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The crystal packing in the title compound, C15H16N2O2S, consists of an N—H...πpyrrole, a C—H...πpyrrole, a C—H...πphenyl and two C—H...O interactions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802002520/wn6081sup1.cif
Contains datablocks default, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802002520/wn6081Isup2.hkl
Contains datablock I

CCDC reference: 182623

Key indicators

  • Single-crystal X-ray study
  • T = 145 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.067
  • wR factor = 0.117
  • Data-to-parameter ratio = 20.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


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Comment top

The title compound, (I), was prepared in an effort to extend the gold-catalyzed synthesis of highly substituted phenols with well defined substitution patterns, from furans as starting materials to the corresponding pyrroles which should provide anilines (for background information, see Hashmi et al., 2000). The title molecule (Fig. 1) has two intramolecular contacts which approach the van der Waals contact distance: H5A···O1 2.43 Å and H6B···O2 2.44 Å. The pyrrole group is planar within experimental uncertainty. The phenyl group shows a small deviation from planarity: atoms S and C15 deviate by 0.061 (3) and 0.081 (4) Å, respectively, in the same direction from the phenyl plane. These deviations from planarity may result from crystal-packing effects.

The crystal packing shows five intermolecular interactions [Fig. 2 and Table 1: Cg(pyrrole) is the centroid of the pyrrole ring and Cg(phenyl) is the centroid of the phenyl ring]. The alkyne group acts as a donor of a C—H···O hydrogen bond with a rather short H···O distance of 2.37 Å. The C1—H1 bond also is involved in a C—H···O interaction, but with an H···O distance of 2.45 Å. The pyrrole groups form a herring-bone pattern in the b direction. Neighboring pyrrole groups are connected by N—H···π interactions. The N—H donors do not point to the centroid of the acceptor pyrrole ring, but point closely to atom C2 of the acceptor ring. The intermolecular H01···C2 distance of 2.44 Å is rather short. N—H···πpyrrole interactions have also been reported by Bennis & Gallagher (1998) and Gallagher & Moriarty (1999). The crystal structure of pyrrole (Goddard et al., 1997) shows a herring-bone pattern of pyrrole groups connected by N—H···π interactions, similar to the structure of (I). The angle between neighboring pyrrole groups is 70.1° in the crystal structure of pyrrole, while a similar value of 69.4 (1)° is observed in (I). Intermolecular C5—H5A···πpyrrole interactions further stabilize the crystal structure. The C5—H5A bond points closer to the C2—C3 bond than to the centroid of the acceptor pyrrole group. Intermolecular C15—H15C···πphenyl interactions connect neighboring tosylate groups in the a direction.

Experimental top

Propargylamine (2.20 ml, 32.1 mmol) was added to a solution of pyrrol-2-carboxaldehyde (3.07 g, 32.3 mmol) in dichloromethane containing MgSO4 (10 g, 83 mmol). The reaction mixture was stirred for 20 h at ambient temperature, then the solvent was removed in vacuo to afford (prop-2-ynyl)(1H-pyrrol-2-ylmethylene)amine (4.17 g, 31.6 mmol) in 98% yield. This crude product was dissolved in dry methanol, sodium borohydride (1.43 g, 37.9 mmol) was added at 288 K and the reaction mixture was stirred for 1.5 h at room temperature. After addition of 100 ml water and extraction with dichloromethane, the organic phase was dried over MgSO4 and the solvent partially removed in vacuo. The resulting solution was mixed with triethylamine (8.80 ml, 63.2 mmol) and 4-(N,N-dimethylamino)pyridine (39.0 mg, 319 µmol). At 273 K, toluene-4-sulfonyl chloride (12.0 g, 63.2 mmol) was slowly added and the reaction mixture was stirred at 273 K for 15 min and another 16 h at ambient temperature. After aqueous work-up, the organic phase was dried over MgSO4 and the solvent removed in vacuo. Column chromatography (silica gel, hexane/acetone = 3:1) provided 3.50 g (38%) of (I). Single crystals were obtained by slow evaporation of a solution in ether at 293 K.

