Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802002520/wn6081sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802002520/wn6081Isup2.hkl |
CCDC reference: 182623
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.
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, H—C(methyl) = 0.98 Å and H—C(alkynyl) = 0.95 Å.
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.
Fig. 1. The structure of (I) with 50% probability displacement ellipsoids. | |
Fig. 2. The crystal packing of (I) viewed down b. |
C15H16N2O2S | F(000) = 608 |
Mr = 288.36 | Dx = 1.334 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 15.926 (4) Å | Cell parameters from 54 reflections |
b = 8.345 (4) Å | θ = 3–23° |
c = 10.955 (3) Å | µ = 0.23 mm−1 |
β = 99.50 (4)° | T = 145 K |
V = 1436.0 (8) Å3 | Block, colorless |
Z = 4 | 0.5 × 0.4 × 0.1 mm |
Siemens SMART CCD diffractometer | 3749 independent reflections |
Radiation source: normal-focus sealed tube | 2144 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.096 |
ω scans | θmax = 29.0°, θmin = 2.6° |
Absorption correction: numerical (SHELXTL; sheldrick, 1996) ? | h = −21→21 |
Tmin = 0.887, Tmax = 0.978 | k = −11→11 |
23670 measured reflections | l = −14→14 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.067 | H-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 reflections | Δρmax = 0.33 e Å−3 |
183 parameters | Δρmin = −0.39 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0049 (10) |
C15H16N2O2S | V = 1436.0 (8) Å3 |
Mr = 288.36 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.926 (4) Å | µ = 0.23 mm−1 |
b = 8.345 (4) Å | T = 145 K |
c = 10.955 (3) Å | 0.5 × 0.4 × 0.1 mm |
β = 99.50 (4)° |
Siemens SMART CCD diffractometer | 3749 independent reflections |
Absorption correction: numerical (SHELXTL; sheldrick, 1996) ? | 2144 reflections with I > 2σ(I) |
Tmin = 0.887, Tmax = 0.978 | Rint = 0.096 |
23670 measured reflections |
R[F2 > 2σ(F2)] = 0.067 | 0 restraints |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.33 e Å−3 |
3749 reflections | Δρmin = −0.39 e Å−3 |
183 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S | 0.26435 (4) | 0.56583 (7) | 0.91530 (6) | 0.02620 (18) | |
O1 | 0.22598 (11) | 0.7131 (2) | 0.94438 (17) | 0.0361 (5) | |
O2 | 0.30927 (10) | 0.5584 (2) | 0.81236 (15) | 0.0340 (4) | |
N1 | −0.00422 (12) | 0.4304 (3) | 0.80364 (18) | 0.0276 (5) | |
H01 | 0.0108 | 0.5172 | 0.7670 | 0.033* | |
N2 | 0.18667 (11) | 0.4337 (2) | 0.88706 (18) | 0.0234 (5) | |
C1 | −0.07630 (16) | 0.3431 (3) | 0.7647 (3) | 0.0336 (7) | |
H1 | −0.1179 | 0.3647 | 0.6939 | 0.040* | |
C2 | −0.07790 (16) | 0.2198 (3) | 0.8455 (3) | 0.0376 (7) | |
H2 | −0.1210 | 0.1405 | 0.8421 | 0.045* | |
C3 | −0.00345 (16) | 0.2317 (3) | 0.9354 (3) | 0.0324 (6) | |
H3 | 0.0128 | 0.1608 | 1.0031 | 0.039* | |
C4 | 0.04094 (15) | 0.3630 (3) | 0.9078 (2) | 0.0239 (6) | |
C5 | 0.12253 (14) | 0.4340 (3) | 0.9714 (2) | 0.0256 (5) | |
H5A | 0.1125 | 0.5453 | 0.9969 | 0.031* | |
H5B | 0.1442 | 0.3712 | 1.0467 | 0.031* | |
C6 | 0.20923 (16) | 0.2726 (3) | 0.8460 (2) | 0.0262 (6) | |
H6A | 0.1598 | 0.2280 | 0.7896 | 0.031* | |
H6B | 0.2567 | 0.2833 | 0.7985 | 0.031* | |
C7 | 0.23433 (16) | 0.1597 (3) | 0.9484 (2) | 0.0276 (6) | |
C8 | 0.25238 (16) | 0.0702 (3) | 1.0319 (3) | 0.0342 (6) | |
H8 | 0.2669 | −0.0019 | 1.0991 | 0.041* | |
C9 | 0.33516 (14) | 0.5051 (3) | 1.0480 (2) | 0.0228 (5) | |
C10 | 0.32019 (15) | 0.5480 (3) | 1.1650 (2) | 0.0261 (6) | |
H10 | 0.2710 | 0.6079 | 1.1747 | 0.031* | |
C11 | 0.37831 (15) | 0.5018 (3) | 1.2672 (2) | 0.0289 (6) | |
H11 | 0.3683 | 0.5301 | 1.3476 | 0.035* | |
C12 | 0.45081 (15) | 0.4152 (3) | 1.2549 (2) | 0.0241 (5) | |
C13 | 0.46317 (15) | 0.3720 (3) | 1.1368 (2) | 0.0279 (6) | |
H13 | 0.5121 | 0.3113 | 1.1270 | 0.034* | |
C14 | 0.40611 (15) | 0.4151 (3) | 1.0337 (2) | 0.0257 (6) | |
H14 | 0.4152 | 0.3835 | 0.9536 | 0.031* | |
C15 | 0.51676 (16) | 0.3725 (3) | 1.3652 (2) | 0.0355 (7) | |
H15A | 0.4905 | 0.3724 | 1.4401 | 0.053* | |
H15B | 0.5629 | 0.4515 | 1.3742 | 0.053* | |
H15C | 0.5398 | 0.2658 | 1.3532 | 0.053* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S | 0.0230 (3) | 0.0198 (3) | 0.0327 (4) | −0.0028 (3) | −0.0043 (3) | 0.0032 (3) |
O1 | 0.0332 (10) | 0.0167 (9) | 0.0521 (12) | 0.0029 (8) | −0.0115 (9) | −0.0024 (8) |
O2 | 0.0310 (10) | 0.0394 (11) | 0.0296 (10) | −0.0093 (9) | −0.0008 (8) | 0.0075 (9) |
N1 | 0.0205 (10) | 0.0291 (11) | 0.0320 (12) | −0.0044 (10) | 0.0009 (9) | 0.0000 (10) |
N2 | 0.0182 (10) | 0.0186 (10) | 0.0316 (12) | −0.0005 (9) | −0.0013 (8) | −0.0039 (9) |
C1 | 0.0206 (13) | 0.0401 (17) | 0.0389 (17) | −0.0025 (12) | 0.0015 (12) | −0.0169 (14) |
C2 | 0.0288 (15) | 0.0328 (16) | 0.0542 (19) | −0.0124 (12) | 0.0154 (14) | −0.0193 (14) |
C3 | 0.0324 (14) | 0.0247 (14) | 0.0419 (17) | −0.0018 (12) | 0.0115 (13) | −0.0046 (12) |
C4 | 0.0220 (13) | 0.0203 (12) | 0.0296 (14) | 0.0006 (10) | 0.0047 (11) | −0.0064 (11) |
C5 | 0.0210 (12) | 0.0242 (12) | 0.0303 (14) | 0.0009 (11) | 0.0007 (10) | −0.0057 (12) |
C6 | 0.0275 (13) | 0.0209 (13) | 0.0299 (14) | −0.0012 (11) | 0.0042 (11) | −0.0051 (11) |
C7 | 0.0285 (14) | 0.0206 (14) | 0.0339 (16) | 0.0015 (11) | 0.0055 (12) | −0.0062 (12) |
C8 | 0.0372 (15) | 0.0249 (13) | 0.0419 (17) | 0.0036 (13) | 0.0108 (13) | 0.0004 (14) |
C9 | 0.0166 (12) | 0.0192 (12) | 0.0313 (14) | −0.0030 (10) | 0.0001 (10) | 0.0001 (11) |
C10 | 0.0185 (12) | 0.0247 (13) | 0.0357 (15) | −0.0017 (10) | 0.0063 (11) | −0.0024 (12) |
C11 | 0.0278 (14) | 0.0323 (14) | 0.0270 (14) | −0.0069 (12) | 0.0059 (11) | −0.0021 (11) |
C12 | 0.0223 (12) | 0.0216 (13) | 0.0271 (14) | −0.0046 (10) | −0.0003 (10) | 0.0026 (11) |
C13 | 0.0239 (13) | 0.0266 (13) | 0.0324 (15) | 0.0044 (11) | 0.0020 (11) | −0.0015 (11) |
C14 | 0.0258 (13) | 0.0269 (14) | 0.0235 (13) | 0.0000 (11) | 0.0014 (10) | −0.0021 (11) |
C15 | 0.0340 (15) | 0.0390 (16) | 0.0309 (16) | −0.0016 (12) | −0.0023 (12) | 0.0050 (13) |
S—O1 | 1.4313 (18) | C6—H6A | 0.9900 |
S—O2 | 1.4331 (19) | C6—H6B | 0.9900 |
S—N2 | 1.648 (2) | C7—C8 | 1.179 (3) |
S—C9 | 1.761 (3) | C8—H8 | 0.9500 |
N1—C4 | 1.366 (3) | C9—C14 | 1.387 (3) |
N1—C1 | 1.367 (3) | C9—C10 | 1.389 (3) |
N1—H01 | 0.8800 | C10—C11 | 1.384 (3) |
N2—C6 | 1.480 (3) | C10—H10 | 0.9500 |
N2—C5 | 1.486 (3) | C11—C12 | 1.387 (3) |
C1—C2 | 1.360 (4) | C11—H11 | 0.9500 |
C1—H1 | 0.9500 | C12—C13 | 1.389 (3) |
C2—C3 | 1.414 (4) | C12—C15 | 1.507 (3) |
C2—H2 | 0.9500 | C13—C14 | 1.375 (3) |
C3—C4 | 1.365 (3) | C13—H13 | 0.9500 |
C3—H3 | 0.9500 | C14—H14 | 0.9500 |
C4—C5 | 1.492 (3) | C15—H15A | 0.9800 |
C5—H5A | 0.9900 | C15—H15B | 0.9800 |
C5—H5B | 0.9900 | C15—H15C | 0.9800 |
C6—C7 | 1.469 (4) | ||
O1—S—O2 | 119.94 (12) | C7—C6—H6A | 108.9 |
O1—S—N2 | 106.34 (11) | N2—C6—H6A | 108.9 |
O2—S—N2 | 106.27 (11) | C7—C6—H6B | 108.9 |
O1—S—C9 | 107.58 (11) | N2—C6—H6B | 108.9 |
O2—S—C9 | 107.61 (11) | H6A—C6—H6B | 107.7 |
N2—S—C9 | 108.72 (11) | C8—C7—C6 | 178.1 (3) |
C4—N1—C1 | 109.9 (2) | C7—C8—H8 | 180.0 |
C4—N1—H01 | 125.1 | C14—C9—C10 | 120.7 (2) |
C1—N1—H01 | 125.1 | C14—C9—S | 119.02 (19) |
C6—N2—C5 | 114.64 (19) | C10—C9—S | 120.24 (18) |
C6—N2—S | 116.89 (15) | C11—C10—C9 | 118.7 (2) |
C5—N2—S | 116.98 (15) | C11—C10—H10 | 120.6 |
C2—C1—N1 | 107.8 (2) | C9—C10—H10 | 120.6 |
C2—C1—H1 | 126.1 | C10—C11—C12 | 121.5 (2) |
N1—C1—H1 | 126.1 | C10—C11—H11 | 119.2 |
C1—C2—C3 | 107.3 (2) | C12—C11—H11 | 119.2 |
C1—C2—H2 | 126.4 | C11—C12—C13 | 118.3 (2) |
C3—C2—H2 | 126.4 | C11—C12—C15 | 121.8 (2) |
C4—C3—C2 | 107.9 (2) | C13—C12—C15 | 119.9 (2) |
C4—C3—H3 | 126.1 | C14—C13—C12 | 121.4 (2) |
C2—C3—H3 | 126.1 | C14—C13—H13 | 119.3 |
C3—C4—N1 | 107.2 (2) | C12—C13—H13 | 119.3 |
C3—C4—C5 | 131.2 (2) | C13—C14—C9 | 119.3 (2) |
N1—C4—C5 | 121.6 (2) | C13—C14—H14 | 120.4 |
N2—C5—C4 | 110.13 (19) | C9—C14—H14 | 120.4 |
N2—C5—H5A | 109.6 | C12—C15—H15A | 109.5 |
C4—C5—H5A | 109.6 | C12—C15—H15B | 109.5 |
N2—C5—H5B | 109.6 | H15A—C15—H15B | 109.5 |
C4—C5—H5B | 109.6 | C12—C15—H15C | 109.5 |
H5A—C5—H5B | 108.1 | H15A—C15—H15C | 109.5 |
C7—C6—N2 | 113.6 (2) | H15B—C15—H15C | 109.5 |
O1—S—N2—C6 | 175.96 (16) | S—N2—C6—C7 | 90.3 (2) |
O2—S—N2—C6 | 47.10 (19) | O1—S—C9—C14 | −151.01 (19) |
C9—S—N2—C6 | −68.47 (19) | O2—S—C9—C14 | −20.5 (2) |
O1—S—N2—C5 | −42.53 (19) | N2—S—C9—C14 | 94.2 (2) |
O2—S—N2—C5 | −171.39 (16) | O1—S—C9—C10 | 28.5 (2) |
C9—S—N2—C5 | 73.04 (19) | O2—S—C9—C10 | 159.07 (19) |
C4—N1—C1—C2 | 0.7 (3) | N2—S—C9—C10 | −86.2 (2) |
N1—C1—C2—C3 | −0.9 (3) | C14—C9—C10—C11 | 1.2 (3) |
C1—C2—C3—C4 | 0.7 (3) | S—C9—C10—C11 | −178.33 (19) |
C2—C3—C4—N1 | −0.3 (3) | C9—C10—C11—C12 | 0.4 (4) |
C2—C3—C4—C5 | 178.9 (2) | C10—C11—C12—C13 | −1.5 (4) |
C1—N1—C4—C3 | −0.3 (3) | C10—C11—C12—C15 | 176.5 (2) |
C1—N1—C4—C5 | −179.6 (2) | C11—C12—C13—C14 | 0.9 (4) |
C6—N2—C5—C4 | −61.3 (3) | C15—C12—C13—C14 | −177.1 (2) |
S—N2—C5—C4 | 156.31 (17) | C12—C13—C14—C9 | 0.7 (4) |
C3—C4—C5—N2 | 119.1 (3) | C10—C9—C14—C13 | −1.8 (4) |
N1—C4—C5—N2 | −61.8 (3) | S—C9—C14—C13 | 177.79 (19) |
C5—N2—C6—C7 | −52.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O1i | 0.95 | 2.45 | 3.210 (4) | 137 |
C8—H8···O2ii | 0.95 | 2.37 | 3.240 (4) | 152 |
C5—H5A···Cg(pyrrole)iii | 0.99 | 2.61 | 3.395 (4) | 136 |
C15—H15C···Cg(phenyl)iv | 0.98 | 2.78 | 3.754 (4) | 173 |
N1—H01···C2v | 0.88 | 2.44 | 3.304 (4) | 167 |
Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) x, −y+1/2, z+1/2; (iii) −x, −y+1, −z+2; (iv) −x+1, y−1/2, −z+5/2; (v) −x, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C15H16N2O2S |
Mr | 288.36 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 145 |
a, b, c (Å) | 15.926 (4), 8.345 (4), 10.955 (3) |
β (°) | 99.50 (4) |
V (Å3) | 1436.0 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.23 |
Crystal size (mm) | 0.5 × 0.4 × 0.1 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Numerical (SHELXTL; Sheldrick, 1996) |
Tmin, Tmax | 0.887, 0.978 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23670, 3749, 2144 |
Rint | 0.096 |
(sin θ/λ)max (Å−1) | 0.682 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.067, 0.117, 1.04 |
No. of reflections | 3749 |
No. of parameters | 183 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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.
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O1i | 0.95 | 2.45 | 3.210 (4) | 137 |
C8—H8···O2ii | 0.95 | 2.37 | 3.240 (4) | 152 |
C5—H5A···Cg(pyrrole)iii | 0.99 | 2.61 | 3.395 (4) | 136 |
C15—H15C···Cg(phenyl)iv | 0.98 | 2.78 | 3.754 (4) | 173 |
N1—H01···C2v | 0.88 | 2.44 | 3.304 (4) | 167 |
Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) x, −y+1/2, z+1/2; (iii) −x, −y+1, −z+2; (iv) −x+1, y−1/2, −z+5/2; (v) −x, y+1/2, −z+3/2. |
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.