(E)-3,4-Dihydroxy­benzaldehyde 4-methyl­thio­semicarbazone

Farina, Y.; Simpson, J.

doi:10.1107/S1600536808034326

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 11| November 2008| Pages o2184-o2185

doi:10.1107/S1600536808034326

Open

access

(E)-3,4-Dihydroxybenzaldehyde 4-methylthiosemicarbazone

Yang Farina ^a ^* and Jim Simpson ^b

^aSchool of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia, and ^bDepartment of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand
^*Correspondence e-mail: farina@pkrisc.cc.ukm.my

(Received 9 October 2008; accepted 21 October 2008; online 25 October 2008)

The title compound, C₉H₁₁N₃O₂S, adopts an E configuration with respect to the C=N bond. The molecule is approximately planar, with an r.m.s. deviation from the mean plane through all 15 non-H atoms of 0.152 Å; the dihedral angle between the benzene ring plane and the least-squares plane through the thiosemicarbazone unit is 12.48 (7)°. A weak intramolecular N—H⋯N interaction contributes to the planarity of the semicarbazone unit. Centrosymmetric pairs of O—H⋯O and N—H⋯S hydrogen bonds form chains along c, generating R₂²(10) and R₂²(8) ring motifs, respectively. In the crystal structure, these chains are further linked by intermolecular O—H⋯S and C—H⋯O interactions, forming stacks down the c axis.

Related literature

For the biological activity of thiosemicarbazones, see: de Sousa et al. (2007 ). For related structures, see: Kayed et al. (2008 ); Tan et al. (2008a ,b ). For hydrogen-bonding patterns, see: Bernstein et al. (1995 ). For reference structural data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₉H₁₁N₃O₂S
M_r = 225.27
Monoclinic, P 2₁ /n
a = 6.8502 (9) Å
b = 14.911 (2) Å
c = 10.6299 (13) Å
β = 107.894 (6)°
V = 1033.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 92 (2) K
0.23 × 0.15 × 0.13 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ) T_min = 0.799, T_max = 0.962
17952 measured reflections
3696 independent reflections
2974 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.112
S = 1.07
3696 reflections
149 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯N1	0.879 (9)	2.220 (18)	2.6282 (17)	108.0 (14)
O3—H3⋯O4ⁱ	0.837 (9)	2.070 (14)	2.8071 (14)	146.5 (19)
O4—H4⋯S1ⁱⁱ	0.836 (9)	2.369 (10)	3.1899 (11)	167.1 (19)
N2—H2N⋯S1ⁱⁱⁱ	0.876 (9)	2.785 (12)	3.5766 (13)	150.9 (15)
C9—H9A⋯O4^iv	0.98	2.56	3.435 (2)	148
Symmetry codes: (i) -x, -y, -z-1; (ii) x-1, y, z-1; (iii) -x+1, -y, -z+1; (iv) x, y, z+1.

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 and SAINT (Bruker 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and TITAN (Hunter & Simpson, 1999 ); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 ), PLATON (Spek, 2003 ) and publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808034326/pv2112sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808034326/pv2112Isup2.hkl

checkCIF report

Comment top

Thiosemicarbazones are a class of compounds that have been extensively investigated because of their biological activity (de Sousa et al., 2007). As a continuation of our work on thiosemicarbazone compounds as potential ligands in transition metal chemistry (Kayed et al., 2008; Tan et al., 2008a,b) we report here the structure of the title compound, (I).

The molecule of (I) (Fig. 1) is approximately planar with a dihedral angle of 12.48 (7)° between the phenyl ring plane and the least squares plane through the C7/N1/N2/C8/S2/N3 thiosemicarbazone moiety. The planarity of this section of the molecule is aided by a weak intramolecular N3—H3N···N1 interaction. The molecule adopts an E configuration with respect to the C═N bond and bond distances are normal (Allen et al., 1987).

Pairs of O3—H3···O4 hydrogen bonds generate a centrosymmetric R²₂(10) ring motif (Bernstein et al., 1995) and, together with the R²₂(8) ring generated by N2—H2N···S1 interactions, form an unusual molecular trimer. The crystal structure is further stabilized by O4—H4···S1 and C9—H9A···O4 contacts, Table 1, Fig. 2.

Related literature top

For the biological activity of thiosemicarbazones, see: de Sousa et al. (2007). For related structures, see: Kayed et al. (2008); Tan et al. (2008a,b). For hydrogen-bonding patterns, see: Bernstein et al. (1995). For reference structural data, see: Allen et al. (1987).

Experimental top

A 1:1 mixture of 3,4-dihydroxybenzaldehyde and N-methylhydrazinecarbothioamide was heated under reflux in ethanol for 2 hours. The solid product which separated upon cooling was filtered and recrystallised from methanol to afford colourless blocks of (I) in 54% yield (m.p. 418-419 K).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006) and SAINT (Bruker 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and TITAN (Hunter & Simpson, 1999); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004), PLATON (Spek, 2003) and publCIF (Westrip, 2008).

Figures top

	Fig. 1. The structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms. An intramolecular hydrogen bond is drawn as a dashed line.
	Fig. 2. Crystal packing of (I) viewed down the c axis with hydrogen bonds drawn as dashed lines. H-atoms not involved in H-bonding have been excluded.

(E)-3,4-Dihydroxybenzaldehyde 4-methylthiosemicarbazone top

Crystal data top

C₉H₁₁N₃O₂S	F(000) = 472
M_r = 225.27	D_x = 1.448 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3847 reflections
a = 6.8502 (9) Å	θ = 2.4–29.8°
b = 14.911 (2) Å	µ = 0.30 mm⁻¹
c = 10.6299 (13) Å	T = 92 K
β = 107.894 (6)°	Plate, colourless
V = 1033.3 (2) Å³	0.23 × 0.15 × 0.13 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	3696 independent reflections
Radiation source: fine-focus sealed tube	2974 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ω scans	θ_max = 33.0°, θ_min = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −10→10
T_min = 0.799, T_max = 0.962	k = −22→18
17952 measured reflections	l = −16→15

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0412P)² + 0.5756P] where P = (F_o² + 2F_c²)/3
3696 reflections	(Δ/σ)_max < 0.001
149 parameters	Δρ_max = 0.49 e Å⁻³
4 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₉H₁₁N₃O₂S	V = 1033.3 (2) Å³
M_r = 225.27	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.8502 (9) Å	µ = 0.30 mm⁻¹
b = 14.911 (2) Å	T = 92 K
c = 10.6299 (13) Å	0.23 × 0.15 × 0.13 mm
β = 107.894 (6)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3696 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	2974 reflections with I > 2σ(I)
T_min = 0.799, T_max = 0.962	R_int = 0.044
17952 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	4 restraints
wR(F²) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.49 e Å⁻³
3696 reflections	Δρ_min = −0.32 e Å⁻³
149 parameters

