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Acta Cryst. (2007). E63, m2281    [ doi:10.1107/S1600536807037725 ]

{3,3'-[Ethane-1,2-diylbis(methylimino)]bis(propane-1-thiolato)}nickel(II)

C. A. Grapperhaus, M. G. O'Toole and M. S. Mashuta

Abstract top

The title compound, [Ni(C10H22N2S2)], contains a square-planar Ni center coordinated by the tetradentate ligand 3,3'-[ethane-1,2-diylbis(methylimino)]dipropane-1-thiolate. Upon chelation, the N2S2 ligand generates one five-membered chelate ring containing the N donors and two six-membered chelate rings in chair conformations, each containing one N and one S donor. The cis S donors, which are not directly linked together, form an acute S-Ni-S angle of 82.965 (18)° due to ligand constraints.

Comment top

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).

Related literature top

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).

Experimental top

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).

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. ORTEP-3 (Farrugia, 1997) drawing of the title compound with atom labels showing 30% probability displacement ellipsoids for non-H atoms.
{3,3'-[ethane-1,2-diylbis(methylimino)]dipropane-1-thiolato}nickel(II) top
Crystal data top
[Ni(C10H22N2S2)]F000 = 624
Mr = 293.13Dx = 1.523 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7691 reflections
a = 8.2290 (16) Åθ = 2.5–28.1º
b = 13.304 (3) ŵ = 1.82 mm−1
c = 11.691 (2) ÅT = 100 (2) K
β = 92.931 (3)ºPrism, dark purple
V = 1278.2 (4) Å30.26 × 0.15 × 0.13 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer		2986 independent reflections
Radiation source: fine-focus sealed tube2699 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.025
T = 100(2) Kθmax = 28.1º
ω scansθmin = 2.3º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)		h = −10→10
Tmin = 0.676, Tmax = 0.779k = −17→17
10969 measured reflectionsl = −15→15
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)] = 0.020H-atom parameters constrained
wR(F2) = 0.063  w = 1/[σ2(Fo2) + (0.0358P)2 + 0.7704P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
2986 reflectionsΔρmax = 0.38 e Å−3
138 parametersΔρmin = −0.31 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Ni(C10H22N2S2)]V = 1278.2 (4) Å3
Mr = 293.13Z = 4
Monoclinic, P21/cMo Kα
a = 8.2290 (16) ŵ = 1.82 mm−1
b = 13.304 (3) ÅT = 100 (2) K
c = 11.691 (2) Å0.26 × 0.15 × 0.13 mm
β = 92.931 (3)º
Data collection top
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 = 0.779Rint = 0.025
10969 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.020138 parameters
wR(F2) = 0.063H-atom parameters constrained
S = 1.02Δρmax = 0.38 e Å−3
2986 reflectionsΔρmin = −0.31 e Å−3
Special details top

