The polysulfonylamines bis(methylsulfonamido) sulfone and bis(trifluoromethylsulfonamido) sulfone

Bis­(methyl­sulfon­amido) sulfone, C₂H₈N₂O₆S₃ or SO₂(NHSO₂CH₃)₂, was synthesized from imidobis­(sulfonyl ­chloride), HN(SO₂Cl)₂, and bis­(tri­methyl­silyl)­methane, CH₂[Si(CH₃)₃]₂, in ­chlorotri­methyl­silane solution. In the solid state, there are two independent mol­ecules linked by two N—H...O hydrogen bridges into infinite chains parallel to the b axis. The central S atoms of the independent molecules each lie on a twofold axis. Bis­(tri­fluoro­methyl­sulf­onamido) sulfone, C₂H₂F₆N₂O₆S₃ or SO₂(NHSO₂CF₃)₂, was formed by the reaction of tri­chloro­phosphazosulfuryl tri­fluoro­methane, Cl₃PNSO₂CF₃, with fluoro­sulfonic acid, FSO₃H. The mol­ecules are connected by bifurcated N—H...O bridges into infinite layers parallel to the [001] plane. The central S atom lies on a twofold axis.

S1. Comment

Crystals of the previously unknown compounds bis(methylsulfamido) sulfone, (I) and bis(trifluoromethylsulfamido) sulfone, (II), were formed adventitiously via unspecified protolysis and condensation processes. Compound (I) is formed by the reaction of HN(SO₂Cl)₂ with CH₂(Si(CH₃)₃)₂. Similar unspecified protolysis and condensation processes are described by Hiemisch et al. (1997) for the reaction of Ph₃GeCl and AgN(SO₂F)₂ leading to SO₂(NHSO₂Ph)₂. Compound (II) was isolated as a major product from a reaction mixture of Cl₃PNSO₂CF₃ and FSO₃H. However, Roesky & Giere (1971) report HN(SO₂CF₃)₂ as the only product of this reaction. Although several related substances, derivatives of diimidotris(sulfuric) acid, SO₂[N(Y)—SO₂—X]₂ (where X is NH₂, Ph or F, and Y is H or CH₃), have been described in the literature (Meuwsen & Papenfuss, 1962; Nannelli et al., 1965; Roesky & Hoff, 1968), no analogous structure other than SO₂(NHSO₂Ph)₂ could be located in the Cambridge Structural Database (Version?; Allen, 2002). Related structures are those of the parent compound sulfamide, SO₂(NH₂)₂ (Belaj et al., 1987), and SO₂(NHSO₂Ph)₂ (Hiemisch et al., 1997). \sch

The bond lengths and angles of both (I) and (II) (Tables 1 and 3) are in good agreement with the corresponding parameters of SO₂(NH₂)₂ and SO₂(NHSO₂Ph)₂. For both symmetry-independent molecules of (I), the S—N, S—O and S—C distance are within the ranges 1.638 (3)–1.669 (3), 1.421 (3)–1.437 (3) and 1.742 (4)–1.743 (4) Å, respectively, while the S—N—S angles range from 123.2 (2) to 125.7 (2)°. The S atoms exist in the tetrahedral configuration (Table 1). For both independent molecules of (II), the S—N, S—O and S—C distances lie in the ranges 1.630 (2)–1.639 (2), 1.4080 (19)–1.4092 (18) and 1.823 (3) Å, respectively, while the S—N—S angle is 126.1 (1)°.

The asymmetric unit of (I) consists of two independent SO₂(NHSO₂CH₃)₂ molecules with point symmetry C₂, hereinafter denoted molecules A and B. Molecule A is depicted in Fig. 1. In the crystal packing (Fig. 2), molecules A and B are joined alternately by double N—H····O hydrogen bonds into [ABAB]∞ strands extending in the b direction (Fig. 2). Details of the four independent N—H····O bonds are shown in Table 2.

The point-group symmetry of compound (II) is C₂. Molecule A is depicted in Fig. 3. The S atom of the central SO₂ group is located on the C₂ axis. The molecules are bonded by two bifurcated N—H····O bridges into infinite layers parallel to the [001] plane (Fig. 4). Details of the two independent N—H····O bonds are shown in Table 4. A l l O atoms are involved in hydrogen bonds to N—H groups of neighbouring molecules.

S2. Experimental

The synthesis of (I) was performed by the reaction of HN(SO₂Cl)₂ with an equimolar amount of CH₂(Si(CH₃)₃)₂. Thus HN(SO₂Cl)₂ (0.8 g, 3.7 mmol) was dissolved in (CH₃)₃SiCl (1 ml) and added to CH₂(Si(CH₃)₃)₂ (0.6 g, 3.7 mmol). The vessel was closed, heated to 353 K in an oil bath for 3–4 h and then left to cool down to room temperature. White transparent needle crystals of (I) were formed on cooling (yield: 0.44 g 1.72 mmol, i.e. 69.7%). The best-looking crystal was selected from the mother liquor and immediately subjected to data collection at 150 K. The synthesis of (II) was performed by the reaction of Cl₃PNSO₂CF₃ with an equimolar amount of FSO₃H. Thus, Cl₃PNSO₂CF₃ (2.8 g, 9.85 mmol) was dissolved in CCl₄ (5 ml) and added to FSO₃H (0.98 g, 0.98 mmol). The vessel was closed, heated to 473 K in an oil bath for 2 h and then left to cool down to room temperature. White transparent needle crystals of (II) were formed on cooling (yield: 0.79 g, 2.20 mmol, i.e. 44.4%). The best-looking crystal was selected from the mother liquor and immediately subjected to data collection at 120 K.

S3. Refinement

H atoms of the CH₃ groups in (I) were positioned by geometry and treated as riding. H atoms in the NH groups of both (I) and (II) were located in a difference Fourier map and refined freely (N—H = 0.88–0.92 Å).

Computing details

For both compounds, data collection: CrysAlis (Oxford Diffraction, 2002); cell refinement: KM-4 Software (Kuma, 1995); data reduction: KM-4 Software; program(s) used to solve structure: SHELXTL (Bruker, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. One of the two independent molecules of (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Perspective view of the hydrogen-bonded chain of (I). Hydrogen bonds are indicated by dashed lines.
	Fig. 3. One of the two independent molecules of (II). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. Perspective view of the hydrogen-bonded chain of (II). Hydrogen bonds are indicated by dashed lines.

(I) Bis(methylsulfamido) sulfone

Crystal data

C2H8N2O6S3	F(000) = 520
Mr = 252.28	Dx = 1.820 Mg m^−3
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71069 Å
a = 10.107 (2) Å	Cell parameters from 1867 reflections
b = 9.715 (2) Å	θ = 3.3–15.2°
c = 10.620 (2) Å	µ = 0.81 mm^−1
β = 118.01 (3)°	T = 153 K
V = 920.6 (3) Å^3	Prism, white
Z = 4	0.30 × 0.15 × 0.15 mm

