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The mol­ecular structures of two salicylaldehyde thio­semi­carba­zone derivatives, namely sali­cylaldehyde 4-phenyl­thio­semicarbazone, C14H13N3OS, (I), and 4-methoxysali­cyl­­aldehyde 4-phenyl­thio­semicarbazone, C15H15N3O2S, (II), both of potential pharmacological inter­est, are found in the keto (thione) tautomeric form. The first compound represents a second triclinic polymorph of composition β-C14H13N3OS. Although both polymorphs crystallize in the same space group (P\overline{1}), the α-polymorph [Seena, Kurup & Suresh (2008). J. Chem. Crystallogr. 38, 93–96] differs from the β form in its unit-cell volume at 293 K. The mol­ecules in the crystal structures of (I) and (II) are linked into centrosymmetric R22(8) dimers by hydrogen bonds of the N—H...S=C type. These dimers are connected through π–π stacking and T-shaped C—H...π inter­actions into three-dimensional net­works.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108029016/av3157sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108029016/av3157Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108029016/av3157IIsup3.hkl
Contains datablock II

CCDC references: 707220; 707221

Comment top

Thiosemicarbazones are a class of organic molecules which belong to a large family of thiourea derivatives (Casas et al., 2000). Widespread interest in the chemistry of thiosemicarbazones is associated with their broad spectrum of biological activities with potential uses in antibacterial, antiviral and antitumour treatments (Bharti et al., 2002; Smee & Sidwell, 2003; Hu et al., 2006; Oliveira et al., 2007). Many of their properties are a function of the parent aldehyde or ketone, and these properties can therefore be elegantly tuned by the appropriate choice of parent. From a structural perspective, thiosemicarbazones attract attention as interesting ligands due to their tendency to undergo tautomerism and form planar highly rigid Schiff bases capable of imposing a variety of mixed-donor coordination environments about metal cations. Thiosemicarbazones derived from salicylaldehyde can exist in several tautomeric forms but the most interesting are those denoted A and B in scheme 1. Such molecular isomerization can result in different binding modes. In form A, the molecule can act as a monoanionic ligand after losing the H atom from the hydroxyl group, or as a dianionic ligand after losing H atoms from the mercapto and hydroxyl groups of form B.

We present here the crystal structures of two closely related thiosemicarbazones derived from salicylaldehyde: salicylaldehyde 4-phenylthiosemicarbazone, (I), and 4-methoxysalicylaldehyde 4-phenylthiosemicarbazone, (II). The structure of (I) has been reported previously (Seena et al., 2008). The compound crystallized in the same space group (P1) and we refer to it as the α-polymorph (obtained from ethanol). We have now obtained a second triclinic polymorph of (I), denoted the β-polymorph (obtained from methanol). Although both polymorphs crystallize in space group No. 2, they have different unit-cell volumes at 293 K and their unit-cell parameters are different [in particular, V = 2002.1 (5) Å3 for the α-polymorph and V = 1339.6 (1) Å3 for the β-polymorph]. These two forms of (I) have different numbers of molecules in the asymmetric unit (three and two, respectively). The asymmetric unit of (I) consists of two crystallographically independent molecules, (Ia) and (Ib) (Fig. 1). The molecular structures of (I) (in both polymorphs) and (II) (Fig. 2) are very similiar, but not equal. The crystal structures are characterized by a great variety of interactions, especially of the N—H···S type, and these will be discussed later.

The atom-labelling schemes are almost the same. In the following discussion, the order of the compounds for a given value is (Ia) and (Ib) of (I), then (II). Selected bond lengths and bond angles for (I) and (II) are given in Tables 1 and 3. Similar to many uncomplexed and unprotonated thiosemicarbazones (Soriano-García et al., 1986; Dinçer et al., 2005; Seena et al., 2008), a trans configuration of atom S1 with respect to atom N3 is observed [S1—C1—N2—N3 = -178.51 (10), -178.04 (10) and 176.30 (9)°] and atom N1 is in a cis configuration with respect to atom N3. The C1—S1 bond distance of 1.6758 (14) Å [1.6827 (13) and 1.6768 (13) Å] does not differ significantly from that found in thiourea (Truter, 1967). This bond, together with the C1—N2 bond of 1.3515 (17) Å [1.3416 (17) and 1.3441 (17) Å] and the C1—N1 bond of 1.3341 (17) Å [1.3361 (17) and 1.3331 (18) Å], indicate that the molecules in the crystal structures of (I) and (II) are in the keto (thione) form. This is also in agreement with the absence of a strong band in the IR spectra centred at 2500 cm-1 [ν(S—H) stretching mode].

