research communications
Crystal structures of two hydrazinecarbothioamide derivatives: (E)-N-ethyl-2-[(4-oxo-4H-chromen-3-yl)methylidene]hydrazinecarbothioamide hemihydrate and (E)-2-[(4-chloro-2H-chromen-3-yl)methylidene]-N-phenylhydrazinecarbothioamide
aDepartment of Physics, Ethiraj College for Women (Autonomous), Chennai 600 008, India, bDepartment of Chemistry, National Institute of Technology, Tiruchirappalli 620 015, India, and cDepartment of Physics, RKM Vivekananda College (Autonomous), Chennai 600 004, India
*Correspondence e-mail: ksethusankar@yahoo.co.in
The title compounds, C13H13N3O2S·0.5H2O, (I), and C17H14ClN3OS, (II), are hydrazinecarbothioamide derivatives. Compound (I) crystallizes with two independent molecules (A and B) and a water molecule of crystallization in the The chromene moiety is essentially planar in molecules A and B, with maximum deviations of 0.028 (3) and 0.016 (3) Å, respectively, for the carbonyl C atoms. In (II), the pyran ring of the chromene moiety adopts a screw-boat conformation and the phenyl ring is inclined by 61.18 (9)° to its mean plane. In the crystal of (I), bifurcated N—H⋯O and C—H⋯O hydrogen bonds link the two independent molecules forming A–B dimers with two R21(6) ring motifs, and R22(10) and R22(14) ring motifs. In addition to these, the water molecule forms tetrafurcated hydrogen bonds which alternately generate R44(12) and R66(22) graph-set ring motifs. There are also π–π [inter-centroid distances = 3.5648 (14) and 3.6825 (15) Å] interactions present, leading to the formation of columns along the c-axis direction. In the crystal of (II), molecules are linked by pairs of N—H⋯S hydrogen bonds, forming inversion dimers with an R22(8) ring motif. The dimers are linked by C—H⋯π interactions, forming ribbons lying parallel to (210).
1. Chemical context
Thiosemicarbazones belong to a large group of thiourea derivatives which are derived from parent ). Derivatives of hydrazinecarbothioamide constitute an important group of multidentate ligands with potential binding sites available for a wide variety of metal ions. The chemistry of thiosemicarbazone complexes has received much attention owing to their significant biological activities and medicinal properties. Presently, the areas in which thiosemicarbazones are receiving the most attention are based on their antitumour, antiprotozoal, antibacterial and antiviral activities (Finch et al., 1999; Antholine et al., 1977). α-N-heterocyclic thiosemicarbazones possess antitumour properties partially related to their ability to inhibit ribonucleoside reductase (RR), an iron-containing enzyme which is essential in DNA synthesis (Sartorelli et al., 1970). The medicinal action of these thiosemicarbazones appears to be directly related to their ability to chelate the iron atom of the active site of RR or by destroying the tyrosinase radical present in a subunit of this protein (Thelander & Graslund, 1983). The structures of the title compounds were determined in order to investigate the extent of electron delocalization, ligand conformations and to illustrate their biological implications.
and The biological activity of these compounds depends on the parent aldehyde and ketone (Beraldo & Gambino, 20042. Structural commentary
In compound (I) (Fig. 1), the chromene moieties of molecules A and B are essentially planar, with maximum deviations of 0.028 (3) and 0.016 (3) Å for atoms C7 and C7′, respectively. However, in compound (II) (Fig. 2), the chromene moiety is not quite planar with a dihedral angle of 5.67 (12)° between the mean planes of the fused six-membered rings. In compound (II), the pyran ring of the chromene moiety adopts a screw-boat conformation [puckering amplitudes and smallest displacement parameters are q = 0.314 (2) Å, θ = 116.4 (4)°, φ = 147.5 (5)° and ΔC2 = 0.7 (3)]. In compound (II), the dihedral angle between the chromene moiety and the phenyl ring is 61.18 (9)°. The deviation of the carbonyl O atoms (O2 and O2′) from the mean plane of the pyran ring in compound (I) are 0.0838 (18) and 0.0386 (19) Å in molecules A and B, respectively, while the deviation of the Cl atom in compound (II) is 0.312 (1) Å.
The hydrazinecarbothioamide backbone is almost planar, with the maximum deviation being exhibited by atom N2 in both compounds; 0.025 (2) and 0.051 (2) Å, respectively, in molecules A and B of compound (I) and 0.072 (2) Å in compound (II).
Thiosemicarbazones exist in the thione form in the solid state and in solution they exist as an equilibrium mixture of thione and thiol forms (Kurup & Joseph, 2003). The fact that the compounds exists in the thione form is confirmed by the N—N, N—C and C=S bond lengths.. The C—S bond lengths are 1.681 (2) and 1.673 (2) Å in molecules A and B, respectively, of compound (I), and 1.668 (2) Å in compound (II). These bond lengths are intermediate between normal S—Csp2 single-bond and S=Csp2 double-bond distances of ca 1.75 and 1.59 Å, respectively, indicating the presence of partial double-bond character (Kumbhar et al., 1997). The N1—N2 bond lengths [varying between 1.367 (2) and 1.369 (2) Å] are very close to that reported for a similar substituted hydrazinecarbothioamide compound (Joseph et al., 2004). The resonance involving the pyran ring would account for the shortening of the N—N distance through extensive delocalization. The C—N bond lengths [varying between 1.324 (3) and 1.361 (3) Å] are shorter than the normal C—N single bond length (ca 1.48 Å), also indicating some degree of delocalization in both compounds. The S1=C11—N2—N1 torsion angles are 177.31 (16) and 174.29 (16)°, respectively, in molecules A and B of compound (I) and −172.62 (17)° in compound (II). This indicates that the thionyl atom S1 is positioned trans to the azomethane nitrogen atom N1 in both compounds.
3. Supramolecular features
The water molecule of crystallization plays an important role in the hydrogen-bonding patterns of the three-dimensional network in compound (I). In the crystal packing of compound (I), bifurcated N—H⋯O and C—H⋯O hydrogen bonds involving carbonyl oxygens O2 and O2′ in adjacent molecules, interconnect them to form A–B dimers with two (6) ring motifs, and (10) and (14) ring motifs (Table 1 and Fig. 3). Similar bifurcated hydrogen bonds between molecule A and the water O atom form an (10) ring motif. In addition to these, the water molecule forms tetrafurcated hydrogen bonds which alternately generate R44(12) and R66(22) graph-set ring motifs. The supramolecular aggregation in the crystal of compound (I) is completed by the presence of slipped parallel π–π interactions, forming columns along the c-axis direction. The most significant interactions are Cg1⋯Cg1i = 3.5648 (14) Å [inter-planar distance = 3.3154 (10) Å, slippage = 1.310 Å, where Cg1 is the centroid of the O1/C1/C6–C9 ring; symmetry code: (i) = −x + 1, −y + 1, −z + 1] and Cg5⋯Cg5ii = 3.6825 (15) Å [inter-planar distance = 3.5441 (11) Å, slippage = 0.999 Å, where Cg5 is the centroid of the C1′–C6′ ring; symmetry code: (ii) = −x + 2, −y + 1, −z].
In the crystal of compound (II), molecules are linked by pairs of N—H⋯S hydrogen bonds, forming inversion dimers with an (8) ring motif (Table 2 and Fig. 4). The dimers are linked by C—H⋯π interactions (Table 2), forming ribbons lying parallel to plane (210).
4. Database survey
A search of the Cambridge Structural Database (Version 5.36; last update Nov. 2014; Groom & Allen, 2014) for similar structures gave 3 hits, one of which is a copper(II) complex, dibromo-(2-{[6-methyl-4-(oxo)-4H-chromen-3-yl]methylene}- N-phenylhydrazinecarbothioamide)copper (Ilies et al., 2014). The other two include, N-methyl-2-[(4-oxo-4H-chromen-3-yl)methylene] hydrazinecarbothioamide (III) (Vimala et al., 2014), which is the N-methyl derivative of compound (I), and (E)-2-[(4-chloro-2H-chromen-3-yl)methylene]-N-cyclohexylhydrazine carbothioamide (IV) (Gangadharan et al., 2014), which is the N-cyclohexane derivative of compound (II). The bond distances and angles in compounds (I) and (III) are very similar, as are those in compounds (II) and (IV).
5. Synthesis and crystallization
Compound (I): 1.19 g (0.01 mol) of N-ethylhydrazinecarbothioamide was dissolved in 20 ml of hot ethanol and to this was added 1.74 g (0.01 mol) of 4-oxo-4H-chromene-3-carbaldehyde in 10 cm3 of ethanol over a period of 10 min with continuous stirring. The reaction mixture was refluxed for 2 h and allowed to cool whereby a shiny white compound began to separate; this was filtered and washed thoroughly with ethanol and then dried in vacuo. The compound was recrystallized from hot ethanol (yield: 96%), giving colourless block-like crystals.
Compound (II): 1.67 g (0.01 mol) of 4(N)-phenylthiosemicarbazide was dissolved in 20 ml of hot ethanol and to this was added 1.94 g (0.01 mol) of 4-chloro-2H-chromene-3-carbaldehyde in 10 ml of ethanol over a period of 10 min with continuous stirring. The reaction mixture was refluxed for 2 h and allowed to cool whereby a shiny yellow compound began to separate. It was filtered and washed thoroughly with ethanol and then dried in vacuo. The compound was recrystallized from hot ethanol (yield: 89%), giving colourless block-like crystals.
6. Refinement
Crystal data, data collection and structure and (II) are summarized in Table 3. For compound (I), the positions of the water H atoms were located from difference electron density maps and freely refined. In compounds (I) and (II), the NH H atoms were included in calculated positions and treated as riding atoms: N—H = 0.86 Å with Uiso(H) = 1.2Ueq(N). The C-bound H atoms in both molecules were included in calculated positions and treated as riding atoms: C—H = 0.93–0.97 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(C) for other H atoms.
details for compounds (I)
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Supporting information
10.1107/S2056989015003369/su5078sup1.cif
contains datablocks I, II, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015003369/su5078Isup2.hkl
Structure factors: contains datablock II. DOI: 10.1107/S2056989015003369/su5078IIsup3.hkl
Supporting information file. DOI: 10.1107/S2056989015003369/su5078Isup4.cml
Supporting information file. DOI: 10.1107/S2056989015003369/su5078IIsup5.cml
Thiosemicarbazones belong to a large group of thiourea derivatives which are derived from parent α-N-heterocyclic thiosemicarbazones possess antitumour properties partially related to their ability to inhibit ribonucleoside reductase (RR), an iron-containing enzyme which is essential in DNA synthesis (Sartorelli et al., 1970).The medicinal action of these thiosemicarbazones appears to be directly related to their ability to chelate the iron atom of the active site of RR or by destroying the tyrosinase radical present in a subunit of this protein (Thelander & Graslund, 1983). The structures of the title compounds were determined in order to investigate the extent of electron delocalization, ligand conformations and to illustrate their biological implications.
and The biological activity of these compounds depends on the parent aldehyde and ketone (Beraldo & Gambino, 2004). Derivatives of hydrazinecarbothioamide constitute an important group of multidentate ligands with potential binding sites available for a wide variety of metal ions. The chemistry of thiosemicarbazone complexes has received much attention owing to their significant biological activities and medicinal properties. Presently, the areas in which thiosemicarbazones are receiving the most attention are based on their antitumour, antiprotozoal, antibacterial and antiviral activities (Finch et al., 1999; Antholine et al., 1977).In compound (I) (Fig. 1), the chromene moieties of molecules A and B are essentially planar, with maximum deviations of 0.028 (3) and 0.016 (3) Å for atoms C7 and C7', respectively. However, in compound (II) (Fig. 2), the chromene moiety is not quite planar with a dihedral angle of 5.67 (12)° between the mean planes of the fused six-membered rings. In compound (II), the pyran ring of the chromene moiety adopts a screw-boat conformation [puckering amplitudes and smallest displacement parameters are q = 0.314 (2) Å, θ = 116.4 (4)°, ϕ = 147.5 (5)° and ΔC2 = 0.7 (3)]. In compound (II), the dihedral angle between the chromene moiety and the phenyl ring is 61.18 (9)°. The deviation of the carbonyl O atoms (O2 and O2') from the mean plane of the pyran ring in compound (I) are 0.0838 (18) and 0.0386 (19) Å in molecules A and B, respectively, while the deviation of the Cl atom in compound (II) is 0.312 (1) Å.
The hydrazinecarbothioamide backbone is almost planar, with the maximum deviation being exhibited by atom N2 in both compounds; 0.025 (2) and 0.051 (2) Å, respectively, in molecules A and B of compound (I) and 0.072 (2) Å in compound (II).
Thiosemicarbazones exist in the thione form in the solid state and in solution they exist as an equilibrium mixture of thione and thiol forms (Kurup & Joseph, 2003). The fact that the compounds exists in the thione form is confirmed by the N—N, N—C and C═S bond lengths.. The C—S bond lengths are 1.681 (2) and 1.673 (2) Å in molecules A and B, respectively, of compound (I), and 1.668 (2) Å in compound (II). These bond lengths are intermediate between normal S—Csp2 single-bond and S═Csp2 double-bond distances of ca 1.75 and 1.59 Å, respectively, indicating the presence of partial double-bond character (Kumbhar et al., 1997). The N1—N2 bond lengths [varying between 1.367 (2) and 1.369 (2) Å] are very close to that reported for a similar substituted hydrazinecarbothioamide compound (Joseph et al., 2004). The resonance involving the pyran ring would account for the shortening of the N—N distance through extensive delocalization. The C—N bond lengths [varying between 1.324 (3) and 1.361 (3) Å] are shorter than the normal C—N single bond length (ca 1.48 Å), also indicating some degree of delocalization in both compounds. The S1═C11—N2—N1 torsion angles are 177.31 (16) and 174.29 (16)°, respectively, in molecules A and B of compound (I) and -172.62 (17)° in compound (II). This indicates that the thionyl atom S1 is positioned trans to the azomethane nitrogen atom N1 in both compounds.
The water molecule of crystallization plays an important role in the hydrogen-bonding patterns of the three-dimensional network in compound (I). In the crystal packing of compound (I), bifurcated N—H···O and C—H···O hydrogen bonds involving carbonyl oxygens O2 and O2' in adjacent molecules, interconnect them to form A–B dimers with two R21(6) ring motifs, and R22(10) and R22(14) ring motifs (Table 1 and Fig. 3). Similar bifurcated hydrogen bonds between molecule A and the water O atom form an R21(10) ring motif. In addition to these, the water molecule forms tetrafurcated hydrogen bonds which alternatively generate R44(12) and R66(22) graph-set ring motifs. The supramolecular aggregation in the crystal of compound (I) is completed by the presence of slipped parallel π–π interactions, forming columns along the c-axis direction. The most significant interactions are Cg1···Cg1i = 3.5648 (14) Å [inter-planar distance = 3.3154 (10) Å, slippage = 1.310 Å, where Cg1 is the centroid of the O1/C1/C6–C9 ring; symmetry code: (i) = -x + 1, -y + 1, -z + 1] and Cg5···Cg5ii = 3.6825 (15) Å [inter-planar distance = 3.5441 (11) Å, slippage = 0.999 Å, where Cg5 is the centroid of the C1'–C6' ring; symmetry code: (ii) = -x + 2, -y + 1, -z].
In the crystal of compound (II), molecules are linked by pairs of N—H···S hydrogen bonds, forming inversion dimers with an R22(8) ring motif (Table 2 and Fig. 4). The dimers are linked by C—H···π interactions (Table 2), forming ribbons lying parallel to plane (210).
A search of the Cambridge Structural Database (Version 5.36; last update Nov. 2014; Groom & Allen, 2014) for similar structures gave 3 hits, one of which is a copper(II) complex, dibromo-(2-{[6-methyl-4-(oxo)-4H-chromen-3-yl]methylene}- N-phenylhydrazinecarbothioamide)copper (Ilies et al., 2014). The other two include, N-methyl-2-[(4-oxo-4H-chromen-3-yl)methylene] hydrazinecarbothioamide (III) (Vimala et al., 2014), which is the N-methyl derivative of compound (I), and (E)-2-[(4-chloro-2H-chromen-3-yl)methylene]-N-cyclohexylhydrazine carbothioamide (IV) (Gangadharan et al., 2014), which is the N-cyclohexane derivative of compound (II). The bond distances and angles in compounds (I) and (III) are very similar, as are those in compounds (II) and (IV).
Compound (I): 1.19 g (0.01 mol) of N-ethylhydrazinecarbothioamide was dissolved in 20 ml of hot ethanol and to this was added 1.74 g (0.01 mol) of 4-oxo-4H-chromene-3-carbaldehyde in 10 cm3 of ethanol over a period of 10 min with continuous stirring. The reaction mixture was refluxed for 2 h and allowed to cool whereby a shiny white compound began to separate; this was filtered and washed thoroughly with ethanol and then dried in vacuo. The compound was recrystallized from hot ethanol (yield: 96%), giving colourless block-like crystals.
Compound (II): 1.67 g (0.01 mol) of 4(N)-phenylthiosemicarbazide was dissolved in 20 ml of hot ethanol and to this was added 1.94 g (0.01 mol) of 4-chloro-2H-chromene-3-carbaldehyde in 10 ml of ethanol over a period of 10 min with continuous stirring. The reaction mixture was refluxed for 2 h and allowed to cool whereby a shiny yellow compound began to separate. It was filtered and washed thoroughly with ethanol and then dried in vacuo. The compound was recrystallized from hot ethanol (yield: 89%), giving colourless block-like crystals.
Crystal data, data collection and structure
details for compounds (I) and (II) are summarized in Table 3. For compound (I), the positions of the water H atoms were located from difference electron density maps and freely refined. In compounds (I) and (II), the NH H atoms were included in calculated positions and treated as riding atoms: N—H = 0.86 Å with Uiso(H) = 1.2Ueq(N). The C-bound H atoms in both molecules were included in calculated positions and treated as riding atoms: C—H = 0.93–0.97 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(C) for other H atoms.For both compounds, data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008). Software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009) for (I); SHELXL97 (Sheldrick, 2008) and PLATON Spek, 2009) for (II).Fig. 1. The molecular structure of the two independent molecules (A and B) of compound (I), showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level. | |
Fig. 2. The molecular structure of compound (II), showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level. | |
Fig. 3. A partial view along the c axis of the crystal packing of compound (I), showing the N—H···O, C—H···O and OW—H···S hydrogen bonds (dashed lines; see Table 1), which result in the formation of two R21(6) ring motifs and R22(10), R22(14), R44(12) and R66(22) ring motifs. H atoms not involved in hydrogen bonding have been omitted for clarity. | |
Fig. 4. A partial view along the b axis of the crystal packing of compound (II), showing the N—H···S hydrogen bonds (dashed lines; see Table 2), which result in the formation of inversion dimers with an R22(8) ring motif. H atoms not involved in hydrogen bonding have been omitted for clarity. |
C13H13N3O2S·0.5H2O | Z = 4 |
Mr = 284.33 | F(000) = 596 |
Triclinic, P1 | Dx = 1.409 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.2858 (2) Å | Cell parameters from 5579 reflections |
b = 12.5422 (4) Å | θ = 1.6–26.6° |
c = 14.3520 (5) Å | µ = 0.25 mm−1 |
α = 114.379 (2)° | T = 296 K |
β = 95.751 (3)° | Block, colourless |
γ = 94.200 (2)° | 0.35 × 0.30 × 0.25 mm |
V = 1340.81 (7) Å3 |
Bruker Kappa APEXII CCD diffractometer | 5579 independent reflections |
Radiation source: fine-focus sealed tube | 2764 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
ω and ϕ scans | θmax = 26.6°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −10→10 |
Tmin = 0.917, Tmax = 0.940 | k = −14→15 |
19142 measured reflections | l = −18→18 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.137 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0658P)2] where P = (Fo2 + 2Fc2)/3 |
5579 reflections | (Δ/σ)max < 0.001 |
362 parameters | Δρmax = 0.26 e Å−3 |
2 restraints | Δρmin = −0.24 e Å−3 |
C13H13N3O2S·0.5H2O | γ = 94.200 (2)° |
Mr = 284.33 | V = 1340.81 (7) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.2858 (2) Å | Mo Kα radiation |
b = 12.5422 (4) Å | µ = 0.25 mm−1 |
c = 14.3520 (5) Å | T = 296 K |
α = 114.379 (2)° | 0.35 × 0.30 × 0.25 mm |
β = 95.751 (3)° |
Bruker Kappa APEXII CCD diffractometer | 5579 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 2764 reflections with I > 2σ(I) |
Tmin = 0.917, Tmax = 0.940 | Rint = 0.046 |
19142 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 2 restraints |
wR(F2) = 0.137 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | Δρmax = 0.26 e Å−3 |
5579 reflections | Δρmin = −0.24 e Å−3 |
362 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 | ||
C1' | 0.7753 (3) | 0.4656 (2) | −0.08664 (19) | 0.0444 (6) | |
C1 | 0.8004 (3) | 0.5298 (2) | 0.46364 (19) | 0.0425 (6) | |
C2' | 0.8576 (3) | 0.5059 (2) | −0.1473 (2) | 0.0557 (7) | |
H2' | 0.8603 | 0.4568 | −0.2163 | 0.067* | |
C2 | 0.8858 (3) | 0.5665 (2) | 0.4025 (2) | 0.0557 (7) | |
H2 | 0.8976 | 0.5138 | 0.3360 | 0.067* | |
C3 | 0.9530 (3) | 0.6821 (2) | 0.4413 (2) | 0.0581 (7) | |
H3 | 1.0107 | 0.7083 | 0.4008 | 0.070* | |
C3' | 0.9351 (3) | 0.6189 (2) | −0.1045 (2) | 0.0593 (8) | |
H3' | 0.9903 | 0.6469 | −0.1448 | 0.071* | |
C4' | 0.9321 (3) | 0.6925 (2) | −0.0009 (2) | 0.0572 (7) | |
H4' | 0.9859 | 0.7690 | 0.0278 | 0.069* | |
C4 | 0.9357 (3) | 0.7602 (2) | 0.5402 (2) | 0.0568 (7) | |
H4 | 0.9835 | 0.8382 | 0.5664 | 0.068* | |
C5 | 0.8487 (3) | 0.7233 (2) | 0.6000 (2) | 0.0487 (6) | |
H5 | 0.8357 | 0.7768 | 0.6660 | 0.058* | |
C5' | 0.8498 (3) | 0.6520 (2) | 0.0583 (2) | 0.0503 (7) | |
H5' | 0.8475 | 0.7017 | 0.1273 | 0.060* | |
C6 | 0.7792 (3) | 0.6059 (2) | 0.56270 (18) | 0.0404 (6) | |
C6' | 0.7691 (3) | 0.5370 (2) | 0.01658 (19) | 0.0408 (6) | |
C7 | 0.6827 (3) | 0.5632 (2) | 0.62307 (19) | 0.0420 (6) | |
C7' | 0.6784 (3) | 0.4911 (2) | 0.07702 (19) | 0.0429 (6) | |
C8' | 0.6037 (3) | 0.3694 (2) | 0.02285 (18) | 0.0409 (6) | |
C8 | 0.6228 (3) | 0.43815 (19) | 0.57379 (18) | 0.0394 (6) | |
C9 | 0.6516 (3) | 0.3722 (2) | 0.47741 (19) | 0.0488 (7) | |
H9 | 0.6102 | 0.2926 | 0.4477 | 0.059* | |
C9' | 0.6189 (3) | 0.3082 (2) | −0.0777 (2) | 0.0535 (7) | |
H9' | 0.5693 | 0.2305 | −0.1106 | 0.064* | |
C10 | 0.5298 (3) | 0.3872 (2) | 0.62971 (18) | 0.0430 (6) | |
H10 | 0.5125 | 0.4350 | 0.6965 | 0.052* | |
C10' | 0.5137 (3) | 0.3172 (2) | 0.07880 (19) | 0.0456 (6) | |
H10' | 0.5090 | 0.3620 | 0.1485 | 0.055* | |
C11 | 0.3128 (3) | 0.1280 (2) | 0.61075 (18) | 0.0412 (6) | |
C11' | 0.2875 (3) | 0.0607 (2) | 0.05910 (19) | 0.0420 (6) | |
C12 | 0.2363 (3) | −0.0610 (2) | 0.45867 (19) | 0.0538 (7) | |
H12A | 0.1249 | −0.0630 | 0.4739 | 0.065* | |
H12B | 0.2923 | −0.1109 | 0.4842 | 0.065* | |
C12' | 0.1908 (3) | −0.1203 (2) | −0.09642 (19) | 0.0524 (7) | |
H12C | 0.0750 | −0.1186 | −0.0915 | 0.063* | |
H12D | 0.2316 | −0.1696 | −0.0645 | 0.063* | |
C13' | 0.2150 (4) | −0.1715 (2) | −0.2081 (2) | 0.0732 (9) | |
H13D | 0.1711 | −0.1241 | −0.2402 | 0.110* | |
H13E | 0.1596 | −0.2505 | −0.2426 | 0.110* | |
H13F | 0.3296 | −0.1725 | −0.2128 | 0.110* | |
C13 | 0.2336 (3) | −0.1086 (2) | 0.3439 (2) | 0.0631 (8) | |
H13A | 0.1773 | −0.0598 | 0.3182 | 0.095* | |
H13B | 0.1782 | −0.1877 | 0.3115 | 0.095* | |
H13C | 0.3437 | −0.1086 | 0.3285 | 0.095* | |
N1 | 0.4719 (2) | 0.27888 (16) | 0.58919 (15) | 0.0431 (5) | |
N1' | 0.4412 (2) | 0.21203 (17) | 0.03521 (15) | 0.0447 (5) | |
N2' | 0.3664 (2) | 0.17184 (16) | 0.09748 (16) | 0.0499 (5) | |
H2'A | 0.3695 | 0.2178 | 0.1618 | 0.060* | |
N2 | 0.3884 (2) | 0.24022 (16) | 0.64915 (15) | 0.0454 (5) | |
H2A | 0.3837 | 0.2878 | 0.7121 | 0.055* | |
N3' | 0.2766 (2) | −0.00132 (17) | −0.04207 (16) | 0.0511 (6) | |
H3'A | 0.3224 | 0.0303 | −0.0773 | 0.061* | |
N3 | 0.3184 (2) | 0.06031 (16) | 0.51214 (15) | 0.0475 (5) | |
H3A | 0.3728 | 0.0889 | 0.4779 | 0.057* | |
O1 | 0.7355 (2) | 0.41240 (14) | 0.42089 (13) | 0.0534 (5) | |
O1' | 0.6999 (2) | 0.35106 (14) | −0.13347 (13) | 0.0575 (5) | |
O2 | 0.6529 (2) | 0.62856 (14) | 0.70913 (13) | 0.0603 (5) | |
O2' | 0.6649 (2) | 0.55142 (14) | 0.16840 (14) | 0.0644 (5) | |
O1W | 0.4956 (3) | 0.10193 (19) | 0.34506 (17) | 0.0689 (6) | |
S1' | 0.21192 (9) | 0.00898 (6) | 0.13833 (5) | 0.0591 (2) | |
S1 | 0.21930 (9) | 0.08415 (6) | 0.68995 (5) | 0.0587 (2) | |
H1WA | 0.569 (4) | 0.054 (3) | 0.326 (4) | 0.18 (2)* | |
H1WB | 0.422 (4) | 0.080 (4) | 0.293 (2) | 0.16 (2)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1' | 0.0496 (15) | 0.0441 (15) | 0.0419 (16) | 0.0038 (12) | 0.0133 (13) | 0.0194 (13) |
C1 | 0.0458 (15) | 0.0384 (14) | 0.0450 (16) | 0.0025 (12) | 0.0109 (13) | 0.0186 (13) |
C2' | 0.0640 (17) | 0.0635 (18) | 0.0423 (16) | 0.0010 (15) | 0.0162 (14) | 0.0244 (15) |
C2 | 0.0649 (18) | 0.0576 (18) | 0.0497 (17) | 0.0082 (15) | 0.0259 (15) | 0.0238 (15) |
C3 | 0.0645 (18) | 0.0609 (18) | 0.0604 (19) | 0.0022 (15) | 0.0229 (15) | 0.0348 (16) |
C3' | 0.0595 (18) | 0.0645 (19) | 0.063 (2) | −0.0021 (15) | 0.0179 (15) | 0.0363 (17) |
C4' | 0.0574 (17) | 0.0525 (17) | 0.064 (2) | −0.0023 (14) | 0.0111 (15) | 0.0284 (16) |
C4 | 0.0595 (17) | 0.0492 (16) | 0.064 (2) | −0.0055 (14) | 0.0125 (15) | 0.0278 (16) |
C5 | 0.0547 (16) | 0.0430 (15) | 0.0467 (16) | −0.0020 (13) | 0.0092 (13) | 0.0181 (13) |
C5' | 0.0566 (16) | 0.0463 (15) | 0.0475 (16) | 0.0018 (13) | 0.0113 (13) | 0.0193 (13) |
C6 | 0.0421 (14) | 0.0411 (14) | 0.0404 (15) | 0.0030 (11) | 0.0084 (12) | 0.0194 (12) |
C6' | 0.0441 (14) | 0.0392 (14) | 0.0422 (15) | 0.0051 (11) | 0.0096 (12) | 0.0196 (12) |
C7 | 0.0483 (15) | 0.0415 (14) | 0.0366 (15) | 0.0032 (12) | 0.0064 (12) | 0.0172 (13) |
C7' | 0.0481 (15) | 0.0405 (14) | 0.0411 (16) | 0.0068 (12) | 0.0129 (13) | 0.0167 (13) |
C8' | 0.0460 (14) | 0.0385 (14) | 0.0389 (15) | 0.0040 (11) | 0.0113 (12) | 0.0162 (12) |
C8 | 0.0462 (14) | 0.0349 (13) | 0.0372 (15) | 0.0031 (11) | 0.0099 (12) | 0.0150 (12) |
C9 | 0.0612 (17) | 0.0384 (14) | 0.0463 (16) | −0.0024 (13) | 0.0167 (14) | 0.0170 (13) |
C9' | 0.0697 (18) | 0.0418 (15) | 0.0472 (17) | −0.0033 (13) | 0.0186 (14) | 0.0163 (14) |
C10 | 0.0531 (15) | 0.0389 (14) | 0.0365 (14) | 0.0013 (12) | 0.0115 (12) | 0.0151 (12) |
C10' | 0.0574 (16) | 0.0398 (14) | 0.0401 (15) | 0.0045 (13) | 0.0167 (13) | 0.0156 (13) |
C11 | 0.0483 (15) | 0.0353 (14) | 0.0417 (15) | 0.0055 (12) | 0.0119 (12) | 0.0169 (12) |
C11' | 0.0468 (15) | 0.0358 (14) | 0.0432 (16) | 0.0027 (12) | 0.0100 (12) | 0.0160 (12) |
C12 | 0.0696 (18) | 0.0405 (14) | 0.0489 (17) | −0.0031 (13) | 0.0164 (14) | 0.0164 (13) |
C12' | 0.0598 (17) | 0.0452 (15) | 0.0488 (17) | −0.0027 (13) | 0.0110 (14) | 0.0174 (13) |
C13' | 0.094 (2) | 0.0668 (19) | 0.0442 (18) | −0.0098 (17) | 0.0102 (17) | 0.0126 (15) |
C13 | 0.0741 (19) | 0.0524 (17) | 0.0506 (18) | −0.0046 (15) | 0.0149 (15) | 0.0105 (14) |
N1 | 0.0539 (13) | 0.0379 (12) | 0.0395 (12) | −0.0002 (10) | 0.0126 (10) | 0.0182 (10) |
N1' | 0.0547 (13) | 0.0400 (12) | 0.0417 (12) | 0.0007 (10) | 0.0154 (10) | 0.0184 (10) |
N2' | 0.0680 (14) | 0.0413 (12) | 0.0389 (12) | −0.0031 (11) | 0.0175 (11) | 0.0150 (10) |
N2 | 0.0614 (13) | 0.0371 (11) | 0.0368 (12) | −0.0003 (10) | 0.0166 (10) | 0.0136 (10) |
N3' | 0.0663 (14) | 0.0437 (12) | 0.0412 (13) | −0.0063 (11) | 0.0148 (11) | 0.0164 (11) |
N3 | 0.0602 (13) | 0.0403 (12) | 0.0422 (13) | −0.0013 (10) | 0.0180 (11) | 0.0166 (10) |
O1 | 0.0716 (12) | 0.0426 (10) | 0.0428 (11) | −0.0008 (9) | 0.0246 (9) | 0.0125 (9) |
O1' | 0.0788 (13) | 0.0477 (11) | 0.0407 (11) | −0.0064 (9) | 0.0234 (10) | 0.0127 (9) |
O2 | 0.0948 (14) | 0.0418 (10) | 0.0390 (11) | −0.0025 (10) | 0.0261 (10) | 0.0101 (9) |
O2' | 0.0966 (14) | 0.0463 (11) | 0.0427 (12) | −0.0063 (10) | 0.0302 (11) | 0.0094 (9) |
O1W | 0.0823 (16) | 0.0636 (14) | 0.0546 (14) | −0.0030 (13) | 0.0150 (13) | 0.0196 (11) |
S1' | 0.0820 (5) | 0.0521 (4) | 0.0441 (4) | −0.0073 (4) | 0.0147 (4) | 0.0227 (4) |
S1 | 0.0800 (5) | 0.0487 (4) | 0.0507 (4) | −0.0004 (4) | 0.0288 (4) | 0.0214 (3) |
C1'—O1' | 1.376 (3) | C9'—O1' | 1.338 (3) |
C1'—C2' | 1.382 (3) | C9'—H9' | 0.9300 |
C1'—C6' | 1.388 (3) | C10—N1 | 1.269 (3) |
C1—C2 | 1.376 (3) | C10—H10 | 0.9300 |
C1—O1 | 1.380 (3) | C10'—N1' | 1.273 (3) |
C1—C6 | 1.385 (3) | C10'—H10' | 0.9300 |
C2'—C3' | 1.366 (3) | C11—N3 | 1.324 (3) |
C2'—H2' | 0.9300 | C11—N2 | 1.356 (3) |
C2—C3 | 1.370 (3) | C11—S1 | 1.681 (2) |
C2—H2 | 0.9300 | C11'—N3' | 1.324 (3) |
C3—C4 | 1.382 (4) | C11'—N2' | 1.354 (3) |
C3—H3 | 0.9300 | C11'—S1' | 1.673 (2) |
C3'—C4' | 1.392 (4) | C12—N3 | 1.465 (3) |
C3'—H3' | 0.9300 | C12—C13 | 1.500 (3) |
C4'—C5' | 1.367 (3) | C12—H12A | 0.9700 |
C4'—H4' | 0.9300 | C12—H12B | 0.9700 |
C4—C5 | 1.369 (3) | C12'—N3' | 1.454 (3) |
C4—H4 | 0.9300 | C12'—C13' | 1.501 (3) |
C5—C6 | 1.396 (3) | C12'—H12C | 0.9700 |
C5—H5 | 0.9300 | C12'—H12D | 0.9700 |
C5'—C6' | 1.398 (3) | C13'—H13D | 0.9600 |
C5'—H5' | 0.9300 | C13'—H13E | 0.9600 |
C6—C7 | 1.461 (3) | C13'—H13F | 0.9600 |
C6'—C7' | 1.458 (3) | C13—H13A | 0.9600 |
C7—O2 | 1.230 (3) | C13—H13B | 0.9600 |
C7—C8 | 1.452 (3) | C13—H13C | 0.9600 |
C7'—O2' | 1.236 (3) | N1—N2 | 1.367 (2) |
C7'—C8' | 1.451 (3) | N1'—N2' | 1.369 (2) |
C8'—C9' | 1.350 (3) | N2'—H2'A | 0.8600 |
C8'—C10' | 1.453 (3) | N2—H2A | 0.8600 |
C8—C9 | 1.344 (3) | N3'—H3'A | 0.8600 |
C8—C10 | 1.457 (3) | N3—H3A | 0.8600 |
C9—O1 | 1.339 (2) | O1W—H1WA | 0.866 (19) |
C9—H9 | 0.9300 | O1W—H1WB | 0.847 (19) |
O1'—C1'—C2' | 116.8 (2) | N1—C10—C8 | 121.4 (2) |
O1'—C1'—C6' | 121.5 (2) | N1—C10—H10 | 119.3 |
C2'—C1'—C6' | 121.7 (2) | C8—C10—H10 | 119.3 |
C2—C1—O1 | 116.5 (2) | N1'—C10'—C8' | 121.9 (2) |
C2—C1—C6 | 122.3 (2) | N1'—C10'—H10' | 119.0 |
O1—C1—C6 | 121.3 (2) | C8'—C10'—H10' | 119.0 |
C3'—C2'—C1' | 119.2 (2) | N3—C11—N2 | 116.8 (2) |
C3'—C2'—H2' | 120.4 | N3—C11—S1 | 124.54 (18) |
C1'—C2'—H2' | 120.4 | N2—C11—S1 | 118.62 (18) |
C3—C2—C1 | 118.8 (2) | N3'—C11'—N2' | 116.0 (2) |
C3—C2—H2 | 120.6 | N3'—C11'—S1' | 123.86 (18) |
C1—C2—H2 | 120.6 | N2'—C11'—S1' | 120.18 (19) |
C2—C3—C4 | 120.5 (2) | N3—C12—C13 | 111.8 (2) |
C2—C3—H3 | 119.8 | N3—C12—H12A | 109.2 |
C4—C3—H3 | 119.8 | C13—C12—H12A | 109.2 |
C2'—C3'—C4' | 120.6 (2) | N3—C12—H12B | 109.2 |
C2'—C3'—H3' | 119.7 | C13—C12—H12B | 109.2 |
C4'—C3'—H3' | 119.7 | H12A—C12—H12B | 107.9 |
C5'—C4'—C3' | 119.9 (2) | N3'—C12'—C13' | 110.4 (2) |
C5'—C4'—H4' | 120.1 | N3'—C12'—H12C | 109.6 |
C3'—C4'—H4' | 120.1 | C13'—C12'—H12C | 109.6 |
C5—C4—C3 | 120.3 (2) | N3'—C12'—H12D | 109.6 |
C5—C4—H4 | 119.8 | C13'—C12'—H12D | 109.6 |
C3—C4—H4 | 119.8 | H12C—C12'—H12D | 108.1 |
C4—C5—C6 | 120.5 (2) | C12'—C13'—H13D | 109.5 |
C4—C5—H5 | 119.7 | C12'—C13'—H13E | 109.5 |
C6—C5—H5 | 119.7 | H13D—C13'—H13E | 109.5 |
C4'—C5'—C6' | 120.8 (2) | C12'—C13'—H13F | 109.5 |
C4'—C5'—H5' | 119.6 | H13D—C13'—H13F | 109.5 |
C6'—C5'—H5' | 119.6 | H13E—C13'—H13F | 109.5 |
C1—C6—C5 | 117.6 (2) | C12—C13—H13A | 109.5 |
C1—C6—C7 | 120.0 (2) | C12—C13—H13B | 109.5 |
