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Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): o742.
Published online 2009 March 11. doi:  10.1107/S160053680900840X
PMCID: PMC2969046

4-Fluoro-N-methyl-N-(1,2,3,4-tetra­hydro­carbazol-3-yl)benzene­sulfonamide

Abstract

In the title compound, C19H19FN2O2S, the hydrogenated six-membered ring of the carbazole unit adopts a half-chair conformation and the plane of the fluoro­phenyl ring forms a dihedral angle of 41.5 (1)° with respect to the carbazole mean plane. The crystal structure is segregated into layers containing the carbazole units and fluoro­phenyl rings in alternate (200) planes. The carbazole units form centrosymmetric face-to-face inter­actions [inter­planar separation = 4.06 (1) Å] and edge-to-face inter­actions in which the N—H group is directed towards an adjacent carbazole face, with a shortest H(...)C contact of 2.53 Å. The fluoro­phenyl rings form face-to-face contacts with an approximate inter­planar separation of 3.75 Å and a centroid–centroid distance of 4.73 (1) Å.

Related literature

For background literature and synthesis details, see: Ulven & Kostenis (2005 [triangle], 2006 [triangle]). For related structures, see: Bjerrum et al. (2009 [triangle]); Löffler et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o742-scheme1.jpg

Experimental

Crystal data

  • C19H19FN2O2S
  • M r = 358.42
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o742-efi1.jpg
  • a = 15.2748 (7) Å
  • b = 12.0319 (6) Å
  • c = 9.4430 (4) Å
  • β = 102.445 (2)°
  • V = 1694.70 (14) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.22 mm−1
  • T = 180 K
  • 0.20 × 0.20 × 0.08 mm

Data collection

  • Bruker–Nonius X8 APEX-II CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003 [triangle]) T min = 0.870, T max = 0.983
  • 29053 measured reflections
  • 4157 independent reflections
  • 2816 reflections with I > 2σ(I)
  • R int = 0.039

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.100
  • S = 1.03
  • 4157 reflections
  • 227 parameters
  • H-atom parameters constrained
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.36 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2003 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680900840X/gk2196sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680900840X/gk2196Isup2.hkl

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

Acknowledgments

We are grateful to the Danish Natural Sciences Research Council and the Carlsberg Foundation for provision of the X-ray equipment.

supplementary crystallographic information

Comment

The title compound is useful as an intermediate in the synthesis of antagonists of the prostaglandin D2 receptor CRTH2 (DP2) (Ulven & Kostenis, 2006).

Experimental

The compound was synthesized as described in Ulven & Kostenis (2005).

Refinement

H atoms bound to C atoms were placed in idealized positions with C—H = 0.95–1.00 Å and refined as riding with Uiso(H) = 1.2 or 1.5Ueq(C). The methyl group was allowed to rotate about its local threefold axis. The H atom of the NH group was visible in a difference Fourier map but was placed geometrically and refined as riding for the final cycles of refinement with N—H = 0.88 Å and Uiso(H) = 1.2Ueq(N).

Figures

Fig. 1.
Molecular structure of the title compound with displacement ellipsoids shown at 50% probability for non-H atoms.
Fig. 2.
Unit-cell contents projected along the b axis, showing segregation of carbazole and fluorophenyl groups in the (200) planes. H atoms are omitted.

Crystal data

C19H19FN2O2SF(000) = 752
Mr = 358.42Dx = 1.405 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6906 reflections
a = 15.2748 (7) Åθ = 2.8–24.2°
b = 12.0319 (6) ŵ = 0.22 mm1
c = 9.4430 (4) ÅT = 180 K
β = 102.445 (2)°Plate, yellow
V = 1694.70 (14) Å30.20 × 0.20 × 0.08 mm
Z = 4

Data collection

Bruker–Nonius X8 APEX-II CCD diffractometer4157 independent reflections
Radiation source: fine-focus sealed tube2816 reflections with I > 2σ(I)
graphiteRint = 0.039
Thin–slice ω and [var phi] scansθmax = 28.4°, θmin = 3.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)h = −20→20
Tmin = 0.870, Tmax = 0.983k = −14→16
29053 measured reflectionsl = −12→12

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100H-atom parameters constrained
S = 1.03w = 1/[σ2(Fo2) + (0.0499P)2 + 0.197P] where P = (Fo2 + 2Fc2)/3
4157 reflections(Δ/σ)max = 0.001
227 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = −0.36 e Å3

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
S10.18551 (2)0.58771 (3)0.65744 (4)0.03103 (13)
F1−0.04364 (7)0.90794 (10)0.28602 (13)0.0644 (4)
O110.23235 (7)0.64670 (9)0.78251 (11)0.0366 (3)
O120.13016 (7)0.49488 (9)0.67472 (12)0.0418 (3)
N10.58988 (8)0.75139 (11)0.61606 (14)0.0345 (3)
H10.60600.80920.57060.041*
N20.26020 (8)0.54273 (11)0.57403 (14)0.0332 (3)
C10.64139 (10)0.70104 (13)0.73606 (16)0.0310 (4)
C20.72812 (10)0.72533 (15)0.81236 (18)0.0392 (4)
H2A0.76090.78630.78620.047*
C30.76405 (11)0.65708 (16)0.92717 (19)0.0440 (5)
H3A0.82300.67130.98130.053*
C40.71637 (11)0.56773 (15)0.96612 (18)0.0417 (4)
H4A0.74350.52201.04550.050*
C50.63012 (10)0.54441 (14)0.89130 (17)0.0346 (4)
H5A0.59790.48360.91910.041*
C60.59115 (9)0.61180 (12)0.77416 (16)0.0275 (3)
C70.50635 (10)0.61190 (12)0.67235 (15)0.0260 (3)
C80.42395 (9)0.54333 (13)0.66823 (16)0.0295 (3)
H8A0.41620.52890.76800.035*
H8B0.42940.47110.62080.035*
C90.34359 (10)0.60775 (13)0.58295 (16)0.0285 (4)
H9A0.33780.67670.63930.034*
C100.35930 (11)0.64426 (13)0.43638 (17)0.0348 (4)
H10A0.30360.67710.37840.042*
H10B0.37490.57880.38330.042*
C110.43474 (10)0.72944 (13)0.45470 (17)0.0351 (4)
H11A0.45760.73380.36440.042*
H11B0.41160.80370.47340.042*
C120.50906 (10)0.69691 (13)0.57835 (16)0.0283 (3)
C130.23280 (12)0.46523 (15)0.45307 (19)0.0449 (5)
H13A0.28340.41710.44580.067*
H13B0.21380.50710.36270.067*
H13C0.18290.41950.46980.067*
C140.11647 (9)0.68484 (13)0.54524 (16)0.0297 (4)
C150.04708 (10)0.64712 (15)0.43564 (18)0.0390 (4)
H15A0.03670.56970.42150.047*
C16−0.00662 (11)0.72264 (16)0.3475 (2)0.0452 (5)
H16A−0.05400.69830.27130.054*
C170.00987 (11)0.83361 (16)0.3721 (2)0.0440 (5)
C180.07783 (11)0.87337 (15)0.4788 (2)0.0439 (4)
H18A0.08740.95100.49240.053*
C190.13208 (11)0.79758 (14)0.56618 (18)0.0366 (4)
H19A0.18010.82280.64070.044*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0310 (2)0.0315 (2)0.0284 (2)−0.00616 (17)0.00148 (16)−0.00040 (17)
F10.0426 (6)0.0621 (8)0.0852 (9)0.0135 (5)0.0064 (6)0.0321 (6)
O110.0376 (6)0.0446 (7)0.0257 (6)−0.0085 (5)0.0024 (5)−0.0055 (5)
O120.0394 (6)0.0390 (7)0.0435 (7)−0.0114 (5)0.0015 (5)0.0075 (6)
N10.0375 (7)0.0345 (8)0.0320 (8)−0.0019 (6)0.0089 (6)0.0072 (6)
N20.0310 (7)0.0302 (7)0.0353 (8)−0.0023 (6)0.0001 (6)−0.0086 (6)
C10.0323 (8)0.0345 (9)0.0270 (8)0.0057 (7)0.0085 (7)−0.0026 (7)
C20.0334 (9)0.0494 (11)0.0352 (10)−0.0026 (8)0.0083 (8)−0.0054 (8)
C30.0327 (9)0.0608 (13)0.0362 (10)0.0064 (9)0.0025 (8)−0.0101 (9)
C40.0408 (10)0.0514 (12)0.0292 (9)0.0172 (9)−0.0005 (8)0.0005 (8)
C50.0403 (9)0.0351 (9)0.0277 (9)0.0089 (7)0.0059 (7)0.0025 (7)
C60.0296 (8)0.0301 (9)0.0237 (8)0.0066 (7)0.0076 (6)−0.0019 (7)
C70.0313 (8)0.0260 (8)0.0213 (8)0.0058 (6)0.0068 (6)0.0001 (6)
C80.0337 (8)0.0290 (8)0.0250 (8)0.0039 (7)0.0044 (6)0.0030 (6)
C90.0296 (8)0.0272 (9)0.0264 (8)0.0005 (6)0.0006 (6)−0.0037 (6)
C100.0420 (9)0.0326 (9)0.0262 (8)0.0060 (8)−0.0007 (7)0.0030 (7)
C110.0411 (9)0.0330 (9)0.0288 (9)0.0049 (7)0.0025 (7)0.0085 (7)
C120.0315 (8)0.0288 (8)0.0249 (8)0.0052 (7)0.0070 (6)0.0000 (6)
C130.0530 (11)0.0365 (10)0.0424 (11)−0.0068 (8)0.0040 (9)−0.0142 (8)
C140.0265 (8)0.0338 (9)0.0296 (8)−0.0027 (7)0.0079 (7)−0.0009 (7)
C150.0331 (9)0.0374 (10)0.0433 (10)−0.0041 (8)0.0016 (8)−0.0004 (8)
C160.0312 (9)0.0528 (12)0.0470 (11)−0.0038 (8)−0.0014 (8)0.0048 (9)
C170.0301 (9)0.0495 (12)0.0541 (12)0.0086 (8)0.0129 (8)0.0181 (9)
C180.0402 (10)0.0322 (10)0.0618 (12)0.0023 (8)0.0167 (9)0.0035 (9)
C190.0325 (8)0.0363 (10)0.0407 (10)−0.0032 (7)0.0070 (7)−0.0035 (8)

Geometric parameters (Å, °)

S1—O111.4305 (11)C8—H8A0.990
S1—O121.4312 (11)C8—H8B0.990
S1—N21.6131 (13)C9—C101.520 (2)
S1—C141.7660 (16)C9—H9A1.000
F1—C171.3572 (19)C10—C111.524 (2)
N1—C11.3733 (19)C10—H10A0.990
N1—C121.3751 (19)C10—H10B0.990
N1—H10.880C11—C121.495 (2)
N2—C131.4640 (19)C11—H11A0.990
N2—C91.4817 (19)C11—H11B0.990
C1—C21.396 (2)C13—H13A0.980
C1—C61.411 (2)C13—H13B0.980
C2—C31.376 (2)C13—H13C0.980
C2—H2A0.950C14—C191.384 (2)
C3—C41.392 (3)C14—C151.388 (2)
C3—H3A0.950C15—C161.378 (2)
C4—C51.383 (2)C15—H15A0.950
C4—H4A0.950C16—C171.369 (3)
C5—C61.397 (2)C16—H16A0.950
C5—H5A0.950C17—C181.368 (2)
C6—C71.437 (2)C18—C191.380 (2)
C7—C121.361 (2)C18—H18A0.950
C7—C81.498 (2)C19—H19A0.950
C8—C91.526 (2)
O11—S1—O12119.71 (7)N2—C9—H9A107.1
O11—S1—N2106.80 (6)C10—C9—H9A107.1
O12—S1—N2106.93 (7)C8—C9—H9A107.1
O11—S1—C14107.14 (7)C9—C10—C11110.79 (13)
O12—S1—C14107.08 (7)C9—C10—H10A109.5
N2—S1—C14108.84 (7)C11—C10—H10A109.5
C1—N1—C12109.04 (13)C9—C10—H10B109.5
C1—N1—H1125.5C11—C10—H10B109.5
C12—N1—H1125.5H10A—C10—H10B108.1
C13—N2—C9118.58 (13)C12—C11—C10109.94 (13)
C13—N2—S1118.77 (11)C12—C11—H11A109.7
C9—N2—S1119.01 (10)C10—C11—H11A109.7
N1—C1—C2130.16 (15)C12—C11—H11B109.7
N1—C1—C6107.44 (13)C10—C11—H11B109.7
C2—C1—C6122.39 (14)H11A—C11—H11B108.2
C3—C2—C1117.05 (16)C7—C12—N1109.95 (13)
C3—C2—H2A121.5C7—C12—C11125.57 (14)
C1—C2—H2A121.5N1—C12—C11124.45 (13)
C2—C3—C4121.77 (16)N2—C13—H13A109.5
C2—C3—H3A119.1N2—C13—H13B109.5
C4—C3—H3A119.1H13A—C13—H13B109.5
C5—C4—C3121.13 (16)N2—C13—H13C109.5
C5—C4—H4A119.4H13A—C13—H13C109.5
C3—C4—H4A119.4H13B—C13—H13C109.5
C4—C5—C6118.89 (16)C19—C14—C15120.47 (15)
C4—C5—H5A120.6C19—C14—S1120.04 (12)
C6—C5—H5A120.6C15—C14—S1119.49 (12)
C5—C6—C1118.77 (14)C16—C15—C14119.64 (16)
C5—C6—C7134.35 (15)C16—C15—H15A120.2
C1—C6—C7106.87 (13)C14—C15—H15A120.2
C12—C7—C6106.70 (13)C17—C16—C15118.47 (16)
C12—C7—C8122.71 (13)C17—C16—H16A120.8
C6—C7—C8130.38 (13)C15—C16—H16A120.8
C7—C8—C9108.04 (12)F1—C17—C18118.30 (17)
C7—C8—H8A110.1F1—C17—C16118.42 (17)
C9—C8—H8A110.1C18—C17—C16123.28 (17)
C7—C8—H8B110.1C17—C18—C19118.16 (16)
C9—C8—H8B110.1C17—C18—H18A120.9
H8A—C8—H8B108.4C19—C18—H18A120.9
N2—C9—C10113.79 (12)C18—C19—C14119.97 (16)
N2—C9—C8110.22 (12)C18—C19—H19A120.0
C10—C9—C8111.13 (12)C14—C19—H19A120.0
O11—S1—N2—C13171.11 (11)C7—C8—C9—N2179.29 (12)
O12—S1—N2—C1341.83 (14)C7—C8—C9—C1052.20 (16)
C14—S1—N2—C13−73.52 (13)N2—C9—C10—C11168.46 (12)
O11—S1—N2—C9−30.69 (13)C8—C9—C10—C11−66.42 (17)
O12—S1—N2—C9−159.97 (11)C9—C10—C11—C1240.74 (18)
C14—S1—N2—C984.67 (12)C6—C7—C12—N1−0.90 (17)
C12—N1—C1—C2179.04 (16)C8—C7—C12—N1174.28 (13)
C12—N1—C1—C60.25 (16)C6—C7—C12—C11−179.17 (14)
N1—C1—C2—C3−177.84 (15)C8—C7—C12—C11−4.0 (2)
C6—C1—C2—C30.8 (2)C1—N1—C12—C70.42 (17)
C1—C2—C3—C4−0.1 (2)C1—N1—C12—C11178.71 (14)
C2—C3—C4—C5−0.6 (3)C10—C11—C12—C7−7.3 (2)
C3—C4—C5—C60.5 (2)C10—C11—C12—N1174.63 (14)
C4—C5—C6—C10.2 (2)O11—S1—C14—C1916.81 (14)
C4—C5—C6—C7178.64 (16)O12—S1—C14—C19146.41 (13)
N1—C1—C6—C5178.01 (13)N2—S1—C14—C19−98.34 (14)
C2—C1—C6—C5−0.9 (2)O11—S1—C14—C15−163.65 (12)
N1—C1—C6—C7−0.79 (16)O12—S1—C14—C15−34.05 (14)
C2—C1—C6—C7−179.70 (14)N2—S1—C14—C1581.21 (13)
C5—C6—C7—C12−177.49 (16)C19—C14—C15—C16−0.1 (2)
C1—C6—C7—C121.04 (16)S1—C14—C15—C16−179.68 (13)
C5—C6—C7—C87.8 (3)C14—C15—C16—C17−0.6 (2)
C1—C6—C7—C8−173.64 (14)C15—C16—C17—F1−179.37 (15)
C12—C7—C8—C9−18.43 (19)C15—C16—C17—C180.9 (3)
C6—C7—C8—C9155.51 (15)F1—C17—C18—C19179.96 (14)
C13—N2—C9—C1036.64 (19)C16—C17—C18—C19−0.3 (3)
S1—N2—C9—C10−121.59 (13)C17—C18—C19—C14−0.5 (2)
C13—N2—C9—C8−88.96 (16)C15—C14—C19—C180.7 (2)
S1—N2—C9—C8112.81 (12)S1—C14—C19—C18−179.72 (12)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2196).

References

  • Bjerrum, J. V., Ulven, T. & Bond, A. D. (2009). Acta Cryst. E65, o579. [PMC free article] [PubMed]
  • Bruker (2003). SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2004). APEX2 Bruker AXS Inc., Madison, Wisconsin, USA.
  • Löffler, P. M. G., Ulven, T. & Bond, A. D. (2009). Acta Cryst. E65, o685. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2003). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Ulven, T. & Kostenis, E. (2005). J. Med. Chem.48, 897–900. [PubMed]
  • Ulven, T. & Kostenis, E. (2006). Curr. Top. Med. Chem.6, 1427–1444. [PubMed]

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