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Acta Cryst. (2009). E65, o1235    [ doi:10.1107/S1600536809016237 ]

Ethyl 6-(4-chlorophenyl)-4-(4-methoxyphenyl)-2-oxocyclohex-3-ene-1-carboxylate

H.-K. Fun, S. R. Jebas, K. S. Girish and B. Kalluraya

Abstract top

In the title compound, C22H21ClO4, the cyclohex-3-ene unit adopts an envelope conformation in both independent molecules comprising the asymmetric unit. The two benzene rings are inclined to each other at a dihedral angle of 82.03 (5)° [86.37 (5)°]. In the crystal, the molecules interact via C-H...O, C-H...Cl and C-H...[pi] interactions.

Comment top

Cyclohexenones are important intermediates in the synthesis of a wide variety of biologically active simple, condensed and bridged heterocycles. These cyclohexenones are also found to possess various types of biological activity, e.g. herbicidal (Keil et al., 1996), in vitro inhibition of human platelet cylooxygenase (Hamon et al., 1996), as an HMG-CoA reductase inhibitor (Honda, 2002), and displays anti-obesity properties (Honda, 2002). Today green chemistry plays an important role in chemical research. The large number of publications clearly indicates the development of this area of chemistry (Hoel & Nielsen, 1999; Larhed et al., 1999).

The asymmetric unit of (I) (Fig. 1) comprises of two crystallographically independent molecules (A & B) with almost similar geometries. The cyclohex-3-ene unit in both the molecules adopt an envelope conformation with puckering parameters Q = 0.5107 (18) Å, θ = 124.6 (2)° and φ = 47.7 (2)° for molecule A, and Q = 0.50 (18) Å, θ = 56.0 (2)° and φ = 231.5 (2)° for molecule B (Cremer & Pople, 1975). The two benzene rings are inclined to each other forming dihedral angles of 66.82 (6)° (C1A—C6A:C13A—C18A) in molecule A and 73.68 (5)° (C1B—C6B: C13B—C18B) in molecule B.

Globally, the crystal packing comprises layers stabilized by C—H···O and C—H···Cl contacts (Fig. 2) together with C—H···π interactions (Table 1).

Related literature top

For the biological activity of cyclohexenones, see: Hamon et al. (1996); Honda (2002); Keil et al. (1996). For green chemistry, see: Hoel & Nielsen (1999); Larhed et al. (1999). For ring puckering analysis, see: Cremer & Pople (1975). For stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

1-(p-Methoxyphenyl)-3-(p-chlorophenyl)-2-propene-1-one (0.01 mol), potassium carbonate (0.04 mol), ethyl acetoacetate (0.02 mol) were ground in a mortar using a pestle for uniform mixing. The paste formed was transferred to a 50 mL beaker and placed in a microwave oven operating at 160 W for 5 mins. The product (I) was poured into cold water, filtered, dried and recrystallized from ethanol-dioxane mixture; m. pt. = 411 - 412 K.

Refinement top

H atoms were positioned geometrically [C–H = 0.93–0.98 Å] and refined using a riding model with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(methyl C). A rotating–group model was used for the methyl groups. The maximum and minimum residual electron density peaks of 1.03 and -0.96 eÅ-3, respectively, were located 0.08 Å and 0.05 Å from the C20A and C21A atoms, respectively

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids and the atom numbering scheme.
[Figure 2] Fig. 2. The crystal packing for (I), viewed along the b axis. Dashed lines indicate C—H···O and C—H···Cl contacts.
Ethyl 6-(4-chlorophenyl)-4-(4-methoxyphenyl)-2-oxocyclohex-3-ene-1-carboxylate top
Crystal data top
C22H21ClO4F000 = 1616
Mr = 384.84Dx = 1.349 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9875 reflections
a = 11.9729 (3) Åθ = 2.7–33.0º
b = 8.1713 (2) ŵ = 0.23 mm−1
c = 39.2033 (8) ÅT = 100 K
β = 98.990 (1)ºPlate, colourless
V = 3788.31 (15) Å30.57 × 0.40 × 0.17 mm
Z = 8
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		14422 independent reflections
Radiation source: fine-focus sealed tube10971 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.043
T = 100 Kθmax = 33.2º
φ and ω scansθmin = 2.6º
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		h = −17→18
Tmin = 0.882, Tmax = 0.962k = −12→11
60118 measured reflectionsl = −60→60
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.072H-atom parameters constrained
wR(F2) = 0.180  w = 1/[σ2(Fo2) + (0.064P)2 + 2.9459P]
where P = (Fo2 + 2Fc2)/3
S = 1.16(Δ/σ)max < 0.002
14422 reflectionsΔρmax = 1.03 e Å−3
473 parametersΔρmin = −0.96 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C22H21ClO4V = 3788.31 (15) Å3
Mr = 384.84Z = 8
Monoclinic, P21/cMo Kα
a = 11.9729 (3) ŵ = 0.23 mm−1
b = 8.1713 (2) ÅT = 100 K
c = 39.2033 (8) Å0.57 × 0.40 × 0.17 mm
β = 98.990 (1)º
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		14422 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		10971 reflections with I > 2σ(I)
Tmin = 0.882, Tmax = 0.962Rint = 0.043
60118 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.072473 parameters
wR(F2) = 0.180H-atom parameters constrained
S = 1.16Δρmax = 1.03 e Å−3
14422 reflectionsΔρmin = −0.96 e Å−3
Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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
Cl1A0.76330 (4)0.14248 (6)0.969549 (11)0.02789 (11)
O1A0.45467 (10)0.75170 (17)0.66944 (3)0.0223 (2)
O2A0.94698 (12)1.01249 (18)0.84718 (3)0.0291 (3)
O3A1.04004 (14)0.7270 (2)0.89626 (4)0.0409 (4)
O4A0.92250 (12)0.85217 (18)0.92726 (3)0.0284 (3)
C1A0.56825 (14)0.6458 (2)0.75979 (4)0.0203 (3)
H10.55170.58060.77780.024*
C2A0.49553 (14)0.6428 (2)0.72817 (4)0.0202 (3)
H20.43200.57580.72520.024*
C3A0.51899 (13)0.7407 (2)0.70113 (4)0.0179 (3)
C4A0.61617 (15)0.8382 (2)0.70575 (4)0.0204 (3)
H30.63260.90310.68770.024*
C5A0.68769 (15)0.8387 (2)0.73694 (4)0.0199 (3)
H40.75250.90310.73950.024*
C6A0.66492 (13)0.7440 (2)0.76511 (4)0.0169 (3)
C7A0.73704 (14)0.7533 (2)0.79924 (4)0.0177 (3)
C8A0.81593 (15)0.8723 (2)0.80671 (4)0.0205 (3)
H50.83070.94000.78890.025*
C9A0.87892 (15)0.9002 (2)0.84112 (4)0.0220 (3)
C10A0.84923 (15)0.7906 (2)0.86985 (4)0.0220 (3)
H10A0.78410.83700.87880.026*
C11A0.81864 (15)0.6186 (2)0.85548 (4)0.0216 (3)
H11A0.88300.57870.84520.026*
C12A0.71788 (14)0.6307 (2)0.82654 (4)0.0190 (3)
H12A0.70360.52400.81590.023*
H12B0.65130.66210.83630.023*
C13A0.80016 (15)0.4985 (2)0.88364 (4)0.0218 (3)
C14A0.87730 (15)0.3722 (2)0.89192 (4)0.0228 (3)
H14A0.93800.36190.87990.027*
C15A0.86513 (15)0.2608 (2)0.91800 (4)0.0227 (3)
H15A0.91680.17600.92320.027*
C16A0.77543 (15)0.2776 (2)0.93598 (4)0.0211 (3)
C17A0.69563 (16)0.4008 (3)0.92803 (5)0.0268 (4)
H17A0.63480.41000.94000.032*
C18A0.70848 (17)0.5101 (3)0.90174 (5)0.0274 (4)
H18A0.65520.59250.89610.033*
C19A0.94980 (17)0.7852 (2)0.89875 (5)0.0250 (3)
C20A1.0027 (2)0.8377 (3)0.95884 (5)0.0350 (3)
H20A1.01110.94220.97070.042*
H20B1.07600.80470.95360.042*
C21A0.9589 (2)0.7117 (3)0.98119 (5)0.0350 (3)
H21A1.00870.70431.00280.052*
H21B0.95510.60740.96980.052*
H21C0.88470.74260.98530.052*
C22A0.35991 (15)0.6440 (3)0.66210 (5)0.0261 (4)
H22A0.32320.66100.63880.039*
H22B0.30750.66600.67770.039*
H22C0.38530.53260.66480.039*
Cl1B0.23527 (5)1.53507 (8)0.970110 (14)0.04101 (15)
O1B−0.03768 (10)0.91313 (17)0.67571 (3)0.0228 (3)
O2B0.45811 (13)0.65728 (19)0.85379 (4)0.0322 (3)
O3B0.55166 (14)0.9617 (3)0.89936 (5)0.0459 (4)
O4B0.45395 (15)0.8167 (2)0.93271 (4)0.0410 (3)
C1B0.07581 (14)1.0158 (2)0.76615 (4)0.0208 (3)
H60.05881.07960.78430.025*
C2B0.00365 (14)1.0205 (2)0.73455 (4)0.0213 (3)
H7−0.05961.08810.73170.026*
C3B0.02715 (14)0.9233 (2)0.70740 (4)0.0183 (3)
C4B0.12421 (14)0.8254 (2)0.71188 (4)0.0200 (3)
H80.14040.76070.69380.024*
C5B0.19597 (14)0.8244 (2)0.74301 (4)0.0196 (3)
H90.26100.76060.74540.023*
C6B0.17279 (13)0.9183 (2)0.77137 (4)0.0171 (3)
C7B0.24481 (13)0.9098 (2)0.80548 (4)0.0177 (3)
C8B0.32596 (15)0.7943 (2)0.81310 (4)0.0211 (3)
H100.34240.72770.79530.025*
C9B0.38899 (15)0.7684 (2)0.84758 (5)0.0233 (3)
C10B0.36130 (15)0.8793 (2)0.87657 (4)0.0230 (3)
H10B0.29990.83060.88700.028*
C11B0.32456 (15)1.0481 (2)0.86175 (4)0.0224 (3)
H11B0.38731.09290.85140.027*
C12B0.22305 (14)1.0301 (2)0.83289 (4)0.0199 (3)
H12C0.15790.99410.84280.024*
H12D0.20521.13610.82230.024*
C13B0.30004 (16)1.1681 (2)0.88921 (5)0.0238 (3)
C14B0.36628 (16)1.3074 (2)0.89537 (4)0.0249 (3)
H14B0.42541.32440.88300.030*
C15B0.34550 (17)1.4219 (3)0.91981 (5)0.0277 (4)
H15B0.38981.51560.92360.033*
C16B0.25847 (17)1.3951 (3)0.93839 (5)0.0284 (4)
C17B0.19055 (19)1.2581 (3)0.93277 (6)0.0389 (5)
H17B0.13151.24200.94520.047*
C18B0.21188 (19)1.1445 (3)0.90817 (6)0.0362 (5)
H18B0.16681.05150.90430.043*
C19B0.46667 (17)0.8930 (3)0.90359 (5)0.0275 (4)
C20B0.5512 (2)0.8290 (3)0.96065 (6)0.0410 (3)
H20C0.61710.77760.95370.049*
H20D0.56880.94290.96590.049*
C21B0.5210 (2)0.7456 (3)0.99117 (6)0.0410 (3)
H21D0.58070.76011.01040.062*
H21E0.51040.63100.98630.062*
H21F0.45230.79140.99670.062*
C22B−0.12906 (15)1.0268 (3)0.66798 (5)0.0269 (4)
H22D−0.16591.01040.64470.040*
H22E−0.10021.13640.67050.040*
H22F−0.18241.00970.68360.040*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl1A0.0339 (2)0.0278 (2)0.02181 (18)−0.00302 (18)0.00375 (15)0.00647 (16)
O1A0.0201 (6)0.0265 (7)0.0197 (5)−0.0030 (5)0.0011 (4)0.0015 (5)
O2A0.0337 (7)0.0281 (7)0.0243 (6)−0.0102 (6)0.0009 (5)−0.0009 (5)
O3A0.0383 (9)0.0536 (11)0.0294 (7)0.0118 (8)0.0007 (6)−0.0097 (7)
O4A0.0331 (7)0.0305 (8)0.0202 (6)0.0055 (6)−0.0002 (5)0.0003 (5)
C1A0.0223 (7)0.0186 (8)0.0208 (7)−0.0019 (6)0.0058 (6)0.0031 (6)
C2A0.0188 (7)0.0208 (8)0.0218 (7)−0.0027 (6)0.0053 (5)0.0007 (6)
C3A0.0181 (7)0.0171 (7)0.0189 (7)0.0018 (6)0.0042 (5)−0.0003 (5)
C4A0.0238 (8)0.0202 (8)0.0176 (7)−0.0035 (6)0.0047 (5)0.0017 (6)
C5A0.0221 (7)0.0196 (8)0.0187 (7)−0.0041 (6)0.0047 (5)−0.0004 (6)
C6A0.0187 (7)0.0151 (7)0.0175 (6)0.0002 (5)0.0047 (5)−0.0001 (5)
C7A0.0194 (7)0.0167 (7)0.0175 (6)0.0029 (6)0.0047 (5)0.0008 (5)
C8A0.0246 (8)0.0191 (8)0.0182 (7)−0.0012 (6)0.0041 (6)0.0015 (6)
C9A0.0263 (8)0.0206 (8)0.0188 (7)−0.0007 (6)0.0030 (6)−0.0007 (6)
C10A0.0254 (8)0.0204 (8)0.0202 (7)0.0028 (6)0.0041 (6)−0.0007 (6)
C11A0.0235 (8)0.0229 (9)0.0187 (7)0.0020 (6)0.0040 (6)0.0011 (6)
C12A0.0210 (7)0.0171 (8)0.0189 (7)0.0011 (6)0.0035 (5)0.0017 (6)
C13A0.0236 (8)0.0215 (8)0.0193 (7)−0.0003 (6)0.0005 (6)0.0026 (6)
C14A0.0230 (8)0.0245 (9)0.0209 (7)0.0004 (6)0.0032 (6)0.0017 (6)
C15A0.0225 (8)0.0221 (9)0.0228 (7)0.0031 (6)0.0015 (6)0.0026 (6)
C16A0.0251 (8)0.0211 (8)0.0166 (6)−0.0017 (6)0.0013 (6)0.0019 (6)
C17A0.0267 (9)0.0311 (10)0.0237 (8)0.0059 (7)0.0076 (6)0.0046 (7)
C18A0.0279 (9)0.0282 (10)0.0264 (8)0.0088 (7)0.0054 (7)0.0076 (7)
C19A0.0312 (9)0.0228 (9)0.0199 (7)0.0003 (7)0.0009 (6)0.0000 (6)
C20A0.0417 (8)0.0371 (9)0.0238 (6)−0.0014 (7)−0.0021 (5)0.0038 (6)
C21A0.0417 (8)0.0371 (9)0.0238 (6)−0.0014 (7)−0.0021 (5)0.0038 (6)
C22A0.0185 (7)0.0328 (10)0.0266 (8)−0.0043 (7)0.0025 (6)−0.0035 (7)
Cl1B0.0409 (3)0.0450 (3)0.0356 (3)0.0091 (2)0.0014 (2)−0.0205 (2)
O1B0.0202 (6)0.0274 (7)0.0204 (5)0.0026 (5)0.0024 (4)0.0002 (5)
O2B0.0327 (7)0.0336 (8)0.0290 (7)0.0127 (6)0.0011 (5)0.0021 (6)
O3B0.0327 (8)0.0601 (12)0.0425 (9)−0.0162 (8)−0.0013 (7)0.0143 (8)
O4B0.0416 (6)0.0488 (7)0.0299 (5)−0.0111 (5)−0.0030 (4)0.0040 (5)
C1B0.0216 (7)0.0197 (8)0.0218 (7)0.0028 (6)0.0058 (6)−0.0030 (6)
C2B0.0187 (7)0.0230 (8)0.0228 (7)0.0044 (6)0.0055 (6)−0.0004 (6)
C3B0.0190 (7)0.0179 (8)0.0187 (7)−0.0015 (6)0.0054 (5)0.0013 (5)
C4B0.0217 (7)0.0197 (8)0.0197 (7)0.0027 (6)0.0068 (5)−0.0009 (6)
C5B0.0212 (7)0.0182 (8)0.0202 (7)0.0034 (6)0.0059 (5)0.0004 (6)
C6B0.0182 (7)0.0150 (7)0.0187 (6)0.0006 (5)0.0049 (5)−0.0002 (5)
C7B0.0175 (7)0.0163 (7)0.0203 (7)−0.0020 (5)0.0056 (5)−0.0009 (5)
C8B0.0220 (7)0.0203 (8)0.0215 (7)0.0021 (6)0.0044 (6)−0.0007 (6)
C9B0.0217 (8)0.0230 (9)0.0252 (8)0.0004 (6)0.0035 (6)0.0007 (6)
C10B0.0239 (8)0.0230 (9)0.0222 (7)−0.0036 (6)0.0036 (6)0.0003 (6)
C11B0.0228 (8)0.0219 (8)0.0226 (7)−0.0016 (6)0.0045 (6)−0.0010 (6)
C12B0.0199 (7)0.0194 (8)0.0206 (7)0.0003 (6)0.0038 (5)−0.0036 (6)
C13B0.0247 (8)0.0241 (9)0.0220 (7)−0.0011 (7)0.0015 (6)−0.0041 (6)
C14B0.0267 (8)0.0275 (9)0.0201 (7)−0.0011 (7)0.0022 (6)−0.0012 (6)
C15B0.0313 (9)0.0242 (9)0.0258 (8)−0.0026 (7)−0.0007 (7)−0.0028 (7)
C16B0.0277 (9)0.0316 (10)0.0243 (8)0.0048 (7)−0.0005 (7)−0.0104 (7)
C17B0.0301 (10)0.0517 (15)0.0371 (11)−0.0113 (10)0.0124 (8)−0.0192 (10)
C18B0.0352 (10)0.0386 (12)0.0375 (10)−0.0153 (9)0.0137 (8)−0.0166 (9)
C19B0.0285 (9)0.0288 (10)0.0238 (8)−0.0024 (7)−0.0002 (7)0.0012 (7)
C20B0.0416 (6)0.0488 (7)0.0299 (5)−0.0111 (5)−0.0030 (4)0.0040 (5)
C21B0.0416 (6)0.0488 (7)0.0299 (5)−0.0111 (5)−0.0030 (4)0.0040 (5)
C22B0.0196 (8)0.0363 (11)0.0250 (8)0.0041 (7)0.0041 (6)0.0058 (7)
Geometric parameters (Å, °) top
Cl1A—C16A1.7412 (18)Cl1B—C16B1.7435 (19)
O1A—C3A1.358 (2)O1B—C3B1.361 (2)
O1A—C22A1.429 (2)O1B—C22B1.431 (2)
O2A—C9A1.226 (2)O2B—C9B1.227 (2)
O3A—C19A1.198 (2)O3B—C19B1.196 (3)
O4A—C19A1.330 (2)O4B—C19B1.331 (2)
O4A—C20A1.448 (2)O4B—C20B1.472 (3)
C1A—C6A1.397 (2)C1B—C2B1.396 (2)
C1A—C2A1.399 (2)C1B—C6B1.397 (2)
C1A—H10.9300C1B—H60.9300
C2A—C3A1.391 (2)C2B—C3B1.392 (2)
C2A—H20.9300C2B—H70.9300
C3A—C4A1.398 (2)C3B—C4B1.399 (2)
C4A—C5A1.379 (2)C4B—C5B1.379 (2)
C4A—H30.9300C4B—H80.9300
C5A—C6A1.410 (2)C5B—C6B1.413 (2)
C5A—H40.9300C5B—H90.9300
C6A—C7A1.477 (2)C6B—C7B1.475 (2)
C7A—C8A1.355 (2)C7B—C8B1.354 (2)
C7A—C12A1.510 (2)C7B—C12B1.509 (2)
C8A—C9A1.457 (2)C8B—C9B1.457 (2)
C8A—H50.9300C8B—H100.9300
C9A—C10A1.524 (2)C9B—C10B1.529 (3)
C10A—C19A1.520 (3)C10B—C19B1.519 (3)
C10A—C11A1.537 (3)C10B—C11B1.534 (3)
C10A—H10A0.9800C10B—H10B0.9800
C11A—C13A1.519 (2)C11B—C13B1.518 (3)
C11A—C12A1.525 (2)C11B—C12B1.533 (2)
C11A—H11A0.9800C11B—H11B0.9800
C12A—H12A0.9700C12B—H12C0.9700
C12A—H12B0.9700C12B—H12D0.9700
C13A—C14A1.389 (3)C13B—C14B1.387 (3)
C13A—C18A1.400 (3)C13B—C18B1.396 (3)
C14A—C15A1.394 (2)C14B—C15B1.389 (3)
C14A—H14A0.9300C14B—H14B0.9300
C15A—C16A1.380 (2)C15B—C16B1.379 (3)
C15A—H15A0.9300C15B—H15B0.9300
C16A—C17A1.389 (3)C16B—C17B1.381 (3)
C17A—C18A1.390 (3)C17B—C18B1.391 (3)
C17A—H17A0.9300C17B—H17B0.9300
C18A—H18A0.9300C18B—H18B0.9300
C20A—C21A1.499 (3)C20B—C21B1.470 (3)
C20A—H20A0.9700C20B—H20C0.9700
C20A—H20B0.9700C20B—H20D0.9700
C21A—H21A0.9600C21B—H21D0.9600
C21A—H21B0.9600C21B—H21E0.9600
C21A—H21C0.9600C21B—H21F0.9600
C22A—H22A0.9600C22B—H22D0.9600
C22A—H22B0.9600C22B—H22E0.9600
C22A—H22C0.9600C22B—H22F0.9600
C3A—O1A—C22A117.53 (14)C3B—O1B—C22B117.52 (14)
C19A—O4A—C20A117.88 (16)C19B—O4B—C20B115.04 (17)
C6A—C1A—C2A121.93 (15)C2B—C1B—C6B122.08 (15)
C6A—C1A—H1119.0C2B—C1B—H6119.0
C2A—C1A—H1119.0C6B—C1B—H6119.0
C3A—C2A—C1A119.54 (16)C3B—C2B—C1B119.46 (16)
C3A—C2A—H2120.2C3B—C2B—H7120.3
C1A—C2A—H2120.2C1B—C2B—H7120.3
O1A—C3A—C2A125.56 (15)O1B—C3B—C2B125.33 (15)
O1A—C3A—C4A114.96 (14)O1B—C3B—C4B115.09 (15)
C2A—C3A—C4A119.47 (15)C2B—C3B—C4B119.58 (15)
C5A—C4A—C3A120.34 (15)C5B—C4B—C3B120.34 (15)
C5A—C4A—H3119.8C5B—C4B—H8119.8
C3A—C4A—H3119.8C3B—C4B—H8119.8
C4A—C5A—C6A121.60 (16)C4B—C5B—C6B121.43 (15)
C4A—C5A—H4119.2C4B—C5B—H9119.3
C6A—C5A—H4119.2C6B—C5B—H9119.3
C1A—C6A—C5A117.10 (15)C1B—C6B—C5B117.08 (15)
C1A—C6A—C7A121.23 (14)C1B—C6B—C7B120.96 (14)
C5A—C6A—C7A121.62 (15)C5B—C6B—C7B121.92 (15)
C8A—C7A—C6A121.44 (15)C8B—C7B—C6B122.04 (15)
C8A—C7A—C12A120.09 (15)C8B—C7B—C12B119.66 (15)
C6A—C7A—C12A118.42 (14)C6B—C7B—C12B118.25 (14)
C7A—C8A—C9A123.66 (15)C7B—C8B—C9B123.75 (16)
C7A—C8A—H5118.2C7B—C8B—H10118.1
C9A—C8A—H5118.2C9B—C8B—H10118.1
O2A—C9A—C8A121.92 (16)O2B—C9B—C8B121.78 (17)
O2A—C9A—C10A121.42 (15)O2B—C9B—C10B120.58 (16)
C8A—C9A—C10A116.49 (15)C8B—C9B—C10B117.54 (16)
C19A—C10A—C9A108.61 (15)C19B—C10B—C9B107.99 (15)
C19A—C10A—C11A111.23 (15)C19B—C10B—C11B110.80 (15)
C9A—C10A—C11A109.63 (14)C9B—C10B—C11B109.50 (14)
C19A—C10A—H10A109.1C19B—C10B—H10B109.5
C9A—C10A—H10A109.1C9B—C10B—H10B109.5
C11A—C10A—H10A109.1C11B—C10B—H10B109.5
C13A—C11A—C12A113.23 (15)C13B—C11B—C12B111.51 (15)
C13A—C11A—C10A112.21 (14)C13B—C11B—C10B112.82 (15)
C12A—C11A—C10A109.22 (14)C12B—C11B—C10B109.90 (15)
C13A—C11A—H11A107.3C13B—C11B—H11B107.5
C12A—C11A—H11A107.3C12B—C11B—H11B107.5
C10A—C11A—H11A107.3C10B—C11B—H11B107.5
C7A—C12A—C11A112.34 (14)C7B—C12B—C11B112.52 (14)
C7A—C12A—H12A109.1C7B—C12B—H12C109.1
C11A—C12A—H12A109.1C11B—C12B—H12C109.1
C7A—C12A—H12B109.1C7B—C12B—H12D109.1
C11A—C12A—H12B109.1C11B—C12B—H12D109.1
H12A—C12A—H12B107.9H12C—C12B—H12D107.8
C14A—C13A—C18A118.50 (16)C14B—C13B—C18B118.69 (17)
C14A—C13A—C11A118.87 (16)C14B—C13B—C11B119.00 (16)
C18A—C13A—C11A122.63 (16)C18B—C13B—C11B122.30 (17)
C13A—C14A—C15A121.00 (17)C13B—C14B—C15B120.91 (18)
C13A—C14A—H14A119.5C13B—C14B—H14B119.5
C15A—C14A—H14A119.5C15B—C14B—H14B119.5
C16A—C15A—C14A119.22 (17)C16B—C15B—C14B119.28 (19)
C16A—C15A—H15A120.4C16B—C15B—H15B120.4
C14A—C15A—H15A120.4C14B—C15B—H15B120.4
C15A—C16A—C17A121.35 (16)C15B—C16B—C17B121.28 (18)
C15A—C16A—Cl1A119.08 (14)C15B—C16B—Cl1B119.37 (16)
C17A—C16A—Cl1A119.57 (14)C17B—C16B—Cl1B119.35 (16)
C16A—C17A—C18A118.69 (17)C16B—C17B—C18B119.0 (2)
C16A—C17A—H17A120.7C16B—C17B—H17B120.5
C18A—C17A—H17A120.7C18B—C17B—H17B120.5
C17A—C18A—C13A121.22 (17)C17B—C18B—C13B120.9 (2)
C17A—C18A—H18A119.4C17B—C18B—H18B119.6
C13A—C18A—H18A119.4C13B—C18B—H18B119.6
O3A—C19A—O4A125.08 (17)O3B—C19B—O4B123.55 (18)
O3A—C19A—C10A124.77 (17)O3B—C19B—C10B124.74 (18)
O4A—C19A—C10A110.14 (16)O4B—C19B—C10B111.70 (17)
O4A—C20A—C21A108.05 (18)C21B—C20B—O4B107.91 (19)
O4A—C20A—H20A110.1C21B—C20B—H20C110.1
C21A—C20A—H20A110.1O4B—C20B—H20C110.1
O4A—C20A—H20B110.1C21B—C20B—H20D110.1
C21A—C20A—H20B110.1O4B—C20B—H20D110.1
H20A—C20A—H20B108.4H20C—C20B—H20D108.4
C20A—C21A—H21A109.5C20B—C21B—H21D109.5
C20A—C21A—H21B109.5C20B—C21B—H21E109.5
H21A—C21A—H21B109.5H21D—C21B—H21E109.5
C20A—C21A—H21C109.5C20B—C21B—H21F109.5
H21A—C21A—H21C109.5H21D—C21B—H21F109.5
H21B—C21A—H21C109.5H21E—C21B—H21F109.5
O1A—C22A—H22A109.5O1B—C22B—H22D109.5
O1A—C22A—H22B109.5O1B—C22B—H22E109.5
H22A—C22A—H22B109.5H22D—C22B—H22E109.5
O1A—C22A—H22C109.5O1B—C22B—H22F109.5
H22A—C22A—H22C109.5H22D—C22B—H22F109.5
H22B—C22A—H22C109.5H22E—C22B—H22F109.5
C6A—C1A—C2A—C3A−0.4 (3)C6B—C1B—C2B—C3B1.2 (3)
C22A—O1A—C3A—C2A−5.5 (2)C22B—O1B—C3B—C2B8.7 (2)
C22A—O1A—C3A—C4A174.43 (15)C22B—O1B—C3B—C4B−171.47 (15)
C1A—C2A—C3A—O1A−178.75 (16)C1B—C2B—C3B—O1B178.15 (16)
C1A—C2A—C3A—C4A1.3 (3)C1B—C2B—C3B—C4B−1.6 (3)
O1A—C3A—C4A—C5A179.41 (16)O1B—C3B—C4B—C5B−179.46 (16)
C2A—C3A—C4A—C5A−0.6 (3)C2B—C3B—C4B—C5B0.4 (3)
C3A—C4A—C5A—C6A−0.9 (3)C3B—C4B—C5B—C6B1.4 (3)
C2A—C1A—C6A—C5A−1.0 (3)C2B—C1B—C6B—C5B0.5 (3)
C2A—C1A—C6A—C7A176.27 (16)C2B—C1B—C6B—C7B−177.18 (16)
C4A—C5A—C6A—C1A1.7 (3)C4B—C5B—C6B—C1B−1.8 (3)
C4A—C5A—C6A—C7A−175.58 (16)C4B—C5B—C6B—C7B175.83 (16)
C1A—C6A—C7A—C8A−165.71 (16)C1B—C6B—C7B—C8B167.12 (17)
C5A—C6A—C7A—C8A11.5 (2)C5B—C6B—C7B—C8B−10.5 (3)
C1A—C6A—C7A—C12A11.8 (2)C1B—C6B—C7B—C12B−10.4 (2)
C5A—C6A—C7A—C12A−171.04 (15)C5B—C6B—C7B—C12B172.03 (15)
C6A—C7A—C8A—C9A171.75 (16)C6B—C7B—C8B—C9B−171.91 (16)
C12A—C7A—C8A—C9A−5.7 (3)C12B—C7B—C8B—C9B5.5 (3)
C7A—C8A—C9A—O2A−177.50 (18)C7B—C8B—C9B—O2B176.40 (18)
C7A—C8A—C9A—C10A−2.1 (3)C7B—C8B—C9B—C10B−0.2 (3)
O2A—C9A—C10A—C19A−28.0 (2)O2B—C9B—C10B—C19B31.1 (2)
C8A—C9A—C10A—C19A156.65 (16)C8B—C9B—C10B—C19B−152.28 (17)
O2A—C9A—C10A—C11A−149.68 (18)O2B—C9B—C10B—C11B151.80 (18)
C8A—C9A—C10A—C11A34.9 (2)C8B—C9B—C10B—C11B−31.5 (2)
C19A—C10A—C11A—C13A53.8 (2)C19B—C10B—C11B—C13B−58.7 (2)
C9A—C10A—C11A—C13A173.98 (15)C9B—C10B—C11B—C13B−177.67 (15)
