Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680301314X/bt6269sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680301314X/bt6269Isup2.hkl |
CCDC reference: 217380
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.007 Å
- R factor = 0.032
- wR factor = 0.093
- Data-to-parameter ratio = 12.7
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 24.97 From the CIF: _reflns_number_total 1695 Count of symmetry unique reflns 1309 Completeness (_total/calc) 129.49% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 386 Fraction of Friedel pairs measured 0.295 Are heavy atom types Z>Si present yes WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure
Zinc diisobutyldithiocarbamoylsulphinate, (I), was prepared following the method reported by Shelkova et al. (1990) for the di-n-butyl isomer. A stirred solution of sodium diisobutyldithiocarbamate (1 molar equivalent) in acetone was treated with hydrogen peroxide (2 molar equivalents) in small portions and kept at 273–278 K. The yellow precipate formed after dilution with water was purified by fractionated crystallization from ethanol/n-hexane to yield colourless crystals of (I). IR spectrum (cm−1): 2975, 2960, 2940, 1530, 1460, 1445, 1435, 1380, 1365, 1350, 1330, 1290, 1275, 1255, 1170, 1165, 1155, 1090, 970, 955, 920, 855, 825, 815, 805, 645.
The molecule of (I) consists of two equivalent parts related by a twofold axis of the space group. The Zn atom occupies a special position on this twofold axis. Atoms C6 and C7 have very large anisotropic displacement parameters indicating a disorder of the corresponding isobutyl group.
Data collection: CAD-4 Operations Manual (Enraf-Nonius, 1977); cell refinement: CAD-4 Operations Manual; data reduction: PROCESS in_MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT (Sheldrick, 1999); software used to prepare material for publication: SHELXTL97.
Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids (SHELXTL; Sheldrick, 1999). H-atom labels have been omitted for clarity·[Symmetry code: (i) −x, −y − 1, z.] |
[Zn(C9H18NO2S2)2] | Dx = 1.365 Mg m−3 |
Mr = 538.10 | Mo Kα radiation, λ = 0.71069 Å |
Tetragonal, P421c | Cell parameters from 25 reflections |
a = 12.557 (2) Å | θ = 12–20° |
c = 16.600 (3) Å | µ = 1.28 mm−1 |
V = 2617.5 (8) Å3 | T = 293 K |
Z = 4 | Prismatic, colourless |
F(000) = 1136 | 0.36 × 0.33 × 0.29 mm |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.042 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.0° |
Graphite monochromator | h = 0→14 |
2θ–ω scans | k = −14→14 |
2940 measured reflections | l = 0→19 |
1695 independent reflections | 3 standard reflections every 120 min |
