3,4-Dihydroxy­benzaldehyde 4-phenyl­thio­semicarbazone

Tan, K.W.; Farina, Y.; Ng, C.H.; Maah, M.J.; Ng, S.W.

doi:10.1107/S1600536808013287

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1035

doi:10.1107/S1600536808013287

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3,4-Dihydroxybenzaldehyde 4-phenylthiosemicarbazone

Kong Wai Tan,^a Yang Farina,^b Chew Hee Ng,^c ^* Mohd Jamil Maah ^d and Seik Weng Ng ^d

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, ^bSchool of Chemical Science and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Malaysia, ^cFaculty of Engineering and Science, Universiti Tunku Abdul Rahman, 53300 Kuala Lumpur, Malaysia, and ^dDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 30 April 2008; accepted 6 May 2008; online 10 May 2008)

Molecules of the title compound, C₁₄H₁₃N₃O₂S, are linked by intermolecular O—H⋯O hydrogen bonds into centrosymmetric dimers forming R₂²(4) rings which are further linked by O—H⋯S hydrogen bonds and weaker N—H⋯S and N—H⋯O hydrogen bonds to form a three-dimensional network.

Related literature

For the structure of 2,3-dihydroxybenzaldehyde thiosemicarbazone hemihydrate, see: Swesi et al. (2006 ). For metal derivatives of the title compound, see: Zhu et al. (1997 ). The graph-set notation is given by Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₄H₁₃N₃O₂S
M_r = 287.33
Monoclinic, P 2₁ /c
a = 9.7261 (2) Å
b = 13.1863 (3) Å
c = 10.7732 (3) Å
β = 99.055 (2)°
V = 1364.46 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 100 (2) K
0.40 × 0.30 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.909, T_max = 0.953
16724 measured reflections
3132 independent reflections
2358 reflections with I > 2σ(I)
R_int = 0.078

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.115
S = 1.04
3132 reflections
197 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 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
O1—H1o⋯O2ⁱ	0.85 (1)	2.03 (2)	2.737 (2)	141 (2)
O2—H2o⋯S1ⁱⁱ	0.85 (1)	2.34 (1)	3.134 (1)	156 (2)
N2—H2n⋯S1ⁱⁱⁱ	0.85 (1)	2.73 (1)	3.487 (2)	150 (2)
N2—H2n⋯O1^iv	0.85 (1)	2.56 (2)	3.022 (2)	115 (2)
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) $[x-1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+2, -y, -z+1; (iv) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808013287/lh2625sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808013287/lh2625Isup2.hkl

checkCIF report

Comment top

A previous study of the Schiff bases derived by condensing substituted benzaldehydes with 4-phenylthiosemicarbazides reported the 2,3-dihydroxy compound, which crystallizes as a hemihydrate. The compound features extensive hydrogen bond (Swesi et al., 2006). In the title 3,4-dihydroxy isomer the 4-hydroxy group functions as hydrogen-bond donor to the 3-hydroxy group of a symmetry-related molecule forming R₂²(4) rings (Bernstein et al., 1995). In addition, the 3-hydroxy group is a donor to the sulfur atom of another molecule; the hydrogen bonding arrangement furnishes a three-dimensional network motif. The amino groups are involved in weaker hydrogen bond interactions.

Further work will investigate the formation of metal deratives of the ligand; some metal complexes have been reported by others but these have not characterized by crystallography yet (Zhu et al., 1997).

Related literature top

For the structure of 2,3-dihydroxybenzaldehyde thiosemicarbazone hemihydrate, see: Swesi et al. (2006). For metal derivatives of the title compound, see: Zhu et al. (1997). The graph-set notation is given by Bernstein et al. (1995).

Experimental top

4-Phenylthiosemicarbazide (0.17 g, 1 mmol) and 3,4-dihydroxybenzaldehyde (0.14 g, 1 mmol) were heated in ethanol (20 ml) for 3 h. Slow evaporation of the solvent yielded yellow crystals.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

Fig. 1. Thermal ellipsoid (Barbour, 2001) plot of C₁₄H₁₃N₃O₂S at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radii.

3,4-Dihydroxybenzaldehyde 4-phenylthiosemicarbazone top

Crystal data top

C₁₄H₁₃N₃O₂S	F(000) = 600
M_r = 287.33	D_x = 1.399 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2291 reflections
a = 9.7261 (2) Å	θ = 2.5–23.4°
b = 13.1863 (3) Å	µ = 0.24 mm⁻¹
c = 10.7732 (3) Å	T = 100 K
β = 99.055 (2)°	Block, yellow
V = 1364.46 (6) Å³	0.40 × 0.30 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	3132 independent reflections
Radiation source: fine-focus sealed tube	2358 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.078
ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.910, T_max = 0.953	k = −17→16
16724 measured reflections	l = −13→13

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0502P)² + 0.2883P] where P = (F_o² + 2F_c²)/3
3132 reflections	(Δ/σ)_max = 0.001
197 parameters	Δρ_max = 0.40 e Å⁻³
4 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₄H₁₃N₃O₂S	V = 1364.46 (6) Å³
M_r = 287.33	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.7261 (2) Å	µ = 0.24 mm⁻¹
b = 13.1863 (3) Å	T = 100 K
c = 10.7732 (3) Å	0.40 × 0.30 × 0.20 mm
β = 99.055 (2)°

Data collection top

Bruker SMART APEX diffractometer	3132 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2358 reflections with I > 2σ(I)
T_min = 0.910, T_max = 0.953	R_int = 0.078
16724 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	4 restraints
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.40 e Å⁻³
3132 reflections	Δρ_min = −0.32 e Å⁻³
197 parameters

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

	x	y	z	U_iso*/U_eq
S1	1.08441 (5)	0.12769 (4)	0.40212 (5)	0.02006 (15)
O1	0.65919 (15)	0.45705 (10)	0.89678 (14)	0.0221 (3)
O2	0.40955 (14)	0.39195 (11)	0.94986 (14)	0.0231 (3)
N1	0.83208 (16)	0.18905 (12)	0.63925 (15)	0.0187 (4)
N2	0.90695 (16)	0.13520 (12)	0.56294 (16)	0.0185 (4)
N3	1.03542 (19)	0.27810 (13)	0.55853 (18)	0.0258 (4)
C1	0.64419 (19)	0.20682 (14)	0.75172 (18)	0.0172 (4)
C2	0.6914 (2)	0.30261 (14)	0.79586 (18)	0.0177 (4)
H2	0.7798	0.3262	0.7814	0.021*
C3	0.61093 (19)	0.36257 (14)	0.85974 (18)	0.0168 (4)
C4	0.48283 (19)	0.32692 (15)	0.88517 (18)	0.0175 (4)
C5	0.4360 (2)	0.23207 (15)	0.84415 (19)	0.0207 (4)
H5	0.3492	0.2077	0.8620	0.025*
C6	0.5160 (2)	0.17194 (15)	0.77643 (19)	0.0204 (4)
H6	0.4831	0.1071	0.7471	0.024*
C7	0.72652 (19)	0.14733 (15)	0.67561 (19)	0.0190 (4)
H7	0.7022	0.0792	0.6536	0.023*
C8	1.00702 (19)	0.18502 (14)	0.51400 (19)	0.0177 (4)
C9	1.1227 (2)	0.35150 (15)	0.5122 (2)	0.0212 (4)
C10	1.2393 (2)	0.38550 (18)	0.5909 (2)	0.0304 (5)
H10	1.2651	0.3565	0.6719	0.037*
C11	1.3183 (3)	0.4624 (2)	0.5504 (2)	0.0386 (6)
H11	1.3986	0.4863	0.6042	0.046*
C12	1.2821 (2)	0.50451 (18)	0.4336 (2)	0.0339 (6)
H12	1.3366	0.5576	0.4070	0.041*
C13	1.1657 (2)	0.46947 (18)	0.3545 (2)	0.0348 (6)
H13	1.1410	0.4977	0.2729	0.042*
C14	1.0858 (2)	0.39327 (17)	0.3946 (2)	0.0287 (5)
H14	1.0053	0.3696	0.3410	0.034*
H1O	0.602 (2)	0.4875 (17)	0.935 (2)	0.035 (7)*
H2O	0.3276 (14)	0.3698 (18)	0.950 (3)	0.043 (8)*
H2N	0.890 (2)	0.0737 (9)	0.542 (2)	0.036 (7)*
H3N	0.995 (2)	0.2960 (17)	0.6187 (16)	0.027 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0175 (2)	0.0195 (3)	0.0249 (3)	0.00003 (19)	0.00859 (19)	−0.0035 (2)
O1	0.0209 (7)	0.0162 (7)	0.0316 (9)	−0.0015 (6)	0.0116 (6)	−0.0063 (6)
O2	0.0158 (7)	0.0226 (8)	0.0328 (9)	−0.0011 (6)	0.0093 (6)	−0.0075 (6)
N1	0.0181 (8)	0.0188 (9)	0.0207 (9)	0.0021 (7)	0.0081 (7)	−0.0017 (7)
N2	0.0173 (8)	0.0148 (9)	0.0250 (9)	−0.0013 (7)	0.0086 (7)	−0.0043 (7)
N3	0.0313 (10)	0.0202 (9)	0.0310 (11)	−0.0081 (8)	0.0202 (8)	−0.0076 (8)
C1	0.0159 (9)	0.0187 (10)	0.0178 (10)	−0.0003 (7)	0.0048 (8)	−0.0011 (8)
C2	0.0146 (9)	0.0178 (10)	0.0216 (10)	−0.0011 (7)	0.0056 (8)	−0.0001 (8)
C3	0.0169 (9)	0.0148 (10)	0.0184 (10)	−0.0004 (7)	0.0016 (7)	0.0000 (7)
C4	0.0148 (9)	0.0204 (10)	0.0183 (10)	0.0026 (7)	0.0052 (7)	−0.0008 (8)
C5	0.0141 (9)	0.0206 (10)	0.0285 (12)	−0.0020 (8)	0.0064 (8)	−0.0007 (8)
C6	0.0199 (10)	0.0175 (10)	0.0246 (11)	−0.0030 (8)	0.0061 (8)	−0.0026 (8)
C7	0.0185 (10)	0.0168 (10)	0.0223 (11)	−0.0018 (8)	0.0054 (8)	−0.0027 (8)
C8	0.0145 (9)	0.0167 (10)	0.0224 (10)	0.0011 (7)	0.0046 (8)	−0.0002 (8)
C9	0.0204 (10)	0.0170 (10)	0.0287 (12)	−0.0037 (8)	0.0114 (8)	−0.0041 (8)
C10	0.0317 (12)	0.0345 (13)	0.0248 (12)	−0.0058 (10)	0.0034 (9)	0.0012 (10)
C11	0.0328 (13)	0.0442 (15)	0.0381 (15)	−0.0193 (11)	0.0032 (11)	−0.0047 (11)
C12	0.0323 (13)	0.0250 (12)	0.0474 (16)	−0.0093 (10)	0.0155 (11)	0.0037 (11)
C13	0.0336 (13)	0.0312 (13)	0.0396 (15)	0.0016 (10)	0.0059 (11)	0.0148 (11)
C14	0.0211 (10)	0.0310 (12)	0.0328 (13)	−0.0033 (9)	0.0011 (9)	0.0030 (10)

Geometric parameters (Å, º) top

S1—C8	1.696 (2)	C3—C4	1.398 (3)
O1—C3	1.368 (2)	C4—C5	1.380 (3)
O1—H1O	0.85 (1)	C5—C6	1.395 (3)
O2—C4	1.373 (2)	C5—H5	0.9500
O2—H2O	0.85 (1)	C6—H6	0.9500
N1—C7	1.279 (2)	C7—H7	0.9500
N1—N2	1.378 (2)	C9—C14	1.376 (3)
N2—C8	1.348 (2)	C9—C10	1.380 (3)
N2—H2N	0.85 (1)	C10—C11	1.383 (3)
N3—C8	1.331 (3)	C10—H10	0.9500
N3—C9	1.428 (3)	C11—C12	1.370 (3)
N3—H3N	0.84 (1)	C11—H11	0.9500
C1—C6	1.393 (3)	C12—C13	1.385 (3)
C1—C2	1.401 (3)	C12—H12	0.9500
C1—C7	1.461 (3)	C13—C14	1.381 (3)
C2—C3	1.372 (3)	C13—H13	0.9500
C2—H2	0.9500	C14—H14	0.9500

C3—O1—H1O	110.7 (17)	C5—C6—H6	119.9
C4—O2—H2O	110.6 (18)	N1—C7—C1	118.55 (17)
C7—N1—N2	119.07 (16)	N1—C7—H7	120.7
C8—N2—N1	117.64 (16)	C1—C7—H7	120.7
C8—N2—H2N	119.3 (17)	N3—C8—N2	115.47 (17)
N1—N2—H2N	123.0 (17)	N3—C8—S1	125.24 (15)
C8—N3—C9	126.89 (17)	N2—C8—S1	119.28 (15)
C8—N3—H3N	116.2 (16)	C14—C9—C10	120.35 (19)
C9—N3—H3N	116.9 (16)	C14—C9—N3	120.67 (19)
C6—C1—C2	119.21 (17)	C10—C9—N3	118.8 (2)
C6—C1—C7	121.05 (18)	C9—C10—C11	119.2 (2)
C2—C1—C7	119.68 (17)	C9—C10—H10	120.4
C3—C2—C1	120.50 (17)	C11—C10—H10	120.4
C3—C2—H2	119.7	C12—C11—C10	120.8 (2)
C1—C2—H2	119.7	C12—C11—H11	119.6
O1—C3—C2	118.33 (17)	C10—C11—H11	119.6
O1—C3—C4	121.62 (17)	C11—C12—C13	119.8 (2)
C2—C3—C4	120.06 (17)	C11—C12—H12	120.1
O2—C4—C5	123.84 (17)	C13—C12—H12	120.1
O2—C4—C3	116.05 (17)	C14—C13—C12	119.7 (2)
C5—C4—C3	120.10 (18)	C14—C13—H13	120.1
C4—C5—C6	119.95 (18)	C12—C13—H13	120.1
C4—C5—H5	120.0	C9—C14—C13	120.1 (2)
C6—C5—H5	120.0	C9—C14—H14	119.9
C1—C6—C5	120.14 (18)	C13—C14—H14	119.9
C1—C6—H6	119.9

C7—N1—N2—C8	172.24 (18)	C2—C1—C7—N1	−7.8 (3)
C6—C1—C2—C3	−1.7 (3)	C9—N3—C8—N2	−171.35 (19)
C7—C1—C2—C3	175.33 (18)	C9—N3—C8—S1	7.8 (3)
C1—C2—C3—O1	−177.55 (17)	N1—N2—C8—N3	8.7 (3)
C1—C2—C3—C4	2.2 (3)	N1—N2—C8—S1	−170.51 (13)
O1—C3—C4—O2	−0.4 (3)	C8—N3—C9—C14	66.2 (3)
C2—C3—C4—O2	179.82 (17)	C8—N3—C9—C10	−118.6 (2)
O1—C3—C4—C5	178.64 (18)	C14—C9—C10—C11	0.3 (3)
C2—C3—C4—C5	−1.1 (3)	N3—C9—C10—C11	−174.9 (2)
O2—C4—C5—C6	178.51 (18)	C9—C10—C11—C12	−0.2 (4)
C3—C4—C5—C6	−0.5 (3)	C10—C11—C12—C13	−0.5 (4)
C2—C1—C6—C5	0.1 (3)	C11—C12—C13—C14	1.0 (4)
C7—C1—C6—C5	−176.89 (18)	C10—C9—C14—C13	0.1 (3)
C4—C5—C6—C1	1.0 (3)	N3—C9—C14—C13	175.3 (2)
N2—N1—C7—C1	−177.22 (16)	C12—C13—C14—C9	−0.8 (4)
C6—C1—C7—N1	169.23 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O2ⁱ	0.85 (1)	2.03 (2)	2.737 (2)	141 (2)
O2—H2O···S1ⁱⁱ	0.85 (1)	2.34 (1)	3.134 (1)	156 (2)
N2—H2N···S1ⁱⁱⁱ	0.85 (1)	2.73 (1)	3.487 (2)	150 (2)
N2—H2N···O1^iv	0.85 (1)	2.56 (2)	3.022 (2)	115 (2)

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₃N₃O₂S
M_r	287.33
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	9.7261 (2), 13.1863 (3), 10.7732 (3)
β (°)	99.055 (2)
V (Å³)	1364.46 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.910, 0.953
No. of measured, independent and observed [I > 2σ(I)] reflections	16724, 3132, 2358
R_int	0.078
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.115, 1.04
No. of reflections	3132
No. of parameters	197
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)	0.40, −0.32

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O2ⁱ	0.85 (1)	2.03 (2)	2.737 (2)	141 (2)
O2—H2O···S1ⁱⁱ	0.85 (1)	2.34 (1)	3.134 (1)	156 (2)
N2—H2N···S1ⁱⁱⁱ	0.85 (1)	2.73 (1)	3.487 (2)	150 (2)
N2—H2N···O1^iv	0.85 (1)	2.56 (2)	3.022 (2)	115 (2)

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

Acknowledgements

We thank the University of Malaya (P0265/2007 A) for supporting this study; KWT thanks the Ministry of Higher Education for an SLAI scholarship in this research.

References

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