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The title compound, C15H15N3OS, exists in the thione form and adopts an E configuration about the hydrazine bond, which is in the Z form with respect to the thiocarbonyl bond. An O—H...N intra­molecular hydrogen bond promotes planarity in part of the mol­ecule.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106014776/ga3010sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106014776/ga3010Isup2.hkl
Contains datablock I

CCDC reference: 618626

Comment top

Thiosemicarbazones of 2-hydroxyacetophenone and its derivatives are a class of versatile tridentate ONS-donor ligands capable of stabilizing both higher and lower oxidation states of transition metal ions. The biological activities of these ligands are related to their chelating ability with transition metal ions through phenol O, azomethine N and thiolate S atoms (John et al., 2004, and references therein). The coordination chemistry of these compounds has been of considerable interest as they can act as dianionic chelating ligands (John et al., 2002). The presence of bulky groups at the terminal 4-position increases the biological activity (Durham et al., 1974). de Sousa et al. (2001) have reported the title compound, (I), and its tin(IV) complexes but without a crystal structure study of (I).

Compound (I) (Fig. 1 and Table 1) adopts an alternative configuration to the recently reported 2-hydroxyacetophenone N(4)-cyclohexyl thiosemicarbazone (Seena et al., 2005; hereafter hapct). Atom S1 is in the Z form with azomethine atom N1 with respect to the N2—C8 bond [S1—C8—N2—N1 = 10.5 (2)°], unlike the E configuration seen in hapct. Furthermore, the E conformation of atom S1 and atom C9 of the phenyl ring in (I) about the C8—N3 bond [S1—C8—N3—C9 = −179.80 (14)°] is different from the Z conformation seen for those atoms in hapct. The N—H···S dimer ring involving intermolecular hydrogen bonds in compound (I) (Table 2), which utilizes atom N3 rather than the N2 atom used in hapct, may promote this conformation change.

The C8S1 and C8—N2 and C8—N3 bond distances (Table 1) are close to CS double bonds and C—N single bonds in thiosemicarbazones (Usman et al., 2002; Chattopadhyay et al., 1988; Latheef et al., 2006) and confirm the thione form for (I). The C8S1 bond length of (I) is in agreement with its di-2-pyridyl (Suni et al., 2006), 2-acetylpyridine (Bermejo et al., 1999) and acetophenone (Jian et al., 2005) counterparts, but is less than the 1.688 (2) Å value in hapct. The decrease of 0.017 (3) Å for the C8—N3 bond distance compared with C8—N2 suggests greater double-bond character to the former and increased electron localization at this substituted end. This is confirmed by the typical double-bond length for N1C7 and the considerable decrease [0.048 (2) Å] from the single-bond length for N3—C9 (Huheey et al., 1993). On complexation, the coordination occurs through the thiolate form, and the C—S bond length increases to 1.734 (3) and 1.754 (8) Å in the SnIV complexes [SnMe2(L)] and [SnBu2(L)], respectively (de Sousa et al., 2001), where L is the doubly deprotonated form of (I). The enolization on coordination leads to changes in the N2—C8, N1—N2 and N3—C8 bond lengths, although the overall conformation of (I) is retained.

The 2-hydroxyacetophenone thiosemicarbazone group excluding atoms S1 and N3 is approximately planar, with a maximum deviation of 0.074 (2) Å for atom C3. This planarity is associated with the six-membered ring (O1/H1O1/N1/C7/C6/C1) formed via the intramolecular O1—H1O1···N1 hydrogen bond (Table 2) as in salicylaldehyde 3-hexamethyleneiminyl thiosemicarbazone (Latheef et al., 2006). As a result, the exocyclic angles around atom C1 and angles subtended at C7 show considerable asymmetry (Table 1). The core thiosemicarbazone group (C7/N1/N2/C8/S1/N3/C9) is also approximately planar, with a maximum deviation from the mean plane of 0.0813 (14) Å for atom N1; this plane makes a dihedral angle of 15.88 (6)° with the plane comprising atoms O1 and C1–C6. The phenyl substituent is twisted away from this thiosemicarbazone plane with an interplanar angle of 48.46 (7)°.

Two kinds of intermolecular hydrogen bonds (Fig. 2) are seen in the packing. The molecules are paired using N3—H1N3···S1 interactions, and a three-dimensional motif is formed using a second weak intermolecular hydrogen bond, C11—H11···O1, and the C10—H10···π interaction (Table 2; Cg1 is the centre of the C1–C6 ring).

Experimental top

2-Hydroxyacetophenone N(4)-phenylthiosemicarbazone was prepared according to the reported method (de Sousa et al., 2001). To a hot methanol (volume?) solution of 4-phenylthiosemicarbazide (0.83615 g m, 5 mmol), a methanol (volume?) solution of 2-hydroxyacetophenone (0.6 ml, 5 mmol) was added with constant stirring. The mixture was refluxed for 4 h. After cooling, the resulting pale-yellow compound was filtered off, washed with methanol and ether, and finally dried over P4O10 in vacuo. Yellow block crystals suitable for X-ray analysis were obtained by slow evaporation from a solution in a mixture of methanol–ethyl ether (1:1) after one week. Elemental analysis found: C 62.61, H 5.35, N 14.57%; calculated: C 63.13, H 5.30, N 14.73%.

Refinement top

Atoms H1O1, H1N2 and H1N3 were located from difference maps and refined with isotropic displacement parameters. All other H atoms were positioned geometrically and treated as riding on their parent C atoms, with C—H distances of 0.93 and 0.96 Å, and with Uiso(H) values of 1.2Ueq(C) for aromatic and 1.5 Ueq(C) for methyl H atoms.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PLATON.

