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

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.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](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

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S1. Comment

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

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).

S2. Experimental

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).

S3. Refinement

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 × U_eq (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 U_eq. The highest peak and deepest trough are located 0.74 Å from C7 and 0.84 Å from Ni1, respectively.

Computing details

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

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)

Crystal data

[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) Å^3	0.26 × 0.15 × 0.13 mm
Z = 4

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.063	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0358P)^2 + 0.7704P] where P = (Fo^2 + 2Fc^2)/3
2986 reflections	(Δ/σ)max = 0.001
138 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)