2,5-Dimethoxy­benzaldehyde thio­semicarbazone

Fun, H.-K.; Jebas, S.R.; D'Silva, E.D.; Patil, P.S.; Dharmaprakash, S.M.

doi:10.1107/S1600536808035198

organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2276

doi:10.1107/S1600536808035198

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2,5-Dimethoxybenzaldehyde thiosemicarbazone

Hoong-Kun Fun,^a ^* Samuel Robinson Jebas,^a ‡ E. Deepak D'Silva,^b P. S. Patil ^b § and S. M. Dharmaprakash ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bDepartment of Studies in Physics, Mangalore University, Mangalagangotri, Mangalore 574 199, India
^*Correspondence e-mail: hkfun@usm.my

(Received 28 October 2008; accepted 28 October 2008; online 8 November 2008)

In the title molecule, C₁₀H₁₃N₃O₂S, the dihedral angle between benzene and –N—C(=S)—N—N=C– planes is 9.20 (6)°. The two methoxy groups are coplanar with the benzene ring [C—O—C—C torsion angles of −2.31 (18) and −6.45 (17)°]. In the crystal structure, molecules are linked by intermolecular N—H⋯S, N—H⋯O and C—H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For the biomedical properties of thiosemicarbazones, see: Beraldo & Gambino (2004 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₀H₁₃N₃O₂S
M_r = 239.29
Orthorhombic, P b c a
a = 11.0713 (1) Å
b = 13.0603 (2) Å
c = 15.7808 (2) Å
V = 2281.82 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 100.0 (1) K
0.34 × 0.28 × 0.22 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.912, T_max = 0.943
18486 measured reflections
3486 independent reflections
2834 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.097
S = 1.06
3486 reflections
157 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯S1ⁱ	0.84 (4)	2.718 (18)	3.5375 (12)	166 (2)
N3—H2N3⋯S1ⁱⁱ	0.86 (1)	2.811 (13)	3.5047 (12)	139 (1)
N3—H1N3⋯O2ⁱⁱⁱ	0.86 (1)	2.145 (11)	2.9617 (15)	159 (2)
C3—H3A⋯O1^iv	0.93	2.51	3.3027 (16)	143
Symmetry codes: (i) -x, -y+2, -z+1; (ii) $[x+{\script{1\over 2}}, -y+{\script{5\over 2}}, -z+1]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{5\over 2}}, -z+1]$ ; (iv) $[x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 and SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808035198/ci2701sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808035198/ci2701Isup2.hkl

checkCIF report

Comment top

Thiosemicarbazones are of great interest because of their profound biomedical properties (Beraldo et al., 2004). Flexibility and bioactivity of these compounds arise due to the presence of amino group (–N═CH–) in addition to thioamino moieties present in the skeleton of the molecule. We have synthesized the title compound and its crystal structure is reported here.

The bond lengths in the title molecule (Fig.1) are found to have normal values (Allen et al., 1987). The two methoxy groups are coplanar with the benzene ring, with C9—O1—C1—C2 and C10—O2—C4—C3 torsion angles of -2.31 (18) and -6.45 (17)°, respectively. The dihedral angle between the C1—C6 and S1/N1—N3/C7/C8 planes is 9.20 (6)°.

In the crystal packing, the molecules are linked together by intermolecular N—H···S, N—H···O and C—H···O hydrogen bonds (Table 1) to form a three-dimensional network (Fig.2).

Related literature top

For the biomedical properties of thiosemicarbazones, see: Beraldo et al. (2004). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was synthesized by refluxing 2,5-dimethoxy benzaldehyde (0.075 mol) and thiosemicarbazone (0.05 mol) in methanol (100 ml) for 2 h. The solution was then allowed to cool, poured into a beaker containing water and stirred for 30 min. The product was separated by filtration and the crude sample obtained was recrystallized twice from hot methanol.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005) and SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The crystal packing of the title compound, viewed along the a axis. Dashed lines indicate hydrogen bonds.

2,5-Dimethoxybenzaldehyde thiosemicarbazone top

Crystal data top

C₁₀H₁₃N₃O₂S	F(000) = 1008
M_r = 239.29	D_x = 1.393 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4233 reflections
a = 11.0713 (1) Å	θ = 2.6–30.0°
b = 13.0603 (2) Å	µ = 0.27 mm⁻¹
c = 15.7808 (2) Å	T = 100 K
V = 2281.82 (5) Å³	Block, colourless
Z = 8	0.34 × 0.28 × 0.22 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3486 independent reflections
Radiation source: fine-focus sealed tube	2834 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ϕ and ω scans	θ_max = 30.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −15→11
T_min = 0.912, T_max = 0.943	k = −14→18
18486 measured reflections	l = −22→19

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0435P)² + 0.8407P] where P = (F_o² + 2F_c²)/3
3486 reflections	(Δ/σ)_max = 0.002
157 parameters	Δρ_max = 0.40 e Å⁻³
2 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₀H₁₃N₃O₂S	V = 2281.82 (5) Å³
M_r = 239.29	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 11.0713 (1) Å	µ = 0.27 mm⁻¹
b = 13.0603 (2) Å	T = 100 K
c = 15.7808 (2) Å	0.34 × 0.28 × 0.22 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3486 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2834 reflections with I > 2σ(I)
T_min = 0.912, T_max = 0.943	R_int = 0.043
18486 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	2 restraints
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.40 e Å⁻³
3486 reflections	Δρ_min = −0.27 e Å⁻³
157 parameters

Special details top

Experimental. The data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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	−0.01083 (3)	1.16558 (3)	0.45083 (2)	0.01697 (9)
O1	0.35907 (8)	0.80559 (7)	0.68704 (6)	0.0191 (2)
O2	0.72695 (8)	1.07776 (7)	0.61508 (6)	0.0165 (2)
N1	0.28066 (10)	1.06262 (9)	0.56220 (6)	0.0150 (2)
N2	0.16335 (10)	1.07175 (9)	0.53426 (7)	0.0157 (2)
N3	0.21269 (11)	1.23005 (9)	0.48405 (7)	0.0178 (2)
C1	0.45590 (12)	0.86889 (10)	0.67348 (7)	0.0150 (2)
C2	0.57116 (12)	0.85165 (10)	0.70424 (8)	0.0174 (3)
H2A	0.5868	0.7939	0.7370	0.021*
C3	0.66395 (12)	0.92047 (10)	0.68638 (8)	0.0175 (3)
H3A	0.7414	0.9085	0.7070	0.021*
C4	0.64053 (11)	1.00689 (10)	0.63780 (7)	0.0144 (2)
C5	0.52450 (12)	1.02595 (10)	0.60844 (7)	0.0145 (2)
H5A	0.5091	1.0846	0.5768	0.017*
C6	0.43114 (11)	0.95785 (10)	0.62609 (7)	0.0138 (2)
C7	0.30819 (12)	0.97659 (10)	0.59612 (8)	0.0153 (2)
H7A	0.2497	0.9259	0.6017	0.018*
C8	0.13017 (11)	1.15736 (10)	0.49192 (7)	0.0142 (2)
C9	0.37938 (13)	0.71375 (11)	0.73357 (9)	0.0231 (3)
H9A	0.3049	0.6766	0.7387	0.035*
H9B	0.4092	0.7304	0.7890	0.035*
H9C	0.4377	0.6724	0.7044	0.035*
C10	0.84490 (12)	1.06643 (11)	0.65093 (8)	0.0184 (3)
H10A	0.8965	1.1200	0.6303	0.028*
H10B	0.8777	1.0012	0.6350	0.028*
H10C	0.8397	1.0705	0.7116	0.028*
H1N2	0.1156 (16)	1.0222 (14)	0.5376 (11)	0.024 (4)*
H2N3	0.2833 (10)	1.2200 (13)	0.5055 (10)	0.025 (4)*
H1N3	0.1967 (18)	1.2835 (10)	0.4545 (10)	0.036 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01117 (16)	0.01533 (17)	0.02441 (16)	0.00118 (11)	−0.00228 (12)	0.00302 (11)
O1	0.0150 (5)	0.0161 (5)	0.0261 (5)	0.0003 (4)	0.0023 (4)	0.0075 (4)
O2	0.0115 (4)	0.0155 (5)	0.0224 (4)	−0.0017 (3)	−0.0022 (3)	0.0021 (3)
N1	0.0109 (5)	0.0158 (5)	0.0184 (5)	0.0003 (4)	−0.0023 (4)	0.0008 (4)
N2	0.0107 (5)	0.0134 (5)	0.0231 (5)	−0.0015 (4)	−0.0029 (4)	0.0036 (4)
N3	0.0139 (5)	0.0143 (5)	0.0251 (5)	−0.0012 (4)	−0.0037 (4)	0.0035 (4)
C1	0.0154 (6)	0.0134 (6)	0.0161 (5)	0.0008 (5)	0.0028 (5)	0.0010 (4)
C2	0.0187 (7)	0.0140 (6)	0.0196 (5)	0.0031 (5)	−0.0001 (5)	0.0035 (4)
C3	0.0143 (6)	0.0176 (6)	0.0205 (6)	0.0035 (5)	−0.0029 (5)	0.0008 (5)
C4	0.0129 (6)	0.0141 (6)	0.0161 (5)	0.0002 (5)	0.0007 (4)	−0.0015 (4)
C5	0.0152 (6)	0.0131 (6)	0.0154 (5)	0.0010 (5)	−0.0009 (4)	0.0013 (4)
C6	0.0125 (6)	0.0137 (6)	0.0151 (5)	0.0016 (5)	0.0000 (4)	0.0004 (4)
C7	0.0130 (6)	0.0152 (6)	0.0176 (5)	−0.0009 (5)	0.0001 (4)	0.0013 (4)
C8	0.0132 (6)	0.0137 (6)	0.0156 (5)	0.0010 (4)	0.0009 (4)	−0.0008 (4)
C9	0.0223 (7)	0.0168 (7)	0.0301 (7)	0.0002 (5)	0.0039 (6)	0.0085 (5)
C10	0.0127 (6)	0.0206 (7)	0.0218 (6)	0.0005 (5)	−0.0025 (5)	−0.0017 (5)

Geometric parameters (Å, º) top

S1—C8	1.6938 (13)	C2—H2A	0.93
O1—C1	1.3706 (16)	C3—C4	1.3888 (18)
O1—C9	1.4242 (16)	C3—H3A	0.93
O2—C4	1.3788 (15)	C4—C5	1.3881 (17)
O2—C10	1.4308 (15)	C5—C6	1.3917 (18)
N1—C7	1.2813 (16)	C5—H5A	0.93
N1—N2	1.3768 (15)	C6—C7	1.4617 (18)
N2—C8	1.3533 (16)	C7—H7A	0.93
N2—H1N2	0.838 (18)	C9—H9A	0.96
N3—C8	1.3235 (17)	C9—H9B	0.96
N3—H2N3	0.861 (9)	C9—H9C	0.96
N3—H1N3	0.857 (9)	C10—H10A	0.96
C1—C2	1.3837 (19)	C10—H10B	0.96
C1—C6	1.4087 (17)	C10—H10C	0.96
C2—C3	1.3938 (19)

C1—O1—C9	117.71 (10)	C6—C5—H5A	119.8
C4—O2—C10	117.46 (10)	C5—C6—C1	119.26 (12)
C7—N1—N2	115.73 (11)	C5—C6—C7	121.33 (11)
C8—N2—N1	119.06 (11)	C1—C6—C7	119.41 (12)
C8—N2—H1N2	119.9 (12)	N1—C7—C6	120.23 (12)
N1—N2—H1N2	120.5 (12)	N1—C7—H7A	119.9
C8—N3—H2N3	118.7 (11)	C6—C7—H7A	119.9
C8—N3—H1N3	119.5 (14)	N3—C8—N2	116.85 (12)
H2N3—N3—H1N3	121.6 (17)	N3—C8—S1	123.70 (10)
O1—C1—C2	124.64 (11)	N2—C8—S1	119.44 (10)
O1—C1—C6	115.35 (11)	O1—C9—H9A	109.5
C2—C1—C6	120.00 (12)	O1—C9—H9B	109.5
C1—C2—C3	120.25 (12)	H9A—C9—H9B	109.5
C1—C2—H2A	119.9	O1—C9—H9C	109.5
C3—C2—H2A	119.9	H9A—C9—H9C	109.5
C4—C3—C2	119.87 (12)	H9B—C9—H9C	109.5
C4—C3—H3A	120.1	O2—C10—H10A	109.5
C2—C3—H3A	120.1	O2—C10—H10B	109.5
O2—C4—C5	115.78 (11)	H10A—C10—H10B	109.5
O2—C4—C3	124.03 (11)	O2—C10—H10C	109.5
C5—C4—C3	120.19 (12)	H10A—C10—H10C	109.5
C4—C5—C6	120.39 (12)	H10B—C10—H10C	109.5
C4—C5—H5A	119.8

C7—N1—N2—C8	−174.96 (11)	C4—C5—C6—C1	−0.54 (18)
C9—O1—C1—C2	−2.31 (18)	C4—C5—C6—C7	179.74 (11)
C9—O1—C1—C6	179.11 (11)	O1—C1—C6—C5	−179.27 (11)
O1—C1—C2—C3	179.55 (12)	C2—C1—C6—C5	2.07 (18)
C6—C1—C2—C3	−1.93 (19)	O1—C1—C6—C7	0.45 (17)
C1—C2—C3—C4	0.25 (19)	C2—C1—C6—C7	−178.20 (11)
C10—O2—C4—C5	173.96 (11)	N2—N1—C7—C6	178.52 (10)
C10—O2—C4—C3	−6.45 (17)	C5—C6—C7—N1	−8.95 (18)
C2—C3—C4—O2	−178.28 (11)	C1—C6—C7—N1	171.33 (11)
C2—C3—C4—C5	1.30 (19)	N1—N2—C8—N3	−3.50 (17)
O2—C4—C5—C6	178.47 (11)	N1—N2—C8—S1	175.42 (9)
C3—C4—C5—C6	−1.14 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···S1ⁱ	0.84 (4)	2.718 (18)	3.5375 (12)	166 (2)
N3—H2N3···S1ⁱⁱ	0.86 (1)	2.81 (1)	3.5047 (12)	139 (1)
N3—H1N3···O2ⁱⁱⁱ	0.86 (1)	2.15 (1)	2.9617 (15)	159 (2)
C3—H3A···O1^iv	0.93	2.51	3.3027 (16)	143

Symmetry codes: (i) −x, −y+2, −z+1; (ii) x+1/2, −y+5/2, −z+1; (iii) x−1/2, −y+5/2, −z+1; (iv) x+1/2, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₃N₃O₂S
M_r	239.29
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	100
a, b, c (Å)	11.0713 (1), 13.0603 (2), 15.7808 (2)
V (Å³)	2281.82 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.34 × 0.28 × 0.22

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.912, 0.943
No. of measured, independent and observed [I > 2σ(I)] reflections	18486, 3486, 2834
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.714

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.097, 1.06
No. of reflections	3486
No. of parameters	157
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.27

Computer programs: , APEX2 (Bruker, 2005) and SAINT (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···S1ⁱ	0.84 (4)	2.718 (18)	3.5375 (12)	166 (2)
N3—H2N3···S1ⁱⁱ	0.86 (1)	2.811 (13)	3.5047 (12)	139 (1)
N3—H1N3···O2ⁱⁱⁱ	0.86 (1)	2.145 (11)	2.9617 (15)	159 (2)
C3—H3A···O1^iv	0.93	2.51	3.3027 (16)	143

Symmetry codes: (i) −x, −y+2, −z+1; (ii) x+1/2, −y+5/2, −z+1; (iii) x−1/2, −y+5/2, −z+1; (iv) x+1/2, y, −z+3/2.

Footnotes

‡Permanent address: Department of Physics, Karunya University, Karunya Nagar, Coimbatore 641 114, India.

§Current address: Department of Physics, KLE Society's KLE Institute of Technology, Gokul, Hubli 590 030, India.

Acknowledgements

HKF and SRJ thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SRJ thanks Universiti Sains Malaysia for a post–doctoral research fellowship. This work was supported by the Department of Science and Technology (DST), Government of India (grant No. SR/S2/LOP-17/2006).

References

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar