Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803009097/om6140sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803009097/om6140Isup2.hkl |
CCDC reference: 214811
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.
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.
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.
C11H10BrNO2S | Dx = 1.668 Mg m−3 |
Mr = 300.17 | Melting point: 105 K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6482 (13) Å | Cell parameters from 7533 reflections |
b = 16.307 (2) Å | θ = 2.8–26.4° |
c = 10.2114 (17) Å | µ = 3.60 mm−1 |
β = 110.233 (3)° | T = 293 K |
V = 1195.0 (3) Å3 | Plate, colorless |
Z = 4 | 0.35 × 0.20 × 0.10 mm |
F(000) = 600 |
Mercury AFC-8S diffractometer | 2437 independent reflections |
Radiation source: fine-focus sealed tube | 2006 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
Detector resolution: 14.6199 pixels mm-1 | θmax = 26.4°, θmin = 2.9° |
ω scans | h = −9→9 |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | k = −20→19 |
Tmin = 0.454, Tmax = 0.698 | l = −11→12 |
11515 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.089 | H-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 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.75 e Å−3 |
C11H10BrNO2S | V = 1195.0 (3) Å3 |
Mr = 300.17 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.6482 (13) Å | µ = 3.60 mm−1 |
b = 16.307 (2) Å | T = 293 K |
c = 10.2114 (17) Å | 0.35 × 0.20 × 0.10 mm |
β = 110.233 (3)° |
Mercury AFC-8S diffractometer | 2437 independent reflections |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | 2006 reflections with I > 2σ(I) |
Tmin = 0.454, Tmax = 0.698 | Rint = 0.029 |
11515 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.48 e Å−3 |
2437 reflections | Δρmin = −0.75 e Å−3 |
145 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Br1 | 0.69840 (8) | 0.57111 (3) | 1.11357 (5) | 0.07736 (19) | |
S1 | 0.84978 (12) | 0.68733 (6) | 0.87941 (10) | 0.0468 (2) | |
O1 | 0.8764 (4) | 0.76468 (16) | 0.8244 (3) | 0.0634 (8) | |
O2 | 0.9796 (4) | 0.65815 (19) | 1.0077 (3) | 0.0626 (8) | |
N1 | 0.6435 (4) | 0.69533 (18) | 0.9018 (3) | 0.0436 (7) | |
C1 | 0.5666 (5) | 0.6468 (2) | 0.9798 (4) | 0.0493 (9) | |
C2 | 0.3860 (6) | 0.6662 (3) | 0.9455 (5) | 0.0652 (11) | |
H2A | 0.3028 | 0.6439 | 0.9840 | 0.078* | |
C3 | 0.3449 (6) | 0.7272 (3) | 0.8397 (5) | 0.0649 (12) | |
H3A | 0.2289 | 0.7515 | 0.7974 | 0.078* | |
C4 | 0.4953 (5) | 0.7441 (2) | 0.8109 (4) | 0.0504 (9) | |
H4A | 0.5041 | 0.7809 | 0.7438 | 0.060* | |
C5 | 0.8154 (5) | 0.6122 (2) | 0.7508 (4) | 0.0417 (8) | |
C6 | 0.7711 (7) | 0.6361 (3) | 0.6136 (4) | 0.0629 (11) | |
H6A | 0.7606 | 0.6914 | 0.5893 | 0.075* | |
C7 | 0.7427 (7) | 0.5760 (3) | 0.5131 (4) | 0.0703 (13) | |
H7A | 0.7141 | 0.5917 | 0.4205 | 0.084* | |
C8 | 0.7551 (5) | 0.4937 (2) | 0.5451 (4) | 0.0537 (9) | |
C9 | 0.7953 (6) | 0.4722 (2) | 0.6818 (4) | 0.0629 (11) | |
H9A | 0.8017 | 0.4169 | 0.7056 | 0.076* | |
C10 | 0.8265 (6) | 0.5304 (2) | 0.7854 (4) | 0.0592 (11) | |
H10A | 0.8548 | 0.5145 | 0.8779 | 0.071* | |
C11 | 0.7252 (7) | 0.4292 (3) | 0.4337 (5) | 0.0748 (13) | |
H11A | 0.7399 | 0.3757 | 0.4754 | 0.112* | 0.50 |
H11B | 0.8148 | 0.4364 | 0.3880 | 0.112* | 0.50 |
H11C | 0.6017 | 0.4344 | 0.3665 | 0.112* | 0.50 |
H11D | 0.8346 | 0.3956 | 0.4548 | 0.112* | 0.50 |
H11E | 0.7012 | 0.4553 | 0.3449 | 0.112* | 0.50 |
H11F | 0.6206 | 0.3956 | 0.4301 | 0.112* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0913 (4) | 0.0759 (3) | 0.0607 (3) | −0.0016 (3) | 0.0210 (2) | 0.0169 (2) |
S1 | 0.0400 (4) | 0.0507 (5) | 0.0512 (5) | −0.0067 (4) | 0.0174 (4) | −0.0122 (4) |
O1 | 0.0665 (18) | 0.0489 (16) | 0.087 (2) | −0.0189 (13) | 0.0415 (16) | −0.0142 (14) |
O2 | 0.0416 (14) | 0.088 (2) | 0.0508 (15) | 0.0005 (14) | 0.0069 (12) | −0.0160 (15) |
N1 | 0.0417 (15) | 0.0439 (16) | 0.0476 (16) | 0.0001 (13) | 0.0187 (13) | −0.0031 (13) |
C1 | 0.059 (2) | 0.047 (2) | 0.0453 (19) | −0.0014 (17) | 0.0223 (18) | −0.0020 (16) |
C2 | 0.058 (3) | 0.063 (3) | 0.088 (3) | −0.002 (2) | 0.043 (2) | −0.005 (2) |
C3 | 0.045 (2) | 0.055 (2) | 0.089 (3) | 0.0164 (19) | 0.016 (2) | −0.006 (2) |
C4 | 0.062 (2) | 0.0383 (19) | 0.052 (2) | −0.0001 (17) | 0.0208 (19) | −0.0022 (16) |
C5 | 0.0410 (18) | 0.0431 (19) | 0.0416 (18) | 0.0019 (15) | 0.0150 (15) | −0.0042 (15) |
C6 | 0.098 (3) | 0.046 (2) | 0.051 (2) | −0.005 (2) | 0.034 (2) | 0.0036 (18) |
C7 | 0.113 (4) | 0.060 (3) | 0.042 (2) | −0.004 (3) | 0.032 (2) | −0.0010 (19) |
C8 | 0.056 (2) | 0.052 (2) | 0.052 (2) | 0.0012 (18) | 0.0173 (18) | −0.0085 (18) |
C9 | 0.087 (3) | 0.040 (2) | 0.055 (2) | 0.014 (2) | 0.015 (2) | −0.0003 (18) |
C10 | 0.076 (3) | 0.052 (2) | 0.042 (2) | 0.014 (2) | 0.0107 (19) | 0.0035 (17) |
C11 | 0.089 (3) | 0.070 (3) | 0.065 (3) | −0.006 (3) | 0.026 (3) | −0.025 (2) |
Br1—C1 | 1.858 (4) | C6—C7 | 1.381 (6) |
S1—O1 | 1.424 (3) | C6—H6A | 0.9300 |
S1—O2 | 1.425 (3) | C7—C8 | 1.377 (6) |
S1—N1 | 1.676 (3) | C7—H7A | 0.9300 |
S1—C5 | 1.748 (3) | C8—C9 | 1.367 (6) |
N1—C1 | 1.389 (4) | C8—C11 | 1.509 (5) |
N1—C4 | 1.432 (5) | C9—C10 | 1.379 (5) |
C1—C2 | 1.340 (5) | C9—H9A | 0.9300 |
C2—C3 | 1.421 (6) | C10—H10A | 0.9300 |
C2—H2A | 0.9300 | C11—H11A | 0.9600 |
C3—C4 | 1.311 (6) | C11—H11B | 0.9599 |
C3—H3A | 0.9300 | C11—H11C | 0.9600 |
C4—H4A | 0.9300 | C11—H11D | 0.9600 |
C5—C10 | 1.375 (5) | C11—H11E | 0.9600 |
C5—C6 | 1.379 (5) | C11—H11F | 0.9601 |
O1—S1—O2 | 120.64 (18) | C9—C8—C7 | 117.7 (4) |
O1—S1—N1 | 104.75 (16) | C9—C8—C11 | 120.9 (4) |
O2—S1—N1 | 106.86 (16) | C7—C8—C11 | 121.4 (4) |
O1—S1—C5 | 109.21 (17) | C8—C9—C10 | 121.6 (4) |
O2—S1—C5 | 109.45 (17) | C8—C9—H9A | 119.2 |
N1—S1—C5 | 104.66 (16) | C10—C9—H9A | 119.2 |
C1—N1—C4 | 106.9 (3) | C5—C10—C9 | 119.4 (4) |
C1—N1—S1 | 129.7 (3) | C5—C10—H10A | 120.3 |
C4—N1—S1 | 121.7 (2) | C9—C10—H10A | 120.3 |
C2—C1—N1 | 108.5 (4) | C8—C11—H11A | 109.5 |
C2—C1—Br1 | 126.7 (3) | C8—C11—H11B | 109.5 |
N1—C1—Br1 | 124.7 (3) | H11A—C11—H11B | 109.5 |
C1—C2—C3 | 107.5 (4) | C8—C11—H11C | 109.4 |
C1—C2—H2A | 126.2 | H11A—C11—H11C | 109.5 |
C3—C2—H2A | 126.2 | H11B—C11—H11C | 109.5 |
C4—C3—C2 | 109.7 (4) | C8—C11—H11D | 109.6 |
C4—C3—H3A | 125.2 | H11A—C11—H11D | 54.7 |
C2—C3—H3A | 125.2 | H11B—C11—H11D | 57.7 |
C3—C4—N1 | 107.3 (3) | H11C—C11—H11D | 141.0 |
C3—C4—H4A | 126.4 | C8—C11—H11E | 109.4 |
N1—C4—H4A | 126.4 | H11A—C11—H11E | 141.0 |
C10—C5—C6 | 120.5 (3) | H11B—C11—H11E | 54.8 |
C10—C5—S1 | 120.4 (3) | H11C—C11—H11E | 57.8 |
C6—C5—S1 | 119.0 (3) | H11D—C11—H11E | 109.4 |
C5—C6—C7 | 118.3 (4) | C8—C11—H11F | 109.5 |
C5—C6—H6A | 120.9 | H11A—C11—H11F | 57.8 |
C7—C6—H6A | 120.9 | H11B—C11—H11F | 141.0 |
C8—C7—C6 | 122.4 (4) | H11C—C11—H11F | 54.7 |
C8—C7—H7A | 118.8 | H11D—C11—H11F | 109.5 |
C6—C7—H7A | 118.8 | H11E—C11—H11F | 109.5 |
O1—S1—N1—C1 | −163.9 (3) | O1—S1—C5—C10 | 165.9 (3) |
O2—S1—N1—C1 | −34.8 (4) | O2—S1—C5—C10 | 31.9 (4) |
C5—S1—N1—C1 | 81.2 (3) | N1—S1—C5—C10 | −82.4 (3) |
O1—S1—N1—C4 | 32.6 (3) | O1—S1—C5—C6 | −16.2 (4) |
O2—S1—N1—C4 | 161.7 (3) | O2—S1—C5—C6 | −150.2 (3) |
C5—S1—N1—C4 | −82.2 (3) | N1—S1—C5—C6 | 95.5 (3) |
C4—N1—C1—C2 | −2.7 (4) | C10—C5—C6—C7 | −1.5 (6) |
S1—N1—C1—C2 | −168.0 (3) | S1—C5—C6—C7 | −179.4 (4) |
C4—N1—C1—Br1 | 179.5 (3) | C5—C6—C7—C8 | 0.7 (7) |
S1—N1—C1—Br1 | 14.1 (5) | C6—C7—C8—C9 | 0.7 (7) |
N1—C1—C2—C3 | 1.7 (5) | C6—C7—C8—C11 | −179.4 (5) |
Br1—C1—C2—C3 | 179.5 (3) | C7—C8—C9—C10 | −1.4 (7) |
C1—C2—C3—C4 | 0.0 (5) | C11—C8—C9—C10 | 178.7 (4) |
C2—C3—C4—N1 | −1.7 (5) | C6—C5—C10—C9 | 0.8 (6) |
C1—N1—C4—C3 | 2.7 (4) | S1—C5—C10—C9 | 178.7 (3) |
S1—N1—C4—C3 | 169.5 (3) | C8—C9—C10—C5 | 0.6 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···O2i | 0.93 | 2.58 | 3.383 (5) | 145 |
C3—H3A···O1i | 0.93 | 2.81 | 3.585 (5) | 141 |
C4—H4A···O2ii | 0.93 | 2.55 | 3.447 (5) | 161 |
C7—H7A···Br1iii | 0.93 | 3.11 | 3.977 (4) | 155 |
C9—H9A···O1iv | 0.93 | 2.80 | 3.622 (5) | 148 |
Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+3/2, z−1/2; (iii) x, y, z−1; (iv) −x+3/2, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C11H10BrNO2S |
Mr | 300.17 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 7.6482 (13), 16.307 (2), 10.2114 (17) |
β (°) | 110.233 (3) |
V (Å3) | 1195.0 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.60 |
Crystal size (mm) | 0.35 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Mercury AFC-8S diffractometer |
Absorption correction | Multi-scan (REQAB; Jacobson, 1998) |
Tmin, Tmax | 0.454, 0.698 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11515, 2437, 2006 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.089, 1.00 |
No. of reflections | 2437 |
No. of parameters | 145 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.48, −0.75 |
Computer programs: CrystalClear (Molecular Structure Corporation/Rigaku, 2001), CrystalClear, SHELXTL-Plus (Sheldrick, 2000), SHELXTL-Plus.
Br1—C1 | 1.858 (4) | C3—C4 | 1.311 (6) |
S1—O1 | 1.424 (3) | C5—C10 | 1.375 (5) |
S1—O2 | 1.425 (3) | C5—C6 | 1.379 (5) |
S1—N1 | 1.676 (3) | C6—C7 | 1.381 (6) |
S1—C5 | 1.748 (3) | C7—C8 | 1.377 (6) |
N1—C1 | 1.389 (4) | C8—C9 | 1.367 (6) |
N1—C4 | 1.432 (5) | C8—C11 | 1.509 (5) |
C1—C2 | 1.340 (5) | C9—C10 | 1.379 (5) |
C2—C3 | 1.421 (6) | ||
O1—S1—O2 | 120.64 (18) | C4—C3—C2 | 109.7 (4) |
O1—S1—N1 | 104.75 (16) | C3—C4—N1 | 107.3 (3) |
O2—S1—N1 | 106.86 (16) | C10—C5—C6 | 120.5 (3) |
O1—S1—C5 | 109.21 (17) | C10—C5—S1 | 120.4 (3) |
O2—S1—C5 | 109.45 (17) | C6—C5—S1 | 119.0 (3) |
N1—S1—C5 | 104.66 (16) | C5—C6—C7 | 118.3 (4) |
C1—N1—C4 | 106.9 (3) | C8—C7—C6 | 122.4 (4) |
C1—N1—S1 | 129.7 (3) | C9—C8—C7 | 117.7 (4) |
C4—N1—S1 | 121.7 (2) | C9—C8—C11 | 120.9 (4) |
C2—C1—N1 | 108.5 (4) | C7—C8—C11 | 121.4 (4) |
C2—C1—Br1 | 126.7 (3) | C8—C9—C10 | 121.6 (4) |
N1—C1—Br1 | 124.7 (3) | C5—C10—C9 | 119.4 (4) |
C1—C2—C3 | 107.5 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···O2i | 0.93 | 2.58 | 3.383 (5) | 145 |
C3—H3A···O1i | 0.93 | 2.81 | 3.585 (5) | 141 |
C4—H4A···O2ii | 0.93 | 2.55 | 3.447 (5) | 161 |
C7—H7A···Br1iii | 0.93 | 3.11 | 3.977 (4) | 155 |
C9—H9A···O1iv | 0.93 | 2.80 | 3.622 (5) | 148 |
Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+3/2, z−1/2; (iii) x, y, z−1; (iv) −x+3/2, y−1/2, −z+3/2. |
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.