organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

N-(1,3-Thia­zol-2-yl)-N′-[(thio­phen-2-yl)carbon­yl]thio­urea hemihydrate

aDepartment of Chemistry, M.M.V., Banaras Hindu University, Varanasi 221 005, India, bErciyes University, Faculty of Sciences, Department of Physics, 38039 Kayseri, Turkey, and cDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
*Correspondence e-mail: rbutcher99@yahoo.com

(Received 18 October 2012; accepted 30 October 2012; online 7 November 2012)

The title compound, C9H7N3OS3·0.5H2O, crystallizes with two independent but similar mol­ecules in the asymmetric unit, both of which are linked by a water mol­ecule through O—H⋯N hydrogen bonds. In addition the water O atom is further linked by N—H⋯O hydrogen bonds to two additional main mol­ecules, forming a tetra­meric unit. These tetra­meric units then form infinite ribbons parallel to the ac plane.The dihedral angle between the thio­phenoyl and thia­zolyl rings is 12.15 (10) and 21.69 (11)° in mol­ecules A and B, respectively. The central thio­urea core makes dihedral angles of 5.77 (11) and 8.61 (9)°, respectively, with the thio­­phen­oyl and thia­zolyl rings in mol­ecule A and 8.41 (10) and 13.43 (12)° in mol­ecule B. Each mol­ecule adopts a trans–cis geometry with respect to the position of thio­phenoyl and thia­zole groups relative to the S atom across the thio­urea C—N bonds. This geometry is stabilized by intra­molecular N—H⋯O hydrogen bonds.

Related literature

For general background to aroyl­thio­urea and its derivatives, see: Aly et al. (2007[Aly, A. A., Ahmed, E. K., El-Mokadem, K. M. & Hegazy, M. E. F. (2007). J. Sulfur Chem. 28, 73-93.]). For related structures, see: Koch (2001[Koch, K. R. (2001). Coord. Chem. Rev. 216-217, 473-488.]); Pérez et al. (2008[Pérez, H., Mascarenhas, Y., Estévez-Hernández, O., Santos Jr, S. & Duque, J. (2008). Acta Cryst. E64, o695.]). For their biological activity, see: Saeed et al. (2008[Saeed, S., Bhatti, M. H., Yunus, U. & Jones, P. G. (2008). Acta Cryst. E64, o1485.]); Gu et al. (2007[Gu, C.-L., Liu, L., Sui, Y., Zhao, J.-L. D., Wang, D. & Chen, Y.-J. (2007). Tetrahedron, 18, 455-463.]); Xu et al. (2004[Xu, Y., Hua, W., Liu, X. & Zhu, D. (2004). Chin. J. Org. Chem. 24, 1217-1222.]); Yan & Xue (2008[Yan, L. & Xue, S.-J. (2008). Chin. J. Struct. Chem. 27, 543-546.]).

[Scheme 1]

Experimental

Crystal data
  • C9H7N3OS3·0.5H2O

  • Mr = 278.37

  • Triclinic, [P \overline 1]

  • a = 7.4489 (4) Å

  • b = 11.1060 (6) Å

  • c = 14.7935 (7) Å

  • α = 93.559 (4)°

  • β = 99.813 (4)°

  • γ = 107.789 (5)°

  • V = 1139.74 (11) Å3

  • Z = 4

  • Cu Kα radiation

  • μ = 5.86 mm−1

  • T = 123 K

  • 0.35 × 0.25 × 0.18 mm

Data collection
  • Oxford Diffraction Xcalibur (Ruby, Gemini CCD) diffractometer

  • Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011[Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England.]) Tmin = 0.441, Tmax = 1.000

  • 7828 measured reflections

  • 4566 independent reflections

  • 3906 reflections with I > 2σ(I)

  • Rint = 0.034

Refinement
  • R[F2 > 2σ(F2)] = 0.039

  • wR(F2) = 0.110

  • S = 1.08

  • 4566 reflections

  • 304 parameters

  • 3 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.43 e Å−3

  • Δρmin = −0.30 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1A—H1AA⋯O1Wi 0.86 2.22 3.003 (3) 152
N1B—H1BA⋯O1Wii 0.86 2.14 2.973 (3) 163
N2A—H2AA⋯O1A 0.86 1.89 2.599 (3) 138
N2B—H2BA⋯O1B 0.86 1.90 2.588 (3) 136
O1W—H1W⋯N3B 0.82 (1) 2.06 (1) 2.852 (3) 163 (4)
O1W—H2W⋯N3A 0.82 (1) 2.09 (1) 2.892 (3) 167 (3)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+1, -y, -z+2.

Data collection: CrysAlis PRO (Agilent, 2011[Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

Aroylthiourea and its derivatives are an important class of organic compounds in which the sulphur atom is a major ligand atom and plays an important role in coordination chemistry with transition metals. These compounds are found to be useful in heterocyclic synthesis and many of these substrates have interesting biological activities (Aly et al., 2007). Aroylthioureas and and its derivatives are also known to exhibit a wide range of biological activities, such as anticancer (Saeed et al., 2010), anti-fungal (Saeed et al., 2008), antibacterial, antiviral, anti-tubercular, insecticidal, organocatalyst (Gu et al., 2007) and as agrochemicals (Xu et al., 2004).

The title compound (Fig. 1), C9H7N3OS3.0.5H2O, crystallizes with two independent but similar molecules in the asymmetric unit both of which are linked by a water molecule through O—H···N hydrogen bonds. In addition the water O is further linked by N-H···O hydrogen bonds to two additional C9H7N3OS3 molecules, forming a tetrameric moiety. These tetrameric moieties then form infinite ribbons parallel to the ac plane (Fig.2).

The main bond lengths and angles are within the range obtained for similar compounds (Koch et al., 2001; Perez et al., 2008). The C6A-S2A [1.657 (2)Å], C6B-S2B [1.659 (2)Å] and C5A-O1A [1.233 (3)Å], C5B-O1B [1.232 (3)Å] bonds show typical double-bond character. However, the C-N bond lengths, C5A-N1A [1.388 (3)Å], C6A-N1A [1.395 (3)Å], C6A-N2A [1.345 (3)Å], C7A-N2A [1.383 (3)Å] and C5B-N1B [1.385 (3)Å], C6B-N1B [1.390 (3)Å], C6B-N2B [1.350 (3)Å], C7B-N2B [1.383 (3)Å] are shorter than the normal C-N single-bond length of about 1.48 Å (Allen, 2002). These results can be explained by the existence of resonance in this part of the molecule. In first molecule(A) the central thiourea fragment (N1A-C6A-S2A-N2A) makes the dihedral angle of 5.77(0.11)° and 8.61(0.09 )° with thiophenoyl (S1A/C4A-C1A) and thiazolyl ring (C7A-S3A-C9A-C8A-N3A). Where as in second molecule(B) the central thiourea fragment (N1B/C6B/S2B/N2B) makes the dihedral angle of 8.41(0.10)° with (S1B/C4B-C1B) group, and the thiazole ring (C7B-S3B-C9B-C8B-N3B) is 13.43(0.12)°, respectively. The dihedral angle between the thiophenoyl and thiazolyl rings is 12.15(0.10)° in molecule A and 21.69(0.11)° in molecule B. The trans-cis geometry in the thiourea moiety of both molecule is stabilized by the N-H···O and C-H···O hydrogen bonds (Fig.2 and Table 1).

Related literature top

For general background to aroylthiourea and its derivatives, see: Aly et al. (2007). For related structures, see: Koch (2001); Pérez et al. (2008). For their biological activity, see: Saeed et al. (2008); Gu et al. (2007); Xu et al. (2004); Yan & Xue (2008).

Experimental top

A solution of 2-thiophenecarbonyl chloride (0.01 mol) in anhydrous acetone (80 ml) was added dropwise to a suspension of ammonium thiocyanate (0.01 mol) in anhydrous acetone (50 ml) and the reaction mixture was refluxed for 50 minutes. After cooling to room temperature, a solution of 4-chloroaniline (0.01 mol) in dry acetone (25 ml) was added and the resulting mixture refluxed for 2 h. The reaction mixture was poured into five times its volume of cold water, upon which the thiourea precipitated. The product was recrystallized from ethanol as colorless block crystals.

Refinement top

Hydrogen atoms on the water molecule were located in a difference-Fourier map and both positional and isotropic displacement parameters were refined. Other H atoms were placed in calculated positions with N—H = 0.88 Å and C—H = 0.95 Å and refined using a riding model, with Uiso(H) = 1.2Ueq(C, N).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound showing the atom labeling scheme and 30% probability displacement ellipsoids. Dashed lines indicate the intramolecular N—H···O and inter-species O—H···N hydrogen bonds.
[Figure 2] Fig. 2. Crystal packing for the title compound viewed along the c axis. Dashed lines indicate an intermolecular N—H···O and O—H···N hydrogen bonds.
N-(1,3-Thiazol-2-yl)-N'-[(thiophen-2-yl)carbonyl]thiourea hemihydrate top
Crystal data top
C9H7N3OS3·0.5H2OZ = 4
Mr = 278.37F(000) = 572
Triclinic, P1Dx = 1.622 Mg m3
Hall symbol: -P 1Cu Kα radiation, λ = 1.54184 Å
a = 7.4489 (4) ÅCell parameters from 3735 reflections
b = 11.1060 (6) Åθ = 3.1–75.6°
c = 14.7935 (7) ŵ = 5.86 mm1
α = 93.559 (4)°T = 123 K
β = 99.813 (4)°Block, colorless
γ = 107.789 (5)°0.35 × 0.25 × 0.18 mm
V = 1139.74 (11) Å3
Data collection top
Oxford Diffraction Xcalibur (Ruby, Gemini CCD)
diffractometer
4566 independent reflections
Radiation source: Enhance (Cu) X-ray Source3906 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
Detector resolution: 10.5081 pixels mm-1θmax = 75.8°, θmin = 3.1°
ω scansh = 96
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
k = 1313
Tmin = 0.441, Tmax = 1.000l = 1218
7828 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.0566P)2 + 0.1264P]
where P = (Fo2 + 2Fc2)/3
4566 reflections(Δ/σ)max = 0.001
304 parametersΔρmax = 0.43 e Å3
3 restraintsΔρmin = 0.30 e Å3
Crystal data top
C9H7N3OS3·0.5H2Oγ = 107.789 (5)°
Mr = 278.37V = 1139.74 (11) Å3
Triclinic, P1Z = 4
a = 7.4489 (4) ÅCu Kα radiation
b = 11.1060 (6) ŵ = 5.86 mm1
c = 14.7935 (7) ÅT = 123 K
α = 93.559 (4)°0.35 × 0.25 × 0.18 mm
β = 99.813 (4)°
Data collection top
Oxford Diffraction Xcalibur (Ruby, Gemini CCD)
diffractometer
4566 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
3906 reflections with I > 2σ(I)
Tmin = 0.441, Tmax = 1.000Rint = 0.034
7828 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0393 restraints
wR(F2) = 0.110H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.43 e Å3
4566 reflectionsΔρmin = 0.30 e Å3
304 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
xyzUiso*/Ueq
S1A0.17373 (9)0.25490 (5)0.47025 (4)0.02167 (15)
S1B0.26874 (10)0.44204 (6)0.98233 (4)0.02371 (15)
S2A0.29573 (10)0.30344 (6)0.38262 (4)0.02567 (16)
S2B0.22859 (9)0.13688 (5)1.07688 (4)0.01906 (14)
S3A0.32482 (9)0.42492 (5)0.56122 (4)0.02351 (15)
S3B0.14624 (9)0.23871 (5)0.89130 (4)0.02046 (15)
O1A0.2481 (3)0.03651 (16)0.55080 (11)0.0221 (4)
O1B0.2523 (3)0.20849 (16)0.90756 (12)0.0243 (4)
O1W0.5774 (2)0.02421 (15)0.75431 (12)0.0196 (4)
N1A0.2661 (3)0.07508 (18)0.41864 (13)0.0171 (4)
H1AA0.26750.07090.36090.021*
N1B0.2789 (3)0.08541 (17)1.04263 (13)0.0149 (4)
H1BA0.30200.08301.10180.018*
N2A0.3233 (3)0.17714 (18)0.54658 (13)0.0172 (4)
H2AA0.32760.10650.57570.021*
N2B0.2633 (3)0.02718 (18)0.91718 (13)0.0158 (4)
H2BA0.28960.03470.89070.019*
N3A0.3823 (3)0.24320 (18)0.69077 (14)0.0198 (4)
N3B0.2608 (3)0.10852 (18)0.77715 (13)0.0187 (4)
C1A0.1092 (4)0.3120 (2)0.36934 (18)0.0230 (5)
H1A0.08580.38940.36650.028*
C1B0.2768 (4)0.5164 (2)1.07967 (18)0.0253 (5)
H1B0.27760.59991.08040.030*
C2A0.0959 (4)0.2312 (2)0.29353 (18)0.0235 (5)
H2A0.06150.24700.23310.028*
C2B0.2821 (4)0.4394 (2)1.15643 (17)0.0228 (5)
H2B0.28630.46471.21530.027*
C3A0.1405 (3)0.1203 (2)0.31700 (17)0.0196 (5)
H3A0.13880.05530.27380.024*
C3B0.2803 (3)0.3171 (2)1.13637 (16)0.0188 (5)
H3B0.28340.25281.18050.023*
C4A0.1863 (3)0.1199 (2)0.41070 (16)0.0163 (5)
C4B0.2735 (3)0.3040 (2)1.04436 (16)0.0164 (5)
C5A0.2352 (3)0.0259 (2)0.46643 (16)0.0161 (5)
C5B0.2672 (3)0.1975 (2)0.99201 (16)0.0161 (5)
C6A0.2953 (3)0.1828 (2)0.45404 (16)0.0170 (5)
C6B0.2569 (3)0.0239 (2)1.00755 (16)0.0152 (4)
C7A0.3461 (3)0.2706 (2)0.60104 (17)0.0167 (5)
C7B0.2328 (3)0.1179 (2)0.86155 (16)0.0149 (4)
C8A0.3920 (4)0.3491 (2)0.73281 (18)0.0226 (5)
H8A0.41580.34810.79670.027*
C8B0.2079 (4)0.2002 (2)0.73046 (17)0.0210 (5)
H8B0.21730.20820.66910.025*
C9A0.3645 (4)0.4542 (2)0.67459 (18)0.0254 (6)
H9A0.36670.53230.69320.030*
C9B0.1420 (4)0.2768 (2)0.77978 (17)0.0219 (5)
H9B0.09980.34170.75700.026*
H1W0.486 (3)0.052 (3)0.750 (3)0.050*
H2W0.531 (4)0.0536 (3)0.744 (2)0.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S1A0.0280 (3)0.0159 (3)0.0215 (3)0.0091 (2)0.0033 (2)0.0003 (2)
S1B0.0384 (4)0.0153 (3)0.0203 (3)0.0137 (3)0.0053 (2)0.0009 (2)
S2A0.0424 (4)0.0177 (3)0.0177 (3)0.0141 (3)0.0017 (3)0.0029 (2)
S2B0.0280 (3)0.0126 (3)0.0167 (3)0.0081 (2)0.0033 (2)0.0014 (2)
S3A0.0336 (3)0.0113 (3)0.0234 (3)0.0059 (2)0.0030 (2)0.0002 (2)
S3B0.0286 (3)0.0172 (3)0.0218 (3)0.0133 (2)0.0095 (2)0.0050 (2)
O1A0.0312 (10)0.0176 (8)0.0176 (9)0.0089 (7)0.0043 (7)0.0004 (6)
O1B0.0396 (11)0.0183 (8)0.0183 (9)0.0139 (8)0.0064 (8)0.0011 (7)
O1W0.0232 (9)0.0117 (8)0.0228 (9)0.0067 (7)0.0012 (7)0.0014 (7)
N1A0.0231 (10)0.0127 (9)0.0151 (9)0.0065 (8)0.0015 (8)0.0000 (7)
N1B0.0183 (9)0.0120 (9)0.0145 (9)0.0060 (7)0.0019 (7)0.0006 (7)
N2A0.0217 (10)0.0104 (9)0.0175 (10)0.0043 (7)0.0018 (8)0.0020 (7)
N2B0.0189 (9)0.0123 (9)0.0181 (10)0.0079 (7)0.0046 (8)0.0001 (7)
N3A0.0210 (10)0.0154 (10)0.0204 (10)0.0035 (8)0.0015 (8)0.0019 (8)
N3B0.0229 (10)0.0139 (9)0.0192 (10)0.0061 (8)0.0042 (8)0.0007 (8)
C1A0.0238 (12)0.0190 (12)0.0285 (13)0.0101 (10)0.0045 (10)0.0058 (10)
C1B0.0376 (15)0.0148 (11)0.0254 (13)0.0125 (10)0.0030 (11)0.0042 (10)
C2A0.0228 (12)0.0283 (13)0.0220 (12)0.0117 (10)0.0037 (10)0.0058 (10)
C2B0.0313 (13)0.0177 (12)0.0184 (12)0.0090 (10)0.0006 (10)0.0026 (9)
C3A0.0189 (11)0.0183 (11)0.0220 (12)0.0066 (9)0.0043 (9)0.0014 (9)
C3B0.0210 (12)0.0130 (11)0.0202 (12)0.0059 (9)0.0009 (9)0.0031 (9)
C4A0.0141 (10)0.0137 (10)0.0195 (11)0.0031 (8)0.0023 (9)0.0008 (9)
C4B0.0153 (10)0.0117 (10)0.0218 (12)0.0055 (8)0.0020 (9)0.0031 (9)
C5A0.0139 (10)0.0120 (10)0.0199 (12)0.0018 (8)0.0022 (9)0.0015 (9)
C5B0.0139 (10)0.0124 (10)0.0212 (12)0.0045 (8)0.0024 (9)0.0010 (9)
C6A0.0164 (11)0.0137 (10)0.0182 (11)0.0030 (8)0.0002 (9)0.0009 (8)
C6B0.0132 (10)0.0100 (10)0.0201 (11)0.0022 (8)0.0009 (8)0.0003 (8)
C7A0.0150 (11)0.0107 (10)0.0219 (12)0.0016 (8)0.0026 (9)0.0003 (8)
C7B0.0137 (10)0.0109 (10)0.0194 (11)0.0042 (8)0.0015 (8)0.0006 (8)
C8A0.0228 (12)0.0218 (12)0.0217 (12)0.0054 (10)0.0026 (10)0.0062 (10)
C8B0.0245 (12)0.0181 (11)0.0196 (12)0.0059 (10)0.0029 (9)0.0042 (9)
C9A0.0304 (14)0.0169 (12)0.0269 (14)0.0048 (10)0.0036 (11)0.0082 (10)
C9B0.0268 (13)0.0195 (12)0.0219 (12)0.0102 (10)0.0042 (10)0.0088 (10)
Geometric parameters (Å, º) top
S1A—C1A1.709 (3)N2B—H2BA0.8600
S1A—C4A1.727 (2)N3A—C7A1.306 (3)
S1B—C1B1.705 (3)N3A—C8A1.379 (3)
S1B—C4B1.725 (2)N3B—C7B1.303 (3)
S2A—C6A1.655 (2)N3B—C8B1.382 (3)
S2B—C6B1.657 (2)C1A—C2A1.362 (4)
S3A—C9A1.721 (3)C1A—H1A0.9300
S3A—C7A1.728 (2)C1B—C2B1.366 (4)
S3B—C7B1.721 (2)C1B—H1B0.9300
S3B—C9B1.726 (2)C2A—C3A1.418 (3)
O1A—C5A1.231 (3)C2A—H2A0.9300
O1B—C5B1.230 (3)C2B—C3B1.411 (3)
O1W—H1W0.8199 (10)C2B—H2B0.9300
O1W—H2W0.8199 (11)C3A—C4A1.370 (3)
N1A—C5A1.387 (3)C3A—H3A0.9300
N1A—C6A1.396 (3)C3B—C4B1.372 (3)
N1A—H1AA0.8600C3B—H3B0.9300
N1B—C5B1.383 (3)C4A—C5A1.463 (3)
N1B—C6B1.393 (3)C4B—C5B1.461 (3)
N1B—H1BA0.8600C8A—C9A1.347 (4)
N2A—C6A1.344 (3)C8A—H8A0.9300
N2A—C7A1.385 (3)C8B—C9B1.340 (4)
N2A—H2AA0.8600C8B—H8B0.9300
N2B—C6B1.348 (3)C9A—H9A0.9300
N2B—C7B1.387 (3)C9B—H9B0.9300
C1A—S1A—C4A91.39 (12)C3A—C4A—C5A131.8 (2)
C1B—S1B—C4B91.37 (12)C3A—C4A—S1A111.53 (18)
C9A—S3A—C7A88.14 (12)C5A—C4A—S1A116.61 (17)
C7B—S3B—C9B88.16 (11)C3B—C4B—C5B131.9 (2)
H1W—O1W—H2W106 (2)C3B—C4B—S1B111.50 (17)
C5A—N1A—C6A127.1 (2)C5B—C4B—S1B116.60 (18)
C5A—N1A—H1AA116.4O1A—C5A—N1A122.3 (2)
C6A—N1A—H1AA116.4O1A—C5A—C4A121.5 (2)
C5B—N1B—C6B126.7 (2)N1A—C5A—C4A116.1 (2)
C5B—N1B—H1BA116.7O1B—C5B—N1B122.6 (2)
C6B—N1B—H1BA116.7O1B—C5B—C4B121.1 (2)
C6A—N2A—C7A128.3 (2)N1B—C5B—C4B116.3 (2)
C6A—N2A—H2AA115.9N2A—C6A—N1A114.9 (2)
C7A—N2A—H2AA115.9N2A—C6A—S2A125.44 (18)
C6B—N2B—C7B128.1 (2)N1A—C6A—S2A119.68 (17)
C6B—N2B—H2BA116.0N2B—C6B—N1B114.6 (2)
C7B—N2B—H2BA116.0N2B—C6B—S2B125.81 (17)
C7A—N3A—C8A110.1 (2)N1B—C6B—S2B119.57 (17)
C7B—N3B—C8B109.9 (2)N3A—C7A—N2A118.5 (2)
C2A—C1A—S1A112.31 (19)N3A—C7A—S3A115.58 (18)
C2A—C1A—H1A123.8N2A—C7A—S3A125.85 (18)
S1A—C1A—H1A123.8N3B—C7B—N2B118.3 (2)
C2B—C1B—S1B112.34 (19)N3B—C7B—S3B115.79 (17)
C2B—C1B—H1B123.8N2B—C7B—S3B125.78 (18)
S1B—C1B—H1B123.8C9A—C8A—N3A115.1 (2)
C1A—C2A—C3A112.5 (2)C9A—C8A—H8A122.4
C1A—C2A—H2A123.7N3A—C8A—H8A122.4
C3A—C2A—H2A123.7C9B—C8B—N3B115.3 (2)
C1B—C2B—C3B112.4 (2)C9B—C8B—H8B122.3
C1B—C2B—H2B123.8N3B—C8B—H8B122.3
C3B—C2B—H2B123.8C8A—C9A—S3A111.08 (19)
C4A—C3A—C2A112.3 (2)C8A—C9A—H9A124.5
C4A—C3A—H3A123.9S3A—C9A—H9A124.5
C2A—C3A—H3A123.9C8B—C9B—S3B110.83 (18)
C4B—C3B—C2B112.4 (2)C8B—C9B—H9B124.6
C4B—C3B—H3B123.8S3B—C9B—H9B124.6
C2B—C3B—H3B123.8
C4A—S1A—C1A—C2A0.6 (2)C7A—N2A—C6A—N1A176.5 (2)
C4B—S1B—C1B—C2B0.3 (2)C7A—N2A—C6A—S2A4.3 (4)
S1A—C1A—C2A—C3A0.5 (3)C5A—N1A—C6A—N2A10.2 (3)
S1B—C1B—C2B—C3B0.3 (3)C5A—N1A—C6A—S2A170.44 (18)
C1A—C2A—C3A—C4A0.1 (3)C7B—N2B—C6B—N1B175.1 (2)
C1B—C2B—C3B—C4B0.1 (3)C7B—N2B—C6B—S2B5.7 (4)
C2A—C3A—C4A—C5A177.8 (2)C5B—N1B—C6B—N2B13.9 (3)
C2A—C3A—C4A—S1A0.3 (3)C5B—N1B—C6B—S2B166.76 (18)
C1A—S1A—C4A—C3A0.49 (19)C8A—N3A—C7A—N2A177.4 (2)
C1A—S1A—C4A—C5A178.44 (19)C8A—N3A—C7A—S3A0.9 (3)
C2B—C3B—C4B—C5B179.2 (2)C6A—N2A—C7A—N3A176.3 (2)
C2B—C3B—C4B—S1B0.1 (3)C6A—N2A—C7A—S3A5.5 (4)
C1B—S1B—C4B—C3B0.2 (2)C9A—S3A—C7A—N3A0.9 (2)
C1B—S1B—C4B—C5B179.44 (19)C9A—S3A—C7A—N2A177.3 (2)
C6A—N1A—C5A—O1A7.0 (4)C8B—N3B—C7B—N2B174.97 (19)
C6A—N1A—C5A—C4A173.1 (2)C8B—N3B—C7B—S3B1.3 (3)
C3A—C4A—C5A—O1A170.5 (2)C6B—N2B—C7B—N3B174.7 (2)
S1A—C4A—C5A—O1A6.9 (3)C6B—N2B—C7B—S3B9.5 (3)
C3A—C4A—C5A—N1A9.6 (4)C9B—S3B—C7B—N3B1.54 (19)
S1A—C4A—C5A—N1A173.01 (16)C9B—S3B—C7B—N2B174.4 (2)
C6B—N1B—C5B—O1B6.8 (4)C7A—N3A—C8A—C9A0.5 (3)
C6B—N1B—C5B—C4B173.2 (2)C7B—N3B—C8B—C9B0.2 (3)
C3B—C4B—C5B—O1B176.5 (2)N3A—C8A—C9A—S3A0.2 (3)
S1B—C4B—C5B—O1B2.5 (3)C7A—S3A—C9A—C8A0.6 (2)
C3B—C4B—C5B—N1B3.5 (4)N3B—C8B—C9B—S3B0.9 (3)
S1B—C4B—C5B—N1B177.49 (16)C7B—S3B—C9B—C8B1.32 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1AA···O1Wi0.862.223.003 (3)152
N1B—H1BA···O1Wii0.862.142.973 (3)163
N2A—H2AA···O1A0.861.892.599 (3)138
N2B—H2BA···O1B0.861.902.588 (3)136
O1W—H1W···N3B0.82 (1)2.06 (1)2.852 (3)163 (4)
O1W—H2W···N3A0.82 (1)2.09 (1)2.892 (3)167 (3)
Symmetry codes: (i) x+1, y, z+1; (ii) x+1, y, z+2.

Experimental details

Crystal data
Chemical formulaC9H7N3OS3·0.5H2O
Mr278.37
Crystal system, space groupTriclinic, P1
Temperature (K)123
a, b, c (Å)7.4489 (4), 11.1060 (6), 14.7935 (7)
α, β, γ (°)93.559 (4), 99.813 (4), 107.789 (5)
V3)1139.74 (11)
Z4
Radiation typeCu Kα
µ (mm1)5.86
Crystal size (mm)0.35 × 0.25 × 0.18
Data collection
DiffractometerOxford Diffraction Xcalibur (Ruby, Gemini CCD)
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2011)
Tmin, Tmax0.441, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
7828, 4566, 3906
Rint0.034
(sin θ/λ)max1)0.629
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.110, 1.08
No. of reflections4566
No. of parameters304
No. of restraints3
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.43, 0.30

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1AA···O1Wi0.862.223.003 (3)151.5
N1B—H1BA···O1Wii0.862.142.973 (3)162.8
N2A—H2AA···O1A0.861.892.599 (3)138.3
N2B—H2BA···O1B0.861.902.588 (3)135.6
O1W—H1W···N3B0.8199 (10)2.056 (11)2.852 (3)163 (4)
O1W—H2W···N3A0.8199 (11)2.088 (8)2.892 (3)167 (3)
Symmetry codes: (i) x+1, y, z+1; (ii) x+1, y, z+2.
 

Acknowledgements

DPS and SP are grateful to Banaras Hindu University, Varanasi, for financial support. RJB acknowledges the NSF– MRI program (grant No. CHE0619278) for funds to purchase the X-ray diffractometer.

References

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