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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o130.
Published online 2007 December 6. doi:  10.1107/S1600536807062964
PMCID: PMC2915200

Bis(1-tosyl-2-pyrrol­yl)ethyne

Abstract

The title mol­ecule, C24H20N2O4S2, has crystallographic inversion symmetry with a triple-bond distance of 1.206 (2) Å. The alkyne is not quite linear, with a C—C C angle of 175.78 (16)°. The planar pyrrole rings are parallel but offset from coplanarity by 0.318 (1) Å. The conformation of the sulfonyl group with respect to the pyrrole ring is such that an O atom is nearly eclipsed with this ring, having an O—S—N—C torsion angle of 3.48 (11)°. C—H(...)O inter­actions [C(...)O 3.278 (2) Å, 136° about H] between pyrrole H and sulfonyl O atoms lead to the formation of ladder-like chains.

Related literature

For related structures, see Abell et al. (1998 [triangle]); Knight et al. (2003 [triangle]); Tanui et al. (2008 [triangle]). For related literature, see: Vogel (1996 [triangle]); Chinchilla & Najera (2007 [triangle]); Desiraju & Steiner (1999 [triangle]).

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Object name is e-64-0o130-scheme1.jpg

Experimental

Crystal data

  • C24H20N2O4S2
  • M r = 464.54
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o130-efi1.jpg
  • a = 8.5127 (15) Å
  • b = 16.822 (2) Å
  • c = 7.5311 (11) Å
  • β = 101.049 (7)°
  • V = 1058.5 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.29 mm−1
  • T = 90 K
  • 0.35 × 0.30 × 0.12 mm

Data collection

  • Nonius KappaCCD diffractometer (with Oxford Cryostream)
  • Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997 [triangle]) T min = 0.896, T max = 0.966
  • 16546 measured reflections
  • 3565 independent reflections
  • 2995 reflections with I > 2σ(I)
  • R int = 0.019

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.100
  • S = 1.05
  • 3565 reflections
  • 147 parameters
  • H-atom parameters constrained
  • Δρmax = 0.39 e Å−3
  • Δρmin = −0.54 e Å−3

Data collection: COLLECT (Nonius, 2000 [triangle]); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997 [triangle]); data reduction: HKL DENZO (Otwinowski & Minor, 1997 [triangle]) and HKL SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807062964/tk2223sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062964/tk2223Isup2.hkl

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

Acknowledgments

The purchase of the diffractometer was made possible by Grant No. LEQSF(1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents.

supplementary crystallographic information

Comment

Bis(1-tosyl-pyrrol-2-yl)ethyne (I) is an important intermediate in the synthesis of porphyrin analogues containing a two-carbon interpyrrolic bridge such as in corrphycene (Vogel, 1996). Compound (I) was prepared by an improved Sonogashira coupling reaction (Chinchilla & Najera, 2007) between 2-bromo-1-tosyl-pyrrole and ethyne-trimethylsilane in the presence of Pd(0) and Cu(I) catalysts at room temperature, see Experimental.

The molecule lies about an inversion center. The pyrrole rings are experimentally planar, but offset 0.318 (1) Å from co-planarity, because of the deviation from linearity of the C—C[equivalent]C—C group. Pyrrole-H atoms form intermolecular C—H···O interactions (Desiraju & Steiner, 1999) with sulfonate-O, C···O 3.278 (2) Å and angle of 136° about H. Thes einteractions lead to the formation of ladder-like chains along the [001] direction, Fig. 2.

The structures of related tosylpyrroles, i.e. 2-bromo-N-(p-toluenesulfonyl)pyrrole (Abell et al., 1998) and 2-chloromethyl-1-(4-methylphenylsulfonyl)pyrrole (Knight et al., 2003) have been reported. A similar compound containing the bis(2-pyrrolyl)ethyne core (Tanui et al., 2008) lies on a twofold axis rather than an inversion center, and has its pyrrole groups twisted by 40.49 (4)° from co-planarity.

Experimental

To a 50 ml round bottom flask was added 2-bromo-1-tosyl-pyrrole (0.3 g, 1 mmol) followed by Pd(PPh)2Cl2(0.042 g, 0.06 mmol) and CuI (0.038 g 0.2 mmol). The flask was sealed and placed in a dry ice bath under N2. Trimethylsilanylethyne (0.072 ml, 0.5 mmol), DBU (0.9 ml, 6 mmol) and water (0.0072 ml, 40 molar equiv.) were dissolved in benzene (5 ml) and added to the reaction flask. After the mixture froze in a dry ice bath, the flask was evacuated and N2 gas added. The resulting reaction mixture was allowed to warm slowly to room temperature and was stirred until complete disappearance of the starting material, by TLC. The reaction mixture was worked up by adding ethyl acetate (100 ml), and washing the organic layer three times with saline. The organic phase was dried over anhydrous sodium bicarbonate and concentrated under reduced pressure. The crude mixture was purified by flash column chromatography using hexane/ethyl acetate (5:1) for elution. The bispyrrole-ethyne (I) was obtained in 8.4% yield (0.0194 g) and recrystallized from dichloromethane to afford colorless crystals. 1H NMR (250 MHz, CDCl3, 293 K, δ): 7.9 (4H, B, CH), 7.4 (4H, B, CH), 7.3 (2H, B, CH), 6.7 (2H, B, CH), 6.3 (2H, B, CH), 2.4 (6H, S, CH3). MS (EI) m/z: 465.0939 (M+). M.P.: 459 K.

Refinement

H atoms were placed in idealized positions with C—H distances 0.95–0.98 Å and thereafter treated as riding. Uiso for H was assigned as 1.2xUeq of the attached C atoms (1.5 for methyl). A torsional parameter was refined for the methyl group.

Figures

Fig. 1.
Molecular structure of (I) showing displacement ellipsoids at the 50% level and H atoms having arbitrary radius. Unlabelled atoms are related by symmetry operation: 1 - x, 1 - y, 1 - z.
Fig. 2.
View approximately down the b axis of the supramolecular chain in (I), showing C—H···O interactions as dashed lines.

Crystal data

C24H20N2O4S2F000 = 484
Mr = 464.54Dx = 1.458 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3246 reflections
a = 8.5127 (15) Åθ = 2.5–32.5º
b = 16.822 (2) ŵ = 0.29 mm1
c = 7.5311 (11) ÅT = 90 K
β = 101.049 (7)ºFragment, colorless
V = 1058.5 (3) Å30.35 × 0.30 × 0.12 mm
Z = 2

Data collection

Nonius KappaCCD (with Oxford Cryostream) diffractometer3565 independent reflections
Radiation source: fine-focus sealed tube2995 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.019
T = 90 Kθmax = 32.6º
ω scans with κ offsetsθmin = 2.7º
Absorption correction: multi-scan(HKL SCALEPACK; Otwinowski & Minor 1997)h = −12→12
Tmin = 0.896, Tmax = 0.966k = −20→24
16546 measured reflectionsl = −11→11

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.037  w = 1/[σ2(Fo2) + (0.0457P)2 + 0.5421P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.100(Δ/σ)max < 0.001
S = 1.05Δρmax = 0.39 e Å3
3565 reflectionsΔρmin = −0.54 e Å3
147 parametersExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0087 (19)
Secondary atom site location: difference Fourier map

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
S10.17966 (3)0.588570 (17)0.18361 (4)0.01389 (9)
O10.03490 (11)0.62987 (6)0.10845 (12)0.0205 (2)
O20.21216 (11)0.51113 (5)0.12117 (12)0.01826 (19)
N10.17450 (12)0.58026 (6)0.40533 (13)0.01363 (19)
C10.04720 (14)0.60559 (7)0.48222 (16)0.0155 (2)
H1−0.04380.63420.42220.019*
C20.07578 (14)0.58208 (7)0.65906 (16)0.0159 (2)
H20.00830.59150.74370.019*
C30.22451 (15)0.54103 (7)0.69389 (15)0.0154 (2)
H30.27360.51810.80610.018*
C40.28522 (14)0.54024 (7)0.53683 (15)0.0135 (2)
C50.43438 (14)0.51145 (7)0.50710 (15)0.0143 (2)
C60.34514 (14)0.64976 (7)0.17831 (15)0.0141 (2)
C70.33400 (15)0.73131 (7)0.20914 (16)0.0169 (2)
H70.23720.75410.23060.020*
C80.46788 (16)0.77829 (7)0.20758 (17)0.0187 (2)
H80.46220.83380.22860.022*
C90.61100 (15)0.74548 (8)0.17564 (16)0.0183 (2)
C100.61811 (15)0.66412 (8)0.14272 (16)0.0172 (2)
H100.71430.64140.11930.021*
C110.48522 (14)0.61580 (7)0.14388 (15)0.0151 (2)
H110.49030.56040.12140.018*
C120.75453 (18)0.79796 (9)0.1772 (2)0.0262 (3)
H12A0.83860.76760.13510.039*
H12B0.79460.81700.30050.039*
H12C0.72380.84350.09680.039*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.01179 (14)0.01874 (15)0.01119 (13)−0.00136 (10)0.00237 (9)0.00013 (9)
O10.0125 (4)0.0318 (5)0.0161 (4)0.0012 (4)0.0001 (3)0.0038 (4)
O20.0202 (4)0.0203 (4)0.0152 (4)−0.0047 (3)0.0056 (3)−0.0036 (3)
N10.0112 (4)0.0182 (5)0.0119 (4)0.0008 (3)0.0032 (3)0.0007 (3)
C10.0121 (5)0.0191 (5)0.0164 (5)0.0016 (4)0.0051 (4)0.0000 (4)
C20.0140 (5)0.0188 (5)0.0160 (5)0.0004 (4)0.0060 (4)−0.0012 (4)
C30.0150 (5)0.0186 (5)0.0136 (5)0.0005 (4)0.0051 (4)0.0003 (4)
C40.0123 (5)0.0160 (5)0.0122 (5)0.0006 (4)0.0028 (4)0.0000 (4)
C50.0141 (5)0.0173 (5)0.0118 (4)0.0001 (4)0.0032 (4)0.0012 (4)
C60.0133 (5)0.0174 (5)0.0117 (5)−0.0011 (4)0.0028 (4)0.0017 (4)
C70.0178 (5)0.0179 (5)0.0151 (5)0.0020 (4)0.0029 (4)0.0012 (4)
C80.0239 (6)0.0159 (5)0.0159 (5)−0.0012 (4)0.0030 (4)0.0015 (4)
C90.0185 (6)0.0211 (6)0.0146 (5)−0.0052 (4)0.0017 (4)0.0034 (4)
C100.0138 (5)0.0214 (6)0.0166 (5)−0.0004 (4)0.0038 (4)0.0037 (4)
C110.0154 (5)0.0161 (5)0.0141 (5)0.0003 (4)0.0039 (4)0.0017 (4)
C120.0254 (7)0.0283 (7)0.0256 (6)−0.0114 (5)0.0062 (5)0.0019 (5)

Geometric parameters (Å, °)

S1—O21.4298 (10)C6—C111.3907 (17)
S1—O11.4333 (10)C6—C71.3977 (17)
S1—N11.6845 (10)C7—C81.3888 (18)
S1—C61.7513 (12)C7—H70.9500
N1—C11.3900 (15)C8—C91.3997 (19)
N1—C41.4016 (15)C8—H80.9500
C1—C21.3656 (17)C9—C101.3945 (18)
C1—H10.9500C9—C121.5056 (18)
C2—C31.4218 (17)C10—C111.3944 (17)
C2—H20.9500C10—H100.9500
C3—C41.3786 (16)C11—H110.9500
C3—H30.9500C12—H12A0.9800
C4—C51.4164 (16)C12—H12B0.9800
C5—C5i1.206 (2)C12—H12C0.9800
O2—S1—O1121.17 (6)C11—C6—S1119.01 (9)
O2—S1—N1107.09 (5)C7—C6—S1119.51 (9)
O1—S1—N1104.35 (5)C8—C7—C6118.37 (11)
O2—S1—C6108.71 (6)C8—C7—H7120.8
O1—S1—C6109.91 (6)C6—C7—H7120.8
N1—S1—C6104.20 (5)C7—C8—C9121.32 (12)
C1—N1—C4108.98 (9)C7—C8—H8119.3
C1—N1—S1123.92 (8)C9—C8—H8119.3
C4—N1—S1126.76 (8)C10—C9—C8119.11 (11)
C2—C1—N1108.07 (10)C10—C9—C12120.93 (12)
C2—C1—H1126.0C8—C9—C12119.96 (12)
N1—C1—H1126.0C11—C10—C9120.54 (12)
C1—C2—C3107.85 (10)C11—C10—H10119.7
C1—C2—H2126.1C9—C10—H10119.7
C3—C2—H2126.1C6—C11—C10119.17 (11)
C4—C3—C2108.26 (10)C6—C11—H11120.4
C4—C3—H3125.9C10—C11—H11120.4
C2—C3—H3125.9C9—C12—H12A109.5
C3—C4—N1106.85 (10)C9—C12—H12B109.5
C3—C4—C5129.33 (11)H12A—C12—H12B109.5
N1—C4—C5123.67 (10)C9—C12—H12C109.5
C5i—C5—C4175.78 (16)H12A—C12—H12C109.5
C11—C6—C7121.47 (11)H12B—C12—H12C109.5
O2—S1—N1—C1−126.14 (10)O2—S1—C6—C11−9.04 (11)
O1—S1—N1—C13.48 (11)O1—S1—C6—C11−143.78 (9)
C6—S1—N1—C1118.78 (10)N1—S1—C6—C11104.90 (10)
O2—S1—N1—C446.48 (11)O2—S1—C6—C7171.15 (9)
O1—S1—N1—C4176.09 (10)O1—S1—C6—C736.41 (11)
C6—S1—N1—C4−68.61 (11)N1—S1—C6—C7−74.92 (10)
C4—N1—C1—C2−0.14 (13)C11—C6—C7—C8−1.01 (17)
S1—N1—C1—C2173.61 (9)S1—C6—C7—C8178.80 (9)
N1—C1—C2—C3−0.01 (14)C6—C7—C8—C90.15 (18)
C1—C2—C3—C40.16 (14)C7—C8—C9—C100.76 (18)
C2—C3—C4—N1−0.24 (13)C7—C8—C9—C12−179.25 (12)
C2—C3—C4—C5175.18 (12)C8—C9—C10—C11−0.83 (18)
C1—N1—C4—C30.23 (13)C12—C9—C10—C11179.17 (11)
S1—N1—C4—C3−173.29 (9)C7—C6—C11—C100.93 (17)
C1—N1—C4—C5−175.51 (11)S1—C6—C11—C10−178.88 (9)
S1—N1—C4—C510.97 (17)C9—C10—C11—C60.01 (17)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C3—H3···O2ii0.952.533.278 (2)136

Symmetry codes: (ii) x, y, z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2223).

References

  • Abell, A. D., Nabbs, B. K. & Battersby, A. R. (1998). J. Org. Chem.63, 8163–8169.
  • Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst.32, 115–119.
  • Chinchilla, R. & Najera, C. (2007). Chem. Rev.107, 874–922. [PubMed]
  • Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond in Structural Chemistry and Biology New York: Oxford University Press Inc.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Knight, L. W., Padgett, C. W., Huffman, J. W. & Pennington, W. T. (2003). Acta Cryst. E59, o762–o764.
  • Nonius (2000). COLLECT Nonius BV, Delft, The Netherlands.
  • Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
  • Sheldrick, G. M. (1997). SHELXL97 University of Göttingen, Germany. [PubMed]
  • Tanui, H. K., Fronczek, F. R. & Vicente, M. G. H. (2008). Acta Cryst. E64, o75. [PMC free article] [PubMed]
  • Vogel, E. (1996). Pure Appl. Chem.68, 1355–1360.

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