organic compounds
(E)-16-(4-Chlorobenzylidene)estrone
aDepartment of Physics, The Madura College, Madurai 625 011, India, bDepartment of Organic Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai 625 021, India, and cDepartment of Food Science and Technology, University of Ruhuna, Mapalana, Kamburupitiya 81100, Sri Lanka
*Correspondence e-mail: plakshmannilantha@ymail.com
In the title compound, C25H25ClO2, the C ring adopts a chair conformation, while the B ring approximates a half-chair conformation. The five-membered ring D has a twist conformation on the C—C bond fused with the C ring. Aromatic rings A and E are not coplanar, as evidenced by the dihedral angle of 7.51 (1)°. In the crystal, O—H⋯O hydrogen bonds form a double chain along the ab plane interconnected by C—H⋯O interactions.
Related literature
For applications of ); Silva et al. (2001); Wang et al. (2003). For related compounds, see: Cooper et al. (1969); Cody et al. (1971); Rajnikant et al. (2006); Gunasekaran et al. (2009). For of ring systems, see: Cremer & Pople (1975); Duax et al. (1976).
as radiodiagnostic compounds and drug delivery systems, see: Katzenellenbogen (1995Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2004); cell SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97.
Supporting information
https://doi.org/10.1107/S1600536812050349/bh2467sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812050349/bh2467Isup2.hkl
A mixture of oestrone (1 mmol), 4-chloro benzaldehyde (1 mmol), potassium hydroxide (5 ml, 20%) in ethanol (5 ml) was refluxed on an oil bath with stirring at 120 °C for 5 h. After completion of the reaction, as indicated by TLC, the reaction mixture was poured into ice-water (50 ml). The product was filtered and washed with water (100 ml) to obtain the title compound, which was dried under vacuum. The compound was further recrystallized from ethanol to obtain suitable crystals for X-ray analysis. Melting point: 185–186 °C, Yield: 82%.
For the title compound, the
expected from the starting reagents was confirmed by the of the (2037 Friedel pairs; Flack, 1983). H atoms were placed at calculated positions and allowed to ride on their carrier atoms with C—H = 0.93–0.98 Å, O—H = 0.82 Å, Uiso(H) =1.2Ueq(carrier C) for CH2 and CH groups, Uiso(H)=1.5Ueq(C14A) for the CH3 group, and Uiso(H1)=1.5Ueq(O1).Synthetic α. The medicinal importance of the compound in conjunction with our research interests prompted us to synthesize and report the X-ray structure of the title compound.
have been proposed as radiodiagnostic compounds (Katzenellenbogen, 1995; Silva et al., 2001; Wang et al., 2003), as well as potential drug delivery systems targeting oestrogen receptor positive breast cancer and other diseases associated with the oestrogen receptor ERIn the title compound (Fig. 1), ring C, with trans fusion to rings B and D, is fixed in a chair conformation, and the ring D adopts a slightly twisted φ = 227.8 (2)° (Cremer & Pople, 1975). The steric repulsive hindrance is reduced by a twisting about the C5—C10 bond (Cooper et al., 1969), leading to a slightly deformed half-chair conformation for ring B (Cody et al., 1971), which is supported by the puckering parameters q2 = 0.528 (3) Å, φ = 128.5 (2) ° and θ = 227.8 (2)°. Ring A displays typical characteristic aromaticity, with delocalization of π electrons producing an average C≐C bond length of 1.381 (3) Å (Duax et al., 1976). Additionally, the C4≐C5≐C6 bond angle is reduced to a value of 117.27 (16)°. These facts are due to a strong interaction of the aromatic atom H4 of ring A and equatorial atom H11 atom on ring C, indicated by an interatomic H···H separation of 2.118 (5) Å. The aromatic rings A and E are not coplanar, as evidenced by the dihedral angle of 7.51 (1)° between them. All these features are consistent with previously reported structures for similar compounds (Rajnikant et al., 2006; Gunasekaran et al., 2009).
as characterized by the puckering parameters, q2 = 0.422 (3) Å andThe
features intermolecular C—H···O and O—H···O interactions in addition to a weak C—H···O intramolecular interaction. The O—H···O interactions form a double chain interconnected by the C—H···O interactions (Fig. 2).For applications of
as radiodiagnostic compounds and drug delivery systems, see: Katzenellenbogen (1995); Silva et al. (2001); Wang et al. (2003). For related compounds, see: Cooper et al. (1969); Cody et al. (1971); Rajnikant et al. (2006); Gunasekaran et al. (2009). For of ring systems, see: Cremer & Pople (1975); Duax et al. (1976).Data collection: APEX2 (Bruker, 2004); cell
SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound, showing 40% probability displacement ellipsoids. | |
Fig. 2. Partial packing diagram showing double chains formation. |
C25H25ClO2 | Dx = 1.294 Mg m−3 |
Mr = 392.90 | Melting point: 458 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 2000 reflections |
a = 6.3601 (3) Å | θ = 2–31° |
b = 11.2012 (6) Å | µ = 0.21 mm−1 |
c = 28.3043 (14) Å | T = 293 K |
V = 2016.42 (18) Å3 | Block, colourless |
Z = 4 | 0.17 × 0.15 × 0.13 mm |
F(000) = 832 |
Bruker Kappa APEXII diffractometer | 4819 independent reflections |
Radiation source: fine-focus sealed tube | 3788 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
Detector resolution: 0 pixels mm-1 | θmax = 27.9°, θmin = 2.3° |
ω and φ scans | h = −8→7 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −14→14 |
Tmin = 0.967, Tmax = 0.974 | l = −37→36 |
23011 measured reflections |
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)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.100 | w = 1/[σ2(Fo2) + (0.0435P)2 + 0.2966P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
4819 reflections | Δρmax = 0.22 e Å−3 |
253 parameters | Δρmin = −0.26 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 2037 Friedel pairs |
0 constraints | Absolute structure parameter: 0.06 (7) |
Primary atom site location: structure-invariant direct methods |
C25H25ClO2 | V = 2016.42 (18) Å3 |
Mr = 392.90 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.3601 (3) Å | µ = 0.21 mm−1 |
b = 11.2012 (6) Å | T = 293 K |
c = 28.3043 (14) Å | 0.17 × 0.15 × 0.13 mm |
Bruker Kappa APEXII diffractometer | 4819 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3788 reflections with I > 2σ(I) |
Tmin = 0.967, Tmax = 0.974 | Rint = 0.034 |
23011 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.100 | Δρmax = 0.22 e Å−3 |
S = 1.02 | Δρmin = −0.26 e Å−3 |
4819 reflections | Absolute structure: Flack (1983), 2037 Friedel pairs |
253 parameters | Absolute structure parameter: 0.06 (7) |
0 restraints |
x | y | z | Uiso*/Ueq | ||
C1 | 0.2517 (3) | −0.05590 (16) | 0.09206 (6) | 0.0420 (4) | |
H1A | 0.1200 | −0.0754 | 0.1041 | 0.050* | |
C2 | 0.3552 (3) | −0.13702 (16) | 0.06397 (7) | 0.0448 (4) | |
C3 | 0.5521 (3) | −0.10893 (17) | 0.04649 (7) | 0.0478 (5) | |
H3 | 0.6251 | −0.1634 | 0.0279 | 0.057* | |
C4 | 0.6387 (3) | 0.00039 (17) | 0.05695 (7) | 0.0451 (4) | |
H4 | 0.7713 | 0.0184 | 0.0451 | 0.054* | |
C5 | 0.5365 (3) | 0.08533 (15) | 0.08452 (6) | 0.0369 (4) | |
C6 | 0.3391 (3) | 0.05456 (16) | 0.10293 (6) | 0.0367 (4) | |
C7 | 0.2169 (3) | 0.13852 (16) | 0.13436 (7) | 0.0452 (5) | |
H7A | 0.1693 | 0.0949 | 0.1620 | 0.054* | |
H7B | 0.0932 | 0.1657 | 0.1174 | 0.054* | |
C8 | 0.3413 (3) | 0.24637 (17) | 0.15048 (7) | 0.0456 (5) | |
H8A | 0.4355 | 0.2234 | 0.1759 | 0.055* | |
H8B | 0.2459 | 0.3067 | 0.1625 | 0.055* | |
C9 | 0.4680 (3) | 0.29775 (15) | 0.10975 (6) | 0.0358 (4) | |
H9 | 0.3731 | 0.3114 | 0.0830 | 0.043* | |
C10 | 0.6358 (3) | 0.20596 (16) | 0.09476 (6) | 0.0367 (4) | |
H10 | 0.7275 | 0.1944 | 0.1222 | 0.044* | |
C11 | 0.7758 (3) | 0.25270 (16) | 0.05509 (7) | 0.0461 (5) | |
H11A | 0.6930 | 0.2589 | 0.0264 | 0.055* | |
H11B | 0.8873 | 0.1954 | 0.0493 | 0.055* | |
C12 | 0.8747 (3) | 0.37515 (17) | 0.06580 (7) | 0.0486 (5) | |
H12A | 0.9754 | 0.3673 | 0.0914 | 0.058* | |
H12B | 0.9489 | 0.4040 | 0.0381 | 0.058* | |
C13 | 0.7053 (3) | 0.46360 (16) | 0.07958 (6) | 0.0394 (4) | |
C14A | 0.5673 (3) | 0.49699 (18) | 0.03654 (7) | 0.0533 (5) | |
H14A | 0.4614 | 0.5531 | 0.0461 | 0.080* | |
H14B | 0.5012 | 0.4264 | 0.0243 | 0.080* | |
H14C | 0.6537 | 0.5322 | 0.0125 | 0.080* | |
C15 | 0.5779 (3) | 0.41378 (15) | 0.12129 (6) | 0.0362 (4) | |
H15 | 0.6805 | 0.3949 | 0.1460 | 0.043* | |
C16 | 0.4532 (3) | 0.52206 (15) | 0.13940 (7) | 0.0420 (4) | |
H16A | 0.3278 | 0.5355 | 0.1206 | 0.050* | |
H16B | 0.4135 | 0.5122 | 0.1723 | 0.050* | |
C17 | 0.6101 (3) | 0.62256 (17) | 0.13336 (7) | 0.0433 (4) | |
C18 | 0.7770 (3) | 0.58149 (17) | 0.10050 (7) | 0.0449 (4) | |
C19 | 0.6214 (3) | 0.73160 (17) | 0.15245 (7) | 0.0464 (5) | |
H19 | 0.7401 | 0.7754 | 0.1442 | 0.056* | |
C20 | 0.4751 (3) | 0.79255 (16) | 0.18433 (7) | 0.0459 (4) | |
C21 | 0.2732 (4) | 0.75169 (18) | 0.19375 (8) | 0.0574 (6) | |
H21 | 0.2274 | 0.6811 | 0.1798 | 0.069* | |
C22 | 0.1395 (4) | 0.8131 (2) | 0.22317 (8) | 0.0610 (6) | |
H22 | 0.0065 | 0.7831 | 0.2299 | 0.073* | |
C23 | 0.2042 (4) | 0.91873 (19) | 0.24246 (7) | 0.0544 (5) | |
C24 | 0.4006 (4) | 0.9632 (2) | 0.23352 (8) | 0.0598 (6) | |
H24 | 0.4434 | 1.0350 | 0.2469 | 0.072* | |
C25 | 0.5342 (4) | 0.90013 (18) | 0.20449 (7) | 0.0538 (5) | |
H25 | 0.6674 | 0.9305 | 0.1983 | 0.065* | |
O1 | 0.2750 (2) | −0.24606 (12) | 0.05227 (6) | 0.0622 (4) | |
H1 | 0.1584 | −0.2538 | 0.0642 | 0.093* | |
O2 | 0.9391 (2) | 0.63375 (13) | 0.09181 (6) | 0.0698 (5) | |
Cl1 | 0.03190 (11) | 0.99936 (6) | 0.27780 (3) | 0.0845 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0336 (9) | 0.0398 (10) | 0.0525 (11) | −0.0008 (8) | 0.0016 (8) | 0.0097 (9) |
C2 | 0.0501 (11) | 0.0320 (10) | 0.0524 (11) | −0.0018 (8) | −0.0056 (9) | 0.0039 (8) |
C3 | 0.0495 (11) | 0.0361 (10) | 0.0577 (11) | 0.0013 (9) | 0.0092 (10) | −0.0032 (9) |
C4 | 0.0377 (9) | 0.0409 (11) | 0.0568 (11) | 0.0017 (8) | 0.0105 (9) | −0.0006 (9) |
C5 | 0.0341 (8) | 0.0333 (9) | 0.0431 (9) | 0.0020 (8) | 0.0006 (7) | 0.0032 (7) |
C6 | 0.0339 (8) | 0.0325 (9) | 0.0438 (9) | 0.0038 (7) | 0.0002 (7) | 0.0062 (8) |
C7 | 0.0378 (9) | 0.0400 (10) | 0.0580 (11) | −0.0005 (8) | 0.0134 (9) | 0.0061 (9) |
C8 | 0.0465 (10) | 0.0391 (11) | 0.0512 (11) | 0.0010 (9) | 0.0156 (9) | −0.0010 (9) |
C9 | 0.0342 (8) | 0.0346 (9) | 0.0386 (9) | 0.0004 (7) | 0.0058 (7) | 0.0005 (7) |
C10 | 0.0312 (8) | 0.0350 (9) | 0.0439 (10) | 0.0017 (7) | 0.0010 (8) | 0.0002 (8) |
C11 | 0.0417 (10) | 0.0403 (10) | 0.0564 (11) | −0.0024 (9) | 0.0148 (9) | −0.0033 (9) |
C12 | 0.0417 (10) | 0.0448 (11) | 0.0592 (12) | −0.0069 (9) | 0.0138 (9) | −0.0033 (9) |
C13 | 0.0384 (9) | 0.0354 (10) | 0.0445 (10) | −0.0052 (8) | 0.0049 (8) | 0.0023 (8) |
C14A | 0.0700 (13) | 0.0475 (12) | 0.0425 (10) | −0.0061 (11) | −0.0005 (9) | 0.0057 (9) |
C15 | 0.0350 (8) | 0.0336 (9) | 0.0399 (9) | −0.0022 (7) | 0.0014 (7) | 0.0010 (7) |
C16 | 0.0439 (9) | 0.0369 (10) | 0.0452 (10) | −0.0026 (8) | 0.0046 (8) | −0.0027 (8) |
C17 | 0.0461 (10) | 0.0369 (10) | 0.0469 (10) | −0.0015 (8) | −0.0024 (8) | 0.0003 (8) |
C18 | 0.0425 (10) | 0.0384 (10) | 0.0538 (11) | −0.0061 (9) | 0.0019 (9) | 0.0023 (9) |
C19 | 0.0480 (11) | 0.0397 (11) | 0.0515 (11) | −0.0076 (9) | −0.0042 (9) | 0.0014 (9) |
C20 | 0.0550 (12) | 0.0349 (10) | 0.0478 (10) | 0.0000 (9) | −0.0085 (9) | −0.0002 (8) |
C21 | 0.0620 (13) | 0.0367 (11) | 0.0733 (14) | −0.0061 (10) | 0.0060 (11) | −0.0110 (10) |
C22 | 0.0599 (13) | 0.0450 (12) | 0.0783 (15) | 0.0008 (10) | 0.0035 (12) | −0.0082 (11) |
C23 | 0.0647 (13) | 0.0475 (12) | 0.0509 (12) | 0.0134 (11) | −0.0067 (10) | −0.0081 (10) |
C24 | 0.0730 (15) | 0.0440 (12) | 0.0625 (13) | 0.0030 (11) | −0.0198 (11) | −0.0163 (10) |
C25 | 0.0563 (12) | 0.0451 (11) | 0.0601 (12) | −0.0018 (10) | −0.0122 (10) | −0.0041 (10) |
O1 | 0.0611 (9) | 0.0404 (8) | 0.0852 (10) | −0.0128 (7) | 0.0066 (8) | −0.0107 (7) |
O2 | 0.0550 (9) | 0.0561 (9) | 0.0982 (12) | −0.0228 (8) | 0.0191 (9) | −0.0089 (9) |
Cl1 | 0.0868 (4) | 0.0770 (5) | 0.0897 (4) | 0.0234 (4) | −0.0009 (4) | −0.0325 (3) |
C1—C2 | 1.375 (3) | C13—C18 | 1.517 (3) |
C1—C6 | 1.391 (3) | C13—C15 | 1.537 (2) |
C1—H1A | 0.9300 | C13—C14A | 1.547 (3) |
C2—O1 | 1.364 (2) | C14A—H14A | 0.9600 |
C2—C3 | 1.382 (3) | C14A—H14B | 0.9600 |
C3—C4 | 1.375 (3) | C14A—H14C | 0.9600 |
C3—H3 | 0.9300 | C15—C16 | 1.537 (2) |
C4—C5 | 1.391 (2) | C15—H15 | 0.9800 |
C4—H4 | 0.9300 | C16—C17 | 1.514 (3) |
C5—C6 | 1.403 (2) | C16—H16A | 0.9700 |
C5—C10 | 1.519 (3) | C16—H16B | 0.9700 |
C6—C7 | 1.510 (3) | C17—C19 | 1.337 (3) |
C7—C8 | 1.515 (3) | C17—C18 | 1.484 (3) |
C7—H7A | 0.9700 | C18—O2 | 1.211 (2) |
C7—H7B | 0.9700 | C19—C20 | 1.465 (3) |
C8—C9 | 1.520 (2) | C19—H19 | 0.9300 |
C8—H8A | 0.9700 | C20—C25 | 1.385 (3) |
C8—H8B | 0.9700 | C20—C21 | 1.389 (3) |
C9—C15 | 1.511 (2) | C21—C22 | 1.375 (3) |
C9—C10 | 1.542 (2) | C21—H21 | 0.9300 |
C9—H9 | 0.9800 | C22—C23 | 1.367 (3) |
C10—C11 | 1.526 (2) | C22—H22 | 0.9300 |
C10—H10 | 0.9800 | C23—C24 | 1.368 (3) |
C11—C12 | 1.539 (3) | C23—Cl1 | 1.737 (2) |
C11—H11A | 0.9700 | C24—C25 | 1.376 (3) |
C11—H11B | 0.9700 | C24—H24 | 0.9300 |
C12—C13 | 1.515 (3) | C25—H25 | 0.9300 |
C12—H12A | 0.9700 | O1—H1 | 0.8200 |
C12—H12B | 0.9700 | ||
C2—C1—C6 | 121.61 (16) | H12A—C12—H12B | 108.2 |
C2—C1—H1A | 119.2 | C12—C13—C18 | 117.13 (15) |
C6—C1—H1A | 119.2 | C12—C13—C15 | 109.59 (14) |
O1—C2—C1 | 123.56 (18) | C18—C13—C15 | 100.06 (14) |
O1—C2—C3 | 117.09 (18) | C12—C13—C14A | 111.03 (16) |
C1—C2—C3 | 119.35 (17) | C18—C13—C14A | 105.50 (15) |
C4—C3—C2 | 119.25 (18) | C15—C13—C14A | 113.17 (15) |
C4—C3—H3 | 120.4 | C13—C14A—H14A | 109.5 |
C2—C3—H3 | 120.4 | C13—C14A—H14B | 109.5 |
C3—C4—C5 | 122.86 (17) | H14A—C14A—H14B | 109.5 |
C3—C4—H4 | 118.6 | C13—C14A—H14C | 109.5 |
C5—C4—H4 | 118.6 | H14A—C14A—H14C | 109.5 |
C4—C5—C6 | 117.27 (16) | H14B—C14A—H14C | 109.5 |