Special details top

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
C1	0.2002 (2)	0.06919 (9)	−0.01216 (13)	0.0157 (2)
C2	0.2338 (2)	0.00229 (9)	−0.09567 (13)	0.0165 (2)
H2	0.3237	−0.0460	−0.0590	0.020*
C3	0.1378 (2)	0.00557 (9)	−0.23119 (13)	0.0160 (2)
O3	0.17512 (16)	−0.06151 (7)	−0.30786 (10)	0.0213 (2)
H3	0.110 (3)	−0.0532 (14)	−0.3876 (10)	0.032*
C4	0.0039 (2)	0.07616 (9)	−0.28381 (13)	0.0166 (2)
O4	−0.09897 (16)	0.07447 (7)	−0.41779 (10)	0.0206 (2)
H4	−0.2160 (18)	0.0940 (13)	−0.424 (2)	0.031*
C5	−0.0247 (2)	0.14471 (9)	−0.20207 (13)	0.0183 (3)
H5	−0.1111	0.1940	−0.2392	0.022*
C6	0.0727 (2)	0.14133 (10)	−0.06654 (14)	0.0180 (3)
H6	0.0523	0.1881	−0.0111	0.022*
C7	0.2988 (2)	0.05936 (9)	0.13036 (13)	0.0168 (2)
H7	0.3900	0.0107	0.1623	0.020*
N1	0.26441 (18)	0.11527 (8)	0.21297 (11)	0.0174 (2)
N2	0.36894 (18)	0.09854 (8)	0.34422 (11)	0.0182 (2)
H2N	0.456 (2)	0.0539 (9)	0.3669 (17)	0.022*
C8	0.3229 (2)	0.14654 (9)	0.43924 (13)	0.0163 (2)
S1	0.46023 (5)	0.12889 (2)	0.60055 (3)	0.01943 (10)
N3	0.17327 (18)	0.20621 (8)	0.39921 (12)	0.0188 (2)
H3N	0.107 (3)	0.2075 (12)	0.3142 (10)	0.023*
C9	0.1019 (2)	0.26414 (10)	0.48622 (16)	0.0259 (3)
H9A	0.0204	0.2289	0.5298	0.039*
H9B	0.0171	0.3123	0.4343	0.039*
H9C	0.2202	0.2902	0.5532	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0148 (5)	0.0165 (6)	0.0166 (5)	−0.0009 (5)	0.0061 (4)	−0.0004 (5)
C2	0.0158 (6)	0.0143 (6)	0.0202 (6)	0.0002 (5)	0.0067 (5)	0.0006 (5)
C3	0.0160 (6)	0.0148 (6)	0.0182 (6)	−0.0020 (5)	0.0067 (5)	−0.0019 (5)
O3	0.0239 (5)	0.0197 (5)	0.0194 (5)	0.0032 (4)	0.0055 (4)	−0.0040 (4)
C4	0.0149 (5)	0.0199 (6)	0.0153 (5)	−0.0006 (5)	0.0052 (4)	−0.0007 (5)
O4	0.0190 (5)	0.0258 (5)	0.0164 (4)	0.0032 (4)	0.0044 (4)	−0.0027 (4)
C5	0.0189 (6)	0.0172 (6)	0.0184 (6)	0.0031 (5)	0.0052 (5)	0.0000 (5)
C6	0.0172 (6)	0.0188 (6)	0.0182 (6)	0.0013 (5)	0.0058 (5)	−0.0009 (5)
C7	0.0157 (6)	0.0158 (6)	0.0187 (6)	0.0002 (5)	0.0050 (5)	0.0016 (5)
N1	0.0163 (5)	0.0198 (6)	0.0152 (5)	0.0012 (4)	0.0037 (4)	0.0011 (4)
N2	0.0200 (5)	0.0181 (6)	0.0160 (5)	0.0049 (4)	0.0050 (4)	0.0005 (4)
C8	0.0165 (6)	0.0141 (6)	0.0193 (6)	−0.0018 (5)	0.0072 (5)	−0.0010 (5)
S1	0.02201 (17)	0.01991 (18)	0.01649 (16)	0.00247 (12)	0.00609 (12)	−0.00049 (12)
N3	0.0184 (5)	0.0162 (5)	0.0214 (5)	0.0019 (4)	0.0056 (4)	−0.0010 (4)
C9	0.0277 (7)	0.0185 (7)	0.0348 (8)	0.0044 (6)	0.0148 (6)	−0.0034 (6)

Geometric parameters (Å, º) top

C1—C6	1.3943 (19)	C6—H6	0.9500
C1—C2	1.4006 (18)	C7—N1	1.2841 (18)
C1—C7	1.4642 (18)	C7—H7	0.9500
C2—C3	1.3886 (18)	N1—N2	1.3812 (15)
C2—H2	0.9500	N2—C8	1.3518 (17)
C3—O3	1.3632 (16)	N2—H2N	0.876 (9)
C3—C4	1.3952 (19)	C8—N3	1.3251 (18)
O3—H3	0.837 (9)	C8—S1	1.7038 (14)
C4—O4	1.3815 (16)	N3—C9	1.4556 (18)
C4—C5	1.3937 (19)	N3—H3N	0.879 (9)
O4—H4	0.836 (9)	C9—H9A	0.9800
C5—C6	1.3901 (19)	C9—H9B	0.9800
C5—H5	0.9500	C9—H9C	0.9800

