The inclusion method was used to isolate a single component from a volatile oil mixture (extracted from the natural medicine,
fructus foeniculi) with 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol as the host molecule and 4-methoxybenzaldehyde as the guest (an oil mixture component). Crystals of the host–guest inclusion complex were obtained as C
30H
22O
2·2C
8H
8O
2, with the host molecule residing on a crystallographic inversion centre and connected to the guest molecule by an intermolecular hydrogen bond [O
O = 2.846 (5) Å]. The host–guest molecules form a layer-type structure, which extends along the
a axis and periodically arranges along the
b axis.
Supporting information
CCDC reference: 202317
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.004 Å
- R factor = 0.058
- wR factor = 0.124
- Data-to-parameter ratio = 13.2
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level A:
DIFF_019 Alert A _diffrn_standards_number is missing
Number of standards used in measurement.
| Author response: Our diffractometer collect data with the
area-detector. Diffraction standards are not needed.
|
DIFF_020 Alert A _diffrn_standards_interval_count and
_diffrn_standards_interval_time are missing. Number of measurements
between standards or time (min) between standards.
| Author response: Our diffractometer collect data with the
area-detector. Diffraction standards are not needed.
|
DIFF_022 Alert A _diffrn_standards_decay_% is missing
Percentage decrease in standards intensity.
| Author response: Our diffractometer collect data with the
area-detector. Diffraction standards are not needed.
|
Alert Level C:
PLAT_373 Alert C Long C(sp)-C(sp) Bond C(15) - C(15)a = 1.39 Ang.
3 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
Fructus foeniculi (100 g) was ground and distilled with water vapor. The volatile oil was dehydrated with anhydrous Na2SO4 and 2 g of material was obtained. 1,1,6,6-Tetraphenylhexa-2,4-diyne-1,6-diol (0.2 g) was added to a 10 ml conical flask and dissolved in ethyl ether (0.6 ml). The volatile oil (0.3 g) and petroleum ether (1 ml) were added to the host solution and the resulting solution stored at 298 K. After the crystals were found, recrystallization was under the same conditions and the title host–guest inclusion complex was obtained.
Data collection: DENZO (MacScience, 1996); cell refinement: SCALE (MacScience, 1996); data reduction: SCALE; program(s) used to solve structure: SHELXS90 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLUTON (Spek, 1990).
1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol–4-methoxybenzaldehyde (1/2)
top
Crystal data top
C30H22O2·2C8H8O2 | F(000) = 724 |
Mr = 686.80 | Dx = 1.244 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3223 reflections |
