Crystal structure and absolute configuration of (3aR,3′aR,7aS,7′aS)-2,2,2′,2′-tetra­methyl-3a,6,7,7a,3′a,6′,7′,7′a-octa­hydro-4,4′-bi[1,3-benzodioxol­yl], obtained from a Pd-catalyzed homocoupling reaction

The crystal structure of a homocoupled compound with absolute configuration 3aR,3′aR,7aS,7′aS was determined. The mol­ecule contains two similar moieties composed of two fused rings. Its supra­molecular structure is controlled mainly by C—H...O inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.027
• wR factor = 0.071
• Data-to-parameter ratio = 15.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT397_ALERT_2_C Deviating  C-O-C  Angle from 120 Deg for  O1A         109.7 Degree
PLAT397_ALERT_2_C Deviating  C-O-C  Angle from 120 Deg for  O1B         109.7 Degree
PLAT397_ALERT_2_C Deviating  C-O-C  Angle from 120 Deg for  O3A         107.7 Degree
PLAT397_ALERT_2_C Deviating  C-O-C  Angle from 120 Deg for  O3B         107.1 Degree

Alert level G
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........         14 Note
PLAT791_ALERT_4_G The Model has Chirality at C3AB    (Chiral SPGR)          R Verify
PLAT791_ALERT_4_G The Model has Chirality at C3AA    (Chiral SPGR)          R Verify
PLAT791_ALERT_4_G The Model has Chirality at C7AB    (Chiral SPGR)          S Verify
PLAT791_ALERT_4_G The Model has Chirality at C7AA    (Chiral SPGR)          S Verify
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          2 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   0 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
   0 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

Computing details

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008, 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

(3aR,3'aR,7aS,7'aS)-2,2,2',2'-Tetramethyl-3a,6,7,7a,3'a,6',7',7'a-octahydro-4,4'-bi[1,3-benzodioxolyl]

Crystal data

C18H26O4	F(000) = 332
Mr = 306.39	Dx = 1.237 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54178 Å
a = 6.2927 (7) Å	Cell parameters from 9685 reflections
b = 17.9903 (19) Å	θ = 4.9–72.4°
c = 7.2991 (8) Å	µ = 0.69 mm^−1
β = 95.216 (4)°	T = 298 K
V = 822.89 (16) Å^3	Parallelepiped, yellow
Z = 2	0.40 × 0.35 × 0.30 mm

Data collection

Bruker D8 Venture/Photon 100 CMOS diffractometer	3232 independent reflections
Radiation source: Cu Incoatec microsource	3135 reflections with I > 2σ(I)
Detector resolution: 10.4167 pixels mm^-1	Rint = 0.026
φ and ω scans	θmax = 72.4°, θmin = 4.9°
Absorption correction: multi-scan (SADABS; Bruker, 2013)	h = −7→7
Tmin = 0.687, Tmax = 0.754	k = −21→22
27011 measured reflections	l = −9→9

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.027	w = 1/[σ^2(Fo^2) + (0.0389P)^2 + 0.0652P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.071	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 0.13 e Å^−3
3232 reflections	Δρmin = −0.10 e Å^−3
204 parameters	Extinction correction: SHELXL, Fc^* = kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0184 (15)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack x determined using 1475 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons et al., 2013)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.04 (4)

Special details

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

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

	x	y	z	Uiso*/Ueq
C7A	0.6166 (3)	1.13949 (11)	0.8000 (3)	0.0486 (4)
H7AA	0.5916	1.1910	0.7652	0.058*
H7AB	0.6639	1.1382	0.9302	0.058*
C6B	0.5034 (4)	0.77162 (12)	0.6693 (3)	0.0621 (6)
H6BA	0.5554	0.7523	0.5577	0.074*
H6BB	0.3603	0.7526	0.6774	0.074*
C2A	0.8127 (3)	1.05458 (10)	0.4052 (2)	0.0451 (4)
C7B	0.6472 (4)	0.74545 (11)	0.8343 (3)	0.0553 (5)
H7BA	0.5835	0.7580	0.9464	0.066*
H7BB	0.6625	0.6919	0.8297	0.066*
C22A	0.6299 (3)	1.01769 (13)	0.2920 (3)	0.0580 (5)
H22D	0.5609	1.0532	0.2084	0.087*
H22E	0.5291	0.9991	0.3719	0.087*
H22F	0.6832	0.9773	0.2235	0.087*
C2B	1.0094 (3)	0.83055 (10)	1.1168 (3)	0.0480 (4)
C21A	0.9882 (4)	1.07986 (15)	0.2908 (3)	0.0674 (6)
H21D	1.0446	1.0377	0.2306	0.101*
H21E	1.1000	1.1030	0.3691	0.101*
H21F	0.9314	1.1149	0.2000	0.101*
C21B	1.2355 (4)	0.85972 (14)	1.1342 (4)	0.0659 (6)
H21A	1.2803	0.8687	1.0139	0.099*
H21B	1.3284	0.8237	1.1970	0.099*
H21C	1.2417	0.9053	1.2029	0.099*
C22B	0.9298 (5)	0.81210 (16)	1.2994 (3)	0.0716 (7)
H22A	0.7901	0.7905	1.2800	0.107*
H22B	0.9231	0.8567	1.3710	0.107*
H22C	1.0254	0.7774	1.3637	0.107*
C6A	0.4092 (3)	1.09664 (11)	0.7669 (3)	0.0548 (5)
H6AA	0.3159	1.1102	0.8602	0.066*
H6AB	0.3389	1.1105	0.6481	0.066*
C5B	0.4969 (3)	0.85505 (11)	0.6607 (3)	0.0491 (4)
H5B	0.3814	0.8774	0.5935	0.059*
C5A	0.4430 (3)	1.01436 (10)	0.7714 (3)	0.0452 (4)
H5A	0.3277	0.9845	0.7940	0.054*
C4B	0.6466 (3)	0.89895 (9)	0.7434 (2)	0.0363 (3)
C4A	0.6263 (2)	0.98093 (9)	0.7455 (2)	0.0354 (4)
C3AB	0.8491 (3)	0.86610 (9)	0.8348 (2)	0.0370 (4)
H3AB	0.9718	0.8867	0.7785	0.044*
O3B	0.8671 (2)	0.88358 (7)	1.02685 (17)	0.0462 (3)
C3AA	0.8247 (2)	1.02504 (9)	0.7153 (2)	0.0355 (3)
H3AA	0.9338	1.0159	0.8173	0.043*
O3A	0.90773 (18)	1.00550 (6)	0.54514 (17)	0.0426 (3)
C7AB	0.8628 (3)	0.78135 (10)	0.8361 (2)	0.0452 (4)
H7B	0.9330	0.7645	0.7290	0.054*
O1B	0.9974 (3)	0.76615 (7)	1.0002 (2)	0.0601 (4)
C7AA	0.7894 (3)	1.10842 (9)	0.6933 (3)	0.0423 (4)
H7A	0.9235	1.1349	0.7263	0.051*
O1A	0.7303 (3)	1.11563 (8)	0.50051 (18)	0.0580 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C7A	0.0564 (11)	0.0367 (9)	0.0508 (10)	0.0081 (8)	−0.0048 (8)	−0.0077 (8)
C6B	0.0703 (14)	0.0432 (11)	0.0720 (14)	−0.0180 (10)	0.0032 (11)	−0.0097 (10)
C2A	0.0536 (10)	0.0381 (9)	0.0439 (9)	0.0048 (8)	0.0056 (8)	0.0063 (7)
C7B	0.0742 (13)	0.0309 (9)	0.0634 (12)	−0.0063 (8)	0.0210 (10)	0.0003 (8)
C22A	0.0607 (11)	0.0618 (13)	0.0506 (11)	0.0013 (10)	−0.0001 (9)	−0.0027 (9)
C2B	0.0613 (11)	0.0383 (9)	0.0438 (9)	0.0127 (8)	0.0026 (8)	0.0052 (7)
C21A	0.0667 (14)	0.0740 (15)	0.0628 (13)	−0.0058 (11)	0.0129 (10)	0.0236 (11)
C21B	0.0605 (13)	0.0570 (13)	0.0785 (15)	0.0122 (10)	−0.0026 (11)	0.0089 (11)
C22B	0.0899 (17)	0.0771 (17)	0.0488 (12)	0.0198 (14)	0.0117 (11)	0.0137 (11)
C6A	0.0462 (10)	0.0513 (12)	0.0652 (12)	0.0139 (8)	−0.0034 (8)	−0.0090 (9)
C5B	0.0524 (10)	0.0445 (10)	0.0495 (10)	−0.0073 (8)	−0.0002 (8)	0.0003 (8)
C5A	0.0372 (8)	0.0459 (10)	0.0521 (10)	−0.0014 (7)	0.0022 (7)	−0.0023 (8)
C4B	0.0419 (8)	0.0333 (8)	0.0342 (8)	−0.0025 (6)	0.0060 (6)	0.0024 (6)
C4A	0.0371 (8)	0.0348 (8)	0.0334 (8)	−0.0008 (6)	−0.0019 (6)	0.0006 (6)
C3AB	0.0435 (8)	0.0295 (8)	0.0386 (8)	0.0007 (6)	0.0074 (6)	0.0005 (6)
O3B	0.0590 (7)	0.0379 (6)	0.0405 (6)	0.0146 (6)	−0.0024 (5)	−0.0036 (5)
C3AA	0.0347 (7)	0.0317 (8)	0.0391 (8)	0.0016 (6)	−0.0025 (6)	0.0019 (6)
O3A	0.0453 (6)	0.0363 (6)	0.0472 (6)	0.0065 (5)	0.0097 (5)	0.0063 (5)
C7AB	0.0606 (11)	0.0331 (9)	0.0433 (9)	0.0062 (8)	0.0133 (8)	−0.0010 (7)
O1B	0.0851 (9)	0.0355 (7)	0.0581 (8)	0.0181 (7)	−0.0034 (7)	0.0022 (6)
C7AA	0.0477 (9)	0.0297 (8)	0.0481 (9)	−0.0021 (7)	−0.0038 (7)	0.0010 (7)
O1A	0.0899 (10)	0.0370 (7)	0.0464 (7)	0.0179 (7)	0.0028 (7)	0.0078 (5)

Geometric parameters (Å, º)

C7A—C7AA	1.502 (3)	C21B—H21B	0.9600
C7A—C6A	1.516 (3)	C21B—H21C	0.9600
C7A—H7AA	0.9700	C22B—H22A	0.9600
C7A—H7AB	0.9700	C22B—H22B	0.9600
C6B—C5B	1.503 (3)	C22B—H22C	0.9600
C6B—C7B	1.514 (3)	C6A—C5A	1.495 (3)
C6B—H6BA	0.9700	C6A—H6AA	0.9700
C6B—H6BB	0.9700	C6A—H6AB	0.9700
C2A—O1A	1.423 (2)	C5B—C4B	1.331 (3)
C2A—O3A	1.439 (2)	C5B—H5B	0.9300
C2A—C22A	1.508 (3)	C5A—C4A	1.329 (2)
C2A—C21A	1.514 (3)	C5A—H5A	0.9300
C7B—C7AB	1.501 (3)	C4B—C4A	1.481 (2)
C7B—H7BA	0.9700	C4B—C3AB	1.505 (2)
C7B—H7BB	0.9700	C4A—C3AA	1.512 (2)
C22A—H22D	0.9600	C3AB—O3B	1.431 (2)
C22A—H22E	0.9600	C3AB—C7AB	1.527 (2)
C22A—H22F	0.9600	C3AB—H3AB	0.9800
C2B—O3B	1.427 (2)	C3AA—O3A	1.434 (2)
C2B—O1B	1.435 (2)	C3AA—C7AA	1.523 (2)
C2B—C22B	1.502 (3)	C3AA—H3AA	0.9800
C2B—C21B	1.511 (3)	C7AB—O1B	1.430 (2)
C21A—H21D	0.9600	C7AB—H7B	0.9800
C21A—H21E	0.9600	C7AA—O1A	1.428 (2)
C21A—H21F	0.9600	C7AA—H7A	0.9800
C21B—H21A	0.9600
C7AA—C7A—C6A	112.42 (16)	H22A—C22B—H22B	109.5
C7AA—C7A—H7AA	109.1	C2B—C22B—H22C	109.5
C6A—C7A—H7AA	109.1	H22A—C22B—H22C	109.5
C7AA—C7A—H7AB	109.1	H22B—C22B—H22C	109.5
C6A—C7A—H7AB	109.1	C5A—C6A—C7A	112.39 (15)
H7AA—C7A—H7AB	107.9	C5A—C6A—H6AA	109.1
C5B—C6B—C7B	110.85 (17)	C7A—C6A—H6AA	109.1
C5B—C6B—H6BA	109.5	C5A—C6A—H6AB	109.1
C7B—C6B—H6BA	109.5	C7A—C6A—H6AB	109.1
C5B—C6B—H6BB	109.5	H6AA—C6A—H6AB	107.9
C7B—C6B—H6BB	109.5	C4B—C5B—C6B	123.93 (18)
H6BA—C6B—H6BB	108.1	C4B—C5B—H5B	118.0
O1A—C2A—O3A	105.85 (14)	C6B—C5B—H5B	118.0
O1A—C2A—C22A	108.30 (16)	C4A—C5A—C6A	124.64 (17)
O3A—C2A—C22A	111.49 (15)	C4A—C5A—H5A	117.7
O1A—C2A—C21A	110.76 (17)	C6A—C5A—H5A	117.7
O3A—C2A—C21A	107.39 (16)	C5B—C4B—C4A	122.49 (16)
C22A—C2A—C21A	112.85 (18)	C5B—C4B—C3AB	120.26 (16)
C7AB—C7B—C6B	110.32 (16)	C4A—C4B—C3AB	117.22 (14)
C7AB—C7B—H7BA	109.6	C5A—C4A—C4B	121.95 (15)
C6B—C7B—H7BA	109.6	C5A—C4A—C3AA	121.45 (15)
C7AB—C7B—H7BB	109.6	C4B—C4A—C3AA	116.60 (14)
C6B—C7B—H7BB	109.6	O3B—C3AB—C4B	109.67 (13)
H7BA—C7B—H7BB	108.1	O3B—C3AB—C7AB	102.38 (13)
C2A—C22A—H22D	109.5	C4B—C3AB—C7AB	116.09 (15)
C2A—C22A—H22E	109.5	O3B—C3AB—H3AB	109.5
H22D—C22A—H22E	109.5	C4B—C3AB—H3AB	109.5
C2A—C22A—H22F	109.5	C7AB—C3AB—H3AB	109.5
H22D—C22A—H22F	109.5	C2B—O3B—C3AB	107.11 (13)
H22E—C22A—H22F	109.5	O3A—C3AA—C4A	111.61 (13)
O3B—C2B—O1B	105.65 (14)	O3A—C3AA—C7AA	102.20 (13)
O3B—C2B—C22B	108.06 (17)	C4A—C3AA—C7AA	114.69 (14)
O1B—C2B—C22B	110.10 (19)	O3A—C3AA—H3AA	109.4
O3B—C2B—C21B	110.69 (17)	C4A—C3AA—H3AA	109.4
O1B—C2B—C21B	109.18 (18)	C7AA—C3AA—H3AA	109.4
C22B—C2B—C21B	112.9 (2)	C3AA—O3A—C2A	107.67 (12)
C2A—C21A—H21D	109.5	O1B—C7AB—C7B	113.01 (16)
C2A—C21A—H21E	109.5	O1B—C7AB—C3AB	102.98 (15)
H21D—C21A—H21E	109.5	C7B—C7AB—C3AB	112.28 (15)
C2A—C21A—H21F	109.5	O1B—C7AB—H7B	109.5
H21D—C21A—H21F	109.5	C7B—C7AB—H7B	109.5
H21E—C21A—H21F	109.5	C3AB—C7AB—H7B	109.5
C2B—C21B—H21A	109.5	C7AB—O1B—C2B	109.73 (13)
C2B—C21B—H21B	109.5	O1A—C7AA—C7A	109.95 (15)
H21A—C21B—H21B	109.5	O1A—C7AA—C3AA	102.46 (14)
C2B—C21B—H21C	109.5	C7A—C7AA—C3AA	114.67 (15)
H21A—C21B—H21C	109.5	O1A—C7AA—H7A	109.8
H21B—C21B—H21C	109.5	C7A—C7AA—H7A	109.8
C2B—C22B—H22A	109.5	C3AA—C7AA—H7A	109.8
C2B—C22B—H22B	109.5	C2A—O1A—C7AA	109.73 (13)
C5B—C6B—C7B—C7AB	−52.6 (2)	C7AA—C3AA—O3A—C2A	−31.87 (16)
C7AA—C7A—C6A—C5A	44.4 (2)	O1A—C2A—O3A—C3AA	17.72 (18)
C7B—C6B—C5B—C4B	21.4 (3)	C22A—C2A—O3A—C3AA	−99.84 (17)
C7A—C6A—C5A—C4A	−21.2 (3)	C21A—C2A—O3A—C3AA	136.07 (17)
C6B—C5B—C4B—C4A	−174.59 (18)	C6B—C7B—C7AB—O1B	172.70 (16)
C6B—C5B—C4B—C3AB	7.3 (3)	C6B—C7B—C7AB—C3AB	56.7 (2)
C6A—C5A—C4A—C4B	−177.19 (17)	O3B—C3AB—C7AB—O1B	−31.08 (16)
C6A—C5A—C4A—C3AA	2.4 (3)	C4B—C3AB—C7AB—O1B	−150.49 (15)
C5B—C4B—C4A—C5A	41.2 (3)	O3B—C3AB—C7AB—C7B	90.79 (17)
C3AB—C4B—C4A—C5A	−140.59 (17)	C4B—C3AB—C7AB—C7B	−28.6 (2)
C5B—C4B—C4A—C3AA	−138.43 (17)	C7B—C7AB—O1B—C2B	−104.65 (19)
C3AB—C4B—C4A—C3AA	39.8 (2)	C3AB—C7AB—O1B—C2B	16.7 (2)
C5B—C4B—C3AB—O3B	−119.03 (18)	O3B—C2B—O1B—C7AB	4.1 (2)
C4A—C4B—C3AB—O3B	62.73 (18)	C22B—C2B—O1B—C7AB	120.57 (19)
C5B—C4B—C3AB—C7AB	−3.7 (2)	C21B—C2B—O1B—C7AB	−114.94 (18)
C4A—C4B—C3AB—C7AB	178.09 (14)	C6A—C7A—C7AA—O1A	63.7 (2)
O1B—C2B—O3B—C3AB	−25.2 (2)	C6A—C7A—C7AA—C3AA	−51.0 (2)
C22B—C2B—O3B—C3AB	−143.02 (19)	O3A—C3AA—C7AA—O1A	33.75 (16)
C21B—C2B—O3B—C3AB	92.87 (19)	C4A—C3AA—C7AA—O1A	−87.19 (17)
C4B—C3AB—O3B—C2B	158.69 (15)	O3A—C3AA—C7AA—C7A	152.83 (14)
C7AB—C3AB—O3B—C2B	34.88 (17)	C4A—C3AA—C7AA—C7A	31.9 (2)
C5A—C4A—C3AA—O3A	−122.95 (16)	O3A—C2A—O1A—C7AA	5.2 (2)
C4B—C4A—C3AA—O3A	56.69 (18)	C22A—C2A—O1A—C7AA	124.91 (17)
C5A—C4A—C3AA—C7AA	−7.3 (2)	C21A—C2A—O1A—C7AA	−110.85 (19)
C4B—C4A—C3AA—C7AA	172.30 (14)	C7A—C7AA—O1A—C2A	−146.62 (16)
C4A—C3AA—O3A—C2A	91.17 (15)	C3AA—C7AA—O1A—C2A	−24.27 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C22A—H22F···O3B^i	0.96	2.56	3.510 (3)	171

Symmetry code: (i) x, y, z−1.