4′-(4-Fluoro­phen­yl)-1′-methyl­dispiro­[indane-2,2′-pyrrolidine-3′,2′′-indane]-1,3,1′′-trione methanol hemisolvate

Mohamed Ashraf Ali; Elumalai Manogaran; Tan Soo Choon; Mohd Mustaqim Rosli; Ibrahim Abdul Razak

doi:10.1107/S1600536813009987

. 2013 Apr 17;69(Pt 5):o746–o747. doi: 10.1107/S1600536813009987

4′-(4-Fluorophenyl)-1′-methyldispiro[indane-2,2′-pyrrolidine-3′,2′′-indane]-1,3,1′′-trione methanol hemisolvate

Mohamed Ashraf Ali ^a, Elumalai Manogaran ^b, Tan Soo Choon ^a, Mohd Mustaqim Rosli ^c, Ibrahim Abdul Razak ^c,^*,^‡

PMCID: PMC3648276 PMID: 23723896

Abstract

The asymmetric unit of the title compound, C₂₉H₂₄FNO₅·0.5CH₃OH, contains two independent molecules and a one methanol solvent molecule. The methanol molecule is O—H⋯O hydrogen bonded to one of the independent molecules. The pyrrolidine rings in both molecules adopt half-chair conformations, while the cyclopentane rings within the indane groups are in flattened envelope conformations, with the spiro C atoms forming the flaps. The benzene rings of the indane ring systems form a dihedral angle of 35.06 (7)° in one independent molecule and 31.16 (8)° in the other. The fluoro-substituted benzene ring forms dihedral angles of 65.35 (6) and 85.87 (7)° with the indane group benzene rings in one molecule, and 72.78 (8) and 77.27 (8)° in the other. In each molecule, a weak intramolecular C—H⋯O hydrogen bond forms an S(6) ring motif. In the crystal, weak C—H⋯O, C—H⋯N and C—H⋯F hydrogen bonds link the molecules into a three-dimensional network.

Related literature

For background to compounds with antitubercular activity, see: Ali et al. (2011 ▶). For related structures, see: Wei et al. (2011 ▶, 2012 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶). graphic file with name e-69-0o746-scheme1.jpg

Experimental

Crystal data

C₂₉H₂₄FNO₅·0.5CH₄O
M _r = 501.52
Monoclinic,
a = 14.6385 (6) Å
b = 12.5099 (6) Å
c = 26.2017 (10) Å
β = 92.645 (1)°
V = 4793.1 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.44 × 0.21 × 0.15 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.957, T _max = 0.985
53390 measured reflections
14094 independent reflections
10283 reflections with I > 2σ(I)
R _int = 0.046

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.147
S = 1.04
14094 reflections
678 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(59.5KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813009987/lh5596sup1.cif

e-69-0o746-sup1.cif^{(59.5KB, cif)}

Click here for additional data file.^{(689KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813009987/lh5596Isup2.hkl

e-69-0o746-Isup2.hkl^{(689KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H1O6⋯O4A	0.97 (3)	1.99 (3)	2.9346 (18)	164 (3)
C8A—H8AA⋯O5A	0.99	2.43	3.088 (2)	124
C8B—H8BA⋯O5B	0.99	2.38	3.0960 (19)	128
C26A—H26A⋯O5A ⁱ	0.95	2.54	3.2430 (18)	131
C27A—H27A⋯N1B ⁱⁱ	0.98	2.42	3.337 (2)	155
C28A—H28A⋯O2B ⁱⁱⁱ	0.98	2.50	3.3478 (19)	145
C28B—H28F⋯O6^iv	0.98	2.46	3.360 (2)	153
C30—H30B⋯F1A ^v	0.98	2.53	3.307 (2)	136

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

The authors wish to express their gratitude and appreciation to the Pharmacogenetics and Novel Therapeutics Research Cluster, Institute for Research in Molecular Medicine, Universiti Sains Malaysia (USM), Penang, for support of this work. This work was funded through Research Grant No. RUC (1001/PSK/8620012) and HiCoE Research Grant No (311.CIPPM.4401005). IAR also thanks USM for the Short Term Grant, No. 304/PFIZIK/6312078.

supplementary crystallographic information

Comment

Tuberculosis (TB) remains a global health problem and has infected about one third of the world population. No new drugs have been discovered for the past 40 years and therefore new anti-TB agents are desperately needed (Ali et al., 2011). As part of our ongoing search for novel heterocyclic compounds with antitubercular activity (Wei et al., 2011, 2012) the crystal structure of the title compound (I) has been determined.

The asymmetric unit of the title compound (Fig. 1) contains two crystallographically independent molecules and a molecule of methanol (Fig. 1). In both molecules, the intramolecular interactions of C8A—H8AA···O5A and C8B—H8BA···O5B (Table 1) form an S(6) ring motif (Fig. 2) (Bernstein et al. 1995). The pyrrolidine ring for both molecules A and B adopt a half-chair conformation with the puckering parameters Q = 0.4612 (16) Å, φ = 127.36 (19)° for molecule A and Q = 0.4332 (16) Å, φ = 125.2 (2)° for molecule B. In both molecules, A and B, the cyclopentane rings (C1—C2/C7—C9 & C12—C14/C19—C20) within the indane moiety (C1—C9 & C12—C20) form flattened envelope conformations (C9 and C12 at the flap) with the puckering parameters Q = 0.1587 (16) Å, φ 146.2 (6)° and Q = 0.1910 (16) Å, φ = 175.0 (5)° for molecule A and Q = 0.1338 (15)å, φ = 155.5 (6)° and Q = 0.2232 (16) Å, φ = 173.6 (4)° for molecule B.

In each molecule, the benzene rings of the indane ring systems form dihedral angles of 35.06 (7) ° [C2A-C7A/C14A-C19A] and 31.16 (8)° [C2B-C7B/C14B-C19B] with each other. The fluoro-substituted benzene ring forms diedral angles of 65.35 (6)° [C14A-C19A/C21A-C26A] and 85.87 (7)° [C2A-C7A/C21A-C26A] with the indane group benzene rings of one molecule and 72.78 (8)° [C14B-C19B/C21B-C26B] and 77.27 (8)° [C2B-C7B/C21B-C26B] in the other.

In the crystal, molecules are connected by weak C—H···O^{i, iii, iv}, C—H···Nⁱⁱ and C—H···F^v (Table 1) hydrogen bonds into a three-dimensional network (Fig. 3).

Experimental

A mixture of 5,6-dimethoxy(E)-2-(4-fluorobenzylidene)-2,3-dihydro-1H-indene-1-one (0.001 mol), ninhydrin (0.001 mol) and sarcosine (0.002 mol) (1:1:2) were dissolved in methanol (10 ml) and refluxed for 4 h. After completion of the reaction as evident from TLC, the excess solvent was evaporated slowly and the product was separated and recrystallized from methanol to reveal the title compound as yellow crystals.