Methyl 12-chloro­dehydro­abietate

The structure of the title compound (systematic name: methyl 6-chloro-7-isopropyl-1,4a-dimethyl-1,2,3,4,4a,9,10,10a-octahydro­phenanthrene-1-carboxyl­ate), C₂₁H₂₉ClO₂, has been determined by X-ray diffraction and is compared with the structures of methyl 12-acetyl­dehydro­abietate and methyl dehydro­abietate.

Key indicators

• Single-crystal X-ray study
• T = 163 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.036
• wR factor = 0.081
• Data-to-parameter ratio = 14.8

checkCIF/PLATON results

No syntax errors found



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           25.35
           From the CIF: _reflns_number_total               3282
           Count of symmetry unique reflns         1885
           Completeness (_total/calc)            174.11%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1397
           Fraction of Friedel pairs measured     0.741
           Are heavy atom types Z>Si present        yes
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C7     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C8     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C14    = .          R

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

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

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Computing details

Data collection: CrystalClear (Rigaku, 1999); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).

methyl 6-chloro-7-isopropyl-1,4a-dimethyl-1,2,3,4,4a,9,10,10a-octahydrophenanthrene- 1-carboxylate

Crystal data

C21H29ClO2	F(000) = 752
Mr = 348.89	Dx = 1.237 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 3656 reflections
a = 13.6507 (17) Å	θ = 3.1–25.3°
b = 6.0856 (6) Å	µ = 0.21 mm^−1
c = 23.120 (3) Å	T = 163 K
β = 102.760 (16)°	Platelet, colourless
V = 1873.2 (4) Å^3	0.56 × 0.41 × 0.06 mm
Z = 4

Data collection

Rigaku Mercury diffractometer	3282 independent reflections
Radiation source: fine-focus sealed tube	3079 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
Detector resolution: 7.31 pixels mm^-1	θmax = 25.4°, θmin = 3.1°
ω scans	h = −16→15
Absorption correction: multi-scan (Jacobson, 1998)	k = −7→6
Tmin = 0.856, Tmax = 0.987	l = −27→27
9174 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.081	w = 1/[σ^2(Fo^2) + (0.0334P)^2 + 0.9195P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
3282 reflections	Δρmax = 0.19 e Å^−3
222 parameters	Δρmin = −0.17 e Å^−3
1 restraint	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (6)

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
Cl1	0.53162 (4)	0.49514 (10)	0.91824 (2)	0.03557 (16)
O1	0.66971 (14)	−0.1660 (3)	0.55486 (8)	0.0413 (4)
O2	0.64227 (12)	0.1780 (2)	0.57863 (7)	0.0308 (4)
C1	0.55802 (15)	0.2461 (4)	0.82713 (9)	0.0219 (4)
H1	0.4881	0.2189	0.8218	0.026*
C2	0.60639 (16)	0.3760 (3)	0.87397 (9)	0.0227 (5)
C3	0.70896 (15)	0.4187 (3)	0.88520 (9)	0.0226 (5)
C4	0.75951 (15)	0.3234 (4)	0.84577 (9)	0.0244 (5)
H4	0.8298	0.3478	0.8519	0.029*
C5	0.71356 (15)	0.1936 (4)	0.79754 (9)	0.0226 (5)
C6	0.61047 (14)	0.1546 (3)	0.78759 (9)	0.0191 (4)
C7	0.55540 (13)	0.0072 (4)	0.73659 (8)	0.0184 (4)
C8	0.61799 (13)	0.0085 (4)	0.68807 (8)	0.0189 (4)
H8	0.6241	0.1674	0.6784	0.023*
C9	0.72577 (15)	−0.0661 (4)	0.71344 (9)	0.0245 (5)
H9A	0.7255	−0.2106	0.7331	0.029*
H9B	0.7620	−0.0821	0.6810	0.029*
C10	0.77859 (15)	0.1031 (4)	0.75811 (10)	0.0279 (5)
H10A	0.8390	0.0346	0.7833	0.034*
H10B	0.8013	0.2263	0.7364	0.034*
C11	0.45038 (14)	0.0987 (4)	0.70904 (9)	0.0218 (5)
H11A	0.4072	0.0828	0.7380	0.026*
H11B	0.4563	0.2575	0.7012	0.026*
C12	0.39958 (14)	−0.0155 (4)	0.65137 (8)	0.0249 (4)
H12A	0.3876	−0.1717	0.6596	0.030*
H12B	0.3336	0.0542	0.6354	0.030*
C13	0.46347 (14)	−0.0020 (4)	0.60542 (8)	0.0231 (4)
H13A	0.4700	0.1538	0.5946	0.028*
H13B	0.4291	−0.0814	0.5692	0.028*
C14	0.56911 (15)	−0.1002 (3)	0.62767 (9)	0.0207 (5)
C15	0.76249 (16)	0.5658 (4)	0.93530 (9)	0.0281 (5)
H15	0.7228	0.5644	0.9668	0.034*
C16	0.76360 (18)	0.8026 (4)	0.91276 (10)	0.0352 (6)
H16A	0.7967	0.8067	0.8792	0.053*
H16B	0.8003	0.8965	0.9447	0.053*
H16C	0.6945	0.8560	0.8999	0.053*
C17	0.86868 (17)	0.4894 (5)	0.96343 (10)	0.0408 (6)
H17A	0.8674	0.3335	0.9738	0.061*
H17B	0.8949	0.5756	0.9993	0.061*
H17C	0.9120	0.5101	0.9352	0.061*
C18	0.54484 (15)	−0.2213 (4)	0.76417 (9)	0.0243 (5)
H18A	0.5147	−0.2042	0.7987	0.037*
H18B	0.6113	−0.2890	0.7766	0.037*
H18C	0.5018	−0.3153	0.7347	0.037*
C19	0.56428 (17)	−0.3530 (3)	0.62907 (10)	0.0288 (5)
H19A	0.5433	−0.4092	0.5885	0.043*
H19B	0.5157	−0.3989	0.6522	0.043*
H19C	0.6308	−0.4117	0.6474	0.043*
C20	0.63266 (15)	−0.0388 (4)	0.58337 (9)	0.0232 (5)
C21	0.70048 (17)	0.2544 (4)	0.53759 (9)	0.0319 (5)
H21A	0.7692	0.1978	0.5495	0.048*
H21B	0.7019	0.4154	0.5377	0.048*
H21C	0.6699	0.2018	0.4976	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0331 (3)	0.0447 (4)	0.0311 (3)	−0.0004 (3)	0.0116 (2)	−0.0103 (3)
O1	0.0620 (12)	0.0260 (9)	0.0471 (10)	−0.0005 (8)	0.0359 (9)	−0.0046 (8)
O2	0.0455 (10)	0.0197 (8)	0.0345 (9)	−0.0049 (7)	0.0245 (8)	−0.0018 (7)
C1	0.0199 (10)	0.0235 (10)	0.0227 (10)	−0.0022 (9)	0.0059 (8)	0.0003 (9)
C2	0.0262 (11)	0.0231 (12)	0.0210 (11)	0.0032 (9)	0.0100 (9)	0.0023 (9)
C3	0.0260 (11)	0.0222 (11)	0.0180 (10)	−0.0021 (9)	0.0013 (9)	0.0048 (9)
C4	0.0188 (10)	0.0275 (12)	0.0257 (11)	−0.0052 (9)	0.0026 (8)	0.0034 (10)
C5	0.0211 (10)	0.0248 (12)	0.0220 (10)	−0.0001 (9)	0.0051 (8)	0.0042 (9)
C6	0.0198 (10)	0.0197 (11)	0.0184 (10)	−0.0006 (9)	0.0054 (8)	0.0034 (9)
C7	0.0163 (9)	0.0177 (10)	0.0212 (9)	−0.0030 (9)	0.0041 (7)	0.0001 (10)
C8	0.0188 (9)	0.0178 (11)	0.0208 (9)	−0.0008 (10)	0.0057 (7)	0.0007 (10)
C9	0.0199 (10)	0.0286 (13)	0.0271 (11)	0.0039 (9)	0.0096 (9)	−0.0012 (9)
C10	0.0160 (10)	0.0389 (14)	0.0293 (12)	−0.0016 (10)	0.0058 (9)	0.0002 (10)
C11	0.0180 (10)	0.0241 (11)	0.0241 (11)	−0.0004 (9)	0.0060 (8)	−0.0001 (9)
C12	0.0177 (9)	0.0304 (12)	0.0254 (10)	0.0007 (10)	0.0022 (8)	−0.0025 (10)
C13	0.0237 (10)	0.0254 (11)	0.0190 (9)	−0.0039 (10)	0.0018 (8)	−0.0022 (10)
C14	0.0237 (11)	0.0160 (10)	0.0226 (11)	0.0010 (9)	0.0057 (9)	−0.0014 (8)
C15	0.0322 (12)	0.0298 (13)	0.0213 (11)	−0.0052 (10)	0.0041 (9)	−0.0015 (9)
C16	0.0426 (14)	0.0291 (14)	0.0314 (12)	−0.0065 (12)	0.0025 (11)	−0.0062 (11)
C17	0.0375 (13)	0.0405 (14)	0.0368 (13)	−0.0027 (13)	−0.0080 (10)	−0.0033 (13)
C18	0.0258 (11)	0.0217 (12)	0.0266 (11)	−0.0034 (10)	0.0081 (9)	0.0001 (9)
C19	0.0380 (13)	0.0173 (11)	0.0336 (13)	−0.0011 (10)	0.0134 (10)	−0.0015 (10)
C20	0.0256 (11)	0.0232 (13)	0.0208 (10)	−0.0038 (10)	0.0052 (8)	−0.0034 (10)
C21	0.0420 (13)	0.0316 (13)	0.0255 (11)	−0.0126 (11)	0.0149 (10)	−0.0016 (10)

Geometric parameters (Å, º)

Cl1—C2	1.754 (2)	C11—H11B	0.9900
O1—C20	1.199 (2)	C12—C13	1.518 (3)
O2—C20	1.333 (3)	C12—H12A	0.9900
O2—C21	1.442 (2)	C12—H12B	0.9900
C1—C2	1.385 (3)	C13—C14	1.541 (3)
C1—C6	1.396 (3)	C13—H13A	0.9900
C1—H1	0.9500	C13—H13B	0.9900
C2—C3	1.391 (3)	C14—C20	1.528 (3)
C3—C4	1.386 (3)	C14—C19	1.540 (3)
C3—C15	1.518 (3)	C15—C17	1.524 (3)
C4—C5	1.397 (3)	C15—C16	1.533 (3)
C4—H4	0.9500	C15—H15	1.0000
C5—C6	1.395 (3)	C16—H16A	0.9800
C5—C10	1.510 (3)	C16—H16B	0.9800
C6—C7	1.539 (3)	C16—H16C	0.9800
C7—C11	1.539 (3)	C17—H17A	0.9800
C7—C18	1.550 (3)	C17—H17B	0.9800
C7—C8	1.553 (2)	C17—H17C	0.9800
C8—C9	1.528 (3)	C18—H18A	0.9800
C8—C14	1.556 (3)	C18—H18B	0.9800
C8—H8	1.0000	C18—H18C	0.9800
C9—C10	1.522 (3)	C19—H19A	0.9800
C9—H9A	0.9900	C19—H19B	0.9800
C9—H9B	0.9900	C19—H19C	0.9800
C10—H10A	0.9900	C21—H21A	0.9800
C10—H10B	0.9900	C21—H21B	0.9800
C11—C12	1.527 (3)	C21—H21C	0.9800
C11—H11A	0.9900
C20—O2—C21	116.85 (17)	C11—C12—H12B	109.3
C2—C1—C6	121.01 (19)	H12A—C12—H12B	108.0
C2—C1—H1	119.5	C12—C13—C14	112.67 (16)
C6—C1—H1	119.5	C12—C13—H13A	109.1
C1—C2—C3	122.62 (19)	C14—C13—H13A	109.1
C1—C2—Cl1	116.99 (16)	C12—C13—H13B	109.1
C3—C2—Cl1	120.35 (16)	C14—C13—H13B	109.1
C4—C3—C2	115.20 (18)	H13A—C13—H13B	107.8
C4—C3—C15	121.54 (19)	C20—C14—C19	106.97 (17)
C2—C3—C15	123.22 (19)	C20—C14—C13	108.03 (16)
C3—C4—C5	124.10 (19)	C19—C14—C13	110.69 (19)
C3—C4—H4	118.0	C20—C14—C8	107.64 (16)
C5—C4—H4	118.0	C19—C14—C8	114.68 (18)
C6—C5—C4	119.12 (18)	C13—C14—C8	108.59 (16)
C6—C5—C10	122.97 (18)	C3—C15—C17	113.4 (2)
C4—C5—C10	117.91 (17)	C3—C15—C16	109.52 (17)
C5—C6—C1	117.94 (19)	C17—C15—C16	110.6 (2)
C5—C6—C7	122.00 (17)	C3—C15—H15	107.7
C1—C6—C7	120.01 (17)	C17—C15—H15	107.7
C11—C7—C6	111.04 (18)	C16—C15—H15	107.7
C11—C7—C18	109.41 (16)	C15—C16—H16A	109.5
C6—C7—C18	106.38 (15)	C15—C16—H16B	109.5
C11—C7—C8	108.05 (15)	H16A—C16—H16B	109.5
C6—C7—C8	107.26 (15)	C15—C16—H16C	109.5
C18—C7—C8	114.70 (18)	H16A—C16—H16C	109.5
C9—C8—C7	110.97 (15)	H16B—C16—H16C	109.5
C9—C8—C14	113.82 (16)	C15—C17—H17A	109.5
C7—C8—C14	116.79 (15)	C15—C17—H17B	109.5
C9—C8—H8	104.6	H17A—C17—H17B	109.5
C7—C8—H8	104.6	C15—C17—H17C	109.5
C14—C8—H8	104.6	H17A—C17—H17C	109.5
C10—C9—C8	109.34 (17)	H17B—C17—H17C	109.5
C10—C9—H9A	109.8	C7—C18—H18A	109.5
C8—C9—H9A	109.8	C7—C18—H18B	109.5
C10—C9—H9B	109.8	H18A—C18—H18B	109.5
C8—C9—H9B	109.8	C7—C18—H18C	109.5
H9A—C9—H9B	108.3	H18A—C18—H18C	109.5
C5—C10—C9	113.76 (17)	H18B—C18—H18C	109.5
C5—C10—H10A	108.8	C14—C19—H19A	109.5
C9—C10—H10A	108.8	C14—C19—H19B	109.5
C5—C10—H10B	108.8	H19A—C19—H19B	109.5
C9—C10—H10B	108.8	C14—C19—H19C	109.5
H10A—C10—H10B	107.7	H19A—C19—H19C	109.5
C12—C11—C7	113.49 (17)	H19B—C19—H19C	109.5
C12—C11—H11A	108.9	O1—C20—O2	122.19 (19)
C7—C11—H11A	108.9	O1—C20—C14	125.58 (19)
C12—C11—H11B	108.9	O2—C20—C14	112.23 (16)
C7—C11—H11B	108.9	O2—C21—H21A	109.5
H11A—C11—H11B	107.7	O2—C21—H21B	109.5
C13—C12—C11	111.46 (16)	H21A—C21—H21B	109.5
C13—C12—H12A	109.3	O2—C21—H21C	109.5
C11—C12—H12A	109.3	H21A—C21—H21C	109.5
C13—C12—H12B	109.3	H21B—C21—H21C	109.5
C6—C1—C2—C3	−1.5 (3)	C6—C5—C10—C9	−10.2 (3)
C6—C1—C2—Cl1	176.43 (17)	C4—C5—C10—C9	170.26 (19)
C1—C2—C3—C4	0.5 (3)	C8—C9—C10—C5	40.7 (3)
Cl1—C2—C3—C4	−177.30 (16)	C6—C7—C11—C12	169.48 (16)
C1—C2—C3—C15	178.2 (2)	C18—C7—C11—C12	−73.4 (2)
Cl1—C2—C3—C15	0.4 (3)	C8—C7—C11—C12	52.1 (2)
C2—C3—C4—C5	0.3 (3)	C7—C11—C12—C13	−57.1 (2)
C15—C3—C4—C5	−177.4 (2)	C11—C12—C13—C14	57.1 (3)
C3—C4—C5—C6	−0.2 (3)	C12—C13—C14—C20	−169.25 (18)
C3—C4—C5—C10	179.3 (2)	C12—C13—C14—C19	73.9 (2)
C4—C5—C6—C1	−0.7 (3)	C12—C13—C14—C8	−52.8 (2)
C10—C5—C6—C1	179.8 (2)	C9—C8—C14—C20	−60.2 (2)
C4—C5—C6—C7	−177.96 (19)	C7—C8—C14—C20	168.44 (17)
C10—C5—C6—C7	2.5 (3)	C9—C8—C14—C19	58.7 (2)
C2—C1—C6—C5	1.5 (3)	C7—C8—C14—C19	−72.7 (2)
C2—C1—C6—C7	178.83 (19)	C9—C8—C14—C13	−176.89 (18)
C5—C6—C7—C11	−142.74 (19)	C7—C8—C14—C13	51.7 (2)
C1—C6—C7—C11	40.1 (3)	C4—C3—C15—C17	−37.6 (3)
C5—C6—C7—C18	98.3 (2)	C2—C3—C15—C17	144.9 (2)
C1—C6—C7—C18	−78.9 (2)	C4—C3—C15—C16	86.5 (3)
C5—C6—C7—C8	−24.9 (3)	C2—C3—C15—C16	−91.0 (2)
C1—C6—C7—C8	157.92 (18)	C21—O2—C20—O1	−0.5 (3)
C11—C7—C8—C9	176.19 (18)	C21—O2—C20—C14	−179.62 (16)
C6—C7—C8—C9	56.4 (2)	C19—C14—C20—O1	1.1 (3)
C18—C7—C8—C9	−61.5 (2)	C13—C14—C20—O1	−118.1 (2)
C11—C7—C8—C14	−51.1 (2)	C8—C14—C20—O1	124.8 (2)
C6—C7—C8—C14	−170.88 (17)	C19—C14—C20—O2	−179.81 (18)
C18—C7—C8—C14	71.2 (2)	C13—C14—C20—O2	61.0 (2)
C7—C8—C9—C10	−66.5 (2)	C8—C14—C20—O2	−56.1 (2)
C14—C8—C9—C10	159.32 (17)