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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 67| Part 12| December 2011| Page o3195
https://doi.org/10.1107/S1600536811045739

(Z)-N,N-Di­methyl-2-[phen­yl(pyridin-2-yl)methyl­­idene]hydrazinecarbo­thio­amide

K. Jayakumar,a M. Sithambaresanb* and M. R. Prathapachandra Kurupa

aDepartment of Applied Chemistry, Cochin University of Science and Technology, Kochi 682 022, India, and bDepartment of Chemistry, Faculty of Science, Eastern University, Sri Lanka, Chenkalady, Sri Lanka
*Correspondence e-mail: eesans@yahoo.com

(Received 5 October 2011; accepted 31 October 2011; online 5 November 2011)

The title compound, C15H16N4S, exists in the Z conformation with the thionyl S atom lying cis to the azomethine N atom. The shortening of the N—N distance [1.3697 (17) Å] is due to extensive delocalization with the pyridine ring. The hydrazine–carbothio­amide unit is almost planar, with a maximum deviation of 0.013 (2) Å for the amide N atom. The stability of this conformation is favoured by the formation of an intra­molecular N—H⋯N hydrogen bond. The packing of the mol­ecules involves no classical inter­molecular hydrogen-bonding inter­actions; however, a C—H⋯π inter­action occurs.

Related literature

For abackground to hydrazinecarbothio­amide and its derivatives, see: Beraldo & Gambino (2004[Beraldo, H. & Gambino, D. (2004). Mini Rev. Med. Chem. 4, 31-39.]). For the synthesis, see: Joseph et al. (2006[Joseph, M., Kuriakose, M., Kurup, M. R. P., Suresh, E., Kishore, A. & Bhat, S. G. (2006). Polyhedron, 25, 61-70.]). For related structures of hydrazinecarbothio­amides, see: Philip et al. (2006[Philip, V., Suni, V., Kurup, M. R. P. & Nethaji, M. (2006). Spectrochim. Acta Part A, 64, 171-177.]); Arumugam et al. (2011[Arumugam, S. R., Dasary, S. S. R., Venkatraman, R., Yu, H. & Fronczek, F. R. (2011). Acta Cryst. E67, m1409-m1410.]). For related structures, see: Seena et al. (2008[Seena, E. B., Kurup, M. R. P. & Suresh, E. (2008). J. Chem. Crystallogr. 38, 93-96.]); Usman et al. (2002[Usman, A., Razak, I. A., Chantrapromma, S., Fun, H.-K., Sreekanth, A., Sivakumar, S. & Prathapachandra Kurup, M. R. (2002). Acta Cryst. C58, m461-m463.]); Huheey et al. (1993[Huheey, J. E., Keiter, E. A. & Keitar, R. L. (1993). Inorganic Chemistry. Principles of Structure and Reactivity, 4th ed. New York: Harper Collins.]); Joseph et al. (2004[Joseph, M., Suni, V., Nayar, C. R., Kurup, M. R. P. & Fun, H.-K. (2004). J. Mol. Struct. 705, 63-70.]).

[Scheme 1]

Experimental

Crystal data

  • C15H16N4S

  • Mr = 284.39

  • Monoclinic, P 21 /c

  • a = 10.011 (2) Å

  • b = 8.888 (2) Å

  • c = 16.256 (4) Å

  • β = 94.528 (3)°

  • V = 1441.9 (6) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.22 mm−1

  • T = 153 K

  • 0.32 × 0.28 × 0.22 mm
Data collection

  • Bruker P4 diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2004[Bruker (2004). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.932, Tmax = 0.953

  • 14231 measured reflections

  • 2828 independent reflections

  • 2405 reflections with I > 2σ(I)

  • Rint = 0.031
Refinement

  • R[F2 > 2σ(F2)] = 0.039

  • wR(F2) = 0.110

  • S = 1.06

  • 2828 reflections

  • 188 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.19 e Å−3

  • Δρmin = −0.20 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the N1/C8–C12 ring.
D—H⋯A D—H H⋯A D⋯A D—H⋯A
N3—H3′⋯N1 0.837 (17) 1.869 (17) 2.602 (2) 145.4 (15)
C5—H5⋯Cgi 0.93 2.66 3.536 (2) 157
Symmetry code: (i) -x+2, -y+1, -z+1.

Data collection: SMART (Bruker, 2004[Bruker (2004). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2004[Bruker (2004). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811045739/fj2463sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811045739/fj2463Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811045739/fj2463Isup3.cml

checkCIF report


Comment top

A large number of studies have been devoted to the search for derivatives of hydrazinecarbothioamide, which have been used as drugs and have the ability to form complexes. The biological activity of these compounds depends on the parent aldehyde or 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. These thiourea derivatives find substantial applications in different facets of contemporary scientific research.

The title compound (Z)-2-N,N-dimethyl-2-[phenyl(pyridin-2-yl)methylidene]hydrazinecarbothioamide is found to exist in Z configuration. A perspective view of the molecular structure of the title compound, along with the atom-labeling scheme, is given in Fig. 1. The S1= C13–N3–N2 torsion-angle [14.4 (2)°] indicates that thionyl atom S1 is positioned cis to azomethane nitrogen atom N2. The hydrazinecarbothioamide moiety adopts an extended conjugation, with electron delocalization throughout the N4/C13/S1/N3/N2 group. The fact that the compound exists in the thione form is confirmed by the N3—N2, N4—C13 and C13=S1 bond distances. The C13=S1 bond distance is close to that expected for a C=S double bond of 1.60 Å (Huheey et al., 1993). The N3—N2 bond distance is very close to the reported similar substituted hydrazinecarbothioamide (Joseph et al., 2004). The resonance form involving pyridine ring would account for the shortening of the N—N distance through extensive electron delocalization.

The hydrazinecarbothioamide moiety, comprising atoms N3, C13, S1 and N4, is almost planar with the maximum deviation of 0.013 (2) Å for atom N4. The pyridyl ring and phenyl ring are not in the same plane and the pyridyl ring is twisted significantly from the hydrazinecarbothioamide plane, with a torsionl angle of -176.3 (2)°.

Two types of intramolecular (classical and non-classical) hydrogen bond interactions are found in this molecule. A classical hydrogen bonding interaction between the hydrogen attached to the N3 nitrogen and the N1 nitrogen with the D···A distance of 2.602 (2) Å and the non-classical hydrogen bonding interaction between one of the hydrogen atom attached to the C14 atom and the S1 atom of the molecule with a D···A distance of 3.030 (2) Å as described in Table 1.

Fig. 2 shows the packing diagram of the title compound. Packing of these molecules does not include any classical intermolecular hydrogen bonding interactions in its molecular array. However, it may be directed by the C—H···π interaction between the pyridine ring and the hydrogen attached at C5 carbon atom of the phenyl ring of the another molecule. There are four very weak π–π interactions present in this molecular array with the distances of 5.5874 (17), 4.8708 (15), 5.5455 (17) and 4.9165 (15) Å between the centroids of the corresponding rings involving interactions.

Related literature top

For abackground to hydrazinecarbothioamide and its derivatives, see: Beraldo & Gambino (2004). For the synthesis, see: Joseph et al. (2006). For related structures of hydrazinecarbothioamides, see: Philip et al. (2006); Arumugam et al. (2011). For related structures, see: Seena et al. (2008); Usman et al. (2002); Huheey et al. (1993); Joseph et al. (2004).

Experimental top

The title compound was prepared by adapting a reported procedure (Joseph et al., 2006) by refluxing a mixture of methanolic solutions of 2-benzoylpyridine (11 mmol, 2.032 g) and N,N-dimethylhydrazinecarbothioamide (11 mmol, 1.320 g) for five hours after adding 5 drops of acetic acid. Yellow crystals were collected, washed with few drops of methanol and dried over P4O10 in vacuo. Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation from its methanolic solution.

Refinement top

All H atoms on C were placed in calculated positions, guided by difference maps, with C—H bond distances 0.93–0.96 Å. H atoms were assigned as Uiso=1.2Ueq (1.5 for Me). N3—H3' hydrogen was located from difference maps and restrained using DFIX instruction.

Structure description top

A large number of studies have been devoted to the search for derivatives of hydrazinecarbothioamide, which have been used as drugs and have the ability to form complexes. The biological activity of these compounds depends on the parent aldehyde or 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. These thiourea derivatives find substantial applications in different facets of contemporary scientific research.

The title compound (Z)-2-N,N-dimethyl-2-[phenyl(pyridin-2-yl)methylidene]hydrazinecarbothioamide is found to exist in Z configuration. A perspective view of the molecular structure of the title compound, along with the atom-labeling scheme, is given in Fig. 1. The S1= C13–N3–N2 torsion-angle [14.4 (2)°] indicates that thionyl atom S1 is positioned cis to azomethane nitrogen atom N2. The hydrazinecarbothioamide moiety adopts an extended conjugation, with electron delocalization throughout the N4/C13/S1/N3/N2 group. The fact that the compound exists in the thione form is confirmed by the N3—N2, N4—C13 and C13=S1 bond distances. The C13=S1 bond distance is close to that expected for a C=S double bond of 1.60 Å (Huheey et al., 1993). The N3—N2 bond distance is very close to the reported similar substituted hydrazinecarbothioamide (Joseph et al., 2004). The resonance form involving pyridine ring would account for the shortening of the N—N distance through extensive electron delocalization.

The hydrazinecarbothioamide moiety, comprising atoms N3, C13, S1 and N4, is almost planar with the maximum deviation of 0.013 (2) Å for atom N4. The pyridyl ring and phenyl ring are not in the same plane and the pyridyl ring is twisted significantly from the hydrazinecarbothioamide plane, with a torsionl angle of -176.3 (2)°.

Two types of intramolecular (classical and non-classical) hydrogen bond interactions are found in this molecule. A classical hydrogen bonding interaction between the hydrogen attached to the N3 nitrogen and the N1 nitrogen with the D···A distance of 2.602 (2) Å and the non-classical hydrogen bonding interaction between one of the hydrogen atom attached to the C14 atom and the S1 atom of the molecule with a D···A distance of 3.030 (2) Å as described in Table 1.

Fig. 2 shows the packing diagram of the title compound. Packing of these molecules does not include any classical intermolecular hydrogen bonding interactions in its molecular array. However, it may be directed by the C—H···π interaction between the pyridine ring and the hydrogen attached at C5 carbon atom of the phenyl ring of the another molecule. There are four very weak π–π interactions present in this molecular array with the distances of 5.5874 (17), 4.8708 (15), 5.5455 (17) and 4.9165 (15) Å between the centroids of the corresponding rings involving interactions.

For abackground to hydrazinecarbothioamide and its derivatives, see: Beraldo & Gambino (2004). For the synthesis, see: Joseph et al. (2006). For related structures of hydrazinecarbothioamides, see: Philip et al. (2006); Arumugam et al. (2011). For related structures, see: Seena et al. (2008); Usman et al. (2002); Huheey et al. (1993); Joseph et al. (2004).

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with displacement ellipsoids are drawn at 50% probability level.
[Figure 2] Fig. 2. Packing diagram of the title compound, the unit cell is viewed down the a axis.
(Z)-N,N-Dimethyl-2-[phenyl(pyridin-2- yl)methylidene]hydrazinecarbothioamide top
Crystal data top
C15H16N4SF(000) = 600.0
Mr = 284.39Dx = 1.310 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8120 reflections
a = 10.011 (2) Åθ = 2.0–26.0°
b = 8.888 (2) ŵ = 0.22 mm−1
c = 16.256 (4) ÅT = 153 K
β = 94.528 (3)°Block, yellow
V = 1441.9 (6) Å30.32 × 0.28 × 0.22 mm
Z = 4
Data collection top
Bruker P4
diffractometer		2828 independent reflections
Radiation source: fine-focus sealed tube2405 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
Detector resolution: 8.33 pixels mm-1θmax = 26.0°, θmin = 2.0°
ω scansh = −12→12
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		k = −10→10
Tmin = 0.932, Tmax = 0.953l = −20→20
14231 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.110 w = 1/[σ2(Fo2) + (0.0606P)2 + 0.2366P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.014
2828 reflectionsΔρmax = 0.19 e Å−3
188 parametersΔρmin = −0.20 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0104 (16)
Crystal data top
C15H16N4SV = 1441.9 (6) Å3
Mr = 284.39Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.011 (2) ŵ = 0.22 mm−1
b = 8.888 (2) ÅT = 153 K
c = 16.256 (4) Å0.32 × 0.28 × 0.22 mm
β = 94.528 (3)°
Data collection top
Bruker P4
diffractometer		2828 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		2405 reflections with I > 2σ(I)
Tmin = 0.932, Tmax = 0.953Rint = 0.031
14231 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.110H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.19 e Å−3
2828 reflectionsΔρmin = −0.20 e Å−3
188 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
S10.75460 (4)0.15132 (5)0.31975 (3)0.05808 (18)
N10.98755 (14)0.68420 (14)0.33757 (8)0.0466 (3)
N20.99018 (12)0.35758 (13)0.36663 (7)0.0413 (3)
N30.87523 (12)0.42001 (16)0.33015 (8)0.0459 (3)
N40.68025 (13)0.41370 (17)0.25113 (9)0.0552 (4)
C11.33165 (15)0.42244 (19)0.39734 (10)0.0496 (4)
H11.33330.49830.35800.059*
C21.44999 (16)0.3531 (2)0.42682 (12)0.0584 (5)
H21.53070.38200.40690.070*
C31.44848 (18)0.2420 (2)0.48527 (12)0.0604 (5)
H31.52800.19560.50480.072*
C41.32983 (18)0.1993 (2)0.51494 (11)0.0586 (5)
H41.32910.12480.55510.070*
C51.21090 (16)0.26692 (18)0.48536 (10)0.0474 (4)
H51.13050.23680.50530.057*
C61.21111 (14)0.37895 (16)0.42634 (9)0.0386 (3)
C71.08395 (14)0.45037 (16)0.39224 (8)0.0383 (3)
C81.07742 (14)0.61797 (16)0.39196 (9)0.0404 (3)
C91.15590 (16)0.70179 (18)0.44910 (10)0.0499 (4)
H91.21730.65460.48650.060*
C101.14187 (19)0.85641 (19)0.44978 (13)0.0600 (5)
H101.19280.91430.48820.072*
C111.05114 (18)0.92430 (19)0.39262 (12)0.0574 (4)
H111.04081.02830.39120.069*
C120.97729 (18)0.83393 (18)0.33834 (11)0.0527 (4)
H120.91650.87930.29980.063*
C130.77074 (15)0.33429 (18)0.29902 (9)0.0442 (4)
C140.56134 (19)0.3425 (3)0.21167 (14)0.0755 (6)
H14A0.57780.31400.15640.113*
H14B0.48770.41190.21010.113*
H14C0.54000.25470.24240.113*
C150.6980 (2)0.5728 (2)0.23277 (14)0.0770 (6)
H15A0.69450.63060.28240.115*
H15B0.62790.60510.19300.115*
H15C0.78330.58740.21080.115*
H3'0.8833 (15)0.511 (2)0.3188 (9)0.043 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0506 (3)0.0477 (3)0.0740 (3)−0.00580 (18)−0.0075 (2)−0.00052 (19)
N10.0516 (8)0.0409 (7)0.0469 (7)0.0035 (6)0.0016 (6)0.0030 (5)
N20.0353 (6)0.0410 (7)0.0462 (7)0.0030 (5)−0.0045 (5)0.0000 (5)
N30.0394 (7)0.0388 (7)0.0574 (8)0.0035 (5)−0.0087 (6)0.0003 (6)
N40.0427 (7)0.0588 (9)0.0613 (8)0.0069 (6)−0.0143 (6)−0.0006 (7)
C10.0441 (9)0.0505 (9)0.0542 (9)0.0001 (7)0.0042 (7)0.0044 (7)
C20.0347 (8)0.0697 (12)0.0705 (11)0.0005 (8)0.0022 (8)−0.0032 (9)
C30.0425 (9)0.0639 (11)0.0711 (11)0.0098 (8)−0.0182 (8)−0.0052 (9)
C40.0562 (10)0.0552 (10)0.0611 (10)0.0010 (8)−0.0157 (8)0.0113 (8)
C50.0418 (8)0.0478 (9)0.0513 (9)−0.0055 (7)−0.0045 (7)0.0039 (7)
C60.0363 (7)0.0361 (7)0.0421 (8)0.0002 (6)−0.0042 (6)−0.0050 (6)
C70.0372 (7)0.0394 (7)0.0380 (7)0.0016 (6)0.0014 (6)−0.0007 (6)
C80.0373 (7)0.0400 (8)0.0442 (8)0.0019 (6)0.0058 (6)0.0004 (6)
C90.0448 (9)0.0463 (9)0.0577 (9)−0.0007 (7)−0.0016 (7)−0.0048 (7)
C100.0582 (11)0.0457 (10)0.0756 (12)−0.0065 (8)0.0024 (9)−0.0123 (8)
C110.0634 (11)0.0360 (8)0.0745 (11)−0.0007 (8)0.0162 (9)−0.0006 (8)
C120.0595 (10)0.0438 (9)0.0553 (9)0.0074 (7)0.0069 (8)0.0092 (7)
C130.0373 (8)0.0499 (9)0.0444 (8)0.0043 (6)−0.0021 (6)−0.0052 (6)
C140.0502 (11)0.0935 (16)0.0781 (13)0.0042 (10)−0.0250 (10)−0.0092 (11)
C150.0699 (13)0.0660 (13)0.0902 (15)0.0183 (10)−0.0245 (11)0.0121 (11)
Geometric parameters (Å, º) top
S1—C131.6712 (17)C5—C61.383 (2)
N1—C121.335 (2)C5—H50.9300
N1—C81.3461 (19)C6—C71.4898 (19)
N2—C71.2934 (18)C7—C81.491 (2)
N2—N31.3697 (17)C8—C91.386 (2)
N3—C131.3591 (19)C9—C101.381 (2)
N3—H3'0.837 (17)C9—H90.9300
N4—C131.3466 (19)C10—C111.385 (3)
N4—C141.452 (2)C10—H100.9300
N4—C151.459 (3)C11—C121.366 (2)
C1—C61.385 (2)C11—H110.9300
C1—C21.387 (2)C12—H120.9300
C1—H10.9300C14—H14A0.9600
C2—C31.371 (3)C14—H14B0.9600
C2—H20.9300C14—H14C0.9600
C3—C41.370 (3)C15—H15A0.9600
C3—H30.9300C15—H15B0.9600
C4—C51.385 (2)C15—H15C0.9600
C4—H40.9300
C12—N1—C8118.54 (14)N1—C8—C7117.75 (13)
C7—N2—N3116.40 (12)C9—C8—C7120.85 (13)
C13—N3—N2121.99 (13)C10—C9—C8119.18 (16)
C13—N3—H3'123.1 (11)C10—C9—H9120.4
N2—N3—H3'113.3 (11)C8—C9—H9120.4
C13—N4—C14121.18 (15)C9—C10—C11119.31 (16)
C13—N4—C15122.61 (14)C9—C10—H10120.3
C14—N4—C15116.16 (14)C11—C10—H10120.3
C6—C1—C2120.13 (16)C12—C11—C10118.02 (15)
C6—C1—H1119.9C12—C11—H11121.0
C2—C1—H1119.9C10—C11—H11121.0
C3—C2—C1120.23 (16)N1—C12—C11123.63 (16)
C3—C2—H2119.9N1—C12—H12118.2
C1—C2—H2119.9C11—C12—H12118.2
C4—C3—C2120.04 (16)N4—C13—N3112.61 (14)
C4—C3—H3120.0N4—C13—S1123.72 (12)
C2—C3—H3120.0N3—C13—S1123.65 (11)
C3—C4—C5120.19 (16)N4—C14—H14A109.5
C3—C4—H4119.9N4—C14—H14B109.5
C5—C4—H4119.9H14A—C14—H14B109.5
C6—C5—C4120.31 (15)N4—C14—H14C109.5
C6—C5—H5119.8H14A—C14—H14C109.5
C4—C5—H5119.8H14B—C14—H14C109.5
C5—C6—C1119.09 (14)N4—C15—H15A109.5
C5—C6—C7121.12 (13)N4—C15—H15B109.5
C1—C6—C7119.77 (13)H15A—C15—H15B109.5
N2—C7—C6115.17 (12)N4—C15—H15C109.5
N2—C7—C8127.26 (13)H15A—C15—H15C109.5
C6—C7—C8117.56 (12)H15B—C15—H15C109.5
N1—C8—C9121.30 (14)
C7—N2—N3—C13178.44 (14)N2—C7—C8—N1−23.7 (2)
C6—C1—C2—C3−0.5 (3)C6—C7—C8—N1157.05 (13)
C1—C2—C3—C4−0.2 (3)N2—C7—C8—C9152.63 (15)
C2—C3—C4—C50.8 (3)C6—C7—C8—C9−26.6 (2)
C3—C4—C5—C6−0.7 (3)N1—C8—C9—C10−0.4 (2)
C4—C5—C6—C10.0 (2)C7—C8—C9—C10−176.54 (16)
C4—C5—C6—C7178.48 (14)C8—C9—C10—C11−0.9 (3)
C2—C1—C6—C50.6 (2)C9—C10—C11—C121.0 (3)
C2—C1—C6—C7−177.91 (14)C8—N1—C12—C11−1.5 (3)
N3—N2—C7—C6−175.96 (12)C10—C11—C12—N10.2 (3)
N3—N2—C7—C84.8 (2)C14—N4—C13—N3179.72 (16)
C5—C6—C7—N2−50.15 (19)C15—N4—C13—N32.5 (2)
C1—C6—C7—N2128.32 (15)C14—N4—C13—S1−1.7 (2)
C5—C6—C7—C8129.21 (15)C15—N4—C13—S1−178.84 (15)
C1—C6—C7—C8−52.32 (19)N2—N3—C13—N4−166.98 (14)
C12—N1—C8—C91.5 (2)N2—N3—C13—S114.4 (2)
C12—N1—C8—C7177.81 (14)
Hydrogen-bond geometry (Å, º) top
Cg is the centroid of the N1/C8–C12 ring.
D—H···AD—HH···AD···AD—H···A
N3—H3′···N10.837 (17)1.869 (17)2.602 (2)145.4 (15)
C14—H14C···S10.962.573.030 (2)109
C5—H5···Cgi0.932.663.536 (2)157
Symmetry code: (i) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formulaC15H16N4S
Mr284.39
Crystal system, space groupMonoclinic, P21/c
Temperature (K)153
a, b, c (Å)10.011 (2), 8.888 (2), 16.256 (4)
β (°) 94.528 (3)
V (Å3)1441.9 (6)
Z4
Radiation typeMo Kα
µ (mm−1)0.22
Crystal size (mm)0.32 × 0.28 × 0.22
Data collection
DiffractometerBruker P4
Absorption correctionMulti-scan
(SADABS; Bruker, 2004)
Tmin, Tmax0.932, 0.953
No. of measured, independent and
observed [I > 2σ(I)] reflections		14231, 2828, 2405
Rint0.031
(sin θ/λ)max (Å−1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.110, 1.06
No. of reflections2828
No. of parameters188
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.19, −0.20

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
Cg is the centroid of the N1/C8–C12 ring.
D—H···AD—HH···AD···AD—H···A
N3—H3'···N10.837 (17)1.869 (17)2.602 (2)145.4 (15)
C14—H14C···S10.962.573.030 (2)109.4
C5—H5···Cgi0.932.663.536 (2)157
Symmetry code: (i) −x+2, −y+1, −z+1.
 

Acknowledgements

KJ thanks the UGC, New Delhi, for the award of a Teacher Fellowship. The authors also thank the STIC, CUSAT, Kochi-22, for providing the single-crystal XRD data.

References

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ISSN: 2056-9890
Volume 67| Part 12| December 2011| Page o3195
https://doi.org/10.1107/S1600536811045739
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