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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 68| Part 3| March 2012| Pages o836-o837
doi:10.1107/S1600536812007039

(2E)-2-(5-Bromo-2-hy­dr­oxy-3-meth­­oxy­benzyl­­idene)-N-cyclo­hexyl­hydrazine­carbo­thio­amide

Jinsa Mary Jacoba and M. R. Prathapachandra Kurupa*

aDepartment of Applied Chemistry, Cochin University of Science and Technology, Kochi 682 022, India
*Correspondence e-mail: mrp@cusat.ac.in

(Received 1 February 2012; accepted 16 February 2012; online 24 February 2012)

The title compound, C15H20BrN3O2S, crystallizes in the thio­amide form and adopts an E,E conformation with respect to the azomethine and hydrazinic bonds, respectively. The mol­ecules are paired through N—H⋯O and O—H⋯S hydrogen bonds, leading to the formation of centrosymmetric dimers in the crystal. These dimers are stacked along the a axis and are inter­connected through N—H⋯S hydrogen bonds to generate polymeric chains. The structure also features C—H⋯π interactions. An intra­molecular O—H⋯O bond is also present.

Related literature

For applications of hydrazinecarbothio­amide and its derivatives, see: Barber et al. (1992[Barber, D. E., Lu, Z., Richardson, T. & Crabtree, R. H. (1992). Inorg. Chem. 31, 4709-4711.]); Parrilha et al. (2011[Parrilha, G. L., Da Silva, J. G., Gouveia, L. F., Gasparoto, A. K., Dias, R. P., Rocha, W. R., Santos, D. A., Speziali, N. L. & Beraldo, H. (2011). Eur. J. Med. Chem. 46, 1473-1482.]). For the synthesis, see: Klayman et al. (1979[Klayman, D. L., Bartosevich, J. F., Griffin, T. S., Mason, C. J. & Scovill, J. P. (1979). J. Med. Chem. 22, 855-862.]). For related structures, see: Dutta et al. (1997[Dutta, S. K., McConville, D. B., Youngs, W. J. & Chaudhury, M. (1997). Inorg. Chem. 36, 2517-2522.]); Seena et al. (2006[Seena, E. B., BessyRaj, B. N., Kurup, M. R. P. & Suresh, E. (2006). J. Chem. Crystallogr. 36, 189-193.], 2008[Seena, E. B., Kurup, M. R. P. & Suresh, E. (2008). J. Chem. Crystallogr. 38, 93-96.]); Nisha et al. (2011[Nisha, K., Sithambaresan, M. & Kurup, M. R. P. (2011). Acta Cryst. E67, o3420.]). For standard bond-length data, see: Huheey et al. (1993[Huheey, J. E., Keiter, E. A. & Keiter, R. L. (1993). Inorganic Chemistry, Principles of Structure and Reactivity, 4th ed. New York: Harper Collins College Publishers.]); March (1992[March, J. (1992). Advanced Organic Chemistry, Reactions, Mechanisms and Structure, 4th ed. New York: Wiley.]). For ring puckering analysis, see: Cremer & Pople (1975[Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.]).

[Scheme 1]

Experimental

Crystal data

  • C15H20BrN3O2S

  • Mr = 386.31

  • Triclinic, [P \overline 1]

  • a = 5.7883 (4) Å

  • b = 11.412 (1) Å

  • c = 13.1312 (12) Å

  • α = 75.194 (4)°

  • β = 86.493 (3)°

  • γ = 83.489 (3)°

  • V = 832.72 (12) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 2.60 mm−1

  • T = 296 K

  • 0.30 × 0.25 × 0.25 mm
Data collection

  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2004[Bruker (2004). SADABS, APEX2, XPREP and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.509, Tmax = 0.562

  • 12149 measured reflections

  • 2923 independent reflections

  • 2521 reflections with I > 2σ(I)

  • Rint = 0.070
Refinement

  • R[F2 > 2σ(F2)] = 0.035

  • wR(F2) = 0.098

  • S = 1.12

  • 2923 reflections

  • 213 parameters

  • 3 restraints

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

  • Δρmax = 0.27 e Å−3

  • Δρmin = −0.41 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.
D—H⋯A D—H H⋯A D⋯A D—H⋯A
O2—H2′⋯O1 0.83 (2) 2.21 (4) 2.616 (3) 110 (3)
O2—H2′⋯S1i 0.83 (2) 2.43 (3) 3.142 (2) 145 (3)
N2—H2⋯O2i 0.84 (2) 2.25 (2) 2.959 (3) 142 (3)
N3—H3′⋯S1ii 0.84 (2) 2.81 (3) 3.483 (3) 138 (3)
C13—H13A⋯Cg1iii 0.97 2.71 3.664 (4) 168
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) x-1, y, z; (iii) x, y+1, z.

Data collection: APEX2 (Bruker, 2004[Bruker (2004). SADABS, APEX2, XPREP and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: APEX2 and SAINT (Bruker, 2004[Bruker (2004). SADABS, APEX2, XPREP and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT and XPREP (Bruker, 2004[Bruker (2004). SADABS, APEX2, XPREP and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SIR92 (Altomare et al., 1993[Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343-350.]); 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: 10.1107/S1600536812007039/fj2514sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812007039/fj2514Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812007039/fj2514Isup3.cml

checkCIF report


Comment top

The hydrazinecarbothioamides of aromatic aldehydes and ketones have been shown to possess a diverse range of biological activities (Parrilha et al., 2011) and catalytic activity (Barber et al., 1992). The pharmacological activity of hydrazinecarbothioamides of o-hydroxyaromatic aldehydes is correlated to their ability to form chelates with biologically important metal ions by bonding through O, N and S atoms (Dutta et al., 1997) and reductive capacity.

The title compound adopts an E configuration with respect to the C8—N2 bond (Fig. 1) similar to salicylaldehyde-N(4)-phenylthiosemicarbazone (Seena et al., 2008) but in contrast to 2-hydroxyacetophenone-N(4)-phenylthiosemicarbazone (Seena et al., 2006), where a Z configuration exists. This is confirmed by the N1—N2—C8—S1 torsion angle of -175.9 (2)°. Also E configuration is perceived about the azomethine bond [N2—N1—C7—C6 = -175.5 (3)°] (Nisha et al., 2011). Atom O1 lies cis to O2, with an O1—C4—C5—O2 torsion angle of 0.7 (4)°. This favours the intramolecular hydrogen bonding interaction between O1 and H attached to O2 atom.

The C8—S1 bond distance [1.685 (3) Å] is closer to C═S bond length [1.60 Å] than to C—S bond length [1.81 Å] (Huheey et al., 1993) which confirms the existence of the compound in the thioamido form in solid state. Also the C7—N1 bond distance [1.267 (4) Å] is appreciably close to that of a C═N double bond [1.28 Å] (March, 1992), confirming the azomethine bond formation.

The mean plane deviation calculations show that the molecule as a whole is non-planar. But the central hydrazinecarbothioamide group (C7/N1/N2/C8/S1/N3/C9) is almost planar with a maximum deviation from the mean plane of -0.054 (2) Å for atom N1. This is similar to that observed in salicylaldehyde-N(4)-phenyl thiosemicarbazone (Seena et al., 2008). The ring Cg1iii (comprising atoms C1—C6, with a maximum deviation of 0.005 (3) Å for C3) makes a dihedral angle of 18.90 (12)° with the hydrazinecarbothioamide moiety. Ring puckering analysis (Cremer & Pople, 1975) and least square plane calculations show that the cyclohexyl ring adopts a chair conformation (QT = 0.568 (4) Å) with the equatorial substitution at C9 for N3.

Fig. 2 shows the packing diagram of the title compound. The crystal packing involves one intramolecular and three intermolecular hydrogen bonds (Table 1). The intramolecular hydrogen bonding interaction, O2—H2'···O1 leads to the formation of a five membered ring comprising of atoms C4, C5, O2, H2' and O1 and facilitates almost planar geometry in part of the molecule. The intermolecular hydrogen bonds N2—H2···O2i and O2—H2'···S1i cause the pairing of molecules leading to the formation of centrosymmetric dimers in the crystal lattice. These dimers are stacked along the a axis and are interconnected through a third intermolecular hydrogen bond N3—H3'···S1ii to produce independent polymeric chains in the packing. Further stabilization is provided by C13—H13A···Cg1iii interaction.

Related literature top

For applications of hydrazinecarbothioamide and its derivatives, see: Barber et al. (1992); Parrilha et al. (2011). For the synthesis, see: Klayman et al. (1979). For related structures, see: Dutta et al. (1997); Seena et al. (2006, 2008); Nisha et al. (2011). For standard bond-length data, see: Huheey et al. (1993); March (1992). For ring puckering analysis, see: Cremer & Pople (1975).

