Ethyl 3′-(2,4-dichloro­phen­yl)-5′-hydr­oxy-5′-methyl-4′,5′-dihydro­spiro­[fluorene-9,2′(3′H)-furan]-4′-carboxyl­ate

NizamMohideen, M.; Thenmozhi, S.; SubbiahPandi, A.; Savitha, G.; Perumal, P.T.

doi:10.1107/S1600536809011854

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Pages o977-o978

doi:10.1107/S1600536809011854

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Ethyl 3′-(2,4-dichlorophenyl)-5′-hydroxy-5′-methyl-4′,5′-dihydrospiro[fluorene-9,2′(3′H)-furan]-4′-carboxylate

M. NizamMohideen,^a S. Thenmozhi,^b A. SubbiahPandi,^b ^* G. Savitha ^c and P. T. Perumal ^c

^aDepartment of Physics, The New College (Autonomous), Chennai 600 014, India, ^bDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India, and ^cOrganic Chemistry Division, Central Leather Research Institute, Chennai 600 020, India
^*Correspondence e-mail: a_spandian@yahoo.com

(Received 12 March 2009; accepted 30 March 2009; online 8 April 2009)

The furan ring and the five-membered fluorene unit in the title compound, C₂₆H₂₂Cl₂O₄, adopt envelope conformations. Intermolecular C—H⋯O interactions between symmetry-related molecules involving two C—H groups and an O atom as a bifurcated acceptor generate centrosymmetric hydrogen-bonded dimers with cyclic R₂²(16) and R₂²(8) ring motifs. A short C—H⋯Cl intramolecular contact occurs in the molecule.

Related literature

For spiro compounds in pharmacologically active alkaloids, see: Cravotto et al. (2001 ). For the anticonvulsant activity of fluorene derivatives, see: Vanvakides et al. (2004 ). Fluorene derivatives, including polyfluorenes and oligofluorenes, are promising candidates for blue light-emitting materials in organic light-emitting devices (Muller et al., 2003 ), organic phototransistors (Saragi et al., 2004 ), non-linear optics (Kim et al., 1998 ) and photochromic materials (Chun et al., 2003 ). For the biological activity of furan derivatives and annulated furan derivatives and their use as precursors for the synthesis of natural products, see: Greve & Friedrichsen (2000 ). For hydrogen-bond motifs and ring puckering parameters, see: Bernstein et al. (1995 ); Cremer & Pople (1975 ); Nardelli (1983 ). For a related spiro-linked system, see: Feng et al. (2004 ).

Experimental

Crystal data

C₂₆H₂₂Cl₂O₄
M_r = 469.34
Monoclinic, C 2/c
a = 28.6811 (13) Å
b = 9.0600 (4) Å
c = 17.4074 (8) Å
β = 92.072 (3)°
V = 4520.4 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker 2004 ) T_min = 0.916, T_max = 0.938
22504 measured reflections
5338 independent reflections
3663 reflections with I > 2σ(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.151
S = 1.04
5338 reflections
291 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O3ⁱ	0.98	2.37	3.331 (3)	167
C6—H6⋯O3ⁱ	0.93	2.55	3.393 (3)	151
C3—H3⋯Cl1	0.98	2.57	3.082 (2)	113
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: APEX2 (Bruker, 2004); cell refinement: 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: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809011854/fl2242sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809011854/fl2242Isup2.hkl

checkCIF report

Comment top

Spiro compounds are often encountered in many pharmacologically active alkaloids (Cravotto et al., 2001) and fluorene derivatives have been found to have anticonvulsant activity (Vanvakides et al., 2004). In addition, fluorene derivatives, including polyfluorenes and oligofluorenes, have been studied extensively in recent years because they are very promising candidates for blue light-emitting materials in organic light-emitting devices (Muller et al., 2003), organic phototransistors (Saragi et al., 2004), nonlinear optics (Kim et al., 1998) and photochromic materials (Chun et al., 2003). Furan derivatives and annulated furan derivatives occur widely in nature and, along with their unnatural analogs, have been shown to have a wide range of biological activity as well as being important precursors for the synthesis of natural products (Greve & Friedrichsen, 2000). In view of these important properties, the crystal structure of the title compound, (I), has been determined.

in (I, Fig. 1) the C4-C5 and C4-C16 bond distances of the fluorene moiety are almost identical to the values reported in another spiro-linked system (Feng et al., 2004).

The benzene ring is planar with the largest displacement observed being -0.014 (1) Å for atom C22. The deviations of the atoms Cl1 and Cl2 from the least-squares plane of the phenyl rings are -0.114 (1) and 0.015 (1) Å, respectively.

The five membered fluorene moiety adopts an envelope conformation (flap atom C4) with a pseudo-twofold axis passing through the C4-C5 bond. The puckering parameters (Cremer & Pople, 1975) and the lowest displacement asymmetry parameters (Nardelli, 1983) for this ring are q₂ = 0.107 (2) Å, ϕ = 355.0 (1)° and Δ_S(C4) is 1.3 (1)°. The tetrahydrofuran ring also adopts an envelope conformation (flap atom C2) with a pseudo-twofold axis passing through the C2-C3 bond. The puckering parameters (Cremer & Pople, 1975) and the lowest displacement asymmetry parameters (Nardelli, 1983) for this ring are q₂ = 0.388 (2) Å, ϕ = 252.1 (2)° and Δ_S(C2) is 2.1 (2)°.

Carbonyl atom O3 acts as a intermolecuar bifurcated acceptor with both C2 and C6 (Table 1 and Fig. 2) from a symmetry-related molecule to form centrosymmetric hydrogen bonded dimers with cyclic R₂²(16) and R₂²(8) (Bernstein, et al., 1995) ring systems, respectively. The structure is further stabilized by C—H···π interactions involing rings C26- H26C···Cg1 (Cg1 is the centroid of the C11—C16 ring).

Related literature top

For general background see: Vanvakides et al. (2004); Muller et al. (2003); Saragi et al. (2004); Kim et al. (1998); Chun et al.(2003); Cravotto et al. (2001); Greve & Friedrichsen (2000). For hydrogen-bond motifs and ring puckering parameters, see: Bernstein et al. (1995); Cremer & Pople (1975); Nardelli (1983). For a related spiro-linked system, see: Feng et al. (2004). Cg1 is the centroid of the C11–C16 ring.

Experimental top

To a stirred mixture of 9-(2,4-Dichloro-benzylidene)-9H-fluorene (1.0 mmol), ethylacetoacetate (1.0 mmol) and NaHCO₃ (3.0 mmol) in acetonitrile (10 ml), ceric ammonium nitrate (2.5 mmol) dissolved in acetonitrile (5 ml) was added dropwise at 0 ° under N₂. The reaction mixture was stirred until completion of the reaction as monitored by TLC. Water was added to the mixture and the product was extracted with ethyl acetate (2 × 20 ml) and then dried over anhydrous Na₂SO₄. Removal of the solvent under reduced pressure gave a crude product, which was purified by column chromatography on silica gel, with ethyl acetate-hexane (4:6) as eluent to afford a pure product in 79% yield. Single crystals of the title compound suitable for X-ray diffraction were obtained by slow evaporation of a solution in ethylacetate.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme for. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal packing of compound (I), showing the R₂²(16) and R₂²(8) rings. Hydrogen bonding is shown as dashed lines. H atoms not involved in the hydrogen bonding have been omitted for clarity. [Symmetry codes: -x + 1/2, -y + 1/2, -z]

Ethyl 3'-(2,4-dichlorophenyl)-5'-hydroxy-5'-methyl-4',5'- dihydrospiro[fluorene-9,2'(3'H)-furan]-4'-carboxylate top

