Literature DB >> 23634120

2,2-Dichloro-3,7,7,11-tetra-methyl-10-aza-tetra-cyclo-[6.5.0.0(1,3).0(9,11)]trideca-ne.

Abdelouahd Oukhrib¹, Ahmed Benharref, Mohamed Saadi, Moha Berraho, Lahcen El Ammari.

Abstract

The title compound, C16H25Cl2N, was synthesized from β-himachalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzocyclo-heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus Atlantica). The mol-ecule is built up from fused six- and seven-membered rings linked to two three-membered rings. The six-membered ring shows a half-chair conformation, whereas the seven-membered ring displays a boat conformation. The dihedral angle between the mean planes through the six- and seven-membered rings is 59.8 (2)°. The two three-membered rings lie to one side and each is nearly perpendicular to the six-membered ring, forming dihedral angles of 83.2 (2) and 86.0 (2)°. The absolute structure was established unambiguously from anomalous dispersion effects. No specific inter-molecular inter-actions are noted in the crystal structure.

Entities: CellLine Chemical Disease Species

Year: 2013 PMID： 23634120 PMCID： PMC3629633 DOI： 10.1107/S1600536813007642

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For the isolation of β-himachalene, see: Joseph & Dev (1968 ▶); Plattier & Teisseire (1974 ▶). For the reactivity of this sesquiterpene, see: Lassaba et al. (1998 ▶); Chekroun et al. (2000 ▶); El Jamili et al. (2002 ▶); Sbai et al. (2002 ▶); Dakir et al. (2004 ▶). For its biological activity, see: Daoubi et al. (2004 ▶). For a similar compound, see: Benharref et al. (2010 ▶). For puckering calculations, see: Cremer & Pople (1975 ▶). For the Flack parameter refinement, see: Flack & Bernardinelli (2000 ▶).

Experimental

Crystal data

C16H25Cl2N M = 302.27 Orthorhombic, a = 8.607 (3) Å b = 13.222 (4) Å c = 13.973 (4) Å V = 1590.2 (8) Å3 Z = 4 Mo Kα radiation μ = 0.40 mm−1 T = 296 K 0.43 × 0.31 × 0.28 mm

Data collection

Bruker X8 APEX Diffractometer 22014 measured reflections 3261 independent reflections 2924 reflections with I > 2σ(I) R int = 0.048

Refinement

R[F 2 > 2σ(F 2)] = 0.049 wR(F 2) = 0.144 S = 1.06 3261 reflections 172 parameters H-atom parameters constrained Δρmax = 0.33 e Å−3 Δρmin = −0.37 e Å−3 Absolute structure: Flack & Bernardinelli (2000 ▶), 1385 Friedel pairs Flack parameter: 0.12 (9) Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶). Click here for additional data file. Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813007642/tk5210sup1.cif Click here for additional data file. Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813007642/tk5210Isup2.hkl Click here for additional data file. Supplementary material file. DOI: 10.1107/S1600536813007642/tk5210Isup3.cml Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₁₆H₂₅Cl₂N	F(000) = 648
M_r = 302.27	D_x = 1.263 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3261 reflections
a = 8.607 (3) Å	θ = 2.8–26.4°
b = 13.222 (4) Å	µ = 0.40 mm⁻¹
c = 13.973 (4) Å	T = 296 K
V = 1590.2 (8) Å³	Block, colourless
Z = 4	0.43 × 0.31 × 0.28 mm

Bruker X8 APEX Diffractometer	2924 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.048
Graphite monochromator	θ_max = 26.4°, θ_min = 2.8°
φ and ω scans	h = −10→10
22014 measured reflections	k = −16→16
3261 independent reflections	l = −17→15

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.049	H-atom parameters constrained
wR(F²) = 0.144	w = 1/[σ²(F_o²) + (0.0883P)² + 0.3114P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
3261 reflections	Δρ_max = 0.33 e Å⁻³
172 parameters	Δρ_min = −0.37 e Å⁻³
0 restraints	Absolute structure: Flack & Bernardinelli (2000), 1385 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.12 (9)

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.

