(1S,3R,8R)-9-(1-Amino-ethyl-idene)-2,2-dichloro-3,7,7-trimethyl-tricyclo-[6.4.0.0]undecan-10-one.

The title compound, C(16)H(23)Cl(2)NO, was synthesised 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 contains a seven membered ring, which is fused to a five- and a three-membered ring. The five-membered ring has a twisted conformation, whereas the seven-membered ring displays a chair conformation. The dihedral angle between the five- and seven-membered rings is 45.26 (9)°. The absolute structure was established unambiguously from anomalous dispersion effects. In the crystal, mol-ecules are linked into chains propagating along the b axis by inter-molecular N-H⋯O hydrogen bonds; an intramolecular N-H⋯O link also occurs.

Related literature

For the isolation of β-himachalene, see: Joseph & Dev (1968 ▶); Plattier & Teisseire (1974 ▶). For the reactivity of β-himachalene, see: Lassaba et al. (1998 ▶); Chekroun et al. (2000 ▶); El Jamili et al. (2002 ▶); Dakir et al. (2004 ▶). For the biological activity of β-himachalene, see: Daoubi et al. (2004 ▶). For conformational analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C16H23Cl2NO

M = 316.25

Monoclinic,

a = 7.7570 (7) Å

b = 9.7041 (9) Å

c = 10.6901 (10) Å

β = 93.432 (3)°

V = 803.25 (13) Å3

Z = 2

Mo Kα radiation

μ = 0.40 mm−1

T = 298 K

0.41 × 0.33 × 0.26 mm

Data collection

Bruker APEXII CCD diffractometer

4954 measured reflections

2355 independent reflections

2297 reflections with I > 2σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.080

S = 1.08

2355 reflections

193 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.24 e Å−3

Δρmin = −0.22 e Å−3

Absolute structure: Flack & Bernardinelli (2000 ▶), 614 Friedel pairs

Flack parameter: −0.02 (5)

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT-Plus (Bruker, 2009 ▶); data reduction: SAINT-Plus; 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, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811005307/fj2396sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811005307/fj2396Isup2.hkl

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

C16H23Cl2NO	F(000) = 336
Mr = 316.25	Dx = 1.308 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 4954 reflections
a = 7.7570 (7) Å	θ = 3.4–26.4°
b = 9.7041 (9) Å	µ = 0.40 mm−1
c = 10.6901 (10) Å	T = 298 K
β = 93.432 (3)°	Prism, colourless
V = 803.25 (13) Å3	0.41 × 0.33 × 0.26 mm
Z = 2

Bruker APEXII CCD diffractometer	2297 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.015
graphite	θmax = 26.4°, θmin = 3.4°
ω and φ scans	h = −9→9
4954 measured reflections	k = −12→6
2355 independent reflections	l = −12→13

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)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.080	w = 1/[σ2(Fo2) + (0.0528P)2 + 0.0821P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max = 0.001
2355 reflections	Δρmax = 0.24 e Å−3
193 parameters	Δρmin = −0.22 e Å−3
1 restraint	Absolute structure: Flack & Bernardinelli (2000), 614 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.02 (5)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

	x	y	z	Uiso*/Ueq
H2	1.000 (3)	−0.257 (3)	0.553 (2)	0.042 (6)*
H1	0.933 (3)	−0.125 (4)	0.502 (3)	0.050 (7)*
Cl1	0.88492 (8)	0.36063 (7)	0.85606 (7)	0.06081 (18)
Cl2	0.79425 (7)	0.12962 (6)	1.00496 (4)	0.05055 (16)
C9	0.7491 (2)	−0.0408 (2)	0.66044 (16)	0.0293 (4)
O1	0.8629 (2)	0.07077 (17)	0.48287 (13)	0.0448 (4)
C8	0.6205 (2)	0.0004 (2)	0.75543 (15)	0.0274 (4)
H8	0.6565	−0.0383	0.8375	0.033*
C1	0.6443 (2)	0.15793 (19)	0.75843 (15)	0.0297 (4)
C12	0.8402 (2)	−0.16350 (19)	0.65295 (17)	0.0321 (4)
C10	0.7797 (2)	0.0713 (2)	0.57971 (17)	0.0333 (4)
N1	0.9341 (3)	−0.1878 (2)	0.5548 (2)	0.0444 (4)
C7	0.4310 (2)	−0.0475 (2)	0.71640 (17)	0.0357 (4)
C3	0.5434 (3)	0.2575 (2)	0.83808 (17)	0.0362 (4)
C2	0.7312 (2)	0.2285 (2)	0.87178 (18)	0.0363 (4)
C4	0.4090 (3)	0.2029 (3)	0.9238 (2)	0.0462 (5)
H4A	0.4656	0.1417	0.9852	0.055*
H4B	0.3620	0.2797	0.9688	0.055*
C16	0.4318 (3)	−0.2036 (3)	0.6976 (2)	0.0451 (5)
H16A	0.5082	−0.2267	0.6333	0.068*
H16B	0.3171	−0.2344	0.6731	0.068*
H16C	0.4707	−0.2478	0.7745	0.068*
C11	0.7012 (3)	0.2010 (2)	0.62976 (17)	0.0386 (5)
H11A	0.6033	0.2311	0.5759	0.046*
H11B	0.7855	0.2747	0.6371	0.046*
C14	0.4943 (4)	0.3966 (3)	0.7812 (2)	0.0543 (6)
H14A	0.5823	0.4261	0.7276	0.082*
H14B	0.4834	0.4629	0.8469	0.082*
H14C	0.3863	0.3887	0.7330	0.082*
C5	0.2612 (3)	0.1259 (3)	0.8557 (2)	0.0551 (6)
H5A	0.2260	0.1757	0.7798	0.066*
H5B	0.1637	0.1242	0.9084	0.066*
C6	0.3060 (3)	−0.0212 (3)	0.8212 (2)	0.0491 (5)
H6A	0.1986	−0.0681	0.7975	0.059*
H6B	0.3545	−0.0657	0.8966	0.059*
C15	0.3604 (3)	0.0199 (3)	0.5944 (2)	0.0512 (6)
H15A	0.3540	0.1178	0.6058	0.077*
H15B	0.2472	−0.0157	0.5721	0.077*
H15C	0.4358	−0.0003	0.5287	0.077*
C13	0.8492 (3)	−0.2716 (3)	0.7522 (2)	0.0488 (5)
H13A	0.9673	−0.2981	0.7700	0.073*
H13B	0.7832	−0.3504	0.7236	0.073*
H13C	0.8028	−0.2358	0.8268	0.073*

	U11	U22	U33	U12	U13	U23
Cl1	0.0562 (3)	0.0361 (3)	0.0907 (4)	−0.0136 (3)	0.0093 (3)	−0.0118 (3)
Cl2	0.0568 (3)	0.0510 (3)	0.0424 (2)	0.0037 (3)	−0.0094 (2)	−0.0038 (2)
C9	0.0310 (8)	0.0247 (9)	0.0331 (8)	−0.0017 (7)	0.0087 (6)	−0.0004 (7)
O1	0.0579 (9)	0.0357 (8)	0.0439 (7)	−0.0015 (7)	0.0276 (6)	0.0035 (6)
C8	0.0315 (8)	0.0246 (9)	0.0266 (7)	−0.0005 (7)	0.0060 (6)	0.0011 (6)
C1	0.0335 (8)	0.0239 (10)	0.0326 (8)	0.0028 (7)	0.0085 (6)	0.0003 (7)
C12	0.0317 (8)	0.0242 (11)	0.0406 (9)	−0.0021 (7)	0.0043 (7)	−0.0033 (7)
C10	0.0380 (9)	0.0274 (10)	0.0354 (8)	−0.0023 (8)	0.0103 (7)	0.0017 (7)
N1	0.0467 (10)	0.0312 (10)	0.0571 (11)	0.0074 (9)	0.0187 (8)	−0.0038 (10)
C7	0.0328 (9)	0.0380 (11)	0.0365 (9)	−0.0049 (8)	0.0048 (7)	−0.0009 (8)
C3	0.0429 (10)	0.0292 (10)	0.0372 (9)	0.0069 (8)	0.0097 (7)	−0.0042 (8)
C2	0.0410 (10)	0.0262 (10)	0.0419 (9)	−0.0012 (8)	0.0055 (8)	−0.0051 (8)
C4	0.0469 (11)	0.0492 (14)	0.0444 (10)	0.0094 (10)	0.0175 (8)	−0.0066 (10)
C16	0.0449 (11)	0.0412 (13)	0.0493 (11)	−0.0131 (10)	0.0039 (9)	−0.0024 (10)
C11	0.0546 (12)	0.0245 (10)	0.0382 (9)	0.0020 (8)	0.0159 (8)	0.0049 (8)
C14	0.0698 (15)	0.0353 (13)	0.0589 (13)	0.0194 (11)	0.0119 (11)	−0.0001 (11)
C5	0.0365 (10)	0.0652 (17)	0.0656 (12)	0.0064 (12)	0.0196 (9)	−0.0057 (14)
C6	0.0361 (10)	0.0549 (15)	0.0579 (12)	−0.0084 (10)	0.0156 (9)	−0.0035 (11)
C15	0.0459 (12)	0.0577 (16)	0.0484 (11)	0.0006 (11)	−0.0093 (9)	0.0019 (11)
C13	0.0531 (12)	0.0324 (12)	0.0613 (12)	0.0075 (10)	0.0052 (10)	0.0115 (10)

