1-(2,3,4-Trihydroxy­benzyl­idene)thio­semicarbazide

Shawish, H.B.; Maah, M.J.; Ng, S.W.

doi:10.1107/S1600536810015850

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1278

https://doi.org/10.1107/S1600536810015850

Open

access

1-(2,3,4-Trihydroxybenzylidene)thiosemicarbazide

Hana Bashir Shawish,^a M. Jamil Maah ^a ^* and Seik Weng Ng ^a

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: mjamil@um.edu.my

(Received 8 April 2010; accepted 29 April 2010; online 8 May 2010)

In the title molecule, C₈H₉N₃O₃S, the thiosemicarbazide =N—NH—C(=S)—NH— fragment is twist a different degree of twist in the three independent molecules [dihedral angles = 7.6 (1), 11.6 (1) and 20.7 (1)°]. Intramolecular O—H⋯N and O—H⋯O hydrogen bonds occur. In the crystal, the hydroxy and amino groups are hydrogen-bond donors and the O—H⋯O, O—H⋯S and N—H⋯O hydrogen bonds generate a layer motif.

Related literature

For the crystal structures of 2,4-dihydroxybenzaldehyde thiosemicarbazone and 3,4-dihydroxybenzaldehyde thiosemicarbazone, see: Swesi et al. (2006 ); Tan et al. (2008 ).

Experimental

Crystal data

C₈H₉N₃O₃S
M_r = 227.24
Triclinic, $[P \overline 1]$
a = 10.3121 (10) Å
b = 11.8797 (12) Å
c = 12.4037 (12) Å
α = 68.969 (1)°
β = 87.487 (1)°
γ = 77.161 (1)°
V = 1381.8 (2) Å³
Z = 6
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 100 K
0.35 × 0.10 × 0.02 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.890, T_max = 0.993
13248 measured reflections
6327 independent reflections
4487 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.114
S = 1.02
6327 reflections
478 parameters
18 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.84 (1)	1.94 (2)	2.682 (2)	147 (3)
O2—H2⋯O3ⁱ	0.83 (1)	2.17 (2)	2.773 (2)	129 (3)
O3—H3⋯S1ⁱⁱ	0.83 (1)	2.36 (1)	3.184 (2)	173 (3)
O4—H4⋯N4	0.84 (1)	1.96 (2)	2.666 (2)	141 (3)
O5—H5⋯O6	0.83 (1)	2.24 (3)	2.730 (2)	118 (3)
O6—H6⋯S2ⁱⁱ	0.84 (1)	2.45 (1)	3.276 (2)	172 (2)
O7—H7⋯N7	0.83 (1)	1.97 (2)	2.710 (2)	148 (3)
O8—H8⋯O9	0.84 (1)	2.24 (3)	2.697 (2)	114 (2)
O9—H9⋯S3ⁱⁱⁱ	0.84 (1)	2.40 (1)	3.237 (2)	174 (2)
N3—H31⋯O2^iv	0.85 (1)	2.09 (1)	2.902 (2)	159 (3)
N6—H61⋯O8^v	0.86 (1)	2.01 (1)	2.847 (2)	164 (2)
N9—H91⋯O5^vi	0.86 (1)	2.11 (2)	2.896 (2)	153 (2)
Symmetry codes: (i) -x, -y+1, -z; (ii) x, y, z-1; (iii) x, y, z+1; (iv) -x, -y+1, -z+1; (v) x, y-1, z; (vi) x, y+1, z.

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); 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, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810015850/pk2242sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810015850/pk2242Isup2.hkl

checkCIF report

Related literature top

For the crystal structures of 2,4-dihydroxybenzaldehyde thiosemicarbazone and 3,4-dihydroxybenzaldehyde thiosemicarbazone, see: Swesi et al. (2006); Tan et al. (2008).

Experimental top

2,3,4-Trihydroxybenzaldehyde (1.54 g, 10 mmol) and thiosemicarbazide (0.91 g, 1 mmol) were heated in ethanol (20 ml). The cool solution was set aside for the growth of crystals.

Structure description top

For the crystal structures of 2,4-dihydroxybenzaldehyde thiosemicarbazone and 3,4-dihydroxybenzaldehyde thiosemicarbazone, see: Swesi et al. (2006); Tan et al. (2008).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of the three independent molecules of C₈H₉N₃O₃S at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

1-(2,3,4-Trihydroxybenzylidene)thiosemicarbazide top

Crystal data top

C₈H₉N₃O₃S	Z = 6
M_r = 227.24	F(000) = 708
Triclinic, P1	D_x = 1.639 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.3121 (10) Å	Cell parameters from 2924 reflections
b = 11.8797 (12) Å	θ = 2.6–28.1°
c = 12.4037 (12) Å	µ = 0.34 mm⁻¹
α = 68.969 (1)°	T = 100 K
β = 87.487 (1)°	Plate, pale brown
γ = 77.161 (1)°	0.35 × 0.10 × 0.02 mm
V = 1381.8 (2) Å³

Data collection top

Bruker SMART APEX diffractometer	6327 independent reflections
Radiation source: fine-focus sealed tube	4487 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω scans	θ_max = 27.5°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→12
T_min = 0.890, T_max = 0.993	k = −15→15
13248 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0572P)² + 0.0368P] where P = (F_o² + 2F_c²)/3
6327 reflections	(Δ/σ)_max < 0.001
478 parameters	Δρ_max = 0.38 e Å⁻³
18 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₈H₉N₃O₃S	γ = 77.161 (1)°
M_r = 227.24	V = 1381.8 (2) Å³
Triclinic, P1	Z = 6
a = 10.3121 (10) Å	Mo Kα radiation
b = 11.8797 (12) Å	µ = 0.34 mm⁻¹
c = 12.4037 (12) Å	T = 100 K
α = 68.969 (1)°	0.35 × 0.10 × 0.02 mm
β = 87.487 (1)°

Data collection top

Bruker SMART APEX diffractometer	6327 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4487 reflections with I > 2σ(I)
T_min = 0.890, T_max = 0.993	R_int = 0.033
13248 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	18 restraints
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.38 e Å⁻³
6327 reflections	Δρ_min = −0.37 e Å⁻³
478 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.04483 (6)	0.85739 (5)	0.67520 (4)	0.01600 (14)
S2	0.39952 (6)	0.72567 (5)	0.55744 (5)	0.01715 (14)
S3	0.32855 (6)	1.02438 (5)	0.19484 (5)	0.01889 (15)
O1	0.02467 (17)	0.58729 (14)	0.32793 (12)	0.0171 (4)
H1	0.030 (3)	0.622 (2)	0.3749 (19)	0.033 (8)*
O2	−0.01767 (17)	0.52286 (14)	0.14650 (13)	0.0185 (4)
H2	0.023 (3)	0.489 (3)	0.103 (2)	0.048 (10)*
O3	0.00587 (16)	0.67307 (14)	−0.07208 (12)	0.0165 (3)
H3	0.019 (3)	0.725 (2)	−0.1352 (14)	0.031 (8)*
O4	0.30904 (16)	0.48727 (14)	0.20588 (12)	0.0159 (3)
H4	0.325 (3)	0.514 (3)	0.257 (2)	0.054 (10)*
O5	0.23954 (17)	0.43594 (14)	0.02850 (13)	0.0180 (4)
H5	0.218 (3)	0.438 (3)	−0.0364 (14)	0.063 (11)*
O6	0.30786 (16)	0.55735 (14)	−0.19098 (13)	0.0166 (3)
H6	0.326 (3)	0.607 (2)	−0.2539 (13)	0.030 (8)*
O7	0.27294 (17)	1.30858 (14)	0.54062 (13)	0.0184 (4)
H7	0.287 (3)	1.270 (2)	0.496 (2)	0.038 (9)*
O8	0.27623 (17)	1.38726 (14)	0.71552 (13)	0.0182 (4)
H8	0.284 (3)	1.399 (3)	0.7771 (16)	0.051 (10)*
O9	0.28539 (16)	1.23273 (14)	0.93746 (12)	0.0168 (3)
H9	0.294 (3)	1.1754 (17)	1.0024 (12)	0.025 (7)*
N1	0.05073 (18)	0.77060 (16)	0.39755 (14)	0.0124 (4)
N2	0.05168 (19)	0.83290 (16)	0.47275 (15)	0.0131 (4)
H21	0.045 (2)	0.9116 (10)	0.445 (2)	0.024 (7)*
N3	0.0408 (2)	0.65715 (17)	0.62610 (16)	0.0194 (4)
H31	0.033 (3)	0.620 (2)	0.6981 (10)	0.036 (8)*
H32	0.038 (2)	0.6192 (19)	0.5797 (17)	0.018 (7)*
N4	0.39153 (18)	0.64797 (15)	0.27613 (15)	0.0126 (4)
N5	0.40933 (19)	0.70383 (17)	0.35334 (15)	0.0135 (4)
H51	0.425 (3)	0.7772 (14)	0.324 (2)	0.045 (9)*
N6	0.3389 (2)	0.54900 (17)	0.49721 (16)	0.0177 (4)
H61	0.325 (2)	0.510 (2)	0.5681 (10)	0.020 (7)*
H62	0.334 (2)	0.515 (2)	0.4482 (16)	0.019 (7)*
N7	0.30054 (19)	1.11133 (16)	0.47366 (15)	0.0153 (4)
N8	0.3167 (2)	1.04604 (17)	0.39915 (15)	0.0163 (4)
H81	0.337 (2)	0.9667 (9)	0.425 (2)	0.019 (7)*
N9	0.2893 (2)	1.22846 (17)	0.24562 (16)	0.0200 (4)
H91	0.284 (2)	1.270 (2)	0.1728 (9)	0.024 (7)*
H92	0.278 (3)	1.265 (2)	0.2949 (18)	0.034 (8)*
C1	0.0359 (2)	0.66793 (19)	0.21952 (17)	0.0121 (4)
C2	0.0183 (2)	0.63384 (18)	0.12652 (18)	0.0129 (4)
C3	0.0300 (2)	0.71265 (19)	0.01372 (17)	0.0123 (4)
C4	0.0646 (2)	0.82510 (19)	−0.00648 (18)	0.0139 (5)
H4A	0.0770	0.8772	−0.0829	0.017*
C5	0.0806 (2)	0.85971 (19)	0.08633 (17)	0.0129 (4)
H5A	0.1033	0.9368	0.0726	0.015*
C6	0.0645 (2)	0.78427 (19)	0.19995 (17)	0.0117 (4)
C7	0.0709 (2)	0.83158 (19)	0.29141 (17)	0.0123 (4)
H7A	0.0908	0.9106	0.2726	0.015*
C8	0.0451 (2)	0.77519 (19)	0.58732 (18)	0.0136 (5)
C9	0.3408 (2)	0.55759 (19)	0.09885 (17)	0.0125 (4)
C10	0.3076 (2)	0.52858 (18)	0.00573 (18)	0.0129 (4)
C11	0.3422 (2)	0.59381 (19)	−0.10491 (17)	0.0120 (4)
C12	0.4069 (2)	0.68949 (19)	−0.12458 (18)	0.0138 (5)
H12	0.4322	0.7323	−0.2002	0.017*
C13	0.4343 (2)	0.72205 (19)	−0.03270 (18)	0.0135 (4)
H13	0.4767	0.7889	−0.0463	0.016*
C14	0.4006 (2)	0.65829 (19)	0.07964 (17)	0.0119 (4)
C15	0.4214 (2)	0.70176 (19)	0.17123 (18)	0.0126 (4)
H15	0.4584	0.7725	0.1532	0.015*
C16	0.3804 (2)	0.65349 (19)	0.46518 (18)	0.0130 (4)
C17	0.2798 (2)	1.22282 (19)	0.64927 (18)	0.0135 (4)
C18	0.2795 (2)	1.26454 (19)	0.74128 (18)	0.0134 (5)
C19	0.2838 (2)	1.1822 (2)	0.85449 (18)	0.0134 (4)
C20	0.2863 (2)	1.0579 (2)	0.87772 (18)	0.0152 (5)
H20	0.2871	1.0021	0.9551	0.018*
C21	0.2877 (2)	1.0171 (2)	0.78646 (18)	0.0153 (5)
H21a	0.2898	0.9324	0.8020	0.018*
C22	0.2860 (2)	1.09729 (19)	0.67167 (18)	0.0133 (4)
C23	0.2966 (2)	1.0449 (2)	0.58130 (18)	0.0146 (5)
H23	0.3008	0.9590	0.6023	0.018*
C24	0.3104 (2)	1.1070 (2)	0.28385 (18)	0.0149 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0281 (4)	0.0122 (3)	0.0102 (2)	−0.0063 (2)	0.0013 (2)	−0.0060 (2)
S2	0.0270 (4)	0.0164 (3)	0.0125 (3)	−0.0084 (2)	0.0028 (2)	−0.0086 (2)
S3	0.0312 (4)	0.0155 (3)	0.0128 (3)	−0.0074 (2)	0.0010 (2)	−0.0070 (2)
O1	0.0326 (10)	0.0128 (8)	0.0088 (7)	−0.0099 (7)	0.0009 (7)	−0.0042 (6)
O2	0.0340 (11)	0.0120 (8)	0.0157 (8)	−0.0124 (7)	0.0038 (7)	−0.0083 (6)
O3	0.0283 (10)	0.0156 (8)	0.0096 (7)	−0.0104 (7)	0.0011 (7)	−0.0059 (6)
O4	0.0279 (10)	0.0134 (8)	0.0093 (7)	−0.0097 (7)	0.0017 (6)	−0.0046 (6)
O5	0.0321 (10)	0.0160 (8)	0.0105 (7)	−0.0138 (7)	−0.0001 (7)	−0.0052 (6)
O6	0.0286 (10)	0.0147 (8)	0.0097 (7)	−0.0082 (7)	0.0000 (7)	−0.0061 (6)
O7	0.0345 (11)	0.0124 (8)	0.0108 (7)	−0.0075 (7)	0.0019 (7)	−0.0060 (6)
O8	0.0319 (10)	0.0132 (8)	0.0141 (8)	−0.0097 (7)	0.0035 (7)	−0.0079 (6)
O9	0.0257 (10)	0.0178 (8)	0.0099 (7)	−0.0080 (7)	0.0008 (7)	−0.0066 (6)
N1	0.0151 (10)	0.0125 (9)	0.0122 (9)	−0.0039 (7)	−0.0017 (7)	−0.0068 (7)
N2	0.0222 (11)	0.0088 (9)	0.0109 (8)	−0.0041 (8)	−0.0001 (7)	−0.0063 (7)
N3	0.0399 (13)	0.0113 (9)	0.0096 (9)	−0.0090 (9)	−0.0003 (9)	−0.0047 (7)
N4	0.0171 (10)	0.0107 (9)	0.0128 (9)	−0.0025 (7)	−0.0020 (7)	−0.0075 (7)
N5	0.0200 (11)	0.0111 (9)	0.0135 (9)	−0.0057 (8)	0.0003 (7)	−0.0079 (7)
N6	0.0321 (12)	0.0126 (9)	0.0107 (9)	−0.0083 (8)	0.0021 (8)	−0.0049 (8)
N7	0.0226 (11)	0.0114 (9)	0.0154 (9)	−0.0053 (8)	0.0004 (8)	−0.0082 (7)
N8	0.0303 (12)	0.0092 (9)	0.0117 (9)	−0.0059 (8)	0.0005 (8)	−0.0056 (7)
N9	0.0373 (13)	0.0114 (9)	0.0119 (9)	−0.0077 (9)	−0.0011 (9)	−0.0034 (8)
C1	0.0140 (12)	0.0109 (10)	0.0107 (10)	−0.0023 (8)	0.0013 (8)	−0.0035 (8)
C2	0.0151 (12)	0.0091 (10)	0.0156 (10)	−0.0040 (8)	0.0003 (9)	−0.0048 (8)
C3	0.0131 (12)	0.0138 (10)	0.0118 (10)	−0.0033 (9)	0.0002 (8)	−0.0065 (8)
C4	0.0166 (12)	0.0126 (10)	0.0109 (10)	−0.0040 (9)	0.0014 (8)	−0.0018 (8)
C5	0.0161 (12)	0.0087 (10)	0.0146 (10)	−0.0035 (8)	−0.0004 (8)	−0.0044 (8)
C6	0.0117 (11)	0.0104 (10)	0.0137 (10)	−0.0022 (8)	−0.0005 (8)	−0.0051 (8)
C7	0.0132 (12)	0.0102 (10)	0.0143 (10)	−0.0039 (8)	−0.0018 (8)	−0.0044 (8)
C8	0.0165 (12)	0.0136 (10)	0.0121 (10)	−0.0044 (9)	0.0006 (8)	−0.0056 (8)
C9	0.0150 (12)	0.0112 (10)	0.0104 (9)	−0.0009 (8)	0.0011 (8)	−0.0040 (8)
C10	0.0169 (12)	0.0077 (10)	0.0150 (10)	−0.0043 (9)	0.0004 (8)	−0.0042 (8)
C11	0.0161 (12)	0.0107 (10)	0.0109 (10)	−0.0014 (8)	−0.0020 (8)	−0.0064 (8)
C12	0.0165 (12)	0.0125 (10)	0.0124 (10)	−0.0039 (9)	0.0015 (8)	−0.0041 (8)
C13	0.0132 (12)	0.0111 (10)	0.0156 (10)	−0.0022 (8)	−0.0016 (8)	−0.0040 (8)
C14	0.0135 (12)	0.0105 (10)	0.0129 (10)	−0.0018 (8)	−0.0020 (8)	−0.0056 (8)
C15	0.0138 (12)	0.0108 (10)	0.0144 (10)	−0.0021 (8)	−0.0016 (8)	−0.0059 (8)
C16	0.0143 (12)	0.0113 (10)	0.0128 (10)	−0.0006 (9)	−0.0007 (8)	−0.0046 (8)
C17	0.0160 (12)	0.0123 (10)	0.0116 (10)	−0.0041 (9)	0.0001 (8)	−0.0031 (8)
C18	0.0163 (12)	0.0120 (10)	0.0148 (10)	−0.0057 (9)	0.0017 (9)	−0.0067 (8)
C19	0.0118 (12)	0.0181 (11)	0.0134 (10)	−0.0050 (9)	0.0033 (8)	−0.0085 (9)
C20	0.0179 (13)	0.0149 (11)	0.0112 (10)	−0.0045 (9)	0.0011 (9)	−0.0025 (8)
C21	0.0202 (13)	0.0102 (10)	0.0161 (11)	−0.0048 (9)	0.0007 (9)	−0.0044 (8)
C22	0.0148 (12)	0.0125 (10)	0.0145 (10)	−0.0045 (9)	0.0005 (8)	−0.0063 (8)
C23	0.0171 (12)	0.0123 (10)	0.0165 (11)	−0.0046 (9)	−0.0007 (9)	−0.0066 (9)
C24	0.0174 (12)	0.0155 (11)	0.0136 (10)	−0.0068 (9)	0.0002 (9)	−0.0052 (9)

Geometric parameters (Å, º) top

S1—C8	1.704 (2)	N7—N8	1.388 (2)
S2—C16	1.698 (2)	N8—C24	1.348 (3)
S3—C24	1.702 (2)	N8—H81	0.858 (10)
O1—C1	1.360 (2)	N9—C24	1.316 (3)
O1—H1	0.836 (10)	N9—H91	0.857 (10)
O2—C2	1.383 (2)	N9—H92	0.861 (10)
O2—H2	0.834 (10)	C1—C2	1.383 (3)
O3—C3	1.360 (2)	C1—C6	1.411 (3)
O3—H3	0.833 (10)	C2—C3	1.394 (3)
O4—C9	1.362 (2)	C3—C4	1.392 (3)
O4—H4	0.835 (10)	C4—C5	1.381 (3)
O5—C10	1.374 (2)	C4—H4A	0.9500
O5—H5	0.831 (10)	C5—C6	1.399 (3)
O6—C11	1.373 (2)	C5—H5A	0.9500
O6—H6	0.835 (10)	C6—C7	1.445 (3)
O7—C17	1.360 (2)	C7—H7A	0.9500
O7—H7	0.830 (10)	C9—C10	1.394 (3)
O8—C18	1.369 (2)	C9—C14	1.406 (3)
O8—H8	0.837 (10)	C10—C11	1.389 (3)
O9—C19	1.367 (2)	C11—C12	1.385 (3)
O9—H9	0.840 (10)	C12—C13	1.386 (3)
N1—C7	1.288 (3)	C12—H12	0.9500
N1—N2	1.385 (2)	C13—C14	1.398 (3)
N2—C8	1.344 (3)	C13—H13	0.9500
N2—H21	0.860 (10)	C14—C15	1.447 (3)
N3—C8	1.320 (3)	C15—H15	0.9500
N3—H31	0.851 (10)	C17—C18	1.398 (3)
N3—H32	0.853 (10)	C17—C22	1.402 (3)
N4—C15	1.285 (3)	C18—C19	1.390 (3)
N4—N5	1.385 (2)	C19—C20	1.394 (3)
N5—C16	1.349 (3)	C20—C21	1.380 (3)
N5—H51	0.865 (10)	C20—H20	0.9500
N6—C16	1.323 (3)	C21—C22	1.399 (3)
N6—H61	0.858 (10)	C21—H21a	0.9500
N6—H62	0.849 (10)	C22—C23	1.454 (3)
N7—C23	1.288 (3)	C23—H23	0.9500

C1—O1—H1	108.4 (19)	N3—C8—N2	118.19 (19)
C2—O2—H2	110 (2)	N3—C8—S1	123.33 (16)
C3—O3—H3	108.4 (19)	N2—C8—S1	118.47 (16)
C9—O4—H4	112 (2)	O4—C9—C10	117.13 (19)
C10—O5—H5	104 (2)	O4—C9—C14	122.83 (19)
C11—O6—H6	107.5 (19)	C10—C9—C14	120.01 (19)
C17—O7—H7	106 (2)	O5—C10—C11	122.75 (19)
C18—O8—H8	109 (2)	O5—C10—C9	117.48 (19)
C19—O9—H9	108.1 (18)	C11—C10—C9	119.76 (19)
C7—N1—N2	114.97 (17)	O6—C11—C12	123.38 (19)
C8—N2—N1	120.71 (17)	O6—C11—C10	115.75 (19)
C8—N2—H21	119.4 (17)	C12—C11—C10	120.87 (19)
N1—N2—H21	119.2 (17)	C13—C12—C11	119.3 (2)
C8—N3—H31	119.2 (19)	C13—C12—H12	120.3
C8—N3—H32	121.1 (16)	C11—C12—H12	120.3
H31—N3—H32	119 (2)	C12—C13—C14	121.2 (2)
C15—N4—N5	116.06 (18)	C12—C13—H13	119.4
C16—N5—N4	119.95 (18)	C14—C13—H13	119.4
C16—N5—H51	122.7 (19)	C13—C14—C9	118.70 (19)
N4—N5—H51	116.4 (19)	C13—C14—C15	119.20 (19)
C16—N6—H61	121.8 (17)	C9—C14—C15	122.01 (19)
C16—N6—H62	119.6 (17)	N4—C15—C14	122.3 (2)
H61—N6—H62	118 (2)	N4—C15—H15	118.9
C23—N7—N8	114.78 (18)	C14—C15—H15	118.9
C24—N8—N7	120.06 (18)	N6—C16—N5	117.59 (19)
C24—N8—H81	118.3 (16)	N6—C16—S2	123.38 (16)
N7—N8—H81	121.4 (16)	N5—C16—S2	119.03 (16)
C24—N9—H91	120.2 (17)	O7—C17—C18	117.13 (19)
C24—N9—H92	118.8 (18)	O7—C17—C22	123.12 (19)
H91—N9—H92	121 (2)	C18—C17—C22	119.74 (19)
O1—C1—C2	118.45 (19)	O8—C18—C19	122.09 (19)
O1—C1—C6	121.89 (18)	O8—C18—C17	117.80 (18)
C2—C1—C6	119.65 (19)	C19—C18—C17	120.11 (19)
O2—C2—C1	119.04 (18)	O9—C19—C18	115.08 (19)
O2—C2—C3	120.19 (18)	O9—C19—C20	124.29 (19)
C1—C2—C3	120.69 (19)	C18—C19—C20	120.6 (2)
O3—C3—C4	123.43 (18)	C21—C20—C19	118.9 (2)
O3—C3—C2	116.36 (18)	C21—C20—H20	120.5
C4—C3—C2	120.20 (19)	C19—C20—H20	120.5
C5—C4—C3	119.01 (19)	C20—C21—C22	121.8 (2)
C5—C4—H4A	120.5	C20—C21—H21a	119.1
C3—C4—H4A	120.5	C22—C21—H21a	119.1
C4—C5—C6	121.78 (19)	C21—C22—C17	118.79 (19)
C4—C5—H5A	119.1	C21—C22—C23	118.05 (19)
C6—C5—H5A	119.1	C17—C22—C23	123.11 (19)
C5—C6—C1	118.54 (19)	N7—C23—C22	122.12 (19)
C5—C6—C7	118.53 (19)	N7—C23—H23	118.9
C1—C6—C7	122.85 (19)	C22—C23—H23	118.9
N1—C7—C6	122.49 (19)	N9—C24—N8	118.0 (2)
N1—C7—H7A	118.8	N9—C24—S3	123.12 (17)
C6—C7—H7A	118.8	N8—C24—S3	118.90 (16)

C7—N1—N2—C8	−173.3 (2)	C11—C12—C13—C14	1.5 (3)
C15—N4—N5—C16	179.99 (19)	C12—C13—C14—C9	1.6 (3)
C23—N7—N8—C24	174.1 (2)	C12—C13—C14—C15	−175.1 (2)
O1—C1—C2—O2	3.8 (3)	O4—C9—C14—C13	177.55 (19)
C6—C1—C2—O2	−176.09 (19)	C10—C9—C14—C13	−4.6 (3)
O1—C1—C2—C3	−179.37 (19)	O4—C9—C14—C15	−5.9 (3)
C6—C1—C2—C3	0.8 (3)	C10—C9—C14—C15	172.0 (2)
O2—C2—C3—O3	−0.7 (3)	N5—N4—C15—C14	−176.27 (18)
C1—C2—C3—O3	−177.53 (19)	C13—C14—C15—N4	179.4 (2)
O2—C2—C3—C4	179.20 (19)	C9—C14—C15—N4	2.9 (3)
C1—C2—C3—C4	2.4 (3)	N4—N5—C16—N6	1.8 (3)
O3—C3—C4—C5	176.8 (2)	N4—N5—C16—S2	−178.53 (15)
C2—C3—C4—C5	−3.1 (3)	O7—C17—C18—O8	−1.8 (3)
C3—C4—C5—C6	0.7 (3)	C22—C17—C18—O8	178.62 (19)
C4—C5—C6—C1	2.4 (3)	O7—C17—C18—C19	178.8 (2)
C4—C5—C6—C7	−174.4 (2)	C22—C17—C18—C19	−0.8 (3)
O1—C1—C6—C5	177.06 (19)	O8—C18—C19—O9	−0.4 (3)
C2—C1—C6—C5	−3.1 (3)	C17—C18—C19—O9	178.91 (19)
O1—C1—C6—C7	−6.3 (3)	O8—C18—C19—C20	179.7 (2)
C2—C1—C6—C7	173.6 (2)	C17—C18—C19—C20	−1.0 (3)
N2—N1—C7—C6	−175.78 (18)	O9—C19—C20—C21	−178.4 (2)
C5—C6—C7—N1	176.6 (2)	C18—C19—C20—C21	1.5 (3)
C1—C6—C7—N1	−0.1 (3)	C19—C20—C21—C22	−0.3 (3)
N1—N2—C8—N3	1.5 (3)	C20—C21—C22—C17	−1.4 (3)
N1—N2—C8—S1	−179.28 (15)	C20—C21—C22—C23	176.0 (2)
O4—C9—C10—O5	3.3 (3)	O7—C17—C22—C21	−177.6 (2)
C14—C9—C10—O5	−174.69 (19)	C18—C17—C22—C21	1.9 (3)
O4—C9—C10—C11	−177.45 (18)	O7—C17—C22—C23	5.2 (4)
C14—C9—C10—C11	4.5 (3)	C18—C17—C22—C23	−175.3 (2)
O5—C10—C11—O6	−2.0 (3)	N8—N7—C23—C22	177.28 (19)
C9—C10—C11—O6	178.77 (19)	C21—C22—C23—N7	−177.5 (2)
O5—C10—C11—C12	177.7 (2)	C17—C22—C23—N7	−0.3 (4)
C9—C10—C11—C12	−1.5 (3)	N7—N8—C24—N9	0.3 (3)
O6—C11—C12—C13	178.2 (2)	N7—N8—C24—S3	−179.20 (16)
C10—C11—C12—C13	−1.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.84 (1)	1.94 (2)	2.682 (2)	147 (3)
O2—H2···O3ⁱ	0.83 (1)	2.17 (2)	2.773 (2)	129 (3)
O3—H3···S1ⁱⁱ	0.83 (1)	2.36 (1)	3.184 (2)	173 (3)
O4—H4···N4	0.84 (1)	1.96 (2)	2.666 (2)	141 (3)
O5—H5···O6	0.83 (1)	2.24 (3)	2.730 (2)	118 (3)
O6—H6···S2ⁱⁱ	0.84 (1)	2.45 (1)	3.276 (2)	172 (2)
O7—H7···N7	0.83 (1)	1.97 (2)	2.710 (2)	148 (3)
O8—H8···O9	0.84 (1)	2.24 (3)	2.697 (2)	114 (2)
O9—H9···S3ⁱⁱⁱ	0.84 (1)	2.40 (1)	3.237 (2)	174 (2)
N3—H31···O2^iv	0.85 (1)	2.09 (1)	2.902 (2)	159 (3)
N6—H61···O8^v	0.86 (1)	2.01 (1)	2.847 (2)	164 (2)
N9—H91···O5^vi	0.86 (1)	2.11 (2)	2.896 (2)	153 (2)

