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Acta Cryst. (2009). E65, o2357    [ doi:10.1107/S1600536809035260 ]

Bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate (Tinuvin 144)

T. Zeng and W.-Z. Ren

Abstract top

The title compound, C42H72N2O5, a hindered amine light stabiliser (HALS) with the trade name Tinuvin 144 was prepared from bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-butylmalonate and 2,6-di-tert-butyl-4-[(dimethylamino)methyl]phenol using lithium amide as a catalyst. In the molecule, both piperidine rings adopt chair conformations. In the crystal, inversion dimers linked by pairs of O-H...O hydrogen bonds occur.

Comment top

Hindered phenols are widely used as antioxidants while hindered amines are used as light stabilizers in polymers and lubricants both because of their special hindered structures (Denisov, 1991; Klemchuk & Gande ,1998; Yamazaki, 1997). The title compound,C42H72N2O5, (1), usally called 'Tinuvin144', is a famous light stabilizer of the hinderedamine class that also contains an oxidant unit of the sterically hindered phenol type (Rasberger,1980). In a former paper,we reported bis(1,2,2,6,6-pentamethylpiperidin-4-yl)butylmalonate, a key intermediate in the peparation of Tinuvin 144 (Zeng, 2006). Then Tinuvin 144 was obtained from reaction of bis(1,2,2,6,6-pentamethylpiperidin-4-yl)butylmalonate and 2,6-di-tert-butyl-4-((dimethylamino)methyl)phenol catalysized by lithium amide.

In the crystal structure both of the piperidine rings was found to adopt chair confirmations. And the phenolic hydroxyl groups are sterically hindered by the adjacent tert-butyl groups.

Related literature top

For further information on Tinuvin 144, see: Eggensperger et al. (1974, 1976). For background on hindered amine light stabilisers, see: Denisov (1991); Klemchuk & Gande (1998); Yamazaki & Seguchi (1997); Rasberger (1980). For a related structure, see: Zeng & Chen (2006).

Experimental top

A mixture of bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-butylmalonate (11.67 g,0.025 mol) and 2,6-di-tert-butyl-4-((dimethylamino)methyl)phenol (6.59 g, 0.025 mol)was dissloved in toluene (100 ml), stirred and heated to reflux. Then 0.2 g lithium amide was added and stirred for a further 4 h and extracted with water (30 ml) and then dried. The solvent was removed by vacuum evaporation at 318 K, and the product was filtered and washed with methanol (10 ml). Tinuvin 144 (15.05 g) was obtained in 87.9% yield. Colourless blocks of (I) (m.p. 420–422 K) were obtained by slow evaporation of a mixture of THF and methanol.

Refinement top

The O-bound H atom was initially located in a difference map and refined with a distant restraint of 0.82 (1) Å. All H other atoms were positioned geometrically and refined using a riding model, in the range of 0.93–0.98 Å, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
Bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate top
Crystal data top
C42H72N2O5F(000) = 1512
Mr = 685.02Dx = 1.081 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4000 reflections
a = 13.736 (6) Åθ = 2.2–21.2°
b = 18.827 (8) ŵ = 0.07 mm−1
c = 17.185 (7) ÅT = 294 K
β = 108.679 (8)°Block, colourless
V = 4210 (3) Å30.24 × 0.22 × 0.20 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer		8524 independent reflections
Radiation source: fine-focus sealed tube4124 reflections with I > 2σ(I)
graphiteRint = 0.060
ω scansθmax = 26.4°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		h = −17→12
Tmin = 0.984, Tmax = 0.986k = −23→23
23750 measured reflectionsl = −11→21
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)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0519P)2]
where P = (Fo2 + 2Fc2)/3
8524 reflections(Δ/σ)max = 0.002
460 parametersΔρmax = 0.15 e Å−3
24 restraintsΔρmin = −0.18 e Å−3
Crystal data top
C42H72N2O5V = 4210 (3) Å3
Mr = 685.02Z = 4
Monoclinic, P21/nMo Kα radiation
a = 13.736 (6) ŵ = 0.07 mm−1
b = 18.827 (8) ÅT = 294 K
c = 17.185 (7) Å0.24 × 0.22 × 0.20 mm
β = 108.679 (8)°
Data collection top
Bruker SMART CCD
diffractometer		8524 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		4124 reflections with I > 2σ(I)
Tmin = 0.984, Tmax = 0.986Rint = 0.060
23750 measured reflectionsθmax = 26.4°
Refinement top
R[F2 > 2σ(F2)] = 0.051H-atom parameters constrained
wR(F2) = 0.133Δρmax = 0.15 e Å−3
S = 1.04Δρmin = −0.18 e Å−3
8524 reflectionsAbsolute structure: ?
460 parametersFlack parameter: ?
24 restraintsRogers 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
O10.11801 (11)0.03727 (8)0.22237 (9)0.0545 (4)
O20.27568 (10)0.03307 (7)0.31285 (8)0.0450 (4)
O30.34336 (10)0.12854 (7)0.21144 (10)0.0518 (4)
O40.44526 (10)0.03948 (7)0.20033 (9)0.0472 (4)
O50.34155 (11)0.00858 (9)−0.17848 (9)0.0580 (5)
H50.40330.0170−0.16470.087*
N10.26679 (14)0.08817 (10)0.54521 (10)0.0545 (5)
N20.47991 (13)0.31688 (9)0.31576 (11)0.0480 (5)
C10.23602 (16)0.03915 (11)0.38210 (12)0.0400 (5)
H10.17120.01310.37050.048*
C20.31606 (18)0.00701 (13)0.45378 (13)0.0592 (7)
H2A0.38120.03040.46070.071*
H2B0.3239−0.04270.44230.071*
C30.2906 (2)0.01285 (14)0.53422 (14)0.0628 (7)
C40.19126 (18)0.12587 (12)0.47700 (14)0.0505 (6)
C50.22108 (18)0.11474 (11)0.39962 (13)0.0502 (6)
H5A0.16780.13480.35310.060*
H5B0.28420.14050.40540.060*
C60.3888 (3)−0.00737 (19)0.60225 (18)0.1186 (13)
H6A0.43800.03040.61010.178*
H6B0.4167−0.05000.58710.178*
H6C0.3737−0.01530.65230.178*
C70.2054 (3)−0.04052 (15)0.53448 (18)0.1022 (11)
H7A0.1872−0.03420.58350.153*
H7B0.2300−0.08810.53290.153*
H7C0.1461−0.03250.48730.153*
C80.2519 (2)0.10123 (17)0.62494 (15)0.0968 (10)
H8A0.25210.15150.63460.145*
H8B0.30650.07930.66770.145*
H8C0.18730.08150.62450.145*
C90.07875 (18)0.10554 (16)0.46096 (17)0.0844 (9)
H9A0.06700.05850.43830.127*
H9B0.03520.13850.42280.127*
H9C0.06340.10680.51160.127*
C100.2038 (3)0.20520 (14)0.49609 (18)0.0944 (10)
H10A0.17550.21630.53900.142*
H10B0.16820.23180.44770.142*
H10C0.27540.21730.51360.142*
C110.20853 (16)0.03224 (10)0.23713 (13)0.0349 (5)
C120.26231 (14)0.01955 (10)0.17326 (12)0.0310 (5)
C130.36247 (16)0.06151 (11)0.19717 (12)0.0340 (5)
C140.42714 (15)0.17905 (11)0.24358 (14)0.0462 (6)
H140.49200.16040.23970.055*
C150.43448 (17)0.19407 (12)0.33117 (14)0.0567 (7)
H15A0.45810.15150.36340.068*
H15B0.36630.20480.33320.068*
C160.50644 (18)0.25553 (13)0.37089 (16)0.0604 (7)
C170.46967 (17)0.30720 (11)0.22855 (15)0.0481 (6)
C180.39650 (16)0.24513 (11)0.19512 (13)0.0462 (6)
H18A0.32810.25850.19450.055*
H18B0.39350.23590.13890.055*
C190.61923 (19)0.23145 (15)0.3955 (2)0.1046 (12)
H19A0.63210.21000.34910.157*
H19B0.63250.19750.43940.157*
H19C0.66350.27180.41330.157*
C200.4818 (3)0.27382 (17)0.45014 (17)0.1064 (11)
H20A0.53100.30760.48170.160*
H20B0.48500.23140.48190.160*
H20C0.41400.29380.43600.160*
C210.53831 (19)0.38095 (12)0.35218 (17)0.0761 (8)
H21A0.60690.37740.34970.114*
H21B0.54070.38510.40850.114*
H21C0.50530.42210.32220.114*
C220.4174 (2)0.37260 (13)0.18116 (17)0.0826 (9)
H22A0.35870.38470.19720.124*
H22B0.39570.36270.12330.124*
H22C0.46490.41160.19310.124*
C230.5712 (2)0.29581 (15)0.20974 (19)0.0859 (9)
H23A0.61820.33350.23400.129*
H23B0.55770.29570.15140.129*
H23C0.60090.25110.23220.129*
C240.27941 (14)−0.06058 (10)0.16759 (12)0.0378 (5)
H24A0.2125−0.08320.14960.045*
H24B0.3102−0.06800.12470.045*
C250.34472 (17)−0.09926 (11)0.24357 (14)0.0513 (6)
H25A0.4141−0.08040.25970.062*
H25B0.3174−0.09050.28820.062*
C260.34825 (19)−0.17811 (13)0.23035 (16)0.0664 (7)
H26A0.3787−0.18680.18750.080*
H26B0.2786−0.19640.21140.080*
C270.4086 (2)−0.21805 (15)0.3066 (2)0.1104 (12)
H27A0.4786−0.20180.32430.166*
H27B0.4068−0.26790.29470.166*
H27C0.3789−0.20980.34930.166*
C280.19051 (14)0.04724 (11)0.08956 (11)0.0366 (5)
H28A0.12500.02300.07700.044*
H28B0.17810.09740.09500.044*
C290.23091 (14)0.03749 (11)0.01788 (12)0.0330 (5)
C300.30080 (14)0.08459 (11)0.00438 (12)0.0357 (5)
H300.32250.12270.04020.043*
C310.34042 (14)0.07772 (11)−0.06046 (12)0.0362 (5)
C320.30647 (15)0.01948 (11)−0.11208 (12)0.0378 (5)
C330.23369 (14)−0.02878 (10)−0.10275 (12)0.0350 (5)
C340.19819 (14)−0.01768 (11)−0.03675 (12)0.0367 (5)
H340.1498−0.0491−0.02900.044*
C350.41828 (15)0.13169 (11)−0.07214 (13)0.0416 (5)
C360.43759 (18)0.19175 (13)−0.00943 (15)0.0628 (7)
H36A0.37410.2158−0.01490.094*
H36B0.48590.2248−0.01890.094*
H36C0.46490.17250.04500.094*
C370.37945 (19)0.16647 (14)−0.15711 (15)0.0730 (8)
H37A0.37200.1309−0.19870.109*
H37B0.42790.2017−0.16160.109*
H37C0.31410.1885−0.16430.109*
C380.52270 (16)0.09604 (13)−0.05867 (16)0.0638 (7)
H38A0.54360.0720−0.00670.096*
H38B0.57280.1315−0.05910.096*
H38C0.51710.0623−0.10180.096*
C390.19313 (15)−0.09002 (11)−0.16316 (13)0.0431 (5)
C400.13682 (18)−0.06090 (14)−0.24902 (14)0.0654 (7)
H40A0.0782−0.0338−0.24750.098*
H40B0.1145−0.0997−0.28680.098*
H40C0.1824−0.0309−0.26650.098*
C410.28074 (18)−0.13933 (13)−0.16708 (17)0.0712 (8)
H41A0.3264−0.1137−0.18910.107*
H41B0.2525−0.1793−0.20170.107*
H41C0.3180−0.1558−0.11280.107*
C420.11634 (18)−0.13606 (13)−0.13825 (15)0.0646 (7)
H42A0.1493−0.1560−0.08490.097*
H42B0.0924−0.1737−0.17750.097*
H42C0.0591−0.1074−0.13680.097*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0375 (9)0.0868 (12)0.0430 (9)0.0038 (8)0.0183 (8)0.0003 (9)
O20.0438 (8)0.0635 (10)0.0301 (8)0.0031 (7)0.0151 (7)−0.0087 (8)
O30.0393 (8)0.0349 (9)0.0828 (12)−0.0058 (7)0.0218 (8)−0.0141 (8)
O40.0355 (8)0.0464 (9)0.0604 (10)0.0016 (7)0.0164 (8)−0.0080 (8)
O50.0559 (9)0.0840 (12)0.0400 (9)−0.0131 (9)0.0236 (8)−0.0162 (9)
N10.0652 (12)0.0677 (14)0.0288 (11)0.0087 (11)0.0125 (10)−0.0133 (10)
N20.0519 (11)0.0357 (11)0.0519 (13)−0.0088 (9)0.0105 (10)−0.0082 (10)
C10.0501 (13)0.0460 (14)0.0292 (12)0.0020 (10)0.0201 (11)−0.0068 (11)
C20.0744 (16)0.0621 (17)0.0389 (15)0.0246 (13)0.0150 (13)−0.0026 (13)
C30.0810 (18)0.0704 (19)0.0333 (14)0.0219 (15)0.0131 (14)−0.0020 (13)
C40.0655 (16)0.0506 (15)0.0399 (14)0.0085 (12)0.0234 (13)−0.0078 (12)
C50.0673 (15)0.0460 (15)0.0408 (14)0.0065 (11)0.0221 (12)−0.0012 (11)
C60.138 (3)0.148 (3)0.0490 (18)0.071 (2)0.0013 (19)0.011 (2)
C70.177 (3)0.073 (2)0.073 (2)−0.011 (2)0.064 (2)0.0078 (17)
C80.133 (3)0.116 (3)0.0400 (17)0.027 (2)0.0262 (18)−0.0164 (17)
C90.0589 (16)0.129 (3)0.070 (2)0.0144 (16)0.0262 (15)−0.0187 (18)
C100.151 (3)0.0592 (19)0.084 (2)0.0199 (18)0.055 (2)−0.0183 (17)
C110.0412 (13)0.0331 (12)0.0317 (13)−0.0006 (10)0.0134 (11)−0.0025 (10)
C120.0337 (11)0.0313 (12)0.0302 (11)−0.0002 (9)0.0134 (10)−0.0018 (9)
C130.0404 (12)0.0323 (13)0.0298 (12)0.0000 (10)0.0120 (10)−0.0014 (10)
C140.0373 (12)0.0326 (13)0.0699 (17)−0.0081 (10)0.0187 (12)−0.0096 (12)
C150.0597 (15)0.0466 (15)0.0571 (17)−0.0088 (12)0.0094 (13)0.0107 (13)
C160.0625 (16)0.0527 (16)0.0538 (17)−0.0094 (12)0.0017 (14)0.0034 (14)
C170.0561 (14)0.0350 (14)0.0571 (16)−0.0046 (11)0.0236 (13)0.0001 (12)
