4-Benzyl-3-(2-fur­yl)-1H-1,2,4-triazole-5(4H)-thione hemihydrate

Zareef, M.; Iqbal, R.; Parvez, M.

doi:10.1107/S1600536808012361

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Pages o952-o953

doi:10.1107/S1600536808012361

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4-Benzyl-3-(2-furyl)-1H-1,2,4-triazole-5(4H)-thione hemihydrate

Muhammad Zareef,^a ^* Rashid Iqbal ^a and Masood Parvez ^b

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, and ^bDepartment of Chemistry, The University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4
^*Correspondence e-mail: mzareef71@yahoo.com

(Received 9 April 2008; accepted 28 April 2008; online 3 May 2008)

In the asymmetric unit of the title compound, C₁₃H₁₁N₃OS·0.5H₂O, there are two independent molecules of 4-benzyl-3-(2-furyl)-1H-1,2,4-triazole-5(4H)-thione and a water molecule of hydration. The conformation of the two organic molecules is slightly different, the dihedral angles formed by the furyl and triazole rings being 5.63 (15) and 17.66 (13)°. The water molecule of hydration links three adjacent triazole molecules to form a cluster via intermolecular O—H⋯S, N—H⋯S and N—H⋯O hydrogen bonds, generating a 10-membered ring of graph set R³₃(10). The crystal structure is further stabilized by intra- and intermolecular C—H⋯S, C—H⋯O and C—H⋯N hydrogen bonds and by π–π stacking interactions involving the furyl and triazole rings of centrosymmetrically related molecules, with a centroid–centroid separation of 3.470 (2) Å.

Related literature

For related literature, see: Ahmad et al. (2001 ); Altman & Solomost (1993 ); Chai et al. (2003 ); Dege et al. (2004 ); Hashimoto et al. (1990 ); Kanazawa et al. (1988 ); Öztürk et al. (2004 ); Yıldırım et al. (2004 ); Bernstein et al. (1995 ); Etter (1990 ).

Experimental

Crystal data

C₁₃H₁₁N₃OS·0.5H₂O
M_r = 266.33
Triclinic, $[P \overline 1]$
a = 6.082 (2) Å
b = 12.069 (4) Å
c = 17.818 (5) Å
α = 92.43 (2)°
β = 94.35 (2)°
γ = 103.83 (2)°
V = 1263.9 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 173 (2) K
0.18 × 0.16 × 0.04 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1997 ) T_min = 0.956, T_max = 0.990
10729 measured reflections
5735 independent reflections
4365 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.096
S = 1.03
5735 reflections
347 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯N5ⁱ	0.85 (2)	2.08 (2)	2.906 (2)	165 (2)
N1—H1A⋯S2ⁱⁱ	0.88 (2)	2.47 (2)	3.267 (2)	151 (2)
N4—H4A⋯O3ⁱⁱⁱ	0.89 (2)	1.81 (2)	2.697 (2)	174 (2)
C7—H7A⋯N2^iv	0.99	2.60	3.304 (3)	128
C7—H7B⋯O1^iv	0.99	2.59	3.440 (2)	144
O3—H3B⋯S1	0.85 (2)	2.50 (2)	3.320 (2)	162 (2)
C7—H7A⋯S1	0.99	2.74	3.237 (2)	112
C9—H9⋯N3	0.95	2.56	2.893 (2)	101
C26—H26⋯N6	0.95	2.58	2.903 (3)	100
C20—H20B⋯S2	0.99	2.78	3.214 (2)	107
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x+1, y-1, z; (iii) x-1, y+1, z; (iv) x-1, y, z.

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808012361/rz2207sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808012361/rz2207Isup2.hkl

checkCIF report

Comment top

Recently, much attention has been focused on disubstituted 1,2,4-triazole derivatives for their broad-spectrum biological and pharmacological activities, such as fungicidal, herbicidal, anticonvulsant, antitumoral and inhibition of cholesterol (Chai et al., 2003; Kanazawa et al., 1988; Hashimoto et al., 1990). In addition, they have many applications in agriculture domain (Altman & Solomost, 1993). In this paper, we report the synthesis and crystal structure of the title compound.

