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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1582.
Published online 2009 June 17. doi:  10.1107/S1600536809021953
PMCID: PMC2969352

N-Ethyl-N-phenyl-N′-tosyl­formamidine

Abstract

The title compound, C16H18N2O2S, was obtained as an unexpected product while attempting to form carbon–nitro­gen bonds by catalytic amidation. The mol­ecule displays an E conformation about the C=N double bond. The planes of the two aromatic rings in the mol­ecule form a dihedral angle of 47.06 (9)°.

Related literature

For the crystal structures of related compounds, see: Cole et al. (2005 [triangle], 2007 [triangle]). For the synthesis of substituted sulfanilamides by catalytic amidation, see: Liu et al. (2008 [triangle]); Xu et al. (2007 [triangle], 2008 [triangle]).

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Object name is e-65-o1582-scheme1.jpg

Experimental

Crystal data

  • C16H18N2O2S
  • M r = 302.38
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1582-efi1.jpg
  • a = 16.306 (5) Å
  • b = 8.122 (4) Å
  • c = 12.674 (4) Å
  • β = 108.22 (2)°
  • V = 1594.3 (10) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.21 mm−1
  • T = 291 K
  • 0.60 × 0.46 × 0.42 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: spherical (WinGX; Farrugia, 1999 [triangle]) T min = 0.885, T max = 0.918
  • 3769 measured reflections
  • 2928 independent reflections
  • 1958 reflections with I > 2σ(I)
  • R int = 0.005
  • 3 standard reflections every 200 reflections intensity decay: 2.7%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.054
  • wR(F 2) = 0.154
  • S = 1.09
  • 2928 reflections
  • 192 parameters
  • H-atom parameters constrained
  • Δρmax = 0.34 e Å−3
  • Δρmin = −0.44 e Å−3

Data collection: DIFRAC (Gabe & White, 1993 [triangle]); cell refinement: DIFRAC; data reduction: NRCVAX (Gabe et al., 1989 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809021953/rz2331sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809021953/rz2331Isup2.hkl

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

supplementary crystallographic information

Comment

In the course of our studies aimed to prepare a substituted sulfanilamide from the corresponding tertiary amines by catalytic amidation using a transition metal salt (Xu et al., 2008; Xu et al., 2007; Liu et al., 2008), the title compound was unexpectedly obtained in about 54% yield.

The molecule of the title compound (Fig. 1) dispays an E conformation about the C8═N1 double bond. The values of the N1-C8 (1.301 (3) Å) and N2-C8 (1.326 (3) Å) bonds indicate some degree of conjugation, which was not observed in the related compounds N,N'-bis(2,6-diisopropylphenyl)-N-(4-(3',4',5'-trifluorophenoxy)butyl)formamidine (Cole et al., 2007) and N-(4-(2,3,4,5-tetrafluorophenoxy)butyl)-N,N'-bis(2,6-diisopropylphenyl)formamidine (Cole et al., 2005). The dihedral angle formed by the phenyl and benzene rings is 47.06 (9)°. The crystal structure (Fig. 2) is enforced only by van der Waals interactions.

Experimental

N,N-Diethylaniline (149 mg, 1 mmol), p-toluenesulfonyl azide (591 mg, 3 mmol), copper(I) chloride(20 mg, 0.2 mmol), TEBA (triethylbenzylammonium chloride) (22.7 mg, 0.1 mmol) and acetonitrile (5 mL) were added into a 25 mL round-bottom flask. The resulting mixture was stirred and refluxed for 8 h, then it was evaporated to almost dryness under reduced pressure. Purification was performed by column chromatography on silica gel with petroleum ether/ethyl acetate (7:1–6:1, v/v) as eluent to give the pure product (163 mg, yield 54%). Colourless crystals suitable for X-ray analysis were obtained by slow evaporation of a cyclohexane/acetyl acetate solution (5:1 v/v) at room temperature.

