In the title compound, C
20H
30O
2, one of the two crystallographically independent molecules lies across a centre of inversion and the other resides in a general position (
Z′ = 1.5). The supramolecular structure exists as an unusual two-dimensional network incorporating centrosymmetric hexameric hydrogen-bonded alcohol (OH)
6 clusters [O
O = 2.6637 (12)–2.6993 (12) Å] as the net nodes. The hexamers adopt a chair conformation [O
O
O = 106.55 (4)–115.81 (4)°] and are connected into a network with a square-grid topology (4
4) by a combination of single and double 1,1′-biadamantanediyl links. The bulky aliphatic groups appear to require specific hexagonal packing and so generate distinct noncovalent hydrophobic layers, which are essential for the stabilization of the hexameric alcohol array rather than the formation of the more commonly encountered tetramer-based arrays.
Supporting information
CCDC reference: 925772
The title compound was prepared from adamantane according to the four-stage
synthesis of Reinhardt (1962). Large colourless prisms of the product,
(I),
were obtained by hydrothermal recrystallization from hot water in an autoclave
(with cooling from 453 K to room temperature).
All the H atoms were found in intermediate difference Fourier maps and were
refined without constraints and with isotropic displacement parameters [C—H
= 0.992 (14)–1.033 (15) Å and O—H = 0.915 (19)–0.93 (2) Å].
Data collection: IPDS Software (Stoe & Cie, 2000); cell refinement: IPDS Software (Stoe & Cie, 2000); data reduction: IPDS Software (Stoe & Cie, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).
1,1'-Biadamantane-3,3'-diol
top
Crystal data top
C20H30O2 | Z = 3 |
Mr = 302.44 | F(000) = 498 |
Triclinic, P1 | Dx = 1.250 Mg m−3 |
a = 11.3855 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.3863 (9) Å | Cell parameters from 11179 reflections |
c = 11.5351 (8) Å | θ = 2.0–26.8° |
α = 62.220 (9)° | µ = 0.08 mm−1 |
β = 81.596 (11)° | T = 173 K |
γ = 65.878 (9)° | Prism, colourless |
V = 1205.7 (2) Å3 | 0.27 × 0.25 × 0.20 mm |
Data collection top
Stoe IPDS diffractometer | 3549 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.033 |
Graphite monochromator | θmax = 26.8°, θmin = 2.0° |
ϕ oscillation scans | h = −14→14 |
11179 measured reflections | k = −14→12 |
5076 independent reflections | l = −14→14 |
Refinement top
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)] = 0.034 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.086 | All H-atom parameters refined |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0446P)2] where P = (Fo2 + 2Fc2)/3 |
5076 reflections | (Δ/σ)max < 0.001 |
478 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.15 e Å−3 |
Crystal data top
C20H30O2 | γ = 65.878 (9)° |
Mr = 302.44 | V = 1205.7 (2) Å3 |
Triclinic, P1 | Z = 3 |
a = 11.3855 (8) Å | Mo Kα radiation |
b = 11.3863 (9) Å | µ = 0.08 mm−1 |
c = 11.5351 (8) Å | T = 173 K |
α = 62.220 (9)° | 0.27 × 0.25 × 0.20 mm |
β = 81.596 (11)° | |
Data collection top
Stoe IPDS diffractometer | 3549 reflections with I > 2σ(I) |
11179 measured reflections | Rint = 0.033 |
5076 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.086 | All H-atom parameters refined |
S = 1.02 | Δρmax = 0.23 e Å−3 |
5076 reflections | Δρmin = −0.15 e Å−3 |
478 parameters | |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.87118 (7) | 0.13492 (9) | 0.14497 (8) | 0.0276 (2) | |
O2 | 0.12926 (8) | 0.03489 (10) | 0.12623 (8) | 0.0342 (2) | |
O3 | 0.78814 (8) | −0.03220 (10) | 0.10116 (9) | 0.0347 (2) | |
C1 | 0.79906 (10) | 0.28003 (12) | 0.05002 (10) | 0.0234 (2) | |
C2 | 0.81465 (11) | 0.29274 (13) | −0.08880 (11) | 0.0258 (3) | |
C3 | 0.73802 (11) | 0.44906 (13) | −0.18681 (11) | 0.0269 (3) | |
C4 | 0.59479 (11) | 0.49151 (14) | −0.15682 (10) | 0.0254 (3) | |
C5 | 0.57370 (10) | 0.47910 (12) | −0.01620 (10) | 0.0212 (2) | |
C6 | 0.65623 (10) | 0.32193 (13) | 0.08006 (11) | 0.0229 (2) | |
C7 | 0.85054 (11) | 0.37840 (13) | 0.06133 (12) | 0.0271 (3) | |
C8 | 0.77332 (11) | 0.53453 (13) | −0.03675 (12) | 0.0288 (3) | |
C9 | 0.78907 (12) | 0.54901 (14) | −0.17631 (12) | 0.0310 (3) | |
C10 | 0.62995 (11) | 0.57705 (13) | −0.00647 (12) | 0.0261 (3) | |
C11 | 0.19495 (10) | −0.02020 (13) | 0.24891 (10) | 0.0236 (2) | |
C12 | 0.16260 (11) | 0.09988 (13) | 0.28765 (12) | 0.0274 (3) | |
C13 | 0.23917 (11) | 0.04039 (14) | 0.41492 (12) | 0.0286 (3) | |
C14 | 0.20265 (12) | −0.07983 (15) | 0.52408 (12) | 0.0333 (3) | |
C15 | 0.23359 (11) | −0.19935 (14) | 0.48485 (11) | 0.0298 (3) | |
C16 | 0.15772 (11) | −0.14033 (14) | 0.35681 (12) | 0.0282 (3) | |
C17 | 0.33916 (10) | −0.07973 (13) | 0.22883 (11) | 0.0235 (2) | |
C18 | 0.42116 (10) | −0.14258 (12) | 0.35549 (10) | 0.0208 (2) | |
C19 | 0.38443 (11) | −0.02047 (14) | 0.39555 (12) | 0.0273 (3) | |
C20 | 0.37888 (11) | −0.26111 (14) | 0.46444 (11) | 0.0281 (3) | |
C21 | 0.75703 (11) | −0.14857 (13) | 0.20228 (11) | 0.0253 (3) | |
C22 | 0.61221 (10) | −0.08828 (13) | 0.22281 (11) | 0.0239 (2) | |
C23 | 0.57020 (10) | −0.20497 (12) | 0.33450 (10) | 0.0212 (2) | |
C24 | 0.60747 (11) | −0.32962 (13) | 0.29805 (12) | 0.0259 (3) | |
C25 | 0.75255 (11) | −0.38952 (13) | 0.27761 (12) | 0.0287 (3) | |
C26 | 0.78852 (11) | −0.26989 (14) | 0.16586 (12) | 0.0280 (3) | |
C27 | 0.83380 (11) | −0.20478 (15) | 0.32837 (12) | 0.0299 (3) | |
C28 | 0.79697 (11) | −0.32366 (14) | 0.43962 (11) | 0.0300 (3) | |
C29 | 0.65202 (11) | −0.26309 (14) | 0.45975 (11) | 0.0267 (3) | |
C30 | 0.82945 (12) | −0.44675 (14) | 0.40446 (13) | 0.0341 (3) | |
H2A | 0.7836 (11) | 0.2250 (14) | −0.0944 (12) | 0.029 (3)* | |
H2B | 0.9089 (13) | 0.2616 (14) | −0.1076 (12) | 0.033 (3)* | |
H3 | 0.7475 (11) | 0.4582 (14) | −0.2788 (13) | 0.030 (3)* | |
H4A | 0.5608 (12) | 0.4285 (15) | −0.1697 (12) | 0.033 (4)* | |
H4B | 0.5459 (12) | 0.5923 (15) | −0.2230 (13) | 0.031 (3)* | |
H6A | 0.6495 (12) | 0.3083 (14) | 0.1736 (13) | 0.033 (3)* | |
H6B | 0.6248 (12) | 0.2520 (15) | 0.0746 (12) | 0.032 (3)* | |
H7A | 0.9440 (13) | 0.3489 (14) | 0.0455 (12) | 0.032 (3)* | |
H7B | 0.8401 (12) | 0.3660 (14) | 0.1549 (13) | 0.034 (3)* | |
H8 | 0.8071 (12) | 0.6003 (15) | −0.0269 (12) | 0.030 (3)* | |
H9A | 0.7397 (12) | 0.6522 (16) | −0.2430 (13) | 0.035 (4)* | |
H9B | 0.8829 (13) | 0.5230 (15) | −0.1981 (13) | 0.040 (4)* | |
H10A | 0.5823 (13) | 0.6807 (16) | −0.0713 (14) | 0.039 (4)* | |
H10B | 0.6191 (12) | 0.5707 (15) | 0.0843 (13) | 0.033 (3)* | |
H12A | 0.0673 (12) | 0.1417 (14) | 0.2986 (12) | 0.031 (3)* | |
H12B | 0.1864 (12) | 0.1789 (15) | 0.2154 (13) | 0.032 (3)* | |
H13 | 0.2177 (12) | 0.1201 (15) | 0.4406 (13) | 0.034 (3)* | |
H14A | 0.2509 (13) | −0.1176 (16) | 0.6098 (14) | 0.044 (4)* | |
H14B | 0.1067 (14) | −0.0405 (16) | 0.5402 (14) | 0.045 (4)* | |
H15 | 0.2102 (12) | −0.2818 (15) | 0.5573 (13) | 0.038 (4)* | |
H16A | 0.1786 (12) | −0.2184 (15) | 0.3288 (13) | 0.035 (4)* | |
H16B | 0.0611 (13) | −0.0985 (14) | 0.3657 (12) | 0.033 (3)* | |
H17A | 0.3600 (12) | 0.0008 (15) | 0.1542 (13) | 0.035 (4)* | |
H17B | 0.3587 (12) | −0.1572 (15) | 0.1998 (13) | 0.035 (4)* | |
H19A | 0.4325 (13) | −0.0577 (15) | 0.4790 (14) | 0.037 (4)* | |
H19B | 0.4098 (12) | 0.0578 (14) | 0.3253 (13) | 0.029 (3)* | |
H20A | 0.3998 (13) | −0.3438 (17) | 0.4408 (14) | 0.043 (4)* | |
H20B | 0.4273 (12) | −0.3041 (15) | 0.5491 (13) | 0.033 (3)* | |
H22A | 0.5650 (12) | −0.0475 (14) | 0.1374 (13) | 0.028 (3)* | |
H22B | 0.5932 (12) | −0.0053 (15) | 0.2423 (13) | 0.032 (3)* | |
H24A | 0.5849 (12) | −0.4103 (15) | 0.3698 (13) | 0.031 (3)* | |
H24B | 0.5581 (12) | −0.2948 (15) | 0.2148 (13) | 0.035 (4)* | |
H25 | 0.7725 (12) | −0.4694 (15) | 0.2533 (12) | 0.030 (3)* | |
H26A | 0.8820 (14) | −0.3051 (16) | 0.1489 (14) | 0.043 (4)* | |
H26B | 0.7382 (12) | −0.2313 (14) | 0.0803 (13) | 0.032 (3)* | |
H27A | 0.8125 (13) | −0.1194 (16) | 0.3490 (13) | 0.041 (4)* | |
H27B | 0.9274 (14) | −0.2447 (15) | 0.3155 (13) | 0.040 (4)* | |
H28 | 0.8458 (12) | −0.3602 (15) | 0.5242 (14) | 0.038 (4)* | |
H29A | 0.6319 (12) | −0.1833 (15) | 0.4851 (13) | 0.033 (4)* | |
H29B | 0.6281 (12) | −0.3405 (15) | 0.5354 (13) | 0.032 (3)* | |
H30A | 0.8063 (13) | −0.5269 (16) | 0.4777 (14) | 0.040 (4)* | |
H30B | 0.9267 (14) | −0.4901 (15) | 0.3917 (13) | 0.042 (4)* | |
H1H | 0.8408 (19) | 0.076 (2) | 0.1336 (19) | 0.083 (7)* | |
H2H | 0.0423 (19) | 0.067 (2) | 0.1360 (18) | 0.076 (6)* | |
H3H | 0.8122 (17) | −0.043 (2) | 0.0264 (19) | 0.074 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0255 (4) | 0.0220 (4) | 0.0263 (4) | −0.0037 (3) | −0.0038 (3) | −0.0072 (3) |
O2 | 0.0257 (4) | 0.0481 (6) | 0.0255 (4) | −0.0089 (4) | −0.0031 (3) | −0.0173 (4) |
O3 | 0.0425 (5) | 0.0381 (5) | 0.0326 (5) | −0.0262 (4) | 0.0153 (4) | −0.0176 (4) |
C1 | 0.0231 (5) | 0.0199 (6) | 0.0226 (5) | −0.0054 (4) | −0.0022 (4) | −0.0076 (4) |
C2 | 0.0236 (6) | 0.0263 (7) | 0.0264 (6) | −0.0077 (5) | 0.0020 (4) | −0.0131 (5) |
C3 | 0.0295 (6) | 0.0275 (7) | 0.0201 (5) | −0.0096 (5) | 0.0028 (4) | −0.0096 (5) |
C4 | 0.0258 (6) | 0.0264 (7) | 0.0197 (5) | −0.0077 (5) | −0.0008 (4) | −0.0085 (5) |
C5 | 0.0223 (5) | 0.0204 (6) | 0.0200 (5) | −0.0068 (4) | −0.0007 (4) | −0.0091 (4) |
C6 | 0.0232 (5) | 0.0217 (6) | 0.0207 (5) | −0.0070 (5) | −0.0002 (4) | −0.0082 (5) |
C7 | 0.0239 (6) | 0.0297 (7) | 0.0295 (6) | −0.0093 (5) | −0.0009 (5) | −0.0149 (5) |
C8 | 0.0269 (6) | 0.0254 (7) | 0.0370 (6) | −0.0118 (5) | 0.0013 (5) | −0.0147 (5) |
C9 | 0.0286 (6) | 0.0263 (7) | 0.0312 (6) | −0.0111 (5) | 0.0046 (5) | −0.0081 (5) |
C10 | 0.0254 (6) | 0.0241 (6) | 0.0308 (6) | −0.0090 (5) | 0.0009 (5) | −0.0144 (5) |
C11 | 0.0224 (5) | 0.0280 (6) | 0.0193 (5) | −0.0085 (5) | −0.0006 (4) | −0.0104 (5) |
C12 | 0.0244 (6) | 0.0259 (7) | 0.0296 (6) | −0.0077 (5) | 0.0011 (5) | −0.0124 (5) |
C13 | 0.0266 (6) | 0.0339 (7) | 0.0329 (6) | −0.0096 (5) | 0.0022 (5) | −0.0229 (6) |
C14 | 0.0274 (6) | 0.0481 (8) | 0.0235 (6) | −0.0125 (6) | 0.0040 (5) | −0.0179 (6) |
C15 | 0.0275 (6) | 0.0316 (7) | 0.0245 (6) | −0.0143 (5) | 0.0049 (5) | −0.0068 (5) |
C16 | 0.0244 (6) | 0.0326 (7) | 0.0318 (6) | −0.0141 (5) | 0.0045 (5) | −0.0160 (5) |
C17 | 0.0239 (5) | 0.0268 (6) | 0.0197 (5) | −0.0101 (5) | 0.0013 (4) | −0.0101 (5) |
C18 | 0.0214 (5) | 0.0217 (6) | 0.0195 (5) | −0.0091 (4) | 0.0006 (4) | −0.0085 (4) |
C19 | 0.0252 (6) | 0.0317 (7) | 0.0312 (6) | −0.0108 (5) | 0.0017 (5) | −0.0192 (5) |
C20 | 0.0271 (6) | 0.0269 (7) | 0.0239 (6) | −0.0115 (5) | 0.0013 (5) | −0.0055 (5) |
C21 | 0.0275 (6) | 0.0286 (6) | 0.0240 (5) | −0.0156 (5) | 0.0056 (4) | −0.0123 (5) |
C22 | 0.0259 (6) | 0.0242 (6) | 0.0224 (5) | −0.0107 (5) | 0.0025 (4) | −0.0107 (5) |
C23 | 0.0222 (5) | 0.0217 (6) | 0.0200 (5) | −0.0093 (4) | 0.0006 (4) | −0.0087 (4) |
C24 | 0.0259 (6) | 0.0235 (6) | 0.0300 (6) | −0.0102 (5) | 0.0022 (5) | −0.0131 (5) |
C25 | 0.0275 (6) | 0.0244 (7) | 0.0355 (6) | −0.0076 (5) | 0.0027 (5) | −0.0170 (5) |
C26 | 0.0256 (6) | 0.0335 (7) | 0.0294 (6) | −0.0118 (5) | 0.0058 (5) | −0.0187 (5) |
C27 | 0.0245 (6) | 0.0399 (8) | 0.0312 (6) | −0.0150 (5) | 0.0034 (5) | −0.0191 (6) |
C28 | 0.0240 (6) | 0.0368 (7) | 0.0251 (6) | −0.0091 (5) | −0.0024 (4) | −0.0120 (5) |
C29 | 0.0253 (6) | 0.0313 (7) | 0.0215 (6) | −0.0105 (5) | −0.0004 (4) | −0.0103 (5) |
C30 | 0.0269 (6) | 0.0292 (7) | 0.0344 (7) | −0.0048 (5) | −0.0011 (5) | −0.0096 (6) |
Geometric parameters (Å, º) top
O1—C1 | 1.4391 (13) | C14—H14A | 1.017 (15) |
O1—H1H | 0.93 (2) | C14—H14B | 1.023 (14) |
O2—C11 | 1.4332 (13) | C15—C16 | 1.5337 (17) |
O2—H2H | 0.915 (19) | C15—C20 | 1.5414 (16) |
O3—C21 | 1.4366 (14) | C15—H15 | 1.029 (14) |
O3—H3H | 0.917 (19) | C16—H16A | 1.012 (15) |
C1—C7 | 1.5201 (17) | C16—H16B | 1.016 (13) |
C1—C2 | 1.5292 (16) | C17—C18 | 1.5480 (15) |
C1—C6 | 1.5321 (15) | C17—H17A | 1.010 (14) |
C2—C3 | 1.5332 (17) | C17—H17B | 1.017 (15) |
C2—H2A | 1.000 (14) | C18—C19 | 1.5455 (17) |
C2—H2B | 1.008 (13) | C18—C20 | 1.5510 (15) |
C3—C9 | 1.5288 (18) | C18—C23 | 1.5804 (14) |
C3—C4 | 1.5360 (16) | C19—H19A | 0.994 (14) |
C3—H3 | 1.011 (13) | C19—H19B | 1.002 (13) |
C4—C5 | 1.5521 (15) | C20—H20A | 1.028 (16) |
C4—H4A | 1.015 (14) | C20—H20B | 0.994 (14) |
C4—H4B | 0.998 (14) | C21—C26 | 1.5183 (17) |
C5—C10 | 1.5454 (17) | C21—C27 | 1.5283 (16) |
C5—C6 | 1.5481 (15) | C21—C22 | 1.5357 (15) |
C5—C5i | 1.585 (2) | C22—C23 | 1.5484 (15) |
C6—H6A | 1.012 (14) | C22—H22A | 1.000 (13) |
C6—H6B | 1.025 (14) | C22—H22B | 1.004 (14) |
C7—C8 | 1.5335 (17) | C23—C24 | 1.5437 (17) |
C7—H7A | 0.994 (13) | C23—C29 | 1.5465 (15) |
C7—H7B | 1.017 (14) | C24—C25 | 1.5378 (16) |
C8—C9 | 1.5308 (18) | C24—H24A | 1.009 (13) |
C8—C10 | 1.5381 (16) | C24—H24B | 1.008 (14) |
C8—H8 | 1.024 (14) | C25—C26 | 1.5329 (17) |
C9—H9A | 1.016 (14) | C25—C30 | 1.5335 (18) |
C9—H9B | 1.012 (13) | C25—H25 | 1.003 (14) |
C10—H10A | 1.009 (14) | C26—H26A | 0.997 (14) |
C10—H10B | 1.008 (14) | C26—H26B | 1.026 (13) |
C11—C12 | 1.5213 (17) | C27—C28 | 1.5304 (17) |
C11—C16 | 1.5273 (16) | C27—H27A | 1.033 (15) |
C11—C17 | 1.5279 (15) | C27—H27B | 0.992 (14) |
C12—C13 | 1.5293 (16) | C28—C30 | 1.5257 (19) |
C12—H12A | 1.007 (13) | C28—C29 | 1.5363 (16) |
C12—H12B | 1.006 (13) | C28—H28 | 1.012 (14) |
C13—C14 | 1.5289 (18) | C29—H29A | 1.011 (15) |
C13—C19 | 1.5379 (16) | C29—H29B | 1.011 (13) |
C13—H13 | 1.010 (15) | C30—H30A | 1.014 (14) |
C14—C15 | 1.5220 (19) | C30—H30B | 1.031 (14) |
| | | |
C1—O1—H1H | 106.3 (12) | C20—C15—H15 | 108.2 (7) |
C11—O2—H2H | 109.2 (12) | C11—C16—C15 | 108.91 (10) |
C21—O3—H3H | 112.8 (12) | C11—C16—H16A | 108.4 (7) |
O1—C1—C7 | 107.71 (9) | C15—C16—H16A | 110.9 (7) |
O1—C1—C2 | 110.63 (9) | C11—C16—H16B | 108.0 (7) |
C7—C1—C2 | 109.81 (10) | C15—C16—H16B | 111.7 (7) |
O1—C1—C6 | 109.28 (9) | H16A—C16—H16B | 108.8 (10) |
C7—C1—C6 | 109.96 (10) | C11—C17—C18 | 111.72 (9) |
C2—C1—C6 | 109.43 (9) | C11—C17—H17A | 107.9 (7) |
C1—C2—C3 | 108.93 (10) | C18—C17—H17A | 111.2 (8) |
C1—C2—H2A | 109.2 (7) | C11—C17—H17B | 108.8 (7) |
C3—C2—H2A | 111.2 (7) | C18—C17—H17B | 110.1 (7) |
C1—C2—H2B | 109.6 (7) | H17A—C17—H17B | 106.9 (11) |
C3—C2—H2B | 111.1 (7) | C19—C18—C17 | 107.24 (9) |
H2A—C2—H2B | 106.7 (10) | C19—C18—C20 | 107.55 (9) |
C9—C3—C2 | 109.64 (10) | C17—C18—C20 | 107.17 (9) |
C9—C3—C4 | 109.61 (10) | C19—C18—C23 | 111.72 (9) |
C2—C3—C4 | 109.63 (10) | C17—C18—C23 | 111.53 (9) |
C9—C3—H3 | 109.6 (7) | C20—C18—C23 | 111.38 (9) |
C2—C3—H3 | 109.4 (7) | C13—C19—C18 | 111.44 (10) |
C4—C3—H3 | 109.0 (7) | C13—C19—H19A | 108.7 (8) |
C3—C4—C5 | 111.53 (9) | C18—C19—H19A | 109.8 (8) |
C3—C4—H4A | 108.8 (7) | C13—C19—H19B | 109.9 (7) |
C5—C4—H4A | 111.4 (7) | C18—C19—H19B | 108.5 (8) |
C3—C4—H4B | 108.6 (7) | H19A—C19—H19B | 108.4 (11) |
C5—C4—H4B | 110.2 (8) | C15—C20—C18 | 111.10 (10) |
H4A—C4—H4B | 106.2 (11) | C15—C20—H20A | 109.7 (8) |
C10—C5—C6 | 107.18 (9) | C18—C20—H20A | 110.2 (8) |
C10—C5—C4 | 107.16 (9) | C15—C20—H20B | 108.6 (7) |
C6—C5—C4 | 107.12 (9) | C18—C20—H20B | 110.8 (8) |
C10—C5—C5i | 111.96 (12) | H20A—C20—H20B | 106.4 (11) |
C6—C5—C5i | 111.27 (11) | O3—C21—C26 | 111.81 (9) |
C4—C5—C5i | 111.87 (11) | O3—C21—C27 | 108.09 (9) |
C1—C6—C5 | 111.86 (9) | C26—C21—C27 | 109.89 (10) |
C1—C6—H6A | 107.5 (7) | O3—C21—C22 | 107.89 (10) |
C5—C6—H6A | 110.8 (8) | C26—C21—C22 | 109.56 (10) |
C1—C6—H6B | 108.3 (7) | C27—C21—C22 | 109.54 (9) |
C5—C6—H6B | 110.2 (7) | C21—C22—C23 | 111.76 (9) |
H6A—C6—H6B | 108.0 (10) | C21—C22—H22A | 107.5 (7) |
C1—C7—C8 | 108.90 (10) | C23—C22—H22A | 111.7 (7) |
C1—C7—H7A | 110.1 (8) | C21—C22—H22B | 108.0 (7) |
C8—C7—H7A | 111.5 (7) | C23—C22—H22B | 111.1 (7) |
C1—C7—H7B | 107.7 (8) | H22A—C22—H22B | 106.6 (10) |
C8—C7—H7B | 110.8 (8) | C24—C23—C29 | 107.60 (9) |
H7A—C7—H7B | 107.7 (10) | C24—C23—C22 | 107.17 (9) |
C9—C8—C7 | 109.52 (10) | C29—C23—C22 | 107.02 (9) |
C9—C8—C10 | 109.68 (10) | C24—C23—C18 | 111.71 (9) |
C7—C8—C10 | 109.82 (10) | C29—C23—C18 | 111.44 (9) |
C9—C8—H8 | 110.6 (7) | C22—C23—C18 | 111.64 (9) |
C7—C8—H8 | 108.4 (7) | C25—C24—C23 | 111.37 (10) |
C10—C8—H8 | 108.8 (7) | C25—C24—H24A | 108.6 (7) |
C3—C9—C8 | 108.92 (10) | C23—C24—H24A | 110.1 (8) |
C3—C9—H9A | 109.5 (8) | C25—C24—H24B | 108.8 (7) |
C8—C9—H9A | 110.8 (8) | C23—C24—H24B | 109.9 (8) |
C3—C9—H9B | 109.9 (8) | H24A—C24—H24B | 108.0 (11) |
C8—C9—H9B | 110.5 (8) | C26—C25—C30 | 109.74 (10) |
H9A—C9—H9B | 107.2 (11) | C26—C25—C24 | 109.62 (10) |
C8—C10—C5 | 111.49 (10) | C30—C25—C24 | 109.61 (10) |
C8—C10—H10A | 107.8 (7) | C26—C25—H25 | 109.0 (7) |
C5—C10—H10A | 110.3 (8) | C30—C25—H25 | 110.0 (7) |
C8—C10—H10B | 109.8 (7) | C24—C25—H25 | 108.8 (7) |
C5—C10—H10B | 109.5 (8) | C21—C26—C25 | 108.92 (10) |
H10A—C10—H10B | 107.9 (11) | C21—C26—H26A | 108.8 (9) |
O2—C11—C12 | 110.27 (9) | C25—C26—H26A | 112.0 (8) |
O2—C11—C16 | 110.75 (9) | C21—C26—H26B | 109.7 (8) |
C12—C11—C16 | 109.49 (10) | C25—C26—H26B | 110.4 (7) |
O2—C11—C17 | 106.78 (9) | H26A—C26—H26B | 107.1 (11) |
C12—C11—C17 | 109.73 (10) | C21—C27—C28 | 109.14 (10) |
C16—C11—C17 | 109.79 (10) | C21—C27—H27A | 108.1 (8) |
C11—C12—C13 | 109.34 (10) | C28—C27—H27A | 111.1 (8) |
C11—C12—H12A | 110.3 (8) | C21—C27—H27B | 109.6 (8) |
C13—C12—H12A | 110.7 (7) | C28—C27—H27B | 109.3 (8) |
C11—C12—H12B | 108.8 (8) | H27A—C27—H27B | 109.5 (11) |
C13—C12—H12B | 109.8 (7) | C30—C28—C27 | 109.23 (10) |
H12A—C12—H12B | 107.9 (10) | C30—C28—C29 | 109.78 (11) |
C14—C13—C12 | 109.43 (10) | C27—C28—C29 | 109.73 (10) |
C14—C13—C19 | 109.22 (11) | C30—C28—H28 | 109.9 (8) |
C12—C13—C19 | 109.92 (10) | C27—C28—H28 | 109.9 (8) |
C14—C13—H13 | 109.1 (7) | C29—C28—H28 | 108.3 (7) |
C12—C13—H13 | 109.3 (7) | C28—C29—C23 | 111.57 (9) |
C19—C13—H13 | 109.9 (7) | C28—C29—H29A | 109.1 (7) |
C15—C14—C13 | 109.14 (10) | C23—C29—H29A | 109.8 (7) |
C15—C14—H14A | 111.1 (9) | C28—C29—H29B | 109.9 (7) |
C13—C14—H14A | 109.9 (8) | C23—C29—H29B | 109.7 (7) |
C15—C14—H14B | 110.2 (9) | H29A—C29—H29B | 106.7 (11) |
C13—C14—H14B | 110.3 (8) | C28—C30—C25 | 109.00 (10) |
H14A—C14—H14B | 106.2 (11) | C28—C30—H30A | 110.2 (8) |
C14—C15—C16 | 110.12 (10) | C25—C30—H30A | 109.4 (8) |
C14—C15—C20 | 109.97 (11) | C28—C30—H30B | 111.2 (8) |
C16—C15—C20 | 108.96 (10) | C25—C30—H30B | 109.5 (8) |
C14—C15—H15 | 110.5 (8) | H30A—C30—H30B | 107.5 (11) |
C16—C15—H15 | 109.1 (8) | | |
| | | |
O1—C1—C2—C3 | −179.22 (9) | C14—C13—C19—C18 | 60.65 (13) |
C7—C1—C2—C3 | −60.46 (12) | C12—C13—C19—C18 | −59.42 (13) |
C6—C1—C2—C3 | 60.33 (13) | C17—C18—C19—C13 | 57.13 (12) |
C1—C2—C3—C9 | 60.10 (12) | C20—C18—C19—C13 | −57.85 (12) |
C1—C2—C3—C4 | −60.27 (13) | C23—C18—C19—C13 | 179.63 (9) |
C9—C3—C4—C5 | −60.33 (13) | C14—C15—C20—C18 | −59.65 (13) |
C2—C3—C4—C5 | 60.06 (14) | C16—C15—C20—C18 | 61.13 (14) |
C3—C4—C5—C10 | 57.62 (12) | C19—C18—C20—C15 | 56.99 (13) |
C3—C4—C5—C6 | −57.12 (13) | C17—C18—C20—C15 | −58.04 (13) |
C3—C4—C5—C5i | −179.31 (12) | C23—C18—C20—C15 | 179.72 (10) |
O1—C1—C6—C5 | 178.16 (9) | O3—C21—C22—C23 | −177.69 (9) |
C7—C1—C6—C5 | 60.12 (12) | C26—C21—C22—C23 | 60.36 (12) |
C2—C1—C6—C5 | −60.57 (13) | C27—C21—C22—C23 | −60.25 (13) |
C10—C5—C6—C1 | −57.23 (12) | C21—C22—C23—C24 | −57.42 (12) |
C4—C5—C6—C1 | 57.51 (13) | C21—C22—C23—C29 | 57.76 (13) |
C5i—C5—C6—C1 | −179.93 (11) | C21—C22—C23—C18 | 179.95 (10) |
O1—C1—C7—C8 | −178.74 (9) | C19—C18—C23—C24 | 178.50 (9) |
C2—C1—C7—C8 | 60.72 (12) | C17—C18—C23—C24 | −61.49 (12) |
C6—C1—C7—C8 | −59.74 (12) | C20—C18—C23—C24 | 58.19 (12) |
C1—C7—C8—C9 | −60.70 (12) | C19—C18—C23—C29 | 58.10 (12) |
C1—C7—C8—C10 | 59.81 (13) | C17—C18—C23—C29 | 178.11 (10) |
C2—C3—C9—C8 | −60.25 (12) | C20—C18—C23—C29 | −62.20 (13) |
C4—C3—C9—C8 | 60.14 (12) | C19—C18—C23—C22 | −61.51 (12) |
C7—C8—C9—C3 | 60.46 (13) | C17—C18—C23—C22 | 58.50 (13) |
C10—C8—C9—C3 | −60.14 (13) | C20—C18—C23—C22 | 178.19 (10) |
C9—C8—C10—C5 | 60.37 (13) | C29—C23—C24—C25 | −57.47 (12) |
C7—C8—C10—C5 | −60.04 (13) | C22—C23—C24—C25 | 57.33 (12) |
C6—C5—C10—C8 | 57.15 (12) | C18—C23—C24—C25 | 179.92 (9) |
C4—C5—C10—C8 | −57.55 (12) | C23—C24—C25—C26 | −60.31 (13) |
C5i—C5—C10—C8 | 179.43 (11) | C23—C24—C25—C30 | 60.19 (13) |
O2—C11—C12—C13 | −177.03 (9) | O3—C21—C26—C25 | −179.82 (9) |
C16—C11—C12—C13 | 60.88 (12) | C27—C21—C26—C25 | 60.15 (12) |
C17—C11—C12—C13 | −59.68 (12) | C22—C21—C26—C25 | −60.25 (12) |
C11—C12—C13—C14 | −60.60 (13) | C30—C25—C26—C21 | −59.99 (13) |
C11—C12—C13—C19 | 59.34 (13) | C24—C25—C26—C21 | 60.43 (13) |
C12—C13—C14—C15 | 59.83 (13) | O3—C21—C27—C28 | 177.02 (10) |
C19—C13—C14—C15 | −60.54 (13) | C26—C21—C27—C28 | −60.72 (13) |
C13—C14—C15—C16 | −59.74 (12) | C22—C21—C27—C28 | 59.70 (13) |
C13—C14—C15—C20 | 60.35 (12) | C21—C27—C28—C30 | 60.60 (13) |
O2—C11—C16—C15 | 178.09 (10) | C21—C27—C28—C29 | −59.79 (14) |
C12—C11—C16—C15 | −60.10 (12) | C30—C28—C29—C23 | −59.86 (13) |
C17—C11—C16—C15 | 60.42 (13) | C27—C28—C29—C23 | 60.19 (14) |
C14—C15—C16—C11 | 59.82 (13) | C24—C23—C29—C28 | 57.28 (13) |
C20—C15—C16—C11 | −60.86 (14) | C22—C23—C29—C28 | −57.62 (13) |
O2—C11—C17—C18 | 179.87 (10) | C18—C23—C29—C28 | −179.93 (10) |
C12—C11—C17—C18 | 60.36 (12) | C27—C28—C30—C25 | −60.45 (13) |
C16—C11—C17—C18 | −60.02 (13) | C29—C28—C30—C25 | 59.90 (13) |
C11—C17—C18—C19 | −57.77 (12) | C26—C25—C30—C28 | 60.33 (13) |
C11—C17—C18—C20 | 57.46 (13) | C24—C25—C30—C28 | −60.10 (13) |
C11—C17—C18—C23 | 179.61 (10) | | |
Symmetry code: (i) −x+1, −y+1, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1H···O3 | 0.93 (2) | 1.77 (2) | 2.6976 (14) | 175.9 (18) |
O2—H2H···O1ii | 0.915 (19) | 1.79 (2) | 2.6993 (12) | 176.6 (18) |
O3—H3H···O2iii | 0.917 (19) | 1.762 (19) | 2.6637 (12) | 167.5 (18) |
Symmetry codes: (ii) x−1, y, z; (iii) −x+1, −y, −z. |
Experimental details
Crystal data |
Chemical formula | C20H30O2 |
Mr | 302.44 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 11.3855 (8), 11.3863 (9), 11.5351 (8) |
α, β, γ (°) | 62.220 (9), 81.596 (11), 65.878 (9) |
V (Å3) | 1205.7 (2) |
Z | 3 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.27 × 0.25 × 0.20 |
|
Data collection |
Diffractometer | Stoe IPDS diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11179, 5076, 3549 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.634 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.086, 1.02 |
No. of reflections | 5076 |
No. of parameters | 478 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.23, −0.15 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1H···O3 | 0.93 (2) | 1.77 (2) | 2.6976 (14) | 175.9 (18) |
O2—H2H···O1i | 0.915 (19) | 1.79 (2) | 2.6993 (12) | 176.6 (18) |
O3—H3H···O2ii | 0.917 (19) | 1.762 (19) | 2.6637 (12) | 167.5 (18) |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z. |
Alcohols are the simplest self-complementary donor–acceptor species suitable for the generation of different catemeric and oligomeric cluster motifs by strong and directional O—H···O hydrogen bonding (McGregor et al., 2006). From the crystal design perspective, these motifs attract attention as versatile synthons for the supramolecular synthesis of hydrogen-bonded frameworks and for the evaluation of subtle packing effects influencing the rich polymorphism of alcohols (Allan & Clark, 1999). Unlike simpler species, the solid-state supramolecular chemistry of bulky tertiary alcohols is dominated by self-assembly of oligomers, with the tetrameric pattern representing the commonest motif. This synthon is equally important for both simple monofunctional species, such as 1-adamantol (Amoureux et al., 1979) and 1-diamantol (Yu et al., 2006), and for the polymeric self-assembly of the structures of bulky aliphatic diols. In this way, tetrameric clusters commonly provide tetrahedral nodes for the generation of elegant three-dimensional arrays, such as the diamondoid framework found for bicyclo[4.4.1]undecane-1,6-diol (White & Bovill, 1977) and the threefold interpenetrated diamondoid framework of diamantane-4,9-diol (Schwertfeger et al., 2008). That higher oligomers could also possess a comparable significance for the solid-state supramolecular chemistry of alcohols was suggested by examination of the hexamer-based structure of phase II of tert-BuOH (McGregor et al., 2006). In the present contribution, the structure of the first entirely aliphatic diol, the title compound, (I), to generate a framework structure based upon hexameric synthons is reported. The extremely bulky 1,1'-biadamantanediyl spacer was essential for constraining molecular alignment and thus facilitating self-assembly of the alcohol hexamers.
The structure of (I) comprises two independent molecules, one of which (A) is situated across a centre of inversion, whilst the second (B) resides in a general position (Fig. 1). Both molecules adopt staggered conformations, but they are different conformers, as shown by the mutual orientation of the –OH groups: pseudo-anti for centrosymmetric molecule A and pseudo-gauche for molecule B [O2···C18—C23···O3 = 59.76 (13)°]. The long central C—C bonds [C5—C5i = 1.585 (2) Å and C18—C23 = 1.5804 (14) Å; symmetry code: (i) -x + 1, -y + 1, -z] agree with the geometric parameters found for 1,1'-biadamantane [1.579 (3) Å; Alden et al., 1968] and for 1,1'-biadamantane-supported bis(1,2,4-triazole) [1.582 (5) Å; Senchyk et al., 2010].
Directional and relatively strong hydrogen bonding of the type O—H···O [O···O = 2.6637 (12)–2.6993 (12) Å; Table 1] is responsible for the assembly of centrosymmetric (OH)6 hexamers (Figs. 1 and 2). Each hexamer involves both A and B molecules. The nonplanar hexagons, defined by the O atoms, possess a chair conformation and adopt an almost perfect cyclohexane-like geometry, with O···O···O angles of 106.55 (4)–115.81 (4)° [average 110.63 (4)°], and the average O···O···O···O pseudo-torsion angle is 57.17 (6)°. This type of self-assembly of alcohol oligomers is relatively rare in the solid state, although hexameric clusters are the predominant species in liquid methanol at room temperature (Sarkar & Joarder, 1993) and the (MeOH)6 cluster has even been captured as a guest entity in a lattice clathrate complex (Penkert et al., 1998). All solid-state examples of ROH hexamers are for bulky alcohols: the low-temperature and high-pressure phase II of tert-butanol (McGregor et al., 2006), bis(pentafluorophenyl)methanol (Ferguson et al., 1995), 2,4,6-tris(trifluoromethyl)benzyl alcohol (Edelmann et al., 2004), and the closely related ferrocenyldimethylsilanol (Sharma et al., 2005). The most closely comparable structure is that of tert-butanol, though the bonding is certainly weaker [O···O = 2.729 (1)–2.779 (1) Å], leading to a slight flattening of the hexagons [average O···O···O···O torsion angle = 50.1°; McGregor et al., 2006].
In (I), the hexamers provide an origin of connectivity for the generation of a layered hydrogen-bonded network, parallel to the ab plane. The topology of this layer may be best described as a `square grid net' (44), with the nodes represented by the hydrogen-bonded hexamers and with two kinds of links in equal proportions: single bridges of molecules A and double bridges of molecules B [internodal distance = 12.3821 (9) Å and a = 11.3855 (8) Å]. The presence of the double links decreases the connectedness of the nodes down to four. The layers are stacked on top of one another at 11.5351 (8) Å (parameter c of the unit cell) (Fig. 3).
The stabilization of hexameric clusters rather than the formation of the more common tetramers is a peculiar feature of the system. No other aliphatic diol adopts such a relatively open architecture and the prototypical monofunctional 1-adamantol also crystallizes as a self-assembled tetramer (Amoureux et al., 1979). The present pattern can be rationalized in terms of the adaptibility of the hydrogen-bonding topology to the steric demands imposed by the alignment of the aliphatic scaffolds. Unlike the simple adamantyl units, the bulky biadamantanediyl carriers have an approximately cylindrical shape and afford solely hexagonal packing in the bc plane, with intermolecular separations r (defined as the distances between the centroids of the carbocyclic frames) in the range 6.486 (2)–7.053 (2) Å. The shortest intermolecular C···C contact is C3···C29(x, y + 1, z - 1) = 3.7960 (17) Å, while the closest C—H···O contact possibly indicates very weak hydrogen bonding [C2···O3 = 3.4270 (16) Å, H2A···O3 = 2.724 (13) Å and C2—H2A···O3 = 127.6 (9)°]. The hydrophobic layers (Fig. 4) have the same hexagonal packing as seen in 1,1'-biadamantane itself, with r = 6.531 (2)–6.577 (2) Å (Alden et al., 1968), and thus the presence of two hydroxy groups in (I) does not influence this specific substructure. In fact, the most appreciable difference is the increase in the interlayer separation, viz. 11.3855 (8) Å (parameter a of the unit cell) for (I) versus 10.4571 (6) Å for 1,1'-biadamantane. Within these noncovalent layers, the hydrogen bonding between three closest neighbours assembles the molecules into triads (Fig. 4), and two such triads from successive layers constitute the above centrosymmetric hexamers.
In brief, the present system is important in view of two major aspects. The hexameric clusters provide new insights into developing framework structures based upon oligomeric alcohol species as reliable supramolecular synthons. At the same time, the shape-complementary packing of biadamantane modules may find further applications, such as designing non-covalent layers or for the generation of hydrophobic molecular coatings.