2005); Grapperhaus & Darensbourg (1998); Grapperhaus et al. (2004); Hatlevik et al. (2004); Linck et al. (2003); Mills et al. (1990); Rao et al. (2004); Allen (2002); Cremer & Pople (1975); Farrugia (1997); Li et al. (2002).
The ligand, 3,3'-[ethane-1,2-diylbis(methylimino)]dipropane-1-thiol, was prepared as the HCl salt from N,N'-dimethylethylenediamine and {[(3-bromopropyl)thio]methyl}benzene by modification of analagous routes (Li et al., 2002). To a degassed aqueous solution (10 ml) of NaOH (0.69 g, 17 mmol) was added the ligand·2HCl (1.3 g, 4.2 mmol) in 15 ml H2O. To the resulting suspension was dropwise added NiCl2·6H2O (1.0 g, 4.2 mmol) via cannula. Following addition, column separation (acetonitrile/alumina) yielded the title compound (0.74 g, 60% yield). Crystals suitable for X-ray analysis were obtained upon slow diffusion of diethylether into a methanolic solution of the title compound at 275 K (2°C).
Hydrogen atoms were placed in their geometrically generated positions and refined as a riding model. Methylene H's were included as fixed contributions with U(H) = 1.2 × Ueq (attached C atom) while methyl groups were allowed to ride on the attached C atom (the torsion angle which defines its orientation was allowed to refine), and these atoms were assigned U(H) = 1.5 x Ueq. The highest peak and deepest trough are located 0.74 Å from C7 and 0.84 Å from Ni1, respectively.
Square planar N2S2 nickel-thiolate complexes have been extensively studied due to their rich sulfur-based reactivity and their relevance to biological systems (Golden et al., 2005; Grapperhaus & Darensbourg, 1998; Grapperhaus et al., 2004; Rao et al., 2004). To our knowledge the title compound represents the first structurally characterized mononuclear square planar N2S2 nickel thiolate complex with a three-carbon aliphatic linker between the nitrogen and sulfur donors. A diamido N2S2 nickel thiolate complex with a three-carbon linker has been reported as the tetraethylammonium salt (Linck et al., 2003; CSD refcode IKEPIX) and its hydrate (Hatlevik et al., 2004; CSD refcode WARJUV). The X-ray structure of a complex related to the title compound with an aliphatic two-carbon linker between the nitrogen and sulfur donors has also been reported (Grapperhaus et al., 2004; CSD refcode AYIDOB).
The nickel atom of the title compound sits 0.018 (1) Å from the N2S2 ligand plane, which has a mean deviation of 0.047 (1) Å. Chelation of the ligand generates two nickel-containing six-membered rings and one five-membered ring. The five-membered ring containing N1 and N2 is best described as twisted, φ = 266.14 (16)° (Cremer & Pople, 1975). The six-membered rings containing N1/S1 and N2/S2 are in chair conformations with θ values of 171.52 (13) and 176.38 (12)°, respectively (Cremer & Pople 1975).
The six-membered chelate rings result in obtuse N—Ni—S bond angles. The N1—Ni—S1 and N2—Ni—S2 bond angles are 94.82 (4)° and 94.97 (4)°, respectively. In the related complex (Grapperhaus et al., 2004; AYIDOB) with five-membered N—Ni—S chelates the angles are slightly accute with values of 89.87 (9)° and 88.63 (9)°. A search of the Cambridge Structural Database (CSD, Version 5.27; Allen, 2002), yielded 27 square planar mononuclear N2S2Ni thiolate complexes that contain five-membered Ni—N—C—C—S chelate rings with N—Ni—S bond angles between 87.61 (7)° (Rao et al., 2004; CSD refcode LAHDAA) and 91.4 (2)° (Mills et al., 1990; CSD refcode VIGBES). The N1—Ni1—N2 bond angle of the title compound of 87.34 (5)° is similar to the value of 88.11 (12)° in the related complex (Grapperhaus et al., 2004; AYIDOB). As a result of these bond angles and the planar nature of the donor atoms, the S1—Ni—S2 bond angle is acute with a value of 82.965 (18)°. Acute S—Ni—S bond angles, 83.40 (4)° and 84.85°, are also observed in the related structures (Linck et al., 2003; IKEPIX & Hatlevik et al., 2003; WARJUV) with a three-carbon linker between nitrogen and sulfur. In the related system (Grapperhaus et al., 2004; AYIDOB) with all five-membered chelate rings, the corresponding S—Ni—S bond angle has a value of 95.16 (4)°.
The bond distances between the donor atoms and nickel are within expected ranges. The Ni—N bond distances of 2.0025 (13) and 2.0094 (13) Å are slightly longer than in the related system, 1.930 (3) and 1.950 (3) Å, (Grapperhaus et al., 2004; AYIDOB). The Ni—S bond distances of 2.1895 (6) and 2.1842 (5) Å display the same trend as compared to AYIDOB, 2.1612 (10) and 2.1612 (10) Å (Grapperhaus et al., 2004).
For related literature, see: Golden et al. (2005); Grapperhaus & Darensbourg (1998); Grapperhaus et al. (2004); Hatlevik et al. (2004); Linck et al. (2003); Mills et al. (1990); Rao et al. (2004); Allen (2002); Cremer & Pople (1975); Farrugia (1997); Li et al. (2002).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.
Fig. 1. ORTEP-3 (Farrugia, 1997) drawing of the title compound with atom labels showing 30% probability displacement ellipsoids for non-H atoms. |
[Ni(C10H22N2S2)] | F(000) = 624 |
Mr = 293.13 | Dx = 1.523 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 7691 reflections |
a = 8.2290 (16) Å | θ = 2.5–28.1° |
b = 13.304 (3) Å | µ = 1.82 mm−1 |
c = 11.691 (2) Å | T = 100 K |
β = 92.931 (3)° | Prism, dark purple |
V = 1278.2 (4) Å3 | 0.26 × 0.15 × 0.13 mm |
Z = 4 |
Bruker SMART APEX CCD diffractometer | 2986 independent reflections |
Radiation source: fine-focus sealed tube | 2699 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω scans | θmax = 28.1°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −10→10 |
Tmin = 0.676, Tmax = 0.779 | k = −17→17 |
10969 measured reflections | l = −15→15 |
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)] = 0.020 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.063 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0358P)2 + 0.7704P] where P = (Fo2 + 2Fc2)/3 |
2986 reflections | (Δ/σ)max = 0.001 |
138 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
[Ni(C10H22N2S2)] | V = 1278.2 (4) Å3 |
Mr = 293.13 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.2290 (16) Å | µ = 1.82 mm−1 |
b = 13.304 (3) Å | T = 100 K |
c = 11.691 (2) Å | 0.26 × 0.15 × 0.13 mm |
β = 92.931 (3)° |
Bruker SMART APEX CCD diffractometer | 2986 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 2699 reflections with I > 2σ(I) |
Tmin = 0.676, Tmax = 0.779 | Rint = 0.025 |
10969 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 0 restraints |
wR(F2) = 0.063 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.38 e Å−3 |
2986 reflections | Δρmin = −0.32 e Å−3 |
138 parameters |
Experimental. Data were collected with a Bruker SMART APEX CCD-based diffractometer using ω-scans of width 0.3° and 30 s duration at a crystal-to-detector distance of 4.908 cm. Intensity decay over the course of the data collection was evaluated by recollecting the first 50 frames of data at the end of the experiment. No significant decay was noted. Absorption correction was based upon symmetry equivalent and repeated intensity measurements using the program SADABS (Sheldrick, 2001). |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.77639 (2) | 0.225962 (14) | 0.772505 (15) | 0.01001 (7) | |
S1 | 0.67345 (5) | 0.37770 (3) | 0.76415 (3) | 0.01477 (10) | |
S2 | 0.95522 (5) | 0.29130 (3) | 0.66245 (3) | 0.01583 (10) | |
N1 | 0.59970 (15) | 0.16883 (10) | 0.86457 (11) | 0.0126 (3) | |
N2 | 0.88108 (15) | 0.08952 (9) | 0.78048 (11) | 0.0120 (2) | |
C1 | 0.58399 (19) | 0.40260 (12) | 0.90067 (13) | 0.0157 (3) | |
H1A | 0.6724 | 0.4048 | 0.9613 | 0.019* | |
H1B | 0.5325 | 0.4699 | 0.8970 | 0.019* | |
C2 | 0.45811 (19) | 0.32662 (13) | 0.93493 (14) | 0.0171 (3) | |
H2A | 0.3743 | 0.3194 | 0.8716 | 0.021* | |
H2B | 0.4038 | 0.3521 | 1.0028 | 0.021* | |
C3 | 0.5312 (2) | 0.22418 (12) | 0.96266 (14) | 0.0170 (3) | |
H3A | 0.6190 | 0.2329 | 1.0230 | 0.020* | |
H3B | 0.4461 | 0.1817 | 0.9951 | 0.020* | |
C4 | 0.6633 (2) | 0.07218 (12) | 0.91345 (14) | 0.0186 (3) | |
H4A | 0.5715 | 0.0293 | 0.9352 | 0.022* | |
H4B | 0.7333 | 0.0856 | 0.9831 | 0.022* | |
C5 | 0.7599 (2) | 0.01856 (12) | 0.82638 (14) | 0.0169 (3) | |
H5A | 0.8168 | −0.0398 | 0.8624 | 0.020* | |
H5B | 0.6861 | −0.0064 | 0.7631 | 0.020* | |
C6 | 0.93557 (19) | 0.04207 (12) | 0.67292 (13) | 0.0144 (3) | |
H6A | 0.8404 | 0.0368 | 0.6179 | 0.017* | |
H6B | 0.9728 | −0.0271 | 0.6911 | 0.017* | |
C7 | 1.07084 (19) | 0.09666 (12) | 0.61458 (13) | 0.0153 (3) | |
H7A | 1.1618 | 0.1089 | 0.6716 | 0.018* | |
H7B | 1.1119 | 0.0526 | 0.5542 | 0.018* | |
C8 | 1.0188 (2) | 0.19613 (12) | 0.56117 (13) | 0.0164 (3) | |
H8A | 0.9275 | 0.1836 | 0.5045 | 0.020* | |
H8B | 1.1105 | 0.2234 | 0.5192 | 0.020* | |
C9 | 0.46702 (19) | 0.14717 (13) | 0.77698 (15) | 0.0186 (3) | |
H9A | 0.5119 | 0.1118 | 0.7122 | 0.028* | |
H9B | 0.4173 | 0.2104 | 0.7502 | 0.028* | |
H9C | 0.3844 | 0.1050 | 0.8108 | 0.028* | |
C10 | 1.02212 (19) | 0.09729 (12) | 0.86542 (13) | 0.0158 (3) | |
H10A | 1.0819 | 0.0335 | 0.8681 | 0.024* | |
H10B | 0.9826 | 0.1120 | 0.9413 | 0.024* | |
H10C | 1.0945 | 0.1514 | 0.8427 | 0.024* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.01079 (11) | 0.00845 (11) | 0.01096 (11) | 0.00005 (7) | 0.00226 (7) | 0.00056 (7) |
S1 | 0.0188 (2) | 0.01017 (18) | 0.01574 (18) | 0.00216 (14) | 0.00438 (15) | 0.00106 (14) |
S2 | 0.0183 (2) | 0.01159 (18) | 0.01839 (19) | −0.00162 (14) | 0.00800 (15) | 0.00055 (14) |
N1 | 0.0120 (6) | 0.0119 (6) | 0.0141 (6) | 0.0005 (5) | 0.0016 (5) | 0.0011 (5) |
N2 | 0.0125 (6) | 0.0112 (6) | 0.0125 (6) | −0.0003 (5) | 0.0014 (5) | 0.0003 (5) |
C1 | 0.0175 (8) | 0.0137 (7) | 0.0160 (7) | 0.0025 (6) | 0.0010 (6) | −0.0032 (6) |
C2 | 0.0165 (8) | 0.0185 (8) | 0.0166 (7) | 0.0038 (6) | 0.0046 (6) | −0.0019 (6) |
C3 | 0.0196 (8) | 0.0178 (8) | 0.0143 (7) | 0.0013 (6) | 0.0071 (6) | 0.0017 (6) |
C4 | 0.0195 (8) | 0.0146 (8) | 0.0223 (8) | 0.0020 (6) | 0.0080 (6) | 0.0080 (6) |
C5 | 0.0170 (8) | 0.0109 (7) | 0.0232 (8) | 0.0004 (6) | 0.0056 (6) | 0.0037 (6) |
C6 | 0.0175 (7) | 0.0121 (7) | 0.0136 (7) | 0.0016 (6) | 0.0004 (6) | −0.0030 (6) |
C7 | 0.0162 (7) | 0.0168 (8) | 0.0130 (7) | 0.0030 (6) | 0.0030 (6) | −0.0016 (6) |
C8 | 0.0180 (8) | 0.0173 (8) | 0.0142 (7) | 0.0012 (6) | 0.0050 (6) | 0.0001 (6) |
C9 | 0.0149 (8) | 0.0169 (8) | 0.0239 (8) | −0.0039 (6) | −0.0006 (6) | −0.0019 (6) |
C10 | 0.0166 (8) | 0.0182 (8) | 0.0125 (7) | 0.0032 (6) | −0.0015 (6) | −0.0011 (6) |
Ni1—N1 | 2.0025 (13) | C4—C5 | 1.503 (2) |
Ni1—N2 | 2.0094 (13) | C4—H4A | 0.9900 |
Ni1—S2 | 2.1842 (5) | C4—H4B | 0.9900 |
Ni1—S1 | 2.1895 (6) | C5—H5A | 0.9900 |
S1—C1 | 1.8219 (16) | C5—H5B | 0.9900 |
S2—C8 | 1.8281 (16) | C6—C7 | 1.520 (2) |
N1—C9 | 1.486 (2) | C6—H6A | 0.9900 |
N1—C4 | 1.491 (2) | C6—H6B | 0.9900 |
N1—C3 | 1.497 (2) | C7—C8 | 1.516 (2) |
N2—C10 | 1.4920 (19) | C7—H7A | 0.9900 |
N2—C5 | 1.493 (2) | C7—H7B | 0.9900 |
N2—C6 | 1.4961 (19) | C8—H8A | 0.9900 |
C1—C2 | 1.516 (2) | C8—H8B | 0.9900 |
C1—H1A | 0.9900 | C9—H9A | 0.9800 |
C1—H1B | 0.9900 | C9—H9B | 0.9800 |
C2—C3 | 1.518 (2) | C9—H9C | 0.9800 |
C2—H2A | 0.9900 | C10—H10A | 0.9800 |
C2—H2B | 0.9900 | C10—H10B | 0.9800 |
C3—H3A | 0.9900 | C10—H10C | 0.9800 |
C3—H3B | 0.9900 | ||
N1—Ni1—N2 | 87.34 (5) | C5—C4—H4A | 109.7 |
N1—Ni1—S2 | 175.77 (4) | N1—C4—H4B | 109.7 |
N2—Ni1—S2 | 94.97 (4) | C5—C4—H4B | 109.7 |
N1—Ni1—S1 | 94.82 (4) | H4A—C4—H4B | 108.2 |
N2—Ni1—S1 | 177.38 (4) | N2—C5—C4 | 109.24 (13) |
S2—Ni1—S1 | 82.965 (18) | N2—C5—H5A | 109.8 |
C1—S1—Ni1 | 107.53 (5) | C4—C5—H5A | 109.8 |
C8—S2—Ni1 | 109.24 (6) | N2—C5—H5B | 109.8 |
C9—N1—C4 | 109.14 (13) | C4—C5—H5B | 109.8 |
C9—N1—C3 | 109.34 (12) | H5A—C5—H5B | 108.3 |
C4—N1—C3 | 105.62 (12) | N2—C6—C7 | 115.69 (13) |
C9—N1—Ni1 | 103.37 (10) | N2—C6—H6A | 108.4 |
C4—N1—Ni1 | 106.44 (9) | C7—C6—H6A | 108.4 |
C3—N1—Ni1 | 122.49 (10) | N2—C6—H6B | 108.4 |
C10—N2—C5 | 108.41 (12) | C7—C6—H6B | 108.4 |
C10—N2—C6 | 109.40 (12) | H6A—C6—H6B | 107.4 |
C5—N2—C6 | 105.65 (12) | C8—C7—C6 | 113.83 (13) |
C10—N2—Ni1 | 106.58 (9) | C8—C7—H7A | 108.8 |
C5—N2—Ni1 | 107.17 (9) | C6—C7—H7A | 108.8 |
C6—N2—Ni1 | 119.23 (9) | C8—C7—H7B | 108.8 |
C2—C1—S1 | 114.99 (11) | C6—C7—H7B | 108.8 |
C2—C1—H1A | 108.5 | H7A—C7—H7B | 107.7 |
S1—C1—H1A | 108.5 | C7—C8—S2 | 114.97 (11) |
C2—C1—H1B | 108.5 | C7—C8—H8A | 108.5 |
S1—C1—H1B | 108.5 | S2—C8—H8A | 108.5 |
H1A—C1—H1B | 107.5 | C7—C8—H8B | 108.5 |
C1—C2—C3 | 112.73 (13) | S2—C8—H8B | 108.5 |
C1—C2—H2A | 109.0 | H8A—C8—H8B | 107.5 |
C3—C2—H2A | 109.0 | N1—C9—H9A | 109.5 |
C1—C2—H2B | 109.0 | N1—C9—H9B | 109.5 |
C3—C2—H2B | 109.0 | H9A—C9—H9B | 109.5 |
H2A—C2—H2B | 107.8 | N1—C9—H9C | 109.5 |
N1—C3—C2 | 116.02 (13) | H9A—C9—H9C | 109.5 |
N1—C3—H3A | 108.3 | H9B—C9—H9C | 109.5 |
C2—C3—H3A | 108.3 | N2—C10—H10A | 109.5 |
N1—C3—H3B | 108.3 | N2—C10—H10B | 109.5 |
C2—C3—H3B | 108.3 | H10A—C10—H10B | 109.5 |
H3A—C3—H3B | 107.4 | N2—C10—H10C | 109.5 |
N1—C4—C5 | 109.71 (13) | H10A—C10—H10C | 109.5 |
N1—C4—H4A | 109.7 | H10B—C10—H10C | 109.5 |
N1—Ni1—S1—C1 | 36.46 (7) | C9—N1—C3—C2 | −62.81 (17) |
S2—Ni1—S1—C1 | −147.17 (6) | C4—N1—C3—C2 | 179.87 (13) |
N2—Ni1—S2—C8 | 36.06 (7) | Ni1—N1—C3—C2 | 58.12 (18) |
S1—Ni1—S2—C8 | −145.57 (6) | C1—C2—C3—N1 | −66.32 (18) |
N2—Ni1—N1—C9 | −99.81 (10) | C9—N1—C4—C5 | 72.07 (16) |
S1—Ni1—N1—C9 | 81.68 (9) | C3—N1—C4—C5 | −170.48 (13) |
N2—Ni1—N1—C4 | 15.12 (10) | Ni1—N1—C4—C5 | −38.88 (15) |
S1—Ni1—N1—C4 | −163.39 (9) | C10—N2—C5—C4 | 79.24 (15) |
N2—Ni1—N1—C3 | 136.49 (12) | C6—N2—C5—C4 | −163.58 (13) |
S1—Ni1—N1—C3 | −42.02 (11) | Ni1—N2—C5—C4 | −35.45 (15) |
N1—Ni1—N2—C10 | −104.72 (10) | N1—C4—C5—N2 | 50.42 (17) |
S2—Ni1—N2—C10 | 78.83 (9) | C10—N2—C6—C7 | −58.73 (16) |
N1—Ni1—N2—C5 | 11.18 (10) | C5—N2—C6—C7 | −175.24 (13) |
S2—Ni1—N2—C5 | −165.26 (9) | Ni1—N2—C6—C7 | 64.21 (15) |
N1—Ni1—N2—C6 | 130.96 (11) | N2—C6—C7—C8 | −69.57 (17) |
S2—Ni1—N2—C6 | −45.49 (10) | C6—C7—C8—S2 | 63.46 (16) |
Ni1—S1—C1—C2 | −55.79 (12) | Ni1—S2—C8—C7 | −50.50 (13) |
S1—C1—C2—C3 | 68.03 (16) |
Experimental details
Crystal data | |
Chemical formula | [Ni(C10H22N2S2)] |
Mr | 293.13 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 8.2290 (16), 13.304 (3), 11.691 (2) |
β (°) | 92.931 (3) |
V (Å3) | 1278.2 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.82 |
Crystal size (mm) | 0.26 × 0.15 × 0.13 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.676, 0.779 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10969, 2986, 2699 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.662 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.063, 1.02 |
No. of reflections | 2986 |
No. of parameters | 138 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.32 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.
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Square planar N2S2 nickel-thiolate complexes have been extensively studied due to their rich sulfur-based reactivity and their relevance to biological systems (Golden et al., 2005; Grapperhaus & Darensbourg, 1998; Grapperhaus et al., 2004; Rao et al., 2004). To our knowledge the title compound represents the first structurally characterized mononuclear square planar N2S2 nickel thiolate complex with a three-carbon aliphatic linker between the nitrogen and sulfur donors. A diamido N2S2 nickel thiolate complex with a three-carbon linker has been reported as the tetraethylammonium salt (Linck et al., 2003; CSD refcode IKEPIX) and its hydrate (Hatlevik et al., 2004; CSD refcode WARJUV). The X-ray structure of a complex related to the title compound with an aliphatic two-carbon linker between the nitrogen and sulfur donors has also been reported (Grapperhaus et al., 2004; CSD refcode AYIDOB).
The nickel atom of the title compound sits 0.018 (1) Å from the N2S2 ligand plane, which has a mean deviation of 0.047 (1) Å. Chelation of the ligand generates two nickel-containing six-membered rings and one five-membered ring. The five-membered ring containing N1 and N2 is best described as twisted, φ = 266.14 (16)° (Cremer & Pople, 1975). The six-membered rings containing N1/S1 and N2/S2 are in chair conformations with θ values of 171.52 (13) and 176.38 (12)°, respectively (Cremer & Pople 1975).
The six-membered chelate rings result in obtuse N—Ni—S bond angles. The N1—Ni—S1 and N2—Ni—S2 bond angles are 94.82 (4)° and 94.97 (4)°, respectively. In the related complex (Grapperhaus et al., 2004; AYIDOB) with five-membered N—Ni—S chelates the angles are slightly accute with values of 89.87 (9)° and 88.63 (9)°. A search of the Cambridge Structural Database (CSD, Version 5.27; Allen, 2002), yielded 27 square planar mononuclear N2S2Ni thiolate complexes that contain five-membered Ni—N—C—C—S chelate rings with N—Ni—S bond angles between 87.61 (7)° (Rao et al., 2004; CSD refcode LAHDAA) and 91.4 (2)° (Mills et al., 1990; CSD refcode VIGBES). The N1—Ni1—N2 bond angle of the title compound of 87.34 (5)° is similar to the value of 88.11 (12)° in the related complex (Grapperhaus et al., 2004; AYIDOB). As a result of these bond angles and the planar nature of the donor atoms, the S1—Ni—S2 bond angle is acute with a value of 82.965 (18)°. Acute S—Ni—S bond angles, 83.40 (4)° and 84.85°, are also observed in the related structures (Linck et al., 2003; IKEPIX & Hatlevik et al., 2003; WARJUV) with a three-carbon linker between nitrogen and sulfur. In the related system (Grapperhaus et al., 2004; AYIDOB) with all five-membered chelate rings, the corresponding S—Ni—S bond angle has a value of 95.16 (4)°.
The bond distances between the donor atoms and nickel are within expected ranges. The Ni—N bond distances of 2.0025 (13) and 2.0094 (13) Å are slightly longer than in the related system, 1.930 (3) and 1.950 (3) Å, (Grapperhaus et al., 2004; AYIDOB). The Ni—S bond distances of 2.1895 (6) and 2.1842 (5) Å display the same trend as compared to AYIDOB, 2.1612 (10) and 2.1612 (10) Å (Grapperhaus et al., 2004).