2-Hy­droxy-7-meth­oxy-9H-carbazole-3-carbaldehyde

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

doi:10.1107/S1600536810033805

. 2010 Aug 28;66(Pt 9):o2418–o2419. doi: 10.1107/S1600536810033805

2-Hydroxy-7-methoxy-9H-carbazole-3-carbaldehyde

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

PMCID: PMC3007870 PMID: 21588744

Abstract

The title compound, C₁₄H₁₁NO₃, was isolated from the roots of Clausena wallichii. The carbazole ring system is approximately planar (r.m.s. deviation = 0.039 Å) and the dihedral angle between the two benzene rings is 4.63 (7)°. An intramolecular O—H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, molecules are linked into a zigzag network extending parallel to the ac plane by O—H⋯N and N—H⋯O hydrogen bonds.

Related literature

For compounds isolated from plants of genera Rutaceae and their pharmacological activity, see: Ito et al. (1997 ▶); 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 ▶); Yenjai et al. 2000 ▶). For a related structure, see: Fun et al. (2009 ▶). For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used in the data collection, see Cosier & Glazer, (1986 ▶).

Experimental

Crystal data

C₁₄H₁₁NO₃
M _r = 241.24
Orthorhombic,
a = 12.4352 (4) Å
b = 17.6564 (5) Å
c = 5.0839 (1) Å
V = 1116.23 (5) Å³
Z = 4
Cu Kα radiation
μ = 0.84 mm⁻¹
T = 100 K
0.23 × 0.19 × 0.10 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.831, T _max = 0.918
25207 measured reflections
2026 independent reflections
2018 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.097
S = 1.31
2026 reflections
170 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.63 e Å⁻³
Absolute structure: Flack (1983 ▶), 851 Friedel pairs
Flack parameter: 0.17 (19)

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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810033805/ci5167sup1.cif

e-66-o2418-sup1.cif^{(18.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810033805/ci5167Isup2.hkl

e-66-o2418-Isup2.hkl^{(99.7KB, 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
O1—H1O1⋯O2	0.81	1.96	2.6453 (17)	143
O1—H1O1⋯N1ⁱ	0.81	2.53	3.0457 (15)	123
N1—H1N1⋯O2ⁱⁱ	0.85 (2)	2.10 (2)	2.941 (2)	172 (2)

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

Acknowledgments

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

supplementary crystallographic information

Comment

Rutaceae plants are known to be rich sources of coumarins and carbazole alkaloids. Many of them have been isolated from several genera of Rutaceae especially from Clausena genus (Laphookhieo et al., 2009; Maneerat et al., 2010; Sripisut & Laphookhieo 2010; Kongkathip & Kongkathip 2009; Ito et al., 1997; Li et al., 1991; Tangyuenyongwatthana et al., 1992) and some of these compounds show interesting pharmacological activities (Maneerat & Laphookhieo 2010; Yenjai et al. 2000). Although Clausena wallichii is one of the Rutaceae plants, however phytochemical reports on the chemical constituents from this plant are rare. As part of our continuing study of chemical constituents and bioactive compounds from Thai medicinal plants, we report herein the crystal structure of the title compound, which was isolated from the roots of C. wallichii collected from Phrae province in the northern region of Thailand.

The non-hydrogen atoms of the title molecule (Fig. 1) are almost coplanar. The carbazole ring system (C1-C12/N1) is planar with an r.m.s. deviation of 0.039 Å [maximum deviation 0.072 (1) Å for atom C7]. The pyrrole ring makes dihedral angle of 1.66 (7) and 3.12 (8)°, respectively, with the C1–C4/C10–C11 and C5–C9/C12 benzene rings. The dihedral angle between the two benzene rings being 4.63 (7)°. The cabaldehyde and methoxy substituents at atoms C3 and C7, respectively, are coplanar with the benzene ring, as indicated by torsion angles C2–C3–C13–O2 = 0.0 (2)° and C14–O3–C7–C8 = 4.0 (2)°. An intramolecular O1—H1O1···O2 hydrogen bond (Table 1) generates an S(6) ring motif (Fig. 1 and Table 1) (Bernstein et al., 1995). The bond distances are within normal ranges (Allen et al., 1987) and comparable to a related structure (Fun et al., 2009).

The crystal packing of the title compound is stabilized by intermolecular O—H···N and N—H···O hydrogen bonds (Table 1) which link the molecules into a zigzag network extending parallel to the ac plane.

Experimental

The roots of C. wallichii (1.02 Kg) were successively extracted with CH₂Cl₂ over the period of 3 days each at room temperature to provide the crude CH₂Cl₂ extract which subjected to quick column chromatography (QCC) over silica gel eluted with a gradient of hexane-EtOAc (100% hexane to 100% EtOAc) to provide nine fractions (A-I). Fraction G (3.12 g) was further separated by QCC with a gradient of 10% EtOAc-hexane to 100% EtOAc to give seven subfractions (G1-G7). Subfraction G4 (118.9 mg) was subjected to repeated column chromatography using 30% EtOAc-hexane to yield the yellow solid of the title compound (12.8 mg). Yellow plate-shaped single crystals of the title compound suitable for X-ray structure determination were recrystallized from CH₂Cl₂/acetone (1:1 v/v) by the slow evaporation of the solvent at room temperature after several days; m.p. 496.7-498.8 K (decomposition).