Crystal structure of N-[(methyl-sulfan-yl)carbon-yl]urea.

The almost planar (r.m.s. deviation = 0.055 Å) title compound, (MeS)C(O)NHC(O)NH2, was formed during an attempted crystallization of dimethyl cyano-carbonimidodi-thio-ate with CrO2Cl2; an unexpected redox reaction converted the cyano-carbonimido moiety to a urea group and removed one methyl-thiol group. In the crystal, hydrogen-bonding inter-actions from the amide and amido N-H groups to carbonyl O atoms of neighbouring mol-ecules result in [010] ribbon-like chains.

Chemical context

We have recently reported that dimethyl cyano­carbon­imido­di­thio­ate (MeS)2C=N—C N is an N-donor ligand, coord­in­ating to metal centres (Diop et al., 2016 ▸). In an attempt to broaden data on the coordination ability of this ligand, we have initiated here a study of the inter­actions between dimethyl cyano­carbonimidodi­thio­ate and CrO2Cl2 which yielded the title compound whose X-ray study is reported in this work. Surprisingly, the dimethyl cyano­carbonimidodi­thio­ate has undergone redox reactivity at both the cyanide (N1/C1) and the imido (N2/C2) functionalities. The carbon atoms associated with these groups have been oxidized to an amide and both nitro­gen atoms now sport hydrogen atoms. One methyl­thiol group has been removed during this reaction. Presumably adventitious water is the source of the oxygen and hydrogen. This was unexpected reactivity. It is not known if or how the CrO2Cl2 plays a role in this reaction.

Structural commentary

The starting dimethyl cyano­carbonimidodi­thio­ate (MeS)2C=N—C N has undergone oxidation yielding the title compound (MeS)C(O)NHC(O)NH2 (Fig. 1 ▸). Bond distances and angles within the mol­ecule are in the expected range (Sow et al., 2014 ▸; Jalový et al., 2011 ▸). Although the C1—N1 [1.3159 (19) Å] bond appears shorter than the C2—N2 [1.3623 (18) Å] and C1—N2 [1.3977 (18) Å] bonds, all three are within expected ranges for urea N—C bond distances (MOGUL analysis; Bruno et al., 2004 ▸) because of the different substituents on the carbon atoms. The C2—S1—C3 bond angle is 99.22 (7)°. The torsion angles are close to zero or 180°, which is consistent with a nearly planar mol­ecule (r.m.s. deviation for the non-hydrogen atoms = 0.055 Å). An intra­molecular N1—H1NB⋯O2 hydrogen bond generates an S(6) ring (see Table 1 ▸).

Figure 1

The mol­ecular structure of the title compound. Displacement ellipsoids are depicted at the 50% probability level and H atoms as spheres of an arbitrary radius.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1NB⋯O1i	0.77 (2)	2.27 (2)	2.8518 (16)	132.3 (19)
N1—H1NB⋯O2	0.77 (2)	2.15 (2)	2.7397 (17)	134 (2)
N1—H1NA⋯O1ii	0.87 (2)	2.05 (2)	2.9221 (16)	178 (2)
N2—H2NA⋯O2iii	0.805 (19)	2.18 (2)	2.9709 (15)	168.9 (16)
C3—H3A⋯O2iv	0.98	2.54	3.494 (2)	166
C3—H3B⋯S1v	0.98	2.85	3.7064 (15)	147

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

Supra­molecular features

In the crystal, the compound forms a hydrogen-bonded dimer with a mol­ecule related through the inversion center at (½, ½, 0) [N1⋯O1ii; symmetry code: (ii) −x + 1, −y + 1, −z). This ‘head-to-head’ arrangement forces the non-inter­acting thio­methyl groups to be on the exterior of the chain. These hydrogen-bonded dimers propagate into a one-dimensional chain parallel to the b axis (Fig. 2 ▸) through hydrogen bonds from N1⋯O1i and N2⋯O2iii [symmetry codes: (i) x, y − 1, z; (iii) x, y + 1, z]. The ribbons are oriented approximately parallel to the [30] plane. The compactness and the stability of the structure are consolidated through van der Waals forces and weak C—H⋯O and C—H⋯S hydrogen bonds(Table 1 ▸).

Figure 2

Packing diagram of the title compound showing one-dimensional hydrogen-bonded chains (dashed lines) viewed along the a axis.

Database survey

To the best of our knowledge there are no reported structures that contain the N-[(methylsulfanyl)carbonyl]urea group (CSD Version 5.37 plus one update; Groom &Allen, 2014 ▸).

Synthesis and crystallization

All chemicals are purchased from Aldrich Company (Germany) and used as received. Dimethyl cyano­carbon­imido­di­thio­ate was mixed in aceto­nitrile with CrO2Cl2 in a 1:1 ratio: a green solution was obtained. Two colourless crystals – one of which being this studied compound – suitable for a single-crystal X-ray diffraction study were obtained after a slow solvent evaporation at room temperature (303 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. Urea hydrogen atoms were located from a difference Fourier map and refined freely. Methyl hydrogen atoms were included in geometrically calculated positions and allowed to rotate to minimize their contribution to electron density with C—H = 0.98 Å and U iso(H) = 1.5U eq(C3).

Table 2

Experimental details

Crystal data
Chemical formula	C3H6N2O2S
M r	134.16
Crystal system, space group	Monoclinic, P21/n
Temperature (K)	120
a, b, c (Å)	9.9388 (13), 5.0999 (6), 10.6755 (14)
β (°)	94.136 (4)
V (Å3)	539.70 (12)
Z	4
Radiation type	Mo Kα
μ (mm−1)	0.50
Crystal size (mm)	0.24 × 0.19 × 0.14
Data collection
Diffractometer	Bruker Kappa X8–APEXII
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 ▸)
T min, T max	0.679, 0.734
No. of measured, independent and observed [I > 2σ(I)] reflections	8437, 1344, 1220
R int	0.024
(sin θ/λ)max (Å−1)	0.669
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.031, 0.084, 1.09
No. of reflections	1344
No. of parameters	86
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.38, −0.23

Computer programs: APEX3 (Bruker, 2015 ▸), SAINT (Bruker, 2015 ▸), SHELXT2014 (Sheldrick, 2015a ▸), SHELXL2014 (Sheldrick, 2015b ▸), XP in SHELXTL (Sheldrick, 2008 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016002322/hb7563sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016002322/hb7563Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989016002322/hb7563Isup3.cml

CCDC reference: 1452062

Additional supporting information: crystallographic information; 3D view; checkCIF report

C3H6N2O2S	F(000) = 280
Mr = 134.16	Dx = 1.651 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.9388 (13) Å	Cell parameters from 3996 reflections
b = 5.0999 (6) Å	θ = 2.7–28.3°
c = 10.6755 (14) Å	µ = 0.50 mm−1
β = 94.136 (4)°	T = 120 K
V = 539.70 (12) Å3	Tablet, colorless
Z = 4	0.24 × 0.19 × 0.14 mm

Bruker Kappa X8-APEXII diffractometer	1344 independent reflections
Radiation source: fine-focus sealed tube	1220 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
Detector resolution: 8.33 pixels mm-1	θmax = 28.4°, θmin = 2.7°
combination of ω and φ–scans	h = −13→13
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −6→6
Tmin = 0.679, Tmax = 0.734	l = −8→14
8437 measured reflections

Refinement on F2	Primary atom site location: real-space vector search
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031	Hydrogen site location: mixed
wR(F2) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0502P)2 + 0.2127P] where P = (Fo2 + 2Fc2)/3
1344 reflections	(Δ/σ)max = 0.001
86 parameters	Δρmax = 0.38 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

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.

	x	y	z	Uiso*/Ueq
S1	0.69406 (4)	0.42571 (7)	0.54507 (3)	0.01914 (14)
O1	0.54686 (11)	0.7074 (2)	0.13127 (9)	0.0204 (2)
O2	0.62689 (10)	0.08127 (18)	0.36859 (10)	0.0183 (2)
N1	0.55218 (13)	0.2665 (2)	0.13289 (12)	0.0186 (3)
H1NB	0.5637 (18)	0.144 (5)	0.1744 (19)	0.025 (5)*
H1NA	0.521 (2)	0.276 (5)	0.055 (2)	0.036 (5)*
N2	0.61955 (13)	0.5113 (2)	0.31095 (12)	0.0162 (3)
H2NA	0.6285 (16)	0.660 (4)	0.3351 (16)	0.013 (4)*
C1	0.57029 (14)	0.4988 (3)	0.18511 (13)	0.0157 (3)
C2	0.64159 (13)	0.3108 (3)	0.39424 (12)	0.0154 (3)
C3	0.70883 (16)	0.1190 (3)	0.62609 (14)	0.0229 (3)
H3A	0.6205	0.0327	0.6228	0.034*
H3B	0.7408	0.1494	0.7139	0.034*
H3C	0.7732	0.0067	0.5860	0.034*

	U11	U22	U33	U12	U13	U23
S1	0.0303 (2)	0.0137 (2)	0.0128 (2)	−0.00005 (12)	−0.00299 (14)	−0.00060 (12)
O1	0.0322 (6)	0.0120 (5)	0.0162 (5)	0.0004 (4)	−0.0045 (4)	0.0002 (4)
O2	0.0258 (5)	0.0117 (5)	0.0169 (5)	−0.0011 (4)	−0.0023 (4)	−0.0009 (4)
N1	0.0296 (7)	0.0110 (6)	0.0143 (6)	0.0009 (5)	−0.0044 (5)	0.0012 (5)
N2	0.0234 (6)	0.0112 (6)	0.0137 (6)	−0.0014 (4)	−0.0009 (4)	−0.0014 (4)
C1	0.0182 (6)	0.0146 (6)	0.0141 (6)	0.0002 (5)	0.0003 (5)	0.0000 (5)
C2	0.0165 (6)	0.0153 (6)	0.0143 (6)	−0.0001 (5)	0.0000 (5)	−0.0006 (5)
C3	0.0336 (8)	0.0172 (7)	0.0170 (7)	−0.0016 (6)	−0.0037 (6)	0.0041 (5)

S1—C2	1.7569 (14)	C2—N2	1.3623 (18)
S1—C3	1.7885 (15)	C1—N2	1.3977 (18)
C1—O1	1.2239 (18)	N2—H2NA	0.805 (19)
C2—O2	1.2088 (17)	C3—H3A	0.9800
C1—N1	1.3159 (19)	C3—H3B	0.9800
N1—H1NB	0.77 (2)	C3—H3C	0.9800
N1—H1NA	0.87 (2)
C2—S1—C3	99.22 (7)	O2—C2—N2	124.61 (13)
C1—N1—H1NB	118.6 (16)	O2—C2—S1	123.61 (11)
C1—N1—H1NA	112.5 (16)	N2—C2—S1	111.78 (10)
H1NB—N1—H1NA	129 (2)	S1—C3—H3A	109.5
C2—N2—C1	128.44 (12)	S1—C3—H3B	109.5
C2—N2—H2NA	119.3 (12)	H3A—C3—H3B	109.5
C1—N2—H2NA	112.0 (12)	S1—C3—H3C	109.5
O1—C1—N1	124.62 (13)	H3A—C3—H3C	109.5
O1—C1—N2	116.95 (13)	H3B—C3—H3C	109.5
N1—C1—N2	118.43 (13)
C2—N2—C1—O1	173.40 (14)	C1—N2—C2—S1	−176.11 (11)
C2—N2—C1—N1	−6.5 (2)	C3—S1—C2—O2	−1.02 (14)
C1—N2—C2—O2	3.7 (2)	C3—S1—C2—N2	178.83 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1NB···O1i	0.77 (2)	2.27 (2)	2.8518 (16)	132.3 (19)
N1—H1NB···O2	0.77 (2)	2.15 (2)	2.7397 (17)	134 (2)
N1—H1NA···O1ii	0.87 (2)	2.05 (2)	2.9221 (16)	178 (2)
N2—H2NA···O2iii	0.805 (19)	2.18 (2)	2.9709 (15)	168.9 (16)
C3—H3A···O2iv	0.98	2.54	3.494 (2)	166
C3—H3B···S1v	0.98	2.85	3.7064 (15)	147