C5—C6—C7 | 122.3 (2) | H13A—C13—H13B | 109.5 |
C1'—C6'—C5' | 117.9 (2) | C12—C13—H13C | 109.5 |
C1'—C6'—C7' | 119.7 (2) | H13A—C13—H13C | 109.5 |
C5'—C6'—C7' | 122.4 (2) | H13B—C13—H13C | 109.5 |
O2—C7—C8 | 122.2 (2) | C10—N1—N2 | 116.40 (19) |
O2—C7—C6 | 122.6 (2) | C10'—N1'—N2' | 116.1 (2) |
C8—C7—C6 | 115.2 (2) | C11'—N2'—N1' | 120.9 (2) |
O2'—C7'—C8' | 121.7 (2) | C11'—N2'—H2'A | 119.6 |
O2'—C7'—C6' | 122.7 (2) | N1'—N2'—H2'A | 119.6 |
C8'—C7'—C6' | 115.7 (2) | C11—N2—N1 | 120.95 (19) |
C9'—C8'—C7' | 119.3 (2) | C11—N2—H2A | 119.5 |
C9'—C8'—C10' | 122.0 (2) | N1—N2—H2A | 119.5 |
C7'—C8'—C10' | 118.7 (2) | C11'—N3'—C12' | 123.2 (2) |
C9—C8—C7 | 119.7 (2) | C11'—N3'—H3'A | 118.4 |
C9—C8—C10 | 121.4 (2) | C12'—N3'—H3'A | 118.4 |
C7—C8—C10 | 119.0 (2) | C11—N3—C12 | 123.1 (2) |
O1—C9—C8 | 125.0 (2) | C11—N3—H3A | 118.5 |
O1—C9—H9 | 117.5 | C12—N3—H3A | 118.5 |
C8—C9—H9 | 117.5 | C9—O1—C1 | 118.76 (18) |
O1'—C9'—C8' | 124.9 (2) | C9'—O1'—C1' | 118.85 (19) |
O1'—C9'—H9' | 117.5 | H1WA—O1W—H1WB | 106 (4) |
C8'—C9'—H9' | 117.5 | ||
O1'—C1'—C2'—C3' | −179.8 (2) | C6'—C7'—C8'—C10' | 179.0 (2) |
C6'—C1'—C2'—C3' | 0.1 (4) | O2—C7—C8—C9 | 176.4 (2) |
O1—C1—C2—C3 | −179.9 (2) | C6—C7—C8—C9 | −2.9 (3) |
C6—C1—C2—C3 | 0.5 (4) | O2—C7—C8—C10 | −2.5 (4) |
C1—C2—C3—C4 | 0.2 (4) | C6—C7—C8—C10 | 178.11 (19) |
C1'—C2'—C3'—C4' | 0.3 (4) | C7—C8—C9—O1 | 0.9 (4) |
C2'—C3'—C4'—C5' | −0.6 (4) | C10—C8—C9—O1 | 179.8 (2) |
C2—C3—C4—C5 | −1.1 (4) | C7'—C8'—C9'—O1' | 0.3 (4) |
C3—C4—C5—C6 | 1.3 (4) | C10'—C8'—C9'—O1' | 180.0 (2) |
C3'—C4'—C5'—C6' | 0.4 (4) | C9—C8—C10—N1 | −0.4 (4) |
C2—C1—C6—C5 | −0.3 (4) | C7—C8—C10—N1 | 178.5 (2) |
O1—C1—C6—C5 | −179.9 (2) | C9'—C8'—C10'—N1' | −1.7 (4) |
C2—C1—C6—C7 | 177.9 (2) | C7'—C8'—C10'—N1' | 177.9 (2) |
O1—C1—C6—C7 | −1.7 (4) | C8—C10—N1—N2 | 179.22 (18) |
C4—C5—C6—C1 | −0.6 (4) | C8'—C10'—N1'—N2' | 177.44 (19) |
C4—C5—C6—C7 | −178.8 (2) | N3'—C11'—N2'—N1' | −5.3 (3) |
O1'—C1'—C6'—C5' | 179.6 (2) | S1'—C11'—N2'—N1' | 174.29 (16) |
C2'—C1'—C6'—C5' | −0.2 (4) | C10'—N1'—N2'—C11' | −179.2 (2) |
O1'—C1'—C6'—C7' | −1.1 (4) | N3—C11—N2—N1 | −2.7 (3) |
C2'—C1'—C6'—C7' | 179.0 (2) | S1—C11—N2—N1 | 177.31 (16) |
C4'—C5'—C6'—C1' | 0.0 (4) | C10—N1—N2—C11 | 175.7 (2) |
C4'—C5'—C6'—C7' | −179.3 (2) | N2'—C11'—N3'—C12' | −177.6 (2) |
C1—C6—C7—O2 | −176.0 (2) | S1'—C11'—N3'—C12' | 2.8 (3) |
C5—C6—C7—O2 | 2.1 (4) | C13'—C12'—N3'—C11' | −174.1 (2) |
C1—C6—C7—C8 | 3.3 (3) | N2—C11—N3—C12 | −177.1 (2) |
C5—C6—C7—C8 | −178.5 (2) | S1—C11—N3—C12 | 2.8 (3) |
C1'—C6'—C7'—O2' | −178.0 (2) | C13—C12—N3—C11 | 168.4 (2) |
C5'—C6'—C7'—O2' | 1.2 (4) | C8—C9—O1—C1 | 1.0 (4) |
C1'—C6'—C7'—C8' | 1.7 (3) | C2—C1—O1—C9 | 179.8 (2) |
C5'—C6'—C7'—C8' | −179.1 (2) | C6—C1—O1—C9 | −0.5 (3) |
O2'—C7'—C8'—C9' | 178.4 (2) | C8'—C9'—O1'—C1' | 0.4 (4) |
C6'—C7'—C8'—C9' | −1.3 (3) | C2'—C1'—O1'—C9' | 179.9 (2) |
O2'—C7'—C8'—C10' | −1.3 (3) | C6'—C1'—O1'—C9' | 0.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2′—H2′A···O2i | 0.86 | 2.09 | 2.900 (3) | 158 |
N2—H2A···O2′i | 0.86 | 2.14 | 2.938 (2) | 155 |
N3—H3A···O1W | 0.86 | 2.31 | 3.131 (3) | 161 |
O1W—H1WB···S1′ | 0.85 (3) | 2.47 (3) | 3.322 (2) | 178 (4) |
O1W—H1WA···S1ii | 0.87 (2) | 2.52 (2) | 3.370 (3) | 167 (4) |
C9—H9···O1W | 0.93 | 2.30 | 3.213 (4) | 169 |
C10—H10···O2′i | 0.93 | 2.51 | 3.297 (3) | 143 |
C10′—H10′···O2i | 0.93 | 2.52 | 3.302 (3) | 142 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1. |
C17H14ClN3OS | F(000) = 712 |
Mr = 343.82 | Dx = 1.431 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3902 reflections |
a = 10.3176 (3) Å | θ = 1.5–28.4° |
b = 5.7589 (2) Å | µ = 0.38 mm−1 |
c = 27.0364 (7) Å | T = 296 K |
β = 96.564 (2)° | Block, colourless |
V = 1595.92 (8) Å3 | 0.30 × 0.25 × 0.20 mm |
Z = 4 |
Bruker Kappa APEXII CCD diffractometer | 3902 independent reflections |
Radiation source: fine-focus sealed tube | 2089 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
ω and ϕ scans | θmax = 28.4°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −13→13 |
Tmin = 0.893, Tmax = 0.927 | k = −7→7 |
14667 measured reflections | l = −35→35 |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.053P)2 + 0.0466P] where P = (Fo2 + 2Fc2)/3 |
3902 reflections | (Δ/σ)max < 0.001 |
208 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C17H14ClN3OS | V = 1595.92 (8) Å3 |
Mr = 343.82 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.3176 (3) Å | µ = 0.38 mm−1 |
b = 5.7589 (2) Å | T = 296 K |
c = 27.0364 (7) Å | 0.30 × 0.25 × 0.20 mm |
β = 96.564 (2)° |
Bruker Kappa APEXII CCD diffractometer | 3902 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 2089 reflections with I > 2σ(I) |
Tmin = 0.893, Tmax = 0.927 | Rint = 0.050 |
14667 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.23 e Å−3 |
3902 reflections | Δρmin = −0.20 e Å−3 |
208 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 | ||
C1 | 0.4918 (3) | −0.2996 (5) | −0.10347 (12) | 0.0665 (8) | |
H1 | 0.4591 | −0.3879 | −0.0789 | 0.080* | |
C2 | 0.4637 (3) | −0.3582 (5) | −0.15313 (13) | 0.0749 (9) | |
H2 | 0.4120 | −0.4872 | −0.1621 | 0.090* | |
C3 | 0.5116 (3) | −0.2267 (6) | −0.18911 (12) | 0.0759 (9) | |
H3 | 0.4921 | −0.2669 | −0.2224 | 0.091* | |
C4 | 0.5882 (3) | −0.0365 (5) | −0.17654 (10) | 0.0622 (7) | |
H4 | 0.6193 | 0.0518 | −0.2015 | 0.075* | |
C5 | 0.6198 (2) | 0.0260 (4) | −0.12710 (8) | 0.0457 (6) | |
C6 | 0.5690 (2) | −0.1087 (4) | −0.09079 (10) | 0.0531 (6) | |
C7 | 0.6397 (3) | 0.1634 (4) | −0.02714 (9) | 0.0563 (7) | |
H7A | 0.6881 | 0.1612 | 0.0058 | 0.068* | |
H7B | 0.5608 | 0.2529 | −0.0251 | 0.068* | |
C8 | 0.7205 (2) | 0.2839 (4) | −0.06223 (8) | 0.0456 (6) | |
C9 | 0.7056 (2) | 0.2157 (4) | −0.11002 (8) | 0.0446 (6) | |
C10 | 0.7994 (2) | 0.4764 (4) | −0.04404 (9) | 0.0490 (6) | |
H10 | 0.8449 | 0.5619 | −0.0656 | 0.059* | |
C11 | 0.8930 (2) | 0.7961 (4) | 0.06460 (8) | 0.0458 (6) | |
C12 | 0.8439 (2) | 0.6739 (4) | 0.14825 (8) | 0.0430 (6) | |
C13 | 0.8894 (2) | 0.4948 (4) | 0.17950 (9) | 0.0497 (6) | |
H13 | 0.9269 | 0.3642 | 0.1667 | 0.060* | |
C14 | 0.8788 (2) | 0.5110 (5) | 0.22994 (9) | 0.0538 (7) | |
H14 | 0.9088 | 0.3902 | 0.2510 | 0.065* | |
C15 | 0.8245 (2) | 0.7033 (5) | 0.24904 (9) | 0.0563 (7) | |
H15 | 0.8189 | 0.7146 | 0.2831 | 0.068* | |
C16 | 0.7784 (2) | 0.8787 (5) | 0.21777 (9) | 0.0580 (7) | |
H16 | 0.7407 | 1.0086 | 0.2307 | 0.070* | |
C17 | 0.7870 (2) | 0.8659 (4) | 0.16725 (9) | 0.0520 (6) | |
H17 | 0.7547 | 0.9856 | 0.1463 | 0.062* | |
N1 | 0.80705 (19) | 0.5309 (3) | 0.00252 (7) | 0.0496 (5) | |
N2 | 0.87785 (19) | 0.7257 (4) | 0.01625 (7) | 0.0533 (5) | |
H2A | 0.9130 | 0.8041 | −0.0058 | 0.064* | |
N3 | 0.84862 (19) | 0.6451 (3) | 0.09615 (7) | 0.0520 (5) | |
H3A | 0.8196 | 0.5154 | 0.0836 | 0.062* | |
O1 | 0.60439 (18) | −0.0669 (3) | −0.04098 (6) | 0.0662 (5) | |
Cl1 | 0.79000 (7) | 0.35034 (13) | −0.15374 (2) | 0.0649 (2) | |
S1 | 0.96413 (7) | 1.05093 (12) | 0.07927 (2) | 0.0565 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0604 (16) | 0.0548 (19) | 0.086 (2) | −0.0045 (14) | 0.0171 (15) | −0.0053 (17) |
C2 | 0.0523 (16) | 0.070 (2) | 0.101 (3) | −0.0045 (15) | 0.0005 (16) | −0.030 (2) |
C3 | 0.0651 (18) | 0.092 (3) | 0.068 (2) | 0.0024 (18) | −0.0059 (15) | −0.0280 (19) |
C4 | 0.0606 (16) | 0.074 (2) | 0.0509 (16) | 0.0048 (15) | 0.0005 (13) | −0.0125 (15) |
C5 | 0.0467 (13) | 0.0493 (15) | 0.0410 (13) | 0.0075 (11) | 0.0046 (10) | −0.0025 (12) |
C6 | 0.0534 (14) | 0.0502 (17) | 0.0564 (16) | 0.0037 (12) | 0.0089 (12) | −0.0055 (13) |
C7 | 0.0773 (17) | 0.0502 (17) | 0.0437 (14) | −0.0077 (14) | 0.0160 (12) | 0.0006 (13) |
C8 | 0.0527 (13) | 0.0474 (15) | 0.0375 (13) | 0.0009 (12) | 0.0093 (10) | 0.0022 (12) |
C9 | 0.0500 (13) | 0.0473 (15) | 0.0374 (12) | 0.0027 (11) | 0.0096 (10) | 0.0037 (11) |
C10 | 0.0584 (15) | 0.0506 (16) | 0.0387 (13) | −0.0022 (12) | 0.0088 (11) | 0.0028 (12) |
C11 | 0.0528 (14) | 0.0441 (15) | 0.0416 (13) | 0.0011 (11) | 0.0103 (11) | 0.0004 (12) |
C12 | 0.0496 (13) | 0.0409 (15) | 0.0397 (13) | −0.0090 (11) | 0.0099 (10) | −0.0015 (11) |
C13 | 0.0582 (15) | 0.0412 (15) | 0.0522 (15) | 0.0008 (12) | 0.0167 (12) | −0.0038 (12) |
C14 | 0.0631 (16) | 0.0518 (17) | 0.0479 (15) | −0.0023 (13) | 0.0123 (12) | 0.0063 (13) |
C15 | 0.0646 (16) | 0.0636 (19) | 0.0428 (14) | −0.0140 (14) | 0.0156 (12) | −0.0079 (14) |
C16 | 0.0673 (16) | 0.0512 (17) | 0.0589 (17) | −0.0020 (13) | 0.0211 (13) | −0.0143 (14) |
C17 | 0.0623 (16) | 0.0413 (15) | 0.0539 (15) | 0.0029 (12) | 0.0128 (12) | 0.0021 (13) |
N1 | 0.0624 (13) | 0.0435 (13) | 0.0433 (12) | −0.0043 (10) | 0.0083 (9) | −0.0006 (10) |
N2 | 0.0713 (13) | 0.0527 (14) | 0.0368 (11) | −0.0131 (11) | 0.0101 (9) | 0.0021 (10) |
N3 | 0.0789 (14) | 0.0406 (12) | 0.0386 (11) | −0.0136 (11) | 0.0148 (10) | −0.0063 (10) |
O1 | 0.0928 (13) | 0.0550 (13) | 0.0525 (11) | −0.0160 (10) | 0.0162 (10) | 0.0034 (10) |
Cl1 | 0.0802 (5) | 0.0762 (5) | 0.0411 (4) | −0.0098 (4) | 0.0189 (3) | 0.0059 (3) |
S1 | 0.0796 (5) | 0.0433 (4) | 0.0488 (4) | −0.0101 (3) | 0.0162 (3) | −0.0023 (3) |
C1—C6 | 1.378 (3) | C10—H10 | 0.9300 |
C1—C2 | 1.383 (4) | C11—N3 | 1.335 (3) |
C1—H1 | 0.9300 | C11—N2 | 1.361 (3) |
C2—C3 | 1.369 (4) | C11—S1 | 1.668 (2) |
C2—H2 | 0.9300 | C12—C17 | 1.378 (3) |
C3—C4 | 1.371 (4) | C12—C13 | 1.381 (3) |
C3—H3 | 0.9300 | C12—N3 | 1.425 (3) |
C4—C5 | 1.387 (3) | C13—C14 | 1.384 (3) |
C4—H4 | 0.9300 | C13—H13 | 0.9300 |
C5—C6 | 1.399 (3) | C14—C15 | 1.369 (3) |
C5—C9 | 1.448 (3) | C14—H14 | 0.9300 |
C6—O1 | 1.375 (3) | C15—C16 | 1.367 (3) |
C7—O1 | 1.414 (3) | C15—H15 | 0.9300 |
C7—C8 | 1.503 (3) | C16—C17 | 1.381 (3) |
C7—H7A | 0.9700 | C16—H16 | 0.9300 |
C7—H7B | 0.9700 | C17—H17 | 0.9300 |
C8—C9 | 1.343 (3) | N1—N2 | 1.367 (3) |
C8—C10 | 1.429 (3) | N2—H2A | 0.8600 |
C9—Cl1 | 1.730 (2) | N3—H3A | 0.8600 |
C10—N1 | 1.291 (3) | ||
C6—C1—C2 | 119.2 (3) | N1—C10—H10 | 120.2 |
C6—C1—H1 | 120.4 | C8—C10—H10 | 120.2 |
C2—C1—H1 | 120.4 | N3—C11—N2 | 114.2 (2) |
C3—C2—C1 | 120.1 (3) | N3—C11—S1 | 126.51 (18) |
C3—C2—H2 | 119.9 | N2—C11—S1 | 119.31 (18) |
C1—C2—H2 | 119.9 | C17—C12—C13 | 120.0 (2) |
C2—C3—C4 | 120.7 (3) | C17—C12—N3 | 121.7 (2) |
C2—C3—H3 | 119.6 | C13—C12—N3 | 118.1 (2) |
C4—C3—H3 | 119.6 | C12—C13—C14 | 119.5 (2) |
C3—C4—C5 | 120.8 (3) | C12—C13—H13 | 120.2 |
C3—C4—H4 | 119.6 | C14—C13—H13 | 120.2 |
C5—C4—H4 | 119.6 | C15—C14—C13 | 120.6 (2) |
C4—C5—C6 | 117.8 (2) | C15—C14—H14 | 119.7 |
C4—C5—C9 | 124.8 (2) | C13—C14—H14 | 119.7 |
C6—C5—C9 | 117.3 (2) | C16—C15—C14 | 119.5 (2) |
O1—C6—C1 | 117.7 (3) | C16—C15—H15 | 120.2 |
O1—C6—C5 | 120.8 (2) | C14—C15—H15 | 120.2 |
C1—C6—C5 | 121.3 (3) | C15—C16—C17 | 121.0 (2) |
O1—C7—C8 | 114.2 (2) | C15—C16—H16 | 119.5 |
O1—C7—H7A | 108.7 | C17—C16—H16 | 119.5 |
C8—C7—H7A | 108.7 | C12—C17—C16 | 119.3 (2) |
O1—C7—H7B | 108.7 | C12—C17—H17 | 120.3 |
C8—C7—H7B | 108.7 | C16—C17—H17 | 120.3 |
H7A—C7—H7B | 107.6 | C10—N1—N2 | 115.8 (2) |
C9—C8—C10 | 123.8 (2) | C11—N2—N1 | 120.31 (19) |
C9—C8—C7 | 117.5 (2) | C11—N2—H2A | 119.8 |
C10—C8—C7 | 118.4 (2) | N1—N2—H2A | 119.8 |
C8—C9—C5 | 121.8 (2) | C11—N3—C12 | 127.5 (2) |
C8—C9—Cl1 | 121.0 (2) | C11—N3—H3A | 116.3 |
C5—C9—Cl1 | 117.22 (17) | C12—N3—H3A | 116.3 |
N1—C10—C8 | 119.6 (2) | C6—O1—C7 | 117.04 (19) |
C6—C1—C2—C3 | −0.3 (4) | C9—C8—C10—N1 | 179.3 (2) |
C1—C2—C3—C4 | 0.2 (4) | C7—C8—C10—N1 | 5.2 (3) |
C2—C3—C4—C5 | 0.6 (4) | C17—C12—C13—C14 | −0.8 (3) |
C3—C4—C5—C6 | −1.2 (4) | N3—C12—C13—C14 | −176.0 (2) |
C3—C4—C5—C9 | 176.4 (2) | C12—C13—C14—C15 | −0.4 (4) |
C2—C1—C6—O1 | −174.5 (2) | C13—C14—C15—C16 | 1.1 (4) |
C2—C1—C6—C5 | −0.3 (4) | C14—C15—C16—C17 | −0.7 (4) |
C4—C5—C6—O1 | 175.1 (2) | C13—C12—C17—C16 | 1.2 (3) |
C9—C5—C6—O1 | −2.7 (3) | N3—C12—C17—C16 | 176.3 (2) |
C4—C5—C6—C1 | 1.1 (3) | C15—C16—C17—C12 | −0.5 (4) |
C9—C5—C6—C1 | −176.8 (2) | C8—C10—N1—N2 | −176.1 (2) |
O1—C7—C8—C9 | 27.7 (3) | N3—C11—N2—N1 | 8.2 (3) |
O1—C7—C8—C10 | −157.8 (2) | S1—C11—N2—N1 | −172.62 (17) |
C10—C8—C9—C5 | −177.1 (2) | C10—N1—N2—C11 | −179.3 (2) |
C7—C8—C9—C5 | −2.9 (3) | N2—C11—N3—C12 | −176.3 (2) |
C10—C8—C9—Cl1 | 3.5 (3) | S1—C11—N3—C12 | 4.7 (4) |
C7—C8—C9—Cl1 | 177.74 (17) | C17—C12—N3—C11 | 52.3 (3) |
C4—C5—C9—C8 | 172.2 (2) | C13—C12—N3—C11 | −132.6 (2) |
C6—C5—C9—C8 | −10.1 (3) | C1—C6—O1—C7 | −157.2 (2) |
C4—C5—C9—Cl1 | −8.4 (3) | C5—C6—O1—C7 | 28.6 (3) |
C6—C5—C9—Cl1 | 169.29 (17) | C8—C7—O1—C6 | −40.3 (3) |
Cg1 is the centroid of the C12–C17 phenyl ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···S1i | 0.86 | 2.61 | 3.456 (2) | 167 |
C2—H2···Cg1ii | 0.93 | 2.86 | 3.697 (3) | 151 |
Symmetry codes: (i) −x+2, −y+2, −z; (ii) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2'—H2'A···O2i | 0.86 | 2.09 | 2.900 (3) | 158 |
N2—H2A···O2'i | 0.86 | 2.14 | 2.938 (2) | 155 |
N3—H3A···O1W | 0.86 | 2.31 | 3.131 (3) | 161 |
O1W—H1WB···S1' | 0.85 (3) | 2.47 (3) | 3.322 (2) | 178 (4) |
O1W—H1WA···S1ii | 0.87 (2) | 2.52 (2) | 3.370 (3) | 167 (4) |
C9—H9···O1W | 0.93 | 2.30 | 3.213 (4) | 169 |
C10—H10···O2'i | 0.93 | 2.51 | 3.297 (3) | 143 |
C10'—H10'···O2i | 0.93 | 2.52 | 3.302 (3) | 142 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1. |
Cg1 is the centroid of the C12–C17 phenyl ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···S1i | 0.86 | 2.61 | 3.456 (2) | 167 |
C2—H2···Cg1ii | 0.93 | 2.86 | 3.697 (3) | 151 |
Symmetry codes: (i) −x+2, −y+2, −z; (ii) −x+1, −y, −z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C13H13N3O2S·0.5H2O | C17H14ClN3OS |
Mr | 284.33 | 343.82 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 296 | 296 |
a, b, c (Å) | 8.2858 (2), 12.5422 (4), 14.3520 (5) | 10.3176 (3), 5.7589 (2), 27.0364 (7) |
α, β, γ (°) | 114.379 (2), 95.751 (3), 94.200 (2) | 90, 96.564 (2), 90 |
V (Å3) | 1340.81 (7) | 1595.92 (8) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.25 | 0.38 |
Crystal size (mm) | 0.35 × 0.30 × 0.25 | 0.30 × 0.25 × 0.20 |
Data collection | ||
Diffractometer | Bruker Kappa APEXII CCD diffractometer | Bruker Kappa APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.917, 0.940 | 0.893, 0.927 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19142, 5579, 2764 | 14667, 3902, 2089 |
Rint | 0.046 | 0.050 |
(sin θ/λ)max (Å−1) | 0.631 | 0.668 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.137, 0.94 | 0.047, 0.124, 0.99 |
No. of reflections | 5579 | 3902 |
No. of parameters | 362 | 208 |
No. of restraints | 2 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.24 | 0.23, −0.20 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009), SHELXL97 (Sheldrick, 2008) and PLATON Spek, 2009).
Acknowledgements
The authors thank Professor D. Velmurugan and Mr T. Srinivasan, CAS in Crystallography and Biophysics, University of Madras, Chennai, India, for the
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