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Acta Crystallographica Section E: Structure Reports Online logoLink to Acta Crystallographica Section E: Structure Reports Online
. 2009 Aug 26;65(Pt 9):o2254. doi: 10.1107/S1600536809032772

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

Ben Capuano a, Ian T Crosby a, Craig M Forsyth b,*, James K Shin a
PMCID: PMC2969904  PMID: 21577651

Abstract

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 ▶).graphic file with name e-65-o2254-scheme1.jpg

Experimental

Crystal data

  • C10H7Cl3O

  • M r = 249.51

  • Monoclinic, Inline graphic

  • 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[F 2 > 2σ(F 2)] = 0.037

  • wR(F 2) = 0.100

  • S = 1.06

  • 2275 reflections

  • 127 parameters

  • H-atom parameters constrained

  • Δρmax = 0.53 e Å−3

  • Δρmin = −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 ▶).

Supplementary Material

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

e-65-o2254-sup1.cif (14.1KB, cif)

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

e-65-o2254-Isup2.hkl (111.8KB, hkl)

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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, CDCl3δ, 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, CDCl3δ, 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%.

Refinement

All H atoms for the primary molecules were initially located in the difference Fourier map but were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances in the range 0.95–1.00 Å and Uiso(H) = 1.2–1.5 Ueq(C).

Figures

Fig. 1.

Fig. 1.

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

Crystal data

C10H7Cl3O F(000) = 504
Mr = 249.51 Dx = 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
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Data collection

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

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(Fo2) + (0.0478P)2 + 0.6127P] where P = (Fo2 + 2Fc2)/3
2275 reflections (Δ/σ)max = 0.001
127 parameters Δρmax = 0.53 e Å−3
0 restraints Δρmin = −0.34 e Å−3
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Special details

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

x y z Uiso*/Ueq
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*
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Atomic displacement parameters (Å2)

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)
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Geometric parameters (Å, °)

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)
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Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2549).

References

  1. Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  2. Capuano, B., Crosby, I. T. & Lloyd, E. J. (2002). Curr. Med. Chem.9, 521–548. [DOI] [PubMed]
  3. Capuano, B., Crosby, I. T., Lloyd, E. J., Podloucka, A. & Taylor, D. A. (2008). Aust. J. Chem.61, 930–940.
  4. Fylaktakidou, K. C., Hadjipavlou-Litina, D. J., Litinas, K. E., Varella, E. A. & Nicolaides, D. N. (2008). Curr. Pharm. Des.14, 1001–1047. [DOI] [PubMed]
  5. Lectard, A. J., Petrissans, J. & Hauw, C. (1973). Cryst. Struct. Commun.2, 1–4.
  6. Lichanot, A., J. Petrissans, J., Hauw, C. & Gaultier, J. (1974). Cryst. Struct. Commun.3, 223–225.
  7. Nonius (1998). COLLECT Nonius BV, Delft, The Netherlands.
  8. Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
  9. Schmidt, K. F. (1923). Angew. Chem.36, 511–524.
  10. Sheldrick, G. M. (1997). CIFTAB University of Göttingen, Germany.
  11. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

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

e-65-o2254-sup1.cif (14.1KB, cif)

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

e-65-o2254-Isup2.hkl (111.8KB, hkl)

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography

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