3-Hydr­oxy-4-methoxy­benzaldehyde thio­semicarbazone hemihydrate

Fun, H.-K.; Kia, R.; D'Silva, E.D.; Patil, P.S.; Dharmaprakash, S.M.

doi:10.1107/S1600536808035617

organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Pages o2274-o2275

doi:10.1107/S1600536808035617

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3-Hydroxy-4-methoxybenzaldehyde thiosemicarbazone hemihydrate

Hoong-Kun Fun,^a ^* Reza Kia,^a E. Deepak D'Silva,^b P. S. Patil ^b,^c and S. M. Dharmaprakash ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bDepartment of Studies in Physics, Mangalore University, Mangalagangotri, Mangalore 574 199, India, and ^cDepartment of Physics, KLE Society's Institute of Technology, Gokul Road, Hubli 590 030, India
^*Correspondence e-mail: hkfun@usm.my

(Received 29 October 2008; accepted 30 October 2008; online 8 November 2008)

The asymmetric unit of the title compound, C₉H₁₁N₃O₂S·0.5H₂O, comprises two crystallograpically independent thiosemicarbazone molecules (A and B) and a water molecule of crystallization. In each of the thiosemicarbazone molecules, intramolecular O—H⋯O and N—H⋯N hydrogen bonds form five-membered rings, producing S(5) ring motifs. Intermolecular O—H⋯S and N—H⋯O interactions between molecule B and the water molecule form a six-membered ring, producing an R₂²(6) ring motif. Intermolecular N—H⋯S hydrogen bonds form dimers involving pairs of both A and B molecules, which form R₂²(8) ring motifs. The angles between the aromatic ring and thiourea unit in the two molecules are 0.80 (6) and 3.28 (5)°, which proves that each molecule is fairly planar. The crystal structure is stabilized by intermolecular O—H⋯S (×2), O—H⋯O, N—H⋯S (×2) and N—H⋯O (×2) hydrogen bonds and C—H⋯O (×2) contacts to form a three-dimensional network.

Related literature

For details of hydrogen-bond motifs, see: Bernstein et al. (1995 ). For background to thiosemicarbazones, see: Al-Awadi et al. (2008 ); Kizilcikli et al. (2004 ); Mishra et al. (2006 ). For a related structure, see: Ferrari et al. (2001 ).

Experimental

Crystal data

C₉H₁₁N₃O₂S·0.5H₂O
M_r = 234.28
Triclinic, $[P \overline 1]$
a = 10.5288 (2) Å
b = 10.7045 (2) Å
c = 11.8154 (2) Å
α = 68.438 (1)°
β = 68.917 (1)°
γ = 68.114 (1)°
V = 1110.28 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 100.0 (1) K
0.45 × 0.32 × 0.10 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.884, T_max = 0.973
45467 measured reflections
10830 independent reflections
8078 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.116
S = 1.10
10830 reflections
314 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.90 e Å⁻³
Δρ_min = −0.63 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H2W1⋯S1B	0.86	2.28	3.1257 (9)	169
O1W—H1W1⋯O1Aⁱ	0.85	1.95	2.7955 (12)	173
N2A—H2NA⋯S1Aⁱⁱ	0.929 (18)	2.450 (18)	3.3732 (9)	172.6 (18)
N2B—H2NB⋯S1Bⁱⁱⁱ	0.842 (19)	2.571 (18)	3.4055 (10)	171.2 (18)
N3A—H3NA⋯N1A	0.847 (19)	2.258 (15)	2.6129 (14)	105.4 (12)
N3A—H3NB⋯O1W^iv	0.864 (16)	2.000 (15)	2.8408 (12)	164.0 (17)
N3B—H3NC⋯O1W	0.833 (19)	2.399 (19)	3.1492 (14)	150.2 (17)
N3B—H3ND⋯N1B	0.875 (19)	2.288 (17)	2.6554 (14)	105.2 (13)
O1A—H1OA⋯O2A	0.81 (2)	2.185 (18)	2.6292 (12)	114.5 (15)
O1B—H1OB⋯S1A^v	0.82 (2)	2.685 (19)	3.2346 (10)	125.9 (16)
O1B—H1OB⋯O2B	0.82 (2)	2.251 (19)	2.6949 (13)	114.4 (16)
C1B—H1BA⋯O1W^vi	0.93	2.40	3.3140 (14)	169
C9B—H9BA⋯O2A^vii	0.96	2.51	3.2286 (15)	131
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+2, -y+1, -z; (iii) -x+1, -y, -z+1; (iv) -x+1, -y+1, -z+1; (v) x-1, y-1, z; (vi) x, y-1, z; (vii) -x, -y, -z.

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); 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, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808035617/tk2321sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808035617/tk2321Isup2.hkl

checkCIF report

Comment top

Intriguing chelating patterns, biomedical properties, structural diversity and ion-sensing abilities (Al-Awadi et al., 2008; Kizilcikli et al., 2004; Mishra et al., 2006) have made thiosemicarbazones a class of compounds of immense importance. We report herein the crystal structure of the title compound, (I).

The bond lengths and angles in (I), Fig. 1, agree with those in a related structure (Ferrari et al. 2001). Intramolecular O—H···O and N—H···N hydrogen bonds, in each molecule of A and B, form five-membered rings, producing S(5) ring motifs (Bernstein et al. 1995). The angle between the aromatic ring and the thiourea unit in each of molecule A and B is 0.80 (6) and 3.28 (5)°, respectively, which indicates each molecule is almost planar. Intermolecular O—H···S and N—H···O interactions between molecule B and the water molecule form a six-membered ring, producing a R₂²(6) ring motif. Intermolecular N—H···S interactions for pairs of molecule A and similarly for pairs of molecules B lead to the formation of dimers with R₂²(8) ring motifs (Bernstein et al. 1995). The crystal structure is stabilized by intermolecular O—H···S, O—H···O, N—H···S (x 2) and N—H···O (x 2) hydrogen bonds and C—H···O (x 2) contacts, see Table 1. In the 3-D crystal structure the water molecules link neghbouring molecules to form 1-D chains along the b-axis of the unit cell (Fig. 2).

Related literature top

For related literature on hydrogen-bond motifs, see: Bernstein et al. (1995). For background on thiosemicarbazones, see: Al-Awadi et al. (2008); Kizilcikli et al. (2004); Mishra et al. (2006). For a related structure, see: Ferrari et al. (2001).

Experimental top

3-Hydroxy-4-methoxy benzaldehyde (0.075 mol) and thiosemicarbazone (0.05 mol) were dissolved in a sufficient volume of methanol and the mixture was refluxed for 4 h until the whole volume of the mixture attains a pale-yellow colour. The mixture was then allowed to cool, poured into a beaker and kept aside for evaporation. The resulting crude sample was recrystallized twice from methanol. Pure light-yellow crystals of (I) were then obtained.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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, 2003).

Figures top

	Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids and the atomic numbering. Dashed lines show intramolecular hydrogen bonds.
	Fig. 2. Partial crystal packing in (I), viewed down the c-axis, showing 1-D chains mediated by the water molecule along the b-axis. Intra- and inter-molecular interactions are drawn as dashed lines.

3-Hydroxy-4-methoxybenzaldehyde thiosemicarbazone hemihydrate top

Crystal data top

C₉H₁₁N₃O₂S·0.5H₂O	Z = 4
M_r = 234.28	F(000) = 492
Triclinic, P1	D_x = 1.402 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.5288 (2) Å	Cell parameters from 9992 reflections
b = 10.7045 (2) Å	θ = 2.5–36.3°
c = 11.8154 (2) Å	µ = 0.28 mm⁻¹
α = 68.438 (1)°	T = 100 K
β = 68.917 (1)°	Plate, light yellow
γ = 68.114 (1)°	0.45 × 0.32 × 0.10 mm
V = 1110.28 (4) Å³

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	10830 independent reflections
Radiation source: fine-focus sealed tube	8078 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ϕ and ω scans	θ_max = 36.6°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −17→17
T_min = 0.884, T_max = 0.973	k = −17→17
45467 measured reflections	l = −19→19

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0547P)² + 0.1125P] where P = (F_o² + 2F_c²)/3
10830 reflections	(Δ/σ)_max = 0.001
314 parameters	Δρ_max = 0.90 e Å⁻³
0 restraints	Δρ_min = −0.63 e Å⁻³

Crystal data top

C₉H₁₁N₃O₂S·0.5H₂O	γ = 68.114 (1)°
M_r = 234.28	V = 1110.28 (4) Å³
Triclinic, P1	Z = 4
a = 10.5288 (2) Å	Mo Kα radiation
b = 10.7045 (2) Å	µ = 0.28 mm⁻¹
c = 11.8154 (2) Å	T = 100 K
α = 68.438 (1)°	0.45 × 0.32 × 0.10 mm
β = 68.917 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	10830 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	8078 reflections with I > 2σ(I)
T_min = 0.884, T_max = 0.973	R_int = 0.040
45467 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.90 e Å⁻³
10830 reflections	Δρ_min = −0.63 e Å⁻³
314 parameters

Special details top

Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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
S1A	0.96703 (3)	0.48913 (3)	0.19973 (2)	0.01747 (6)
O1A	0.51514 (8)	0.27402 (9)	−0.26347 (7)	0.02001 (15)
O2A	0.30169 (8)	0.21411 (9)	−0.07261 (7)	0.01997 (15)
N1A	0.71556 (9)	0.38149 (9)	0.09845 (8)	0.01559 (15)
N2A	0.82582 (9)	0.42443 (9)	0.09440 (8)	0.01634 (15)
N3A	0.72833 (10)	0.41202 (10)	0.30323 (9)	0.01863 (16)
C1A	0.60929 (10)	0.32375 (11)	−0.13430 (9)	0.01602 (17)
H1AA	0.6832	0.3453	−0.2035	0.019*
C2A	0.50692 (10)	0.28289 (11)	−0.14735 (9)	0.01535 (16)
C3A	0.39489 (10)	0.25053 (10)	−0.04411 (9)	0.01556 (16)
C4A	0.38655 (10)	0.25938 (11)	0.07304 (9)	0.01677 (17)
H4AA	0.3126	0.2376	0.1421	0.020*
C5A	0.48947 (10)	0.30101 (11)	0.08621 (9)	0.01594 (17)
H5AA	0.4835	0.3078	0.1643	0.019*
C6A	0.60192 (10)	0.33279 (10)	−0.01652 (9)	0.01479 (16)
C7A	0.71238 (10)	0.37674 (11)	−0.00763 (9)	0.01642 (17)
H7AA	0.7819	0.4018	−0.0799	0.020*