C19A—C10A—C11A—C12A−179.76 (14)C19B—C10B—C11B—C12B176.23 (14)
C9A—C10A—C11A—C12A−59.61 (18)C9B—C10B—C11B—C12B57.21 (18)
C8A—C7A—C12A—C11A−20.7 (2)C8B—C7B—C12B—C11B21.9 (2)
C6A—C7A—C12A—C11A161.77 (14)C6B—C7B—C12B—C11B−160.50 (15)
C13A—C11A—C12A—C7A178.76 (14)C13B—C11B—C12B—C7B−179.27 (15)
C10A—C11A—C12A—C7A52.94 (18)C10B—C11B—C12B—C7B−53.39 (19)
C12A—C11A—C13A—C14A124.12 (18)C12B—C11B—C13B—C14B−119.08 (18)
C10A—C11A—C13A—C14A−111.67 (19)C10B—C11B—C13B—C14B116.67 (19)
C12A—C11A—C13A—C18A−56.1 (2)C12B—C11B—C13B—C18B59.9 (2)
C10A—C11A—C13A—C18A68.1 (2)C10B—C11B—C13B—C18B−64.3 (2)
C18A—C13A—C14A—C15A−1.0 (3)C18B—C13B—C14B—C15B−0.2 (3)
C11A—C13A—C14A—C15A178.80 (16)C11B—C13B—C14B—C15B178.82 (17)
C13A—C14A—C15A—C16A−0.6 (3)C13B—C14B—C15B—C16B0.7 (3)
C14A—C15A—C16A—C17A1.6 (3)C14B—C15B—C16B—C17B−1.0 (3)
C14A—C15A—C16A—Cl1A−177.76 (14)C14B—C15B—C16B—Cl1B177.82 (15)
C15A—C16A—C17A—C18A−1.1 (3)C15B—C16B—C17B—C18B0.9 (4)
Cl1A—C16A—C17A—C18A178.31 (16)Cl1B—C16B—C17B—C18B−178.01 (19)
C16A—C17A—C18A—C13A−0.5 (3)C16B—C17B—C18B—C13B−0.3 (4)
C14A—C13A—C18A—C17A1.5 (3)C14B—C13B—C18B—C17B0.0 (3)
C11A—C13A—C18A—C17A−178.23 (18)C11B—C13B—C18B—C17B−179.0 (2)
C20A—O4A—C19A—O3A−7.5 (3)C20B—O4B—C19B—O3B2.9 (3)
C20A—O4A—C19A—C10A171.64 (17)C20B—O4B—C19B—C10B−178.08 (19)
C9A—C10A—C19A—O3A−65.2 (3)C9B—C10B—C19B—O3B68.3 (3)
C11A—C10A—C19A—O3A55.6 (3)C11B—C10B—C19B—O3B−51.6 (3)
C9A—C10A—C19A—O4A115.70 (17)C9B—C10B—C19B—O4B−110.75 (19)
C11A—C10A—C19A—O4A−123.55 (17)C11B—C10B—C19B—O4B129.32 (18)
C19A—O4A—C20A—C21A−105.0 (2)C19B—O4B—C20B—C21B177.3 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C11A—H11A···O1Bi0.982.533.492 (2)167
C11B—H11B···O1Aii0.982.533.501 (2)170
C12A—H12B···O2B0.972.513.450 (2)162
C12B—H12C···O2Aiii0.972.563.441 (2)151
C15B—H15B···O4Biv0.932.593.485 (3)163
C20B—H20D···Cl1Aiv0.972.833.585 (2)136
C22A—H22A···Cg1ii0.972.833.666 (2)146
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2; (iii) x−1, y, z; (iv) x, y+1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C11A—H11A···O1Bi0.982.533.492 (2)167
C11B—H11B···O1Aii0.982.533.501 (2)170
C12A—H12B···O2B0.972.513.450 (2)162
C12B—H12C···O2Aiii0.972.563.441 (2)151
C15B—H15B···O4Biv0.932.593.485 (3)163
C20B—H20D···Cl1Aiv0.972.833.585 (2)136
C22A—H22A···Cg1ii0.972.833.666 (2)146
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2; (iii) x−1, y, z; (iv) x, y+1, z.
Acknowledgements top

HKF and SRJ thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SRJ thanks Universiti Sains Malaysia for a post–doctoral research fellowship. HKF also thanks Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

references
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