Glycozolidal

Hoong-Kun Fun; Wisanu Maneerat; Surat Laphookhieo; Suchada Chantrapromma

doi:10.1107/S1600536811024160

. 2011 Jun 25;67(Pt 7):o1811–o1812. doi: 10.1107/S1600536811024160

Glycozolidal

Hoong-Kun Fun ^a,^*,^‡, Wisanu Maneerat ^b, Surat Laphookhieo ^b, Suchada Chantrapromma ^c,^§

PMCID: PMC3151865 PMID: 21837182

Abstract

The title compound known as glycozolidal (systematic name: 2,7-dimethoxy-9H-carbazole-3-carbaldehyde), C₁₅H₁₃NO₃, is a naturally occurring carbazole, which was isolated from the roots of Clausena lansium. The carbazole ring system is essentially planar, with an r.m.s. deviation of 0.0093 (1) Å. In the crystal, intermolecular N—H⋯O hydrogen bonds connect the molecules into a chain along the c axis. C—H⋯O, C—H⋯π and π–π interactions, with centroid–centroid distances of 3.5924 (6), 3.6576 (6) and 3.8613 (6) Å, are also observed.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For background to carbazole alkaloids and their activities, see: Kongkathip & Kongkathip (2009 ▶); Laphookhieo et al. (2009 ▶); Li et al. (1991 ▶); Maneerat & Laphookhieo (2010 ▶); Maneerat et al. (2010 ▶); Sripisut & Laphookhieo (2010 ▶); Tangyuenyongwatthana et al. (1992 ▶); Thongthoom et al. (2010 ▶); Yenjai et al. (2000 ▶). For related structures, see: Fun et al. (2007 ▶, 2009 ▶, 2010 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₅H₁₃NO₃
M _r = 255.26
Monoclinic,
a = 20.5756 (4) Å
b = 8.1298 (1) Å
c = 14.0411 (3) Å
β = 98.871 (1)°
V = 2320.64 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.53 × 0.42 × 0.16 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.947, T _max = 0.984
13003 measured reflections
3381 independent reflections
3032 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.115
S = 1.04
3381 reflections
178 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811024160/is2736sup1.cif

e-67-o1811-sup1.cif^{(18.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811024160/is2736Isup2.hkl

e-67-o1811-Isup2.hkl^{(165.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811024160/is2736Isup3.cml

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

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

Cg2 is the centroid of the C1–C4/C11/C12 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O3ⁱ	0.890 (17)	2.106 (17)	2.9758 (11)	165.2 (15)
C15—H15C⋯O2ⁱⁱ	0.98	2.44	3.3888 (14)	162
C15—H15A⋯Cg2ⁱⁱⁱ	0.98	2.91	3.6613 (12)	134

Open in a new tab

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

Acknowledgments

SL and WM thank Mae Fah Luang University and the Thailand Research Fund through the TRF-research scholar (grant No. RSA5280011) and the Royal Golden Jubilee PhD Program (grant No. PHD/0006/2552) for financial support. SC thanks the Prince of Songkla University for generous support through the Crystal Materials Research Unit. The authors also Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160.

supplementary crystallographic information

Comment

Carbazole alkaloids are major compounds found in Rutaceae plants, especially in Clausena genus (Laphookhieo et al., 2009; Li et al., 1991; Maneerat et al., 2010; Sripisut & Laphookhieo, 2010; Tangyuenyongwatthana et al., 1992) which showed diverse pharmacological activities such as anti-cancer, anti-malaria, anti-TB and anti-HIV (Kongkathip & Kongkathip, 2009; Yenjai et al., 2000; Thongthoom et al., 2010) properties. During the course of our on-going research on chemical constituents and bioactive compounds from Clausena plants (Maneerat et al., 2010; Maneerat & Laphookhieo, 2010; Sripisut & Laphookhieo, 2010), the title compound (I) which was known as glycozolidal (Li et al., 1991) was isolated from the roots of C. lansium which was collected from Nan province in the northern part of Thailand. Herein the isolation and crystal structure of (I) was reported.

In the structure of (I), C₁₅H₁₃NO₃ (Fig. 1), the carbazole ring system (C1–C12/N1) is essentially planar with an r.m.s. deviation of 0.0093 (1) Å. The aldehyde substituent is planarly attached to the benzene ring which can be indicated by the torsion angle C4–C3–C14–O2 = -3.35 (16)°. whereas the two methoxy groups are slightly deviated from their attached benzene rings with the torsion angles C13–O1–C2–C1 = -6.03 (14)° and C15–O3–C6–C7 = 13.32 (13)°. The bond lengths and angles in (I) are within normal ranges (Allen et al., 1987) and are comparable to the related structures (Fun et al., 2007, 2009, 2010).

In the crystal packing (Fig. 2), N—H···O intermolecular hydrogen bonds (Table 1) connected the molecules into one dimensional chains along the [0 0 1] direction. The crystal is consolidated by short N···O [2.9758 (11) Å] contact, as well as by N—H···O hydrogen bonds, C—H···O and C—H···π (Table 1) and π–π interactions with the distances of Cg1···Cg1^iv = 3.8613 (6) Å Cg1···Cg2^iv = 3.5924 (6) Å and Cg2···Cg3^iv = 3.6576 (6) Å [symmetry code: (iv) 1/2 - x, 1/2 - y, 1 - z; Cg1, Cg2 and Cg3 are the centroids of the C9–C12/N1, C1–C4/C11/C12 and C5–C10 rings, respectively]. .

Experimental

The air dried roots of C. lansium (2.92 kg) were successively extracted with acetone over the period of 3 days at room temperature. The solvent was removed under reduced pressure to provide the acetone extract (61.46 g) which was subjected to quick column chromatography (QCC) over silica gel and eluted with a gradient of hexanes-EtOAc (100% hexane to 100% EtOAc) to provide eight fractions (A—H). Fraction C (14.79 g) was further separated by sephadex LH-20 with CH₃OH to give six subfractions (C1—6). Subfraction C4 (5.70 g) was subjected to repeated QCC using 20% hexanes-EtOAc yielding the title compound (I) (19.6 mg). Yellow block-shaped single crystals of the title compound suitable for x-ray structure determination were recrystallized from CH₂Cl₂/acetone (1:4, v/v) after several days, Mp 469.6–470.7 K.