Experimental top

The preparation of this compound involves a two step process (Klayman et al., 1979). In the first step, cyclohexyl isothiocyanate (15 mmol, 2 ml) in 15 ml methanol and hydrazine hydrate (90 mmol, 4.3 ml) in 15 ml methanol were mixed and the resulting solution was stirred for an hour. The white product, N(4)-cyclohexylthiosemicarbazide formed was filtered, washed with methanol and dried in vacuo. In the second step, a methanolic (20 ml) solution of 4-cyclohexylthiosemicarbazide (1 mmol, 0.1732 g) was added to a solution of 5-bromo-3-methoxysalicylaldehyde (1 mmol, 0.2310 g) in 15 ml methanol and the reaction mixture was refluxed for 2 h in acid medium. The product formed was filtered, washed with methanol and dried in vacuo. Suitable crystals were grown by slow evaporation of its solution in 1:1 mixture of DMF and methanol over 2 days.

Refinement top

All H atoms on C were placed in calculated positions, guided by difference maps, with C—H bond distances 0.93–0.97 Å. H atoms were assigned as Uiso=1.2Ueq (1.5 for Me). N2—H2, N3—H3' and O2—H2' H atoms were located from difference maps and restrained using DFIX instructions.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); 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 title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. A view of the unit cell along a axis.
(2E)-2-(5-Bromo-2-hydroxy-3-methoxybenzylidene)-N- cyclohexylhydrazinecarbothioamide top
Crystal data top
C15H20BrN3O2SZ = 2
Mr = 386.31F(000) = 396
Triclinic, P1Dx = 1.541 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.7883 (4) ÅCell parameters from 6391 reflections
b = 11.412 (1) Åθ = 2.7–27.9°
c = 13.1312 (12) ŵ = 2.60 mm−1
α = 75.194 (4)°T = 296 K
β = 86.493 (3)°Block, colourless
γ = 83.489 (3)°0.30 × 0.25 × 0.25 mm
V = 832.72 (12) Å3
Data collection top
Bruker APEXII CCD
diffractometer		2923 independent reflections
Radiation source: fine-focus sealed tube2521 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.070
Detector resolution: 8.33 pixels mm-1θmax = 25.0°, θmin = 2.7°
ω and ϕ scanh = −6→6
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		k = −13→13
Tmin = 0.509, Tmax = 0.562l = −15→15
12149 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)] = 0.035H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.098 w = 1/[σ2(Fo2) + (0.0194P)2 + 0.6265P]
where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max = 0.001
2923 reflectionsΔρmax = 0.27 e Å−3
213 parametersΔρmin = −0.41 e Å−3
3 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0142 (18)
Crystal data top
C15H20BrN3O2Sγ = 83.489 (3)°
Mr = 386.31V = 832.72 (12) Å3
Triclinic, P1Z = 2
a = 5.7883 (4) ÅMo Kα radiation
b = 11.412 (1) ŵ = 2.60 mm−1
c = 13.1312 (12) ÅT = 296 K
α = 75.194 (4)°0.30 × 0.25 × 0.25 mm
β = 86.493 (3)°
Data collection top
Bruker APEXII CCD
diffractometer		2923 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		2521 reflections with I > 2σ(I)
Tmin = 0.509, Tmax = 0.562Rint = 0.070
12149 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0353 restraints
wR(F2) = 0.098H atoms treated by a mixture of independent and constrained refinement
S = 1.12Δρmax = 0.27 e Å−3
2923 reflectionsΔρmin = −0.41 e Å−3
213 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
Br1−0.42662 (6)0.51878 (3)0.63154 (3)0.05382 (17)
S10.75115 (13)0.88705 (7)0.80347 (7)0.0448 (2)
O1−0.1322 (4)0.2029 (2)0.97526 (18)0.0520 (6)
O20.1901 (4)0.3362 (2)0.99890 (19)0.0471 (6)
N10.2789 (4)0.6672 (2)0.8130 (2)0.0377 (6)
N20.4703 (4)0.7170 (2)0.8316 (2)0.0398 (6)
N30.3358 (5)0.8967 (2)0.7247 (2)0.0407 (6)
C1−0.0696 (5)0.5340 (3)0.7638 (2)0.0384 (7)
H1−0.05230.60890.71670.046*
C2−0.2371 (5)0.4647 (3)0.7502 (2)0.0391 (7)
C3−0.2709 (5)0.3530 (3)0.8186 (2)0.0405 (7)
H3−0.38770.30810.80820.049*
C4−0.1268 (5)0.3105 (3)0.9024 (2)0.0379 (7)
C50.0459 (5)0.3795 (3)0.9177 (2)0.0358 (7)
C60.0749 (5)0.4910 (3)0.8492 (2)0.0360 (7)
C70.2600 (5)0.5588 (3)0.8659 (2)0.0370 (7)
H70.36810.52180.91690.044*
C80.5028 (5)0.8331 (3)0.7839 (2)0.0350 (7)
C90.3347 (5)1.0238 (3)0.6669 (2)0.0387 (7)
H90.49491.03990.64390.046*
C100.1921 (7)1.0438 (3)0.5704 (3)0.0517 (9)
H10A0.03691.02060.59180.062*
H10B0.26260.99220.52620.062*
C110.1758 (8)1.1755 (4)0.5079 (3)0.0687 (11)
H11A0.32861.19570.47880.082*
H11B0.07341.18660.44960.082*
C120.0842 (8)1.2596 (4)0.5760 (4)0.0710 (12)
H12A−0.07471.24510.59920.085*
H12B0.08381.34350.53510.085*
C130.2320 (7)1.2397 (3)0.6707 (3)0.0602 (10)
H13A0.16751.29300.71450.072*
H13B0.38821.26010.64760.072*
C140.2423 (6)1.1085 (3)0.7344 (3)0.0481 (8)
H14A0.34231.09690.79360.058*
H14B0.08781.08980.76200.058*
C15−0.2900 (7)0.1217 (3)0.9629 (3)0.0551 (9)
H15A−0.44660.15770.96930.083*
H15B−0.26590.04681.01650.083*
H15C−0.26430.10550.89470.083*
H3'0.211 (4)0.866 (3)0.723 (3)0.041 (9)*
H20.576 (5)0.672 (3)0.868 (2)0.040 (9)*
H2'0.144 (6)0.277 (2)1.042 (2)0.055 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0582 (3)0.0553 (3)0.0480 (2)−0.01859 (17)−0.01714 (16)−0.00386 (17)
S10.0339 (4)0.0390 (5)0.0610 (5)−0.0161 (3)−0.0082 (4)−0.0048 (4)
O10.0655 (15)0.0405 (13)0.0502 (14)−0.0291 (11)−0.0122 (11)0.0010 (11)
O20.0522 (14)0.0394 (13)0.0484 (14)−0.0181 (11)−0.0168 (11)0.0008 (11)
N10.0335 (13)0.0323 (14)0.0491 (15)−0.0107 (10)−0.0055 (11)−0.0096 (12)
N20.0335 (14)0.0287 (14)0.0568 (17)−0.0083 (11)−0.0134 (12)−0.0050 (12)
N30.0372 (15)0.0336 (14)0.0506 (16)−0.0158 (11)−0.0100 (12)−0.0019 (12)
C10.0387 (16)0.0334 (16)0.0433 (17)−0.0078 (13)−0.0013 (13)−0.0081 (14)
C20.0411 (17)0.0388 (17)0.0390 (17)−0.0107 (13)−0.0054 (13)−0.0088 (14)
C30.0400 (17)0.0419 (18)0.0435 (18)−0.0168 (13)−0.0023 (13)−0.0123 (14)
C40.0413 (17)0.0338 (16)0.0396 (17)−0.0147 (13)0.0013 (13)−0.0068 (13)
C50.0368 (16)0.0323 (16)0.0402 (17)−0.0090 (12)−0.0027 (13)−0.0097 (13)
C60.0351 (16)0.0311 (16)0.0443 (17)−0.0081 (12)−0.0020 (13)−0.0117 (13)
C70.0358 (16)0.0312 (16)0.0451 (18)−0.0089 (12)−0.0047 (13)−0.0083 (14)
C80.0333 (15)0.0342 (16)0.0393 (17)−0.0099 (12)0.0014 (12)−0.0103 (13)
C90.0399 (16)0.0325 (16)0.0429 (17)−0.0129 (12)−0.0049 (13)−0.0030 (13)
C100.066 (2)0.044 (2)0.0432 (19)−0.0136 (16)−0.0122 (16)−0.0028 (15)
C110.094 (3)0.050 (2)0.054 (2)−0.014 (2)−0.016 (2)0.0069 (19)
C120.067 (3)0.044 (2)0.086 (3)−0.0003 (18)0.001 (2)0.010 (2)
C130.071 (3)0.0349 (19)0.075 (3)−0.0115 (17)0.014 (2)−0.0166 (18)
C140.057 (2)0.0419 (19)0.048 (2)−0.0148 (15)0.0006 (16)−0.0106 (15)
C150.064 (2)0.044 (2)0.060 (2)−0.0312 (17)−0.0025 (18)−0.0071 (17)
Geometric parameters (Å, º) top
Br1—C21.891 (3)C7—H70.9300
S1—C81.685 (3)C9—C141.506 (4)
O1—C41.352 (4)C9—C101.508 (4)
O1—C151.417 (4)C9—H90.9800
O2—C51.351 (4)C10—C111.513 (5)
O2—H2'0.826 (19)C10—H10A0.9700
N1—C71.267 (4)C10—H10B0.9700
N1—N21.363 (3)C11—C121.507 (6)
N2—C81.342 (4)C11—H11A0.9700
N2—H20.840 (18)C11—H11B0.9700
N3—C81.308 (4)C12—C131.507 (6)
N3—C91.454 (4)C12—H12A0.9700
N3—H3'0.842 (18)C12—H12B0.9700
C1—C21.366 (4)C13—C141.513 (5)
C1—C61.392 (4)C13—H13A0.9700
C1—H10.9300C13—H13B0.9700
C2—C31.385 (4)C14—H14A0.9700
C3—C41.374 (4)C14—H14B0.9700
C3—H30.9300C15—H15A0.9600
C4—C51.394 (4)C15—H15B0.9600
C5—C61.379 (4)C15—H15C0.9600
C6—C71.449 (4)
C4—O1—C15118.5 (3)C10—C9—H9108.5
C5—O2—H2'113 (3)C9—C10—C11111.4 (3)
C7—N1—N2115.6 (3)C9—C10—H10A109.3
C8—N2—N1120.9 (2)C11—C10—H10A109.3
C8—N2—H2120 (2)C9—C10—H10B109.3
N1—N2—H2119 (2)C11—C10—H10B109.3
C8—N3—C9125.6 (2)H10A—C10—H10B108.0
C8—N3—H3'119 (2)C12—C11—C10111.1 (3)
C9—N3—H3'115 (2)C12—C11—H11A109.4
C2—C1—C6119.1 (3)C10—C11—H11A109.4
C2—C1—H1120.4C12—C11—H11B109.4
C6—C1—H1120.4C10—C11—H11B109.4
C1—C2—C3122.6 (3)H11A—C11—H11B108.0
C1—C2—Br1119.6 (2)C11—C12—C13110.8 (3)
C3—C2—Br1117.8 (2)C11—C12—H12A109.5
C4—C3—C2118.1 (3)C13—C12—H12A109.5
C4—C3—H3120.9C11—C12—H12B109.5
C2—C3—H3120.9C13—C12—H12B109.5
O1—C4—C3126.0 (3)H12A—C12—H12B108.1
O1—C4—C5113.8 (3)C12—C13—C14110.8 (3)
C3—C4—C5120.2 (3)C12—C13—H13A109.5
O2—C5—C6119.3 (3)C14—C13—H13A109.5
O2—C5—C4120.0 (3)C12—C13—H13B109.5
C6—C5—C4120.7 (3)C14—C13—H13B109.5
C5—C6—C1119.2 (3)H13A—C13—H13B108.1
C5—C6—C7119.2 (3)C9—C14—C13110.4 (3)
C1—C6—C7121.5 (3)C9—C14—H14A109.6
N1—C7—C6121.9 (3)C13—C14—H14A109.6
N1—C7—H7119.1C9—C14—H14B109.6
C6—C7—H7119.1C13—C14—H14B109.6
N3—C8—N2116.6 (3)H14A—C14—H14B108.1
N3—C8—S1124.5 (2)O1—C15—H15A109.5
N2—C8—S1118.8 (2)O1—C15—H15B109.5
N3—C9—C14111.7 (3)H15A—C15—H15B109.5
N3—C9—C10108.2 (2)O1—C15—H15C109.5
C14—C9—C10111.4 (3)H15A—C15—H15C109.5
N3—C9—H9108.5H15B—C15—H15C109.5
C14—C9—H9108.5
C7—N1—N2—C8−176.8 (3)C2—C1—C6—C7178.1 (3)
C6—C1—C2—C30.5 (5)N2—N1—C7—C6−175.5 (3)
C6—C1—C2—Br1−177.5 (2)C5—C6—C7—N1−172.0 (3)
C1—C2—C3—C4−1.0 (5)C1—C6—C7—N110.1 (5)
Br1—C2—C3—C4177.1 (2)C9—N3—C8—N2179.5 (3)
C15—O1—C4—C33.8 (5)C9—N3—C8—S1−0.6 (5)
C15—O1—C4—C5−175.5 (3)N1—N2—C8—N34.1 (4)
C2—C3—C4—O1−178.6 (3)N1—N2—C8—S1−175.9 (2)
C2—C3—C4—C50.7 (5)C8—N3—C9—C14−86.2 (4)
O1—C4—C5—O20.7 (4)C8—N3—C9—C10150.8 (3)
C3—C4—C5—O2−178.7 (3)N3—C9—C10—C11178.1 (3)
O1—C4—C5—C6179.4 (3)C14—C9—C10—C1154.9 (4)
C3—C4—C5—C60.0 (5)C9—C10—C11—C12−54.6 (5)
O2—C5—C6—C1178.2 (3)C10—C11—C12—C1355.9 (5)
C4—C5—C6—C1−0.4 (5)C11—C12—C13—C14−57.4 (4)
O2—C5—C6—C70.2 (4)N3—C9—C14—C13−177.2 (3)
C4—C5—C6—C7−178.4 (3)C10—C9—C14—C13−56.0 (4)
C2—C1—C6—C50.2 (5)C12—C13—C14—C957.3 (4)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C1-C6 ring.
D—H···AD—HH···AD···AD—H···A
O2—H2′···O10.83 (2)2.21 (4)2.616 (3)110 (3)
O2—H2′···S1i0.83 (2)2.43 (3)3.142 (2)145 (3)
N2—H2···O2i0.84 (2)2.25 (2)2.959 (3)142 (3)
N3—H3′···S1ii0.84 (2)2.81 (3)3.483 (3)138 (3)
C13—H13A···Cg1iii0.972.713.664 (4)168
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x−1, y, z; (iii) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC15H20BrN3O2S
Mr386.31
Crystal system, space groupTriclinic, P1
Temperature (K)296
a, b, c (Å)5.7883 (4), 11.412 (1), 13.1312 (12)
α, β, γ (°)75.194 (4), 86.493 (3), 83.489 (3)
V (Å3)832.72 (12)
Z2
Radiation typeMo Kα
µ (mm−1)2.60
Crystal size (mm)0.30 × 0.25 × 0.25
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2004)
Tmin, Tmax0.509, 0.562
No. of measured, independent and
observed [I > 2σ(I)] reflections		12149, 2923, 2521
Rint0.070
(sin θ/λ)max (Å−1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.098, 1.12
No. of reflections2923
No. of parameters213
No. of restraints3
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.27, −0.41

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SIR92 (Altomare et al., 1993), SHELXTL (Sheldrick, 2008) and ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C1-C6 ring.
D—H···AD—HH···AD···AD—H···A
O2—H2'···O10.826 (19)2.21 (4)2.616 (3)110 (3)
O2—H2'···S1i0.826 (19)2.43 (3)3.142 (2)145 (3)
N2—H2···O2i0.840 (18)2.25 (2)2.959 (3)142 (3)
N3—H3'···S1ii0.842 (18)2.81 (3)3.483 (3)138 (3)
C13—H13A···Cg1iii0.972.713.664 (4)168
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x−1, y, z; (iii) x, y+1, z.
 

Acknowledgements

The authors are grateful to the Sophisticated Analytical Instruments Facility, Cochin University of Science and Technology, Kochi-22, India, for providing the single-crystal X-ray diffraction data. JMJ thanks the Council of Scientific and Industrial Research, New Delhi, India, for financial support in the form of a Junior Research Fellowship.

References

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ISSN: 2056-9890
Volume 68| Part 3| March 2012| Pages o836-o837
doi:10.1107/S1600536812007039
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