3-Iodo-8β,9α,14α-estra-1,3,5(10)-trien-17-one

Ketuly, K.A.; Hadi, A.H.A.; Ng, S.W.

doi:10.1107/S1600536809014603

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1195

doi:10.1107/S1600536809014603

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3-Iodo-8β,9α,14α-estra-1,3,5(10)-trien-17-one

Kamal Aziz Ketuly,^a A. Hamid A. Hadi ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 18 April 2009; accepted 20 April 2009; online 7 May 2009)

In the title compound, C₁₈H₂₁IO, the cyclohexane ring adopts a chair conformation, whereas the cyclopentane ring and the ten-membered tetraline portions each adopt an envelope conformation. For the five-membered ring, the methine C atom deviates by 0.638 (4) Å (r.m.s. of the four other atoms is 0.005 Å) and for the ten-membered ring, the methine C atom constituting the flap deviates by 0.671 (3) Å (r.m.s. of the other nine atoms is 0.066 Å).

Related literature

There are only a few crystal structure reports of similar compounds; for the methoxyl-substituted derivative, see: Herrmann et al. (2006 ). For the synthesis of the 3-amino-substituted reagent, see: Conrow & Bernstein (1968 ).

Experimental

Crystal data

C₁₈H₂₁IO
M_r = 380.25
Orthorhombic, P 2₁ 2₁ 2₁
a = 9.9636 (2) Å
b = 10.5246 (2) Å
c = 14.3535 (2) Å
V = 1505.15 (5) Å³
Z = 4
Mo Kα radiation
μ = 2.12 mm⁻¹
T = 100 K
0.20 × 0.15 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.636, T_max = 0.746 (expected range = 0.690–0.809)
10547 measured reflections
3452 independent reflections
3353 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.018
wR(F²) = 0.045
S = 1.03
3452 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.39 e Å⁻³
Absolute structure: Flack (1983 ), 1473 Friedel pairs
Flack parameter: 0.01 (2)

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809014603/tk2435sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809014603/tk2435Isup2.hkl

checkCIF report

Related literature top

There are only few crystal structure reports of similar compounds; for the methoxyl-substituted derivative, see: Herrmann et al. (2006). For the synthesis of the 3-amino-substituted reagent, see: Conrow & Bernstein (1968).

Experimental top

The reactant, 3-amino-estra-1,3,5(1)-trien-17-one, was synthesized by using a literature procedure (Conrow & Bernstein, 1968). The compound (390 mg) was dissolved in hydrobromic acid (54% w/v). Concentrated sulfuric acid (2 ml) and water (4 ml) were added. The solution was cooled in an ice-bath. Sodium nitrite (147 mg) in water (2 ml) was added followed by the addition of excess potassium iodide (1.02 g) dissolved in water (4 ml).

The solution was filtered and the gummy product collected and dissolved in ether–ethyl acetate. The solvent was removed and the crude product (537 mg) chromatographed on a silica-gel (40 g) column. The compound was eluted by chloroform–ethyl acetate (3:1 v/v). The second fraction (465 mg) was a tan glassy material. This was recrystallized from chloroform, methanol and ethyl acetate to give single crystals.

Computing details top

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

Figures top

Fig. 1. Displacement ellipsoid plot (Barbour, 2001) of C₁₈H₂₁IO at the 70% probability level. H atoms are drawn as spheres of arbitrary radius.

3-Iodo-8β,9α,14α-estra-1,3,5(10)-trien-17-one top

Crystal data top

C₁₈H₂₁IO	F(000) = 760
M_r = 380.25	D_x = 1.678 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6954 reflections
a = 9.9636 (2) Å	θ = 2.4–28.3°
b = 10.5246 (2) Å	µ = 2.12 mm⁻¹
c = 14.3535 (2) Å	T = 100 K
V = 1505.15 (5) Å³	Irregular block, colorless
Z = 4	0.20 × 0.15 × 0.10 mm

Data collection top

Bruker SMART APEX diffractometer	3452 independent reflections
Radiation source: fine-focus sealed tube	3353 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.636, T_max = 0.746	k = −13→13
10547 measured reflections	l = −18→18

Refinement top

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)] = 0.018	H-atom parameters constrained
wR(F²) = 0.045	w = 1/[σ²(F_o²) + (0.0262P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
3452 reflections	Δρ_max = 0.47 e Å⁻³
181 parameters	Δρ_min = −0.39 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1473 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (2)

Crystal data top

C₁₈H₂₁IO	V = 1505.15 (5) Å³
M_r = 380.25	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 9.9636 (2) Å	µ = 2.12 mm⁻¹
b = 10.5246 (2) Å	T = 100 K
c = 14.3535 (2) Å	0.20 × 0.15 × 0.10 mm

Data collection top

Bruker SMART APEX diffractometer	3452 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3353 reflections with I > 2σ(I)
T_min = 0.636, T_max = 0.746	R_int = 0.021
10547 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.018	H-atom parameters constrained
wR(F²) = 0.045	Δρ_max = 0.47 e Å⁻³
S = 1.03	Δρ_min = −0.39 e Å⁻³
3452 reflections	Absolute structure: Flack (1983), 1473 Friedel pairs
181 parameters	Absolute structure parameter: 0.01 (2)
0 restraints

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

	x	y	z	U_iso*/U_eq
I1	0.398911 (14)	1.187407 (14)	0.171916 (11)	0.01746 (5)
O1	0.05863 (18)	0.21965 (16)	0.45415 (13)	0.0230 (4)
C1	0.0408 (2)	0.3314 (2)	0.46921 (16)	0.0164 (5)
C2	−0.0646 (3)	0.3860 (2)	0.53518 (19)	0.0192 (6)
H2A	−0.0492	0.3557	0.5996	0.023*
H2B	−0.1558	0.3604	0.5155	0.023*
C3	−0.0483 (3)	0.5320 (2)	0.52963 (18)	0.0185 (5)
H3A	−0.1362	0.5755	0.5333	0.022*
H3B	0.0108	0.5641	0.5798	0.022*
C4	0.0166 (2)	0.5494 (2)	0.43324 (16)	0.0133 (5)
H4	−0.0548	0.5300	0.3864	0.016*
C5	0.0771 (2)	0.6760 (2)	0.40501 (15)	0.0117 (4)
H5	0.1566	0.6930	0.4456	0.014*
C6	−0.0183 (2)	0.7883 (2)	0.41237 (16)	0.0146 (5)
H6A	−0.0606	0.7891	0.4748	0.018*
H6B	−0.0903	0.7799	0.3652	0.018*
C7	0.0573 (2)	0.9119 (2)	0.39693 (17)	0.0143 (5)
H7A	0.1071	0.9338	0.4544	0.017*
H7B	−0.0081	0.9808	0.3848	0.017*
C8	0.1562 (2)	0.9044 (2)	0.31532 (16)	0.0126 (5)
C9	0.2161 (2)	1.0179 (2)	0.28663 (17)	0.0139 (5)
H9	0.1950	1.0952	0.3175	0.017*
C10	0.3063 (2)	1.0176 (2)	0.21308 (17)	0.0144 (5)
C11	0.3359 (2)	0.9057 (2)	0.16548 (19)	0.0169 (5)
H11	0.3958	0.9061	0.1140	0.020*
C12	0.2762 (2)	0.7942 (2)	0.19494 (15)	0.0168 (5)
H12	0.2962	0.7176	0.1628	0.020*
C13	0.1868 (2)	0.7901 (2)	0.27081 (16)	0.0129 (5)
C14	0.1260 (2)	0.6646 (2)	0.30264 (15)	0.0128 (5)
H14	0.0443	0.6503	0.2636	0.015*
C15	0.2184 (3)	0.5497 (2)	0.28692 (18)	0.0176 (5)
H15A	0.2341	0.5399	0.2192	0.021*
H15B	0.3061	0.5670	0.3167	0.021*
C16	0.1628 (2)	0.4241 (2)	0.32552 (19)	0.0162 (5)
H16A	0.0849	0.3967	0.2876	0.019*
H16B	0.2326	0.3574	0.3215	0.019*
C17	0.1194 (2)	0.4408 (2)	0.42701 (15)	0.0133 (5)
C18	0.2423 (2)	0.4595 (2)	0.49110 (18)	0.0191 (5)
H18A	0.2991	0.5274	0.4661	0.029*
H18B	0.2939	0.3804	0.4941	0.029*
H18C	0.2119	0.4827	0.5538	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01720 (7)	0.01525 (7)	0.01993 (8)	−0.00127 (6)	0.00318 (6)	0.00288 (7)
O1	0.0296 (10)	0.0126 (9)	0.0269 (10)	−0.0016 (7)	0.0042 (8)	−0.0013 (7)
C1	0.0185 (11)	0.0152 (12)	0.0155 (11)	−0.0005 (10)	−0.0024 (9)	0.0012 (10)
C2	0.0233 (13)	0.0143 (12)	0.0199 (13)	−0.0021 (10)	0.0064 (10)	0.0013 (10)
C3	0.0237 (12)	0.0134 (12)	0.0185 (12)	−0.0014 (9)	0.0064 (10)	−0.0010 (10)
C4	0.0161 (11)	0.0123 (11)	0.0115 (11)	−0.0015 (9)	0.0001 (9)	−0.0008 (9)
C5	0.0114 (10)	0.0119 (10)	0.0118 (10)	0.0016 (9)	−0.0003 (8)	−0.0013 (9)
C6	0.0148 (11)	0.0152 (12)	0.0138 (11)	0.0014 (9)	0.0031 (9)	−0.0015 (9)
C7	0.0186 (12)	0.0119 (11)	0.0124 (11)	0.0014 (9)	0.0029 (9)	−0.0016 (9)
C8	0.0114 (9)	0.0138 (11)	0.0125 (12)	0.0017 (8)	−0.0034 (9)	0.0005 (10)
C9	0.0148 (12)	0.0131 (11)	0.0137 (11)	0.0008 (9)	−0.0031 (9)	−0.0006 (9)
C10	0.0124 (10)	0.0152 (11)	0.0158 (11)	0.0009 (9)	−0.0013 (9)	0.0014 (9)
C11	0.0182 (11)	0.0187 (11)	0.0137 (11)	0.0004 (9)	0.0030 (10)	−0.0012 (11)
C12	0.0221 (12)	0.0153 (12)	0.0131 (11)	0.0011 (9)	0.0023 (9)	−0.0023 (9)
C13	0.0126 (10)	0.0126 (12)	0.0135 (11)	−0.0009 (9)	−0.0020 (8)	0.0016 (9)
C14	0.0141 (11)	0.0125 (11)	0.0116 (11)	−0.0012 (8)	0.0010 (8)	−0.0008 (8)
C15	0.0232 (13)	0.0132 (12)	0.0165 (12)	0.0008 (10)	0.0080 (10)	−0.0022 (10)
C16	0.0210 (11)	0.0095 (10)	0.0181 (11)	−0.0012 (9)	0.0067 (11)	−0.0038 (12)
C17	0.0161 (12)	0.0115 (10)	0.0124 (11)	−0.0023 (10)	0.0002 (9)	−0.0016 (9)
C18	0.0185 (11)	0.0137 (11)	0.0250 (13)	0.0014 (9)	−0.0075 (10)	0.0028 (11)

Geometric parameters (Å, º) top

I1—C10	2.097 (2)	C8—C9	1.397 (3)
O1—C1	1.209 (3)	C8—C13	1.396 (3)
C1—C2	1.526 (3)	C9—C10	1.386 (3)
C1—C17	1.518 (3)	C9—H9	0.9500
C2—C3	1.547 (3)	C10—C11	1.393 (3)
C2—H2A	0.9900	C11—C12	1.382 (3)
C2—H2B	0.9900	C11—H11	0.9500
C3—C4	1.538 (3)	C12—C13	1.407 (3)
C3—H3A	0.9900	C12—H12	0.9500
C3—H3B	0.9900	C13—C14	1.524 (3)
C4—C5	1.517 (3)	C14—C15	1.537 (3)
C4—C17	1.539 (3)	C14—H14	1.0000
C4—H4	1.0000	C15—C16	1.537 (3)
C5—C6	1.520 (3)	C15—H15A	0.9900
C5—C14	1.553 (3)	C15—H15B	0.9900
C5—H5	1.0000	C16—C17	1.529 (3)
C6—C7	1.520 (3)	C16—H16A	0.9900
C6—H6A	0.9900	C16—H16B	0.9900
C6—H6B	0.9900	C17—C18	1.544 (3)
C7—C8	1.533 (3)	C18—H18A	0.9800
C7—H7A	0.9900	C18—H18B	0.9800
C7—H7B	0.9900	C18—H18C	0.9800

O1—C1—C2	125.3 (2)	C8—C9—H9	120.0
O1—C1—C17	126.2 (2)	C9—C10—C11	120.9 (2)
C2—C1—C17	108.5 (2)	C9—C10—I1	119.85 (18)
C1—C2—C3	105.6 (2)	C11—C10—I1	119.26 (18)
C1—C2—H2A	110.6	C12—C11—C10	118.4 (2)
C3—C2—H2A	110.6	C12—C11—H11	120.8
C1—C2—H2B	110.6	C10—C11—H11	120.8
C3—C2—H2B	110.6	C11—C12—C13	122.3 (2)
H2A—C2—H2B	108.7	C11—C12—H12	118.8
C4—C3—C2	102.1 (2)	C13—C12—H12	118.8
C4—C3—H3A	111.4	C8—C13—C12	117.8 (2)
C2—C3—H3A	111.4	C8—C13—C14	121.5 (2)
C4—C3—H3B	111.4	C12—C13—C14	120.7 (2)
C2—C3—H3B	111.4	C13—C14—C15	113.55 (18)
H3A—C3—H3B	109.2	C13—C14—C5	109.98 (19)
C5—C4—C3	120.79 (19)	C15—C14—C5	112.83 (19)
C5—C4—C17	111.87 (18)	C13—C14—H14	106.7
C3—C4—C17	104.08 (19)	C15—C14—H14	106.7
C5—C4—H4	106.4	C5—C14—H14	106.7
C3—C4—H4	106.4	C16—C15—C14	114.06 (19)
C17—C4—H4	106.4	C16—C15—H15A	108.7
C4—C5—C6	114.57 (18)	C14—C15—H15A	108.7
C4—C5—C14	108.02 (18)	C16—C15—H15B	108.7
C6—C5—C14	108.79 (18)	C14—C15—H15B	108.7
C4—C5—H5	108.4	H15A—C15—H15B	107.6
C6—C5—H5	108.4	C17—C16—C15	110.27 (19)
C14—C5—H5	108.4	C17—C16—H16A	109.6
C5—C6—C7	110.23 (18)	C15—C16—H16A	109.6
C5—C6—H6A	109.6	C17—C16—H16B	109.6
C7—C6—H6A	109.6	C15—C16—H16B	109.6
C5—C6—H6B	109.6	H16A—C16—H16B	108.1
C7—C6—H6B	109.6	C1—C17—C16	116.02 (19)
H6A—C6—H6B	108.1	C1—C17—C4	101.32 (18)
C6—C7—C8	112.71 (19)	C16—C17—C4	109.19 (19)
C6—C7—H7A	109.1	C1—C17—C18	105.57 (19)
C8—C7—H7A	109.1	C16—C17—C18	111.01 (19)
C6—C7—H7B	109.1	C4—C17—C18	113.48 (19)
C8—C7—H7B	109.1	C17—C18—H18A	109.5
H7A—C7—H7B	107.8	C17—C18—H18B	109.5
C9—C8—C13	120.6 (2)	H18A—C18—H18B	109.5
C9—C8—C7	117.1 (2)	C17—C18—H18C	109.5
C13—C8—C7	122.3 (2)	H18A—C18—H18C	109.5
C10—C9—C8	119.9 (2)	H18B—C18—H18C	109.5
C10—C9—H9	120.0

O1—C1—C2—C3	−179.5 (2)	C8—C13—C14—C15	−148.7 (2)
C17—C1—C2—C3	1.1 (3)	C12—C13—C14—C15	31.4 (3)
C1—C2—C3—C4	24.3 (3)	C8—C13—C14—C5	−21.2 (3)
C2—C3—C4—C5	−167.6 (2)	C12—C13—C14—C5	158.9 (2)
C2—C3—C4—C17	−41.0 (2)	C4—C5—C14—C13	179.61 (18)
C3—C4—C5—C6	−55.3 (3)	C6—C5—C14—C13	54.7 (2)
C17—C4—C5—C6	−178.27 (19)	C4—C5—C14—C15	−52.5 (2)
C3—C4—C5—C14	−176.7 (2)	C6—C5—C14—C15	−177.42 (19)
C17—C4—C5—C14	60.3 (2)	C13—C14—C15—C16	175.6 (2)
C4—C5—C6—C7	171.42 (19)	C5—C14—C15—C16	49.6 (3)
C14—C5—C6—C7	−67.6 (2)	C14—C15—C16—C17	−50.9 (3)
C5—C6—C7—C8	43.4 (3)	O1—C1—C17—C16	36.6 (3)
C6—C7—C8—C9	170.8 (2)	C2—C1—C17—C16	−144.0 (2)
C6—C7—C8—C13	−9.4 (3)	O1—C1—C17—C4	154.7 (2)
C13—C8—C9—C10	0.3 (3)	C2—C1—C17—C4	−25.9 (2)
C7—C8—C9—C10	−179.9 (2)	O1—C1—C17—C18	−86.8 (3)
C8—C9—C10—C11	1.6 (4)	C2—C1—C17—C18	92.6 (2)
C8—C9—C10—I1	−178.76 (17)	C15—C16—C17—C1	169.9 (2)
C9—C10—C11—C12	−1.8 (4)	C15—C16—C17—C4	56.3 (2)
I1—C10—C11—C12	178.55 (18)	C15—C16—C17—C18	−69.6 (2)
C10—C11—C12—C13	0.2 (4)	C5—C4—C17—C1	173.37 (18)
C9—C8—C13—C12	−1.9 (3)	C3—C4—C17—C1	41.4 (2)
C7—C8—C13—C12	178.3 (2)	C5—C4—C17—C16	−63.7 (2)
C9—C8—C13—C14	178.2 (2)	C3—C4—C17—C16	164.26 (19)
C7—C8—C13—C14	−1.6 (3)	C5—C4—C17—C18	60.7 (3)
C11—C12—C13—C8	1.7 (4)	C3—C4—C17—C18	−71.3 (2)
C11—C12—C13—C14	−178.4 (2)

Experimental details

Crystal data
Chemical formula	C₁₈H₂₁IO
M_r	380.25
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	9.9636 (2), 10.5246 (2), 14.3535 (2)
V (Å³)	1505.15 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.12
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.636, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	10547, 3452, 3353
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.045, 1.03
No. of reflections	3452
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.39
Absolute structure	Flack (1983), 1473 Friedel pairs
Absolute structure parameter	0.01 (2)

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Acknowledgements

We thank the University of Malaya for supporting this study.

References

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