Fluoren-9-one oxime

Bernhard Bugenhagen; Yosef Al Jasem; Mariam Al-Azani; Thies Thiemann

doi:10.1107/S1600536814002669

. 2014 Feb 8;70(Pt 3):o265. doi: 10.1107/S1600536814002669

Fluoren-9-one oxime

Bernhard Bugenhagen ^a, Yosef Al Jasem ^b, Mariam Al-Azani ^c, Thies Thiemann ^c,^*

PMCID: PMC3998413 PMID: 24764980

Abstract

In the title molecule, C₁₃H₉NO, the fluorene system and the oxime group non-H atoms are essentially coplanar, with a maximum deviation from the fluorene mean plane of 0.079 (2) Å for the oxime O atom. A short intramolecular C—H⋯O generates an S(6) ring. In the crystal, molecules related by a twofold screw axis are connected by O—H⋯N hydrogen bonds, forming [100] chains Within these chains, molecules related by a unit translation along [100] show π–π stacking interactions between their fluorene ring systems with an interplanar distance of 3.347 (2) Å. The dihedral angle between the fluorene units of adjacent molecules along the helix is 88.40 (2)°. There is a short C—H⋯π contact between the fluorene groups belonging to neighbouring chains.

Related literature

For the original procedure for the preparation of the title compound, see: Moore & Huntress (1927 ▶). For the use of the title compound as a starting material for the synthesis of bioactive compounds, see: Amlaiky et al. (1983 ▶); Ni et al. (2009 ▶); Rad et al. (2012 ▶).

Experimental

Crystal data

C₁₃H₉NO
M _r = 195.21
Orthorhombic,
a = 4.8009 (1) Å
b = 12.2309 (2) Å
c = 16.0247 (3) Å
V = 940.96 (3) Å³
Z = 4
Cu Kα radiation
μ = 0.70 mm⁻¹
T = 100 K
0.16 × 0.13 × 0.13 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ▶) T _min = 0.890, T _max = 1.000
7588 measured reflections
1942 independent reflections
1865 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.075
S = 1.05
1942 reflections
140 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.18 e Å⁻³
Absolute structure: Flack parameter determined using 735 quotients [(I ⁺)−(I ⁻)]/[(I ⁺)+(I ⁻)] (Parsons et al., 2013 ▶)
Absolute structure parameter: 0.16 (13)

Data collection: CrysAlis PRO (Agilent, 2013 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) within OLEX2 (Dolomanov et al., 2009 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814002669/gk2601sup1.cif

e-70-0o265-sup1.cif^{(20.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814002669/gk2601Isup2.hkl

e-70-0o265-Isup2.hkl^{(107KB, hkl)}

Click here for additional data file.^{(3.7KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814002669/gk2601Isup3.cml

CCDC reference: http://scripts.iucr.org/cgi-bin/cr.cgi?rm=csd&csdid=985317

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯O1	0.95	2.38	2.898 (2)	114
O1—H1⋯N1ⁱ	0.98 (3)	1.80 (3)	2.7758 (18)	169 (3)
C5—H5⋯Cg1ⁱⁱ	0.95	3.08	3.873	142

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Symmetry codes: (i) Inline graphic ; (ii) .

supplementary crystallographic information

1. Comment

The title compound, which was prepared according to a known procedure (Moore & Huntress, 1927) has found extensive use as a starting material for preparation of medicinal active compounds such as novel cyclophilin A inhibitors (Ni et al., 2009), novel analogs of beta-adrenoceptor antagonists (Rad et al., 2012) and beta-blocker (Amlaiky et al., 1983).

The ring atoms, N and O atoms in the title compound molecule, are essentially coplanar with a maximum deviation of 0.079 (2) Å for the O atom from the averaged ring plane (13 carbon atoms). The molecule in the crystal exhibits a C12—H12···O1 intramolecular interaction (Table 1), (Figure 1). The molecules related by a twofold screw axis are connected by O1—H1···N1 hydrogen bonds (Table 1) within a helical bonding network extending along the a axis (Figure 2). Within one helical bonding network, the neighboring molecules related by a unit translation along [100] show π–π stacking interactions between their fluorene ring systems with the interplanar distance of 3.347 (2) Å (Figure 2). The neighboring helical bonding networks in parallel alignment are linked to each other by C5—H5··· π (Cg1) (Table 1) close contact between their fluorene groups (Figure 3). The dihedral angle between the fluorene units of adjacent molecules along the helix is 88.40 (2)°.

2. Experimental

To a solution of fluoren-9-one (1.8 g, 10 mmol) in EtOH (47 ml) was given a solution of hydroxylamine hydrochloride (NH₂OH^.HCl, 2.75 g, 39.6 mmol) in water (7 ml), and the resulting mixture was stirred at 70 ^oC for 5 h. Thereafter, the reaction mixture was cooled and given into water (150 ml). The colorless precipitate was extracted with CH₂Cl₂ (2 × 75 ml). The organic phase was dried over anhydrous MgSO₄ and concentrated in vacuo to give fluoren-9-one oxime (1.79 g, 92%) as a colorless solid, mp. 471 – 472 K; ν_max (KBr/cm^-1) 3500 – 2800 (bs, OH), 1604 (w), 1602, 1450, 1405, 1317, 1156, 1089, 998, 937, 780, 732, 640; δ_H (400 MHz, CDCl₃) 7.28 – 7.47 (4H, m), 7.62 (1H, d, ³J = 7.6 Hz), 7.66 (1H, d, ³J = 7.2 Hz), 7.77 (1H, d, ³J = 7.2 Hz), 8.42 (1H, d, ³J = 7.6 Hz); δ_C (100.5 MHz, CDCl₃) 119.8 (CH), 119.9 (CH), 121.7 (CH), 128.0 (CH), 128.4 (CH), 129.7 (CH), 130.2 (CH), 130.3 (C_quat), 131.3 (CH), 135.1 (C_quat), 140.5 (C_quat), 141.4 (C_quat), 153.6 (C_quat). Single crystals were obtained from cold CH₂Cl₂.