Figures top
[Figure 1] Fig. 1. Compound (I), with 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms are shown as small spheres of arbitrary radii
[Figure 2] Fig. 2. A view of the unit cell of (I) along the b axis. The intermolecular and main intramolecular hydrogen bonds (Table 2) are shown as dashed lines. The atom labels * and # correspond to symmetry codes i and ii in Table 2.
2-Hydroxyacetophenone 4-phenylthiosemicarbazone top
Crystal data top
C15H15N3OSF(000) = 1200
Mr = 285.36Dx = 1.299 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 7838 reflections
a = 16.858 (2) Åθ = 3.1–30.0°
b = 7.449 (2) ŵ = 0.22 mm1
c = 23.312 (7) ÅT = 293 K
β = 94.390 (15)°Block, yellow
V = 2918.7 (12) Å30.30 × 0.25 × 0.20 mm
Z = 8
Data collection top
Oxford Diffraction Xcalibur-S
diffractometer
2552 independent reflections
Radiation source: Enhanced (Mo) X-ray Source1947 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
Detector resolution: 15.9948 pixels mm-1θmax = 25.0°, θmin = 3.1°
ω scansh = 2020
Absorption correction: multi-scan
Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm in CrysAlis RED (Oxford Diffraction, 2006)
k = 88
Tmin = 0.867, Tmax = 0.959l = 2726
12882 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0534P)2 + 0.928P]
where P = (Fo2 + 2Fc2)/3
2552 reflections(Δ/σ)max < 0.001
194 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C15H15N3OSV = 2918.7 (12) Å3
Mr = 285.36Z = 8
Monoclinic, C2/cMo Kα radiation
a = 16.858 (2) ŵ = 0.22 mm1
b = 7.449 (2) ÅT = 293 K
c = 23.312 (7) Å0.30 × 0.25 × 0.20 mm
β = 94.390 (15)°
Data collection top
Oxford Diffraction Xcalibur-S
diffractometer
2552 independent reflections
Absorption correction: multi-scan
Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm in CrysAlis RED (Oxford Diffraction, 2006)
1947 reflections with I > 2σ(I)
Tmin = 0.867, Tmax = 0.959Rint = 0.021
12882 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.095H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.14 e Å3
2552 reflectionsΔρmin = 0.28 e Å3
194 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
xyzUiso*/Ueq
S10.06579 (3)0.62773 (8)0.335836 (18)0.0710 (2)
N10.00345 (8)0.71367 (19)0.44695 (5)0.0506 (3)
N20.05294 (9)0.66726 (19)0.40384 (5)0.0517 (4)
N30.08904 (8)0.6221 (2)0.30838 (6)0.0556 (4)
O10.14659 (10)0.8045 (2)0.47266 (6)0.0854 (5)
C10.12289 (12)0.8300 (2)0.52616 (7)0.0629 (5)
C20.18009 (14)0.8945 (3)0.56731 (9)0.0794 (6)
H20.23140.91730.55710.095*
C30.16157 (18)0.9246 (3)0.62259 (9)0.0872 (7)
H30.20030.96700.64980.105*
C40.08616 (18)0.8926 (3)0.63797 (9)0.0923 (8)
H40.07360.91420.67550.111*
C50.02904 (14)0.8286 (3)0.59808 (7)0.0748 (6)
H50.02190.80670.60920.090*
C60.04526 (11)0.7952 (2)0.54096 (6)0.0537 (4)
C70.01801 (10)0.7331 (2)0.49855 (6)0.0500 (4)
C80.02948 (10)0.6404 (2)0.34983 (6)0.0503 (4)
C90.17258 (9)0.6297 (2)0.31309 (6)0.0464 (4)
C100.20886 (10)0.5342 (2)0.35468 (7)0.0538 (4)
H100.17850.46500.38130.065*
C110.29042 (11)0.5421 (3)0.35637 (8)0.0672 (5)
H110.31480.47980.38480.081*
C120.33573 (11)0.6409 (3)0.31664 (8)0.0692 (5)
H120.39070.64550.31800.083*
C130.29976 (11)0.7329 (3)0.27475 (8)0.0632 (5)
H130.33050.79920.24750.076*
C140.21861 (10)0.7279 (2)0.27275 (6)0.0542 (4)
H140.19460.79060.24420.065*
C150.10042 (11)0.6981 (3)0.51574 (7)0.0672 (5)
H15A0.12850.80980.51770.101*
H15B0.09750.64080.55270.101*
H15C0.12800.62140.48780.101*
H1N20.1021 (11)0.696 (3)0.4067 (8)0.068 (6)*
H1N30.0745 (11)0.622 (3)0.2752 (8)0.069 (6)*
H1O10.1082 (14)0.770 (3)0.4518 (11)0.099 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0587 (3)0.1139 (5)0.0424 (2)0.0003 (3)0.01542 (19)0.0021 (2)
N10.0658 (8)0.0516 (8)0.0353 (6)0.0042 (6)0.0084 (6)0.0036 (6)
N20.0560 (8)0.0649 (10)0.0353 (7)0.0063 (7)0.0112 (6)0.0013 (6)
N30.0573 (8)0.0786 (10)0.0326 (7)0.0005 (7)0.0139 (6)0.0007 (7)
O10.0818 (10)0.1256 (14)0.0497 (7)0.0303 (9)0.0104 (7)0.0099 (8)
C10.0919 (14)0.0524 (11)0.0437 (9)0.0053 (9)0.0001 (9)0.0111 (7)
C20.1000 (15)0.0638 (13)0.0714 (13)0.0127 (11)0.0124 (11)0.0129 (10)
C30.135 (2)0.0579 (13)0.0634 (13)0.0111 (13)0.0287 (13)0.0078 (10)
C40.139 (2)0.0872 (17)0.0491 (11)0.0371 (16)0.0068 (13)0.0164 (11)
C50.1036 (16)0.0771 (14)0.0438 (10)0.0283 (11)0.0057 (9)0.0071 (9)
C60.0811 (12)0.0427 (9)0.0377 (8)0.0115 (8)0.0062 (7)0.0050 (7)
C70.0720 (11)0.0412 (9)0.0380 (8)0.0123 (8)0.0126 (7)0.0072 (7)
C80.0619 (10)0.0536 (10)0.0367 (8)0.0023 (8)0.0124 (7)0.0043 (7)
C90.0592 (9)0.0455 (9)0.0359 (7)0.0016 (7)0.0127 (6)0.0031 (6)
C100.0703 (11)0.0505 (10)0.0421 (8)0.0020 (8)0.0140 (7)0.0061 (7)
C110.0760 (12)0.0766 (13)0.0523 (10)0.0146 (10)0.0265 (9)0.0007 (9)
C120.0593 (10)0.0877 (15)0.0629 (11)0.0029 (10)0.0193 (9)0.0085 (10)
C130.0688 (11)0.0625 (12)0.0583 (10)0.0106 (9)0.0039 (8)0.0001 (9)
C140.0710 (11)0.0519 (10)0.0405 (8)0.0046 (8)0.0106 (7)0.0061 (7)
C150.0786 (12)0.0784 (13)0.0472 (9)0.0125 (10)0.0214 (8)0.0078 (9)
Geometric parameters (Å, º) top
S1—C81.6659 (16)C5—C61.402 (2)
N1—C71.2905 (19)C5—H50.9300
N1—N21.3736 (19)C6—C71.472 (2)
N2—C81.3631 (19)C7—C151.498 (2)
N2—H1N20.864 (19)C9—C141.382 (2)
N3—C81.346 (2)C9—C101.383 (2)
N3—C91.422 (2)C10—C111.380 (2)
N3—H1N30.829 (19)C10—H100.9300
O1—C11.352 (2)C11—C121.369 (3)
O1—H1O10.82 (2)C11—H110.9300
C1—C21.393 (3)C12—C131.372 (3)
C1—C61.403 (3)C12—H120.9300
C2—C31.368 (3)C13—C141.373 (2)
C2—H20.9300C13—H130.9300
C3—C41.368 (3)C14—H140.9300
C3—H30.9300C15—H15A0.9600
C4—C51.372 (3)C15—H15B0.9600
C4—H40.9300C15—H15C0.9600
C7—N1—N2118.85 (14)C6—C7—C15120.94 (14)
C8—N2—N1118.64 (14)N3—C8—N2115.14 (14)
C8—N2—H1N2117.2 (12)N3—C8—S1122.07 (11)
N1—N2—H1N2119.6 (12)N2—C8—S1122.78 (12)
C8—N3—C9128.99 (13)C14—C9—C10119.61 (15)
C8—N3—H1N3114.4 (13)C14—C9—N3118.46 (13)
C9—N3—H1N3115.9 (13)C10—C9—N3121.83 (15)
C1—O1—H1O1108.4 (17)C11—C10—C9119.56 (16)
O1—C1—C2116.49 (19)C11—C10—H10120.2
O1—C1—C6123.24 (16)C9—C10—H10120.2
C2—C1—C6120.28 (18)C12—C11—C10120.62 (16)
C3—C2—C1120.6 (2)C12—C11—H11119.7
C3—C2—H2119.7C10—C11—H11119.7
C1—C2—H2119.7C11—C12—C13119.74 (17)
C2—C3—C4120.1 (2)C11—C12—H12120.1
C2—C3—H3119.9C13—C12—H12120.1
C4—C3—H3119.9C12—C13—C14120.43 (17)
C3—C4—C5120.1 (2)C12—C13—H13119.8
C3—C4—H4120.0C14—C13—H13119.8
C5—C4—H4120.0C13—C14—C9120.03 (15)
C4—C5—C6121.8 (2)C13—C14—H14120.0
C4—C5—H5119.1C9—C14—H14120.0
C6—C5—H5119.1C7—C15—H15A109.5
C5—C6—C1117.02 (18)C7—C15—H15B109.5
C5—C6—C7120.62 (17)H15A—C15—H15B109.5
C1—C6—C7122.31 (14)C7—C15—H15C109.5
N1—C7—C6114.88 (15)H15A—C15—H15C109.5
N1—C7—C15124.18 (15)H15B—C15—H15C109.5
C7—N1—N2—C8177.59 (15)C5—C6—C7—C152.0 (2)
O1—C1—C2—C3179.90 (19)C1—C6—C7—C15179.70 (16)
C6—C1—C2—C30.1 (3)C9—N3—C8—N21.1 (3)
C1—C2—C3—C40.4 (3)C9—N3—C8—S1179.80 (14)
C2—C3—C4—C50.6 (4)N1—N2—C8—N3170.43 (14)
C3—C4—C5—C60.4 (3)N1—N2—C8—S110.5 (2)
C4—C5—C6—C10.1 (3)C8—N3—C9—C14135.13 (18)
C4—C5—C6—C7177.66 (18)C8—N3—C9—C1048.5 (3)
O1—C1—C6—C5179.74 (18)C14—C9—C10—C111.8 (2)
C2—C1—C6—C50.1 (3)N3—C9—C10—C11178.12 (15)
O1—C1—C6—C72.0 (3)C9—C10—C11—C121.2 (3)
C2—C1—C6—C7177.79 (17)C10—C11—C12—C130.0 (3)
N2—N1—C7—C6175.87 (13)C11—C12—C13—C140.6 (3)
N2—N1—C7—C153.6 (2)C12—C13—C14—C90.0 (3)
C5—C6—C7—N1177.46 (16)C10—C9—C14—C131.2 (2)
C1—C6—C7—N10.2 (2)N3—C9—C14—C13177.65 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H1N3···S1i0.829 (19)2.604 (19)3.4148 (18)166.0 (17)
O1—H1O1···N10.82 (2)1.81 (2)2.534 (2)146 (2)
C11—H11···O1ii0.932.553.471 (3)168
C10—H10···Cg1iii0.932.833.681 (2)152
Symmetry codes: (i) x, y, z+1/2; (ii) x1/2, y1/2, z; (iii) x, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC15H15N3OS
Mr285.36
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)16.858 (2), 7.449 (2), 23.312 (7)
β (°) 94.390 (15)
V3)2918.7 (12)
Z8
Radiation typeMo Kα
µ (mm1)0.22
Crystal size (mm)0.30 × 0.25 × 0.20
Data collection
DiffractometerOxford Diffraction Xcalibur-S
diffractometer
Absorption correctionMulti-scan
Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm in CrysAlis RED (Oxford Diffraction, 2006)
Tmin, Tmax0.867, 0.959
No. of measured, independent and
observed [I > 2σ(I)] reflections
12882, 2552, 1947
Rint0.021
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.095, 1.06
No. of reflections2552
No. of parameters194
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.14, 0.28

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), CrysAlis RED, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003), SHELXL97 and PLATON.

Selected geometric parameters (Å, º) top
S1—C81.6659 (16)N2—C81.3631 (19)
N1—C71.2905 (19)N3—C81.346 (2)
N1—N21.3736 (19)N3—C91.422 (2)
C7—N1—N2118.85 (14)O1—C1—C6123.24 (16)
C8—N2—N1118.64 (14)N1—C7—C6114.88 (15)
C8—N3—C9128.99 (13)N1—C7—C15124.18 (15)
O1—C1—C2116.49 (19)
C8—N3—C9—C1048.5 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H1N3···S1i0.829 (19)2.604 (19)3.4148 (18)166.0 (17)
O1—H1O1···N10.82 (2)1.81 (2)2.534 (2)146 (2)
C11—H11···O1ii0.932.553.471 (3)168
C10—H10···Cg1iii0.932.833.681 (2)152
Symmetry codes: (i) x, y, z+1/2; (ii) x1/2, y1/2, z; (iii) x, y+1, z+1.
 

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