3-(2-Hy­droxy­phen­yl)-1-{(E)-[1-(pyrazin-2-yl)ethyl­idene]amino}­thio­urea monohydrate

Normaya, E.; Farina, Y.; Halim, S.N.A.; Tiekink, E.R.T.

doi:10.1107/S1600536811010038

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Pages o943-o944

doi:10.1107/S1600536811010038

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3-(2-Hydroxyphenyl)-1-{(E)-[1-(pyrazin-2-yl)ethylidene]amino}thiourea monohydrate

Erna Normaya,^a Yang Farina,^b ‡ Siti Nadiah Abd Halim ^c and Edward R. T. Tiekink ^c ^*

^aInternational Islamic University Malaysia (IIUM), PO Box 141, Kuantan, Malaysia, ^bSchool of Chemical Sciences and Food Technology, Faculty Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 16 March 2011; accepted 17 March 2011; online 23 March 2011)

In the title compound, C₁₃H₁₃N₅OS·H₂O, the thiourea molecules closely resemble each other and are approximately planar; the dihedral angles formed between the terminal benzene rings are 7.88 (8) and 7.20 (8)°, respectively. The observed planarity correlates with the presence of bifurcated N—H⋯(O,N) hydrogen bonds. In the crystal, the molecules are connected into supramolecular double chains via a combination of N—H⋯S (linking the two independent molecules), O—H⋯O and O—H⋯N (linking dimeric aggregates into a supramolecular chain via hydroxy–water, water–water and water–pyrazine interactions) and O—H⋯S hydrogen bonds (connecting two chains). The chains are further connected by C—H⋯N and C—H⋯S interactions.

Related literature

For biological activity of thiourea derivatives, see: Venkatachalam et al. (2004 ). For related structures, see: Gunasekaran et al. (2010 ); Dzulkifli et al. (2011 ). For additional geometric analysis, see: Spek (2009 ).

Experimental

Crystal data

C₁₃H₁₃N₅OS·H₂O
M_r = 305.36
Triclinic, $[P \overline 1]$
a = 7.9808 (5) Å
b = 11.7557 (8) Å
c = 16.4160 (11) Å
α = 99.638 (1)°
β = 94.128 (1)°
γ = 109.200 (1)°
V = 1420.54 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 100 K
0.18 × 0.14 × 0.11 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.656, T_max = 0.746
18244 measured reflections
6505 independent reflections
5267 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.110
S = 1.04
6505 reflections
411 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1n⋯O1	0.88 (1)	2.11 (2)	2.5720 (15)	112 (1)
N1—H1n⋯N3	0.88 (1)	2.04 (2)	2.5435 (18)	116 (1)
N6—H6n⋯O2	0.87 (1)	2.11 (2)	2.5676 (15)	112 (1)
N6—H6n⋯N8	0.87 (1)	2.02 (2)	2.5358 (17)	117 (1)
O1—H1o⋯O1w	0.83 (1)	1.86 (1)	2.6820 (15)	170 (2)
O2—H2o⋯O2wⁱ	0.83 (1)	1.83 (1)	2.6481 (16)	169 (2)
O1w—H1w⋯N9ⁱⁱ	0.84 (1)	1.96 (1)	2.7958 (17)	169 (2)
O1w—H2w⋯S2ⁱⁱⁱ	0.83 (2)	2.82 (2)	3.4648 (13)	136 (2)
O2w—H3w⋯N4	0.84 (1)	2.02 (1)	2.8547 (17)	171 (2)
O2w—H4w⋯O1w	0.85 (2)	2.00 (2)	2.8357 (18)	169 (2)
N2—H2n⋯S2^iv	0.87 (1)	2.67 (1)	3.4802 (12)	156 (1)
N7—H7n⋯S1^v	0.87 (1)	2.58 (1)	3.4508 (12)	176 (2)
C16—H16⋯N5^vi	0.95	2.58	3.517 (2)	172
C22—H22a⋯S1^v	0.98	2.79	3.4454 (16)	125
Symmetry codes: (i) x, y, z-1; (ii) x, y, z+1; (iii) -x+1, -y+2, -z+1; (iv) x-1, y-1, z; (v) x+1, y+1, z; (vi) -x+2, -y+2, -z.

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ), DIAMOND (Brandenburg, 2006 ) and Qmol (Gans & Shalloway, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811010038/hg5012sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811010038/hg5012Isup2.hkl

checkCIF report

Comment top

Thiourea derivatives have biological potential (Venkatachalam et al., 2004) and attract continuing structural studies (Gunasekaran et al., 2010; Dzulkifli et al., 2011).

