(N,N-Diiso­butyl­di­thio­carbamoyl­sulfinato)­zinc(II)

Zinc di­alkyl di­thio­carbamoyl­sulfinates have been proposed as intermediates in the antioxidant action of the respective zinc di­alkyl di­thio­carbamate additives in hydro­carbon-based plastics and lubricants. As a model compound, zinc diiso­butyl di­thio­carbamoyl­sulfinate, [Zn(C₉H₁₈NO₂S₂)₂], has been prepared and its crystal structure determined.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](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

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S1. Comment

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.

S2. Experimental

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.

S3. Refinement

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.

Computing details

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.

Figures

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.]

zinc diisobutyldithiocarbamoylsulphinate

Crystal data

[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) Å^3	T = 293 K
Z = 4	Prismatic, colourless
F(000) = 1136	0.36 × 0.33 × 0.29 mm

Data collection

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

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.032	w = 1/[σ^2(Fo^2) + (0.0545P)^2 + 0.3208P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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+0.001xFc^2λ^3/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)

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

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

Geometric parameters (Å, º)

Zn1—O1	1.957 (2)	C8—H81	0.9600
Zn1—O1^i	1.957 (2)	C8—H82	0.9600
Zn1—S1^i	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—O1^i	121.40 (15)	H81—C8—H83	109.5
O1—Zn1—S1^i	119.47 (9)	H82—C8—H83	109.5
O1^i—Zn1—S1^i	90.23 (8)	C5—C9—H91	109.5
O1—Zn1—S1	90.23 (8)	C5—C9—H92	109.5
O1^i—Zn1—S1	119.47 (9)	H91—C9—H92	109.5
S1^i—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.