Refinement

H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.97 Å and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms.

Figures

Fig. 1.
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.
Fig. 2.
A packing diagram of the title compound approximately viewed along the b axis.

Crystal data

C16H18N2O2SF(000) = 640
Mr = 302.38Dx = 1.260 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 16.306 (5) Åθ = 4.7–7.7°
b = 8.122 (4) ŵ = 0.21 mm1
c = 12.674 (4) ÅT = 291 K
β = 108.22 (2)°Block, colourless
V = 1594.3 (10) Å30.60 × 0.46 × 0.42 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer1958 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.005
graphiteθmax = 25.5°, θmin = 1.3°
ω–2θ scansh = −6→19
Absorption correction: for a sphere (WinGX; Farrugia, 1999)k = −9→0
Tmin = 0.885, Tmax = 0.918l = −15→14
3769 measured reflections3 standard reflections every 200 reflections
2928 independent reflections intensity decay: 2.7%

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)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.154H-atom parameters constrained
S = 1.09w = 1/[σ2(Fo2) + (0.0973P)2] where P = (Fo2 + 2Fc2)/3
2928 reflections(Δ/σ)max < 0.001
192 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = −0.44 e Å3

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 (Å2)

xyzUiso*/Ueq
S10.22480 (4)0.35989 (7)0.03686 (5)0.0502 (2)
O10.29488 (10)0.4299 (2)0.00582 (16)0.0589 (5)
O20.20033 (12)0.4417 (2)0.12215 (16)0.0671 (5)
N10.24137 (12)0.1667 (2)0.07283 (17)0.0519 (5)
N20.33809 (12)−0.0487 (2)0.10219 (16)0.0499 (5)
C1−0.0882 (2)0.3571 (5)−0.3731 (3)0.1032 (13)
H1A−0.13620.4031−0.35470.155*
H1B−0.10200.2469−0.40030.155*
H1C−0.07630.4232−0.42940.155*
C2−0.00939 (19)0.3541 (4)−0.2704 (3)0.0693 (8)
C3−0.01841 (18)0.3645 (4)−0.1664 (3)0.0808 (9)
H3−0.07340.3725−0.15950.097*
C40.05244 (17)0.3632 (4)−0.0724 (3)0.0706 (8)
H40.04520.3694−0.00260.085*
C50.13384 (15)0.3529 (3)−0.0822 (2)0.0488 (6)
C60.14362 (18)0.3421 (4)−0.1855 (3)0.0739 (8)
H60.19850.3331−0.19280.089*
C70.0719 (2)0.3447 (5)−0.2784 (3)0.0844 (10)
H70.07910.3399−0.34830.101*
C80.31639 (14)0.1071 (3)0.07690 (19)0.0465 (5)
