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The title compound, C11H10BrNO2S, crystallizes in a columnar structure consisting of interdigitated C—H...O doubly bonded chains. The columns pack in a herring-bone fashion and are linked through additional weak hydrogen bonding. The structure is very nearly isomorphous to one in which the bromo substituent on the pyrrole ring is replaced by a chloro­methyl group, in spite of the difference in size, shape and interactions involving these two groups.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803009097/om6140sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803009097/om6140Isup2.hkl
Contains datablock I

CCDC reference: 214811

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.046
  • wR factor = 0.089
  • Data-to-parameter ratio = 16.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

Since the discovery of cannabimimetic properties in select aminoalkylindoles by the Sterling–Winthrop group (Bell et al., 1991), researchers around the world have assumed the task of finding a pharmacophore for the cannabinoid receptor that encompasses the four main classes of cannabinoid ligands, viz. aminoalkylindoles, endogenous cannabinoids, non-traditional cannabinoids and traditional cannabinoids (Huffman & Lainton, 1996). It has been proposed that aromatic stacking may play an important role in the affinity of highly aromatic ligands, such as the aminoalkylindoles (Reggio et al., 1998). In an attempt to test the significance of the benzenoid moiety of the indole, a series of N-alkyl-3-(1-naphthoyl)pyrroles was synthesized and shown to possess reduced affinity for the cannabinoid receptor compared with similarly substituted indoles (Lainton et al., 1995). To follow-up on this development, a series of N-alkyl-2-phenyl-3-(1-naphthoyl)pyrroles was synthesized and found to exhibit significantly increased affinity over the previous pyrrole series (Huffman & Isherwood, 2003). In order to further study the effects promoted by the 2-aryl functionality, an easily derivatizable synthon of 2-arylpyrrole is required. One such route proceeds through N-(p-toluenesulfonyl)-2-bromopyrrole, (I), the subject of this paper.

The bonding parameters of (I) (Fig. 1) are very similar to those of related tosylpyrroles (Abell et al., 1998), pyrrolidines (Sambyal et al., 1995; Gupta et al., 1995), and other related sulfonylamides (Ohwada et al., 1998). As opposed to the majority of the latter, the bonding about the N atom is nearly planar with a bond angle sum of 358.4°, while the average value for 349 sulfonylamides was found to be 352.4° (Ohwada et al., 1998). The pyrrole ring in (I) has a slight envelope conformation, as the N atom lies 0.041 (6) Å out of the plane of the four ring C atoms which are planar to 0.0005 Å. The molecular conformation can be described by the dihedral angles between three-atom planes consisting of the pyrrole bridgehead (C1/N1/C4), the sulfur linkage between the two rings (N1/S1/C5), and aryl bridgehead (C6/C5/C10. Sulfonylamides often have a pseudo-staggered conformation with the sulfonyl O atoms equally disposed to one side of a given ring plane and the S-bidgehead vector of the other ring to the opposite side. In this conformation, both ring planes are orthogonal to the sulfur linkage plane (Abell et al., 1998). This is indeed the case for the pyrrole plane, but the aryl ring is rotated to a value of 83.5(?)°. The sulfonyl group is in a pseudo-staggered orientation with respect to the aryl group, with a dihderal angle of 89.3(?)° between the three-atom planes C6/C5/C10 and C5/S1/N1, but deviates with respect to the pyrrole ring as the dihedral angle between the C5/S1/N1 and C1/N1/C4 planes is 83.5(?)°. This deviation is most likely due to steric interaction between the Br atom on the pyrrole ring and a neighboring sulfonyl O atom.

The crystal packing is dominated by double C—H···O hydrogen bonds between the C—H bonds at the 3- and 4-positions of the pyrrole ring with the sulfonyl O atoms of a molecule related by translation along the a axis. The resulting ribbons mesh with those related by inversion symmetry (1/2, 1/2, 1/2) to form a column with interdigitated aryl groups (Fig. 2). The columns pack in a herring-bone fashion, with C—H···Br and additional C—H···O interactions linking columns related by glide symmetry (Fig. 3). Although not discussed, the packing of N-tosyl-2-chloromethylpyrrole (Abell et al., 1998) is almost identical that observed for (I), and in fact the two structures are nearly isomorphous.

Experimental top

The title compound, (I), was synthesized through a one-pot procedure that first brominates the pyrrole, and then protects it before the compound is removed from solution. A detailed experimental procedure for this synthesis will be published elsewhere. The compound is then purified through recrystallization from 2-propanol, and data quality crsytals were grown from methylene chloride.

Refinement top

All H atoms were refined with isotropic displacement parameters, except for those of the methyl group, which were found to be disordered over two rotationally related sites. Two sets of half-occupancy H atoms were constrained to ride on the methyl C atom at positions optimized from those obtained from a difference Fourier map.

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation/Rigaku, 2001); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 2000); program(s) used to refine structure: SHELXTL-Plus; molecular graphics: SHELXTL-Plus; software used to prepare material for publication: SHELXTL-Plus.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I). Displacement ellipsoids are shown at the 50% probability level and H atoms are of arbitrary radii. Only one set of the disordered methyl H atoms is shown.
[Figure 2] Fig. 2. C—H···O hydrogen-bonded chains of (I), interdigitated to form columns.
[Figure 3] Fig. 3. Herring-bone packing of columns of (I), viewed down the a axis.
2-Bromo-N(p-Toluenesulfonyl)pyrrole top
Crystal data top
C11H10BrNO2SDx = 1.668 Mg m3
Mr = 300.17Melting point: 105 K
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 7.6482 (13) ÅCell parameters from 7533 reflections
b = 16.307 (2) Åθ = 2.8–26.4°
c = 10.2114 (17) ŵ = 3.60 mm1
β = 110.233 (3)°T = 293 K
V = 1195.0 (3) Å3Plate, colorless
Z = 40.35 × 0.20 × 0.10 mm
F(000) = 600
Data collection top
Mercury AFC-8S
diffractometer
2437 independent reflections
Radiation source: fine-focus sealed tube2006 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
Detector resolution: 14.6199 pixels mm-1θmax = 26.4°, θmin = 2.9°
ω scansh = 99
Absorption correction: multi-scan
(REQAB; Jacobson, 1998)
k = 2019
Tmin = 0.454, Tmax = 0.698l = 1112
11515 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: difference Fourier map
wR(F2) = 0.089H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.001P)2 + 3.06P]
where P = (Fo2 + 2Fc2)/3
2437 reflections(Δ/σ)max = 0.001
145 parametersΔρmax = 0.48 e Å3
0 restraintsΔρmin = 0.75 e Å3
Crystal data top
C11H10BrNO2SV = 1195.0 (3) Å3
Mr = 300.17Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.6482 (13) ŵ = 3.60 mm1
b = 16.307 (2) ÅT = 293 K
c = 10.2114 (17) Å0.35 × 0.20 × 0.10 mm
β = 110.233 (3)°
Data collection top
Mercury AFC-8S
diffractometer
2437 independent reflections
Absorption correction: multi-scan
(REQAB; Jacobson, 1998)
2006 reflections with I > 2σ(I)
Tmin = 0.454, Tmax = 0.698Rint = 0.029
11515 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.089H-atom parameters constrained
S = 1.00Δρmax = 0.48 e Å3
2437 reflectionsΔρmin = 0.75 e Å3
145 parameters
Special details top

Experimental. REQABA Empirical Absorption Correction, Version 1.1, R·A·Jacobson, Molecular Structure Corp. 1996–1998