a = 8.593 (1) Å | θ = 2–25° |
b = 18.181 (1) Å | µ = 0.08 mm−1 |
c = 12.649 (1) Å | T = 296 K |
β = 111.38 (1)° | Block, pale yellow |
V = 1840.2 (3) Å3 | 0.40 × 0.30 × 0.22 mm |
Z = 2 | |
Data collection top
MAC DIP 2030K diffractometer | 3101 reflections with F2 ≥ 2σ(F2) |
Radiation source: rotate anode | Rint = 0.032 |
Graphite monochromator | θmax = 25.0°, θmin = 0.0° |
ω scans | h = 0→11 |
5896 measured reflections | k = −21→20 |
3223 independent reflections | l = −16→15 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.058 | w = 1/[σ2(Fo2) + (0.1082P)2 + 0.627P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.124 | (Δ/σ)max = 0.007 |
S = 1.46 | Δρmax = 0.12 e Å−3 |
3101 reflections | Δρmin = −0.28 e Å−3 |
235 parameters | |
Crystal data top
C30H22O2·2C8H8O2 | V = 1840.2 (3) Å3 |
Mr = 686.80 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.593 (1) Å | µ = 0.08 mm−1 |
b = 18.181 (1) Å | T = 296 K |
c = 12.649 (1) Å | 0.40 × 0.30 × 0.22 mm |
β = 111.38 (1)° | |
Data collection top
MAC DIP 2030K diffractometer | 3101 reflections with F2 ≥ 2σ(F2) |
5896 measured reflections | Rint = 0.032 |
3223 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.124 | H-atom parameters not refined |
S = 1.46 | Δρmax = 0.12 e Å−3 |
3101 reflections | Δρmin = −0.28 e Å−3 |
235 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.7685 (2) | 0.1736 (1) | 0.1652 (1) | 0.042 (1) | |
C1 | 0.9789 (3) | 0.0771 (1) | 0.2107 (2) | 0.034 (1) | |
C2 | 1.0160 (3) | 0.0206 (1) | 0.1511 (2) | 0.042 (1) | |
C3 | 1.1818 (4) | 0.0069 (2) | 0.1631 (3) | 0.053 (2) | |
C4 | 1.3084 (4) | 0.0496 (2) | 0.2351 (3) | 0.056 (2) | |
C5 | 1.2721 (4) | 0.1055 (2) | 0.2960 (3) | 0.053 (2) | |
C6 | 1.1088 (3) | 0.1196 (1) | 0.2842 (2) | 0.042 (1) | |
C7 | 0.7995 (3) | 0.0978 (1) | 0.1979 (2) | 0.034 (1) | |
C8 | 0.7758 (3) | 0.0874 (1) | 0.3114 (2) | 0.034 (1) | |
C9 | 0.7848 (4) | 0.0169 (1) | 0.3552 (3) | 0.047 (2) | |
C10 | 0.7641 (4) | 0.0054 (2) | 0.4572 (3) | 0.058 (2) | |
C11 | 0.7351 (4) | 0.0639 (2) | 0.5165 (3) | 0.061 (2) | |
C12 | 0.7264 (4) | 0.1340 (2) | 0.4738 (3) | 0.057 (2) | |
C13 | 0.7481 (4) | 0.1461 (2) | 0.3712 (2) | 0.046 (2) | |
C14 | 0.6725 (3) | 0.0523 (2) | 0.1101 (2) | 0.036 (1) | |
C15 | 0.5635 (3) | 0.0193 (1) | 0.0406 (2) | 0.037 (1) | |
O2 | 0.3304 (3) | 0.1737 (1) | 0.6777 (2) | 0.069 (2) | |
O3 | −0.1216 (3) | 0.1844 (1) | 0.9791 (2) | 0.069 (2) | |
C16 | 0.2685 (4) | 0.1764 (2) | 0.7627 (3) | 0.051 (2) | |
C17 | 0.0950 (4) | 0.1753 (2) | 0.7255 (3) | 0.049 (2) | |
C18 | 0.0170 (4) | 0.1781 (1) | 0.8024 (3) | 0.048 (1) | |
C19 | 0.1100 (4) | 0.1817 (1) | 0.9185 (3) | 0.049 (2) | |
C20 | 0.2831 (5) | 0.1821 (2) | 0.9535 (3) | 0.063 (2) | |
C21 | 0.3631 (4) | 0.1796 (2) | 0.8769 (3) | 0.062 (2) | |
C22 | 0.5064 (5) | 0.1680 (3) | 0.7063 (4) | 0.075 (4) | |
C23 | 0.0290 (5) | 0.1844 (2) | 1.0012 (3) | 0.063 (2) | |
H1 | 0.798 | 0.182 | 0.110 | 0.049 | |
H2 | 0.925 | −0.011 | 0.102 | 0.050 | |
H3 | 1.207 | −0.033 | 0.119 | 0.061 | |
H4 | 1.424 | 0.040 | 0.243 | 0.063 | |
H5 | 1.363 | 0.136 | 0.348 | 0.060 | |
H6 | 1.083 | 0.159 | 0.328 | 0.049 | |
H9 | 0.807 | −0.025 | 0.313 | 0.056 | |
H10 | 0.770 | −0.045 | 0.488 | 0.064 | |
H11 | 0.722 | 0.057 | 0.589 | 0.068 | |
H12 | 0.704 | 0.175 | 0.516 | 0.066 | |
H13 | 0.744 | 0.197 | 0.341 | 0.054 | |
H17 | 0.029 | 0.172 | 0.643 | 0.058 | |
H18 | −0.106 | 0.178 | 0.776 | 0.058 | |
H20 | 0.349 | 0.184 | 1.035 | 0.067 | |
H21 | 0.486 | 0.180 | 0.904 | 0.066 | |
H22 | 0.558 | 0.215 | 0.731 | 0.085 | |
H23 | 0.530 | 0.151 | 0.642 | 0.085 | |
H24 | 0.540 | 0.133 | 0.766 | 0.085 | |
H25 | 0.103 | 0.186 | 1.082 | 0.071 | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.056 (1) | 0.048 (1) | 0.052 (1) | 0.004 (1) | 0.019 (1) | 0.005 (1) |
C1 | 0.036 (1) | 0.049 (2) | 0.040 (2) | −0.004 (1) | 0.009 (1) | 0.004 (1) |
C2 | 0.046 (2) | 0.059 (2) | 0.050 (2) | 0.001 (1) | 0.013 (1) | −0.002 (2) |
C3 | 0.057 (2) | 0.082 (3) | 0.066 (2) | 0.018 (2) | 0.025 (2) | 0.004 (2) |
C4 | 0.039 (2) | 0.099 (3) | 0.075 (2) | 0.009 (2) | 0.020 (2) | 0.021 (2) |
C5 | 0.039 (2) | 0.083 (3) | 0.069 (2) | −0.012 (2) | 0.007 (2) | 0.008 (2) |
C6 | 0.043 (2) | 0.058 (2) | 0.051 (2) | −0.004 (1) | 0.008 (1) | 0.001 (2) |
C7 | 0.036 (2) | 0.042 (2) | 0.044 (2) | −0.003 (1) | 0.008 (1) | −0.002 (1) |
C8 | 0.032 (1) | 0.057 (2) | 0.036 (1) | −0.005 (1) | 0.007 (1) | −0.004 (1) |
C9 | 0.063 (2) | 0.063 (2) | 0.051 (2) | 0.001 (2) | 0.020 (1) | 0.004 (2) |
C10 | 0.076 (2) | 0.084 (3) | 0.057 (2) | −0.004 (2) | 0.021 (2) | 0.018 (2) |
C11 | 0.071 (2) | 0.116 (3) | 0.047 (2) | −0.016 (2) | 0.022 (2) | −0.001 (2) |
C12 | 0.069 (2) | 0.098 (3) | 0.051 (2) | −0.011 (2) | 0.025 (2) | −0.021 (2) |
C13 | 0.057 (2) | 0.065 (2) | 0.051 (2) | −0.007 (2) | 0.018 (2) | −0.009 (2) |
C14 | 0.036 (2) | 0.055 (2) | 0.043 (2) | 0.001 (1) | 0.012 (1) | 0.001 (1) |
C15 | 0.036 (1) | 0.058 (2) | 0.042 (2) | −0.002 (1) | 0.009 (1) | −0.001 (1) |
O2 | 0.068 (2) | 0.099 (2) | 0.103 (2) | −0.001 (1) | 0.043 (2) | −0.003 (2) |
O3 | 0.117 (2) | 0.082 (2) | 0.079 (2) | 0.018 (2) | 0.052 (2) | 0.021 (1) |
C16 | 0.064 (2) | 0.051 (2) | 0.077 (2) | 0.003 (2) | 0.025 (2) | 0.002 (2) |
C17 | 0.055 (2) | 0.066 (2) | 0.058 (2) | 0.001 (2) | 0.013 (2) | 0.002 (2) |
C18 | 0.058 (2) | 0.058 (2) | 0.065 (2) | 0.004 (2) | 0.020 (2) | 0.009 (2) |
C19 | 0.081 (2) | 0.048 (2) | 0.054 (2) | 0.005 (2) | 0.019 (2) | 0.009 (2) |
C20 | 0.085 (3) | 0.073 (3) | 0.058 (2) | 0.001 (2) | 0.001 (2) | 0.006 (2) |
C21 | 0.058 (2) | 0.078 (3) | 0.084 (3) | 0.003 (2) | 0.008 (2) | 0.006 (2) |
C22 | 0.074 (2) | 0.100 (2) | 0.118 (2) | −0.003 (2) | 0.046 (2) | −0.009 (2) |
C23 | 0.119 (3) | 0.059 (2) | 0.060 (2) | 0.004 (2) | 0.031 (2) | 0.013 (2) |
Geometric parameters (Å, º) top
O1—C7 | 1.436 (3) | C11—H11 | 0.978 |
O1—H1 | 0.841 | C12—C13 | 1.394 (4) |
C1—C2 | 1.379 (4) | C12—H12 | 0.980 |
C1—C6 | 1.397 (4) | C13—H13 | 0.990 |
C1—C7 | 1.537 (4) | C14—C15 | 1.187 (4) |
C2—C3 | 1.398 (4) | O2—C16 | 1.364 (4) |
C2—H2 | 0.982 | O2—C22 | 1.424 (5) |
C3—C4 | 1.376 (5) | O3—C23 | 1.220 (5) |
C3—H3 | 0.988 | C16—C17 | 1.390 (4) |
C4—C5 | 1.378 (5) | C16—C21 | 1.376 (5) |
C4—H4 | 0.980 | C17—C18 | 1.369 (5) |
C5—C6 | 1.380 (4) | C17—H17 | 0.987 |
C5—H5 | 0.981 | C18—C19 | 1.395 (4) |
C6—H6 | 0.982 | C18—H18 | 0.984 |
C7—C8 | 1.534 (4) | C19—C20 | 1.389 (5) |
C7—C14 | 1.491 (4) | C19—C23 | 1.453 (5) |
C8—C9 | 1.388 (4) | C20—C21 | 1.379 (6) |
C8—C13 | 1.379 (4) | C20—H20 | 0.980 |
C9—C10 | 1.382 (4) | C21—H21 | 0.984 |
C9—H9 | 0.991 | C22—H22 | 0.957 |
C10—C11 | 1.376 (6) | C22—H23 | 0.958 |
C10—H10 | 0.991 | C22—H24 | 0.957 |
C11—C12 | 1.375 (6) | C23—H25 | 0.987 |
| | | |
C7—O1—H1 | 108.9 | C12—C11—H11 | 119.3 |
C2—C1—C6 | 119.2 (3) | C11—C12—C13 | 120.3 (3) |
C2—C1—C7 | 123.2 (2) | C11—C12—H12 | 119.5 |
C6—C1—C7 | 117.5 (3) | C13—C12—H12 | 120.1 |
C1—C2—C3 | 120.2 (3) | C8—C13—C12 | 119.8 (3) |
C1—C2—H2 | 119.1 | C8—C13—H13 | 119.6 |
C3—C2—H2 | 120.7 | C12—C13—H13 | 120.6 |
C2—C3—C4 | 120.0 (3) | C7—C14—C15 | 175.6 (3) |
C2—C3—H3 | 119.5 | C16—O2—C22 | 119.0 (3) |
C4—C3—H3 | 120.4 | O2—C16—C17 | 114.2 (3) |
C3—C4—C5 | 120.0 (3) | O2—C16—C21 | 125.3 (3) |
C3—C4—H4 | 119.7 | C17—C16—C21 | 120.4 (3) |
C5—C4—H4 | 120.3 | C16—C17—C18 | 120.1 (3) |
C4—C5—C6 | 120.4 (3) | C16—C17—H17 | 119.6 |
C4—C5—H5 | 119.7 | C18—C17—H17 | 120.3 |
C6—C5—H5 | 119.9 | C17—C18—C19 | 120.6 (3) |
C1—C6—C5 | 120.2 (3) | C17—C18—H18 | 120.1 |
C1—C6—H6 | 119.3 | C19—C18—H18 | 119.3 |
C5—C6—H6 | 120.5 | C18—C19—C20 | 118.2 (3) |
O1—C7—C1 | 109.8 (2) | C18—C19—C23 | 121.2 (3) |
O1—C7—C8 | 108.3 (2) | C20—C19—C23 | 120.6 (3) |
O1—C7—C14 | 108.1 (2) | C19—C20—C21 | 121.8 (3) |
C1—C7—C8 | 110.0 (2) | C19—C20—H20 | 118.3 |
C1—C7—C14 | 112.1 (2) | C21—C20—H20 | 120.0 |
C8—C7—C14 | 108.5 (2) | C16—C21—C20 | 118.9 (4) |
C7—C8—C9 | 118.7 (3) | C16—C21—H21 | 120.6 |
C7—C8—C13 | 121.8 (3) | C20—C21—H21 | 120.5 |
C9—C8—C13 | 119.4 (3) | O2—C22—H22 | 110.1 |
C8—C9—C10 | 120.3 (3) | O2—C22—H23 | 110.0 |
C8—C9—H9 | 119.2 | O2—C22—H24 | 103.7 |
C10—C9—H9 | 120.5 | H22—C22—H23 | 109.9 |
C9—C10—C11 | 120.2 (3) | H22—C22—H24 | 111.5 |
C9—C10—H10 | 120.2 | H23—C22—H24 | 111.5 |
C11—C10—H10 | 119.6 | O3—C23—C19 | 125.5 (3) |
C10—C11—C12 | 119.8 (3) | O3—C23—H25 | 117.7 |
C10—C11—H11 | 120.9 | C19—C23—H25 | 116.8 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.84 | 2.01 | 2.846 (5) | 171 |
Symmetry code: (i) x+1, y, z−1. |
Experimental details
Crystal data |
Chemical formula | C30H22O2·2C8H8O2 |
Mr | 686.80 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 8.593 (1), 18.181 (1), 12.649 (1) |
β (°) | 111.38 (1) |
V (Å3) | 1840.2 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.40 × 0.30 × 0.22 |
|
Data collection |
Diffractometer | MAC DIP 2030K diffractometer |
Absorption correction | – |
No. of measured, independent and observed [F2 ≥ 2σ(F2)] reflections | 5896, 3223, 3101 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.124, 1.46 |
No. of reflections | 3101 |
No. of parameters | 235 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.12, −0.28 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.84 | 2.01 | 2.846 (5) | 171 |
Symmetry code: (i) x+1, y, z−1. |
An important direction for pharmaceutical research is to achieve bioactive leading compounds from natural products. Volatile oils exist in many natural products and they have important implications in pharmacodynamics research. Most of these oils belong to monoterpenoids, sesquiterpenoids and aromatic compounds, and they have functional groups such as alcohol, aldehyde, ketone and lactone. The similarity in chemical structure and volatility makes it more difficult to extract and isolate components from the mother oil.
The inclusion method used by us depends on two essential factors: (i) the similar geometric topology and (ii) intermolecular hydrogen bond/van der Waals forces between the host–guest molecules (Lehn, 1988). We chose 4-methoxybenzaldehyde (anisaldehyde) in the volatile oil mixture as the guest molecule, which has bioactivity such as antifungal (Sun & Sheng, 1998), and selected 1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol as the host molecule, which can include many guest molecules, such as alcohol, aldehyde, ketone and lactone (Takumi et al., 1996). We obtained a crystal of the 1:2 host–guest 1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol–4-methoxybenzaldehyde (1/2), (I).
In (I), the inversion centre of the host molecule matches with the crystallographic inversion centre (1/2,0,0) (Fig. 1). An asymmetric unit includes half of the host molecule and one guest molecule, viz. in a 1:2 ratio. With van der Waals forces, the host–guest molecules form a level-like tunnel structure, which extends along the a and c axes and periodically arranges along the b axis (Fig. 2). The guest molecule is planar, as expected. The hydroxyl group of the host molecule is associated with the aldehyde group of the guest molecule (details in Table 1).