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The title compound, [Ni(C5H10NS2)3], belongs to the symmetry point group C2. The Ni atom, one ring C atom and its adjacent N atom are located on a twofold rotation axis. Thus, there is just one half-molecule in the asymmetric unit. The compound is isostructural with the Fe and Co analogues.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803006044/na6214sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803006044/na6214Isup2.hkl
Contains datablock I

CCDC reference: 209895

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.022
  • wR factor = 0.060
  • Data-to-parameter ratio = 28.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

The title compound, (I), belongs to the symmetry point group C2. Atoms Ni1, C1 and N1 are located on a twofold rotation axis. Thus, there is just half a molecule in the asymmetric unit. Compound (I) is isostructural with the Fe (Leipoldt & Coppens, 1973) and Co analogues (Brennan & Bernal, 1969; Merlino, 1968; Healy et al., 1990; Kong et al., 1998).

Experimental top

In an effort to synthesize a macrocyclic transition metal complex, we added the compounds nickel nitrate hexahydrate, tris(2-aminoethyl)amine and sodium diethyldithiocarbamate to DMSO as solvent medium. From the product mixture, we isolated suitable single crystals. The crystal data showed an entirely different structure from what we expected.

Refinement top

All H atoms could be located by difference Fourier synthesis and were refined with fixed individual displacement parameters [Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl)] using a riding model, with secondary C—H = 0.99 Å or methyl C—H = 0.98 Å.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991).

Figures top
[Figure 1] Fig. 1. Perspective view of the title compound with the atom numbering; displacement ellipsoids are at the 50% probability level. H atoms have been omitted for clarity. [Symmetry code: (i) 1 − x, y, 3/2 − z.]
Tris(N,N-diethyldithiocarbamato-κ2S,S')nickel(II) top
Crystal data top
[Ni(C5H10NS2)3]F(000) = 1060
Mr = 503.49Dx = 1.464 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 15127 reflections
a = 14.0208 (9) Åθ = 3.7–29.9°
b = 10.2305 (7) ŵ = 1.40 mm1
c = 16.9031 (11) ÅT = 173 K
β = 109.630 (5)°Block, light violet
V = 2283.7 (3) Å30.20 × 0.20 × 0.10 mm
Z = 4
Data collection top
Stoe IPDS-II two-circle
diffractometer
3232 independent reflections
Radiation source: fine-focus sealed tube2635 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
ω scansθmax = 29.7°, θmin = 3.9°
Absorption correction: multi-scan
(MULABS; Spek, 1990; Blessing, 1995)
h = 1918
Tmin = 0.767, Tmax = 0.872k = 1414
16440 measured reflectionsl = 2323
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)] = 0.022Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.061H-atom parameters constrained
S = 0.96 w = 1/[σ2(Fo2) + (0.0409P)2]
where P = (Fo2 + 2Fc2)/3
3232 reflections(Δ/σ)max = 0.002
115 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.80 e Å3
Crystal data top
[Ni(C5H10NS2)3]V = 2283.7 (3) Å3
Mr = 503.49Z = 4
Monoclinic, C2/cMo Kα radiation
a = 14.0208 (9) ŵ = 1.40 mm1
b = 10.2305 (7) ÅT = 173 K
c = 16.9031 (11) Å0.20 × 0.20 × 0.10 mm
β = 109.630 (5)°
Data collection top
Stoe IPDS-II two-circle
diffractometer
3232 independent reflections
Absorption correction: multi-scan
(MULABS; Spek, 1990; Blessing, 1995)
2635 reflections with I > 2σ(I)
Tmin = 0.767, Tmax = 0.872Rint = 0.037
16440 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0220 restraints
wR(F2) = 0.061H-atom parameters constrained
S = 0.96Δρmax = 0.39 e Å3
3232 reflectionsΔρmin = 0.80 e Å3
115 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
xyzUiso*/Ueq
Ni10.50000.25100 (2)0.75000.02044 (7)
C10.50000.01879 (19)0.75000.0230 (4)
C20.40977 (15)0.22287 (16)0.74875 (11)0.0387 (4)
H2A0.40560.30360.71540.046*
H2B0.34870.16990.72040.046*
C30.4101 (2)0.2595 (2)0.83540 (14)0.0556 (6)
H3A0.34820.30830.83070.083*
H3B0.41280.18000.86840.083*
H3C0.46930.31400.86330.083*
C40.35964 (10)0.38592 (13)0.62047 (8)0.0201 (2)
C50.29340 (12)0.43897 (15)0.47172 (8)0.0272 (3)
H5A0.22290.43160.43260.033*
H5B0.32990.35820.46670.033*
C60.22847 (12)0.55200 (16)0.57631 (10)0.0329 (3)
H6A0.26370.63710.58160.040*
H6B0.22030.53250.63100.040*
C70.34366 (16)0.5549 (2)0.44681 (12)0.0429 (4)
H7A0.34190.54400.38870.064*
H7B0.41420.56080.48420.064*
H7C0.30750.63500.45140.064*
C80.12560 (12)0.5640 (2)0.51083 (13)0.0439 (4)
H8A0.08740.63310.52710.066*
H8B0.08940.48080.50590.066*
H8C0.13280.58610.45670.066*
N10.50000.14880 (17)0.75000.0293 (4)
N20.29225 (9)0.45005 (12)0.55808 (7)0.0245 (2)
S10.37317 (3)0.39993 (3)0.72495 (2)0.02400 (8)
S20.39946 (2)0.07687 (3)0.75000 (2)0.02308 (8)
S30.44642 (2)0.27616 (3)0.608522 (19)0.02077 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.02321 (12)0.01827 (12)0.02022 (12)0.0000.00779 (9)0.000
C10.0291 (9)0.0186 (8)0.0182 (8)0.0000.0040 (7)0.000
C20.0506 (10)0.0215 (7)0.0353 (8)0.0116 (7)0.0030 (7)0.0015 (6)
C30.0709 (14)0.0481 (11)0.0452 (11)0.0183 (10)0.0160 (10)0.0084 (9)
C40.0230 (6)0.0183 (5)0.0198 (6)0.0001 (4)0.0082 (5)0.0006 (4)
C50.0318 (7)0.0310 (7)0.0176 (6)0.0030 (6)0.0068 (5)0.0016 (5)
C60.0346 (8)0.0326 (8)0.0291 (7)0.0122 (6)0.0075 (6)0.0009 (6)
C70.0487 (10)0.0465 (10)0.0387 (9)0.0071 (8)0.0216 (8)0.0052 (8)
C80.0260 (7)0.0474 (10)0.0524 (10)0.0072 (7)0.0054 (7)0.0094 (8)
N10.0391 (10)0.0173 (7)0.0262 (8)0.0000.0037 (7)0.000
N20.0281 (6)0.0257 (6)0.0196 (5)0.0064 (5)0.0081 (4)0.0015 (4)
S10.03101 (16)0.02389 (16)0.01844 (14)0.00734 (13)0.01007 (12)0.00035 (11)
S20.02316 (15)0.02081 (15)0.02484 (15)0.00264 (12)0.00750 (11)0.00091 (12)
S30.02337 (15)0.02119 (15)0.01871 (14)0.00227 (11)0.00833 (11)0.00149 (11)
Geometric parameters (Å, º) top
Ni1—S3i2.2676 (3)C4—S31.7166 (13)
Ni1—S32.2677 (4)C4—S11.7178 (13)
Ni1—S12.2709 (4)C5—N21.4696 (18)
Ni1—S1i2.2709 (4)C5—C71.510 (2)
Ni1—S22.2717 (4)C5—H5A0.9900
Ni1—S2i2.2717 (4)C5—H5B0.9900
C1—N11.330 (2)C6—N21.4723 (19)
C1—S21.7161 (11)C6—C81.499 (2)
C1—S2i1.7161 (11)C6—H6A0.9900
C2—N11.469 (2)C6—H6B0.9900
C2—C31.510 (3)C7—H7A0.9800
C2—H2A0.9900C7—H7B0.9800
C2—H2B0.9900C7—H7C0.9800
C3—H3A0.9800C8—H8A0.9800
C3—H3B0.9800C8—H8B0.9800
C3—H3C0.9800C8—H8C0.9800
C4—N21.3289 (17)N1—C2i1.469 (2)
S3i—Ni1—S3166.97 (2)N2—C5—C7112.23 (13)
S3i—Ni1—S194.687 (13)N2—C5—H5A109.2
S3—Ni1—S176.466 (12)C7—C5—H5A109.2
S3i—Ni1—S1i76.466 (13)N2—C5—H5B109.2
S3—Ni1—S1i94.687 (13)C7—C5—H5B109.2
S1—Ni1—S1i95.72 (2)H5A—C5—H5B107.9
S3i—Ni1—S294.285 (13)N2—C6—C8113.89 (14)
S3—Ni1—S295.929 (13)N2—C6—H6A108.8
S1—Ni1—S294.538 (14)C8—C6—H6A108.8
S1i—Ni1—S2166.699 (14)N2—C6—H6B108.8
S3i—Ni1—S2i95.931 (13)C8—C6—H6B108.8
S3—Ni1—S2i94.283 (13)H6A—C6—H6B107.7
S1—Ni1—S2i166.698 (14)C5—C7—H7A109.5
S1i—Ni1—S2i94.536 (14)C5—C7—H7B109.5
S2—Ni1—S2i76.71 (2)H7A—C7—H7B109.5
N1—C1—S2124.77 (5)C5—C7—H7C109.5
N1—C1—S2i124.77 (5)H7A—C7—H7C109.5
S2—C1—S2i110.46 (11)H7B—C7—H7C109.5
N1—C2—C3113.11 (15)C6—C8—H8A109.5
N1—C2—H2A109.0C6—C8—H8B109.5
C3—C2—H2A109.0H8A—C8—H8B109.5
N1—C2—H2B109.0C6—C8—H8C109.5
C3—C2—H2B109.0H8A—C8—H8C109.5
H2A—C2—H2B107.8H8B—C8—H8C109.5
C2—C3—H3A109.5C1—N1—C2121.06 (10)
C2—C3—H3B109.5C1—N1—C2i121.06 (10)
H3A—C3—H3B109.5C2—N1—C2i117.9 (2)
C2—C3—H3C109.5C4—N2—C5120.53 (12)
H3A—C3—H3C109.5C4—N2—C6120.24 (11)
H3B—C3—H3C109.5C5—N2—C6118.20 (11)
N2—C4—S3124.94 (10)C4—S1—Ni186.83 (5)
N2—C4—S1125.32 (10)C1—S2—Ni186.42 (5)
S3—C4—S1109.74 (7)C4—S3—Ni186.96 (4)
S2—C1—N1—C20.91 (8)S1i—Ni1—S1—C493.59 (5)
S2i—C1—N1—C2179.09 (8)S2—Ni1—S1—C494.89 (5)
S2—C1—N1—C2i179.10 (8)S2i—Ni1—S1—C446.69 (8)
S2i—C1—N1—C2i0.91 (8)N1—C1—S2—Ni1180.0
C3—C2—N1—C193.33 (17)S2i—C1—S2—Ni10.002 (1)
C3—C2—N1—C2i86.67 (17)S3i—Ni1—S2—C195.091 (15)
S3—C4—N2—C55.43 (19)S3—Ni1—S2—C193.018 (14)
S1—C4—N2—C5174.64 (11)S1—Ni1—S2—C1169.852 (13)
S3—C4—N2—C6173.66 (12)S1i—Ni1—S2—C149.76 (6)
S1—C4—N2—C66.4 (2)S2i—Ni1—S2—C10.0
C7—C5—N2—C4100.31 (17)N2—C4—S3—Ni1179.76 (12)
C7—C5—N2—C668.15 (19)S1—C4—S3—Ni10.18 (6)
C8—C6—N2—C4148.52 (16)S3i—Ni1—S3—C448.29 (5)
C8—C6—N2—C543.0 (2)S1—Ni1—S3—C40.13 (5)
N2—C4—S1—Ni1179.76 (12)S1i—Ni1—S3—C494.90 (5)
S3—C4—S1—Ni10.18 (6)S2—Ni1—S3—C493.12 (5)
S3i—Ni1—S1—C4170.43 (5)S2i—Ni1—S3—C4170.18 (5)
S3—Ni1—S1—C40.13 (5)
Symmetry code: (i) x+1, y, z+3/2.

Experimental details

Crystal data
Chemical formula[Ni(C5H10NS2)3]
Mr503.49
Crystal system, space groupMonoclinic, C2/c
Temperature (K)173
a, b, c (Å)14.0208 (9), 10.2305 (7), 16.9031 (11)
β (°) 109.630 (5)
V3)2283.7 (3)
Z4
Radiation typeMo Kα
µ (mm1)1.40
Crystal size (mm)0.20 × 0.20 × 0.10
Data collection
DiffractometerStoe IPDS-II two-circle
diffractometer
Absorption correctionMulti-scan
(MULABS; Spek, 1990; Blessing, 1995)
Tmin, Tmax0.767, 0.872
No. of measured, independent and
observed [I > 2σ(I)] reflections
16440, 3232, 2635
Rint0.037
(sin θ/λ)max1)0.698
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.022, 0.061, 0.96
No. of reflections3232
No. of parameters115
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.39, 0.80

Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991).

Selected bond lengths (Å) top
Ni1—S32.2677 (4)C1—S21.7161 (11)
Ni1—S12.2709 (4)C4—S31.7166 (13)
Ni1—S22.2717 (4)C4—S11.7178 (13)
 

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