Crystal structure of 2-[(1R,2R,4aS,8aS)-2-hy-droxy-2,5,5,8a-tetra-methyl-deca-hydro-naphthalen-1-yl]-N-(o-tol-yl)acetamide.

The title compound, C23H35NO2, is an amide derivative of the lactone (+)-sclareolide, and was synthesized from natural sclareol. In the mol-ecular structure, the two six-membered rings (A and B) of the labdane skeleton are trans-fused, and adopt chair conformations. There is an intra-molecular N-H⋯O hydrogen bond present forming an S(7) ring motif. In the crystal, O-H⋯O hydrogen bonds link the mol-ecules into helical chains propagating along the b-axis direction. The chains are linked via C-H⋯π inter-actions, forming a three-dimensional structure.

Related literature

For the chemistry and biological importance of sclareol and sclareolide, see: Barrero et al. (2004 ▸); Huang et al. (2001 ▸); Mohamad et al. (2005 ▸); Sy & Brown (1997 ▸). For the synthesis of coronarin and chinensines, see: Margaros & Vassilikogiannakis (2007 ▸). For related structures, see: Bernardinelli & Giersch (1985 ▸); Shi et al. (2015 ▸).

Experimental

Crystal data

C23H35NO2

M = 357.52

Monoclinic,

a = 6.3001 (5) Å

b = 13.2663 (10) Å

c = 12.7082 (10) Å

β = 96.983 (2)°

V = 1054.26 (14) Å3

Z = 2

Mo Kα radiation

μ = 0.07 mm−1

T = 296 K

0.22 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2002 ▸) T min = 0.985, T max = 0.987

3714 measured reflections

3714 independent reflections

3121 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.095

S = 1.06

3714 reflections

242 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.11 e Å−3

Δρmin = −0.13 e Å−3

Data collection: SMART (Bruker, 2002 ▸); cell refinement: SAINT (Bruker, 2002 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: SHELXTL (Sheldrick, 2008 ▸); software used to prepare material for publication: SHELXTL).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015017600/su5209sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015017600/su5209Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015017600/su5209Isup3.cdx

Click here for additional data file.

. DOI: 10.1107/S2056989015017600/su5209fig1.tif

A view of the mol­ecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level. The intra­molecular N—H⋯O hydrogen bonds is shown as a dashed line (see Table 1).

Click here for additional data file.

a . DOI: 10.1107/S2056989015017600/su5209fig2.tif

Crystal packing of the title compound, viewed along the a axis. The hydrogen bonds are shown as dashed lines (see Table 1), and C-bound H atoms have been omitted for clarity.

CCDC reference: 1426216

Additional supporting information: crystallographic information; 3D view; checkCIF report

C23H35NO2	F(000) = 392
Mr = 357.52	Dx = 1.126 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2068 reflections
a = 6.3001 (5) Å	θ = 3.1–23.4°
b = 13.2663 (10) Å	µ = 0.07 mm−1
c = 12.7082 (10) Å	T = 296 K
β = 96.983 (2)°	Block, colorless
V = 1054.26 (14) Å3	0.22 × 0.20 × 0.18 mm
Z = 2

Bruker SMART APEX CCD diffractometer	3714 independent reflections
Radiation source: fine-focus sealed tube	3121 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
phi and ω scans	θmax = 25.4°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −7→7
Tmin = 0.985, Tmax = 0.987	k = −15→14
3714 measured reflections	l = 0→15

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0452P)2 + 0.0489P] where P = (Fo2 + 2Fc2)/3
3714 reflections	(Δ/σ)max < 0.001
242 parameters	Δρmax = 0.11 e Å−3
1 restraint	Δρmin = −0.13 e Å−3

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	Uiso*/Ueq
O1	0.4624 (2)	0.38763 (11)	0.90592 (12)	0.0598 (4)
H1O	0.5362	0.4362	0.9269	0.090*
O2	0.3383 (3)	0.06216 (10)	1.00512 (14)	0.0661 (4)
N1	0.2698 (2)	0.22934 (12)	1.01913 (11)	0.0413 (4)
H1	0.3134	0.2876	1.0012	0.050*
C1	0.0998 (3)	0.23103 (14)	1.08233 (13)	0.0373 (4)
C2	0.0322 (3)	0.32517 (14)	1.11475 (15)	0.0449 (5)
C3	−0.1453 (4)	0.32833 (19)	1.16972 (18)	0.0601 (6)
H3	−0.1947	0.3906	1.1900	0.072*
C4	−0.2502 (4)	0.2428 (2)	1.19504 (17)	0.0647 (6)
H4	−0.3692	0.2472	1.2315	0.078*
C5	−0.1783 (4)	0.1515 (2)	1.16623 (18)	0.0608 (6)
H5	−0.2466	0.0931	1.1848	0.073*
C6	−0.0049 (3)	0.14439 (16)	1.10965 (17)	0.0503 (5)
H6	0.0419	0.0815	1.0898	0.060*
C7	0.3739 (3)	0.15013 (14)	0.98281 (15)	0.0412 (4)
C8	0.5396 (3)	0.17800 (15)	0.91191 (16)	0.0448 (5)
H8A	0.6079	0.1167	0.8914	0.054*
H8B	0.6485	0.2187	0.9523	0.054*
C9	0.4531 (3)	0.23662 (13)	0.80977 (13)	0.0351 (4)
H9	0.2994	0.2439	0.8135	0.042*
C10	0.5404 (3)	0.34563 (14)	0.81224 (16)	0.0461 (5)
C11	0.4370 (4)	0.40191 (15)	0.71547 (18)	0.0601 (6)
H11A	0.5034	0.4677	0.7131	0.072*
H11B	0.2869	0.4123	0.7224	0.072*
C12	0.4552 (4)	0.34729 (15)	0.61180 (17)	0.0584 (6)
H12A	0.6046	0.3408	0.6016	0.070*
H12B	0.3838	0.3862	0.5532	0.070*
C13	0.3536 (3)	0.24265 (16)	0.61310 (15)	0.0458 (5)
H13	0.2113	0.2551	0.6342	0.055*
C14	0.4691 (3)	0.17743 (14)	0.70513 (14)	0.0380 (4)
C15	0.7835 (4)	0.35592 (19)	0.82392 (19)	0.0667 (7)
H15A	0.8226	0.4244	0.8415	0.100*
H15B	0.8349	0.3379	0.7584	0.100*
H15C	0.8459	0.3120	0.8793	0.100*
C16	0.7032 (3)	0.15146 (18)	0.69257 (18)	0.0558 (5)
H16A	0.7818	0.1407	0.7612	0.084*
H16B	0.7663	0.2061	0.6578	0.084*
H16C	0.7073	0.0913	0.6508	0.084*
C17	0.3428 (3)	0.07858 (15)	0.71010 (17)	0.0507 (5)
H17A	0.4192	0.0347	0.7628	0.061*
H17B	0.2047	0.0936	0.7329	0.061*
C18	0.3081 (5)	0.02307 (19)	0.6044 (2)	0.0782 (8)
H18A	0.4451	0.0016	0.5847	0.094*
H18B	0.2220	−0.0366	0.6116	0.094*
C19	0.1974 (4)	0.0897 (2)	0.5183 (2)	0.0848 (9)
H19A	0.0535	0.1032	0.5343	0.102*
H19B	0.1858	0.0530	0.4518	0.102*
C20	0.3085 (4)	0.1906 (2)	0.50341 (17)	0.0658 (6)
C21	0.5087 (5)	0.1731 (3)	0.4470 (2)	0.0896 (9)
H21A	0.6003	0.1248	0.4861	0.134*
H21B	0.5843	0.2356	0.4431	0.134*
H21C	0.4663	0.1482	0.3767	0.134*
C22	0.1549 (6)	0.2562 (3)	0.4303 (2)	0.1163 (13)
H22A	0.1083	0.2197	0.3664	0.174*
H22B	0.2268	0.3167	0.4131	0.174*
H22C	0.0333	0.2732	0.4655	0.174*
C23	0.1454 (4)	0.42079 (16)	1.0915 (2)	0.0669 (7)
H23A	0.0722	0.4774	1.1175	0.100*
H23B	0.1467	0.4273	1.0164	0.100*
H23C	0.2897	0.4188	1.1259	0.100*

	U11	U22	U33	U12	U13	U23
O1	0.0856 (11)	0.0399 (8)	0.0583 (9)	−0.0191 (7)	0.0266 (8)	−0.0166 (7)
O2	0.0854 (11)	0.0327 (8)	0.0842 (11)	0.0119 (8)	0.0266 (9)	0.0162 (8)
N1	0.0510 (9)	0.0274 (8)	0.0467 (9)	−0.0027 (7)	0.0110 (7)	0.0035 (7)
C1	0.0414 (9)	0.0384 (10)	0.0314 (9)	−0.0004 (9)	0.0012 (7)	0.0030 (8)
C2	0.0536 (12)	0.0420 (11)	0.0392 (11)	0.0005 (9)	0.0056 (9)	−0.0023 (8)
C3	0.0650 (14)	0.0676 (16)	0.0497 (13)	0.0086 (13)	0.0145 (11)	−0.0088 (11)
C4	0.0582 (13)	0.092 (2)	0.0467 (13)	0.0002 (14)	0.0160 (10)	0.0072 (13)
C5	0.0603 (13)	0.0724 (16)	0.0495 (13)	−0.0172 (12)	0.0059 (11)	0.0188 (12)
C6	0.0605 (13)	0.0429 (11)	0.0473 (12)	−0.0045 (10)	0.0051 (10)	0.0092 (9)
C7	0.0497 (11)	0.0344 (11)	0.0379 (10)	0.0053 (9)	−0.0009 (8)	0.0056 (8)
C8	0.0452 (11)	0.0438 (11)	0.0449 (11)	0.0107 (9)	0.0044 (8)	−0.0001 (9)
C9	0.0365 (9)	0.0314 (9)	0.0383 (10)	0.0025 (8)	0.0075 (7)	0.0001 (8)
C10	0.0594 (12)	0.0352 (11)	0.0459 (12)	−0.0093 (9)	0.0151 (9)	−0.0071 (8)
C11	0.0855 (16)	0.0337 (12)	0.0642 (15)	−0.0013 (11)	0.0215 (12)	0.0091 (10)
C12	0.0787 (15)	0.0495 (13)	0.0489 (13)	0.0011 (11)	0.0152 (11)	0.0159 (10)
C13	0.0433 (10)	0.0532 (12)	0.0415 (11)	0.0001 (9)	0.0079 (8)	0.0025 (9)
C14	0.0395 (10)	0.0366 (10)	0.0397 (10)	−0.0017 (8)	0.0116 (8)	−0.0019 (7)
C15	0.0656 (14)	0.0696 (16)	0.0664 (15)	−0.0320 (12)	0.0143 (11)	−0.0156 (12)
C16	0.0493 (12)	0.0572 (13)	0.0639 (14)	0.0062 (10)	0.0193 (10)	−0.0053 (11)
C17	0.0610 (13)	0.0417 (12)	0.0520 (13)	−0.0102 (10)	0.0172 (10)	−0.0090 (9)
C18	0.104 (2)	0.0623 (17)	0.0738 (19)	−0.0359 (15)	0.0339 (16)	−0.0293 (13)
C19	0.0888 (19)	0.111 (2)	0.0561 (17)	−0.0440 (17)	0.0149 (14)	−0.0369 (16)
C20	0.0702 (14)	0.0887 (18)	0.0385 (12)	−0.0182 (13)	0.0066 (11)	−0.0055 (11)
C21	0.106 (2)	0.117 (2)	0.0529 (16)	−0.0345 (18)	0.0368 (15)	−0.0212 (15)
C22	0.117 (3)	0.166 (4)	0.0575 (17)	−0.009 (2)	−0.0239 (17)	0.0145 (19)
C23	0.0797 (16)	0.0373 (12)	0.0870 (18)	−0.0010 (11)	0.0236 (14)	−0.0140 (11)

O1—C10	1.453 (2)	C13—C20	1.551 (3)
O1—H1O	0.8200	C13—C14	1.562 (3)
O2—C7	1.228 (2)	C13—H13	0.9800
N1—C7	1.349 (2)	C14—C17	1.539 (3)
N1—C1	1.415 (2)	C14—C16	1.541 (3)
N1—H1	0.8600	C15—H15A	0.9600
C1—C6	1.390 (3)	C15—H15B	0.9600
C1—C2	1.398 (3)	C15—H15C	0.9600
C2—C3	1.390 (3)	C16—H16A	0.9600
C2—C23	1.502 (3)	C16—H16B	0.9600
C3—C4	1.371 (3)	C16—H16C	0.9600
C3—H3	0.9300	C17—C18	1.524 (3)
C4—C5	1.358 (4)	C17—H17A	0.9700
C4—H4	0.9300	C17—H17B	0.9700
C5—C6	1.382 (3)	C18—C19	1.510 (4)
C5—H5	0.9300	C18—H18A	0.9700
C6—H6	0.9300	C18—H18B	0.9700
C7—C8	1.506 (3)	C19—C20	1.533 (4)
C8—C9	1.554 (3)	C19—H19A	0.9700
C8—H8A	0.9700	C19—H19B	0.9700
C8—H8B	0.9700	C20—C22	1.529 (4)
C9—C10	1.546 (3)	C20—C21	1.542 (4)
C9—C14	1.558 (2)	C21—H21A	0.9600
C9—H9	0.9800	C21—H21B	0.9600
C10—C11	1.516 (3)	C21—H21C	0.9600
C10—C15	1.527 (3)	C22—H22A	0.9600
C11—C12	1.520 (3)	C22—H22B	0.9600
C11—H11A	0.9700	C22—H22C	0.9600
C11—H11B	0.9700	C23—H23A	0.9600
C12—C13	1.530 (3)	C23—H23B	0.9600
C12—H12A	0.9700	C23—H23C	0.9600
C12—H12B	0.9700
C10—O1—H1O	109.5	C17—C14—C16	108.65 (16)
C7—N1—C1	129.73 (16)	C17—C14—C9	107.87 (14)
C7—N1—H1	115.1	C16—C14—C9	111.29 (15)
C1—N1—H1	115.1	C17—C14—C13	107.85 (15)
C6—C1—C2	119.63 (17)	C16—C14—C13	114.27 (15)
C6—C1—N1	122.93 (18)	C9—C14—C13	106.69 (14)
C2—C1—N1	117.40 (16)	C10—C15—H15A	109.5
C3—C2—C1	117.90 (19)	C10—C15—H15B	109.5
C3—C2—C23	120.25 (19)	H15A—C15—H15B	109.5
C1—C2—C23	121.85 (18)	C10—C15—H15C	109.5
C4—C3—C2	122.2 (2)	H15A—C15—H15C	109.5
C4—C3—H3	118.9	H15B—C15—H15C	109.5
C2—C3—H3	118.9	C14—C16—H16A	109.5
C5—C4—C3	119.3 (2)	C14—C16—H16B	109.5
C5—C4—H4	120.4	H16A—C16—H16B	109.5
C3—C4—H4	120.4	C14—C16—H16C	109.5
C4—C5—C6	120.8 (2)	H16A—C16—H16C	109.5
C4—C5—H5	119.6	H16B—C16—H16C	109.5
C6—C5—H5	119.6	C18—C17—C14	113.26 (17)
C5—C6—C1	120.2 (2)	C18—C17—H17A	108.9
C5—C6—H6	119.9	C14—C17—H17A	108.9
C1—C6—H6	119.9	C18—C17—H17B	108.9
O2—C7—N1	123.46 (17)	C14—C17—H17B	108.9
O2—C7—C8	122.06 (17)	H17A—C17—H17B	107.7
N1—C7—C8	114.48 (16)	C19—C18—C17	111.1 (2)
C7—C8—C9	115.10 (15)	C19—C18—H18A	109.4
C7—C8—H8A	108.5	C17—C18—H18A	109.4
C9—C8—H8A	108.5	C19—C18—H18B	109.4
C7—C8—H8B	108.5	C17—C18—H18B	109.4
C9—C8—H8B	108.5	H18A—C18—H18B	108.0
H8A—C8—H8B	107.5	C18—C19—C20	115.0 (2)
C10—C9—C8	111.30 (15)	C18—C19—H19A	108.5
C10—C9—C14	115.40 (14)	C20—C19—H19A	108.5
C8—C9—C14	114.09 (15)	C18—C19—H19B	108.5
C10—C9—H9	104.9	C20—C19—H19B	108.5
C8—C9—H9	104.9	H19A—C19—H19B	107.5
C14—C9—H9	104.9	C22—C20—C19	107.9 (2)
O1—C10—C11	108.73 (17)	C22—C20—C21	107.2 (2)
O1—C10—C15	108.72 (17)	C19—C20—C21	109.7 (2)
C11—C10—C15	111.21 (18)	C22—C20—C13	109.0 (2)
O1—C10—C9	102.74 (14)	C19—C20—C13	108.33 (18)
C11—C10—C9	109.11 (16)	C21—C20—C13	114.47 (19)
C15—C10—C9	115.82 (17)	C20—C21—H21A	109.5
C10—C11—C12	113.45 (17)	C20—C21—H21B	109.5
C10—C11—H11A	108.9	H21A—C21—H21B	109.5
C12—C11—H11A	108.9	C20—C21—H21C	109.5
C10—C11—H11B	108.9	H21A—C21—H21C	109.5
C12—C11—H11B	108.9	H21B—C21—H21C	109.5
H11A—C11—H11B	107.7	C20—C22—H22A	109.5
C11—C12—C13	110.33 (17)	C20—C22—H22B	109.5
C11—C12—H12A	109.6	H22A—C22—H22B	109.5
C13—C12—H12A	109.6	C20—C22—H22C	109.5
C11—C12—H12B	109.6	H22A—C22—H22C	109.5
C13—C12—H12B	109.6	H22B—C22—H22C	109.5
H12A—C12—H12B	108.1	C2—C23—H23A	109.5
C12—C13—C20	115.19 (17)	C2—C23—H23B	109.5
C12—C13—C14	110.69 (16)	H23A—C23—H23B	109.5
C20—C13—C14	116.36 (18)	C2—C23—H23C	109.5
C12—C13—H13	104.3	H23A—C23—H23C	109.5
C20—C13—H13	104.3	H23B—C23—H23C	109.5
C14—C13—H13	104.3
C7—N1—C1—C6	−6.7 (3)	C11—C12—C13—C20	164.77 (19)
C7—N1—C1—C2	175.54 (18)	C11—C12—C13—C14	−60.6 (2)
C6—C1—C2—C3	−2.8 (3)	C10—C9—C14—C17	−170.84 (16)
N1—C1—C2—C3	175.04 (18)	C8—C9—C14—C17	58.41 (19)
C6—C1—C2—C23	177.3 (2)	C10—C9—C14—C16	70.1 (2)
N1—C1—C2—C23	−4.9 (3)	C8—C9—C14—C16	−60.7 (2)
C1—C2—C3—C4	1.8 (3)	C10—C9—C14—C13	−55.19 (19)
C23—C2—C3—C4	−178.3 (2)	C8—C9—C14—C13	174.06 (14)
C2—C3—C4—C5	0.4 (3)	C12—C13—C14—C17	173.35 (16)
C3—C4—C5—C6	−1.7 (3)	C20—C13—C14—C17	−52.6 (2)
C4—C5—C6—C1	0.6 (3)	C12—C13—C14—C16	−65.7 (2)
C2—C1—C6—C5	1.7 (3)	C20—C13—C14—C16	68.3 (2)
N1—C1—C6—C5	−176.07 (18)	C12—C13—C14—C9	57.69 (19)
C1—N1—C7—O2	−3.4 (3)	C20—C13—C14—C9	−168.28 (15)
C1—N1—C7—C8	176.65 (17)	C16—C14—C17—C18	−70.6 (2)
O2—C7—C8—C9	120.4 (2)	C9—C14—C17—C18	168.6 (2)
N1—C7—C8—C9	−59.7 (2)	C13—C14—C17—C18	53.7 (2)
C7—C8—C9—C10	113.33 (18)	C14—C17—C18—C19	−56.3 (3)
C7—C8—C9—C14	−113.93 (17)	C17—C18—C19—C20	55.1 (3)
C8—C9—C10—O1	−60.06 (18)	C18—C19—C20—C22	−168.8 (2)
C14—C9—C10—O1	167.86 (14)	C18—C19—C20—C21	74.7 (3)
C8—C9—C10—C11	−175.33 (16)	C18—C19—C20—C13	−51.0 (3)
C14—C9—C10—C11	52.6 (2)	C12—C13—C20—C22	−60.1 (3)
C8—C9—C10—C15	58.3 (2)	C14—C13—C20—C22	168.0 (2)
C14—C9—C10—C15	−73.8 (2)	C12—C13—C20—C19	−177.2 (2)
O1—C10—C11—C12	−163.68 (17)	C14—C13—C20—C19	50.8 (3)
C15—C10—C11—C12	76.6 (2)	C12—C13—C20—C21	60.0 (3)
C9—C10—C11—C12	−52.3 (2)	C14—C13—C20—C21	−72.0 (3)
C10—C11—C12—C13	58.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	2.09	2.894 (2)	155
O1—H1O···O2i	0.82	2.00	2.8054 (19)	168
C8—H8B···Cgii	0.97	2.79	3.632 (2)	146
C22—H22A···Cgiii	0.96	2.98	3.808 (3)	145

Table 1

Hydrogen-bond geometry (, )

Cg is the centroid of benzene ring C1C6.

DHA	DH	HA	D A	DHA
N1H1O1	0.86	2.09	2.894(2)	155
O1H1OO2i	0.82	2.00	2.8054(19)	168
C8H8B Cg ii	0.97	2.79	3.632(2)	146
C22H22A Cg iii	0.96	2.98	3.808(3)	145

Symmetry codes: (i) ; (ii) ; (iii) .