C4—C5—C10 | 121.40 (16) | C9—C15—C13 | 112.96 (14) |
C6—C5—C10 | 121.32 (16) | C9—C15—C16 | 120.79 (14) |
C1—C6—C5 | 119.63 (16) | C13—C15—C16 | 103.99 (13) |
C1—C6—C7 | 118.60 (16) | C9—C15—H15 | 106.0 |
C5—C6—C7 | 121.77 (16) | C13—C15—H15 | 106.0 |
C6—C7—C8 | 113.92 (15) | C16—C15—H15 | 106.0 |
C6—C7—H7A | 108.8 | C17—C16—C15 | 102.05 (14) |
C8—C7—H7A | 108.8 | C17—C16—H16A | 111.4 |
C6—C7—H7B | 108.8 | C15—C16—H16A | 111.4 |
C8—C7—H7B | 108.8 | C17—C16—H16B | 111.4 |
H7A—C7—H7B | 107.7 | C15—C16—H16B | 111.4 |
C7—C8—C9 | 110.52 (15) | H16A—C16—H16B | 109.2 |
C7—C8—H8A | 109.5 | C19—C17—C18 | 119.86 (18) |
C9—C8—H8A | 109.5 | C19—C17—C16 | 131.97 (18) |
C7—C8—H8B | 109.5 | C18—C17—C16 | 108.15 (15) |
C9—C8—H8B | 109.5 | O2—C18—C17 | 125.89 (18) |
H8A—C8—H8B | 108.1 | O2—C18—C13 | 126.68 (18) |
C15—C9—C8 | 114.01 (14) | C17—C18—C13 | 107.43 (15) |
C15—C9—C10 | 108.23 (14) | C17—C19—C20 | 129.83 (18) |
C8—C9—C10 | 108.86 (14) | C17—C19—H19 | 115.1 |
C15—C9—H9 | 108.5 | C20—C19—H19 | 115.1 |
C8—C9—H9 | 108.5 | C25—C20—C21 | 117.27 (19) |
C10—C9—H9 | 108.5 | C25—C20—C19 | 119.16 (19) |
C5—C10—C11 | 114.03 (15) | C21—C20—C19 | 123.48 (17) |
C5—C10—C9 | 110.97 (14) | C22—C21—C20 | 121.56 (19) |
C11—C10—C9 | 112.19 (14) | C22—C21—H21 | 119.2 |
C5—C10—H10 | 106.4 | C20—C21—H21 | 119.2 |
C11—C10—H10 | 106.4 | C23—C22—C21 | 119.3 (2) |
C9—C10—H10 | 106.4 | C23—C22—H22 | 120.4 |
C10—C11—C12 | 113.53 (15) | C21—C22—H22 | 120.4 |
C10—C11—H11A | 108.9 | C22—C23—C24 | 121.1 (2) |
C12—C11—H11A | 108.9 | C22—C23—Cl1 | 119.36 (18) |
C10—C11—H11B | 108.9 | C24—C23—Cl1 | 119.57 (17) |
C12—C11—H11B | 108.9 | C23—C24—C25 | 119.16 (19) |
H11A—C11—H11B | 107.7 | C23—C24—H24 | 120.4 |
C13—C12—C11 | 110.05 (15) | C25—C24—H24 | 120.4 |
C13—C12—H12A | 109.7 | C24—C25—C20 | 121.7 (2) |
C11—C12—H12A | 109.7 | C24—C25—H25 | 119.2 |
C13—C12—H12B | 109.7 | C20—C25—H25 | 119.2 |
C11—C12—H12B | 109.7 | C2—O1—H1 | 109.5 |
C6—C1—C2—O1 | −179.72 (17) | C10—C9—C15—C16 | −177.53 (15) |
C6—C1—C2—C3 | 0.8 (3) | C12—C13—C15—C9 | −61.04 (19) |
O1—C2—C3—C4 | 179.40 (17) | C18—C13—C15—C9 | 175.26 (14) |
C1—C2—C3—C4 | −1.1 (3) | C14A—C13—C15—C9 | 63.48 (19) |
C2—C3—C4—C5 | −0.1 (3) | C12—C13—C15—C16 | 166.24 (15) |
C3—C4—C5—C6 | 1.6 (3) | C18—C13—C15—C16 | 42.54 (17) |
C3—C4—C5—C10 | −179.11 (17) | C14A—C13—C15—C16 | −69.24 (18) |
C2—C1—C6—C5 | 0.7 (3) | C9—C15—C16—C17 | −165.37 (15) |
C2—C1—C6—C7 | −179.44 (17) | C13—C15—C16—C17 | −37.32 (17) |
C4—C5—C6—C1 | −1.8 (2) | C15—C16—C17—C19 | −161.1 (2) |
C10—C5—C6—C1 | 178.84 (16) | C15—C16—C17—C18 | 17.24 (19) |
C4—C5—C6—C7 | 178.34 (17) | C19—C17—C18—O2 | 7.3 (3) |
C10—C5—C6—C7 | −1.0 (3) | C16—C17—C18—O2 | −171.3 (2) |
C1—C6—C7—C8 | 170.23 (16) | C19—C17—C18—C13 | −172.01 (17) |
C5—C6—C7—C8 | −9.9 (2) | C16—C17—C18—C13 | 9.4 (2) |
C6—C7—C8—C9 | 43.0 (2) | C12—C13—C18—O2 | 30.6 (3) |
C7—C8—C9—C15 | 173.49 (15) | C15—C13—C18—O2 | 148.9 (2) |
C7—C8—C9—C10 | −65.58 (19) | C14A—C13—C18—O2 | −93.5 (2) |
C4—C5—C10—C11 | 31.8 (2) | C12—C13—C18—C17 | −150.10 (16) |
C6—C5—C10—C11 | −148.94 (16) | C15—C13—C18—C17 | −31.83 (18) |
C4—C5—C10—C9 | 159.62 (16) | C14A—C13—C18—C17 | 85.80 (17) |
C6—C5—C10—C9 | −21.1 (2) | C18—C17—C19—C20 | 178.14 (18) |
C15—C9—C10—C5 | 177.72 (14) | C16—C17—C19—C20 | −3.7 (4) |
C8—C9—C10—C5 | 53.30 (19) | C17—C19—C20—C25 | 171.5 (2) |
C15—C9—C10—C11 | −53.43 (19) | C17—C19—C20—C21 | −12.1 (3) |
C8—C9—C10—C11 | −177.85 (15) | C25—C20—C21—C22 | −2.2 (3) |
C5—C10—C11—C12 | 179.77 (15) | C19—C20—C21—C22 | −178.62 (19) |
C9—C10—C11—C12 | 52.5 (2) | C20—C21—C22—C23 | 2.1 (3) |
C10—C11—C12—C13 | −53.1 (2) | C21—C22—C23—C24 | −1.0 (3) |
C11—C12—C13—C18 | 168.38 (16) | C21—C22—C23—Cl1 | 177.52 (17) |
C11—C12—C13—C15 | 55.4 (2) | C22—C23—C24—C25 | 0.2 (3) |
C11—C12—C13—C14A | −70.4 (2) | Cl1—C23—C24—C25 | −178.34 (16) |
C8—C9—C15—C13 | 179.84 (15) | C23—C24—C25—C20 | −0.4 (3) |
C10—C9—C15—C13 | 58.55 (18) | C21—C20—C25—C24 | 1.4 (3) |
C8—C9—C15—C16 | −56.2 (2) | C19—C20—C25—C24 | 177.93 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.82 | 2.03 | 2.762 (3) | 148 |
C14A—H14A···O1ii | 0.96 | 2.55 | 3.454 (3) | 157 |
Symmetry codes: (i) x−1, y−1, z; (ii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C25H25ClO2 |
Mr | 392.90 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 6.3601 (3), 11.2012 (6), 28.3043 (14) |
V (Å3) | 2016.42 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.21 |
Crystal size (mm) | 0.17 × 0.15 × 0.13 |
Data collection | |
Diffractometer | Bruker Kappa APEXII |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.967, 0.974 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23011, 4819, 3788 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.659 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.100, 1.02 |
No. of reflections | 4819 |
No. of parameters | 253 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.26 |
Absolute structure | Flack (1983), 2037 Friedel pairs |
