3,5,5,6,8,8-Hexamethyl-5,6,7,8-tetra-hydro-2-naphthoic acid (AHTN-COOH).

The title compound, C(17)H(24)O(2), is the product of a haloform reaction of 6-acetyl-1,1,2,4,4,7-hexa-methyl-tetra-line (AHTN). The compound is a racemic mixture with a disorder in its aliphatic ring [occupany ratio 0.683 (4):0.317 (4)] due to two possible half-chair forms. The carb-oxy-lic acid unit is slightly twisted out of coplanarity with the aromatic system [dihedral angle = 29.26 (6)°]. In the crystal, pairs of short classical inter-molecular O-H⋯O hydrogen bonds link pairs of mol-ecules around a center of symmetry.

Related literature

For a similar synthesis of AHTN-COOH and the mechanism of the haloform reaction, see: Valdersnes et al. (2006 ▶); Fuson & Bull (1934 ▶). For the crystal structure of AHTN, see: De Ridder et al. (1990 ▶). For environmental occurrence and estrogenic activity of AHTN, see: Heberer (2003 ▶); Bitsch et al. (2002 ▶). For industrial synthesis of AHTN and annual production amounts, see: Sell (2006 ▶); Kupper et al. (2004 ▶).

Experimental

Crystal data

C17H24O2

M = 260.36

Monoclinic,

a = 8.9718 (2) Å

b = 10.1447 (3) Å

c = 17.7058 (5) Å

β = 112.3100 (19)°

V = 1490.88 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.07 mm−1

T = 100 K

0.44 × 0.44 × 0.28 mm

Data collection

Stoe IPDS-2t diffractometer

5695 measured reflections

2933 independent reflections

2525 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.130

S = 1.04

2933 reflections

206 parameters

30 restraints

H-atom parameters constrained

Δρmax = 0.29 e Å−3

Δρmin = −0.34 e Å−3

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810038572/fl2316sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810038572/fl2316Isup2.hkl

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

C17H24O2	F(000) = 568
Mr = 260.36	Dx = 1.160 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 30064 reflections
a = 8.9718 (2) Å	θ = 2.3–30.9°
b = 10.1447 (3) Å	µ = 0.07 mm−1
c = 17.7058 (5) Å	T = 100 K
β = 112.3100 (19)°	Fragment, colourless
V = 1490.88 (7) Å3	0.44 × 0.44 × 0.28 mm
Z = 4

Stoe IPDS-2t diffractometer	2525 reflections with I > 2σ(I)
Radiation source: long fine focus sealed X-ray tube	Rint = 0.016
planar graphite	θmax = 26.0°, θmin = 2.8°
Detector resolution: 6.67 pixels mm-1	h = −11→10
ω–rotation,ω–incr.=1°,319 exposures scans	k = −12→12
5695 measured reflections	l = −21→10
2933 independent reflections

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0771P)2 + 0.4377P] where P = (Fo2 + 2Fc2)/3
2933 reflections	(Δ/σ)max < 0.001
206 parameters	Δρmax = 0.29 e Å−3
30 restraints	Δρmin = −0.34 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	Occ. (<1)
O1	−0.40903 (12)	0.07719 (11)	−0.05516 (6)	0.0301 (3)
O2	−0.31528 (12)	0.04014 (11)	0.07904 (6)	0.0274 (3)
H2	−0.4096	−0.0008	0.0723	0.099 (10)*
C1	−0.30126 (16)	0.08804 (13)	0.01415 (8)	0.0198 (3)
C2	−0.14885 (15)	0.15904 (13)	0.02749 (8)	0.0191 (3)
C3	−0.07123 (16)	0.22058 (13)	0.10232 (8)	0.0192 (3)
H3	−0.1154	0.2127	0.1419	0.029*
C4	0.06989 (16)	0.29353 (13)	0.12086 (8)	0.0192 (3)
C5	0.13789 (16)	0.30168 (13)	0.06178 (8)	0.0196 (3)
C6	0.05971 (16)	0.23646 (14)	−0.01268 (8)	0.0230 (3)
H6	0.1069	0.2400	−0.0512	0.034*
C7	−0.08302 (16)	0.16713 (14)	−0.03275 (8)	0.0219 (3)
C8	−0.15681 (19)	0.10224 (17)	−0.11538 (9)	0.0316 (4)
H8A	−0.2521	0.1494	−0.1483	0.047*
H8B	−0.1846	0.0128	−0.1088	0.047*
H8C	−0.0807	0.1032	−0.1416	0.047*
C9	0.29440 (16)	0.37676 (14)	0.07460 (8)	0.0231 (3)
C10A	0.3364 (4)	0.4704 (4)	0.1476 (2)	0.0292 (7)	0.683 (4)
H10A	0.2582	0.5428	0.1321	0.044*	0.683 (4)
C11A	0.3210 (3)	0.3998 (3)	0.21971 (13)	0.0272 (7)	0.683 (4)
H11A	0.3627	0.4560	0.2675	0.041*	0.683 (4)
H11B	0.3858	0.3202	0.2310	0.041*	0.683 (4)
C15A	0.5059 (12)	0.5308 (12)	0.1732 (6)	0.0497 (14)	0.683 (4)
H15A	0.5265	0.5866	0.2198	0.075*	0.683 (4)
H15B	0.5123	0.5819	0.1288	0.075*	0.683 (4)
H15C	0.5847	0.4615	0.1867	0.075*	0.683 (4)
C10B	0.3736 (8)	0.4188 (8)	0.1699 (4)	0.0292 (15)	0.317 (4)
H10B	0.4204	0.3404	0.2026	0.044*	0.317 (4)
C11B	0.2488 (7)	0.4758 (5)	0.1983 (3)	0.0297 (14)	0.317 (4)
H11C	0.1851	0.5417	0.1600	0.045*	0.317 (4)
H11D	0.3005	0.5171	0.2513	0.045*	0.317 (4)
C15B	0.507 (3)	0.524 (3)	0.1870 (15)	0.0497 (14)	0.317 (4)
H15D	0.4578	0.6093	0.1706	0.075*	0.317 (4)
H15E	0.5725	0.5038	0.1568	0.075*	0.317 (4)
H15F	0.5720	0.5256	0.2443	0.075*	0.317 (4)
C14A	0.0479 (4)	0.4785 (3)	0.20837 (16)	0.0297 (6)	0.683 (4)
H14A	−0.0611	0.4526	0.1978	0.045*	0.683 (4)
H14B	0.0488	0.5422	0.1684	0.045*	0.683 (4)
H14C	0.0947	0.5166	0.2619	0.045*	0.683 (4)
C14B	−0.0085 (8)	0.4464 (7)	0.2128 (4)	0.0297 (6)	0.317 (4)
H14D	0.0298	0.4937	0.2635	0.045*	0.317 (4)
H14E	−0.0922	0.3865	0.2118	0.045*	0.317 (4)
H14F	−0.0504	0.5075	0.1683	0.045*	0.317 (4)
C12	0.14176 (18)	0.36242 (15)	0.20370 (8)	0.0261 (3)
C13	0.1649 (2)	0.26665 (17)	0.27301 (9)	0.0393 (4)
H13A	0.2261	0.3084	0.3241	0.059*
H13B	0.2217	0.1902	0.2663	0.059*
H13C	0.0617	0.2407	0.2725	0.059*
C16	0.42374 (19)	0.27774 (17)	0.07668 (13)	0.0408 (4)
H16A	0.5219	0.3237	0.0843	0.061*
H16B	0.3887	0.2300	0.0261	0.061*
H16C	0.4420	0.2172	0.1210	0.061*
C17	0.2657 (2)	0.4705 (2)	0.00255 (13)	0.0492 (5)
H17A	0.1800	0.5304	−0.0016	0.074*
H17B	0.2367	0.4204	−0.0470	0.074*
H17C	0.3623	0.5195	0.0111	0.074*

	U11	U22	U33	U12	U13	U23
O1	0.0218 (5)	0.0408 (6)	0.0227 (5)	−0.0104 (4)	0.0028 (4)	−0.0008 (4)
O2	0.0213 (5)	0.0348 (6)	0.0255 (5)	−0.0064 (4)	0.0081 (4)	0.0061 (4)
C1	0.0183 (6)	0.0202 (6)	0.0202 (6)	−0.0005 (5)	0.0066 (5)	0.0002 (5)
C2	0.0172 (6)	0.0191 (7)	0.0203 (6)	−0.0001 (5)	0.0063 (5)	0.0007 (5)
C3	0.0206 (6)	0.0198 (7)	0.0187 (6)	0.0008 (5)	0.0092 (5)	0.0012 (5)
C4	0.0200 (6)	0.0170 (6)	0.0185 (6)	−0.0001 (5)	0.0050 (5)	−0.0002 (5)
C5	0.0177 (6)	0.0175 (6)	0.0227 (6)	−0.0001 (5)	0.0067 (5)	0.0012 (5)
C6	0.0238 (7)	0.0266 (7)	0.0223 (7)	−0.0025 (5)	0.0130 (6)	−0.0021 (5)
C7	0.0228 (7)	0.0233 (7)	0.0197 (6)	−0.0024 (5)	0.0081 (5)	−0.0024 (5)
C8	0.0328 (8)	0.0414 (9)	0.0230 (7)	−0.0119 (7)	0.0135 (6)	−0.0100 (6)
C9	0.0188 (7)	0.0235 (7)	0.0271 (7)	−0.0041 (5)	0.0088 (5)	−0.0006 (6)
C10A	0.0318 (16)	0.0283 (16)	0.0270 (15)	−0.0133 (12)	0.0106 (12)	−0.0039 (12)
C11A	0.0238 (12)	0.0336 (15)	0.0201 (10)	−0.0111 (11)	0.0038 (9)	−0.0039 (10)
C15A	0.0487 (12)	0.068 (2)	0.036 (4)	−0.0383 (13)	0.019 (2)	−0.016 (2)
C10B	0.026 (3)	0.026 (3)	0.028 (3)	−0.006 (2)	0.001 (2)	0.004 (2)
C11B	0.038 (3)	0.023 (3)	0.024 (2)	−0.006 (2)	0.006 (2)	0.000 (2)
C15B	0.0487 (12)	0.068 (2)	0.036 (4)	−0.0383 (13)	0.019 (2)	−0.016 (2)
C14A	0.0400 (18)	0.0209 (14)	0.0221 (9)	−0.0016 (11)	0.0048 (11)	−0.0056 (9)
C14B	0.0400 (18)	0.0209 (14)	0.0221 (9)	−0.0016 (11)	0.0048 (11)	−0.0056 (9)
C12	0.0300 (7)	0.0291 (8)	0.0189 (6)	−0.0107 (6)	0.0087 (5)	−0.0050 (6)
C13	0.0526 (10)	0.0349 (9)	0.0199 (7)	0.0117 (8)	0.0020 (7)	0.0004 (6)
C16	0.0247 (8)	0.0343 (9)	0.0677 (12)	−0.0011 (7)	0.0224 (8)	0.0013 (8)
C17	0.0290 (9)	0.0488 (11)	0.0625 (12)	−0.0103 (8)	0.0092 (8)	0.0271 (9)

O1—C1	1.2458 (17)	C15A—H15B	0.9600
O2—C1	1.2969 (16)	C15A—H15C	0.9600
O2—H2	0.9088	C10B—C11B	1.505 (9)
C1—C2	1.4830 (18)	C10B—C15B	1.546 (12)
C2—C3	1.3892 (18)	C10B—H10B	0.9800
C2—C7	1.4040 (18)	C11B—C12	1.524 (5)
C3—C4	1.3939 (19)	C11B—H11C	0.9700
C3—H3	0.9300	C11B—H11D	0.9700
C4—C5	1.3992 (19)	C15B—H15D	0.9600
C4—C12	1.5289 (18)	C15B—H15E	0.9600
C5—C6	1.4020 (19)	C15B—H15F	0.9600
C5—C9	1.5366 (18)	C14A—C12	1.468 (3)
C6—C7	1.3839 (19)	C14A—H14A	0.9600
C6—H6	0.9300	C14A—H14B	0.9600
C7—C8	1.5089 (18)	C14A—H14C	0.9600
C8—H8A	0.9600	C14B—C12	1.653 (7)
C8—H8B	0.9600	C14B—H14D	0.9600
C8—H8C	0.9600	C14B—H14E	0.9600
C9—C16	1.525 (2)	C14B—H14F	0.9600
C9—C10A	1.532 (3)	C12—C13	1.516 (2)
C9—C17	1.533 (2)	C13—H13A	0.9600
C9—C10B	1.620 (6)	C13—H13B	0.9600
C10A—C11A	1.515 (4)	C13—H13C	0.9600
C10A—C15A	1.540 (7)	C16—H16A	0.9600
C10A—H10A	0.9800	C16—H16B	0.9600
C11A—C12	1.570 (3)	C16—H16C	0.9600
C11A—H11A	0.9700	C17—H17A	0.9600
C11A—H11B	0.9700	C17—H17B	0.9600
C15A—H15A	0.9600	C17—H17C	0.9600
C1—O2—H2	117.0	C15B—C10B—C9	112.8 (11)
O1—C1—O2	122.65 (12)	C11B—C10B—H10B	108.7
O1—C1—C2	121.59 (12)	C15B—C10B—H10B	108.7
O2—C1—C2	115.76 (11)	C9—C10B—H10B	108.7
C3—C2—C7	119.68 (12)	C10B—C11B—C12	107.3 (4)
C3—C2—C1	117.92 (11)	C10B—C11B—H11C	110.3
C7—C2—C1	122.39 (12)	C12—C11B—H11C	110.3
C2—C3—C4	123.01 (12)	C10B—C11B—H11D	110.3
C2—C3—H3	118.5	C12—C11B—H11D	110.3
C4—C3—H3	118.5	H11C—C11B—H11D	108.5
C3—C4—C5	118.05 (12)	C10B—C15B—H15D	109.5
C3—C4—C12	118.89 (12)	C10B—C15B—H15E	109.5
C5—C4—C12	123.05 (12)	H15D—C15B—H15E	109.5
C4—C5—C6	118.07 (12)	C10B—C15B—H15F	109.5
C4—C5—C9	123.51 (12)	H15D—C15B—H15F	109.5
C6—C5—C9	118.41 (11)	H15E—C15B—H15F	109.5
C7—C6—C5	124.41 (12)	C12—C14A—H14A	109.5
C7—C6—H6	117.8	C12—C14A—H14B	109.5
C5—C6—H6	117.8	C12—C14A—H14C	109.5
C6—C7—C2	116.73 (12)	C12—C14B—H14D	109.5
C6—C7—C8	119.56 (12)	C12—C14B—H14E	109.5
C2—C7—C8	123.70 (12)	C12—C14B—H14F	109.5
C7—C8—H8A	109.5	C14A—C12—C13	111.94 (16)
C7—C8—H8B	109.5	C13—C12—C11B	129.6 (2)
H8A—C8—H8B	109.5	C14A—C12—C4	112.25 (15)
C7—C8—H8C	109.5	C13—C12—C4	111.21 (12)
H8A—C8—H8C	109.5	C11B—C12—C4	109.3 (2)
H8B—C8—H8C	109.5	C14A—C12—C11A	111.49 (18)
C16—C9—C10A	116.56 (19)	C13—C12—C11A	101.08 (15)
C16—C9—C17	108.36 (14)	C4—C12—C11A	108.28 (12)
C10A—C9—C17	103.15 (19)	C13—C12—C14B	96.8 (3)
C16—C9—C5	108.75 (12)	C11B—C12—C14B	100.0 (3)
C10A—C9—C5	110.50 (14)	C4—C12—C14B	105.4 (2)
C17—C9—C5	109.21 (12)	C12—C13—H13A	109.5
C16—C9—C10B	96.9 (3)	C12—C13—H13B	109.5
C17—C9—C10B	124.9 (3)	H13A—C13—H13B	109.5
C5—C9—C10B	107.4 (2)	C12—C13—H13C	109.5
C11A—C10A—C9	110.2 (2)	H13A—C13—H13C	109.5
C11A—C10A—C15A	109.7 (4)	H13B—C13—H13C	109.5
C9—C10A—C15A	113.2 (5)	C9—C16—H16A	109.5
C11A—C10A—H10A	107.9	C9—C16—H16B	109.5
C9—C10A—H10A	107.9	H16A—C16—H16B	109.5
C15A—C10A—H10A	107.9	C9—C16—H16C	109.5
C10A—C11A—C12	112.1 (2)	H16A—C16—H16C	109.5
C10A—C11A—H11A	109.2	H16B—C16—H16C	109.5
C12—C11A—H11A	109.2	C9—C17—H17A	109.5
C10A—C11A—H11B	109.2	C9—C17—H17B	109.5
C12—C11A—H11B	109.2	H17A—C17—H17B	109.5
H11A—C11A—H11B	107.9	C9—C17—H17C	109.5
C11B—C10B—C15B	106.6 (14)	H17A—C17—H17C	109.5
C11B—C10B—C9	111.2 (5)	H17B—C17—H17C	109.5
O1—C1—C2—C3	150.42 (13)	C5—C9—C10A—C15A	170.1 (5)
O2—C1—C2—C3	−28.69 (18)	C10B—C9—C10A—C15A	83.1 (9)
O1—C1—C2—C7	−28.8 (2)	C9—C10A—C11A—C12	−67.0 (3)
O2—C1—C2—C7	152.14 (13)	C15A—C10A—C11A—C12	167.7 (6)
C7—C2—C3—C4	1.2 (2)	C16—C9—C10B—C11B	−157.8 (5)
C1—C2—C3—C4	−177.96 (12)	C10A—C9—C10B—C11B	55.8 (7)
C2—C3—C4—C5	−1.7 (2)	C17—C9—C10B—C11B	84.1 (5)
C2—C3—C4—C12	177.34 (12)	C5—C9—C10B—C11B	−45.6 (6)
C3—C4—C5—C6	0.27 (19)	C16—C9—C10B—C15B	82.6 (15)
C12—C4—C5—C6	−178.78 (13)	C10A—C9—C10B—C15B	−63.9 (16)
C3—C4—C5—C9	−178.97 (12)	C17—C9—C10B—C15B	−35.5 (15)
C12—C4—C5—C9	2.0 (2)	C5—C9—C10B—C15B	−165.3 (14)
C4—C5—C6—C7	1.8 (2)	C15B—C10B—C11B—C12	−164.9 (11)
C9—C5—C6—C7	−178.93 (13)	C9—C10B—C11B—C12	71.8 (6)
C5—C6—C7—C2	−2.3 (2)	C10B—C11B—C12—C14A	−166.0 (4)
C5—C6—C7—C8	179.27 (14)	C10B—C11B—C12—C13	85.6 (4)
C3—C2—C7—C6	0.74 (19)	C10B—C11B—C12—C4	−56.4 (5)
C1—C2—C7—C6	179.90 (12)	C10B—C11B—C12—C11A	38.6 (4)
C3—C2—C7—C8	179.11 (13)	C10B—C11B—C12—C14B	−166.8 (5)
C1—C2—C7—C8	−1.7 (2)	C3—C4—C12—C14A	−73.3 (2)
C4—C5—C9—C16	113.07 (15)	C5—C4—C12—C14A	105.7 (2)
C6—C5—C9—C16	−66.16 (17)	C3—C4—C12—C13	52.99 (17)
C4—C5—C9—C10A	−16.1 (2)	C5—C4—C12—C13	−127.97 (15)
C6—C5—C9—C10A	164.7 (2)	C3—C4—C12—C11B	−157.5 (3)
C4—C5—C9—C17	−128.86 (16)	C5—C4—C12—C11B	21.5 (3)
C6—C5—C9—C17	51.91 (18)	C3—C4—C12—C11A	163.19 (15)
C4—C5—C9—C10B	9.2 (3)	C5—C4—C12—C11A	−17.8 (2)
C6—C5—C9—C10B	−170.0 (3)	C3—C4—C12—C14B	−50.8 (3)
C16—C9—C10A—C11A	−78.0 (3)	C5—C4—C12—C14B	128.2 (3)
C17—C9—C10A—C11A	163.4 (2)	C10A—C11A—C12—C14A	−74.4 (3)
C5—C9—C10A—C11A	46.8 (3)	C10A—C11A—C12—C13	166.5 (2)
C10B—C9—C10A—C11A	−40.1 (6)	C10A—C11A—C12—C11B	−48.5 (3)
C16—C9—C10A—C15A	45.3 (6)	C10A—C11A—C12—C4	49.6 (3)
C17—C9—C10A—C15A	−73.3 (6)	C10A—C11A—C12—C14B	−83.4 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1i	0.91	1.72	2.6305 (16)	178

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1i	0.91	1.72	2.6305 (16)	178

Symmetry code: (i) .