Crystal structure of N-[(methyl­sulfan­yl)carbon­yl]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 cyano­carbonimidodi­thio­ate with CrO₂Cl₂; an unexpected redox reaction converted the cyano­carbonimido moiety to a urea group and removed one methyl­thiol group. In the crystal, hydrogen-bonding inter­actions from the amide and amido N—H groups to carbonyl O atoms of neighbouring mol­ecules result in [010] ribbon-like chains.

1. 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.

2. 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).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1NB⋯O1^i	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⋯O1^ii	0.87 (2)	2.05 (2)	2.9221 (16)	178 (2)
N2—H2NA⋯O2^iii	0.805 (19)	2.18 (2)	2.9709 (15)	168.9 (16)
C3—H3A⋯O2^iv	0.98	2.54	3.494 (2)	166
C3—H3B⋯S1^v	0.98	2.85	3.7064 (15)	147
Symmetry codes: (i) x, y-1, z; (ii) -x+1, -y+1, -z; (iii) x, y+1, z; (iv) -x+1, -y, -z+1; (v) .

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.

3. 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.

4. 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).

5. 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).

6. 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
Mr	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 (Å^3)	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)
Tmin, Tmax	0.679, 0.734
No. of measured, independent and observed [I > 2σ(I)] reflections	8437, 1344, 1220
Rint	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).

Supporting information

S1. 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 this ligand coordination ability, 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.

S2. 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).

S3. Supra­molecular features

In the crystal, the compound forms a hydrogen-bonded dimer with a molecule related through the inversion center at (1/2, 1/2, 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 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 [301] 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).

S4. Database survey

To the best of our knowledge there are no reported structures that contain the N-(thio­methyl­methanoyl) urea group (CSD Version 5.37 + 1 update; Groom &Allen, 2014).

S5. 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).

S6. 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) .

Structure description

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 this ligand coordination ability, 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.

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).

In the crystal, the compound forms a hydrogen-bonded dimer with a molecule related through the inversion center at (1/2, 1/2, 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 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 [301] 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).

To the best of our knowledge there are no reported structures that contain the N-(thio­methyl­methanoyl) urea group (CSD Version 5.37 + 1 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 details

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) .

Computing details

Data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 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.
	Fig. 2. Packing diagram of the title compound showing one-dimensional hydrogen-bonded chains (dashed lines) viewed along the a axis.

N-[(Methylsulfanyl)carbonyl]urea

Crystal data

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) Å^3	Tablet, colorless
Z = 4	0.24 × 0.19 × 0.14 mm

Data collection

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

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

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1NB···O1^i	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···O1^ii	0.87 (2)	2.05 (2)	2.9221 (16)	178 (2)
N2—H2NA···O2^iii	0.805 (19)	2.18 (2)	2.9709 (15)	168.9 (16)
C3—H3A···O2^iv	0.98	2.54	3.494 (2)	166
C3—H3B···S1^v	0.98	2.85	3.7064 (15)	147

Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z; (iii) x, y+1, z; (iv) −x+1, −y, −z+1; (v) −x+3/2, y−1/2, −z+3/2.