







Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808009148/hg2389sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536808009148/hg2389Isup2.hkl |
CCDC reference: 688923
Key indicators
- Single-crystal X-ray study
- T = 91 K
- Mean
(C-C) = 0.005 Å
- Disorder in main residue
- R factor = 0.059
- wR factor = 0.169
- Data-to-parameter ratio = 12.1
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT415_ALERT_2_B Short Inter D-H..H-X H3A .. H9A .. 2.09 Ang. PLAT416_ALERT_2_B Short Intra D-H..H-D H4 .. H5A .. 1.88 Ang. PLAT417_ALERT_2_B Short Inter D-H..H-D H4 .. H4 .. 1.35 Ang. PLAT417_ALERT_2_B Short Inter D-H..H-D H4 .. H5A .. 1.93 Ang.
Alert level C DIFMX01_ALERT_2_C The maximum difference density is > 0.1*ZMAX*0.75 _refine_diff_density_max given = 1.412 Test value = 1.200 DIFMX02_ALERT_1_C The maximum difference density is > 0.1*ZMAX*0.75 The relevant atom site should be identified. SHFSU01_ALERT_2_C Test not performed. _refine_ls_shift/su_max and _refine_ls_shift/esd_max not present. Absolute value of the parameter shift to su ratio given 0.001 PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.20 PLAT097_ALERT_2_C Maximum (Positive) Residual Density ............ 1.41 e/A PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.66 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.03 Ratio PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.52 PLAT301_ALERT_3_C Main Residue Disorder ......................... 6.00 Perc. PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5 PLAT432_ALERT_2_C Short Inter X...Y Contact O3 .. C9 .. 2.98 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H2 .. O5 .. 2.65 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2
0 ALERT level A = In general: serious problem 4 ALERT level B = Potentially serious problem 12 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 11 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound C10H13N3O2S was prepared by heating an ethanolic (35 ml) solution of 3,4-dihydroxybenzaldehyde (1.4 g, 10 mmol) and 4-ethyl-3-thiosemicarbazide (1.2 g, 10 mmol) under reflux for 1 h. The resulting product was isolated and recrystallized from ethanol to afford red block-shaped crystals in 71% yield (m.p. 464–467 K).
The aromatic H atoms of the two disorder components were located in a difference Fourier map and refined with fixed isotropic displacement parameters with C—H distances restrained to 0.95 (1) Å. All other H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.95 Å, Uiso=1.2Ueq (C) for aromatic 0.99 Å, Uiso = 1.2Ueq (C) for CH2, 0.98 Å, Uiso = 1.5Ueq (C) for CH3 0.88 Å, Uiso = 1.2Ueq (N) for NH and 0.84 Å, Uiso = 1.5Ueq (O) for the OH atoms. Close contacts involving the H atoms of the OH substituents, suggest that there may be unresolved disorder particularly with the location of the H atoms. The highest residual electron density peak is located at 2.56 Å from O5 and the deepest hole is located at 0.81 Å from S1.
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) and TITAN2000 (Hunter & Simpson, 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and TITAN2000 (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) and PLATON (Spek, 2003).
C10H13N3O2S | F(000) = 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 = 2.6–25.0° |
b = 12.9020 (16) Å | µ = 0.28 mm−1 |
c = 8.6375 (11) Å | T = 91 K |
β = 107.910 (4)° | 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) |
Graphite monochromator | Rint = 0.040 |
ω scans | θmax = 25.1°, θmin = 3.1° |
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 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.168 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0718P)2 + 1.7231P] where P = (Fo2 + 2Fc2)/3 |
1998 reflections | (Δ/σ)max < 0.001 |
165 parameters | Δρmax = 1.41 e Å−3 |
2 restraints | Δρmin = −0.64 e Å−3 |
C10H13N3O2S | V = 1129.9 (2) Å3 |
Mr = 239.29 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.6549 (12) Å | µ = 0.28 mm−1 |
b = 12.9020 (16) Å | T = 91 K |
c = 8.6375 (11) Å | 0.44 × 0.11 × 0.09 mm |
β = 107.910 (4)° |
Bruker APEXII CCD area-detector diffractometer | 1998 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | 1507 reflections with I > 2σ(I) |
Tmin = 0.818, Tmax = 0.975 | Rint = 0.040 |
12327 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 2 restraints |
wR(F2) = 0.168 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 1.41 e Å−3 |
1998 reflections | Δρmin = −0.64 e Å−3 |
165 parameters |
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 |
Symmetry code: (i) x−1, −y+1/2, z+1/2. |
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 |
Symmetry codes: (i) x−1, −y+1/2, z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) −x+2, y−1/2, −z+1/2; (iv) −x+1, −y, −z+1; (v) −x+2, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C10H13N3O2S |
Mr | 239.29 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 91 |
a, b, c (Å) | 10.6549 (12), 12.9020 (16), 8.6375 (11) |
β (°) | 107.910 (4) |
V (Å3) | 1129.9 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.28 |
Crystal size (mm) | 0.44 × 0.11 × 0.09 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2006) |
Tmin, Tmax | 0.818, 0.975 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12327, 1998, 1507 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.168, 1.05 |
No. of reflections | 1998 |
No. of parameters | 165 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.41, −0.64 |
Computer programs: , APEX2 (Bruker 2006) and SAINT (Bruker 2006), SAINT (Bruker 2006), SHELXS97 (Sheldrick, 2008) and TITAN2000 (Hunter & Simpson, 1999), SHELXL97 (Sheldrick, 2008) and TITAN2000 (Hunter & Simpson, 1999), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004) and PLATON (Spek, 2003).
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) | 102.3 |
C2—H2···O5ii | 0.95 | 2.65 | 3.335 (8) | 129.1 |
N2—H2A···S1iii | 0.88 | 2.52 | 3.392 (4) | 172.0 |
O4—H4···O4iv | 0.84 | 2.16 | 2.988 (5) | 168.8 |
C9—H9A···O3v | 0.99 | 2.46 | 2.985 (5) | 112.6 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+2, y−1/2, −z+1/2; (iii) −x+1, −y, −z+1; (iv) −x+2, −y+1, −z; (v) x−1, −y+1/2, z+1/2. |
For example the structure of the related molecule 2,3-dihydroxybenzaldehyde thiosemicarbazone hemihydrate has been reported by Swesi et al. (2006) as have the structures of a phenylthiocarbazole with a single hydroxy-substituent on the benzylidene ring (Jian & Li, 2006) and of a palladium(II) complex of an ethylthiosemicarbonate ligand deprotonated at the phenolate ring (Kovala-Demertzi et al., 2004).
The molecule adopts an E configuration with respect to the C=N bond and bond distances and angles are normal (Allen et al., 1987). One of the OH substituents on the dihydroxy benzene ring is disordered over the two possible 3-positions (labelled O3 and O5) on either side of the ordered O4 hydroxo group. Occupancy of the O3 and H5 atoms of the major disorder component refines to 0.633 (7). The molecule is essentially planar with an r.m.s. deviation through all non-hydrogen atoms of 0.0862 Å. An intramolecular N3—H3B···N1 hydrogen bond forms between the outer amine residue and the imine N atom generating an S(5) ring motif (Bernstein et al., 1995) which contributes to the planarity of the molecule.
In the crystal structure N2—H2A···S1 hydrogen bonds, Table 1, generate centrosymmetric R22(8) rings. Other classical O—H···O and O—H···S hydrogen bonds combine with weak C—H···O and S1···O4i interactions (d(S1···O4) = 3.301 (3) Å; i = -1 + x, 1/2 - y, 1/2 + z) to form sheets running approximately parallel to the ac diagonal, Fig 2.