	x	y	z	U_iso*/U_eq
C1	0.4201 (3)	0.11081 (16)	0.12828 (15)	0.0369 (4)
C2	0.5296 (3)	0.16233 (19)	0.1977 (2)	0.0484 (6)
C3	0.3732 (3)	0.20831 (17)	0.18198 (19)	0.0434 (5)
C4	0.2502 (3)	0.1978 (2)	0.2585 (2)	0.0565 (7)
H4A	0.2472	0.2589	0.2968	0.068*
H4B	0.2763	0.1418	0.3002	0.068*
C5	0.0892 (4)	0.1794 (3)	0.2136 (3)	0.0702 (9)
H5A	0.0222	0.1493	0.2616	0.084*
H5B	0.0446	0.2442	0.1962	0.084*
C6	0.0895 (3)	0.1110 (3)	0.1247 (2)	0.0659 (8)
H6A	−0.0176	0.1018	0.1047	0.079*
H6B	0.1420	0.1472	0.0737	0.079*
C7	0.1632 (3)	0.0070 (2)	0.1324 (2)	0.0580 (7)
C8	0.3404 (3)	0.01312 (17)	0.15959 (18)	0.0417 (5)
H8	0.3455	0.0116	0.2296	0.050*
C9	0.4322 (4)	−0.07729 (18)	0.1245 (2)	0.0571 (7)
H9	0.3835	−0.1432	0.1356	0.069*
C10	0.5372 (4)	−0.0736 (2)	0.0465 (2)	0.0587 (7)
C11	0.5738 (4)	0.0256 (2)	−0.0032 (2)	0.0586 (7)
H11A	0.5704	0.0151	−0.0718	0.070*
H11B	0.6788	0.0458	0.0134	0.070*
C12	0.4628 (3)	0.11134 (17)	0.02269 (18)	0.0463 (5)
H12A	0.5110	0.1755	0.0069	0.056*
H12B	0.3689	0.1050	−0.0152	0.056*
C13	0.3622 (4)	0.30807 (19)	0.1274 (2)	0.0622 (8)
H13A	0.2553	0.3283	0.1229	0.093*
H13B	0.4041	0.2995	0.0643	0.093*
H13C	0.4201	0.3592	0.1607	0.093*
C14	0.0838 (5)	−0.0597 (4)	0.2083 (4)	0.1120 (17)
H14A	0.1340	−0.1245	0.2105	0.168*
H14B	−0.0237	−0.0685	0.1919	0.168*
H14C	0.0915	−0.0277	0.2698	0.168*
C15	0.1378 (5)	−0.0448 (3)	0.0346 (3)	0.0918 (13)
H15A	0.1827	−0.1113	0.0358	0.138*
H15B	0.1865	−0.0055	−0.0148	0.138*
H15C	0.0285	−0.0499	0.0219	0.138*
C16	0.5914 (7)	−0.1679 (2)	−0.0021 (3)	0.0979 (15)
H16A	0.6623	−0.1507	−0.0526	0.147*
H16B	0.5037	−0.2031	−0.0285	0.147*
H16C	0.6429	−0.2106	0.0435	0.147*
N1	0.5979 (4)	−0.0721 (2)	0.1464 (2)	0.0727 (8)
H1	0.6735	−0.0698	0.1866	0.087*
Cl1	0.69426 (9)	0.22566 (7)	0.15164 (8)	0.0806 (3)
Cl2	0.57859 (12)	0.10793 (7)	0.30962 (6)	0.0787 (3)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0393 (10)	0.0313 (9)	0.0401 (11)	0.0019 (9)	−0.0026 (9)	0.0007 (8)
C2	0.0426 (13)	0.0495 (13)	0.0530 (14)	0.0034 (10)	−0.0124 (11)	−0.0055 (12)
C3	0.0428 (12)	0.0363 (11)	0.0511 (13)	0.0038 (9)	−0.0107 (10)	−0.0061 (10)
C4	0.0541 (15)	0.0578 (15)	0.0577 (16)	0.0119 (13)	−0.0002 (13)	−0.0190 (12)
C5	0.0458 (15)	0.0760 (19)	0.089 (2)	0.0104 (14)	0.0044 (16)	−0.0241 (17)
C6	0.0408 (13)	0.0736 (18)	0.083 (2)	0.0009 (13)	−0.0108 (14)	−0.0123 (16)
C7	0.0523 (16)	0.0500 (14)	0.0716 (19)	−0.0133 (12)	−0.0001 (14)	−0.0002 (13)
C8	0.0499 (13)	0.0351 (10)	0.0402 (11)	0.0013 (9)	0.0042 (10)	0.0026 (9)
C9	0.0725 (18)	0.0337 (11)	0.0652 (16)	0.0058 (11)	0.0107 (15)	0.0050 (11)
C10	0.081 (2)	0.0435 (13)	0.0513 (14)	0.0133 (13)	0.0098 (14)	−0.0016 (11)
C11	0.0768 (19)	0.0514 (13)	0.0476 (14)	0.0046 (13)	0.0133 (15)	0.0026 (12)
C12	0.0583 (14)	0.0389 (10)	0.0417 (12)	−0.0006 (11)	0.0012 (11)	0.0066 (9)
C13	0.0754 (19)	0.0315 (11)	0.080 (2)	0.0063 (12)	−0.0126 (16)	−0.0043 (12)
C14	0.073 (3)	0.111 (3)	0.152 (4)	−0.030 (2)	0.025 (3)	0.043 (3)
C15	0.086 (3)	0.076 (2)	0.113 (3)	−0.021 (2)	−0.016 (2)	−0.032 (2)
C16	0.158 (4)	0.0552 (17)	0.080 (2)	0.038 (2)	0.038 (3)	−0.0021 (16)
N1	0.0837 (19)	0.0743 (16)	0.0603 (14)	0.0316 (14)	−0.0066 (14)	0.0046 (13)
Cl1	0.0445 (4)	0.0787 (5)	0.1185 (8)	−0.0163 (3)	−0.0029 (4)	−0.0138 (5)
Cl2	0.0834 (6)	0.0917 (6)	0.0611 (4)	0.0245 (5)	−0.0341 (4)	−0.0037 (4)

C1—C2	1.514 (3)	C9—N1	1.460 (5)
C1—C12	1.521 (3)	C9—H9	0.9800
C1—C8	1.527 (3)	C10—C16	1.495 (4)
C1—C3	1.545 (3)	C10—N1	1.491 (4)
C2—C3	1.493 (3)	C10—C11	1.517 (4)
C2—Cl1	1.767 (3)	C11—C12	1.526 (4)
C2—Cl2	1.772 (3)	C11—H11A	0.9700
C3—C4	1.511 (4)	C11—H11B	0.9700
C3—C13	1.527 (4)	C12—H12A	0.9700
C4—C5	1.540 (4)	C12—H12B	0.9700
C4—H4A	0.9700	C13—H13A	0.9600
C4—H4B	0.9700	C13—H13B	0.9600
C5—C6	1.537 (5)	C13—H13C	0.9600
C5—H5A	0.9700	C14—H14A	0.9600
C5—H5B	0.9700	C14—H14B	0.9600
C6—C7	1.518 (4)	C14—H14C	0.9600
C6—H6A	0.9700	C15—H15A	0.9600
C6—H6B	0.9700	C15—H15B	0.9600
C7—C14	1.539 (5)	C15—H15C	0.9600
C7—C15	1.545 (5)	C16—H16A	0.9600
C7—C8	1.574 (4)	C16—H16B	0.9600
C8—C9	1.515 (3)	C16—H16C	0.9600
C8—H8	0.9800	N1—H1	0.8600
C9—C10	1.416 (4)

C2—C1—C12	118.0 (2)	N1—C9—C8	113.8 (2)
C2—C1—C8	118.5 (2)	C10—C9—H9	115.3
C12—C1—C8	112.99 (19)	N1—C9—H9	115.3
C2—C1—C3	58.42 (15)	C8—C9—H9	115.3
C12—C1—C3	122.04 (19)	C9—C10—C16	121.3 (3)
C8—C1—C3	116.70 (19)	C9—C10—N1	60.2 (2)
C3—C2—C1	61.83 (16)	C16—C10—N1	109.1 (3)
C3—C2—Cl1	118.46 (19)	C9—C10—C11	121.0 (2)
C1—C2—Cl1	118.6 (2)	C16—C10—C11	116.7 (3)
C3—C2—Cl2	120.6 (2)	N1—C10—C11	110.1 (3)
C1—C2—Cl2	122.04 (18)	C10—C11—C12	113.8 (2)
Cl1—C2—Cl2	108.84 (14)	C10—C11—H11A	108.8
C2—C3—C4	119.4 (2)	C12—C11—H11A	108.8
C2—C3—C13	118.8 (2)	C10—C11—H11B	108.8
C4—C3—C13	112.9 (2)	C12—C11—H11B	108.8
C2—C3—C1	59.75 (15)	H11A—C11—H11B	107.7
C4—C3—C1	116.7 (2)	C1—C12—C11	112.2 (2)
C13—C3—C1	119.6 (2)	C1—C12—H12A	109.2
C3—C4—C5	110.9 (2)	C11—C12—H12A	109.2
C3—C4—H4A	109.5	C1—C12—H12B	109.2
C5—C4—H4A	109.5	C11—C12—H12B	109.2
C3—C4—H4B	109.5	H12A—C12—H12B	107.9
C5—C4—H4B	109.5	C3—C13—H13A	109.5
H4A—C4—H4B	108.0	C3—C13—H13B	109.5
C6—C5—C4	114.9 (2)	H13A—C13—H13B	109.5
C6—C5—H5A	108.5	C3—C13—H13C	109.5
C4—C5—H5A	108.5	H13A—C13—H13C	109.5
C6—C5—H5B	108.5	H13B—C13—H13C	109.5
C4—C5—H5B	108.5	C7—C14—H14A	109.5
H5A—C5—H5B	107.5	C7—C14—H14B	109.5
C7—C6—C5	118.4 (3)	H14A—C14—H14B	109.5
C7—C6—H6A	107.7	C7—C14—H14C	109.5
C5—C6—H6A	107.7	H14A—C14—H14C	109.5
C7—C6—H6B	107.7	H14B—C14—H14C	109.5
C5—C6—H6B	107.7	C7—C15—H15A	109.5
H6A—C6—H6B	107.1	C7—C15—H15B	109.5
C6—C7—C14	112.5 (3)	H15A—C15—H15B	109.5
C6—C7—C15	106.3 (3)	C7—C15—H15C	109.5
C14—C7—C15	107.0 (3)	H15A—C15—H15C	109.5
C6—C7—C8	112.1 (2)	H15B—C15—H15C	109.5
C14—C7—C8	107.0 (3)	C10—C16—H16A	109.5
C15—C7—C8	111.9 (3)	C10—C16—H16B	109.5
C9—C8—C1	109.9 (2)	H16A—C16—H16B	109.5
C9—C8—C7	112.8 (2)	C10—C16—H16C	109.5
C1—C8—C7	114.2 (2)	H16A—C16—H16C	109.5
C9—C8—H8	106.5	H16B—C16—H16C	109.5
C1—C8—H8	106.5	C9—N1—C10	57.3 (2)
C7—C8—H8	106.5	C9—N1—H1	151.3
C10—C9—N1	62.4 (2)	C10—N1—H1	151.3
C10—C9—C8	123.7 (2)

6 in total

1. Regio- and stereoselectivity of beta-himachalene epoxidation by m-CPBA. A theoretical study.

Authors: A Chekroun; A Jarid; A Benharref; A Boutalib
Journal: J Org Chem Date: 2000-07-14 Impact factor: 4.354

2. Screening study for potential lead compounds for natural product-based fungicides: I. Synthesis and in vitro evaluation of coumarins against Botrytis cinerea.

Authors: Mourad Daoubi; Rosa Durán-Patrón; Mohamed Hmamouchi; Rosario Hernández-Galán; Ahmed Benharref; Isidro G Collado
Journal: Pest Manag Sci Date: 2004-09 Impact factor: 4.845

3. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

4. (1S,3R,8S,9S,10R)-2,2-Dichloro-9,10-epoxy-3,7,7,10-tetramethyltricyclo[6.4.0.0(1,3)]dodecane and (1S,3R,8S,10R)-2,2-dichloro-3,7,7,10-tetramethyltricyclo[6.4.0.0(1,3)]dodecan-9-one.

Authors: F Sbai; M Dakir; A Auhmani; H El Jamili; M Akssira; A Benharref; A Kenz; M Pierrot
Journal: Acta Crystallogr C Date: 2002-07-31 Impact factor: 1.172

5. (1S,3R,8S,9R,10S)-2,2-Dichloro-3,7,7,10-tetra-methyl-9,10-ep-oxy-tricyclo-[6.4.0.0]dodeca-ne.

Authors: Ahmed Benharref; Lahcen El Ammari; Daniel Avignant; Abdelghani Oudahmane; Moha Berraho
Journal: Acta Crystallogr Sect E Struct Rep Online Date: 2010-11-10

6. Structure validation in chemical crystallography.

Authors: Anthony L Spek
Journal: Acta Crystallogr D Biol Crystallogr Date: 2009-01-20