Data collection

Kuma KM-4 CCD area-detector diffractometer	1337 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.047
Graphite monochromator	θmax = 25.0°, θmin = 3.8°
Detector resolution: 0.06 mm pixels mm^-1	h = −12→7
ω scans	k = −11→11
5552 measured reflections	l = −12→12
1599 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	w = 1/[σ^2(Fo^2) + (0.0784P)^2 + 1.2973P] where P = (Fo^2 + 2Fc^2)/3
1599 reflections	(Δ/σ)max < 0.001
121 parameters	Δρmax = 0.56 e Å^−3
0 restraints	Δρmin = −0.61 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
S11	0.77640 (10)	−0.26416 (8)	−0.04137 (9)	0.0233 (3)
S21	0.7500	−0.47429 (11)	−0.2500	0.0215 (3)
N1	0.8472 (3)	−0.3761 (3)	−0.1106 (3)	0.0236 (6)
H1	0.9454	−0.3838	−0.0692	0.028*
O11	0.8986 (3)	−0.1732 (3)	0.0405 (3)	0.0331 (6)
O21	0.6414 (3)	−0.2095 (2)	−0.1551 (3)	0.0296 (6)
O31	0.6379 (3)	−0.5443 (2)	−0.2302 (2)	0.0292 (6)
C1	0.7336 (5)	−0.3629 (4)	0.0716 (4)	0.0328 (9)
H1A	0.6895	−0.3038	0.1169	0.049*
H1B	0.8253	−0.4055	0.1451	0.049*
H1C	0.6617	−0.4348	0.0162	0.049*
S12	0.74742 (10)	0.23541 (8)	0.04881 (9)	0.0225 (3)
S22	0.7500	0.03091 (11)	0.2500	0.0210 (3)
N2	0.8368 (3)	0.1303 (3)	0.1874 (3)	0.0242 (7)
H2	0.9353	0.1279	0.2290	0.029*
O12	0.8610 (3)	0.3334 (2)	0.0658 (3)	0.0290 (6)
O22	0.6135 (3)	0.2838 (2)	0.0462 (3)	0.0301 (6)
O32	0.6333 (3)	−0.0393 (2)	0.1327 (2)	0.0269 (6)
C2	0.7039 (4)	0.1305 (4)	−0.0991 (4)	0.0299 (8)
H2A	0.6394	0.0547	−0.1001	0.045*
H2B	0.7965	0.0930	−0.0936	0.045*
H2C	0.6514	0.1848	−0.1866	0.045*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S11	0.0272 (5)	0.0187 (5)	0.0235 (5)	0.0023 (3)	0.0115 (4)	−0.0016 (3)
S21	0.0258 (7)	0.0161 (6)	0.0225 (6)	0.000	0.0111 (5)	0.000
N1	0.0237 (15)	0.0209 (14)	0.0252 (15)	0.0014 (11)	0.0108 (12)	−0.0008 (11)
O11	0.0348 (15)	0.0264 (13)	0.0345 (14)	−0.0024 (11)	0.0132 (12)	−0.0090 (11)
O21	0.0305 (14)	0.0265 (12)	0.0303 (13)	0.0063 (11)	0.0130 (11)	−0.0007 (10)
O31	0.0342 (15)	0.0248 (12)	0.0283 (13)	−0.0032 (10)	0.0144 (11)	0.0034 (10)
C1	0.044 (2)	0.0313 (19)	0.0337 (19)	0.0050 (17)	0.0268 (18)	0.0008 (16)
S12	0.0255 (5)	0.0188 (5)	0.0242 (5)	0.0000 (3)	0.0125 (4)	0.0015 (3)
S22	0.0241 (6)	0.0161 (6)	0.0221 (6)	0.000	0.0102 (5)	0.000
N2	0.0245 (15)	0.0214 (14)	0.0281 (15)	−0.0006 (12)	0.0135 (13)	0.0013 (11)
O12	0.0310 (14)	0.0220 (12)	0.0374 (14)	−0.0028 (10)	0.0189 (11)	0.0043 (10)
O22	0.0289 (14)	0.0276 (13)	0.0359 (14)	0.0037 (11)	0.0169 (11)	0.0054 (10)
O32	0.0302 (14)	0.0228 (12)	0.0262 (13)	−0.0044 (10)	0.0120 (11)	−0.0042 (9)
C2	0.041 (2)	0.0254 (18)	0.0232 (17)	−0.0004 (16)	0.0147 (16)	−0.0007 (14)

Geometric parameters (Å, º)

S11—O11	1.433 (3)	S12—O22	1.421 (3)
S11—O21	1.434 (3)	S12—O12	1.436 (2)
S11—N1	1.652 (3)	S12—N2	1.666 (3)
S11—C1	1.742 (4)	S12—C2	1.747 (3)
S21—O31	1.419 (2)	S22—O32	1.424 (2)
S21—O31^i	1.419 (2)	S22—O32^ii	1.424 (2)
S21—N1	1.644 (3)	S22—N2	1.640 (3)
S21—N1^i	1.644 (3)	S22—N2^ii	1.640 (3)
N1—H1	0.8800	N2—H2	0.8800
C1—H1A	0.9800	C2—H2A	0.9800
C1—H1B	0.9800	C2—H2B	0.9800
C1—H1C	0.9800	C2—H2C	0.9800
O11—S11—O21	119.40 (15)	O22—S12—O12	118.75 (15)
O11—S11—N1	104.26 (15)	O22—S12—N2	109.64 (15)
O21—S11—N1	107.98 (14)	O12—S12—N2	103.04 (14)
O11—S11—C1	110.10 (18)	O22—S12—C2	109.90 (18)
O21—S11—C1	109.76 (18)	O12—S12—C2	110.43 (17)
N1—S11—C1	104.09 (16)	N2—S12—C2	103.86 (15)
O31—S21—O31^i	122.8 (2)	O32—S22—O32^ii	122.8 (2)
O31—S21—N1	108.97 (13)	O32—S22—N2	107.96 (13)
O31^i—S21—N1	103.36 (14)	O32^ii—S22—N2	104.79 (14)
O31—S21—N1^i	103.36 (14)	O32—S22—N2^ii	104.79 (14)
O31^i—S21—N1^i	108.97 (13)	O32^ii—S22—N2^ii	107.96 (13)
N1—S21—N1^i	109.0 (2)	N2—S22—N2^ii	107.9 (2)
S21—N1—S11	125.64 (18)	S22—N2—S12	123.21 (18)
S21—N1—H1	117.2	S22—N2—H2	118.4
S11—N1—H1	117.2	S12—N2—H2	118.4
S11—C1—H1A	109.5	S12—C2—H2A	109.5
S11—C1—H1B	109.5	S12—C2—H2B	109.5
H1A—C1—H1B	109.5	H2A—C2—H2B	109.5
S11—C1—H1C	109.5	S12—C2—H2C	109.5
H1A—C1—H1C	109.5	H2A—C2—H2C	109.5
H1B—C1—H1C	109.5	H2B—C2—H2C	109.5

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O12^iii	0.88	2.00	2.790 (4)	149
N2—H2···O21^iv	0.88	2.02	2.834 (4)	154

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

(II) Bis(trifluoromethylsulfamido) sulfone

Crystal data

C2H2F6N2O6S3	F(000) = 712
Mr = 360.24	Dx = 2.318 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
a = 9.007 (2) Å	Cell parameters from 1166 reflections
b = 5.537 (1) Å	θ = 2.8–22.8°
c = 20.776 (4) Å	µ = 0.84 mm^−1
β = 94.97 (3)°	T = 120 K
V = 1032.2 (4) Å^3	Prism, white
Z = 4	0.25 × 0.13 × 0.02 mm

Data collection

Kuma KM-4 CCD area-detector diffractometer	1183 independent reflections
Radiation source: fine-focus sealed tube	1046 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.062
Detector resolution: 0.06 mm pixels mm^-1	θmax = 28.4°, θmin = 4.3°
ω scans	h = −11→7
Absorption correction: ψ (SHELXTL; Bruker, 1997)	k = −6→7
Tmin = 0.672, Tmax = 1.000	l = −27→27
3536 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.041P)^2 + 2.8145P] where P = (Fo^2 + 2Fc^2)/3
1183 reflections	(Δ/σ)max < 0.001
87 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.48 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
S1	0.52386 (6)	0.41078 (11)	0.35463 (3)	0.01624 (18)
O1	0.4295 (2)	0.6031 (3)	0.36883 (9)	0.0235 (4)
O2	0.66811 (18)	0.4421 (3)	0.33465 (9)	0.0200 (4)
C1	0.5439 (3)	0.2231 (5)	0.42745 (13)	0.0222 (6)
F1	0.41143 (18)	0.1626 (4)	0.44422 (8)	0.0364 (5)
F2	0.61334 (19)	0.3539 (3)	0.47399 (8)	0.0333 (4)
F3	0.62159 (19)	0.0280 (3)	0.41865 (8)	0.0290 (4)
N1	0.4298 (2)	0.2368 (4)	0.30260 (9)	0.0157 (4)
H1	0.3281	0.2494	0.2989	0.050*
S2	0.5000	0.05867 (15)	0.2500	0.0148 (2)
O3	0.62478 (19)	−0.0623 (3)	0.28032 (9)	0.0202 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0110 (3)	0.0164 (3)	0.0215 (3)	−0.0007 (2)	0.0027 (2)	−0.0016 (2)
O1	0.0169 (9)	0.0217 (10)	0.0323 (10)	0.0025 (7)	0.0049 (7)	−0.0073 (8)
O2	0.0102 (8)	0.0209 (9)	0.0294 (10)	−0.0027 (7)	0.0044 (7)	0.0002 (7)
C1	0.0166 (12)	0.0281 (14)	0.0222 (13)	−0.0021 (11)	0.0022 (10)	0.0007 (10)
F1	0.0237 (9)	0.0572 (13)	0.0296 (9)	−0.0075 (8)	0.0096 (7)	0.0123 (8)
F2	0.0319 (9)	0.0416 (11)	0.0247 (9)	0.0025 (8)	−0.0073 (7)	−0.0092 (7)
F3	0.0341 (9)	0.0251 (9)	0.0281 (9)	0.0050 (7)	0.0038 (7)	0.0051 (7)
N1	0.0087 (9)	0.0206 (11)	0.0180 (10)	0.0001 (8)	0.0030 (7)	−0.0022 (8)
S2	0.0106 (4)	0.0150 (4)	0.0193 (4)	0.000	0.0035 (3)	0.000
O3	0.0149 (8)	0.0207 (9)	0.0253 (9)	0.0050 (7)	0.0039 (7)	0.0036 (7)

Geometric parameters (Å, º)

S1—O2	1.4085 (18)	C1—F2	1.321 (3)
S1—O1	1.4091 (19)	N1—S2	1.639 (2)
S1—N1	1.630 (2)	N1—H1	0.9150
S1—C1	1.831 (3)	S2—O3^i	1.4093 (18)
C1—F3	1.308 (3)	S2—O3	1.4093 (17)
C1—F1	1.315 (3)	S2—N1^i	1.639 (2)
O2—S1—O1	123.85 (12)	F2—C1—S1	107.46 (19)
O2—S1—N1	108.48 (11)	S1—N1—S2	126.13 (12)
O1—S1—N1	107.30 (11)	S1—N1—H1	118.0
O2—S1—C1	106.60 (12)	S2—N1—H1	115.5
O1—S1—C1	105.90 (13)	O3^i—S2—O3	123.24 (17)
N1—S1—C1	102.77 (12)	O3^i—S2—N1	104.20 (10)
F3—C1—F1	109.6 (2)	O3—S2—N1	109.07 (10)
F3—C1—F2	109.3 (2)	O3^i—S2—N1^i	109.07 (10)
F1—C1—F2	109.2 (2)	O3—S2—N1^i	104.20 (10)
F3—C1—S1	111.64 (19)	N1—S2—N1^i	106.00 (15)
F1—C1—S1	109.66 (18)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3^ii	0.92	2.11	2.963 (3)	154
N1—H1···O2^iii	0.92	2.39	2.989 (3)	123

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