organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

aUniversity of Southern Denmark, Department of Physics and Chemistry, Campusvej 55, 5230 Odense M, Denmark
*Correspondence e-mail: adb@chem.sdu.dk

(Received 19 February 2009; accepted 1 March 2009; online 6 March 2009)

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[Ulven, T. & Kostenis, E. (2005). J. Med. Chem. 48, 897-900.], 2006[Ulven, T. & Kostenis, E. (2006). Curr. Top. Med. Chem. 6, 1427-1444.]). For a related structure, see: Bjerrum et al. (2009[Bjerrum, J. V., Ulven, T. & Bond, A. D. (2009). Acta Cryst. E65, o579.]).

[Scheme 1]

Experimental

Crystal data
  • C18H21NO4

  • Mr = 315.36

  • Monoclinic, P 21 /c

  • 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[Sheldrick, G. M. (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.847, Tmax = 0.991

  • 25055 measured reflections

  • 3851 independent reflections

  • 3174 reflections with I > 2σ(I)

  • Rint = 0.025

Refinement
  • R[F2 > 2σ(F2)] = 0.040

  • wR(F2) = 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[Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2003[Bruker (2003). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

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

Related literature top

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

Experimental top

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

Refinement top

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.

Computing details top

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

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound with displacement ellipsoids shown at 50% probability for non-H atoms.
[Figure 2] Fig. 2. Packing diagram viewed along the c axis, showing stacked carbazole units. H atoms are omitted.
Ethyl 2-(1,2,3,4-tetrahydrospiro[carbazole-3,2'-[1,3]dioxolan]-9-yl)acetate top
Crystal data top
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 top
Bruker-Nonius X8 APEXII CCD
diffractometer
3851 independent reflections
Radiation source: fine-focus sealed tube3174 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
thin–slice ω and ϕ scansθmax = 28.3°, θmin = 3.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 1313
Tmin = 0.847, Tmax = 0.991k = 2321
25055 measured reflectionsl = 1111
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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112H-atom parameters constrained
S = 1.04 w = 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
Crystal data top
C18H21NO4V = 1583.05 (10) Å3
Mr = 315.36Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.5533 (4) ŵ = 0.09 mm1
b = 17.3773 (6) ÅT = 180 K
c = 8.9637 (3) Å0.50 × 0.50 × 0.10 mm
β = 105.629 (1)°
Data collection top
Bruker-Nonius X8 APEXII CCD
diffractometer
3851 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
3174 reflections with I > 2σ(I)
Tmin = 0.847, Tmax = 0.991Rint = 0.025
25055 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.112H-atom parameters constrained
S = 1.04Δρmax = 0.28 e Å3
3851 reflectionsΔρmin = 0.25 e Å3
208 parameters
Special details top

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) top
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*
H18B0.35340.00060.38350.061*
H18C0.26130.07290.32850.061*
Atomic displacement parameters (Å2) top
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, º) top
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—C2179.74 (11)C7—C8—C9—O276.13 (12)
C15—N1—C1—C20.15 (19)C7—C8—C9—O1167.60 (9)
C12—N1—C1—C61.15 (12)C7—C8—C9—C1045.32 (13)
C15—N1—C1—C6178.96 (9)O2—C9—C10—C1161.20 (12)
N1—C1—C2—C3178.46 (12)O1—C9—C10—C11176.27 (9)
C6—C1—C2—C30.54 (18)C8—C9—C10—C1162.32 (13)
C1—C2—C3—C40.1 (2)C9—C10—C11—C1243.12 (13)
C2—C3—C4—C50.5 (2)C6—C7—C12—N10.87 (12)
C3—C4—C5—C60.20 (19)C8—C7—C12—N1176.05 (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—C71.28 (12)
C2—C1—C6—C50.80 (16)C15—N1—C12—C7178.83 (10)
N1—C1—C6—C70.62 (11)C1—N1—C12—C11178.72 (10)
C2—C1—C6—C7179.82 (10)C15—N1—C12—C111.39 (16)
C5—C6—C7—C12178.95 (12)C10—C11—C12—C712.73 (15)
C1—C6—C7—C120.15 (12)C10—C11—C12—N1170.22 (10)
C5—C6—C7—C82.3 (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—O223.07 (16)
C6—C7—C8—C9161.45 (11)C1—N1—C15—C1697.30 (13)
C14—O2—C9—O129.21 (13)C12—N1—C15—C1682.58 (13)
C14—O2—C9—C10147.26 (10)C17—O4—C16—O33.87 (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—O4174.47 (9)
C13—O1—C9—C8105.93 (13)C16—O4—C17—C18176.84 (10)

Experimental details

Crystal data
Chemical formulaC18H21NO4
Mr315.36
Crystal system, space groupMonoclinic, P21/c
Temperature (K)180
a, b, c (Å)10.5533 (4), 17.3773 (6), 8.9637 (3)
β (°) 105.629 (1)
V3)1583.05 (10)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.50 × 0.50 × 0.10
Data collection
DiffractometerBruker-Nonius X8 APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.847, 0.991
No. of measured, independent and
observed [I > 2σ(I)] reflections
25055, 3851, 3174
Rint0.025
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.112, 1.04
No. of reflections3851
No. of parameters208
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.28, 0.25

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

 

Acknowledgements

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

References

First citationBjerrum, J. V., Ulven, T. & Bond, A. D. (2009). Acta Cryst. E65, o579.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationBruker (2003). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationSheldrick, G. M. (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationUlven, T. & Kostenis, E. (2005). J. Med. Chem. 48, 897–900.  Web of Science CrossRef PubMed CAS Google Scholar
First citationUlven, T. & Kostenis, E. (2006). Curr. Top. Med. Chem. 6, 1427–1444.  Web of Science CrossRef PubMed CAS Google Scholar

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
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