(E)-3,4-Dihydroxy-benzaldehyde 4-ethyl-thio-semicarbazone.

The title compound, C(10)H(13)N(3)O(2)S, was prepared by condensation of 3,4-dihydroxy-benzaldehyde with 4-ethyl-3-thio-semicarbazide. The mol-ecule adopts an E configuration with respect to the C=N bond. One of the OH substituents on the dihydroxy-benzene ring is disordered over the two possible 3-positions on either side of the ordered 4-hydr-oxy group. The occupancy of the major disorder component refined to 0.633 (7). The mol-ecule is essentially planar, with an r.m.s. deviation through all non-H atoms of 0.0862 Å. An intra-molecular N-H⋯N hydrogen bond forms between the outer amine residue and the imine N atom, generating an S(5) ring motif and contributing to the planarity of the mol-ecule. In the crystal structure, an extensive network of classical O-H⋯O, O-H⋯S and N-H⋯S hydrogen bonds and weak C-H⋯O and S⋯O [3.301 (3) Å] inter-actions link mol-ecules into sheets running approximately parallel to the ab plane.

Related literature

For related structures, see: Swesi et al. (2006 ▶); Kovala-Demertzi et al. (2004 ▶); Jian & Li (2006 ▶). For reference structural data, see: Allen et al. (1987 ▶). For ring motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C10H13N3O2S

M = 239.29

Monoclinic,

a = 10.6549 (12) Å

b = 12.9020 (16) Å

c = 8.6375 (11) Å

β = 107.910 (4)°

V = 1129.9 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.28 mm−1

T = 91 (2) K

0.44 × 0.11 × 0.09 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T min = 0.818, T max = 0.975

12327 measured reflections

1998 independent reflections

1507 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.168

S = 1.05

1998 reflections

165 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.41 e Å−3

Δρmin = −0.64 e Å−3

Data collection: APEX2 (Bruker 2006 ▶); cell refinement: APEX2 and SAINT (Bruker 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶) and TITAN2000 (Hunter & Simpson, 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and TITAN2000; molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 ▶) and PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808009148/hg2389sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808009148/hg2389Isup2.hkl

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

C10H13N3O2S	F000 = 504
Mr = 239.29	Dx = 1.407 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3071 reflections
a = 10.6549 (12) Å	θ = 2.6–25.0º
b = 12.9020 (16) Å	µ = 0.28 mm−1
c = 8.6375 (11) Å	T = 91 (2) K
β = 107.910 (4)º	Block, red
V = 1129.9 (2) Å3	0.44 × 0.11 × 0.09 mm
Z = 4

Bruker APEXII CCD area-detector diffractometer	1998 independent reflections
Radiation source: fine-focus sealed tube	1507 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.040
T = 92(2) K	θmax = 25.1º
ω scans	θmin = 3.1º
Absorption correction: multi-scan(SADABS; Bruker, 2006)	h = −12→12
Tmin = 0.818, Tmax = 0.975	k = −15→15
12327 measured reflections	l = −10→8

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)] = 0.059	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.168	w = 1/[σ2(Fo2) + (0.0718P)2 + 1.7231P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
1998 reflections	Δρmax = 1.41 e Å−3
165 parameters	Δρmin = −0.64 e Å−3
2 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.7990 (3)	0.2409 (2)	0.2636 (3)	0.0304 (7)
C2	0.9009 (3)	0.1922 (2)	0.2235 (3)	0.0342 (7)
H2	0.9097	0.1190	0.2323	0.041*
C3	0.9897 (3)	0.2493 (3)	0.1712 (4)	0.0382 (8)
H3	1.048 (11)	0.201 (8)	0.147 (17)	0.046*	0.367 (7)
O3	1.0884 (4)	0.2059 (4)	0.1330 (6)	0.0525 (14)	0.633 (7)
H3A	1.1301	0.2516	0.0999	0.079*	0.633 (7)
C5	0.8761 (3)	0.4051 (3)	0.1995 (4)	0.0394 (8)
H5	0.862 (11)	0.477 (2)	0.177 (13)	0.047*	0.633 (7)
O5	0.8733 (10)	0.5042 (5)	0.1953 (12)	0.045 (2)	0.367 (7)
H5A	0.8856	0.5248	0.1089	0.068*	0.367 (7)
C4	0.9776 (3)	0.3557 (3)	0.1580 (4)	0.0381 (8)
O4	1.0659 (2)	0.4115 (2)	0.1053 (3)	0.0503 (7)
H4	1.0294	0.4656	0.0584	0.075*
C6	0.7871 (3)	0.3484 (2)	0.2514 (3)	0.0334 (7)
H6	0.7178	0.3825	0.2787	0.040*
C7	0.7094 (3)	0.1775 (3)	0.3225 (3)	0.0357 (7)
H7	0.7228	0.1047	0.3322	0.043*
N1	0.6134 (2)	0.2175 (2)	0.3612 (3)	0.0390 (7)
N2	0.5403 (3)	0.1489 (3)	0.4216 (3)	0.0442 (7)
H2A	0.5567	0.0819	0.4244	0.053*
C8	0.4433 (3)	0.1862 (3)	0.4763 (4)	0.0458 (9)
S1	0.36442 (11)	0.10262 (10)	0.56744 (13)	0.0685 (4)
N3	0.4168 (3)	0.2853 (3)	0.4565 (3)	0.0506 (8)
H3B	0.4660	0.3233	0.4133	0.061*
C9	0.3112 (4)	0.3371 (4)	0.5010 (5)	0.0678 (13)
H9A	0.3118	0.3133	0.6102	0.081*
H9B	0.2252	0.3177	0.4224	0.081*
C10	0.3260 (5)	0.4506 (5)	0.5024 (6)	0.0804 (15)
H10A	0.4042	0.4708	0.5917	0.121*
H10B	0.2476	0.4831	0.5179	0.121*
H10C	0.3361	0.4735	0.3987	0.121*

	U11	U22	U33	U12	U13	U23
C1	0.0251 (14)	0.0466 (18)	0.0195 (14)	−0.0048 (12)	0.0069 (11)	0.0028 (12)
C2	0.0353 (16)	0.0376 (17)	0.0304 (15)	0.0009 (13)	0.0112 (13)	0.0039 (13)
C3	0.0292 (16)	0.057 (2)	0.0319 (16)	0.0021 (14)	0.0146 (13)	0.0001 (15)
O3	0.037 (3)	0.075 (3)	0.059 (3)	0.009 (2)	0.036 (2)	−0.002 (2)
C5	0.0427 (18)	0.0392 (18)	0.0365 (17)	−0.0057 (15)	0.0122 (14)	0.0051 (15)
O5	0.048 (4)	0.035 (4)	0.053 (5)	−0.010 (4)	0.015 (3)	0.013 (4)
C4	0.0331 (16)	0.056 (2)	0.0265 (15)	−0.0149 (15)	0.0113 (13)	0.0037 (14)
O4	0.0449 (14)	0.0657 (17)	0.0471 (14)	−0.0192 (12)	0.0241 (12)	0.0093 (12)
C6	0.0304 (15)	0.0422 (17)	0.0295 (16)	0.0020 (13)	0.0119 (13)	0.0009 (13)
C7	0.0348 (16)	0.0476 (19)	0.0252 (15)	−0.0110 (14)	0.0099 (13)	0.0018 (13)
N1	0.0281 (13)	0.0639 (18)	0.0267 (13)	−0.0131 (12)	0.0110 (11)	0.0059 (12)
N2	0.0380 (14)	0.0675 (19)	0.0319 (14)	−0.0205 (14)	0.0178 (12)	−0.0021 (13)
C8	0.0331 (17)	0.082 (3)	0.0250 (16)	−0.0237 (18)	0.0133 (13)	−0.0102 (17)
S1	0.0738 (7)	0.0931 (9)	0.0585 (7)	−0.0513 (6)	0.0497 (6)	−0.0299 (6)
N3	0.0305 (14)	0.092 (3)	0.0352 (15)	−0.0037 (15)	0.0181 (12)	0.0076 (16)
C9	0.038 (2)	0.131 (4)	0.039 (2)	0.008 (2)	0.0176 (16)	0.000 (2)
C10	0.076 (3)	0.122 (5)	0.053 (3)	0.036 (3)	0.034 (2)	0.000 (3)

C1—C2	1.388 (4)	C7—N1	1.278 (4)
C1—C6	1.395 (5)	C7—H7	0.9500
C1—C7	1.462 (4)	N1—N2	1.384 (3)
C2—C3	1.380 (4)	N2—C8	1.350 (4)
C2—H2	0.9500	N2—H2A	0.8800
C3—O3	1.319 (5)	C8—N3	1.310 (5)
C3—C4	1.380 (5)	C8—S1	1.702 (3)
C3—H3	0.950 (10)	S1—O4i	3.301 (2)
O3—H3A	0.8400	N3—C9	1.457 (5)
C5—O5	1.279 (7)	N3—H3B	0.8800
C5—C6	1.376 (4)	C9—C10	1.473 (7)
C5—C4	1.394 (5)	C9—H9A	0.9900
C5—H5	0.950 (10)	C9—H9B	0.9900
O5—H5A	0.8400	C10—H10A	0.9800
C4—O4	1.369 (3)	C10—H10B	0.9800
O4—H4	0.8400	C10—H10C	0.9800
C6—H6	0.9500
C2—C1—C6	119.4 (3)	N1—C7—C1	121.7 (3)
C2—C1—C7	118.6 (3)	N1—C7—H7	119.1
C6—C1—C7	121.9 (3)	C1—C7—H7	119.1
C3—C2—C1	120.6 (3)	C7—N1—N2	115.4 (3)
C3—C2—H2	119.7	C8—N2—N1	119.0 (3)
C1—C2—H2	119.7	C8—N2—H2A	120.5
O3—C3—C4	117.6 (3)	N1—N2—H2A	120.5
O3—C3—C2	122.3 (4)	N3—C8—N2	117.4 (3)
C4—C3—C2	120.1 (3)	N3—C8—S1	124.2 (3)
C4—C3—H3	133 (8)	N2—C8—S1	118.4 (3)
C2—C3—H3	107 (8)	C8—N3—C9	124.5 (3)
C3—O3—H3A	109.5	C8—N3—H3B	117.8
O5—C5—C6	121.9 (5)	C9—N3—H3B	117.8
O5—C5—C4	117.6 (5)	N3—C9—C10	111.6 (4)
C6—C5—C4	120.5 (3)	N3—C9—H9A	109.3
C6—C5—H5	120 (7)	C10—C9—H9A	109.3
C4—C5—H5	119 (7)	N3—C9—H9B	109.3
C5—O5—H5A	109.5	C10—C9—H9B	109.3
O4—C4—C3	119.6 (3)	H9A—C9—H9B	108.0
O4—C4—C5	120.8 (3)	C9—C10—H10A	109.5
C3—C4—C5	119.6 (3)	C9—C10—H10B	109.5
C4—O4—H4	109.5	H10A—C10—H10B	109.5
C5—C6—C1	119.9 (3)	C9—C10—H10C	109.5
C5—C6—H6	120.1	H10A—C10—H10C	109.5
C1—C6—H6	120.1	H10B—C10—H10C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···N1	0.88	2.23	2.626 (4)	107
O5—H5A···S1ii	0.84	2.82	3.106 (9)	102
C2—H2···O5iii	0.95	2.65	3.335 (8)	129
N2—H2A···S1iv	0.88	2.52	3.392 (4)	172
O4—H4···O4v	0.84	2.16	2.988 (5)	169
C9—H9A···O3i	0.99	2.46	2.985 (5)	113

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯N1	0.88	2.23	2.626 (4)	107
O5—H5A⋯S1i	0.84	2.82	3.106 (9)	102
C2—H2⋯O5ii	0.95	2.65	3.335 (8)	129
N2—H2A⋯S1iii	0.88	2.52	3.392 (4)	172
O4—H4⋯O4iv	0.84	2.16	2.988 (5)	169
C9—H9A⋯O3v	0.99	2.46	2.985 (5)	113

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