Rauniticine-allo-oxindole B methanol monosolvate

Salim, F.; Ahmad, R.; Ismail, N.H.; Hazni, H.; Ng, S.W.

doi:10.1107/S1600536811016710

organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1345

doi:10.1107/S1600536811016710

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Rauniticine-allo-oxindole B methanol monosolvate

Fatimah Salim,^a Rohaya Ahmad,^a Nor Hadiani Ismail,^a Hazrina Hazni ^b and Seik Weng Ng ^b ^*

^aFaculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 3 May 2011; accepted 3 May 2011; online 7 May 2011)

The title pentacyclic oxindole alkadoid, isolated from Uncaria longiflora, crystallizes as a methanol solvate, C₂₀H₂₂N₂O₄·CH₄O. The five-membered ring comprising the indole fused ring is nearly planar [maximum atomic deviation = 0.031 (2) Å], whereas the five-membered ring having alphatic C atoms adopts an envelope shape (with the tertiary N atom representing the flap). The six-membered ring that shares an N atom with the envelope-shaped ring adopts a chair shape; the six-membered ring having an O atom is sofa-shaped. The carboxylic acid group acts as a hydrogen-bond donor to a methanol molecule; this, in turn, acts as a hydrogen-bond donor to the double-bond carboxyl O atom of an adjacent molecule, generating a chain. Adjacent chains are linked by N—H⋯O hydrogen bonds, forming a layer motif.

Related literature

For the spectroscopic identification of rauniticine-allo-oxindole B, see: Seki et al. (1993 ).

Experimental

Crystal data

C₂₀H₂₂N₂O₄·CH₄O
M_r = 386.44
Monoclinic, P 2₁
a = 9.2330 (3) Å
b = 7.2110 (2) Å
c = 14.7678 (4) Å
β = 99.313 (3)°
V = 970.27 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.20 × 0.10 × 0.05 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.981, T_max = 0.995
9109 measured reflections
2381 independent reflections
2181 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.093
S = 1.05
2381 reflections
266 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O5	0.84 (3)	1.83 (3)	2.662 (3)	173 (4)
O5—H5⋯O2ⁱ	0.84 (3)	1.91 (3)	2.728 (2)	165 (4)
N2—H2⋯O4ⁱⁱ	0.88 (3)	1.97 (3)	2.805 (3)	158 (3)
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+2]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+1]$ .

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811016710/xu5205sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811016710/xu5205Isup2.hkl

checkCIF report

Comment top

The genus Uncaria is a source of diverse bioactive compounds, and parts of the plant are use for medicinal purposes. The structure of rauniticine-allo-oxindole B was previously elucidated by NMR spectroscopy in on study on heteroyohimbine-type oxindole alkaloids (Seki et al., 1993). The assignment is confirmed in the present study on the methanol-solvated compound (Scheme I) isolated from Uncaria longiflora. The pentacyclic oxindole alkadoid, C₂₀H₂₂N₂O₄, features a five-membered ring that adopts the shape of an envelope (with the tertiary N atom representing the flap). The six-membered ring that shares an N atom with the envelope-shaped ring adopts the shape of a chair; the six-membered ring having an O atom is sofa-shaped (Fig. 1). The carboxylic acid portion of the molecule is hydrogen-bond donor to a methanol molecule; this, in turn, is hydrogen-bond donor to the double-bond carboxyl O atom of an adjacent molecule to generate a chain. Adjacent chains are linked by an N–H···O hydrogen bond to form a layer motif (Table 1, Fig. 2).

Related literature top

For the spectroscopic identification of rauniticine-allo-oxindole B, see: Seki et al. (1993).

Experimental top

Uncaria longiflora plant material was collected from Hutan Simpan Bangi, Selangor, Malaysia, and specimens were deposited at Taman Botani Putrajaya, Malaysia. Dried and ground stems were extracted with methanol for 72 h to give 25 g of crude extract. This was acidified with 5% hydrochloric acid, and non-alkaloidal material was removed followed with basification with 37% ammonium hydroxide to release the alkaloid. The alkaloid was extracted into chloroform to give 2.25 g of a crude alkaloid fraction. The fraction was dissolved in methanol and subjected to radial chromatography (4 mm thickness silica-gel plate) with dichloromethane:ethyl acetate followed by ethyl acetate:methanol with a gradual increase of solvent polarity. Rauniticine-allo-oxindole B was separated and purified by repeated preparative thin layer chromatography using chloroform:methanol (120:5). The polar fraction afforded colorless crystals when the solvent was allowed to evaporate (53 mg).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); 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, 2010).

Figures top

	Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₂₀H₂₂N₂O₄^.CH₃OH at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Hydrogen-bonded layer structure.

2-oxo-1,2,2',3',5',5'a,6',9'a,10',10'a-decahydrospiro[indole-3,1'- pyrano[3,4-f]indolizine]-9'-carboxylic acid methanol monosolvate top

Crystal data top

C₂₀H₂₂N₂O₄·CH₄O	F(000) = 412
M_r = 386.44	D_x = 1.323 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 4552 reflections
a = 9.2330 (3) Å	θ = 2.4–29.2°
b = 7.2110 (2) Å	µ = 0.10 mm⁻¹
c = 14.7678 (4) Å	T = 100 K
β = 99.313 (3)°	Prism, colorless
V = 970.27 (5) Å³	0.20 × 0.10 × 0.05 mm
Z = 2

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	2381 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2181 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.039
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.5°, θ_min = 2.4°
ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −9→9
T_min = 0.981, T_max = 0.995	l = −19→19
9109 measured reflections

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0455P)² + 0.2288P] where P = (F_o² + 2F_c²)/3
2381 reflections	(Δ/σ)_max = 0.001
266 parameters	Δρ_max = 0.21 e Å⁻³
4 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₂₀H₂₂N₂O₄·CH₄O	V = 970.27 (5) Å³
M_r = 386.44	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 9.2330 (3) Å	µ = 0.10 mm⁻¹
b = 7.2110 (2) Å	T = 100 K
c = 14.7678 (4) Å	0.20 × 0.10 × 0.05 mm
β = 99.313 (3)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	2381 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	2181 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.995	R_int = 0.039
9109 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	4 restraints
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.21 e Å⁻³
2381 reflections	Δρ_min = −0.19 e Å⁻³
266 parameters

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

	x	y	z	U_iso*/U_eq
O1	1.30437 (18)	1.0011 (3)	0.98971 (12)	0.0253 (4)
O2	1.06782 (16)	0.9207 (3)	0.96906 (11)	0.0226 (4)
O3	1.42440 (17)	0.5574 (3)	0.85208 (12)	0.0257 (4)
O4	1.04085 (17)	0.6078 (3)	0.54863 (11)	0.0214 (4)
O5	1.20768 (17)	1.2803 (3)	1.08162 (11)	0.0233 (4)
N1	0.9975 (2)	0.3485 (3)	0.71523 (12)	0.0181 (4)
N2	0.8390 (2)	0.7963 (3)	0.52546 (13)	0.0204 (4)
C1	1.1933 (2)	0.8909 (3)	0.95551 (14)	0.0180 (5)
C2	1.2329 (2)	0.7332 (4)	0.90209 (15)	0.0180 (5)
C3	1.3739 (2)	0.6984 (4)	0.89692 (15)	0.0224 (5)
H3	1.4447	0.7818	0.9280	0.027*
C4	1.3173 (3)	0.4343 (4)	0.79913 (16)	0.0218 (5)
H4	1.2837	0.4902	0.7373	0.026*
C5	1.3986 (3)	0.2554 (4)	0.7878 (2)	0.0339 (6)
H5A	1.4810	0.2807	0.7553	0.051*
H5B	1.3316	0.1667	0.7525	0.051*
H5C	1.4359	0.2032	0.8484	0.051*
C6	1.1853 (2)	0.4113 (4)	0.84882 (15)	0.0188 (5)
H6	1.2229	0.3627	0.9117	0.023*
C9	1.0709 (2)	0.2749 (4)	0.80272 (15)	0.0200 (5)
H9A	1.1188	0.1557	0.7924	0.024*
H9B	0.9975	0.2512	0.8433	0.024*
C10	0.9215 (2)	0.5222 (3)	0.72771 (15)	0.0163 (5)
H10	0.8512	0.4990	0.7713	0.020*
C11	1.0279 (2)	0.6712 (3)	0.76820 (14)	0.0168 (5)
H11A	0.9735	0.7855	0.7786	0.020*
H11B	1.0963	0.7006	0.7251	0.020*
C12	1.1150 (2)	0.6013 (3)	0.86019 (15)	0.0164 (5)
H12	1.0443	0.5862	0.9043	0.020*
C13	0.8837 (3)	0.2265 (4)	0.66791 (16)	0.0229 (5)
H13A	0.8237	0.1735	0.7114	0.028*
H13B	0.9272	0.1239	0.6368	0.028*
C14	0.7913 (3)	0.3531 (4)	0.59816 (15)	0.0201 (5)
H14A	0.6853	0.3293	0.5968	0.024*
H14B	0.8151	0.3324	0.5359	0.024*
C15	0.8317 (2)	0.5561 (3)	0.63129 (15)	0.0167 (5)
C16	0.9193 (2)	0.6518 (3)	0.56509 (15)	0.0179 (5)
C17	0.7091 (2)	0.8212 (4)	0.56293 (15)	0.0189 (5)
C18	0.6022 (2)	0.9545 (4)	0.54169 (16)	0.0223 (5)
H18	0.6081	1.0452	0.4958	0.027*
C19	0.4849 (3)	0.9504 (4)	0.59050 (16)	0.0242 (5)
H19	0.4095	1.0408	0.5780	0.029*
C20	0.4765 (2)	0.8163 (4)	0.65720 (16)	0.0239 (5)
H20	0.3963	0.8172	0.6902	0.029*
C21	0.5849 (2)	0.6802 (4)	0.67598 (15)	0.0205 (5)
H21	0.5786	0.5875	0.7209	0.025*
C22	0.7016 (2)	0.6830 (3)	0.62794 (14)	0.0165 (5)
C23	1.2794 (3)	1.4465 (4)	1.11555 (17)	0.0266 (6)
H23A	1.2064	1.5366	1.1290	0.040*
H23B	1.3332	1.4979	1.0693	0.040*
H23C	1.3483	1.4195	1.1718	0.040*
H1	1.273 (3)	1.083 (4)	1.0219 (19)	0.041 (9)*
H5	1.1180 (14)	1.304 (5)	1.065 (2)	0.043 (9)*
H2	0.870 (3)	0.878 (3)	0.4885 (16)	0.034 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0214 (8)	0.0253 (10)	0.0282 (9)	−0.0040 (8)	0.0009 (7)	−0.0078 (8)
O2	0.0186 (8)	0.0237 (10)	0.0254 (8)	0.0002 (7)	0.0033 (6)	−0.0060 (8)
O3	0.0181 (8)	0.0299 (11)	0.0298 (9)	0.0030 (8)	0.0052 (7)	−0.0029 (8)
O4	0.0241 (8)	0.0194 (9)	0.0225 (8)	0.0002 (7)	0.0096 (6)	−0.0014 (7)
O5	0.0190 (8)	0.0246 (10)	0.0255 (9)	−0.0013 (8)	0.0017 (6)	−0.0026 (8)
N1	0.0226 (9)	0.0140 (10)	0.0174 (9)	0.0007 (8)	0.0022 (7)	−0.0008 (8)
N2	0.0237 (10)	0.0199 (11)	0.0180 (9)	−0.0018 (9)	0.0045 (8)	0.0034 (8)
C1	0.0185 (10)	0.0188 (13)	0.0155 (10)	−0.0008 (10)	−0.0004 (8)	0.0021 (9)
C2	0.0176 (10)	0.0196 (12)	0.0169 (10)	−0.0003 (9)	0.0033 (8)	0.0034 (9)
C3	0.0199 (10)	0.0266 (14)	0.0205 (11)	−0.0017 (11)	0.0026 (9)	0.0017 (11)
C4	0.0219 (11)	0.0238 (13)	0.0206 (10)	0.0037 (10)	0.0063 (9)	−0.0016 (11)
C5	0.0315 (13)	0.0286 (15)	0.0446 (16)	0.0093 (12)	0.0153 (12)	0.0015 (13)
C6	0.0209 (11)	0.0187 (12)	0.0169 (10)	0.0030 (10)	0.0027 (8)	0.0011 (10)
C9	0.0232 (11)	0.0160 (12)	0.0212 (11)	0.0008 (10)	0.0046 (9)	0.0035 (10)
C10	0.0182 (10)	0.0154 (11)	0.0159 (10)	0.0010 (9)	0.0051 (8)	0.0014 (9)
C11	0.0176 (10)	0.0153 (11)	0.0172 (10)	0.0013 (9)	0.0019 (8)	0.0001 (9)
C12	0.0173 (10)	0.0165 (11)	0.0156 (10)	0.0015 (9)	0.0035 (8)	0.0001 (9)
C13	0.0284 (12)	0.0188 (13)	0.0216 (11)	−0.0028 (10)	0.0040 (9)	−0.0010 (10)
C14	0.0241 (11)	0.0173 (12)	0.0191 (11)	−0.0031 (10)	0.0040 (9)	−0.0011 (10)
C15	0.0187 (10)	0.0157 (12)	0.0161 (10)	0.0002 (9)	0.0042 (8)	−0.0015 (9)
C16	0.0214 (10)	0.0173 (12)	0.0146 (10)	−0.0041 (9)	0.0015 (8)	−0.0036 (9)
C17	0.0198 (10)	0.0190 (13)	0.0168 (10)	−0.0048 (10)	−0.0001 (8)	−0.0024 (9)
C18	0.0258 (11)	0.0188 (12)	0.0198 (11)	−0.0026 (10)	−0.0039 (9)	0.0001 (10)
C19	0.0239 (11)	0.0209 (13)	0.0248 (12)	0.0033 (11)	−0.0052 (9)	−0.0036 (11)
C20	0.0209 (11)	0.0275 (15)	0.0234 (12)	0.0021 (11)	0.0033 (9)	−0.0040 (11)
C21	0.0226 (11)	0.0197 (12)	0.0186 (10)	−0.0016 (10)	0.0019 (9)	−0.0005 (10)
C22	0.0191 (10)	0.0140 (11)	0.0150 (10)	−0.0028 (9)	−0.0010 (8)	−0.0032 (9)
C23	0.0237 (11)	0.0261 (14)	0.0296 (13)	−0.0006 (11)	0.0030 (10)	−0.0057 (12)