C8A	0.83058 (10)	0.43992 (10)	0.20092 (9)	0.01451 (16)
C9A	0.18681 (12)	0.17340 (13)	0.02852 (11)	0.0237 (2)
H9AA	0.1261	0.1552	−0.0041	0.036*
H9AB	0.1337	0.2473	0.0688	0.036*
H9AC	0.2236	0.0904	0.0886	0.036*
S1B	0.47040 (3)	0.21971 (3)	0.47447 (3)	0.02029 (6)
O1B	0.02689 (9)	−0.32448 (8)	0.32698 (8)	0.02095 (15)
O2B	−0.18810 (8)	−0.11332 (8)	0.24783 (7)	0.01905 (14)
N1B	0.20913 (9)	0.10835 (9)	0.38890 (8)	0.01597 (15)
N2B	0.31944 (9)	0.10741 (9)	0.42677 (8)	0.01711 (15)
N3B	0.23043 (10)	0.34380 (10)	0.39796 (9)	0.02002 (17)
C1B	0.10696 (10)	−0.16764 (10)	0.36407 (9)	0.01606 (17)
H1BA	0.1780	−0.2427	0.3942	0.019*
C2B	0.01113 (10)	−0.19098 (10)	0.32466 (9)	0.01548 (16)
C3B	−0.09831 (10)	−0.07809 (10)	0.28235 (9)	0.01488 (16)
C4B	−0.10910 (10)	0.05636 (10)	0.27978 (9)	0.01613 (17)
H4BA	−0.1822	0.1310	0.2526	0.019*
C5B	−0.01134 (10)	0.07990 (10)	0.31756 (9)	0.01574 (16)
H5BA	−0.0188	0.1701	0.3152	0.019*
C6B	0.09823 (10)	−0.03191 (10)	0.35910 (9)	0.01469 (16)
C7B	0.20549 (10)	−0.01329 (10)	0.39715 (9)	0.01585 (17)
H7BA	0.2733	−0.0917	0.4283	0.019*
C8B	0.32919 (10)	0.22659 (11)	0.43096 (9)	0.01633 (17)
C9B	−0.30345 (11)	−0.00063 (12)	0.20815 (11)	0.0222 (2)
H9BA	−0.3624	−0.0365	0.1894	0.033*
H9BB	−0.2670	0.0658	0.1342	0.033*
H9BC	−0.3583	0.0444	0.2743	0.033*
O1W	0.34588 (8)	0.53871 (8)	0.45766 (7)	0.02077 (15)
H2W1	0.3911	0.4524	0.4611	0.031*
H1W1	0.3945	0.5902	0.3981	0.031*
H2NA	0.8880 (18)	0.4499 (18)	0.0167 (16)	0.037 (4)*
H2NB	0.3777 (17)	0.0311 (18)	0.4514 (15)	0.032 (4)*
H3NA	0.6636 (16)	0.3855 (16)	0.3001 (14)	0.025 (4)*
H3NB	0.7234 (15)	0.4214 (16)	0.3744 (14)	0.025 (4)*
H3NC	0.2333 (17)	0.4172 (18)	0.4051 (15)	0.033 (4)*
H3ND	0.1594 (16)	0.3384 (16)	0.3798 (14)	0.026 (4)*
H1OA	0.4418 (18)	0.2630 (18)	−0.2614 (16)	0.036 (4)*
H1OB	−0.0391 (18)	−0.3255 (18)	0.3063 (16)	0.037 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1A	0.01803 (11)	0.02175 (12)	0.01820 (11)	−0.01016 (9)	−0.00575 (8)	−0.00572 (9)
O1A	0.0214 (3)	0.0294 (4)	0.0160 (3)	−0.0126 (3)	−0.0040 (3)	−0.0087 (3)
O2A	0.0179 (3)	0.0289 (4)	0.0197 (3)	−0.0134 (3)	−0.0029 (3)	−0.0087 (3)
N1A	0.0144 (3)	0.0177 (4)	0.0181 (4)	−0.0063 (3)	−0.0058 (3)	−0.0050 (3)
N2A	0.0165 (3)	0.0214 (4)	0.0155 (3)	−0.0096 (3)	−0.0047 (3)	−0.0048 (3)
N3A	0.0176 (4)	0.0251 (4)	0.0174 (4)	−0.0100 (3)	−0.0029 (3)	−0.0079 (3)
C1A	0.0152 (4)	0.0199 (4)	0.0155 (4)	−0.0075 (3)	−0.0031 (3)	−0.0057 (3)
C2A	0.0166 (4)	0.0179 (4)	0.0149 (4)	−0.0063 (3)	−0.0049 (3)	−0.0057 (3)
C3A	0.0144 (4)	0.0174 (4)	0.0179 (4)	−0.0066 (3)	−0.0047 (3)	−0.0054 (3)
C4A	0.0162 (4)	0.0203 (4)	0.0156 (4)	−0.0079 (3)	−0.0031 (3)	−0.0048 (3)
C5A	0.0163 (4)	0.0197 (4)	0.0141 (4)	−0.0068 (3)	−0.0042 (3)	−0.0049 (3)
C6A	0.0142 (4)	0.0165 (4)	0.0160 (4)	−0.0052 (3)	−0.0051 (3)	−0.0047 (3)
C7A	0.0151 (4)	0.0193 (4)	0.0172 (4)	−0.0070 (3)	−0.0045 (3)	−0.0048 (3)
C8A	0.0147 (4)	0.0142 (4)	0.0167 (4)	−0.0042 (3)	−0.0058 (3)	−0.0045 (3)
C9A	0.0193 (4)	0.0321 (6)	0.0253 (5)	−0.0151 (4)	−0.0009 (4)	−0.0105 (4)
S1B	0.01952 (11)	0.01809 (12)	0.02886 (13)	−0.00806 (9)	−0.01069 (10)	−0.00520 (9)
O1B	0.0208 (3)	0.0155 (3)	0.0330 (4)	−0.0036 (3)	−0.0123 (3)	−0.0099 (3)
O2B	0.0178 (3)	0.0175 (3)	0.0280 (4)	−0.0032 (3)	−0.0118 (3)	−0.0089 (3)
N1B	0.0142 (3)	0.0186 (4)	0.0181 (4)	−0.0064 (3)	−0.0052 (3)	−0.0054 (3)
N2B	0.0157 (3)	0.0157 (4)	0.0236 (4)	−0.0053 (3)	−0.0086 (3)	−0.0049 (3)
N3B	0.0193 (4)	0.0159 (4)	0.0279 (4)	−0.0046 (3)	−0.0095 (3)	−0.0061 (3)
C1B	0.0148 (4)	0.0152 (4)	0.0201 (4)	−0.0028 (3)	−0.0063 (3)	−0.0065 (3)
C2B	0.0158 (4)	0.0141 (4)	0.0191 (4)	−0.0044 (3)	−0.0049 (3)	−0.0067 (3)
C3B	0.0146 (4)	0.0169 (4)	0.0164 (4)	−0.0057 (3)	−0.0047 (3)	−0.0059 (3)
C4B	0.0168 (4)	0.0152 (4)	0.0187 (4)	−0.0045 (3)	−0.0072 (3)	−0.0045 (3)
C5B	0.0170 (4)	0.0137 (4)	0.0183 (4)	−0.0050 (3)	−0.0058 (3)	−0.0044 (3)
C6B	0.0148 (4)	0.0156 (4)	0.0158 (4)	−0.0055 (3)	−0.0041 (3)	−0.0050 (3)
C7B	0.0150 (4)	0.0164 (4)	0.0182 (4)	−0.0050 (3)	−0.0054 (3)	−0.0051 (3)
C8B	0.0165 (4)	0.0172 (4)	0.0173 (4)	−0.0073 (3)	−0.0039 (3)	−0.0045 (3)
C9B	0.0193 (4)	0.0214 (5)	0.0322 (5)	−0.0022 (4)	−0.0141 (4)	−0.0104 (4)
O1W	0.0225 (4)	0.0180 (3)	0.0206 (3)	−0.0044 (3)	−0.0056 (3)	−0.0051 (3)

Geometric parameters (Å, º) top

S1A—C8A	1.6988 (10)	O1B—C2B	1.3668 (12)
O1A—C2A	1.3794 (11)	O1B—H1OB	0.820 (17)
O1A—H1OA	0.814 (17)	O2B—C3B	1.3633 (12)
O2A—C3A	1.3593 (12)	O2B—C9B	1.4324 (12)
O2A—C9A	1.4322 (13)	N1B—C7B	1.2836 (13)
N1A—C7A	1.2857 (12)	N1B—N2B	1.3824 (11)
N1A—N2A	1.3794 (12)	N2B—C8B	1.3373 (13)
N2A—C8A	1.3486 (12)	N2B—H2NB	0.841 (17)
N2A—H2NA	0.928 (17)	N3B—C8B	1.3292 (13)
N3A—C8A	1.3219 (13)	N3B—H3NC	0.832 (17)
N3A—H3NA	0.847 (16)	N3B—H3ND	0.875 (16)
N3A—H3NB	0.864 (15)	C1B—C2B	1.3816 (13)
C1A—C2A	1.3776 (13)	C1B—C6B	1.4016 (14)
C1A—C6A	1.4028 (13)	C1B—H1BA	0.9300
C1A—H1AA	0.9300	C2B—C3B	1.4037 (13)
C2A—C3A	1.3993 (14)	C3B—C4B	1.3905 (14)
C3A—C4A	1.3912 (13)	C4B—C5B	1.3888 (13)
C4A—C5A	1.3890 (14)	C4B—H4BA	0.9300
C4A—H4AA	0.9300	C5B—C6B	1.3966 (13)
C5A—C6A	1.3977 (14)	C5B—H5BA	0.9300
C5A—H5AA	0.9300	C6B—C7B	1.4547 (13)
C6A—C7A	1.4550 (13)	C7B—H7BA	0.9300
C7A—H7AA	0.9300	C9B—H9BA	0.9600
C9A—H9AA	0.9600	C9B—H9BB	0.9600
C9A—H9AB	0.9600	C9B—H9BC	0.9600
C9A—H9AC	0.9600	O1W—H2W1	0.8600
S1B—C8B	1.7090 (10)	O1W—H1W1	0.8531

C2A—O1A—H1OA	109.5 (12)	C3B—O2B—C9B	115.87 (8)
C3A—O2A—C9A	117.44 (8)	C7B—N1B—N2B	114.34 (8)
C7A—N1A—N2A	115.51 (8)	C8B—N2B—N1B	120.11 (8)
C8A—N2A—N1A	118.54 (8)	C8B—N2B—H2NB	119.9 (11)
C8A—N2A—H2NA	123.0 (10)	N1B—N2B—H2NB	119.9 (11)
N1A—N2A—H2NA	118.2 (10)	C8B—N3B—H3NC	118.1 (11)
C8A—N3A—H3NA	120.0 (10)	C8B—N3B—H3ND	118.5 (10)
C8A—N3A—H3NB	122.4 (10)	H3NC—N3B—H3ND	122.8 (15)
H3NA—N3A—H3NB	117.6 (14)	C2B—C1B—C6B	120.65 (9)
C2A—C1A—C6A	119.93 (9)	C2B—C1B—H1BA	119.7
C2A—C1A—H1AA	120.0	C6B—C1B—H1BA	119.7
C6A—C1A—H1AA	120.0	O1B—C2B—C1B	118.58 (9)
C1A—C2A—O1A	119.54 (9)	O1B—C2B—C3B	121.76 (9)
C1A—C2A—C3A	120.63 (9)	C1B—C2B—C3B	119.67 (9)
O1A—C2A—C3A	119.82 (8)	O2B—C3B—C4B	125.42 (9)
O2A—C3A—C4A	126.57 (9)	O2B—C3B—C2B	114.74 (9)
O2A—C3A—C2A	113.56 (8)	C4B—C3B—C2B	119.84 (9)
C4A—C3A—C2A	119.86 (9)	C5B—C4B—C3B	120.41 (9)
C5A—C4A—C3A	119.55 (9)	C5B—C4B—H4BA	119.8
C5A—C4A—H4AA	120.2	C3B—C4B—H4BA	119.8
C3A—C4A—H4AA	120.2	C4B—C5B—C6B	120.01 (9)
C4A—C5A—C6A	120.79 (9)	C4B—C5B—H5BA	120.0
C4A—C5A—H5AA	119.6	C6B—C5B—H5BA	120.0
C6A—C5A—H5AA	119.6	C5B—C6B—C1B	119.39 (9)
C5A—C6A—C1A	119.24 (9)	C5B—C6B—C7B	122.48 (9)
C5A—C6A—C7A	122.91 (8)	C1B—C6B—C7B	118.13 (9)
C1A—C6A—C7A	117.85 (9)	N1B—C7B—C6B	121.82 (9)
N1A—C7A—C6A	121.12 (9)	N1B—C7B—H7BA	119.1
N1A—C7A—H7AA	119.4	C6B—C7B—H7BA	119.1
C6A—C7A—H7AA	119.4	N3B—C8B—N2B	118.02 (9)
N3A—C8A—N2A	117.23 (9)	N3B—C8B—S1B	123.94 (8)
N3A—C8A—S1A	123.10 (7)	N2B—C8B—S1B	118.01 (7)
N2A—C8A—S1A	119.64 (7)	O2B—C9B—H9BA	109.5
O2A—C9A—H9AA	109.5	O2B—C9B—H9BB	109.5
O2A—C9A—H9AB	109.5	H9BA—C9B—H9BB	109.5
H9AA—C9A—H9AB	109.5	O2B—C9B—H9BC	109.5
O2A—C9A—H9AC	109.5	H9BA—C9B—H9BC	109.5
H9AA—C9A—H9AC	109.5	H9BB—C9B—H9BC	109.5
H9AB—C9A—H9AC	109.5	H2W1—O1W—H1W1	109.0
C2B—O1B—H1OB	109.3 (12)

C7A—N1A—N2A—C8A	176.03 (9)	C7B—N1B—N2B—C8B	−175.36 (9)
C6A—C1A—C2A—O1A	−179.88 (9)	C6B—C1B—C2B—O1B	177.67 (9)
C6A—C1A—C2A—C3A	0.19 (15)	C6B—C1B—C2B—C3B	−1.69 (15)
C9A—O2A—C3A—C4A	−3.53 (16)	C9B—O2B—C3B—C4B	−1.14 (14)
C9A—O2A—C3A—C2A	177.37 (9)	C9B—O2B—C3B—C2B	178.05 (9)
C1A—C2A—C3A—O2A	179.06 (9)	O1B—C2B—C3B—O2B	1.74 (14)
O1A—C2A—C3A—O2A	−0.87 (14)	C1B—C2B—C3B—O2B	−178.92 (9)
C1A—C2A—C3A—C4A	−0.10 (15)	O1B—C2B—C3B—C4B	−179.02 (9)
O1A—C2A—C3A—C4A	179.97 (9)	C1B—C2B—C3B—C4B	0.33 (15)
O2A—C3A—C4A—C5A	−178.74 (10)	O2B—C3B—C4B—C5B	179.85 (9)
C2A—C3A—C4A—C5A	0.30 (15)	C2B—C3B—C4B—C5B	0.69 (15)
C3A—C4A—C5A—C6A	−0.61 (15)	C3B—C4B—C5B—C6B	−0.35 (15)
C4A—C5A—C6A—C1A	0.70 (15)	C4B—C5B—C6B—C1B	−1.00 (15)
C4A—C5A—C6A—C7A	−179.96 (10)	C4B—C5B—C6B—C7B	178.61 (9)
C2A—C1A—C6A—C5A	−0.49 (15)	C2B—C1B—C6B—C5B	2.03 (15)
C2A—C1A—C6A—C7A	−179.86 (9)	C2B—C1B—C6B—C7B	−177.59 (9)
N2A—N1A—C7A—C6A	179.81 (9)	N2B—N1B—C7B—C6B	−178.82 (9)
C5A—C6A—C7A—N1A	3.67 (16)	C5B—C6B—C7B—N1B	−3.38 (15)
C1A—C6A—C7A—N1A	−176.98 (9)	C1B—C6B—C7B—N1B	176.23 (9)
N1A—N2A—C8A—N3A	0.26 (14)	N1B—N2B—C8B—N3B	0.04 (14)
N1A—N2A—C8A—S1A	178.63 (7)	N1B—N2B—C8B—S1B	−178.29 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W1···S1B	0.86	2.28	3.1257 (9)	169
O1W—H1W1···O1Aⁱ	0.85	1.95	2.7955 (12)	173
N2A—H2NA···S1Aⁱⁱ	0.929 (18)	2.450 (18)	3.3732 (9)	172.6 (18)
N2B—H2NB···S1Bⁱⁱⁱ	0.842 (19)	2.571 (18)	3.4055 (10)	171.2 (18)
N3A—H3NA···N1A	0.847 (19)	2.258 (15)	2.6129 (14)	105.4 (12)
N3A—H3NB···O1W^iv	0.864 (16)	2.000 (15)	2.8408 (12)	164.0 (17)
N3B—H3NC···O1W	0.833 (19)	2.399 (19)	3.1492 (14)	150.2 (17)
N3B—H3ND···N1B	0.875 (19)	2.288 (17)	2.6554 (14)	105.2 (13)
O1A—H1OA···O2A	0.81 (2)	2.185 (18)	2.6292 (12)	114.5 (15)
O1B—H1OB···S1A^v	0.82 (2)	2.685 (19)	3.2346 (10)	125.9 (16)
O1B—H1OB···O2B	0.82 (2)	2.251 (19)	2.6949 (13)	114.4 (16)
C1B—H1BA···O1W^vi	0.93	2.40	3.3140 (14)	169
C9B—H9BA···O2A^vii	0.96	2.51	3.2286 (15)	131

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

Experimental details

Crystal data
Chemical formula	C₉H₁₁N₃O₂S·0.5H₂O
M_r	234.28
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	10.5288 (2), 10.7045 (2), 11.8154 (2)
α, β, γ (°)	68.438 (1), 68.917 (1), 68.114 (1)
V (Å³)	1110.28 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.45 × 0.32 × 0.10

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.884, 0.973
No. of measured, independent and observed [I > 2σ(I)] reflections	45467, 10830, 8078
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.839

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.116, 1.10
No. of reflections	10830
No. of parameters	314
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.90, −0.63

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W1···S1B	0.86	2.28	3.1257 (9)	169
O1W—H1W1···O1Aⁱ	0.85	1.95	2.7955 (12)	173
N2A—H2NA···S1Aⁱⁱ	0.929 (18)	2.450 (18)	3.3732 (9)	172.6 (18)
N2B—H2NB···S1Bⁱⁱⁱ	0.842 (19)	2.571 (18)	3.4055 (10)	171.2 (18)
N3A—H3NA···N1A	0.847 (19)	2.258 (15)	2.6129 (14)	105.4 (12)
N3A—H3NB···O1W^iv	0.864 (16)	2.000 (15)	2.8408 (12)	164.0 (17)
N3B—H3NC···O1W	0.833 (19)	2.399 (19)	3.1492 (14)	150.2 (17)
N3B—H3ND···N1B	0.875 (19)	2.288 (17)	2.6554 (14)	105.2 (13)
O1A—H1OA···O2A	0.81 (2)	2.185 (18)	2.6292 (12)	114.5 (15)
O1B—H1OB···S1A^v	0.82 (2)	2.685 (19)	3.2346 (10)	125.9 (16)
O1B—H1OB···O2B	0.82 (2)	2.251 (19)	2.6949 (13)	114.4 (16)
C1B—H1BA···O1W^vi	0.93	2.40	3.3140 (14)	169
C9B—H9BA···O2A^vii	0.96	2.51	3.2286 (15)	131

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

Acknowledgements

H-KF and RK thank the Malaysian Government and Universiti Sains Malaysia for Science Fund grant No. 305/PFIZIK/613312. RK thanks Universiti Sains Malaysia for a postdoctoral research fellowship. This work was supported by the Department of Science and Technology (DST), Government of India (grant No. SR/S2/LOP-17/2006).

References

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