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).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.77639 (2)0.225962 (14)0.772505 (15)0.01001 (7)
S10.67345 (5)0.37770 (3)0.76415 (3)0.01477 (10)
S20.95522 (5)0.29130 (3)0.66245 (3)0.01583 (10)
N10.59970 (15)0.16883 (10)0.86457 (11)0.0126 (3)
N20.88108 (15)0.08952 (9)0.78048 (11)0.0120 (2)
C10.58399 (19)0.40260 (12)0.90067 (13)0.0157 (3)
H1A0.67240.40480.96130.019*
H1B0.53250.46990.89700.019*
C20.45811 (19)0.32662 (13)0.93493 (14)0.0171 (3)
H2A0.37430.31940.87160.021*
H2B0.40380.35211.00280.021*
C30.5312 (2)0.22418 (12)0.96266 (14)0.0170 (3)
H3A0.61900.23291.02300.020*
H3B0.44610.18170.99510.020*
C40.6633 (2)0.07218 (12)0.91345 (14)0.0186 (3)
H4A0.57150.02930.93520.022*
H4B0.73330.08560.98310.022*
C50.7599 (2)0.01856 (12)0.82638 (14)0.0169 (3)
H5A0.8168−0.03980.86240.020*
H5B0.6861−0.00640.76310.020*
C60.93557 (19)0.04207 (12)0.67292 (13)0.0144 (3)
H6A0.84040.03680.61790.017*
H6B0.9728−0.02710.69110.017*
C71.07084 (19)0.09666 (12)0.61458 (13)0.0153 (3)
H7A1.16180.10890.67160.018*
H7B1.11190.05260.55420.018*
C81.0188 (2)0.19613 (12)0.56117 (13)0.0164 (3)
H8A0.92750.18360.50450.020*
H8B1.11050.22340.51920.020*
C90.46702 (19)0.14717 (13)0.77698 (15)0.0186 (3)
H9A0.51190.11180.71220.028*
H9B0.41730.21040.75020.028*
H9C0.38440.10500.81080.028*
C101.02212 (19)0.09729 (12)0.86542 (13)0.0158 (3)
H10A1.08190.03350.86810.024*
H10B0.98260.11200.94130.024*
H10C1.09450.15140.84270.024*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.01079 (11)0.00845 (11)0.01096 (11)0.00005 (7)0.00226 (7)0.00056 (7)
S10.0188 (2)0.01017 (18)0.01574 (18)0.00216 (14)0.00438 (15)0.00106 (14)
S20.0183 (2)0.01159 (18)0.01839 (19)−0.00162 (14)0.00800 (15)0.00055 (14)
N10.0120 (6)0.0119 (6)0.0141 (6)0.0005 (5)0.0016 (5)0.0011 (5)
N20.0125 (6)0.0112 (6)0.0125 (6)−0.0003 (5)0.0014 (5)0.0003 (5)
C10.0175 (8)0.0137 (7)0.0160 (7)0.0025 (6)0.0010 (6)−0.0032 (6)
C20.0165 (8)0.0185 (8)0.0166 (7)0.0038 (6)0.0046 (6)−0.0019 (6)
C30.0196 (8)0.0178 (8)0.0143 (7)0.0013 (6)0.0071 (6)0.0017 (6)
C40.0195 (8)0.0146 (8)0.0223 (8)0.0020 (6)0.0080 (6)0.0080 (6)
C50.0170 (8)0.0109 (7)0.0232 (8)0.0004 (6)0.0056 (6)0.0037 (6)
C60.0175 (7)0.0121 (7)0.0136 (7)0.0016 (6)0.0004 (6)−0.0030 (6)
C70.0162 (7)0.0168 (8)0.0130 (7)0.0030 (6)0.0030 (6)−0.0016 (6)
C80.0180 (8)0.0173 (8)0.0142 (7)0.0012 (6)0.0050 (6)0.0001 (6)
C90.0149 (8)0.0169 (8)0.0239 (8)−0.0039 (6)−0.0006 (6)−0.0019 (6)
C100.0166 (8)0.0182 (8)0.0125 (7)0.0032 (6)−0.0015 (6)−0.0011 (6)
Geometric parameters (Å, °) top
Ni1—N12.0025 (13)C4—C51.503 (2)
Ni1—N22.0094 (13)C4—H4A0.9900
Ni1—S22.1842 (5)C4—H4B0.9900
Ni1—S12.1895 (6)C5—H5A0.9900
S1—C11.8219 (16)C5—H5B0.9900
S2—C81.8281 (16)C6—C71.520 (2)
N1—C91.486 (2)C6—H6A0.9900
N1—C41.491 (2)C6—H6B0.9900
N1—C31.497 (2)C7—C81.516 (2)
N2—C101.4920 (19)C7—H7A0.9900
N2—C51.493 (2)C7—H7B0.9900
N2—C61.4961 (19)C8—H8A0.9900
C1—C21.516 (2)C8—H8B0.9900
C1—H1A0.9900C9—H9A0.9800
C1—H1B0.9900C9—H9B0.9800
C2—C31.518 (2)C9—H9C0.9800
C2—H2A0.9900C10—H10A0.9800
C2—H2B0.9900C10—H10B0.9800
C3—H3A0.9900C10—H10C0.9800
C3—H3B0.9900
N1—Ni1—N287.34 (5)C5—C4—H4A109.7
N1—Ni1—S2175.77 (4)N1—C4—H4B109.7
N2—Ni1—S294.97 (4)C5—C4—H4B109.7
N1—Ni1—S194.82 (4)H4A—C4—H4B108.2
N2—Ni1—S1177.38 (4)N2—C5—C4109.24 (13)
S2—Ni1—S182.965 (18)N2—C5—H5A109.8
C1—S1—Ni1107.53 (5)C4—C5—H5A109.8
C8—S2—Ni1109.24 (6)N2—C5—H5B109.8
C9—N1—C4109.14 (13)C4—C5—H5B109.8
C9—N1—C3109.34 (12)H5A—C5—H5B108.3
C4—N1—C3105.62 (12)N2—C6—C7115.69 (13)
C9—N1—Ni1103.37 (10)N2—C6—H6A108.4
C4—N1—Ni1106.44 (9)C7—C6—H6A108.4
C3—N1—Ni1122.49 (10)N2—C6—H6B108.4
C10—N2—C5108.41 (12)C7—C6—H6B108.4
C10—N2—C6109.40 (12)H6A—C6—H6B107.4
C5—N2—C6105.65 (12)C8—C7—C6113.83 (13)
C10—N2—Ni1106.58 (9)C8—C7—H7A108.8
C5—N2—Ni1107.17 (9)C6—C7—H7A108.8
C6—N2—Ni1119.23 (9)C8—C7—H7B108.8
C2—C1—S1114.99 (11)C6—C7—H7B108.8
C2—C1—H1A108.5H7A—C7—H7B107.7
S1—C1—H1A108.5C7—C8—S2114.97 (11)
C2—C1—H1B108.5C7—C8—H8A108.5
S1—C1—H1B108.5S2—C8—H8A108.5
H1A—C1—H1B107.5C7—C8—H8B108.5
C1—C2—C3112.73 (13)S2—C8—H8B108.5
C1—C2—H2A109.0H8A—C8—H8B107.5
C3—C2—H2A109.0N1—C9—H9A109.5
C1—C2—H2B109.0N1—C9—H9B109.5
C3—C2—H2B109.0H9A—C9—H9B109.5
H2A—C2—H2B107.8N1—C9—H9C109.5
N1—C3—C2116.02 (13)H9A—C9—H9C109.5
N1—C3—H3A108.3H9B—C9—H9C109.5
C2—C3—H3A108.3N2—C10—H10A109.5
N1—C3—H3B108.3N2—C10—H10B109.5
C2—C3—H3B108.3H10A—C10—H10B109.5
H3A—C3—H3B107.4N2—C10—H10C109.5
N1—C4—C5109.71 (13)H10A—C10—H10C109.5
N1—C4—H4A109.7H10B—C10—H10C109.5
N1—Ni1—S1—C136.46 (7)C9—N1—C3—C2−62.81 (17)
S2—Ni1—S1—C1−147.17 (6)C4—N1—C3—C2179.87 (13)
N2—Ni1—S2—C836.06 (7)Ni1—N1—C3—C258.12 (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—C572.07 (16)
S1—Ni1—N1—C981.68 (9)C3—N1—C4—C5−170.48 (13)
N2—Ni1—N1—C415.12 (10)Ni1—N1—C4—C5−38.88 (15)
S1—Ni1—N1—C4−163.39 (9)C10—N2—C5—C479.24 (15)
N2—Ni1—N1—C3136.49 (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—N250.42 (17)
S2—Ni1—N2—C1078.83 (9)C10—N2—C6—C7−58.73 (16)
N1—Ni1—N2—C511.18 (10)C5—N2—C6—C7−175.24 (13)
S2—Ni1—N2—C5−165.26 (9)Ni1—N2—C6—C764.21 (15)
N1—Ni1—N2—C6130.96 (11)N2—C6—C7—C8−69.57 (17)
S2—Ni1—N2—C6−45.49 (10)C6—C7—C8—S263.46 (16)
Ni1—S1—C1—C2−55.79 (12)Ni1—S2—C8—C7−50.50 (13)
S1—C1—C2—C368.03 (16)
Acknowledgements top

This research was supported by the National Science Foundation (grant No. CHE-0238137). MSM thanks the Kentucky Research Challenge Trust Fund for the purchase of CCD X-ray equipment and the upgrade of our X-ray facility.

references
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