Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108025997/gd3236sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108025997/gd3236Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108025997/gd3236IIsup3.hkl |
CCDC references: 703746; 703747
Details of the synthesis have been previously reported (Siddiqui et al., 1995; Njar et al., 1998; Moreira et al., 2007). Compounds (I) and (II) were each crystallized from a solution in mixture of ethyl acetate and n-hexane [Ratio of solvents?] by slow evaporation.
All H atoms were refined as riding on their parent atoms, with C—H = 0.93–0.98 Å and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). Atoms O2, C31 and C32 (and their riding H atoms) are disordered over two alternative conformations. The final refined occupancy of the major components was 0.504 (9). The disordered atoms were refined isotropically. The absolute configuration known from the synthesis route was confirmed from the X-ray data.
For both compounds, data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C22H29ClO3 | F(000) = 808 |
Mr = 376.90 | Dx = 1.253 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 4667 reflections |
a = 6.0689 (2) Å | θ = 2.3–18.6° |
b = 13.2879 (4) Å | µ = 0.21 mm−1 |
c = 24.7664 (8) Å | T = 293 K |
V = 1997.24 (11) Å3 | Prism, colourless |
Z = 4 | 0.42 × 0.17 × 0.09 mm |
Bruker APEX CCD area-detector diffractometer | 3757 independent reflections |
Radiation source: fine-focus sealed tube | 2563 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.084 |
ϕ and ω scans | θmax = 25.7°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −7→7 |
Tmin = 0.863, Tmax = 0.98 | k = −16→16 |
38455 measured reflections | l = −29→30 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.105 | w = 1/[σ2(Fo2) + (0.0469P)2 + 0.1552P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
3757 reflections | Δρmax = 0.14 e Å−3 |
238 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with 1551 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.02 (10) |
C22H29ClO3 | V = 1997.24 (11) Å3 |
Mr = 376.90 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.0689 (2) Å | µ = 0.21 mm−1 |
b = 13.2879 (4) Å | T = 293 K |
c = 24.7664 (8) Å | 0.42 × 0.17 × 0.09 mm |
Bruker APEX CCD area-detector diffractometer | 3757 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 2563 reflections with I > 2σ(I) |
Tmin = 0.863, Tmax = 0.98 | Rint = 0.084 |
38455 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.105 | Δρmax = 0.14 e Å−3 |
S = 1.03 | Δρmin = −0.23 e Å−3 |
3757 reflections | Absolute structure: Flack (1983), with 1551 Friedel pairs |
238 parameters | Absolute structure parameter: 0.02 (10) |
0 restraints |
Experimental. Quantum-mechanical calculations of the equilibrium geometry of the free molecules were performed with the computer program GAMESS (Schmidt et al., 1993). A molecular-orbital Roothan Hartree–Fock method was used with an extended 6-31 G(d,p) basis set. Tight conditions for convergence of both the self-consistent field cycles and the maximum density and energy gradients were imposed (10-5 atomic units). |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.25370 (14) | 0.70059 (8) | 0.81619 (3) | 0.0985 (3) | |
C1 | 0.3556 (4) | 0.4315 (2) | 1.09415 (10) | 0.0544 (7) | |
H11 | 0.2592 | 0.4892 | 1.0986 | 0.065* | |
H12 | 0.2756 | 0.3814 | 1.0735 | 0.065* | |
C2 | 0.4055 (4) | 0.3878 (2) | 1.15016 (10) | 0.0554 (7) | |
H21 | 0.4692 | 0.4397 | 1.1729 | 0.067* | |
H22 | 0.2697 | 0.3652 | 1.1669 | 0.067* | |
C3 | 0.5625 (4) | 0.3014 (2) | 1.14567 (9) | 0.0510 (7) | |
H3 | 0.4922 | 0.2464 | 1.1257 | 0.061* | |
O1 | 0.6090 (3) | 0.26842 (14) | 1.20060 (7) | 0.0563 (5) | |
C31 | 0.6815 (5) | 0.1745 (2) | 1.20749 (13) | 0.0670 (8) | |
O2 | 0.7134 (5) | 0.11780 (17) | 1.17084 (9) | 0.0949 (8) | |
C32 | 0.7140 (6) | 0.1511 (3) | 1.26598 (12) | 0.0908 (11) | |
H31 | 0.6263 | 0.0937 | 1.2756 | 0.136* | |
H32 | 0.6699 | 0.2080 | 1.2873 | 0.136* | |
H33 | 0.8666 | 0.1367 | 1.2726 | 0.136* | |
C4 | 0.7714 (4) | 0.3324 (2) | 1.11704 (9) | 0.0511 (7) | |
H41 | 0.8657 | 0.2741 | 1.1126 | 0.061* | |
H42 | 0.8498 | 0.3811 | 1.1390 | 0.061* | |
C5 | 0.7234 (4) | 0.37796 (18) | 1.06227 (9) | 0.0420 (6) | |
C6 | 0.8202 (4) | 0.34268 (18) | 1.01840 (10) | 0.0480 (6) | |
H6 | 0.9131 | 0.2875 | 1.0224 | 0.058* | |
C7 | 0.7920 (4) | 0.38455 (18) | 0.96276 (9) | 0.0493 (6) | |
H71 | 0.7051 | 0.3379 | 0.9415 | 0.059* | |
H72 | 0.9355 | 0.3906 | 0.9458 | 0.059* | |
C8 | 0.6800 (4) | 0.48692 (18) | 0.96248 (9) | 0.0410 (6) | |
H8 | 0.7869 | 0.5385 | 0.9730 | 0.049* | |
C9 | 0.4856 (4) | 0.48758 (18) | 1.00291 (9) | 0.0416 (6) | |
H9 | 0.3904 | 0.4315 | 0.9922 | 0.050* | |
C10 | 0.5582 (4) | 0.46448 (18) | 1.06133 (9) | 0.0418 (6) | |
C11 | 0.3424 (4) | 0.5825 (2) | 0.99809 (11) | 0.0583 (8) | |
H111 | 0.2093 | 0.5724 | 1.0191 | 0.070* | |
H112 | 0.4218 | 0.6384 | 1.0141 | 0.070* | |
C12 | 0.2761 (4) | 0.6118 (2) | 0.94048 (9) | 0.0605 (8) | |
H121 | 0.1724 | 0.5629 | 0.9263 | 0.073* | |
H122 | 0.2045 | 0.6771 | 0.9408 | 0.073* | |
C13 | 0.4797 (4) | 0.6158 (2) | 0.90426 (10) | 0.0497 (6) | |
C14 | 0.5897 (4) | 0.51183 (18) | 0.90722 (10) | 0.0432 (6) | |
H14 | 0.4689 | 0.4639 | 0.9018 | 0.052* | |
C15 | 0.7266 (5) | 0.50465 (19) | 0.85556 (9) | 0.0543 (7) | |
H151 | 0.8708 | 0.5349 | 0.8602 | 0.065* | |
H152 | 0.7439 | 0.4354 | 0.8439 | 0.065* | |
C16 | 0.5876 (5) | 0.5636 (2) | 0.81674 (10) | 0.0557 (7) | |
C161 | 0.6006 (6) | 0.5532 (3) | 0.75833 (13) | 0.0741 (9) | |
H161 | 0.5132 | 0.5955 | 0.7374 | 0.089* | |
O3 | 0.7159 (5) | 0.4940 (2) | 0.73529 (8) | 0.0925 (8) | |
C17 | 0.4456 (5) | 0.6211 (2) | 0.84412 (11) | 0.0574 (7) | |
C18 | 0.6321 (5) | 0.7036 (2) | 0.91963 (12) | 0.0667 (8) | |
H181 | 0.5600 | 0.7662 | 0.9118 | 0.100* | |
H182 | 0.7662 | 0.6991 | 0.8992 | 0.100* | |
H183 | 0.6655 | 0.7002 | 0.9575 | 0.100* | |
C19 | 0.6669 (5) | 0.55694 (19) | 1.08863 (11) | 0.0608 (8) | |
H191 | 0.5574 | 0.6077 | 1.0949 | 0.091* | |
H192 | 0.7797 | 0.5834 | 1.0655 | 0.091* | |
H193 | 0.7310 | 0.5370 | 1.1224 | 0.091* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0769 (5) | 0.1319 (8) | 0.0866 (6) | 0.0260 (6) | −0.0113 (5) | 0.0407 (5) |
C1 | 0.0399 (14) | 0.075 (2) | 0.0487 (16) | 0.0110 (14) | 0.0053 (12) | −0.0010 (14) |
C2 | 0.0464 (15) | 0.0729 (19) | 0.0470 (16) | 0.0047 (15) | 0.0063 (12) | −0.0010 (15) |
C3 | 0.0557 (15) | 0.0568 (17) | 0.0407 (15) | −0.0009 (14) | −0.0013 (13) | −0.0077 (13) |
O1 | 0.0691 (12) | 0.0532 (12) | 0.0466 (11) | 0.0048 (10) | 0.0041 (9) | 0.0021 (9) |
C31 | 0.0616 (18) | 0.062 (2) | 0.078 (2) | 0.0073 (17) | 0.0160 (16) | 0.0059 (18) |
O2 | 0.122 (2) | 0.0661 (15) | 0.0969 (17) | 0.0189 (16) | 0.0274 (16) | −0.0055 (13) |
C32 | 0.102 (3) | 0.090 (2) | 0.080 (2) | 0.024 (2) | 0.013 (2) | 0.0322 (18) |
C4 | 0.0464 (14) | 0.0600 (17) | 0.0469 (14) | 0.0071 (14) | 0.0004 (13) | −0.0042 (13) |
C5 | 0.0368 (13) | 0.0495 (15) | 0.0398 (13) | 0.0009 (13) | −0.0009 (11) | −0.0025 (11) |
C6 | 0.0455 (14) | 0.0468 (16) | 0.0517 (16) | 0.0069 (12) | 0.0005 (12) | −0.0005 (12) |
C7 | 0.0524 (15) | 0.0523 (16) | 0.0432 (14) | 0.0034 (14) | 0.0077 (12) | −0.0039 (12) |
C8 | 0.0380 (13) | 0.0432 (15) | 0.0419 (14) | −0.0017 (12) | −0.0002 (11) | −0.0069 (11) |
C9 | 0.0356 (12) | 0.0492 (16) | 0.0401 (15) | 0.0009 (12) | 0.0000 (11) | −0.0045 (12) |
C10 | 0.0371 (13) | 0.0485 (16) | 0.0399 (14) | 0.0048 (12) | −0.0017 (11) | −0.0083 (12) |
C11 | 0.0478 (15) | 0.072 (2) | 0.0550 (17) | 0.0202 (15) | 0.0047 (13) | −0.0001 (14) |
C12 | 0.0464 (15) | 0.075 (2) | 0.0601 (17) | 0.0172 (16) | −0.0012 (14) | 0.0088 (14) |
C13 | 0.0444 (14) | 0.0556 (17) | 0.0491 (16) | 0.0023 (14) | −0.0047 (12) | 0.0030 (13) |
C14 | 0.0410 (13) | 0.0495 (16) | 0.0392 (14) | −0.0052 (12) | −0.0013 (11) | −0.0028 (12) |
C15 | 0.0569 (16) | 0.0600 (17) | 0.0461 (15) | −0.0005 (15) | 0.0030 (14) | −0.0027 (12) |
C16 | 0.0589 (17) | 0.0660 (19) | 0.0421 (16) | −0.0132 (15) | −0.0066 (14) | 0.0070 (14) |
C161 | 0.079 (2) | 0.090 (3) | 0.053 (2) | −0.017 (2) | −0.0013 (18) | 0.0097 (19) |
O3 | 0.117 (2) | 0.1088 (19) | 0.0517 (13) | −0.0194 (18) | 0.0144 (14) | −0.0061 (12) |
C17 | 0.0476 (15) | 0.0644 (19) | 0.0603 (18) | −0.0055 (15) | −0.0090 (14) | 0.0134 (16) |
C18 | 0.0742 (19) | 0.0536 (18) | 0.072 (2) | −0.0001 (17) | −0.0086 (16) | −0.0016 (15) |
C19 | 0.0693 (18) | 0.0581 (18) | 0.0550 (17) | −0.0001 (16) | −0.0091 (15) | −0.0116 (14) |
Cl1—C17 | 1.717 (3) | C8—H8 | 0.9800 |
C1—C2 | 1.534 (4) | C9—C11 | 1.536 (3) |
C1—C10 | 1.538 (3) | C9—C10 | 1.543 (3) |
C1—H11 | 0.9700 | C9—H9 | 0.9800 |
C1—H12 | 0.9700 | C10—C19 | 1.550 (3) |
C2—C3 | 1.497 (4) | C11—C12 | 1.533 (3) |
C2—H21 | 0.9700 | C11—H111 | 0.9700 |
C2—H22 | 0.9700 | C11—H112 | 0.9700 |
C3—O1 | 1.457 (3) | C12—C13 | 1.528 (3) |
C3—C4 | 1.510 (3) | C12—H121 | 0.9700 |
C3—H3 | 0.9800 | C12—H122 | 0.9700 |
O1—C31 | 1.335 (3) | C13—C17 | 1.505 (4) |
C31—O2 | 1.195 (3) | C13—C14 | 1.536 (3) |
C31—C32 | 1.494 (4) | C13—C18 | 1.536 (4) |
C32—H31 | 0.9600 | C14—C15 | 1.529 (3) |
C32—H32 | 0.9600 | C14—H14 | 0.9800 |
C32—H33 | 0.9600 | C15—C16 | 1.500 (4) |
C4—C5 | 1.514 (3) | C15—H151 | 0.9700 |
C4—H41 | 0.9700 | C15—H152 | 0.9700 |
C4—H42 | 0.9700 | C16—C17 | 1.337 (4) |
C5—C6 | 1.321 (3) | C16—C161 | 1.456 (4) |
C5—C10 | 1.526 (3) | C161—O3 | 1.197 (4) |
C6—C7 | 1.496 (3) | C161—H161 | 0.9300 |
C6—H6 | 0.9300 | C18—H181 | 0.9600 |
C7—C8 | 1.521 (3) | C18—H182 | 0.9600 |
C7—H71 | 0.9700 | C18—H183 | 0.9600 |
C7—H72 | 0.9700 | C19—H191 | 0.9600 |
C8—C14 | 1.511 (3) | C19—H192 | 0.9600 |
C8—C9 | 1.547 (3) | C19—H193 | 0.9600 |
C2—C1—C10 | 115.3 (2) | C5—C10—C1 | 107.6 (2) |
C2—C1—H11 | 108.4 | C5—C10—C9 | 110.59 (18) |
C10—C1—H11 | 108.4 | C1—C10—C9 | 108.91 (19) |
C2—C1—H12 | 108.4 | C5—C10—C19 | 108.12 (19) |
C10—C1—H12 | 108.4 | C1—C10—C19 | 109.6 (2) |
H11—C1—H12 | 107.5 | C9—C10—C19 | 111.9 (2) |
C3—C2—C1 | 110.4 (2) | C12—C11—C9 | 115.4 (2) |
C3—C2—H21 | 109.6 | C12—C11—H111 | 108.4 |
C1—C2—H21 | 109.6 | C9—C11—H111 | 108.4 |
C3—C2—H22 | 109.6 | C12—C11—H112 | 108.4 |
C1—C2—H22 | 109.6 | C9—C11—H112 | 108.4 |
H21—C2—H22 | 108.1 | H111—C11—H112 | 107.5 |
O1—C3—C2 | 106.54 (19) | C13—C12—C11 | 110.1 (2) |
O1—C3—C4 | 111.0 (2) | C13—C12—H121 | 109.6 |
C2—C3—C4 | 111.1 (2) | C11—C12—H121 | 109.6 |
O1—C3—H3 | 109.4 | C13—C12—H122 | 109.6 |
C2—C3—H3 | 109.4 | C11—C12—H122 | 109.6 |
C4—C3—H3 | 109.4 | H121—C12—H122 | 108.2 |
C31—O1—C3 | 117.7 (2) | C17—C13—C12 | 118.1 (2) |
O2—C31—O1 | 123.1 (3) | C17—C13—C14 | 98.6 (2) |
O2—C31—C32 | 125.7 (3) | C12—C13—C14 | 107.0 (2) |
O1—C31—C32 | 111.2 (3) | C17—C13—C18 | 107.0 (2) |
C31—C32—H31 | 109.5 | C12—C13—C18 | 111.6 (2) |
C31—C32—H32 | 109.5 | C14—C13—C18 | 114.1 (2) |
H31—C32—H32 | 109.5 | C8—C14—C15 | 123.2 (2) |
C31—C32—H33 | 109.5 | C8—C14—C13 | 113.4 (2) |
H31—C32—H33 | 109.5 | C15—C14—C13 | 104.62 (19) |
H32—C32—H33 | 109.5 | C8—C14—H14 | 104.6 |
C3—C4—C5 | 111.6 (2) | C15—C14—H14 | 104.6 |
C3—C4—H41 | 109.3 | C13—C14—H14 | 104.6 |
C5—C4—H41 | 109.3 | C16—C15—C14 | 101.4 (2) |
C3—C4—H42 | 109.3 | C16—C15—H151 | 111.5 |
C5—C4—H42 | 109.3 | C14—C15—H151 | 111.5 |
H41—C4—H42 | 108.0 | C16—C15—H152 | 111.5 |
C6—C5—C4 | 120.6 (2) | C14—C15—H152 | 111.5 |
C6—C5—C10 | 123.2 (2) | H151—C15—H152 | 109.3 |
C4—C5—C10 | 116.2 (2) | C17—C16—C161 | 126.4 (3) |
C5—C6—C7 | 125.1 (2) | C17—C16—C15 | 109.6 (2) |
C5—C6—H6 | 117.5 | C161—C16—C15 | 123.8 (3) |
C7—C6—H6 | 117.5 | O3—C161—C16 | 124.6 (3) |
C6—C7—C8 | 112.84 (19) | O3—C161—H161 | 117.7 |
C6—C7—H71 | 109.0 | C16—C161—H161 | 117.7 |
C8—C7—H71 | 109.0 | C16—C17—C13 | 112.7 (2) |
C6—C7—H72 | 109.0 | C16—C17—Cl1 | 125.8 (2) |
C8—C7—H72 | 109.0 | C13—C17—Cl1 | 121.4 (2) |
H71—C7—H72 | 107.8 | C13—C18—H181 | 109.5 |
C14—C8—C7 | 111.24 (19) | C13—C18—H182 | 109.5 |
C14—C8—C9 | 107.97 (18) | H181—C18—H182 | 109.5 |
C7—C8—C9 | 110.06 (19) | C13—C18—H183 | 109.5 |
C14—C8—H8 | 109.2 | H181—C18—H183 | 109.5 |
C7—C8—H8 | 109.2 | H182—C18—H183 | 109.5 |
C9—C8—H8 | 109.2 | C10—C19—H191 | 109.5 |
C11—C9—C10 | 113.4 (2) | C10—C19—H192 | 109.5 |
C11—C9—C8 | 112.7 (2) | H191—C19—H192 | 109.5 |
C10—C9—C8 | 112.83 (18) | C10—C19—H193 | 109.5 |
C11—C9—H9 | 105.7 | H191—C19—H193 | 109.5 |
C10—C9—H9 | 105.7 | H192—C19—H193 | 109.5 |
C8—C9—H9 | 105.7 | ||
C10—C1—C2—C3 | −55.6 (3) | C8—C9—C10—C19 | 77.7 (3) |
C1—C2—C3—O1 | 177.1 (2) | C10—C9—C11—C12 | 176.9 (2) |
C1—C2—C3—C4 | 56.1 (3) | C8—C9—C11—C12 | 47.2 (3) |
C2—C3—O1—C31 | 157.8 (2) | C9—C11—C12—C13 | −51.3 (3) |
C4—C3—O1—C31 | −81.1 (3) | C11—C12—C13—C17 | 167.1 (2) |
C3—O1—C31—O2 | 1.5 (4) | C11—C12—C13—C14 | 57.2 (3) |
C3—O1—C31—C32 | −178.0 (3) | C11—C12—C13—C18 | −68.3 (3) |
O1—C3—C4—C5 | −173.50 (19) | C7—C8—C14—C15 | −50.8 (3) |
C2—C3—C4—C5 | −55.2 (3) | C9—C8—C14—C15 | −171.6 (2) |
C3—C4—C5—C6 | −126.4 (3) | C7—C8—C14—C13 | −178.5 (2) |
C3—C4—C5—C10 | 53.1 (3) | C9—C8—C14—C13 | 60.6 (3) |
C4—C5—C6—C7 | −177.4 (2) | C17—C13—C14—C8 | 171.4 (2) |
C10—C5—C6—C7 | 3.2 (4) | C12—C13—C14—C8 | −65.6 (3) |
C5—C6—C7—C8 | 12.8 (4) | C18—C13—C14—C8 | 58.4 (3) |
C6—C7—C8—C14 | −162.0 (2) | C17—C13—C14—C15 | 34.5 (2) |
C6—C7—C8—C9 | −42.4 (3) | C12—C13—C14—C15 | 157.5 (2) |
C14—C8—C9—C11 | −49.1 (3) | C18—C13—C14—C15 | −78.5 (3) |
C7—C8—C9—C11 | −170.7 (2) | C8—C14—C15—C16 | −164.5 (2) |
C14—C8—C9—C10 | −179.2 (2) | C13—C14—C15—C16 | −33.1 (3) |
C7—C8—C9—C10 | 59.2 (3) | C14—C15—C16—C17 | 18.1 (3) |
C6—C5—C10—C1 | 131.0 (3) | C14—C15—C16—C161 | −158.4 (3) |
C4—C5—C10—C1 | −48.4 (3) | C17—C16—C161—O3 | −172.7 (3) |
C6—C5—C10—C9 | 12.2 (3) | C15—C16—C161—O3 | 3.2 (5) |
C4—C5—C10—C9 | −167.3 (2) | C161—C16—C17—C13 | −179.0 (3) |
C6—C5—C10—C19 | −110.6 (3) | C15—C16—C17—C13 | 4.6 (3) |
C4—C5—C10—C19 | 69.9 (3) | C161—C16—C17—Cl1 | −3.2 (4) |
C2—C1—C10—C5 | 49.6 (3) | C15—C16—C17—Cl1 | −179.6 (2) |
C2—C1—C10—C9 | 169.5 (2) | C12—C13—C17—C16 | −139.3 (3) |
C2—C1—C10—C19 | −67.8 (3) | C14—C13—C17—C16 | −24.8 (3) |
C11—C9—C10—C5 | −172.6 (2) | C18—C13—C17—C16 | 93.8 (3) |
C8—C9—C10—C5 | −42.9 (3) | C12—C13—C17—Cl1 | 44.6 (3) |
C11—C9—C10—C1 | 69.3 (3) | C14—C13—C17—Cl1 | 159.2 (2) |
C8—C9—C10—C1 | −161.0 (2) | C18—C13—C17—Cl1 | −82.2 (3) |
C11—C9—C10—C19 | −52.0 (3) |
C21H29ClO2 | F(000) = 752 |
Mr = 348.89 | Dx = 1.211 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 4499 reflections |
a = 6.0271 (2) Å | θ = 2.4–19.2° |
b = 15.4064 (6) Å | µ = 0.21 mm−1 |
c = 20.6081 (9) Å | T = 293 K |
V = 1913.58 (13) Å3 | Prism, colourless |
Z = 4 | 0.36 × 0.13 × 0.09 mm |
Bruker APEX CCD area-detector diffractometer | 3615 independent reflections |
Radiation source: fine-focus sealed tube | 2487 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.076 |
ϕ and ω scans | θmax = 25.7°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −7→7 |
Tmin = 0.861, Tmax = 0.98 | k = −18→18 |
35093 measured reflections | l = −25→25 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.063 | H-atom parameters constrained |
wR(F2) = 0.165 | w = 1/[σ2(Fo2) + (0.0733P)2 + 0.1121P] where P = (Fo2 + 2Fc2)/3 |
S = 1.26 | (Δ/σ)max < 0.001 |
3615 reflections | Δρmax = 0.42 e Å−3 |
219 parameters | Δρmin = −0.25 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with 1496 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.14 (13) |
C21H29ClO2 | V = 1913.58 (13) Å3 |
Mr = 348.89 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.0271 (2) Å | µ = 0.21 mm−1 |
b = 15.4064 (6) Å | T = 293 K |
c = 20.6081 (9) Å | 0.36 × 0.13 × 0.09 mm |
Bruker APEX CCD area-detector diffractometer | 3615 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 2487 reflections with I > 2σ(I) |
Tmin = 0.861, Tmax = 0.98 | Rint = 0.076 |
35093 measured reflections |
R[F2 > 2σ(F2)] = 0.063 | H-atom parameters constrained |
wR(F2) = 0.165 | Δρmax = 0.42 e Å−3 |
S = 1.26 | Δρmin = −0.25 e Å−3 |
3615 reflections | Absolute structure: Flack (1983), with 1496 Friedel pairs |
219 parameters | Absolute structure parameter: −0.14 (13) |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cl1 | 0.2582 (2) | 0.86349 (7) | 0.36536 (6) | 0.0872 (4) | |
O1 | 0.7517 (5) | 0.15522 (16) | 0.39783 (13) | 0.0808 (8) | |
C1 | 0.4533 (6) | 0.3690 (2) | 0.4171 (2) | 0.0631 (10) | |
H11 | 0.3640 | 0.3907 | 0.4528 | 0.076* | |
H12 | 0.3602 | 0.3681 | 0.3787 | 0.076* | |
C2 | 0.5249 (7) | 0.2760 (3) | 0.4327 (2) | 0.0707 (11) | |
H21 | 0.6037 | 0.2751 | 0.4737 | 0.085* | |
H22 | 0.3946 | 0.2395 | 0.4369 | 0.085* | |
C3 | 0.6730 (6) | 0.2408 (2) | 0.37979 (19) | 0.0646 (10) | |
H3 | 0.5907 | 0.2376 | 0.3388 | 0.078* | |
O2 | 0.4771 (13) | 0.0950 (5) | 0.3462 (4) | 0.103 (3)* | 0.504 (9) |
C31 | 0.653 (2) | 0.0892 (6) | 0.3759 (4) | 0.069 (3)* | 0.504 (9) |
C32 | 0.824 (2) | 0.0095 (6) | 0.3812 (5) | 0.077 (3)* | 0.504 (9) |
H31 | 0.7874 | −0.0334 | 0.3492 | 0.116* | 0.504 (9) |
H32 | 0.8142 | −0.0158 | 0.4237 | 0.116* | 0.504 (9) |
H33 | 0.9721 | 0.0301 | 0.3739 | 0.116* | 0.504 (9) |
O2' | 0.6819 (15) | 0.1018 (5) | 0.3057 (4) | 0.128 (4)* | 0.496 (9) |
C31' | 0.7452 (18) | 0.0900 (6) | 0.3607 (5) | 0.064 (2)* | 0.496 (9) |
C32' | 0.744 (2) | 0.0036 (6) | 0.3942 (5) | 0.071 (3)* | 0.496 (9) |
H31' | 0.7978 | −0.0402 | 0.3650 | 0.106* | 0.496 (9) |
H32' | 0.5955 | −0.0104 | 0.4073 | 0.106* | 0.496 (9) |
H33' | 0.8383 | 0.0060 | 0.4317 | 0.106* | 0.496 (9) |
C4 | 0.8747 (6) | 0.2988 (2) | 0.3717 (2) | 0.0647 (10) | |
H41 | 0.9634 | 0.2967 | 0.4110 | 0.078* | |
H42 | 0.9649 | 0.2773 | 0.3362 | 0.078* | |
C5 | 0.8094 (5) | 0.3915 (2) | 0.35818 (17) | 0.0522 (9) | |
C6 | 0.8875 (6) | 0.4341 (2) | 0.30731 (17) | 0.0587 (9) | |
H6 | 0.9814 | 0.4036 | 0.2797 | 0.070* | |
C7 | 0.8403 (6) | 0.5251 (2) | 0.29013 (17) | 0.0586 (9) | |
H71 | 0.7436 | 0.5263 | 0.2525 | 0.070* | |
H72 | 0.9780 | 0.5537 | 0.2784 | 0.070* | |
C8 | 0.7314 (5) | 0.5747 (2) | 0.34514 (15) | 0.0489 (8) | |
H8 | 0.8435 | 0.5893 | 0.3778 | 0.059* | |
C9 | 0.5495 (5) | 0.5174 (2) | 0.37662 (16) | 0.0487 (8) | |
H9 | 0.4528 | 0.4991 | 0.3409 | 0.058* | |
C10 | 0.6468 (5) | 0.4324 (2) | 0.40545 (16) | 0.0485 (8) | |
C11 | 0.3987 (6) | 0.5665 (2) | 0.42431 (18) | 0.0613 (10) | |
H111 | 0.2720 | 0.5301 | 0.4344 | 0.074* | |
H112 | 0.4801 | 0.5759 | 0.4643 | 0.074* | |
C12 | 0.3136 (6) | 0.6544 (2) | 0.39980 (19) | 0.0603 (9) | |
H121 | 0.2077 | 0.6453 | 0.3650 | 0.072* | |
H122 | 0.2385 | 0.6847 | 0.4348 | 0.072* | |
C13 | 0.5064 (5) | 0.7094 (2) | 0.37514 (16) | 0.0512 (8) | |
C14 | 0.6210 (5) | 0.6572 (2) | 0.32176 (15) | 0.0475 (8) | |
H14 | 0.5001 | 0.6374 | 0.2936 | 0.057* | |
C15 | 0.7441 (7) | 0.7262 (2) | 0.28149 (18) | 0.0639 (9) | |
H151 | 0.8891 | 0.7390 | 0.2995 | 0.077* | |
H152 | 0.7600 | 0.7085 | 0.2366 | 0.077* | |
C16 | 0.5877 (7) | 0.8022 (3) | 0.2883 (2) | 0.0686 (11) | |
H16 | 0.5858 | 0.8506 | 0.2613 | 0.082* | |
C17 | 0.4554 (6) | 0.7901 (3) | 0.33777 (19) | 0.0602 (10) | |
C18 | 0.6594 (6) | 0.7353 (2) | 0.43210 (18) | 0.0655 (10) | |
H181 | 0.7920 | 0.7617 | 0.4154 | 0.098* | |
H182 | 0.6978 | 0.6845 | 0.4566 | 0.098* | |
H183 | 0.5836 | 0.7758 | 0.4597 | 0.098* | |
C19 | 0.7688 (7) | 0.4496 (2) | 0.47003 (16) | 0.0647 (10) | |
H191 | 0.8463 | 0.3981 | 0.4832 | 0.097* | |
H192 | 0.6629 | 0.4653 | 0.5028 | 0.097* | |
H193 | 0.8730 | 0.4961 | 0.4643 | 0.097* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0749 (7) | 0.0736 (7) | 0.1132 (9) | 0.0154 (6) | 0.0010 (7) | 0.0005 (6) |
O1 | 0.097 (2) | 0.0541 (15) | 0.0916 (19) | 0.0028 (17) | −0.0363 (18) | −0.0016 (14) |
C1 | 0.0428 (19) | 0.065 (2) | 0.081 (3) | −0.0043 (17) | 0.0097 (18) | 0.015 (2) |
C2 | 0.054 (2) | 0.069 (3) | 0.089 (3) | −0.008 (2) | 0.002 (2) | 0.017 (2) |
C3 | 0.062 (2) | 0.061 (2) | 0.071 (2) | 0.0033 (18) | −0.017 (2) | 0.0060 (19) |
C4 | 0.055 (2) | 0.069 (2) | 0.070 (2) | 0.0117 (19) | 0.005 (2) | −0.001 (2) |
C5 | 0.0421 (18) | 0.060 (2) | 0.054 (2) | −0.0020 (15) | 0.0009 (16) | −0.0019 (17) |
C6 | 0.052 (2) | 0.069 (2) | 0.055 (2) | 0.0034 (19) | 0.0085 (18) | −0.0078 (19) |
C7 | 0.0483 (19) | 0.073 (2) | 0.055 (2) | −0.0045 (18) | 0.0120 (18) | −0.0016 (18) |
C8 | 0.0397 (16) | 0.063 (2) | 0.0437 (17) | −0.0079 (17) | 0.0017 (15) | −0.0031 (15) |
C9 | 0.0351 (16) | 0.061 (2) | 0.0499 (19) | 0.0009 (14) | 0.0029 (14) | −0.0026 (17) |
C10 | 0.0356 (15) | 0.061 (2) | 0.0490 (18) | −0.0028 (15) | 0.0043 (15) | 0.0026 (16) |
C11 | 0.0450 (19) | 0.067 (2) | 0.072 (2) | 0.0023 (18) | 0.0181 (18) | 0.006 (2) |
C12 | 0.0440 (19) | 0.067 (2) | 0.070 (2) | −0.0007 (17) | 0.0138 (17) | −0.0011 (19) |
C13 | 0.0431 (18) | 0.057 (2) | 0.053 (2) | −0.0062 (16) | −0.0008 (17) | −0.0023 (17) |
C14 | 0.0423 (17) | 0.056 (2) | 0.0441 (18) | −0.0072 (16) | −0.0052 (15) | −0.0001 (16) |
C15 | 0.063 (2) | 0.070 (2) | 0.059 (2) | −0.009 (2) | 0.004 (2) | 0.0082 (18) |
C16 | 0.075 (3) | 0.064 (3) | 0.067 (3) | −0.010 (2) | −0.005 (2) | 0.009 (2) |
C17 | 0.052 (2) | 0.057 (2) | 0.071 (3) | −0.0007 (17) | −0.010 (2) | −0.0067 (19) |
C18 | 0.056 (2) | 0.080 (3) | 0.060 (2) | 0.0017 (19) | −0.0089 (19) | −0.010 (2) |
C19 | 0.058 (2) | 0.080 (2) | 0.056 (2) | 0.007 (2) | 0.0002 (19) | −0.0001 (18) |
Cl1—C17 | 1.736 (4) | C7—H71 | 0.9700 |
O1—C31 | 1.262 (10) | C7—H72 | 0.9700 |
O1—C31' | 1.264 (9) | C8—C14 | 1.513 (5) |
O1—C3 | 1.450 (4) | C8—C9 | 1.550 (4) |
C1—C2 | 1.530 (5) | C8—H8 | 0.9800 |
C1—C10 | 1.540 (4) | C9—C11 | 1.538 (4) |
C1—H11 | 0.9700 | C9—C10 | 1.553 (5) |
C1—H12 | 0.9700 | C9—H9 | 0.9800 |
C2—C3 | 1.510 (6) | C10—C19 | 1.544 (5) |
C2—H21 | 0.9700 | C11—C12 | 1.533 (5) |
C2—H22 | 0.9700 | C11—H111 | 0.9700 |
C3—C4 | 1.518 (6) | C11—H112 | 0.9700 |
C3—H3 | 0.9800 | C12—C13 | 1.526 (5) |
O2—C31 | 1.228 (11) | C12—H121 | 0.9700 |
C31—C32 | 1.606 (14) | C12—H122 | 0.9700 |
C32—H31 | 0.9600 | C13—C17 | 1.494 (5) |
C32—H32 | 0.9600 | C13—C14 | 1.528 (5) |
C32—H33 | 0.9600 | C13—C18 | 1.545 (5) |
O2'—C31' | 1.209 (10) | C14—C15 | 1.539 (4) |
C31'—C32' | 1.500 (13) | C14—H14 | 0.9800 |
C32'—H31' | 0.9600 | C15—C16 | 1.510 (5) |
C32'—H32' | 0.9600 | C15—H151 | 0.9700 |
C32'—H33' | 0.9600 | C15—H152 | 0.9700 |
C4—C5 | 1.506 (5) | C16—C17 | 1.307 (5) |
C4—H41 | 0.9700 | C16—H16 | 0.9300 |
C4—H42 | 0.9700 | C18—H181 | 0.9600 |
C5—C6 | 1.324 (5) | C18—H182 | 0.9600 |
C5—C10 | 1.519 (5) | C18—H183 | 0.9600 |
C6—C7 | 1.474 (5) | C19—H191 | 0.9600 |
C6—H6 | 0.9300 | C19—H192 | 0.9600 |
C7—C8 | 1.517 (5) | C19—H193 | 0.9600 |
C31—O1—C3 | 119.2 (5) | C8—C9—C10 | 111.9 (2) |
C31'—O1—C3 | 123.9 (5) | C11—C9—H9 | 105.7 |
C2—C1—C10 | 114.4 (3) | C8—C9—H9 | 105.7 |
C2—C1—H11 | 108.7 | C10—C9—H9 | 105.7 |
C10—C1—H11 | 108.7 | C5—C10—C1 | 109.0 (3) |
C2—C1—H12 | 108.7 | C5—C10—C19 | 108.5 (3) |
C10—C1—H12 | 108.7 | C1—C10—C19 | 109.6 (3) |
H11—C1—H12 | 107.6 | C5—C10—C9 | 110.4 (3) |
C3—C2—C1 | 110.6 (3) | C1—C10—C9 | 108.0 (3) |
C3—C2—H21 | 109.5 | C19—C10—C9 | 111.4 (3) |
C1—C2—H21 | 109.5 | C12—C11—C9 | 115.0 (3) |
C3—C2—H22 | 109.5 | C12—C11—H111 | 108.5 |
C1—C2—H22 | 109.5 | C9—C11—H111 | 108.5 |
H21—C2—H22 | 108.1 | C12—C11—H112 | 108.5 |
O1—C3—C2 | 109.6 (3) | C9—C11—H112 | 108.5 |
O1—C3—C4 | 107.5 (3) | H111—C11—H112 | 107.5 |
C2—C3—C4 | 110.0 (3) | C13—C12—C11 | 110.2 (3) |
O1—C3—H3 | 109.9 | C13—C12—H121 | 109.6 |
C2—C3—H3 | 109.9 | C11—C12—H121 | 109.6 |
C4—C3—H3 | 109.9 | C13—C12—H122 | 109.6 |
O2—C31—O1 | 121.8 (8) | C11—C12—H122 | 109.6 |
O2—C31—C32 | 130.0 (8) | H121—C12—H122 | 108.1 |
O1—C31—C32 | 106.9 (9) | C17—C13—C12 | 118.5 (3) |
O2'—C31'—O1 | 117.2 (8) | C17—C13—C14 | 99.2 (3) |
O2'—C31'—C32' | 124.3 (8) | C12—C13—C14 | 106.9 (3) |
O1—C31'—C32' | 115.3 (8) | C17—C13—C18 | 107.5 (3) |
C31'—C32'—H31' | 109.5 | C12—C13—C18 | 110.2 (3) |
C31'—C32'—H32' | 109.5 | C14—C13—C18 | 114.4 (3) |
H31'—C32'—H32' | 109.5 | C8—C14—C13 | 114.3 (3) |
C31'—C32'—H33' | 109.5 | C8—C14—C15 | 122.7 (3) |
H31'—C32'—H33' | 109.5 | C13—C14—C15 | 104.0 (3) |
H32'—C32'—H33' | 109.5 | C8—C14—H14 | 104.7 |
C5—C4—C3 | 111.6 (3) | C13—C14—H14 | 104.7 |
C5—C4—H41 | 109.3 | C15—C14—H14 | 104.7 |
C3—C4—H41 | 109.3 | C16—C15—C14 | 100.6 (3) |
C5—C4—H42 | 109.3 | C16—C15—H151 | 111.6 |
C3—C4—H42 | 109.3 | C14—C15—H151 | 111.6 |
H41—C4—H42 | 108.0 | C16—C15—H152 | 111.6 |
C6—C5—C4 | 121.6 (3) | C14—C15—H152 | 111.6 |
C6—C5—C10 | 122.1 (3) | H151—C15—H152 | 109.4 |
C4—C5—C10 | 116.3 (3) | C17—C16—C15 | 110.0 (3) |
C5—C6—C7 | 126.4 (3) | C17—C16—H16 | 125.0 |
C5—C6—H6 | 116.8 | C15—C16—H16 | 125.0 |
C7—C6—H6 | 116.8 | C16—C17—C13 | 113.3 (3) |
C6—C7—C8 | 112.6 (3) | C16—C17—Cl1 | 125.4 (3) |
C6—C7—H71 | 109.1 | C13—C17—Cl1 | 120.9 (3) |
C8—C7—H71 | 109.1 | C13—C18—H181 | 109.5 |
C6—C7—H72 | 109.1 | C13—C18—H182 | 109.5 |
C8—C7—H72 | 109.1 | H181—C18—H182 | 109.5 |
H71—C7—H72 | 107.8 | C13—C18—H183 | 109.5 |
C14—C8—C7 | 112.1 (3) | H181—C18—H183 | 109.5 |
C14—C8—C9 | 107.5 (3) | H182—C18—H183 | 109.5 |
C7—C8—C9 | 109.4 (3) | C10—C19—H191 | 109.5 |
C14—C8—H8 | 109.3 | C10—C19—H192 | 109.5 |
C7—C8—H8 | 109.3 | H191—C19—H192 | 109.5 |
C9—C8—H8 | 109.3 | C10—C19—H193 | 109.5 |
C11—C9—C8 | 113.9 (3) | H191—C19—H193 | 109.5 |
C11—C9—C10 | 113.2 (3) | H192—C19—H193 | 109.5 |
C10—C1—C2—C3 | −55.9 (5) | C2—C1—C10—C19 | −70.1 (4) |
C31—O1—C3—C2 | 97.4 (7) | C2—C1—C10—C9 | 168.4 (3) |
C31'—O1—C3—C2 | 131.4 (7) | C11—C9—C10—C5 | −175.0 (3) |
C31—O1—C3—C4 | −143.1 (7) | C8—C9—C10—C5 | −44.7 (4) |
C31'—O1—C3—C4 | −109.1 (7) | C11—C9—C10—C1 | 65.9 (4) |
C1—C2—C3—O1 | 175.8 (3) | C8—C9—C10—C1 | −163.7 (3) |
C1—C2—C3—C4 | 57.8 (4) | C11—C9—C10—C19 | −54.4 (4) |
C31'—O1—C31—O2 | −117.0 (18) | C8—C9—C10—C19 | 75.9 (3) |
C3—O1—C31—O2 | −8.9 (13) | C8—C9—C11—C12 | 46.1 (4) |
C31'—O1—C31—C32 | 51.1 (13) | C10—C9—C11—C12 | 175.4 (3) |
C3—O1—C31—C32 | 159.2 (6) | C9—C11—C12—C13 | −51.0 (4) |
C31—O1—C31'—O2' | 94.8 (16) | C11—C12—C13—C17 | 168.5 (3) |
C3—O1—C31'—O2' | 4.7 (14) | C11—C12—C13—C14 | 57.7 (4) |
C31—O1—C31'—C32' | −65.9 (15) | C11—C12—C13—C18 | −67.2 (4) |
C3—O1—C31'—C32' | −156.0 (8) | C7—C8—C14—C13 | 179.4 (3) |
O1—C3—C4—C5 | −175.4 (3) | C9—C8—C14—C13 | 59.2 (3) |
C2—C3—C4—C5 | −56.1 (4) | C7—C8—C14—C15 | −53.3 (4) |
C3—C4—C5—C6 | −126.5 (4) | C9—C8—C14—C15 | −173.5 (3) |
C3—C4—C5—C10 | 52.6 (4) | C17—C13—C14—C8 | 170.6 (3) |
C4—C5—C6—C7 | −178.3 (3) | C12—C13—C14—C8 | −65.8 (3) |
C10—C5—C6—C7 | 2.7 (5) | C18—C13—C14—C8 | 56.5 (4) |
C5—C6—C7—C8 | 13.2 (5) | C17—C13—C14—C15 | 34.2 (3) |
C6—C7—C8—C14 | −162.5 (3) | C12—C13—C14—C15 | 157.9 (3) |
C6—C7—C8—C9 | −43.4 (4) | C18—C13—C14—C15 | −79.8 (3) |
C14—C8—C9—C11 | −47.3 (4) | C8—C14—C15—C16 | −164.3 (3) |
C7—C8—C9—C11 | −169.2 (3) | C13—C14—C15—C16 | −32.7 (3) |
C14—C8—C9—C10 | −177.3 (3) | C14—C15—C16—C17 | 18.4 (4) |
C7—C8—C9—C10 | 60.8 (3) | C15—C16—C17—C13 | 4.0 (4) |
C6—C5—C10—C1 | 131.9 (3) | C15—C16—C17—Cl1 | 176.9 (3) |
C4—C5—C10—C1 | −47.2 (4) | C12—C13—C17—C16 | −139.6 (4) |
C6—C5—C10—C19 | −108.9 (4) | C14—C13—C17—C16 | −24.6 (4) |
C4—C5—C10—C19 | 72.1 (4) | C18—C13—C17—C16 | 94.7 (4) |
C6—C5—C10—C9 | 13.5 (4) | C12—C13—C17—Cl1 | 47.1 (4) |
C4—C5—C10—C9 | −165.6 (3) | C14—C13—C17—Cl1 | 162.1 (2) |
C2—C1—C10—C5 | 48.5 (4) | C18—C13—C17—Cl1 | −78.5 (3) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C22H29ClO3 | C21H29ClO2 |
Mr | 376.90 | 348.89 |
Crystal system, space group | Orthorhombic, P212121 | Orthorhombic, P212121 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 6.0689 (2), 13.2879 (4), 24.7664 (8) | 6.0271 (2), 15.4064 (6), 20.6081 (9) |
V (Å3) | 1997.24 (11) | 1913.58 (13) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.21 | 0.21 |
Crystal size (mm) | 0.42 × 0.17 × 0.09 | 0.36 × 0.13 × 0.09 |
Data collection | ||
Diffractometer | Bruker APEX CCD area-detector diffractometer | Bruker APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000) | Multi-scan (SADABS; Sheldrick, 2000) |
Tmin, Tmax | 0.863, 0.98 | 0.861, 0.98 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 38455, 3757, 2563 | 35093, 3615, 2487 |
Rint | 0.084 | 0.076 |
(sin θ/λ)max (Å−1) | 0.609 | 0.610 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.105, 1.03 | 0.063, 0.165, 1.26 |
No. of reflections | 3757 | 3615 |
No. of parameters | 238 | 219 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.14, −0.23 | 0.42, −0.25 |
Absolute structure | Flack (1983), with 1551 Friedel pairs | Flack (1983), with 1496 Friedel pairs |
Absolute structure parameter | 0.02 (10) | −0.14 (13) |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976).
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Treatment of 17-oxoandrost-5-en-3β-yl acetate with POCl3 and dimethylformamide (Vilsmeier reagent) afforded 17-chloro-16-formylandrosta-5,16-dien-3β-yl acetate, (I), as the major and 17-chloroandrosta-5,16-dien-3β-yl acetate, (II), as the minor reaction product (Sciaky & Pallini, 1964; Marson, 1992; Siddiqui et al., 1995). Compound (I) was found to be an important precursor for the synthesis of steroidal inhibitors of cytochrome P450 17α-hydroxylase-C17,20-lyase as potential agents for prostate cancer treatment (Njar et al., 1998; Handratta et al., 2005; Moreira et al., 2007). We report here the molecular structures of (I) and (II) determined by single-crystal X-ray analysis, and compare them with those of the free molecules as given by quantum-mechanical ab initio calculations.
An ORTEPII (Johnson, 1976) plot of (I) is shown in Fig. 1 and a plot of (II) in Fig. 2. The two compounds are very similar: both have acetoxy and chloro substituents at the 3 and 17 positions and compound (I) has an extra formyl group at the 16 position. In both compounds, the A/B junction is quasi-trans and the remaining rings are trans fused. The acetoxy substituents at C3 are in equatorial positions, with angles to the normal (Cremer & Pople, 1975) of ring A of 68.43 (15) and 68.4 (2)°, respectively, for (I) and (II). In compound (II) the substituent is disordered, with atoms O2 and C31 and methyl group C32 occupying two positions with near-equal occupancy. Rings A and C have slightly flattened chair conformations, as shown by the mean values of their torsion angles [52.97 (12)–55.33 (14)°]. The unsaturated ring B adopts a half-chair conformation, with puckering parameters (Cremer & Pople, 1975) Q = 0.474 (3) Å, θ = 52.0 (4)° and ϕ = 210.0 (4)° for (I), and Q = 0.491 (3) Å, θ = 51.5 (3)° and ϕ = 211.0 (5)° for (II).
The five-membered ring D features a double bond at C16—C17 and shows a conformation that can be described as an envelope on C14, with P = 11.3 (3) and τ = 36.0 (2)° [P = 12.0 (4) and τ = 35.7 (2)° for (II)]. The values of the bowing angles, the angle between the least-squares plane of ring A and the least-squares plane that includes the atoms of rings B, C and D, are 23.43 (9) for (I) and 21.35 (4)° for (II). The corresponding distances between terminal atoms C3 and C16 are 8.921 (5) and 8.867 (5) Å, and the values for the pseudo torsion angle C19—C10···C13—C18 are 12.9 (5) for (I) and 9.4 (5)° for (II).
We have performed a quantum mechanical calculation of the equilibrium geometry of the free molecule using GAMESS (Schmidt et al., 1993) under conditions described previously (Ramos Silva et al., 2008). By comparing the calculated and experimental structural parameters it is possible to infer whether the molecular conformation is intrinsic to the free steroid molecule or is rather due to intermolecular interactions. The calculations reproduce the twist of the molecules as measured by the pseudo torsion angle C19—C10···C13—C18, slightly decreased for (I) at 10.2°, and slightly increased for (II) at 9.9°. Such twists are therefore intrinsic to the molecule and not a packing effect, as confirmed by previous studies (Ramos Silva et al., 2008; Pinto et al., 2008; Paixão et al., 2004). For compound (I), the geometry of the isolated molecule that corresponds to the energy minimum is quite similar to that observed in the solid state. Larger differences are found for the head and tail groups; the calculated C3—O1—C31—O2 torsion angle is 0.6° [observed 1.5 (4)°] and the calculated C15—C16—C161—O3 torsion angle is -1.7° [observed 3.2 (5)°].
There are no hydrogen bonds joining the molecules [of (I)?]. They pack in such a way that the terminal acetoxy/formyl groups come close, with the shortest intermolecular contact being O3···O1i at a distance of 3.440 (3)Å [symmetry code: (i) 3/2 - x, 1 - y, -1/2 + z]. Without the formyl substituent, the molecules of (II) pack in a different way. They assemble head to tail, with the shortest intermolecular contact being C14···O2'ii at a distance of 3.311 (9) Å [symmetry code: (ii) -x + 1, -1/2 + y, 1/2 - z].
Packing effects have a significant impact on the conformation of the molecule of (II), as seen by comparison with the calculation for the isolated molecule. The minimum energy for compound (II) is achieved with the acetoxy group in-plane with atoms C3 and C4, and C3—O1—C31—O2 converges to -0.3°, while in the solid state both alternative positions for the acetoxy group result in higher torsion angles [C3—O1—C31—O2 = -8.9 (13) and C3—O1—C31'—O2' = 4.7 (14)°].