C180.0587 (14)0.0410 (14)0.0419 (14)−0.0037 (11)0.0201 (12)−0.0067 (11)
C190.0642 (19)0.073 (2)0.134 (3)−0.0026 (15)−0.0278 (19)0.024 (2)
C200.143 (3)0.113 (3)0.0535 (19)−0.037 (2)0.018 (2)−0.0120 (19)
C210.0805 (18)0.0462 (16)0.088 (2)−0.0164 (13)0.0086 (16)−0.0188 (15)
C220.105 (2)0.0506 (17)0.081 (2)−0.0068 (15)0.0141 (18)0.0184 (16)
C230.0838 (19)0.073 (2)0.123 (3)−0.0210 (16)0.0640 (19)−0.0103 (18)
C240.0392 (11)0.0368 (13)0.0393 (13)−0.0024 (9)0.0155 (10)−0.0049 (10)
C250.0612 (15)0.0411 (15)0.0506 (15)0.0058 (11)0.0167 (13)0.0033 (12)
C260.0808 (18)0.0451 (16)0.083 (2)0.0121 (13)0.0396 (16)0.0094 (15)
C270.122 (3)0.071 (2)0.131 (3)0.0336 (19)0.030 (2)0.043 (2)
C280.0362 (11)0.0399 (13)0.0342 (12)0.0005 (9)0.0121 (10)0.0010 (10)
C290.0332 (11)0.0382 (13)0.0267 (11)0.0016 (10)0.0083 (9)0.0044 (10)
C300.0391 (11)0.0403 (13)0.0262 (12)−0.0011 (10)0.0082 (10)−0.0013 (10)
C310.0330 (11)0.0453 (13)0.0291 (12)−0.0013 (10)0.0081 (10)0.0010 (11)
C320.0393 (12)0.0508 (14)0.0243 (12)0.0034 (10)0.0117 (10)−0.0002 (11)
C330.0350 (11)0.0375 (13)0.0293 (12)−0.0001 (10)0.0056 (10)0.0013 (10)
C340.0357 (11)0.0409 (13)0.0321 (12)−0.0027 (10)0.0088 (10)0.0055 (11)
C350.0383 (12)0.0516 (14)0.0360 (13)−0.0075 (10)0.0135 (10)−0.0006 (11)
C360.0630 (15)0.0611 (17)0.0757 (19)−0.0231 (13)0.0384 (14)−0.0153 (14)
C370.0814 (18)0.081 (2)0.0544 (17)−0.0234 (15)0.0185 (15)0.0149 (15)
C380.0458 (14)0.0762 (18)0.0735 (18)−0.0095 (13)0.0249 (13)−0.0129 (15)
C390.0428 (12)0.0423 (14)0.0402 (13)−0.0002 (11)0.0079 (11)−0.0070 (11)
C400.0672 (16)0.0757 (19)0.0423 (15)−0.0060 (14)0.0021 (13)−0.0114 (14)
C410.0646 (16)0.0589 (17)0.083 (2)0.0072 (13)0.0141 (15)−0.0181 (15)
C420.0752 (17)0.0543 (16)0.0656 (18)−0.0193 (13)0.0242 (15)−0.0134 (14)
Geometric parameters (Å, °) top
O1—C111.191 (2)C20—H20A0.9600
O2—C111.333 (2)C20—H20B0.9600
O2—C11.463 (2)C20—H20C0.9600
O3—C131.328 (2)C21—H21A0.9600
O3—C141.458 (2)C21—H21B0.9600
O4—C131.195 (2)C21—H21C0.9600
O5—C321.389 (2)C22—H22A0.9600
O5—H50.8200C22—H22B0.9600
N1—C81.470 (3)C22—H22C0.9600
N1—C41.475 (3)C23—H23A0.9600
N1—C31.481 (3)C23—H23B0.9600
N2—C161.464 (3)C23—H23C0.9600
N2—C171.471 (3)C24—C251.513 (3)
N2—C211.473 (3)C24—H24A0.9700
C1—C51.482 (3)C24—H24B0.9700
C1—C21.492 (3)C25—C261.505 (3)
C1—H10.9800C25—H25A0.9700
C2—C31.535 (3)C25—H25B0.9700
C2—H2A0.9700C26—C271.508 (4)
C2—H2B0.9700C26—H26A0.9700
C3—C61.524 (4)C26—H26B0.9700
C3—C71.543 (4)C27—H27A0.9600
C4—C51.526 (3)C27—H27B0.9600
C4—C101.527 (3)C27—H27C0.9600
C4—C91.529 (3)C28—C291.516 (3)
C5—H5A0.9700C28—H28A0.9700
C5—H5B0.9700C28—H28B0.9700
C6—H6A0.9600C29—C341.375 (3)
C6—H6B0.9600C29—C301.380 (3)
C6—H6C0.9600C30—C311.394 (3)
C7—H7A0.9600C30—H300.9300
C7—H7B0.9600C31—C321.393 (3)
C7—H7C0.9600C31—C351.534 (3)
C8—H8A0.9600C32—C331.398 (3)
C8—H8B0.9600C33—C341.386 (3)
C8—H8C0.9600C33—C391.532 (3)
C9—H9A0.9600C34—H340.9300
C9—H9B0.9600C35—C361.526 (3)
C9—H9C0.9600C35—C371.532 (3)
C10—H10A0.9600C35—C381.533 (3)
C10—H10B0.9600C36—H36A0.9600
C10—H10C0.9600C36—H36B0.9600
C11—C121.525 (3)C36—H36C0.9600
C12—C131.524 (3)C37—H37A0.9600
C12—C241.535 (3)C37—H37B0.9600
C12—C281.551 (3)C37—H37C0.9600
C14—C181.481 (3)C38—H38A0.9600
C14—C151.503 (3)C38—H38B0.9600
C14—H140.9800C38—H38C0.9600
C15—C161.533 (3)C39—C421.529 (3)
C15—H15A0.9700C39—C401.531 (3)
C15—H15B0.9700C39—C411.539 (3)
C16—C191.538 (4)C40—H40A0.9600
C16—C201.544 (4)C40—H40B0.9600
C17—C221.523 (3)C40—H40C0.9600
C17—C181.528 (3)C41—H41A0.9600
C17—C231.545 (3)C41—H41B0.9600
C18—H18A0.9700C41—H41C0.9600
C18—H18B0.9700C42—H42A0.9600
C19—H19A0.9600C42—H42B0.9600
C19—H19B0.9600C42—H42C0.9600
C19—H19C0.9600
C11—O2—C1118.27 (15)H20A—C20—H20B109.5
C13—O3—C14120.73 (15)C16—C20—H20C109.5
C32—O5—H5109.5H20A—C20—H20C109.5
C8—N1—C4112.82 (19)H20B—C20—H20C109.5
C8—N1—C3112.4 (2)N2—C21—H21A109.5
C4—N1—C3119.17 (17)N2—C21—H21B109.5
C16—N2—C17118.96 (18)H21A—C21—H21B109.5
C16—N2—C21112.47 (18)N2—C21—H21C109.5
C17—N2—C21113.32 (18)H21A—C21—H21C109.5
O2—C1—C5110.61 (17)H21B—C21—H21C109.5
O2—C1—C2105.78 (16)C17—C22—H22A109.5
C5—C1—C2109.58 (18)C17—C22—H22B109.5
O2—C1—H1110.3H22A—C22—H22B109.5
C5—C1—H1110.3C17—C22—H22C109.5
C2—C1—H1110.3H22A—C22—H22C109.5
C1—C2—C3113.23 (18)H22B—C22—H22C109.5
C1—C2—H2A108.9C17—C23—H23A109.5
C3—C2—H2A108.9C17—C23—H23B109.5
C1—C2—H2B108.9H23A—C23—H23B109.5
C3—C2—H2B108.9C17—C23—H23C109.5
H2A—C2—H2B107.7H23A—C23—H23C109.5
N1—C3—C6108.6 (2)H23B—C23—H23C109.5
N1—C3—C2107.9 (2)C25—C24—C12118.61 (17)
C6—C3—C2105.8 (2)C25—C24—H24A107.7
N1—C3—C7115.1 (2)C12—C24—H24A107.7
C6—C3—C7108.7 (2)C25—C24—H24B107.7
C2—C3—C7110.3 (2)C12—C24—H24B107.7
N1—C4—C5108.04 (18)H24A—C24—H24B107.1
N1—C4—C10107.3 (2)C26—C25—C24112.54 (19)
C5—C4—C10106.2 (2)C26—C25—H25A109.1
N1—C4—C9115.8 (2)C24—C25—H25A109.1
C5—C4—C9110.3 (2)C26—C25—H25B109.1
C10—C4—C9108.7 (2)C24—C25—H25B109.1
C1—C5—C4113.70 (18)H25A—C25—H25B107.8
C1—C5—H5A108.8C25—C26—C27113.3 (2)
C4—C5—H5A108.8C25—C26—H26A108.9
C1—C5—H5B108.8C27—C26—H26A108.9
C4—C5—H5B108.8C25—C26—H26B108.9
H5A—C5—H5B107.7C27—C26—H26B108.9
C3—C6—H6A109.5H26A—C26—H26B107.7
C3—C6—H6B109.5C26—C27—H27A109.5
H6A—C6—H6B109.5C26—C27—H27B109.5
C3—C6—H6C109.5H27A—C27—H27B109.5
H6A—C6—H6C109.5C26—C27—H27C109.5
H6B—C6—H6C109.5H27A—C27—H27C109.5
C3—C7—H7A109.5H27B—C27—H27C109.5
C3—C7—H7B109.5C29—C28—C12115.05 (15)
H7A—C7—H7B109.5C29—C28—H28A108.5
C3—C7—H7C109.5C12—C28—H28A108.5
H7A—C7—H7C109.5C29—C28—H28B108.5
H7B—C7—H7C109.5C12—C28—H28B108.5
N1—C8—H8A109.5H28A—C28—H28B107.5
N1—C8—H8B109.5C34—C29—C30117.61 (18)
H8A—C8—H8B109.5C34—C29—C28121.44 (18)
N1—C8—H8C109.5C30—C29—C28120.95 (19)
H8A—C8—H8C109.5C29—C30—C31123.05 (19)
H8B—C8—H8C109.5C29—C30—H30118.5
C4—C9—H9A109.5C31—C30—H30118.5
C4—C9—H9B109.5C32—C31—C30116.44 (18)
H9A—C9—H9B109.5C32—C31—C35122.89 (18)
C4—C9—H9C109.5C30—C31—C35120.67 (19)
H9A—C9—H9C109.5O5—C32—C31120.39 (18)
H9B—C9—H9C109.5O5—C32—C33116.58 (19)
C4—C10—H10A109.5C31—C32—C33122.98 (18)
C4—C10—H10B109.5C34—C33—C32116.60 (19)
H10A—C10—H10B109.5C34—C33—C39121.39 (18)
C4—C10—H10C109.5C32—C33—C39121.99 (18)
H10A—C10—H10C109.5C29—C34—C33123.26 (19)
H10B—C10—H10C109.5C29—C34—H34118.4
O1—C11—O2123.79 (19)C33—C34—H34118.4
O1—C11—C12124.9 (2)C36—C35—C37106.6 (2)
O2—C11—C12111.18 (17)C36—C35—C38105.98 (18)
C13—C12—C11109.16 (16)C37—C35—C38110.76 (19)
C13—C12—C24112.53 (15)C36—C35—C31111.67 (17)
C11—C12—C24108.59 (15)C37—C35—C31111.30 (17)
C13—C12—C28109.08 (15)C38—C35—C31110.38 (18)
C11—C12—C28107.70 (15)C35—C36—H36A109.5
C24—C12—C28109.66 (15)C35—C36—H36B109.5
O4—C13—O3124.26 (18)H36A—C36—H36B109.5
O4—C13—C12126.58 (19)C35—C36—H36C109.5
O3—C13—C12109.12 (17)H36A—C36—H36C109.5
O3—C14—C18106.68 (17)H36B—C36—H36C109.5
O3—C14—C15107.08 (17)C35—C37—H37A109.5
C18—C14—C15108.72 (18)C35—C37—H37B109.5
O3—C14—H14111.4H37A—C37—H37B109.5
C18—C14—H14111.4C35—C37—H37C109.5
C15—C14—H14111.4H37A—C37—H37C109.5
C14—C15—C16114.51 (19)H37B—C37—H37C109.5
C14—C15—H15A108.6C35—C38—H38A109.5
C16—C15—H15A108.6C35—C38—H38B109.5
C14—C15—H15B108.6H38A—C38—H38B109.5
C16—C15—H15B108.6C35—C38—H38C109.5
H15A—C15—H15B107.6H38A—C38—H38C109.5
N2—C16—C15108.42 (19)H38B—C38—H38C109.5
N2—C16—C19115.5 (2)C42—C39—C40106.97 (18)
C15—C16—C19110.4 (2)C42—C39—C33111.77 (18)
N2—C16—C20108.4 (2)C40—C39—C33110.21 (18)
C15—C16—C20105.6 (2)C42—C39—C41106.84 (19)
C19—C16—C20108.0 (3)C40—C39—C41109.55 (19)
N2—C17—C22108.62 (19)C33—C39—C41111.35 (17)
N2—C17—C18108.33 (17)C39—C40—H40A109.5
C22—C17—C18106.05 (19)C39—C40—H40B109.5
N2—C17—C23115.6 (2)H40A—C40—H40B109.5
C22—C17—C23107.6 (2)C39—C40—H40C109.5
C18—C17—C23110.16 (19)H40A—C40—H40C109.5
C14—C18—C17113.36 (18)H40B—C40—H40C109.5
C14—C18—H18A108.9C39—C41—H41A109.5
C17—C18—H18A108.9C39—C41—H41B109.5
C14—C18—H18B108.9H41A—C41—H41B109.5
C17—C18—H18B108.9C39—C41—H41C109.5
H18A—C18—H18B107.7H41A—C41—H41C109.5
C16—C19—H19A109.5H41B—C41—H41C109.5
C16—C19—H19B109.5C39—C42—H42A109.5
H19A—C19—H19B109.5C39—C42—H42B109.5
C16—C19—H19C109.5H42A—C42—H42B109.5
H19A—C19—H19C109.5C39—C42—H42C109.5
H19B—C19—H19C109.5H42A—C42—H42C109.5
C16—C20—H20A109.5H42B—C42—H42C109.5
C16—C20—H20B109.5
C11—O2—C1—C5−86.2 (2)C14—C15—C16—C19−77.4 (3)
C11—O2—C1—C2155.23 (18)C14—C15—C16—C20166.1 (2)
O2—C1—C2—C3176.37 (19)C16—N2—C17—C22166.47 (19)
C5—C1—C2—C357.1 (3)C21—N2—C17—C22−57.9 (2)
C8—N1—C3—C6−59.7 (3)C16—N2—C17—C1851.7 (2)
C4—N1—C3—C6165.0 (2)C21—N2—C17—C18−172.70 (17)
C8—N1—C3—C2−173.9 (2)C16—N2—C17—C23−72.5 (2)
C4—N1—C3—C250.7 (3)C21—N2—C17—C2363.1 (2)
C8—N1—C3—C762.4 (3)O3—C14—C18—C17172.24 (17)
C4—N1—C3—C7−72.9 (3)C15—C14—C18—C1757.1 (2)
C1—C2—C3—N1−52.0 (3)N2—C17—C18—C14−54.1 (2)
C1—C2—C3—C6−168.0 (2)C22—C17—C18—C14−170.6 (2)
C1—C2—C3—C774.5 (3)C23—C17—C18—C1473.2 (3)
C8—N1—C4—C5174.1 (2)C13—C12—C24—C2560.3 (2)
C3—N1—C4—C5−50.7 (3)C11—C12—C24—C25−60.6 (2)
C8—N1—C4—C1060.0 (3)C28—C12—C24—C25−178.05 (16)
C3—N1—C4—C10−164.8 (2)C12—C24—C25—C26175.83 (18)
C8—N1—C4—C9−61.7 (3)C24—C25—C26—C27−177.1 (2)
C3—N1—C4—C973.5 (3)C13—C12—C28—C2962.9 (2)
O2—C1—C5—C4−173.54 (18)C11—C12—C28—C29−178.77 (17)
C2—C1—C5—C4−57.3 (3)C24—C12—C28—C29−60.8 (2)
N1—C4—C5—C152.2 (3)C12—C28—C29—C3499.7 (2)
C10—C4—C5—C1167.1 (2)C12—C28—C29—C30−81.4 (2)
C9—C4—C5—C1−75.3 (3)C34—C29—C30—C31−1.3 (3)
C1—O2—C11—O11.2 (3)C28—C29—C30—C31179.76 (18)
C1—O2—C11—C12−175.33 (15)C29—C30—C31—C32−0.6 (3)
O1—C11—C12—C13143.1 (2)C29—C30—C31—C35−179.78 (18)
O2—C11—C12—C13−40.4 (2)C30—C31—C32—O5179.72 (18)
O1—C11—C12—C24−93.9 (2)C35—C31—C32—O5−1.1 (3)
O2—C11—C12—C2482.60 (19)C30—C31—C32—C332.4 (3)
O1—C11—C12—C2824.8 (3)C35—C31—C32—C33−178.40 (18)
O2—C11—C12—C28−158.72 (16)O5—C32—C33—C34−179.63 (17)
C14—O3—C13—O4−8.6 (3)C31—C32—C33—C34−2.2 (3)
C14—O3—C13—C12173.73 (17)O5—C32—C33—C39−0.9 (3)
C11—C12—C13—O4131.1 (2)C31—C32—C33—C39176.51 (18)
C24—C12—C13—O410.5 (3)C30—C29—C34—C331.5 (3)
C28—C12—C13—O4−111.4 (2)C28—C29—C34—C33−179.55 (18)
C11—C12—C13—O3−51.2 (2)C32—C33—C34—C290.2 (3)
C24—C12—C13—O3−171.84 (16)C39—C33—C34—C29−178.58 (18)
C28—C12—C13—O366.2 (2)C32—C31—C35—C36177.27 (19)
C13—O3—C14—C18135.29 (19)C30—C31—C35—C36−3.6 (3)
C13—O3—C14—C15−108.4 (2)C32—C31—C35—C3758.3 (3)
O3—C14—C15—C16−170.24 (18)C30—C31—C35—C37−122.5 (2)
C18—C14—C15—C16−55.3 (3)C32—C31—C35—C38−65.1 (3)
C17—N2—C16—C15−49.6 (3)C30—C31—C35—C38114.0 (2)
C21—N2—C16—C15174.4 (2)C34—C33—C39—C42−2.7 (3)
C17—N2—C16—C1974.9 (3)C32—C33—C39—C42178.66 (19)
C21—N2—C16—C19−61.1 (3)C34—C33—C39—C40116.1 (2)
C17—N2—C16—C20−163.8 (2)C32—C33—C39—C40−62.5 (2)
C21—N2—C16—C2060.3 (3)C34—C33—C39—C41−122.1 (2)
C14—C15—C16—N250.1 (3)C32—C33—C39—C4159.3 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5···O4i0.822.583.200 (3)134
Symmetry codes: (i) −x+1, −y, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5···O4i0.822.583.200 (3)134
Symmetry codes: (i) −x+1, −y, −z.
Acknowledgements top

The authors gratefully acknowledge financial support from the Start Foundation (YT07B14) and the Youth Foundation (YT08Z13) of Yantai University and the Yantai Science Development Project (2008302).

references
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