Fluoren-9-one oxime

Bugenhagen, B.; Al Jasem, Y.; Al-Azani, M.; Thiemann, T.

doi:10.1107/S1600536814002669

organic compounds

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Volume 70| Part 3| March 2014| Page o265

doi:10.1107/S1600536814002669

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Fluoren-9-one oxime

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

^aInstitute for Inorganic and Applied Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, D-20146 Hamburg, Germany, ^bDepartment of Chemical Engineering, United Arab Emirates University, AL Ain, Abu Dhabi, United Arab Emirates, and ^cDepartment of Chemistry, United Arab Emirates University, AL Ain, Abu Dhabi, United Arab Emirates
^*Correspondence e-mail: thies@uaeu.ac.ae

(Received 13 January 2014; accepted 5 February 2014; online 8 February 2014)

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.

CCDC reference: 985317

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, P 2₁ 2₁ 2₁
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[F² > 2σ(F²)] = 0.029
wR(F²) = 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)

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
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

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.

Supporting information

CCDC reference: 985317

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

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

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

checkCIF report

Comment top

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)°.

Related literature top

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 top

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.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); 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 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. A view of the title molecule with displacement ellipsoids shown at the 50% probability level, showing the intramolecular contact within the molecule.
	Fig. 2. Intermolecular interactions between molecules of the title compound, including the π–π stacking interactions (represented by arrows in yellow). [Symmetry codes: i: 1 + x,y,z; ii: 1/2 + x,1.5 - y,1 - z; iii: -1/2 + x,1.5 - y,1 - z; iv: x, y, z; v: -1/2 + x, 1/2 - y, 1 - z; vi: x, -1 + y, z]
	Fig. 3. The crystal packing diagram showing the O—H···N close contacts (colored in green) between adjacent molecules in each helical bonding network, C—H···π intermolecular interaction between molecules within different helices (colored in blue) and π–π stacking interactions (arrows in yellow).

Fluoren-9-one oxime top

Crystal data top

C₁₃H₉NO	D_x = 1.378 Mg m⁻³
M_r = 195.21	Melting point = 471–472 K
Orthorhombic, P2₁2₁2₁	Cu Kα radiation, λ = 1.5418 Å
a = 4.8009 (1) Å	Cell parameters from 3850 reflections
b = 12.2309 (2) Å	θ = 4.5–76.1°
c = 16.0247 (3) Å	µ = 0.70 mm⁻¹
V = 940.96 (3) Å³	T = 100 K
Z = 4	Block, colourless
F(000) = 408	0.16 × 0.13 × 0.13 mm

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	1942 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	1865 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.029
Detector resolution: 10.4127 pixels mm^-1	θ_max = 76.3°, θ_min = 4.6°
ω scans	h = −6→5
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −14→15
T_min = 0.890, T_max = 1.000	l = −19→20
7588 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.029	w = 1/[σ²(F_o²) + (0.0384P)² + 0.1723P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.075	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.13 e Å⁻³
1942 reflections	Δρ_min = −0.18 e Å⁻³
140 parameters	Absolute structure: Flack parameter determined using 735 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.16 (13)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₃H₉NO	V = 940.96 (3) Å³
M_r = 195.21	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 4.8009 (1) Å	µ = 0.70 mm⁻¹
b = 12.2309 (2) Å	T = 100 K
c = 16.0247 (3) Å	0.16 × 0.13 × 0.13 mm

Data collection top

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

Refinement top

R[F² > 2σ(F²)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.075	Δρ_max = 0.13 e Å⁻³
S = 1.05	Δρ_min = −0.18 e Å⁻³
1942 reflections	Absolute structure: Flack parameter determined using 735 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
140 parameters	Absolute structure parameter: 0.16 (13)
0 restraints

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.

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

	x	y	z	U_iso*/U_eq
C1	0.5506 (4)	0.58330 (13)	0.40422 (10)	0.0189 (4)
C10	0.8197 (4)	0.44386 (15)	0.17647 (10)	0.0251 (4)
C11	0.9543 (4)	0.53953 (15)	0.20052 (10)	0.0242 (4)
C12	0.8830 (4)	0.59306 (14)	0.27456 (10)	0.0219 (4)
C13	0.6741 (4)	0.54803 (13)	0.32367 (10)	0.0196 (3)
C2	0.3367 (4)	0.50126 (13)	0.42679 (10)	0.0194 (3)
C3	0.1613 (4)	0.49391 (13)	0.49503 (10)	0.0209 (3)
C4	−0.0178 (4)	0.40413 (13)	0.50050 (11)	0.0228 (4)
C5	−0.0177 (4)	0.32387 (14)	0.43891 (11)	0.0246 (4)
C6	0.1590 (4)	0.33133 (14)	0.37017 (11)	0.0235 (4)
C7	0.3353 (4)	0.42037 (13)	0.36414 (10)	0.0195 (3)
C8	0.5403 (4)	0.45037 (13)	0.30001 (10)	0.0198 (4)
C9	0.6112 (4)	0.39797 (14)	0.22607 (11)	0.0239 (4)
H1	0.898 (6)	0.773 (2)	0.4668 (17)	0.068 (9)*
H10	0.8703	0.4093	0.1256	0.030*
H11	1.0969	0.5689	0.1661	0.029*
H12	0.9750	0.6584	0.2908	0.026*
H3	0.1626	0.5485	0.5372	0.025*
H4	−0.1408	0.3978	0.5467	0.027*
H5	−0.1399	0.2631	0.4438	0.029*
H6	0.1583	0.2764	0.3283	0.028*
H9	0.5200	0.3325	0.2097	0.029*
N1	0.6059 (3)	0.66488 (11)	0.45230 (8)	0.0202 (3)
O1	0.8178 (3)	0.73127 (10)	0.42014 (7)	0.0233 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0217 (9)	0.0194 (8)	0.0158 (7)	0.0029 (6)	−0.0016 (6)	0.0013 (6)
C10	0.0300 (10)	0.0290 (8)	0.0164 (7)	0.0078 (8)	−0.0003 (7)	−0.0031 (7)
C11	0.0257 (9)	0.0289 (9)	0.0179 (8)	0.0060 (7)	0.0018 (7)	0.0038 (7)
C12	0.0266 (9)	0.0206 (7)	0.0186 (8)	0.0025 (7)	−0.0013 (7)	0.0015 (6)
C13	0.0228 (9)	0.0204 (7)	0.0155 (7)	0.0050 (7)	−0.0024 (7)	−0.0007 (6)
C2	0.0216 (8)	0.0185 (7)	0.0181 (8)	0.0028 (7)	−0.0048 (7)	0.0005 (6)
C3	0.0233 (8)	0.0219 (7)	0.0174 (7)	0.0043 (7)	−0.0018 (7)	0.0005 (6)
C4	0.0223 (8)	0.0248 (8)	0.0214 (8)	0.0028 (6)	0.0007 (8)	0.0042 (7)
C5	0.0259 (9)	0.0210 (8)	0.0268 (9)	−0.0024 (7)	−0.0015 (7)	0.0030 (7)
C6	0.0277 (10)	0.0200 (7)	0.0228 (8)	0.0012 (7)	−0.0040 (7)	−0.0025 (6)
C7	0.0209 (8)	0.0200 (7)	0.0177 (7)	0.0037 (6)	−0.0021 (6)	−0.0002 (6)
C8	0.0212 (9)	0.0202 (7)	0.0181 (8)	0.0034 (7)	−0.0032 (7)	−0.0001 (6)
C9	0.0287 (10)	0.0220 (8)	0.0209 (8)	0.0030 (7)	−0.0039 (7)	−0.0034 (6)
N1	0.0236 (8)	0.0184 (6)	0.0185 (7)	0.0010 (6)	−0.0008 (6)	0.0014 (5)
O1	0.0283 (6)	0.0217 (5)	0.0198 (6)	−0.0058 (5)	0.0010 (5)	−0.0023 (4)

Geometric parameters (Å, º) top

C1—C13	1.484 (2)	C4—H4	0.9500
C1—C2	1.481 (2)	C5—C6	1.393 (2)
C10—C11	1.391 (3)	C5—H5	0.9500
C10—H10	0.9500	C6—C7	1.383 (2)
C11—C12	1.398 (2)	C6—H6	0.9500
C11—H11	0.9500	C7—C8	1.469 (2)
C12—C13	1.389 (2)	C8—C13	1.408 (2)
C12—H12	0.9500	C8—C9	1.389 (2)
C2—C7	1.410 (2)	C9—C10	1.396 (3)
C2—C3	1.383 (2)	C9—H9	0.9500
C3—C4	1.397 (2)	N1—C1	1.288 (2)
C3—H3	0.9500	O1—H1	0.98 (3)
C4—C5	1.392 (2)	O1—N1	1.4000 (19)

N1—O1—H1	107.7 (17)	C6—C7—C2	120.39 (16)
C1—N1—O1	112.25 (13)	C6—C7—C8	130.96 (16)
N1—C1—C2	121.43 (15)	C9—C8—C7	130.19 (16)
N1—C1—C13	131.53 (16)	C9—C8—C13	120.61 (16)
C2—C1—C13	107.00 (14)	C13—C8—C7	109.20 (14)
C3—C2—C1	131.26 (15)	C8—C9—H9	120.8
C3—C2—C7	120.97 (15)	C8—C9—C10	118.41 (16)
C7—C2—C1	107.75 (14)	C10—C9—H9	120.8
C2—C3—H3	120.8	C9—C10—H10	119.6
C2—C3—C4	118.38 (15)	C11—C10—C9	120.89 (16)
C4—C3—H3	120.8	C11—C10—H10	119.6
C3—C4—H4	119.7	C10—C11—H11	119.5
C5—C4—C3	120.63 (16)	C10—C11—C12	121.04 (17)
C5—C4—H4	119.7	C12—C11—H11	119.5
C4—C5—H5	119.5	C11—C12—H12	120.9
C4—C5—C6	120.97 (17)	C13—C12—C11	118.17 (17)
C6—C5—H5	119.5	C13—C12—H12	120.9
C5—C6—H6	120.7	C8—C13—C1	107.38 (15)
C7—C6—C5	118.66 (16)	C12—C13—C1	131.75 (16)
C7—C6—H6	120.7	C12—C13—C8	120.87 (15)
C2—C7—C8	108.64 (14)

O1—N1—C1—C2	178.85 (14)	C5—C6—C7—C2	0.5 (3)
O1—N1—C1—C13	1.2 (2)	C5—C6—C7—C8	−179.68 (17)
N1—C1—C2—C3	1.5 (3)	C6—C7—C8—C9	1.3 (3)
N1—C1—C2—C7	−177.14 (15)	C6—C7—C8—C13	−178.35 (18)
N1—C1—C13—C8	177.82 (17)	C7—C2—C3—C4	0.0 (2)
N1—C1—C13—C12	−1.4 (3)	C7—C8—C9—C10	−178.93 (17)
C1—C2—C3—C4	−178.52 (16)	C7—C8—C13—C1	−0.88 (18)
C1—C2—C7—C6	178.38 (15)	C7—C8—C13—C12	178.46 (15)
C1—C2—C7—C8	−1.52 (18)	C8—C9—C10—C11	0.3 (3)
C2—C1—C13—C8	−0.04 (18)	C9—C8—C13—C1	179.46 (15)
C2—C1—C13—C12	−179.28 (17)	C9—C8—C13—C12	−1.2 (2)
C2—C3—C4—C5	0.4 (2)	C9—C10—C11—C12	−0.6 (3)
C2—C7—C8—C9	−178.86 (18)	C10—C11—C12—C13	0.1 (3)
C2—C7—C8—C13	1.53 (18)	C11—C12—C13—C1	179.97 (17)
C3—C2—C7—C6	−0.5 (2)	C11—C12—C13—C8	0.8 (2)
C3—C2—C7—C8	179.64 (15)	C13—C1—C2—C3	179.66 (16)
C3—C4—C5—C6	−0.4 (3)	C13—C1—C2—C7	0.98 (18)
C4—C5—C6—C7	0.0 (3)	C13—C8—C9—C10	0.6 (2)

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) x−1/2, −y+1/2, −z+1.

Hydrogen-bond geometry (Å, º) top

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	3.076	3.873	142

Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) x−1/2, −y+1/2, −z+1.

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