Bis(N-methyl-N-phenyl­carbamo­yl)disulfane

Alayne L Schroll; Maren Pink; George Barany

doi:10.1107/S1600536812016030

. 2012 Apr 28;68(Pt 5):o1550. doi: 10.1107/S1600536812016030

Bis(N-methyl-N-phenylcarbamoyl)disulfane

Alayne L Schroll ^a, Maren Pink ^b, George Barany ^c,^*

PMCID: PMC3344649 PMID: 22590411

Abstract

The title compound, C₁₆H₁₆N₂O₂S₂, 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 interest to our research program over 30 years ago. We now confirm the proposed molecular structure in which the molecule exhibits a twofold axis of symmetry through the mid-point of the S—S bond and the two planes defined by the (carbamoyl)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 _r = 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
Δρ_max = 0.21 e Å⁻³
Δρ_min = −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.

Supplementary Material

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

e-68-o1550-sup1.cif^{(13.3KB, cif)}

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

e-68-o1550-Isup2.hkl^{(72.6KB, hkl)}

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

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

Acknowledgments

We thank Dr Victor G. Young, Jr, Director of the X-Ray Crystallographic Facility at the University of Minnesota (where the data was obtained), who provided invaluable assistance and discussions during the preparation of this manuscript, Dr Jed Fisher for useful discussions and Tat’Yana Kenigsberg for assistance with the literature. Prior synthetic and mechanistic work involving the title compound were carried out by (in chronological order ending with most recent): David A. Halsrud, Dr Andrew W. Mott, Dr Steven J. Eastep, Matt Swenson, Michael J. Barany, Alex M. Schrader and Phillip T. Goldblatt.

supplementary crystallographic information

Comment

Bis(N-methyl-N-phenylcarbamoyl)disulfane (C₁₆H₁₆N₂O₂S₂) was first reported by Kobayashi et al. (1973). The compound became of interest to our research program over thirty years ago (Barany et al., 1983; Schroll and Barany, 1986) and has been synthesized by several different high-yield routes, as well as encountered as a co-product in a number of reaction pathways (Barany et al., 1983; Schroll and Barany, 1986; Schrader et al., 2011). We now confirm the molecular structure of the title compound by single-crystal X-ray analysis. The disulfane reported herein is the flagship of the homologous series of bis(N-methyl-N-phenylcarbamoyl)polysulfanes, C₁₆H₁₆N₂O₂S_n , which have been prepared and structurally characterized for n = 1–6.

The title compound exhibits a twofold axis of symmetry through the center of the S–S bond, and all bond distances and angles are within expected ranges. The N–C bond distance is 1.35 Å, consistent with ~60% double bond character, with the consequence that the (carbamoyl)sulfenyl atoms (S1,C1,O1,N1,C2,C3) are in a plane. The aromatic ring is nearly perpendicular to the (carbamoyl)sulfenyl plane, with a torsion angle of 92.5° (C2–N1–C3–C4). The S–S bond length of 2.03 Å is slightly shorter than the 2.07 Å reported for the S–S bond length in elemental sulfur (S₈), suggesting that some partial double bond character extends through the S–S bond due to its adjacency to carbonyl groups on both sides. Several other reference compounds also have an S–S bond length of 2.01–2.03 Å (Bereman et al., 1983; Rout et al., 1983; Paul and Srikrishnan, 2004; Fun et al., 2001; Raya et al., 2005; Li et al., 2006; Singh et al., 2011). The most noteworthy feature of the title compound is the torsion angle about the disulfane, which is 81.6° and as such is somewhat smaller than the theoretical optimum of 90.0° (Pauling, 1949; Torrico-Vallejos et al., 2010) that has been explained as allowing for minimal mutual repulsion of pπ orbital electron lone pairs in sulfur. A comparable deviation from theory was reported for dibenzoyl disulfide (Rout et al., 1983; Paul & Srikrishnan, 2004), where the torsion angle is 80.8°. Bis(N-methyl-N-phenylthiocarbamoyl)disulfane, which only differs from the title compound by two thiocarbonyls in place of two carbonyls, has a torsion angle about the disulfane of 89.8° and shows a conformation that is not completely superimposable on the title compound (Fun et al., 2001).

Note regarding nomenclature: The title compound is named in a manner that is consistent with our prior publications. The closely related C₁₆H₁₆N₂S₄ was named bis(N-methyl-N-phenylthiocarbamoyl) disulfide by Fun et al. (2001), but we have chosen the "disulfane" revised name for consistency.

Table 1 Selected geometric parameters (Å, °)

N1–C1 1.345 (3)

N1–C2 1.461 (3)

N1–C3 1.442 (2)

C1–O1 1.209 (2)

C1–S1 1.825 (2)

S1–S1 2.0262 (11)

C2–N1–C3–C4 92.5 (3)

C1–S1–S1–C1 81.55 (14)

Symmetry operator (a): -x + 1, y, -z + 1/2

Experimental

The title compound was prepared in high yield from the reaction of N-methylaniline with bis(chlorocarbonyl)disulfane, and recrystallized from hot carbon tetrachloride/chloroform (3:2) in 60–85% recovery or from hot acetone in 75% recovery (Barany et al., 1983).

Figures

Fig. 1. — Crystallographic structure of the title compound showing 50% probability displacement ellipsoids and with all non-hydrogen atoms labelled and numbered.

Crystal data

C₁₆H₁₆N₂O₂S₂	F(000) = 696
M_r = 332.43	D_x = 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

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Data collection

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

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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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0553P)² + 1.0043P] where P = (F_o² + 2F_c²)/3
1468 reflections	(Δ/σ)_max = 0.001
101 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

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Special details

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.

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Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²)

	x	y	z	U_iso*/U_eq
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*

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Atomic displacement parameters (Å²)

	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)

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Geometric parameters (Å, º)

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)

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Symmetry code: (i) −x+1, y, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: QM2060).

References

Barany, G., Schroll, A. L., Mott, A. W. & Halsrud, D. A. (1983). J. Org. Chem. 48, 4750–4761.
Bereman, R. D., Baird, D. M., Bordner, J. & Dorfman, J. R. (1983). Polyhedron, 2, 25–30.
Bruker (2001). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2010). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
Fun, H.-K., Chantrapromma, S., Razak, I. A., Bei, F.-L., Jian, F.-F., Yang, X.-J., Lu, L. & Wang, X. (2001). Acta Cryst. E57, o717–o718. [DOI] [PubMed]
Kobayashi, N., Osawa, A. & Fujisawa, T. (1973). Chem. Lett. 12, 1315–1318.
Li, F., Yin, H.-D., Hong, M., Zhai, J. & Wang, D.-Q. (2006). Acta Cryst. E62, m1417–m1418.
Paul, C. & Srikrishnan, T. (2004). J. Chem. Crystallogr. 34, 211–217.
Pauling, L. (1949). Proc. Natl Acad. Sci. USA, 35, 495–499. [DOI] [PMC free article] [PubMed]
Raya, I., Baba, I., Rosli, F. Z. & Yamin, B. M. (2005). Acta Cryst. E61, o3131–o3132.
Rout, G. C., Seshasayee, M., Subrahmanyan, T. & Aravamudan, G. (1983). Acta Cryst. C39, 1387–1389.
Schrader, A. M., Schroll, A. L. & Barany, G. (2011). J. Org. Chem. 76, 7882–7892. [DOI] [PubMed]
Schroll, A. L. & Barany, G. (1986). J. Org. Chem. 51, 1866–1881.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
Singh, S., Chaturvedi, J., Bhattacharya, S. & Noth, H. (2011). Polyhedron, 30, 93–97.
Torrico-Vallejos, S., Erben, M. F., Boese, R. & Vedova, C. O. D. (2010). New J. Chem. 34, 1365–1372.
Wang, Y. & Liao, J. H. (1989). Acta Cryst. B45, 65–69.

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

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

e-68-o1550-sup1.cif^{(13.3KB, cif)}

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

e-68-o1550-Isup2.hkl^{(72.6KB, hkl)}

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

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

[bb1] Barany, G., Schroll, A. L., Mott, A. W. & Halsrud, D. A. (1983). J. Org. Chem. 48, 4750–4761.

[bb2] Bereman, R. D., Baird, D. M., Bordner, J. & Dorfman, J. R. (1983). Polyhedron, 2, 25–30.

[bb3] Bruker (2001). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.

[bb4] Bruker (2010). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.

[bb5] Fun, H.-K., Chantrapromma, S., Razak, I. A., Bei, F.-L., Jian, F.-F., Yang, X.-J., Lu, L. & Wang, X. (2001). Acta Cryst. E57, o717–o718. [DOI] [PubMed]

[bb6] Kobayashi, N., Osawa, A. & Fujisawa, T. (1973). Chem. Lett. 12, 1315–1318.

[bb7] Li, F., Yin, H.-D., Hong, M., Zhai, J. & Wang, D.-Q. (2006). Acta Cryst. E62, m1417–m1418.

[bb8] Paul, C. & Srikrishnan, T. (2004). J. Chem. Crystallogr. 34, 211–217.

[bb9] Pauling, L. (1949). Proc. Natl Acad. Sci. USA, 35, 495–499. [DOI] [PMC free article] [PubMed]

[bb10] Raya, I., Baba, I., Rosli, F. Z. & Yamin, B. M. (2005). Acta Cryst. E61, o3131–o3132.

[bb11] Rout, G. C., Seshasayee, M., Subrahmanyan, T. & Aravamudan, G. (1983). Acta Cryst. C39, 1387–1389.

[bb12] Schrader, A. M., Schroll, A. L. & Barany, G. (2011). J. Org. Chem. 76, 7882–7892. [DOI] [PubMed]

[bb13] Schroll, A. L. & Barany, G. (1986). J. Org. Chem. 51, 1866–1881.

[bb14] Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]

[bb15] Singh, S., Chaturvedi, J., Bhattacharya, S. & Noth, H. (2011). Polyhedron, 30, 93–97.

[bb16] Torrico-Vallejos, S., Erben, M. F., Boese, R. & Vedova, C. O. D. (2010). New J. Chem. 34, 1365–1372.

[bb17] Wang, Y. & Liao, J. H. (1989). Acta Cryst. B45, 65–69.

PERMALINK

Bis(N-methyl-N-phenylcarbamoyl)disulfane

Alayne L Schroll

Maren Pink

George Barany

Abstract

Related literature

Experimental

Crystal data

Data collection

Refinement

Supplementary Material

Acknowledgments

supplementary crystallographic information

Comment

Experimental

Refinement

Figures

Fig. 1.

Crystal data

Data collection

Refinement

Special details

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²)

Atomic displacement parameters (Å²)

Geometric parameters (Å, º)

Footnotes

References

Associated Data

Supplementary Materials

ACTIONS

PERMALINK

RESOURCES

Cite

Add to Collections

PERMALINK

Bis(N-methyl-N-phenyl­carbamo­yl)disulfane

Alayne L Schroll

Maren Pink

George Barany

Abstract

Related literature

Experimental

Crystal data

Data collection

Refinement

Supplementary Material

Acknowledgments

supplementary crystallographic information

Comment

Experimental

Refinement

Figures

Fig. 1.

Crystal data

Data collection

Refinement

Special details

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

Atomic displacement parameters (Å2)

Geometric parameters (Å, º)

Footnotes

References

Associated Data

Supplementary Materials

ACTIONS

PERMALINK

RESOURCES

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Bis(N-methyl-N-phenylcarbamoyl)disulfane

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²)

Atomic displacement parameters (Å²)