(E)-2-[(1H-Imidazol-4-yl)methyl­­idene]hydrazinecarbo­thio­amide monohydrate

In the title compound, C₅H₇N₅S·H₂O, the main mol­ecule is approximately planar, with a maximum deviation from the mean plane through the non-H atoms of 0.1478 (12) Å for the amine N atom. In the crystal, the components are connected via N—H⋯O, N—H⋯S and O—H⋯N hydrogen bonds, forming a three-dimensional network.

Related literature

For the biological activity of thio­simecarbazone derivatives, see: Finch et al. (2000). For the crystal structures of related compounds, see: Alomar et al. (2013).

Experimental

Crystal data

• C₅H₇N₅S·H₂O

• M_r = 187.23

• Monoclinic, P 2₁ /c

• a = 10.8734 (5) Å

• b = 11.2416 (5) Å

• c = 7.0822 (3) Å

• β = 75.601 (2)°

• V = 838.50 (6) ų

• Z = 4

• Mo Kα radiation

• μ = 0.35 mm⁻¹

• T = 150 K

• 0.4 × 0.23 × 0.16 mm

Data collection

• Bruker APEXII CCD diffractometer

• 6537 measured reflections

• 1903 independent reflections

• 1726 reflections with I > 2σ(I)

• R_int = 0.031

Refinement

• R[F² > 2σ(F²)] = 0.030

• wR(F²) = 0.083

• S = 1.06

• 1903 reflections

• 127 parameters

• H-atom parameters not refined

• Δρ_max = 0.38 e Å⁻³

• Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O21	0.92 (2)	2.34 (2)	3.2325 (16)	163.2 (18)
N8—H8⋯S1^i	0.90 (2)	2.51 (2)	3.3334 (13)	153.0 (18)
O21—H21B⋯N10	0.87 (2)	2.17 (2)	3.0399 (15)	172 (2)
Symmetry code: (i) x, y-1, z.

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1999); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012) and CRYSCAL (T. Roisnel, local program).

Supporting information

S1. Comment

Our interest in thiosemicarbazone derivatives stems from their wide spectrum of biological activity (Finch et al., 2000; Alomar et al. 2013). As part of our study of thiosemicarbazone derivatives, we report herein the crystal structure of the title compound (I). The molecular structure of (I) is shown in Fig. 1. The molecule is approximately planar and the maximum deviation from the least squares plane through the 11 non-hydrogen atoms is -0.1478 (12) Å for N1. The bond angles suggest sp² hybridization for the C and N atoms which contributes to the planarity of the molecule. The crystal packing is stabilized by intermolecular N—H···O and N—H···S hydrogen bonds (Fig. 2 and Table 1) forming a three-dimensional network.

Related literature

For the biological activity of thiosimecarbazone derivatives, see: Finch et al. (2000). For the crystal structures of related compounds, see: Alomar et al. (2013).

S2. Experimental

All the chemicals were purchased from Merck and were used as received. An equimolar amount of thiosemicarbazide 10 mmol (0.91 g) and imidazolecarboxaldehyde 10 mmol (0.96 g) were dissolved in a mixture of ethanol and water (30 ml, 50%) and refluxed for 5 h in the presence of a catalytic amount of glacial acetic acid. Yellow crystals suitable for X-ray analysis were obtained after slow evaporation of the solution.

S3. Refinement

H atoms bonded to C atoms were placed in calculated positions with C—H = 0.95 Å and refined in a riding-model approximation with U_iso(H) = 1.2U_eq(C). The H atoms bonded to O and N atoms were refined independently with fixed isotropic displacement parameters.

Computing details

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1999); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012) and CRYSCAL (T. Roisnel, local program).

Figures

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Part of the crystal structure with hydrogen bonds shown as dashed lines.

(I)

Crystal data

C5H7N5S·H2O	Dx = 1.483 Mg m^−3
Mr = 187.23	Melting point: 0 K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.8734 (5) Å	Cell parameters from 3274 reflections
b = 11.2416 (5) Å	θ = 2.7–27.5°
c = 7.0822 (3) Å	µ = 0.35 mm^−1
β = 75.601 (2)°	T = 150 K
V = 838.50 (6) Å^3	Prism, colourless
Z = 4	0.4 × 0.23 × 0.16 mm
F(000) = 392

Data collection

Bruker APEXII CCD diffractometer	Rint = 0.031
Graphite monochromator	θmax = 27.5°, θmin = 3.5°
CCD rotation images, thin slices scans	h = −13→14
6537 measured reflections	k = −14→13
1903 independent reflections	l = −9→9
1726 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.083	H-atom parameters not refined
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0438P)^2 + 0.2645P] where P = (Fo^2 + 2Fc^2)/3
1903 reflections	(Δ/σ)max = 0.003
127 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.22 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq
S1	−0.87437 (3)	0.64372 (3)	0.33879 (5)	0.02064 (13)
N1	−0.66924 (10)	0.51441 (11)	0.17680 (17)	0.0192 (3)
H1A	−0.6294 (19)	0.443 (2)	0.140 (3)	0.05*
H1B	−0.6319 (19)	0.583 (2)	0.135 (3)	0.05*
C2	−0.79042 (12)	0.51613 (11)	0.27634 (18)	0.0154 (3)
N3	−0.84841 (10)	0.41073 (10)	0.32669 (17)	0.0177 (2)
H3	−0.928 (2)	0.408 (2)	0.406 (3)	0.05*
N4	−0.77834 (10)	0.30715 (10)	0.28202 (16)	0.0170 (2)
C5	−0.84105 (12)	0.21003 (12)	0.32281 (19)	0.0168 (3)
H5	−0.9299	0.2125	0.38	0.02*
C6	−0.77714 (12)	0.09669 (12)	0.28214 (18)	0.0165 (3)
C7	−0.82981 (13)	−0.01458 (12)	0.3055 (2)	0.0203 (3)
H7	−0.9172	−0.0336	0.3521	0.024*
N8	−0.73164 (11)	−0.09260 (11)	0.24822 (17)	0.0214 (3)
H8	−0.743 (2)	−0.172 (2)	0.251 (3)	0.05*
C9	−0.62411 (13)	−0.02867 (13)	0.1925 (2)	0.0218 (3)
H9	−0.5421	−0.0627	0.1467	0.026*
N10	−0.64591 (10)	0.08743 (10)	0.20915 (17)	0.0191 (3)
O21	−0.50826 (10)	0.29013 (9)	−0.04044 (17)	0.0250 (2)
H21A	−0.552 (2)	0.3077 (19)	−0.118 (3)	0.05*
H21B	−0.552 (2)	0.237 (2)	0.038 (3)	0.05*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.01797 (19)	0.01144 (19)	0.0285 (2)	0.00167 (11)	0.00184 (13)	0.00089 (13)
N1	0.0159 (5)	0.0133 (6)	0.0254 (6)	−0.0002 (4)	0.0004 (4)	0.0000 (5)
C2	0.0159 (6)	0.0146 (6)	0.0152 (6)	0.0002 (5)	−0.0030 (4)	−0.0003 (5)
N3	0.0154 (5)	0.0117 (6)	0.0224 (6)	0.0018 (4)	0.0025 (4)	−0.0001 (4)
N4	0.0174 (5)	0.0131 (6)	0.0185 (6)	0.0028 (4)	−0.0009 (4)	−0.0010 (4)
C5	0.0158 (6)	0.0158 (7)	0.0178 (6)	−0.0005 (5)	−0.0022 (5)	−0.0003 (5)
C6	0.0171 (6)	0.0162 (7)	0.0158 (6)	−0.0002 (5)	−0.0030 (5)	−0.0002 (5)
C7	0.0207 (6)	0.0163 (7)	0.0230 (7)	−0.0019 (5)	−0.0034 (5)	−0.0006 (5)
N8	0.0279 (6)	0.0114 (6)	0.0240 (6)	−0.0005 (5)	−0.0046 (5)	−0.0013 (5)
C9	0.0224 (7)	0.0167 (7)	0.0240 (7)	0.0032 (5)	−0.0015 (5)	−0.0012 (5)
N10	0.0177 (5)	0.0139 (6)	0.0233 (6)	0.0013 (4)	−0.0006 (4)	−0.0001 (4)
O21	0.0221 (5)	0.0221 (6)	0.0298 (6)	−0.0038 (4)	−0.0047 (4)	0.0068 (4)

Geometric parameters (Å, º)

S1—C2	1.6986 (13)	C6—C7	1.3685 (18)
N1—C2	1.3309 (17)	C6—N10	1.3955 (16)
N1—H1A	0.92 (2)	C7—N8	1.3630 (18)
N1—H1B	0.88 (2)	C7—H7	0.95
C2—N3	1.3480 (17)	N8—C9	1.3453 (18)
N3—N4	1.3844 (15)	N8—H8	0.90 (2)
N3—H3	0.90 (2)	C9—N10	1.3264 (18)
N4—C5	1.2816 (17)	C9—H9	0.95
C5—C6	1.4456 (18)	O21—H21A	0.83 (2)
C5—H5	0.95	O21—H21B	0.87 (2)
C2—N1—H1A	119.8 (13)	C7—C6—C5	127.99 (12)
C2—N1—H1B	118.5 (14)	N10—C6—C5	122.42 (12)
H1A—N1—H1B	121.2 (19)	N8—C7—C6	106.20 (12)
N1—C2—N3	117.63 (12)	N8—C7—H7	126.9
N1—C2—S1	123.18 (10)	C6—C7—H7	126.9
N3—C2—S1	119.18 (10)	C9—N8—C7	107.62 (12)
C2—N3—N4	118.96 (11)	C9—N8—H8	129.8 (14)
C2—N3—H3	120.5 (14)	C7—N8—H8	122.6 (14)
N4—N3—H3	119.7 (14)	N10—C9—N8	112.12 (12)
C5—N4—N3	115.68 (11)	N10—C9—H9	123.9
N4—C5—C6	120.23 (12)	N8—C9—H9	123.9
N4—C5—H5	119.9	C9—N10—C6	104.47 (11)
C6—C5—H5	119.9	H21A—O21—H21B	106 (2)
C7—C6—N10	109.59 (11)
N1—C2—N3—N4	3.30 (18)	C5—C6—C7—N8	−179.86 (12)
S1—C2—N3—N4	−177.56 (9)	C6—C7—N8—C9	−0.07 (15)
C2—N3—N4—C5	−175.73 (11)	C7—N8—C9—N10	−0.24 (16)
N3—N4—C5—C6	180.00 (11)	N8—C9—N10—C6	0.43 (15)
N4—C5—C6—C7	−175.90 (13)	C7—C6—N10—C9	−0.46 (15)
N4—C5—C6—N10	3.9 (2)	C5—C6—N10—C9	179.72 (12)
N10—C6—C7—N8	0.33 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O21	0.92 (2)	2.34 (2)	3.2325 (16)	163.2 (18)
N8—H8···S1^i	0.90 (2)	2.51 (2)	3.3334 (13)	153.0 (18)
O21—H21B···N10	0.87 (2)	2.17 (2)	3.0399 (15)	172 (2)

Symmetry code: (i) x, y−1, z.