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Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): o685.
Published online 2009 March 6. doi:  10.1107/S160053680900748X
PMCID: PMC2969037

Ethyl 2-(1,2,3,4-tetrahydro­spiro­[carba­zole-3,2′-[1,3]dioxolan]-9-yl)acetate

Abstract

In the title compound, C18H21NO4, the hydrogenated six-membered ring of the carbazole unit adopts a half-chair conformation. The dioxolane ring and ethyl­acetate substituent point to opposite sides of the carbazole plane. The ethyl­acetate substituent adopts an essentially fully extended conformation, and its mean plane forms a dihedral angle of 83.8 (1)° with respect to the carbazole mean plane. The mol­ecules are arranged into stacks in which the carbazole planes form a dihedral angle of 4.4 (1)° and have an approximate inter­planar separation of 3.6 Å.

Related literature

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

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Object name is e-65-0o685-scheme1.jpg

Experimental

Crystal data

  • C18H21NO4
  • M r = 315.36
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o685-efi1.jpg
  • a = 10.5533 (4) Å
  • b = 17.3773 (6) Å
  • c = 8.9637 (3) Å
  • β = 105.629 (1)°
  • V = 1583.05 (10) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 180 K
  • 0.50 × 0.50 × 0.10 mm

Data collection

  • Bruker-Nonius X8 APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003 [triangle]) T min = 0.847, T max = 0.991
  • 25055 measured reflections
  • 3851 independent reflections
  • 3174 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.112
  • S = 1.04
  • 3851 reflections
  • 208 parameters
  • H-atom parameters constrained
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.25 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/S160053680900748X/xu2485sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680900748X/xu2485Isup2.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 = 0.95–0.99 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.

Figures

Fig. 1.
Molecular structure of the title compound with displacement ellipsoids shown at 50% probability for non-H atoms.
Fig. 2.
Packing diagram viewed along the c axis, showing stacked carbazole units. H atoms are omitted.

Crystal data

C18H21NO4F(000) = 672
Mr = 315.36Dx = 1.323 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7203 reflections
a = 10.5533 (4) Åθ = 2.0–28.2°
b = 17.3773 (6) ŵ = 0.09 mm1
c = 8.9637 (3) ÅT = 180 K
β = 105.629 (1)°Plate, brown
V = 1583.05 (10) Å30.50 × 0.50 × 0.10 mm
Z = 4

Data collection

Bruker-Nonius X8 APEXII CCD diffractometer3851 independent reflections
Radiation source: fine-focus sealed tube3174 reflections with I > 2σ(I)
graphiteRint = 0.025
thin–slice ω and [var phi] scansθmax = 28.3°, θmin = 3.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)h = −13→13
Tmin = 0.847, Tmax = 0.991k = −23→21
25055 measured reflectionsl = −11→11

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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.0568P)2 + 0.4296P] where P = (Fo2 + 2Fc2)/3
3851 reflections(Δ/σ)max < 0.001
208 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = −0.25 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
O11.21234 (9)0.15818 (7)1.12008 (10)0.0460 (3)
O21.17774 (8)0.16828 (5)0.85930 (9)0.0310 (2)
O30.54620 (9)0.18009 (6)0.72948 (11)0.0431 (2)
O40.48419 (8)0.12028 (5)0.50032 (10)0.0319 (2)
N10.76683 (9)0.24098 (6)0.66065 (11)0.0269 (2)
C10.76918 (11)0.32014 (7)0.67550 (13)0.0271 (2)
C20.68683 (13)0.37599 (8)0.58858 (16)0.0375 (3)
H2A0.61370.36240.50480.045*
C30.71574 (15)0.45191 (8)0.62915 (18)0.0459 (3)
H3A0.66110.49120.57190.055*
C40.82262 (15)0.47257 (8)0.75148 (18)0.0428 (3)
H4A0.83990.52540.77560.051*
C50.90393 (13)0.41716 (7)0.83833 (15)0.0339 (3)
H5A0.97660.43160.92190.041*
C60.87768 (11)0.33951 (6)0.80135 (13)0.0263 (2)
C70.93961 (10)0.26886 (6)0.86264 (13)0.0256 (2)
C81.06186 (12)0.25587 (8)0.99027 (14)0.0324 (3)
H8A1.04270.26301.09160.039*
H8B1.12960.29400.98250.039*
C91.11382 (11)0.17469 (7)0.98003 (13)0.0305 (3)
C101.00563 (12)0.11489 (7)0.95185 (14)0.0334 (3)
H10A0.96250.11701.03710.040*
H10B1.04480.06310.95260.040*
C110.90183 (12)0.12724 (7)0.79701 (14)0.0311 (3)
H11A0.93590.10860.71090.037*
H11B0.82130.09770.79580.037*
C120.86989 (10)0.21090 (6)0.77637 (13)0.0255 (2)
C131.33628 (14)0.16069 (11)1.09153 (17)0.0486 (4)
H13A1.37740.10901.10430.058*
H13B1.39500.19681.16360.058*
C141.31189 (12)0.18790 (9)0.92705 (15)0.0398 (3)
H14A1.32570.24410.92280.048*
H14B1.37040.16120.87400.048*
C150.67326 (11)0.19717 (7)0.54503 (13)0.0290 (2)
H15A0.71920.15370.51070.035*
H15B0.63610.23040.45400.035*
C160.56219 (11)0.16596 (6)0.60498 (13)0.0264 (2)
C170.37837 (12)0.08256 (8)0.54942 (15)0.0373 (3)
H17A0.32300.12150.58260.045*
H17B0.41560.04770.63770.045*
C180.29786 (13)0.03789 (8)0.41509 (16)0.0407 (3)
H18A0.22590.01200.44500.061*
H18B0.3534−0.00060.38350.061*
H18C0.26130.07290.32850.061*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0307 (5)0.0794 (7)0.0284 (5)0.0149 (5)0.0090 (4)0.0144 (4)
O20.0270 (4)0.0428 (5)0.0261 (4)0.0009 (3)0.0119 (3)0.0002 (3)
O30.0339 (5)0.0658 (6)0.0338 (5)−0.0159 (4)0.0163 (4)−0.0132 (4)
O40.0255 (4)0.0388 (5)0.0317 (4)−0.0088 (3)0.0081 (3)−0.0039 (3)
N10.0220 (5)0.0306 (5)0.0275 (5)−0.0043 (4)0.0057 (4)−0.0010 (4)
C10.0241 (5)0.0308 (6)0.0295 (5)−0.0023 (4)0.0126 (4)0.0011 (4)
C20.0323 (6)0.0439 (7)0.0371 (6)0.0055 (5)0.0106 (5)0.0077 (5)
C30.0507 (8)0.0371 (7)0.0540 (8)0.0124 (6)0.0211 (7)0.0119 (6)
C40.0532 (8)0.0284 (6)0.0553 (8)0.0005 (6)0.0294 (7)−0.0007 (6)
C50.0356 (6)0.0329 (6)0.0385 (6)−0.0058 (5)0.0193 (5)−0.0072 (5)
C60.0247 (5)0.0302 (6)0.0280 (5)−0.0022 (4)0.0138 (4)−0.0017 (4)
C70.0227 (5)0.0307 (6)0.0256 (5)−0.0016 (4)0.0100 (4)−0.0027 (4)
C80.0264 (6)0.0425 (7)0.0270 (6)0.0004 (5)0.0051 (4)−0.0068 (5)
C90.0264 (6)0.0444 (7)0.0221 (5)0.0054 (5)0.0092 (4)0.0046 (5)
C100.0331 (6)0.0362 (6)0.0350 (6)0.0046 (5)0.0160 (5)0.0083 (5)
C110.0299 (6)0.0284 (6)0.0361 (6)−0.0026 (4)0.0109 (5)−0.0010 (5)
C120.0216 (5)0.0300 (6)0.0263 (5)−0.0019 (4)0.0088 (4)−0.0005 (4)
C130.0301 (7)0.0766 (11)0.0369 (7)−0.0055 (7)0.0054 (5)−0.0011 (7)
C140.0288 (6)0.0552 (8)0.0383 (7)−0.0054 (6)0.0142 (5)−0.0041 (6)
C150.0241 (5)0.0381 (6)0.0252 (5)−0.0066 (5)0.0073 (4)−0.0031 (5)
C160.0204 (5)0.0315 (6)0.0265 (5)−0.0005 (4)0.0050 (4)0.0002 (4)
C170.0277 (6)0.0442 (7)0.0404 (7)−0.0096 (5)0.0099 (5)0.0018 (6)
C180.0340 (7)0.0403 (7)0.0445 (7)−0.0114 (5)0.0049 (5)0.0023 (6)

Geometric parameters (Å, °)

O1—C131.3995 (17)C8—H8A0.990
O1—C91.4268 (14)C8—H8B0.990
O2—C141.4233 (15)C9—C101.5140 (18)
O2—C91.4254 (13)C10—C111.5340 (17)
O3—C161.1982 (14)C10—H10A0.990
O4—C161.3311 (14)C10—H10B0.990
O4—C171.4613 (14)C11—C121.4926 (16)
N1—C11.3817 (15)C11—H11A0.990
N1—C121.3872 (14)C11—H11B0.990
N1—C151.4412 (14)C13—C141.503 (2)
C1—C21.3926 (17)C13—H13A0.990
C1—C61.4146 (16)C13—H13B0.990
C2—C31.381 (2)C14—H14A0.990
C2—H2A0.950C14—H14B0.990
C3—C41.392 (2)C15—C161.5154 (15)
C3—H3A0.950C15—H15A0.990
C4—C51.382 (2)C15—H15B0.990
C4—H4A0.950C17—C181.4910 (18)
C5—C61.3993 (16)C17—H17A0.990
C5—H5A0.950C17—H17B0.990
C6—C71.4293 (16)C18—H18A0.980
C7—C121.3591 (16)C18—H18B0.980
C7—C81.4929 (15)C18—H18C0.980
C8—C91.5252 (18)
C13—O1—C9109.16 (9)H10A—C10—H10B107.9
C14—O2—C9106.09 (9)C12—C11—C10109.32 (10)
C16—O4—C17115.65 (9)C12—C11—H11A109.8
C1—N1—C12108.24 (9)C10—C11—H11A109.8
C1—N1—C15125.89 (10)C12—C11—H11B109.8
C12—N1—C15125.87 (10)C10—C11—H11B109.8
N1—C1—C2130.37 (11)H11A—C11—H11B108.3
N1—C1—C6107.66 (10)C7—C12—N1109.97 (10)
C2—C1—C6121.97 (11)C7—C12—C11125.57 (10)
C3—C2—C1117.28 (13)N1—C12—C11124.41 (10)
C3—C2—H2A121.4O1—C13—C14105.53 (11)
C1—C2—H2A121.4O1—C13—H13A110.6
C2—C3—C4121.92 (13)C14—C13—H13A110.6
C2—C3—H3A119.0O1—C13—H13B110.6
C4—C3—H3A119.0C14—C13—H13B110.6
C5—C4—C3120.83 (13)H13A—C13—H13B108.8
C5—C4—H4A119.6O2—C14—C13103.35 (10)
C3—C4—H4A119.6O2—C14—H14A111.1
C4—C5—C6119.03 (12)C13—C14—H14A111.1
C4—C5—H5A120.5O2—C14—H14B111.1
C6—C5—H5A120.5C13—C14—H14B111.1
C5—C6—C1118.98 (11)H14A—C14—H14B109.1
C5—C6—C7134.14 (11)N1—C15—C16112.31 (9)
C1—C6—C7106.87 (10)N1—C15—H15A109.1
C12—C7—C6107.24 (10)C16—C15—H15A109.1
C12—C7—C8123.20 (11)N1—C15—H15B109.1
C6—C7—C8129.47 (10)C16—C15—H15B109.1
C7—C8—C9110.13 (10)H15A—C15—H15B107.9
C7—C8—H8A109.6O3—C16—O4124.27 (10)
C9—C8—H8A109.6O3—C16—C15124.99 (10)
C7—C8—H8B109.6O4—C16—C15110.74 (9)
C9—C8—H8B109.6O4—C17—C18107.80 (10)
H8A—C8—H8B108.1O4—C17—H17A110.1
O2—C9—O1105.70 (9)C18—C17—H17A110.1
O2—C9—C10108.03 (10)O4—C17—H17B110.1
O1—C9—C10110.29 (10)C18—C17—H17B110.1
O2—C9—C8111.67 (10)H17A—C17—H17B108.5
O1—C9—C8108.76 (10)C17—C18—H18A109.5
C10—C9—C8112.19 (10)C17—C18—H18B109.5
C9—C10—C11112.18 (10)H18A—C18—H18B109.5
C9—C10—H10A109.2C17—C18—H18C109.5
C11—C10—H10A109.2H18A—C18—H18C109.5
C9—C10—H10B109.2H18B—C18—H18C109.5
C11—C10—H10B109.2
C12—N1—C1—C2−179.74 (11)C7—C8—C9—O276.13 (12)
C15—N1—C1—C20.15 (19)C7—C8—C9—O1−167.60 (9)
C12—N1—C1—C61.15 (12)C7—C8—C9—C10−45.32 (13)
C15—N1—C1—C6−178.96 (9)O2—C9—C10—C11−61.20 (12)
N1—C1—C2—C3−178.46 (12)O1—C9—C10—C11−176.27 (9)
C6—C1—C2—C30.54 (18)C8—C9—C10—C1162.32 (13)
C1—C2—C3—C40.1 (2)C9—C10—C11—C12−43.12 (13)
C2—C3—C4—C5−0.5 (2)C6—C7—C12—N10.87 (12)
C3—C4—C5—C60.20 (19)C8—C7—C12—N1−176.05 (9)
C4—C5—C6—C10.41 (16)C6—C7—C12—C11178.28 (10)
C4—C5—C6—C7179.11 (12)C8—C7—C12—C111.36 (17)
N1—C1—C6—C5178.40 (10)C1—N1—C12—C7−1.28 (12)
C2—C1—C6—C5−0.80 (16)C15—N1—C12—C7178.83 (10)
N1—C1—C6—C7−0.62 (11)C1—N1—C12—C11−178.72 (10)
C2—C1—C6—C7−179.82 (10)C15—N1—C12—C111.39 (16)
C5—C6—C7—C12−178.95 (12)C10—C11—C12—C712.73 (15)
C1—C6—C7—C12−0.15 (12)C10—C11—C12—N1−170.22 (10)
C5—C6—C7—C8−2.3 (2)C9—O1—C13—C145.60 (16)
C1—C6—C7—C8176.51 (11)C9—O2—C14—C1331.96 (14)
C12—C7—C8—C914.73 (15)O1—C13—C14—O2−23.07 (16)
C6—C7—C8—C9−161.45 (11)C1—N1—C15—C16−97.30 (13)
C14—O2—C9—O1−29.21 (13)C12—N1—C15—C1682.58 (13)
C14—O2—C9—C10−147.26 (10)C17—O4—C16—O3−3.87 (17)
C14—O2—C9—C888.91 (12)C17—O4—C16—C15176.02 (10)
C13—O1—C9—O214.11 (14)N1—C15—C16—O35.41 (17)
C13—O1—C9—C10130.64 (12)N1—C15—C16—O4−174.47 (9)
C13—O1—C9—C8−105.93 (13)C16—O4—C17—C18176.84 (10)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2485).

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.
  • 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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