C6—C1—C2	119.39 (12)	N1—C7—C1	121.28 (12)
C6—C1—C7	122.50 (12)	N1—C7—H7	119.4
C2—C1—C7	118.10 (12)	C1—C7—H7	119.4
C3—C2—C1	120.98 (12)	C7—N1—N2	115.24 (12)
C3—C2—H2	119.5	C8—N2—N1	119.45 (11)
C1—C2—H2	119.5	C8—N2—H2N	119.4 (12)
O3—C3—C2	118.57 (12)	N1—N2—H2N	120.9 (12)
O3—C3—C4	122.33 (12)	N3—C8—N2	116.78 (12)
C2—C3—C4	119.08 (12)	N3—C8—S1	124.08 (11)
C3—O3—H3	111.0 (14)	N2—C8—S1	119.13 (10)
O4—C4—C5	122.08 (12)	C8—N3—C9	124.91 (13)
O4—C4—C3	117.63 (12)	C8—N3—H3N	116.8 (12)
C5—C4—C3	120.28 (12)	C9—N3—H3N	118.1 (12)
C4—O4—H4	104.4 (14)	N3—C9—H9A	109.5
C6—C5—C4	120.34 (13)	N3—C9—H9B	109.5
C6—C5—H5	119.8	H9A—C9—H9B	109.5
C4—C5—H5	119.8	N3—C9—H9C	109.5
C5—C6—C1	119.83 (13)	H9A—C9—H9C	109.5
C5—C6—H6	120.1	H9B—C9—H9C	109.5
C1—C6—H6	120.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···N1	0.88 (1)	2.22 (2)	2.6282 (17)	108 (1)
O3—H3···O4ⁱ	0.84 (1)	2.07 (1)	2.8071 (14)	147 (2)
O4—H4···S1ⁱⁱ	0.84 (1)	2.37 (1)	3.1899 (11)	167 (2)
N2—H2N···S1ⁱⁱⁱ	0.88 (1)	2.79 (1)	3.5766 (13)	151 (2)
C9—H9A···O4^iv	0.98	2.56	3.435 (2)	148

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

Experimental details

Crystal data
Chemical formula	C₉H₁₁N₃O₂S
M_r	225.27
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	92
a, b, c (Å)	6.8502 (9), 14.911 (2), 10.6299 (13)
β (°)	107.894 (6)
V (Å³)	1033.3 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.23 × 0.15 × 0.13

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2006)
T_min, T_max	0.799, 0.962
No. of measured, independent and observed [I > 2σ(I)] reflections	17952, 3696, 2974
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.765

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.112, 1.07
No. of reflections	3696
No. of parameters	149
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.32

Computer programs: , APEX2 (Bruker, 2006) and SAINT (Bruker 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and TITAN (Hunter & Simpson, 1999), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004), PLATON (Spek, 2003) and publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···N1	0.879 (9)	2.220 (18)	2.6282 (17)	108.0 (14)
O3—H3···O4ⁱ	0.837 (9)	2.070 (14)	2.8071 (14)	146.5 (19)
O4—H4···S1ⁱⁱ	0.836 (9)	2.369 (10)	3.1899 (11)	167.1 (19)
N2—H2N···S1ⁱⁱⁱ	0.876 (9)	2.785 (12)	3.5766 (13)	150.9 (15)
C9—H9A···O4^iv	0.98	2.56	3.435 (2)	148.3

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

Acknowledgements

We thank the Universiti Kebangsaan Malaysia and the Ministry of Higher Education, Malaysia, for supporting this research through grants UKM-ST-01-FRGS0022–2006 and UKM-GUP-NBT-08–27-112 and Mr M. A. I. Yim for preparing the title compound. We also thank the University of Otago for purchase of the diffractometer.

References

Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335–338. Web of Science CrossRef CAS IUCr Journals Google Scholar
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2006). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hunter, K. A. & Simpson, J. (1999). TITAN2000. University of Otago, New Zealand. Google Scholar
Kayed, S. F., Farina, Y., Baba, I. & Simpson, J. (2008). Acta Cryst. E64, o824–o825. Web of Science CSD CrossRef IUCr Journals Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sousa, G. F. de, Manso, L. C. C., Lang, E. S., Gatto, C. C. & Mahieu, B. (2007). J. Mol. Struct. 826, 185–191. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tan, K. W., Farina, Y., Ng, C. H., Maah, M. J. & Ng, S. W. (2008a). Acta Cryst. E64, o1035. Web of Science CSD CrossRef IUCr Journals Google Scholar
Tan, K. W., Farina, Y., Ng, C. H., Maah, M. J. & Ng, S. W. (2008b). Acta Cryst. E64, o1073. Web of Science CSD CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar