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Acta Crystallogr Sect E Struct Rep Online. 2010 March 1; 66(Pt 3): o506–o507.
Published online 2010 February 3. doi:  10.1107/S1600536810003326
PMCID: PMC2983512

N-(4-Chloro­phen­yl)-1,1,1-trifluoro-N-(trifluoro­methyl­sulfon­yl)methane­sulfonamide

Abstract

The title mol­ecule, also called 4-chloro-N,N-bis­(trifluoro­methane­sulfon­yl)aniline, C8H4ClF6NO4S2, has non-crystallographic twofold symmetry with the pseudo-axis aligned along the Cl—C(...)C—N backbone of the mol­ecule: the SO2CF3 residues lie to either side of the benzene ring. In the crystal, the presence of C—H(...)O contacts lead to the formation of a sequence of 12-membered {(...)HC2NSO}2 synthons within a supra­molecular chain aligned along [101].

Related literature

For uses of N,N-bis­(trifluoro­methane­sulfon­yl)aniline derivatives, see: Zeller (2001 [triangle]); Wulff et al. (1986 [triangle]). For general background to the synthesis, see: Deprez et al. (1995 [triangle]); Greenfield & Crosanu (2008 [triangle]). For a previous synthesis of the title compound, see: Laali et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o506-scheme1.jpg

Experimental

Crystal data

  • C8H4ClF6NO4S2
  • M r = 391.70
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o506-efi1.jpg
  • a = 11.5998 (3) Å
  • b = 13.4423 (4) Å
  • c = 9.0548 (2) Å
  • β = 108.014 (2)°
  • V = 1342.69 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.68 mm−1
  • T = 120 K
  • 0.40 × 0.25 × 0.25 mm

Data collection

  • Nonius KappaCCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2007 [triangle]) T min = 0.821, T max = 1.000
  • 17100 measured reflections
  • 3047 independent reflections
  • 2806 reflections with I > 2σ(I)
  • R int = 0.023

Refinement

  • R[F 2 > 2σ(F 2)] = 0.031
  • wR(F 2) = 0.082
  • S = 1.04
  • 3047 reflections
  • 199 parameters
  • H-atom parameters constrained
  • Δρmax = 0.62 e Å−3
  • Δρmin = −0.41 e Å−3

Data collection: COLLECT (Hooft, 1998 [triangle]); cell refinement: DENZO (Otwinowski & Minor, 1997 [triangle]) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and DIAMOND (Brandenburg, 2006 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810003326/hb5319sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810003326/hb5319Isup2.hkl

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

Acknowledgments

The use of the EPSRC X-ray crystallographic service at the University of Southampton, England, and the valuable assistance of the staff there is gratefully acknowledged. JLW acknowledges support from CAPES (Brazil).

supplementary crystallographic information

Comment

N,N-Bis(trifluoromethanesulfonyl)aniline derivatives find use in synthetic chemistry such as mild triflating reagents (Zeller, 2001; Wulff et al., 1986). Following a literature procedure to p-ClC6H4NHSO2CF3, using p-ClC6H4NH2, (F3CSO2)O and Et3N in CH2Cl2 at 213 K, a little of the di-substituted compound, p-ClC6H4(NSO2CF3), (I), was isolated as a side-product (Greenfield & Crosanu, 2008; Deprez et al., 1995). Compound (I) has been reported previously (Laali et al., 2007) and the X-ray structure determination is reported herein.

In (I), the SO2CF3 groups occupy approximately orthogonal positions to either side of the aromatic ring: the C3/C4/N1/S1, S2 torsion angles are 77.44 (17) and -101.55 (15) °, respectively; the dihedral angle formed between the benzene ring and NS2 group is 78.13 (6) °. The CF3 groups lie to either side of the molecule and fold back over the benzene ring so that, overall, the molecule has non-crystallographic 2-fold symmetry when viewed down the Cl1–C1–C4–N1 axis.

Supramolecular aggregation in (I) is dominated by C–H···O interactions that lead to the formation of a sequence of 12-membered {···HC2NSO}2 synthons aligned along [1 0 1], Fig. 2 and Table 1. Chains are connected into layers through the agency of C–Cl···π interactions between centrosymmetrically related residues [C1–Cl1···ring centroid(C1–C6)i = 3.4592 (8) Å with angle at Cl1 = 92.46 (6) ° for i: 2-x, 2-y, 1-z]. The layers thus formed stack along the b axis with the closest contacts between successive layers being of the type C–F···π [C8–F4···ring centroid(C1–C6)ii = 3.4708 (16) Å with angle at F4 = 122.83 (11) ° for ii: x, 3/2-y,1/2+z].

