N-(4-Chloro­phen­yl)-9H-fluoren-9-imine

Crundwell, G.; Glagovich, N.M.; Reed Heinrich, E.M.; Ouellette, P.

doi:10.1107/S2414314619005558

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 4| April 2019| x190555

https://doi.org/10.1107/S2414314619005558

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N-(4-Chlorophenyl)-9H-fluoren-9-imine

Guy Crundwell,^a ^* Neil M. Glagovich,^a Elizabeth M. Reed Heinrich ^a and Paul Ouellette ^a

^aDepartment of Chemistry & Biochemistry, Central Connecticut State University, 1619 Stanley Street, New Britain, CT 06050, USA
^*Correspondence e-mail: crundwellg@ccsu.edu

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 10 April 2019; accepted 23 April 2019; online 30 April 2019)

The title compound, C₁₉H₁₂ClN, was synthesized via reaction of 9-fluorenone and 4-chloroaniline using p-toluenesulfonic acid in toluene. The dihedral angle between the fluorene moiety (r.m.s. deviation = 0.027 Å) and the chlorophenyl ring is 64.59 (6)° and a possible weak intramolecular C—H⋯π interaction occurs.

Keywords: crystal structure; imine; fluorenone derivative.

CCDC reference: 1911702

Structure description

Acid-catalyzed imine formation reactions between 9-fluorenone and anilines are easy, high-yield projects for undergraduate research. Fluoren-9-imines are of interest because of their interesting fluorescence (Dufresne et al., 2011 ) and use as potential organics in materials with tunable HLG (HOMO–LUMO gap) systems (Eakins et al., 2013 ). The crystal structure of N-phenyl-9H-fluoren-9-imine, the stripped-down combination between 9-fluorenone and aniline, has been published three times. The first paper described the structure of a monoclinic benzene solvate (Peters et al., 1998 ). Unsolvated monoclinic and orthorhombic forms were published by Eakins et al. (2013) and Dufresne et al. (2011), respectively. Four additional complexes made from 9-fluorenone and substituted anilines have been published: a 4-methylaniline derivate (Bai et al., 2009 ) and 3,4-dimethylaniline, 2-methoxy aniline and 4-methoxyaniline derivatives (Glagovich et al., 2004a ,b ,c ). Finally, the crystal structure of N-mesityl-9H-fluoren-9-imine was communicated privately to the CSD in 2016 (Evans et al. 2016 ). As part of our studies in this area, we now describe the synthesis and structure of the title compound.

In the title molecule (Fig. 1), all bond lengths and angles are within expected values: the dihedral angle between the fluorene ring system and the chlorophenyl ring is 64.59 (6)°. A possible weak intramolecular C3—H3⋯π interaction (Table 1) occurs. In the crystal, the molecules pack in interweaving layers (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

Cg4 is the centroid of the C14–C19 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cg4	0.93	2.98	3.7347 (16)	139

Figure 1
The molecular structure of the title compound showing 50% probability displacement ellipsoids.

Figure 2
The unit-cell packing in the title compound as viewed along [010]. The C—H⋯π contact is shown as a black dashed line.

Synthesis and crystallization

To a 100 ml round-bottom flask were added 0.326 g (1.81 mmol) of 9-fluorenone, 0.46 g (3.62 mmol) of 4-chloroaniline, 0.0017 g (9.05 × 10 ⁻⁶ mol) p-toluenesulfonic acid, and 25 ml of toluene. The flask was fitted with a Hickman still and condenser and the solution was refluxed for 16 h. After this time, the toluene was removed under reduced pressure and the resulting brown solid was purified by column chromatography (SiO₂, 95% hexane/5% EtOAc) to produce 0.395 g (79%) of product. Yellow needles for the diffraction study were crystallized from methylene chloride solution (m.p. 420 K). ATR–IR (cm⁻¹) 3063, 2962, 1640, 838, 816, 732; ¹H NMR (300 MHz, CDCl₃): δ 7.92 (dd, 1H), 7.63 (dd, 2H), 7.44 (dt, 1H), 7.40 (m, 4H), 7.00 (m, 3H), 6.68 (d, 1H); ¹³C (75 MHz, CDCl₃): δ 163.45, 150.22, 143.97, 141.90, 137.32, 132.11, 132.08, 131.06, 129.46, 129.32, 128.54, 127.78, 127.03, 123.39, 120.40, 119.83, 119.70. FTIR, ¹H NMR, COSY and ¹³C NMR are given in the supplementary materials.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₁₂ClN
M_r	289.75
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	14.2842 (14), 5.2148 (2), 25.923 (3)
β (°)	132.024 (17)
V (Å³)	1434.5 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.26
Crystal size (mm)	0.45 × 0.21 × 0.20

Data collection
Diffractometer	Rigaku Oxford Diffraction Xcalibur, Sapphire3
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.767, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	35328, 5301, 3925
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.780

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.134, 1.03
No. of reflections	5301
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.36
Computer programs: CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1911702

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619005558/hb4296sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619005558/hb4296Isup2.hkl

Supplementary Info: 1H, COSY, 13C, and IR data. DOI: https://doi.org/10.1107/S2414314619005558/hb4296sup3.pdf

Supporting information file. DOI: https://doi.org/10.1107/S2414314619005558/hb4296Isup4.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

N-(4-Chlorophenyl)-9H-fluoren-9-imine top

Crystal data top

C₁₉H₁₂ClN	D_x = 1.342 Mg m⁻³
M_r = 289.75	Melting point: 420 K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.2842 (14) Å	Cell parameters from 7600 reflections
b = 5.2148 (2) Å	θ = 4.5–32.3°
c = 25.923 (3) Å	µ = 0.26 mm⁻¹
β = 132.024 (17)°	T = 293 K
V = 1434.5 (2) Å³	Needle, yellow
Z = 4	0.45 × 0.21 × 0.20 mm
F(000) = 600

Data collection top

Rigaku Oxford Diffraction Xcalibur, Sapphire3 diffractometer	5301 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3925 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 16.1790 pixels mm^-1	θ_max = 33.7°, θ_min = 4.2°
ω scans	h = −21→21
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2015)	k = −8→7
T_min = 0.767, T_max = 1.000	l = −38→39
35328 measured reflections

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0519P)² + 0.4392P] where P = (F_o² + 2F_c²)/3
5301 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

The H atoms were included in calculated positions (C—H = 0.93Å) and refined as riding with Uĩso~ = 1.2U_eq (carrier atom).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	−0.45087 (4)	0.83251 (10)	0.46185 (2)	0.06331 (14)
N1	0.00458 (10)	0.2458 (2)	0.57276 (5)	0.0404 (2)
C1	0.09621 (12)	0.2050 (2)	0.63725 (6)	0.0355 (2)
C2	0.12964 (12)	0.3141 (2)	0.70134 (6)	0.0362 (2)
C3	0.07819 (14)	0.5127 (3)	0.71103 (7)	0.0443 (3)
H3	0.0092	0.6045	0.6734	0.053*
C4	0.13234 (15)	0.5717 (3)	0.77866 (8)	0.0521 (4)
H4	0.0984	0.7032	0.7860	0.063*
C5	0.23516 (16)	0.4380 (4)	0.83459 (8)	0.0545 (4)
H5	0.2686	0.4785	0.8791	0.065*
C6	0.28949 (15)	0.2448 (3)	0.82579 (7)	0.0495 (3)
H6	0.3596	0.1566	0.8638	0.059*
C7	0.23708 (12)	0.1852 (3)	0.75893 (7)	0.0383 (3)
C8	0.27774 (12)	−0.0020 (3)	0.73491 (6)	0.0375 (3)
C9	0.37545 (14)	−0.1769 (3)	0.77105 (8)	0.0481 (3)
H9	0.4302	−0.1882	0.8192	0.058*
C10	0.38990 (16)	−0.3354 (3)	0.73379 (9)	0.0537 (4)
H10	0.4555	−0.4535	0.7573	0.064*
C11	0.30817 (15)	−0.3205 (3)	0.66212 (9)	0.0516 (4)
H11	0.3199	−0.4283	0.6383	0.062*
C12	0.20892 (13)	−0.1468 (3)	0.62532 (7)	0.0441 (3)
H12	0.1532	−0.1386	0.5771	0.053*
C13	0.19547 (12)	0.0136 (2)	0.66253 (6)	0.0360 (2)
C14	−0.10002 (12)	0.3955 (3)	0.54933 (6)	0.0373 (3)
C15	−0.13495 (13)	0.6099 (3)	0.50817 (7)	0.0425 (3)
H15	−0.0860	0.6625	0.4984	0.051*
C16	−0.24244 (14)	0.7457 (3)	0.48156 (7)	0.0460 (3)
H16	−0.2651	0.8912	0.4547	0.055*
C17	−0.31558 (12)	0.6632 (3)	0.49532 (7)	0.0426 (3)
C18	−0.28392 (14)	0.4484 (3)	0.53493 (8)	0.0477 (3)
H18	−0.3345	0.3942	0.5435	0.057*
C19	−0.17632 (14)	0.3145 (3)	0.56179 (8)	0.0456 (3)
H19	−0.1545	0.1687	0.5885	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0434 (2)	0.0768 (3)	0.0626 (2)	−0.01057 (18)	0.03256 (19)	0.0050 (2)
N1	0.0410 (5)	0.0500 (6)	0.0365 (5)	−0.0016 (5)	0.0285 (5)	0.0018 (5)
C1	0.0387 (6)	0.0387 (6)	0.0366 (6)	0.0032 (5)	0.0283 (5)	0.0029 (5)
C2	0.0398 (6)	0.0382 (6)	0.0381 (6)	0.0052 (5)	0.0292 (5)	0.0057 (5)
C3	0.0463 (7)	0.0457 (7)	0.0460 (7)	0.0008 (6)	0.0330 (6)	0.0067 (6)
C4	0.0576 (8)	0.0556 (9)	0.0557 (8)	0.0057 (7)	0.0431 (8)	0.0174 (7)
C5	0.0591 (9)	0.0689 (10)	0.0416 (7)	0.0081 (8)	0.0363 (7)	0.0162 (7)
C6	0.0509 (8)	0.0590 (9)	0.0361 (6)	0.0022 (7)	0.0281 (6)	0.0047 (6)
C7	0.0421 (6)	0.0410 (6)	0.0373 (6)	0.0056 (5)	0.0288 (5)	0.0044 (5)
C8	0.0405 (6)	0.0379 (6)	0.0393 (6)	0.0034 (5)	0.0289 (5)	0.0021 (5)
C9	0.0472 (7)	0.0489 (8)	0.0463 (7)	−0.0053 (6)	0.0304 (6)	−0.0048 (6)
C10	0.0517 (8)	0.0469 (8)	0.0658 (10)	−0.0086 (6)	0.0407 (8)	−0.0033 (7)
C11	0.0542 (8)	0.0486 (8)	0.0640 (9)	−0.0005 (6)	0.0444 (8)	0.0097 (7)
C12	0.0468 (7)	0.0488 (7)	0.0462 (7)	0.0036 (6)	0.0351 (6)	0.0082 (6)
C13	0.0388 (6)	0.0376 (6)	0.0393 (6)	0.0033 (5)	0.0292 (5)	0.0035 (5)
C14	0.0372 (6)	0.0465 (7)	0.0319 (5)	0.0017 (5)	0.0246 (5)	0.0048 (5)
C15	0.0449 (7)	0.0513 (8)	0.0413 (6)	0.0007 (6)	0.0330 (6)	−0.0006 (6)
C16	0.0486 (7)	0.0505 (8)	0.0416 (7)	−0.0043 (6)	0.0314 (6)	−0.0045 (6)
C17	0.0357 (6)	0.0525 (8)	0.0372 (6)	0.0007 (5)	0.0234 (5)	0.0096 (6)
C18	0.0453 (7)	0.0559 (8)	0.0544 (8)	0.0052 (6)	0.0385 (7)	0.0043 (7)
C19	0.0482 (7)	0.0502 (8)	0.0488 (7)	0.0000 (6)	0.0367 (6)	−0.0034 (6)

Geometric parameters (Å, º) top

Cl1—C17	1.7384 (14)	C9—H9	0.9300
N1—C1	1.2742 (17)	C9—C10	1.388 (2)
N1—C14	1.4127 (17)	C10—H10	0.9300
C1—C2	1.4999 (16)	C10—C11	1.384 (2)
C1—C13	1.4805 (18)	C11—H11	0.9300
C2—C3	1.3869 (18)	C11—C12	1.389 (2)
C2—C7	1.4029 (19)	C12—H12	0.9300
C3—H3	0.9300	C12—C13	1.3840 (17)
C3—C4	1.397 (2)	C14—C15	1.3870 (19)
C4—H4	0.9300	C14—C19	1.3936 (18)
C4—C5	1.376 (2)	C15—H15	0.9300
C5—H5	0.9300	C15—C16	1.384 (2)
C5—C6	1.381 (2)	C16—H16	0.9300
C6—H6	0.9300	C16—C17	1.379 (2)
C6—C7	1.3871 (18)	C17—C18	1.375 (2)
C7—C8	1.4702 (18)	C18—H18	0.9300
C8—C9	1.381 (2)	C18—C19	1.379 (2)
C8—C13	1.3986 (18)	C19—H19	0.9300

C1—N1—C14	121.21 (10)	C11—C10—C9	121.05 (14)
N1—C1—C2	132.51 (12)	C11—C10—H10	119.5
N1—C1—C13	122.11 (11)	C10—C11—H11	119.5
C13—C1—C2	105.36 (10)	C10—C11—C12	120.96 (13)
C3—C2—C1	132.03 (13)	C12—C11—H11	119.5
C3—C2—C7	120.00 (12)	C11—C12—H12	121.0
C7—C2—C1	107.90 (11)	C13—C12—C11	118.00 (13)
C2—C3—H3	120.8	C13—C12—H12	121.0
C2—C3—C4	118.46 (14)	C8—C13—C1	109.18 (10)
C4—C3—H3	120.8	C12—C13—C1	129.62 (12)
C3—C4—H4	119.5	C12—C13—C8	121.06 (12)
C5—C4—C3	120.97 (14)	C15—C14—N1	120.55 (11)
C5—C4—H4	119.5	C15—C14—C19	119.23 (12)
C4—C5—H5	119.4	C19—C14—N1	119.92 (12)
C4—C5—C6	121.13 (13)	C14—C15—H15	119.9
C6—C5—H5	119.4	C16—C15—C14	120.22 (12)
C5—C6—H6	120.8	C16—C15—H15	119.9
C5—C6—C7	118.49 (14)	C15—C16—H16	120.3
C7—C6—H6	120.8	C17—C16—C15	119.39 (14)
C2—C7—C8	109.16 (11)	C17—C16—H16	120.3
C6—C7—C2	120.88 (13)	C16—C17—Cl1	119.58 (12)
C6—C7—C8	129.95 (13)	C18—C17—Cl1	119.11 (11)
C9—C8—C7	131.12 (12)	C18—C17—C16	121.31 (13)
C9—C8—C13	120.55 (12)	C17—C18—H18	120.4
C13—C8—C7	108.32 (11)	C17—C18—C19	119.19 (13)
C8—C9—H9	120.8	C19—C18—H18	120.4
C8—C9—C10	118.37 (14)	C14—C19—H19	119.7
C10—C9—H9	120.8	C18—C19—C14	120.62 (14)
C9—C10—H10	119.5	C18—C19—H19	119.7

Hydrogen-bond geometry (Å, º) top

Cg4 is the centroid of the C14–C19 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cg4	0.93	2.98	3.7347 (16)	139

Funding information

Funding for this research was provided by: CSU-AAUP Reseach Grant.

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