4-{[(1,3-Benzothia-zolium-2-yl)hydra-zono](phen-yl)meth-yl}-3-methyl-1-phenyl-1H-pyrazol-5-olate monohydrate.

The title compound, C(24)H(19)N(5)OS·H(2)O, was synthesized by the reaction of 4-benzoyl-3-methyl-1-phenyl-pyrazol-5-one and 2-hydrazino-1,3-benzothia-zole. Proton transfer leads to the formation of a zwitterionic structure and the mol-ecule exists in the enolate form. The pyrazolone ring makes dihedral angles of 35.4 (3), 69.7 (3) and 40.1 (3)° with the 1-phenyl, indirectly bound phenyl and benzothia-zole ring systems, respectively. The mol-ecules are linked into one-dimensional chains by a combination of N-H⋯O, O-H⋯N and O-H⋯O hydrogen bonds.

Related literature

For related literature, see: Akama & Tong (1996 ▶); Eller & Holzer (2004 ▶); Morakot et al. (2008 ▶); Rana et al. (2007 ▶); Sieroń (2007 ▶); Kim et al. (2005 ▶); Costa et al. (2006 ▶); Usman et al. (2003 ▶). Two related compounds we have previously reported exist in the enamine–keto tautomeric form (Sun et al., 2006 ▶, 2007 ▶).

Experimental

Crystal data

C24H19N5OS·H2O

M = 443.52

Triclinic,

a = 7.1059 (16) Å

b = 12.906 (3) Å

c = 13.439 (3) Å

α = 67.173 (4)°

β = 85.597 (4)°

γ = 76.226 (4)°

V = 1103.1 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.18 mm−1

T = 273 (2) K

0.15 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.974, T max = 0.982

5750 measured reflections

3850 independent reflections

3210 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.139

S = 1.09

3850 reflections

290 parameters

3 restraints

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.19 e Å−3

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808006193/lh2599sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808006193/lh2599Isup2.hkl

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

C24H19N5OS·H2O	Z = 2
Mr = 443.52	F000 = 464
Triclinic, P1	Dx = 1.335 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 7.1059 (16) Å	Cell parameters from 2939 reflections
b = 12.906 (3) Å	θ = 3.0–27.6º
c = 13.439 (3) Å	µ = 0.18 mm−1
α = 67.173 (4)º	T = 273 (2) K
β = 85.597 (4)º	Block, yellow
γ = 76.226 (4)º	0.15 × 0.12 × 0.10 mm
V = 1103.1 (4) Å3

Bruker SMART CCD area-detector diffractometer	3850 independent reflections
Radiation source: fine-focus sealed tube	3210 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.018
T = 273(2) K	θmax = 25.0º
φ and ω scans	θmin = 1.6º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.974, Tmax = 0.982	k = −11→15
5750 measured reflections	l = −15→15

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051	H-atom parameters constrained
wR(F2) = 0.139	w = 1/[σ2(Fo2) + (0.0377P)2 + 1.1858P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max < 0.001
3850 reflections	Δρmax = 0.27 e Å−3
290 parameters	Δρmin = −0.19 e Å−3
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0158 (18)

