2-(Toluene-4-sulfonyl­amino)­benzoyl fluoride

The title compound, C₁₄H₁₂FNO₃S, was used as an activating agent for a chemical synthesis, from which it recrystallized immediately. In the structure, one intramolecular hydrogen bond was found, which leads to the formation of a six-membered ring within one half of the mol­ecule. In the other half of the mol­ecule, there is a disubstituted benzene ring. The electron-withdrawing effect of the S atom and the electron-releasing effect of the opposite methyl substituent are both observed in this structure.

Key indicators

• Single-crystal X-ray study
• T = 180 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.030
• wR factor = 0.082
• Data-to-parameter ratio = 13.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

The title compound, (I), was used as an activating agent for N-containing heterocycles in order to produce iminium salts. During the reaction of those salts with nucleophiles, crystals of (I) suitable for X-ray studies were formed. In the structure of (I), one hydrogen bond between N—H and the acidic O atom was found (Fig. 1), leading to the formation of a six-membered ring. The sum of its endocyclic angles is 719.4 (2)°, i.e. near the ideal value of a planar hexagon. As a consequence, this portion of the molecule forms a common plane including the attached benzene ring and fluorine. The root-mean-square deviation of the atoms from this plane is 0.031 Å. The para-substituted benzene ring shows approximately the expected C_2v symmetry so that for the two matching endocyclic bond angles this holds true even at the 2σ level (Table 1). Therefore, it may be concluded that the angles at C1 [120.99 (13)°] and C4 [118.47 (14)°] are significantly enlarged and diminished, respectively. According to the conclusions of Domenicano et al. (1975), it follows that the S atom introduces a small electron-withdrawing effect in (I), whereas the methyl substituent introduces electron-releasing properties.

S2. Experimental

2-(Toluene-4-sulfonylamino)benzoic acid, synthesized according to Nandi & Debenath (1987), reacts with 1.2 equivalents of cyanuric fluoride in dichloromethane at 263 K. After 1 h of reaction, the product was poured into ice water. From this mixture, the aqueous layer was extracted with dichloromethane. The combined organic phases were dried over MgSO₄ and evaporated under reduced pressure affording (I) in 93% yield.

S3. Refinement

Methyl was refined as a rigid group, the other C-bound H atoms as riding. The fractional coordinates of the H atom bound at nitrogen were freely refined, but its displacement-parameter constraint to equal that of nitrogen.

Computing details

Data collection: IPDS2.87 (Stoe & Cie, 1997); cell refinement: IPDS2.87; data reduction: IPDS2.87; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids (Farrugia, 1997). Only the N-bound H atom is shown.

2-(Toluene-4-sulfonylamino)benzoyl fluoride

Crystal data

C14H12FNO3S	F(000) = 608
Mr = 293.31	Dx = 1.464 Mg m^−3
Monoclinic, P21/a	Mo Kα radiation, λ = 0.71073 Å
a = 11.908 (3) Å	Cell parameters from 5000 reflections
b = 8.2396 (14) Å	θ = 2.9–24.8°
c = 13.925 (4) Å	µ = 0.26 mm^−1
β = 103.14 (3)°	T = 180 K
V = 1330.6 (5) Å^3	Prism, colorless
Z = 4	0.60 × 0.36 × 0.28 mm

Data collection

Stoe IPDS diffractometer	2439 independent reflections
Radiation source: fine-focus sealed X-ray tube	2048 reflections with I > 2σ(I)
Planar graphite monochromator	Rint = 0.031
Detector resolution: 6.667 pixels mm^-1	θmax = 25.8°, θmin = 3.0°
ϕ–oscill., ϕ–incr. = 1.5°, 153 exposures scans	h = −14→14
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983)	k = −9→9
Tmin = 0.859, Tmax = 0.931	l = −17→17
8860 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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0476P)^2 + 0.2945P] where P = (Fo^2 + 2Fc^2)/3
2439 reflections	(Δ/σ)max = 0.009
186 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Special details

Experimental. During data collection the crystal was in cold N₂ gas of the Cryostream Cooler (Oxford Cryosystems, 1992) mounted on a ϕ-axis diffractometer supplied with an area detector.

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
C1	0.31945 (11)	0.16595 (18)	0.13239 (10)	0.0210 (3)
C2	0.41513 (12)	0.2625 (2)	0.13106 (11)	0.0268 (3)
H2	0.4496	0.3263	0.1868	0.029*
C3	0.45902 (13)	0.2639 (2)	0.04734 (12)	0.0303 (4)
H3	0.5247	0.3288	0.0462	0.033*
C4	0.40883 (13)	0.1720 (2)	−0.03582 (11)	0.0293 (4)
C5	0.31386 (14)	0.0759 (2)	−0.03227 (11)	0.0314 (4)
H5	0.2790	0.0123	−0.0880	0.035*
C6	0.26902 (13)	0.0712 (2)	0.05169 (11)	0.0272 (3)
H6	0.2047	0.0041	0.0537	0.030*
C7	0.45660 (17)	0.1789 (3)	−0.12715 (13)	0.0439 (5)
H7A	0.4336	0.2812	−0.1620	0.057*
H7B	0.4264	0.0876	−0.1704	0.057*
H7C	0.5409	0.1724	−0.1084	0.057*
C8	0.41828 (12)	−0.03038 (18)	0.34324 (10)	0.0212 (3)
C9	0.35881 (14)	−0.1752 (2)	0.31468 (11)	0.0292 (4)
H9	0.2790	−0.1726	0.2840	0.032*
C10	0.41620 (15)	−0.3226 (2)	0.33112 (12)	0.0345 (4)
H10	0.3750	−0.4201	0.3110	0.038*
C11	0.53272 (15)	−0.3304 (2)	0.37645 (12)	0.0346 (4)
H11	0.5708	−0.4323	0.3876	0.038*
C12	0.59240 (13)	−0.1885 (2)	0.40508 (11)	0.0293 (4)
H12	0.6720	−0.1931	0.4363	0.032*
C13	0.53704 (12)	−0.03778 (19)	0.38869 (10)	0.0231 (3)
C14	0.60319 (13)	0.1112 (2)	0.42067 (10)	0.0269 (3)
F	0.71528 (8)	0.08033 (14)	0.46345 (7)	0.0429 (3)
N	0.36022 (11)	0.12047 (17)	0.33194 (9)	0.0250 (3)
H1	0.4009 (17)	0.203 (3)	0.3561 (15)	0.043 (6)*
O1	0.16583 (9)	0.05831 (14)	0.22224 (8)	0.0322 (3)
O2	0.23569 (9)	0.34048 (14)	0.25538 (8)	0.0312 (3)
O3	0.57127 (10)	0.24832 (15)	0.41463 (8)	0.0356 (3)
S	0.25781 (3)	0.17382 (5)	0.23630 (3)	0.02227 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0198 (6)	0.0233 (9)	0.0200 (7)	0.0033 (5)	0.0051 (5)	0.0005 (6)
C2	0.0233 (7)	0.0330 (10)	0.0234 (8)	−0.0031 (6)	0.0039 (6)	−0.0030 (6)
C3	0.0238 (7)	0.0376 (11)	0.0314 (8)	−0.0009 (6)	0.0097 (6)	0.0042 (7)
C4	0.0316 (8)	0.0338 (10)	0.0240 (8)	0.0150 (7)	0.0093 (6)	0.0061 (6)
C5	0.0376 (8)	0.0321 (10)	0.0226 (8)	0.0058 (7)	0.0030 (6)	−0.0071 (6)
C6	0.0247 (7)	0.0261 (9)	0.0303 (8)	−0.0012 (6)	0.0052 (6)	−0.0044 (6)
C7	0.0539 (11)	0.0547 (14)	0.0287 (9)	0.0202 (9)	0.0211 (8)	0.0095 (8)
C8	0.0274 (7)	0.0230 (9)	0.0145 (6)	0.0015 (6)	0.0071 (5)	0.0006 (5)
C9	0.0308 (8)	0.0266 (10)	0.0293 (8)	−0.0041 (6)	0.0051 (6)	−0.0013 (6)
C10	0.0463 (10)	0.0230 (10)	0.0348 (9)	−0.0039 (7)	0.0106 (7)	−0.0032 (7)
C11	0.0468 (10)	0.0245 (10)	0.0346 (9)	0.0096 (7)	0.0132 (7)	0.0027 (7)
C12	0.0315 (8)	0.0328 (10)	0.0244 (8)	0.0074 (7)	0.0078 (6)	0.0031 (6)
C13	0.0283 (7)	0.0269 (9)	0.0155 (7)	−0.0005 (6)	0.0077 (6)	0.0008 (6)
C14	0.0289 (8)	0.0343 (11)	0.0179 (7)	−0.0051 (7)	0.0061 (6)	−0.0002 (6)
F	0.0320 (5)	0.0518 (7)	0.0395 (6)	−0.0102 (4)	−0.0029 (4)	−0.0004 (5)
N	0.0313 (7)	0.0215 (8)	0.0213 (6)	0.0012 (5)	0.0040 (5)	−0.0014 (5)
O1	0.0242 (5)	0.0370 (8)	0.0369 (6)	−0.0018 (5)	0.0101 (5)	0.0046 (5)
O2	0.0385 (6)	0.0281 (7)	0.0296 (6)	0.0103 (5)	0.0134 (5)	0.0010 (5)
O3	0.0428 (7)	0.0287 (8)	0.0357 (7)	−0.0083 (5)	0.0094 (5)	−0.0042 (5)
S	0.02115 (19)	0.0249 (2)	0.02186 (19)	0.00365 (14)	0.00718 (14)	0.00199 (14)

Geometric parameters (Å, º)

C1—C6	1.388 (2)	C8—N	1.414 (2)
C1—C2	1.393 (2)	C9—C10	1.387 (2)
C1—S	1.7662 (15)	C9—H9	0.9500
C2—C3	1.382 (2)	C10—C11	1.389 (2)
C2—H2	0.9500	C10—H10	0.9500
C3—C4	1.399 (2)	C11—C12	1.379 (3)
C3—H3	0.9500	C11—H11	0.9500
C4—C5	1.391 (2)	C12—C13	1.400 (2)
C4—C7	1.508 (2)	C12—H12	0.9500
C5—C6	1.392 (2)	C13—C14	1.472 (2)
C5—H5	0.9500	C14—O3	1.189 (2)
C6—H6	0.9500	C14—F	1.3564 (18)
C7—H7A	0.9800	N—S	1.6481 (14)
C7—H7B	0.9800	N—H1	0.85 (2)
C7—H7C	0.9800	O1—S	1.4305 (12)
C8—C9	1.398 (2)	O2—S	1.4344 (12)
C8—C13	1.413 (2)
C6—C1—C2	120.99 (13)	C10—C9—C8	120.10 (15)
C6—C1—S	120.01 (11)	C10—C9—H9	119.9
C2—C1—S	118.91 (11)	C8—C9—H9	119.9
C3—C2—C1	118.91 (14)	C9—C10—C11	121.30 (16)
C3—C2—H2	120.5	C9—C10—H10	119.3
C1—C2—H2	120.5	C11—C10—H10	119.3
C2—C3—C4	121.42 (15)	C12—C11—C10	119.20 (16)
C2—C3—H3	119.3	C12—C11—H11	120.4
C4—C3—H3	119.3	C10—C11—H11	120.4
C5—C4—C3	118.47 (14)	C11—C12—C13	120.81 (15)
C5—C4—C7	121.16 (16)	C11—C12—H12	119.6
C3—C4—C7	120.37 (16)	C13—C12—H12	119.6
C4—C5—C6	121.05 (14)	C12—C13—C8	119.82 (14)
C4—C5—H5	119.5	C12—C13—C14	119.39 (14)
C6—C5—H5	119.5	C8—C13—C14	120.78 (14)
C1—C6—C5	119.14 (14)	O3—C14—F	118.44 (14)
C1—C6—H6	120.4	O3—C14—C13	129.10 (14)
C5—C6—H6	120.4	F—C14—C13	112.46 (14)
C4—C7—H7A	109.5	C8—N—S	125.30 (11)
C4—C7—H7B	109.5	C8—N—H1	115.7 (14)
H7A—C7—H7B	109.5	S—N—H1	110.9 (14)
C4—C7—H7C	109.5	O1—S—O2	119.68 (7)
H7A—C7—H7C	109.5	O1—S—N	109.64 (7)
H7B—C7—H7C	109.5	O2—S—N	103.82 (7)
C9—C8—C13	118.76 (14)	O1—S—C1	108.14 (7)
C9—C8—N	121.02 (13)	O2—S—C1	108.36 (7)
C13—C8—N	120.14 (13)	N—S—C1	106.45 (7)
C6—C1—C2—C3	0.6 (2)	N—C8—C13—C12	176.11 (13)
S—C1—C2—C3	−176.05 (12)	C9—C8—C13—C14	−179.58 (13)
C1—C2—C3—C4	0.6 (2)	N—C8—C13—C14	−2.86 (19)
C2—C3—C4—C5	−1.0 (2)	C12—C13—C14—O3	−178.72 (15)
C2—C3—C4—C7	178.48 (15)	C8—C13—C14—O3	0.3 (2)
C3—C4—C5—C6	0.3 (2)	C12—C13—C14—F	0.46 (18)
C7—C4—C5—C6	−179.18 (15)	C8—C13—C14—F	179.43 (11)
C2—C1—C6—C5	−1.3 (2)	C9—C8—N—S	−40.23 (18)
S—C1—C6—C5	175.33 (12)	C13—C8—N—S	143.13 (12)
C4—C5—C6—C1	0.8 (2)	C8—N—S—O1	56.51 (14)
C13—C8—C9—C10	0.1 (2)	C8—N—S—O2	−174.49 (11)
N—C8—C9—C10	−176.63 (14)	C8—N—S—C1	−60.23 (14)
C8—C9—C10—C11	0.4 (2)	C6—C1—S—O1	6.50 (15)
C9—C10—C11—C12	−0.4 (2)	C2—C1—S—O1	−176.84 (12)
C10—C11—C12—C13	−0.2 (2)	C6—C1—S—O2	−124.62 (13)
C11—C12—C13—C8	0.7 (2)	C2—C1—S—O2	52.03 (14)
C11—C12—C13—C14	179.67 (13)	C6—C1—S—N	124.24 (13)
C9—C8—C13—C12	−0.6 (2)	C2—C1—S—N	−59.10 (14)