Geometric parameters (Å, º) top

O1—C1	1.331 (3)	C10—C11	1.512 (3)
O1—H1	0.84 (3)	C10—C15	1.547 (3)
O2—C1	1.227 (3)	C10—H10	1.0000
O3—C3	1.338 (3)	C11—C12	1.547 (3)
O3—C4	1.458 (3)	C11—H11A	0.9900
O4—C16	1.228 (3)	C11—H11B	0.9900
O5—C23	1.421 (3)	C12—H12	1.0000
O5—H5	0.84 (3)	C13—C14	1.529 (3)
N1—C9	1.458 (3)	C13—H13A	0.9900
N1—C13	1.459 (3)	C13—H13B	0.9900
N1—C10	1.462 (3)	C14—C15	1.569 (3)
N2—C16	1.356 (3)	C14—H14A	0.9900
N2—C17	1.411 (3)	C14—H14B	0.9900
N2—H2	0.88 (3)	C15—C22	1.505 (3)
C1—C2	1.464 (3)	C15—C16	1.530 (3)
C2—C3	1.340 (3)	C17—C18	1.377 (3)
C2—C12	1.502 (3)	C17—C22	1.393 (3)
C3—H3	0.9500	C18—C19	1.395 (3)
C4—C5	1.515 (4)	C18—H18	0.9500
C4—C6	1.530 (3)	C19—C20	1.392 (4)
C4—H4	1.0000	C19—H19	0.9500
C5—H5A	0.9800	C20—C21	1.397 (3)
C5—H5B	0.9800	C20—H20	0.9500
C5—H5C	0.9800	C21—C22	1.383 (3)
C6—C9	1.522 (3)	C21—H21	0.9500
C6—C12	1.537 (3)	C23—H23A	0.9800
C6—H6	1.0000	C23—H23B	0.9800
C9—H9A	0.9900	C23—H23C	0.9800
C9—H9B	0.9900

C1—O1—H1	109 (2)	H11A—C11—H11B	108.3
C3—O3—C4	117.88 (17)	C2—C12—C6	108.58 (17)
C23—O5—H5	108 (3)	C2—C12—C11	113.2 (2)
C9—N1—C13	113.6 (2)	C6—C12—C11	111.30 (19)
C9—N1—C10	111.33 (18)	C2—C12—H12	107.8
C13—N1—C10	104.68 (17)	C6—C12—H12	107.8
C16—N2—C17	111.6 (2)	C11—C12—H12	107.8
C16—N2—H2	125 (2)	N1—C13—C14	104.1 (2)
C17—N2—H2	122 (2)	N1—C13—H13A	110.9
O2—C1—O1	121.6 (2)	C14—C13—H13A	110.9
O2—C1—C2	123.3 (2)	N1—C13—H13B	110.9
O1—C1—C2	115.10 (19)	C14—C13—H13B	110.9
C3—C2—C1	120.4 (2)	H13A—C13—H13B	109.0
C3—C2—C12	120.3 (2)	C13—C14—C15	105.55 (18)
C1—C2—C12	119.10 (19)	C13—C14—H14A	110.6
O3—C3—C2	126.2 (2)	C15—C14—H14A	110.6
O3—C3—H3	116.9	C13—C14—H14B	110.6
C2—C3—H3	116.9	C15—C14—H14B	110.6
O3—C4—C5	105.80 (19)	H14A—C14—H14B	108.8
O3—C4—C6	109.42 (18)	C22—C15—C16	101.90 (19)
C5—C4—C6	114.1 (2)	C22—C15—C10	115.61 (18)
O3—C4—H4	109.1	C16—C15—C10	113.55 (18)
C5—C4—H4	109.1	C22—C15—C14	114.13 (18)
C6—C4—H4	109.1	C16—C15—C14	110.19 (18)
C4—C5—H5A	109.5	C10—C15—C14	101.82 (18)
C4—C5—H5B	109.5	O4—C16—N2	124.5 (2)
H5A—C5—H5B	109.5	O4—C16—C15	127.2 (2)
C4—C5—H5C	109.5	N2—C16—C15	108.30 (19)
H5A—C5—H5C	109.5	C18—C17—C22	122.9 (2)
H5B—C5—H5C	109.5	C18—C17—N2	128.5 (2)
C9—C6—C4	113.91 (19)	C22—C17—N2	108.6 (2)
C9—C6—C12	110.48 (18)	C17—C18—C19	117.1 (2)
C4—C6—C12	109.8 (2)	C17—C18—H18	121.5
C9—C6—H6	107.5	C19—C18—H18	121.5
C4—C6—H6	107.5	C20—C19—C18	121.2 (2)
C12—C6—H6	107.5	C20—C19—H19	119.4
N1—C9—C6	110.5 (2)	C18—C19—H19	119.4
N1—C9—H9A	109.5	C19—C20—C21	120.5 (2)
C6—C9—H9A	109.5	C19—C20—H20	119.7
N1—C9—H9B	109.5	C21—C20—H20	119.7
C6—C9—H9B	109.5	C22—C21—C20	118.7 (2)
H9A—C9—H9B	108.1	C22—C21—H21	120.6
N1—C10—C11	111.33 (17)	C20—C21—H21	120.6
N1—C10—C15	102.46 (18)	C21—C22—C17	119.6 (2)
C11—C10—C15	117.98 (19)	C21—C22—C15	131.2 (2)
N1—C10—H10	108.2	C17—C22—C15	109.2 (2)
C11—C10—H10	108.2	O5—C23—H23A	109.5
C15—C10—H10	108.2	O5—C23—H23B	109.5
C10—C11—C12	109.15 (19)	H23A—C23—H23B	109.5
C10—C11—H11A	109.8	O5—C23—H23C	109.5
C12—C11—H11A	109.8	H23A—C23—H23C	109.5
C10—C11—H11B	109.8	H23B—C23—H23C	109.5
C12—C11—H11B	109.8

O2—C1—C2—C3	−173.7 (2)	N1—C10—C15—C22	158.78 (18)
O1—C1—C2—C3	5.8 (3)	C11—C10—C15—C22	−78.6 (3)
O2—C1—C2—C12	0.8 (3)	N1—C10—C15—C16	−83.9 (2)
O1—C1—C2—C12	−179.7 (2)	C11—C10—C15—C16	38.7 (3)
C4—O3—C3—C2	3.7 (4)	N1—C10—C15—C14	34.5 (2)
C1—C2—C3—O3	178.6 (2)	C11—C10—C15—C14	157.11 (19)
C12—C2—C3—O3	4.1 (4)	C13—C14—C15—C22	−135.9 (2)
C3—O3—C4—C5	−158.8 (2)	C13—C14—C15—C16	110.2 (2)
C3—O3—C4—C6	−35.5 (3)	C13—C14—C15—C10	−10.6 (2)
O3—C4—C6—C9	−176.11 (19)	C17—N2—C16—O4	−175.5 (2)
C5—C4—C6—C9	−57.8 (3)	C17—N2—C16—C15	5.0 (2)
O3—C4—C6—C12	59.4 (2)	C22—C15—C16—O4	174.9 (2)
C5—C4—C6—C12	177.6 (2)	C10—C15—C16—O4	49.9 (3)
C13—N1—C9—C6	−178.73 (19)	C14—C15—C16—O4	−63.6 (3)
C10—N1—C9—C6	−60.9 (2)	C22—C15—C16—N2	−5.7 (2)
C4—C6—C9—N1	−68.4 (3)	C10—C15—C16—N2	−130.7 (2)
C12—C6—C9—N1	55.7 (2)	C14—C15—C16—N2	115.8 (2)
C9—N1—C10—C11	62.3 (2)	C16—N2—C17—C18	178.7 (2)
C13—N1—C10—C11	−174.57 (18)	C16—N2—C17—C22	−2.0 (3)
C9—N1—C10—C15	−170.65 (18)	C22—C17—C18—C19	1.9 (3)
C13—N1—C10—C15	−47.5 (2)	N2—C17—C18—C19	−178.8 (2)
N1—C10—C11—C12	−57.0 (2)	C17—C18—C19—C20	−0.4 (3)
C15—C10—C11—C12	−174.97 (18)	C18—C19—C20—C21	−0.9 (4)
C3—C2—C12—C6	20.8 (3)	C19—C20—C21—C22	0.9 (3)
C1—C2—C12—C6	−153.8 (2)	C20—C21—C22—C17	0.5 (3)
C3—C2—C12—C11	−103.4 (3)	C20—C21—C22—C15	−178.8 (2)
C1—C2—C12—C11	82.0 (2)	C18—C17—C22—C21	−2.0 (3)
C9—C6—C12—C2	−177.57 (17)	N2—C17—C22—C21	178.6 (2)
C4—C6—C12—C2	−51.1 (2)	C18—C17—C22—C15	177.5 (2)
C9—C6—C12—C11	−52.3 (2)	N2—C17—C22—C15	−1.9 (2)
C4—C6—C12—C11	74.2 (2)	C16—C15—C22—C21	−176.1 (2)
C10—C11—C12—C2	175.10 (18)	C10—C15—C22—C21	−52.5 (3)
C10—C11—C12—C6	52.4 (2)	C14—C15—C22—C21	65.2 (3)
C9—N1—C13—C14	162.01 (19)	C16—C15—C22—C17	4.5 (2)
C10—N1—C13—C14	40.4 (2)	C10—C15—C22—C17	128.1 (2)
N1—C13—C14—C15	−17.1 (2)	C14—C15—C22—C17	−114.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O5	0.84 (3)	1.83 (3)	2.662 (3)	173 (4)
O5—H5···O2ⁱ	0.84 (3)	1.91 (3)	2.728 (2)	165 (4)
N2—H2···O4ⁱⁱ	0.88 (3)	1.97 (3)	2.805 (3)	158 (3)

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

Experimental details

Crystal data
Chemical formula	C₂₀H₂₂N₂O₄·CH₄O
M_r	386.44
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	100
a, b, c (Å)	9.2330 (3), 7.2110 (2), 14.7678 (4)
β (°)	99.313 (3)
V (Å³)	970.27 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.10 × 0.05

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.981, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	9109, 2381, 2181
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.093, 1.05
No. of reflections	2381
No. of parameters	266
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.19

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O5	0.84 (3)	1.83 (3)	2.662 (3)	173 (4)
O5—H5···O2ⁱ	0.84 (3)	1.91 (3)	2.728 (2)	165 (4)
N2—H2···O4ⁱⁱ	0.88 (3)	1.97 (3)	2.805 (3)	158 (3)

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

Acknowledgements

We thank the University of Malaya for supporting this study.

References

Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar