14-Hydroxy-14-hydroxymethyl-5,5,9-trimethyl­tetra­cyclo­[11.2.1.0^1,10.0^4,9]hexa­decane hemihydrate

The title compound, C₂₀H₃₄O₂·0.5H₂O, is a diterpene known as ent-16β-17α-dihydroxy­kaurane. The cyclo­hexane rings adopt chair conformations and the cyclo­pentane ring adopts a half-chair form. The hydroxyl and hydroxymethyl substituents are attached pseudo-axially to the cyclo­pentane ring. The uncoordinated water mol­ecule participates in inter­molecular O—H...O hydrogen bonds, which link the mol­ecules into ribbons extending along the a axis.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.086
• wR factor = 0.251
• Data-to-parameter ratio = 9.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT415_ALERT_2_B Short Inter D-H..H-X       H1O2   ..  H13A    ..       2.05 Ang.

Alert level C
RFACR01_ALERT_3_C  The value of the weighted R factor is > 0.25
            Weighted R factor given   0.251
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT213_ALERT_2_C Atom C1      has ADP max/min Ratio .............       3.80 oblate
PLAT213_ALERT_2_C Atom C9      has ADP max/min Ratio .............       3.70 oblate
PLAT213_ALERT_2_C Atom C14     has ADP max/min Ratio .............       3.80 oblate
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.70
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          8
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          3

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           26.00
           From the CIF: _reflns_number_total               1894
           Count of symmetry unique reflns         1894
           Completeness (_total/calc)            100.00%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
  11 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).

5,5,9-Trimethyl-14-hydroxy-14- hydroxymethyl-tetracyclo[11.2.1.0^1,10.0^4,9] hexadecane hemihydrate

Crystal data

C20H34O2·0.5H2O	F(000) = 700
Mr = 315.48	Dx = 1.194 Mg m^−3
Monoclinic, C2	Melting point: 447-448 K K
Hall symbol: C 2y	Mo Kα radiation, λ = 0.71073 Å
a = 12.8348 (13) Å	Cell parameters from 6362 reflections
b = 6.2254 (5) Å	θ = 0.9–26.0°
c = 22.202 (2) Å	µ = 0.08 mm^−1
β = 98.493 (5)°	T = 100 K
V = 1754.5 (3) Å^3	Slab, colourless
Z = 4	0.28 × 0.19 × 0.07 mm

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer	1894 independent reflections
Radiation source: fine-focus sealed tube	1506 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.063
Detector resolution: 8.33 pixels mm^-1	θmax = 26.0°, θmin = 0.9°
ω scans	h = −13→15
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −6→7
Tmin = 0.983, Tmax = 0.995	l = −27→23
6362 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.086	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.251	H atoms treated by a mixture of independent and constrained refinement
S = 1.19	w = 1/[σ^2(Fo^2) + (0.1537P)^2 + 0.3783P] where P = (Fo^2 + 2Fc^2)/3
1894 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 0.56 e Å^−3
3 restraints	Δρmin = −0.38 e Å^−3

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1W	0.0000	0.5697 (10)	0.0000	0.0295 (15)
H1W1	−0.048 (3)	0.493 (4)	0.011 (3)	0.05 (3)*
O1	0.1478 (3)	0.8847 (7)	0.05063 (18)	0.0261 (11)
H1O1	0.1163	0.7707	0.0437	0.039*
O2	0.3512 (4)	0.7579 (7)	0.01959 (19)	0.0285 (11)
H1O2	0.3414	0.6649	−0.0068	0.043*
C1	0.2112 (4)	0.9714 (9)	0.2001 (3)	0.0175 (9)
C2	0.1187 (4)	0.9771 (10)	0.2355 (3)	0.0214 (13)
H2A	0.1101	0.8358	0.2525	0.026*
H2B	0.0551	1.0098	0.2076	0.026*
C3	0.1316 (4)	1.1416 (10)	0.2869 (3)	0.0218 (13)
H3A	0.0704	1.1382	0.3078	0.026*
H3B	0.1372	1.2846	0.2703	0.026*
C4	0.2314 (4)	1.0899 (9)	0.3321 (2)	0.0178 (12)
H4	0.2260	0.9356	0.3398	0.021*
C5	0.2364 (4)	1.1947 (10)	0.3959 (3)	0.0203 (13)
C6	0.3371 (5)	1.1170 (11)	0.4360 (3)	0.0240 (14)
H6A	0.3455	1.1963	0.4740	0.029*
H6B	0.3287	0.9666	0.4456	0.029*
C7	0.4372 (5)	1.1422 (11)	0.4074 (3)	0.0253 (14)
H7A	0.4522	1.2938	0.4033	0.030*
H7B	0.4959	1.0783	0.4339	0.030*
C8	0.4265 (5)	1.0358 (10)	0.3452 (3)	0.0246 (14)
H8A	0.4214	0.8818	0.3505	0.030*
H8B	0.4901	1.0636	0.3277	0.030*
C9	0.3310 (4)	1.1109 (9)	0.2997 (3)	0.0171 (12)
C10	0.3162 (4)	0.9515 (9)	0.2442 (2)	0.0172 (12)
H10	0.3137	0.8086	0.2624	0.021*
C11	0.4099 (4)	0.9411 (10)	0.2073 (3)	0.0209 (13)
H11A	0.4725	0.9915	0.2333	0.025*
H11B	0.4216	0.7918	0.1978	0.025*
C12	0.3983 (4)	1.0692 (11)	0.1479 (3)	0.0227 (14)
H12A	0.4210	1.2157	0.1572	0.027*
H12B	0.4452	1.0083	0.1220	0.027*
C13	0.2868 (5)	1.0746 (9)	0.1124 (3)	0.0180 (13)
H13A	0.2836	1.1652	0.0761	0.022*
C14	0.2393 (4)	0.8513 (9)	0.0961 (3)	0.0175 (9)
C15	0.2023 (5)	0.7764 (9)	0.1552 (3)	0.0207 (14)
H15A	0.2460	0.6587	0.1730	0.025*
H15B	0.1299	0.7269	0.1470	0.025*
C16	0.2131 (4)	1.1587 (10)	0.1552 (3)	0.0202 (13)
H16A	0.1433	1.1875	0.1334	0.024*
H16B	0.2407	1.2883	0.1759	0.024*
C17	0.1426 (4)	1.1190 (11)	0.4254 (3)	0.0241 (14)
H17A	0.1523	1.1616	0.4674	0.036*
H17B	0.1373	0.9654	0.4227	0.036*
H17C	0.0791	1.1825	0.4046	0.036*
C18	0.2344 (5)	1.4439 (10)	0.3942 (3)	0.0246 (14)
H18A	0.2219	1.4979	0.4330	0.037*
H18B	0.1792	1.4915	0.3632	0.037*
H18C	0.3009	1.4964	0.3855	0.037*
C19	0.3544 (5)	1.3412 (9)	0.2815 (3)	0.0195 (13)
H19A	0.3921	1.4151	0.3159	0.029*
H19B	0.2894	1.4147	0.2680	0.029*
H19C	0.3964	1.3383	0.2491	0.029*
C20	0.3104 (5)	0.6878 (10)	0.0719 (3)	0.0242 (14)
H20A	0.3686	0.6551	0.1037	0.029*
H20B	0.2709	0.5563	0.0622	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1W	0.019 (3)	0.014 (3)	0.057 (4)	0.000	0.012 (3)	0.000
O1	0.027 (2)	0.018 (2)	0.030 (2)	−0.002 (2)	−0.0067 (18)	−0.0057 (19)
O2	0.047 (3)	0.014 (2)	0.027 (2)	−0.003 (2)	0.015 (2)	−0.0069 (19)
C1	0.019 (2)	0.0022 (18)	0.031 (2)	0.0004 (17)	0.0029 (17)	−0.0005 (17)
C2	0.019 (3)	0.014 (3)	0.032 (3)	−0.004 (3)	0.004 (2)	−0.004 (3)
C3	0.020 (3)	0.013 (3)	0.034 (3)	0.002 (3)	0.006 (2)	−0.002 (3)
C4	0.019 (3)	0.005 (3)	0.030 (3)	−0.001 (2)	0.005 (2)	0.005 (2)
C5	0.017 (3)	0.015 (3)	0.029 (3)	−0.001 (2)	0.002 (2)	−0.001 (3)
C6	0.028 (3)	0.018 (3)	0.026 (3)	−0.001 (3)	0.007 (2)	0.002 (3)
C7	0.023 (3)	0.022 (3)	0.030 (3)	−0.002 (3)	0.000 (2)	0.001 (3)
C8	0.025 (3)	0.016 (3)	0.034 (3)	0.001 (3)	0.005 (3)	−0.001 (3)
C9	0.022 (3)	0.002 (3)	0.027 (3)	−0.001 (2)	0.003 (2)	0.000 (2)
C10	0.020 (3)	0.005 (3)	0.026 (3)	0.002 (3)	0.001 (2)	−0.001 (2)
C11	0.018 (3)	0.017 (3)	0.028 (3)	0.001 (3)	0.004 (2)	−0.003 (3)
C12	0.022 (3)	0.019 (3)	0.027 (3)	−0.006 (3)	0.004 (2)	−0.002 (3)
C13	0.021 (3)	0.007 (3)	0.025 (3)	−0.005 (2)	0.001 (2)	0.007 (2)
C14	0.019 (2)	0.0022 (18)	0.031 (2)	0.0004 (17)	0.0029 (17)	−0.0005 (17)
C15	0.022 (3)	0.006 (3)	0.034 (4)	0.001 (2)	0.004 (3)	0.001 (2)
C16	0.017 (3)	0.005 (3)	0.037 (3)	0.003 (2)	0.000 (3)	0.002 (3)
C17	0.019 (3)	0.022 (3)	0.032 (3)	−0.009 (3)	0.006 (2)	−0.001 (3)
C18	0.031 (3)	0.009 (3)	0.035 (3)	0.003 (3)	0.010 (3)	−0.003 (3)
C19	0.025 (3)	0.007 (3)	0.026 (3)	−0.006 (2)	0.003 (2)	0.002 (2)
C20	0.031 (3)	0.011 (3)	0.029 (3)	−0.002 (3)	−0.002 (3)	−0.003 (3)

Geometric parameters (Å, º)

O1W—H1W1	0.84 (4)	C9—C19	1.532 (7)
O1—C14	1.446 (7)	C9—C10	1.572 (8)
O1—H1O1	0.8200	C10—C11	1.552 (8)
O2—C20	1.412 (8)	C10—H10	0.9800
O2—H1O2	0.8200	C11—C12	1.529 (8)
C1—C2	1.518 (8)	C11—H11A	0.9700
C1—C16	1.536 (8)	C11—H11B	0.9700
C1—C10	1.549 (7)	C12—C13	1.529 (8)
C1—C15	1.564 (8)	C12—H12A	0.9700
C2—C3	1.525 (8)	C12—H12B	0.9700
C2—H2A	0.9700	C13—C16	1.529 (8)
C2—H2B	0.9700	C13—C14	1.540 (8)
C3—C4	1.540 (7)	C13—H13A	0.98
C3—H3A	0.9700	C14—C20	1.517 (8)
C3—H3B	0.9700	C14—C15	1.533 (9)
C4—C5	1.552 (8)	C15—H15A	0.9700
C4—C9	1.563 (8)	C15—H15B	0.9700
C4—H4	0.9800	C16—H16A	0.9700
C5—C17	1.527 (8)	C16—H16B	0.9700
C5—C6	1.536 (8)	C17—H17A	0.9600
C5—C18	1.552 (8)	C17—H17B	0.9600
C6—C7	1.523 (8)	C17—H17C	0.9600
C6—H6A	0.9700	C18—H18A	0.9600
C6—H6B	0.9700	C18—H18B	0.9600
C7—C8	1.519 (8)	C18—H18C	0.9600
C7—H7A	0.9700	C19—H19A	0.9600
C7—H7B	0.9700	C19—H19B	0.9600
C8—C9	1.541 (8)	C19—H19C	0.9600
C8—H8A	0.9700	C20—H20A	0.9700
C8—H8B	0.9700	C20—H20B	0.9700
C14—O1—H1O1	109.5	C9—C10—H10	104.8
C20—O2—H1O2	109.5	C12—C11—C10	116.7 (5)
C2—C1—C16	114.0 (5)	C12—C11—H11A	108.1
C2—C1—C10	110.4 (5)	C10—C11—H11A	108.1
C16—C1—C10	112.0 (4)	C12—C11—H11B	108.1
C2—C1—C15	111.0 (5)	C10—C11—H11B	108.1
C16—C1—C15	100.5 (4)	H11A—C11—H11B	107.3
C10—C1—C15	108.4 (4)	C13—C12—C11	114.9 (5)
C1—C2—C3	113.4 (5)	C13—C12—H12A	108.5
C1—C2—H2A	108.9	C11—C12—H12A	108.5
C3—C2—H2A	108.9	C13—C12—H12B	108.5
C1—C2—H2B	108.9	C11—C12—H12B	108.5
C3—C2—H2B	108.9	H12A—C12—H12B	107.5
H2A—C2—H2B	107.7	C12—C13—C16	107.7 (5)
C2—C3—C4	109.6 (5)	C12—C13—C14	114.2 (5)
C2—C3—H3A	109.8	C16—C13—C14	101.2 (5)
C4—C3—H3A	109.8	C12—C13—H13A	111
C2—C3—H3B	109.8	C16—C13—H13A	111
C4—C3—H3B	109.8	C14—C13—H13A	111
H3A—C3—H3B	108.2	O1—C14—C20	108.6 (5)
C3—C4—C5	115.2 (5)	O1—C14—C15	108.6 (5)
C3—C4—C9	109.9 (4)	C20—C14—C15	112.1 (5)
C5—C4—C9	117.3 (4)	O1—C14—C13	106.7 (4)
C3—C4—H4	104.2	C20—C14—C13	116.8 (5)
C5—C4—H4	104.2	C15—C14—C13	103.6 (5)
C9—C4—H4	104.2	C14—C15—C1	107.9 (5)
C17—C5—C6	107.7 (5)	C14—C15—H15A	110.1
C17—C5—C4	109.4 (5)	C1—C15—H15A	110.1
C6—C5—C4	108.4 (5)	C14—C15—H15B	110.1
C17—C5—C18	107.9 (5)	C1—C15—H15B	110.1
C6—C5—C18	109.7 (5)	H15A—C15—H15B	108.4
C4—C5—C18	113.6 (5)	C13—C16—C1	102.4 (4)
C7—C6—C5	114.5 (5)	C13—C16—H16A	111.3
C7—C6—H6A	108.6	C1—C16—H16A	111.3
C5—C6—H6A	108.6	C13—C16—H16B	111.3
C7—C6—H6B	108.6	C1—C16—H16B	111.3
C5—C6—H6B	108.6	H16A—C16—H16B	109.2
H6A—C6—H6B	107.6	C5—C17—H17A	109.5
C8—C7—C6	111.5 (5)	C5—C17—H17B	109.5
C8—C7—H7A	109.3	H17A—C17—H17B	109.5
C6—C7—H7A	109.3	C5—C17—H17C	109.5
C8—C7—H7B	109.3	H17A—C17—H17C	109.5
C6—C7—H7B	109.3	H17B—C17—H17C	109.5
H7A—C7—H7B	108.0	C5—C18—H18A	109.5
C7—C8—C9	114.8 (5)	C5—C18—H18B	109.5
C7—C8—H8A	108.6	H18A—C18—H18B	109.5
C9—C8—H8A	108.6	C5—C18—H18C	109.5
C7—C8—H8B	108.6	H18A—C18—H18C	109.5
C9—C8—H8B	108.6	H18B—C18—H18C	109.5
H8A—C8—H8B	107.5	C9—C19—H19A	109.5
C19—C9—C8	106.8 (5)	C9—C19—H19B	109.5
C19—C9—C4	113.9 (5)	H19A—C19—H19B	109.5
C8—C9—C4	107.4 (5)	C9—C19—H19C	109.5
C19—C9—C10	113.0 (5)	H19A—C19—H19C	109.5
C8—C9—C10	108.4 (4)	H19B—C19—H19C	109.5
C4—C9—C10	107.2 (4)	O2—C20—C14	113.5 (5)
C1—C10—C11	109.8 (4)	O2—C20—H20A	108.9
C1—C10—C9	116.0 (4)	C14—C20—H20A	108.9
C11—C10—C9	115.2 (4)	O2—C20—H20B	108.9
C1—C10—H10	104.8	C14—C20—H20B	108.9
C11—C10—H10	104.8	H20A—C20—H20B	107.7
C16—C1—C2—C3	−76.5 (6)	C19—C9—C10—C1	−74.1 (6)
C10—C1—C2—C3	50.6 (6)	C8—C9—C10—C1	167.8 (5)
C15—C1—C2—C3	170.9 (5)	C4—C9—C10—C1	52.2 (6)
C1—C2—C3—C4	−59.5 (6)	C19—C9—C10—C11	56.2 (6)
C2—C3—C4—C5	−161.5 (5)	C8—C9—C10—C11	−61.9 (6)
C2—C3—C4—C9	63.3 (6)	C4—C9—C10—C11	−177.5 (4)
C3—C4—C5—C17	59.7 (6)	C1—C10—C11—C12	33.2 (7)
C9—C4—C5—C17	−168.5 (5)	C9—C10—C11—C12	−100.0 (6)
C3—C4—C5—C6	176.9 (5)	C10—C11—C12—C13	−36.0 (7)
C9—C4—C5—C6	−51.3 (7)	C11—C12—C13—C16	55.0 (6)
C3—C4—C5—C18	−60.9 (7)	C11—C12—C13—C14	−56.6 (7)
C9—C4—C5—C18	70.9 (6)	C12—C13—C14—O1	−165.9 (5)
C17—C5—C6—C7	169.2 (5)	C16—C13—C14—O1	78.6 (5)
C4—C5—C6—C7	50.9 (7)	C12—C13—C14—C20	−44.3 (7)
C18—C5—C6—C7	−73.6 (7)	C16—C13—C14—C20	−159.7 (5)
C5—C6—C7—C8	−54.0 (7)	C12—C13—C14—C15	79.6 (6)
C6—C7—C8—C9	54.8 (7)	C16—C13—C14—C15	−35.9 (5)
C7—C8—C9—C19	70.9 (6)	O1—C14—C15—C1	−103.5 (5)
C7—C8—C9—C4	−51.6 (7)	C20—C14—C15—C1	136.5 (5)
C7—C8—C9—C10	−167.1 (5)	C13—C14—C15—C1	9.7 (6)
C3—C4—C9—C19	67.5 (6)	C2—C1—C15—C14	141.0 (5)
C5—C4—C9—C19	−66.7 (6)	C16—C1—C15—C14	20.1 (5)
C3—C4—C9—C8	−174.5 (5)	C10—C1—C15—C14	−97.5 (5)
C5—C4—C9—C8	51.4 (6)	C12—C13—C16—C1	−70.3 (5)
C3—C4—C9—C10	−58.3 (6)	C14—C13—C16—C1	49.8 (5)
C5—C4—C9—C10	167.6 (5)	C2—C1—C16—C13	−161.4 (4)
C2—C1—C10—C11	178.9 (5)	C10—C1—C16—C13	72.3 (5)
C16—C1—C10—C11	−52.9 (6)	C15—C1—C16—C13	−42.6 (5)
C15—C1—C10—C11	57.0 (6)	O1—C14—C20—O2	63.8 (6)
C2—C1—C10—C9	−48.3 (6)	C15—C14—C20—O2	−176.2 (5)
C16—C1—C10—C9	79.9 (6)	C13—C14—C20—O2	−56.9 (7)
C15—C1—C10—C9	−170.1 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O1W	0.82	2.08	2.842 (6)	156
O1W—H1W1···O2^i	0.84 (4)	1.98 (3)	2.802 (6)	164 (5)
O2—H1O2···O1^ii	0.82	2.01	2.799 (6)	161

Symmetry codes: (i) x−1/2, y−1/2, z; (ii) −x+1/2, y−1/2, −z.