Experimental

To a cooled (213 K) solution of p-ClC6H4NH2 (11.5 g, 9.0 mmol) and triethylamine (1.50 ml; 10.8 mmol, 1.20 eq.) in CH2Cl2 (40 ml) was slowly added a solution of trifluoromethanesulfonic anhydride (2.40 ml; 13.5 mmol, 1.50 eq) in CH2Cl2 (40 ml). After the mixture was stirred at 213-223 K for 1 h, water (30 ml) was added. The mixture was allowed to warm to room temperature, and the organic layer was decanted, washed with water, dried, and evaporated. The products, N-(4-chlorophenyl)trifluoromethylsulfonamide and N-(4-chlorophenyl)-bis-trifluoromethylsulfonamide, (I), were purified by chromatography on silica gel with hexane as eluent. Products were recrystallized from hexane. Characterisation data for (I): m.pt. 346-348 K, 1H-NMR (500 MHz, CDCl3) δ: 7.34 (2H), 7.50 (2H) p.p.m. 13C-NMR (125 MHz, CDCl3) δ: 119.36 (q, 1J(C,F) = 325 Hz), 125.17 (C3), 130.06, 132.18, 138.84 p.p.m. 19F-NMR (376 MHz, CDCl3) δ: 71.11 p.p.m.

Refinement

The C-bound H atoms were geometrically placed (C–H = 0.95 Å) and refined as riding with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of (I) showing displacement ellipsoids at the 50% probability level.
Fig. 2.
A view of the supramolecular chain in (I) aligned along [1 0 1] and mediated by C–H···O interactions (blue dashed lines). Colour code: Cl, cyan; S, yellow; F, pink; O, red; N, blue; C, grey; and H, green.
Fig. 3.
View of the stacking of layers in (I). The C–H···O interactions are shown as blue dashed lines. Colour code: Cl, cyan; S, yellow; F, pink; O, red; N, blue; C, grey; and H, green.

Crystal data

C8H4ClF6NO4S2F(000) = 776
Mr = 391.70Dx = 1.938 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2983 reflections
a = 11.5998 (3) Åθ = 2.9–27.5°
b = 13.4423 (4) ŵ = 0.68 mm1
c = 9.0548 (2) ÅT = 120 K
β = 108.014 (2)°Block, colourless
V = 1342.69 (6) Å30.40 × 0.25 × 0.25 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer3047 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode2806 reflections with I > 2σ(I)
10 cm confocal mirrorsRint = 0.023
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.9°
[var phi] and ω scansh = −15→15
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)k = −17→17
Tmin = 0.821, Tmax = 1.000l = −11→11
17100 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.082H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.0407P)2 + 1.1662P] where P = (Fo2 + 2Fc2)/3
3047 reflections(Δ/σ)max = 0.001
199 parametersΔρmax = 0.62 e Å3
0 restraintsΔρmin = −0.41 e Å3

