3,4-Dihydroxy­benzaldehyde thio­semi­carbazone

Tan, K.W.; Farina, Y.; Ng, C.H.; Maah, M.J.; Ng, S.W.

doi:10.1107/S160053680801386X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1073

doi:10.1107/S160053680801386X

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3,4-Dihydroxybenzaldehyde thiosemicarbazone

Kong Wai Tan,^a Yang Farina,^b Chew Hee Ng,^c ^* Mohd Jamil Maah ^a and Seik Weng Ng ^a

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, ^bSchool of Chemical Science and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Malaysia, and ^cFaculty of Engineering and Science, Universiti Tunku Abdul Rahman, 53300 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 6 May 2008; accepted 9 May 2008; online 14 May 2008)

The asymmetric unit of the title compound, C₈H₉N₃O₂S, contains three independent molecules which are stacked approximately over each other. In the crystal structure, centrosymmetric pairs of molecules are formed through intermolecular hydroxy–hydroxy O—H⋯O and hydroxy–sulfur O—H⋯S hydrogen bonds which are, in turn, linked into a two-dimensional network by N—H⋯O(hydroxy) hydrogen bonds.

Related literature

For the structure of 3,4-dihydroxybenzaldehyde 4-phenylthiosemicarbazone, see: Swesi et al. (2006 ). For some metal complexes of the ligand, see: Zhu et al. (1991 , 1997 ).

Experimental

Crystal data

C₈H₉N₃O₂S
M_r = 211.24
Triclinic, $[P \overline 1]$
a = 10.657 (2) Å
b = 11.794 (2) Å
c = 12.356 (2) Å
α = 111.657 (2)°
β = 104.082 (2)°
γ = 90.929 (2)°
V = 1390.2 (4) Å³
Z = 6
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 100 (2) K
0.20 × 0.18 × 0.04 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.938, T_max = 0.987
8792 measured reflections
6298 independent reflections
3727 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.189
S = 1.01
6298 reflections
397 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1o⋯O6ⁱ	0.84 (1)	2.07 (3)	2.784 (3)	143 (4)
O2—H2o⋯S1ⁱⁱ	0.84 (1)	2.47 (1)	3.300 (2)	171 (4)
N1—H1n2⋯O5ⁱⁱⁱ	0.88	2.00	2.856 (4)	163
O3—H3o⋯O4ⁱ	0.84 (1)	2.11 (4)	2.732 (3)	130 (4)
O4—H4o⋯S2ⁱⁱ	0.84 (1)	2.38 (1)	3.219 (2)	174 (4)
N4—H4n2⋯O3ⁱⁱⁱ	0.88	2.05	2.900 (4)	162
O5—H5o⋯O2ⁱ	0.84 (1)	2.16 (4)	2.742 (3)	127 (4)
O6—H6o⋯S3ⁱⁱ	0.84 (1)	2.40 (1)	3.244 (2)	177 (4)
N7—H7n2⋯O1ⁱⁱⁱ	0.88	2.13	2.981 (4)	161
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) x, y, z+1; (iii) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680801386X/lh2626sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680801386X/lh2626Isup2.hkl

checkCIF report

Comment top

A previous study of Schiff bases derived by condensing substituted benzaldehydes with 4-phenylthiosemicarbazides describes the 3,4-dihydroxybenzaldehyde derivative, which crystallizes as a hemihydrate. The compound features extensive hydrogen bonds (Swesi et al., 2006). The condensation product of the reaction between thiosemicarbazide and 3,4-dihydroxybenzaldehyde has an amino –NH₂ group in place of the phenyl group. In the crystal structure, a molecule is linked to an adjacent molecule by a hydrogen bond [O–H_3-hydroxy···O_4-hydroxy]; it is linked to another adjacent molecule by another hydrogen bond [O–H_4-hydroxy···S]. The structure is consolidated into a two-dimensional network motif by a N_terminal–H···O_4-hydroxy hydrogen bond. The asymmetric unit features three molecules that are approximately stacked over each other (Fig. 1).

Related literature top

For the structure of 3,4-dihydroxybenzaldehyde 4-phenylthiosemicarbazone, see: Swesi et al. (2006). For some metal complexes of the ligand, see: Zhu et al. (1991, 1997).

Experimental top

Thiosemicarbazide (0.09 g, 1 mmol) and 2,4-dihydroxybenzaldehyde (0.14 g, 1 mmol) were heated in an ethanol/water mixture (20/5 ml) for 3 h. Slow evaporation of the solvent yielded yellow crystals.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

Fig. 1. Thermal ellipsoid (Barbour, 2001) plot of the three independent molecules of C₁₄H₁₃N₃O₂S at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radii.

3,4-Dihydroxybenzaldehyde thiosemicarbazone top

Crystal data top

C₈H₉N₃O₂S	Z = 6
M_r = 211.24	F(000) = 660
Triclinic, P1	D_x = 1.514 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.657 (2) Å	Cell parameters from 1478 reflections
b = 11.794 (2) Å	θ = 2.7–27.8°
c = 12.356 (2) Å	µ = 0.33 mm⁻¹
α = 111.657 (2)°	T = 100 K
β = 104.082 (2)°	Block, yellow
γ = 90.929 (2)°	0.20 × 0.18 × 0.04 mm
V = 1390.2 (4) Å³

Data collection top

Bruker SMART APEX diffractometer	6298 independent reflections
Radiation source: fine-focus sealed tube	3727 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω scans	θ_max = 27.5°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.938, T_max = 0.987	k = −15→9
8792 measured reflections	l = −14→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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.189	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.1004P)²] where P = (F_o² + 2F_c²)/3
6298 reflections	(Δ/σ)_max = 0.001
397 parameters	Δρ_max = 0.51 e Å⁻³
6 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₈H₉N₃O₂S	γ = 90.929 (2)°
M_r = 211.24	V = 1390.2 (4) Å³
Triclinic, P1	Z = 6
a = 10.657 (2) Å	Mo Kα radiation
b = 11.794 (2) Å	µ = 0.33 mm⁻¹
c = 12.356 (2) Å	T = 100 K
α = 111.657 (2)°	0.20 × 0.18 × 0.04 mm
β = 104.082 (2)°

Data collection top

Bruker SMART APEX diffractometer	6298 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3727 reflections with I > 2σ(I)
T_min = 0.938, T_max = 0.987	R_int = 0.028
8792 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	6 restraints
wR(F²) = 0.189	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.51 e Å⁻³
6298 reflections	Δρ_min = −0.40 e Å⁻³
397 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.84547 (10)	0.94314 (8)	0.21803 (8)	0.0401 (3)
S2	0.45653 (10)	0.85179 (8)	0.31556 (7)	0.0359 (2)
S3	0.10237 (10)	0.74686 (8)	0.41416 (8)	0.0390 (3)
O1	0.7414 (3)	0.5896 (2)	0.7057 (2)	0.0440 (7)
H1O	0.750 (4)	0.566 (4)	0.763 (3)	0.066*
O2	0.7519 (2)	0.7405 (2)	0.9368 (2)	0.0333 (6)
H2O	0.769 (4)	0.797 (3)	1.0057 (17)	0.050*
O3	0.4715 (4)	0.5066 (2)	0.8312 (2)	0.0615 (9)
H3O	0.476 (5)	0.496 (5)	0.895 (3)	0.092*
O4	0.4659 (3)	0.6536 (2)	1.05646 (19)	0.0359 (6)
H4O	0.464 (4)	0.710 (3)	1.122 (2)	0.054*
O5	0.2270 (3)	0.4329 (2)	0.9629 (2)	0.0441 (7)
H5O	0.232 (4)	0.426 (4)	1.029 (2)	0.066*
O6	0.1658 (3)	0.5600 (2)	1.1704 (2)	0.0370 (6)
H6O	0.152 (4)	0.609 (3)	1.235 (2)	0.056*
N1	0.7685 (3)	0.7537 (3)	0.2628 (2)	0.0407 (8)
H1N1	0.7486	0.7210	0.3109	0.049*
H1N2	0.7622	0.7072	0.1868	0.049*
N2	0.8145 (3)	0.9368 (2)	0.4209 (2)	0.0328 (7)
H2N	0.8332	1.0172	0.4520	0.039*
N3	0.7922 (3)	0.8755 (2)	0.4912 (2)	0.0316 (6)
N4	0.4570 (3)	0.6598 (3)	0.3786 (3)	0.0438 (8)
H4N1	0.4531	0.6259	0.4305	0.053*
H4N2	0.4637	0.6141	0.3061	0.053*
N5	0.4424 (3)	0.8421 (2)	0.5209 (2)	0.0294 (6)
H5N	0.4379	0.9218	0.5460	0.035*
N6	0.4390 (3)	0.7808 (2)	0.5960 (2)	0.0282 (6)
N7	0.1429 (3)	0.5636 (3)	0.4892 (3)	0.0470 (9)
H7N1	0.1457	0.5309	0.5431	0.056*
H7N2	0.1607	0.5210	0.4205	0.056*
N8	0.0866 (3)	0.7341 (3)	0.6182 (2)	0.0334 (7)
H8N	0.0617	0.8082	0.6370	0.040*
N9	0.1000 (3)	0.6760 (2)	0.6982 (2)	0.0299 (6)
C1	0.8075 (3)	0.8720 (3)	0.3043 (3)	0.0300 (7)
C2	0.7942 (3)	0.9415 (3)	0.5994 (3)	0.0306 (7)
H2	0.8072	1.0284	0.6258	0.037*
C3	0.7772 (3)	0.8876 (3)	0.6840 (3)	0.0279 (7)
C4	0.7636 (3)	0.7614 (3)	0.6542 (3)	0.0296 (7)
H4	0.7605	0.7070	0.5743	0.035*
C5	0.7545 (3)	0.7147 (3)	0.7389 (3)	0.0293 (7)
C6	0.7597 (3)	0.7934 (3)	0.8565 (3)	0.0257 (7)
C7	0.7714 (3)	0.9180 (3)	0.8871 (3)	0.0319 (8)
H7C	0.7737	0.9719	0.9670	0.038*
C8	0.7799 (3)	0.9652 (3)	0.8013 (3)	0.0327 (8)
H8	0.7875	1.0516	0.8228	0.039*
C9	0.4526 (3)	0.7787 (3)	0.4095 (3)	0.0273 (7)
C10	0.4204 (3)	0.8443 (3)	0.6983 (3)	0.0288 (7)
H10	0.4054	0.9277	0.7164	0.035*
C11	0.4218 (3)	0.7917 (3)	0.7876 (3)	0.0252 (7)
C12	0.4409 (3)	0.6698 (3)	0.7657 (3)	0.0298 (7)
H12	0.4459	0.6164	0.6879	0.036*
C13	0.4526 (3)	0.6261 (3)	0.8557 (3)	0.0321 (8)
C14	0.4480 (3)	0.7039 (3)	0.9711 (3)	0.0257 (7)
C15	0.4243 (3)	0.8234 (3)	0.9921 (3)	0.0316 (8)
H15	0.4172	0.8760	1.0694	0.038*
C16	0.4107 (3)	0.8671 (3)	0.9006 (3)	0.0304 (7)
H16	0.3936	0.9495	0.9153	0.036*
C17	0.1122 (3)	0.6761 (3)	0.5111 (3)	0.0306 (7)
C18	0.0760 (3)	0.7363 (3)	0.7984 (3)	0.0286 (7)
H18	0.0465	0.8147	0.8120	0.034*
C19	0.0928 (3)	0.6872 (3)	0.8926 (3)	0.0264 (7)
C20	0.1458 (3)	0.5772 (3)	0.8812 (3)	0.0288 (7)
H20	0.1662	0.5295	0.8081	0.035*
C21	0.1686 (3)	0.5376 (3)	0.9745 (3)	0.0291 (7)
C22	0.1375 (3)	0.6051 (3)	1.0814 (3)	0.0270 (7)
C23	0.0804 (3)	0.7116 (3)	1.0922 (3)	0.0295 (7)
H23	0.0556	0.7566	1.1637	0.035*
C24	0.0594 (3)	0.7524 (3)	0.9982 (3)	0.0300 (7)
H24	0.0214	0.8264	1.0064	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0718 (7)	0.0287 (5)	0.0288 (5)	0.0104 (4)	0.0234 (4)	0.0146 (4)
S2	0.0636 (6)	0.0242 (4)	0.0253 (4)	0.0079 (4)	0.0172 (4)	0.0123 (4)
S3	0.0631 (6)	0.0330 (5)	0.0286 (5)	0.0124 (4)	0.0187 (4)	0.0164 (4)
O1	0.083 (2)	0.0205 (12)	0.0354 (14)	0.0112 (13)	0.0242 (14)	0.0123 (11)
O2	0.0527 (15)	0.0269 (13)	0.0263 (12)	0.0067 (11)	0.0144 (11)	0.0144 (10)
O3	0.137 (3)	0.0278 (15)	0.0344 (15)	0.0361 (17)	0.0385 (18)	0.0173 (13)
O4	0.0637 (17)	0.0257 (13)	0.0238 (12)	0.0131 (12)	0.0166 (12)	0.0123 (10)
O5	0.083 (2)	0.0266 (13)	0.0343 (14)	0.0200 (13)	0.0278 (14)	0.0167 (12)
O6	0.0633 (17)	0.0276 (13)	0.0252 (12)	0.0146 (12)	0.0162 (12)	0.0127 (11)
N1	0.075 (2)	0.0255 (16)	0.0245 (15)	0.0053 (15)	0.0198 (15)	0.0091 (13)
N2	0.0565 (19)	0.0214 (14)	0.0249 (14)	0.0070 (13)	0.0161 (13)	0.0105 (12)
N3	0.0492 (18)	0.0255 (15)	0.0270 (14)	0.0069 (13)	0.0133 (13)	0.0156 (12)
N4	0.085 (3)	0.0232 (16)	0.0285 (16)	0.0122 (16)	0.0230 (16)	0.0106 (13)
N5	0.0500 (18)	0.0194 (13)	0.0235 (14)	0.0081 (12)	0.0140 (12)	0.0107 (11)
N6	0.0444 (17)	0.0221 (14)	0.0230 (13)	0.0032 (12)	0.0105 (12)	0.0131 (11)
N7	0.088 (3)	0.0285 (17)	0.0371 (17)	0.0156 (17)	0.0319 (17)	0.0165 (14)
N8	0.0529 (19)	0.0271 (15)	0.0302 (15)	0.0141 (13)	0.0172 (13)	0.0179 (13)
N9	0.0426 (17)	0.0239 (14)	0.0293 (14)	0.0056 (12)	0.0133 (12)	0.0147 (12)
C1	0.043 (2)	0.0262 (17)	0.0261 (17)	0.0123 (15)	0.0121 (15)	0.0143 (15)
C2	0.044 (2)	0.0221 (16)	0.0274 (17)	0.0042 (15)	0.0093 (15)	0.0119 (14)
C3	0.0387 (19)	0.0247 (17)	0.0249 (16)	0.0075 (14)	0.0106 (14)	0.0134 (14)
C4	0.042 (2)	0.0221 (16)	0.0261 (17)	0.0081 (14)	0.0122 (14)	0.0087 (14)
C5	0.0412 (19)	0.0190 (16)	0.0316 (17)	0.0082 (14)	0.0128 (15)	0.0119 (14)
C6	0.0326 (18)	0.0267 (17)	0.0235 (16)	0.0092 (14)	0.0116 (13)	0.0132 (14)
C7	0.050 (2)	0.0246 (17)	0.0223 (16)	0.0063 (15)	0.0118 (15)	0.0086 (14)
C8	0.049 (2)	0.0179 (16)	0.0316 (18)	0.0037 (15)	0.0121 (16)	0.0094 (14)
C9	0.0363 (18)	0.0234 (17)	0.0245 (16)	0.0080 (14)	0.0089 (14)	0.0111 (14)
C10	0.0357 (19)	0.0256 (17)	0.0293 (17)	0.0079 (14)	0.0114 (14)	0.0137 (14)
C11	0.0315 (17)	0.0240 (16)	0.0250 (16)	0.0059 (13)	0.0099 (13)	0.0133 (14)
C12	0.046 (2)	0.0250 (17)	0.0211 (15)	0.0092 (15)	0.0134 (14)	0.0092 (14)
C13	0.050 (2)	0.0209 (16)	0.0306 (17)	0.0120 (15)	0.0156 (15)	0.0126 (14)
C14	0.0371 (18)	0.0245 (16)	0.0211 (15)	0.0062 (14)	0.0111 (13)	0.0128 (13)
C15	0.047 (2)	0.0236 (17)	0.0259 (17)	0.0085 (15)	0.0163 (15)	0.0074 (14)
C16	0.048 (2)	0.0191 (16)	0.0296 (17)	0.0078 (14)	0.0133 (15)	0.0132 (14)
C17	0.0397 (19)	0.0259 (17)	0.0288 (17)	0.0040 (15)	0.0122 (15)	0.0116 (15)
C18	0.0333 (18)	0.0267 (17)	0.0289 (17)	0.0061 (14)	0.0096 (14)	0.0131 (14)
C19	0.0337 (18)	0.0221 (16)	0.0242 (16)	0.0019 (13)	0.0079 (13)	0.0098 (13)
C20	0.042 (2)	0.0212 (16)	0.0262 (16)	0.0048 (14)	0.0140 (14)	0.0094 (14)
C21	0.0408 (19)	0.0205 (16)	0.0300 (17)	0.0070 (14)	0.0141 (14)	0.0111 (14)
C22	0.0361 (18)	0.0240 (16)	0.0242 (16)	0.0036 (14)	0.0103 (14)	0.0115 (14)
C23	0.0405 (19)	0.0252 (17)	0.0245 (16)	0.0092 (15)	0.0131 (14)	0.0084 (14)
C24	0.0375 (19)	0.0248 (17)	0.0281 (17)	0.0067 (14)	0.0089 (14)	0.0103 (14)

Geometric parameters (Å, º) top

S1—C1	1.693 (3)	N9—C18	1.270 (4)
S2—C9	1.689 (3)	C2—C3	1.453 (4)
S3—C17	1.680 (3)	C2—H2	0.9500
O1—C5	1.372 (4)	C3—C4	1.391 (4)
O1—H1O	0.837 (10)	C3—C8	1.393 (4)
O2—C6	1.369 (4)	C4—C5	1.372 (4)
O2—H2O	0.840 (10)	C4—H4	0.9500
O3—C13	1.358 (4)	C5—C6	1.392 (4)
O3—H3O	0.836 (10)	C6—C7	1.371 (4)
O4—C14	1.367 (4)	C7—C8	1.387 (4)
O4—H4O	0.841 (10)	C7—H7C	0.9500
O5—C21	1.368 (4)	C8—H8	0.9500
O5—H5O	0.838 (10)	C10—C11	1.450 (4)
O6—C22	1.364 (4)	C10—H10	0.9500
O6—H6O	0.844 (10)	C11—C16	1.385 (4)
N1—C1	1.316 (4)	C11—C12	1.390 (4)
N1—H1N1	0.8800	C12—C13	1.369 (4)
N1—H1N2	0.8800	C12—H12	0.9500
N2—C1	1.341 (4)	C13—C14	1.396 (4)
N2—N3	1.375 (3)	C14—C15	1.375 (4)
N2—H2N	0.8800	C15—C16	1.385 (4)
N3—C2	1.269 (4)	C15—H15	0.9500
N4—C9	1.316 (4)	C16—H16	0.9500
N4—H4N1	0.8800	C18—C19	1.457 (4)
N4—H4N2	0.8800	C18—H18	0.9500
N5—C9	1.335 (4)	C19—C24	1.384 (4)
N5—N6	1.377 (3)	C19—C20	1.397 (4)
N5—H5N	0.8800	C20—C21	1.368 (4)
N6—C10	1.276 (4)	C20—H20	0.9500
N7—C17	1.316 (4)	C21—C22	1.390 (4)
N7—H7N1	0.8800	C22—C23	1.380 (4)
N7—H7N2	0.8800	C23—C24	1.386 (4)
N8—C17	1.344 (4)	C23—H23	0.9500
N8—N9	1.380 (3)	C24—H24	0.9500
N8—H8N	0.8800

C5—O1—H1O	115 (3)	C3—C8—H8	119.6
C6—O2—H2O	107 (3)	N4—C9—N5	116.7 (3)
C13—O3—H3O	106 (4)	N4—C9—S2	123.5 (2)
C14—O4—H4O	107 (3)	N5—C9—S2	119.8 (2)
C21—O5—H5O	103 (3)	N6—C10—C11	121.2 (3)
C22—O6—H6O	112 (3)	N6—C10—H10	119.4
C1—N1—H1N1	120.0	C11—C10—H10	119.4
C1—N1—H1N2	120.0	C16—C11—C12	119.0 (3)
H1N1—N1—H1N2	120.0	C16—C11—C10	118.9 (3)
C1—N2—N3	118.9 (3)	C12—C11—C10	122.0 (3)
C1—N2—H2N	120.5	C13—C12—C11	120.3 (3)
N3—N2—H2N	120.5	C13—C12—H12	119.8
C2—N3—N2	116.4 (3)	C11—C12—H12	119.8
C9—N4—H4N1	120.0	O3—C13—C12	118.8 (3)
C9—N4—H4N2	120.0	O3—C13—C14	120.7 (3)
H4N1—N4—H4N2	120.0	C12—C13—C14	120.5 (3)
C9—N5—N6	118.9 (3)	O4—C14—C15	124.2 (3)
C9—N5—H5N	120.6	O4—C14—C13	116.4 (3)
N6—N5—H5N	120.6	C15—C14—C13	119.4 (3)
C10—N6—N5	116.1 (3)	C14—C15—C16	120.0 (3)
C17—N7—H7N1	120.0	C14—C15—H15	120.0
C17—N7—H7N2	120.0	C16—C15—H15	120.0
H7N1—N7—H7N2	120.0	C15—C16—C11	120.6 (3)
C17—N8—N9	119.0 (3)	C15—C16—H16	119.7
C17—N8—H8N	120.5	C11—C16—H16	119.7
N9—N8—H8N	120.5	N7—C17—N8	115.9 (3)
C18—N9—N8	115.9 (3)	N7—C17—S3	124.0 (3)
N1—C1—N2	116.6 (3)	N8—C17—S3	120.0 (3)
N1—C1—S1	123.3 (2)	N9—C18—C19	121.1 (3)
N2—C1—S1	120.1 (2)	N9—C18—H18	119.5
N3—C2—C3	121.7 (3)	C19—C18—H18	119.5
N3—C2—H2	119.2	C24—C19—C20	118.6 (3)
C3—C2—H2	119.2	C24—C19—C18	119.6 (3)
C4—C3—C8	118.5 (3)	C20—C19—C18	121.8 (3)
C4—C3—C2	122.7 (3)	C21—C20—C19	120.4 (3)
C8—C3—C2	118.8 (3)	C21—C20—H20	119.8
C5—C4—C3	120.7 (3)	C19—C20—H20	119.8
C5—C4—H4	119.7	O5—C21—C20	119.0 (3)
C3—C4—H4	119.7	O5—C21—C22	120.3 (3)
O1—C5—C4	118.7 (3)	C20—C21—C22	120.6 (3)
O1—C5—C6	121.0 (3)	O6—C22—C23	123.8 (3)
C4—C5—C6	120.3 (3)	O6—C22—C21	116.6 (3)
O2—C6—C7	123.0 (3)	C23—C22—C21	119.6 (3)
O2—C6—C5	117.1 (3)	C22—C23—C24	119.5 (3)
C7—C6—C5	119.9 (3)	C22—C23—H23	120.2
C6—C7—C8	119.8 (3)	C24—C23—H23	120.2
C6—C7—H7C	120.1	C19—C24—C23	121.2 (3)
C8—C7—H7C	120.1	C19—C24—H24	119.4
C7—C8—C3	120.8 (3)	C23—C24—H24	119.4
C7—C8—H8	119.6

C1—N2—N3—C2	−176.9 (3)	C11—C12—C13—C14	−1.3 (5)
C9—N5—N6—C10	−175.5 (3)	O3—C13—C14—O4	1.2 (5)
C17—N8—N9—C18	179.2 (3)	C12—C13—C14—O4	−177.4 (3)
N3—N2—C1—N1	5.5 (5)	O3—C13—C14—C15	−177.8 (3)
N3—N2—C1—S1	−175.4 (2)	C12—C13—C14—C15	3.7 (5)
N2—N3—C2—C3	−177.5 (3)	O4—C14—C15—C16	178.4 (3)
N3—C2—C3—C4	2.9 (5)	C13—C14—C15—C16	−2.7 (5)
N3—C2—C3—C8	−179.7 (3)	C14—C15—C16—C11	−0.5 (5)
C8—C3—C4—C5	−0.8 (5)	C12—C11—C16—C15	2.9 (5)
C2—C3—C4—C5	176.6 (3)	C10—C11—C16—C15	−173.6 (3)
C3—C4—C5—O1	−179.9 (3)	N9—N8—C17—N7	3.0 (5)
C3—C4—C5—C6	−0.4 (5)	N9—N8—C17—S3	−177.6 (2)
O1—C5—C6—O2	0.4 (5)	N8—N9—C18—C19	−177.0 (3)
C4—C5—C6—O2	−179.1 (3)	N9—C18—C19—C24	−176.7 (3)
O1—C5—C6—C7	−179.3 (3)	N9—C18—C19—C20	5.3 (5)
C4—C5—C6—C7	1.2 (5)	C24—C19—C20—C21	−2.5 (5)
O2—C6—C7—C8	179.5 (3)	C18—C19—C20—C21	175.5 (3)
C5—C6—C7—C8	−0.9 (5)	C19—C20—C21—O5	−176.6 (3)
C6—C7—C8—C3	−0.3 (5)	C19—C20—C21—C22	1.1 (5)
C4—C3—C8—C7	1.1 (5)	O5—C21—C22—O6	−1.2 (5)
C2—C3—C8—C7	−176.4 (3)	C20—C21—C22—O6	−178.8 (3)
N6—N5—C9—N4	0.9 (5)	O5—C21—C22—C23	179.0 (3)
N6—N5—C9—S2	179.8 (2)	C20—C21—C22—C23	1.4 (5)
N5—N6—C10—C11	−176.7 (3)	O6—C22—C23—C24	177.8 (3)
N6—C10—C11—C16	175.3 (3)	C21—C22—C23—C24	−2.5 (5)
N6—C10—C11—C12	−1.1 (5)	C20—C19—C24—C23	1.4 (5)
C16—C11—C12—C13	−2.0 (5)	C18—C19—C24—C23	−176.6 (3)
C10—C11—C12—C13	174.4 (3)	C22—C23—C24—C19	1.0 (5)
C11—C12—C13—O3	−179.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···O6ⁱ	0.84 (1)	2.07 (3)	2.784 (3)	143 (4)
O2—H2o···S1ⁱⁱ	0.84 (1)	2.47 (1)	3.300 (2)	171 (4)
N1—H1n2···O5ⁱⁱⁱ	0.88	2.00	2.856 (4)	163
O3—H3o···O4ⁱ	0.84 (1)	2.11 (4)	2.732 (3)	130 (4)
O4—H4o···S2ⁱⁱ	0.84 (1)	2.38 (1)	3.219 (2)	174 (4)
N4—H4n2···O3ⁱⁱⁱ	0.88	2.05	2.900 (4)	162
O5—H5o···O2ⁱ	0.84 (1)	2.16 (4)	2.742 (3)	127 (4)
O6—H6o···S3ⁱⁱ	0.84 (1)	2.40 (1)	3.244 (2)	177 (4)
N7—H7n2···O1ⁱⁱⁱ	0.88	2.13	2.981 (4)	161

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

Experimental details

Crystal data
Chemical formula	C₈H₉N₃O₂S
M_r	211.24
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	10.657 (2), 11.794 (2), 12.356 (2)
α, β, γ (°)	111.657 (2), 104.082 (2), 90.929 (2)
V (Å³)	1390.2 (4)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.20 × 0.18 × 0.04

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.938, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	8792, 6298, 3727
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.189, 1.01
No. of reflections	6298
No. of parameters	397
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.40

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···O6ⁱ	0.84 (1)	2.07 (3)	2.784 (3)	143 (4)
O2—H2o···S1ⁱⁱ	0.84 (1)	2.47 (1)	3.300 (2)	171 (4)
N1—H1n2···O5ⁱⁱⁱ	0.88	2.00	2.856 (4)	163
O3—H3o···O4ⁱ	0.84 (1)	2.11 (4)	2.732 (3)	130 (4)
O4—H4o···S2ⁱⁱ	0.84 (1)	2.38 (1)	3.219 (2)	174 (4)
N4—H4n2···O3ⁱⁱⁱ	0.88	2.05	2.900 (4)	162
O5—H5o···O2ⁱ	0.84 (1)	2.16 (4)	2.742 (3)	127 (4)
O6—H6o···S3ⁱⁱ	0.84 (1)	2.40 (1)	3.244 (2)	177 (4)
N7—H7n2···O1ⁱⁱⁱ	0.88	2.13	2.981 (4)	161

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

Acknowledgements

We thank the University of Malaya (P0265/2007A) for supporting this study. KWT thanks the Ministry of Higher Education for a SLAI scholarship in this research.

References

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