The asymmetric unit of the title compound is composed of two independent molecules (hereafter called A and B) depicted in Fig. 1 and 2, respectively, and a water molecule of hydration. The furyl and triazole rings in molecule A are substantially planar (maximum deviation 0.0586 (13) Å for atom N2), with the S1 atom 0.1980 (16) Å out of this plane; the mean-planes of the furyl and triazole form a dihedral angle of 5.63 (15)°. The corresponding furyl and triazole rings in molecule B are far from planar with atoms O2 and C17 deviating from the plane by 0.2571 (11) and -0.1633 (15) Å, respectively. The mean-planes of the five-membered rings in molecule B form an angle 17.66 (13)°. In both molecules, the benzyl rings are oriented at 80.72 (4) and 80.70 (4)°, from the planes formed by the ten atoms of the furyl and triazole rings in the molecules A and B, respectively. Bond distances and angles in the two molecules agree well with each other. Similar bond distances and bond angles have been reported in compounds closely related to the title compound, e.g., 4-chlorophenyl analogue (Öztürk et al., 2004), 4-methoxyphenyl analogue (Yıldırım et al., 2004) and 4-p-tolyl (Dege et al., 2004); in all these compounds, the mean-planes of the phenyl rings and those of the furyl and triazole rings lie close to right angles. The water molecule of hydration links three adjacent molecules of the title compound to form a cluster via intermolecular hydrogen bonds (Fig. 3, Table 1), forming a 10-membered ring of graph set R³₃(10) (Etter, 1990; Bernstein et al., 1995). Nonconventional intermolecular C—H···N and C—H···O H-bonds are also present in addition to intramolecular C—H···S and C—H···N hydrogen interactions (Table 1). The crystal structure is further stabilized by π-π stacking interactions involving centrosymmetrically related furyl and triazole rings at (x, y, z) and (1-x, -y, -z) with a centroid-centroid separation of 3.470 (2) Å.

Related literature top

For related literature, see: Ahmad et al. (2001); Altman & Solomost (1993); Chai et al. (2003); Dege et al. (2004); Hashimoto et al. (1990); Kanazawa et al. (1988); Öztürk et al. (2004); Yıldırım et al. (2004); Bernstein et al. (1995); Etter (1990).

Experimental top

The title compound was prepared from the corresponding thiosemicarbazide by following the reported procedure (Ahmad et al., 2001). 4-Benzyl-1-(2-furoyl)thiosemicarbazide (10 mmol) was dissolved in an aqueous 4 N sodium hydroxide solution (50 ml). The solution was heated to reflux for 7 h, cooled and filtered. The filtrate was acidified to pH of 4–5, with 4 N hydrochloric acid. The solid crude product was filtered off, washed with water and recrystallized from aqueous ethanol (60%). Crystals of the title compound were grown by slow evaporation of an ethanol solution over 11 days at room temperature (yield 81%).

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP-3 (Farrugia, 1997) drawing of molecule A with displacement ellipsoids plotted at the 50% probability level.
	Fig. 2. ORTEP-3 (Farrugia, 1997) drawing of molecule B with displacement ellipsoids plotted at the 50% probability level.
	Fig. 3. Packing diagram of the title compound showing intermolecular hydrogen bonds as dashed lines. H atoms not involved in H bonding are omitted for clarity.

4-Benzyl-3-(2-furyl)-1H-1,2,4-triazole-5(4H)-thione hemihydrate top

Crystal data top

C₁₃H₁₁N₃OS·0.5H₂O	Z = 4
M_r = 266.33	F(000) = 556
Triclinic, P1	D_x = 1.400 Mg m⁻³
Hall symbol: -P 1	Melting point = 458–459 K
a = 6.082 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.069 (4) Å	Cell parameters from 10729 reflections
c = 17.818 (5) Å	θ = 3.0–27.5°
α = 92.43 (2)°	µ = 0.25 mm⁻¹
β = 94.35 (2)°	T = 173 K
γ = 103.83 (2)°	Plate, colourless
V = 1263.9 (7) Å³	0.18 × 0.16 × 0.04 mm

Data collection top

Nonius KappaCCD diffractometer	5735 independent reflections
Radiation source: fine-focus sealed tube	4365 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω and ϕ scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	h = −7→7
T_min = 0.956, T_max = 0.990	k = −15→15
10729 measured reflections	l = −23→23

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.096	w = 1/[σ²(F_o²) + (0.0384P)² + 0.468P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
5735 reflections	Δρ_max = 0.22 e Å⁻³
347 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.012 (2)

Crystal data top

C₁₃H₁₁N₃OS·0.5H₂O	γ = 103.83 (2)°
M_r = 266.33	V = 1263.9 (7) Å³
Triclinic, P1	Z = 4
a = 6.082 (2) Å	Mo Kα radiation
b = 12.069 (4) Å	µ = 0.25 mm⁻¹
c = 17.818 (5) Å	T = 173 K
α = 92.43 (2)°	0.18 × 0.16 × 0.04 mm
β = 94.35 (2)°

Data collection top

Nonius KappaCCD diffractometer	5735 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	4365 reflections with I > 2σ(I)
T_min = 0.956, T_max = 0.990	R_int = 0.031
10729 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.22 e Å⁻³
5735 reflections	Δρ_min = −0.24 e Å⁻³
347 parameters

Special details top

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	0.34044 (8)	0.05680 (4)	0.28003 (3)	0.03056 (13)
S2	−0.20179 (8)	0.77953 (4)	0.25164 (2)	0.02763 (13)
O1	0.8468 (2)	0.08820 (11)	−0.01137 (7)	0.0305 (3)
O2	0.5602 (2)	0.82229 (11)	0.51122 (7)	0.0325 (3)
O3	0.7588 (3)	0.03225 (11)	0.40424 (8)	0.0333 (3)
H3A	0.752 (4)	0.0567 (19)	0.4491 (13)	0.040*
H3B	0.633 (4)	0.0293 (19)	0.3796 (13)	0.040*
N1	0.6822 (3)	0.01773 (13)	0.20087 (8)	0.0260 (3)
H1A	0.725 (3)	−0.0312 (17)	0.2307 (11)	0.031*
N2	0.7734 (3)	0.03375 (13)	0.13290 (8)	0.0268 (3)
N3	0.4856 (2)	0.11614 (11)	0.14138 (8)	0.0213 (3)
N4	0.0028 (3)	0.87457 (12)	0.38823 (8)	0.0247 (3)
H4A	−0.085 (3)	0.9228 (17)	0.3954 (11)	0.030*
N5	0.1725 (3)	0.86844 (12)	0.44183 (8)	0.0254 (3)
N6	0.1475 (2)	0.74212 (11)	0.34577 (8)	0.0222 (3)
C1	0.5050 (3)	0.06404 (14)	0.20819 (9)	0.0232 (4)
C2	0.6504 (3)	0.09428 (14)	0.09778 (9)	0.0223 (4)
C3	0.6860 (3)	0.13059 (14)	0.02235 (9)	0.0240 (4)
C4	0.5984 (4)	0.19649 (17)	−0.02503 (10)	0.0371 (5)
H4	0.4838	0.2354	−0.0155	0.044*
C5	0.7116 (4)	0.19619 (17)	−0.09219 (11)	0.0393 (5)
H5	0.6871	0.2351	−0.1361	0.047*
C6	0.8591 (3)	0.13059 (16)	−0.08148 (10)	0.0331 (4)
H6	0.9580	0.1156	−0.1173	0.040*
C7	0.3061 (3)	0.17367 (14)	0.12078 (10)	0.0243 (4)
H7A	0.1900	0.1564	0.1574	0.029*
H7B	0.2319	0.1417	0.0705	0.029*
C8	0.3862 (3)	0.30216 (14)	0.11841 (9)	0.0246 (4)
C9	0.5982 (3)	0.36345 (15)	0.14907 (10)	0.0296 (4)
H9	0.7004	0.3246	0.1729	0.035*
C10	0.6630 (4)	0.48138 (16)	0.14531 (11)	0.0371 (5)
H10	0.8090	0.5228	0.1665	0.045*
C11	0.5153 (4)	0.53864 (17)	0.11072 (11)	0.0404 (5)
H11	0.5599	0.6192	0.1079	0.048*
C12	0.3028 (4)	0.47821 (17)	0.08038 (12)	0.0414 (5)
H12	0.2006	0.5174	0.0570	0.050*
C13	0.2381 (3)	0.36062 (16)	0.08393 (11)	0.0335 (4)
H13	0.0918	0.3195	0.0627	0.040*
C14	−0.0174 (3)	0.79991 (14)	0.32916 (9)	0.0223 (4)
C15	0.2585 (3)	0.78665 (14)	0.41473 (9)	0.0233 (4)
C16	0.4402 (3)	0.74833 (15)	0.45380 (9)	0.0242 (4)
C17	0.5195 (3)	0.65286 (16)	0.44984 (10)	0.0303 (4)
H17	0.4653	0.5884	0.4151	0.036*
C18	0.7002 (3)	0.66805 (17)	0.50797 (10)	0.0321 (4)
H18	0.7905	0.6157	0.5196	0.039*
C19	0.7177 (3)	0.77051 (17)	0.54297 (11)	0.0332 (4)
H19	0.8252	0.8028	0.5843	0.040*
C20	0.2004 (3)	0.65628 (14)	0.29446 (9)	0.0239 (4)
H20A	0.3674	0.6670	0.2974	0.029*
H20B	0.1489	0.6693	0.2422	0.029*
C21	0.0932 (3)	0.53434 (14)	0.31051 (9)	0.0226 (4)
C22	0.1902 (3)	0.44799 (16)	0.28516 (10)	0.0307 (4)
H22	0.3270	0.4668	0.2610	0.037*
C23	0.0880 (4)	0.33463 (17)	0.29509 (11)	0.0389 (5)
H23	0.1549	0.2760	0.2774	0.047*
C24	−0.1094 (4)	0.30642 (17)	0.33038 (12)	0.0405 (5)
H24	−0.1788	0.2285	0.3369	0.049*
C25	−0.2063 (4)	0.39117 (18)	0.35627 (12)	0.0410 (5)
H25	−0.3424	0.3719	0.3808	0.049*
C26	−0.1044 (3)	0.50534 (16)	0.34637 (11)	0.0318 (4)
H26	−0.1714	0.5637	0.3644	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0307 (3)	0.0369 (3)	0.0255 (2)	0.0094 (2)	0.00647 (18)	0.00482 (19)
S2	0.0285 (3)	0.0262 (2)	0.0270 (2)	0.00626 (19)	−0.00410 (18)	0.00176 (17)
O1	0.0316 (7)	0.0369 (7)	0.0265 (6)	0.0140 (6)	0.0061 (5)	0.0016 (5)
O2	0.0357 (8)	0.0306 (7)	0.0296 (7)	0.0091 (6)	−0.0090 (6)	−0.0012 (5)
O3	0.0415 (9)	0.0352 (7)	0.0271 (7)	0.0190 (7)	−0.0012 (6)	−0.0030 (6)
N1	0.0273 (8)	0.0293 (8)	0.0243 (7)	0.0114 (7)	0.0023 (6)	0.0072 (6)
N2	0.0280 (8)	0.0299 (8)	0.0256 (8)	0.0116 (7)	0.0040 (6)	0.0065 (6)
N3	0.0206 (8)	0.0218 (7)	0.0225 (7)	0.0071 (6)	0.0008 (6)	0.0029 (5)
N4	0.0268 (8)	0.0231 (7)	0.0253 (7)	0.0093 (6)	−0.0010 (6)	0.0007 (6)
N5	0.0266 (8)	0.0262 (7)	0.0237 (7)	0.0083 (6)	−0.0019 (6)	0.0009 (6)
N6	0.0233 (8)	0.0199 (7)	0.0232 (7)	0.0055 (6)	0.0011 (6)	0.0008 (6)
C1	0.0241 (9)	0.0213 (8)	0.0230 (8)	0.0044 (7)	−0.0010 (7)	0.0003 (7)
C2	0.0221 (9)	0.0212 (8)	0.0243 (8)	0.0072 (7)	0.0009 (7)	0.0005 (7)
C3	0.0236 (9)	0.0258 (9)	0.0235 (8)	0.0073 (7)	0.0040 (7)	−0.0004 (7)
C4	0.0512 (13)	0.0423 (11)	0.0282 (10)	0.0277 (10)	0.0126 (9)	0.0110 (8)
C5	0.0592 (14)	0.0384 (11)	0.0263 (10)	0.0194 (10)	0.0126 (9)	0.0103 (8)
C6	0.0382 (12)	0.0355 (10)	0.0256 (9)	0.0070 (9)	0.0097 (8)	0.0007 (8)
C7	0.0211 (9)	0.0257 (9)	0.0276 (9)	0.0093 (7)	0.0002 (7)	0.0019 (7)
C8	0.0304 (10)	0.0245 (9)	0.0210 (8)	0.0109 (8)	0.0022 (7)	0.0008 (7)
C9	0.0339 (11)	0.0281 (9)	0.0272 (9)	0.0108 (8)	−0.0036 (8)	0.0004 (7)
C10	0.0440 (12)	0.0290 (10)	0.0328 (10)	0.0016 (9)	−0.0062 (9)	−0.0021 (8)
C11	0.0609 (15)	0.0250 (10)	0.0350 (11)	0.0113 (10)	−0.0012 (10)	0.0037 (8)
C12	0.0549 (14)	0.0336 (11)	0.0405 (11)	0.0231 (10)	−0.0070 (10)	0.0053 (9)
C13	0.0327 (11)	0.0320 (10)	0.0371 (10)	0.0131 (9)	−0.0046 (8)	0.0007 (8)
C14	0.0213 (9)	0.0193 (8)	0.0262 (8)	0.0034 (7)	0.0038 (7)	0.0052 (7)
C15	0.0238 (9)	0.0227 (8)	0.0224 (8)	0.0037 (7)	0.0020 (7)	0.0022 (7)
C16	0.0238 (9)	0.0274 (9)	0.0207 (8)	0.0055 (7)	−0.0001 (7)	0.0013 (7)
C17	0.0305 (10)	0.0340 (10)	0.0280 (9)	0.0123 (8)	0.0009 (8)	−0.0012 (8)
C18	0.0279 (10)	0.0413 (11)	0.0308 (10)	0.0150 (9)	0.0016 (8)	0.0057 (8)
C19	0.0281 (10)	0.0427 (11)	0.0281 (9)	0.0090 (9)	−0.0058 (8)	0.0069 (8)
C20	0.0253 (9)	0.0244 (9)	0.0228 (8)	0.0068 (7)	0.0053 (7)	0.0005 (7)
C21	0.0246 (9)	0.0237 (8)	0.0202 (8)	0.0080 (7)	−0.0001 (7)	0.0011 (7)
C22	0.0390 (11)	0.0327 (10)	0.0248 (9)	0.0165 (9)	0.0043 (8)	0.0012 (7)
C23	0.0612 (15)	0.0280 (10)	0.0306 (10)	0.0201 (10)	−0.0055 (10)	−0.0015 (8)
C24	0.0527 (14)	0.0241 (9)	0.0384 (11)	0.0019 (9)	−0.0137 (10)	0.0062 (8)
C25	0.0339 (12)	0.0383 (11)	0.0485 (12)	0.0020 (9)	0.0050 (9)	0.0146 (10)
C26	0.0296 (11)	0.0277 (9)	0.0402 (11)	0.0091 (8)	0.0085 (8)	0.0049 (8)

Geometric parameters (Å, º) top

S1—C1	1.676 (2)	C8—C9	1.382 (3)
S2—C14	1.682 (2)	C8—C13	1.394 (2)
O1—C6	1.370 (2)	C9—C10	1.389 (3)
O1—C3	1.372 (2)	C9—H9	0.9500
O2—C19	1.364 (2)	C10—C11	1.383 (3)
O2—C16	1.369 (2)	C10—H10	0.9500
O3—H3A	0.85 (2)	C11—C12	1.380 (3)
O3—H3B	0.85 (2)	C11—H11	0.9500
N1—C1	1.339 (2)	C12—C13	1.385 (3)
N1—N2	1.372 (2)	C12—H12	0.9500
N1—H1A	0.88 (2)	C13—H13	0.9500
N2—C2	1.309 (2)	C15—C16	1.440 (2)
N3—C1	1.380 (2)	C16—C17	1.353 (2)
N3—C2	1.380 (2)	C17—C18	1.425 (3)
N3—C7	1.460 (2)	C17—H17	0.9500
N4—C14	1.335 (2)	C18—C19	1.338 (3)
N4—N5	1.370 (2)	C18—H18	0.9500
N4—H4A	0.89 (2)	C19—H19	0.9500
N5—C15	1.314 (2)	C20—C21	1.509 (2)
N6—C14	1.374 (2)	C20—H20A	0.9900
N6—C15	1.378 (2)	C20—H20B	0.9900
N6—C20	1.461 (2)	C21—C26	1.382 (3)
C2—C3	1.447 (2)	C21—C22	1.390 (2)
C3—C4	1.349 (3)	C22—C23	1.386 (3)
C4—C5	1.425 (3)	C22—H22	0.9500
C4—H4	0.9500	C23—C24	1.375 (3)
C5—C6	1.340 (3)	C23—H23	0.9500
C5—H5	0.9500	C24—C25	1.377 (3)
C6—H6	0.9500	C24—H24	0.9500
C7—C8	1.514 (2)	C25—C26	1.394 (3)
C7—H7A	0.9900	C25—H25	0.9500
C7—H7B	0.9900	C26—H26	0.9500

C6—O1—C3	106.50 (14)	C12—C11—H11	120.1
C19—O2—C16	106.33 (14)	C10—C11—H11	120.1
H3A—O3—H3B	108 (2)	C11—C12—C13	120.22 (18)
C1—N1—N2	114.05 (14)	C11—C12—H12	119.9
C1—N1—H1A	126.0 (13)	C13—C12—H12	119.9
N2—N1—H1A	118.8 (13)	C12—C13—C8	120.44 (19)
C2—N2—N1	103.59 (14)	C12—C13—H13	119.8
C1—N3—C2	107.51 (14)	C8—C13—H13	119.8
C1—N3—C7	124.11 (14)	N4—C14—N6	104.29 (14)
C2—N3—C7	128.16 (14)	N4—C14—S2	128.50 (13)
C14—N4—N5	113.20 (14)	N6—C14—S2	127.21 (13)
C14—N4—H4A	126.2 (13)	N5—C15—N6	110.73 (15)
N5—N4—H4A	120.5 (13)	N5—C15—C16	123.67 (15)
C15—N5—N4	104.25 (14)	N6—C15—C16	125.58 (15)
C14—N6—C15	107.53 (14)	C17—C16—O2	109.93 (15)
C14—N6—C20	124.07 (14)	C17—C16—C15	135.42 (16)
C15—N6—C20	128.21 (14)	O2—C16—C15	114.60 (14)
N1—C1—N3	103.46 (14)	C16—C17—C18	106.48 (17)
N1—C1—S1	128.34 (13)	C16—C17—H17	126.8
N3—C1—S1	128.17 (13)	C18—C17—H17	126.8
N2—C2—N3	111.36 (15)	C19—C18—C17	106.48 (16)
N2—C2—C3	122.82 (15)	C19—C18—H18	126.8
N3—C2—C3	125.81 (15)	C17—C18—H18	126.8
C4—C3—O1	109.95 (15)	C18—C19—O2	110.79 (16)
C4—C3—C2	135.93 (17)	C18—C19—H19	124.6
O1—C3—C2	114.11 (15)	O2—C19—H19	124.6
C3—C4—C5	106.47 (17)	N6—C20—C21	114.33 (14)
C3—C4—H4	126.8	N6—C20—H20A	108.7
C5—C4—H4	126.8	C21—C20—H20A	108.7
C6—C5—C4	106.89 (17)	N6—C20—H20B	108.7
C6—C5—H5	126.6	C21—C20—H20B	108.7
C4—C5—H5	126.6	H20A—C20—H20B	107.6
C5—C6—O1	110.20 (16)	C26—C21—C22	119.00 (17)
C5—C6—H6	124.9	C26—C21—C20	122.02 (15)
O1—C6—H6	124.9	C22—C21—C20	118.90 (16)
N3—C7—C8	114.60 (14)	C23—C22—C21	120.24 (19)
N3—C7—H7A	108.6	C23—C22—H22	119.9
C8—C7—H7A	108.6	C21—C22—H22	119.9
N3—C7—H7B	108.6	C24—C23—C22	120.41 (19)
C8—C7—H7B	108.6	C24—C23—H23	119.8
H7A—C7—H7B	107.6	C22—C23—H23	119.8
C9—C8—C13	118.95 (17)	C23—C24—C25	119.95 (19)
C9—C8—C7	122.93 (15)	C23—C24—H24	120.0
C13—C8—C7	118.12 (16)	C25—C24—H24	120.0
C8—C9—C10	120.53 (17)	C24—C25—C26	119.9 (2)
C8—C9—H9	119.7	C24—C25—H25	120.1
C10—C9—H9	119.7	C26—C25—H25	120.1
C11—C10—C9	120.12 (19)	C21—C26—C25	120.52 (18)
C11—C10—H10	119.9	C21—C26—H26	119.7
C9—C10—H10	119.9	C25—C26—H26	119.7
C12—C11—C10	119.73 (18)

C1—N1—N2—C2	1.32 (19)	C7—C8—C13—C12	179.87 (18)
C14—N4—N5—C15	−0.33 (19)	N5—N4—C14—N6	0.32 (19)
N2—N1—C1—N3	−1.84 (19)	N5—N4—C14—S2	−179.83 (13)
N2—N1—C1—S1	176.30 (13)	C15—N6—C14—N4	−0.18 (18)
C2—N3—C1—N1	1.59 (18)	C20—N6—C14—N4	−175.62 (14)
C7—N3—C1—N1	176.47 (14)	C15—N6—C14—S2	179.97 (13)
C2—N3—C1—S1	−176.56 (13)	C20—N6—C14—S2	4.5 (2)
C7—N3—C1—S1	−1.7 (2)	N4—N5—C15—N6	0.20 (19)
N1—N2—C2—N3	−0.20 (19)	N4—N5—C15—C16	−178.34 (16)
N1—N2—C2—C3	−179.37 (16)	C14—N6—C15—N5	−0.02 (19)
C1—N3—C2—N2	−0.90 (19)	C20—N6—C15—N5	175.17 (15)
C7—N3—C2—N2	−175.50 (15)	C14—N6—C15—C16	178.48 (16)
C1—N3—C2—C3	178.23 (16)	C20—N6—C15—C16	−6.3 (3)
C7—N3—C2—C3	3.6 (3)	C19—O2—C16—C17	0.2 (2)
C6—O1—C3—C4	0.6 (2)	C19—O2—C16—C15	177.89 (15)
C6—O1—C3—C2	−179.92 (15)	N5—C15—C16—C17	159.8 (2)
N2—C2—C3—C4	−175.6 (2)	N6—C15—C16—C17	−18.5 (3)
N3—C2—C3—C4	5.4 (3)	N5—C15—C16—O2	−17.1 (2)
N2—C2—C3—O1	5.1 (2)	N6—C15—C16—O2	164.55 (16)
N3—C2—C3—O1	−173.93 (15)	O2—C16—C17—C18	−0.2 (2)
O1—C3—C4—C5	−0.4 (2)	C15—C16—C17—C18	−177.2 (2)
C2—C3—C4—C5	−179.8 (2)	C16—C17—C18—C19	0.1 (2)
C3—C4—C5—C6	0.1 (2)	C17—C18—C19—O2	0.0 (2)
C4—C5—C6—O1	0.3 (2)	C16—O2—C19—C18	−0.1 (2)
C3—O1—C6—C5	−0.5 (2)	C14—N6—C20—C21	−98.91 (19)
C1—N3—C7—C8	111.39 (18)	C15—N6—C20—C21	86.6 (2)
C2—N3—C7—C8	−74.8 (2)	N6—C20—C21—C26	25.8 (2)
N3—C7—C8—C9	−13.9 (2)	N6—C20—C21—C22	−157.33 (16)
N3—C7—C8—C13	166.36 (16)	C26—C21—C22—C23	0.8 (3)
C13—C8—C9—C10	−0.3 (3)	C20—C21—C22—C23	−176.17 (16)
C7—C8—C9—C10	180.00 (17)	C21—C22—C23—C24	−0.3 (3)
C8—C9—C10—C11	0.0 (3)	C22—C23—C24—C25	−0.2 (3)
C9—C10—C11—C12	0.4 (3)	C23—C24—C25—C26	0.2 (3)
C10—C11—C12—C13	−0.5 (3)	C22—C21—C26—C25	−0.7 (3)
C11—C12—C13—C8	0.3 (3)	C20—C21—C26—C25	176.14 (17)
C9—C8—C13—C12	0.1 (3)	C24—C25—C26—C21	0.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···N5ⁱ	0.85 (2)	2.08 (2)	2.906 (2)	165 (2)
N1—H1A···S2ⁱⁱ	0.88 (2)	2.47 (2)	3.267 (2)	151 (2)
N4—H4A···O3ⁱⁱⁱ	0.89 (2)	1.81 (2)	2.697 (2)	174 (2)
C7—H7A···N2^iv	0.99	2.60	3.304 (3)	128
C7—H7B···O1^iv	0.99	2.59	3.440 (2)	144
O3—H3B···S1	0.85 (2)	2.50 (2)	3.320 (2)	162 (2)
C7—H7A···S1	0.99	2.74	3.237 (2)	112
C9—H9···N3	0.95	2.56	2.893 (2)	101
C26—H26···N6	0.95	2.58	2.903 (3)	100
C20—H20B···S2	0.99	2.78	3.214 (2)	107

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₁N₃OS·0.5H₂O
M_r	266.33
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	6.082 (2), 12.069 (4), 17.818 (5)
α, β, γ (°)	92.43 (2), 94.35 (2), 103.83 (2)
V (Å³)	1263.9 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.18 × 0.16 × 0.04

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1997)
T_min, T_max	0.956, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	10729, 5735, 4365
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.096, 1.03
No. of reflections	5735
No. of parameters	347
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.24

Computer programs: COLLECT (Hooft, 1998), DENZO (Otwinowski & Minor, 1997), SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···N5ⁱ	0.85 (2)	2.08 (2)	2.906 (2)	165 (2)
N1—H1A···S2ⁱⁱ	0.88 (2)	2.47 (2)	3.267 (2)	151 (2)
N4—H4A···O3ⁱⁱⁱ	0.89 (2)	1.81 (2)	2.697 (2)	174 (2)
C7—H7A···N2^iv	0.99	2.60	3.304 (3)	128
C7—H7B···O1^iv	0.99	2.59	3.440 (2)	144
O3—H3B···S1	0.85 (2)	2.50 (2)	3.320 (2)	162 (2)
C7—H7A···S1	0.99	2.74	3.237 (2)	112
C9—H9···N3	0.95	2.56	2.893 (2)	101
C26—H26···N6	0.95	2.58	2.903 (3)	100
C20—H20B···S2	0.99	2.78	3.214 (2)	107

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

References

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Volume 64| Part 6| June 2008| Pages o952-o953

doi:10.1107/S1600536808012361

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