1,2-Di­hydro­spiro­[carbazole-3(4H),2′-[1,3]dioxolane]

Bjerrum, J.V.; Ulven, T.; Bond, A.D.

doi:10.1107/S1600536809005558

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o579

doi:10.1107/S1600536809005558

Open

access

1,2-Dihydrospiro[carbazole-3(4H),2′-[1,3]dioxolane]

Janni Vester Bjerrum,^a Trond Ulven ^a and Andrew D. Bond ^a ^*

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

(Received 29 January 2009; accepted 16 February 2009; online 21 February 2009)

In the title compound, C₁₄H₁₅NO₂, the hydrogenated six-membered ring of the carbazole unit adopts a half-chair conformation and the dioxolane ring points to one side of the carbazole plane. Neighbouring molecules form edge-to-face interactions in which the NH group is directed towards an adjacent carbazole unit, with a shortest H⋯C contact of 2.72 Å. These interactions arrange the molecules into one-dimensional herringbone-type motifs, which pack so that the methylene groups of the dioxolane ring lie over the face of a neighbouring carbazole unit with a shortest H⋯C contact of 2.85 Å.

Related literature

For background literature and synthesis details, see: Ulven & Kostenis (2006 ); Urrutia & Rodriguez (1999 ).

Experimental

Crystal data

C₁₄H₁₅NO₂
M_r = 229.27
Monoclinic, P 2₁
a = 9.3781 (6) Å
b = 6.1467 (4) Å
c = 10.5740 (7) Å
β = 115.232 (2)°
V = 551.38 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 180 K
0.50 × 0.50 × 0.40 mm

Data collection

Bruker–Nonius X8 APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.812, T_max = 0.964
7776 measured reflections
1485 independent reflections
1427 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.080
S = 1.05
1485 reflections
154 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯C1ⁱ	0.88	2.72	3.527 (2)	154
C14—H14A⋯C12ⁱⁱ	0.99	2.85	3.518 (3)	126
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2003 ); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809005558/ya2088sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809005558/ya2088Isup2.hkl

checkCIF report

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); Urrutia & Rodriguez (1999).

Experimental top

The compound was synthesized as described in Urrutia & Rodriguez (1999).

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

	Fig. 1. Molecular structure of the title compound with displacement ellipsoids shown at 50% probability for non-H atoms.
	Fig. 2. Projection along b showing interactions between carbazole units (e.g. about the origin), and between dioxolane rings and carbazole units (e.g. at the centre of the unit cell). H atoms are omitted.

1,2-Dihydrospiro[carbazole-3(4H),2'-[1,3]dioxolane] top

Crystal data top

C₁₄H₁₅NO₂	F(000) = 244
M_r = 229.27	D_x = 1.381 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 5883 reflections
a = 9.3781 (6) Å	θ = 2.4–28.4°
b = 6.1467 (4) Å	µ = 0.09 mm⁻¹
c = 10.5740 (7) Å	T = 180 K
β = 115.232 (2)°	Block, colourless
V = 551.38 (6) Å³	0.50 × 0.50 × 0.40 mm
Z = 2

Data collection top

Bruker–Nonius X8 APEXII CCD diffractometer	1485 independent reflections
Radiation source: fine-focus sealed tube	1427 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
Thin–slice ω and ϕ scans	θ_max = 28.4°, θ_min = 3.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −12→12
T_min = 0.812, T_max = 0.964	k = −8→8
7776 measured reflections	l = −11→14

Refinement top

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0581P)² + 0.0517P] where P = (F_o² + 2F_c²)/3
1485 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.33 e Å⁻³
1 restraint	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₄H₁₅NO₂	V = 551.38 (6) Å³
M_r = 229.27	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 9.3781 (6) Å	µ = 0.09 mm⁻¹
b = 6.1467 (4) Å	T = 180 K
c = 10.5740 (7) Å	0.50 × 0.50 × 0.40 mm
β = 115.232 (2)°

