1,5-Bis[(E)-1-(2-hydroxyphenyl)ethyl­idene]thiocarbonohydrazide mono­hydrate

Affan, M.A.; Chee, D.N.A.; Ahmad, F.B.; Tiekink, E.R.T.

doi:10.1107/S1600536810004241

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o555

doi:10.1107/S1600536810004241

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1,5-Bis[(E)-1-(2-hydroxyphenyl)ethylidene]thiocarbonohydrazide monohydrate

Md. Abu Affan,^a ‡ Dayang N. A. Chee,^a Fasihuddin B. Ahmad ^a and Edward R. T. Tiekink ^b ^*

^aDepartment of Chemistry, Faculty of Resource Science and Technology, Universiti Malaysia Sarawak, 94300 Kota Samarahan, Sarawak, Malaysia, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: Edward.Tiekink@gmail.com

(Received 2 February 2010; accepted 2 February 2010; online 6 February 2010)

In the title compound, C₁₇H₁₈N₄O₂S·H₂O, the thiourea derivative is almost planar, with an r.m.s. deviation for the non-H atoms of 0.057 Å. The hydroxyl groups lie to the same side of the molecule as the thione S atom, a conformation that allows the formation of intramolecular O—H⋯S and O—H⋯N hydrogen bonds. In the crystal structure, the thiourea and water molecules self-assemble into a two-dimensional array by a combination of O_water—H⋯O_hydroxyl, N—H⋯O_water and O_water—H⋯S hydrogen bonds and C—H⋯π interactions.

Related literature

For background and recent studies of the biological activity of organotin compounds, see: Gielen & Tiekink (2005 ); Affan et al. (2009 ). For the structure of the ketone analogue of the title compound, see: Zukerman-Schpector et al. (2009 ).

Experimental

Crystal data

C₁₇H₁₈N₄O₂S·H₂O
M_r = 360.43
Monoclinic, P 2₁ /n
a = 15.8654 (3) Å
b = 7.3938 (1) Å
c = 16.3697 (3) Å
β = 115.922 (1)°
V = 1727.06 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 100 K
0.44 × 0.13 × 0.07 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.905, T_max = 1
15464 measured reflections
3968 independent reflections
3136 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.102
S = 1.03
3968 reflections
246 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C4–C9 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯N2	0.83 (2)	1.79 (2)	2.5191 (17)	147 (2)
O1—H1O⋯S1	0.83 (2)	2.86 (2)	3.5126 (13)	138 (2)
O2—H2O⋯N4	0.82 (2)	1.81 (2)	2.542 (2)	148 (2)
O2—H2O⋯S1	0.82 (2)	2.96 (2)	3.6220 (15)	139 (2)
O3—H3O⋯O1	0.84 (2)	1.91 (2)	2.7525 (18)	174 (2)
O3—H4O⋯S1ⁱ	0.82 (2)	2.76 (2)	3.5089 (14)	154 (2)
N1—H1N⋯O3ⁱⁱ	0.87 (2)	2.04 (2)	2.8169 (19)	150 (2)
N3—H3N⋯O3ⁱⁱ	0.88 (2)	2.04 (2)	2.854 (2)	154 (2)
C11—H11C⋯Cg1ⁱⁱⁱ	0.98	2.61	3.4497 (17)	144
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (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: SHELXS86 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810004241/hb5327sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810004241/hb5327Isup2.hkl

checkCIF report

Comment top

The molecule in the title hydrate, (I), was synthesised as part of an on-going study into biological studies of organotin compounds (Gielen & Tiekink, 2005; Affan et al., 2009). The thiourea derivative in (I) is effectively planar with the maximum deviation of any of the torsion angles from 0 or 180° being 4.6 (2)° for N4—C10—C12—C13 and -174.62 (15)° for C11—C10—C12—C13. The r.m.s. deviation for all non-hydrogen atoms in the thiourea molecule = 0.057 Å. The conformation about each of the C1═N2 [1.290 (2) Å] and C10═N4 [1.2956 (19) Å] double bonds is E. Finally, the hydroxyl groups are orientated to the same side of the molecule as the thione-S atom. The described molecular conformation is stabilised by intramolecular O_hydroxyl—H···N_imine and O_hydroxyl—H···S_thione hydrogen bonds, Table 1. Allowing for substitution of the thione by a ketone group, the described molecular conformation for the thiourea molecule in (I) resembles that in the recently reported ketone derivative (Zukerman-Schpector et al., 2009).

In addition to the intramolecular hydrogen bonds, the crystal structure features O_water—H···O_hydroxyl, N—H···O_water and O_water—H···S hydrogen bonds, Table 1. The N—H atoms of one molecule connect to a water molecule which in turn forms a hydrogen bond with a hydroxyl-O1 atom of a second thiourea derivative. These interactions give rise to a supramolecular chain with base vector [101]. However, this does not take into account a second donor hydrogen bond involving the water molecule. This forms a hydrogen bond with a thione-S atom of a third thiourea derivative, Fig. 2. The latter interactions link chains into a 2-D array with additional stabilisation afforded by C—H···π, Table 1, and π···π interactions. The latter occur between the benzene rings: ring centroid(C4–C9)···ring centroid(C12–C17)ⁱ distance = 3.7821 (10) Å, with a dihedral angle between the least-squares plane through the rings of 2.25 (7)°; symmetry operation i: 1 - x, -y, 1 - z.

Related literature top

For background and recent studies of the biological activity of organotin compounds, see: Gielen & Tiekink (2005); Affan et al. (2009). For the structure of the ketone analogue of the title compound, see: Zukerman-Schpector et al. (2009).

Experimental top

A mixture of thiocarbohydrazone (0.53 g, 0.005 mol) and 2-hydroxyacetophenone (1.36 g, 0.01 mol) in absolute ethanol was heated under reflux for 4–5 h in the presence of 1–2 drops of glacial acetic acid. The reaction mixture was allowed to cool to room temperature for 1 h. The light-yellow precipitate was filtered off and washed several times using absolute ethanol, and was purified by recrystallization from hot absolute ethanol and dried under vacuum over P₂O₅. Colourless prisms of (I) were obtained by slow evaporation of acetone solution at room temperature. Yield: 1.66 g, 88.0%. m.p. = 494–496 K. IR (KBr): ν_OH (3561–3391), ν_NH 3230, ν_C_═_N 1619, ν_N—N 963, ν_C_═_S 857 cm^-1.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of (I) showing displacement ellipsoids at the 50% probability level.
	Fig. 2. Supramolecular 2-D array in (I) mediated by O—H···O (orange dashed lines), N—H···O (blue dashed lines) and O—H···S (green dashed lines) hydrogen bonds. Colour code: S, yellow; O, red; N, blue; C, grey; H, green.

1,5-Bis[(E)-1-(2-hydroxyphenyl)ethylidene]thiocarbonohydrazide monohydrate top

Crystal data top

C₁₇H₁₈N₄O₂S·H₂O	F(000) = 760
M_r = 360.43	D_x = 1.386 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4324 reflections
a = 15.8654 (3) Å	θ = 2.9–27.4°
b = 7.3938 (1) Å	µ = 0.21 mm⁻¹
c = 16.3697 (3) Å	T = 100 K
β = 115.922 (1)°	Prism, colourless
V = 1727.06 (5) Å³	0.44 × 0.13 × 0.07 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD diffractometer	3968 independent reflections
Radiation source: sealed tube	3136 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ϕ and ω scans	θ_max = 27.5°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −20→20
T_min = 0.905, T_max = 1	k = −9→8
15464 measured reflections	l = −21→21

