supplementary materials


fj2615 scheme

Acta Cryst. (2013). E69, o424    [ doi:10.1107/S1600536813004625 ]

5,17-Diformyl-25,26,27,28-tetrapropoxycalix[4]arene

Z. Li, H. Ma, Y. Lai, L. Chen and X. Sun

Abstract top

The title compound, C42H48O6, was obtained via formylation of 25,26,27,28-tetrapropoxycalix[4]arene with dichloromethyl methyl ether and tin tetrachloride. It adopts a pinched cone conformation, which leads to an open cavity. The two opposite aromatic rings bearing formyl groups are almost parallel, making a dihedral angle of 29.1 (2)°. The other pair of opposite rings are close to being perpendicular, making a dihedral angle of 73.6 (1)°. Adjacent rings are almost perpendicular, making dihedral angles of 78.8 (2), 81.6 (1), 78.2 (1) and 74.7 (1)°.

Comment top

Regioselective formylation at the upper rim of calixarenes is an important way to obtain functional calixarene because aldehyde group can be easily transformed into hydroxy and carboxyl which are very useful in organic synthesis (Arduini et al., 1995) and the suparamolecular self-assembly (Kennedy et al., 2010). Although the crystal structures of 5,17-diformyl-25,27-dipropoxycalix[4]arene (Seigle-Ferrand et al., 2006) and 5,17-Diformyl-25,26,27,28-tetrabenzyloxycalix[4]arene (Decken et al., 2004) have been reported, we herein present the structure of 5,17-diformyl-25,26,27,28-tetrapropoxycalix[4]arene (Fig. 1).

The title compound adopts a pinched cone conformation with a small cavity. All phenyl rings are tilted to from the calix cavity, as defined by the angles which the aromatic rings make with the plane of the four bridging CH2 moieties (C7, C14, C21 and C28) which link them, viz. 36.8 (1)° (C1–C6 or C15–C20), 77.2 (1)° (C8–C13) and 73.5 (2)° (C22–C27), respectively. Two opposite aromatic rings (C8–C13 and C22–C27) with formyl groups are almost parallel [dihedral angle 29.1 (2)°], while the other pair of opposite rings (C1–C6 and C15–20) are close to being perpendicular to one another [dihedral angle 73.6 (1)°], and adjacent phenyl rings are almost perpendicular [dihedral angles 78.8 (2)°, 81.6 (1)°, 78.2 (1)° and 74.7 (1)°, respectively].

Related literature top

For general background to calix[4]arenes, see: Arduini et al. (1995); Decken et al. (2004); Seigle-Ferrand et al. (2006); Kennedy et al. (2010).

Experimental top

To a solution of 25,26,27,28-tetrapropoxycalix[4]arene (0.5 g, 0.84 mmol) in dry CHCl3 (35 ml) cooled at -35 °C were added 1,1-dichlorodimethyl ether (0.15 ml, 1.68 mmol) and tin tetrachloride (0.19 ml, 1.68 mmol). The reaction mixture was stirred at -35 °C for 5 min and then treated with water (50 ml). The organic layer was washed twice with water and dried by Na2SO4, and the solvent was evaporated under reduced pressure. Purification by column chromatography (petroleum ether/ethyl acetate 5:1) afforded white solid (0.23 g, yield 42.2%, m.p. > 573 K). Single crystals suitable for X-ray diffraction were obtained by evaporation of an enthanol solution.

Refinement top

All the H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.93–0.97 Å, and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. All H atoms have been omitted for clarity.
5,17-Diformyl-25,26,27,28-tetrapropoxycalix[4]arene top
Crystal data top
C42H48O6F(000) = 2784
Mr = 648.80Dx = 1.157 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 6648 reflections
a = 14.7121 (15) Åθ = 2.3–21.5°
b = 17.5133 (19) ŵ = 0.08 mm1
c = 28.912 (3) ÅT = 296 K
V = 7449.5 (14) Å3Block, colourless
Z = 80.20 × 0.18 × 0.15 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
6924 independent reflections
Radiation source: fine-focus sealed tube3908 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.085
phi and ω scansθmax = 25.5°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1713
Tmin = 0.985, Tmax = 0.989k = 2121
41325 measured reflectionsl = 3135
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.066Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.220H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.1343P)2 + 0.050P]
where P = (Fo2 + 2Fc2)/3
6924 reflections(Δ/σ)max < 0.001
437 parametersΔρmax = 0.34 e Å3
1 restraintΔρmin = 0.22 e Å3
Crystal data top
C42H48O6V = 7449.5 (14) Å3
Mr = 648.80Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 14.7121 (15) ŵ = 0.08 mm1
b = 17.5133 (19) ÅT = 296 K
c = 28.912 (3) Å0.20 × 0.18 × 0.15 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
6924 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
3908 reflections with I > 2σ(I)
Tmin = 0.985, Tmax = 0.989Rint = 0.085
41325 measured reflectionsθmax = 25.5°
Refinement top
R[F2 > 2σ(F2)] = 0.066H-atom parameters constrained
wR(F2) = 0.220Δρmax = 0.34 e Å3
S = 1.00Δρmin = 0.22 e Å3
6924 reflectionsAbsolute structure: ?
437 parametersFlack parameter: ?
1 restraintRogers parameter: ?
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
xyzUiso*/Ueq
O60.75730 (12)0.16233 (10)0.59545 (6)0.0746 (5)
O40.98908 (12)0.13116 (9)0.59448 (6)0.0711 (5)
O50.91208 (13)0.31123 (10)0.61795 (7)0.0767 (5)
O31.14504 (13)0.28445 (10)0.60310 (7)0.0763 (5)
O20.86628 (16)0.06906 (13)0.80074 (8)0.1001 (7)
C10.88905 (18)0.36103 (13)0.65298 (9)0.0620 (6)
C110.84777 (15)0.08053 (13)0.70120 (9)0.0592 (6)
H110.87480.03560.71140.071*
C100.82985 (15)0.13841 (13)0.73289 (9)0.0566 (6)
C120.82641 (15)0.08821 (13)0.65480 (9)0.0572 (6)
C261.07862 (15)0.21843 (14)0.73661 (9)0.0614 (6)
C251.06269 (16)0.29248 (14)0.72202 (9)0.0639 (7)
H251.03800.32750.74260.077*
C241.08283 (16)0.31549 (13)0.67726 (9)0.0605 (6)
C90.79508 (15)0.20714 (12)0.71674 (9)0.0573 (6)
H90.78750.24740.73730.069*
C130.78363 (15)0.15595 (13)0.64102 (9)0.0580 (6)
C231.12262 (16)0.26208 (14)0.64775 (9)0.0609 (6)
C60.80146 (18)0.35706 (13)0.67044 (10)0.0656 (7)
C271.11350 (16)0.16595 (14)0.70534 (9)0.0634 (7)
H271.12180.11570.71480.076*
O11.02457 (15)0.23488 (13)0.81322 (7)0.0954 (6)
C201.01733 (18)0.06375 (13)0.61494 (8)0.0602 (6)
C20.95571 (18)0.40740 (13)0.67259 (10)0.0658 (7)
C221.13630 (15)0.18610 (14)0.66045 (9)0.0598 (6)
C80.77141 (15)0.21727 (13)0.67091 (9)0.0590 (6)
C140.85238 (18)0.02586 (14)0.62104 (9)0.0697 (7)
H14A0.81720.01980.62740.084*
H14B0.83900.04220.58970.084*
C420.84557 (16)0.12809 (16)0.78227 (10)0.0681 (7)
H420.83900.17080.80110.082*
C150.95255 (17)0.00841 (13)0.62548 (9)0.0631 (7)
C70.73768 (17)0.29499 (14)0.65468 (10)0.0719 (7)
H7A0.73360.29540.62120.086*
H7B0.67740.30440.66710.086*
C281.05459 (18)0.39427 (14)0.66110 (11)0.0760 (8)
H28A1.09170.43270.67620.091*
H28B1.06370.39860.62800.091*
C211.16861 (17)0.12626 (15)0.62629 (10)0.0706 (7)
H21A1.16820.14740.59530.085*
H21B1.23040.11140.63370.085*
C191.10750 (18)0.05747 (14)0.62828 (9)0.0636 (7)
C181.1346 (2)0.01116 (16)0.64855 (10)0.0752 (8)
H181.19510.01780.65710.090*
C30.9293 (2)0.45609 (14)0.70747 (11)0.0797 (8)
H30.97200.48860.72060.096*
C50.7783 (2)0.40644 (15)0.70581 (10)0.0775 (8)
H50.71980.40520.71800.093*
C160.9842 (2)0.05922 (14)0.64578 (10)0.0772 (8)
H160.94330.09820.65230.093*
C171.0738 (2)0.06872 (16)0.65606 (11)0.0844 (9)
H171.09380.11490.66830.101*
C40.8413 (2)0.45786 (16)0.72333 (11)0.0860 (9)
H40.82410.49330.74570.103*
C411.05586 (19)0.19441 (17)0.78352 (11)0.0760 (8)
H411.06640.14360.79110.091*
C380.6601 (2)0.15937 (19)0.58853 (11)0.0884 (9)
H38A0.64660.17540.55720.106*
H38B0.63140.19540.60940.106*
C331.0501 (4)0.1401 (4)0.51739 (16)0.173 (2)
H33A1.07880.18720.52730.207*
H33B1.09280.09890.52300.207*
C320.9706 (3)0.1274 (2)0.54593 (13)0.1158 (12)
H32A0.92490.16530.53830.139*
H32B0.94550.07760.53880.139*
C350.9231 (3)0.3447 (2)0.57389 (13)0.1139 (12)
H35A0.96490.31390.55580.137*
H35B0.94980.39500.57750.137*
C390.6201 (2)0.0831 (2)0.59624 (14)0.1087 (11)
H39A0.63400.06620.62740.130*
H39B0.64700.04690.57480.130*
C370.8426 (4)0.3775 (5)0.50134 (19)0.215 (3)
H37A0.87260.42620.50080.323*
H37B0.78320.38240.48790.323*
H37C0.87750.34130.48390.323*
C400.5179 (3)0.0840 (3)0.58954 (17)0.1420 (16)
H40A0.49110.12040.61030.213*
H40B0.49370.03420.59590.213*
H40C0.50400.09790.55820.213*
C291.2359 (3)0.3127 (2)0.59968 (13)0.1179 (13)
H29A1.27860.27230.60700.142*
H29B1.24480.35390.62170.142*
C360.8345 (3)0.3518 (4)0.54810 (17)0.1536 (18)
H36A0.80470.30240.54810.184*
H36B0.79550.38710.56470.184*
C341.0344 (4)0.1447 (4)0.46906 (16)0.207 (3)
H34A0.99740.10240.45950.311*
H34B1.09140.14310.45300.311*
H34C1.00370.19170.46210.311*
C311.2117 (6)0.4091 (4)0.5406 (2)0.224 (3)
H31A1.15230.39920.52820.337*
H31B1.24780.43520.51790.337*
H31C1.20630.44030.56770.337*
C301.2528 (4)0.3410 (4)0.55198 (19)0.178 (2)
H30A1.31790.34680.54790.214*
H30B1.23240.30230.53030.214*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O60.0729 (12)0.0742 (12)0.0766 (12)0.0064 (9)0.0042 (9)0.0019 (10)
O40.0751 (12)0.0508 (10)0.0873 (13)0.0007 (8)0.0014 (9)0.0081 (9)
O50.0787 (13)0.0567 (11)0.0945 (14)0.0011 (9)0.0069 (10)0.0133 (10)
O30.0785 (12)0.0700 (12)0.0805 (13)0.0166 (9)0.0020 (9)0.0046 (10)
O20.1230 (18)0.0842 (15)0.0930 (15)0.0323 (13)0.0075 (12)0.0146 (12)
C10.0727 (17)0.0399 (12)0.0733 (16)0.0093 (11)0.0103 (13)0.0059 (12)
C110.0534 (14)0.0419 (12)0.0823 (18)0.0012 (10)0.0040 (12)0.0014 (12)
C100.0467 (13)0.0506 (14)0.0724 (16)0.0019 (10)0.0015 (11)0.0018 (12)
C120.0516 (13)0.0436 (13)0.0763 (17)0.0072 (10)0.0053 (11)0.0038 (12)
C260.0529 (14)0.0570 (15)0.0744 (16)0.0010 (11)0.0077 (12)0.0006 (13)
C250.0556 (14)0.0537 (15)0.0825 (18)0.0016 (11)0.0064 (12)0.0102 (13)
C240.0542 (14)0.0472 (14)0.0802 (17)0.0067 (11)0.0140 (12)0.0006 (12)
C90.0526 (13)0.0431 (13)0.0762 (17)0.0008 (10)0.0005 (11)0.0075 (12)
C130.0545 (14)0.0538 (14)0.0656 (16)0.0089 (11)0.0024 (11)0.0026 (12)
C230.0536 (14)0.0595 (15)0.0697 (16)0.0120 (11)0.0071 (12)0.0013 (13)
C60.0715 (17)0.0421 (13)0.0832 (18)0.0125 (12)0.0155 (14)0.0021 (12)
C270.0570 (15)0.0491 (14)0.0841 (18)0.0059 (11)0.0073 (12)0.0021 (13)
O10.1027 (16)0.0954 (16)0.0880 (14)0.0065 (12)0.0118 (12)0.0073 (13)
C200.0727 (17)0.0428 (13)0.0649 (15)0.0022 (12)0.0119 (12)0.0082 (11)
C20.0771 (17)0.0356 (12)0.0848 (18)0.0024 (11)0.0151 (13)0.0014 (12)
C220.0493 (13)0.0527 (14)0.0774 (17)0.0021 (10)0.0044 (11)0.0036 (13)
C80.0481 (13)0.0452 (13)0.0837 (18)0.0015 (10)0.0044 (11)0.0018 (12)
C140.0741 (17)0.0510 (14)0.0840 (18)0.0116 (12)0.0090 (13)0.0123 (13)
C420.0585 (15)0.0652 (17)0.0806 (18)0.0095 (12)0.0005 (13)0.0045 (14)
C150.0722 (17)0.0449 (13)0.0722 (16)0.0002 (12)0.0131 (12)0.0099 (12)
C70.0595 (15)0.0566 (15)0.099 (2)0.0061 (12)0.0153 (13)0.0031 (14)
C280.0765 (18)0.0500 (15)0.102 (2)0.0113 (13)0.0134 (15)0.0018 (14)
C210.0599 (16)0.0685 (17)0.0834 (18)0.0052 (12)0.0054 (13)0.0056 (14)
C190.0701 (17)0.0505 (14)0.0702 (16)0.0068 (12)0.0108 (12)0.0087 (12)
C180.0794 (18)0.0635 (17)0.0826 (19)0.0203 (15)0.0069 (14)0.0080 (15)
C30.092 (2)0.0448 (14)0.102 (2)0.0049 (14)0.0246 (17)0.0098 (15)
C50.0831 (19)0.0543 (16)0.095 (2)0.0209 (14)0.0003 (15)0.0026 (15)
C160.097 (2)0.0399 (14)0.094 (2)0.0013 (13)0.0215 (16)0.0024 (13)
C170.102 (2)0.0497 (16)0.101 (2)0.0205 (16)0.0168 (18)0.0045 (15)
C40.111 (3)0.0561 (17)0.091 (2)0.0193 (17)0.0109 (18)0.0174 (15)
C410.0706 (18)0.0704 (18)0.087 (2)0.0004 (14)0.0032 (15)0.0008 (16)
C380.087 (2)0.090 (2)0.089 (2)0.0096 (17)0.0133 (16)0.0021 (17)
C330.150 (4)0.257 (7)0.110 (4)0.012 (4)0.023 (3)0.004 (4)
C320.139 (3)0.114 (3)0.094 (3)0.012 (2)0.012 (2)0.031 (2)
C350.124 (3)0.124 (3)0.094 (3)0.001 (2)0.003 (2)0.019 (2)
C390.103 (3)0.100 (3)0.123 (3)0.025 (2)0.024 (2)0.009 (2)
C370.194 (6)0.329 (10)0.123 (4)0.008 (6)0.002 (4)0.032 (5)
C400.099 (3)0.133 (3)0.194 (4)0.035 (2)0.046 (3)0.010 (3)
C290.100 (3)0.137 (3)0.117 (3)0.047 (2)0.016 (2)0.016 (3)
C360.151 (4)0.195 (5)0.115 (3)0.008 (3)0.009 (3)0.024 (3)
C340.215 (6)0.300 (9)0.107 (4)0.033 (6)0.025 (4)0.003 (5)
C310.376 (11)0.171 (6)0.127 (4)0.023 (6)0.033 (5)0.048 (4)
C300.170 (5)0.214 (6)0.151 (4)0.078 (5)0.037 (4)0.046 (4)
Geometric parameters (Å, º) top
O6—C131.378 (3)C21—H21A0.9700
O6—C381.445 (3)C21—H21B0.9700
O4—C201.384 (3)C19—C181.395 (4)
O4—C321.432 (4)C18—C171.365 (4)
O5—C11.379 (3)C18—H180.9300
O5—C351.411 (4)C3—C41.373 (4)
O3—C231.389 (3)C3—H30.9300
O3—C291.429 (4)C5—C41.388 (4)
O2—C421.203 (3)C5—H50.9300
C1—C61.386 (4)C16—C171.363 (4)
C1—C21.394 (3)C16—H160.9300
C11—C121.384 (3)C17—H170.9300
C11—C101.391 (3)C4—H40.9300
C11—H110.9300C41—H410.9300
C10—C91.389 (3)C38—C391.477 (4)
C10—C421.458 (4)C38—H38A0.9700
C12—C131.401 (3)C38—H38B0.9700
C12—C141.514 (3)C33—C341.418 (6)
C26—C251.384 (3)C33—C321.449 (6)
C26—C271.388 (3)C33—H33A0.9700
C26—C411.459 (4)C33—H33B0.9700
C25—C241.388 (4)C32—H32A0.9700
C25—H250.9300C32—H32B0.9700
C24—C231.395 (3)C35—C361.508 (6)
C24—C281.515 (3)C35—H35A0.9700
C9—C81.382 (3)C35—H35B0.9700
C9—H90.9300C39—C401.516 (5)
C13—C81.390 (3)C39—H39A0.9700
C23—C221.395 (3)C39—H39B0.9700
C6—C51.382 (4)C37—C361.430 (7)
C6—C71.507 (3)C37—H37A0.9600
C27—C221.386 (3)C37—H37B0.9600
C27—H270.9300C37—H37C0.9600
O1—C411.205 (3)C40—H40A0.9600
C20—C191.386 (4)C40—H40B0.9600
C20—C151.393 (3)C40—H40C0.9600
C2—C31.377 (4)C29—C301.486 (6)
C2—C281.510 (4)C29—H29A0.9700
C22—C211.516 (4)C29—H29B0.9700
C8—C71.523 (3)C36—H36A0.9700
C14—C151.510 (4)C36—H36B0.9700
C14—H14A0.9700C34—H34A0.9600
C14—H14B0.9700C34—H34B0.9600
C42—H420.9300C34—H34C0.9600
C15—C161.401 (4)C31—C301.377 (8)
C7—H7A0.9700C31—H31A0.9600
C7—H7B0.9700C31—H31B0.9600
C28—H28A0.9700C31—H31C0.9600
C28—H28B0.9700C30—H30A0.9700
C21—C191.504 (4)C30—H30B0.9700
C13—O6—C38114.1 (2)C4—C3—H3119.2
C20—O4—C32115.9 (2)C2—C3—H3119.2
C1—O5—C35115.4 (2)C6—C5—C4120.7 (3)
C23—O3—C29112.6 (2)C6—C5—H5119.6
O5—C1—C6117.7 (2)C4—C5—H5119.6
O5—C1—C2119.6 (2)C17—C16—C15121.1 (3)
C6—C1—C2122.4 (2)C17—C16—H16119.5
C12—C11—C10121.6 (2)C15—C16—H16119.5
C12—C11—H11119.2C16—C17—C18120.6 (3)
C10—C11—H11119.2C16—C17—H17119.7
C9—C10—C11118.7 (2)C18—C17—H17119.7
C9—C10—C42119.7 (2)C3—C4—C5119.5 (3)
C11—C10—C42121.6 (2)C3—C4—H4120.2
C11—C12—C13117.4 (2)C5—C4—H4120.2
C11—C12—C14119.8 (2)O1—C41—C26125.5 (3)
C13—C12—C14122.7 (2)O1—C41—H41117.3
C25—C26—C27119.0 (2)C26—C41—H41117.3
C25—C26—C41121.0 (2)O6—C38—C39114.0 (3)
C27—C26—C41120.0 (2)O6—C38—H38A108.8
C26—C25—C24121.4 (2)C39—C38—H38A108.8
C26—C25—H25119.3O6—C38—H38B108.8
C24—C25—H25119.3C39—C38—H38B108.8
C25—C24—C23117.7 (2)H38A—C38—H38B107.7
C25—C24—C28119.6 (2)C34—C33—C32116.0 (5)
C23—C24—C28122.5 (2)C34—C33—H33A108.3
C8—C9—C10121.8 (2)C32—C33—H33A108.3
C8—C9—H9119.1C34—C33—H33B108.3
C10—C9—H9119.1C32—C33—H33B108.3
O6—C13—C8119.7 (2)H33A—C33—H33B107.4
O6—C13—C12117.8 (2)O4—C32—C33113.4 (4)
C8—C13—C12122.4 (2)O4—C32—H32A108.9
O3—C23—C24118.6 (2)C33—C32—H32A108.9
O3—C23—C22118.7 (2)O4—C32—H32B108.9
C24—C23—C22122.6 (2)C33—C32—H32B108.9
C5—C6—C1117.9 (2)H32A—C32—H32B107.7
C5—C6—C7121.4 (3)O5—C35—C36112.4 (4)
C1—C6—C7120.3 (2)O5—C35—H35A109.1
C22—C27—C26122.1 (2)C36—C35—H35A109.1
C22—C27—H27119.0O5—C35—H35B109.1
C26—C27—H27119.0C36—C35—H35B109.1
O4—C20—C19118.3 (2)H35A—C35—H35B107.9
O4—C20—C15118.8 (2)C38—C39—C40111.5 (3)
C19—C20—C15122.6 (2)C38—C39—H39A109.3
C3—C2—C1117.4 (3)C40—C39—H39A109.3
C3—C2—C28121.9 (2)C38—C39—H39B109.3
C1—C2—C28120.0 (2)C40—C39—H39B109.3
C27—C22—C23117.0 (2)H39A—C39—H39B108.0
C27—C22—C21120.6 (2)C36—C37—H37A109.5
C23—C22—C21122.2 (2)C36—C37—H37B109.5
C9—C8—C13117.7 (2)H37A—C37—H37B109.5
C9—C8—C7119.5 (2)C36—C37—H37C109.5
C13—C8—C7122.8 (2)H37A—C37—H37C109.5
C15—C14—C12109.7 (2)H37B—C37—H37C109.5
C15—C14—H14A109.7C39—C40—H40A109.5
C12—C14—H14A109.7C39—C40—H40B109.5
C15—C14—H14B109.7H40A—C40—H40B109.5
C12—C14—H14B109.7C39—C40—H40C109.5
H14A—C14—H14B108.2H40A—C40—H40C109.5
O2—C42—C10125.6 (3)H40B—C40—H40C109.5
O2—C42—H42117.2O3—C29—C30109.7 (3)
C10—C42—H42117.2O3—C29—H29A109.7
C20—C15—C16116.9 (2)C30—C29—H29A109.7
C20—C15—C14120.5 (2)O3—C29—H29B109.7
C16—C15—C14122.0 (2)C30—C29—H29B109.7
C6—C7—C8110.41 (19)H29A—C29—H29B108.2
C6—C7—H7A109.6C37—C36—C35114.9 (4)
C8—C7—H7A109.6C37—C36—H36A108.5
C6—C7—H7B109.6C35—C36—H36A108.5
C8—C7—H7B109.6C37—C36—H36B108.5
H7A—C7—H7B108.1C35—C36—H36B108.5
C2—C28—C24109.6 (2)H36A—C36—H36B107.5
C2—C28—H28A109.8C33—C34—H34A109.5
C24—C28—H28A109.8C33—C34—H34B109.5
C2—C28—H28B109.8H34A—C34—H34B109.5
C24—C28—H28B109.8C33—C34—H34C109.5
H28A—C28—H28B108.2H34A—C34—H34C109.5
C19—C21—C22110.0 (2)H34B—C34—H34C109.5
C19—C21—H21A109.7C30—C31—H31A109.5
C22—C21—H21A109.7C30—C31—H31B109.5
C19—C21—H21B109.7H31A—C31—H31B109.5
C22—C21—H21B109.7C30—C31—H31C109.5
H21A—C21—H21B108.2H31A—C31—H31C109.5
C20—C19—C18117.3 (2)H31B—C31—H31C109.5
C20—C19—C21119.9 (2)C31—C30—C29115.9 (6)
C18—C19—C21122.3 (3)C31—C30—H30A108.3
C17—C18—C19121.0 (3)C29—C30—H30A108.3
C17—C18—H18119.5C31—C30—H30B108.3
C19—C18—H18119.5C29—C30—H30B108.3
C4—C3—C2121.7 (3)H30A—C30—H30B107.4
C35—O5—C1—C6108.8 (3)C11—C12—C14—C1553.0 (3)
C35—O5—C1—C277.7 (3)C13—C12—C14—C15124.8 (2)
C12—C11—C10—C94.2 (3)C9—C10—C42—O2171.8 (3)
C12—C11—C10—C42175.0 (2)C11—C10—C42—O27.4 (4)
C10—C11—C12—C131.7 (3)O4—C20—C15—C16179.5 (2)
C10—C11—C12—C14176.2 (2)C19—C20—C15—C167.2 (4)
C27—C26—C25—C241.5 (4)O4—C20—C15—C148.6 (3)
C41—C26—C25—C24179.0 (2)C19—C20—C15—C14164.7 (2)
C26—C25—C24—C232.1 (3)C12—C14—C15—C2063.7 (3)
C26—C25—C24—C28173.1 (2)C12—C14—C15—C16107.8 (3)
C11—C10—C9—C85.1 (3)C5—C6—C7—C8106.7 (3)
C42—C10—C9—C8174.1 (2)C1—C6—C7—C866.5 (3)
C38—O6—C13—C874.2 (3)C9—C8—C7—C649.8 (3)
C38—O6—C13—C12109.0 (3)C13—C8—C7—C6127.2 (3)
C11—C12—C13—O6176.3 (2)C3—C2—C28—C24107.4 (3)
C14—C12—C13—O65.9 (3)C1—C2—C28—C2462.3 (3)
C11—C12—C13—C87.0 (3)C25—C24—C28—C249.5 (3)
C14—C12—C13—C8170.8 (2)C23—C24—C28—C2125.5 (3)
C29—O3—C23—C2491.3 (3)C27—C22—C21—C1946.3 (3)
C29—O3—C23—C2292.1 (3)C23—C22—C21—C19129.5 (2)
C25—C24—C23—O3178.7 (2)O4—C20—C19—C18179.6 (2)
C28—C24—C23—O36.3 (3)C15—C20—C19—C187.1 (4)
C25—C24—C23—C224.8 (3)O4—C20—C19—C218.2 (3)
C28—C24—C23—C22170.2 (2)C15—C20—C19—C21165.1 (2)
O5—C1—C6—C5179.5 (2)C22—C21—C19—C2065.1 (3)
C2—C1—C6—C56.1 (4)C22—C21—C19—C18106.7 (3)
O5—C1—C6—C76.0 (3)C20—C19—C18—C171.9 (4)
C2—C1—C6—C7167.3 (2)C21—C19—C18—C17170.2 (3)
C25—C26—C27—C222.6 (4)C1—C2—C3—C41.6 (4)
C41—C26—C27—C22179.9 (2)C28—C2—C3—C4168.3 (3)
C32—O4—C20—C19108.0 (3)C1—C6—C5—C40.4 (4)
C32—O4—C20—C1578.4 (3)C7—C6—C5—C4172.9 (2)
O5—C1—C2—C3180.0 (2)C20—C15—C16—C172.2 (4)
C6—C1—C2—C36.7 (4)C14—C15—C16—C17169.6 (2)
O5—C1—C2—C289.9 (4)C15—C16—C17—C182.7 (4)
C6—C1—C2—C28163.4 (2)C19—C18—C17—C162.9 (4)
C26—C27—C22—C230.0 (3)C2—C3—C4—C53.8 (4)
C26—C27—C22—C21176.1 (2)C6—C5—C4—C34.4 (4)
O3—C23—C22—C27179.7 (2)C25—C26—C41—O11.9 (4)
C24—C23—C22—C273.8 (3)C27—C26—C41—O1179.3 (3)
O3—C23—C22—C214.3 (3)C13—O6—C38—C3971.0 (3)
C24—C23—C22—C21172.2 (2)C20—O4—C32—C3387.1 (4)
C10—C9—C8—C130.1 (3)C34—C33—C32—O4173.9 (5)
C10—C9—C8—C7177.2 (2)C1—O5—C35—C3685.5 (4)
O6—C13—C8—C9177.2 (2)O6—C38—C39—C40178.7 (3)
C12—C13—C8—C96.2 (3)C23—O3—C29—C30175.7 (4)
O6—C13—C8—C75.7 (3)O5—C35—C36—C37173.5 (5)
C12—C13—C8—C7170.9 (2)O3—C29—C30—C3173.4 (7)
Acknowledgements top

We gratefully acknowledge the financial support from the Natural Science Foundation of China (No. 21002009), the Major Program for Natural Science Research of Jiangsu Colleges and Universities (12 K J A150002), the Scientific and Technological Project of Changzhou (CJ20115019), and the Qing-Lan Project of Jiangsu Province.

references
References top

Arduini, A., Fanni, S., Manfredi, G., Pochini, A., Ungaro, R., Sicuri, A. R. & Ugozzoli, F. (1995). J. Org. Chem. 60, 1448–1453.

Bruker (2000). SAINT, SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Decken, A., Harvey, P. D. & Douville, J. (2004). Acta Cryst. E60, o1170–o1171.

Kennedy, S., Teat, S. J. & Dalgarno, S. J. (2010). Dalton Trans. 39, 384–387.

Seigle-Ferrand, P., Sdira, S. B., Felix, C., Lamartine, R., Bavoux, C., Fenet, B., Bayard, F. & Vocanson, F. (2006). Mater. Sci. Eng. C, 26, 181–185.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.