9,10-Dimethyl-9,10-per­oxy-9,10-dihydro­anthracene

Wang, Y.-W.

doi:10.1107/S1600536807068456

organic compounds

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Volume 64| Part 4| April 2008| Page o660

doi:10.1107/S1600536807068456

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9,10-Dimethyl-9,10-peroxy-9,10-dihydroanthracene

Yun-Wu Wang ^a ^*

^aSchool of Computer and Computing Science, Zhejiang University City College, Hangzhou, Zhejiang 310015, People's Republic of China
^*Correspondence e-mail: wangyw@zucc.edu.cn

(Received 10 July 2007; accepted 27 December 2007; online 5 March 2008)

The structure of the title compound, C₁₆H₁₄O₂, contains one half-molecule in the asymmetric unit and the molecule is located on a mirror plane. The dihedral angle between the two benzene ring planes is 53.07 (6)°. The crystal structure involves intermolecular C—H⋯O hydrogen bonds.

Related literature

For related literature, see: Burrows et al. (1999 ); Gable et al. (1996 ); Karolak-Wojciechowska et al. (1998 ); Larson (1970 ); Price (1946 ); Simpson et al. (2004 ).

Experimental

Crystal data

C₁₆H₁₄O₂
M_r = 238.29
Orthorhombic, C m c 2₁
a = 12.9873 (7) Å
b = 11.0810 (8) Å
c = 8.8368 (8) Å
V = 1271.72 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 (1) K
0.40 × 0.35 × 0.30 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.958, T_max = 0.976
5690 measured reflections
812 independent reflections
585 reflections with F² > 2σ(F²)
R_int = 0.083

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.107
S = 1.00
699 reflections
94 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O2ⁱ	0.93	2.64	3.526 (2)	159
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: CrystalStructure.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807068456/ww2092sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807068456/ww2092Isup2.hkl

checkCIF report

Comment top

The Friedel–Crafts reaction of an alkyl halide with an aromatic hydrocarbon in the presence of aluminium chloride yields a substituted phenyl compound (Price, 1946). The reaction does not, however, stop at the stage of mono-substitution, an unpredictable compound was reported and determined by X-ray crystal structure analysis. The molecule of the title compound lie on a crystallographic mirror plane, which pass through atoms C1/O1/O2/C8/C9/C10 (Fig. 1). The geometrical parameters for (1) are similar to those of related 9,10-bridged anthracene derivatives (Simpson et al., 2004; Gable et al., 1996; Burrows et al., 1999). Atoms C1, C8 are almost coplanar with the benzene ring plane, and the deviating distance from the benzene ring are 0.0074 Å, -0.066 Å respectively. The dihedral angle between the plane of bridge atoms C1—O1—O2—C8 and the benzene ring plane is 63.45 (5)°. The benzene ring plane and its symmetry-related one form the dihedral angle of 53.07 (6)°, which is smaller than that of 9,10-bridged anthrancene systems, e.g. the corresponding dihedral angle in 11,12-bis(N,N-dimethyl-aminomethyl)-9,10-dihydro-9,10-ethanoanthrancene (Karolak-Wojciechowska et al., 1998) is 58.8 (2)°. The three six-membered rings of the bicycle core of (1) [C1—C2—C7—C8—C7ⁱ—C2ⁱ, C1—C2—C7—C8—O2—O1, C1—C2ⁱ—C7ⁱ—C8—O2—O1, symmetric code (i): 1 - x,y,z] are all forced into boat forms. Intermolecular weak interactions, C4—H4···O2ⁱⁱ [symmetric code (ii): 1/2 + x, 1/2 - y, -1/2 + z] and C6—H6···C4ⁱⁱⁱ [symmctric code (iii): x, 1 - y, 1/2 + z], link the molecules into circles (Fig. 2). The bridged O2 atom attached to H4 atom of neighbouring benzene ring may result in the longer distance O2—C8, compared with the bond length C1—O1 (Table 1).

Related literature top

For related literature, see: Burrows et al. (1999); Gable et al. (1996); Karolak-Wojciechowska et al. (1998); Larson (1970); Price (1946); Simpson et al. (2004).

Experimental top

Ethyl 2-bromo-2-methylpropionate (3.84 g, 20 mmol) was added to a 50 ml flask equipped with a reflux condenser and large magnetic stirrer. Anhydrous benzene (20 ml) was added to the flask, followed by fresh anhydrous AlCl₃ (9.00 g, 67.5 mmol) in small portions. The solution was then slowly heated to the reflux temperature and at this time the exit of the reflux condenser was connected to a flowing-water HBr trap. The mixture was heated a total of 24 h without interruption. The reaction mixture was then cooled to 278k. and treated with 20 ml of 50/50 (by volume) conc. HCl/H₂O to decompose the catalyst complex. The benzene layer was then separated, washed once with ice-cold H₂O (12 ml) and twice with dilute aqueous sodium hydroxide. The organic phase was evaporate. After 6 days, a single-crystal suitable for X-ray analysis was obtained by recrystallization from ethanol.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004).

Figures top

	Fig. 1. A view of (1). Displacement ellipsoids are drawn at 30% probability level and H atoms are shown as small circles of arbitary radii. Symmetry code (i): 1 - x, y, z
	Fig. 2. Packing arrangement for (1).

9,10-Dimethyl-9,10-peroxy-9,10-dihydroanthracene top

Crystal data top

C₁₆H₁₄O₂	F(000) = 504.00
M_r = 238.29	D_x = 1.244 Mg m⁻³
Orthorhombic, Cmc2₁	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: C 2c -2	Cell parameters from 2234 reflections
a = 12.9873 (7) Å	θ = 2.4–27.3°
b = 11.0810 (8) Å	µ = 0.08 mm⁻¹
c = 8.8368 (8) Å	T = 296 K
V = 1271.72 (16) Å³	Chunk, yellow
Z = 4	0.40 × 0.35 × 0.30 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	585 reflections with F² > 2σ(F²)
Detector resolution: 10.00 pixels mm^-1	R_int = 0.083
ω scans	θ_max = 27.5°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −16→16
T_min = 0.958, T_max = 0.976	k = −14→12
5690 measured reflections	l = −11→11
812 independent reflections

Refinement top

Refinement on F²	w = 1/[0.0011F_o² + σ(F_o²)]/(4F_o²)
R[F² > 2σ(F²)] = 0.042	(Δ/σ)_max < 0.001
wR(F²) = 0.107	Δρ_max = 0.23 e Å⁻³
S = 1.00	Δρ_min = −0.19 e Å⁻³
699 reflections	Extinction correction: (Larson, 1970)
94 parameters	Extinction coefficient: 132 (34)
H-atom parameters constrained

Crystal data top

C₁₆H₁₄O₂	V = 1271.72 (16) Å³
M_r = 238.29	Z = 4
Orthorhombic, Cmc2₁	Mo Kα radiation
a = 12.9873 (7) Å	µ = 0.08 mm⁻¹
b = 11.0810 (8) Å	T = 296 K
c = 8.8368 (8) Å	0.40 × 0.35 × 0.30 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	812 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	585 reflections with F² > 2σ(F²)
T_min = 0.958, T_max = 0.976	R_int = 0.083
5690 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	94 parameters
wR(F²) = 0.107	H-atom parameters constrained
S = 1.00	Δρ_max = 0.23 e Å⁻³
699 reflections	Δρ_min = −0.19 e Å⁻³

Special details top

Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0σ(F²) is used only for calculating R-factor (gt).

Data collection(812 indenpent reflections but 699 in refinement): The author of the software, Dr Lee Daniels (ldaniels@RigakuMSC.com) explain this problem (see following). The number of reflections used to refine the cell is taken from the diffractometer program, which uses all available reflections measured in different scans. Even though some reflections are used more than once, they measured at different psi angles and therefore represent independent observations for determination of the cell dimensions.

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

	x	y	z	U_iso*/U_eq
O1	0.5000	0.1212 (2)	0.7053 (3)	0.0584 (7)
O2	0.5000	0.1937 (2)	0.8453 (2)	0.0547 (6)
C1	0.5000	0.1992 (2)	0.5707 (4)	0.0488 (9)
C2	0.59500 (13)	0.27732 (18)	0.5847 (2)	0.0466 (6)
C3	0.67877 (17)	0.2829 (2)	0.4883 (3)	0.0631 (8)
C4	0.76037 (19)	0.3580 (2)	0.5212 (3)	0.0750 (10)
C5	0.75816 (19)	0.4289 (3)	0.6492 (3)	0.0769 (9)
C6	0.67600 (18)	0.4228 (2)	0.7475 (3)	0.0655 (8)
C7	0.59468 (14)	0.3466 (2)	0.7153 (2)	0.0482 (5)
C8	0.5000	0.3253 (3)	0.8122 (4)	0.0502 (9)
C9	0.500000 (10)	0.1104 (4)	0.4404 (5)	0.0734 (12)
C10	0.500000 (10)	0.3808 (4)	0.9660 (5)	0.0786 (13)
H3	0.6800	0.2359	0.4011	0.076*
H4	0.8170	0.3608	0.4569	0.090*
H5	0.8125	0.4811	0.6693	0.092*
H6	0.6753	0.4696	0.8349	0.079*
H101	0.5603	0.3555	1.0201	0.094*
H102	0.5000	0.4671	0.9567	0.094*
H901	0.5604	0.0606	0.4462	0.088*
H902	0.5000	0.1538	0.3464	0.088*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0637 (13)	0.0364 (11)	0.0750 (17)	0.0000	0.0000	0.0017 (13)
O2	0.0565 (13)	0.0537 (13)	0.0538 (15)	0.0000	0.0000	0.0087 (11)
C1	0.0523 (17)	0.0373 (15)	0.057 (2)	0.0000	0.0000	−0.0067 (16)
C2	0.0403 (12)	0.0385 (10)	0.0608 (15)	0.0054 (8)	0.0021 (10)	0.0028 (10)
C3	0.0594 (14)	0.0578 (15)	0.072 (2)	0.0127 (11)	0.0150 (14)	0.0089 (14)
C4	0.0450 (13)	0.081 (2)	0.099 (2)	0.0072 (13)	0.0146 (15)	0.032 (2)
C5	0.0440 (13)	0.0784 (19)	0.108 (2)	−0.0167 (13)	−0.0131 (16)	0.037 (2)
C6	0.0569 (14)	0.0614 (15)	0.078 (2)	−0.0120 (12)	−0.0224 (14)	0.0061 (14)
C7	0.0400 (10)	0.0440 (10)	0.0606 (14)	0.0016 (8)	−0.0061 (10)	0.0019 (12)
C8	0.0492 (16)	0.0492 (18)	0.052 (2)	0.0000	0.0000	−0.0027 (15)
C9	0.089 (2)	0.054 (2)	0.077 (2)	0.0000	0.0000	−0.019 (2)
C10	0.089 (2)	0.089 (2)	0.058 (2)	0.0000	0.0000	−0.017 (2)

Geometric parameters (Å, º) top

O1—O2	1.475 (3)	C7—C8	1.517 (3)
O1—C1	1.470 (4)	C8—C10	1.492 (6)
O2—C8	1.487 (4)	C3—H3	0.930
C1—C2	1.512 (2)	C4—H4	0.930
C1—C2ⁱ	1.512 (2)	C5—H5	0.930
C1—C9	1.514 (5)	C6—H6	0.930
C2—C3	1.383 (3)	C9—H901	0.960
C2—C7	1.386 (3)	C9—H901ⁱ	0.960
C3—C4	1.378 (3)	C9—H902	0.960
C4—C5	1.377 (4)	C10—H101	0.960
C5—C6	1.378 (3)	C10—H101ⁱ	0.960
C6—C7	1.382 (3)	C10—H102	0.960

O2—O1—C1	111.0 (2)	C7—C8—C10	116.76 (19)
O1—O2—C8	111.6 (2)	C7ⁱ—C8—C10	116.75 (19)
O1—C1—C2	105.68 (18)	C2—C3—H3	119.9
O1—C1—C2ⁱ	105.68 (18)	C4—C3—H3	119.9
O1—C1—C9	103.5 (2)	C3—C4—H4	119.9
C2—C1—C2ⁱ	109.3 (2)	C5—C4—H4	119.9
C2—C1—C9	115.72 (18)	C4—C5—H5	119.8
C2ⁱ—C1—C9	115.72 (18)	C6—C5—H5	119.8
C1—C2—C3	128.1 (2)	C5—C6—H6	120.3
C1—C2—C7	112.5 (2)	C7—C6—H6	120.3
C3—C2—C7	119.37 (19)	C1—C9—H901	109.5
C2—C3—C4	120.1 (2)	C1—C9—H901ⁱ	109.5
C3—C4—C5	120.1 (2)	C1—C9—H902	109.5
C4—C5—C6	120.4 (2)	H901—C9—H901ⁱ	109.5
C5—C6—C7	119.4 (2)	H901—C9—H902	109.5
C2—C7—C6	120.5 (2)	H901ⁱ—C9—H902	109.5
C2—C7—C8	112.7 (2)	C8—C10—H101	109.5
C6—C7—C8	126.7 (2)	C8—C10—H101ⁱ	109.5
O2—C8—C7	105.30 (19)	C8—C10—H102	109.5
O2—C8—C7ⁱ	105.30 (19)	H101—C10—H101ⁱ	109.4
O2—C8—C10	103.0 (3)	H101—C10—H102	109.5
C7—C8—C7ⁱ	108.3 (2)	H101ⁱ—C10—H102	109.5

O2—O1—C1—C2	57.93 (16)	C1—C2—C7—C6	179.4 (2)
O2—O1—C1—C2ⁱ	−57.93 (16)	C1—C2—C7—C8	0.8 (2)
O1—O2—C8—C7	−57.16 (18)	C3—C2—C7—C6	1.5 (3)
O1—O2—C8—C7ⁱ	57.16 (18)	C3—C2—C7—C8	−177.1 (2)
O1—C1—C2—C3	118.2 (2)	C7—C2—C3—C4	−0.8 (3)
O1—C1—C2—C7	−59.5 (2)	C2—C3—C4—C5	−0.9 (4)
O1—C1—C2ⁱ—C3ⁱ	−118.2 (2)	C3—C4—C5—C6	1.9 (4)
O1—C1—C2ⁱ—C7ⁱ	59.5 (2)	C4—C5—C6—C7	−1.2 (4)
C2—C1—C2ⁱ—C3ⁱ	128.5 (2)	C5—C6—C7—C2	−0.5 (3)
C2—C1—C2ⁱ—C7ⁱ	−53.8 (3)	C5—C6—C7—C8	177.9 (2)
C2ⁱ—C1—C2—C3	−128.5 (2)	C2—C7—C8—O2	57.3 (2)
C2ⁱ—C1—C2—C7	53.8 (3)	C2—C7—C8—C10	170.8 (2)
C9—C1—C2—C3	4.3 (4)	C2—C7—C8—C7ⁱ	−55.0 (3)
C9—C1—C2—C7	−173.3 (2)	C6—C7—C8—O2	−121.2 (2)
C9—C1—C2ⁱ—C3ⁱ	−4.3 (4)	C6—C7—C8—C10	−7.7 (4)
C9—C1—C2ⁱ—C7ⁱ	173.3 (2)	C6—C7—C8—C7ⁱ	126.5 (2)
C1—C2—C3—C4	−178.4 (2)

Symmetry code: (i) −x+1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O2ⁱⁱ	0.93	2.64	3.526 (2)	159

Symmetry code: (ii) x+1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₄O₂
M_r	238.29
Crystal system, space group	Orthorhombic, Cmc2₁
Temperature (K)	296
a, b, c (Å)	12.9873 (7), 11.0810 (8), 8.8368 (8)
V (Å³)	1271.72 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.40 × 0.35 × 0.30

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.958, 0.976
No. of measured, independent and observed [F² > 2σ(F²)] reflections	5690, 812, 585
R_int	0.083
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.107, 1.00
No. of reflections	699
No. of parameters	94
No. of restraints	?
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.19

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 1997), CRYSTALS (Betteridge et al., 2003), ORTEP-3 for Windows (Farrugia, 1997).

Selected bond lengths (Å) top

O1—C1

1.470 (4)

O2—C8

1.487 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O2ⁱ	0.930	2.643	3.526 (2)	158.68

Symmetry code: (i) x+1/2, −y+1/2, z−1/2.

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page o660

doi:10.1107/S1600536807068456

Open

access