N-Ethyl-N-phenyl-N′-tosyl­formamidine

Shen, H.-S.; Liu, N.; Li, Z.-C.; Huang, W.-C.

doi:10.1107/S1600536809021953

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1582

doi:10.1107/S1600536809021953

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N-Ethyl-N-phenyl-N′-tosylformamidine

Heng-Shui Shen,^a Nan Liu,^a Zi-Cheng Li ^b and Wen-Cai Huang ^b ^*

^aKey Laboratory of Drug Targeting and Drug-Delivery Systems of the Ministry of Education, Department of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu 610041, People's Republic of China, and ^bDepartment of Pharmaceutical and Bioengineering, School of Chemical Engineering, Sichuan University, Chengdu 610065, People's Republic of China
^*Correspondence e-mail: hwc@scu.edu.cn

(Received 30 May 2009; accepted 9 June 2009; online 17 June 2009)

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 , 2007 ). For the synthesis of substituted sulfanilamides by catalytic amidation, see: Liu et al. (2008 ); Xu et al. (2007 , 2008 ).

Experimental

Crystal data

C₁₆H₁₈N₂O₂S
M_r = 302.38
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.054
wR(F²) = 0.154
S = 1.09
2928 reflections
192 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.44 e Å⁻³

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

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

For the crystal structure of related compounds, see: Cole et al. (2005, 2007). For the synthesis of substituted sulfanilamide by catalytic amidation, see: Liu et al. (2008); Xu et al. (2007, 2008).

Experimental top

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.

Computing details top

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

Figures top

	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.

N-Ethyl-N-phenyl-N'-tosylformamidine top

Crystal data top

C₁₆H₁₈N₂O₂S	F(000) = 640
M_r = 302.38	D_x = 1.260 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 16.306 (5) Å	θ = 4.7–7.7°
b = 8.122 (4) Å	µ = 0.21 mm⁻¹
c = 12.674 (4) Å	T = 291 K
β = 108.22 (2)°	Block, colourless
V = 1594.3 (10) Å³	0.60 × 0.46 × 0.42 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1958 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.005
Graphite monochromator	θ_max = 25.5°, θ_min = 1.3°
ω–2θ scans	h = −6→19
Absorption correction: for a sphere (WinGX; Farrugia, 1999)	k = −9→0
T_min = 0.885, T_max = 0.918	l = −15→14
3769 measured reflections	3 standard reflections every 200 reflections
2928 independent reflections	intensity decay: 2.7%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.154	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0973P)²] where P = (F_o² + 2F_c²)/3
2928 reflections	(Δ/σ)_max < 0.001
192 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

C₁₆H₁₈N₂O₂S	V = 1594.3 (10) Å³
M_r = 302.38	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.306 (5) Å	µ = 0.21 mm⁻¹
b = 8.122 (4) Å	T = 291 K
c = 12.674 (4) Å	0.60 × 0.46 × 0.42 mm
β = 108.22 (2)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1958 reflections with I > 2σ(I)
Absorption correction: for a sphere (WinGX; Farrugia, 1999)	R_int = 0.005
T_min = 0.885, T_max = 0.918	3 standard reflections every 200 reflections
3769 measured reflections	intensity decay: 2.7%
2928 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.154	H-atom parameters constrained
S = 1.09	Δρ_max = 0.34 e Å⁻³
2928 reflections	Δρ_min = −0.44 e Å⁻³
192 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
S1	0.22480 (4)	0.35989 (7)	0.03686 (5)	0.0502 (2)
O1	0.29488 (10)	0.4299 (2)	0.00582 (16)	0.0589 (5)
O2	0.20033 (12)	0.4417 (2)	0.12215 (16)	0.0671 (5)
N1	0.24137 (12)	0.1667 (2)	0.07283 (17)	0.0519 (5)
N2	0.33809 (12)	−0.0487 (2)	0.10219 (16)	0.0499 (5)
C1	−0.0882 (2)	0.3571 (5)	−0.3731 (3)	0.1032 (13)
H1A	−0.1362	0.4031	−0.3547	0.155*
H1B	−0.1020	0.2469	−0.4003	0.155*
H1C	−0.0763	0.4232	−0.4294	0.155*
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	−0.0734	0.3725	−0.1595	0.097*
C4	0.05244 (17)	0.3632 (4)	−0.0724 (3)	0.0706 (8)
H4	0.0452	0.3694	−0.0026	0.085*
C5	0.13384 (15)	0.3529 (3)	−0.0822 (2)	0.0488 (6)
C6	0.14362 (18)	0.3421 (4)	−0.1855 (3)	0.0739 (8)
H6	0.1985	0.3331	−0.1928	0.089*
C7	0.0719 (2)	0.3447 (5)	−0.2784 (3)	0.0844 (10)
H7	0.0791	0.3399	−0.3483	0.101*
C8	0.31639 (14)	0.1071 (3)	0.07690 (19)	0.0465 (5)
H8	0.3564	0.1767	0.0614	0.056*
C9	0.27942 (17)	−0.1647 (3)	0.1310 (3)	0.0654 (8)
H9A	0.2849	−0.2722	0.1006	0.078*
H9B	0.2203	−0.1278	0.0979	0.078*
C10	0.2990 (2)	−0.1785 (4)	0.2552 (3)	0.0852 (9)
H10A	0.3586	−0.2073	0.2887	0.128*
H10B	0.2631	−0.2620	0.2716	0.128*
H10C	0.2877	−0.0749	0.2844	0.128*
C11	0.42519 (15)	−0.1012 (3)	0.11568 (19)	0.0459 (6)
C12	0.49282 (16)	−0.0216 (3)	0.1901 (2)	0.0597 (7)
H12	0.4828	0.0657	0.2320	0.072*
C13	0.57586 (17)	−0.0723 (4)	0.2023 (3)	0.0689 (8)
H13	0.6220	−0.0188	0.2529	0.083*
C14	0.59129 (19)	−0.1996 (4)	0.1413 (3)	0.0700 (8)
H14	0.6477	−0.2328	0.1505	0.084*
C15	0.5245 (2)	−0.2778 (4)	0.0673 (3)	0.0753 (9)
H15	0.5352	−0.3637	0.0249	0.090*
C16	0.44046 (19)	−0.2311 (3)	0.0543 (2)	0.0611 (7)
H16	0.3946	−0.2867	0.0047	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0381 (3)	0.0471 (4)	0.0608 (4)	0.0024 (2)	0.0089 (3)	−0.0001 (3)
O1	0.0414 (9)	0.0505 (9)	0.0797 (12)	−0.0026 (7)	0.0118 (9)	0.0065 (9)
O2	0.0571 (11)	0.0710 (12)	0.0682 (12)	0.0060 (9)	0.0124 (9)	−0.0151 (10)
N1	0.0370 (10)	0.0499 (11)	0.0639 (13)	0.0017 (8)	0.0084 (9)	0.0074 (9)
N2	0.0409 (11)	0.0454 (11)	0.0538 (12)	0.0006 (8)	0.0010 (9)	0.0040 (9)
C1	0.067 (2)	0.126 (3)	0.089 (2)	0.013 (2)	−0.0152 (19)	−0.004 (2)
C2	0.0511 (15)	0.0738 (18)	0.0694 (19)	0.0089 (13)	−0.0011 (14)	−0.0040 (15)
C3	0.0391 (14)	0.114 (3)	0.084 (2)	0.0170 (16)	0.0112 (15)	0.0069 (18)
C4	0.0431 (14)	0.099 (2)	0.0668 (17)	0.0185 (14)	0.0139 (13)	0.0050 (16)
C5	0.0368 (12)	0.0470 (12)	0.0596 (15)	0.0059 (10)	0.0108 (11)	0.0012 (11)
C6	0.0446 (15)	0.107 (2)	0.0693 (19)	0.0033 (15)	0.0162 (14)	−0.0107 (17)
C7	0.0657 (19)	0.125 (3)	0.0575 (18)	0.0086 (19)	0.0119 (16)	−0.0106 (18)
C8	0.0403 (12)	0.0481 (13)	0.0452 (13)	−0.0006 (10)	0.0047 (10)	0.0019 (10)
C9	0.0468 (14)	0.0541 (14)	0.083 (2)	−0.0065 (11)	0.0022 (14)	0.0118 (14)
C10	0.092 (2)	0.082 (2)	0.091 (2)	−0.0002 (18)	0.042 (2)	0.0094 (19)
C11	0.0457 (13)	0.0448 (12)	0.0417 (12)	0.0060 (10)	0.0058 (10)	0.0057 (10)
C12	0.0460 (13)	0.0597 (15)	0.0631 (16)	0.0036 (12)	0.0022 (12)	−0.0096 (12)
C13	0.0440 (14)	0.0769 (18)	0.0763 (19)	0.0044 (13)	0.0054 (14)	0.0058 (16)
C14	0.0548 (16)	0.0751 (18)	0.085 (2)	0.0171 (14)	0.0291 (16)	0.0245 (17)
C15	0.087 (2)	0.0697 (19)	0.079 (2)	0.0193 (17)	0.0405 (19)	0.0017 (16)
C16	0.0689 (17)	0.0584 (15)	0.0520 (15)	−0.0008 (13)	0.0132 (13)	−0.0049 (12)

Geometric parameters (Å, º) top

S1—O2	1.428 (2)	C6—H6	0.9300
S1—O1	1.4371 (18)	C7—H7	0.9300
S1—N1	1.633 (2)	C8—H8	0.9300
S1—C5	1.755 (3)	C9—C10	1.510 (5)
N1—C8	1.301 (3)	C9—H9A	0.9700
N2—C8	1.326 (3)	C9—H9B	0.9700
N2—C11	1.441 (3)	C10—H10A	0.9600
N2—C9	1.467 (3)	C10—H10B	0.9600
C1—C2	1.517 (4)	C10—H10C	0.9600
C1—H1A	0.9600	C11—C12	1.369 (3)
C1—H1B	0.9600	C11—C16	1.379 (4)
C1—H1C	0.9600	C12—C13	1.377 (4)
C2—C7	1.363 (4)	C12—H12	0.9300
C2—C3	1.373 (4)	C13—C14	1.361 (4)
C3—C4	1.376 (4)	C13—H13	0.9300
C3—H3	0.9300	C14—C15	1.353 (4)
C4—C5	1.374 (3)	C14—H14	0.9300
C4—H4	0.9300	C15—C16	1.381 (4)
C5—C6	1.371 (4)	C15—H15	0.9300
C6—C7	1.376 (4)	C16—H16	0.9300

O2—S1—O1	117.23 (12)	N1—C8—N2	122.7 (2)
O2—S1—N1	107.27 (12)	N1—C8—H8	118.6
O1—S1—N1	112.35 (10)	N2—C8—H8	118.6
O2—S1—C5	107.76 (11)	N2—C9—C10	111.4 (2)
O1—S1—C5	107.95 (12)	N2—C9—H9A	109.3
N1—S1—C5	103.32 (11)	C10—C9—H9A	109.3
C8—N1—S1	116.09 (17)	N2—C9—H9B	109.3
C8—N2—C11	119.30 (19)	C10—C9—H9B	109.3
C8—N2—C9	121.8 (2)	H9A—C9—H9B	108.0
C11—N2—C9	118.42 (19)	C9—C10—H10A	109.5
C2—C1—H1A	109.5	C9—C10—H10B	109.5
C2—C1—H1B	109.5	H10A—C10—H10B	109.5
H1A—C1—H1B	109.5	C9—C10—H10C	109.5
C2—C1—H1C	109.5	H10A—C10—H10C	109.5
H1A—C1—H1C	109.5	H10B—C10—H10C	109.5
H1B—C1—H1C	109.5	C12—C11—C16	120.1 (2)
C7—C2—C3	118.3 (3)	C12—C11—N2	119.6 (2)
C7—C2—C1	121.3 (3)	C16—C11—N2	120.3 (2)
C3—C2—C1	120.4 (3)	C11—C12—C13	119.2 (3)
C2—C3—C4	121.2 (3)	C11—C12—H12	120.4
C2—C3—H3	119.4	C13—C12—H12	120.4
C4—C3—H3	119.4	C14—C13—C12	120.9 (3)
C5—C4—C3	119.7 (3)	C14—C13—H13	119.5
C5—C4—H4	120.2	C12—C13—H13	119.5
C3—C4—H4	120.2	C15—C14—C13	119.9 (3)
C6—C5—C4	119.6 (3)	C15—C14—H14	120.0
C6—C5—S1	120.3 (2)	C13—C14—H14	120.0
C4—C5—S1	120.1 (2)	C14—C15—C16	120.5 (3)
C5—C6—C7	119.7 (3)	C14—C15—H15	119.8
C5—C6—H6	120.2	C16—C15—H15	119.8
C7—C6—H6	120.2	C11—C16—C15	119.4 (3)
C2—C7—C6	121.6 (3)	C11—C16—H16	120.3
C2—C7—H7	119.2	C15—C16—H16	120.3
C6—C7—H7	119.2

O2—S1—N1—C8	−125.18 (19)	C5—C6—C7—C2	−1.5 (5)
O1—S1—N1—C8	5.1 (2)	S1—N1—C8—N2	−178.33 (18)
C5—S1—N1—C8	121.1 (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—C5	0.6 (5)	C11—N2—C9—C10	76.0 (3)
C3—C4—C5—C6	−0.7 (4)	C8—N2—C11—C12	55.5 (3)
C3—C4—C5—S1	177.3 (2)	C9—N2—C11—C12	−116.7 (3)
O2—S1—C5—C6	154.6 (2)	C8—N2—C11—C16	−124.7 (3)
O1—S1—C5—C6	27.1 (3)	C9—N2—C11—C16	63.1 (3)
N1—S1—C5—C6	−92.1 (2)	C16—C11—C12—C13	0.3 (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—C14	0.2 (4)
N1—S1—C5—C4	89.9 (2)	C12—C13—C14—C15	0.2 (5)
C4—C5—C6—C7	1.1 (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—C6	1.3 (5)	N2—C11—C16—C15	179.1 (2)
C1—C2—C7—C6	179.9 (3)	C14—C15—C16—C11	1.5 (4)

Experimental details

Crystal data
Chemical formula	C₁₆H₁₈N₂O₂S
M_r	302.38
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	16.306 (5), 8.122 (4), 12.674 (4)
β (°)	108.22 (2)
V (Å³)	1594.3 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.60 × 0.46 × 0.42

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	For a sphere (WinGX; Farrugia, 1999)
T_min, T_max	0.885, 0.918
No. of measured, independent and observed [I > 2σ(I)] reflections	3769, 2928, 1958
R_int	0.005
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.154, 1.09
No. of reflections	2928
No. of parameters	192
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.44

Computer programs: DIFRAC (Gabe & White, 1993), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

References

Cole, M. L., Deacon, G. B., Forsyth, C. M., Junk, P. C., Konstas, K. & Wang, J. (2007). Chem. Eur. J. 13, 8092–8110. Web of Science CSD CrossRef PubMed CAS Google Scholar
Cole, M. L., Deacon, G. B., Junk, P. C. & Konstas, K. (2005). Chem. Commun. pp. 1581–1583. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
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