organic compounds
N-Ethyl-N-phenyl{[ethyl(phenyl)carbamothioyl]disulfanyl}carbothioamide
aDepartment of Chemistry, University of Fort Hare, Private Bag X1314, Alice 5700, South Africa, and bSchool of Chemistry and Physics, University of KwaZulu-Natal, Westville Campus, Private Bag X54001, Durban, 4000, South Africa
*Correspondence e-mail: owaga@ukzn.ac.za
The 18H20N2S4, contains one half-molecule, the complete molecule being generated by a twofold rotation axis. The plane through the NCS2 group [maximum deviation = 0.01 (7) Å] is orthogonal to the phenyl ring, forming a dihedral angle of 89.4 (3)°. The is stabilized by intermolecular C—H⋯π interactions.
of the title compound, CRelated literature
For background to the chemistry of thiuram disulfides and their potential applications, see: Chieh (1977); McCleverty & Morrison (1976); Victoriano (2000). For related structures, see: Fun et al. (2001); Raya et al. (2005).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2008); cell SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus and XPREP (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
https://doi.org/10.1107/S1600536812027808/ru2038sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812027808/ru2038Isup2.hkl
A mixture of 6.44 ml of ethylaniline and 15.00 ml of concentrated aqueous ammonia in ice was added into 3.00 ml of ice-cold carbon disulfide and the resultant solution stirred for 6–7 h. The solid product obtained was filtered and rinsed three times with ice cold ethanol three times. The yellowish white was recrystallized in water/methanol mixture to yield crystal suitable for X-ray crystallographic analysis.
Thiuram disulfides are semi-esters of dialkyldithiocarbamic acids (Victoriano, 2000). They are unique among thiolato type ligands in that reductive scission of the S—S bond leads to chelating dithiocarbamtes anions which are particularly well suited to stabilize high
transition metals like dithiocarbamate ligands (Victoriano, 2000). Metal species with closed shell configuration typically react with thiuram disulfides to yield adducts. Some adducts of well defined thiuram complexes have been obtained by the reaction of group 12 halides and the ligands McCleverty & Morrison (1976)).The structure of (I) Fig. 1, consists of two Nethyl-N-phenyldithiocarbamate units linked by an S–S bond. The plane of NCS2 group is orthogonal to the plane of the phenyl ring forming a dihedral angle of 89.40 (3)° between them. The torsion angle between the thiocarbamate moieties (NCS2) is 79.01 (8)°. The lattice is stabilized by C—H···π intermolecular interactions with a Cg···H distance of 3.7972 (14) Å.
The S–C, S==C and C–N bond distances are comparable to those of related structures (Fun et al. 2001; Raya et al. 2005).
For background to the chemistry of thiuram disulfides and their potential applications, see: Chieh (1977); McCleverty & Morrison (1976); Victoriano (2000). For related structures, see: Fun et al. (2001); Raya et al. (2005).
Data collection: APEX2 (Bruker, 2008); cell
SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus and XPREP (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).Fig. 1. The asymmetric unit of the title compound with displacement ellipsoids drawn at the 50% probability level. |
C18H20N2S4 | F(000) = 824 |
Mr = 392.6 | Dx = 1.32 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 20252 reflections |
a = 15.1923 (2) Å | θ = 2.3–28.5° |
b = 11.5954 (2) Å | µ = 0.48 mm−1 |
c = 12.3762 (2) Å | T = 100 K |
β = 115.039 (1)° | Block, yellow |
V = 1975.31 (5) Å3 | 0.4 × 0.37 × 0.15 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | 2405 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
φ and ω scans | θmax = 28.4°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −20→18 |
Tmin = 0.830, Tmax = 0.931 | k = −15→15 |
19720 measured reflections | l = −16→16 |
2481 independent reflections |
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)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.068 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0364P)2 + 1.5002P] where P = (Fo2 + 2Fc2)/3 |
2481 reflections | (Δ/σ)max = 0.003 |
110 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C18H20N2S4 | V = 1975.31 (5) Å3 |
Mr = 392.6 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 15.1923 (2) Å | µ = 0.48 mm−1 |
b = 11.5954 (2) Å | T = 100 K |
c = 12.3762 (2) Å | 0.4 × 0.37 × 0.15 mm |
β = 115.039 (1)° |
Bruker APEXII CCD diffractometer | 2481 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 2405 reflections with I > 2σ(I) |
Tmin = 0.830, Tmax = 0.931 | Rint = 0.027 |
19720 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.068 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.40 e Å−3 |
2481 reflections | Δρmin = −0.29 e Å−3 |
110 parameters |
Experimental. Carbon-bound H-atoms were placed in calculated positions [C—H = 0.98 Å for Me H atoms, 0.99 Å for Methylene H atoms and 0.95 Å for aromatic H atoms; Uiso(H) = 1.2Ueq(C) and were included in the refinement in the riding model approximation. |
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. The following ALERTS were generated. Each ALERT has the format test-name_ALERT_alert-type_alert-level. PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 18 PLAT153_ALERT_1_G The su's on the Cell Axes are Equal ···. 0.00020 A ng. PLAT960_ALERT_3_G Number of Intensities with I. LT. - 2*sig(I) ··· 1 |
x | y | z | Uiso*/Ueq | ||
C1 | 0.20064 (7) | 0.61036 (8) | 0.15533 (8) | 0.01472 (18) | |
C2 | 0.19847 (7) | 0.51377 (9) | 0.08775 (9) | 0.01904 (19) | |
H2 | 0.143 | 0.4979 | 0.0157 | 0.023* | |
C3 | 0.27850 (8) | 0.44056 (9) | 0.12688 (10) | 0.0220 (2) | |
H3 | 0.2781 | 0.3747 | 0.081 | 0.026* | |
C4 | 0.35898 (8) | 0.46347 (9) | 0.23282 (10) | 0.0204 (2) | |
H4 | 0.4137 | 0.4136 | 0.259 | 0.025* | |
C5 | 0.35949 (8) | 0.55942 (9) | 0.30067 (9) | 0.0201 (2) | |
H5 | 0.4141 | 0.5739 | 0.3739 | 0.024* | |
C6 | 0.28059 (7) | 0.63409 (9) | 0.26191 (9) | 0.01764 (19) | |
H6 | 0.2812 | 0.7003 | 0.3075 | 0.021* | |
C7 | 0.12241 (7) | 0.78155 (9) | 0.03173 (9) | 0.01789 (19) | |
H7A | 0.1905 | 0.8075 | 0.0581 | 0.021* | |
H7B | 0.0839 | 0.8481 | 0.0378 | 0.021* | |
C8 | 0.08306 (9) | 0.74308 (10) | −0.09751 (10) | 0.0250 (2) | |
H8A | 0.1227 | 0.6795 | −0.1047 | 0.038* | |
H8B | 0.0853 | 0.8078 | −0.1472 | 0.038* | |
H8C | 0.0157 | 0.7171 | −0.1241 | 0.038* | |
C9 | 0.04038 (7) | 0.67095 (8) | 0.13196 (8) | 0.01398 (18) | |
N1 | 0.11909 (6) | 0.68889 (7) | 0.11179 (7) | 0.01472 (16) | |
S1 | 0.060555 (17) | 0.55219 (2) | 0.23600 (2) | 0.01695 (8) | |
S2 | −0.060995 (17) | 0.74667 (2) | 0.07505 (2) | 0.01764 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0137 (4) | 0.0164 (4) | 0.0163 (4) | 0.0020 (3) | 0.0085 (3) | 0.0022 (3) |
C2 | 0.0173 (4) | 0.0203 (5) | 0.0180 (4) | 0.0012 (4) | 0.0059 (4) | −0.0024 (4) |
C3 | 0.0231 (5) | 0.0197 (5) | 0.0247 (5) | 0.0045 (4) | 0.0116 (4) | −0.0020 (4) |
C4 | 0.0171 (4) | 0.0211 (5) | 0.0250 (5) | 0.0055 (4) | 0.0107 (4) | 0.0056 (4) |
C5 | 0.0163 (5) | 0.0234 (5) | 0.0180 (4) | 0.0005 (4) | 0.0048 (4) | 0.0032 (4) |
C6 | 0.0186 (4) | 0.0184 (4) | 0.0164 (4) | −0.0001 (4) | 0.0078 (4) | −0.0005 (3) |
C7 | 0.0202 (5) | 0.0167 (4) | 0.0188 (4) | 0.0004 (4) | 0.0102 (4) | 0.0032 (4) |
C8 | 0.0332 (6) | 0.0274 (5) | 0.0183 (5) | 0.0015 (4) | 0.0146 (5) | 0.0031 (4) |
C9 | 0.0152 (4) | 0.0147 (4) | 0.0121 (4) | 0.0013 (3) | 0.0058 (3) | −0.0007 (3) |
N1 | 0.0151 (4) | 0.0154 (4) | 0.0150 (4) | 0.0025 (3) | 0.0075 (3) | 0.0020 (3) |
S1 | 0.01842 (13) | 0.01685 (13) | 0.01994 (13) | 0.00345 (8) | 0.01235 (10) | 0.00384 (8) |
S2 | 0.01423 (13) | 0.02036 (14) | 0.01803 (13) | 0.00421 (8) | 0.00654 (10) | 0.00127 (8) |
C1—C2 | 1.3898 (13) | C7—N1 | 1.4768 (12) |
C1—C6 | 1.3910 (13) | C7—C8 | 1.5183 (15) |
C1—N1 | 1.4454 (12) | C7—H7A | 0.99 |
C2—C3 | 1.3910 (14) | C7—H7B | 0.99 |
C2—H2 | 0.95 | C8—H8A | 0.98 |
C3—C4 | 1.3884 (15) | C8—H8B | 0.98 |
C3—H3 | 0.95 | C8—H8C | 0.98 |
C4—C5 | 1.3920 (15) | C9—N1 | 1.3372 (12) |
C4—H4 | 0.95 | C9—S2 | 1.6495 (9) |
C5—C6 | 1.3892 (14) | C9—S1 | 1.8205 (9) |
C5—H5 | 0.95 | S1—S1i | 2.0112 (5) |
C6—H6 | 0.95 | ||
C2—C1—C6 | 121.25 (9) | N1—C7—H7A | 109.1 |
C2—C1—N1 | 119.01 (8) | C8—C7—H7A | 109.1 |
C6—C1—N1 | 119.71 (9) | N1—C7—H7B | 109.1 |
C1—C2—C3 | 119.19 (9) | C8—C7—H7B | 109.1 |
C1—C2—H2 | 120.4 | H7A—C7—H7B | 107.8 |
C3—C2—H2 | 120.4 | C7—C8—H8A | 109.5 |
C4—C3—C2 | 120.17 (10) | C7—C8—H8B | 109.5 |
C4—C3—H3 | 119.9 | H8A—C8—H8B | 109.5 |
C2—C3—H3 | 119.9 | C7—C8—H8C | 109.5 |
C3—C4—C5 | 120.03 (9) | H8A—C8—H8C | 109.5 |
C3—C4—H4 | 120 | H8B—C8—H8C | 109.5 |
C5—C4—H4 | 120 | N1—C9—S2 | 125.78 (7) |
C6—C5—C4 | 120.41 (9) | N1—C9—S1 | 110.70 (7) |
C6—C5—H5 | 119.8 | S2—C9—S1 | 123.49 (6) |
C4—C5—H5 | 119.8 | C9—N1—C1 | 121.70 (8) |
C5—C6—C1 | 118.93 (9) | C9—N1—C7 | 121.70 (8) |
C5—C6—H6 | 120.5 | C1—N1—C7 | 116.18 (8) |
C1—C6—H6 | 120.5 | C9—S1—S1i | 103.26 (3) |
N1—C7—C8 | 112.52 (8) | ||
C6—C1—C2—C3 | −0.94 (15) | S2—C9—N1—C7 | −0.83 (13) |
N1—C1—C2—C3 | 177.36 (9) | S1—C9—N1—C7 | −179.17 (7) |
C1—C2—C3—C4 | 0.63 (16) | C2—C1—N1—C9 | 85.13 (12) |
C2—C3—C4—C5 | 0.48 (16) | C6—C1—N1—C9 | −96.55 (11) |
C3—C4—C5—C6 | −1.31 (16) | C2—C1—N1—C7 | −87.62 (11) |
C4—C5—C6—C1 | 1.01 (15) | C6—C1—N1—C7 | 90.70 (11) |
C2—C1—C6—C5 | 0.12 (15) | C8—C7—N1—C9 | −87.47 (11) |
N1—C1—C6—C5 | −178.16 (9) | C8—C7—N1—C1 | 85.28 (11) |
S2—C9—N1—C1 | −173.18 (7) | N1—C9—S1—S1i | 174.72 (6) |
S1—C9—N1—C1 | 8.48 (11) | S2—C9—S1—S1i | −3.66 (7) |
Symmetry code: (i) −x, y, −z+1/2. |
Cg is the centroid of the C1–C6 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8B···Cgii | 0.98 | 2.97 | 3.7972 (14) | 143 |
Symmetry code: (ii) −x+1/2, −y+3/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C18H20N2S4 |
Mr | 392.6 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 100 |
a, b, c (Å) | 15.1923 (2), 11.5954 (2), 12.3762 (2) |
β (°) | 115.039 (1) |
V (Å3) | 1975.31 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.48 |
Crystal size (mm) | 0.4 × 0.37 × 0.15 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.830, 0.931 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19720, 2481, 2405 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.670 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.068, 1.06 |
No. of reflections | 2481 |
No. of parameters | 110 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.40, −0.29 |
Computer programs: APEX2 (Bruker, 2008), SAINT-Plus (Bruker, 2008), SAINT-Plus and XPREP (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).
Cg is the centroid of the C1–C6 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8B···Cgi | 0.98 | 2.97 | 3.7972 (14) | 143 |
Symmetry code: (i) −x+1/2, −y+3/2, −z. |
Acknowledgements
We thank the University of KwaZulu-Natal and the National Research Foundation (NRF) for financial support.
References
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Thiuram disulfides are semi-esters of dialkyldithiocarbamic acids (Victoriano, 2000). They are unique among thiolato type ligands in that reductive scission of the S—S bond leads to chelating dithiocarbamtes anions which are particularly well suited to stabilize high oxidation state transition metals like dithiocarbamate ligands (Victoriano, 2000). Metal species with closed shell configuration typically react with thiuram disulfides to yield adducts. Some adducts of well defined thiuram complexes have been obtained by the reaction of group 12 halides and the ligands McCleverty & Morrison (1976)).
The structure of (I) Fig. 1, consists of two Nethyl-N-phenyldithiocarbamate units linked by an S–S bond. The plane of NCS2 group is orthogonal to the plane of the phenyl ring forming a dihedral angle of 89.40 (3)° between them. The torsion angle between the thiocarbamate moieties (NCS2) is 79.01 (8)°. The lattice is stabilized by C—H···π intermolecular interactions with a Cg···H distance of 3.7972 (14) Å.
The S–C, S==C and C–N bond distances are comparable to those of related structures (Fun et al. 2001; Raya et al. 2005).