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Br10.69840 (8)0.57111 (3)1.11357 (5)0.07736 (19)
S10.84978 (12)0.68733 (6)0.87941 (10)0.0468 (2)
O10.8764 (4)0.76468 (16)0.8244 (3)0.0634 (8)
O20.9796 (4)0.65815 (19)1.0077 (3)0.0626 (8)
N10.6435 (4)0.69533 (18)0.9018 (3)0.0436 (7)
C10.5666 (5)0.6468 (2)0.9798 (4)0.0493 (9)
C20.3860 (6)0.6662 (3)0.9455 (5)0.0652 (11)
H2A0.30280.64390.98400.078*
C30.3449 (6)0.7272 (3)0.8397 (5)0.0649 (12)
H3A0.22890.75150.79740.078*
C40.4953 (5)0.7441 (2)0.8109 (4)0.0504 (9)
H4A0.50410.78090.74380.060*
C50.8154 (5)0.6122 (2)0.7508 (4)0.0417 (8)
C60.7711 (7)0.6361 (3)0.6136 (4)0.0629 (11)
H6A0.76060.69140.58930.075*
C70.7427 (7)0.5760 (3)0.5131 (4)0.0703 (13)
H7A0.71410.59170.42050.084*
C80.7551 (5)0.4937 (2)0.5451 (4)0.0537 (9)
C90.7953 (6)0.4722 (2)0.6818 (4)0.0629 (11)
H9A0.80170.41690.70560.076*
C100.8265 (6)0.5304 (2)0.7854 (4)0.0592 (11)
H10A0.85480.51450.87790.071*
C110.7252 (7)0.4292 (3)0.4337 (5)0.0748 (13)
H11A0.73990.37570.47540.112*0.50
H11B0.81480.43640.38800.112*0.50
H11C0.60170.43440.36650.112*0.50
H11D0.83460.39560.45480.112*0.50
H11E0.70120.45530.34490.112*0.50
H11F0.62060.39560.43010.112*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0913 (4)0.0759 (3)0.0607 (3)0.0016 (3)0.0210 (2)0.0169 (2)
S10.0400 (4)0.0507 (5)0.0512 (5)0.0067 (4)0.0174 (4)0.0122 (4)
O10.0665 (18)0.0489 (16)0.087 (2)0.0189 (13)0.0415 (16)0.0142 (14)
O20.0416 (14)0.088 (2)0.0508 (15)0.0005 (14)0.0069 (12)0.0160 (15)
N10.0417 (15)0.0439 (16)0.0476 (16)0.0001 (13)0.0187 (13)0.0031 (13)
C10.059 (2)0.047 (2)0.0453 (19)0.0014 (17)0.0223 (18)0.0020 (16)
C20.058 (3)0.063 (3)0.088 (3)0.002 (2)0.043 (2)0.005 (2)
C30.045 (2)0.055 (2)0.089 (3)0.0164 (19)0.016 (2)0.006 (2)
C40.062 (2)0.0383 (19)0.052 (2)0.0001 (17)0.0208 (19)0.0022 (16)
C50.0410 (18)0.0431 (19)0.0416 (18)0.0019 (15)0.0150 (15)0.0042 (15)
C60.098 (3)0.046 (2)0.051 (2)0.005 (2)0.034 (2)0.0036 (18)
C70.113 (4)0.060 (3)0.042 (2)0.004 (3)0.032 (2)0.0010 (19)
C80.056 (2)0.052 (2)0.052 (2)0.0012 (18)0.0173 (18)0.0085 (18)
C90.087 (3)0.040 (2)0.055 (2)0.014 (2)0.015 (2)0.0003 (18)
C100.076 (3)0.052 (2)0.042 (2)0.014 (2)0.0107 (19)0.0035 (17)
C110.089 (3)0.070 (3)0.065 (3)0.006 (3)0.026 (3)0.025 (2)
Geometric parameters (Å, º) top
Br1—C11.858 (4)C6—C71.381 (6)
S1—O11.424 (3)C6—H6A0.9300
S1—O21.425 (3)C7—C81.377 (6)
S1—N11.676 (3)C7—H7A0.9300
S1—C51.748 (3)C8—C91.367 (6)
N1—C11.389 (4)C8—C111.509 (5)
N1—C41.432 (5)C9—C101.379 (5)
C1—C21.340 (5)C9—H9A0.9300
C2—C31.421 (6)C10—H10A0.9300
C2—H2A0.9300C11—H11A0.9600
C3—C41.311 (6)C11—H11B0.9599
C3—H3A0.9300C11—H11C0.9600
C4—H4A0.9300C11—H11D0.9600
C5—C101.375 (5)C11—H11E0.9600
C5—C61.379 (5)C11—H11F0.9601
O1—S1—O2120.64 (18)C9—C8—C7117.7 (4)
O1—S1—N1104.75 (16)C9—C8—C11120.9 (4)
O2—S1—N1106.86 (16)C7—C8—C11121.4 (4)
O1—S1—C5109.21 (17)C8—C9—C10121.6 (4)
O2—S1—C5109.45 (17)C8—C9—H9A119.2
N1—S1—C5104.66 (16)C10—C9—H9A119.2
C1—N1—C4106.9 (3)C5—C10—C9119.4 (4)
C1—N1—S1129.7 (3)C5—C10—H10A120.3
C4—N1—S1121.7 (2)C9—C10—H10A120.3
C2—C1—N1108.5 (4)C8—C11—H11A109.5
C2—C1—Br1126.7 (3)C8—C11—H11B109.5
N1—C1—Br1124.7 (3)H11A—C11—H11B109.5
C1—C2—C3107.5 (4)C8—C11—H11C109.4
C1—C2—H2A126.2H11A—C11—H11C109.5
C3—C2—H2A126.2H11B—C11—H11C109.5
C4—C3—C2109.7 (4)C8—C11—H11D109.6
C4—C3—H3A125.2H11A—C11—H11D54.7
C2—C3—H3A125.2H11B—C11—H11D57.7
C3—C4—N1107.3 (3)H11C—C11—H11D141.0
C3—C4—H4A126.4C8—C11—H11E109.4
N1—C4—H4A126.4H11A—C11—H11E141.0
C10—C5—C6120.5 (3)H11B—C11—H11E54.8
C10—C5—S1120.4 (3)H11C—C11—H11E57.8
C6—C5—S1119.0 (3)H11D—C11—H11E109.4
C5—C6—C7118.3 (4)C8—C11—H11F109.5
C5—C6—H6A120.9H11A—C11—H11F57.8
C7—C6—H6A120.9H11B—C11—H11F141.0
C8—C7—C6122.4 (4)H11C—C11—H11F54.7
C8—C7—H7A118.8H11D—C11—H11F109.5
C6—C7—H7A118.8H11E—C11—H11F109.5
O1—S1—N1—C1163.9 (3)O1—S1—C5—C10165.9 (3)
O2—S1—N1—C134.8 (4)O2—S1—C5—C1031.9 (4)
C5—S1—N1—C181.2 (3)N1—S1—C5—C1082.4 (3)
O1—S1—N1—C432.6 (3)O1—S1—C5—C616.2 (4)
O2—S1—N1—C4161.7 (3)O2—S1—C5—C6150.2 (3)
C5—S1—N1—C482.2 (3)N1—S1—C5—C695.5 (3)
C4—N1—C1—C22.7 (4)C10—C5—C6—C71.5 (6)
S1—N1—C1—C2168.0 (3)S1—C5—C6—C7179.4 (4)
C4—N1—C1—Br1179.5 (3)C5—C6—C7—C80.7 (7)
S1—N1—C1—Br114.1 (5)C6—C7—C8—C90.7 (7)
N1—C1—C2—C31.7 (5)C6—C7—C8—C11179.4 (5)
Br1—C1—C2—C3179.5 (3)C7—C8—C9—C101.4 (7)
C1—C2—C3—C40.0 (5)C11—C8—C9—C10178.7 (4)
C2—C3—C4—N11.7 (5)C6—C5—C10—C90.8 (6)
C1—N1—C4—C32.7 (4)S1—C5—C10—C9178.7 (3)
S1—N1—C4—C3169.5 (3)C8—C9—C10—C50.6 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···O2i0.932.583.383 (5)145
C3—H3A···O1i0.932.813.585 (5)141
C4—H4A···O2ii0.932.553.447 (5)161
C7—H7A···Br1iii0.933.113.977 (4)155
C9—H9A···O1iv0.932.803.622 (5)148
Symmetry codes: (i) x1, y, z; (ii) x1/2, y+3/2, z1/2; (iii) x, y, z1; (iv) x+3/2, y1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC11H10BrNO2S
Mr300.17
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)7.6482 (13), 16.307 (2), 10.2114 (17)
β (°) 110.233 (3)
V3)1195.0 (3)
Z4
Radiation typeMo Kα
µ (mm1)3.60
Crystal size (mm)0.35 × 0.20 × 0.10
Data collection
DiffractometerMercury AFC-8S
diffractometer
Absorption correctionMulti-scan
(REQAB; Jacobson, 1998)
Tmin, Tmax0.454, 0.698
No. of measured, independent and
observed [I > 2σ(I)] reflections
11515, 2437, 2006
Rint0.029
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.089, 1.00
No. of reflections2437
No. of parameters145
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.48, 0.75

