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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o1822.
Published online 2009 July 11. doi:  10.1107/S1600536809025987
PMCID: PMC2977202

2-Bromo­beclometasone dipropionate

Abstract

In the crystal structure of 2-bromo­beclometasone dipropionate [systematic name: (8S,9R,10S,11S,13S,14S,16S,17R)-2-bromo-9α-chloro-11-hydr­oxy-10,13,16-trimethyl-3-oxo-17-[2-(propion­yloxy)acet­yl]-6,7,8,9,10,11,12,13,14,15,16,17-dodeca­hydro-3H-cyclo­penta­[a]phenanthren-17-yl propionate], C28H36BrClO7, the six-membered ring with the 1,4-diene-3-one composition is planar (r.m.s. deviations = 0.03 and 0.04 Å for the two independent mol­ecules), whereas the remaining six-membered rings have chair conformations. Each of the independent mol­ecules self-associates via O—H(...)Opropionate hydrogen bonding, generating a supra­molecular chain running along the b axis. The crystal is twinned, with the monoclinic unit cell emulating an orthorhomic crystal system; the major twin component constitutes approximately 60%.

Related literature

For the NMR and crystal structure of the asthma drug beclometasone dipropionate monohydrate, see: Othman et al. (2008 [triangle]); Duax et al. (1981 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1822-scheme1.jpg

Experimental

Crystal data

  • C28H36BrClO7
  • M r = 599.93
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1822-efi1.jpg
  • a = 12.0999 (3) Å
  • b = 13.8673 (3) Å
  • c = 16.7971 (4) Å
  • β = 90.106 (1)°
  • V = 2818.4 (1) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.60 mm−1
  • T = 140 K
  • 0.22 × 0.11 × 0.02 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.642, T max = 0.746 (expected range = 0.834–0.969)
  • 23151 measured reflections
  • 12754 independent reflections
  • 9841 reflections with I > 2σ(I)
  • R int = 0.045

Refinement

  • R[F 2 > 2σ(F 2)] = 0.046
  • wR(F 2) = 0.086
  • S = 0.94
  • 12754 reflections
  • 680 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.61 e Å−3
  • Δρmin = −0.52 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 6028 Friedel pairs
  • Flack parameter: 0.001 (7)

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809025987/tk2487sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809025987/tk2487Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank the University of Malaya for supporting this study.

supplementary crystallographic information

Experimental

The synthesis of the compound is described in a 1988 study commissioned by the Glaxo company (now called Glaxo Smith Kline), External Report No. WAP/88/007.

The brominated compound was isolated from the mother liquor of the first crystallization of beclomethasone dipropionate (10 g). This was dissolved in hexane:ethyl acetate (8:1 v/v) and eluted by flash-column silica gel chromatography with nitrogen at 20 psi. This procedure was repeated for other batches to accumulate more material. The combined fractions were further fractioniated on fresh silica gel. One of the fractions (162 mg) yielded crystals that were recrystallized from hexane:ethyl acetate (3:1 v/v) (47 mg); 490–491 K. Elemental analysis: Calc. for C28H36BrClO7: C 56.19, H 6.02, Br 13.21, Cl, 5.85%. Found: C 56.03, H 6.12, Br 12.97, Cl, 5.76% . MS+. 599.

Refinement

Hydrogen atoms were placed at calculated positions (C–H 0.95–1.00 Å, O–H 0.82 Å) and were treated as riding on their parent carbon atoms, with U(H) set to 1.2–1.5 times Ueq(C,O).

The monoclinic unit cell emulates an orthorhombic unit cell as the β-angle is nearly a right angle. The twin law (-1 0 0 0 -1 0 0 0 1) showed that the major twin component is 60%.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of one independent molecule of C28H36BrClO7 at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.
Fig. 2.
Thermal ellipsoid plot (Barbour, 2001) of the second independent molecule of C28H36BrClO7 at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C28H36BrClO7F(000) = 1248
Mr = 599.93Dx = 1.414 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 4369 reflections
a = 12.0999 (3) Åθ = 2.5–22.4°
b = 13.8673 (3) ŵ = 1.60 mm1
c = 16.7971 (4) ÅT = 140 K
β = 90.106 (1)°Plate, colorless
V = 2818.4 (1) Å30.22 × 0.11 × 0.02 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer12754 independent reflections
Radiation source: fine-focus sealed tube9841 reflections with I > 2σ(I)
graphiteRint = 0.045
ω scansθmax = 27.5°, θmin = 1.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −15→15
Tmin = 0.642, Tmax = 0.746k = −17→17
23151 measured reflectionsl = −21→21

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.086w = 1/[σ2(Fo2) + (0.0055P)2] where P = (Fo2 + 2Fc2)/3
S = 0.94(Δ/σ)max = 0.001
12754 reflectionsΔρmax = 0.61 e Å3
680 parametersΔρmin = −0.52 e Å3
1 restraintAbsolute structure: Flack (1983), 6028 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.001 (7)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Br10.54075 (6)0.49998 (4)0.19693 (4)0.04545 (18)
Br20.47284 (6)0.38183 (4)0.69368 (4)0.04703 (18)
Cl10.31003 (12)0.21093 (9)0.14232 (8)0.0266 (3)
Cl20.67988 (12)0.69926 (9)0.65968 (7)0.0273 (3)
O10.6876 (4)0.3240 (3)0.2194 (3)0.0657 (16)
O20.2810 (3)0.3459 (2)−0.0630 (2)0.0241 (9)
H20.23470.3857−0.07690.036*
O3−0.0895 (3)0.1241 (3)−0.1469 (2)0.0288 (9)
O4−0.2209 (3)0.2617 (3)−0.0927 (2)0.0288 (9)
O5−0.0790 (3)0.3584 (3)−0.1263 (2)0.0286 (9)
O6−0.0029 (3)0.1104 (2)0.05595 (19)0.0188 (8)
O7−0.1480 (3)0.0108 (2)0.0430 (2)0.0258 (8)
O80.3216 (5)0.5484 (4)0.7329 (3)0.0651 (15)
O90.7133 (3)0.5636 (2)0.4572 (2)0.0234 (9)
H90.74950.51430.45070.035*
O101.0599 (3)0.8016 (2)0.3561 (2)0.0280 (9)
O111.2091 (3)0.6755 (3)0.4091 (2)0.0289 (9)
O121.0782 (3)0.5674 (3)0.3757 (3)0.0324 (10)
O130.9919 (3)0.8182 (2)0.56103 (18)0.0181 (8)
O141.1285 (3)0.9212 (2)0.5346 (2)0.0237 (8)
C10.4654 (4)0.3656 (4)0.0826 (3)0.0243 (12)
H10.41460.41540.06930.029*
C20.5368 (5)0.3808 (4)0.1419 (3)0.0327 (14)
C30.6175 (5)0.3074 (4)0.1685 (4)0.0369 (16)
C40.6101 (5)0.2152 (4)0.1282 (4)0.0350 (14)
H40.65840.16490.14460.042*
C50.5382 (5)0.1970 (4)0.0688 (3)0.0288 (13)
C60.4617 (4)0.2731 (3)0.0360 (3)0.0223 (12)
C70.5041 (5)0.2971 (4)−0.0489 (3)0.0300 (14)
H7A0.58480.3024−0.04800.045*
H7B0.47210.3584−0.06660.045*
H7C0.48210.2457−0.08570.045*
C80.3392 (4)0.2315 (3)0.0368 (3)0.0195 (11)
C90.3330 (4)0.1346 (3)−0.0066 (3)0.0200 (12)
H9a0.35330.1462−0.06350.024*
C100.4151 (4)0.0613 (3)0.0274 (4)0.0253 (13)
H10A0.39250.04410.08220.030*
H10B0.41280.0020−0.00530.030*
C110.5332 (5)0.1001 (4)0.0290 (4)0.0338 (14)
H11A0.58130.05420.05810.041*
H11B0.56120.1057−0.02610.041*
C120.2493 (4)0.3049 (3)0.0116 (3)0.0179 (11)
H120.24700.35770.05210.021*
C130.1328 (4)0.2587 (3)0.0063 (3)0.0184 (11)
H13A0.10600.24600.06090.022*
H13B0.08170.3056−0.01860.022*
C140.1283 (4)0.1650 (3)−0.0409 (3)0.0159 (11)
C150.1439 (4)0.1828 (4)−0.1301 (3)0.0227 (12)
H15A0.22170.1975−0.14090.034*
H15B0.09790.2374−0.14680.034*
H15C0.12220.1250−0.15990.034*
C160.2154 (4)0.0949 (3)−0.0053 (3)0.0168 (11)
H160.19550.08580.05190.020*
C170.1884 (4)0.0007 (4)−0.0474 (3)0.0224 (11)
H17A0.2214−0.0548−0.01890.027*
H17B0.21600.0013−0.10280.027*
C180.0620 (4)−0.0044 (4)−0.0457 (3)0.0165 (10)
H180.0425−0.04190.00310.020*
C190.0216 (4)0.1023 (3)−0.0301 (3)0.0180 (11)
C200.0102 (5)−0.0589 (3)−0.1159 (3)0.0266 (13)
H20A0.0446−0.1226−0.12060.040*
H20B0.0222−0.0224−0.16510.040*
H20C−0.0693−0.0664−0.10680.040*
C21−0.0750 (4)0.1418 (3)−0.0776 (3)0.0213 (12)
C22−0.1497 (4)0.2152 (4)−0.0356 (3)0.0247 (12)
H22A−0.19490.18200.00510.030*
H22B−0.10360.2642−0.00830.030*
C23−0.1728 (5)0.3310 (3)−0.1386 (3)0.0238 (12)
C24−0.2494 (5)0.3645 (4)−0.2015 (4)0.0364 (14)
H24A−0.32420.3715−0.17840.044*
H24B−0.25350.3147−0.24360.044*
C25−0.2165 (6)0.4583 (4)−0.2385 (4)0.0375 (15)
H25A−0.26780.4741−0.28180.056*
H25B−0.14140.4530−0.25980.056*
H25C−0.21870.5094−0.19820.056*
C26−0.0847 (4)0.0556 (3)0.0855 (3)0.0206 (12)
C27−0.0835 (5)0.0551 (4)0.1745 (3)0.0284 (13)
H27A−0.03490.00210.19280.034*
H27B−0.15910.04110.19370.034*
C28−0.0439 (6)0.1494 (4)0.2124 (3)0.0505 (17)
H28A−0.04880.14440.27040.076*
H28B−0.09050.20270.19390.076*
H28C0.03300.16150.19700.076*
C290.5366 (5)0.5327 (4)0.5906 (3)0.0254 (13)
H290.59060.48740.57370.030*
C300.4678 (5)0.5071 (5)0.6483 (3)0.0330 (14)
C310.3842 (6)0.5721 (5)0.6799 (4)0.0439 (18)
C320.3840 (5)0.6696 (5)0.6466 (4)0.0449 (18)
H320.33300.71520.66720.054*
C330.4528 (5)0.6975 (4)0.5883 (3)0.0287 (13)
C340.5335 (4)0.6289 (3)0.5506 (3)0.0212 (12)
C350.4887 (5)0.6095 (4)0.4648 (3)0.0274 (13)
H35A0.41280.58500.46800.041*
H35B0.53560.56160.43840.041*
H35C0.48960.66960.43420.041*
C360.6517 (4)0.6758 (4)0.5533 (3)0.0198 (11)
C370.7467 (4)0.6092 (3)0.5292 (3)0.0198 (12)
H370.75430.55830.57100.024*
C380.8584 (4)0.6604 (3)0.5215 (3)0.0192 (11)
H38A0.88630.67620.57540.023*
H38B0.91190.61580.49650.023*
C390.8529 (4)0.7532 (3)0.4722 (3)0.0168 (11)
C400.8294 (5)0.7317 (4)0.3834 (3)0.0240 (12)
H40A0.75320.70880.37740.036*
H40B0.88060.68190.36450.036*
H40C0.83960.79060.35210.036*
C410.7662 (4)0.8197 (3)0.5097 (3)0.0190 (11)
H410.78840.83060.56640.023*
C420.6501 (4)0.7747 (3)0.5103 (3)0.0223 (12)
H420.62820.76290.45370.027*
C430.5653 (5)0.8430 (4)0.5463 (4)0.0277 (13)
H43A0.59060.86270.59990.033*
H43B0.56060.90170.51290.033*
C440.4498 (5)0.7981 (4)0.5531 (4)0.0349 (15)
H44A0.40300.83990.58690.042*
H44B0.41560.79530.49950.042*
C450.7821 (4)0.9145 (3)0.4656 (3)0.0238 (12)
H45A0.74990.96900.49580.029*
H45B0.74770.91210.41210.029*
C460.9079 (4)0.9239 (3)0.4597 (3)0.0218 (12)
H460.93130.96600.50500.026*
C470.9425 (5)0.9759 (4)0.3841 (3)0.0341 (14)
H47A0.90901.04020.38300.051*
H47B0.91770.93900.33760.051*
H47C1.02320.98200.38300.051*
C480.9565 (4)0.8212 (3)0.4772 (3)0.0182 (11)
C491.0518 (5)0.7834 (3)0.4268 (3)0.0249 (12)
C501.1341 (5)0.7155 (4)0.4666 (3)0.0272 (12)
H50A1.17640.75120.50760.033*
H50B1.09360.66270.49340.033*
C511.1673 (5)0.6009 (4)0.3650 (3)0.0229 (12)
C521.2503 (5)0.5698 (4)0.3026 (4)0.0332 (14)
H52A1.32520.57040.32640.040*
H52B1.24950.61680.25830.040*
C531.2268 (5)0.4703 (4)0.2700 (4)0.0389 (16)
H53A1.28650.45110.23410.058*
H53B1.15660.47120.24070.058*
H53C1.22180.42420.31410.058*
C541.0753 (4)0.8780 (4)0.5826 (3)0.0223 (11)
C551.0950 (4)0.8777 (4)0.6712 (3)0.0205 (11)
H55A1.13450.81790.68630.025*
H55B1.02300.87810.69910.025*
C561.1626 (4)0.9647 (3)0.6976 (3)0.0291 (12)
H56A1.17510.96150.75520.044*
H56B1.12241.02400.68470.044*
H56C1.23390.96460.67000.044*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0424 (4)0.0454 (3)0.0485 (4)−0.0172 (3)−0.0005 (3)−0.0155 (4)
Br20.0408 (4)0.0540 (4)0.0462 (4)−0.0229 (3)−0.0093 (3)0.0218 (4)
Cl10.0282 (7)0.0265 (7)0.0252 (7)−0.0061 (6)−0.0008 (5)0.0004 (6)
Cl20.0296 (7)0.0288 (7)0.0235 (6)−0.0042 (6)−0.0012 (6)−0.0027 (6)
O10.061 (3)0.051 (3)0.085 (4)−0.027 (3)−0.052 (3)0.023 (3)
O20.018 (2)0.0180 (18)0.036 (2)0.0011 (15)0.0028 (16)0.0126 (16)
O30.027 (2)0.033 (2)0.027 (2)0.0012 (17)−0.0083 (17)−0.0044 (18)
O40.018 (2)0.0268 (19)0.042 (2)0.0001 (16)−0.0097 (17)0.0128 (18)
O50.027 (2)0.029 (2)0.030 (2)−0.0105 (16)−0.0026 (17)0.0069 (17)
O60.023 (2)0.0160 (16)0.0180 (17)−0.0030 (14)0.0040 (14)−0.0002 (14)
O70.024 (2)0.0196 (18)0.033 (2)−0.0063 (16)−0.0001 (16)0.0000 (17)
O80.066 (4)0.075 (3)0.054 (3)−0.031 (3)0.035 (3)−0.007 (3)
O90.020 (2)0.0162 (18)0.034 (2)0.0022 (15)−0.0036 (17)−0.0077 (17)
O100.027 (2)0.0278 (19)0.029 (2)−0.0021 (16)0.0040 (17)0.0047 (17)
O110.016 (2)0.0262 (19)0.044 (2)−0.0025 (16)0.0029 (17)−0.0063 (18)
O120.022 (2)0.030 (2)0.045 (3)−0.0079 (17)0.0014 (19)−0.0019 (19)
O130.0177 (19)0.0170 (17)0.0195 (17)−0.0057 (14)−0.0020 (14)0.0042 (14)
O140.027 (2)0.0197 (17)0.024 (2)−0.0121 (16)0.0016 (17)0.0034 (16)
C10.021 (3)0.021 (3)0.031 (3)−0.006 (3)0.004 (2)−0.001 (2)
C20.036 (3)0.030 (3)0.032 (3)−0.019 (3)−0.002 (3)0.004 (3)
C30.031 (3)0.036 (3)0.044 (4)−0.026 (3)−0.020 (3)0.019 (3)
C40.023 (3)0.029 (3)0.053 (4)−0.010 (3)−0.006 (3)0.011 (3)
C50.018 (3)0.027 (3)0.042 (3)0.003 (3)0.001 (3)0.004 (3)
C60.016 (3)0.021 (3)0.029 (3)0.003 (2)0.000 (2)0.002 (2)
C70.021 (3)0.033 (3)0.036 (3)−0.001 (2)0.008 (3)0.005 (3)
C80.021 (3)0.016 (2)0.021 (3)0.001 (2)0.000 (2)−0.001 (2)
C90.021 (3)0.013 (2)0.026 (3)0.003 (2)0.001 (2)−0.002 (2)
C100.018 (3)0.013 (2)0.045 (3)0.003 (2)0.000 (3)−0.001 (3)
C110.029 (3)0.025 (3)0.047 (4)0.010 (3)−0.004 (3)0.005 (3)
C120.011 (3)0.011 (2)0.032 (3)0.0002 (19)0.003 (2)−0.005 (2)
C130.016 (3)0.013 (2)0.026 (3)0.001 (2)−0.002 (2)−0.002 (2)
C140.011 (2)0.013 (2)0.024 (3)0.0014 (19)−0.001 (2)0.000 (2)
C150.025 (3)0.020 (3)0.023 (3)−0.002 (2)0.004 (2)−0.003 (2)
C160.017 (3)0.008 (2)0.026 (3)0.0011 (19)0.001 (2)0.004 (2)
C170.033 (3)0.010 (2)0.025 (3)0.000 (2)0.001 (2)0.000 (2)
C180.018 (3)0.017 (2)0.014 (2)0.000 (2)0.0024 (19)0.003 (2)
C190.025 (3)0.017 (2)0.012 (2)−0.004 (2)−0.004 (2)−0.0023 (19)
C200.030 (3)0.021 (3)0.029 (3)−0.004 (2)0.003 (2)−0.004 (2)
C210.016 (3)0.020 (3)0.028 (3)−0.007 (2)−0.001 (2)0.000 (2)
C220.022 (3)0.020 (3)0.033 (3)0.003 (2)0.000 (2)0.005 (2)
C230.028 (3)0.017 (2)0.026 (3)0.001 (2)0.001 (2)−0.002 (2)
C240.029 (3)0.040 (4)0.041 (3)0.003 (3)−0.005 (3)0.001 (3)
C250.043 (4)0.032 (3)0.037 (3)0.003 (3)−0.001 (3)0.012 (3)
C260.017 (3)0.014 (3)0.031 (3)0.005 (2)0.001 (2)0.005 (2)
C270.038 (3)0.023 (3)0.025 (3)0.004 (2)0.011 (2)0.006 (2)
C280.087 (5)0.039 (3)0.026 (3)−0.005 (4)0.012 (3)0.002 (3)
C290.017 (3)0.028 (3)0.032 (3)−0.002 (2)0.001 (3)−0.004 (2)
C300.021 (3)0.048 (3)0.029 (3)−0.015 (3)−0.004 (3)0.008 (3)
C310.037 (4)0.048 (4)0.046 (4)−0.024 (3)0.006 (3)−0.009 (3)
C320.025 (3)0.052 (4)0.058 (4)−0.002 (3)0.016 (3)−0.034 (4)
C330.015 (3)0.026 (3)0.045 (3)−0.002 (2)−0.005 (3)−0.011 (3)
C340.012 (3)0.021 (2)0.031 (3)−0.004 (2)−0.003 (2)−0.003 (2)
C350.018 (3)0.032 (3)0.032 (3)−0.006 (2)−0.003 (2)−0.001 (3)
C360.016 (3)0.020 (2)0.023 (3)−0.003 (2)0.003 (2)−0.003 (2)
C370.019 (3)0.012 (2)0.028 (3)0.003 (2)−0.006 (2)−0.001 (2)
C380.013 (3)0.016 (2)0.029 (3)−0.001 (2)−0.001 (2)0.000 (2)
C390.018 (3)0.018 (2)0.015 (2)0.000 (2)−0.001 (2)−0.002 (2)
C400.022 (3)0.017 (3)0.033 (3)−0.004 (2)−0.004 (2)0.000 (2)
C410.019 (3)0.010 (2)0.028 (3)0.004 (2)−0.004 (2)−0.006 (2)
C420.023 (3)0.015 (2)0.029 (3)0.002 (2)−0.004 (2)0.001 (2)
C430.026 (3)0.018 (2)0.039 (3)0.012 (2)−0.001 (2)−0.002 (2)
C440.017 (3)0.029 (3)0.059 (4)0.009 (2)−0.003 (3)−0.010 (3)
C450.022 (3)0.018 (2)0.032 (3)−0.002 (2)−0.003 (2)0.001 (2)
C460.029 (3)0.015 (2)0.022 (3)−0.003 (2)−0.002 (2)0.004 (2)
C470.045 (4)0.025 (3)0.033 (3)−0.004 (3)0.001 (3)0.012 (3)
C480.017 (3)0.016 (2)0.021 (3)−0.002 (2)0.000 (2)−0.001 (2)
C490.022 (3)0.020 (3)0.033 (3)−0.009 (2)−0.003 (2)0.000 (2)
C500.026 (3)0.027 (3)0.029 (3)−0.002 (3)0.005 (2)−0.005 (3)
C510.024 (3)0.016 (2)0.028 (3)0.003 (2)−0.005 (2)−0.001 (2)
C520.026 (3)0.045 (3)0.029 (3)0.001 (3)−0.005 (3)−0.005 (3)
C530.042 (4)0.043 (4)0.033 (3)0.007 (3)−0.003 (3)−0.001 (3)
C540.019 (3)0.015 (2)0.032 (3)−0.002 (2)−0.004 (2)0.001 (3)
C550.019 (2)0.020 (2)0.022 (3)0.001 (2)−0.0003 (19)0.000 (2)
C560.030 (3)0.028 (3)0.029 (3)0.003 (2)−0.003 (3)0.004 (3)

Geometric parameters (Å, °)

Br1—C21.895 (6)C24—H24A0.9900
Br2—C301.898 (6)C24—H24B0.9900
Cl1—C81.830 (5)C25—H25A0.9800
Cl2—C361.847 (5)C25—H25B0.9800
O1—C31.224 (7)C25—H25C0.9800
O2—C121.428 (6)C26—C271.495 (7)
O2—H20.8200C27—C281.531 (7)
O3—C211.202 (6)C27—H27A0.9900
O4—C231.364 (6)C27—H27B0.9900
O4—C221.442 (6)C28—H28A0.9800
O5—C231.215 (6)C28—H28B0.9800
O6—C261.343 (6)C28—H28C0.9800
O6—C191.481 (6)C29—C301.328 (8)
O7—C261.217 (6)C29—C341.494 (7)
O8—C311.214 (8)C29—H290.9500
O9—C371.423 (6)C30—C311.455 (9)
O9—H90.8200C31—C321.464 (10)
O10—C491.217 (6)C32—C331.344 (8)
O11—C511.369 (6)C32—H320.9500
O11—C501.438 (6)C33—C341.505 (7)
O12—C511.187 (6)C33—C441.515 (8)
O13—C541.355 (6)C34—C351.562 (7)
O13—C481.472 (6)C34—C361.571 (7)
O14—C541.194 (6)C35—H35A0.9800
C1—C21.334 (8)C35—H35B0.9800
C1—C61.504 (7)C35—H35C0.9800
C1—H10.9500C36—C371.529 (7)
C2—C31.479 (9)C36—C421.551 (7)
C3—C41.450 (9)C37—C381.532 (7)
C4—C51.346 (8)C37—H371.0000
C4—H40.9500C38—C391.531 (7)
C5—C111.503 (8)C38—H38A0.9900
C5—C61.507 (7)C38—H38B0.9900
C6—C71.552 (8)C39—C401.547 (7)
C6—C81.590 (7)C39—C411.533 (7)
C7—H7A0.9800C39—C481.571 (7)
C7—H7B0.9800C40—H40A0.9800
C7—H7C0.9800C40—H40B0.9800
C8—C91.530 (7)C40—H40C0.9800
C8—C121.549 (7)C41—C451.521 (7)
C9—C161.526 (7)C41—C421.536 (7)
C9—C101.531 (7)C41—H411.0000
C9—H9a1.0000C42—C431.523 (7)
C10—C111.527 (8)C42—H421.0000
C10—H10A0.9900C43—C441.534 (8)
C10—H10B0.9900C43—H43A0.9900
C11—H11A0.9900C43—H43B0.9900
C11—H11B0.9900C44—H44A0.9900
C12—C131.551 (7)C44—H44B0.9900
C12—H121.0000C45—C461.531 (7)
C13—C141.523 (7)C45—H45A0.9900
C13—H13A0.9900C45—H45B0.9900
C13—H13B0.9900C46—C471.519 (7)
C14—C151.531 (7)C46—C481.568 (6)
C14—C161.552 (6)C46—H461.0000
C14—C191.568 (7)C47—H47A0.9800
C15—H15A0.9800C47—H47B0.9800
C15—H15B0.9800C47—H47C0.9800
C15—H15C0.9800C48—C491.525 (7)
C16—C171.521 (7)C49—C501.523 (7)
C16—H161.0000C50—H50A0.9900
C17—C181.531 (7)C50—H50B0.9900
C17—H17A0.9900C51—C521.515 (8)
C17—H17B0.9900C52—C531.510 (8)
C18—C201.534 (7)C52—H52A0.9900
C18—C191.579 (7)C52—H52B0.9900
C18—H181.0000C53—H53A0.9800
C19—C211.517 (7)C53—H53B0.9800
C20—H20A0.9800C53—H53C0.9800
C20—H20B0.9800C54—C551.507 (7)
C20—H20C0.9800C55—C561.523 (7)
C21—C221.534 (7)C55—H55A0.9900
C22—H22A0.9900C55—H55B0.9900
C22—H22B0.9900C56—H56A0.9800
C23—C241.479 (7)C56—H56B0.9800
C24—C251.496 (8)C56—H56C0.9800
C12—O2—H2109.5C27—C28—H28C109.5
C23—O4—C22115.8 (4)H28A—C28—H28C109.5
C26—O6—C19117.8 (4)H28B—C28—H28C109.5
C37—O9—H9109.5C30—C29—C34123.5 (5)
C51—O11—C50114.9 (4)C30—C29—H29118.3
C54—O13—C48117.0 (4)C34—C29—H29118.3
C2—C1—C6122.8 (5)C29—C30—C31122.6 (6)
C2—C1—H1118.6C29—C30—Br2121.2 (5)
C6—C1—H1118.6C31—C30—Br2116.2 (4)
C1—C2—C3122.9 (6)O8—C31—C32122.0 (7)
C1—C2—Br1121.2 (5)O8—C31—C30122.3 (7)
C3—C2—Br1115.9 (4)C32—C31—C30115.6 (6)
O1—C3—C4122.2 (6)C33—C32—C31123.0 (6)
O1—C3—C2122.5 (6)C33—C32—H32118.5
C4—C3—C2115.2 (5)C31—C32—H32118.5
C5—C4—C3123.4 (6)C32—C33—C34121.8 (5)
C5—C4—H4118.3C32—C33—C44122.4 (5)
C3—C4—H4118.3C34—C33—C44115.7 (5)
C4—C5—C11121.5 (5)C33—C34—C29113.1 (5)
C4—C5—C6122.4 (5)C33—C34—C35105.8 (4)
C11—C5—C6116.0 (5)C29—C34—C35105.6 (4)
C1—C6—C5112.9 (5)C33—C34—C36108.5 (4)
C1—C6—C7106.6 (4)C29—C34—C36109.6 (4)
C5—C6—C7106.4 (5)C35—C34—C36114.3 (5)
C1—C6—C8109.3 (4)C34—C35—H35A109.5
C5—C6—C8108.4 (4)C34—C35—H35B109.5
C7—C6—C8113.3 (4)H35A—C35—H35B109.5
C6—C7—H7A109.5C34—C35—H35C109.5
C6—C7—H7B109.5H35A—C35—H35C109.5
H7A—C7—H7B109.5H35B—C35—H35C109.5
C6—C7—H7C109.5C37—C36—C42114.8 (4)
H7A—C7—H7C109.5C37—C36—C34115.3 (4)
H7B—C7—H7C109.5C42—C36—C34110.0 (4)
C9—C8—C12114.4 (4)C37—C36—Cl2103.0 (4)
C9—C8—C6111.0 (4)C42—C36—Cl2107.3 (3)
C12—C8—C6114.4 (4)C34—C36—Cl2105.5 (4)
C9—C8—Cl1108.4 (3)O9—C37—C38112.5 (4)
C12—C8—Cl1103.4 (3)O9—C37—C36106.3 (4)
C6—C8—Cl1104.3 (3)C38—C37—C36114.0 (4)
C16—C9—C8110.8 (4)O9—C37—H37107.9
C16—C9—C10111.1 (4)C38—C37—H37107.9
C8—C9—C10111.9 (4)C36—C37—H37107.9
C16—C9—H9a107.6C39—C38—C37113.5 (4)
C8—C9—H9a107.6C39—C38—H38A108.9
C10—C9—H9a107.6C37—C38—H38A108.9
C11—C10—C9112.3 (4)C39—C38—H38B108.9
C11—C10—H10A109.1C37—C38—H38B108.9
C9—C10—H10A109.1H38A—C38—H38B107.7
C11—C10—H10B109.1C38—C39—C40111.5 (4)
C9—C10—H10B109.1C38—C39—C41108.2 (4)
H10A—C10—H10B107.9C40—C39—C41112.8 (4)
C5—C11—C10111.1 (5)C38—C39—C48116.2 (4)
C5—C11—H11A109.4C40—C39—C48108.2 (4)
C10—C11—H11A109.4C41—C39—C4899.4 (4)
C5—C11—H11B109.4C39—C40—H40A109.5
C10—C11—H11B109.4C39—C40—H40B109.5
H11A—C11—H11B108.0H40A—C40—H40B109.5
O2—C12—C8108.2 (4)C39—C40—H40C109.5
O2—C12—C13111.1 (4)H40A—C40—H40C109.5
C8—C12—C13112.4 (4)H40B—C40—H40C109.5
O2—C12—H12108.3C45—C41—C42118.0 (4)
C8—C12—H12108.3C45—C41—C39103.4 (4)
C13—C12—H12108.3C42—C41—C39112.6 (4)
C14—C13—C12114.5 (4)C45—C41—H41107.4
C14—C13—H13A108.6C42—C41—H41107.4
C12—C13—H13A108.6C39—C41—H41107.4
C14—C13—H13B108.6C43—C42—C41111.5 (4)
C12—C13—H13B108.6C43—C42—C36111.9 (4)
H13A—C13—H13B107.6C41—C42—C36110.6 (4)
C13—C14—C15111.6 (4)C43—C42—H42107.5
C13—C14—C16108.1 (4)C41—C42—H42107.5
C15—C14—C16113.2 (4)C36—C42—H42107.5
C13—C14—C19116.2 (4)C44—C43—C42113.1 (4)
C15—C14—C19107.8 (4)C44—C43—H43A109.0
C16—C14—C1999.6 (4)C42—C43—H43A109.0
C14—C15—H15A109.5C44—C43—H43B109.0
C14—C15—H15B109.5C42—C43—H43B109.0
H15A—C15—H15B109.5H43A—C43—H43B107.8
C14—C15—H15C109.5C33—C44—C43112.4 (5)
H15A—C15—H15C109.5C33—C44—H44A109.1
H15B—C15—H15C109.5C43—C44—H44A109.1
C17—C16—C9120.2 (4)C33—C44—H44B109.1
C17—C16—C14102.4 (4)C43—C44—H44B109.1
C9—C16—C14113.6 (4)H44A—C44—H44B107.8
C17—C16—H16106.6C41—C45—C46103.4 (4)
C9—C16—H16106.6C41—C45—H45A111.1
C14—C16—H16106.6C46—C45—H45A111.1
C16—C17—C18104.2 (4)C41—C45—H45B111.1
C16—C17—H17A110.9C46—C45—H45B111.1
C18—C17—H17A110.9H45A—C45—H45B109.0
C16—C17—H17B110.9C47—C46—C45111.8 (4)
C18—C17—H17B110.9C47—C46—C48118.9 (5)
H17A—C17—H17B108.9C45—C46—C48106.5 (4)
C20—C18—C17114.5 (4)C47—C46—H46106.3
C20—C18—C19117.5 (4)C45—C46—H46106.3
C17—C18—C19105.6 (4)C48—C46—H46106.3
C20—C18—H18106.1C46—C47—H47A109.5
C17—C18—H18106.1C46—C47—H47B109.5
C19—C18—H18106.1H47A—C47—H47B109.5
O6—C19—C21109.3 (4)C46—C47—H47C109.5
O6—C19—C14103.8 (4)H47A—C47—H47C109.5
C21—C19—C14111.9 (4)H47B—C47—H47C109.5
O6—C19—C18107.2 (4)O13—C48—C49107.6 (4)
C21—C19—C18119.3 (4)O13—C48—C46108.3 (4)
C14—C19—C18104.2 (4)C49—C48—C46119.5 (4)
C18—C20—H20A109.5O13—C48—C39105.4 (4)
C18—C20—H20B109.5C49—C48—C39111.6 (4)
H20A—C20—H20B109.5C46—C48—C39103.7 (4)
C18—C20—H20C109.5O10—C49—C48122.1 (5)
H20A—C20—H20C109.5O10—C49—C50120.1 (5)
H20B—C20—H20C109.5C48—C49—C50117.6 (4)
O3—C21—C19123.1 (5)O11—C50—C49110.9 (4)
O3—C21—C22119.7 (5)O11—C50—H50A109.4
C19—C21—C22116.9 (4)C49—C50—H50A109.4
O4—C22—C21110.0 (4)O11—C50—H50B109.4
O4—C22—H22A109.7C49—C50—H50B109.4
C21—C22—H22A109.7H50A—C50—H50B108.0
O4—C22—H22B109.7O12—C51—O11123.2 (5)
C21—C22—H22B109.7O12—C51—C52126.6 (5)
H22A—C22—H22B108.2O11—C51—C52110.2 (5)
O5—C23—O4121.6 (5)C51—C52—C53112.7 (5)
O5—C23—C24127.5 (5)C51—C52—H52A109.1
O4—C23—C24110.9 (5)C53—C52—H52A109.1
C23—C24—C25113.7 (5)C51—C52—H52B109.1
C23—C24—H24A108.8C53—C52—H52B109.1
C25—C24—H24A108.8H52A—C52—H52B107.8
C23—C24—H24B108.8C52—C53—H53A109.5
C25—C24—H24B108.8C52—C53—H53B109.5
H24A—C24—H24B107.7H53A—C53—H53B109.5
C24—C25—H25A109.5C52—C53—H53C109.5
C24—C25—H25B109.5H53A—C53—H53C109.5
H25A—C25—H25B109.5H53B—C53—H53C109.5
C24—C25—H25C109.5O14—C54—O13121.9 (5)
H25A—C25—H25C109.5O14—C54—C55125.8 (5)
H25B—C25—H25C109.5O13—C54—C55112.2 (4)
O7—C26—O6122.4 (5)C54—C55—C56111.7 (4)
O7—C26—C27126.1 (5)C54—C55—H55A109.3
O6—C26—C27111.5 (5)C56—C55—H55A109.3
C26—C27—C28114.4 (4)C54—C55—H55B109.3
C26—C27—H27A108.6C56—C55—H55B109.3
C28—C27—H27A108.6H55A—C55—H55B107.9
C26—C27—H27B108.6C55—C56—H56A109.5
C28—C27—H27B108.6C55—C56—H56B109.5
H27A—C27—H27B107.6H56A—C56—H56B109.5
C27—C28—H28A109.5C55—C56—H56C109.5
C27—C28—H28B109.5H56A—C56—H56C109.5
H28A—C28—H28B109.5H56B—C56—H56C109.5
C6—C1—C2—C3−1.3 (9)C34—C29—C30—C31−1.7 (9)
C6—C1—C2—Br1178.3 (4)C34—C29—C30—Br2177.6 (4)
C1—C2—C3—O1175.1 (6)C29—C30—C31—O8−179.9 (6)
Br1—C2—C3—O1−4.5 (9)Br2—C30—C31—O80.8 (8)
C1—C2—C3—C4−3.0 (9)C29—C30—C31—C32−2.9 (9)
Br1—C2—C3—C4177.3 (4)Br2—C30—C31—C32177.8 (5)
O1—C3—C4—C5−175.9 (6)O8—C31—C32—C33179.7 (6)
C2—C3—C4—C52.2 (9)C30—C31—C32—C332.7 (9)
C3—C4—C5—C11−179.7 (6)C31—C32—C33—C342.0 (9)
C3—C4—C5—C62.9 (10)C31—C32—C33—C44178.6 (6)
C2—C1—C6—C56.0 (7)C32—C33—C34—C29−6.2 (8)
C2—C1—C6—C7−110.5 (6)C44—C33—C34—C29177.1 (5)
C2—C1—C6—C8126.7 (5)C32—C33—C34—C35108.9 (6)
C4—C5—C6—C1−6.8 (8)C44—C33—C34—C35−67.8 (5)
C11—C5—C6—C1175.7 (5)C32—C33—C34—C36−128.0 (6)
C4—C5—C6—C7109.8 (6)C44—C33—C34—C3655.3 (6)
C11—C5—C6—C7−67.7 (6)C30—C29—C34—C336.1 (8)
C4—C5—C6—C8−128.0 (6)C30—C29—C34—C35−109.1 (6)
C11—C5—C6—C854.5 (6)C30—C29—C34—C36127.3 (6)
C1—C6—C8—C9−177.2 (4)C33—C34—C36—C37170.9 (5)
C5—C6—C8—C9−53.8 (6)C29—C34—C36—C3747.0 (6)
C7—C6—C8—C964.1 (5)C35—C34—C36—C37−71.3 (6)
C1—C6—C8—C1251.5 (6)C33—C34—C36—C42−57.4 (6)
C5—C6—C8—C12174.9 (4)C29—C34—C36—C42178.7 (4)
C7—C6—C8—C12−67.3 (6)C35—C34—C36—C4260.4 (5)
C1—C6—C8—Cl1−60.7 (4)C33—C34—C36—Cl258.0 (5)
C5—C6—C8—Cl162.7 (5)C29—C34—C36—Cl2−65.9 (5)
C7—C6—C8—Cl1−179.4 (4)C35—C34—C36—Cl2175.8 (3)
C12—C8—C9—C16−48.9 (6)C42—C36—C37—O9−81.9 (5)
C6—C8—C9—C16179.8 (4)C34—C36—C37—O947.6 (6)
Cl1—C8—C9—C1665.8 (5)Cl2—C36—C37—O9161.9 (3)
C12—C8—C9—C10−173.5 (4)C42—C36—C37—C3842.7 (6)
C6—C8—C9—C1055.2 (6)C34—C36—C37—C38172.1 (4)
Cl1—C8—C9—C10−58.8 (5)Cl2—C36—C37—C38−73.6 (5)
C16—C9—C10—C11−178.4 (5)O9—C37—C38—C3972.8 (5)
C8—C9—C10—C11−54.0 (6)C36—C37—C38—C39−48.3 (6)
C4—C5—C11—C10128.5 (6)C37—C38—C39—C40−68.4 (6)
C6—C5—C11—C10−54.0 (7)C37—C38—C39—C4156.2 (5)
C9—C10—C11—C551.4 (7)C37—C38—C39—C48166.9 (4)
C9—C8—C12—O2−77.7 (5)C38—C39—C41—C45170.5 (4)
C6—C8—C12—O252.0 (5)C40—C39—C41—C45−65.7 (5)
Cl1—C8—C12—O2164.7 (3)C48—C39—C41—C4548.8 (5)
C9—C8—C12—C1345.3 (6)C38—C39—C41—C42−60.9 (5)
C6—C8—C12—C13175.0 (4)C40—C39—C41—C4262.9 (5)
Cl1—C8—C12—C13−72.2 (4)C48—C39—C41—C42177.3 (4)
O2—C12—C13—C1472.4 (5)C45—C41—C42—C43−58.4 (6)
C8—C12—C13—C14−49.0 (6)C39—C41—C42—C43−178.8 (4)
C12—C13—C14—C15−70.9 (5)C45—C41—C42—C36176.4 (4)
C12—C13—C14—C1654.1 (5)C39—C41—C42—C3656.0 (6)
C12—C13—C14—C19164.9 (4)C37—C36—C42—C43−170.9 (5)
C8—C9—C16—C17177.9 (4)C34—C36—C42—C4357.1 (6)
C10—C9—C16—C17−57.0 (6)Cl2—C36—C42—C43−57.1 (5)
C8—C9—C16—C1456.3 (6)C37—C36—C42—C41−45.9 (6)
C10—C9—C16—C14−178.7 (5)C34—C36—C42—C41−177.9 (4)
C13—C14—C16—C17170.5 (4)Cl2—C36—C42—C4167.9 (4)
C15—C14—C16—C17−65.4 (5)C41—C42—C43—C44−176.1 (5)
C19—C14—C16—C1748.8 (5)C36—C42—C43—C44−51.6 (7)
C13—C14—C16—C9−58.4 (6)C32—C33—C44—C43133.0 (6)
C15—C14—C16—C965.7 (6)C34—C33—C44—C43−50.3 (7)
C19—C14—C16—C9179.9 (4)C42—C43—C44—C3346.7 (7)
C9—C16—C17—C18−170.0 (4)C42—C41—C45—C46−166.4 (4)
C14—C16—C17—C18−42.9 (5)C39—C41—C45—C46−41.3 (5)
C16—C17—C18—C20150.3 (4)C41—C45—C46—C47148.0 (4)
C16—C17—C18—C1919.3 (5)C41—C45—C46—C4816.7 (5)
C26—O6—C19—C2167.2 (5)C54—O13—C48—C4966.3 (5)
C26—O6—C19—C14−173.3 (4)C54—O13—C48—C46−64.1 (5)
C26—O6—C19—C18−63.4 (5)C54—O13—C48—C39−174.5 (4)
C13—C14—C19—O6−39.6 (5)C47—C46—C48—O13134.3 (5)
C15—C14—C19—O6−165.7 (4)C45—C46—C48—O13−98.5 (4)
C16—C14—C19—O676.1 (4)C47—C46—C48—C4910.8 (7)
C13—C14—C19—C2178.1 (5)C45—C46—C48—C49138.0 (5)
C15—C14—C19—C21−48.0 (5)C47—C46—C48—C39−114.1 (5)
C16—C14—C19—C21−166.3 (4)C45—C46—C48—C3913.1 (5)
C13—C14—C19—C18−151.7 (4)C38—C39—C48—O13−39.2 (5)
C15—C14—C19—C1882.2 (4)C40—C39—C48—O13−165.5 (4)
C16—C14—C19—C18−36.0 (5)C41—C39—C48—O1376.6 (4)
C20—C18—C19—O6132.2 (4)C38—C39—C48—C4977.3 (5)
C17—C18—C19—O6−98.6 (4)C40—C39—C48—C49−49.0 (5)
C20—C18—C19—C217.4 (6)C41—C39—C48—C49−167.0 (4)
C17—C18—C19—C21136.7 (5)C38—C39—C48—C46−152.9 (4)
C20—C18—C19—C14−118.2 (4)C40—C39—C48—C4680.8 (5)
C17—C18—C19—C1411.0 (5)C41—C39—C48—C46−37.1 (5)
O6—C19—C21—O3−161.9 (5)O13—C48—C49—O10−159.1 (4)
C14—C19—C21—O383.8 (6)C46—C48—C49—O10−35.2 (7)
C18—C19—C21—O3−38.1 (7)C39—C48—C49—O1085.8 (6)
O6—C19—C21—C2224.2 (5)O13—C48—C49—C5024.9 (6)
C14—C19—C21—C22−90.2 (5)C46—C48—C49—C50148.8 (4)
C18—C19—C21—C22147.9 (4)C39—C48—C49—C50−90.2 (5)
C23—O4—C22—C21−76.7 (5)C51—O11—C50—C49−78.9 (5)
O3—C21—C22—O4−7.2 (7)O10—C49—C50—O11−4.3 (7)
C19—C21—C22—O4167.0 (4)C48—C49—C50—O11171.7 (4)
C22—O4—C23—O5−7.2 (7)C50—O11—C51—O12−4.2 (7)
C22—O4—C23—C24172.7 (4)C50—O11—C51—C52175.8 (4)
O5—C23—C24—C25−16.9 (8)O12—C51—C52—C53−18.3 (8)
O4—C23—C24—C25163.2 (5)O11—C51—C52—C53161.7 (5)
C19—O6—C26—O7−10.5 (7)C48—O13—C54—O14−10.4 (7)
C19—O6—C26—C27167.5 (4)C48—O13—C54—C55172.9 (4)
O7—C26—C27—C28−149.2 (5)O14—C54—C55—C5620.5 (7)
O6—C26—C27—C2832.9 (7)O13—C54—C55—C56−162.9 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2···O7i0.822.112.817 (5)145
O9—H9···O14ii0.821.982.754 (5)158

Symmetry codes: (i) −x, y+1/2, −z; (ii) −x+2, y−1/2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2487).

References

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