Refinement top

The H atoms were taken from a difference Fourier synthesis. They were refined with fixed individual displacement parameters [U(H) = 1.2Ueq(Cnon-methyl), U(H) = 1.5Ueq(Cmethyl) and U(H) = 1.2Ueq(N)], using a riding model with fixed distances: H—N = 0.88 Å, H—C(secondary) = 0.99 Å, H—C(aromatic) = 0.95 Å, HC(methyl) = 0.98 Å and H—C(alkynyl) = 0.95 Å.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Sheldrick, 1996); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The structure of (I) with 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. The crystal packing of (I) viewed down b.
4-methyl-N-(prop-2-ynyl)-N-(1H-pyrrol-2-ylmethyl)-benzenesulfonamide. top
Crystal data top
C15H16N2O2SF(000) = 608
Mr = 288.36Dx = 1.334 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 15.926 (4) ÅCell parameters from 54 reflections
b = 8.345 (4) Åθ = 3–23°
c = 10.955 (3) ŵ = 0.23 mm1
β = 99.50 (4)°T = 145 K
V = 1436.0 (8) Å3Block, colorless
Z = 40.5 × 0.4 × 0.1 mm
Data collection top
Siemens SMART CCD
diffractometer
3749 independent reflections
Radiation source: normal-focus sealed tube2144 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.096
ω scansθmax = 29.0°, θmin = 2.6°
Absorption correction: numerical (SHELXTL; sheldrick, 1996)
?
h = 2121
Tmin = 0.887, Tmax = 0.978k = 1111
23670 measured reflectionsl = 1414
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.067H-atom parameters constrained
wR(F2) = 0.117 w = 1/[σ2(Fo2) + (0.03P)2 + P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
3749 reflectionsΔρmax = 0.33 e Å3
183 parametersΔρmin = 0.39 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0049 (10)
Crystal data top
C15H16N2O2SV = 1436.0 (8) Å3
Mr = 288.36Z = 4
Monoclinic, P21/cMo Kα radiation
a = 15.926 (4) ŵ = 0.23 mm1
b = 8.345 (4) ÅT = 145 K
c = 10.955 (3) Å0.5 × 0.4 × 0.1 mm
β = 99.50 (4)°
Data collection top
Siemens SMART CCD
diffractometer
3749 independent reflections
Absorption correction: numerical (SHELXTL; sheldrick, 1996)
?
2144 reflections with I > 2σ(I)
Tmin = 0.887, Tmax = 0.978Rint = 0.096
23670 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0670 restraints
wR(F2) = 0.117H-atom parameters constrained
S = 1.04Δρmax = 0.33 e Å3
3749 reflectionsΔρmin = 0.39 e Å3
183 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
xyzUiso*/Ueq
S0.26435 (4)0.56583 (7)0.91530 (6)0.02620 (18)
O10.22598 (11)0.7131 (2)0.94438 (17)0.0361 (5)
O20.30927 (10)0.5584 (2)0.81236 (15)0.0340 (4)
N10.00422 (12)0.4304 (3)0.80364 (18)0.0276 (5)
H010.01080.51720.76700.033*
N20.18667 (11)0.4337 (2)0.88706 (18)0.0234 (5)
C10.07630 (16)0.3431 (3)0.7647 (3)0.0336 (7)
H10.11790.36470.69390.040*
C20.07790 (16)0.2198 (3)0.8455 (3)0.0376 (7)
H20.12100.14050.84210.045*
C30.00345 (16)0.2317 (3)0.9354 (3)0.0324 (6)
H30.01280.16081.00310.039*
C40.04094 (15)0.3630 (3)0.9078 (2)0.0239 (6)
C50.12253 (14)0.4340 (3)0.9714 (2)0.0256 (5)
H5A0.11250.54530.99690.031*
H5B0.14420.37121.04670.031*
C60.20923 (16)0.2726 (3)0.8460 (2)0.0262 (6)
H6A0.15980.22800.78960.031*
H6B0.25670.28330.79850.031*
C70.23433 (16)0.1597 (3)0.9484 (2)0.0276 (6)
C80.25238 (16)0.0702 (3)1.0319 (3)0.0342 (6)
H80.26690.00191.09910.041*
C90.33516 (14)0.5051 (3)1.0480 (2)0.0228 (5)
C100.32019 (15)0.5480 (3)1.1650 (2)0.0261 (6)
H100.27100.60791.17470.031*
C110.37831 (15)0.5018 (3)1.2672 (2)0.0289 (6)
H110.36830.53011.34760.035*
C120.45081 (15)0.4152 (3)1.2549 (2)0.0241 (5)
C130.46317 (15)0.3720 (3)1.1368 (2)0.0279 (6)
H130.51210.31131.12700.034*
C140.40611 (15)0.4151 (3)1.0337 (2)0.0257 (6)
H140.41520.38350.95360.031*
C150.51676 (16)0.3725 (3)1.3652 (2)0.0355 (7)
H15A0.49050.37241.44010.053*
H15B0.56290.45151.37420.053*
H15C0.53980.26581.35320.053*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S0.0230 (3)0.0198 (3)0.0327 (4)0.0028 (3)0.0043 (3)0.0032 (3)
O10.0332 (10)0.0167 (9)0.0521 (12)0.0029 (8)0.0115 (9)0.0024 (8)
O20.0310 (10)0.0394 (11)0.0296 (10)0.0093 (9)0.0008 (8)0.0075 (9)
N10.0205 (10)0.0291 (11)0.0320 (12)0.0044 (10)0.0009 (9)0.0000 (10)
N20.0182 (10)0.0186 (10)0.0316 (12)0.0005 (9)0.0013 (8)0.0039 (9)
C10.0206 (13)0.0401 (17)0.0389 (17)0.0025 (12)0.0015 (12)0.0169 (14)
C20.0288 (15)0.0328 (16)0.0542 (19)0.0124 (12)0.0154 (14)0.0193 (14)
C30.0324 (14)0.0247 (14)0.0419 (17)0.0018 (12)0.0115 (13)0.0046 (12)
C40.0220 (13)0.0203 (12)0.0296 (14)0.0006 (10)0.0047 (11)0.0064 (11)
C50.0210 (12)0.0242 (12)0.0303 (14)0.0009 (11)0.0007 (10)0.0057 (12)
C60.0275 (13)0.0209 (13)0.0299 (14)0.0012 (11)0.0042 (11)0.0051 (11)
C70.0285 (14)0.0206 (14)0.0339 (16)0.0015 (11)0.0055 (12)0.0062 (12)
C80.0372 (15)0.0249 (13)0.0419 (17)0.0036 (13)0.0108 (13)0.0004 (14)
C90.0166 (12)0.0192 (12)0.0313 (14)0.0030 (10)0.0001 (10)0.0001 (11)
C100.0185 (12)0.0247 (13)0.0357 (15)0.0017 (10)0.0063 (11)0.0024 (12)
C110.0278 (14)0.0323 (14)0.0270 (14)0.0069 (12)0.0059 (11)0.0021 (11)
C120.0223 (12)0.0216 (13)0.0271 (14)0.0046 (10)0.0003 (10)0.0026 (11)
C130.0239 (13)0.0266 (13)0.0324 (15)0.0044 (11)0.0020 (11)0.0015 (11)
C140.0258 (13)0.0269 (14)0.0235 (13)0.0000 (11)0.0014 (10)0.0021 (11)
C150.0340 (15)0.0390 (16)0.0309 (16)0.0016 (12)0.0023 (12)0.0050 (13)
Geometric parameters (Å, º) top
S—O11.4313 (18)C6—H6A0.9900
S—O21.4331 (19)C6—H6B0.9900
S—N21.648 (2)C7—C81.179 (3)
S—C91.761 (3)C8—H80.9500
N1—C41.366 (3)C9—C141.387 (3)
N1—C11.367 (3)C9—C101.389 (3)
N1—H010.8800C10—C111.384 (3)
N2—C61.480 (3)C10—H100.9500
N2—C51.486 (3)C11—C121.387 (3)
C1—C21.360 (4)C11—H110.9500
C1—H10.9500C12—C131.389 (3)
C2—C31.414 (4)C12—C151.507 (3)
C2—H20.9500C13—C141.375 (3)
C3—C41.365 (3)C13—H130.9500
C3—H30.9500C14—H140.9500
C4—C51.492 (3)C15—H15A0.9800
C5—H5A0.9900C15—H15B0.9800
C5—H5B0.9900C15—H15C0.9800
C6—C71.469 (4)
O1—S—O2119.94 (12)C7—C6—H6A108.9
O1—S—N2106.34 (11)N2—C6—H6A108.9
O2—S—N2106.27 (11)C7—C6—H6B108.9
O1—S—C9107.58 (11)N2—C6—H6B108.9
O2—S—C9107.61 (11)H6A—C6—H6B107.7
N2—S—C9108.72 (11)C8—C7—C6178.1 (3)
C4—N1—C1109.9 (2)C7—C8—H8180.0
C4—N1—H01125.1C14—C9—C10120.7 (2)
C1—N1—H01125.1C14—C9—S119.02 (19)
C6—N2—C5114.64 (19)C10—C9—S120.24 (18)
C6—N2—S116.89 (15)C11—C10—C9118.7 (2)