Data collection top

Bruker–Nonius X8 APEXII CCD diffractometer	1485 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1427 reflections with I > 2σ(I)
T_min = 0.812, T_max = 0.964	R_int = 0.017
7776 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	1 restraint
wR(F²) = 0.080	H-atom parameters constrained
S = 1.05	Δρ_max = 0.33 e Å⁻³
1485 reflections	Δρ_min = −0.16 e Å⁻³
154 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

	x	y	z	U_iso*/U_eq
O1	0.23032 (12)	0.56670 (18)	0.55448 (11)	0.0256 (2)
O2	0.36610 (11)	0.26085 (18)	0.56040 (10)	0.0238 (2)
N1	0.10724 (14)	−0.0286 (2)	0.12685 (12)	0.0259 (3)
H1A	0.0579	−0.1545	0.1083	0.031*
C1	0.17592 (15)	0.0682 (3)	0.04893 (14)	0.0240 (3)
C2	0.18695 (18)	−0.0023 (3)	−0.07194 (15)	0.0321 (3)
H2A	0.1415	−0.1362	−0.1153	0.038*
C3	0.2665 (2)	0.1299 (4)	−0.12652 (16)	0.0373 (4)
H3A	0.2752	0.0863	−0.2092	0.045*
C4	0.3344 (2)	0.3267 (3)	−0.06233 (18)	0.0368 (4)
H4A	0.3891	0.4134	−0.1017	0.044*
C5	0.32330 (18)	0.3972 (3)	0.05741 (15)	0.0296 (3)
H5A	0.3694	0.5312	0.1000	0.036*
C6	0.24301 (15)	0.2675 (3)	0.11475 (13)	0.0223 (3)
C7	0.21109 (15)	0.2855 (2)	0.23567 (13)	0.0206 (3)
C8	0.25187 (17)	0.4636 (2)	0.34150 (14)	0.0229 (3)
H8A	0.1820	0.5900	0.3001	0.027*
H8B	0.3620	0.5107	0.3687	0.027*
C9	0.23321 (15)	0.3857 (2)	0.47164 (14)	0.0202 (3)
C10	0.08364 (15)	0.2549 (3)	0.43550 (14)	0.0235 (3)
H10A	−0.0086	0.3484	0.3823	0.028*
H10B	0.0775	0.2110	0.5231	0.028*
C11	0.07498 (17)	0.0513 (2)	0.34942 (15)	0.0249 (3)
H11A	0.1428	−0.0641	0.4112	0.030*
H11B	−0.0347	−0.0034	0.3056	0.030*
C12	0.12847 (15)	0.1046 (2)	0.23882 (13)	0.0217 (3)
C13	0.39081 (17)	0.6225 (3)	0.63924 (16)	0.0275 (3)
H13A	0.4055	0.6671	0.7340	0.033*
H13B	0.4255	0.7426	0.5965	0.033*
C14	0.48246 (17)	0.4138 (3)	0.64530 (17)	0.0303 (3)
H14A	0.5615	0.4393	0.6079	0.036*
H14B	0.5372	0.3606	0.7427	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0236 (5)	0.0230 (5)	0.0319 (5)	0.0007 (4)	0.0134 (4)	−0.0055 (4)
O2	0.0198 (4)	0.0193 (5)	0.0280 (5)	0.0008 (4)	0.0061 (4)	0.0010 (4)
N1	0.0248 (6)	0.0226 (6)	0.0263 (6)	−0.0051 (5)	0.0071 (5)	−0.0031 (5)
C1	0.0195 (6)	0.0260 (7)	0.0206 (6)	0.0007 (5)	0.0029 (5)	0.0009 (5)
C2	0.0297 (7)	0.0371 (9)	0.0223 (6)	0.0005 (7)	0.0042 (5)	−0.0049 (6)
C3	0.0367 (8)	0.0505 (11)	0.0229 (6)	0.0035 (8)	0.0110 (6)	0.0002 (7)
C4	0.0379 (8)	0.0461 (10)	0.0293 (7)	−0.0009 (8)	0.0171 (7)	0.0055 (7)
C5	0.0315 (7)	0.0307 (7)	0.0266 (6)	−0.0033 (7)	0.0123 (6)	0.0037 (6)
C6	0.0200 (5)	0.0221 (6)	0.0209 (6)	0.0013 (5)	0.0049 (5)	0.0021 (5)
C7	0.0188 (5)	0.0195 (6)	0.0217 (6)	0.0003 (5)	0.0069 (5)	0.0024 (5)
C8	0.0271 (6)	0.0168 (6)	0.0263 (6)	−0.0022 (5)	0.0130 (5)	0.0012 (5)
C9	0.0192 (5)	0.0169 (6)	0.0251 (6)	0.0009 (5)	0.0100 (5)	−0.0009 (5)
C10	0.0191 (6)	0.0245 (7)	0.0283 (6)	−0.0021 (5)	0.0113 (5)	0.0002 (6)
C11	0.0246 (6)	0.0212 (7)	0.0303 (7)	−0.0056 (5)	0.0128 (5)	−0.0005 (5)
C12	0.0186 (5)	0.0195 (6)	0.0239 (6)	−0.0004 (5)	0.0062 (5)	0.0009 (5)
C13	0.0284 (7)	0.0233 (7)	0.0283 (6)	−0.0032 (6)	0.0099 (6)	−0.0020 (5)
C14	0.0227 (6)	0.0304 (8)	0.0323 (7)	−0.0011 (6)	0.0065 (6)	−0.0065 (6)

