Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803006044/na6214sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803006044/na6214Isup2.hkl |
CCDC reference: 209895
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.
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.
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).
[Ni(C5H10NS2)3] | F(000) = 1060 |
Mr = 503.49 | Dx = 1.464 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 15127 reflections |
a = 14.0208 (9) Å | θ = 3.7–29.9° |
b = 10.2305 (7) Å | µ = 1.40 mm−1 |
c = 16.9031 (11) Å | T = 173 K |
β = 109.630 (5)° | Block, light violet |
V = 2283.7 (3) Å3 | 0.20 × 0.20 × 0.10 mm |
Z = 4 |
Stoe IPDS-II two-circle diffractometer | 3232 independent reflections |
Radiation source: fine-focus sealed tube | 2635 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
ω scans | θmax = 29.7°, θmin = 3.9° |
Absorption correction: multi-scan (MULABS; Spek, 1990; Blessing, 1995) | h = −19→18 |
Tmin = 0.767, Tmax = 0.872 | k = −14→14 |
16440 measured reflections | l = −23→23 |
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)] = 0.022 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.061 | H-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 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.80 e Å−3 |
[Ni(C5H10NS2)3] | V = 2283.7 (3) Å3 |
Mr = 503.49 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 14.0208 (9) Å | µ = 1.40 mm−1 |
b = 10.2305 (7) Å | T = 173 K |
c = 16.9031 (11) Å | 0.20 × 0.20 × 0.10 mm |
β = 109.630 (5)° |
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 = 0.872 | Rint = 0.037 |
16440 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 0.96 | Δρmax = 0.39 e Å−3 |
3232 reflections | Δρmin = −0.80 e Å−3 |
115 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.5000 | 0.25100 (2) | 0.7500 | 0.02044 (7) | |
C1 | 0.5000 | −0.01879 (19) | 0.7500 | 0.0230 (4) | |
C2 | 0.40977 (15) | −0.22287 (16) | 0.74875 (11) | 0.0387 (4) | |
H2A | 0.4056 | −0.3036 | 0.7154 | 0.046* | |
H2B | 0.3487 | −0.1699 | 0.7204 | 0.046* | |
C3 | 0.4101 (2) | −0.2595 (2) | 0.83540 (14) | 0.0556 (6) | |
H3A | 0.3482 | −0.3083 | 0.8307 | 0.083* | |
H3B | 0.4128 | −0.1800 | 0.8684 | 0.083* | |
H3C | 0.4693 | −0.3140 | 0.8633 | 0.083* | |
C4 | 0.35964 (10) | 0.38592 (13) | 0.62047 (8) | 0.0201 (2) | |
C5 | 0.29340 (12) | 0.43897 (15) | 0.47172 (8) | 0.0272 (3) | |
H5A | 0.2229 | 0.4316 | 0.4326 | 0.033* | |
H5B | 0.3299 | 0.3582 | 0.4667 | 0.033* | |
C6 | 0.22847 (12) | 0.55200 (16) | 0.57631 (10) | 0.0329 (3) | |
H6A | 0.2637 | 0.6371 | 0.5816 | 0.040* | |
H6B | 0.2203 | 0.5325 | 0.6310 | 0.040* | |
C7 | 0.34366 (16) | 0.5549 (2) | 0.44681 (12) | 0.0429 (4) | |
H7A | 0.3419 | 0.5440 | 0.3887 | 0.064* | |
H7B | 0.4142 | 0.5608 | 0.4842 | 0.064* | |
H7C | 0.3075 | 0.6350 | 0.4514 | 0.064* | |
C8 | 0.12560 (12) | 0.5640 (2) | 0.51083 (13) | 0.0439 (4) | |
H8A | 0.0874 | 0.6331 | 0.5271 | 0.066* | |
H8B | 0.0894 | 0.4808 | 0.5059 | 0.066* | |
H8C | 0.1328 | 0.5861 | 0.4567 | 0.066* | |
N1 | 0.5000 | −0.14880 (17) | 0.7500 | 0.0293 (4) | |
N2 | 0.29225 (9) | 0.45005 (12) | 0.55808 (7) | 0.0245 (2) | |
S1 | 0.37317 (3) | 0.39993 (3) | 0.72495 (2) | 0.02400 (8) | |
S2 | 0.39946 (2) | 0.07687 (3) | 0.75000 (2) | 0.02308 (8) | |
S3 | 0.44642 (2) | 0.27616 (3) | 0.608522 (19) | 0.02077 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.02321 (12) | 0.01827 (12) | 0.02022 (12) | 0.000 | 0.00779 (9) | 0.000 |
C1 | 0.0291 (9) | 0.0186 (8) | 0.0182 (8) | 0.000 | 0.0040 (7) | 0.000 |
C2 | 0.0506 (10) | 0.0215 (7) | 0.0353 (8) | −0.0116 (7) | 0.0030 (7) | 0.0015 (6) |
C3 | 0.0709 (14) | 0.0481 (11) | 0.0452 (11) | −0.0183 (10) | 0.0160 (10) | 0.0084 (9) |
C4 | 0.0230 (6) | 0.0183 (5) | 0.0198 (6) | −0.0001 (4) | 0.0082 (5) | −0.0006 (4) |
C5 | 0.0318 (7) | 0.0310 (7) | 0.0176 (6) | 0.0030 (6) | 0.0068 (5) | 0.0016 (5) |
C6 | 0.0346 (8) | 0.0326 (8) | 0.0291 (7) | 0.0122 (6) | 0.0075 (6) | −0.0009 (6) |
C7 | 0.0487 (10) | 0.0465 (10) | 0.0387 (9) | −0.0071 (8) | 0.0216 (8) | 0.0052 (8) |
C8 | 0.0260 (7) | 0.0474 (10) | 0.0524 (10) | 0.0072 (7) | 0.0054 (7) | −0.0094 (8) |
N1 | 0.0391 (10) | 0.0173 (7) | 0.0262 (8) | 0.000 | 0.0037 (7) | 0.000 |
N2 | 0.0281 (6) | 0.0257 (6) | 0.0196 (5) | 0.0064 (5) | 0.0081 (4) | 0.0015 (4) |
S1 | 0.03101 (16) | 0.02389 (16) | 0.01844 (14) | 0.00734 (13) | 0.01007 (12) | 0.00035 (11) |
S2 | 0.02316 (15) | 0.02081 (15) | 0.02484 (15) | −0.00264 (12) | 0.00750 (11) | 0.00091 (12) |
S3 | 0.02337 (15) | 0.02119 (15) | 0.01871 (14) | 0.00227 (11) | 0.00833 (11) | −0.00149 (11) |
Ni1—S3i | 2.2676 (3) | C4—S3 | 1.7166 (13) |
Ni1—S3 | 2.2677 (4) | C4—S1 | 1.7178 (13) |
Ni1—S1 | 2.2709 (4) | C5—N2 | 1.4696 (18) |
Ni1—S1i | 2.2709 (4) | C5—C7 | 1.510 (2) |
Ni1—S2 | 2.2717 (4) | C5—H5A | 0.9900 |
Ni1—S2i | 2.2717 (4) | C5—H5B | 0.9900 |
C1—N1 | 1.330 (2) | C6—N2 | 1.4723 (19) |
C1—S2 | 1.7161 (11) | C6—C8 | 1.499 (2) |
C1—S2i | 1.7161 (11) | C6—H6A | 0.9900 |
C2—N1 | 1.469 (2) | C6—H6B | 0.9900 |
C2—C3 | 1.510 (3) | C7—H7A | 0.9800 |
C2—H2A | 0.9900 | C7—H7B | 0.9800 |
C2—H2B | 0.9900 | C7—H7C | 0.9800 |
C3—H3A | 0.9800 | C8—H8A | 0.9800 |
C3—H3B | 0.9800 | C8—H8B | 0.9800 |
C3—H3C | 0.9800 | C8—H8C | 0.9800 |
C4—N2 | 1.3289 (17) | N1—C2i | 1.469 (2) |
S3i—Ni1—S3 | 166.97 (2) | N2—C5—C7 | 112.23 (13) |
S3i—Ni1—S1 | 94.687 (13) | N2—C5—H5A | 109.2 |
S3—Ni1—S1 | 76.466 (12) | C7—C5—H5A | 109.2 |
S3i—Ni1—S1i | 76.466 (13) | N2—C5—H5B | 109.2 |
S3—Ni1—S1i | 94.687 (13) | C7—C5—H5B | 109.2 |
S1—Ni1—S1i | 95.72 (2) | H5A—C5—H5B | 107.9 |
S3i—Ni1—S2 | 94.285 (13) | N2—C6—C8 | 113.89 (14) |
S3—Ni1—S2 | 95.929 (13) | N2—C6—H6A | 108.8 |
S1—Ni1—S2 | 94.538 (14) | C8—C6—H6A | 108.8 |
S1i—Ni1—S2 | 166.699 (14) | N2—C6—H6B | 108.8 |
S3i—Ni1—S2i | 95.931 (13) | C8—C6—H6B | 108.8 |
S3—Ni1—S2i | 94.283 (13) | H6A—C6—H6B | 107.7 |
S1—Ni1—S2i | 166.698 (14) | C5—C7—H7A | 109.5 |