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
S1	0.85393 (12)	0.44604 (7)	0.44483 (6)	0.0482 (2)
O1	0.8025 (3)	0.58715 (19)	0.03090 (16)	0.0513 (5)
O2	0.9942 (3)	0.28493 (19)	0.14541 (16)	0.0551 (6)
H25	0.8965	0.2751	0.1203	0.066*
H26	1.0389	0.3328	0.0912	0.066*
N1	0.9422 (3)	0.3293 (2)	0.32447 (18)	0.0416 (5)
H1	0.9531	0.3109	0.2689	0.050*
N2	0.7798 (3)	0.5218 (2)	0.23487 (19)	0.0448 (6)
H2	0.7755	0.5181	0.1726	0.054*
N3	0.7050 (4)	0.6224 (2)	0.25456 (19)	0.0475 (6)
N4	0.5118 (3)	0.6743 (2)	−0.06729 (18)	0.0425 (6)
N5	0.3329 (4)	0.7428 (2)	−0.0612 (2)	0.0483 (6)
C1	0.8564 (4)	0.4347 (2)	0.3203 (2)	0.0379 (6)
C2	0.9815 (4)	0.3026 (3)	0.5016 (2)	0.0458 (7)
C3	1.0124 (4)	0.2522 (2)	0.4260 (2)	0.0424 (6)
C4	1.1057 (5)	0.1373 (3)	0.4546 (3)	0.0580 (8)
H4	1.1238	0.1024	0.4046	0.070*
C5	1.1705 (6)	0.0766 (3)	0.5594 (3)	0.0730 (11)
H5	1.2329	−0.0009	0.5805	0.088*
C6	1.1459 (6)	0.1268 (3)	0.6336 (3)	0.0743 (11)
H6	1.1942	0.0836	0.7036	0.089*
C7	1.0508 (5)	0.2401 (3)	0.6061 (3)	0.0618 (9)
H7	1.0334	0.2741	0.6567	0.074*
C8	0.5842 (4)	0.7029 (2)	0.1837 (2)	0.0424 (6)
C9	0.5070 (4)	0.8052 (2)	0.2121 (2)	0.0450 (7)
C10	0.5184 (6)	0.9135 (3)	0.1387 (3)	0.0637 (10)
H10	0.5788	0.9211	0.0732	0.076*
C11	0.4416 (7)	1.0104 (3)	0.1612 (3)	0.0761 (12)
H11	0.4489	1.0829	0.1106	0.091*
C12	0.3545 (6)	0.9999 (3)	0.2576 (3)	0.0722 (11)
H12	0.2995	1.0654	0.2723	0.087*
C13	0.3485 (6)	0.8927 (3)	0.3327 (3)	0.0683 (10)
H13	0.2921	0.8854	0.3991	0.082*
C14	0.4252 (5)	0.7953 (3)	0.3107 (2)	0.0544 (8)
H14	0.4217	0.7228	0.3626	0.065*
C15	0.5207 (4)	0.7042 (2)	0.0832 (2)	0.0400 (6)
C16	0.6280 (4)	0.6487 (2)	0.0189 (2)	0.0412 (6)
C17	0.3392 (4)	0.7598 (3)	0.0289 (2)	0.0462 (7)
C18	0.1601 (5)	0.8263 (3)	0.0615 (3)	0.0729 (11)
H18A	0.1789	0.9005	0.0529	0.109*
H18B	0.1335	0.7847	0.1357	0.109*
H18C	0.0528	0.8363	0.0168	0.109*
C19	0.5566 (4)	0.6468 (3)	−0.1605 (2)	0.0432 (7)
C20	0.4799 (5)	0.7263 (3)	−0.2587 (2)	0.0567 (8)
H20	0.4028	0.7975	−0.2639	0.068*
C21	0.5176 (6)	0.7001 (4)	−0.3495 (3)	0.0697 (10)
H21	0.4660	0.7539	−0.4161	0.084*
C22	0.6305 (6)	0.5954 (4)	−0.3418 (3)	0.0713 (11)
H22	0.6546	0.5776	−0.4030	0.086*
C23	0.7080 (5)	0.5169 (3)	−0.2440 (3)	0.0656 (10)
H23	0.7860	0.4461	−0.2391	0.079*
C24	0.6718 (5)	0.5417 (3)	−0.1523 (3)	0.0533 (8)
H24	0.7245	0.4881	−0.0859	0.064*