Geometric parameters (Å, º) top

O1—C9	1.4234 (17)	C7—C12	1.3639 (19)
O1—C13	1.4270 (17)	C7—C8	1.4936 (19)
O2—C9	1.4233 (16)	C8—C9	1.5358 (18)
O2—C14	1.4303 (18)	C8—H8A	0.990
N1—C1	1.3785 (19)	C8—H8B	0.990
N1—C12	1.3822 (18)	C9—C10	1.5177 (18)
N1—H1A	0.880	C10—C11	1.529 (2)
C1—C2	1.395 (2)	C10—H10A	0.990
C1—C6	1.417 (2)	C10—H10B	0.990
C2—C3	1.384 (3)	C11—C12	1.4922 (18)
C2—H2A	0.950	C11—H11A	0.990
C3—C4	1.400 (3)	C11—H11B	0.990
C3—H3A	0.950	C13—C14	1.530 (2)
C4—C5	1.383 (2)	C13—H13A	0.990
C4—H4A	0.950	C13—H13B	0.990
C5—C6	1.400 (2)	C14—H14A	0.990
C5—H5A	0.950	C14—H14B	0.990
C6—C7	1.4364 (18)

C9—O1—C13	106.42 (10)	O2—C9—C10	109.62 (11)
C9—O2—C14	106.18 (11)	O1—C9—C10	108.13 (11)
C1—N1—C12	108.84 (12)	O2—C9—C8	110.90 (10)
C1—N1—H1A	125.6	O1—C9—C8	110.32 (11)
C12—N1—H1A	125.6	C10—C9—C8	112.68 (11)
N1—C1—C2	130.52 (15)	C9—C10—C11	113.10 (11)
N1—C1—C6	107.60 (12)	C9—C10—H10A	109.0
C2—C1—C6	121.87 (14)	C11—C10—H10A	109.0
C3—C2—C1	117.59 (16)	C9—C10—H10B	109.0
C3—C2—H2A	121.2	C11—C10—H10B	109.0
C1—C2—H2A	121.2	H10A—C10—H10B	107.8
C2—C3—C4	121.30 (15)	C12—C11—C10	109.68 (12)
C2—C3—H3A	119.3	C12—C11—H11A	109.7
C4—C3—H3A	119.3	C10—C11—H11A	109.7
C5—C4—C3	121.20 (16)	C12—C11—H11B	109.7
C5—C4—H4A	119.4	C10—C11—H11B	109.7
C3—C4—H4A	119.4	H11A—C11—H11B	108.2
C4—C5—C6	118.84 (16)	C7—C12—N1	109.75 (12)
C4—C5—H5A	120.6	C7—C12—C11	125.61 (13)
C6—C5—H5A	120.6	N1—C12—C11	124.58 (13)
C5—C6—C1	119.19 (13)	O1—C13—C14	104.37 (12)
C5—C6—C7	134.15 (14)	O1—C13—H13A	110.9
C1—C6—C7	106.65 (12)	C14—C13—H13A	110.9
C12—C7—C6	107.16 (13)	O1—C13—H13B	110.9
C12—C7—C8	123.08 (12)	C14—C13—H13B	110.9
C6—C7—C8	129.75 (12)	H13A—C13—H13B	108.9
C7—C8—C9	110.64 (11)	O2—C14—C13	105.08 (11)
C7—C8—H8A	109.5	O2—C14—H14A	110.7
C9—C8—H8A	109.5	C13—C14—H14A	110.7
C7—C8—H8B	109.5	O2—C14—H14B	110.7
C9—C8—H8B	109.5	C13—C14—H14B	110.7
H8A—C8—H8B	108.1	H14A—C14—H14B	108.8
O2—C9—O1	104.87 (11)

C12—N1—C1—C2	179.41 (15)	C13—O1—C9—O2	36.02 (13)
C12—N1—C1—C6	0.36 (15)	C13—O1—C9—C10	152.93 (12)
N1—C1—C2—C3	−178.93 (15)	C13—O1—C9—C8	−83.44 (13)
C6—C1—C2—C3	0.0 (2)	C7—C8—C9—O2	79.85 (14)
C1—C2—C3—C4	0.4 (3)	C7—C8—C9—O1	−164.41 (11)
C2—C3—C4—C5	−0.6 (3)	C7—C8—C9—C10	−43.46 (16)
C3—C4—C5—C6	0.3 (3)	O2—C9—C10—C11	−64.65 (14)
C4—C5—C6—C1	0.2 (2)	O1—C9—C10—C11	−178.44 (11)
C4—C5—C6—C7	178.70 (16)	C8—C9—C10—C11	59.37 (16)
N1—C1—C6—C5	178.86 (13)	C9—C10—C11—C12	−42.89 (16)
C2—C1—C6—C5	−0.3 (2)	C6—C7—C12—N1	0.49 (15)
N1—C1—C6—C7	−0.06 (15)	C8—C7—C12—N1	179.18 (12)
C2—C1—C6—C7	−179.21 (13)	C6—C7—C12—C11	177.82 (13)
C5—C6—C7—C12	−178.94 (16)	C8—C7—C12—C11	−3.5 (2)
C1—C6—C7—C12	−0.27 (14)	C1—N1—C12—C7	−0.54 (15)
C5—C6—C7—C8	2.5 (3)	C1—N1—C12—C11	−177.90 (13)
C1—C6—C7—C8	−178.84 (13)	C10—C11—C12—C7	16.12 (19)
C12—C7—C8—C9	16.67 (18)	C10—C11—C12—N1	−166.94 (12)
C6—C7—C8—C9	−164.96 (13)	C9—O1—C13—C14	−22.68 (15)
C14—O2—C9—O1	−34.81 (13)	C9—O2—C14—C13	20.17 (14)
C14—O2—C9—C10	−150.69 (12)	O1—C13—C14—O2	1.51 (16)
C14—O2—C9—C8	84.26 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···C1ⁱ	0.88	2.72	3.527 (2)	154
C14—H14A···C12ⁱⁱ	0.99	2.85	3.518 (3)	126

Symmetry codes: (i) −x, y−1/2, −z; (ii) −x+1, y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₅NO₂
M_r	229.27
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	180
a, b, c (Å)	9.3781 (6), 6.1467 (4), 10.5740 (7)
β (°)	115.232 (2)
V (Å³)	551.38 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.50 × 0.50 × 0.40

Data collection
Diffractometer	Bruker–Nonius X8 APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.812, 0.964
No. of measured, independent and observed [I > 2σ(I)] reflections	7776, 1485, 1427
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.080, 1.05
No. of reflections	1485
No. of parameters	154
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.16

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···C1ⁱ	0.88	2.72	3.527 (2)	154.1
C14—H14A···C12ⁱⁱ	0.99	2.85	3.518 (3)	125.9

Symmetry codes: (i) −x, y−1/2, −z; (ii) −x+1, y+1/2, −z+1.

Acknowledgements

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

References

Bruker (2003). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ulven, T. & Kostenis, E. (2006). Curr. Top. Med. Chem. 6, 1427–1444. Web of Science CrossRef PubMed CAS Google Scholar
Urrutia, A. & Rodriguez, J. G. (1999). Tetrahedron, 55, 11095–11108. Web of Science CrossRef CAS Google Scholar