Bis(N-methyl-N-phenyl-carbamo-yl)disulfane.

The title compound, C(16)H(16)N(2)O(2)S(2), has been synthesized by several different high-yield routes, and has been encountered as a co-product in a number of reaction pathways, ever since it became of inter-est to our research program over 30 years ago. We now confirm the proposed mol-ecular structure in which the mol-ecule exhibits a twofold axis of symmetry through the mid-point of the S-S bond and the two planes defined by the (carbamo-yl)sulfenyl moieties are essentially perpendicular to each other [dihedral angle = 81.55 (14)°].

Related literature

For the preparation of the title compound, and of very closely related chemical structures, see: Kobayashi et al. (1973 ▶); Barany et al. (1983 ▶); Schroll & Barany (1986 ▶); Schrader et al. (2011 ▶). For related structures, see: CSD refcodes BOWGAV (Bereman et al., 1983 ▶), DBZOSS01&03 (Rout et al., 1983 ▶; Paul & Srikrishnan, 2004 ▶), METHUS03 (Wang & Liao, 1989 ▶), NELTUT (Fun et al., 2001 ▶), JAXPOO (Raya et al., 2005 ▶), UDALER (Li et al., 2006 ▶) and EMASIV (Singh et al., 2011 ▶). For the theoretical optimum torsion angle about the disulfane, see: Pauling (1949 ▶); Torrico-Vallejos et al. (2010 ▶) and references cited therein.

Experimental

Crystal data

C16H16N2O2S2

M = 332.43

Monoclinic,

a = 15.286 (3) Å

b = 9.7849 (18) Å

c = 11.597 (2) Å

β = 107.433 (3)°

V = 1654.9 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.33 mm−1

T = 296 K

0.40 × 0.16 × 0.13 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2010 ▶) T min = 0.880, T max = 0.958

5726 measured reflections

1468 independent reflections

1140 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.110

S = 1.05

1468 reflections

101 parameters

H-atom parameters constrained

Δρmax = 0.21 e Å−3

Δρmin = −0.18 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812016030/qm2060sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812016030/qm2060Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812016030/qm2060Isup3.cml

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

C16H16N2O2S2	F(000) = 696
Mr = 332.43	Dx = 1.334 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.286 (3) Å	Cell parameters from 1966 reflections
b = 9.7849 (18) Å	θ = 2.5–24.4°
c = 11.597 (2) Å	µ = 0.33 mm−1
β = 107.433 (3)°	T = 296 K
V = 1654.9 (5) Å3	Needle, colorless
Z = 4	0.40 × 0.16 × 0.13 mm

Bruker SMART CCD diffractometer	1468 independent reflections
Radiation source: sealed tube	1140 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
φ and ω scans	θmax = 25.1°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −18→17
Tmin = 0.880, Tmax = 0.958	k = 0→11
5726 measured reflections	l = 0→13

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0553P)2 + 1.0043P] where P = (Fo2 + 2Fc2)/3
1468 reflections	(Δ/σ)max = 0.001
101 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.18 e Å−3

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 > 2σ(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
S1	0.56058 (4)	0.49722 (6)	0.73116 (5)	0.0567 (2)
O1	0.47025 (9)	0.69997 (17)	0.58995 (15)	0.0626 (5)
N1	0.61329 (11)	0.65722 (19)	0.57979 (17)	0.0514 (5)
C1	0.54116 (13)	0.6361 (2)	0.62131 (19)	0.0481 (5)
C2	0.60771 (17)	0.7649 (3)	0.4905 (2)	0.0697 (7)
H2A	0.5446	0.7887	0.4530	0.105*
H2B	0.6341	0.7328	0.4301	0.105*
H2C	0.6407	0.8438	0.5298	0.105*
C3	0.69962 (13)	0.5872 (2)	0.62742 (19)	0.0466 (5)
C4	0.76230 (16)	0.6332 (3)	0.7319 (2)	0.0681 (7)
H4A	0.7486	0.7071	0.7739	0.082*
C5	0.84668 (17)	0.5672 (4)	0.7739 (3)	0.0852 (9)
H5A	0.8893	0.5962	0.8451	0.102*
C6	0.86714 (18)	0.4597 (3)	0.7107 (3)	0.0806 (9)
H6A	0.9235	0.4159	0.7393	0.097*
C7	0.80540 (18)	0.4168 (3)	0.6063 (3)	0.0716 (7)
H7A	0.8202	0.3449	0.5631	0.086*
C8	0.72070 (16)	0.4796 (2)	0.5640 (2)	0.0562 (6)
H8A	0.6782	0.4493	0.4932	0.067*