H80.35640.17670.06140.056*
C90.27942 (17)−0.1647 (3)0.1310 (3)0.0654 (8)
H9A0.2849−0.27220.10060.078*
H9B0.2203−0.12780.09790.078*
C100.2990 (2)−0.1785 (4)0.2552 (3)0.0852 (9)
H10A0.3586−0.20730.28870.128*
H10B0.2631−0.26200.27160.128*
H10C0.2877−0.07490.28440.128*
C110.42519 (15)−0.1012 (3)0.11568 (19)0.0459 (6)
C120.49282 (16)−0.0216 (3)0.1901 (2)0.0597 (7)
H120.48280.06570.23200.072*
C130.57586 (17)−0.0723 (4)0.2023 (3)0.0689 (8)
H130.6220−0.01880.25290.083*
C140.59129 (19)−0.1996 (4)0.1413 (3)0.0700 (8)
H140.6477−0.23280.15050.084*
C150.5245 (2)−0.2778 (4)0.0673 (3)0.0753 (9)
H150.5352−0.36370.02490.090*
C160.44046 (19)−0.2311 (3)0.0543 (2)0.0611 (7)
H160.3946−0.28670.00470.073*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0381 (3)0.0471 (4)0.0608 (4)0.0024 (2)0.0089 (3)−0.0001 (3)
O10.0414 (9)0.0505 (9)0.0797 (12)−0.0026 (7)0.0118 (9)0.0065 (9)
O20.0571 (11)0.0710 (12)0.0682 (12)0.0060 (9)0.0124 (9)−0.0151 (10)
N10.0370 (10)0.0499 (11)0.0639 (13)0.0017 (8)0.0084 (9)0.0074 (9)
N20.0409 (11)0.0454 (11)0.0538 (12)0.0006 (8)0.0010 (9)0.0040 (9)
C10.067 (2)0.126 (3)0.089 (2)0.013 (2)−0.0152 (19)−0.004 (2)
C20.0511 (15)0.0738 (18)0.0694 (19)0.0089 (13)−0.0011 (14)−0.0040 (15)
C30.0391 (14)0.114 (3)0.084 (2)0.0170 (16)0.0112 (15)0.0069 (18)
C40.0431 (14)0.099 (2)0.0668 (17)0.0185 (14)0.0139 (13)0.0050 (16)
C50.0368 (12)0.0470 (12)0.0596 (15)0.0059 (10)0.0108 (11)0.0012 (11)
C60.0446 (15)0.107 (2)0.0693 (19)0.0033 (15)0.0162 (14)−0.0107 (17)
C70.0657 (19)0.125 (3)0.0575 (18)0.0086 (19)0.0119 (16)−0.0106 (18)
C80.0403 (12)0.0481 (13)0.0452 (13)−0.0006 (10)0.0047 (10)0.0019 (10)
C90.0468 (14)0.0541 (14)0.083 (2)−0.0065 (11)0.0022 (14)0.0118 (14)
C100.092 (2)0.082 (2)0.091 (2)−0.0002 (18)0.042 (2)0.0094 (19)
C110.0457 (13)0.0448 (12)0.0417 (12)0.0060 (10)0.0058 (10)0.0057 (10)
C120.0460 (13)0.0597 (15)0.0631 (16)0.0036 (12)0.0022 (12)−0.0096 (12)
C130.0440 (14)0.0769 (18)0.0763 (19)0.0044 (13)0.0054 (14)0.0058 (16)
C140.0548 (16)0.0751 (18)0.085 (2)0.0171 (14)0.0291 (16)0.0245 (17)
C150.087 (2)0.0697 (19)0.079 (2)0.0193 (17)0.0405 (19)0.0017 (16)
C160.0689 (17)0.0584 (15)0.0520 (15)−0.0008 (13)0.0132 (13)−0.0049 (12)