Cl1—C2	1.766 (2)	C4—C5	1.517 (4)
Cl2—C2	1.762 (2)	C4—H4A	0.9700
C9—C12	1.389 (3)	C4—H4B	0.9700
C9—C10	1.418 (3)	C16—H16A	0.9600
C9—C8	1.519 (2)	C16—H16B	0.9600
O1—C10	1.253 (2)	C16—H16C	0.9600
C8—C1	1.539 (3)	C11—H11A	0.9700
C8—C7	1.574 (2)	C11—H11B	0.9700
C8—H8	0.9800	C14—H14A	0.9600
C1—C2	1.515 (3)	C14—H14B	0.9600
C1—C11	1.528 (2)	C14—H14C	0.9600
C1—C3	1.533 (2)	C5—C6	1.519 (4)
C12—N1	1.334 (3)	C5—H5A	0.9700
C12—C13	1.490 (3)	C5—H5B	0.9700
C10—C11	1.509 (3)	C6—H6A	0.9700
N1—H2	0.84 (3)	C6—H6B	0.9700
N1—H1	0.83 (3)	C15—H15A	0.9600
C7—C16	1.528 (3)	C15—H15B	0.9600
C7—C15	1.531 (3)	C15—H15C	0.9600
C7—C6	1.546 (3)	C13—H13A	0.9600
C3—C2	1.506 (3)	C13—H13B	0.9600
C3—C14	1.520 (3)	C13—H13C	0.9600
C3—C4	1.524 (3)
C12—C9—C10	121.23 (16)	C5—C4—H4B	108.7
C12—C9—C8	128.39 (17)	C3—C4—H4B	108.7
C10—C9—C8	110.19 (16)	H4A—C4—H4B	107.6
C9—C8—C1	101.12 (14)	C7—C16—H16A	109.5
C9—C8—C7	112.64 (14)	C7—C16—H16B	109.5
C1—C8—C7	114.08 (16)	H16A—C16—H16B	109.5
C9—C8—H8	109.6	C7—C16—H16C	109.5
C1—C8—H8	109.6	H16A—C16—H16C	109.5
C7—C8—H8	109.6	H16B—C16—H16C	109.5
C2—C1—C11	117.28 (17)	C10—C11—C1	103.64 (15)
C2—C1—C3	59.21 (12)	C10—C11—H11A	111.0
C11—C1—C3	120.82 (16)	C1—C11—H11A	111.0
C2—C1—C8	120.85 (16)	C10—C11—H11B	111.0
C11—C1—C8	107.05 (14)	C1—C11—H11B	111.0
C3—C1—C8	124.93 (16)	H11A—C11—H11B	109.0
N1—C12—C9	120.03 (19)	C3—C14—H14A	109.5
N1—C12—C13	115.56 (19)	C3—C14—H14B	109.5
C9—C12—C13	124.34 (17)	H14A—C14—H14B	109.5
O1—C10—C9	127.82 (19)	C3—C14—H14C	109.5
O1—C10—C11	122.38 (17)	H14A—C14—H14C	109.5
C9—C10—C11	109.76 (15)	H14B—C14—H14C	109.5
C12—N1—H2	120.9 (16)	C4—C5—C6	113.71 (19)
C12—N1—H1	115.2 (19)	C4—C5—H5A	108.8
H2—N1—H1	123 (2)	C6—C5—H5A	108.8
C16—C7—C15	108.37 (18)	C4—C5—H5B	108.8
C16—C7—C6	105.49 (18)	C6—C5—H5B	108.8
C15—C7—C6	109.80 (18)	H5A—C5—H5B	107.7
C16—C7—C8	108.48 (17)	C5—C6—C7	119.6 (2)
C15—C7—C8	112.35 (17)	C5—C6—H6A	107.4
C6—C7—C8	112.04 (16)	C7—C6—H6A	107.4
C2—C3—C14	118.5 (2)	C5—C6—H6B	107.4
C2—C3—C4	118.56 (17)	C7—C6—H6B	107.4
C14—C3—C4	112.69 (18)	H6A—C6—H6B	107.0
C2—C3—C1	59.77 (12)	C7—C15—H15A	109.5
C14—C3—C1	117.47 (17)	C7—C15—H15B	109.5
C4—C3—C1	120.35 (18)	H15A—C15—H15B	109.5
C3—C2—C1	61.01 (12)	C7—C15—H15C	109.5
C3—C2—Cl2	120.86 (14)	H15A—C15—H15C	109.5
C1—C2—Cl2	119.26 (15)	H15B—C15—H15C	109.5
C3—C2—Cl1	119.40 (16)	C12—C13—H13A	109.5
C1—C2—Cl1	121.53 (14)	C12—C13—H13B	109.5
Cl2—C2—Cl1	108.41 (11)	H13A—C13—H13B	109.5
C5—C4—C3	114.04 (18)	C12—C13—H13C	109.5
C5—C4—H4A	108.7	H13A—C13—H13C	109.5
C3—C4—H4A	108.7	H13B—C13—H13C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2···O1i	0.85 (3)	2.03 (3)	2.865 (3)	170 (2)
N1—H1···O1	0.83 (4)	1.98 (4)	2.672 (3)	140 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H2⋯O1i	0.85 (3)	2.03 (3)	2.865 (3)	170 (2)
N1—H1⋯O1	0.83 (4)	1.98 (4)	2.672 (3)	140 (3)

Symmetry code: (i) .