9-Ethyl-3,6-diformyl-9H-carbazole

Wang, J.J.; Zhang, X.; Zhang, B.Q.; Wang, G.; Yu, X.Q.

doi:10.1107/S1600536808017923

organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1293

doi:10.1107/S1600536808017923

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9-Ethyl-3,6-diformyl-9H-carbazole

Jun Jie Wang,^a Xian Zhang,^b Bao Qin Zhang,^a Gang Wang ^c and Xiao Qiang Yu ^a ^*

^aState Key Laboratory of Crystalline Materials, Institute of Crystalline Materials, Shandong University, Jinan 250100, People's Republic of China, ^bSchool of Materials Science and Engineering, Shandong Institute of Light Industry, Jinan 250353, People's Republic of China, and ^cSchool of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, People's Republic of China
^*Correspondence e-mail: yuxq@sdu.edu.cn

(Received 6 May 2008; accepted 12 June 2008; online 19 June 2008)

The structure of the title compound, C₁₆H₁₃NO₂, was determined as a part of a project on the synthesis of new compounds which can make two-photon absorptions. In the crystal structure, both aldehyde groups are located within the carbazole plane. One of these groups is disordered and was refined using a split model with site-occupation factors for each position of 0.5.

Related literature

For the synthesis of 9-ethyicarbazole, see: Li et al. (2001 ).

Experimental

Crystal data

C₁₆H₁₃NO₂
M_r = 251.27
Monoclinic, P 2₁ /n
a = 13.5475 (3) Å
b = 6.69540 (10) Å
c = 14.1840 (2) Å
β = 100.5100 (10)°
V = 1264.99 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 (2) K
0.46 × 0.32 × 0.28 mm

Data collection

Bruker APEX2 CCD area-detector diffractometer
Absorption correction: multi-scan (APEX2; Bruker, 2005 ) T_min = 0.962, T_max = 0.978
7890 measured reflections
2810 independent reflections
2123 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.112
S = 1.05
2810 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808017923/nc2104sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808017923/nc2104Isup2.hkl

checkCIF report

Related literature top

For the synthesis of 9-ethyicarbazole, see: Li et al. (2001).

Experimental top

9-Ethylcarbazole was synthesized according to the literature (Li et al. , 2001). Anhydrous DMF (22 mL, 0.3 mol) was added dropwisely to POCl₃ (28 ml, 0.3 mol) under stirring in an ice bath. After 30 minute a white precipitate is obtained and a solution of 9-ethylcarbazole (3.155 g, 16 mmol) in DMF (20 mL) were added. The reaction mixture was slowly heated to 373 K and stirred at this temperature for 30 h and then cooled to room temperature. The brown viscous oily production was poured into the ice-water and shaken; the pH value of the solution was adjusted to 8 by dropping aqueous sodium hydroxide and sodium bicarbonate. It was stirred for another 2 h at pH=8 at room temperature. The aqueous layer was extracted with dichloromethane (3 × 100 ml) and the combined organic layers were washed three times with 100 mL of water and dried over anhydrous magnesium sulfate. Afterwards the solvent was evaporated under reduced pressure. The residue was dissolved in a minimal amount of dichloromethane and then purified by silica-gel column chromatography using dichloromethane as eluent. The product was recrystallized from dichloromethane to give high quality dark yellow crystals used for X-ray structure analysis.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: APEX2 (Bruker, 2005); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia,1999).

Figures top

Fig. 1. : The molecular structure of title compound with labelling and 50% probability displacement ellipsoids.

9-Ethyl-3,6-diformyl-9H-carbazole top

Crystal data top

C₁₆H₁₃NO₂	F(000) = 528
M_r = 251.27	D_x = 1.319 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.5475 (3) Å	Cell parameters from 3121 reflections
b = 6.6954 (1) Å	θ = 2.9–27.0°
c = 14.1840 (2) Å	µ = 0.09 mm⁻¹
β = 100.510 (1)°	T = 293 K
V = 1264.99 (4) Å³	Block, colourless
Z = 4	0.46 × 0.32 × 0.28 mm

Data collection top

Bruker APEX2 CCD area-detector diffractometer	2810 independent reflections
Radiation source: fine-focus sealed tube	2123 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ and ω scans	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: multi-scan (APEX2; Bruker, 2005)	h = −15→17
T_min = 0.962, T_max = 0.978	k = −8→8
7890 measured reflections	l = −18→18

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.112	w = 1/[σ²(F_o²) + (0.0515P)² + 0.1926P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
2810 reflections	Δρ_max = 0.17 e Å⁻³
183 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.020 (3)

