3-(9H-Carbazol-9-yl)-2H-chromen-2-one.

The title compound, C(21)H(13)NO(2), was prepared as an example of a new synthesis of carbazoles from a cyclic dibenzo-iodo-lium salt via a twofold Pd-catalysed aryl-ation of a primary amine. The two essentially planar π-subsystems [maximum deviations from the mean square plane of 0.038 (2) Å in the carbazole and 0.059 (2) Å in the coumarine unit] open a dihedral angle of 63.05 (4)°. Two mol-ecules form a centrosymmetrical pair connected via π-π inter-actions between the pyrrole and pyrone rings [centroid-centroid distance = 3.882 (1) Å] and one benzene of the carbazole and the pyrone unit [centroid-centroid distance 3.824 (1) Å]. The lattice is stabilized by C-H⋯O bridging to both coumarin O atoms.

Related literature

For alkaloids based on the carbazole core, see: Kapil (1971 ▶). For information on carbazoles used as electron-rich and rigid units in functional materials for photoconducting, sensing and luminescence purposes, see: Wakim et al. (2004 ▶); Schmitt et al. (2008 ▶). For carbazoles and δ-carbolines using the iodo­lium salt route, see Letessier (2011 ▶); Letessier et al. (2011 ▶). For the construction of carbazoles and their heteroanalogous derivatives, see: Nissen & Detert (2011 ▶); Dassonneville et al. (2011 ▶); Letessier et al. (2011 ▶). For the synthesis of annulated heterocycles, see: Nemkovich et al. (2009 ▶); Preis et al. (2011 ▶).

Experimental

Crystal data

C21H13NO2

M = 311.32

Monoclinic,

a = 8.9451 (12) Å

b = 11.5412 (7) Å

c = 15.0477 (17) Å

β = 105.871 (12)°

V = 1494.3 (3) Å3

Z = 4

Cu Kα radiation

μ = 0.72 mm−1

T = 193 K

0.50 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (CORINC; Dräger & Gattow, 1971 ▶) T min = 0.716, T max = 0.932

2826 measured reflections

2826 independent reflections

2171 reflections with I > 2σ(I)

3 standard reflections every 60 min intensity decay: 5%

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.142

S = 1.04

2826 reflections

217 parameters

H-atom parameters constrained

Δρmax = 0.21 e Å−3

Δρmin = −0.30 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: CORINC (Dräger & Gattow, 1971 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811034660/bt5627sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811034660/bt5627Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811034660/bt5627Isup3.cml

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

C21H13NO2	F(000) = 648
Mr = 311.32	Dx = 1.384 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 8.9451 (12) Å	θ = 45–50°
b = 11.5412 (7) Å	µ = 0.72 mm−1
c = 15.0477 (17) Å	T = 193 K
β = 105.871 (12)°	Block, colourless
V = 1494.3 (3) Å3	0.50 × 0.20 × 0.10 mm
Z = 4

Enraf–Nonius CAD-4 diffractometer	2171 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.000
graphite	θmax = 69.9°, θmin = 4.9°
ω/2θ scans	h = 0→10
Absorption correction: ψ scan (CORINC; Dräger & Gattow, 1971)	k = 0→14
Tmin = 0.716, Tmax = 0.932	l = −18→17
2826 measured reflections	3 standard reflections every 60 min
2826 independent reflections	intensity decay: 5%

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.142	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0895P)2 + 0.1404P] where P = (Fo2 + 2Fc2)/3
2826 reflections	(Δ/σ)max < 0.001
217 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

Experimental. 1H-NMR (400 MHz, CDCl3): δ = 8.12 (d, J=8.3Hz, 2H), 8.04 (s, 1H), 7.66 (m, 1H), 7.60 (dd, J=7.8Hz, J=1.5Hz, 1H), 7.51 (d, J=8.3Hz, 1H), 7.43 (m, 3H), 7.31 (m, 4H).

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.

	x	y	z	Uiso*/Ueq
N1	0.35522 (19)	0.44252 (14)	0.28217 (10)	0.0344 (4)
C2	0.2569 (2)	0.34605 (16)	0.26142 (12)	0.0326 (4)
C3	0.2417 (2)	0.26376 (18)	0.19169 (13)	0.0389 (5)
H3	0.3027	0.2677	0.1491	0.047*
C4	0.1339 (2)	0.17589 (19)	0.18704 (14)	0.0434 (5)
H4	0.1218	0.1181	0.1407	0.052*
C5	0.0427 (2)	0.17044 (19)	0.24880 (14)	0.0431 (5)
H5	−0.0308	0.1096	0.2435	0.052*
C6	0.0580 (2)	0.25207 (18)	0.31729 (13)	0.0384 (5)
H6	−0.0048	0.2484	0.3589	0.046*
C7	0.1674 (2)	0.34055 (16)	0.32474 (12)	0.0314 (4)
C8	0.2154 (2)	0.43659 (17)	0.38781 (12)	0.0324 (4)
C9	0.1733 (2)	0.47311 (19)	0.46582 (13)	0.0410 (5)
H9	0.0967	0.4321	0.4862	0.049*
C10	0.2444 (2)	0.5697 (2)	0.51302 (14)	0.0454 (5)
H10	0.2155	0.5958	0.5659	0.054*
C11	0.3578 (3)	0.62901 (19)	0.48398 (14)	0.0439 (5)
H11	0.4059	0.6947	0.5180	0.053*
C12	0.4028 (2)	0.59507 (17)	0.40682 (14)	0.0394 (5)
H12	0.4800	0.6363	0.3872	0.047*
C13	0.3298 (2)	0.49793 (16)	0.35928 (12)	0.0328 (4)
C14	0.4510 (2)	0.48169 (16)	0.22789 (12)	0.0319 (4)
C15	0.5679 (2)	0.41781 (16)	0.21408 (13)	0.0338 (4)
H15	0.5963	0.3477	0.2476	0.041*
C16	0.6506 (2)	0.45360 (17)	0.14968 (12)	0.0335 (4)
C17	0.7664 (2)	0.38761 (19)	0.12769 (15)	0.0421 (5)
H17	0.7984	0.3165	0.1588	0.051*
C18	0.8348 (2)	0.4251 (2)	0.06098 (16)	0.0497 (6)
H18	0.9123	0.3793	0.0456	0.060*
C19	0.7902 (2)	0.5300 (2)	0.01643 (15)	0.0477 (6)
H19	0.8376	0.5552	−0.0295	0.057*
C20	0.6781 (2)	0.5980 (2)	0.03778 (14)	0.0408 (5)
H20	0.6483	0.6699	0.0074	0.049*
C21	0.6100 (2)	0.55910 (17)	0.10453 (12)	0.0329 (4)
O22	0.49743 (15)	0.62816 (11)	0.12387 (9)	0.0355 (3)
C23	0.4108 (2)	0.59401 (16)	0.18148 (12)	0.0329 (4)
O24	0.30993 (17)	0.65883 (13)	0.19049 (10)	0.0444 (4)

	U11	U22	U33	U12	U13	U23
N1	0.0407 (9)	0.0321 (8)	0.0342 (8)	−0.0038 (7)	0.0168 (7)	−0.0014 (6)
C2	0.0344 (9)	0.0291 (9)	0.0332 (9)	0.0008 (7)	0.0075 (7)	0.0032 (7)
C3	0.0452 (11)	0.0376 (11)	0.0344 (10)	0.0005 (9)	0.0116 (8)	−0.0011 (8)
C4	0.0493 (12)	0.0377 (11)	0.0387 (10)	−0.0030 (9)	0.0044 (9)	−0.0039 (8)
C5	0.0384 (11)	0.0419 (12)	0.0434 (11)	−0.0079 (9)	0.0015 (9)	0.0026 (9)
C6	0.0319 (9)	0.0435 (11)	0.0385 (10)	−0.0030 (8)	0.0077 (8)	0.0074 (8)
C7	0.0300 (9)	0.0327 (10)	0.0300 (9)	0.0036 (7)	0.0056 (7)	0.0043 (7)
C8	0.0300 (9)	0.0353 (10)	0.0311 (9)	0.0040 (7)	0.0071 (7)	0.0048 (7)
C9	0.0391 (10)	0.0509 (12)	0.0352 (10)	0.0038 (9)	0.0136 (8)	0.0017 (9)
C10	0.0487 (12)	0.0541 (13)	0.0355 (10)	0.0092 (10)	0.0153 (9)	−0.0059 (9)
C11	0.0516 (12)	0.0377 (11)	0.0390 (11)	0.0013 (10)	0.0067 (9)	−0.0070 (9)
C12	0.0440 (11)	0.0347 (11)	0.0400 (10)	−0.0018 (8)	0.0121 (9)	−0.0008 (8)
C13	0.0350 (9)	0.0319 (10)	0.0312 (9)	0.0035 (8)	0.0089 (7)	0.0010 (7)
C14	0.0360 (9)	0.0301 (10)	0.0311 (9)	−0.0027 (8)	0.0116 (7)	0.0007 (7)
C15	0.0348 (10)	0.0307 (10)	0.0351 (9)	−0.0001 (8)	0.0081 (7)	0.0023 (7)
C16	0.0279 (9)	0.0373 (10)	0.0342 (9)	−0.0026 (8)	0.0065 (7)	−0.0036 (8)
C17	0.0332 (10)	0.0436 (12)	0.0483 (12)	0.0012 (9)	0.0088 (9)	−0.0051 (9)
C18	0.0327 (10)	0.0636 (15)	0.0574 (13)	−0.0040 (10)	0.0199 (10)	−0.0120 (11)
C19	0.0363 (10)	0.0658 (15)	0.0451 (11)	−0.0154 (10)	0.0183 (9)	−0.0081 (10)
C20	0.0367 (10)	0.0480 (12)	0.0375 (10)	−0.0120 (9)	0.0097 (8)	−0.0006 (9)
C21	0.0284 (9)	0.0375 (10)	0.0324 (9)	−0.0051 (8)	0.0074 (7)	−0.0032 (7)
O22	0.0365 (7)	0.0329 (7)	0.0384 (7)	0.0004 (6)	0.0125 (6)	0.0054 (5)
C23	0.0341 (9)	0.0320 (10)	0.0333 (9)	−0.0012 (8)	0.0106 (7)	−0.0002 (7)
O24	0.0466 (8)	0.0391 (8)	0.0512 (8)	0.0094 (6)	0.0197 (7)	0.0023 (6)

N1—C13	1.397 (2)	C11—H11	0.9500
N1—C2	1.400 (2)	C12—C13	1.392 (3)
N1—C14	1.410 (2)	C12—H12	0.9500
C2—C3	1.394 (3)	C14—C15	1.342 (3)
C2—C7	1.404 (3)	C14—C23	1.470 (3)
C3—C4	1.388 (3)	C15—C16	1.431 (3)
C3—H3	0.9500	C15—H15	0.9500
C4—C5	1.395 (3)	C16—C21	1.393 (3)
C4—H4	0.9500	C16—C17	1.397 (3)
C5—C6	1.375 (3)	C17—C18	1.380 (3)
C5—H5	0.9500	C17—H17	0.9500
C6—C7	1.397 (3)	C18—C19	1.388 (3)
C6—H6	0.9500	C18—H18	0.9500
C7—C8	1.446 (3)	C19—C20	1.379 (3)
C8—C9	1.393 (3)	C19—H19	0.9500
C8—C13	1.405 (3)	C20—C21	1.384 (3)
C9—C10	1.380 (3)	C20—H20	0.9500
C9—H9	0.9500	C21—O22	1.376 (2)
C10—C11	1.390 (3)	O22—C23	1.369 (2)
C10—H10	0.9500	C23—O24	1.208 (2)
C11—C12	1.385 (3)
C13—N1—C2	108.33 (15)	C11—C12—H12	121.4
C13—N1—C14	126.66 (16)	C13—C12—H12	121.4
C2—N1—C14	124.73 (15)	C12—C13—N1	129.46 (18)
C3—C2—N1	129.48 (18)	C12—C13—C8	121.80 (17)
C3—C2—C7	121.57 (18)	N1—C13—C8	108.71 (16)
N1—C2—C7	108.95 (16)	C15—C14—N1	122.45 (17)
C4—C3—C2	117.34 (19)	C15—C14—C23	120.71 (16)
C4—C3—H3	121.3	N1—C14—C23	116.74 (16)
C2—C3—H3	121.3	C14—C15—C16	121.02 (17)
C3—C4—C5	121.60 (19)	C14—C15—H15	119.5
C3—C4—H4	119.2	C16—C15—H15	119.5
C5—C4—H4	119.2	C21—C16—C17	118.19 (18)
C6—C5—C4	120.78 (19)	C21—C16—C15	117.93 (17)
C6—C5—H5	119.6	C17—C16—C15	123.86 (19)
C4—C5—H5	119.6	C18—C17—C16	120.4 (2)
C5—C6—C7	118.99 (19)	C18—C17—H17	119.8
C5—C6—H6	120.5	C16—C17—H17	119.8
C7—C6—H6	120.5	C17—C18—C19	119.9 (2)
C6—C7—C2	119.70 (18)	C17—C18—H18	120.0
C6—C7—C8	133.52 (18)	C19—C18—H18	120.0
C2—C7—C8	106.77 (16)	C20—C19—C18	121.03 (19)
C9—C8—C13	119.51 (18)	C20—C19—H19	119.5
C9—C8—C7	133.24 (18)	C18—C19—H19	119.5
C13—C8—C7	107.23 (16)	C19—C20—C21	118.5 (2)
C10—C9—C8	119.06 (19)	C19—C20—H20	120.8
C10—C9—H9	120.5	C21—C20—H20	120.8
C8—C9—H9	120.5	O22—C21—C20	117.27 (18)
C9—C10—C11	120.62 (18)	O22—C21—C16	120.75 (16)
C9—C10—H10	119.7	C20—C21—C16	121.97 (18)
C11—C10—H10	119.7	C23—O22—C21	122.72 (14)
C12—C11—C10	121.9 (2)	O24—C23—O22	117.53 (17)
C12—C11—H11	119.1	O24—C23—C14	125.86 (17)
C10—C11—H11	119.1	O22—C23—C14	116.60 (16)
C11—C12—C13	117.11 (19)
C13—N1—C2—C3	−179.12 (19)	C7—C8—C13—C12	−178.87 (17)
C14—N1—C2—C3	6.6 (3)	C9—C8—C13—N1	177.92 (16)
C13—N1—C2—C7	0.6 (2)	C7—C8—C13—N1	−0.8 (2)
C14—N1—C2—C7	−173.62 (16)	C13—N1—C14—C15	123.2 (2)
N1—C2—C3—C4	179.88 (18)	C2—N1—C14—C15	−63.6 (3)
C7—C2—C3—C4	0.1 (3)	C13—N1—C14—C23	−60.6 (2)
C2—C3—C4—C5	0.7 (3)	C2—N1—C14—C23	112.6 (2)
C3—C4—C5—C6	−0.6 (3)	N1—C14—C15—C16	172.20 (16)
C4—C5—C6—C7	−0.5 (3)	C23—C14—C15—C16	−3.9 (3)
C5—C6—C7—C2	1.3 (3)	C14—C15—C16—C21	2.5 (3)
C5—C6—C7—C8	−178.49 (19)	C14—C15—C16—C17	−175.69 (18)
C3—C2—C7—C6	−1.2 (3)	C21—C16—C17—C18	−1.9 (3)
N1—C2—C7—C6	179.02 (16)	C15—C16—C17—C18	176.35 (18)
C3—C2—C7—C8	178.68 (17)	C16—C17—C18—C19	1.0 (3)
N1—C2—C7—C8	−1.1 (2)	C17—C18—C19—C20	0.1 (3)
C6—C7—C8—C9	2.6 (4)	C18—C19—C20—C21	−0.4 (3)
C2—C7—C8—C9	−177.3 (2)	C19—C20—C21—O22	−179.40 (16)
C6—C7—C8—C13	−179.0 (2)	C19—C20—C21—C16	−0.5 (3)
C2—C7—C8—C13	1.2 (2)	C17—C16—C21—O22	−179.53 (16)
C13—C8—C9—C10	0.5 (3)	C15—C16—C21—O22	2.1 (3)
C7—C8—C9—C10	178.82 (19)	C17—C16—C21—C20	1.6 (3)
C8—C9—C10—C11	−0.8 (3)	C15—C16—C21—C20	−176.71 (17)
C9—C10—C11—C12	0.7 (3)	C20—C21—O22—C23	173.28 (16)
C10—C11—C12—C13	−0.3 (3)	C16—C21—O22—C23	−5.6 (3)
C11—C12—C13—N1	−177.60 (19)	C21—O22—C23—O24	−176.57 (16)
C11—C12—C13—C8	0.1 (3)	C21—O22—C23—C14	4.2 (2)
C2—N1—C13—C12	178.00 (19)	C15—C14—C23—O24	−178.58 (19)
C14—N1—C13—C12	−7.9 (3)	N1—C14—C23—O24	5.1 (3)
C2—N1—C13—C8	0.1 (2)	C15—C14—C23—O22	0.6 (3)
C14—N1—C13—C8	174.22 (16)	N1—C14—C23—O22	−175.71 (15)
C9—C8—C13—C12	−0.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···O24i	0.95	2.43	3.366 (2)	169
C11—H11···O22ii	0.95	2.58	3.522 (2)	170

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15⋯O24i	0.95	2.43	3.366 (2)	169
C11—H11⋯O22ii	0.95	2.58	3.522 (2)	170

Symmetry codes: (i) ; (ii) .