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

Experimental details

Crystal data
Chemical formula	C₈H₉N₃O₃S
M_r	227.24
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	10.3121 (10), 11.8797 (12), 12.4037 (12)
α, β, γ (°)	68.969 (1), 87.487 (1), 77.161 (1)
V (Å³)	1381.8 (2)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.35 × 0.10 × 0.02

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.890, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	13248, 6327, 4487
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.114, 1.02
No. of reflections	6327
No. of parameters	478
No. of restraints	18
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.37

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.84 (1)	1.94 (2)	2.682 (2)	147 (3)
O2—H2···O3ⁱ	0.83 (1)	2.17 (2)	2.773 (2)	129 (3)
O3—H3···S1ⁱⁱ	0.83 (1)	2.36 (1)	3.184 (2)	173 (3)
O4—H4···N4	0.84 (1)	1.96 (2)	2.666 (2)	141 (3)
O5—H5···O6	0.83 (1)	2.24 (3)	2.730 (2)	118 (3)
O6—H6···S2ⁱⁱ	0.84 (1)	2.45 (1)	3.276 (2)	172 (2)
O7—H7···N7	0.83 (1)	1.97 (2)	2.710 (2)	148 (3)
O8—H8···O9	0.84 (1)	2.24 (3)	2.697 (2)	114 (2)
O9—H9···S3ⁱⁱⁱ	0.84 (1)	2.40 (1)	3.237 (2)	174 (2)
N3—H31···O2^iv	0.85 (1)	2.09 (1)	2.902 (2)	159 (3)
N6—H61···O8^v	0.86 (1)	2.01 (1)	2.847 (2)	164 (2)
N9—H91···O5^vi	0.86 (1)	2.11 (2)	2.896 (2)	153 (2)

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

Acknowledgements

We thank the University of Malaya (PS354/2009) and MOHE (FRGS-FP001/2009) for supporting this study. HBS thanks the Libyan People's Bureau in Malaysia for a scholarship.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Swesi, A. T., Farina, Y., Kassim, M. & Ng, S. W. (2006). Acta Cryst. E62, o5457–o5458. Web of Science CSD CrossRef IUCr Journals Google Scholar
Tan, K. W., Farina, Y., Ng, C. H., Maah, M. J. & Ng, S. W. (2008). Acta Cryst. E64, o1073. Web of Science CSD CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43. Submitted. Google Scholar