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

Ajibade, P.A.; Ejelonu, B.C.; Omondi, B.

doi:10.1107/S1600536812027808

organic compounds

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Volume 68| Part 7| July 2012| Page o2182

https://doi.org/10.1107/S1600536812027808

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

Peter A. Ajibade,^a Benjamin C. Ejelonu ^a and Bernard Omondi ^b ^*

^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

(Received 13 June 2012; accepted 19 June 2012; online 23 June 2012)

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, C 2/c
a = 15.1923 (2) Å
b = 11.5954 (2) Å
c = 12.3762 (2) Å
β = 115.039 (1)°
V = 1975.31 (5) Å³
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[F² > 2σ(F²)] = 0.024
wR(F²) = 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

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⋯Cgⁱ	0.98	2.97	3.7972 (14)	143
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ .

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812027808/ru2038sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812027808/ru2038Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Structure description top

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).

Computing details top

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).

Figures top

Fig. 1. The asymmetric unit of the title compound with displacement ellipsoids drawn at the 50% probability level.

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

Crystal data top

C₁₈H₂₀N₂S₄	F(000) = 824
M_r = 392.6	D_x = 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 top

Bruker APEXII CCD diffractometer	2405 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
φ and ω scans	θ_max = 28.4°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −20→18
T_min = 0.830, T_max = 0.931	k = −15→15
19720 measured reflections	l = −16→16
2481 independent reflections

Refinement top

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(F_o²) + (0.0364P)² + 1.5002P] where P = (F_o² + 2F_c²)/3
2481 reflections	(Δ/σ)_max = 0.003
110 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₈H₂₀N₂S₄	V = 1975.31 (5) Å³
M_r = 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)°

Data collection top

Bruker APEXII CCD diffractometer	2481 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2405 reflections with I > 2σ(I)
T_min = 0.830, T_max = 0.931	R_int = 0.027
19720 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.068	H-atom parameters constrained
S = 1.06	Δρ_max = 0.40 e Å⁻³
2481 reflections	Δρ_min = −0.29 e Å⁻³
110 parameters

Special details top

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; U_iso(H) = 1.2U_eq(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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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) top

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) top

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
M_r	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)
T_min, T_max	0.830, 0.931
No. of measured, independent and observed [I > 2σ(I)] reflections	19720, 2481, 2405
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2182

https://doi.org/10.1107/S1600536812027808

Open

access