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The carbazole unit of the title mol­ecule, C15H15NO3, is not planar. The dihedral angle between the benzene ring and the fused pyrrole ring is 0.9 (1)°. The cyclo­hexene ring is in a half-chair form. The ester group has an equatorial orientation. In the crystal structure, the mol­ecules are stabilized by inter­molecular C—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680702644X/bq2018sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680702644X/bq2018Isup2.hkl
Contains datablock I

CCDC reference: 654869

Key indicators

  • Single-crystal X-ray study
  • T = 203 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.067
  • wR factor = 0.177
  • Data-to-parameter ratio = 21.0

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.67 mm PLAT128_ALERT_4_C Non-standard setting of Space group P21/c .... P21/a
Alert level G PLAT793_ALERT_1_G Check the Absolute Configuration of C2 = ... S
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The molecular structure of (I), with atomic numbering scheme, is shown in Fig. 1. The carbazole unit is not planar. The dihedral angle between the benzene ring and the fused pyrrole ring is 0.9 (1)°. The cyclohexene ring is in half-chair form. In the crystal structure, the molecules are stabilized by intermolecular C9—H9A···O21(x + 1, y, z) and C22—H22B···O1(-x + 1/2, y + 1/2, -z) hydrogen bonds (Fig. 2).

Related literature top

For related literature, see: Knolker & Reddy (2002); Gunaseelan et al. (2007a,b). Due to the interesting and important properties of carbazoles, a number of methodologies for the construction of the carbazole ring with other heterocyclic compounds have been reported (Knolker & Reddy, 2002). Gunaseelan et al. (2007a,b) have reported crystal structures of substituted carbazole derivatives, wherein the carbazole units are not planar.

Experimental top

The mixture of 9-methyl-1,2,3,4-tetrahydrocarbazol-1-one (200 mg, 0.001 mol), dimethyl carbonate (2 ml), sodium hydride in mineral oil (300 mg), catalytic amount of potassium hydride (0.030 mg) [CAUTION: Potassium hydride is highly pyrophoric in dry condition] was refluxed on a water bath for 3 h. After cooling the mixture was carefully neutralized using glacial acetic acid and then poured into crushed ice. It was extracted with ethyl acetate and purified by column chromatography over silica gel using petroleum ether/ethyl acetate (98:2) as eluant to get the pure compound (I) (205 mg, 80%). It was recrystallized using glacial acetic acid.

Refinement top

All H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93–0.98 Å and Uiso(H) = 1.2 to 1.5 times Ueq(C).

Structure description top

The molecular structure of (I), with atomic numbering scheme, is shown in Fig. 1. The carbazole unit is not planar. The dihedral angle between the benzene ring and the fused pyrrole ring is 0.9 (1)°. The cyclohexene ring is in half-chair form. In the crystal structure, the molecules are stabilized by intermolecular C9—H9A···O21(x + 1, y, z) and C22—H22B···O1(-x + 1/2, y + 1/2, -z) hydrogen bonds (Fig. 2).

For related literature, see: Knolker & Reddy (2002); Gunaseelan et al. (2007a,b). Due to the interesting and important properties of carbazoles, a number of methodologies for the construction of the carbazole ring with other heterocyclic compounds have been reported (Knolker & Reddy, 2002). Gunaseelan et al. (2007a,b) have reported crystal structures of substituted carbazole derivatives, wherein the carbazole units are not planar.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. The molecular packing of (I), viewed down the b axis. Dashed lines indicate hydrogen bonds.
Methyl 9-methyl-1-oxo-2,3,4,9-tetrahydro-1H-carbazole-2-carboxylate top
Crystal data top
C15H15NO3F(000) = 544
Mr = 257.28Dx = 1.324 Mg m3
Monoclinic, P21/aMelting point: 361(1) K
Hall symbol: -P 2yabMo Kα radiation, λ = 0.71073 Å
a = 9.1267 (3) ÅCell parameters from 7041 reflections
b = 8.2114 (3) Åθ = 4.7–30.7°
c = 17.2304 (9) ŵ = 0.09 mm1
β = 91.151 (4)°T = 203 K
V = 1291.04 (9) Å3Plate, colourless
Z = 40.67 × 0.35 × 0.32 mm
Data collection top
Oxford Diffraction Gemini
diffractometer
2639 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray SourceRint = 0.038
Graphite monochromatorθmax = 30.7°, θmin = 4.7°
φ and ω scansh = 1312
13753 measured reflectionsk = 1110
3646 independent reflectionsl = 2323
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)] = 0.067Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.177H-atom parameters constrained
S = 1.14 w = 1/[σ2(Fo2) + (0.0581P)2 + 0.8204P]
where P = (Fo2 + 2Fc2)/3
3646 reflections(Δ/σ)max < 0.001
174 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C15H15NO3V = 1291.04 (9) Å3
Mr = 257.28Z = 4
Monoclinic, P21/aMo Kα radiation
a = 9.1267 (3) ŵ = 0.09 mm1
b = 8.2114 (3) ÅT = 203 K
c = 17.2304 (9) Å0.67 × 0.35 × 0.32 mm
β = 91.151 (4)°
Data collection top
Oxford Diffraction Gemini
diffractometer
2639 reflections with I > 2σ(I)
13753 measured reflectionsRint = 0.038
3646 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0670 restraints
wR(F2) = 0.177H-atom parameters constrained
S = 1.14Δρmax = 0.35 e Å3
3646 reflectionsΔρmin = 0.18 e Å3
174 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
O10.41622 (18)0.4836 (2)0.11376 (10)0.0517 (5)
O210.06438 (19)0.5261 (2)0.15535 (11)0.0624 (7)
O220.17217 (18)0.7308 (2)0.09356 (9)0.0506 (5)
N90.66243 (17)0.4350 (2)0.22709 (11)0.0383 (5)
C10.4145 (2)0.5367 (2)0.17927 (12)0.0360 (6)
C20.2865 (2)0.6423 (2)0.20840 (12)0.0375 (6)
C30.2474 (2)0.5956 (3)0.29114 (13)0.0439 (6)
C40.3767 (2)0.6254 (3)0.34675 (12)0.0444 (7)
C4A0.5123 (2)0.5489 (2)0.31546 (12)0.0359 (6)
C4B0.6424 (2)0.4969 (2)0.35477 (12)0.0380 (6)
C50.6906 (3)0.5009 (3)0.43246 (14)0.0485 (7)
C60.8261 (3)0.4360 (3)0.45130 (16)0.0572 (8)
C70.9150 (3)0.3685 (3)0.39403 (17)0.0557 (9)
C80.8729 (2)0.3644 (3)0.31774 (16)0.0486 (8)
C8A0.7334 (2)0.4271 (2)0.29785 (13)0.0383 (6)
C90.7206 (2)0.3755 (3)0.15384 (14)0.0473 (7)
C9A0.5280 (2)0.5097 (2)0.23855 (12)0.0348 (6)
C210.1608 (2)0.6243 (3)0.15081 (13)0.0418 (6)
C220.0692 (3)0.7132 (4)0.02922 (15)0.0645 (10)
H20.318300.757540.208470.0450*
H3A0.163140.660140.307560.0526*
H3B0.219730.480360.292730.0526*
H4A0.391990.742740.353280.0533*
H4B0.355600.578710.397670.0533*
H50.631870.546800.470940.0583*
H60.859430.437000.503280.0686*
H71.006550.324710.408810.0669*
H80.934600.321310.279810.0584*
H9A0.825700.360470.159350.0709*
H9B0.699920.454220.113090.0709*
H9C0.674700.272420.140520.0709*
H22A0.088880.612570.001870.0968*
H22B0.079420.804500.005990.0968*
H22C0.029820.710840.048630.0968*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0440 (9)0.0605 (10)0.0508 (9)0.0004 (7)0.0052 (7)0.0159 (8)
O210.0402 (9)0.0697 (12)0.0770 (13)0.0125 (8)0.0038 (8)0.0176 (10)
O220.0592 (10)0.0453 (9)0.0472 (9)0.0008 (8)0.0009 (7)0.0056 (7)
N90.0304 (8)0.0309 (8)0.0540 (11)0.0005 (6)0.0114 (7)0.0041 (7)
C10.0320 (9)0.0334 (9)0.0430 (11)0.0033 (7)0.0087 (8)0.0001 (8)
C20.0336 (9)0.0316 (9)0.0475 (11)0.0045 (7)0.0060 (8)0.0026 (8)
C30.0311 (9)0.0505 (12)0.0504 (12)0.0118 (9)0.0100 (8)0.0041 (10)
C40.0383 (10)0.0569 (13)0.0383 (11)0.0125 (9)0.0099 (8)0.0017 (9)
C4A0.0315 (9)0.0316 (9)0.0450 (11)0.0014 (7)0.0090 (8)0.0040 (8)
C4B0.0308 (9)0.0325 (9)0.0509 (12)0.0006 (7)0.0077 (8)0.0079 (8)
C50.0401 (11)0.0558 (14)0.0499 (13)0.0037 (10)0.0061 (9)0.0109 (10)
C60.0436 (12)0.0669 (16)0.0609 (15)0.0017 (12)0.0019 (11)0.0159 (12)
C70.0348 (11)0.0501 (14)0.0822 (19)0.0085 (10)0.0021 (11)0.0109 (12)
C80.0333 (10)0.0353 (11)0.0776 (17)0.0060 (8)0.0088 (10)0.0010 (10)
C8A0.0303 (9)0.0266 (9)0.0583 (13)0.0002 (7)0.0077 (8)0.0036 (8)
C90.0374 (10)0.0412 (11)0.0638 (14)0.0042 (9)0.0158 (10)0.0125 (10)
C9A0.0295 (9)0.0277 (9)0.0476 (11)0.0009 (7)0.0100 (7)0.0004 (8)
C210.0381 (10)0.0401 (11)0.0474 (12)0.0054 (8)0.0073 (9)0.0016 (9)
C220.0790 (19)0.0707 (18)0.0437 (14)0.0033 (15)0.0046 (12)0.0015 (12)
Geometric parameters (Å, º) top
O1—C11.210 (3)C6—C71.404 (4)
O21—C211.197 (3)C7—C81.363 (4)
O22—C211.324 (3)C8—C8A1.409 (3)
O22—C221.446 (3)C2—H20.9900
N9—C8A1.371 (3)C3—H3A0.9800
N9—C91.463 (3)C3—H3B0.9800
N9—C9A1.389 (2)C4—H4A0.9800
C1—C21.547 (3)C4—H4B0.9800
C1—C9A1.457 (3)C5—H50.9400
C2—C31.526 (3)C6—H60.9400
C2—C211.509 (3)C7—H70.9400
C3—C41.525 (3)C8—H80.9400
C4—C4A1.498 (3)C9—H9A0.9700
C4A—C4B1.421 (3)C9—H9B0.9700
C4A—C9A1.374 (3)C9—H9C0.9700
C4B—C51.401 (3)C22—H22A0.9700
C4B—C8A1.419 (3)C22—H22B0.9700
C5—C61.379 (4)C22—H22C0.9700
O1···O223.028 (2)C9···H82.9200
O1···N92.974 (2)C9A···H8v2.9400
O1···C92.984 (3)C9A···H3B2.9900
O1···C22i3.217 (3)C22···H22Aix3.0800
O1···C22ii3.321 (3)H2···C4A3.0600
O21···C9iii3.372 (3)H2···H4A2.5700
O22···C1iv3.391 (2)H2···N9iv2.9200
O22···O13.028 (2)H3A···C4Aiv2.7600
O1···H22Bii2.3700H3A···C4Biv2.9400
O1···H9B2.6000H3B···O212.7600
O1···H22Ci2.8000H3B···C9A2.9900
O21···H9Aiii2.5700H4A···H22.5700
O21···H3B2.7600H4B···C5viii3.0400
O21···H9Cv2.6600H4B···H5viii2.4900
O21···H22A2.7500H5···H4Bviii2.4900
O21···H22C2.5200H7···C4Bx3.0700
O22···H9Biv2.6200H8···C92.9200
O22···H22Ci2.8800H8···H9A2.3100
N9···O12.974 (2)H8···C9Ax2.9400
N9···H2i2.9200H9A···O21vi2.5700
C1···O22i3.391 (2)H9A···C82.7500
C9···O21vi3.372 (3)H9A···H82.3100
C9···O12.984 (3)H9B···O12.6000
C9A···C21i3.586 (3)H9B···C12.9400
C21···C9Aiv3.586 (3)H9B···O22i2.6200
C22···O1iv3.217 (3)H9C···O21x2.6600
C22···O1vii3.321 (3)H22A···O212.7500
C1···H9B2.9400H22A···C22ix3.0800
C4A···H23.0600H22A···H22Aix2.4600
C4A···H3Ai2.7600H22B···O1vii2.3700
C4B···H3Ai2.9400H22C···O212.5200
C4B···H7v3.0700H22C···O1iv2.8000
C5···H4Bviii3.0400H22C···O22iv2.8800
C8···H9A2.7500
C21—O22—C22116.47 (19)C3—C2—H2108.00
C8A—N9—C9125.34 (16)C21—C2—H2108.00
C8A—N9—C9A107.30 (17)C2—C3—H3A109.00
C9—N9—C9A127.36 (17)C2—C3—H3B110.00
O1—C1—C2121.91 (18)C4—C3—H3A109.00
O1—C1—C9A125.21 (17)C4—C3—H3B110.00
C2—C1—C9A112.88 (17)H3A—C3—H3B108.00
C1—C2—C3110.78 (16)C3—C4—H4A110.00
C1—C2—C21107.51 (16)C3—C4—H4B110.00
C3—C2—C21113.63 (16)C4A—C4—H4A110.00
C2—C3—C4110.75 (16)C4A—C4—H4B110.00
C3—C4—C4A109.94 (17)H4A—C4—H4B108.00
C4—C4A—C4B130.02 (18)C4B—C5—H5121.00
C4—C4A—C9A123.25 (17)C6—C5—H5121.00
C4B—C4A—C9A106.68 (16)C5—C6—H6119.00
C4A—C4B—C5133.8 (2)C7—C6—H6120.00
C4A—C4B—C8A106.68 (18)C6—C7—H7119.00
C5—C4B—C8A119.54 (19)C8—C7—H7119.00
C4B—C5—C6118.6 (2)C7—C8—H8121.00
C5—C6—C7121.0 (2)C8A—C8—H8121.00
C6—C7—C8122.1 (2)N9—C9—H9A109.00
C7—C8—C8A117.5 (2)N9—C9—H9B109.00
N9—C8A—C4B108.85 (16)N9—C9—H9C109.00
N9—C8A—C8130.0 (2)H9A—C9—H9B109.00
C4B—C8A—C8121.2 (2)H9A—C9—H9C109.00
N9—C9A—C1125.80 (18)H9B—C9—H9C109.00
N9—C9A—C4A110.49 (17)O22—C22—H22A110.00
C1—C9A—C4A123.64 (17)O22—C22—H22B109.00
O21—C21—O22124.2 (2)O22—C22—H22C109.00
O21—C21—C2125.0 (2)H22A—C22—H22B109.00
O22—C21—C2110.82 (17)H22A—C22—H22C109.00
C1—C2—H2108.00H22B—C22—H22C109.00
C22—O22—C21—C2172.37 (19)C1—C2—C3—C461.9 (2)
C22—O22—C21—O216.8 (3)C2—C3—C4—C4A50.2 (2)
C9—N9—C8A—C80.4 (3)C3—C4—C4A—C9A20.5 (3)
C9A—N9—C8A—C4B0.30 (19)C3—C4—C4A—C4B156.62 (19)
C8A—N9—C9A—C1177.24 (16)C4—C4A—C4B—C51.6 (4)
C8A—N9—C9A—C4A0.2 (2)C9A—C4A—C4B—C8A0.19 (19)
C9A—N9—C8A—C8179.3 (2)C4—C4A—C4B—C8A177.68 (19)
C9—N9—C8A—C4B180.00 (17)C9A—C4A—C4B—C5179.1 (2)
C9—N9—C9A—C4A179.87 (19)C4B—C4A—C9A—N90.0 (2)
C9—N9—C9A—C13.1 (3)C4B—C4A—C9A—C1177.13 (16)
O1—C1—C2—C2114.5 (2)C4—C4A—C9A—N9177.72 (17)
O1—C1—C2—C3139.23 (19)C4—C4A—C9A—C10.6 (3)
O1—C1—C9A—N97.6 (3)C4A—C4B—C5—C6179.1 (2)
C9A—C1—C2—C340.5 (2)C4A—C4B—C8A—C8179.35 (18)
C9A—C1—C2—C21165.21 (16)C8A—C4B—C5—C60.1 (3)
C2—C1—C9A—C4A10.6 (2)C4A—C4B—C8A—N90.30 (19)
C2—C1—C9A—N9172.67 (16)C5—C4B—C8A—C81.3 (3)
O1—C1—C9A—C4A169.09 (18)C5—C4B—C8A—N9179.10 (18)
C21—C2—C3—C4176.95 (18)C4B—C5—C6—C70.6 (4)
C1—C2—C21—O2192.4 (2)C5—C6—C7—C80.3 (4)
C3—C2—C21—O2130.6 (3)C6—C7—C8—C8A1.7 (4)
C3—C2—C21—O22150.21 (18)C7—C8—C8A—C4B2.1 (3)
C1—C2—C21—O2286.8 (2)C7—C8—C8A—N9178.3 (2)
Symmetry codes: (i) x+1/2, y+3/2, z; (ii) x+1/2, y1/2, z; (iii) x1, y, z; (iv) x1/2, y+3/2, z; (v) x1/2, y+1/2, z; (vi) x+1, y, z; (vii) x+1/2, y+1/2, z; (viii) x+1, y+1, z+1; (ix) x, y+1, z; (x) x+1/2, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9A···O21vi0.972.573.372 (3)140
C22—H22B···O1vii0.972.373.321 (3)167
Symmetry codes: (vi) x+1, y, z; (vii) x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formulaC15H15NO3
Mr257.28
Crystal system, space groupMonoclinic, P21/a
Temperature (K)203
a, b, c (Å)9.1267 (3), 8.2114 (3), 17.2304 (9)
β (°) 91.151 (4)
V3)1291.04 (9)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.67 × 0.35 × 0.32
Data collection
DiffractometerOxford Diffraction Gemini
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
13753, 3646, 2639
Rint0.038
(sin θ/λ)max1)0.719
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.067, 0.177, 1.14
No. of reflections3646
No. of parameters174
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.35, 0.18

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis CCD, CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997b), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9A···O21i0.972.573.372 (3)140
C22—H22B···O1ii0.972.373.321 (3)167
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, y+1/2, z.
 

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