The title compound (I), Fig. 1, features two independent thiourea derivatives and two water molecules of crystallization in the asymmetric unit. As seen from the overlay diagram, Fig. 2, there are small differences between the independent thiourea molecules. These relate to the relative orientations of the terminal benzene rings; the r.m.s. deviation of bond distances = 0.0032 Å (Spek, 2009). The similarity between the molecules is seen in the dihedral angle formed between the rings = 7.88 (8) ° for the S1-containing molecule and 7.20 (8) ° for the other. The planarity of each molecule is readily explained in terms of bifurcated intramolecular N—H···O,N hydrogen bonds, Table 1.

The most prominent feature of the crystal packing is the formation of supramolecular double chains along [111]. The two molecules comprising the asymmetric unit are connected via an eight-membered {···HNC═S}₂ synthon and the resulting dimeric aggregates are connected by two molecules of water via a sequence of O—H···O hydrogen bonds. Thus, the hydroxyl group of one molecule is connected to a water molecule which hydrogen bonds to the second water molecule which in turn links the second hydroxyl group. Hydrogen bonds between the water molecules and pyrazine-N atoms close two fused 16-membered {···HOH···NC₃N₂CNC₂OH···O} synthons. This arrangement is stabilized by the intramolecular interactions outlined above. The result is a supramolecular chain, Fig. 3. Pairs of chains are linked via water-O—H···S hydrogen bonds leading to a double chain, Fig. 4. The chains are consolidated in the crystal packing by C—H···N and C—H···S interactions, Table 1 and Fig. 5.

Related literature top

For biological activity of thiourea derivatives, see: Venkatachalam et al. (2004). For related structures, see: Gunasekaran et al. (2010); Dzulkifli et al. (2011). For additional geometric analysis, see: Spek (2009).

Experimental top

The reaction of 2-acetylpyrazine with methyl hydrazinecarbodithioate (II) formed (E)-methyl-2-(1-(pyrazin-2-yl)ethylidene)hydrazinecarbodithioate (III). The condensation reaction of (III) with 2-phenolamine produced the title compound, (I), i.e. (E)-N-(2-hydroxyphenyl)-2-(1-(pyrazin-2- yl)ethylidene)hydrazinecarbothioamide (yield:73.3%, M.pt. 469—471 K).

Slow recrystallization of its butanol solution afforded yellow crystals of (I). Elemental anal. (calc.): C, 51.80 (51.13); H, 4.91 (4.95), N, 24.10 (22.94) %. FT—IR (ν_max; cm^-1): (O—H) 3459, (N—H) 3209, (C\b C) 3016, (CH₃) 2925, (C═N) 1609, (C≐C aromatic) 1555, (C—N) 1366, (pyrazyl) 1162, (N —N) 1121 and (C═S) 1023.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997), DIAMOND (Brandenburg, 2006) and Qmol (Gans & Shalloway, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structures of the components defining the asymmetric unit of (I) showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level.
	Fig. 2. Overlay diagram showing the superimposition of the S1-containing molecule (red) with the S2-containing molecule (blue).
	Fig. 3. Supramolecular chain in (I) mediated by O—H···O (orange), O—H···N (blue) and N—H···S (purple) hydrogen bonding shown as dashed lines.
	Fig. 4. Supramolecular double chain in (I) whereby the chain in Fig. 3 is connected via O—H···S hydrogen bonds shown as green dashed lines.
	Fig. 5. View in projection down the a axis of the crystal packing for (I). The C—H···N and C—H···S contacts are shown as pink dashed lines.

3-(2-Hydroxyphenyl)-1-{(E)-[1-(pyrazin-2-yl)ethylidene]amino}thiourea monohydrate top

Crystal data top

C₁₃H₁₃N₅OS·H₂O	Z = 4
M_r = 305.36	F(000) = 640
Triclinic, P1	D_x = 1.428 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9808 (5) Å	Cell parameters from 6288 reflections
b = 11.7557 (8) Å	θ = 2.5–30.6°
c = 16.4160 (11) Å	µ = 0.24 mm⁻¹
α = 99.638 (1)°	T = 100 K
β = 94.128 (1)°	Block, yellow
γ = 109.200 (1)°	0.18 × 0.14 × 0.11 mm
V = 1420.54 (16) Å³

Data collection top

Bruker SMART APEX diffractometer	6505 independent reflections
Radiation source: fine-focus sealed tube	5267 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω scans	θ_max = 27.5°, θ_min = 1.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.656, T_max = 0.746	k = −15→15
18244 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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0586P)² + 0.4197P] where P = (F_o² + 2F_c²)/3
6505 reflections	(Δ/σ)_max = 0.001
411 parameters	Δρ_max = 0.39 e Å⁻³
12 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₃H₁₃N₅OS·H₂O	γ = 109.200 (1)°
M_r = 305.36	V = 1420.54 (16) Å³
Triclinic, P1	Z = 4
a = 7.9808 (5) Å	Mo Kα radiation
b = 11.7557 (8) Å	µ = 0.24 mm⁻¹
c = 16.4160 (11) Å	T = 100 K
α = 99.638 (1)°	0.18 × 0.14 × 0.11 mm
β = 94.128 (1)°

Data collection top

Bruker SMART APEX diffractometer	6505 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	5267 reflections with I > 2σ(I)
T_min = 0.656, T_max = 0.746	R_int = 0.031
18244 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	12 restraints
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.39 e Å⁻³
6505 reflections	Δρ_min = −0.30 e Å⁻³
411 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	−0.09788 (5)	0.17115 (3)	0.34884 (2)	0.02054 (11)
O1	0.19179 (14)	0.50524 (9)	0.62276 (6)	0.0191 (2)
H1O	0.223 (2)	0.5485 (15)	0.6707 (7)	0.029*
N1	0.06763 (16)	0.35848 (11)	0.48035 (7)	0.0160 (3)
H1N	0.1553 (18)	0.4298 (10)	0.4942 (10)	0.019*
N2	0.17706 (16)	0.37485 (11)	0.35765 (7)	0.0155 (3)
H2N	0.176 (2)	0.3458 (15)	0.3051 (6)	0.019*
N3	0.30025 (16)	0.48289 (11)	0.40124 (7)	0.0151 (2)
N4	0.63006 (17)	0.80104 (11)	0.55376 (8)	0.0187 (3)
N5	0.65300 (16)	0.74828 (11)	0.38282 (8)	0.0173 (3)
C1	0.04480 (19)	0.40506 (13)	0.62335 (9)	0.0157 (3)
C2	−0.0340 (2)	0.38248 (14)	0.69423 (9)	0.0193 (3)
H2	0.0134	0.4390	0.7459	0.023*
C3	−0.1821 (2)	0.27734 (14)	0.68991 (9)	0.0201 (3)
H3	−0.2360	0.2619	0.7386	0.024*
C4	−0.2515 (2)	0.19499 (14)	0.61453 (9)	0.0194 (3)
H4	−0.3522	0.1228	0.6119	0.023*
C5	−0.17480 (19)	0.21715 (13)	0.54249 (9)	0.0175 (3)
H5	−0.2234	0.1606	0.4910	0.021*
C6	−0.02660 (19)	0.32252 (13)	0.54647 (8)	0.0148 (3)
C7	0.05216 (19)	0.30635 (13)	0.39999 (9)	0.0153 (3)
C8	0.42014 (19)	0.55019 (13)	0.36458 (8)	0.0147 (3)
C9	0.4445 (2)	0.52302 (14)	0.27451 (8)	0.0187 (3)
H9A	0.4149	0.4342	0.2557	0.028*
H9B	0.5692	0.5659	0.2680	0.028*
H9C	0.3653	0.5512	0.2410	0.028*
C10	0.53888 (18)	0.66744 (13)	0.41919 (9)	0.0146 (3)
C11	0.52873 (19)	0.69459 (13)	0.50503 (9)	0.0167 (3)
H11	0.4468	0.6349	0.5290	0.020*
C12	0.7435 (2)	0.88265 (14)	0.51665 (9)	0.0201 (3)
H12	0.8179	0.9601	0.5491	0.024*
C13	0.7538 (2)	0.85604 (14)	0.43227 (10)	0.0210 (3)
H13	0.8353	0.9162	0.4084	0.025*
S2	1.07562 (5)	1.30651 (3)	0.14135 (2)	0.01929 (10)
O2	0.78422 (15)	0.96845 (10)	−0.13104 (6)	0.0210 (2)
H2O	0.746 (2)	0.9237 (16)	−0.1782 (7)	0.032*
N6	0.91194 (16)	1.11695 (11)	0.01014 (7)	0.0157 (2)
H6N	0.8277 (18)	1.0449 (10)	−0.0021 (10)	0.019*
N7	0.80922 (16)	1.09918 (11)	0.13407 (7)	0.0157 (3)
H7N	0.829 (2)	1.1201 (15)	0.1885 (6)	0.019*
N8	0.68925 (16)	0.98922 (10)	0.09106 (7)	0.0150 (2)
N9	0.35318 (18)	0.67259 (12)	−0.06046 (8)	0.0230 (3)
N10	0.34629 (17)	0.72072 (12)	0.11192 (8)	0.0194 (3)
C14	0.92330 (19)	1.07099 (13)	−0.13441 (9)	0.0164 (3)
C15	0.9944 (2)	1.09597 (14)	−0.20668 (9)	0.0201 (3)
H15	0.9453	1.0394	−0.2581	0.024*
C16	1.1376 (2)	1.20380 (14)	−0.20400 (10)	0.0212 (3)
H16	1.1856	1.2213	−0.2536	0.025*
C17	1.2101 (2)	1.28569 (14)	−0.12866 (10)	0.0212 (3)
H17	1.3081	1.3591	−0.1271	0.025*
C18	1.1413 (2)	1.26184 (14)	−0.05531 (9)	0.0185 (3)
H18	1.1926	1.3182	−0.0039	0.022*
C19	0.99712 (19)	1.15496 (13)	−0.05791 (8)	0.0154 (3)
C20	0.93076 (18)	1.16914 (13)	0.09055 (8)	0.0143 (3)
C21	0.57203 (19)	0.92136 (13)	0.12853 (9)	0.0157 (3)
C22	0.5460 (2)	0.94878 (14)	0.21817 (9)	0.0215 (3)
H22A	0.5889	1.0380	0.2386	0.032*
H22B	0.6137	0.9122	0.2512	0.032*
H22C	0.4185	0.9141	0.2233	0.032*
C23	0.45390 (19)	0.80368 (13)	0.07433 (9)	0.0158 (3)
C24	0.4564 (2)	0.77884 (14)	−0.01203 (9)	0.0200 (3)
H24	0.5342	0.8397	−0.0367	0.024*
C25	0.2466 (2)	0.58978 (14)	−0.02229 (10)	0.0238 (3)
H25	0.1707	0.5126	−0.0547	0.029*
C26	0.2442 (2)	0.61369 (14)	0.06273 (10)	0.0227 (3)
H26	0.1674	0.5520	0.0872	0.027*
O1W	0.29296 (15)	0.66684 (11)	0.76876 (7)	0.0240 (3)
H1W	0.320 (3)	0.6634 (19)	0.8187 (7)	0.036*
H2W	0.209 (2)	0.6932 (18)	0.7662 (11)	0.036*
O2W	0.62751 (16)	0.80846 (11)	0.72836 (7)	0.0264 (3)
H4W	0.5218 (15)	0.7672 (16)	0.7342 (11)	0.040*
H3W	0.634 (3)	0.8147 (19)	0.6783 (7)	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0241 (2)	0.01728 (19)	0.01090 (18)	−0.00349 (15)	0.00142 (14)	−0.00018 (13)
O1	0.0207 (5)	0.0182 (5)	0.0111 (5)	−0.0003 (4)	0.0027 (4)	−0.0024 (4)
N1	0.0165 (6)	0.0149 (6)	0.0117 (6)	−0.0001 (5)	0.0033 (5)	0.0003 (5)
N2	0.0180 (6)	0.0140 (6)	0.0091 (5)	−0.0001 (5)	0.0020 (5)	−0.0006 (5)
N3	0.0156 (6)	0.0141 (6)	0.0125 (6)	0.0027 (5)	0.0002 (5)	0.0000 (5)
N4	0.0196 (6)	0.0176 (6)	0.0157 (6)	0.0040 (5)	−0.0003 (5)	0.0009 (5)
N5	0.0162 (6)	0.0180 (6)	0.0154 (6)	0.0026 (5)	0.0029 (5)	0.0038 (5)
C1	0.0171 (7)	0.0164 (7)	0.0136 (7)	0.0060 (5)	0.0022 (5)	0.0025 (5)
C2	0.0243 (8)	0.0221 (7)	0.0125 (7)	0.0089 (6)	0.0043 (6)	0.0033 (6)
C3	0.0241 (8)	0.0241 (8)	0.0159 (7)	0.0106 (6)	0.0090 (6)	0.0075 (6)
C4	0.0191 (7)	0.0189 (7)	0.0211 (7)	0.0054 (6)	0.0078 (6)	0.0064 (6)
C5	0.0181 (7)	0.0181 (7)	0.0144 (7)	0.0050 (6)	0.0022 (5)	0.0006 (6)
C6	0.0175 (7)	0.0168 (7)	0.0113 (6)	0.0070 (6)	0.0043 (5)	0.0033 (5)
C7	0.0161 (7)	0.0162 (7)	0.0127 (7)	0.0047 (5)	0.0012 (5)	0.0025 (5)
C8	0.0165 (7)	0.0154 (7)	0.0113 (6)	0.0049 (5)	0.0013 (5)	0.0019 (5)
C9	0.0213 (7)	0.0202 (7)	0.0112 (7)	0.0034 (6)	0.0034 (6)	0.0017 (6)
C10	0.0138 (7)	0.0158 (7)	0.0140 (7)	0.0048 (5)	0.0017 (5)	0.0033 (5)
C11	0.0189 (7)	0.0157 (7)	0.0133 (7)	0.0035 (6)	0.0007 (5)	0.0027 (5)
C12	0.0202 (7)	0.0152 (7)	0.0200 (7)	0.0015 (6)	0.0000 (6)	0.0010 (6)
C13	0.0192 (7)	0.0184 (7)	0.0211 (8)	0.0008 (6)	0.0017 (6)	0.0046 (6)
S2	0.0241 (2)	0.01506 (18)	0.01128 (18)	−0.00166 (14)	0.00061 (14)	0.00055 (13)
O2	0.0234 (6)	0.0209 (5)	0.0113 (5)	0.0005 (4)	0.0013 (4)	−0.0016 (4)
N6	0.0174 (6)	0.0131 (6)	0.0116 (6)	−0.0005 (5)	0.0031 (5)	0.0001 (5)
N7	0.0198 (6)	0.0135 (6)	0.0093 (5)	0.0010 (5)	0.0018 (5)	−0.0003 (5)
N8	0.0170 (6)	0.0118 (6)	0.0135 (6)	0.0026 (5)	0.0008 (5)	0.0004 (4)
N9	0.0229 (7)	0.0214 (7)	0.0180 (6)	0.0018 (5)	0.0023 (5)	−0.0022 (5)
N10	0.0179 (6)	0.0185 (6)	0.0187 (6)	0.0013 (5)	0.0022 (5)	0.0057 (5)
C14	0.0183 (7)	0.0169 (7)	0.0150 (7)	0.0073 (6)	0.0030 (5)	0.0029 (6)
C15	0.0251 (8)	0.0255 (8)	0.0117 (7)	0.0116 (6)	0.0033 (6)	0.0032 (6)
C16	0.0264 (8)	0.0259 (8)	0.0181 (7)	0.0138 (7)	0.0106 (6)	0.0097 (6)
C17	0.0223 (8)	0.0212 (7)	0.0225 (8)	0.0076 (6)	0.0088 (6)	0.0079 (6)
C18	0.0196 (7)	0.0189 (7)	0.0167 (7)	0.0057 (6)	0.0052 (6)	0.0034 (6)
C19	0.0187 (7)	0.0182 (7)	0.0110 (6)	0.0079 (6)	0.0037 (5)	0.0035 (5)
C20	0.0158 (7)	0.0146 (6)	0.0114 (6)	0.0042 (5)	0.0015 (5)	0.0021 (5)
C21	0.0173 (7)	0.0167 (7)	0.0127 (7)	0.0054 (6)	0.0019 (5)	0.0029 (5)
C22	0.0231 (8)	0.0217 (8)	0.0136 (7)	0.0011 (6)	0.0044 (6)	0.0003 (6)
C23	0.0150 (7)	0.0160 (7)	0.0153 (7)	0.0040 (5)	0.0018 (5)	0.0027 (5)
C24	0.0202 (7)	0.0194 (7)	0.0154 (7)	0.0015 (6)	0.0021 (6)	0.0006 (6)
C25	0.0215 (8)	0.0166 (7)	0.0264 (8)	0.0008 (6)	0.0015 (6)	−0.0016 (6)
C26	0.0194 (7)	0.0188 (7)	0.0248 (8)	−0.0001 (6)	0.0017 (6)	0.0055 (6)
O1W	0.0261 (6)	0.0278 (6)	0.0161 (5)	0.0115 (5)	−0.0008 (5)	−0.0039 (5)
O2W	0.0304 (6)	0.0284 (6)	0.0128 (5)	0.0032 (5)	0.0014 (5)	−0.0014 (5)

Geometric parameters (Å, º) top

S1—C7	1.6797 (14)	O2—H2O	0.832 (9)
O1—C1	1.3638 (17)	N6—C20	1.3347 (17)
O1—H1O	0.834 (9)	N6—C19	1.4094 (18)
N1—C7	1.3370 (18)	N6—H6N	0.871 (9)
N1—C6	1.4087 (18)	N7—N8	1.3671 (16)
N1—H1N	0.878 (9)	N7—C20	1.3782 (18)
N2—N3	1.3656 (16)	N7—H7N	0.874 (9)
N2—C7	1.3727 (18)	N8—C21	1.2830 (18)
N2—H2N	0.872 (9)	N9—C24	1.3294 (19)
N3—C8	1.2837 (18)	N9—C25	1.342 (2)
N4—C11	1.3289 (18)	N10—C26	1.3379 (19)
N4—C12	1.3471 (19)	N10—C23	1.3403 (18)
N5—C10	1.3372 (18)	C14—C15	1.386 (2)
N5—C13	1.3425 (19)	C14—C19	1.4122 (19)
C1—C2	1.385 (2)	C15—C16	1.392 (2)
C1—C6	1.4078 (19)	C15—H15	0.9500
C2—C3	1.389 (2)	C16—C17	1.387 (2)
C2—H2	0.9500	C16—H16	0.9500
C3—C4	1.387 (2)	C17—C18	1.392 (2)
C3—H3	0.9500	C17—H17	0.9500
C4—C5	1.394 (2)	C18—C19	1.389 (2)
C4—H4	0.9500	C18—H18	0.9500
C5—C6	1.391 (2)	C21—C23	1.4844 (19)
C5—H5	0.9500	C21—C22	1.4972 (19)
C8—C10	1.4854 (19)	C22—H22A	0.9800
C8—C9	1.5000 (19)	C22—H22B	0.9800
C9—H9A	0.9800	C22—H22C	0.9800
C9—H9B	0.9800	C23—C24	1.402 (2)
C9—H9C	0.9800	C24—H24	0.9500
C10—C11	1.4061 (19)	C25—C26	1.380 (2)
C11—H11	0.9500	C25—H25	0.9500
C12—C13	1.383 (2)	C26—H26	0.9500
C12—H12	0.9500	O1W—H1W	0.845 (9)
C13—H13	0.9500	O1W—H2W	0.829 (9)
S2—C20	1.6799 (14)	O2W—H4W	0.845 (9)
O2—C14	1.3562 (18)	O2W—H3W	0.842 (9)

C1—O1—H1O	109.1 (13)	C20—N6—C19	133.48 (12)
C7—N1—C6	133.34 (12)	C20—N6—H6N	111.9 (11)
C7—N1—H1N	112.4 (11)	C19—N6—H6N	114.6 (11)
C6—N1—H1N	114.2 (11)	N8—N7—C20	117.62 (11)
N3—N2—C7	117.93 (11)	N8—N7—H7N	123.7 (11)
N3—N2—H2N	123.7 (11)	C20—N7—H7N	117.2 (11)
C7—N2—H2N	118.4 (11)	C21—N8—N7	120.02 (12)
C8—N3—N2	120.36 (12)	C24—N9—C25	116.48 (13)
C11—N4—C12	116.55 (13)	C26—N10—C23	116.37 (13)
C10—N5—C13	116.46 (13)	O2—C14—C15	124.21 (13)
O1—C1—C2	123.55 (13)	O2—C14—C19	115.96 (12)
O1—C1—C6	116.29 (12)	C15—C14—C19	119.83 (14)
C2—C1—C6	120.16 (13)	C14—C15—C16	120.11 (14)
C1—C2—C3	120.07 (14)	C14—C15—H15	119.9
C1—C2—H2	120.0	C16—C15—H15	119.9
C3—C2—H2	120.0	C17—C16—C15	119.82 (14)
C4—C3—C2	119.96 (14)	C17—C16—H16	120.1
C4—C3—H3	120.0	C15—C16—H16	120.1
C2—C3—H3	120.0	C16—C17—C18	120.92 (15)
C3—C4—C5	120.61 (14)	C16—C17—H17	119.5
C3—C4—H4	119.7	C18—C17—H17	119.5
C5—C4—H4	119.7	C19—C18—C17	119.41 (14)
C6—C5—C4	119.63 (13)	C19—C18—H18	120.3
C6—C5—H5	120.2	C17—C18—H18	120.3
C4—C5—H5	120.2	C18—C19—N6	126.65 (13)
C5—C6—C1	119.56 (13)	C18—C19—C14	119.91 (13)
C5—C6—N1	127.05 (13)	N6—C19—C14	113.44 (12)
C1—C6—N1	113.39 (12)	N6—C20—N7	113.11 (12)
N1—C7—N2	113.40 (12)	N6—C20—S2	128.34 (11)
N1—C7—S1	127.44 (11)	N7—C20—S2	118.52 (10)
N2—C7—S1	119.15 (10)	N8—C21—C23	113.87 (12)
N3—C8—C10	114.04 (12)	N8—C21—C22	127.09 (13)
N3—C8—C9	126.55 (13)	C23—C21—C22	119.03 (12)
C10—C8—C9	119.37 (12)	C21—C22—H22A	109.5
C8—C9—H9A	109.5	C21—C22—H22B	109.5
C8—C9—H9B	109.5	H22A—C22—H22B	109.5
H9A—C9—H9B	109.5	C21—C22—H22C	109.5
C8—C9—H9C	109.5	H22A—C22—H22C	109.5
H9A—C9—H9C	109.5	H22B—C22—H22C	109.5
H9B—C9—H9C	109.5	N10—C23—C24	121.20 (13)
N5—C10—C11	121.07 (13)	N10—C23—C21	116.94 (12)
N5—C10—C8	117.13 (12)	C24—C23—C21	121.86 (13)
C11—C10—C8	121.77 (13)	N9—C24—C23	121.95 (14)
N4—C11—C10	122.14 (13)	N9—C24—H24	119.0
N4—C11—H11	118.9	C23—C24—H24	119.0
C10—C11—H11	118.9	N9—C25—C26	121.75 (14)
N4—C12—C13	121.38 (14)	N9—C25—H25	119.1
N4—C12—H12	119.3	C26—C25—H25	119.1
C13—C12—H12	119.3	N10—C26—C25	122.24 (14)
N5—C13—C12	122.38 (14)	N10—C26—H26	118.9
N5—C13—H13	118.8	C25—C26—H26	118.9
C12—C13—H13	118.8	H1W—O1W—H2W	109.0 (16)
C14—O2—H2O	111.0 (14)	H4W—O2W—H3W	110.5 (16)

C7—N2—N3—C8	179.84 (13)	C20—N7—N8—C21	−179.19 (13)
O1—C1—C2—C3	−179.12 (13)	O2—C14—C15—C16	−179.93 (14)
C6—C1—C2—C3	0.9 (2)	C19—C14—C15—C16	−0.3 (2)
C1—C2—C3—C4	−0.1 (2)	C14—C15—C16—C17	0.6 (2)
C2—C3—C4—C5	−0.6 (2)	C15—C16—C17—C18	−0.1 (2)
C3—C4—C5—C6	0.4 (2)	C16—C17—C18—C19	−0.6 (2)
C4—C5—C6—C1	0.4 (2)	C17—C18—C19—N6	179.92 (14)
C4—C5—C6—N1	179.51 (14)	C17—C18—C19—C14	0.8 (2)
O1—C1—C6—C5	178.95 (13)	C20—N6—C19—C18	5.0 (3)
C2—C1—C6—C5	−1.1 (2)	C20—N6—C19—C14	−175.84 (15)
O1—C1—C6—N1	−0.25 (18)	O2—C14—C19—C18	179.25 (13)
C2—C1—C6—N1	179.70 (13)	C15—C14—C19—C18	−0.4 (2)
C7—N1—C6—C5	−2.7 (3)	O2—C14—C19—N6	0.05 (18)
C7—N1—C6—C1	176.41 (15)	C15—C14—C19—N6	−179.61 (13)
C6—N1—C7—N2	−179.14 (14)	C19—N6—C20—N7	176.62 (14)
C6—N1—C7—S1	0.5 (2)	C19—N6—C20—S2	−1.4 (2)
N3—N2—C7—N1	1.30 (19)	N8—N7—C20—N6	0.04 (18)
N3—N2—C7—S1	−178.38 (10)	N8—N7—C20—S2	178.23 (10)
N2—N3—C8—C10	177.27 (12)	N7—N8—C21—C23	−178.68 (12)
N2—N3—C8—C9	−0.6 (2)	N7—N8—C21—C22	0.9 (2)
C13—N5—C10—C11	−0.9 (2)	C26—N10—C23—C24	0.7 (2)
C13—N5—C10—C8	177.13 (13)	C26—N10—C23—C21	−178.17 (13)
N3—C8—C10—N5	−172.44 (13)	N8—C21—C23—N10	170.53 (13)
C9—C8—C10—N5	5.6 (2)	C22—C21—C23—N10	−9.1 (2)
N3—C8—C10—C11	5.6 (2)	N8—C21—C23—C24	−8.3 (2)
C9—C8—C10—C11	−176.37 (13)	C22—C21—C23—C24	172.12 (14)
C12—N4—C11—C10	0.2 (2)	C25—N9—C24—C23	−0.3 (2)
N5—C10—C11—N4	0.4 (2)	N10—C23—C24—N9	−0.1 (2)
C8—C10—C11—N4	−177.57 (13)	C21—C23—C24—N9	178.71 (14)
C11—N4—C12—C13	−0.3 (2)	C24—N9—C25—C26	0.0 (2)
C10—N5—C13—C12	0.9 (2)	C23—N10—C26—C25	−0.9 (2)
N4—C12—C13—N5	−0.2 (2)	N9—C25—C26—N10	0.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···O1	0.88 (1)	2.11 (2)	2.5720 (15)	112 (1)
N1—H1n···N3	0.88 (1)	2.04 (2)	2.5435 (18)	116 (1)
N6—H6n···O2	0.87 (1)	2.11 (2)	2.5676 (15)	112 (1)
N6—H6n···N8	0.87 (1)	2.02 (2)	2.5358 (17)	117 (1)
O1—H1o···O1w	0.83 (1)	1.86 (1)	2.6820 (15)	170 (2)
O2—H2o···O2wⁱ	0.83 (1)	1.83 (1)	2.6481 (16)	169 (2)
O1w—H1w···N9ⁱⁱ	0.84 (1)	1.96 (1)	2.7958 (17)	169 (2)
O1w—H2w···S2ⁱⁱⁱ	0.83 (2)	2.82 (2)	3.4648 (13)	136 (2)
O2w—H3w···N4	0.84 (1)	2.02 (1)	2.8547 (17)	171 (2)
O2w—H4w···O1w	0.85 (2)	2.00 (2)	2.8357 (18)	169 (2)
N2—H2n···S2^iv	0.87 (1)	2.67 (1)	3.4802 (12)	156 (1)
N7—H7n···S1^v	0.87 (1)	2.58 (1)	3.4508 (12)	176 (2)
C16—H16···N5^vi	0.95	2.58	3.517 (2)	172
C22—H22a···S1^v	0.98	2.79	3.4454 (16)	125

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₃N₅OS·H₂O
M_r	305.36
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.9808 (5), 11.7557 (8), 16.4160 (11)
α, β, γ (°)	99.638 (1), 94.128 (1), 109.200 (1)
V (Å³)	1420.54 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.18 × 0.14 × 0.11

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.656, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	18244, 6505, 5267
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.110, 1.04
No. of reflections	6505
No. of parameters	411
No. of restraints	12
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.30

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), DIAMOND (Brandenburg, 2006) and Qmol (Gans & Shalloway, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···O1	0.878 (13)	2.107 (16)	2.5720 (15)	112.3 (12)
N1—H1n···N3	0.878 (13)	2.038 (15)	2.5435 (18)	115.5 (13)
N6—H6n···O2	0.871 (12)	2.112 (16)	2.5676 (15)	111.9 (12)
N6—H6n···N8	0.871 (12)	2.023 (15)	2.5358 (17)	116.7 (13)
O1—H1o···O1w	0.833 (12)	1.857 (13)	2.6820 (15)	170.3 (16)
O2—H2o···O2wⁱ	0.833 (13)	1.826 (14)	2.6481 (16)	168.9 (17)
O1w—H1w···N9ⁱⁱ	0.844 (13)	1.962 (12)	2.7958 (17)	169 (2)
O1w—H2w···S2ⁱⁱⁱ	0.827 (18)	2.822 (18)	3.4648 (13)	136.0 (16)
O2w—H3w···N4	0.841 (13)	2.021 (12)	2.8547 (17)	171 (2)
O2w—H4w···O1w	0.845 (15)	2.001 (16)	2.8357 (18)	169.1 (16)
N2—H2n···S2^iv	0.871 (10)	2.667 (10)	3.4802 (12)	155.9 (14)
N7—H7n···S1^v	0.874 (10)	2.579 (10)	3.4508 (12)	175.6 (15)
C16—H16···N5^vi	0.95	2.58	3.517 (2)	172
C22—H22a···S1^v	0.98	2.79	3.4454 (16)	125

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

Footnotes

‡Additional correspondence author, e-mail: farina@ukm.my.

Acknowledgements

We thank to University Kebangsaan Malaysia, the International Islamic University Malaysia and the Ministry of Higher Education, Malaysia, for supporting this research through grant GUP-NBT-08–27-112. The authors also thank the University of Malaya for support of the crystallographic facility and acknowledge an UMRG grant (RG125/10AFR).

References

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dzulkifli, N. N., Farina, Y., Yamin, B. M., Baba, I. & Tiekink, E. R. T. (2011). Acta Cryst. E67, o872. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Gans, J. & Shalloway, D. (2001). J. Mol. Graph. Model. 19, 557–559. Web of Science CrossRef PubMed CAS Google Scholar
Gunasekaran, N., Karvembu, R., Ng, S. W. & Tiekink, E. R. T. (2010). Acta Cryst. E66, o2572–o2573. Web of Science CSD CrossRef IUCr Journals 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
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Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 67| Part 4| April 2011| Pages o943-o944

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

3-(2-Hy­dr­oxy­phen­yl)-1-{(E)-[1-(pyrazin-2-yl)ethyl­­idene]amino}­thio­urea monohydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Footnotes

Acknowledgements

References

organic compounds

3-(2-Hydroxyphenyl)-1-{(E)-[1-(pyrazin-2-yl)ethylidene]amino}thiourea monohydrate