3,4-Dihydroxy-benzaldehyde 4-phenyl-thio-semicarbazone.

Mol-ecules of the title compound, C(14)H(13)N(3)O(2)S, are linked by inter-molecular O-H⋯O hydrogen bonds into centrosymmetric dimers forming R(2) (2)(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 = 287.33

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.115

S = 1.04

3132 reflections

197 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.40 e Å−3

Δρmin = −0.32 e Å−3

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 ▶).

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C14H13N3O2S	F000 = 600
Mr = 287.33	Dx = 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 = 2.5–23.4º
b = 13.1863 (3) Å	µ = 0.24 mm−1
c = 10.7732 (3) Å	T = 100 (2) K
β = 99.055 (2)º	Block, yellow
V = 1364.46 (6) Å3	0.40 × 0.30 × 0.20 mm
Z = 4

Bruker SMART APEX diffractometer	3132 independent reflections
Radiation source: fine-focus sealed tube	2358 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.078
T = 100(2) K	θmax = 27.5º
ω scans	θmin = 2.1º
Absorption correction: Multi-scan(SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.910, Tmax = 0.953	k = −17→16
16724 measured reflections	l = −13→13

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.115	w = 1/[σ2(Fo2) + (0.0502P)2 + 0.2883P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
3132 reflections	Δρmax = 0.40 e Å−3
197 parameters	Δρmin = −0.32 e Å−3
4 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

	x	y	z	Uiso*/Ueq
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)*

	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)

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)

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···O1iv	0.85 (1)	2.56 (2)	3.022 (2)	115 (2)

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⋯O1iv	0.85 (1)	2.56 (2)	3.022 (2)	115 (2)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .