4-[(E)-(4-Hy­droxy-2-oxo-2H-chromen-3-yl)methyl­idene­amino]-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one monohydrate

Asad, M.; Oo, C.-W.; Osman, H.; Quah, C.K.; Fun, H.-K.

doi:10.1107/S160053681003480X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Pages o2491-o2492

doi:10.1107/S160053681003480X

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4-[(E)-(4-Hydroxy-2-oxo-2H-chromen-3-yl)methylideneamino]-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one monohydrate

Mohammad Asad,^a Chuan-Wei Oo,^a Hasnah Osman,^a Ching Kheng Quah ^b ‡ and Hoong-Kun Fun ^b ^*§

^aSchool of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 20 August 2010; accepted 29 August 2010; online 4 September 2010)

In the title compound, C₂₁H₁₇N₃O₄·H₂O, the coumarin ring system is almost planar (r.m.s. deviation = 0.002 Å) and makes dihedral angles of 1.50 (7) and 57.75 (7)° with the pyrazole and phenyl rings, respectively. The dihedral angle between the pyrazole and phenyl rings is 56.60 (9)°. The pyrazole ring adopts a twisted comformation. The molecular conformation is stabilized by intramolecular N—H⋯O and C—H⋯O hydrogen bonds, both of which form S(6) ring motifs. In the crystal, each water molecule is linked to its adjacent organic molecule via pairs of O—H⋯O hydrogen bonds. The packing is further consolidated by pairs of intermolecular C—H⋯O hydrogen bonds, which link the molecules into dimers; the dimers are stacked along the b axis.

Related literature

For general background and biological activity of pyranocoumarin and substituted coumarin derivatives, see: Aries (1974 ); da Silva et al. (2009 ); Huang et al. (2010 ); Skulnick et al. (1997 ); Spino et al. (1998 ); Kokil et al. (2010 ); Abdelhafez et al. (2010 ); Honmantgad et al. (1985 ); Delporte et al. (1998 ); Ibrahim et al. (2006 ); Bissonnette et al. (2009 ). For a related structure, see: Arshad et al. (2010 ). For reference bond lengths, see: Allen et al. (1987 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For ring conformations, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₂₁H₁₇N₃O₄·H₂O
M_r = 393.39
Monoclinic, C 2/c
a = 35.225 (4) Å
b = 6.4269 (7) Å
c = 17.6163 (18) Å
β = 108.008 (3)°
V = 3792.7 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.19 × 0.13 × 0.12 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.981, T_max = 0.989
35398 measured reflections
5044 independent reflections
3412 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.172
S = 1.03
5044 reflections
268 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1OW⋯O4	0.87	2.06	2.923 (2)	173
O1W—H2OW⋯O2	0.88	2.03	2.899 (2)	170
N1—H1N1⋯O3	0.93 (3)	1.79 (3)	2.6132 (18)	146 (2)
C3—H3A⋯O2ⁱ	0.93	2.60	3.450 (2)	153
C10—H10A⋯O4	0.93	2.35	3.007 (2)	127
Symmetry code: (i) $[-x, y, -z+{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681003480X/hb5618sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681003480X/hb5618Isup2.hkl

checkCIF report

Comment top

A number of pyranocoumarin and substituted coumarin derivatives reported to possess multiple biological activities (Aries, 1974) are used in the treatment of vitiligo (da Silva et al., 2009) and other dermal diseases. Coumarins show various activities such as anticancer (Huang et al., 2010), anti-HIV agents (Skulnick et al., 1997; Spino et al., 1998), antifungal (Kokil et al., 2010), anticoagulant (Abdelhafez et al., 2010), antibacterial (Honmantgad et al., 1985), antipyretic (Delporte et al., 1998), analgesic (Ibrahim et al., 2006) and anti-inflammatory (Bissonnette et al., 2009) properties.

The title compound (Fig. 1) consists of a 4-[(E)-(4-hydroxy-2-oxo-2H- chromen-3-yl)methylidene]amino-1,5-dimethyl-2-phenyl-1,2-dihydro-3H- pyrazol-3-one molecule and a water molecule in the asymmetric unit. The coumarin ring system (C1—C9/O1/O2) is almost planar with a maximum deviation of 0.003 (1) Å for atom C7 and makes dihedral angles of 1.50 (7) and 57.75 (7)° with least-squares planes of pyrazole (N2/N3/C11—C13) and phenyl (C14—C19) rings, respectively. The dihedral angle between least-squares planes of pyrazole and phenyl rings is 56.60 (9)°. The comformation of pyrazole ring is twisted as reflected by the puckering parameters, Q = 0.0683 (16) Å and Θ = 22.9 (14)° with torsion angle C12–N2–N3–C13 being -8.12 (18) °. The crystal structure is stabilized by intramolecular N1–H1N1···O3 and C10–H10A···O4 hydrogen bonds, forming S(6) ring motifs (Bernstein et al., 1995).

In the solid state (Fig. 2), water molecules are linked to main molecules via intermolecular O1W–H1OW···O4 and O1W–H2OW···O2 hydrogen bonds. The crystal packing is further consolidated by pairs of intermolecular C3–H3A···O2 hydrogen bonds linking the molecules into dimers which are stacked down the b axis.

Related literature top

For general background to and the biological activity of pyranocoumarin and substituted coumarin derivatives, see: Aries (1974); da Silva et al. (2009); Huang et al. (2010); Skulnick et al. (1997); Spino et al. (1998); Kokil et al. (2010); Abdelhafez et al. (2010); Honmantgad et al. (1985); Delporte et al. (1998); Ibrahim et al. (2006); Bissonnette et al. (2009). For a related structure, see: Arshad et al. (2010). For reference bond lengths, see: Allen et al. (1987). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986). For hydrogen-bond motifs, see: Bernstein et al. (1995). For ring conformations, see: Cremer & Pople (1975).

Experimental top

3-Formyl-4-hydroxycoumarin (0.52 mmol, 100 mg) was dissolved in methanol (10 ml) and 4-aminoantipyrine (0.52 mmol, 106 mg) was then added to the mixture. The reaction mixture was refluxed on water bath for 2 h. The precipitated yellow solid was filtered and washed with ethanol to afford the product which was recrystallized from chloroform to reveal yellow blocks of (I) in 70% yield.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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 showing 50% probability displacement ellipsoids for non-H atoms and the atom-numbering scheme. Hydrogen bonds are shown as dashed lines.
	Fig. 2. The crystal structure of the title compound viewed along the b axis. H atoms not involved in hydrogen bonding (dashed lines) have been omitted for clarity.

4-{[(E)-(4-Hydroxy-2-oxo-2H-chromen-3-yl)methylidene]amino}-1,5- dimethyl-2-phenyl-1H-pyrazol-3(2H)-one monohydrate top

Crystal data top

C₂₁H₁₇N₃O₄·H₂O	F(000) = 1648
M_r = 393.39	D_x = 1.378 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6036 reflections
a = 35.225 (4) Å	θ = 2.4–29.9°
b = 6.4269 (7) Å	µ = 0.10 mm⁻¹
c = 17.6163 (18) Å	T = 100 K
β = 108.008 (3)°	Block, yellow
V = 3792.7 (7) Å³	0.19 × 0.13 × 0.12 mm
Z = 8

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	5044 independent reflections
Radiation source: fine-focus sealed tube	3412 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
ϕ and ω scans	θ_max = 29.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −47→48
T_min = 0.981, T_max = 0.989	k = −8→8
35398 measured reflections	l = −23→24

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.172	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0911P)² + 2.8654P] where P = (F_o² + 2F_c²)/3
5044 reflections	(Δ/σ)_max < 0.001
268 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.66 e Å⁻³

Crystal data top

C₂₁H₁₇N₃O₄·H₂O	V = 3792.7 (7) Å³
M_r = 393.39	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 35.225 (4) Å	µ = 0.10 mm⁻¹
b = 6.4269 (7) Å	T = 100 K
c = 17.6163 (18) Å	0.19 × 0.13 × 0.12 mm
β = 108.008 (3)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	5044 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3412 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.989	R_int = 0.052
35398 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.172	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.40 e Å⁻³
5044 reflections	Δρ_min = −0.66 e Å⁻³
268 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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
O1	0.00970 (3)	0.25568 (17)	0.35782 (6)	0.0201 (3)
O2	0.07480 (4)	0.2578 (2)	0.41212 (7)	0.0269 (3)
O3	−0.00816 (3)	0.24563 (17)	0.57775 (6)	0.0212 (3)
O4	0.15875 (3)	0.2277 (2)	0.65776 (7)	0.0275 (3)
N1	0.06937 (4)	0.24627 (19)	0.64206 (7)	0.0160 (3)
N2	0.13874 (4)	0.2275 (2)	0.83849 (8)	0.0246 (3)
N3	0.16474 (4)	0.2441 (2)	0.79281 (8)	0.0258 (3)
C1	0.04266 (5)	0.2552 (2)	0.42474 (9)	0.0183 (3)
C2	−0.02838 (5)	0.2533 (2)	0.36347 (9)	0.0173 (3)
C3	−0.05929 (5)	0.2540 (2)	0.29108 (9)	0.0210 (3)
H3A	−0.0537	0.2560	0.2428	0.025*
C4	−0.09821 (5)	0.2515 (2)	0.29271 (10)	0.0239 (3)
H4A	−0.1191	0.2517	0.2450	0.029*
C5	−0.10675 (5)	0.2486 (3)	0.36506 (10)	0.0245 (3)
H5A	−0.1331	0.2471	0.3654	0.029*
C6	−0.07578 (5)	0.2482 (2)	0.43627 (10)	0.0207 (3)
H6A	−0.0815	0.2462	0.4844	0.025*
C7	−0.03600 (4)	0.2507 (2)	0.43656 (9)	0.0170 (3)
C8	−0.00234 (5)	0.2493 (2)	0.51080 (9)	0.0160 (3)
C9	0.03653 (4)	0.2519 (2)	0.50194 (8)	0.0155 (3)
C10	0.07103 (5)	0.2515 (2)	0.56840 (9)	0.0170 (3)
H10A	0.0959	0.2551	0.5602	0.020*
C11	0.10243 (4)	0.2456 (2)	0.71053 (8)	0.0169 (3)
C12	0.10082 (5)	0.2418 (2)	0.78734 (9)	0.0188 (3)
C13	0.14344 (5)	0.2403 (3)	0.71201 (9)	0.0202 (3)
C14	0.20606 (5)	0.1917 (3)	0.82639 (10)	0.0273 (4)
C15	0.21734 (6)	0.0144 (4)	0.87239 (12)	0.0404 (5)
H15A	0.1982	−0.0713	0.8826	0.048*
C16	0.25772 (6)	−0.0340 (4)	0.90322 (13)	0.0462 (5)
H16A	0.2657	−0.1526	0.9343	0.055*
C17	0.28592 (5)	0.0944 (4)	0.88758 (11)	0.0376 (5)
H17A	0.3129	0.0606	0.9074	0.045*
C18	0.27429 (6)	0.2720 (4)	0.84276 (12)	0.0389 (5)
H18A	0.2935	0.3589	0.8334	0.047*
C19	0.23402 (5)	0.3225 (3)	0.81140 (11)	0.0348 (4)
H19A	0.2261	0.4422	0.7809	0.042*
C20	0.06538 (5)	0.2483 (3)	0.81601 (10)	0.0260 (4)
H20A	0.0660	0.1315	0.8504	0.039*
H20B	0.0415	0.2427	0.7712	0.039*
H20C	0.0657	0.3751	0.8450	0.039*
C21	0.15162 (6)	0.3240 (4)	0.91767 (10)	0.0374 (5)
H21A	0.1323	0.2962	0.9446	0.056*
H21B	0.1541	0.4716	0.9122	0.056*
H21C	0.1770	0.2674	0.9482	0.056*
O1W	0.15736 (5)	0.1509 (3)	0.49339 (10)	0.0663 (6)
H1OW	0.1580	0.1624	0.5429	0.099*
H2OW	0.1317	0.1766	0.4741	0.099*
H1N1	0.0428 (7)	0.242 (3)	0.6406 (15)	0.042 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0195 (5)	0.0275 (6)	0.0130 (5)	−0.0004 (4)	0.0046 (4)	0.0006 (4)
O2	0.0213 (6)	0.0427 (8)	0.0191 (5)	−0.0003 (5)	0.0096 (4)	0.0011 (5)
O3	0.0200 (5)	0.0289 (6)	0.0164 (5)	0.0001 (5)	0.0080 (4)	−0.0006 (4)
O4	0.0190 (6)	0.0454 (8)	0.0194 (5)	−0.0011 (5)	0.0078 (4)	0.0002 (5)
N1	0.0158 (6)	0.0177 (6)	0.0136 (6)	−0.0001 (5)	0.0033 (5)	0.0000 (4)
N2	0.0210 (7)	0.0384 (9)	0.0141 (6)	0.0003 (6)	0.0051 (5)	−0.0001 (5)
N3	0.0172 (6)	0.0425 (9)	0.0164 (6)	0.0005 (6)	0.0033 (5)	0.0015 (6)
C1	0.0197 (7)	0.0196 (7)	0.0153 (6)	−0.0004 (6)	0.0049 (5)	−0.0002 (5)
C2	0.0186 (7)	0.0155 (7)	0.0171 (7)	0.0002 (6)	0.0043 (5)	0.0008 (5)
C3	0.0241 (8)	0.0187 (7)	0.0170 (7)	−0.0006 (6)	0.0018 (6)	0.0003 (6)
C4	0.0227 (8)	0.0184 (7)	0.0239 (8)	0.0011 (6)	−0.0023 (6)	0.0000 (6)
C5	0.0173 (7)	0.0221 (8)	0.0308 (8)	−0.0003 (6)	0.0025 (6)	−0.0011 (6)
C6	0.0197 (7)	0.0200 (8)	0.0224 (7)	0.0002 (6)	0.0065 (6)	−0.0007 (6)
C7	0.0188 (7)	0.0150 (7)	0.0163 (6)	0.0005 (6)	0.0039 (5)	0.0000 (5)
C8	0.0188 (7)	0.0147 (7)	0.0154 (6)	−0.0001 (5)	0.0065 (5)	−0.0003 (5)
C9	0.0170 (7)	0.0163 (7)	0.0133 (6)	−0.0004 (5)	0.0048 (5)	−0.0002 (5)
C10	0.0180 (7)	0.0166 (7)	0.0166 (6)	−0.0007 (6)	0.0056 (5)	0.0005 (5)
C11	0.0167 (7)	0.0183 (7)	0.0145 (6)	−0.0005 (6)	0.0030 (5)	−0.0001 (5)
C12	0.0190 (7)	0.0210 (7)	0.0158 (6)	0.0002 (6)	0.0046 (5)	0.0002 (5)
C13	0.0178 (7)	0.0259 (8)	0.0158 (7)	−0.0009 (6)	0.0037 (5)	0.0009 (6)
C14	0.0185 (8)	0.0411 (10)	0.0191 (7)	−0.0001 (7)	0.0010 (6)	−0.0022 (7)
C15	0.0260 (9)	0.0465 (12)	0.0448 (11)	−0.0014 (8)	0.0052 (8)	0.0132 (9)
C16	0.0326 (11)	0.0538 (14)	0.0462 (12)	0.0088 (10)	0.0034 (9)	0.0155 (10)
C17	0.0217 (8)	0.0586 (13)	0.0287 (9)	0.0060 (9)	0.0022 (7)	−0.0027 (9)
C18	0.0220 (9)	0.0563 (14)	0.0369 (10)	−0.0061 (8)	0.0071 (8)	−0.0008 (9)
C19	0.0251 (9)	0.0437 (11)	0.0333 (9)	−0.0014 (8)	0.0056 (7)	0.0051 (8)
C20	0.0256 (8)	0.0354 (9)	0.0197 (7)	0.0016 (7)	0.0112 (6)	−0.0004 (7)
C21	0.0329 (10)	0.0572 (13)	0.0189 (8)	−0.0017 (9)	0.0032 (7)	−0.0078 (8)
O1W	0.0463 (10)	0.1070 (17)	0.0457 (9)	0.0156 (10)	0.0145 (8)	−0.0139 (10)

Geometric parameters (Å, º) top

O1—C1	1.3753 (18)	C8—C9	1.425 (2)
O1—C2	1.3755 (19)	C9—C10	1.403 (2)
O2—C1	1.219 (2)	C10—H10A	0.9300
O3—C8	1.2583 (17)	C11—C12	1.3718 (19)
O4—C13	1.2367 (19)	C11—C13	1.437 (2)
N1—C10	1.3175 (19)	C12—C20	1.485 (2)
N1—C11	1.3937 (18)	C14—C19	1.381 (3)
N1—H1N1	0.93 (2)	C14—C15	1.383 (3)
N2—C12	1.364 (2)	C15—C16	1.392 (3)
N2—N3	1.3977 (19)	C15—H15A	0.9300
N2—C21	1.465 (2)	C16—C17	1.383 (3)
N3—C13	1.3890 (19)	C16—H16A	0.9300
N3—C14	1.432 (2)	C17—C18	1.376 (3)
C1—C9	1.4416 (19)	C17—H17A	0.9300
C2—C7	1.394 (2)	C18—C19	1.392 (3)
C2—C3	1.398 (2)	C18—H18A	0.9300
C3—C4	1.380 (2)	C19—H19A	0.9300
C3—H3A	0.9300	C20—H20A	0.9600
C4—C5	1.397 (2)	C20—H20B	0.9600
C4—H4A	0.9300	C20—H20C	0.9600
C5—C6	1.385 (2)	C21—H21A	0.9600
C5—H5A	0.9300	C21—H21B	0.9600
C6—C7	1.400 (2)	C21—H21C	0.9600
C6—H6A	0.9300	O1W—H1OW	0.8673
C7—C8	1.469 (2)	O1W—H2OW	0.8763

C1—O1—C2	121.45 (12)	C12—C11—N1	125.13 (14)
C10—N1—C11	124.94 (14)	C12—C11—C13	109.24 (13)
C10—N1—H1N1	109.0 (16)	N1—C11—C13	125.59 (13)
C11—N1—H1N1	126.1 (16)	N2—C12—C11	108.80 (14)
C12—N2—N3	107.25 (12)	N2—C12—C20	122.12 (14)
C12—N2—C21	123.53 (15)	C11—C12—C20	129.07 (14)
N3—N2—C21	116.80 (14)	O4—C13—N3	124.51 (15)
C13—N3—N2	110.25 (13)	O4—C13—C11	131.58 (14)
C13—N3—C14	125.28 (14)	N3—C13—C11	103.87 (13)
N2—N3—C14	120.50 (13)	C19—C14—C15	121.39 (17)
O2—C1—O1	115.41 (13)	C19—C14—N3	118.14 (17)
O2—C1—C9	126.19 (14)	C15—C14—N3	120.47 (17)
O1—C1—C9	118.40 (13)	C14—C15—C16	119.12 (19)
O1—C2—C7	122.50 (13)	C14—C15—H15A	120.4
O1—C2—C3	115.85 (14)	C16—C15—H15A	120.4
C7—C2—C3	121.64 (15)	C17—C16—C15	119.9 (2)
C4—C3—C2	118.66 (15)	C17—C16—H16A	120.0
C4—C3—H3A	120.7	C15—C16—H16A	120.0
C2—C3—H3A	120.7	C18—C17—C16	120.30 (18)
C3—C4—C5	120.96 (14)	C18—C17—H17A	119.9
C3—C4—H4A	119.5	C16—C17—H17A	119.9
C5—C4—H4A	119.5	C17—C18—C19	120.48 (19)
C6—C5—C4	119.67 (15)	C17—C18—H18A	119.8
C6—C5—H5A	120.2	C19—C18—H18A	119.8
C4—C5—H5A	120.2	C14—C19—C18	118.77 (19)
C5—C6—C7	120.71 (15)	C14—C19—H19A	120.6
C5—C6—H6A	119.6	C18—C19—H19A	120.6
C7—C6—H6A	119.6	C12—C20—H20A	109.5
C2—C7—C6	118.36 (14)	C12—C20—H20B	109.5
C2—C7—C8	119.30 (14)	H20A—C20—H20B	109.5
C6—C7—C8	122.34 (14)	C12—C20—H20C	109.5
O3—C8—C9	122.90 (14)	H20A—C20—H20C	109.5
O3—C8—C7	120.93 (14)	H20B—C20—H20C	109.5
C9—C8—C7	116.16 (13)	N2—C21—H21A	109.5
C10—C9—C8	121.49 (13)	N2—C21—H21B	109.5
C10—C9—C1	116.33 (13)	H21A—C21—H21B	109.5
C8—C9—C1	122.18 (13)	N2—C21—H21C	109.5
N1—C10—C9	122.09 (14)	H21A—C21—H21C	109.5
N1—C10—H10A	119.0	H21B—C21—H21C	109.5
C9—C10—H10A	119.0	H1OW—O1W—H2OW	94.6

C12—N2—N3—C13	−8.12 (18)	C8—C9—C10—N1	0.8 (2)
C21—N2—N3—C13	−151.71 (16)	C1—C9—C10—N1	−179.23 (14)
C12—N2—N3—C14	−166.83 (15)	C10—N1—C11—C12	179.45 (15)
C21—N2—N3—C14	49.6 (2)	C10—N1—C11—C13	−3.2 (2)
C2—O1—C1—O2	−179.86 (13)	N3—N2—C12—C11	6.06 (18)
C2—O1—C1—C9	0.1 (2)	C21—N2—C12—C11	146.60 (17)
C1—O1—C2—C7	0.1 (2)	N3—N2—C12—C20	−174.70 (15)
C1—O1—C2—C3	−179.95 (13)	C21—N2—C12—C20	−34.2 (3)
O1—C2—C3—C4	179.93 (13)	N1—C11—C12—N2	175.77 (14)
C7—C2—C3—C4	−0.1 (2)	C13—C11—C12—N2	−1.98 (18)
C2—C3—C4—C5	0.1 (2)	N1—C11—C12—C20	−3.4 (3)
C3—C4—C5—C6	0.0 (2)	C13—C11—C12—C20	178.85 (16)
C4—C5—C6—C7	0.1 (2)	N2—N3—C13—O4	−171.06 (16)
O1—C2—C7—C6	−179.92 (13)	C14—N3—C13—O4	−13.6 (3)
C3—C2—C7—C6	0.1 (2)	N2—N3—C13—C11	6.66 (17)
O1—C2—C7—C8	−0.3 (2)	C14—N3—C13—C11	164.13 (16)
C3—C2—C7—C8	179.73 (14)	C12—C11—C13—O4	174.61 (18)
C5—C6—C7—C2	−0.1 (2)	N1—C11—C13—O4	−3.1 (3)
C5—C6—C7—C8	−179.68 (15)	C12—C11—C13—N3	−2.89 (17)
C2—C7—C8—O3	−179.56 (14)	N1—C11—C13—N3	179.38 (14)
C6—C7—C8—O3	0.0 (2)	C13—N3—C14—C19	68.3 (2)
C2—C7—C8—C9	0.3 (2)	N2—N3—C14—C19	−136.40 (18)
C6—C7—C8—C9	179.91 (14)	C13—N3—C14—C15	−111.6 (2)
O3—C8—C9—C10	−0.3 (2)	N2—N3—C14—C15	43.7 (2)
C7—C8—C9—C10	179.79 (13)	C19—C14—C15—C16	−0.9 (3)
O3—C8—C9—C1	179.74 (14)	N3—C14—C15—C16	179.04 (19)
C7—C8—C9—C1	−0.2 (2)	C14—C15—C16—C17	−0.1 (3)
O2—C1—C9—C10	−0.1 (2)	C15—C16—C17—C18	1.1 (3)
O1—C1—C9—C10	180.00 (13)	C16—C17—C18—C19	−1.2 (3)
O2—C1—C9—C8	179.89 (15)	C15—C14—C19—C18	0.8 (3)
O1—C1—C9—C8	0.0 (2)	N3—C14—C19—C18	−179.13 (17)
C11—N1—C10—C9	180.00 (14)	C17—C18—C19—C14	0.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1OW···O4	0.87	2.06	2.923 (2)	173
O1W—H2OW···O2	0.88	2.03	2.899 (2)	170
N1—H1N1···O3	0.93 (3)	1.79 (3)	2.6132 (18)	146 (2)
C3—H3A···O2ⁱ	0.93	2.60	3.450 (2)	153
C10—H10A···O4	0.93	2.35	3.007 (2)	127

Symmetry code: (i) −x, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₁H₁₇N₃O₄·H₂O
M_r	393.39
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	35.225 (4), 6.4269 (7), 17.6163 (18)
β (°)	108.008 (3)
V (Å³)	3792.7 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.19 × 0.13 × 0.12

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.981, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	35398, 5044, 3412
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.172, 1.03
No. of reflections	5044
No. of parameters	268
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.66

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), 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
O1W—H1OW···O4	0.87	2.06	2.923 (2)	173
O1W—H2OW···O2	0.88	2.03	2.899 (2)	170
N1—H1N1···O3	0.93 (3)	1.79 (3)	2.6132 (18)	146 (2)
C3—H3A···O2ⁱ	0.93	2.60	3.450 (2)	153
C10—H10A···O4	0.93	2.35	3.007 (2)	127

Symmetry code: (i) −x, y, −z+1/2.

Footnotes

‡Thomson Reuters ResearcherID: A-5525-2009.

§Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

The authors are thankful to Universiti Sains Malaysia (USM) for providing the necessary research facilities and Research University Grants No. 1001/PKIMIA/811134 and No. 1001/PFIZIK/811160. MA also thanks USM for the award of post doctoral fellowship and CKQ also thanks USM for a research fellowship.

References

Abdelhafez, O. M., Amin, K. M., Batran, R. Z., Maher, T. J., Nada, S. A. & Sethumadhavan, S. (2010). Bioorg. Med. Chem. 18, 3371–3378. Web of Science CrossRef CAS PubMed Google Scholar
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Aries, R. (1974). Chem. Abstr. 80, 146152z. Google Scholar
Arshad, A., Osman, H., Lam, C. K., Quah, C. K. & Fun, H.-K. (2010). Acta Cryst. E66, o1446–o1447. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bissonnette, E. Y., Tremblay, G. M., Turmel, V., Pirotte, B. & Reboud-Ravaux, M. (2009). Int. Immunopharmacol. 9, 49–54. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107. CrossRef CAS Web of Science IUCr Journals Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Delporte, C., Backhouse, N., Negrete, R., Salinas, P., Rivas, P., Cassels, B. K. & San, F. A. (1998). Phytother. Res. 12, 118–122. CrossRef CAS Google Scholar
Honmantgad, S. S., Kulkarni, M. V. & Patil, V. D. (1985). Indian J. Chem. Sect. B, 24, 459–461. Google Scholar
Huang, W. Y., Cai, Y. Z. & Zhang, Y. (2010). Nutr. Cancer, 62, 1–20. Web of Science CrossRef CAS PubMed Google Scholar
Ibrahim, G., Yaro, A. H. & Abdurahman, E. M. (2006). Niger. J. Nat. Prod. Med. 10, 66–68. CAS Google Scholar
Kokil, G. R., Rewatkar, P. V., Gosain, S., Aggarwal, S., Verma, A., Kalra, A. & Thareja, S. (2010). Lett. Drug Des. Discov. 7, 46–49. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Silva, V. B. da, Kawano, D. F., Carvalho, I., Conceição, E., Freitas, O. & de Paula Silva, C. H. T. (2009). J. Pharm. Pharm. Sci. 12, 378–387. PubMed Google Scholar
Skulnick, H. I., Johnson, P. D., Aristoff, P. A., Morris, J. K. & Lovasz, K. D. (1997). J. Med. Chem. 40, 1149–1164. CrossRef CAS PubMed Web of Science Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spino, C., Dodier, M. & Sotheeswaren, S. (1998). Bioorg. Med. Chem. Lett. 8, 3475–3478. Web of Science CrossRef CAS PubMed Google Scholar

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