N-Ethyl-N-phen­yl{[eth­yl(phen­yl)carbamothio­yl]disulfan­yl}carbothio­amide

Abstract

The asymmetric unit of the title compound, C₁₈H₂₀N₂S₄, 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 crystal structure is stabilized by inter­molecular C—H⋯π inter­actions.

Related 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  

• C₁₈H₂₀N₂S₄

• M _r = 392.6

• Monoclinic,

• a = 15.1923 (2) Å

• b = 11.5954 (2) Å

• c = 12.3762 (2) Å

• β = 115.039 (1)°

• V = 1975.31 (5) ų

• Z = 4

• Mo Kα radiation

• μ = 0.48 mm⁻¹

• T = 100 K

• 0.40 × 0.37 × 0.15 mm

Data collection  

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.830, T _max = 0.931

• 19720 measured reflections

• 2481 independent reflections

• 2405 reflections with I > 2σ(I)

• R _int = 0.027

Refinement  

• R[F ² > 2σ(F ²)] = 0.024

• wR(F ²) = 0.068

• S = 1.06

• 2481 reflections

• 110 parameters

• H-atom parameters constrained

• Δρ_max = 0.40 e Å⁻³

• Δρ_min = −0.29 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: 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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯Cg i	0.98	2.97	3.7972 (14)	143

Symmetry code: (i) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Figures

Fig. 1.

The asymmetric unit of the title compound with displacement ellipsoids drawn at the 50% probability level.

Crystal data

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

Data collection

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

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

Special details

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)

Atomic displacement parameters (Ų)

	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)

Geometric parameters (Å, º)

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.

Hydrogen-bond geometry (Å, º)

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.