Crystal data top

C₂₆H₂₂Cl₂O₄	F(000) = 1952
M_r = 469.34	D_x = 1.379 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7176 reflections
a = 28.6811 (13) Å	θ = 2.5–25°
b = 9.0600 (4) Å	µ = 0.32 mm⁻¹
c = 17.4074 (8) Å	T = 293 K
β = 92.072 (3)°	Prismatic, yellow
V = 4520.4 (4) Å³	0.25 × 0.20 × 0.20 mm
Z = 8

Data collection top

Bruker Kappa APEXII CCD diffractometer	5338 independent reflections
Radiation source: fine-focus sealed tube	3663 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
ω and ϕ scans	θ_max = 27.8°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker 2004)	h = −36→37
T_min = 0.916, T_max = 0.938	k = −11→11
22504 measured reflections	l = −21→22

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.151	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0729P)² + 2.471P] where P = (F_o² + 2F_c²)/3
5338 reflections	(Δ/σ)_max < 0.001
291 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₂₆H₂₂Cl₂O₄	V = 4520.4 (4) Å³
M_r = 469.34	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 28.6811 (13) Å	µ = 0.32 mm⁻¹
b = 9.0600 (4) Å	T = 293 K
c = 17.4074 (8) Å	0.25 × 0.20 × 0.20 mm
β = 92.072 (3)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	5338 independent reflections
Absorption correction: multi-scan (SADABS; Bruker 2004)	3663 reflections with I > 2σ(I)
T_min = 0.916, T_max = 0.938	R_int = 0.056
22504 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.151	H-atom parameters constrained
S = 1.04	Δρ_max = 0.38 e Å⁻³
5338 reflections	Δρ_min = −0.35 e Å⁻³
291 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Cl1	0.06337 (2)	−0.03027 (7)	0.10063 (4)	0.0663 (2)
Cl2	0.00329 (2)	0.39144 (8)	−0.09056 (4)	0.0652 (2)
O1	0.21156 (5)	0.19309 (19)	0.21266 (8)	0.0476 (4)
O2	0.23543 (6)	−0.03879 (18)	0.17193 (10)	0.0550 (4)
H2	0.2506	−0.0562	0.2117	0.082*
O3	0.25673 (6)	0.04006 (18)	−0.01270 (10)	0.0540 (4)
O4	0.18812 (5)	−0.06733 (17)	0.00380 (9)	0.0455 (4)
C1	0.23639 (7)	0.1143 (2)	0.15672 (13)	0.0411 (5)
C2	0.20777 (6)	0.1382 (2)	0.08249 (11)	0.0331 (4)
H2A	0.2135	0.2389	0.0645	0.040*
C3	0.15806 (6)	0.1308 (2)	0.10976 (11)	0.0301 (4)
H3	0.1508	0.0267	0.1186	0.036*