Special details

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

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

xyzUiso*/Ueq
Cl10.97286 (4)0.86092 (3)0.34987 (5)0.02733 (12)
S10.78053 (4)1.09197 (3)0.91222 (4)0.01889 (11)
S20.59031 (4)0.94255 (3)0.78741 (5)0.01943 (11)
F10.70006 (16)1.20000 (9)0.66292 (14)0.0497 (4)
F20.75847 (13)1.28200 (9)0.87505 (16)0.0449 (3)
F30.58975 (12)1.20628 (11)0.8139 (2)0.0551 (4)
F40.69058 (14)0.77016 (10)0.86879 (18)0.0525 (4)
F50.71980 (16)0.87281 (11)1.05802 (17)0.0663 (5)
F60.54674 (13)0.80495 (10)0.96076 (16)0.0478 (3)
O10.90194 (11)1.10259 (10)0.91208 (15)0.0280 (3)
O20.74816 (13)1.08338 (10)1.04986 (15)0.0293 (3)
O30.54372 (11)0.89593 (10)0.64061 (14)0.0254 (3)
O40.52094 (12)1.00882 (11)0.84680 (16)0.0308 (3)
N10.72049 (12)0.99798 (10)0.79108 (15)0.0167 (3)
C10.89885 (15)0.90047 (12)0.4795 (2)0.0192 (3)
C20.79853 (15)0.96166 (12)0.42518 (19)0.0201 (3)
H20.77060.98120.31920.024*
C30.73954 (14)0.99385 (12)0.52852 (18)0.0182 (3)
H30.67041.03580.49430.022*
C40.78292 (14)0.96396 (12)0.68241 (18)0.0162 (3)
C50.88287 (15)0.90243 (12)0.73621 (19)0.0198 (3)
H50.91060.88240.84200.024*
C60.94185 (15)0.87055 (12)0.6327 (2)0.0218 (3)
H61.01100.82860.66680.026*
C70.70024 (18)1.20199 (13)0.8072 (2)0.0258 (4)
C80.64203 (18)0.84073 (14)0.9298 (2)0.0301 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0291 (2)0.0285 (2)0.0294 (2)−0.00347 (16)0.01644 (18)−0.01089 (17)
S10.0231 (2)0.0187 (2)0.01481 (19)−0.00119 (14)0.00583 (15)−0.00231 (13)
S20.0178 (2)0.0220 (2)0.0187 (2)−0.00101 (14)0.00585 (15)0.00126 (14)
F10.0996 (12)0.0286 (6)0.0236 (6)0.0191 (7)0.0229 (7)0.0060 (5)
F20.0691 (9)0.0188 (5)0.0461 (7)−0.0062 (6)0.0167 (7)−0.0067 (5)
F30.0402 (7)0.0402 (7)0.0918 (12)0.0177 (6)0.0303 (8)0.0267 (7)
F40.0650 (9)0.0347 (7)0.0620 (9)0.0206 (7)0.0257 (8)0.0194 (6)
F50.0872 (11)0.0427 (8)0.0367 (7)−0.0277 (8)−0.0281 (7)0.0189 (6)
F60.0593 (9)0.0433 (7)0.0469 (8)−0.0179 (6)0.0252 (7)0.0100 (6)
O10.0216 (6)0.0317 (7)0.0290 (7)−0.0046 (5)0.0053 (5)−0.0099 (5)
O20.0462 (8)0.0276 (7)0.0174 (6)−0.0026 (6)0.0146 (6)−0.0025 (5)
O30.0211 (6)0.0313 (7)0.0216 (6)−0.0065 (5)0.0032 (5)−0.0025 (5)
O40.0267 (7)0.0358 (7)0.0357 (7)0.0025 (6)0.0182 (6)−0.0020 (6)
N10.0178 (6)0.0171 (6)0.0158 (6)−0.0006 (5)0.0060 (5)−0.0025 (5)
C10.0216 (8)0.0159 (7)0.0226 (8)−0.0044 (6)0.0105 (6)−0.0059 (6)
C20.0241 (8)0.0204 (8)0.0152 (7)−0.0020 (6)0.0055 (6)−0.0020 (6)
C30.0182 (7)0.0175 (7)0.0171 (7)0.0018 (6)0.0027 (6)0.0002 (6)
C40.0163 (7)0.0166 (7)0.0160 (7)−0.0004 (6)0.0055 (6)−0.0015 (6)
C50.0197 (8)0.0207 (8)0.0176 (8)0.0021 (6)0.0038 (6)0.0024 (6)
C60.0190 (8)0.0193 (8)0.0269 (8)0.0029 (6)0.0069 (7)−0.0003 (6)
C70.0371 (10)0.0185 (8)0.0244 (9)0.0017 (7)0.0134 (7)0.0002 (6)
C80.0360 (10)0.0247 (9)0.0258 (9)−0.0082 (7)0.0040 (8)0.0053 (7)

Geometric parameters (Å, °)