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0487P)² + 0.7503P] where P = (F_o² + 2F_c²)/3
3968 reflections	(Δ/σ)_max = 0.001
246 parameters	Δρ_max = 0.35 e Å⁻³
7 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₇H₁₈N₄O₂S·H₂O	V = 1727.06 (5) Å³
M_r = 360.43	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 15.8654 (3) Å	µ = 0.21 mm⁻¹
b = 7.3938 (1) Å	T = 100 K
c = 16.3697 (3) Å	0.44 × 0.13 × 0.07 mm
β = 115.922 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	3968 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3136 reflections with I > 2σ(I)
T_min = 0.905, T_max = 1	R_int = 0.033
15464 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	7 restraints
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.35 e Å⁻³
3968 reflections	Δρ_min = −0.27 e Å⁻³
246 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.65089 (3)	0.17338 (6)	0.56929 (3)	0.02002 (12)
O1	0.65341 (7)	0.31213 (16)	0.77557 (8)	0.0213 (3)
H1O	0.6224 (14)	0.300 (3)	0.7201 (15)	0.032*
O2	0.70052 (8)	−0.01110 (17)	0.38996 (7)	0.0225 (3)
H2O	0.6629 (14)	0.041 (3)	0.4040 (14)	0.034*
O3	0.82009 (8)	0.13214 (18)	0.86971 (9)	0.0240 (3)
H3O	0.7673 (15)	0.180 (3)	0.8392 (15)	0.036*
H4O	0.8143 (14)	0.022 (3)	0.8646 (15)	0.036*
N1	0.47863 (9)	0.29267 (19)	0.53363 (9)	0.0179 (3)
H1N	0.4205 (13)	0.313 (2)	0.4972 (12)	0.022*
N2	0.51214 (9)	0.33207 (18)	0.62387 (8)	0.0166 (3)
N3	0.49527 (9)	0.19563 (19)	0.41174 (9)	0.0179 (3)
H3N	0.4365 (13)	0.229 (3)	0.3827 (13)	0.021*
N4	0.54462 (9)	0.12100 (18)	0.36967 (9)	0.0172 (3)
C1	0.53819 (10)	0.2217 (2)	0.50290 (11)	0.0170 (3)
C2	0.45776 (10)	0.4008 (2)	0.65560 (10)	0.0158 (3)
C3	0.35589 (10)	0.4419 (2)	0.59818 (11)	0.0203 (3)
H3A	0.3499	0.5603	0.5693	0.030*
H3B	0.3227	0.4433	0.6365	0.030*
H3C	0.3287	0.3488	0.5513	0.030*
C4	0.50342 (10)	0.4407 (2)	0.75353 (10)	0.0163 (3)
C5	0.59838 (11)	0.3942 (2)	0.80910 (11)	0.0175 (3)
C6	0.63916 (11)	0.4332 (2)	0.90125 (11)	0.0206 (3)
H6	0.7024	0.3997	0.9379	0.025*
C7	0.58878 (11)	0.5202 (2)	0.94020 (11)	0.0225 (4)
H7	0.6175	0.5468	1.0033	0.027*
C8	0.49609 (11)	0.5689 (2)	0.88708 (11)	0.0223 (4)
H8	0.4613	0.6295	0.9136	0.027*
C9	0.45484 (11)	0.5287 (2)	0.79543 (11)	0.0191 (3)
H9	0.3913	0.5619	0.7598	0.023*
C10	0.50214 (11)	0.0843 (2)	0.28371 (10)	0.0172 (3)
C11	0.39945 (11)	0.1186 (2)	0.22693 (11)	0.0235 (4)
H11A	0.3647	0.0869	0.2618	0.035*
H11B	0.3771	0.0445	0.1718	0.035*
H11C	0.3896	0.2468	0.2101	0.035*
C12	0.56124 (11)	0.0036 (2)	0.24484 (10)	0.0178 (3)
C13	0.65610 (11)	−0.0429 (2)	0.29941 (11)	0.0187 (3)
C14	0.70852 (11)	−0.1286 (2)	0.26121 (11)	0.0227 (4)
H14	0.7713	−0.1634	0.2990	0.027*
C15	0.67062 (12)	−0.1635 (2)	0.16938 (12)	0.0242 (4)
H15	0.7073	−0.2212	0.1440	0.029*
C16	0.57851 (12)	−0.1140 (2)	0.11390 (11)	0.0247 (4)
H16	0.5523	−0.1360	0.0504	0.030*
C17	0.52543 (12)	−0.0331 (2)	0.15140 (11)	0.0217 (4)
H17	0.4624	−0.0010	0.1128	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01439 (18)	0.0259 (2)	0.01724 (19)	0.00368 (15)	0.00456 (14)	0.00086 (17)
O1	0.0168 (5)	0.0242 (6)	0.0187 (6)	0.0036 (5)	0.0039 (5)	−0.0026 (5)
O2	0.0162 (5)	0.0326 (7)	0.0167 (6)	0.0010 (5)	0.0054 (5)	−0.0034 (5)
O3	0.0144 (5)	0.0226 (7)	0.0283 (6)	0.0009 (5)	0.0031 (5)	−0.0023 (6)
N1	0.0135 (6)	0.0230 (8)	0.0150 (6)	0.0015 (5)	0.0042 (5)	−0.0006 (6)
N2	0.0165 (6)	0.0166 (7)	0.0148 (6)	−0.0005 (5)	0.0049 (5)	0.0007 (5)
N3	0.0142 (6)	0.0210 (7)	0.0162 (6)	0.0020 (5)	0.0046 (5)	−0.0002 (6)
N4	0.0170 (6)	0.0167 (7)	0.0176 (6)	−0.0003 (5)	0.0075 (5)	0.0003 (5)
C1	0.0168 (7)	0.0155 (8)	0.0180 (8)	−0.0017 (6)	0.0069 (6)	0.0014 (6)
C2	0.0152 (7)	0.0135 (8)	0.0181 (7)	−0.0021 (6)	0.0066 (6)	0.0014 (6)
C3	0.0165 (7)	0.0247 (9)	0.0182 (8)	−0.0006 (6)	0.0062 (6)	−0.0005 (7)
C4	0.0162 (7)	0.0139 (8)	0.0179 (7)	−0.0031 (6)	0.0066 (6)	0.0008 (6)
C5	0.0175 (7)	0.0130 (8)	0.0212 (8)	−0.0013 (6)	0.0078 (6)	0.0005 (6)
C6	0.0179 (7)	0.0185 (9)	0.0200 (8)	−0.0027 (6)	0.0032 (6)	0.0014 (7)
C7	0.0253 (8)	0.0226 (9)	0.0177 (8)	−0.0057 (7)	0.0075 (7)	−0.0023 (7)
C8	0.0247 (8)	0.0211 (9)	0.0243 (8)	−0.0022 (7)	0.0136 (7)	−0.0031 (7)
C9	0.0167 (7)	0.0194 (8)	0.0209 (8)	−0.0015 (6)	0.0081 (6)	0.0008 (7)
C10	0.0186 (7)	0.0132 (8)	0.0176 (7)	−0.0033 (6)	0.0058 (6)	0.0015 (6)
C11	0.0193 (8)	0.0236 (9)	0.0226 (8)	−0.0014 (6)	0.0046 (7)	0.0001 (7)
C12	0.0212 (8)	0.0136 (8)	0.0170 (7)	−0.0025 (6)	0.0069 (6)	0.0014 (6)
C13	0.0206 (7)	0.0181 (8)	0.0172 (7)	−0.0049 (6)	0.0080 (6)	0.0006 (6)
C14	0.0190 (8)	0.0249 (9)	0.0243 (8)	−0.0027 (6)	0.0096 (7)	0.0006 (7)
C15	0.0319 (9)	0.0202 (9)	0.0263 (9)	−0.0032 (7)	0.0181 (7)	−0.0024 (7)
C16	0.0360 (9)	0.0202 (9)	0.0169 (8)	−0.0018 (7)	0.0105 (7)	−0.0019 (7)
C17	0.0248 (8)	0.0168 (8)	0.0186 (8)	0.0003 (6)	0.0050 (7)	0.0008 (7)

Geometric parameters (Å, º) top

S1—C1	1.6754 (15)	C6—C7	1.380 (2)
O1—C5	1.3606 (19)	C6—H6	0.9500
O1—H1O	0.83 (2)	C7—C8	1.389 (2)
O2—C13	1.3550 (19)	C7—H7	0.9500
O2—H2O	0.82 (2)	C8—C9	1.382 (2)
O3—H3O	0.84 (2)	C8—H8	0.9500
O3—H4O	0.82 (2)	C9—H9	0.9500
N1—C1	1.355 (2)	C10—C12	1.470 (2)
N1—N2	1.3649 (18)	C10—C11	1.503 (2)
N1—H1N	0.865 (18)	C11—H11A	0.9800
N2—C2	1.290 (2)	C11—H11B	0.9800
N3—C1	1.356 (2)	C11—H11C	0.9800
N3—N4	1.3650 (18)	C12—C17	1.406 (2)
N3—H3N	0.876 (18)	C12—C13	1.416 (2)
N4—C10	1.2956 (19)	C13—C14	1.392 (2)
C2—C4	1.472 (2)	C14—C15	1.378 (2)
C2—C3	1.503 (2)	C14—H14	0.9500
C3—H3A	0.9800	C15—C16	1.391 (2)
C3—H3B	0.9800	C15—H15	0.9500
C3—H3C	0.9800	C16—C17	1.377 (2)
C4—C9	1.396 (2)	C16—H16	0.9500
C4—C5	1.420 (2)	C17—H17	0.9500
C5—C6	1.387 (2)

C5—O1—H1O	108.2 (14)	C8—C7—H7	120.0
C13—O2—H2O	107.0 (14)	C9—C8—C7	119.54 (16)
H3O—O3—H4O	109 (2)	C9—C8—H8	120.2
C1—N1—N2	118.65 (13)	C7—C8—H8	120.2
C1—N1—H1N	121.2 (12)	C8—C9—C4	122.18 (14)
N2—N1—H1N	120.2 (12)	C8—C9—H9	118.9
C2—N2—N1	120.48 (12)	C4—C9—H9	118.9
C1—N3—N4	119.32 (13)	N4—C10—C12	115.31 (13)
C1—N3—H3N	117.4 (12)	N4—C10—C11	123.03 (15)
N4—N3—H3N	123.3 (12)	C12—C10—C11	121.65 (14)
C10—N4—N3	119.45 (13)	C10—C11—H11A	109.5
N1—C1—N3	111.55 (13)	C10—C11—H11B	109.5
N1—C1—S1	124.15 (12)	H11A—C11—H11B	109.5
N3—C1—S1	124.30 (12)	C10—C11—H11C	109.5
N2—C2—C4	114.84 (13)	H11A—C11—H11C	109.5
N2—C2—C3	123.59 (14)	H11B—C11—H11C	109.5
C4—C2—C3	121.55 (14)	C17—C12—C13	116.86 (15)
C2—C3—H3A	109.5	C17—C12—C10	121.22 (14)
C2—C3—H3B	109.5	C13—C12—C10	121.91 (14)
H3A—C3—H3B	109.5	O2—C13—C14	116.31 (14)
C2—C3—H3C	109.5	O2—C13—C12	123.28 (15)
H3A—C3—H3C	109.5	C14—C13—C12	120.40 (15)
H3B—C3—H3C	109.5	C15—C14—C13	120.93 (15)
C9—C4—C5	117.19 (14)	C15—C14—H14	119.5
C9—C4—C2	120.92 (13)	C13—C14—H14	119.5
C5—C4—C2	121.88 (14)	C14—C15—C16	119.74 (16)
O1—C5—C6	117.06 (14)	C14—C15—H15	120.1
O1—C5—C4	122.53 (14)	C16—C15—H15	120.1
C6—C5—C4	120.40 (15)	C17—C16—C15	119.75 (15)
C7—C6—C5	120.68 (15)	C17—C16—H16	120.1
C7—C6—H6	119.7	C15—C16—H16	120.1
C5—C6—H6	119.7	C16—C17—C12	122.27 (15)
C6—C7—C8	120.00 (15)	C16—C17—H17	118.9
C6—C7—H7	120.0	C12—C17—H17	118.9

C1—N1—N2—C2	179.58 (14)	C7—C8—C9—C4	−0.4 (3)
C1—N3—N4—C10	175.22 (15)	C5—C4—C9—C8	−0.4 (2)
N2—N1—C1—N3	−178.03 (13)	C2—C4—C9—C8	−179.56 (15)
N2—N1—C1—S1	1.7 (2)	N3—N4—C10—C12	−179.77 (13)
N4—N3—C1—N1	−178.53 (13)	N3—N4—C10—C11	−0.5 (2)
N4—N3—C1—S1	1.8 (2)	N4—C10—C12—C17	−176.26 (15)
N1—N2—C2—C4	−178.58 (13)	C11—C10—C12—C17	4.5 (2)
N1—N2—C2—C3	0.2 (2)	N4—C10—C12—C13	4.6 (2)
N2—C2—C4—C9	174.83 (15)	C11—C10—C12—C13	−174.62 (15)
C3—C2—C4—C9	−4.0 (2)	C17—C12—C13—O2	178.25 (15)
N2—C2—C4—C5	−4.3 (2)	C10—C12—C13—O2	−2.6 (2)
C3—C2—C4—C5	176.85 (15)	C17—C12—C13—C14	−2.9 (2)
C9—C4—C5—O1	−178.43 (14)	C10—C12—C13—C14	176.31 (15)
C2—C4—C5—O1	0.8 (2)	O2—C13—C14—C15	−178.53 (15)
C9—C4—C5—C6	1.0 (2)	C12—C13—C14—C15	2.5 (3)
C2—C4—C5—C6	−179.76 (15)	C13—C14—C15—C16	−0.5 (3)
O1—C5—C6—C7	178.47 (15)	C14—C15—C16—C17	−1.0 (3)
C4—C5—C6—C7	−1.0 (2)	C15—C16—C17—C12	0.6 (3)
C5—C6—C7—C8	0.3 (3)	C13—C12—C17—C16	1.4 (2)
C6—C7—C8—C9	0.4 (3)	C10—C12—C17—C16	−177.81 (15)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C4–C9 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N2	0.83 (2)	1.79 (2)	2.5191 (17)	147 (2)
O1—H1O···S1	0.83 (2)	2.86 (2)	3.5126 (13)	138 (2)
O2—H2O···N4	0.82 (2)	1.81 (2)	2.542 (2)	148 (2)
O2—H2O···S1	0.82 (2)	2.96 (2)	3.6220 (15)	139 (2)
O3—H3O···O1	0.84 (2)	1.91 (2)	2.7525 (18)	174 (2)
O3—H4O···S1ⁱ	0.82 (2)	2.76 (2)	3.5089 (14)	154 (2)
N1—H1N···O3ⁱⁱ	0.87 (2)	2.04 (2)	2.8169 (19)	150 (2)
N3—H3N···O3ⁱⁱ	0.88 (2)	2.04 (2)	2.854 (2)	154 (2)
C11—H11C···Cg1ⁱⁱⁱ	0.98	2.61	3.4497 (17)	144

Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₈N₄O₂S·H₂O
M_r	360.43
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	15.8654 (3), 7.3938 (1), 16.3697 (3)
β (°)	115.922 (1)
V (Å³)	1727.06 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.44 × 0.13 × 0.07

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.905, 1
No. of measured, independent and observed [I > 2σ(I)] reflections	15464, 3968, 3136
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.102, 1.03
No. of reflections	3968
No. of parameters	246
No. of restraints	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.27

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS86 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C4–C9 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N2	0.83 (2)	1.79 (2)	2.5191 (17)	147 (2)
O1—H1O···S1	0.83 (2)	2.86 (2)	3.5126 (13)	138 (2)
O2—H2O···N4	0.82 (2)	1.81 (2)	2.542 (2)	148 (2)
O2—H2O···S1	0.82 (2)	2.96 (2)	3.6220 (15)	139 (2)
O3—H3O···O1	0.84 (2)	1.91 (2)	2.7525 (18)	174 (2)
O3—H4O···S1ⁱ	0.82 (2)	2.76 (2)	3.5089 (14)	154 (2)
N1—H1N···O3ⁱⁱ	0.87 (2)	2.037 (18)	2.8169 (19)	149.5 (19)
N3—H3N···O3ⁱⁱ	0.88 (2)	2.04 (2)	2.854 (2)	153.8 (18)
C11—H11C···Cg1ⁱⁱⁱ	0.98	2.61	3.4497 (17)	144

Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+1, −y+1, −z+1.

Footnotes

‡Additional correspondence author: maaffan@frst.unimas.my.

Acknowledgements

The authors express their gratitude to the Ministry of Science, Technology and Innovation (MOSTI) for a research grant (No. 06-01-09-SF0046), and to Universiti Malaysia Sarawak (UNIMAS) for financial support.

References

Affan, M. A., Foo, S. W., Jusoh, I., Hanapi, S. & Tiekink, E. R. T. (2009). Inorg. Chim. Acta, 362, 5031–5037. Web of Science CSD CrossRef Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Gielen, M. & Tiekink, E. R. T. (2005). Editors. Metallotherapeutic Drugs and Metal-Based Diagnostic Agents: The Use of Metals in Medicine, pp. 421–439. Chichester: John Wiley & Sons. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
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Zukerman-Schpector, J., Affan, M. A., Foo, S. W. & Tiekink, E. R. T. (2009). Acta Cryst. E65, o2951. Web of Science CrossRef IUCr Journals Google Scholar

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