C4	0.16289 (7)	0.2080 (2)	0.19036 (12)	0.0349 (4)
C5	0.14777 (8)	0.3679 (2)	0.19083 (12)	0.0401 (5)
C6	0.16812 (10)	0.4898 (2)	0.15801 (13)	0.0536 (6)
H6	0.1963	0.4821	0.1336	0.064*
C7	0.14497 (14)	0.6249 (3)	0.16271 (16)	0.0709 (9)
H7	0.1579	0.7085	0.1409	0.085*
C8	0.10342 (13)	0.6362 (3)	0.19909 (17)	0.0722 (9)
H8	0.0883	0.7269	0.2005	0.087*
C9	0.08401 (11)	0.5172 (3)	0.23298 (16)	0.0628 (7)
H9	0.0561	0.5263	0.2581	0.075*
C10	0.10643 (8)	0.3822 (2)	0.22951 (12)	0.0438 (5)
C11	0.09519 (8)	0.2392 (3)	0.26364 (13)	0.0442 (5)
C12	0.05912 (10)	0.1956 (4)	0.30938 (16)	0.0650 (7)
H12	0.0350	0.2601	0.3201	0.078*
C13	0.05993 (12)	0.0536 (4)	0.33873 (18)	0.0767 (9)
H13	0.0359	0.0223	0.3693	0.092*
C14	0.09547 (12)	−0.0415 (3)	0.32353 (16)	0.0690 (8)
H14	0.0959	−0.1349	0.3457	0.083*
C15	0.13054 (9)	−0.0010 (3)	0.27593 (14)	0.0505 (6)
H15	0.1540	−0.0672	0.2639	0.061*
C16	0.13012 (7)	0.1400 (2)	0.24653 (11)	0.0378 (5)
C17	0.12017 (6)	0.1925 (2)	0.05700 (11)	0.0300 (4)
C18	0.12700 (7)	0.3165 (2)	0.01180 (12)	0.0369 (5)
H18	0.1564	0.3597	0.0125	0.044*
C19	0.09199 (8)	0.3780 (2)	−0.03393 (13)	0.0431 (5)
H19	0.0978	0.4604	−0.0640	0.052*
C20	0.04839 (7)	0.3160 (2)	−0.03454 (12)	0.0405 (5)
C21	0.03967 (7)	0.1925 (2)	0.00810 (12)	0.0413 (5)
H21	0.0101	0.1506	0.0074	0.050*
C22	0.07576 (7)	0.1313 (2)	0.05219 (12)	0.0355 (4)
C23	0.28555 (8)	0.1735 (3)	0.15764 (15)	0.0597 (7)
H23A	0.3002	0.1568	0.2073	0.089*
H23B	0.2848	0.2774	0.1471	0.089*
H23C	0.3029	0.1239	0.1192	0.089*
C24	0.22049 (7)	0.0327 (2)	0.01982 (12)	0.0356 (4)
C25	0.19678 (9)	−0.1675 (3)	−0.05956 (14)	0.0541 (6)
H25A	0.2275	−0.2115	−0.0531	0.065*
H25B	0.1952	−0.1145	−0.1080	0.065*
C26	0.16055 (11)	−0.2826 (3)	−0.05889 (18)	0.0685 (8)
H26A	0.1637	−0.3381	−0.0120	0.103*
H26B	0.1641	−0.3474	−0.1019	0.103*
H26C	0.1303	−0.2373	−0.0623	0.103*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0460 (4)	0.0596 (4)	0.0915 (5)	−0.0247 (3)	−0.0215 (3)	0.0354 (3)
Cl2	0.0504 (4)	0.0691 (4)	0.0743 (5)	0.0082 (3)	−0.0234 (3)	0.0176 (3)
O1	0.0330 (8)	0.0669 (10)	0.0423 (9)	−0.0021 (7)	−0.0079 (7)	−0.0085 (7)
O2	0.0522 (10)	0.0538 (10)	0.0579 (10)	0.0060 (8)	−0.0121 (8)	0.0140 (8)
O3	0.0441 (10)	0.0515 (10)	0.0677 (11)	−0.0063 (7)	0.0194 (8)	−0.0078 (8)
O4	0.0390 (8)	0.0434 (8)	0.0540 (9)	−0.0071 (7)	−0.0003 (7)	−0.0137 (7)
C1	0.0308 (11)	0.0483 (12)	0.0439 (12)	−0.0006 (9)	−0.0042 (9)	0.0008 (9)
C2	0.0267 (10)	0.0317 (10)	0.0406 (11)	−0.0033 (7)	−0.0025 (8)	0.0009 (8)
C3	0.0268 (10)	0.0263 (9)	0.0368 (10)	−0.0033 (7)	−0.0030 (8)	0.0011 (7)
C4	0.0318 (10)	0.0345 (10)	0.0381 (11)	−0.0020 (8)	−0.0041 (8)	0.0015 (8)
C5	0.0517 (13)	0.0346 (11)	0.0333 (10)	−0.0043 (9)	−0.0074 (9)	−0.0035 (8)
C6	0.0795 (18)	0.0389 (12)	0.0423 (13)	−0.0168 (12)	−0.0022 (12)	−0.0051 (10)
C7	0.130 (3)	0.0322 (13)	0.0493 (15)	−0.0157 (15)	−0.0189 (17)	0.0005 (11)
C8	0.110 (3)	0.0433 (15)	0.0613 (17)	0.0191 (15)	−0.0230 (18)	−0.0063 (13)
C9	0.0715 (18)	0.0554 (16)	0.0603 (16)	0.0205 (13)	−0.0138 (14)	−0.0078 (13)
C10	0.0489 (13)	0.0430 (12)	0.0387 (11)	0.0062 (10)	−0.0081 (10)	−0.0037 (9)
C11	0.0400 (12)	0.0532 (13)	0.0392 (12)	−0.0001 (10)	−0.0028 (10)	−0.0026 (10)
C12	0.0506 (15)	0.085 (2)	0.0606 (17)	0.0010 (14)	0.0145 (13)	−0.0025 (15)
C13	0.071 (2)	0.092 (2)	0.069 (2)	−0.0250 (18)	0.0225 (16)	0.0101 (17)
C14	0.089 (2)	0.0612 (17)	0.0574 (17)	−0.0222 (16)	0.0069 (16)	0.0162 (13)
C15	0.0611 (16)	0.0435 (13)	0.0467 (13)	−0.0029 (11)	−0.0020 (12)	0.0064 (10)
C16	0.0388 (11)	0.0412 (11)	0.0330 (10)	−0.0042 (9)	−0.0033 (9)	0.0019 (8)
C17	0.0281 (9)	0.0277 (9)	0.0340 (10)	−0.0013 (7)	−0.0029 (8)	−0.0039 (7)
C18	0.0336 (11)	0.0337 (10)	0.0430 (11)	−0.0071 (8)	−0.0048 (9)	0.0018 (9)
C19	0.0471 (13)	0.0347 (11)	0.0469 (12)	−0.0054 (9)	−0.0079 (10)	0.0077 (9)
C20	0.0370 (11)	0.0400 (11)	0.0434 (12)	0.0052 (9)	−0.0107 (9)	−0.0004 (9)
C21	0.0309 (11)	0.0431 (11)	0.0493 (13)	−0.0056 (9)	−0.0070 (9)	−0.0004 (10)
C22	0.0317 (10)	0.0322 (10)	0.0424 (11)	−0.0061 (8)	−0.0030 (9)	0.0027 (8)
C23	0.0327 (12)	0.0820 (18)	0.0634 (16)	−0.0086 (12)	−0.0113 (11)	−0.0038 (14)
C24	0.0340 (11)	0.0305 (10)	0.0419 (11)	0.0004 (8)	−0.0020 (9)	0.0041 (8)
C25	0.0615 (16)	0.0469 (13)	0.0534 (14)	0.0042 (12)	−0.0065 (12)	−0.0132 (11)
C26	0.078 (2)	0.0479 (15)	0.0779 (19)	−0.0077 (13)	−0.0150 (16)	−0.0140 (13)

Geometric parameters (Å, º) top

Cl1—C22	1.733 (2)	C11—C16	1.386 (3)
Cl2—C20	1.732 (2)	C11—C12	1.386 (3)
O1—C1	1.420 (3)	C12—C13	1.384 (4)
O1—C4	1.442 (2)	C12—H12	0.9300
O2—C1	1.412 (3)	C13—C14	1.368 (4)
O2—H2	0.8200	C13—H13	0.9300
O3—C24	1.203 (3)	C14—C15	1.376 (4)
O4—C24	1.320 (2)	C14—H14	0.9300
O4—C25	1.456 (3)	C15—C16	1.376 (3)
C1—C23	1.508 (3)	C15—H15	0.9300
C1—C2	1.521 (3)	C17—C22	1.389 (3)
C2—C24	1.506 (3)	C17—C18	1.389 (3)
C2—C3	1.520 (3)	C18—C19	1.377 (3)
C2—H2A	0.9800	C18—H18	0.9300
C3—C17	1.505 (3)	C19—C20	1.371 (3)
C3—C4	1.569 (3)	C19—H19	0.9300
C3—H3	0.9800	C20—C21	1.371 (3)
C4—C16	1.512 (3)	C21—C22	1.382 (3)
C4—C5	1.512 (3)	C21—H21	0.9300
C5—C6	1.383 (3)	C22—Cl1	1.733 (2)
C5—C10	1.391 (3)	C23—H23A	0.9600
C6—C7	1.396 (4)	C23—H23B	0.9600
C6—H6	0.9300	C23—H23C	0.9600
C7—C8	1.373 (4)	C25—C26	1.472 (4)
C7—H7	0.9300	C25—H25A	0.9700
C8—C9	1.358 (4)	C25—H25B	0.9700
C8—H8	0.9300	C26—H26A	0.9600
C9—C10	1.384 (3)	C26—H26B	0.9600
C9—H9	0.9300	C26—H26C	0.9600
C10—C11	1.466 (3)

C1—O1—C4	111.55 (15)	C14—C13—H13	119.4
C1—O2—H2	109.5	C12—C13—H13	119.4
C24—O4—C25	116.72 (17)	C13—C14—C15	121.0 (3)
O2—C1—O1	110.58 (18)	C13—C14—H14	119.5
O2—C1—C23	111.83 (19)	C15—C14—H14	119.5
O1—C1—C23	107.81 (18)	C14—C15—C16	118.4 (3)
O2—C1—C2	106.62 (17)	C14—C15—H15	120.8
O1—C1—C2	104.00 (16)	C16—C15—H15	120.8
C23—C1—C2	115.72 (19)	C15—C16—C11	121.2 (2)
C24—C2—C3	116.91 (16)	C15—C16—C4	128.4 (2)
C24—C2—C1	112.78 (17)	C11—C16—C4	110.23 (18)
C3—C2—C1	102.23 (16)	C22—C17—C18	115.87 (18)
C24—C2—H2A	108.2	C22—C17—C3	121.93 (17)
C3—C2—H2A	108.2	C18—C17—C3	122.18 (17)
C1—C2—H2A	108.2	C19—C18—C17	122.68 (19)
C17—C3—C2	117.24 (16)	C19—C18—H18	118.7
C17—C3—C4	114.73 (15)	C17—C18—H18	118.7
C2—C3—C4	101.89 (15)	C20—C19—C18	119.0 (2)
C17—C3—H3	107.5	C20—C19—H19	120.5
C2—C3—H3	107.5	C18—C19—H19	120.5
C4—C3—H3	107.5	C19—C20—C21	120.98 (19)
O1—C4—C16	113.98 (16)	C19—C20—Cl2	120.33 (17)
O1—C4—C5	111.29 (16)	C21—C20—Cl2	118.68 (16)
C16—C4—C5	101.64 (17)	C20—C21—C22	118.69 (19)
O1—C4—C3	104.61 (15)	C20—C21—H21	120.7
C16—C4—C3	111.10 (16)	C22—C21—H21	120.7
C5—C4—C3	114.56 (16)	C21—C22—C17	122.71 (18)
C6—C5—C10	120.4 (2)	C21—C22—Cl1	116.49 (15)
C6—C5—C4	129.6 (2)	C17—C22—Cl1	120.78 (15)
C10—C5—C4	109.98 (18)	C21—C22—Cl1	116.49 (15)
C5—C6—C7	117.9 (3)	C17—C22—Cl1	120.78 (15)
C5—C6—H6	121.1	C1—C23—H23A	109.5
C7—C6—H6	121.1	C1—C23—H23B	109.5
C8—C7—C6	121.0 (3)	H23A—C23—H23B	109.5
C8—C7—H7	119.5	C1—C23—H23C	109.5
C6—C7—H7	119.5	H23A—C23—H23C	109.5
C9—C8—C7	121.2 (3)	H23B—C23—H23C	109.5
C9—C8—H8	119.4	O3—C24—O4	123.5 (2)
C7—C8—H8	119.4	O3—C24—C2	122.80 (19)
C8—C9—C10	119.0 (3)	O4—C24—C2	113.70 (17)
C8—C9—H9	120.5	O4—C25—C26	107.2 (2)
C10—C9—H9	120.5	O4—C25—H25A	110.3
C9—C10—C5	120.6 (2)	C26—C25—H25A	110.3
C9—C10—C11	130.8 (2)	O4—C25—H25B	110.3
C5—C10—C11	108.50 (19)	C26—C25—H25B	110.3
C16—C11—C12	119.9 (2)	H25A—C25—H25B	108.5
C16—C11—C10	108.35 (19)	C25—C26—H26A	109.5
C12—C11—C10	131.6 (2)	C25—C26—H26B	109.5
C13—C12—C11	118.3 (3)	H26A—C26—H26B	109.5
C13—C12—H12	120.8	C25—C26—H26C	109.5
C11—C12—H12	120.8	H26A—C26—H26C	109.5
C14—C13—C12	121.1 (3)	H26B—C26—H26C	109.5

C4—O1—C1—O2	−89.2 (2)	C10—C11—C12—C13	−174.5 (3)
C4—O1—C1—C23	148.26 (19)	C11—C12—C13—C14	0.4 (5)
C4—O1—C1—C2	24.9 (2)	C12—C13—C14—C15	−2.7 (5)
O2—C1—C2—C24	−48.0 (2)	C13—C14—C15—C16	2.7 (4)
O1—C1—C2—C24	−164.86 (16)	C14—C15—C16—C11	−0.5 (3)
C23—C1—C2—C24	77.1 (2)	C14—C15—C16—C4	−176.5 (2)
O2—C1—C2—C3	78.44 (19)	C12—C11—C16—C15	−1.9 (3)
O1—C1—C2—C3	−38.47 (19)	C10—C11—C16—C15	175.3 (2)
C23—C1—C2—C3	−156.49 (19)	C12—C11—C16—C4	174.9 (2)
C24—C2—C3—C17	−73.5 (2)	C10—C11—C16—C4	−8.0 (2)
C1—C2—C3—C17	162.79 (16)	O1—C4—C16—C15	−52.6 (3)
C24—C2—C3—C4	160.35 (16)	C5—C4—C16—C15	−172.4 (2)
C1—C2—C3—C4	36.69 (18)	C3—C4—C16—C15	65.3 (3)
C1—O1—C4—C16	120.28 (19)	O1—C4—C16—C11	131.00 (19)
C1—O1—C4—C5	−125.50 (19)	C5—C4—C16—C11	11.2 (2)
C1—O1—C4—C3	−1.3 (2)	C3—C4—C16—C11	−111.1 (2)
C17—C3—C4—O1	−150.41 (16)	C2—C3—C17—C22	145.93 (19)
C2—C3—C4—O1	−22.69 (18)	C4—C3—C17—C22	−94.6 (2)
C17—C3—C4—C16	86.2 (2)	C2—C3—C17—C18	−35.9 (3)
C2—C3—C4—C16	−146.11 (16)	C4—C3—C17—C18	83.6 (2)
C17—C3—C4—C5	−28.3 (2)	C22—C17—C18—C19	1.4 (3)
C2—C3—C4—C5	99.43 (19)	C3—C17—C18—C19	−176.88 (19)
O1—C4—C5—C6	49.6 (3)	C17—C18—C19—C20	0.7 (3)
C16—C4—C5—C6	171.4 (2)	C18—C19—C20—C21	−1.5 (3)
C3—C4—C5—C6	−68.8 (3)	C18—C19—C20—Cl2	179.31 (17)
O1—C4—C5—C10	−132.24 (18)	C19—C20—C21—C22	0.2 (3)
C16—C4—C5—C10	−10.5 (2)	Cl2—C20—C21—C22	179.34 (16)
C3—C4—C5—C10	109.4 (2)	C20—C21—C22—C17	2.1 (3)
C10—C5—C6—C7	−2.3 (3)	C20—C21—C22—Cl1	−176.59 (17)
C4—C5—C6—C7	175.7 (2)	C20—C21—C22—Cl1	−176.59 (17)
C5—C6—C7—C8	0.3 (4)	C18—C17—C22—C21	−2.8 (3)
C6—C7—C8—C9	1.4 (4)	C3—C17—C22—C21	175.45 (19)
C7—C8—C9—C10	−0.9 (4)	C18—C17—C22—Cl1	175.82 (15)
C8—C9—C10—C5	−1.1 (4)	C3—C17—C22—Cl1	−5.9 (3)
C8—C9—C10—C11	176.4 (2)	C18—C17—C22—Cl1	175.82 (15)
C6—C5—C10—C9	2.7 (3)	C3—C17—C22—Cl1	−5.9 (3)
C4—C5—C10—C9	−175.6 (2)	C25—O4—C24—O3	−3.3 (3)
C6—C5—C10—C11	−175.3 (2)	C25—O4—C24—C2	176.29 (18)
C4—C5—C10—C11	6.4 (2)	C3—C2—C24—O3	170.8 (2)
C9—C10—C11—C16	−176.7 (2)	C1—C2—C24—O3	−71.1 (3)
C5—C10—C11—C16	1.0 (2)	C3—C2—C24—O4	−8.7 (3)
C9—C10—C11—C12	−0.1 (4)	C1—C2—C24—O4	109.3 (2)
C5—C10—C11—C12	177.7 (3)	C24—O4—C25—C26	171.0 (2)
C16—C11—C12—C13	1.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O3ⁱ	0.98	2.37	3.331 (3)	167
C6—H6···O3ⁱ	0.93	2.55	3.393 (3)	151
C3—H3···Cl1	0.98	2.57	3.082 (2)	113
C26—H26C···Cg1ⁱⁱ	0.96	2.95	3.556 (1)	122

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

Experimental details

Crystal data
Chemical formula	C₂₆H₂₂Cl₂O₄
M_r	469.34
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	28.6811 (13), 9.0600 (4), 17.4074 (8)
β (°)	92.072 (3)
V (Å³)	4520.4 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.25 × 0.20 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker 2004)
T_min, T_max	0.916, 0.938
No. of measured, independent and observed [I > 2σ(I)] reflections	22504, 5338, 3663
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.657

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.151, 1.04
No. of reflections	5338
No. of parameters	291
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.35

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O3ⁱ	0.98	2.37	3.331 (3)	167.3
C6—H6···O3ⁱ	0.93	2.55	3.393 (3)	151.4
C3—H3···Cl1	0.98	2.57	3.082 (2)	112.8
C26—H26C···Cg1ⁱⁱ	0.96	2.95	3.556 (1)	122.0

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

Acknowledgements

The authors thank Dr Babu Vargheese, SAIF, IIT, Madras, India, for his help in collecting the X-ray intensity data. MNM and ASP thank Dr J. Jothi Kumar, Principal of Presidency College (Autonomous), Chennai, India, for providing the computer and internet facilities.

References

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Volume 65| Part 5| May 2009| Pages o977-o978

doi:10.1107/S1600536809011854

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Ethyl 3′-(2,4-di­chloro­phen­yl)-5′-hydr­­oxy-5′-methyl-4′,5′-di­hydro­spiro­[fluorene-9,2′(3′H)-furan]-4′-carboxyl­ate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Ethyl 3′-(2,4-dichlorophenyl)-5′-hydroxy-5′-methyl-4′,5′-dihydrospiro[fluorene-9,2′(3′H)-furan]-4′-carboxylate