4,4-Dimethyl-2-tosyl-1,2,3,3a,4,11b-hexa­hydro-11H-pyrrolo[3,4-c]pyrano[5,6-c]chromen-11-one 0.125-hydrate

Chinnakali, K.; Sudha, D.; Jayagobi, M.; Raghunathan, R.; Fun, H.-K.

doi:10.1107/S1600536809044730

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Pages o2943-o2944

https://doi.org/10.1107/S1600536809044730

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4,4-Dimethyl-2-tosyl-1,2,3,3a,4,11b-hexahydro-11H-pyrrolo[3,4-c]pyrano[5,6-c]chromen-11-one 0.125-hydrate

K. Chinnakali,^a ^* D. Sudha,^a ‡ M. Jayagobi,^b R. Raghunathan ^b and Hoong-Kun Fun ^c §

^aDepartment of Physics, Anna University Chennai, Chennai 600 025, India, ^bDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India, and ^cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: kali@annauniv.edu

(Received 26 October 2009; accepted 27 October 2009; online 31 October 2009)

In the title compound, C₂₃H₂₃NO₅S·0.125H₂O, the pyrrolidine ring has a twist conformation and the dihydropyran ring adopts a half-chair conformation; the two rings are cis-fused. The molecule adopts a folded conformation. The sulfonyl-bound phenyl ring and the pyran ring of the coumarin ring system are stacked over one another, with a centroid–centroid distance of 3.7470 (7) Å; the dihedral angle between the two rings is 18.93 (2)°. An intramolecular C—H⋯O hydrogen bond is observed. The solvent water molecule, lying on a twofold rotation axis, is only partially occupied with an occupancy of 0.125 (relative occupancy with respect to the main molecule) and is involved in O—H⋯O and C—H⋯O hydrogen bonding.

Related literature

For the biological activity of pyranocoumarin compounds, see: Kawaii et al. (2001 ); Hossain et al. (1996 ); Goel et al. (1997 ); Su et al. (2009 ); Xu et al. (2006 ). For asymmetry parameters, see: Duax et al. (1976 ).

Experimental

Crystal data

C₂₃H₂₃NO₅S·0.125H₂O
M_r = 427.74
Tetragonal, P 4₂ /n
a = 15.1932 (2) Å
c = 17.7180 (3) Å
V = 4089.91 (10) Å³
Z = 8
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 100 K
0.50 × 0.44 × 0.13 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.845, T_max = 0.976
97892 measured reflections
6004 independent reflections
5114 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.109
S = 1.05
6004 reflections
282 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O5	0.97	2.47	3.0588 (15)	119
O1W—H1W1⋯O2	0.83 (2)	2.05 (8)	2.837 (2)	161 (8)
C16—H16B⋯O1Wⁱ	0.96	2.43	3.345 (5)	160
C16—H16B⋯O1Wⁱⁱ	0.96	2.43	3.345 (5)	160
C14—H14B⋯O1Wⁱⁱⁱ	0.96	2.44	3.282 (2)	147
C14—H14B⋯O1W^iv	0.96	2.44	3.282 (2)	147
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, -z+1]$ ; (iii) $[y, -x+{\script{3\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-y+{\script{3\over 2}}, x, -z+{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809044730/bt5116sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809044730/bt5116Isup2.hkl

checkCIF report

Comment top

Pyranocoumarins show strong activity against cancer cell lines (Kawaii et al., 2001) and exhibit monoamine oxidase inhibitory activity (Hossain et al., 1996). Antiulcer activity of some naturally occurring pyrano-coumarin has been reported (Goel et al., 1997). They also show anti-hepatitis B virus and cytotoxic activities (Su et al., 2009) and anti-TB activity (Xu et al., 2006). We report here the crystal structure of the title pyranocoumarin derivative.

In the title molecule (Fig.1), the coumarin ring system is planar with an r.m.s. deviation of 0.036 Å. The pyrrolidine ring has a twist conformation, with asymmetry parameter (Duax et al., 1976) ΔC₂[N1] = ΔC₂[C2—C3] = 1.7 (1)°. The tosyl group is equatorially attached to the pyrrolidine ring. The dihydropyran ring adopts a half-chair conformation, with the asymmetry parameter ΔC₂[C2—C5] = 7.4 (1)°. The pyrrolidine ring is cis-fused to the dihydropyran ring. The sulfonyl group has a distorted tetrahedral geometry [O1—S1—O2 = 119.79 (6)°]. The molecule adopts a folded conformation, with the sulfonyl-bound phenyl ring and the pyran ring of the coumarin ring system being stacked over one another. The dihedral angle between the above two rings is 18.93 (2)° and their centroid-to-centroid separation is 3.7470 (7) Å. An intramolecular C4—H4A···O5 hydrogen bond is observed.

In the crystal structure, the water molecule with a fractional occupancy of 0.125 is involved in O—H···O and C—H···O hydrogen bonding with the coumarin derivative leading to the formation of a three-dimensional network (Fig.2).

Related literature top

For the biological activity of pyranocoumarin compounds, see: Kawaii et al. (2001); Hossain et al. (1996); Goel et al. (1997); Su et al. (2009); Xu et al. (2006). For asymmetry parameters, see: Duax et al. (1976).

Experimental top

To a solution of 4-hydroxycoumarin (1 mmol) in toluene (20 ml), the corresponding 2-(N-prenyl-N-tosylamino)acetaldehyde (1 mmol) and a catalytic amount of the base ethylenediamine-N,N'-diacetate (EDDA, 1 mmol) were added and the reaction mixture was refluxed for 12 h. After completion of the reaction, the solvent was evaporated under reduced pressure and the crude product was chromatographed using a hexane-ethyl acetate (8:2 v/v) mixture to obtain the title compound. The compound was recrystallized from ethyl acetate solution by slow evaporation.

Structure description top

For the biological activity of pyranocoumarin compounds, see: Kawaii et al. (2001); Hossain et al. (1996); Goel et al. (1997); Su et al. (2009); Xu et al. (2006). For asymmetry parameters, see: Duax et al. (1976).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. The water molecule has a fractional occupancy of 0.125. One of the water H atoms is generated by the symmetry operation (3/2 - x, 3/2 - y, z). Dashed lines indicate hydrogen bonds.
	Fig. 2. Crystal packing of the title compound, viewed along the c axis. The water molecule has a fractional occupancy of 0.125. Hydrogen bonds are shown as dashed lines. For the sake of clarity, H atoms not involved in the interactions have been omitted.

4,4-Dimethyl-2-tosyl-1,2,3,3a,4,11b-hexahydro-11H- pyrrolo[3,4-c]pyrano[5,6-c]chromen-11-one 0.125-hydrate top

Crystal data top

C₂₃H₂₃NO₅S·0.125H₂O	D_x = 1.389 Mg m⁻³
M_r = 427.74	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4₂/n	Cell parameters from 9971 reflections
Hall symbol: -P 4bc	θ = 2.2–29.7°
a = 15.1932 (2) Å	µ = 0.20 mm⁻¹
c = 17.7180 (3) Å	T = 100 K
V = 4089.91 (10) Å³	Block, colourless
Z = 8	0.50 × 0.44 × 0.13 mm
F(000) = 1802

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	6004 independent reflections
Radiation source: fine-focus sealed tube	5114 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
φ and ω scans	θ_max = 30.1°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −19→21
T_min = 0.845, T_max = 0.976	k = −19→21
97892 measured reflections	l = −24→25

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0592P)² + 1.3394P] where P = (F_o² + 2F_c²)/3
6004 reflections	(Δ/σ)_max = 0.001
282 parameters	Δρ_max = 0.44 e Å⁻³
1 restraint	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₂₃H₂₃NO₅S·0.125H₂O	Z = 8
M_r = 427.74	Mo Kα radiation
Tetragonal, P4₂/n	µ = 0.20 mm⁻¹
a = 15.1932 (2) Å	T = 100 K
c = 17.7180 (3) Å	0.50 × 0.44 × 0.13 mm
V = 4089.91 (10) Å³

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	6004 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	5114 reflections with I > 2σ(I)
T_min = 0.845, T_max = 0.976	R_int = 0.058
97892 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	1 restraint
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.44 e Å⁻³
6004 reflections	Δρ_min = −0.36 e Å⁻³
282 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	Occ. (<1)
S1	0.581635 (19)	0.56278 (2)	0.395952 (15)	0.02140 (8)
O1	0.62409 (6)	0.47960 (7)	0.40829 (5)	0.0292 (2)
O2	0.61326 (6)	0.63995 (7)	0.43408 (5)	0.0313 (2)
O3	0.30418 (6)	0.47680 (5)	0.26574 (4)	0.01818 (16)
O4	0.35320 (6)	0.73448 (6)	0.20657 (5)	0.02448 (19)
O5	0.35668 (6)	0.77642 (6)	0.32563 (5)	0.02305 (18)
N1	0.47990 (6)	0.55091 (7)	0.42058 (5)	0.01870 (19)
C1	0.43048 (8)	0.47357 (8)	0.39346 (6)	0.0190 (2)
H1A	0.4416	0.4226	0.4250	0.023*
H1B	0.4460	0.4595	0.3418	0.023*
C2	0.33383 (7)	0.50282 (7)	0.39921 (6)	0.0168 (2)
H2	0.3125	0.4905	0.4503	0.020*
C3	0.33722 (7)	0.60314 (7)	0.38784 (6)	0.0165 (2)
H3	0.2865	0.6312	0.4120	0.020*
C4	0.42234 (8)	0.62880 (8)	0.42864 (6)	0.0191 (2)
H4A	0.4489	0.6801	0.4054	0.023*
H4B	0.4111	0.6414	0.4814	0.023*
C5	0.27372 (8)	0.45698 (7)	0.34279 (6)	0.0180 (2)
C6	0.32304 (7)	0.56163 (7)	0.25100 (6)	0.0161 (2)
C7	0.33841 (7)	0.62372 (7)	0.30463 (6)	0.0163 (2)
C8	0.58331 (7)	0.58347 (8)	0.29825 (6)	0.0191 (2)
C9	0.56995 (11)	0.66848 (9)	0.27189 (7)	0.0313 (3)
H9	0.5634	0.7150	0.3056	0.038*
C10	0.56654 (12)	0.68315 (9)	0.19508 (8)	0.0387 (4)
H10	0.5564	0.7399	0.1775	0.046*
C11	0.57777 (10)	0.61547 (9)	0.14336 (7)	0.0284 (3)
C12	0.59130 (8)	0.53099 (8)	0.17059 (7)	0.0211 (2)
H12	0.5989	0.4848	0.1367	0.025*
C13	0.59373 (8)	0.51415 (8)	0.24766 (6)	0.0195 (2)
H13	0.6022	0.4571	0.2653	0.023*
C14	0.57659 (14)	0.63433 (12)	0.05996 (8)	0.0496 (5)
H14A	0.5511	0.5853	0.0337	0.074*
H14B	0.6357	0.6435	0.0425	0.074*
H14C	0.5422	0.6862	0.0505	0.074*
C15	0.17906 (8)	0.48882 (8)	0.34908 (7)	0.0229 (2)
H15A	0.1432	0.4582	0.3130	0.034*
H15B	0.1768	0.5509	0.3391	0.034*
H15C	0.1575	0.4775	0.3991	0.034*
C16	0.27884 (9)	0.35747 (8)	0.34841 (7)	0.0244 (2)
H16A	0.2400	0.3315	0.3119	0.037*
H16B	0.2617	0.3393	0.3982	0.037*
H16C	0.3381	0.3386	0.3387	0.037*
C17	0.32585 (7)	0.58344 (8)	0.17165 (6)	0.0180 (2)
C18	0.31166 (8)	0.52190 (8)	0.11395 (6)	0.0211 (2)
H18	0.3007	0.4633	0.1258	0.025*
C19	0.31403 (9)	0.54850 (9)	0.03950 (7)	0.0252 (3)
H19	0.3041	0.5078	0.0013	0.030*
C20	0.33121 (10)	0.63606 (10)	0.02134 (7)	0.0307 (3)
H20	0.3327	0.6532	−0.0290	0.037*
C21	0.34609 (10)	0.69774 (9)	0.07730 (7)	0.0307 (3)
H21	0.3584	0.7560	0.0651	0.037*
C22	0.34229 (8)	0.67083 (8)	0.15238 (6)	0.0223 (2)
C23	0.35020 (8)	0.71478 (8)	0.28241 (6)	0.0190 (2)
O1W	0.7500	0.7500	0.4887 (3)	0.0379 (14)	0.25
H1W1	0.714 (5)	0.723 (5)	0.463 (4)	0.057*	0.25

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01678 (14)	0.03109 (17)	0.01633 (13)	0.00006 (10)	−0.00130 (9)	0.00123 (10)
O1	0.0219 (4)	0.0431 (6)	0.0225 (4)	0.0104 (4)	−0.0003 (3)	0.0089 (4)
O2	0.0238 (5)	0.0462 (6)	0.0241 (4)	−0.0101 (4)	−0.0015 (3)	−0.0076 (4)
O3	0.0253 (4)	0.0136 (4)	0.0156 (3)	−0.0018 (3)	0.0003 (3)	0.0007 (3)
O4	0.0349 (5)	0.0179 (4)	0.0207 (4)	−0.0063 (3)	−0.0050 (3)	0.0041 (3)
O5	0.0261 (4)	0.0163 (4)	0.0267 (4)	−0.0019 (3)	−0.0023 (3)	−0.0015 (3)
N1	0.0163 (4)	0.0216 (5)	0.0182 (4)	0.0010 (4)	−0.0001 (3)	0.0003 (3)
C1	0.0199 (5)	0.0190 (5)	0.0181 (5)	0.0011 (4)	−0.0008 (4)	0.0009 (4)
C2	0.0188 (5)	0.0164 (5)	0.0152 (4)	0.0000 (4)	0.0006 (4)	0.0013 (4)
C3	0.0178 (5)	0.0157 (5)	0.0161 (4)	0.0005 (4)	0.0008 (4)	−0.0007 (4)
C4	0.0208 (5)	0.0195 (5)	0.0169 (5)	0.0003 (4)	−0.0013 (4)	−0.0022 (4)
C5	0.0214 (5)	0.0162 (5)	0.0164 (5)	−0.0020 (4)	0.0005 (4)	0.0027 (4)
C6	0.0161 (5)	0.0148 (5)	0.0173 (5)	0.0006 (4)	−0.0008 (4)	0.0018 (4)
C7	0.0167 (5)	0.0152 (5)	0.0171 (5)	0.0003 (4)	−0.0011 (4)	0.0013 (4)
C8	0.0175 (5)	0.0223 (5)	0.0175 (5)	−0.0005 (4)	0.0009 (4)	0.0016 (4)
C9	0.0501 (9)	0.0184 (6)	0.0253 (6)	0.0008 (5)	0.0106 (6)	−0.0021 (5)
C10	0.0695 (11)	0.0195 (6)	0.0272 (6)	0.0099 (6)	0.0134 (7)	0.0065 (5)
C11	0.0404 (8)	0.0249 (6)	0.0200 (5)	0.0089 (5)	0.0051 (5)	0.0053 (5)
C12	0.0240 (6)	0.0204 (5)	0.0190 (5)	0.0016 (4)	0.0005 (4)	−0.0004 (4)
C13	0.0201 (5)	0.0183 (5)	0.0201 (5)	0.0014 (4)	0.0004 (4)	0.0027 (4)
C14	0.0861 (14)	0.0409 (9)	0.0217 (6)	0.0300 (9)	0.0102 (7)	0.0097 (6)
C15	0.0194 (5)	0.0235 (6)	0.0256 (6)	−0.0029 (4)	−0.0004 (4)	0.0019 (4)
C16	0.0322 (7)	0.0161 (5)	0.0250 (6)	−0.0025 (4)	−0.0019 (5)	0.0029 (4)
C17	0.0184 (5)	0.0194 (5)	0.0162 (5)	−0.0007 (4)	−0.0012 (4)	0.0021 (4)
C18	0.0237 (6)	0.0209 (5)	0.0188 (5)	0.0017 (4)	−0.0024 (4)	0.0008 (4)
C19	0.0290 (6)	0.0290 (6)	0.0177 (5)	0.0018 (5)	−0.0036 (4)	−0.0004 (4)
C20	0.0389 (8)	0.0351 (7)	0.0180 (5)	−0.0040 (6)	−0.0036 (5)	0.0072 (5)
C21	0.0424 (8)	0.0273 (7)	0.0225 (6)	−0.0088 (5)	−0.0046 (5)	0.0090 (5)
C22	0.0266 (6)	0.0207 (6)	0.0195 (5)	−0.0039 (4)	−0.0039 (4)	0.0030 (4)
C23	0.0188 (5)	0.0173 (5)	0.0208 (5)	−0.0010 (4)	−0.0023 (4)	0.0027 (4)
O1W	0.055 (4)	0.037 (3)	0.022 (2)	−0.029 (3)	0.000	0.000

Geometric parameters (Å, º) top

S1—O1	1.4355 (10)	C9—C10	1.3799 (19)
S1—O2	1.4359 (10)	C9—H9	0.93
S1—N1	1.6161 (10)	C10—C11	1.3878 (19)
S1—C8	1.7597 (12)	C10—H10	0.93
O3—C6	1.3459 (13)	C11—C12	1.3865 (17)
O3—C5	1.4727 (13)	C11—C14	1.5054 (18)
O4—C22	1.3728 (14)	C12—C13	1.3897 (15)
O4—C23	1.3774 (14)	C12—H12	0.93
O5—C23	1.2137 (14)	C13—H13	0.93
N1—C1	1.4749 (15)	C14—H14A	0.96
N1—C4	1.4784 (15)	C14—H14B	0.96
C1—C2	1.5376 (16)	C14—H14C	0.96
C1—H1A	0.97	C15—H15A	0.96
C1—H1B	0.97	C15—H15B	0.96
C2—C5	1.5225 (15)	C15—H15C	0.96
C2—C3	1.5382 (15)	C16—H16A	0.96
C2—H2	0.98	C16—H16B	0.96
C3—C7	1.5072 (14)	C16—H16C	0.96
C3—C4	1.5320 (16)	C17—C22	1.3935 (16)
C3—H3	0.98	C17—C18	1.4021 (16)
C4—H4A	0.97	C18—C19	1.3800 (16)
C4—H4B	0.97	C18—H18	0.93
C5—C16	1.5172 (16)	C19—C20	1.3934 (19)
C5—C15	1.5215 (17)	C19—H19	0.93
C6—C7	1.3592 (15)	C20—C21	1.383 (2)
C6—C17	1.4449 (14)	C20—H20	0.93
C7—C23	1.4497 (15)	C21—C22	1.3929 (16)
C8—C9	1.3883 (17)	C21—H21	0.93
C8—C13	1.3920 (16)	O1W—H1W1	0.83 (2)

O1—S1—O2	119.79 (6)	C8—C9—H9	120.4
O1—S1—N1	106.89 (6)	C9—C10—C11	121.80 (12)
O2—S1—N1	106.50 (6)	C9—C10—H10	119.1
O1—S1—C8	107.49 (6)	C11—C10—H10	119.1
O2—S1—C8	108.18 (6)	C12—C11—C10	118.31 (12)
N1—S1—C8	107.42 (5)	C12—C11—C14	121.30 (12)
C6—O3—C5	116.27 (8)	C10—C11—C14	120.38 (12)
C22—O4—C23	121.68 (9)	C11—C12—C13	121.08 (11)
C1—N1—C4	111.59 (9)	C11—C12—H12	119.5
C1—N1—S1	119.20 (8)	C13—C12—H12	119.5
C4—N1—S1	120.17 (8)	C12—C13—C8	119.36 (11)
N1—C1—C2	103.55 (9)	C12—C13—H13	120.3
N1—C1—H1A	111.1	C8—C13—H13	120.3
C2—C1—H1A	111.1	C11—C14—H14A	109.5
N1—C1—H1B	111.1	C11—C14—H14B	109.5
C2—C1—H1B	111.1	H14A—C14—H14B	109.5
H1A—C1—H1B	109.0	C11—C14—H14C	109.5
C5—C2—C1	113.40 (9)	H14A—C14—H14C	109.5
C5—C2—C3	112.79 (9)	H14B—C14—H14C	109.5
C1—C2—C3	104.22 (9)	C5—C15—H15A	109.5
C5—C2—H2	108.7	C5—C15—H15B	109.5
C1—C2—H2	108.7	H15A—C15—H15B	109.5
C3—C2—H2	108.7	C5—C15—H15C	109.5
C7—C3—C4	113.50 (9)	H15A—C15—H15C	109.5
C7—C3—C2	109.51 (9)	H15B—C15—H15C	109.5
C4—C3—C2	102.63 (9)	C5—C16—H16A	109.5
C7—C3—H3	110.3	C5—C16—H16B	109.5
C4—C3—H3	110.3	H16A—C16—H16B	109.5
C2—C3—H3	110.3	C5—C16—H16C	109.5
N1—C4—C3	104.48 (9)	H16A—C16—H16C	109.5
N1—C4—H4A	110.9	H16B—C16—H16C	109.5
C3—C4—H4A	110.9	C22—C17—C18	118.96 (10)
N1—C4—H4B	110.9	C22—C17—C6	117.53 (10)
C3—C4—H4B	110.9	C18—C17—C6	123.50 (10)
H4A—C4—H4B	108.9	C19—C18—C17	119.85 (11)
O3—C5—C16	104.38 (9)	C19—C18—H18	120.1
O3—C5—C15	107.45 (9)	C17—C18—H18	120.1
C16—C5—C15	111.13 (10)	C18—C19—C20	120.34 (12)
O3—C5—C2	109.06 (9)	C18—C19—H19	119.8
C16—C5—C2	112.46 (9)	C20—C19—H19	119.8
C15—C5—C2	111.93 (9)	C21—C20—C19	120.80 (11)
O3—C6—C7	124.44 (10)	C21—C20—H20	119.6
O3—C6—C17	114.50 (9)	C19—C20—H20	119.6
C7—C6—C17	121.06 (10)	C20—C21—C22	118.62 (12)
C6—C7—C23	119.59 (10)	C20—C21—H21	120.7
C6—C7—C3	122.54 (10)	C22—C21—H21	120.7
C23—C7—C3	117.72 (9)	O4—C22—C21	117.14 (11)
C9—C8—C13	120.26 (11)	O4—C22—C17	121.43 (10)
C9—C8—S1	119.68 (9)	C21—C22—C17	121.41 (11)
C13—C8—S1	119.99 (9)	O5—C23—O4	116.44 (10)
C10—C9—C8	119.17 (12)	O5—C23—C7	125.11 (11)
C10—C9—H9	120.4	O4—C23—C7	118.45 (10)

O1—S1—N1—C1	−47.47 (10)	O2—S1—C8—C9	−31.08 (12)
O2—S1—N1—C1	−176.63 (8)	N1—S1—C8—C9	83.53 (12)
C8—S1—N1—C1	67.65 (10)	O1—S1—C8—C13	21.34 (11)
O1—S1—N1—C4	168.19 (8)	O2—S1—C8—C13	152.02 (10)
O2—S1—N1—C4	39.03 (10)	N1—S1—C8—C13	−93.37 (10)
C8—S1—N1—C4	−76.69 (9)	C13—C8—C9—C10	0.5 (2)
C4—N1—C1—C2	−10.44 (11)	S1—C8—C9—C10	−176.44 (12)
S1—N1—C1—C2	−157.62 (7)	C8—C9—C10—C11	−1.3 (3)
N1—C1—C2—C5	152.39 (9)	C9—C10—C11—C12	1.1 (3)
N1—C1—C2—C3	29.36 (10)	C9—C10—C11—C14	−178.00 (17)
C5—C2—C3—C7	−39.60 (12)	C10—C11—C12—C13	−0.1 (2)
C1—C2—C3—C7	83.82 (10)	C14—C11—C12—C13	178.96 (14)
C5—C2—C3—C4	−160.46 (9)	C11—C12—C13—C8	−0.66 (19)
C1—C2—C3—C4	−37.03 (10)	C9—C8—C13—C12	0.48 (18)
C1—N1—C4—C3	−12.70 (12)	S1—C8—C13—C12	177.37 (9)
S1—N1—C4—C3	134.11 (8)	O3—C6—C17—C22	178.02 (10)
C7—C3—C4—N1	−87.73 (11)	C7—C6—C17—C22	−1.85 (16)
C2—C3—C4—N1	30.35 (10)	O3—C6—C17—C18	−0.97 (16)
C6—O3—C5—C16	−166.93 (9)	C7—C6—C17—C18	179.16 (11)
C6—O3—C5—C15	74.98 (11)	C22—C17—C18—C19	−0.09 (18)
C6—O3—C5—C2	−46.55 (12)	C6—C17—C18—C19	178.89 (11)
C1—C2—C5—O3	−60.12 (12)	C17—C18—C19—C20	0.55 (19)
C3—C2—C5—O3	58.06 (12)	C18—C19—C20—C21	0.0 (2)
C1—C2—C5—C16	55.17 (12)	C19—C20—C21—C22	−0.9 (2)
C3—C2—C5—C16	173.35 (9)	C23—O4—C22—C21	179.72 (12)
C1—C2—C5—C15	−178.89 (9)	C23—O4—C22—C17	1.34 (18)
C3—C2—C5—C15	−60.71 (12)	C20—C21—C22—O4	−176.96 (13)
C5—O3—C6—C7	18.19 (15)	C20—C21—C22—C17	1.4 (2)
C5—O3—C6—C17	−161.67 (9)	C18—C17—C22—O4	177.39 (11)
O3—C6—C7—C23	−174.40 (10)	C6—C17—C22—O4	−1.65 (17)
C17—C6—C7—C23	5.45 (16)	C18—C17—C22—C21	−0.91 (19)
O3—C6—C7—C3	0.98 (17)	C6—C17—C22—C21	−179.95 (12)
C17—C6—C7—C3	−179.17 (10)	C22—O4—C23—O5	−176.80 (11)
C4—C3—C7—C6	124.43 (11)	C22—O4—C23—C7	2.28 (16)
C2—C3—C7—C6	10.40 (15)	C6—C7—C23—O5	173.33 (11)
C4—C3—C7—C23	−60.11 (13)	C3—C7—C23—O5	−2.27 (17)
C2—C3—C7—C23	−174.13 (10)	C6—C7—C23—O4	−5.67 (16)
O1—S1—C8—C9	−161.76 (11)	C3—C7—C23—O4	178.73 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O5	0.97	2.47	3.0588 (15)	119
O1W—H1W1···O2	0.83 (2)	2.05 (8)	2.837 (2)	161 (8)
C16—H16B···O1Wⁱ	0.96	2.43	3.345 (5)	160
C16—H16B···O1Wⁱⁱ	0.96	2.43	3.345 (5)	160
C14—H14B···O1Wⁱⁱⁱ	0.96	2.44	3.282 (2)	147
C14—H14B···O1W^iv	0.96	2.44	3.282 (2)	147

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1/2, y−1/2, −z+1; (iii) y, −x+3/2, −z+1/2; (iv) −y+3/2, x, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₃H₂₃NO₅S·0.125H₂O
M_r	427.74
Crystal system, space group	Tetragonal, P4₂/n
Temperature (K)	100
a, c (Å)	15.1932 (2), 17.7180 (3)
V (Å³)	4089.91 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.50 × 0.44 × 0.13

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.845, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	97892, 6004, 5114
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.706

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.109, 1.05
No. of reflections	6004
No. of parameters	282
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.36

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O5	0.97	2.47	3.0588 (15)	119
O1W—H1W1···O2	0.83 (2)	2.05 (8)	2.837 (2)	161 (8)
C16—H16B···O1Wⁱ	0.96	2.43	3.345 (5)	160
C16—H16B···O1Wⁱⁱ	0.96	2.43	3.345 (5)	160
C14—H14B···O1Wⁱⁱⁱ	0.96	2.44	3.282 (2)	147
C14—H14B···O1W^iv	0.96	2.44	3.282 (2)	147

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1/2, y−1/2, −z+1; (iii) y, −x+3/2, −z+1/2; (iv) −y+3/2, x, −z+1/2.

Footnotes

‡Working at: Department of Physics, R. M. K. Engineering Collge, R. S. M. Nagar, Kavaraipettai 601 206, Tamil Nadu, India.

§Additional correspondence author, e-mail: hkfun@usm.my.

Acknowledgements

HKF thanks Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

References

Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Duax, W. L., Weeks, C. M. & Rohrer, D. C. (1976). Topics in Stereochemistry, Vol. 9, edited by E. L. Eliel & N. L. Allinger, pp. 271–383. New York: John Wiley. Google Scholar
Goel, R. K., Maiti, R. N., Manickam, M. & Ray, A. B. (1997). Indian J. Exp. Biol. 35, 1080–1083. CAS PubMed Google Scholar
Hossain, C. F., Okuyama, E. & Yamazaki, M. (1996). Chem. Pharm. Bull. (Tokyo), 44, 1535–1539. CrossRef CAS PubMed Google Scholar
Kawaii, S., Tomono, Y., Ogawa, K., Sugiura, M., Yano, M., Yoshizawa, Y., Ito, C. & Furukawa, H. (2001). Anticancer Res. 21, 1905–1911. Web of Science PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Su, C. R., Yeh, S. F., Liu, C. M., Damu, A. G., Kuo, T. H., Chiang, P. C., Bastow, K. F., Lee, K. H. & Wu, T. S. (2009). Bioorg. Med. Chem. 17, 6137–6143. Web of Science CrossRef PubMed CAS Google Scholar
Xu, Z. Q., Pupek, K., Suling, W. J., Enache, L. & Flavin, M. T. (2006). Bioorg. Med. Chem. 14, 4610–4626. Web of Science CrossRef PubMed CAS Google Scholar

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