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The title compound, C14H19N3OS, is in the thio­keto form, with the thione S and hydrazine N atoms cis with respect to each other so that the S atom is involved in inter- and intra­molecular hydrogen bonds simultaneously. Inter­molecular C—H...S and C—H...O hydrogen bonds result in one-dimensional polymeric chains of mol­ecules along the a axis. A weak C—H...π ring inter­action binds the polymeric chains together.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010503564X/ga1110sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010503564X/ga1110Isup2.hkl
Contains datablock I

CCDC reference: 279328

Comment top

Thiosemicarbazones are considered as an important class of nitrogen–sulfur donor ligands because of their highly interesting chemical, biological and medicinal properties (Campbell 1975; Scovill et al., 1982). The biological activity of thiosemicarbazones is related to their chelating ability with transition metal ions, bonding through N, N and S atoms (Sartorelli et al., 1977), or O, N and S atoms (Bindu et al., 1999, 1997; Lu et al., 1993; Dutta et al., 1997). The presence of substituents at the 4-position has been shown to affect the activity of thiosemicarbazones and their metal complexes (Liberta & West, 1992). For example, metal complexes of 2-acetylpyridine thiosemicarbazones are found to exhibit increased antineoplastic activity when the 4-position is a part of the hexamethyleneiminyl ring instead of propyl- or dipropyl-carrying amine groups (Kovala-Demertzi et al., 1997). The 3-hexamethyleneiminyl thiosemicarbazone of 2-acetylpyridine has been screened against HSV-1, HSV-2 and leukemia P388 (Klayman et al., 1983). The coordination chemistry of ONS donor ligands has been of considerable interest because of their remarkable structural and biological properties (John et al., 2002; Casas et al., 2000). However, thiosemicarbazones of salicylaldehyde where the 4-position is a part of a ring system have not been widely investigated. We have reported the 2-hydroxyacetophenone-3-hexamethyleneiminyl thiosemicarbazone and its metal complexes (John et al., 2002, 2003, 2004, 2005). We report here a new O,N,S-tridentate ligand, viz. the title compound, (I), shown in the scheme with the conventional numbering for thiosemicarbazones. Hereafter we use labels for (I) (Fig. 1) consistent with those used for salicylaldehyde thiosemicarbazone (Chattopadhyay et al., 1988).

Compound (I) shows an E configuration about the N3—C8 and C7—N2 bonds relative to the N3—N2 bond (Fig. 1). The N3—N2—C7—S1 torsion angle of -6.0 (3)° indicates that thione S1 and hydrazine N3 atoms are in the Z configuration with respect to the C7—N2 bond, similar to 2-pyridineformamide 3-hexamethyleneiminyl thiosemicarbazone (Bermejo et al., 2004) but in contrast to the parent salicylaldehyde thiosemicarbazone (Chattopadhyay et al., 1988), where an E configuration exists. The Z configuration eliminates the possibility of any steric repulsion between the bulky rings. As a result, atom N3 lies trans to N1, with an N3—N2—C7—N1 torsion angle of 174.1 (2)°.

The C7—S1 and C7—N2 bond distances (Table 1) are similar to the CS double and C—N single bonds in thiosemicarbazones (Usman et al., 2002; Chattopadhyay et al., 1988; Philip et al., 2004) and suggest the thione form for (I). It is implicit from the literature that the delocalization of electron density along the thiosemicarbazide moiety is a characteristic of thiosemicarbazones. For instance, the C—S distance is always intermediate between a C—S single bond and a CS double bond (1.82 and 1.56 Å, respectively; Huheey et al., 1993). Palenik et al. (1974) pointed that apparently the parent aldehyde or ketone moiety has a strong influence on the C—S bond distance. The C7—S1 bond length in (I) is in agreement with values in salicylaldehyde thiosemicarbazone (Chattopadhyay et al., 1988) and does not differ significantly from the corresponding lengths in the thiosemicarbazones of some different aldehydes and ketones (Palenik et al., 1974; Mathew & Palenik, 1971; Dincer et al., 2005; Bain et al., 1997; Sreekanth & Kurup, 2004; Sreekanth et al., 2005; Rapheal et al., 2005). The presence of electron density delocalization is again confirmed by the N3—N2, N2—C7 and C7—N1 bond lengths (Table 1). Of the two C7—N bonds of (I), C7—N1 is significantly shorter than C7—N2, suggesting greater double-bond character to the former bond and indicating an increased electron localization at this substituted end. This is confirmed by the typical double-bond nature [1.269 (3) Å] of the C8N3 bond.

The salicylaldehyde thiosemicarbazone moiety excluding atom N1 is almost planar, with a maximum deviation from the mean plane of 0.151 (1) Å for atom S1. The hexamethyleneiminyl ring adopts a chair conformation [the puckering parameters (Cremer & Pople, 1975) are QT = 0.799 (3) Å, Θ2 = 38.4 (3)°, φ2 = 45.6 (3)° and φ3 = 73.95 (3)°]. The Cg1 plane [comprising atoms C1–C6, with a maximum deviation of 0.003 (2) Å for C6] makes an angle of 40.59 (13)° with the mean plane Cg2, through the hexamethyleneiminyl ring (atoms N1/C9–C14).

There are two intramolecular and two intermolecular hydrogen bonds (Table 2 and Fig. 2) in (I). The intramolecular N3···H1O1—O1 hydrogen bond is very strong, as indicated by the bond length of 1.76 (3)°, shorter than the 1.96 (3)° seen in salicylaldehyde thiosemicarbazone (Chattopadhyay et al., 1988) and similar to values in some hydrazones (Liu & Li, 2004; Ali et al., 2005). Simultaneously, atom H1O1 is involved in a weaker hydrogen bond with atom S1, forming a five-membered ring, N3/H1O1/S1/C7/N2. The intermolecular hydrogen bonds involving atoms H6 and H8 with atoms O1 and S1 (symmetry code: 1 + x, y, z), respectively, form infinite one-dimensional chains of molecules along the a axis. The strength of these four hydrogen bonds has direct influence on the angles subtended at C2 and C7 (Table 2). The weak C9—H9B···π interaction (Table 2) with Cg1 reinforces packing stability along the c axis.

Experimental top

4-Methyl-4-phenyl thiosemicarbazide was prepared as described by Scovill (1991). A solution of 4-methyl-4-phenyl thiosemicarbazide (1 g, 5.52 mmol) in acetonitrile (5 ml) was treated with salicylaldehyde (0.58 ml, 5.52 mmol) and hexamethyleneimine (0.62 ml, 5.52 mmol) and refluxed for 15 min. The solution was allowed to cool and fine colorless needles of the title compound separated out. These were filtered off, washed with cold acetonitrile and dried in vacuo over P4O10. Single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation from an absolute ethanol solution. Elemental analysis found: C 60.25, H 7.37, N 15.08%; calculated: C 60.62, H 6.9, N 15.15%.

Refinement top

All C-bound H atoms were positioned geometrically and treated as riding on the parent C atoms, with C—H distances of 0.93 and 0.97 Å, and with Uiso(H) values of 1.2Ueq(C). Atom H1O1 (on O1) and atom H2N (on N2) were located in difference maps and were refined with isotropic displacement parameters.

Structure description top

Thiosemicarbazones are considered as an important class of nitrogen–sulfur donor ligands because of their highly interesting chemical, biological and medicinal properties (Campbell 1975; Scovill et al., 1982). The biological activity of thiosemicarbazones is related to their chelating ability with transition metal ions, bonding through N, N and S atoms (Sartorelli et al., 1977), or O, N and S atoms (Bindu et al., 1999, 1997; Lu et al., 1993; Dutta et al., 1997). The presence of substituents at the 4-position has been shown to affect the activity of thiosemicarbazones and their metal complexes (Liberta & West, 1992). For example, metal complexes of 2-acetylpyridine thiosemicarbazones are found to exhibit increased antineoplastic activity when the 4-position is a part of the hexamethyleneiminyl ring instead of propyl- or dipropyl-carrying amine groups (Kovala-Demertzi et al., 1997). The 3-hexamethyleneiminyl thiosemicarbazone of 2-acetylpyridine has been screened against HSV-1, HSV-2 and leukemia P388 (Klayman et al., 1983). The coordination chemistry of ONS donor ligands has been of considerable interest because of their remarkable structural and biological properties (John et al., 2002; Casas et al., 2000). However, thiosemicarbazones of salicylaldehyde where the 4-position is a part of a ring system have not been widely investigated. We have reported the 2-hydroxyacetophenone-3-hexamethyleneiminyl thiosemicarbazone and its metal complexes (John et al., 2002, 2003, 2004, 2005). We report here a new O,N,S-tridentate ligand, viz. the title compound, (I), shown in the scheme with the conventional numbering for thiosemicarbazones. Hereafter we use labels for (I) (Fig. 1) consistent with those used for salicylaldehyde thiosemicarbazone (Chattopadhyay et al., 1988).

Compound (I) shows an E configuration about the N3—C8 and C7—N2 bonds relative to the N3—N2 bond (Fig. 1). The N3—N2—C7—S1 torsion angle of -6.0 (3)° indicates that thione S1 and hydrazine N3 atoms are in the Z configuration with respect to the C7—N2 bond, similar to 2-pyridineformamide 3-hexamethyleneiminyl thiosemicarbazone (Bermejo et al., 2004) but in contrast to the parent salicylaldehyde thiosemicarbazone (Chattopadhyay et al., 1988), where an E configuration exists. The Z configuration eliminates the possibility of any steric repulsion between the bulky rings. As a result, atom N3 lies trans to N1, with an N3—N2—C7—N1 torsion angle of 174.1 (2)°.

The C7—S1 and C7—N2 bond distances (Table 1) are similar to the CS double and C—N single bonds in thiosemicarbazones (Usman et al., 2002; Chattopadhyay et al., 1988; Philip et al., 2004) and suggest the thione form for (I). It is implicit from the literature that the delocalization of electron density along the thiosemicarbazide moiety is a characteristic of thiosemicarbazones. For instance, the C—S distance is always intermediate between a C—S single bond and a CS double bond (1.82 and 1.56 Å, respectively; Huheey et al., 1993). Palenik et al. (1974) pointed that apparently the parent aldehyde or ketone moiety has a strong influence on the C—S bond distance. The C7—S1 bond length in (I) is in agreement with values in salicylaldehyde thiosemicarbazone (Chattopadhyay et al., 1988) and does not differ significantly from the corresponding lengths in the thiosemicarbazones of some different aldehydes and ketones (Palenik et al., 1974; Mathew & Palenik, 1971; Dincer et al., 2005; Bain et al., 1997; Sreekanth & Kurup, 2004; Sreekanth et al., 2005; Rapheal et al., 2005). The presence of electron density delocalization is again confirmed by the N3—N2, N2—C7 and C7—N1 bond lengths (Table 1). Of the two C7—N bonds of (I), C7—N1 is significantly shorter than C7—N2, suggesting greater double-bond character to the former bond and indicating an increased electron localization at this substituted end. This is confirmed by the typical double-bond nature [1.269 (3) Å] of the C8N3 bond.

The salicylaldehyde thiosemicarbazone moiety excluding atom N1 is almost planar, with a maximum deviation from the mean plane of 0.151 (1) Å for atom S1. The hexamethyleneiminyl ring adopts a chair conformation [the puckering parameters (Cremer & Pople, 1975) are QT = 0.799 (3) Å, Θ2 = 38.4 (3)°, φ2 = 45.6 (3)° and φ3 = 73.95 (3)°]. The Cg1 plane [comprising atoms C1–C6, with a maximum deviation of 0.003 (2) Å for C6] makes an angle of 40.59 (13)° with the mean plane Cg2, through the hexamethyleneiminyl ring (atoms N1/C9–C14).

There are two intramolecular and two intermolecular hydrogen bonds (Table 2 and Fig. 2) in (I). The intramolecular N3···H1O1—O1 hydrogen bond is very strong, as indicated by the bond length of 1.76 (3)°, shorter than the 1.96 (3)° seen in salicylaldehyde thiosemicarbazone (Chattopadhyay et al., 1988) and similar to values in some hydrazones (Liu & Li, 2004; Ali et al., 2005). Simultaneously, atom H1O1 is involved in a weaker hydrogen bond with atom S1, forming a five-membered ring, N3/H1O1/S1/C7/N2. The intermolecular hydrogen bonds involving atoms H6 and H8 with atoms O1 and S1 (symmetry code: 1 + x, y, z), respectively, form infinite one-dimensional chains of molecules along the a axis. The strength of these four hydrogen bonds has direct influence on the angles subtended at C2 and C7 (Table 2). The weak C9—H9B···π interaction (Table 2) with Cg1 reinforces packing stability along the c axis.

Computing details top

Data collection: Argus-MACH3 (Nonius, 1997); cell refinement: Argus-MACH3; data reduction: maXus (Mackay et al., 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); 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 WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. Compound (I), with 50% probability displacement ellipsoids and the atom-numbering scheme (Farrugia, 1997). H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The packing of (I), viewed along the a axis, showing intra- and intermolecular hydrogen bonds as brocken lines.
Salicylaldehyde 4,4'-(hexane-1,6-diyl)thiosemicarbazone top
Crystal data top
C14H19N3OSF(000) = 592
Mr = 277.38Dx = 1.277 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 6.4480 (11) Åθ = 5.1–10.4°
b = 14.099 (2) ŵ = 0.22 mm1
c = 15.924 (2) ÅT = 293 K
β = 94.617 (12)°Block, colourless
V = 1443.0 (4) Å30.35 × 0.30 × 0.25 mm
Z = 4
Data collection top
Nonius MACH3
diffractometer
Rint = 0.020
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 1.9°
Graphite monochromatorh = 70
ω/θ scansk = 160
2764 measured reflectionsl = 1818
2524 independent reflections3 standard reflections every 200 reflections
1290 reflections with I > 2σ(I) intensity decay: <3%
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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110H atoms treated by a mixture of independent and constrained refinement
S = 0.98 w = 1/[σ2(Fo2) + (0.0454P)2]
where P = (Fo2 + 2Fc2)/3
2524 reflections(Δ/σ)max < 0.001
180 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = 0.16 e Å3
Crystal data top
C14H19N3OSV = 1443.0 (4) Å3
Mr = 277.38Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.4480 (11) ŵ = 0.22 mm1
b = 14.099 (2) ÅT = 293 K
c = 15.924 (2) Å0.35 × 0.30 × 0.25 mm
β = 94.617 (12)°
Data collection top
Nonius MACH3
diffractometer
Rint = 0.020
2764 measured reflections3 standard reflections every 200 reflections
2524 independent reflections intensity decay: <3%
1290 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.110H atoms treated by a mixture of independent and constrained refinement
S = 0.98Δρmax = 0.14 e Å3
2524 reflectionsΔρmin = 0.16 e Å3
180 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
S10.21929 (11)0.56737 (6)0.10776 (5)0.0770 (3)
O10.3863 (3)0.33725 (19)0.18426 (15)0.0889 (7)
N10.4799 (3)0.69895 (16)0.05486 (13)0.0583 (6)
N20.6187 (4)0.55296 (17)0.08523 (15)0.0595 (7)
N30.6053 (3)0.46472 (16)0.11829 (13)0.0570 (6)
C10.7457 (4)0.31658 (19)0.15758 (16)0.0556 (7)
C20.5586 (5)0.2834 (2)0.18579 (17)0.0648 (8)
C30.5480 (6)0.1925 (3)0.2169 (2)0.0881 (10)
H30.42370.17050.23550.106*
C40.7150 (7)0.1352 (3)0.22059 (19)0.0916 (11)
H40.70400.07410.24190.110*
C50.9023 (6)0.1649 (2)0.1936 (2)0.0914 (10)
H51.01680.12460.19610.110*
C60.9152 (5)0.2559 (2)0.16264 (17)0.0712 (8)
H61.04100.27700.14470.085*
C70.4484 (4)0.6105 (2)0.08094 (15)0.0565 (7)
C80.7626 (4)0.41038 (19)0.12273 (15)0.0573 (7)
H80.88770.43090.10370.069*
C90.3082 (4)0.76605 (19)0.04709 (18)0.0713 (8)
H9A0.17810.73120.04320.086*
H9B0.31470.80170.00470.086*
C100.3098 (5)0.8346 (2)0.12009 (19)0.0801 (9)
H10A0.16920.85720.12470.096*
H10B0.35270.80070.17160.096*
C110.4501 (5)0.9184 (2)0.1129 (2)0.0912 (10)
H11A0.44470.95690.16320.109*
H11B0.39630.95650.06530.109*
C120.6746 (5)0.8952 (2)0.1019 (2)0.0900 (10)
H12A0.73180.86190.15180.108*
H12B0.75080.95420.09850.108*
C130.7128 (4)0.83558 (19)0.02532 (18)0.0752 (9)
H13A0.61690.85600.02130.090*
H13B0.85260.84820.00990.090*
C140.6889 (4)0.73076 (18)0.03630 (18)0.0664 (8)
H14A0.72510.69950.01480.080*
H14B0.78780.71010.08170.080*
H2N0.721 (3)0.5682 (15)0.0652 (14)0.039 (8)*
H1O10.413 (5)0.396 (2)0.162 (2)0.125 (14)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0578 (5)0.0863 (6)0.0890 (6)0.0154 (4)0.0192 (4)0.0135 (5)
O10.0728 (16)0.0959 (18)0.1019 (18)0.0198 (14)0.0317 (13)0.0132 (15)
N10.0523 (15)0.0601 (15)0.0618 (15)0.0038 (12)0.0014 (11)0.0059 (12)
N20.0529 (16)0.0614 (17)0.0663 (16)0.0150 (14)0.0170 (13)0.0066 (13)
N30.0595 (15)0.0580 (15)0.0541 (14)0.0151 (13)0.0093 (12)0.0051 (12)
C10.0609 (19)0.0585 (18)0.0465 (17)0.0165 (16)0.0009 (14)0.0058 (14)
C20.072 (2)0.072 (2)0.0491 (18)0.0213 (18)0.0001 (15)0.0014 (15)
C30.100 (3)0.093 (3)0.070 (2)0.035 (2)0.001 (2)0.018 (2)
C40.123 (3)0.080 (3)0.067 (2)0.030 (3)0.025 (2)0.0174 (19)
C50.107 (3)0.078 (3)0.083 (2)0.002 (2)0.028 (2)0.0062 (19)
C60.071 (2)0.075 (2)0.065 (2)0.0143 (18)0.0065 (16)0.0019 (17)
C70.0523 (18)0.0658 (19)0.0514 (17)0.0067 (15)0.0048 (13)0.0148 (15)
C80.0497 (18)0.070 (2)0.0529 (17)0.0165 (15)0.0059 (13)0.0074 (15)
C90.0607 (19)0.075 (2)0.077 (2)0.0009 (16)0.0024 (16)0.0065 (17)
C100.077 (2)0.084 (2)0.079 (2)0.0112 (19)0.0052 (17)0.0096 (19)
C110.097 (3)0.080 (2)0.095 (3)0.005 (2)0.002 (2)0.0164 (19)
C120.090 (3)0.070 (2)0.109 (3)0.0126 (18)0.001 (2)0.013 (2)
C130.071 (2)0.074 (2)0.081 (2)0.0083 (16)0.0073 (17)0.0163 (18)
C140.0613 (19)0.0666 (19)0.072 (2)0.0089 (15)0.0094 (15)0.0034 (15)
Geometric parameters (Å, º) top
S1—C71.684 (3)C6—H60.9300
O1—C21.344 (3)C8—H80.9300
O1—H1O10.92 (3)C9—C101.511 (3)
N1—C71.336 (3)C9—H9A0.9700
N1—C91.454 (3)C9—H9B0.9700
N1—C141.472 (3)C10—C111.498 (4)
N2—N31.356 (3)C10—H10A0.9700
N2—C71.362 (3)C10—H10B0.9700
N2—H2N0.78 (2)C11—C121.508 (4)
N3—C81.269 (3)C11—H11A0.9700
C1—C61.386 (4)C11—H11B0.9700
C1—C21.401 (4)C12—C131.517 (4)
C1—C81.442 (3)C12—H12A0.9700
C2—C31.378 (4)C12—H12B0.9700
C3—C41.344 (4)C13—C141.497 (3)
C3—H30.9300C13—H13A0.9700
C4—C51.379 (4)C13—H13B0.9700
C4—H40.9300C14—H14A0.9700
C5—C61.379 (4)C14—H14B0.9700
C5—H50.9300
C2—O1—H1O1110 (2)C10—C9—H9A109.0
C7—N1—C9120.0 (2)N1—C9—H9B109.0
C7—N1—C14120.8 (2)C10—C9—H9B109.0
C9—N1—C14119.2 (2)H9A—C9—H9B107.8
N3—N2—C7119.3 (3)C11—C10—C9114.4 (3)
N3—N2—H2N119.4 (17)C11—C10—H10A108.7
C7—N2—H2N121.1 (17)C9—C10—H10A108.7
C8—N3—N2120.0 (2)C11—C10—H10B108.7
C6—C1—C2118.1 (3)C9—C10—H10B108.7
C6—C1—C8120.4 (3)H10A—C10—H10B107.6
C2—C1—C8121.5 (3)C10—C11—C12115.4 (3)
O1—C2—C3117.8 (3)C10—C11—H11A108.4
O1—C2—C1122.5 (3)C12—C11—H11A108.4
C3—C2—C1119.6 (3)C10—C11—H11B108.4
C4—C3—C2120.9 (3)C12—C11—H11B108.4
C4—C3—H3119.6H11A—C11—H11B107.5
C2—C3—H3119.6C11—C12—C13115.7 (3)
C3—C4—C5121.5 (3)C11—C12—H12A108.4
C3—C4—H4119.3C13—C12—H12A108.4
C5—C4—H4119.3C11—C12—H12B108.4
C6—C5—C4118.3 (3)C13—C12—H12B108.4
C6—C5—H5120.9H12A—C12—H12B107.4
C4—C5—H5120.9C14—C13—C12115.3 (2)
C5—C6—C1121.7 (3)C14—C13—H13A108.4
C5—C6—H6119.2C12—C13—H13A108.4
C1—C6—H6119.2C14—C13—H13B108.4
N1—C7—N2115.4 (2)C12—C13—H13B108.4
N1—C7—S1125.0 (2)H13A—C13—H13B107.5
N2—C7—S1119.5 (2)N1—C14—C13115.4 (2)
N3—C8—C1119.4 (2)N1—C14—H14A108.4
N3—C8—H8120.3C13—C14—H14A108.4
C1—C8—H8120.3N1—C14—H14B108.4
N1—C9—C10113.1 (2)C13—C14—H14B108.4
N1—C9—H9A109.0H14A—C14—H14B107.5
C7—N2—N3—C8180.0 (2)C14—N1—C7—S1177.40 (18)
C6—C1—C2—O1179.3 (3)N3—N2—C7—N1174.1 (2)
C8—C1—C2—O11.8 (4)N3—N2—C7—S16.0 (3)
C6—C1—C2—C30.4 (4)N2—N3—C8—C1179.7 (2)
C8—C1—C2—C3178.5 (3)C6—C1—C8—N3179.7 (2)
O1—C2—C3—C4179.6 (3)C2—C1—C8—N30.8 (4)
C1—C2—C3—C40.1 (5)C7—N1—C9—C10101.1 (3)
C2—C3—C4—C50.0 (5)C14—N1—C9—C1076.9 (3)
C3—C4—C5—C60.3 (5)N1—C9—C10—C1183.0 (3)
C4—C5—C6—C10.7 (4)C9—C10—C11—C1256.2 (4)
C2—C1—C6—C50.7 (4)C10—C11—C12—C1358.7 (4)
C8—C1—C6—C5178.2 (3)C11—C12—C13—C1483.4 (3)
C9—N1—C7—N2179.4 (2)C7—N1—C14—C13167.7 (2)
C14—N1—C7—N22.6 (3)C9—N1—C14—C1310.3 (3)
C9—N1—C7—S10.6 (3)C12—C13—C14—N161.8 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O1···N30.92 (3)1.76 (3)2.562 (3)144 (3)
O1—H1O1···S10.92 (3)2.82 (3)3.600 (3)143 (3)
C6—H6···O1i0.932.423.239 (4)147
C8—H8···S1i0.932.873.706 (6)150
C9—H9B···Cg1ii0.972.963.758 (1)141
Symmetry codes: (i) x+1, y, z; (ii) x+1, y+1, z.

Experimental details

Crystal data
Chemical formulaC14H19N3OS
Mr277.38
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)6.4480 (11), 14.099 (2), 15.924 (2)
β (°) 94.617 (12)
V3)1443.0 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.22
Crystal size (mm)0.35 × 0.30 × 0.25
Data collection
DiffractometerNonius MACH3
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2764, 2524, 1290
Rint0.020
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.110, 0.98
No. of reflections2524
No. of parameters180
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.14, 0.16

Computer programs: Argus-MACH3 (Nonius, 1997), Argus-MACH3, maXus (Mackay et al., 1998), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003), SHELXL97 and WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
S1—C71.684 (3)N2—C71.362 (3)
N1—C71.336 (3)N3—C81.269 (3)
N2—N31.356 (3)
N3—N2—C7119.3 (3)N1—C7—N2115.4 (2)
C8—N3—N2120.0 (2)N1—C7—S1125.0 (2)
O1—C2—C3117.8 (3)N2—C7—S1119.5 (2)
O1—C2—C1122.5 (3)N3—C8—C1119.4 (2)
C3—C2—C1119.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O1···N30.92 (3)1.76 (3)2.562 (3)144 (3)
O1—H1O1···S10.92 (3)2.82 (3)3.600 (3)143 (3)
C6—H6···O1i0.932.423.239 (4)147
C8—H8···S1i0.932.873.706 (6)150
C9—H9B···Cg1ii0.972.963.758 (1)141
Symmetry codes: (i) x+1, y, z; (ii) x+1, y+1, z.
 

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