1523 reflections with I > 2σ(I) | intensity decay: 0.5% |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.032 | w = 1/[σ2(Fo2) + (0.0545P)2 + 0.3208P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.093 | (Δ/σ)max = 0.001 |
S = 1.11 | Δρmax = 0.53 e Å−3 |
1695 reflections | Δρmin = −0.31 e Å−3 |
133 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0101 (10) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.02 (3) |
[Zn(C9H18NO2S2)2] | Z = 4 |
Mr = 538.10 | Mo Kα radiation |
Tetragonal, P421c | µ = 1.28 mm−1 |
a = 12.557 (2) Å | T = 293 K |
c = 16.600 (3) Å | 0.36 × 0.33 × 0.29 mm |
V = 2617.5 (8) Å3 |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.042 |
2940 measured reflections | 3 standard reflections every 120 min |
1695 independent reflections | intensity decay: 0.5% |
1523 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.093 | Δρmax = 0.53 e Å−3 |
S = 1.11 | Δρmin = −0.31 e Å−3 |
1695 reflections | Absolute structure: Flack (1983) |
133 parameters | Absolute structure parameter: −0.02 (3) |
1 restraint |
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 | ||
Zn1 | 0.0000 | −0.5000 | −0.87762 (3) | 0.0513 (2) | |
S1 | 0.01766 (7) | −0.65813 (9) | −0.80688 (7) | 0.0687 (3) | |
S2 | −0.20087 (6) | −0.62201 (7) | −0.88583 (5) | 0.0457 (2) | |
O1 | −0.1229 (2) | −0.5581 (2) | −0.93532 (14) | 0.0575 (7) | |
O2 | −0.2442 (3) | −0.5577 (2) | −0.81989 (16) | 0.0696 (8) | |
N1 | −0.1422 (2) | −0.7923 (2) | −0.79122 (16) | 0.0441 (6) | |
C1 | −0.1049 (2) | −0.7058 (3) | −0.82410 (19) | 0.0424 (7) | |
C2 | −0.2452 (3) | −0.8403 (3) | −0.8144 (2) | 0.0509 (8) | |
H2A | −0.2963 | −0.7838 | −0.8239 | 0.061* | |
H2B | −0.2713 | −0.8830 | −0.7699 | 0.061* | |
C3 | −0.0819 (3) | −0.8482 (3) | −0.7268 (2) | 0.0511 (8) | |
H31 | −0.0079 | −0.8545 | −0.7427 | 0.061* | |
H32 | −0.1103 | −0.9196 | −0.7202 | 0.061* | |
C8 | −0.0196 (4) | −0.8465 (4) | −0.5856 (2) | 0.0780 (13) | |
H81 | 0.0520 | −0.8515 | −0.6055 | 0.117* | |
H82 | −0.0472 | −0.9167 | −0.5763 | 0.117* | |
H83 | −0.0199 | −0.8072 | −0.5359 | 0.117* | |
C9 | −0.2018 (4) | −0.7793 (4) | −0.6174 (3) | 0.0726 (12) | |
H91 | −0.2434 | −0.7422 | −0.6570 | 0.109* | |
H92 | −0.2027 | −0.7401 | −0.5677 | 0.109* | |
H93 | −0.2314 | −0.8489 | −0.6088 | 0.109* | |
C5 | −0.0884 (3) | −0.7897 (3) | −0.6468 (2) | 0.0532 (9) | |
H5 | −0.0596 | −0.7179 | −0.6546 | 0.064* | |
C4 | −0.2389 (4) | −0.9085 (5) | −0.8878 (4) | 0.0999 (19) | |
H4 | −0.2272 | −0.8575 | −0.9316 | 0.120* | |
C7 | −0.3507 (5) | −0.9530 (7) | −0.9047 (5) | 0.142 (3) | |
H7A | −0.4023 | −0.8969 | −0.8998 | 0.212* | |
H7B | −0.3667 | −1.0082 | −0.8665 | 0.212* | |
H7C | −0.3530 | −0.9818 | −0.9582 | 0.212* | |
C6 | −0.1510 (6) | −0.9825 (7) | −0.8954 (6) | 0.205 (5) | |
H6A | −0.1556 | −1.0185 | −0.9463 | 0.307* | |
H6B | −0.1542 | −1.0337 | −0.8526 | 0.307* | |
H6C | −0.0849 | −0.9443 | −0.8924 | 0.307* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0491 (3) | 0.0481 (3) | 0.0567 (3) | −0.0169 (2) | 0.000 | 0.000 |
S1 | 0.0378 (5) | 0.0709 (7) | 0.0974 (7) | −0.0176 (5) | −0.0146 (5) | 0.0314 (6) |
S2 | 0.0404 (4) | 0.0413 (4) | 0.0553 (4) | −0.0046 (3) | −0.0080 (4) | −0.0009 (4) |
O1 | 0.0617 (15) | 0.0595 (16) | 0.0513 (13) | −0.0197 (13) | −0.0124 (12) | 0.0083 (12) |
O2 | 0.0708 (18) | 0.0633 (17) | 0.0745 (16) | 0.0205 (15) | 0.0068 (16) | −0.0059 (15) |
N1 | 0.0388 (13) | 0.0377 (13) | 0.0559 (14) | −0.0048 (12) | 0.0007 (12) | −0.0005 (12) |
C1 | 0.0358 (16) | 0.0404 (16) | 0.0508 (16) | 0.0000 (14) | −0.0015 (14) | 0.0004 (14) |
C2 | 0.0436 (17) | 0.0420 (17) | 0.067 (2) | −0.0120 (16) | 0.0031 (17) | −0.0040 (17) |
C3 | 0.0492 (18) | 0.0360 (15) | 0.0682 (19) | 0.0047 (16) | 0.0097 (17) | 0.0074 (16) |
C8 | 0.077 (3) | 0.083 (3) | 0.074 (2) | 0.008 (3) | −0.007 (2) | 0.015 (2) |
C9 | 0.062 (2) | 0.086 (3) | 0.069 (2) | 0.011 (2) | 0.003 (2) | −0.021 (2) |
C5 | 0.055 (2) | 0.0445 (18) | 0.0598 (19) | −0.0011 (17) | −0.0076 (17) | 0.0035 (16) |
C4 | 0.077 (3) | 0.107 (4) | 0.116 (4) | 0.003 (3) | −0.015 (3) | −0.060 (4) |
C7 | 0.094 (4) | 0.150 (6) | 0.181 (6) | −0.024 (4) | −0.030 (5) | −0.103 (6) |
C6 | 0.128 (7) | 0.201 (10) | 0.285 (11) | −0.013 (7) | 0.035 (8) | −0.179 (10) |
Zn1—O1 | 1.957 (2) | C8—H81 | 0.9600 |
Zn1—O1i | 1.957 (2) | C8—H82 | 0.9600 |
Zn1—S1i | 2.3175 (11) | C8—H83 | 0.9600 |
Zn1—S1 | 2.3175 (11) | C9—C5 | 1.511 (6) |
S1—C1 | 1.676 (3) | C9—H91 | 0.9600 |
S2—O2 | 1.465 (3) | C9—H92 | 0.9600 |
S2—O1 | 1.509 (3) | C9—H93 | 0.9600 |
S2—C1 | 1.899 (3) | C5—H5 | 0.9800 |
N1—C1 | 1.303 (4) | C4—C6 | 1.449 (7) |
N1—C2 | 1.477 (4) | C4—C7 | 1.537 (8) |
N1—C3 | 1.487 (4) | C4—H4 | 0.9800 |
C2—C4 | 1.490 (6) | C7—H7A | 0.9600 |
C2—H2A | 0.9700 | C7—H7B | 0.9600 |
C2—H2B | 0.9700 | C7—H7C | 0.9600 |
C3—C5 | 1.519 (5) | C6—H6A | 0.9600 |
C3—H31 | 0.9700 | C6—H6B | 0.9600 |
C3—H32 | 0.9700 | C6—H6C | 0.9600 |
C8—C5 | 1.513 (5) | ||
O1—Zn1—O1i | 121.40 (15) | H81—C8—H83 | 109.5 |
O1—Zn1—S1i | 119.47 (9) | H82—C8—H83 | 109.5 |
O1i—Zn1—S1i | 90.23 (8) | C5—C9—H91 | 109.5 |
O1—Zn1—S1 | 90.23 (8) | C5—C9—H92 | 109.5 |
O1i—Zn1—S1 | 119.47 (9) | H91—C9—H92 | 109.5 |
S1i—Zn1—S1 | 119.11 (7) | C5—C9—H93 | 109.5 |
C1—S1—Zn1 | 97.55 (12) | H91—C9—H93 | 109.5 |
O2—S2—O1 | 110.77 (17) | H92—C9—H93 | 109.5 |
O2—S2—C1 | 97.92 (16) | C9—C5—C8 | 111.2 (3) |
O1—S2—C1 | 100.17 (16) | C9—C5—C3 | 112.0 (3) |
S2—O1—Zn1 | 116.31 (13) | C8—C5—C3 | 109.2 (3) |
C1—N1—C2 | 123.0 (3) | C9—C5—H5 | 108.1 |
C1—N1—C3 | 120.8 (3) | C8—C5—H5 | 108.1 |
C2—N1—C3 | 116.2 (3) | C3—C5—H5 | 108.1 |
N1—C1—S1 | 123.8 (2) | C6—C4—C2 | 118.7 (5) |
N1—C1—S2 | 117.4 (2) | C6—C4—C7 | 116.5 (6) |
S1—C1—S2 | 118.5 (2) | C2—C4—C7 | 108.0 (5) |
N1—C2—C4 | 113.7 (3) | C6—C4—H4 | 103.8 |
N1—C2—H2A | 108.8 | C2—C4—H4 | 103.8 |
C4—C2—H2A | 108.8 | C7—C4—H4 | 103.8 |
N1—C2—H2B | 108.8 | C4—C7—H7A | 109.5 |
C4—C2—H2B | 108.8 | C4—C7—H7B | 109.5 |
H2A—C2—H2B | 107.7 | H7A—C7—H7B | 109.5 |
N1—C3—C5 | 111.9 (3) | C4—C7—H7C | 109.5 |
N1—C3—H31 | 109.2 | H7A—C7—H7C | 109.5 |
C5—C3—H31 | 109.2 | H7B—C7—H7C | 109.5 |
N1—C3—H32 | 109.2 | C4—C6—H6A | 109.5 |
C5—C3—H32 | 109.2 | C4—C6—H6B | 109.5 |
H31—C3—H32 | 107.9 | H6A—C6—H6B | 109.5 |
C5—C8—H81 | 109.5 | C4—C6—H6C | 109.5 |
C5—C8—H82 | 109.5 | H6A—C6—H6C | 109.5 |
H81—C8—H82 | 109.5 | H6B—C6—H6C | 109.5 |
C5—C8—H83 | 109.5 |
Symmetry code: (i) −x, −y−1, z. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C9H18NO2S2)2] |
Mr | 538.10 |
Crystal system, space group | Tetragonal, P421c |
Temperature (K) | 293 |
a, c (Å) | 12.557 (2), 16.600 (3) |
V (Å3) | 2617.5 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.28 |
Crystal size (mm) | 0.36 × 0.33 × 0.29 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2940, 1695, 1523 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.093, 1.11 |
No. of reflections | 1695 |
No. of parameters | 133 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.53, −0.31 |
Absolute structure | Flack (1983) |
Absolute structure parameter | −0.02 (3) |
Computer programs: CAD-4 Operations Manual (Enraf-Nonius, 1977), CAD-4 Operations Manual, PROCESS in_MolEN (Fair, 1990), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL-NT (Sheldrick, 1999), SHELXTL97.
Zinc dialkylthiocarbamoylsulphinates, (I), and zinc dialkyldithiopercarbamates, (II), have been discussed as possible oxidation products in the antioxidant action of zinc dialkyldithiocarbamates additives in plastics and liquid hydrocarbons. (II) has been identified as derivative of (III) in model systems using autoxidizing liquid hydrocarbons (Al-Malaika et al., 1985; Shelkova et al., 1990) and vegetable oil based lubricants (Becker et al., 1996) and could be shown to display antioxidant activity itself. Though it has been demonstrated that (I) exhibits antioxidant activity (Shelkova et al., 1990) there is no evidence that it accumulates in these materials amounts during auto-oxidation.
While the solid-state structure of (II) (R1 = R2 = n-butyl) has been reported (Reck et al., 1995), structure proposals for (I), to the best of our knowledge, are based on their IR spectra only. Here, the solid-state structure of zinc diisobutyldithiocarbamoylsulphinate, (I) [R1 = R2 = –CH2CH(CH3)2], is reported.