2-[1-(2-Hy­droxy-4-meth­oxy­phen­yl)ethyl­idene]-N-methyl­hydrazinecarbo­thio­amide

Anderson, B.J.; Freedman, M.B.; Millikan, S.P.; Jasinski, J.P.

doi:10.1107/S1600536813019831

organic compounds

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doi:10.1107/S1600536813019831

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2-[1-(2-Hydroxy-4-methoxyphenyl)ethylidene]-N-methylhydrazinecarbothioamide

Brian J. Anderson,^a Michael B. Freedman,^a Sean P. Millikan ^a and Jerry P. Jasinski ^a ^*

^aDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA
^*Correspondence e-mail: jjasinski@keene.edu

(Received 16 July 2013; accepted 17 July 2013; online 24 July 2013)

In the title compound, C₁₁H₁₅N₃O₂S, the dihedral angle between the mean planes of the benzene ring and hydrazinecarbothioamide group is 9.2 (1)°. An intramolecular O—H⋯N hydrogen bond is observed, serving to maintain an approximately planar conformation for the molecule. In the crystal, inversion dimers linked by C—H⋯O interactions occur. Further C—H⋯O contacts link dimers into (010) chains.

Related literature

For the synthesis and structure of thiosemicarbazones as ligands, see: Lobana et al. (2009 , 2012 ). For palladium complexes with thiosemicarbazone ligands, see: Chellan et al. (2010 ). For related structures, see: Anderson et al. (2012 , 2013 ). For bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₁H₁₅N₃O₂S
M_r = 253.32
Monoclinic, P 2₁ /n
a = 10.9881 (8) Å
b = 9.1468 (6) Å
c = 12.5575 (9) Å
β = 109.400 (8)°
V = 1190.45 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 173 K
0.42 × 0.38 × 0.14 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ) T_min = 0.728, T_max = 1.000
13894 measured reflections
4104 independent reflections
3320 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.076
wR(F²) = 0.231
S = 1.16
4104 reflections
158 parameters
H-atom parameters constrained
Δρ_max = 1.21 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.85	2.566 (3)	145
C10—H10A⋯O2ⁱ	0.96	2.59	3.301 (4)	132
C10—H10C⋯O1ⁱⁱ	0.96	2.57	3.481 (4)	158
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1.

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813019831/hg5331sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813019831/hg5331Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813019831/hg5331Isup3.cml

checkCIF report

Comment top

Thiosemicarbazones are a versatile class of ligands that can adopt multiple modes of binding to a metal (Lobana, et al., 2009) and the synthesis and structure determination of these metal complexes is an active area of research. (Lobana, et al., 2012) Palladium complexes with thiosemicarbazone ligands have been shown to have a variety of biological activity including anti-fungal and anti-tumor activity. (Chellan, et al., 2010). We have previously reported the structure of two analogous novel thiosemicarbazones (Anderson, et al., 2012; Anderson, et al., 2013). Here, we report the synthesis and crystal structure of a novel thiosemicarbazone ligand, (I), C₁₁H₁₅N₃O₂S .

In (I), the dihedral angle between the mean planes of the benzene ring and hydrazinecarbothioamide group (N1/N2/C8/S1/N3) is 9.2 (1)° (Fig. 1). Bond lengths are in normal ranges (Allen et al., 1987). In the crystal, an intramolecular O—H···N hydrogen bond is observed serving to keep the molecule in a nearly planar conformation. Additional weak and C—H···O intermolecular interactions (Table 1) assist in linking the molecules into dimers along (010) and influence crystal packing (Fig. 2).

Related literature top

For the synthesis and structure of thiosemicarbazones as ligands that bind to metals, see: Lobana et al. (2009, 2012). For palladium complexes with thiosemicarbazone ligands, see: Chellan et al. (2010). For related structures, see: Anderson et al. (2012, 2013). For bond lengths, see: Allen et al. (1987).

Experimental top

A 50 mL round bottom flask was charged with 0.218 g (1.31 mmol) of 2'-hydroxy-4'-methoxyacetophenone, 0.138 g (1.31 mmol) of 4-methyl-3- thiosemicarbazide, dissolved in 20 mL of methanol. The resulting colorless solution was refluxed for 48 hours and then a drop of concentrated HCl was added and the solution was refluxed for an additional 48 hours. The resulting yellow solution was transferred to a 125 mL separatory funnel. Dichloromethane (10 mL) and water (10 mL) were added, and the organic layer was separated. The aqueous layer was extracted with an additional 10 mL of dichloromethane. The organic layers were combined, washed with brine (2 x 10 mL), dried with magnesium sulfate, and the solvent was removed in vacuo to give a yellow solid (Fig. 3). The solid was dissolved in hot acetonitrile, allowed to cool to room temperature and then stored at 273 K resulting in colorless crystals (58 mg, 18%) after 24 hours. M.p. 448-453 K.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. ORTEP drawing of (I) showing the atom labeling scheme and 30% probability displacement ellipsoids. Dashed lines indicate O1—H1···N1 intramolecular hydrogen bonds.
	Fig. 2. Molecular packing for (I) viewed along the b axis. Dashed lines indicate O—H···N intramolecular hydrogen bonds and weak C—H···O intermolecular interactions linking the molecules into dimers along (010).
	Fig. 3. Synthesis of (I).

2-[1-(2-Hydroxy-4-methoxyphenyl)ethylidene]-N-methylhydrazinecarbothioamide top

Crystal data top

C₁₁H₁₅N₃O₂S	F(000) = 536
M_r = 253.32	D_x = 1.413 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.7107 Å
a = 10.9881 (8) Å	Cell parameters from 4367 reflections
b = 9.1468 (6) Å	θ = 3.0–32.9°
c = 12.5575 (9) Å	µ = 0.27 mm⁻¹
β = 109.400 (8)°	T = 173 K
V = 1190.45 (15) Å³	Irregular, colourless
Z = 4	0.42 × 0.38 × 0.14 mm

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	4104 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3320 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
Detector resolution: 16.0416 pixels mm^-1	θ_max = 33.0°, θ_min = 3.0°
ω scans	h = −15→16
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	k = −12→13
T_min = 0.728, T_max = 1.000	l = −18→18
13894 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.076	H-atom parameters constrained
wR(F²) = 0.231	w = 1/[σ²(F_o²) + (0.0907P)² + 2.429P] where P = (F_o² + 2F_c²)/3
S = 1.16	(Δ/σ)_max < 0.001
4104 reflections	Δρ_max = 1.21 e Å⁻³
158 parameters	Δρ_min = −0.46 e Å⁻³
0 restraints

Crystal data top

C₁₁H₁₅N₃O₂S	V = 1190.45 (15) Å³
M_r = 253.32	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.9881 (8) Å	µ = 0.27 mm⁻¹
b = 9.1468 (6) Å	T = 173 K
c = 12.5575 (9) Å	0.42 × 0.38 × 0.14 mm
β = 109.400 (8)°

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	4104 independent reflections
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	3320 reflections with I > 2σ(I)
T_min = 0.728, T_max = 1.000	R_int = 0.043
13894 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.076	0 restraints
wR(F²) = 0.231	H-atom parameters constrained
S = 1.16	Δρ_max = 1.21 e Å⁻³
4104 reflections	Δρ_min = −0.46 e Å⁻³
158 parameters

Special details top

Experimental. ¹H NMR [(CD₃)₂CO]: 11.7 (br s, 1H, NH) 9.52 (br s, 1H, OH) 7.73 (br s, 1H, NH) 7.5 (d, J = 8.6, 1H Ar) 6.47 (d, J = 8.6 1H Ar) 6.42 (d, 1H Ar) 3.80 (s, 3H, CH₃) 3.13 (d, J = 4.7, 3H, CH₃) 2.43 (s, 3H, CH₃)

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.

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

	x	y	z	U_iso*/U_eq
S1	0.21259 (6)	0.28834 (7)	0.36426 (6)	0.02286 (19)
O1	0.55069 (19)	0.2003 (2)	0.50127 (19)	0.0280 (4)
H1	0.4936	0.2530	0.4608	0.042*
O2	0.9881 (2)	0.0943 (3)	0.60376 (19)	0.0309 (5)
N1	0.4600 (2)	0.4175 (3)	0.36942 (19)	0.0220 (4)
N2	0.3540 (2)	0.5019 (3)	0.31878 (19)	0.0220 (4)
H2	0.3628	0.5869	0.2929	0.026*
N3	0.1393 (2)	0.5407 (3)	0.2551 (2)	0.0240 (4)
H3	0.1595	0.6225	0.2317	0.029*
C1	0.5729 (2)	0.4652 (3)	0.3762 (2)	0.0198 (4)
C2	0.6806 (2)	0.3678 (3)	0.4335 (2)	0.0201 (5)
C3	0.6655 (2)	0.2410 (3)	0.4935 (2)	0.0207 (5)
C4	0.7702 (3)	0.1533 (3)	0.5478 (2)	0.0245 (5)
H4	0.7585	0.0703	0.5862	0.029*
C5	0.8923 (3)	0.1875 (3)	0.5459 (2)	0.0232 (5)
C6	0.9109 (3)	0.3099 (3)	0.4871 (2)	0.0260 (5)
H6	0.9923	0.3327	0.4844	0.031*
C7	0.8055 (3)	0.3967 (3)	0.4329 (2)	0.0250 (5)
H7	0.8182	0.4786	0.3939	0.030*
C8	0.2350 (2)	0.4514 (3)	0.3095 (2)	0.0192 (4)
C9	0.0037 (3)	0.5110 (4)	0.2322 (3)	0.0299 (6)
H9A	−0.0070	0.4535	0.2924	0.045*
H9B	−0.0298	0.4582	0.1624	0.045*
H9C	−0.0422	0.6016	0.2264	0.045*
C10	0.5946 (3)	0.6111 (3)	0.3322 (3)	0.0255 (5)
H10A	0.5542	0.6133	0.2517	0.038*
H10B	0.6856	0.6278	0.3508	0.038*
H10C	0.5580	0.6860	0.3658	0.038*
C11	1.1161 (3)	0.1303 (4)	0.6095 (3)	0.0349 (7)
H11A	1.1420	0.2195	0.6510	0.052*
H11B	1.1191	0.1425	0.5344	0.052*
H11C	1.1736	0.0529	0.6467	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0232 (3)	0.0190 (3)	0.0279 (3)	−0.0010 (2)	0.0104 (2)	0.0013 (2)
O1	0.0214 (9)	0.0276 (10)	0.0383 (11)	−0.0008 (8)	0.0143 (8)	0.0071 (8)
O2	0.0216 (9)	0.0354 (11)	0.0358 (11)	0.0056 (8)	0.0094 (8)	0.0128 (9)
N1	0.0192 (10)	0.0224 (10)	0.0245 (10)	0.0012 (8)	0.0072 (8)	0.0009 (8)
N2	0.0172 (9)	0.0207 (10)	0.0287 (11)	−0.0001 (8)	0.0083 (8)	0.0027 (8)
N3	0.0197 (10)	0.0212 (10)	0.0320 (11)	0.0019 (8)	0.0099 (8)	0.0049 (8)
C1	0.0193 (11)	0.0200 (11)	0.0199 (10)	−0.0012 (8)	0.0063 (8)	−0.0006 (8)
C2	0.0193 (11)	0.0198 (10)	0.0212 (10)	−0.0014 (9)	0.0068 (8)	−0.0001 (8)
C3	0.0203 (11)	0.0217 (11)	0.0221 (11)	−0.0022 (9)	0.0098 (9)	−0.0007 (9)
C4	0.0262 (12)	0.0228 (12)	0.0266 (12)	−0.0002 (10)	0.0115 (10)	0.0047 (9)
C5	0.0209 (11)	0.0251 (12)	0.0239 (11)	0.0009 (9)	0.0076 (9)	0.0021 (9)
C6	0.0197 (11)	0.0277 (13)	0.0314 (13)	−0.0024 (10)	0.0096 (10)	0.0042 (10)
C7	0.0205 (11)	0.0247 (12)	0.0308 (13)	−0.0024 (9)	0.0101 (10)	0.0044 (10)
C8	0.0200 (11)	0.0191 (10)	0.0200 (10)	−0.0002 (8)	0.0086 (8)	−0.0020 (8)
C9	0.0203 (12)	0.0316 (14)	0.0383 (15)	0.0048 (10)	0.0103 (11)	0.0067 (12)
C10	0.0200 (11)	0.0207 (11)	0.0348 (14)	−0.0013 (9)	0.0080 (10)	0.0026 (10)
C11	0.0204 (12)	0.0417 (17)	0.0424 (17)	0.0044 (12)	0.0104 (11)	0.0084 (14)

Geometric parameters (Å, º) top

S1—C8	1.695 (3)	C3—C4	1.383 (4)
O1—H1	0.8200	C4—H4	0.9300
O1—C3	1.350 (3)	C4—C5	1.386 (4)
O2—C5	1.362 (3)	C5—C6	1.393 (4)
O2—C11	1.423 (4)	C6—H6	0.9300
N1—N2	1.366 (3)	C6—C7	1.383 (4)
N1—C1	1.290 (3)	C7—H7	0.9300
N2—H2	0.8600	C9—H9A	0.9600
N2—C8	1.354 (3)	C9—H9B	0.9600
N3—H3	0.8600	C9—H9C	0.9600
N3—C8	1.328 (3)	C10—H10A	0.9600
N3—C9	1.446 (4)	C10—H10B	0.9600
C1—C2	1.465 (4)	C10—H10C	0.9600
C1—C10	1.494 (4)	C11—H11A	0.9600
C2—C3	1.422 (4)	C11—H11B	0.9600
C2—C7	1.400 (4)	C11—H11C	0.9600

C3—O1—H1	109.5	C7—C6—H6	120.8
C5—O2—C11	117.3 (2)	C2—C7—H7	118.3
C1—N1—N2	119.4 (2)	C6—C7—C2	123.4 (2)
N1—N2—H2	120.1	C6—C7—H7	118.3
C8—N2—N1	119.8 (2)	N2—C8—S1	122.13 (19)
C8—N2—H2	120.1	N3—C8—S1	123.55 (19)
C8—N3—H3	117.4	N3—C8—N2	114.3 (2)
C8—N3—C9	125.1 (2)	N3—C9—H9A	109.5
C9—N3—H3	117.4	N3—C9—H9B	109.5
N1—C1—C2	115.4 (2)	N3—C9—H9C	109.5
N1—C1—C10	123.1 (2)	H9A—C9—H9B	109.5
C2—C1—C10	121.5 (2)	H9A—C9—H9C	109.5
C3—C2—C1	122.5 (2)	H9B—C9—H9C	109.5
C7—C2—C1	121.1 (2)	C1—C10—H10A	109.5
C7—C2—C3	116.4 (2)	C1—C10—H10B	109.5
O1—C3—C2	122.7 (2)	C1—C10—H10C	109.5
O1—C3—C4	116.6 (2)	H10A—C10—H10B	109.5
C4—C3—C2	120.7 (2)	H10A—C10—H10C	109.5
C3—C4—H4	119.6	H10B—C10—H10C	109.5
C3—C4—C5	120.8 (2)	O2—C11—H11A	109.5
C5—C4—H4	119.6	O2—C11—H11B	109.5
O2—C5—C4	115.5 (2)	O2—C11—H11C	109.5
O2—C5—C6	124.2 (2)	H11A—C11—H11B	109.5
C4—C5—C6	120.3 (2)	H11A—C11—H11C	109.5
C5—C6—H6	120.8	H11B—C11—H11C	109.5
C7—C6—C5	118.5 (2)

O1—C3—C4—C5	−179.1 (3)	C3—C2—C7—C6	−0.4 (4)
O2—C5—C6—C7	−179.2 (3)	C3—C4—C5—O2	179.1 (2)
N1—N2—C8—S1	2.8 (3)	C3—C4—C5—C6	−1.2 (4)
N1—N2—C8—N3	−177.6 (2)	C4—C5—C6—C7	1.0 (4)
N1—C1—C2—C3	−9.8 (4)	C5—C6—C7—C2	−0.2 (4)
N1—C1—C2—C7	171.0 (2)	C7—C2—C3—O1	179.8 (2)
N2—N1—C1—C2	179.1 (2)	C7—C2—C3—C4	0.3 (4)
N2—N1—C1—C10	0.7 (4)	C9—N3—C8—S1	−1.7 (4)
C1—N1—N2—C8	178.8 (2)	C9—N3—C8—N2	178.7 (3)
C1—C2—C3—O1	0.6 (4)	C10—C1—C2—C3	168.6 (2)
C1—C2—C3—C4	−179.0 (2)	C10—C1—C2—C7	−10.6 (4)
C1—C2—C7—C6	178.9 (3)	C11—O2—C5—C4	−176.4 (3)
C2—C3—C4—C5	0.5 (4)	C11—O2—C5—C6	3.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.85	2.566 (3)	145
C10—H10A···O2ⁱ	0.96	2.59	3.301 (4)	132
C10—H10C···O1ⁱⁱ	0.96	2.57	3.481 (4)	158

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.85	2.566 (3)	144.6
C10—H10A···O2ⁱ	0.96	2.59	3.301 (4)	131.5
C10—H10C···O1ⁱⁱ	0.96	2.57	3.481 (4)	157.8

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

Acknowledgements

JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

References

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2-[1-(2-Hy­dr­oxy-4-meth­­oxy­phen­yl)ethyl­­idene]-N-methyl­hydrazinecarbo­thio­amide

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2-[1-(2-Hydroxy-4-methoxyphenyl)ethylidene]-N-methylhydrazinecarbothioamide