(2E)-2-{[3-Methyl-5-(2-naphth-yloxy)-1-phenyl-1H-pyrazol-4-yl]methyl-idene}hydrazinecarbothio-amide monohydrate.

In the title compound, C(22)H(19)N(5)OS·H(2)O, the naphthalene ring system and the benzene ring [dihedral angle = 85.19 (8)°] make dihedral angles of 87.02 (9) and 14.41 (10)°, respectively, with the pyrazole ring. The mean plane through the 2-methyl-enehydrazinecarbothio-amide group [C-N-N-C(=S)-N; maximum deviation = 0.022 (1) Å] is slightly twisted from the pyrazole ring [dihedral angle = 5.60 (11)°]. In the crystal, mol-ecules are linked by N-H⋯S, N-H⋯O, O-H⋯S, O-H⋯N and C-H⋯S hydrogen bonds into sheets parallel to the ab plane. π-π inter-actions are also observed [centroid-to-centroid distances = 3.7778 (12) and 3.7010 (12) Å].

Related literature

For the biological activities of pyrazoles and their derivatives, see: Rai et al. (2008 ▶); Hall et al. (2008 ▶); Isloor et al. (2009 ▶); Girisha et al. (2010 ▶). For the stability of the temperature controller used for data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C22H19N5OS·H2O

M = 419.50

Triclinic,

a = 7.9384 (2) Å

b = 11.1512 (2) Å

c = 13.0325 (3) Å

α = 113.481 (1)°

β = 90.942 (1)°

γ = 107.359 (1)°

V = 997.81 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.19 mm−1

T = 100 K

0.41 × 0.22 × 0.17 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.925, T max = 0.967

15860 measured reflections

4542 independent reflections

3499 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.124

S = 1.04

4542 reflections

292 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.33 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 datablock(s) global, I. DOI: 10.1107/S1600536812039815/rz5007sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812039815/rz5007Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812039815/rz5007Isup3.cml

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

C22H19N5OS·H2O	Z = 2
Mr = 419.50	F(000) = 440
Triclinic, P1	Dx = 1.396 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9384 (2) Å	Cell parameters from 5898 reflections
b = 11.1512 (2) Å	θ = 2.7–29.9°
c = 13.0325 (3) Å	µ = 0.19 mm−1
α = 113.481 (1)°	T = 100 K
β = 90.942 (1)°	Block, yellow
γ = 107.359 (1)°	0.41 × 0.22 × 0.17 mm
V = 997.81 (4) Å3

Bruker SMART APEXII CCD diffractometer	4542 independent reflections
Radiation source: fine-focus sealed tube	3499 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
φ and ω scans	θmax = 27.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→10
Tmin = 0.925, Tmax = 0.967	k = −14→14
15860 measured reflections	l = −16→16

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0598P)2 + 0.5141P] where P = (Fo2 + 2Fc2)/3
4542 reflections	(Δ/σ)max < 0.001
292 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.33 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems 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
S1	0.57687 (7)	0.72177 (5)	0.01468 (4)	0.02486 (14)
O1	−0.19366 (17)	0.59419 (13)	0.21670 (11)	0.0213 (3)
O1W	0.3788 (2)	1.05291 (17)	0.10581 (15)	0.0346 (4)
N1	−0.3199 (2)	0.39469 (16)	0.25166 (13)	0.0191 (3)
N2	−0.2933 (2)	0.27084 (16)	0.23124 (14)	0.0206 (3)
N3	0.1454 (2)	0.55365 (17)	0.11750 (14)	0.0232 (4)
N4	0.3012 (2)	0.57326 (18)	0.07115 (14)	0.0233 (4)
N5	0.3021 (2)	0.79095 (19)	0.10655 (15)	0.0248 (4)
C1	0.0100 (2)	0.7186 (2)	0.39444 (16)	0.0198 (4)
H1A	−0.0239	0.6386	0.4094	0.024*
C2	0.1399 (2)	0.84368 (19)	0.47281 (16)	0.0197 (4)
C3	0.2230 (3)	0.8533 (2)	0.57417 (16)	0.0216 (4)
H3A	0.1904	0.7752	0.5916	0.026*
C4	0.3494 (3)	0.9740 (2)	0.64713 (17)	0.0245 (4)
H4A	0.4040	0.9788	0.7147	0.029*
C5	0.3998 (3)	1.0916 (2)	0.62329 (17)	0.0237 (4)
H5A	0.4885	1.1748	0.6744	0.028*
C6	0.3209 (3)	1.0856 (2)	0.52650 (17)	0.0226 (4)
H6A	0.3550	1.1652	0.5111	0.027*
C7	0.1886 (2)	0.96195 (19)	0.44872 (16)	0.0192 (4)
C8	0.1020 (3)	0.9522 (2)	0.34795 (16)	0.0220 (4)
H8A	0.1321	1.0312	0.3317	0.026*
C9	−0.0238 (3)	0.8314 (2)	0.27380 (16)	0.0217 (4)
H9A	−0.0822	0.8266	0.2074	0.026*
C10	−0.0654 (2)	0.71408 (19)	0.29778 (16)	0.0193 (4)
C11	−0.5279 (3)	0.5262 (2)	0.30213 (16)	0.0229 (4)
H11A	−0.4700	0.5811	0.2646	0.027*
C12	−0.6720 (3)	0.5495 (2)	0.35584 (17)	0.0248 (4)
H12A	−0.7104	0.6229	0.3569	0.030*
C13	−0.7608 (3)	0.4676 (2)	0.40784 (17)	0.0258 (4)
H13A	−0.8606	0.4835	0.4431	0.031*
C14	−0.7026 (3)	0.3621 (2)	0.40795 (17)	0.0252 (4)
H14A	−0.7634	0.3053	0.4432	0.030*
C15	−0.5566 (3)	0.3391 (2)	0.35700 (16)	0.0222 (4)
H15A	−0.5162	0.2675	0.3582	0.027*
C16	−0.4695 (2)	0.42118 (19)	0.30412 (16)	0.0190 (4)
C17	−0.1488 (2)	0.2736 (2)	0.18121 (16)	0.0203 (4)
C18	−0.0785 (2)	0.3980 (2)	0.16783 (16)	0.0205 (4)
C19	−0.1928 (2)	0.47093 (19)	0.21273 (16)	0.0191 (4)
C20	0.0800 (3)	0.4335 (2)	0.11819 (16)	0.0223 (4)
H20A	0.1373	0.3665	0.0853	0.027*
C21	0.3835 (3)	0.6963 (2)	0.06758 (15)	0.0196 (4)
C22	−0.0798 (3)	0.1541 (2)	0.14558 (18)	0.0269 (4)
H22A	−0.1585	0.0808	0.1632	0.040*
H22B	0.0410	0.1853	0.1863	0.040*
H22C	−0.0768	0.1180	0.0639	0.040*
H1N4	0.353 (3)	0.504 (3)	0.044 (2)	0.039 (7)*
H2N5	0.346 (4)	0.872 (3)	0.103 (2)	0.049 (8)*
H1N5	0.206 (3)	0.770 (3)	0.137 (2)	0.039 (7)*
H2W1	0.367 (4)	1.077 (3)	0.045 (3)	0.066 (10)*
H1W1	0.478 (4)	1.114 (4)	0.152 (3)	0.071 (10)*

	U11	U22	U33	U12	U13	U23
S1	0.0260 (3)	0.0226 (3)	0.0313 (3)	0.0092 (2)	0.0110 (2)	0.0157 (2)
O1	0.0210 (7)	0.0147 (7)	0.0275 (7)	0.0045 (5)	0.0013 (5)	0.0095 (6)
O1W	0.0398 (9)	0.0229 (8)	0.0378 (9)	0.0026 (7)	−0.0007 (8)	0.0156 (7)
N1	0.0204 (8)	0.0158 (8)	0.0233 (8)	0.0078 (6)	0.0040 (6)	0.0092 (7)
N2	0.0230 (8)	0.0155 (8)	0.0258 (8)	0.0080 (7)	0.0042 (7)	0.0098 (7)
N3	0.0234 (8)	0.0221 (9)	0.0245 (8)	0.0069 (7)	0.0065 (7)	0.0106 (7)
N4	0.0250 (9)	0.0214 (9)	0.0271 (9)	0.0100 (7)	0.0104 (7)	0.0118 (7)
N5	0.0272 (9)	0.0199 (9)	0.0307 (9)	0.0092 (7)	0.0101 (8)	0.0129 (8)
C1	0.0203 (9)	0.0176 (9)	0.0258 (10)	0.0082 (8)	0.0084 (8)	0.0118 (8)
C2	0.0197 (9)	0.0185 (9)	0.0243 (10)	0.0097 (8)	0.0081 (7)	0.0098 (8)
C3	0.0245 (10)	0.0190 (10)	0.0261 (10)	0.0102 (8)	0.0071 (8)	0.0119 (8)
C4	0.0255 (10)	0.0247 (11)	0.0240 (10)	0.0104 (8)	0.0040 (8)	0.0097 (9)
C5	0.0229 (10)	0.0193 (10)	0.0267 (10)	0.0064 (8)	0.0040 (8)	0.0079 (8)
C6	0.0243 (10)	0.0165 (9)	0.0295 (10)	0.0085 (8)	0.0091 (8)	0.0108 (8)
C7	0.0201 (9)	0.0183 (9)	0.0227 (9)	0.0097 (7)	0.0087 (7)	0.0095 (8)
C8	0.0261 (10)	0.0181 (9)	0.0269 (10)	0.0099 (8)	0.0091 (8)	0.0124 (8)
C9	0.0243 (10)	0.0208 (10)	0.0235 (10)	0.0091 (8)	0.0064 (8)	0.0117 (8)
C10	0.0157 (9)	0.0167 (9)	0.0255 (10)	0.0058 (7)	0.0061 (7)	0.0084 (8)
C11	0.0243 (10)	0.0219 (10)	0.0253 (10)	0.0095 (8)	0.0052 (8)	0.0115 (8)
C12	0.0256 (10)	0.0225 (10)	0.0302 (11)	0.0125 (8)	0.0046 (8)	0.0116 (9)
C13	0.0230 (10)	0.0276 (11)	0.0288 (11)	0.0111 (9)	0.0083 (8)	0.0119 (9)
C14	0.0247 (10)	0.0219 (10)	0.0292 (11)	0.0060 (8)	0.0073 (8)	0.0122 (9)
C15	0.0234 (10)	0.0184 (10)	0.0257 (10)	0.0076 (8)	0.0033 (8)	0.0098 (8)
C16	0.0177 (9)	0.0178 (9)	0.0202 (9)	0.0064 (7)	0.0029 (7)	0.0063 (8)
C17	0.0210 (9)	0.0167 (9)	0.0212 (9)	0.0055 (7)	0.0012 (7)	0.0068 (8)
C18	0.0218 (9)	0.0177 (9)	0.0226 (9)	0.0061 (8)	0.0037 (7)	0.0094 (8)
C19	0.0190 (9)	0.0152 (9)	0.0220 (9)	0.0033 (7)	0.0014 (7)	0.0086 (8)
C20	0.0237 (10)	0.0199 (10)	0.0257 (10)	0.0091 (8)	0.0053 (8)	0.0106 (8)
C21	0.0251 (10)	0.0169 (9)	0.0168 (9)	0.0065 (8)	0.0016 (7)	0.0077 (8)
C22	0.0270 (10)	0.0210 (10)	0.0348 (11)	0.0108 (8)	0.0083 (9)	0.0116 (9)

S1—C21	1.6859 (19)	C6—C7	1.421 (3)
O1—C19	1.357 (2)	C6—H6A	0.9500
O1—C10	1.403 (2)	C7—C8	1.422 (3)
O1W—H2W1	0.94 (3)	C8—C9	1.369 (3)
O1W—H1W1	0.88 (3)	C8—H8A	0.9500
N1—C19	1.359 (2)	C9—C10	1.410 (3)
N1—N2	1.380 (2)	C9—H9A	0.9500
N1—C16	1.428 (2)	C11—C12	1.388 (3)
N2—C17	1.327 (2)	C11—C16	1.391 (3)
N3—C20	1.289 (2)	C11—H11A	0.9500
N3—N4	1.383 (2)	C12—C13	1.384 (3)
N4—C21	1.352 (2)	C12—H12A	0.9500
N4—H1N4	0.93 (3)	C13—C14	1.386 (3)
N5—C21	1.335 (3)	C13—H13A	0.9500
N5—H2N5	0.89 (3)	C14—C15	1.385 (3)
N5—H1N5	0.88 (3)	C14—H14A	0.9500
C1—C10	1.362 (3)	C15—C16	1.390 (3)
C1—C2	1.423 (3)	C15—H15A	0.9500
C1—H1A	0.9500	C17—C18	1.414 (3)
C2—C3	1.417 (3)	C17—C22	1.497 (3)
C2—C7	1.420 (3)	C18—C19	1.381 (3)
C3—C4	1.366 (3)	C18—C20	1.446 (3)
C3—H3A	0.9500	C20—H20A	0.9500
C4—C5	1.411 (3)	C22—H22A	0.9800
C4—H4A	0.9500	C22—H22B	0.9800
C5—C6	1.368 (3)	C22—H22C	0.9800
C5—H5A	0.9500
C19—O1—C10	116.98 (14)	C1—C10—C9	122.20 (18)
H2W1—O1W—H1W1	107 (3)	O1—C10—C9	115.16 (16)
C19—N1—N2	110.16 (15)	C12—C11—C16	118.91 (18)
C19—N1—C16	131.06 (16)	C12—C11—H11A	120.5
N2—N1—C16	118.75 (15)	C16—C11—H11A	120.5
C17—N2—N1	105.70 (15)	C13—C12—C11	121.09 (19)
C20—N3—N4	114.56 (16)	C13—C12—H12A	119.5
C21—N4—N3	119.81 (16)	C11—C12—H12A	119.5
C21—N4—H1N4	118.9 (16)	C12—C13—C14	119.39 (18)
N3—N4—H1N4	121.3 (16)	C12—C13—H13A	120.3
C21—N5—H2N5	120.8 (18)	C14—C13—H13A	120.3
C21—N5—H1N5	117.0 (17)	C15—C14—C13	120.44 (19)
H2N5—N5—H1N5	122 (2)	C15—C14—H14A	119.8
C10—C1—C2	119.59 (17)	C13—C14—H14A	119.8
C10—C1—H1A	120.2	C14—C15—C16	119.67 (18)
C2—C1—H1A	120.2	C14—C15—H15A	120.2
C3—C2—C7	119.00 (17)	C16—C15—H15A	120.2
C3—C2—C1	121.73 (17)	C15—C16—C11	120.46 (17)
C7—C2—C1	119.27 (17)	C15—C16—N1	118.54 (17)
C4—C3—C2	120.58 (18)	C11—C16—N1	121.00 (17)
C4—C3—H3A	119.7	N2—C17—C18	111.53 (16)
C2—C3—H3A	119.7	N2—C17—C22	120.73 (17)
C3—C4—C5	120.78 (19)	C18—C17—C22	127.74 (17)
C3—C4—H4A	119.6	C19—C18—C17	104.38 (16)
C5—C4—H4A	119.6	C19—C18—C20	130.63 (18)
C6—C5—C4	119.91 (19)	C17—C18—C20	124.98 (17)
C6—C5—H5A	120.0	O1—C19—N1	122.18 (16)
C4—C5—H5A	120.0	O1—C19—C18	129.54 (17)
C5—C6—C7	120.90 (18)	N1—C19—C18	108.22 (16)
C5—C6—H6A	119.6	N3—C20—C18	121.63 (18)
C7—C6—H6A	119.6	N3—C20—H20A	119.2
C2—C7—C6	118.82 (17)	C18—C20—H20A	119.2
C2—C7—C8	118.63 (17)	N5—C21—N4	116.22 (17)
C6—C7—C8	122.55 (17)	N5—C21—S1	123.99 (15)
C9—C8—C7	121.42 (18)	N4—C21—S1	119.79 (14)
C9—C8—H8A	119.3	C17—C22—H22A	109.5
C7—C8—H8A	119.3	C17—C22—H22B	109.5
C8—C9—C10	118.83 (18)	H22A—C22—H22B	109.5
C8—C9—H9A	120.6	C17—C22—H22C	109.5
C10—C9—H9A	120.6	H22A—C22—H22C	109.5
C1—C10—O1	122.62 (17)	H22B—C22—H22C	109.5
C19—N1—N2—C17	0.7 (2)	C14—C15—C16—C11	0.0 (3)
C16—N1—N2—C17	179.09 (16)	C14—C15—C16—N1	−179.64 (17)
C20—N3—N4—C21	−178.93 (17)	C12—C11—C16—C15	1.4 (3)
C10—C1—C2—C3	−179.63 (17)	C12—C11—C16—N1	−178.98 (17)
C10—C1—C2—C7	0.0 (3)	C19—N1—C16—C15	−166.70 (19)
C7—C2—C3—C4	−0.7 (3)	N2—N1—C16—C15	15.3 (2)
C1—C2—C3—C4	178.93 (18)	C19—N1—C16—C11	13.6 (3)
C2—C3—C4—C5	0.1 (3)	N2—N1—C16—C11	−164.33 (17)
C3—C4—C5—C6	0.4 (3)	N1—N2—C17—C18	−0.1 (2)
C4—C5—C6—C7	−0.3 (3)	N1—N2—C17—C22	−179.62 (17)
C3—C2—C7—C6	0.8 (3)	N2—C17—C18—C19	−0.6 (2)
C1—C2—C7—C6	−178.83 (16)	C22—C17—C18—C19	178.93 (19)
C3—C2—C7—C8	−178.74 (16)	N2—C17—C18—C20	178.86 (17)
C1—C2—C7—C8	1.6 (3)	C22—C17—C18—C20	−1.6 (3)
C5—C6—C7—C2	−0.3 (3)	C10—O1—C19—N1	106.6 (2)
C5—C6—C7—C8	179.23 (18)	C10—O1—C19—C18	−76.5 (2)
C2—C7—C8—C9	−1.1 (3)	N2—N1—C19—O1	176.39 (16)
C6—C7—C8—C9	179.36 (18)	C16—N1—C19—O1	−1.7 (3)
C7—C8—C9—C10	−1.0 (3)	N2—N1—C19—C18	−1.1 (2)
C2—C1—C10—O1	179.76 (16)	C16—N1—C19—C18	−179.22 (18)
C2—C1—C10—C9	−2.2 (3)	C17—C18—C19—O1	−176.24 (18)
C19—O1—C10—C1	−24.8 (2)	C20—C18—C19—O1	4.3 (3)
C19—O1—C10—C9	157.06 (16)	C17—C18—C19—N1	1.0 (2)
C8—C9—C10—C1	2.8 (3)	C20—C18—C19—N1	−178.40 (19)
C8—C9—C10—O1	−179.09 (16)	N4—N3—C20—C18	177.44 (17)
C16—C11—C12—C13	−2.0 (3)	C19—C18—C20—N3	5.4 (3)
C11—C12—C13—C14	1.2 (3)	C17—C18—C20—N3	−173.91 (19)
C12—C13—C14—C15	0.3 (3)	N3—N4—C21—N5	−2.4 (3)
C13—C14—C15—C16	−0.9 (3)	N3—N4—C21—S1	178.15 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H1N4···S1i	0.93 (3)	2.56 (3)	3.466 (2)	165 (3)
N5—H2N5···O1W	0.89 (3)	1.94 (3)	2.805 (3)	164 (3)
O1W—H2W1···S1ii	0.94 (4)	2.58 (4)	3.397 (2)	145 (3)
O1W—H1W1···N2iii	0.89 (4)	2.01 (4)	2.876 (3)	167 (4)
C20—H20A···S1i	0.95	2.87	3.741 (2)	153

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H1N4⋯S1i	0.93 (3)	2.56 (3)	3.466 (2)	165 (3)
N5—H2N5⋯O1W	0.89 (3)	1.94 (3)	2.805 (3)	164 (3)
O1W—H2W1⋯S1ii	0.94 (4)	2.58 (4)	3.397 (2)	145 (3)
O1W—H1W1⋯N2iii	0.89 (4)	2.01 (4)	2.876 (3)	167 (4)
C20—H20A⋯S1i	0.95	2.87	3.741 (2)	153

Symmetry codes: (i) ; (ii) ; (iii) .