	U11	U22	U33	U12	U13	U23
S1	0.0465 (3)	0.0663 (4)	0.0681 (4)	0.0096 (3)	0.0337 (3)	0.0104 (3)
O1	0.0407 (8)	0.0691 (10)	0.0836 (12)	0.0153 (7)	0.0269 (8)	0.0072 (8)
N1	0.0395 (9)	0.0581 (11)	0.0632 (11)	0.0094 (8)	0.0255 (8)	0.0135 (9)
C1	0.0387 (11)	0.0530 (12)	0.0566 (13)	0.0036 (9)	0.0205 (9)	−0.0051 (10)
C2	0.0644 (15)	0.0712 (16)	0.0834 (18)	0.0110 (13)	0.0370 (14)	0.0239 (14)
C3	0.0349 (10)	0.0546 (12)	0.0573 (13)	0.0039 (9)	0.0244 (9)	0.0078 (10)
C4	0.0496 (13)	0.0865 (18)	0.0723 (16)	0.0010 (13)	0.0244 (12)	−0.0099 (14)
C5	0.0468 (14)	0.120 (3)	0.0796 (19)	−0.0082 (16)	0.0043 (13)	0.0141 (19)
C6	0.0438 (14)	0.092 (2)	0.114 (2)	0.0204 (14)	0.0361 (16)	0.0376 (19)
C7	0.0624 (15)	0.0610 (15)	0.105 (2)	0.0186 (13)	0.0467 (16)	0.0171 (15)
C8	0.0508 (13)	0.0567 (14)	0.0675 (14)	0.0032 (10)	0.0274 (11)	0.0033 (11)

S1—O1i	3.0078 (18)	C3—C8	1.377 (3)
S1—C1	1.825 (2)	C4—C5	1.393 (4)
S1—S1i	2.0262 (11)	C4—H4A	0.9300
O1—C1	1.209 (2)	C5—C6	1.371 (4)
N1—C1	1.345 (3)	C5—H5A	0.9300
N1—C3	1.442 (2)	C6—C7	1.359 (4)
N1—C2	1.461 (3)	C6—H6A	0.9300
C2—H2A	0.9600	C7—C8	1.384 (3)
C2—H2B	0.9600	C7—H7A	0.9300
C2—H2C	0.9600	C8—H8A	0.9300
C3—C4	1.376 (3)
C1—S1—S1i	100.51 (7)	C3—C4—C5	118.9 (3)
C1—N1—C3	122.98 (17)	C3—C4—H4A	120.5
C1—N1—C2	118.97 (17)	C5—C4—H4A	120.5
C3—N1—C2	117.79 (17)	C6—C5—C4	120.3 (3)
O1—C1—N1	124.8 (2)	C6—C5—H5A	119.8
O1—C1—S1	122.58 (16)	C4—C5—H5A	119.8
N1—C1—S1	112.64 (14)	C7—C6—C5	120.3 (2)
N1—C2—H2A	109.5	C7—C6—H6A	119.8
N1—C2—H2B	109.5	C5—C6—H6A	119.8
H2A—C2—H2B	109.5	C6—C7—C8	120.3 (3)
N1—C2—H2C	109.5	C6—C7—H7A	119.8
H2A—C2—H2C	109.5	C8—C7—H7A	119.8
H2B—C2—H2C	109.5	C3—C8—C7	119.6 (2)
C4—C3—C8	120.5 (2)	C3—C8—H8A	120.2
C4—C3—N1	119.9 (2)	C7—C8—H8A	120.2
C8—C3—N1	119.5 (2)
C3—N1—C1—O1	174.2 (2)	C8—C3—C4—C5	−1.3 (4)
C2—N1—C1—O1	0.2 (3)	N1—C3—C4—C5	−177.6 (2)
C3—N1—C1—S1	−6.4 (3)	C3—C4—C5—C6	1.0 (4)
C2—N1—C1—S1	179.66 (17)	C4—C5—C6—C7	0.2 (4)
S1i—S1—C1—O1	−0.1 (2)	C5—C6—C7—C8	−1.2 (4)
S1i—S1—C1—N1	−179.48 (15)	C4—C3—C8—C7	0.4 (3)
C1—N1—C3—C4	−81.5 (3)	N1—C3—C8—C7	176.7 (2)
C2—N1—C3—C4	92.5 (3)	C6—C7—C8—C3	0.9 (4)
C1—N1—C3—C8	102.2 (3)	C1—S1—S1i—C1i	−81.55 (14)
C2—N1—C3—C8	−83.8 (3)