S1i—Ni1—S2i | 94.536 (14) | C5—C7—H7B | 109.5 |
S2—Ni1—S2i | 76.71 (2) | H7A—C7—H7B | 109.5 |
N1—C1—S2 | 124.77 (5) | C5—C7—H7C | 109.5 |
N1—C1—S2i | 124.77 (5) | H7A—C7—H7C | 109.5 |
S2—C1—S2i | 110.46 (11) | H7B—C7—H7C | 109.5 |
N1—C2—C3 | 113.11 (15) | C6—C8—H8A | 109.5 |
N1—C2—H2A | 109.0 | C6—C8—H8B | 109.5 |
C3—C2—H2A | 109.0 | H8A—C8—H8B | 109.5 |
N1—C2—H2B | 109.0 | C6—C8—H8C | 109.5 |
C3—C2—H2B | 109.0 | H8A—C8—H8C | 109.5 |
H2A—C2—H2B | 107.8 | H8B—C8—H8C | 109.5 |
C2—C3—H3A | 109.5 | C1—N1—C2 | 121.06 (10) |
C2—C3—H3B | 109.5 | C1—N1—C2i | 121.06 (10) |
H3A—C3—H3B | 109.5 | C2—N1—C2i | 117.9 (2) |
C2—C3—H3C | 109.5 | C4—N2—C5 | 120.53 (12) |
H3A—C3—H3C | 109.5 | C4—N2—C6 | 120.24 (11) |
H3B—C3—H3C | 109.5 | C5—N2—C6 | 118.20 (11) |
N2—C4—S3 | 124.94 (10) | C4—S1—Ni1 | 86.83 (5) |
N2—C4—S1 | 125.32 (10) | C1—S2—Ni1 | 86.42 (5) |
S3—C4—S1 | 109.74 (7) | C4—S3—Ni1 | 86.96 (4) |
S2—C1—N1—C2 | 0.91 (8) | S1i—Ni1—S1—C4 | 93.59 (5) |
S2i—C1—N1—C2 | −179.09 (8) | S2—Ni1—S1—C4 | −94.89 (5) |
S2—C1—N1—C2i | −179.10 (8) | S2i—Ni1—S1—C4 | −46.69 (8) |
S2i—C1—N1—C2i | 0.91 (8) | N1—C1—S2—Ni1 | 180.0 |
C3—C2—N1—C1 | −93.33 (17) | S2i—C1—S2—Ni1 | −0.002 (1) |
C3—C2—N1—C2i | 86.67 (17) | S3i—Ni1—S2—C1 | −95.091 (15) |
S3—C4—N2—C5 | −5.43 (19) | S3—Ni1—S2—C1 | 93.018 (14) |
S1—C4—N2—C5 | 174.64 (11) | S1—Ni1—S2—C1 | 169.852 (13) |
S3—C4—N2—C6 | −173.66 (12) | S1i—Ni1—S2—C1 | −49.76 (6) |
S1—C4—N2—C6 | 6.4 (2) | S2i—Ni1—S2—C1 | 0.0 |
C7—C5—N2—C4 | −100.31 (17) | N2—C4—S3—Ni1 | −179.76 (12) |
C7—C5—N2—C6 | 68.15 (19) | S1—C4—S3—Ni1 | 0.18 (6) |
C8—C6—N2—C4 | −148.52 (16) | S3i—Ni1—S3—C4 | −48.29 (5) |
C8—C6—N2—C5 | 43.0 (2) | S1—Ni1—S3—C4 | −0.13 (5) |
N2—C4—S1—Ni1 | 179.76 (12) | S1i—Ni1—S3—C4 | −94.90 (5) |
S3—C4—S1—Ni1 | −0.18 (6) | S2—Ni1—S3—C4 | 93.12 (5) |
S3i—Ni1—S1—C4 | 170.43 (5) | S2i—Ni1—S3—C4 | 170.18 (5) |
S3—Ni1—S1—C4 | 0.13 (5) |
Symmetry code: (i) −x+1, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C5H10NS2)3] |
Mr | 503.49 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 173 |
a, b, c (Å) | 14.0208 (9), 10.2305 (7), 16.9031 (11) |
β (°) | 109.630 (5) |
V (Å3) | 2283.7 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.40 |
Crystal size (mm) | 0.20 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Stoe IPDS-II two-circle diffractometer |
Absorption correction | Multi-scan (MULABS; Spek, 1990; Blessing, 1995) |
Tmin, Tmax | 0.767, 0.872 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16440, 3232, 2635 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.698 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.061, 0.96 |
No. of reflections | 3232 |
No. of parameters | 115 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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).
Ni1—S3 | 2.2677 (4) | C1—S2 | 1.7161 (11) |
Ni1—S1 | 2.2709 (4) | C4—S3 | 1.7166 (13) |
Ni1—S2 | 2.2717 (4) | C4—S1 | 1.7178 (13) |
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).