Crystal data top

C₁₆H₁₃NO₂	V = 1264.99 (4) Å³
M_r = 251.27	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.5475 (3) Å	µ = 0.09 mm⁻¹
b = 6.6954 (1) Å	T = 293 K
c = 14.1840 (2) Å	0.46 × 0.32 × 0.28 mm
β = 100.510 (1)°

Data collection top

Bruker APEX2 CCD area-detector diffractometer	2810 independent reflections
Absorption correction: multi-scan (APEX2; Bruker, 2005)	2123 reflections with I > 2σ(I)
T_min = 0.962, T_max = 0.978	R_int = 0.016
7890 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 1.05	Δρ_max = 0.17 e Å⁻³
2810 reflections	Δρ_min = −0.16 e Å⁻³
183 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	Occ. (<1)
O1	1.02612 (11)	0.7739 (2)	0.65681 (10)	0.1009 (5)
O2	0.8577 (2)	−0.1440 (4)	1.19028 (19)	0.0963 (8)	0.50
O2'	0.9276 (2)	−0.1336 (4)	1.1217 (2)	0.0830 (8)	0.50
N1	0.73234 (8)	0.68042 (17)	0.96028 (7)	0.0500 (3)
C1	0.55071 (11)	0.7452 (3)	0.91838 (13)	0.0713 (4)
H1A	0.5513	0.7464	0.8508	0.107*
H1B	0.4989	0.8327	0.9318	0.107*
H1C	0.5381	0.6119	0.9381	0.107*
C2	0.65035 (10)	0.8149 (2)	0.97202 (11)	0.0573 (4)
H2A	0.6642	0.9470	0.9495	0.069*
H2B	0.6473	0.8252	1.0396	0.069*
C3	0.79421 (9)	0.69945 (19)	0.89373 (9)	0.0459 (3)
C4	0.79749 (10)	0.8498 (2)	0.82587 (10)	0.0557 (3)
H4	0.7532	0.9571	0.8198	0.067*
C5	0.86839 (11)	0.8333 (2)	0.76856 (10)	0.0585 (4)
H5	0.8715	0.9308	0.7225	0.070*
C6	0.93648 (10)	0.6734 (2)	0.77748 (9)	0.0523 (3)
C7	0.93244 (9)	0.5240 (2)	0.84424 (8)	0.0485 (3)
H7	0.9774	0.4178	0.8501	0.058*
C8	0.86064 (9)	0.53478 (19)	0.90209 (8)	0.0440 (3)
C9	0.83555 (9)	0.40894 (19)	0.97708 (8)	0.0452 (3)
C10	0.75611 (9)	0.5055 (2)	1.01106 (8)	0.0473 (3)
C11	0.71439 (11)	0.4259 (2)	1.08601 (10)	0.0582 (4)
H11	0.6627	0.4907	1.1088	0.070*
C12	0.75280 (12)	0.2485 (2)	1.12461 (10)	0.0626 (4)
H12	0.7263	0.1923	1.1745	0.075*
C13	0.83086 (11)	0.1487 (2)	1.09134 (9)	0.0573 (4)
C14	0.87244 (10)	0.2299 (2)	1.01732 (9)	0.0510 (3)
H14	0.9244	0.1646	0.9952	0.061*
C15	1.01501 (12)	0.6612 (3)	0.71893 (11)	0.0666 (4)
H15	1.0603	0.5559	0.7315	0.080*
C16	0.87062 (18)	−0.0411 (3)	1.13397 (14)	0.0825 (6)
H16A	0.9220	−0.0876	1.1043	0.099*	0.50
H16B	0.8377	−0.0871	1.1818	0.099*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1167 (11)	0.1034 (10)	0.1002 (9)	−0.0055 (8)	0.0663 (9)	0.0204 (8)
O2	0.128 (2)	0.0828 (17)	0.0829 (16)	−0.0009 (16)	0.0324 (16)	0.0299 (14)
O2'	0.0887 (18)	0.0589 (14)	0.1029 (18)	0.0237 (13)	0.0213 (14)	0.0161 (13)
N1	0.0436 (6)	0.0549 (7)	0.0544 (6)	0.0046 (5)	0.0166 (5)	0.0001 (5)
C1	0.0504 (8)	0.0671 (10)	0.0958 (11)	0.0074 (7)	0.0122 (8)	−0.0025 (9)
C2	0.0514 (8)	0.0556 (8)	0.0688 (8)	0.0064 (6)	0.0212 (6)	−0.0073 (7)
C3	0.0385 (6)	0.0522 (7)	0.0475 (6)	−0.0009 (5)	0.0090 (5)	−0.0009 (5)
C4	0.0505 (7)	0.0547 (8)	0.0619 (8)	0.0052 (6)	0.0103 (6)	0.0085 (6)
C5	0.0575 (8)	0.0622 (9)	0.0573 (7)	−0.0046 (7)	0.0142 (6)	0.0120 (7)
C6	0.0461 (7)	0.0622 (8)	0.0505 (7)	−0.0081 (6)	0.0140 (5)	−0.0001 (6)
C7	0.0404 (6)	0.0550 (8)	0.0509 (6)	−0.0004 (5)	0.0103 (5)	−0.0014 (6)
C8	0.0386 (6)	0.0494 (7)	0.0440 (6)	−0.0013 (5)	0.0078 (5)	−0.0001 (5)
C9	0.0405 (6)	0.0512 (7)	0.0441 (6)	−0.0021 (5)	0.0078 (5)	−0.0012 (5)
C10	0.0429 (6)	0.0535 (7)	0.0461 (6)	−0.0024 (5)	0.0102 (5)	−0.0035 (5)
C11	0.0570 (8)	0.0691 (9)	0.0531 (7)	−0.0048 (7)	0.0218 (6)	−0.0034 (7)
C12	0.0695 (9)	0.0721 (10)	0.0492 (7)	−0.0153 (8)	0.0189 (7)	0.0023 (7)
C13	0.0637 (9)	0.0550 (8)	0.0507 (7)	−0.0098 (7)	0.0040 (6)	0.0046 (6)
C14	0.0483 (7)	0.0521 (8)	0.0519 (7)	−0.0001 (6)	0.0074 (5)	0.0003 (6)
C15	0.0654 (9)	0.0742 (10)	0.0657 (9)	−0.0152 (8)	0.0268 (7)	−0.0035 (8)
C16	0.1016 (15)	0.0660 (11)	0.0722 (11)	−0.0161 (11)	−0.0043 (10)	0.0172 (10)

Geometric parameters (Å, º) top

O1—C15	1.1902 (19)	C6—C7	1.3852 (18)
O2—C16	1.093 (3)	C6—C15	1.466 (2)
O2—H16B	0.4697	C7—C8	1.3842 (17)
O2'—C16	1.029 (3)	C7—H7	0.9300
N1—C3	1.3778 (16)	C8—C9	1.4453 (17)
N1—C10	1.3818 (17)	C9—C14	1.3816 (18)
N1—C2	1.4628 (16)	C9—C10	1.4134 (17)
C1—C2	1.498 (2)	C10—C11	1.3974 (18)
C1—H1A	0.9600	C11—C12	1.370 (2)
C1—H1B	0.9600	C11—H11	0.9300
C1—H1C	0.9600	C12—C13	1.403 (2)
C2—H2A	0.9700	C12—H12	0.9300
C2—H2B	0.9700	C13—C14	1.3896 (19)
C3—C4	1.3990 (18)	C13—C16	1.467 (2)
C3—C8	1.4144 (17)	C14—H14	0.9300
C4—C5	1.371 (2)	C15—H15	0.9300
C4—H4	0.9300	C16—H16A	0.9300
C5—C6	1.404 (2)	C16—H16B	0.9300
C5—H5	0.9300

C3—N1—C10	108.81 (10)	C7—C8—C9	133.70 (12)
C3—N1—C2	126.20 (11)	C3—C8—C9	106.54 (11)
C10—N1—C2	124.89 (11)	C14—C9—C10	119.79 (11)
C2—C1—H1A	109.5	C14—C9—C8	133.94 (12)
C2—C1—H1B	109.5	C10—C9—C8	106.27 (11)
H1A—C1—H1B	109.5	N1—C10—C11	129.17 (12)
C2—C1—H1C	109.5	N1—C10—C9	109.24 (11)
H1A—C1—H1C	109.5	C11—C10—C9	121.58 (13)
H1B—C1—H1C	109.5	C12—C11—C10	117.24 (13)
N1—C2—C1	112.52 (12)	C12—C11—H11	121.4
N1—C2—H2A	109.1	C10—C11—H11	121.4
C1—C2—H2A	109.1	C11—C12—C13	122.20 (13)
N1—C2—H2B	109.1	C11—C12—H12	118.9
C1—C2—H2B	109.1	C13—C12—H12	118.9
H2A—C2—H2B	107.8	C14—C13—C12	120.13 (13)
N1—C3—C4	129.60 (12)	C14—C13—C16	118.77 (16)
N1—C3—C8	109.13 (11)	C12—C13—C16	121.09 (15)
C4—C3—C8	121.26 (12)	C9—C14—C13	119.05 (13)
C5—C4—C3	117.61 (13)	C9—C14—H14	120.5
C5—C4—H4	121.2	C13—C14—H14	120.4
C3—C4—H4	121.2	O1—C15—C6	125.94 (17)
C4—C5—C6	121.85 (13)	O1—C15—H15	117.0
C4—C5—H5	119.1	C6—C15—H15	117.0
C6—C5—H5	119.1	O2'—C16—C13	133.0 (3)
C7—C6—C5	120.34 (12)	O2—C16—C13	138.7 (3)
C7—C6—C15	118.06 (13)	O2—C16—H16A	110.6
C5—C6—C15	121.58 (13)	C13—C16—H16A	110.6
C8—C7—C6	119.15 (12)	O2'—C16—H16B	113.5
C8—C7—H7	120.4	C13—C16—H16B	113.5
C6—C7—H7	120.4	H16A—C16—H16B	135.8
C7—C8—C3	119.75 (11)

C3—N1—C2—C1	94.54 (16)	C3—N1—C10—C11	179.12 (13)
C10—N1—C2—C1	−81.23 (17)	C2—N1—C10—C11	−4.5 (2)
C10—N1—C3—C4	179.26 (13)	C3—N1—C10—C9	0.26 (14)
C2—N1—C3—C4	2.9 (2)	C2—N1—C10—C9	176.66 (11)
C10—N1—C3—C8	−0.76 (13)	C14—C9—C10—N1	−179.99 (11)
C2—N1—C3—C8	−177.10 (12)	C8—C9—C10—N1	0.34 (13)
N1—C3—C4—C5	179.09 (13)	C14—C9—C10—C11	1.04 (18)
C8—C3—C4—C5	−0.88 (19)	C8—C9—C10—C11	−178.63 (11)
C3—C4—C5—C6	−0.7 (2)	N1—C10—C11—C12	−179.57 (12)
C4—C5—C6—C7	1.2 (2)	C9—C10—C11—C12	−0.83 (19)
C4—C5—C6—C15	−177.23 (13)	C10—C11—C12—C13	0.1 (2)
C5—C6—C7—C8	−0.16 (19)	C11—C12—C13—C14	0.5 (2)
C15—C6—C7—C8	178.34 (12)	C11—C12—C13—C16	179.97 (14)
C6—C7—C8—C3	−1.36 (17)	C10—C9—C14—C13	−0.47 (18)
C6—C7—C8—C9	179.95 (13)	C8—C9—C14—C13	179.09 (13)
N1—C3—C8—C7	−178.05 (11)	C12—C13—C14—C9	−0.2 (2)
C4—C3—C8—C7	1.92 (18)	C16—C13—C14—C9	−179.78 (12)
N1—C3—C8—C9	0.96 (13)	C7—C6—C15—O1	177.41 (16)
C4—C3—C8—C9	−179.07 (12)	C5—C6—C15—O1	−4.1 (2)
C7—C8—C9—C14	−1.6 (2)	C14—C13—C16—O2'	1.6 (4)
C3—C8—C9—C14	179.62 (13)	C12—C13—C16—O2'	−177.9 (3)
C7—C8—C9—C10	178.03 (13)	C14—C13—C16—O2	179.8 (3)
C3—C8—C9—C10	−0.78 (13)	C12—C13—C16—O2	0.3 (4)

Experimental details

Crystal data
Chemical formula	C₁₆H₁₃NO₂
M_r	251.27
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	13.5475 (3), 6.6954 (1), 14.1840 (2)
β (°)	100.510 (1)
V (Å³)	1264.99 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.46 × 0.32 × 0.28

Data collection
Diffractometer	Bruker APEX2 CCD area-detector diffractometer
Absorption correction	Multi-scan (APEX2; Bruker, 2005)
T_min, T_max	0.962, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	7890, 2810, 2123
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.112, 1.05
No. of reflections	2810
No. of parameters	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.16

Computer programs: APEX2 (Bruker, 2005), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), WinGX (Farrugia,1999).

Acknowledgements

This work was supported by a grant for the National Science Foundation of China (50673053), the State Key Program of China (2004CB719803), NSFC/RGC (50218001), the National Science Foundation of China (50173015). We also thank Dr Wang Xin Qiang for looking at this paper.

References

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