Geometric parameters (Å, °)

S1—O21.428 (2)C6—H60.9300
S1—O11.4371 (18)C7—H70.9300
S1—N11.633 (2)C8—H80.9300
S1—C51.755 (3)C9—C101.510 (5)
N1—C81.301 (3)C9—H9A0.9700
N2—C81.326 (3)C9—H9B0.9700
N2—C111.441 (3)C10—H10A0.9600
N2—C91.467 (3)C10—H10B0.9600
C1—C21.517 (4)C10—H10C0.9600
C1—H1A0.9600C11—C121.369 (3)
C1—H1B0.9600C11—C161.379 (4)
C1—H1C0.9600C12—C131.377 (4)
C2—C71.363 (4)C12—H120.9300
C2—C31.373 (4)C13—C141.361 (4)
C3—C41.376 (4)C13—H130.9300
C3—H30.9300C14—C151.353 (4)
C4—C51.374 (3)C14—H140.9300
C4—H40.9300C15—C161.381 (4)
C5—C61.371 (4)C15—H150.9300
C6—C71.376 (4)C16—H160.9300
O2—S1—O1117.23 (12)N1—C8—N2122.7 (2)
O2—S1—N1107.27 (12)N1—C8—H8118.6
O1—S1—N1112.35 (10)N2—C8—H8118.6
O2—S1—C5107.76 (11)N2—C9—C10111.4 (2)
O1—S1—C5107.95 (12)N2—C9—H9A109.3
N1—S1—C5103.32 (11)C10—C9—H9A109.3
C8—N1—S1116.09 (17)N2—C9—H9B109.3
C8—N2—C11119.30 (19)C10—C9—H9B109.3
C8—N2—C9121.8 (2)H9A—C9—H9B108.0
C11—N2—C9118.42 (19)C9—C10—H10A109.5
C2—C1—H1A109.5C9—C10—H10B109.5
C2—C1—H1B109.5H10A—C10—H10B109.5
H1A—C1—H1B109.5C9—C10—H10C109.5
C2—C1—H1C109.5H10A—C10—H10C109.5
H1A—C1—H1C109.5H10B—C10—H10C109.5
H1B—C1—H1C109.5C12—C11—C16120.1 (2)
C7—C2—C3118.3 (3)C12—C11—N2119.6 (2)
C7—C2—C1121.3 (3)C16—C11—N2120.3 (2)
C3—C2—C1120.4 (3)C11—C12—C13119.2 (3)
C2—C3—C4121.2 (3)C11—C12—H12120.4
C2—C3—H3119.4C13—C12—H12120.4
C4—C3—H3119.4C14—C13—C12120.9 (3)
C5—C4—C3119.7 (3)C14—C13—H13119.5
C5—C4—H4120.2C12—C13—H13119.5
C3—C4—H4120.2C15—C14—C13119.9 (3)
C6—C5—C4119.6 (3)C15—C14—H14120.0
C6—C5—S1120.3 (2)C13—C14—H14120.0
C4—C5—S1120.1 (2)C14—C15—C16120.5 (3)
C5—C6—C7119.7 (3)C14—C15—H15119.8
C5—C6—H6120.2C16—C15—H15119.8
C7—C6—H6120.2C11—C16—C15119.4 (3)
C2—C7—C6121.6 (3)C11—C16—H16120.3
C2—C7—H7119.2C15—C16—H16120.3
C6—C7—H7119.2
O2—S1—N1—C8−125.18 (19)C5—C6—C7—C2−1.5 (5)
O1—S1—N1—C85.1 (2)S1—N1—C8—N2−178.33 (18)
C5—S1—N1—C8121.1 (2)C11—N2—C8—N1−173.9 (2)
C7—C2—C3—C4−0.9 (5)C9—N2—C8—N1−1.9 (4)
C1—C2—C3—C4−179.5 (3)C8—N2—C9—C10−96.1 (3)
C2—C3—C4—C50.6 (5)C11—N2—C9—C1076.0 (3)
C3—C4—C5—C6−0.7 (4)C8—N2—C11—C1255.5 (3)
C3—C4—C5—S1177.3 (2)C9—N2—C11—C12−116.7 (3)
O2—S1—C5—C6154.6 (2)C8—N2—C11—C16−124.7 (3)
O1—S1—C5—C627.1 (3)C9—N2—C11—C1663.1 (3)
N1—S1—C5—C6−92.1 (2)C16—C11—C12—C130.3 (4)
O2—S1—C5—C4−23.4 (2)N2—C11—C12—C13−179.9 (2)
O1—S1—C5—C4−150.9 (2)C11—C12—C13—C140.2 (4)
N1—S1—C5—C489.9 (2)C12—C13—C14—C150.2 (5)
C4—C5—C6—C71.1 (5)C13—C14—C15—C16−1.0 (5)
S1—C5—C6—C7−176.9 (3)C12—C11—C16—C15−1.2 (4)
C3—C2—C7—C61.3 (5)N2—C11—C16—C15179.1 (2)
C1—C2—C7—C6179.9 (3)C14—C15—C16—C111.5 (4)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2331).

References

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