Absolute structure parameter | 0.06 (7) |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.82 | 2.03 | 2.762 (3) | 148 |
C14A—H14A···O1ii | 0.96 | 2.55 | 3.454 (3) | 157 |
Symmetry codes: (i) x−1, y−1, z; (ii) x, y+1, z. |
Acknowledgements
JS thanks the UGC for the FIST support. JS and HT thank the management of Madura College for their encouragement and support. RRK thanks the DST, New Delhi for funds under the fast-track scheme (No. SR/FT/CS-073/2009)
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Synthetic steroids have been proposed as radiodiagnostic compounds (Katzenellenbogen, 1995; Silva et al., 2001; Wang et al., 2003), as well as potential drug delivery systems targeting oestrogen receptor positive breast cancer and other diseases associated with the oestrogen receptor ERα. The medicinal importance of the compound in conjunction with our research interests prompted us to synthesize and report the X-ray structure of the title compound.
In the title compound (Fig. 1), ring C, with trans fusion to rings B and D, is fixed in a chair conformation, and the ring D adopts a slightly twisted envelope conformation, as characterized by the puckering parameters, q2 = 0.422 (3) Å and φ = 227.8 (2)° (Cremer & Pople, 1975). The steric repulsive hindrance is reduced by a twisting about the C5—C10 bond (Cooper et al., 1969), leading to a slightly deformed half-chair conformation for ring B (Cody et al., 1971), which is supported by the puckering parameters q2 = 0.528 (3) Å, φ = 128.5 (2) ° and θ = 227.8 (2)°. Ring A displays typical characteristic aromaticity, with delocalization of π electrons producing an average C≐C bond length of 1.381 (3) Å (Duax et al., 1976). Additionally, the C4≐C5≐C6 bond angle is reduced to a value of 117.27 (16)°. These facts are due to a strong interaction of the aromatic atom H4 of ring A and equatorial atom H11 atom on ring C, indicated by an interatomic H···H separation of 2.118 (5) Å. The aromatic rings A and E are not coplanar, as evidenced by the dihedral angle of 7.51 (1)° between them. All these features are consistent with previously reported structures for similar compounds (Rajnikant et al., 2006; Gunasekaran et al., 2009).
The crystal structure features intermolecular C—H···O and O—H···O interactions in addition to a weak C—H···O intramolecular interaction. The O—H···O interactions form a double chain interconnected by the C—H···O interactions (Fig. 2).