(2E)-2-{[3-Methyl-5-(2-naphth­yloxy)-1-phenyl-1H-pyrazol-4-yl]methyl­idene}hydrazinecarbothio­amide monohydrate

Fun, H.-K.; Chia, T.S.; Shetty, S.; Kalluraya, B.; Nithinchandra

doi:10.1107/S1600536812039815

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 10| October 2012| Pages o3055-o3056

https://doi.org/10.1107/S1600536812039815

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(2E)-2-{[3-Methyl-5-(2-naphthyloxy)-1-phenyl-1H-pyrazol-4-yl]methylidene}hydrazinecarbothioamide monohydrate

Hoong-Kun Fun,^a,^b ^*‡ Tze Shyang Chia,^a § Shobhitha Shetty,^c Balakrishna Kalluraya ^c and Nithinchandra ^c

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bDepartment of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia, and ^cDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore 574 199, India
^*Correspondence e-mail: hkfun@usm.my

(Received 14 September 2012; accepted 19 September 2012; online 29 September 2012)

In the title compound, C₂₂H₁₉N₅OS·H₂O, 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-methylenehydrazinecarbothioamide 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, molecules 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 interactions 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_r = 419.50
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.044
wR(F²) = 0.124
S = 1.04
4542 reflections
292 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.33 e Å⁻³

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) -x+1, -y+1, -z; (ii) -x+1, -y+2, -z; (iii) x+1, y+1, z.

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: https://doi.org/10.1107/S1600536812039815/rz5007sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812039815/rz5007Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812039815/rz5007Isup3.cml

checkCIF report

Comment top

Pyrazoles and their derivatives play an important role in medicinal chemistry (Rai et al., 2008). Several derivatives of pyrazole are of pharmaceutical interest due to their analgesic action. Pyrazole molecules also exhibit anticancer (Hall et al., 2008), anti-inflammatory, antidepressant, anticonvulsant and anti-HIV properties (Isloor et al., 2009). During the past years, considerable evidence has been accumulated to demonstrate the efficacy of pyrazole derivatives. The incorporation of an aryl system into the pyrazole ring enhances the biological activities to a great extent (Girisha et al., 2010). In view of the importance of these molecules, we report herein the crystal structure of the title compound.

The asymmetric unit of the title compound (Fig. 1) consists of one (2E)-2-{[3-methyl-5-(2-naphthayloxy)-1-phenyl-1H-pyrazol-4-yl]methylidene}hydrazinocarbothioamide molecule and one water molecule. The C1–C10 naphthalene ring system [maximum deviation = 0.025 (2) Å at atom C10] and C11–C16 benzene ring [dihedral angle between them = 85.19 (8)°] make dihedral angles of 87.02 (9)° and 14.41 (10)°, respectively, with the N1/N2/C17–C19 pyrazole ring. The 2-methylenehydrazinecarbothioamide group [C20/N3/N4/C21/S1/N5; maximum deviation = 0.022 (1) Å at atom N4] is slightly twisted from pyrazole ring as indicated by the dihedral angle of 5.60 (11)°. In the crystal (Fig. 2), molecules are linked by intermolecular N4—H1N4···S1, N5—H2N5···O1W, O1W—H2W1···S1, O1W—H1W1···N2 and C20—H20A···S1 hydrogen bonds into sheets parallel to (001) plane. π–π interactions are also observed with Cg1···Cg2 = 3.7778 (12) Å [symmetry code = -x, 2 - y, 1 - z] and Cg3···Cg3 = 3.7010 (12) Å [symmetry code = -1 - x, 1 - y, 1 - z], where Cg1, Cg2 and Cg3 are the centroids of the C1/C2/C7–C10, C2–C7 and C11–C16 rings, respectively.

Related literature top

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 top

The title compound was obtained by refluxing a mixture of 3-methyl-5-(2-naphthyloxy)-1-phenyl-1H-pyrazole-4-carbaldehyde (0.01 mol) and thiosemicarbazide (0.01 mol) in ethanol (30 ml) with 3 drops of concentrated sulfuric acid for 1 h. Excess ethanol was removed from the reaction mixture under reduced pressure. The solid product obtained was filtered, washed with ethanol and dried. Yellow block-shaped crystals suitable for X-ray analysis were obtained by slow evaporation from ethanol–N,N-dimethylformamide (3:1 v/v) solution.

Structure description top

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).

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 with 50% probability displacement ellipsoids.
	Fig. 2. The crystal packing of the title compound. The dashed lines represent the hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted.

(2E)-2-{[3-Methyl-5-(2-naphthyloxy)-1-phenyl-1H- pyrazol-4-yl]methylidene}hydrazinecarbothioamide monohydrate top

Crystal data top

C₂₂H₁₉N₅OS·H₂O	Z = 2
M_r = 419.50	F(000) = 440
Triclinic, P1	D_x = 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

Data collection top

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

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)] = 0.044	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(F_o²) + (0.0598P)² + 0.5141P] where P = (F_o² + 2F_c²)/3
4542 reflections	(Δ/σ)_max < 0.001
292 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₂₂H₁₉N₅OS·H₂O	γ = 107.359 (1)°
M_r = 419.50	V = 997.81 (4) Å³
Triclinic, P1	Z = 2
a = 7.9384 (2) Å	Mo Kα radiation
b = 11.1512 (2) Å	µ = 0.19 mm⁻¹
c = 13.0325 (3) Å	T = 100 K
α = 113.481 (1)°	0.41 × 0.22 × 0.17 mm
β = 90.942 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	4542 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3499 reflections with I > 2σ(I)
T_min = 0.925, T_max = 0.967	R_int = 0.031
15860 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.33 e Å⁻³
4542 reflections	Δρ_min = −0.33 e Å⁻³
292 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) −x+1, −y+1, −z; (ii) −x+1, −y+2, −z; (iii) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula	C₂₂H₁₉N₅OS·H₂O
M_r	419.50
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.9384 (2), 11.1512 (2), 13.0325 (3)
α, β, γ (°)	113.481 (1), 90.942 (1), 107.359 (1)
V (Å³)	997.81 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.19
Crystal size (mm)	0.41 × 0.22 × 0.17

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.925, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	15860, 4542, 3499
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.124, 1.04
No. of reflections	4542
No. of parameters	292
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.33

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
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	0.9500	2.8700	3.741 (2)	153.00

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: F-8816-2012.

Acknowledgements

HKF and TSC thank the Universiti Sains Malaysia (USM) for a Research University Grant (No. 1001/PFIZIK/811160). TSC thanks the Malaysian government and USM for the award of a Research Fellowship.

References

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