	U11	U22	U33	U12	U13	U23
S1	0.0615 (5)	0.0509 (5)	0.0402 (4)	−0.0127 (4)	−0.0018 (3)	−0.0254 (3)
O1	0.0423 (12)	0.0656 (14)	0.0433 (11)	−0.0049 (10)	0.0022 (9)	−0.0223 (10)
O2	0.0562 (13)	0.0765 (15)	0.0451 (12)	−0.0244 (11)	0.0044 (10)	−0.0317 (11)
N1	0.0471 (13)	0.0462 (13)	0.0386 (12)	−0.0140 (11)	0.0022 (10)	−0.0219 (11)
N2	0.0536 (15)	0.0465 (14)	0.0398 (13)	−0.0094 (11)	−0.0044 (11)	−0.0225 (11)
N3	0.0593 (16)	0.0439 (14)	0.0441 (14)	−0.0107 (12)	−0.0025 (12)	−0.0217 (12)
N4	0.0437 (13)	0.0494 (14)	0.0378 (12)	−0.0101 (11)	0.0015 (10)	−0.0207 (11)
N5	0.0455 (14)	0.0536 (15)	0.0499 (14)	−0.0085 (12)	−0.0035 (11)	−0.0251 (12)
C1	0.0398 (15)	0.0432 (15)	0.0370 (14)	−0.0147 (12)	0.0009 (11)	−0.0189 (12)
C2	0.0505 (17)	0.0499 (17)	0.0410 (15)	−0.0163 (14)	−0.0009 (13)	−0.0183 (13)
C3	0.0420 (15)	0.0445 (16)	0.0437 (15)	−0.0146 (13)	0.0014 (12)	−0.0174 (13)
C4	0.063 (2)	0.0499 (19)	0.061 (2)	−0.0114 (16)	0.0041 (16)	−0.0227 (16)
C5	0.074 (2)	0.052 (2)	0.077 (3)	−0.0050 (18)	−0.012 (2)	−0.0091 (19)
C6	0.081 (3)	0.072 (3)	0.055 (2)	−0.014 (2)	−0.0184 (19)	−0.0072 (19)
C7	0.074 (2)	0.066 (2)	0.0454 (18)	−0.0179 (18)	−0.0098 (16)	−0.0188 (16)
C8	0.0502 (17)	0.0423 (16)	0.0381 (15)	−0.0157 (13)	0.0042 (13)	−0.0165 (13)
C9	0.0537 (17)	0.0456 (16)	0.0399 (15)	−0.0136 (14)	−0.0020 (13)	−0.0190 (13)
C10	0.105 (3)	0.0468 (18)	0.0417 (17)	−0.0216 (18)	0.0103 (17)	−0.0185 (14)
C11	0.130 (4)	0.0421 (18)	0.057 (2)	−0.024 (2)	0.013 (2)	−0.0198 (16)
C12	0.097 (3)	0.054 (2)	0.072 (2)	−0.009 (2)	0.013 (2)	−0.0373 (19)
C13	0.078 (2)	0.072 (2)	0.060 (2)	−0.0152 (19)	0.0226 (18)	−0.0352 (19)
C14	0.065 (2)	0.0505 (18)	0.0456 (17)	−0.0155 (16)	0.0107 (15)	−0.0167 (14)
C15	0.0466 (16)	0.0393 (15)	0.0368 (14)	−0.0130 (12)	0.0011 (12)	−0.0154 (12)
C16	0.0446 (16)	0.0427 (15)	0.0362 (14)	−0.0158 (13)	0.0031 (12)	−0.0121 (12)
C17	0.0479 (17)	0.0460 (16)	0.0473 (16)	−0.0101 (13)	0.0000 (13)	−0.0208 (14)
C18	0.060 (2)	0.085 (3)	0.077 (3)	0.0082 (19)	−0.0081 (19)	−0.047 (2)
C19	0.0476 (16)	0.0533 (17)	0.0388 (15)	−0.0244 (14)	0.0074 (12)	−0.0221 (13)
C20	0.060 (2)	0.069 (2)	0.0448 (17)	−0.0205 (17)	−0.0010 (15)	−0.0217 (16)
C21	0.068 (2)	0.107 (3)	0.0412 (18)	−0.035 (2)	0.0035 (16)	−0.028 (2)
C22	0.071 (2)	0.116 (3)	0.061 (2)	−0.052 (2)	0.0242 (19)	−0.057 (2)
C23	0.065 (2)	0.078 (2)	0.081 (3)	−0.0356 (19)	0.0250 (19)	−0.053 (2)
C24	0.0599 (19)	0.0571 (19)	0.0522 (18)	−0.0248 (16)	0.0109 (15)	−0.0259 (15)

S1—C1	1.735 (3)	C9—C14	1.377 (4)
S1—C2	1.744 (3)	C9—C10	1.379 (4)
O1—C16	1.287 (3)	C10—C11	1.377 (5)
O2—H25	0.8500	C10—H10	0.9300
O2—H26	0.8500	C11—C12	1.365 (5)
N1—C1	1.332 (3)	C11—H11	0.9300
N1—C3	1.384 (4)	C12—C13	1.369 (5)
N1—H1	0.8600	C12—H12	0.9300
N2—C1	1.297 (3)	C13—C14	1.379 (5)
N2—N3	1.397 (3)	C13—H13	0.9300
N2—H2	0.8600	C14—H14	0.9300
N3—C8	1.288 (4)	C15—C16	1.400 (4)
N4—C16	1.361 (3)	C15—C17	1.418 (4)
N4—N5	1.382 (3)	C17—C18	1.495 (4)
N4—C19	1.424 (3)	C18—H18A	0.9600
N5—C17	1.317 (4)	C18—H18B	0.9600
C2—C7	1.380 (4)	C18—H18C	0.9600
C2—C3	1.384 (4)	C19—C20	1.373 (4)
C3—C4	1.384 (4)	C19—C24	1.375 (4)
C4—C5	1.372 (5)	C20—C21	1.379 (5)
C4—H4	0.9300	C20—H20	0.9300
C5—C6	1.365 (5)	C21—C22	1.367 (6)
C5—H5	0.9300	C21—H21	0.9300
C6—C7	1.371 (5)	C22—C23	1.368 (5)
C6—H6	0.9300	C22—H22	0.9300
C7—H7	0.9300	C23—C24	1.379 (4)
C8—C15	1.449 (4)	C23—H23	0.9300
C8—C9	1.484 (4)	C24—H24	0.9300
C1—S1—C2	89.71 (13)	C12—C11—H11	120.0
H25—O2—H26	104.4	C10—C11—H11	120.0
C1—N1—C3	114.1 (2)	C11—C12—C13	119.7 (3)
C1—N1—H1	122.9	C11—C12—H12	120.2
C3—N1—H1	122.9	C13—C12—H12	120.2
C1—N2—N3	113.0 (2)	C12—C13—C14	120.6 (3)
C1—N2—H2	123.5	C12—C13—H13	119.7
N3—N2—H2	123.5	C14—C13—H13	119.7
C8—N3—N2	116.6 (2)	C9—C14—C13	120.1 (3)
C16—N4—N5	111.7 (2)	C9—C14—H14	119.9
C16—N4—C19	128.9 (2)	C13—C14—H14	119.9
N5—N4—C19	119.3 (2)	C16—C15—C17	104.9 (2)
C17—N5—N4	105.4 (2)	C16—C15—C8	126.7 (3)
N2—C1—N1	125.9 (2)	C17—C15—C8	128.4 (3)
N2—C1—S1	121.5 (2)	O1—C16—N4	123.3 (3)
N1—C1—S1	112.7 (2)	O1—C16—C15	130.4 (3)
C7—C2—C3	120.3 (3)	N4—C16—C15	106.3 (2)
C7—C2—S1	128.5 (3)	N5—C17—C15	111.8 (3)
C3—C2—S1	111.2 (2)	N5—C17—C18	118.1 (3)
C4—C3—N1	126.9 (3)	C15—C17—C18	130.1 (3)
C4—C3—C2	120.8 (3)	C17—C18—H18A	109.5
N1—C3—C2	112.2 (3)	C17—C18—H18B	109.5
C5—C4—C3	117.7 (3)	H18A—C18—H18B	109.5
C5—C4—H4	121.2	C17—C18—H18C	109.5
C3—C4—H4	121.2	H18A—C18—H18C	109.5
C6—C5—C4	121.8 (4)	H18B—C18—H18C	109.5
C6—C5—H5	119.1	C20—C19—C24	120.5 (3)
C4—C5—H5	119.1	C20—C19—N4	118.8 (3)
C5—C6—C7	120.7 (3)	C24—C19—N4	120.7 (3)
C5—C6—H6	119.6	C19—C20—C21	119.7 (3)
C7—C6—H6	119.6	C19—C20—H20	120.2
C6—C7—C2	118.6 (3)	C21—C20—H20	120.2
C6—C7—H7	120.7	C22—C21—C20	120.2 (4)
C2—C7—H7	120.7	C22—C21—H21	119.9
N3—C8—C15	127.9 (3)	C20—C21—H21	119.9
N3—C8—C9	113.3 (2)	C21—C22—C23	119.8 (3)
C15—C8—C9	118.8 (2)	C21—C22—H22	120.1
C14—C9—C10	118.6 (3)	C23—C22—H22	120.1
C14—C9—C8	121.8 (3)	C22—C23—C24	120.7 (4)
C10—C9—C8	119.7 (3)	C22—C23—H23	119.6
C11—C10—C9	121.0 (3)	C24—C23—H23	119.6
C11—C10—H10	119.5	C19—C24—C23	119.1 (3)
C9—C10—H10	119.5	C19—C24—H24	120.5
C12—C11—C10	119.9 (3)	C23—C24—H24	120.5
C1—N2—N3—C8	−162.4 (3)	C11—C12—C13—C14	−1.6 (6)
C16—N4—N5—C17	0.3 (3)	C10—C9—C14—C13	3.1 (5)
C19—N4—N5—C17	−175.6 (2)	C8—C9—C14—C13	−177.5 (3)
N3—N2—C1—N1	−178.3 (2)	C12—C13—C14—C9	−0.7 (6)
N3—N2—C1—S1	2.1 (3)	N3—C8—C15—C16	−30.2 (5)
C3—N1—C1—N2	179.8 (3)	C9—C8—C15—C16	149.0 (3)
C3—N1—C1—S1	−0.6 (3)	N3—C8—C15—C17	149.2 (3)
C2—S1—C1—N2	−178.6 (2)	C9—C8—C15—C17	−31.6 (4)
C2—S1—C1—N1	1.7 (2)	N5—N4—C16—O1	−179.2 (2)
C1—S1—C2—C7	176.8 (3)	C19—N4—C16—O1	−3.8 (4)
C1—S1—C2—C3	−2.5 (2)	N5—N4—C16—C15	−0.8 (3)
C1—N1—C3—C4	179.2 (3)	C19—N4—C16—C15	174.6 (3)
C1—N1—C3—C2	−1.4 (3)	C17—C15—C16—O1	179.2 (3)
C7—C2—C3—C4	2.8 (5)	C8—C15—C16—O1	−1.2 (5)
S1—C2—C3—C4	−177.9 (2)	C17—C15—C16—N4	0.9 (3)
C7—C2—C3—N1	−176.7 (3)	C8—C15—C16—N4	−179.5 (3)
S1—C2—C3—N1	2.6 (3)	N4—N5—C17—C15	0.4 (3)
N1—C3—C4—C5	177.6 (3)	N4—N5—C17—C18	−176.6 (3)
C2—C3—C4—C5	−1.7 (5)	C16—C15—C17—N5	−0.8 (3)
C3—C4—C5—C6	−0.4 (6)	C8—C15—C17—N5	179.7 (3)
C4—C5—C6—C7	1.5 (6)	C16—C15—C17—C18	175.6 (3)
C5—C6—C7—C2	−0.4 (6)	C8—C15—C17—C18	−3.9 (5)
C3—C2—C7—C6	−1.7 (5)	C16—N4—C19—C20	−142.4 (3)
S1—C2—C7—C6	179.2 (3)	N5—N4—C19—C20	32.7 (4)
N2—N3—C8—C15	−2.5 (4)	C16—N4—C19—C24	38.7 (4)
N2—N3—C8—C9	178.3 (2)	N5—N4—C19—C24	−146.2 (3)
N3—C8—C9—C14	−52.3 (4)	C24—C19—C20—C21	0.5 (5)
C15—C8—C9—C14	128.3 (3)	N4—C19—C20—C21	−178.4 (3)
N3—C8—C9—C10	127.0 (3)	C19—C20—C21—C22	0.1 (5)
C15—C8—C9—C10	−52.3 (4)	C20—C21—C22—C23	−0.7 (5)
C14—C9—C10—C11	−3.1 (6)	C21—C22—C23—C24	0.7 (5)
C8—C9—C10—C11	177.5 (3)	C20—C19—C24—C23	−0.5 (4)
C9—C10—C11—C12	0.7 (7)	N4—C19—C24—C23	178.4 (3)
C10—C11—C12—C13	1.6 (7)	C22—C23—C24—C19	−0.1 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H25···N5i	0.85	1.97	2.815 (3)	178
O2—H26···O1ii	0.85	2.00	2.829 (3)	166
N1—H1···O2	0.86	1.81	2.662 (3)	173
N2—H2···O1	0.86	1.78	2.541 (3)	146

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H25⋯N5i	0.85	1.97	2.815 (3)	178
O2—H26⋯O1ii	0.85	2.00	2.829 (3)	166
N1—H1⋯O2	0.86	1.81	2.662 (3)	173
N2—H2⋯O1	0.86	1.78	2.541 (3)	146

Symmetry codes: (i) ; (ii) .