The molecular structures of (I) and (II) consist of three structural fragments: salicyl and phenyl parts separated by the central thiosemicarbazone part. The salicyl–thiosemicarbazone parts of molecules are almost planar. Maximum deviations from the plane in molecule (Ia) are -0.214 (1), 0.183 (1) and -0.138 (2) Å for N11, O1 and C17, respectively [-0.192 (1), 0.107 (1) and 0.097 (1) Å for N21, N22 and O2 in (Ib) and 0.285 (2), -0.140 (2), -0.092 (1) Å for N1, C15 and C1 in (II)]. The dihedral angle between the planes of the salicyl–thiosemicarbazone parts and the phenyl ring on the N1 substituents of 64.44 (4)° [and 53.07 (4)° and 52.16 (5)°] indicates non-planarity of the ligands, although the thiosemicarbazone parts themselves are planar. Such an arrangement allows delocalization of the π-electrons in the N1—C1—N2—N3—C2 moieties. The salicylaldimine parts of the molecules in the crystal structures of (I) and (II) are characterized by a six-membered pseudoaromatic rings(N3—C2—C3—C4—O1—H1O). Rings are formed by an intramolecular hydrogen bond [S(6)] which is enhanced by π-electron delocalization as can be seen easily from the bond lengths within the rings (Tables 1 and 3). Such resonance-assisted hydrogen bonds seem to be the general features of the crystal structures of thiosemicarbazones and Schiff bases derived from salicylaldehyde (Soriano-García et al., 1986; Popović et al., 2002). The C4—O1 bond lengths are comparable with those found in phenols: 1.3563 (17), 1.3575 (16) and 1.3551 (17) Å (Allen et al., 1987). In contrast, C2—N3 [1.2816 (17), 1.2790 (17), 1.2797 (17) Å] is assigned as a double bond. The endocyclic bond distances and angles found in the phenyl rings, with the exception of that at C3, do not differ from those in normal sp2 hybridized moieties. The measured collapse of the C4—C3—C8 angles together with good electron donor properties of the O atom may be a consequence of the conjugation of the phenyl ring with the thiosemicarbazone parts of the molecules.

The crystal packings are characterized by a great variety of hydrogen bonds (presented in Tables 2 and 4). A close inspection of the unit cells (Figs. 3 and 4) and two-dimensional fingerprint plots derived from Hirshfeld surfaces (McKinnon et al., 2004) of both polymorphs of (I) and (II) revealed very specific N—H···S hydrogen bonding (spikes centred around 2.6 Å). This type of structural motif [denoted R22(8); Etter et al., 1990] is very common in the crystal structures of thiosemicarbazones (Soriano-García et al., 1986; Sampath et al., 2003; Dinçer et al., 2005).

Figs. 5(a) and 5(b) unambiguously show that different intermolecular interactions are present in the polymorphs α and β, which results in different packing modes. In polymorph α, the shortest contacts corespond to the very close H···H contacts [H25···H25i and H3···H27ii are 2.25 (4) and 2.25 (6) Å; symmetry codes: (i) -x, -y, 2 - z ; (ii) 1 - x, -y, 1 - z]. In plots of (I) and (II) (Figs. 5b and 5c) `wings' are more pronounced, which resemble [indicate?] aromatic interactions [π···π stacking, C14···C214 and C114···C24 distances are 3.237 (2) and 3.267 (2) Å in (I)] and there are T-shaped C—H···π contacts between the molecules in (II) [C12···H5iii and C10···H15Biv = 2.93 and 2.86 Å; symmetry codes: (iii) 2 - x, -y, -z ; (iv) -2 + x, 1 + y, z)].

Related literature top

For related literature, see: Allen et al. (1987); Bharti et al. (2002); Casas et al. (2000); Dinçer et al. (2005); Etter et al. (1990); Hu et al. (2006); McKinnon et al. (2004); Oliveira et al. (2007); Popović et al. (2002); Purohit et al. (1989); Sampath et al. (2003); Seena et al. (2008); Smee & Sidwell (2003); Soriano-García, Valdés-Martínez, Toscano, Gómez-Lara & Villalobos-Peñaloza (1986); Truter (1967).

Experimental top

Compound (I) was prepared by slight modification of the procedure described by Purohit et al. (1989), using methanol as the solvent instead of ethanol. White needle-like crystals were obtained directly from the reaction mixture as the first form of compound (I). The structure of this α-polymorph, obtained from ethanol, was recently published by Seena et al. (2008). The remaining mother liquor was kept at room temperature and after 2–3 weeks yielded the β-polymorph of compound (I), in the form of transparent plates [prismatic in CIF tables - please clarify]. The crystals were filtered off and dried over KOH. From this batch were picked single crystals suitable for X-ray diffraction.

Compound (II) was prepared by adopting a similar procedure as for (I). Equimolar amounts of 4-phenylthiosemicarbazide and 4-methoxysalicylaldehyde were dissolved in methanol and stirred until white needle-like crystals started to precipitate (4–5 h). After standing overnight, the compound was filtered off and dried over KOH [identification of this product?]. The mother liquor was kept at room temperature and after 6 d yielded single crystals of (II) suitable for X-ray diffraction. Elemental analysis, calculated for C15H15N3O2S: C 59.78, H 5.02, N 13.94, S 10.64%; found: C 59.67, H 4.96, N 13.87, S 10.60%.

Refinement top

H atoms were constrained to ideal geometry using an appropriate riding model, with C—H = 0.93–0.96 Å, N—H = 0.86 Å and O—H = 0.82 Å, and with Uiso(H) = 1.2Ueq(C, N) or 1.5Ueq(O).

Computing details top

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED (Oxford Diffraction, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of the centrosymmetric dimer of (I), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are indicated by dashed lines. [Symmetry code: (A) 1+x, y, z.]
[Figure 2] Fig. 2. A view of the molecular structure of (II), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 3] Fig. 3. The crystal packing of (I), viewed down (a) the b axis and (b) the c axis. Hydrogen bonds and ππ stacking interactions are indicated by dashed lines.
[Figure 4] Fig. 4. The crystal packing of (II), viewed down (a) the a axis and (b) the b axis. Hydrogen bonds and C—H···π interactions are indicated by dashed lines.
[Figure 5] Fig. 5. Two-dimensional fingerprint plots for (a) the α-polymorph of (I), (b) the β-polymorph of (I) and (c) (II).
(I) salicylaldehyde 4-phenylthiosemicarbazone top
Crystal data top
C14H13N3OSZ = 4
Mr = 271.34F(000) = 568
Triclinic, P1Dx = 1.345 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.6328 (3) ÅCell parameters from 13724 reflections
b = 11.1114 (3) Åθ = 3.8–34.8°
c = 12.8839 (10) ŵ = 0.24 mm1
α = 75.251 (5)°T = 293 K
β = 65.652 (2)°Prismatic, colourless
γ = 81.539 (2)°0.79 × 0.59 × 0.20 mm
V = 1339.56 (12) Å3
Data collection top
Oxford Diffraction Xcalibur CCD
diffractometer
4676 independent reflections
Radiation source: fine-focus sealed tube4184 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.012
ω scansθmax = 25.0°, θmin = 3.8°
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2003)
h = 1212
Tmin = 0.856, Tmax = 0.936k = 1313
14306 measured reflectionsl = 1315
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)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.038P)2 + 0.3482P]
where P = (Fo2 + 2Fc2)/3
4676 reflections(Δ/σ)max = 0.001
345 parametersΔρmax = 0.15 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C14H13N3OSγ = 81.539 (2)°
Mr = 271.34V = 1339.56 (12) Å3
Triclinic, P1Z = 4
a = 10.6328 (3) ÅMo Kα radiation
b = 11.1114 (3) ŵ = 0.24 mm1
c = 12.8839 (10) ÅT = 293 K
α = 75.251 (5)°0.79 × 0.59 × 0.20 mm
β = 65.652 (2)°
Data collection top
Oxford Diffraction Xcalibur CCD
diffractometer
4676 independent reflections
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2003)
4184 reflections with I > 2σ(I)
Tmin = 0.856, Tmax = 0.936Rint = 0.012
14306 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.079H-atom parameters constrained
S = 1.03Δρmax = 0.15 e Å3
4676 reflectionsΔρmin = 0.20 e Å3
345 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
C110.57661 (13)0.79953 (12)0.39556 (11)0.0371 (3)
C120.38367 (14)0.79827 (13)0.69151 (12)0.0396 (3)
H120.44260.84820.69710.048*
C130.26358 (14)0.75380 (13)0.79479 (11)0.0390 (3)
C140.15581 (15)0.69642 (14)0.79333 (12)0.0448 (3)
C150.04261 (17)0.65928 (16)0.89493 (14)0.0541 (4)
H150.02890.62190.89290.065*
C160.03510 (18)0.67723 (16)0.99887 (14)0.0579 (4)
H160.04160.65221.06700.070*
C170.14072 (19)0.73219 (17)1.00292 (13)0.0597 (4)
H170.13600.74321.07360.072*
C180.25273 (17)0.77046 (15)0.90198 (13)0.0501 (4)
H180.32310.80840.90500.060*
C190.52114 (14)0.70249 (13)0.26887 (12)0.0412 (3)
C1100.62569 (16)0.61911 (16)0.22067 (14)0.0546 (4)
H1100.68830.58520.25500.066*
C1110.6362 (2)0.58653 (17)0.12048 (16)0.0662 (5)
H1110.70690.53110.08670.079*
C1120.5424 (2)0.63580 (19)0.07068 (15)0.0674 (5)
H1120.54870.61230.00430.081*
C1130.43998 (19)0.71922 (18)0.11876 (14)0.0628 (5)
H1130.37720.75280.08450.075*
C1140.42906 (16)0.75399 (15)0.21795 (13)0.0487 (4)
H1140.36010.81160.24990.058*
N110.49815 (12)0.72982 (12)0.37811 (10)0.0443 (3)
H11N0.42760.69860.43780.053*
N120.53128 (11)0.82126 (11)0.50405 (10)0.0406 (3)
H12N0.57810.86730.51820.049*
N130.41248 (11)0.77191 (11)0.59270 (9)0.0386 (3)
O10.15616 (12)0.67825 (14)0.69303 (10)0.0675 (4)
H1O0.23160.69500.64000.101*
S10.72434 (4)0.86032 (4)0.29361 (3)0.04948 (12)
C210.15678 (13)0.89188 (12)0.56879 (11)0.0363 (3)
C220.00350 (13)0.67580 (12)0.39304 (11)0.0368 (3)
H220.05840.69390.35650.044*
C230.10949 (13)0.57819 (12)0.36235 (11)0.0342 (3)
C240.21183 (13)0.54659 (12)0.40808 (11)0.0370 (3)
C250.31164 (14)0.45392 (13)0.37349 (13)0.0460 (3)
H250.37890.43280.40450.055*
C260.31156 (16)0.39288 (14)0.29318 (14)0.0509 (4)
H260.38010.33170.26910.061*
C270.21119 (16)0.42124 (14)0.24788 (13)0.0496 (4)
H270.21140.37900.19410.059*
C280.11097 (15)0.51243 (13)0.28288 (12)0.0420 (3)
H280.04260.53080.25300.050*
C290.12202 (14)0.91015 (12)0.74222 (11)0.0371 (3)
C2100.25224 (16)0.89519 (15)0.82987 (14)0.0511 (4)
H2100.32110.86380.81880.061*
C2110.27949 (18)0.92724 (16)0.93415 (14)0.0595 (4)
H2110.36730.91780.99340.071*
C2120.1778 (2)0.97295 (16)0.95089 (14)0.0603 (4)
H2120.19650.99361.02150.072*
C2130.04887 (19)0.98809 (16)0.86358 (14)0.0576 (4)
H2130.01961.01990.87480.069*
C2140.01993 (16)0.95638 (13)0.75878 (13)0.0446 (3)
H2140.06790.96620.69980.054*
N210.08594 (12)0.86846 (11)0.63721 (10)0.0408 (3)
H21N0.01050.82340.61560.049*
N220.11577 (11)0.82821 (10)0.48379 (10)0.0389 (3)
H22N0.15790.84420.43700.047*
N230.00950 (11)0.73849 (10)0.46782 (9)0.0351 (2)
O20.21752 (10)0.60625 (11)0.48570 (9)0.0519 (3)
H2O0.15090.65580.50290.078*
S20.29168 (4)0.99553 (4)0.58034 (4)0.05216 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C110.0352 (7)0.0416 (7)0.0377 (7)0.0042 (5)0.0193 (6)0.0084 (6)
C120.0394 (7)0.0455 (7)0.0396 (7)0.0028 (6)0.0211 (6)0.0118 (6)
C130.0423 (7)0.0418 (7)0.0363 (7)0.0027 (6)0.0190 (6)0.0109 (6)
C140.0456 (8)0.0543 (8)0.0408 (8)0.0003 (6)0.0205 (6)0.0165 (6)
C150.0502 (9)0.0627 (10)0.0512 (9)0.0130 (7)0.0178 (7)0.0128 (7)
C160.0625 (10)0.0623 (10)0.0401 (8)0.0157 (8)0.0114 (7)0.0036 (7)
C170.0745 (11)0.0728 (11)0.0341 (8)0.0144 (9)0.0196 (8)0.0119 (7)
C180.0578 (9)0.0592 (9)0.0406 (8)0.0110 (7)0.0228 (7)0.0124 (7)
C190.0390 (7)0.0468 (8)0.0372 (7)0.0094 (6)0.0097 (6)0.0129 (6)
C1100.0465 (9)0.0595 (10)0.0556 (9)0.0001 (7)0.0144 (7)0.0195 (8)
C1110.0679 (11)0.0625 (11)0.0577 (10)0.0073 (9)0.0030 (9)0.0301 (9)
C1120.0834 (13)0.0781 (12)0.0431 (9)0.0297 (11)0.0133 (9)0.0223 (9)
C1130.0672 (11)0.0811 (12)0.0471 (9)0.0179 (9)0.0267 (8)0.0098 (9)
C1140.0471 (8)0.0547 (9)0.0451 (8)0.0045 (7)0.0175 (7)0.0118 (7)
N110.0367 (6)0.0599 (8)0.0368 (6)0.0097 (5)0.0094 (5)0.0159 (5)
N120.0352 (6)0.0530 (7)0.0374 (6)0.0032 (5)0.0160 (5)0.0125 (5)
N130.0345 (6)0.0473 (6)0.0354 (6)0.0035 (5)0.0160 (5)0.0103 (5)
O10.0509 (7)0.1168 (11)0.0488 (6)0.0156 (7)0.0181 (5)0.0371 (7)
S10.0430 (2)0.0681 (3)0.0388 (2)0.01540 (17)0.01489 (16)0.00862 (17)
C210.0359 (7)0.0354 (7)0.0393 (7)0.0017 (5)0.0146 (6)0.0110 (6)
C220.0367 (7)0.0406 (7)0.0353 (7)0.0003 (5)0.0161 (6)0.0098 (6)
C230.0336 (7)0.0355 (7)0.0306 (6)0.0030 (5)0.0094 (5)0.0071 (5)
C240.0341 (7)0.0416 (7)0.0345 (7)0.0051 (5)0.0107 (5)0.0097 (5)
C250.0369 (7)0.0462 (8)0.0543 (9)0.0028 (6)0.0192 (7)0.0103 (7)
C260.0451 (8)0.0424 (8)0.0606 (10)0.0066 (6)0.0140 (7)0.0198 (7)
C270.0550 (9)0.0468 (8)0.0494 (8)0.0019 (7)0.0166 (7)0.0235 (7)
C280.0453 (8)0.0451 (8)0.0399 (7)0.0010 (6)0.0189 (6)0.0131 (6)
C290.0416 (7)0.0354 (7)0.0367 (7)0.0003 (5)0.0170 (6)0.0100 (5)
C2100.0453 (8)0.0578 (9)0.0524 (9)0.0088 (7)0.0131 (7)0.0227 (7)
C2110.0588 (10)0.0633 (10)0.0464 (9)0.0089 (8)0.0037 (8)0.0205 (8)
C2120.0838 (12)0.0606 (10)0.0424 (8)0.0094 (9)0.0242 (9)0.0183 (7)
C2130.0693 (11)0.0644 (10)0.0520 (9)0.0166 (8)0.0310 (9)0.0144 (8)
C2140.0475 (8)0.0465 (8)0.0411 (8)0.0095 (6)0.0188 (6)0.0050 (6)
N210.0361 (6)0.0501 (7)0.0426 (6)0.0081 (5)0.0187 (5)0.0209 (5)
N220.0399 (6)0.0418 (6)0.0402 (6)0.0079 (5)0.0207 (5)0.0147 (5)
N230.0331 (6)0.0366 (6)0.0342 (6)0.0010 (4)0.0115 (5)0.0098 (5)
O20.0424 (6)0.0719 (7)0.0555 (6)0.0082 (5)0.0258 (5)0.0326 (6)
S20.0526 (2)0.0511 (2)0.0677 (3)0.01951 (17)0.0352 (2)0.03039 (19)
Geometric parameters (Å, º) top
C11—N111.3341 (17)C21—N211.3361 (17)
C11—N121.3515 (17)C21—N221.3416 (17)
C11—S11.6758 (14)C21—S21.6827 (13)
C12—N131.2816 (17)C22—N231.2790 (17)
C12—C131.447 (2)C22—C231.4470 (18)
C12—H120.9300C22—H220.9300
C13—C181.3955 (19)C23—C281.3953 (18)
C13—C141.400 (2)C23—C241.4019 (18)
C14—O11.3563 (17)C24—O21.3575 (16)
C14—C151.380 (2)C24—C251.3810 (19)
C15—C161.372 (2)C25—C261.374 (2)
C15—H150.9300C25—H250.9300
C16—C171.380 (2)C26—C271.378 (2)
C16—H160.9300C26—H260.9300
C17—C181.371 (2)C27—C281.373 (2)
C17—H170.9300C27—H270.9300
C18—H180.9300C28—H280.9300
C19—C1141.375 (2)C29—C2141.3779 (19)
C19—C1101.379 (2)C29—C2101.379 (2)
C19—N111.4300 (17)C29—N211.4251 (17)
C110—C1111.385 (2)C210—C2111.381 (2)
C110—H1100.9300C210—H2100.9300
C111—C1121.376 (3)C211—C2121.372 (2)
C111—H1110.9300C211—H2110.9300
C112—C1131.367 (3)C212—C2131.369 (2)
C112—H1120.9300C212—H2120.9300
C113—C1141.383 (2)C213—C2141.382 (2)
C113—H1130.9300C213—H2130.9300
C114—H1140.9300C214—H2140.9300
N11—H11N0.8600N21—H21N0.8600
N12—N131.3770 (16)N22—N231.3764 (15)
N12—H12N0.8600N22—H22N0.8600
O1—H1O0.8200O2—H2O0.8200
N11—C11—N12116.32 (12)N21—C21—N22117.08 (12)
N11—C11—S1124.73 (10)N21—C21—S2125.10 (10)
N12—C11—S1118.95 (10)N22—C21—S2117.82 (10)
N13—C12—C13122.93 (13)N23—C22—C23123.47 (12)
N13—C12—H12118.5N23—C22—H22118.3
C13—C12—H12118.5C23—C22—H22118.3
C18—C13—C14117.73 (13)C28—C23—C24118.09 (12)
C18—C13—C12118.56 (13)C28—C23—C22118.70 (12)
C14—C13—C12123.70 (12)C24—C23—C22123.22 (12)
O1—C14—C15117.54 (13)O2—C24—C25118.02 (12)
O1—C14—C13121.92 (13)O2—C24—C23121.65 (12)
C15—C14—C13120.51 (13)C25—C24—C23120.32 (12)
C16—C15—C14120.26 (15)C26—C25—C24119.99 (13)
C16—C15—H15119.9C26—C25—H25120.0
C14—C15—H15119.9C24—C25—H25120.0
C15—C16—C17120.37 (15)C25—C26—C27120.82 (14)
C15—C16—H16119.8C25—C26—H26119.6
C17—C16—H16119.8C27—C26—H26119.6
C18—C17—C16119.56 (14)C28—C27—C26119.39 (14)
C18—C17—H17120.2C28—C27—H27120.3
C16—C17—H17120.2C26—C27—H27120.3
C17—C18—C13121.54 (14)C27—C28—C23121.38 (13)
C17—C18—H18119.2C27—C28—H28119.3
C13—C18—H18119.2C23—C28—H28119.3
C114—C19—C110120.78 (14)C214—C29—C210120.21 (13)
C114—C19—N11117.98 (13)C214—C29—N21118.24 (12)
C110—C19—N11121.04 (13)C210—C29—N21121.32 (12)
C19—C110—C111119.08 (16)C29—C210—C211119.46 (14)
C19—C110—H110120.5C29—C210—H210120.3
C111—C110—H110120.5C211—C210—H210120.3
C112—C111—C110120.31 (17)C212—C211—C210120.38 (15)
C112—C111—H111119.8C212—C211—H211119.8
C110—C111—H111119.8C210—C211—H211119.8
C113—C112—C111120.00 (16)C213—C212—C211119.98 (15)
C113—C112—H112120.0C213—C212—H212120.0
C111—C112—H112120.0C211—C212—H212120.0
C112—C113—C114120.44 (17)C212—C213—C214120.34 (15)
C112—C113—H113119.8C212—C213—H213119.8
C114—C113—H113119.8C214—C213—H213119.8
C19—C114—C113119.36 (15)C29—C214—C213119.61 (14)
C19—C114—H114120.3C29—C214—H214120.2
C113—C114—H114120.3C213—C214—H214120.2
C11—N11—C19125.71 (12)C21—N21—C29126.94 (11)
C11—N11—H11N117.1C21—N21—H21N116.5
C19—N11—H11N117.1C29—N21—H21N116.5
C11—N12—N13122.03 (11)C21—N22—N23123.14 (11)
C11—N12—H12N119.0C21—N22—H22N118.4
N13—N12—H12N119.0N23—N22—H22N118.4
C12—N13—N12115.18 (11)C22—N23—N22114.62 (11)
C14—O1—H1O109.5C24—O2—H2O109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11N···O20.862.373.0881 (16)141
O1—H1O···N130.822.012.7252 (16)145
N21—H21N···O10.862.563.2806 (18)142
O2—H2O···N230.821.982.6984 (14)146
N12—H12N···S2i0.862.583.4391 (12)175
N22—H22N···S1ii0.862.593.4398 (11)172
Symmetry codes: (i) x+1, y, z; (ii) x1, y, z.
(II) 4-methoxysalicylaldehyde 4-phenylthiosemicarbazone top
Crystal data top
C15H15N3O2SZ = 2
Mr = 301.37F(000) = 316
Triclinic, P1Dx = 1.353 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 4.73851 (17) ÅCell parameters from 6731 reflections
b = 11.3244 (4) Åθ = 3.7–33.8°
c = 14.0775 (5) ŵ = 0.23 mm1
α = 78.390 (3)°T = 293 K
β = 89.547 (3)°Prismatic, colourless
γ = 89.364 (3)°0.40 × 0.35 × 0.30 mm
V = 739.90 (5) Å3
Data collection top
Oxford Diffraction Xcalibur CCD
diffractometer
2230 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.015
Graphite monochromatorθmax = 25.0°, θmin = 3.8°
Detector resolution: 16.3426 pixels mm-1h = 55
ω scansk = 1313
8408 measured reflectionsl = 1616
2591 independent 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)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0475P)2 + 0.1004P]
where P = (Fo2 + 2Fc2)/3
2591 reflections(Δ/σ)max < 0.001
192 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = 0.17 e Å3
Crystal data top
C15H15N3O2Sγ = 89.364 (3)°
Mr = 301.37V = 739.90 (5) Å3
Triclinic, P1Z = 2
a = 4.73851 (17) ÅMo Kα radiation
b = 11.3244 (4) ŵ = 0.23 mm1
c = 14.0775 (5) ÅT = 293 K
α = 78.390 (3)°0.40 × 0.35 × 0.30 mm
β = 89.547 (3)°
Data collection top
Oxford Diffraction Xcalibur CCD
diffractometer
2230 reflections with I > 2σ(I)
8408 measured reflectionsRint = 0.015
2591 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.087H-atom parameters constrained
S = 1.08Δρmax = 0.16 e Å3
2591 reflectionsΔρmin = 0.17 e Å3
192 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
C10.5985 (3)0.07055 (12)0.32843 (9)0.0415 (3)
C21.0970 (3)0.16180 (12)0.39226 (10)0.0426 (3)
H21.09460.16250.45840.051*
C31.2862 (3)0.24382 (11)0.35530 (10)0.0391 (3)
C41.3019 (3)0.25023 (12)0.25711 (10)0.0437 (3)
C51.4833 (3)0.33096 (13)0.22599 (10)0.0504 (4)
H51.49250.33400.16050.060*
C61.6512 (3)0.40717 (12)0.29157 (11)0.0454 (3)
C71.6416 (3)0.40270 (12)0.38908 (11)0.0463 (3)
H71.75510.45370.43340.056*
C81.4602 (3)0.32108 (12)0.41937 (10)0.0445 (3)
H81.45410.31770.48480.053*
C90.4741 (3)0.16797 (14)0.16067 (10)0.0533 (4)
C100.4706 (4)0.28905 (17)0.15462 (13)0.0741 (5)
H100.57150.32300.19860.089*
C110.3151 (6)0.3616 (2)0.08225 (17)0.1031 (8)
H110.31000.44450.07860.124*
C120.1710 (6)0.3140 (3)0.01704 (17)0.1147 (11)
H120.06840.36370.03150.138*
C130.1767 (5)0.1937 (3)0.02275 (16)0.1095 (9)
H130.07790.16080.02240.131*
C140.3273 (5)0.1185 (2)0.09482 (13)0.0801 (5)
H140.32910.03550.09860.096*
C151.9818 (4)0.57121 (15)0.31744 (14)0.0673 (5)
H15A2.11070.53070.35200.101*
H15B2.08590.62040.28100.101*
H15C1.85880.62110.36270.101*
N10.6337 (3)0.08887 (13)0.23256 (9)0.0638 (4)
H1N0.76730.04850.21180.077*
N20.7574 (2)0.01767 (10)0.38096 (8)0.0444 (3)
H2N0.74940.03020.44320.053*
N30.9333 (2)0.08853 (10)0.33659 (8)0.0436 (3)
O11.1397 (3)0.17907 (11)0.18946 (7)0.0654 (3)
H1O1.03910.13550.21570.098*
O21.8185 (2)0.48431 (10)0.25302 (8)0.0623 (3)
S10.37321 (8)0.14895 (3)0.38499 (3)0.05153 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0420 (7)0.0420 (7)0.0416 (7)0.0050 (6)0.0008 (5)0.0114 (6)
C20.0418 (7)0.0435 (7)0.0431 (7)0.0055 (6)0.0023 (6)0.0103 (6)
C30.0365 (7)0.0367 (7)0.0447 (7)0.0003 (5)0.0032 (5)0.0098 (5)
C40.0455 (7)0.0412 (7)0.0429 (7)0.0056 (6)0.0012 (6)0.0054 (6)
C50.0577 (9)0.0515 (8)0.0429 (8)0.0089 (7)0.0071 (6)0.0124 (6)
C60.0415 (7)0.0391 (7)0.0570 (8)0.0027 (6)0.0083 (6)0.0136 (6)
C70.0425 (7)0.0418 (7)0.0542 (8)0.0076 (6)0.0038 (6)0.0089 (6)
C80.0460 (7)0.0455 (8)0.0430 (7)0.0051 (6)0.0014 (6)0.0118 (6)
C90.0574 (9)0.0637 (10)0.0365 (7)0.0174 (7)0.0066 (6)0.0062 (6)
C100.0951 (13)0.0663 (11)0.0599 (10)0.0216 (10)0.0044 (9)0.0119 (8)
C110.145 (2)0.0838 (15)0.0679 (14)0.0565 (15)0.0207 (14)0.0094 (11)
C120.1098 (19)0.161 (3)0.0539 (13)0.0687 (19)0.0109 (12)0.0215 (15)
C130.0959 (17)0.176 (3)0.0514 (12)0.0026 (18)0.0183 (11)0.0108 (15)
C140.0984 (14)0.0874 (14)0.0524 (10)0.0047 (11)0.0009 (10)0.0086 (9)
C150.0602 (10)0.0570 (10)0.0842 (12)0.0223 (8)0.0091 (9)0.0144 (9)
N10.0761 (9)0.0729 (9)0.0407 (7)0.0394 (7)0.0047 (6)0.0097 (6)
N20.0461 (6)0.0470 (7)0.0403 (6)0.0141 (5)0.0034 (5)0.0100 (5)
N30.0427 (6)0.0422 (6)0.0467 (6)0.0085 (5)0.0049 (5)0.0117 (5)
O10.0807 (8)0.0710 (7)0.0427 (6)0.0338 (6)0.0051 (5)0.0086 (5)
O20.0645 (7)0.0565 (6)0.0679 (7)0.0223 (5)0.0098 (5)0.0188 (5)
S10.0608 (2)0.0498 (2)0.0441 (2)0.02026 (17)0.00687 (16)0.01125 (16)
Geometric parameters (Å, º) top
C1—N11.3331 (18)C9—N11.4249 (19)
C1—N21.3441 (17)C10—C111.385 (3)
C1—S11.6768 (13)C10—H100.9300
C2—N31.2797 (17)C11—C121.348 (4)
C2—C31.4514 (17)C11—H110.9300
C2—H20.9300C12—C131.348 (4)
C3—C81.3916 (18)C12—H120.9300
C3—C41.4000 (19)C13—C141.383 (3)
C4—O11.3551 (17)C13—H130.9300
C4—C51.3802 (19)C14—H140.9300
C5—C61.381 (2)C15—O21.423 (2)
C5—H50.9300C15—H15A0.9600
C6—O21.3618 (16)C15—H15B0.9600
C6—C71.384 (2)C15—H15C0.9600
C7—C81.3823 (19)N1—H1N0.8600
C7—H70.9300N2—N31.3812 (15)
C8—H80.9300N2—H2N0.8600
C9—C101.356 (2)O1—H1O0.8200
C9—C141.373 (2)
N1—C1—N2115.97 (12)C11—C10—H10120.3
N1—C1—S1124.46 (10)C12—C11—C10121.0 (2)
N2—C1—S1119.57 (10)C12—C11—H11119.5
N3—C2—C3122.02 (12)C10—C11—H11119.5
N3—C2—H2119.0C11—C12—C13119.5 (2)
C3—C2—H2119.0C11—C12—H12120.2
C8—C3—C4117.58 (12)C13—C12—H12120.2
C8—C3—C2119.39 (12)C12—C13—C14120.9 (2)
C4—C3—C2123.03 (12)C12—C13—H13119.5
O1—C4—C5117.53 (12)C14—C13—H13119.5
O1—C4—C3121.81 (12)C9—C14—C13119.1 (2)
C5—C4—C3120.66 (13)C9—C14—H14120.4
C4—C5—C6120.32 (13)C13—C14—H14120.4
C4—C5—H5119.8O2—C15—H15A109.5
C6—C5—H5119.8O2—C15—H15B109.5
O2—C6—C5115.28 (13)H15A—C15—H15B109.5
O2—C6—C7124.30 (13)O2—C15—H15C109.5
C5—C6—C7120.42 (12)H15A—C15—H15C109.5
C8—C7—C6118.76 (13)H15B—C15—H15C109.5
C8—C7—H7120.6C1—N1—C9127.14 (12)
C6—C7—H7120.6C1—N1—H1N116.4
C7—C8—C3122.26 (13)C9—N1—H1N116.4
C7—C8—H8118.9C1—N2—N3121.11 (11)
C3—C8—H8118.9C1—N2—H2N119.4
C10—C9—C14120.08 (16)N3—N2—H2N119.4
C10—C9—N1121.90 (15)C2—N3—N2116.46 (11)
C14—C9—N1118.00 (16)C4—O1—H1O109.5
C9—C10—C11119.3 (2)C6—O2—C15118.18 (13)
C9—C10—H10120.3
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···N30.821.942.6642 (15)146
C13—H13···O1i0.932.543.387 (2)151
C14—H14···O1ii0.932.673.487 (3)147
N2—H2N···S1iii0.862.583.3862 (12)156
Symmetry codes: (i) x+1, y, z; (ii) x1, y, z; (iii) x+1, y, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC14H13N3OSC15H15N3O2S
Mr271.34301.37
Crystal system, space groupTriclinic, P1Triclinic, P1
Temperature (K)293293
a, b, c (Å)10.6328 (3), 11.1114 (3), 12.8839 (10)4.73851 (17), 11.3244 (4), 14.0775 (5)
α, β, γ (°)75.251 (5), 65.652 (2), 81.539 (2)78.390 (3), 89.547 (3), 89.364 (3)
V3)1339.56 (12)739.90 (5)
Z42
Radiation typeMo KαMo Kα
µ (mm1)0.240.23
Crystal size (mm)0.79 × 0.59 × 0.200.40 × 0.35 × 0.30
Data collection
DiffractometerOxford Diffraction Xcalibur CCD
diffractometer
Oxford Diffraction Xcalibur CCD
diffractometer
Absorption correctionAnalytical
(CrysAlis RED; Oxford Diffraction, 2003)
Tmin, Tmax0.856, 0.936
No. of measured, independent and
observed [I > 2σ(I)] reflections
14306, 4676, 4184 8408, 2591, 2230
Rint0.0120.015
(sin θ/λ)max1)0.5950.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.079, 1.03 0.030, 0.087, 1.08
No. of reflections46762591
No. of parameters345192
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.15, 0.200.16, 0.17

Computer programs: CrysAlis CCD (Oxford Diffraction, 2003), CrysAlis RED (Oxford Diffraction, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006), PLATON (Spek, 2003).

Selected bond lengths (Å) for (I) top
C11—N111.3341 (17)C21—N211.3361 (17)
C11—N121.3515 (17)C21—N221.3416 (17)
C11—S11.6758 (14)C21—S21.6827 (13)
C12—N131.2816 (17)C22—N231.2790 (17)
C12—C131.447 (2)C22—C231.4470 (18)
C13—C141.400 (2)C23—C241.4019 (18)
C14—O11.3563 (17)C24—O21.3575 (16)
C19—N111.4300 (17)C29—N211.4251 (17)
N12—N131.3770 (16)N22—N231.3764 (15)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N11—H11N···O20.862.373.0881 (16)140.7
O1—H1O···N130.822.012.7252 (16)144.9
N21—H21N···O10.862.563.2806 (18)142.4
O2—H2O···N230.821.982.6984 (14)145.9
N12—H12N···S2i0.862.583.4391 (12)174.8
N22—H22N···S1ii0.862.593.4398 (11)172.0
Symmetry codes: (i) x+1, y, z; (ii) x1, y, z.
Selected bond lengths (Å) for (II) top
C1—N11.3331 (18)C3—C41.4000 (19)
C1—N21.3441 (17)C4—O11.3551 (17)
C1—S11.6768 (13)C9—N11.4249 (19)
C2—N31.2797 (17)N2—N31.3812 (15)
C2—C31.4514 (17)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···N30.821.942.6642 (15)146
C13—H13···O1i0.932.543.387 (2)151
C14—H14···O1ii0.932.673.487 (3)147
N2—H2N···S1iii0.862.583.3862 (12)156
Symmetry codes: (i) x+1, y, z; (ii) x1, y, z; (iii) x+1, y, z+1.
 

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