Computer programs: CrystalClear (Molecular Structure Corporation/Rigaku, 2001), CrystalClear, SHELXTL-Plus (Sheldrick, 2000), SHELXTL-Plus.

Selected geometric parameters (Å, º) top
Br1—C11.858 (4)C3—C41.311 (6)
S1—O11.424 (3)C5—C101.375 (5)
S1—O21.425 (3)C5—C61.379 (5)
S1—N11.676 (3)C6—C71.381 (6)
S1—C51.748 (3)C7—C81.377 (6)
N1—C11.389 (4)C8—C91.367 (6)
N1—C41.432 (5)C8—C111.509 (5)
C1—C21.340 (5)C9—C101.379 (5)
C2—C31.421 (6)
O1—S1—O2120.64 (18)C4—C3—C2109.7 (4)
O1—S1—N1104.75 (16)C3—C4—N1107.3 (3)
O2—S1—N1106.86 (16)C10—C5—C6120.5 (3)
O1—S1—C5109.21 (17)C10—C5—S1120.4 (3)
O2—S1—C5109.45 (17)C6—C5—S1119.0 (3)
N1—S1—C5104.66 (16)C5—C6—C7118.3 (4)
C1—N1—C4106.9 (3)C8—C7—C6122.4 (4)
C1—N1—S1129.7 (3)C9—C8—C7117.7 (4)
C4—N1—S1121.7 (2)C9—C8—C11120.9 (4)
C2—C1—N1108.5 (4)C7—C8—C11121.4 (4)
C2—C1—Br1126.7 (3)C8—C9—C10121.6 (4)
N1—C1—Br1124.7 (3)C5—C10—C9119.4 (4)
C1—C2—C3107.5 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···O2i0.932.583.383 (5)145
C3—H3A···O1i0.932.813.585 (5)141
C4—H4A···O2ii0.932.553.447 (5)161
C7—H7A···Br1iii0.933.113.977 (4)155
C9—H9A···O1iv0.932.803.622 (5)148
Symmetry codes: (i) x1, y, z; (ii) x1/2, y+3/2, z1/2; (iii) x, y, z1; (iv) x+3/2, y1/2, z+3/2.
 

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