Cl1—C11.7380 (16)F5—C81.304 (2)
S1—O21.4131 (13)F6—C81.313 (2)
S1—O11.4160 (13)N1—C41.4637 (19)
S1—N11.6769 (13)C1—C61.381 (2)
S1—C71.8470 (18)C1—C21.385 (2)
S2—O41.4135 (13)C2—C31.388 (2)
S2—O31.4168 (13)C2—H20.9500
S2—N11.6749 (14)C3—C41.387 (2)
S2—C81.8483 (19)C3—H30.9500
F1—C71.306 (2)C4—C51.384 (2)
F2—C71.317 (2)C5—C61.388 (2)
F3—C71.303 (2)C5—H50.9500
F4—C81.309 (3)C6—H60.9500
O2—S1—O1123.00 (9)C2—C3—H3120.5
O2—S1—N1110.21 (8)C5—C4—C3122.06 (15)
O1—S1—N1106.70 (7)C5—C4—N1119.00 (14)
O2—S1—C7106.88 (8)C3—C4—N1118.94 (14)
O1—S1—C7105.19 (9)C4—C5—C6118.75 (15)
N1—S1—C7103.02 (8)C4—C5—H5120.6
O4—S2—O3122.60 (8)C6—C5—H5120.6
O4—S2—N1109.14 (8)C1—C6—C5119.21 (15)
O3—S2—N1107.18 (7)C1—C6—H6120.4
O4—S2—C8107.55 (9)C5—C6—H6120.4
O3—S2—C8105.91 (8)F3—C7—F1110.51 (18)
N1—S2—C8102.67 (8)F3—C7—F2108.18 (16)
C4—N1—S2118.56 (10)F1—C7—F2109.00 (16)
C4—N1—S1118.91 (10)F3—C7—S1110.98 (13)
S2—N1—S1122.53 (8)F1—C7—S1110.08 (12)
C6—C1—C2122.17 (15)F2—C7—S1108.03 (13)
C6—C1—Cl1119.27 (13)F5—C8—F4110.23 (19)
C2—C1—Cl1118.56 (13)F5—C8—F6109.09 (18)
C1—C2—C3118.74 (15)F4—C8—F6108.97 (16)
C1—C2—H2120.6F5—C8—S2111.24 (13)
C3—C2—H2120.6F4—C8—S2109.37 (13)
C4—C3—C2119.07 (15)F6—C8—S2107.89 (14)
C4—C3—H3120.5
O4—S2—N1—C4−155.34 (12)N1—C4—C5—C6−179.88 (14)
O3—S2—N1—C4−20.57 (14)C2—C1—C6—C50.1 (3)
C8—S2—N1—C490.75 (13)Cl1—C1—C6—C5179.81 (13)
O4—S2—N1—S123.61 (12)C4—C5—C6—C1−0.4 (2)
O3—S2—N1—S1158.38 (9)O2—S1—C7—F3−40.94 (16)
C8—S2—N1—S1−90.29 (11)O1—S1—C7—F3−173.17 (14)
O2—S1—N1—C4−151.50 (12)N1—S1—C7—F375.21 (15)
O1—S1—N1—C4−15.75 (14)O2—S1—C7—F1−163.59 (14)
C7—S1—N1—C494.75 (13)O1—S1—C7—F164.17 (16)
O2—S1—N1—S229.55 (12)N1—S1—C7—F1−47.44 (16)
O1—S1—N1—S2165.30 (9)O2—S1—C7—F277.50 (14)
C7—S1—N1—S2−84.20 (11)O1—S1—C7—F2−54.73 (14)
C6—C1—C2—C30.0 (2)N1—S1—C7—F2−166.35 (12)
Cl1—C1—C2—C3−179.66 (12)O4—S2—C8—F5−67.64 (18)
C1—C2—C3—C40.1 (2)O3—S2—C8—F5159.68 (16)
C2—C3—C4—C5−0.4 (2)N1—S2—C8—F547.42 (18)
C2—C3—C4—N1−179.97 (14)O4—S2—C8—F4170.36 (13)
S2—N1—C4—C5−102.12 (15)O3—S2—C8—F437.69 (16)
S1—N1—C4—C578.89 (17)N1—S2—C8—F4−74.58 (15)
S2—N1—C4—C377.44 (17)O4—S2—C8—F651.97 (16)
S1—N1—C4—C3−101.55 (15)O3—S2—C8—F6−80.71 (15)
C3—C4—C5—C60.6 (2)N1—S2—C8—F6167.02 (13)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C3—H3···O3i0.952.573.496 (2)164
C5—H5···O1ii0.952.593.385 (2)141

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5319).

References

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