4-[(E)-(4-Hy-droxy-2-oxo-2H-chromen-3-yl)methyl-idene-amino]-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one monohydrate.

In the title compound, C(21)H(17)N(3)O(4)·H(2)O, 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 mol-ecular conformation is stabilized by intra-molecular N-H⋯O and C-H⋯O hydrogen bonds, both of which form S(6) ring motifs. In the crystal, each water mol-ecule is linked to its adjacent organic mol-ecule via pairs of O-H⋯O hydrogen bonds. The packing is further consolidated by pairs of inter-molecular C-H⋯O hydrogen bonds, which link the mol-ecules 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 = 393.39

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.172

S = 1.03

5044 reflections

268 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.40 e Å−3

Δρmin = −0.66 e Å−3

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 ▶).

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

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

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

C21H17N3O4·H2O	F(000) = 1648
Mr = 393.39	Dx = 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

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

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(Fo2) + (0.0911P)2 + 2.8654P] where P = (Fo2 + 2Fc2)/3
5044 reflections	(Δ/σ)max < 0.001
268 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.66 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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)

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

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) .