2,2,7-Trichloro-3,4-dihydro­naphthalen-1(2H)-one

Capuano, B.; Crosby, I.T.; Forsyth, C.M.; Shin, J.K.

doi:10.1107/S1600536809032772

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2254

doi:10.1107/S1600536809032772

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2,2,7-Trichloro-3,4-dihydronaphthalen-1(2H)-one

Ben Capuano,^a Ian T. Crosby,^a Craig M. Forsyth ^b ^* and James K. Shin ^a

^aMedicinal Chemistry and Drug Action, Monash Institute of Pharmaceutical Sciences, Monash University (Parkville Campus), 381 Royal Parade, Parkville, Victoria 3052, Australia, and ^bSchool of Chemistry, Monash University, Clayton, Victoria 3800, Australia
^*Correspondence e-mail: craig.forsyth@sci.monash.edu.au

(Received 7 August 2009; accepted 18 August 2009; online 26 August 2009)

The title compound, C₁₀H₇Cl₃O, obtained as a major byproduct from a classical Schmidt reaction. The cyclohexyl ring is distorted from a classical chair conformation, as observed for monocyclic analogues, presumably due to conjugation of the planar annulated benzo ring and the ketone group (r.m.s. deviation 0.024 Å). There are no significant intermolecular interactions.

Related literature

For the Schmidt reaction, see: Schmidt (1923 ). Lactams and their derived amidines are common structural moieties in a variety of phamaceutical agents (Fylaktakidou et al., 2008 ), and are common in antipsychotics (Capuano et al., 2002 , 2008 ). For the conformation of the cyclohexyl ring in monocyclic analogues, see: Lectard et al. (1973 ); Lichanot et al. (1974 ).

Experimental

Crystal data

C₁₀H₇Cl₃O
M_r = 249.51
Monoclinic, P 2₁ /c
a = 8.5233 (1) Å
b = 8.0182 (2) Å
c = 14.8698 (3) Å
β = 102.561 (1)°
V = 991.90 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.88 mm⁻¹
T = 123 K
0.28 × 0.10 × 0.10 mm

Data collection

Nonius Kappa CCD diffractometer
Absorption correction: none
9399 measured reflections
2275 independent reflections
1859 reflections with I > 2σ(I)
R_int = 0.064

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.100
S = 1.06
2275 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997 ); data reduction: DENZO–SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: CIFTAB (Sheldrick, 1997 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809032772/hg2549sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809032772/hg2549Isup2.hkl

checkCIF report

Comment top

The reaction between hydrazoic acid and carbonyl compounds in the presence of strong acid is known as the Schmidt reaction (Schmidt, 1923) and provides a method for conversion of cyclic ketones to lactams. Lactams as well as their derived amidines are common structural moieties in a variety of phamaceutical agents (Fylaktakidou, et al. 2008), but are specifically of interest to our group as they are common in antipsychotics (Capuano, et al. 2002, 2008). In the current study, reaction of 7-chloro-1-tetralone with sodium azide and hydrochloric acid gave the desired alkyl migration lactam, 8-chloro-2,3,4,5-tetrahydro-1 H-2-benzazepin-1-one, but also a significant amount of the title compound. The solid state structure shows a typical bicyclic ketone framework with two fused six-membered rings and a gem-dichloro substituent in the 2 position. The cyclohexyl ring is distorted from a classical chair conformation, as observed for monocyclic analogues (Lectard, et al., 1973, Lichanot, et al., 1974), presumably due to conjugation of the planar annulated benzo ring and the ketone group (RMS deviation 0.024Å). There are no significant intermolecular interactions.

Related literature top

For the Schmidt reaction, see: Schmidt (1923). Lactams and their derived amidines are common structural moieties in a variety of phamaceutical agents (Fylaktakidou et al., 2008), and are common in antipsychotics (Capuano et al., 2002, 2008). For the conformation of the cyclohexyl ring in monocyclic analogues, see: Lectard et al. (1973); Lichanot et al. (1974).

Experimental top

Sodium azide (1.30 g, 20.0 mmol) was added to a stirred solution of 7-chloro-3,4-dihydronaphthalen-1(2H)-one (1.00 g, 5.54 mmol) in concentrated HCl maintained at 0 °C. After warming to room temperature and stirring overnight, the mixture was poured into water and neutralized with K₂CO₃. The crude product mixture was extracted with CH₂Cl₂ and purified by flash chromatography (silica; ethyl acetate). The fractions containing the title compound were evaporated and the residue was recrystallized from CHCl₃/hexane yielding beige prismatic crystals. (m.p. 435–436 K). ¹H NMR (300 MHz, CDCl₃ δ, p.p.m.): 8.12 (d, 1H, J = 2.5 Hz, H8), 7.52 (dd, 1H, J = 8.0, 2.5 Hz, H6), 7.23 (d, 1H, J = 8.0 Hz, H5), 3.18 (t, 2H, J = 6.0 Hz, H4), 2.95 (t, 2H, J = 6.0 Hz, H3). ¹³C NMR (75 MHz, CDCl₃ δ, p.p.m.): 183.0, 140.4, 134.6, 133.9, 130.3, 129.8, 129.4, 85.7, 43.0, 27.0. m/z (EI, 70 ev): 254 (1%, M⁺[³⁷Cl]₃), 252 (7, M⁺[³⁵Cl][³⁷Cl]₂, 250 (24, M⁺[³⁵Cl]₂[³⁷Cl]), 248 (26, M⁺[³⁵Cl]₃), 213 (20), 152 (100), 124 (36), 89 (19). Calcd. for C₁₀H₇Cl₃O: C 48.1, H 2.8, Cl 42.6; found C 48.1, H 2.9, Cl 42.6%.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: CIFTAB (Sheldrick, 1997).

Figures top

Fig. 1. Molecular diagram of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

2,2,7-Trichloro-3,4-dihydronaphthalen-1(2H)-one top

Crystal data top

C₁₀H₇Cl₃O	F(000) = 504
M_r = 249.51	D_x = 1.671 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9399 reflections
a = 8.5233 (1) Å	θ = 2.8–27.5°
b = 8.0182 (2) Å	µ = 0.88 mm⁻¹
c = 14.8698 (3) Å	T = 123 K
β = 102.561 (1)°	Prism, colourless
V = 991.90 (3) Å³	0.28 × 0.10 × 0.10 mm
Z = 4

Data collection top

Nonius Kappa CCD diffractometer	1859 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.064
Graphite monochromator	θ_max = 27.5°, θ_min = 2.8°
ϕ and ω scans	h = −11→11
9399 measured reflections	k = −10→10
2275 independent reflections	l = −19→19

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0478P)² + 0.6127P] where P = (F_o² + 2F_c²)/3
2275 reflections	(Δ/σ)_max = 0.001
127 parameters	Δρ_max = 0.53 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₀H₇Cl₃O	V = 991.90 (3) Å³
M_r = 249.51	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.5233 (1) Å	µ = 0.88 mm⁻¹
b = 8.0182 (2) Å	T = 123 K
c = 14.8698 (3) Å	0.28 × 0.10 × 0.10 mm
β = 102.561 (1)°

Data collection top

Nonius Kappa CCD diffractometer	1859 reflections with I > 2σ(I)
9399 measured reflections	R_int = 0.064
2275 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.06	Δρ_max = 0.53 e Å⁻³
2275 reflections	Δρ_min = −0.34 e Å⁻³
127 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
Cl1	−0.11870 (6)	0.58915 (7)	0.26554 (4)	0.02493 (16)
Cl2	0.48515 (6)	1.11552 (6)	0.63056 (4)	0.02410 (15)
Cl3	0.25735 (6)	0.91201 (7)	0.70159 (4)	0.02542 (16)
O1	0.20373 (18)	1.05238 (18)	0.48477 (11)	0.0256 (4)
C1	0.2039 (2)	0.7561 (2)	0.48441 (13)	0.0167 (4)
C2	0.2751 (2)	0.6089 (2)	0.52503 (14)	0.0165 (4)
C3	0.2196 (2)	0.4562 (3)	0.48443 (14)	0.0199 (4)
H3	0.2659	0.3555	0.5116	0.024*
C4	0.0986 (2)	0.4492 (3)	0.40537 (14)	0.0200 (4)
H4	0.0616	0.3449	0.3786	0.024*
C5	0.0320 (2)	0.5981 (3)	0.36575 (14)	0.0187 (4)
C6	0.0818 (2)	0.7514 (2)	0.40393 (13)	0.0180 (4)
H6	0.0346	0.8514	0.3763	0.022*
C7	0.2542 (2)	0.9236 (2)	0.52247 (14)	0.0182 (4)
C8	0.3773 (2)	0.9241 (2)	0.61578 (14)	0.0173 (4)
C9	0.4939 (2)	0.7787 (3)	0.62603 (14)	0.0200 (4)
H9A	0.5645	0.7810	0.6884	0.024*
H9B	0.5627	0.7904	0.5806	0.024*
C10	0.4060 (2)	0.6127 (2)	0.61131 (14)	0.0198 (4)
H10A	0.4845	0.5231	0.6079	0.024*
H10B	0.3583	0.5894	0.6650	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0203 (3)	0.0295 (3)	0.0223 (3)	−0.0046 (2)	−0.0012 (2)	−0.0031 (2)
Cl2	0.0264 (3)	0.0186 (3)	0.0248 (3)	−0.0065 (2)	0.0002 (2)	−0.0013 (2)
Cl3	0.0253 (3)	0.0289 (3)	0.0240 (3)	0.0017 (2)	0.0097 (2)	0.0008 (2)
O1	0.0284 (8)	0.0142 (7)	0.0295 (8)	0.0003 (6)	−0.0037 (7)	0.0008 (6)
C1	0.0165 (9)	0.0157 (10)	0.0181 (9)	−0.0002 (7)	0.0043 (8)	0.0014 (8)
C2	0.0156 (9)	0.0158 (10)	0.0188 (9)	0.0010 (7)	0.0054 (7)	0.0017 (8)
C3	0.0206 (10)	0.0152 (10)	0.0250 (10)	0.0018 (8)	0.0070 (8)	0.0012 (8)
C4	0.0207 (10)	0.0168 (9)	0.0240 (10)	−0.0026 (8)	0.0083 (8)	−0.0040 (8)
C5	0.0157 (9)	0.0225 (11)	0.0178 (9)	−0.0038 (8)	0.0035 (8)	−0.0020 (8)
C6	0.0176 (9)	0.0176 (10)	0.0190 (10)	0.0012 (8)	0.0043 (8)	0.0017 (8)
C7	0.0173 (9)	0.0169 (10)	0.0198 (10)	0.0005 (8)	0.0029 (8)	0.0006 (8)
C8	0.0190 (9)	0.0148 (9)	0.0186 (9)	−0.0027 (8)	0.0050 (8)	0.0006 (8)
C9	0.0174 (9)	0.0214 (10)	0.0203 (10)	−0.0007 (8)	0.0021 (8)	0.0012 (8)
C10	0.0208 (10)	0.0157 (10)	0.0215 (10)	0.0012 (8)	0.0018 (8)	0.0027 (8)

Geometric parameters (Å, º) top

Cl1—C5	1.744 (2)	C4—C5	1.396 (3)
Cl2—C8	1.778 (2)	C4—H4	0.9500
Cl3—C8	1.803 (2)	C5—C6	1.382 (3)
O1—C7	1.208 (2)	C6—H6	0.9500
C1—C2	1.402 (3)	C7—C8	1.547 (3)
C1—C6	1.405 (3)	C8—C9	1.518 (3)
C1—C7	1.484 (3)	C9—C10	1.520 (3)
C2—C3	1.401 (3)	C9—H9A	0.9900
C2—C10	1.506 (3)	C9—H9B	0.9900
C3—C4	1.386 (3)	C10—H10A	0.9900
C3—H3	0.9500	C10—H10B	0.9900

C2—C1—C6	120.99 (18)	C1—C7—C8	115.33 (16)
C2—C1—C7	122.35 (17)	C9—C8—C7	112.93 (16)
C6—C1—C7	116.65 (17)	C9—C8—Cl2	109.90 (14)
C3—C2—C1	118.42 (18)	C7—C8—Cl2	110.16 (13)
C3—C2—C10	120.16 (17)	C9—C8—Cl3	110.33 (14)
C1—C2—C10	121.41 (17)	C7—C8—Cl3	104.88 (13)
C4—C3—C2	121.35 (19)	Cl2—C8—Cl3	108.46 (11)
C4—C3—H3	119.3	C8—C9—C10	111.50 (16)
C2—C3—H3	119.3	C8—C9—H9A	109.3
C3—C4—C5	118.84 (19)	C10—C9—H9A	109.3
C3—C4—H4	120.6	C8—C9—H9B	109.3
C5—C4—H4	120.6	C10—C9—H9B	109.3
C6—C5—C4	121.79 (19)	H9A—C9—H9B	108.0
C6—C5—Cl1	119.40 (16)	C2—C10—C9	112.99 (16)
C4—C5—Cl1	118.80 (15)	C2—C10—H10A	109.0
C5—C6—C1	118.60 (18)	C9—C10—H10A	109.0
C5—C6—H6	120.7	C2—C10—H10B	109.0
C1—C6—H6	120.7	C9—C10—H10B	109.0
O1—C7—C1	123.49 (19)	H10A—C10—H10B	107.8
O1—C7—C8	121.17 (18)

Experimental details

Crystal data
Chemical formula	C₁₀H₇Cl₃O
M_r	249.51
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	123
a, b, c (Å)	8.5233 (1), 8.0182 (2), 14.8698 (3)
β (°)	102.561 (1)
V (Å³)	991.90 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.88
Crystal size (mm)	0.28 × 0.10 × 0.10

Data collection
Diffractometer	Nonius Kappa CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9399, 2275, 1859
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.100, 1.06
No. of reflections	2275
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.34

Computer programs: COLLECT (Nonius, 1998), DENZO–SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), CIFTAB (Sheldrick, 1997).

Acknowledgements

We acknowledge support from Monash University and the Monash Institue of Pharmaceutical Sciences (Clayton and Parkville campuses) for funding this work.

References

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