C5—N2—S116.98 (15)C11—C10—H10120.6
C2—C1—N1107.8 (2)C9—C10—H10120.6
C2—C1—H1126.1C10—C11—C12121.5 (2)
N1—C1—H1126.1C10—C11—H11119.2
C1—C2—C3107.3 (2)C12—C11—H11119.2
C1—C2—H2126.4C11—C12—C13118.3 (2)
C3—C2—H2126.4C11—C12—C15121.8 (2)
C4—C3—C2107.9 (2)C13—C12—C15119.9 (2)
C4—C3—H3126.1C14—C13—C12121.4 (2)
C2—C3—H3126.1C14—C13—H13119.3
C3—C4—N1107.2 (2)C12—C13—H13119.3
C3—C4—C5131.2 (2)C13—C14—C9119.3 (2)
N1—C4—C5121.6 (2)C13—C14—H14120.4
N2—C5—C4110.13 (19)C9—C14—H14120.4
N2—C5—H5A109.6C12—C15—H15A109.5
C4—C5—H5A109.6C12—C15—H15B109.5
N2—C5—H5B109.6H15A—C15—H15B109.5
C4—C5—H5B109.6C12—C15—H15C109.5
H5A—C5—H5B108.1H15A—C15—H15C109.5
C7—C6—N2113.6 (2)H15B—C15—H15C109.5
O1—S—N2—C6175.96 (16)S—N2—C6—C790.3 (2)
O2—S—N2—C647.10 (19)O1—S—C9—C14151.01 (19)
C9—S—N2—C668.47 (19)O2—S—C9—C1420.5 (2)
O1—S—N2—C542.53 (19)N2—S—C9—C1494.2 (2)
O2—S—N2—C5171.39 (16)O1—S—C9—C1028.5 (2)
C9—S—N2—C573.04 (19)O2—S—C9—C10159.07 (19)
C4—N1—C1—C20.7 (3)N2—S—C9—C1086.2 (2)
N1—C1—C2—C30.9 (3)C14—C9—C10—C111.2 (3)
C1—C2—C3—C40.7 (3)S—C9—C10—C11178.33 (19)
C2—C3—C4—N10.3 (3)C9—C10—C11—C120.4 (4)
C2—C3—C4—C5178.9 (2)C10—C11—C12—C131.5 (4)
C1—N1—C4—C30.3 (3)C10—C11—C12—C15176.5 (2)
C1—N1—C4—C5179.6 (2)C11—C12—C13—C140.9 (4)
C6—N2—C5—C461.3 (3)C15—C12—C13—C14177.1 (2)
S—N2—C5—C4156.31 (17)C12—C13—C14—C90.7 (4)
C3—C4—C5—N2119.1 (3)C10—C9—C14—C131.8 (4)
N1—C4—C5—N261.8 (3)S—C9—C14—C13177.79 (19)
C5—N2—C6—C752.1 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···O1i0.952.453.210 (4)137
C8—H8···O2ii0.952.373.240 (4)152
C5—H5A···Cg(pyrrole)iii0.992.613.395 (4)136
C15—H15C···Cg(phenyl)iv0.982.783.754 (4)173
N1—H01···C2v0.882.443.304 (4)167
Symmetry codes: (i) x, y1/2, z+3/2; (ii) x, y+1/2, z+1/2; (iii) x, y+1, z+2; (iv) x+1, y1/2, z+5/2; (v) x, y+1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC15H16N2O2S
Mr288.36
Crystal system, space groupMonoclinic, P21/c
Temperature (K)145
a, b, c (Å)15.926 (4), 8.345 (4), 10.955 (3)
β (°) 99.50 (4)
V3)1436.0 (8)
Z4
Radiation typeMo Kα
µ (mm1)0.23
Crystal size (mm)0.5 × 0.4 × 0.1
Data collection
DiffractometerSiemens SMART CCD
diffractometer
Absorption correctionNumerical (SHELXTL; Sheldrick, 1996)
Tmin, Tmax0.887, 0.978
No. of measured, independent and
observed [I > 2σ(I)] reflections
23670, 3749, 2144
Rint0.096
(sin θ/λ)max1)0.682
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.067, 0.117, 1.04
No. of reflections3749
No. of parameters183
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.33, 0.39

Computer programs: SMART (Siemens, 1995), SMART, SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL (Sheldrick, 1996), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···O1i0.952.453.210 (4)137
C8—H8···O2ii0.952.373.240 (4)152
C5—H5A···Cg(pyrrole)iii0.992.613.395 (4)136
C15—H15C···Cg(phenyl)iv0.982.783.754 (4)173
N1—H01···C2v0.882.443.304 (4)167
Symmetry codes: (i) x, y1/2, z+3/2; (ii) x, y+1/2, z+1/2; (iii) x, y+1, z+2; (iv) x+1, y1/2, z+5/2; (v) x, y+1/2, z+3/2.
 

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